JPH09304856A - Silver halide photographic sensitive material and its image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material which hardly causes decrease in sensitivity or low contrast, shows excellent reproducibility of small dots and does not produce defects of black spots even in continuous processes and to provide its image forming method. SOLUTION: This photosensitive material is produced to satisfy the following requirements (1) to (3). (1) The silver halide photographic sensitive material has at least two silver halide emulsion layers and at least one nonphotosensitive hydrophilic colloid layer on one surface of a base body. At least one of the silver halide emulsion layers and/or nonphotosensitive hydrophilic colloid layer contains a water-soluble dye and a dye dispersed in a solid state. Further, the silver halide emulsion layers and/or nonphotosensitive hydrophilic colloid layer adjacent to the emulsion layers contain a hydrazine deriv. (2) The layer containing a dye dispersed in a solid state has 0.05 to 1.0 reflection density, while the layer containing a water-soluble dye has 0.05 to 1.0 transmission density. (3) The dye dispersed in a solid state is included in the nonphotosensitive hydrophilic colloid layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high contrast black and white silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for printing plate making and an image forming method thereof.

[0002]

2. Description of the Related Art In recent years, a screening system for forming an image with a smaller halftone dot than before, such as high definition and FM screening, has begun to spread in the printing plate making scanner market. For such a screening method, a super-hard contrast type photosensitive material which is easy to get a small density is suitable.

In the silver halide photographic light-sensitive material for printing plate making, various techniques are known as a photographic technique for obtaining an ultrahigh contrast image. Among them, for example, US Pat.
Silver halide photographic light-sensitive material containing hydrazine derivative disclosed in JP-A-4-982.
A silver halide photographic light-sensitive material containing a nucleation accelerator as disclosed in No. 39 is widely known.

However, the silver halide photographic light-sensitive material containing a hydrazine derivative has a problem in that its major point is that it tends to be fat because of utilizing the nucleation promoting reaction, and that its linearity is poor.

As a technique for improving this, a method using a water-soluble dye is known. However, in order to obtain a sufficient effect, there was a problem that the sensitivity was significantly reduced.

In recent years, there has been known a technique of incorporating a non-water-soluble dye dispersed in a solid state into a light-sensitive material for the purpose of reducing sensitivity deterioration due to the water-soluble dye. However, there is a drawback that the running process is easily affected by fluctuations in the pH of the processing solution, and particularly when the pH of the developing solution is low, the effect of improving linearity is further reduced, and further improvement has been desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is free from sensitivity deterioration and softening even during running processing, has excellent dot reproducibility, and is free from black spot defects. It is to provide the image forming method.

[0008]

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

(1) In a silver halide photographic light-sensitive material having at least two silver halide emulsion layers and at least one non-photosensitive hydrophilic colloid layer on one surface of a support, the silver halide emulsion layers And / or at least one of the non-photosensitive hydrophilic colloid layers contains a water-soluble dye and a solid-dispersed dye, and the non-photosensitive hydrophilic layer adjacent to the silver halide emulsion layer and / or A silver halide photographic light-sensitive material comprising a hydrazine derivative in a colloid layer.

(2) The reflection density of the layer containing the dye dispersed in a solid state is 0.05 to 1.0, and the transmission density of the layer containing the water-soluble dye is 0.05 to 1.0. The silver halide photographic light-sensitive material as described in the item (1), which is present.

(3) The silver halide photographic light-sensitive material according to the item (1) or (2), wherein the solid-state dispersed dye is contained in the non-photosensitive hydrophilic colloid layer.

(4) A layer containing a dye dispersed in a solid state is a layer closer to the support than a layer containing a water-soluble dye, which is one of the items (1) to (3). The silver halide photographic light-sensitive material as described in the item 1.

(5) The emulsion layer closest to the support and / or the non-photosensitive hydrophilic colloid layer adjacent to the emulsion layer contains a redox compound which is oxidized to release a development inhibitor (1). ~ The silver halide photographic light-sensitive material described in any one of (4).

(6) The silver halide photographic light-sensitive material described in any one of the above items (1) to (5) has a pH of 9.5 to 1.
An image forming method for a silver halide photographic light-sensitive material, wherein γ is 10 to 30 after processing with the developer of 1.2.

Hereinafter, the present invention will be described in detail.

In the present invention, the layer containing a water-soluble or solid-dispersed dye may be a layer constituting a photographic material, for example, a photosensitive silver halide emulsion layer, which does not directly contribute to image formation. Examples thereof include a non-photosensitive hydrophilic colloid layer, a non-photosensitive silver halide emulsion layer, an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer and a backing layer.

In the present invention, the water-soluble dye means a dye which is soluble in pure water at 25 ° C. by 0.5 wt% or more.

The water-soluble dye in the present invention is preferably a water-soluble dye having an absorption maximum value within ± 50 nm with respect to the light absorption maximum value of the emulsion layer. Here, the maximum light-sensitivity value of the emulsion layer is defined as a wavelength which gives maximum sensitivity when spectral light is applied to the light-sensitive material of the present invention. Further, the absorption maximum value is a wavelength at which the value of the spectral absorption of the dye to be added becomes the maximum, and is defined as the absorption wavelength in the state of being dispersed in the binder to form a film. In the above, in the case of a dye having no absorption maximum value within ± 50 nm, the effect of suppressing the large point shift and improving the linearity, which is the object of the present invention, cannot be obtained.

Among the water-soluble dyes used in the present invention, specific examples of dyes having a spectral maximum of spectral sensitivity near 488 nm as a photosensitive material for an argon laser are shown below.
The present invention is not limited to these.

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

Next, among the water-soluble dyes used in the present invention, 633n is used as a light-sensitive material for a helium neon laser.
Specific examples of the dye having a spectral sensitivity maximum in the vicinity of m and the dye having a spectral sensitivity maximum in the vicinity of 670 nm as a photosensitive material for red laser are shown below, but the present invention is not limited thereto. .

[0024]

Embedded image

[0025]

Embedded image

[0026]

[Chemical 6]

[0027]

[Chemical 7]

The above-mentioned amount of the water-soluble dye added to the silver halide photographic light-sensitive material is 0 when the transmission density of the water-soluble dye-containing layer is measured at the wavelength of the light source used for exposing the light-sensitive material.
It is preferably 05 to 1.0, and more preferably 0.1 to
Most preferably, it is 0.8. The dyes may be used in combination of two or more kinds.

The above-mentioned water-soluble dye is dissolved in water or a hydrophilic solvent such as methanol or ethanol and added to the coating solution.

In the present invention, the layer containing the water-soluble dye is particularly preferably a layer farther from the support than the layer containing the dye dispersed in a solid state as described below.

Next, the dye dispersed in a solid state which can be used in the present invention will be described. The solid-state dispersed dye used in the present invention is not particularly limited, but compounds represented by the following general formulas [1] to [6] are preferably used.

[0032]

Embedded image

In the formula, A and A'may be the same or different and each represents an acidic nucleus, B represents a basic nucleus,
Q represents an aryl group or a heterocyclic group; Q ′ represents a heterocyclic group; X ₄ and Y ₁ may be the same or different and each represents an electron-withdrawing group; L ₁ , L ₂ and L ₃ Each represents a methine group. m ₂ represents 0 or 1, t is 0,
Represents 1 or 2, and p ₂ represents 0 or 1. However, the dyes represented by the general formulas [1] to [6] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule.

The acidic nuclei represented by A and A'in the general formulas [1], [2] and [3] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin and thio. Hydantoin, oxazolone,
Examples include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, and pyrazolopyridone.

The basic nucleus represented by B in the general formulas [3] and [5] is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole,
Thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole, indole.

