EP0294104B1 - Photographic element containing a cyan dye-forming coupler - Google Patents
Photographic element containing a cyan dye-forming coupler Download PDFInfo
- Publication number
- EP0294104B1 EP0294104B1 EP19880304780 EP88304780A EP0294104B1 EP 0294104 B1 EP0294104 B1 EP 0294104B1 EP 19880304780 EP19880304780 EP 19880304780 EP 88304780 A EP88304780 A EP 88304780A EP 0294104 B1 EP0294104 B1 EP 0294104B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- photographic element
- cyan dye
- recurring units
- dye
- bleaching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 239000000975 dye Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 27
- 229920000126 latex Polymers 0.000 claims description 26
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- 239000004816 latex Substances 0.000 claims description 19
- -1 silver halide Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000004061 bleaching Methods 0.000 claims description 14
- 239000000839 emulsion Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910006069 SO3H Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 claims 1
- 239000001043 yellow dye Substances 0.000 claims 1
- 238000011160 research Methods 0.000 description 19
- 239000007844 bleaching agent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229960002380 dibutyl phthalate Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GVEYRUKUJCHJSR-UHFFFAOYSA-N (4-azaniumyl-3-methylphenyl)-ethyl-(2-hydroxyethyl)azanium;sulfate Chemical compound OS(O)(=O)=O.OCCN(CC)C1=CC=C(N)C(C)=C1 GVEYRUKUJCHJSR-UHFFFAOYSA-N 0.000 description 1
- ILKZXYARHQNMEF-UHFFFAOYSA-N (4-azaniumyl-3-methylphenyl)-ethyl-(2-methoxyethyl)azanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CC1=CC=C(S(O)(=O)=O)C=C1.COCCN(CC)C1=CC=C(N)C(C)=C1 ILKZXYARHQNMEF-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 description 1
- LMSDCGXQALIMLM-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;iron Chemical compound [Fe].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LMSDCGXQALIMLM-UHFFFAOYSA-N 0.000 description 1
- XTBFKMDOQMQYPP-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C=C1 XTBFKMDOQMQYPP-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- MPLZNPZPPXERDA-UHFFFAOYSA-N [4-(diethylamino)-2-methylphenyl]azanium;chloride Chemical compound [Cl-].CC[NH+](CC)C1=CC=C(N)C(C)=C1 MPLZNPZPPXERDA-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 210000004088 microvessel Anatomy 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- FECCTLUIZPFIRN-UHFFFAOYSA-N n-[2-[2-amino-5-(diethylamino)phenyl]ethyl]methanesulfonamide;hydrochloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C(CCNS(C)(=O)=O)=C1 FECCTLUIZPFIRN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- G03C7/392—Additives
- G03C7/396—Macromolecular 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
Definitions
- This invention relates to color photography and more particularly to photographic elements and methods for producing color images employing a light-sensitive silver halide emulsion comprising cyan dye-forming couplers in association with certain lower alkoxyalkyl acrylate polymer latices.
- a dye image is formed during a process which includes the treatment of an imagewise exposed light-sensitive material comprising at least one silver halide emulsion layer and a dye-forming coupler in a developing solution, followed by bleaching and fixing.
- a color developing agent usually a p-phenylenediamine
- Oxidized developing agent then reacts with the coupler to form a dye whose color is determined by the chromophoric structure of the dye contributed by the coupler.
- the developed silver is reoxidized by a bleaching agent and further fixed with a silver halide solubilizing agent for removal during the final wash cycle.
- An optional stabilizing treatment may be included prior to drying the so processed material.
- the bleaching of the developed silver and the fixing of the silver halide for final removal from the element can be performed either in sequential steps using separate bleach and fix solutions or in one step using a single solution wherein the bleaching and fixing agents are combined.
- the latter solution is commonly referred to as a bleach-fix solution.
- oxidizing agents are known for use as silver bleaching agents in such bleach and bleach-fix solutions
- metal complex salts of an organic acid such as an EDTA-iron complex salt, have become a common bleaching agent because of their low toxicity and environmental safety.
