CA1317500C - Processing method for silver halide color photographic light-sensitive material and color developer used therein - Google Patents
Processing method for silver halide color photographic light-sensitive material and color developer used thereinInfo
- Publication number
- CA1317500C CA1317500C CA000556170A CA556170A CA1317500C CA 1317500 C CA1317500 C CA 1317500C CA 000556170 A CA000556170 A CA 000556170A CA 556170 A CA556170 A CA 556170A CA 1317500 C CA1317500 C CA 1317500C
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- Prior art keywords
- group
- silver halide
- sensitive material
- atom
- alkyl group
- Prior art date
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/407—Development processes or agents therefor
Abstract
ABSTRACT OF DISCLOSURE
The present inventions relate to a processing method for processing, with a developing time of not more than 180 sec-onds, a silver halide color photographic light-sensitive mate-rial comprising a support, provided thereon, with at least one silver halide emulsion layer, and at least one emulsion layer containing silver iodo-bromide with not less than 0.5 mole% of silver iodine, in particular to an active processing method wherein, a light-sensitive material B not only contain-ing silver iodo-bromide with an iodine content of not less than 0.5 mole% but also a magenta coupler and providing a maximum magenta density, after exposed, and being capable of only satisfying the maximum magenta dye density M of M<2.0 if exposed under specific conditions and then subjected to color developing of a duration of three minutes 15 seconds at 38°C
with a specific developer solution, is capable of offering a maximum magenta density satisfying M?22.0, when the light-sensitive material is exposed under the exposure conditions and subjected to color developing with a duration of not more than 2.5 minutes, whereby excellent image in terms of image quality is resulted.
The present inventions relate to a processing method for processing, with a developing time of not more than 180 sec-onds, a silver halide color photographic light-sensitive mate-rial comprising a support, provided thereon, with at least one silver halide emulsion layer, and at least one emulsion layer containing silver iodo-bromide with not less than 0.5 mole% of silver iodine, in particular to an active processing method wherein, a light-sensitive material B not only contain-ing silver iodo-bromide with an iodine content of not less than 0.5 mole% but also a magenta coupler and providing a maximum magenta density, after exposed, and being capable of only satisfying the maximum magenta dye density M of M<2.0 if exposed under specific conditions and then subjected to color developing of a duration of three minutes 15 seconds at 38°C
with a specific developer solution, is capable of offering a maximum magenta density satisfying M?22.0, when the light-sensitive material is exposed under the exposure conditions and subjected to color developing with a duration of not more than 2.5 minutes, whereby excellent image in terms of image quality is resulted.
Description
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1 31 7~0U
PROCESSING METHOD FOR SILVER HALIDE COLOR PHOTOGRAPHIC
LIGHT-SENSITIVE MATERIAL AND COLOR DEVELOPER USED THEREIN
FIELD OF THE INVENTION
The present invention relates to a processing method for a silver halide color photographic light-sensitive material and a color developer used therein, in particular to a processing method for a silver halide color photographic light-sensitive material providing a dye image with excellent graininess and a color developer used to em~odying this method.
BACKGROUND OF THE INVENTION
Recently, miniaturization of a silver halide color photo-graphc light-sensitive material has been in progress. More specifically, to miniature a camera for better portability, miniaturization of an image size on a film is in progress. It is, however, well known such an arrangement incurs a deterio-rated printed image quality. More specifically, a smaller image size in a color photographic light sensitive-material necessitates a greater enlargemen~ ratio for preparing a specific size of final print, and such a printed image accord-ingly has poor graininess as well as poor sharpness. There-fore, it is mandatory, in preparing an excellent print even with a miniaturized image size on a film, to improve the graininess, resolution and sharpness of a film.
As the method to improve graininess, among these re~uire-ments for improved silver halide color photographic light-sensitive materials, the following are available: a method, as described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I.
Publication) No. 62454 1980 published May 10, 1980, for using a rapid-reacting type coupler; a method, as described in the Theory of the Photographic Process, 4th Ed., pp. 620 - 621, by T.H. James, increasing the number of silver halide particles per unit of photographic material; a method, as described in British Patent No. 2,080,640A, for using a non-diffusion type coupler for forming a diffusion type dye which emit an appropriately small amount of dye upon reaction with an oxidation product of color developing agent; a method, as described in Japanese Patent O.P.I. Publication No. 128443/1985 published July 9, 1985, for increasing a ratio of silver iodide content to more than 8 mol~; other improvement methods as described in Japanese Patent O.P.I. Publications No.
191036/1984, No. 3682/1985, No. 128440/1985 and the like respectively published October 30, 1984, January 10, 1985 and July 9, 1985; a technique, as described in Japanese Patent Examined Publication No. 15495/1~74, Japanese Patent O.P.I.
Publications No. 7230/1978, No. 155539/1982 and the like respectively publlshed ~pril 15, 1974, January 23, 1978 and September 25, 1982 wherein an improvement is achieved by modifying the constitution of structural layers in a silver halide color photographic liqht-sensitive material.
Though the above-mentioned methods for improving a light-sensitive material positively improves graininess, the degree of improvement is not yet satisfactory. Insufficience in graininess poses an obstacle against common use of a light-sensitive material have an extremely small format for example in the case of so-called "disk-film", and therefore has neces-sitated improvement.
In Chiba University, Engineering Department, Research-Report Vol. 33 (1), Vol. 63 in whole number, ~1980), pp. 45 -48, is described the technique of "Image improvement of color negative film by rapid processing" by Arai et. al. In this report, it is mentioned that two layers i.e. cyan and magenta layers which are separated from a suppo:r~_ are provided with approximately 20 to 30% increase in image information by means of highly active color developer as well as high-temperature rapid processing, and results in increase in sharpness, at a cost of deteriorated graininess in an image. This has been a theory established in the photographic art.
The present invention is intended to solve the above dis-advantage. Therefore, the object of the invention is to a B
1 3 1 75~
rapid processing method for a silver halide color photographic light-sensitive material providing a dye image with excellent sharpness and graininess, as well as a color developer used to embodying this method.
DISCLOSURE OF THE INVENTION
The inventors have continued devoted research in order to attain the above object, and found that such a processing method compries with the above object. That is a processing method for processing a silver halide color photographic light-sensitive material comprising a support, provided there-on, at least one silver halide emulsion layer, and at least one silver halide contains silver iodo-bromide with not less than 0.4 mol% iodine, wherein the development time is not more than 180 seconds and the method satisfies the following criteria.
The processing method of the invention is characterized in that an image defined below is obtained when light-sensi-tive material B specified below containing silver iodo-bromide with iodine content of not less than 0.5 mol% as well as magenta coupler is exposed under the following conditions C
and then subjected to color developing with a duration of 3 min. 15 sec. by using developer A specified below, with an assumption that the maximum magenta density of the light sen-sitive material satisfies the expression M < 2Ø
~ 5 ~ 1 317~0 In other words, it is a processing method, for a silver halide color photographic light-sensitive material, according to the first invention in the present application that a dye image having maximum magenta density M < 2.0 is available from the light-sensitive material B, of which magenta dye image has maximum density of M > 2, when the light-sensitive material B
is exposed under exposure conditions identical with the above and then the exposed material is subjected to color developing with a duration of shorter than 2 min.
Developer A used for specifying light-sensitive material B is as follows:
Developer A
_ Potassium carbonate 37.5 g Sodium sulfite 4.25 g Potassium iodide 2 g Sodium bromide 1.3 g Hydroxylamine sulfate 2.0 g 3-methyl-4-amino-N-ethyl-(~-hydroxyethyl)-aniline sulfate 4.75 g Water is added to the above components to prepare one liter solution, which is adjusted to pH 10.0 with 50~ sulfuric acid.
The exposure conditions C mentioned above are as follows:
using a tungsten light source and filter, a color temperature is adjusted to 4800K, in order ro provide 3.2 CMS wedge ex-- 6 ~ 1 3 1 7~
posure light.
The above processing method of the invention may be de-fined as a processing method which is capable of forming an image having a density higher than a color density, by sub-jecting a light-sensitive material B, which only produces an image of lower color density when developed under a specific condition, to color developing with a duration of not more than 2.5 min.
The above developer A and the developing conditions C
used to specify the light-sensitive material B are those con-ventionally used in the art. In contrast, the processing method of the invention, which is capable of attaining magenta coloration of M ~ 2.0 when the light-sensitive material B
otherwise only having magenta coloration of M 2 2.0, may be called a process performed under an unconventionally active condition.
It is an unexpected fact even for the inventors that the above ob]ect. i.e. improved graininess is attained by a rapid and active process of which color developing time is unconven-tionally short, not more than 180 seconds.
The operation of the invention is yet to be known. How-ever, the estimated reason is that performing a color develop-ing process under such an active condition as of the invention somehow prevents dye formed around silver halide particles from being dispersed, and, resultingly, an image of excellent ~ 7 - l 3 1 75~0 graininess is obtained.
The second invention in the present application is char-acterized by a developing temperature of higher than 40C in performing the above color developing process. The developing temperature of not lower than 40C ensures a rapid and active developing process.
The third invention in the present application is that the concentration of developing agent in developer solution is not lower than 1.5 x 10 1 mol/liter in performing the color developing process. Such a high concentration of color devel-oping agent ensures a rapid and active developing process.
The fourth invention in the present application is the developing time ranges from 20 to 150 seconds in performing the color developing process.
The fifth invention in the present application is the membrane swelling rate in relation to the light-sensitive material in the course of the color developing process is not more than 20 seconds.
This feature enables image quality, in particular, graininess.
In embodying the respective inventions in the present application, incorporating a combination composed of a com-pound represented by any of general formulas [R-I] through [R-IV] described layer, a compound represented by any of gen-eral formulas [A-I] through [A-VI], and at least one compound - 8 - t317500 selected from polymers individually having a pyrolidone nucle-us in the molecular structure, into a color developer solution is capable of effectively suppressing fog in a non-exposure portion, adjust a tone properly, and further improves image quality. For this reason, the above compounds are favorably used in embodying the above respective inventions.
The sixth invention in the present application is the use of above processing method for a silver halide color photo-graphic light-sensitive material comprising a support, pro-vided thereon, at least one silver halide emulsion layer con-taining a coupler represented by the following general formula lM-I], wherein at least one emulsion layer contains silver iodo-bromide.
[M-I]
X m R m ~ "
N N ~
zm represents a plurality of non-metal atoms necessary for forming a nitrogen heterocycle. The heterocycle formed by zm may have a substituent.
xm represents a hydrogen atom, or a group capable of split off upon reaction with an oxidation production of a color developing agent.
9 1 31 7~00 Rm represents a hydrogen atom, or a substituent.
The seventh invention in the present application is use of the above-mentioned processing method in treating a silver halide color photographic light-sensitive material comprising a support, provided thereon, at least one silver halide emul-sion layer containing a coupler represented by the following general formula O[C-I], wherein at least one emulsion layer contains silver iodo-bromide.
General formula [C-I]
f H
Rc 3 ~/~ NHCO(NH)m t Rc~
RczCONH ~ ~
In this formula, RCl and RC2 independently represent an alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group. Each of these groups may have a substi-tuent. Rc3 represents a hydrogen atom, halogen atom, alkyl group or alkoxy group. Such an alkyl or alkoxy group may have a substituent. Such a substituent may be a ring which RC2 and Rc3 combinedly form. X represents a hydrogen atom, or a group capable of split off upon reaction with an oxidation product of a color developing agent. mc represents O or 1.
The eighth invention in the present application is a lo - I 31 7500 color developer for a silver halide color photographic light-sensitive material, containing at least one compound selected from the following group ~A] and subjected to at least one means selected from the following group lB].
Group [A]
(A-l) Compounds represented by the following general for-mula [R-I]
General formula [R-I]
. ' / ( X r I ) n r ;Z r '.
( X r ) m r ~ -- X r Z
"'"' C /
In this formula, X'r and X'rl independently represent a halogen atom, alkyl group, aryl group, amino group, hydroxy group, nitro group, carboxyl group or sulfonyl group. X'r2 represents a hydrogen atom, alkyl group, aryl group, or a double-bond capable of forming a ring. Zr represents a plu-rality of atoms comprising a carbon atom, oxygen atom, nitro-gen atom and sulfur atom, being necessary for forming a ring.
nr and mr independently represent 0, 1, 2 or 3.
(A-2) Compounds represented by the following general for-mula [R-II]
7 3 1 ~
General formula [R-II]
Y r a -- Y r I
Y r 3 Y r Z
In this formula, Yra, Rrl, Yr2 and Yr3 independently re-present a hydrogen atom, halogen atom, alkyl group, amino group, hydroxy group, nitro group, carboxyl group or sulfonyl group.
(A-3) Compounds represented by the following general for-mula [R-III]
General formula [R-III]
, " Y 4 ,' ~1) Y r s --7 r x 2 x r ~
In this formula, Tr represents a nitrogen atom, or phos-phor atom. Xr2 and Xr3 independently represent a hydrogen atom, alkyl group, aryl group, or halogen atom. Yr4 and Yrs independently represent an alkyl group, or aryl group. Yr4 and Yrs may jointly undergo ring closure to form a hetero-cycle.
(A-4) Compounds represented by the following general for-mula [R-IV]
General formula [R-IV]
f Rsl "-- C~
iX s Y s R 2 0 / \ Z ~ j 0 R 3 Rss In Formula [R-IV], Rsl represents -OH, -oRs4 or -N~
Rs4 and Rss independently represent an alkyl group. The alkyl group represented either by Rs 4 or Rss may have a substituent (for example, an aryl group such as a hydroxyl group and phenyl group) and is typified by a methyl group, ethyl group, propyl group, butyl group, benzyl group, ~-hydroxyethyl group, dodecyl group or the like.
Rs 2 and Rs 3 independently represent -H or - C - Rs 6, Rs6 represents an alkyl group or aryl group. The examples of the alkyl group represented by Rs 6 include a long-chained alkyl group such an undecyl group.
Xs and Ys respectively represent a carbon atom and a hy-drogen atom, each of which forms a six-membered ring together with other plurality of atoms. Zs represents -N= or -CH=.
If Zs is -N=, a compound of the invention represented by - 13 ~ l 3 1 750~
general formula ~R-IV] is typically a citradinic derivative.
If Z represents -C=, a compound of the invention represented by general formula [R-IV] is typically a bezoic derivative.
The six-membered ring within this compound may have a substi-tuent such as a halogen atom.
Zs is favorably -N=.
(A-5) Polymer or copolymer, which has a pyrolidone nucle-us within the molecular structure (A-6) Polyethylene glycol derivative [Group B]
(B-I) Concentration of p-phenylenediamine developing agent within color developer solution is higher than l.S x 10~
mol/liter (B-II) pH of color developer solution is greater than 10.4 (B-III) Concentration of sulfite in color developer solu-tion is less than 1.5 x 10~l mol/liter (B-IV) Concentration of bromide in color developer solu-tion is less than 0.8 x 10~l mol/liter (B-V) Color developer contains at least one of compound selected from those represented by the following general for-mulas [A-I] through [A-VI]
General formula [A-I]
X ~ ( C ~I Z ~ n a l t X a Z - ( C 1I z~) n a Z )~ X a :1 - ( CHz ~n a ~ X a 4 In this formula, Xa2 and Xa3 indepenaently represent a sulfur atom or oxygen atom. Xal and Xa4 independently repre-sent a SH group or OH group. na1, naz~ na3 and mal indepen-dently represent an integer ranging from 0 to 500, whereby at least one of nal, na2 and na3 is an integer greater than 0.
Additionally, at least one of Xa1, Xa2, Xa3, and Xa4 is a sulfur atom.
General formula [A-II]
Qa z Aa 3 A a I ~-- N <
A a 4 R a 2 In this formula, Ral and Ra2 independently represent a hydrogen atom; or an alkyl group such as a methyl group, ethyl group or propyl group; or a heterocyclic group which is capa-ble of forming a ring, in~ol~ing an oxygen or nitrogen atom, together with Ral and Ra2. Aa2, Aa3 and Aa4 independently represent a hydrogen atom; or an alkyl group such as a methyl or ethyl group; or a halogen atom such as a chlorine, fluo-rine, or bromine atom. Aa1 repreesnts a hydroxy group or ~ Ra~
-N~ . Additionally, Ra3 and Ra4 independently represent a Ra"
hydrogen atom, or an alkyl group having 1 to 3 carbon atoms.
- 15 - 1 3 1 7~0~
General formula [A-III]
Ra 1.
I
Ras ~iaz Ras Xas e Ra 7 In this formula, Ras, Ra6, Ra~ and Ra8 independently re-present a hydrogen atom, alkyl group, aralkyl group; or a sub-stituted or unsubstituted aryl group. Aa2 represents a nitro-gen or phosphor atom. Ra8 represent a substituted or unsub-stituted alkylene group. Ras and RaB may form a ring, or in-dependently be substituted or unsubstituted pyridinium group.
XaS represents an anion group such as a halogen atom, OH, sulfuric group or nitric group.
General formula [A-IV]
Ra I o / I
X N - (CHz)na4 - (C)ma2 Y a (Ra 9) ~ a na I I
In this formula, Ya represents a hydrogen atom, hydroxy /Ra 12 group or -N . Rag, Ra1D, Ra11, Ra12 and Ra13 independ-Ral3 ently represent a hydrogen atom; or a substituted or unsub-stituted group, having 1 to 3 carbon atoms, such as an alkyl group, carbamoyl group, acetyl group and amino group. X re-presents an oxygen atom, sulfur atom or N-Ral4. At the same time, Rall represents a hydrogen atom, or a substituted or un-substituted alkyl group having 1 to 3 carbon atoms. la, ma2 na4 independently represent an integer 0, 1, 2 or 3.
General formula [A-V]
Rb, > N (A b ) n b O R b 3 n b 2 In this formula Rbl and Rb2 independently represent a hydrogen atom, alkyl group, alkoxy group, aryl group; or a nitrogen-containing heterocycle which may be formed by Rb1 and Rb2; or a nitrogen-containing heterocycle which may be formed by Rbl and Ab, or by Rb2 and Ab. Rb3 represents an alkyl group. Ab represents an alkylene group. nb represents an integer ranging from O to 6.
General formula [A-VI]
~ Rb 2 Rb I '--N ~
Rb 3 In this formula, Rbl' represents a hydroxy alkyl group having 2 to 6 carbon atoms. Rb2' and Rb3' independently re-present a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms; or a hydroxy alkyl group or benzyl group each having 2 to 6 carbon atoms; or -Cnb', H2nb', -N . In ~ Zb - 17 - t317500 these formulas, nb' represents an integer ranging from 1 to 6; Xb and Zb independently represent a hydrogen atom, an alkyl group having 1 to 6 carbona toms or a hydroxy alkyl group hav-ing 2 to 6 carbon atoms.
The respective inventions are described in detail below.
The first inventi,on is hereinunder described.
The first invention in the present application is a proc-essing method for a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer disposed on a support, wherein at least one emulsion layer contains silver iodo-bromide having more than 0.5 mol%
of iodine content.
A light-sensitive material subject to the process of the invention is arbitrarily selected from those satisfying the previously specified conditions.
Light-sensitive material B, which is a standard sample for specifying the method of the invention, contains not only silver iodo-bromide with more than 0.5 mol% of iodine content, but a magenta coupler. This light-sensitive material B, when exposed and then subjected to a color developing process under the conditions of 33C and three minutes 15 seconds using the previously specified developer A, provides maximum magenta density M of M ~ 2Ø The processing method of the invention is capable of produce a dye image of which maximum magenta density M available from the light-sensitive material B satis-- 18 - l 31 7500 fies M > 2.0, when the light-sensitive material in compliance with the above conditions is subjected to color developing 2.5 minutes after the exposure in compliance with the above speci-fied conditions. (As mentioned previously, light-sensitive material B is a standard sample for specifying the processing method. Correspondingly, any color light-sensitive material treated by the method of the invention is arbitrarily used, as far as it contains the above-mentioned type of silver iodo-bromide.) Light-sensitive material B, i.e. a standard sample for specifying the processing method, may contain arbitrary magenta coupler, and have an arbitrary silver halide composi-tion, as far as the composition comprises silver iodo-bromide with not less than 0.5 mol~ of iodine. Any processing method is included in the scope of the invention, as far as the method is capable of satlsfying M 2 2.0 when subjecting light-sensi-tive material B having undergone exposure under a specific exposure condition to processing with a duration not longer than 2.5 minutes and if the same light-sensitive material hav-ing undergone exposure under the same specific exposure condi-tion produces a magenta dye image with M < 2.0 when treated in the above specified conditions using the above developer A.
The exposure condition for exposing light-sensitive mate-rial B used to specify the processing method is as follows;
using a tungsten source, color temperature is adjusted to 4800K with a filter, in order to provide 3.2 CMS wedge ex-posure.
An arbitrary magenta coupler is contained in light-sen-sitive materia] B. For example, light-sensitive material B
may contain, as a coupler, a compound of general formula lM-I].
A preferred embodiment of the processing method of the invention is a method being capable of forming a dye image of which magenta fog density in the non-exposure portion is less than 0.5, if light-sensitive material B is subjected to the above-mentioned processing with a duration of less than 2.5 minutes.
The first invention in the present application is further described in detail below.
A silver halide color photographic light-sensitive mate-rial used in the processing according to the invention con-tains, in at least one silver halide emulsion layer, silver iodo-bromide with not less than 0.5 mol% of silver iodide.
However, the preferred light-sensitive material in embodying the invention has not less than 1.0 mol%, in particular, 3 to 10 mol%, or more favorably, 5 to 8 mol% of silver iodide con-tent.
The scope of silver halide particles including the above-mentioned silver iodide is not specifically limited. However, in embodying the invention, the preferred silver halide par-ticles are core/shell type silver halide particles, and tabular silver halide particles.
The core/shell type silver halide particles, and tabular silver halide particles respectively having silver iodide con-tent of not less than 0.5 mol% are advantageously used in em-bodying the invention. These types of silver halide particles are hereinunder described in detail.
With the core/shell type silver halide emulsion particles advantageously used in embodying the invention, individual particles have a particle structure comprising more than two layers respectively having a different silver iodide content.
The preferred silver halide particles are silver iodo-bromide particles, wherein a layer having maximum silver iodide con-tent (referred to as shell) is any layer other than the outer-most layer (referred to as core). The preferred silver iodide content in the internal layer (core), which has the maximum silver iodide content, is 6 to 40 mol~, in particular, 10 to 20 mol%. The preferred silver iodide content in the outermost layer (shell) is less than 6 mol%, in particular, 0.1 to 4.0 mol%.
When using the core/shell type silver halide particles, the preferred proportion of shell portions is 10 to 80%, in particular, 15 to 70%, more specifically, 20 to 60%.
The preferred proportion of core portions among total particles is lO to 80%, in particular, 20 to 50%.
According to the invention, if the silver halide parti - 21 ~ l 3 1 7 500 cles are core/shell type particles, individually comprising a core portion having a higher silver iodide content and a shell portion having a lower silver iodide content, there may be a clear-cut border in terms of difference in iodine contents, or, otherwise, the content may continuously change from the core to shell portion. Additionally, such particles individ-ually having an intermediate layer between the core and shell portions, whereby the silver iodide content of the intermedi-ate layer is virtually an average of those of the core and shell portions.
When using core/shell type silver halide particles having the above-mentioned intermediate layers, the volume of inter-mediate layers is 5 to 60%, and, favorably, 20 to 55% of the total volume of all the particles. The difference in silver iodide content between the shell and the intermediate layer, as well as the difference in the intermediate layer and the core, should be respectively not less than 3 mol%. The dif-ference in silver iodide content between the shell and the core should be favorably not less than 6 mol~.
When using the core/shell type silver halide particles in embodying the invention, the preferred average silver iodide content of such aprticles should be ~ to 20 mol%, in particu-lar, 5 to 15 mol~. Also, such particles may contain silver chloride, as far as the amount of silver chloride does not deteriorate the effect of the invention.
- 22 ~ l 3 1 7 50 0 The core/shell type emulsion used for a light-sensitive material subjected to the processing method of the invention may be prepared in compliance with known methods disclosed, for example, in Japanese Patent O.P.I. Publications No.
177535/1984, No. 138538/1985, No. 52238/1984, No. 143331/1985, No. 35276/1985 and No. 258536/1985.
When preparing core/shell type silver halide emulsion starting from seed particles, as in a method described in an example in Japanese Patent o.P.I. Publication No. 138538/1985, some particles may have, in the respective center portions, an area with a different silver halide composition. In such a method, the halide composition of the seed particles is ar-bitrarily selected from silver bromide, silver iodo-bromide, silver chloro-iodo-bromide, silver bromide, silver chloride and others. However, the preferred compositions are silver iodo-bromide or silver bromide respectively having not more than 10 mol% of silver iodide conetnt. Additionally, the pre-ferred proportion of seed particles to the total silver halide is not more than 50 mol~, in particular, less than 10 mol~.
The status of silver iodide distribution in the above-.
mentioned core/shell type silver halide particles is deter-mined using various physical measuring methods. Such methods include the measurement of luminescence in a low temperature range, and the X-ray diffraction method both described in ex-cerpts of lectures in 1981 Annua1 Meeting of the Photographic - 23 _ 1 3 1 7 5 00 Society of Japan.
The above-mentioned core/shell type silver halide parti-cles may be regular crystals such as cubic, tetrahedral or octahedral crystals, or may be twin crystals, or include mix-ture of any of these crystals. However, the regular crystals are advantageous.
The preferred core/shell type silver halide emulsion according to the invention is a monodispersed emulsion. A
monodispersed silver halide emulsion means the emulsion of which weight of silver halide particles having particle sizes within +20~ of an average aprticle diameter r accounts for more than 60% of the total weight of silver halide particles.
Preferably, this percentage is more than 70%, in particular, more than 80%.
The average particle diameter r is defined as ri, where the product of frequency ni of particles individually having the particle diameter ri and ri 3 i.e. the product ni x ri 3 becomes maximum. (A least significant figure is rounded up or down to provide a three significant figures.) The term "particle diameter" in this text means a dia-meter of an individual silver halide particle if it is a spherical crystal, or, a diameter of an circular image which is converted from a projected image of an individual silver halide particle having an area equal to that of the circular image if an individual particle is not spherical.
Additionally, the particle diameter may be determined by projecting an image of an individual silver halide particle magnified ten thousand times to fifty thousand times using an electron microscope, and, by actually measuring the diameter on a photographic print or the area of the projected image.
(The number of particles to be measured is for more than one thousand of arbitrarily selected particles.) The particularly preferred high-grade monodispersed emul-sion has a distribution of less than 20%, or, more specifical-ly, less than 15~ when defined by the following expression for wideness of distribution;
Standard deviation x 100 = Wideness of distribution (%) Average particle diameter The average particle diameter as well as the standard deviation in this expression are determined by the previously defined ri.
A monodispersed emulsion is prepared by a double jet precipitation method, wherein an aqueous solution of water soluble silver salt and an aqueous solution of water soluble halide are added to gelatin solution containing seed parti-cles, with the pAg and pH being controlled. In specifying the rate of addition, Japanese Patent O.P.I. Publications No.
48521/1979 and No. 49938/1983 may be referred to.
Furthermore, as a method for preparing more improved monodispersed emulsion, a particle-growing method with the presence of tetrazaindene disclosed in Japanese Patent o.P.I.
Publication No. 122935/1985 is applicable.
The scope of the present invention includes a case where an silver halide emulsion for forming at least one silver halide emulsion layer in a light-sensitive material to be processed is an emulsion having tabular silver halide parti-cles. More specifically, with the preferred silver halide emulsion used for forming silver halide emulsion layer accord-ing to the invention, the silver halide particles are as fol-lows:
(1) the previously mentioned core/shell type silver halide particles (2) the tabular silver halide particles (such tabular silver halide particles may be either core/shell type particles of another type of particles) (3) the mixture of the above-defined (1) and (2).
Any of these types of silver halide particles are included as preferred embodiments in the invention.
The tabular silver halide particles advantageously used in embodying the invention are hereinunder described in de-tail.
When using the tabular silver halide particles in embody-ing the invention, the preferred diameters of these particles are five times as large as their thicknesses. Such tabular silver ha]ide particles may be prepared using any conventional method such as described in Japanese Patent O.P.I. Publica-tions No. 113930/1983, No. 113934/1983, No. 127921/1983, and No. 108532/1983. In consideration of image quality or the like, the preferred particle diameters are more than five times, in particular, five to 100 times, or, more specifical-ly, seven to 30 times as large as the particles thicknesses.
The preferred particle diameters are not less than 0.3 ~m, in particular, 0.5 to 6 ~m. When contained in at least one sil-ver halide emulsion layer at a rate of at least 50~ by weight, these tabular silver halide particles more advantageously attain the effect of the invention. If most of the silver halide particles are the above-defined tabular silver halide particles, the effect of the invention is optimized.
The present invention is especially effective when the tabular silver halide particles are core/shell type particles.
In this case, the core/shell type particles should preferably satisfy all the requirements previously specified.
Generally, an tabular silver halide particle has two parallel faces. Accordingly, the "thickness" of such a parti-cle is defined as a distance between the two parallel faces constituting an individual tabular silver halide particle.
The preferred halide composition of the tabular silver halide particles are silver iodo-bromide particles having a silver iodine content of not less than 0.5 mol~, in particular, 3 to 10 mol%.
- 27 ~ 1 3 ~ 7~00 The preparation of the tabular silver halide particles is hereinunder described.
The tabular silver halide particles may be prepared using arbitrarily combining methods known in the photographic art.
Such particles are obtained, for example, at first by forming seed crystals involving more than 40% by weight of tabular silver halide particles in a comparatively high pAg atmosphere of not more than 1.3 of pBr, and then, by growing the seed particles with silver and halogen solutions being simultaneously added while maintaining the pBr value roughly constant.
However, in the course of particle growth, it is prefer-able that silver and halogen solutions be further added in order to prevent further generation of new crystal nuclei.
The sizes of the tabular silver halide particles are ad-justed by controlling a temperature, by deliberately selecting the types and amounts of solutions, and by controlling the adding rates of silver salt and halide used during the parti-cle growth.
Using a silver halide solvent in compliance with a speci-fic requirement in the course of preparation of the tabular silver halide particles controls the particles sizes, particle configurations (diameter/thickness ratio and others), the particle size distribution, the growth rate of the particles.
The amount of added silver halide solvent is 1 x 10- 3 to 1.0 - 28 ~ l 3 1 7500 weight%, or, preferably, 1 x 10-2 to 1 x 10~l weight~ per amount of a reaction solution.
Increasing the amount of silver halide solvent being added positively makes the silver halide particle size distri-bution more monodispersed, and accelerates the particle growth rate. On the other hand, the increase in the amount of silver halide solution at the same time increases the thicknesses of the silver halide particles.
The silver halide solvents useful in this process are ammonia solution, thioether solution, and thiourea solution.
In using a thioether solution, U.S. Patents No. 3,271,157, No. 3,790,387, No. 3,574,628 and others may be referred to.
In preparing the tabular silver halide particles, pre-ferred methods are such that the adding rates, added amounts, adding concentrations of the silver salt solution (for exam-ple, aqueous AgNO3 solution) and halide solution (for example, aqueous KBr solution) are incrased in order to accelerate the particle growth.
For details of these methods, British Patent No.
1,335,925, U.S. Patents No. 3,672,900, No. 3,650,757, and No.
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1 31 7~0U
PROCESSING METHOD FOR SILVER HALIDE COLOR PHOTOGRAPHIC
LIGHT-SENSITIVE MATERIAL AND COLOR DEVELOPER USED THEREIN
FIELD OF THE INVENTION
The present invention relates to a processing method for a silver halide color photographic light-sensitive material and a color developer used therein, in particular to a processing method for a silver halide color photographic light-sensitive material providing a dye image with excellent graininess and a color developer used to em~odying this method.
BACKGROUND OF THE INVENTION
Recently, miniaturization of a silver halide color photo-graphc light-sensitive material has been in progress. More specifically, to miniature a camera for better portability, miniaturization of an image size on a film is in progress. It is, however, well known such an arrangement incurs a deterio-rated printed image quality. More specifically, a smaller image size in a color photographic light sensitive-material necessitates a greater enlargemen~ ratio for preparing a specific size of final print, and such a printed image accord-ingly has poor graininess as well as poor sharpness. There-fore, it is mandatory, in preparing an excellent print even with a miniaturized image size on a film, to improve the graininess, resolution and sharpness of a film.
As the method to improve graininess, among these re~uire-ments for improved silver halide color photographic light-sensitive materials, the following are available: a method, as described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I.
Publication) No. 62454 1980 published May 10, 1980, for using a rapid-reacting type coupler; a method, as described in the Theory of the Photographic Process, 4th Ed., pp. 620 - 621, by T.H. James, increasing the number of silver halide particles per unit of photographic material; a method, as described in British Patent No. 2,080,640A, for using a non-diffusion type coupler for forming a diffusion type dye which emit an appropriately small amount of dye upon reaction with an oxidation product of color developing agent; a method, as described in Japanese Patent O.P.I. Publication No. 128443/1985 published July 9, 1985, for increasing a ratio of silver iodide content to more than 8 mol~; other improvement methods as described in Japanese Patent O.P.I. Publications No.
191036/1984, No. 3682/1985, No. 128440/1985 and the like respectively published October 30, 1984, January 10, 1985 and July 9, 1985; a technique, as described in Japanese Patent Examined Publication No. 15495/1~74, Japanese Patent O.P.I.
Publications No. 7230/1978, No. 155539/1982 and the like respectively publlshed ~pril 15, 1974, January 23, 1978 and September 25, 1982 wherein an improvement is achieved by modifying the constitution of structural layers in a silver halide color photographic liqht-sensitive material.
Though the above-mentioned methods for improving a light-sensitive material positively improves graininess, the degree of improvement is not yet satisfactory. Insufficience in graininess poses an obstacle against common use of a light-sensitive material have an extremely small format for example in the case of so-called "disk-film", and therefore has neces-sitated improvement.
In Chiba University, Engineering Department, Research-Report Vol. 33 (1), Vol. 63 in whole number, ~1980), pp. 45 -48, is described the technique of "Image improvement of color negative film by rapid processing" by Arai et. al. In this report, it is mentioned that two layers i.e. cyan and magenta layers which are separated from a suppo:r~_ are provided with approximately 20 to 30% increase in image information by means of highly active color developer as well as high-temperature rapid processing, and results in increase in sharpness, at a cost of deteriorated graininess in an image. This has been a theory established in the photographic art.
The present invention is intended to solve the above dis-advantage. Therefore, the object of the invention is to a B
1 3 1 75~
rapid processing method for a silver halide color photographic light-sensitive material providing a dye image with excellent sharpness and graininess, as well as a color developer used to embodying this method.
DISCLOSURE OF THE INVENTION
The inventors have continued devoted research in order to attain the above object, and found that such a processing method compries with the above object. That is a processing method for processing a silver halide color photographic light-sensitive material comprising a support, provided there-on, at least one silver halide emulsion layer, and at least one silver halide contains silver iodo-bromide with not less than 0.4 mol% iodine, wherein the development time is not more than 180 seconds and the method satisfies the following criteria.
The processing method of the invention is characterized in that an image defined below is obtained when light-sensi-tive material B specified below containing silver iodo-bromide with iodine content of not less than 0.5 mol% as well as magenta coupler is exposed under the following conditions C
and then subjected to color developing with a duration of 3 min. 15 sec. by using developer A specified below, with an assumption that the maximum magenta density of the light sen-sitive material satisfies the expression M < 2Ø
~ 5 ~ 1 317~0 In other words, it is a processing method, for a silver halide color photographic light-sensitive material, according to the first invention in the present application that a dye image having maximum magenta density M < 2.0 is available from the light-sensitive material B, of which magenta dye image has maximum density of M > 2, when the light-sensitive material B
is exposed under exposure conditions identical with the above and then the exposed material is subjected to color developing with a duration of shorter than 2 min.
Developer A used for specifying light-sensitive material B is as follows:
Developer A
_ Potassium carbonate 37.5 g Sodium sulfite 4.25 g Potassium iodide 2 g Sodium bromide 1.3 g Hydroxylamine sulfate 2.0 g 3-methyl-4-amino-N-ethyl-(~-hydroxyethyl)-aniline sulfate 4.75 g Water is added to the above components to prepare one liter solution, which is adjusted to pH 10.0 with 50~ sulfuric acid.
The exposure conditions C mentioned above are as follows:
using a tungsten light source and filter, a color temperature is adjusted to 4800K, in order ro provide 3.2 CMS wedge ex-- 6 ~ 1 3 1 7~
posure light.
The above processing method of the invention may be de-fined as a processing method which is capable of forming an image having a density higher than a color density, by sub-jecting a light-sensitive material B, which only produces an image of lower color density when developed under a specific condition, to color developing with a duration of not more than 2.5 min.
The above developer A and the developing conditions C
used to specify the light-sensitive material B are those con-ventionally used in the art. In contrast, the processing method of the invention, which is capable of attaining magenta coloration of M ~ 2.0 when the light-sensitive material B
otherwise only having magenta coloration of M 2 2.0, may be called a process performed under an unconventionally active condition.
It is an unexpected fact even for the inventors that the above ob]ect. i.e. improved graininess is attained by a rapid and active process of which color developing time is unconven-tionally short, not more than 180 seconds.
The operation of the invention is yet to be known. How-ever, the estimated reason is that performing a color develop-ing process under such an active condition as of the invention somehow prevents dye formed around silver halide particles from being dispersed, and, resultingly, an image of excellent ~ 7 - l 3 1 75~0 graininess is obtained.
The second invention in the present application is char-acterized by a developing temperature of higher than 40C in performing the above color developing process. The developing temperature of not lower than 40C ensures a rapid and active developing process.
The third invention in the present application is that the concentration of developing agent in developer solution is not lower than 1.5 x 10 1 mol/liter in performing the color developing process. Such a high concentration of color devel-oping agent ensures a rapid and active developing process.
The fourth invention in the present application is the developing time ranges from 20 to 150 seconds in performing the color developing process.
The fifth invention in the present application is the membrane swelling rate in relation to the light-sensitive material in the course of the color developing process is not more than 20 seconds.
This feature enables image quality, in particular, graininess.
In embodying the respective inventions in the present application, incorporating a combination composed of a com-pound represented by any of general formulas [R-I] through [R-IV] described layer, a compound represented by any of gen-eral formulas [A-I] through [A-VI], and at least one compound - 8 - t317500 selected from polymers individually having a pyrolidone nucle-us in the molecular structure, into a color developer solution is capable of effectively suppressing fog in a non-exposure portion, adjust a tone properly, and further improves image quality. For this reason, the above compounds are favorably used in embodying the above respective inventions.
The sixth invention in the present application is the use of above processing method for a silver halide color photo-graphic light-sensitive material comprising a support, pro-vided thereon, at least one silver halide emulsion layer con-taining a coupler represented by the following general formula lM-I], wherein at least one emulsion layer contains silver iodo-bromide.
[M-I]
X m R m ~ "
N N ~
zm represents a plurality of non-metal atoms necessary for forming a nitrogen heterocycle. The heterocycle formed by zm may have a substituent.
xm represents a hydrogen atom, or a group capable of split off upon reaction with an oxidation production of a color developing agent.
9 1 31 7~00 Rm represents a hydrogen atom, or a substituent.
The seventh invention in the present application is use of the above-mentioned processing method in treating a silver halide color photographic light-sensitive material comprising a support, provided thereon, at least one silver halide emul-sion layer containing a coupler represented by the following general formula O[C-I], wherein at least one emulsion layer contains silver iodo-bromide.
General formula [C-I]
f H
Rc 3 ~/~ NHCO(NH)m t Rc~
RczCONH ~ ~
In this formula, RCl and RC2 independently represent an alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group. Each of these groups may have a substi-tuent. Rc3 represents a hydrogen atom, halogen atom, alkyl group or alkoxy group. Such an alkyl or alkoxy group may have a substituent. Such a substituent may be a ring which RC2 and Rc3 combinedly form. X represents a hydrogen atom, or a group capable of split off upon reaction with an oxidation product of a color developing agent. mc represents O or 1.
The eighth invention in the present application is a lo - I 31 7500 color developer for a silver halide color photographic light-sensitive material, containing at least one compound selected from the following group ~A] and subjected to at least one means selected from the following group lB].
Group [A]
(A-l) Compounds represented by the following general for-mula [R-I]
General formula [R-I]
. ' / ( X r I ) n r ;Z r '.
( X r ) m r ~ -- X r Z
"'"' C /
In this formula, X'r and X'rl independently represent a halogen atom, alkyl group, aryl group, amino group, hydroxy group, nitro group, carboxyl group or sulfonyl group. X'r2 represents a hydrogen atom, alkyl group, aryl group, or a double-bond capable of forming a ring. Zr represents a plu-rality of atoms comprising a carbon atom, oxygen atom, nitro-gen atom and sulfur atom, being necessary for forming a ring.
nr and mr independently represent 0, 1, 2 or 3.
(A-2) Compounds represented by the following general for-mula [R-II]
7 3 1 ~
General formula [R-II]
Y r a -- Y r I
Y r 3 Y r Z
In this formula, Yra, Rrl, Yr2 and Yr3 independently re-present a hydrogen atom, halogen atom, alkyl group, amino group, hydroxy group, nitro group, carboxyl group or sulfonyl group.
(A-3) Compounds represented by the following general for-mula [R-III]
General formula [R-III]
, " Y 4 ,' ~1) Y r s --7 r x 2 x r ~
In this formula, Tr represents a nitrogen atom, or phos-phor atom. Xr2 and Xr3 independently represent a hydrogen atom, alkyl group, aryl group, or halogen atom. Yr4 and Yrs independently represent an alkyl group, or aryl group. Yr4 and Yrs may jointly undergo ring closure to form a hetero-cycle.
(A-4) Compounds represented by the following general for-mula [R-IV]
General formula [R-IV]
f Rsl "-- C~
iX s Y s R 2 0 / \ Z ~ j 0 R 3 Rss In Formula [R-IV], Rsl represents -OH, -oRs4 or -N~
Rs4 and Rss independently represent an alkyl group. The alkyl group represented either by Rs 4 or Rss may have a substituent (for example, an aryl group such as a hydroxyl group and phenyl group) and is typified by a methyl group, ethyl group, propyl group, butyl group, benzyl group, ~-hydroxyethyl group, dodecyl group or the like.
Rs 2 and Rs 3 independently represent -H or - C - Rs 6, Rs6 represents an alkyl group or aryl group. The examples of the alkyl group represented by Rs 6 include a long-chained alkyl group such an undecyl group.
Xs and Ys respectively represent a carbon atom and a hy-drogen atom, each of which forms a six-membered ring together with other plurality of atoms. Zs represents -N= or -CH=.
If Zs is -N=, a compound of the invention represented by - 13 ~ l 3 1 750~
general formula ~R-IV] is typically a citradinic derivative.
If Z represents -C=, a compound of the invention represented by general formula [R-IV] is typically a bezoic derivative.
The six-membered ring within this compound may have a substi-tuent such as a halogen atom.
Zs is favorably -N=.
(A-5) Polymer or copolymer, which has a pyrolidone nucle-us within the molecular structure (A-6) Polyethylene glycol derivative [Group B]
(B-I) Concentration of p-phenylenediamine developing agent within color developer solution is higher than l.S x 10~
mol/liter (B-II) pH of color developer solution is greater than 10.4 (B-III) Concentration of sulfite in color developer solu-tion is less than 1.5 x 10~l mol/liter (B-IV) Concentration of bromide in color developer solu-tion is less than 0.8 x 10~l mol/liter (B-V) Color developer contains at least one of compound selected from those represented by the following general for-mulas [A-I] through [A-VI]
General formula [A-I]
X ~ ( C ~I Z ~ n a l t X a Z - ( C 1I z~) n a Z )~ X a :1 - ( CHz ~n a ~ X a 4 In this formula, Xa2 and Xa3 indepenaently represent a sulfur atom or oxygen atom. Xal and Xa4 independently repre-sent a SH group or OH group. na1, naz~ na3 and mal indepen-dently represent an integer ranging from 0 to 500, whereby at least one of nal, na2 and na3 is an integer greater than 0.
Additionally, at least one of Xa1, Xa2, Xa3, and Xa4 is a sulfur atom.
General formula [A-II]
Qa z Aa 3 A a I ~-- N <
A a 4 R a 2 In this formula, Ral and Ra2 independently represent a hydrogen atom; or an alkyl group such as a methyl group, ethyl group or propyl group; or a heterocyclic group which is capa-ble of forming a ring, in~ol~ing an oxygen or nitrogen atom, together with Ral and Ra2. Aa2, Aa3 and Aa4 independently represent a hydrogen atom; or an alkyl group such as a methyl or ethyl group; or a halogen atom such as a chlorine, fluo-rine, or bromine atom. Aa1 repreesnts a hydroxy group or ~ Ra~
-N~ . Additionally, Ra3 and Ra4 independently represent a Ra"
hydrogen atom, or an alkyl group having 1 to 3 carbon atoms.
- 15 - 1 3 1 7~0~
General formula [A-III]
Ra 1.
I
Ras ~iaz Ras Xas e Ra 7 In this formula, Ras, Ra6, Ra~ and Ra8 independently re-present a hydrogen atom, alkyl group, aralkyl group; or a sub-stituted or unsubstituted aryl group. Aa2 represents a nitro-gen or phosphor atom. Ra8 represent a substituted or unsub-stituted alkylene group. Ras and RaB may form a ring, or in-dependently be substituted or unsubstituted pyridinium group.
XaS represents an anion group such as a halogen atom, OH, sulfuric group or nitric group.
General formula [A-IV]
Ra I o / I
X N - (CHz)na4 - (C)ma2 Y a (Ra 9) ~ a na I I
In this formula, Ya represents a hydrogen atom, hydroxy /Ra 12 group or -N . Rag, Ra1D, Ra11, Ra12 and Ra13 independ-Ral3 ently represent a hydrogen atom; or a substituted or unsub-stituted group, having 1 to 3 carbon atoms, such as an alkyl group, carbamoyl group, acetyl group and amino group. X re-presents an oxygen atom, sulfur atom or N-Ral4. At the same time, Rall represents a hydrogen atom, or a substituted or un-substituted alkyl group having 1 to 3 carbon atoms. la, ma2 na4 independently represent an integer 0, 1, 2 or 3.
General formula [A-V]
Rb, > N (A b ) n b O R b 3 n b 2 In this formula Rbl and Rb2 independently represent a hydrogen atom, alkyl group, alkoxy group, aryl group; or a nitrogen-containing heterocycle which may be formed by Rb1 and Rb2; or a nitrogen-containing heterocycle which may be formed by Rbl and Ab, or by Rb2 and Ab. Rb3 represents an alkyl group. Ab represents an alkylene group. nb represents an integer ranging from O to 6.
General formula [A-VI]
~ Rb 2 Rb I '--N ~
Rb 3 In this formula, Rbl' represents a hydroxy alkyl group having 2 to 6 carbon atoms. Rb2' and Rb3' independently re-present a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms; or a hydroxy alkyl group or benzyl group each having 2 to 6 carbon atoms; or -Cnb', H2nb', -N . In ~ Zb - 17 - t317500 these formulas, nb' represents an integer ranging from 1 to 6; Xb and Zb independently represent a hydrogen atom, an alkyl group having 1 to 6 carbona toms or a hydroxy alkyl group hav-ing 2 to 6 carbon atoms.
The respective inventions are described in detail below.
The first inventi,on is hereinunder described.
The first invention in the present application is a proc-essing method for a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer disposed on a support, wherein at least one emulsion layer contains silver iodo-bromide having more than 0.5 mol%
of iodine content.
A light-sensitive material subject to the process of the invention is arbitrarily selected from those satisfying the previously specified conditions.
Light-sensitive material B, which is a standard sample for specifying the method of the invention, contains not only silver iodo-bromide with more than 0.5 mol% of iodine content, but a magenta coupler. This light-sensitive material B, when exposed and then subjected to a color developing process under the conditions of 33C and three minutes 15 seconds using the previously specified developer A, provides maximum magenta density M of M ~ 2Ø The processing method of the invention is capable of produce a dye image of which maximum magenta density M available from the light-sensitive material B satis-- 18 - l 31 7500 fies M > 2.0, when the light-sensitive material in compliance with the above conditions is subjected to color developing 2.5 minutes after the exposure in compliance with the above speci-fied conditions. (As mentioned previously, light-sensitive material B is a standard sample for specifying the processing method. Correspondingly, any color light-sensitive material treated by the method of the invention is arbitrarily used, as far as it contains the above-mentioned type of silver iodo-bromide.) Light-sensitive material B, i.e. a standard sample for specifying the processing method, may contain arbitrary magenta coupler, and have an arbitrary silver halide composi-tion, as far as the composition comprises silver iodo-bromide with not less than 0.5 mol~ of iodine. Any processing method is included in the scope of the invention, as far as the method is capable of satlsfying M 2 2.0 when subjecting light-sensi-tive material B having undergone exposure under a specific exposure condition to processing with a duration not longer than 2.5 minutes and if the same light-sensitive material hav-ing undergone exposure under the same specific exposure condi-tion produces a magenta dye image with M < 2.0 when treated in the above specified conditions using the above developer A.
The exposure condition for exposing light-sensitive mate-rial B used to specify the processing method is as follows;
using a tungsten source, color temperature is adjusted to 4800K with a filter, in order to provide 3.2 CMS wedge ex-posure.
An arbitrary magenta coupler is contained in light-sen-sitive materia] B. For example, light-sensitive material B
may contain, as a coupler, a compound of general formula lM-I].
A preferred embodiment of the processing method of the invention is a method being capable of forming a dye image of which magenta fog density in the non-exposure portion is less than 0.5, if light-sensitive material B is subjected to the above-mentioned processing with a duration of less than 2.5 minutes.
The first invention in the present application is further described in detail below.
A silver halide color photographic light-sensitive mate-rial used in the processing according to the invention con-tains, in at least one silver halide emulsion layer, silver iodo-bromide with not less than 0.5 mol% of silver iodide.
However, the preferred light-sensitive material in embodying the invention has not less than 1.0 mol%, in particular, 3 to 10 mol%, or more favorably, 5 to 8 mol% of silver iodide con-tent.
The scope of silver halide particles including the above-mentioned silver iodide is not specifically limited. However, in embodying the invention, the preferred silver halide par-ticles are core/shell type silver halide particles, and tabular silver halide particles.
The core/shell type silver halide particles, and tabular silver halide particles respectively having silver iodide con-tent of not less than 0.5 mol% are advantageously used in em-bodying the invention. These types of silver halide particles are hereinunder described in detail.
With the core/shell type silver halide emulsion particles advantageously used in embodying the invention, individual particles have a particle structure comprising more than two layers respectively having a different silver iodide content.
The preferred silver halide particles are silver iodo-bromide particles, wherein a layer having maximum silver iodide con-tent (referred to as shell) is any layer other than the outer-most layer (referred to as core). The preferred silver iodide content in the internal layer (core), which has the maximum silver iodide content, is 6 to 40 mol~, in particular, 10 to 20 mol%. The preferred silver iodide content in the outermost layer (shell) is less than 6 mol%, in particular, 0.1 to 4.0 mol%.
When using the core/shell type silver halide particles, the preferred proportion of shell portions is 10 to 80%, in particular, 15 to 70%, more specifically, 20 to 60%.
The preferred proportion of core portions among total particles is lO to 80%, in particular, 20 to 50%.
According to the invention, if the silver halide parti - 21 ~ l 3 1 7 500 cles are core/shell type particles, individually comprising a core portion having a higher silver iodide content and a shell portion having a lower silver iodide content, there may be a clear-cut border in terms of difference in iodine contents, or, otherwise, the content may continuously change from the core to shell portion. Additionally, such particles individ-ually having an intermediate layer between the core and shell portions, whereby the silver iodide content of the intermedi-ate layer is virtually an average of those of the core and shell portions.
When using core/shell type silver halide particles having the above-mentioned intermediate layers, the volume of inter-mediate layers is 5 to 60%, and, favorably, 20 to 55% of the total volume of all the particles. The difference in silver iodide content between the shell and the intermediate layer, as well as the difference in the intermediate layer and the core, should be respectively not less than 3 mol%. The dif-ference in silver iodide content between the shell and the core should be favorably not less than 6 mol~.
When using the core/shell type silver halide particles in embodying the invention, the preferred average silver iodide content of such aprticles should be ~ to 20 mol%, in particu-lar, 5 to 15 mol~. Also, such particles may contain silver chloride, as far as the amount of silver chloride does not deteriorate the effect of the invention.
- 22 ~ l 3 1 7 50 0 The core/shell type emulsion used for a light-sensitive material subjected to the processing method of the invention may be prepared in compliance with known methods disclosed, for example, in Japanese Patent O.P.I. Publications No.
177535/1984, No. 138538/1985, No. 52238/1984, No. 143331/1985, No. 35276/1985 and No. 258536/1985.
When preparing core/shell type silver halide emulsion starting from seed particles, as in a method described in an example in Japanese Patent o.P.I. Publication No. 138538/1985, some particles may have, in the respective center portions, an area with a different silver halide composition. In such a method, the halide composition of the seed particles is ar-bitrarily selected from silver bromide, silver iodo-bromide, silver chloro-iodo-bromide, silver bromide, silver chloride and others. However, the preferred compositions are silver iodo-bromide or silver bromide respectively having not more than 10 mol% of silver iodide conetnt. Additionally, the pre-ferred proportion of seed particles to the total silver halide is not more than 50 mol~, in particular, less than 10 mol~.
The status of silver iodide distribution in the above-.
mentioned core/shell type silver halide particles is deter-mined using various physical measuring methods. Such methods include the measurement of luminescence in a low temperature range, and the X-ray diffraction method both described in ex-cerpts of lectures in 1981 Annua1 Meeting of the Photographic - 23 _ 1 3 1 7 5 00 Society of Japan.
The above-mentioned core/shell type silver halide parti-cles may be regular crystals such as cubic, tetrahedral or octahedral crystals, or may be twin crystals, or include mix-ture of any of these crystals. However, the regular crystals are advantageous.
The preferred core/shell type silver halide emulsion according to the invention is a monodispersed emulsion. A
monodispersed silver halide emulsion means the emulsion of which weight of silver halide particles having particle sizes within +20~ of an average aprticle diameter r accounts for more than 60% of the total weight of silver halide particles.
Preferably, this percentage is more than 70%, in particular, more than 80%.
The average particle diameter r is defined as ri, where the product of frequency ni of particles individually having the particle diameter ri and ri 3 i.e. the product ni x ri 3 becomes maximum. (A least significant figure is rounded up or down to provide a three significant figures.) The term "particle diameter" in this text means a dia-meter of an individual silver halide particle if it is a spherical crystal, or, a diameter of an circular image which is converted from a projected image of an individual silver halide particle having an area equal to that of the circular image if an individual particle is not spherical.
Additionally, the particle diameter may be determined by projecting an image of an individual silver halide particle magnified ten thousand times to fifty thousand times using an electron microscope, and, by actually measuring the diameter on a photographic print or the area of the projected image.
(The number of particles to be measured is for more than one thousand of arbitrarily selected particles.) The particularly preferred high-grade monodispersed emul-sion has a distribution of less than 20%, or, more specifical-ly, less than 15~ when defined by the following expression for wideness of distribution;
Standard deviation x 100 = Wideness of distribution (%) Average particle diameter The average particle diameter as well as the standard deviation in this expression are determined by the previously defined ri.
A monodispersed emulsion is prepared by a double jet precipitation method, wherein an aqueous solution of water soluble silver salt and an aqueous solution of water soluble halide are added to gelatin solution containing seed parti-cles, with the pAg and pH being controlled. In specifying the rate of addition, Japanese Patent O.P.I. Publications No.
48521/1979 and No. 49938/1983 may be referred to.
Furthermore, as a method for preparing more improved monodispersed emulsion, a particle-growing method with the presence of tetrazaindene disclosed in Japanese Patent o.P.I.
Publication No. 122935/1985 is applicable.
The scope of the present invention includes a case where an silver halide emulsion for forming at least one silver halide emulsion layer in a light-sensitive material to be processed is an emulsion having tabular silver halide parti-cles. More specifically, with the preferred silver halide emulsion used for forming silver halide emulsion layer accord-ing to the invention, the silver halide particles are as fol-lows:
(1) the previously mentioned core/shell type silver halide particles (2) the tabular silver halide particles (such tabular silver halide particles may be either core/shell type particles of another type of particles) (3) the mixture of the above-defined (1) and (2).
Any of these types of silver halide particles are included as preferred embodiments in the invention.
The tabular silver halide particles advantageously used in embodying the invention are hereinunder described in de-tail.