Examples of the aryl group represented by Q in the general formulas [1] and [4] include a phenyl group and a naphthyl group. Examples of the heterocyclic group represented by Q and Q 'in formulas [1], [4] and [6] include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group and an indolyl group. Group, furyl group,
And a thienyl group. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include an amino group of the compounds represented by the aforementioned general formulas [1] to [5],
Examples of the substituent such as a heterocyclic group and the like, and the like,
You may have these substituents in combination of 2 or more types. 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.),
Hydroxy group, cyano group, halogen atom, (for example, fluorine atom, chlorine atom), alkoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, butoxy group, etc.) A substituted amino group (eg, dimethylamino group, diethylamino group,
Di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group, sulfonamide group (Eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (eg, sulfamoyl group,
(Methylsulfamoyl group, phenylsulfamoyl group, etc.), and these substituents may be combined.

The electron withdrawing groups represented by X ₄ and Y ₁ in the general formulas [4] and [5] may be the same or different,
Substituent constant Hammett's σp value (Toshio Fujita eds., "Chemical Region Special Issue No. 122, Structure-Activity Relationship of Drugs", 96-1
Page 03 (1979), Nankodo, and the like. ) Is 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, a phenoxycarbonyl group, 4 -Hydroxyphenoxycarbonyl group), carbamoyl group (eg, carbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group (eg, methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group) , 4-
And an ethylsulfonyl group (eg, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, etc.) and an arylsulfonyl group (eg, a phenylsulfonyl group, a 4-chlorosulfonyl group, etc.). .

L ₁ , L ₂ and L _{3 of the} general formulas [1] to [5]
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a hexyl group, etc.), an aryl group (for example, a 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.), substituted amino group (eg dimethylamino group, diethylamino group) , Anilino groups, etc.) and alkylthio groups (eg, methylthio groups, etc.).

In the present invention, among the dyes represented by the general formulas [1] to [6], a dye having at least one carboxyl group in the molecule is preferably used, and more preferably the general formula [1]. A dye represented by the formula, and particularly preferably a dye in which Q is a furyl group in the general formula [1].

Specific examples of dyes that are preferably used are shown below, but the dyes are not limited thereto.

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

Other preferable specific examples of the compounds represented by the general formulas [1] to [6] include Japanese Patent Application No. 5-27.
No. 7011, pages 19 to 30. I-1 to No. 1;
I-30, II-1 to II-12, III-1 to III-8, IV-
1 to IV-9, V-1 to V-8 and VI-1 to VI-5 can be mentioned, but the invention is not limited thereto.

In the present invention, the addition amount of the above dye dispersed in a solid state is such that the reflection density of the dye-containing layer is 0.05 to
It is 1.0, preferably 0.06 to 0.09.

In the present invention, the dye dispersed in a solid state is at least one of the silver halide photographic light-sensitive materials of the present invention.
It is contained in the non-photosensitive hydrophilic colloid layer of the layer.

A method for producing a solid fine particle dispersion of a dye according to the present invention is described in JP-A-52-92716 and JP-A-5-92716.
5-155350, 55-155351, 63
The methods described in, for example, No. 197943, No. 3-182743, and WO88 / 04794 can be used. Specifically, it can be manufactured using a fine dispersing machine such as a ball mill, a planetary mill, a vibration mill, a sand mill, a roller mill, a jet mill, and a disk impeller mill. When the compound in which solid fine particles are dispersed is water-insoluble at a relatively low pH and water-soluble at a relatively high pH, after dissolving the compound in a weak alkaline aqueous solution,
The method of precipitating fine particle solids by lowering the pH to weakly acidic or a method of preparing a fine particle solid by simultaneously mixing a weak alkaline solution of the compound and an acidic aqueous solution while adjusting the pH of the compound A dispersion can be obtained.

The solid fine particle dispersion of the present invention may be used alone, or two or more kinds may be mixed and used, or may be used by mixing with a solid fine particle dispersion other than the present invention. When two or more kinds are used as a mixture, they may be dispersed individually and then mixed, or they may be dispersed simultaneously.

The solid fine particle dispersion used in the present invention is
In the case of producing in the presence of an aqueous dispersion medium, it is preferable that a surfactant is present during or after dispersion. As such a surfactant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used, but preferably, for example, an alkyl sulfonate, an alkylbenzene sulfonic acid. salt,
Anionic surfactants such as alkylnaphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, N-acyl-N-alkyl taurines and saponins, alkylene oxide derivatives, and the like.
It is a nonionic surfactant such as an alkyl ester of sugar. Particularly preferred are the above-mentioned anionic surfactants. Specific examples of the surfactant include Japanese Patent Application No. 5-2.
Examples of the compounds include Nos. 1 to 32 described in 77011, pages 32 to 46, but are not limited to these. The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion liquid of the dye, but usually 0.1 mg to 20 mg per 1 g of the dye.
00 mg is preferable, and more preferably 0.5 mg to 10 mg.
It may be 00 mg, particularly preferably 1 mg to 500 mg.

The concentration of the dye in the dispersion is 0.01
It is preferably used so as to be about 50% by weight,
More preferably, it is 0.1 to 30% by weight. The addition position of the surfactant is preferably added before the start of dispersion of the dye,
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 may be combined with both activators.

The solid fine particle dispersion used in 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, particularly preferably 0.01 to 0.5 μm.
μm. The dispersion coefficient 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 The solid fine particle dispersion used in the present invention is a hydrophilic colloid used as a binder of a photographic constituent layer before the start of dispersion or after the end of dispersion. Can be added. As the hydrophilic colloid, it is advantageous to use gelatin, but other than that, for example, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin and the like, and gelatin and a monomer having a polymerizable ethylene group are used. Graft polymer, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol,
Partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-
Synthetic hydrophilic polymers such as N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin, casein and the like can be used. These may be used in combination of two or more. The addition amount of the hydrophilic colloid added to the solid fine particle dispersion of the present invention is preferably 0.1% to 12% by weight, more preferably 0.5% to 8%. is there.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention or the hydrophilic colloid layer adjacent thereto contains a hydrazine derivative. As the hydrazine derivative, a compound represented by the following general formula [H] can be preferably used.

[0054]

[Chemical 12]

In the formula, A represents an aryl group or a heterocycle containing at least one sulfur atom or oxygen atom, and G represents-.
(CO) n-group, sulfonyl group, sulfoxy group, -P
(＝ O) represents a R ₂ — group or an iminomethylene group, n represents an integer of 1 or 2, both A ₁ and A ₂ are a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a heterocyclic oxy group, an amino group. A carbamoyl group or an oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group or the like.

Of the compounds represented by the general formula [H], the compounds represented by the following general formula [Ha] are more preferred.

[0057]

Embedded image

In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or heterocyclic group (eg, pyridyl group, thienyl group, Represents a furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

The anti-diffusion group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group is an alkyl group having 8 or more carbon atoms and relatively inert to photographic properties. , Alkenyl group, 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 adsorptive group described in JP-A-64-90439.

In the general formula [Ha], X represents a group capable of substituting for a phenyl group, m represents an integer of 0 to 4, and m
Is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and both are preferably hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ² is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ₃ group and —CON (R ₄ )
(R ₅₎ groups (R ₃ represents an alkynyl group or a saturated heterocyclic group, R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group,
R ₅ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

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

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

Specific examples of other preferred hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in columns 59 to 80 of No. 29,248.

The amount of addition may be any amount that makes the contrast higher (the amount of the higher contrast), and the particle size of the silver halide grains, the halogen composition,
Although the optimum amount varies depending on the degree of chemical sensitization and the type of the inhibitor, it is generally 10 ^-6 to 10 per mol of silver halide.
It is in the range of ^-1 mol, preferably in the range of ^10-5 to ^10-2 mol.

The hydrazine derivative preferably used in the present invention is added to the silver halide emulsion layer and / or its adjacent layer. The hydrazine compound used in the present invention can be used in any layer as long as it is on the silver halide emulsion layer side, but it is preferably used in the silver halide emulsion layer or its adjacent layer. The optimum addition amount varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. A molar range is preferred,
Particularly, the range of 10 ⁻⁵ to 10 ⁻² mol is preferable.

In order to effectively promote the contrast increase by the hydrazine derivative, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb].

[0076]

Embedded image

In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. 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. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

Particularly preferred as the general formula [Na] is a compound having at least one thioether group as a silver halide adsorbing group in the molecule.

