EP0464435B1 - Matériau de reproduction photographique pour la couleur - Google Patents

Matériau de reproduction photographique pour la couleur Download PDF

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Publication number
EP0464435B1
EP0464435B1 EP91109845A EP91109845A EP0464435B1 EP 0464435 B1 EP0464435 B1 EP 0464435B1 EP 91109845 A EP91109845 A EP 91109845A EP 91109845 A EP91109845 A EP 91109845A EP 0464435 B1 EP0464435 B1 EP 0464435B1
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EP
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Prior art keywords
layer
couplers
compounds
acid
color
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EP91109845A
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German (de)
English (en)
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EP0464435A1 (fr
Inventor
Reinhart Dr. Matejec
Günter Dr. Helling
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/327—Macromolecular coupling substances
    • 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
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C7/392—Additives
    • G03C7/396—Macromolecular additives

Definitions

  • the invention relates to a color photographic recording material containing polymeric color couplers with particularly thin, low-gelatin silver halide emulsion layers, at least one of the light-sensitive, color coupler-containing layers or partial layers having a gelatin content of not more than 40% by weight.
  • Color coupler-containing silver halide emulsion layers with a gelatin content of less than 40% by weight are known, e.g. from EP-A 0 320 821.
  • Thin photographic layers are particularly easy to produce using polymeric couplers (latex couplers) and low gelatin content.
  • polymeric couplers latex couplers
  • low gelatin content because low-gelatin casting solutions solidify only poorly, this usually results in a rather poor casting quality.
  • the invention relates to a color photographic recording material having at least one light-sensitive silver halide emulsion layer which contains a polymeric color coupler and not more than 40% by weight of gelatin, characterized in that this silver halide emulsion layer in addition to gelatin per 100 parts by weight of the polymeric color coupler 2.5 contains up to 50 parts by weight of a polymeric viscosity-increasing agent.
  • the silver halide emulsion layer contains no more than 30% by weight gelatin.
  • the polymeric color couplers (latex couplers) used according to the invention are obtained by homopolymerizing polymerizable monomeric couplers (monomer K), by copolymerizing monomer K with at least one further ethylenically unsaturated copolymerizable compound (monomer C), by polymer-analogous reaction of a pre-formed polymer with a coupling compound or by polyaddition or polycondensation of bifunctional compounds containing color couplers, such as, for example in EP-A 0 357 069.
  • Monomeric couplers are described in, for example, DE-A 1 908 674, DE-A 3 217 200, DE-A-31 48 125, DE-A-33 00 665, DE-A-32 14 567, DE-A-32 26 163, DE-A-33 05 718, DE-A-32 21 883, DE- A-27 25 591, DE-A-34 01 455, DE-PS 1 297 471, DE-PS 1 570 672, DE-A-24 07 569, EP-A-00 27 284, DE-A-33 31 743, DE-A-33 36 582, EP-A-0 136 924, DE-A-34 32 396, EP-A-0 133 262, US 4,874,689, EP-A-0 322 003, EP-A -0 316 955.
  • couplers are understood to mean compounds which, together with the oxidation product of a color developer, give an optionally colored organic compound.
  • the polymeric color couplers used can contain, in addition to the repeating units from the coupler-containing monomer K, further copolymerized monomers C.
  • comonomers C include esters and amides of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, for example acrylic acid, ⁇ -chloroacrylic acid, an (alk) acrylic acid such as methacrylic acid, for example acrylamide, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n- Butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate, lauryl methacrylate and methylene bisacrylamide) vinyl esters (for example vinyl acetate, vinyl propionate and vinyl laurate, acrylonitrile, Methacrylonitrile, aromatic vinyl compounds (e.g.
  • styrene and its derivatives such as vinyltoluene, divinylbenzene, vinyl acetophenone and styrene sulfonic acid, itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-pyridine and Vinyl pyridine.
  • vinyl alkyl ether e.g. vinyl ethyl ether, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-pyridine and Vinyl pyridine.
  • polymeric couplers, urea and / or urethane group-containing monomers can be contained in polymerized form as described in DE-A 3 536 608.
  • the molecular weights of the polymeric color couplers used according to the invention are preferably greater than 5,000, in particular greater than 20,000, in order to ensure sufficient diffusion resistance.
  • the upper limit is not critical and can reach values of over 10 million, in particular if bifunctional or polyfunctional monomers are used as additional comonomer C.
  • Two or more of the comonomer compounds C described above can be used together.
  • the ethylenically unsaturated monomer C can be selected such that it has a favorable effect on the physical properties and / or chemical properties of the copolymer to be produced, for example the solubility, compatibility with a binder such as gelatin in the photographic colloid composition or other photographic ultraviolet ray absorbing agents, known photographic antioxidants and known color image forming agents, the flexibility and thermal stability thereof, etc.
  • the polymeric couplers are obtained by polymerization reactions which have been carried out using polymerization regulators having 8 or more carbon atoms, as described in US Pat. No. 4,874,689.
  • the polymeric color coupler used in the present invention can be prepared by an emulsion polymerization process or by polymerizing a monomer or monomer mixture in an organic solvent and then dispersing the solution in latex form in an aqueous solution of gelatin.
  • the free radical polymerization of an ethylenically unsaturated monomer is initiated by adding a free radical, which is formed by thermal decomposition of a chemical initiator, by the action of a reducing agent on an oxidizing compound (redox initiator) or by physical action, such as irradiation with ultraviolet rays or other high-energy radiations, high frequencies.
  • a free radical which is formed by thermal decomposition of a chemical initiator, by the action of a reducing agent on an oxidizing compound (redox initiator) or by physical action, such as irradiation with ultraviolet rays or other high-energy radiations, high frequencies.