- the use of such complexes in color photographic bleach and bleach-fix processing solutions is taught in, for example, U.S. Patent Nos. 3,615,508; 3,770,437; 3,870,520; 4,242,442 and 4,288,618.
- ferric complex salts as color photographic bleaching agents does, however, have certain disadvantages.
- One such disadvantage is the lower density of image dye derived from naphtholic and certain phenolic couplers in color photographic materials treated after color development in a solution containing such an organic complex salt as the bleaching agent.
- secondary conditions may contribute to an objectionably low density of image dye in any processed photographic material, it is the conversion of cyan image dye derived from naphtholic and certain phenolic couplers to a leuco compound which is generally recognized as the basic cause of the problem.
- U.S. Patents 3,706,561; 3,770,437; 4,033,771; 4,301,236; 4,469,781 and 4,563,405 describe approaches which involve changing the concentration or composition of the bleach or bleach-fix solutions.
- U.S. Patent 4,366,233 proposes to reduce the total amount of silver contained in layers disposed below the cyan dye-forming layer of a color photographic element.
- U.S. Patents 3,820,997 and 4,469,781 and U.K. Patent 1,393,335 relate to the treatment of the bleached photographic material with a variety of chemicals contained in a separate processing bath.
- Patents 4,151,680 and 4,374,922; 4,591,548 disclose preferred classes of cyan dye-forming couplers for overcoming the above cited problem.
- the 548 patent also points to the presence of ferrous ions in the bleach solution as the cause for the conversion of cyan image dye to a leuco compound.
- color photographic silver halide materials can contain acrylate and/or acrylic acid polymer latices for a variety of purposes. See U.S. Patents 3,926,436; 4,201,589; 4,214,047; 4,214,627; 4,358,533; 4,612,278; German OLS 3,336,582; and Research Disclosure Item 19551, July 1980.
- our invention is directed to a process of bleaching silver from a photographic element containing a cyan image dye, wherein bleaching is performed in the presence of a polymer latex free of recurring units containing coupler moieties, the polymer comprising recurring units of the monomer of formula (I).
- our invention is directed to photographic elements containing cyan dye images formed by a process that includes this bleaching process.
- our invention relates to such materials and processes in which the polymer latex further contains recurring units of an ionic monomer, as described, as an ionomer, of formula (II):
- monomer (I) can comprise from 5 to 100% by weight of the total polymer, and ionomer (II) can comprise from 0 to 20%, and preferably from 2 to 10%, by weight of the total polymer.
- one or more other ethylenically unsaturated comonomers can be present in the latex polymers employed in this invention.
- Such additional monomers are selected to modify such physical and chemical properties of the polymer as solubility, compatibility, stability and flexibility.
- the latex polymer is incorporated in the photographic element in a location and an amount that will be effective to reduce, or inhibit leuco dye formation in coupler-derived cyan dye as a result of bleaching in the presence of ferrous ions. In a common color negative format this amount can be in the range of 0.05 to 5.0 grams per square meter.
- the latex polymer is in the same layer as the cyan dye-forming coupler.
- polymeric latices containing units of formula (I) are useful to inhibit leuco dye formation while polymers derived from closely analogous acrylates are ineffective for this purpose.
- cyan couplers are represented by one of the structural formulae III and IV, wherein
- Photographic elements of the invention can be single color elements or multicolor elements.
- Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the visible spectrum.
- Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
- the layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art.
- the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer, e.g., as by the use of microvessels as described in Whitmore U.S. Patent 4,362,806 issued December 7, 1982.
- the silver halide emulsions employed in the elements of this invention can be either negative-working or positive-working. Suitable emulsions and their preparation are described in Research Disclosure Sections I and II and the publications cited therein. Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure Section IX and the publications cited therein.
- the elements of the invention can include additional couplers as described in Research Disclosure Section VII, paragraphs D, E, F and G and the publications cited therein. These couplers can be incorporated in the elements and emulsions as described in Research Disclosure Section VII, paragraph C and the publications cited therein.
