EP0777153B1 - Produit photographique couleur à l'halogénure d'argent sensible à la lumière - Google Patents

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

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Publication number
EP0777153B1
EP0777153B1 EP96119208A EP96119208A EP0777153B1 EP 0777153 B1 EP0777153 B1 EP 0777153B1 EP 96119208 A EP96119208 A EP 96119208A EP 96119208 A EP96119208 A EP 96119208A EP 0777153 B1 EP0777153 B1 EP 0777153B1
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EP
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Prior art keywords
group
silver halide
silver
sensitive material
color
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EP96119208A
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German (de)
English (en)
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EP0777153A1 (fr
Inventor
Koichi Nakamura
Masakazu Morigaki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • G03C7/39296—Combination of 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/061—Hydrazine compounds
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/267—Packaging; Storage
    • 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
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
    • 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
    • G03C7/39208—Organic compounds
    • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material.
  • the present invention further relates to a silver halide color photographic light-sensitive material that is excellent in processing stability and suitable for low-replenishment-rate processing.
  • the present invention also relates to a silver halide color photographic light-sensitive material that provides an image good in color-forming property and excellent in image stability and stained less in terms of long-term storage of the image.
  • silver halide color photographic light-sensitive materials are processed through a color development step and a desilvering step, to form an image.
  • a color development step silver halide grains that have been exposed to light are developed (reduced) with an aromatic primary amine developing agent, and the subsequent reaction of the oxidized product thereof, with couplers, gives a color-developed image.
  • the color development is carried out in an alkali bath containing 4-amino-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)-aniline sulfate, as an aromatic primary amine developing agent.
  • sulfonylamidohydrazine-type compound has the drawback that when a two-equivalent coupler is used, color is hardly formed.
  • two-equivalent couplers have the advantages that stain due to storage of couplers themselves can be reduced, and that coupling split-off groups can be made to have various functions.
  • a coupling split-off group means a substituent which a coupler has at its coupling reactive position, and that is capable of being split-off upon coupling reaction with an oxidation product of a color-forming reducing agent (a developing agent).
  • the color-forming reducing agent according to the present invention such as a sulfonylhydrazine or a carbamoylhydrazine
  • the storage preservability of the color-formed dye image obtained by processing is poor and formation of stain is conspicuous.
  • An object of the present invention is to provide a silver halide color photographic light-sensitive material suitable for greatly reducing both the replenishment rate and processing chemicals.
  • Another object of the present invention is to provide a silver halide color photographic light-sensitive material improved in fastness of a dye image to the long-term storage of the light-sensitive material, and restrained from forming stain.
  • the present invention provides:
  • the image obtained by using the color-forming reducing agent and the coupler for use in the present invention exhibits high color density and low minimum density and is excellent in long-term storage preservability.
  • the obtained image is stored for a long period of time under high temperature and high humidity, an increase in stain is observed, but stain that will occur during storage can be reduced greatly by using the sulfinic acid compound according to the present invention.
  • the color-forming reducing agent represented by formula (II) or (III) is used, the effect of suppressing stain by the sulfinic acid compound according to the present invention is particularly great.
  • a combination of the color-forming reducing agent of formula (II) or (III) with a two-equivalent coupler gives a high-quality image with less stain.
  • X 11 represents a hydrogen atom, some other atom, or a group of atoms, which atom or atoms forms an inorganic salt (e.g. Li, Na, K, Ca, and Mg) or an organic salt (e.g. NH 4 + , HN(C 2 H 5 ) 3 + , and N(CH 3 ) 4 + ).
  • an inorganic salt e.g. Li, Na, K, Ca, and Mg
  • organic salt e.g. NH 4 + , HN(C 2 H 5 ) 3 + , and N(CH 3 ) 4 + .
  • R 41 to R 45 which are the same or different, each represent a hydrogen atom or a substituent.
  • substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a nitro group, a sulfo group, a sulfino group, a hydroxy group, an alkoxy group, an alkenoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an alkenylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an alkenylamino group, an arylamino group, a heterocyclic amino group, an acylamino group, a sulfonamido group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl
  • the groups of R 41 to R 45 in the ortho-positions each other may bond together to form a 5- to 6-membered ring. Provided that the sum total of the carbon atoms of R 41 to R 45 is 10 or more.
  • X 11 preferably represents a hydrogen atom, Na, or K, and the sum total of the carbon atoms of R 41 to R 45 is preferably 12 or more, more preferably 15 or more.
  • Preferable substituents represented by R 41 to R 45 include an alkyl group, an aryl group, a halogen atom, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an acylamino group, a sulfonamido group, an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, and a ureido group.
  • the usage amount of the compound represented by formula (S) according to the present invention is generally 0.01 to 10 times, preferably 0.05 to 2 times, and more preferably 0.1 to 1 times, the usage amount of the color-forming reducing agent to be used in a color-forming layer, in terms of mol.
  • the color-forming reducing agent represented by formula (I) to be used in the present invention is a compound characterized in that the compound is oxidized by reacting in an alkaline solution directly with a silver halide that has been exposed to light, or it is oxidized by undergoing a redox reaction with an auxiliary developing agent oxidized with a silver halide that has been exposed to light, and its oxidation product reacts with a dye-forming coupler, to form a dye.
  • R 11 represents an aryl group or a heterocyclic group, which may be substituted.
  • the aryl group represented by R 11 has preferably 6 to 14 carbon atoms, and examples are phenyl and naphthyl.
  • the heterocyclic group represented by R 11 is preferably a saturated or unsaturated, 5-membered, 6-membered, or 7-membered heterocyclic ring containing at least one of nitrogen, oxygen, sulfur, and selenium, to which a benzene ring or a heterocyclic ring may be condensed.
  • heterocyclic ring represented by R 11 examples include furanyl, thienyl, oxazolyl, thiazolyl, imidazolyl, triazolyl, pyrrolidinyl, benzoxazolyl, benzthiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, purinyl, pteridinyl, azepinyl, and benzooxepinyl.
  • the substituent possessed by R 11 includes, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an acyloxy group, an acylthio group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an amino group, an alkylamino group, an arylamino group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a ureido group, a sulfonamido group, a sulfamoylamino group, an acyl
  • R 12 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, which may be substituted.
  • the alkyl group represented by R 12 is a straight-chain, branched, or cyclic alkyl group having preferably 1 to 16 carbon atoms, such as methyl, ethyl, hexyl, dodecyl, 2-octyl, t-butyl, cyclopentyl, and cylooctyl.
  • the akenyl group represented by R 12 is a chain or cyclic alkenyl group having preferably 2 to 16 carbon atoms, such as vinyl, 1-octenyl, and cyclohexenyl.
  • the alkynyl group represented by R 12 is an alkynyl group having preferably 2 to 16 carbon atoms, such as 1-butynyl and phenylethynyl.
  • the aryl group and the heterocyclic group represented by R 12 include those mentioned for R 11 .
  • the substituent possessed by R 12 includes those mentioned for the substituent of R 11 .
  • X is a -SO 2 -, -CO-, -COCO-, -CO-O-, -CON(R 13 )-, -COCO-O-, -COCO-N(R 13 )-, or -SO 2 -N(R 13 )- group, in which R 13 represents a hydrogen atom or a group represented by R 12 that is defined above.
  • Z 1 represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group
  • Z 2 represents a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group.
  • the acyl group preferably has 1 to 50 carbon atoms, and more preferably 2 to 40 carbon atoms.
  • Specific examples include an acetyl group, a 2-methylpropanoyl group, a cyclohexylcarbonyl group, an n-octanoyl group, a 2-hexyldecanoyl group, a dodecanoyl group, a chloroacetyl group, a trifluoroacetyl group, a benzoyl group, a 4-dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group, and a 3-(N-hydroxy-N-methylaminocarbonyl)propanoyl group.
  • the alkoxycarbonyl group and the aryloxycarbonyl group have 2 to 50 carbon atoms, and more preferably 2 to 40 carbon atoms.
  • Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, an isobutyloxycarbonyl group, a cyclohexyloxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, a phenoxycarbonyl group, a 4-octyloxyphenoxycarbonyl 2-hydroxymethylphenoxycarbonyl group, and a 2-dodecyloxyphenoxycarbonyl group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 each represent a hydrogen atom or a substituent.
  • substituents include a straight-chain or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (e.g.
  • ethynyl and 1-propinyl an aryl group having 6 to 50 carbon atoms (e.g. phenyl, naphthyl, and anthryl), an acyloxy group having 1 to 50 carbon atoms (e.g. acetoxy, tetradecanoyloxy, and benzoyloxy), a carbamoyloxy group having 1 to 50 carbon atoms (e.g. N,N-dimethylcarbamoyloxy), a carbonamido group having 1 to 50 carbon atoms (e.g.
  • aryloxy group having 6 to 50 carbon atoms e.g. phenoxy, 4-methoxyphenoxy, and naphthoxy
  • an aryloxycarbonyl group having 7 to 50 carbon atoms e.g. phenoxycarbonyl and naphthoxycarbonyl
  • an alkoxycarbonyl group having 2 to 50 carbon atoms e.g.
  • N-acylsulfamoyl group having 1 to 50 carbon atoms e.g. N-tetradecanoylsulfamoyl and N-benzoylsulfamoyl
  • alkylsulfonyl group having 1 to 50 carbon atoms e.g. methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, and 2-hexyldecylsulfonyl
  • an arylsulfonyl group having 6 to 50 carbon atoms e.g.
  • a cyano group a nitro group, a carboxyl group, a hydroxy group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 50 carbon atoms (e.g. methanesulfinyl and octanesulfinyl), an arylsulfinyl having 6 to 50 carbon atoms (e.g.
  • N-butylsulfamoylamino and N-phenylsulfamoylamino a silyl group having 3 to 50 carbon atoms (e.g. trimethylsilyl, dimethyl-t-butylsilyl, and triphenylsilyl), and a halogen atom (e.g. a fluorine atom, a chlorine atom, and a bromine atom).
  • the above substituents may have a substituent, and examples of such a substituent include those mentioned above.
  • X 1 , X 2 , X 3 , X 4 , and X 5 may bond together to form a condensed ring.
  • condensed ring 5-membered to 7-membered ring is preferable, and 5-membered to 6-membered ring is more preferable.
  • the number of carbon atoms of the substituent is preferably 50 or below, more preferably 42 or below, and most preferably 34 or below, and there is preferably 1 or more carbon atom(s).
  • the sum of the Hammett substituent constant ⁇ p values of X 1 , X 3 , and X 5 and the Hammett substituent constant ⁇ m values of X 2 and X 4 is 0.80 or more but 3.80 or below.
  • X 6 , X 7 , X 8 , X 9 , and X 10 in formula (VI) each represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group, or a heterocyclic group, which may have a substituent and may bond together to form a condensed ring.
  • the sum of the Hammett substituent constant ⁇ p values of X 6 , X 8 , and X 10 and the Hammett substituent constant ⁇ m values of X 7 and X 9 is 1.20 or more but 3.80 or below, preferably 1.50 or more but 3.80 or below, and more preferably 1.70 or more but 3.80 or below.
  • Hammett substituent constants ⁇ p and ⁇ m are described in detail in such books as "Hammett no Hosoku/Kozo to Hannousei,” written by Naoki Inamoto (Maruzen); “Shin-jikken Kagaku-koza 14/Yukikagoubutsu no Gosei to Hanno V,” page 2605 (edited by Nihonkagakukai, Maruzen); “Riron Yukikagaku Kaisetsu,” written by Tadao Nakaya, page 217 (Tokyo Kagakudojin); and “Chemical Review” (Vol. 91), pages 165 to 195 (1991).
