JPH1048771A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to process the photosensitive material with an alkaline solution small in deterioration with the lapse of time and containing no color developing agent and to reduce stains due to the long storage of the photosensitive material and to enhance fastness of a color image by incorporating a specified reducing agent for color development in a photographic constituent layer in a solid dispersion and a dye forming coupler. SOLUTION: One of the photographic constituent layers formed on a support contains the dye forming coupler and the color developing reducing agent represented by the formula in which Ar is an aromatic hydrocarbon or heterocyclic group; X is a -CO- or -SO2 - group; (n) is 1 or 0; and R is an H atom or a straight or branched or cyclic alkyl or aromatic hydrocarbon group. This color developing reducing agent can be added in a solid dispersion state into the photosensitive material and it is dissolved in the alkaline solution and reacts directly with the exposed silver halide to be oxidized and this oxidation product reacts with the dye forming coupler to form the dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photographic technology, and more particularly to a silver halide photographic light-sensitive material which can cope with environmental protection and simple and rapid processing, and has good color-forming properties, storage stability and hue. The present invention relates to a color image forming method.

[0002]

2. Description of the Related Art Generally, a color photographic light-sensitive material is subjected to color development after exposure, whereby an oxidized p-phenylenediamine derivative reacts with a coupler to form a color image. In this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having respective complementary colors are formed. Color development is achieved by immersing the exposed color photographic light-sensitive material in an aqueous alkaline solution (color developing solution) in which a p-phenylenediamine derivative is dissolved. However, the p-phenylenediamine derivative in the form of an aqueous alkaline solution is unstable and easily deteriorates with time. Therefore, there is no problem when the replenisher is frequently replenished with a large amount of treatment, When replenishment is small, there is a problem that the color developing solution cannot be used for a long time and needs to be replaced. When the processing amount is large, a large amount of the used color developing solution containing the p-phenylenediamine derivative is discharged. The disposal of the used color developing solution is complicated, and the processing of the used color developing solution discharged in large quantities is a serious problem.

[0003] If the p-phenylenediamine derivative in the color developing solution is removed from the processing solution, it is possible to solve the problems of the color developing solution over time and complicated waste liquid treatment. However, when p-phenylenediamine is removed from the processing solution, no color development naturally occurs. In order to perform color development with an alkaline solution from which the p-phenylenediamine derivative has been removed, p-phenylenediamine or a compound having a similar function may be contained in the photosensitive material. A method of incorporating a primary amine or a precursor thereof into a light-sensitive material is known. Examples of an aromatic primary amine developing agent or a precursor thereof which can be incorporated are US Patents 2,507,114 and 376432.
No. 8, No. 4060418, JP-A-56-6235,
And the compounds described in JP-A-58-192031. However, since these aromatic primary amines and precursors thereof are unstable, they have a drawback that stain is generated during long-term storage or color development of unprocessed photosensitive materials. Another effective means is, for example, European Patent 05
No. 45491A1, No. 565165A1, and the like, and a method of incorporating a sulfonylhydrazine type compound into a hydrophilic colloid layer. However, even the sulfonylhydrazine-type compounds mentioned here are not sufficiently stable, and stains under high-temperature and high-humidity conditions due to long-term storage after treatment are still at a practically problematic level. In response to the above problems, development of a technique for improving storage stability has been desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to enable processing with an alkali solution (activator solution) substantially free of color developing agent and having little deterioration over time, and reducing the stain due to long-term storage of the photosensitive material. Another object of the present invention is to provide a light-sensitive material having excellent color image fastness.

[0005]

The object of the present invention has been found to be achieved by the following method. (1) At least one kind of a color-forming reducing agent represented by the following general formula (D-1) is contained in any of the photographic constituent layers on the support in a solid dispersion state, and at least one kind of a dye-forming coupler is contained. A silver halide photographic light-sensitive material characterized by being contained.

[0006]

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In the formula, Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. X is -CO- group or -SO ₂ -
And n represents 1 or 0. R represents a hydrogen atom, a linear, branched or cyclic alkyl group, an aromatic hydrocarbon group, an aromatic or non-aromatic heterocyclic group, an acyloxy group, an alkoxy group, an aryloxy group or an amino group. (2) X in the general formula (D-1) is a -CO- group, and n
Is 1, the silver halide photographic light-sensitive material as described in the above item (1). (3) The method according to the above item (1) or (2), wherein the total amount of silver halide applied to all coating layers is 0.003 to 0.3 g / m ² in terms of silver. The silver halide photographic light-sensitive material as described above. (4) The exposure time per pixel is 10 ^-8 to 10 ^-4 seconds,
The silver halide color photographic material as described in (1), (2) or (3) above, which is used for scanning exposure with a beam having an overlap between adjacent rasters.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION 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 (D-1) used in the present invention can be added to a light-sensitive material in a solid dispersion state, and is dissolved in an alkali solution and exposed. Is a compound that directly reacts with and is oxidized, and the oxidized product reacts with a dye-forming coupler to form a dye. The reducing agent for solid dispersion color development used in the present invention is represented by the following general formula.

[0009]

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In the formula, Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. X is -CO- group or -SO ₂ -
Y represents a simple bond or -NH-. R represents a hydrogen atom, a linear or branched, chain or cyclic alkyl group, an aromatic hydrocarbon group, an aromatic or non-aromatic heterocyclic group, an acyloxy group, an alkoxy group, an aryloxy group or an amino group . When Ar is an aromatic hydrocarbon group, the sum of Hammett's sigma para values (σp) of substituents on the aromatic hydrocarbon ring is preferably from 0.8 to 4.0, more preferably from 1.2 to 3.5. Preferably, 1.5 to 3.0 is most preferable. When Ar is an aromatic heterocyclic group, it is preferable that one or more substituents having a positive Hammett σp value are substituted on the aromatic heterocyclic ring. This aromatic hetero ring is preferably a 3- to 8-membered ring, more preferably a 5- to 8-membered ring.
It is a six-membered ring. Examples of this include a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring,
2,4-triazine ring, 1,3,5-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, 1,2,2
4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,3,4-oxadiazole ring, 1,2,4-oxadiazole ring, 1,2,5-oxadiazole ring,
A thiazole ring, an oxazole ring, an isothiazole ring, an isoxazole ring, a thiophene ring and the like are preferable, and a condensed ring in which these rings are condensed with each other is also preferably used. The Hammett's substituent constants σp and σm are described in, for example, Naoki Inamoto, “Hammet Rule—Structure and Reactivity—”.
(Maruzen), "New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds V", p. 2605 (Chemical Society of Japan, Maruzen), Tadao Nakaya, "Explanation of Theoretical Organic Chemistry", p. 217 (Tokyo Kagaku Dojin), Chemical Review (vol. 91), pp. 165-195 (19
(1991) and other detailed books.

X is more preferably a -CO- group. n is preferably 0 when X is a —SO ₂ — group, and is preferably 1 when X is a —CO— group. Most preferably, X is -CO
A group, and n is 1. When R is an alkyl group, the number of carbon atoms is preferably 1 to 30, more preferably 1 to 18, and most preferably 1 to 6. Examples include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, dodecyl and the like. When R is an aromatic hydrocarbon group, the carbon number is 6 to
30 is preferable, 6 to 24 is more preferable, and 6 to 16 is most preferable. Examples thereof include a phenyl group and a naphthyl group, and those further condensed are also preferable.
Preferred as a condensed ring is a benzene ring. When R is an aromatic or non-aromatic heterocyclic group, it preferably has 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms,
6 is most preferred. Examples include furyl, pyrrolidino, morpholino, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidyl, pyrazyl, oxazolyl, thiazolyl, and the like. A fused ring is also preferable. Preferred as a condensed ring is a benzene ring. When R is an acyloxy group, it is preferably 1 to 30, more preferably 1 to 20, and most preferably 1 to 8.
Examples include an acetoxy group, a benzoyloxy group and the like. When R is an alkoxy group, the carbon number is 1 to
30 is preferable, 1 to 18 is more preferable, and 1 to 6 is most preferable. Examples include methoxy, ethoxy, butoxy, cyclohexyloxy, decyloxy and the like. When R is an aryloxy group, it preferably has 6 to 30 carbon atoms, more preferably 6 to 24 carbon atoms, and 6 to 1 carbon atoms.
6 is most preferred. Examples include phenoxy, naphthyloxy and the like. When R is an amino group, it preferably has 0 to 30 carbon atoms, more preferably 1 to 18 carbon atoms, and 1
~ 6 is most preferred. Examples include amino, methylamino, ethylamino, propylamino, hexylamino and the like. R is preferably an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, or a non-aromatic heterocyclic ring, and most preferably an alkyl group or an aromatic hydrocarbon group.