Specific examples of these nucleation accelerators [Na] will be given below.

[0080]

Embedded image

[0081]

[Chemical 21]

[0082]

Embedded image

[0083]

Embedded image

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ is a hydrogen atom,
Represents an alkyl group, an alkynyl group, or an aryl group;
And R ₁₄ may be linked by a linking group to form a ring. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

Specific examples of the compound of the general formula [Nb] include those shown below.

[0086]

Embedded image

[0087]

Embedded image

Specific examples of other preferable nucleation promoting compounds include the compounds (2-1) to (2-20) described in JP-A-6-258751 and 6-2587.
The compounds of (3-1) to (3-6) described in No. 51.

The nucleation accelerator used in the present invention can be used in any layer on the silver halide emulsion layer side, but is preferably used in the silver halide emulsion layer or its adjacent layer. . The optimum amount to be added depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. It is preferably in the range of mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

In the silver halide photographic light-sensitive material of the present invention, a redox compound which releases a development inhibitor in the emulsion layer closest to the support and / or the non-photosensitive hydrophilic colloid layer adjacent thereto is released. Is contained.

The redox compounds capable of releasing the development inhibitor by being oxidized in the present invention include hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines and reductones as redox groups. , Α-aminoketones and the like. Preferred redox compounds are compounds having a -NHNH- group as a redox group and the following general formulas [7], [8],

[9], [10], [11] or [1
2].

[0092]

[Chemical formula 26]

[0093]

Embedded image

The compound having a --NHNH-- group as a redox group is represented by the following general formula [RE-a] or [RE-
b].

General Formula [RE-a] T-NHNHCOV- (Time) -PUG General Formula [RE-b] T-NHNHCOCOV- (Time) -PUG In General Formula [RE-a] and [RE-b], T and V each represent an optionally substituted aryl group or an optionally substituted alkyl group. Examples of the aryl group represented by T and V include a benzene ring and a naphthalene ring, and these rings may be substituted with various substituents. A preferable substituent is a linear or branched alkyl group (preferably Are those having 2 to 20 carbon atoms, such as methyl, ethyl, isopropyl group, dodecyl group, etc., alkoxy groups (preferably those having 2 to 21 carbon atoms, such as methoxy group, ethoxy group, etc.),
Aliphatic acylamino groups (preferably having an alkyl group having 2 to 21 carbon atoms, such as acetylamino group, heptylamino group, etc.), aromatic acylamino groups, and the like,
These other, for example, a substituted or unsubstituted aromatic rings, such as described above -CONH -, - O -, - SO 2 NH -, - NH
CONH -, - including those attached with a linking group such as CH ₂ CHN-. As PUG, 5-nitroindazole, 4-nitroindazole, 1-phenyltetrazole, 1- (3-sulfophenyl) tetrazole, 5
-Nitrobenzotriazole, 4-nitrobenzotriazole, 5-nitroimidazole, 4-nitroimidazole and the like can be mentioned.

These development-inhibiting compounds are T-NHNH
It can be connected to the CO site of —CO— directly via a hetero atom such as N or S, or further via an N or S hetero atom via an alkylene, phenylene, aralkylene or aryl group. In addition, a development inhibitor such as triazole, indazole, imidazole, thiazole or thiadiazole may be introduced into a hydroquinone compound having a ballast group. For example, 2- (dodecylethylene oxide thiopropionamide) -5-
(5-nitroindazol-2-yl) hydroquinone, 2- (stearylamido) -5- (1-phenyltetrazol-5-thio) hydroquinone, 2- (2,4
-Di-t-amylphenoxypropionamide) -5
-(5-nitrotriazol-2-yl) hydroquinone, 2-dodecylthio-5- (2-mercaptothiothiadiazole-5-thio) hydroquinone and the like. Redox compounds are disclosed in US Pat. No. 4,269,929.
The compound can be synthesized with reference to the description of the symbol.

The redox compound can be contained in the emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in the hydrophilic colloid layer via the intermediate layer. The amount of redox compound added is 1 per mol of silver halide.
It is preferably 0 ^-6 to 10 ^-1 mol, more preferably 1
It is in the range of 0 ^-4 mol to 10 ^-2 mol.

In the present invention, a redox compound which is substantially water-insoluble and releases a development inhibitor upon being dissolved is dissolved in a volatile organic solvent, and the solution is added and mixed in a hydrophilic colloid to remove the solvent. By doing so, the redox compound can be dispersed in the hydrophilic colloid as solid dispersion fine particles in the hydrophilic colloid. In the present invention, the volatile organic solvent may be either a water-miscible solvent, a water-immiscible solvent, or a water-miscible solvent to some extent, but the solubility in water of 25% by weight at room temperature (20 ° C.). Preferably. 2-10 at room temperature (20 ° C)
It is even more preferred to have a solubility in water of wt%. Furthermore, the above solvents have boiling points below 130 ° C.
It is preferred to have a vapor pressure high enough to be easily removed from the dispersion by applying a reduced pressure of 10 to 500 mmHg at -80 ° C. Preferred examples of the volatile organic solvent include methylene chloride, ethyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, methyl propionate, and ethyl propionate. Nitrate, n-butyl alcohol, diethyl ketone, methyl n-propyl ketone, diisopropyl ether, cyclohexane, methylcyclohexane, benzene, toluene and the like.

In the present invention, when a redox compound is added and mixed in a hydrophilic colloid for emulsification and dispersion,
Conventionally used dispersion methods can be used. The solid fine particle dispersion of the present invention may be used alone, or two or more kinds may be mixed and used, or may be used by mixing with a solid fine particle dispersion other than the present invention. When two or more kinds are used as a mixture, they may be dispersed individually and then mixed, or they may be dispersed simultaneously.

When the solid fine particle dispersion used in the present invention is produced in the presence of an aqueous dispersion medium, it is preferable that a surfactant is allowed to coexist during or after the dispersion.
As such a surfactant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used, but preferably,
For example, alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers,
Anionic surfactants such as N-acyl-N-alkyltaurines and nonionic surfactants such as saponins, alkylene oxide derivatives and alkyl esters of sugars. Particularly preferred are the above-mentioned anionic surfactants. Specific examples of the surfactant include compounds of 1 to 32 described in Japanese Patent Application No. 5-277011, pages 46 to 32, but are not limited thereto.

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 of the redox compound, but it is usually
0.1 mg to 2000 mg per 1 g of redox compound
Is preferred, and more preferably 0.5 mg to 1000 mg
And particularly preferably 1 mg to 500 mg.

The concentration of the redox compound in the dispersion is preferably 0.01 to 50% by weight, more preferably 0.1 to 30% by weight. The surfactant may be added at a position before the dispersion of the redox compound is started, and 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, respectively, or two or more kinds may be combined, and both activators may be combined.

The solid fine particle dispersion used in 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, particularly preferably 0.01 to 0.5 μm.
μm. The dispersion coefficient of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the coefficient of variation of the particle size distribution is a value represented by the following formula.

(Standard deviation of particle size) / (Average value of particle size) × 100 As the hydrophilic colloid to which the redox compound used in the present invention is added, it is advantageous to use gelatin. Gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin, graft polymers of gelatin and a monomer having a polymerizable ethylene group, cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose, and cellulose sulfate, polyvinyl alcohol,
Partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-
Synthetic hydrophilic polymers such as N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin, casein and the like can be used. These may be used in combination of two or more. The addition amount of the hydrophilic colloid added to the solid fine particle dispersion of the present invention is preferably 0.1% to 12% by weight, more preferably 0.5% to 8%. is there.

Among the compounds represented by the formula [RE-a] or [RE-b], particularly preferred compounds are shown below.

[0107]

Embedded image

[0108]

[Chemical 29]

Specific examples of other preferred redox compounds are described in JP-A-4-245243, 236.
(8) page “0053” to 250 (22) page “0068”
R-1 to R-50 described in 1.

Further, the above general formulas [7], [8],

[9],
The redox compound represented by [10], [11] or [12] will be described.

