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

Definitions

• the invention relates to a color photographic recording material with at least one red and / or green-sensitive silver halide emulsion layer containing a color coupler and to a method for producing photographic images.
• Color photographic recording materials which contain silver halide emulsions and so-called color couplers for the formation of dyes are already known.
• the color images are created by implementing the developer oxidation product with the color couplers.
• Color couplers and the dyes resulting from them should generally be stored in a diffusion-resistant manner and the dyes formed should have good stability against light as well as in the dark, in particular in the case of heat and moisture.
• Image dyes are broken down under the influence of atmospheric oxygen, humidity and temperature, which results in a decrease in the color density formed (dark fading).
• the white couplers compete with the color coupler for developer oxidation products. In this way sensitivity and gradation can be influenced.
• At least one red- and / or green-sensitive layer contains a polymer which has repeating units 1 with a 5-pyrazolone white coupler residue and repeating units 11 with a sulfonic acid residue.
• the polymer additionally contains a polymerized ethylenically unsaturated compound M.
• each in% by weight are contained:
• the polymer is contained in a layer which contains a phenol, a-naphthol or 5-pyrazolone as color coupler.
• the invention further relates to a process for the production of color photographic images, which is characterized in that the image-wise exposed recording material according to the invention is developed and subjected to the usual further processing.
• the polymers according to the invention preferably have a glass transition temperature (Tg) of at most + 20 ° C.
• Tg glass transition temperature
• layers of a mixture of polymer latices according to the invention and gelatin in the ratios 70:30 to 90:10 after drying are clear.
• Examples of comonomers M include an ester, preferably a lower alkyl ester and an amide derived from an acrylic acid, e.g. acrylic acid, one ⁇ -chloroacrylic acid, an ⁇ -alkyl acrylic acid such as methacrylic acid, etc. (e.g., acrylamide, methyl ethacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate, lauryl methacrylate and methylene bisacrylamide, etc.) Vinyl esters (e.g.,
• vinyl acetate, vinyl propionate and vinyl laurate, etc. acrylonitrile, methacrylonitrile, an aromatic vinyl compound (e.g. vinyl white styrene and a derivative thereof, such as vinyl toluene, divinylbenzene, vinyl acetophenone, etc.), itaconic acid, zitroconic acid chloride (a), tritonic acid chloride, e.g. vinyl ethyl ether, etc.), an ester of maleic acid, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and 4-vinylpyridine, etc.
• aromatic vinyl compound e.g. vinyl white styrene and a derivative thereof, such as vinyl toluene, divinylbenzene, vinyl acetophenone, etc.
• itaconic acid e.g. vinyl white styrene and a derivative thereof, such as vinyl toluene, divinylbenzene, vinyl aceto
• ethylenically unsaturated compounds M are used whose homopolymerized materials have a low glass transition temperature, e.g. Ethyl acrylate, butyl acrylate, ethyl hexyl acrylate, butadiene, isoprene, 2-ethoxyethyl acrylate, 3-ethoxypropyl acrylate, 4-dodecylstyrene, vinyl butyl ether.
• Particularly suitable recurring units II are: vinylsulfonic acid sodium salt, methallylsulfonic acid sodium salt, allylsulfonic acid potassium salt, 2-acrylamino-2-methylpropanesulfonic acid, sodium sulfoethyl methacrylate, potassium sulfopropylacrylate, lithium sulfopropyl methacrylate, styrenesulfonic acid, methacrylaminophenylsulfonic acid, sodium sulfonic acid, potassium sulfonate, potassium sulfonate.
• the polymers according to the invention preferably have a glass transition temperature of less than 20 ° C.
• the glass transition temperature is determined by the methods known from differential thermal analysis and differential calorimetry, which are described, for example, in the book "Polymeranalytik 11" by Hoffmann, Krämer and Kuhn, Thieme Verlag, Stuttgart 1977.
• the use of the polymers in photographic materials also results in improves the mechanical properties, especially the breaking strength.
