JPH05307239A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and to improve shadow description performance by providing a photosensitive layer incorporating a black image forming compound and in corporating at least one kind of specified compound in the photosensitive layer. CONSTITUTION:At least one silver halide photosensitive layer contains >=90mol% silver chloride and a black image forming coupler, and another silver halide photosensitive layer contg. black image forming compound is provided separately from the silver photosensitive layer contg. the color coupler and at least one kind of compound represented by formula I or II is incorporated in the photosensitive layer, in which each or R1 and R2 is -CNM or -COR5 or the like; each of R3 and R4 is H, an alkyl, or the like; each of L1-L3 is a methine group; R5 is H, an aryl, or the like; k is 0, 1, or 2; each of V1 and V2 is H, CN, or the like; each or W1 and W2 is H, an aralkyl, or the like; each of X1 and X2 is H, a carboxy, or the like; m is 0, 1, or 2; n is 1, 2, or 3; and M<n+> is an m- valent cation.

Description

Detailed Description of the Invention

[0001]

The present invention has rapid processing suitability,
It also relates to a silver halide color photographic light-sensitive material having improved image sharpness and tone reproducibility.

[0002]

BACKGROUND OF THE INVENTION Conventionally, in order to form a color image with a silver halide color photographic light-sensitive material, a halogenation method which is usually sensitive to blue, green and red containing yellow, magenta and cyan dye-forming couplers is used. A silver halide color photographic light-sensitive material comprising a silver emulsion layer is imagewise exposed and then developed with a color developing agent to obtain a color image. By such color development processing, the aromatic primary amine of the color developing agent and the coupler are oxidatively coupled to form a color dye image, and the color of the subject can be reproduced.

In recent years, this color development processing time has been remarkably shortened, and a high-quality color photographic light-sensitive material suitable for so-called rapid processing, that is, having excellent sharpness and capable of reproducing delicate shadow depiction properties. There is a strong demand for a color photographic light-sensitive material that can be used.

Many proposals have heretofore been made to solve these problems. For example, a method for improving sharpness by selecting the particle size of titanium oxide contained in a polyolefin resin layer coating both sides of a support is disclosed in JP-A-3-2749, and JP-A-62-25753. In JP-A-2003-242, a method of using a support in which titanium oxide is surface-treated with a polyether-modified siloxane is proposed. Further, various methods for improving the sharpness by using a certain kind of dye have been proposed. For example, JP-A-6
0-225155, 62-164043, 62-165656 and the like. Furthermore, anti-halation dye (A
HU) is also known. US Patent No.
No. 2326057, No. 2882156, No. 2839401, JP-A-62-178245
No. etc. Further, JP-A-62-275246 describes a technique for improving sharpness by using an oxonol dye and a titanium oxide content. On the other hand, in order to improve the depiction of the shadow
-67537, 62-121453, 62-258453, 64-68754,
Japanese Patent Application Laid-Open Nos. 2-100046 and 2-129628 describe a technique for enhancing shadow depiction by using different spectral dyes and different color developing dyes in the same layer. In a color print photographic light-sensitive material, increasing the sharpness is a very important technique for producing high-quality prints required by users. However, the higher the sharpness is, the higher the visual contrast is, and it is a big problem that the print is inferior in the shadow depiction property, and there is a strong demand for a technique that solves both of them.

[0005]

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide a rapid-processing silver halide color photographic light-sensitive material having improved sharpness and improved shadow depiction. ..

[0006]

The above object of the present invention is to provide a silver halide color photographic light-sensitive material having a photosensitive layer containing cyan, magenta and yellow couplers on a support and at least one layer having a silver chloride content of 90 mol. % Or more, and further having a silver halide photosensitive layer containing a compound that produces a black image, in addition to the silver halide photosensitive layer containing the above color coupler, the photosensitive layer has the above-mentioned general formula [1 ]
This is achieved by a silver halide color photographic light-sensitive material characterized by containing at least one of the compounds represented by (Chemical formula 1) and [2] (Chemical formula 2).

The dye represented by the general formula [1] used in the present invention can be synthesized by reacting a dioxopyrazolopyridine compound with an appropriate monomethine source, trimethine source or pentamethine source compound. Specifically,
Japanese Patent Publication No. 39-22069, 43-3504, 52-38056, 54-
38129, 55-10059, JP-A-49-99620, 59-1683
It can be synthesized using the method described in U.S. Pat. No. 4, or U.S. Pat. No. 4,181,225.

Next, the compound represented by the general formula [1] will be described. Examples of the alkyl group represented by R ₃ to ₈ include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and the like, and the alkyl group includes those having a substituent, and examples of the substituent include Hydroxyl group, sulfo group, carboxyl group, halogen atom (eg fluorine, chlorine, bromine etc.), alkoxy group (eg methoxy, ethoxy etc.) Aryloxy group (eg phenoxy, 4-sulfophenoxy, 2,4-disulfone) Phenoxy, etc.), aryl groups (eg phenyl, 4-sulfophenyl, 2,5-disulfophenyl etc.), cyano groups, alkoxycarbonyl groups (eg methoxycarbonyl) and the like.

Examples of the aryl group represented by R ₃ to ₈ include a phenyl group and a naphthyl group, and the aryl group includes those having a substituent. As the aryl group having a substituent, 2-methoxyphenyl, 4-nitrophenyl, 3-chlorophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 4-methanesulfonylphenyl, 4-sulfophenyl, 3-sulfophenyl, 2 -Methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 4-chloro-3-sulfophenyl, 2-chloro-5-sulfophenyl, 2-methoxy-5-sulfophenyl, 2-hydroxy-4- Sulfophenyl, 2,5-
Dichloro-4-sulfophenyl, 2,6-diethyl-4-sulfophenyl, 2,5-disulfophenyl, 3,5-disulfophenyl, 2,4-disulfophenyl, 4-phenoxy-3-sulfophenyl , 2-chloro-6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 4-carboxyphenyl, 2,5-dicarboxyphenyl, 3,5-dicarboxyphenyl, 2, 4-dicarboxyphenyl, 3,6-disulfo
Examples include -α-naphthyl, 8-hydroxy-3,6-disulfo-α-naphthyl, 5-hydroxy-7-sulfo-β-naphthyl, and 6,8-disulfo-β-naphthyl.

Examples of the alkenyl group represented by R ₁₉ and R ₂₀ include vinyl and allyl, and the alkenyl group includes those having a substituent.

Examples of the heterocyclic group represented by R ₃ , R ₄ , R ₇ and R ₈ include pyridyl groups (2-pyridyl, 3-pyridyl, 4-pyridyl, 5-sulfo-2-pyridyl, 5- Carboxy-
2-pyridyl, 3,5-dichloro-2-pyridyl, 4,6-dimethyl-
2-pyridyl, 6-hydroxy-2-pyridyl, 2,3,5,6-tetrafluoro-4-pyridyl, 3-nitro-2-pyridyl, etc., oxazolyl group (5-sulfo-2-benzoxazolyl) , 2-benzoxazolyl, 2-oxazolyl, etc.), thiazolyl group (5-sulfo-2-benzothiazolyl, 2-benzothiazolyl, 2-thiazolyl etc.), imidazolyl group (1-methyl-2-
Imidazolyl, 1-methyl-5-sulfo-2-benzimidazolyl, etc.), furyl group (3-furyl, etc.), pyrrolyl group (3-pyrrolyl, etc.), thienyl group (2-thienyl, etc.), pyrazinyl group (2-pyrazinyl, etc.) ), A pyrimidinyl group (2-pyrimidinyl, 4-chloro-2-pyrimidinyl, etc.), a pyridazinyl group (2
-Pyridazinyl etc.), purinyl group (8-purinyl etc.), isoxazolinyl group (3-isoxazolinyl etc.), selenazolyl group (5-sulfo-2-selenazolyl etc.), sulforanyl (3-sulfolanyl etc.), Piperidinyl group (1-methyl
-3-piperidinyl etc.), pyrazolyl (3-pyrazolyl etc.), tetrazolyl group (1-tetrazolyl etc.) and the like.

Examples of the cycloalkyl group represented by R ₁₆ and R ₁₇ include cyclopentyl and cyclohexyl, and the cycloalkyl group includes those having a substituent.

The methine groups represented by L ₁ to ₃ include those having a substituent (for example, an alkyl group, an aryl group, etc.).

Examples of the 5- or 6-membered ring formed by combining R ₇ and R ₈ together with the nitrogen atom include pyrrolidine, piperazine, piperidine and morpholine.

Examples of the water-soluble group contained in R ₁ to ₄ or at least one of these include a sulfo group, a carboxyl group, a sulforanyl group and the like, and the water-soluble group is a salt such as sodium salt or potassium salt. Including.

Typical specific examples of the dye of the present invention represented by the above general formula [1] are shown below, but not limited thereto.

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

Next, the compound represented by the general formula [2] will be described.