  • chemical initiators include persulfates (e.g. ammonium persulfate or potassium persulfate, hydrogen peroxide, organic peroxides (e.g. benzoyl peroxide or t-butyl peroctoate and azonitrile compounds (e.g. 4,4'-azobis-4-cyanovaleric acid or azobisisobutyronitrile).
  • persulfates e.g. ammonium persulfate or potassium persulfate
  • hydrogen peroxide e.g. benzoyl peroxide or t-butyl peroctoate
  • azonitrile compounds e.g. 4,4'-azobis-4-cyanovaleric acid or azobisisobutyronitrile
  • Examples of conventional redox initiators include hydrogen peroxide iron (II) salt, potassium persulfate, sodium metabisulfite and cerium IV salt alcohol.
  • a compound with a surface-active effect is used as the emulsifier which can be used in the emulsion polymerization.
  • Preferred examples thereof include soap, a sulfonate, a sulfate, a cationic compound, an amphoteric compound and a high molecular weight protective colloid.
  • Specific examples of the emulsifiers and their functions are described in Belgische Chemische Industrie, vol. 28, pages 16 to 20, 1963.
  • a latex is obtained directly in the emulsion polymerization process.
  • the coupler latex used according to the invention can, however, also be obtained by dispersing a polymeric coupler which may have been prepared in a different manner in aqueous gelatin solution. An organic solvent which may be present here is expediently removed before the casting.
  • Suitable solvents are those which have a certain degree of water solubility so that they are suitable for removal by washing with water in a gelatin noodle state and those which can be removed by spray drying, vacuum or steam rinsing.
  • organic solvents examples include esters, especially lower alkyl esters, lower alkyl ethers, ketones, halogenated hydrocarbons (e.g. methylene chloride, trichlorethylene, fluorinated hydrocarbons, alcohols (e.g. methyl alcohol to butyl alcohol) and a combination thereof.
  • esters especially lower alkyl esters, lower alkyl ethers, ketones, halogenated hydrocarbons (e.g. methylene chloride, trichlorethylene, fluorinated hydrocarbons, alcohols (e.g. methyl alcohol to butyl alcohol) and a combination thereof.
  • dispensing agent Any type of dispensing agent can be used in the dispersion. However, ionic surfactants and especially anionic surfactants are preferred.
  • ampholytic surfactants such as C-cetylbetaine, an N-alkylaminopropionate and an N-alkyliminodipropionate.
  • a small amount (not more than 50% by weight, based on the monomer K) of a permanent solvent namely a water-immiscible organic solvent with a high boiling point (ie above 200 ° C), for example, dibutyl phosphate and / or tricresyl phosphate can be added.
  • the concentration of the permanent solvent be sufficiently low to plasticize the polymer while it is kept in a solid particle state. Furthermore, when using a permanent solvent, it is preferable that the amount thereof is as small as possible so that the thickness of the final emulsion layer or hydrophilic colloid layer is reduced to maintain good sharpness.
  • Viscosity-increasing agents which do not meet these requirements are unsuitable because of a reduction in the hardening activity, insufficient increase in viscosity or deterioration in the surface properties of the finished material, such as, for example, wet scratch resistance and dirt acceptance.
  • Suitable viscosity-increasing agents which meet the above requirements are high-molecular natural products or to the high molecular semi or fully synthetic products.
  • Examples are homo- or copolymers of ethylene sulfonic acid, fumaric acid, monomethyl fumarate, monoethyl fumarate, 3-acrylamido-3-methylbutyric acid, monomethyl itaconate, bis (3-sulfopropyl) itaconate, itaconic acid, maleic acid, mesaconic acid, ⁇ -methylene glutaric acid, 2-acryloyl acid acid, 2-acryloyl acid acid, 2-acryloyl acid acid -Methacryloyloxyethylsulfonic acid, monoamidomaleic acid, crotonic acid, 3-acrylamidopropane-1-sulfonic acid, N- (n- and p-vinylbenzyl) -iminodiacetic acid, 2-methacryloyloxyethyl-1-sulfonic acid, o- and p-styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid , Vinyl
  • suitable thickeners are polyvinyl alcohol, polyvinyl alcohol graft polymers e.g. with acrylic acid, cellulose derivatives such as carboxymethyl cellulose, cellulose ether and cellulose sulfate, gelatin derivatives, gelatin graft polymers, polyethylene oxides, polysaccharides such as pectins, alginic acid and alginic acid derivatives, carraghenans, agar derivatives, guar derivatives, xanthan and xanthan derivatives and polydextranes.
  • polyvinyl alcohol polyvinyl alcohol graft polymers e.g. with acrylic acid, cellulose derivatives such as carboxymethyl cellulose, cellulose ether and cellulose sulfate, gelatin derivatives, gelatin graft polymers, polyethylene oxides, polysaccharides such as pectins, alginic acid and alginic acid derivatives, carraghenans, agar derivatives, guar derivatives, xanthan and x
  • Polyacrylamide, poly-methacrylic acid and polyacrylic acid salts, copolymers of acrylamide and methacrylic acid or acrylic acid salts, copolymers of 2-acrylamido-2-methylpropanesulfonic acids and their salts, polyvinyl alcohol, alginate, carraghenan, xanthan and polydextranes are particularly preferred.
  • Alkyl esters of sugar e.g. a carboxy group, a sulfo group, a phospho group, a sulfate group and a phosphate group, e.g.
  • Alkyl carboxylic acid salts alkyl sulfonic acid salts, alkyl benzene sulfonic acid salts, alkyl naphthalene sulfonic acid salts, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphates; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines and amine oxides; and cationic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts, e.g. Pyridinium and imidazolium compounds and aliphatic or heterocyclic surfactant phospho
  • anionic surface active agents having a sulfo group and fluorinated surface active agents are particularly preferred.
  • the thickeners used according to the invention are added to the comparatively low-gelatin casting solutions containing the polymeric color couplers in amounts of 2.5-50 parts by weight per 100 parts by weight of the polymeric coupler. In this way, flawless layers can be produced despite the low gelatin content. This in turn makes it possible to achieve a certain desired maximum color density with thinner layers using latex couplers, which has an overall advantageous effect on the sharpness of the photographic recording material.