- the photographic elements of this invention or individual layers thereof can contain brighteners (see Research Disclosure Section V), antifoggants and stabilizers (See Research Disclosure Section VI), antistain agents and image dye stabilizers (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section VIII), hardeners (see Research Disclosure Section XI), plasticizers and lubricants (See Research Disclosure Section XII), antistatic agents (see Research Disclosure Section XIII), matting agents (see Research Disclosure Section XVI) and development modifiers (see Research Disclosure Section XXI).
- the photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.
- Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX.
- Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
- Preferred color developing agents useful in the invention are p-phenylene diamines.
- Preferred color developing agents useful in the invention are 4-amino-N,N-diethyl-aniline hydrochloride, 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N- ⁇ -(methanesulfonamido)-ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate, 4-amino-3- ⁇ -(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluenesulfonic acid.
- the processing step described above gives a negative image.
- this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniformly fogging the element to render unexposed silver halide developable.
- a direct positive emulsion can be employed to obtain a positive image.
- the polymer latices employed in this invention can be prepared by procedures known in the art and illustrated below. Typically this will be a free radical polymerization leading to an aqueous latex polymer.
- the resulting polymer typically is a high polymer having a molecular weight above about 1 ⁇ 104.
- each film segment was sensitometrically exposed through a graduated density test object for 3 seconds and then processed using the Kodak C-41 R process as described in the British Journal of Photography 1982 Annual, pp. 209-211.
- each element was further treated for 5 minutes in a continuously-stirred, nitrogen-purged bath having the following composition:
- each sample was reevaluated by another density reading (designated D f ) of the same step on the sensitometric curve.
- D f another density reading
- each element contained the coupler C-1, dispersed in half its weight of tricresyl phosphate.
- Elements 2, 3, 4, and 5 contained the homopolymer consisting of recurring units of the monomer.
- Each element in this example contained the cyan dye-forming coupler C-1, dispersed in half its weight of dibutylphthalate.
- Elements 8, 9, 10, 11 and 12 contained increasing amounts, as listed in Table 2, of the homopolymer employed in element 5.
- Elements 13 to 16 contained the cyan dye-forming coupler C-2, incorporated in the silver halide emulsion without a coupler solvent.
- Elements 17 to 20 contained the cyan dye-forming coupler C-2, dispersed in half its weight of dibutylphthalate.
- Elements 14-16 and 18-20 contained the homopolymer consisting of recurring units of the monomer
- Elements 21 to 25 contained the coupler C-1 dispersed in half its weight of tricresyl phosphate.
- Elements 26 to 31 contained the coupler C-2 dispersed in half its weight of dibutylphthalate.
- Elements 22 to 25 and elements 27 to 31 contained the copolymer consisting of recurring units of the copolymerized monomers in which the proportion of acid was varied.
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
- This invention relates to color photography and more particularly to photographic elements and methods for producing color images employing a light-sensitive silver halide emulsion comprising cyan dye-forming couplers in association with certain lower alkoxyalkyl acrylate polymer latices.
- In color photography a dye image is formed during a process which includes the treatment of an imagewise exposed light-sensitive material comprising at least one silver halide emulsion layer and a dye-forming coupler in a developing solution, followed by bleaching and fixing. During development, a color developing agent, usually a p-phenylenediamine, is oxidized in a reaction with silver halide, producing free silver. Oxidized developing agent then reacts with the coupler to form a dye whose color is determined by the chromophoric structure of the dye contributed by the coupler. Then, in the subsequent silver removing cycle, the developed silver is reoxidized by a bleaching agent and further fixed with a silver halide solubilizing agent for removal during the final wash cycle. An optional stabilizing treatment may be included prior to drying the so processed material.
- The bleaching of the developed silver and the fixing of the silver halide for final removal from the element can be performed either in sequential steps using separate bleach and fix solutions or in one step using a single solution wherein the bleaching and fixing agents are combined. The latter solution is commonly referred to as a bleach-fix solution. Although a variety of oxidizing agents are known for use as silver bleaching agents in such bleach and bleach-fix solutions, metal complex salts of an organic acid, such as an EDTA-iron complex salt, have become a common bleaching agent because of their low toxicity and environmental safety. The use of such complexes in color photographic bleach and bleach-fix processing solutions is taught in, for example, U.S. Patent Nos. 3,615,508; 3,770,437; 3,870,520; 4,242,442 and 4,288,618.