V ₁ , V ₂ , W ₁ , W _2. X ₁ , X ₂ , R _{1 to} R ₆
Examples of the alkyl group represented by include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, etc., and these alkyl groups further include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom (for example, fluorine, chlorine, Bromine, etc.), alkoxy group (eg, methoxy, ethoxy, etc.), aryloxy group (eg, phenoxy, 4-
Sulfophenoxy, 2,4-disulfophenoxy etc.), aryl group (eg phenyl, 4-sulfophenyl, 2,5-disulfophenyl etc.), cyano group, alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl etc.) ) It may be substituted with an aryloxycarbonyl group (eg, phenoxycarbonyl) or the like.

V ₁ , V ₂ , W ₁ , W _2. X ₁ , X ₂ , R _{1 to} R ₆
Examples of the aryl group represented by are phenyl, 2-methoxyphenyl, 4-nitrophenyl, 3-chlorophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 4-methanesulfonylphenyl, 4-sulfophenyl and 3-sulfophenyl. Phenyl, 2-methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 4-chloro-3-sulfophenyl, 2-chloro-5-
Sulfophenyl, 2-methoxy-5-sulfophenyl, 2-hydroxy-4-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 2,6-diethyl-4-sulfophenyl, 2,5-disulfophenyl , 3,5-disulfophenyl, 2,4-disulfophenyl, 4-phenoxy-3-sulfophenyl, 2-chloro-6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5
-Sulfophenyl, 4-carboxyphenyl, 2,5-dicarboxyphenyl, 3,5-dicarboxyphenyl, 2,4-dicarboxyphenyl, 3,6-disulfo-α-naphthyl, 8-hydroxy-3,6 -Disulfo-α-naphthyl, 5-hydroxy-7-sulfo-β-naphthyl, 6,8-disulfo-β-naphthyl and the like can be mentioned.

V ₁ , V ₂ , W ₁ , W _2. X ₁ , X ₂ , R _{1 to} R ₆
The heterocyclic group represented by, for example, pyridyl group (2-pyridyl, 3-pyridyl, 4-pyridyl, 5-sulfo-2-pyridyl, 5-carboxy-2-pyridyl, 3,5-dichloro-2- Pyridyl, 4,6-dimethyl-2-pyridyl, 6-hydroxy-2-pyridyl, 2,3,5,6-tetrafluoro-4-pyridyl, 3-nitro-2-
Pyridyl), oxazolyl group (5-sulfo-2-benzoxazolyl, 2-benzoxazol, 2-oxazolyl, etc.), thiasolyl group (5-sulfo-2-benzothiazolyl, 2
-Benzothiazolyl, 2-thiazolyl etc.), imidazolyl group (1-methyl-2-imidazolyl, 1-meth-5-sulfo-2-benzimidazolyl etc.), furyl group (3-furyl etc.), pyrrolyl group (3-pyrrolyl etc.) ), A thienyl group (2-thienyl group), a pyrazinyl group (2-pyrazinyl, etc.), a pyrimidinyl group (2-pyrimidinyl, 4-chloro-2-pyrimidinyl, etc.),
Pyridazinyl group (2-pyridazinyl, etc.), Purinyl group (8-
Purinyl group), isooxolinyl group (3-isoxazolinyl etc.), selenazolyl group (5-sulfo-2-selenazolyl etc.), sulforanyl (3-sulfolanyl etc.), piperidinyl group (1-methyl-3-piperidinyl etc.), Pyrazolyl (3-
Pyrazolyl etc.), tetrazolyl group (1-tetrazolyl etc.)
Etc.

The methine groups represented by L ₁ , L ₂ and L ₃ include those having a substituent (eg, methyl group, ethyl group, phenyl group, chlorine atom, etc.).

As the n-valent cation represented by M ^{n +} ,
For example, Na ⁺ , K ⁺ , Ca ⁺ , NH ₄ ⁺ , HN (C ₂ H ₅ ) ₃ ⁺ , C ₅ H ₆ N ^{+ and the} like are shown.

Typical specific examples of the dye of the present invention represented by the general formula [2] are shown below, but the dye of the present invention is not limited thereto.

[0029]

[Chemical 8]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical formula 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

These dyes are described in British Patent Nos. 1278627 and 1512.
It can be synthesized by the method described in No. 863, No. 1579899 or the like. General formulas [1] and [2] used for the black color-dye-containing layer
The addition amount of the dye represented by is not particularly limited, but 1 to 100 m
g / m ² is preferable, and 5-500 mg / m ² is more preferable. The dyes of the general formulas [1] and [2] may be used alone or in combination. Further, they may be the same as or different from the irradiation swelling preventing dye contained in the silver halide photosensitive layer, or they may be used in combination.

Next, the photosensitivity of the silver halide emulsion layer (hereinafter referred to as black layer) containing a compound forming a black dye image may be any of blue, green and red photosensitivity forming a color image. Also, for example, 2 for blue and green sensitivity
It may be spectrally sensitized in one spectral region, or may be spectrally sensitized in all spectral regions of blue, green and red sensitivities. This black layer may be one layer or two or more layers. Further, the sensitivity of the spectrally sensitized black layer is 1/3 or less, and more preferably 1/4 to 1 of the sensitivity of the silver halide emulsion layer containing each coupler spectrally sensitized in the same spectral region. The sensitivity is 1/10. The black layer of the present invention reacts with the oxidation product of the color developing agent to form a black dye image, and the maximum density of the black dye image is preferably 0.1 to 0.7, more preferably 0.2 to 0.5. When the maximum density is 0.1 or less, the reproducibility or stability of neutral gray or black is low, and when it exceeds 0.7, the color separation of the shadow part is deteriorated.

The silver halide grains forming the black dye are not particularly limited.

Various compounds can be used as the compound for forming the black dye image used in the present invention, and among them, particularly preferably used are those disclosed in JP-A-52-4.
2725, JP-A-53-46029, Japanese Patent Application No. 52-48790, and other black couplers. These black couplers can form a good black dye image by reaction with a commonly used para-phenylenediamine type color developing agent. Among these, as a black coupler which forms a typical black dye image, there is a compound represented by the following general formula [B].

[0041]

[Chemical 16]

Here, R ₁ and R ₂ are each a hydrogen atom,
It represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group, and R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a hydroxy, an alkyl group, an alkoxy group, an alkylamide group, an arylamide group, an alkylsulfonamide group or an arylsulfone. Represents an amide group, and X and Y are each a hydrogen atom, a halogen atom (eg, chloro, prom, etc.) or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent (hereinafter simply referred to as split Off group), or one of X and Y is hydroxyl, mercapto, amino,
It is an alkylamino group or an arylamino group, and the other is a hydrogen atom, a halogen atom or the above split-off group.

The alkyl group represented by R ₁ and R ₂ is preferably an alkyl group having 1 to 32 carbon atoms, and more preferably an alkyl group having 1 to 22 carbon atoms. May be linear or branched, or may be an alkyl group having a substituent. Examples of alkyl include methyl, ethyl, isopropyl, n-
Butyl, n-dodecyl, n-octadecyl, sec-octadecyl, n-docosyl and the like can be mentioned. Further, as the substituent of the substituted alkyl, any group can be selected, but preferably hydroxyl, carboxyl, sulfo, alkylcarbamoyl group, alkylsulfamoyl group, arylcarbamoyl group, arylsulfamoyl group, alkoxycarbonyl group, Examples thereof include an alkoxysulfonyl group, an aryloxycarbonyl group, an aryloxysulfonyl group, an alkoxy group, an aryloxy group, an alkylamide group, an arylamide group, an alkylsulfonamide group and an arylsulfonamide group.

The aralkyl group represented by R ₁ and R ₂ is preferably the number of carbon atoms in the alkylene chain connecting the nitrogen atom of the compound represented by the general formula [B] and the aryl moiety of the aralkyl group. May be 1 to 32, more preferably 1 to 12 carbon atoms, and the aryl moiety may be phenyl, which may be an aralkyl having a substituent. Examples of aralkyl include benzyl, phenethyl-β-naphthylmethyl, phenylheptyl and the like. Although any group can be selected as the substituent of the substituted aralkyl, for example, hydroxyl, carboxyl, halogen atom (eg, chloro, bromo, etc.), alkyl group, alkylamide group, arylamide group, alkylsulfonamide group are preferable. , Arylsulfonamide groups and the like.

The aryl group represented by R ₁ and R ₂ is preferably a phenyl group and may be an aryl having a substituent. Examples of the aryl include phenyl and the like. Further, as the substituent of the substituted aryl, any group can be selected, but preferably, for example, a halogen atom (eg, chlorine, bromine, etc.), an alkylamido group,
Examples thereof include an arylamide group, an alkylsulfonamide group, and an arylsulfonamide group.

The alkenyl group represented by R ₁ and R ₂ is preferably a linear or branched alkenyl having 3 to 22 carbon atoms and has a substituent even if it has a cyclic structure. May be. Examples of alkenyl include allyl, octenyl, cyclohexenylethyl, 5,9-dimethyl-9-dodecenyl, 9-octadecenyl and the like.
Further, the substituent of the substituted alkenyl is preferably a halogen atom (eg, chlorine, bromine, etc.).