When using the tabular silver halide particles in embody-ing the invention, the preferred diameters of these particles are five times as large as their thicknesses. Such tabular silver ha]ide particles may be prepared using any conventional method such as described in Japanese Patent O.P.I. Publica-tions No. 113930/1983, No. 113934/1983, No. 127921/1983, and No. 108532/1983. In consideration of image quality or the like, the preferred particle diameters are more than five times, in particular, five to 100 times, or, more specifical-ly, seven to 30 times as large as the particles thicknesses.
The preferred particle diameters are not less than 0.3 ~m, in particular, 0.5 to 6 ~m. When contained in at least one sil-ver halide emulsion layer at a rate of at least 50~ by weight, these tabular silver halide particles more advantageously attain the effect of the invention. If most of the silver halide particles are the above-defined tabular silver halide particles, the effect of the invention is optimized.
The present invention is especially effective when the tabular silver halide particles are core/shell type particles.
In this case, the core/shell type particles should preferably satisfy all the requirements previously specified.
Generally, an tabular silver halide particle has two parallel faces. Accordingly, the "thickness" of such a parti-cle is defined as a distance between the two parallel faces constituting an individual tabular silver halide particle.
The preferred halide composition of the tabular silver halide particles are silver iodo-bromide particles having a silver iodine content of not less than 0.5 mol~, in particular, 3 to 10 mol%.
- 27 ~ 1 3 ~ 7~00 The preparation of the tabular silver halide particles is hereinunder described.
The tabular silver halide particles may be prepared using arbitrarily combining methods known in the photographic art.
Such particles are obtained, for example, at first by forming seed crystals involving more than 40% by weight of tabular silver halide particles in a comparatively high pAg atmosphere of not more than 1.3 of pBr, and then, by growing the seed particles with silver and halogen solutions being simultaneously added while maintaining the pBr value roughly constant.
However, in the course of particle growth, it is prefer-able that silver and halogen solutions be further added in order to prevent further generation of new crystal nuclei.
The sizes of the tabular silver halide particles are ad-justed by controlling a temperature, by deliberately selecting the types and amounts of solutions, and by controlling the adding rates of silver salt and halide used during the parti-cle growth.
Using a silver halide solvent in compliance with a speci-fic requirement in the course of preparation of the tabular silver halide particles controls the particles sizes, particle configurations (diameter/thickness ratio and others), the particle size distribution, the growth rate of the particles.
The amount of added silver halide solvent is 1 x 10- 3 to 1.0 - 28 ~ l 3 1 7500 weight%, or, preferably, 1 x 10-2 to 1 x 10~l weight~ per amount of a reaction solution.
Increasing the amount of silver halide solvent being added positively makes the silver halide particle size distri-bution more monodispersed, and accelerates the particle growth rate. On the other hand, the increase in the amount of silver halide solution at the same time increases the thicknesses of the silver halide particles.
The silver halide solvents useful in this process are ammonia solution, thioether solution, and thiourea solution.
In using a thioether solution, U.S. Patents No. 3,271,157, No. 3,790,387, No. 3,574,628 and others may be referred to.
In preparing the tabular silver halide particles, pre-ferred methods are such that the adding rates, added amounts, adding concentrations of the silver salt solution (for exam-ple, aqueous AgNO3 solution) and halide solution (for example, aqueous KBr solution) are incrased in order to accelerate the particle growth.
For details of these methods, British Patent No.
1,335,925, U.S. Patents No. 3,672,900, No. 3,650,757, and No.
4,424,445, and Japanese Patent O.P.I. Publications No. 142329/
1980, No. 158124/1980 and others may be referred to.
The tabular silver halide particles may be chemically sensitized in compliance with a specific requirement. For the chemical sensitization method, the description of sensitiza-- 29 - l 37 7i~ 0 tion methods previously described for the core/shell type par-ticles may be referred to. More specifically, in considera-tion of more economically using silver, the tabular silver halide particles should be preferably sensitized with a gold sensitization method or sulfur sensitization method or combi-nation of these two methods.
In a layer containing the tabular silver halide parti-cles, such aprticles should be present at a rate by weight of more than 40~, in particular, more than 60~ per total silver halide particles of the smae layer.
The silver halide color photographic light-sensitive materials subjected to the process of the invention are not limited only to the above-described materials, but include the materials having the tabular silver halide particles described below.
For example, Japanese Patent O.P.I. Publication No.
113930/1983 discloses a multi-layered color photographic light-sensitive material comprising a two-layered dye forming unit including an upper emulsion layer containing tabular silver halide particles with an aspect ratio of greater than 8:1; Japanese Patent O.P.I. Publication No. 113934/1983 dis-closes a multi-layered color photographic light-sensitive material comprising green-sensitive and red-sensitive layers containing tabular silver iodo-bromide or silver bromide emul-sion of which particles having an aspect ratio of greater than - 30 - l 3 1 7500 8:1; Japanese Patent O.P.I. Publication No. 113927/19a3 dis-closes a multi-layered color photographic light-sensitive material having tabular silver halide particles having an as-pect ratio of greater than 8:1, wherein the center region o~
individual particles has a higher silver iodine content than the outer circular region; Japanese Patent O.P.I. Publication No. 55426/1984 discloses a silver halide photographic light-sensitive material containing tabular silver halide particles having an aspect ratio of greater than 3:1 as well as a speci-fic sensitizing dye, wherein the material may be also used as a color photographic light-sensitive material; Japanese Patent O.P.I. Publication No. 111696/1985 discloses a silver halide photographic light-sensitive material containing tabular sil-ver halide particles having an aspect ratio of greater than 3:1, wherein the particles mainly composed of (111) faces.
These silver halide color photographic light-sensitive mate-rials may be subjected to the processing method of the inven-tion.
It is also advantageous to incorporate silver halide particles having epitaxy bonds described in Japanese Patent O.P.I. Publication No. 103725/1978 and the like into emulsions of the invention.
The present invention is applicable to any silver halide color photographic light-sensitive material containing, in at least one silver halide emulsion layer, silver halide parti-cles with silver iodine (the preferred embodiment of such silver halide particles are the previously defined core/shell type silver halide particles and/or tabular silver halide par-ticles). A11 or only one of the silver halide emulsion layers disposed on a support may contain the above-mentioned silver halide particles with the above-mentioned silver iodide.
One preferred embodiment of the invention is a silver halide color photagraphic light-sensitive material of which total silver halide applied on a support is at a rate of more than 30 mg per 100 cm2, or, preferably, 30 to 150 mg per 100 cm2, in particular, 30 to 100 mg per 100 cmZ support. In addition, generally speaking, a silver halide emulsion layer nearer to the support should preferably have a greater silver amount.
The silver halide color photographic light~sensitive material used in embodying the invention should preferably contain a compound capable of releasing ~or allowing elution of), in the course of color developing, an inhibitor which forms silver salt with the solubility product with silver ion of not more than 1 x 10-9.
A compound advantageously used in embodying the invention and capable of releasing, in the course of color developing, an inhibitor which forms silver salt with the solubility pro-duct with silver ion of not more than l x 10-9 may be a com-pound which is present as an inhibitor precursor within a pre-- 32 - l 3 1 7500 developing light-sensitive material and capable of releasing an inhibitor in the course of developing, or a compound which is present as an inhibitor within the light-sensitive material and capable of being eluted into a color developer solution in the course of developing. According to the invention, a DIR
compound, tetrazaindene derivative, and 6-aminopurine deriva-tive are advantageously used. Among them, a DIR compound is especially favorably used, as being capable of excellently attaining the objects of the invention. In addition to the DIR compound, a compound being capable of releasing a develop-ment inhibitor upon developing is included in the scope of the invention. The examples of such a compound include those des-cribed in U.S. Patents No. 3,297,445, and No. 3,379,529, West German OLS No. 2,417,914, and Japanese Patent O.P.I. Publica-tions No. 15271/1977, No. 9116/1978, No. 123838/1984 and No.
127038/1984.
A DIR compound advantageously incorporated in a light-sensitive material used in embodying the invention is a com-pound being capable of releasing a development inhibitor upon reaction with an oxidation product of a color developing agent.
Such a DIR compound, becuase releasing a development in-hibitor in the course of color development, prevents eccessive color developing in processing steps following the color de-veloping, thus supressing eccessive increase in image density _ 33 _ 1317500 and providing an image which is in compliance with a designed tone pattern and preventing hardness of the image.
The typical examples of such a DIR compound include DIR
couplers individually incorporating, into the active site of the coupler, a group being capable of forming a compound hav-ing development inhibition activity once split off the active site. These DIR couplers are describe, for example, British Patent No. 935,454, U.S. Patents No. 3,227,544, No. 4,095,984 and No. 4,149,386.
With the above-mentioned DIR couplers, a parent nucleus of coupler is capable of not only forming dye upon coupling reaction with an oxidation product of a color developing agent but releasing a development inhibitor. According to the in-vention, additionally, a compound capable of releasing a de-velopment inhibitor upon coupling reaction with an oxidation produGt of a color developing agent though not releasing a development inhibitor may be used as a DIR compound. The examples of such a compound are described in ~.S. Patents No.
3,652,345, No. 3,928,041, No. 3,958,993, No. 3,961,959, and No. 4,052,213, and Japanese Patent O.P.I. Publications No.
110529/1978, No. 13333/1979, and No. 161237/1980.
Furthremore, according to the invention, a so-called tim-ing DIR compound may be used. With a timing DIR compound, when it is allowed to react with an oxidation product of a color developing agent, the parent nucleus is capable of form-- 34 - t317500 ing a dye or a colorless compound, and, at the same time, the split timing group release a development inhibitor by intra-molecular nucleophilic substitution reaction or elimination reaction. The exmaples of such a timing DIR compound are des-cribed in Japanese Patent O.P.I. Publications No. 145135/1979, No. 114946/1981, and 154234/1982.
Additionally, other useful timing DIR compounds are those described in Japanese Patent O.P.I. Publications No. 160954/
1983 and No. 162949/1983, wherein the above-described timing group connects to a coupler nucleus being capable of forming a perfectly diffusible dye upon reaction with an oxidation pro-duct of a color developing agent.
More advantageous DIR compounds may be represented the following general formula [D] or (D-1). The most advantageous DIR compounds are the compounds represented by the following general formula (D-1) and having diffusibility greater than 0.40.
General formula [D]
Adl - Zdl In this formula, Ad1 represents a coupler component (com-pound) being capable of coupling with an oxidation product of p-phenylenediamine color developing agent. More specifically, the examples of such a coupler component are as follows: dye forming couplers including closed-chain ketomethylene com-pounds such as acylacetanilide, and acyl acetate; pyrazolones, ~ 35 ~ 1 31 7500 pyrazolotriazoles, pyrazolinobenzimidazoles, indazolones, phenols, and naphthols; and coupling components, which do not form dyes, such as acetophenones, indanones, and oxazolones.
In the above formula, Zdl represents a component (com-pound) being capable of split off upon reaction with an oxida-tion product of p-phenylenediamine color developing agent, and inhibit development of silver halide. The preferred examples of such a compound include heterocyclic compounds such as benzotriazole, 3-octylthio-1,2,~-triazolei and heterocyclic mercapto compounds (as an example of heterocyclic mercapto compound, 1-phenyltetrazolylthio group or the like is avail-able).
The examples of the above-mentioned heterocyclic group include a tetrazolyl group, thiazolyl group, oxadiazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, triazolyl group and the like.
In the above general formula [D], Zs~ is bonded to the active site on Adl.
Diffusibility of the above DIR compound may be evaluated using the following procedure.
Light-sensitive material samples (a) and (b) respectively comprising layers of the following compositions being disposed on a transparent support.
Sample (a): Sample having a green-sensitive silver halide emulsion layer - 36 ~ 1 3 1 7500 Gelatin coating solution containing silver iodo-bromide (silver iodide, 6 mol%; average particle size, 0.48 ~m) spec-trally sensitized to have green-sensitivity, as well as the following coupler at a rate of 0.07 mol per mol silver, is applied so that the amount of coated silver is at a rate of 1.1 g/mZ, and the amount of deposited gelatin is 3.0 g/m2.
Upon this emulsion layer is formed a protective layer, by ap-plying gelatin coating solution containing silver iodo-bromide (silver iodide, 2 mol~; average particle size, 0.008 ~m) not undergone either chemical or spectral sensitization, so that the amount of coated silver is at a rate of 0.1 g/m2 and the amount of deposited gelatin is 0.8 g/m2.
NHC0 ~9 c 5 H,,(t) O ')~ \=~ NHCOCH 2 0 ~ CsH,, ( l .
c e ~ C e c e Sample (b~: Identical with the above Sample (a), except that silver iodo-bromide not contained in the protective layer.
Each layer incorporates, in addition to the above com-ponents, a gelatin-hardening agent and a surfactant.
Samples (a) and (b) are subjected to white exposure using an optical wedge, and the treated in the following manner.
~ ~7 - t 3 1 7 5 00 One developer solution contains various 'cypes of development inhibitors with a total amount to suppress the sensitivity of Sample (b) to 60~ (in logarithmic expression, -A log E = 0.22).
The other developer solution does not contain such inhibitors.
Processing (38C) Color developing 2 min 40 sec Bleaching 6 min 30 sec Washing 3 min 15 sec Fixing 6 min 30 sec Stabilizing 1 min 30 sec Drying Compositions of the processing solutions used in the re-spective processing steps are as follows:
IColor developer solution) 4-amino-3-methyl-N-ethyl-N-(~-hydroxyethyl)-aniline sulfate 4.75 g Sodium sulfite anhydride 4.25 g Hydroxylamine.1/2 sulfate 2.0 g Potassium carbonate anhydride 37.5 g Trisodium nitrilotriacetage (monohydride)2.5 g Ptassium hydroxide 1.0 g Water is added to the above components to prepare one liter solution.
(Bleacher) Ferric ammonium ethylenediamine tetraacetate 100 g l3l7soa Diammonium ethylenediamine tetraacetate10.0 g Ammonium bromide 150.0 g Glacial~acetic acid 10.0 g Water is added to the above components to prepare one liter solution, which is adjusted to pH = 6.0 using aqueous ammonium.
(Fixer) Ammonium thiosulfate 175.0 g Sodium sulfite anhydride 8.5 g Sodium metasulfite 2.3 g Water is added to the above components to prepare one liter solution, which is adjusted to pH = 6.0 using acetic acid.
(Stabilizer) Formalin (37~ aqueous solution) 1.5 mQ
Konidax (manufactured by Konica Corporation) 7.5 mQ
Water is added to the above components to prepare one liter solution.
Assuming that the sensitivity of Sample (a) with a devel-opment inhibitor not addes is S0' the sensitivity of Sam,ple (b) with a development inhibitor not added is S0', and that the sensitivity of Sample (a) with a development inhibitor added is SA, and the sensitivity of Sample (b) with develop-ment inhibitor added is SB, the following expressions are valid:
* Trade mark.
~ 39 ~ 1 31 7500 Desensitization ratio: AS = SO - SA
Desensitization ratio: ~S = SO' - SB
Diffusibility = ~S/~SO
wherein each sensitivity is defined as a logarithmic number (-log E) of a reciprocal of an exposure amount corre-sponding with a density status of "fog density + 0.3".
Diffusibility of several types of development inhibitors, determined in this method, is listed in the following table.
- ~- 13~7~
Table _ Amo~mt added Desensiti~ation Diffusibili~y Structure _ , _ (mol/Q) ~SO ! ~S ~S/~SO
HS--i/ 11 . 1.3X10-s 0.22 ~ 0.05 0.23 ~N~`N=C~N~ ; 3 ~'0 ' 0.2 0.08 0 14 CH3 _ HSY~CII~ 2. 5 X 10- S 0. æ 0. 10 0. 45 HS //N-~
1ZHS 3 O~l0- S 0 21 0.10 0 4B
HO~ N0z ~1 CHzN -C~H~ N N 1. 4 x 10~ 5 0. 23 0.11 0. 48 N - i 2.5X10-5 0.22 0.13 0.59 011 .
Table (continued) Amount added Desen3itization l~iffusibility Structure ... _ .,_ .. _ (mol/Q) So S ~S/~Sa ~N ~ C~ ~ 3~l05 023 0l5 _ _ ~N ~ CH3 ~ _ _ ~ l.7~l0-' ~ 0.21 0.~0 ~ 0 ~ ~
Next, a compound indicating diffusibility of greater than 0.40 and therefore favorably used in embodying the invention, that is, a compound represented by the previously mentioned general formula (D-l) and known as a diffusible DIR compound is hereinunder described.
As the diffusible DIR compound, any compound having any chemical structure may be used, as far as the compound releases a group of which diffusibility is within the above-defined range.
The typical structural formula of general formula (D-l) is given below.
General formula (D-l) A t ( Y d ) m d - 42 ~ 1 3 1 7 5 0 wherein Ad represents a coupler residue; md represents 1 or 2; Yd represents a group being capable of split off upon reaction with an oxidation product of a color developing agent by coupling with the coupling site on the coupler residue A, and, more specifically, represents a group being capable of releasing a development inhibitor group or development in-hibitor with diffusibility of greater than 0.40.
Yd in general formula (D-1) is typically represented each of the following general formulas (D-2) through (D-l9).
General formula (D-2) - N N
~--(Rd ~ ) n d General formula (D-3) General formula (D-4) , / N~ tRdl)nd - OCH 2 - N N ~ N ~ /
(Rd,)n d General formula (D-5) General formula ~-6) N ~ (Rdl)n~ - SyX~d, General formula (D-7) General formula (D-~) --N~ ~ ( R d I ) n d --S
Rd 2 Ge~eral formula (D-9) N - N
- S ~ N ~ Rd<
Rd 3 In general formulas (D-2) through (D-l9), Rdl represents a hydrogen atom or halogen atom, or an alkyl group, alkoxy qroup, acylamino group, alkoxycarbonyl group, thiazolydene group, aryloxycarbonyl group, acyloxy group, carbamoyl group, N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group, arylthio group, aryl group, hetero-cyclic group, cyano group, alkylsufonyl group or aryloxycar-bonylamino group. nd represents 0, 1 or 2. When nd is 2, Rd s may be identical or different with each other. The total number of carbon atoms contained within n units of Rdls ranges from O to 10. Additionally, the total number of carbon atoms contained within Rdls in general formula (D-6) ranges from O
to 15.
Xd in this general formula (D-6) represents an oxygen atom or a sulfur atom.
In general formula (D-8), Rd2 represents an alkyl group, aryl group or heterocyclic group.
In general formula (D-8), Rd3 represents a hydrogen atom, or an alkyl group, cycloalkyl group, aryl group or hetero-cyclic group. Rd" represents a hydrogen atom or halogen atom, or an alkyl group, cycloalkyl group, aryl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkanesulfonamide group, cyano group, heterocyclic group, al-kylthio group or amino group.
If Rdl, Rd2, Rd3 or Rd4 represents an alkyl group, such an alkyl group may have a substituent, and be either straight-chained or branched.
If Rdl, Rd2, Rd3 or Rd4 represents an aryl group, such an alkyl group may have a substituent.
If Rdl, Rd2, Rd3 or Rd4 represents a heterocyclic group, such a heterocyclic group may have a substituent. More speci-~ 45 ~ 1317500 fically, such a heterocyclic group is a five- or six-membered single or condensed ring containing at least one hetero atom selected from a nitrogen atom oxygen atom and sulfur atom.
The preferred heterocyclic group is selected from a pyridyl group, ~uinolyl group, furil group, benzothiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group, triazolyl group, benzotriazolyl group, imide group, oxadine group and the like.
The number of carbon atoms contained in Rd2 of general formula (D-6) or (D-81 is O to 15.
The number of carbon atoms contained in Rd3 or Rd4 of general formula (D-9) is O to 15.
General formula (D-10 - TIME - INHIBIT
In this formula, TIME group is a group being capable of bonding to the coupling site on A and also capable of split off upon reaction with an oxidation product of a color devel-oping agent; once split off from the coupler, this group con-trollingly releases an INHIBIT group. The INHIBIT group is a group which serves, once released as mentioned above, as a development inhibitor (a group, for example, represented any of the above-mentioned general formulas (D-2) through ( D-9)).
-TIME-INHIBIT group is general formula (D-10) is typical-ly represented by any of the following general formulas (D-11) through (D-19).
- 46 - l 3 1 7500 General formula (D-ll) _ O ~, ( n ds) e d (CHz) kd- N- Co - INHIBIT
Rd b General formula (D-12) General formula (D-13) (Rd 5 ) e d -O ~ - O ~ CH 2 -INHIBIT
CHz-INHIBIT (Rds) e d General formula lD-14) General formula (D-15) Rd 6 0~( CH 2 ) k- NCO -INHlBlT
/N~ - N ~ Rd b - O ~ N \==~(Rds) Q
/ Rds General formula (D-16) ~ 'I (Rd7)md -N ~ tCH 2 ) KdBd -CO -INH1BIT
- 47 ~ l 3 1 7 500 General formula (D-17) o N - Rd 7 ,~L ( C H Z ) X d B d --C O I ~i HIBIT
General formula (D-18) (Rds) Q d O (CHz)K d B d - CO INHIBIT
General formula (D-l9) 7du -- O (C) ,~ d N--CO --I Nll I BIT
Rdq Rdo In general formula (D-ll) through (D-15) and (D-18), Rds represents a hydrogen atom or halogen atom, or an alkyl group, cycloalkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureide group, cyano group, nitro group, sulfonamide group, sulfamoyl 1317~
group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group or alkanesulfonyl group. In regards to general formulas (D-ll) through (D-13), (D-15) and (D-18), Rdss may bond together to form a condensed ring. In general formulas (D-ll), (D-14), (D-15) and (D-l9), Rds represents an alkyl group, alkenyl group, aralkyl group, cycloalkyl group, heterocyclic group or aryl group. In general formulas (D-16) and (D-17), Rd7 represents a hydrogen atom, or alkyl group, alkenyl group, aralkyl group, cycloalkyl group, heterocyclic group or aryl group. Rda and Rdg in general formula (D-l9) independently represent a hydrogen atom, or an alkyl group (favorably, an alkyl group having 1 to 4 carbon atoms). k in general formulas (D-ll), (D-15) through (D-18) represents an integer 0, 1 or 2. Qd in general formulas (D-ll), (D-15) through (D-18) represents an integer 1 to 4. md in general formula (D-16) represents an integer 1 or 2. If md is 2, the respèctive Rd7 may be either identical or different with each other. n'a in general formula (D-l9) represents an integer 2 to 4. n'd units of respective Rd8s or Rdgs may be either identical or different with each other. B in general formulas (D-16) through (D-18) represents an oxygen atom, or - N - (Rd6 Rd6 is identical with the previously defined Rd6). ... .. in general formula (D-16) means either single bond or double bond is possible. In the case of single bond, md represents 2; in ~ 49 ~ 131750G
the case of double bond, md represents 1. The definition of INHIBIT group is identical with a group represented by any of general formulas (D-2) through (D-9), except the number of carbon atoms.
With an INHIBIT group, the total number of carbon atoms w thin Rls in one molecule represented any of general formulas (D-2) through (D-7) is O to 32. The number of carbon atoms within R2s in one molecule represented general formula (D-8) is 1 to 32. The total number of carbon atoms within Rd3s and Rd4s in one molecule represented general formula (D-9) is O to 32.
When Rd~, Rd~ or Rd7 represents an alkyl group, aryl group or cycloalkyl group, such a group may have a substituent.
Among diffusible DIR compounds, the preferred is a com-pound of which Yd is represented by general formula (D-2), (D-3) or (D-10). With the examples of Yd represented by (D-10), those preferred have an INHIBIT group represented by any of general formulas (D-2), (D-6) (especially when Xd is gen-eral formula (D-6) is an oxygen atom), and (D-8) (especially when Rd2 is general formula (D-8) is a hydroxyaryl group; or an alkyl group having 1 to 3 carbon atoms).
The exmaples of a coupler component represented by Ad in general formula (D-l) include a yellow dye image-forming coup-ler residue, magenta dye image-forming coupler residue, cyan dye-image forming coupler residue, and colorless coupler - 50 - l 31 7500 residue.
The typical examples of the preferred diffusible DIR com-pounds useful in embodying the invention are those described, for exmaple, in U.S. Patents No. 4,234,678, No. 3,227,554, No. 3,617,291, No. 3,958,993, No. 4,149,886, and No.
3,933,500, Japanese Patent O.P.I. Publications No. 56837/1982, and No. 13239/1976, U.S. Patents No. 2,072,363, and No.
2,070,266, and Research Disclosure, 1981, Dec., No. 21228.
When incorporating any of the above-mentioned DIR com-pounds into the light-sensitive material of the invention, the preferred amount of addition is 0.0001 to 0.1 mol, in parti-cular, 0,001 to 0.05 mols per mol silver halide.
In embodying the invention, a DIR compound represented by general formula (D-1) among those described above is capable of much excellent effects.
The typical examples of DIR compounds represented general formula [D] or (D-1) are listed below. However, the scope of the invention is not limited only to these compounds.
(Example compounds of general formula [D]) ~d l-COC I CO - RJ Z
Example compound No. R d I ~ R d 2 ¦ Y d D - I ~ 1 ( 2) ( 4) (78) D - I ~ 2 ( 2) ( 4) (55) D - I - 3 ( 2) ( 3) (38) D - I - 4 ( 2) ( 3) (30) D - I - 5 ( 1) ( 1) (30) D - I - 6 t 67) (67) (34) D - I - 7 ( 7) (68) (84) D - I - 8 (58) (58) (~0) D ~ I - 9 ( 2) ( 4) ~91) D - I - 10 ( 2) ( 4) (90) D - I - 11 t 62) (62) (76) D ~ I - 12 (68) (68) (~
D - I - 13 (66) (74) (~
D - I - 14 (66) (64) (82) D - I - 15 ( 2) ( 4) (83) D - I - 16 ( 5) ( 6) (31) D - I - 17 (67) (67) (34) D - I - 18 . _ ( 4) (32) R d l l ¦ Y d N~ ~
N O
I
Rd z _ Example compound No. R d R d Y d I
D - I - 19 (69) (10) (30) D - I - 20 (70) (10) (87) D - I - 21 (12) ( 7) (34) D - I - 22 (11) ~ 10) (79) D - I - 23 ( 7) (72) (32) D - I - 24 (15) (73) (92) D - I - 25 ~ 71) t 10) (36) D - I - 26 ( 9) (10) (30) D - I - 27 (12) (13) (35) D - I - 28 (60) (10) (85) D - I - 29 (59) (10) (86) D - I - 30 (57) (10) (30) D - I - 31 (75) (72) (78) _ 53 - l 3 1 7500 O H
R d Y d Example compound No-¦ R d Y d D - I - 32 (63) (78) D - I - 33 (63) (40) D - I - 34 (65) (93) D - I - 35 (65) (38) D - I - 36 (63) (43) D - I - 37 t 63) (77) D - I - 38 (19) (95) D - I - 39 (94) (47) D - I - 40 (21) (47) D - I - 41 (19) (46) D - I - 42 (94) (46) The symbols representing substituents Rdl, Rd2 and Ydl in the above tables are used for convenience of classifying the compounds of general formula [D].
- 54 - 1 3 1 7~03 HOCO C5H 1 1 ( t) ~NII ~ O~NIICbCIIZO ~ CSIII~(t) 110 C O N C H z S
D -- I -- Ll ~I
C ~ ~ H 3 7 O N O
S 11 1~
N
OC I aH 3 7 (n) N H C O ~
S ~ .~ N H z O N N
- 55 - 1 3 1 7 50~
OC, 4 H z 9 NN ~) N
~NHCOCHO~,\\--Cslll ~ (t) C H 3 C Q CzH5 C 5 H,, (t) \N-N~ C2H5 C, 3H27CONH
~ / N
.. o.
r~
CoocllzCONH~
(Example compounds of general formula (D-1) ) C I ~ H Z 7 C O N H
/ N
l \>
( I
~ ' C O O C H z C O N H ~) ~d I - COCHCO--I
Y d EYample compound No. R . ~ R . y .
..
D ' -- 2 ( 1 ) ( 1 ) (30) D ' -- 3 ( 2 ) ( 3 ) (30) D ' - 4 ( 2 ) ( 4 ) (30) D -- S ( 5 ) ( 6 ) (31) D -- 6 ( 2 ) ( 4 ) (32) D - 7 ( 2 ) ( 3 ) (32) D -- 8 ( 7 ) ( 8 ) (33) D -- 3 3 _ ( 4 ) ( 5 5 ) t 31 7~0 Rt, 1l I Yd N O
R,l Z
Example compound ~o. ~ __ Y ~
D ' -- 9 t 9 ) ( 10) (30) D ' -- 10 ( 11 ) ( 10 ) ~30) D ' -- 11 (12) ( 7 ) (34) D ' -- 1 2 ( 1 2 ) ( 1 3 ) ( 3 5 ) D -- 13 ( 9 ) ( 14 ) (36) D -- 14 ( 15 ) ( 16 ) ( 3 7 ) 1 3 ~ 7500 o xa:Qle compound No. R
D ' - 15 (17)(38) .D - 16 (17)(39) D ' - 17 (18)(40) D - 18 (20)(41) D ' - 19 (18)t42) D ' - 20 (18)(43) D ' - 21 (18)(44) D ' - 22 (18)(45) D ' - 23 (19)(46) D ' - 24 (21). (47) D ' - 25 (21)(48) D ' - 26 (22)(49) D ' - 27 (22)(50) D ' - 28 (22)(51) D ' - 29 (23)(52) D ' - 30 (18)(53) D ' - 31 (18)(54) D ' - 32 123)(49) D - 33 (63)(96) 1 3 1 7~00 (1) through (95) in the tables above represent the fol~
lowing species.
( 1 ) ~ 2 ) C ~ , .
NH~ -- C(CH3) 3 COOCHCOOC~2H2s ( 3 ) C ~
- NH ~ CsHIl(t) NHCOCHzO - ~ CsHIltt) ( 4 ) C Q
- NH ~ CsHI~(t) ~ NHCO(CH2) 3 - ~ CsHIl(t) ( 5 ) ( 6 ) - OCII 3 , - NH - ~
O C 1 4 Hz 9 - 60 ~ 1 3 1 7500 ( 7 ) ( 8 ) c e ---N 11~/~
C O O ~I
( 9 ) --NIICO--,~ CsHI I (t) NllCOf HO --~ C s H ~ ~ ( t) C z H s ( 1 0 ) ( 1 1 ) C ~
-~ C Q -- NHCOfHO --c e , C2 ( 1 2 ) ( 1 3 ) -- C l 7113 5 < N 3 ( 1 ~ ) ( 1 5 ) ~ c e - C~13 - 61 ~ 13~7500 (16) (17) ~ SO3H . - CONHCI~H37 , (18) (19) - CONH ~ - CONH ~
OCI~Hz9 , OC, 4 Hz 9 ( n) , (20) CsH I I (t) - CONH(CU2)30 ~ C5H,,(t) (21) . - CONH ~ OC,,H2 9 (n) t22) - CONHCHzCHzCOOH
t23) - CONHCHzCH2COOCH3 ~ 62 - 1 3~ 7500 (30) (31) ~ N ~ N = N ~ N 11 2 (32) C H z N C O S ~/; ¦¦
CzHs (33) 1~ c 11 z s--. ¦ `N COO~I
CsHI I (t) NI~COCII zO ~CsH I I ( t) 34 ) (35) ~N~Br S--lS~L NllCOCsHI I
(36) -N ~=O
N- N
Cl12N- COS ~/ ll ¦ N- N
(37) -OCHzCHzjCOS ~ ~ CH3 N - N
C3H7(i) (38) (39) ~N~ ,CH3 11 \N ~ CH3 . / ~ Nll2 ~ N
(40) (41) -S ~/ ll -OCH2- N N
N- N
C 2 Hs CH3 Cl13 - 64 ~ 1 3 1 7~
(42) --O C H z--N N
COO~
(43) O ~ N ~
CHzNCO N N
Czlls iYOz ~
CO 2CH zCH zCN
t44) O N N
~CHzI COS~
~j/C 3 H
NO z ~ .
(45) N N
N ~L
NO z \/ , - 65 ~ t 3 1 7500 (46) O N N
c C N z--S
~N CH 3 t47) O N--N
/~ C H z--S
N I N N
=/ ~N'---CH3 CzHs (48) C H z--S ~ ~ C H 3 ~N CH3 N N
(49) O N--N
2 N~ /~ CH z--S
~N Cl ~Hz3 OH
13~750~
(50) O N--N
O z N ~ N~C C H Z--S ~
C2~s (Sl) OzN ~ ~ CIlHz~ N - N
(52) O N N
02N ~ ~ CH2----~\/
~N C~IHza (53) (5~)1 CH2S ~ CH2 -S
NHCOCH~
NHCOCHzCH2COOH J
( 55 ) (56) --~ N= C~ N H ~3 ( 57 ). ( 58 ) c e --NH~ -- CZHs N H COC1 3 Hz 7 ( 59 ) c e --NH~NHCOCHO--~ OH
C z H 5 C ~ H 9 ( t ) 60 ) c e --NH~ O
\ N~ C . 8 H 3 7 -68- 131750~
( 61 ) (62) O H ---NH~CH3 -- OC, zHzs ~y N--N
\S~/ 11 N--N
I
CzHs ( 63 ) (64) C O O H
--CONH~3 --NH~
OC I 4 H z 9 . OCH 3 ( 65 ) . (66) -- C O N 11 C 1 8 11 ;s 7 ~ ~ O C ~ 8 H 3 7 ( 67 ) (68) --NHC~ --N11~3 COOC~ 2Hz5 , COOC, zHz 5 ( 69 ) CsHI ~ (t) --N HCOC H O ~C 5 H,, (t) C z 1~ 5 - 69 _ 13175~
(70) c e NllCOC~3Hz~
t71) - NHCO ~ C\sHIl(t) NHCOCH20 ~ C5H,,~t) (72) C5H,,(t) NHCOCHO ~ Csllll(t) CzNs (73) - ~ NNCOCHO ~
CzHs C~sH 31 t74) (75) - Nll ~ - N
O C 2 Hs 13t7500 - 70 ~
(76) (77) _ O -CH2 N~ ~ NNCOC4Hs ~ ~ COO-(78) (79).
N ~3\ 0 C ~ N .
(80) (81) , N ~ NHCOCsH~ N ~ C z ll s (82) .
~N~\NNCOC,N,~ .
- 71 - l 3~ 7500 (83) O ~ CHz ~
- N\ . HCHOC~H, 3 0 \CH2NCOS
CH J
\CHJ
(84) ~ ~ N - N
O CH2NCOS ~ ¦¦
I N - N
CzHs ~
~ , .
(85) (86) N - N N - N
-s~ 11 -s~ 1~
N - N N - N
OH
- 72 - ~ 3 1 7500 (87) (88) --S ~/ ¦¦ -- N N ~N
N--N
C z H s CH~ CH3 (89) t90) O~<N >~O
-- S~5~NHCOC5H, I , (~NCOS~
C3~7 ~ .
(91) (92) I
O~,<N~O O~<N~O
C 11 ~--N C O S--~
N N ¦ N N
C~H7 ¦ CzH 5 . ~ ,211~.C Q, - 73 - 1 3 1 15~
(93) --S~
N N H
(94), -- CONII (CIJ2) ~O ~C5H ,, ( S) C 5 H I , ( t ) (95) ,~ C H Z N C O S ~
~ IN--N
C 2 ~I 5 NOZ CH (CH3) Z
(98) 1_CHZCH2NCOS N--C2H5 Il C 3 H 7 ( i S O) \ND
- 74 - 13t7~00 The other preferred examples of DIR compounds advantage-ously used are the following example compounds.
[Example compounds]
( D~
C~
(Cl13) 3CCOCHCONH ~ ~
S NIICO(CI12) sO Cslll I (t) N IN ~3 N= N
(Dd-2 ) C~
(Clls) sCCOCllCONII~ Cslll I (t) NIICO (CH 2) 30 ~ Csll I I ( t) N ~3 N=<
Cl~3 ~ 75 ~ 1 3 1 7~00 ( D - 3 ) N-N ~ ~ N ~
CsHIl~t) NHCOCHO ~ CsHI~(t) CzHs ( D~- 4 ) CONH
N
N = N
~ 76 - 1 31 7~00 (D--5 ) OH
CONH
' IN I--C zHs ( Dd- 6 ) C~
(CH3)3CCOCHCONII ~ Csllll(t) O NHCO(CHz)30 ~ CsHll(t) CH2NCOS 11 IN- C2Hs NOz CzHs N~N~N
~ 31~50~
( D--7 ) ce (CHJ)aCCOCHCONH ~ CsHI~(t) NHCO(CHz)10 ~ C5YI I ( t) CHz- S
NO 2 N~N~N
( D~--8 ) C~
(CHa)JCCOCHCONH ~
O NHSO2CI~H33 C ,, .--s T' N ~- 011 N N
~N~
-78- t3~7500 (D--9 ) 1--N ~r (CH z) 3 ~ NHCOCHO ~ OCOCII 3 CH3 N/lN~N C~zHzs H
N C O S ~ N
C3R7 (iso)~N~
t D~--10) ~\~CONH ~
O C I .I H z 9 CHzNCOS ¦¦ IN~3 C3H? (iso) N N
NO z ~Ns~
( D'L-ll) CONN ~
OCHzCH2NCOS 11 IN - CzHs C3H7 (iso) N ~N
t Dd--12) OH C 5 Hll(t) CONH(CHz) 40 ~ CsHIl(t) N~N"N
( Dd-13) OH
O C ~ 4 H z q ~2 ~ ~ N
( Dd-14) tCH3) 3CCOICHCONH ~ SOZNH2 C, ,H3, N N
NO z ~N~
~ 81 - l 31 7500 ( D -15) HOCO \~_~ CsHIl~t) NH ~ O ~ NHCOCH20 ~ CsHIl(t) CHzS 11 IN ~
N~N~N
( Dd-16) OH
CONH ~ COOH
~ CHz- S T N
¦~N/~C" H 23 ~ N~
NOz - 82 _ 1 3 1 7500 ( D--17) OH
,.X~ CONHCH2COOH
O fH3 ~NCOS 11 IN ~ OH
COO C I z H 2 5 ~Ns~N
( D~--18) l--C~ 8H37 O~\N/~O
~S 11---IN~
~ N
( D~--19) OC, ~H37 (n) NHCO ~
~P 1' 5 ~r ~ 83 _ t 31 7503 ( D~-20) OC~Hzs S ¦¦ IN ~3 ' N ~ O \N~
( D~-21) C~H,l(t) NHCOCH20 ~ C5 Hl,(t) O ~ NHSOzCH3 O CHzS ~ N
~ N ~N
t D¢-22) ~ NHCO(CHz) 30~Csll I I ( t) (cH3)3ccoFHcoNH ~ CsHll(t) ~ N ~ cc HH 3 - 84 _ t 3 t 7500 ( D -23) NIICO(CH2)30 ~ Csllll(t) (CH3)3CC0fHC0NH ~ Csllll(t) CQ
N~ ~ COO
D~-24) C,zHz500CCHooc ~ ~NHCOCHCONH ~ , CH~
~N ~ COO
t D~-25) C,2H2sOOC ~ NHCO~HCONH ~ COOCIzH2s N N ~ Br ( D -26) C2Hs /N~
CsH" tt) ~ OCNCONN~ r~
' C~ ~ CQ
( DL-27) CO2CI2Rzs COFHCONH
i C~
N O
Cz~ls ~
( ~-28) C 1 2H zsOOCfHCOOCI2112s N~ ~ CO
- 86 - 1 3~ 7 5 00 ( D~- 29) ~ NH ~ S ~ N-IN
C,3}1Z7CONH `N O CZH5 CQ ~ ~CQ
CQ
( D~-30) C5~3, 1 (t) ( t) C511" ~ OCHZCONH
~ 4~ N--N
O C~H9 ( Dd-31) OH
CONHC~H37 S
N N
1-1, ' H NHz ( Dd-32) NllCO(CNz)30 ~ CsHIl(t~
~CH3)3CCOfNCONH ~ CsHIl(t) O ~ N ~ O CQ
~ N- N
CKz- NCOS ~/ ll ¦ N- N
~. . `
( D~--33) NHCO(CHz) ~0~3Cslll I (t) (CN3) ~CCOICHCONH~ CsHI ~ ~t) 0~N~O CQ
N--N
C~H
( D--3~1) OH
~CONHCI ~H37 N~N
( D~--35) OH
~ NHCOCHO ~ CsHI~(t) CH3 ~ C~ C2Hs Csllll(t) N N - C2Hs 1_1 ( D~--36) Cl7H3s N
~0(~
Br go 1 31 7500 ( Dd-37) ,N~
~ OCHCONH ~ N
C,sH31 CzH5 ~N O
¦ OC,H~
CQ~_ Ce ce ( Dd- 38) C ~ 2HZ50CO ICHCOOC~zH2s N N ~ NHCOC~Hq ( Dd-39) C~zH2sOOC ~ NHCOCHCONH ~ COOCI2H 2 5 N~N ~ NllCOCsllll - 91- t317500 ( Dd- 40) OH
, ~ O C I z H z 9 CH zNCON~
NO2CzHs COzCHzCH2CIY
( D~--41) OH
~CONHCI bH33 ~CII:S~
NO2 , OH
- 92- t317500 ( D~--42) CONH ~
CH NCOS ~ ~ NHz ( D~-43) COzC1~13 2 9 (CH3)3CCOCHCONH
O C
NOz I N -N
CHzS ~ ll N- N
I ~ C21~s CH2CH2N, ~C211s ~ 93- 1317500 ( Dd- 44) OH
~CONH(CH2~ 30Cl zHzs O N--N
~N~S~N~LC~Hg ( Dd- 45) ~; ~0 ~ N O z C z H s NHCOfHO ~CsHI I (t) C z H 5 C s H I I ( t ) - 94_ 13~7500 ( D ~--4 6 ) C~sH370 ~ COfHCONH
N~ OCzHs ~N~Czlls ( Dd~47) COzH
ClsH~70 ~ COCHCONH
~N~y~ OCH~
~N ~ NHCOC~H,~
( Dd--4 8) o CH~
. C2Hs C2H~C~
hHCOCIHO
C2Hs C~sH~
1 31 ~500 ( D~-49) NHCO(CN2)30 ~ CsHll(t) (CH~)3CCOfHCONH - ~ CsHIl(t~
y ~ H NHC0CbH,3 ¦ CHzlCOS ~ NN
( Dd-50) Cl3H2~CONH
~ N N
O ~ , COOCHzCONH ~
( D~--51 CH30COfllCONII
IN I ~3NH2 N--N
- ( Dd- 52) ( t ) C 5 H I I ~ O C H 2 C O N 11 C5H" (t) CONII 11 ~N2~
~N/~O CIIZNCII3 CQ~CQ COS~/N_ IN
CQ
CO2~3 ~ 97 -1 ~1 7 5 00 ( D - 53) OH
~ CONH(CHZ)30 ~ C5H" (t) ~ CsHIl(t) N ~ CH2S ~ N -IN
`N CH3 t Dd-54) ~ COzCHCOzC~zHz 5 (CH3)3CCOCHCONH ~ CH 3 c~ .
~' CZHS
¦ CHzCHzCOz ~
1 ~ 1 7500 ( Dd- 5~) CzHs ( t) C 5H " ~ OCHCONH ~ N~N~N
CsHI I (t) CONH~ ~
CQ~ CQ I ~3 CQ
( Dd_56) ~1--N
S~ 1~ NHCOCsH
C,7H~,~ \S/
N~N
, ( D ~ 57) ce N--N
O ~ UH~S
c e ,~3~ c Q
CON~ 2 C~
t D"--58) CzHs HO $~ OCHCONH ~ C ~ S _</N--IIN
C4N,, (t) NN~ N--N
,¢~, C~
loo- 1317~00 t D--59 ) ( n ) N " C ., O C N N
ce~ce ce ( D~--60) ClzN2sOOC~ ~ NHCOjHCONH ~ 3 ~COOCI2112s / N ~3~B r ( D--61) ON
,CONHC, sH 17 N--N
l3l7son 62) OH
OCI~Hz9 CHz ,N ~ COO
( D~-63) OH
CONHCH2CHzCOOH
N
CHZS ~
N- N
CI,HZ3 '' ~3 - 102 ~ l 31 7500 ( Dd 64) OH
~ CONHCHzCHzCOOll NO2 ~ N
CH2S ~ ll N- N
Cl~Hz3 ( D -65) OH
~ CONHCH2GH2COOH
NO2 ~ N
CH2S ~ ll N- N
Cl~Hz~ ¦
- 103 - 1 3 1 75~
. .
( D--66) OH
~ CONHCHzCH2COOH
OzN ~ N
CHzS ~ ll I N- N
OH
( D~--6 7 ) O H
~CONHCHzCHzCOOH
Nl ~1 N~ C H z S ~ ll N--N
C~sH31 ~3 OH
- 104 - l 3 1 7500 ( D--6 8 ) O H
CONH ~3 OC, 4Hz~
N
~\ C H 2 S ~ ll N--N
~3 t D--6 9 ) O H
O C, ~ H z 9 ~N
~\ CH 2S~ ll N--N
COOH
( D~-70) OH
~CONH~30CI ~H2g tn) I ~1 2 ~ N_IN
CZHS
( Dd--71) OH C5H " (t) CONH -(CH2)~0 ~ C5H " tt) ~ Nl ~1 CHZS ~ N_IN
CzHs ~ 3 1 ~ 3 0 10 ( Dd 72) OH
CONH ~
~ OC,~H29 NO2 ~ - Nl ~
~\ C H Z S ~ 11 N- N
COOH
( D--73) OH
CONH ~
~ OCI4H29 CH2S ~ ll ~3 -107_ l 3~7~
( D~--74) OH
~ O C ~ ,~ H z 9 NO2~Nl~¦
C H 2 S ~N--¦¦
CH3 ~3 OH
( D--75) OH
~, C O N H
NOz~ 1~1 !i~ N~ N--N
CzHs ( D -76) OH
CONH - Cl12CHzCOOH
N
~f \ 1 CIIHz~ N N
t D -77) OH
CONH - CHzCHzCOOII
CH2S ~ k CH~
- log - 1 31 7500 ( D~-78) OH
CONH- CH 2 CHzCOOH
I ,~
CHzS ~ ~ CH3 Cl3Hz7 N N
( D -79) OH
CONH- CHzCHzCOOH
~3 Nl ~1 CHzS ~ k CH3 1317:5`~0 ( D~--80) OH
OC,4 H z~
N ~
( D~--81) OH
OC, 4 H z ~3 Nl~
~\CHzSl~ ~ CH3 ( D ~--82) OH
O C, 4 H 2 9 N
~\ C H z S 1/ ~r C H 3 ( Dd- 83) C O N H ~
OC, ~Hzq I ~1 ~\ C H 2 S 1' k C H 5 ( D~--84) OH
OC, ~llz~
C~
> C = N
C~
N N ~3 N = N
( D~--85) OH
C O N N ~) , N O z >C = N~
N IN ~ O H
N = N
( Dd- 86) OH CsHI I (t) 3~ C O N N ~ C H 2 ) .~ O ~ C s I I I ( t ) >C=N~
CQ
N
N = N
( D - 87) CQ
tCH3)3CCoCHCoNH ~ CsHIl~t) ¦ NHCO (CH 2) J ~ C sH ~ I ( t) > C=N ~ C9 ; N
~ N
- 114 - l 3 1 7500 Any of the above-mentioned DIR compounds may be incorpo-rated into the light-sensitive silver halide emulsion layer and/or the non-light-sensitive photogrpahic structural layer;
preferably it is included in the light-sensitive silver halide emulsion layer.
Two or more kinds of DIR compounds may be included in one layer, or one and same kind of such compound may be included in two or more different layers.
These DIR compounds are preferably included in the emul-sion layer in the amount of 2 x 10-5 to 5 x 10~l mols, more favorably 1 x 10-4 to 1 x 10~l mols, per mol of the silver in the emulsion layer.
To incorporate such DIR compounds in the silver halide emulsion or in the coating solution for another photographic structural layer, where the DIR compound is alkali-soluble, it may be added in the form of an alkaline solution. If the com-pound is oil-soluble, it is preferred that the compound is added to the silver halide emulsion according to any of the procedures described in the respective specifications of, for example, U.S. Patent Nos. 2,322,027; 2,801,171; 2,272,191;
and 2,304,940, that is, the DIR compound is dissolved in a high-boiling solvent, or if necessary, in a combination of such solvent and a low-boiling solvent, so that it is dis-persed as fine particles therein, such dispersion can be added to the emulsion. In this conjunction, a mixture of two or 1 3 ~ 7 5 ~ 0 more kinds of DIR compounds may be used. A further preferred method for addition of such DIR compound will be described in detail. The preferred method comprises dissolving one or more kinds of the above-mentioned DIR compounds in organic acid imides, carbamates, esters, ketones, urea derivatives, eithers, or hydrocarbons, or in particular, any of such high-boiling solvents di-n-butyl phthalate, tri-cresyl phosphate, triphenyl phosphate, di-isoctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamide butyl, N,N-diethyl laurylamide, n-pentadecyl phenylether, di-octylphthalate, n-nonyl phenol, 3-pentadecyl phenylethyl ether, 2,5-di-sec-amylphenyl butylether, monophenyl-di-o-chlorophenyl phosphate, and fluoroparaffin, and/or any of such low-boiling solvents as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetonitrile, dimethylforma-mide, dioxane, and methyl ethyl ketone, mixing the solution with an aqueous solution containing anionic surfactants, such as alkyl benzosulfonic acid and alkyl naphthalenesulfonic acid, and/or nonionic surfactants, such as sorbitan sesqui-oleate and sorbitan mono-laurate, and/or a hydrophilic binder, such as gelatin or the like, then emulsifying and dispersing the mixture in a high-speed rotary mixer or a colloid mill, or in an ultrasonic dispersion apparatus, and adding the disper-- 116 - 1 31 7 ~ 0 sion to the silver halide emulsion.
Alternatively, the DIR compound or compounds may be dis-persed by employing any of known latex dispersion techniques.
Various latex dispersion methods and their advantages are des-cribed in Japanese Patent O.P.I. Publication Nos. 74538/1974, 59943/1976, and 32552/1979, and also in "Research Disclosure", No. 14850, August 1976, pp 77 to 79.
Examples of latex suitable for this purpose are homopoly-mers, copolymers, and terpolymers of various monometers, such as styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxy ethyl methacrylate, 2-(methacryloyloxy)ethyl trimethyl ammonium methosulfate, 3-(methacryloyloxy)propane-l-sodium sulfonate, N-isopropyl acrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, and 2-acrylamide-2-methylpropane sul-fonic acid.
Aforesaid DIR compounds may be synthesized according to various methods described in the following publications: U.S.
Patent Nos. 3,227,554; 3,615,506; 3,617,291; 3,632,345;
3,928,041; 3,933,500; 3,938,996; 3,958,992; 3,961,959;
4,046,574; 4,052,213; 4,063,950; 4,095,984; 4,149,886; and 4,234,678; U.K. Patent Nos. 2,072,363 and 2,070,266; Research Disclosure No. 21228 (1981); Japanese Patent O.P.I. Publica-tion Nos. 81144/1975, 81145/1975, 13239/1976, 64927/1976, 104825/1976, 105819/1976, 65433/1977, 82423/1977, 117627/1977, 130327/1977, 154631/1977, 7232/1978, 9116/1978, 29717/1978, - 117 ~ l 3 1 7500 70821/1978, 103472/1978, 10529/1978, 135333/1978, 143223/1978, 13333/1979, 49138/1979, 114241/1979, 35858/1982, 145135/1979, 161237/1980, 114946/1981, 154234/1982, and 56837/1982; and Japanese Patent Application Nos. 44831/19a2 and 45809/1982.
The DIR compound or compounds may be added to the light-sensitive silver halide emulsion layer and/or the non-light-sensitive photographic structural layer as stated above, but preferably such compound or compounds are incorporated into at least one silver-halide emulsion layer. For example, for use with a multi-layered color photographic light-sensitive mate-rial of the conventional type having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emul-sion layer, and a red-sensitive silver halide emulsion layer, such compound may be incorporated in one or more of these layers.
The tetrazaindene derivatives which can be used in the practice of the present invention are known as stabilizers for silver halide emulsions in light-sensitive materials, and among them, especially one expressed by the following general formula[T-VIII] can be advantageously used:
General formula [T-VIII]
(OH)~
Rt 9 N N
wherein m and n respectively stand for an integer of 2 or 3; Rt~ and Rtg independently represent a hydrogen atom, or an alkenyl or alkyl group having 1 to 4 carbon atoms which may have a substituent group, or an acryl group which may have substituent group.
While the tetrazaindene derivatives expressed by the foregoing general formula [T-VIII] are especially effective for the purpose of the invention, there are various other tetrazaindene derivatives which can be advantageously used in the practice of the invention, as enumerated below by way of example and not by way of limitation.
[Example compounds]
T-l: 4-hydroxy-1,3,3a,7-tetrazaindene;
T-2: 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene;
T-3: 4-hydroxy-6-hydroxy-1,3,3a,7-tetrazaindene;
T-4: 4-hydroxy-6-butyl-1,3,3a,7-tetrazaindene;
T-5; 4-hydroxy-5,6-dimethyl-1,3,3a,7-tetrazaindene;
T-6: 2-ethyl-4-hydroxy-6-propyl-1,3,3a,7-tetrazaindene;
T-7: 2-allyl-4-hydroxy-1,3,3a,7-tetrazaindene;
T-8: 4-hydroxy-6-phenyl-1,3,3a,7-tetrazaindene.
The compounds can be synthesized with reference to the relevant descriptions given in Japanese Patent Publication Nos. 18102/1971 and 2533/1969. Of these compounds, those hav-ing a hydroxy group at the 4-position are preferred, and those having an alkyl or aryl group at the 6-position are particu-larly preferred.
The 6-aminopurine derivatives useful for the purpose of the invention embrace those known as stabilizers for silver halide emulsions in light-sensitive materials, and in parti-cular, those expressed by the following general formula [P-IX]
can be advantageously used:
General formula [P-IX]
NH~ H
~ N
Rrlo ~ N ~ N ~
wherein Rp1o represents a hydrogen atom or hydroxy group;
or an alkyl group with 1 to 4 carbon atoms which may have a substituent group; and Rpll represents a hydrogen atom; or an alkyl group with 1 to 4 carbon atoms which may have a substi-tuent group; or an aryl group which may have a substituent group.
- 120 _ l 31 7500 When the 6-aminopurine derivatives expressed by the fore-going general formula [P-IX] are especially effective for the purpose of the invention, there are various other 6-amino-purine derivatives which can be advantageously used in the practice of the invention, as enumerated below by way of exam-ple and not by way of limitation.
[Compounds exemplified]
P-l: 6-aminopurine;
P-2: 2-hydroxy-6-aminopurine;
P-3: 2-methyl-6-aminopurine;
P-4: 6-amino-8-methylpurine;
P-5: 6-amino-8-phenylpurine;
P-6: 2-hydroxy-6-amino-8-phenylpurine;
P-7: 2-hydroxymethyl-6-aminopurine.
These tetrazaindene derivatives and 6-aminopurine deriva-tives are highly effective for the purpose of the invention if they are added to the silver halide emulsion, preferably with-in the range of from 5 mg to 18 g per mol silver halide.
Of these compounds, which can form a silver salt having a solubility product constant of not more than 1 x 10 9 in con-junction with silver ions, those which are not more than 1 x 10 ll in solubility product terms are especially effective.
With respect to DIR compounds, tetrazaindene derivatives, and 6-aminopurine derivatives, it has been known that when added to conventional silver halide emulsions, they contribute - 121 ~ 1 3 1 75 00 for improvement of image quality and can also inhibit repening fogging that may possibly develop in the process of emulsion preparation. Prior to the present invention, however, it was not known in the art that when used in conjunction with the process to which the invention is directed, those compounds would contribute to improve graininess.
In the present invention, the silver-halide color photo-graphic light-sensitive material to be processed is preferably such that the thickness of its photographic structural layer is not more than 25 ~m. The expression "thickness of the photographic structural layer" used herein means the total thickness of all constituent layers of the photographic structural layer other than the support, that is, all the hydrophilic colloidal layers including the silver-halide emul-sion layer (which consists of at least three layers in the case of a full color photographic material), and other layers formed as required, such as subbing layer, antihalation lay-er, intermediate layer, filter layer, and protective layer, which thickness refers to dry state thickness. For the hy-drophilic colloid, gelatin is often used, in which case the layer thickness may be referred to as the gelatin coat thick-ness. Thickness measurements may be carried out on a micro-meter. The total thickness of the photographic structural layer is more favorably not more the 22 ~m, still more favor-ably less than 20 ~m, and especially preferably not more than - 122 - l 3 1 750~
18 ~m. From the standpoint of photographic performance, a layer thickness of not less than 8 ~m is preferred.