A substituent may be further bonded to Ar and R. Examples thereof include a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (for example, trifluoromethyl, methyl, ethyl, Propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-
Ethylhexyl, dodecyl, etc.), a linear, branched or cyclic alkenyl group having 2 to 30 carbon atoms (for example, vinyl,
1-methylvinyl, cyclohexen-1-yl and the like), an alkynyl group having a total of 2 to 30 carbon atoms (for example, ethynyl,
-Propynyl, etc.), an aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, anthryl, etc.),
30 acyloxy groups (eg, acetoxy, tetradecanoyloxy, benzoyloxy, etc.), having 1 to 3 carbon atoms
A carbamoyloxy group (e.g., N, N-dimethylcarbamoyloxy, etc.), a carbonamide group having 1 to 30 carbon atoms (e.g., formamide, N-methylacetamide, acetamide, N-methylformamide, benzamide, etc.), carbon Sulfonamide groups of numbers 1 to 30 (for example, methanesulfonamide, dodecanesulfonamide,
Benzenesulfonamide, p-toluenesulfonamide, etc.), a carbamoyl group having 1 to 30 carbon atoms (for example, N-
Methylcarbamoyl, N, N-diethylcarbamoyl,
N-mesylcarbamoyl and the like, a sulfamoyl group having 0 to 30 carbon atoms (for example, N-butylsulfamoyl, N,
N-diethylsulfamoyl, N-methyl-N- (4-
Methoxyphenyl) sulfamoyl, etc.), having 1 to 3 carbon atoms
An alkoxy group of 0 (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 30 carbon atoms (for example, phenoxy, 4-methoxyphenoxy,
Naphthoxy, etc.), an aryloxycarbonyl group having 7 to 30 carbon atoms (eg, phenoxycarbonyl, naphthoxycarbonyl, etc.),

An alkoxycarbonyl group having 2 to 30 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), an N-acylsulfamoyl group having 1 to 30 carbon atoms (eg, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 30 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 30 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 30 carbon atoms (eg, ethoxycarbonylamino), an aryloxycarbonylamino group having 7 to 30 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 30 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 30 carbon atoms (eg, methanesulfinyl, octanesulfinyl and the like), an arylsulfinyl group having 6 to 30 carbon atoms (eg, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl), having 1 to 3 carbon atoms
An alkylthio group of 0 (eg,

Methylthio, octylthio, cyclohexylthio, etc.), arylthio groups having 6 to 30 carbon atoms (eg, phenylthio, naphthylthio, etc.), 1 to 30 carbon atoms
Ureido group (eg, 3-methylureido, 3,3-
Dimethylureide, 1,3-diphenylureide, etc.),
A heterocyclic group having 2 to 30 carbon atoms (for example, a 3- to 12-membered monocyclic or condensed ring containing at least one heteroatom such as 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 30 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), carbon Sulfamoylamino groups of numbers 0 to 30 (eg, N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), and silyl groups of 3 to 30 carbon atoms (eg, 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 solid-dispersed color-forming reducing agent used in the present invention exists as fine solid particles in the light-sensitive material before the light-sensitive material is developed, and can exhibit a function as a developer when immersed in a developing solution. Things. Accordingly, it is necessary that the reducing agent for solid dispersion color development of the present invention undergoes some change from the solid state depending on the chemical species contained in the developing solution. The most preferable change is dissociation due to alkali present in the developing solution. In this case, the reducing agent for solid color dispersion of the present invention has a pKa of 5 to 12 (pKa).
Is the value for a solution of tetrahydrofuran / water = 6/4)
It is preferable to have at least one dissociating group having the value of
More preferably, it has one or more dissociating groups having a pKa of 6 to 11. Further, a method of dispersing a color-forming reducing agent as a complex of aluminum, zinc, boron or the like in a solid state and supplying these decomplexing agents from a developing solution to change the solid dispersion state (chelate exchange method) is also preferably used. Can be Next, specific examples of the color-forming reducing agent represented by formula (D-1) are shown, but the scope of the present invention is not limited to these specific examples.

[0016]

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[0017]

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[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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Some of the compounds represented by formula (D-1) of the present invention are described in, for example, US Pat. No. 2,424,256,
No. 4,481,268, EP 565,165
No., JP-A-61-259249 and the like,
Other compounds can be synthesized by the methods described therein.

The method for dispersing the color-forming reducing agent of the present invention in a solid state is not particularly limited, and can be prepared by a known method. The details of the production method are described in Functional Pigment Application Technology (CMC, 1991). Media distribution is one of the common methods. In this method, the color-forming reducing agent powder or its wet cake, which is called a wet cake, is wetted with water or an organic solvent to form an aqueous slurry. Sand mill, roller mill,
Presence of dispersion media (steel balls, ceramic balls, glass beads, alumina beads, zirconia silicate beads, zirconia beads, polymer beads, Ottawa sand, etc.) using pin mills, co-ball mills, caddy mills, horizontal sand mills, attritors, etc. Grind by mechanical force below. Among these, the average diameter of the beads is preferably 2 mm to 0.3 mm, more preferably 1 mm to 0.3 mm, and still more preferably 0.5 mm to 0.3 mm.
m to 0.3 mm are used. In addition to these, a pulverization method using a jet mill, a roll mill, a homogenizer, a colloid mill or a dissolver, and a pulverization method using an ultrasonic disperser can also be used. Average particle size 0.005 μm to 10 μm, preferably 0.01 μm
m to 1 μm, more preferably 0.01 μm to 0.7 μm, is a solid-liquid mixture dispersed in a solvent, and the color-forming reducing agent is not substantially dissolved in a solvent in a molecular state. Also, as disclosed in U.S. Pat. No. 2,870,012, after dissolving in a homogeneous solution, a poor solvent is added to precipitate solid fine particles, or as disclosed in, for example, JP-A-3-182743. Alternatively, a method of dissolving in an alkaline solution and lowering the pH to precipitate solid fine particles can also be used during the primary dispersion.

When preparing these solid fine particle dispersions, it is preferable to add a dispersing aid. Dispersing aids that have been conventionally disclosed include alkylphenoxyethoxysulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkylsulfate, alkylsulfosuccinate, sodium oleylmethyltauride, and naphthalenesulfonic acid. Formaldehyde degenerate, polyacrylic acid, polymethacrylic acid, maleic acrylic acid copolymer, anionic dispersants such as carboxymethylcellulose, cellulose sulfate, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Nonionic dispersants, cationic dispersants and betaine dispersants. In the present invention, the amount of the dispersing aid to be used in the color-forming reducing agent of the present invention is preferably 0.05 to 0.5, more preferably 0.1 to 0.3 in weight ratio. Also, at the time of preparing the solid fine particle dispersion, and / or
Alternatively, after the preparation, a hydrophilic colloid such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polysaccharide, and gelatin can be coexistent for the purpose of stabilizing the dispersion and reducing the viscosity. It is particularly preferable to use gelatin for preventing aggregation. There is no limitation on the method of adding the dispersing aid, and examples thereof include dispersion and / or preparation of solid fine particles.

