JPH09230539A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic sensitive material less liable to fog and having improved aging stability by forming at least one hydrophilic colloidal layer contg. a specified dye on a substrate. SOLUTION: This sensitive material has at least one hydrophilic colloidal layer contg. a dye represented by the formula, wherein each of R1 and R2 is an alkyl, each of Z1 and Z2 is a group of atoms required to form an N-contg. hetero ring, each of L1 -L7 is methine, at least one of L1 -L7 has COR3 (R3 is an alkyl, aryl, amino or a heterocyclic group) as a substituent, L3 and L5 may form a ring by bonding to each other, X1 <-> is an anion and each of p1 , p2 , m, n1 , n2 and n3 is 0 or 1 but n1 , n2 and n3 are not simultaneously 0. A dye having at least one carboxyl, sulfonamido or sulfamoyl group in one molecule is preferably used as the dye represented by the formula.

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, it contains a dye which is less adversely affected by fog and desensitization and which is decolorized during rapid processing and has excellent residual color. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, silver halide photographic light-sensitive materials (hereinafter abbreviated as photographic 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 photographic light-sensitive material for the purpose of absorbing the light, and dyeing a hydrophilic colloid layer with the dye has been carried out. 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 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 It should have excellent stability over time and satisfy various conditions such as no discoloration or fading.

To date, many studies have been conducted with the aim of finding dyes satisfying the above conditions. For example, benzylidene dyes are disclosed in JP-A-51-3623, oxonol dyes in JP-B-39-22069, merocyanine dyes in US Pat. No. 2,493,747, and styryl dyes in US Pat. No. 1,845,404. And other dyes have been proposed.

Some of these conventional dyes have a relatively small effect on emulsion performance, and bleaching and
Although it has properties such as elution and discoloration, it was insufficient from the viewpoint of diffusion resistance. That is, when a specific layer among a plurality of emulsion layers is selectively colored and used as a filter layer or an antihalation layer, not only the light absorption effect is lowered due to remarkable diffusion to other layers, On the other hand, there was a defect that it gave an unfavorable effect such as sensitivity deterioration, gradation change and fog abnormality. Further, when conventional dyes are applied to today's rapid processing steps, and further ultra-rapid processing steps, there is a problem in decolorizing property, and there is a drawback that residual color contamination occurs.

In recent years, as a means for preventing the diffusion of dyes,
A method of dyeing a specific layer using a solid fine particle dispersion of a dye that is insoluble in a neutral to acidic aqueous solution and is soluble in an alkaline aqueous solution has been proposed. For example, US Pat. Nos. 4,855,221 and 4,857,446.
No. 4,948,717, JP-A-52-92716.
No. 55-155350, No. 55-155351
No. 56-12639, No. 63-197943,
JP-A-2-110453, JP-A2-1838, and JP-A-2-
No. 1839, No. 2-191942, No. 2-26424
No. 7, No. 2-264936, No. 2-277044,
No. 4-37841, World Patent 88/04794, etc. are disclosed.

However, although this method is effective as a means for making the dye resistant to diffusion, it has a drawback that it is difficult to obtain a dye having a desired absorption spectrum, and it can be said that the decolorization property in rapid processing is sufficient. However, there is still a problem that residual color contamination occurs. Therefore, there is a strong demand for a diffusion resistant dye that has good decolorization property even in rapid processing and does not cause residual color contamination after the processing, and in particular, a dye having an absorption spectrum in the infrared region is used as an output in the electronic plate making field. There is a strong demand for photographic light-sensitive materials for scanners.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which meets the above-mentioned requirements and has less fog and improved stability over time by using a diffusion-resistant dye. is there. Another object is to provide a silver halide photographic light-sensitive material having high sensitivity and excellent contrast. Still another object is to provide a silver halide photographic light-sensitive material which gives an image with less residual color contamination by a rapid processing in a short time.

[0009]

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

(1) A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer containing a dye represented by the following general formula (I) on a support.

[0011]

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In the formula, R ₁ and R ₂ each represent an alkyl group, and Z ₁ and Z ₂ each represent a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle. L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ each represent a methine group. However, L ₁ , L ₂ , L ₃ ,
At least one of L ₄ , L ₅ , L ₆ and L ₇ has a COR ₃ group (R ₃ represents an alkyl group, an aryl group, an amino group or a heterocyclic group) as a substituent, and L ₃ and L ₅ May combine with each other to form a ring. X ₁ ^- represents an anion,
p ₁ , p ₂ , m, n ₁ , n ₂ and n ₃ each represent 0 or 1. However, n ₁ , n ₂ and n ₃ do not become 0 at the same time.

(2) The silver halide photographic light-sensitive material according to (1), which has at least one non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of the dye represented by the general formula (I).

(3) The silver halide photographic light-sensitive material described in (1) or (2), wherein the dye of the general formula (I) is a dye represented by the following general formula (II).

[0015]

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In the formula, R ₁ and R ₂ each represent an alkyl group, R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₄ and R ₅ , R ₆ And R ₇ may combine with each other to form a ring. Z ₃ and Z ₄ each represent a nonmetallic atom group necessary for forming an aromatic ring or a heterocycle. L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ each represent a methine group. However, at least one of L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ represents a COR ₃ group (R ₃ represents an alkyl group, an aryl group, an amino group or a heterocyclic group). Having a substituent, L ₁ and R ₅ , L ₃ and L _5, and L ₇ and R ₆ may be bonded to each other to form a ring. X ₁ ⁻ represents an anion, and m, n ₁ , n ₂ and n ₃ each represent 0 or 1. However, n ₁ , n ₂ and n ₃ do not become 0 at the same time.

(4) The silver halide photographic light-sensitive material as described in (1), (2) or (3), wherein at least one hydrophilic colloid layer contains a hydrazine compound.