  • R 1 and R 2 in formulae (IV) and (V), and R 4 and R 5 in formulae (VI) and (VII), each represent a hydrogen atom or a substituent, and examples of the substituent are the same as those described for X 1 , X 2 , X 3 , X 4 , and X 5 ; preferably each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, or a substituted or unsubstituted heterocyclic group having 1 to 50 carbon atoms, and more preferably at least one of R 1 and R 2 , and at least one of R 4 and R 5 , are each a hydrogen atom.
  • R 3 represents a heterocyclic group.
  • a preferable heterocyclic group has 1 to 50 carbon atoms, and the heterocyclic group contains at least one hetero atom, such as a nitrogen atom, an oxygen atom, and a sulfur atom, and further the heterocyclic group is a saturated or unsaturated 3-membered 8-membered) to 12-membered (preferably 3-membered to monocyclic or condensed ring.
  • heterocyclic ring examples include furan, pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole, pyridazine, indole, pyrazole, triazole, and quinoxaline.
  • These heterocyclic groups may have a substituent, and preferably they have one or more electron-attracting groups.
  • an electron-attracting group means one wherein the Hammett ⁇ p value is a positive value.
  • the 5- to 8-membered nitrogen-containing heterocyclic group formed by Q 1 and the C may contain other hetero atom such as a sulfur atom and an oxygen atom, and may be condensed with another ring such as a benzene ring.
  • the heterocyclic group formed by Q 1 and the C preferably contains 1 to 3 nitrogen atoms and is preferably a 5- to 6-membered heterocyclic group.
  • These heterocyclic groups formed by Q 1 and the C may have a substituent, which are described in detail for the above R 3 .
  • a ballasting group means a group, having 5 to 50, preferably 8 to 40 carbon atoms, which makes the color-forming reducing agent that has a ballasting group, easily-soluble in a high-boiling organic solvent, and been hardly deposited even after emulsifying and dispersing, and which makes the color-forming reducing agent immobilized in a hydrophilic colloid.
  • couplers that are preferably used in the present invention, compounds having structures described by the following formulae (1) to (12) are mentioned. They are compounds collectively generally referred to as active methylenes, pyrazoloolones, pyrazoloazoles, phenols, naphthols, and pyrrolotriazoles, respectively, which are compounds known in the art.
  • Formulae (1) to (4) represent couplers that are called active methylene-seires couplers, and, in the formulae, R 14 represents an acyl group, a cyano group, a nitro group, an aryl group, a heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, optionally substituted.
  • R 15 represents an optionally substituted alkyl group, aryl group, or heterocyclic residue.
  • R 16 represents an optionally substituted aryl group or heterocyclic residue. Examples of the substituent that may be possessed by R 14 , R 15 , and R 16 include those mentioned for X 1 to X 5 .
  • Y represents a hydrogen atom or a group capable of coupling split-off by coupling reaction with the oxidation product of the color-forming reducing agent.
  • Y are a heterocyclic group (a saturated or unsaturated 5-membered to 7-membered monocyclic or condensed ring having, as a hetero atom, at least one nitrogen atom, oxygen atom, sulfur atom, or the like, e.g.
  • a chlorine atom and a bromine atom an aryloxy group (e.g. phenoxy and 1-naphthoxy), a heterocyclic oxy group (e.g. pyridyloxy and pyrazolyoxy), an acyloxy group (e.g. acetoxy and benzoyloxy), an alkoxy group (e.g. methoxy and dodecyloxy), a carbamoyloxy group (e.g. N,N-diethylcarbamoyloxy and morpholinocarbonyloxy), an aryloxycarbonyloxy group (e.g. phenylcarbonyloxy), an alkoxycarbonyloxy group (e.g.
  • methoxycarbonyloxy and ethoxycarbonyloxy an arylthio group (e.g. phenylthio and naphthylthio), a heterocyclic thio group (e.g. tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxadiazolylthio, and benzimidazolylthio), an alkylthio group (e.g. methylthio, octylthio, and hexadecylthio), an alkylsulfonyloxy group (e.g. methanesulfonyloxy), an arylsulfonyloxy group (e.g.
  • benzenesulfonyloxy and toluenesulfonyloxy a carbonamido group (e.g. acetamido and trifluoroacetamido), a sulfonamido group (e.g. methanesulfonamido and benzenesulfonamido), an alkylsulfonyl group (e.g. methanesulfonyl), an arylsulfonyl group (e.g. benzenesulfonyl), an alkylsulfinyl group (e.g. methanesulfinyl), an arylsulfinyl group (e.g. benzenesulfinyl), an arylazo group (e.g. phenylazo and naphthylazo), and a carbamoylamino group (e.g. N-methylcarbamoylamino).
  • Y may be substituted, and examples of the substituent that may be possessed by Y include those mentioned for X 1 to X 5 .
  • Y represents a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group.
  • R 14 and R 15 , and R 14 and R 16 may bond together to form a ring.
  • Formula (5) represents a coupler that is called a 5-pyrazolone-series coupler, and in the formula, R 17 represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group.
  • R 18 represents a phenyl group or a phenyl group that is substituted by one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or acylamino groups.
  • Preferable 5-pyrazolone-series couplers represented by formula (5) are those wherein R 17 represents an aryl group or an acyl group, and R 18 represents a phenyl group that is substituted by one or more halogen atoms.
  • R 17 is an aryl group, such as a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-chloro-5-tetradecaneamidophenyl group, a 2-chloro-5-(3-octadecenyl-1-succinimido)phenyl group, a 2-chloro-5-octadecylsulfonamidophenyl group, and a 2-chloro-5-[2-(4-hydroxy-3-t-butylphenoxy)tetradecaneamido]phenyl group; or R 17 is an acyl group, such as an acetyl group, a 2-(2,4-di-t-pentylphenoxy)butanoyl group, a benzoyl group, and a 3-(2,4-di-t-amylphenoxyacetamido)benzoyl group;
  • R 18 represents a substituted phenyl group, such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group, and a 2-chlorophenyl group.
  • Formula (6) represents a coupler that is called a pyrazoloazole-series coupler, and, in the formula, R 19 represents a hydrogen atom or a substituent.
  • Q 3 represents a group of nonmetal atoms required to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, which azole ring may have a substituent (including a condensed ring).
  • Preferable pyrazoloazole-series couplers represented by formula (6) in view of spectral absorption characteristics of the color-formed dyes, are imidazo[1,2-b]pyrazoles described in U.S. Patent No. 4,500,630, pyrazolo[1,5-b]-1,2,4-triazoles described in U.S. Patent No. 4,500,654, and pyrazolo[5,1-c]-1,2,4-triazoles described in U.S. Patent No. 3,725,067.
  • pyrazoloazole couplers are pyrazoloazole couplers having a branched alkyl group directly bonded to the 2-, 3-, or 6-position of the pyrazolotriazole group, as described in JP-A ("JP-A" means unexamined published Japanese patent application) No. 65245/1986; pyrazoloazole couplers containing a sulfonamido group in the molecule, as described in JP-A No.
  • pyrazoloazole couplers having an alkoxyphenylsulfonamido ballasting group as described in JP-A No. 147254/1986
  • pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in JP-A No. 209457/1987 or 307453/1988
  • pyrazolotriazole couplers having a carbonamido group in the molecule as described in JP-A No. 201443/1990.
  • Y has the same meaning as defined above.
  • Formulae (7) and (8) are respectively called phenol-series couplers and naphthol-series couplers, and in the formulae R 20 represents a hydrogen atom or a group selected from the group consisting of -CONR 22 R 23 , -SO 2 NR 22 R 23 , -NHCOR 22 , -NHCONR 22 R 23 , and -NHSO 2 NR 22 R 23 .
  • R 22 and R 23 each represent a hydrogen atom or a substituent.
  • R 21 represents a substituent
  • 1 is an integer selected from 0 to 2
  • m is an integer selected from 0 to 4.
  • R 21 's may be different.
  • the substituents of R 21 to R 23 include those mentioned above as examples for X 1 to X 5 of formulae (II) and (IV).
  • Y has the same meaning as defined above.
  • phenol-series couplers represented by formula (7) include 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.
  • Y has the same meaning as defined above.
  • naphthol-series couplers represented by formula (8) include 2-carbamoyl-1-naphthol couplers described, for example, in U.S. Patent Nos. 2,474,293, 4,052,212, 4,146,396, 4,282,233, and 4,296,200; and 2-carbamoyl-5-amido-1-naphthol couplers described, for example, in U.S. Patent No. 4,690,889. Y has the same meaning as defined above.
  • Formulas (9) to (12) are couplers called pyrrolotriazoles, and R 32 , R 33 , and R 34 each represent a hydrogen atom or a substituent.
  • Y has the same meaning as defined above.
  • substituent of R 32 , R 33 , and R 34 include those mentioned for X 1 , X 2 , X 3 , X 4 , and X 5 .
  • Preferable examples of the pyrrolotriazole-series couplers represented by formulae (9) to (12) include those wherein at least one of R 32 and R 33 is an electron-attracting group, which specific couplers are described in European Patent Nos. 488,248A1, 491,197A1, and 545,300. Y has the same meaning as defined above.
  • fused-ring phenol imidazole, pyrrole, 3-hydroxypyridine, active methylene (other than those mentioned above), active methine, 5,5-ring-fused heterocyclic, and 5,6-ring-fused heterocyclic coupler, can be used.
  • fused-ring phenol-series couplers those described, for example, in U.S. Patent Nos. 4,327,173, 4,564,586, and 4,904,575, can be used.
  • imidazole-series couplers those described, for example, in U.S. Patent Nos. 4,818,672 and 5,051,347, can be used.
  • 3-hydroxypyridine-series couplers those described, for example, in JP-A No. 315736/1989, can be used.
  • active methylene-series and active methine-series couplers those described, for example, in U.S. Patent Nos. 5,104,783 and 5,162,196, can be used.
  • pyrrolopyrazole couplers described in U.S. Patent No. 5,164,289, and pyrroloimidazole couplers described in JP-A No. 174429/1992 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.
  • couplers described for example, in West Germany Patent Nos. 3,819,051A and 3,823,049, U.S. Patent Nos. 4,840,883, 5,024,930, 5,051,347, and 4,481,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, and 386,930A1, and JP-A Nos.
  • the color-forming reducing agent according to the present invention is preferably used in an amount of 0.01 to 10 mmol/m 2 in one color-forming layer, in order to obtain satisfactory color density. More preferably the amount to be used is 0.05 to 5 mmol/m 2 , and particularly preferably 0.1 to 1 mmol/m 2 .
  • a preferable amount of the coupler to be used in the color-forming layer in which the color-forming reducing agent according to the present invention is used is 0.05 to 20 times, more preferably 0.1 to 10 times, and particularly preferably 0.2 to 5 times, the amount of the color-forming reducing agent in terms of mol.
  • the color light-sensitive material of the present invention comprises, basically, at least one photographic constitutional layer comprising a hydrophilic colloid layer coated on a support (base), and in at least one photographic constitutional layers are contained a photosensitive silver halide, a coupler for forming a dye (also referred to as a dye-forming coupler or a coupler), a color-forming reducing agent, and a sulfinic acid compound.
  • the dye-forming coupler, the color-forming reducing agent and the sulfinic acid compound to be used in the present invention are added to the same layer, which is the most general mode, but they may be added separately to separate layers if they are placed in the reactive state.
  • these components are added to a silver halide emulsion layer of the light-sensitive material or a layer adjacent to it, and particularly preferably all of these components are added to a silver halide emulsion layer.
  • the color-forming reducing agent, the sulfinic acid compound, and the coupler according to the present invention can be introduced into the light-sensitive material by various known dispersion methods.
  • the oil-in-water dispersion method is used, in which they are dissolved in a high-boiling organic solvent (and, if necessary, together with a low-boiling organic solvent), the solution is emulsified and dispersed in an aqueous gelatin solution, and the emulsified dispersion is added to a silver halide emulsion.