The color-forming reducing agent of the present invention has the property of dissolving under alkaline conditions. For this purpose, the pH of the dispersion is preferably kept at 8 or less, more preferably at 7 or less. For such pH adjustment, a known acid or alkali can be used. After the preparation of the solid fine particles, the dispersion is preferably subjected to a dispersibility stabilization treatment. Examples of the stabilization treatment include dialysis with a semipermeable membrane (for example, a cellulose membrane), ultrasonic treatment, and addition of a dispersing aid.
In order to incorporate the fine particles of the color-forming reducing agent into the light-sensitive material, the fine particles thus obtained are dispersed in an appropriate binder to prepare a solid dispersion of substantially uniform particles, which is then mixed with a desired dispersion. It can be provided by coating on a support. The binder is not particularly limited as long as it is a hydrophilic colloid that can be used for the photosensitive emulsion layer and the non-photosensitive layer, and usually gelatin or a synthetic polymer such as polyvinyl alcohol or polyacrylamide is used. The color-forming reducing agent of the present invention is used in an amount of 0.01 to 10 per color-forming layer in order to obtain a sufficient color-forming density.
It is preferred to use mmol / 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 reducing agent for color formation of the present invention may be added at any position in the photographic constituting layer, but is added to the emulsion layer or a layer adjacent to the emulsion layer in order to develop the silver halide emulsion quickly during processing. Is preferred.

As couplers preferably used in the present invention, there are compounds having structures represented by the following general formulas (1) to (12). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

[0029]

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[0030]

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[0031]

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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 optionally substituted alkyl group, aryl group or heterocyclic residue. In the general formula (4), R ¹⁶ is an aryl group or a heterocyclic residue which may have a substituent. R
^14, as the R ^15, the substituent that may be R ¹⁶ has, include those mentioned as examples of X ¹ to X ⁵ as described above.

In the general formulas (1) to (4), Y is a hydrogen atom or 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 heterocyclic atom is a saturated or unsaturated monocyclic or condensed 5- to 7-membered ring containing at least one nitrogen, oxygen, sulfur or the like, and examples thereof include succinimide and maleic Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidin-2,4-dione , Thiazolidine-2,4-dione, imidazolidine-2-one, oxazolin-2-one, thiazoline-2
-One, benzimidazolin-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.), halogen atom (eg, chlorine atom, bromine atom, etc.), aryloxy group (eg, phenoxy, 1-naphthoxy, etc.), hetero A ring oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), an acyloxy group (eg, acetoxy, benzoyloxy, etc.),
Alkoxy group (eg, methoxy, dodecyloxy, etc.), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy, etc.), alkoxycarbonyl An oxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), an arylthio group (eg, phenylthio, naphthylthio, etc.), a heterocyclic thio group (eg, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3, 4-oxadiazolylthio, benzimidazolylthio, etc.), alkylthio groups (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy groups (eg, methanesulfonyloxy, etc.), arylsulfonyloxy Si group (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), carbonamide group (eg, acetamide, trifluoroacetamide, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl group ( For example, methanesulfonyl and the like, an arylsulfonyl group (eg, benzenesulfonyl), an alkylsulfinyl group (eg, methanesulfinyl), an arylsulfinyl group (eg, benzenesulfinyl), an arylazo group (eg, phenylazo, naphthylazo) Carbamoylamino group (for example, N-methylcarbamoylamino and the like).

Y may be substituted by a substituent,
Examples of the substituent for substituting Y include those described for X ^{1 to} X ⁵ . Y is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group. General formula (1)
In (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-based 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 with one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or acylamino groups.

In the 5-pyrazolone coupler represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group,
A phenyl group in which ¹⁸ is substituted with one or more halogen atoms is preferred. To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-
Methoxyphenyl group, 2-chloro-5-tetradecanamidophenyl group, 2-chloro-5- (3-octadecenyl-1-succinimido) phenyl group, 2-chloro-5
An aryl group such as -octadecylsulfonamidophenyl group or 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group or an acetyl 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. The general formula (6) represents a coupler called a pyrazoloazole coupler, wherein 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), imidazo [1,2-b] pyrazoles described in U.S. Pat. U.S. Patent No. 4,
No. 500,654, pyrazolo [1,5-b]-
1,2,4-triazoles, U.S. Pat.
No. 067, pyrazolo [5,1-c] -1,2,4
-Triazoles are preferred.

For details of the azole ring substituents represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of a pyrazolotriazole group; A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147245;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 201443 is a pyrazolotriazole coupler having a carboxamide group in the molecule. Y has the same meaning as described above.

Formulas (7) and (8) are couplers referred to as phenol couplers and naphthol couplers, 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 a positive number selected from 0 to 2, and m represents a positive number 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 of R ^{21 to} R ²³ include those described as examples of X ^{1 to} X ^{5 in} the general formulas (II) and (IV). Y has the same meaning as described above.

Preferred examples of the phenolic coupler represented by the general formula (7) include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396;
Nos. 4,334,011, 4,327,173
No. 3,329,729, West German Patent Publication No.
Nos. 2,166-9656, 2,5-diacylaminophenols, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427, No. 767, etc., and 2-phenylureido-5-acylaminophenols. Y is the same as described above.

Preferred examples of the naphthol coupler represented by the general formula (8) include US Pat. No. 2,474,29.
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
No. 200, etc., and 2-carbamoyl-1-naphthols described in US Pat. No. 4,960,889 and the like.
-Carbamoyl-5-amido-1-naphthol type and the like. 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. As the substituents for R ³² , R ³³ and R ³⁴ , X ^{1 to} X
Examples described in ⁵ are given. General formula (9)
Preferable examples of the pyrrolotriazole coupler represented by (12) include EP 488,248 A1,
Couplers in which at least one of R ³² and R ³³ described in JP-A-491,197A1 and JP-A-545,300 are electron-withdrawing groups are exemplified. Y is the same as described above. In addition, couplers having a structure such as fused phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-fused heterocycle, and 5,6-fused heterocycle other than those described above can be used.

US Pat. Nos. 4,327,173 and 4,564,586 disclose fused ring phenol couplers.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used. As the imidazole coupler, couplers described in U.S. Pat. Nos. 4,818,672 and 5,051,347 can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used.

As active methylene and active methine couplers, US Pat. Nos. 5,104,783 and 5,16
The couplers described in 2,196 and the like can be used. 5,5
-As a fused heterocyclic coupler, US Pat.
Pyrrolopyrazole couplers described in JP-A-4,289, and pyrroleimidazole couplers described in JP-A-4-174429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585 and JP-A-4-20473.
No. 0, pyrrolotriazine couplers described in EP-A-556700, and the like can be used.

In the present invention, besides 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. 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 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 20 times the molar amount of the color-forming reducing agent.
It is 1 to 10 times, particularly preferably 0.2 to 5 times.
This range is preferred in that a sufficient color density can be obtained.