(5) The silver halide photographic light-sensitive material as described in (1), (2) or (3), wherein at least one hydrophilic colloid layer contains a tetrazolium salt compound.

(6) A development processing method in which the silver halide photographic light-sensitive material described in any one of (1) to (5) is processed for a total processing time of 90 seconds or less.

(7) The development processing method according to (6), wherein processing is performed for a total processing time of 45 seconds or less.

(8) A dye represented by the following general formula (II).

[0022]

[Chemical 6]

In the formula, R ₁ and R ₂ each represent an alkyl group, R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₄ and R ₅ , R ₆ And R ₇ may combine with each other to form a ring. Z ₃ and Z ₄ each represent a nonmetallic atom group necessary for forming an aromatic ring or a heterocycle. L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ each represent a methine group. However, at least one of L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ represents a COR ₃ group (R ₃ represents an alkyl group, an aryl group, an amino group or a heterocyclic group). Having a substituent, L ₁ and R ₅ , L ₃ and L _5, and L ₇ and R ₆ may be bonded to each other to form a ring. X ₁ ⁻ represents an anion, and m, n ₁ , n ₂ and n ₃ each represent 0 or 1. However, n ₁ , n ₂ and n ₃ do not become 0 at the same time.

The present invention will be described in more detail below.

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

The alkyl group represented by R ₁ and R ₂ in formula (I) or (II) is preferably an alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, i-.
Each group such as propyl, butyl, i-butyl, t-butyl, hexyl, octyl and the like can be mentioned. The alkyl group includes those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxyl group, a cyano group, Hydroxyl group, mercapto group, amino group, alkoxy group,
Examples thereof include an aryloxy group, an acyl group, a carbamoyl group, an acylamino group, a ureido group, a sulfonamide group, and a sulfamoyl group, and these substituents may have two or more kinds in combination. A preferred substituent has 1 carbon atom.
~ 8 alkyl group (methyl, ethyl, t-butyl, octyl, etc.), hydroxyl group, cyano group, halogen atom (fluorine element, chlorine, etc.), alkoxy group having 1 to 6 carbon atoms (methoxy, ethoxy, 2-hydroxy). Ethoxy, methylenedioxy, butoxy, etc.), substituted amino groups (dimethylamino, diethylamino, N-ethyl-N-hydroxyethylamino, N-ethyl-N-methanesulfonamidoethylamino, morpholino, piperidino, pyrrolidino, etc.),
Carboxyl group, carbamoyl group (carbamoyl, methylcarbamoyl, ethylcarbamoyl, butylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl,
4-carboxyphenylcarbamoyl etc.), alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl etc.), acyl group (methylcarbonyl, ethylcarbonyl, butylcarbonyl, phenylcarbonyl, 4-ethylsulfonamidophenylcarbonyl etc.) ), A sulfonamide group (methanesulfonamide, benzenesulfonamide, etc.), and a sulfamoyl group (sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.), and these substituents may be combined. Specific examples of the alkyl group having a substituent include 2-hydroxyethyl, 2-methoxyethyl, 2-cyanoethyl, 2-methanesulfonamidoethyl, 2-ethoxycarbonylpropyl, p-carboxybenzyl, p-carboxyphenethyl, and the like. Carboxymethyl, 2-acylaminoethyl, 2
-Methylcarbamoylethyl, 3-methylureidopropyl, 2-methanesulfonamidocarbonylethyl,
Each group such as 2,2,2-trifluoroethyl may be mentioned.

Examples of the nitrogen-containing heterocyclic group formed by Z ₁ and Z ₂ in the general formula (I) include pyridyl, quinolyl, pyrrolyl, indolyl, imidazolyl, benzimidazolyl, thiazolyl, benzthiazolyl, oxazolyl, benzoxazolyl. And the like. These nitrogen-containing heterocyclic groups include those having a substituent, and as the substituent, the groups exemplified as the substituents of the alkyl group represented by R ₁ and R ₂ are preferable.

L ₁ , L _{2 of} the general formula (I) or (II),
At least one of the methine groups represented by L ₃ , L ₄ , L ₅ , L ₆ and L ₇ has a COR ₃ group. The alkyl group represented by R ₃ is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl and hexyl groups. . Examples of the aryl group represented by R ₃ include phenyl and naphthyl groups. Examples of the amino group represented by R ₃ include amino, N-methylamino, N-ethylamino, N, N-dimethylamino, N, N-diethylamino, N-methyl-N-phenylamino, and anilino. Groups. Examples of the heterocyclic group represented by R ₃ include pyridyl, quinolyl, isoquinolyl, pyrrolyl, indolyl, pyrazolyl, imidazolyl, benzimidazolyl, furyl, benzofuryl, thienyl, benzothienyl, thiazolyl, benzthiazolyl, oxazolyl and benzoxazoli. Examples thereof include groups such as le, morpholino, pyrrolidino, and piperidino. These alkyl group, aryl group, amino group and heterocyclic group include those having a substituent, and the substituent is preferably the group mentioned as the substituent of the alkyl group represented by R ₁ and R ₂ .

R ₃ is preferably methyl, ethyl,
2-hydroxyethyl, 2-methoxyethyl, 2- (methanesulfonamido) ethyl, benzyl, phenyl, 4
-Carboxyphenyl, 4-ethoxycarbonylphenyl, 3,4-dimethoxyphenyl, amino, N-methylamino, N-ethylamino, N, N-dimethylamino,
N, N-diethylamino, N-methoxyethylamino,
Each group such as N, N-dimethoxyethylamino, anilino, 4-carboxyanilino, pyridyl, furyl, thienyl, thiazolyl, oxazolyl, morpholino, pyrrolidino, piperidino and the like can be mentioned.

[0030] X ₁ in the general formula (I) or (II) ^- Examples of the anion represented by, for example, a chlorine ion, a bromine ion, an iodine ion, sulfate ion, hydrogen sulfate ion, tetrafluoride, boron ions, perchlorate Ion, perbromate ion, p-toluenesulfonate ion, acetate ion, benzoate ion and the like.