  • the high-boiling organic solvent to be used in the present invention is preferably a compound nonmiscible with water, and having a melting point of 100 °C or below and a boiling point of 140 °C or over, that is a good solvent for the color-forming reducing agents, sulfinic acid compounds, and couplers.
  • the melting point of the high-boiling organic solvent is preferably 80 °C or below.
  • the boiling point of the high-boiling organic solvent is more preferably 160 °C or over, and even further preferably 170 °C or over. Details of these high-boiling organic solvents are described in JP-A No. 215272/1987, page 137, lower right column, to page 144, upper right column.
  • the amount of the high-boiling organic solvent to be used may be any amount, but preferably the amount is such that the weight ratio of the high-boiling organic solvent to the color-forming reducing agent is from 20 or less : 1, more preferably from 0.02 to 5 : 1, and particularly preferably from 0.2 to 4 : 1.
  • known polymer dispersion methods can be used. Specific examples of steps, effects, and latexes for impregnation of the latex dispersion method, which is one polymer dispersion method, are described, for example, in U.S. Patent No. 4,199,363, West Germany Patent Application (OLS) Nos. 2,541,274 and 2,541,230, JP-B ("JP-B" means examined Japanese patent publication) No. 41091/1978, and European Patent Publication No. 029104, and as a more preferable method, a dispersion method using a polymer which is water-insoluble and organic solvent-soluble is described in PCT International Publication No. WO 88/00723.
  • the lipophilic fine particles containing the color-forming reducing agent according to the present invention may have any average grain size.
  • the average particle size is preferably 0.05 to 0.3 ⁇ m, and further preferably 0.05 to 0.2 ⁇ m.
  • To make the average particle size of lipophilic fine particles small is generally accomplished, for example, by choosing a type of surface-active agent, by increasing the amount of the surface-active agent to be used, by elevating the viscosity of the hydrophilic colloid solution, by lowering the viscosity of the lipophilic organic layer, through use of an additional low-boiling organic solvent, by increasing the rotational frequency of the stirring blades of an emulsifying apparatus, to increase the shearing force, or by prolonging the emulsifying time.
  • a type of surface-active agent by increasing the amount of the surface-active agent to be used, by elevating the viscosity of the hydrophilic colloid solution, by lowering the viscosity of the lipophilic organic layer, through use of an additional low-boiling organic solvent, by increasing the rotational frequency of the stirring blades of an emulsifying apparatus, to increase the shearing force, or by prolonging the emulsifying time.
  • the particle size of lipophilic fine particles can be measured by an apparatus, such as a Nanosizer (trade name, manufactured by British Coulter Co.).
  • the dye that is produced from the color-forming reducing agent and the dye-forming coupler is a diffusible dye
  • a mordant is added to the light-sensitive material. If the present invention is applied to such a mode, it is not required to dip the material in an alkali to form color, and therefore image stability after processing is remarkably improved.
  • the mordant according to the present invention can be used in any layer, if the mordant is added to a layer containing the color-forming reducing agent according to the present invention, the stability of the color-forming reducing agent is deteriorated. Therefore preferably the mordant is used in a layer that does not contain the color-forming reducing agent according to the present invention.
  • the dye that is produced from a color-forming reducing agent and a coupler diffuses into the gelatin film that has been swelled during the processing, to dye the mordant. Therefore, in order to obtain good sharpness, the shorter the diffusion distance is, the more preferred it is. Accordingly, the layer to which the mordant is added is preferably a layer adjacent to the layer containing the color-forming reducing agent.
  • the dye that is produced from the color-forming reducing agent according to the present invention and the coupler for use in the present invention is a water-soluble dye
  • the layer to which the mordant is added is situated on the same side of the base and opposite to (more remote from the base than) the layer containing the color-forming reducing agent.
  • a barrier layer as described in JP-A No.
  • a layer in which the mordant is added is situated on the same side of the base and nearer the base than the layer containing the color-forming reducing agent.
  • mordant for use in the present invention may also be added to several layers, and in particular, when several layers contain the color-forming reducing agent, also preferably the mordant is added to each layer adjacent thereto.
  • the coupler that forms a diffusible dye may be any coupler that results in a diffusible dye formed by coupling with the color-forming reducing agent according to the present invention, the resultant diffusible dye being capable of reaching the mordant.
  • the coupler is a coupler that results in a diffusible dye having one or more dissociable groups with a pKa (an acid dissociation constant) of 12 or less, more preferably 8 or less, and particularly preferably 6 or less.
  • the molecular weight of the diffusible dye that will be formed is 200 or more but 2,000 or less.
  • the ratio (the molecular weight of the dye that will be formed/the number of dissociable groups with a pKa of 12 or less) is 100 or more but 2,000 or less, and more preferably 100 or more but 1,000 or less.
  • the value of pKa is the value measured by using, as a solvent, dimethylformamide/water (1 : 1).
  • the coupler that forms a diffusible dye is preferably one that results in a diffusible dye formed by coupling with the color-forming reducing agent according to the present invention, the resultant diffusible dye being dissolvable, in an alkali solution having a pH of 11, in an amount of 1 x 10 -6 mol/liter or more, more preferably 1 x 10 -5 mol/liter or more, and particularly preferably 1 x 10 -4 mol/liter or more, at 25 °C.
  • the coupler that forms a diffusible dye is preferably one that results in a diffusible dye formed by coupling with the color-forming reducing agent according to the present invention, the resultant diffusible dye having a diffusion constant of 1 x 10 -8 m 2 /s -1 or more, more preferably 1 x 10 -7 m 2 /s -1 or more, and particularly preferably 1 x 10 -6 m 2 /s -1 or more, at 25 °C when dissolved in an alkali solution of pH 11, at a concentration of 10 -4 mol/liter.
  • the mordant that can be used in the present invention can be suitably chosen from among mordants that are usually used, and among them, in particular, polymer mordants are preferable.
  • polymer mordant is meant a polymer containing a tertiary amino group, polymers having a nitrogen-containing heterocyclic moiety, polymers containing a quaternary cation group thereof, etc.
  • homopolymers and copolymers containing vinyl monomer units with a tertiary imidazole group are described, for example, in U.S. Patent Nos. 4,282,305, 4,115,124, and 3,148,061 and JP-A Nos. 118834/1985, 122941/1985, 244043/1987, and 244036/1987.
  • homopolymers and copolymers containing vinyl monomer units with a quaternary imidazolium salt are described, for example, in British Patent Nos. 2,056,101, 2,093,041, and 1,594,961, U.S. Patent Nos. 4,124,386, 4,115,124, and 4,450,224, and JP-A No. 28325/1973.
  • homopolymers and copolymers having vinyl monomer units with a quaternary ammonium salt are described, for example, in U.S. Patent Nos.3,709,690, 3,898,088, and 3,958,995, and JP-A Nos. 57836/1985, 60643/1985, 122940/1985, 122942/1985, and 235134/1985.
  • vinylpyridine polymers and vinylpyridinium cation polymers as disclosed, for example, in U.S. Patent Nos. 2,548,564, 2,484,430, 3,148,161, and 3,756,814; polymer mordants capable of being crosslinked to gelatin or the like, as disclosed, for example, in U.S. Patent Nos. 3,625,694, 3,859,096, and 4,128,538, and British Patent No. 1,277,453; aqueous sol-type mordants disclosed, for example, in U.S. Patent Nos. 3,958,995, 2,721,852, and 2,798,063, and JP-A Nos.
  • the molecular weight of the polymer mordants for use in the present invention is suitably 1,000 to 1,000,000, and particularly preferably 10,000 to 200,000.
  • the above polymer mordants are used generally by mixing them with a hydrophilic colloid.
  • a hydrophilic colloid and/or a highly hygroscopic polymer can be used, and gelatin is most typically used.
  • the mixing ratio of the polymer mordant to the hydrophilic colloid, and the coating amount of the polymer mordant can be determined easily by those skilled in the art in accordance with the amount of the dye to be mordanted, the type and composition of the polymer mordant, and the image formation process to be used.
  • the mordant/hydrophilic colloid ratio is from 20/80 to 80/20 (by weight), and the coating amount of the mordant is suitably 0.2 to 15 g/m 2 , and preferably 0.5 to 8 g/m 2 , for use.
  • an auxiliary developing agent and/or its precursor are used in the light-sensitive material. These compounds are described below.
  • auxiliary developing agent that may be used in the present invention, is meant a compound having a function for promoting the transfer of electrons from a color-forming reducing agent to a silver halide, in the process of development of silver halide grains.
  • the auxiliary developing agent is a compound that can develop silver halide grains that have been exposed to light, and its oxidation product can oxidize (hereinafter referred to as cross-oxidize) a color-forming reducing agent.
  • auxiliary developing agent that may be used in the present invention, preferably pyrazolidones, dihydroxybenzenes, reductones, or aminophenols are used, with particular preference given to pyrazolidones.
  • the diffusibility of these compounds in hydrophilic colloid layers is low, and, for example, the solubility (25 °C) in water is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less.
  • the precursor of the auxiliary developing agent that may be used in the present invention is a compound that can exist stably in the light-sensitive material, but it can quickly release the above auxiliary developing agent, upon processing with a processing solution.
  • this compound preferably the diffusibility in hydrophilic colloid layers is low.
  • the solubility (25 °C) in water is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less.
  • the solubility of the auxiliary developing agent that will be released from the precursor, but preferably the solubility of the auxiliary developing agent itself is low.
  • the auxiliary developing agent precursor for use in the present invention is represented by formula (A): formula (A) A-(L) n -PUG wherein A represents a blocking group whose bond to (L) n -PUG will be split upon development processing, L represents a linking group whose bond to PUG will be split off after the split of the bond between L and A in formula (A), n is an integer of 0 to 3, and PUG represents an auxiliary developing agent.
  • auxiliary developing agent use can be made of compounds that can emit electrons in accordance with the Kendall-Pelz's rule, excluding p-phenylenediamine compounds, and preferably pyrazolidones mentioned above are used.
  • blocking groups such as an acyl group and a sulfonyl group, as described, for example, in U.S. Patent No. 3,311,476; blocking groups that use the reverse Michael reaction, as described, for example, in JP-A No. 105642/1984; blocking groups that use quinonemethide or compounds similar to quinonemethide by intramolecular electron transfer, as described, for example, in JP-A No. 280140/1990; blocking groups that use an intramolecular nucleophilic substitution reaction, as described, for example, in JP-A No. 318555/1988 (European Patent Publication No.
  • blocking groups such as an acyl group and a sulfonyl group, as described, for example, in U.S. Patent No. 3,311,476
  • blocking groups that use the reverse Michael reaction as described, for example, in JP-A No. 105642/1984
  • blocking groups that use an addition reaction of a nucleophilic agent to a conjugated unsaturated bond as described, for example, in JP-A No. 186344/1992; blocking groups that use a ⁇ -elimination reaction, as described in JP-A No. 163051/1987; blocking groups that use a nucleophilic substitution reaction of diarylmethanes, as described in JP-A No. 188540/1986; blocking groups that use a Lossen rearrangement reaction, as described in JP-A No. 187850/1987; blocking groups that use a reaction of an N-acyl product of thiazolidin-2-thione with an amine, as described in JP-A No. 147457/1987; and blocking groups that have two electrophilic groups and react with two nucleophilic agents, as described in International Publication Patent No. 93/03419.
  • the group represented by L is a linking group that can be split from the group represented by A, upon development processing, and that then can split (L) n-1 -PUG. There are no particular restrictions on the linking group, as long as that function is attained.
  • auxiliary developing agent and its precursor are shown below, but compounds that may be used in the present invention are not restricted to these examples.
  • auxiliary developing agent may be added to any of light-sensitive layers, intermediate layers, undercoat layers, and protective layers.