  • the recording material according to the invention preferably has a total dry layer thickness (without layer support) of less than 20 ⁇ m.
  • color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper.
  • Suitable supports for the production of color photographic materials are, for example, films and foils of semisynthetic and synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate, and paper laminated with a baryta layer or ⁇ -olefin polymer layer (eg polyethylene).
  • These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
  • the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
  • the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
  • Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.
  • Each of the light-sensitive layers of different spectral sensitivity can consist of a single layer or 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 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.
  • the green or Red-sensitive layers can be selected by dispensing with the yellow filter layer, in which, for example, the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow the support.
  • 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.
  • Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877, 0 125 522.
  • sub-layers of the same spectral spectral sensitivity can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
  • a sub-layer with higher sensitivity will be arranged further away from the support than a sub-layer with lower sensitivity.
  • Partial layers of the same spectral sensitivity can be adjacent to one another or separated by other layers, for example by layers of a different spectral sensitivity.
  • all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
  • At least one layer or partial layer has the features according to the invention, ie it contains, in addition to light-sensitive silver halide, a latex coupler, gelatin in an amount of not more than 40% by weight, preferably not more than 30% by weight and a thickener in an amount of 2.5 to 50 parts by weight per 100 parts by weight latex coupler.
  • the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
  • the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
  • silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions. It can be predominantly compact crystals, e.g.
  • platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
  • the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, e.g. 12: 1 to 30: 1.
  • the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different.
  • the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
  • the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
  • Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
  • the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
  • the procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
  • Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium).
  • Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described for example by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 18, pp. 431 ff. And Research Disclosure 17643 (Dec. 1978), Chapter III).
  • a reduction sensitization can be carried out with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid) using hydrogen, by means of low pAg (eg less than 5) and / or high pH (eg above 8) .
  • reducing agents titanium-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidine sulfinic acid
  • 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 pentaazaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Furthermore, 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, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
  • metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can be used as antifoggants.
  • Heterocycles containing mercapto groups are particularly suitable, for example mercaptobenzothiazoles, hercaptobenzimidazoles, mercaptotetrazoles, hercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles can also contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • mercaptobenzothiazoles hercaptobenzimidazoles, mercaptotetrazoles, hercaptothiadiazoles, mercaptopyrimidines
  • these mercaptoazoles can also contain a water-solubilizing group, for example a carboxyl group or sulfo group.
  • Other suitable compounds are published in Research Disclosure 17643 (Dec. 1978), Chapter VI.
  • the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
  • the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
  • the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active 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 for improving the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • coating aids for preventing electrical charging, for improving the sliding properties, for emulsifying the dispersion, for preventing adhesion and for improving the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
  • non-ionic surfactants for example alkylene oxide compounds, glycerol compounds or glycidol compounds
  • cationic surfactants for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds
  • sulfonium compounds or phosphonium compounds anionic surfactants containing one Acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group
  • ampholytic surfactants for example amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
  • 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 bromides.
  • the differently sensitized 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.
  • cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
  • Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
  • Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone type, for example 3-acylaminopyrazolone or 3-anilino-pyrazolone of the indazolone or the pyrazoloazole.
  • Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; Suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
  • the color photographic recording material can also contain low molecular weight color couplers, both in the layer containing the latex coupler and in other layers.
  • the latex couplers as well as the low-molecular 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 point, 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 or through with the color coupling the color of the image dye produced is replaced (mask coupler), and the white couplers which, when reacted with color developer oxidation products, give essentially colorless products.
  • the 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling point, 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 known DIR couplers as well as DAR or. FAR coupler.