• the polymers according to the invention surprisingly have the advantage that they superadditively increase the viscosity of the casting solutions without further additives when gelatin is used as a binder, so that a further addition of viscosity-increasing agents can be dispensed with.
• the polymeric compounds according to the invention are preferably prepared in the form of solution or precipitation polymerization.
• Compounds in which the starting monomers used are soluble, such as e.g. lower alcohols, ketones, esters, amides, sulfoxides and ethers.
• the free radical polymerization of an ethylenically unsaturated monomer is initiated by adding a free radical which is formed by thermal decomposition setting 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 radiation, high frequencies, etc.
• a free radical which is formed by thermal decomposition setting 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 radiation, high frequencies, etc.
• principal chemical initiators include a persulfate (e.g. ammonium persulfate or potassium persulfate, etc.), hydrogen peroxide, a peroxide (e.g. benzoyl peroxide or tert.butyl peroctoate, etc.) and an azonitrile compound (e.g. 4,4'-azobis-4-cyanovaleric acid and azobisisobutyronitrile, etc .), etc.
• a persulfate e.g. ammonium persulfate or potassium persulfate, etc.
• hydrogen peroxide e.g. benzoyl peroxide or tert.butyl peroctoate, etc.
• an azonitrile compound e.g. 4,4'-azobis-4-cyanovaleric acid and azobisisobutyronitrile, etc .
• Examples of conventional redox initiators include hydrogen iron (II) salt, potassium persulfate, sodium metabisulfite and cerium IV salt alcohol, etc.
• the solution of the polymers dissolved in organic solvents is mixed with water and then the solvent by known methods such as e.g. Distillation, dialysis or ultrafiltration removed. In this way, almost transparent polymer solutions can be obtained.
• the mixture is then diluted with 450 ml of n-propanol, 300 ml of water are added, the pH is adjusted to 6 with 10% sodium hydroxide solution, and the mixture is diluted with 700 ml of water and the n-propanol is largely removed by distillation.
• the compounds according to the invention can be incorporated into the casting solution of the silver halide emulsion layers or other colloid layers in a known manner, preferably in the form of aqueous dispersions, as can be obtained in the preparation, if appropriate in the presence of a wetting or dispersing agent added to a hydrophilic colloid solution.
• the hydrophilic casting solution can of course contain other conventional additives in addition to the binder.
• the substances to be used according to the invention are preferably used in a range from 1 to 200 g of polymer, in particular from 10 to 100 g of polymer per mole of silver halide in an emulsion layer.
• the addition takes place preferably as an aqueous dispersion and can in principle be carried out at any time, but preferably after spectral senibilization.
• the recording material according to the invention has at least one blue, green and red sensitive layer.
• at least one layer thereof is preferably split into two sub-layers L and H. It is particularly preferred to divide all spectrally sensitized layers into at least two sub-layers of different sensitivity.
• the sub-layers of the same spectral sensitivity can be combined adjacent to form double or multiple-layer packages, but the sub-layers of one spectral sensitivity can also be combined with the layers of another spectral sensitivity.
• At least one blue-sensitive layer lies above the green- and red-sensitive layers and is separated from them by a yellow filter layer.
• additional protective and intermediate layers can be used.
• the polymers to be used according to the invention are preferably used in the partial layer with a higher color coupler concentration.
• the sub-layers can additionally contain the usual components, e.g. Scavenger, DIR coupler as well as DAR coupler.
• auxiliary layers can be present in the color photographic recording material according to the invention, e.g. Adhesive layers, antihalation layers or cover layers, in particular intermediate layers between the light-sensitive layers, as a result of which the diffusion of developer oxidation products from one layer into another is to be effectively prevented.
• intermediate layers of this type can furthermore contain certain compounds which are able to react with developer oxidation products.
• Such layers are preferably arranged between adjacent light-sensitive layers of different spectral sensitivity.