The general formulas [7], [8],

[9], [1
[0], [11] or [12], R ₁ represents an alkyl group, an aryl group or a heterocyclic group. R ₂ and R ₃ represent a hydrogen atom, an acyl group, a carbamoyl group, a cyano group, a nitro group, a sulfonyl group, an aryl group, an oxalyl group, a heterocyclic group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ₄ represents a hydrogen atom. R ₅ to R ₉ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. r
₁ , r ₂ and r ₃ each represent a substituent capable of substituting on the benzene ring. X ₁ and X ₂ represent O or NH. Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. W is N (R
₁₀ ) R ₁₁ or OH, wherein R ₁₀ and R ₁₁ are a hydrogen atom,
It represents an alkyl group, an aryl group or a heterocyclic group. COUP
Represents a coupler residue capable of causing a coupling reaction with an oxidized form of an aromatic primary amine developing agent, and * represents a coupling site of the coupler. Tm represents a timing group.
m ₁ and p ₁ represent an integer of 0 to 3. q ₁ represents an integer of 0 to 4. n represents 0 or 1. PUG represents a development inhibitor.

The general formulas [7], [8],

[9], [1
0], [11] or [12] (hereinafter, in the formula)
Alkyl groups and aryl groups represented by R ₁ and R _{5 to} R ₁₁ ,
Preferred examples of the heterocyclic group include a methyl group, a p-methoxyphenyl group, and a pyridyl group. Of the acyl groups, carbamoyl groups, cyano groups, nitro groups, sulfonyl groups, aryl groups, oxalyl groups, heterocyclic groups, alkoxycarbonyl groups, and aryloxycarbonyl groups represented by R ₂ and R ₃ , preferably an acyl group, carbamoyl Group, a cyano group. The total number of carbon atoms in these groups is preferably 1 to 20. R _{1 to} R ₁₁ may further have a substituent, for example, a halogen atom (a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group,
Ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc., cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl group (eg, benzyl group, 2-phenethyl group) Etc.), an aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, butoxy group, etc.), an aryloxy group (eg, phenoxy group) Group), cyano group, acylamino group (eg, acetylamino group, propionylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, butylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonylamino group (eg, Methanesulfonylamino group, ben Emissions sulfonylamino group),
Ureido group (for example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.),
Sulfamoylamino group (dimethylsulfamoylamino group etc.), carbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group etc.), sulfamoyl group (eg ethylsulfamoyl group, dimethylsulfamoyl group etc.) , An alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), a sulfonyl group (eg, methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group, etc.), an acyl group (eg, Acetyl group, propanoyl group, butyroyl group etc.), amino group (eg methylamino group, ethylamino group, dimethylamino group etc.), hydroxyl group, nitro group, imide group (eg phthalimido group etc.), heterocyclic group (eg. , A pyridyl group, benzimidazolyl group, benzothiazolyl group, benzoxazolyl group). Examples of the coupler residue represented by COUP include the following.

Examples of the cyan coupler residue include a phenol coupler and a naphthol coupler. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolone couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, and indazolone couplers.
Examples of the yellow coupler residue include a benzoylacetanilide coupler, a pivaloylacetanilide coupler, and a malondianilide coupler. Colorless coupler residues include open-chain or cyclic active methylene compounds (eg, indanone, cyclopentanone, malonic acid diester, imidazolinone, oxazolinone, thiazolinone, etc.).
Further, among the coupler residues represented by COUP, those which are preferably used in the present invention are represented by the general formula (Coup-
It can be represented by 1) to the general formula (Coup-8).

[0114]

Embedded image

In the formula, R ₁₆ represents an acylamide group, anilino group or ureido group, and R ₁₇ represents a phenyl group which may be substituted with one or more halogen atoms, alkyl groups, alkoxy groups or cyano groups. .

[0116]

[Chemical 31]

In the formula, R ₁₈ and R ₁₉ represent a halogen atom, an acylamido group, an alkoxycarbonylamido group, a sulfouride group, an alkoxy group, an alkylthio group, a hydroxy group or an aliphatic group, and R ₂₀ and R ₂₁ are each a fatty acid. It represents a group group, an aromatic group or a heterocyclic group. One of R ₂₀ and R ₂₁ may be a hydrogen atom. a is an integer of 1 to 4, b is 0
Represents an integer of 5. When a and b are plural, R ₁₈ may be the same or different, and R ₁₉ may be the same or different.

[0118]

Embedded image

In the formula, R ₂₂ represents a tertiary alkyl group or an aromatic group, and R ₂₃ represents a hydrogen atom, a halogen atom or an alkoxy group. R ₂₄ represents an acylamide group, an aliphatic group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group,
Represents an alkoxy group, a halogen atom or a sulfonamide group.

[0120]

[Chemical 33]

In the formula, R ₂₅ represents an aliphatic group, an alkoxy group, an acylamino group, a sulfonamide group, a sulfamoyl group,
A diacylamino group and R ₂₆ represent a hydrogen atom, a halogen atom, or a nitro group.

[0122]

Embedded image

R ₂₇ and R ₂₈ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The 5- or 6-membered heterocycle represented by Z ₁ may be a monocycle or a condensed ring, and examples thereof include a 5- or 6-membered heterocycle having at least one kind of O, S and N atoms in the ring. These rings may have a substituent, and specific examples thereof include the above-mentioned substituents.

The timing group represented by Tm is preferably —OCH ₂ — or another divalent timing group, for example, US Pat. Nos. 4,248,962 and 4,409,3.
No. 23, or No. 3,674,478, Research
Disclosure 21228 (December 1981)
Month), or JP-A-57-56837 and JP-A-4-43.
Examples thereof include those described in JP-A-8.

Preferred development inhibitors for PUG include, for example, US Pat. No. 4,477,563 and JP-A-60-218.
No. 644, No. 60-221750, No. 60-2336
No. 50, or the development inhibitor described in No. 61-11743.

General formula [7] used in the present invention will be described below.
Specific examples of the compound represented by [12] are listed, but the present invention is not limited thereto.

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

General formula [7] preferably used in the present invention
The compound represented by [12] is preferably contained in an amount of 1 × 10 ⁻⁶ to 5 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁴ to 2 × 10 ⁻² mol per mol of silver halide. Is preferred.

The solid fine particle dispersion used in the present invention comprises a layer constituting a photographic material such as a silver halide emulsion layer, an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer,
It can also be used in layers such as backing layers. In particular, it is preferable that at least one of the non-photosensitive hydrophilic colloid layers is contained in these layers. Furthermore, it is preferably added to a layer closer to the support than a layer containing a water-soluble dye.

The amount of the dye dispersed in the solid state is not uniform depending on the kind of the dye and the characteristics of the photographic light-sensitive material, but it is preferably 1 mg to 1 g per m ^{2 of} the light-sensitive material, and more preferably 5 mg. To 800 mg, particularly preferably 10 mg to 500 mg.

The solid disperse dye may be contained in any layer opposite to the emulsion layer. A water-soluble dye may be used in any layer.

The addition amount of the dye dispersed in the solid state in the present invention is preferably such that a reflection density of 0.05 to 1.0 can be obtained in the wavelength region of the light source used for exposure. , And particularly preferably 0.1 to 0.8 is added. Further, in the present invention, dyes having other absorption wavelengths can be used together in any layer.

The light-sensitive material of the present invention is most effectively used as an output light-sensitive material, and Ar is used as a light source.
A laser, a HeNe laser, a red laser diode, an infrared semiconductor laser, and a red LED laser are typical, but in addition, an arbitrary laser such as a blue laser such as a HeCd laser can be used. The effects of the present invention are not limited to laser output light-sensitive materials, but are also effective in applications such as shooting light-sensitive materials and return light-sensitive materials.

In the present invention, generally known sulfur sensitization, Se, Te sensitization, reduction sensitization and noble metal sensitization methods may be appropriately selected and used in combination. Further, the chemical sensitization may not be performed.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, rhodanins and polysulfide compounds can be used in addition to the sulfur compounds contained in gelatin.