The couplers and other additives used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.
High boiling organic solvent (use low boiling organic solvent if necessary)
In water, and then emulsified and dispersed in an aqueous gelatin solution and added to the silver halide emulsion. The high boiling organic solvent that can be used in the present invention is a compound that is immiscible with water having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher and can be used as long as it is a good solvent for the coupler. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C.
That is all. Details of these high-boiling organic solvents are described in Japanese Patent Application Laid-Open No. 62-215272, No. 137.
It is described in the lower right column of the page to the upper right column of page 144. A known polymer dispersion method may be used for dispersing the coupler.
Specific examples of the latex dispersion process as a polymer dispersion and the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application No. (OLS) 2,541,274
No. 2,541,230, JP-B-53-4109
No. 1 and European Patent Publication No. 029104, and a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723. The average particle size of the lipophilic fine particles containing a coupler or the like used in the present invention is not particularly limited, but is preferably 0.05 to 0.3 μm from the viewpoint of color development. Further, the thickness is more preferably 0.05 μm to 0.2 μm. Generally, in order to reduce the average particle size of lipophilic fine particles, it is necessary to select the type of surfactant, increase the amount of surfactant used, increase the viscosity of the hydrophilic colloid solution, This can be achieved by lowering the viscosity by using a low boiling organic solvent in combination, or by increasing the shearing force such as increasing the rotation of the stirring blade of the emulsifying device, or by lengthening the emulsifying time. The particle size of the lipophilic fine particles can be measured by, for example, a device such as Nanosizer manufactured by Coulter, UK.

In the present invention, when the dye formed from the color-forming reducing agent and the dye-forming coupler is a diffusible dye, it is preferable to add a mordant to the light-sensitive material. When the present invention is applied to such a form, it is not necessary to immerse the film in an alkali to form a color, so that the image stability after processing is remarkably improved. The mordant may be used in any of the layers, but when added to a layer containing the color-forming reducing agent of the present invention, the stability of the color-forming reducing agent deteriorates. It is preferably used for a layer that does not contain.
Furthermore, the dye formed from the color-forming reducing agent and the coupler diffuses through the swollen gelatin film during the treatment and dyes 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, since the dye formed from the color-forming reducing agent of the present invention and the coupler of the present invention is a water-soluble dye, it 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, when a barrier layer as described in JP-A-7-168335 is provided on the side opposite to the support with respect to the layer to which the mordant is added, the layer to which the mordant is added contains a color-forming reducing agent. It is also preferably on the same side as the support with respect to the layer being made.

The mordant of the present invention may be added to a plurality of layers. Particularly, when a plurality of layers contain a color-forming reducing agent, the mordant is added to each adjacent layer. Is also preferred. The coupler forming the diffusible dye may be any coupler as long as the diffusible dye formed by coupling with the color-forming reducing agent of the present invention reaches the mordant, but the diffusible dye formed is pKa
(Acid dissociation constant) It is preferable to have one or more dissociating groups of 12 or less, more preferably one or more dissociating groups of pKa 8 or less, and particularly preferably a dissociating group of pKa 6 or less. The molecular weight of the formed diffusible dye 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.
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 coupler for forming the diffusible dye is 1 × 10 4 in an alkaline solution having a pH of 11 until the solubility of the diffusible dye formed by coupling with the reducing agent for color formation of the present invention is up to 25 ° C.
^-6 mol / liter or more is preferable, and 1 × 10
^-5 mol / liter or more preferably 1 ×
It is particularly preferred that the dissolution is 10 ^-4 mol / l or more.
The coupler forming the diffusible dye is dissolved in an alkaline solution having a diffusion constant of 25 ° C. and a pH of 11 at a concentration of 10 ⁻⁴ mol / liter in an alkaline solution having a diffusible dye formed by coupling with the color-forming reducing agent of the present invention. In this case, it is preferably 1 × 10 ⁻⁸ m ² / s ⁻¹ or more, more preferably 1 × 10 ⁻⁷ m ² / s ⁻¹ or more, and 1 × 10 ⁻⁶ m ² / s ^−. It is particularly preferred that it is ¹ or more.

The mordant that can be used in the present invention can be arbitrarily selected from mordants commonly used.
Among them, a polymer mordant is particularly preferable. Here, the polymer mordant is a polymer having a tertiary amino group,
Examples of the polymer include a polymer having a nitrogen-containing heterocyclic moiety, and a polymer including a quaternary cation group. Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include U.S. Pat.
No. 05, No. 4,115,124, No. 3,148,
No. 061, JP-A-60-118834 and JP-A-60-12
No. 2941, No. 62-244043, No. 62-244
The following may be mentioned, including the mordant layer described in No. 036 and the like.

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. No. 4,124,386 and U.S. Pat. No. 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. 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.

Other 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
No. 8, No. 1,277,453, and the like, polymer mordants crosslinkable with gelatin and the like; US Pat. Nos. 3,958,995 and 2,721,85
No. 2,798,063, JP-A-54-115
No. 228, No. 54-145529, No. 54-2602
No. 7,898,088; water-insoluble mordant disclosed in U.S. Pat. No. 3,898,088; U.S. Pat. No. 137333) Reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification and the like; further, U.S. Pat. Nos. 3,709,690, 3,788,855, and 3,642,482. 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. As the hydrophilic colloid, a hydrophilic colloid, a highly hygroscopic polymer or both of them can be used, and gelatin is 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, preferably for use in the 0.5 to 8 g / m ^2. In the present invention, it is not necessary to use the auxiliary developing agent and its precursor in the light-sensitive material or the developing solution, but they may be used if necessary. The auxiliary developing agent used in the present invention is a compound having an action of promoting electron transfer from a color-forming reducing agent to silver halide in the course of developing silver halide grains, and is preferably an exposed silver halide. A compound capable of developing particles and oxidizing the particles to oxidize a color-forming reducing agent (hereinafter referred to as cross-oxidation). As the auxiliary developing agent, pyrazolidones, dihydroxybenzenes, reductones or aminophenols are preferably used, and pyrazolidones are particularly preferably used. The diffusivity of these compounds in the hydrophilic colloid layer is preferably 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% or less. 0.01% or less. 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).

Formula (A) A- (L) _n -PUG A represents a block group in which the bond to (L) _n -PUG is cleaved during development processing, and L represents L and A in formula (A). Represents a linking group in which the bond between L and PUG is cleaved after the bond is cleaved, n represents an integer of 0 to 3, and PUG represents an auxiliary developing agent. As the auxiliary developing agent, an electron-emitting compound according to the Kender Rupertz rule other than the p-phenylenediamine compounds is used, and the above-mentioned pyrazolidones are preferably used. As the blocking group represented by A, the following known ones can be applied. That is, a blocking group such as an acyl group or a sulfonyl group described in U.S. Pat. No. 3,311,476, a blocking group utilizing a reverse Michael reaction described in JP-A-59-105542 or the like;
No. 280140, a blocking group utilizing quinone methide or a compound similar to quinone methide by intramolecular electron transfer, JP-A-63-318555 (European Patent Publication 0)
No. 295729), a blocking group utilizing an intramolecular nucleophilic substitution reaction, a blocking group utilizing an addition reaction of a nucleophile to a conjugated unsaturated bond described in JP-A-4-186344, and the like. 62-163051, a blocking group utilizing a β-elimination reaction, JP-A-61-188540, a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes, and JP-A-62-187850. Group utilizing the Rossen rearrangement reaction of
No. 7457, a blocking group utilizing the reaction between an N-acyl compound of thiazolidine-2-thione and an amine, and a di-reactive compound having two electrophilic groups described in WO 93/03419. Blocking groups that react with a nucleating agent can be exemplified. 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, and is not particularly limited as long as it has this function. . Specific examples of the auxiliary developing agent or its precursor are shown below, but the compounds used in the present invention are not specifically limited thereto.

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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, but when the auxiliary developing agent is contained, it is preferably used by adding it to the non-photosensitive layer. As a method of incorporating these compounds into the photosensitive material, a method of dissolving in a water-miscible organic solvent such as methanol and directly adding the compound to the hydrophilic colloid layer, and coexisting with a surfactant to form an aqueous solution or a colloidal dispersion. The method of addition, after dissolving in a solvent or oil that is substantially immiscible with water,
A method of adding a substance dispersed in water or a hydrophilic colloid, a method of adding a dispersion in the form of a solid fine particle dispersion, and the like can be used, and a conventionally known method can be applied alone or in combination. The method for preparing the solid fine particle dispersion is described in detail in page 20 of JP-A-2-23544. The amount added to the light-sensitive material is from 1 mole% to the color-forming reducing agent.
It is 200 mole%, preferably 5 mole% to 100 mole%, more preferably 10 mole% to 50 mole%.

