EP0329016A2 - Colour-photographic recording material - Google Patents

Abstract

A colour-photographic recording material consisting of a base and at least one silver halide emulsion layer applied to a base, and associated with at least one colour coupler having a coupling rate constant at pH = 10.2 and 38 DEG C of >/=10<4> [l/mol x sec] and at least one DIR coupler having a coupling rate constant at pH = 10.2 and 38 DEG C of >/= 10<4> [l/mol x sec], wherein a silver halide emulsion is used which, with the abovementioned colour couplers and DIR couplers, gives at 38 DEG C in a colour developer of the following composition sodium tripolyphosphate 2.0 g sodium sulphite (anhydrous) 2.0 g sodium hydrogen carbonate 8.0 g potassium or sodium hydrogen sulphate 7.0 g potassium bromide 1.8 g potassium or sodium carbonate (anhydrous) 30.0 g hydroxylamine sulphate 3.0 g N<1>-ethyl-N<1>-(2-hydroxyethyl)-3-methyl-1,4-phenylenediammonium sulphate (monohydrate) 2.6 g water to make up to 1000 ml pH = 10.2 a relative maximum colour density = <IMAGE> of at least 50 %, shows a small range of variation with respect to sensitometric data (sensitivity, gradation and fog) in the event of variations of the processing conditions.

Description

The invention relates to a color photographic recording material, the sensiometric data (e.g. sensitivity, gradation and fog) of which are significantly less influenced by fluctuations in the processing conditions (e.g. duration, temperature, pH of the developer, concentration of the developer, etc.) than conventional material.

It is known that in the development process of color photographic recording materials (eg: color negative / positive process), the uniformity of the color reproduction depends very much on the uniformity of the processing. Even small fluctuations in the processing time and in the composition of the processing baths, especially the color developer solution, as they occur due to different or irregular regeneration, can lead to uncontrollable deviations in the color reproduction, especially with shorter processing times. (See manual for photo finishers Agfa-Gevaert, Leverkusen, 1985).

The invention is based on the object of developing a color photographic recording material which, with very good and constant color reproduction, is less susceptible to fluctuations during processing, in particular with regard to shorter process times.

von mindestens 50 % liefert.The invention relates to a color photographic recording material comprising a support and at least one silver halide emulsion layer applied to the support, the at least one color coupler with a coupling rate constant at pH = 10.2 and 38 ° C of ≧ 10⁴ [l / mol · sec] and at least one DIR -Coupler with a coupling rate constant at pH = 10.2 and 38 ° C of ≧ 10⁴ [l / mol · sec] is assigned, characterized in that a silver halide emulsion is used, which with the above-mentioned color and DIR couplers at 38 ° C in a color developer of the following composition Sodium tripolyphosphate 2.0 g Sodium sulfite (anhydrous) 2.0 g Sodium bicarbonate 8.0 g Potassium or sodium bisulfate 7.0 g Potassium bromide 1.8 g Potassium or sodium carbonate (anhydrous) 30.0 g Hydroxylamine sulfate 3.0 g N¹-ethyl-N¹- (2-hydroxyethyl) -3-methyl-1,4-phenylenediammonium sulfate (monohydrate) 2.6 g Water to make up to 1000 ml pH = 10.2 a relative maximum color density

of at least 50%.

The relative maximum color density should preferably be 70%.

The silver halide emulsions used in the material according to the invention must therefore develop very quickly.

With a color development time of 195 seconds in the standard process, all those silver halide emulsions are understood as developing fast enough for the material according to the invention which, with a shortened color development time of 65 seconds in combination with the couplers and DIR couplers according to the invention, result in a relative maximum density of at least 50%.

The inhibitors split off from the DIR coupler should preferably have a diffusibility of ≧ 0.4.

The diffusibility is a measure of the distance covered by the inhibitor after the cleavage in the coupling process of the DIR coupler within the emulsion layers, on which it develops its inhibitory effect.

The method of measuring diffusibility used in the present invention is described in EP-A-101 621.

The color photographic recording material contains in particular at least one blue-sensitive silver halide emulsion layer to which a yellow coupler is assigned, at least one green-sensitive silver halide emulsion layer to which a magenta coupler is assigned and at least one red-sensitive silver halide emulsion layer to which a cyan coupler is associated, preferably at least one layer corresponding to the conditions according to the invention for each spectral range.

The color couplers of the higher sensitive sub-layers preferably have an even higher coupling rate constant than that of the lower sensitive sub-layers (cf. DE-OS-1 958 709).

To achieve the desired gradation, mixtures of several rapidly developing emulsions and / or mixtures of several rapidly coupling color couplers and / or mixtures of several fast coupling DIR couplers, the inhibitors of which have high diffusibility, can also be used in the partial layers of the material according to the invention.

To accelerate development, it is also advantageous to add development accelerators, development aids and / or swelling accelerators to the material according to the invention. The following table shows an overview of such additives, without any such additives being restricted to these substances.

- Kationische Polyethylenglykole mit 2 Pyridiniumresten an den Enden

- Anionische Polyethylenglykole mit Sulfogruppen an den Enden z.B.
H^⊕[^⊖O₃S-O-(CH₂-CH₂O)₃₅-CH₂CH₂-OSO₃^⊖]H^⊕ .For example, 1-phenyl-3-pyrazolone is used as a development aid. Development accelerators are, for example, substances from the following classes of substances:
- quaternary ammonium, phosphonium and sulfonium salts,
- Neutral polyethylene glycols with an ether, ester or amide residue

- Cationic polyethylene glycols with 2 pyridinium residues at the ends

- Anionic polyethylene glycols with sulfo groups at the ends, for example
H ^⊕ [ ^⊖ O₃S-O- (CH₂-CH₂O) ₃₅-CH₂CH₂-OSO₃ ^⊖ ] H ^⊕ .

Development is also accelerated by amines such as p-chlorobenzylamine, α- (p-chlorophenyl) ethylamine, p-nitrobenzylamine, β-phenoxyethylamine, β-4-bromophenoxyethylamine, γ-4-chlorophenoxypropylamine or 2-aminomethylthiophene, furfurylamine, 5-aminomethylamine 1-methyl-4-imidazolone reached. Furthermore, thioethers can also be used as development accelerators.

• E 1
  
• E 2 Laurylpyridinium-p-toluolsulfonat
• E 3 3.6-Thiaoctan-1.8-diol

From the multitude of possible development accelerators, the following examples are given:

• E 1
  
• E 2 lauryl pyridinium p-toluenesulfonate
• E 3 3.6-thiaoctane-1.8-diol

Examples of suitable swelling accelerators are:
Urea and its derivatives, phenols and their derivatives, for example resorcinol, salicylic acid. Compounds such as polyacrylamides, dextrans, dextrans, polymeric N-vinyl lactams, polysaccharides, polyvinyl alcohols, copolymers of acrylic acids and acrylamides, polyvinylpyrrolidone and its derivatives, polymers of ethylenically unsaturated compounds with acrylic acid, maleic acid, vinyl acetate and styrene can also be added to the layer.

Preparation of the silver halide emulsions

The silver halide emulsions according to the invention can e.g. by single entry, double entry, continuous precipitation, accelerated precipitation or interrupted precipitation in the presence of a hydrophilic colloid, e.g. Gelatin, which is also modified, e.g. by reaction with phthalic anhydride, or modified or even oxidized in molecular weight (P. Glafkides, Chimie et Physique Photographiques, P. Montel Paris (1967); GF Duffin Photographic Emulsion Chemistry, The Focal Press London (1966); Research Disclosure (1983) No. 225, 22534). Furthermore, the method of ultrafiltration can be used to separate off the alkali metal nitrates released during the silver halide precipitation. It is also possible to use synthetic polymers. In the preparation of the emulsions, compounds which influence the growth of the silver halide crystals, so-called growth modifiers, can be used. Metal compounds can also be used as doping substances. When the silver halide is precipitated, optical sensitizers, densitizers or electron acceptors can also be present.

The silver halide can be precipitated at pH values between 2-8. The pAg values can range between 6 and 10. These values can change continuously during the felling process; however, they can also be kept constant during the precipitation.

The halides used can consist of silver bromide, silver bromide chloride, silver bromide iodide and silver chloride bromide iodide, the total iodide content being <15 mol%, preferably <10 mol% and depending on the type of developer, e.g. is the content of silver halide solvent in the developer, and the position of the emulsion in the layer structure. E.g. the iodide content of the bottom layer may be lower than that of the top layer.

