JPH08201972A - Silver halide photographic sensitive material and processing method - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material small in fog and high in sensitivity and sharpness and superior in dot quality by forming a nonphotosensitive hydrophilic colloidal layer containing the dispersed fine solid particles of a specified dye on a support. CONSTITUTION: This nonphotosensitive hydrophilic colloidal layer formed on the support contains the dispersed fine solid particles of the dye selected from formulae I-III in which Q is an aryl or heterocyclic group; each of G1 and G2 is an electron withdrawing group, at least one of them being a craboxy, sulfonamide, or sulf-amoyl group, having a Hammett's substituent constant σP of >=0.3; Y is a carbonyl or sulfonyl group or the like; Z is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring; each of L1 -L3 is a methine group; each of (l), (n), and (p) is 1 or 2; and (m) is 1, 2, or 3.

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, and more specifically, a novel silver halide photographic light-sensitive material which has less adverse effects such as fog and desensitization and is bleached during rapid processing and has excellent residual color. The present invention relates to a silver halide photographic light-sensitive material containing a diffusion resistant dye.

[0002]

2. Description of the Related Art Conventionally, a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material) has a light absorption filter,
It is well known that a dye is contained in a constituent layer of a light-sensitive material in order to absorb light having a specific wavelength for the purpose of preventing halation, preventing irradiation or adjusting the sensitivity of a photosensitive emulsion. Dyeing of layers has been done. Dyes for the purpose of substituting yellow colloidal silver in color photographic light-sensitive materials, dyeing dyes for crossover cut layers in X-ray photographic light-sensitive materials, dyes for dyeing non-photosensitive emulsion layers in printed photographic light-sensitive materials It has spread.

The dye used for such purpose has not only good absorption spectrum characteristics depending on the purpose of use, but it is also completely decolorized during development processing and easily eluted from the light-sensitive material. After processing, no residual color contamination by dye occurs, it does not adversely affect fog or desensitization on the photosensitive emulsion, does not diffuse from the colored layer to other layers, in the light-sensitive material or coating solution, 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 that the binder in the photosensitive material constituent layer, for example, gelatin forms an aggregate with the mordant, or increases the viscosity, resulting in uneven coating properties,
It has the drawback of causing serious damage such as cissing, the diffusion resistance between layers is not sufficient, and the elution and decoloring properties during processing are poor, requiring a processing bath with a high pH and being inferior in rapid processing suitability. There was a flaw.

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]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material and a processing method which meet the above-mentioned requirements for a dye which has been made diffusion resistant and which has less fog. Another object is to provide a silver halide photographic light-sensitive material having high sensitivity, sharpness and excellent halftone dot quality, and a processing method. Another object of the present invention is to provide a silver halide photographic light-sensitive material and a processing method which can provide an image with less residual color contamination even in a short-time development processing with a low pH developer.

[0009]

The above objects of the present invention have been achieved by the following constitutions.

[0010] 1. A silver halide photographic light-sensitive material having a non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye selected from the following general formula (1), general formula (2) or general formula (3) on a support.

[0011]

Embedded image

In the formula, Q represents an aryl group or a heterocyclic group,
G ₁ and G ₂ represent an electron-withdrawing group having a Hammett's σp value of 0.3 or more, and Y represents a carbonyl group, a sulfonyl group or> C.
= C (G ₃ ) (G ₄ ) group (where G ₃ and G ₄ are Hammett's σ
represents a electron-withdrawing group having a p value of 0.3 or more), and Z is 5
A non-metal atom group necessary for forming a 6-membered or 6-membered nitrogen-containing heterocycle, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a monovalent substituent, and R ₅ is an alkyl group. Represents a group, L ₁ ,
L ₂ and L ₃ represent a methine group, l represents an integer of 1 or 2, m represents an integer of 1, 2 or 3, n represents an integer of 1 or 2, p represents an integer of 1 or 2. Represents However, at least one of G _{1 and} G ₂ is an electron-withdrawing group having a group selected from a carboxyl group, a sulfonamide group or a sulfamoyl group. ] 2. G ₁ and G _{2 in the} general formula (1), the general formula (2) or the general formula (3) are cyano group, trifluoromethyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acyl group, alkylsulfonyl. Group, an arylsulfonyl group, and at least one of G ₁ and G ₂ has a group selected from a carboxyl group, a sulfonamide group, and a sulfamoyl group. .

3. 3. The silver halide photographic light-sensitive material as described in 1 or 2 above, wherein the aryl group represented by Q in the general formula (1) is a substituted or unsubstituted phenyl group.

4. Q in the general formula (1) is pyridyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indolyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, furyl group, benzofuryl group, thienyl group, benzothienyl group, thiazolyl group, 3. The halogen according to 1 or 2 above, which is a substituted or unsubstituted heterocyclic group selected from a benzothiazolyl group, an oxazolyl group, a benzoxazolyl group, a 4-oxoquinolyl group, a coumaryl group, a chromonyl group or a thiochromonyl group. Silver halide photographic light-sensitive material.

5. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support and containing the hydrazine derivative represented by the following general formula (4) in the emulsion layer or another hydrophilic colloid layer, And a non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye selected from the general formula (1), the general formula (2) or the general formula (3) between the silver halide emulsion layer and the silver halide emulsion layer. A silver halide photographic light-sensitive material characterized by:

General formula (4) A-NHNH-V-B In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group,
B represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and V is -CO.
- group, -SO- group, a thiocarbonyl group or an iminomethylene group - group, -COCO- group, -SO _2.

6. A processing method comprising developing the silver halide photographic light-sensitive material described in 5 above with a developer having a pH of 11.0 or less.