Next, preferred conditions for development and other photographic processing steps in connection with the practice of the invention will be explained.
One preferred mode for carrying out the invention is such that the concentration of the developing agent in the devel-oper solution used is not less than 1.5 x 10-2 mols/Q. This condition constitutes an essential feature of the third inven-tion which will be hereinafter described in detail. The de-veloping agent to be used and further preferred conditions will be discussed hereinafter.
Another preferred mode for carrying out the invention is such that the pH of the developer solution is 10.4 or higher.
By adopting such high pH value it is possible to accelerate development and also to obtain further improved graininess.
The pH is more favorably 10.5 to 12.0, still more favorably 10.6 to 11.5.
A further preferred mode for carrying out the invention is such that the developing temperature is not less than 40C.
Processing at such high temperature can accelerate development and provide further improved graininess. Development is per-formed preferably at temperatures of 40C to 70C, more favor-ably 45C to 60C. This condition constitutes an essential feature of the second invention, which will be discussed here-- 123 - t317500 inafter in further detail.
Another preferred mode for carrying out the invention is such that the concentration of the sulfite in the developer solution used is not more than 1.5 x 10-2 mols/Q. Such low concentration of sulfite in the developer solution is intended to accelerate development and also to provide improved graini-ness. The concentration range of the sulfite is preferably O
to 1.0 x 10-2 mols/Q, inclusive of zero, more favorably O to 0.5 x 10-2 mols/Q, inclusive of zero.
For preferred types of sulfite to be included in the developer solution, the following are mentioned.
Typical examples include potassium sulfite, sodium sul-fite, lithium sulfite, potassium metabisulfite, and sodium metabisulfite. Also, those compounds which, when dissolved in the developer solution, can release sulfite ions are useful for the purpose of the invention. Examples of these compounds are formaldehyde bisulfite adduct, glutaric aldehyde bisulfite adduct, and the like, which are also included in the scope of sulfites which can be used the purpose of the invention.
Another preferred mode for carrying out the invention is such that the concentration of the bromide in the developer solution used is not more than 0.8 x 10-2 mols/Q. By limiting the concentration of the bromide to such low degree it is pos-sible to obtain same effect as above mentioned. The bromide concentration is more favorably 0.05 x 10-2 to 0.7 x 10-2 - 124 - 1 31 7~
mols/~, still more favorably 0.2 x 10-2 to 0.6 x 10-2 mols/~.
For preferred types of bromides for inclusion in the de-veloper solution, sodium bromide, potassium bromide, and lithium bromide are available.
Another preferred mode for carrying out the invention is such that the developer solution used contains at least one kind of compound of those expressed respectively by the gen-eral formulas lA-I] through [A-VI] shown hereinbelow. Any of these compounds functions as a development accelerator.
General formula [A-I]
X a I - ( C 11 2 ) n a I ~ t X a z - ( C H 2 ) n a z ) o ~ I X a 3 - t C 1I z )--~ X ~ ~1 In the above formula, Xa2 and Xa3 independently represent a sulfur or oxygen atom; Xa1 and Xa4 independently represent SH or OH groups; and na1, na2, na3, each stands for a positive integer of 0 to 500, at least one of the above-mentioned na1, na2, and na3 being an integer larger than zero; provided that at least one of the above-mentioned Xa1, Xa2, Xa3, and Xa4 is a sulfur atom.
General formula [A-II]
A a z A a 3 - N <
Aa 4 Ra z - 125 ~ l 31 7500 In the above formula [A-II], Ral and Ra2 independently represent a hydrogen atom; or an alkyl group, such as methyl, ethyl, or propyl group, or a heterocyclic group which is a ring Ral and Ra2 may form together with an oxygen or nitrogen atom; Aa2, Aa3, and Aa4 independently represent a hydrogen atom; or an alkyl group, such as methyl or ethyl group; or a halogen atom, such as fluorine or bromine atom; and Aal repre-Ra3 sents a hydroxyl group, or -N in which Ra 3 and Ra4 in-Ra4 dependently represent a hydrogen atom, or an alkyl group hav-ing 1 to 3 carbon atoms.
General formula [A-III]
.
Ras Aa ~ Ra8 Xa5 ~) ~1 Ra 7 In the above formula [A-III], Ras, Ra6, Ra~, and Ra8 in-dependently represent a hydrogen atom, or an alkyl group, aralkyl group, or substituted or unsubstituted allyl group;
and Aa2 represents a nitrogen or phosphorus atom. Ra8 may be a substituted or unsubstituted alkylene group; and Ras and Ra8 may form a ring; or may be substituted or unsubstituted pyridinium groups. Symbol XaS represents an anion group such as a halogen atom, OH, or an anionic group, such as sulfate or nitrate group.
General formula [A-IV]
R~ I o X N--(CH z) n, ~--(C) ma 2 Ya \+/ I
(R" 9 ) Q a R a l l In the above formula [A-IV], Ya represents a hydrogen Ra 12 atom, a hydroxyl group, or -N ; Rag, Ra10, Rall, Ral2, Ral3 and Ral3 independently represent a hydrogen atom, or a substi-tuted or unsubstituted alkyl, carbamoyl, acetyl, or amino group having 1 to 3 carbon atoms; X represents an oxygen or sulfur atom, or N-Ral4, in which Ral4 represents a hydrogen atom, or a subsi-ituted or unsubstituted alkyl group having 1 to 3 carbon atoms; and Qa, ma2, and na4, each represents 0, 1, 2, or 3.
General formula [A-V]
Rb ~ \ ' / N --tA b ) n b O R b 3 R b 2 In the above formula [A-V], Rbl and Rb2 independently re-present a hydrogen atom, or an alkyl, alkoxy, or aryl group, or a nitrogen-containing heterocycle in which Rbl and Rb2 may form a ring or in which Rbl or Rb2 together with Ab may form a ring; Rb3 represents an alkyl group; Ab represents an alkylene group; and nb represents an integer of O to 6.
General formula [A-VI]
N / Rbz ' \ Rb3 In the above formula [A-VI], Rb1' represents a hydroxy-alkyl group having 2 to 6 carbon atoms; Rb2' and Rb3' indepen-dently represent a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl or benzyl group having 2 Xb to 6 carbon atoms, or formula Cnb' H2nb' -N , in which nb' Zb represents an in~eger of 1 to 6; and Xb and Zb independently represent a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms.
Examples of the compounds expressed by the general for-mula [A-I] are enumerated below.
A-I-l HO(CH2)2S(CH2)2S(CH2)20H
A-I-2 HO(CH2)l0s(cH2)2s(cH2)looH
A-I-3 HS-(CH2CH20)3s-CH 2 CH 2 SH
A-I-4 (HoCH2CH2t2 A-I-5 HO(CH2)3S(CH2)3S(CH2)30H
- 128 - 13175~
A-I-6 Ho(cH2)2s(cH2)2o(cH2)2o(cH2)2s(cH2)2oH
A-I-7 HO(CH2CH20)l5CH2CH2SH
A-I-8 HO(CH2)4S(CH2)3S(CH2)40H
A-I-10 H0(CH2)3S(CHz)2S(CH2)30H
A-I-11 HO(CH2)2S(CH2)20H
Illustrative of the compounds expressed by the general formula [A-II] are as follows:
1~9 1 3~ 7500 A ~ 1 ~ C H ~
H 2 ~ N O
~ , ,, A ~ 2 F~
H z N ~3 < C z H s A -- 11 -- 3 C N, > ~3 < C N
A -- 11 -- 4 H 0 ~3 < C 11 3 A -- 11 -- 5 C ~
~I z N ~3--N <
U, N ~ N~O
- 130 - l 3 1 7~
A -- 11 -- 7H z N ~3 N~ ~
A -- 11 -- 8 ~OH
H z N ~ N~) F
N H z A -- ~ --10C z H 5 ~ C z H 5 ~ F
C H 3 /~
A -- ~ --11 0 C ~ ~ C - ~
N H z B r ~ B r ~,IJ
N ll 2 A -- 11 -- 13 f~
B.r ~ Br ~C113 Exmaples of the compounds expressed by the genearl for-mula [A-III] are enuemrated below.
A-III-l (1-carboxyethyl)methyl dodecylsulfonium hydroxide A-III-2 (4-sulfobutyl)dimethyl dodecylammonium hydroxide A-III-3 (carboxymethyl)dimethyl octadecylammonium hydroxide A-III-4 (1-carboxyethyl)methyl hexadecyl sulfonium hydroxide Illustrative of the compounds expressed by the general formula [A-IV] are as follows:
- 132 - 1~t7500 0~1-- C H z C 112 C 112 N 112 A -- IV -- 2 ~
O N--CIIzCII--Cl13 \ I
A -- N -- 3 ~
\ I
Nll 2 A -- IV -- ~1 ~ C 11:~
O~N-- CllzCI12 -- N<
A -- IV - 5 ~
HN~N--CllzC112C112NI12 A -- IV -- 6 C IJ a \~ ` C11 3 HN N-- CHzCllz --N<
~< C 11 3 Cll 3 - 133 - t 31 7500 HN 3 - CHz- CH- NHz A - ~ - 8 /--~
S~ N - C~lzCHzCHzNHz A - ~ - 9 r ~
S~ N - CHzCHzOH
A - ~ -10 COCH 3 HN 3 - CHz- 1- NHz C ~I 3 A - ~ - 11 r-\
HN ~ N - CH- NHz A - N - 12 ~
O~ N - Cll- Nllz C~l 3 A - N -13 ~ A - N - 14 O~ NH
A ~ 15 /--\
Il--N N--C z H s A -- N ~ 16 ~
O~N--C z H s A -- IV --17 /--\
O ~N--C 2 H 4 0 H
H--N ~N--C3H7 A -- IV --19 /--\
. 0~ C 3 H 7 The compounds expressed by the foregoing general formulas [A-I] to [A-IV] can easily be synthesized according to the methods described in Japanese Patent O.P.I. Publication No.
15554/1975, USP 3,201,242, USP 2,950,970, USP3,706,562, USP
3,893,862, and RD 15176.
The compounds expressed by these general formulas lA-I]
to [A-IV] may be added to the color developer solution, pre-ferably in the amount of 0.01 g to 60 g/liter, more favorably in the amount of 0.1 g to 30 gtliter-General formula [A-V]
R b I \
/,~' (A b 3 n b R b 3 R b Z
In the above formula, Rbl and Rb2 independently represent a hydrogen atom, or an alkyl, alkoxy, or aryl group, or a nitrogen-containing heterocycle, in which Rbl and Rb2 may form a ring together with Ab, or in which Rbl or Rb2 together with Ab may form a ring; Rb 3 represents an alkyl group; Ab repre-sents an alkylene group; and nb represents an integer O to 6.
In the above-mentioned general formula ~A-V], the alkyl groups represented by Rbl and Rb2 are preferably those having 1 to 5 carbon atoms, such as a methyl, ethyl, propyl, isopro-pyl, or butyl group; if each of them is an alkoxy group, it is preferably one having 1 to 5 carbon atoms, such as a methoxy, ethoxy, or propoxy group; if each of them is an aryl group, it may be, for exmaple, a phenyl, 4-hydroxyphenyl, or 4-sulfophenyl group. If Rbl and Rb2 form a nitrogen-containing heterocyclic ring, it may be, for example, a piperidine, mor-pholine, piperazine, or 1,4-thiazine ring. If Rbl or Rb2 to-gether with Ab form a nitrogen-containing heterocyclic ring, it may be, for example, a piperidine ring. The alkyl group represented by Rb 3 iS preferably one having 1 to 8 carbon atoms, such as a methyl, ethyl, propyl, isopropyl, butyl, or - 136 ~ 13 1 75~G
hexyl group. The alkylene group represented by Ab may be of a branched chain configuration, for example, a methylene, ethy-lene, trimethylene, 2-methyl trimethylene, 2-methyl tetra-methylene, propylene, 1-methyl trimethylene, or tetramethylene group.
Preferred typical examples of the compounds expressed by the general formula [A-V] are as follows:
_ _ _ _ . . . . . .. . . .
HzN --~CHz~O - CHz - CH ~
A - V - 2 HzN (CHz~O - C 3 H 7 ( i a O) A - V - 3 HzN (Cllz-~O - C3H~
A - V - 4 HzN (CHz~O - CH3 A - V - 5 H 2 N- t CHz~O - C 2 Hs - 137 _ 1 31 75~
A -- V -- 6 N z N ( C H 2~r 0 --C ~ H q A -- V -- 8 CH3~
~ NtCH z~30-- C zH 5 H--N ~N (Cllz~30--CB3 A -- V --10 ~
J~ C ll 2 ~2 0--C z 11 s - 138 _ l 3 ~ 7500 A - V - 11 9 2 N-~CHz~0 -C 2 Hs A - V - 12 HzN ~CHz~0 -C3H7 A - V -13 H2N-~CHz~0 -C3H 7 ( i S O) A - V -14 HzN - CHz - 0 -CzHs A - V -15 HzN - CHz - 0 - C 3 H7 A - V -16 HzN - CHCHz -0- C2Hs A - V - 17 HzN - 0 - CzH5 i A - V - 18 ~
O~ N--~CHz~-zO ~ CzH 5 A - V - 19 H,N-~CH2t~0 - C3H7 A - V - 20 HzN ~CHzt~0 - CzHs ~CHz~0 - CH3 H
H- N ~ CHz~20 -CH3 - 139 - l 31 7~0() Of these compounds expressed by the general formula [A-V], those of (A-V-2), (A-V-4), (A-V-5), (A-V-7), (A-V-ll), (A-V-150, and (A-V-18) are especially preferably used for the pur-pose of the invention.
These compounds are available from a commercial source (for example, Koei Chemical Co., Ltd.).
Any of the compounds expressed by the general formula [A-V] is used for addition to the color developer solution, preferably in the amount of 0.01 to 100 g, more favorably 0.1 to 50 g, per liter of the solution.
Of the compounds expressed by the foregoing general for-mula [A-VI], those expressed by the following general formula A-VI'] are preferably used.
General formula [A-VI'~
/ R b S
R' b~ - N ~
R b b In the formula, R'b4 represents a hydroxyalkyl group hav-ing 2 to 4 carbon atoms; R'bs and R'b6 independently represent an alkyl group having 1 to 4 carbon atoms; or a hydroxyalkyl group having 2 to 4 carbon atoms.
Preferred examples of the compounds expressed by afore-said general formula [A-V] are as follows.
Namely, ethanolamine, diethanol amine, triethanol amine, diisopropanol amine, 2-methyl aminoethanol, 2-ethyl amino-ethanol, 2-dimethyl aminoethanol, 2-diethyl amino ether, 1-diethyl amino-2-propanol, 3-diethyl amino-l-propanol, 3-dimethylamino-l-propanol, isopropyl aminoethanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, ethylene diamine tetraisopropanol, benzyl diethanolamine, and 2-amino-2-(hydroxymethyl)-1,3-propanediol.
Any of the compounds expressed by the general formula [A-VI] is used preferably in the amount of 3 g to 100 g, more favorably in the amount of 6 g to 50 g, per liter of the color developer solution.
A further preferred mode for carrying out the invention is such that the developer solution used contains at least one kind of compound of those expressed by the following general formulas ER-I] through lR-III]-General formula lR-I]
".~ ' ,~ ~ ( X r I ) n r ;Z r ( X r ) m r~ ~ X r Z
In the formula, X'r and X'R1 independently represent a halogen atom, or alkyl, aryl, amino, hydroxyl, nitro, carboxyl, or sulfonyl group; X'rz represents a hydrogen atom, an alkyl or aryl group, or a double bond for ring formation; zr repre-sents a plurality of atoms composed of carbon, oxygen, nitro-- 141 - l 31 7500 gen, and sulfur atoms necessary for ring formation; and n and m, each represents 0, 1, 2, or 3.
General formula [R-II]
,~Y r a ~ Y r I
Y r 3 Y r 2 In the formula, Yra, Yrl, Yr2, and Yr3 independently re-present a hydrogen or halogen atom; or an alkyl, amino, hy-droxyl, nitro, carboxyl, or sulfonyl group.
General formula [R-III]
,. Y r ~
Y r ~TF X r 2 X r 3 In the formula, Tr represents a nitrogen or phosphorus atom; Xr2 and Xr3 independently represent a hydrogen atom, or an alkyl or aryl group, or a halogen atom; Yr4 and Yrs inde-pendently represent an alkyl or aryl groups, where Yr4 and Yr5 may form a heterocyclic ring through ring closure.
Any of the compounds expressed by the foregoing general formulas [R-I] through [R-III] can act as an inhibitor. In the practice of the invention, if an organic inhibitor is used in the developer solution, various compounds may be mentioned - 142 ~ 1 3 1 75~a as those suitable for such use, including nitrogen-containing heterocyclic compounds, mercapto group-containing compounds, aromatic compounds, onium compounds, and compounds having iodine atoms in their substituent groups; among these, those expressed by aforesaid general formulas [R-I], [R-II], and [R-III] are preferred.
The compounds expressed by the general formula [R-I] are more favorably those expressed by the general formula [R'-IV]
or [R'-V], most preferably those expressed by the general for-mulas [R'-VI] through [R'-XI].
Whilst, the compounds expressed by the general formula [R-II] are most favorably those expressed by the general for-mula [R'-XII] or [R'-XIII].
These compounds are used in the developer solution, pre-ferably in the amount of 0.005 to 20 g, more favorably in the amount of 0.01 to 5 g, per liter of the solution.
- 143 - ~317~
General formula [R'-VI] R r _ NH 11 R r ,/~N~ N
General formula [R'-VII] (0~l) m ~ N ~J` R r General formula 1R'-VIII] ( Rj) m ( n, r ) ~ H--/N
General formula [R'-IX] (R r ) H
(R, r ) n ~ R r z N
General formula [R'-X] ( n r ) ~ N~
- 144 - 1317~0 - ~ .
General formula ~R'XI] IR r T r ~ y r I
N - N yr 2 . _ _ . .. . .
(where Tr is C or N) General formula [R'XII] (NOz) n r R r R r I
. . .
General formula [R'-XIII] OH
Rr ~ OH
Rr l In the above formulas, Rr, Rrl, and Rr2 independently re-present a hydrogen atom or halogen atom (CQ, Br, I, etc.), or an alkyl group which may have a substituent group, aryl group which may have a substituent group, carboxylic group, benzyl group, -NHCORr' (in which Rr' represents an alkyl or aryl group), thiocarboxylic group, carboxy alkylate group (such as -COOCH3, -COOC2H5, and COOC3H7), alkoxy group (such as a methoxy, ethoxy, or propioxy group), hydroxyl group, sulfonyl halide group (-S02CQ, -SO2Br, etc.) amino group which may have - 145 ~ l 31 7500 substituent group, sulfonic group, nitro group, mercapto group, or cyano group.
Symbols Yrl and Yrz respectively have same meanings as Yrl and Yr2 in the foregoing formula ~R-II].
General formula [R'-IV]
. .
A compound having 1 to 9 carbon atoms of which 2 to 5 are replaced by nitrogen atoms, or its derivative.
General formula lR'-V]
,- , Z~ 5 A compound having 1 to 5 carbon atoms of which 2 to 4 are replaced by nitrogen atoms, or its derivatives.
Preferred examples illustrative of the organic inhibitors expressed by aforesaid formulas are given hereinbelow. Need-less to say, however, it is understood that the compounds of the formulas which are useful for the purpose of the invention are not limited to those exemplified below.
- 146 - ~3~7500 (Examples of organic inhibitors) Il 5C zOOC~
HOOC ~ N ~ SH
~0 J' S 11 HOOC ~ N~N~N
~ N N
CH3 ~ N ~ N~
- 147 - t 3 1 7~00 Z 6 ~ S ~>
CH3 / SO3~CH~, 011 ~3 O H
- Z 8CzHsOCHz~ y, ~
~N--N
OH
HS ~,N~NH2 N N
\Nlt/ \~1/
- 148 - ~ 31 7~00 Zll CH 3 II S ~ N ~I C O ~3 N - N
HS y N ~ NHCOCH 3 Z13 f 2 Hs HS ~ N ~ NHCOCH 3 N N
N~ N
~N ~ SH
N N
Z16 NO2 ~ COOII
.. . .
Z 17 ~ C--S~N--i OH
( ~ P ~3Noz CQ e Z 19 ~yN~
OH
/~\
Z 21 ~S>
CH~/\ CH2COOe Z 2 2~3~ C H 2--N H 11 Z 23NO2 ~ COOH
~--COOII
NO~--~ Cl ~ NO 2 Z26NO2~H
Z 27 ~ N
~S~\ N
SO~M ll ~ 3 1 7500 1~, ~/~ N H z ~ COSH
C H a ~ N
HO [~OH
COOCzHs 7~32 N 0 ~ ~ N N ~
1~,~ N H 2 Z34 ~
~ ~ CN z--Br [~0,~ CH zBr Z 36 NOz~H~N
~L ( C H z ) z H H
Z 38 Cll,~N
N O z ~, Z40 SOzC~
~3 COOH
Z41 SO 2 Br ~ COOH
Z42 SO3Na NOz ~ NO2 ND~ ~ N~
H
Z44 ~ N
(where R represents -H, -SH, or -NH2) 1 31 750~
Z45 ~I
SH
N N (where R represents X -H, -SH, or -NHz) .
Z46 N(where Yb; alkyl group, N - N ~ ~ group, or ~ group) N
Z4~ CzHs HO N Sll O~/C~13 N~N
Sll ~011 COOC~Hq(t) - 155 _ l 31 7500 Z50 ll C N~ 3 \N~
Y' Y \
N ~Y
0~1 Z 52 Cll 3--~C= C~--Cll 3 ~ C ~
I
S~l Z 53 HOOC--CHz y N~ N~
~>
OH
- 156 _ ' 1317500 Z54 Cll3~/N ~N
YN ~ c 2 ~3 OH
~Ny N~
N~ N ~>
OH
Z 56 CH~Y/NY/N\
\ N
OH
oll - 157- ' 1317500 Z 58 CH3~Ny/N\
OH
Z 5 9 C l1 3 y/
~N~N~
OH
Z 60 CH3y/NyN\
~N~N~
OH
Z 61 CH~N~
N~
13175~
Z 62 7~12~
Y Y N
~,N~
Z 63 ~y N~
OH
Z 6 4~ N~ N ~ O 11 N j,~'~
OH ~J
~ N
C113/~N/ \~
Z 66 Cl13 y/N \1~ N ~
;~N
OH
ce Z 67 ~N ~ N
C2Hsco2 /~/N~
Z 68 CHJ y/N\~N
N \ N //~
-160 13175~
H~N~N~
~N~N~
CH3~N~N~
N~
OH ~
~N
OH
~,1 OH
> ~y / \ NCHzC ~ ~ \
N~
OH
Of the above exemplified compounds of those expressed by the general formulas [R-I] through [R-III], the Z-4, Z-5, Z-7, Z-14, Z-20, Z-26, Z-30, Z-49, and Z-51 compounds are especial-ly advantageously used for the purpose of the invention.
Another preferred embodiment of the invention is such that the developer solution used contains at least one kind of polymer or copolymer having a pyrolidone nucleus in the indi-vidual molecular structure, or at least one type of polyethy-lene glycol.
By this arrangement, it is possible to accelerate devel-opment and provide improved graininess.
The polymer or copolymer having a pyrolidone nucleus in the molecular structure and can be used in embodying the in-vention is every polymerizable polymer in which main chain or side chain of polymeric unit are replaced with pyrolidone nu-clear units at any positions and in any number, and such a polymer or copolymer may be a monopolymer of such polymeriz-able polymers, or may be a copolymer formed by copolymeriza-tion of two or more kinds of copolymeric units. In the latter case, the copolymer is preferably such that one polymer as a copolymeric unit which has pyrolidone nuclear units in its molecular structure is included in the proportion of 20% or more in the copolymer produced by copolymerizing the above-mentioned one polymer with another polymer which as no pyroli-done nuclear unit in its molecular structure. More favorably, the above-mentioned one polymer is so included in the propor-tion of 30% or more. For the above-mentioned other polymer having no pyrolidone nuclear unit which is to be copolymerized with the above-mentioned one polymer as a copolymeric consti-tuent which has pyrolidone nuclear units in its molecular structure any polymer may be used insofar as a hydrophilic copolymer can be obtained.
Preferably, aforesaid polymer or copolymer has an average molecular weight of 1,000 to 70,000, typical examples of which are as follows.
[Example compounds]
[1] Poly-N-vinyl-2-pyrolidone (*No tel) [2] Poly-N-(2-acryloyloxy)ethyl-1-pyrolidone [3] Poly-N-glycidyl-2-pyrolidone [4] Poly-N-allyl-2-pyrolidone [5] Poly-N,N-dimethyl-N-[3(1-pyrolidonyl)-2-hydroxy]propyl-amine-N'-acryloylimine [6] Copoly-N-vinyl-2-pyrolidone/N-acryloyl morpholine (molar ratio, 42:58) [7] Copoly-N-vinyl-2-pyrolidone/N-acryloyl piperidine (molar ratio, 35:65) [8] Poly-N-vinyl-2-pyrolidone/N-methacryloyl-2-methylimida-zole (molar ratio, 55:45) [9] Copoly-N-(2-acryloyloxy)-ethyl-2-pyrolidone/diethylamide acrylate (molar ratio, 60:40) [10] Copoly-N-(2-methacryloyloxy)ethyl-2-pyrolidone/sodium acrylate (molar ratio, 75:25) [11] Copoly-N-(3-acryloyloxy)propyl-2-pyrolidone/methyl metha-crylate (molar ratio, 65:35) [12] Copoly-N,N-dimethyl-N-(3-(1-pyrrolidonyl)-2-hydroxy]-propylamine-N'-acryloylimine/ethyl acrylate (molar ratio, 70:30) [13] Copoly-N-vinyl-2-pyrolidone/vinyl acetate (molar ratio 70:30) [14] Copoly-N-vinyl-2-pyrolidone/methyl acrylate (molar ratio, 70:30) [15] Copoly-N-vinyl-2-pyrolidone/styrene (molar ratio, 80:20) [16] Co~oly-N-vinyl-2-pyrolidOne/amide acrylate/N-vinyl-2-methylimdazole ~molar ratio, 50:30:20) [17] Copoly-N-vinyl-2-pyrolidone/N-(l,l-dimethyl-3-oxo)-butyl-acrylamide (molar ratio, 70:30) [18] Copoly-N-allyl-2-pyrolidone/vinyl acetate (molar ratio, 64:36) [19] Copoly-N-vinyl-2-pyrolidone/4-vinyl pyridine (molar ratio, 60:40) [203 Copoly-N-vinyl-2-pyrolidone/ethyl acrylate/monoethanola-mine acrylate (molar ratio, 50:45:5) [21] Copoly-N-vinyl-2-pyrolidone/piperidinomaleamic piperidine (molar ratio, 53:47) [22] Copoly-N-vinyl pyrolidone/4-vinylpyridino-N-methyliodide (molar ratio, 42:58) E23] Copoly-N-vinyl pyrolidone/thiourea half ammonium maleate (molar ratio, 60:40) *Note (l); Varieties of the example compound (1) are commer-cially available from General Aniline and Film Corp. under the * * * *
tradenames of PVP K-15, PVP K-17, PVP K-30, PVP K-60 and PVP
*
K-90, and also from BASF Aktien~esellschaft (Japan) under the trade marksof "Coridone 12", "Coridone 17", "Coridone 25", "Coridone 30", "Coridone 90", "Rubiscol K-17", "Rubiscol K-30", and "Rubiscol K-90".
* Trade mark.
B
-- 1 31 7~00 The above exemplified polymers and/or copolymers, some of which are commercially available as above noted, can easily be synthes~zed according to the methods described in W.R. Sorenson and T.W. Campbell, "Preparative Methods of Polymer Chemistry", John Wilery and Sons, Inc., 1961.
Such polymers or copolymers may be used either singly or ~n a combination of two or more kinds. The amount of such polymer or copolymer used is preferably within a range of 0.01 g to 100 g, in particular 0.05 g to 10 g, per liter of the color developing solution. Such a polymer or copolymer may be added directly to the solution in the color developer tank, or added to a replenishing tànk solution for subsequent' replenishing of the color developing tank solution, or may be used in a combination of both ways.
Polyethylene glycol compounds useful in connection with the above described embodiment will now be explained.
In the practice of the invention, polyethylene glycol compounds expressed by the following formula can be preferably used:
HO(CH2CHzO)nCH2CH2OH (n=1 to 1000) More specifically, carbowax 1000, carbowax 1540, carbowax * * *
2000, carbowax 4000, and carbowax 6000 are mentioned as useful compounds for the purpose. The amount of such polyethylene glycol to be added is generally at least 1 g/liter, preferably 1.5 g/liter to 40 g/liter.
* Trade mark.
B
- 166 _ l 3 1 7 500 Besides aforesaid polyethylene glycols, thelr derivatives can be used, though they are somewhat less effective.
Of the above-mentioned derivatives, polyethylene glycol-bis-pyridinium methane sulfonate, polyethylene glycol-bis-tri-(~-hydroxyethyl)ammonium methane sulfonate, polyethoxyethyl-bis(3,5-disulfobenzoate) tetrasodium, polyethylene glycol-bis-sulfonic acid, and polyethoxyethyl-bis-carboglutamic acid are rather less effective.
Next, the second invention of the present application will be explained.
This invention is characterized in that in the above des-cribed processing method of the first invention, a developing temperature is higher than 40C. Processing at more than 40C
can acceleraet development and provide improved graininess.
Processing is performed preferably at a temperature within a range of 42C to 70C, in particular, within a range of 45C
to 65C.
Where development is performed at higher than 40C, satisfactory development effect can be obtained even if a p-phenylenediamine-based developing agent is used in the concen-tration of 1.0 x 10-2 to 1.5 x 10 2 mol/liter. In this con-junction, a pH range of 10.2 and a processing time range of 20 to 150 seconds are even acceptable.
However, if the developing temperature condition of not lower than 40C is combined with such other conditions as a - 167 - l 3 1 7500 developing agent concentration of not lower than 1.5 x 10-2 mol/liter, or a pH value of not lower than 10.4, or a sulfite concentration of lower than 1.5 x 10-2 mol/liter, or a bromide concentration of not higher than 0.8 x 10-2 mol/liter, or use of any of developing accelerators [A-I] through [A-VI], the object of the invention can be more satisfactorily accomplish-ed.
Next, the third invention of the present application will be explained.
This third invention is characterized ln that in the processing method of the first invention, the concentration of the developing agent in the developer solution is not lower than 1.5 x 10-2 mol/liter. By using the developing agent in such high concentration, it is possible to effect active proc-essing and provide improved grainess. Preferably, the color deveoper solution contains the developing agent at a concen-tration of not lower than 2 x 10-2 mol per liter solution, more favorably in a concentration range of 2.5 x 10-2 to 2 x 10~l more/liter, still more favorably 3 x 10-2 to 1 x 10~
mol/liter.
The color developing agents useful in the practice of the invention will be discussed hereinbelow. The following expla-nation on the color developing agents is applicable to the other inventions of the present application as well, unless it is contradictory to their respective essential features.
- 168 - l 3 1 7500 In the practice of the invention, there may be used, for exmaple, aromatic primary amine-based color developing agents, including various kinds of known agents widely used as such in the art of color photographic processing. These developing agents include aminophenol and p-pheniline diamine derivatives.
These compounds are generally used in the form of salt, for example, in the form of hydrochloride, phosphate, or sulfate, since they are more stable in such form than in their free state.
Among the aminophenol developing agents there are, for example, o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, and 2-oxy-3-amino-1,4-dimethyl benzene.
Especially useful aromatic primary amine-based color developing agents are those having an amino group with at least one water-soluble group, and especially preferably, they are compounds expressed by the following general formula [X].
General formula [X]
R, 4 N - R~s ~ R, 3 In the formula, Rl3 represents a hydrogen atom, a halogen atom, or an alkyl group, wherein the above-mentioned alkyl group is a straight-chained or branched alkyl group having 1 to 5 carbon atoms, and may have a substituent group. R14 and Rls independently represent a hydrogen atom, or an alkyl or aryl groups, which may have a substituted group, wherein at least one of the R14 and Rls being an alkyl group having a water-soluble substituent, such as a hydroxyl group, carboxy-lic group, sulfonic group, amino group, or sulfonamide group;
or ~ tCIIz~ O J p R,~ Such an alkyl group further may have a substituent.
It is noted that Rl6 represents a hydrogen atom or an alkyl group, wherein the alkyl group being a straight-chained or branched alkyl group having 1 to 5 carbon atoms; and p and q respectively stands for an integer of 1 to 5.
Examples illustrative of the compounds expressed by the general formula [X] are given below; it is understood, how-ever, that the scope of the compounds according to the inven-tion is not limited to these examples.
[Example compounds ]
( E -- 1 ') C 2 R 5--N--C z H 4 N 1I S 0 2 C H J
~\CH 3 ~ ~I 2 ( E -- 2 ) C 2 ~I S--I --C 2 ~1 4 0 H
. , ~ .
~\ C H
NH z E -- 3 ) C 2 H 5--N--C 2 H 4 0 H
N ll 2 ( E -- 4 ) C 2 H s--N--C z 11 4 0 C 11 i ~, ~CII, N ll 2 ( E -- 5 ) CzHs--N--C3H6SO3H
~\C~13 E -- 6 ) C H 3--N--C z H ~ O H
Nll z t E -- 7 ) HOOCzH~--N--CzH~OII
. ~
NH z ~3~7500 E -- 8 ) C 4 H 9--N--C 4 11 11 S O :~ H
`~1 NH Z
E -- 9 ) C ~ H 4--N--C 3 H ~ S 0 3 H
NH z ( E -- 10 ) H--N--CH 2COOH
N H z E -- l 1 ) C 2 H s--N ~ C 11 z C ll 2 O ~2 C ll 3 ( E -- 12 ) C 2 H 5--NtCH 2 C HzO~CH~
NH z E -- 1 3 ) C 2 H s--N t C H 2 C H Z 0 3~ C Z 1l S
'' . .~
~/~CH 3 E -- 1 4 ) C 2 H 5--N--~ C 13 z C ll z O ~z C z ll 5 ~`3'c~
NH z ( E -- 15 ) Cll 3--N--~CII 2 r~ll "~Czlls NH z t317500 ( E - l6) 1( ~ CUzCll~CU~t~C~U5 C Q
Nll 2 The p-phenylenediamine derivatives expressed by the gen-eral formula [X] may be used in the form of organic or inor-ganic acidic salt. For example, various salts such as hydro-chloride, sulfate, phosphate, p-toluene sulfonate, sulfite, oxalate, and benzene sulfonate can be used for the purpose of the invention.
In the practice of the invention, among the p-phenylene-diamine derivatives expressed by the above-mentioned formula [X], those in which R14 and/or R15 are expressed by the for-mula ~ (C~lz)~ 0 ~ p R,~ (in which p, q, and Rl6 are as above defined) are especially effective for purposes of the inventions of the present application.
Next, the fourth invention of the present application will be explained.
This fourth invention is characterized in that in the processing method of the first invention, the developing time is less than 180 seconds.
In this fourth invention, the time for processing the silver halide color photographic light-sensitive material ac-cording to the above described processing method is within the range of 20 seconds to 150 seconds, preferably 30 to 120 sec-onds, more favorably 30 to 120 seconds, and still more favor-ably 40 to 100 seconds.
According to this invention, the silver halide color photographic light-sensitive material is processed for such a specific duration by employing the above described method, and surprisingly it has been found that this can result in con-siderably improved dye image graininess.
Next, the fifth invention of the present application is hereinunder described.
This fifth invention is characterized in that in the processing method of the first invention, the rate of layer swelling during the process of color development is less than 20 seconds.
Swelling rate T 1/2 can be measured according to any measurement technique known in the art. For example, it can be measured by employing a swellometer of the type described in a report made by A. Green et al in Photographic Science and Engineering, Vol. 10, No. 2, pp. 124 to 129. The above-mentioned T 1/2 is defined as the duration taken until 1/2 of a saturated gelatin thickness is reached, wherein the term "saturated gelatin thickness" means a maximum gelatin thick-ness resulting from 90% swelling which can be reached when processing is performed with the color developer solution at - 176 - ` 1317500 30C for 3 minutes and 15 seconds~ Referring to Fig. 1, time T 1/2 or one half o~ the time taken until the gelatin thick-ness is saturated by swelling (that is, the gelatin thickness levels off in the graph) is taken as the speed of gelatin swelling.
The swelling rate T 1/2 can be adjusted by adding a hardening agent to gelatin serving as a binder, or through varying combinations between the amounts of the hardening agent and gelatin in the photographic light-sensitive material on one hand and the characteristics of the developer solution on the other hand. For example, it can be adjusted by adding the hardening agent to the developer solution and/or by increasing the concentration of the salt in the solution.
For the hardening agent, various types of hardening agents can be used, including aldehyde-based ones, aziridine-based ones (e.g., those described in PB report 19,921, U.S.
Patent Nos. 2,950,197, 2,964,404, 2,983,611, and 3,271,175, Japanese Patent Examined Publication No. 40898/1971 published December 3, 1971, and Japanese Patent O.P.I. Publication No.
91315/1975 published July 22, 1975), isooxazolium-based ones (e.g., those described in U.S. Patent No. 3,321,323), epoxy-based ones (e.g., those described in U.S. Patent No.
3,047,394, German Patent No. 1,086,663, British Patent No.
1,033,518, and Japanese Patent Examined Publication No.
35495/1973 published October 29, 1973), vinylsulfone-based ones (e.g., those described in PB Report 19,920, German Patent ~ .~
V
- 177 ~ 1 3 1 7 500 Nos. 1,100,942, 2,337,412, 2,545,722, 2,635,518, 2,742,308, and 2,749,260, British Patent No. 1,251,091, and U.S. Patent Nos.
3,539,644 and 3,490,911), acryloyl-based ones (e.g., those described in U.S. Patent No. 3,640,720), carbodiimide-based ones (e~.g., those described in U.S. Patent Nos. 2,938,892, 4,043,818, 4,061,499, and Japanese Patent Examined Publication No. 38715/1971 published November 15, 1971), triazine-based ones (e.g., those described in German Patent Nos. 2,410,973 and 2,553,915, U.S. Patent No. 3,325,287, and high-polymeric ones (e.g., those described in British Patent No. 822,061, U.S. Patent Nos. 3,623,878, 3,396,029 and 3,226,234, and Japanese Patent Examined Publication Nos. 18578/1972, 18579/1972, 48896/1972 respectively published May 29, May 29 and December 8, 1972). There are also known maleimide-based, acetylene-based, methane sulfonate-based, and N-methylol-based hardening agent. These hardening agents can be used either alone as such or in combination. Various useful combinations are disclosed in various publications including, for example, German Patent Nos. 2,447,587, 2,505,746, and 2,514,245, U.S.
Patent Nos. 4,047,957, 3,832,181, and 3,840,370, Japanese Patent O.P.I. Publication No. 43319/1973, 63062/1975, and 127329/1977 respectively published June 22, 1973, May 29, 1975 and October 25, 1977, and Japanese Patent Examined Publication No. 32364/1973 published October 5, 1973.
Wlth the binder for photographic structural layers which is used in the color photographic lighl-sensitive material according to the invention, the smaller the speed of its B
swelling T 1/2, the better. However, if the lower limit of such speed is excessively small, gelatin hardening will not take place and thus scratches and the like troubles are likely to occur. Therefore, it is preferred that the lower limit should be more than 1 second. More favorably, the swelling rate is more than 2 seconds and not more than 20 seconds, especially preferably less than 15 seconds, and most favorably less than 10 seconds. If the rate of gelatin swelling is greater than 20 seconds, desilvering of the photogrpahic mate-rial, and more particularly the process of bleach-fixing, are seriously hindered.
Next, the sixth invention of the present application will be described.
This sixth invention is characterized in that in the processing method of the first invention, the light-sensitive material to be processed has, on its support, at least one silver-halide emulsion layer containing a coupler expressed by the following general formula [M-I].
~ eneral formula [M-I]
nm ~ Z~
N N- -In the above general formula [M-I], Zm represents a plurality of non-metal atoms necessary for forming a nitrogen-containing heterocycle, and the ring formed by the above-mentioned Zm may have a suhstituent group.
Symbol Xm represents hydrogen atom, or a group capable of split off upon the reaction an oxidation product of the color developing agent.
Symbol Rm represents a hydrogen atom, or a substituent group.
The substituent group represented by Rm is not particu-larly limited but is typically any of the following groups, namely, alkyl, aryl, anilino, acylamino, sulfonamide, alkyl-thio, arylthio, alkenyl, and cycloalkyl groups. Among others, the following are mentioned: halogen atom; cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxy carbony-lamino, alkoxycarbonyl, aryloxy carbonyl, and heterocyclic thio groups; and spiro residue and bridged hydrocarbon residue.
The alkyl group expressed by Rm is preferably any of those having 1 to 32 carbon atoms, and may be straight-chained or branched.
The aryl group expressed by Rm is preferably a phenyl group.
- 180 -` 1317~00 Exmaples of the acylamino group expressed by Rm include alkylcarbonylamino and arylcarbonylamino groups.
Examples of the sulfonamide group represented by Rm in-clude alkylsulfonylamino and arylsulfonylamino groups.
Examples of the alkyl and aryl components in the alkyl-thio and arylthio groups represented by Rm are alkyl and aryl groups each represented by Rm.
The alkenyl group expressed by Rm is preferably one hav-ing 2 to 32 carbon atoms, and the cycloalkyl group expressed by Rm is preferably one having 3 to 12, more favorably 5 to 7 carbon atoms; the alkenyl group may be straight-chained or branched.
The cycloalkenyl group expressed by Rm is preferably one having 3 to 12 carbon atoms, more favorably 5 to 7 carbon atoms.
Examples of the sulfonyl group expressed by Rm include alkylsulfonyl and arylsulfonyl groups.
Examples of the sulfinyl group expressed by Rm include alkylsulfinyl and arylsulfinyl groups.
Examples of the phosphonyl group expressed by Rm include alkylphosphonyl, aryloxysulfonyl, and arylphosphonyl groups.
Exmaples of acyl group expressed by Rm include alkyl-carbonyl and arylcarbonyl groups.
Examples of carbamoyl group expressed by Rm include alkylcarbamoyl and arylcarbamoyl groups.
Examples of sulfamoyl group expressed by Rm include alkylsulfamoyl and arylsulfamoyl groups.
Exmaples of acyloxy group expressed by Rm include alkyl-carbonyloxy and arylcarbonyloxy groups.
Examples of carbamoyloxy group expressed by Rm include alkylcarbamoyloxy and ary'carbamoyloxy groups.
Examples of ureido group expressed by Rm include alkyl-ureido and arylureido groups.
Exmaples of sulfamoylamino group expressed by Rm include alkylsulfamoyl amino and arylsulfamoyl amino groups.
The heterocyclic group expressed by Rm is preferably five- to seven-membered one, and more specifically, 2-furil, 2-thienyl, 2-pyrimidinyl, or 2-benzothiazolyl group.
The heterocyclic oxy group expressed by Rm is preferably one having a five- to seven-membered heterocyclic ring, and typically, 3,4,5,6-tetrahydropyranyl-2-oxy group or l-phenyl-tetrazole-5-oxy group.
The heterocyclic thio group expressed by Rm is preferably a five- to seven-membered heterocyclic thio group, for exam-ple, 2-pyridylthio, 2-benzothiazolylthio, or 2,4,-diphenoxy-1,3,5-triazole--thio group.
Examples of the siloxy group expressed by Rm include trimethylsiloxy, triethylsiloxy, and dimethylbutylsiloxy groups.
Examples of the imido group expressed by Rm include 13t7500 succinimido, 3-heptadecyl succinimido, phthalimide, and glutarimido groups.
Examples of spiro residue expressed by Rm include spiro [3,3]heptane-1-yl.
Examples of the bridged hydrocarbon residue expressed by Rm include bicyclo [2,2,1]heptane-1-yl, tricyclo[3,3,1,13 "]
decnae-1-yl, and 7,7-dimethyl-bicyclo[2,2,1]heptane-1-yl.
Examples of the group expressed by Xm which is capable of split off upon the reaction with an oxidation product of the color developing agent are a halogen atom (e.g., chlorine, bromine, and fluorine atoms); alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, acyloxy, sulfonyloxy, alkoxycar-bonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythio carbonyl-thio, acylamino, sulfonamide, N-atom bonded nitrogen-contain-ing heterocycle, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and I
R2 '--C-- R~ ' R, ' b~ z N - N--.--(in which Rl' has same meaning as aforesaid Rm; Z' has samemeaning as aforesaid Zm; and R2' and R3' independently repre-- 183 _ 1 31 7 5 00 sent a hydrogen atom, or aryl, alkyl, or heterocyclic group)O
Among the examples above, however, a particularly preferred one is a halogen atom, especially, chlorine atom.
Examples of the nitrogen-containing heterocyclic ring formed by Z or Z' include pyrazole, imidazole, triazole, and tetrazole rings. For the substituent groups which any of these rings may have, those mentioned with respect to the pre-viously defined R are available.
The couplers expressed by the general formula [M-I] are more specifically expressed by the following general formulas [M-II] through lM-VII]:
General formula [M-II]
X m 11 Rml 1 N
~/~,/ ' N
Il I L
N N R m 2 General formula [M-III]
X m 11 Rm '~N Rm 3 N--N--N
General formula [M-IV]
Xm Rm4 R m I ~ N
General formula ~M-V]
X m 11 R m.l ~h~N R m 5 N N Rm General formula [M-VI]
Xm Rm7 R m I ~R 8 N N- NH
General formula [M-VII]
X~ H
Rm l 1 N
\N
N--N N
- 185 ~ I 3 1 7500 In the foregoing formulas [M-II] through [M-VII], Rml through Rm8 and Xm have same meanings as previously mentioned Rm and Xm.
Among the couplers expressed by the general formula ~M-I], particularly preferred are those expressed by the fol-lowing general formula [M-VIII].
General formula [M-VIII]
Xm H
R m I ~N `''``z m I
N N -In the formula, Rm1, Xm, and Zml have smae meanings are Rml, Xm, and Zm in the general formula [M-I].
of the magenta couplers expressed by the general formulas [M-II] to [M-VII], most advantageous are those expressed by the general formula [M-II].
As the substituent which a ring formed by Zm in general formula [M-I], or a ring formed by Zml in the general formula [M-VIII], may have, or as any of Rml through Rmg in the gen-eral formulas [M-II] through [M-VI], those expressed by the following general formula [M-IX] are particularly preferred.
General formula [M-IX]
- Rml - SO2 - Rm2 In the formula, Rml represents an alkylene group, and Rm2 represents an alkyl group, a cycloalkyl group, or an aryl - 186 - l 3 1 7500 group.
The alkylene group expressed by Rml has a straight chain portion having preferably 2 or more carbon atoms, in particu-lar, 3 to 6 carbon atoms, and may be of either straight chained or branched configuration.
As the cycloalkyl group expressed by Rm2, a five- to six-membered one is preferred.
For the substituent groups Rm and Rml on the previously mentioned heterocyclic ring, if the light-sensitive material is used for positive image formation, those expressed by the following general formula [M-X] are most favorable.
- General formula [M-X~
R ~9 R m l O ~
R m l I
In the formula, Rmg, RmlO, and Rmll are synonymous with afore-mentioned R.
Two of the above-mentioned Rmg, RmlO, and Rmll, for ex-ample, Rmg and Rm1O may be combined with each other to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, or heterocycle), and further, Rmll may be combined with the ring to form a bridged hydrocarbon residue group.
In the general formula [M-X], it is preferred that (i) at least two of Rmg through Rmll are alkyl groups, or that (ii) one of Rmg through Rmll, for example, Rmll is a hydrogen atom, whereby the other two i.e. Rmg and Rm10 are combined with each other to form cycloalkyl together with a root carbon atom.
Further, in the above case (i), it is preferred that two of Rmg through Rmll are alkyl groups, while the other one is a hydrogen atom or an alkyl group.
As the substituent groups Rm and Rml on the above-men-tioned heterocycle, if the light-sensitive material of the in-vention is used for positive image formation, those expressed by the following general formula [M-XI] are most favorable.
General formula ~M-XI]
Rml2 - CH2 ~
where Rml2 is synonymous with aforesaid R.
Rml2 is preferably a hydrogen atom, or an alkyl group.
Typical examples of the compounds according to the inven-tion will be given below.
~- 1317~00 ce C ll 3 ~,N~
1l (Cll 2) 3 ~ NIIS0 2 ~ OC I 21i z s ce Cll3~,,N~
I--N l~-(CI12)3~NIJCOCI10~ 3 Cl ollz~
~ - 50 ~3011 C~ H
C D 3 ~N~N
N N 1l CllCHzS02C~ 8H37 I
Cl13 ce H
C H 3 \~ N~
C 11 2 C li 2 S 0 2 C 11 2 C 11 ~
C811, 7 ~ 189 _ 1 3 1 7 500 C~ H
Cll3 ~N~ Cll3 ¦¦ ¦ N I
N N 11 C--Cll2SO2CI81137 I
N~
~ .
H
CZIIS~ ~N~ OC4119 11 (CH2) ~SO2--~
CBH I 7 (t) Cl 2ll25O~SOZNH--~ (Cll2) 3\~N~
N N 11 C4ll9(t) c, 21l 2 5 n ~ S o 2 N 11--~
N N 11 Cll 3 C~IIII 3~ C ~ H
~ CIICIIZSOZCIIZCIIZ~,N~
1 o c o 11 CH3 ~ N~
N - ~Y 1I CH2CH2S02- ~ NHCOCHCH2COOII
C~s~137 C~ H
Cl13 ~ N~
N I l~ C}12CH2NHSOz- ~ OCI2Hzs (,'~ ~I
Cl13 ~ N~ Cl13 - N 1l CHzCH2S02- ~ NHCOCHO ~ C ~ 011 C~ollz~ Cl13 C~ 1 Csll~7SOzCH2CH2 ~ N~
N N 11 C]ICIIZSOZC~ 2HZ5 Cl13 CQ N
Cl sll~l~N~
N l 1l (Cllz)30--~3NIIS02N(CI13)2 1 5 S-~
COOII
H
CH3~ ~.,,N~ Cl sH37 b 1 ll ( C H z ) 3 ~3 N~ C O )/
C211s~.~N~ Csll I I ( t~
N N 1l - (CHz)2~73NllCOCI10--~C511l I tt) C~lls C Q ~I
Cll 3 ~N~ OC ,911 1 7 CHC112CH2S02C112C112S02 ~
CH3 Cl13 .
t317500 ce n Cl13 ~ N~ Cl13 C- CHzSO2- ~ NIISO C hll33 O -~3 OCII I
¦ H
CH3~ N~ CHI OC.119 CHzCH2CNlJSOz ~
CH3 C~11 7(t) ce n C113 ~ N~ OC 8 D 1 7 N - I 1l CHCH2NHS02 ~ O ~ 7 CH 3 NHSO 2 - ~
C~1~ 7(t) ce H
(i)C3U7 ~ N~ O
N N 11 (CH2)1S02- ~
CBH 7(t) - 193 _ 1 3 1 7 500 ce H
(i)C3H7 ~ N~
N - N 11 CHCHzCHzSOzCI~H33 C~ H
(i)C3H7 ~ N~ CH3 N 1I C- CHzSOz ~ OC~zN25 (i)C3H7 ~ N~
N - N 1I CHzCH2SOz- ~ NHSO2C,~H33 ce H
(i)C3117 ~ N~ OC H'3 N N 11 (CHz)3S02- ~ OC4H9 NHSOz ~
C~ll 7(t) C~ H
(i)C3117 ~ N~ . OC8HI7 ,l N 1~ CHCHzCH2SnzClJ2CI12SOz~
.
COOH
~I
(i)C3117~ ~,N~ C.81135 1l ( C~l z ) 3 ~3 \ C O ~/
Br H
(i)C3H7 ~ N~N C ~ (t) N N 1~ CHO ~ C511,l(t) C6,~1. 3 CQ H
(i)C3117 ~ ,N~ C ~ (t) N---N 1l (CHz) 2 ~ NHCOCHO ~ Csll I, (~j C4H., - 195 _ ~ 31 7500 C4~9~ C e ~1 , CH ~ N~ CQ . CQ
1 1~ CH2CHzCH0 - ~ SOz ~ 011 C7H, 5 CQ H
(i)C3H7 ~ N~ CH3 O(CH2)~S02C,H9 ~ C~zCH2- C - NHS02 ~
\=<
CH3 C8H,7(t) (t)C4119 ~ N~ 0 N - N 1l (CH 2 ) 3S0 2 - ~
C~H, 7 (t) C ~ ~J
(t)C~H9 ~ N~ 0 N N 1l (CHz)3SOz - ~
C~H,7(t) ce H
t t ) C ~ N~
N N1l (ClJz) 3S02CI 81137 ce ( t ) C J 11 ~ \/~N~
--1 1l (C~12) 2SOZC~ ~13q ce ( t ) C ~ H 9 ~N~
N N1l C~ C H z C H 2 S O 2 C ~ t 11 3 3 CHs ce H
( t ) C ~ N~
N N 1l CHCHzSOzCI 81137 I
C~13 ce ~1 ( t) C .,11,, ~,N~ Cll 3 ¦¦ ¦ N I
N N 1l C--Cll2so2cl ~113q C~3 CQ ~I
tt)C~119 ~ N~ Cl13 N N ll C- CHzS02- ~ OCIzHzs Cl13 ce H
(t)C~lly ~ N~ CH3 C51i" (t) N N 1l C- CHzS02- ~ NHCOCHzO ~ ~
~ -Csll,,(t) C Q H
(t)C~II.,~ ~ N~ C411.,(1) I N 1l (CH2~ 3 ~NIiCOCI10 - ~ 011 C, 2112s ce H
(t)C 4H~ ~ N~ Cl13 N N 1I CHzCHzC-N}lCOCI10 ~ NllSOzN(CI13)z C113 Cl zllzs - 198 ~ 1317500 O -~ COOCII 3 1 11 .
(t)C~.lls~N~ C"ls (t) (C112) 3SOz--e~NllCOCHO~ 3 C~HI 3.
C4.Hs ( t) ~ -S~OII
ce n (t)C411s ,N~ OC<lls (CH z) 3 ~ NHSO z O C ~ ~1 9 ~,,~
(~
ce N 1I CllCl12S02~3NllCOCllCI12SO2C~zllzs CONH W N O ~ )zOC~z}lzs N N 11 (CHz)2 ~ NHSOz ~
NHCONH ~ N~ CQ
N N 11 (CH2)30 ~ OCl2Hzs CQ
C~ H
CH30 ~ N~ C~3 - N 1l C -CH20 - ~ COOCIzHz5 4 9 OC~9 S-~
C~1~,7(t) C2}1sS ~ ~ N~ C ~ (t) N N ll-CH2CH2NHCOCHO- ~ C5H " tt) S
~, C ~ 11 N I
N--N 1I C--CH2CRzSOzC~ zHz5 C~13 CQ H
(Cl13) 3CC112~N~ OC811~ 7 (CHz) 3SOz--~
OC~H, 7 5 "
ce C e H
C 11 z ~ N~ C H 3 ~- J ~ ~CIi3 C ~ 3 N 1~ S O z C J b 1l 3 J
C~
~I~N 1l (Cll 2) 3 ~ NIICOCIIO ~ 3 Cl oHzl 3~ -SOz~OII
~ 201 -N~ O C ll z C O N ( C z H s ) z N N ll Cl12CH2SOz--~
C~H 17 ~t) CQ CQ
C H 3 ~N ~ (C H 2 ) 3 ~ N H C O C H O--~3 S O z ~ O ll N--N--N Cl311z~
Cl13~N~CHCH2S02 ~OCI zHz5 CQ CQ
HO ~~SOz ~OCIICONII~ (Cllz) 3~N~CI13 Cl oR21 N N N
- 202 _ 1317500 CH3 OCHII, 7 CH 5 ~ N ~ tCHZ)z- C- NHS0 2 ~ OC H 11 1 7 N - N - N C113 NHSOz- ~
' C811~ 7 (t) C~ H
Cll,`~ ~ N ~ CHCH2CH2S02C,~113 N ~ N I ~ Nl1502C,~H33 OC"II. 7 Cll3 ~ N ~ CHCllzNHS02 ~ OCHII I 7 N N N CH3 NHS02- ~
C~H, 7 ( t) - t 3 1 7~00 6 ~ .
