JPH08201971A - Silver halide photographic sensitive material and its development processing method - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material capable of forming an image small in fog, improved in stability with the lapse of time, high in sensitivity and sharpness, and small in residual dye stains by development processing in a short time, and to provide the method for processing this photosensitive material. CONSTITUTION: This photosensitive material has at least one layer containing at least one kind of azomethine dye represented by the formula: A<1> =N-A<2> -R<1> on a support and it is processed with a developing solution having a pH of <=11. In the formula, A<1> is an atomic group needed to allow the azomethine dye to have absorption in the visible to near infrared regions;A<2> is a nonmetallic atomic group necessary to form an optionally substituted and optionally condensed 5- or 6-membered hetero ring; R<1> is a -OH or -NR<2> R<3> group; and each of R<2> and R<3> is, independently, an H atom or the like, and each of (R<2> and R<3> ), (R<2> and A<2> ), and (R<3> and A<3> ) may combine with each other to form a ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a dye, more specifically, it has less adverse effects such as fog and desensitization and is bleached even in rapid processing.
The present invention relates to a silver halide photographic light-sensitive material containing a novel diffusion resistant dye having excellent residual color.

[0002]

2. Description of the Related Art Conventionally, silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials) have a specific wavelength for the purpose of light absorption filter, halation prevention, irradiation prevention or sensitivity adjustment of photosensitive emulsion. It is well known to incorporate a dye into a constituent layer of a light-sensitive material in order to absorb light, and dyeing a hydrophilic colloid layer with the dye has been performed. Dyes for the purpose of substituting yellow colloidal silver in color light-sensitive materials, dyes for crossover cut layers in X-ray light-sensitive materials, dyes for dyeing non-light-sensitive emulsion layers in printed photographic light-sensitive materials, and their applications are expanding. There is.

The dye used for such a purpose has not only good absorption spectrum characteristics depending on the purpose of use but also is completely decolorized during development processing and easily eluted from the photographic light-sensitive material. , No residual color contamination by dye after processing, no adverse effect such as fog or desensitization on photosensitive emulsion, no diffusion from colored layer to other layers, in photographic light-sensitive material or coating solution In the above, it must satisfy various conditions such as excellent stability over time and no discoloration or fading.

To date, many studies have been carried out with the aim of finding dyes satisfying the above conditions.
For example, U.S. Patents 3,540,887, 3,544,325 and 3,560,
No. 214, Japanese Patent Publication No. 31-10578 and Japanese Patent Publication No. 51-3623 disclose benzylidene dyes, and British Patent No. 506,385 and Japanese Patent Publication No.
Oxonol dyes in US Pat. No. 2,493,747 in 9-22069
No. 1,845,404, and styryl dyes are proposed in US Pat. No. 1,845,404.

Some of these conventional dyes have a relatively small effect on the emulsion performance and have the ability to be bleached / eluted / bleached in the processing step, but from the viewpoint of diffusion resistance. It was not enough to see. That is, when a specific layer of a plurality of emulsion layers is selectively colored and used as a filter layer or an antihalation layer, not only the diffusion to other layers is remarkable, but the light absorption effect is lowered,
There was a defect that it gave an unfavorable effect to other layers such as sensitivity deterioration, gradation change and fog abnormality.

As a means for preventing the dye from diffusing into other layers, the dye itself is made diffusion resistant, for example, US Pat. No. 2,538,008.
No. 2,539,009, 4,420,555, JP-A-61-204630
Nos. 62-32460 and 63-184749 are disclosed. Each of these dyes has a drawback that the decolorizing property and the solubility in a processing liquid are inferior, resulting in residual color contamination. Also, a dissociative dye is fixed using a mordant,
As a method for making the material resistant to diffusion, for example, US Pat.
Nos. 3,625,694 and 4,124,386 are disclosed. However, the method using a mordant is a binder in the photographic light-sensitive material constituting layer, for example, gelatin, which forms an aggregate with the mordant or increases the viscosity, which causes serious problems such as uneven coating and cissing. In addition, there are drawbacks such as inconvenience, diffusion resistance between layers is not sufficient, elution and decoloring properties during treatment are poor, a treatment bath having a high pH is required, and rapid treatment suitability is poor.

Further, as a means for preventing the diffusion of the dye, there is a method of dyeing a specific layer with a solid fine particle dispersion of a dye which is water-insoluble and easily dissolved in a solution having a high pH, for example, US Pat. No. 4,855,221, No. 4,857,446, No. 4,948,717
No., JP-A-52-92716, JP-A-55-155350, JP-A-55-155351
No. 56-12639, No. 63-197943, JP-A-2-110453
No. 2, No. 2-1838, No. 2-1839, No. 2-119942, No. 2-2642
No. 47, No. 2-264936, No. 2-277044, No. 4-37841, and World Patent No. 88/04794 are disclosed. However, the method, although the effect as a means of diffusion resistance of the dye is seen, there is a drawback that a dye having a desired absorption spectrum is difficult to obtain, decolorization in rapid processing can not be said to be sufficient, There was still a problem of residual color contamination. Therefore, even in rapid processing, there is a strong demand for a diffusion resistant dye that has good decolorizing properties and does not cause residual color contamination after processing.

[0008]

In order to solve the above problems, an object of the present invention is to provide a diffusion-resistant dye,
It is an object of the present invention to provide a silver halide photographic light-sensitive material which meets the above requirements and has less fog and improved stability over time.
Another object is to provide a silver halide photographic light-sensitive material having high sensitivity and excellent sharpness. Another object of the present invention is to provide a silver halide photographic light-sensitive material which gives an image with little residual color contamination by a short development process.

[0009]

The above-mentioned problems of the present invention can be solved by the following means.

1) A silver halide photographic light-sensitive material characterized by having a layer containing an azomethine dye represented by the general formula (1) on a support.

2) The silver halide photographic light-sensitive material as described in 1) above, which has a non-photosensitive layer containing an azomethine dye represented by the general formula (1) on a support.

3) The silver halide photographic light-sensitive material described in 1) or 2), wherein the azomethine dye represented by the general formula (1) is contained as a solid fine particle dispersion.

4) 1) to 3), wherein A ^{2 of the} azomethine dye represented by the general formula (1) is a 5- or 6-membered optionally substituted nitrogen-containing heterocycle. The silver halide photographic light-sensitive material according to any one of items.

5) R ^{1 of the} azomethine dye represented by the general formula (1) is NR ² R ³ (R ² and R ³ are each independently a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group), and the silver halide photographic light-sensitive material according to any one of 1) to 4).

6) The azomethine dye represented by the general formula (1) is a dye having at least one of a phenolic hydroxyl group, a carboxyl group, a sulfamoyl group or a sulfonamide group in the molecule. ) ~
5) The silver halide photographic light-sensitive material according to any one of items.

7) At least one silver halide emulsion layer is provided on a support, and at least the hydrazine derivative represented by the general formula (2) is contained in the emulsion layer or another hydrophilic colloid layer. In a silver halide photographic light-sensitive material containing one kind, at least one kind of solid fine particle dispersion of the dye represented by the general formula (1) is contained between the support and the silver halide emulsion layer. 7. The silver halide photographic light-sensitive material as described in any one of 1) to 6), which has a non-photosensitive hydrophilic colloid layer.

8) A development processing method, which comprises processing the silver halide photographic light-sensitive material described in any one of 1) to 7) above with a developer having a pH of 11 or less.

The present invention will be specifically described below.

First, A ¹ , A ² and R ¹ of the azomethine dye represented by the general formula (1) will be described in detail.

In the general formula (1), A ¹ represents an atomic group necessary for the azomethine dye to have absorption in the visible region and / or the near infrared region, R ¹ represents OH and NR ² R ³ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ² and R ³ , R ² and A ² and R ³ and A ² may cooperate with each other to form a ring, and A ² may further have a condensed ring. A ² is a group of non-metal atoms necessary for forming an optionally substituted 5-membered or 6-membered heterocycle, and is a ring formed by an element selected from the group consisting of carbon, nitrogen, oxygen and sulfur atoms. Are preferably formed.
Preferred following general formula as a ^{-A 2 -R 1 A 2 -A~A 2} -
L is mentioned.

[0021]

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In the formula, R ⁶ represents a hydrogen atom or a substituent.
R ⁷ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an acylamino group, an amino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group. , An arylthio group, an alkoxycarbonylamino group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an aryloxycarbonylamino group, an imide group, and a heterocyclic thio group. These are alkyl groups,
Further substituted with an alkenyl group, alkynyl group, aryl group, hydroxyl group, nitro group, cyano group, halogen atom, carboxylic acid group, sulfonic acid group or other substituents formed by oxygen, nitrogen, sulfur or carbon atoms. May be. * Is bonded to N in the general formula (1). n is 1
Or 2, m is 1, 2 or 3, and n or m is 2
In the above case, R ₆ may be the same or different,
When R ⁶ and R ⁷ are groups capable of forming a ring, they may form a ring. Described in more detail for the case with R ^6, R ⁷ and ring closure structure in A ² -A~A ² -L.

R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an acylamino group, Amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy Represents a group, an azo group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, and an acyl group. These are alkyl groups, alkynyl groups, alkynyl groups, aryl groups, hydroxyl groups, nitro groups, cyano groups, halogen atoms, carboxylic acid groups, sulfonic acid groups or other substituents formed by oxygen, nitrogen, sulfur or carbon atoms. Further, it may be replaced.

More specifically, examples of the substituent of R ⁶ will be shown. Examples of the halogen atom include a fluorine atom, a chlorine atom, and an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms.
Is a linear, branched or cyclic alkyl group of, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxycarbonylethyl, 2-methoxyethyl, benzyl, 2-methanesulfonamidoethyl, 2-methanesulfonyl. Ethyl, cyclopentyl and 2-acetamidoethyl. The aryl group is an aryl group having a carbon number of 6 to 18, and examples thereof include phenyl, naphthyl and p-hydroxycarbonylphenyl. The heterocyclic group is a 5- or 6-membered heterocyclic ring having at least one oxygen, nitrogen or sulfur atom having 1 to 5 carbon atoms, and examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl and 2-benzotria. They are zolyl, imidazolyl and pyrazolyl.

The alkoxy group is an alkoxy group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methoxy, ethoxy and 2-methoxyethoxy. The aryloxy group is an aryloxy group having 6 to 18 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy and p-tolyloxy. The acylamino group is an acylamino group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetamide, 2-methoxypropionamide and benzoylamino. The alkylamino group has 1 to 12 carbon atoms,
Preferably, it is an alkylamino group having 1 to 6 carbon atoms, such as dimethylamino, diethylamino or 2-hydroxyamino. The anilino group is an anilino group having 6 to 18 carbon atoms, and examples thereof include anilino, m-nitroanilino, and N-methylanilino. The ureido group is a ureido group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, such as methylureido, N,
It is N-dimethylureido.