- The use of such ferric complex salts as color photographic bleaching agents does, however, have certain disadvantages. One such disadvantage is the lower density of image dye derived from naphtholic and certain phenolic couplers in color photographic materials treated after color development in a solution containing such an organic complex salt as the bleaching agent. Although a variety of secondary conditions may contribute to an objectionably low density of image dye in any processed photographic material, it is the conversion of cyan image dye derived from naphtholic and certain phenolic couplers to a leuco compound which is generally recognized as the basic cause of the problem. Attempts made to overcome this problem have included a variety of approaches, such as modifying the bleach solution and/or the photographic element, treating the photographic element in a separate bath subsequent to the bleach step, or restricting the use of cyan dye-forming couplers to selected limited classes of compounds.
- For example, U.S. Patents 3,706,561; 3,770,437; 4,033,771; 4,301,236; 4,469,781 and 4,563,405 describe approaches which involve changing the concentration or composition of the bleach or bleach-fix solutions. U.S. Patent 4,366,233 proposes to reduce the total amount of silver contained in layers disposed below the cyan dye-forming layer of a color photographic element. U.S. Patents 3,820,997 and 4,469,781 and U.K. Patent 1,393,335 relate to the treatment of the bleached photographic material with a variety of chemicals contained in a separate processing bath. U.S. Patents 4,151,680 and 4,374,922; 4,591,548 disclose preferred classes of cyan dye-forming couplers for overcoming the above cited problem. The 548 patent also points to the presence of ferrous ions in the bleach solution as the cause for the conversion of cyan image dye to a leuco compound.
- The art also recognizes that color photographic silver halide materials can contain acrylate and/or acrylic acid polymer latices for a variety of purposes. See U.S. Patents 3,926,436; 4,201,589; 4,214,047; 4,214,627; 4,358,533; 4,612,278; German OLS 3,336,582; and Research Disclosure Item 19551, July 1980.
- Also known in the art are polymeric couplers which contain acrylate recurring units and recurring units containing coupler moieties as described in US-A-4612278.
- However, none of the art identified in the preceding paragraphs recognizes any connection between the problem of leuco dye formation and the presence of certain polymers, not does it suggest the use of such polymers in conjunction with cyan couplers susceptible to leuco dye formation.
- We have found that leuco dye conversion of cyan image dye by ferrous ions formed during the bleaching of imagewise developed silver in color photographic materials can be inhibited in the presence of certain polymer latices.
- In one aspect, our invention is directed to a photographic element comprising a light-sensitive silver halide emulsion, a cyan dye-forming coupler and a polymer latex free of recurring units containing coupler moieties, the polymer having recurring units derived from a lower alkoxyalkyl acrylate monomer having the formula (I):
- In another aspect, our invention is directed to a process of bleaching silver from a photographic element containing a cyan image dye, wherein bleaching is performed in the presence of a polymer latex free of recurring units containing coupler moieties, the polymer comprising recurring units of the monomer of formula (I).
- In yet another aspect, our invention is directed to photographic elements containing cyan dye images formed by a process that includes this bleaching process.
-
- wherein
- m = 1 to 4;
- n = 0 to 10;
- X, when n = 0, represents ―OH, and
- X, when n = 1 to 10, represents ―CO₂H, ―SO₃H, ―O-PO(OH)₂ or a metal salt thereof.
- In the polymer latices used in this invention, monomer (I) can comprise from 5 to 100% by weight of the total polymer, and ionomer (II) can comprise from 0 to 20%, and preferably from 2 to 10%, by weight of the total polymer. In addition, one or more other ethylenically unsaturated comonomers can be present in the latex polymers employed in this invention. Such additional monomers are selected to modify such physical and chemical properties of the polymer as solubility, compatibility, stability and flexibility.