CH3 OC~ 3 (i)C3117 ~ N ~ (CHz)2- C-NIIS02 ~ 0C~ 3 N - N - N Cl13 C~ H
(i)C~H7 ~ N ~ C- CN2SO2C~sH37 N N N CH~
C~119 (t) ~ ~ OCHCONH- ~ N ~ N
OC~HI7 (t)C411~ ~ N ~ CHCllzNHS02 ~
N - N - N C2~1s NIIS02- ~
C~11,7(t) t317~00 O(CIIz)zO(CH 2) 20CII 3 (t)C4119 ~ N ~ (CHz)3S02- ~
N N N C~ 7(t) .
CP
(t)C~Hq ~ N ~ (CH 2 ) 3 ~ NHC0CH0- ~ S02-N - N - N CloH2l CQ
~ ~011 (t)C~IIq ~ N ~ CIIzCllzC- NllS0 ~ 0C, Z1125 N - N N Cll~
(t)C~.IIq ~ N ~ CH2CHzS02 ~ NHSOzC~ 3 N N - N
ce NIICOCIIO- ~ G5R,,(t) N N Cloll2l CQ tCHZ)3- ~ NHSO2 ~ 0C~2Hz5 (t)C~N9 ~
Cl13SOz ~ ce (t)C~114 ~ (CH2)30 ~ C~
N N - NH NliCOCHO
Cl 21125 ~ O(CH2)3CONll(CHz)2C _ ~ ,N~
Cl511l, Cl13 N N - N
;= o ~ o - _ ~
", ~ .
/ ~ t~
_ X ~ C, o ~ ~ X ~ ..
n _ O
~ X
_ _ o O
r~
- 207 _~ 1317500 o o C~ _ t, U~
o ~ ~ .
.~ 1"
X ~ o ,_ ~ X , ..
Z~ ~..
~Z/ - I ~
V~ ¦ Z
:r :: Z
. N N
1 31 750~
In addition to the above given typical examples, the compounds shown by Nos. 1 to 4, 6, 8 to 17, 19 to 24, 26 to 43, 45 to 59, 61 to iO4, 106 to 121, 123 to 162, and 164 to 223, of those described pp. 66 to 122 of the specification of Japanese Patent Application No. 9791/1986, are mentioned as examples of the couplers expressed by the general formula [M-I].
The foregoing couplers can be synthesized ~ith reference to the Journal of the Chemical Society, Perkin I (1977), pp.
2047 to 2052; U.S. Patent No. 3,725,067, and Japanese Patent O.P.I. Publication Nos. 99437/1984, 42045/1983, 162548/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985, and 190779/
1985.
The above-mentioned couplers are normally used in the amount of 1 x 10- 3 mol to 1 mol, preferably 1 x 10- 2 mol to 8 x 10~l mols, per mol silver halide.
The couplers according to the invention can be used in combination with other kinds of magenta couplers.
Next, the seventh invention of the present application will be explained.
This seventh.invention is characterized in that in the processing method of the first invention, the light-sensitive material to be processed has, on the support, at least one silver-halide emulsion layer containing a coupler expressed by the following general formula CC-I].
General formula [C-I]
OH
R,~ ~ NNCD(N~)..Rc~
Rc 2 CONH
X c In the above formula, Rc2 represent an alkyl, cycloalkyl, alkenyl, aryl, or heterocyclic group, each of which may have a substituent group. Rc 3 represents a hydrogen atom, halogen atom; or an alkyl or alkoxy group, which may have a substituent group. Provided that Rc 2 and Rc 3 may be those which form a ring in conjunction with each other. Symbol Xc represents a hydrogen atom; or a group being capable of split off upon the reaction with an oxidation product of the color de~eloping agent. M stands for 0 or 1.
As the alkyl group represented by Rcl or Rc 2 . those hav-ing 1 to 32 carbon atoms are available; and as the similarly represented cycloalkyl group, those having 3 to 12 carbon atoms are available; as the similarly represented alkenyl group, those having 3 to 12 carbon atoms are available. These alkyl, alkenyl, and cycloalkyl groups include those having a substitu-ent group.
As the aryl group represented by Rcl or Rc2, a phenyl groups is preferred, which may have a substituent group.
As the heterocyclic group represented by Rcl or Rc2, a five- to seven-menbered one is preferred, which may be sub-stituted or condensed group.
Symbol Rc 3 represents a hydrogen or halogen atom, or an alkyl or alkoxy group, or, preferably, a hydrogen atom.
As the ring formed jointly by Rc2 and Rc3, a five- to six-membered ring is preferred. Examples of 5 to 6-membered rings so formed include C ~ 2 H 2 5 ~ \
~ ) ' ~ ) O N O N
H H
Examples of the group represented by Xc being capable of split off upon the reaction with an oxidation product of the color developing agent include a halogen atom, alkoxy, aryloxy, acyloxy, sulfonyloxy, acylamino, sulfonylamino, alkoxycarbonyl-oxy, aryloxycarbonyloxy, and imido groups. Of these, a halogen atom, and aryloxy and alkoxy groups are preferred.
Of said cyan couplers, those expressed by the following general formula CC-A] are especially preferred.
General formula CC-A]
OH
~ NIICOR A
~ 3 1 7500 In the formula, RA1 represents a phenyl group including a substituent of at least one halogen atom, wherein such a phenyl group may have a substituent other than a halogen atom.
Symbol RA2 is synonymous with Rc2 in the foregoing general form-ula [C-I]. Symbol XA represents a halogen atom, or an aryloxy or alkoxy group.
RA1 is preferably a phenyl group substituted by 2 to 5 halogen atoms.
The above-mentioned cyan couplers include, for example, the diacylamino phenol type cyan couplers described in the specification of Japanese Patent application No. 21843/1986, pp. 26 to 35, and Japanese Patent O.P.I. Publication No. 225155/
1985, the diacylaminophenol type cyan couplers described in Japanese Patent O.P.I. Publication No. 222853/1985, the diacyl and ureidoaminophenol type cyan couplers described in Japanese Patent O.P.I. Publication No. 185335/1985, and the ureide-aminophenol type cyan couplers described in Japanese Patent O.P.I. Publication No. 139031/1984. They can be synthesized according to the methods described in above cited publications.
The above-mentioned cyan couplers are usually incorporated in the silver halide emulsion layers, and more particularly, in the red-sensitive emulsion layer. The amount of such a cyan coupler used is within a range of 2 x 1 O- 3' to 8 x 10-l, pre-ferably 1 x 10~l to 5 x 10~l mols, per mol silver halide.
Typical examples of the cyan couplers expressed by afore-said general formula [C-I] are given below, but it is under-stood that the scope of said cyan couplers is not limited only to these examples.
[Example compounds]
CC-l (t)~CsH11 ~ NHCON ~ CN
(t)CsH1l ~ O- CHCONH
(t)csHll ~ NHCON ~ CN
(t)CsHll ~ O- CHCONH ~ ~ OCH3 (t)-CsHll ~ NHCON ~ CN
(t)CsHll ~ O- CHCONH
C6Hl3 (t)C~H17 1 31 7~0~
C
C, 5 H,, ~/NHCONH
.<,~ O -CHCONH F
C2Ns cc 5 ~NHCONH
110--~ O -CNCONH
( t)C~H, C~ 21~2s Cc_ G
OH
~NHCONHC, sH3, UO _~30-CHCONH lC~
(t.)C.,119 C,,~135 . . .
Cc_ 7 (t)CsH~ NHCONIl ~ CQ
(L)CsHIl ~ O-CHCONH CQ
C2Hs (t)CsH" ~ ~ ~I/NHcoNH ~ 3 so C~H, (L )C5 H " ~ O-CHCONH
Cz~ls Cc_ 9 ~ JHCONH ~ CN
Cl2H2sO { ~-O-CHCONH NO2 CH, ~NHCONH~ CN
HO~ O--CHCONH/~
(t) C4Hg C4Hg OCH2COOc2H5 CC-ll (t) C4Hg ~NHCON~SO2C2Hs (t) C4Hg~O--fHCONH/~ CN
Cl2H25 CQ
~,NHCONH~CQ
C4HgSO2N}~V O--fHCONH CN
~NHCON}~ COOCH3 (CH3) 3CCOO~O--CHCONH~
Cl2H25 OCH2CONHCH2CH20CH3 (t)C4Hg~t)C~Hg J~ ~cNo3 C12H25 NHS02{~CH3 (t) CsHll ~NHCON~SO2NHC4Hs (t ) CsHll~ O--~ CH2 ) 3CON
~NHCON1~3 COC 2H5 (n ) Cl2H25NHCO~ O--CH2CONH/~ CF3 .~ :
- 218 - l 3 1 7500 Cc_ 17 CH~
(t,)C5Hl,~O-CNCON~
C~H, ~, L _ ¦ 8 (t)CsH" ~/NHcoNH ~OC~
(L)c~H~, ~ O-C~CONH
C, 2H2s CC_ I ~
' 011 S
NHCONH
O-CHCONH
~ ICQ
Cl2H2sO C2Hs ~ 219- t317500 cc_ 20 ~NHCONH ~ 3 ( t )C5~11 1~0 -CHCONH
( ~)CsH
cc_ 21 OH
~ NHCONH ~ SO 2 CH
( L )CsH~ O-CHCONH CQ
(L)CsH~
CC~ 22 OH
f i~ NHCONH ~ SOzC2Hs ( ~)C~Hs ~3SozCUCONH ~0 ~--OCzHs C~oH21 .. .. .
( t)CsN, I ~/NHCNH ~3So2~3N7 ( t)C,H"~O-CNCONH
CzHs cc_ 2~1 .
~t)C~H~ ~/NHcoNH~502C6H"
( L )C~H g ~0-1 CONH
CH~
C ~ 25 ~NIICONH ~SOC2Hs ~O-CHCONH /~
~=/ I CQ
C H C2Hs , s ,, C --~G
NHCONII ~11\OCCH
~H2sO ~_", O I~CO CQ
C2Hs ~ ~NHCON~ ÇC~
C12~1 2jO ~\~-0-CUCO ~ CQ
OCON ( CH ~ ) z C7Hs CC~ 28 CH C ~ il/NHlCI ~) ~ I ~ CQ
CH, -CH 2 -C--<J \`)--OCNCNH r 11 c~.
~, 0 CU, ~NHC
CH, -CH~ -C--<~OCHCNH
I \=< 11 CQ
CH ~ CQ ~
NUC
CH ~ -CH z -C ~OCl~CN~ C~J
CU ~ CQ
CHJ C, oH2, ~3/ 11 ~9 ' Cll ~ -CH 2 -C--~OCHCNH
I \=~ 11 ~Q
CH ~ CQ o - 223 - 13i75~0 N5iC
CH J C ~ 21~Z 5)~/ 1 CH, -CH z -C ~OCHCNII
I \=< 11 CQ
CH, CQ
C
C ~ 33 NUC ~3 CH, Cl, H " )~/ 1 C>=/
CH, -(CH2)2 -C~OCHCNH
CH, C0 o CC--3~ ;
NHC
CH~ C8~ / bi~
CH~-(CH2)z-C ~ OCHCNH
I \=(~ 11 CQ
C~ ~ CQ
C ~ 35 -OH
1 NHCOC~F7 CH~ C,H" p ~/
CK 3 CH z C ~OCHCNH
CH~ CQ
CC~ 36 ~NHCONII ~CQ
( t )CsH I I ~OCHCONH
C~lls Cll 37 NHCONK 4~S02CzUs CsH~ I (t) f~
( t ) C s H I I ~ OCUCONII CQ
C21~s CC~ 38 NHCaNII ~3F
~ s H ~
(~)CsHIl ~OCHCONH
C,Hs CC~ 39 CQ
NHCONH ~>
( t)C~H 17 ~OCHCONI{~3/ C3 CcH~
CC- ~
CQ
~/ CQ
( t )CaH I 1 ~OCHCONH
C~ll, ' C ~
-`
( t)C~H, 7 ~OCHCONH
C~Hg NHCONH ~CQ
/C,~,7(t) ~1~
(t)C~HI7 ~ 0CHCONH ~
OCH2CH2SO2CH, C,H,, C - ~3 (t)C~H, 7~0CHCONH
I OCH2CHzSOzCOOH
C2Hs C - ~4 CQ ~ NHCONH ~ CN
(t)CsHI~ ~ OCHCONH
I
CCH, .7 CQ ~NHCON~SO2C3H7 (t)C5Hll- ~ OICHCON
H ~ CQ
(t)C5Hll ~ O- CHCON
OH
~NHS02NHC4Hg C4HgSO2NI~O--ICHCON~
~ NHCONHC ~ SO2CH
(t)C4H9 ~ S - CHCONH
I F
~,NHCoNHso2~$
(n) C12H2s~o--CHCONH F F.
I
~,NHCON~ SO2CF3 CONH
~=/ F
Cl 6H330 OH ~
~,NHCON\JO
U~ S CF3 C4HgSO2N~ CON
~ C~
`4,~f j OH
~,NHCO- lcHcH2so2cl2H25 (t) C4E~9N}~CSN
CQ
(t) C5Hll ~NHCO ICH~3 (t ) C5Hll C2H5SO2~NHCONH/~J C4Hg ~NHCO~CONHCl2H25 CH2NHCONH/~N--INI
N--N
C --5~
C2Hs h/NHCOCHzo ~OC, 2H2s NCONH~
C C 2 11 s OH
(t)CsH" ~fNI~CO--C~F'7 ( ~ ) Cs H I ,~0--CHCONH~
C~H, ( ~ ) C 1 U g ~ ~/
C~Ug F
~,1~ NHCO ~ F
HO ~ û--CHCONH
( t)C~HY C, 2H25 C - BO
OH
(t)CsH " ~ NHCOCJF~
(t)CsHIl ~ O- CHCONH ~ ' C2Hs C ~ Gl OH
~ ~r~NH~O(CF2)2CHF~Q
Cl2H2sO ~ 0--fHCONHJ ~ JJ
C2Hs /(~)CsHl~ ~ ~ OCF2CHFCQ
(t)CsHIl ~ O - CHCONH OCF2CHFCQ
C2Hs C - ~3 OH
F~Us ~ NIICO(CF2CF2)2H
(l)CsHIl ~ O - lHCONH' (t)CsHIl -232- 13~75~0 cc 64 OH
,~NHCO(CF2 ) 3H
Cl 2H2sO ~O--CHCONH~
C.~1~9 F
C,51,SO2NH ~ ICI2~2s~3/NHco~3 CQ
C~oH2~ ~NHCO~
~O--CHCONH~. C 1 2H 2 s NHS0 2CH ~ CQ
C ~ 67 (t)Cs~ /NHC0 ( t ) C s U "~ O ~ CHCONH NHSO 2 Cll C2Hs OH
~NHS02CH3 CllH23C
OH
~ ~NHCOCls HO~ S02NI~
~NHCo~3 Cl3H27-cH=cHcH2clHcoN
~ IC12H25 ~ ~3 ~r - 234 _ 1317500 OH
~3 0--CHCONH/¢~
( CH2 ) 20C2Hs ~,NHCO~) ¢~ O--CHCONH
~3 CH2 - S 2 -NH
C~
~3~NHCo~3 C6Hl3~CHCoNH F
(t ) CsH" ~ J~3 F
. ~.
OH
CQ ~ NHCOC(CH3)3 CQ ~ O- ICHCONH
(t)C4Hg OCHCON
>==~ CQ
Cl5H3l(n) (t)C4H
OCHCON
~=J CQ
H ~ (t)C4Hg 02N ~ OCHCON
CQ
- 236 - 13175~0 cc 80 . C~ 2U2~ ~/NHCO~(t)C~Hs OCUCONH
CQCQ
Cl 2H2s ~/NHC0~3 C O ~ OIHCONH--~ -CQ CQ
cc_ 82 Cl 2H2s ~NIICO~
OIIICONH ~ CQ
CQ C
cc_ 83 ~OCHCONH ~~/
CQ CQ
- 237 _ 1 31 75 0 C12H25 ~NHC~
OCHCONH ~ CH3 CQ C
~ NHC
Cl2H25 ~ S(CH2)3CON ~
OH
(t)C5Hll ~ NHCOCH2CH=CH2 (t)C5Hll ~ O-(CH2)3CONH ~
F
~ NHCONH ~ S2 (t)C4H ~ O-CHCON
- 238 - 1 3 1 7~00 C,zH2s,~1 NHCONH ~ CFJ
SO,--N~ CONH~3/
I H ~ ~
1~3 ' NHCONH
C, CH,7C0NH
cc_ 90 OH
~t)CsHI I~NHCoNH~3So2CH~
(l)c5H,r~o--CHCONII
Cl 2H2s cc_ 9 ~NHCONH ~SO2NH
~3 0--CHCûNU
C~HgSO2NH OCOCH~
OH
~H ~ ~ NHCONII ~ S020CH, C,2H2~0 ~ 0 - CHCONH J
C~
C - ~3 ~ NHC0NH ~ C0N <CH
(t)C~U, ~ ~ O - CH2CON
(t)C~, cc _ 9 OH
~ NHCONH ~ SOzNHCzHs C,6HJ,OCHCONH J
C, zH2s ~3 . ' OCH2CH20CH, CC~ 95 t)CsH~ 3/NIICOCH2~NIICOCH3 (t)Cslll r~a--(C~2)3CONH
C ~ 96 Cl 2~25 ~/NHC
NC--.~} OC~CONII ,l~
CQ
C ~ 97 C12 H2~ NHC ~3 OCNCONH ~ CQ
CN CQ
C -- 9 8 ~
C~ ~ lC~2Hz5~3/NNCO~3 CN CQ
-241- 13~7500 3i~ ,?~;7 cC_ y~ ' O~i C~ Cr2H2s ,~/NHco ~0--CHCONH J~ CQ
C~ CQ
Especially preferred cyan couplers are tabulated in the following pages.
. . .
llc3~ NllCU(Nll)r~
R~ 2CONII ~
Ex~mple _ . _ R . 2 R " ~ m I C~ (tj . ... __. . . . .
C ~ 1 ~ (Cll2) 4ll (l)C~III I -~OCIll- ll -ce o C4lls _ I c- ~ I ~tl)C~II"-~ C~ -ce o C-3 ~ ~l)C~ O~ ~l -CQ O
C~ ~1 _~1~ Cl~.lla~~ -ce -ce U
l ._ C--S ~. tCII~) ~NSO~NII--~ OCO-- . _ O~C ~ 7 t t) O
C-G ~ (t)c~ ocllllo)~ ll . . O
,.. ... ,,_ I I I_ c - 7 ~1,~511 " t l) . - ce, O
. I~ ce C411~
. ce .. _._ C - O ~( l) C~ I ~OCII- 11 - ce O
¦ NIISO2C~117C511m tl; _ ' C~ 9 ~ ~)C5llll~~ulcll- ,11 0~0Cll3 O
NIISU2C6ll1 1 C4ll~ _ 243 - 1 31 7sao ~e l~cl _ n........ xe _ , _I , ~ .
C--10 ~ - (I;lln) ~N'il)nNII -(~-()CII-- 11 , -ce O
. ce 112~(:, 2 _ _~ ___ .__ _ c - 1l ~ce c, ~ -(~SO2NII~) 11 -ce o ce I ce _ C ~ 12 ~ Ce~OCII-- - 11 - OCllzCONllCall7 O
_ ce c,OIlz' I_ ce c,~
C -~3 ~ C~1170-~OCII 11 -ce - o I ce C~117 (~ ..
c - 1~ ~--~ce I10-~OCII 11 ce o NllSOzCN3 C~ 2112~
_ _ C-15 ~Oz(Cllz)~O-~/~C~ ) oJ~I -ce o _ C-l~; ' ~1~ C~2ll~o~l? -ce O
. . _ C--17 ~(Cll~)~NSO~Nli-e30CII-- 11 -ce o ~ P~C1211~ _ C--111 ~i~ (Cllla) ~NSO~NII~OCII- 11 -ce O
P 11Cl zll2s I . ---- I _ C - I!l _ I tCnlln) ~N';I)~NII-e3-oCII- 11 Og~OCllJ O
- 244- 131750~
. _ com,oound No. 1~ c I ]~ . R ~ 7 X ~ ; m _ _ . ._ __ .. ~
C - 20 ~ OCII:~ ( L) C~ 0 ~ 11 - ce o C - 2l ~ C~ ll - ce o I P ~ C~ 5 _ l~lt C - 22 ~ Cll7CUO -~/3-OC~ ll - ce o P 1~ ~ ) C,.llz!.
l l l _ C-23 ' ~1~ ~l)C~ o~ ll ~ O
P 1l C3117 (1) C~lll 7 (~) ce c e ~ . _ _ .C - 2~ ~/3 ( ~) c~ll 1 l e~ o Icll ll ce o I . I _ P p .c~ll" (~) , C--25 ~ (l)C~IIIl-~OCll-- ll OCII,CONIICII,CII,OCII, O
P P C,ll, (I) -C511~ (1) _.
C--2G ~CN ~ l . N l I c~l" (L) -- ----I
C -27 ~SO,C~ (n)(l)C~IIm ~OCN-- N N
C - 2~ ~ce ~5,11~ ) _ ~ _ CN C ~ . . _ C -2~ ~S0~C~ (l)C~ -~OCII- n -ce l . c.ll. . _ ~ompound No . n ~, 1~ ~ 2 R . ~ X . ¦ nl . I ~~~ Csll~ )' ' ' .. ... ~ _ C--3U ~sozc4llq(n)(t)C~II"--~OCII-- ll OCII~CONll(Cllz)zOCllJ 1 l Czlls I _ C.-31 ~C-NCe~l)Collll ~OI~ll 11 O~C~1117(t) I
.. IlCsllll O _ C--:12 ~ CN IC ~ 11 1, _~ OCII-- . C - Cll, I ~c,~" 1- _ C--33, -n--CJII, IC,III, -(~OCII-- 11 11 O
I LCsllll _ C--3-1 --n--C~117 lcOlllI-~OCII-- ll ll U t I ___ _ I_ c - 35 ~ce IcOIl 17 ~~ O~ll - . ll . ce _ I nC~ I_ C-3G ~c,ll"-~o-cll- ll ce o ce ce nC~II, J _ C_37 ~) C~ SU~ 3__C!II_ 11 ce o _ I_ _ . __ I , . ,~ _ C -33 ~SO~C~117lC~III I -~`OCII-- ll 11 I
l tCsllll ~ _ C ~ 3~ ~ CNIC s ll l 1 -~ O(,II-- ll ~3 _ n--C~ J _ OCI~II 17 _ Next, the eighth invention of the present Application will be explained.
This eighth invention relates to color developer solutions and provides a color developer solution for silver halide color photographic light-sensitive materials, which comprises at least one compound selected from the following group CA] and at least one means selected from the following group CB].
Group CA]
(A-1) Compounds expressed by the following general formula CR-I]:
General formula CR-I]
X r ~ ) n r ~'- C /
In the formula Xr', Xri' independently represent a halogen atom, or an alkyl, aryl, amino, hydroxyl, nitro, carboxyl, or sulfonyl group; Xr2' represents a hydrogen atom, or an alkyl, or aryl group, or a double bond for ring formation; Zr r~pre-sents a plurality of atoms consisting of a carbon atom, oxygen atom, nitrogen atom, and sulfur atom, which are necessary for forming a ring; nr, and mr independently represent 0, 1, 2 , or 3.
(A-2) Compounds expressed by the following general formula [R-II];
- 247 ~ 1 3 1 7 5 0~
General formula [R-II]
Y,, ~$Y
Y r ~ Y r In the formula, Yr , Yrl, Ur2, and Yr3 independently re-present a hydrogen atom, halogen atom, or an amino group, hydro-xyl group, nitro group, carboxyl group, or sulfonyl group.
IA-3) Compounds expressed by the following general formula [R-III]:
General formula CR-III]
.. . . .
Yrs -- Tr ~ Xr2 I
Xr 3 In the formula, Tr represents a nitrogen or phosphor atom;
Xr2, Xr3 independently represent a hydrogen atom, or an alXyl group, aryl group, or halogen atom; Yr4 and Yrs independently represent an alkyl or aryl group; ~r4 and Yrs may form a hetero-cyclic ring through ring closure.
(A-4) compounds expressed by the following general formula [R-IV]:
- 248 - 13t7500 General formula ~R-IV]
C - R
C - -X, Y s Rs20 \ Z ~ \ OR,~
In the formula [R-IV], Rsl represent -OH, -oRs4, or -N HRS ; Rs4 and Rss independently represent an alkyl group, typified by a methyl, ethyl, propyl, butyl, benzyl, ~-hydro-xyethyl, or dodecyl group, wherein each of such a group may have a substituent (for example, an aryl group such as hydroxyl or phenyl group).
Rs2 and Rs3 represent -H or -C-Rs6, in which Rs6 represents an alkyl or aryl group, illustrative o~ which is a long-chain alkyl group, such as an undecyl group.
Xs and Ys respectively represent a carbon and hydrogen atoms which respectively form together with other plurality of atoms six-membered rings; and Zs represents -N= or -CH=.
Where Zs represents -N=, citra~ic acid derivatives are typical compounds illustrative of the compounds expressed by the general formula CR-IV~. If Z represents -CS=, benzoic acid - 249 ~ 1 3 1 7500 derivatives are typical compounds illustrative of the compounds expressed by the general formula [R-IV]. It is further noted that six-membered rings include those having a substituent group such as a halogen atom.
As far as Zs is concerned, -N= is preferred.
The compounds expressed by the general formula CR-I]
through CR-IV] are same as the earlier explained ones, examples of which have already been given.
(A-5) Polymers or copolymers respectively having pyrolidone nucleus in the molecular structure ~A-6) Polyethylene glycol derivatives The groups (A-5) and (A-6) are correspondingly identical with the earlier described "polymers or copolymers having pyrolidone nucleus in the molecular structure" and "polyethyl-ene glycol compounds".
CGroup B]
(B-I) The concentration of the p-phenylenediamine-based color developing agent in the color developer solution is higher than 1.5 x 102 mol/liter.
(B-II) The pH of the color developer solution of 10.4 or high-er.
(B-III) The concentration of the sulfite in the color developer solution is lower than 1.5 x 102 mol/liter.
(B-IV) The concentration of the bromide in the color developer solution is lower than 0.8 x 10-2 mol/liter.
- 250 ~ 1 31 75~
(B-V) The color developer solution contains at least one of those kinds of compounds expressed by the general formulas (A-I) through (A-VI).
The general formulas (A-I) through ~A-VI) are same as those earlier described, and examples illustrative of the com-pounds expressed by the formulas are same as those earlier given.
In this conjunction, the following combinations are shown, by way of example, as preferred combinations.
o (A-1) + ~B-1) (in which + means combination) o (A-1) + (B-2) o (A-1) + (B-3) o (A-1) + (B-4) o (A-1) + (B-5) o (A-2) + (B-1) o (A-1) + (B-1) + (B-2) o (A-2) + (B-2) o (A-3) + (B-1) + (B-2) o (A-1) + (B-1) + (B-5) o (A-1) + (A-2) + (B-1) + (B-2) o (A-3) + (B-1) o (A-2) + (B-3) + (B-4) o (A-1) + (B-1) + (B-3) o (A-1) + (A-5) + (B-1) + (B-2) O (A-1) + (A-6) + (B-1) + (B-2) + (B-5) O (A-5) + (A-1) + (B-1) O (A-1) + (A-5) + (B-1) + (B-2) + (B-5) O (A-1) + (A-5) + (b-1) + (B-5) Examples illustrative of the compounds expressed by the General formula CR-IV] are shown below. Needless to say, how-ever, the CR-IV] compounds are not limited by these examples.
( 1 ) COOH
~10/~\0~1 ( 2 ) COOH
HO OH
- 252 - 13~7500 ( 3 ) COOCH3 HO N OH
( 4 ) COOC2H~
,~, HO N OH
( 5 ) COOC3H7 HO N OH
( 6 ) COOC~H 9 HO N Oll ( 7 ) /=\
COOCHz~d ~1' H O N O H
( 8 ) COOC~ zNzs HO N OH
g ) CONH 2 HO N OH
OH
(10) / C H z C H z H O /~3\ O ll ( 11 ) COOH
,~
CH3 (Cll z) I oCOO N OCO tCI12) 1 oCH3 (12) COO~
,~
H O N O C O t C ll 2 ), O C H
( 13 ) COOH
C ~
HO 1~N~ON
( 14 ) COOC}~3 H O /~\ O N
(1~) COOC2H5 110/~ ON
( 16) COOC3N7 (n) HO )~\ OH
- 255 ~ 1 ~ 75`0~
, ( 17 ) COOC4H 9 (n) ~10/~\011 ( 1 8 ) C O O C 1 2 H z 5 ( n ) HO OH
( 19 3 CONH2 ~ O ,e~ O H
( 20 ) COOH
Cll~ tCIIZ) ~ oCOO/~\OCO(Cllz), oCH~
1980, No. 158124/1980 and others may be referred to.
The tabular silver halide particles may be chemically sensitized in compliance with a specific requirement. For the chemical sensitization method, the description of sensitiza-- 29 - l 37 7i~ 0 tion methods previously described for the core/shell type par-ticles may be referred to. More specifically, in considera-tion of more economically using silver, the tabular silver halide particles should be preferably sensitized with a gold sensitization method or sulfur sensitization method or combi-nation of these two methods.
In a layer containing the tabular silver halide parti-cles, such aprticles should be present at a rate by weight of more than 40~, in particular, more than 60~ per total silver halide particles of the smae layer.
The silver halide color photographic light-sensitive materials subjected to the process of the invention are not limited only to the above-described materials, but include the materials having the tabular silver halide particles described below.
For example, Japanese Patent O.P.I. Publication No.
113930/1983 discloses a multi-layered color photographic light-sensitive material comprising a two-layered dye forming unit including an upper emulsion layer containing tabular silver halide particles with an aspect ratio of greater than 8:1; Japanese Patent O.P.I. Publication No. 113934/1983 dis-closes a multi-layered color photographic light-sensitive material comprising green-sensitive and red-sensitive layers containing tabular silver iodo-bromide or silver bromide emul-sion of which particles having an aspect ratio of greater than - 30 - l 3 1 7500 8:1; Japanese Patent O.P.I. Publication No. 113927/19a3 dis-closes a multi-layered color photographic light-sensitive material having tabular silver halide particles having an as-pect ratio of greater than 8:1, wherein the center region o~
individual particles has a higher silver iodine content than the outer circular region; Japanese Patent O.P.I. Publication No. 55426/1984 discloses a silver halide photographic light-sensitive material containing tabular silver halide particles having an aspect ratio of greater than 3:1 as well as a speci-fic sensitizing dye, wherein the material may be also used as a color photographic light-sensitive material; Japanese Patent O.P.I. Publication No. 111696/1985 discloses a silver halide photographic light-sensitive material containing tabular sil-ver halide particles having an aspect ratio of greater than 3:1, wherein the particles mainly composed of (111) faces.
These silver halide color photographic light-sensitive mate-rials may be subjected to the processing method of the inven-tion.
It is also advantageous to incorporate silver halide particles having epitaxy bonds described in Japanese Patent O.P.I. Publication No. 103725/1978 and the like into emulsions of the invention.
The present invention is applicable to any silver halide color photographic light-sensitive material containing, in at least one silver halide emulsion layer, silver halide parti-cles with silver iodine (the preferred embodiment of such silver halide particles are the previously defined core/shell type silver halide particles and/or tabular silver halide par-ticles). A11 or only one of the silver halide emulsion layers disposed on a support may contain the above-mentioned silver halide particles with the above-mentioned silver iodide.
One preferred embodiment of the invention is a silver halide color photagraphic light-sensitive material of which total silver halide applied on a support is at a rate of more than 30 mg per 100 cm2, or, preferably, 30 to 150 mg per 100 cm2, in particular, 30 to 100 mg per 100 cmZ support. In addition, generally speaking, a silver halide emulsion layer nearer to the support should preferably have a greater silver amount.
The silver halide color photographic light~sensitive material used in embodying the invention should preferably contain a compound capable of releasing ~or allowing elution of), in the course of color developing, an inhibitor which forms silver salt with the solubility product with silver ion of not more than 1 x 10-9.
A compound advantageously used in embodying the invention and capable of releasing, in the course of color developing, an inhibitor which forms silver salt with the solubility pro-duct with silver ion of not more than l x 10-9 may be a com-pound which is present as an inhibitor precursor within a pre-- 32 - l 3 1 7500 developing light-sensitive material and capable of releasing an inhibitor in the course of developing, or a compound which is present as an inhibitor within the light-sensitive material and capable of being eluted into a color developer solution in the course of developing. According to the invention, a DIR
compound, tetrazaindene derivative, and 6-aminopurine deriva-tive are advantageously used. Among them, a DIR compound is especially favorably used, as being capable of excellently attaining the objects of the invention. In addition to the DIR compound, a compound being capable of releasing a develop-ment inhibitor upon developing is included in the scope of the invention. The examples of such a compound include those des-cribed in U.S. Patents No. 3,297,445, and No. 3,379,529, West German OLS No. 2,417,914, and Japanese Patent O.P.I. Publica-tions No. 15271/1977, No. 9116/1978, No. 123838/1984 and No.
127038/1984.
A DIR compound advantageously incorporated in a light-sensitive material used in embodying the invention is a com-pound being capable of releasing a development inhibitor upon reaction with an oxidation product of a color developing agent.
Such a DIR compound, becuase releasing a development in-hibitor in the course of color development, prevents eccessive color developing in processing steps following the color de-veloping, thus supressing eccessive increase in image density _ 33 _ 1317500 and providing an image which is in compliance with a designed tone pattern and preventing hardness of the image.
The typical examples of such a DIR compound include DIR
couplers individually incorporating, into the active site of the coupler, a group being capable of forming a compound hav-ing development inhibition activity once split off the active site. These DIR couplers are describe, for example, British Patent No. 935,454, U.S. Patents No. 3,227,544, No. 4,095,984 and No. 4,149,386.
With the above-mentioned DIR couplers, a parent nucleus of coupler is capable of not only forming dye upon coupling reaction with an oxidation product of a color developing agent but releasing a development inhibitor. According to the in-vention, additionally, a compound capable of releasing a de-velopment inhibitor upon coupling reaction with an oxidation produGt of a color developing agent though not releasing a development inhibitor may be used as a DIR compound. The examples of such a compound are described in ~.S. Patents No.
3,652,345, No. 3,928,041, No. 3,958,993, No. 3,961,959, and No. 4,052,213, and Japanese Patent O.P.I. Publications No.
110529/1978, No. 13333/1979, and No. 161237/1980.
Furthremore, according to the invention, a so-called tim-ing DIR compound may be used. With a timing DIR compound, when it is allowed to react with an oxidation product of a color developing agent, the parent nucleus is capable of form-- 34 - t317500 ing a dye or a colorless compound, and, at the same time, the split timing group release a development inhibitor by intra-molecular nucleophilic substitution reaction or elimination reaction. The exmaples of such a timing DIR compound are des-cribed in Japanese Patent O.P.I. Publications No. 145135/1979, No. 114946/1981, and 154234/1982.
Additionally, other useful timing DIR compounds are those described in Japanese Patent O.P.I. Publications No. 160954/
1983 and No. 162949/1983, wherein the above-described timing group connects to a coupler nucleus being capable of forming a perfectly diffusible dye upon reaction with an oxidation pro-duct of a color developing agent.
More advantageous DIR compounds may be represented the following general formula [D] or (D-1). The most advantageous DIR compounds are the compounds represented by the following general formula (D-1) and having diffusibility greater than 0.40.
General formula [D]
Adl - Zdl In this formula, Ad1 represents a coupler component (com-pound) being capable of coupling with an oxidation product of p-phenylenediamine color developing agent. More specifically, the examples of such a coupler component are as follows: dye forming couplers including closed-chain ketomethylene com-pounds such as acylacetanilide, and acyl acetate; pyrazolones, ~ 35 ~ 1 31 7500 pyrazolotriazoles, pyrazolinobenzimidazoles, indazolones, phenols, and naphthols; and coupling components, which do not form dyes, such as acetophenones, indanones, and oxazolones.
In the above formula, Zdl represents a component (com-pound) being capable of split off upon reaction with an oxida-tion product of p-phenylenediamine color developing agent, and inhibit development of silver halide. The preferred examples of such a compound include heterocyclic compounds such as benzotriazole, 3-octylthio-1,2,~-triazolei and heterocyclic mercapto compounds (as an example of heterocyclic mercapto compound, 1-phenyltetrazolylthio group or the like is avail-able).
The examples of the above-mentioned heterocyclic group include a tetrazolyl group, thiazolyl group, oxadiazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, triazolyl group and the like.
In the above general formula [D], Zs~ is bonded to the active site on Adl.
Diffusibility of the above DIR compound may be evaluated using the following procedure.
Light-sensitive material samples (a) and (b) respectively comprising layers of the following compositions being disposed on a transparent support.
Sample (a): Sample having a green-sensitive silver halide emulsion layer - 36 ~ 1 3 1 7500 Gelatin coating solution containing silver iodo-bromide (silver iodide, 6 mol%; average particle size, 0.48 ~m) spec-trally sensitized to have green-sensitivity, as well as the following coupler at a rate of 0.07 mol per mol silver, is applied so that the amount of coated silver is at a rate of 1.1 g/mZ, and the amount of deposited gelatin is 3.0 g/m2.
Upon this emulsion layer is formed a protective layer, by ap-plying gelatin coating solution containing silver iodo-bromide (silver iodide, 2 mol~; average particle size, 0.008 ~m) not undergone either chemical or spectral sensitization, so that the amount of coated silver is at a rate of 0.1 g/m2 and the amount of deposited gelatin is 0.8 g/m2.
NHC0 ~9 c 5 H,,(t) O ')~ \=~ NHCOCH 2 0 ~ CsH,, ( l .
c e ~ C e c e Sample (b~: Identical with the above Sample (a), except that silver iodo-bromide not contained in the protective layer.
Each layer incorporates, in addition to the above com-ponents, a gelatin-hardening agent and a surfactant.
Samples (a) and (b) are subjected to white exposure using an optical wedge, and the treated in the following manner.
~ ~7 - t 3 1 7 5 00 One developer solution contains various 'cypes of development inhibitors with a total amount to suppress the sensitivity of Sample (b) to 60~ (in logarithmic expression, -A log E = 0.22).
The other developer solution does not contain such inhibitors.
Processing (38C) Color developing 2 min 40 sec Bleaching 6 min 30 sec Washing 3 min 15 sec Fixing 6 min 30 sec Stabilizing 1 min 30 sec Drying Compositions of the processing solutions used in the re-spective processing steps are as follows:
IColor developer solution) 4-amino-3-methyl-N-ethyl-N-(~-hydroxyethyl)-aniline sulfate 4.75 g Sodium sulfite anhydride 4.25 g Hydroxylamine.1/2 sulfate 2.0 g Potassium carbonate anhydride 37.5 g Trisodium nitrilotriacetage (monohydride)2.5 g Ptassium hydroxide 1.0 g Water is added to the above components to prepare one liter solution.
(Bleacher) Ferric ammonium ethylenediamine tetraacetate 100 g l3l7soa Diammonium ethylenediamine tetraacetate10.0 g Ammonium bromide 150.0 g Glacial~acetic acid 10.0 g Water is added to the above components to prepare one liter solution, which is adjusted to pH = 6.0 using aqueous ammonium.
(Fixer) Ammonium thiosulfate 175.0 g Sodium sulfite anhydride 8.5 g Sodium metasulfite 2.3 g Water is added to the above components to prepare one liter solution, which is adjusted to pH = 6.0 using acetic acid.
(Stabilizer) Formalin (37~ aqueous solution) 1.5 mQ
Konidax (manufactured by Konica Corporation) 7.5 mQ
Water is added to the above components to prepare one liter solution.
Assuming that the sensitivity of Sample (a) with a devel-opment inhibitor not addes is S0' the sensitivity of Sam,ple (b) with a development inhibitor not added is S0', and that the sensitivity of Sample (a) with a development inhibitor added is SA, and the sensitivity of Sample (b) with develop-ment inhibitor added is SB, the following expressions are valid:
* Trade mark.
~ 39 ~ 1 31 7500 Desensitization ratio: AS = SO - SA
Desensitization ratio: ~S = SO' - SB
Diffusibility = ~S/~SO
wherein each sensitivity is defined as a logarithmic number (-log E) of a reciprocal of an exposure amount corre-sponding with a density status of "fog density + 0.3".
Diffusibility of several types of development inhibitors, determined in this method, is listed in the following table.
- ~- 13~7~
Table _ Amo~mt added Desensiti~ation Diffusibili~y Structure _ , _ (mol/Q) ~SO ! ~S ~S/~SO
HS--i/ 11 . 1.3X10-s 0.22 ~ 0.05 0.23 ~N~`N=C~N~ ; 3 ~'0 ' 0.2 0.08 0 14 CH3 _ HSY~CII~ 2. 5 X 10- S 0. æ 0. 10 0. 45 HS //N-~
1ZHS 3 O~l0- S 0 21 0.10 0 4B
HO~ N0z ~1 CHzN -C~H~ N N 1. 4 x 10~ 5 0. 23 0.11 0. 48 N - i 2.5X10-5 0.22 0.13 0.59 011 .
Table (continued) Amount added Desen3itization l~iffusibility Structure ... _ .,_ .. _ (mol/Q) So S ~S/~Sa ~N ~ C~ ~ 3~l05 023 0l5 _ _ ~N ~ CH3 ~ _ _ ~ l.7~l0-' ~ 0.21 0.~0 ~ 0 ~ ~
Next, a compound indicating diffusibility of greater than 0.40 and therefore favorably used in embodying the invention, that is, a compound represented by the previously mentioned general formula (D-l) and known as a diffusible DIR compound is hereinunder described.
As the diffusible DIR compound, any compound having any chemical structure may be used, as far as the compound releases a group of which diffusibility is within the above-defined range.
The typical structural formula of general formula (D-l) is given below.
General formula (D-l) A t ( Y d ) m d - 42 ~ 1 3 1 7 5 0 wherein Ad represents a coupler residue; md represents 1 or 2; Yd represents a group being capable of split off upon reaction with an oxidation product of a color developing agent by coupling with the coupling site on the coupler residue A, and, more specifically, represents a group being capable of releasing a development inhibitor group or development in-hibitor with diffusibility of greater than 0.40.
Yd in general formula (D-1) is typically represented each of the following general formulas (D-2) through (D-l9).
General formula (D-2) - N N
~--(Rd ~ ) n d General formula (D-3) General formula (D-4) , / N~ tRdl)nd - OCH 2 - N N ~ N ~ /
(Rd,)n d General formula (D-5) General formula ~-6) N ~ (Rdl)n~ - SyX~d, General formula (D-7) General formula (D-~) --N~ ~ ( R d I ) n d --S
Rd 2 Ge~eral formula (D-9) N - N
- S ~ N ~ Rd<
Rd 3 In general formulas (D-2) through (D-l9), Rdl represents a hydrogen atom or halogen atom, or an alkyl group, alkoxy qroup, acylamino group, alkoxycarbonyl group, thiazolydene group, aryloxycarbonyl group, acyloxy group, carbamoyl group, N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group, arylthio group, aryl group, hetero-cyclic group, cyano group, alkylsufonyl group or aryloxycar-bonylamino group. nd represents 0, 1 or 2. When nd is 2, Rd s may be identical or different with each other. The total number of carbon atoms contained within n units of Rdls ranges from O to 10. Additionally, the total number of carbon atoms contained within Rdls in general formula (D-6) ranges from O
to 15.
Xd in this general formula (D-6) represents an oxygen atom or a sulfur atom.
In general formula (D-8), Rd2 represents an alkyl group, aryl group or heterocyclic group.
In general formula (D-8), Rd3 represents a hydrogen atom, or an alkyl group, cycloalkyl group, aryl group or hetero-cyclic group. Rd" represents a hydrogen atom or halogen atom, or an alkyl group, cycloalkyl group, aryl group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkanesulfonamide group, cyano group, heterocyclic group, al-kylthio group or amino group.
If Rdl, Rd2, Rd3 or Rd4 represents an alkyl group, such an alkyl group may have a substituent, and be either straight-chained or branched.
If Rdl, Rd2, Rd3 or Rd4 represents an aryl group, such an alkyl group may have a substituent.
If Rdl, Rd2, Rd3 or Rd4 represents a heterocyclic group, such a heterocyclic group may have a substituent. More speci-~ 45 ~ 1317500 fically, such a heterocyclic group is a five- or six-membered single or condensed ring containing at least one hetero atom selected from a nitrogen atom oxygen atom and sulfur atom.
The preferred heterocyclic group is selected from a pyridyl group, ~uinolyl group, furil group, benzothiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group, triazolyl group, benzotriazolyl group, imide group, oxadine group and the like.
The number of carbon atoms contained in Rd2 of general formula (D-6) or (D-81 is O to 15.
The number of carbon atoms contained in Rd3 or Rd4 of general formula (D-9) is O to 15.
General formula (D-10 - TIME - INHIBIT
In this formula, TIME group is a group being capable of bonding to the coupling site on A and also capable of split off upon reaction with an oxidation product of a color devel-oping agent; once split off from the coupler, this group con-trollingly releases an INHIBIT group. The INHIBIT group is a group which serves, once released as mentioned above, as a development inhibitor (a group, for example, represented any of the above-mentioned general formulas (D-2) through ( D-9)).
-TIME-INHIBIT group is general formula (D-10) is typical-ly represented by any of the following general formulas (D-11) through (D-19).
- 46 - l 3 1 7500 General formula (D-ll) _ O ~, ( n ds) e d (CHz) kd- N- Co - INHIBIT
Rd b General formula (D-12) General formula (D-13) (Rd 5 ) e d -O ~ - O ~ CH 2 -INHIBIT
CHz-INHIBIT (Rds) e d General formula lD-14) General formula (D-15) Rd 6 0~( CH 2 ) k- NCO -INHlBlT
/N~ - N ~ Rd b - O ~ N \==~(Rds) Q
/ Rds General formula (D-16) ~ 'I (Rd7)md -N ~ tCH 2 ) KdBd -CO -INH1BIT
- 47 ~ l 3 1 7 500 General formula (D-17) o N - Rd 7 ,~L ( C H Z ) X d B d --C O I ~i HIBIT
General formula (D-18) (Rds) Q d O (CHz)K d B d - CO INHIBIT
General formula (D-l9) 7du -- O (C) ,~ d N--CO --I Nll I BIT
Rdq Rdo In general formula (D-ll) through (D-15) and (D-18), Rds represents a hydrogen atom or halogen atom, or an alkyl group, cycloalkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureide group, cyano group, nitro group, sulfonamide group, sulfamoyl 1317~
group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group or alkanesulfonyl group. In regards to general formulas (D-ll) through (D-13), (D-15) and (D-18), Rdss may bond together to form a condensed ring. In general formulas (D-ll), (D-14), (D-15) and (D-l9), Rds represents an alkyl group, alkenyl group, aralkyl group, cycloalkyl group, heterocyclic group or aryl group. In general formulas (D-16) and (D-17), Rd7 represents a hydrogen atom, or alkyl group, alkenyl group, aralkyl group, cycloalkyl group, heterocyclic group or aryl group. Rda and Rdg in general formula (D-l9) independently represent a hydrogen atom, or an alkyl group (favorably, an alkyl group having 1 to 4 carbon atoms). k in general formulas (D-ll), (D-15) through (D-18) represents an integer 0, 1 or 2. Qd in general formulas (D-ll), (D-15) through (D-18) represents an integer 1 to 4. md in general formula (D-16) represents an integer 1 or 2. If md is 2, the respèctive Rd7 may be either identical or different with each other. n'a in general formula (D-l9) represents an integer 2 to 4. n'd units of respective Rd8s or Rdgs may be either identical or different with each other. B in general formulas (D-16) through (D-18) represents an oxygen atom, or - N - (Rd6 Rd6 is identical with the previously defined Rd6). ... .. in general formula (D-16) means either single bond or double bond is possible. In the case of single bond, md represents 2; in ~ 49 ~ 131750G
the case of double bond, md represents 1. The definition of INHIBIT group is identical with a group represented by any of general formulas (D-2) through (D-9), except the number of carbon atoms.
With an INHIBIT group, the total number of carbon atoms w thin Rls in one molecule represented any of general formulas (D-2) through (D-7) is O to 32. The number of carbon atoms within R2s in one molecule represented general formula (D-8) is 1 to 32. The total number of carbon atoms within Rd3s and Rd4s in one molecule represented general formula (D-9) is O to 32.
When Rd~, Rd~ or Rd7 represents an alkyl group, aryl group or cycloalkyl group, such a group may have a substituent.
Among diffusible DIR compounds, the preferred is a com-pound of which Yd is represented by general formula (D-2), (D-3) or (D-10). With the examples of Yd represented by (D-10), those preferred have an INHIBIT group represented by any of general formulas (D-2), (D-6) (especially when Xd is gen-eral formula (D-6) is an oxygen atom), and (D-8) (especially when Rd2 is general formula (D-8) is a hydroxyaryl group; or an alkyl group having 1 to 3 carbon atoms).
The exmaples of a coupler component represented by Ad in general formula (D-l) include a yellow dye image-forming coup-ler residue, magenta dye image-forming coupler residue, cyan dye-image forming coupler residue, and colorless coupler - 50 - l 31 7500 residue.
The typical examples of the preferred diffusible DIR com-pounds useful in embodying the invention are those described, for exmaple, in U.S. Patents No. 4,234,678, No. 3,227,554, No. 3,617,291, No. 3,958,993, No. 4,149,886, and No.
3,933,500, Japanese Patent O.P.I. Publications No. 56837/1982, and No. 13239/1976, U.S. Patents No. 2,072,363, and No.
2,070,266, and Research Disclosure, 1981, Dec., No. 21228.
When incorporating any of the above-mentioned DIR com-pounds into the light-sensitive material of the invention, the preferred amount of addition is 0.0001 to 0.1 mol, in parti-cular, 0,001 to 0.05 mols per mol silver halide.
In embodying the invention, a DIR compound represented by general formula (D-1) among those described above is capable of much excellent effects.
The typical examples of DIR compounds represented general formula [D] or (D-1) are listed below. However, the scope of the invention is not limited only to these compounds.
(Example compounds of general formula [D]) ~d l-COC I CO - RJ Z
Example compound No. R d I ~ R d 2 ¦ Y d D - I ~ 1 ( 2) ( 4) (78) D - I ~ 2 ( 2) ( 4) (55) D - I - 3 ( 2) ( 3) (38) D - I - 4 ( 2) ( 3) (30) D - I - 5 ( 1) ( 1) (30) D - I - 6 t 67) (67) (34) D - I - 7 ( 7) (68) (84) D - I - 8 (58) (58) (~0) D ~ I - 9 ( 2) ( 4) ~91) D - I - 10 ( 2) ( 4) (90) D - I - 11 t 62) (62) (76) D ~ I - 12 (68) (68) (~
D - I - 13 (66) (74) (~
D - I - 14 (66) (64) (82) D - I - 15 ( 2) ( 4) (83) D - I - 16 ( 5) ( 6) (31) D - I - 17 (67) (67) (34) D - I - 18 . _ ( 4) (32) R d l l ¦ Y d N~ ~
N O
I
Rd z _ Example compound No. R d R d Y d I
D - I - 19 (69) (10) (30) D - I - 20 (70) (10) (87) D - I - 21 (12) ( 7) (34) D - I - 22 (11) ~ 10) (79) D - I - 23 ( 7) (72) (32) D - I - 24 (15) (73) (92) D - I - 25 ~ 71) t 10) (36) D - I - 26 ( 9) (10) (30) D - I - 27 (12) (13) (35) D - I - 28 (60) (10) (85) D - I - 29 (59) (10) (86) D - I - 30 (57) (10) (30) D - I - 31 (75) (72) (78) _ 53 - l 3 1 7500 O H
R d Y d Example compound No-¦ R d Y d D - I - 32 (63) (78) D - I - 33 (63) (40) D - I - 34 (65) (93) D - I - 35 (65) (38) D - I - 36 (63) (43) D - I - 37 t 63) (77) D - I - 38 (19) (95) D - I - 39 (94) (47) D - I - 40 (21) (47) D - I - 41 (19) (46) D - I - 42 (94) (46) The symbols representing substituents Rdl, Rd2 and Ydl in the above tables are used for convenience of classifying the compounds of general formula [D].
- 54 - 1 3 1 7~03 HOCO C5H 1 1 ( t) ~NII ~ O~NIICbCIIZO ~ CSIII~(t) 110 C O N C H z S
D -- I -- Ll ~I
C ~ ~ H 3 7 O N O
S 11 1~
N
OC I aH 3 7 (n) N H C O ~
S ~ .~ N H z O N N
- 55 - 1 3 1 7 50~
OC, 4 H z 9 NN ~) N
~NHCOCHO~,\\--Cslll ~ (t) C H 3 C Q CzH5 C 5 H,, (t) \N-N~ C2H5 C, 3H27CONH
~ / N
.. o.
r~
CoocllzCONH~
(Example compounds of general formula (D-1) ) C I ~ H Z 7 C O N H
/ N
l \>
( I
~ ' C O O C H z C O N H ~) ~d I - COCHCO--I
Y d EYample compound No. R . ~ R . y .
..
D ' -- 2 ( 1 ) ( 1 ) (30) D ' -- 3 ( 2 ) ( 3 ) (30) D ' - 4 ( 2 ) ( 4 ) (30) D -- S ( 5 ) ( 6 ) (31) D -- 6 ( 2 ) ( 4 ) (32) D - 7 ( 2 ) ( 3 ) (32) D -- 8 ( 7 ) ( 8 ) (33) D -- 3 3 _ ( 4 ) ( 5 5 ) t 31 7~0 Rt, 1l I Yd N O
R,l Z
Example compound ~o. ~ __ Y ~
D ' -- 9 t 9 ) ( 10) (30) D ' -- 10 ( 11 ) ( 10 ) ~30) D ' -- 11 (12) ( 7 ) (34) D ' -- 1 2 ( 1 2 ) ( 1 3 ) ( 3 5 ) D -- 13 ( 9 ) ( 14 ) (36) D -- 14 ( 15 ) ( 16 ) ( 3 7 ) 1 3 ~ 7500 o xa:Qle compound No. R
D ' - 15 (17)(38) .D - 16 (17)(39) D ' - 17 (18)(40) D - 18 (20)(41) D ' - 19 (18)t42) D ' - 20 (18)(43) D ' - 21 (18)(44) D ' - 22 (18)(45) D ' - 23 (19)(46) D ' - 24 (21). (47) D ' - 25 (21)(48) D ' - 26 (22)(49) D ' - 27 (22)(50) D ' - 28 (22)(51) D ' - 29 (23)(52) D ' - 30 (18)(53) D ' - 31 (18)(54) D ' - 32 123)(49) D - 33 (63)(96) 1 3 1 7~00 (1) through (95) in the tables above represent the fol~
lowing species.
( 1 ) ~ 2 ) C ~ , .
NH~ -- C(CH3) 3 COOCHCOOC~2H2s ( 3 ) C ~
- NH ~ CsHIl(t) NHCOCHzO - ~ CsHIltt) ( 4 ) C Q
- NH ~ CsHI~(t) ~ NHCO(CH2) 3 - ~ CsHIl(t) ( 5 ) ( 6 ) - OCII 3 , - NH - ~
O C 1 4 Hz 9 - 60 ~ 1 3 1 7500 ( 7 ) ( 8 ) c e ---N 11~/~
C O O ~I
( 9 ) --NIICO--,~ CsHI I (t) NllCOf HO --~ C s H ~ ~ ( t) C z H s ( 1 0 ) ( 1 1 ) C ~
-~ C Q -- NHCOfHO --c e , C2 ( 1 2 ) ( 1 3 ) -- C l 7113 5 < N 3 ( 1 ~ ) ( 1 5 ) ~ c e - C~13 - 61 ~ 13~7500 (16) (17) ~ SO3H . - CONHCI~H37 , (18) (19) - CONH ~ - CONH ~
OCI~Hz9 , OC, 4 Hz 9 ( n) , (20) CsH I I (t) - CONH(CU2)30 ~ C5H,,(t) (21) . - CONH ~ OC,,H2 9 (n) t22) - CONHCHzCHzCOOH
t23) - CONHCHzCH2COOCH3 ~ 62 - 1 3~ 7500 (30) (31) ~ N ~ N = N ~ N 11 2 (32) C H z N C O S ~/; ¦¦
CzHs (33) 1~ c 11 z s--. ¦ `N COO~I
CsHI I (t) NI~COCII zO ~CsH I I ( t) 34 ) (35) ~N~Br S--lS~L NllCOCsHI I
(36) -N ~=O
N- N
Cl12N- COS ~/ ll ¦ N- N
(37) -OCHzCHzjCOS ~ ~ CH3 N - N
C3H7(i) (38) (39) ~N~ ,CH3 11 \N ~ CH3 . / ~ Nll2 ~ N
(40) (41) -S ~/ ll -OCH2- N N
N- N
C 2 Hs CH3 Cl13 - 64 ~ 1 3 1 7~
(42) --O C H z--N N
COO~
(43) O ~ N ~
CHzNCO N N
Czlls iYOz ~
CO 2CH zCH zCN
t44) O N N
~CHzI COS~
~j/C 3 H
NO z ~ .