Among the dyes represented by the general formula (I), a dye having at least one carboxyl group, sulfonamide group or sulfamoyl group in the molecule is preferably used. More preferably, it is a dye represented by the general formula (II), and has a carboxyl group, a sulfonamide group,
It is a dye having at least one sulfamoyl group.

The alkyl group represented by R ₄ , R ₅ , R ₆ and R ₇ in the general formula (II) is preferably an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, i-propyl, Each group such as butyl, i-butyl, t-butyl, hexyl and the like can be mentioned, and the aryl group can include phenyl, naphthyl and the like. These alkyl groups and aryl groups include those having a substituent, and the substituent is preferably the group exemplified as the substituent of the alkyl group represented by R ₁ and R ₂ .

Examples of the aromatic ring represented by Z ₃ and Z ₄ in the general formula (II) include benzene and naphthalene rings.
Examples of the heterocycle include pyridine, quinoline, pyrazole and imidazole rings. These aromatic rings and heterocycles include those having a substituent, and the substituent is the R
_The groups mentioned as the substituents of the alkyl group represented by ₁ and R ₂ are preferable.

Specific examples of the dye represented by formula (I) or (II) of the present invention are shown below, but the dye is not limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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Specific synthetic examples are shown below. Other dyes used in the present invention can be produced by the same synthetic method.

Synthesis Example 1 (Synthesis of Exemplified Dye 5) The raw material 4-carbamoyl-1- (2,4-dinitrophenyl) pyridinium chloride was prepared according to US Pat.
It was synthesized by the method described in No. 1,494.

In a mixed solvent of 25 ml of ethanol and 5 ml of N, N-dimethylformaldehyde, 6.5 g of 5-carboxy-1-methoxyethyl-2,3,3-trimethylindolenium chloride and 4-carbamoyl-1-
3.2 g of (2,4-dinitrophenyl) pyridinium chloride was added, 3.0 g of triethylamine was further added, and the mixture was stirred at 40 ° C. for 3 hours and then left overnight. The precipitated crystals were collected by filtration, washed with ethanol, then sufficiently washed with acetone and dried to obtain 3.4 g of crystals. 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 is described in JP-A-52-92716 and JP-A-55-155.
No. 350, No. 55-155351, No. 63-1979.
No. 43, No. 3-182743, World Patent WO88 / 0
The method described in 4794 or 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, and 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. A dye dispersion can be obtained by a method of producing a fine particle solid. 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 is preferably dispersed so that the average particle size is 0.01 to 5 μm, more preferably 0.01 to 1 μm, and particularly preferably 0.01 to 5 μm. It is 0.5 μm. The coefficient of variation of the 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 equation.

(Standard deviation of particle size) / (Average value of particle size) × 100 (%) A surfactant may be used when producing a solid fine particle dispersion of a dye, and as the surfactant, , Any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, but preferably alkyl sulfonates, alkyl benzene sulfonates,
Anionic surfactants such as alkylnaphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines and saponins, alkylene oxide derivatives, Nonionic surfactants such as alkyl esters of sugars.

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. If necessary, it may be further added to the dye dispersion 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 surfactant used is not uniform depending on the type of the surfactant or the conditions of the dispersion liquid of the dye, but it is usually 0.1 to 2000 mg, preferably 0.5 to 1000 mg, per 1 g of the dye. , And more preferably 1 to 500 mg.

The concentration of the dye in the dispersion is 0.01
It is used so as to be 10 to 10% by weight, preferably 0.1
~ 5% by weight.

To the dye dispersion, 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; grafting of gelatin with a monomer having a polymerizable ethylene group Polymers; Cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose, cellulose sulfate ester;
Synthetic hydrophilic polymers such as polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-N-vinylpyrrolidone, polymethacrylic acid; agar, gum arabic, alginic acid, albumin, casein, etc. Can be used. You may use these in combination of 2 or more types.

The dye dispersion can be used in layers constituting the photographic light-sensitive material, for example, non-light-sensitive hydrophilic colloid layers such as emulsion layer upper layer, emulsion layer lower layer, protective layer, support undercoat layer and backing layer. . The preferred amount of dye used is not uniform depending on the type of dye, the characteristics of the photographic light-sensitive material, etc.
Depending on the purpose, the optical density in the photographic light-sensitive material is 0.05-
It is used so as to be 3.0, and is 0.1 to 1000 mg per 1 m ^{2 of} the photographic light-sensitive material, more preferably 1 to 5
The amount is 00 mg, particularly preferably 3 to 200 mg.

In the photographic light-sensitive material of the present invention, the solid fine particle dispersion of the dye is preferably contained in at least one non-photosensitive hydrophilic colloid layer. Preferably gelatin as hydrophilic colloid, examples of the coating amount, preferably from 0.01 to 2.0 g / m ^2, still preferably 0.1~1.7g / m ^2, particularly preferably 0.2 ~
It is 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. Photographic materials for printing and plate making are preferred.

Gelatin used in the photographic light-sensitive material of the present invention includes alkali-processed gelatin which is treated with lime or the like and acid-processed gelatin which is treated with hydrochloric acid in the process of producing collagen, which is used in the present invention. Any gelatin may be used, but the jelly strength of gelatin (according to the PAGI method) is preferably 250 g or more. Calcium content of gelatin (by PAGI method)
Is preferably 4000 ppm or less, and particularly preferably 3000 ppm or less.

Further, gelatin is hardened by a hardener,
The swelling ratio and film strength of the coating film can be adjusted by the amount of the hardener in the photographic light-sensitive material. Examples of the hardener include aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), mucohalogenoic acid (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. ),
Organic hardeners such as ethyleneimines, carbodiimides, methanesulfonic acid esters and isoxazoles, inorganic hardeners such as chrome alum, US Pat. No. 3,057,723
Nos. 3,396,029, 4,161,407 and the like can be used, and the polymeric hardeners can be used alone or in combination.

