EP0881535A1 - Matériau photographique couleur à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0881535A1
EP0881535A1 EP97108611A EP97108611A EP0881535A1 EP 0881535 A1 EP0881535 A1 EP 0881535A1 EP 97108611 A EP97108611 A EP 97108611A EP 97108611 A EP97108611 A EP 97108611A EP 0881535 A1 EP0881535 A1 EP 0881535A1
Authority
EP
European Patent Office
Prior art keywords
silver halide
sensitive material
photographic light
color photographic
halide color
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.)
Withdrawn
Application number
EP97108611A
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German (de)
English (en)
Inventor
Osamu Takahashi
Hidekazu Sakai
Junichi Yamanouchi
Masashi Ogiyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to EP97108611A priority Critical patent/EP0881535A1/fr
Publication of EP0881535A1 publication Critical patent/EP0881535A1/fr
Withdrawn legal-status Critical Current

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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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03517—Chloride content
    • 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
    • G03C7/3006—Combinations of phenolic or naphtholic 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material (hereinafter also referred to as a light-sensitive material), and more particularly to a silver halide color photographic light-sensitive material excellent in rapid processibility, wherein the density due to the change of the cyan dye in an image to a leuco dye in a bleaching bath or a bleach-fix bath is prevented from decreasing.
  • a silver halide color photographic light-sensitive material hereinafter also referred to as a light-sensitive material
  • three color photographic couplers i.e. a yellow coupler, a magenta coupler, and a cyan coupler
  • a color developer containing a color-developing agent.
  • the oxidation product of an aromatic primary amine, and the couplers undergo coupling reactions with each other, to give color-formed dyes.
  • a standard process of processing silver halide color light-sensitive materials comprises a color-developing step of forming a color image, a desilvering step of eliminating developed silver and undeveloped silver, and a washing step and/or an image stabilizing step.
  • the above desilvering step of eliminating developed silver and undeveloped silver, silver halide is carried out by reoxidizing developed silver with a bleaching agent and fixing with a silver halide solubilizing agent.
  • the said desilvering can be performed by carrying out successively two separate steps, i.e. a step using a bleaching solution, and a step using a fixing solution, or by carrying out a single step using a single solution of a combination of a bleaching agent with a fixing agent.
  • the solution used in the latter is generally called a bleach-fix (blix) solution.
  • the shortening of time in a color-developing step can be attained by combining suitably, for example, use of a coupler high in coupling speed, use of a silver halide emulsion high in developing speed, use of a color developer high in development activity, and an increase in temperature of a color developer.
  • T.H. James "The Theory of the Photographic Process," Section 15, E. Bleach-Fix System (Macmillan Publishing Co., Inc.), describes that, to shorten the time in a desilvering step, it is effective to lower the pH of the bleaching solution or the bleach-fix solution.
  • to lower the pH of a bleaching solution or a bleach-fix solution disadvantageously facilitates the above blix fading of a cyan dye.
  • JP-A means unexamined published Japanese patent application
  • No. 316857/1988 describes that reduction fading is reduced by using a certain hydroquinone or quinone derivative.
  • JP-A Nos. 51136/1989 and 289840/1990 describe that the change of the cyan dye to a leuco dye is suppressed by using an aqueous latex of a polymer having a specified structure.
  • U.S. Patent Nos. 4,151,680, 4,374,922, and 4,591,546 describe a group of cyan couplers that are preferable for overcoming the foregoing problem.
  • an object of the present invention is to provide a silver halide color photographic light-sensitive material that can be color-developed in a short period of time, that is high in color-forming properties, that can produce a dye image improved with regard to blix fading, and that can be processed to give a color photograph that keeps the color balance of the image from being destroyed and is improved in image quality.
  • the inventors of the present invention have found that the above object can be attained by the following silver halide color photographic light-sensitive material.
  • the polymer to be used in the present invention will be further described.
  • Examples of the monomer that can give the repeating unit (recurring unit) represented by A include, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and the followings.
  • these monomers may form a salt in the form of -COOM.
  • Examples of the cation represented by M include, for example, a metal ion (e.g. an alkali metal ion and an alkaline earth metal ion such as a sodium ion and a potassium ion) and an ammonium ion (e.g. an ammonium ion, a dimethyl ammonium ion, and a triethyl ammonium ion).
  • a metal ion e.g. an alkali metal ion and an alkaline earth metal ion such as a sodium ion and a potassium ion
  • an ammonium ion e.g. an ammonium ion, a dimethyl ammonium ion, and a triethyl ammonium ion.
  • Examples of the ethylenically unsaturated monomer represented by B are acrylates, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, n-decyl acrylate, n-dodecyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, meth
  • butyl crotonate, hexyl crotonate e.g. dimethyl itaconate, dibutyl itaconate
  • maleates e.g. diethyl maleate, dimethyl maleate, dibutyl maleate
  • fumarates e.g. diethyl fumarate, dimethyl fumarate, dibutyl fumarate
  • vinyl ketones e.g.
  • B may be copolymerized with a monomer having an anionic group (e.g. a sulfonic acid group or a sulfate group) other than -COOM represented by A, and such an ethylenically unsaturated monomer may be, for example, styrenesulfoninc acid, vinylbenzylsulfonic acid, vinylsulfonic acid, an acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, and acryloyloxypropylsulfonic acid; a methacryloyloxyalkylsulfonic acid, such as methacryloyloxymethylsulfontic acid, methacryloyloxyethylsulfonic acid, and methacryloyloxypropylsulfonic acid; an acrylamidoalkylsulfonic acid, such as 2-
  • the ethylenically unsaturated monomer represented by B a monomer that will form a water-insoluble homopolymer is preferably used.
  • the proportion of the monomer, which will form a water-soluble homopolymer, out of B, is preferably about 0 to 20% based on all the monomers.
  • the ethylenically unsaturated monomer represented by the above B is preferably an acrylate, a methacrylate, and a vinyl ester, and particularly preferably it is an acrylate and a methacrylate.
  • the monomers represented by the above A and the monomers represented by the above B may be used in a combination of two or more, respectively.
  • x and y represent weight percentages of the respective components, and preferable ranges thereof vary depending on the structures of the ethylenically unsaturated monomers represented by A and B.
  • x is 15 to 85, preferably 20 to 80, and particularly preferably 25 to 70
  • the polymer for use in the present invention is preferably soluble in water, and out of the water-soluble polymers, particularly preferable ones are represented by the above formula [II].
  • R 2 represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
  • the substituent may be, for example, a phenyl group, a substituted phenyl group, -OH, an alkoxy group, a phenoxy group, a halogen atom, an alkylcarbonyl group, or an alkylcarbonamido group. Specific examples are those described for the above B, and preferably R 2 is a hydrocarbon group.
  • R 2 are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, benzyl, 2-phenylethyl, and p-methylbenzyl.
  • a methacrylic acid/n-butyl acrylate copolymer is most preferable.
  • the copolymerization ratio (in weight ratio) of the methacrylic acid monomer to the n-butyl acrylate monomer is in the range of (40 : 60) to (60 : 40) is preferable.
  • the polymer for use in the present invention is preferably a water-soluble polymer that can be dissolved in an amount of 1 g or more, more preferably 5 g or more, and further preferably 20 g or more, per 100 g of water at 25 °C.