The alkyl moiety of the alkylcarbamoyl group, alkylsulfamoyl group, alkoxycarbonyl group, and alkoxysulfonyl group, which are mentioned as the substituents of the alkyl group represented by R ₁ and R ₂ , preferably have 1 carbon atom. To 22 linear or branched alkyl moieties, which may further have a substituent. Examples of the unsubstituted alkyl moiety include methyl, ethyl, tert-butyl, octyl, n-octadecyl, sec-octadecyl, n-
Docosyl and the like, and examples of the substituted alkyl moiety include 1- (n-octadecylcarbamoyl) ethyl, 2- (2-sulfooctadecamido) ethyl, octadecylsuccinimidopropyl, and 2- (N-octadecyl-N-carboxyl. Methylaminoacetamido) ethyl, n-dodecyloxymethoxypropyl, 2,4-di-tert-amylphenoxybutyl, 3-pentadecylphenoxypropyl and the like.

The aryl moiety of the arylcarbamoyl group, the arylsulfamoyl group, the aryloxycarbonyl group and the aryloxysulfonyl group, which are mentioned as the substituents of the alkyl group represented by R ₁ and R ₂ , is preferably phenyl, It is naphthyl, more preferably phenyl. Examples of the unsubstituted aryl moiety include phenyl and naphthyl, and the substituted aryl moiety includes, for example, p-dodecylphenyl, m-pentadecylphenyl, o-tetradecyloxyphenyl, p-octadecyloxyphenyl, 2- Methoxy-5-tetradecyloxycarbonylphenyl, 3,4-di-n-butyloxycarbonylphenyl, p-tert-butylphenoxyphenyl, m-lauroylamidophenyl, m-dodecylbenzenesulfonamidephenyl, 4-lauroylamidonaphthyl , 5-octadecyloxynaphthyl, 2-chloro-5- (2,4-di-tert-amylphenoxybutyramide) phenyl and the like.

As the alkyl moiety of the alkoxy group mentioned as the substituent of the alkyl group represented by R ₁ and R ₂ ,
Preferred is a linear or branched alkyl moiety having 1 to 22 carbon atoms, which may further have a substituent. Examples of the unsubstituted alkyl moiety include methyl, propyl, peptyl, n-dodecyl, n-octadecyl and the like, and examples of the alkyl moiety having a substituent include p-
Examples thereof include tert-butylphenoxyethyl, p-octadecylphenoxyethyl, dodecyloxyethyl and the like.

The aryl moiety of the aryloxy group mentioned as the substituent of the alkyl group represented by R ₁ and R ₂ is
Substituted or unsubstituted phenyl is preferred. Examples of the substituted phenyl include p-dodecylphenyl, p-lauroylamidophenyl, p-tert-butylphenoxyphenyl, m-octadecylsulfonamidophenyl and the like.

The alkylamido group mentioned as the substituent of the alkyl group, aralkyl group and aryl group represented by R ₁ and R ₂ is preferably an alkanoic acid amide having 1 to 22 carbon atoms, and these are further It may have a substituent.
Examples of the alkylamide include butanamide, octaamide, dodecamide, hexadecamide, and the like.
Examples of the substituted alkylamide include m-pentadecylphenoxyacetamide, 2,4-di-tert-amylphenoxybutanamide, p-tert-amylphenoxycarbonylpropanamide, m-decyloxyphenoxyacetamide,
2-n-butoxide decanamide and the like can be mentioned. The arylamide group mentioned as the substituent of the alkyl group, aralkyl group and aryl group represented by R ₁ and R ₂ is
A benzamide group and a naphthamide group are preferred, and a benzamide group is even more preferred. Examples of arylamides include benzamide and α-naphthamide. As the substituted arylamide, for example, preferably p-methylbenzamide, p-tert-butylbenzamide, m-lauroylamide benzamide, o-dodecyloxybenzamide, m- (p-tert-amylphenoxy) benzamide and the like. Is mentioned.

The alkylsulfonamide group mentioned as the substituent of the alkyl group, aralkyl group and aryl group represented by R ₁ and R ₂ preferably has 1 to 22 carbon atoms.
And a linear or branched alkylsulfonamide group, which may further have a substituent. Examples of the alkyl sulfonamide include methyl sulfonamide, butyl sulfonamide, tert-butyl sulfonamide, n-dodecyl sulfonamide, and n-docosyl sulfonamide. Examples of the substituted alkylsulfonamide include N-methyllauroylamide ethylsulfonamide, N-
Examples thereof include phenyl octadecane amide ethyl sulfonamide and lauroyl amide ethyl sulfonamide.

The arylsulfonamide group mentioned as the substituent of the alkyl group, aralkyl group and aryl group represented by R ₁ and R ₂ is preferably a phenylsulfonamide group or a naphthylsulfonamide group, and these are further It may have a substituent. The arylsulfonamide is preferably, for example, benzenesulfonamide or naphthalenesulfonamide. Examples of the substituted aryl sulfonamide include tolyl sulfonamide, p-octadecane amide phenyl sulfonamide, p-dodecyl phenyl sulfonamide, 4,8-di-isopropylnaphtho-2-yl-
Examples thereof include sulfonamide and 3-methoxy-6-octadecanamide phenyl sulfonamide.

The alkyl group mentioned as the substituent of the aralkyl group represented by R ₁ and R ₂ is preferably a linear or branched alkyl group having 1 to 22 carbon atoms. Preferred examples include methyl, ethyl, dodecyl and the like.

The alkyl group represented by R ₃ and R ₄ is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. It may be a chain or a branch. For example, alkyl includes methyl, ethyl, tert-butyl and the like.

The alkoxy group represented by R ₃ and R ₄ is preferably an alkoxy group having 1 to 22 carbon atoms, preferably, for example, methoxy, ethoxy, butoxy, dodecyloxy, octadecyloxy, sec-octadecyl. Oxy etc. are mentioned. The alkylamido group represented by R ₃ and R ₄ preferably has 1 carbon atom.
To 22 alkyl amides, which may be linear or branched. Preferable examples of the alkylamide include acetamide, propionamide, hexadecamide and the like.

The alkylsulfonamide group represented by R ₃ and R ₄ is preferably an alkylsulfonamide having 1 to 22 carbon atoms, which may be linear or branched. As the alkyl sulfonamide,
For example, methanesulfonamide, propanesulfonamide, sec-butanesulfonamide, n-dodecylsulfonamide, n-octadecylsulfonamide and the like are preferable.

The arylamide group and arylsulfonamide group represented by R ₃ and R ₄ are the arylamide groups and examples of the substituents of the alkyl group, aralkyl group and aryl group represented by R ₁ and R _2. Group has the same meaning as arylsulfonamide group.

The split-off group represented by X and Y is preferably, for example, sulfo (-SO ₃ H) or a salt thereof, carboxyl (-COOH) or a salt thereof, an alkoxy group, an allyloxy group, an alkylcarbonyloxy group. , Alkylsulfonyloxy group, arylcarbonyloxy group, arylsulfonyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, alkylamide group, arylamide group, alkylsulfonamide group, arylsulfonamide group, 5- or 6-membered ring Examples thereof include an imide group, an arylthio group, an arylseleno group, an arylsulfonyl group, an arylazo group, and a 5- or 6-membered heterocyclic thio group having 1 to 4 nitrogen atoms in its molecular structure.

The alkyl moiety of the alkoxy group as the split-off group is preferably a linear or branched alkyl moiety having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and these further have a substituent. You may. Unsubstituted alkyl moieties include methyl, ethyl, is
Examples include o-propyl and the like. As the substituent of the alkyl moiety having a substituent, any group can be selected, but for example, a halogen atom, an alkyloxycarbonyl group, an alkylcarbamoyl group, an aryloxycarbonyl group, an arylcarbamoyl group and the like can be mentioned. Specific examples of the substituted alkyl moiety include, for example, chloroethyl, butoxycarbonylmethyl, β-hydroxyethoxycarbonylmethyl, m-hexadecaamidophenoxycarbonylmethyl, p-methoxyethoxycarbonylpropyl, is
Examples thereof include o-propylcarbamoylmethyl, n-dodecylcarbamoylmethyl, m-dodecanamidophenylcarbamoylpropyl, m-hexadecaamidophenoxycarbonylmethyl and o-dodecyloxyphenylcarbamoylmethyl.

The aryloxy group as the split-off group is preferably a phenyloxy group, which may further have a substituent. Examples of aryloxy include phenoxy. Examples of the substituent of the substituted aryloxy include carboxyl or a salt thereof, sulfo or a salt thereof, a halogen atom and the like.

The alkyl moiety of the alkylcarbonyloxy group as the split-off group is preferably a linear or branched alkyl moiety having 1 to 22 carbon atoms, which may further have a substituent. The unsubstituted alkyl moiety is preferably methyl, ethyl, tert-butyl, n-dodecyl, n-docosyl or the like. The substituent of the alkyl moiety having a substituent is preferably a halogen atom (eg, fluorine, chlorine, bromine, etc.).