The silver halides can be obtained from regular crystals, e.g. Cubes or octahedra or tetradecahedra exist. However, tabular shaped twin crystals with an aspect ratio of 3: 1 to 30: 1 or more can also be used.

The crystals, both the regular crystals and the tabular crystals, can have a layer structure, the halide composition of the individual layers being different.

The layer structures are preferably constructed as core / shell crystals, it being possible for the iodide to be present in the core preferably in amounts of up to 40 mol%, while the shell has an iodide content between 0-5 mol%. The total iodide content of the crystals can be adjusted by the ratio of core to shell and is <15 mol%, iodide based on the total silver of the crystal, but preferably <10 mol% iodide.

The crystals can also be made up of several shells, wherein AgBrCl and AgBrICl can also be present in the layers in addition to AgBr, AgBrI.

The silver halides can also be produced by converting already precipitated silver halides with another halide. E.g. silver chloride with alkali or ammonium bromide can easily be converted into silver bromide, likewise silver chloride or bromide can be easily or completely converted into silver iodide. The reverse process is also possible, the concentration of the conversion halide having to be calculated according to the solubility differences, depending on the type of halide present.

The silver halide crystals can also be produced by producing very fine-grained emulsions and subsequent redissolving. The redissolution can also be carried out by mixing two emulsions which differ in crystal size and / or the halide composition. The redissolution takes place by lowering the pBr value to values from 0.6 to 2, preferably from 0.8 to 1.2, at temperatures between 40 ° C. and 80 ° C. Silver halide solvents such as ammonia, thiocyanates or thioethers can also be added.

The silver halides can be crystals which can be obtained by epitaxial growth, for example silver chloride can grow on silver bromide or silver iodide on silver bromide. Emulsions this Containing crystal forms show rapid developability (JE Makasky, Photogr. Sci. Eng. 25 (1981), No. 3, pp. 96-101).

The emulsions can have monodisperse crystals, i.e. at least 90% of the grains have grain sizes that are ± 60%, preferably ± 40% within the mean grain size.

The emulsions can also be polydisperse.

For tabular crystals, the projection area of the tabular crystals is at least 75% of the projection area of all existing crystals. The thickness of the tabular crystals is between 0.4 µm and 0.1 µm. These grains are distinguished by a very rapid development (Research Disclosure (1983), No. 225 (22534)), pp. 20-58).

The silver halides can also have an internal image which is obtained by chemically ripening the crystals and then depositing a further layer of a silver halide on the ripened crystals.

The (colorless and colored) color couplers used in the material according to the invention are those which couple very quickly in the color winder used under the respective development conditions (e.g. development temperature).

The method for measuring the clutch speed is given in DE-OS-2 704 797. The measuring methodology and the equipment for determining the coupling rate constants of the couplers and DIR couplers used in the material according to the invention are described below.

It has been shown that the relative reaction rate constants of a coupler or DIR coupler determined according to one of the known methods can assume different values, depending on how these compounds are dispersed. It is conceivable that the same coupler can be used both as an aqueous alkaline solution or in the form of an emulsate using a so-called coupler solvent or oil-forming agent. Hydrophobic couplers can be used in the form of aqueous dispersions, which can optionally be prepared using low-boiling organic solvents, or in the form of the aforementioned emulsions. In the case of emulsifiers, the k value can also depend on the type and amount of the solvent (oil former) as well as on the type of wetting agent and the size of the droplets. For this reason, it is desirable as a decision criterion for the usability of the couplers or DIR couplers in the sense of the present invention directly on the effective reaction gene to use the velocity constant (k _eff ) of the couplers in their respective dispersion form. It is therefore expedient to use the couplers in the same dispersion form in which they are also to be used in the color photographic material in order to determine the relative reaction rate.

An electrochemical method was developed which allows the determination of the reactivity of dissolved or emulsified couplers in the form of an effective reaction rate _constant (k _eff [l / mol · sec]) approximately in vitro. A measure of the reactivity is the consumption of the developer oxidation product, which can be determined by measuring the redox potential in a "stopped flow" apparatus. The k _eff values given in the present description were determined by the method described below.

• Fig. 3 eine Prinzipskizze der Meßapparatur,
• Fig. 4 ein mit Hilfe dieser Meßapparatur erhaltenes Diagramm zur Bestimmung eines k_eff-Wertes.

The structure and mode of operation of the measuring apparatus used are explained below with reference to FIGS. 3 and 4. It shows

• 3 is a schematic diagram of the measuring apparatus,
• Fig. 4 is a diagram obtained with the aid of this measuring apparatus for determining a k _eff value.

The measuring apparatus shown in Fig. 3 consists of the cylindrical, approximately 25 cm high storage containers 1 and 2, the supply lines 3 equipped with check valves, the mixing chamber 4, the solenoid valve 5, which is closed in the idle state and opened via the pulse generator 6 can be net, the collecting vessel 7, in which a negative pressure is generated and maintained, the measuring electrode 8a, the reference electrode 8b, the digital mV meter 9 and the recorder 10th

The solenoid valve 5 is opened for a time t by means of the pulse generator 6. As a result of the pressure gradient between the collecting vessel 7 and the storage containers 1 and 2, the liquids contained in the latter flow via the feed lines 3 into the mixing chamber, where intensive mixing takes place. The mixture then passes through the solenoid valve 5 into the collecting vessel 7. Storage container 1 contains an oxidizing agent, e.g. a 10⁻³ molar aqueous solution of K₃ [Fe (CN) ₆]. Storage container 2 contains a color developer, the coupler to be examined and means for adjusting the desired pH (buffer), all in aqueous solution. As a color developer, N¹-ethyl-N¹ (2-hydroxyethyl) -3-methyl-1,4-diammonium sulfate (monohydrate) = speziell CD 4 was used (concentration: 2x10⁻³ mol / l). The concentration of the coupler to be measured was 10⁻³ mol / l. Couplers that are not soluble in water can be used in the form of an emulsified from coupler, coupler solvent and hydrophilic binder produced in a known manner. The pH was adjusted to 10.2 using a carbonate / bicarbonate buffer.

The redox potential in the mixture is measured with the measuring electrode 8a (platinum wire ⌀ 1 mm); An Ag / AgCl electrode (eg Argenthal cartridge) serves as the reference electrode 8b, which in this embodiment is located in the Zulei device of the storage container 2 to the mixing chamber, but can also be attached as usual next to the platinum electrode. The measured redox potential of the mixed solutions can be read with the aid of the digital mV meter 9 and the time course can be recorded by means of the recorder 10 (compensation recorder, oscillograph, light-point line recorder).

worin bedeuten:
k_eff = Reaktionsgeschwindigkeitskonstante [l/Mol·sec]
K₀ = Anfangskonzentration an Kuppler (Mol/l)
f = elektrochemische Konstante

α_K = Winkel α, erhalten wenn Kuppler zugegen ist
α₀ = Winkel α, erhalten wenn kein Kuppler zugegen istThe time course of the change in the redox potential is shown in FIG. 4. The measured redox potential is plotted in mV (ordinate) as a function of time in sec (abscissa). t represents the opening time of the solenoid valve. The effective reaction rate _constant k _eff can be calculated from the angle α using the following equation:

in which mean:
k _eff = reaction rate _constant [l / mol · sec]
K₀ = initial concentration at coupler (mol / l)
f = electrochemical constant

α _K = angle α obtained when coupler is present
α₀ = angle α, obtained when no coupler is present

After the solutions have been filled into the storage containers 1 and 2, the mixing chamber 4 and the supply and discharge lines are rinsed vigorously by opening the solenoid valve 5 for a longer time and the containers are then refilled to the original level. The potential-time curve shown in FIG. 4 can then be recorded by briefly opening the solenoid valve 5. The angle α (FIG. 4) between the time axis and the tangent to the measurement curve at the start of the reaction is determined, once with the coupler to be measured (α _K ) and once again without a coupler (α₀). The effective reaction rate _constant k _eff can be determined by inserting the two α values in the above equation.