  • the copolymer for use in the present invention exhibits excellent effects independent of its molecular weight, but taking into consideration diffusion to other layers when the copolymer is applied or processed, and viscosity of its coating solution, its molecular weight is preferably 5 x 10 3 to 1 x 10 7 , more preferably 1 x 10 4 to 5 x 10 6 , and particularly preferably 2 x 10 4 to 1 x 10 6 , in terms of weight-average molecular weight.
  • the water-soluble co-polymer for use in the present invention exhibits excellent effects, but taking into account, for example, the pH when the polymer is mixed with an aqueous gelatin solution, preferably the neutralization degree is 20 to 100%, and particularly preferably 50 to 100%.
  • the copolymer for use in the present invention is used, a method can be mentioned wherein the copolymer is dissolved in water and a coating liquid containing the resultant aqueous solution is applied, thereby introducing the copolymer into a photographic light-sensitive material.
  • a suitable alkali and salt are used.
  • a water-miscible organic solvent e.g. acetone, methanol, ethanol, isopropyl alcohol, and acetonitrile
  • auxiliary solvent e.g. acetone, methanol, ethanol, isopropyl alcohol, and acetonitrile
  • the polymer of formula [I] is contained in a cyan coupler-containing layer, and further the polymer may also be added to another photographic constitutional layer, such as a layer (e.g. a UV absorbing layer and an intermediate layer) adjacent to the cyan coupler-containing layer, a magenta coupler-containing layer, and a yellow coupler-containing layer.
  • a layer e.g. a UV absorbing layer and an intermediate layer
  • magenta coupler-containing layer e.g. a magenta coupler-containing layer
  • a yellow coupler-containing layer e.g. a layer adjacent to the cyan coupler-containing layer
  • hydrophilic colloid that forms the hydrophilic colloid layer containing the copolymer for use in the present invention
  • gelatin is preferably used, and as the gelatin, lime-processed gelatin, as well as an acid-processed gelatin and an enzyme-processed gelatin, may be used, and also a hydrolyzate and an enzymolyzate of gelatin can be used.
  • hydrophilic colloid other than gelatin can be used, such as a protein, for example albumin and casein; a cellulose derivative, for example hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate; a saccharide derivative, for example sodium alginate, dextran, and a starch derivative; and a synthetic hydrophilic polymeric substance that includes a homopolymer and a copolymer, for example a polyvinyl alcohol, a polyvinyl alcohol partial acetal, a poly-N-vinyl pyrrolidone, a polyacrylamide, a polyvinylimidazole, and a polyvinylpyrazole.
  • a protein for example albumin and casein
  • a cellulose derivative for example hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate
  • saccharide derivative for example sodium alginate, dextran, and a starch derivative
  • synthetic hydrophilic polymeric substance that includes
  • the pH of the coating liquid is 5.0 to 8.0, more preferably 5.5 to 7.0, and further preferably 5.8 to 6.5.
  • the ratio of the copolymer and the hydrophilic colloid used in the present invention (polymer content ratio by weight), and preferably the value of the polymer ratio given by the below-shown formula is 0.02 to 0.30, more preferably 0.03 to 0.20, and further preferably 0.04 to 0.15. If the value of the polymer ratio is too large, there arises a problem that the film quality changes.
  • Polymer ratio (the coating amount of the copolymer for use in the present invention)/(the coating amount of the gelatin)
  • Examples of the cyan coupler include a phenol, a naphthol, a fused-ring phenol, a pyrazoloazole, an imidazole, a pyrrole, a 3-hydroxypyridine, an active methylene, an active methine, a 5,5-ring-fused heterocyclic, and a 5,6-ring-fused heterocyclic coupler.
  • phenol couplers use can be made of those, for example, 2-acylamino-5-alkylphenol couplers described, for example, in U.S. Patent Nos. 2,369,929, 2,801,171, 2,772,162, 2,895,826, and 3,772,002; 2,5-diacylaminophenol couplers described, for example, in U.S. Patent Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, West Germany Patent Publication No. 3,329,729, and JP-A No. 166956/1984; and 2-phenylureido-5-acylaminophenol couplers described, for example, in U.S. Patent Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427,767.
  • naphthol couplers use can be made of those, for example, 2-carbamoyl-1-naphthol couplers described, for example, in U.S. Patent Nos. 2,474,293, 4,052,212, 4,146,396, 4,228,233, and 4,296,200; and 2-carbamoyl-5-amido-1-naphthol couplers described, for example, in U.S. Patent No. 4,690,889.
  • fused-ring phenol couplers those described, for example, in U.S. Patent Nos. 4,327,173, 4,564,586, and 4,904,575, can be used.
  • pyrazoloazole couplers those described, for example, in U.S. Patent Nos. 4,873,183 and 4,916,051, JP-A Nos. 199352/1988, 105250/1989, and 105251/1989, can be used.
  • imidazole couplers those described, for example, in U.S. Patent Nos. 4,818,672 and 5,051,347, can be used.
  • pyrrole couplers those described, for example, in JP-A Nos. 188137/1992 and 190347/1992, can be used.
  • 3-hydroxypyridine couplers those described, for example, in JP-A No. 315736/1989, can be used.
  • active methylene and active methine couplers those described, for example, in U.S. Patent Nos. 5,104,783 and 5,162,196, can be used.
  • 5,5-ring-fused heterocyclic couplers for example, pyrrolopyrazole couplers described in U.S. Patent No. 5,164,289, pyrroloimidazole couplers described in JP-A No. 174429/1992, and pyrrotriazole couplers described, for example, in Europe Patent Nos. 488,248A1, 491,197A1, and 545,300, can be used.
  • pyrazolopyrimidine couplers described in U.S. Patent No. 4,950,585, pyrrolotriazine couplers described in JP-A No. 204730/1992, and couplers described in European Patent No. 556,700 can be used.
  • cyan couplers having such a structures as a phenol, a naphthol, and a pyrrotriazole are preferable.
  • cyan couplers that can be used in the present invention are shown below.
  • couplers described in the above-mentioned patent specifications use can be made of couplers described, for example, in West Germany Patent Nos. 3,819,051A1 and 3,823,049, U.S. Patent No. 4,840,883, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, and 386,931A1, U.S. Patent Nos. 5,024,930 and 5,051,347, and JP-A Nos.
  • the amount of the cyan coupler to be added there is no particular restriction on the amount of the cyan coupler to be added, and the amount of the cyan coupler to be added is generally 10 -3 to 1 mol, preferably 0.1 to 0.8 mol, and more preferably 0.25 to 0.5 mol, per mol of silver halide.
  • amounts that are generally used can be used.
  • the color light-sensitive material of the present invention is made up by layering, on a base, at least one yellow color-forming silver halide emulsion layer, at least one magenta color-forming silver halide emulsion layer, and at least one cyan color-forming silver halide emulsion layer.
  • color couplers capable of forming dyes complementary to the lights to which the silver halide emulsions are sensitive, respectively, are contained, so that color reproduction by the subtractive color process can be effected.
  • the silver halide emulsion grains are spectrally sensitized with blue-sensitive, green-sensitive, and red-sensitive spectral-sensitizing dyes, in the above-mentioned order of the color-forming layers, respectively, and are applied on a base in the above-mentioned order.
  • the order may be changed. That is, in some cases, in view of rapid processing, preferably a light-sensitive layer containing silver halide grains whose average grain size is the greatest is placed as an uppermost layer, or in some cases, in view of the preservability under irradiation with light, preferably the lowermost layer is a magenta color-forming light-sensitive layer.
