JP2000019698A - Treatment of silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treating method of a silver halide photographic sensitive material by which a rapid treatment is possible, high image density is obtd. without using a high pH treating liquid and excellent preservable property of a dye image to be formed is obtd. SOLUTION: In this method, a silver halide photographic sensitive material containing photosensitive silver halides, at least one kind of a coupler, at least one kind of a color developing agent expressed by formula of (L)n-D, and at least one kind of hardly-soluble metal hydroxide on a support is image-exposed and then, treated with a soln. containing at least one kind of a complex forming compd. In the formula, L represents electron withdrawing groups which can be released in a developing process, D represents a residue derived from HnD having developing activity by removing n of hydrogen atoms and n is an integer 1 to 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material. The present invention relates to a method for treating a material.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) have been increasingly developed. For example, in a method called ordinary color photography, photographing is performed using a color negative film, Color prints are obtained by optically printing the image information recorded on the developed color negative film onto color photographic paper.In recent years, this process has advanced to a high degree, and small-sized, simple printers have been used to print the film that has already been shot. By bringing a so-called minilab, which is a processor, to a minilab store installed in a store, a high-quality color image can be obtained within one hour.

However, in recent years, in order to counter the immediateness of competing electrophotographic materials such as digital still cameras and digital hard copy materials, the processing time of silver halide photographic materials has been further shortened. That is, rapid processing is required.

Generally, in the development processing of a silver halide color photographic light-sensitive material, a color developing solution containing a color developing agent is used to obtain a dye image. In such processing, the color developing agent is exposed to light. Speeding has been limited because of the time required to diffuse into the emulsion layer of the material.

In order to meet the above-mentioned demand, Japanese Patent Laid-Open No. 5-241282 discloses a technique for processing a color photographic light-sensitive material containing a specific color developing agent by treating it with an alkaline activator solution. 8-2
No. 02002, 8-286340 and the like. According to these techniques, although the effect that the development time is reduced by the amount that the color developing agent is not required to be diffused is obtained, the activator solution used as the processing solution is generally a high pH (strongly alkaline) solution. Therefore, a great deal of care is required for handling, and it is not environmentally preferable.

Further, the activator solution having a high pH absorbs carbon dioxide in the air, making it difficult to maintain the pH.
It has been clarified that there is a problem that photographic performance varies when continuous processing is performed.

Therefore, there has been a demand for a method of processing a silver halide photographic material which can rapidly obtain a high quality image without using a color developing solution and a high pH processing solution.

[0008]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material capable of rapid processing. Another object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material capable of obtaining a high image density without using a processing solution of the present invention. Another object of the present invention is to provide an improved method for processing a silver halide photographic material.

[0009]

The above object of the present invention has been attained by the following method.

[0010] 1. A silver halide containing a photosensitive silver halide, at least one coupler, at least one color developing agent represented by the following general formula [A], and at least one hardly soluble metal hydroxide on a support. A method for processing a silver halide photographic light-sensitive material, comprising subjecting a photographic light-sensitive material to image exposure and then processing with a solution containing at least one complex forming compound.

General formula [A] (L) _n -D wherein L represents an electron-withdrawing group capable of leaving during the development process, and D represents n hydrogen atoms from H _n D having development activity. And n represents an integer of 1 to 3. ] 2. Photosensitive silver halide, at least one coupler, at least one color developing agent represented by formula (A), at least one poorly soluble metal hydroxide, and at least one metal on a support A method for processing a silver halide photographic light-sensitive material, comprising subjecting a silver halide photographic light-sensitive material containing an ion-containing compound to image exposure and then treating with a solution containing at least one complex-forming compound.

3. Photosensitive silver halide, at least one coupler, at least one color developing agent represented by formula (A), at least one auxiliary developing agent, and at least one poorly soluble metal water on a support A method for processing a silver halide photographic light-sensitive material, which comprises subjecting a silver halide photographic light-sensitive material containing an oxide to image exposure and then treating with a solution containing at least one complex-forming compound.

4. Silver halide containing photosensitive silver halide, at least one kind of coupler, at least one kind of color developing agent represented by formula (A) and at least one kind of poorly soluble metal hydroxide on a support A method for processing a silver halide photographic light-sensitive material, comprising subjecting a photographic light-sensitive material to image exposure and then processing with a solution containing at least one complex-forming compound and at least one oxidizing agent.

5. Silver halide containing photosensitive silver halide, at least one kind of coupler, at least one kind of color developing agent represented by formula (A) and at least one kind of poorly soluble metal hydroxide on a support A method for processing a silver halide photographic light-sensitive material, comprising subjecting a photographic light-sensitive material to image exposure and then processing with a solution containing at least one complex-forming compound and at least one metal ion-containing compound.

6. 6. The method for processing a silver halide photographic material as described in any one of items 1 to 5, wherein the solution containing at least one complex forming compound further contains at least one auxiliary developing agent.

[7] 7. The method for processing a silver halide photographic material as described in any one of 1 to 6, wherein the hardly soluble metal hydroxide is zinc hydroxide.

8. 8. The method for processing a silver halide photographic light-sensitive material according to any one of 1 to 7, wherein the complex-forming compound is at least one selected from picolinic acid and picolinate.

Hereinafter, the present invention will be described in detail.

First, the color developing agent represented by the general formula [A] of the present invention will be described.

Formula (A) (L) _n -D [wherein L represents an electron-withdrawing group capable of leaving during the development process, and D represents n hydrogen atoms from H _n D having development activity. And n represents an integer of 1 to 3. Among the color developing agents represented by the general formula [A], particularly preferred are the color developing agents represented by the following general formulas (1) to (5).

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[Wherein, R _{1 to} R ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyl group, Represents an arylcarbonyl group or an acyloxy group. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. Z represents an atomic group forming an aromatic ring. R
₆ represents a substituted or unsubstituted alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring. Among the color developing agents represented by the general formulas (1) to (5), the color developing agent represented by the general formula (1) is a compound generally called sulfonamidophenol. In the formula, R _{1 to} R ₄ are each a hydrogen atom, a halogen atom (eg, a chloro group, a bromo group), an alkyl group (eg, a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group), an aryl group (For example, phenyl group, tolyl group, xylyl group), alkylcarbonamide group (for example, acetylamino group, propionylamino group, butyroylamino group), arylcarbonamide group (for example, benzoylamino group), alkylsulfonamide group (for example, methane Sulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (for example, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (for example, methoxy group, ethoxy group, butoxy group), aryloxy group (for example, phenoxy group), Alkylthio groups (eg, methylthio , Ethylthio, butylthio), arylthio (eg, phenylthio, tolylthio), alkylcarbamoyl (eg, methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidylcarbamoyl, morpholy) Carbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group) , Ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), Arylsulfamoyl group (for example, phenylsulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, Represents a propionyl group, a butyroyl group), an arylcarbonyl group (eg, a benzoyl group, an alkylbenzoyl group), or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group). Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. Further, it is preferable that the sum of the Hammett constant σp values of R _{1 to} R ₄ is 0 or more.

R ₅ is an alkyl group (for example, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group,
A stearyl group), an aryl group (e.g., phenyl, tolyl, xylyl, 4-methoxyphenyl, dodecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl, 4-dodecyloxyphenyl, 3,5-di-
(Methoxycarbonyl) group) or a heterocyclic group (eg, a pyridyl group).

The color developing agent represented by the general formula (2) is a compound generically called sulfonylhydrazine. Also,
The color developing agent represented by the general formula (4) is a compound generally called carbamoylhydrazine.

In the formula, Z represents an atomic group forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable.