Of course, the method can also be modified in many ways. So other color developers can be used and the reaction can be run at different pH values. To measure the reactivity of couplers which are very quickly oxidized by ferricyanide, the apparatus can be changed so that instead of the one mixing chamber 4 a system of two series-connected mixing chambers is used, the developer oxidation product in the first mixing chamber by mixing developer and ferricyanide together is generated, which is then mixed together in the second mixing chamber with the coupler to be measured. The concentration on the developer oxidation product is mainly detected by the measuring electrode, which is probably the quinone diimine of the corresponding color developer used. Regarding the basics of redox measurement, reference is made, for example, to J. Eggers "About the subsequent reactions at Oxidation of p-amino-N-dialkylanilines "in" Messages from Agfa's Research Laboratories ", Volume III, page 73 (1961).

The couplers or DIR couplers are converted into an emulsifier with which the measurements described above are carried out in the following manner:

2 g of coupler are dissolved in 8 ml of a solvent mixture consisting of one part of dibutyl phthalate, three parts of ethyl acetate and 0.1 part of di-n-octyl sulfosuccinate (mannoxol) and emulsified in 37.5 g of 7.5% gelatin. The emulsate is then stirred for 6 min at about 1000 rpm, during which it heats up to a maximum of 60 ° C. and the ethyl acetate is then suctioned off in a water jet vacuum (200-300 mbar). Then make up to 60 g with water. The part corresponding to 1 mmol of coupler is removed from this solution and made up to 100 g with 4% gelatin. 20 ml of solution are used for each measurement.

The coupling rate constants designated k in the further course relate to the effective reaction rate _constants k _eff determined with the method described above.

All those couplers are suitable for the material according to the invention whose coupling rate constant at the pH of the color developer is k ≧ 10⁴ [l / mol · sec].

Examples for sufficiently fast (clutch speed constant k ≧ 10⁴ [l / mol · sec.] At pH = 10.2) and for couplers that are too slow (k ≦ 10⁴ l / mol · sec] can be found in the following tables, for example, without that the couplers that can be used for the material according to the invention should remain limited to the substances listed there.

• a) 2-Äquivalentgelbkuppler vom Benzoylacetanilidtyp und/oder Pivaloylacetanilidtyp
• b) Purpurkuppler von Pyrazolo-azoltyp und/oder Acyl­aminopyrazolontyps
• c) Blaugrünkuppler vom 2-Ureidophenoltyp und/oder 5-­Amino-1-naphtholtyp
• d) Rotmaskenkuppler mit O-Fluchtgruppe der allgemeinen Formel:
  Cp-O-L_(0-1)-Dye
  in der
  Cp Blaugrünkuppler
  L Bindeglied
  Dye Farbstoff mit λ_max zwischen 510-590 nm
  bedeuten.

Fast couplers of the following classes are preferred for the material according to the invention:

• a) 2-equivalent yellow coupler of the benzoylacetanilide type and / or pivaloylacetanilide type
• b) Purple couplers of pyrazolo-azole type and / or acylaminopyrazolone type
• c) Teal couplers of the 2-ureidophenol type and / or 5-amino-1-naphthol type
• d) red mask coupler with O-escape group of the general formula:
  Cp-OL _(0-1) dye
  in the
  Cp teal coupler
  L link
  Dye dye with λ _max between 510-590 nm
  mean.

The DIR couplers used in the color photographic recording material according to the invention must also have a high coupling speed (k ≧ 10⁴ [l / mol · sec]) so that they can compete with color and mask couplers in color coupling in the color developer. Otherwise they provide no or only insufficient DIR effects in the image-relevant color density range. The same measuring method is used to measure the coupling speed as for the color and color mask couplers.

In addition, those DIR couplers whose inhibitors have a high diffusibility (D ≧ 0.4) are preferably used in the color photographic recording material according to the invention. A high diffusibility of the inhibitors is known to be advantageous for high sharpness (due to large edge effects) and good color rendering (due to large inter-image effects = IIE).

In the following overview, some DIR couplers with a sufficiently high diffusibility (D ≧ 0.4) are compiled, both those that couple sufficiently quickly in the sense of this invention (k ≧ 10⁴ [l / mol · sec]) without the DIR couplers to be used in the material according to the invention are to be restricted to these substances.

Furthermore, the difference in the coupling rate constant between the color and DIR couplers should not be more than a factor of 5, preferably not more than a factor of 2.

Gelatin is preferably used as a binder for the emulsions according to the invention. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates. Semi-synthetic gelatin substitutes are usually modified natural products. Examples of these are cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers.

The binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin which is preferably used can be obtained by acidic or alkaline digestion. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff. The gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). Gelatins with a high viscosity and a low content of calcium and iron ions are particularly advantageous.

After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.

The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benztria can also be used as antifoggants zoles or benzothiazolium salts are used. Heterocycles containing mercapto groups, e.g. B. mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles also containing a water-solubilizing group, for example a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.

The stabilizers can be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.

Mixtures of two or more of the compounds mentioned can also be used.

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the present invention may contain surfactants, viscosity-increasing agents or other agents for various purposes, such as coating aids, for preventing electrical charging, for improving the sliding properties, for emulsifying the dispersion, for preventing adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.) Fluorosurfactants are particularly advantageous as casting aids.

The photographic emulsions can be spectrally sensitized using methine dyes or other dyes. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromide or silver bromide iodide.

The emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.

Taking into account the color couplers described above, the coupler types listed below can also be used.

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type; suitable examples of this are known in the literature.

Color couplers for generating the yellow partial color image are usually couplers with an open-chain ketomethylene group, in particular couplers of the type α-acylacetamids; Suitable examples of this are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers, which are also known from the literature.

Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; Suitable examples of this are described in large numbers in the literature.

The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling. The 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), the white couplers that react with Color developer oxidation products result in essentially colorless products. The 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( e.g. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the DIR couplers described above as well as DAR or. FAR coupler. Quick-coupling 2-equivalent couplers, which split off those escape groups which accelerate the development, are particularly advantageous for the material according to the invention.

Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-1 547 640). Because of the small amounts in which such auxiliary couplers are used, it is hardly a disadvantage if these auxiliary couplers provide a different color for the color coupling than the color couplers contained in the layer in question.

The cleavable residue can also be a ballast residue, so that when reacting with color developer oxidation products, coupling products are obtained which are diffusible or at least have a weak or restricted mobility, so that the color granularity is reduced by washing away the microfiber clouds (US Pat. No. 4,420,556) ).

High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.

When using the couplers (color and DIR couplers) it must be ensured that they meet the requirements according to the invention with regard to the coupling speed.

The couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question. The selection of the suitable solvent or dispersing agent depends on the solubility of the compound.

Methods for introducing compounds which are essentially insoluble in water by grinding processes are described, for example, in DE-A-2 609 741 and DE-A-2 609 742.

Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Appropriate Methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.

Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.

The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-2 541 230, DE-A-2 541 274, DE-A-2 835 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, U.S.-A-4,291,113.

The diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out with the help of cationic polymers, so-called pickling polymers.

Suitable oil formers are e.g. Alkyl phthalates, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters and trimesic acid esters.

A color photographic material typically comprises at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of these layers can be varied as desired. Usually blue-green, purple and yellow dyes forming couplers are in the red, green and blue sensitive Emulsion layers incorporated. However, different combinations can also be used.

Each of the light-sensitive layers for a spectral range can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). Red-sensitive silver halide emulsion layers are often arranged closer to the layer support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

With a suitably low intrinsic sensitivity of the green or Red-sensitive layers can be chosen without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.

If there are several sub-layers of the same spectral sensitization, these can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sub-layer with the higher sensitivity will be arranged further away from the support than the sub-layer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, e.g. separated by layers of other spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A 1 958 709, DE-A 2 530 645, DE-A 2 622 922).

Also layer arrangements in which more than two sub-layers are sensitive to the same spectral range, e.g. a high, a medium and a low sensitive sub-layer have proven to be advantageous. Here, e.g. the middle and the low-sensitive sub-layer can be combined, while the most sensitive sub-layer for the same area can be arranged alternately above it with the most sensitive sub-layers of the other spectral ranges. Intermediate layers insensitive to light can also be applied between the layers with the same color sensitivity.

The photographic material may further contain UV light absorbing compounds, spacers, filter dyes, formalin scavengers and others.

Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film. Connections of different structures are usually used for the two tasks. Examples are aryl substituted benzotriazole compounds (US-A 3 533 794), 4-thiazolidone compounds (US-A 3 314 794 and 3 352 681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US-A 3 705 805 and 3 707) 375), butadiene compounds (US-A 4 045 229) or benzoxazole compounds (US-A 3 700 455).