  • light-sensitive layers and color-forming hues may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can also be used.
  • any support can be used if it is a support on which a photographic emulsion layer can be coated, such as glass, paper, and plastic film, and reflective support is most preferable.
  • the reflective support refers to a support that increases the reflecting properties to make bright the dye image formed in the silver halide emulsion layer, and such a reflective support includes a support coated with a hydrophobic resin containing a light-reflecting substance, such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, dispersed therein, or a support made of a hydrophobic resin itself containing a dispersed light-reflecting substance.
  • a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate
  • Examples are a polyethylene-coated paper, a polyethylene trephthalate-coated paper, a polypropylene-series synthetic paper, a transparent support having a reflective layer or using a reflecting substance, such as a glass sheet; a polyester film made, for example, of a polyethylene terephthalate, cellulose triacetate, or cellulose nitrate; a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.
  • the reflective support to be used in the present invention is preferably a paper support, both surfaces of which are coated with a water-resistant resin layer, and at least one of the water-resistant resin layers contains fine particles of a white pigment.
  • water-resistant resin of the reflective-type base to be used in the present invention is meant a resin having a water absorption (in % by weight) of 0.5 or less, and preferably 0.1 or less, and examples thereof include a polyolefin, such as a polyethylene, a polypropylene, and a polyethylene-series polymer; a vinyl polymer or a vinyl copolymer (e.g. a polystyrene, a polyacrylate, and their copolymers); a polyester (e.g. a polyethylene terephthalate and a polyethylene isophthalate), and its copolymer, with particular preference given to a polyethylene and a polyester.
  • a polyolefin such as a polyethylene, a polypropylene, and a polyethylene-series polymer
  • vinyl polymer or a vinyl copolymer e.g. a polystyrene, a polyacrylate, and their copolymers
  • a polyester e.
  • the polyethylene a high-density polyethylene, a low-density polyethylene, a linear low-density polyethylene, and a blend of these polyethylenes can be used.
  • the melt flow rate (hereinafter abbreviated to MFR) of these polyethylene resins before processing is preferably in the range of 1.2 g/10 min to 12 g/10 min, in terms of the value measured under conditions 4 in Table 1 in JIS K 7210.
  • MFR of the polyolefin resin before processing indicates the MFR of the resin into which a bluing agent and a white pigment have not yet been kneaded.
  • polyester a polyester synthesized by condensation polymerization of a dicarboxylic acid with a diol is preferred.
  • dicarboxylic acid for example, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid can be mentioned.
  • diol for example, ethylene glycol, butylene glycol, neopentyl glycol, triethylene glycol, butanediol, hexylene glycol, bisphenol A/ethylene oxide adduct (2,2-bis(4-(2-hydroxyethyloxy)phenyl)propane), and 1,4-dihydroxymethylcyclohexane can be mentioned.
  • dicarboxylic acids preferably terephthalic acid.
  • dicarboxylic acid component a mixture of terephthalic acid and isophthalic acid (in a mole ratio of from 9 : 1 to 2 : 8), or a mixture of terephthalic acid and naphthalenedicarboxylic acid (in a mole ratio of from 9 : 1 to 2 : 8), is also preferably used.
  • diol ethylene glycol, or a mixed diol containing ethylene glycol, is preferably used.
  • the molecular weight of these polymers is 30,000 to 50,000.
  • a mixture of these polyesters different in composition is used.
  • a mixture of these polyesters with another resin is also preferably used.
  • the other resins to be mixed a wide variety of resins can be chosen, as long as the resins can be extruded at 270 to 350 °C, and examples include polyolefins, such as a polyethylene and a polypropylene; polyethers, such as a polyethylene glycol, a polyoxymethylene, and a polyoxypropylene; a polyester-series polyurethane, a polyether polyurethane, a polycarbonate, and a polystyrene. These resins to be blended may be used singly or in a combination of two or more.
  • the polyester and other resins can be mixed in the range of from 100/0 to 50/50 in terms of weight ratio.
  • the mixing ratio of the above water-resistant resin to a white pigment is from 98/2 to 30/70, preferably from 95/5 to 50/50, and particularly preferably from 90/10 to 60/40, in terms of weight ratio (water-resistant resin/white pigment). If the amount of white pigment is too small, it contributes to the whiteness unsatisfactorily, while if the amount is too large, the surface smoothness of the obtainable photographic base is unsatisfactory and a photographic base excellent in glossiness cannot be secured.
  • these water-resistant resin layers are coated on a base to have a thickness of 2 to 200 ⁇ m, and more preferably 5 to 80 ⁇ m. If the thickness is too thick, the brittleness of the resin is enhanced, and there arise problems of physical properties that will cause breakage or the like. If the thickness is too thin, the waterproofness, which is the fundamental purpose of the coating, is impaired, and in addition the whiteness and the surface smoothness cannot be satisfied simultaneously, and further the layer unfavorably becomes physically too soft.
  • the thickness of the resin or resin composition that will be applied to the surface of the base where the light-sensitive layers are not applied is preferably 5 to 100 ⁇ m, and more preferably 10 to 50 ⁇ m. If the thickness exceeds that range, the brittleness of the resin is enhanced, and there arise problems of physical properties that will cause breakage or the like. On the other hand, if the thickness is below the range, the waterproofness, which is the fundamental purpose of the coating, is impaired, and further the layer unfavorably becomes physically too soft.
  • the reflective base is a reflective base in which a water-resistant resin coat layer on the side where the light-sensitive layer is applied comprises two or more water-resistant resin coat layers different in content of a white pigment, in view, for example, of the cost and the suitability for production of the base.
  • the water-resistant resin coat layer situated nearest to the base has preferably a white pigment content lower than that of at least one water-resistant resin coat layer located above the former water-resistant resin coat layer.
  • a reflective base in which, out of the water-resistant resin coat layers different in white pigment content, the water-resistant resin coat layer nearest to the light-sensitive layer has the highest white pigment content, or a reflective base in which the reflective base comprises at least three water-resistant resin coat layers, and, of the multilayer water-resistant resin layer, any one of intermediate layers other than the water-resistant resin coat layer located nearest to the light-sensitive layer, and other than the water-resistant resin coat layer located nearest to the base, has the highest white pigment content.
  • the white pigment content of each layer of the multilayer water-resistant resin layer is generally 0 to 70% by weight, preferably 0 to 50% by weight, and more preferably 0 to 40% by weight.
  • the white pigment content of the layer having the highest white pigment content in the multilayer water-resistant resin layers is generally 9 to 70% by weight, preferably 15 to 50% by weight, and more preferably 20 to 40% by weight. If the white pigment content of this layer is too small, the sharpness of the image is low, while if the white pigment content of this layer is too large, the melted and extruded film will be broken with causing a breakage of film.
  • each layer of the multilayer water-resistant resin layer is preferably 0.5 to 50 ⁇ m.
  • the thickness of each layer is preferably 0.5 to 50 ⁇ m, and the total thickness obtained by combining them is preferably within the above range (2 to 200 ⁇ m).
  • the thickness of the uppermost layer is 0.5 to 10 ⁇ m
  • the thickness of the intermediate layer is 5 to 50 ⁇ m
  • the thickness of the lowermost layer is 0.5 to 10 ⁇ m.
  • the white pigment highly loaded into the intermediate layer is apt to cause die lip streaks.
  • the thickness of the uppermost layer and the lowermost layer, particularly the uppermost layer is too thick, the sharpness is apt to be lowered.