In the photographic light-sensitive material of the present invention, the swelling ratio of the coating film during the development processing is preferably 150 to 250%, 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, divided by the film thickness before processing, and multiplied by 100. If it exceeds 250%, poor drying occurs, and if the swelling ratio is less than 150%, uneven development and residual color tend to increase during development.

Halogenated emulsions used in the photographic light-sensitive material of the present invention include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Although any of silver chloroiodobromide, silver chloride and the like can be used, 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 ranges from 0.1 μm or less to 15 μm.
May be large particles.

The emulsion used can be produced by a known method. For example, Research Disclosure (RD) 17
643 (December 1978), pp. 22-23, 1, Emulsion Preparation Method (Emulsion Preparation)
and Types) and ibid 18716 (1979, 1).
January), page 648. Also, T. H. James, The Theory of
The Photographic Process (The Theo)
ry of the PhotographicPro
4th edition ", published by Macmillan (197)
7 years) The method described on pages 38-104, G. F. Dauf
Fin's "Photoemulsion Chemistry (Photographic
Emulsion Chemistry) ", Foca
1 Press, Inc. (1966), P.I. Glafki
Des "Physics and Chemistry of Photography (Chimie et P
hysque Photographie) ",
Paul Montel, Inc. (1967), V.I. L.
Zelikman et al., "Making and Coating Photographic Emulsions (Mak
ing and Coating Photograph
hic Emulsion) ", Focal Pres
It is prepared by the method described in, for example, s company (1964). In other words, under the solution conditions such as neutral method, acidic method, ammonia method, etc., forward mixing method, back mixing method, double jet method, controlled double jet method, etc., mixing method, conversion method, particle preparation such as core / shell method, etc. It can be manufactured using conditions and combinations of these.

During the formation of silver halide grains, for example, ammonia, thioether compounds, thione compounds and the like can be used as a silver halide solvent for controlling the grain growth. Further, metal salts such as zinc, lead, thallium, iridium and rhodium can be made to coexist during physical aging and chemical aging.

The silver halide can be sensitized with a sulfur compound, a selenium compound, or a noble metal salt such as 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.

Examples of the dye used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye and hemioxonol dye, and particularly useful dyes are cyanine,
It is a dye belonging to merocyanine and complex merocyanine dyes. These spectral sensitizing dyes are used in an amount of 1 mg to 2 g, preferably 1 mg to 500 mg, per mol of silver halide.

A photographic light-sensitive material can be obtained by coating an emulsion prepared by dispersing silver halide in a hydrophilic colloid medium, for example, gelatin on a polyethylene terephthalate or triacetate cellulose support.

When the photographic light-sensitive material of the present invention is applied for printing plate making, a tetrazolium compound is used as a contrast-increasing agent in a light-sensitive silver halide emulsion layer or a hydrophilic colloid layer adjacent to it, or in another hydrophilic colloid layer. Alternatively, it is preferable to contain a hydrazine compound, an amine compound as a contrast enhancement aid, or a redox compound that releases a development inhibitor by a redox reaction during development.

Examples of the tetrazolium compound include compounds represented by the following general formula [T].

[0066]

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In the formula, R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom or a substituent, and X ₁₁ ⁻ represents an anion.

Preferred examples of the substituents represented by R ₁₁ , R ₁₂ and R ₁₃ include alkyl groups (methyl, ethyl, cyclopropyl, propyl, i-propyl, cyclobutyl, butyl, i-butyl, pentyl, cyclohexyl, etc.). , Amino group, acylamino group (acetylamino etc.), hydroxyl group, alkoxy group (methoxy, ethoxy, propoxy, butoxy, pentoxy etc.), acyloxy group (acetyloxy etc.), halogen atom (fluorine, chlorine, bromine etc.), carbamoyl Groups such as groups, acylthio groups (acetylthio, etc.), alkoxycarbonyl groups (ethoxycarbonyl, etc.), carboxyl groups, acyl groups (acetyl, benzoyl, etc.), cyano groups, nitro groups, mercapto groups, sulfooxy groups, amino sulfoxy groups. Is mentioned.

[0069] X ₁₁ ^- as the anion represented by, for example, chloride, bromide, halide ions such as iodide ions, nitric acid, sulfuric acid, acid roots of inorganic acids such as perchloric acid, sulphonic acids, such as carboxylic acid Acid radicals of organic acids, anionic activators, specifically, lower alkylbenzene sulfonate anions such as p-toluene sulfonate anion, p
A higher alkylbenzene sulfonate anion such as dodecylbenzene sulfonate anion, a higher alkyl sulfate ester anion such as lauryl sulfate anion, a boric acid anion such as tetraphenylboron, a dialkylsulfosuccinate anion such as di-2-ethylhexylsulfosuccinate anion Examples thereof include polyether alcohol sulfate anion such as cetyl polyethenoxysulfate anion, higher aliphatic anion such as stearic acid anion, and polymer having acid radical such as polyacrylic acid anion.

Specific examples of the compound represented by the general formula [T] used in the present invention are shown below, but the invention is not limited thereto.

[0071]

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[0072]

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[0073]

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[0074]

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The tetrazolium compound used in the present invention is, for example, a chemical review (Chemical Review).
Evids) 55, 35-483, and can be easily synthesized.

The tetrazolium compound is about 1 mg to 10 mg per mol of silver halide contained in the photographic light-sensitive material.
g, preferably in the range of about 10 mg to 2 g.

The hydrazine derivative used in the present invention is, for example, a compound represented by the following general formula [H].

[0078]

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In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, and B represents a substituent.

The aliphatic group represented by A preferably has 1 to 30 carbon atoms, and is particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Examples thereof include methyl, ethyl, t-butyl, octyl, cyclohexyl, benzyl and the like, and these are further suitable substituents (aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, Acylamino group, ureido group, etc.).