The sulfamoylamino group has 0 carbon atoms.
To 12, preferably a sulfamoylamino group having 0 to 6 carbon atoms, such as dimethylsulfamoylamino and methylsulfamoylamino. The alkylthio group is an alkylthio group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methylthio, ethylthio and 2-phenoxyethylthio. The arylthio group is an arylthio group having 6 to 18 carbon atoms, and examples thereof include phenylthio and 4-cyanophenylthio. The alkoxycarbonylamino group is an alkoxycarbonylamino group having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, and examples thereof include methoxycarbonylamino, ethoxycarbonylamino and 3-methanesulfonylpropoxycarbonylamino. The sulfonamide group is a sulfonamide group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfonamide, p-toluenesulfonamide, and 2-methoxyethanesulfonamide. The carbamoyl group is a carbamoyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include carbamoyl, N, N-dimethylcarbamoyl and N-ethylcarbamoyl. The sulfamoyl group is a sulfamoyl group having 0 to 12 carbon atoms, preferably 0 to 6 carbon atoms, and examples thereof include sulfamoyl, dimethylsulfamoyl and ethylsulfamoyl. The sulfonyl group has 1 to 12 carbon atoms,
Preferably, it is an aliphatic or aromatic sulfonyl group having 1 to 6 carbon atoms, for example, methanesulfonyl, ethanesulfonyl,
2-chloroethanesulfonyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and t-butylcarbonyl.
The heterocyclic oxy group is a 5- or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and forms a ring-forming heterocycle. The number of atoms and the number of elements may be one or plural, and examples thereof include 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy, and 2-pyridyloxy.

The azo group is an azo group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include phenylazo, 2-hydroxy-4-propanoylphenylazo and 4-methanesulfonylphenylazo. The acyloxy group is an acyloxy group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group is a carbamoyloxy group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy and N-phenylcarbamoyloxy. The silyl group is a silyl group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, and examples thereof include trimethylsilyl, isopropyldiethylsilyl and t-butyldimethylsilyl. Silyloxy group has 3 to 1 carbon atoms
2, preferably a silyloxy group having 3 to 6 carbon atoms, such as trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy. The aryloxycarbonylamino group is an aryloxycarbonylamino group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonylamino, 4-cyanophenoxycarbonylamino, and 2,6-dimethoxyphenoxycarbonylamino. The imide group is an imide group having a carbon number of 4 to 12, and examples thereof include N-succinimide and N-phthalimide. The heterocyclic thio group is a 5- or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and forms a hetero ring. The number of atoms and the types of elements may be one or more,
For example, 2-benzothiazolylthio and 2-pyridylthio.

The sulfinyl group is a sulfinyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfinyl, benzenesulfinyl and ethanesulfinyl. The phosphonyl group is a phosphonyl group having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, and examples thereof include methoxyphosphonyl, ethoxyphosphonyl, and phenoxyphosphonyl. The aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl, 2-methylphenoxycarbonyl, 4-
Sulfophenoxycarbonyl. The acyl group is an acyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetyl, benzoyl and 4-chlorobenzoyl. When R ⁶ is a hydroxyl group, an amino group or an alkylamino group, the compounds represented by the general formulas A ² -A to A ² -L may have a tautomeric structure, formula a ² -A~A ² -L it is naturally also include such compounds.

Of these, R ⁶ is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an acylamino group having 1 to 6 carbon atoms,
A dialkylamino group having 2 to 12 carbon atoms, a ureido group having 1 to 6 carbon atoms, a sulfamoylamino group having 2 to 12 carbon atoms,
Alkoxycarbonylamino group having 1 to 6 carbon atoms, sulfonamide group having 1 to 6 carbon atoms, carbamoyl group having 1 to 6 carbon atoms, sulfamoyl group having 2 to 12 carbon atoms, and 1 to 1 carbon atoms
A sulfonyl group having 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, a carboxylic acid group and a sulfonic acid group, and more preferably a hydrogen atom and 1 to 6 carbon atoms.
Alkyl group, C6-12 aryl group, cyano group, C1-6 alkoxy group, C1-6 acylamino group, C2-12 dialkylamino group, C1-6 Ureido group, C2-C12 sulfamoylamino group, C1-C6 alkoxycarbonylamino group, C1-C6 sulfonamide group, C1-C6
Carbamoyl group, a C2-C12 sulfamoyl group,
A sulfonyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carboxylic acid group, and a sulfonic acid group.

R ⁷ is hydrogen atom, alkyl group, aryl group, heterocyclic group, hydroxyl group, alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group. , An alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an aryloxycarbonylamino group, an imide group, and a heterocyclic thio group. These are alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, nitro groups, cyano groups, halogen atoms, carboxylic acid groups, sulfonic acid groups or other substituents formed by oxygen, nitrogen, sulfur or carbon atoms. It may be further substituted, and specific examples thereof are the same as those for R ⁶ . R ⁷ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an acylamino group having 1 to 6 carbon atoms, an amino group, a dialkylamino group having 2 to 12 carbon atoms. , A C1-6 ureido group, a C1-6 sulfamoylamino group, a C1
~ 6 alkoxycarbonylamino group, C1-6 sulfonamide group, C2-12 sulfamoyl group,
A sulfonyl group having 1 to 6 carbon atoms and an imide group having 4 to 8 carbon atoms are more preferable, and a hydrogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable.

In the above general formulas A ² -A to A ² -L,
In the case of having a condensed ring structure, the number of ring members may be any number of rings, but it is preferably 5 to 7 members.

R ² and R ^{3, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which are an alkyl group, an alkenyl group, an alkynyl group, a hydroxyl group or a nitro group. , Carboxyl group, cyano group, halogen atom, aryl group, heterocyclic group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxy Carbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group , A heterocyclic thio group, It may be further substituted with a substituent linked with a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group or an acyl group.

More specific examples of R ² and R ³ will be shown. The alkyl group has 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms
A linear, branched or cyclic alkyl group of, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-
Hydroxyethyl, 3-hydroxypropyl, benzyl,
2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-methoxycarbonylethyl, 2-carbamoylethyl, hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-cyanoethyl, 2-acetoxyethyl. The aryl group is an aryl group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl. As the heterocyclic group, an oxygen atom having 1 to 5 carbon atoms,
A 5- or 6-membered saturated or unsaturated heterocycle containing at least one nitrogen atom or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element may be one or plural. , For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl, pyrazolyl.

R ² and R ³ may cooperate with each other to form a ring. The ring to be formed is not particularly limited, but is preferably a group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom, for example, pyrrolidino, piperazino and morpholino. These rings may have a substituent allowed by R ² . R ² and R ³ are unsubstituted alkyl groups, or alkyl groups substituted with a substituent group linked by a hydroxyl group, an alkoxycarbonyl group, a cyano group, an alkoxy group, an acylamino group, an acyloxy group or a sulfonamide group. Is preferred.

A ¹ represents an atomic group necessary for the azomethine dye of the general formula (1) to have absorption in the visible region and / or near infrared region, and A ¹ represents an oxidative coupling reaction with p-phenylenediamines. It is the same as that derived from a coupler compound which gives an azomethine dye. Examples of the coupler compound which gives A ¹ include phenols, naphthols, heterocyclic compounds having active hydrogen, and open-chain active methylene compounds. Preferred A ¹ = N- is represented by the following general formulas (α) to (ψ).

[0036]

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[0037]

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[0038]

[Chemical 4]

General formulas (α), (β), (γ) and (δ)
I will describe. Rα ¹ , Rα ² , Rα ³ , Rα ⁴ , R
β ¹ , Rβ ² , Rβ ³ , Rβ ⁴ , Rβ ⁵ , Rβ ⁶ , Rγ ¹ , R
^{γ 2, Rγ 3, Rδ 1} , Rδ 2 and Aruderuta ³ represents a hydrogen atom or a nonmetallic substituent are the same as those described in R ⁶ and R ⁷ in A ^2, specific examples are also the same. Formulas (α), (γ),
In (δ), Rα ¹ , Rγ ¹ , and Rδ ² are preferably an acylamino group (eg, acetylamino, furoylamino, 4-hydroxycarbonylbenzoylamino, pivaloylamino), a carboxylic acid group or a sulfonic acid group. Rα ⁴ , Rγ ³ , R
δ ¹ is preferably an acylamino group (eg pivaloylamino) or an alkyl group (eg methyl, ethyl, n-decyl). Rα ² and Rδ ³ are preferably hydrogen atoms, and Rα ³ and Rγ ²
Is preferably a chlorine atom or a hydrogen atom. Rβ ^{1 in the} formula (β)
Is preferably a carbamoyl group (eg, 2-hydroxycarbonylphenylcarbamoyl, methylcarbamoyl, t-butylcarbamoyl), a carboxylic acid group or a sulfonic acid group. Rβ ² , Rβ ³ , Rβ ⁴ , and Rβ ⁵ are preferably hydrogen atoms, and Rβ ⁶ is a hydrogen atom, an acylamino group (eg, acetylamino), a urethane group (eg, methylurethane).
Is preferred.

Next, equations (ε) and (ζ) will be described. R
ε ^1, Rε ^{2, Rζ 1} and Aruzeta ² represents a hydrogen atom or a nonmetallic substituent are the same as those described in R ⁶ and R ⁷ in A ² R ^2, specific examples are also the same. Among them, an aryl group (eg, 2-acetylaminophenyl, 4-hydroxycarbonylphenyl, phenyl), an alkyl group (eg, methyl, ethyl, t-butyl, 2-sulfophenylmethyl), a heterocyclic group (eg, 2-pyridyl) , 2-thienyl) is preferred.

Next, formulas (η) and (θ) will be described. R
η ¹ , Rη ² , Rη ³ , Rθ ¹ , Rθ ² and Rθ ³ represent a hydrogen atom or a non-metal substituent and are the same as those described for R ⁶ and R ⁷ of A ² , and specific examples are also the same. Is. In addition, Rη ¹
And Rη ² and / or Rη ² and Rη ³ , Rθ ¹ and Rθ ² and /
Alternatively, Rθ ² and Rθ ³ may combine with each other to form a ring structure. Among them, Rη ¹ , Rη ² , Rη ³ , Rθ ¹ , Rθ ² ,
At least one of Rθ ³ has a Hammett substituent constant σp of 0.
It is preferably a 30 or more electron-withdrawing group, and specific examples, a cyano _{group, -CCl 4, -CF 3, -CHO} , -COOCH 3, -
COCH _3, nitro group, etc. -SO ₂ CH ₃ and the like. At that time, the other two are cyano group, acyl group (having 2 to 12 carbon atoms such as acetyl, pivaloyl, P-hydroxycarbonylbenzoyl), alkoxycarbonyl (having 2 to 12 carbon atoms such as methoxycarbonyl, ethoxycarbonyl), aryloxy. Carbonyl (C7-18, such as phenoxycarbonyl, p-sulfophenylcarbonyl), aminocarbonyl group (C1-12, such as methylaminocarbonyl, anilinocarbonyl), aryl group (C6-18, such as phenyl) , Tolyl, p-methoxyphenyl, o-hydroxyphenyl), alkyl groups (C1-C1)
12, such as methyl, ethyl, allyl, prenyl) are preferred.