In the case of a benzene ring, the substituent is
Alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), halogen atom (for example, chloro group,
Bromyl group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenyl) Carbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group) A famoyl group, a piperidylsulfamoyl group, a morpholylsulfamoyl group), an arylsulfamoyl group (for example, a phenylsulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, Examples thereof include a propionyl group, a butyroyl group) and an arylcarbonyl group (for example, a benzoyl group and an alkylbenzoyl group). The sum of the Hammett constant σ values of the above substituents is 1 or more.

The color developing agent represented by the general formula (3) is a compound generally called sulfonylhydrazone. Also,
The color developing agent represented by the general formula (5) is a compound generally called carbamoylhydrazone.

In the formula, R ₆ represents a substituted or unsubstituted alkyl group (for example, a methyl group or an ethyl group). X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl- or aryl-substituted tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring.

The specific examples of the color developing agents represented by formulas (1) to (5) are shown below, but the compounds of the present invention are not limited thereto.

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In the present invention, the addition amount of the color developing agent has a wide range.
It is suitably from 100 to 100 times, more preferably from 0.1 to 10 times.

Next, the coupler of the present invention will be described.

As the coupler preferably used in the present invention, there are compounds having structures represented by the following general formulas (6) to (17). These are compounds generally called active methylene, pyrazolone, pyrazoloazole, phenol and naphthol, respectively.

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Formulas (6) to (9) represent couplers referred to as active methylene couplers, wherein R ²⁴ represents an optionally substituted acyl group, cyano group, nitro group, or aryl group. , A heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas (6) to (8), R ²⁵ is an optionally substituted alkyl group, aryl group or heterocyclic group. In the general formula (9), R ²⁶ is an aryl group or a heterocyclic group which may have a substituent. R
Examples of the substituent which ²⁴ , R ²⁵ and R ²⁶ may have include, for example, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a cyano group, and a halogen atom. Examples of the substituent include various substituents such as an atom, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylamino group, an arylamino group, a hydroxyl group, and a sulfo group.
Preferred examples of R ²⁴ include an acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group.

In the general formulas (6) to (9), Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized developing agent. Examples of Y include groups acting as an anionic leaving group of a 2-equivalent coupler, such as a halogen atom (for example, chromium group, bromo group), an alkoxy group (for example, methoxy group, ethoxy group), an aryloxy group (for example, phenoxy group) , 4-cyanophenoxy group, 4-alkoxycarbonylphenyl group), alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, tolylthio group),
Alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group,
Diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl Groups (eg, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidylsulfamoyl, morpholylsulfamoyl), arylsulfamoyl Moyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group Alkylsulfonyl groups (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl groups (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkylcarbonyloxy groups (eg, acetyloxy group, propionyloxy group, Butyloyloxy group), arylcarbonyloxy group (for example, benzoyloxy group, toluyloxy group, anisyloxy group), nitrogen-containing heterocyclic group (for example, imidazolyl group, benzotriazolyl group) and the like.

Examples of the group acting as a cationic leaving group of the 4-equivalent coupler include a hydrogen atom, a formyl group, a carbamoyl group, and a methylene group having a substituent (substituents include an aryl group, a sulfamoyl group, a carbamoyl group, An alkoxy group, an amino group, a hydroxyl group, etc.), an acyl group,
And a sulfonyl group.

In the general formulas (6) to (9), R ²⁴ and R
²⁵ , R ²⁴ and R ²⁶ may combine with each other to form a ring.

The formula (10) represents a coupler called a 5-pyrazolone-based magenta coupler, wherein R ²⁷ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. R ²⁸ represents a phenyl group or a phenyl group substituted by one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group. Y is the same as in general formulas (6) to (9).

Among the 5-pyrazolone magenta couplers represented by the general formula (10), those wherein R ²⁷ is an aryl group or an acyl group and R ²⁸ is a phenyl group substituted by one or more halogen atoms are preferred.

To describe these preferred groups in detail, R ²⁷ is phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5- (3-octadecenyl-1-succinimide) Phenyl, 2-chloro-5-octadecylsulfonamidophenyl or 2-chloro-5- [2
-(4-hydroxy-3-t-butylphenoxy) tetradecanamido] aryl group such as phenyl, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-
Di-t-pentylphenoxy) acetyl, 2- (2,4
Acyl groups such as -di-t-pentylphenoxy) butanoyl, benzoyl, and 3- (2,4-di-t-amylphenoxyacetamido) benzoyl; these groups may further have a substituent; Is an organic substituent or a halogen atom connected by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.

R ²⁸ is 2,4,6-trichlorophenyl,
Substituted phenyl groups such as 2,5-dichlorophenyl and 2-chlorophenyl groups are preferred.

The general formula (11) represents a coupler called a pyrazoloazole coupler, wherein R ²⁹ represents a hydrogen atom or a substituent. Z is 5 containing 2 to 4 nitrogen atoms
Represents a group of nonmetallic atoms necessary to form a membered azole ring, and the azole ring may have a substituent (including a condensed ring). Y is the same as in general formulas (6) to (9).

Among the pyrazoloazole couplers represented by the general formula (11), imidazo [1,2] described in US Pat. No. 4,500,630 is preferred in view of the absorption characteristics of a coloring dye.
-B] pyrazoles, pyrazolo [1,5-b] [1, 2, 4] triazoles described in U.S. Pat. No. 4,540,654, and pyrazolo [US Pat. No. 3,725,067]. 5,1-c] [1,2,4] triazoles are preferable, and among these, pyrazolo [1,5-b] [1,2,4] triazole is preferable from the viewpoint of light fastness.

For details of the substituents on the azole ring represented by the substituents R ²⁹ , Y and Z, see, for example, US Pat.
No. 540,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61
Pyrazoloazole couplers in which a branched alkyl group is directly linked to the 2, 3 or 6 position of the pyrazolotriazole group as described in JP-A-65245;
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 01443 is a pyrazolotriazole coupler having a carboxamide group in the molecule.

Formulas (12) and (13) are couplers referred to as phenol couplers and naphthol couplers, respectively, wherein R ³⁰ is a hydrogen atom or -NHCO
_{^{R 32, -SO 2 NR 32 R}} 33, -NHSO 2 R 32, -NHC
^{OR 32, -NHCONR 32 R 33,} -NHSO 2 NR 32 R
Represents a group selected from ³³ . R ³² and R ³³ represent a hydrogen atom or a substituent. In the general formulas (12) and (13), R
³¹ represents a substituent, p represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. Y is the same as in general formulas (6) to (9). Examples of R ^{31 to} R ³³ include those described above as the substituents for R ^{24 to} R ²⁶ .

Preferred examples of the phenolic coupler represented by the general formula (12) include US Pat. No. 2,369,
No. 929, No. 2,801,171, No. 2,77
No. 2,162, No. 2,895,826, No. 3,7
2-alkylamino-5-alkylphenols described in U.S. Pat. No. 72,002 and the like, U.S. Pat. No. 2,772,162
No. 3,758,308, No. 4,126,39
No. 6, No. 4,334,011, No. 4,327,1
No. 73, West German Patent Publication No. 3,329,729, 2,5-diacylaminophenols described in JP-A-59-166956 and the like; U.S. Pat. Nos. 3,446,622 and 4,333. No. 999, No. 4,451,559,
And 4-phenylureido-5-acylaminophenols described in 4,427,767 and the like.

Preferred examples of the naphthol coupler represented by the general formula (12) include US Pat. No. 2,474,2.
No. 93, 4,052, 212, 4,146
No. 396, No. 4,228,233, No. 4,29
Examples thereof include 2-carbamoyl-1-naphthol described in US Pat. No. 6,200 and the like and 2-carbamoyl-5-amide-1-naphthol described in U.S. Pat. No. 4,690,889 and the like.