The present invention will be described in more detail below.

First, the dye represented by the general formula (1), the general formula (2) or the general formula (3) of the present invention (hereinafter also referred to as the dye of the present invention) will be described.

Examples of the aryl group represented by Q in the general formula (1), the general formula (2) or the general formula (3) include a phenyl group, a naphthyl group and a julolidyl group.
In addition, general formula (1), general formula (2) or general formula (3)
The heterocyclic group represented by Q is, for example, a pyridyl group,
Quinolyl group, isoquinolyl group, pyrrolyl group, indolyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, furyl group, benzofuryl group, thienyl group, benzothienyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, pyrazolopyridone, 4-oxoquinolyl group, coumaryl group, chromonyl Group or thiochromonyl group and the like, preferably pyridyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indolyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, free Group, benzofuryl group, thienyl group, benzothienyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, 4-oxoquinolyl group, coumaryl group, chromonyl group or thiochromonyl group.

The above-mentioned aryl group and heterocyclic group include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group,
Halogen atom, alkoxycarbonyl group, aryloxycarbonyl group, carboxyl group, cyano group, hydroxyl group, mercapto group, amino group, alkoxy group, aryloxy group, acyl group, carbamoyl group, acylamino group, ureido group, sulfonamide group, Examples thereof include a sulfamoyl group, and these substituents may have two or more kinds in combination. As a preferable substituent, an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, t-butyl group, octyl group, 2-hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxyl group, cyano group, Halogen atom (eg, fluorine atom, chlorine atom, etc.), C1-C6 alkoxy group (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, 2-methoxyethoxy group, methylenedioxy group, butoxy group, etc.), Substituted amino group (eg, dimethylamino group, diethylamino group, dibutylamino group, N-
Ethyl-N- (2-hydroxyethyl) amino group, N-ethyl- (2
-N-methanesulfonamidoethyl) amino group, di (2-methoxyethyl) amino group, morpholino group, piperidino group,
Pyrrolidino group, etc., carboxyl group, carbamoyl group (eg carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group etc.), alkoxycarbonyl group (eg methoxy) Carbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), acyl group (eg, methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-ethylsulfonamidophenylcarbonyl group, etc.), sulfone Amido group (for example, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (for example, sulfamoyl group, methylsulfamoyl group,
Phenylsulfamoyl group), and these substituents may be combined. Particularly preferred are a hydroxy group, the above alkoxy group, and the above substituted amino group.

The electron withdrawing groups represented by G ₁ and G ₂ in the general formula (1), the general formula (2) or the general formula (3) may be the same or different, and the substituent constant Hammett's σp A group having a value (described by Toshio Fujita, “Chemical Region Special Issue No. 122, Structure-Activity Relationship of Drugs”, 96-103 (1979) Nankodo, etc.) is preferably 0.3 or more, for example, a cyano group or trifluoro group. Methyl group, alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, 4-carboxyphenethyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, 4-
Hydroxyphenoxycarbonyl group, 4-carboxyphenoxycarbonyl group, etc.), carbamoyl group (eg, carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, 3-carboxyphenyl group) Carboxybenzylcarbamoyl group etc.), acyl group (eg methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-carboxyphenylcarbonyl group, 4-ethylsulfonamidophenylcarbonyl group etc.), alkylsulfonyl group (eg Methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, etc.),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorosulfonyl group, 4-carboxyphenylsulfonyl group, etc.), and at least one of G ₁ and G ₂ is an electron-withdrawing group having at least one of a carboxyl group, a sulfonamide group and a sulfamoyl group as a substituent. Is.

Y in the general formula (1) or the general formula (3) is
Carbonyl group, a sulfonyl group, or _{a> C = C (G 3)} (G 4)
Represents a group, G ₃ and G ₄ may be a σp value of 0.3 or more group's substituent constant Hammett, for example said G ₁ and G
_The groups listed in ₂ .

5 or 6 represented by Z in the general formula (3)
The group of non-metal atoms necessary to form a membered nitrogen-containing heterocycle may include a condensed ring, for example, pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzothiazole, naphthothiazole, indolenine, Examples include pyrrole, indole, imidazole, benzimidazole and the like. These nitrogen-containing heterocycles include those having a substituent, and as the substituent, the substituent described in the description of Q in the general formula (1), the general formula (2) or the general formula (3) can be used. Can be mentioned.

As the monovalent substituents of R ₁ , R ₂ , R ₃ or R _{4 in} the general formula (1), the general formula (2) or the general formula (3), the general formula (1) and the general formula (2) or the substituents described in the description of Q in the general formula (3) are mentioned, and preferably an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, t-butyl group, octyl group, 2- Hydroxyethyl group, 2-methoxyethyl group, etc.), hydroxy group, cyano group, halogen atom (eg, fluorine atom, chlorine atom, etc.),
Alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, butoxy group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, dibutylamino group, N- Ethyl-N- (2-hydroxyethyl) amino group, N-ethyl-N- (2-
(Methanesulfonamidoethyl) amino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxyl group, sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (eg, sulfamoyl group, methylsulfamoyl group) Base,
Phenylsulfamoyl group), and these substituents may be combined.

The alkyl group represented by R ₅ in the general formula (3) includes those having a substituent, preferably an alkyl group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group, Octyl group, dodecyl group, 2-methoxyethyl group, 2-ethoxycarbonylethyl group, N, N-dimethylcarbamoylpropyl group, N- (2-methoxyethyl) carbamoylethyl group, 2-hydroxypropyl group, 3-methanesulfone Amidopropyl group, benzyl group, 4-carboxybenzyl group, 4-carboxyphenethyl group and the like).