Next, equations (ι) and (κ) will be described. R
ι ¹ , Rι ² , Rι ³ , Rκ ¹ , Rκ ² and Rκ ³ represent a hydrogen atom or a non-metal substituent, and are the same as those described for R ⁶ and R ⁷ of A ² , and specific examples are also the same. Is. Rι ¹ and Rι ² and Rκ ¹ and Rκ ² may be bonded to each other to form a ring structure. Among them, Rι ¹ and Rκ ¹ are preferably electron withdrawing groups having a Hammett's substituent constant σp of 0.15 or more, and examples thereof include trichloromethyl, trifluoromethyl, cyano, methoxycarbonyl, acetyl, chlorine atom, and methanesulfonyl. is there. Rι ² and Rκ ² are cyano groups and acyl groups (having 2 to 12 carbon atoms, such as acetyl, pivaloyl, p-
Hydroxycarbonylbenzoyl), alkoxycarbonyl (having 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl (having 7 to 18 carbon atoms, such as phenoxycarbonyl, p-sulfophenylcarbonyl), aminocarbonyl group (having 1 carbon atom). ~ 1
2, eg methylaminocarbonyl, anilinocarbonyl), aryl groups (having 6 to 18 carbon atoms, eg phenyl,
Trilyl, p-methoxyphenyl, o-hydroxyphenyl) and alkyl groups (having 1 to 12 carbon atoms, such as methyl, ethyl, allyl and prenyl) are preferred. Rι ³ and Rκ ³ are preferably an alkyl group (having 1 to 12 carbon atoms, for example, methyl, ethyl, methoxyethyl) and an aryl group (having 6 to 18 carbon atoms, for example, phenyl, o-chlorophenyl, 3,5-dihydroxycarbonylphenyl). .

Next, formulas (λ) and (μ) will be described. R
λ ¹ , Rλ ² , Rλ ³ , Rμ ¹ , Rμ ² and Rμ ³ represent a hydrogen atom or a non-metal substituent and are the same as those described for R ⁶ and R ⁷ of A ² , and specific examples are also the same. Is. Also, Rλ ¹
And Rλ ² and Rμ ¹ and Rμ ² may be bonded to each other to form a ring structure. Among them, Rλ ¹ and Rμ ¹ are preferably electron withdrawing groups having a Hammett's substituent constant σp of 0.15 or more, and specific examples thereof are the same as those described for Rι ¹ in the formula (ι). As Rλ ² and Rμ ² , the preferable examples described for Rι ² in the formula (ι) are also preferable here. Rλ ³ and Rμ ³ are R of the formula (ι)
The preferred examples mentioned under i ³ are also preferred here.

Next, equations (ν) and (ξ) will be described. R
ν ¹ , Rν ² , Rν ³ , Rν ⁴ , Rξ ¹ , Rξ ² , Rξ ³ and Rξ ⁴ represent a hydrogen atom or a non-metal substituent, and R ^{6 of} A ²
And R ⁷ and the specific examples are also the same. Further, Rν ¹ and Rν ² and / or Rν ² and Rν ³ and / or
Or Rν ³ and Rν ⁴ , Rξ ¹ and Rξ ² and / or Rξ ² and R
xi] ³ and / or Arukushi ³ and Arukushi ⁴ may be bonded together to form a ring structure. Among them, Rν ¹ and Rξ ¹ are preferably electron-withdrawing groups having Hammett's substituent constant σp of 0.15 or more, and specific examples thereof are the same as those described for Rι ¹ in the formula (ι). Rν ^2, Rξ ² is preferred preferred example described Aruiota ² of formula (iota) here as well. Rν ³ and Rξ ³ are an alkyl group (having 1 to 12 carbon atoms, for example, methyl, ethyl, t-butyl), an aryl group (having 6 to 18 carbon atoms, for example, phenyl,
Tolyl, p-methoxyphenyl, o-hydroxyphenyl), cyano group, acyl group (having 2 to 12 carbon atoms, such as acetyl, pivaloyl, p-hydroxycarbonylbenzoyl), alkoxycarbonyl group (having 2 to 12 carbon atoms, such as methoxycarbonyl) , Ethoxycarbonyl), aryloxycarbonyl (having 7 to 18 carbon atoms, for example, phenoxycarbonyl, p-methoxyphenylcarbonyl) and aminocarbonyl group (having 1 to 12 carbon atoms, for example, methylaminocarbonyl, anilinocarbonyl). Rν ⁴ , R
xi] ⁴ is preferably Preferred examples described in Aruiota ³ of formula (iota) here as well.

Next, equations (ο) and (π) will be described. R
ο ¹ , R ο ² , R ο ³ , R π ¹ , R π ² and R π ³ represent a hydrogen atom or a non-metal substituent and are the same as those described for R ⁶ and R ⁷ of A ² , and specific examples are also the same. Is. Rο ¹ , Rπ ¹
Is an alkyl group (having 1 to 12 carbon atoms, such as methyl, ethyl,
t-butyl, pentafluoroethyl), aryl groups (eg phenyl, trichlorophenyl, O-sulfophenyl,
m-chlorophenyl, 3,5-dichlorophenyl, m-cyanophenyl, m-trifluoromethylphenyl) are preferred.
Rο ² , Rο ³ , Rπ ² and Rπ ³ are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group,
An alkoxycarbonyl group, an aminocarbonyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and among them, an alkyl group (including those having a substituent.
t-butyl, i-propyl, methyl, ethyl, n-propyl,
Most preferred are n-butyl, trifluoromethyl, etc.) and aryl groups (including those having a substituent. C6-C18, such as phenyl, 4-hydroxycarbonylphenyl, etc.). Also preferred are those in which R o ² and R o ³ and Rπ ² and Rπ ³ are combined to form an aromatic or heteroaromatic ring (for example, a pyrimidine ring).

Next, equations (ρ) and (σ) will be described. R
ρ ^1, Rρ ² and Arushiguma ¹ represents a hydrogen atom or a nonmetallic substituent are the same as those described in R ⁶ and R ⁷ in A ^2, specific examples are also the same. Rρ ¹ and Rσ ¹ are an acylamino group (eg, acetylamino, benzoylamino), an anilino group (eg, methylamino, anilino, o-chloroanilino), and an alkyl group (eg, methyl, ethyl, t-).
Butyl), carbamoyl group (for example, carbamoyl, methylcarbamoyl), cyano group and carboxylic acid group are preferable. Rρ ² is a hydrogen atom, an alkyl group (having 1 to 12 carbon atoms,
For example, methyl, ethyl, hydroxyethyl, 2-hydroxycarbonylbenzyl, 2,4,6-trichlorophenylmethyl, 2-phenethyl), aryl group (eg phenyl, 2,
4,6-trichlorophenyl, 3,5-dichlorophenyl, 4-hydroxycarbonylphenyl) are preferred.

Next, formulas (τ) and (υ) will be described. R
τ ¹ , R τ ² , R τ ³ , R υ ¹ and R υ ² represent a hydrogen atom or a non-metal substituent, and are the same as those described for R ⁶ and R ⁷ of A ² , and specific examples are also the same. In formula (υ), Rυ ¹
Is preferably an electron-withdrawing group, and is preferably a phenyl group, a naphthyl group, a furan ring or a chroman ring. In equation (τ),
Rτ ¹ may be an electron withdrawing group such as a cyano group, a phenyl group or a heterocyclic group, or an electron donating group such as an amino group. R
One of τ ² and Rτ ³ is preferably a cyano group, and the other is preferably a cyano group or an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl).

Next, the formula (φ) will be described. Rφ ¹ , R
φ ² and Rφ ³ represent a hydrogen atom or a non-metal substituent,
It is the same as that described for R ⁶ and R ⁷ of ² and the same applies to specific examples. In addition, Rη ¹ and Rη ² may combine with each other to form a ring structure. Among them, Rφ ¹ is an alkyl group (having 1 to 12 carbon atoms, for example, methyl, ethyl, methoxyethyl, p-
(Sulfobenzyl), aryl groups (having 6 to 18 carbon atoms, such as phenyl, o-hydroxycarbonylphenyl, 3,5-dihydroxycarbonylphenyl), heterocyclic groups (having 4 carbon atoms)
~ 18, for example 2-furyl, 2-thienyl, 2-pyrimidinyl,
Imidazolyl and pyrazolyl) are preferred. Rφ ² is a cyano group, an acyl group (having 2 to 12 carbon atoms such as acetyl, pivaloyl, P-hydroxycarbonylbenzoyl), an alkoxycarbonyl (having 2 to 12 carbon atoms such as methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl (having carbon atoms). 7 to 18, such as phenoxycarbonyl, p-
Sulfophenylcarbonyl), an aminocarbonyl group (having 1 to 12 carbon atoms such as methylaminocarbonyl, anilinocarbonyl), an aryl group (having 6 to 18 carbon atoms such as phenyl, tolyl, p-methoxyphenyl, o-hydroxyphenyl), Alkyl group (C1-C12, such as methyl,
(Ethyl, allyl, prenyl) are preferred. Rφ3 is an alkyl group (having 1 to 12 carbon atoms, for example, methyl, ethyl, hydroxycarbonylethyl), an aryl group (having 6 to 18 carbon atoms,
For example, phenyl, o-chlorophenyl and 3,5-dihydroxycarbonylphenyl) are preferable.

Next, the formula (χ) will be described. Rχ ¹ , R
χ ² represents a hydrogen atom or a non-metal substituent, and is the same as that described for R ⁶ and R ⁷ of A ² , and the specific examples are also the same.
Rχ ¹ and Rχ ² may combine to form a ring structure. Among them, Rχ ¹ is preferably an alkyl group, an amino group (including alkylamino and anilino), an aryl group, and a heterocyclic group. Rχ ² is preferably a heterocyclic group and Rχ ³ -CO-. Rχ ³ represents an alkyl group, an aryl group, an amino group (including alkylamino and anilino), and an alkoxy group (including an aryloxy group). Rχ ² is particularly preferably Rχ ³ -CO-, and Rχ ³ is an alkyl group (eg ethyl, i-butyl, t-butyl), an aryl group (eg phenyl, o-sulfophenyl, o-hydroxyphenyl), an amino group ( Anilino) is particularly preferred.