The aromatic group represented by A is preferably a monocyclic or condensed ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A is preferably a monocyclic or condensed ring heterocyclic group containing at least one heteroatom selected from nitrogen, sulfur and oxygen, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, Examples of the residue include morpholine ring, pyridine ring, pyrimidine ring, quinoline ring, thiazole ring, benzothiazole ring, thiophene ring, and furan ring.

Particularly preferred as A is an aryl group and a heterocyclic group.

The aryl group and the heterocyclic group may have a substituent, and typical examples of the substituent include an alkyl group (preferably having a carbon number of 1 to 20) and an aralkyl group (preferably having an alkyl moiety). Monocyclic or condensed ring having 1 to 3 carbon atoms), alkoxy group (preferably having 1 to 20 carbon atoms in the alkyl moiety), substituted amino group (preferably alkyl group having 1 to 20 carbon atoms or alkylidene) Group substituted amino group), acylamino group (preferably having 1 carbon atom)
~ 40), sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms)
40), hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), hydroxyl group, phosphoamide group (preferably having 1 to 40 carbon atoms), and the like.

Further, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group which is commonly used in a non-moving photographic additive such as a coupler is preferable, and as the ballast group, an alkyl group or an alkenyl group having 8 or more carbon atoms which is relatively inactive to photographic properties. , Alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

B is specifically an acyl group (formyl, acetyl, propionyl, trifluoroacetyl, methoxyacetyl, phenoxyacetyl, methylthioacetyl,
Chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc.), alkylsulfonyl group (methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl group (benzenesulfonyl, etc.), alkylsulfinyl group (methanesulfinyl, etc.), Arylsulfinyl group (benzenesulfinyl etc.), carbamoyl group (methylcarbamoyl, phenylcarbamoyl etc.), alkoxycarbonyl group (methoxycarbonyl, methoxyethoxycarbonyl etc.), aryloxycarbonyl group (phenoxycarbonyl etc.), sulfamoyl group (dimethylsulfamoyl) Etc.), sulfinamoyl group (dimethylsulfinamoyl, etc.), alkoxysulfonyl group (methoxysulfonyl, etc.), thioacyl group (methylthiocal, etc.) Sulfonyl, etc.), thiocarbamoyl group (methyl thiocarbamoyl, etc.), is described later oxalyl group (formula [H ']), or a Hajime Tamaki (pyridine ring,
Pyridinium ring).

B in the general formula [H] may form —N═C (R ₂₁ ) (R ₂₂ ) together with A ₂ and the nitrogen atom to which they are bonded. Here, R ₂₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₂₂ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

As B, an acyl group or an oxalyl group is particularly preferable.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.) or an oxalyl group (ethoxalyl, etc.). Etc.).

Among the hydrazine compounds used in the present invention, the compounds represented by the following general formula [H '] are particularly preferable.

[0092]

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In the formula, R ₂₃ represents an aryl group or a heterocyclic group, and R ₂₄ represents a —N (R ₂₅ ) (R ₂₆ ) group or a —OR ₂₇ group.

R ₂₅ and R ₂₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or It represents a heterocyclic oxy group, and R ₂₅ and R ₂₆ may form a ring together with a nitrogen atom. R ₂₇ is a hydrogen atom, an alkyl group,
It represents an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. A ₁ and A ₂ to A ₁ and A ₂ in formula (H), each represent the same groups as those.

The general formula [H '] will be described in more detail.

The aryl group represented by R ₂₃ is preferably a monocyclic ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₂₃ is preferably a 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, which is a monocyclic ring or a condensed ring. Ring, quinoline ring, pyrimidine ring,
Examples thereof include residues such as a thiophene ring, a furan ring, a thiazole ring or a benzothiazole ring.

Preferred as R ₂₃ is a substituted or unsubstituted aryl group. Examples of the substituent include those having the same meaning as the substituent of A in the general formula [H].
When the contrast is increased with a developing solution of 11.2 or less, it is preferable to have at least one sulfonamide group.

A ₁ and A ₂ are A of the general formula [H], respectively.
₁ and A ₂ have the same meanings as A ₂ , but it is most preferable that both are hydrogen atoms.

In the --N (R ₂₅ ) (R ₂₆ ) group represented by R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.), an alkenyl group (allyl, butenyl, etc.). , Alkynyl groups (propargyl, butynyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl, quinolidinyl, N, N '. -Diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy, ethoxy, etc.), alkenyloxy group (Allyloxy, etc.), alkynyloxy group (propargyloxy, etc.), aryloxy group (phenoxy, etc.), or heterocyclic oxy group ( Pyridyloxy, etc.) and a ring (piperidine, morpholine, etc.) together with a nitrogen atom at R ₂₅ and R ₂₆
May be formed.

In the —OR ₂₇ group represented by R ₂₄ , R ₂₇ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.). ), An aryl group (phenyl, naphthyl, etc.), and a heterocyclic group (2,2,6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl, etc.).

Specific examples of the compound represented by the general formula [H] are shown below, but the invention is not limited thereto.

[0103]

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[0104]

[Chemical 21]

[0105]

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[0106]

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[0107]

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[0108]

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The synthetic method of the compound represented by the general formula [H] is described in JP-A Nos. 62-180361 and 62-178.
No. 246, No. 63-234245, No. 63-2342
46, 64-90439, JP-A-2-37, 2-841, 2--947, 2-120736.
No. 2-230233, No. 3-125134, and U.S. Pat. Nos. 4,686,167 and 4,988,604.
No. 4,994,365, European Patent 253.
The methods described in No. 665 and No. 333,435 can be referred to.

The amount of the compound represented by the general formula [H] used is 5 × 10 ^{-7 to} 5 × 10 ^-1 per mol of silver halide.
It is preferably molar, and particularly 5 × 10 ^{−6 to} 5 × 10
A range of ^-2 mol is preferred.