Formulas (14) to (17) are couplers called pyrrolotriazoles, and R ⁴² , R ⁴³ and R ⁴⁴ each represent a hydrogen atom or a substituent. Y is the same as in general formulas (6) to (9). As the substituents for R ⁴² , R ⁴³ and R ⁴⁴ , those described above as the substituents for R ^{24 to} R ²⁶ can be mentioned. Preferable examples of the pyrrolotriazole-based couplers represented by the general formulas (14) to (17) include European Patent Nos. 488,248A1 and 491,197A.
No. 1, No. 545, 300A1, R ⁴² and R ⁴³
Is a coupler in which at least one of them is an electron-withdrawing group.

In addition, fused ring phenol, imidazole,
Pyrrole, 3-hydroxypyridine, active methine, 5,
Couplers having a structure such as a 5-fused heterocycle and a 5,6-fused heterocycle can be used.

As condensed phenol couplers, US Pat. Nos. 4,327,173 and 4,564,586.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used.

As the imidazole coupler, couplers described in US Pat. Nos. 4,818,672 and 5,051,347 can be used.

As the pyrrole coupler, JP-A-4-14-1
The couplers described in Nos. 88137 and 4-190347 can be used.

As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 can be used.

As active methine couplers, couplers described in US Pat. Nos. 5,104,783 and 5,162,196 can be used.

The 5,5-fused heterocyclic couplers include
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289, pyrroloimidazole couplers described in JP-A-4-174429, and the like can be used.

The 5,6-fused heterocyclic couplers include:
Pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, EP 556,70.
The couplers described in No. 0 can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
81,268, European Patent Nos. 304,856A2, 329,036A2, and 354,549A2,
No. 374, 781A2 and No. 379, 110A2
No. 386,930A1, JP-A-63-1410
No. 55, No. 64-32260, No. 64-32261
JP-A-2-29747, JP-A-2-44340,
2-110555, 3-7938, 3-16
No. 0440, No. 3-172839, No. 4-17244
No. 7, 4-179949, 4-182645,
4-184337, 4-188138, 4-
Nos. 188139, 4-194847, 4-204
No. 532, No. 4-204731, No. 4-204732
The couplers described in the above publications can also be used.

Specific examples of the coupler usable in the present invention are shown below, but the present invention is of course not limited thereto.

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Further, the following functional couplers may be contained. As couplers for correcting unnecessary absorption of color-forming dyes, yellow colored cyan couplers described in European Patent No. 456,257A1, yellow colored magenta couplers described in the aforementioned European Patent, US Pat. No. 4,833,069 Magenta colored cyan coupler described in U.S. Pat. No. 4,837,136 (2);
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplary compounds on pages 36-45). Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Compounds of formulas (I) to (IV) described on page 11 of EP 378,236 A1, EP 436,
A compound represented by the formula (I) described on page 7 of 938A2, a compound represented by the formula (1) of Japanese Patent Application No. 4-134523, and a compound described on pages 5 and 6 of EP 440,195A2. Compounds represented by formulas (I), (II) and (III),
No. 4,555,47. The compound-ligand releasing compound of formula (I) of claim 1 of U.S. Pat.
A compound represented by LIG-X according to claim 1 of Claim 8.

The amount of the coupler to be added depends on the molar extinction coefficient (ε), but in order to obtain an image density of 1.0 or more in reflection density, the ε of the dye formed by coupling is about 5,000 to 500,000. In the case of the coupler described above, the coating amount is about 0.001 to 100 mmol / m ² , preferably 0.01 to 10 mmol / m ² , and more preferably about 0.05 to 5 mmol / m ² .

A hydrophobic additive such as a coupler or a color developing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat. No. 4,555,470,
Nos. 4,536,466, 4,536,467, 4,587,206, 4,555,476, 4,599,296, and JP-B-3-62256. Such a high-boiling organic solvent may be used, if necessary,
It can be used in combination with an organic solvent having a low boiling point of from 1 to 160 ° C. Two or more of these dye-donating couplers and high-boiling organic solvents can be used in combination. The amount of the high boiling organic solvent is 10 g per 1 g of the hydrophobic additive used.
Or less, preferably 5 g or less, more preferably 1 g to 0.1 g.
1 g. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39853, JP-A-51-59
A dispersion method using a polymer described in No. 943 or a method of adding a fine particle dispersion described in JP-A-62-30242 can be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, the surfactants described in Research Disclosure described in JP-A-59-157636, pages (37) to (38) can be used. Japanese Patent Application Nos. 5-204325 and 6-
Phosphate ester type surfactants described in 19247 and West German Patent Publication No. 1,932,299A can also be used.

Next, the hardly soluble metal hydroxide of the present invention will be described.

The hardly soluble metal hydroxide of the present invention includes metal hydroxides which are hardly soluble in water, such as zinc hydroxide, nickel hydroxide, cobalt hydroxide, iron hydroxide, manganese hydroxide, and the like.
Examples thereof include calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. Among these metal hydroxides, zinc hydroxide is particularly preferred.

Next, the complex-forming compound of the present invention will be described.

The complex-forming compound used in the present invention has an organic base, and forms a metal salt constituting a metal hydroxide and a complex salt having a stability constant of log K of 1 or more using water as a medium. Things.

These complex-forming compounds are described, for example, in E. Martel, R.E.
rtell, R .; M. Smith), “Critical Stability Konstanz (Critical S)
facility Constants), 1st to 5th
Vol. ", Plenum Press.

Specifically, amino carboxylic acids, iminodiacetic acid and derivatives thereof, aniline carboxylic acids, pyridine carboxylic acids, amino phosphoric acids, carboxylic acids (mono, di, tri, tetracarboxylic acids and further phosphono, hydroxy, oxo, ester, Compounds having a substituent such as amide, alkoxy, mercapto, alkylthio, and phosphino), salts with organic bases such as hydroxamic acids, polyacrylates, and polyphosphoric acids.

Preferred specific examples include picolinic acid,
2,6-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 4-dimethylaminopyridine-2,6-dicarboxylic acid, 5-ethylpyridine-2-carboxylic acid, quinoline-2-carboxylic acid, 2-pyridylacetic acid , Oxalic acid,
Citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), CyDTA (1,2-cyclohexanediaminetetraacetic acid), hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, poly Acrylic acid, o-aminobenzoic acid,

[0119]

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And the like and salts with organic bases.

Among them, an aromatic heterocyclic compound having at least one —CO ₂ HM and one nitrogen atom in the ring is preferable. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring.
And it is particularly preferable that -CO ₂ HM is at the α-position relative to the position where it is bonded to the ring, or to the N atom. Here, M is an organic base.

More preferred compounds include those represented by the following formula.

[0123]

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In the above formula, R represents a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, -CO ₂ HM, a hydroxycarbonyl group, an amino group, a substituted amino group,
Represents any one of electron donating groups such as an alkyl group.
Two Rs may be the same or different.

Z ₁ and Z ₂ are the same as defined for R, and Z ₁ and Z ₂ may combine to form a ring fused to a pyridine ring.

M is an organic base as described above.

As the organic base, those having a pKa of 7 or more and a carbon number of 12 or less are preferable.
It is a low-volatile base having a10 or more and a boiling point of 150 ° C. or more, and particularly preferred are guanidines, cyclic guanidines, amidines, cyclic amidines, and tetraalkylammonium hydroxides. Preferred examples of the organic base include piperidine, piperazine, ethylenediamine, N, N'-dimethylethylenediamine, acetamidine, diazabicyclononene, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide,

[0128]

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And the like.

Next, the metal ion-containing compound of the present invention will be described.

