JPH1055048A - Silver halide photograhic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable extremely rapid processing with an activator solution containing substantially no developing agent by forming a first layer and a second layer and a third layer by coating and interposing a second layer between the first layer and a third layer and incorporating a specified color developing reducing agent in a layer containing a dye forming coupler. SOLUTION: The dye forming coupler is the one for producing a diffusive dye, and the first layer contains an auxiliary developing agent or its precursor, the second layer contains a polymer having anionic groups, and the third layer contains a mordant for immobilizing the diffusive dye, and the first layer is located on the side of the second layer reverse to the third layer, and the layer containing the dye forming coupler contains at least one kind of color developing reducing agent represented by the formula 10 which Ca is a carbon atom; Z is a carbamoyl, acyl, alkoxycarbonyl, or aryloxycarbonyl group; and Q is an atomic group necessary to form an unsaturated ring together with the Cα group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material, and more specifically, to a silver halide photographic light-sensitive material capable of rapidly forming an image by processing in an alkali bath (developer) substantially free of a developing agent. More particularly, the present invention relates to a silver halide color photographic light-sensitive material excellent in color developing property and preservability of the light-sensitive material before exposure.

[0002]

2. Description of the Related Art In general, a color photographic light-sensitive material undergoes color development after exposure, whereby an oxidized p-phenylenediamine derivative and a coupler react to form an image. In this method, a color reproduction method using a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed. Conventional color development is achieved by immersing the exposed color photographic light-sensitive material in an aqueous alkali solution (color developer) in which a p-phenylenediamine derivative is dissolved. However, the p-phenylenediamine derivative in an alkaline aqueous solution is unstable and easily deteriorates with time, and it is necessary to frequently replenish the color developing solution to maintain stable developing performance. Further, the used color developing solution containing a p-phenylenediamine derivative is complicated to dispose, and there is a problem in treating the used color developing solution discharged in large quantities. In order to simplify the handling of such a color developing solution and the waste liquid treatment, it is desired to form an image by processing with an alkaline solution (hereinafter referred to as an activator solution) not containing an unstable compound such as a p-phenylenediamine derivative. Have been.

One of the methods of forming an image by the above-described activator solution treatment is to incorporate an aromatic primary amine developing agent or a precursor thereof into a hydrophilic colloid layer. Examples of the primary amine developing agent or a precursor thereof include, for example, US Pat.
114, 3,764,328, 4,060,4
No. 18, JP-A-56-6235 and JP-A-58-19203
No. 1 and the like. However, since these aromatic primary amine developing agents and their precursors are unstable, they have a disadvantage that stain is generated during long-term storage or color development of unprocessed photosensitive materials. As another means, for example, European Patent No. 0,545,49
No. 1A1, No. 565, 165A1, etc., in which the sulfonylhydrazine type compound is incorporated in the hydrophilic colloid layer. Even with the sulfonylhydrazine-type compounds mentioned here, there is still a problem that a sufficient color-forming density cannot be obtained during color development, and this sulfonylhydrazine-type compound hardly forms a color when a 2-equivalent coupler is used. Compared with 4-equivalent couplers, 2-equivalent couplers have advantages such as reduction of coupler-derived stain, easy control of the activity of the coupler, and addition of various functions to the leaving group. There was a need for technology development that could take advantage of these advantages.

On the other hand, hydrazine compounds such as carbamoylhydrazine compounds can react with two equivalents of a dye-forming coupler to form a dissociative dye. For example, a dissociative dye can be obtained by reacting an oxidized auxiliary developing agent generated by silver development with a hydrazine compound and coupling the generated oxidized hydrazine compound with a dye-forming coupler. The dissociative dye is colored by being immersed in an alkali solution or the like (separate from the above-described activator solution) and dissociated after the development processing. However, under such conditions that the dye is dissociated, the remaining hydrazine compound itself is also dissociated and easily oxidized, and there is a problem that it reacts with the coupler to generate stain after treatment.

[0005]

As means for achieving both the above-mentioned improvement in color development and prevention of stain after treatment, a reaction between a coupler and a hydrazine compound and a dissociative dye formed by the reaction produce a color. It is conceivable to provide the space separately. That is, a method in which the generated dissociative dye is diffused, the dye is captured by a mordant in another photographic constituent layer, dissociated and fixed. in this way,
Alkali treatment after the development treatment is not required, and the processing speed and simplicity are improved. In order to further improve the rapid processing property, it is effective to incorporate an auxiliary developing agent or a precursor thereof into the light-sensitive material.

The present inventors have devised the above means,
The inventors have developed a method capable of preventing post-processing stain while improving color development. However, when a layer containing an auxiliary developing agent or a precursor thereof is applied, when the photosensitive material before exposure is stored under high temperature and high humidity and then exposed and processed, the color density is significantly reduced as compared with before storage. It has been found that a new problem occurs. A first object of the present invention is to provide a silver halide photographic light-sensitive material which can be rapidly developed with an activator solution containing substantially no developing agent. It is a second object of the present invention to provide a silver halide color photographic light-sensitive material having a high color density and preventing a reduction in the color density during storage of the light-sensitive material before exposure.

[0007]

It has been found that the object of the present invention can be attained by using the following light-sensitive materials. (1) A support having at least one layer containing a dye-forming coupler on a support, and a light-sensitive silver halide emulsion in a layer containing the dye-forming coupler or in a layer not containing the dye-forming coupler. In the silver halide photographic light-sensitive material, the dye-forming coupler is a coupler that generates a diffusible dye, and the first layer containing the auxiliary developing agent or the precursor of the auxiliary developing agent has an anionic group. It has a second layer containing a polymer and a third layer containing a mordant for immobilizing a diffusible dye,
Is coated on the side opposite to the third layer via the second layer, and is contained in the above-mentioned dye-forming coupler-containing layer in the color-forming reducing agent represented by the following general formula (I). A silver halide photographic material comprising at least one kind of General formula (I)

[0008]

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In the formula, Cα represents a carbon atom. Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Q represents an atom group forming an unsaturated ring with Cα. (2) In the above item (1), the first layer and the third layer are photographic constituent layers provided separately from a layer containing a dye-forming coupler or a layer containing a photosensitive silver halide emulsion, And the second layer is a photographic component layer provided between a photosensitive silver halide emulsion layer furthest from the support and a third layer further away from the support than this emulsion layer. 2. The silver halide photographic light-sensitive material according to claim 1, wherein (3) In the first mode, the first layer, the second layer, and the third
Is a photographic component layer provided separately from a layer containing a dye-forming coupler or a layer containing a photosensitive silver halide emulsion. material. (4) The mordant is a mordant having a tertiary amino group or a quaternary ammonium salt as a functional group, and has a total carbon number of 1
At least one anionic compound having a molecular weight of 0 or more and a molecular weight of 1000 or less is contained in an optional photographic constituent layer in a proportion of 10 mol% or more of a tertiary amino group or a quaternary ammonium salt in the mordant. (1) The silver halide photographic material as described in (1) above. In the present invention, the diffusible dye refers to a dye having sufficient diffusibility to diffuse a photographic constituent layer after development and to capture and mordant with a mordant.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail. Hereinafter, the color-forming reducing agent used in the present invention will be described in detail. The color-forming reducing agent represented by the general formula (I) used in the present invention undergoes an oxidation-reduction reaction with a compound oxidized by exposed silver halide or an oxidized auxiliary developing agent in an alkaline solution,
A compound to be oxidized, and the oxidized product is a compound characterized by further reacting with a dye-forming coupler to form a dye.

Next, the compound represented by formula (I) used in the present invention will be described in detail. In the general formula (I), Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Of these, a carbamoyl group is preferable, and a carbamoyl group having a hydrogen atom on a nitrogen atom is particularly preferable. The carbamoyl group is preferably a carbamoyl group having 1 to 50 carbon atoms, more preferably 1 to 40 carbon atoms. Specific examples include a carbamoyl group, a methylcarbamoyl group,
Ethyl carbamoyl group, n-propyl carbamoyl group,
sec-butylcarbamoyl group, n-octylcarbamoyl group, cyclohexylcarbamoyl group, tert-butylcarbamoyl group, dodecylcarbamoyl group, 3-dodecyloxypropylcarbamoyl group, octadecylcarbamoyl group, 3- (2,4-tert-pentylphenoxy) Propylcarbamoyl group, 2-hexyldecylcarbamoyl group, phenylcarbamoyl group, 4-dodecyloxyphenylcarbamoyl group, 2-chloro-5-dodecyloxycarbonylphenylcarbamoyl group, naphthylcarbamoyl group, 3-pyridylcarbamoyl group,
3,5-bis-octyloxycarbonylphenylcarbamoyl group, 3,5-bis-tetradecyloxyphenylcarbamoyl group, benzyloxycarbamoyl group,
A 2,5-dioxo-1-pyrrolidinylcarbamoyl group.