  • auxiliary developing agent When the auxiliary developing agent is contained, it is preferably added to non-light-sensitive layers, for use.
  • a method wherein the compound is dissolved in an organic solvent miscible with water, such as methanol, and the solution is added directly to a hydrophilic colloid layer; a method wherein an aqueous solution or colloid dispersion of the compound prepared in the presence of a surface-active agent, is added; a method wherein the compound is dissolved in a solvent or oil substantially immiscible with water, the solution is dispersed in water or a hydrophilic colloid, and the dispersion is added; or a method wherein the compound in the state of a solid fine particle dispersion is added, and these conventionally known methods can be applied alone or in combination. Details of a method of preparing a solid fine particle dispersion are described in JP-A No. 235044/1992, page 20.
  • the amount to be added to the light-sensitive material is generally 1 to 200 mol%, preferably 5 to 100 mol %, and more preferably 10 to 50 mol%, based on the color-forming reducing agent.
  • any support can be used if it is a transmissible support or a reflective support, on which a photographic emulsion layer can be coated, such as glass, paper, and plastic film.
  • plastic film to be used in the present invention for example, polyester films made, for example, of polyethylene terephthalates, polyethylene naphthalates, cellulose triacetate, or cellulose nitrate; polyamide films, polycarbonate films, and polystyrene films can be used.
  • 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 hydrophilic resin containing a light-reflecting substance, such as titanium oxide, zinc oxide, calcium oxide, and calcium sulfate, dispersed therein, or a support made of a hydrophilic resin itself containing a dispersed light-reflecting substance.
  • a hydrophilic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium oxide, and calcium sulfate
  • Examples are a polyethylene-coated paper, a polyester-coated paper, a polypropylene-series synthetic paper, a 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 polyester-coated paper particularly a polyester-coated paper whose major component is a polyethylene terephthalate, as described in European Patent EP 0,507,489, is preferably used.
  • 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.
  • the particles of a white pigment are contained in a density of 12% or more by weight, and more preferably 14% or more by weight.
  • the light-reflecting white pigment is kneaded well in the presence of a surface-active agent, and the surface of the pigment particles is treated with a dihydric to tetrehydric alcohol.
  • a support having the second kind diffuse reflective surface can also be used, preferably.
  • the second kind diffuse reflectivity means diffuse reflectivity obtained by making a specular surface uneven, to form finely divided specular surfaces facing different directions.
  • the unevenness of the second kind diffuse reflective surface has a three-dimensional average coarseness of generally 0.1 to 2 ⁇ m, and preferably 0.1 to 1.2 ⁇ m, for the center surface. Details about such a support are described in JP-A No. 239244/1990.
  • a combination of at least three silver halide emulsion layers photosensitive to respectively different spectral regions.
  • a combination of three layers of a blue-sensitive red-sensitive layer, a green-sensitive layer, and a layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer, and the like can be coated on the above support.
  • the photosensitive layers can be arranged in various orders known generally for color light-sensitive materials. Further, each of these light-sensitive layers can be divided into two or more layers if necessary.
  • photographic constitutional layers comprising the above photosensitive layers and various non-light-sensitive layers, such as a protective layer, an underlayer, an intermediate layer, an antihalation layer, and a backing layer, can be provided. Further, in order to improve the color separation, various filter dyes can be added to the photographic constitutional layer.
  • a gelatin is advantageously used, and other hydrophilic colloids can be used alone or in combination with a gelatin.
  • the calcium content of gelatin is preferably 800 ppm or less, more preferably 200 ppm or less, and the iron content of the gelatin is preferably 5 ppm or less, more preferably 3 ppm or less.
  • mildew-proofing agents as described in JP-A No. 271247/1988, are added.
  • 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 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 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.
  • the lower limit is not particularly restricted, but it is preferably 10 -8 sec. More preferably, the exposure time per picture element is in a range between 10 -8 to 10 -4 sec.
  • the silver halide grains used in the present invention are made of silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide.
  • Other silver salts such as silver rhodanate, silver sulfide, silver selenide, silver carbonate, silver phosphate, or a silver salt of an organic acid, may be contained in the form of independent grains or as part of silver halide grains. If it is desired to make the development/desilvering (bleaching, fixing, and bleach-fix) step rapid, a so-called high-silver-choloride grains having a silver chloride content of 90 mol% or more are desirable. Further, if the development is to be restrained moderately, it is preferable to contain silver iodide. The preferable silver iodide content varies depending on the intended light-sensitive material.
  • a high-silver-chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in a layered manner, or a non-layered manner, in the silver halide grains, and/or on the surface of the silver halide grains.
  • the halogen composition of said localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably of more than 20 mol%.
  • the silver bromide content of the silver bromide localized layer can be analyzed, for example, by using X-ray diffractometry (e.g. described in "Shinjikken Kagaku-koza 6, Kozo Kaiseki", edited by Nihonkagaku-kai, Maruzen).
  • the localized phase can be present in the grains, or on the edges, corners, or planes of the surfaces of the grains. As a preferable example, a localized phase grown epitaxially on the corners of grains, can be mentioned.
  • an emulsion comprising nearly pure silver chloride for example having a silver chloride content of 98 to 100 mol%, is also preferably used.
  • the grains of the silver halide emulsion for use in the present invention preferably have a distribution or a structure with respect to the halogen composition. Typical examples thereof are disclosed, for example, in JP-B No. 13162/1968, JP-A Nos. 215540/1986, 222845/1985, 143331/1985, 75337/1986 and 222844/1985.
  • junctioned structure In order to make the inside of grains have a structure, not only the enclosing structure, as mentioned above, but also a so-called junctioned structure can be used to form grains. Examples thereof are disclosed, for example, in JP-A Nos. 133540/1984 and 108526/1983, European Patent No. 199,290A2, JP-B No. 24772/1983, and JP-A No. 16254/1984.
  • junctioned structure not only a combination of silver halides but also a combination of a silver halide with a silver salt compound having no rock salt structure, such as silver rhodanate and silver carbonate, can be used for the junctioned structure.
  • a preferable mode is one wherein the core part has higher silver iodide content than the shell part. Reversely, in some cases, grains having a lower silver iodide content in the core part than in the shell part are preferable. Similarly, in the case of grains having a junctioned structure, the silver iodide content of the host crystals is relatively higher than that of the junctioned crystals, or this may be reversed.
  • the boundary part of the grains having these structures in which different halogen compositions are present may be distinct or indistinct. Also preferable is a mode wherein the composition is continuously changed positively.
  • the halogen composition distribution between grains is controlled.
  • the method of measuring the halogen composition distribution between grains is described in JP-A No. 254032/1985.
  • a highly uniform emulsion having a deviation coefficient of halogen composition distribution of 20% or below is preferable.
  • any of regular crystals having no twin plane those described in "Shashin Kogyo no Kiso, Ginen Shashin-hen", edited by Nihon Shashin-gakkai (Corona Co.), page 163 (1979), parallel multiple twins having two or more parallel twin planes, and nonparallel multiple twins having two or more nonparallel twin planes, can be chosen and used.
  • An example in which grains different in shape are mixed is disclosed in U.S. Patent No. 4,865,964.
  • Grains having two or more planes in one grain such as tetradecahedral grains having (100) and (111) planes in one grain, grains having (100) and (110) planes in one grain, or grains having (111) and (110) planes in one grain, can also be chosen and used in accordance with the purpose.
  • Tabular grains having an aspect ratio of greater than 1 can be used in the present invention.
  • Tabular grains can be prepared by methods described, for example, by Cleve in "Photography Theory and Practice” (1930), page 131; by Gutoff in "Photographic Science and Engineering", Vol. 14, pages 248 to 257 (1970); and in U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent No. 2,112,157.
  • the average aspect ratio of 80% or more of all the projected areas of grains is desirably 1 or more but less than 100, more preferably 2 or more but less than 20, and particularly preferably 3 or more but less than 10.
  • a triangle, a hexagon, a circle, and the like can be chosen.
  • a regular hexagonal shape having six approximately equal sides, described in U.S. Patent No. 4,797,354, is a preferable mode.
  • the grain size of tabular grains is expressed by the diameter of the projected area assumed to be a circle, and grains having an average diameter of 0.6 microns or below, as described in U.S. Patent No. 4,748,106, are preferable, because the quality of the image is made high.
  • It is preferable to restrict the shape of tabular grains so that the thickness of the grains may be 0.5 microns or below, and more preferably 0.3 microns or below, because the sharpness is increased.
  • an emulsion in which the grains are highly uniform in thickness, with the deviation coefficient of grain thickness being 30% or below is also preferable.
  • Grains in which the thickness of the grains and the plane distance between twin planes are defined, as described in JP-A No. 163451/1988, are also preferable.
  • dislocation introduced straight in a special direction in the crystal orientation of grains, or curved dislocation can be chosen, and it is possible to choose from, for example, dislocation introduced throughout grains, dislocation introduced in a particular part of grains, and dislocation introduced limitedly to a particular part such as fringes of grains.
  • dislocation introduced into tabular grains also preferable is the case of introduction of dislocation lines into regular crystalline grains or irregular grains, represented by potato grains.
  • the silver halide emulsion used in the present invention may be subjected to a treatment for making grains round, as disclosed, for example, in European Patent Nos. 96,727B1 and 64,412B1, or it may be improved in the surface, as disclosed in West German Patent No. 2,306,447C2 and JP-A No. 221320/1985.
  • the grain surface has a flat structure, but it is also preferable in some cases to make the grain surface uneven intentionally. Examples are described, for example, in JP-A Nos. 106532/1983 and 221320/1985, and U.S. Patent No. 4,643,966.
  • the grain size of the emulsion used in the present invention is evaluated, for example, by the diameter of the projected area equivalent to a circle using an electron microscope; by the diameter of the grain volume equivalent to a sphere, calculated from the projected area and the grain thickness; or by the diameter of a volume equivalent to a sphere, using the Coulter Counter method.
  • a selection can be made with wide range of grains from ultrafine grains having a sphere-equivalent diameter of 0.01 microns or below, to coarse grains having a sphere-equivalent diameter of 10 microns or more.
  • grains of 0.1 microns or more but 3 microns or below are used as photosensitive silver halide grains.
  • an emulsion having a wide grain size distribution that is, a so-called polydisperse emulsion, or an emulsion having a narrow grain size distribution, that is, a so-called monodisperse emulsion
  • the scale for representing the size distribution the diameter of the projected area of the grain equivalent to a circle, or the deviation coefficient of the diameters of the grain volume equivalent to a sphere, can be used. If a monodisperse emulsion is used, it is preferable to use an emulsion having such a size distribution that the deviation coefficient is 25% or below, more preferably 20% or below, and further more preferably 15% or below.
  • two or more monodisperse silver halide emulsions different in grain size are mixed and applied to the same layer or are applied as overlaid layers.
  • two or more polydisperse silver halide emulsions can be used as a mixture; or they can be used to form overlaid layers; or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture; or the combination can be used to form overlaid layers.
  • the photographic emulsion for use in the present invention can be prepared by a method described, for example, by P. Glafkides in "Chemie et Physique 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.
  • a method wherein grains are formed in the presence of excess silver ions can also be used.
  • the so-called controlled 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.
  • a silver halide emulsion wherein the crystals are regular in shape and whose grain size is approximately uniform, can be obtained.
  • a method in which previously precipitated and formed silver halide grains are added to a reaction vessel for the preparation of an emulsion are preferable in some cases. These can be used as seed crystals, or they are effective when they are supplied as a silver halide for growth. Further, in some cases, it is also effective to add fine grains having different halogen compositions in order to modify the surface.
  • grain formation methods wherein the concentration is changed or the flow rate is changed, as described in British Patent No. 1,469,480 and U.S. Patent Nos. 3,650,757 and 4,242,445, are preferable methods.