In the present invention, a metal ion-containing compound (hereinafter, also referred to as a metal source) refers to a compound which supplies a metal ion capable of chelating with a chelating group of a coupler, a color developing agent or a dye. Examples of such a metal source include inorganic or organic salts and metal complexes of metal ions, and among them, organic acid salts and complexes are preferable. Examples of the metal include monovalent and polyvalent metals belonging to Groups I to VIII of the periodic table. Among them, Al, Co, Cr,
Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferred, and particularly Ni, Cu, Cr, Co and Zn
Is preferred.

Specific examples of the metal source include Ni ²⁺ ,
^Examples include salts of Cu ²⁺ , Cr ²⁺ , Co ^2+, and Zn ²⁺ with aliphatic acids such as acetic acid and stearic acid, and salts with aromatic carboxylic acids such as benzoic acid and salicylic acid. Further, the ligand may be a precursor of a coupler, and is preferably used from the viewpoint of coloring properties.

The complex represented by the following formula (M) can be particularly preferably used.

The general formula (M) [M (Q ₁ ) _s (Q ₂ ) _t (Q
^{_{3) u] + r (T}} -) in _r formula, M is a metal ion, preferably Ni ^2+, Cu ^2+, C
r ²⁺ , Co ²⁺ , and Zn ²⁺ . Q ₁ , Q ₂ and Q ₃ each represent a coordination compound capable of coordinating with the metal ion represented by M, and may be the same or different. These coordination compounds can be selected, for example, from the coordination compounds described in Chelate Science (5) (Nankodo). T ⁻ represents an organic anion group, and specific examples include a tetraphenylboron anion and an alkylbenzenesulfonic acid anion. s, t and u each represent an integer of 0 to 3;
Seating coordination or, or is determined by whether 6-coordinated, or is determined by Q _1, the number of ligands Q ₂ and Q _3. r
Represents 1 or 2.

Among the complexes represented by the general formula (M), the following general formula (M-1) (when s, t, u = 0) is more preferable.

[0136] formula ^{_{(M-1) M 1 2+}} (W -) ₂ wherein, M ₁ ²⁺ represents a divalent transition metal ion, W ^- is to form a divalent metal ion and complex Represents a coordination compound represented by the following general formula (M-2).

Formula (M-2) R ₁₁ COC (Z ₁₁ ) =
C (R ₁₂₎ O ^- wherein, Z ₁₁ represents an alkyl group, an aryl group, an aryloxycarbonyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom or a hydrogen atom. R ₁₁ and R ₁₂ each represent an alkyl group or an aryl group, and may be the same or different, and R ₁₁ and Z ₁₁ or R ₁₂ and Z ₁₁ may combine to form a ring. However, when Z ₁₁ is a hydrogen atom, R
₁₁ and R ₁₂ are not both methyl groups.

Examples of typical compounds of the metal source are shown below, but the present invention is not limited to these.

[0139]

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[0140]

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One form for forming a metal chelate image is to perform treatment with a solution containing a metal source. This solution may be the color developing solution itself,
It may be a subsequently used processing solution, such as an alkaline fixing solution, or a separate metal chelating solution.
Metal chelation can be carried out at pH 5.0 to 12.0 at normal processing temperatures.

When a metal source is added to a processing solution, the compound can be selected so as to be easily dissolved in a processing solution, for example, a fixing solution. 0.1-120g for metal sauce
/ L, preferably 1-30 g / l.

When processing is performed with a solution containing a metal source, the processing can be performed by immersing the photosensitive material in the solution. Alternatively, the solution may be sprayed or applied to the photosensitive material. Chelation with a metal source may be performed before or after development, and can be performed before or after bleach-fixing.

Another mode for forming a metal chelate image is a processing method using a sheet containing a metal ion compound. The sheet may be the same as a processing sheet for color development. That is, an alkali precursor, a bleach-fixing agent, a mordant and the like may be simultaneously contained, or only a metal source may be contained.

The chelated sheet can be used as it is or with the addition of water. As a method of adding water, a method of applying a small amount of water to a light-sensitive material or a processing sheet or spraying water can be used. Alternatively, the photosensitive material may be immersed in a water bath, and excess water may be squeezed (squeezed) before use.

Another mode for forming a metal chelate image is to add a metal source to a light-sensitive material. The layer to be added may be the same layer as the coupler or a layer adjacent thereto. The metal source may be water-soluble or oil-soluble, but when the coupler is oil-soluble, the metal source is preferably oil-soluble, and can be added by dissolving it in a high-boiling solvent like the coupler.

The amount of the metal source to be added is 0.01 to 100 times, preferably 0.1 to 10 times, more preferably 0.2 to 5 times the weight of the coupler.

Next, the oxidizing agent of the present invention will be described.

As the oxidizing agent of the present invention, ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ , H ₂ O ₂ .H ₂
O, 2NaCO ₃ .H ₂ O ₂ , Na ₄ P ₂ O ₇ .H ₂ O ₂ , 2N
aSO ₄ .H ₂ O ₂ .2H ₂ O), peroxy acid salt (for example, K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ) peroxy complex compound (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] · 3H ₂
O, 4K ₂ SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O,
Na ₃ [VO (O ₂ ) (C ₂ O ₄ ) ₂ ] · 6H ₂ O), permanganate (eg, KMnO ₄ ), chromate (eg, K ₂
Oxygenates such as CrO ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), salts of high valent metals (eg, potassium hexacyanoferric acid) and thiosulfonic acid Salts and the like can be mentioned, and among these oxidizing agents, hydrogen peroxide and its adduct are particularly preferable.

Next, the auxiliary developing agent of the present invention will be described.

In the present invention, an auxiliary developing agent can be preferably used. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the color developing agent to the silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably a compound of the general formula It is an electron-emitting compound according to the Kendall-Peltz rule represented by (B-1) or the general formula (B-2). Among them, those represented by (B-1) are particularly preferred.

[0152]

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In the general formulas (B-1) and (B-2),
R ^{51 to} R ⁵⁴ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

R ^{55 to} R ⁵⁹ are a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic oxy group. Group, silyloxy group, acyloxy group, amino group, anilino group, heterocyclic amino group, alkylthio group, arylthio group, heterocyclic thio group, silyl group, hydroxyl group,
Nitro group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group,
Cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group,
Represents a sulfamoylamino group, an alkylsulfinyl group, an arenesulfinyl group, an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, a sulfo group, a phosphinoyl group, and a phosphinoylamino group.

Q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different from each other. R ⁶⁰ represents an alkyl group or an aryl group.

Specific examples of the compound represented by formula (B-1) or (B-2) are shown below, but the auxiliary developing agent used in the present invention is not limited to these specific examples.

[0157]

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[0158]

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[0159]

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The light-sensitive material of the present invention is basically a material having a light-sensitive silver halide, a color developing agent, a coupler, and a binder on a support, and these components are often added to the same layer. If it can react, it can be added in separate layers.

The hydrophobic additive such as a coupler used in the present invention can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, US Pat. No. 4,555,470
No. 4,536,466 and No. 4,536,46
No. 7, No. 4,587,206, No. 4,555, 4
No. 76, No. 4,599,296, Tokuhei 3-622
A high-boiling organic solvent as described in No. 56 or the like can be used in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C. as necessary. Two or more of these color developing agents, couplers, high-boiling organic solvents and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 to 0.1 g, based on 1 g of the color image forming compound used. 1g of binder
1 cc or less, more preferably 0.5 cc or less,
3 cc or less is appropriate. In addition, Japanese Patent Publication No. 51-3985
No. 3, JP-A-51-59943, a dispersion method using a polymer described in JP-A-62-30242 and JP-A-6-30242.
A method of adding a fine particle dispersion described in JP-A-2-271339 or the like can also be used. In the case of a compound that is substantially unnecessary in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636
Nos. (37)-(38), R shown in the table below
The surfactants described in the magazine D can be used. 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.