The acyl group is preferably an acyl group having 1 to 50 carbon atoms, and more preferably 1 to 40 carbon atoms. Specific examples include formyl group, acetyl group, 2
-Methylpropanoyl group, cyclohexylcarbonyl group, n-octanoyl group, 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. As the alkoxycarbonyl group and the aryloxycarbonyl group, an alkoxycarbonyl group and an aryloxycarbonyl group having 2 to 50 carbon atoms are preferable, 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,
Examples thereof include a 4-octyloxyphenoxycarbonyl group, a 2-hydroxymethylphenoxycarbonyl group, and a 4-dodecyloxyphenoxycarbonyl group.

Q represents an atomic group which forms an unsaturated ring together with Cα, and the unsaturated ring formed is preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring. Examples thereof include a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,2,4-triazine ring,
3,5-triazine ring, pyrrole ring, imidazole ring,
Pyrazole ring, 1,2,3-triazole ring, 1,2,
4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,4-thiadiazole ring, 1,
2,5-thiadiazole ring, 1,3,4-oxadiazole ring, 1,2,4-oxadiazole ring, 1,2,5
-Oxadiazole ring, thiazole ring, oxazole ring, isothiazole ring, isoxazole ring, thiophene ring and the like are preferable, and a condensed ring in which these rings are condensed with each other is also preferably used. Further, these rings may have a substituent, and examples of the substituent include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (for example, trifluoromethyl, methyl, Ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl,
Dodecyl, etc.), a linear or branched, chain or cyclic alkenyl group having 2 to 50 carbon atoms (eg, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), a total of 2 to 2 carbon atoms.
50 alkynyl groups (eg, ethynyl, 1-propynyl, etc.), aryl groups having 6 to 50 carbon atoms (eg, phenyl, naphthyl, anthryl, etc.), and acyloxy groups having 1 to 50 carbon atoms (eg,

Acetoxy, tetradecanoyloxy, benzoyloxy, etc., a carbamoyloxy group having 1 to 50 carbon atoms (eg, N, N-dimethylcarbamoyloxy), a carbonamide group having 1 to 50 carbon atoms (eg, formamide) , N-methylacetamide, acetamide,
N-methylformamide, benzamide, etc.), having 1 carbon atom
~ 50 sulfonamide groups (e.g., methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.);
Carbamoyl group (for example, N-methylcarbamoyl,
N, N-diethylcarbamoyl, N-mesylcarbamoyl, etc.), a sulfamoyl group having 0 to 50 carbon atoms (for example,
N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) sulfamoyl and the like, an alkoxy group having 1 to 50 carbon atoms (for example, methoxy, propoxy, isopropoxy, Octyloxy, t-octyloxy, dodecyloxy, 2-
(2,4-di-t-pentylphenoxy) ethoxy and the like), an aryloxy group having 6 to 50 carbon atoms (for example, phenoxy, 4-methoxyphenoxy, naphthoxy and the like),
An aryloxycarbonyl group having 7 to 50 carbon atoms (for example, phenoxycarbonyl, naphthoxycarbonyl, etc.),

An alkoxycarbonyl group having 2 to 50 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), an N-acylsulfamoyl group having 1 to 50 carbon atoms (eg, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 50 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 50 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 50 carbon atoms (eg, ethoxycarbonylamino, etc.), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 50 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl A hydroxy group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 50 carbon atoms (eg, methanesulfinyl, octanesulfinyl and the like), an arylsulfinyl group having 6 to 50 carbon atoms (eg, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl, etc.), having 1 to 5 carbon atoms
An alkylthio group of 0 (eg,

Methylthio, octylthio, cyclohexylthio, etc., arylthio groups having 6 to 50 carbon atoms (for example, phenylthio, naphthylthio, etc.), 1 to 50 carbon atoms
Ureido group (eg, 3-methylureido, 3,3-
Dimethylureide, 1,3-diphenylureide, etc.),
A heterocyclic group having 2 to 50 carbon atoms (as a hetero atom, for example, a 3- to 12-membered monocyclic or condensed ring containing at least one or more of nitrogen, oxygen and sulfur;
Furyl, 2-pyranyl, 2-pyridyl, 2-thienyl,
2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), carbon Sulfamoylamino groups of numbers 0 to 50 (e.g., N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), silyl groups of 3 to 50 carbon atoms (e.g., trimethylsilyl, dimethyl-t-butylsilyl, Triphenylsilyl and the like, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like). The above substituents may further have a substituent,
Examples of the substituent include the substituents mentioned here.

The number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less. Q and Cα
The total number of carbon atoms of the unsaturated ring and its substituents formed by is preferably 30 or less, more preferably 24 or less,
Most preferably 18 or less. When the ring is formed only of carbon atoms (for example, a benzene ring, a naphthalene ring, and an anthracene ring), the substituent of the ring formed by Q and Cα is Hammett's substituent constant σ for all the substituents. The sum of the values (the σp value is used when the relationship is 1, 2, 1, 4,... With respect to Cα, and the σm is used when the relationship is 1, 3, 1, 5,... With respect to Cα). Is 0.8 or more, more preferably 1.2 or more, and most preferably 1.5 or more. The upper limit is not particularly limited, but is preferably 3.8 or less from the viewpoint of easy availability of the compound. The Hammett's substituent constants σp and σm are described, for example, by Naoki Inamoto, “Hammet Rule—Structure and Reactivity—” (Maruzen), “New Experimental Chemistry Lecture 14, Synthesis and Reaction of Organic Compounds V”, page 2605 (Japan). Chemical Society, Maruzen), Tadao Nakaya, "Explanation on Theoretical Organic Chemistry", 217 pages (Tokyo Kagaku Dojin), Chemical Review (91), 165-195 (199)
(1 year). Next, the color-forming reducing agent represented by the general formula (I) will be specifically shown, but the scope of the present invention is not limited to these specific examples.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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The color-forming reducing agent of the present invention is a compound (coupler) that forms a diffusible dye by an oxidative coupling reaction.
Use with In the present invention, 2-equivalent couplers are preferred. Specific examples of couplers are described in Theory of the Photographic Process (4th. Ed., THJ
ames editing, Macmillan, 1977) 291
Pp. 334 to 354 and 354 to 361, JP-A-58
-12353, 58-149046, 58-1
No. 49047, No. 59-11114, No. 59-124
No. 399, No. 59-174835, No. 59-2315
No. 39, No. 59-231540, No. 60-2951
Nos. 60-14242, 60-23474 and 60-66249.

The coupler of the present invention may be any coupler as long as the diffusible dye formed by coupling with the oxidized form of the color-forming reducing agent of the present invention reaches the mordant. Preferably has one or more dissociating groups having a pKa of 12 or less, more preferably has one or more dissociating groups having a pKa of 8 or less, and particularly preferably has a dissociating group having a pKa of 6 or less. The molecular weight of the diffusible dye formed from the viewpoint of imparting diffusivity is preferably 200 or more and 2000 or less. Further, (the molecular weight of the formed dye / the number of dissociating groups having a pKa of 12 or less) is 100 to 20.
It is preferably 00 or less, more preferably 100 or more and 1000 or less. Here, as the value of pKa, a value measured using dimethylformamide: water = 1: 1 as a solvent is used.

The solubility of the diffusible dye formed by coupling the coupler of the present invention with the oxidized form of the reducing agent of the present invention is at least 1 × 10 ^-6 mol / l in an alkaline solution having a pH of 11 at 25 ° C. It is preferably soluble, more preferably 1 × 10 ⁻⁵ mol / liter or more, more preferably 1 × 1 ⁻⁵ mol / l.
It is particularly preferable to dissolve ^0-4 mol / l or more. The diffusion constant of the diffusible dye formed by coupling the coupler of the present invention and the oxidized form of the color-forming reducing agent of the present invention is 10 ^{で 4} mol / liter in an alkaline solution at 25 ° C. and pH11. When melted, it is preferably at least 1 × 10 ⁻⁸ m ² / s ^−1, more preferably at least 1 × 10 ⁻⁷ m ² / s ^{−1, and} more preferably 1 × 10 ⁻⁶ m ² / s ^−1. It is particularly preferred that it is ^-1 or more. Examples of the coupler preferably used in the present invention are listed below. The couplers preferably used in the present invention include the following general formulas (1) to (12)
There is a compound having a structure as described in (1). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

[0036]

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[0037]

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[0038]

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Formulas (1) to (4) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl group, cyano group, nitro group, aryl group, A heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group. In the general formulas (1) to (3), R ¹⁵ is an alkyl group, an aryl group or a heterocyclic residue which may have a substituent. In the general formula (4), R ¹⁶ is an aryl group or a heterocyclic residue which may have a substituent. R ¹⁴ , R
Examples of the substituent which may be possessed by ¹⁵ and R ¹⁶ include the examples of the substituent on the ring formed by Q and Cα.