  • the white pigment fine particles are homogeneously dispersed in the reflective layer without forming aggregates of particles, and the magnitude of the distribution can be found by measuring the occupied area proportions (%) (Ri) of fine particles projected on a unit area.
  • the deviation coefficient of the occupied area proportions (%) can be found by the ratio s/R of the standard deviation s of Ri to the average value (R) of Ri.
  • the deviation coefficient of the occupied area proportions (%) of the fine particles of the pigment is 0.15 or less, more preferably 0.12 or less, and particularly preferably 0.08 or less.
  • a support having a diffuse reflective surface of a second kind can be preferably used.
  • "Diffuse reflectivity of a second kind” means diffuse reflectivity obtained by making a specular surface uneven, to form finely divided specular surfaces facing different directions, which finely divided surfaces, specular surfaces, are dispersed in their directions.
  • the unevenness of the diffuse reflective surface of the second kind preferably has a three-dimensional average coarseness of 0.1 to 2 ⁇ m, and more preferably 0.1 to 1.2 ⁇ m, for the center surface.
  • the frequency of unevenness of the surface is preferably in the range of 0.1 to 2000 cycle/mm, and more preferably 50 to 600 cycle/mm, per unevenness having coarseness of 0.1 ⁇ m or more. Details about such a support are described in JP-A No. 239244/1990.
  • silver halide grains preferably grains of silver chloroiodobromide, silver chlorobromide, or silver chloride, respectively made up of 95 mol % or more of silver chloride.
  • grains made up of silver chloride or silver chlorobromide substantially free from silver iodide can be preferably used in order to shorten the development processing time.
  • substantially free from silver iodide means that the silver iodide content is 1 mol % or less, and preferably 0.2 mol % or less.
  • high-silver-chloride grains containing 0.01 to 3 mol % of silver iodide on the emulsion surface are preferably used.
  • the halogen composition of the emulsion may be different or the same from grain to grain. When an emulsion whose halogen composition is the same from grain to grain is used, the properties may be easily made homogeneous from grain to grain.
  • halogen composition distribution within silver halide emulsion grains for example, grains having the so-called uniform-type structure, wherein the composition of every part of the silver halide grains is the same; grains having the so-called layered structure, wherein the halogen composition of the cores inside the silver halide grains is different from that of the shells (each comprising a single layer or layers) surrounding the cores; or grains having a structure having parts different in halogen composition within the grains or on the surfaces of the grains in a non-layered manner (a structure wherein the parts different in halogen composition are conjugated on the edges, corners, or planes of the surface of the grain, when such parts exist on the grain surface.), can be suitably chosen for use.
  • the grains of any of the latter two types of grains are advantageous for use and also preferable in view of pressure resistance.
  • the boundary of parts different in halogen composition may be distinctive or obscure by forming mixed crystals due to different compositions, or the said boundary may be positively continuously changed in structure.
  • the high-silver-chloride emulsion used in the present invention has preferably a structure in which a silver bromide localized phase is present within the silver halide grains and/or on the surface of the silver halide grains in a layered manner or non-layered manner, as described above.
  • the halogen composition of the above localized phase has a silver bromide content of at least 10 mol %, and more preferably over 20 mol %.
  • the silver bromide content of the silver bromide localized phase can be analyzed by X-ray diffractometry (e.g. described in Shinjikken Kagaku-koza 6, Kozo Kaiseki , edited by Nihon Kagaku-kai and published by Maruzen) or the like.
  • the localized phase can be present within the grains or on the edges, corners, or planes of the surfaces of the grains. As one preferable example of the localized phase, a localized phase epitaxially grown on the corners of the grains can be mentioned.
  • an emulsion of a nearly pure silver chloride for example, having a silver chloride content of 98 to 100 mol %, is also preferably used.
  • the average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention is preferably 0.1 to 2 ⁇ m.
  • the grain size distribution is preferably a so-called monodisperse distribution having a deviation coefficient (obtained by dividing the standard deviation of the grain size distribution by the average grain size) of generally 20% or less, desirably 15% or less, and more preferably 10% or less.
  • a deviation coefficient obtained by dividing the standard deviation of the grain size distribution by the average grain size
  • a regular crystal shape such as a cubic shape, a tetradecahedral shape, and an octahedral shape
  • an irregular crystal shape such as a spherical shape and a tabular shape
  • a complex shape of these can be used.
  • a mixture of various crystal shapes may be used.
  • recommendably grains having the above regular crystal shape are contained in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.
  • an emulsion wherein tabular grains having an average aspect ratio (circle equivalent diameter/thickness) of 5 or more, and preferably 8 or more, are present in an amount of more than 50% in all grains in terms of projected areas, can also be preferably used.
  • the silver (bromo)chloride emulsion used in the present invention can be prepared by a method described, for example, by P. Glafkides in "Chemie et Phisique Photographique,” Paul Montel, 1967; by G. F. Duffin in “Photographic Emulsion Chemistry,” Focal Press, 1966; or by V. L. Zelikman et al. in “Making and Coating Photographic Emulsion,” Focal Press, 1964. That is, any of the acid process, the neutral process, the ammonia process, and the like can be used; and to react a soluble silver salt with a soluble halogen salt, any of the single-jet method, the double-jet method, a combination thereof, and the like can be used.
  • a method wherein grains are formed in the presence of excess silver ions can also be used.
  • the double-jet method a method wherein pAg in the liquid phase, in which a silver halide will be formed, is kept constant, that is, the so-called controlled double-jet method, can also be used. According to this method, a silver halide emulsion wherein the crystals are regular in shape and whose grain size is approximately uniform, can be obtained.
  • the localized phase or the substrate of the silver halide grains for use in the present invention preferably contains different metal ions or their complex ions.
  • Preferable metals are chosen from among ions or complexes of metals of Groups VIII and IIb of the Periodic Table, lead ions, and thallium ions.
  • ions or complex ions chosen from among ions or complex ions of iridium, rhodium, iron, and the like can be used alone or in combination
  • ions or complex ions chosen from among ions or complex ions of osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron, and the like can be used alone or in combination.
  • the types of metal ions and the concentrations of metal ions may be different. These metals may be used in a combination of two or more. Particularly preferably an iron compound and an iridium compound are present in the silver bromide localized phase.
  • the compounds providing these metal ions are put into the localized phase and/or other grain part (substrate) of the silver halide grains for use in the present invention, for example, by means of dissolving them in an aqueous gelatin solution, an aqueous halide solution, an aqueous silver salt solution, or some other aqueous solution that will serve as a dispersion medium when the silver halide grains are formed, or they are so put by means of adding and dissolving silver halide fine particles in which metal ions are allowed to be contained previously.
  • the metal ions to be used in the present invention can be contained in emulsion grains before, during, or immediately after the formation of the grains. This timing will depend on where the metal ions are located in the grains.
  • the silver halide emulsion to be used in the present invention is chemically and spectrally sensitized.
  • the type using a chalcogen sensitizer specifically, sulfur sensitization, represented by addition of an unstable sulfur compound; selenium sensitization, using a selenium compound; and tellurium sensitization, using a tellurium compound, can be mentioned
  • noble metal sensitization represented by gold sensitization, reduction sensitization, and the like can be used singly or in combination.
  • compounds used in the chemical sensitization those described in JP-A No. 215272/1987, page 18, right lower column, to page 22, right upper column, can be preferably used.
