US3615478A - Method of fixing photographic material containing a free radial producing compound - Google Patents
Method of fixing photographic material containing a free radial producing compound Download PDFInfo
- Publication number
- US3615478A US3615478A US623234A US3615478DA US3615478A US 3615478 A US3615478 A US 3615478A US 623234 A US623234 A US 623234A US 3615478D A US3615478D A US 3615478DA US 3615478 A US3615478 A US 3615478A
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- United States
- Prior art keywords
- light
- photographic material
- sensitive
- image
- sodium
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- G03C1/00—Photosensitive materials
- G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
Definitions
- Juten ABSTRACT Light-sensitive photographic material comprising a light-sensitive generator of free radicals and a color modifier capable of showing a visible color change by the acnon of such free radical lS fixed against photolytic color change by contact with a salt of hydrogen sulfide or a salt of a sulfur-containing oxygen acid.
- fixation of a light-sensitive photographic material of the above-specified type was accomplished by a thermal fixing method or a solvent fixing method.
- the former fixing method the light-sensitive photographic material on which an image is formed by irnagewise exposure to light is heated so that the remaining light-sensitive component decomposed or sublimed. The photographic material then no longer shows color change when exposed to light.
- a composition which comprises diphenyl amine and carbon tetrabromide and one which comprises brilliant green and carbon tetrabromide.
- aroyl trihalogenated hydrocarbons are preferred as photoactivators.
- carbon tetrabromide is extremely toxic and volatile at an elevated temperature. During handling, therefore, a special care should be taken to prevent from inhalation of the carbon tetrabromide vapor.
- Aroyl trihalogenated hydrocarbon also is incon- .venient because of its lachrymatory nature and volatility.
- a light-sensitive photographic composition which is used in a thermally fixable, light-sensitive photographic material should be readily heat-decomposable or sublimable, and such light-sensitive photographic composition usually is rather unstable even at an ordinary temperature.
- a light-sensitive photographic material useful in thermal fixation has rather poor storage ability, whereas a well storable light-sensitive photographic material is not so suitable for thermal fixation.
- Another fixing method is a solvent fixing process wherein a light-sensitive photographic material is treated with an appropriate solvent to remove the residual light-sensitive component so that the the photographic material becomes insensitive to further light-exposure. It is essential to use a solvent that dissolves the residual light-sensitive component well, but does not dissolve the formed image. If a solvent is used which has even a little dissolving power for the image, an unsatisfactory reproduction will be obtained due to lowered resolution resulting from the exudation of the image. Suitable solvents for solvent fixing process are very few and they are expensive, and therefore, it is a difiicult problem to find an appropriate solvent. Furthermore, the solvent-fixing process is to wash out so-called nonimage area, and so, it is required for complete washing-out to use a selected solvent in large amount or to replenish a fresh solvent from time to time. Thus, this process is rather expensive and impractical.
- An object of the present invention is to provide a fixing method which effectively prevents postexposure fogging of the noted type of photographic material, which has no adverse influence on the quality of an image formed, and which is free from health hazard.
- the fixing agents are used in the form of aqueous solutions which may be applied to exposed light-sensitive photographic materials. Exposed lightsensitive photographic materials are coated with or dipped into aqueous solutions containing the fixing agents.
- the fixing agents used in this invention diminish the photo activity of a photoactivator remaining intact, i.e. which do not take part in image formation, by a chemical reaction in which such agents capture halogen contained in the photoactivator to render the activator inactive.
- Typical compounds useful as fixing agents referred to above are as follows:
- any one of the above-listed compounds is prepared to an aqueous solution (about 1-30 percent concentration) which is then applied to exposed, light-sensitive photographic material.
- the amount of the aqueous solution (thls solution will be simply referred to as a fixer" hereafter) will vary depending on the type of a photoactivator used and the thickness of the light-sensitive layer, but it usually is sufficient in such an amount as used for development of a diazo-type copying paper, i.e. in an amount necessary to moisten the surface of the light-sensitive photographic material.
- a fixing method according to the invention can be deemed as semidry process.
- the fixer may be added with a binder such as cellulose derivative, vinyl polymer, synthetic rubber, etc.
- the required operation is quite similar to, the fixation of a silver halide photographic material.
- the required dipping time will vary, but it usually is within the range of from several seconds to several minutes.