  • concentration is changed or the flow rate is changed, as described in British Patent No. 1,469,480 and U.S. Patent Nos. 3,650,757 and 4,242,445
  • the amount of the silver halide to be supplied can be changed as a linear function, a quadratic function, or a more complex function, of the addition time.
  • a mixing vessel that is used when a solution of a soluble silver salt and a solution of a soluble halogen salt are reacted can be selected for use from methods described in U.S. Patent Nos. 2,996,287, 3,342,605, 3,415,650, and 3,785,777, and West German Publication Patent Nos. 2,556,885 and 2,555,364.
  • a silver halide solvent is useful for the purpose of promoting the ripening.
  • other ripening agent can be used. All of the amount of these ripening agents may be blended in the dispersion medium in the reaction vessel before silver salts and halide salts are added, or their introduction into the reaction vessel may be carried out together with the addition of a halide salt, a silver salt, or a peptizer.
  • ammonia thiocyanates (e.g. potassium rhodanate and ammonium rhodanate), organic thioether compounds (e.g. compounds described, for example, in U.S. Patent Nos. 3,574,628, 3,021,215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130, and 4,782,013, and JP-A No. 104926/1982), thion compounds (e.g. tetra-substituted thioureas described, for example, in JP-A Nos. 82408/1978 and 77737/1980, and U.S. Patent No.
  • thiocyanates e.g. potassium rhodanate and ammonium rhodanate
  • organic thioether compounds e.g. compounds described, for example, in U.S. Patent Nos. 3,574,628, 3,021,215, 3,057,724, 3,038,805, 4,27
  • gelatin is used advantageously, but another hydrophilic colloid can also be used.
  • Use can be made of, for example, a gelatin derivative, a graft polymer of gelatin with another polymer, a protein, such as albumin and casein; a cellulose derivative, such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; a saccharide derivative, such as sodium alginate, a starch derivative; and many synthetic hydrophilic polymers, including homopolymers and copolymers, such as a polyvinyl alcohol, a polyvinyl alcohol partial acetal, a poly-N-vinylpyrrolidone, a polyacrylic acid, a polymethacrylic acid, a polyacrylamide, a polyvinylimidazole, and a polyvinylpyrazole.
  • a gelatin derivative such as albumin and casein
  • a cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates
  • a saccharide derivative such as sodium alg
  • gelatin in addition to lime-processed gelatin, acid-processed gelatin, and enzyme-processed gelatin described in Bull. Soc. Sci. Photo. Japan, No. 16, page 30 (1966), can be used. Further a hydrolyzate or enzymolyzate of gelatin can also be used.
  • a low-molecular-weight gelatin described in JP-A No. 158426/1989.
  • the silver halide emulsion according to the present invention is washed with water for desalting and is dispersed in a freshly prepared protective colloid.
  • the temperature at which the washing with water is carried out can be selected in accordance with the purpose, and preferably the temperature is selected in the range of 5 to 50 °C.
  • the pH at which the washing is carried out can be selected in accordance with the purpose, and preferably the pH is selected in the range of 2 to 10, and more preferably in the range of 3 to 8.
  • the pAg at which the washing is carried out can be selected in accordance with the purpose, and preferably the pAg is selected in the range of 5 to 10.
  • a method of washing with water one can be selected from the noodle washing method, the dialysis method using a diaphragm, the centrifugation method, the coagulation settling method, and the ion exchange method.
  • selection can be made from, for example, the method wherein sulfuric acid salt is used, the method wherein an organic solvent is used, the method wherein a water-soluble polymer is used, and the method wherein a gelatin derivative is used.
  • the silver halide emulsion according to the present invention is prepared, in accordance with the purpose, it is preferable to allow a salt of a metal ion to be present, for example, at the time when grains are formed, in the step of desalting, at the time when the chemical sensitization is carried out, or before the application.
  • the addition is preferably carried out at the time when the grains are formed; or after the formation of the grains but before the completion of the chemical sensitization, when the surface of the grains is modified or when the salt of a metal ion is used as a chemical sensitizer.
  • the doping of grains selection can be made from a case in which the whole grains are doped, one in which only the core parts of the grains are doped, one in which only the shell parts of the grains are doped, one in which only the epitaxial parts of the grains are doped, and one in which only the substrate grains are doped.
  • Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used.
  • These metals can be added if they are in the form of a salt that is soluble at the time when grains are formed, such as an ammonium salt, an acetate, a nitrate, a sulfate, a phosphate, a hydroxide, a six-coordinate complex, and a four-coordinate complex.
  • a salt that is soluble at the time when grains are formed such as an ammonium salt, an acetate, a nitrate, a sulfate, a phosphate, a hydroxide, a six-coordinate complex, and a four-coordinate complex.
  • Examples include CdBr 2 , CdCl 2 , Cd(NO 3 ) 2 , Pb(NO 3 ) 2 , Pb(CH 3 COO) 2 , K 3 [Fe(CN) 6 ], (NH 4 ) 4 [Fe(CN) 6 ], K 3 IrCl 6 , (NH 4 ) 3 RhCl 6
  • a ligand of the coordination compound one can be preferably selected from halogen, H 2 O, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. With respect to these metal compounds, only one can be used, but two or more can also be used in combination.
  • a method wherein a chalcogen compound is added during the preparation of the emulsion is also useful.
  • a cyanate, a thiocyanate, a selenocyanate, a carbonate, a phosphate, or an acetate may be present.
  • the silver halide grains for used in the present invention can be subjected to at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three are called chalcogen sensitization, collectively), noble metal sensitization, and reduction sensitization, in any step of the production for the silver halide emulsion.
  • a combination of two or more sensitizations is preferable.
  • Various types of emulsions can be produced, depending on the steps in which the chemical sensitization is carried out. There are a type wherein chemical sensitizing nuclei are embedded in grains, a type wherein chemical sensitizing nuclei are embedded at parts near the surface of grains, and a type wherein chemical sensitizing nuclei are formed on the surface.
  • the location at which chemical sensitizing nuclei are situated can be selected in accordance with the purpose.
  • Chemical sensitizations that can be carried out preferably in the present invention are chalcogen sensitization and noble metal sensitization, which may be used singly or in combination; and the chemical sensitization can be carried out by using active gelatin, as described by T. H.
  • an unstable sulfur compound is used, and specifically, thiosulfates (e.g. hypo), thioureas (e.g. diphenylthiourea, triethylthiourea, and allylthiourea), rhodanines, mercaptos, thioamides, thiohydantoins, 4-oxo-oxazolidin-2-thions, di- or polysulfides, polythionic acids, and elemental sulfur, and known sulfur-containing compounds described in U.S. Patent Nos. 3,857,711, 4,266,018, and 4,054,457, can be used. In many cases, sulfur sensitization is used in combination with noble metal sensitization.
  • thiosulfates e.g. hypo
  • thioureas e.g. diphenylthiourea, triethylthiourea, and allylthiourea
  • rhodanines e.g. dipheny
  • a preferable amount of a sulfur sensitizing agent used for the silver halide grains is 1 x 10 -7 to 1 x 10 -3 mol, and more preferably 5 x 10 -7 to 1 x 10 -4 mol, per mol of the silver halide.
  • selenium compounds are used, such as those described, for example, in U.S. Patent Nos. 3,297,446 and 3,297,447, specific such selenium compounds are colloidal metal selenium, selenoureas (e.g. N,N-dimethylselenourea and tetramethylselenourea), selenoketones (e.g. selenoacetone), selenoamides (e.g. selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (e.g.
  • selenium sensitization is used in combination with one or both of sulfur sensitization and noble metal sensitization.
  • the amount of the selenium sensitizing agent to be used varies depending on the selenium compound, the type of the silver halide grains, the chemical ripening conditions, and the like that are used, and the amount is generally of the order of 10 -8 to 10 -4 mol, and preferably 10 -7 to 10 -5 mol, per mol of the silver halide.
  • tellurium sensitizing agent used in the present invention compounds described, for example, in Canadian Patent No. 800,958, British Patent Nos. 1,295,462 and 1,396,696, and Japanese patent application Nos. 333819/1990 and 131598/1991 can be used.
  • a salt of a noble metal such as gold, platinum, palladium, and iridium
  • gold sensitization a known compound, such as chloroauric acid, potassium chloroaurate, potassium auriothiocyanate, gold sulfide, and gold selenide, can be used.
  • the palladium compound means salts of divalent or tetravalent palladium salt.
  • a preferable palladium compound is represented by R 2 PdX 6 or R 2 PdX 4 , wherein R represents a hydrogen atom, an alkali metal atom, or an ammonium radical; and X represents a halogen atom, i.e. a chlorine atom, a bromine atom, or an iodine atom.
  • K 2 PdCl 4 , (NH 4 ) 2 PdCl 6 , Na 2 PdCl 4 , (NH 4 ) 2 PdCl 4 , Li 2 PdCl 4 , Na 2 PdCl 6 , or K 2 PdBr 4 is preferable.
  • a gold compound and a palladium compound are used in combination with a thiocyanate or a selenocyanate.
  • the emulsion for use in the present invention is used in combination with gold sensitization.
  • a preferable amount of the gold sensitizing agent is 1 x 10 -7 to 1 x 10 -3 mol, and more preferably 5 x 10 -7 to 5 x 10 -4 mol, per mol of the silver halide.
  • a preferable amount of the palladium compound is in the range of 5 x 10 -7 to 1 x 10 -3 mol.
  • a preferable amount of the thiocyan compound and the selenocyan compound is in the range of 1 x 10 -6 to 5 x 10 -2 mol.
  • the silver halide emulsion is subjected to reduction sensitization during the formation of the grains, after the formation of the grains but before the chemical sensitization, or during or after the chemical sensitization.
  • the reduction sensitization can be selected from a method wherein a reduction sensitizer is added to a silver halide emulsion; a method called silver ripening, wherein the growth or ripening is made in an atmosphere having a pAg as low as 1 to 7; and a method called high-pH ripening, wherein the growth or ripening is made in an atmosphere having a pH as high as 8 to 11. Two or more methods can also be used in combination.
  • reduction sensitizer known reduction sensitizers can be selected and used, such as stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidinesufinic acid, silane compounds, and boran compounds; and two or more compounds can be used in combination.
  • preferable compounds are stannous chloride, aminoiminomethanesulfinic acid (popularly called thiourea dioxide), dimethylamineboran, and ascorbic acid and its derivatives.
  • the chemical sensitization can be carried out in the presence of a so-called chemical sensitization auxiliary.
  • a useful chemical sensitization auxiliary a compound is used that is known to suppress fogging and to increase the sensitivity in the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine.
  • Examples of chemical sensitization auxiliary are described in U.S. Patent Nos. 2,131,038, 3,411,914, and 3,554,757, JP-A No. 126526/1983, and by G. F. Duffin in "Photographic Emulsion Chemistry" mentioned above, pages 138 to 143.
  • an oxidizing agent for silver is added during the process of the production of the emulsion.
  • the oxidizing agent for silver refers to a compound that acts on metal silver to convert it to silver ions. Particularly useful is a compound that converts quite fine silver grains, which are concomitantly produced during the formation of silver halide grains and during the chemical sensitization, to silver ions.
  • the thus produced silver ions may form a silver salt that is hardly soluble in water, such as a silver halide, silver sulfide, and silver selenide, or they may form a silver salt that is readily soluble in water, such as silver nitrate.
  • the oxidizing agent for silver may be inorganic or organic compound.
  • Example inorganic oxidizing agents include ozone, hydrogen peroxide and its adducts (e.g. NaBO 2 •H 2 O 2 •3H 2 O, 2NaCO 3 •3H 2 O 2 , Na 4 P 2 O 7 •2H 2 O 2 , and 2Na 2 SO 4 •H 2 O 2 •2H 2 O); oxygen acid salts, such as peroxyacid salts (e.g. K 2 S 2 O 8 , K 2 C 2 O 6 , and K 2 P 2 O 8 ), peroxycomplex compounds (e.g.