  • Examples of white couplers are: Examples of mask couplers are:
  • DIR couplers the development inhibitors of the azole type, e.g. Release triazoles and benzotriazoles are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281.28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416.
  • Other advantages for color rendering, i.e. Color separation and color purity, and for detail reproduction, i.e. Sharpness and graininess can be achieved with such DIR couplers, e.g. do not split off the development inhibitor directly as a result of the coupling with an oxidized color developer, but only after a further subsequent reaction, which is achieved, for example, with a timing group.
  • DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-0 167 168 and 0 219 713. This measure ensures trouble-free development and processing consistency.
  • the DIR couplers can be added to a wide variety of layers in a multilayer photographic material, e.g. also light-insensitive or intermediate layers. However, they are preferably added to the photosensitive silver halide emulsion layers, the characteristics of the silver halide emulsion, e.g. whose iodide content, the structure of the silver halide grains or their grain size distribution influence the photographic properties achieved.
  • the influence of the inhibitors released can be limited, for example, by the incorporation of an inhibitor catch report according to DE-A-24 31 223.
  • DAR or FAR couplers can be used, which release a development accelerator or an fogger.
  • Compounds of this type are described, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-0 089 834; 0 110 511, 0 118 087, 0 147 765 and in U.S.-A-4,618,572 and 4,656,123.
  • DIR, DAR or FAR couplers mainly the effectiveness of the residue released during coupling is 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-15 47 640).
  • the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are capable of diffusion or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
  • the material may further contain compounds other than couplers, which include, for example, a development inhibitor, a development accelerator, can release a bleach accelerator, a developer, a silver halide solvent, a fogging agent or an anti-fogging agent, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4,636,546, 4,345,024, 4,684,604 and in DE -A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
  • couplers include, for example, a development inhibitor, a development accelerator, can release a bleach accelerator, a developer, a silver halide solvent, a fogging agent or an anti-fogging agent, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4,636,546, 4,345,024, 4,684,
  • the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion from 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.
  • Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding 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.
  • oligomers or polymers 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.
  • anionic water-soluble compounds e.g. dyes
  • pickling polymers e.g. acrylic acid
  • Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
  • oil formers are dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, tridecoxyphosphate, 2-ethylhexylphosphate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, Dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-dibutyl-2-butoxy-5-t
  • the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
  • 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 ⁇ -naphthol type cyan couplers
  • 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, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes, Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
  • Suitable whiteners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
  • 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-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
  • photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
  • the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
  • 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.
  • suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
  • Suitable formalin scavengers include H 2 N-CONH- (CH 2 ) 2 -NH-CONH 2 ,
  • Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
  • the layers of the photographic material can be hardened with the usual hardening agents.
  • Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207), divinyl sulfone compounds, 5-acetyl-1,3-di-acryloylhexahydro-1, 3,5-triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316
  • the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
  • 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 and the swelling of the layer structure occurs as a result of the crosslinking reaction .
  • 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).
  • hardening agents which react very quickly with gelatin are, for example, 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 with the formation of peptide bonds and crosslinking of the gelatin.
  • Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step.
  • All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound.
  • Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
  • bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used.
  • Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
  • Persulfates and peroxides e.g. Hydrogen peroxide.
  • the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
  • the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
  • this stabilizing bath also acts as a final bath.
  • a color photographic recording material for color negative color development was produced (layer structure 1 A - comparison) by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application. All silver halide emulsions per 100 g of AgNO 3 were stabilized with 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • the achievable casting quality was excellent due to the addition of the thickener to the above-mentioned partial layers containing low-gelatin polymer couplers.
  • the modulation transfer function was determined on the two layer structures 1 A and 1 C as a measure of the image sharpness. The method is described by T.H. James, The Theory of the Photographic Process, 4th ed. Macmillan Publ. Co. Inc. New York / London (1977), p. 605.
  • Table 1 shows the spatial frequencies (in lines per mm) at which the MTF has a value of 50% as a measure of the image sharpness.
  • the layer structure 1 C according to the invention has a significantly higher image sharpness.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (2)