The arylcarbonyloxy group as the split-off group is preferably a phenylcarbonyloxy group, which may have a substituent. Preferable examples of arylcarbonyloxy include phenylcarbonyloxy and the like. Examples of the substituent of the substituted arylcarbonyloxy include an alkyl group and an alkylamido group. The alkyl group is preferably alkyl, and examples thereof include methyl and tert-butyl. Examples of the alkylamide group include dodecane amide, 2,4-di-tert-amylphenoxyacetamide and the like.

The alkyl moiety of the alkylsulfonyloxy group as the split-off group is preferably a linear or branched alkyl moiety having 1 to 22 carbon atoms, which may further have a substituent. Unsubstituted alkyl moieties include methyl, tert-butyl, n-dodecyl, n
-Docosyl and the like. Any group can be selected as the substituent of the alkyl moiety having a substituent, preferably an alkylamide group, more preferably an alkylamide, such as lauroylamide, N-methyllauroylamide. ..

The aryl moiety of the arylsulfonyloxy group as the split-off group is preferably a phenyl group, which may further have a substituent. The unsubstituted aryl moiety is, for example, phenyl or the like.
As the substituent of the aryl moiety having a substituent, for example, alkyl having 1 to 22 carbon atoms is preferable.

The alkylcarbamoyloxy group as the split-off group is preferably alkylcarbamoyloxy having 1 to 4 carbon atoms.

The arylcarbamoyloxy group as the split-off group is preferably a phenylcarbamoyloxy group. Examples of arylcarbamoyloxy include phenylcarbamoyloxy and the like. As the substituent of the substituted arylcarbamoyloxy, any group can be selected, and examples thereof include a halogen atom, an alkoxy group (preferably unsubstituted alkoxy, such as methoxy, ethoxy, etc.), an alkylamide group (preferably alkylamide). And, for example, propionamide, dodecane amide, etc.), cyano group and the like.

The alkylamide group as the split-off group is particularly preferably a halogen-substituted alkylamide, and examples thereof include trichloroacetamide, trifluoroacetamide, heptafluoropropionamide and octafluoropentanamide.

The arylamide group as the split-off group is preferably a benzamide group, more preferably a halogen-substituted benzamide, and examples thereof include pentachlorobenzimide and pentafluorobenzamide.

The alkylsulfonamide group as the split-off group, the alkyl moiety of the arylsulfonamide group, and the aryl moiety have the same meanings as the alkylsulfonyloxy group as the split-off group and the alkyl moiety and the aryl moiety of the arylsulfonyloxy group, respectively. Is.

The 5- or 6-membered imide group as the split-off group is preferably a succinimide group or a glutarimide group, and these groups further include an alkyl group (preferably a straight chain or branched chain having 1 to 22 carbon atoms). Alkyl), and may form a condensed ring like phthalimide.

The arylazo group as the split-off group is preferably a phenylazo group, and for example, phenylazo substituted with a halogen atom or an alkyloxycarbonyl group having 1 to 22 carbon atoms is preferable. The part may be further substituted. An example of this is 2-chloro-5- {α
Examples include-(dodecyloxycarbonyl) ethoxycarbonyl} -phenylazo and o-octadecyloxycarbonylphenylazo.

The 5- or 6-membered heterocyclic thio group containing 1 to 4 nitrogen atoms in the molecular structure as a split-off group is an imidazole group, a triazole group, a tetrazole group, an oxazole group or a thiazole group. Represents a heterocyclic thio group such as a thiadiazine group, and this heterocyclic moiety may form a condensed ring with another unsaturated or saturated hydrocarbon. Examples of these include 1-phenyltetrazolyl-5-thio, benztriazolylthio, benzoxazolylthio, benzthiazolylthio and 3-benzoyl.
-5-methyl-1,3,4-thiadiazin-2-yl-thio and the like can be mentioned.

Of the arylthio group, the arylseleno group and the arylsulfonyl group as the split-off group, phenylthio, phenylseleno and phenylsulfonyl are specifically preferable.

According to a preferred embodiment of the present invention, when X and Y in the general formula [B] are hydrogen atom, halogen atom or split-off group, the compound of the present invention is composed of two molecules of aromatic primary amine. Different from the usual cyan color-forming dyes (which are dyes coupled with one molecule of an aromatic primary amine-based developing agent, as is well known in the art) by coupling with a color-developing agent. Produces a pure black color pigment.

Further, according to a further preferred embodiment of the present invention, in the general formula [B], at least one of R ₁ and R ₂ is a hydrogen atom.

These black image-forming couplers used in the present invention do not contain a color-developing agent portion in the molecular structure and therefore are extremely stable against oxidation, and an excellent image free from contamination can be obtained. it can.

Next, typical examples of black couplers preferably used in the present invention will be given, but the present invention is not limited thereto.

[Representative example of black coupler] (B-1) N-octadecyl-m-aminophenol (B-2) N- {α- (dodecylcarbamoyl) ethyl} -m-aminophenol (B-3) 4 -(4-Lauroylamidophenethyl) -m-aminophenol (B-4) 4-chloro-N-octadecyl-m-aminophenol (B-5) 6-chloro-N-octadecyl-m-aminophenol (B- 6) 2-chloro-4- (isopropylcarbamoylmethoxy) -5-N-octadecylaminophenol (B-7) 4- (iso-propylcarbamoylmethoxy) -3-N-
Octadecylaminophenol (B-8) 4-benzenesulfonyloxy-3-N-octadecylaminophenol The compound that produces the black dye image used in the present invention is
The color coupler is not limited to the above black coupler and may be a mixture of two or more color couplers. Specifically, two or more color couplers can be mixed to obtain a black dye image according to the present invention. For example, a black dye image can be obtained by mixing a magenta coupler having a large amount of secondary absorption and a cyan coupler, and a normal color coupler, that is, yellow,
It is also possible to form a black dye image by appropriately selecting and mixing color couplers such as magenta and cyan. Further, it is also possible to form a black dye image by mixing 4 or 5 or more color couplers having different absorption characteristics. That is, the compound which forms the black dye image of the present invention may be any compound or a combination of a plurality of compounds as long as it is a compound which reacts with an oxidation product of a commonly used color developing agent to form a black dye image.

Next, the addition amount and timing of the compound (hereinafter, referred to as a black dye forming compound) for forming a black dye image used in the present invention will be explained (the adding method will be described later). That is, the amount of the black dye-forming compound added is 1 to 1000 g, preferably 5 to 500 g per mol of silver, and the addition timing is spectrally sensitized after oil protection or Fisher dispersion and before coating. It is desirable to add it to the silver halide emulsion. In the silver halide photographic light-sensitive material of the present invention (hereinafter sometimes abbreviated as light-sensitive material), the silver halide grains contained in at least one of the silver halide emulsion layers have a silver chloride content of 90 mol% or more. Of silver chloride or silver chlorobromide which does not substantially contain silver iodide.

The silver chloride content is preferably 95 mol% or more, and particularly preferably in the range of 98 to 99.9 mol% for demonstrating the effects of the present invention, which simultaneously satisfies the effects of the present invention and rapid processability. In addition, it means that it does not substantially contain silver iodide,
Silver chloroiodobromide having a silver iodide content of 0.5 mol% or less, and silver chlorobromide containing no silver iodide is preferred. That is, in the present invention, silver chlorobromide having a silver bromide content of 0.1 to 2 mol% is preferably used.

The silver halide emulsion according to the present invention may be composed of grains having a single composition, or may be a mixture of silver halide grains having different compositions. Further, it may be used by mixing with silver halide grains having a silver chloride content of 90 mol% or less within a range in which the effects of the present invention are not impaired.

In the silver halide emulsion layer containing the silver halide grains having a silver chloride content of 90 mol% or more according to the present invention, the chloride contained in all silver halide grains contained in the emulsion layer is The proportion of silver halide grains having a silver content of 90 mol% or more is 60 wt% or more, preferably 80 wt% or more.

The silver halide grain of the present invention preferably contains an iridium-containing compound and at least one kind of metal-containing compound belonging to Group VIII of the periodic table other than iridium.

Metal-containing compounds other than iridium belonging to Group VIII of the Periodic Table are iron-, cobalt-, nickel-, ruthenium-, rhodium-, palladium-, osmium-, and platinum-containing compounds, respectively. Salt, yellow blood salt, ferrous thiocyanate, ferric thiocyanate
Iron, ferrous chloride, ferric chloride, cobalt chloride, cobalt nitrate, ruthio salt, nickel chloride, nickel sulfate, ruthenium chloride, ruthenium hydroxide, rhodium chloride, ammonium hexachlororhodate, palladium chloride, palladium nitrate, hexachloropalladium Examples thereof include potassium acid salt, osmium chloride, ammonium hexachloroplatinate and potassium hexachloroplatinate. or,
Complex salts containing a nitrosyl or thionitrosyl ligand described in JP-A 2-20852 are also preferably used.

The iridium-containing compound used in combination therewith is a trivalent or tetravalent salt or complex salt. Typical compounds include first iridium chloride, first iridium bromide, second iridium chloride, potassium hexachloroiridium (III), potassium hexachloroiridium (IV), hexaammineiridium (III) salt, hexaammineiridium. (IV) salt, trioxalatoiridium (III) salt, and trioxalatoiridium (IV) salt.