  • permanganates e.g. KMnO 4
  • chromates e.g. K 2 Cr 2 O 7
  • halogen elements such as iodine and bromine
  • perhalates e.g. potassium periodate
  • salts of metals having higher valences e.g. potassium hex
  • organic oxidizing agents examples include quinones, such as p-quinone; organic peroxides, such as peracetic acid and perbenzoic acid; and compounds that can release active halogen (e.g. N-bromosuccinimido, chloramine T, and chloramine B).
  • various compounds can be incorporated for the purpose of preventing fogging during the process of the production of the light-sensitive material, during the storage of the light-sensitive material, or during the photographic processing, or for the purpose of stabilizing the photographic performance.
  • compounds known as antifoggants or stabilizers can be added, such as thiazoles including benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (such as 1-phenyl-5-mercaptotetrazole, and 1-(5-methylureidphenyl)-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines; thioketo compounds, such as oxazolinthione; and azaindenes, such as triazaindenes; tetraazaindenes (particularly 4-hydroxy-6-methyl-1,3,3a,7-te
  • the antifoggant and the stabilizer can be added at various times, for example, before the formation of the grains, during the formation of the grains, after the formation of the grains, in the step of washing with water, at the time of dispersion after the washing with water, before the chemical sensitization, during the chemical sensitization, after the chemical sensitization, and before the application.
  • the photographic emulsion to be used in the present invention is spectrally sensitized with methine dyes and the like.
  • Dyes that can be used include a cyanine dye, a merocyanine dye, a composite cyanin dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxonol dye.
  • Particularly useful dyes are those belonging to a cyanine dye, a merocyanine dye, and a composite merocyanine dye. In these dyes, any of nuclei generally used in cyanine dyes as base heterocyclic nuclei can be applied.
  • a 5- to 6-membered heterocyclic nucleus such as a pyrazolin-5-one nucleus, a thiohydantoine nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus, can be applied.
  • sensitizing dyes can be used singly or in combination, and a combination of these sensitizing dyes is often used, particularly for the purpose of supersensitization.
  • Typical examples thereof are described in U.S. Patent Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, and 4,026,707, British Patent Nos. 1,344,218 and 1,507,803, JP-B Nos. 4,936/1968 and 12,375/1978, and JP-A Nos. 110,618/1977 and 109,925/1977.
  • a dye having no spectral sensitizing action itself, or a compound that does not substantially absorb visible light and that exhibits supersensitization may be included in the emulsion.
  • the timing when the sensitizing dye is added to the emulsion may be at any stage known to be useful in the preparation of emulsions.
  • the addition is carried out most usually at a time after the completion of chemical sensitization and before coating, but it can be carried out at the same time as the addition of a chemical sensitizer, to carry out spectral sensitization and chemical sensitization simultaneously, as described in U.S, Patent Nos. 3,628,969 and 4,225,666; it can be carried out prior to chemical sensitization, as described in JP-A No. 113,928; or it can be carried out before the completion of the formation of the precipitate of silver halide grains to start spectral sensitization. Further, as taught in U.S. Patent No.
  • these foregoing compounds may be added in portions, i.e., part of these compounds is added prior to chemical sensitization, and the rest is added after the chemical sensitization, and also the addition may be carried out at any time during the formation of silver halide grains, as disclosed, for example, in U.S. Patent No. 4,183,756.
  • the amount of the sensitizing dye to be added is of the order of 4 x 10 -6 to 8 x 10 -3 mol per mol of the silver halide, but when the silver halide grain size is 0.2 to 1.2 ⁇ m, which is more preferable, the amount of the sensitizing dye to be added is more effectively about 5 x 10 -5 to 2 x 10 -3 mol per mol of the silver halide.
  • the total coated amount of silver of the light-sensitive material of the present invention preferably 0.003 to 12 g per m 2 in terms of silver is used.
  • the total coated amount of silver is preferably 1 to 12 g, and more preferably 3 to 10 g.
  • the total coated amount of silver is preferably 0.003 to 1 g, in view of rapid processing or low rate replenishment, and in that case, the added amount in each layer is preferably 0.001 to 0.4 g per light-sensitive layer.
  • the amount is preferably 0.003 to 0.3 g, more preferably 0.01 to 0.1 g, and particularly preferably 0.015 to 0.05 g.
  • the amount per light-sensitive layer is preferably 0.001 to 0.1 g, and more preferably 0.003 to 0.03 g.
  • the coated amount of silver of each light-sensitive layer is too small, the dissolution of the silver salt proceeds, and therefore a satisfactory color density cannot be obtained.
  • intensification is carried out, if the coated amount of silver of each light-sensitive layer is too large, an increase in Dmin or formation of bubbles occurs, to make the appreciation of the resultant product difficult.
  • the total amount of gelatin of the light-sensitive material of the present invention is generally 1.0 to 30 g, and preferably 2.0 to 20 g, per m 2 .
  • the time for the swollen film thickness to reach 1/2 of the saturated swollen film thickness (90% of the maximum swollen film thickness) is preferably 15 sec or less, and more preferably 10 sec or less.
  • the swell ratio ([(maximum swollen film thickness - film thickness)/film thickness] x 100) is preferably 50 to 300%, and particularly preferably 100 to 200%.
  • the light-sensitive material is developed (silver development/cross oxidation of the built-in reducing agent), desilvered, and washed with water or stabilized. In some cases, after the washing with water or the stabilizing processing, a treatment of alkalinization for color formation intensification is carried out.
  • the developing solution may contain a compound that serves as a developing agent of silver halides and/or allows the developing agent oxidation product resulting from the silver development to cross-oxidize the color-forming reducing agent built in the light-sensitive material.
  • a compound that serves as a developing agent of silver halides and/or allows the developing agent oxidation product resulting from the silver development to cross-oxidize the color-forming reducing agent built in the light-sensitive material.
  • pyrazolidones, dihydroxybenzenes, reductones, and aminophenols are used, and particularly preferably pyrazolidones are used.
  • 1-phenyl-3-pyrazolidones are preferable, and they include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p-chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, and 1-phenyl-2-hydroxymethyl-5-phenyl-3-pyrazolidone.
  • Dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone, and potassium hydroquinonemonosulfonate.
  • ascorbic acid and its derivatives are preferable, and compounds described in JP-A No. 148822/1994, pages 3 to 10, can be used.
  • sodium L-ascorbate and sodium erysorbate are preferable.
  • p-Aminophenols include N-methyl-p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, and 2-methyl-p-aminophenol.
  • the amount of these compounds to be used in the developing solution is generally 2.5 x 10 -4 to 0.2 mol/liter, preferably 0.0025 to 0.1 mol/liter, and more preferably 0.001 to 0.05 mol/liter.
  • Example preservatives for use in the developing solution include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde/sodium bisulfite adduct, and hydroxylamine ⁇ sulfate, which can be used in an amount in the range of generally 0.1 mol/liter or below, and preferably 0.001 to 0.02 mol/liter. If a high-silver-chloride emulsion is used in the light-sensitive material, the above compound is used in an amount of generally 0.001 mol/liter or below, and preferably it is not used at all.
  • organic preservatives such as diethylhydroxylamine, dialkylhydroxylamines described in JP-A No. 97355/1992, can be preferably used.
  • the developing solution may contain halide ions, such as chloride ions, bromide ions, and iodide ions.
  • halide ions may be added directly to the developing solution, or they may be dissolved out from the light-sensitive material into the developing solution during the development processing.
  • the developing solution used in the present invention preferably has a pH of 8 to 13, and more preferably 9 to 12.
  • buffers Preferably, carbonates, phosphates, tetraborates, and hydroxybenzoates are used.
  • the amount of the buffers to be added to the developing solution is preferably 0.05 mol/liter or over, and particularly preferably 0.1 to 0.4 mol/liter.
  • various chelating agents can be used.
  • these chelating agents preferably the amount is enough to sequester the metal ions in the developing solution, and, for example, these chelating agents are generally used in an amount in the order of 0.1 to 10 g per liter.
  • an arbitrary antifoggant can be added.
  • nitrogen-containing heterocyclic compounds, and alkali metal halide, such as sodium chloride, potassium bromide, and potassium iodide can be used.
  • the amount of the nitrogen-containing heterocyclic compounds to be added is generally 1 x 10 -5 to 1 x 10 -2 mol/liter, and preferably 2.5 x 10 -5 to 1 x 10 -3 mol/liter.
  • the developing solution contains a fluorescent whitening agent.
  • a fluorescent whitening agent it is preferable to use 4,4'-diamino-2,2'-disulfostilbene-series compounds.
  • the processing temperature of the developing solution to be applied to the present invention is generally 20 to 50 °C, and preferably 30 to 45 °C.
  • the processing time is generally 5 sec to 2 min, and preferably 10 sec to 1 min.
  • the replenishing rate is generally 15 to 600 ml, preferably 25 to 200 ml, and more preferably 35 to 100 ml, per m 2 of the light-sensitive material.
  • the desilvering process comprises a fixing process, or both bleaching process and a fixing process.
  • the bleaching process and the fixing process may be carried out separately or simultaneously (bleach-fixing process).
  • the processing may be carried out in a bleach-fixing bath having two successive tanks; or the fixing process may be carried out before the bleach-fixing process; or the bleaching process may be carried out after the bleach-fixing process.
  • the stabilizing process it is preferable to carry out the stabilizing process, to stabilize silver salts and dye images, without carrying out the desilvering process after the development.
  • image-intensifying process can be performed using peroxides, halorous acids, iodoso compounds, and cobalt(III) complex compounds described, for example, in West Germany Patent (OLS) Nos. 1,813,920, 2,044,993, and 2,735,262, and JP-A Nos. 9728/1973, 84240/1974, 102314/1974, 53826/1976, 13336/1977, and 73731/1977.
  • an oxidizing agent for intensifying the image can be added to the above developer, so that the development and the intensification may be carried out at the same time in one bath.
  • hydrogen peroxide is preferable, because the amplification rate is high.
  • intensification methods are preferable processing methods in view of environmental conservation. This is because the amount of silver in the light-sensitive material can be reduced considerably, and therefore, for example, a bleaching process is not required and silver (or silver salts) will not be released, for example, by a stabilizing process or the like.
  • Example bleaching agents for use in the bleaching solution or the bleach-fix solution include, for example, compounds of polyvalent metals, such as iron (III), cobalt (III), cromium (IV), and copper (II); peracids; qunones; and nitro compounds.
  • polyvalent metals such as iron (III), cobalt (III), cromium (IV), and copper (II); peracids; qunones; and nitro compounds.
  • aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt; hydrogen peroxide, persulfates, and the like are preferred, in view of rapid processing and the prevention of environmental pollution.
  • the bleaching solution and bleach-fix solution that use these aminopolycarboxylic acid iron (III) complex salts can be used at a pH of generally 3 to 8, and preferably 5 to 7.
  • the bleaching solution that uses persulfates or hydrogen peroxide can be used at a pH of generally 4 to 11, and preferably 5 to 10.
  • a bleach-accelerating agent can be used.
  • the bleaching solution use can be made of known additives, such as a rehalogenating agent, a pH buffering agent, and a metal corrosion-preventive agent.
  • a rehalogenating agent such as sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate
  • Example fixing agents for use in the fixing solution and the bleach-fix solution include thiosulfates, thiocyanates, thioureas, a large amount of iodide salts, and thioether compounds, metho-ionic compounds, and nitrogen-containing heterocyclic compounds, having a sulfide group, as described in JP-A No. 365037/1992, pages 11 to 21, and JP-A No. 66540/1993, pages 1088 to 1092.
