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
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
  • G03C7/3005—Combinations of couplers and photographic additives
• • 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
• • 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
  • G03C7/392—Additives
  • G03C7/396—Macromolecular additives

Definitions

• the present invention relates generally to color photography and more particularly to a color photographic lgiht-sensitive element having a photographic layer containing an improved color turbidity-preventing agent.
• color-turbidity is meant the phenomenon caused by poor silver removal after color developing a color photographic light-sensitive element in an oxidizingbleaching bath, whereby a Wide spectral absorption band of the remaining silver overlaps a sharp spectral absorption band of the developed color image. That is, the phenomenon is fundamentally different from so-called fogging, or blacking of the unexposed portions of the light-sensitive element.
• color photographic light-sensitive elements which have photographic silver halide emulsion layers containing couplers capable of forming dye images by coupling with the oxidation prodnot of an N,N-dialkyl-p-phenylenediamine developing agent.
• a coupler containing an oil-soluble group in the coupler molecule such that the coupler can be dissolved in a water-immiscible (oily) organic solvent having a high boiling point is dissolved in an oily solvent having a high boiling point.
• the solution is then dispersed in a gelatin solution containing a dispersing agent such as sodium alkylbenzene sulfonate, and after mixing the dispersion thus prepared with a photographic silver halide emulsion, the resulting mixture is applied to a support.
• an oil-soluble coupler is incorporated in a photographic silver halide emulsion directly without using the aforesaid .water-immiscible organic solvent having a h gh boiling point and the mixture is applied to a support.
• a water-soluble or alkali-soluble group s incorporated in the long-chain aliphatic hydrocarbon group of a coupler molecule and after adding the coupler directly to a photographic silverhalide emulsion, the resulting emulsion is applied to a support.
• the monomer to be copolymerized with vinyl pyrrolidone may be a vinyl ester (such as vinyl acetate, vinyl propionate, vinyl butyrate, etc.), acrylic ester, methacrylic ester, acrylic acid, methacrylic acid, and styrene.
• vinyl ester such as vinyl acetate, vinyl propionate, vinyl butyrate, etc.
• acrylic ester methacrylic ester
• acrylic acid methacrylic acid
• methacrylic acid and styrene
• An object of this invention is to provide a color photographic light-sensitive element having little or no residual developed silver image accompanying the dye images after processing to provide more brilliant dye images, and having reduced development suppressing properties.
• the inventors have found'that by incorporating (1) a copolymer of vinyl alcohol and vinyl pyrrolidone in a specific monomer ratio, (2) a partially saponificated polyvinyl alcohol, or (3) a copolymer of vinyl alcohol and cyanoethylvinyl ether or a copolymer of vinyl alcohol and alkylvinyl ether in a photographic layer of a color photographic light-sensitive element, in particular, a color photographic silver halide emulsion having incorporated therein an oil-soluble coupler and an oily solvent having a high boiling point, the silver removal or silver bleaching of developed silver in the bleaching process after color development is effectively improved whereby the color turbidity of colored images can be reduced. Also, the suppression of color development is markedly reduced.
• a color photographic light-sensitive element comprising a support bearing thereon photographic silver halide emulsion layers, a protective layer, insulating layers, filter layers, and an antihalation layer, at least one of said photographic layers having incorporated therein either (1) a copolymer of vinyl alcohol and vinyl pyrrolidone represented by the general formula l rho-H2 n (1) wherein the ratio of x to y ranges from 95/5 to 40/ 60, and wherein n is a positive integer of from 400 to 2000; (2) a partially saponificated polyvinyl alcohol represented by the general formula wherein the ratio of x to y ranges from 95/5 to 70/30 and n is a positive integer of from 400 to 2000, or (3) a copolymer of vinyl alcohol and cyanoethylvinyl ether or a copolymer of vinyl alcohol and an alkyl vinyl ether represented by the general formula wherein R represents
• the effect of the above-mentioned copolymer of vinyl alcohol and vinyl pyrrolidone depends upon the monomer ratio (x/ y) of the copolymer.
• the optimum monomer ratio of x to y is suitably from 95/5 to 40/ 60 and more preferably from 80/20 to 90/10.
• copolymer of vinyl alcohol and vinyl pyrrolidone used in this invention is soluble or can be dispersed in the collodial state in water, alkali or preferably in organic solvents.