In order to obtain a wide range of colors on the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are combined. Used. For example, there are a combination of three layers of a blue-sensitive layer, 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.

The light-sensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer, and a back layer. Further, various filter dyes can be added to improve color separation.

The silver halide grains used in the present invention are silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. Other silver salts, for example, silver rhodan silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as part of halogen atom grains. Development and desilvering (bleaching, fixing and bleach-fixing)
When speeding up the process is desired, silver halide grains having a high silver chloride content are desirable.

The silver halide emulsion used in the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. A typical example is Japanese Patent Publication No. 43-1
No. 3162, Japanese Patent Application Laid-Open No. 61-215540, Japanese Patent Application Laid-Open
These are core-shell type or double structure particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions, as disclosed in JP-A-22845 and JP-A-61-75337.
In addition, it is not a simple double structure.
Or a multilayer structure having three or more layers as disclosed in the above-mentioned publication, or a silver halide having a different composition may be thinly applied to the surface of a core-shell double-structured grain.

In order to provide a structure inside the particle, not only the wrapping structure as described above, but also a particle having a so-called junction structure can be produced. These examples are disclosed in
No. 133540, JP-A-58-108526, European Patent No. 199,290A2, JP-B-58-24772.
And JP-A-59-16254.
The crystal to be bonded can be formed by bonding to the edge, corner, or surface of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure.

In the case of a junction structure, a combination of silver halides is of course possible, but a silver salt compound having no silver salt structure such as silver rhodanate or silver carbonate can be combined with silver halide to form a junction structure. Further, a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible.

It is important to control the silver halide composition near the surface of the grains. Increasing the amount of silver iodide in the vicinity of the surface or increasing the content of silver chloride can be selected according to the purpose because the adsorption of the dye and the developing speed are changed. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, the halogen composition may be changed on only one side of the tetrahedral grain composed of the (100) plane and the (111) plane, or the halogen composition on one of the main plane and the side face of the tabular grain may be changed.

The silver halide grains used in the present invention may be normal crystals having no twin planes, as described in the Photographic Society of Japan, Fundamentals of the Photographic Industry, Silver Salt Photography (Corona), page 163. Examples include single twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, and non-parallel multiple twins containing two or more non-parallel twin planes. You can select and use it. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube consisting of (100) planes, (111)
Octahedral particles composed of planes and dodecahedral particles composed of (110) planes disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. Jou
rnalof Imaging Science 30
Volume, page 247 (1986), (h11) plane particles represented by the (211) plane, and (33)
1) The (hh1) plane particle representing the plane, the (hk0) plane particle represented by the (210) plane, and the (hk1) plane particle represented by the (321) plane also require some contrivance in the adjustment method. They can be selected and used according to the requirements. (100) face and (11)
1) a tetrahedral particle whose plane coexists in one particle, (10
0) and (110) coexisting particles, or (11)
Particles in which two surfaces or many surfaces coexist, such as particles in which 1) and (110) surfaces coexist, can be selected and used according to the purpose.

The value obtained by dividing the circle equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described in "Theory and Practice of Photography" by Cleave (Cleav, Photography The).
ory and Practice (1930)), 1
Page 31; Gatov, Photographic Science
And Engineering (Gutof, Photog
raphic science and engineering
ering), 14, 248-257 (1970).
U.S. Pat. Nos. 4,434,226 and 4,41.
No. 4,310, No. 4,433,048, No. 4,4
39,520 and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in the efficiency of color sensitization by a sensitizing dye, which is described in detail in U.S. Pat. No. 4,434,226 cited above. . 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. U.S. Pat. No. 4,798,35
No. 4, a regular hexagon having substantially equal lengths of six sides is a preferable form.

Although the circle equivalent diameter of the projected area is often used as the particle size of the average particle, US Pat.
No. 8,106 has an average diameter of 0.6.
Submicron particles are preferred for high image quality. Also preferred are emulsions having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617. 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. JP 63
Also preferred are particles described in JP-A-163451 in which the thickness of the particles and the distance between twin planes are specified.

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. It is also possible to select dislocations introduced linearly or bent dislocations in a specific direction of the crystal orientation of the grains, or to introduce them all over the grains, or to introduce them only into 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 silver halide emulsion used in the present invention may be prepared by subjecting a grain to a roundness as disclosed in European Patent No. 96,412B1 or the like, or by a method disclosed in West German Patent No. 2,30.
The surface may be modified as disclosed in JP-A-6-447C2 and JP-A-60-221320.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally.
JP-A-58-106532, JP-A-60-22132
0, for example, a method of making a hole in a part of a crystal, for example, a vertex or a center of a face, or US Pat.
Raffle particles described in U.S. Pat. No. 3,966 are examples.

The grain size of the emulsion used in the present invention is determined by the equivalent circle diameter of the projected area using an electron microscope, the equivalent sphere diameter of the particle volume calculated from the projected area and the grain thickness, or the equivalent sphere diameter of the volume by the Coulter counter method. Can be evaluated. Ultrafine particles having a sphere equivalent diameter of 0.05 μm or less and coarse particles exceeding 10 μm can be selected and used. Preferably 0.1 micron or more 3
Submicron grains can be used as the photosensitive silver halide grains.

Emulsions for use in the present invention may be selected from so-called polydisperse emulsions having a wide grain size distribution, and monodisperse emulsions having a narrow size distribution, depending on the purpose. In some cases, a variation coefficient of the projected area circle equivalent diameter or sphere equivalent diameter of a particle is used as a scale representing the size distribution. When a monodisperse emulsion is used, it is preferable to use an emulsion having a variation coefficient of 25% or less, more preferably 20% or less, and still more preferably 15% or less.

A monodisperse emulsion is sometimes defined as an average grain size distribution by grain or weight. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte Co. (PG
refkides, Chemie et Physiq
uePhotographique, Paul Mon
tel., 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Phot).
optic Emulsion Chemist
ry, FocalPress, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL Zelikman, et al., Maki).
ng and Coating Photograph
ic Emulsion, Focal Press, 1
964), etc., any of which can be used. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-side mixing method, a double-mixing method, and a combination thereof. . A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of keeping the pAg of a liquid phase in which silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, US Pat. No. 4,33
No. 4,012, No. 4,301,241, No. 4-1
50,994 is optionally preferred. These can be used as seed crystals, and are also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from a total amount addition at a time, a plurality of additions, or a continuous addition. Also,
It is sometimes effective to add particles of various halogen compositions to modify the surface.

A method of converting most of the halogen composition of silver halide grains by a halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
No. 2,900, European Patent Nos. 273,429 and 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a more insoluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously.

In addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate for grain growth, UK Patent No. 1
469,480; U.S. Pat. No. 3,650,757;
The particle formation method in which the concentration is changed or the flow rate is changed as described in US Pat. No. 4,242,445 is a preferred method. By changing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions or adding a plurality of soluble halide salts having different solution compositions, an addition method of increasing one and decreasing the other is also an effective method. It is.

A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in US Pat. No. 2,996,287.
No. 3,342,605 and No. 3,415,65
No. 0, No. 3,785,777, West German Patent No. 2,
556,885 and 2,555,364.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have excess halide ions present in the reactor to promote ripening. Other ripening agents can be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, or can be added together with the halide salts, silver salts or deflocculants and added to the reactor. Can also be introduced. As another variant, the ripening agent can be introduced independently during the silver halide and silver salt addition step.