• a less sensitive silver halide emulsion with an average grain diameter of about 0.1 ⁇ m or smaller, which contains chloride, bromide and optionally iodide, can also be embedded in these intermediate layers. Such a layer has a particularly beneficial effect on the sensitivity of the adjacent layers.
• the less sensitive silver halide emulsion can, however, also be introduced directly into the light-sensitive layers.
• the material according to the invention is preferably a reversal material which, after imagewise exposure, is subjected to black and white and then color development.
• Color couplers which can react with color developer oxidation products to form a dye, are preferably assigned to the light-sensitive silver halide emulsion layers.
• the color couplers are preferably directly adjacent to and in particular contained in the silver halide emulsion layer.
• the red-sensitive layer can contain a color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
• the green-sensitive layer can contain, for example, at least one color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone type usually being used.
• the blue-sensitive layer can contain, for example, at least one color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
• the color couplers can be, for example, 6-, 4- and 2-X equivalent couplers.
• Suitable couplers are known, for example, from the publications "Color Coupler” by W. Pelz in “Messages from the Research Laboratories of Agfa, Leverkusen / Kunststoff", Volume III, page 111 (1961), K. Venkataraman in “The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971) and TH James, "The Theory of the Photographic Process", 4th Ed., Pp. 353-362, as well as from Research Disclosure No. 17643 of December 1978, Section VII, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, P09 1 EF in the UK.
• the usual mask couplers can be used to improve the color rendering.
• the recording material can also contain DIR compounds and other white couplers which do not give any dye when reacted with color developer oxidation products.
• the inhibitors which can be split off from the DIR compounds can be split off directly or via non-inhibiting intermediate compounds.
• the light-sensitive silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide.
• the halide content of at least one layer consists of 0 to 12 mol-X of AgI, 0 to 50 mol-X of AgCl and 50 to 100% of AgBr.
• the crystals are predominantly compact, for example cubic or octahedral or have transition forms. They can be characterized in that they essentially have a thickness of more than 0.2 ⁇ m.
• the average ratio of diameter to thickness is preferably less than 8: 1, it being true that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
• all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.
• the emulsions can be monodisperse emulsions, which preferably have an average grain size of 0.3 ⁇ m to 1.2 ⁇ m.
• the silver halide grains can have a layered grain structure.
• the emulsions can be chemically sensitized.
• the usual sensitizers are suitable for chemical sensitization of the silver halide grains.
• Sulfur-containing compounds for example allyl isothiocyanate, allyl thiourea and thiosulfates, are particularly preferred.
• Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss.Phot. 46, 65-72 (1951). It is also possible to sensitize the emulsions with polyalkylene oxide derivatives. Reference is also made to Research Disclosure No. 17 643, section 111, given above.
• the emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• Such sensitizers are from F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 18, pages 431 ff and to Research Disclosure No. 17 643, section IV, given above.
• antifoggants and stabilizers can be used.
• Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups.
• Such a verb Examples are in the article by Birr, Z.Wiss.Phot. 47, 1952), pp. 2-58.
• Further suitable stabilizers and antifoggants are given in Research Disclosure No. 17 643 given in Section IV. Suitable compounds for improving the resistance to formalin are given in US-A 464 463.
• the recording material can contain stabilizers against visible and UV light and to improve the storage stability, which may optionally be in polymeric form. Particularly good stabilizers in this sense are e.g. Amino allyl malonitriles.
• the additional components of the photographic material can be incorporated by customary, known methods. If the compounds are soluble in water or alkali, they can be added in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide. If they are insoluble in water or alkali, they can be incorporated into the recording materials in dispersed form in a manner known per se. For example, a solution of these compounds in a low-boiling organic solvent can be mixed directly with the silver halide emulsion or initially with an aqueous gelatin solution and the organic solvent can then be removed. The dispersion of the respective compound thus obtained can then be mixed with the silver halide emulsion. If necessary, use too In addition, so-called oil formers, generally higher-boiling organic compounds, which include the compounds to be dispersed in the form of oily droplets.