A general formula (φ) will be described. Arupusai ¹ represents a hydrogen atom or non-metallic substituent, Za, Zb and Zc each -N =, or -C (Rψ ⁹⁾ = represents a. Rψ ⁹ represents a hydrogen atom or a non-metal substituent. Among the formulas (ψ), those represented by the following general formulas (ψ1) to (ψ6) are more preferable.

[0051]

Embedded image

R ψ ¹ represents a hydrogen atom or a non-metal substituent, and is the same as that described for R ⁶ and R ⁷ of A ² , and its specific examples are also the same. Rψ ¹ is an alkyl group (having 1 to 12 carbon atoms), an alkoxy group (having 1 to 12 carbon atoms), an aryl group (having 1 to 12 carbon atoms), a heterocyclic group (having 2 to 12 carbon atoms), a carboxylic acid group, A sulfonic acid group or an acylamino group (having 2 to 12 carbon atoms) is preferable. R ψ ² , R ψ ³ and R ψ ⁴ represent a hydrogen atom or a non-metal substituent. Of these, a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an amino group, an acyl group, an alkoxycarbonyl group, an aminocarbonyl group, a carboxylic acid group, and a sulfonic acid group are preferable, and among them, an alkyl group (including those having a substituent is included. 1 to 12 carbon atoms, for example, t-butyl, i-propyl, methyl, ethyl, n-propyl, n-butyl, trifluoromethyl, etc.), aryl groups (including those having a substituent. 6 to 18 carbon atoms, For example, phenyl, 4-hydroxycarbonylphenyl, etc.) are most preferable. Rψ ⁵ , Rψ ⁶ , Rψ ⁷ , and Rψ ⁸ are R ^{6 of} A ¹ .
And R ⁷ and the specific examples are also the same. The most preferable ones of Rψ ⁵ , Rψ ⁶ , Rψ ⁷ , and Rψ ⁸ are a hydrogen atom, an alkyl group (having 1 to 12 carbon atoms), a halogen atom, a carboxylic acid group, a sulfonic acid group, and a hydroxyl group.

Among the dyes used in the present invention, the most preferable one is that A ¹ of the general formula (1) is (α), (β),
(Ε), (ζ), (ρ), (σ), (φ), and (ψ)
It is a dye having a structure of.

Specific examples of the partial structure of the dye used in the present invention, A ¹ = N-, -A ² -R ¹ and the dye of the present invention are shown below, but the present invention is not limited thereto. is not.

[0055]

[Chemical 6]

[0056]

[Chemical 7]

[0057]

Embedded image

[0058]

[Chemical 9]

[0059]

[Chemical 10]

[0060]

[Chemical 11]

[0061]

[Chemical 12]

[0062]

[Chemical 13]

[0063]

Embedded image

[0064]

[Chemical 15]

[0065]

Embedded image

[0066]

[Chemical 17]

[0067]

Embedded image

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

The dye of the present invention comprises: (1) a method of oxidatively coupling a p-aminophenol derivative or a p-phenylenediamine derivative to a corresponding coupler compound; (2) a p-nitrosophenol derivative or a p-nitroso derivative. Condensation of aniline derivative (3) Condensation of quinone imine-N-chloridate (4) Synthesis by known synthesis methods such as electrode oxidation with p-aminophenol derivative or p-phenylenediamine derivative it can. The following shows a synthesis example.

Synthesis Example Synthesis of Exemplified Compound (43) 5- (1-Hydroxy-2-naphthoylamino) isophthalic acid 1
Disperse 5 g in 200 ml of methanol and add 20 ml of triethylamine.
ml, 3-amino-6-diethylamino-2-methylpyridine 10g
Was added.

40 ml of an aqueous solution of 25 g of ammonium persulfate was added dropwise to the obtained solution at room temperature. After stirring for 2 hours at room temperature, 500 ml of water was added, and the precipitated crystals were filtered off. 20 g of the obtained crude crystals were washed with 50 ml of methanol by heating, cooled, separated, and dried to obtain 15 g of dye. The structure of the obtained dye was confirmed by NMR spectrum and mass spectrum.

A method for producing a solid fine particle dispersion of a dye according to the present invention is described in JP-A-52-92716 and JP-A-55-15535.
No. 0, 55-155351, 63-197943, JP-A-3-182743
The method described in Japanese Patent No. WO88 / 04794 and the like can be used. Specifically, it can be prepared by using a surfactant and using a fine disperser such as a ball mill, a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill or a disc impeller mill. Further, after dissolving the dye in a weak alkaline aqueous solution, a method of precipitating fine particulate solids by lowering the pH to weakly acidic or a weak alkaline solution of the dye and an acidic aqueous solution are simultaneously mixed while adjusting the pH. Dispersions of dyes can be obtained by the method of making finely divided solids. The dyes may be used alone or in combination of two or more. When two or more kinds are mixed and used, they may be dispersed individually and then mixed, or may be simultaneously dispersed.

The dye dispersed in the form of solid fine particles according to the present invention is preferably dispersed so that the average particle diameter is 0.01 μm to 5 μm, more preferably 0.01 μm to 1 μm, and particularly preferably 0.01 μm. ~ 0.5 μm. Also,
The coefficient of variation of particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following formula.

(Standard deviation of particle size) / (Average value of particle size) × 100 A surfactant may be used in the production of the solid fine particle dispersion of the dye, and the surfactant may be an anion. Any of the cationic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but, for example, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates are preferred. , Anionic surfactants such as sulfosuccinates, sulfoalkyl polyoxyethiene alkylphenyl ethers, N-acyl-N-alkyl taurines and nonionics such as saponins, alkylene oxide derivatives and alkyl esters of sugars It is a surfactant.

The surfactant may be added at any position before dispersion, during dispersion, or after dispersion, but it is preferably added before the dispersion of the dye is started. Further, if necessary, it may be added to the dye dispersion liquid after the dispersion is completed. These anionic activators and / or nonionic activators may be used alone or in combination of two or more kinds, and both activators may be used in combination. The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion liquid of the dye, but it is usually 0.1 to 2000 mg per 1 g of the dye, preferably 0.5 to 1000m
g, more preferably 1 to 500 mg. The concentration of the dye in the dispersion is 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

To the dye dispersion of the present invention, a hydrophilic colloid used as a binder for a photographic constituent layer can be added before the start of dispersion or after the end of dispersion. As the hydrophilic colloid, it is advantageous to use gelatin, but in addition, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin and phthalated gelatin, and gelatin and a monomer having a polymerizable ethylene group can be used. Graft polymers, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N
-Dimethyl acrylamide, poly-N-vinyl pyrrolidone,
Synthetic hydrophilic polymers such as polymethacrylic acid, agar, gum arabic, alginic acid, albumin and casein can be used. You may use these in combination of 2 or more types.

The dispersion of the dye of the present invention is used for a layer constituting a photographic light-sensitive material, for example, a non-photosensitive hydrophilic colloid layer such as an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer and a backing layer. be able to. The dispersion of the dye of the present invention is
More preferably, it is contained in the non-photosensitive hydrophilic colloid layer, and substantially not contained in the photosensitive layer, and it is desirable that the sensitivity is not affected.

The preferable amount of the dye used is not uniform depending on the type of the dye, the characteristics of the photographic light-sensitive material and the like, but it is used in the photographic light-sensitive material so as to have an optical density of 0.05 to 3.0 depending on the purpose. It is 1 mg to 1000 mg, more preferably 3 mg to 500 mg, and particularly preferably 5 mg to 250 mg per 1 m ^{2 of the} light-sensitive material.

In the photographic light-sensitive material of the present invention, the solid fine particle dispersion of the dye may be contained in at least one non-photosensitive hydrophilic colloid layer. Gelatin is preferred as the hydrophilic colloid, and its coating amount is preferably
0.01 g / m was ^{2 ~2.0g} / m ^2, more preferably 0.1 g /
m ² was ~1.7g / m ^2, particularly preferably 0.2 g / m ² to 1.4
g / m ² .

The photographic light-sensitive material of the present invention may have at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer on one side of the support, and A photographic light-sensitive material having the emulsion layer and the colloid layer on both sides of the support is also preferably used. Photographic materials include medical X-ray photographic materials, printing plate photographic materials, color negative photographic materials, color reversal photographic materials, color photographic paper photographic materials, direct positive photographic materials, and heat-developable color photographic materials. , Diffusion transfer type color photographic materials and the like.

The gelatin used in the light-sensitive material of the present invention is generally produced from cow bone, cow hide, pig skin, etc. as a raw material. In the process of producing collagen, gelatin treated with lime etc., alkali treated gelatin, hydrochloric acid etc. There is acid-processed gelatin accompanied with processing, and any gelatin can be used in the present invention. For details of the manufacturing method and properties of these gelatins, see, for example, “T by Arthur Veis”.
he Macromolecular Chemistry of Gelatin '', 187-217
P. (1964) (Academic Press), TH James, The Theor
y of the photographic Process '' 4th.ed, p. 55 (1977)
(Macmillan), "Niwato Gelatin", published by Japan Nawa Gelatin Industry Association (1987), "Basics of Photographic Engineering-Silver Salt Photographs", pp. 119-124 (Corona Publishing Co.). The jelly strength (by PAGI method) of gelatin is preferably 250.
g or more. Calcium content of the gelatin of the present invention (PA
(By GI method) is preferably 4000 ppm or less, particularly preferably 3000 ppm or less.

Gelatin is hardened by a hardener, and the swelling ratio and film strength of the coating film can be adjusted by the amount of hardener in the photosensitive material. Examples of hardening agents include aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), mucohalogenoic acids (mucochloric acid, mucophenoxycycloric acid, etc.), epoxy compounds, active halogen compounds (2,4-dichloro-6-hydroxy-s). -Triazine etc.),
Active vinyl derivatives [1,3,5-triacryloylhexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis (β-vinylsulfonylpropionamide), etc.] ethyleneimines, carbodiimides, Methanesulfonic acid esters, organic hardeners such as isoxazoles, inorganic hardeners such as chromium alum, polymer hardeners described in U.S. Patents 3,057,723, 3,396,029, 4,161,407, etc. Can be used and can be used alone or in combination. The light-sensitive material of the present invention preferably has a swelling ratio of the coating film during development processing of 150 to 250%,
The film thickness after expansion is preferably 70 μm or less. The swelling rate means the difference between the film thickness after swelling in each processing solution and the film thickness before the development processing, and this is divided by the film thickness before processing and multiplied by 100, and the swelling rate is 250. If it exceeds%, poor drying occurs, and if the swelling ratio is less than 150%, uneven development and residual color tend to deteriorate during development.