The methine groups represented by L ₁ , L ₂ and L ₃ of the general formula (1), the general formula (2) or the general formula (3) include those having a substituent, and the substituent is For example, an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group,
Hexyl group etc.), aryl group (eg phenyl group, tolyl group, 4-hydroxyphenyl group etc.), aralkyl group (eg benzyl group, phenethyl group etc.), heterocyclic group (eg pyridyl group, furyl group, thienyl group etc.) A substituted amino group (eg, dimethylamino group, diethylamino group, anilino group, etc.), alkylthio group (eg, methylthio group, etc.),
Cyano group, alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, 2-methoxyethoxycarbonyl group, etc.), carbamoyl group (eg carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, P-carboxycarbamoyl group) Groups and the like).

In the dye represented by formula (1), formula (2) or formula (3) of the present invention, at least one of G _{1 and} G ₂ is a carboxyl group, a sulfonamide group or A dye having an electron-withdrawing group having a substituent selected from a sulfamoyl group as a substituent is preferable, and a dye having an electron-withdrawing group having a carboxyl group as a substituent is more preferable.

In the general formula (1), Q is a substituted or unsubstituted phenyl group, pyridyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indolyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, furyl group. Group, benzofuryl group, thienyl group, benzothienyl group,
Thiazolyl group, benzothiazolyl group, oxazolyl group,
A dye which is a benzoxazolyl group, a 4-oxoquinolyl group, a coumaryl group, a chromonyl group or a thiochromonyl group is advantageously used, and particularly, a substituted or unsubstituted phenyl group, a pyridyl group, a pyrrolyl group, an indolyl group, a pyrazolyl group,
Preferred are an imidazolyl group, a furyl group, a benzofuryl group, a thienyl group, a benzothienyl group, a thiazolyl group, an oxazolyl group and a coumaryl group. Preferred substituents include
Particularly, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms (eg, methoxy group, ethoxy group, 2-hydroxyethoxy group,
2-methoxyethoxy group, methylenedioxy group, butoxy group, etc., substituted amino group (eg, dimethylamino group, diethylamino group, dibutylamino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methane Sulfonamide ethylamino group, di (2-methoxyethyl) amino group,
Morpholino group, piperidino group, pyrrolidino group, etc.) and carboxyl group.

Next, specific examples of the dye represented by formula (1), formula (2) or formula (3) of the present invention are shown.

[0031]

Embedded image

[0032]

[Chemical 4]

[0033]

Embedded image

[0034]

[Chemical 6]

[0035]

[Chemical 7]

[0036]

Embedded image

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

Embedded image

[0043]

[Chemical 15]

[0044]

Embedded image

[0045]

[Chemical 17]

[0046]

Embedded image

[0047]

[Chemical 19]

[0048]

Embedded image

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

The dyes of the present invention are, for example, J. Griffiths, K.
A. Bello, and L. Cheng, J. Chem. Soc., Perkin Trans. 2,
815 pages (1987), CHChen, GAReynolds, HRLuss,
and JHPerlstein, J.Org.Chem., 51, 3382 (1986
It can be produced by utilizing the synthetic method described in the literature such as (Year). A specific synthesis example is shown below.

Synthesis Example 1 Exemplified Dye 1 1200 g of 1,3-indandione and 14.9 g of N, N-dimethylaminobenzaldehyde were added to 200 ml of ethanol, and the mixture was heated under reflux for 5 hours. Ethanol was partially distilled off under reduced pressure, water was added to dilute it, and the precipitated crystals were collected by filtration and washed with ethanol,
Dried. 17.4 g of these crystals were put in 200 ml of acetic anhydride and stirred, and 12.2-cyanoacetylaminobenzoic acid 12.2 was added.
g and 9.8 g of sodium acetate were added, and the mixture was heated at 100 ° C. for 2 hours. After cooling, the reaction solution was poured into water and stirred, and the precipitated crystals were collected by filtration. It was washed with methanol and ethyl acetate and dried to obtain 15.7 g of dye.

Synthesis Example 2 Exemplified dye 54 3-oxo-2,3-dihydrothianaphthene was added to 200 ml of ethyl acetate.
-1,1-dioxide 18.2g and 5-bis (2-methoxyethyl)
22.7 g of aminofurfural was added, and the mixture was heated under reflux for 4 hours. Part of ethyl acetate was distilled off under reduced pressure, and the precipitated crystals were collected by filtration. It was washed with a small amount of ethanol and dried. This crystal 2
0.5 g was put into 100 ml of N, N-dimethylformamide and stirred, 11.7 g of 4-cyanoacetylaminobenzoic acid and 5.0 g of sodium acetate were added, and the mixture was heated at 100 ° C. for 2 hours. After cooling, the reaction solution was poured into water and stirred, and the precipitated crystals were collected by filtration. Wash with methanol, ethyl acetate, dry, dye
13.2 g was obtained.

A method for producing a solid fine particle dispersion of the dye of the present invention is described in JP-A-52-92716 and JP-A-55-155350.
No. 55-155351, No. 63-197943, Japanese Patent Laid-Open No. 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 producing 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, 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, etc.
It may be 0.1 to 2000 mg per 1 g of dye, preferably 0.5 to 100
It may be 0 mg, 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 of 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-
Synthetic hydrophilic polymers such as N, N-dimethylacrylamide, poly-N-vinylpyrrolidone and 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 dye dispersion of the present invention is used in a layer constituting a light-sensitive material, for example, a non-light-sensitive 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. You can The preferred amount of the dye, the kind of the dye, but not uniform due characteristics of the photosensitive material, the optical density according to the purpose in the light-sensitive material is used so that 0.05 to 3.0, the photosensitive material 1 m ² per 1mg To 1000 mg, more preferably 3 mg to 500 mg, particularly preferably 5 mg to 250 mg.

