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
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
• • 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
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
• • 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
  • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
  • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
• • 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

• ABSTRACT Color-photographic multi-layer materials having redsensitized, green-sensitized, and blue-sensitized silver halide emulsion layers, each emulsion layer containing a color coupler, and gelatin interlayers for preventing undesirable coupling of developer oxidation products diffused in adjacent silver halide emulsion layers, contain in the gelatin interlayers 5 to 30 percent by weight of polyerms which contain acid groups. These interlayers are more effective in preventing the diffusion of developer oxidation products, as compared with pure gelatin interlayers. Thus it is possible to have interlayers of half the thickness of conventional interlayers. The materials have improved non-curling properties.
• This invention relates to a multi-layer colorphotographic material in which polymers containing acid groups are added to the gelatin intermediate layers arranged between the differently sensitized silver halide emulsion layers in order to improve the noncurling properties of the material.
• colored images can be produced using a multi-layer color-photographic material comprising at least one red-sensitized silver halide emulsion layer containing a cyan-forming coupler, a greensensitized silver halide emulsion layer containing a magenta-forming coupler and a blue-sensitive silver halide emulsion layer containing a yellow-forming coupler.
• a multi-layer color-photographic material comprising at least one red-sensitized silver halide emulsion layer containing a cyan-forming coupler, a greensensitized silver halide emulsion layer containing a magenta-forming coupler and a blue-sensitive silver halide emulsion layer containing a yellow-forming coupler.
• the differently sensitized silver halide emulsion layers are usually separated from one another by gelatin intermediate layers which can, if desired also contain filter dyes.
• the main object of these gelatin intermediate layers is to prevent or hinder oxidation products of the color developer formed in a layer during development diffusing into other coupler-containing layers where they could couple with the couplers in these other layers.
• These intermediate layers thus prevent the formation of undesirable dyes in the other layers.
• This effect of formation of undesirable dyes by coupling of diffused developer oxidation product is referred to herein as co-coupling.
• co-coupling This effect of formation of undesirable dyes by coupling of diffused developer oxidation product is referred to herein as co-coupling.
• the intermediate layers must have a certain thickness which can vary between one and several um, depending upon the particular type of color coupler and color developer used.
• the intermediate layer must be sufficiently thick to ensure that color developer oxidation products which are capable of coupling are destroyed by hydrolysis before reaching an adjacent coupler-containing layer.
• gelatin expands to a greater extent than the layer support and conversely in low relative humidity the gelatin shrinks to a greater extent than the layer support.
• the color-photographic material after processing shows a troublesome tendency to curl up, depending upon the relative humidity.
• this tendency can only be controlled to a limited extent by varying (i.e., by reducing) the layer thicknesses.
• the invention seeks to provide a material which shows little or no tendency to curl irrespective of the relative humidity.
• the thicknesses of the gelatin intermediate layers can be reduced and hence the non-curling properties of multi-layer colour photographic materials can be improved by replacing some of the gelatin of the gelatin intermediate layers arranged between the differently sensitised silver halide emulsion layers to prevent co-coupling, by polymers containing acid groups.
• the invention relates to a photosensitive color-photographic material which comprises at least one red-sensitized silver halide emulsion layer containing a cyan-forming coupler, a green-sensitized silver halide emulsion layer containing a magentadorming coupler and a blue-sensitive silver halide eulsion layer containing a yellow-forming coupler with gelatin intermediate layers between the aforementioned silver halide emulsion layers.
• the material is characterized by the fact that at least one intermediate layer contains a polymer containing acid groups in a quantity of from 5 to 30 percent by weight and preferably in a quantity of from 15 to 25 percent by weight, based on the gelatin.
• polymers containing acid groups are polymers compatible with gelatin which are diffusion-fast in gelatin layers and, hence whose acid groups are present in the form of diffusionresistant anions at the pI-I-value at which color development is carried out.
• polymers containing acid groups include polymers and copolymers of acrylic acid, copolymers of maleic acid, styrene sulfonic acid, and cellulose derivatives containing acid groups.
• the polymers and copolymers of acrylic acid and the copolymers of maleic acid contain on an average 0.2 to l carboxylic acid groups per monomeric unit, the polystyrene sulfonic acid contains on an average 0.5 to l sulfonic acid group per styrene unit.
• the carboxymethyl cellulose contains 0.5 'to .lcarboxylic group per glucose unit and the cellulo'sesulfat contains 1 2 sulfuric acid groups per glucose unit.
• copolymers of acrylic acid and maleic acid may contain other comonomeric units for example selected from the group consisting of alkylvinyl ethers having up to four carbon atoms in the alkyl group, vinylesters such as vinyl acetate or vinyl propionate, vinyl alkohol, styrene, alkyl acrylates and alkyl methacrylates having up to four carbon atoms in the alkyl group, and acrylamide.