(45) N N
N ~L
NO z \/ , - 65 ~ t 3 1 7500 (46) O N N
c C N z--S
~N CH 3 t47) O N--N
/~ C H z--S
N I N N
=/ ~N'---CH3 CzHs (48) C H z--S ~ ~ C H 3 ~N CH3 N N
(49) O N--N
2 N~ /~ CH z--S
~N Cl ~Hz3 OH
13~750~
(50) O N--N
O z N ~ N~C C H Z--S ~
C2~s (Sl) OzN ~ ~ CIlHz~ N - N
(52) O N N
02N ~ ~ CH2----~\/
~N C~IHza (53) (5~)1 CH2S ~ CH2 -S
NHCOCH~
NHCOCHzCH2COOH J
( 55 ) (56) --~ N= C~ N H ~3 ( 57 ). ( 58 ) c e --NH~ -- CZHs N H COC1 3 Hz 7 ( 59 ) c e --NH~NHCOCHO--~ OH
C z H 5 C ~ H 9 ( t ) 60 ) c e --NH~ O
\ N~ C . 8 H 3 7 -68- 131750~
( 61 ) (62) O H ---NH~CH3 -- OC, zHzs ~y N--N
\S~/ 11 N--N
I
CzHs ( 63 ) (64) C O O H
--CONH~3 --NH~
OC I 4 H z 9 . OCH 3 ( 65 ) . (66) -- C O N 11 C 1 8 11 ;s 7 ~ ~ O C ~ 8 H 3 7 ( 67 ) (68) --NHC~ --N11~3 COOC~ 2Hz5 , COOC, zHz 5 ( 69 ) CsHI ~ (t) --N HCOC H O ~C 5 H,, (t) C z 1~ 5 - 69 _ 13175~
(70) c e NllCOC~3Hz~
t71) - NHCO ~ C\sHIl(t) NHCOCH20 ~ C5H,,~t) (72) C5H,,(t) NHCOCHO ~ Csllll(t) CzNs (73) - ~ NNCOCHO ~
CzHs C~sH 31 t74) (75) - Nll ~ - N
O C 2 Hs 13t7500 - 70 ~
(76) (77) _ O -CH2 N~ ~ NNCOC4Hs ~ ~ COO-(78) (79).
N ~3\ 0 C ~ N .
(80) (81) , N ~ NHCOCsH~ N ~ C z ll s (82) .
~N~\NNCOC,N,~ .
- 71 - l 3~ 7500 (83) O ~ CHz ~
- N\ . HCHOC~H, 3 0 \CH2NCOS
CH J
\CHJ
(84) ~ ~ N - N
O CH2NCOS ~ ¦¦
I N - N
CzHs ~
~ , .
(85) (86) N - N N - N
-s~ 11 -s~ 1~
N - N N - N
OH
- 72 - ~ 3 1 7500 (87) (88) --S ~/ ¦¦ -- N N ~N
N--N
C z H s CH~ CH3 (89) t90) O~<N >~O
-- S~5~NHCOC5H, I , (~NCOS~
C3~7 ~ .
(91) (92) I
O~,<N~O O~<N~O
C 11 ~--N C O S--~
N N ¦ N N
C~H7 ¦ CzH 5 . ~ ,211~.C Q, - 73 - 1 3 1 15~
(93) --S~
N N H
(94), -- CONII (CIJ2) ~O ~C5H ,, ( S) C 5 H I , ( t ) (95) ,~ C H Z N C O S ~
~ IN--N
C 2 ~I 5 NOZ CH (CH3) Z
(98) 1_CHZCH2NCOS N--C2H5 Il C 3 H 7 ( i S O) \ND
- 74 - 13t7~00 The other preferred examples of DIR compounds advantage-ously used are the following example compounds.
[Example compounds]
( D~
C~
(Cl13) 3CCOCHCONH ~ ~
S NIICO(CI12) sO Cslll I (t) N IN ~3 N= N
(Dd-2 ) C~
(Clls) sCCOCllCONII~ Cslll I (t) NIICO (CH 2) 30 ~ Csll I I ( t) N ~3 N=<
Cl~3 ~ 75 ~ 1 3 1 7~00 ( D - 3 ) N-N ~ ~ N ~
CsHIl~t) NHCOCHO ~ CsHI~(t) CzHs ( D~- 4 ) CONH
N
N = N
~ 76 - 1 31 7~00 (D--5 ) OH
CONH
' IN I--C zHs ( Dd- 6 ) C~
(CH3)3CCOCHCONII ~ Csllll(t) O NHCO(CHz)30 ~ CsHll(t) CH2NCOS 11 IN- C2Hs NOz CzHs N~N~N
~ 31~50~
( D--7 ) ce (CHJ)aCCOCHCONH ~ CsHI~(t) NHCO(CHz)10 ~ C5YI I ( t) CHz- S
NO 2 N~N~N
( D~--8 ) C~
(CHa)JCCOCHCONH ~
O NHSO2CI~H33 C ,, .--s T' N ~- 011 N N
~N~
-78- t3~7500 (D--9 ) 1--N ~r (CH z) 3 ~ NHCOCHO ~ OCOCII 3 CH3 N/lN~N C~zHzs H
N C O S ~ N
C3R7 (iso)~N~
t D~--10) ~\~CONH ~
O C I .I H z 9 CHzNCOS ¦¦ IN~3 C3H? (iso) N N
NO z ~Ns~
( D'L-ll) CONN ~
OCHzCH2NCOS 11 IN - CzHs C3H7 (iso) N ~N
t Dd--12) OH C 5 Hll(t) CONH(CHz) 40 ~ CsHIl(t) N~N"N
( Dd-13) OH
O C ~ 4 H z q ~2 ~ ~ N
( Dd-14) tCH3) 3CCOICHCONH ~ SOZNH2 C, ,H3, N N
NO z ~N~
~ 81 - l 31 7500 ( D -15) HOCO \~_~ CsHIl~t) NH ~ O ~ NHCOCH20 ~ CsHIl(t) CHzS 11 IN ~
N~N~N
( Dd-16) OH
CONH ~ COOH
~ CHz- S T N
¦~N/~C" H 23 ~ N~
NOz - 82 _ 1 3 1 7500 ( D--17) OH
,.X~ CONHCH2COOH
O fH3 ~NCOS 11 IN ~ OH
COO C I z H 2 5 ~Ns~N
( D~--18) l--C~ 8H37 O~\N/~O
~S 11---IN~
~ N
( D~--19) OC, ~H37 (n) NHCO ~
~P 1' 5 ~r ~ 83 _ t 31 7503 ( D~-20) OC~Hzs S ¦¦ IN ~3 ' N ~ O \N~
( D~-21) C~H,l(t) NHCOCH20 ~ C5 Hl,(t) O ~ NHSOzCH3 O CHzS ~ N
~ N ~N
t D¢-22) ~ NHCO(CHz) 30~Csll I I ( t) (cH3)3ccoFHcoNH ~ CsHll(t) ~ N ~ cc HH 3 - 84 _ t 3 t 7500 ( D -23) NIICO(CH2)30 ~ Csllll(t) (CH3)3CC0fHC0NH ~ Csllll(t) CQ
N~ ~ COO
D~-24) C,zHz500CCHooc ~ ~NHCOCHCONH ~ , CH~
~N ~ COO
t D~-25) C,2H2sOOC ~ NHCO~HCONH ~ COOCIzH2s N N ~ Br ( D -26) C2Hs /N~
CsH" tt) ~ OCNCONN~ r~
' C~ ~ CQ
( DL-27) CO2CI2Rzs COFHCONH
i C~
N O
Cz~ls ~
( ~-28) C 1 2H zsOOCfHCOOCI2112s N~ ~ CO
- 86 - 1 3~ 7 5 00 ( D~- 29) ~ NH ~ S ~ N-IN
C,3}1Z7CONH `N O CZH5 CQ ~ ~CQ
CQ
( D~-30) C5~3, 1 (t) ( t) C511" ~ OCHZCONH
~ 4~ N--N
O C~H9 ( Dd-31) OH
CONHC~H37 S
N N
1-1, ' H NHz ( Dd-32) NllCO(CNz)30 ~ CsHIl(t~
~CH3)3CCOfNCONH ~ CsHIl(t) O ~ N ~ O CQ
~ N- N
CKz- NCOS ~/ ll ¦ N- N
~. . `
( D~--33) NHCO(CHz) ~0~3Cslll I (t) (CN3) ~CCOICHCONH~ CsHI ~ ~t) 0~N~O CQ
N--N
C~H
( D--3~1) OH
~CONHCI ~H37 N~N
( D~--35) OH
~ NHCOCHO ~ CsHI~(t) CH3 ~ C~ C2Hs Csllll(t) N N - C2Hs 1_1 ( D~--36) Cl7H3s N
~0(~
Br go 1 31 7500 ( Dd-37) ,N~
~ OCHCONH ~ N
C,sH31 CzH5 ~N O
¦ OC,H~
CQ~_ Ce ce ( Dd- 38) C ~ 2HZ50CO ICHCOOC~zH2s N N ~ NHCOC~Hq ( Dd-39) C~zH2sOOC ~ NHCOCHCONH ~ COOCI2H 2 5 N~N ~ NllCOCsllll - 91- t317500 ( Dd- 40) OH
, ~ O C I z H z 9 CH zNCON~
NO2CzHs COzCHzCH2CIY
( D~--41) OH
~CONHCI bH33 ~CII:S~
NO2 , OH
- 92- t317500 ( D~--42) CONH ~
CH NCOS ~ ~ NHz ( D~-43) COzC1~13 2 9 (CH3)3CCOCHCONH
O C
NOz I N -N
CHzS ~ ll N- N
I ~ C21~s CH2CH2N, ~C211s ~ 93- 1317500 ( Dd- 44) OH
~CONH(CH2~ 30Cl zHzs O N--N
~N~S~N~LC~Hg ( Dd- 45) ~; ~0 ~ N O z C z H s NHCOfHO ~CsHI I (t) C z H 5 C s H I I ( t ) - 94_ 13~7500 ( D ~--4 6 ) C~sH370 ~ COfHCONH
N~ OCzHs ~N~Czlls ( Dd~47) COzH
ClsH~70 ~ COCHCONH
~N~y~ OCH~
~N ~ NHCOC~H,~
( Dd--4 8) o CH~
. C2Hs C2H~C~
hHCOCIHO
C2Hs C~sH~
1 31 ~500 ( D~-49) NHCO(CN2)30 ~ CsHll(t) (CH~)3CCOfHCONH - ~ CsHIl(t~
y ~ H NHC0CbH,3 ¦ CHzlCOS ~ NN
( Dd-50) Cl3H2~CONH
~ N N
O ~ , COOCHzCONH ~
( D~--51 CH30COfllCONII
IN I ~3NH2 N--N
- ( Dd- 52) ( t ) C 5 H I I ~ O C H 2 C O N 11 C5H" (t) CONII 11 ~N2~
~N/~O CIIZNCII3 CQ~CQ COS~/N_ IN
CQ
CO2~3 ~ 97 -1 ~1 7 5 00 ( D - 53) OH
~ CONH(CHZ)30 ~ C5H" (t) ~ CsHIl(t) N ~ CH2S ~ N -IN
`N CH3 t Dd-54) ~ COzCHCOzC~zHz 5 (CH3)3CCOCHCONH ~ CH 3 c~ .
~' CZHS
¦ CHzCHzCOz ~
1 ~ 1 7500 ( Dd- 5~) CzHs ( t) C 5H " ~ OCHCONH ~ N~N~N
CsHI I (t) CONH~ ~
CQ~ CQ I ~3 CQ
( Dd_56) ~1--N
S~ 1~ NHCOCsH
C,7H~,~ \S/
N~N
, ( D ~ 57) ce N--N
O ~ UH~S
c e ,~3~ c Q
CON~ 2 C~
t D"--58) CzHs HO $~ OCHCONH ~ C ~ S _</N--IIN
C4N,, (t) NN~ N--N
,¢~, C~
loo- 1317~00 t D--59 ) ( n ) N " C ., O C N N
ce~ce ce ( D~--60) ClzN2sOOC~ ~ NHCOjHCONH ~ 3 ~COOCI2112s / N ~3~B r ( D--61) ON
,CONHC, sH 17 N--N
l3l7son 62) OH
OCI~Hz9 CHz ,N ~ COO
( D~-63) OH
CONHCH2CHzCOOH
N
CHZS ~
N- N
CI,HZ3 '' ~3 - 102 ~ l 31 7500 ( Dd 64) OH
~ CONHCHzCHzCOOll NO2 ~ N
CH2S ~ ll N- N
Cl~Hz3 ( D -65) OH
~ CONHCH2GH2COOH
NO2 ~ N
CH2S ~ ll N- N
Cl~Hz~ ¦
- 103 - 1 3 1 75~
. .
( D--66) OH
~ CONHCHzCH2COOH
OzN ~ N
CHzS ~ ll I N- N
OH
( D~--6 7 ) O H
~CONHCHzCHzCOOH
Nl ~1 N~ C H z S ~ ll N--N
C~sH31 ~3 OH
- 104 - l 3 1 7500 ( D--6 8 ) O H
CONH ~3 OC, 4Hz~
N
~\ C H 2 S ~ ll N--N
~3 t D--6 9 ) O H
O C, ~ H z 9 ~N
~\ CH 2S~ ll N--N
COOH
( D~-70) OH
~CONH~30CI ~H2g tn) I ~1 2 ~ N_IN
CZHS
( Dd--71) OH C5H " (t) CONH -(CH2)~0 ~ C5H " tt) ~ Nl ~1 CHZS ~ N_IN
CzHs ~ 3 1 ~ 3 0 10 ( Dd 72) OH
CONH ~
~ OC,~H29 NO2 ~ - Nl ~
~\ C H Z S ~ 11 N- N
COOH
( D--73) OH
CONH ~
~ OCI4H29 CH2S ~ ll ~3 -107_ l 3~7~
( D~--74) OH
~ O C ~ ,~ H z 9 NO2~Nl~¦
C H 2 S ~N--¦¦
CH3 ~3 OH
( D--75) OH
~, C O N H
NOz~ 1~1 !i~ N~ N--N
CzHs ( D -76) OH
CONH - Cl12CHzCOOH
N
~f \ 1 CIIHz~ N N
t D -77) OH
CONH - CHzCHzCOOII
CH2S ~ k CH~
- log - 1 31 7500 ( D~-78) OH
CONH- CH 2 CHzCOOH
I ,~
CHzS ~ ~ CH3 Cl3Hz7 N N
( D -79) OH
CONH- CHzCHzCOOH
~3 Nl ~1 CHzS ~ k CH3 1317:5`~0 ( D~--80) OH
OC,4 H z~
N ~
( D~--81) OH
OC, 4 H z ~3 Nl~
~\CHzSl~ ~ CH3 ( D ~--82) OH
O C, 4 H 2 9 N
~\ C H z S 1/ ~r C H 3 ( Dd- 83) C O N H ~
OC, ~Hzq I ~1 ~\ C H 2 S 1' k C H 5 ( D~--84) OH
OC, ~llz~
C~
> C = N
C~
N N ~3 N = N
( D~--85) OH
C O N N ~) , N O z >C = N~
N IN ~ O H
N = N
( Dd- 86) OH CsHI I (t) 3~ C O N N ~ C H 2 ) .~ O ~ C s I I I ( t ) >C=N~
CQ
N
N = N
( D - 87) CQ
tCH3)3CCoCHCoNH ~ CsHIl~t) ¦ NHCO (CH 2) J ~ C sH ~ I ( t) > C=N ~ C9 ; N
~ N
- 114 - l 3 1 7500 Any of the above-mentioned DIR compounds may be incorpo-rated into the light-sensitive silver halide emulsion layer and/or the non-light-sensitive photogrpahic structural layer;
preferably it is included in the light-sensitive silver halide emulsion layer.
Two or more kinds of DIR compounds may be included in one layer, or one and same kind of such compound may be included in two or more different layers.
These DIR compounds are preferably included in the emul-sion layer in the amount of 2 x 10-5 to 5 x 10~l mols, more favorably 1 x 10-4 to 1 x 10~l mols, per mol of the silver in the emulsion layer.
To incorporate such DIR compounds in the silver halide emulsion or in the coating solution for another photographic structural layer, where the DIR compound is alkali-soluble, it may be added in the form of an alkaline solution. If the com-pound is oil-soluble, it is preferred that the compound is added to the silver halide emulsion according to any of the procedures described in the respective specifications of, for example, U.S. Patent Nos. 2,322,027; 2,801,171; 2,272,191;
and 2,304,940, that is, the DIR compound is dissolved in a high-boiling solvent, or if necessary, in a combination of such solvent and a low-boiling solvent, so that it is dis-persed as fine particles therein, such dispersion can be added to the emulsion. In this conjunction, a mixture of two or 1 3 ~ 7 5 ~ 0 more kinds of DIR compounds may be used. A further preferred method for addition of such DIR compound will be described in detail. The preferred method comprises dissolving one or more kinds of the above-mentioned DIR compounds in organic acid imides, carbamates, esters, ketones, urea derivatives, eithers, or hydrocarbons, or in particular, any of such high-boiling solvents di-n-butyl phthalate, tri-cresyl phosphate, triphenyl phosphate, di-isoctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamide butyl, N,N-diethyl laurylamide, n-pentadecyl phenylether, di-octylphthalate, n-nonyl phenol, 3-pentadecyl phenylethyl ether, 2,5-di-sec-amylphenyl butylether, monophenyl-di-o-chlorophenyl phosphate, and fluoroparaffin, and/or any of such low-boiling solvents as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetonitrile, dimethylforma-mide, dioxane, and methyl ethyl ketone, mixing the solution with an aqueous solution containing anionic surfactants, such as alkyl benzosulfonic acid and alkyl naphthalenesulfonic acid, and/or nonionic surfactants, such as sorbitan sesqui-oleate and sorbitan mono-laurate, and/or a hydrophilic binder, such as gelatin or the like, then emulsifying and dispersing the mixture in a high-speed rotary mixer or a colloid mill, or in an ultrasonic dispersion apparatus, and adding the disper-- 116 - 1 31 7 ~ 0 sion to the silver halide emulsion.
Alternatively, the DIR compound or compounds may be dis-persed by employing any of known latex dispersion techniques.
Various latex dispersion methods and their advantages are des-cribed in Japanese Patent O.P.I. Publication Nos. 74538/1974, 59943/1976, and 32552/1979, and also in "Research Disclosure", No. 14850, August 1976, pp 77 to 79.
Examples of latex suitable for this purpose are homopoly-mers, copolymers, and terpolymers of various monometers, such as styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxy ethyl methacrylate, 2-(methacryloyloxy)ethyl trimethyl ammonium methosulfate, 3-(methacryloyloxy)propane-l-sodium sulfonate, N-isopropyl acrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, and 2-acrylamide-2-methylpropane sul-fonic acid.
Aforesaid DIR compounds may be synthesized according to various methods described in the following publications: U.S.
Patent Nos. 3,227,554; 3,615,506; 3,617,291; 3,632,345;
3,928,041; 3,933,500; 3,938,996; 3,958,992; 3,961,959;
4,046,574; 4,052,213; 4,063,950; 4,095,984; 4,149,886; and 4,234,678; U.K. Patent Nos. 2,072,363 and 2,070,266; Research Disclosure No. 21228 (1981); Japanese Patent O.P.I. Publica-tion Nos. 81144/1975, 81145/1975, 13239/1976, 64927/1976, 104825/1976, 105819/1976, 65433/1977, 82423/1977, 117627/1977, 130327/1977, 154631/1977, 7232/1978, 9116/1978, 29717/1978, - 117 ~ l 3 1 7500 70821/1978, 103472/1978, 10529/1978, 135333/1978, 143223/1978, 13333/1979, 49138/1979, 114241/1979, 35858/1982, 145135/1979, 161237/1980, 114946/1981, 154234/1982, and 56837/1982; and Japanese Patent Application Nos. 44831/19a2 and 45809/1982.
The DIR compound or compounds may be added to the light-sensitive silver halide emulsion layer and/or the non-light-sensitive photographic structural layer as stated above, but preferably such compound or compounds are incorporated into at least one silver-halide emulsion layer. For example, for use with a multi-layered color photographic light-sensitive mate-rial of the conventional type having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emul-sion layer, and a red-sensitive silver halide emulsion layer, such compound may be incorporated in one or more of these layers.
The tetrazaindene derivatives which can be used in the practice of the present invention are known as stabilizers for silver halide emulsions in light-sensitive materials, and among them, especially one expressed by the following general formula[T-VIII] can be advantageously used:
General formula [T-VIII]
(OH)~
Rt 9 N N
wherein m and n respectively stand for an integer of 2 or 3; Rt~ and Rtg independently represent a hydrogen atom, or an alkenyl or alkyl group having 1 to 4 carbon atoms which may have a substituent group, or an acryl group which may have substituent group.
While the tetrazaindene derivatives expressed by the foregoing general formula [T-VIII] are especially effective for the purpose of the invention, there are various other tetrazaindene derivatives which can be advantageously used in the practice of the invention, as enumerated below by way of example and not by way of limitation.
[Example compounds]
T-l: 4-hydroxy-1,3,3a,7-tetrazaindene;
T-2: 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene;
T-3: 4-hydroxy-6-hydroxy-1,3,3a,7-tetrazaindene;
T-4: 4-hydroxy-6-butyl-1,3,3a,7-tetrazaindene;
T-5; 4-hydroxy-5,6-dimethyl-1,3,3a,7-tetrazaindene;
T-6: 2-ethyl-4-hydroxy-6-propyl-1,3,3a,7-tetrazaindene;
T-7: 2-allyl-4-hydroxy-1,3,3a,7-tetrazaindene;
T-8: 4-hydroxy-6-phenyl-1,3,3a,7-tetrazaindene.
The compounds can be synthesized with reference to the relevant descriptions given in Japanese Patent Publication Nos. 18102/1971 and 2533/1969. Of these compounds, those hav-ing a hydroxy group at the 4-position are preferred, and those having an alkyl or aryl group at the 6-position are particu-larly preferred.
The 6-aminopurine derivatives useful for the purpose of the invention embrace those known as stabilizers for silver halide emulsions in light-sensitive materials, and in parti-cular, those expressed by the following general formula [P-IX]
can be advantageously used:
General formula [P-IX]
NH~ H
~ N
Rrlo ~ N ~ N ~
wherein Rp1o represents a hydrogen atom or hydroxy group;
or an alkyl group with 1 to 4 carbon atoms which may have a substituent group; and Rpll represents a hydrogen atom; or an alkyl group with 1 to 4 carbon atoms which may have a substi-tuent group; or an aryl group which may have a substituent group.
- 120 _ l 31 7500 When the 6-aminopurine derivatives expressed by the fore-going general formula [P-IX] are especially effective for the purpose of the invention, there are various other 6-amino-purine derivatives which can be advantageously used in the practice of the invention, as enumerated below by way of exam-ple and not by way of limitation.
[Compounds exemplified]
P-l: 6-aminopurine;
P-2: 2-hydroxy-6-aminopurine;
P-3: 2-methyl-6-aminopurine;
P-4: 6-amino-8-methylpurine;
P-5: 6-amino-8-phenylpurine;
P-6: 2-hydroxy-6-amino-8-phenylpurine;
P-7: 2-hydroxymethyl-6-aminopurine.
These tetrazaindene derivatives and 6-aminopurine deriva-tives are highly effective for the purpose of the invention if they are added to the silver halide emulsion, preferably with-in the range of from 5 mg to 18 g per mol silver halide.
Of these compounds, which can form a silver salt having a solubility product constant of not more than 1 x 10 9 in con-junction with silver ions, those which are not more than 1 x 10 ll in solubility product terms are especially effective.
With respect to DIR compounds, tetrazaindene derivatives, and 6-aminopurine derivatives, it has been known that when added to conventional silver halide emulsions, they contribute - 121 ~ 1 3 1 75 00 for improvement of image quality and can also inhibit repening fogging that may possibly develop in the process of emulsion preparation. Prior to the present invention, however, it was not known in the art that when used in conjunction with the process to which the invention is directed, those compounds would contribute to improve graininess.
In the present invention, the silver-halide color photo-graphic light-sensitive material to be processed is preferably such that the thickness of its photographic structural layer is not more than 25 ~m. The expression "thickness of the photographic structural layer" used herein means the total thickness of all constituent layers of the photographic structural layer other than the support, that is, all the hydrophilic colloidal layers including the silver-halide emul-sion layer (which consists of at least three layers in the case of a full color photographic material), and other layers formed as required, such as subbing layer, antihalation lay-er, intermediate layer, filter layer, and protective layer, which thickness refers to dry state thickness. For the hy-drophilic colloid, gelatin is often used, in which case the layer thickness may be referred to as the gelatin coat thick-ness. Thickness measurements may be carried out on a micro-meter. The total thickness of the photographic structural layer is more favorably not more the 22 ~m, still more favor-ably less than 20 ~m, and especially preferably not more than - 122 - l 3 1 750~
18 ~m. From the standpoint of photographic performance, a layer thickness of not less than 8 ~m is preferred.
Next, preferred conditions for development and other photographic processing steps in connection with the practice of the invention will be explained.
One preferred mode for carrying out the invention is such that the concentration of the developing agent in the devel-oper solution used is not less than 1.5 x 10-2 mols/Q. This condition constitutes an essential feature of the third inven-tion which will be hereinafter described in detail. The de-veloping agent to be used and further preferred conditions will be discussed hereinafter.
Another preferred mode for carrying out the invention is such that the pH of the developer solution is 10.4 or higher.
By adopting such high pH value it is possible to accelerate development and also to obtain further improved graininess.
The pH is more favorably 10.5 to 12.0, still more favorably 10.6 to 11.5.
A further preferred mode for carrying out the invention is such that the developing temperature is not less than 40C.
Processing at such high temperature can accelerate development and provide further improved graininess. Development is per-formed preferably at temperatures of 40C to 70C, more favor-ably 45C to 60C. This condition constitutes an essential feature of the second invention, which will be discussed here-- 123 - t317500 inafter in further detail.
Another preferred mode for carrying out the invention is such that the concentration of the sulfite in the developer solution used is not more than 1.5 x 10-2 mols/Q. Such low concentration of sulfite in the developer solution is intended to accelerate development and also to provide improved graini-ness. The concentration range of the sulfite is preferably O
to 1.0 x 10-2 mols/Q, inclusive of zero, more favorably O to 0.5 x 10-2 mols/Q, inclusive of zero.
For preferred types of sulfite to be included in the developer solution, the following are mentioned.
Typical examples include potassium sulfite, sodium sul-fite, lithium sulfite, potassium metabisulfite, and sodium metabisulfite. Also, those compounds which, when dissolved in the developer solution, can release sulfite ions are useful for the purpose of the invention. Examples of these compounds are formaldehyde bisulfite adduct, glutaric aldehyde bisulfite adduct, and the like, which are also included in the scope of sulfites which can be used the purpose of the invention.
Another preferred mode for carrying out the invention is such that the concentration of the bromide in the developer solution used is not more than 0.8 x 10-2 mols/Q. By limiting the concentration of the bromide to such low degree it is pos-sible to obtain same effect as above mentioned. The bromide concentration is more favorably 0.05 x 10-2 to 0.7 x 10-2 - 124 - 1 31 7~
mols/~, still more favorably 0.2 x 10-2 to 0.6 x 10-2 mols/~.
For preferred types of bromides for inclusion in the de-veloper solution, sodium bromide, potassium bromide, and lithium bromide are available.
Another preferred mode for carrying out the invention is such that the developer solution used contains at least one kind of compound of those expressed respectively by the gen-eral formulas lA-I] through [A-VI] shown hereinbelow. Any of these compounds functions as a development accelerator.
General formula [A-I]
X a I - ( C 11 2 ) n a I ~ t X a z - ( C H 2 ) n a z ) o ~ I X a 3 - t C 1I z )--~ X ~ ~1 In the above formula, Xa2 and Xa3 independently represent a sulfur or oxygen atom; Xa1 and Xa4 independently represent SH or OH groups; and na1, na2, na3, each stands for a positive integer of 0 to 500, at least one of the above-mentioned na1, na2, and na3 being an integer larger than zero; provided that at least one of the above-mentioned Xa1, Xa2, Xa3, and Xa4 is a sulfur atom.
General formula [A-II]
A a z A a 3 - N <
Aa 4 Ra z - 125 ~ l 31 7500 In the above formula [A-II], Ral and Ra2 independently represent a hydrogen atom; or an alkyl group, such as methyl, ethyl, or propyl group, or a heterocyclic group which is a ring Ral and Ra2 may form together with an oxygen or nitrogen atom; Aa2, Aa3, and Aa4 independently represent a hydrogen atom; or an alkyl group, such as methyl or ethyl group; or a halogen atom, such as fluorine or bromine atom; and Aal repre-Ra3 sents a hydroxyl group, or -N in which Ra 3 and Ra4 in-Ra4 dependently represent a hydrogen atom, or an alkyl group hav-ing 1 to 3 carbon atoms.
General formula [A-III]
.
Ras Aa ~ Ra8 Xa5 ~) ~1 Ra 7 In the above formula [A-III], Ras, Ra6, Ra~, and Ra8 in-dependently represent a hydrogen atom, or an alkyl group, aralkyl group, or substituted or unsubstituted allyl group;
and Aa2 represents a nitrogen or phosphorus atom. Ra8 may be a substituted or unsubstituted alkylene group; and Ras and Ra8 may form a ring; or may be substituted or unsubstituted pyridinium groups. Symbol XaS represents an anion group such as a halogen atom, OH, or an anionic group, such as sulfate or nitrate group.
General formula [A-IV]
R~ I o X N--(CH z) n, ~--(C) ma 2 Ya \+/ I
(R" 9 ) Q a R a l l In the above formula [A-IV], Ya represents a hydrogen Ra 12 atom, a hydroxyl group, or -N ; Rag, Ra10, Rall, Ral2, Ral3 and Ral3 independently represent a hydrogen atom, or a substi-tuted or unsubstituted alkyl, carbamoyl, acetyl, or amino group having 1 to 3 carbon atoms; X represents an oxygen or sulfur atom, or N-Ral4, in which Ral4 represents a hydrogen atom, or a subsi-ituted or unsubstituted alkyl group having 1 to 3 carbon atoms; and Qa, ma2, and na4, each represents 0, 1, 2, or 3.
General formula [A-V]
Rb ~ \ ' / N --tA b ) n b O R b 3 R b 2 In the above formula [A-V], Rbl and Rb2 independently re-present a hydrogen atom, or an alkyl, alkoxy, or aryl group, or a nitrogen-containing heterocycle in which Rbl and Rb2 may form a ring or in which Rbl or Rb2 together with Ab may form a ring; Rb3 represents an alkyl group; Ab represents an alkylene group; and nb represents an integer of O to 6.
General formula [A-VI]
N / Rbz ' \ Rb3 In the above formula [A-VI], Rb1' represents a hydroxy-alkyl group having 2 to 6 carbon atoms; Rb2' and Rb3' indepen-dently represent a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl or benzyl group having 2 Xb to 6 carbon atoms, or formula Cnb' H2nb' -N , in which nb' Zb represents an in~eger of 1 to 6; and Xb and Zb independently represent a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms.
Examples of the compounds expressed by the general for-mula [A-I] are enumerated below.
A-I-l HO(CH2)2S(CH2)2S(CH2)20H
A-I-2 HO(CH2)l0s(cH2)2s(cH2)looH
A-I-3 HS-(CH2CH20)3s-CH 2 CH 2 SH
A-I-4 (HoCH2CH2t2 A-I-5 HO(CH2)3S(CH2)3S(CH2)30H
- 128 - 13175~
A-I-6 Ho(cH2)2s(cH2)2o(cH2)2o(cH2)2s(cH2)2oH
A-I-7 HO(CH2CH20)l5CH2CH2SH
A-I-8 HO(CH2)4S(CH2)3S(CH2)40H
A-I-10 H0(CH2)3S(CHz)2S(CH2)30H
A-I-11 HO(CH2)2S(CH2)20H
Illustrative of the compounds expressed by the general formula [A-II] are as follows:
1~9 1 3~ 7500 A ~ 1 ~ C H ~
H 2 ~ N O
~ , ,, A ~ 2 F~
H z N ~3 < C z H s A -- 11 -- 3 C N, > ~3 < C N
A -- 11 -- 4 H 0 ~3 < C 11 3 A -- 11 -- 5 C ~
~I z N ~3--N <
U, N ~ N~O
- 130 - l 3 1 7~
A -- 11 -- 7H z N ~3 N~ ~
A -- 11 -- 8 ~OH
H z N ~ N~) F
N H z A -- ~ --10C z H 5 ~ C z H 5 ~ F
C H 3 /~
A -- ~ --11 0 C ~ ~ C - ~
N H z B r ~ B r ~,IJ
N ll 2 A -- 11 -- 13 f~
B.r ~ Br ~C113 Exmaples of the compounds expressed by the genearl for-mula [A-III] are enuemrated below.
A-III-l (1-carboxyethyl)methyl dodecylsulfonium hydroxide A-III-2 (4-sulfobutyl)dimethyl dodecylammonium hydroxide A-III-3 (carboxymethyl)dimethyl octadecylammonium hydroxide A-III-4 (1-carboxyethyl)methyl hexadecyl sulfonium hydroxide Illustrative of the compounds expressed by the general formula [A-IV] are as follows:
- 132 - 1~t7500 0~1-- C H z C 112 C 112 N 112 A -- IV -- 2 ~
O N--CIIzCII--Cl13 \ I
A -- N -- 3 ~
\ I
Nll 2 A -- IV -- ~1 ~ C 11:~
O~N-- CllzCI12 -- N<
A -- IV - 5 ~
HN~N--CllzC112C112NI12 A -- IV -- 6 C IJ a \~ ` C11 3 HN N-- CHzCllz --N<
~< C 11 3 Cll 3 - 133 - t 31 7500 HN 3 - CHz- CH- NHz A - ~ - 8 /--~
S~ N - C~lzCHzCHzNHz A - ~ - 9 r ~
S~ N - CHzCHzOH
A - ~ -10 COCH 3 HN 3 - CHz- 1- NHz C ~I 3 A - ~ - 11 r-\
HN ~ N - CH- NHz A - N - 12 ~
O~ N - Cll- Nllz C~l 3 A - N -13 ~ A - N - 14 O~ NH
A ~ 15 /--\
Il--N N--C z H s A -- N ~ 16 ~
O~N--C z H s A -- IV --17 /--\
O ~N--C 2 H 4 0 H
H--N ~N--C3H7 A -- IV --19 /--\
. 0~ C 3 H 7 The compounds expressed by the foregoing general formulas [A-I] to [A-IV] can easily be synthesized according to the methods described in Japanese Patent O.P.I. Publication No.
15554/1975, USP 3,201,242, USP 2,950,970, USP3,706,562, USP
3,893,862, and RD 15176.
The compounds expressed by these general formulas lA-I]
to [A-IV] may be added to the color developer solution, pre-ferably in the amount of 0.01 g to 60 g/liter, more favorably in the amount of 0.1 g to 30 gtliter-General formula [A-V]
R b I \
/,~' (A b 3 n b R b 3 R b Z
In the above formula, Rbl and Rb2 independently represent a hydrogen atom, or an alkyl, alkoxy, or aryl group, or a nitrogen-containing heterocycle, in which Rbl and Rb2 may form a ring together with Ab, or in which Rbl or Rb2 together with Ab may form a ring; Rb 3 represents an alkyl group; Ab repre-sents an alkylene group; and nb represents an integer O to 6.
In the above-mentioned general formula ~A-V], the alkyl groups represented by Rbl and Rb2 are preferably those having 1 to 5 carbon atoms, such as a methyl, ethyl, propyl, isopro-pyl, or butyl group; if each of them is an alkoxy group, it is preferably one having 1 to 5 carbon atoms, such as a methoxy, ethoxy, or propoxy group; if each of them is an aryl group, it may be, for exmaple, a phenyl, 4-hydroxyphenyl, or 4-sulfophenyl group. If Rbl and Rb2 form a nitrogen-containing heterocyclic ring, it may be, for example, a piperidine, mor-pholine, piperazine, or 1,4-thiazine ring. If Rbl or Rb2 to-gether with Ab form a nitrogen-containing heterocyclic ring, it may be, for example, a piperidine ring. The alkyl group represented by Rb 3 iS preferably one having 1 to 8 carbon atoms, such as a methyl, ethyl, propyl, isopropyl, butyl, or - 136 ~ 13 1 75~G
hexyl group. The alkylene group represented by Ab may be of a branched chain configuration, for example, a methylene, ethy-lene, trimethylene, 2-methyl trimethylene, 2-methyl tetra-methylene, propylene, 1-methyl trimethylene, or tetramethylene group.
Preferred typical examples of the compounds expressed by the general formula [A-V] are as follows:
_ _ _ _ . . . . . .. . . .
HzN --~CHz~O - CHz - CH ~
A - V - 2 HzN (CHz~O - C 3 H 7 ( i a O) A - V - 3 HzN (Cllz-~O - C3H~
A - V - 4 HzN (CHz~O - CH3 A - V - 5 H 2 N- t CHz~O - C 2 Hs - 137 _ 1 31 75~
A -- V -- 6 N z N ( C H 2~r 0 --C ~ H q A -- V -- 8 CH3~
~ NtCH z~30-- C zH 5 H--N ~N (Cllz~30--CB3 A -- V --10 ~
J~ C ll 2 ~2 0--C z 11 s - 138 _ l 3 ~ 7500 A - V - 11 9 2 N-~CHz~0 -C 2 Hs A - V - 12 HzN ~CHz~0 -C3H7 A - V -13 H2N-~CHz~0 -C3H 7 ( i S O) A - V -14 HzN - CHz - 0 -CzHs A - V -15 HzN - CHz - 0 - C 3 H7 A - V -16 HzN - CHCHz -0- C2Hs A - V - 17 HzN - 0 - CzH5 i A - V - 18 ~
O~ N--~CHz~-zO ~ CzH 5 A - V - 19 H,N-~CH2t~0 - C3H7 A - V - 20 HzN ~CHzt~0 - CzHs ~CHz~0 - CH3 H
H- N ~ CHz~20 -CH3 - 139 - l 31 7~0() Of these compounds expressed by the general formula [A-V], those of (A-V-2), (A-V-4), (A-V-5), (A-V-7), (A-V-ll), (A-V-150, and (A-V-18) are especially preferably used for the pur-pose of the invention.
These compounds are available from a commercial source (for example, Koei Chemical Co., Ltd.).
Any of the compounds expressed by the general formula [A-V] is used for addition to the color developer solution, preferably in the amount of 0.01 to 100 g, more favorably 0.1 to 50 g, per liter of the solution.
Of the compounds expressed by the foregoing general for-mula [A-VI], those expressed by the following general formula A-VI'] are preferably used.
General formula [A-VI'~
/ R b S
R' b~ - N ~
R b b In the formula, R'b4 represents a hydroxyalkyl group hav-ing 2 to 4 carbon atoms; R'bs and R'b6 independently represent an alkyl group having 1 to 4 carbon atoms; or a hydroxyalkyl group having 2 to 4 carbon atoms.
Preferred examples of the compounds expressed by afore-said general formula [A-V] are as follows.
Namely, ethanolamine, diethanol amine, triethanol amine, diisopropanol amine, 2-methyl aminoethanol, 2-ethyl amino-ethanol, 2-dimethyl aminoethanol, 2-diethyl amino ether, 1-diethyl amino-2-propanol, 3-diethyl amino-l-propanol, 3-dimethylamino-l-propanol, isopropyl aminoethanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, ethylene diamine tetraisopropanol, benzyl diethanolamine, and 2-amino-2-(hydroxymethyl)-1,3-propanediol.
Any of the compounds expressed by the general formula [A-VI] is used preferably in the amount of 3 g to 100 g, more favorably in the amount of 6 g to 50 g, per liter of the color developer solution.
A further preferred mode for carrying out the invention is such that the developer solution used contains at least one kind of compound of those expressed by the following general formulas ER-I] through lR-III]-General formula lR-I]
".~ ' ,~ ~ ( X r I ) n r ;Z r ( X r ) m r~ ~ X r Z
In the formula, X'r and X'R1 independently represent a halogen atom, or alkyl, aryl, amino, hydroxyl, nitro, carboxyl, or sulfonyl group; X'rz represents a hydrogen atom, an alkyl or aryl group, or a double bond for ring formation; zr repre-sents a plurality of atoms composed of carbon, oxygen, nitro-- 141 - l 31 7500 gen, and sulfur atoms necessary for ring formation; and n and m, each represents 0, 1, 2, or 3.
General formula [R-II]
,~Y r a ~ Y r I
Y r 3 Y r 2 In the formula, Yra, Yrl, Yr2, and Yr3 independently re-present a hydrogen or halogen atom; or an alkyl, amino, hy-droxyl, nitro, carboxyl, or sulfonyl group.
General formula [R-III]
,. Y r ~
Y r ~TF X r 2 X r 3 In the formula, Tr represents a nitrogen or phosphorus atom; Xr2 and Xr3 independently represent a hydrogen atom, or an alkyl or aryl group, or a halogen atom; Yr4 and Yrs inde-pendently represent an alkyl or aryl groups, where Yr4 and Yr5 may form a heterocyclic ring through ring closure.
Any of the compounds expressed by the foregoing general formulas [R-I] through [R-III] can act as an inhibitor. In the practice of the invention, if an organic inhibitor is used in the developer solution, various compounds may be mentioned - 142 ~ 1 3 1 75~a as those suitable for such use, including nitrogen-containing heterocyclic compounds, mercapto group-containing compounds, aromatic compounds, onium compounds, and compounds having iodine atoms in their substituent groups; among these, those expressed by aforesaid general formulas [R-I], [R-II], and [R-III] are preferred.
The compounds expressed by the general formula [R-I] are more favorably those expressed by the general formula [R'-IV]
or [R'-V], most preferably those expressed by the general for-mulas [R'-VI] through [R'-XI].
Whilst, the compounds expressed by the general formula [R-II] are most favorably those expressed by the general for-mula [R'-XII] or [R'-XIII].
These compounds are used in the developer solution, pre-ferably in the amount of 0.005 to 20 g, more favorably in the amount of 0.01 to 5 g, per liter of the solution.
- 143 - ~317~
General formula [R'-VI] R r _ NH 11 R r ,/~N~ N
General formula [R'-VII] (0~l) m ~ N ~J` R r General formula 1R'-VIII] ( Rj) m ( n, r ) ~ H--/N
General formula [R'-IX] (R r ) H
(R, r ) n ~ R r z N
General formula [R'-X] ( n r ) ~ N~
- 144 - 1317~0 - ~ .
General formula ~R'XI] IR r T r ~ y r I
N - N yr 2 . _ _ . .. . .
(where Tr is C or N) General formula [R'XII] (NOz) n r R r R r I
. . .
General formula [R'-XIII] OH
Rr ~ OH
Rr l In the above formulas, Rr, Rrl, and Rr2 independently re-present a hydrogen atom or halogen atom (CQ, Br, I, etc.), or an alkyl group which may have a substituent group, aryl group which may have a substituent group, carboxylic group, benzyl group, -NHCORr' (in which Rr' represents an alkyl or aryl group), thiocarboxylic group, carboxy alkylate group (such as -COOCH3, -COOC2H5, and COOC3H7), alkoxy group (such as a methoxy, ethoxy, or propioxy group), hydroxyl group, sulfonyl halide group (-S02CQ, -SO2Br, etc.) amino group which may have - 145 ~ l 31 7500 substituent group, sulfonic group, nitro group, mercapto group, or cyano group.
Symbols Yrl and Yrz respectively have same meanings as Yrl and Yr2 in the foregoing formula ~R-II].
General formula [R'-IV]
. .
A compound having 1 to 9 carbon atoms of which 2 to 5 are replaced by nitrogen atoms, or its derivative.
General formula lR'-V]
,- , Z~ 5 A compound having 1 to 5 carbon atoms of which 2 to 4 are replaced by nitrogen atoms, or its derivatives.
Preferred examples illustrative of the organic inhibitors expressed by aforesaid formulas are given hereinbelow. Need-less to say, however, it is understood that the compounds of the formulas which are useful for the purpose of the invention are not limited to those exemplified below.
- 146 - ~3~7500 (Examples of organic inhibitors) Il 5C zOOC~
HOOC ~ N ~ SH
~0 J' S 11 HOOC ~ N~N~N
~ N N
CH3 ~ N ~ N~
- 147 - t 3 1 7~00 Z 6 ~ S ~>
CH3 / SO3~CH~, 011 ~3 O H
- Z 8CzHsOCHz~ y, ~
~N--N
OH
HS ~,N~NH2 N N
\Nlt/ \~1/
- 148 - ~ 31 7~00 Zll CH 3 II S ~ N ~I C O ~3 N - N
HS y N ~ NHCOCH 3 Z13 f 2 Hs HS ~ N ~ NHCOCH 3 N N
N~ N
~N ~ SH
N N
Z16 NO2 ~ COOII
.. . .
Z 17 ~ C--S~N--i OH
( ~ P ~3Noz CQ e Z 19 ~yN~
OH
/~\
Z 21 ~S>
CH~/\ CH2COOe Z 2 2~3~ C H 2--N H 11 Z 23NO2 ~ COOH
~--COOII
NO~--~ Cl ~ NO 2 Z26NO2~H
Z 27 ~ N
~S~\ N
SO~M ll ~ 3 1 7500 1~, ~/~ N H z ~ COSH
C H a ~ N
HO [~OH
COOCzHs 7~32 N 0 ~ ~ N N ~
1~,~ N H 2 Z34 ~
~ ~ CN z--Br [~0,~ CH zBr Z 36 NOz~H~N
~L ( C H z ) z H H
Z 38 Cll,~N
N O z ~, Z40 SOzC~
~3 COOH
Z41 SO 2 Br ~ COOH
Z42 SO3Na NOz ~ NO2 ND~ ~ N~
H
Z44 ~ N
(where R represents -H, -SH, or -NH2) 1 31 750~
Z45 ~I
SH
N N (where R represents X -H, -SH, or -NHz) .
Z46 N(where Yb; alkyl group, N - N ~ ~ group, or ~ group) N
Z4~ CzHs HO N Sll O~/C~13 N~N
Sll ~011 COOC~Hq(t) - 155 _ l 31 7500 Z50 ll C N~ 3 \N~
Y' Y \
N ~Y
0~1 Z 52 Cll 3--~C= C~--Cll 3 ~ C ~
I
S~l Z 53 HOOC--CHz y N~ N~
~>
OH
- 156 _ ' 1317500 Z54 Cll3~/N ~N
YN ~ c 2 ~3 OH
~Ny N~
N~ N ~>
OH
Z 56 CH~Y/NY/N\
\ N
OH
oll - 157- ' 1317500 Z 58 CH3~Ny/N\
OH
Z 5 9 C l1 3 y/
~N~N~
OH
Z 60 CH3y/NyN\
~N~N~
OH
Z 61 CH~N~
N~
13175~
Z 62 7~12~
Y Y N
~,N~
Z 63 ~y N~
OH
Z 6 4~ N~ N ~ O 11 N j,~'~
OH ~J
~ N
C113/~N/ \~
Z 66 Cl13 y/N \1~ N ~
;~N
OH
ce Z 67 ~N ~ N
C2Hsco2 /~/N~
Z 68 CHJ y/N\~N
N \ N //~
-160 13175~
H~N~N~
~N~N~
CH3~N~N~
N~
OH ~
~N
OH
~,1 OH
> ~y / \ NCHzC ~ ~ \
N~
OH
Of the above exemplified compounds of those expressed by the general formulas [R-I] through [R-III], the Z-4, Z-5, Z-7, Z-14, Z-20, Z-26, Z-30, Z-49, and Z-51 compounds are especial-ly advantageously used for the purpose of the invention.
Another preferred embodiment of the invention is such that the developer solution used contains at least one kind of polymer or copolymer having a pyrolidone nucleus in the indi-vidual molecular structure, or at least one type of polyethy-lene glycol.
By this arrangement, it is possible to accelerate devel-opment and provide improved graininess.
The polymer or copolymer having a pyrolidone nucleus in the molecular structure and can be used in embodying the in-vention is every polymerizable polymer in which main chain or side chain of polymeric unit are replaced with pyrolidone nu-clear units at any positions and in any number, and such a polymer or copolymer may be a monopolymer of such polymeriz-able polymers, or may be a copolymer formed by copolymeriza-tion of two or more kinds of copolymeric units. In the latter case, the copolymer is preferably such that one polymer as a copolymeric unit which has pyrolidone nuclear units in its molecular structure is included in the proportion of 20% or more in the copolymer produced by copolymerizing the above-mentioned one polymer with another polymer which as no pyroli-done nuclear unit in its molecular structure. More favorably, the above-mentioned one polymer is so included in the propor-tion of 30% or more. For the above-mentioned other polymer having no pyrolidone nuclear unit which is to be copolymerized with the above-mentioned one polymer as a copolymeric consti-tuent which has pyrolidone nuclear units in its molecular structure any polymer may be used insofar as a hydrophilic copolymer can be obtained.
Preferably, aforesaid polymer or copolymer has an average molecular weight of 1,000 to 70,000, typical examples of which are as follows.
[Example compounds]
[1] Poly-N-vinyl-2-pyrolidone (*No tel) [2] Poly-N-(2-acryloyloxy)ethyl-1-pyrolidone [3] Poly-N-glycidyl-2-pyrolidone [4] Poly-N-allyl-2-pyrolidone [5] Poly-N,N-dimethyl-N-[3(1-pyrolidonyl)-2-hydroxy]propyl-amine-N'-acryloylimine [6] Copoly-N-vinyl-2-pyrolidone/N-acryloyl morpholine (molar ratio, 42:58) [7] Copoly-N-vinyl-2-pyrolidone/N-acryloyl piperidine (molar ratio, 35:65) [8] Poly-N-vinyl-2-pyrolidone/N-methacryloyl-2-methylimida-zole (molar ratio, 55:45) [9] Copoly-N-(2-acryloyloxy)-ethyl-2-pyrolidone/diethylamide acrylate (molar ratio, 60:40) [10] Copoly-N-(2-methacryloyloxy)ethyl-2-pyrolidone/sodium acrylate (molar ratio, 75:25) [11] Copoly-N-(3-acryloyloxy)propyl-2-pyrolidone/methyl metha-crylate (molar ratio, 65:35) [12] Copoly-N,N-dimethyl-N-(3-(1-pyrrolidonyl)-2-hydroxy]-propylamine-N'-acryloylimine/ethyl acrylate (molar ratio, 70:30) [13] Copoly-N-vinyl-2-pyrolidone/vinyl acetate (molar ratio 70:30) [14] Copoly-N-vinyl-2-pyrolidone/methyl acrylate (molar ratio, 70:30) [15] Copoly-N-vinyl-2-pyrolidone/styrene (molar ratio, 80:20) [16] Co~oly-N-vinyl-2-pyrolidOne/amide acrylate/N-vinyl-2-methylimdazole ~molar ratio, 50:30:20) [17] Copoly-N-vinyl-2-pyrolidone/N-(l,l-dimethyl-3-oxo)-butyl-acrylamide (molar ratio, 70:30) [18] Copoly-N-allyl-2-pyrolidone/vinyl acetate (molar ratio, 64:36) [19] Copoly-N-vinyl-2-pyrolidone/4-vinyl pyridine (molar ratio, 60:40) [203 Copoly-N-vinyl-2-pyrolidone/ethyl acrylate/monoethanola-mine acrylate (molar ratio, 50:45:5) [21] Copoly-N-vinyl-2-pyrolidone/piperidinomaleamic piperidine (molar ratio, 53:47) [22] Copoly-N-vinyl pyrolidone/4-vinylpyridino-N-methyliodide (molar ratio, 42:58) E23] Copoly-N-vinyl pyrolidone/thiourea half ammonium maleate (molar ratio, 60:40) *Note (l); Varieties of the example compound (1) are commer-cially available from General Aniline and Film Corp. under the * * * *
tradenames of PVP K-15, PVP K-17, PVP K-30, PVP K-60 and PVP
*
K-90, and also from BASF Aktien~esellschaft (Japan) under the trade marksof "Coridone 12", "Coridone 17", "Coridone 25", "Coridone 30", "Coridone 90", "Rubiscol K-17", "Rubiscol K-30", and "Rubiscol K-90".
* Trade mark.
B
-- 1 31 7~00 The above exemplified polymers and/or copolymers, some of which are commercially available as above noted, can easily be synthes~zed according to the methods described in W.R. Sorenson and T.W. Campbell, "Preparative Methods of Polymer Chemistry", John Wilery and Sons, Inc., 1961.
Such polymers or copolymers may be used either singly or ~n a combination of two or more kinds. The amount of such polymer or copolymer used is preferably within a range of 0.01 g to 100 g, in particular 0.05 g to 10 g, per liter of the color developing solution. Such a polymer or copolymer may be added directly to the solution in the color developer tank, or added to a replenishing tànk solution for subsequent' replenishing of the color developing tank solution, or may be used in a combination of both ways.
Polyethylene glycol compounds useful in connection with the above described embodiment will now be explained.
In the practice of the invention, polyethylene glycol compounds expressed by the following formula can be preferably used:
HO(CH2CHzO)nCH2CH2OH (n=1 to 1000) More specifically, carbowax 1000, carbowax 1540, carbowax * * *
2000, carbowax 4000, and carbowax 6000 are mentioned as useful compounds for the purpose. The amount of such polyethylene glycol to be added is generally at least 1 g/liter, preferably 1.5 g/liter to 40 g/liter.
* Trade mark.
B
- 166 _ l 3 1 7 500 Besides aforesaid polyethylene glycols, thelr derivatives can be used, though they are somewhat less effective.
Of the above-mentioned derivatives, polyethylene glycol-bis-pyridinium methane sulfonate, polyethylene glycol-bis-tri-(~-hydroxyethyl)ammonium methane sulfonate, polyethoxyethyl-bis(3,5-disulfobenzoate) tetrasodium, polyethylene glycol-bis-sulfonic acid, and polyethoxyethyl-bis-carboglutamic acid are rather less effective.
Next, the second invention of the present application will be explained.
This invention is characterized in that in the above des-cribed processing method of the first invention, a developing temperature is higher than 40C. Processing at more than 40C
can acceleraet development and provide improved graininess.
Processing is performed preferably at a temperature within a range of 42C to 70C, in particular, within a range of 45C
to 65C.
Where development is performed at higher than 40C, satisfactory development effect can be obtained even if a p-phenylenediamine-based developing agent is used in the concen-tration of 1.0 x 10-2 to 1.5 x 10 2 mol/liter. In this con-junction, a pH range of 10.2 and a processing time range of 20 to 150 seconds are even acceptable.
However, if the developing temperature condition of not lower than 40C is combined with such other conditions as a - 167 - l 3 1 7500 developing agent concentration of not lower than 1.5 x 10-2 mol/liter, or a pH value of not lower than 10.4, or a sulfite concentration of lower than 1.5 x 10-2 mol/liter, or a bromide concentration of not higher than 0.8 x 10-2 mol/liter, or use of any of developing accelerators [A-I] through [A-VI], the object of the invention can be more satisfactorily accomplish-ed.
Next, the third invention of the present application will be explained.
This third invention is characterized ln that in the processing method of the first invention, the concentration of the developing agent in the developer solution is not lower than 1.5 x 10-2 mol/liter. By using the developing agent in such high concentration, it is possible to effect active proc-essing and provide improved grainess. Preferably, the color deveoper solution contains the developing agent at a concen-tration of not lower than 2 x 10-2 mol per liter solution, more favorably in a concentration range of 2.5 x 10-2 to 2 x 10~l more/liter, still more favorably 3 x 10-2 to 1 x 10~
mol/liter.
The color developing agents useful in the practice of the invention will be discussed hereinbelow. The following expla-nation on the color developing agents is applicable to the other inventions of the present application as well, unless it is contradictory to their respective essential features.