The silver halide emulsion used in the light-sensitive material of the present invention may be any of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride and the like. However, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide are particularly preferable.

The silver halide grains in the silver halide emulsion are all isotropically grown crystal type such as cube, octahedron, and tetrahedron, or polyhedral crystal type such as sphere. It may be a twin crystal having a plane defect, or a mixed type or a composite type thereof. The grain size of these silver halide grains may be from fine grains of 0.1 μm or less to large grains of 15 μm.

The silver halide emulsion used in the light-sensitive material of the present invention can be produced by a known method. For example, research
Disclosure (RD) No.17643 (December 1978), 22-2
Page 3 of 1; Emulsion Preparation and Types
And No. 18716 (November, 1979), p.648. Also, TH James, "The theory
of the photographic process "4th edition, published by Macmillan (19
1977) Method described on pages 38-104, "Photographic Emulsion Chemistry", Focal Pr by GF Dauffin.
Published by ess (1966), P. Glafkides "Physics and Chemistry of Photography""Chimie et Physique Photographique", Paul Monte
Published in 1967, VL Zelikman et al., "Making and Coating Photographic Emulsion", F
It is prepared by the method described in Ocal Press (1964). That is, a neutral method, an acidic method, a solution method such as an ammonia method, a forward mixing method, a reverse mixing method, a double jet method,
It can be produced using mixing conditions such as a controlled double jet method, conversion methods, particle preparation conditions such as a core / shell method, and combinations thereof.

The silver halide emulsion preferably used in the present invention is, for example, JP-A-59-177535 and 61-802238.
No. 61-132943, No. 63-49751, and the like, high internal iodine type monodisperse particles are disclosed. The crystal habit may be a cube, an octahedron, a tetrahedron, or an intermediate (111) plane and (100) plane. The monodisperse emulsion as used herein means, for example, when the average grain diameter is measured by a conventional method, halogen having at least 95% of grains by number or weight is within ± 40% of the average grain size, preferably within ± 30%. It is a silver halide grain. The grain size distribution of silver halide grains is
It may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The definition of monodispersity described here is described in JP-A-60-162244, and the coefficient of variation with respect to particle diameter is 0.2 or less. The crystal structure of silver halide may be composed of different silver halide compositions inside and outside. For example, a core / shell type monodisperse emulsion having a two-layer structure composed of a high-iodity core portion and a low-iodity shell layer can be mentioned. A method for producing a monodisperse emulsion is known, for example, JP-A-48-36890 and JP-A-52-16364.
Nos. 55-142329, 58-49938, 60-14331, British Patents 1,027,146, 1,413,748, U.S. Patents 3,505,06.
No. 8, No. 3,574,628, No. 3,655,394, No. 4,444,877 and the like.

The silver halide emulsion preferably used in the present invention includes tabular grains having an aspect ratio of 3 or more. The advantages of such tabular grains include improved spectral sensitization efficiency and improved image graininess and sharpness. For example, British Patent 2,112,157 and U.S. Pat.
Issue 4,433,048, Issue 4,414,310, Issue 4,434,226,
JP-A-58-113927, 58-127921, 63-138342,
No. 63-284272, No. 63-305343, etc.,
The emulsion can be produced by the methods described in these publications. The tabular silver halide grains according to the present invention are preferably monodisperse emulsions having a narrow grain size distribution, and the coefficient of variation is preferably 25% or less, more preferably 20% or less, particularly preferably 15%. % Or less. As tabular silver halide grains, at least 80% or more of the total projected area of silver halide grains contained in the emulsion should have an aspect ratio of 3.0 to 12.0 indicated by the (grain size) / (thickness) ratio. Is preferred, and more preferably the aspect ratio is 3.
0 to 8.0. The thickness of tabular silver halide grains is 0.05.
~ 1 μm is preferable, more preferably 0.05 ~
It is 0.5 μm. When the ratio (t / l) of the longest distance (l) between two or more parallel twin planes of the tabular silver halide grain and the thickness (t) of the tabular grain is 5 or more, It is preferable that it is, more preferably 7 or more.
The tabular silver halide grains preferably used are core /
Shell type grains having, for example, a double structure type grain having a silver halide composition whose surface is different from the grain interior.
Examples thereof include multi-structured particles shown in No. 151 and the like.

As a silver halide solvent, for example, ammonia, a thioether compound, a thione compound or the like can be used for controlling the growth of silver halide grains during the formation thereof. Also, during physical aging and chemical aging, zinc,
A metal salt such as lead, thallium, iridium or rhodium can coexist. The silver halide can be sensitized with a noble metal salt such as a sulfur compound or a gold salt. Further, reduction sensitization can be performed, and these methods can be combined for sensitization. Further, a silver halide spectrally sensitized to a desired wavelength region with a spectral sensitizing dye can be used. Dyes used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye, and hemioxonol dye, and particularly useful dyes belong to cyanine, merocyanine, and complex merocyanine dye. It is a pigment.

An emulsion prepared by dispersing the above silver halide in a hydrophilic colloid medium, for example, gelatin is coated on a polyethylene terephthalate or triacetate cellulose support to obtain the light-sensitive material of the present invention. For the cross-linking of gelatin, aldehydes such as glyoxal and mucochloric acid, cyanuric acid, aziridine, vinyl sulfones and the like can be used.

When the light-sensitive material of the present invention is applied for printing plate making, the tone of the light-sensitive silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto, and other hydrophilic colloid layer are hardened to adjust the tone. A hydrazine compound or a tetrazolium compound may be contained as an agent, an amine compound may be contained as a contrast enhancing agent, or a redox compound which releases a development inhibitor by a redox reaction during development may be contained.

As the hydrazine compound, --NH in the molecule
A compound having an NH- group, and a compound represented by the following general formula (2) is preferable.

In the general formula (2) R ⁴ —NHNH—Y—R ⁵ formula, R ₄ represents an aliphatic group, an aromatic group or a heterocyclic group,
R ⁵ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and Y represents —CO—.
Represents a group, —COCO— group, —SO ₂ — group, —SO— group, thiocarbonyl group or iminomethylene group.

The general formula (2) will be described in more detail. The aliphatic group represented by R ⁴ is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
Is an alkyl group, and may be branched or cyclic. R
^The aromatic group represented by ⁴ is preferably a monocyclic or condensed ring aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocyclic group represented by R ⁴ is preferably a monocyclic or condensed ring heterocyclic group containing at least one hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and examples thereof include a pyridyl group, a quinolyl group and an imidazolyl group. Base,
Examples thereof include furyl group, thienyl group, thiazolyl group, benzthiazolyl group, pyrrolidyl group and morpholyl group. These aliphatic group, aromatic group or heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an alkylthio group, an amino group, a ureido group, a sulfamoyl group and a carbamoyl group. Group, a sulfonamide group, an acylamino group, a hydroxy group, a halogen atom, a cyano group, an acyl group, an alkoxycarbonyl group, a carboxy group and the like, preferably, an alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms Alkoxy group, carbon number 1
An amino group substituted with 20 alkyl groups, a sulfonamide group having 1 to 30 carbon atoms, and an acylamino group having 1 to 30 carbon atoms.

R ⁴ is preferably an aryl group or an aromatic heterocyclic group. Particularly preferably, R ⁴ is an aryl group or an aromatic heterocyclic group having a diffusion resistant group or a silver halide adsorption promoting group. As the anti-diffusion group, a ballast group used as an immobilizing group for a photographic coupler (eg, an alkyl group and its derivative having 10 or more carbon atoms in total, an aryl group and its derivative) is preferable, and a halogenated group is preferable. As the silver adsorption promoting group, thiourea group, thiourethane group, mercapto group, thioether group, thione group,
Examples thereof include a mercapto heterocyclic group, a thioamide heterocyclic group, a sulfur-containing heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

As Y in the general formula (2), --CO--
The group, -COCO- group is preferable.

The alkyl group represented by R ⁵ in the general formula (2) is an alkyl group having 1 to 8 carbon atoms (for example, a methyl group,
An ethyl group, an octyl group, a methoxyethyl group, a 2-hydroxyethyl group, a 3-methanesulfonamidopropyl group and the like) are preferable, and the aryl group is a monocyclic or bicyclic aryl group (for example, a phenyl group, 3-methanesulfonamide). Phenyl group, 4-cyanophenyl group, 4-acetylphenyl group, naphthyl group, etc.) are preferred, and the alkoxy group is an alkoxy group having 1 to 8 carbon atoms (eg, ethoxy group, butoxy group, 2-methoxyethoxy group, etc.). Preferably, the aryloxy group is a monocyclic or bicyclic aryloxy group (eg, phenoxy group, 4-methanesulfonylphenyl group, 4-cyanophenyl group, naphthyloxy group, etc.), and the amino group is mono-substituted or Di-substituted amino groups (eg methylamino, dimethylamino, propylamino, anilino, dimethoxy) Ciethylamino group, N-ethyl
-N-methanesulfonylethylamino group, 2,2,6,6-tetramethylpiperidylamino group, morpholino group, pyrrolidyl group and the like) are preferable.

Preferred hydrazine compounds include JP-A-3-36540, JP-A-6-194774 and US Pat. No. 4,269,9.
The compounds described in No. 29 are mentioned, for example, the following compounds are mentioned.

1-formyl-2-{[4- (n-butylureido) phenyl]} hydrazine, 1-formyl-2- {4- [2- (2,4-di-ter
t-Pentylphenoxy) butylamido] phenyl} hydrazine, 1- (2,2,6,6-tetramethyl-4-piperidylaminooxalyl) -2- {4- [2- (2,4-di-tert- (Pentylphenoxy)
Butyramido] phenyl} hydrazine, 1- {4- (2,2,6,6-tetramethylpiperidyl) aminooxalyl} -2- {4- [2- (2,
4-di-tert-pentylphenoxy) butyramide] phenylsulfonamidophenyl} hydrazine, 1- {4- (2,2,6,6-
(Tetramethylpiperidyl) aminooxalyl} -2- {3- [1-
Phenyl-1′-p-chlorophenylmethylthioacetamidophenyl] sulfonamidophenyl} hydrazine, 1-formyl-2-{[4- (2- (2- (2-ethoxy) ethoxy) ethoxy)
Ethylthioacetamidophenyl] sulfonamidophenyl} hydrazine, 1- (N-pyridiniummethylcarbonyl) -2-{[4- (2- (2- (2-ethoxy) ethoxy) ethoxy) ethylthioacetamidophenyl] sulfonamidophenyl }
Examples thereof include hydrazine chloride.

The hydrazine compound is added by adding alcohols such as methanol and ethanol, ethylene glycols,
It can be added after being dissolved in ethers, ketones and the like, and the addition amount is 10 ^-6 to 10 ^-1 mol, preferably 10 ^-4 to 10 ^-2 mol per mol of silver halide. A light-sensitive material containing a hydrazine compound is developed with a developer having a pH of 10.8 or less for a development time of 30 seconds or less, and the contrast is
Can be 10 or more.