• the effect of the copolymer of vinyl alcohol and vinyl pyrrolidone used in this invention depends to a certain extent on the degree of polymerization. That is, a copolymer having any degree of polymerization may be employed if it is soluble in water, a liquid or solid having a high boiling point (at least 200 C.). However, the degree of polymerization affects the characteristics of the emulsion and the color turbidity of the yellow image and accordingly, it is preferred that the degree of polymerization ranges from 400 to 2000.
• the saponification value of the above-mentioned partially saponified polyvinyl alcohol used in this invention is too high or too low, the solubility thereof in water or organic solvents becomes poor and hence the color turbidity preventing effect thereof is reduced.
• the suitable ratio of x to y is from 95/5 to 70/30 or more but preferably from 80/20 to 90/ 10.
• the partially saponified polyvinyl alcohol used in this invention is water soluble or can be dispersed in the colloidal state in water, alkali or preferably in organic solvents.
• the color turbidity-preventing effect of the partially saponified polyvinyl alcohol used in this invention is influenced by the degree of polymerization thereof. Too low a degree of polymerization may cause the color turbidity-preventing effect to be reduced during storage, while o h a deg ee Qt r ymsriaa iq m y result i the reduced solubility of the polymer in water or in organic solvents.
• a suitable degree of polymerization is from 400 to 2000 as mentioned above or most preferably from 500 to 1000.
• the color turbiditypreventing agent of this invention may be a copolymer of vinyl alcohol and cyanoethylvinyl ether or a copolymer of vinyl alcohol and an alkyl vinyl ether.
• the color turbidity-preventing effect of the copolymers is not greatly influenced by the monomer ratio in the copolymers, too small a proportion of vinyl alcohol may cause a reduction in the fixing rate of silver halide during processing.
• the ratio of x to y of the aforesaid general Formula II is /5 to 30/70.
• copolymer of vinyl alcohol and cyanoethylvinyl ether or the copolymer of vinyl alcohol and an alkyl vinyl ether used in this invention is soluble or dispersible in a colloidal state in water, an alkali or organic solvents.
• the turbidity-preventing effect of the copolymer of vinyl alcohol and cyanoethylvinyl ether or the copolymer of vinyl alcohol and an alkylvinyl ether used in this invention is influenced only slightly by the degree of polymerization, a copolymer having any degree of polymerization can be employed effectively in this invention if it is a liquid or a solid having a high boiling point, and is soluble in aqueous solution and alkali, and preferably in organic solvents.
• the emulsion characteristics are affected by the degree of polymerization and accordingly it is preferred that the degree of polymerization range from 400 to 2000.
• a binder for the emulsion used for the color photographic light-sensitive element of this invention there may be employed a suitable protective colloid such as gelatin, polyvinyl alcohol, a derivative of polyvinyl alcohol, polyaclylamide, a derivative of polyacrylamide, a celluose derivative, casein, an alginate and the like, but among them gelatin is most preferable.
• a suitable protective colloid such as gelatin, polyvinyl alcohol, a derivative of polyvinyl alcohol, polyaclylamide, a derivative of polyacrylamide, a celluose derivative, casein, an alginate and the like, but among them gelatin is most preferable.
• organic solvent utilized for incorporating the copolymer of this invention in photographic emulsions there may be employed alcohols, such as, methanol, ethanol, isopropanol, etc.; ether alcohols, such as Cellosolve, Carbitol, etc.; esters such as ethyl ether, dioxane, tetrahydrofuran, etc.; ketones such as acetone, methyl athyl ketone, etc.; amides such as lactams, dialkylcarbamides, etc., and the like.
• alcohols such as, methanol, ethanol, isopropanol, etc.
• ether alcohols such as Cellosolve, Carbitol, etc.
• esters such as ethyl ether, dioxane, tetrahydrofuran, etc.
• ketones such as acetone, methyl athyl ketone, etc.
• amides such as lactams, dialky
• the amount of the copolymer of vinyl alcohol and vinyl pyrrolidone or the copolymer of vinyl alcohol and cyanoethylvinyl ether or a copolymer of vinyl alcohol and alkyl vinyl ether used in this invention to be incorporated in a photographic silver halide emulsion depends upon the kind and the amount of the coupler in the emulsion. In general, the color turbidity-preventing effect reaches a maximum when about 5% by weight is added based on the weight of gelatin present in the emulsion layer although more or less amounts may of course be employed. However, when the amount of the copolymer is over 20% by weight of the gelatin, the coupling efficiency and the quality of layers are reduced. Hence, amounts of from about 1 to about 15% by weight are suitable in general.
