US3155510A - Diffusion-resistant organic resin-coupler reaction products for photographic gelatin ayers - Google Patents

Diffusion-resistant organic resin-coupler reaction products for photographic gelatin ayers Download PDF

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Publication number
US3155510A
US3155510A US125079A US12507961A US3155510A US 3155510 A US3155510 A US 3155510A US 125079 A US125079 A US 125079A US 12507961 A US12507961 A US 12507961A US 3155510 A US3155510 A US 3155510A
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US
United States
Prior art keywords
diffusion
color
acid
photographic
coupler
Prior art date
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.)
Expired - Lifetime
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US125079A
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English (en)
Inventor
Nogradi Josef
Ulrich Hans
Pelz Willibald
Puschel Walter
Schellenberger Hans
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Agfa Gevaert NV
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Agfa AG
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/327—Macromolecular coupling substances
    • G03C7/3275—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/835—Macromolecular substances therefor, e.g. mordants

Definitions

  • This invention relates to organic, polymeric compounds in photographic gelatin layers, particularly photographic sflver halide gelatin emulsion layers being fast to diffusion.
  • organic compounds to be incorporated into the individual layers can be obtained by linle'ng these compounds to more highly polymeric compounds.
  • synthetic compounds of high molecular weight for example polyvinyl alcohol, like an acetal to color couplers and to add these polymers to the emulsion.
  • linkages through carbonamide bridges between coupler and copolymers have already been described.
  • polyethylene imines described for example in United States Patent No. 2,307,399
  • Couplers linked to synthetic polymers have various disadvantages. For example, those containing amino groups tend to fog various emulsions. Others cannot be added to the amulsion in the necessary concentration, because they are not suificiently miscible with the binding agent of the photographic layer e.g. gelatin. Thus only low color intensities are obtained. Many synthetic polymers to which the color couplers are linked, for example copolymers of styrene and maleic anhydride, increase the viscosity of the coating solution to an alarming degree thus complicating the casting procedure. In general this cannot be compensated by adding water, since the drying of the applied layer is then rendered more difficult. Color couplers with long-chain diffusion-inhibiting radicals have similar disadvantages.
  • copolymers of N vinylpyrrolidone with polymerizable unsaturated acid chlorides such as methacrylic acid chloride, acrylic acid chloride fumaric acid dichloride, crotom'c acid chloride or polymerizable acid anhydrides, such as maleic acid anhydride.
  • N-vinylpyrrolidone and acid derivatives can be varied, the preferred ratio being from 20 to mol percent of N-vinylpyrrolidone to 80 to 20 mol percent of acid derivative.
  • the copolymers are preferably prepared in an inert solvent, for example cyclic ethers such as dioxane, tetrahydrofuran, aromatic hydrocarbons such as benzene or toluene, or dialkyl amides such as dimethylformamide.
  • cyclic ethers such as dioxane, tetrahydrofuran, aromatic hydrocarbons such as benzene or toluene, or dialkyl amides such as dimethylformamide.
  • polymerization catalysts can be used the peroxides usual for this purpose, azodiisobutyric acid dinitrile and the like.
  • the polymerization temperature depends on the decomposition temperature of the polymerization catalyst being used and lies, in general, between 50 and C.
  • copolymers can be linked with all monomeric organic compounds which are to be incorporated in difiusion-resisting manner into photographic layers containing gelatin. More particularly color couplers generally used in color photography coupling components such as described in British Patent No. 861,138, dyestuffs, such as filter dyestuffs, substances absorbing ultraviolet light, organic developing substances, stabilizers and the like can be reacted with the N-vinyl pyrrolidone copolymers.
  • the polymeric couplers, filter dyestuffs, developers, stabilizers and the like which are obtained can be added alone or in combination with suitable monomeric com pounds to the photographic layers. They can, in general, be used both with photographic black-and-white materials and with color photographic multi-layer materials and may be added both to the silver halide emulsion layer and to one of the photographic auxiliary layers.
  • the reaction of the copolymers with the monomeric organic compounds in question is effected by known methods and depends on Whether acid chlorides or acid anhydrides have been used for the production of the copolymers, and whether the monomeric organic compound comprises a free hydroxyl group or a primary or secondary amino group.
  • the reaction can be carried out quantitatively with equimolecular quantities of the reactants; it is also possible to use only some of the acid chloride or acid anhydride groups for the acylation and to convert the remainder by hydrolysis into carboxyl groups.
  • the monomeric unsaturated acid derivatives can also be directly reacted with the monomeric organic compound to be incorporated. This product can then be copolymerized with N-vinyl-pyrrolidone.
  • 3-aminophenol or 2-chloro-5- aminophenol may, for example be reacted.
  • EXAMPLE 1 1.5 g. of the polymeric yellow color coupler described under 1(a) are dissolved in 20 cc. of methanol and 20 cc. of 4 percent sodium hydroxide solution and, in admixture with 100 cc. of a conventional gelatino-silver halide emulsion, applied to a subbed cellulose ester support, dried, exposed to light and subjected to a color development.
  • a yellow dyestulf is obtained upon development.
  • EXAMPLE 2 A subbed support of polycarbonate on the basis of bis- (di-oxyphenyl-alkane) as described for example in British Patent No. 808,629 is coated with a photographic emulsion layer prepared by adding 1.5 g. of the polymeric magenta coupler 2(a), described above under preparation of difiusion resistant magenta couplers, solved in 20 ml. of methanol and 20 m1. of 4 percent aqueous sodium hydroxide to 100 ml. of a conventional silver halide gelatin emulsion. After exposure and usual color processing After imagewise exposure and conventional color processing using N,N-diethyl-aminoaniline as color-forming developer a cyan image is obtained.
  • EXAMPLE 41 A support of baryta-coated paper is coated with an ordinary silver chloride emulsion being sensitized to red light and containing 15 g. per kg. emulsion of the polymeric cyan coupler 3(a), described above under preparation of diffusion resistant color couplers. This layer is overcoated with a silver chloride emulsion layer sensitized to green light and containing 15 g. per leg. of the emulsion of the polymeric magenta coupler 1(a), as described above under preparation of diffusion-resistant color coupler.
  • the material After casting an interlayer, containing colloidal silver as yellow filter layer, the material is over-coated with a third silver halide emulsion layer, containing equal amounts as the layers mentioned above of the polymeric yellow coupler 1(a), as described under preparation of diilusionresistant color couplers.
  • EXAMPLE 5 A multi-layer color-photographic material is prepared according to Example 4 with the exception that between the layer sensitive to red and green light a separation layer is interposed. Said layer is cast from 5 percent aqueous gelatin solution containing per litre 15 g. of the colorless coupler 4 dissolved in 50 ml. of methanol and 20 ml. of 4 percent aqueous sodium hydroxide.
  • Said colorless couplers react with the oxidation products of a phenylyenediamine developer to form colorless products.
  • the material is exposed and color processed according to Example 4.
  • the color separation is far better compared with a photographic multi-color material containing no separation layer or only pure gelatin layers as separation layers.
  • binding agents of the photographic layers are not limited to those previously mentioned, because many other water-permeable, film-forming binding agents are suitable such as polyvinylalcohol, carboxymethylcellulose and derivatives, synthetic organic polymers and mixtures thereof with gelatin.
  • a photographic material comprising a support coated with a plurality of emulsion layers, at least one of which is a photosensitive silver halide emulsion layer
  • the improvement which consists in adding to one of the emulsion layers a reaction product of (i) a color coupler containing a radical of the group consisting of hydroxy and amino radicals which is capable of forming a dye upon development with a primary amine developer, and
  • reaction product the color coupler and the diffusion-resistant copolymer are linked through a bivalent radical of the group consisting of CO--O and CONH radicals.
  • a process as defined in claim 1 in which the color coupler from which the reaction product is produced is a substance that is capable of forming upon development with a primary amine developer a dye of the group consisting of azomethine, indoaniline and phenazonium dyes.
  • a photographic material comprising a support coated with a plurality of emulsion layers, at least one of which is a photosensitive silver halide emulsion layer and at least one of which contains the reaction product of (i) a color coupler containing a radical of the group consisting of hydroxy and amino radicals which is capable of forming a dye upon development with a primary amine developer, and
  • reaction product the color coupler and the diffusion-resistant copolymer are linked through a bivalent radical of the group consisting of --COO and -CONH- radicals.
  • a photographic material as defined in claim 4 in which the color coupler from which the reaction product is produced is a substance that is capable of forming upon development with a primary amine developer a dye of the group consisting of azomethine, indoaniline and phenazonium dyes.
  • a photographic material as defined in claim 4 in which the copolymer of N-vinylpyrrolidone and maleic anhydride (ii) from which the reaction product is produced contains between 20 and 80 mols of N-vinylpyrrolidone per 100 mols of copolymer.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US125079A 1960-07-26 1961-07-19 Diffusion-resistant organic resin-coupler reaction products for photographic gelatin ayers Expired - Lifetime US3155510A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA35206A DE1123913B (de) 1960-07-26 1960-07-26 Verfahren zur diffusionsfesten Einlagerung von organischen Verbindungen in gelatinehaltige photographische Schichten