In the 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 preferable as the hydrophilic colloid, and its coating amount is preferably 0.01
a ^{g / m 2 ~2.0g / m 2} , more preferably 0.1 g / m ² ~
1.7 g / m ² , particularly preferably 0.2 g / m ^{2 to} 1.4 g / m
²

The 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 surface 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. As the light-sensitive material, medical X-ray photographic material, printing plate-making photographic material, color negative photographic material, color reversal photographic material, color photographic paper photographic material, direct positive photographic material,
Examples thereof include heat-developable color photographic materials and diffusion transfer type color photographic materials.

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, and in the production process from collagen, alkali treated gelatin accompanied by treatment with lime, etc., and 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 photographic light-sensitive 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- (vinylsulfonyl) propionamide), etc.) , Ethyleneimines, carbodiimides, methanesulfonic acid esters, organic hardeners such as isoxazoles, inorganic hardeners such as chromium alum, U.S. Patents 3,057,723, 3,396,029, 4,161,40
Polymer hardeners described in No. 7 and the like can be used, and they can be used alone or in combination. The light-sensitive material of the present invention has a swelling ratio of the coating film during development of 150 to 250%.
Is preferable, and 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. %, Poor drying occurs, and if the swelling ratio is less than 150%, uneven development occurs when developed.
The residual color tends to deteriorate.

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

The silver halide grains in the photographic emulsion are all isotropically grown crystal types such as cubes, octahedra, and tetrahedra, or polyhedral crystal types such as spheres, and plane defects. It may be of a twin crystal having, 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 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), pages 22 to 23, 1; Emulsion Preparation and Types and No. 1
8716 (November 1979), page 648. Also, TH James, “The theory of the pho
tographic process ”4th edition, published by Macmillan (1977) 38
~ Method described on page 104, GF Daufin "Photoemulsion Chemistry"
“Photographic Emulsion Chemistry”, published by Focal Press (1966), P. Glafkides “Physics and Chemistry of Photography” “Chi
mie et Physique Photographique ”, published by Paul Montel
(1967), VL Zelikman et al., "Making and Coating Photographic Emulsion",
It is prepared by the method described in Focal Press (1964). That is, a neutral method, an acidic method, a mixing method such as a forward mixing method, a reverse mixing method, a double jet method, a controlled double jet method, etc. under a solution condition such as an ammonia method,
It can be produced using a particle preparation condition such as a conversion method, a core / shell method, or a combination thereof.

The silver halide emulsions preferably used in the present invention are, 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 habits are cubic, octahedron, tetrahedron and the intermediate (111) plane and (10
0) planes may be mixed arbitrarily. The monodisperse emulsion referred to here is a halogen having at least 95% of the grains by number or weight within ± 40% of the average grain size, preferably within ± 30% when the average grain diameter is measured by a conventional method. It is a silver halide grain. The grain size distribution of the silver halide grains 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,
The coefficient of variation of particle size 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, and examples thereof include JP-A-48-36890, JP-A-52-16364,
55-142329, 58-49938, 60-14331, British patent
1,027,146, 1,413,748, U.S. Patent 3,505,068,
No. 3,574,628, No. 3,655,394, No. 4,444,877, etc.

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., and the emulsion can be produced by the methods described in these patents. The tabular silver halide grains used in the present invention are preferably monodisperse emulsions having a narrow grain size distribution, and those having a variation coefficient of 25% or less are preferable, and 20% are more preferable.
It is as follows, and particularly preferably 15% or less. As the tabular silver halide grains, at least 80% or more of the total projected area of silver halide grains contained in the emulsion is
Aspect ratio shown by (particle size) / (thickness) ratio 3.0 to 12.
It is preferably 0, and more preferably, the aspect ratio is 3.0 to 8.0. The thickness of the tabular silver halide grains is
It is preferably 0.05 to 1 μm, more preferably 0.1.
05-0.5 μm. If the average of 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 grain preferably used is a core / shell type grain, for example, a double structure type grain having a silver halide composition in which the inside of the grain is different from the surface thereof.
-245151 and the like can be cited as multi-structure type particles.

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 to perform 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 are cyanine, merocyanine and complex merocyanine dyes. is there.

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, a high-contrast image is formed in the light-sensitive silver halide emulsion layer or a hydrophilic colloid layer adjacent to the light-sensitive silver halide emulsion layer for adjusting the gradation. 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.

The hydrazine compound of the present invention is a compound having a —NHNH— group in the molecule and is a compound represented by the following general formula (4).

General formula (4) A-NHNH-V-B In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group,
B represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and V is -CO.
- group, -SO- group, a thiocarbonyl group or an iminomethylene group - group, -COCO- group, -SO _2.

The general formula (4) will be described in more detail. The aliphatic group represented by A is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and may be branched or cyclic. A
The aromatic group represented by 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 A is preferably a monocyclic or condensed ring heterocyclic group containing at least one heteroatom 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. ,
Examples thereof include furyl group, thienyl group, thiazolyl group, benzothiazolyl 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. A is preferably an aryl group or an aromatic heterocyclic group. Particularly preferably, A 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, a thiourea group, a thiourethane group, a mercapto group, a thioether group,
Thione group, mercapto heterocyclic group, thioamide heterocyclic group,
Examples thereof include a sulfur-containing heterocyclic group or an adsorption group described in JP-A-64-90439.

