JPH0682203B2 - Photothermographic material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photothermographic material which forms an image by heat development, and in particular, a heat capable of forming a dye by a coupling reaction with an oxidant of a developing agent by heat development. The present invention relates to a photothermographic material containing a coupler suitable for development.

BACKGROUND OF THE INVENTION Conventionally known photographic methods using photosensitive silver halide are superior to other photographic methods in terms of photosensitivity, gradation and image storability, and have been most widely put into practical use. It is a photography method.

However, in this method, since a wet processing method is used for processing steps such as development, fixing, and washing with water, the processing takes time and labor, and there is concern that the processing chemicals may affect the human body, or the processing room or work There are many problems such as concern about contamination of the person by the above-mentioned chemicals, and consideration of pollution caused by waste liquid. Therefore, it has been desired to develop a light-sensitive material that uses light-sensitive silver halide and can be dry-processed.

Although many proposals have been made regarding the above dry processing photographic method, a photothermographic material capable of performing a developing step by heat treatment has been attracting attention as a photosensitive material satisfying the above demand.

For such a photothermographic material, for example, Japanese Patent Publication No. 43-4
Nos. 921 and 43-4924 disclose the same, and a light-sensitive material comprising an organic silver salt, a silver halide and a reducing agent is disclosed.

Attempts have been made to improve the photothermographic material and obtain a color image by various methods.

For example, in U.S. Pat. Nos. 3,531,286, 3,761,270 and 3,764,328, a heat-developable color light-sensitive material for forming a color image by reacting an oxidant of an aromatic primary amine developing agent with a coupler. Is disclosed.

Research Disclosure No. 15108 and 1
Japanese Patent No. 5127 discloses a heat-developable color light-sensitive material which forms a color image by reacting an oxidized product of a sulfonamidephenol or sulfonamideaniline derivative developing agent with a coupler.

However, the couplers used in the photothermographic materials disclosed in these publications, particularly the cyan couplers, have the drawback of remarkably poor color developability,
Further, it has been difficult to obtain a satisfactory color forming property even with a cyan coupler which is currently used in a normal silver halide color light-sensitive material.

[Object of the Invention] An object of the present invention is to solve the problems that the above-described cyan coupler for a photothermographic material has.

That is, an object of the present invention is to provide a cyan coupler having good color forming property and less fog, and a photothermographic material having the cyan coupler.

[Structure of the Invention] The inventors of the present invention have conducted extensive studies to achieve the above object. As a result, the above object of the present invention is to provide at least a photosensitive silver halide, an organic silver salt, a reducing agent, a binder and It has been found that this can be achieved by a photothermographic material containing a coupler represented by the general formula (1).

General formula (1) In the formula, Z represents an atomic group necessary for forming a benzene ring or a naphthalene ring, R ₁ represents an alkyl group or a hydrogen atom, R ₂ represents a hydrogen atom, an aliphatic group or an aromatic group, and R ₃ And R ₄ each represent a hydrogen atom or a substituent, a represents an integer of 1 or 2, and when a is 2, R ₃ may be the same or different. b represents an integer of 1 or 2 when Z forms a benzene ring;
When forming a naphthalene ring with, b represents an integer of 1 to 6, and when b is 2 to 6, R ₄ may be the same or different. However, in R ₂ , R ₃ and R ₄ , all are not hydrogen atoms, and at least one substituent is a ballast group.

[Specific Structure of the Invention] When Z represents an atomic group necessary for forming a benzene ring in the general formula (1), the cyan coupler represented by the general formula (1) is preferably the following general formula (2). ) And Z represents an atomic group necessary for forming a naphthalene ring, the cyan coupler represented by the general formula (1) is preferably represented by the following general formula (3).

General formula (2) General formula (3) In the general formula (2) and (3), R ₁ and R ₂ have the same meanings as R ₁ and R ₂ in the general formula (1). That is, R ₁ is an alkyl group or a hydrogen atom. In, when R ₁ is a hydrogen atom, Represents a salt thereof, for example, an alkali metal salt or an ammonium salt), and R ₂ represents a hydrogen atom, an aliphatic group or an aromatic group.

Examples of the alkyl group represented by R ₁ include an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group and an n-butyl group. The alkyl group includes those having a substituent, and the substituent is, for example, a phenyl group or an alkoxy group. R ₁ is preferably a hydrogen atom.

The aliphatic group represented by R ₂ is preferably an alkyl group (eg, methyl group, ethyl group, n-propyl group, n-butyl group, etc.), and the aromatic group is represented by an aryl group (eg, phenyl group). Preferably, the aliphatic group and aromatic group represented by R ₂ may have a substituent, and R ₂ may be a ballast group.