Publications (1)

Publication Number Publication Date
US3155510A true US3155510A (en) 1964-11-03

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US (1) US3155510A (en))
BE (1) BE606548A (en))
CH (1) CH402604A (en))
DE (1) DE1123913B (en))
FR (1) FR1303090A (en))
GB (1) GB954924A (en))

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876428A (en) * 1969-02-24 1975-04-08 Borys Murin Multilayer silver halide material containing a white coupler

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9119518D0 (en) * 1991-09-12 1991-10-23 Minnesota Mining & Mfg Silver halide imaging materials

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2712995A (en) * 1949-07-04 1955-07-12 Agfa Ag Process for the direct production of positive photographic images
US2882262A (en) * 1956-05-14 1959-04-14 Eastman Kodak Co N-(acryloxyalkyl)- and n-(methacryloxyalkyl)-2-pyrrolidones and polymers thereof
FR1233875A (fr) * 1958-08-27 1960-10-12 Du Pont Perfectionnements aux émulsions photographiques à base d'halogénures d'argent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2712995A (en) * 1949-07-04 1955-07-12 Agfa Ag Process for the direct production of positive photographic images
US2882262A (en) * 1956-05-14 1959-04-14 Eastman Kodak Co N-(acryloxyalkyl)- and n-(methacryloxyalkyl)-2-pyrrolidones and polymers thereof
FR1233875A (fr) * 1958-08-27 1960-10-12 Du Pont Perfectionnements aux émulsions photographiques à base d'halogénures d'argent
GB867900A (en) * 1958-08-27 1961-05-10 Du Pont Improvements in or relating to photographic silver halide emulsions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876428A (en) * 1969-02-24 1975-04-08 Borys Murin Multilayer silver halide material containing a white coupler

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Publication number Publication date
FR1303090A (fr) 1962-09-07
CH402604A (de) 1965-11-15
DE1123913B (de) 1962-02-15
GB954924A (en) 1964-04-08
BE606548A (en))

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