In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used.
Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51-52. Using three primary colors of yellow, magenta and cyan,
In order to obtain a wide range of colors on the chromaticity diagram, at least three silver halide emulsion layers having sensitivity to different spectral regions are used in combination. For example, blue layer,
There are three layers of a green sensitive layer and a red sensitive layer, a combination of a green sensitive layer, a red sensitive layer, and an infrared sensitive layer. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary. Photosensitive materials include protective layers, undercoat layers, intermediate layers,
Various auxiliary layers such as an antihalation layer and a back layer can be provided. Further, various filter dyes can be added to improve color separation.

The silver halide emulsion which can be used in the present invention includes:
Any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Also,
A so-called core-shell emulsion having a layer in which the inside of the grain and the surface layer of the grain are different may be used, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and a method of adjusting the gradation by mixing monodispersed emulsions as described in JP-A-1-167,743 and JP-A-4-223,643 is preferably used. . The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other. Specifically, US Pat. No. 4,500,626
No. 50, column 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,0
29 (1978), No. 17, 643 (December, 1978), pp. 22-23, and No. 18, 716 (1979).
No. 307, 105 (198).
Nov. 9, pp. 863-865, JP-A-62-253,
No. 159, No. 64-13,546, JP-A-2-23
No. 6,546, No. 3-110, 555, and Grafkid, "Physics and Chemistry of Photography", published by Paul Monte (P.Gl.
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), Duffin's Photographic Emulsion Chemistry, published by Focal Press (GFDuffin, Photographic Emulsion Che)
mistry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman, Focal Press (VLZelikma)
n et al., Making and Coating Photographic Emulsion,
Focal Press, 1964) and the like can be used.

The use of the above tabular grains has advantages such as an increase in covering power and an increase in the color sensitization efficiency of a sensitizing dye. I have. The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. As the shape of the average particle, a triangle, a hexagon, a circle, or the like can be selected. A regular hexagon having approximately equal six sides as described in U.S. Pat. No. 4,798,354 is a preferred form. The equivalent circle diameter of the projected area is often used as the average particle size. However, particles having an average diameter of 0.6 μm or less as described in US Pat. preferable. Also, U.S. Pat.
Emulsions having a narrow grain size distribution as described in US Pat. No. 5,617 are also preferred. It is preferable to limit the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, are also preferable. In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. Also, it is possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, to introduce them throughout the grains, or to introduce them only to a specific portion of the grains, For example, dislocations can be introduced only in the fringe portion of the particles. Introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of irregular grains typified by normal crystal grains or potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron, osmium and chromium for various purposes. These compounds may be used alone or in combination of two or more. In addition, these compounds can be added as salts such as chlorides, bromides, and cyanides, as well as various complex salts. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide.
Also, when it is contained, it may be uniformly introduced into the particles,
Further, it may be localized inside or on the surface of the particle. Specifically, Japanese Patent Application Laid-Open Nos. 2-236542 and 1-11663
No. 7, JP-A-5-181246 and the like are preferably used. Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the added silver salt and halogen salt may be increased (Japanese Patent Application Laid-Open No. 55-142,329).
No. 55-158,124; U.S. Pat.
No. 0,757). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is between 2.2 and 8.5, more preferably between 2.5 and 7.5. The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. Chemical sensitization of the photosensitive silver halide emulsion of the present invention includes:
Known sulfur sensitization method, selenium sensitization method, chalcogen sensitization method such as tellurium sensitization method, noble metal sensitization method using gold, platinum, palladium and the like, reduction sensitization method and the like may be used alone or in combination. (For example, see JP-A-3-110,5)
No. 55, JP-A-5-241267, etc.). Examples of tellurium sensitizers include Canadian Patent No. 800,958, British Patent Nos. 1,295,462 and 1,396,696.
The compounds described in Japanese Patent Application Nos. 2-333819 and 3-131598 can be used, and specific tellurium sensitizers include colloidal tellurium and telluroureas (for example,
Tetramethyltellurourea, N-carboxyethyl-
N ′, N′-dimethyltellurourea, N, N′-dimethylethylenetellurourea), isotellurocyanates, telluroketones, telluramides, tellurohydrazides, telluroesters, phosphine tellurides (for example, tributylphosphine) Butyldiisopropylphosphine telluride), other tellurium compounds (for example, potassium tellurocyanate, telluropentathionate sodium salt) and the like. The amount of tellurium sensitizer used is about 10 ^{-7 to} 5 × 10 ^-2 mol, preferably about 5 × 10 ^-7 to 10 ^-3 mol, per mol of silver halide. It is preferable to use an oxidizing agent for silver during the production process of the silver halide emulsion. Preferred oxidants are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidants of thiosulfonates and organic oxidants of quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. A method of performing reduction sensitization after using an oxidizing agent,
The reverse method or a method in which both coexist simultaneously can be used. These methods can be selectively used in both the grain formation step and the chemical sensitization step.
These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, the methods described in JP-A-5-45,833 and JP-A-62-40,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.
5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 10.5, more preferably 6.8 to 8.5.
9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to make the photosensitive silver halide used in the present invention have green sensitivity, red sensitivity and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, heminanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat.
Sensitizing dyes described in JP-A-617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The addition amount is generally 10 ^-5 to 10 ^-2 per mol of silver halide.
It is about a mole.

The additives used in such a process and known photographic additives which can be used for the light-sensitive material and the dye-fixing material are described in RD Nos. 17,643 and 18,71.
No. 6 and Nos. 307, 105, and the relevant portions are summarized in the following table.

Types of Additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right column 866-868 Page Supersensitizer 剤 Right column on page 649 4. Fluorescent brightener 24 page 648 right column 868 page 5. Fogging prevention 24-25 page 649 right column 868-870 agent, stabilizer 6. Light absorber Page 25-26 page 649 right column page 873 filter ~ page 650 left column dyes, ultraviolet absorbers. Anti-stain agent, page 25, right column, page 650, left column to right column, page 872 8. Dye image, page 25, page 650, left column, page 872 Stabilizer 9. Hardening agent, page 26, page 651, left column, 874-875 10. Binder, page 26 Page 651, left column 873-874 11. Plasticizer, page 27 page 650 right column 876 lubricant Lubricant 12. Coating aid, page 26-27 page 650 right column 875-876 Surface active agent 13. Static 27 pages 650 Right column on page 876-877 Inhibitor 14. Matto agent 878-879

As the binder for the constituent layers of the light-sensitive material, hydrophilic binders are preferably used. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13 / 1988.
No. 546, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, and examples thereof include gelatin and gelatin derivatives. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination.