In the general formulas (1) to (4), Y is a group which imparts diffusion resistance to the coupler and is a group which can be eliminated by a coupling reaction with an oxidized form of a color-forming reducing agent.
Examples of Y include a heterocyclic group (a hetero atom is nitrogen,
A saturated or unsaturated 5- to 7-membered monocyclic or condensed ring containing at least one oxygen, sulfur or the like, for example, succinimide, maleimide, phthalimide,
Diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2 , 4-
Dione, imidazolidine-2-one, oxazoline-2
-One, thiazolin-2-one, benzimidazoline-
2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione,
2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3 , 4-thiazolidine, 2-imino-1,3,4-thiazolidine-4-one, etc.), a halogen atom (eg, chlorine atom, bromine atom, etc.), an aryloxy group (eg, phenoxy, 1-naphthoxy, etc.), Heterocyclic oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), acyloxy group (eg, acetoxy, benzoyloxy, etc.), alkoxy group (eg, methoxy, dodecyloxy, etc.), carbamoyloxy group (eg, N, N-diethylcarbamoyl) Oxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy groups (for example, Alkoxycarbonyloxy, etc.), an alkoxycarbonyl group (e.g., methoxycarbonyloxy, ethoxycarbonyloxy, etc.), an arylthio group (e.g., phenylthio, naphthylthio, etc.), a heterocyclic thio group (e.g., tetrazolylthio, 1,3,4
Thiadiazolylthio, 1,3,4-oxadiazolylthio, benzimidazolylthio, etc.), alkylthio group (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy group (eg, methanesulfonyloxy, etc.), arylsulfonyl An oxy group (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), a carbonamide group (eg, acetamide,
Trifluoroacetamide, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl group (eg, methanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.), alkylsulfinyl group (eg, , Methanesulfinyl, etc.), arylsulfinyl group (for example,
Benzenesulfinyl, etc.), arylazo group (for example,
Phenylazo, naphthylazo and the like), carbamoylamino group (for example, N-methylcarbamoylamino and the like) and the like.

Y may be substituted by a substituent,
Examples of the substituent that substitutes for Y include the examples of the substituent on the ring formed by Q and Cα. The total number of carbon atoms contained in Y is preferably from 6 to 50, and from 8 to 4
It is more preferably 0 or less, most preferably 10 or more and 30 or less. Y is preferably an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group. In the general formulas (1) to (4), R ¹⁴ and R ¹⁵ , and R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring.

Formula (5) represents a coupler called a 5-pyrazolone coupler, wherein 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 substituted by one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups or acylamino groups. Among the 5-pyrazolone couplers represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group,
R ¹⁸ is preferably a phenyl group substituted by one or more halogen atoms. To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, 2
-Methoxyphenyl group, 2-chloro-5-tetradecanamidophenyl group, 2-chloro-5- (3-octadecenyl-1-succinimido) phenyl group, 2-chloro-
5-octadecylsulfonamidophenyl group or 2-
Aryl or acetyl group such as chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group, 2- (2,4-di-t-pentylphenoxy) butanoyl group, benzoyl Group, 3-
(2,4-di-t-amylphenoxyacetamido) is an acyl group such as a benzoyl group, and these groups may further have a substituent, and these groups may be a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a connecting organic substituent or a halogen atom. Y has the same meaning as described above.

R ¹⁸ is preferably 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 called a pyrazoloazole-based coupler,
In the formula, R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of nonmetallic atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Among the pyrazoloazole couplers represented by the general formula (6), U.S. Pat.
[1,2-b] pyrazoles described in U.S. Pat. No. 4,500,654 and pyrazolo [1,5] described in U.S. Pat. No. 4,500,654.
-B] -1,2,4-triazoles, U.S. Pat.
No. 725,067, pyrazolo [5,1-c]-.
1,2,4-triazoles are preferred.

For details of the substituents on the azole ring represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 40,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61
Pyrazoloazole couplers having a branched alkyl group directly linked to the 2,3 or 6 position of the pyrazolotriazole group as described in JP-A-65245.
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-2-209457 or JP-A-63-307453;
A pyrazolotriazole coupler having a carboxamide group in the molecule described in US Pat. Y has the same meaning as described above.

The general formulas (7) and (8) are couplers called a phenol coupler and a naphthol coupler, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R
_{^{23, -SO 2 NR 22 R 23}} , -NHCOR 22, -NHCO
NR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent.
In the general formulas (7) and (8), R ²¹ represents a substituent, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. Examples of the substituent for R ^{21 to} R ²³ include those described as the substituent for the unsaturated ring formed by Q. Y has the same meaning as described above.

Preferred examples of the phenolic coupler represented by the general formula (7) are described in US Pat.
No. 929, No. 2,801,171, No. 2,77
No. 2,162, No. 2,895,826, No. 3,7
72-002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729,
9,166,956 and the like, U.S. Patent Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427. , 767, and the like. Y is the same as described above.

Preferred examples of the naphthol coupler represented by the general formula (8) include US Pat. No. 2,474,2.
No. 93, 4,052, 212, 4,146
No. 396, No. 4,282,233, No. 4,29
Examples thereof include 2-carbamoyl-1-naphthols described in US Pat. No. 6,200 and the like and 2-carbamoyl-5-amide-1-naphthols described in US Pat. No. 4,690,889. Y is the same as described above. Formula (9) to (12) are couplers called ^{pyrrolotriazoles, R 32, R 33, R} 34 represents a hydrogen atom or a substituent. Y is as described above. Examples of the substituent of R ³² , R ³³ and R ³⁴ include those described as examples of the substituent which can be substituted on the ring formed by Q and Cα in the general formula (I). General formula (9)
Preferred examples of the pyrrolotriazole-based couplers represented by formulas (12) to (12) include EP-A-488,248 A1.
And at least one of R ³² and R ³³ described in JP-A Nos. 491,197A1 and 545,300 is an electron-withdrawing group. Y is the same as described above.

In addition, couplers having structures such as fused phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-fused heterocycle, and 5,6-fused heterocycle can be used. U.S. Pat. No. 4,327,173 discloses fused ring phenolic couplers.
No. 4,564,586 and 4,904,57
The couplers described in No. 5, etc. can be used. U.S. Pat. No. 4,818,672, as imidazole couplers,
The couplers described in JP-A-5,051,347 and the like can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used. Active methylene and active methine couplers are described in US Pat. Nos. 5,104,783 and 5,162,196.
The couplers described in (1) and (2) can be used. 5,5-Fused heterocyclic couplers include US Pat. No. 5,164,289.
Pyrropyrazole-based couplers described in
Pyrroloimidazole couplers described in No. 74429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, and EP 556.
The couplers described in No. 700 can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 can also be used. In the coupler used in the present invention, the total number of carbon atoms in the portion except for Y is 3 or more because the released dye tends to be diffusible.
The following is preferable, 3 or more and 24 or less are more preferable, and 3 or more and 18 or less are most preferable. Specific examples of the coupler that can be used in the present invention are shown below, but the present invention is of course not limited thereto.

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The color-forming reducing agent of the present invention is used in an amount of 0.01 to 10 mmol per one color-forming layer in order to obtain a sufficient color-forming density.
/ M ² . A more preferred amount is 0.05 to 5 mmol / m ² , and a particularly preferred amount is 0.1 to 1 mmol / m ² . The amount of the coupler in the color-forming layer in which the color-forming reducing agent of the present invention is used is preferably 0.05 to 20 times, more preferably 0.1 to 10 times, particularly preferably 0.1 to 10 times the molar amount of the color-forming reducing agent. Is 0.2 to 5 times.

The mordant of the present invention will be described. In the present invention, the mordant may be used in any of the layers. Although a mordant may be added to the layer containing the color-forming reducing agent,
It is more preferable to use the layer containing no color-forming reducing agent. Further, in the latter case, the dye formed from the color-forming reducing agent and the coupler diffuses through the swollen gelatin film during the treatment and is dyed by the mordant. Therefore, it is preferable that the diffusion distance is short in order to obtain good sharpness. Therefore, the layer to which the mordant is added is preferably added to the layer adjacent to the layer containing the color-forming reducing agent. Further, in the present invention, since the color-forming reducing agent and the dye formed from the coupler are water-soluble dyes, they may flow out into the processing solution.
Therefore, the layer to which the mordant is added to prevent this is preferably on the side opposite to the support with respect to the layer containing the color-forming reducing agent. However, JP-A-7-168
In the case where the barrier layer as described in JP-A-335 is provided on the side opposite to the support with respect to the layer to which the mordant is added (the side farther from the support), the layer to which the mordant is added contains the color-forming reducing agent. It is also preferred that it is on the side closer to the support with respect to the layer contained.