• the amount of the partially saponificated polyvinyl alcohol used in this invention is influenced by the kind and the'amount of coupler in the emulsion but in general the color turbidity-preventing effect reaches maximum when about 5% by weight is added based on the weight of gelatin in the emulsion although other amounts may be employed.
• the amount of the copolymer is larger than 20% by weight of the gelatin, the coupling effect and the quality of coating are degraded.
• the amount of the copolymer is suitably 110% by weight.
• Coupler 1 -4-benzoylacetamido-N-butyl-N- octylbenzamide (C H2)1C H3 Coupler 2.l-hydroxy-4chloro-dodecyl-Z-naphthamide on @Ucomnomhom Coupler 3.1( 2,4,6-trichlorophenyl)-3-[3-(N-butyltetradecanamido) -propanamide]py1azoline-5-on CH3(CH2) 2C O NCHzCHzCONH-CCH2 CHa(CH2)a
• the color turbidity-preventing polymer used in this invention may be incorporated in a coating composition for photographic layers at any stage of preparation, for example, during dispersing of the coupler, mixing the emulsion or just before applying the coating composition to a support, but it is most preferable to incorporate it at the stage of dispersing the coupler.
• the aforesaid copolymer may be most effectively incorporated in a silver halide emulsion layer but may also be effectively incorporated in at least one contiguous layer, such as the antihalation layer, insulating layer, filter. layer, or a protective layer.
• the copolymer may be incorporated in the layer in an amount of up to 50% by weight of the gelatin therein without having any adverse influences on the physical properties of the layer, the coupling efliciency of couplers, etc.
• the entire amount of the emulsified dispersion was mixed with a gelatino silver halide emulsion containing 7.0 g. of silver bromide and 5.0 g. of gelatin and the resulting mixture was applied to a film base and dried.
• the light-sensitive film thus prepared was exposed and subjected to photographic processings, such as, color development, water washing, potassium ferricyanide-bromide bleaching, and fixing.
• EXAMPLE 2 A photographic light-sensitive film was prepared as in Example 1 while using 2.4 g. of Coupler 2 mentioned above instead of the coupler used in Example 1. The light-sensitive layer thus formed exposed and subjected to color photographic processings, such as, color development, water washing, potassium ferricyanide-bromide bleaching, etc.
• EXAMPLE 3 A photographic light-sensitive emulsion layer was prepared as in Example 1 while using Coupler 3 mentioned above instead of the coupler used in Example 1. The light-sensitive layer thus prepared was exposed and subjected to color photographic processings such as color development, water washing, potassium ferricyanide-bromide bleaching, etc.
• Coupler 1 (yellow) None (control)- do Added 2 Couple1'2 (cyan) None do Added 3 Coupler?) (magenta).- None do Added
• the table shows that in any cases of using the yellow, cyan and magneta couplers, the color turbidity measured by the optical density in an unnecessary wavelength region for the respective dye proper was markedly reduced by incorporating in the color photographic silver halide emulsions containing them the copolymer of vinyl alcohol and vinyl pyrrolidone.
• EXAMPLE 4 A photographic light-sensitive film was prepared as in Example 1 using the following copolymers set forth in Table 2 instead of the copolymer used in Example 1. The light-sensitive layer thus prepared was exposed and subjected to photographic processings as in Example 1.
• the red optical density of the yellow image was measured with the relative value at the point where the blue optical density of the yellow image was 1.0.
• the light-sensitive layers were exposed and subjected to color photographic processings such as color development, water washing, potassium ferricyanide-bromide bleaching, etc.
• the image turbidity in terms of the red optical density in the case of using the color turbidity-preventing agent of this invention was much lower than that of the control.
• EXAMPLE 6 A comparison with respect to the development rate suppressing degree was made between the photographic light-sensitive layers of this invention and known vinyl pyrrolidone-vinyl acetate (monomer ratio 7:3, 21:1000) copolymer (Copolymer 5) and vinyl pyrrolidone-styrene (7:3) copolymer (Copolymer 6) shown in Japanese Pat. 705/66.
• the light-sensitive layer thus prepared was exposed and subjected to color photographic processings such as color development, water Washing, potassium ferricyanide-bromide bleaching, etc.
• color photographic processings such as color development, water Washing, potassium ferricyanide-bromide bleaching, etc.
• the red optical density of the dye image was measured, the results of which are shown in Table 5.