Ultraviolet absorbing couplers (such as α-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.

Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styrene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.

Certain binder layers, in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).

The average particle diameter of the spacers is in particular in the range from 0.2 to 10 μm. The spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.

The binders of the material according to the invention, in particular if gelatin is used as the binder, are hardened with suitable hardeners, for example with hardeners of the epoxy type, the ethyleneium type, the acryloyl type or the vinylsulfone type. Diazine, triazine or 1,2-dihydroquinoline series hardeners are also suitable.

The binders of the material according to the invention are preferably hardened with instant hardeners.

Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs . Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

These hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.

• (a)
  
  worin
  R₁ Alkyl, Aryl oder Aralkyl bedeutet,
  R₂ die gleiche Bedeutung wie R₁ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel
  
  verknüpft ist, oder
  R₁ und R₂ zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Pipe­razin- oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C₁-­C₃-Alkyl oder Halogen substituiert sein kann,
  R₃ für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR₄-COR₅, -(CH₂)_m-NR₈R₉, -(CH₂)_n-CONR₁₃R₁₄ oder
  
  oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei
  R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, und R₁₉ Wasserstoff oder C₁-C₄-Alkyl,
  R₅ Wasserstoff, C₁-C₄-Alkyl oder NR₆R₇,
  R₈ -COR₁₀
  R₁₀ NR₁₁R₁₂
  R₁₁ C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
  R₁₂ Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbeson­dere Phenyl,
  R₁₃ Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbeson­dere Phenyl,
  R₁₆ Wasserstoff, C₁-C₄-Alkyl, COR₁₈ oder CONHR₁₉,
  m eine Zahl 1 bis 3
  n eine Zahl 0 bis 3
  p eine Zahl 2 bis 3 und
  Y O oder NR₁₇ bedeuten oder
  R₁₃ und R₁₄ gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten hetero­cyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,
  Z die zur Vervollständigung eines 5- oder 6-­gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Ben­zolring, erforderlichen C-Atome und
  X^⊖ ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist;
• (b)
  
  worin
  R₁, R₂, R₃ und X^⊖ die für Formel (a) angegebene Bedeutung besitzen.

Suitable examples of instant hardeners are, for example, compounds of the general formulas

• (a)
  
  wherein
  R₁ denotes alkyl, aryl or aralkyl,
  R₂ has the same meaning as R₁ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula
  
  is linked, or
  R₁ and R₂ together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted, for example, by C₁-C₃alkyl or halogen,
  R₃ for hydrogen, alkyl, aryl, alkoxy, -NR₄-COR₅, - (CH₂) _m -NR₈R₉, - (CH₂) _n -CONR₁₃R₁₄ or
  
  or a bridge link or a direct bond to a polymer chain, wherein
  R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, and R₁₉ are hydrogen or C₁-C₄-alkyl,
  R₅ is hydrogen, C₁-C₄-alkyl or NR₆R₇,
  R₈ -COR₁₀
  R₁₀ NR₁₁R₁₂
  R₁₁ C₁-C₄ alkyl or aryl, especially phenyl,
  R₁₂ is hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
  R₁₃ is hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
  R₁₆ is hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,
  m is a number 1 to 3
  n is a number 0 to 3
  p is a number 2 to 3 and
  YO or NR₁₇ mean or
  R₁₃ and R₁₄ together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted, for example, by C₁-C₃alkyl or halogen,
  Z the C atoms and required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring
  X ^{⊖ is} an anion which is omitted if an anionic group is already linked to the rest of the molecule;
• (b)
  
  wherein
  R₁, R₂, R₃ and X ^{⊖ have} the meaning given for formula (a).

Antistatic agents for reducing the electrostatic charge can be applied on the back and / or on the surface of the materials according to the invention.

The materials according to the invention are processed in the usual manner according to the processes recommended for this.

Preparation of the emulsions used in layer construction examples 1 and 2: Emulsion 1 (comparison, slow developing, highly sensitive)

A highly sensitive AgBrI emulsion with 11 mol% iodide was prepared by running the silver nitrate solution into a solution which contained gelatin in addition to potassium bromide and potassium iodide. The temperature was 70 ° C., the pH 6.5 and the pAg at the end of the precipitation 8.7.

After the silver halide had precipitated, polystyrene sulfonic acid was added to the emulsion, the temperature was brought to 25 ° C. and the pH was lowered to 3.5. The emulsion flocculated and was washed until the pAg was 7.5.

The redispersion was carried out by raising the pH to 6.5 and heating the emulsion to 40 ° C. Gelatin was added to the emulsion until the gelatin / silver ratio was 0.7. The emulsion was then ripened to the optimum sensitivity with the addition of sulfur compounds and gold salts. The average grain diameter of the polydisperse emulsion was 0.9 µm. The electron microscopic examination showed that in addition to compact crystals, plate-shaped crystals were also present.

The silver halide concentration is equivalent to 100 g AgNO₃ per kg emulsion.

The emulsion was stabilized as indicated in the layer structure example 1A, mixed with the additives indicated in layer no. 4 of structure 1A (based on 100 g of AgNO₃) and cast with an order of 6.0 g of AgNO₃ per m².

Emulsion 2 (comparison, slow developing, low sensitive)

A less sensitive AgBrI emulsion with 8 mol% iodide was prepared by simultaneously running a 2 molar silver nitrate solution and a 2 molar potassium bromide solution into a gelatin solution which additionally contained potassium bromide and the corresponding amount of potassium iodide. The temperature was 55 ° C., the pAg was kept constant at 8.3 during the precipitation. After the silver halide had been precipitated, the procedure described in Example 1 was followed.

Crystals with a preferably cubic shape were obtained, the mean grain diameter being 0.45 μm. The silver halide concentration is equivalent to 100 g AgNO₃ per kg emulsion.

The emulsion was stabilized as indicated in layer structure 1A, mixed with the additives indicated in layer no. 3 of structure 1A (based on 100 g of AgNO₃) and cast with an order of 4.0 g of AgNO₃ per m².

Emulsion 3 (fast developing, highly sensitive)

A highly sensitive silver bromide iodide emulsion containing 7 mol% iodide was prepared by mixing an aqueous gelatin solution with KBr (pBr 1.45) and 350 mg of 1,8-dihydroxy-3,6-dithiaoctane as the silver halide solvent. The temperature was brought to 70 ° C. In this solution, an aqueous AgNO₃ solution and a mixture of KBr and KI, dissolved in water, were run in simultaneously, the AgNO₃ content 30% of the total amount of silver and the amount of KI 24 mol%, based on the added silver nitrate amounted to. In a further feed, the remaining 70% of the silver nitrate solution was run in simultaneously with the KBr solution, the pBr value being kept at 1.45. The inflow took place with increasing flow velocity, the inflow being increased by a factor of 6. The silver halide concentration is equivalent to 100 g AgNO₃ per kg.

The emulsion was stabilized like emulsions 1 and 2, mixed with the additives specified in layer no. 13 of layer structure 2C (based on 100 g of AgNO₃) and poured with an order of 6.0 g of AgNO₃ per m².

Emulsion 4 (fast developing, low sensitivity)

A less sensitive AgBrI emulsion with 5 mol% iodide was prepared by mixing an aqueous gelatin solution with the calculated amount of KI and KBr, with the pBr set to 1.65. The temperature was set at 55 ° C. and the silver nitrate solution and the equimolar potassium bromide solution were run in in 15 minutes. Cube-shaped crystals with an average diameter of 0.42 μm were obtained, 90% of the grains deviating from the average grain size by no more than ± 60%. The silver halide concentration is equivalent to 100 g AgNO₃ per kg emulsion. The silver halide concentration is equivalent to 100 g AgNO₃ per kg emulsion. The emulsion was stabilized like emulsions 1 and 2, mixed with the additives indicated in layer no. 3 of layer structure 1D (based on 100 g of AgNO₃) and poured with an order of 4.0 g of AgNO₃.