In the present invention, when the compound represented by the general formula [H] is contained in the photographic light-sensitive material, it is contained in the silver halide emulsion layer or the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

Next, as the nucleation accelerator, the following general formula [N
And those shown in [A-I] or [NA-II].

[0113]

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In the general formula [NA-I], R ₃₁ , R ₃₂
And R ₃₃ each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, an alkynyl group or a substituted or unsubstituted aryl group. In addition, R ₃₁ , R
₃₂ and R ₃₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds.

In the general formula [NA-II], Ar represents an aryl group and R ₃₄ represents a hydrogen atom or a substituent.

These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable. Examples of preferable adsorption groups include a heterocyclic group, a mercapto group, a thioether group, a thione group and a thiourea group.

Specific examples of the nucleation accelerator include those shown below.

[0118]

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[0119]

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[0120]

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[0121]

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The redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, reductones and the like as redox groups, and 5-nitroindazole and 4-nitro as development inhibitor moieties. Indazole, 1
-Phenyltetrazole, 1- (3-sulfophenyl)
Tetrazole, 5-nitrobenztriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4
-Nitroimidazole and the like, for example, JP-A-3-249643 and US Pat. No. 4,269,92.
Examples thereof include compounds described in No. 9 and the like.

Addition of the redox compound was carried out with methanol,
Ethanol, ethylene glycol, triethylene glycol, propylene glycol, dimethylformamide,
It can be added by being dissolved in an organic solvent such as dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, acetone, 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 thereof is 10 ^-6 to 10 ^-1 mol, preferably 10 ^-4 to 10 ^-2 mol per mol of silver halide.

Preferred redox compounds are 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-t-pentylphenoxy) butylamido] phenyl} hydrazine, 1- (4-nitrotriazol-2-yl-carbonyl) -2- {4- [2-
(2,4-di-t-pentylphenoxy) butyramide]
Phenyl} hydrazine, 1- (4-nitroimidazol-2-yl-carbonyl) -2- {4- [2- (2,4
-Di-t-pentylphenoxy) butylamide] phenylsulfonamidophenyl} hydrazine and the like.

If necessary, various techniques and additives known in the art can be used in the photographic light-sensitive material. 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. Color sensitizers, couplers, high boiling point solvents, antifoggants, stabilizers, development inhibitors, bleaching accelerators, fixing accelerators, color mixing inhibitors, formalin scavengers, color tones, hardeners, surfactants, thickeners Agents, plasticizers, slip agents, ultraviolet absorbers, polymer latices, antistatic agents, matting agents and the like can be incorporated by various methods.

As the support that can be used in the photographic light-sensitive material, cellulose triacetate (TAC), cellulose nitrate, polyester such as polyethylene terephthalate (PET), polyolefin such as polyethylene, polystyrene, baryta paper, polyethylene, etc. 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, the above-mentioned additives are RD17.
643 (December 1978), page 23, section III to page 28, XVI.
Item I, ibid. 18716 (November 1979), p.648 upper right to p.651 upper left, ibid. 308119 (1989 12).
Mon), page 996, section III-A to page 1009, section XVII-G.

To develop the photographic light-sensitive material of the present invention, for example, The Theory of the Photographic Process 4th Edition (supra), pages 291-334 and Journal of the American Chemical.・ Society (J. Amer. Chem. Soc.) 73, 310
The developer as described on page 0 (1951) is effectively used. Specific examples of the developing agent include dihydroxybenzenes (hydroquinone etc.), 3-pyrazolidones (1-phenyl-3-pyrazolidone, 1-phenyl-4).
-Methyl-4-hydroxymethyl-3-pyrazolidone,
5,5-dimethyl-1-phenyl-3-pyrazolidone, etc.), aminophenols (p-aminophenol, N
-Methyl-p-aminophenol, etc.), ascorbic acid, etc. may be used alone or in combination.

The photographic light-sensitive material of 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. Can be processed. Furthermore, development processing can be performed even by ultra-rapid processing with a development processing time of 30 seconds or less. The treatment temperature is preferably 25 to 50
C., and more preferably 30 to 40.degree.

[0130]

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 Silver Halide >> pAg =
7.7, pH = 3.0, mixing temperature 40 ° C. constant, halogen composition AgCl / Br = 70/30, average particle size 0.
A 28 μm silver halide emulsion was obtained.

During the mixing step from the formation of 5% of the final reached average particle size to the final reached average particle size, potassium hexabromorhodate and potassium hexabromoiridate were added to 1 mol of silver each. Per 4.0 x 10 ^-8
Moles and 8.0 × 10 ⁻⁷ moles were added. The obtained emulsion was desalted with water 3 times by adding 15 g of modified gelatin treated with phenyl isocyanate to 1 mol of silver and adjusting the pH to 4.4.

After adjusting these emulsions to pH = 5.8 and pAg = 7.0 using citric acid and sodium chloride, chloroauric acid was added in an amount of 2 × 10 ^-5 mol per 1 mol of silver and a polysulfide compound. Add 2 mg per 1 mol of silver, 90 at 55 ° C
Achieved the maximum sensitivity by chemical aging. Then, 40 mg of 1-phenyl-5-mercaptotetrazole (inhibitor) and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (stabilizer) were added per 1 mol of silver.
And 600 mg were added to stop the aging.

1.2 g of potassium bromide was added to the emulsion thus obtained (hereinafter, per mol of silver unless otherwise specified), and 10 mg of each of sensitizing dyes SD-1 and SD-2 was added. Then, 100 mg of the additive (W-1) was further added to prepare an emulsion.

Using this emulsion, an emulsion layer coating solution having the following composition was prepared.