As V in the general formula (4), especially -CO-
The group, -COCO- group is preferable.

The alkyl group represented by B in the general formula (4) is an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, octyl group, methoxyethyl group, 2-hydroxyethyl group, 3-methane). (Sulfonamidopropyl group, etc.) are preferred, and the aryl group is a monocyclic or bicyclic aryl group (eg, phenyl group, 3-methanesulfonamidophenyl group, 4-cyanophenyl group, 4-acetylphenyl group, naphthyl group, etc.) The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms (eg, ethoxy group, butoxy group, 2-methoxyethoxy group, etc.), and the aryloxy group is a monocyclic or bicyclic aryloxy group (eg, phenoxy group). Group, 4-methanesulfonylphenyl group, 4-
Cyanophenyl group, naphthyloxy group, etc.) are preferable,
As the amino group, a mono-substituted or di-substituted amino group (eg, methylamino group, dimethylamino group, propylamino group, anilino group, dimethoxyethylamino group, N-
Ethyl-N- (2-methanesulfonylethyl) amino group, 2,2,
6,6-tetramethylpiperidylamino group, morpholino group,
Pyrrolidyl group) is preferred.

Preferred hydrazine compounds include JP-A-3-36540, JP-A-6-194774 and US Pat. No. 4,269,9.
Examples of the compounds described in No. 29, for example 1-formyl-2-{[4- (butylureido) phenyl]} hydrazine, 1-formyl-2- {4- [2- (2,4-di -tert-pentylphenoxy) butylamido] phenyl} hydrazine, 1- (2,2,
6,6-Tetramethyl-4-piperidylaminooxalyl) -2-
{4- [2- (2,4-Di-tert-pentylphenoxy) butylamido] phenyl} hydrazine, 1- {4- (2,2,6,6-tetramethylpiperidyl) aminooxalyl} -2- {4- 〔2- (2,4-di-te
rt-Pentylphenoxy) butyramide] phenylsulfonamidephenyl} 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-pyridinium methylcarbonyl)-
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, for example, 2,3-di (p-methoxyphenyl) -5-phenyltetrazolium chloride; 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 enhancing 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
3,046,134, 3,523,787, 3,746,545, and
No. 4,013,471, No. 4,038,075, No. 4,072,523, No. 4,0
The compounds described in 72,526 and the like can be appropriately selected and used.

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 nitrobenzotriazole, 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- (butylureido) phenyl]} hydrazine , 1- (5-nitroindazol-2-yl-carbonyl) -2- {4- [2- (2,4-di-tert-pentylphenoxy) butylamido] 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) butyramide] phenylsulfonamidophenyl} hydrazine and the like.

Various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention, if necessary. For example, in addition to the photosensitive silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer,
Photographic layers such as a crossover light cut layer and a backing layer can be provided, and in these layers, a supersensitizer, a coupler, a high boiling point solvent, an antifoggant, a stabilizer, a development inhibitor, and a bleaching agent can be provided. Accelerator, fixing accelerator, anti-color mixing agent, formalin scavenger, toning 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 a support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose triacetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, polyethylene laminated paper, etc. 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.

The above-mentioned additives are described in more detail in Research Disclosure (RD) -17643 (December 1978).
18) (November 1979) and 308119 (December 1989). 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 23 648 Upper right 996 Sensitizing dye 23 648-649 996-8 Desensitizing dye 23 998 B Dye 25-26 649-650 1003 Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 649 Upper right 1006-7 Whitening agent 24 998 Hardener 26 651 Left 1004-5 Surfactant 26-27 XI 650 Right 1005-6 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 Silver halide photographic light-sensitive material of the present invention Can be processed by, for example, The Theory of
The Photographic Process 4th Edition (TheTheory
of the Photographic Process, fourth Edition) 293-1
Page 34 and the Journal of the American Chemical S
ociety) Volume 73, page 3,100 (1951). 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, etc. Or in combination. The light-sensitive material according to the present invention can be developed by a rapid processing in which the development processing time from development to drying is 90 seconds or less, and also in the rapid processing in which the development processing time is 45 seconds or less. it can. The treatment temperature is preferably 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
It is 9.0, more preferably pH 11.0 to pH 9.5.

[0085]

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 2.5 N silver nitrate aqueous solution 2825 ml C1 potassium bromide 824 g iodinated Potassium 23.5 g Finish with water to 2825 ml 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 is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have 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% aqueous ethanol solution) 1.4 ml Emulsion -1 0.10 mol equivalent Finish with water to 550 ml B2 ossein gelatin 5.9 g Potassium bromide 6.2 g Iodide Potassium 0.8g Finish to 145ml with water C2 Silver nitrate 10.1g Finish to 145ml with water D2 Ocein gelatin 6.1g Potassium bromide 94g Finish to 304ml with water E2 Silver nitrate 137g Finish to 304ml with water Solution B2 and solution C2 were added in 58 minutes by the double jet method. 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 grain size of 0.96 μm, a grain size distribution width of 19%, and an average aspect ratio of 4.5 were 81% of the projected area. 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 grain emulsion 280 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI)
50 mg

[0097]

[Chemical formula 23]

The solid fine particle dispersion of the spectral sensitizing dye was prepared according to the method described in Japanese Patent Application No. 4-99437. 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.