- The latex polymer is incorporated in the photographic element in a location and an amount that will be effective to reduce, or inhibit leuco dye formation in coupler-derived cyan dye as a result of bleaching in the presence of ferrous ions. In a common color negative format this amount can be in the range of 0.05 to 5.0 grams per square meter. Preferably the latex polymer is in the same layer as the cyan dye-forming coupler.
- It is surprising that the polymeric latices containing units of formula (I) are useful to inhibit leuco dye formation while polymers derived from closely analogous acrylates are ineffective for this purpose.
- The advantageous effects of this invention are especially obtained when bleaching is in a process which generates ferrous ions, such as one in which the bleaching agent is a ferric complex of a polycarboxylic acid, e.g., an iron-ethylene diamine tetracetic acid complex. Preferred cyan couplers are represented by one of the structural formulae III and IV,
- BALL is a ballast group,
- R¹ is halogen,
- R² is hydrogen, lower alkyl or lower alkoxy, and
- Y is hydrogen or a coupling-off group.
- Suitable couplers are described in U.S. Patents 3,476,563 and 4,004,929.
- Photographic elements of the invention can be single color elements or multicolor elements. Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the visible spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer, e.g., as by the use of microvessels as described in Whitmore U.S. Patent 4,362,806 issued December 7, 1982.
- In the following discussion of suitable materials for use in the emulsions and elements of this invention, reference will be made to Research Disclosure, December 1978, Item 17643, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, PO9 1EF, U.K. This publication will be identified hereafter by the term "Research Disclosure".
- The silver halide emulsions employed in the elements of this invention can be either negative-working or positive-working. Suitable emulsions and their preparation are described in Research Disclosure Sections I and II and the publications cited therein. Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure Section IX and the publications cited therein.
- In addition to the cyan dye-forming couplers generally described above, the elements of the invention can include additional couplers as described in Research Disclosure Section VII, paragraphs D, E, F and G and the publications cited therein. These couplers can be incorporated in the elements and emulsions as described in Research Disclosure Section VII, paragraph C and the publications cited therein.
- The photographic elements of this invention or individual layers thereof, can contain brighteners (see Research Disclosure Section V), antifoggants and stabilizers (See Research Disclosure Section VI), antistain agents and image dye stabilizers (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section VIII), hardeners (see Research Disclosure Section XI), plasticizers and lubricants (See Research Disclosure Section XII), antistatic agents (see Research Disclosure Section XIII), matting agents (see Research Disclosure Section XVI) and development modifiers (see Research Disclosure Section XXI).
- The photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.
- Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
- Preferred color developing agents useful in the invention are p-phenylene diamines. Especially preferred are 4-amino-N,N-diethyl-aniline hydrochloride, 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β-(methanesulfonamido)-ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-β-(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluenesulfonic acid.
- With negative working silver halide, the processing step described above gives a negative image. To obtain a positive (or reversal) image, this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniformly fogging the element to render unexposed silver halide developable. Alternatively, a direct positive emulsion can be employed to obtain a positive image.
- Development is followed by the steps of bleaching, fixing, or bleach-fixing, as described above, washing and drying.
- The polymer latices employed in this invention can be prepared by procedures known in the art and illustrated below. Typically this will be a free radical polymerization leading to an aqueous latex polymer. The resulting polymer typically is a high polymer having a molecular weight above about 1 × 10⁴.
-
- To a 500 ml 3-necked round bottom flask equipped with a mechanical stirrer, a nitrogen inlet tube and a reflux condenser, set in an 80°C constant temperature bath, was added with stirring an aqueous solution of sodium dodecyl sulfate (50 ml, 0.1 M), N₂-purged distilled water (50 ml), acrylate monomer (0.1 molar equiv.) and an aqueous solution of sodium bisulfite (6 ml, 0.5 M). An aqueous solution of ammonium persulfate (15 ml, 0.2 M) was added dropwise over a 10-minute period. After stirring for 2 hours, the mixture was cooled to room temperature and filtered. The clear latex was dialyzed for 3 days and then collected.
-
- In the following examples each film segment was sensitometrically exposed through a graduated density test object for 3 seconds and then processed using the Kodak C-41 R process as described in the British Journal of Photography 1982 Annual, pp. 209-211.