Emulsion layer coating solution Saponin 5100 mg Surfactant (SU-1) 500 mg Hydroquinone 150 mg Latex (LA-1) 12.5 g Styrene-maleic acid copolymer (thickener) 1800 mg Layer, backing layer, backing protective layer and dye layer coating solutions were also prepared (all of which are shown in the amount per 1 m ^{2 of the} coated sample).

Emulsion protective layer coating surfactant (SU-2) 23 mg Fog inhibitor (AF-1) 1 mg Amorphous silica (average particle size 3 μm) 23 mg Sodium oxalic acid 5 mg Styrene / maleic acid copolymer 3.5 mg Formaldehyde (Hardener) 18 mg Glyoxal (Hardener) 8 mg Backing layer coating liquid Gelatin 2.3 g Dye (F-1) 30 mg Dye (F-2) 23 mg Dye (F-3) 20 mg Dye (F-4) 100 mg Saponin 12 mg 5-nitroindazole (development inhibitor) 30 mg latex (LA-2) 200 mg preservative (DI-1) 3 mg oxalic acid 15 mg styrene-maleic acid copolymer (thickener) 40 mg curing agent A 55 mg backing protective layer coating solution gelatin 1.1g matting agent (PMMA; particle size 5 [mu] m) 40 mg surfactant (SU-2) 12 mg Glyoxal (hardener) 7 mg Hardener (H-1) 34 mg << Preparation of dye layer >> Solid fine particle dispersion dye Amount shown in Table 1 Gelatin 0.3 g Surfactant (SU-1) 4 mg saponin 12 mg hardener (H-1) 5 mg A solid fine particle dispersion of a dye is described in World Patent 88/04794.
It was prepared according to the method described in No. That is, 21.7 ml of water and the surfactant Triton X-2 were placed in a dispersion container.
00 (manufactured by Rohm & Haas) 2.6% solution 2.6
5 g, 1.0 g of powder dyed with a cutter mill was added, and zirconium oxide beads (0.5 mm
(Diameter) 40 ml was added, and the mixture was subjected to sand mill dispersion for 10 hours.

After dispersion, 12.5% gelatin aqueous solution 8.0
g was added and mixed well, and the zirconium oxide beads were removed by filtration to obtain a solid fine particle dispersion of the dye (average particle size of the dye: 0.10 μm).

SU-1: sodium p-dodecylbenzenesulfonate SU-2: sodium sulfosuccinate (i-pentyldecyl) PMMA: polymethylmethacrylate H-1: 2,4-dichloro-6-hydroxy-s- Triazine sodium

[0140]

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[0141]

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[0142]

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First, the coating solution prepared as described below was subjected to the undercoating shown in JP-A-59-19941 to obtain a thickness of 100 μm.
After applying corona discharge at a rate of 10 W / m ² · min on a PET base of m, a roll-fit coating pan and air knife having the following composition (shown per liter) were used to apply a coating amount of 10 cc / m ² Was applied. It should be noted that the drying was 90 ° C and the overall heat transfer coefficient was 25 kcal / m.
^{It was} performed for 30 seconds under a parallel flow drying condition of ² · hr · ° C, and subsequently at 140 ° C for 90 seconds. The thickness of the layer after drying is 1μ
m, the surface resistivity of the layer is 1 × 10 ⁸ at 23 ° C. and 55% RH
Ω.

Water-soluble conductive polymer (P-1) 70 g Hydrophobic polymer particles (P-2) 40 g Ammonium sulfate 0.5 g Polyethylene oxide compound (average molecular weight 600) 6 g Curing agent B 12 g

[0145]

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On this base, a dye layer, an emulsion layer, and an emulsion protective layer were formed in this order from the side closer to the support as the emulsion side.
Simultaneous multi-layer coating while adding hardener solution by slide hopper method while keeping at 35 ° C, set in cool air set zone (5
C.), the backing layer and the backing protective layer were applied while adding a hardening agent with an arrow tension slide hopper, and set with cold air (5.degree. C.). At the time of passing through each set zone, the coating liquid showed sufficient setting properties.
Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions.

After coating both sides of the backing, it was conveyed until it was wound up in a roller and without any contact with other parts. At this time, the coating speed was 100 m / min.

Photographic material samples 1 to 1 thus prepared
Photographic properties of No. 15 were evaluated according to the following methods.
The results are shown in Table 1.

(Sensitivity) Using a high-illuminance photometer (xenon lamp) manufactured by Yamashita Dentsu Co., Ltd., an interference filter of 780 nm and a step wedge were used, exposure was carried out for 10 ^-5 seconds, and development processing was performed to obtain sensitivity. The sensitivity was shown as relative sensitivity with sample 1 being 100.

(Development processing) The developer CDM671 / fixer CFL871 (both manufactured by Konica) is used, and the automatic processor is GR-27 manufactured by Konica. Development time is 28 ° C./3.
The processing time was set to 0 seconds and the total processing time was 90 seconds.

(Residual color) The sample was developed while unexposed,
Five sheets were piled up and visually evaluated. The sample containing no dye was set to 5 and was evaluated on a scale of 5 with 1 being an extremely poor level. Four
The above is the practical level.

(Gamma) Density was determined from the slope of the exposure amount giving 0.1 and 2.5.

[0153]

[Table 1]

[0154]

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As is clear from Table 1, it is possible to provide a photographic light-sensitive material having less fog and residual color, excellent sharpness and good storage stability.

Example 2 The sample of Example 1 was subjected to development processing conditions under the conditions of 34 ° C. and 15 seconds (referred to as Samples 16 to 30). Table 2 shows the results.

[0157]

[Table 2]

As is clear from Table 2, it is possible to provide a silver halide photographic light-sensitive material having little residual color, excellent sharpness and high contrast even if the developing time is shortened.

Example 3 The procedure of Example 1 was repeated, except that the composition of the emulsion coating solution, the composition of the emulsion protective layer (both indicated in the amount per 1 m ^{2 of the} coated sample) and the treatment were changed as follows.