- 168 - l 3 1 7500 In the practice of the invention, there may be used, for exmaple, aromatic primary amine-based color developing agents, including various kinds of known agents widely used as such in the art of color photographic processing. These developing agents include aminophenol and p-pheniline diamine derivatives.
These compounds are generally used in the form of salt, for example, in the form of hydrochloride, phosphate, or sulfate, since they are more stable in such form than in their free state.
Among the aminophenol developing agents there are, for example, o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, and 2-oxy-3-amino-1,4-dimethyl benzene.
Especially useful aromatic primary amine-based color developing agents are those having an amino group with at least one water-soluble group, and especially preferably, they are compounds expressed by the following general formula [X].
General formula [X]
R, 4 N - R~s ~ R, 3 In the formula, Rl3 represents a hydrogen atom, a halogen atom, or an alkyl group, wherein the above-mentioned alkyl group is a straight-chained or branched alkyl group having 1 to 5 carbon atoms, and may have a substituent group. R14 and Rls independently represent a hydrogen atom, or an alkyl or aryl groups, which may have a substituted group, wherein at least one of the R14 and Rls being an alkyl group having a water-soluble substituent, such as a hydroxyl group, carboxy-lic group, sulfonic group, amino group, or sulfonamide group;
or ~ tCIIz~ O J p R,~ Such an alkyl group further may have a substituent.
It is noted that Rl6 represents a hydrogen atom or an alkyl group, wherein the alkyl group being a straight-chained or branched alkyl group having 1 to 5 carbon atoms; and p and q respectively stands for an integer of 1 to 5.
Examples illustrative of the compounds expressed by the general formula [X] are given below; it is understood, how-ever, that the scope of the compounds according to the inven-tion is not limited to these examples.
[Example compounds ]
( E -- 1 ') C 2 R 5--N--C z H 4 N 1I S 0 2 C H J
~\CH 3 ~ ~I 2 ( E -- 2 ) C 2 ~I S--I --C 2 ~1 4 0 H
. , ~ .
~\ C H
NH z E -- 3 ) C 2 H 5--N--C 2 H 4 0 H
N ll 2 ( E -- 4 ) C 2 H s--N--C z 11 4 0 C 11 i ~, ~CII, N ll 2 ( E -- 5 ) CzHs--N--C3H6SO3H
~\C~13 E -- 6 ) C H 3--N--C z H ~ O H
Nll z t E -- 7 ) HOOCzH~--N--CzH~OII
. ~
NH z ~3~7500 E -- 8 ) C 4 H 9--N--C 4 11 11 S O :~ H
`~1 NH Z
E -- 9 ) C ~ H 4--N--C 3 H ~ S 0 3 H
NH z ( E -- 10 ) H--N--CH 2COOH
N H z E -- l 1 ) C 2 H s--N ~ C 11 z C ll 2 O ~2 C ll 3 ( E -- 12 ) C 2 H 5--NtCH 2 C HzO~CH~
NH z E -- 1 3 ) C 2 H s--N t C H 2 C H Z 0 3~ C Z 1l S
'' . .~
~/~CH 3 E -- 1 4 ) C 2 H 5--N--~ C 13 z C ll z O ~z C z ll 5 ~`3'c~
NH z ( E -- 15 ) Cll 3--N--~CII 2 r~ll "~Czlls NH z t317500 ( E - l6) 1( ~ CUzCll~CU~t~C~U5 C Q
Nll 2 The p-phenylenediamine derivatives expressed by the gen-eral formula [X] may be used in the form of organic or inor-ganic acidic salt. For example, various salts such as hydro-chloride, sulfate, phosphate, p-toluene sulfonate, sulfite, oxalate, and benzene sulfonate can be used for the purpose of the invention.
In the practice of the invention, among the p-phenylene-diamine derivatives expressed by the above-mentioned formula [X], those in which R14 and/or R15 are expressed by the for-mula ~ (C~lz)~ 0 ~ p R,~ (in which p, q, and Rl6 are as above defined) are especially effective for purposes of the inventions of the present application.
Next, the fourth invention of the present application will be explained.
This fourth invention is characterized in that in the processing method of the first invention, the developing time is less than 180 seconds.
In this fourth invention, the time for processing the silver halide color photographic light-sensitive material ac-cording to the above described processing method is within the range of 20 seconds to 150 seconds, preferably 30 to 120 sec-onds, more favorably 30 to 120 seconds, and still more favor-ably 40 to 100 seconds.
According to this invention, the silver halide color photographic light-sensitive material is processed for such a specific duration by employing the above described method, and surprisingly it has been found that this can result in con-siderably improved dye image graininess.
Next, the fifth invention of the present application is hereinunder described.
This fifth invention is characterized in that in the processing method of the first invention, the rate of layer swelling during the process of color development is less than 20 seconds.
Swelling rate T 1/2 can be measured according to any measurement technique known in the art. For example, it can be measured by employing a swellometer of the type described in a report made by A. Green et al in Photographic Science and Engineering, Vol. 10, No. 2, pp. 124 to 129. The above-mentioned T 1/2 is defined as the duration taken until 1/2 of a saturated gelatin thickness is reached, wherein the term "saturated gelatin thickness" means a maximum gelatin thick-ness resulting from 90% swelling which can be reached when processing is performed with the color developer solution at - 176 - ` 1317500 30C for 3 minutes and 15 seconds~ Referring to Fig. 1, time T 1/2 or one half o~ the time taken until the gelatin thick-ness is saturated by swelling (that is, the gelatin thickness levels off in the graph) is taken as the speed of gelatin swelling.
The swelling rate T 1/2 can be adjusted by adding a hardening agent to gelatin serving as a binder, or through varying combinations between the amounts of the hardening agent and gelatin in the photographic light-sensitive material on one hand and the characteristics of the developer solution on the other hand. For example, it can be adjusted by adding the hardening agent to the developer solution and/or by increasing the concentration of the salt in the solution.
For the hardening agent, various types of hardening agents can be used, including aldehyde-based ones, aziridine-based ones (e.g., those described in PB report 19,921, U.S.
Patent Nos. 2,950,197, 2,964,404, 2,983,611, and 3,271,175, Japanese Patent Examined Publication No. 40898/1971 published December 3, 1971, and Japanese Patent O.P.I. Publication No.
91315/1975 published July 22, 1975), isooxazolium-based ones (e.g., those described in U.S. Patent No. 3,321,323), epoxy-based ones (e.g., those described in U.S. Patent No.
3,047,394, German Patent No. 1,086,663, British Patent No.
1,033,518, and Japanese Patent Examined Publication No.
35495/1973 published October 29, 1973), vinylsulfone-based ones (e.g., those described in PB Report 19,920, German Patent ~ .~
V
- 177 ~ 1 3 1 7 500 Nos. 1,100,942, 2,337,412, 2,545,722, 2,635,518, 2,742,308, and 2,749,260, British Patent No. 1,251,091, and U.S. Patent Nos.
3,539,644 and 3,490,911), acryloyl-based ones (e.g., those described in U.S. Patent No. 3,640,720), carbodiimide-based ones (e~.g., those described in U.S. Patent Nos. 2,938,892, 4,043,818, 4,061,499, and Japanese Patent Examined Publication No. 38715/1971 published November 15, 1971), triazine-based ones (e.g., those described in German Patent Nos. 2,410,973 and 2,553,915, U.S. Patent No. 3,325,287, and high-polymeric ones (e.g., those described in British Patent No. 822,061, U.S. Patent Nos. 3,623,878, 3,396,029 and 3,226,234, and Japanese Patent Examined Publication Nos. 18578/1972, 18579/1972, 48896/1972 respectively published May 29, May 29 and December 8, 1972). There are also known maleimide-based, acetylene-based, methane sulfonate-based, and N-methylol-based hardening agent. These hardening agents can be used either alone as such or in combination. Various useful combinations are disclosed in various publications including, for example, German Patent Nos. 2,447,587, 2,505,746, and 2,514,245, U.S.
Patent Nos. 4,047,957, 3,832,181, and 3,840,370, Japanese Patent O.P.I. Publication No. 43319/1973, 63062/1975, and 127329/1977 respectively published June 22, 1973, May 29, 1975 and October 25, 1977, and Japanese Patent Examined Publication No. 32364/1973 published October 5, 1973.
Wlth the binder for photographic structural layers which is used in the color photographic lighl-sensitive material according to the invention, the smaller the speed of its B
swelling T 1/2, the better. However, if the lower limit of such speed is excessively small, gelatin hardening will not take place and thus scratches and the like troubles are likely to occur. Therefore, it is preferred that the lower limit should be more than 1 second. More favorably, the swelling rate is more than 2 seconds and not more than 20 seconds, especially preferably less than 15 seconds, and most favorably less than 10 seconds. If the rate of gelatin swelling is greater than 20 seconds, desilvering of the photogrpahic mate-rial, and more particularly the process of bleach-fixing, are seriously hindered.
Next, the sixth invention of the present application will be described.
This sixth invention is characterized in that in the processing method of the first invention, the light-sensitive material to be processed has, on its support, at least one silver-halide emulsion layer containing a coupler expressed by the following general formula [M-I].
~ eneral formula [M-I]
nm ~ Z~
N N- -In the above general formula [M-I], Zm represents a plurality of non-metal atoms necessary for forming a nitrogen-containing heterocycle, and the ring formed by the above-mentioned Zm may have a suhstituent group.
Symbol Xm represents hydrogen atom, or a group capable of split off upon the reaction an oxidation product of the color developing agent.
Symbol Rm represents a hydrogen atom, or a substituent group.
The substituent group represented by Rm is not particu-larly limited but is typically any of the following groups, namely, alkyl, aryl, anilino, acylamino, sulfonamide, alkyl-thio, arylthio, alkenyl, and cycloalkyl groups. Among others, the following are mentioned: halogen atom; cycloalkenyl, alkinyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxy carbony-lamino, alkoxycarbonyl, aryloxy carbonyl, and heterocyclic thio groups; and spiro residue and bridged hydrocarbon residue.
The alkyl group expressed by Rm is preferably any of those having 1 to 32 carbon atoms, and may be straight-chained or branched.
The aryl group expressed by Rm is preferably a phenyl group.
- 180 -` 1317~00 Exmaples of the acylamino group expressed by Rm include alkylcarbonylamino and arylcarbonylamino groups.
Examples of the sulfonamide group represented by Rm in-clude alkylsulfonylamino and arylsulfonylamino groups.
Examples of the alkyl and aryl components in the alkyl-thio and arylthio groups represented by Rm are alkyl and aryl groups each represented by Rm.
The alkenyl group expressed by Rm is preferably one hav-ing 2 to 32 carbon atoms, and the cycloalkyl group expressed by Rm is preferably one having 3 to 12, more favorably 5 to 7 carbon atoms; the alkenyl group may be straight-chained or branched.
The cycloalkenyl group expressed by Rm is preferably one having 3 to 12 carbon atoms, more favorably 5 to 7 carbon atoms.
Examples of the sulfonyl group expressed by Rm include alkylsulfonyl and arylsulfonyl groups.
Examples of the sulfinyl group expressed by Rm include alkylsulfinyl and arylsulfinyl groups.
Examples of the phosphonyl group expressed by Rm include alkylphosphonyl, aryloxysulfonyl, and arylphosphonyl groups.
Exmaples of acyl group expressed by Rm include alkyl-carbonyl and arylcarbonyl groups.
Examples of carbamoyl group expressed by Rm include alkylcarbamoyl and arylcarbamoyl groups.
Examples of sulfamoyl group expressed by Rm include alkylsulfamoyl and arylsulfamoyl groups.
Exmaples of acyloxy group expressed by Rm include alkyl-carbonyloxy and arylcarbonyloxy groups.
Examples of carbamoyloxy group expressed by Rm include alkylcarbamoyloxy and ary'carbamoyloxy groups.
Examples of ureido group expressed by Rm include alkyl-ureido and arylureido groups.
Exmaples of sulfamoylamino group expressed by Rm include alkylsulfamoyl amino and arylsulfamoyl amino groups.
The heterocyclic group expressed by Rm is preferably five- to seven-membered one, and more specifically, 2-furil, 2-thienyl, 2-pyrimidinyl, or 2-benzothiazolyl group.
The heterocyclic oxy group expressed by Rm is preferably one having a five- to seven-membered heterocyclic ring, and typically, 3,4,5,6-tetrahydropyranyl-2-oxy group or l-phenyl-tetrazole-5-oxy group.
The heterocyclic thio group expressed by Rm is preferably a five- to seven-membered heterocyclic thio group, for exam-ple, 2-pyridylthio, 2-benzothiazolylthio, or 2,4,-diphenoxy-1,3,5-triazole--thio group.
Examples of the siloxy group expressed by Rm include trimethylsiloxy, triethylsiloxy, and dimethylbutylsiloxy groups.
Examples of the imido group expressed by Rm include 13t7500 succinimido, 3-heptadecyl succinimido, phthalimide, and glutarimido groups.
Examples of spiro residue expressed by Rm include spiro [3,3]heptane-1-yl.
Examples of the bridged hydrocarbon residue expressed by Rm include bicyclo [2,2,1]heptane-1-yl, tricyclo[3,3,1,13 "]
decnae-1-yl, and 7,7-dimethyl-bicyclo[2,2,1]heptane-1-yl.
Examples of the group expressed by Xm which is capable of split off upon the reaction with an oxidation product of the color developing agent are a halogen atom (e.g., chlorine, bromine, and fluorine atoms); alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, acyloxy, sulfonyloxy, alkoxycar-bonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythio carbonyl-thio, acylamino, sulfonamide, N-atom bonded nitrogen-contain-ing heterocycle, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and I
R2 '--C-- R~ ' R, ' b~ z N - N--.--(in which Rl' has same meaning as aforesaid Rm; Z' has samemeaning as aforesaid Zm; and R2' and R3' independently repre-- 183 _ 1 31 7 5 00 sent a hydrogen atom, or aryl, alkyl, or heterocyclic group)O
Among the examples above, however, a particularly preferred one is a halogen atom, especially, chlorine atom.
Examples of the nitrogen-containing heterocyclic ring formed by Z or Z' include pyrazole, imidazole, triazole, and tetrazole rings. For the substituent groups which any of these rings may have, those mentioned with respect to the pre-viously defined R are available.
The couplers expressed by the general formula [M-I] are more specifically expressed by the following general formulas [M-II] through lM-VII]:
General formula [M-II]
X m 11 Rml 1 N
~/~,/ ' N
Il I L
N N R m 2 General formula [M-III]
X m 11 Rm '~N Rm 3 N--N--N
General formula [M-IV]
Xm Rm4 R m I ~ N
General formula ~M-V]
X m 11 R m.l ~h~N R m 5 N N Rm General formula [M-VI]
Xm Rm7 R m I ~R 8 N N- NH
General formula [M-VII]
X~ H
Rm l 1 N
\N
N--N N
- 185 ~ I 3 1 7500 In the foregoing formulas [M-II] through [M-VII], Rml through Rm8 and Xm have same meanings as previously mentioned Rm and Xm.
Among the couplers expressed by the general formula ~M-I], particularly preferred are those expressed by the fol-lowing general formula [M-VIII].
General formula [M-VIII]
Xm H
R m I ~N `''``z m I
N N -In the formula, Rm1, Xm, and Zml have smae meanings are Rml, Xm, and Zm in the general formula [M-I].
of the magenta couplers expressed by the general formulas [M-II] to [M-VII], most advantageous are those expressed by the general formula [M-II].
As the substituent which a ring formed by Zm in general formula [M-I], or a ring formed by Zml in the general formula [M-VIII], may have, or as any of Rml through Rmg in the gen-eral formulas [M-II] through [M-VI], those expressed by the following general formula [M-IX] are particularly preferred.
General formula [M-IX]
- Rml - SO2 - Rm2 In the formula, Rml represents an alkylene group, and Rm2 represents an alkyl group, a cycloalkyl group, or an aryl - 186 - l 3 1 7500 group.
The alkylene group expressed by Rml has a straight chain portion having preferably 2 or more carbon atoms, in particu-lar, 3 to 6 carbon atoms, and may be of either straight chained or branched configuration.
As the cycloalkyl group expressed by Rm2, a five- to six-membered one is preferred.
For the substituent groups Rm and Rml on the previously mentioned heterocyclic ring, if the light-sensitive material is used for positive image formation, those expressed by the following general formula [M-X] are most favorable.
- General formula [M-X~
R ~9 R m l O ~
R m l I
In the formula, Rmg, RmlO, and Rmll are synonymous with afore-mentioned R.
Two of the above-mentioned Rmg, RmlO, and Rmll, for ex-ample, Rmg and Rm1O may be combined with each other to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, or heterocycle), and further, Rmll may be combined with the ring to form a bridged hydrocarbon residue group.
In the general formula [M-X], it is preferred that (i) at least two of Rmg through Rmll are alkyl groups, or that (ii) one of Rmg through Rmll, for example, Rmll is a hydrogen atom, whereby the other two i.e. Rmg and Rm10 are combined with each other to form cycloalkyl together with a root carbon atom.
Further, in the above case (i), it is preferred that two of Rmg through Rmll are alkyl groups, while the other one is a hydrogen atom or an alkyl group.
As the substituent groups Rm and Rml on the above-men-tioned heterocycle, if the light-sensitive material of the in-vention is used for positive image formation, those expressed by the following general formula [M-XI] are most favorable.
General formula ~M-XI]
Rml2 - CH2 ~
where Rml2 is synonymous with aforesaid R.
Rml2 is preferably a hydrogen atom, or an alkyl group.
Typical examples of the compounds according to the inven-tion will be given below.
~- 1317~00 ce C ll 3 ~,N~
1l (Cll 2) 3 ~ NIIS0 2 ~ OC I 21i z s ce Cll3~,,N~
I--N l~-(CI12)3~NIJCOCI10~ 3 Cl ollz~
~ - 50 ~3011 C~ H
C D 3 ~N~N
N N 1l CllCHzS02C~ 8H37 I
Cl13 ce H
C H 3 \~ N~
C 11 2 C li 2 S 0 2 C 11 2 C 11 ~
C811, 7 ~ 189 _ 1 3 1 7 500 C~ H
Cll3 ~N~ Cll3 ¦¦ ¦ N I
N N 11 C--Cll2SO2CI81137 I
N~
~ .
H
CZIIS~ ~N~ OC4119 11 (CH2) ~SO2--~
CBH I 7 (t) Cl 2ll25O~SOZNH--~ (Cll2) 3\~N~
N N 11 C4ll9(t) c, 21l 2 5 n ~ S o 2 N 11--~
N N 11 Cll 3 C~IIII 3~ C ~ H
~ CIICIIZSOZCIIZCIIZ~,N~
1 o c o 11 CH3 ~ N~
N - ~Y 1I CH2CH2S02- ~ NHCOCHCH2COOII
C~s~137 C~ H
Cl13 ~ N~
N I l~ C}12CH2NHSOz- ~ OCI2Hzs (,'~ ~I
Cl13 ~ N~ Cl13 - N 1l CHzCH2S02- ~ NHCOCHO ~ C ~ 011 C~ollz~ Cl13 C~ 1 Csll~7SOzCH2CH2 ~ N~
N N 11 C]ICIIZSOZC~ 2HZ5 Cl13 CQ N
Cl sll~l~N~
N l 1l (Cllz)30--~3NIIS02N(CI13)2 1 5 S-~
COOII
H
CH3~ ~.,,N~ Cl sH37 b 1 ll ( C H z ) 3 ~3 N~ C O )/
C211s~.~N~ Csll I I ( t~
N N 1l - (CHz)2~73NllCOCI10--~C511l I tt) C~lls C Q ~I
Cll 3 ~N~ OC ,911 1 7 CHC112CH2S02C112C112S02 ~
CH3 Cl13 .
t317500 ce n Cl13 ~ N~ Cl13 C- CHzSO2- ~ NIISO C hll33 O -~3 OCII I
¦ H
CH3~ N~ CHI OC.119 CHzCH2CNlJSOz ~
CH3 C~11 7(t) ce n C113 ~ N~ OC 8 D 1 7 N - I 1l CHCH2NHS02 ~ O ~ 7 CH 3 NHSO 2 - ~
C~1~ 7(t) ce H
(i)C3U7 ~ N~ O
N N 11 (CH2)1S02- ~
CBH 7(t) - 193 _ 1 3 1 7 500 ce H
(i)C3H7 ~ N~
N - N 11 CHCHzCHzSOzCI~H33 C~ H
(i)C3H7 ~ N~ CH3 N 1I C- CHzSOz ~ OC~zN25 (i)C3H7 ~ N~
N - N 1I CHzCH2SOz- ~ NHSO2C,~H33 ce H
(i)C3117 ~ N~ OC H'3 N N 11 (CHz)3S02- ~ OC4H9 NHSOz ~
C~ll 7(t) C~ H
(i)C3117 ~ N~ . OC8HI7 ,l N 1~ CHCHzCH2SnzClJ2CI12SOz~
.
COOH
~I
(i)C3117~ ~,N~ C.81135 1l ( C~l z ) 3 ~3 \ C O ~/
Br H
(i)C3H7 ~ N~N C ~ (t) N N 1~ CHO ~ C511,l(t) C6,~1. 3 CQ H
(i)C3117 ~ ,N~ C ~ (t) N---N 1l (CHz) 2 ~ NHCOCHO ~ Csll I, (~j C4H., - 195 _ ~ 31 7500 C4~9~ C e ~1 , CH ~ N~ CQ . CQ
1 1~ CH2CHzCH0 - ~ SOz ~ 011 C7H, 5 CQ H
(i)C3H7 ~ N~ CH3 O(CH2)~S02C,H9 ~ C~zCH2- C - NHS02 ~
\=<
CH3 C8H,7(t) (t)C4119 ~ N~ 0 N - N 1l (CH 2 ) 3S0 2 - ~
C~H, 7 (t) C ~ ~J
(t)C~H9 ~ N~ 0 N N 1l (CHz)3SOz - ~
C~H,7(t) ce H
t t ) C ~ N~
N N1l (ClJz) 3S02CI 81137 ce ( t ) C J 11 ~ \/~N~
--1 1l (C~12) 2SOZC~ ~13q ce ( t ) C ~ H 9 ~N~
N N1l C~ C H z C H 2 S O 2 C ~ t 11 3 3 CHs ce H
( t ) C ~ N~
N N 1l CHCHzSOzCI 81137 I
C~13 ce ~1 ( t) C .,11,, ~,N~ Cll 3 ¦¦ ¦ N I
N N 1l C--Cll2so2cl ~113q C~3 CQ ~I
tt)C~119 ~ N~ Cl13 N N ll C- CHzS02- ~ OCIzHzs Cl13 ce H
(t)C~lly ~ N~ CH3 C51i" (t) N N 1l C- CHzS02- ~ NHCOCHzO ~ ~
~ -Csll,,(t) C Q H
(t)C~II.,~ ~ N~ C411.,(1) I N 1l (CH2~ 3 ~NIiCOCI10 - ~ 011 C, 2112s ce H
(t)C 4H~ ~ N~ Cl13 N N 1I CHzCHzC-N}lCOCI10 ~ NllSOzN(CI13)z C113 Cl zllzs - 198 ~ 1317500 O -~ COOCII 3 1 11 .
(t)C~.lls~N~ C"ls (t) (C112) 3SOz--e~NllCOCHO~ 3 C~HI 3.
C4.Hs ( t) ~ -S~OII
ce n (t)C411s ,N~ OC<lls (CH z) 3 ~ NHSO z O C ~ ~1 9 ~,,~
(~
ce N 1I CllCl12S02~3NllCOCllCI12SO2C~zllzs CONH W N O ~ )zOC~z}lzs N N 11 (CHz)2 ~ NHSOz ~
NHCONH ~ N~ CQ
N N 11 (CH2)30 ~ OCl2Hzs CQ
C~ H
CH30 ~ N~ C~3 - N 1l C -CH20 - ~ COOCIzHz5 4 9 OC~9 S-~
C~1~,7(t) C2}1sS ~ ~ N~ C ~ (t) N N ll-CH2CH2NHCOCHO- ~ C5H " tt) S
~, C ~ 11 N I
N--N 1I C--CH2CRzSOzC~ zHz5 C~13 CQ H
(Cl13) 3CC112~N~ OC811~ 7 (CHz) 3SOz--~
OC~H, 7 5 "
ce C e H
C 11 z ~ N~ C H 3 ~- J ~ ~CIi3 C ~ 3 N 1~ S O z C J b 1l 3 J
C~
~I~N 1l (Cll 2) 3 ~ NIICOCIIO ~ 3 Cl oHzl 3~ -SOz~OII
~ 201 -N~ O C ll z C O N ( C z H s ) z N N ll Cl12CH2SOz--~
C~H 17 ~t) CQ CQ
C H 3 ~N ~ (C H 2 ) 3 ~ N H C O C H O--~3 S O z ~ O ll N--N--N Cl311z~
Cl13~N~CHCH2S02 ~OCI zHz5 CQ CQ
HO ~~SOz ~OCIICONII~ (Cllz) 3~N~CI13 Cl oR21 N N N
- 202 _ 1317500 CH3 OCHII, 7 CH 5 ~ N ~ tCHZ)z- C- NHS0 2 ~ OC H 11 1 7 N - N - N C113 NHSOz- ~
' C811~ 7 (t) C~ H
Cll,`~ ~ N ~ CHCH2CH2S02C,~113 N ~ N I ~ Nl1502C,~H33 OC"II. 7 Cll3 ~ N ~ CHCllzNHS02 ~ OCHII I 7 N N N CH3 NHS02- ~
C~H, 7 ( t) - t 3 1 7~00 6 ~ .
CH3 OC~ 3 (i)C3117 ~ N ~ (CHz)2- C-NIIS02 ~ 0C~ 3 N - N - N Cl13 C~ H
(i)C~H7 ~ N ~ C- CN2SO2C~sH37 N N N CH~
C~119 (t) ~ ~ OCHCONH- ~ N ~ N
OC~HI7 (t)C411~ ~ N ~ CHCllzNHS02 ~
N - N - N C2~1s NIIS02- ~
C~11,7(t) t317~00 O(CIIz)zO(CH 2) 20CII 3 (t)C4119 ~ N ~ (CHz)3S02- ~
N N N C~ 7(t) .
CP
(t)C~Hq ~ N ~ (CH 2 ) 3 ~ NHC0CH0- ~ S02-N - N - N CloH2l CQ
~ ~011 (t)C~IIq ~ N ~ CIIzCllzC- NllS0 ~ 0C, Z1125 N - N N Cll~
(t)C~.IIq ~ N ~ CH2CHzS02 ~ NHSOzC~ 3 N N - N
ce NIICOCIIO- ~ G5R,,(t) N N Cloll2l CQ tCHZ)3- ~ NHSO2 ~ 0C~2Hz5 (t)C~N9 ~
Cl13SOz ~ ce (t)C~114 ~ (CH2)30 ~ C~
N N - NH NliCOCHO
Cl 21125 ~ O(CH2)3CONll(CHz)2C _ ~ ,N~
Cl511l, Cl13 N N - N
;= o ~ o - _ ~
", ~ .
/ ~ t~
_ X ~ C, o ~ ~ X ~ ..
n _ O
~ X
_ _ o O
r~
- 207 _~ 1317500 o o C~ _ t, U~
o ~ ~ .
.~ 1"
X ~ o ,_ ~ X , ..
Z~ ~..
~Z/ - I ~
V~ ¦ Z
:r :: Z
. N N
1 31 750~
In addition to the above given typical examples, the compounds shown by Nos. 1 to 4, 6, 8 to 17, 19 to 24, 26 to 43, 45 to 59, 61 to iO4, 106 to 121, 123 to 162, and 164 to 223, of those described pp. 66 to 122 of the specification of Japanese Patent Application No. 9791/1986, are mentioned as examples of the couplers expressed by the general formula [M-I].
The foregoing couplers can be synthesized ~ith reference to the Journal of the Chemical Society, Perkin I (1977), pp.
2047 to 2052; U.S. Patent No. 3,725,067, and Japanese Patent O.P.I. Publication Nos. 99437/1984, 42045/1983, 162548/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985, and 190779/
1985.
The above-mentioned couplers are normally used in the amount of 1 x 10- 3 mol to 1 mol, preferably 1 x 10- 2 mol to 8 x 10~l mols, per mol silver halide.
The couplers according to the invention can be used in combination with other kinds of magenta couplers.
Next, the seventh invention of the present application will be explained.
This seventh.invention is characterized in that in the processing method of the first invention, the light-sensitive material to be processed has, on the support, at least one silver-halide emulsion layer containing a coupler expressed by the following general formula CC-I].
General formula [C-I]
OH
R,~ ~ NNCD(N~)..Rc~
Rc 2 CONH
X c In the above formula, Rc2 represent an alkyl, cycloalkyl, alkenyl, aryl, or heterocyclic group, each of which may have a substituent group. Rc 3 represents a hydrogen atom, halogen atom; or an alkyl or alkoxy group, which may have a substituent group. Provided that Rc 2 and Rc 3 may be those which form a ring in conjunction with each other. Symbol Xc represents a hydrogen atom; or a group being capable of split off upon the reaction with an oxidation product of the color de~eloping agent. M stands for 0 or 1.
As the alkyl group represented by Rcl or Rc 2 . those hav-ing 1 to 32 carbon atoms are available; and as the similarly represented cycloalkyl group, those having 3 to 12 carbon atoms are available; as the similarly represented alkenyl group, those having 3 to 12 carbon atoms are available. These alkyl, alkenyl, and cycloalkyl groups include those having a substitu-ent group.
As the aryl group represented by Rcl or Rc2, a phenyl groups is preferred, which may have a substituent group.
As the heterocyclic group represented by Rcl or Rc2, a five- to seven-menbered one is preferred, which may be sub-stituted or condensed group.
Symbol Rc 3 represents a hydrogen or halogen atom, or an alkyl or alkoxy group, or, preferably, a hydrogen atom.
As the ring formed jointly by Rc2 and Rc3, a five- to six-membered ring is preferred. Examples of 5 to 6-membered rings so formed include C ~ 2 H 2 5 ~ \
~ ) ' ~ ) O N O N
H H
Examples of the group represented by Xc being capable of split off upon the reaction with an oxidation product of the color developing agent include a halogen atom, alkoxy, aryloxy, acyloxy, sulfonyloxy, acylamino, sulfonylamino, alkoxycarbonyl-oxy, aryloxycarbonyloxy, and imido groups. Of these, a halogen atom, and aryloxy and alkoxy groups are preferred.
Of said cyan couplers, those expressed by the following general formula CC-A] are especially preferred.
General formula CC-A]
OH
~ NIICOR A
~ 3 1 7500 In the formula, RA1 represents a phenyl group including a substituent of at least one halogen atom, wherein such a phenyl group may have a substituent other than a halogen atom.
Symbol RA2 is synonymous with Rc2 in the foregoing general form-ula [C-I]. Symbol XA represents a halogen atom, or an aryloxy or alkoxy group.
RA1 is preferably a phenyl group substituted by 2 to 5 halogen atoms.
The above-mentioned cyan couplers include, for example, the diacylamino phenol type cyan couplers described in the specification of Japanese Patent application No. 21843/1986, pp. 26 to 35, and Japanese Patent O.P.I. Publication No. 225155/
1985, the diacylaminophenol type cyan couplers described in Japanese Patent O.P.I. Publication No. 222853/1985, the diacyl and ureidoaminophenol type cyan couplers described in Japanese Patent O.P.I. Publication No. 185335/1985, and the ureide-aminophenol type cyan couplers described in Japanese Patent O.P.I. Publication No. 139031/1984. They can be synthesized according to the methods described in above cited publications.
The above-mentioned cyan couplers are usually incorporated in the silver halide emulsion layers, and more particularly, in the red-sensitive emulsion layer. The amount of such a cyan coupler used is within a range of 2 x 1 O- 3' to 8 x 10-l, pre-ferably 1 x 10~l to 5 x 10~l mols, per mol silver halide.
Typical examples of the cyan couplers expressed by afore-said general formula [C-I] are given below, but it is under-stood that the scope of said cyan couplers is not limited only to these examples.
[Example compounds]
CC-l (t)~CsH11 ~ NHCON ~ CN
(t)CsH1l ~ O- CHCONH
(t)csHll ~ NHCON ~ CN
(t)CsHll ~ O- CHCONH ~ ~ OCH3 (t)-CsHll ~ NHCON ~ CN
(t)CsHll ~ O- CHCONH
C6Hl3 (t)C~H17 1 31 7~0~
C
C, 5 H,, ~/NHCONH
.<,~ O -CHCONH F
C2Ns cc 5 ~NHCONH
110--~ O -CNCONH
( t)C~H, C~ 21~2s Cc_ G
OH
~NHCONHC, sH3, UO _~30-CHCONH lC~
(t.)C.,119 C,,~135 . . .
Cc_ 7 (t)CsH~ NHCONIl ~ CQ
(L)CsHIl ~ O-CHCONH CQ
C2Hs (t)CsH" ~ ~ ~I/NHcoNH ~ 3 so C~H, (L )C5 H " ~ O-CHCONH
Cz~ls Cc_ 9 ~ JHCONH ~ CN
Cl2H2sO { ~-O-CHCONH NO2 CH, ~NHCONH~ CN
HO~ O--CHCONH/~
(t) C4Hg C4Hg OCH2COOc2H5 CC-ll (t) C4Hg ~NHCON~SO2C2Hs (t) C4Hg~O--fHCONH/~ CN
Cl2H25 CQ
~,NHCONH~CQ
C4HgSO2N}~V O--fHCONH CN
~NHCON}~ COOCH3 (CH3) 3CCOO~O--CHCONH~
Cl2H25 OCH2CONHCH2CH20CH3 (t)C4Hg~t)C~Hg J~ ~cNo3 C12H25 NHS02{~CH3 (t) CsHll ~NHCON~SO2NHC4Hs (t ) CsHll~ O--~ CH2 ) 3CON
~NHCON1~3 COC 2H5 (n ) Cl2H25NHCO~ O--CH2CONH/~ CF3 .~ :
- 218 - l 3 1 7500 Cc_ 17 CH~
(t,)C5Hl,~O-CNCON~
C~H, ~, L _ ¦ 8 (t)CsH" ~/NHcoNH ~OC~
(L)c~H~, ~ O-C~CONH
C, 2H2s CC_ I ~
' 011 S
NHCONH
O-CHCONH
~ ICQ
Cl2H2sO C2Hs ~ 219- t317500 cc_ 20 ~NHCONH ~ 3 ( t )C5~11 1~0 -CHCONH
( ~)CsH
cc_ 21 OH
~ NHCONH ~ SO 2 CH
( L )CsH~ O-CHCONH CQ
(L)CsH~
CC~ 22 OH
f i~ NHCONH ~ SOzC2Hs ( ~)C~Hs ~3SozCUCONH ~0 ~--OCzHs C~oH21 .. .. .
( t)CsN, I ~/NHCNH ~3So2~3N7 ( t)C,H"~O-CNCONH
CzHs cc_ 2~1 .
~t)C~H~ ~/NHcoNH~502C6H"
( L )C~H g ~0-1 CONH
CH~
C ~ 25 ~NIICONH ~SOC2Hs ~O-CHCONH /~
~=/ I CQ
C H C2Hs , s ,, C --~G
NHCONII ~11\OCCH
~H2sO ~_", O I~CO CQ
C2Hs ~ ~NHCON~ ÇC~
C12~1 2jO ~\~-0-CUCO ~ CQ
OCON ( CH ~ ) z C7Hs CC~ 28 CH C ~ il/NHlCI ~) ~ I ~ CQ
CH, -CH 2 -C--<J \`)--OCNCNH r 11 c~.
~, 0 CU, ~NHC
CH, -CH~ -C--<~OCHCNH
I \=< 11 CQ
CH ~ CQ ~
NUC
CH ~ -CH z -C ~OCl~CN~ C~J
CU ~ CQ
CHJ C, oH2, ~3/ 11 ~9 ' Cll ~ -CH 2 -C--~OCHCNH
I \=~ 11 ~Q
CH ~ CQ o - 223 - 13i75~0 N5iC
CH J C ~ 21~Z 5)~/ 1 CH, -CH z -C ~OCHCNII
I \=< 11 CQ
CH, CQ
C
C ~ 33 NUC ~3 CH, Cl, H " )~/ 1 C>=/
CH, -(CH2)2 -C~OCHCNH
CH, C0 o CC--3~ ;
NHC
CH~ C8~ / bi~
CH~-(CH2)z-C ~ OCHCNH
I \=(~ 11 CQ
C~ ~ CQ
C ~ 35 -OH
1 NHCOC~F7 CH~ C,H" p ~/
CK 3 CH z C ~OCHCNH
CH~ CQ
CC~ 36 ~NHCONII ~CQ
( t )CsH I I ~OCHCONH
C~lls Cll 37 NHCONK 4~S02CzUs CsH~ I (t) f~
( t ) C s H I I ~ OCUCONII CQ
C21~s CC~ 38 NHCaNII ~3F
~ s H ~
(~)CsHIl ~OCHCONH
C,Hs CC~ 39 CQ
NHCONH ~>
( t)C~H 17 ~OCHCONI{~3/ C3 CcH~
CC- ~
CQ
~/ CQ
( t )CaH I 1 ~OCHCONH
C~ll, ' C ~
-`
( t)C~H, 7 ~OCHCONH
C~Hg NHCONH ~CQ
/C,~,7(t) ~1~
(t)C~HI7 ~ 0CHCONH ~
OCH2CH2SO2CH, C,H,, C - ~3 (t)C~H, 7~0CHCONH
I OCH2CHzSOzCOOH
C2Hs C - ~4 CQ ~ NHCONH ~ CN
(t)CsHI~ ~ OCHCONH
I
CCH, .7 CQ ~NHCON~SO2C3H7 (t)C5Hll- ~ OICHCON
H ~ CQ
(t)C5Hll ~ O- CHCON
OH
~NHS02NHC4Hg C4HgSO2NI~O--ICHCON~
~ NHCONHC ~ SO2CH
(t)C4H9 ~ S - CHCONH
I F
~,NHCoNHso2~$
(n) C12H2s~o--CHCONH F F.
I
~,NHCON~ SO2CF3 CONH
~=/ F
Cl 6H330 OH ~
~,NHCON\JO
U~ S CF3 C4HgSO2N~ CON
~ C~
`4,~f j OH
~,NHCO- lcHcH2so2cl2H25 (t) C4E~9N}~CSN
CQ
(t) C5Hll ~NHCO ICH~3 (t ) C5Hll C2H5SO2~NHCONH/~J C4Hg ~NHCO~CONHCl2H25 CH2NHCONH/~N--INI
N--N
C --5~
C2Hs h/NHCOCHzo ~OC, 2H2s NCONH~
C C 2 11 s OH
(t)CsH" ~fNI~CO--C~F'7 ( ~ ) Cs H I ,~0--CHCONH~
C~H, ( ~ ) C 1 U g ~ ~/
C~Ug F
~,1~ NHCO ~ F
HO ~ û--CHCONH
( t)C~HY C, 2H25 C - BO
OH
(t)CsH " ~ NHCOCJF~
(t)CsHIl ~ O- CHCONH ~ ' C2Hs C ~ Gl OH
~ ~r~NH~O(CF2)2CHF~Q
Cl2H2sO ~ 0--fHCONHJ ~ JJ
C2Hs /(~)CsHl~ ~ ~ OCF2CHFCQ
(t)CsHIl ~ O - CHCONH OCF2CHFCQ
C2Hs C - ~3 OH
F~Us ~ NIICO(CF2CF2)2H
(l)CsHIl ~ O - lHCONH' (t)CsHIl -232- 13~75~0 cc 64 OH
,~NHCO(CF2 ) 3H
Cl 2H2sO ~O--CHCONH~
C.~1~9 F
C,51,SO2NH ~ ICI2~2s~3/NHco~3 CQ
C~oH2~ ~NHCO~
~O--CHCONH~. C 1 2H 2 s NHS0 2CH ~ CQ
C ~ 67 (t)Cs~ /NHC0 ( t ) C s U "~ O ~ CHCONH NHSO 2 Cll C2Hs OH
~NHS02CH3 CllH23C
OH
~ ~NHCOCls HO~ S02NI~
~NHCo~3 Cl3H27-cH=cHcH2clHcoN
~ IC12H25 ~ ~3 ~r - 234 _ 1317500 OH
~3 0--CHCONH/¢~
( CH2 ) 20C2Hs ~,NHCO~) ¢~ O--CHCONH
~3 CH2 - S 2 -NH
C~
~3~NHCo~3 C6Hl3~CHCoNH F
(t ) CsH" ~ J~3 F
. ~.
OH
CQ ~ NHCOC(CH3)3 CQ ~ O- ICHCONH
(t)C4Hg OCHCON
>==~ CQ
Cl5H3l(n) (t)C4H
OCHCON
~=J CQ
H ~ (t)C4Hg 02N ~ OCHCON
CQ
- 236 - 13175~0 cc 80 . C~ 2U2~ ~/NHCO~(t)C~Hs OCUCONH
CQCQ
Cl 2H2s ~/NHC0~3 C O ~ OIHCONH--~ -CQ CQ
cc_ 82 Cl 2H2s ~NIICO~
OIIICONH ~ CQ
CQ C
cc_ 83 ~OCHCONH ~~/
CQ CQ
- 237 _ 1 31 75 0 C12H25 ~NHC~
OCHCONH ~ CH3 CQ C
~ NHC
Cl2H25 ~ S(CH2)3CON ~
OH
(t)C5Hll ~ NHCOCH2CH=CH2 (t)C5Hll ~ O-(CH2)3CONH ~
F
~ NHCONH ~ S2 (t)C4H ~ O-CHCON
- 238 - 1 3 1 7~00 C,zH2s,~1 NHCONH ~ CFJ
SO,--N~ CONH~3/
I H ~ ~
1~3 ' NHCONH
C, CH,7C0NH
cc_ 90 OH
~t)CsHI I~NHCoNH~3So2CH~
(l)c5H,r~o--CHCONII
Cl 2H2s cc_ 9 ~NHCONH ~SO2NH
~3 0--CHCûNU
C~HgSO2NH OCOCH~
OH
~H ~ ~ NHCONII ~ S020CH, C,2H2~0 ~ 0 - CHCONH J
C~
C - ~3 ~ NHC0NH ~ C0N <CH
(t)C~U, ~ ~ O - CH2CON
(t)C~, cc _ 9 OH
~ NHCONH ~ SOzNHCzHs C,6HJ,OCHCONH J
C, zH2s ~3 . ' OCH2CH20CH, CC~ 95 t)CsH~ 3/NIICOCH2~NIICOCH3 (t)Cslll r~a--(C~2)3CONH
C ~ 96 Cl 2~25 ~/NHC
NC--.~} OC~CONII ,l~
CQ
C ~ 97 C12 H2~ NHC ~3 OCNCONH ~ CQ
CN CQ
C -- 9 8 ~
C~ ~ lC~2Hz5~3/NNCO~3 CN CQ
-241- 13~7500 3i~ ,?~;7 cC_ y~ ' O~i C~ Cr2H2s ,~/NHco ~0--CHCONH J~ CQ
C~ CQ
Especially preferred cyan couplers are tabulated in the following pages.
. . .
llc3~ NllCU(Nll)r~
R~ 2CONII ~
Ex~mple _ . _ R . 2 R " ~ m I C~ (tj . ... __. . . . .
C ~ 1 ~ (Cll2) 4ll (l)C~III I -~OCIll- ll -ce o C4lls _ I c- ~ I ~tl)C~II"-~ C~ -ce o C-3 ~ ~l)C~ O~ ~l -CQ O
C~ ~1 _~1~ Cl~.lla~~ -ce -ce U
l ._ C--S ~. tCII~) ~NSO~NII--~ OCO-- . _ O~C ~ 7 t t) O
C-G ~ (t)c~ ocllllo)~ ll . . O
,.. ... ,,_ I I I_ c - 7 ~1,~511 " t l) . - ce, O
. I~ ce C411~
. ce .. _._ C - O ~( l) C~ I ~OCII- 11 - ce O
¦ NIISO2C~117C511m tl; _ ' C~ 9 ~ ~)C5llll~~ulcll- ,11 0~0Cll3 O
NIISU2C6ll1 1 C4ll~ _ 243 - 1 31 7sao ~e l~cl _ n........ xe _ , _I , ~ .
C--10 ~ - (I;lln) ~N'il)nNII -(~-()CII-- 11 , -ce O
. ce 112~(:, 2 _ _~ ___ .__ _ c - 1l ~ce c, ~ -(~SO2NII~) 11 -ce o ce I ce _ C ~ 12 ~ Ce~OCII-- - 11 - OCllzCONllCall7 O
_ ce c,OIlz' I_ ce c,~
C -~3 ~ C~1170-~OCII 11 -ce - o I ce C~117 (~ ..
c - 1~ ~--~ce I10-~OCII 11 ce o NllSOzCN3 C~ 2112~
_ _ C-15 ~Oz(Cllz)~O-~/~C~ ) oJ~I -ce o _ C-l~; ' ~1~ C~2ll~o~l? -ce O
. . _ C--17 ~(Cll~)~NSO~Nli-e30CII-- 11 -ce o ~ P~C1211~ _ C--111 ~i~ (Cllla) ~NSO~NII~OCII- 11 -ce O
P 11Cl zll2s I . ---- I _ C - I!l _ I tCnlln) ~N';I)~NII-e3-oCII- 11 Og~OCllJ O
- 244- 131750~
. _ com,oound No. 1~ c I ]~ . R ~ 7 X ~ ; m _ _ . ._ __ .. ~
C - 20 ~ OCII:~ ( L) C~ 0 ~ 11 - ce o C - 2l ~ C~ ll - ce o I P ~ C~ 5 _ l~lt C - 22 ~ Cll7CUO -~/3-OC~ ll - ce o P 1~ ~ ) C,.llz!.
l l l _ C-23 ' ~1~ ~l)C~ o~ ll ~ O
P 1l C3117 (1) C~lll 7 (~) ce c e ~ . _ _ .C - 2~ ~/3 ( ~) c~ll 1 l e~ o Icll ll ce o I . I _ P p .c~ll" (~) , C--25 ~ (l)C~IIIl-~OCll-- ll OCII,CONIICII,CII,OCII, O
P P C,ll, (I) -C511~ (1) _.
C--2G ~CN ~ l . N l I c~l" (L) -- ----I
C -27 ~SO,C~ (n)(l)C~IIm ~OCN-- N N
C - 2~ ~ce ~5,11~ ) _ ~ _ CN C ~ . . _ C -2~ ~S0~C~ (l)C~ -~OCII- n -ce l . c.ll. . _ ~ompound No . n ~, 1~ ~ 2 R . ~ X . ¦ nl . I ~~~ Csll~ )' ' ' .. ... ~ _ C--3U ~sozc4llq(n)(t)C~II"--~OCII-- ll OCII~CONll(Cllz)zOCllJ 1 l Czlls I _ C.-31 ~C-NCe~l)Collll ~OI~ll 11 O~C~1117(t) I
.. IlCsllll O _ C--:12 ~ CN IC ~ 11 1, _~ OCII-- . C - Cll, I ~c,~" 1- _ C--33, -n--CJII, IC,III, -(~OCII-- 11 11 O
I LCsllll _ C--3-1 --n--C~117 lcOlllI-~OCII-- ll ll U t I ___ _ I_ c - 35 ~ce IcOIl 17 ~~ O~ll - . ll . ce _ I nC~ I_ C-3G ~c,ll"-~o-cll- ll ce o ce ce nC~II, J _ C_37 ~) C~ SU~ 3__C!II_ 11 ce o _ I_ _ . __ I , . ,~ _ C -33 ~SO~C~117lC~III I -~`OCII-- ll 11 I
l tCsllll ~ _ C ~ 3~ ~ CNIC s ll l 1 -~ O(,II-- ll ~3 _ n--C~ J _ OCI~II 17 _ Next, the eighth invention of the present Application will be explained.
This eighth invention relates to color developer solutions and provides a color developer solution for silver halide color photographic light-sensitive materials, which comprises at least one compound selected from the following group CA] and at least one means selected from the following group CB].
Group CA]
(A-1) Compounds expressed by the following general formula CR-I]:
General formula CR-I]
X r ~ ) n r ~'- C /
In the formula Xr', Xri' independently represent a halogen atom, or an alkyl, aryl, amino, hydroxyl, nitro, carboxyl, or sulfonyl group; Xr2' represents a hydrogen atom, or an alkyl, or aryl group, or a double bond for ring formation; Zr r~pre-sents a plurality of atoms consisting of a carbon atom, oxygen atom, nitrogen atom, and sulfur atom, which are necessary for forming a ring; nr, and mr independently represent 0, 1, 2 , or 3.
(A-2) Compounds expressed by the following general formula [R-II];
- 247 ~ 1 3 1 7 5 0~
General formula [R-II]
Y,, ~$Y
Y r ~ Y r In the formula, Yr , Yrl, Ur2, and Yr3 independently re-present a hydrogen atom, halogen atom, or an amino group, hydro-xyl group, nitro group, carboxyl group, or sulfonyl group.
IA-3) Compounds expressed by the following general formula [R-III]:
General formula CR-III]
.. . . .
Yrs -- Tr ~ Xr2 I
Xr 3 In the formula, Tr represents a nitrogen or phosphor atom;
Xr2, Xr3 independently represent a hydrogen atom, or an alXyl group, aryl group, or halogen atom; Yr4 and Yrs independently represent an alkyl or aryl group; ~r4 and Yrs may form a hetero-cyclic ring through ring closure.
(A-4) compounds expressed by the following general formula [R-IV]:
- 248 - 13t7500 General formula ~R-IV]
C - R
C - -X, Y s Rs20 \ Z ~ \ OR,~
In the formula [R-IV], Rsl represent -OH, -oRs4, or -N HRS ; Rs4 and Rss independently represent an alkyl group, typified by a methyl, ethyl, propyl, butyl, benzyl, ~-hydro-xyethyl, or dodecyl group, wherein each of such a group may have a substituent (for example, an aryl group such as hydroxyl or phenyl group).
Rs2 and Rs3 represent -H or -C-Rs6, in which Rs6 represents an alkyl or aryl group, illustrative o~ which is a long-chain alkyl group, such as an undecyl group.
Xs and Ys respectively represent a carbon and hydrogen atoms which respectively form together with other plurality of atoms six-membered rings; and Zs represents -N= or -CH=.
Where Zs represents -N=, citra~ic acid derivatives are typical compounds illustrative of the compounds expressed by the general formula CR-IV~. If Z represents -CS=, benzoic acid - 249 ~ 1 3 1 7500 derivatives are typical compounds illustrative of the compounds expressed by the general formula [R-IV]. It is further noted that six-membered rings include those having a substituent group such as a halogen atom.
As far as Zs is concerned, -N= is preferred.
The compounds expressed by the general formula CR-I]
through CR-IV] are same as the earlier explained ones, examples of which have already been given.
(A-5) Polymers or copolymers respectively having pyrolidone nucleus in the molecular structure ~A-6) Polyethylene glycol derivatives The groups (A-5) and (A-6) are correspondingly identical with the earlier described "polymers or copolymers having pyrolidone nucleus in the molecular structure" and "polyethyl-ene glycol compounds".
CGroup B]
(B-I) The concentration of the p-phenylenediamine-based color developing agent in the color developer solution is higher than 1.5 x 102 mol/liter.
(B-II) The pH of the color developer solution of 10.4 or high-er.
(B-III) The concentration of the sulfite in the color developer solution is lower than 1.5 x 102 mol/liter.
(B-IV) The concentration of the bromide in the color developer solution is lower than 0.8 x 10-2 mol/liter.
- 250 ~ 1 31 75~
(B-V) The color developer solution contains at least one of those kinds of compounds expressed by the general formulas (A-I) through (A-VI).
The general formulas (A-I) through ~A-VI) are same as those earlier described, and examples illustrative of the com-pounds expressed by the formulas are same as those earlier given.
In this conjunction, the following combinations are shown, by way of example, as preferred combinations.
o (A-1) + ~B-1) (in which + means combination) o (A-1) + (B-2) o (A-1) + (B-3) o (A-1) + (B-4) o (A-1) + (B-5) o (A-2) + (B-1) o (A-1) + (B-1) + (B-2) o (A-2) + (B-2) o (A-3) + (B-1) + (B-2) o (A-1) + (B-1) + (B-5) o (A-1) + (A-2) + (B-1) + (B-2) o (A-3) + (B-1) o (A-2) + (B-3) + (B-4) o (A-1) + (B-1) + (B-3) o (A-1) + (A-5) + (B-1) + (B-2) O (A-1) + (A-6) + (B-1) + (B-2) + (B-5) O (A-5) + (A-1) + (B-1) O (A-1) + (A-5) + (B-1) + (B-2) + (B-5) O (A-1) + (A-5) + (b-1) + (B-5) Examples illustrative of the compounds expressed by the General formula CR-IV] are shown below. Needless to say, how-ever, the CR-IV] compounds are not limited by these examples.
( 1 ) COOH
~10/~\0~1 ( 2 ) COOH
HO OH
- 252 - 13~7500 ( 3 ) COOCH3 HO N OH
( 4 ) COOC2H~
,~, HO N OH
( 5 ) COOC3H7 HO N OH
( 6 ) COOC~H 9 HO N Oll ( 7 ) /=\
COOCHz~d ~1' H O N O H
( 8 ) COOC~ zNzs HO N OH
g ) CONH 2 HO N OH
OH
(10) / C H z C H z H O /~3\ O ll ( 11 ) COOH
,~
CH3 (Cll z) I oCOO N OCO tCI12) 1 oCH3 (12) COO~
,~
H O N O C O t C ll 2 ), O C H
( 13 ) COOH
C ~
HO 1~N~ON
( 14 ) COOC}~3 H O /~\ O N
(1~) COOC2H5 110/~ ON
( 16) COOC3N7 (n) HO )~\ OH
- 255 ~ 1 ~ 75`0~
, ( 17 ) COOC4H 9 (n) ~10/~\011 ( 1 8 ) C O O C 1 2 H z 5 ( n ) HO OH
( 19 3 CONH2 ~ O ,e~ O H
( 20 ) COOH
Cll~ tCIIZ) ~ oCOO/~\OCO(Cllz), oCH~
21 ) COOH
ce ~
HO OH
- 256 ' 1 ~1 7500 The concentration of any of the compounds expressed by the general formula [R-IV] in the color developer solution is, for example, preferably 0.1 g to 50 g per liter of the solu-tion, more preferably 0.2 g to 20 g/liter.
The color developer solution used in each of the inven-tions of the present application may contain various ingre-dients conventionally used in such a solution, for example, alkaline agents, such as sodium hydroxide and sodium carbonate, alkali metal hiocyanate, alkali metal halide, benzyl alcohol, water softener, and thickening agent, also development accel-erator and the like, other than those mentioned above, as desired.
Other additives than above mentioned which may be added to the color developer solution include an anti-stain agent, sludge preventive agent, preservative, interlayer effect pro-motor, and chelating agent.
If a compound expressed by the following general formula ~H-I3 is added to the color developer solution of this eighth invention of the present application or to the color developer solution used in any of the other inventions of the present application, tar generation in the color developer solution is inhibited and thus the object of the inventi0n can be more effectively accomplished.
General formula CH-I] ~~-R hl~
~ N O H
- 257 - ~3t7500 ' h1 and Rh2 independently represent an alkyl group or hydrogen atom, provide, however, that in no case both Rh1 and Rh2 are hydrogen atoms; Rh1 and Rh2 may bond together to form a ring.
In the general formula CH-I~, while Rh1 and Rh2 are, as above mentioned, alkyl groups or hydrogen atoms except that not both of them are hydrogen atoms, the alkyl groups expres-sed respectively by Rh1 and Rh2 may be identical with or dif-ferent from each other, being preferably alkyl groups having 1 to 3 carbon atoms. Rh1 and Rh2 may bond together to form a ring, for example, a heterocyclic ring such as piperidine or morpholine.
While various specific examples of the hydroxyamine com-pounds expressed by the general formula CH-I] are given in U.S. Patent Nos. 3,287,125, 3,293,034, and 3,287,124, parti-cularly preferred [H-I] compounds are exemplified below.
- 258 -' l3l7500 R hl ~
/ N - O H
R hZ
.. .