- a coating technique in fixing it will be better to use a fixer having a higher concentration in comparison with the case when dipping is employed.
- drying of the photographic material by heating at a temperatureof l00l80 C. (by means of hot rolls, hot plates, etc., having a surface temperature of l00-l C.) after fixation treatment is desirable to have increased fixing effect, while it makes possible to use a fixer having a lower concentration.
- Addition of 2-15 percent of a bufier agent e.g. sodium carbonate, borax, sodium acetate, sodium dihydrogen phosphate or the like alkaline substance
- a bufier agent e.g. sodium carbonate, borax, sodium acetate, sodium dihydrogen phosphate or the like alkaline substance
- addition of 2-l0 g. of hydroquinone, metol or similar reducing substance per cc. of a fixer is recommendable to prevent discoloration of the background and degradation of the resulting image.
- a fixer usable in this invention may contain one or more additives or adjuvants which are commonly known in the photographic art.
- a lightsensitive photographic material which comprises a photoactivator being capable of generating a free radical by the action of light and a color modifier showing a visible color change through the action of said free radical also may contain one or more auxiliary components.
- alkyl, haloalkyl, acetyl, haloacetyl, alkaryl and alkoxy include, for example, o-nitro- 01,11,a-tribromo-acetophenone, m-nitro-a,a,a-tribromoacetophenone, p-nitro-a,a,atribromo-acetophenone, a,a,a-tribromo-acetophenone, a,a,a mtetrabromo-acetophenone, a,a,a-tribromo-3,4- dichloroacetophenone. a,a,a-tribromo-2,S-dimethylacetophenone. a,a,a-p-tetrabromo-acetophenone, a,a,a',a ',a'[lll]
- R-SO o-nitro- 01,11,a-tribromo-acetophenone
- A is a heterocyclic group which may be substituted.
- R R and R individually means H. C] or Br, excepting the case where all of R,, R and R are hydrogen.
- They include, for example, m,cu,w-tribromoquinaldine, (0,0)- dibromoquinaldine, 2-w,w,m-tribromomethyl-4-methylquinoline, w,w-diChlromethyl-quinoline, wbromolepidine, 2w-bromomethyl-isoquinoline, 4-w,w,mtribromomethyl-pyrimidine, 4-phenyl-6-m,w,wtribromopyrimidine, 2-w,m,w-trichloromethyl-6-nitrobenzthiazole, lphenyl-3-m,w,w-trichloromethyl-5- pyrazolone, w,w,w-tribr0molepidine, bromomethylate, aw,w-dibromomethyl-4-chl0ropyridine, l-methyl- 2(
- Typical examples are hexabromo-dimethyl sulfoxide, pentabromodimethyl sulfoxide, hexabromo-dimethyl sulfone, trichloromethyl-phenyl sulfone, tribromomethyl-phenyl sulfone, trichloromethyl-p-chlorophenyl sulfone, tribomomethylp-nitrophenyl sulfone, sulfone, Z-trichloromethylbenzothiazolyl sulfone-(2), 4,6-dimethyl-pyrimidyl-2- tribromomethyl sulfone, tetrabromo dimethyl sulfone, 2,4- dichlorophenyl-trichloromethyl sulfone, 2-methyl-4- chlorophenyl-trichloromethyl sulfone, 2,5-dimethyl-4- chlorophenyl-trichloromethyl sulf
- a color 0 modifier of the one type is that which originally is a colorless substance capable of converting into colored state by the action of a free radical generated from a photoactivator. Such color modifier is useful in so-called negative-positive system.
- a color'modifier of the other type is that which originally has a color, but can be converted into bleached or differently colored state by the action of a free radical. Such color modifier is useful in so-called positive-positive system.
- color modifiers are the following; diphenylamine, dibenzylamine, triphenylamine, N-hydroxyethyl-N-ethyl aniline, p,p'-methylenebis (N,N-diethylaniline) and the like amine compounds; leuco bases of such dyes as leuco crystal violet, leuco malachite green, michleris hydrol, leuco methylene blue, etc.; and various classes of dyes, e.g.
- diphenylmethane dyes triphenylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, anthraquinone dyes, iminonaphthoquinone dyes, azomethine dyes.
- a method of the present invention comprises dipping or coating exposed light-sensitive photographic material into or with an aqueous solution of the beforedefined fixing agent and then, if desired, drying said photographic material by heating. According, it is entirely free from generation of noxious vapor or from decrease in image resolution. This enables us to obtain an excellent and stable copy through simple operations.