The amount of the iridium-containing compound used is 1 × 10 ^{−11 to} 5 × 10 ⁻⁵ mol, preferably 1 × 10 ⁵ mol, per mol of silver.
^{-9 to} 5 x 10 ^-6 mol.

The amount of the metal-containing compound of Group VIII of the periodic table used is appropriately 1 × 10 ^-9 to 1 × 10 ^-3 mol, and further 1 × 10 9
^-8 to 1 × 10 ^-4 mol is preferable because the effect of the present invention is large.

In the present invention, the iridium compound and the
In order to include the Group VIII metal-containing compound in the particles,
It suffices that the above compound is present at the time of silver halide grain formation, and rush addition, continuous addition or divided addition may be performed.

It is preferable that the iridium compound and the Group VIII metal-containing compound are present at the same time when the silver halide grains are formed.

In the present invention, chemical sensitization, that is, so-called gold sensitization is preferably performed by at least a gold-containing compound.

As the gold sensitizer (gold-containing compound) for gold sensitization, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used.
Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like.

The addition amount of the gold sensitizer also varies depending on various conditions, but the addition amount of the gold compound is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol per mol of silver halide, and 2 × 10 ^{−. 6} ~
1 × 10 ⁻⁴ is more preferable, and 2.6 × 10 ⁻⁶ to 4 × 10 ⁻⁵ mol is further preferable.

A particularly preferable chemical sensitizing means in carrying out the present invention is to use chalcogen sensitization and gold sensitization in combination. Thereby, a remarkable sensitizing effect can be obtained.

As the chalcogen sensitizer applied to the silver halide emulsion used in the present invention, sulfur sensitizer, selenium sensitizer, tellurium sensitizer and the like can be used. Of these, sulfur sensitizers are preferable.

Among the above, the combined use of sulfur sensitization and gold sensitization is particularly useful because not only the sensitizing effect but also the effect of suppressing fog can be obtained.

Various sulfur sensitizers can be used for the above sulfur sensitization. Examples thereof include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like. Other U.S. Patents 1,574,944
3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-24937
The sulfur sensitizers described in JP-A No. 55-45016 and the like can also be used.

The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is 10 ^-7 to 10 ^-1 mol per mol of silver halide. Is preferred.

The silver halide emulsion of the present invention may be reduction sensitized.

A known method can be used for reduction sensitizing the silver halide emulsion used in the present invention. For example, a method of adding various reducing agents can be used, or a method of aging under conditions of high silver ion concentration or a method of aging under conditions of high pH can be used.

The reducing agent used for reduction sensitization of the silver halide emulsion used in the present invention includes stannous salts such as stannous chloride, boranes such as tri-t-butylamineborane, sodium sulfite and potassium sulfite. Sulfites, reductones such as ascorbic acid, thiourea dioxide and the like can be used. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is carried out by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or they are added at the time of forming silver halide grains to reduce and increase them simultaneously with grain formation. You may feel.

The amount of these reducing agents added needs to be adjusted according to the pH and silver ion concentration of the silver halide emulsion, but generally 1 mol of the silver halide emulsion is from 10 ^-7 to 10 -10.
^-2 mol is preferred.

After the reduction sensitization, a small amount of an oxidizing agent may be used to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of compounds used for such purposes include:
Examples thereof include potassium hexacyanosilver (III), bromosuccinimide, p-quinone, potassium perchlorate, hydrogen peroxide and the like.

The temperature of the chemical ripening in the present invention is arbitrary as long as the desired sensitization is achieved, but it is preferably 90 to 20 ° C, more preferably 80 to 30 ° C, and particularly preferably 70. ~ 35 ° C.

The grain size of the silver halide grains used in the present invention is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to It is in the range of 1.2 μm.

The grain size distribution of silver halide grains may be polydisperse or monodisperse. Monodisperse silver halide grains having a variation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred.

The coefficient of variation is the ratio (σ / r _m ) of the standard deviation (σ) to the average particle size (r _m ).

In the present invention, the silver halide grains used in the emulsion may be those obtained by any of the acidic method, the neutral method and the ammonium method. The particles may be grown at one time, or may be grown after forming seed particles.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. It is also possible to use particles having a shape such as an octahedron, a tetrahedron or a dodecahedron. Further, grains having twin planes may be used.

The silver halide emulsion used in the present invention has the purpose of preventing fog occurring during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fog occurring during development. Antifoggant known in
Stabilizers can be used. Examples of compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific compounds thereof include: 8 of the publication
(IIa-1) to (IIa-8) and (IIb-1) to
Examples thereof include the compound (IIb-7) and 1- (3-methoxyphenyl) -5-mercaptotetrazole. These compounds are added in steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution, depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ^-6 to 1 × 10 ^-2 mol, and 1 × 10 ^{-5 to} 5 × 10 ^-3 mol per mol of silver halide. More preferable. When it is added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and 1 × 10 ^-5 to 1 × 10 ^{5. -2} mol is more preferred. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol.

When the light-sensitive material according to the present invention is used as a color light-sensitive material, it is combined with a yellow coupler, a magenta coupler and a cyan coupler to spectrally sensitize a silver halide emulsion spectrally sensitized to a specific region in the wavelength range of 400 to 900 nm. Having a layer containing. The silver halide emulsion contains one or more spectral sensitizing dyes in combination.

As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used. As the blue-sensitive layer sensitizing dye, Japanese Patent Application No.
BS-1 to BS-8 described in JP-A-51124, pages 108 to 109 can be preferably used alone or in combination, and as the green-sensitized sensitizing dye, GS-1 to BS-110 described in page 110 of the specification can be used. 5 is preferably used. Examples of the red-sensitizing sensitizing dye include RS described on pages 111 to 112 of the same specification.
-1 to 8 are preferably used. When exposing the silver halide photographic light-sensitive material according to the present invention by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, and as the infrared-sensitive sensitizing dye,
The supersensitizers SS-1 to SS-9 described on pages 12 to 14 of Japanese Patent Application No. 3-73619 are preferably used in combination with these dyes.

When the silver halide photographic light-sensitive material according to the present invention is exposed using a laser, it is advantageous to use it in an exposure device using a semiconductor laser in terms of downsizing of the device. In scanning exposure, when the exposure time per image corresponds to the exposure time actually received by the silver halide emulsion, in the spatial change in the intensity of the luminous flux,
The outer edge of the light flux is defined as the point where the light density becomes 1/2 of the maximum value, and the distance between two points where the outer edge of the light flux intersects with the line that is parallel to the scanning line and has the maximum light intensity. When the diameter is used, the (light flux diameter) / (scanning speed) can be considered as the exposure time per pixel. As the exposure time per pixel becomes shorter, the relationship between the exposure time and the color density tends to become more complicated, and the present invention is particularly effective when an apparatus having a short exposure time per pixel is used.

As a laser printer device considered to be applicable to such a system, for example, Japanese Patent Laid-Open No. 55-4
071, JP-A-59-11062, JP-A-63-197947, JP-A
2-74942, Japanese Patent Laid-Open No. 2-236538, Japanese Patent Publication No. 56-14963, Japanese Patent Publication No. 56-40822, European Wide Area Patent 77410, Department of Electronics and Communication Technology Research Report 80, Volume 244, and Movie Television Technical Journal 1984. /
6 (382), pages 34-36.

Dyes having absorption in various wavelength regions can be used in the light-sensitive material of the present invention for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used, and particularly as a dye having absorption in the visible region, Japanese Patent Application No. 2-51124 117.
The dyes of AI-1 to 11 described on pages 118 to 118 are preferable, and the infrared absorbing dyes are represented by the general formulas (I), (II) and (III) described in JP-A 1-280750, page 2, lower left column. The compounds represented are preferable because they have preferable spectral characteristics, have no influence on the photographic characteristics of the silver halide photographic emulsion, and have no contamination due to residual color. As specific examples of preferable compounds, the exemplified compounds (1) to (4) described in the same publication, page 3, lower left column to page 5, lower left column.
5) can be mentioned.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Other than the yellow coupler of the present invention, a typical example is a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm. It has been known.

As the yellow coupler preferably used in the silver halide photographic light-sensitive material according to the present invention, Japanese Patent Application No.
Examples thereof include couplers represented by the general formula (YI) described on page 8 of 2-234208. Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same specification. Among these, YC-8, Y
C-9 is preferable because it can reproduce a preferable yellow color.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Japanese Patent Application No. 2-234208, the general formula (C-
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in CC in pages 18 to 21 of the specification.
Examples thereof include those described as -1 to CC-9.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, If necessary, a bottom boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and the resulting mixture is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a coro middle, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high-boiling organic solvent that can be used to dissolve and disperse the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic-solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent as necessary to prepare a gelatin aqueous solution. A method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described on page 33 of Japanese Patent Application No. 2-234208 and the compound (A'- on page 35 of the specification).
Compounds such as 1) can be used. Further, a fluorescent dye-releasing compound described in U.S. Pat.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but it is preferably 1.times.10@-3 to 5 mol, and more preferably 1 mol per mol of silver halide. It is used in the range of 10 −2 to 1 mol.