• the whole amount of the dispersion was mixed with a gelatino silver halide emulsion containing 5.0 g. of gelatin and 7.0 g. of silver bromide and the resulting mixture ,was applied to a film based and dried.
• the lightsensitive color film thus prepared was exposed and subjected to color photographic processings such as color development, water washing, bleaching by potassium ferricyanide and bromide, etc.
• EXAMPLE 9 A color photographic light-sensitive emulsion layer was prepared as in Example 7 but using 2.4 g. of a cyan coupler. Coupler 2 mentioned above instead of the coupler used in Example 8 and after exposure, the lightsensitive layer was subjected to color photographic processings such as color development, water washing, potassium ferricyanide-bromide bleaching, etc.
• EXAMPLE 10 A color photographic light-sensitive emulsion layer was prepared as in Example 8 but using 4.3 g. of a magenta coupler, Coupler 3 mentioned above instead of the coupler used in Example 8 and after exposure, the
• Table 6 shows that by incorporating the color turbiditypreventing copolymer of this invention in the color photographic silver halide emulsion containing the coupler, the formation of color turbidity measured by the optical density in an unnecessary wave length regions to the respective dye proper was effectively prevented in each case.
• EXAMPLE 11 A color photographic light-sensitive film was prepared as in Example 8 while using, instead of the copolymer of vinyl alcohol and cyanoethylvinyl ether (x/3 :88:12, 12:1000), each of the following copolymers:
• the layer After exposing the light-sensitive layer, the layer was subjected to color photographic processings such as color development, water Washing, potassium ferricyanide-bromide bleaching, etc.
• the image turbidity measured in terms of the optical density in the case of using the color turbidity-preventing copolymer of this invention was much lower than that of the control cases.
• EXAMPLE 12 A comparison with respect to the development rate suppressing degree was made between the photographic lightsensitive layers of this invention, each containing one of the copolymers of viny alcohol and cyanoethylvinyl ether shown in Examples 8-11, and photographic lightsensitive layers, each containing one of the color turbidity preventing agents disclosed in Japanese patent publication No. 705/66 shown below:
• Control copolymer 5 Copolymer of vinylpyrrolidione and vinyl acetate (monomer ratio 7:3, 11:1000), and
• Control copolymer 6 Copolymer of vinylpyrrolidone and styrene (monomer ratio 7:3).
• the photographic light-sensitive layers shown in Examples 8-11 and the control photographic light-sensitive layers prepared above were exposed and subjected to a color development.
• the development rate was measured in terms of the density obtained in three minutes of development compared with that obtained in fifteen minutes. In the table, the larger the density ratio, the faster the development rate, or the lower the development suppressing tendency.
• EXAMPLE 13 Color photographic light-sensitive layers were prepared as in Example 1 While using, instead of the copolymer of vinyl alcohol and cyanoethylvenyl ether used in Example 8, the following copolymers of vinyl alcohol and alkylvinyl ethers;
• the light-sensitive layers Were exposed and subjected to color photographic processings such as color development, water washing, potassium ferricyanide-bromide bleaching, etc.
• the red optical density in the case of using the color turbidity-preventing copolymer of this invention was much lower than that of the control case.
• color photographic processings such as color development, water washing, potassium ferricyanide-bromide bleaching, etc.
• Coupler 1 yellow coupler
• the whole amount of the emulsified dispersion was mixed with a gelatino silver halide emulsion containing 6.0 g. of silver bromide, 6.0 g. of gelatin and 88 g. of water and the resulting emulsion was applied to a triacetyl cellulose film followed by drying.
• the light-sensitive film thus prepared was exposed and subjected to color photographic processings at 24 C., such as, color development, water washing, potassium ferricyanide-bromide bleaching, and fixing.
• EXAMPLE 16 A color photographic light-sensitive emulsion layer was prepared as in Example 15 but using 2.4 g. of Coupler 2 (cyan coupler) mentioned above instead of the coupler used in Example 15. The light-sensitive layer was exposed and subjected to color photographic processing such as color development, water washing, potassium ferricyanide-bromide bleaching, and fixing. For determining the extent of cyan turbidity, the blue optical density of the color image was measured, the results of which are shown in Table 11 shown below.
• Coupler 2 cyan coupler
• Coupler 1 None 0. 52 do Added 0.10
• the light-sensitive layers thus prepared were exposed and subjected to color photographic processings, such as, color development, water washing, potassium ferricyanidebromide bleaching, and fixing.