  • the effect of the constitution of the light-sensitive material of the present invention is more remarkable when a high-silver-chloride emulsion sensitized with gold is used.
  • the emulsion to be used in the present invention is a so-called surface-latent-image-type emulsion, wherein a latent image will be formed mainly on the grain surfaces.
  • Specific examples of these compounds that are preferably used are those described in the above-mentioned JP-A No. 215272/1987, pages 39 to 72.
  • 5-Arylamino-1,2,3,4-thiatriazole compounds, wherein the aryl residue has at least one electron-attracting group, described in European Patent No. 0,447,647, are also preferably used.
  • the spectral sensitization is carried out for the purpose of spectrally sensitizing, in a desired wavelength range, the emulsion of each layer in the light-sensitive material of the present invention.
  • spectral sensitizing dye to be used for spectral sensitization in the blue, green, and red ranges in the light-sensitive material of the present invention for example, those described by F.M. Harmer in Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons, New York, London, 1964) can be mentioned.
  • Specific exemplary compounds and spectral sensitizations are those described in the above-mentioned JP-A No. 215272/1987, page 22, right upper column, to page 38, which are preferably used.
  • red-sensitive spectral sensitizing dyes for silver halide emulsion grains particularly high in silver chloride content those described in JP-A No. 123340/1991 are very preferred in view, for example, of the stability and the intensity of absorption and the temperature dependency of exposure.
  • spectral sensitizing dyes may be directly dispersed in the emulsion or may be dissolved in a solvent or a mixed solvent, for example, of water, methanol, ethanol, propanol, methyl cellosolve, and/or 2,2,3,3-tetrafluoropropanol, to be added to the emulsion.
  • a solvent or a mixed solvent for example, of water, methanol, ethanol, propanol, methyl cellosolve, and/or 2,2,3,3-tetrafluoropropanol.
  • the spectral sensitizing dye may be made into an aqueous solution by allowing an acid or a base to coexist, as described, for example, in JP-B Nos.
  • the said dye may be made into an aqueous solution or a colloid dispersion by allowing a surface-active agent to coexist, as described in U.S. Patent Nos. 3,822,135 and 4,006,025, and the thus prepared aqueous solution or colloid dispersion may be added to the emulsion.
  • the spectral sensitizing dye may be dissolved in a solvent substantially incompatible with water, such as phenoxyethanol, and the resultant solution may be dispersed in water or a hydrophilic colloid and added to the emulsion.
  • the spectral sensitizing dye may be directly dispersed in a hydrophilic colloid, as described in JP-A Nos. 102733/1978 and 105141/1983, and the resultant dispersion may be added to the emulsion.
  • the addition to the emulsion may be carried out at any stage for the preparation of the emulsion that is hitherto known to be effective. Specifically, the addition can be carried out before the formation of the grains of the silver halide emulsion, during the formation of the grains, during the period from immediately after the formation of the grains to before the washing step, before or during the chemical sensitization, during the period from immediately after the chemical sensitization to the cooling and solidification of the emulsion, or during the preparation of the coating liquid.
  • the addition is carried out during the period from after the completion of the chemical sensitization to before the coating.
  • the addition can also be carried out simultaneously with the addition of a chemical sensitizer to effect the spectral sensitization and the chemical sensitization simultaneously, as described in U.S. Patent Nos. 3,628,969 and 4,225,666, or the addition can also be carried out prior to the chemical sensitization as described in JP-A No. 113928/1983, or it can also be carried out before the completion of the formation of the precipitate of the silver halide grains to start the spectral sensitization. Further, as taught in U.S. Patent No.
  • the spectral sensitizing dye can also be added in portions; that is, part of the spectral sensitizing dye is added prior to the chemical sensitization, and the remainder is added after the chemical sensitization, and the addition may be carried out at any time during the formation of the silver halide grains using, for example, a method taught in U.S. Patent No 4,183,756.
  • the sensitizing dye is preferably added before the step of washing the emulsion or before the chemical sensitization.
  • the amount of these spectral sensitizing dyes to be added varies widely depending on the particular case, but it is preferably in the range of 0.5 x 10 -6 mol to 1.0 x 10 -2 mol, and more preferably 1.0 x 10 -6 mol to 5.0 x 10 -3 mol, per mol of the silver halide.
  • a sensitizing dye having a spectral sensitizing sensitivity particularly in the range from the red region to the infrared region preferably compounds described in JP-A No. 157749/1990, page 13, right lower column, to page 22, right lower column, are additionally used.
  • these compounds the preservability of the light-sensitive material, the stability of the processing, and the supersensitization effect can be specifically increased.
  • compounds of formulae (IV), (V), and (VI) described in that patent are additionally used.
  • These compounds can be used in an amount of generally 0.5 x 10 -5 mol to 5.0 x 10 -2 mol, and preferably 5.0 x 10 -5 mol to 5.0 x 10 -3 mol, per mol of the silver halide, and an advantageous amount is in the range of generally 0.1 to 10,000 times, and preferably 0.5 to 5,000 times, the mole of the sensitizing dye.
  • the light-sensitive material of the present invention is used in a print system using usual negative printers, and also it is preferably used for digital scanning exposure that uses monochromatic high-density light, such as a second high harmonic generating light source (SHG) that comprises a combination of a nonlinear optical crystal with a semiconductor laser or a solid state laser using a semiconductor laser as an excitation light source, a gas laser, a light-emitting diode, or a semiconductor laser.
  • SHG second high harmonic generating light source
  • a semiconductor laser or a second harmonic generating light source (SHG) that comprises a combination of a nonlinear optical crystal with a semiconductor laser or a solid state laser.
  • the use of a semiconductor laser is preferable, and it is desired to use a semiconductor laser for at least one of the exposure light sources.
  • the spectral sensitivity maximum of the light-sensitive material of the present invention can arbitrarily be set by the wavelength of the light source for the scanning exposure to be used.
  • an SHG light source obtained by combining a nonlinear optical crystal with a semiconductor laser or a solid state laser that uses a semiconductor laser as an excitation light source
  • the spectral sensitivity maximum of the light-sensitive material can be present in each of the usual three regions, the blue region, the green region and the red region.
  • each of at least two layers has a spectral sensitivity maximum at 670 nm or over. This is because the emitting wavelength range of the available, inexpensive, and stable III-V group semiconductor laser is present now only in from the red region to the infrared region.
  • the oscillation of a II-VI group semiconductor laser in the green or blue region is confirmed and it is highly expected that these semiconductor lasers can be used inexpensively and stably if production technique for the semiconductor lasers is developed. In that event, the necessity that each of at least two layers has a spectral sensitivity maximum at 670 nm or over becomes lower.
  • the time for which the silver halide in the light-sensitive material is exposed is the time for which a certain very small area is required to be exposed.
  • the very small area the minimum unit that controls the quantity of light from each digital data is generally used and is called a picture element. Therefore, the exposure time per picture element is changed depending on the size of the picture element.
  • the size of the picture element is dependent on the density of the picture element, and the actual range is from 50 to 2,000 dpi. If the exposure time is defined as the time for which a picture size is exposed with the density of the picture element being 400 dpi, preferably the exposure time is 10 -4 sec or less, more preferably 10 -6 sec or less. When the above value of the optical density is within the preferable range, the sharpness of the image is further improved.
  • the hydrophilic colloid layer of the light-sensitive material may be preferably added dyes (particularly oxonol dyes and cyanine dyes) capable of being decolored by processing, as described in European Patent No. 0,337,490 A2, pages 27 to 76.