In the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can be used.

As the reflective support according to the present invention, any material may be used, such as white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support according to the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfur, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, aluminum hydrate, and oxidation. Examples include titanium, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the waterproof resin layer, and further, 13% by weight or more is preferable, and 15% by weight or more is particularly preferable. The dispersity of the white pigment in the water-resistant resin layer of the paper support can be measured by the method described in JP-A-2-28640, and when measured by this method, the dispersity of the white pigment is the above-mentioned publication. The coefficient of variation described in (4) is preferably 0.20 or less, more preferably 0.15 or less, still more preferably 0.10 or less.

The light-sensitive material according to the present invention may be subjected to corona discharge, irradiation of ultraviolet rays, flame treatment, etc. on the surface of the support, if necessary, and then, directly or undercoat layer (adhesiveness of support surface, antistatic property, It may be applied via one or more undercoating layers) for improving dimensional stability, abrasion resistance, hardness, antihalation property, frictional properties and / or other properties.

At the time of coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As a coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

As the aromatic primary amine type developing agent used in the present invention, known compounds can be used. The following can be mentioned as examples of these compounds.

CD-1 N, N-diethyl-p-phenylenediamine CD-2 2-amino-5-diethylaminotoluene CD-3 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 4- (N-ethyl-N- (β-hydroxyethylamino) aniline CD-5 2-methyl-4- (N-ethyl-N- (β-hydroxyethylamino) aniline CD-6 4-amino-3- Methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline CD-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8 N, N-dimethyl-p-phenylenediamine CD -9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10 4-Amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline CD-11 4-amino- 3-Methyl-N-ethyl-N- (β-butoxyethyl) aniline In the image forming method according to the present invention, Compounds in terms of the image processing represented by the following general formula (CD-I) are more preferably used.

[0132]

[Chemical 17]

In the formula, R represents a linear or branched alkylene group having 3 carbon atoms, m and n each represent an integer of 1 to 4,
HA represents an inorganic or organic acid, for example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid or the like.

These color developing agents are available from Journal of American Chemical Society, Vol. 73, 3100 (1
It can be easily synthesized by the method described in 951).

Specific examples of the compound represented by formula (CD-I) are shown below.

[0136]

[Chemical 18]

The color developing agent according to the present invention is usually a developing agent.
1 x 10 per liter of liquid^-2~ 2 x 10 ^-1Used in the molar range
From the viewpoint of rapid processing, 1 liter of color developer is 1.5
× 10^-2~ 2 x 10^-1A molar range is preferably used.

The color developing agent used in the image forming method of the present invention may be used alone or in combination with other known p-phenylenediamine derivatives. In the image forming method according to the present invention, the compounds used in combination with the compound represented by the general formula (I) include (CD-5) and (C
D-6) and (CD-9) are preferred.

These p-phenylenediamine derivatives are
It is generally used in the form of a salt such as sulfate, hydrochloride, sulfite, nitrate, p-toluenesulfonate.

The color developer according to the present invention may contain the following developer components in addition to the above components. For example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicates, etc., alone or in combination as alkaline agents, do not cause precipitation and stabilize pH. It can be used in combination within a range that maintains the effect. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate may be used for the necessity of preparation or for the purpose of increasing ionic strength.

If necessary, inorganic and organic antifoggants can be added. Although halide ions are often used for the purpose of suppressing development, in the present invention, chloride ions are mainly used because development must be completed in an extremely short time, and potassium chloride, sodium chloride, etc. Is used. The amount of chloride ion is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol per liter of the color developing solution. Bromide ions can also be used within a range that does not impair the effects of the present invention, but since they have a large effect of suppressing development, they are approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ or less, per liter of color developing solution. Is desirable.

If necessary, a development accelerator can be used. As a development accelerator, US Pat.
4, 3,671,247, various pyridinium compounds represented by JP-B-44-9503 and other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. Issue No. 2,53
1,832, 2,950,970, 2,577,127 and Japanese Patent Publication No.44-
Polyethylene glycol and its derivatives described in 9504,
Nonionic compounds such as polythioethers, JP-B-44-9
Organic solvents described in No. 509, organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like are included. Also, U.S. Pat.
In addition to the phenethyl alcohols described in No. 1, acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like.

Further, in the color developer according to the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378 and 44-9509. And the like can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N,
N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount is usually 1
It is used in an amount of 0.01 to 1.0 g per liter. In addition to these, competing couplers, fogging agents, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds, and the like can be added as required.

Furthermore, various additives such as other stain preventing agents, sludge preventing agents, and multi-layer effect accelerators can be used.

Each component of the above color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. in this case,
A component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine.
Further, more generally, a color developing solution may be prepared by adding a plurality of components, each of which can coexist stably, in a concentrated aqueous solution or in a solid state prepared in advance in a small container into water and stirring. it can.

In the present invention, the above-mentioned color developing solution can be used in any pH range, but from the viewpoint of rapid processing, it has a pH of 9.5 to 13.
It is preferably 0, and more preferably used in the range of 9.8 to 12.0.

The processing temperature for color development according to the present invention is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature is, the shorter the treatment time can be. However, it is preferable that the treatment liquid is not so high in view of the stability of the treatment liquid, and the treatment is preferably performed at 35 ° C. or higher and 60 ° C. or lower.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is within 60 seconds. Further, it is preferable to carry out in the range of 10 to 45 seconds.

The processing step essentially consists of a color development step, a bleach-fixing step, and a water washing step (including a stabilizing treatment as an alternative to water washing). However, steps may be added or equivalent to the extent that the effects of the present invention are not impaired. It can be replaced with a meaningful process. For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or the bleaching step can be performed before the bleach-fixing step. As the processing step used in the image forming method of the present invention, it is preferable to provide a bleach-fixing step immediately after the color developing step.

The bleaching agent that can be used in the bleach-fixing solution used in the image forming method of the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is a polycarboxylic acid,
Aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid are coordinated with metal ions such as iron, cobalt and copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids and aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of these compounds are described in JP-A-1-
The compounds [2] to [20] described in No. 205262, pages 58 to 59 can be mentioned.

These bleaching agents are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fixing solution.
As the bleach-fixing solution, a solution containing a silver halide fixing agent other than the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition containing a large amount of a halide such as ammonium bromide in addition to an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a silver halide fixing agent, and further an ethylenediaminetetraacetic acid iron (III) complex salt. It is also possible to use a special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide or the like can be used in addition to ammonium bromide.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide used in ordinary fixing processing to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate and thio. Typical examples are thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are added per liter of bleach-fixing solution.
5g or more, used in an amount that can be dissolved, but generally 70
Use at ~ 250g. The bleach-fix solution contains boric acid, borax,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Various pH buffering agents such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide can be contained alone or in combination of two or more kinds. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. Further, preservatives such as bisulfite adducts of hydroxylamine, hydrazine and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, organic solvents such as methanol, dimethylformamide and dimethylsulfoxide. And the like can be appropriately contained.

The bleach-fixing solution according to the present invention is described in JP-A-46-2
No. 80, Japanese Patent Publication No. 45-8506, No. 46-556, Belgium Patent 77
0,910, JP-B-45-8836, JP-A-53-9854, JP-A-54-71
Various bleaching accelerators described in No. 634, No. 49-42349 and the like can be added.

The bleach-fixing solution is used at a pH of 4.0 or higher, but it is generally used in the range of pH 4.0 to 9.5, preferably
The pH is 4.5 to 8.5. Most preferably, it is used in the pH range of 5.0 to 8.5.

The temperature of the bleach-fixing treatment is 80 ° C. or lower, preferably 55 ° C. or lower, and evaporation is suppressed before use. The treatment time is preferably 60 seconds or less, and more preferably 10 to 45 seconds.

In the processing step according to the present invention, the color development processing and the bleach-fixing processing are followed by a water washing processing. Further, a stabilizing treatment may be performed as an alternative to the washing treatment, or the washing treatment and the stabilizing treatment may be used in combination. The compound preferably used in the washing solution as the stabilization treatment,
A chelating agent having a chelate stabilization constant of 8 or more is preferable. The chelate stabilization constant here is llen, AEMartell
By `` Stability Constants of Metalion Comple The Chem
ical Society, London (1964), S.Chaberek, AEMarte
ll, "Oranic Sequestering Agents", Willey (195
9) Means a constant that is generally known from the above.

Further, as a compound added to the washing solution, an ammonium compound is mentioned as a particularly preferable compound. These are supplied by ammonium salts of various inorganic compounds, and specific examples thereof are JP-A 1-205162 65.
The compounds described on page 5, line 6 to page 66, line 11 are mentioned. The amount of the ammonium compound added is preferably 1.0 × 10 ⁻⁵ mol or more, more preferably 1 × 10 ⁻⁵ mol, per liter of the washing water
It is in the range of 0.001 to 5.0 mol, more preferably 0.002 to
It is in the range of 1.0 mole.