[0102] The first layer (dye layer) Solid particle dispersion dyes Table 1 the amount of gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound according (I) 5mg / 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 The solid fine particle dispersion of the dye is based on the method described in World Patent 88/04794. It was made. That is, in a 60 ml screw cap container, 21.7 ml of water and the surfactant Triton X-2.
2.65 g of 6.7% solution of 00 (made by Rohm & Haas),
1.0 g of the dye powdered in a mortar was added to this solution, and 40 ml of zirconium oxide beads (2 mm diameter) was added. Place the cap on the ball mill, disperse at room temperature for 4 days, add 8.0g of 12.5% gelatin aqueous solution and mix well.
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-sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² C 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 but 1.0 as gelatin It was prepared at / 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

[0105]

[Chemical formula 24]

[0106]

[Chemical 25]

[0107]

[Chemical formula 26]

The amount of additive added was for one side, and the coating amount of silver 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] The obtained sample was sandwiched between two intensifying screens KO-250 (manufactured by Konica Corp.), and a tube voltage of 80 kvp, a tube current of 100 mA, and an X of 0.05 seconds were passed through an aluminum wedge. Exposure was performed by irradiating a line. Then automatic processor for rapid processing SRX-50
2 (manufactured by Konica Corp.) was processed with the developer and 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.

The sensitivity was calculated by taking the reciprocal of the exposure amount at the fog density + 0.5 and setting the sensitivity of the sample No. 1 in Table 1 immediately after coating and drying to 1
The relative value was set to 00.

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 MTF was evaluated as follows. That is, MTF containing a 0.5 to 10 lines / mm lead rectangular wave.
The chart was brought into close contact with the front side back surface of the fluorescent screen KO-250 (made by Konica Corporation), and X-ray was applied so that the density of the part not covered by the lead chart on the film surface would be about 1.0 on both sides. After irradiating and developing, the recorded rectangular wave pattern was recorded with Sakura Micro Densitometer M-5.
It was measured with a mold (manufactured by Konica Corporation). 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.
m, and the magnification was 20 times. The MTF is shown as a value at a spatial frequency of 2.0 lines / mm. The results obtained are shown in Table 1.

<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 1.2g 1-Phenyl-5-mercaptotetrazole 0.2g Hydroquinone 340g Add water to finish to 5000ml Part-B (for 12 liter finish) Glacial acetic acid 170g Triethylene glycol 185g 1-Phenyl-3-pyrazolidone 22g 5-Nitroindazole 0.4 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1000 ml Add Part-A and Part-B above to about 5 liters of water at the same time,
The mixture was adjusted to 12 l with water while stirring, and the pH was adjusted to 10.4 with glacial acetic acid. This is used as a development replenisher. This development replenisher 1
20 ml of the above starter was added to 1 liter, and the pH was 10.26.
To prepare a developer.

(Fixing solution formulation) Prat-A (for 18 l finishing) 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-dimethylamino) ) -Ethyl-5-mercaptotetrazole 18g Prat-B (for 18l finishing) Aluminum sulfate (anhydrous salt equivalent) 800g Part-A and Part-B are added to about 5l of water at the same time, and water is added with stirring to 18l. Finish and adjust pH to 4.40 with sulfuric acid and sodium hydroxide.

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

[0118]

[Table 1]

As is clear from the results shown in Table 1, the photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention has a photographic characteristic such as sensitivity and fog at a low pH of 11.0 or less and even during short-time processing. It can be seen that there are few adverse effects, excellent sharpness, very little residual color contamination after processing, and excellent storage stability over time.

Example 2 (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, add the following SD-3 to 80 mg per mol of silver
added. After that, desalting was carried out with modified gelatin treated with phenyl isocyanate, and the following compound [A],
A bactericide composed of a mixture of [B] and [C] and ossein gelatin were added and redispersed. The resulting emulsion has an average grain size of 0.
The emulsion consisted of cubic grains having a diameter of 2 μm and a coefficient of variation of 10%. To the emulsion thus obtained, 60 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mol of silver.
In addition, 5 mg of chloroauric acid and 0.5 mg of sulfur flower were added to 1 mol of silver, and chemical ripening was performed at 60 ° C. for 80 minutes under the conditions of pH 5.8 and pAg 7.5. After completion of aging 4-hydroxy-6-methyl-1,3,
900 mg of 3a, 7-tetrazaindene was added per 1 mol of silver, 300 mg of KI and 350 mg of SD-4 were further added.

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate films having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) An antihalation layer of the following formulation (1) was coated on the undercoat layer so that the amount of gelatin was 0.5 g / m ^2, and a silver halide emulsion layer of (2) had a gelatin amount of 2.6.
g / m ^2, by coating as the silver amount is 3.2 g / m ^2, further amounts gelatin 1.0 g / m protective layer having the following formulation (3) thereon
^It was painted so that it would be ² . 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 samples 9 to 16.

Formulation (1) [antihalation layer composition] Gelatin 0.5 g / m ² solid fine particle dispersion dye Amount shown in Table 2 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 (average particle size) Diameter 0.014 μm) 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 Dura Agent: 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: 20 mg silica with an average particle size of 3.5 μm / m ² polymer latex 2 0.5 g / m ² surfactant: sodium sulfosuccinic acid di (2-ethylhexyl) ester 10mg / ² Surfactant F-1
2 mg / m ² accelerator: 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 (0.014 μm) 0.4 g / m ² Hardener: HD 60 mg / m ² Formulation (5) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: Polymethylmethacrylate with an average particle size of 4.0 μm 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 25 mg / m ²

[0124]

[Chemical 27]

[0125]

[Chemical 28]

[0126]

[Chemical 29]

The obtained samples 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 development 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 to light, 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 obtained results are shown in Table 2.

Processing was carried out under the following conditions in 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, and the solution was made up to 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-mentioned composition A and composition B were dissolved in this order, and the solution was made up to 1 l and used. The pH of this fixer 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

[0135]

[Table 2]

As is clear from the results shown in Table 2, 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, and has excellent halftone dot quality. It can be seen that the residual color contamination after the development processing is extremely high.