Examples of the tetrazolium compound include compounds described in JP-A No. 3-15039, and examples thereof include 2,3-di (p-methoxyphenyl) -5-phenyltetrazolium chloride and 2,3-di ( Examples include p-methylphenyl) -5-phenyltetrazolium chloride and 2,3,5-tri (p-methylphenyl) tetrazolium chloride.

The amine compound as a contrast enhancement agent contains at least one nitrogen atom, and is disclosed in, for example, JP-A-57-120434.
No. 57, No. 57-129435, No. 57-129436, No. 60-129746,
56-94347, 60-140340, 60-218642, 60-6
6248, U.S. Pat.Nos. 417,498, 3,021,215, and
No. 3,046,134, No. 3,523,787, No. 3,746,545, No. 4,013,471, No. 4,038,075, No. 4,072,523,
The compounds described in No. 4,072,526 and the like can be appropriately selected and used.

In the present invention, it is preferable to use a redox compound together with the hydrazine derivative.

The redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones and the like as redox groups, and 5-nitroindazole and 4-nitroindazole as development inhibitors. , 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole, 5-
It is a compound having nitrobenztriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4-nitroimidazole and the like, and examples thereof include compounds described in JP-A No. 3-249643 and US Pat. No. 4,269,929. The redox compound is added by methanol, ethanol, ethylene glycol, triethylene glycol, propylene glycol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate,
It can be added after being dissolved in an organic solvent such as acetone or methyl ethyl ketone. Further, those which are difficult to dissolve in water or an organic solvent can be added after being dispersed in the form of solid fine particles by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like. The addition amount is from 10 ^-6 to 10 ^-1 mol, and preferably from 10 ^-4 , per mol of silver halide.
It is 10 ^-2 mol. Preferred redox compounds include:
For example, 2- (stearylamide) -5- (1-phenyltetrazole-5-thio) hydroquinone, 2- (2,4-di-t-amylphenopropionamide-5- (5-nitrotriazol-2-yl) )
Hydroquinone, 2-dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone, 1- (4-nitroindazol-2-yl-carbonyl) -2-{[4- (n-butylureido) phenyl] } Hydrazine, 1- (5-nitroindazol-2-yl-carbonyl) -2- {4- [2- (2,4-di-tert-pentylphenoxy) butyramide] phenyl} hydrazine, 1-
(4-Nitrotriazol-2-yl-carbonyl) -2- {4- [2-
(2,4-di-tert-pentylphenoxy) butylamido] phenyl} hydrazine, 1- (4-nitroimidazol-2-yl-carbonyl) -2- {4- [2- (2,4-di-tert-pentyl Phenoxy) butylamide] phenylsulfonamidophenyl} hydrazine and the like.

If necessary, various techniques and additives known in the art can be used in the silver halide photographic material of the present invention. For example, in addition to the photosensitive silver halide emulsion layer, a photographic constituent layer such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer can be provided. , Supersensitizer, coupler, high boiling point solvent, antifoggant, stabilizer, development inhibitor, bleaching accelerator, fixing accelerator, color mixture inhibitor, formalin scavenger, color tone agent, hardener, surfactant, A thickener, a plasticizer, a slip agent, an ultraviolet absorber, a polymer latex, an antistatic agent, a matting agent and the like can be contained by various methods.

As the support that can be used in the silver halide light-sensitive material of the present invention, cellulose triacetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, polyethylene and the like are laminated. Paper, glass, metal, etc. can also be used. The surface of these supports is provided with an undercoat layer to improve the adhesion of the coating layer, or is subjected to an undercoating process such as corona discharge or ultraviolet irradiation as required.

More specifically, these additives described above are described in Research Disclosure No. 17643 (December 1978).
No. 18716 (November 1979), No. 308119 (December 1989)
Month). The types of compounds shown in these Research Disclosures and their locations are shown below.

Additives RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 IVB Dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26 to 27 XI 650 Right 1005 to 6 XI Antistatic agent 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 to 9 XVI Binder 26 XXII 1009 XXII Support 28 XVII 1009 XVII To develop the silver halide light-sensitive material of the present invention, for example, The James of The Theory of the Photographic Process 4th Edition (The Theory of th)
e Photographic Process, fourth Edition) 291-334 and Journal of the American Chemical
Society (Journal of the AmericanChemical Societ
y) The developer as described in Volume 73, page 3,100 (1951) is effectively used. Specific examples of the developing agent include dihydroxybenzenes (eg, hydroquinone), 3-
Pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone), aminophenols (eg p-aminophenol, N-methyl)
-p-aminophenol), 1-phenyl-3-pyrazolines,
Ascorbic acid and the like can be used alone or in combination.

The silver halide photosensitive material according to the present invention is
The development processing time from development to drying is 90 seconds or less, which enables rapid development processing.
Development processing can be performed even by rapid processing of less than a second.
Furthermore, development processing can be performed even by rapid processing with a development processing time of 30 seconds or less. The treatment temperature is preferably
The temperature is 25 to 50 ° C, more preferably 30 to 40 ° C. The pH of the developer is usually pH 12.0 to pH 9.0, preferably pH 11.5 to pH 9.0. More preferably, pH 11.0
Is about pH 9.5.

[0112]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate Na salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 824 g iodination Potassium 23.5g Finished to 2825ml with water D1 1.75N Potassium bromide aqueous solution Solution A1 solution B1 and solution using the mixing stirrer described in JP-B-58-58288 and 58-58289 at the following silver potential control amount of 35 ° C. 46 of each C1
Nucleation was carried out by adding 4.3 ml by the simultaneous mixing method over 1.5 minutes.

After stopping the addition of solution B1 and solution C1, it took 60 minutes to raise the temperature of solution A1 to 60 ° C., adjust the pH to 5.0 with 3% potassium hydroxide, and then re-solution. 55.4 ml / each of B1 and solution C1 by the simultaneous mixing method
It was added for 42 minutes at a flow rate of min. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during this temperature increase from 35 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B1 and C1 was +8 mv each using the solution D1. And +
Controlled to be 16mv. After the addition was completed, the pH was adjusted to 6 with 3% potassium hydroxide, and the mixture was immediately desalted and washed with water.

In this seed emulsion, 90% or more of the total projected area of silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains had an average thickness of 0.06 μm and an average grain size ( It was confirmed by an electron microscope that the circle diameter was 0.59 μm. The variation coefficient of thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Emulsion Em-1) Tabular emulsion Em-1 having a core / shell structure was prepared using seed emulsion-1 and the following solutions.

A2 ossein gelatin 11.7 g polypropyleneoxy-polyethyleneoxy-disuccinate Na salt (10% ethanol aqueous solution) 1.4 ml seed emulsion-1 0.10 mole equivalent Finish with water to 550 ml B2 ossein gelatin 5.9 g potassium bromide 6.2 g iodine Potassium iodide 0.8g Finish with water to 145ml C2 Silver nitrate 10.1g Finish with water to 145ml D2 Ocein gelatin 6.1g Potassium bromide 94g Finish with water 304ml E2 Silver nitrate 137g Finish with water 304ml A2 liquid vigorously stirred at 67 ℃ The solution B2 and the solution C2 were added by the double jet method in 58 minutes. Next, in the same liquid, D2
Solution and E2 solution were added by the double jet method in 48 minutes. During this time, pH was kept at 5.8 and pH was kept at 8.7 throughout.

After completion of the addition, desalting and precipitation were carried out in the same manner as in the seed emulsion-1, and the average silver iodide contents of pAg8.5 and pH5.85 were obtained at 40 ° C.
An emulsion of 0.5 mol% was obtained.

Observation of the obtained emulsion with an electron microscope revealed that tabular silver halide grains having an average aspect ratio of 4.5 with 81% of the projected area having an average grain size of 0.96 μm and a broad grain size distribution of 19%. Met. The average distance between twin planes is 0.019 μm.
And the coefficient of variation was 28%.

Next, after the emulsion (Em-1) was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye was added as a solid fine particle dispersion, and then adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added. Was added to the mixed solution of triphenylphosphine selenide in a mixed solvent of ethyl acetate and methanol, and after 60 minutes, a silver iodide fine grain emulsion was added, and ripening was performed for a total of 2 hours. 4-hydroxy-6-methyl- as a stabilizer at the end of aging
A predetermined amount of 1,3,3a, 7-tetrazaindene (TAI) was added.

The above-mentioned additives and their addition amounts (per mol of AgX) are shown below.

Spectral sensitizing dye (SD-1) 2.0 mg Spectral sensitizing dye (SD-2) 120 mg Adenine 15 mg Ammonium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Silver iodide Fine particle emulsion 280 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 50 mg A solid fine particle dispersion of a spectral sensitizing dye is disclosed in Japanese Patent Application No. 4-99437.
It was prepared according to the method described in No. That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been adjusted to 27 ° C. in advance, and the mixture was stirred by a high speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes to obtain the dye.

The average iodine content on the outermost surface of the silver halide grains contained in the silver halide emulsion (Em-1) by the addition of the silver iodide fine grain emulsion was about 4 mol%. The following additives were added to the emulsion thus sensitized to prepare an emulsion layer coating solution, and at the same time, a protective layer coating solution was prepared.

Next, a blue-colored polyethylene terephthalate film base for X-rays having a density of 0.15 (thickness: 175 μm)
The copolymer aqueous dispersion obtained by diluting both sides of m) so that the concentration of the copolymer consisting of three kinds of monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt% and butyl methacrylate 40 wt% is 10 wt% is obtained. After coating and undercoating, the following dye layers were coated on both sides of the support. Further, the emulsion layer coating solution and the protective layer coating solution were simultaneously multi-layer coated in the following predetermined coating amounts and dried. First layer (dye layer) Solid fine particle dispersion dye Amount shown in Table 5 Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4-dichloro-6-hydroxy- 1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² A solid fine particle dispersion of dye was prepared according to the method described in World Patent 88/04794. . That is, in a 60 ml screw cap container, 21.7 ml of water and the surfactant Triton X.
-200 (manufactured by Rohm & Haas) and 6.7% solution 2.65g, and put into this solution 1.0g powdered dye in a mortar,
40 ml of zirconium oxide beads (2 mm diameter) was added. After the cap was closed and placed in a ball mill and dispersed at room temperature for 4 days, 8.0 g of a 12.5% gelatin aqueous solution was added and mixed well, and the zirconium oxide beads were filtered and removed to obtain a solid fine particle dispersion of the dye.