Further, it is desirable that the washing solution contains sulfite within a range where bacteria are not generated. The sulfite contained in the washing solution may be any one such as an organic substance or an inorganic substance, as long as it releases a sulfite ion, but is preferably an inorganic salt, and preferably a specific compound is sodium sulfite, potassium sulfite, or sulfite. Ammonium sulfate, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartaraldehyde bis sodium bisulfite, succinic acid bis bis sodium bisulfite, etc. Can be mentioned.

The above sulfite is preferably added in an amount of at least 1.0 × 10 ^-5 mol per liter of the washing solution, preferably 5 × 1.
More preferably, it is 0 ^{−5 to} 1.0 × 10 ⁻¹ mol. It may be added directly to the washing solution, but it is preferably added to the washing replenisher.

The water-washing solution used in the present invention preferably contains a mildew-proofing agent, which can prevent sulfidation and improve image storability. Examples of the mildew-proofing agent that can be used in the washing liquid according to the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guadinine compounds, morpholine compounds, and quaternary phosphonium compounds. ,
Ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfide compounds, pyronone compounds and amino compounds. Specific compounds are described in JP-A 1-205162.
The compounds described on page 68, line 10 to page 72, line 16 are mentioned. Among these compounds, particularly preferably used compounds are thiazole compounds, sulfamide compounds and pyronone compounds.

The amount of the mildew-proofing agent added to the aqueous solution is preferably 0.001 to 30 g, and more preferably 0.003 to 5 g, per liter of the washing solution.

The washing liquid according to the present invention preferably contains a metal compound in combination with a chelating agent. Such metal compounds include Ba, Ca, Ce, Co, In, Mn, Ni, Bi, P
Examples thereof include compounds of b, Sn, Zn, Ti, Zr, Mg, Al and Sr. These metal compounds can be supplied as an inorganic or organic salt such as a halide salt, a sulfate salt, a carbonate salt, a phosphate salt or an acetate salt, a hydroxide or a water-soluble chelate compound. The amount of these compounds added is preferably 1.0 × 10 ^{-4 to} 1.0 × 10 ^-1 mol per liter after washing with water, and 4.0 × 10 4
^{-4 to} 2.0 × 10 ^-2 mol is more preferable.

In addition to the above, a compound having an aldehyde group may be used as the component contained in the present invention. Specific compounds include Exemplified Compound 1 to Exemplified Compound 32 described on pages 73 to 75 of JP-A 1-205162.
Can be mentioned. The compound having an aldehyde group is preferably used in the range of 0.1 to 50 g per liter of washing water.

Ion exchange water treated with an ion exchange resin may be used as the washing water according to the present invention.

The pH of the wash water applicable to the present invention is 5.5 to 1
It is in the range of 0.0. As the pH adjuster applicable to the present invention, any of generally known alkali agents and acid agents can be used.

The treatment temperature of the water washing treatment is preferably 15 ° C to 60 ° C, more preferably 20 ° C to 45 ° C. Further, the time of the water washing treatment is preferably 10 to 90, more preferably 5 to 60 seconds. When the washing treatment is carried out in a plurality of tanks, it is preferable that the earlier tank is treated in a shorter time and the latter tank is treated in a longer time. Particularly, it is preferable to sequentially perform the treatment with a treatment time of 20% to 50% longer than that in the previous tank.

When the multi-tank counter flow current system is used as the method for supplying the washing liquid in the washing treatment step according to the present invention, it is preferable that the washing liquid is supplied to the subsequent bath and allowed to overflow into the previous bath. Of course, various methods can be used, such as adding as a concentrated solution to a single tank, or adding the above compound and other additives to a washing solution supplied to a washing tank and using this as a washing replenisher.

The amount of washing water in the washing step according to the present invention is preferably 0.1 to 50 times, especially 0.5 to 50 times the carry-in amount of the pre-bath (normal bleach-fixing solution or fixing solution) per unit area of the light-sensitive material.
30 times is preferable.

The washing tank in the washing treatment according to the present invention is 1
˜5 tanks are preferable, and 1 to 3 tanks are more preferable.

As a developing processing apparatus for the silver halide photographic light-sensitive material used in the image forming method of the present invention, any known apparatus may be used. A specific example may be a roller transport type in which a photosensitive material is sandwiched between rollers arranged in a processing tank to be conveyed, but the processing tank is formed in a slit shape and the processing liquid is supplied to this processing tank. In addition, a method of transporting the light-sensitive material, a spray method of spraying the processing liquid, a web method by contact with a carrier impregnated with the processing liquid, and the like can be used.

[0173]

EXAMPLES The present invention will be described below with reference to examples, but the 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 paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support.

On this reflective support, each layer having the constitution shown in Table 1 and Table 2 was coated to prepare a multilayer photosensitive material sample 105. Hereinafter, samples 101 to 115 were prepared as shown in Table 3.

The coating liquid was prepared as follows.

(Preparation of Black Layer Coating Solution) BW-1 Black coupler 4-chloro-N-octadecyl-m-
Aminophenol (B-1) was dissolved in dioctyl phthalate, an aqueous gelatin solution and a surfactant (Su-1) were added, and protect dispersion was carried out to obtain the same sensitizing dye (GS as the following green-sensitive silver halide emulsion layer layer). -1) was mixed with the green-sensitive silver halide emulsion (G-2) sensitized to prepare a coating solution for the first layer (black layer).

BW-2 Yellow, magenta, and cyan couplers were dispersed and mixed to prepare a black coupler, and the first layer coating solution BW-2 was prepared in the same manner as above.

The dye added to the black layer was added as an aqueous solution as shown in Table 3 so that the total amount was 20 mg.

(Preparation of coating solution for yellow layer) Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0
g, (ST-2) 6.67 g, additive (HQ-1) 0.67 g and high boiling point organic solvent (DNP) 6.67 g were dissolved by adding 60 ml of ethyl acetate, and this solution was dissolved in 15% surfactant (SU- 1) 9.
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 cc. Of 10% gelatin aqueous solution containing 5 cc. Using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the second layer. The coating solutions for the third to eighth layers were prepared in the same manner as the coating solution for the second layer. Further, as a hardening agent, (H-1) was added to the third and fifth layers, and (H-2) was added to the eighth layer. As the coating aid, surfactants (SU-2), (S
U-3) was added to adjust the surface tension.

[0181]

[Table 1]

[0182]

[Table 2]

The additives used for sample preparation are as follows.

HQ-1 2,5-di-t-octylhydroquinone HQ-2 2-hexadecyl-5-methylhydroquinone HBS-11-dodecyl-4-p-toluenesulfonamidebenzene DOP dioctylphthalate DNP dinonylphthalate DIDP Di-i-decylphthalate PVP Polyvinylpyrrolidone SU-1 Sodium tri-i-propylnaphthalene sulfonate SU-2 Sulfosuccinic acid di (2-ethylhexyl) ester sodium SU-1 Sulfosuccinic acid di (2,2,3, 3,4,4,5,5-Octafluoropentyl) ester sodium H-1 2,4-dichloro-6-hydroxy-s-triazine sodium H-2 tetrakis (vinylsulfonylmethyl) methane

[0185]

[Chemical 19]

[0186]

[Chemical 20]

[0187]

[Chemical 21]

[0188]

[Chemical formula 22]

[0189]

[Chemical formula 23]

[0190]

[Chemical formula 24]

[0191]

[Chemical 25]

(Preparation of blue-sensitive silver halide emulsion) The following (solution A) was added to 1000 cc. Of a 2% gelatin aqueous solution kept at 40 ° C.
And (Solution B) were simultaneously added over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and the following (Solution C) and (Solution D) were added to pAg = 7.
3. Simultaneously added over 180 minutes while controlling pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water was added to 200 cc. (Solution B) Silver nitrate 10 g Water was added to 200 cc. (Solution C) Sodium chloride 102.7 g Potassium bromide 2.10 g Water was added 600 cc. (Liquid D) 300 g of silver nitrate Water is added to 600 cc. After the addition is complete, desalting is performed using a 5% aqueous solution of Demol N and 20% magnesium sulfate manufactured by Kao Atlas, and then mixed with an aqueous gelatin solution. Thus, a monodisperse cubic emulsion EMP-1 having an average grain size of 0.85 μm, a coefficient of variation (S / R) of 0.07 and a silver chloride content of 99.0 mol% was obtained.

Next, EMP was performed except that the halogen composition was changed.
A cubic emulsion (EMP-2) having a silver chloride content of 80 mol% was obtained in the same manner as in -1. Furthermore, temperature from EMP-1
The average particle size is 0.15μ by changing the time of liquids A, B and C, D
EMP-3 having m, variation coefficient (standard deviation / average particle size) of 0.07, and 99 mol% of silver chloride was obtained.

The following compounds were used for Emulsion EMP-1.
Chemical ripening was carried out at 50 ° C. for 90 minutes to obtain a blue-sensitive silver halide emulsion (EMB-1).