  1. Matériau d'enregistrement pour la photographie en couleurs, comprenant au moins une couche photosensible d'émulsion à l'halogénure d'argent qui contient un copulant chromogène polymère et pas plus de 40% en poids de gélatine, caractérisé en ce que cette couche d'émulsion à l'halogénure d'argent contient, en plus de la gélatine, par 100 parties en poids du copulant chromogène polymère, de 2,5 à 50 parties en poids d'un agent polymère augmentant la viscosité.
  2. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que l'épaisseur de couche totale à l'état sec (sans le support de couches) est inférieure à 20 µm.
EP91109845A 1990-06-29 1991-06-15 Matériau de reproduction photographique pour la couleur Expired - Lifetime EP0464435B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4020688A DE4020688A1 (de) 1990-06-29 1990-06-29 Farbfotografisches aufzeichnungsmaterial
DE4020688 1990-06-29

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EP0464435A1 EP0464435A1 (fr) 1992-01-08
EP0464435B1 true EP0464435B1 (fr) 1997-02-05

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EP0768570A1 (fr) * 1995-10-09 1997-04-16 Konica Corporation Méthode de formation d'image

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DE3113009A1 (de) * 1981-04-01 1982-10-21 Agfa-Gevaert Ag, 5090 Leverkusen Fotografisches aufzeichnungsmaterial
JP2540320B2 (ja) * 1987-03-25 1996-10-02 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JP2640236B2 (ja) * 1987-12-11 1997-08-13 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料

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EP0464435A1 (fr) 1992-01-08
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