¦ Example compound No. R I R z H - 1 ~ C2Hs - CzHs H - 3 - C3H7 (n) - CaH7 (n) H - 4 - C,H7(i) - CaH7(i) H - 5 - CH3 - CzHs H ~ 6 - CzHs - C3R7(i) H ~ 7 ~ CH3 - C~H7(i) H - 8 _ ~ - CzHs H - 9 - H -- C3R7~n) H - 11 - H - C3H 7 (i) H ~ 12 ~ C 2 H 5 ~ CzH 4 0 C 11 3 H ~ 13 - CzH~ON - CzH~OH
H - 14 - CzH~SO 3 H - CzH 5 H - 15 - CzH4COOH - CzH~COOII
H - 16 f--~
HN N - O}l , /
H -17 f--~
HOCHzCHz- N ~ N - OH
H -18 f--~
O ~ N- OH
13175~0 CH3- N~__JN - OH
_ . I
Example compound No. R ~ R z H - 20 - CH3 - Cz114-OC113 H ~ 21 - C 2 H4-OCH3 - CzH40CI13 H - 22 - CzB4-OC 2 H~ - CzH~OCzH 5 H -23 - C3HbOCH3 - C3HbOCH3 H - 24 - CzHs -C 2 H~OCzlls H - 26 - CH3 - C 2 H~OC 2 H 5 . H - 27 - CHs ~ CHzOCH3 H -28 - CzHs - CHzOCzHs H -29 - CHzOCH3 - Cl120CII~
H - 30 - CzHs - Czll~OC~li .H -31 - C3HbOC~H7 ~ C3HbOC311, Of these, especially preferred compounds are H-I, H-2, H-8, H-9, H-12, H-18, and H-21.
These compounds are used in the form of ordinary free amine, hydrochloride, sulfate, p-toluene sulfonate, oxalate, phosphate, acetate or the like.
The concentration of the compound, represented by form-ula CH-I], in the color developer solution is usually prefer-ably 0.2 to 50 g/liter, more favorably, 0.5 to 30 g/liter, still more favorably 1 to 15 g/liter.
In the practice of any of the inventions in the present application, any known processing method for light-sensitive materials can be applied with no particular limitation, In one typical way, for example, after color developing, bleach-fixing is performed, and then washing or alternative stabili-zation processing is performed according to a specific require-ment. In another way, pre-hardening, neutralization, color developing, stop fixing, washing (or stabilization processing in place of washing), bleaching, washing (or stabilization processing in place of washing), after-hardening, and washing (or stabilization processing in place of washing) are carried out in order of mention. In another procedure, color develop-ing, washing (or stabilization processing in place of washing), supplementary color developing, stopping, bleaching, fixing, washing (or stabilization processing in place of washing), and stabilization are carried out in that order. In another devel-oping procedure, post-developed silver due to color developing is halogenation-bleached, developing is repeated to increase dye formation.
"Processing in a processing bath having bleaching ability"
means processing in a bleaching bath or a mono-bath bleach-fixing bath. The effects of the invention is advantageously attained with mono-bath bleach-fixing.
For use as bleaching agents in the bleaching solution or bleach-fixing solution in the bleaching stage, there are gene-rally known those in which metallic ions, such as iron, cobalt, or copper ions, are coordinated with organic acid, such as - 261 - ' 1317500 aminocarboxylic acid, oxalic acid, or citric acid. Typical examples of such aminocarboxylic acid are:
ethylenediamine tetraacetic acid;
diethylenetriamine pentaacetic acid;
propylenediamine tetraacetic acid;
nitrilotriacetic acidi iminodiacetic acid;
glycoletherdiamine tetraacetic acid;
ethylenediamine tetrapropionic acid;
disodium ethylenediamine tetraacetate;
pentasodium diethylenetriamine pentaacetate;
and, sodium nitrilotriacetate.
The bleaching solution and the bleach-fixing solution are used in a pH range of 0.2 to 9.5, preferably 4.0 and above, in particular, 5.0 and above. The range of processing temperatures used is 20 C to 80 C, preferably 40 ~C and above.
The bleaching solution may contain, together with afore-said bleaching agent (preferably organoacidic ferric complex salt), various additives. For this purpose, alkali halide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, and ammonium iodide, are especially preferred. Also, it is possible to add, as required, pH buffers, such as borate, oxalate, acetate, carbonate, a~d phosphate, solubilizers, such a~ triethanolamine and the like, and/or other additives, such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organophosphoric acid, oxycarboxylic acid, polycarbo-xylic acid, alkylamines, and polyethylene oxides, which are conventionally known for addition to the bleaching solution.
For the bleach-fixing bath, it is possible to use a bleach-fixing solution slightly loaded with halide, such as potassiun halide, or a bleach-fix solution of the type which is largely loaded with such halide as potassium bromide or ammonium bromide, or a special type of bleach-fixing solution composed of a combination of the bleaching agent of the inven-tion and a large amount of such halide as potassium bromide.
In addition to potassium bromide, it is possible to use other halogen compounds, such as hydrochloric acid, hydro-bromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide, and ammonium iodide.
The silver halide fixer used in the bleach-fixing bath is a compound of the type conventionally used in the process of fixing which reacts with silver halide to form a water-soluble complex salt, typical examples of which are thiosulfates, such~
as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, thiocyanates, such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, thio-ether, high-concentration bromides, and iodides. These fixers can be used within the solubility range of more than 5 g/liter, preferably more than 50 g/liter, in particular, more than 70 g/
liter.
As ~s the case with the bleaching solution, the bleach-fixing solution may contain pH buffers composed of various acids, such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bi-carbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide, either in one kind alone or in a com-bination of two or more kinds. Further, the bleach-fix bath may contain various kinds of fluorescent whitening agents, anti-foaming agents, surfactants, or anti-mordant agents.
Also, the bath may contain, as re~uired, preservatives, such as hydroxyamine, hydrazine, sulfite, isomeric bisulfite, and bisulfite adducts of aldehyde or ketone compounds; organic chelating agents, such as acetylacetone, phosphonocarboxylic acid, polycarboxylic acid, dicarboxylic acid, and aminopoly-carboxylic acid; stabilizers, such as nitro alcohol, and nitrate; solubilizers, such as alkanol amine and the like;
anti-stain agents, such as organic amine and the like, other additives; and organic solvents, such as methanol, dimethyl-formamide, and dimethylsulfoxide.
In the practice of the inventions of the present applica-tion, it is most advantageous that bleaching or bleach-fixing is performed immedi~ately after color developing; however, it is also possible that after color developing, such steps as washing or rinsing and stopping are performed, and then bleach-- 264 ~ 1 3 1 7500 ing or bleach-fixing is performed, or that a prebath contain-ing a bleach promoter may be used prior to bleaching or bleach-fixing.
In the conduct of the inventions of the present applica-tion, processing steps, other than color developing of the silver halide color photographic material e.g. bleach-fixing (or bleaching and fixing), and, where required, washing or stabilizing in place of washing are performed preferably at a temperature of 20 C to 80 C, more favorably, higher than Also, it is desirable to perform the step of stabilizing in place of washing as described in Japanese Patent O.P.I.
Publication Nos. 14834/1983, 105145/1983, 134634/1983, and 18~31/1985, and Japanese Patent Examined Publication Nos.
2709/1983 and 89288/1984.
The silver halide emulsion layers of the color pho~o-graphic light-sensitive material may contain corresponding couplers, that is, compounds which can react with an oxidation product of the color developing agent in order to form a dye.
For this purpose, except as specified for the inventions claimed herein, various kinds of yellow couplers, magenta couplers, and cyan couplers, can be used with no particular limitation. These couplers may be of the so-called two equiv-alent type or of the so-called four equivalent type. It is also possible to use any of these couplers in combination with 1~17500 a diffusible dye releasing type coupler.
For said yellow couplers, various compounds can be ef-fectively used as such, including closed-chain ketomethylene compounds; and the so-called two equivalent type couplers, such as coupler having -o-aryl substituent on the active si~e, coupler having -o-acyl substituent on the active site, coupler having hydantoin compound substituent in the active site, coupler having succinimide compound substituent in the active site, coupler having urazole compound substituent in the active site, and coupler having imide succucinate substituent in the active site, coupler having fluorine substituent in the active site, coupler having chrorine or bromine substituent in the active site, and coupler having -o-sulfonyl substituent in the active site. For the typical examples of useful yellow coupl-ers, reference is maae to those mentioned in U.S. Patent Nos.
2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072, and 3,891,445, West German Patent No. 1,547,868, West German Laid-Open Application Nos. 2,219,917, 2,261,361, and 2,414,006, British Patent No. 1,425,020, Japanese Patent Examined Publication No. 10783/1976, and Japanese Patent O.P.I.
Publication No. 26133/1972, 73147/1973, 102636/1976, 6341/1975, 123342/1975, 130442/1975, 21827/1976, 87650/1975, 82424/1977, 115219/1977, and 95346/1983.
For magenta couplers, except as specifically mentioned with respect to the general formula [rl-I], or in conjunction with the CM-I] couplers, compounds of the following types may be mentioned: pyrazolone, pyrazolotriazole, pyrazolinobenz-imidazole, and indazolone. As is the case with the yellow couplers, these magenta couplers can be not only of the 4 equivalent type but also of the 2 equivalent type. For typic-al examples of useful magenta couplers, reference is made to those mentioned in V.S. Patent Nos. 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,746, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908, and 3,891,445, German Patent No. 1,810,464, German Laid-Open Specification Nos. 2,408,665, 2,417,945, 2,148,959, and 2,424,467, Japanese Patent examined Publication No. 6031/1965, Japanese Patent O.P.I. Publication Nos. 20826/1976, 58922/1977, 129538/1974, 74027/1974, 159336/1975, 42121/1977, 74028/1974, 60233/1975, 26541/1976, and 55122/1978, and Japanese Patent Application No. 110943/1980.
For useful cyan couplers, as specifically mentioned with respect to the general formula CC-I], or in conjunction with the CC-I] couplers, phenolic and naphtolic couplers may be mentioned. These cyan couplers, as is the case with the yel-low~couplers, may be either of the 4 equivalent type or of the 2 equivalent type. For typical examples of cyan couplers, re-ference is made to those mentioned in U.S. Patent Nos.
2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383, 3,767,411, 3,772,002, 3,933,494, and 4,004,929, German Laid-Open Specification Nos. 2,414,830, and 2,454,329, Japanese Patent ~.P.I. Publication No. 59838/1973, 26034/1976 5055/1973, 146827/1976, 69624/1977, 90932/1977, and 95346/
1983, and Japanese Patent Examined Publication No. of 11572/
1974.
The silver halide emulsion layers and other structural layers of the photographic light-sensitive material may simultaneously contain colored magenta or cyan coupler, and other couplers such as polymer coupler. For colored magenta or cyan couplers, reference is made to the relevant descrip-tion in Japanese Patent Application No. 1193611/1984 of the present applicant, and for the above-mentioned polymer coupl-ers, reference is made to the relevant description in Japanese Patent Application No. 172151/1984 of the applicant.
Aforesaid couplers may be added to the photographic structural layers according to a conventional procedure. The amount of the coupler to be added, though not definite, is preferably 1 x 10-3 to 5 mol, in particular, 1 x 10-2 to 10~
mol per mol silver.
In the practice of the inventions of the present applica-tion, various other photographic additives may be incorporated into the islver hlide color photographic light-sensitive mate-rial. For example, various agents mentioned in "Reseach Dis-closure" No. 17643, such as antifoggant, stabilizer, ultra~
~- - 268 - 1 31 7 5~0 violet absorbent, anti-stain agent, fluorescent whitening agent, dye-image stabilizer, antistatic aget, hardening agent, surfactant, plasticizer, and wetting agent, may be used.
In the silver halide color photographic light-sensitive material, the hydrophilic colloid used for emulsion prepara-tion contains any of the following: gelatin, gelatin deriva-tive, graft polymers of gelatin with other polymer; proteins, such as albumine and casein; cellulose derivatives, such as hydroxyethyl cellulose derivatives and carboxymethyl cellu-lose: starch derivatives; and synthesized hydrophilic mono-and/or co-polymers, such as polyvinyl alcohol, polyvinyl imidazole, and polyacrylamide.
As the support of the silver halide color photographic light-sensitive material, there may be mentioned, for example, glass plate; polyester film made of cellulose acetate, cellu-lose nitrate, polyethylene terephthalate; polyamide film, polycarbonate film, and polystyrene film. These base materials can be selectively used according to the purpose for which the light-sensitive material is used.
According to the intended use, it is possible to provide an intermediate layer of a suitable thickness. Further, vari-ous layers, such as filter layer, anticurl layer, protective layer, and antihalation layer, may be suitably used in combi-nation. any hydrophilic colloid which can be used as binder in aforesaid emulsion layer can be similarly used in these - 269 ~ 1 31 7500 structural layers. These layers may contain such various photographic additives as are used in aforesaid emulsion layer.
The processing method of the present invention is ap-plicable to silver halide color photographic light-sensitive materials, such as color negative film, color positive film, slide color reversal film, cinema color reversal film, and TV color reversal film.
BRIEF DESCRIPTION OF DRAWING
Fig. 1 is a graph used ~o explain the layer swelling rate, in disclosing the present invention.
EXAMPLES
The typical examples of the invention are described as follows. However, the scope of embodiments of the invention is not limited only to these examples.
With each of the following examples, the amount of addi-tion to a silver halide photographic light-sensitive material, unless otherwise specified, is expressed by an amount per m2 light-sensitive material, and the amount of ~ilver halide or colloidal silver means the converted value representing equiv-alent silver.
Example 1 Standard light sensitive material B was prepared by the following process.
In accordance with the layer constitution commonly used in the photographic art, a black colloidal silver anti-hala-tion layer, red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer were sequentially formed upon a support (triacetate film base) in this order, incorporating various auxiliary layers between arbitrary adjacent layers, whereby, upon the above blue-sensitive silver halide emulsion layer, was disposed a high sensitivity monodispersed silver halide emulsion layer, thus preparing light-sensitive mate-rial B, wherein the amount of silver applied was 53 mg/100 cm2 and the thickness of dried layers was 23 m.
First layer: An anti-halation layer formed by applying dispersion prepared by first reducing silver nitrate using a hydroquinone as a reductant to obtain a black colloidal silver featuring a high absorptivity toward light having a wavelen~th of 400 to 700 nm, and then dispersing 0.8 g of this colloidal silver into 3 g of gelatin.
Second layer: An intermediate layer comprising gelatin Third layer: A low-sensitivity red-sensitive silver halide emulsion layer containing 1.5 g of low-sensitivity red-sensitive silver iodo-bromide emulsion (AgI; 7 mol%), 1.6 g of gelatin; as well as 0.4 g of tricresyl phosphate (here-inafter referred to as TCP) having dissolved 0.85 g of 1-- 271 - 1 31 7 ~ 00 hydroxy-4-(~-methoxyethylaminocarbonylmethoxy)-N-[~-(2,4-di-t- amylphenoxy)butyl]-2-naphthamide (hereinafter referred to as cyan coupler (C'-0), 0.030 g of disodium 1-hydroxy-4-C4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazoOphenoxy]-N-C~-~2,4-di-amylphenoxy)butyl]-2-naphthamide (hereinafter referred to as colored cyan coupler (CC'-1)).
Fourth layer: A high-sensitivity red-sensitive silver halide emulsion layer containing 1.1 g of high-sensitivity red-sensitive silver iodo-bromide emulsion (AgI; 6 mol~), 1.2 g of gelatin; as well as 0.17 g of TCP having dissolved 0.25 g of cyan coupler (C'-0), and 0.020 g of colored cyan coupler (CC ' - 1 ) .
Fifth layer: An intermediate layer containing 0.04 g of dibutyl phthalate (hereinafter referred to as DBP) having dis-solved 0.07 g of 2,5-di-t-octylhydroquinon~ (hereinafter re-ferred to as anti-stain agent ~HQ'-1)); as well as 1.2 g of gelatin.
Sixth layer: A low-sensitivity green-sensitive silver halide emulsion layer containing 1;6 g of low-sensitivity green-sensitive silver iodo-bromide emulsion (AgI; 6 mol~), 1.7 g of gelatin; as well as 0.3 g of TCP having dissolved three types of couplers i.e. 0.32 g of 1-(2,4,6-trichloro-phenyl)-3-~3-(2,4-di-t-amylphenoxyacetamido)benzenamido]-5-pyrazolone (hereinafter referred to magenta coupler (M'-1)), 0.20 g of 4,4-methylenebis-11-(2,4,6-trichlorophenyl)-3-C3-- 272 ~ 1 ~ t 7500 12,4-di-t-amylphenoxyacetamido)benzenamido]-5-pyrazolone (hereinafter referred to as magenta coupler (M'-2)) and 0.066 g of 1-(2,4,6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidanilino)- 5-pyrazolone (hereinafter referred to as colored magenta coupler (CM'-1).
Seventh layer: A high-sensitivity green-sensitive silver halide emulsion layer containing 1.5 g of high-sensitivity green-sensitive silver iodo-bromide emulsion (AgI; 8 mol%), 1.9 g of gelatin; as well as 0.12 g of TCP having dissolved 0.10 g of magenta coupler (M'-1), 0.098 g of magenta coupler (M'-2), and 0.049 g of colored magenta coupler (CM'-1).
Eighth layer: A yellow filter layer containing 0.2 g of yellow colloidal silver; 0.11 g of DBP having dissolved 0.2 g of anti-stain agent (HQ'-1); as well as 2.1 g of gelatin.
Ninth layer: A low-sensitivity blue-sensitive silver halide emulsion layer containing 0.95 g of low-sensitivity blue-sensitive silver iodo-bromide emulsion (AgI; 7 mol%), 1.9 g of gelatin; as well as 0.93 g of DBP having dissolved 1.84 g of ~-C4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolydinyl)]-~-pyvaloyl-2-chloro-5-[~-(2,4-di-t-amylphenoxy)butanamido]~;cet-anilide (hereinafter referred to as yellow coupler (Y'-1)).
Tenth layer: A high-sensitivity blue-sensitive silve;
halide emulsion layer containing 1.2 g of high-sensitivity monodispersed blue-sensitive iodo-bromide emulsion (AgI; 6 mol%), 2.0 g of gelatin; as well as 0.23 g of DBP having ~ 273 -t 3 ~ ~500 dissolved 0.46 g of yellow coupler (Y'-1).
Eleventh layer: The second protective layer comprising gelatin.
Twelfth layer: The first intermediate layer containing 2.3 g of gelatin.
this light-sensitive material B was exposed under the following exposure conditions using a tungsten light source and filter, whereby a color temperature was adjusted to 4800 K, in order to provide 3,2 CMS wedge exposure light.
(Exposure condit1Ons C) The exposured light-sensitive material B was subjected to color developing at a temperature of 38 C with a duration of 3 min. 15 sec. by using developer A. :[n this course, the maximum magenta dye density M of light-sensitive material B
in terms of a maximum transmitting density was 1.80, which was measured with a SAKURA photoelectric densitometer PDA-65 manu-factured by Konica Corporation).
Developer A
Potassium carbonate 37.5 g Sodium sulfite 4.25 g Potassium iodide 2 mg Sodium bromide 1.3 g Hydroxylamine sulfate 2.0 g 3-methyl-4-amino-N-ethyl-N-(~-hydroxyethyl)-4.75 g aniline sulfate * Trade mark.
B
.
- 274 - ~ ~1 7~ 00 LWater was added to the above components to prepare one liter solution, which was adjusted to pH 10.0 with 45 ~ potas-sium hydroxide or 50 % sulfuric acid.
Next, samples were prepared as follows.
Silver halide emulsions in Table 1 i.e. emulsions con-taining spherical silver halide particles were prepared using a conventional double-jet precipitation process.
The following layers were sequentially formed, in this order, on a cellulose triacetate support, to prepare a multi-layer color film sample.
First layer: Anti-halation layer (HC layer) An anti-halation layer containing 0.18 g of black colloid-al silver, and 1.5 g of gelatin.
Second layer: Subbing layer (IG layer) A subbing layer containing 2.0 g of gelatin.
Third layer: Red-sensitive silver halide emulsion layer ~R layer).
A red-sensitive silver halide emulsion layer containing not only each of the silver halide emulsions listed in Table 1 and sensitized to have red-sensitivity, but dispersion pre-pared by emulsifying and dispersing tricresyl phosphate (here-inafter referred to as TCP) having dissolved 0.2 mol/molAg of the following cyan coupler (C-1), 0.006 mol/molAg of the follow-ing colored cyan coupler (CC-1) and the example DIR compound (No. D-24), but methanol having dissolved an inhibitor, into - 275 ~ 1 3 t 75 0 0 aqueous solution containing gelatin.
Fourth layer: Intermediate layer (2G layer) An intermediate layer comprising 0.14 g of 2,5-di-t-butylhydroquinone, and 0.07 g of dibutyl phthalate (herein-after referred to as DBP).
Fifth layer: Green-sensitive silver halide emulsion layer (G layer) A green-sensitive silver halide emulsion layer containing not only each of the silver halide emulsions listed in Table 1 and sensitized to have green-sensitivity, but dispersion pre-pared by emulsifying and dispersing TCP having dissolved 0.15 mol/molAg of the follwing magenta coupler (m-1), 0.015 mol/
molAg of the following colored magenta coupler (CM-1) and the example DIR compound (No. D-5), into aqueous solution contain-ing gelatin.
Sixth layer: Yellow filter layer A yellow filter layer containing 0.3 g ye~low colloidal silver, and 0.11 g of DBP having dissolved 0.2 g anti-stain agent (2,5-di-t-octylhydroquinone); as well as 2.1 g bf gelatin.
Seventh layer: Low-sensitivity blue-sensitive silver halide emulsion layer (B layer) A blue-sensitive silver halide emulsion layer containing not only each of the silver halide emulsions listed in Table 1 and sensitized to have blue-sensitivity, but dispersion pre-pared by emulsifying and dispersing TCP having dissolved 0.3 - 276 - t 31 75 on mol/molAg of the following yellow coupler (Y-1) and the example DIR compound (No. D-62), into aqueous solution containing gel-atin.
Eighth layer: High-sensitivity monodispersed blue-sensi-tive silver halide emulsion layer (B layer) A layer similar to the seventh layer, except that slightly larger silver halide particles were used.
Ninth layer: Protective layer (3G layer) A protective layer containing 0.8 g of gelatin In addition to the above components, each layer was allow-ed to contain gelatin-hardening agents (1,2-bisvinylsulphonyl-ethane and sodium 2,4-dichloro-y-hydroxy-s-triadine), surfact-ant and the like.
The amount of silver applied was 50 mg/100 cm2.
The couplers used in the respective layers were as follows.
Cyan coupler (Cl-1) 2-~ , y, ~ -octafluorohexanamide)5-[2-(2,4-di-t-amylphenoxy)hexanamide]phenol Colored cyan coupler (CC1-1) Disodium 1-hydroxy-4-C4-(1-hydroxy-8-acetamide-3,6-disulfo-2-naphthylazo)phenoxy]-N-C~-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide Magenta coupler (Ml-1) 1-(2,4,6-trichlorophenyl)-3-{C2,4-di-t-amylphenoxy)-acet-amido]benzamido}-3-pyrazolone and 1-(2,4,6-trichlorophenyl)-1 3 ~ 7~00 3-{C~-(2,4-di-t-amylphenoxy)}-acetamide]benzamido-4-(4-meth-oxyphenylazo)-5-pyrazolone Colored magenta coupler (CM~
1-(2,4,6-trichlorophenyl)-4~ naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidanilino)-5-pyrazolone Yellow coupler (Yl-1) -~ -C4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolydinyl-~-pyvaloyl-2-chloro-5-Cy-(2,4-di-t-amylphenoxy)butanamido]acet-anilide Samples 1 through 19 were prepared respectively using the above specified compositions specified in Table 1 as the com-position of silver halide, and varying the amounts of applica-tion in the third, fi~th, sixth and seventh layers, varying the amount of gelatin-hardening agent in the eighth layer and add-ing gelatin-hardening agent into the blue-sensitive silver halide emulsion layer so as to reduce T1/2 of certain samples.
Next, the layer thicknesses, as well as layer swelling rates T1/2, were measured. Table 1 lists the measurement results.
Each sample was exposed with green light, red light or green/red light (16 CMS) through an optical wedge, thereby treated with the following treatment steps, so as to form a dye image.
Treatment Color developing Time and temperature specified in Table 2 Bleaching 4 min (38 C) 1 3 ~ 750~
Fixing 3 min (30 to 38 C) Washing 1 min (20 to 33 C) Stabilizing 1 min (20 to 33 C~
Drying The compositions of processing solutions used in the respective processing steps are as follows.
(Color developer) Sulfate of the previously mentioned 3 x 10-2 mol example compound (E-2) Sodium sulfite anhydride 4.25 g Hydroxylamine - 1/2 sulfate2.0 g Potassium carbonate anhydride30.0 g Sodium bromide 1.3 g Trisodium nitrilotriacetate (monohydride) 2.5 g Potassium hydroxide 1.0 g Inhibitor (Z-5) 0-5 g Water was added to the above components to prepare one liter solution, which was adjusted to pH=10.2 using 50 ~ KOH
and 50 ~ H2SO4.
(Bleacher) Ferric (III) ammonium ethylene-200 g diamine tetraacetate Ammonium bromide 150.0 g Glacial acetic acid 10.0 mQ
Water was added to the above components to prepare one liter solution, which was adjusted to pH=6.0 using aqueous ammonium and acetic acid.
(Fixer) Ammonium thiosulfate 175.0 g Sodium sulfite anhydride 8.5 g Sodium metabisulfite 2.3 g Water was added to the above components to prepare one liter solution, which was adjusted to p~=7.0 using acetic acid.
(Stabilizer) Formalin (37 % aqueous solution) 1.5 mQ
Konidax (manufactured by Knonica Corporation) 7.5 mQ
Water was added to the above components to prepare one liter solution.
Graininess (RMS) of each obtained cyan dye is listed in Table 2. Incidentally, the addition of DIR compound into each color-sensitive layer was controlled so that the layer may indicate the same degree of desensitization and density de-crease.
Using the above processing solutions and the above treat-ment steps, the above standard light-sensitive material B hav-ing been exposed under the above mentioned exposure conditions was treated at a temperature of 40 C with a color developing time of 2 minutes, whereby the minimum transmitting magenta dye density was 2.2 and the magenta density in non-exposed areas was 0.38.
- 280'- 1317500 Table 1 ~ight- S$ Lver hal$de thic~- Layer swelling, mater$a L Ag I AgBr AgC e ~ m Tl/2 (sec) l _ 100 _ 20 12 _ 2 _ 90 10 20 12 3 0.~ 90 1 9.5 20 12 _ 0.5 89.7 9.8 30 2a . 5 0.5 99.5 _ 30 16 ~ 0.5 99.5 _ 20 16 7 6.0 1 94 _ 20_ 5 8 6.0 1 94 _ 20 t~
: 9 6.0 94 Z~ 16 6.0 94 _ 20 2U
11_ 6.0 94 _ 20 25 12 6.0 9~ _ 20 30 13 G.0 94 15 14 6.0 94 _ 1~ 11 _ 6.0 94 _ 22 10 16 G.0 94 _ 25 11 17 6.0 94 _ 2~ 13 l~ 6.0 94 1 _ 31 13 19 6.0 94 1 _ 35 14 - 281 ~ t 31 7soa Table 2 Graininess (RMS values) time ~sec) i 2 1 0 ( ~ 180 ¦lS a 1 2 0 9 0 fi () Color developing 3 3 ( C )¦ 3 5 ¦ 3 7 . 5 4 42 ----_ 52 150 48 46 4~ .ll I
2 53 51 49 49 48 1 5u 3 49 ,!6 47 46 46 4 47 45 1 ~2 13~ ! 33 32 146 4~ 1 ~7 133 ! 32 31 6 146 38 1 36 13~ 1 33 32 o l z 7 145 3~ 1 ~0 129 1 26 1 25 8 4~ 34 1 31 130 26 25 . 9 46 36 1 33 31 29 27 3 '15 31 30 28 25 25 1~ ~5 3 3 31 29 25 25 _ lS 47 35 32 35 27 26 16 ~8 39 35 34 30 2 . 1~ 149 46 4~ 39 39 3~
Gralniness: Smaller RMS values are more advantegous. Values enclosed ln heavv lines correspond wlth preferred embodiments of the lnventlon.
- 282 - t 31 7 5 00 As can be understood from the results in Table 2, satisfactory graininess is obtained, when using each of the light-sensitive materials 3 through 19 and the treatment steps of the invention. Further, it is apparent that a sample with a layer thickness (i.e. a thickness of dried layers determined by subtracting a thickness of support from the whole layer thickness) of less than 25 ~m is more satisfactory, and that sample with a layer swelling rate (T1/2) of less than 20 sec is more satisfactory, and that samples treated with a color developing time of 180 seconds shoed satisfactory results;
samples treated with a color developing time of shorter than 120 seconds showed especially excellent results.
Example 2 Silver iodo-bromide emulsions listed in Table 4 were prepared in accordance with the following method. Emulsion A through C were prepared using a conventional double jet precipitation process. Emulsions D through K, respectively core/shell type monodispersed emulsions, were prepared using a functional addition method. Emulsion L, a silver halide emulsion containing tabular particles, was prepared using a double jet precipitation process with pH and pAg being cont-rolled.
Next, using the above emulsions A through L, light-sensi-tive material Samples Nos. 20 through 43 respectively having layer thicknesse~ listed in Table 4 were prepared in compliance - 283 ~ l 3 ~ 75 00 with the preparation method for a light-sensitive material in Example 1.
Each sample was tested in a manner identical with Example 1. The obtained data with regards to graininess (RMS value) and yellow-stain are listed in Table 5.
~ T~ ~ s ~ 3~ ~9 .~, a~ ~1~ ~ 3 .~
l ,~}1 A ~ ~ o _ _ o o o o o e~
E~ ~t ,m 0~ cq u~ c~ u~ o o o o l~u ~ L~-~ ~ rl ~
~ i~i W ~o _ IA W C ~0 r- ~`1 CO 1_ '7 O
3~ ~ ~ ~ ~ ~ o~ ~ ~ x ~
1 31 750() -- 28~ --_ . .
---- b C~t ~ ,_ C~J C`l O ~ ~O C`l l_ _ C`~ OD ell C'~ OO C`l __ C`l C`l C`l C~ __ .. _. __ _ ~J ~
3 _ N _ ._ O _ . C`J C~ C ~ _ O C`J _ _ _ _ _ ~r _ _ _ _ _ _ _ _ 3 O _ _ O _~ _~ _ _~ ~1 ~ ~ _~ O O O O O O O O O O O O
~3 O O O O O O O O O O O O O O O O O O O O O O O O ~
_ D _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ H
Y u ;l OD CO _~ D __ _ _ _ _~ __ __ _._ __ __ ~ ._._ UD D .. __ _. U _._ UD C`~
~ O V O O I O C`l tLD OD n cn OD OD ~_ cn o o c~ o o c- c~ c~ ~ o~ c- o .. U _ O O O O O O O O O O O O O O O O O O ID O O O O _ 1/~ g o ~ o cn cn o o c~ _, o c~ cn ,- ~ n Ir7 w oo cn cn o cn cn o OD
a) u ~ 1/~ ~ ~ er ~r Ir~ n ~ Ir~ n ~" er 1~ ~ ~ ~r ~r ~r ~ Lo ~r ~r 1~ ~ b ~ ~ ~ - -. - - - - -. - - - - - - .- - - - - - - -- - - - ~
N V C~ C~ C~ C~ C. O O O C~ C~ N C~ O C~ ~ C. C~ O C~ C~ C~ O C. C~ ~
_ _ ~ O O O O O O O O O O O O O O O O O O O O O O O O _ U _ _ _ _ _ _ _. _ _ _ _ _ _ _ _ _ _. _ _ _ _ _ .__ _ ~ 7 ~n ~ In ~ ~ In r- In u~ In ~D '~r cn w o cn cn OD O cn co o cn cn c~ C~ C~l C~ C~ C~ C~ C~ C~ C~ C~ C~ . _ _. _.
__ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ ~ ~ C~ C~ ~ ~ ~ C~ C.~ e~, ~ ~ o o o o o o o o o ~1 ' C~ ~1 '~ ~ ~ V ~ ~ '~4 ~ ~: _.' _~ X ~7 ~ ~ ~ ~ ~ ~ V ~ _, ., ; . .'1 V~
--- - 1- - - - -I - - - - - - - ~ - - -- - - u ~ o o ~ c~ W er In ~o t--W cn I _I c~ ~ er m co t--OD cn O _I C`J W -~- c~ _ c~ c~ c~ c~ c~ _ c~ c~ :~ _ _ _ _ ~ c~ _ ~ _ ~r _ ~r _ As shown in Table 5, the light-sensitive material of the invention is excellent in graininess.
Example 3 With Example 1, amounts of example compound (E-2) used as a color developing agent were changed as listed in Table 6, whereby each sample was treated with a developing temperature listed in Table 6. Other conditions were identica] with Example 1. However, samples used i.e. light-sensitive materials Nos. 26 and 38 are identical with those prepared in Example 2. (See Table 5.) As can be understood in Table 6, a concentration of color developing agent, higher than 1.5 x 10-2 mol/liter apparently attains favorable result. In particular, a concentration of color developing agent, higher than 2.0 x 10-2 mol/liter attains more favorable result.
The similar test was performed with samples respectively using example compounds (E-1), (E-3), (E-4) and (E-8) as a color developing agent, instead of color developing agent (E-2), thereby the similar results were obtained.
t 31 7500 Table 6 Light- IColor developing ¦ Developing ¦ R M S
sensitive agent (E-2) temperature sample No. (mol/Q) (C) 26 1. 2 X 10- Z 153 4 2 . S X 10 -Z 50 3 8 2- 0 X ~ 4 7 28 l _ 3. 0 X 1 0- Z 4 5 2 5 5. 0 X 1 0~ 2 4 2 2 5 38 1. 2 X 1 0- Z 53 4 0 ~_ 1. 5 X 1 0- Z 15 o 3 5 .~ 2. 0 X 10- Z 4 7 27 . ~ 3. 0 X 1 0~ 2 4 5 2 3 .
5. 0 X 1 0~ 2 4 2 23 Developing time: 60 sec.
t 3t 7500 Example 4 Using emulsion G in Example 2, and in compliance with the preparation method in Example 1, respective samples were prepared by changing the amounts of applied silver as listed below. More specifically, by changing the amounts of silver added in the third, fifth, seventh and eighth layers, the respective samples independently having a specific amount of silver were prepared. Additionally, the layer thicknesses and amounts of silver added were modified as listed in Table 7.
Furthermore, as shown in Table 7, some samples were provided with specific layer thicknesses and T1/2:so that they consti-tuted the preferred embodiments of the invention, while the other samples were not. For each sample, the RMS value and yellow stain value are listed in Table 7. As can be under-stood, the amount of applied silver is favorably 30 mg/100 cm2, more favorably 30 to 150 mg/cm2, most favorably 35 to 100 mg/
cm2 .
1 3 1 7 5 0 () Table 7 Layer thickness Amount of applied R M S value Tl/2(mg/100 cm') . 2 0 5 7 ~ 0 . l 0 3 0 4 .5 0 . ] 1 Layer thickness is 3 5 4 t 0 . l 2 controlled to be 28 to 30 ~m; Tl/2 is 8 0 3 5 0 . 12 controlled to be 25 to 28 sec. 1 0 0 3 4 0 . 13 . - 150 33 0.13 200 33 0.14 56 0. 03 ~ 1 0.03 Layer thickness i8 3 5 3 7 0 . 0 3 controlled to be 18 . to 20 ~m~ Tl/2 is a 0 3 4 0. 0 3 controlled to be 8 to 11 sec.
. 100 33 0.04 150 32 0. 04 _ _.
___ - 200 32 0.07 ' - 290 - ~ 3 1 7500 Example 5 The following samples were treated at a temperature of 42 C with a color developing time of 60 sec, using the example compound E-2 as a color developing agent and changing the con-centration to 5 x 10-2 mol/liter. More specifically, in accord-ance with the preparation method for light-sensitive material Samples Nos. 27 and 39 in Example 1, Samples Nos. 27-1 through 27-5 and 39-1 through 39-S were prepared using the DIR com-pounds and inhibitors listed in Table 8 instead of the example DIR compound. With each sample, the RMS value and the yellow stain value were measured as in Example 4. Table 8 lists the obtained results.
Table 8 ___ ¦RMSYellow stain material DIR compound or inhibitor value value sample No .
2 7 -- 1 None 3 3 O . 12 27 - 2Dd-- 10 2~ O. 11 27- 3Dd 59 125 0.11 27-- 4 A -- 2 ¦25 O. 11 2 7 - 5 B -- 1 2 7O . 0 9 3 9 -- 1 None 3 0 O . 0 4 ._ 39 - 2 D~l-- 10 23 O . 03 39 - 3 Dd_ 59 23 O. 03 39 - 4 T - 2 23 O. 03 39- S P- 1 24 0.03 As can be understood from the results in Table 8, when a specific DIR compound or inhibitor is used, the samples of the invention attain more favorable results. More specifically, even without any of the DIR compounds or inhibitors, the samples of the invention attain considerably favorable results, while with any of the DIR compounds or inhibitors the same examples can attain much more favorable results.
With the above light-sensitive material Sample No. 39-2, even when each of Dd-2, Dd~8, Dd-12, Dd-14, Dd-16, Dd-20, Dd-23, D -27, D -30, Dd-33, Dd-36, Dd-40, Dd-44, Dd-48, Dd-52, Dd-62, Dd-66, Dd-68, Dd-72, Dd-77, Dd-80, Dd-84 and D -88 was added as a DIR compound, instead of the example compound D -10, the same results were obtalned. Additionally, with Sample No. 39-4, when each of the compounds T-1, T-3, T-5 and T-7 was added as an inhibitor instead of the example compound T-2, the same re-sults were obtained. Further, with Sample No. 39-5, when each of the compounds P-3, P-5 and P-6 was added as an inhibitor in-stead of example compound P-1, the same results were obtained.
Example 6 Light-sensitive material Sample No. 39 in Example 2 was treated using developer prepared by incorporating each of the following inhibitors into the color developer in Example 1, whereby the RMS values and yellow stain values were measured as in Example 5. The results in addition indicate that adding an inhibitor is effective.
Table 9 Inhibitor R M S Yellow . stain Compound Amount added G (magenta) ' R (cyan) I value . , None . 30 28 O .03 Z -4 30(~e/~) 27 23 ! 0 03 Z -27 20(~g/~1 27 23 1 0.03 Z-42 2.0(~g/~) 24 23 1 0 03 ... ....
Z - 20 1 2.0 ( ~ g / e ) 24 22 ! 03 Z - 1~ SO(~g/ e ) 21 22 ¦ O.U3 7, ~ 26 50(me/ Q ) 21 22 ~ 3 7. - 18 lOO(mg/ e ) 23 22 1 0.03 Z - 21 lOO(mg/ e ) 23 22 0.(~3 ~ - 28 2000(mg/ e ) 23 22 0.03 __ _ . Z - 7 50 ( m e / e ) 23 22 0.03 .
Z - 30 20 (me/ Q ) 23 22 0.03 Z - 39 20 (m~/ e ) 23 22 0.03 . _ .
Z - 65 500 (mg/ e ) 24 22 0.03 - 294 - 131750(~
Example 7 Silver iodo-bromide emulsions listed in Table 10 were prepared in accordance with the following method. Emulsions A through C were prepared using a conventional double jet pre-cipitation process. Emulsions D through K, respectively core/
shell type monodispersed emulsions, were prepared using a func-tional addition method. Emulsion L, a silver halide emulsion containing tabular particles, was prepared using a double jet precipitation process with pH and pAg being controlled.
.9.~ 75~-~
~ 1 ~' ~ ~ ~ ~ ~ ~ o 5 0-- h 0 0 O O ~ O O O o O O 0 !~ s5 u __ _ _ _-- ~ ~ ,s, .
~'o''~a) ~ v~- ~u ~ ~ ~ ~ ~D CD O O gU'~
gv- 8~ 9~ 5~ _ ~ _ _ _ _ ~s ,~ o C~-~ ~o o ~ o o 9o ,~5~ o o _ o o o o o o o o 1~
_}7 _ _ __ __ 3~33~ o lo lo ~ o~ .7 ~ ~ ~ ~ ~ o .
o I ~ ~n u~ ~ ~ u7 u~ ~ u~ u~ u~ ~ u~
3- o o o o o o o o o o o o g g -- _--a _ _ _ _ _-- S __ _ The following layers were sequentially formed, in this order, on a cellulose triacetate support, in order to prepare the respective multi-layer color film samples.
First layer: Anti-halation layer (HC layer) An anti-halation layer containing 0.18 g of black colloid-al silver, and 1.5 g of gelatin.
Second layer: Subbing layer (IG layer) A subbing layer containing 2.0 g of gelatin.
Third layer: Red-sensitive silver halide emulsion layer (R layer) A red-sensitive silver halide emulsion layer containing not only the respective silver iodo-bromide emulsions listed in Table 1 and sensitized to have red-sensitivity, but dis-persion prepared by emulsifying and dispersing 0.5 g of tri-cresyl phosphate (hereinafter referred to as TCP) having dis-solved 0.4 g of 0.08 mol/molAg of the following cyan coupler (C7-1), 0.006 mol/molAg of the following colored cyan coupler (CC7-1) and the example DIR compound, but methanol having dis-solved an inhibitor, into aqueous solution containing 1.80 g of gelatin.
Fourth layer: Intermediate layer (2G layer) An intermediate layer comprising 0.14 g of 2,5-di-t-butyl-hydroquinone, and 0.07 g of dibutyl phthalate (hereinafter re-ferred to as DBP).
Fifth layer: Green-sensitive silver halide emulsion layer 1 31 7~00 fG layer) A green-sensitive silver halide emulsion layer containing 4.0 g of the respective silver iodo-bromide emulsions listed in Table 10 and sensitized to have green-sensitivity, and dis-persion prepared by emulsifying and dispersing 0.64 g of TCP
having dissolved 0.07 mol/molAg of the following magenta couple (M7-1), 0.015 mol/molAg of the following colored magenta coupler (CM7-1) and example DIR compound (No. MDd-14), into aqueous solution containing 1.4 g of gelatin.
Sixth layer: Protective layer (3G layer) A protective layer containing 0.8 g of gelatin.
In addition to the above components, each layer was allow-ed to contain gelatin-hardening agent (1,2-bisvinylsulphonyl-ethane) and surfactant; further, into the third layer i.e. R
layer and the fifth layer i.e. G layer, the respective silver halide emulsions listed in Table 10 and the respective DIR
compounds or inhibitors listed in Table 11 were incorporated, in order to prepared samples.
Cyan coupler (C~-1) 2-(~ , y, ~ -octafluorohexanamido)5-[2-(2,4-di-t-amylphenoxy)hexanamido]phenol Colored cyan coupler (CC7-1) Disodium 1-hydroxy-4-C4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-N-[~-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide Magenta coupler (M7-1) 1-(2,4,6-trichlorophenyl)-3-{Ca-(2,4-di-t-amylphenoxy)-acetamide]benzamido}-3-pyrazolone and 1-(2,4,6-trichloropnenyl) -3-{[~-(2,4-di-t-amylphenoxy)-acetamide~benzamide}-4-(4-meth-oxyphenylazo)-5-pyrazolone Colored magenta coupler (CM-1) 1-(2,4,6-trichlorophenyl)-4-(1-naphtylazo)-3-(2-chloro-5-octadecenylsuccinimidanilino)-5-pyrazolone Each sample was exposed with green light, red light or green/red light (16 CMS) through an optical wedge, thereby treated with the following treatment steps, so as to form a dye image.
Treatment Color developing Time and temperature specifed in Table 2 and 3 (40 C) Bleach-fixing 4 min (38 C) Washing 1 min (20 to 33 C) Stabilizing 30 sec (20 to 33 C) Drying The compositions of processing solutions used in the respective processing steps are as follows.
(Color developer) Sulfate of the previously mentioned example compound (E-2) (Amount of addition specified in Table 11 or 12) Sodium sulfite anhydride 4.25 g - 299 ~ l 3175~
Hydroxylamine 1/2 sulfate 2.0 g Potassium carbonate anhydride30.0 g Sodium bromide 30.0 g Trisodium nitrilotriacetate (monohydride) 2.5 g Potassium hydroxide 1.0 g Water was added to the above components to prepare one liter solution.
(Bleach-fixer) Ferric ammonium ethylenediamine200 g tetraacetate Diammonium ethylenediamine tetraacetate 2.0 g Aqueous ammonia ~28 ~ aqueous solution) 20.0 g Ammonium thiosulfate 175.0 g Sodium sulfite anhydride 8.5 g Sodium metabisulfite 2.3 g 2-amino-5-mercapto-1,3,4-thiadiazole1.5 g Water was added to the above components to prepare one liter solution, which was adjusted to pH=6.6 using acetic acid and aqueous ammonium.
(Washing) Tap water (Stabilizer) Formalin (37 ~ aqueous solution)1.5 mQ
Konidax (manufactured by Konica Corporation) 7.5 m~
Water was added to the above components to prepare one liter solution.
Silver halide light-sensitive material sample No. 7-1 through 7-12 prepared using the above mentioned emulsions were treated with the above processing solutions and the treatment steps (wherein the concentration of color developing agent and the color developing time were varied as listed in Tables 11 and 12. Graininess (RMS value) and sharpness (MTF value) of each obtained magenta dye image are listed in Tables 11 and 12.
Incidentally, RMS values indicating graininess are obtain-ed by multiplying 1000 times standard deviations in fluctuation of density values available when scanning a dye image having a density of 1.0 by using a microdensitometer having a circular scanning aperture diameter of 25 ~m.
MTF (Modulation Transfer Function) granularities were determined by comparing degrees of MTF relative to a spatial frequency of 30 lines/mm.
Smaller RMS values of magenta dye images indicate better graininess. Larger MTF values indicate better sharpness.
DEMANDES OU BREVETS VOLlJlVllNEUX
LA PRÉSENTE PARTIE DE CETTE DEMANDE OU CE BREVET
COMPREND PLUS D'IJN TOME.
CECI EST LE TOME / DE Z
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l3/~Sc5' . ~......... ~... .......
JUMBO APPLICATIONS/PATENTS
THIS SECTION OF THE APPLICATION/PATENT CONTAINS MORE
THAN ONE VOLUME
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ce ~
HO OH
- 256 ' 1 ~1 7500 The concentration of any of the compounds expressed by the general formula [R-IV] in the color developer solution is, for example, preferably 0.1 g to 50 g per liter of the solu-tion, more preferably 0.2 g to 20 g/liter.
The color developer solution used in each of the inven-tions of the present application may contain various ingre-dients conventionally used in such a solution, for example, alkaline agents, such as sodium hydroxide and sodium carbonate, alkali metal hiocyanate, alkali metal halide, benzyl alcohol, water softener, and thickening agent, also development accel-erator and the like, other than those mentioned above, as desired.
Other additives than above mentioned which may be added to the color developer solution include an anti-stain agent, sludge preventive agent, preservative, interlayer effect pro-motor, and chelating agent.
If a compound expressed by the following general formula ~H-I3 is added to the color developer solution of this eighth invention of the present application or to the color developer solution used in any of the other inventions of the present application, tar generation in the color developer solution is inhibited and thus the object of the inventi0n can be more effectively accomplished.
General formula CH-I] ~~-R hl~
~ N O H
- 257 - ~3t7500 ' h1 and Rh2 independently represent an alkyl group or hydrogen atom, provide, however, that in no case both Rh1 and Rh2 are hydrogen atoms; Rh1 and Rh2 may bond together to form a ring.
In the general formula CH-I~, while Rh1 and Rh2 are, as above mentioned, alkyl groups or hydrogen atoms except that not both of them are hydrogen atoms, the alkyl groups expres-sed respectively by Rh1 and Rh2 may be identical with or dif-ferent from each other, being preferably alkyl groups having 1 to 3 carbon atoms. Rh1 and Rh2 may bond together to form a ring, for example, a heterocyclic ring such as piperidine or morpholine.
While various specific examples of the hydroxyamine com-pounds expressed by the general formula CH-I] are given in U.S. Patent Nos. 3,287,125, 3,293,034, and 3,287,124, parti-cularly preferred [H-I] compounds are exemplified below.
- 258 -' l3l7500 R hl ~
/ N - O H
R hZ
.. .
¦ Example compound No. R I R z H - 1 ~ C2Hs - CzHs H - 3 - C3H7 (n) - CaH7 (n) H - 4 - C,H7(i) - CaH7(i) H - 5 - CH3 - CzHs H ~ 6 - CzHs - C3R7(i) H ~ 7 ~ CH3 - C~H7(i) H - 8 _ ~ - CzHs H - 9 - H -- C3R7~n) H - 11 - H - C3H 7 (i) H ~ 12 ~ C 2 H 5 ~ CzH 4 0 C 11 3 H ~ 13 - CzH~ON - CzH~OH
H - 14 - CzH~SO 3 H - CzH 5 H - 15 - CzH4COOH - CzH~COOII
H - 16 f--~
HN N - O}l , /
H -17 f--~
HOCHzCHz- N ~ N - OH
H -18 f--~
O ~ N- OH
13175~0 CH3- N~__JN - OH
_ . I
Example compound No. R ~ R z H - 20 - CH3 - Cz114-OC113 H ~ 21 - C 2 H4-OCH3 - CzH40CI13 H - 22 - CzB4-OC 2 H~ - CzH~OCzH 5 H -23 - C3HbOCH3 - C3HbOCH3 H - 24 - CzHs -C 2 H~OCzlls H - 26 - CH3 - C 2 H~OC 2 H 5 . H - 27 - CHs ~ CHzOCH3 H -28 - CzHs - CHzOCzHs H -29 - CHzOCH3 - Cl120CII~
H - 30 - CzHs - Czll~OC~li .H -31 - C3HbOC~H7 ~ C3HbOC311, Of these, especially preferred compounds are H-I, H-2, H-8, H-9, H-12, H-18, and H-21.
These compounds are used in the form of ordinary free amine, hydrochloride, sulfate, p-toluene sulfonate, oxalate, phosphate, acetate or the like.
The concentration of the compound, represented by form-ula CH-I], in the color developer solution is usually prefer-ably 0.2 to 50 g/liter, more favorably, 0.5 to 30 g/liter, still more favorably 1 to 15 g/liter.
In the practice of any of the inventions in the present application, any known processing method for light-sensitive materials can be applied with no particular limitation, In one typical way, for example, after color developing, bleach-fixing is performed, and then washing or alternative stabili-zation processing is performed according to a specific require-ment. In another way, pre-hardening, neutralization, color developing, stop fixing, washing (or stabilization processing in place of washing), bleaching, washing (or stabilization processing in place of washing), after-hardening, and washing (or stabilization processing in place of washing) are carried out in order of mention. In another procedure, color develop-ing, washing (or stabilization processing in place of washing), supplementary color developing, stopping, bleaching, fixing, washing (or stabilization processing in place of washing), and stabilization are carried out in that order. In another devel-oping procedure, post-developed silver due to color developing is halogenation-bleached, developing is repeated to increase dye formation.
"Processing in a processing bath having bleaching ability"
means processing in a bleaching bath or a mono-bath bleach-fixing bath. The effects of the invention is advantageously attained with mono-bath bleach-fixing.
For use as bleaching agents in the bleaching solution or bleach-fixing solution in the bleaching stage, there are gene-rally known those in which metallic ions, such as iron, cobalt, or copper ions, are coordinated with organic acid, such as - 261 - ' 1317500 aminocarboxylic acid, oxalic acid, or citric acid. Typical examples of such aminocarboxylic acid are:
ethylenediamine tetraacetic acid;
diethylenetriamine pentaacetic acid;
propylenediamine tetraacetic acid;
nitrilotriacetic acidi iminodiacetic acid;
glycoletherdiamine tetraacetic acid;
ethylenediamine tetrapropionic acid;
disodium ethylenediamine tetraacetate;
pentasodium diethylenetriamine pentaacetate;
and, sodium nitrilotriacetate.
The bleaching solution and the bleach-fixing solution are used in a pH range of 0.2 to 9.5, preferably 4.0 and above, in particular, 5.0 and above. The range of processing temperatures used is 20 C to 80 C, preferably 40 ~C and above.
The bleaching solution may contain, together with afore-said bleaching agent (preferably organoacidic ferric complex salt), various additives. For this purpose, alkali halide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, and ammonium iodide, are especially preferred. Also, it is possible to add, as required, pH buffers, such as borate, oxalate, acetate, carbonate, a~d phosphate, solubilizers, such a~ triethanolamine and the like, and/or other additives, such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organophosphoric acid, oxycarboxylic acid, polycarbo-xylic acid, alkylamines, and polyethylene oxides, which are conventionally known for addition to the bleaching solution.
For the bleach-fixing bath, it is possible to use a bleach-fixing solution slightly loaded with halide, such as potassiun halide, or a bleach-fix solution of the type which is largely loaded with such halide as potassium bromide or ammonium bromide, or a special type of bleach-fixing solution composed of a combination of the bleaching agent of the inven-tion and a large amount of such halide as potassium bromide.
In addition to potassium bromide, it is possible to use other halogen compounds, such as hydrochloric acid, hydro-bromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide, and ammonium iodide.
The silver halide fixer used in the bleach-fixing bath is a compound of the type conventionally used in the process of fixing which reacts with silver halide to form a water-soluble complex salt, typical examples of which are thiosulfates, such~
as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, thiocyanates, such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, thio-ether, high-concentration bromides, and iodides. These fixers can be used within the solubility range of more than 5 g/liter, preferably more than 50 g/liter, in particular, more than 70 g/
liter.
As ~s the case with the bleaching solution, the bleach-fixing solution may contain pH buffers composed of various acids, such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bi-carbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide, either in one kind alone or in a com-bination of two or more kinds. Further, the bleach-fix bath may contain various kinds of fluorescent whitening agents, anti-foaming agents, surfactants, or anti-mordant agents.
Also, the bath may contain, as re~uired, preservatives, such as hydroxyamine, hydrazine, sulfite, isomeric bisulfite, and bisulfite adducts of aldehyde or ketone compounds; organic chelating agents, such as acetylacetone, phosphonocarboxylic acid, polycarboxylic acid, dicarboxylic acid, and aminopoly-carboxylic acid; stabilizers, such as nitro alcohol, and nitrate; solubilizers, such as alkanol amine and the like;
anti-stain agents, such as organic amine and the like, other additives; and organic solvents, such as methanol, dimethyl-formamide, and dimethylsulfoxide.
In the practice of the inventions of the present applica-tion, it is most advantageous that bleaching or bleach-fixing is performed immedi~ately after color developing; however, it is also possible that after color developing, such steps as washing or rinsing and stopping are performed, and then bleach-- 264 ~ 1 3 1 7500 ing or bleach-fixing is performed, or that a prebath contain-ing a bleach promoter may be used prior to bleaching or bleach-fixing.
In the conduct of the inventions of the present applica-tion, processing steps, other than color developing of the silver halide color photographic material e.g. bleach-fixing (or bleaching and fixing), and, where required, washing or stabilizing in place of washing are performed preferably at a temperature of 20 C to 80 C, more favorably, higher than Also, it is desirable to perform the step of stabilizing in place of washing as described in Japanese Patent O.P.I.
Publication Nos. 14834/1983, 105145/1983, 134634/1983, and 18~31/1985, and Japanese Patent Examined Publication Nos.
2709/1983 and 89288/1984.
The silver halide emulsion layers of the color pho~o-graphic light-sensitive material may contain corresponding couplers, that is, compounds which can react with an oxidation product of the color developing agent in order to form a dye.
For this purpose, except as specified for the inventions claimed herein, various kinds of yellow couplers, magenta couplers, and cyan couplers, can be used with no particular limitation. These couplers may be of the so-called two equiv-alent type or of the so-called four equivalent type. It is also possible to use any of these couplers in combination with 1~17500 a diffusible dye releasing type coupler.
For said yellow couplers, various compounds can be ef-fectively used as such, including closed-chain ketomethylene compounds; and the so-called two equivalent type couplers, such as coupler having -o-aryl substituent on the active si~e, coupler having -o-acyl substituent on the active site, coupler having hydantoin compound substituent in the active site, coupler having succinimide compound substituent in the active site, coupler having urazole compound substituent in the active site, and coupler having imide succucinate substituent in the active site, coupler having fluorine substituent in the active site, coupler having chrorine or bromine substituent in the active site, and coupler having -o-sulfonyl substituent in the active site. For the typical examples of useful yellow coupl-ers, reference is maae to those mentioned in U.S. Patent Nos.
2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072, and 3,891,445, West German Patent No. 1,547,868, West German Laid-Open Application Nos. 2,219,917, 2,261,361, and 2,414,006, British Patent No. 1,425,020, Japanese Patent Examined Publication No. 10783/1976, and Japanese Patent O.P.I.