• Copolymer (partially-saponified Red optical polyvinyl alcohol): density (1) 0.38
• the image-turbidity measured in the term of the red optical density in the case of using the color turbidity preventing polymer of this invention was much lower than that of the control case.
• Photographic light-sensitive films for comparison were prepared as in Example 15 using Coupler 1 (yellow) and the known vinylpyrrolidonevinyl acetate (monomer ratio 7:3, 11:1000) copolymer (Copolymer 5) and vinylpyrrolidonestyrene (7:3) copolymer (Copolymer 6) described in Japanese patent publication No. 705/66 and compared with the photographic light-sensitive films containin g the partially saponified vinyl alcohols of this invention prepared in Examples 15-18 about development suppression.
• EXAMPLE 21 The relation between the polymerization degree and the effect in promoting silver-bleaching is illustrated hereinafter.
• the red optical density of the yellow image gave the lowest value in the case of using a copolymer of this invention having a polymerization degree of 11:800. This represents the lowest color turbidity of the yellow image and the highest effect for the promotion of silver-bleaching. In the case of copolymers having a. polymerization degree outside the region of from 400 to 2000, on the other hand, this eifect was markedly decreased.
• This example shows an embodiment in which the copolymer according to the present invention is incorporated in the antihalation layer.
• copolymers used in this example were as follows:
• Coupler 2 (cyan coupler) described above was added to a mixed solution of 2.0 ml, of dibutyl phthalate and 3.0 ml. of ethyl acetate, and heated to dissolve, and was added to 10 ml. of 10% by weight of an aqueous gelatin solution containing 2.0 ml. of 10% sodium alkylbenzene sulfonate, and stirred at high speed using a homoblender at 50 C. for 10 minutes to obtain a dispersion of Coupler 2 emulsified in an aqueous gelatin solution.
• This emulsion dispersion was mixed with a gelatino silver halide emulsion containing 6.0 g. of silver bromide, 6.0 g. of gelatin, 5.0 ml. of a 0.1% methanol solution of anhydro-5,5'-dichloro-3',9- diethyl-3-(6-sulfobutyl)-'selenacarbocyanine hydroxide, as a spectral sensitizing dye for red light, and 88 ml. of water, added with a hardening agent and a coating assistant to prepare a coating liquid for a. red sensitive emulsion.
• a gelatino silver halide emulsion containing 6.0 g. of silver bromide, 6.0 g. of gelatin, 5.0 ml. of a 0.1% methanol solution of anhydro-5,5'-dichloro-3',9- diethyl-3-(6-sulfobutyl)-'
• This coating liquid was coated on each of the above five antihalation coating layers at a thickness of 3.0 1. and dried to prepare five samples coated with a red-sensitive emulsion containing a cyan coupler on five antihalation layers, four of which contain copolymers (1) to (4) according to the present invention on a support and the fifth not containing such a copolymer.
• the photosensitive elements containing the copolymers according to the present invention are markedly lower in blue optical density value in comparison with the material not having such a copolymer and the cyan colored image is lower in color turbidity and therefore extremely preferred.
• EXAMPLE 23 This example shows an embodiment in which the copolymer according to the present invention is incorporated in an intermediate layer.
• copolymers used in this example were the same as those used in Example 22.
• This emulsified dispersion was mixed with a gelatino silver halide photographic emulsion containing 6.0 g. of silver bromide, 6.0 g. of gelatin, 5 ml. of a 0.1% solution of 3,3,9-triethyl-5,5'-diphenyl-oxacarbocyanine iodide in methanol, as a green spectral sensitizing dye, and 88 ml. of water, and was added with a hardening agent and a coating assistant.
• the green sensitive silver halide photographic emulsion sols so prepared were separately coated on the abovedescribed intermediate layers and dried to obtain five types of photosensitive elements, four of which contain separately copolymers (1) to (4) described above in the intermediate layer, and the fifth element Without such a copolymer.
• the blue optical density was measured to examine the turbidity of the cyan colored image, and the red optical density was measured for the same purpose as the above, except for the magenta image.
• photosensitive elements containing copolymers (1) to (4) according to the present invention are markedly lower in optical density value and have less color turbidity in the cyan colored image (measurement of blue optical density) and the magenta colored (measurement of red optical density) than the element without such a copolymer.
• the red optical density of the magenta colored image was measured for color turbidity.
• the results obtained are as shown in Table 20.
• the photosensitive elements containing copolymers (1) to (4) according to the present invention are markedly lower in red optical density value and have less in turbidity of magenta colored image than the element not having such a copolymer.