Emulsion 5 (comparison, highly sensitive, slowly developing)

A platelet-shaped emulsion containing 12 mol% iodide was prepared by mixing a 1% by weight gelatin solution with enough KBr that a pBr of 1.0 was achieved. In this solution, a 1.2 molar AgNO₃ solution and a 1.2 molar KBr solution ran at 55 ° C. in 5 minutes. in an amount equal to 2.5% of the total silver used for the emulsion preparation. Then the pBr with AgNO₃ Superscripted to 1.36. In the further course, a mixture of 1.06 mol KBr and 0.14 mol KI was fed simultaneously with 1.2 mol AgNO₃ in 52 min with increasing dosage. A total of 205 g AgNO₃ were consumed.

The gelatin silver halide emulsion was flocculated, washed, redispersed and additional gelatin was added. Then it was ripened optimally with sulfur and gold compounds. The silver bromide iodide grains contained 12 mol% iodide and preferably showed platelet-shaped crystals with an average grain diameter of 1.85 μm. The thickness was approximately 0.15 to 0.20 µm. The silver halide concentration is equivalent to 100 g AgNO₃ per kg emulsion.

The emulsion was stabilized like emulsions 1 and 2, provided with the additives indicated in layer no. 9 of layer structure 2A (based on 100 g of AgNO₃) and cast with an order of 6.0 g of AgNO₃ per m².

Emulsion 6 (highly sensitive, fast developing)

An emulsion containing platelet-shaped crystals and containing 8 mol% iodide was prepared analogously to emulsion 5; however, only 65% of the total AgNO₃ was consumed in the precipitation with the mixture of KBr and KI. Then again with a 1.2 molar KBr solution and the remaining 1.2 molar AgNO₃ solution until the end.

The emulsion was flocculated, washed, redispersed and gelatin was additionally added and optimally ripened with sulfur and gold salts.

The silver bromide iodide crystals contained 8 mol% iodide and were preferably platelet-shaped with an average grain diameter of 1.8 μm. The thickness was about 0.12 µm.

The silver halide concentration is equivalent to 100 g AgNO₃ per kg emulsion.

The emulsion was stabilized like emulsions 1 and 2, provided with the additives indicated in layer 9 of layer structure 2D (based on 100 g AgNO₃) and poured with an order of 6.0 g AgNO₃ per m².

Emulsion 7 (fast developing, low sensitivity)

A fine-grained, less sensitive emulsion, the silver halide crystals of which consist of several layers with different halide compositions, was prepared by the double-jet process using methylimidazole as silver halide solvent at a pAg of 8. For nucleation, a 0.5 molar AgNO₃ solution and a 0.5 molar KBr solution were simultaneously in the gelatin solution at 63 ° C run until 10% of the total silver was used up. Thereafter, in a second double inlet with a 2 molar AgNO₃ solution and a further solution which contained 1.76 mol of KBr and 0.24 mol of KI, a further 60% of the silver was added for crystal formation.

In the 3rd double inlet a further 30% of the silver was added with a 2 molar AgNO₃ solution and a 2 molar KBr solution. Cubic crystals with a total content of 7 mol% of iodide were obtained, which had an edge length of 0.5 μm. The silver halide crystal consists of three zones, the core consisting of pure AgBr, followed by a zone which contains 12 mol% iodide and an outer zone, which in turn consists of pure AgBr.

The emulsion was flocculated as usual, washed and, after adding further gelatin, optimally ripened with sulfur and gold compounds. The silver halide concentration is equivalent to 100 g AgNO₃ per kg emulsion.

The emulsion was stabilized like emulsions 1 and 2, provided with the additives indicated in layer 3 of layer structure 2D (based on 100 g AgNO₃) and poured with an order of 2.5 g AgNO₃ per m².

Emulsion 8 (fast developing, low sensitivity)

A fine grain, low sensitivity emulsion was prepared as in Example 7, but with an additional one AgClBr layer was installed. The structure of the finished crystal had the following composition: innermost layer (34%): AgBr, 2nd layer (36%): AgBrI with 20 mol% iodide, 3rd layer (4%): AgClBr and 50 mol% chloride , outermost layer (26%); AgBrI and 5 mol% iodide.

The crystals were cube-shaped with an edge length of 0.5 µm. The emulsion was flocked, washed, provided with additional gelatin and optimally ripened with sulfur compounds and gold salts. The silver halide concentration is equivalent to 100 g AgNO₃ per kg emulsion.

The emulsion was stabilized like emulsions 1 and 2, provided with the additives indicated in layer no. 7 of layer structure 2D (based on 100 g of AgNO₃) and cast with an order of 1.0 g of AgNO₃ per m².

The differently large AgNO₃ orders for the emulsion test pieces 1 to 8 had to be selected in order to achieve a sufficiently high measuring accuracy with the color development (= 195 sec.) According to the following measuring method.

Two test specimens each of the emulsion layers were exposed behind a gray step wedge with white light (exposure time 1 / 100˝) and processed in the processing process given in layer structure example 1: 1 test specimen each with the type-specific color development time (= 195 seconds) and one test specimen with the shortened one Processing time of 65 seconds (= 1/3 type time).

The results are summarized in Table 1. It can be seen from this that only emulsions 3, 4, 6, 7 and 8 meet the conditions according to the invention.

example 1

To demonstrate the advantages according to the invention, four layer structures of a color photographic recording material are produced, the layer structures mentioned below with 1A, 1B and 1C serving as a comparison and 1D representing the layer structure according to the invention.

• 1A: Langsam entwickelnde Emulsionen (Nr. 1 und Nr. 2) und langsam kuppelnde Farbkuppler und DIR-­Kuppler (k < 10⁴ [l/Mol·sec].
• 1B: Langsam entwickelnde Emulsionen (Nr. 1 und Nr. 2) wie bei 1A,
  schnell kuppelnde Farbkuppler und DIR-Kuppler (k < 10⁴ [l/Mol·sec].
• 1C: schnell entwickelnde Emulsionen (Nr. 3 und Nr. 4), langsam kuppelnde Farb- und DIR-Kuppler wie bei 1A.
• 1D: schnell entwickelnde Emulsionen (Nr. 3 und Nr. 4) (wie bei 1C) und
  schnell kuppelnde Farb- und DIR-Kuppler (wie bei 1B).

Tabelle 2 Farb-, DIR- und Maskenkuppler für Beispiel 1 k < 10⁴ [1/Mol′sec] k > 10⁴ [1/Mol′sec] In Schicht Nr: Farbkuppler k(x10⁴) [1/Mol′sec] DIR-Kuppler k(x10⁴) [1/Mol′sec] Maskenkuppler k(x10⁴) [1/Mol′sec] Farbkuppler k(x10⁴) [1/Mol′sec] DIR-Kuppler k(x10⁴) [1/Mol′sec] Maskenkuppler k(x10⁴) [1/Mol′sec] 3 C11 DIR-8 RM3 C3 DIR-2 RM1 0,14 0,46 0,8 3,2 1,1 3,5 4 C9 - RM3 C1 - RM1 0,66 0,8 7,0 3,5 6 M17 DIR-8 YM4 M11 DIR-5 YM2 0,32 0,46 0,11 3,7 2,8 1,4 7 M16 - YM6 M9 - YM3 0,42 0,18 7,0 3,0 9 Y27 DIR-10+DIR-9 Y5 DIR-5+DIR-2 0,011 0,34 0,9 4,4 2,8 1,1 10 Y27 Y5 0,011 4,4 The individual layer structures are designed according to the following principles:

• 1A: Slowly developing emulsions (No. 1 and No. 2) and slowly coupling color couplers and DIR couplers (k <10⁴ [l / mol · sec].
• 1B: Slowly developing emulsions (No. 1 and No. 2) as in 1A,
  fast-coupling color couplers and DIR couplers (k <10⁴ [l / mol · sec].
• 1C: fast developing emulsions (No. 3 and No. 4), slow coupling color and DIR couplers as in 1A.
• 1D: rapidly developing emulsions (No. 3 and No. 4) (as in 1C) and
  fast coupling color and DIR couplers (like 1B).