- the photographic material having the negative image is dipped into a fixer of:
- the fixer used further contains 5 g. of hydroquinone.
- the resulting fixed reproduction showed a clean, white background even when stored over a long period.
- Acetone-100 cc. is coated on a photographic paper which is then dried.
- the light-sensitive photographic material thus obtained is subjected to light exposure in the same manner as in example 1 and then passed through a wet-diazotype-developing machine in which a fixer of:
- Water-100 cc. is applied in an amount just sufficient to moisten the surface of said photographic material. A blue image which is stable against further light exposure is obtained.
- EXAMPLE 4 On a white base paper, the surface of which is pretreated with a 10 percent aqueous solution of polyvinyl chloride (polymerization degree 600), a light-sensitive solution of the following formulation is coated:
- the light-sensitive photographic material is a bluish green color and useful in positive-positive system, i.e., bleach-out. Exposure of the photographic material to light yields a clear bluish green image, which can be stabilized in the same manner as in example 2 by using a fixer of the following formulation:
- Acetone-1 00 cc The light-sensitive photographic material obtained is sensitive over the wide range of wavelength including a visible region, since it includes a photo-sensitizing dye.
- the photographic material is subjected to light exposure by imagewise irradiation at a distance of 30 cm. and for 15- 1) seconds by means of a slide projector, with a 500 w. tungsten lamp as light source, having an image-bearing photographic negative placed therein. A clear blue image is obtained.
- the imaged photographic material is then treated by using the same apparatus and fixer as used in example 2, to obtain stabilized image which is entirely safe against further light exposure.
- an imaging material comprising a photoactivator capable of generating a halogen free radical by the action of light and a color modifier capable of producing a visible color change by the action of said halogen free radical; exposing said material imagewise to light thereby effecting imagewise halogen free radical generation and a coincident visible color change; and fixing the resulting image; the improvement which comprises a fixing method wherein said material, after light exposure, is contacted with an aqueous solution of a sulfur compound selected from the group consisting of watersoluble salts of hydrogen sulfide and water-soluble salts of sulfur-containing oxygen acids for a time sufficient to inactivate said photoactivator.
- a sulfur compound selected from the group consisting of watersoluble salts of hydrogen sulfide and water-soluble salts of sulfur-containing oxygen acids for a time sufficient to inactivate said photoactivator.
- drying step comprises contacting said material with a surface heated to about C.
Abstract
Description
Claims (5)
- 2. The improvement according to Claim 1 comprising the further step of drying the material thus contacted at a temperature between about 100*-180* C.
- 3. The improvement according to Claim 1 wherein said material is coated with said solution.
- 4. The improvement according to Claim 1 wherein said material is dipped into said solution.
- 5. The improvement according to claim 1 wherein said solution further comprises up to about 10 percent of a hydroxy benzene reducing agent.
- 6. The improvement according to claim 2 wherein said drying step comprises contacting said material with a surface heated to about 150* C.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1671166 | 1966-03-18 |
Publications (1)
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US3615478A true US3615478A (en) | 1971-10-26 |
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US623234A Expired - Lifetime US3615478A (en) | 1966-03-18 | 1967-03-15 | Method of fixing photographic material containing a free radial producing compound |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050085144A1 (en) * | 2003-10-16 | 2005-04-21 | Kimberly-Clark Worldwide, Inc. | Durable charged particle coatings and materials |
US7413550B2 (en) * | 2003-10-16 | 2008-08-19 | Kimberly-Clark Worldwide, Inc. | Visual indicating device for bad breath |
US7438875B2 (en) | 2003-10-16 | 2008-10-21 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using metal-modified silica particles |