• Preferred copolymers of acrylic acid contain 20 to 50 mols percent of acrylic acid and 50 to mols percent of ethyl acrylate.
• a preferred copolymer of maleic acid contains about 50 mols percent of maleic acid and about 50 mols percent of styrene.
• the carboxymethylcellulose preferably has a viscosity of 800 cps (2 percent aqueous solution, C; this corresponds to a molekular weight 40,000 200,000) and the cellulose sulfate preferably has a viscosity of 12 80 cps. (2 percent aqueous solution, 25). Standard carboxy-methyl cellulose and cellulose sulfate have proved to be particularly suitable.
• the negatively charged ion groups evidently act as a barrier to the diffusing color developer oxidation product which probably migrates in the form of a positively charged immonium ion, thus preventing its diffusion.
• the separating effect obtained with the intermediate layers according to the invention is equal to-that obtained with pure gelatin layers of about twice the layer thickness. This is a considerable advantage because better mechanical properties are obtained with lower layer thicknesses. The reduction in the layer thicknesses that is possible in this way evidently makes a considerable contribution towards improving the noncurling properties of color-photographic materials as well. The ability of the polymers containing acid groups according to the invention to swell rapidly with water may possibly also have a favourable effect upon the non-curling properties.
• the layer thickness of the intermediate layers according to the invention is between 1 and 1.5 pm. Conventional gelatin intermediate layers are considerably thicker, their layer thickness amount-- ing to about 2 am.
• the aforementioned polymers containing acid groups can be added to the gelatin either by mixing the dry gelatin with the powdered polymer and dissolving the resulting mixture in water, or by preparing separate solutions in water of the gelatin and of the polymer containing acid groups and subsequently mixing the resulting solutions in the required ratio.
• Suitable layer supports for the material according to theinven-tion include the usual supports such as, for example, baryta paper, hydrophibized paper such as polyethylene-lined paper, or films of polyethylene terephthalate, cellulose ester, polycarbonat or other film forming materials.
• Preventing the difussion of oxidized color developer from a layer containing color coupler into an adjacent layer during color development by the incorporation of polymers which are present as negatively charged polyions at the pH-value of the developer is of course not confined to a certain layer support or certain color developers of color couplers, but instead applies generally to multi-layer color-photographic systems which are developed with color developers of the phenylene diamine series.
• the material is processed as described above. When photographically tested for color purity, this material is as good in its color reproduction as comparison sample A despite the thin intermediate layers.
• Sample D 7 in the intermediate layers the polystyrene sulfonic acid is replaced by 5 g of a copolymer of 25 percent of acrylic acid, 35 percent of ethyacrylate and 40 percent of ethylmethacrylate, the structure of the material being otherwise the same.
• the application amounts to 1.1 g/m (layer thickness 1.1 pm). This material as well shows the same excellent color separation as sample A.
• Sample E Intermediate layers are applied from the following casting solution (the structure of the material being otherwise the same):
• Sample H In another test, 4 g of cellulose sulfate (viscosity of the 2 percent aqueous solution cps at 25C) are dissolved and added to 500 ml of the 4 percent gelatin solution. The casting solution thus obtained is applied as an intermediate layer. The application is regulated in such a way that 1.0 g of solids is applied per square metre (layer thickness 1.0 pm). This material is also equal in its color separation to sample A.
• samples A to H show distinct differences in their curling behaviour under different climatic conditions, as shown in the following Table.
• a photosensitive color-photographic material comprising at least one red-sensitized silver halide emulsion layer containing a cyan-forming coupler, a green-sensitized silver halide emulsion containing a magenta-forming coupler and a blue-sensitive silver emulsion layer containing a yellow-forming coupler, and having gelatin intermediate layers arranged between the aforementioned silver halide emulsion layers, the improvement according to which at least one gelatin intermediate layer contains a polymer containing acid groups in a quantity of from 5 to 30 percent by weight based on the gelatin.
• the polymer containing acid groups is selected from the group consisting of polymers and copolymers of acrylic acid and copolymers of maleic acid containing 0.2 to l carboxylic acid groups per monomeric unit, poly styrene sulfonic acid containing 0.5 to 1 sulfonic acid groups per styrene unit, carboxy methyl cellulose containing 0.5 to 1 carboxylic acid groups per glucose unit, and cellulose sulfate containing 1 to 2 sulfuric acid groups per glucose unit.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (5)

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• 1971
  • 1971-05-12 DE DE2123456A patent/DE2123456C2/de not_active Expired
• 1972
  • 1972-05-10 IT IT50165/72A patent/IT957854B/it active
  • 1972-05-10 GB GB2195672A patent/GB1348766A/en not_active Expired
  • 1972-05-10 BE BE783235A patent/BE783235A/xx unknown
  • 1972-05-10 US US00252025A patent/US3765893A/en not_active Expired - Lifetime
  • 1972-05-12 FR FR7217109A patent/FR2137858B1/fr not_active Expired
  • 1972-05-12 JP JP4629872A patent/JPS5441206B1/ja active Pending

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