Example 3 (Preparation of Silver Halide Emulsion) Silver chloride was prepared by a double-blending method.
A silver chlorobromide emulsion consisting of 70 mol% and the rest silver bromide was prepared. When mixed simultaneously, K ₃ RhBr ₆ was added at 8.1 × 10 per mol of silver.
^-8 mol was added. 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 gelatin having an amino group substituted 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 then the temperature was adjusted to 60 ° C., and chloroauric acid was added per mol of silver.
After 2.2 × 10 ^-5 mol was added and stirred for 2 minutes, 2.9 × 10 ^-6 mol of S ₈ was added per 1 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 An emulsion liquid was added.

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of the polyethylene terephthalate film having a thickness of 100 μm and subjected to the antistatic treatment described in Example 2,
An antihalation layer having the following formulation 1 was applied. On this upper layer, the silver halide emulsion of the following Formulation 2 is added in an amount of 3.3 g.
/ M ² , and the amount of gelatin was 1.7 g / m ² .

Furthermore, the following formulation 3 was provided as a protective layer on the upper layer.
Was coated so that the amount of gelatin would be 0.8 g / m ² . On the opposite undercoat layer, 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 coated on the upper layer with 1 g / m ^{2 of} gelatin.
To obtain the sample shown in Table 3.

Formulation 1 (Antihalation layer composition) Gelatin 0.4 g / m ² Solid fine particle dispersion dye Amount shown in Table 3 Alkanol XC (manufactured by DuPont) 3.5 mg / m ² Colloidal silica (average particle size 0.014 μm) 10 mg / m ² N, N′-methylenebis [β- (vinylsulfonyl) propionamide] 25 mg / m ² The solid fine particle dispersion of dye was prepared in the same manner as in Example 1.

Formulation 2 (composition of silver halide emulsion layers)

[0144]

Embedded image

[0145]

[Chemical 31]

[0146] Sodium - iso - amyl - decyl sulfosuccinate 0.64 mg / m ² 2-mercapto-6-hydroxy purine ^{1.7g / m 2 EDTA 50mg / m} 2 hydroquinone 50 mg / m ² Formulation 3 (Emulsion protective layer composition) Sodium -Iso-amyl-decyl sulfosuccinate 12mg / m ² Matting agent: Monodispersed silica 22mg / m ² 1,3-vinylsulfonyl-2-propanol 40mg / m ^{2 with an} average particle size of 3.5μm

[0147]

Embedded image

The coating surface 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-decylsulfosuccinate 6 mg / m ² Colloidal silica (average particle size 0.014 μm) 100 mg / m ²

[0150]

[Chemical 33]

Formulation 5 (composition of backing protective layer) Matting agent: monodisperse polymethylmethacrylate having an average particle size of 5.0 μm 50 mg / m
² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10mg / m ^{2 The} obtained sample was brought into close contact with a step wedge and exposed at a wavelength of 633nm as a substitute characteristic for He-Ne laser light, and then developed with the following composition. The solution and the fixing solution were used and processed under the following conditions by an automatic processor for rapid processing (GR-26SR, manufactured by Konica Corporation).

(Developer Solution Formulation) Sodium sulfite 55 g / liter Potassium carbonate 40 g / liter Hydroquinone 24 g / liter 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (Dimezone S) 0.9 g / liter Potassium bromide 5 g / L 5-methyl-benzotriazole 0.13 g / l boric acid 2.2 g / l diethylene glycol 40 g / l 6-propyl-2-thiouracil 60 mg / l Add water and potassium hydroxide to make 1 l / pH 10.4.

(Fixer Formulation) (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (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 converted content is 8.1% W / V aqueous solution) 26.5 g The composition A and the composition B were melted in this order and finished to 1 liter before use. Of this fixer
The pH 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 Sensitivity of the obtained sample in the same manner as in Example 2 The gamma, halftone dot quality and residual color were evaluated. The results obtained are shown below.

[0155]

[Table 3]

As is clear from the results shown in Table 3, the photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention rarely 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 development processing is extremely small.

Example 4 While maintaining pH3.5 and pAg8.0 in the above-mentioned solution A kept at 38 ° C, the above-mentioned solutions B and C were simultaneously added functionally over 90 minutes, and after further stirring for 10 minutes, Na was added. _The pH was adjusted to 5.8 with a ₂ CO ₃ aqueous solution, and ordinary desalting was performed using MgSO ₄ and polynaphthalene sulfonic acid. 35 mol% of silver bromide, 65 mol% of silver chloride, and a salty odor with an average particle size of 0.25 μm Silver halide grains were obtained.

(Preparation of silver halide photographic light-sensitive material) The following antihalation layer was coated on one undercoat layer of polyethylene terephthalate film having a thickness of 100 μm and subjected to antistatic treatment in the same manner as in Example 3.

A silver halide emulsion layer and a protective layer were coated on this upper layer, and a backing layer and its protective layer were coated on the opposite undercoat layer to prepare a sample.

(Antihalation Layer) Gelatin 0.5 g / m ² solid fine particle dispersion dye Amount shown in Table 4 Sodium dodecylbenzenesulfonate 3.0 mg / m ² N, N′-methylenebis [β- (vinylsulfonyl) propionamide] 24 mg / m ² The solid fine particle dispersion of dye was prepared in the same manner as in Example 1.