  • 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.
  • any of various fluorescent whitening agents, antifoaming agents, surface-active agents, polyvinylpyrolidones, and methanol can be contained.
  • the processing temperature of the desilvering step is generally 20 to 50 °C, and preferably 30 to 45 °C.
  • the processing time is generally 5 sec to 2 min, and preferably 10 sec to 1 min.
  • the replenishing rate is generally 15 to 600 ml, preferably 25 to 200 ml, and more preferably 35 to 100 ml, per m 2 of the light-sensitive material.
  • the processing is also preferably carried out without replenishment in such a way that the evaporated amount is supplemented with water.
  • the light-sensitive material of the present invention is generally passed through a washing step after the desilvering process. If a stabilizing process is carried out, the washing step can be omitted.
  • a stabilizing process processes described in JP-A Nos. 8543/1982, 14834/1983, and 220345/1985, and all known processes described in JP-A Nos. 127926/1983, 137837/1983, and 140741/1983, can be used.
  • a washing-stabilizing process in which a stabilizing bath containing a dye stabilizer and a surface-active agent typically used for the processing of color light-sensitive materials for photographing is used as a final bath, can be carried out.
  • washing solution washing water
  • stabilizing solution use can be made of a water softener, such as sulfites, inorganic phosphoric acids, polyaminocarboxylic acids, and organic aminophosphonic acids; a metal salt, such as Mg salts, Al salts, and Bi salts; a surface-active agent, a hardener, a pH buffer, a fluorescent whitening agent, and a silver-salt-forming agent, such as nitrogen-containing heterocyclic compounds.
  • a water softener such as sulfites, inorganic phosphoric acids, polyaminocarboxylic acids, and organic aminophosphonic acids
  • metal salt such as Mg salts, Al salts, and Bi salts
  • surface-active agent such as Mg salts, Al salts, and Bi salts
  • a hardener such as a hardener, a pH buffer, a fluorescent whitening agent, and a silver-salt-forming agent, such as nitrogen-containing heterocyclic compounds.
  • Example dye-stabilizing agents of the stabilizing solution include, for example, aldehydes, such as formalin and glutaraldehyde; N-methylol compounds, hexamethylenetetramine, or aldehyde sulfite adducts.
  • the pH of the washing water and the stabilizing solution is generally 4 to 9, and preferably 5 to 8.
  • the processing temperature is generally 15 to 45 °C, and preferably 25 to 40 °C.
  • the processing time is generally 5 sec to 2 min, and preferably 10 sec to 40 sec.
  • the overflow solution associated with the replenishment of the above washing water and/or the stabilizing solution can be reused in other processes, such as the desilvering process.
  • the amount of the washing water and/or the stabilizing solution can be set in a wide range depending on various conditions, and the replenishing rate is preferably 15 to 360 ml, and more preferably 25 to 120 ml, per m 2 of the light-sensitive material. To reduce the replenishing rate, it is preferable to use multiple tanks and a multi-stage countercurrent system.
  • water in order to save water, water can be used that has been obtained by treating the overflow solution or the in-tank liquid using a reverse osmosis membrane.
  • the treatment by reverse osmosis is preferably carried out for water from the second tank, or the more latter tank of the multi-stage countercurrent washing process and/or the stabilizing process.
  • the stirring is intensified as much as possible.
  • intensify the stirring specifically a method wherein a jet stream of a processing solution 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.
  • any state of the solution opening rate [contact area of air (cm 2 )/solution volume (cm 3 )] of any of the baths can exhibit excellent performance, but in view of the stability of the solution components, preferably the solution opening rate is 0 to 0.1 cm -1 .
  • the solution opening rate is preferably 0.001 to 0.05 cm -1 , and more preferably 0.002 to 0.03 cm -1 .
  • the automatic developing machine used for the light-sensitive material of the present invention is preferably provided with a means of transporting a light-sensitive material, as described in JP-A No. 191257/1985, 191258/1985, and 191259/1985.
  • a transporting means can reduce remarkably the carry-in of the processing solution from a preceding bath to a succeeding bath. Therefore it is high in the effect of preventing the performance of a processing solution from being deteriorated. Such an effect is particularly effective in shortening the processing time of each process and in reducing the process replenishing rate.
  • crossover time the aerial time
  • a method wherein a light-sensitive material is transported between processes through a blade having a screening effect as described, for example, in JP-A No. 86659/1992, Fig. 4, 5, or 6, and JP-A No. 66540/1993, Fig. 4 or 5, is preferable.
  • each of the processing solutions in the continuous process is concentrated due to evaporation, preferably water is added to compensate for the evaporation.
  • the processing time in each process according to the present invention means the time required from the start of the processing of the light-sensitive material at any process, to the start of the processing in the next process.
  • the actual processing time in an automatic developing machine is determined generally by the linear speed and the volume of the processing bath, and in the present invention, as the linear speed, 500 to 4,000 mm/min can be mentioned as a guide. Particularly in the case of a small-sized developing machine, 500 to 2,500 mm/min is preferable.
  • the processing time in the whole processing steps is preferably 360 sec or below, more preferably 120 sec or below, and particularly preferably 90 to 30 sec.
  • the processing time means the time from the dipping of the light-sensitive material into the developing solution, till the emergence from the drying part of the processor.
  • Processing agent Page Developing agents 536 Preservatives of developing agents 537, left column Antifoggants 537 Chelating agents 537, right column Buffers 537, right column Surface-active agents 538, left column, and 539, left column Bleaching agents 538, Bleach-accelerating agents 538, right column to 539, left column Chelating agents for bleaching 539, left column Rehaloganating agents 539, left column Fixing agents 539, right column Preservatives for fixing agents 539, right column Chelating agents for fixing 540, left column Surface-active agents for stabilization 540, left Scum-preventing agents for stabilization 540, right Chelating agents for stabilization 540, right Antifungus/mildew-proofing agents 540, right Image dye stabilizers 540, right
  • an image having low minimum density and high color density can be obtained. Further, an image high in clarity (color definition) can be obtained that, when stored for a long period of time, produces less stain, for example, due to color formation with the lapse of time.
  • the coating solutions were prepared as follows.
  • a silver bromochloride emulsion A (cubes; average grain size: 0.18 ⁇ m; silver bromide: 25 mol %) was prepared.
  • red-sensitive sensitizing dyes A-1 and A-2 To this emulsion, had been added red-sensitive sensitizing dyes A-1 and A-2. The chemical ripening of this emulsion was carried out optimally with a sulfur sensitizer and a gold sensitizer being added.
  • the second-layer to seventh-layer coating solutions were prepared in the similar manner as that for the first-layer coating solution.
  • gelatin hardener for each layer 1-oxy-3,5-dichloro-s-triazine sodium salt was used.
  • Cpd-4 and Cpd-5 were added to each layer so that the total amount would be 25.0 mg/m 2 and 50 mg/m 2 , respectively.
  • the red-sensitive emulsion layer was added 1-(5-methylureidophenyl)-5-mercaptotetrazole in amounts of 3.0 x 10 -4 mol, 2.0 x 10 -4 mol, and 8.0 x 10 -4 mol, respectively, per mol of the silver halide.
  • the following dye (the figure in the parenthesises shows the coated amount) was added to the emulsion layers: and
  • composition of each layer is shown below.
  • the figures indicate coated amounts (g/m 2 ).
  • the amounts are given in terms of silver.
  • the polyethylene on the first layer side contained a white pigment (TiO 2 , 15 wt%) and a bluish dye (ultramarine)]
  • Second layer (color-mixing inhibition layer) Gelatin 1.00 Color-mixing inhibitor (Cpd-1) 0.08 Solvent (Solv-1) 0.25 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.13
  • Third layer Silver chlorobromide emulsion (cubes; average grain size: 0.12 ⁇ m; silver bromide: 25 mol %) 0.20 Gelatin 1.25 Magenta coupler (ExM-1) 0.26 Color-forming reducing agent (I-16) 0.22 Solvent (Solv-4) 0.78 Fourth layer (color-mixing inhibition layer) Gelatin 1.00 Color-mixing inhibitor (Cpd-1) 0.08 Solvent (Solv-1) 0.25 Solvent (Solv-2) 0.15
  • Sample (101) was prepared in the same manner as Sample (100), except that, to the second and fourth layers, i.e. the intermediate layers, was added an auxiliary developing agent (ETA-6) in the state of a fine particle solid dispersion in an amount of 1.4 x 10 -4 mol per m 2 , respectively.
  • ETA-6 auxiliary developing agent
  • Samples (102) to (109) were prepared in the same manner as Sample (100) or (101), except that a sulfinic acid compound (S-3) was added to the blue-sensitive emulsion, the green-sensitive emulsion, and the red-sensitive emulsion, respectively, in multiple amounts, shown in Table 1, based on the added amount (in terms of mol) of the color-forming reducing agent.
  • S-3 a sulfinic acid compound
  • the thus prepared samples were cut; then they were given gradation exposure to light through a three-color separation filters for sensitometry by using a sensitometer (manufactured by Fuji Photo Film Co., Ltd.; FW type; color temperature of the light source: 3,200 °K), respectively.
  • a sensitometer manufactured by Fuji Photo Film Co., Ltd.; FW type; color temperature of the light source: 3,200 °K
  • Processing step Temperature Replenishment rate Time Tank volume (liter) Development 40 °C 30 ml 20 sec 1.0 Bleach-fix 40 °C 30 ml 15 sec 1.0 Rinse (1) 30 °C - 3 sec 0.3 Rinse (2) 30 °C - 3 sec 0.3 Rinse (3) 30 °C - 3 sec 0.3 Rinse (4) 30 °C - 3 sec 0.3 Rinse (5) 30 °C 60 ml 5 sec 0.3 (the replenishment rate was the amount per m 2 of the light-sensitive material) (the rinse was conducted in a 5-tank counter-current system of Rinse (5) to Rinse (1))
  • the water of Rinse (4) was pumped to a reverse osmosis membrane, and the passed water was supplied to Rinse (5), while the concentrated water not passed through the reverse osmosis membrane was returned to Rinse (4).
  • a blade was placed between the tanks, and the sample was passed between them.
  • Samples (100) and (102) to (105) were developed with Developer-1, and Samples (101) and (106) to (109) were developed with Developer-2 (alkali activation solution).
  • Developer-1 Tank solution Replenishing solution Water 800 ml 800 ml Tripotassium phosphate 30 g 39 g 5-Nitrobenzotriazole 0.1 g 0.25 g Disodium-N,N-bis sulfonatoethyl)hydroxylamine 3.3 g 6.6 g Potassium chloride 10 g - Hydroxyethylidene-1,1-diphosphonic acid (30% solution) 4 ml 4 ml ETA-6 0.2 g - Water to make 1 liter pH: 12.0
  • Blix solution Tank solution Replenishing solution Water 600 ml 150 ml Ammonium thiosulfate (700 g/liter) 100 ml 250 ml Ammonium sulfite monohydrate 40 g 40 g Etylenediaminetetraacetic acid iron(III) ammonium 77 g 154 g Ethylenediaminetetraacetic acid 5 g 10 g Ammonium bromide 10 g 20 g Acetic acid (50 %) 70 ml 140 ml Water to make 1000 ml 1000 ml Rinse solution Tap water
  • the yellow, magenta, and cyan image densities were measured through B, G, and R filters corresponding to the dyes, to measure the minimum density (Dmin) and the maximum density (Dmax).
  • Samples (201), (202), (203), (204), (205), (206), and (207) were prepared in the same manner as Sample (107) in the above Example 1, except that, in place of the sulfinic acid compound (S-3) in the Sample (107), a sulfinic acid compound (S-2), (S-6), (S-7), (S-9), (S-16), (S-18), or (S-23) was used, respectively, each in the same molar amount.