The mordant of the present invention may be added to a plurality of layers. In particular, when a plurality of layers contain a color-forming reducing agent, the mordant is added to each adjacent layer. Is also preferred. The mordant that can be used in the present invention is a mordant usually used in photographic materials, and can be arbitrarily selected from those capable of fixing a diffusible dye. Among them, a polymer mordant is particularly preferable. Here, the polymer mordant includes a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, and a polymer having a quaternary cationic group. Preferred specific examples of the homopolymer or copolymer containing a vinyl monomer unit having a tertiary amino group include the following. The numbers in the monomer units represent mol%. (same as below)

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Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include US Pat. Nos. 4,282,305 and 4,11.
No. 5,124, No. 3,148,061, JP-A-60
No. 118834, No. 60-122941, No. 62-
The following may be mentioned, including the mordants described in Nos. 240443 and 62-244036.

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Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, and 1,594. U.S. Pat. Nos. 4,124,386 and 4,115,12.
4, No. 4,450,224, JP-A-48-283.
The following may be mentioned, including the mordants described in No. 25 and the like.

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Other preferred examples of homopolymers and copolymers having a vinyl monomer unit having a quaternary ammonium salt include US Pat. No. 3,709,690.
No. 3,898,088, No. 3,958,99
No. 5, JP-A-60-57836 and JP-A-60-60643.
No. 60-122940, No. 60-122942
And mordants described in JP-A-60-235134 and the like.

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In addition, US Pat. No. 2,548,564
No. 2,484,430 and 3,148,16
No. 3,756,814 and the like, vinylpyridine polymer and vinylpyridinium cationic polymer; US Pat. No. 3,625,694
No. 3,859,096, No. 4,128,53
8, polymer mordants crosslinkable with gelatin and the like disclosed in GB 1,277,453 and the like; US Pat. Nos. 3,958,995 and 2,721,852
No. 2,798,063, JP-A-54-1152.
No. 28, No. 54-145529, No. 54-26027
Sol-type mordant disclosed in the specification of US Pat. No. 3,898,088; water-insoluble mordant disclosed in the specification of US Pat. No. 3,898,088; US Pat. No. 3,709,690, 3,788,855, and 3,642,482. Reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification. No. 3,488,706,
No. 3,557,066, No. 3,271,147
No., JP-A-50-71332 and JP-A-53-30328.
Nos. 52-155528, 53-125, 5
Examples include mordants disclosed in the specification of JP-A-3-1024. Other US Pat. No. 2,675,316
And the mordants described in JP-A-2,882,156.

The molecular weight of the polymer mordant of the present invention is 1,0.
100 to 1,000,000 is suitable, and especially 10,000
00 to 200,000 is preferred. The above-mentioned polymer mordant is usually used by being mixed with a hydrophilic colloid. Gelatin, a highly hygroscopic synthetic polymer or both can be used as the hydrophilic colloid, but gelatin is the most typical. The mixing ratio between the polymer mordant and the hydrophilic colloid, and the amount of the polymer mordant applied, are easily determined by those skilled in the art according to the amount of the dye to be morded, the type and composition of the polymer mordant, and the image forming process used. But the mordant / hydrophilic colloid ratio is 20/80
~ 80/20 (weight ratio), mordant applied amount is 0.2 ~ 15
g / m ² is suitable, and preferably 0.5 to 8 g / m ²
It is preferable to use them.

Next, the polymer having an anionic group used in the present invention will be described in detail. The polymer having an anionic group used in the present invention is coated between a photographic constituent layer containing an auxiliary developing agent or a precursor of the auxiliary developing agent and a photographic constituent layer containing a mordant. The anionic group referred to herein is a water-soluble dissociative group having a pKa of 7 or less, for example, -COOM, -OCOOM, -SO _{2
OM, -OSO 2 OM, -OPO (} OM) 2, (- O)
₂ POOM and the like. Here, M represents hydrogen, an alkali metal (eg, Na, K, etc.) or an ammonium residue. The anionic group may form a salt with an alkaline earth metal. The structure of the main chain of the polymer having an anionic group used in the present invention is not particularly limited, and examples thereof include a vinyl polymer, a polyester obtained by condensing a polyhydric alcohol and a polybasic acid, and a polyamine and a polyamine. The main chain is formed by a polyamide obtained by condensation with a basic acid or a polyamide obtained by condensation of an aminocarboxylic acid. The polymer having an anionic group used in the present invention may be a natural polymer or a synthetic polymer. Examples of the preferred natural polymer include gelatin, and gelatin having an isoelectric point of 6 or less is particularly preferable. preferable. The synthetic polymer that can be used in the present invention may be composed of only a monomer having an anionic group, or a monomer having an anionic group and a monomer having no anionic group may be copolymerized. .

Examples of vinyl monomers having an anionic group include acrylic acid, methacrylic acid, itaconic acid,
Maleic acid, monoalkyl itaconate (eg, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.), monoalkyl maleate (eg, monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.), citraconic acid, styrene sulfonic acid,
Vinylbenzylsulfonic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid (eg, acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.), methacryloyloxyalkylsulfonic acid (eg, methacryloyloxymethylsulfonic acid) ,
Methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.), acrylamidoalkylsulfonic acid (for example, 2-acrylamido-
2-methylethanesulfonic acid, 2-acrylamide-
2-methylpropanesulfonic acid, 2-acrylamide-2-methylbutanesulfonic acid, etc.), methacrylamide alkylsulfonic acid (2-methacrylamide-2)
-Methylethanesulfonic acid, 2-methacrylamide-
2-methylpropanesulfonic acid, 2-methacrylamide-2-methylbutanesulfonic acid, and the like). These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Examples of the vinyl monomer having no anionic group include acrylates, methacrylates, vinyl esters, acrylamides, methacrylamides, and olefins. And monomers forming a vinyl polymer described on pages (7) to (9) of No. 38639.

As the polyester having an anionic group, a polymer represented by the following general formula (E) is used.

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In the formula, R ₁ represents an alkylene, an arylene, an aralkylene, or a cycloalkylene; X represents a carbonyl group or a sulfonyl group; L represents a residue of a polyester diol having an average molecular weight of 500 to 20,000; Represents 0 or 1 and n is 0 to 3
0, preferably 0-10, and m + n ≧ 1. These polymers may be in the form of a salt, and examples of the salt include salts of alkali metal ions and ammonium ions. Examples of polyhydric alcohols and polybasic acids constituting the polyester diol residue are described in JP-A-3-3.
And polyhydric alcohols and polybasic acids described on page (10) of No. 8639.

As the polyamide having an anionic group, a polymer represented by the following general formula (F) is used.

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In the formula, R ₂ represents alkylene, arylene, aralkylene, or cycloalkylene; X represents a carbonyl group or a sulfonyl group; L ′ represents a residue of a polyamide diamine having an average molecular weight of 500 to 20,000; Represents 0 or 1, and n represents 0 to 3.
0, preferably 0-10, and m + n ≧ 1. These polymers may be in the form of a salt, and examples of the salt include salts of alkali metal ions and ammonium ions. Examples of the polybasic acid constituting the polyamide diamine residue include polybasic acids described in JP-A-3-38639, page (10). Examples of the polyvalent amine include ethylenediamine, 1,1 2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, isobutylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,
13-tridecanediamine and the like.

The molecular weight and the degree of polymerization of the polymer having an anionic group used in the present invention have substantially no effect on the effect of the present invention as long as it is a certain size or more. , The coating material is difficult to produce, and the surface condition of the photosensitive material is likely to be deteriorated. Therefore, the molecular weight of the polymer that can be used in the present invention is preferably 1,000,000 or less, 2000 or more, more preferably 400,000 or less, 5000 or more, and further preferably 150,000 or less 500
0 or more. The polymer having an anionic group used in the present invention may be used alone or as a mixture of two or more. The amount of the polymer having an anionic group is preferably in the range of 0.01 to 10 g / m ² ,
The range is more preferably from ^{3 to 3} g / m ² . Specific examples of the polymer having an anionic group used in the present invention are shown below, but the present invention is not limited thereto.