  • dyes particularly oxonol dyes and cyanine dyes
  • water-soluble dyes When some of these water-soluble dyes are used in an increased amount, color separation and safelight immunity are deteriorated. As dyes that can be used without deteriorating color separation, water-soluble dyes described in European Patent No. 0,539,978 A1 and JP-A Nos. 127325/1993 and 127324/1993 are preferable.
  • a colored layer that can be decolored by processing may be used instead of the water-soluble dye or in combination with the water-soluble dye.
  • the colored layer to be used that can be decolored by processing may be directly adjacent to the emulsion layer, or it may be arranged to be adjacent to the emulsion layer through an intermediate layer containing a processing color-mixing inhibitor, such as gelatin and hydroquinone.
  • a processing color-mixing inhibitor such as gelatin and hydroquinone.
  • the colored layer is arranged below (on the side of the support) an emulsion layer that will form the same primary color as the color of the colored layer. All or some of colored layers corresponding to respective or arbitrarily selected primary colors may be arranged. Also, colored layer corresponding to plural primary color regions may be arranged.
  • the optical reflection density of the colored layer is preferably such that the optical density value at the wavelength having the highest optical density in the wavelength region used for exposure (the visible light region of from 400 nm to 700 nm, in the case of usual printer exposure, and the wavelength of the scanning exposure light source to be used, in the case of scanning exposure) is 0.2 or more but 3.0 or less, more preferably 0.5 or more but 2.5 or less, and particularly preferably 0.8 or more but 2.0 or less.
  • the colored layer conventionally known methods can be applied. For example, use can be made of a method wherein dyes described in JP-A No. 282244/1990 (page 3, upper right column, to page 8), or dyes described in JP-A No. 7931/1991 (page 3, upper right column, to page 11, lower left column), are made into a solid fine particle dispersion state and are contained in a hydrophilic colloid layer; a method wherein a cationic polymer is mordanted with an anionic dye; a method wherein a dye is adsorbed to fine particles, for example, of a silver halide, and is fixed in a layer; and a method, as described in JP-A No.
  • colloidal silver is used.
  • a fine powder of a dye is dispersed in the solid state
  • a fine powder dye which is substantially insoluble in water, at least at a pH of 6 or below, but which is substantially soluble in water, at least at a pH of 8 or over, is contained.
  • a method wherein a cation polymer is mordanted with an anionic dye is described in JP-A No. 84637/1990 (pages 18 to 26).
  • Methods of the preparation of colloidal silver as a light absorber are described in U.S. Patent Nos. 2,688,601 and 3,459,563. Among these methods, one in which a fine powder dye is contained, and one in which colloidal silver is used, are preferable.
  • a gelatin As a binder or a protective colloid that can be used in the light-sensitive material according to the present invention, a gelatin is advantageously used, and other hydrophilic colloids can be used alone or in combination with a gelatin.
  • a gelatin a low-calcium gelatin having a calcium content of 800 ppm or less, and more preferably 200 ppm or less, is preferably used.
  • mildew-proofing agents as described in JP-A No. 271247/1988, are added.
  • the exposed light-sensitive material can be subjected to conventional color development processing.
  • a desilvering process is carried out.
  • a bleaching process and a fixing process may be carried out separately or simultaneously (a bleach-fix process).
  • a mode of the desilvering process in the present invention comprises a bleach-fix process after color development, for the purpose of rapid processing.
  • the pH of the bleaching solution is about 6.5 or less, more preferably about 6.0 or less, and further preferably about 5.5 or less, for the purpose, for example, of accelerating the desilvering.
  • a processing method wherein, after a bleaching process, a bleach-fix process is carried out may be used. Further, a process wherein use is made of bleach-fix solutions contained in two consecutive baths, a process wherein a fixing process is carried out before a bleach-fix process, or a process wherein a bleaching process is carried out after a bleach-fix process, can be carried out arbitrarily to meet an intended purpose.
  • Example bleaching agents for use in the bleaching solution or the bleach-fix solution include, for example, iron salts; compounds of polyvalent metals, such as iron(III), cobalt(III), chromium(IV), and copper(II); peracids; quinones; and nitro compounds.
  • Typical bleaching agents are iron chloride, ferricyanides, dichromates, organic complex salts of iron(III) (e.g.
  • aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol-ether-diaminetetraacetic acid), persulfates, bromates, permanganates, and nitrobenzenes.
  • aminopolycarboxylic acid iron(III) complex salts such as ethylenediaminetetraacetatic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt, are preferred, in view of rapid processing and the prevention of environmental pollution.
  • aminopolycarboxylic acid iron (III) complex salts are particularly useful in a bleaching solution and a bleach-fix solution.
  • the bleaching solution and bleach-fix solution that use these aminopolycarboxylic acid irons(III) complex salts can be generally used at a pH of 3 to 8.
  • a rehalogenating agent including ammonium bromide and ammonium chloride
  • a pH buffering agent including ammonium nitrate
  • a metal corrosion-preventive agent including ammonium sulfate
  • an organic acid for the purpose of preventing bleach stain.
  • the particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5.5, and specifically acetic acid, and propionic acid are preferable.
  • Example fixing agents for use in the fixing solution and the bleach-fix solution include thiosulfates, thiocyanates, thioether-series compounds, thioureas, a large amount of iodide salts, and use of thiosulfates is usual, and especially ammonium thiosulfate is most widely used.
  • Preferable preservatives for the fixing solution and the bleach-fix solution are sulfites, bisulfites, carbonylbisulfite adducts, and sulfinic acid compounds described in European Patent No. 294769A. Further, in the fixing solution and the bleach-fix solution, to stabilize the solutions, it is preferable to add any of various aminopolycarboxylic acids, organic phosphonic acids (e.g. 1-hydroxyethylidene-1,1-diphosphonic acid, N,N,N',N'-ethylenediaminetetraphosphonic acid).
  • organic phosphonic acids e.g. 1-hydroxyethylidene-1,1-diphosphonic acid, N,N,N',N'-ethylenediaminetetraphosphonic acid.
  • any of various fluorescent whitening agents, antifoaming agents, surface-active agents, polyvinylpyrolidones, and methanol can be contained.
  • a bleach-accelerating agent in the bleaching solution, the bleach-fix solution, and the bath preceding them, if required, a bleach-accelerating agent can be used.
  • useful bleach-accelerating agents include compounds having a mercapto group or a disulfide bond, as described, for example, in U.S. Patent No. 3,893,856, West German Patent No. 1,290,812, JP-A No. 95630/1978, and Research Disclosure No. 17129 (July 1978); thiazolidine derivatives described in JP-A No. 140129/1975; thiourea derivatives described in U.S. Patent No. 3,706,561; iodide salts described in JP-A No. 16235/1983; polyoxyethylene compounds described in West Germany Patent No.
  • a preferable total time is 5 sec to 1 min, and more preferably 5 sec to 25 sec.
  • the processing temperature is generally 25 to 50 °C and preferably 35 to 45 °C. Within the preferable range of the processing temperature, the desilvering rate is increased and the occurrence of stain after the processing can be effectively prevented.
  • any known stirring method can be applied in each steps, and preferably the stirring is intensified as much as possible.
  • intensify the stirring specifically a method wherein a jet stream of a processing liquid is caused to impinge on the emulsion surface of a light-sensitive material, as described in JP-A Nos. 183460/1987 and 183461/1987; a method wherein a rotating means is used to increase the stirring effect, as described in JP-A No.