Triphenylselenophosphine and the like are preferably used as the selenium sensitizer. A wide variety of selenium compounds can be used as the selenium sensitizer.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), selenoureas (eg, N, N).
-Dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylseleno Urea, N, N,
N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), seleno Carboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-
3-selenobutylate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Examples thereof include selenides (eg, triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides and selenoketones, and selenides.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. The temperature of the chemical ripening using the selenium sensitizer is preferably in the range of 40 to 90 ° C, more preferably 45.
The temperature is not less than 0 ° C and not more than 80 ° C. The pH is 4-9, pAg
Is preferably in the range of 6 to 9.5.

As a method for adding these sensitizers, if they are water-soluble, they can be added as they are, but if they are poorly soluble in water, various methods can be adopted. For example, there is a method in which a sulfur sensitizer and / or a selenium sensitizer and / or a tellurium sensitizer are sufficiently mixed in advance with a gelatin solution and then added. Alternatively, a method of dissolving in a low-boiling organic solvent in which a sensitizer is dissolved and then emulsifying and dispersing in the presence of a surfactant to add the sensitizer can also be adopted.
In this method, it is preferable to remove the low-boiling organic solvent after emulsification and dispersion. Further, the method disclosed in JP-A-4-140739 may be added in the form of an emulsified dispersion of a mixed solution of a water-insoluble polymer and an organic solvent-soluble polymer. Further, a method of arbitrarily dispersing the average particle diameter from 0.01 to 6 μm by high speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like can also be adopted. The gold sensitization method is a typical one of the noble metal sensitization methods, and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium, and rhodium may be contained.

Examples of the reduction sensitizer include stannous salt, amines,
Formamidinesulfinic acid, silane compounds and the like can be used.

Oxidizing agent In the present invention, an oxidizing agent for silver can be used in the process of producing a light-sensitive material. Examples of the oxidizing agent that can be used in the present invention include inorganic oxidizing agents such as hydrogen peroxide (water) and hydrogen peroxide adducts (for example, NaBO ₂ .H ₂ 0 ₂ .3H ₂ O,
2NaCO ₃ · 3H ₂ O ₂ , Na ₄ P ₂ O ₇ · 2H ₂ O ₂ , 2N
a ₂ SO ₄ · H ₂ O ₂ · 2H ₂ O etc.), peroxy acid salts (eg K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₄ P ₂ O ₈ etc.), peroxy complex compounds (eg K 2 ₂ [Ti (O ₂ ) C ₂ O ₄ ]
・ 3H ₂ O, 4K ₂ SO ₄・ Ti (O ₂ ) ・ OH ・ SO ₄・
2H ₂ O, Na ₂ [VO (O ₂ ) (C ₂ O ₄ ) ₂ ] · 6H ₂ O
Oxyacids such as permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ CrO), halogen elements such as iodine and bromine, and perhalates (eg, potassium periodate) , High valent metal salts (such as potassium ferricyanide) and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine). (B etc.) are mentioned as an example. A particularly preferred oxidant is ozone,
Hydrogen peroxide and its adducts, inorganic oxidants of halogen elements, quinones and organic oxidants that release active halogens.

The addition amount of the oxidizing agent to silver used in the present invention is preferably 10 ^-7 to 10 ^-1 mol per mol of silver halide. More preferably, 10 ^-6 to 10
^-2 mol, particularly preferably 10 ^-5 to 10 ^-3 mol.

In order to add the oxidizing agent for silver used in the present invention during the chemical sensitization step, a method usually used for adding an additive to a photographic emulsion can be applied. For example, a water-soluble compound is prepared as an aqueous solution having an appropriate concentration, and a water-insoluble or hardly soluble compound is dissolved in a suitable organic solvent miscible with water, such as alcohols, glycols, ketones, esters, and amides. Can be dissolved in a solvent that does not adversely affect the photographic properties and can be added. Further, it can be added in a solid dispersion state.

The oxidizing agent for silver used in the present invention may be added at any time during the production process of the amount of the halogenated sensitizing material, but the preferred time is from the step of preparing silver halide grains to the coating on the support. This is the process up to immediately before.

In the present invention, the halogen composition of the silver halide in the silver halide emulsion is pure silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or chloroiodo containing 60 mol% or more of silver chloride. It is preferably silver bromide. The average grain size of silver halide is preferably 0.7 μm or less, and particularly preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see C.I. E. FIG.
Mees & T. H. James: The Theory
of the photographic proc
Ess, 3rd edition, pp. 36-43 (1966, published by Macmillan).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrow, and in particular, the total number of particles is 9% within a particle size range of ± 40% of the average particle size.
A so-called monodisperse emulsion containing 0%, preferably 95%, is preferable.

In the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a nearly uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, ruthenium salt in at least one of the grain forming process and the growing process. It is preferable to add a complex salt containing an element of Groups 3 to 13 of the periodic table such as an osmium salt, an iron salt, a copper salt, a platinum salt, and a palladium salt. As the ligand of these complex salts, a halogen atom, a nitrosyl group, a cyano group, an aquo group, an alkyl group, a pseudohalogen group, an alkoxy group, an ammonium group, and any combination thereof can be used.
The surface of the silver halide grains can be controlled in the halogen composition by using a water-soluble halide or silver halide fine grains. This technique is known in the art as conversion and is widely known.

The silver halide grains may be uniform from the inside to the surface, or may be composed of a plurality of layers having different halogen compositions, dopant species and amounts, distribution of lattice defects and the like. In the present invention, as the silver halide grains, particle size, sensitivity, crystal habit, photosensitive wavelength, halogen composition, monodispersity, amount and type of doping agent, potential, pH, desalting method and other production conditions, surface A plurality of types of particles having different states, chemically sensitized states, and the like can be used in combination. In that case,
These silver halide grains may be contained in the same layer, or may be contained in a plurality of different layers.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (RD).
176, 17643, 22-23 (December 1978)
Monthly) or cited.

The silver halide emulsion of the present invention can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used are cyanine, merocyanine, complex cyanine,
Included are complex merocyanines, holopolar cyanines, hemicyanines, styryl dyes and hemioxonol dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole , Quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.
In the merocyanine or complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,4-
A 5- or 6-membered heterocyclic ring such as a dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

The sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles,
Bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-
Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazoline thione; azaindenes such as triazaindenes, tetrazaindenes (particularly 4-hydroxy-substituted-1,3,3) 3a, 7-Tetrazaindenes), pentazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, potassium bromide and the like. Can be added. Particularly preferred is a substituted or unsubstituted heterocycle or heterocondensed ring containing any of N, O, S and Se, and a water-soluble halide.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalic acids (mucochloric acid, phenoxymucochloric acid and the like) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin , Isocyan Over preparative acids, the carboxyl group activated hardeners, etc., may be used alone or in combination.

The light-sensitive emulsion layer and / or the non-light-sensitive hydrophilic colloid layer of the present invention may be used for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , Polyvinyl alcohol partial acetal, poly-N-
Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability, reducing silver sludge and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth)
Acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, alone or in combination thereof, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, A polymer having a combination of hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used. A monomer having a plurality of ethylenically unsaturated groups may be used as a monomer component.

These monomers may have a water-soluble group such as a hydroxyl group, a sulfone group, a carboxyl group and an amide group, and may have a primary to quaternary amino group, a phosphonium group, an aliphatic group, an aromatic group, --NR. ₁ NR ₂ —R ₃ (R ₁ , R ₂ , and R ₃ may be different from each other, a hydrogen atom, an aliphatic group, an aromatic group, a sulfinic acid residue, a carbonyl group, an oxalyl group,
Carbamoyl group, amino group, sulfonyl group, sulfoxy group, iminomethylene group, alkenyl group, alkynyl group,
An arbitrary group bonded through an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, etc.), a cation group, or the like. As a synthesis method, in addition to a usual synthesis method, polymerization may be performed in the presence of a water-soluble organic substance such as gelatin or polyvinyl alcohols. After completion of the synthesis, shelling may be performed with gelatin or a silane coupling agent.