Publication No. 26133/1972, 73147/1973, 102636/1976, 6341/1975, 123342/1975, 130442/1975, 21827/1976, 87650/1975, 82424/1977, 115219/1977, and 95346/1983.
For magenta couplers, except as specifically mentioned with respect to the general formula [rl-I], or in conjunction with the CM-I] couplers, compounds of the following types may be mentioned: pyrazolone, pyrazolotriazole, pyrazolinobenz-imidazole, and indazolone. As is the case with the yellow couplers, these magenta couplers can be not only of the 4 equivalent type but also of the 2 equivalent type. For typic-al examples of useful magenta couplers, reference is made to those mentioned in V.S. Patent Nos. 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,746, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908, and 3,891,445, German Patent No. 1,810,464, German Laid-Open Specification Nos. 2,408,665, 2,417,945, 2,148,959, and 2,424,467, Japanese Patent examined Publication No. 6031/1965, Japanese Patent O.P.I. Publication Nos. 20826/1976, 58922/1977, 129538/1974, 74027/1974, 159336/1975, 42121/1977, 74028/1974, 60233/1975, 26541/1976, and 55122/1978, and Japanese Patent Application No. 110943/1980.
For useful cyan couplers, as specifically mentioned with respect to the general formula CC-I], or in conjunction with the CC-I] couplers, phenolic and naphtolic couplers may be mentioned. These cyan couplers, as is the case with the yel-low~couplers, may be either of the 4 equivalent type or of the 2 equivalent type. For typical examples of cyan couplers, re-ference is made to those mentioned in U.S. Patent Nos.
2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383, 3,767,411, 3,772,002, 3,933,494, and 4,004,929, German Laid-Open Specification Nos. 2,414,830, and 2,454,329, Japanese Patent ~.P.I. Publication No. 59838/1973, 26034/1976 5055/1973, 146827/1976, 69624/1977, 90932/1977, and 95346/
1983, and Japanese Patent Examined Publication No. of 11572/
1974.
The silver halide emulsion layers and other structural layers of the photographic light-sensitive material may simultaneously contain colored magenta or cyan coupler, and other couplers such as polymer coupler. For colored magenta or cyan couplers, reference is made to the relevant descrip-tion in Japanese Patent Application No. 1193611/1984 of the present applicant, and for the above-mentioned polymer coupl-ers, reference is made to the relevant description in Japanese Patent Application No. 172151/1984 of the applicant.
Aforesaid couplers may be added to the photographic structural layers according to a conventional procedure. The amount of the coupler to be added, though not definite, is preferably 1 x 10-3 to 5 mol, in particular, 1 x 10-2 to 10~
mol per mol silver.
In the practice of the inventions of the present applica-tion, various other photographic additives may be incorporated into the islver hlide color photographic light-sensitive mate-rial. For example, various agents mentioned in "Reseach Dis-closure" No. 17643, such as antifoggant, stabilizer, ultra~
~- - 268 - 1 31 7 5~0 violet absorbent, anti-stain agent, fluorescent whitening agent, dye-image stabilizer, antistatic aget, hardening agent, surfactant, plasticizer, and wetting agent, may be used.
In the silver halide color photographic light-sensitive material, the hydrophilic colloid used for emulsion prepara-tion contains any of the following: gelatin, gelatin deriva-tive, graft polymers of gelatin with other polymer; proteins, such as albumine and casein; cellulose derivatives, such as hydroxyethyl cellulose derivatives and carboxymethyl cellu-lose: starch derivatives; and synthesized hydrophilic mono-and/or co-polymers, such as polyvinyl alcohol, polyvinyl imidazole, and polyacrylamide.
As the support of the silver halide color photographic light-sensitive material, there may be mentioned, for example, glass plate; polyester film made of cellulose acetate, cellu-lose nitrate, polyethylene terephthalate; polyamide film, polycarbonate film, and polystyrene film. These base materials can be selectively used according to the purpose for which the light-sensitive material is used.
According to the intended use, it is possible to provide an intermediate layer of a suitable thickness. Further, vari-ous layers, such as filter layer, anticurl layer, protective layer, and antihalation layer, may be suitably used in combi-nation. any hydrophilic colloid which can be used as binder in aforesaid emulsion layer can be similarly used in these - 269 ~ 1 31 7500 structural layers. These layers may contain such various photographic additives as are used in aforesaid emulsion layer.
The processing method of the present invention is ap-plicable to silver halide color photographic light-sensitive materials, such as color negative film, color positive film, slide color reversal film, cinema color reversal film, and TV color reversal film.
BRIEF DESCRIPTION OF DRAWING
Fig. 1 is a graph used ~o explain the layer swelling rate, in disclosing the present invention.
EXAMPLES
The typical examples of the invention are described as follows. However, the scope of embodiments of the invention is not limited only to these examples.
With each of the following examples, the amount of addi-tion to a silver halide photographic light-sensitive material, unless otherwise specified, is expressed by an amount per m2 light-sensitive material, and the amount of ~ilver halide or colloidal silver means the converted value representing equiv-alent silver.
Example 1 Standard light sensitive material B was prepared by the following process.
In accordance with the layer constitution commonly used in the photographic art, a black colloidal silver anti-hala-tion layer, red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer were sequentially formed upon a support (triacetate film base) in this order, incorporating various auxiliary layers between arbitrary adjacent layers, whereby, upon the above blue-sensitive silver halide emulsion layer, was disposed a high sensitivity monodispersed silver halide emulsion layer, thus preparing light-sensitive mate-rial B, wherein the amount of silver applied was 53 mg/100 cm2 and the thickness of dried layers was 23 m.
First layer: An anti-halation layer formed by applying dispersion prepared by first reducing silver nitrate using a hydroquinone as a reductant to obtain a black colloidal silver featuring a high absorptivity toward light having a wavelen~th of 400 to 700 nm, and then dispersing 0.8 g of this colloidal silver into 3 g of gelatin.
Second layer: An intermediate layer comprising gelatin Third layer: A low-sensitivity red-sensitive silver halide emulsion layer containing 1.5 g of low-sensitivity red-sensitive silver iodo-bromide emulsion (AgI; 7 mol%), 1.6 g of gelatin; as well as 0.4 g of tricresyl phosphate (here-inafter referred to as TCP) having dissolved 0.85 g of 1-- 271 - 1 31 7 ~ 00 hydroxy-4-(~-methoxyethylaminocarbonylmethoxy)-N-[~-(2,4-di-t- amylphenoxy)butyl]-2-naphthamide (hereinafter referred to as cyan coupler (C'-0), 0.030 g of disodium 1-hydroxy-4-C4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazoOphenoxy]-N-C~-~2,4-di-amylphenoxy)butyl]-2-naphthamide (hereinafter referred to as colored cyan coupler (CC'-1)).
Fourth layer: A high-sensitivity red-sensitive silver halide emulsion layer containing 1.1 g of high-sensitivity red-sensitive silver iodo-bromide emulsion (AgI; 6 mol~), 1.2 g of gelatin; as well as 0.17 g of TCP having dissolved 0.25 g of cyan coupler (C'-0), and 0.020 g of colored cyan coupler (CC ' - 1 ) .
Fifth layer: An intermediate layer containing 0.04 g of dibutyl phthalate (hereinafter referred to as DBP) having dis-solved 0.07 g of 2,5-di-t-octylhydroquinon~ (hereinafter re-ferred to as anti-stain agent ~HQ'-1)); as well as 1.2 g of gelatin.
Sixth layer: A low-sensitivity green-sensitive silver halide emulsion layer containing 1;6 g of low-sensitivity green-sensitive silver iodo-bromide emulsion (AgI; 6 mol~), 1.7 g of gelatin; as well as 0.3 g of TCP having dissolved three types of couplers i.e. 0.32 g of 1-(2,4,6-trichloro-phenyl)-3-~3-(2,4-di-t-amylphenoxyacetamido)benzenamido]-5-pyrazolone (hereinafter referred to magenta coupler (M'-1)), 0.20 g of 4,4-methylenebis-11-(2,4,6-trichlorophenyl)-3-C3-- 272 ~ 1 ~ t 7500 12,4-di-t-amylphenoxyacetamido)benzenamido]-5-pyrazolone (hereinafter referred to as magenta coupler (M'-2)) and 0.066 g of 1-(2,4,6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidanilino)- 5-pyrazolone (hereinafter referred to as colored magenta coupler (CM'-1).
Seventh layer: A high-sensitivity green-sensitive silver halide emulsion layer containing 1.5 g of high-sensitivity green-sensitive silver iodo-bromide emulsion (AgI; 8 mol%), 1.9 g of gelatin; as well as 0.12 g of TCP having dissolved 0.10 g of magenta coupler (M'-1), 0.098 g of magenta coupler (M'-2), and 0.049 g of colored magenta coupler (CM'-1).
Eighth layer: A yellow filter layer containing 0.2 g of yellow colloidal silver; 0.11 g of DBP having dissolved 0.2 g of anti-stain agent (HQ'-1); as well as 2.1 g of gelatin.
Ninth layer: A low-sensitivity blue-sensitive silver halide emulsion layer containing 0.95 g of low-sensitivity blue-sensitive silver iodo-bromide emulsion (AgI; 7 mol%), 1.9 g of gelatin; as well as 0.93 g of DBP having dissolved 1.84 g of ~-C4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolydinyl)]-~-pyvaloyl-2-chloro-5-[~-(2,4-di-t-amylphenoxy)butanamido]~;cet-anilide (hereinafter referred to as yellow coupler (Y'-1)).
Tenth layer: A high-sensitivity blue-sensitive silve;
halide emulsion layer containing 1.2 g of high-sensitivity monodispersed blue-sensitive iodo-bromide emulsion (AgI; 6 mol%), 2.0 g of gelatin; as well as 0.23 g of DBP having ~ 273 -t 3 ~ ~500 dissolved 0.46 g of yellow coupler (Y'-1).
Eleventh layer: The second protective layer comprising gelatin.
Twelfth layer: The first intermediate layer containing 2.3 g of gelatin.
this light-sensitive material B was exposed under the following exposure conditions using a tungsten light source and filter, whereby a color temperature was adjusted to 4800 K, in order to provide 3,2 CMS wedge exposure light.
(Exposure condit1Ons C) The exposured light-sensitive material B was subjected to color developing at a temperature of 38 C with a duration of 3 min. 15 sec. by using developer A. :[n this course, the maximum magenta dye density M of light-sensitive material B
in terms of a maximum transmitting density was 1.80, which was measured with a SAKURA photoelectric densitometer PDA-65 manu-factured by Konica Corporation).
Developer A
Potassium carbonate 37.5 g Sodium sulfite 4.25 g Potassium iodide 2 mg Sodium bromide 1.3 g Hydroxylamine sulfate 2.0 g 3-methyl-4-amino-N-ethyl-N-(~-hydroxyethyl)-4.75 g aniline sulfate * Trade mark.
B
.
- 274 - ~ ~1 7~ 00 LWater was added to the above components to prepare one liter solution, which was adjusted to pH 10.0 with 45 ~ potas-sium hydroxide or 50 % sulfuric acid.
Next, samples were prepared as follows.
Silver halide emulsions in Table 1 i.e. emulsions con-taining spherical silver halide particles were prepared using a conventional double-jet precipitation process.
The following layers were sequentially formed, in this order, on a cellulose triacetate support, to prepare a multi-layer color film sample.
First layer: Anti-halation layer (HC layer) An anti-halation layer containing 0.18 g of black colloid-al silver, and 1.5 g of gelatin.
Second layer: Subbing layer (IG layer) A subbing layer containing 2.0 g of gelatin.
Third layer: Red-sensitive silver halide emulsion layer ~R layer).
A red-sensitive silver halide emulsion layer containing not only each of the silver halide emulsions listed in Table 1 and sensitized to have red-sensitivity, but dispersion pre-pared by emulsifying and dispersing tricresyl phosphate (here-inafter referred to as TCP) having dissolved 0.2 mol/molAg of the following cyan coupler (C-1), 0.006 mol/molAg of the follow-ing colored cyan coupler (CC-1) and the example DIR compound (No. D-24), but methanol having dissolved an inhibitor, into - 275 ~ 1 3 t 75 0 0 aqueous solution containing gelatin.
Fourth layer: Intermediate layer (2G layer) An intermediate layer comprising 0.14 g of 2,5-di-t-butylhydroquinone, and 0.07 g of dibutyl phthalate (herein-after referred to as DBP).
Fifth layer: Green-sensitive silver halide emulsion layer (G layer) A green-sensitive silver halide emulsion layer containing not only each of the silver halide emulsions listed in Table 1 and sensitized to have green-sensitivity, but dispersion pre-pared by emulsifying and dispersing TCP having dissolved 0.15 mol/molAg of the follwing magenta coupler (m-1), 0.015 mol/
molAg of the following colored magenta coupler (CM-1) and the example DIR compound (No. D-5), into aqueous solution contain-ing gelatin.
Sixth layer: Yellow filter layer A yellow filter layer containing 0.3 g ye~low colloidal silver, and 0.11 g of DBP having dissolved 0.2 g anti-stain agent (2,5-di-t-octylhydroquinone); as well as 2.1 g bf gelatin.
Seventh layer: Low-sensitivity blue-sensitive silver halide emulsion layer (B layer) A blue-sensitive silver halide emulsion layer containing not only each of the silver halide emulsions listed in Table 1 and sensitized to have blue-sensitivity, but dispersion pre-pared by emulsifying and dispersing TCP having dissolved 0.3 - 276 - t 31 75 on mol/molAg of the following yellow coupler (Y-1) and the example DIR compound (No. D-62), into aqueous solution containing gel-atin.
Eighth layer: High-sensitivity monodispersed blue-sensi-tive silver halide emulsion layer (B layer) A layer similar to the seventh layer, except that slightly larger silver halide particles were used.
Ninth layer: Protective layer (3G layer) A protective layer containing 0.8 g of gelatin In addition to the above components, each layer was allow-ed to contain gelatin-hardening agents (1,2-bisvinylsulphonyl-ethane and sodium 2,4-dichloro-y-hydroxy-s-triadine), surfact-ant and the like.
The amount of silver applied was 50 mg/100 cm2.
The couplers used in the respective layers were as follows.
Cyan coupler (Cl-1) 2-~ , y, ~ -octafluorohexanamide)5-[2-(2,4-di-t-amylphenoxy)hexanamide]phenol Colored cyan coupler (CC1-1) Disodium 1-hydroxy-4-C4-(1-hydroxy-8-acetamide-3,6-disulfo-2-naphthylazo)phenoxy]-N-C~-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide Magenta coupler (Ml-1) 1-(2,4,6-trichlorophenyl)-3-{C2,4-di-t-amylphenoxy)-acet-amido]benzamido}-3-pyrazolone and 1-(2,4,6-trichlorophenyl)-1 3 ~ 7~00 3-{C~-(2,4-di-t-amylphenoxy)}-acetamide]benzamido-4-(4-meth-oxyphenylazo)-5-pyrazolone Colored magenta coupler (CM~
1-(2,4,6-trichlorophenyl)-4~ naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidanilino)-5-pyrazolone Yellow coupler (Yl-1) -~ -C4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolydinyl-~-pyvaloyl-2-chloro-5-Cy-(2,4-di-t-amylphenoxy)butanamido]acet-anilide Samples 1 through 19 were prepared respectively using the above specified compositions specified in Table 1 as the com-position of silver halide, and varying the amounts of applica-tion in the third, fi~th, sixth and seventh layers, varying the amount of gelatin-hardening agent in the eighth layer and add-ing gelatin-hardening agent into the blue-sensitive silver halide emulsion layer so as to reduce T1/2 of certain samples.
Next, the layer thicknesses, as well as layer swelling rates T1/2, were measured. Table 1 lists the measurement results.
Each sample was exposed with green light, red light or green/red light (16 CMS) through an optical wedge, thereby treated with the following treatment steps, so as to form a dye image.
Treatment Color developing Time and temperature specified in Table 2 Bleaching 4 min (38 C) 1 3 ~ 750~
Fixing 3 min (30 to 38 C) Washing 1 min (20 to 33 C) Stabilizing 1 min (20 to 33 C~
Drying The compositions of processing solutions used in the respective processing steps are as follows.
(Color developer) Sulfate of the previously mentioned 3 x 10-2 mol example compound (E-2) Sodium sulfite anhydride 4.25 g Hydroxylamine - 1/2 sulfate2.0 g Potassium carbonate anhydride30.0 g Sodium bromide 1.3 g Trisodium nitrilotriacetate (monohydride) 2.5 g Potassium hydroxide 1.0 g Inhibitor (Z-5) 0-5 g Water was added to the above components to prepare one liter solution, which was adjusted to pH=10.2 using 50 ~ KOH
and 50 ~ H2SO4.
(Bleacher) Ferric (III) ammonium ethylene-200 g diamine tetraacetate Ammonium bromide 150.0 g Glacial acetic acid 10.0 mQ
Water was added to the above components to prepare one liter solution, which was adjusted to pH=6.0 using aqueous ammonium and acetic acid.
(Fixer) Ammonium thiosulfate 175.0 g Sodium sulfite anhydride 8.5 g Sodium metabisulfite 2.3 g Water was added to the above components to prepare one liter solution, which was adjusted to p~=7.0 using acetic acid.
(Stabilizer) Formalin (37 % aqueous solution) 1.5 mQ
Konidax (manufactured by Knonica Corporation) 7.5 mQ
Water was added to the above components to prepare one liter solution.
Graininess (RMS) of each obtained cyan dye is listed in Table 2. Incidentally, the addition of DIR compound into each color-sensitive layer was controlled so that the layer may indicate the same degree of desensitization and density de-crease.
Using the above processing solutions and the above treat-ment steps, the above standard light-sensitive material B hav-ing been exposed under the above mentioned exposure conditions was treated at a temperature of 40 C with a color developing time of 2 minutes, whereby the minimum transmitting magenta dye density was 2.2 and the magenta density in non-exposed areas was 0.38.
- 280'- 1317500 Table 1 ~ight- S$ Lver hal$de thic~- Layer swelling, mater$a L Ag I AgBr AgC e ~ m Tl/2 (sec) l _ 100 _ 20 12 _ 2 _ 90 10 20 12 3 0.~ 90 1 9.5 20 12 _ 0.5 89.7 9.8 30 2a . 5 0.5 99.5 _ 30 16 ~ 0.5 99.5 _ 20 16 7 6.0 1 94 _ 20_ 5 8 6.0 1 94 _ 20 t~
: 9 6.0 94 Z~ 16 6.0 94 _ 20 2U
11_ 6.0 94 _ 20 25 12 6.0 9~ _ 20 30 13 G.0 94 15 14 6.0 94 _ 1~ 11 _ 6.0 94 _ 22 10 16 G.0 94 _ 25 11 17 6.0 94 _ 2~ 13 l~ 6.0 94 1 _ 31 13 19 6.0 94 1 _ 35 14 - 281 ~ t 31 7soa Table 2 Graininess (RMS values) time ~sec) i 2 1 0 ( ~ 180 ¦lS a 1 2 0 9 0 fi () Color developing 3 3 ( C )¦ 3 5 ¦ 3 7 . 5 4 42 ----_ 52 150 48 46 4~ .ll I
2 53 51 49 49 48 1 5u 3 49 ,!6 47 46 46 4 47 45 1 ~2 13~ ! 33 32 146 4~ 1 ~7 133 ! 32 31 6 146 38 1 36 13~ 1 33 32 o l z 7 145 3~ 1 ~0 129 1 26 1 25 8 4~ 34 1 31 130 26 25 . 9 46 36 1 33 31 29 27 3 '15 31 30 28 25 25 1~ ~5 3 3 31 29 25 25 _ lS 47 35 32 35 27 26 16 ~8 39 35 34 30 2 . 1~ 149 46 4~ 39 39 3~
Gralniness: Smaller RMS values are more advantegous. Values enclosed ln heavv lines correspond wlth preferred embodiments of the lnventlon.
- 282 - t 31 7 5 00 As can be understood from the results in Table 2, satisfactory graininess is obtained, when using each of the light-sensitive materials 3 through 19 and the treatment steps of the invention. Further, it is apparent that a sample with a layer thickness (i.e. a thickness of dried layers determined by subtracting a thickness of support from the whole layer thickness) of less than 25 ~m is more satisfactory, and that sample with a layer swelling rate (T1/2) of less than 20 sec is more satisfactory, and that samples treated with a color developing time of 180 seconds shoed satisfactory results;
samples treated with a color developing time of shorter than 120 seconds showed especially excellent results.
Example 2 Silver iodo-bromide emulsions listed in Table 4 were prepared in accordance with the following method. Emulsion A through C were prepared using a conventional double jet precipitation process. Emulsions D through K, respectively core/shell type monodispersed emulsions, were prepared using a functional addition method. Emulsion L, a silver halide emulsion containing tabular particles, was prepared using a double jet precipitation process with pH and pAg being cont-rolled.
Next, using the above emulsions A through L, light-sensi-tive material Samples Nos. 20 through 43 respectively having layer thicknesse~ listed in Table 4 were prepared in compliance - 283 ~ l 3 ~ 75 00 with the preparation method for a light-sensitive material in Example 1.
Each sample was tested in a manner identical with Example 1. The obtained data with regards to graininess (RMS value) and yellow-stain are listed in Table 5.
~ T~ ~ s ~ 3~ ~9 .~, a~ ~1~ ~ 3 .~
l ,~}1 A ~ ~ o _ _ o o o o o e~
E~ ~t ,m 0~ cq u~ c~ u~ o o o o l~u ~ L~-~ ~ rl ~
~ i~i W ~o _ IA W C ~0 r- ~`1 CO 1_ '7 O
3~ ~ ~ ~ ~ ~ o~ ~ ~ x ~
1 31 750() -- 28~ --_ . .
---- b C~t ~ ,_ C~J C`l O ~ ~O C`l l_ _ C`~ OD ell C'~ OO C`l __ C`l C`l C`l C~ __ .. _. __ _ ~J ~
3 _ N _ ._ O _ . C`J C~ C ~ _ O C`J _ _ _ _ _ ~r _ _ _ _ _ _ _ _ 3 O _ _ O _~ _~ _ _~ ~1 ~ ~ _~ O O O O O O O O O O O O
~3 O O O O O O O O O O O O O O O O O O O O O O O O ~
_ D _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ H
Y u ;l OD CO _~ D __ _ _ _ _~ __ __ _._ __ __ ~ ._._ UD D .. __ _. U _._ UD C`~
~ O V O O I O C`l tLD OD n cn OD OD ~_ cn o o c~ o o c- c~ c~ ~ o~ c- o .. U _ O O O O O O O O O O O O O O O O O O ID O O O O _ 1/~ g o ~ o cn cn o o c~ _, o c~ cn ,- ~ n Ir7 w oo cn cn o cn cn o OD
a) u ~ 1/~ ~ ~ er ~r Ir~ n ~ Ir~ n ~" er 1~ ~ ~ ~r ~r ~r ~ Lo ~r ~r 1~ ~ b ~ ~ ~ - -. - - - - -. - - - - - - .- - - - - - - -- - - - ~
N V C~ C~ C~ C~ C. O O O C~ C~ N C~ O C~ ~ C. C~ O C~ C~ C~ O C. C~ ~
_ _ ~ O O O O O O O O O O O O O O O O O O O O O O O O _ U _ _ _ _ _ _ _. _ _ _ _ _ _ _ _ _ _. _ _ _ _ _ .__ _ ~ 7 ~n ~ In ~ ~ In r- In u~ In ~D '~r cn w o cn cn OD O cn co o cn cn c~ C~ C~l C~ C~ C~ C~ C~ C~ C~ C~ C~ . _ _. _.
__ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ~ ~ ~ C~ C~ ~ ~ ~ C~ C.~ e~, ~ ~ o o o o o o o o o ~1 ' C~ ~1 '~ ~ ~ V ~ ~ '~4 ~ ~: _.' _~ X ~7 ~ ~ ~ ~ ~ ~ V ~ _, ., ; . .'1 V~
--- - 1- - - - -I - - - - - - - ~ - - -- - - u ~ o o ~ c~ W er In ~o t--W cn I _I c~ ~ er m co t--OD cn O _I C`J W -~- c~ _ c~ c~ c~ c~ c~ _ c~ c~ :~ _ _ _ _ ~ c~ _ ~ _ ~r _ ~r _ As shown in Table 5, the light-sensitive material of the invention is excellent in graininess.
Example 3 With Example 1, amounts of example compound (E-2) used as a color developing agent were changed as listed in Table 6, whereby each sample was treated with a developing temperature listed in Table 6. Other conditions were identica] with Example 1. However, samples used i.e. light-sensitive materials Nos. 26 and 38 are identical with those prepared in Example 2. (See Table 5.) As can be understood in Table 6, a concentration of color developing agent, higher than 1.5 x 10-2 mol/liter apparently attains favorable result. In particular, a concentration of color developing agent, higher than 2.0 x 10-2 mol/liter attains more favorable result.
The similar test was performed with samples respectively using example compounds (E-1), (E-3), (E-4) and (E-8) as a color developing agent, instead of color developing agent (E-2), thereby the similar results were obtained.
t 31 7500 Table 6 Light- IColor developing ¦ Developing ¦ R M S
sensitive agent (E-2) temperature sample No. (mol/Q) (C) 26 1. 2 X 10- Z 153 4 2 . S X 10 -Z 50 3 8 2- 0 X ~ 4 7 28 l _ 3. 0 X 1 0- Z 4 5 2 5 5. 0 X 1 0~ 2 4 2 2 5 38 1. 2 X 1 0- Z 53 4 0 ~_ 1. 5 X 1 0- Z 15 o 3 5 .~ 2. 0 X 10- Z 4 7 27 . ~ 3. 0 X 1 0~ 2 4 5 2 3 .
5. 0 X 1 0~ 2 4 2 23 Developing time: 60 sec.
t 3t 7500 Example 4 Using emulsion G in Example 2, and in compliance with the preparation method in Example 1, respective samples were prepared by changing the amounts of applied silver as listed below. More specifically, by changing the amounts of silver added in the third, fifth, seventh and eighth layers, the respective samples independently having a specific amount of silver were prepared. Additionally, the layer thicknesses and amounts of silver added were modified as listed in Table 7.
Furthermore, as shown in Table 7, some samples were provided with specific layer thicknesses and T1/2:so that they consti-tuted the preferred embodiments of the invention, while the other samples were not. For each sample, the RMS value and yellow stain value are listed in Table 7. As can be under-stood, the amount of applied silver is favorably 30 mg/100 cm2, more favorably 30 to 150 mg/cm2, most favorably 35 to 100 mg/
cm2 .
1 3 1 7 5 0 () Table 7 Layer thickness Amount of applied R M S value Tl/2(mg/100 cm') . 2 0 5 7 ~ 0 . l 0 3 0 4 .5 0 . ] 1 Layer thickness is 3 5 4 t 0 . l 2 controlled to be 28 to 30 ~m; Tl/2 is 8 0 3 5 0 . 12 controlled to be 25 to 28 sec. 1 0 0 3 4 0 . 13 . - 150 33 0.13 200 33 0.14 56 0. 03 ~ 1 0.03 Layer thickness i8 3 5 3 7 0 . 0 3 controlled to be 18 . to 20 ~m~ Tl/2 is a 0 3 4 0. 0 3 controlled to be 8 to 11 sec.
. 100 33 0.04 150 32 0. 04 _ _.
___ - 200 32 0.07 ' - 290 - ~ 3 1 7500 Example 5 The following samples were treated at a temperature of 42 C with a color developing time of 60 sec, using the example compound E-2 as a color developing agent and changing the con-centration to 5 x 10-2 mol/liter. More specifically, in accord-ance with the preparation method for light-sensitive material Samples Nos. 27 and 39 in Example 1, Samples Nos. 27-1 through 27-5 and 39-1 through 39-S were prepared using the DIR com-pounds and inhibitors listed in Table 8 instead of the example DIR compound. With each sample, the RMS value and the yellow stain value were measured as in Example 4. Table 8 lists the obtained results.
Table 8 ___ ¦RMSYellow stain material DIR compound or inhibitor value value sample No .
2 7 -- 1 None 3 3 O . 12 27 - 2Dd-- 10 2~ O. 11 27- 3Dd 59 125 0.11 27-- 4 A -- 2 ¦25 O. 11 2 7 - 5 B -- 1 2 7O . 0 9 3 9 -- 1 None 3 0 O . 0 4 ._ 39 - 2 D~l-- 10 23 O . 03 39 - 3 Dd_ 59 23 O. 03 39 - 4 T - 2 23 O. 03 39- S P- 1 24 0.03 As can be understood from the results in Table 8, when a specific DIR compound or inhibitor is used, the samples of the invention attain more favorable results. More specifically, even without any of the DIR compounds or inhibitors, the samples of the invention attain considerably favorable results, while with any of the DIR compounds or inhibitors the same examples can attain much more favorable results.
With the above light-sensitive material Sample No. 39-2, even when each of Dd-2, Dd~8, Dd-12, Dd-14, Dd-16, Dd-20, Dd-23, D -27, D -30, Dd-33, Dd-36, Dd-40, Dd-44, Dd-48, Dd-52, Dd-62, Dd-66, Dd-68, Dd-72, Dd-77, Dd-80, Dd-84 and D -88 was added as a DIR compound, instead of the example compound D -10, the same results were obtalned. Additionally, with Sample No. 39-4, when each of the compounds T-1, T-3, T-5 and T-7 was added as an inhibitor instead of the example compound T-2, the same re-sults were obtained. Further, with Sample No. 39-5, when each of the compounds P-3, P-5 and P-6 was added as an inhibitor in-stead of example compound P-1, the same results were obtained.
Example 6 Light-sensitive material Sample No. 39 in Example 2 was treated using developer prepared by incorporating each of the following inhibitors into the color developer in Example 1, whereby the RMS values and yellow stain values were measured as in Example 5. The results in addition indicate that adding an inhibitor is effective.
Table 9 Inhibitor R M S Yellow . stain Compound Amount added G (magenta) ' R (cyan) I value . , None . 30 28 O .03 Z -4 30(~e/~) 27 23 ! 0 03 Z -27 20(~g/~1 27 23 1 0.03 Z-42 2.0(~g/~) 24 23 1 0 03 ... ....
Z - 20 1 2.0 ( ~ g / e ) 24 22 ! 03 Z - 1~ SO(~g/ e ) 21 22 ¦ O.U3 7, ~ 26 50(me/ Q ) 21 22 ~ 3 7. - 18 lOO(mg/ e ) 23 22 1 0.03 Z - 21 lOO(mg/ e ) 23 22 0.(~3 ~ - 28 2000(mg/ e ) 23 22 0.03 __ _ . Z - 7 50 ( m e / e ) 23 22 0.03 .
Z - 30 20 (me/ Q ) 23 22 0.03 Z - 39 20 (m~/ e ) 23 22 0.03 . _ .
Z - 65 500 (mg/ e ) 24 22 0.03 - 294 - 131750(~
Example 7 Silver iodo-bromide emulsions listed in Table 10 were prepared in accordance with the following method. Emulsions A through C were prepared using a conventional double jet pre-cipitation process. Emulsions D through K, respectively core/
shell type monodispersed emulsions, were prepared using a func-tional addition method. Emulsion L, a silver halide emulsion containing tabular particles, was prepared using a double jet precipitation process with pH and pAg being controlled.
.9.~ 75~-~
~ 1 ~' ~ ~ ~ ~ ~ ~ o 5 0-- h 0 0 O O ~ O O O o O O 0 !~ s5 u __ _ _ _-- ~ ~ ,s, .
~'o''~a) ~ v~- ~u ~ ~ ~ ~ ~D CD O O gU'~
gv- 8~ 9~ 5~ _ ~ _ _ _ _ ~s ,~ o C~-~ ~o o ~ o o 9o ,~5~ o o _ o o o o o o o o 1~
_}7 _ _ __ __ 3~33~ o lo lo ~ o~ .7 ~ ~ ~ ~ ~ o .
o I ~ ~n u~ ~ ~ u7 u~ ~ u~ u~ u~ ~ u~
3- o o o o o o o o o o o o g g -- _--a _ _ _ _ _-- S __ _ The following layers were sequentially formed, in this order, on a cellulose triacetate support, in order to prepare the respective multi-layer color film samples.
First layer: Anti-halation layer (HC layer) An anti-halation layer containing 0.18 g of black colloid-al silver, and 1.5 g of gelatin.
Second layer: Subbing layer (IG layer) A subbing layer containing 2.0 g of gelatin.
Third layer: Red-sensitive silver halide emulsion layer (R layer) A red-sensitive silver halide emulsion layer containing not only the respective silver iodo-bromide emulsions listed in Table 1 and sensitized to have red-sensitivity, but dis-persion prepared by emulsifying and dispersing 0.5 g of tri-cresyl phosphate (hereinafter referred to as TCP) having dis-solved 0.4 g of 0.08 mol/molAg of the following cyan coupler (C7-1), 0.006 mol/molAg of the following colored cyan coupler (CC7-1) and the example DIR compound, but methanol having dis-solved an inhibitor, into aqueous solution containing 1.80 g of gelatin.
Fourth layer: Intermediate layer (2G layer) An intermediate layer comprising 0.14 g of 2,5-di-t-butyl-hydroquinone, and 0.07 g of dibutyl phthalate (hereinafter re-ferred to as DBP).
Fifth layer: Green-sensitive silver halide emulsion layer 1 31 7~00 fG layer) A green-sensitive silver halide emulsion layer containing 4.0 g of the respective silver iodo-bromide emulsions listed in Table 10 and sensitized to have green-sensitivity, and dis-persion prepared by emulsifying and dispersing 0.64 g of TCP
having dissolved 0.07 mol/molAg of the following magenta couple (M7-1), 0.015 mol/molAg of the following colored magenta coupler (CM7-1) and example DIR compound (No. MDd-14), into aqueous solution containing 1.4 g of gelatin.
Sixth layer: Protective layer (3G layer) A protective layer containing 0.8 g of gelatin.
In addition to the above components, each layer was allow-ed to contain gelatin-hardening agent (1,2-bisvinylsulphonyl-ethane) and surfactant; further, into the third layer i.e. R
layer and the fifth layer i.e. G layer, the respective silver halide emulsions listed in Table 10 and the respective DIR
compounds or inhibitors listed in Table 11 were incorporated, in order to prepared samples.
Cyan coupler (C~-1) 2-(~ , y, ~ -octafluorohexanamido)5-[2-(2,4-di-t-amylphenoxy)hexanamido]phenol Colored cyan coupler (CC7-1) Disodium 1-hydroxy-4-C4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-N-[~-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide Magenta coupler (M7-1) 1-(2,4,6-trichlorophenyl)-3-{Ca-(2,4-di-t-amylphenoxy)-acetamide]benzamido}-3-pyrazolone and 1-(2,4,6-trichloropnenyl) -3-{[~-(2,4-di-t-amylphenoxy)-acetamide~benzamide}-4-(4-meth-oxyphenylazo)-5-pyrazolone Colored magenta coupler (CM-1) 1-(2,4,6-trichlorophenyl)-4-(1-naphtylazo)-3-(2-chloro-5-octadecenylsuccinimidanilino)-5-pyrazolone Each sample was exposed with green light, red light or green/red light (16 CMS) through an optical wedge, thereby treated with the following treatment steps, so as to form a dye image.
Treatment Color developing Time and temperature specifed in Table 2 and 3 (40 C) Bleach-fixing 4 min (38 C) Washing 1 min (20 to 33 C) Stabilizing 30 sec (20 to 33 C) Drying The compositions of processing solutions used in the respective processing steps are as follows.
(Color developer) Sulfate of the previously mentioned example compound (E-2) (Amount of addition specified in Table 11 or 12) Sodium sulfite anhydride 4.25 g - 299 ~ l 3175~
Hydroxylamine 1/2 sulfate 2.0 g Potassium carbonate anhydride30.0 g Sodium bromide 30.0 g Trisodium nitrilotriacetate (monohydride) 2.5 g Potassium hydroxide 1.0 g Water was added to the above components to prepare one liter solution.
(Bleach-fixer) Ferric ammonium ethylenediamine200 g tetraacetate Diammonium ethylenediamine tetraacetate 2.0 g Aqueous ammonia ~28 ~ aqueous solution) 20.0 g Ammonium thiosulfate 175.0 g Sodium sulfite anhydride 8.5 g Sodium metabisulfite 2.3 g 2-amino-5-mercapto-1,3,4-thiadiazole1.5 g Water was added to the above components to prepare one liter solution, which was adjusted to pH=6.6 using acetic acid and aqueous ammonium.
(Washing) Tap water (Stabilizer) Formalin (37 ~ aqueous solution)1.5 mQ
Konidax (manufactured by Konica Corporation) 7.5 m~
Water was added to the above components to prepare one liter solution.
Silver halide light-sensitive material sample No. 7-1 through 7-12 prepared using the above mentioned emulsions were treated with the above processing solutions and the treatment steps (wherein the concentration of color developing agent and the color developing time were varied as listed in Tables 11 and 12. Graininess (RMS value) and sharpness (MTF value) of each obtained magenta dye image are listed in Tables 11 and 12.
Incidentally, RMS values indicating graininess are obtain-ed by multiplying 1000 times standard deviations in fluctuation of density values available when scanning a dye image having a density of 1.0 by using a microdensitometer having a circular scanning aperture diameter of 25 ~m.
MTF (Modulation Transfer Function) granularities were determined by comparing degrees of MTF relative to a spatial frequency of 30 lines/mm.
Smaller RMS values of magenta dye images indicate better graininess. Larger MTF values indicate better sharpness.
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Claims (11)
1. A processing method for processing a silver halide color photographic light-sensitive material with color developing of not more than 180 seconds, comprising color developing in a first developer solution for not more than 180 seconds, a silver halide color photographic light-sensitive material having a support, provided thereon, with at least one silver halide emulsion layer, and at least one of said emulsion layers containing silver iodo-bromide with not less than 0.5 mole % of silver iodide; said color developing for not more than 180 seconds being accomplished under color developing condition wherein said processing method when used to process a silver halide color photographic light-sensitive material B, will provide a dye image with a maximum magenta density M satisfying M ? 2.0, when said light-sensitive material is exposed under exposure conditions C described below and subjected to said color developing but for a duration of not more than
2.5 minutes;
said light-sensitive material being defined by properties whereby said light-sensitive material B
provides a maximum magenta density of M <2.0 when said light-sensitive material B contains, in a silver halide emulsion layer, both of a silver iodo-bromide with an iodine content of not less than 0.5 mole % and a magenta coupler, and is exposed under the exposure conditions C specified below and then subjected to color developing for a duration of three minutes 15 seconds at 38°C with the following developer A:
water is added to the above components to prepare a one liter solution, which is adjusted to pH
10.0 with 45% potassium hydroxide or 50% sulfuric acid exposure conditions C;
using a tungsten light source and filter, a color temperature is adjusted to 4800°K, in order to provide 3.2 CMS wedge exposure light.
2. Processing method as claimed in claim 1 for a silver halide color photographic light-sensitive material, and which is capable of forming with said light-sensitive material B a dye image whereby the magenta fog density in a non-exposure portion is lower than 0.5.
said light-sensitive material being defined by properties whereby said light-sensitive material B
provides a maximum magenta density of M <2.0 when said light-sensitive material B contains, in a silver halide emulsion layer, both of a silver iodo-bromide with an iodine content of not less than 0.5 mole % and a magenta coupler, and is exposed under the exposure conditions C specified below and then subjected to color developing for a duration of three minutes 15 seconds at 38°C with the following developer A:
water is added to the above components to prepare a one liter solution, which is adjusted to pH
10.0 with 45% potassium hydroxide or 50% sulfuric acid exposure conditions C;
using a tungsten light source and filter, a color temperature is adjusted to 4800°K, in order to provide 3.2 CMS wedge exposure light.
2. Processing method as claimed in claim 1 for a silver halide color photographic light-sensitive material, and which is capable of forming with said light-sensitive material B a dye image whereby the magenta fog density in a non-exposure portion is lower than 0.5.
3. Processing method as claimed in claim 1 or 2 for a silver halide color photographic light-sensitive material, wherein the concentration of color developing agent in said first developer solution used is not lower than 1.5 X 10-2 mole/liter.
4. Processing method as claimed in claim 1 or 2 for a silver halide color photographic light-sensitive material, wherein the pH of said first developer solution is not lower than 10.4.
5. Processing method as claimed in claim 1 or 2 for a silver halide color photographic light-sensitive material, wherein the color in said first developing temperature is not lower than 40°C.
6. Processing method as claimed in claim 1 or 2 for a silver halide color photographic light-sensitive material, wherein the sulfite concentration in the said first developer solution is not higher than 1.5 X
10-2 mole/liter.
10-2 mole/liter.
7. Processing method as claimed in claim 1 or 2 for a silver halide color photographic light-sensitive material, wherein the bromide concentration in the said first developer solution used is not higher than 0.8 X 10-2 mole/liter.
8. Processing method as claimed in claim 1 or 2 for a silver halide color photographic light-sensitive material, wherein said first developer solution contains at least one of compounds represented by any of the following general formulas [A-1] through [A-VI];
General formula [A-1]:
Xa1-(CH2)na1(Xa2-(CH2)na2)ma1Xa3-(CH2)na3Xa4 wherein Xa2 and Xa3 independently represent a sulfur atom or oxygen atom; Xa1 and Xa4 independently represent a SII group or OH group; na1, na2, na3 and ma1 independently represent an integer ranging from 0 to 500, whereby at least one of na1, na2 and na3 is an integer greater than 0, additionally, at least one of Xa1, Xa2, Xa3 and Xa4 is a sulfur atom;
wherein Ra1 and Ra2 independently represent a hydrogen atom, or an alkyl group such as a methyl group, ethyl group or propyl group, or a heterocyclic group which is capable of forming a ring, involving an oxygen or nitrogen atom, together with Ra1 and Ra2; Aa2 Aa3 and Aa4 independently represent a hydrogen atom, or an alkyl group such as a methyl or ethyl group, or a halogen atom such as a chlorine, fluorine, or bromine atom; Aa1 represents a hydroxy group or additionally, Ra3 and Ra4 independently represent a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms;
X a 5 ?
wherein Ra5, Ra6, Ra7 and Ra8 independently represent a hydrogen atom aryl group, aralkyl group, or a substituted or unsubstituted aryl group, Aa2 represents a nitrogen or phosphorus atom; Ra8 represents a substituted or unsubstituted alkylene group; Ra5 and Ra8 may form a ring, or independently be substituted or unsubstituted pyridinium group; Xa5 represents an anion group such as a halogen atom, OH, sulfuric group or nitric group;
wherein Ya represents a hydrogen atom, hydroxy group or Ra9, Ra10, Ra11, Ra12 and Ra13 independently represent a hydrogen atom; or a substituted or unsubstituted group, having 1 to 3 carbon atoms, such as an alkyl group, carbamoyl group, acetyl group and amino group;
X represents an oxygen atom, sulfur atom or at the same time, Ra14 represents a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms; 1a na2 and na4 independently represent an integer 0, 1, 2 or 3;
wherein Rb1 and Rb2 independently represent a hydrogen atom, alkyl group, alkoxy group, aryl group; or a nitrogen-containing heterocyclic which may be formed by Rb1 and Rb2 or a nitrogen-containing heterocycle which may be formed by Rb1 and Ab, or by Rb2 and Ab;
Rb3 represents an alkyl group; Ab represents an alkylene group; nb represents an integer ranging from 0 to 6;
wherein Rb1, represents a hydroxy alkyl group having 2 to 6 carbon atoms; Rb2, and Rb3, independently represent a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms, or a hydroxy alkyl group or benzyl group each having 2 to 6 carbon atoms, or in these formulas, nb represents an integer ranging from 1 to 6; Xb and Zb independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxy alkyl group having 2 to 6 carbon atoms.
General formula [A-1]:
Xa1-(CH2)na1(Xa2-(CH2)na2)ma1Xa3-(CH2)na3Xa4 wherein Xa2 and Xa3 independently represent a sulfur atom or oxygen atom; Xa1 and Xa4 independently represent a SII group or OH group; na1, na2, na3 and ma1 independently represent an integer ranging from 0 to 500, whereby at least one of na1, na2 and na3 is an integer greater than 0, additionally, at least one of Xa1, Xa2, Xa3 and Xa4 is a sulfur atom;
wherein Ra1 and Ra2 independently represent a hydrogen atom, or an alkyl group such as a methyl group, ethyl group or propyl group, or a heterocyclic group which is capable of forming a ring, involving an oxygen or nitrogen atom, together with Ra1 and Ra2; Aa2 Aa3 and Aa4 independently represent a hydrogen atom, or an alkyl group such as a methyl or ethyl group, or a halogen atom such as a chlorine, fluorine, or bromine atom; Aa1 represents a hydroxy group or additionally, Ra3 and Ra4 independently represent a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms;
X a 5 ?
wherein Ra5, Ra6, Ra7 and Ra8 independently represent a hydrogen atom aryl group, aralkyl group, or a substituted or unsubstituted aryl group, Aa2 represents a nitrogen or phosphorus atom; Ra8 represents a substituted or unsubstituted alkylene group; Ra5 and Ra8 may form a ring, or independently be substituted or unsubstituted pyridinium group; Xa5 represents an anion group such as a halogen atom, OH, sulfuric group or nitric group;
wherein Ya represents a hydrogen atom, hydroxy group or Ra9, Ra10, Ra11, Ra12 and Ra13 independently represent a hydrogen atom; or a substituted or unsubstituted group, having 1 to 3 carbon atoms, such as an alkyl group, carbamoyl group, acetyl group and amino group;
X represents an oxygen atom, sulfur atom or at the same time, Ra14 represents a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms; 1a na2 and na4 independently represent an integer 0, 1, 2 or 3;
wherein Rb1 and Rb2 independently represent a hydrogen atom, alkyl group, alkoxy group, aryl group; or a nitrogen-containing heterocyclic which may be formed by Rb1 and Rb2 or a nitrogen-containing heterocycle which may be formed by Rb1 and Ab, or by Rb2 and Ab;
Rb3 represents an alkyl group; Ab represents an alkylene group; nb represents an integer ranging from 0 to 6;
wherein Rb1, represents a hydroxy alkyl group having 2 to 6 carbon atoms; Rb2, and Rb3, independently represent a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms, or a hydroxy alkyl group or benzyl group each having 2 to 6 carbon atoms, or in these formulas, nb represents an integer ranging from 1 to 6; Xb and Zb independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxy alkyl group having 2 to 6 carbon atoms.
9. Processing method as claimed in claim 1 or 2 for a silver halide color photographic light-sensitive material, wherein said first developer solution contains at least one of compounds represented by any of the following general formulas [R-I] through [R-III]; General formula [R-I]
wherein X'r and X'r1 independently represent a halogen atom, alkyl group, aryl group, amino group, hydroxy group, nitro group, carboxyl group or sulfonyl group;
X'r2 represents a hydrogen atom, alkyl group, aryl group, or a divalent group for forming a ring; Zr represents a plurality of atoms selected from the group consisting of a carbon atom, oxygen atom, nitrogen atom and sulfur atom, being necessary for forming a ring; nr and mr independently represent 0, 1, 2 or 3:
wherein Yra, [Rr1] Yr1, Yr2 and Yr3 independently represent a hydrogen atom, halogen atom, alkyl group, amino group, hydroxy group, nitro group, carboxyl group or sulfonyl group;
wherein Tr represents a nitrogen atom, or phosphorus atom; Xr2 and Xr3 independently represent a hydrogen atom, alkyl group, aryl group or halogen atom, Yr4 and Yr5, independently represent an alkyl group, or aryl group; Yr4 and Yr5 may jointly undergo ring closure to form a heterocycle.
wherein X'r and X'r1 independently represent a halogen atom, alkyl group, aryl group, amino group, hydroxy group, nitro group, carboxyl group or sulfonyl group;
X'r2 represents a hydrogen atom, alkyl group, aryl group, or a divalent group for forming a ring; Zr represents a plurality of atoms selected from the group consisting of a carbon atom, oxygen atom, nitrogen atom and sulfur atom, being necessary for forming a ring; nr and mr independently represent 0, 1, 2 or 3:
wherein Yra, [Rr1] Yr1, Yr2 and Yr3 independently represent a hydrogen atom, halogen atom, alkyl group, amino group, hydroxy group, nitro group, carboxyl group or sulfonyl group;
wherein Tr represents a nitrogen atom, or phosphorus atom; Xr2 and Xr3 independently represent a hydrogen atom, alkyl group, aryl group or halogen atom, Yr4 and Yr5, independently represent an alkyl group, or aryl group; Yr4 and Yr5 may jointly undergo ring closure to form a heterocycle.
10. Processing method as claimed in claim 1 or 2 for a silver halide color photographic light-sensitive material, wherein said light-sensitive material contains at least one of compounds represented by the following general formula [R-IV]:
in Formula [R-IV], Rs represents OH, DRs4 or Rs4 and Rs5 independently represent an alkyl group;
said alkyl group represented either by Rs4 or Rs5 may have a substituent:
Rs4 and Rs5 independently represent II or Rs represents an alkyl group or aryl group each of which may have a substituent:
Xs and Ys respectively represent a carbon atom and a hydrogen atom, each of which forms a six-membered ring together with other plurality of atoms;
Zs represents N.
in Formula [R-IV], Rs represents OH, DRs4 or Rs4 and Rs5 independently represent an alkyl group;
said alkyl group represented either by Rs4 or Rs5 may have a substituent:
Rs4 and Rs5 independently represent II or Rs represents an alkyl group or aryl group each of which may have a substituent:
Xs and Ys respectively represent a carbon atom and a hydrogen atom, each of which forms a six-membered ring together with other plurality of atoms;
Zs represents N.
11. Processing method as claimed in claim 1 or 2 for a silver halide color photographic light-sensitive material, wherein said first developer solution contains at least polymer or copolymer which has within the molecular structure a pyrolidone nucleus;
or at least one ethylene glycol.
or at least one ethylene glycol.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16288586 | 1986-07-10 | ||
| JP18409086 | 1986-08-05 | ||
| JP18408786 | 1986-08-05 | ||
| JP19110586 | 1986-08-14 | ||
| JP29455486 | 1986-12-10 | ||
| JP29849786 | 1986-12-15 | ||
| JP5770087 | 1987-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1317500C true CA1317500C (en) | 1993-05-11 |
Family
ID=27564934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000556170A Expired - Fee Related CA1317500C (en) | 1986-07-10 | 1988-01-08 | Processing method for silver halide color photographic light-sensitive material and color developer used therein |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4937178A (en) |
| EP (1) | EP0273986B1 (en) |
| KR (1) | KR880701904A (en) |
| AU (1) | AU597408B2 (en) |
| CA (1) | CA1317500C (en) |
| DE (1) | DE3751236D1 (en) |
| WO (1) | WO1988000724A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2915095B2 (en) * | 1989-12-28 | 1999-07-05 | コニカ株式会社 | Color developing solution for silver halide color photographic material and processing method |
| EP0439142B1 (en) * | 1990-01-24 | 1998-04-01 | Fuji Photo Film Co., Ltd. | Composition for color-development and method for processing using same |
| JP2866947B2 (en) * | 1990-03-13 | 1999-03-08 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
| JP2729542B2 (en) * | 1991-02-22 | 1998-03-18 | 富士写真フイルム株式会社 | Processing solution for silver halide color photographic light-sensitive material and processing method using the same |
| US5262285A (en) * | 1992-05-04 | 1993-11-16 | Eastman Kodak Company | Methods and compositions for retouching film images |
| US5489961A (en) * | 1993-04-02 | 1996-02-06 | Burbury; Robert L. | Chemical developer sensing system for film processors |
| DE69426048T2 (en) * | 1993-07-28 | 2001-05-10 | Chugai Shashin Yakuhin | Composition containing a color developer substance, color developer for processing silver halide color photographic materials and their use |
| DE69713929T2 (en) * | 1996-02-29 | 2003-02-13 | Chugai Shashin Yakuhin | Color developer composition and method for processing a silver halide color photographic material |
| US5935767A (en) * | 1998-01-29 | 1999-08-10 | Eastman Kodak Company | Process of producing color negative image at shortened development times |
| US5968718A (en) * | 1998-07-14 | 1999-10-19 | Eastman Kodak Company | Color development process that results in high observed speeds |
| US6383726B1 (en) | 2000-11-03 | 2002-05-07 | Eastman Kodak Company | Method for formulating a photographic developer composition and process conditions to optimize developed images for digital scanning |
| EP1203993A1 (en) * | 2000-11-03 | 2002-05-08 | Eastman Kodak Company | Developer composition and method of development for photographic color negative films |
| US6589721B1 (en) | 2001-12-20 | 2003-07-08 | Eastman Kodak Company | Method of developing a color negative element intended for scanning |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE622218A (en) * | 1961-09-11 | |||
| FR1585284A (en) * | 1967-10-02 | 1970-01-16 | ||
| US3985564A (en) * | 1973-01-30 | 1976-10-12 | Eastman Kodak Company | Photographic element and process for developing |
| JPS5562451A (en) * | 1978-11-02 | 1980-05-10 | Konishiroku Photo Ind Co Ltd | Processing method for silver halide color photographic material |
| JPS5562450A (en) * | 1978-11-02 | 1980-05-10 | Konishiroku Photo Ind Co Ltd | Processing method for silver halide color photographic material |
| JPS5846010B2 (en) * | 1978-11-29 | 1983-10-13 | コニカ株式会社 | Silver halide color photographic material processing method |
| JPS5821256B2 (en) * | 1979-01-16 | 1983-04-28 | コニカ株式会社 | Silver halide color photographic material processing method |
| JPS57144547A (en) * | 1981-03-03 | 1982-09-07 | Fuji Photo Film Co Ltd | Silver halide color photosensitive material and its processing method |
| EP0093536B1 (en) * | 1982-04-29 | 1986-10-08 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Stabilised photographic color developer compositions and processes |
| JPS5971047A (en) * | 1982-10-18 | 1984-04-21 | Fuji Photo Film Co Ltd | Developing process for silver halide photosensitive material |
| US4546068A (en) * | 1983-06-09 | 1985-10-08 | Konishiroku Photo Industry Co., Ltd. | Method for processing of light-sensitive silver halide color photographic material |
| JPS6019140A (en) * | 1983-07-13 | 1985-01-31 | Konishiroku Photo Ind Co Ltd | Dye image forming method |
| JPS6066250A (en) * | 1983-09-21 | 1985-04-16 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
| JPS60232544A (en) * | 1983-12-08 | 1985-11-19 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
| JPS60254032A (en) * | 1983-12-29 | 1985-12-14 | Fuji Photo Film Co Ltd | Photosensitive silver halide emulsion |
| JPS60143331A (en) * | 1983-12-29 | 1985-07-29 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
| JPS60162253A (en) * | 1984-02-01 | 1985-08-24 | Konishiroku Photo Ind Co Ltd | Method for processing silver halide color photosensitive material |
| JPH0654375B2 (en) * | 1986-01-24 | 1994-07-20 | 富士写真フイルム株式会社 | Color image forming method |
| JPH0656483B2 (en) * | 1986-01-29 | 1994-07-27 | 富士写真フイルム株式会社 | Color image forming method |
| US4774167A (en) * | 1986-02-24 | 1988-09-27 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic materials wherein the color developer contains low concentrations of benzyl alcohol, hydroxylamine and sulfite |
| JP3328322B2 (en) * | 1992-07-13 | 2002-09-24 | トヨタ自動車株式会社 | Exhaust gas purification method |
-
1987
- 1987-07-10 DE DE3751236T patent/DE3751236D1/en not_active Expired - Lifetime
- 1987-07-10 US US07/171,867 patent/US4937178A/en not_active Expired - Lifetime
- 1987-07-10 AU AU76911/87A patent/AU597408B2/en not_active Ceased
- 1987-07-10 WO PCT/JP1987/000494 patent/WO1988000724A1/en active IP Right Grant
- 1987-07-10 EP EP87904560A patent/EP0273986B1/en not_active Expired - Lifetime
-
1988
- 1988-01-08 CA CA000556170A patent/CA1317500C/en not_active Expired - Fee Related
- 1988-03-09 KR KR1019880700264A patent/KR880701904A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE3751236D1 (en) | 1995-05-18 |
| AU7691187A (en) | 1988-02-10 |
| EP0273986A1 (en) | 1988-07-13 |
| US4937178A (en) | 1990-06-26 |
| WO1988000724A1 (en) | 1988-01-28 |
| EP0273986A4 (en) | 1989-11-07 |
| AU597408B2 (en) | 1990-05-31 |
| EP0273986B1 (en) | 1995-04-12 |
| KR880701904A (en) | 1988-11-07 |
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