  • silver halide emulsions other materials (e.g. additives), and photographic constitutional layers (e.g. layer arrangement) that can be applied to the light-sensitive material according to the present invention; and, as the processing methods and the processing additives that can be applied for processing the light-sensitive material, those described in the below-mentioned patent gazettes, in particular, in the specification of European Patent No. 0,355,660 A2 (JP-A No. 139544/1987), are preferably used.
  • a cyan coupler, a magenta coupler, or a yellow coupler is impregnated into a loadable latex polymer (e.g. those described in U.S. Patent No. 4,203,716) in the presence (or absence) of a high-boiling point organic solvent listed in the above-mentioned Table, or such a coupler is dissolved together with a water-insoluble organic-solvent-soluble polymer and is emulsified and dispersed in an aqueous hydrophilic colloid solution.
  • a loadable latex polymer e.g. those described in U.S. Patent No. 4,203,716
  • a high-boiling point organic solvent listed in the above-mentioned Table
  • Water-insoluble organic-solvent-soluble polymers that can be preferably used include homopolymers or copolymers described in U.S. Patent No. 4,857,449, columns 7 to 15, and International Publication No. WO 88/00723, pages 12 to 30. More preferably, water-insoluble organic-solvent-soluble polymers are methacrylate-series or acrylamide-series polymers, and particularly use of acrylamide-series polymers is preferable, in view of dye image stability or the like.
  • a dye-image-preservability-improving compound as described in the specification of European Patent No. 0,277,589A2, together with a coupler.
  • a coupler preferably use is made of a dye-image-preservability-improving compound, as described in the specification of European Patent No. 0,277,589A2, together with a coupler.
  • a dye-image-preservability-improving compound as described in the specification of European Patent No. 0,277,589A2
  • a coupler preferably use is made of a dye-image-preservability-improving compound, as described in the specification of European Patent No. 0,277,589A2, together with a coupler.
  • a pyrazoloazole coupler preferably pyrrolotriazole coupler, or a yellow coupler.
  • magenta couplers to be used in the present invention 5-pyrazolone-series magenta couplers and pyrazoloazole-type couplers, as described in the gazettes in the above table, can be mentioned.
  • 5-pyrazolone-series magenta couplers 5-pyrazolone-series magenta couplers of arylthio coupling split-off, described in International Publication WO Nos. 92/18901, 92/18902, and 92/18903, are preferable, because of the image preservability and less fluctuation of the image quality after processing.
  • pyrazoloazole-series couplers pyrazolotriazole couplers in which a secondary or tertiary alkyl group is directly bonded to the 2-, 3-, or 6-position of the pyrazolotriazole ring, as described in JP-A No. 65245/1986; pyrazoloazole couplers containing a sulfonamide group in the molecule, as described in JP-A No. 65246/1986; pyrazoloazole couplers having an alkoxyphenylsulfonamido ballasting group, as described in JP-A No.
  • acylacetanilide-type couplers are preferably used, and above all, pivaloylacetanilide-type couplers having a halogen atom or an alkoxy group in the ortho-position of the anilide ring; acylacetanilide-type couplers in which the acyl group is a 1-position-substituted cycloalkanecarbonyl group, which are described, for example, in European Patent No. 0,447,969A, JP-A Nos. 107701/1993, and 113642/1993; and malondianilide-type couplers described, for example, in European Patent Nos. 0,482,552A and 0,524,540A, are preferably used.
  • the color photographic light-sensitive material of the present invention is excellent in rapid processibility; it is not substantially subject to blix fading, which will result from a decrease in the color density due to the leuco dye formation of a produced cyan dye in a blix solution; and it is capable of forming a color photograph excellent in image quality, high in color density, and free from destruction of the color balance of the image with the lapse of time after processing.
  • a cyan coupler ExC
  • UV-B Ultraviolet Absorbing Agent
  • 25.2 g of a color image stabilizer (Cpd-1), 1.2 g of a color image stabilizer (Cpd-6), 1.2 g of a color image stabilizer (Cpd-8), 1.2 g of a color image stabilizer (Cpd-9), and 1.3 g of a color image stabilizer (Cpd-10) were dissolved in 1.3 g of a solvent (Solv-1), 24 g of a solvent (Solv-6), and 180 ml of ethyl acetate, and the resulting solution was emulsified and dispersed into 800 g of a 10% aqueous gelatin solution containing 60 ml of 10% sodium dodecylbenzenesulfonate, to prepare an emulsified dispersion C.
  • a silver chlorobromide emulsion C (cubes, a mixture of a large-size emulsion C having an average grain size of 0.50 ⁇ m, and a small-size emulsion C having an average grain size of 0.41 ⁇ m (1 : 4 in terms of mol of silver), the deviation coefficients of the grain size distributions being 0.09 and 0.11, respectively, and each emulsion having 0.8 mol% of silver bromide locally contained in part of the grain surface whose substrate was made up of silver chloride) was prepared.
  • the above emulsified dispersion C and this silver chlorobromide emulsion C were mixed and dissolved, and a fifth-layer coating liquid was prepared so that it would have the composition shown below.
  • the coating amount of the emulsion is in terms of silver.
  • coating liquids for the other layers were prepared.
  • gelatin hardeners for each layers 1-oxy-3,5-dichloro-s-triazine sodium salt was used.
  • the sensitizing dye D was added to the large-size emulsion in an amount of 3.0 x 10 -4 mol per mol of the silver halide, and to the small-size emulsion in an amount of 3.6 x 10 -4 mol per mol of the silver halide;
  • the sensitizing dye E was added to the large-size emulsion in an amount of 4.0 x 10 -5 mol per mol of the silver halide, and to the small-size emulsion in an amount of 7.0 x 10 -5 mol per mol of the silver halide;
  • the sensitizing dye F was added to the large-size emulsion in an amount of 2.0 x 10 -4 mol per mol of the silver halide, and to the small-size emulsion in an amount of 2.8 x 10 -4 mol per mol of the silver halide.
  • additive X was added in an amount of 2.6 x 10 -3 mol per mol of the silver halide.
  • the fourth layer, the sixth layer, and the seventh layer were added the same compound, so that the amounts would be 0.2 mg/m 2 , 0.2 mg/m 2 , 0.6 mg/m 2 , and 0.1 mg/m 2 , respectively.
  • each layer is shown below.
  • the numbers show coating amounts (g/m 2 ).
  • the coating amount is in terms of silver.
  • Polyethylene-Laminated Paper [The polyethylene on the first layer side contained a white pigment (TiO 2 ; in a content of 15% by weight) and a blue dye (ultramarine)]
  • Silver chlorobromide emulsion A (cubes, a mixture of a large-size emulsion A having an average grain size of 0.88 ⁇ m, and a small-size emulsion A having an average grain size of 0.70 ⁇ m (3 : 7 in terms of mol of silver), the deviation coefficients of the grain size distributions being 0.08 and 0.10, respectively, and each emulsion having 0.3 mol% of silver bromide locally contained in part of the grain surface whose substrate was made up of silver chloride) 0.25 Gelatin 1.38 Yellow coupler (ExY) 0.60 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) 0.02 Solvent (Solv-1) 0.22
  • Second Layer Color Mixing Inhibiting Layer
  • a silver chlorobromide emulsion (cubes, a mixture of a large-size emulsion B having an average grain size of 0.55 ⁇ m, and a small-size emulsion B having an average grain size of 0.39 ⁇ m (1 : 3 in terms of mol of silver).