US7488520B2 (en) | 2003-10-16 | 2009-02-10 | Kimberly-Clark Worldwide, Inc. | High surface area material blends for odor reduction, articles utilizing such blends and methods of using same |
US7582485B2 (en) | 2003-10-16 | 2009-09-01 | Kimberly-Clark Worldride, Inc. | Method and device for detecting ammonia odors and helicobacter pylori urease infection |
US7582308B2 (en) | 2002-12-23 | 2009-09-01 | Kimberly-Clark Worldwide, Inc. | Odor control composition |
US7666410B2 (en) | 2002-12-20 | 2010-02-23 | Kimberly-Clark Worldwide, Inc. | Delivery system for functional compounds |
US7678367B2 (en) | 2003-10-16 | 2010-03-16 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using metal-modified particles |
US7754197B2 (en) | 2003-10-16 | 2010-07-13 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using coordinated polydentate compounds |
US20100211034A1 (en) * | 2003-10-16 | 2010-08-19 | Kimberly-Clark Worldwide, Inc. | Odor absorbing extrudates |
US7837663B2 (en) | 2003-10-16 | 2010-11-23 | Kimberly-Clark Worldwide, Inc. | Odor controlling article including a visual indicating device for monitoring odor absorption |
US7879350B2 (en) | 2003-10-16 | 2011-02-01 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using colloidal nanoparticles |
-
1967
- 1967-03-15 US US623234A patent/US3615478A/en not_active Expired - Lifetime
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7666410B2 (en) | 2002-12-20 | 2010-02-23 | Kimberly-Clark Worldwide, Inc. | Delivery system for functional compounds |
US7582308B2 (en) | 2002-12-23 | 2009-09-01 | Kimberly-Clark Worldwide, Inc. | Odor control composition |
US7678367B2 (en) | 2003-10-16 | 2010-03-16 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using metal-modified particles |
US7754197B2 (en) | 2003-10-16 | 2010-07-13 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using coordinated polydentate compounds |
US7488520B2 (en) | 2003-10-16 | 2009-02-10 | Kimberly-Clark Worldwide, Inc. | High surface area material blends for odor reduction, articles utilizing such blends and methods of using same |
US7582485B2 (en) | 2003-10-16 | 2009-09-01 | Kimberly-Clark Worldride, Inc. | Method and device for detecting ammonia odors and helicobacter pylori urease infection |
US7413550B2 (en) * | 2003-10-16 | 2008-08-19 | Kimberly-Clark Worldwide, Inc. | Visual indicating device for bad breath |
US7141518B2 (en) | 2003-10-16 | 2006-11-28 | Kimberly-Clark Worldwide, Inc. | Durable charged particle coatings and materials |
US20050085144A1 (en) * | 2003-10-16 | 2005-04-21 | Kimberly-Clark Worldwide, Inc. | Durable charged particle coatings and materials |
US7438875B2 (en) | 2003-10-16 | 2008-10-21 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using metal-modified silica particles |
US20100211034A1 (en) * | 2003-10-16 | 2010-08-19 | Kimberly-Clark Worldwide, Inc. | Odor absorbing extrudates |
US7794737B2 (en) | 2003-10-16 | 2010-09-14 | Kimberly-Clark Worldwide, Inc. | Odor absorbing extrudates |
US7837663B2 (en) | 2003-10-16 | 2010-11-23 | Kimberly-Clark Worldwide, Inc. | Odor controlling article including a visual indicating device for monitoring odor absorption |
US7879350B2 (en) | 2003-10-16 | 2011-02-01 | Kimberly-Clark Worldwide, Inc. | Method for reducing odor using colloidal nanoparticles |
US8211369B2 (en) | 2003-10-16 | 2012-07-03 | Kimberly-Clark Worldwide, Inc. | High surface area material blends for odor reduction, articles utilizing such blends and methods of using same |
US8221328B2 (en) | 2003-10-16 | 2012-07-17 | Kimberly-Clark Worldwide, Inc. | Visual indicating device for bad breath |
US8702618B2 (en) | 2003-10-16 | 2014-04-22 | Kimberly-Clark Worldwide, Inc. | Visual indicating device for bad breath |
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AS | Assignment |
Owner name: CHEMICAL BANK, A BANKING INSTITUTION OF, NEW YORK Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: BANK OF CALIFORNIA N.A. THE; A NATIONAL BANKING AS Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: CONTINENTAL ILLINOIS NATIONAL BANK & TRUST CO., OF Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: CHEMICAL BANK, A BANKING INSTITUTION OF NY. Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: CHASE MANHATTAN BANK, N.A. THE; A NATIONAL BANKING Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 Owner name: SECURITY NATIONAL BANK, A NATIONAL BANKING ASSOCIA Free format text: SECURITY INTEREST;ASSIGNOR:KEUFFEL & ESSER COMPANY A.N.J. CORP;REEL/FRAME:003969/0808 Effective date: 19820323 |