Other techniques and inorganic / organic materials which can be used in the color photographic light-sensitive material of the present invention are described in the following portions of European Patent No. 436,938A2 and the patents cited below. 1. 1. Layer structure: page 146, line 34 to page 147, line 25 2. Yellow coupler: page 137, line 35 to page 146, line 33, page 149, lines 21 to 23 3. Magenta coupler: page 149, line 24 to line 28; EP 421,453A1, page 3, line 5 to page 25, line 55 4. Cyan coupler: page 149, lines 29 to 33; EP 432, 804A2, page 3, line 28 to page 40, line 2 5. Polymer coupler: page 149, lines 34 to 38; EP 435, 334A2, page 113, line 39 to page 123, line 37 6. Colored coupler: page 53, line 42 to page 137, line 34, page 149, line 39 to line 45 Other functionality: page 7, line 1 to page 53, line 41, page 149, 46 coupler line to page 150, line 3; EP 435, 334A2, page 3, line 1 to Page 29, line 50 8. 8. Antiseptic / antifungal agent: page 150, lines 25-28 Formalin: page 149, lines 15 to 17 Scavenger 10. Other additives: page 153, lines 38 to 47; Line 27, page 40 to page 37, line 40 11. Dispersion method: page 150, lines 4 to 24 12. Support: page 150, lines 32 to 34 13. Film thickness -Film properties: page 150, lines 35 to 49 14. Desilvering step: page 151, line 48 to page 152, line 53 15. Automatic developing machine: page 152, line 54 to page 153, 2 Line 16. Washing and stabilization process: page 153, lines 3 to 37

Examples of a method of exposing and recording an image on a photosensitive material include a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or a enlarger, Scanning and exposing the original image through slits and the like using a copier exposure device, etc., light emitting diodes and various lasers (laser diodes,
A method of performing scanning exposure by emitting light such as a gas laser (Japanese Patent Application Laid-Open No. 2-129625, Japanese Patent Application Laid-Open No. 5-17614)
No. 4, No. 5-199372, No. 6-127022), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., directly or through an optical system. Exposure method.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No. 4,500,626, column 56, natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc., JP-A-2-53,37.
No. 8, No. 2-54, 672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of expressing nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate, potassium dihydrogen phosphate (KD)
P), lithium iodate, BaB ₂ O _{4 and} other inorganic compounds, urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. An image signal generated using a computer represented by a signal, CG, or CAD can be used.

The method of developing after exposure of the light-sensitive material containing a color-forming reducing agent of the present invention includes an activator processing method of developing with an alkaline processing solution not containing a color-developing agent, and 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 photosensitive material and is developed with a processing solution containing no color-forming developing agent. In the present invention, the "activator liquid" is characterized in that it does not substantially contain a p-phenylenediamine-based color developing agent as conventionally used, and other components (eg, alkali, halogen, chelating agent, etc.) ) May be included. 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 / l or less, more preferably 0.1 mmol / l or less. In particular, it is preferable not to contain at all. The pH of the alkaline treatment liquid is preferably from 9 to 14, and particularly preferably from 10 to 13. For the activator processing photosensitive material and its processing,
For example, Japanese Patent Application Nos. 7-63572 and 7-334190.
Nos. 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). The photosensitive material having a mordant layer for capturing and mordanting a diffusible dye formed from the photosensitive layer / dye-forming layer on the same support or on a separate support is subjected to alkaline treatment. This means that the liquid is developed with a thickness of about 500 μm or less, preferably 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. In the case of the diffusion transfer method, the pH of the alkaline treatment liquid is preferably from 10 to 14, and particularly preferably from 12 to 14. See THJames, The Theory of Photo
Graphic Process 4th Edition (1977, Macmillan)
The specific structure of the 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
No. 252551, U.S. 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 light-sensitive material after developing the alkaline processing solution is described in JP-B-7-122753, U.S. Pat. No. 4,139,383, and RD-No. 16102. The timing layer used in combination with the neutralizing layer is described in JP-A-54-136328, U.S. Pat. Nos. 4,267,262 and 4,009,030.
No. 4,268,604. Although any emulsion can be used as the silver halide emulsion, preferred autopositive emulsions as photosensitive materials for photography include JP-A-7-333770 and JP-A-7-337377. In addition, if necessary, a light-shielding layer, a reflective layer, an intermediate layer, an isolation layer, an ultraviolet absorbing 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.
No.

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,
Nebletts Handbook of Photography and Reprography,
7th Ed. (Van Nostrand and Reinhold Company) 32-
33 pages, U.S. Pat. Nos. 3,152,904 and 3,3
No. 01,678, No. 3,392,020, No. 3,
No. 457,075, British Patent No. 1,131,108,
No. 1,167,777 and Research Disclosure Magazine, June 1978, pages 9 to 15 (RD-17).
029).

The light-sensitive material of the present invention is prepared in accordance with US Pat.
Nos. 4,657,848 and 5 (published by Aztec Co., Ltd. on March 22, 1991), pages 55 to 86, etc. 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 heat-treat a low-boiling solvent or a mixed solvent of a low-boiling solvent and water or the basic aqueous solution in a light-sensitive material or a processing sheet. As a method using water, JP-A-63-144354 and JP-A-63-14 are known.
4,355, 62-38,460, JP-A-3-2
10,555, JP-A-62-253,159, and 6
3-85,544, EP 210,660 and U.S. Pat. No. 4,740,445. The present invention relates to JP-A-7-261336 and JP-A-7-268.
No. 045, No. 8-30103, No. 8-46822, and No. 8-97344. The heating temperature in the thermal development step is about 50 ° C to 200 ° C.
C. to 150.degree. C. is useful, and when a solvent is used, it is preferably used at a temperature not higher than its boiling point.

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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 (Preparation of Coloring Reducing Agent Solid Dispersion (K-1)) 500 m
140 ml of pure water, 20 g of a 5% aqueous solution of polyethylene glycol (average molecular weight 2000) in a 1 l dispersion container,
40 g of a color-forming reducing agent (21) and a diameter of 0.5 to 0.75
200 ml of glass beads of 3000 mm. p. m. For 30 minutes. 200 m of a 10% aqueous solution of the obtained dispersion and lime-processed gelatin
and the pH is adjusted to 6.5 with 2N sulfuric acid, and a solid dispersion of a color-forming reducing agent having a particle size of 1.0 μm or less (K-1)
I got Solid dispersions K-2 to K-5 of the color-forming reducing agent in the same manner as in the preparation of K-1, except that the color-forming reducing agent in K-1 was replaced with the color-forming reducing agent shown in Table A in an equimolar amount. Was prepared.

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[Table 1]

(Preparation of Photosensitive Material) 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. A multilayer color printing paper (100) having the following layer configuration was produced. The coating liquid was prepared as follows: 17 g of coupler (C-76) and a color-forming reducing agent (I-1)
20 g and a solvent (Solv-1) 80 g were dissolved in ethyl acetate, and this solution was added to a 16% gelatin solution 400% containing 10% sodium dodecylbenzenesulfonate and citric acid.
Then, emulsified dispersion A was prepared by emulsifying and dispersing the mixture in an amount of 1 g. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of large-sized emulsion A having an average grain size of 0.88 μm and small-sized emulsion A having an average grain size of 0.80 μm (silver molar ratio). Coefficient of variation in grain size distribution) And 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the surface of silver chloride-based grains in each size emulsion). This emulsion contains the following blue-sensitive sensitizing dyes A, B, and C in an amount of 1.4 × 10 ⁻⁴ mol per mol of silver per mol of silver, and 1.4 × 10 ^-4 mol per mol of silver. , Each 1.7 × 10 ^-4
Mole is added. 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.

The coating solutions for the second to seventh 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, was added to a 50.0 mg / m ² and 10.0 mg / m ^2. The size of the silver chlorobromide emulsion in each photosensitive emulsion layer was adjusted by the same adjustment method as that for the silver chlorobromide A, and the following spectral sensitizing dyes were used. Blue-sensitive emulsion layer

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Green-sensitive emulsion layer

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(The sensitizing dye D was used in an amount of 3.0 × 10 ^-4 mol for a large-size emulsion, 3.6 × 10 ^-4 mol for a small-size emulsion, and Sensitizing dye E was used in an amount of 4.0 × 10 ^-5 mol per mol of silver halide and 7.0 mol per mol of silver halide.
× 10 ^-5 mol, and 2.0 × 10 ^-4 mol of sensitizing dye F per mol of silver halide per mol of silver halide, and 2.8 × 10 ^-4 mol of sensitizing dye F per mol of silver halide. Red-sensitive emulsion layer

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(Each mole of silver halide was added in an amount of 5.0 × 10 ⁻⁵ mol for a large-sized emulsion and 8.0 × 10 ⁻⁵ mol for a small-sized emulsion, respectively.) The following compound was further added to the layer (red-sensitive layer) in an amount of 2.6 × 10 ⁻² mol per mol of silver halide.