EMP-2 was also obtained in the same manner as EMP-2. Further, EMB-3 used in the black layer was obtained in the same manner as in EMB-1, except that the addition amounts of EMP-3 and sensitizing dyes BS-1 and BS-2 were changed. The sensitivity of this EMB-3 is B
It was about 1/5 with respect to the -1 emulsion.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation of green-sensitive silver halide emulsion) (solution A) and solution (B)
The average particle size is 0.43μ in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (D liquid) are changed.
A monodisperse cubic emulsion EMP-4 having m, a coefficient of variation (S / R) of 0.07 and a silver chloride content of 99.0 mol% was obtained.

Next, E was changed except that the silver halide composition was changed.
EMP- with a silver chloride content of 80 mol% in the same manner as MP-3
Got 5. EMG-2 was similarly obtained from EMP-5.

The following compounds were used for EMP-4:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX EMP- 4, the temperature and the addition time of each liquid of A, B, C and D were further changed to obtain monodisperse EMP-6 having an average particle size of 0.15 μm, a coefficient of variation of 0.06 and a silver chloride content of 99 mol%.

By changing the amounts of sodium thiosulfate, the amount of gold and the amount of sensitizing dye of the compound used in EMG-1 with respect to EMP-6, a green-sensitive emulsion EMG-3 used in the black layer was obtained. The sensitivity of this emulsion was about 1/4 that of the EMG-1 emulsion.

(Method for preparing red-sensitive silver halide emulsion)
(A solution) and (B solution) addition time, and (C solution) and (D
A monodispersed cubic emulsion EMP-6 having an average particle size of 0.50 μm, a coefficient of variation (S / R) of 0.08, and a silver chloride content of 99.0 mol% was obtained in the same manner as EMP-1, except that the addition time of the solution was changed. It was

Further, an emulsion EMP-7 having a silver chloride content of 80 mol% was obtained in the same manner except that the silver halide composition was changed.

For EMP-6, the following compounds were used.
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R1) was obtained. Similarly for EMP-7, EMR-2
Got

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX STAB- 11- (3-acetamido) phenyl-5-mercaptotetrazole Samples 101 to 1 were prepared by combining the above emulsions as shown in Table 3.
Created 15.

[0206]

[Table 3]

These samples 101 to 115 were produced by Konica KS
After exposure through a step wedge with a density difference of 0.75 using a tungsten light source (color temperature: 3200 ° K) with a -7B type sensitometer, development processing was performed with the following developers A and B. Developer A
Table 4 shows the results of using the developer, and Table 5 shows the results of using the developer B.

The evaluation was performed by visually observing the details of a single color.

[0209] ○ is excellent, Δ is normal, and × is inferior. MTF (Moduration Transfer Funct
Ion) After exposure to white light through a measuring wedge, development was carried out in the same manner as above, and the MTF of the silver halide emulsion layer was measured using a microdensitometer PDM-5 (manufactured by Konica Corporation), and the space was measured. The monochromatic MTF values at a frequency of 5 lines / mm were compared.

For the MTF value, see "The theory of the
The method described in "photographic process 3rd edit in" was used. (Processing step A) Processing temperature Processing temperature Time Color development A 38.0 ± 0.3 ° C 20 seconds Bleaching and fixing A 35.0 ± 0.5 ° C 20 seconds Water washing A 30 to 34 ° C 60 seconds Dry 60 to 80 ° C 30 seconds (Processing step B ) Processing process Processing temperature Time Color development B 35.0 ± 0.3 ℃ 45 seconds Bleach fixing B 35.0 ± 0.5 ℃ 45 seconds Water wash B 30 to 34 ℃ 90 seconds Dry 60 to 80 ℃ 60 seconds Composition of developing solution is as follows. Show.

Color developer A tank liquid Pure water 800 cc. Triethylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl- 4-Aminoaniline sulfate 6.0g N, N-diethylhydroxylamine 6.8g Triethanolamine 10.0g Diethylenetriaminepentaacetic acid sodium salt 2.0g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0g Potassium carbonate 30g Add water to bring the total volume to 1000 cc. And adjust the pH to 10.10.

Color developer B tank liquid Pure water 800 cc. Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonate disodium 1.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4 , 4'-Diaminostilbenedisulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to bring the total volume to 1000 cc. Adjust the pH to 10.60.

Bleach-fixing solution A Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc. 5-Amino-1,3,4-thiadiazole-2- Thiol 2.0g Ammonium sulfite (40% aqueous solution) 27.5cc. Add water to make 1000cc. Adjust the pH to 6.5 with potassium carbonate or glacial acetic acid.

Bleach-fixing solution B tank solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100cc. Ammonium sulfite (40% aqueous solution) 27.5cc. Add water to make a total volume of 1000cc And adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

[0215]Washing liquid A tank liquid o-Phenylphenol 1.0g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-Methyl-4-isothiazolin-3-one 0.02g Diethylene glycol 1.0g Optical brightener (Tinopearl SFP) 2.0g 1 -Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g Ammonia water (ammonium hydroxide 25% aqueous solution) 2.5 g Nitrilotan Acetic acid / trisodium salt 1.5g Add water to make 1000cc.
Adjust pH to 7.5 with. Washing liquid B tank liquid 5-Chloro-2-methyl-4-isothiazolin-3-one 1.0g Ethylene glycol 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Ethylenediaminetetraacetic acid 1.0g Ammonium hydroxide (20% aqueous solution) 3.0g Fluorescence Whitening agent (4,4'-diaminostilbenedisulfonic acid derivative) 1.5g Add water to make 1000cc. And add sulfuric acid or potassium hydroxide.
Adjust the pH to 7.0 with a glass.

[0216]

[Table 4]

[0217]

[Table 5]

From the results of Tables 4 and 5, comparative samples 101, 103 and 104
In contrast, Samples 105 to 115 of the present invention have improved MTF and good detail. The MTF of the comparative sample 102 is also improved, but the monochromatic detail is inferior, and the monochromatic detail of 103 is improved, but the MTF is not improved. Ten
In No. 4, due to the low density, both MTF and monochromatic detail were inferior.

Example 2 The emulsions of the black layer used for the first layer were changed from EMG-3 to EMB-3.
Samples 201 to 215 were prepared in the same manner as in Example 1 except that the above was changed. The samples 201 to 215 were exposed in the same manner except that they were exposed to blue light, and were treated with the treatment liquid A.

[0220]

[Table 6]

From the results shown in Table 6, the same results as in Example 1 were obtained.

[0222]

According to the present invention, it is possible to provide a rapidly processable silver halide color photographic light-sensitive material having improved sharpness and improved shadow depiction.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a photosensitive layer containing a cyan, magenta and yellow coupler on a support, wherein at least one layer has a silver chloride content of 90 mol% or more, and In addition to the silver halide photosensitive layer containing a color coupler, a silver halide photosensitive layer containing a compound that produces a black image is provided, and the photosensitive layer is represented by the following general formulas [1] and [2]. A silver halide color photographic light-sensitive material containing at least one of the compounds described above. [Chemical 1] [In the formula, R ₁ and R ₂ are each —CN, —COR ₅ , —COOR ₆ or —CONR ₇ R ₈
R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and L ₁ , L ₂ and
L ₃ each represents a methine group, k represents 0, 1 or 2, and when k is 2, -L ₂ = L ₃ -may be the same or different. R ₅ , R ₆
Represents a hydrogen atom, an alkyl group or an aryl group. R ₇ , R
Each of ₈ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R ₇ and R ₈ and an adjacent nitrogen atom may form a 5-membered ring or a 6-membered ring. However,
R ₇ and R ₈ are not hydrogen atoms at the same time. or,
At least one of R ₁ , R ₂ , R ₃ , and R ₄ is a water-soluble group or a group containing a water-soluble group. ] [Chemical 2] [In the formula, V ₁ and V ₂ are each a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, -COOR ₁ , -COR ₁ , CONR ₁ R ₂ , -OR ₁ ,
-NR ₁ R ₂ , -NR ₁ COR ₂ , -NR ₁ SO ₂ R ₂ , alkyl group, aralkyl group,
It represents a cycloalkyl group, an aryl group, a heterocycle or an amino group, and W ₁ and W ₂ are each a hydrogen atom, -NR ₃ R ₄ , -NR ₃ COR ₄ , -NR ₃ SO ₂
R ₄ , an aralkyl group, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an amino group is represented, and X ₁ and X ₂ are each a hydrogen atom, a cyano group, a carboxyl group, a sulfo group, -COOR ₅ , -CO
R ₅ , -CONR ₅ R ₆ , -NR ₅ R ₆ , -NR ₅ COR ₆ , -NR ₅ SO ₂ R ₆ , -SO ₂ R ₅ , alkyl group, aralkyl group, cycloalkyl group, aryl group or heterocycle Group, L ₁ , L ₂ and L ₃ each represent a methine group, m represents 0, 1 or 2, n represents 1, 2 or 3, and M ^{n +} represents an n-valent cation. R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ are linked to each other and have 5 or 6 members. You may form a ring. However, at least one of V ₁ , V ₂ , W ₁ , W ₂ , X ₁ , and X ₂
Represents a group containing a carboxyl group or a sulfo group. ]