Ammonia, thiocyanates (rhodancali, rhodanammonium, etc.) and organic thioether compounds (for example, US Pat. Nos. 3,574,628 and 3,
Nos. 021, 215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130,
No. 4,782,013, JP-A-57-104926
And thione compounds (for example, tetra-substituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. -144319), mercapto compounds capable of promoting the growth of silver halide grains described in JP-A-57-202531, amine compounds (for example, JP-A-54-100717) and the like. Is mentioned.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxycellulose, carboxymethylcellulose and cellulose sulfate, sodium alginate, starch derivatives, gum arabic , Dextran, sugar derivatives such as natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. And various kinds of synthetic hydrophilic high-molecular substances such as a single or copolymer. Further, superabsorbent polymers described in U.S. Pat. No. 4,960,681 and JP-A-62-245260, that is, -COOM or -SO
₃ M (M represents a hydrogen atom or an alkali metal) copolymer (for example, sodium methacrylate and a copolymer or a vinyl monomer together or with other vinyl monomers, a vinyl monomer having, ammonium methacrylate, Sumitomo Chemical (Co. Sumikagel L-5H)) is also used. These binders can be used in combination of two or more kinds. Combinations of gelatin and the above binders are also preferred.

As the gelatin, in addition to lime-processed gelatin,
It may be selected from acid-treated gelatin and so-called demineralized gelatin having a reduced content of calcium and the like, and it is also preferable to use them in combination. Bull. Soc. Sci. P
photo. Japan. No. 16. p30 (196
Enzyme-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used. The use of low molecular weight gelatin described in JP-A-1-58426 is preferred for preparing tabular grains.

In the case of a photothermographic material, an organic silver salt oxidizing agent may be used together with the photosensitive silver halide emulsion. Examples of the organic compound which can be used for forming the same include US Pat. There are benzotriazoles, fatty acids and other compounds described in column Nos. 52 to 53 of 500,626. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination.
The above organic silver salt is used per mole of the photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of the photosensitive silver halide emulsion and the organic silver salt is preferably from 0.7 to 3.5 g / m ² in terms of silver. More preferably, 1.0 to 2.0 g /
m ² . If the amount of silver increases, the desilvering process may be insufficient. If the amount is too low, the image density is too low, which may affect image information.

The emulsion used in the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose,
It is preferable to select within the range. The pH at the time of washing can be selected depending on the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

The silver halide grains used in the present invention are at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization, or reduction sensitization. Can be applied in any step of the production process of the silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded inside the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

The chemical sensitization which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination thereof, and is described in TH James, The.
Photographic Process, 4th Edition, Macmillan, 1977 (TH James, The Pho
graphical Process, 4th ed.
Macmillan, 1977), pages 67-76, and can be performed using active gelatin, or can be performed using Research Disclosure Item 120.
08 (April 1974), Item 13452 (19
June 1975), Item 307105 (January 1989)
January), US Patent Nos. 2,642,361 and 3,2
No. 97,446, No. 3,772,031, No. 3,
PAg 5-10 as described in 857,711, 3,901,714, 4,266,018 and 3,904,415 and British Patent 1,315,755. , Selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers at a pH of 5 to 8 and a temperature of 30 to 80 ° C.

In sulfur sensitization, an unstable sulfur chemical is used, specifically, thiosulfate (eg, hypo),
Thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanines, mercaptos, thioamides, thiohydantoins, 4-oxooxazolidin-2-thiones, di- or polysulfides, polythionates And elemental sulfur, and U.S. Patent Nos. 3,857,711 and 4,266,018.
And the known sulfur-containing compounds described in U.S. Pat. No. 4,054,457. Sulfur sensitization is often used in combination with noble metal sensitization.

The preferred amount of the sulfur sensitizer to be used for the silver halide grains used in the present invention is as follows.
It is 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol per mol, more preferably 5 × 10 ⁻⁷ to 1 × 10 ⁻⁴ mol.

In selenium sensitization, a known unstable selenium compound is used, for example, US Pat. No. 3,297,446.
No. 3,297,447 and the like, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, tetramethylselenium urea) Etc.), seleno ketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), seleno Phosphates (eg, tri-p-
Selenium compounds such as trisylselenophosphate) can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or precious metal sensitization.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally from 10 ^{-8 to} 110 per mol of silver halide.
^-4 mol, preferably about 10 ^-7 to 10 ^-5 mol is used.

The tellurium sensitizers used in the present invention include Canadian Patent No. 800,958 and British Patent Nos. 1,2.
No. 95,462, No. 1,396,696, Japanese Patent Application No. 2
Compounds described in JP-A-333819 and JP-A-3-131598 can be used. Specific examples of 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 (eg, tributylphosphine telluride, butyldiisopropylphosphine) Telluride), other tellurium compounds (eg, potassium tellurocyanate, sodium telluropentathionate)
And the like.

The tellurium sensitizer was used in an amount of 1 silver halide.
It is about 1 × 10 ^{−7 to} 5 × 10 ⁻² mol, preferably about 5 × 10 ⁻⁷ to 1 × 10 ⁻³ mol per mol.

In the noble metal sensitization, noble metal salts such as platinum, gold, palladium, and iridium can be used. Among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent salt or a tetravalent salt of palladium. Preferred palladium compounds are R ₂ PdX ₆ or R
₂ PdX ₄ Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, urea or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₅ , NaPdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂
PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

The emulsion used in the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-7 to 1 × 10 ^-3 mol, more preferably 5 × 10 ^{-7 to} 5 × 10 ^-4 mol, per mol of silver halide. The preferred range of the palladium compound is 5 × 10 ^-7 to 1 × 10 ^-3 mol. The preferred range of the thiocyan compound or selenocyan compound is 1 × 10 ^{−6 to} 5 × 10 ⁻² mol.

The silver halide emulsion of the present invention is preferably subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, reduction sensitization refers to a method in which a reduction sensitizer is added to a silver halide emulsion, or a pAg 1 called silver ripening.
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because it has an advantage that the level of reduction sensitization can be finely adjusted.

As the reduction sensitizer, known reduction sensitizers such as stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidine sulfinic acid, silane compounds and borane compounds are selected. And two or more compounds can be used in combination. Stannous chloride, aminoiminomethanesulfinic acid (common name: thiourea dioxide) as reduction sensitizer,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reducing agent sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization auxiliary. Useful chemical sensitizers include compounds known as azaindene, azapyridazine, azapyrimidine, which suppress fog in the course of chemical sensitization and increase sensitivity. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,4,
No. 11,914, No. 3,554,757;
No. 8-126526 and the above-mentioned book by Duffin, "Photographic Emulsion Chemistry, pp. 138-143".

It is preferable to use an oxidizing agent for silver in the emulsion used in the present invention during the production process. The oxidizing agent for silver refers to a compound having an effect of acting on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains that are replicated in the course of forming silver halide grains and in the course of chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ , H ₂ O ₂ .H ₂ O, 2NaCO ₃ .H ₂ O
₂ , Na ₄ P ₂ O ₇ .H ₂ O ₂ , 2NaSO ₄ .H ₂ O ₂ .2H ₂
O), peroxyacid salts (eg, K ₂ S ₂ O ₈ , K ₂ C)
₂ O ₆ , K ₂ P ₂ O ₈ ) peroxy complex compound (for example, K _{2
[Ti (O 2) C 2 O} 4 ] _{· 3H 2 O, 4K 2 SO} 4 · Ti
(O ₂ ) OH.SO ₄ .2H ₂ O, Na ₃ [VO (O ₂ )
(C ₂ O ₄ ) ₂ ] · 6H ₂ O), permanganate (eg, K
Oxyacids such as MnO ₄ ), chromates (eg, K ₂ CrO ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), and salts of high-valent metals (eg, , Potassium hexacyanoferrate) and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen (eg, N-bromosuccinimide, chloramine). T, chloramine B) are mentioned by way of example.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazole salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), mercaptopyrimidine, mercaptotriazine, thioketo compounds such as oxazolinethione, azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl-1,3,3) Many compounds known as antifoggants or stabilizers can be added, such as 3a, 7-tetraazaindene), pentaazaindenes and the like. For example, US Pat.
No. 474, No. 3,982,947, Japanese Patent Publication No. 52-2
No. 8660 can be used. One of the preferred compounds is a compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers can be used at various times before, during and after particle formation, during the washing step, during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose.
In addition to exhibiting the original fogging prevention and stabilizing effects when added during emulsion preparation, it also controls grain walls, reduces grain size, reduces grain solubility, and controls chemical sensitization. It can be used for various purposes such as controlling the arrangement of dyes.