<< Preparation of Emulsion Coating Solution >> The same procedure as in Example 1 was carried out except that the following additions were made in the preparation of silver halide in Example 1.

Saponin (surfactant) 0.1 g Surfactant (SU-2) 8 mg Hydrazine compound (H-27) 25 mg Nucleation accelerator (NA-I-15) 20 mg Latex polymer (LA-1) 1 g Polyethylene Glycol (molecular weight 4000) 0.1 g Ethylenediaminetetraacetic acid 50 mg << Preparation of emulsion protective layer >> Gelatin 0.9 g Surfactant (SU-3) 10 g Surfactant (SU-4) 5 mg Matting agent (monodisperse silica; average particle size) Diameter 3.5 μm) 5 mg Hardener (H-2) 80 mg SU-3: Sodium di (2-ethylhexyl) sulfosuccinate SU-4: Sodium p-heptafluorononylbenzenesulfonate developer composition Potassium sulfite 52.5 g Hydroquinone 20.0 g 4-methyl-4-hydroxymethyl-1-phenyl-3 -Pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 2.0 g Potassium carbonate 12.0 g Potassium bromide 5.0 g 5-Methylbenzotriazole 0.3 g 5-Nitroindazole 0.1 g Diethylene glycol 25.0 g General formula of the present invention [ H] compound The amount shown in Table 1 was added to make 1 liter, and the pH was adjusted to 1 with potassium hydroxide.
Adjusted to 0.4. For comparison, an alkanolamine compound was added to the above developing solution.

Fixer composition Ammonium thiosulfate (72.5% W / V aqueous solution) 200 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium oxalate dihydrate 2.0 g Pure water (ion Exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 2.0 g Aluminum sulfate (aqueous solution having an Al ₂ O ₃ equivalent content of 8.1% W / V) 8.5 g Used to make up to 1 liter. P of this fixer
H was adjusted to 4.8 with acetic acid.

The development processing conditions are as follows.

(Process) (Temperature) (Time) * Development 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Washing 30 ° C. 10 seconds Drying 50 ° C. 13 seconds Total 45 seconds * Including wading time.

The results are shown in Table 3.

[0166]

[Table 3]

As is clear from Table 3, it is possible to provide a silver halide photographic light-sensitive material which has a small residual color even if the total development processing time is shortened, has excellent contrast and has a high contrast.

[0168]

According to the present invention, it is possible to provide a photographic light-sensitive material having less fog and improved stability over time.
The photographic light-sensitive material was high in sensitivity and excellent in toning property, and gave an image with little residual color contamination even after a short development process.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 7/00 520 G03C 7/00 520 530 530

Claims (8)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one hydrophilic colloid layer containing a dye represented by the following general formula (I) on a support. Embedded image [In the formula, R ₁ and R ₂ each represent an alkyl group, and Z ₁ and Z ₂ each represent a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle. L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ each represent a methine group. However, L ₁ , L ₂ , L ₃ , L ₄ ,
At least one of L ₅ , L ₆ and L ₇ has a COR ₃ group (R ₃ represents an alkyl group, an aryl group, an amino group or a heterocyclic group) as a substituent, and L ₃ and L ₅ are bonded to each other. To form a ring. X ₁ ^- represents an anion, p _1, p _2,
m, n ₁ , n ₂ and n ₃ each represent 0 or 1. However,
n ₁ , n ₂ and n ₃ do not become 0 at the same time. ] 2. A silver halide photographic light-sensitive material according to claim 1, which has at least one non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye represented by formula (I). material. 3. A dye represented by the general formula (I) is represented by the following general formula (II).
A dye represented by the following formula:
The silver halide photographic light-sensitive material as described above. Embedded image [In the formula, R ₁ and R ₂ each represent an alkyl group, and R ₄ ,
R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₄ and R ₅ and R ₆ and R ₇ may be bonded to each other to form a ring. Z ₃ and Z ₄ each represent a nonmetallic atom group necessary for forming an aromatic ring or a heterocycle. L ₁ ,
L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ each represent a methine group. However, at least one of L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ represents a COR ₃ group (R ₃ represents an alkyl group, an aryl group, an amino group or a heterocyclic group). Having a substituent, L ₁ and R ₅ , L ₃ and L _5, and L ₇ and R ₆ may be bonded to each other to form a ring. X ₁ ^- represents an anion, m,
n ₁ , n ₂ and n ₃ each represent 0 or 1. However, n ₁ ,
n ₂ and n ₃ cannot be 0 at the same time. ] 4. A hydrazine compound is contained in at least one hydrophilic colloid layer.
4. The silver halide photographic light-sensitive material according to 2 or 3. 5. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein at least one hydrophilic colloid layer contains a tetrazolium salt compound. 6. A development processing method comprising processing the silver halide photographic light-sensitive material according to claim 1 for a total processing time of 90 seconds or less. 7. The development processing method according to claim 6, wherein processing is performed for a total processing time of 45 seconds or less. 8. A dye represented by the following general formula (II). Embedded image [In the formula, R ₁ and R ₂ each represent an alkyl group, and R ₄ ,
R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an alkyl group or an aryl group, and R ₄ and R ₅ and R ₆ and R ₇ may be bonded to each other to form a ring. Z ₃ and Z ₄ each represent a nonmetallic atom group necessary for forming an aromatic ring or a heterocycle. L ₁ ,
L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ each represent a methine group. However, at least one of L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ and L ₇ represents a COR ₃ group (R ₃ represents an alkyl group, an aryl group, an amino group or a heterocyclic group). Having a substituent, L ₁ and R ₅ , L ₃ and L _5, and L ₇ and R ₆ may be bonded to each other to form a ring. X ₁ ^- represents an anion, m,
n ₁ , n ₂ and n ₃ each represent 0 or 1. However, n ₁ ,
n ₂ and n ₃ cannot be 0 at the same time. ]