Second Layer (Emulsion Layer) The following various additives were added to the emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino -1,3,5-triazine 5 mg / m ² t-butylcatechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000 ) 35 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenylphosphonium chloride 20 mg / m ² 1, Ammonium 3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m ² colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² However, as gelatin 1. It was adjusted to be 0 g / m ² .

Third Layer (Protective Layer) Gelatin 0.8 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7 mg / m ² Polymethyl methacrylate matting agent 50 mg / m ² (Area average particle size 7.0 μm) Formaldehyde 20 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Bis (vinylsulfonylmethyl) ether 36 mg / m ² latex (L ) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² C ₉ F ₁₉ -O- (CH ₂ CH ₂ O ) ₁₁ -H 3mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ -H 2mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) _{(CH 2 CH 2 O) 4} - (CH 2) 4 SO 3 Na 1mg / m 2

[0129]

[Chemical 19]

[0130]

Embedded image

The amount of additive added was for one side, and the coated silver amount was adjusted to be 1.6 g / m ² for one side.

Each of the samples Nos. 1 to 10 thus obtained was stored under two kinds of storage conditions (condition A: 23 ° C./55% R
H, condition B: 40 ° C./80% RH), and the photographic performance was evaluated after storage for 4 days.

[Evaluation of Photographic Performance] Sample
It is sandwiched between sheets of intensifying screen KO-250 (made by Konica Corporation), a tube voltage of 80 kvp, a tube current of 100 mA, and an X of 0.05 seconds through an aluminum wedge.
Exposure was performed by irradiating a line. Then automatic processor SR for rapid processing
X-502 (manufactured by Konica Corp.) was used for processing with a developer and a fixer having the following formulations.

The processed sample was subjected to density measurement with an optical densitometer PDA-65 (manufactured by Konica Corp.) to evaluate sensitivity, fog and residual color. Sensitivity is the reciprocal of the exposure amount at fog density + 0.5, and the sensitivity immediately after coating and drying of sample No. 1 in Table 5 is 100.
It was shown by the relative value.

The residual color was visually evaluated by treating the obtained sample without exposing it. The best sample with no residual color is 5,
1 is a level where the residual color is extremely bad, and 4 or more is a practical level.

The evaluation of MTF was performed as follows. That is, an MTF chart containing a rectangular wave of 0.5 to 10 lines / mm made of lead was brought into close contact with the front side back surface of the fluorescent screen KO-250 (made by Konica Corp.) and shielded by the lead chart on the film surface. After irradiating with X-rays so that the density of the non-exposed area is about 1.0 on both sides and developing, the recorded rectangular wave pattern is the Sakura Micro Densitometer M-5 type (manufactured by Konica Corporation). It was measured at. The aperture size at this time is 300 μm in the direction of the rectangular wave and 25 μm in the direction of the right angle.
And the magnification was 20 times. MTF spatial frequency 2.0
The value is shown in line / mm. Table 5 shows the obtained results.

<Preparation of Processing Agent> (Developer formulation) Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% aqueous solution) 2280 g Sodium hydrogencarbonate 132 g Diethylenetetraamine pentaacetic acid 120 g 5-Methylbenzo Triazole 1.2 g 1-Phenyl-5-mercaptotetrazole 0.2 g Hydroquinone 340 g Water is added to make 5000 ml.

Part-B (for finishing 12 liters) Glacial acetic acid 170g Triethylene glycol 185g 1-Phenyl-3-pyrazolidone 22g 5-Nitroindazole 0.4g Starter glacial acetic acid 120g Potassium bromide 225g Add water to make 1000ml About water Part-A and Part-B above were added to 5 liters at the same time, and while stirring, make up to 12 liters with water and add glacial acetic acid.
The pH was adjusted to 10.4. This is used as a development replenisher. 20 ml of the starter for 1 liter of this developer replenisher
It was added and the pH was adjusted to 10.26 to obtain a developer.

(Fixer Solution Formulation) Prat-A (for 18 liter finish) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethyl) Amino) -ethyl-5-mercaptotetrazole 18g Prat-B (for 18 liters finish) Aluminum sulfate (anhydrous salt equivalent) 800g Part-A and Part-B are added at the same time to about 5 liters of water,
Water was added with stirring to make 18 liters, and the pH was adjusted to 4.40 using sulfuric acid and sodium hydroxide.

The processing was carried out at development 35 ° C., fixing 33 ° C., water washing 20 ° C. and drying 50 ° C., respectively, and the processing time was dry to dry for 45 seconds.

[0141]

[Table 5]

[0142]

[Chemical 21]

As is clear from the results in Table 5, the light-sensitive material containing the solid fine particle dispersion of the dye of the present invention has less adverse effect on photographic characteristics such as sensitivity and fog, has excellent sharpness, It can be seen that the residual color contamination afterward is extremely small and the storage stability over time is excellent.

Example 2 In the same manner as in Example 1, Samples 11 to 18 were prepared by changing the coating amount of the solid fine particle dispersion of the dye according to the present invention. The coating amount of the dye is shown in Table 6. These samples are 23 ℃ / 55% RH
After storing for 4 days under the conditions described above, the sensitivity, fog, and residual color were evaluated in the same manner as in Example 1. However, the treatment was carried out by using the developing solution and the fixing solution described in Example 1 at a developing temperature of 35 ° C., a fixing temperature of 33 ° C., a water washing temperature of 20 ° C. and a drying temperature of 50 ° C., and the processing time was dry to dry for 25 seconds. .. The obtained results are shown in Table 6.

[0145]

[Table 6]

As is clear from the results shown in Table 6, the light-sensitive material containing the solid fine particle dispersion of the dye of the present invention hardly adversely affects the photographic characteristics such as sensitivity and fog even in the ultra-rapid processing, and It can be seen that the residual color contamination after is extremely small.

Example 3 (Preparation of silver halide emulsion) 70 mol% of silver chloride, 30 of silver bromide
A silver nitrate aqueous solution and a mixed aqueous solution of NaCl and KBr were mixed by a controlled double jet method to grow a silver halide grain so as to have a mol% silver halide composition. At this time, the mixing was carried out under the conditions of 36 ° C., pH 7.8 and pH 3.0, and NaRhCl ₆ was added at 2 × 10 ⁻⁷ mol per mol of silver during grain formation. After mixing, 80 mg of the following SD-3 was added per 1 mol of silver. After that, desalting was carried out with modified gelatin treated with phenylisocyanate to obtain the following compounds (A) and (B)
A bactericide consisting of the mixture of (C) and ossein gelatin were added and redispersed. The obtained emulsion was cubic grains having an average grain size of 0.2 μm and a coefficient of variation of 10%. The emulsion thus obtained contains 4-hydroxy-6- per mole of silver.
Add 60 mg of methyl-1,3,3a, 7-tetrazaindene, and then add 5 mg of chloroauric acid and 0.5 mg of sulfur flower per mol of silver.
Chemical aging was carried out at 60 ° C. for 80 minutes under the conditions of H5.8 and pAg7.5. After ripening, add 900 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene per 1 mol of silver, and add KI 30
0 mg and SD-4 350 mg were added.

(Preparation of silver halide light-sensitive material) Undercoat layer having a thickness of 0.1 μm on both surfaces (see Example 1 of JP-A-59-19941).
An antihalation layer of the following prescription (1) was coated on one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm, which was coated so that the amount of gelatin would be 0.5 g / m ^2, and the halogen of (2) was applied. The amount of gelatin in the silver halide emulsion layer is 2.6 g.
/ M ² , and the amount of silver is 3.2 g / m ² , the protective layer of the following formulation (3) is 1.0 g / m ²
It was painted so that On the other undercoat layer on the opposite side, a backing layer was coated according to the following prescription (4) so that the amount of gelatin would be 3.1 g / m ² , and on top of that, a protective layer of the following prescription (5). Was coated so that the amount of gelatin would be 1.0 g / m ² to prepare a sample.

Formulation (1) [Antihalation layer composition] Gelatin 0.5 g / m ² Solid fine particle dispersion dye Amount shown in Table 3 Surfactant: Sodium dodecylbenzenesulfonate 5 mg / m ² Colloidal silica (average particle size 0.014 μm 18 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Hardener: HD 25 mg / m ² A solid fine particle dispersion of dye was prepared in the same manner as in Example 1.

Formulation (2) [Silver halide emulsion layer composition] Gelatin 2.6 g / m ² Silver halide emulsion Silver amount 3.2 g / m ² Antifoggant: 4-mercaptobenzoic acid 2 mg / m ² 5-Nitroindazole 10 mg / M ² Nucleating agent: Z-1 3 × 10 ^-5 mol / m ² Nucleating accelerator: Z-2 1 × 10 ^-4 mol / m ² Polymer latex-1 1.0 g / m ² Colloidal silica 0.5 g / m ² Compound P 45 mg / m ² Water-soluble polymer: V-1 20 mg / m ² Surfactant: Saponin 0.1 g / m ² Sodium sulfosuccinate isopentyl normal decyl ester 8 mg / m ² Hardener: 2-hydroxy-4 , 6-Dichloro-1,3,5-triazine 60 mg / m ² formulation (3) [emulsion protective layer composition] Gelatin 1.0 g / m ² matting agent: silica having an average particle size of 3.5 μm 20 mg / m ² polymer latex 2 0.5 g / m ² surfactant: sodium sulfosuccinic acid di (2-ethylhexyl) ester 10 mg / m ² surfactant F 1 2 mg / m ² promoter: hydroquinone 50 mg / m ² 1-phenyl-4-hydroxymethyl-4'-methyl-3-pyrazolidone 5 mg / m ² Hardener: HD 30 mg / m ² Formulation (4) [backing layer Composition] Dye (D-1) 50 mg / m ² Dye (D-2) 40 mg / m ² Dye (D-3) 30 mg / m ² Gelatin 3.1 g / m ² Surfactant: Sodium dodecylbenzenesulfonate 50 mg / m ² 1-Phenyl-5-mercaptotetrazole 5 mg / m ² Colloidal silica 0.4 g / m ² Hardener: HD 60 mg / m ² Formulation (5) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: Average particle size 4.0 μm polymethylmethacrylate 50 mg / m ² Surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² Hardener: HD 25 mg / m ² 2-hydroxy-4,6-dichloro-1,3 , 5-triazine 25mg / m ²

[0151]

[Chemical formula 22]

[0152]

[Chemical formula 23]

[0153]

[Chemical formula 24]

The samples obtained were evaluated by the following methods.

[Sensitivity and Gamma] The obtained sample was brought into close contact with a step wedge, exposed to a tungsten light of 3200 ° K for 3 seconds, and subjected to a developing and fixing treatment to determine the sensitivity. The sensitivity is the reciprocal of the exposure amount that gives a fog density + 3.0 transmission density, and was determined as a relative value under each condition with the sensitivity of Sample No. 1 being 100. Gamma has a transmission density of 1.0 to 3.0.
It was calculated from the slope of the characteristic curve in. Gamma needs to be 10 or more for practical use.