  • the deviation coefficients of the grain size distributions were 0.10 and 0.08, respectively, and each emulsion had 0.8 mol% of AgBr contained locally in part of the grain surface whose substrate was made up of silver chloride.
  • Cpd-4) 0.08 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.12 Solvent (Solv-7) 0.09 Color image stabilizer (Cpd-7) 0.07
  • a silver chlorobromide emulsion (cubes, a mixture of a large-size emulsion having an average grain size of 0.50 ⁇ m, and a small-size emulsion having an average grain size of 0.41 ⁇ m (1 : 4 in terms of mol of silver).
  • the deviation coefficients of the grain size distributions were 0.09 and 0.11, respectively, and each emulsion had 0.8 mol% of silver bromide locally contained in part of the grain surface whose substrate was made up of silver chloride.) 0.19 Gelatin 0.74 Cyan coupler (ExC) 0.24 Ultraviolet absorbing agent (UV-B) 0.21 Color image stabilizer (Cpd-1) 0.20 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0.20
  • UV-C Ultraviolet absorbing agent
  • Cpd-7 Color image stabilizer
  • Solv-9 Solvent
  • light-sensitive materials 102 to 119 were prepared with the same method to the light-sensitive material 101, except that the cyan coupler and a polymer were used as shown in Table 2 in the fifth red-sensitive layer.
  • the molecular weight of the used polymer according to the present invention was 100,000 to 500,000, in terms of weight average molecular weight.
  • the ratio of polymer to be used was 30% by weight of the coupler.
  • Processing step Temperature Time Replenisher Tank volume Color Development 38.5 °C 45 sec 73 ml 500 ml Bleach-fix 30-35 °C 45 sec 60 ml 500 ml Rinse (1) 30-35 °C 20 sec - 500 ml Rinse (2) 30-35 °C 20 sec - 500 ml Rinse (3) 30-35 °C 20 sec 370 ml 500 ml Drying 70-80 °C 60 sec (Rinsing was conducted in a three tanks counter current system from (3) to (1).)
  • composition of each processing solution are as follows.
  • the light-sensitive material samples 101 to 119 were processed in the above processing steps.
  • the cyan reflection density (D A ) of the D max part of each sample was measured; then, after the sample was dipped in a bleaching solution for color negative film, CN-16N2X (trade name, manufactured by Fuji Photo Film Co., Ltd.; described in a manual for CN-16X), for 30 min, to cause the leuco dye of the cyan dye partially formed during the above processing to be restored to the cyan dye (color-restoration), the cyan reflection density (D B ) of the D max part was measured again.
  • the measured D B for each sample was approximately 2.5.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP97108611A 1997-05-28 1997-05-28 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Withdrawn EP0881535A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97108611A EP0881535A1 (fr) 1997-05-28 1997-05-28 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière

Applications Claiming Priority (1)

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EP97108611A EP0881535A1 (fr) 1997-05-28 1997-05-28 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière

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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619195A (en) * 1968-11-01 1971-11-09 Eastman Kodak Co Photographic coupler dispersions
US4203716A (en) 1976-11-24 1980-05-20 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic addenda uniformly loaded in latex polymer particles
JPS62215272A (ja) 1986-02-17 1987-09-21 Fuji Photo Film Co Ltd カラ−画像形成方法
EP0277589A2 (fr) 1987-01-28 1988-08-10 Fuji Photo Film Co., Ltd. Photographies en couleurs, un procédé pour les préparer et matériaux photographiques couleurs employés à cet effet
US4914005A (en) * 1987-06-01 1990-04-03 Eastman Kodak Company Photographic element containing a cyan dye forming coupler
US4950585A (en) 1987-08-18 1990-08-21 Konica Corporation Coupler for photographic use
JPH02289840A (ja) * 1989-01-10 1990-11-29 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
EP0447647A2 (fr) 1990-03-22 1991-09-25 Minnesota Mining And Manufacturing Company Eléments photographiques d'halogénure d'argent sensibles à l'infrarouge
US5104783A (en) 1988-10-04 1992-04-14 Fuji Photo Film Co., Ltd. Silver halide color photographic material
JPH04204730A (ja) 1990-11-30 1992-07-27 Fuji Photo Film Co Ltd 新規な色素形成カプラーおよび該カプラーを含有するハロゲン化銀カラー写真感光材料
US5162196A (en) 1989-11-20 1992-11-10 Fuji Photo Film Co., Ltd. Color coupler for photography and silver halide photographic material comprising the same
EP0539978A1 (fr) 1991-10-30 1993-05-05 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent et procédé de formation d'images couleur avec celui-ci
JPH05127325A (ja) 1991-10-30 1993-05-25 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料及びカラー画像形成方法
JPH05127324A (ja) 1991-10-30 1993-05-25 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料及びカラー画像形成方法
EP0556700A1 (fr) 1992-02-19 1993-08-25 Fuji Photo Film Co., Ltd. Matériau photosensible couleur à l'halogénure d'argent
EP0614116A1 (fr) * 1993-03-02 1994-09-07 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensibles à la lumière

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619195A (en) * 1968-11-01 1971-11-09 Eastman Kodak Co Photographic coupler dispersions
US4203716A (en) 1976-11-24 1980-05-20 Eastman Kodak Company Photographic elements having hydrophilic colloid layers containing hydrophobic addenda uniformly loaded in latex polymer particles
JPS62215272A (ja) 1986-02-17 1987-09-21 Fuji Photo Film Co Ltd カラ−画像形成方法
EP0277589A2 (fr) 1987-01-28 1988-08-10 Fuji Photo Film Co., Ltd. Photographies en couleurs, un procédé pour les préparer et matériaux photographiques couleurs employés à cet effet
US4914005A (en) * 1987-06-01 1990-04-03 Eastman Kodak Company Photographic element containing a cyan dye forming coupler
US4950585A (en) 1987-08-18 1990-08-21 Konica Corporation Coupler for photographic use
US5104783A (en) 1988-10-04 1992-04-14 Fuji Photo Film Co., Ltd. Silver halide color photographic material
JPH02289840A (ja) * 1989-01-10 1990-11-29 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5047316A (en) * 1989-01-10 1991-09-10 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5162196A (en) 1989-11-20 1992-11-10 Fuji Photo Film Co., Ltd. Color coupler for photography and silver halide photographic material comprising the same
EP0447647A2 (fr) 1990-03-22 1991-09-25 Minnesota Mining And Manufacturing Company Eléments photographiques d'halogénure d'argent sensibles à l'infrarouge
JPH04204730A (ja) 1990-11-30 1992-07-27 Fuji Photo Film Co Ltd 新規な色素形成カプラーおよび該カプラーを含有するハロゲン化銀カラー写真感光材料
EP0539978A1 (fr) 1991-10-30 1993-05-05 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent et procédé de formation d'images couleur avec celui-ci
JPH05127325A (ja) 1991-10-30 1993-05-25 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料及びカラー画像形成方法
JPH05127324A (ja) 1991-10-30 1993-05-25 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料及びカラー画像形成方法
EP0556700A1 (fr) 1992-02-19 1993-08-25 Fuji Photo Film Co., Ltd. Matériau photosensible couleur à l'halogénure d'argent
EP0614116A1 (fr) * 1993-03-02 1994-09-07 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensibles à la lumière

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