Table 2 Color, DIR and mask couplers for example 1 k <10⁴ [1 / mol′sec] k> 10⁴ [1 / mol′sec] In layer no: Color coupler k (x10⁴) [1 / Mol′sec] DIR coupler k (x10⁴) [1 / mol′sec] Mask coupler k (x10⁴) [1 / Mol′sec] Color coupler k (x10⁴) [1 / Mol′sec] DIR coupler k (x10⁴) [1 / mol′sec] Mask coupler k (x10⁴) [1 / Mol′sec] 3rd C11 DIR-8 RM3 C3 DIR-2 RM1 0.14 0.46 0.8 3.2 1.1 3.5 4th C9 - RM3 C1 - RM1 0.66 0.8 7.0 3.5 6 M17 DIR-8 YM4 M11 DIR-5 YM2 0.32 0.46 0.11 3.7 2.8 1.4 7 M16 - YM6 M9 - YM3 0.42 0.18 7.0 3.0 9 Y27 DIR-10 + DIR-9 Y5 DIR-5 + DIR-2 0.011 0.34 0.9 4.4 2.8 1.1 10th Y27 Y5 0.011 4.4

Production of layer structures 1A to 1D:

The following layers were applied to a transparent cellulose triacetate substrate in the order given here.

The quantities given relate to 1 m². For the silver halide application, the equivalent amounts of AgNO₃ are given.

All silver halide emulsions were stabilized with 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraaazaindene per 100 g of AgNO₃.

Layer structure 1A (comparison) 1st layer (antihalo layer)

0.2 g / m² black colloidal silver
1.2 g / m² gelatin
0.1 g / m² UV absorber UV 1
0.2 g / m² UV absorber UV 2
0.02 g / m² tricresyl phosphate
0.03 g / m² dibutyl phthalate

2nd layer (intermediate layer )

0.25 g AgNO₃ a Mikrat-Ag (Br, J) emulsion: medium grain ⌀ = 0.07 µm, 0.5 mol% iodide
1.0 g / m² gelatin
0.05 g / m² colored coupler RM3
0.10 g / m² tricresyl phosphate

3rd layer (low red sensitive layer)

2.8 g / m² AgNO₃ of the spectrally red-sensitive emulsion No. 2
1.8 g / m² gelatin
0.6 g / m² colorless coupler C11
0.03 g / m² DIR coupler DIR-8
0.04 g / m² colored coupler RM3
0.36 g / m² tricresyl phosphate
0.16 g / m² dibutyl phthalate

4th layer (highly red-sensitive layer)

2.4 g / m² AgNO₃ of the spectrally red-sensitive emulsion No. 1
1.5 g / m² gelatin
0.12 g / m² colorless coupler C9
0.02 g / m² colored coupler RM3
0.01 g / m² tricresyl phosphate
0.08 g / m² dibutyl phosphate

5th layer (separation layer)

0.8 g / m² gelatin
0.05 g / m² 2,5-di-t-pentadecyl hydroquinone
0.05 g / m² tricresyl phosphate
0.05 g / m² dibutyl phthalate

6th layer (low green sensitive layer)

1.8 g / m² AgNO₃ of the spectrally green-sensitive emulsion No. 2
1.2 g / m² gelatin
0.52 g / m² colorless coupler M17
0.06 g / m² DIR coupler DIR-8
0.15 g / m² colored coupler YM4
0.6 g / m² tricresyl phosphate

7th layer (highly green-sensitive layer)

2.0 g / m² AgNO₃ of spectrally green sensitized emulsion No. 1
1.2 g / m² gelatin
0.14 g / m² colorless coupler M16
0.04 g / m² colored coupler YM6
0.20 g / m² tricresyl phosphate

8th layer (yellow filter layer )

0.04 g / m² yellow colloidal silver passivated by 6 mg 1-phenyl-5-mercaptotetrazole / g Ag
0.8 g / m² gelatin
0.15 g / m² 2,5-di-t-pentadecylhydroquinone
0.4 g / m² tricresyl phosphate

9th layer (low blue-sensitive layer)

0.65 g / m² AgNO₃ of spectrally blue-sensitized emulsion No. 2
1.0 g / m² gelatin
0.75 g / m² colorless coupler Y27
0.20 g / m² DIR coupler DIR-10
0.10 g / m² DIR coupler DIR-9
0.30 g / m² tricresyl phosphate
0.25 g / m² polyethyl acrylate

10th layer (highly blue-sensitive layer)

1.05 g / m² AgNO₃ of spectrally blue-sensitized emulsion No. 1
0.8 g / m² gelatin
0.25 g / m² colorless coupler Y27
0.15 g / m² tricresyl phosphate
0.15 g / m² polyethyl acrylate

11th layer (protective layer)

1.5 g / m² gelatin
0.1 g / m² UV absorber UV1
0.2 g / m² UV absorber UV2
0.02 g / m² tricresyl phosphate
0.02 g / m² dibutyl phthalate

12th layer (protective layer)

0.5 g / m² AgNO₃ of a Mikrat-Ag (Br, J) emulsion, medium grain ⌀ 0.07 µm, 0.5 mol% iodide,
1.2 g / m² gelatin
0.4 g / m² hardener
1.0 g / m² formaldehyde scavenger
0.25 g / m² polymethacrylate particles with an average diameter of 1.5 µm

Layer structure 1B (comparison)

Like layer structure 1A, however:

in the 2nd layer:

0.05 g / m² colored coupler RM1 (instead of RM3)

in the 3rd layer:

0.6 g / m² colorless coupler C3 (instead of C11)
0.03 g / m² DIR coupler DIR-2 (instead of DIR-8)
0.04 g / m² colored coupler RM1 (instead of RM3)

in the 4th layer

0.12 g / m² colorless coupler C1 (instead of C9)
0.02 g / m² colored coupler RM1 (instead of RM3)

in the 6th layer:

0.4 g / m² colorless coupler M11 (instead of M17)
0.06 g / m² DIR coupler DIR-5 (instead of DIR-8) 0.15 g / m² colored coupler YM2 (instead of YM4)

in the 7th layer:

0.14 g / m² colorless coupler M9 (instead of M16)
0.04 g / m² colored coupler YM3 (instead of YM6)

in the 9th layer:

0.75 g / m² colorless coupler Y5 (instead of Y27)
0.02 g / m² DIR coupler DIR-5 (instead of DIR-10)
0.10 g / m² DIR coupler DIR-2 (instead of DIR-9)

in the 10th layer:

0.25 g / m² colorless coupler Y5 (instead of Y27)

Layer structure 1C (comparison)

like layer structure 1A, however

in the 3rd layer

2.8 g / m² AgNO₃ of spectrally red-sensitive emulsion No. 4 (instead of emulsion No. 2)

in the 4th layer

2.4 g / m² AgNO₃ of spectrally red-sensitive emulsion No. 3 (instead of emulsion No. 1)

in the 6th layer

1.8 g / m² AgNO₃ of spectrally green-sensitive emulsion No. 4 (instead of emulsion No. 2)

in the 7th layer

2.0 g / m² AgNO₃ of the spectrally green-sensitive emulsion No. 3 (instead of emulsion No. 1)

in the 9th shift

0.65 g / m² AgNO₃ of spectrally blue-sensitized emulsion No. 4 (instead of emulsion No. 2)

in the 10th shift

1.05 g / m² AgNO₃ of spectrally blue-sensitized emulsion No. 3 (instead of emulsion No. 1)

Layer structure 1D (according to the invention)

Like layer structure 1B, but with the rapidly developing emulsions used in layer structure 1C:
Emulsion No. 4 in the 3rd, 6th and 9th layers
Emulsion No. 3 in the 4th, 7th and 10th layers
(Quantities as specified for layer structure A to C).