In the case where the light-sensitive silver halide used in the present invention has green-, red-, and infrared-sensitive color 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.

The dyes used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as base heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, such as an alicyclic hydrocarbon ring fused to these nuclei, and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus,
That is, indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
Heterocyclic nuclei such as a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a thiobarbituric acid nucleus and the like can be applied. These nuclei may be substituted on carbon atoms. Specific examples include sensitizing dyes described in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-64-13546, Japanese Patent Application Nos. 5-45828, 5-45834, and the like. Can be

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, 5 to 5 such as rhodanine nucleus and thiobarbituric acid nucleus
Six-membered heterocyclic nuclei can be applied.

These dyes may be used alone or in combination, and a combination of sensitizing dyes is often used for the purpose of supersensitization and adjusting the wavelength of spectral sensitivity. A representative example is U.S. Pat. No. 2,688,5.
No. 45, No. 3,397,060, No. 2,977,
No. 229, No. 3,522,052, No. 3,52
No. 7,64, No. 3,617,293, No. 3,62
No. 8,964, No. 3,672,898, No. 3,6
No. 79,428, No. 3,703,377, No. 3,
Nos. 769,301; 3,814,609; 3,837,862; 4,026,707; British Patents 1,344,281 and 1,507,80.
No. 3, JP-B-43-4936, and JP-B No. 53-12375
JP-A-52-110618, JP-A-52-110992
No.5.

Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, U.S. Pat. No. 3,615,641 and those described in JP-A-63-23145).

The time when these sensitizing dyes are added to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful.

Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat. No. 3,628,96
As described in JP-A-58-113928, the addition of a chemical sensitizer at the same time as that described in JP-A Nos. Can be performed prior to chemical sensitization as described in (1). Further, it can be added before the completion of precipitation of silver halide grains to start spectral sensitization. Further, according to U.S. Pat. Nos. 4,183,756 and 4,225,666, it may be before or after the nucleation of silver halide grains, a part of chemicals is added before chemical sensitization, and the remainder is chemically sensitized. Separate additions, such as those added later, are also possible.

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 about 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide, but more preferably about 5 × when the silver halide grain size is 0.2 to 1.2 μm. 10 ^{-5 to} 2 × 10 ^-3 mol is more effective.

The above-mentioned various additives are used in the light-sensitive material according to the present technology, and other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978) and Item 18716 (November 1979).
And Item 307105 (November 1989), and the relevant portions are summarized in the table below.

[0220]

[Table 1]

As hardening agents, in addition to those described above, US Pat. No. 4,678,739, column 41 and 4,791,04.
No. 2, JP-A-59-116655 and JP-A-62-2452.
No. 61, 61-18942, JP-A-4-21804
No. 4 and the like. More specifically,
Aldehyde hardener (such as formaldehyde), azirine hardener, epoxy hardener, vinyl sulfone hardener (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane, etc.), N-methylol Hardeners (such as dimethylol urea) or polymeric hardeners (JP-A-6
2-234157). These hardeners are used in an amount of 0.001 g to 1 g, preferably 0.005 g to 0.5 g per g of gelatin applied.
Is used. The layer to be added may be any of constituent layers such as a light-sensitive material and a dye-fixing material, or may be added in two or more layers.

In the light-sensitive material of the present invention, a matting agent can be used for the purpose of preventing adhesion, improving slipperiness, and giving a non-glossy surface. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A Nos. 63-274944 and 63-2, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads, in addition to the compounds described on page 56 (29).
No. 74952. In addition, the compounds described in the aforementioned RD magazine can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as needed. In addition, the constituent layers of the photothermographic material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, a fungicide, colloidal silica, and the like. Specific examples of these additives are disclosed in
No. 88256, pages 26 to 32, JP-A-3-113
No. 38, JP-B-2-51496 and the like.

In the constituent layers of the light-sensitive material of the present invention, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of lubricity, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are described in the above-mentioned RD Magazine and JP-A-62-1746.
No. 3, No. 62-183457 and the like. In the case of a photothermographic material, it is also preferable to include an organic fluoro compound in the constituent layers for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-9053.
No. -20944, No. 62-135836 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin Is mentioned.

In the light-sensitive material of the present invention, known anti-fading agents can be used. Organic anti-fading agents include hydroquinones, 5-hydroxychromans, 5-hydroxycoumarins, paraalkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, amino Representative examples include phenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used. Compounds having both hindered amine and hindered phenol partial structures in the same molecule as described in U.S. Pat. No. 4,268,593 can prevent the yellow dye image from deteriorating due to heat, humidity and light. give. Further, spiroindanes described in JP-A-56-159644 may be used to prevent the deterioration of magenta dye images, especially deterioration due to light.
And chromans substituted with hydroquinone diether or monoether described in JP-A-55-89835 give preferable results.

In the constituent layers of the light-sensitive material of the present invention, various antifoggants or photographic stabilizers and precursors thereof can be used. As a specific example, the RD
Magazine, U.S. Pat. Nos. 5,089,378 and 4,50.
0,627, 4,614,702, JP-A-64
No. 13546, pages (7) to (9), (57) to (71)
Page and pages (81)-(97), U.S. Pat.
No. 610, No. 4,626,500, No. 4,98
No. 3,494, JP-A-62-174747, JP-A-62-274.
239148, 63-264747, JP-A-1-
No. 150135, No. 2-110557, No. 2-178
No. 650, Research Disclosure 17643 (1
978), pages 24 to 25, and the like. These compounds are 5 × 10 ^-6 per mole of silver.
To 1 × 10 ^−1, more preferably 1 × 10 ⁻⁵ to 1 × 10 ^−2.
Is preferably used.

Suitable supports that can be used in the present invention include synthetic plastic films such as polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalate and polyvinyl chloride, as well as photographic base paper and printing. Paper supports such as paper, baryta paper, and resin-coated paper; and supports in which a reflective layer is provided on the above-mentioned plastic film, JP-A-62-253195 (29-3)
1) described as a support. Page 28 of the aforementioned Research Disclosure 17643,
No. 18716, from the right column on page 647 to the left column on page 648; Those described on page 879 of 307105 can also be preferably used. Syndiotactic polystyrenes are also preferred. These are disclosed in JP-A-62-1770.
No. 8, JP-A-1-46912 and JP-A-1-178505. These supports include U.S. Pat. No. 4,141,7.
As described in No. 35, by performing a heat treatment of Tg or less, it is possible to use a material which is less likely to have a curl. The surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and the emulsion undercoat layer. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Further known technology No. 5
No. (issued by Aztec Co., Ltd. on March 22, 1991) at pages 44 to 149 can also be used.
A transparent support such as polyethylene dinaphthalenedicarboxylate or a support on which a transparent magnetic substance is applied can be used.