Various other additives are used in the light-sensitive material used in the present invention. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, colloidal silica, and the like can be used. Regarding these additives, specifically, those described in RD-17643 (December 1978) can be used.

The silver halide photographic light-sensitive material of the present invention is a multilayer having two or more emulsion layers. In the case of multiple layers, an intermediate layer or the like may be provided between them. Further, it is composed of at least one non-photosensitive hydrophilic colloid layer.
The non-photosensitive hydrophilic colloid layer is an arbitrary number of layers between the support and the emulsion layer closest to the support, between the plurality of emulsion layers, and outside the emulsion layer farthest from the support. Can be provided. In these layers, a state in which a water-soluble or water-insoluble dye, an imagewise or non-imagewise development adjusting (suppression or acceleration) agent, a contrasting agent, a physical property adjusting agent, etc. are dissolved in an aqueous solution or an organic solvent, Alternatively, it can be contained in a form dispersed in solid fine particles (which may or may not be protected by oil). The emulsion layer may be one side or both sides with respect to the support. Even on one side, an arbitrary number of hydrophilic or non-hydrophilic layers can be provided in combination on the opposite side. In particular, if a layer of a hydrophobic polymer is provided outside the hydrophilic colloid layer with respect to the support pair, the drying property can be improved.

In the light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Useful as flexible supports are films of synthetic polymers of cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polyethylene terephthalate (which may contain colored contents), polyethylene or Examples include paper supports coated with polymers such as polyethylene terephthalate. These supports are magnetic recording layers,
You may have an antistatic layer and a peeling layer.

In the image forming method of the silver halide photographic light-sensitive material of the present invention, the pH of the developer is 9.5 to 11.2.
Is processed to form an image having a gamma (γ) of 10 to 30. The gamma (γ) here means the tangent of the densities of 0.1 and 3.0. The present invention is an image forming method in which the pH of the developer is preferably processed in the range of 9.5 to 10.8 and gamma (γ) of 12 to 30 is obtained.

The developing agents that can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone,
2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc., 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1- Phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol,
2,4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3 -Aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl)-
3-aminopyrazoline, etc.), transition metal complex salts (Ti,
It is a complex salt of a transition metal such as V, Cr, Mn, Fe, Co, Ni or Cu, and these may be in a form having a reducing power to be used as a developing solution. For example, Ti ³⁺ , V ²⁺ , Cr
^It takes the form of a complex salt of ²⁺ , Fe ^2+, etc., and as the ligand, an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) and salts thereof, hexametapolyphosphoric acid, tetrapolyphosphoric acid Examples thereof include phosphoric acids such as acids and salts thereof. ), Etc., can be used alone or in combination, a combination of 3-pyrazolidones and dihydroxybenzenes, or a combination of aminophenols and dihydroxybenzenes or a combination of 3-pyrazolidones and ascorbic acids, A combination of aminophenols and ascorbic acid, a combination of 3-pyrazolidones and transition metal complex salts,
It is preferable to use a combination of aminophenols and transition metal complexes. The developing agent is usually 0.01 to
It is preferably used in an amount of 1.4 mol / l.

In the present invention, as a silver sludge inhibitor, Japanese Patent Publication No. 62702/1987, JP-A-3-51844,
4-26838, 4-362942, 1-3
Examples thereof include compounds described in No. 19031.

The developing waste liquid can be regenerated by energizing it. Specifically, a cathode (for example, an electric conductor or a semiconductor such as stainless steel wool) is placed in a developing waste solution, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in an electrolyte solution, and anion exchange is performed. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the membrane, and both electrodes are energized for regeneration. The light-sensitive material according to the present invention can be processed while energizing. At that time, various additives added to the developer, for example, a preservative, an alkali agent, a pH buffer, a sensitizer, an antifoggant, a silver sludge inhibitor which can be added to the developer are additionally added. You can do it. In addition, there is a method of processing the photosensitive material while supplying electricity to the developing solution. In this case, an additive that can be added to the developing solution as described above can be added. In the case where the waste developer is recycled, the transition agent complex is preferably used as the developing agent of the developer used.

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter.

If necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (for example, carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) may be added to the developer. , Solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.),
Surfactants, defoamers, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), and a development accelerator (for example, US Pat.
No. 025, JP-B-47-45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent. The pH of the developer is preferably adjusted to 8.5 to 12.0, particularly preferably 9.0 to 10.9.

The developing solution used in the processing of the silver halide photographic light-sensitive material of the present invention may contain substantially no dihydroxybenzene compound. In this case, it is preferable that the compound represented by the following general formula (A) is contained.

[0178]

Embedded image

In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, and R ₁ and R ₂ are mutually They may combine to form a ring. k represents 0 or 1, and k
When is 1, X represents a -CO- or -CS- group. M ₁ ,
Each M ₂ represents a hydrogen atom or an alkali metal atom.

In the present invention, R ₁ and R ₂ in the above formula are
Compounds represented by the following general formula (A-a) in which are bonded to each other to form a ring are preferable.

[0181]

Embedded image

In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, It represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ have the same meaning as in formula (A).

The alkyl group in formula (A) or (A-a) is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group or a lower group. An amino group substituted with an alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent, Examples of the substitutable group include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group, and the like.

The general formula (A) or (A-
Specific examples of the compound represented by a) are shown below, but the invention is not limited thereto.

[0185]

Embedded image

[0186]

Embedded image

These compounds are typically ascorbic acid or erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods.

The amount of reductone used is 0.05 to 120 g, preferably 10 to 60 g, per liter of developer.
More preferably, it is 40 to 50 g. The general formula (A)
Alternatively, examples of the auxiliary developer which exhibits superadditivity with the developer represented by (Aa) include a 3-pyrazolidone derivative and a p-aminophenol derivative.

In the method of processing a silver halide photographic light-sensitive material of the present invention, a developer containing substantially no hydroquinone (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, hydroquinone monosulfonate, etc.) is used. Can be The term "substantially free from" means an amount of less than 0.01 mol per liter of the developing solution.

In the present invention, a developing agent comprising the transition metal complex salt according to the present invention and 3-pyrazolidones (for example, 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones and aminophenols are usually used in an amount of 0.01 to 1.4 per liter of developer.
It is preferably used in molar amounts.

In the processing method of the silver halide photographic light-sensitive material of the present invention, the developer contains a compound represented by the following formula (S).

General formula (S) Z ₁ -SM _{1 In the} formula, Z ₁ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a SO ₃ M group or a —COOM group (M is a hydrogen atom, Alkali metal atom or substituted or unsubstituted ammonium group), substituted or unsubstituted amino group, substituted or unsubstituted ammonio group, at least one selected from the group consisting of or at least one selected from this group Represents what has been replaced by. M ₁ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted amidino group (which may form a hydrohalide salt or a sulfonate salt).

As a special form of the development processing of the light-sensitive material of the present invention, it is used as an activator processing solution containing a developing agent in a light-sensitive material, for example, an emulsion layer, and processing the light-sensitive material in an alkaline aqueous solution for development. May be. Such development processing is often used as one of the rapid processing methods for photosensitive materials in combination with silver salt stabilization processing using thiocyanate, and can be applied to such processing solutions. In the case of such rapid processing, the effect of the present invention is particularly large.

As the fixing solution, those having a generally used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, etc. can be added to the fixing solution. The fixing solution optionally contains compounds such as a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), and a chelating agent capable of softening water. be able to. In the development processing, washing is performed after fixing, and the washing layer may be a method in which fresh water is supplied at a rate of several liters per minute depending on the processing, or the washing water is circulated.
A method of reusing after treating with a chemical, a filter, ozone, light, or the like, or a method of replenishing a small amount of a stabilizing solution in accordance with a treatment amount by using a washing bath as a stabilizing bath containing a stabilizer is used. This step is usually at room temperature, but it may be heated to 30 ° C to 50 ° C. In addition, when a stabilizing bath is used, it is possible to perform a pipeless treatment that does not need to be directly connected to the water supply. A rinsing bath can be provided before and after each treatment layer.