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The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
3.5 × 10 ^-4 mole, 3.0 × 10 ^-3 mole per mole,
2.5 × 10 ^-4 mol was added. In addition, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. To prevent irradiation, the following dyes were added to the emulsion layer (the values in parentheses indicate the coating amount).

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.20 gelatin 1.50 Yellow coupler (C-76) 0.17 Coloring reducing agent (I-1) 0.20 Solvent (Solv-1) 0.80

Second layer (color mixture prevention layer) Gelatin 1.09 Color mixture inhibitor (Cpd-7) 0.11 Solvent (Solv-2) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 Solvent (Solv-5) 0.09 1,5-diphenyl-3-pyrazolidone 0.03 (fine particle solid dispersion state) Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B (cubic, A 1: 3 mixture (Ag molar ratio) of a large emulsion B having an average grain size of 0.55 μm and a small emulsion B having a mean grain size of 0.39 μm, the variation coefficients of the grain size distribution being 0.10 and 0.08, respectively. For each size emulsion, 0.8 mol% of AgBr was locally contained on a part of the surface of silver chloride-based particles.) 0.20 Gelatin 1.50 Magenta coupler (C-56) 0.24 For coloring Reducing agent (I-1) 0 solvent (Solv-1) 0.80

Fourth layer (color mixture prevention layer) Gelatin 0.77 Color mixture prevention agent (Cpd-7) 0.08 Solvent (Solv-2) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 1,5-diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state) Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture (Ag molar ratio) of large-size emulsion C with an average grain size of 0.5 μm and small-size emulsion of 0.41 μm, with a variation coefficient of particle size distribution of 0.09 and 0.11, each size In the emulsion, 0.8 mol% of AgBr was locally contained in part of the surface of the silver chloride-based grains.) 0.20 gelatin 0.15 cyan coupler (C-43) 0.21 reducing agent for color formation (I-1) 0.20 Solvent (So lv-1) 0.80

Sixth layer (ultraviolet absorbing layer) Gelatin 0.64 Ultraviolet absorbing agent (UV-1) 0.39 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.05 Seventh 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

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Sample (100) was prepared in exactly the same manner as Sample (100) except that the coupler and the color-forming reducing agent were replaced with the couplers and color-forming reducing agents shown in Table a in equimolar amounts. 101) to (104) were produced. Sample (1
00) to remove the color-forming reducing agent in the emulsified dispersion,
The couplers were replaced with the couplers shown in Table a in equimolar amounts, and a solid dispersion of the color-forming reducing agent shown in Table a was added to each emulsion layer so that the amount of the color-forming reducing agent contained was equimolar. Further, except that 1,5-diphenyl-3-pyrazolidone was removed from the second layer and the third layer which were the color mixture preventing layers, the sample (20) was produced in the same manner as in the preparation of the sample (100).
0) to Sample (204) were prepared. However, the total amount of gelatin in each emulsion layer was matched with the sample (100).

For the sample (200), the couplers were replaced with the couplers shown in Table a in an equimolar amount, and the solid dispersions of the color-forming reducing agents in the first, third and fifth layers were colored as shown in Table a. The solid dispersion of the reducing agent is replaced by an equal weight, and the solid dispersion of the reducing agent for coloring in the first layer, the third layer and the fifth layer is further changed to the second layer and the fourth layer which are the color mixture preventing layers. A sample (30) was prepared in exactly the same manner as the sample (200) except that the sample (30) was evenly distributed.
0) to (304) were prepared. However, the total amount of gelatin in each layer was matched with the sample (200). All the samples prepared as described above were subjected to gradation exposure of a three-color separation filter for sensitometry using a FWH type photometer (color temperature of light source: 3200 ° K) manufactured by Fuji Film Co., Ltd.
The exposed sample was processed in the following processing steps using the following processing solutions. Processing process Temperature Time Color development 40 ° C 30 seconds Bleaching and fixing 40 ° C 45 seconds Rinse Room temperature 90 seconds

Developing solution (alkali activating solution) Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml Fluorescent whitening agent (UVX) 2 g Add water 1000 ml pH (at 25 ° C / potassium hydroxide) 12

Bleaching / fixing solution Water 600 ml Ammonium thiosulfate (700 g / l) 93 ml Ammonium sulfite 40 g Ammonium iron (III) ethylenediaminetetraacetate 55 g 2 g ethylenediaminetetraacetic acid 30 g Nitric acid (67%) 30 g Water was added and 1000 ml pH (at 25 ° C./acetic acid and aqueous ammonia) 5.8 Rinse solution 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

[0131]

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The maximum color density of the processed sample was measured with red light, green light and blue light. The results are shown in Table a.
Each untreated sample was left for one week at a temperature of 80 ° C. and a humidity of 70%, and then subjected to the following treatment steps. Processing time Temperature Time Bleaching and fixing 40 ° C 45 seconds Rinse Room temperature 45 seconds

[0133]

[Table 2]

[0134]

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The bleach-fixing solution and the rinsing solution described above were used. Each sample after the treatment was measured with red light, green light, and blue light. Unexposed stain (Dm
inR, DminG, DminB) are shown in Table a. As is clear from Table a, when the color-forming reducing agent was contained in the emulsified dispersion of oil, the stain of the unexposed portion increased when the unprocessed photosensitive material was stored for a long time under high temperature and high humidity. However, in the sample using the solid dispersion of the color-forming reducing agent of the present invention, such an increase in stain is suppressed. Further, it can be seen that when the solid dispersion of the color-forming reducing agent of the present invention is used, high color-forming properties are exhibited as in the case where the color-forming reducing agent is contained in an oil emulsified dispersion. Furthermore, comparing the case where the solid dispersion of the color-forming reducing agent of the present invention is added to the photosensitive emulsion layer containing the coupler and the case where it is added to the color mixture preventing layer adjacent to the photosensitive emulsion layer, the latter is the former. It can be seen that, although the color density is slightly lower than that of the above, the stain in the unexposed portion can be further suppressed. In a similar experiment in which a sample after treatment was stored for a long period of time under high temperature and high humidity, it was found that the increase in stain was similarly suppressed in the sample using the solid dispersion of the coloring agent of the present invention. . Further, the sample using the solid dispersion of the color-forming reducing agent of the present invention had lower color mixing than the comparative sample.

Example 2 The silver chlorobromide emulsions A, B and C of the first layer, the third layer and the fifth layer of the sample (100) of Example 1 are shown below as silver chlorobromide emulsions D, E and A sample (400) having exactly the same components as in Example F except that the coated silver amount was changed to 0.01 g, 0.01 g and 0.015 g per 1 m ² , respectively. Silver chlorobromide emulsion D: cubic, average grain size 0.10 μm
3: 7 mixture of large size emulsion D of the formula (1) and small size emulsion D of 0.08 μm (Ag molar ratio). The variation coefficients of the grain size distribution were 0.08 and 0.10, respectively, and 0.3 mol% of AgBr was locally contained in a part of the grain surface containing silver chloride as a base in each size emulsion. Chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer.

For the silver chlorobromide emulsion D, the following blue-sensitive sensitizing dyes A, B, and C used in Example 1 were used. (Sensitizing dyes A, B, and C were each contained in 7.0 × 10 ^-4 mole for large-size emulsion D and ^8.10-4 mole for small-size emulsion D, respectively, per mole of silver halide. 5x
10 ^-4 mol was added. ) Silver chlorobromide emulsion E: cubic, average grain size 0.10 μm
1: 3 mixture (Ag molar ratio) of the large size emulsion E and the small size emulsion E of 0.08 μm. 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.