A-1 polyacrylic acid A-2 acrylic acid-ethyl acrylate 85:15 copolymer A-3 acrylic acid-vinyl acetate 90:10 copolymer A-4 acrylic acid-n-butyl vinyl ether 95: 5 copolymer A-5 acrylic acid-acrylonitrile 85:15 copolymer A-6 acrylic acid-methacrylamide 85:15 copolymer A-7 acrylic acid-methyl methacrylate 90:10 copolymer A-8 acrylic Acid-vinylpyrrolidone 70:30 copolymer A-9 acrylic acid-acrylamide 80:20 copolymer A-10 acrylic acid-N, N-diethylacrylamide 90:10 copolymer A-11 acrylic acid-acrylamide-acetic acid Vinyl 80:10:10 copolymer A-12 Acrylic acid-vinyl propionate 90:10 copolymer A-13 Acrylic acid-acrylonitrile-acrylamide 70:10:20 copolymer A-14 Acrylic acid-N, N-diethylacrylamide-vinyl acetate 90: 5: 5 copolymer A-15 Acrylic acid-Nt-butylacrylamide 95: 5 copolymer A-16 Acrylic acid-acrylonitrile- Vinyl acetate 80:10:10 copolymer A-17 Acrylic acid-N-hydroxymethylacrylamide 70:30 copolymer A-18 Acrylic acid-styrene-p-sulfonic acid 60:40 copolymer A-19 Acrylic Acid-vinyl chloride 95: 5 copolymer A-20 Acrylic acid-vinyl alcohol-vinyl acetate 18: 80: 2 copolymer

A-21 polymethacrylic acid A-22 methacrylic acid-ethyl methacrylate 95: 5 copolymer A-23 methacrylic acid-methyl methacrylate 90:10 copolymer A-24 methacrylic acid-acrylonitrile 90:10 copolymer Polymer A-25 methacrylic acid-vinyl pyrrolidone 80:20 copolymer A-26 methacrylic acid-methacrylamide 80:20 copolymer A-27 methacrylic acid-vinyl acetate 90:10 copolymer A-28 methacrylic acid- Ethyl acrylate 90:10 copolymer A-29 Methacrylic acid-n-butyl vinyl ether 90:10 copolymer A-30 Methacrylic acid-acrylamide 80:20 copolymer A-31 Methacrylic acid-Nt-butylacrylamide 95: 5 copolymer A-32 methacrylic acid-N, N-diethylacrylamide 90:10 copolymer A-33 methacrylic acid-N, N-di Methylacrylamide 90:10 copolymer A-34 methacrylic acid-N, N-diethylacrylamide-butyl acrylate 90: 5: 5 copolymer A-35 methacrylic acid-N, N-diethylacrylamide-acrylamide 85: 5: 10 copolymer A-36 methacrylic acid-methyl acrylate 90:10 copolymer A-37 methacrylic acid-styrene 95: 5 copolymer A-38 methacrylic acid-vinyl chloride 90:10 copolymer A-39 methacryl Acid-styrene-vinylsulfonamide 80:10:10 copolymer A-40 Maleic acid-ethyl acrylate-vinyl acetate 80:10:10 copolymer

A-41 Maleic acid-ethyl acrylate 80:20 copolymer A-42 Maleic acid-vinyl acetate 85:15 copolymer A-43 Maleic acid-n-butyl vinyl ether 80:20 copolymer A- 44 Maleic acid-methacrylamide 70:30 copolymer A-45 Maleic acid-vinyl propionate 90:10 copolymer A-46 Maleic acid-iso-butyl vinyl ether 90:10 copolymer A-47 Maleic acid-styrene 90:10 copolymer A-48 maleic acid-vinyl acetate-styrene 80:10:10 copolymer A-49 maleic acid-methyl vinyl ether 90:10 copolymer A-50 maleic acid-methyl methacrylate 90:10 Copolymer A-51 Maleic acid-vinyl benzoate 95: 5 copolymer A-52 Maleic acid-vinyl pyrrolidone 60:40 copolymer A-53 Maleic acid-N, N-diethylacrylic Luamide 70:30 copolymer A-54 Maleic acid-ethylene 80:20 copolymer A-55 Maleic acid-p-hydroxystyrene 70:30 copolymer A-56 Maleic acid-acrylamide 70:30 copolymer A -57 Maleic acid-acrylic acid 60:40 copolymer A-58 Styrenesulfonic acid-ethyl acrylate 95: 5 copolymer A-59 Styrenesulfonic acid-methyl acrylate 95: 5 copolymer

A-60 Styrenesulfonic acid-acrylonitrile 90:10 copolymer A-61 Polystyrenesulfonic acid A-62 Styrenesulfonic acid-N, N-diethylacrylamide 90:10 copolymer A-63 Styrenesulfonic acid-methacrylic Methyl acrylate 90:10 copolymer A-64 Styrenesulfonic acid-N-hydroxymethyl acrylamide 70:30 copolymer A-65 Styrenesulfonic acid-vinylpyrrolidone 75:25 copolymer A-66 Styrenesulfonic acid-methacrylic acid Hydroxyethyl 80:20 copolymer A-67 Styrenesulfonic acid-vinylpyrrolidone-acrylamide 80:10:10 copolymer A-68 Styrenesulfonic acid-acrylamide 80:20 copolymer A-69 Vinylbenzoic acid-N -iso-Provylacrylamide 90:10 copolymer A-70 vinyl benzoate 95-5 copolymer of perfumed acid-n-butyl acrylate A-71 Polyvinyl benzoic acid A-72 Butyl methacrylate-3-acryloxybutane-1-sulfonic acid 10:90 copolymer A-73 Cellulose sulfate A -74 Gelatin (isoelectric point 4.7) A-75 Gelatin (isoelectric point 2.5)

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When the color-forming reducing agent of the present invention is dispersed in a lipophilic high-boiling organic solvent, the redox reaction cannot be directly carried out with silver halide. Therefore, in order to form a color image from the imagewise exposed silver halide, a compound having a function of performing cross-oxidation between the silver halide and the color-forming reducing agent (hereinafter referred to as an auxiliary developing agent) is used. is necessary.

The auxiliary developing agent and its precursor used in the light-sensitive material of the present invention are described below. As the auxiliary developing agent used in the present invention, pyrazolidones, dihydroxybenzenes, reductones or aminophenols are preferably used, and pyrazolidones are particularly preferably used. It is preferable that the diffusivity in the hydrophilic colloid layer is low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less. It is as follows. The precursor of the auxiliary developing agent used in the present invention is a compound which is stably present in the light-sensitive material, but rapidly releases the above-mentioned auxiliary developing agent once processed with a processing solution. It is also preferable that the diffusivity in the hydrophilic colloid layer is low. For example, the solubility in water (25 ° C.) 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 released from the precursor is not particularly limited, but the auxiliary developing agent itself preferably has low solubility. The auxiliary developing agent precursor of the present invention is preferably represented by the general formula (A), and the auxiliary developing agent is preferably represented by the general formulas (B-1) and (B-2).

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Formula (A) A- (L) n-PUG

A represents a blocking group in which the bond with (L) n-PUG is cleaved during development processing, and L is the bond between L and PUG after the bond between L and A in formula (A) is cleaved. Represents a linking group which is cleaved, n represents an integer of 0 to 3, and PUG represents a group which is released and becomes an auxiliary developing agent.

The group represented by formula (A) will be described below. As the blocking group represented by A, the following known ones can be applied. That is, JP-B-48-9968, JP-A-52-8828, and
No. 7-82834, U.S. Pat. No. 3,311,476,
And JP-B-47-44805 (U.S. Pat.
No. 5,617), and block groups such as an acyl group and a sulfonyl group, and Japanese Patent Publication Nos. Nos. 791,830) and 55-349
No. 27 (U.S. Pat. No. 4,009,029);
6-77842 (U.S. Pat. No. 4,307,175)
No.), 59-105640, 59-105564
And a blocking group utilizing a reverse Michael reaction described in JP-B-59-105542 and the like.
No. 9727, U.S. Pat. Nos. 3,674,478;
Nos. 932,480 and 3,993,661;
Nos. 7-135944 and 57-135,945 (U.S. Pat. No. 4,420,554) and 57-136640.
Nos. 61-196239 and 61-196240 (U.S. Pat. No. 4,702,999) and 61-185.
Nos. 743 and 61-124941 (U.S. Pat.
39,408) and JP-A-2-280140, and the like.