The mother liquor or replenisher of the developing solution, fixing solution, stabilizing solution is usually supplied by diluting the working solution or the concentrated solution immediately before. The stock of the mother liquor or the replenishing liquid may be in the form of a working liquid, a concentrated liquid, a viscous liquid having a high viscosity in a semi-kneaded state, or a system in which a simple substance or a mixture of solid components is dissolved at the time of use. When a mixture is used, a method in which components that are difficult to react with each other are adjacently packed in layers and then vacuum-packaged, and then opened and dissolved at the time of use, or a method of tableting can be used. In particular, the method of adding the tablet-formed product to the dissolution layer or the direct treatment layer is a workability,
The method is extremely excellent in terms of space saving and preservability, and can be used particularly preferably.

In the development processing of the present invention, the development temperature can be set within a usual temperature range of 20 to 50 ° C. The black-and-white light-sensitive material according to the present invention is preferably processed using an automatic processor. At this time, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material. The development replenishment amount and the fixing replenishment amount are 300 ml or less per 1 m ² in order to reduce the amount of waste liquid. Preferably it is 75 to 200 ml per m ² .

In the present invention, when processing is carried out using an automatic processor due to the demand for shortening the developing time, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out to the drying zone is It is preferably 10 to 150 seconds. The total processing time referred to here includes all process times required for processing the black-and-white light-sensitive material, and specifically, for processing, for example, developing, fixing, bleaching, washing, stabilizing, drying, etc. Time including all process time, that is, D
It is the time of ry to Dry.

In the drying zone of the automatic processor, a method of drying with hot air is usually used. However, a heat transfer member having a temperature of 90 ° C. or higher (for example, a heat roller of 90 ° C. to 130 ° C.) or a temperature of 150 ° C. or higher is used. Radiation object (for example, tungsten, carbon, nichrome, mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc., to directly generate electric current and radiate heat. That has a zone for drying by transmitting the infrared rays to the radiator to generate heat and emitting infrared rays), or those equipped with a known drying means such as a dehumidifier, a microwave generator, and a water absorbent resin. . Further, a control mechanism for a dry state may be provided.

[0200]

EXAMPLES Hereinafter, the effects of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A1) An average diameter of 70 mol% silver chloride and the balance silver bromide of 0.0
9 μm silver chlorobromide core particles were prepared. When the core particles were mixed, K ₃ Rh (N0) ₄ (H ₂ O) ₂ was added in an amount of 7 × 10 ^-8 mol per 1 mol of silver per 1 mol of silver and K ₃ Os.
Cl ₆ at 40 ° C., pH in the presence of 8 × 10 ⁻⁶ mol addition
While maintaining the silver potential (EAg) at 165 mV at 3.0, the silver nitrate aqueous solution and the water-soluble halide solution were simultaneously mixed.

To this core particle, EAg was added to the salt by 125 m.
V and shelled using a double jet method. At that time, K ₂ IrCl ₆ was added to the halide solution in an amount of 3 × 10 ⁻⁷ per mol of silver.
And 9 × 10 ⁻⁸ mol of K ₃ RhCl ₆ . Further, KI conversion was performed using silver iodide fine particles, and the obtained emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide having an average diameter of 0.15 μm (silver chloride: 70 mol%,
(A silver iodobromide 0.2 mol%, the balance being silver bromide). Then, a modified gelatin described in JP-A-2-280139 (in which an amino group in gelatin is substituted with phenylcarbamyl, for example, as disclosed in JP-A-2-28013)
No. 9, 287 (3) (exemplified compound G-8) and desalted. The EAg after desalting was 190 mV at 50 ° C.

In the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.5 × 10 ^-3 mol per mol of silver, and potassium bromide in an amount of 8.5 × 10 5.
PH 5.6, EAg12 with addition of ^-4 mol and citric acid
After adjusting to 3 mv, 1 × 10 ⁻³ mol of p-toluenesulfonylchloroamide sodium trihydrate (chloramine T) was added and reacted, and then inorganic sulfur S8 dispersed in solid
An appropriate amount of a compound (a mixture of sulfur methanol solution and water and dispersed to an average particle size of 0.3 μm) and chloroauric acid were added in an amount of 1.
5 × 10 ⁻⁵ mol was added and chemical ripening was carried out at a temperature of 55 ° C. until the maximum sensitivity was obtained.
0mg, 5mg of trihexylamine was added, and further 40 ℃
After cooling to 4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene was added in an amount of 2 × per mole of silver.
10 ^-3 mol, 3 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and 5 × 10 ^-3 addition of potassium iodide.
After the molar addition, the pH was adjusted to 5.1 with citric acid.

(Preparation of silver halide emulsion A2) With respect to silver halide emulsion A1, the reaction temperature was raised to 50 ° C. to make the grain size 0.19 μm, and K ₃ RhCl ₆ in the shell portion was added to 6 × 10.
Except that the ^-8 mol exactly the same silver halide emulsion A
2 was prepared. With the same chemical sensitization, the emulsion of A2 is 40% faster than the emulsion of A1.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner containing hydrazine derivative) The following two patterns were coated on a support.

(A) A gelatin subbing layer, a silver halide emulsion layer having the following Formulation 2 thereon, a silver halide emulsion layer having a Formulation 3 thereon, and a protective layer having a Formulation 4 thereon, which were simultaneously multilayer coated. .

(B) A gelatin subbing layer, a silver halide emulsion layer having the following formulation 2 thereon, a Latin layer having the same formulation as the gelatin subbing layer thereon, and a silver halide emulsion layer having a formulation 3 thereon, Furthermore, a protective layer of Formulation 4 was simultaneously and multilayer coated thereon.
The following materials according to the present invention were used for each prescription.

On the subbing layer of the support on the side opposite to the emulsion layer, a backing layer having the following formulation 5 was added in an amount of 1.5 g of gelatin.
/ M ² and a backing protective layer of the following formulation 6 on the emulsion layer side so that the amount of gelatin is 0.8 g / m ² and the curtain coating method at a speed of 200 m / min. After simultaneous multilayer coating and cooling setting, the backing layer side was simultaneously multilayer coated, cooled and set at -1 ° C, and both surfaces were simultaneously dried to obtain a sample.

[0209] Formulation 1 (gelatin subbing layer composition) Gelatin 0.45 g / m ² Saponin 56.5 mg / m ² sodium polystyrenesulfonate (average molecular weight 500000) 15 mg / m ² fungicide z 0.5 mg / m ² Formulation 2 (Composition of silver halide emulsion layer 1) Gelatin 0.65 g / m ² Silver halide emulsion A1 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye d-1 200 mg / Ag 1 mol Hydrazine compound H-1 2 × 10 ^-3 mol / Ag 1 mol Amino compound AM-1 7 mg / m ² redox compound Compound a shown in Table 1 100 mg / m ² 2-pyridinol 1 mg / m ² Polymer latex L1 (particle size 0.25 μm) 0.25 g / m ² hardener h1 5 mg / m ² sodium - iso - amyl -n- decyl sulfosuccinate 0.7 mg / m ² naphthalenesulfonic acid sodium 8 mg / m ² Saponin 20 mg / m ² hydroquinone 20 mg / m ² 2-mercapto-6-hydroxy-purine 2 mg / m ² 2-mercapto pyrimidine 1 mg / m ² Colloidal silica (average particle size 0.05μm) 150mg / m ² of ascorbic acid 20 mg / m ² EDTA 25 mg / m ² sodium polystyrene sulfonate 15 mg / m ² Coating solution pH was 5.2.

The redox compound was used after being dispersed by the following dispersing method.

(Method of Dispersing Redox Compound) Redox compound 2 g Ethyl acetate 80 g The redox compound is dissolved according to the above formulation and mixed with the following gelatin solution.

10% TK-AX (manufactured by Takemoto Yushi Co., Ltd.) 6 g 15% aqueous gelatin 180 g After preliminarily dispersing the mixed liquid at 40 ° C. for 5 minutes with a homogenizer, the main dispersion was carried out and the pressure was reduced to 130 mmHg to remove ethyl acetate. Remove. Make up to 280g with water.