• EXAMPLE 25 This example shows an embodiment in which the copolymer according to the present invention is incorporated in the protective layer.
• Coupler 1 yellow coupler
• ethyl acetate 3.0 g. of the Coupler 1 (yellow coupler) described above dissolved in 2.0 ml. of dibutyl phthalate and 3.0 ml. of ethyl acetate were added to 20 ml. of 10% by weight gelatino aqueous solution containing 2.0 ml. of aqueous solution of sodium alkyl benzene sulfonate, and blended using a homoblender of 50 C. for 10 minutes to prepare an emulsified dispersion.
• This emulsified dispersion was mixed with a gelatino-silver halide emulsion sol containing 7.0 g. of silver bromide and 5.0 g. of gelatin, and added with a hardening agent and a coating assistant.
• the silver halide photographic emulsion containing this yellow coupler was coated on a support at a dried thickness of 4.0a and dried.
• emulsion sols prepared by separately adding copolymers (1) to (4) as used in Example 22 to g. of 4% by weight, of an aqueous gelatino solution, one prepared by adding 30 ml. of 2% by weight of polyvinyl pyrrolidone-acrylic acid (monomer ratio 7:3) thereto as a comparative sample, and another emulsion sol not containing such a copolymer were separately added with a hardening agent and a coat ing assistant to prepare a coating liquid for a protective layer.
• the photosensitive elements containing copolymers (1) to (4) are markedly lower in red optical density value and had less turbidity of yellow image than the others.
• a photographic light-sensitive element containing a member selected from the group consisting of a copolymer of vinyl alcohol and vinyl pyrrolidone of the formula above described with an x/y ratio ranging from 95/5 to 60/40 and a degree of polymerization of 400 to 2000; a partially saponificated polyvinyl alcohol of the formula above described with an x/ y ratio ranging from 95/5 to 70/30 and a degree of polymerization of 400 to 2000; and a copolymer of vinyl alcohol and cyanoethyl vinyl ether or an alkyl vinyl ether having the formula above described with an x/ y ratio ranging from 95/5 to 30/70 and a degree of polymerization of from 400 to 2000; in one of the layers of the photographic light sensitive element possesses markedly reduced color turbidity due to improvement of silver removal or silver bleaching.
• a color photographic light-sensitive element comprising a support bearing thereon at least one oil-soluble coupler-containing silver halide photographic emulsion layer, a protective layer, insulating layers, filter layers, and a antihalation layer
• the improvement comprising incorporating additionally in said silver halide photographic emulsion layer, in a layer contiguous to said silver halide photographic emulsion layer or in said silver halide photographic emulsion layer and said layer contiguous to said silver halide photographic emulsion layer of a polymer selected from the group consisting of:
• a copolymer of vinyl alcohol and a vinyl ether represented by the general formula wherein R represents a member selected from the group consisting of an alkyl group having from 1 to 4 carbon atoms and -CH CH CN, the ratio of x to y ranges from 95/5 to 30/70 and n is a positive integer of from 400 to 2000.
• said compound represented by general Formula II is selected from the group consisting of a partially saponified polyvinyl alcohol wherein the x/y ratio is 88/12 and n is 500; a partially saponified polyvinyl alcohol wherein the x/y ratio is /20, and n is 500; a partially saponified polyvinyl alcohol wherein the x/y ratio is 88/12 and n is 1000; a partially saponified polyvinyl alcohol wherein the x/y ratio is 88/12 and n is 1700; and a partially saponified polyvinyl alcohol wherein the x/y ratio is 95/5 and n is 500.
• the color photographic light-sensitive element as claimed in claim 1 wherein said coupler is selected from the group consisting of 4-benzoylacetamido-N-butyl-N- octylbenzamide, 1 hydroxy-4-chloro-N-dodecyl-2-naphthamide, and 1-(2,4,6-trichlorophenyl) 3 [3-(N-butyltetradecaneamido)-propanamide]pyrraZolidone-5-one.

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

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• 1968
  • 1968-03-27 DE DE1772074A patent/DE1772074C3/de not_active Expired
  • 1968-03-28 FR FR1588198D patent/FR1588198A/fr not_active Expired
  • 1968-03-29 GB GB1226158D patent/GB1226158A/en not_active Expired
• 1970
  • 1970-09-14 US US00072116A patent/US3730726A/en not_active Expired - Lifetime

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