US Pat. Nos. 4,358,525 and 4,358,525;
No. 330,617, JP-A-55-53330 (U.S. Pat. No. 4,310,612), and JP-A-59-121328.
Nos. 59-218439 and 63-3185
No. 55 (European Patent Publication No. 0295729) and other blocking groups utilizing an intramolecular nucleophilic substitution reaction.
No. 0) and No. 57-135949 (U.S. Pat.
No. 0,752), No. 57-179842, No. 59-1
Nos. 37945, 59-140445 and 59-21
No. 9741, No. 59-202059, No. 60-410
No. 34 (U.S. Pat. No. 4,618,563),
No. 59945 (U.S. Pat. No. 4,888,268) and No. 62-65039 (U.S. Pat. No. 4,772,537).
No. 62-80647, JP-A-3-236047.
Groups utilizing ring opening of a 5- or 6-membered ring described in JP-A-5-238445 and JP-A-3-238445.
No. 9-201057 (U.S. Pat. No. 4,518,685)
No. 61-95346 (U.S. Pat.
No. 885) and No. 61-95347 (U.S. Pat.
No. 92,811), JP-A-64-7035, JP-A-6-7035
4-42650 (U.S. Pat. No. 5,066,573)
No.), JP-A-1-245255 and 2-207249.
No. 2,235,055 (U.S. Pat. No. 5,118,5)
No. 96) and 4-186344 and the like, a blocking group utilizing the addition reaction of a nucleophile to a conjugated unsaturated bond,

JP-A-59-93442 and JP-A-61-32
Nos. 839 and 62-163051 and 5-3
No. 7299 and the like, a blocking group utilizing a β-elimination reaction, a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes described in JP-A-61-188540, No. 187850, a block group utilizing the Rossen rearrangement reaction.
Nos. 80646, 62-144163 and 62-
No. 147457, a block group utilizing the reaction of an N-acyl compound of thiazolidine-2-thione with an amine, JP-A-2-296240 (U.S. Pat.
No. 19,492), No. 4-177243, No. 4-17
No. 7244, No. 4-177245, No. 4-177724
No. 6, 4-177247, 4-177248,
4-177249, 4-179948, 4-
184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419 and JP-A-5-4581.
JP-A-3-236047 and JP-A-3-238445, a blocking group having two electrophilic groups and reacting with a dinucleophile described in JP-A No. 6-360.

In the compound represented by formula (A), the group represented by L is a linking group capable of cleaving (L) _n-1 -PUG after leaving from the group represented by A during development processing. Anything is acceptable. For example, U.S. Patent Nos. 4,146,396 and 4,652,51
No. 6,4,698,297, a group utilizing cleavage of a hemiacetyl tar ring, US Pat.
48,962, 4,847,185 or 4,857,440, a timing group for causing an intramolecular nucleophilic substitution reaction, US Pat. No. 4,409,3.
Utilizing a timing group for causing a cleavage reaction by utilizing an electron transfer reaction described in No. 23 or 4,421,845, and utilizing a hydrolysis reaction of imino ketal described in US Pat. No. 4,546,073. To cause a cleavage reaction, a group to cause a cleavage reaction by utilizing an ester hydrolysis reaction described in West German Patent Application No. 2,626,317, or a sulfite ion described in European Patent No. 0572844. And a group that causes a cleavage reaction by utilizing the reaction with

Next, PUG in the general formula (A) will be described. The auxiliary developing agent in the present invention is preferably an electron-emitting compound represented by the general formula (B-1) or the general formula (B-2) according to the Kendall-Peltz rule. Among them, those represented by (B-1) are particularly preferred. In the general formulas (B-1) and (B-2), R ^{51 to} R
⁵⁴ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ⁵⁵ ~R ⁵⁹
Is a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group,

Heterocyclic oxy, silyloxy, acyloxy, amino, anilino, heterocyclic amino, alkylthio, arylthio, heterocyclic thio, silyl, hydroxyl, nitro, alkoxycarbonyloxy, Cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group,

Aryloxycarbonyl, carbamoyl, carbonamido, ureido, imide, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamoylamino, alkylsulfinyl, arenesulfinyl, It represents an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, a sulfo group, a phosphinoyl group, and a phosphinoylamino group. q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different. R ⁶⁰ represents an alkyl group or an aryl group. When the auxiliary developing agent represented by the general formulas (B-1) and (B-2) is PUG of the general formula (A), the bonding position is an oxygen atom or a nitrogen atom of the auxiliary developing agent. Specific examples of the compound represented by formula (A), (B-1) or (B-2) are given below. However, the auxiliary developing agent and its precursor used in the present invention are not limited to these specific examples. Absent.

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These compounds may be added to any of the photosensitive layer, the intermediate layer, the undercoat layer, and the protective layer. However, the compound of the present invention must be provided between the layer containing the compound and the layer containing the mordant. It is added so that a layer containing a polymer having an anionic group is located. As a method for incorporating these compounds into the photosensitive material, a method of dissolving in a water-miscible organic solvent such as methanol and directly adding the solution to a coating solution, or a method of forming an aqueous solution or a colloidal dispersion in the presence of a surfactant in the presence of a surfactant. A method of dissolving in water or a hydrophilic colloid after dissolving in a solvent or oil substantially immiscible with water, or adding to a coating solution in the form of a solid fine particle dispersion. Methods and the like are adopted, and these conventional known methods can be applied alone or in combination. The amount added to the light-sensitive material is 1 mol% to 200 mol%, preferably 5 mol% to 100 mol%, more preferably 10 mol%, based on the color-forming reducing agent.
Mol% to 50 mol%.

The order in which the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention are applied is such that a photographic constituent layer containing a mordant and a photographic constituent layer containing a polymer having an anionic group according to the present invention. The coating order may be any as long as it is coated on the side opposite to the photographic constituent layer containing the auxiliary developing agent or the precursor of the auxiliary developing agent of the present invention. Specifically, from the support side, "a photographic constituent layer containing an auxiliary developing agent or a precursor of an auxiliary developing agent" / "a photographic constituent layer containing a polymer having an anionic group" / "a photographic constituent containing a mordant The order of application of the “layer” may be the order from the support side, “the photographic constituent layer containing a mordant” / “the photographic constituent layer containing a polymer having an anionic group” / “the auxiliary developing agent or the precursor of the auxiliary developing agent”. The coating order of the “photo-constituting layer to be contained” may be applied, and the coating position of the coupler-containing layer can be selected arbitrarily from the three types of photographic constituent layers. The coupler-containing layer may be the same photographic constituent layer as the “photographic constituent layer containing a polymer having an anionic group”. The photosensitive silver halide emulsion may be contained in the above-mentioned coupler-containing layer, or may be contained in a photographic component layer other than the coupler-containing layer. Further, a color mixture inhibitor, an ultraviolet absorber, and the like may be contained in the photographic constituent layer,
In addition to the above photographic constituent layers, a color mixture preventing layer, an ultraviolet absorbing layer, a protective layer and a light reflecting layer (for example, a layer containing titanium dioxide) may be coated.

Next, the anionic compound having a total carbon number of 10 or more and a molecular weight of 1000 or less, which is preferably used in the present invention, will be described in detail. An anionic compound having a total carbon number of 10 or more and a molecular weight of 1000 or less,
It has at least one anionic group, and the anionic group has the same meaning as the above-described anionic group of the anionic water-soluble polymer. Examples of the anionic compound preferably used in the present invention include those represented by the following formulas (D-1) to (D-15).

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In the formula, R ₁ and R ₂ each represent an aliphatic hydrocarbon group, one of which is an aliphatic hydrocarbon group having at least 4 carbon atoms, and the total number of carbon atoms in the molecule is 10 or more. It is. M represents a hydrogen ion, an alkali metal ion or an ammonium ion. m and n represent 1-10.

When the anionic compound having a total carbon number of 10 or more and a molecular weight of 1000 or less is used in the present invention, the amount of the tertiary amino group or quaternary ammonium salt in the mordant is not less than 10 mol%. The desired effect is exhibited by the addition, but if the amount is too large, the solution viscosity becomes too high or agglomerates with the mordant, thereby deteriorating the surface condition of the photosensitive material. Therefore, the amount of the anionic compound is preferably 10 to 200 mol%, more preferably 20 to 100 mol% of the tertiary amino group or quaternary ammonium salt in the mordant. In the present invention, the anionic compound may be added to any of the photographic constituent layers, but is preferably added to the same layer as the mordant, the layer adjacent to the layer containing the mordant, or both the same layer and the adjacent layer. The compounds represented by formulas (D-1) to (D-15) are specifically shown, but the anionic compound preferably used in the present invention is not limited to these specific examples.

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The dye-forming coupler and the color-forming reducing agent used in the present invention are most typically added to the same layer. However, if they can react, they are separately added to different layers. be able to. These components are preferably added to a silver halide emulsion layer in a light-sensitive material or an adjacent layer thereof, and particularly preferably to the same silver halide emulsion layer together. In this embodiment, both compounds are preferably co-emulsified in a high boiling organic solvent.

In the silver halide photographic light-sensitive material of the present invention,
Conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmissive support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) and polyesters of NDCA, terephthalic acid and EG. And the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable. Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent can be used, and more preferably, a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is used. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight based on the resin, more preferably 0.05 to 3% by weight.
01 to 0.5% by weight.

The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface. The silver halide emulsion for use in the present invention is preferably a silver chloride or silver chlorobromide emulsion having a silver chloride content of 95 mol% or more, and more preferably a silver chloride content of 98 mol% or more, from the viewpoint of rapid processing. Silver halide emulsions are preferred. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable because high sensitivity can be obtained and photographic performance can be stabilized.