The method of exposing and recording an image on the light-sensitive material of the present invention includes, for example, a method of directly photographing a landscape or a person using a camera or the like, and a method of exposing through a reversal film or a negative film using a printer or a enlarger. Scanning method using an exposure device of a copier to scan and expose the original image through slits, etc., and scan by emitting light emitting diodes and various lasers (laser diodes, gas lasers, etc.) via image information and electric signals. A method of exposing (a method described in JP-A-2-129625), a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposing directly or via an optical system. and so on.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No.4, such as natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
500,626, column 56, JP-A-2-53378,
The light source and the exposure method described in JP-A-2-54672 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 nonlinear optical material is
It is a material that can exhibit nonlinearity between localization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, and BaB ₂ O ₄ Such as inorganic compounds,
Urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM);
Compounds described in JP-A-53462 and JP-A-62-210432 can be 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 is obtained by dividing an image signal obtained from a video camera, an electronic still camera, or the like, a television signal represented by the Nippon Television Signal Standard (NTSC), or an original image into a plurality of pixels such as a scanner. Image signal,
Images created using a computer represented by CG and CAD can be used.

[0230]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as follows.

First layer coating solution 5.68 g of yellow coupler (YC-1), 6.68 g of color-forming reducing agent (D-34), high boiling organic solvent (DBP)
To 3.33 g and 1.67 g of a high boiling point organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution was mixed with 220 ml of a 10% gelatin aqueous solution containing 7 ml of a 20% surfactant (SU-1) using an ultrasonic homogenizer. The mixture was emulsified and dispersed to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 2 and 3.

(H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension.
Further, F-1 was added to each layer so that the total amount became 0.04 g / m ² .

[0235]

[Table 2]

[0236]

[Table 3]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2 -Sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone

[0238]

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[0239]

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[0240]

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(Preparation of Blue-Sensitive Silver Halide Emulsion)
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, EMP was carried out except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
As in the case of -1, the average particle diameter is 0.64 μm, and the coefficient of variation is 0.1.
07, a monodispersed cubic emulsion EMP-1B having a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%.

Next, a monodispersed cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-3 was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In the red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{-3 was} added.

[0251]

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[0252]

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The light-sensitive material thus prepared was used as Sample 1
And

Next, the same procedure as in Sample 1 was conducted except that 0.5 g / m ² of zinc hydroxide was added in a solid dispersion state to the seventh layer of Sample 1.
Sample 2 was prepared in the same manner as described above.

Next, the first layer, the third layer, and the fifth layer
Each layer contains 0.1 g / m ² of a metal ion-containing compound MS-
Sample 3 was prepared in the same manner as Sample 2 except that 11 was added.

A sample was prepared in the same manner as in Sample 2 except that 0.03 g / m ² of 1,5-diphenyl-3-pyrazolidone was added to each of the second and fourth layers in a solid dispersion state. 4 was produced.

Further, 0.1 g / m ² of the metal ion-containing compound MS was applied to the first, third and fifth layers of Sample 2, respectively.
Sample 5 was prepared in the same manner as in Sample 2, except that -11 was added to the second and fourth layers, respectively, in the form of solid dispersion of 0.03 g / m ² of 1,5-diphenyl-3-pyrazolidone. .

<< Evaluation Method >><< Highest Concentration >> Samples 1 to 5 prepared as described above
Was exposed to light by a sensitometer, and then subjected to the following processing steps to determine the maximum density of each of blue light (B), green light (G), and red light (R).

Each activator processing solution was applied by applying 50 ml per 1 m ² of the light-sensitive material sample.

<< Light Resistance >> Further, the portion having an optical density of 1.0 of each treated sample was irradiated with a xenon fade meter for 4 days, and the density was measured to determine the residual ratio (%) of the dye after the light resistance test. I asked. Table 4 also shows the results.

<< Treatment Step >> Activator Treatment 50 ° C. for 20 seconds Bleaching and Fixing 50 ° C. for 15 seconds Stabilization 50 ° C. for 15 seconds Drying 80 ° C. for 20 seconds << Composition of Treatment Solution >> <Activator Treatment Solution> Composition Treatment Solution ABC DEF Potassium picolinate 20g Same left Same left Same left Same left Same left Same potassium chloride 5g Same left Same left Same left Same left Same left Same left Same left Same left Same as left 30% hydrogen peroxide solution 5g Same as left-5g Add water 1000ml Same left Same left Same left Same left Same as left Add 25ml water and add 10 Make up to 00 ml <Stabilizing solution>: 1% trisodium phosphate aqueous solution

[0262]

[Table 4]

As is clear from Table 4, Sample No. containing no hardly soluble metal hydroxide was used. Experiment No. 1 in which the process of the present invention was performed using 1 to Experiment No. 1 In the case of 3, almost no image is obtained.

On the other hand, the sample No. containing the hardly soluble metal hydroxide of the present invention. No. 2 to sample no. Experiment No. 5 in which the treatment was carried out with the treatment liquid containing the complex-forming compound of the present invention using No. 5 4 to Experiment No. 4 In Experiment No. 12, a high maximum concentration was obtained in each case, and in Experiment No. 12 in which either the photosensitive material sample or the processing solution contained the metal ion-containing compound of the present invention. 6 ~
Experiment No. 9, Experiment No. 11, Experiment No. In 12,
Very good light fastness.

[0265]

According to the present invention, firstly, there is provided a method for processing a silver halide photographic light-sensitive material capable of rapid processing. Secondly, high image quality can be obtained without using a high pH processing solution. The present invention provides a method for processing a silver halide photographic light-sensitive material capable of obtaining a density, and thirdly, a method for processing a silver halide photographic light-sensitive material in which the image storability of a formed dye is sufficiently improved. I was able to.

Claims (8)

[Claims] 1. A support comprising a photosensitive silver halide, at least one coupler, at least one color developing agent represented by the following general formula [A], and at least one poorly soluble metal hydroxide. A method for processing a silver halide photographic light-sensitive material, comprising subjecting a silver halide photographic light-sensitive material to image exposure and then treating with a solution containing at least one complex-forming compound. General formula [A] (L) _n -D [wherein, L represents an electron-withdrawing group capable of leaving during the development process, and D is derived from H _n D having development activity by removing n hydrogen atoms. And n represents an integer of 1 to 3. ] 2. A photosensitive silver halide, at least one kind of coupler, at least one kind of a color developing agent represented by the general formula [A], at least one kind of hardly soluble metal hydroxide, A silver halide photographic light-sensitive material containing at least one metal ion-containing compound, which is subjected to image exposure and then treated with a solution containing at least one complex-forming compound. Processing method. 3. A photosensitive silver halide, at least one kind of coupler, at least one kind of a color developing agent represented by the general formula [A], at least one kind of auxiliary developing agent and at least one kind of a developing agent on a support. A silver halide photographic light-sensitive material containing a sparingly soluble metal hydroxide of the formula (I), followed by processing with a solution containing at least one complex forming compound. Processing method. 4. A support comprising a photosensitive silver halide, at least one kind of coupler, at least one kind of a color developing agent represented by the general formula [A], and at least one kind of hardly soluble metal hydroxide. Processing of a silver halide photographic material containing silver halide photographic material, after the image exposure, is treated with a solution containing at least one complex forming compound and at least one oxidizing agent. Method. 5. A support comprising a photosensitive silver halide, at least one coupler, at least one color developing agent represented by the above general formula [A], and at least one hardly soluble metal hydroxide. A silver halide photographic light-sensitive material containing at least one complex-forming compound and at least one metal ion-containing compound after imagewise exposing the silver halide photographic light-sensitive material containing the same. Processing method. 6. The silver halide according to claim 1, wherein the solution containing at least one complex forming compound further contains at least one auxiliary developing agent. Processing method of photographic photosensitive material. 7. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the hardly soluble metal hydroxide is zinc hydroxide. 8. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the complex-forming compound is at least one selected from picolinic acid and picolinate. .