-
- After subsequent washing for 5 minutes and final drying, each sample was reevaluated by another density reading (designated Df) of the same step on the sensitometric curve. The percent dye loss as recorded in the following tables was calculated by dividing the initial density values (Di) into the final density values (Df).
- In this example each element contained the coupler C-1, dispersed in half its weight of tricresyl phosphate. Elements 2, 3, 4, and 5 contained the homopolymer consisting of recurring units of the monomer.
-
- The data in Table 1 show the superiority of the latex in Elements 5 and 6 in reducing cyan dye loss.
-
-
- The data in Table 2 show the effectiveness of this polymeric latex even at low concentration.
- Elements 13 to 16 contained the cyan dye-forming coupler C-2, incorporated in the silver halide emulsion without a coupler solvent. Elements 17 to 20 contained the cyan dye-forming coupler C-2, dispersed in half its weight of dibutylphthalate. Elements 14-16 and 18-20 contained the homopolymer consisting of recurring units of the monomer
- The data illustrate again the effectiveness of the compounds in elements 15 and 19 of the invention.
-
- Elements 21 to 25 contained the coupler C-1 dispersed in half its weight of tricresyl phosphate. Elements 26 to 31 contained the coupler C-2 dispersed in half its weight of dibutylphthalate. Elements 22 to 25 and elements 27 to 31 contained the copolymer consisting of recurring units of the copolymerized monomers
- The data show the improvement in dye stability attainable in the presence of copolymer latices of the invention.
Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US5619487A | 1987-06-01 | 1987-06-01 | |
US56194 | 1987-06-01 |
Publications (2)
Publication Number | Publication Date |
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EP0294104A1 EP0294104A1 (en) | 1988-12-07 |
EP0294104B1 true EP0294104B1 (en) | 1991-09-18 |
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ID=22002801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19880304780 Expired EP0294104B1 (en) | 1987-06-01 | 1988-05-26 | Photographic element containing a cyan dye-forming coupler |
Country Status (3)
Country | Link |
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EP (1) | EP0294104B1 (en) |
JP (1) | JP2721177B2 (en) |
DE (1) | DE3864910D1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1991019224A2 (en) * | 1990-06-01 | 1991-12-12 | Eastman Kodak Company | Color photographic materials containing polymers which improve photographic performance |
JP3571462B2 (en) * | 1996-06-11 | 2004-09-29 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
JPH1020460A (en) * | 1996-06-28 | 1998-01-23 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5125133A (en) * | 1974-08-26 | 1976-03-01 | Fuji Photo Film Co Ltd | HAROGENKAGINSHASHINKANKOZAIRYO |
US4201589A (en) * | 1974-08-26 | 1980-05-06 | Fuji Photo Film Co., Ltd. | Silver halide photo-sensitive material prepared with solvent and solvent soluble polymer |
DE2946465A1 (en) * | 1979-11-17 | 1981-06-11 | Agfa-Gevaert Ag, 5090 Leverkusen | NEW POLYMERS, METHOD FOR THEIR PRODUCTION AND THEIR USE FOR THE PRODUCTION OF PHOTOGRAPHIC EMULSIONS AND PHOTOGRAPHIC MATERIALS |
JPS5946644A (en) * | 1982-08-30 | 1984-03-16 | Konishiroku Photo Ind Co Ltd | Color photographic sensitive silver halide material |
JPS60205447A (en) * | 1984-03-29 | 1985-10-17 | Konishiroku Photo Ind Co Ltd | Photosensitive silver halide material |
-
1988
- 1988-05-26 DE DE8888304780T patent/DE3864910D1/en not_active Expired - Fee Related
- 1988-05-26 EP EP19880304780 patent/EP0294104B1/en not_active Expired
- 1988-06-01 JP JP63132881A patent/JP2721177B2/en not_active Expired - Lifetime
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Publication number | Publication date |
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JP2721177B2 (en) | 1998-03-04 |
EP0294104A1 (en) | 1988-12-07 |
DE3864910D1 (en) | 1991-10-24 |
JPS6452136A (en) | 1989-02-28 |
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