The above-mentioned reflective supports and silver halide emulsions,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

[0127]

[Table 1]

[0128]

[Table 2]

As the antibacterial and antifungal agents usable in the present invention, those described in JP-A-63-271247 are useful.
The light-sensitive material of the present invention can be used in a cathode ray tube (CRT) in addition to being used in a printing system using a normal negative printer.
Also, it is suitable for a scanning exposure method using. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at one time, ie, the cathode ray tube is exposed. The image signal of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
However, in general, field-sequential exposure is preferable for improving image quality because a cathode ray tube with high resolution can be used. The light-sensitive material of the present invention may be a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. It is preferably used for a digital scanning exposure system using density light. The system is compact,
In order to reduce the cost, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) in which a semiconductor laser or a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. If the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less. Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table.

The method of developing the light-sensitive material containing the color-forming reducing agent of the present invention after exposure is as follows: an activator processing method of developing with an alkaline processing solution not containing a color developing agent; an auxiliary developing agent / base. , A method in which the alkaline processing solution is spread on a photosensitive material by a diffusion transfer method, and a method in which thermal processing is performed.

Activator processing refers to a processing method in which a color-forming reducing agent is incorporated in a light-sensitive material and is developed with a processing solution containing no color-developing agent. In the present invention, the "activator solution" is substantially free of a p-phenylenediamine-based color developing agent and a reducing agent for color development as conventionally used, but an alkali for increasing the pH of the solution. , And may contain other components (buffering agent, halogen, chelating agent, etc.). In some cases, it is preferable that a reducing agent is not contained in order to maintain processing stability. In this case, it is preferable that an auxiliary developing agent, hydroxyamines, sulfites, and the like are not substantially contained. Here, "substantially not contained" means preferably 0.5 mmol / liter or less, more preferably 0.1 mmol / liter or less. In particular, it is preferable not to contain at all. The pH of the alkaline processing solution (aqueous solution) as an activator solution is
It is preferably 9 to 14, particularly preferably 10 to 13.
It is. The activator processing photosensitive material and its processing are described in, for example, Japanese Patent Application Nos. 7-63572 and 7-33419.
Nos. 0, 7-334192, 7-334197, and 7-344396.

The process of developing an alkaline processing solution by the diffusion transfer method is known in the art as an instant processing system, and includes at least one photosensitive layer / dye-forming layer (the photosensitive layer and the dye-forming layer are composed of the same layer). And an image-receiving element having a mordant layer for capturing and mordanting the diffusible dye formed from the photosensitive layer / dye-forming layer, and a photosensitive material having the same support or on a separate support. Is developed with a thickness of about 500 μm or less, and preferably with a liquid thickness of 50 to 200 μm. When an auxiliary developing agent is incorporated, it is preferable that the alkaline processing liquid does not contain the auxiliary developing agent for production and storage of the processing solution. The pH of the alkaline processing liquid in the diffusion transfer method is preferably from 10 to 14, and particularly preferably from 12 to 14. For the process of instant photographic materials, see T.A. H. James, The The
ory of Photographic Process
ss fourth edition, Macmillan Publisher
ng Co. , Inc. New York (1977)
The structure of a specific film unit is described in JP-A-63-226649. Examples of the materials included in the film unit and various layers including the same are described below.

The dye image-receiving layer and the mordant contained therein are described in JP-A-61-252551, US Pat. Nos. 2,548,564, 3,756,814 and 4,124,386. No. 3,625,694. The neutralizing layer for lowering the pH of the photosensitive material after developing the alkaline processing solution is described in
-122753, U.S. Pat. No. 4,139,383,
RD-No. 16102, and the timing layer used in combination with the neutralizing layer is disclosed in JP-A-54-136328, U.S. Pat. No. 4,267,262.
No. 4,009,030 and 4,268,60
No. 4. Any emulsion can be used as the emulsion. Preferred autopositive emulsions for photographic light-sensitive materials are described in JP-A-7-333770 and JP-A-7-333.
No. 771 and the like. In addition, if necessary, a light shielding layer, a reflection layer, an intermediate layer, an isolation layer, an ultraviolet absorption layer,
A filter layer, an overcoat layer, an adhesion improving layer, and the like can be provided. The processing solution for processing the above-mentioned light-sensitive material contains processing components necessary for development, and usually contains a thickening agent and spreads uniformly on the light-sensitive material. Thickening agents such as carboxymethylcellulose and hydroxyethylcellulose are preferable as the thickener. Details of the photosensitive layer and the processing solution are described in JP-A-7-337377.

The heat treatment in the heat development of the light-sensitive material is known in the art and can be applied to the light-sensitive material of the present invention. The photothermographic material and its process are described, for example, in Photo Industry Fundamentals (1979, published by Corona Co., Ltd.).
53-555 pages, 40 pages of video information issued in April 1978,
Nebbetts Handbook of Photo
OGRAPHY AND REPROGRAPHY , 7
th Ed. (Van Nostrand and R
Einhold Company), pages 32-33, U.S. Patent Nos. 3,152,904 and 3,301,67.
No. 8, No. 3,392,020, No. 3,457,0
No. 75, British Patent Nos. 1,131,108 and 1,1
67,777 and Research Disclosure Magazine 1
It is described in June 978, pages 9 to 15 (RD-17029).

The light-sensitive material of the present invention is prepared in accordance with US Pat. No. 4,514,49 for the purpose of accelerating silver development and a dye-forming reaction.
No. 3, the first 4,657,848 and No. prior art No. 5 (March 22, 1991, AZTEC Co., Ltd. issued) of 55 pages in which the base precursor and European Patent Publication 210 is described to 86 pages and the like, No. 660, U.S. Pat.
It is preferable to apply the base generation method described in No. 0,445. To the light-sensitive material of the present invention, a heat solvent described in U.S. Pat. Nos. 3,347,675 and 3,667,959 may be added for the purpose of accelerating thermal development. When the light-sensitive material of the present invention is subjected to heat treatment, in order to promote development and / or diffusion transfer of the processing material,
Water, an aqueous solution containing an inorganic alkali metal salt or an organic base,
It is also preferable to include a low-boiling solvent or a mixed solvent of a low-boiling solvent and water or the above-mentioned basic aqueous solution in a light-sensitive material or a processing sheet and heat-treat it. Examples of the method using water include JP-A-63-144354 and JP-A-63-144.
355, 62-38460, JP-A-3-2105
No. 55, JP-A-62-253159 and 63-855
44, EP 210,660 and U.S. Pat. No. 4,740,445. The present invention relates to JP-A-7-261336 and JP-A-7-268045.
, JP-A-8-30103, JP-A-8-46822, JP-A-8-97344 and the like. The heating temperature in the thermal development step is from about 50 ° C. to 200 ° C., and particularly from 60 ° C. to 150 ° C. is useful.

[0138]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but it should be understood that the present invention is not limited to these Examples.

Example 1 A corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Further, six types of photographic constituent layers were coated. (100) was produced. The coating solution was prepared as follows. First layer coating solution 17 g of coupler (EXY), color reducing agent (36) 20
g, a solvent (Solv-1) 80 g was dissolved in ethyl acetate, and this solution was dissolved in 400 g of a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid.
To prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, a large-sized emulsion A having an average grain size of 0.88 μm and a small-sized emulsion A having an average grain size of 0.70 μm:
7 mixtures (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion). did. This emulsion contains the following blue-sensitive sensitizing dyes A, B, and C in an amount of 7.0 × 10 ^-4 mol per mol of silver per mol of silver, and 7.0 × 10 ^-4 mol per mol of silver. , 8.5 × 10 ^-4 mol each. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition. The emulsion coating amount indicates a silver equivalent coating amount.

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The coating solutions for the second to sixth layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 60.0mg / m} 2, 50.0mg / m 2
And 10.0 mg / m ² .

Further, to each of the photographic constituent layers, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. (Layer Structure) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support polyethylene-laminated paper [polyethylene on the first layer side contains white pigment (TiO ₂ 15% by weight) and bluish dye (ultramarine)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.20 Gelatin 1.50 Yellow coupler (ExY) 0.17 Color reducing agent (36) 0.20 Solvent (Solv-1) 0 .80

Second layer (color mixture prevention layer) Gelatin 1.09 Color mixture prevention agent (Cpd-6) 0.11 Solvent (Solv-1) 0.19 Solvent (Solv-2) 0.07 Solvent (Solv-3) 0.25 Solvent (Solv-4) 0.09 1,5-diphenyl-3-pyrazolidone 0.065 (fine particle solid dispersion state)

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B 0.20 Gelatin 1.50 Magenta coupler (ExM1) 0.24 Color-forming reducing agent (36) 0.20 Solvent (Solv-1) 0 .80

Fourth layer (color mixture preventing layer) Gelatin 0.77 Color mixture inhibitor (Cpd-6) 0.08 Solvent (Solv-1) 0.14 Solvent (Solv-2) 0.05 Solvent (Solv-3) 0.14 Solvent (Solv-4) 0.06 1,5-diphenyl-3-pyrazolidone 0.046 (fine particle solid dispersion state)

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C 0.20 Gelatin 0.15 Cyan coupler (ExC1) 0.21 Color-forming reducing agent (36) 0.20 Solvent (Solv-1) ) 0.80

Sixth layer (protective layer) Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

Silver chlorobromide emulsion B: cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.55 μm and small-size emulsion B having an average grain size of 0.39 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface containing silver chloride as a base in each size emulsion.