After exposure behind a gray step wedge (exposure time = 1 / 100˝), samples of the assemblies 1A to 1D were processed according to the color negative processing method described below: Color development 3 min 15 sec 38.0 ° C bleaching 4 min 20 sec 38.0 ° C Water 1 min 05 sec 38.0 ° C Fix 4 min 20 sec 38.0 ° C To wash 3 min 15 sec 38.0 ° C stabilization 1 min 05 sec 24.0 ° C dry <43 ° C 17 min 20 sec

The color development, bleaching, fixing and stabilizing baths had the following composition. The quantities refer to 1000 ml. Color development bath: Sodium tripolyphosphate 2.0 g Sodium sulfite (anhydrous) 2.0 g Sodium bicarbonate 8.0 g Potassium or sodium bisulfate 7.0 g Potassium bromide 1.8 g Potassium or sodium carbonate (anhydrous) 30.0 g Hydroxylamine sulfate 3.0 g N¹-ethyl-N¹- (2-hydroxyethyl) -3-methyl-1,4-phenylenediammonium sulfate (monohydrate) = ̂ CD 4 2.6 g Water to make up to 1000 ml pH = 10.2 Bleaching bath: Ethylenediaminetetraacetic acid (sodium-iron salt) 100.0 g Potassium bromide 50.0 g 20% ammonia solution 6.0 ml Water to make up to 1000 ml pH = 5.9-6.1 Fixing bath: Ammonium thiosulfate 120.0 g Sodium sulfite (anhydrous) 20.0 g Potassium metabisulfite (crystalline) 20.0 g Water to make up to 1000 ml Stabilizing bath: Di-n-octyl sulfosuccinate (10% solution) 10.0 ml Formalin 35-37% 6.0 ml Water to make up to 1000 ml

Processing fluctuations were simulated by
Variation of the development time (type time = 195 sec .; ± 30 sec.)
Variation of the development temperature (type temp. = 38 ° C; ± 2 °)
Variation of developer pH (type pH = 10.2; ± 0.2)
Variation of developer concentration (± 20%)
Variation of the KBr content in the developer (type = 1.8 g / l; ± 0.5 g)

• 1a: Variation der Entwicklungszeit ± 30 sec.
• 1b: Variation der Entwicklungstemperatur ± 2°C
• 1c: Variation der Entwickler-pH-Wertes ± 0,2
• 1d: Variation der Entwicklerkonzentration ± 20%
• 1e: Variation des Kaliumbromidgehalts im Entwickler ± 0,5 g/l.

FIG. 1 shows the deviations from sensitivity, gradation (with color density = 1.0 via fog) and fog when these development parameters are varied compared to the values obtained with precise type processing. In detail, the diagrams in FIG. 1 show the variations in the following development parameters:

• 1a: variation of the development time ± 30 sec.
• 1b: variation of the development temperature ± 2 ° C
• 1c: variation of developer pH ± 0.2
• 1d: variation of developer concentration ± 20%
• 1e: variation of the potassium bromide content in the developer ± 0.5 g / l.

It can be seen from these diagrams that the layer structure 1D according to the invention is much more resistant to the deviations from the exact type conditions than the comparison structures 1A to 1C.

It would have been expected that the edge effects and the interimage effects would be reduced by using the rapidly developed emulsions. Surprisingly, it has been found that this almost does not occur when these rapidly developed emulsions are combined with fast color and DIR couplers.

The size of the "edge effects" was also determined on these four layer structures 1A to 1D as in T.H. James, The Theory of the Photographic Process, 4th ed. Macmillan Publ. Co. Inc. New York / London (1977) pp. 609-614, (to avoid light scattering) determined by means of X-ray radiation: on each sample of the layered structures 1A to 1D, both a macro field and a 30 μm wide slit were exposed with the same X-ray dose. The samples were then processed using the color-negative method known from "The British Journal of Photography", 1974, pages 597 and 598. The density difference measured on these samples between the gap (= micro density) and the macro field (= macro density) at the X-ray dose which gives the macro density = 1.0 (via fog) is used in Table 4 as a measure of the size of the edge effect.

The interimage effect which improves the color quality also remains increased by the combination 1D according to the invention. Table 4, for example, shows the interimage effect the percentage by which the magenta gradation (or blue-green gradation) is greater for green exposure (or red exposure) than for additive white exposure at the point on the color density curve where the color density obtained with additive white exposure is D = 1.0 (via fog).

The processing of the layer structures when determining the interimage effect takes place in the same color negative process as stated above when determining the edge effect. Table 3 Layer structure Edge effect with macro density = 1.0 (over veil) IEE (%) with macro density = 1.0 (over veil) Blue green purple Blue green purple 1A 0.48 0.42 40 38 1B 0.32 0.28 30th 26 1C 0.22 0.19 20th 18th 1D 0.47 0.40 40 37

It can be seen from this table that the edge effects and the interimage effects of the construction 1D according to the invention are surprisingly practically not reduced compared to the comparison construction 1A (in contrast to 1B and 1C).

Example 2

Analogously to Example 1, four layer structures are compared with one another, layer structures 2A, 2B and 2C serving as a comparison and 2D representing the layer structure according to the invention. Table 4 Color, DIR and mask couplers for example 2 k <10⁴ [1 / mol.sec] k> 10⁴ [1 / mol.sec] In layer no: Color coupler k (x10⁴) [1 / mol · sec] DIR coupler k (x10⁴) [1 / mol · sec] Mask coupler k (x10⁴) [1 / mol · sec] Color coupler k (x10⁴) [1 / mol · sec] DIR coupler k (x10⁴) [1 / mol · sec] Mask coupler k (x10⁴) [1 / mol · sec] 3rd C12 DIR-9 + DIR-10 RM4 C7 DIR-1 + DIR-2 RM1 0.08 0.9 0.34 0.17 1.3 4.2 1.1 3.5 9 C10 DIR-9 RM4 C6 DIR-2 RM1 0.19 0.9 0.17 2.5 1.1 3.5 5 M19 DIR-10 YM6 M2 DIR-2 YM1 0.03 0.34 0.18 3.5 1.1 1.2 11 M17 DIR-10 YM6 M1 DIR-2 YM1 0.32 0.34 0.18 6.7 1.1 1.2 7 Y36 DIR-9 - Y1 DIR-7 - 0.01 0.9 5.0 1.5 13 Y28 DIR-8 - Y7 DIR-2 - 0.038 0.46 7.0 1.1

Production of the layer structures 2A to 2D

Layer support, quantitative data and stabilization of the emulsions as in Example 1.

Layer structure 2A (comparison) 1st layer (antihalo layer)

as in example 1 (see structure 1A).

2nd layer (intermediate layer )

0.4 g / m² AgNO₃ a Mikrat-Ag (BrJ) emulsion, average grain diameter 0.05 µm, 2 mol% iodide
1.2 g / m² gelatin
0.08 g / m² colored coupler RM 4
0.15 g / m² dibutyl phthalate

3rd layer (low red sensitive layer)

2.0 g / m² AgNO₃ of the spectrally red-sensitive emulsion No. 2
2.0 g / m² gelatin
0.58 g / m² colorless coupler C12
0.02 g / m² DIR coupler DIR 9
0.02 g / m² DIR coupler DIR 10
0.05 g / m² colored coupler RM 4
0.40 g / m² tricresyl phosphate
0.15 g / m² dibutyl phthalate

4th layer (separation layer)

0.8 g gelatin
0.05 g 2,5-di-t-pentadecyl hydroquinone
0.05 g tricresyl phosphate
0.05 g dibutyl phthalate

5th layer (low green sensitive layer)

1.8 g / m² AgNO₃ of the spectrally green-sensitive emulsion No. 2
1.6 g / m² gelatin
0.45 g / m² colorless coupler M19
0.05 g / m² DIR coupler DIR-10
0.12 g / m² colored coupler YM 6
0.52 g / m² tricresyl phosphate

6th layer (yellow filter layer )

0.02 g of yellow colloidal silver, passivated by 6 mg of 1-phenyl-5-mercaptotetrazole / g of AgNO₃ 0.8 g of gelatin
0.15 g 2,5-di-t-pentadecyl hydroquinone
0.2 g tricresyl phosphate

7th layer (low blue-sensitive layer)

0.65 g / m² of spectrally blue-sensitized emulsion No. 2
1.95 g / m² gelatin
0.85 g / m² colorless coupler Y 36
0.15 g / m² DIR coupler DIR-9
0.90 g / m² tricresyl phosphate

8th layer (separation layer)

like 4th layer

9th layer (highly red-sensitive layer)

2.2 g / m² AgNO₃ of the spectrally red-sensitized emulsion No. 5
1.2 g / m² gelatin
0.20 g / m² colorless coupler C 10
0.01 g / m² DIR coupler DIR-9
0.02 g / m² colored coupler RM 4
0.15 g / m² tricresyl phosphate
0.10 g / m² dibutyl phthalate

10th layer (separating layer)

like 4th layer

11th layer (highly green-sensitive layer)

2.0 g / m² AgNO₃ of the spectrally green-sensitized emulsion No. 5
1.2 g / m² gelatin
0.16 g / m² colorless coupler M17
0.01 g / m² DIR coupler DIR-10
0.03 g / m² colored coupler YM 6
0.15 g / m² tricresyl phosphate

12th layer (yellow filter layer )

like 6th layer.