(Silver Halide Emulsion Layer) (Preparation of Coating Sample) 0.12 g of citric acid and Na were added to the obtained emulsion.
Br3 was added to adjust the pH to 5.5 and pAg7, and then 0.12 g of sodium thiosulfate and 0.16 g of chloroauric acid were added and chemical ripening was performed at 60 ° C. so that the maximum sensitivity was obtained.

Next, the sensitizing dyes D-41 and D-42 are respectively added.
140 mg was added for spectral sensitization. Further, the following amounts of additives were added per mol of silver halide.

Saponin (manufactured by Merck) 3.4 g Compound 1.3 g Hydroquinone 4.0 g KBr 2.83 g Ethyl acrylate polymer latex 14.16 g Citric acid 113 mg Compound 283 mg Styrene-maleic acid copolymer 2.8 g Compound 2.5 × 10 ^{− 4} mol / mol Ag compound 2.5 × 10 ^-4 mol / mol Ag (emulsion protective layer) Gelatin 60 g Amorphous silica (average particle size 2.8 μm) 1.4 g Bis- (2-ethylhexyl) sulfosuccinate ester 0.8 g KBr 1 g (backing Layer) Gelatin 60 g Compound 1.5 g Compound 0.7 g Compound 10 g Saponin (Merck) 2.5 g Sodium dodecylbenzene sulfonate 0.2 g Butyl acrylate vinylidene chloride copolymer 3.0 g Citric acid 0.4 g Sulfone-maleic acid copolymer 0.1 g ( Backing protective layer) Gelatin 60g Polymethylmethacrylate (average particle size 13μm) 7.8g Bis- (2ethylhexyl) sul Succinic acid ester 0.6 g NaCl 0.2 g Polysiloxane 60 g Gelatin amount for the backing layer was 3.2 g / m ² , gelatin amount for the backing protective layer was 1.0 g / m ² , and glyoxal was added as a hardening agent, and they were simultaneously coated.

The emulsion layer has a silver content of 3.6 g / m ² and a gelatin content of 2.8 mg.
/ M ² , and the emulsion protective layer was coated such that the amount of gelatin was 0.7 g / m ² . The hardener is triazine per 1 g of gelatin.
14 mg and formalin 14 mg were added.

[0165]

Embedded image

[0166]

Embedded image

[0167]

Embedded image

The obtained sample was evaluated in the same manner as in Example 2, and the results are shown in Table 4.

[0169]

[Table 4]

As is clear from the results shown in Table 4, the photographic 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, and has excellent halftone dot quality. It can be seen that the residual color contamination after development processing is extremely small.

[0171]

INDUSTRIAL APPLICABILITY The silver halide photographic light-sensitive material according to the present invention has high sensitivity and excellent sharpness, and an image with less residual color contamination can be obtained even by a developing treatment for a short time with a developing solution having a low pH.

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

Claims (6)

[Claims] 1. A non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye selected from the following general formula (1), general formula (2) or general formula (3) on a support. A characteristic silver halide photographic light-sensitive material. Embedded image [In the formula, Q represents an aryl group or a heterocyclic group, and G ₁ and G ₂
Represents an electron-withdrawing group having a Hammett's σp value of 0.3 or more,
Y is a carbonyl group, a sulfonyl group or> C = C (G ₃ ).
(G ₄ ) group (where G ₃ and G ₄ have a Hammett σp value of 0.3
The above represents an electron-withdrawing group), and Z is 5 or 6
Represents a group of non-metal atoms necessary to form a nitrogen-containing heterocyclic ring, wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a monovalent substituent, and R ₅ represents an alkyl group. , L ₁ , L ₂ and L ₃ represent a methine group, l represents an integer of 1 or 2,
m represents an integer of 1, 2 or 3, n represents an integer of 1 or 2, and p represents an integer of 1 or 2. However, at least one of G _{1 and} G ₂ is an electron-withdrawing group having a group selected from a carboxyl group, a sulfonamide group or a sulfamoyl group. ] 2. G ₁ and G _{2 in the} general formula (1), the general formula (2) or the general formula (3) are a cyano group, a trifluoromethyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Represents an acyl group, an alkylsulfonyl group, an arylsulfonyl group, and is G ₁ or G ₂
2. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of them has a group selected from a carboxyl group, a sulfonamide group or a sulfamoyl group. 3. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the aryl group represented by Q in formula (1) is a substituted or unsubstituted phenyl group. 4. Q in the general formula (1) is pyridyl group, quinolyl group, isoquinolyl group, pyrrolyl group, indolyl group,
Pyrazolyl group, imidazolyl group, benzimidazolyl group, furyl group, benzofuryl group, thienyl group, benzothienyl group, thiazolyl group, benzothiazolyl group, oxazolyl group, benzoxazolyl group, 4-oxoquinolyl group, coumaryl group, chromonyl group or thiochromonyl group 3. A silver halide photographic light-sensitive material according to claim 1, which is a substituted or unsubstituted heterocyclic group selected from the group. 5. A silver halide emulsion layer is provided on a support,
In a silver halide photographic light-sensitive material containing a hydrazine derivative represented by the following general formula (4) in the emulsion layer or another hydrophilic colloid layer, the above-mentioned general formula is provided between the support and the silver halide emulsion layer. A silver halide photographic light-sensitive material comprising a non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye selected from (1), general formula (2) or general formula (3). General formula (4) A-NHNH-V-B [In formula, A represents an aliphatic group, an aromatic group, or a heterocyclic group, B is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or Represents an amino group, V is-
It represents group, an -SO- group, a thiocarbonyl group or an iminomethylene group - CO- group, -COCO- group, -SO _2. ] 6. A processing method comprising developing the silver halide photographic light-sensitive material according to claim 5 with a developer having a pH of 11.0 or less.