In the silver chlorobromide emulsion B, green sensitizing dyes D, E,
F was used in the amount shown below.

(The sensitizing dye D was used in an amount of 1.5 × 10 ⁻³ mol for a large-sized emulsion, 1.8 × 10 ⁻³ mol for a small-sized emulsion, and Sensitizing dye E was used in an amount of 2.0 × 10 ^-4 mol per mol of silver halide and 3.5 mol per mol of silver halide.
× 10 ^-4 mol of sensitizing dye F per mol of silver halide, 1.0 × 10 ^-3 mol for large-size emulsion, and 1.4 × 10 ^-3 mol for small-size emulsion. Added)

Silver chlorobromide emulsion C: cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C of 0.41 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and 0.8 mol% of AgBr was locally contained in a part of the grain surface having silver chloride as a base in each size emulsion.

In the silver chlorobromide emulsion C, the red sensitizing dyes G and H were used in the following amounts.

(Per mol of silver halide, 2.5 × 10 ^-4 mol was added to a large-size emulsion, and 4.0 × 10 ^-4 mol was added to a small-size emulsion.)

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The couplers and color-forming reducing agents in the coating solutions of the first, third and fifth layers were replaced with the couplers and color-forming reducing agents shown in Table a in equimolar amounts, or the coating of the sixth layer was As shown in Table a, the mordant was added to the solution in an amount of 3.21 per m ^2.
Samples (101) to (105) were produced in exactly the same manner as in the production of Sample (100), except that g was added. Samples (10) to (105) were the same as Samples (100) to (105) except that a polymer-containing layer having an anionic group having the following composition shown in Table a was provided between the fifth layer and the sixth layer.
Samples (110) to (110) in exactly the same manner as in (0) to (105).
(115) was produced. Furthermore, as shown in Table a, exactly the same as the sample (113) except that a polymer-containing layer having an anionic group was coated on the opposite side of the sixth layer from the support (in this case, the uppermost layer). The sample (116) was produced. Further, as shown in Table b, the sample (11) was prepared in exactly the same manner as the sample (113) except that an anionic compound having a carbon number of 10 or more and a molecular weight of 1000 or less was added.
7) to (124) were produced.

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[Table 3]

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[Table 4]

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Samples (100) to (100)
(105), (110)-(124) at 25 ° C. 60% R
After 2 days at H, FWH manufactured by Fuji Photo Film Co., Ltd.
Tone exposure was given using a sensitometer (color temperature of light source: 3200 ° K) using a three-color separation filter for sensitometry.

The exposed sample was processed in the following processing steps. Processing process temperature Time development 40 ° C 20 seconds Bleaching and fixing 40 ° C 45 seconds Rinse Room temperature 45 seconds

Developing solution (activator solution) Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml UVX 2 g Add water and 1000 ml with 1N potassium hydroxide PH was adjusted to 12 (25 ° C.).

Bleaching-fixing solution Water 600 ml Ammonium thiosulfate (700 g / liter) 93 ml Ammonium sulfite 40 g Ammonium iron (III) ethylenediaminetetraacetate 55 g 2 g ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water is added to 1000 ml PH = 5.8 (25 ° C) with acetic acid and aqueous ammonia
Was adjusted.

Rinse solution Chlorinated sodium isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

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The maximum color density of the yellow color portion of the obtained sample was measured with blue light, the maximum color density of the magenta color portion was measured with green light, and the maximum color density of the cyan color portion was measured with red light. Further, each of the above samples was immersed in the following alkaline treatment solution at 25 ° C. for 10 seconds, and the density of each color-developed portion was measured. Alkali treatment liquid Water 800 ml Potassium carbonate 30 g Add water 1000 ml pH (1N sulfuric acid or 1N potassium hydroxide) 10 Also, samples (100) to (105), (11) immediately after application
After aged 2) at 50 ° C. and 80% RH for 2 days, exposure / development treatment (no alkali immersion after treatment) and concentration measurement were performed in the same manner as described above. The results of the above concentration measurement are shown in Table c.

[0173]

[Table 5]

As is clear from Table c, Samples (101) and (103) which were coated with a mordant and used the coupler of the present invention and a color-forming reducing agent were Samples (100) and (10).
As compared with 2), a high color density can be obtained without alkali immersion after the development processing, but it can be seen that the density decrease due to the high temperature and high humidity thermostat before exposure is large. Samples (111) and (113) to (115) using the coupler, coloring reducing agent and mordant of the present invention, and coating the polymer having an anionic group of the present invention between the fifth layer and the sixth layer using the coupler. In (3), a high color-forming density was obtained even without alkali immersion after the development processing, and a decrease in density due to high-temperature and high-humidity thermo was significantly suppressed as compared with Samples (101) and (103). On the other hand, in the sample (116) in which the polymer having an anionic group of the present invention was coated on the side opposite to the support with respect to the sixth layer, the decrease in concentration due to the high-temperature and high-humidity thermo was hardly suppressed. Further, in Samples (119) to (123) coated with the anionic compound of the present invention, the decrease in concentration due to the high-temperature and high-humidity thermostat was further suppressed as compared with Sample (113). The processing steps shown in the above embodiments are:
Since the processing solution does not contain a p-phenylenediamine-based developing agent, the replenishment and discharge amounts of the processing solution components are reduced. From the above results, using the coupler of the present invention, a color-forming reducing agent and a mordant, a layer containing the polymer having an anionic group of the present invention is provided between the auxiliary developing agent-containing layer and the mordant-containing layer. By doing so, a silver halide color photographic light-sensitive material that can reduce the replenishment and discharge of the developing processing solution component, has high color-forming properties, and has a small decrease in color density even after storage of the light-sensitive material before exposure can be obtained. It can be seen that it can be obtained.

Example 2 In Example 1, the auxiliary developing agent was replaced with the precursor ETA-39 or ETA-41 of the auxiliary developing agent represented by the general formula (A) of the present invention. The effect was obtained.

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According to the present invention, it is possible to reduce the replenishment and discharge of the components of the developing solution, and to obtain a photosensitive material exhibiting high color development regardless of whether or not the photosensitive material has been exposed to light before exposure.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 7/396 G03C 7/396

Claims (4)

[Claims] 1. A support comprising at least one layer containing a dye-forming coupler on a support, and a light-sensitive silver halide emulsion in a layer containing the dye-forming coupler or a layer not containing the dye-forming coupler. A silver halide photographic light-sensitive material, wherein the dye-forming coupler is a coupler for generating a diffusible dye, and the first layer containing an auxiliary developing agent or a precursor of the auxiliary developing agent, And a third layer containing a mordant for immobilizing a diffusible dye, wherein the first layer has a third layer through a second layer. A halogen which is coated on the side opposite to the layer and which contains at least one color-forming reducing agent represented by the following general formula (I) in the dye-forming coupler-containing layer. Silver halide photographic material. General formula (I) In the formula, Cα represents a carbon atom. Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Q represents an atom group forming an unsaturated ring with Cα. 2. The photographic component layer according to claim 1, wherein the first layer and the third layer are provided separately from a layer containing a dye-forming coupler or a layer containing a photosensitive silver halide emulsion. And the second layer is a photographic constituting layer provided between a photosensitive silver halide emulsion layer furthest from the support and a third layer further away from the support than this emulsion layer. The silver halide photographic light-sensitive material according to claim 1, characterized in that: 3. The method of claim 1, wherein the first, second, and third layers are provided separately from a layer containing a dye-forming coupler or a layer containing a photosensitive silver halide emulsion. 2. The silver halide photographic material according to claim 1, which is a photographic constituent layer. 4. The mordant which is a mordant having a tertiary amino group or a quaternary ammonium salt as a functional group, and at least one anionic compound having a total carbon number of 10 or more and a molecular weight of 1000 or less, 2. The silver halide photographic light-sensitive material according to claim 1, wherein the tertiary amino group or quaternary ammonium salt in the silver halide photographic material is contained in an optional photographic component layer in an amount of 10 mol% or more.