Formulation 3 (composition of silver halide emulsion layer 2) Gelatin 0.65 g / m ² Silver halide emulsion A2 Silver amount 1.5 g / m ² equivalent amount Sensitizing dye d-2 300 mg / Ag 1 mol Hydrazine compound H -2 4 x 10 ^-3 mol / Ag 1 mol Amino compound AM-1 7 mg / m ² redox compound Sodium-iso-amyl-n-decylsulfosuccinate 1.7 mg / m ² 2-mercapto-6- shown in Table 2 Hydroxypurine 1 mg / m ² Nicotinic acid amide 1 mg / m ² Gallic acid n-propyl ester 50 mg / m ² Mercaptopyrimidine 1 mg / m ² EDTA 50 mg / m ² Styrene-maleic acid copolymer (molecular weight 70,000) 10 mg / m ² Polymer latex L2 <Compound described in Example 3 of JP-A-5-66512, type Lx-3 composition (9)> 0.25 / M ² Colloidal silica (average particle size 0.05 .mu.m) 150 mg / m ² gelatin with a phthalated gelatin, pH of the coating solution is 4.
It was 8.

Formulation 4 (Emulsion protective layer composition) Gelatin 1.3 g / m ² Amino compound AM-1 14 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² Matting agent: Average particle size 3 0.5 μm spherical polymethylmethacrylate 25 mg / m ² average particle size 8 μm indeterminate silica 12.5 mg / m ² surfactant S1 26.5 mg / m ² lubricant (silicone oil) 4 mg / m ² compound a 50 mg / m ² Polymer latex L4 (particle size 0.10 μm) 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² dye f1 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener h2 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Bactericide z 0.5 mg / m ² Prescription 5 (Back Layer composition) Gelatin 0.6 g / m ² Sodium-iso-amyl-n-decylsulfosuccinate 5 mg / m ² Polymer latex L3 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 100 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Dye f1 65 mg / m ² Dye f2 15 mg / m ² Dye f3 100 mg / m ² 1-Phenyl-5-mercaptotetrazole 10 mg / m ² Hardener h3 100 mg / m ² Zinc hydroxide 50 mg / M ² EDTA 50 mg / m ² Formulation 6 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: Monodisperse polymethylmethacrylate with average particle size 5 μm 50 mg / m ² Average particle size 3 μm Indeterminate silica 12.5 mg / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² interface Activator S1 1 mg / m ² dye f1 65 mg / m ² dye f2 15 mg / m ² dye f3 100 mg / m ² compound a 50 mg / m ² hardening agent h2 20 mg / m ² sodium polystyrene sulfonate 10 mg
In the case of adding / m ² solid disperse dye, Dye Exemplified SF2 was dissolved in an alkali, and then 1.2 times equivalent amount of citric acid was added to the acid group for acid precipitation. Other dyes (including those after Example 2) were dispersed with ZrO beads to obtain a powder dispersion having a particle size of 0.1 μm.

[0215]

Embedded image

[0216]

Embedded image

[0219]

Embedded image

(Developer composition) Diethylene-triamine pentaacetic acid / 5 sodium salt 1 g per 1 liter of solution used 1 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g hydroquinone 20 g 1-phenyl-4-methyl-4-hydroxymethyl -3-Pyrazolidone 0.85 g Potassium bromide 4 g 5-Methylbenzotriazole 0.2 g Boric acid 8 g Diethylene glycol 40 g 8-Mercaptoadenine 0.3 g KOH was added so that the pH of the working solution was 10.4.

(Composition of fixing solution) Per 1 liter of working solution Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Sulfuric acid Aluminum (27% aqueous solution) 25 ml With sulfuric acid, the pH of the working solution was adjusted to 4.9.

The followings were evaluated for the obtained samples.

(Processing Conditions) (Process) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Washing at room temperature 20 seconds Squeeze / drying 50 ° C. 30 seconds Total 100 seconds In addition, a film 1 m as a running processing developer is used. While replenishing 120 ml each of the developing solution and the fixing solution per ² days, 100 sheets of large-size films in which 80% of the area was blackened were processed per day, and this was carried out for 8 days to process 800 sheets in total. The obtained developing solution was used as a running solution and compared with the developing solution before running.

(Evaluation of Sensitivity and Gamma) For exposure, step exposure was performed with a laser sensitometer using a HeNe laser of 633 nm as a light source while changing the light amount at 1.5 × 10 ⁻⁷ seconds, and Konica was developed under the above developing conditions. Automatic developing machine GR-2
Processing was carried out at 7.

The developed sample thus obtained was measured with PDA-65 (Konica Digital Densitometer).

The sensitivities in the table are for the sample No. The relative sensitivity was expressed assuming that the sensitivity at a density of 1 was 2.5 at 100.
Also, gamma is expressed by the tangent of density 0.1 and 3.0,
It is shown that a super-high contrast image can be obtained only when the gamma value in the table is 10 or more.

(Evaluation method of dot reproducibility) The dot reproducibility is S
G-747RU has a 8 μm random pattern halftone dot (F
When the exposure amount is changed with M screen) and the processing is performed under the above conditions, the theoretically 2% portion is actually reproduced to 2%, but the theoretically 95% point is what percentage. Whether or not it was measured in a dot% measurement mode of an X-Rite 361T densitometer (manufactured by Konica [Co.]).
The measured value is preferably close to 95%.

(Evaluation of Black Spots) The obtained developed sample was visually evaluated using a magnifying glass of 100 times, and was classified into 5 grades of 5, 4, 3, 2, 1 in the order of less black spots. Ranked. Ranks 1 and 2 are levels that are not practically desirable. The details of the film samples are shown in Tables 1 and 2 below, and the obtained results are shown in Table 3.

[0227]

[Table 1]

[0228]

[Table 2]

[0229]

[Table 3]

As is clear from the results shown in Table 3, the samples of the present invention are less likely to cause a decrease in sensitivity, gamma, and black spots, and
It can be seen that the dot reproducibility is excellent. Further, it can be seen that the sample of the present invention has less deterioration in sensitivity and gamma and generation of black spots even in severe running treatment, and has less deterioration in halftone dot reproducibility.

[0231]

As demonstrated in the examples, according to the present invention, there is little deterioration in sensitivity and softening even during the running process, the reproducibility of fine halftone dots is excellent, and there are few black spot defects in silver halide photography. A photosensitive material and an image forming method thereof are obtained.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having at least two silver halide emulsion layers and at least one non-photosensitive hydrophilic colloid layer on one surface of a support,
At least one layer of the silver halide emulsion layer and / or the non-photosensitive hydrophilic colloid layer contains a water-soluble dye and a dye dispersed in a solid state, and the silver halide emulsion layer and / or
Alternatively, a silver halide photographic light-sensitive material containing a hydrazine derivative in a non-light-sensitive hydrophilic colloid layer adjacent thereto. 2. The reflection density of the layer containing the dye dispersed in a solid state is 0.05 to 1.0, and the transmission density of the layer containing the water-soluble dye is 0.05 to 1.0. 2. The silver halide photographic light-sensitive material according to claim 1, wherein 3. The silver halide photographic light-sensitive material according to claim 1, wherein the solid-state dispersed dye is contained in the non-photosensitive hydrophilic colloid layer. 4. The layer containing a dye dispersed in a solid state is a layer closer to a support than a layer containing a water-soluble dye, according to claim 1. Silver halide photographic light-sensitive material. 5. The emulsion layer closest to the support and / or the non-photosensitive hydrophilic colloid layer adjacent to the emulsion layer contains a redox compound which is oxidized to release a development inhibitor. 4. The silver halide photographic light-sensitive material as described in any one of 4 above. 6. The silver halide photographic light-sensitive material according to any one of claims 1 to 5 is treated with a developer having a pH of 9.5 to 11.2, and γ is 10 to 30. A method for forming an image on a silver halide photographic light-sensitive material.