• so-called oil formers generally higher-boiling organic compounds, which include the compounds to be
• hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin. Casting aids and plasticizers can be used. Reference is made to the compounds indicated in Research Disclosure 17,643 above in Sections IX, XI and XII.
• the layers of the photographic material can be hardened in the usual manner, for example with hardeners of the epoxy type, the heterocyclic ethylene imine and the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German Offenlegungsschrift 2 218 009 in order to achieve color photographic materials which are suitable for a high temperature processing are suitable. It is also possible to harden the photographic layers with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Further suitable hardening agents are known from German laid-open documents 2 439 551, 2 225 230, 2 317 672 and from Research Disclosure 17 643, section XI, specified above.
• Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, e.g. 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N- ⁇ - (methanesulfonamido) ethyl aniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N-ß-hydroxyethylaniline sulfate; 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine. Further useful color developers are described, for example, in J.Amer.Chem.Soc. 73, 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wi
• the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
• the usual compounds can be used as bleaching agents, for example Fe 3 * salts and Fe 3 + complex salts such as ferricyanides, dichromates, and water-soluble ones Cobalt complexes etc.
• Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
• Persulphates are also suitable as bleaching agents.
• the following layers were applied in each case in the order given here on a transparent layer support made of cellulose triacetate.
• Example 2 of EP-A-62 202 The materials were exposed to white light behind a step wedge and then subjected to a custom color reversal development, see Example 2 of EP-A-62 202.
• the samples thus produced and developed were stored in the dark at 80 ° C. and 40% relative atmospheric humidity.
• the maximum color density of the samples was measured fresh and every 7 days and the relative densities were determined. This showed a clear improvement in the dark stability of the corresponding image dyes, depending on the concentration of the compound according to the invention in the layer containing the color coupler.
• the quantities given relate to lm 2 .
• the corresponding amounts of AgNO 3 are given for the silver halide application.
• the following layers were applied in each case in the order given here on a transparent layer support made of cellulose triacetate.
• the layer structure variant 23 differs from variant 21 in that 34 g of compound A are added per mole of silver halide.
• the third layer contained all the components listed for variant 21 in order to achieve the same gradation and color density in an amount increased by a factor of 1.08.
• This third layer also contained 1.84 g of purple coupler M2, emulsified (1 part by weight of coupler with 1.0 part by weight of oil former).
• the layer structure variant 25 differs from variant 24 in that 34 g of compound A are added per mole of silver halide.
• the third layer contained the components listed for variant 21 in order to achieve the same gradation and color density in an amount increased by a factor of 1.08.
• This third layer also contained 1.84 g of purple coupler M1, emulsified (1 part by weight of coupler with 0.45 part by weight of oil former).
• the layer structure variant 27 differs from variant 26 in that 34 g of compound A are added per mole of silver halide.
• the third layer contained all the components listed for variant 21 in order to achieve the same gradation and color density in an amount increased by a factor of 1.08.
• Example 2 of EP-A-62 202 The materials were exposed to white light behind a step wedge and then subjected to a custom color reversal development, see Example 2 of EP-A-62 202.
• the samples thus produced and developed were stored in the dark at 80 ° C. and 40% relative atmospheric humidity.
• the maximum color density of the samples became fresh and at a distance measured from 7 days each and the relative densities determined. This showed a clear improvement in the dark stability of the corresponding image dyes, depending on the concentration of the compound according to the invention in the layer containing the color coupler.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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• 1985
  • 1985-06-29 DE DE19853523395 patent/DE3523395A1/de not_active Withdrawn
• 1986
  • 1986-06-20 DE DE8686108434T patent/DE3665637D1/de not_active Expired
  • 1986-06-20 EP EP86108434A patent/EP0207400B1/fr not_active Expired
  • 1986-06-27 JP JP61149830A patent/JPS627051A/ja active Pending

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