The following amounts of the green sensitizing dyes D, E and F used in Example 1 were used in the silver chlorobromide emulsion E. (Sensitizing dye D was used in an amount of 1.5 × 10 ⁻³ mol per mol of silver halide and 1.8 × 10 ³ mol per mol of silver halide.
× 10 ^-3 mol, and 2.0 × 10 ^-4 mol of the sensitizing dye E per mol of silver halide for a large-sized emulsion and 3.5 × 10 ^-4 mol for a small-sized emulsion. The sensitizing dye F was used in an amount of 1.0 × 10 ⁻³ mol per mol of silver halide per mol of silver halide, and 1.0 × 10 ⁻³ mol per mol of silver halide.
4 × 10 ^-3 mol) Silver chlorobromide emulsion F: cubic, average grain size 0.10 μm
1: 4 mixture of a large-size emulsion F and a small-size emulsion F of 0.08 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and AgBr was used for each size emulsion.
0.8 mol% was locally contained in a part of the surface of the silver chloride-based grain.

The red sensitizing dyes G and H used in Example 1 were used in the silver chlorobromide emulsion F in the following amounts. (2.5 × 1 each for large size emulsions per mole of silver halide)
0 ^-4 moles, and 4.0 × 10 ^-4 for small size emulsions
Mole was added. Table b) Couplers and reducing agents for coloring for sample (400)
The sample (4) was prepared in exactly the same manner as in the preparation of the sample (400) except that the coupler and the color-forming reducing agent were replaced by equimolar amounts.
01) to (404). For Sample (400), the color-forming reducing agent in the emulsified dispersion was removed, the couplers were replaced with the couplers shown in Table b in equimolar amounts, and the solid-state dispersion of the color-forming reducing agent shown in Table b in each emulsion layer. Was added in such a manner that the amount of the color-forming reducing agent contained was equimolar, and further, the 1,5-
Samples (500) to (504) were prepared in the same manner as in the preparation of Sample (400) except that diphenyl-3-pyrazolidone was removed. However, the total amount of gelatin in each emulsion layer was combined with the sample (400).

For the sample (500), the couplers were replaced with the couplers shown in Table b in equimolar amounts, and the solid dispersions of the color-forming reducing agents in the first, third and fifth layers were colored as shown in Table b. The solid dispersion of the reducing agent is replaced by an equal weight, and the solid dispersion of the reducing agent for coloring in the first layer, the third layer, and the fifth layer is replaced with the second layer, the fourth layer, which is a color mixture prevention layer. A sample (60) was prepared in exactly the same manner as the sample (500) except that the sample was transferred evenly.
0) to (604). However, the total amount of gelatin in each layer was matched with the sample (500).

[0141]

[Table 3]

After the same exposure as in Example 1 was performed using this sample, the developing solution used in Example 1 was intensified with a 0.3% aqueous solution of hydrogen peroxide at pH 12.0 to which hydrogen peroxide was added. As a result of processing, an image having a high maximum density similar to that of Example 1 was obtained even when a photosensitive material having a significantly reduced silver content was used.
Further, the sample using the solid dispersion of the color-forming reducing agent of the present invention had good storability of the photosensitive material, and obtained a clear image with little stain and little color mixing even after storage under high temperature and high humidity conditions. . It has been found that the light-sensitive material of the present invention is also preferable for amplified image formation by intensifying processing of a low silver light-sensitive material.

Example 3 Samples (100) to (104) and (200) to of Example 1
Using (204) and (300) to (304), the same processing and evaluation as in Example 1 were performed, except for performing the following exposure. (Exposure) As a light source, a semiconductor laser GaAlAs (oscillation wavelength,
YAG solid-state laser (oscillation wavelength: 946 nm) with excitation light source of 808.5 nm) was converted to a wavelength of 473 nm by a KNbO ₃ SHG crystal, and a semiconductor laser GaAlAs was obtained.
(Oscillation wavelength, 808.7 nm) as excitation light source YVO ₄
532nm AlGaInP obtained by converting the wavelength of a solid laser (oscillation wavelength, 1064nm) using KTP SHG crystal
(Oscillation wavelength, about 670nm: Toshiba type No.TOLD921
1) was used. Each of the laser beams is a device capable of sequentially scanning and exposing a color photographic paper moving in a direction perpendicular to a scanning direction by a rotating polyhedron. Using this apparatus, the relationship D-log E between the density (D) of the photosensitive material and the light amount (E) was obtained by changing the light amount. At this time, the laser light of three wavelengths modulates the light amount using an external modulator,
Exposure was controlled. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 10 ⁻⁸ seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress fluctuations in light quantity due to temperature. As a result, even in an image formed by high-illuminance digital exposure, an image having a high maximum density can be obtained, and the sample using the solid dispersion of the color-forming reducing agent of the present invention has good storability of the photosensitive material. Thus, a clear image with less stain and less color mixture was obtained even after storage under high temperature and high humidity conditions.

[0144]

The present invention is characterized in that the color-forming reducing agent is contained in a solid dispersion state. The most commonly considered method of incorporating a color-forming reducing agent into a light-sensitive material is a method of co-emulsifying oil with a coupler in oil. However, in this method, since the color-forming reducing agent and the coupler are present in the same oil droplet, when the color-forming reducing agent is oxidized during raw storage of the photosensitive material or during storage after processing, a coupling reaction with the coupler is easily caused. As a result, stains are generated by the formed dye. Such stains can be reduced by using the color-forming reducing agent of the present invention,
Was not enough. However, by dispersing the color-forming reducing agent of the present invention in a solid state, it was possible to separate the coupler from the coupler during storage, and such stains could be prevented. Further, when a color-forming reducing agent is contained in the oil droplets, it is unlikely to cause a direct oxidation-reduction reaction with silver halide, and therefore, an auxiliary developing agent must be contained in the processing solution or the photosensitive material. When the auxiliary developing agent is contained in the processing solution, the stability of the processing solution becomes a problem. When the auxiliary developing agent is contained in the photographic material, the stability of the auxiliary developing agent in the photographic material becomes a problem. When an auxiliary developing agent is used when two or more photosensitive emulsion layers are used, color mixing occurs due to diffusion of the oxidized auxiliary developing agent.
By containing the color-forming reducing agent in the photosensitive material in a solid dispersion state as in the present invention, the color-forming reducing agent can directly cause a redox reaction with silver halide, eliminating the need to use an auxiliary developing agent. It was possible to solve the above-mentioned problem derived from such an auxiliary developing agent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication G03C 7/00 530 G03C 7/00 530

Claims (4)

[Claims] 1. A color forming reducing agent represented by the following general formula (D-1) in a solid dispersion state in any one of photographic constituent layers on a support, and at least one kind of dye formation. A silver halide photographic material comprising a coupler. Embedded image In the formula, Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. X represents a —CO— group or a —SO ₂ — group;
Represents 1 or 0. R represents a carbon atom, a linear, branched or cyclic alkyl group, an aromatic hydrocarbon group, an aromatic or non-aromatic heterocyclic group, an acyloxy group, an alkoxy group, an aryloxy group or an amino group. 2. The silver halide photographic material according to claim 1, wherein X in the general formula (D-1) is a —CO— group, and n is 1. 3. The coated silver halide amount obtained by adding the silver halide amounts of all the coated layers is 0.003 to 0.3 g in terms of silver.
/ M ^{2. The} silver halide photographic light-sensitive material according to claim 1 or 2, wherein 4. An exposure time per pixel of 10 ^-8 to 10
^{4. The} silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material is used for scanning exposure with a beam having an overlap between adjacent rasters in ^-4 seconds.