  • Example 2 For the thus prepared Samples, the processing was carried out in the same manner in Example 1 using the alkali activation solution (Developer 2) of Example 1, and the evaluation was carried out in the same manner in Example 1. The results are shown in Table 2, along with that in Sample (101) in Example 1 as a comparison.
  • Samples (301), (302), (303), (304), (305), and (306) were prepared in the same manner as Sample (107) in the above Example 1, except that, in place of the color-forming reducing agent in RL (red-sensitive layer) in the Sample (107), a color-forming reducing agent (I-1), (I-17), (I-23), (I-24), (I-61), or (I-72) was used, respectively, each in the same molar amount. Samples wherein Compound (S-3) was removed from these samples were also prepared.
  • Example 2 For the thus-prepared Samples, the processing was carried out in the same manner in Example 1 using the alkali activation solution (Developer 2) of Example 1, and the evaluation was carried out in the same manner in Example 1. The results are shown in Table 3.
  • Sample (400) On the same base used in Example 1, layers having the below-described constitution were formed, to prepare a multi-layer color printing paper. This was named Sample (400).
  • the coating solutions were prepared as follows.
  • a silver chlorobromide emulsion D (cubes; a mixture of a large-size emulsion having an average grain size of 0.88 ⁇ m, and a small-size emulsion 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) was prepared.
  • coating solutions for the third layer and the fifth layer were prepared in the following manner.
  • a silver chlorobromide emulsion E (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 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) for the third layer was prepared.
  • a silver chlorobromide emulsion F (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 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) for the fifth layer was prepared.
  • Example 2 the same A-2 compound as used in Example 1 was added to the fifth layer in an amount of 2.6 x 10 -3 mol per mol of silver.
  • the second, sixth and seventh layers were prepared such that they would have the compositions shown below.
  • auxiliary developing agent ETA-6
  • ETA-6 auxiliary developing agent
  • gelatin hardener of each layer 1-oxy-3,5-dichloro-s-triazine sodium salt was used.
  • Cpd-4 and Cpd-5 were added to each layer so that the total amount would be 25 mg/m 2 and 50 mg/m 2 , respectively.
  • each layer is shown below. Each figure indicates the coated amount (g/m 2 ).
  • the amounts are given in terms of silver.
  • the polyethylene on the first layer side contained a white pigment (TiO 2 ) and a bluish dye (ultramarine)]
  • Second layer (color-mixing inhibition layer) Gelatin 1.00 Color-mixing inhibitor (Cpd-1) 0.08 Solvent (Solv-1) 0.25 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.13 Third layer (green-sensitive emulsion layer) Silver Chlorobromide Emulsion E 0.20 Gelatin 1.55 Magenta coupler (ExM-2) 0.34 Color-forming reducing agent (I-32) 0.26 Solvent (Solv-4) 0.78 Fourth layer (color-mixing inhibition layer) Gelatin 1.00 Color-mixing inhibitor (Cpd-1) 0.08 Solvent (Solv-1) 0.25 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.13 Fifth layer (blue-sensitive emulsion layer) Silver
  • Sample (401) was prepared in the same manner as Sample (400), except that a sulfinic acid compound (S-1) was added to the blue-sensitive emulsion, the green-sensitive emulsion, and the red-sensitive emulsion, respectively, in an amount of 0.2 times, in terms of mol, the added amount of the color-forming reducing agent.
  • S-1 a sulfinic acid compound
  • the thus prepared samples were cut; then they were given gradation exposure to light through a three-color separation filters for sensitometry by using a sensitometer (manufactured by Fuji Photo Film Co., Ltd.; FW type; color temperature of the light source: 3,200 °K), respectively.
  • a sensitometer manufactured by Fuji Photo Film Co., Ltd.; FW type; color temperature of the light source: 3,200 °K
  • Processing step Temperature Time Development 40 °C 30 sec Blix 40 °C 15 sec Stabilization 30 °C 10 sec Drying 80 °C 10 sec Developer-3 (alkali activation bath) Tank solution Water 800 ml Sodium 5-sulfosalicylate 29 g Potassium chloride 10 g Hydroxyethylidene-1,1-diphosphonic acid (30% solution) 4 ml Water to make 1 liter pH: 12.0
  • Example 2 As for the blix solution, the same tank solution as used in Example 1 was used. Stabilizing solution Water 900 ml Citric acid 4.2 g Hydroxyethylidene-1,1-diphosphonic acid (30% solution) 1.0 ml 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g Water to make 1 liter pH: 6.0
  • Samples (501), (502), (503), (504), (505), and (506) were prepared in the same manner as Sample (401) in the above Example 4, except that the color-forming reducing agent in BL (blue-sensitive layer) in the Sample (401) was replaced with a color-forming reducing agent (I-27), (I-29), (I-31), (I-39), (I-40), or (I-67), respectively, each in the same molar amount. Samples wherein Compound (S-1) was not used in these samples were also prepared.
  • Sample (601) was prepared in the same manner as Sample (107) in the above Example 1, except that the coating amounts of silver in the first, third, and fifth layers were 0.01 g, 0.01 g, and 0.015 g, respectively, per m 2 .
  • Example 2 This sample was exposed to light in the same manner as in Example 1, and then it was processed with an intensifier of a 0.3% aqueous hydrogen peroxide solution having a pH of 12.0, which was prepared by adding hydrogen peroxide to Developer-2. The result showed that, even when the light-sensitive material considerably reduced in silver was used, an image having high maximum density, similar to in Example 1, was obtained. A distinct image having good storage preservability with less stain after the storage was obtained.
  • the light-sensitive material of the present invention is also preferable for the formation of an image by a light-sensitive material with a low silver content amplified with an intensifying processing.
  • Sample (401) of Example 4 was processed and evaluated in the same manner as in Example 4, with the following alteration of exposure to light.
  • TOLD 9211 manufactured by Toshiba Co.
  • the apparatus was such that the laser beams could be scanned, by respective rotating polyhedrons, successively over a color printing paper moved perpendicularly to the scanning direction.
  • the amount of light was varied, to find the relationship (D - log E) between the density (D) of the light-sensitive material and the amount of light (E).
  • the amounts of lights of the laser beams having three wavelengths were modulated using an external modulator, to control the exposure amount.
  • 400 dpi was used, and the average exposure time per picture element was about 5 x 10 -8 sec.
  • a Peltier element was used to keep the temperature constant.

Claims (8)

  1. Matériau photosensible photographique couleur à l'halogénure d'argent présentant au moins une couche d'émulsion d'halogénure d'argent photosensible sur un support, dans lequel au moins une couche constitutionnelle photographique contient au moins un copulant formateur de colorant, et au moins un agent réducteur formateur de couleur représenté par la formule (I) : formule (I)    R11-NHNH-X-R12 dans laquelle R11 représente un groupe aryle ou un groupe hétérocyclique; R12 représente un groupe alkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, ou un groupe hétérocyclique; et X représente un groupe choisi dans l'ensemble comprenant -SO2-, -CO-, -COCO-, -CO-O-, -CO-N(R13)-, -COCO-O-, -COCO-N(R13)-, et -SO2-N(R13)-, dans lesquels R13 représente un atome d'hydrogène ou un groupe représenté par R12; et au moins une couche constitutionnelle photographique contient un composé représenté par la formule (S) :
    Figure 01900001
    dans laquelle X11 représente un atome d'hydrogène, certain autre atome, ou un groupe d'atomes, lequel ou lesquels atomes forment un sel minéral ou organique; et R41, R42, R43, R44, et R45, qui sont identiques ou différents, représentent chacun un atome d'hydrogène ou un substituant, ou les groupes R41, R42, R43, R44, et R45 dans les positions ortho peuvent se lier ensemble pour former un noyau à 5 ou 6 chaínons, pourvu que le total de la somme des atomes de carbone de R41, R42, R43, R44, et R45 soit de 10 ou plus.
  2. Matériau photosensible photographique couleur à l'halogénure d'argent selon la revendication 1, dans lequel le composé représenté par la formule (I) est représenté par la formule (II) ou (III):
    Figure 01910001
    formule (III)    R3-NHNH-Z2 dans lesquelles Z1 représente un groupe acyle, un groupe carbamoyle, un groupe alcoxycarbonyle, ou un groupe aryloxycarbonyle; Z2 représente un groupe carbamoyle, un groupe alcoxycarbonyle, ou un groupe aryloxycarbonyle; X1, X2, X3, X4, et X5 représentent chacun un atome d'hydrogène ou un substituant, avec la condition que la somme des valeurs σp de la constante de substituants de Hammet de X1, X3, et X5, et des valeurs σm de la constante de substituants de Hammet de X2 et X4, soit de 0,80 ou plus mais 3,80 ou moins; et R3 représente un groupe hétérocyclique.
  3. Matériau photosensible photographique couleur à l'halogénure d'argent selon la revendication 2, dans lequel le composé représenté par la formule (II) ou (III) est représenté par la formule (IV) ou (V), respectivement:
    Figure 01910002
    dans lesquelles R1 et R2 représentent chacun un atome d'hydrogène ou un substituant; X1, X2, X3, X4, et X5 représentent chacun un atome d'hydrogène ou un substituant, avec la condition que la somme des valeurs σp de la constante de substituants de Hammet de X1, X3, et X5, et des valeurs σm de la constante de substituants de Hammet de X2 et X4, soit de 0,80 ou plus mais 3,80 ou moins; et R3 représente un groupe hétérocyclique.
  4. Matériau photosensible photographique couleur à l'halogénure d'argent selon la revendication 3, dans lequel le composé représenté par la formule (IV) ou (V) est représenté par la formule (VI) ou (VII), respectivement:
    Figure 01920001
    dans lesquelles R4 et R5 représentent chacun un atome d'hydrogène ou un substituant; X6, X7, X8, X9, et X10 représentent chacun un atome d'hydrogène, un groupe cyano, un groupe sulfonyle, un groupe sulfinyle, un groupe sulfamoyle, un groupe carbamoyle, un groupe alcoxycarbonyle, un groupe aryloxycarbonyle, un groupe acyle, un groupe trifluorométhyle, un atome d'halogène, un groupe acyloxy, un groupe acylthio, ou un groupe hétérocyclique, avec la condition que la somme des valeurs ap de la constante de substituants de Hammet de X6, X8, et X10, et des valeurs σm de la constante de substituants de Hammet de X7 et X9, soit de 1,20 ou plus mais 3,80 ou moins; et Q1 représente un groupe d'atomes non-métalliques requis pour former, ensemble avec le C, un groupe hétérocyclique contenant de l'azote, à 5 à 8 chaínons.
  5. Matériau photosensible photographique couleur à l'halogénure d'argent selon la revendication 1, 2, 3, ou 4, comprenant un agent de développement auxiliaire et/ou son précurseur.
  6. Matériau photosensible photographique couleur à l'halogénure d'argent selon la revendication 1, 2, 3, 4, ou 5, comprenant un halogénure d'argent tel que la quantité d'argent totale appliquée de toutes les couches appliquées est de 0,003 à 0,3 g/m2 en termes d'argent.
  7. Matériau photosensible photographique couleur à l'halogénure d'argent selon la revendication 1, 2, 3, 4, 5, ou 6, dans lequel ledit matériau photosensible photographique couleur à l'halogénure d'argent est exposé à la lumière par exposition par balayage, avec un temps d'exposition par élément d'image de 10-8 à 10-4 sec.
  8. Matériau photosensible photographique couleur à l'halogénure d'argent selon la revendication 1, 2, 3, 4, 5, 6, ou 7, dans lequel le copulant formateur de colorant présente un substituant dans la position réactive de couplage.
EP96119208A 1995-11-30 1996-11-29 Produit photographique couleur à l'halogénure d'argent sensible à la lumière Expired - Lifetime EP0777153B1 (fr)

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