13th layer (highly blue-sensitive layer

0.85 g / m² AgNO₃ of spectrally blue-sensitized emulsion No. 5
1.2 g / m² gelatin
0.15 g / m² colorless coupler Y 28
0.01 g / m² DIR coupler DIR-8
0.25 g / m² tricresyl phosphate

14th layer (protective and hardening layer )

1,0 g/m² Formaldehydfänger der Formel

0,08 g/m² Dibutylphthalat
0,24 g/m² UV-Absorbergemisch gemäß 1. Schicht
0,25 g/m² Polymethacrylat-Teilchen mit mittleren Teilchendurchmesser von 1,45 µm0.5 g / m² AgNO₃ of a Mikrat-Ag (Br, J) emulsion, average grain diameter 0.07 µm, 0.5 mol% iodide,
1.2 g / m² gelatin
0.4 g / m² hardening agent of the formula

1.0 g / m² formaldehyde scavenger of the formula

0.08 g / m² dibutyl phthalate
0.24 g / m² UV absorber mixture according to the 1st layer
0.25 g / m² polymethacrylate particles with an average particle diameter of 1.45 µm

Layer structure 2B (comparison)

like layer structure 2A, but:

in the 2nd layer:

0.08 g / m² colored coupler RM 1 (instead of RM 4)

in the 3rd layer:

0.58 g / m² colorless coupler C 7 (instead of C 12)
0.02 g / m² DIR coupler DIR 1 (instead of DIR 9)
0.02 g / m² DIR coupler DIR 2 (instead of DIR 10)
0.05 g / m² colored coupler RM 1 (instead of RM 4)

in the 5th layer:

0.45 g / m² colorless coupler M 2 (instead of M 19
0.05 g / m² DIR coupler DIR 2 (instead of DIR 10)
0.12 g / m² colored coupler YM 1 (instead of YM 6)

in the 7th layer:

0.85 g / m² colorless coupler Y 1 (instead of Y 36)
0.15 g / m² DIR coupler DIR 7 (instead of DIR 8)

in the 9th layer:

0.20 g / m² colorless coupler C 6 (instead of C 10)
0.01 g / m² DIR coupler DIR 2 (instead of DIR 9)
0.02 g / m² colored coupler RM 1 (instead of RM 4)

in the 11th layer:

0.16 g / m² colorless coupler M 1 (instead of M 18)
0.01 g / m² DIR coupler DIR 2 (instead of DIR 10)
0.03 g / m² colored coupler YM 1 (instead of YM 6)

in the 13th layer:

0.15 g / m² colorless dome Y 7 (instead of Y 28)
0.01 g / m² DIR coupler DIR 2 (instead of DIR 8)

Layer structure 2C (comparison)

Like layer structure 2A, but:

in the 3rd layer:

2.0 g / m² AgNO₃ of spectrally red-sensitive emulsion No. 7 (instead of No. 2)

in the 5th layer:

1.8 g / m² AgNO₃ of spectrally green-sensitized emulsion No. 7 (instead of No. 2)

in the 7th layer:

0.65 g / m² AgNO₃ of spectrally blue-sensitized emulsion No. 8 (instead of No. 2)

in the 9th layer:

2.2 g / m² AgNO₃ of the spectrally red-sensitive emulsion No. 6 (instead of No. 5),
10 mg / m² of the development accelerator E 1

in the 11th layer:

2.0 g / m² AgNO₃ of spectrally green-sensitized emulsion No. 6 (instead of No. 5)
10 mg / m² of the development accelerator E 1

in the 13th layer:

0.85 g / m² AgNO₃ of spectrally blue-sensitized emulsion No. 3 (instead of No. 5)
5 mg / m² of the development accelerator E 1

Layer structure 2D (according to the invention)

Like layer structure 2B, but with the rapidly developing emulsions used in layer structure 2C.

The samples of the layer structures 2A to 2D were exposed and processed like those from Example 1.

FIG. 2 shows the deviations from sensitivity, gradation (with color density = 1.0 via fog) and fog with variation of the development parameters compared to those values which have been obtained with typical processing.

• 1a: Variation der Entwicklungszeit ± 30 sec.
• 1b: Variation der Entwicklungstemperatur ± 2°C
• 1c: Variation des Entwickler-pH-Wertes ± 0,2
• 1d: Variation der Entwicklerkonzentration ± 20 %
• 1e: Variation des Kaliumbromidgehaltes im Entwick ler ± 0,5 g/l

In detail, the diagrams in FIG. 2 show the variations in the following development parameters:

• 1a: variation of the development time ± 30 sec.
• 1b: variation of the development temperature ± 2 ° C
• 1c: variation of the developer pH ± 0.2
• 1d: variation of developer concentration ± 20%
• 1e: variation of the potassium bromide content in the developer ± 0.5 g / l

The edge effects and the interimage effects were also determined on the four layer structures 2A to 2D (as indicated in Example 1); the results are shown in Table 5. Table 5 Layer structure Edge effect with macro density = 1.0 (over veil) Interimage effect IIE (%) with macro density = 1.0 (over layer) Blue green purple Blue green purple 2A 0.54 0.50 52 45 2 B 0.38 0.33 34 29 2C 0.27 0.23 22 20th 2D 0.55 0.48 50 44

The conclusions that can be drawn from the results listed in the table are analogous to those from Example 1 with regard to edge effects and interimage effects.

Claims (9)

1. Color photographic recording material comprising a support and at least one silver halide emulsion layer applied to the support, which has at least one color coupler with a coupling rate constant at pH = 10.2 and 38 ° C. of ≧ 10⁴ [l / mol · sec] and at least one DIR coupler is assigned a coupling rate constant at pH = 10.2 and 38 ° C of ≧ 10⁴ [l / mol · sec], characterized in that a silver halide emulsion is used which is in contact with the above-mentioned color and DIR couplers at 38 ° C a color developer of the following composition Sodium tripolyphosphate 2.0 g Sodium sulfite (anhydrous) 2.0 g Sodium bicarbonate 8.0 g Potassium or sodium bisulfate 7.0 g Potassium bromide 1.8 g Potassium or sodium carbonate (anhydrous) 30.0 g Hydroxylamine sulfate 3.0 g N¹-ethyl-N¹- (2-hydroxyethyl) -3-methyl-1,4-phenylenediammonium sulfate (monohydrate) 2.6 g Water to make up to 1000 ml pH = 10.2 a relative maximum color density

of at least 50%. 2. Color photographic recording material according to claim 1, characterized in that the silver halide emulsion has a relative maximum color density of at least 70%. 3. Color photographic recording material according to claim 1, characterized in that the inhibitor split off from the DIR coupler has a diffusibility of ≧ 0.4. 4. Color photographic recording material according to claim 1, characterized in that it contains couplers of the following classes: a) 2-equivalent yellow coupler of the benzoylacetanilide type and / or pivaloylacetanilide type b) Purple couplers of the pyrazolo-azole type and / or acylaminopyrazolone type c) Teal couplers of the 2-ureidophenol type and / or 5-amino-1-naphthol type d) red mask coupler with O-escape group of the general formula
Cp-OL _(0-1) dye
in the
Cp teal coupler
L link
Dye dye with λ _max between 510-590 nm
mean. 5. Color photographic recording material, characterized in that in the case of multiple layers having the same spectral sensitivity, the color couplers of the higher-sensitive sub-layers have a higher coupling rate constant than that of the lower-sensitive sub-layers. 6. Color photographic recording material according to claim 1, characterized in that in the sub-layers of the color photographic recording material also mixtures of several rapidly developing emulsions and / or mixtures of several rapidly coupling color couplers and / or mixtures of several rapidly coupling DIR couplers, the inhibitors of which have high diffusibility , are included. 7. Color photographic recording material according to claim 1, each having at least one blue, green and red sensitive layer, characterized in that at least one of the blue, green or red sensitive layers is a silver halide emulsion with a relative maximum color density of at least 50%, color coupler with a coupling rate constant at pH = 10.2 and 38 ° C of ≧ 10⁴ [l / mol · sec], DIR couplers with a coupling rate constant at pH = 10.2 and 38 ° C of ≧ 10⁴ [l / mol · sec] and those split off from DIR couplers Inhibitors with a diffusibility of ≧ 0.4 has. 8. Color photographic recording material according to claim 1, characterized in that it contains development accelerators and / or source accelerators. 9. Color photographic recording material according to claim 1, characterized in that the difference in the coupling speed constant between the color coupler and DIR coupler is at most a factor of 5.

Images