[Dot Quality] Dot area on the step wedge
A part of a 50% reticulated screen (150 lines / inch) is attached, the sample is brought into close contact with it, exposed for 5 seconds with a xenon light source, and the following development processing is performed to obtain a sample halftone quality of 100.
It was visually observed with a double magnifying glass, the sample having the best halftone dot quality was 5, 1 was an extremely bad level, and 4 or more was a practical level.

[Residual Color] The obtained sample was processed without being exposed, and five sheets were piled up and visually evaluated. The best sample with little residual color was set to 5, 1 was a level where the residual color was extremely bad, and 4 or more was a practical level.

The results obtained are shown in Table 7.

Processing was carried out under the following conditions with a rapid automatic developing machine using a developing solution and a fixing solution having the compositions shown below.

Developer Formulation (Composition A) Pure Water (Ion Exchange Water) 150 ml Ethylenediaminetetraacetic acid disodium 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1- Phenyl-5-mercaptotetrazole 30 mg Potassium bromide 4.5 g Potassium hydroxide Amount to make the pH of the used solution 10.4 (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order to make 1 liter.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Sodium citrate dihydrate 2 g Boric acid 6 g Acetic acid (90% aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 26.5 g Water 500 ml when using fixer The above composition A and composition B were dissolved in that order, and the solution was finished to 1 liter and used. Of this fixer
The pH was about 4.3.

Development Processing Conditions (Process) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 33 ° C. 20 seconds Water washing 15 minutes at room temperature Dry 45 ° C. 15 seconds

[0163]

[Table 7]

[0164]

[Chemical 25]

As is clear from the results shown in Table 7, the light-sensitive material containing the solid fine particle dispersion of the dye of the present invention hardly adversely affects photographic characteristics such as sensitivity and fog, and has excellent halftone dot quality. It can be seen that the residual color contamination after the development processing is extremely small.

Example 4 (Preparation of Silver Halide Emulsion) Silver chloride was prepared by the simultaneous mixing method.
A silver chlorobromide emulsion consisting of 70 mol% and the rest silver bromide was prepared. At the time of simultaneous mixing, K ₃ RhBr ₆ was added at 8.1 × 10 ⁻⁸ mol per mol of silver. The obtained emulsion was a cubic emulsion having an average grain size of 0.20 μm and monodisperse grains (variation coefficient: 9%). Then, the emulsion was desalted with a modified gelatin described in JP-A-2-280139 (a substitution of amino group in gelatin with phenylcarbamyl, for example, G-8 in JP-A-2-280139).
The EAg after desalting was 190 mV at 50 ° C.

The emulsion thus obtained was adjusted to pH 5.58 and EAg123 mV, and the temperature was adjusted to 60 ° C., and chloroauric acid was added to 2.2 mol per mol of silver.
After adding ^{x10 -5} mol and stirring for 2 minutes, S8 was added in an amount of 2.9 x 10 ^-6 mol per mol of silver, and chemical ripening was further performed for 78 minutes.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol and gelatin 28.4 g were added. To obtain an emulsion liquid.

(Preparation of silver halide light-sensitive material) Example 3
An antihalation layer of the following Formulation 1 was applied on one undercoat layer of the 100 μm-thick pyriethylene terephthalate film which had been subjected to the antistatic treatment described in 1. On this upper layer, a silver halide emulsion having the following formulation 2 was added, the silver amount of which was 3.3 g / m ² ,
It was coated so that the amount of gelatin was 1.7 g / m ² .

Further, a coating solution having the following formulation 3 was applied as a protective layer on the upper layer so that the amount of gelatin would be 0.8 g / m ² . On the undercoat layer on the opposite side, a backing layer of the following formulation 4 was coated so that the amount of gelatin would be 1.5 g / m ^2, and a protective layer of the following formulation 5 was added to the upper layer on the backing layer of the formulation 1 g / m ²
Was applied so that the samples shown in Table 8 were prepared.

Formulation 1 (antihalation layer composition) Gelatin 0.4 g / m ² Solid fine particle dispersion dye Amount shown in Table 8 Alkanol-XC (manufactured by DuPont) 3.5 mg / m ² Colloidal silica (average particle size 0.014 μm) 10 mg A solid fine particle dispersion of 25 mg / m ² N, N-methylenebis (β- (vinylsulfonyl) propionacid) / m ² dye was prepared in the same manner as in Example 1.

Formulation 2 (composition of silver halide emulsion layer) Sensitizing dye (SD-5) 6.0 mg / m ² hydrazine derivative (Z-3) 2 × 10 ⁻⁴ mol / mol Ag compound (C-1) 150 mg / Mol Ag compound (C-2) 100 mg / m ² Nucleation accelerator (Z-4) 1 × 10 ⁻³ mol / mol Ag latex polymer (L-1) 0.5 g / m ² Hardener (HD-1) 60 mg / m ² HCHO 30 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 0.64 mg / m ² 2-Mercapto-6-hydroxypurine 1.7 g / m ² EDTA 50 mg / m ² Hydroquinone 50 mg / m ² formulation 3 Sodium-iso-amyl-n-decylsulfosuccinate 12mg / m ² Matting agent: Monodisperse silica 22mg / m ² 1,3-vinylsulfonyl-2-propanol 40mg / m ² surfactant with an average particle size of 3.5μm (F-2) 0.6 mg / m ^{2 The} pH of each coating solution on the emulsion side was adjusted to 5.5 with sodium acetate.

Formulation 4 (Backing layer composition) Saponin 133 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 6 mg / m ² Colloidal silica 100 mg / m ² Dye (D-4) 30 mg / m ² Dye (D -5) 75 mg / m ² Dye (D-6) 30 mg / m ² Hardener (HD-2) 100 mg / m ² Recipe 5 (Backing Protective Layer Composition) Matting Agent: Single Mole Polymethyl with Average Particle Diameter 5.0 μm Methacrylate 50 mg / m ² Sodium-di- (2-ethylhexyl) sulfosuccinate 10 mg / m ²

[0174]

[Chemical formula 26]

[0175]

[Chemical 27]

The obtained sample was brought into close contact with a step wedge, and a wavelength of 633 nm was used as a substitute characteristic of He-Ne laser light.
After exposure, the automatic processor for rapid processing (made by GR-26SR Konica Corporation) using the developer and fixer of the following composition
Was processed under the following conditions.

(Developer formulation) Sodium sulfite 55 g Potassium carbonate 40 g Hydroquinone 24 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (dimesone S) 0.9 g Potassium bromide 5 g 5-Methyl-benzotriazole 0.13 g Boric acid 2.2g Diethylene glycol 40g Compound P-1 60mg

[0178]

[Chemical 28]

Water and potassium hydroxide were added to make 1 liter. This pH was 10.4.

(Fixer Formulation) (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240
ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6.0g Sodium citrate dihydrate 2.0g (Composition B) Pure water (ion exchange water) 17ml Sulfuric acid (50% W / V aqueous solution) 4.7g Aluminum sulfate (Aqueous solution having an Al ₂ O ₃ conversion content of 8.1% W / V) 26.5 g When the fixing solution was used, the above composition A and composition B were dissolved in this order in 500 ml of water to make 1 liter. P of this fixer
H was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development 35 ° C. 25 seconds Fixing 33 ° C. 17 seconds Washing at room temperature 15 seconds Drying 40 ° C. 30 seconds For the obtained sample, in the same manner as in Example 3, sensitivity,
Gamma, halftone dot quality, and residual color were evaluated. Table 8 shows the obtained results.

[0182]

[Table 8]

[0183]

[Chemical 29]

As is clear from the results shown in Table 8, the light-sensitive material containing the solid fine particle dispersion of the dye of the present invention has less adverse effect on photographic characteristics such as sensitivity and fog, has excellent sharpness, and is excellent in processing. It can be seen that the residual color contamination afterward is extremely small and the storage stability over time is excellent.

[0185]

According to the present invention, there is provided a silver halide photographic light-sensitive material having less fog, improved stability over time, high sensitivity and excellent sharpness, and giving an image with little residual color contamination after a short development process. We were able to. Further, according to the present invention, a processing method of a silver halide photographic light-sensitive material, which gives an image with little residual color contamination by a short-time development processing, was obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yamato Komamura Konica Stock Company, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (8)

[Claims] 1. A silver halide photographic light-sensitive material comprising a support and a layer containing an azomethine dye represented by the following general formula (1). Formula ^{(1) A 1 = N-} A 2 -R 1 wherein, A ¹ is azomethine dyes of the general formula (1) is an atomic group necessary to have absorption in the visible region and / or near-infrared region A ² represents a non-metallic atomic group necessary for forming an optionally substituted 5-membered or 6-membered heterocycle. R
¹ represents OH and NR ² R ³ , R ² and R ³ are each independently a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group. R ² and R ³ , R ² and A ² and R ³ and A ² may cooperate with each other to form a ring, and A ² may further have a condensed ring. ] 2. The silver halide photographic light-sensitive material according to claim 1, which has a non-photosensitive layer containing an azomethine dye represented by the general formula (1) on a support. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the azomethine dye represented by the general formula (1) is contained as a solid fine particle dispersion. 4. The azomethine dye represented by the general formula (1), wherein A ² is an optionally substituted 5-membered or 6-membered nitrogen-containing heterocycle. The silver halide photographic light-sensitive material according to any one of items. 5. R ^{1 of the} azomethine dye represented by the general formula (1) is NR ² R ³ (R ² and R ³ are each independently a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group), and the silver halide photographic light-sensitive material according to claim 1. 6. The azomethine dye represented by the general formula (1) is a dye having at least one of a phenolic hydroxyl group, a carboxyl group, a sulfamoyl group or a sulfonamide group in the molecule. Item 1
5. A silver halide photographic light-sensitive material according to any one of 5 to 5. 7. A silver halide photographic light-sensitive material containing a hydrazine derivative represented by the following general formula (2) in a silver halide emulsion layer or another hydrophilic colloid layer, a support and the halogen. 7. A non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of the dye represented by the general formula (1) is provided between silver halide emulsion layers. Silver halide photographic light-sensitive material. Formula (2) R ⁴ -NHNH-Y-R ⁵ [wherein, R ⁴ represents an aliphatic group, an aromatic group or a heterocyclic group, R ⁵ is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, Represents an aryloxy group or an amino group, Y
Represents a —CO— group, a —COCO— group, a —SO ₂ — group, a —SO— group, a thiocarbonyl group, or an iminomethylene group. ] 8. A development processing method, which comprises processing the silver halide photographic light-sensitive material according to claim 1 with a developer having a pH of 11 or less.