R ₅ , R ₆ and R _{7 in the} general formula (2) each represent a hydrogen atom or a substituent, and not all R _{5 to} R ₇ are hydrogen atoms.

R _{8 in the} general formula (3) represents a substituent.

However, at least one of the substituents represented by R ₅ , R ₆ and R ₇ in the general formula (2) and the substituent represented by R ₈ in the general formula (3) are each a ballast group.

In the general formula (2), examples of the substituent represented by R ₅ , R ₆ and R ₇ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, An acylamino group,
Alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, cyano group, nitro group, sulfonyl group, ureido Group, sulfamoylamino group, sulfonyloxy group, sulfonamide group, alkylthio group,
Examples thereof include an arylthio group, an imide group, a heterocyclic residue, and a halogen atom.

Further, these substituents are further an ethylenically unsaturated group, a group having an ethylenically unsaturated group, a hydroxyl group, an alkoxy group,
Cyano group, nitro group, alkyl group, cycloalkyl group,
Aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, sulfo group,
It may be substituted with a carboxy group, an acylamino group, an alkylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a sulfamoylamino group, an imide group, a halogen atom and the like.

The substituent represented by R ₈ is a group capable of forming a ballast group among the substituents represented by R _{5 to} R ₇ .

Examples of the halogen atom represented by R _{5 to} R ₈ include a chlorine atom and a bromine atom, and a chlorine atom is particularly preferable.

The alkyl group represented by R _{5 to} R ₈ has 1 to 32 carbon atoms.
And alkenyl groups having 2 to 32 carbon atoms, and cycloalkyl groups having 3 to 12 carbon atoms, especially 5 to 7 carbon atoms, and the alkyl group and alkenyl group may be linear or branched.

Examples of the aryl group represented by R _{5 to} R ₈ include a phenyl group and the like.

The alkoxy group represented by R _{5 to} R ₈ may be further substituted, and examples thereof include a methoxy group, a propoxy group and 2-
Examples thereof include an ethoxyethoxy group, a pentadecyloxy group, a 2-dodecyloxyethoxy group, and a phenethyloxyethoxy group.

The aryloxy group represented by R _{5 to} R ₈ may be further substituted, for example, a phenoxy group, p-t-
Examples thereof include a butylphenoxy group and an m-pentadecylphenoxy group.

Examples of the acyl group represented by R _{5 to} R ₈ include an acetyl group, a phenylacetyl group, a dodecanoyl group, and α-2,4-di-t.
Examples thereof include an alkylcarbonyl group such as an amylphenoxybutanoyl group, a benzoyl group, a 3-pentadecyloxybenzoyl group, and an arylcarbonyl group such as a p-chlorobenzoyl group.

Examples of the acyloxy group represented by R _{5 to} R ₈ include an alkylcarbonyloxy group and an arylcarbonyloxy group, and specific examples include an acetyloxy group, an α-chloroacetyloxy group and a benzoyloxy group.

Examples of the acylamino group represented by R _{5 to} R ₈ include an alkylcarbonylamino group and an arylcarbonylamino group (preferably a phenylcarbonylamino group).
It may further have a substituent, specifically, an acetamide group,
Examples include an α-ethylpropanamide group, an N-phenylacetamide group, a dodecane amide group, a 2,4-di-t-amylphenoxyacetamide group, an α-3-t-butyl 4-hydroxyphenoxybutanamide group.

The alkoxycarbonyl group represented by R _{5 to} R ₈ may further have a substituent, for example, methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyl group, benzyl. An oxycarbonyl group and the like can be mentioned.

The aryloxycarbonyl group represented by R _{5 to} R ₈ may further have a substituent, and examples thereof include a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and an m-pentadecyloxyphenoxycarbonyl group.

Examples of the alkoxycarbonyloxy group represented by R _{5 to} R ₈ include a methoxycarbonyloxy group, a dodecyloxycarbonyloxy group, a methoxyethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

Examples of the aryloxycarbonyloxy group represented by R _{5 to} R ₈ include a phenoxycarbonyloxy group and p-
Examples thereof include a chlorophenoxycarbonyloxy group.

The alkoxycarbonylamino group represented by R _{5 to} R ₈ is
It may further have a substituent, for example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group,
Examples include octadecyloxycarbonylamino group.

The aryloxycarbonylamino group represented by R _{5 to} R ₈ may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The carbamoyl group represented by R _{5 to} R ₈ may have a substituent, for example, an N-methylcarbamoyl group, N, N-
Dibutylcarbamoyl group, N- (2-pentadecyloctylethyl) carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl group, etc. Can be mentioned.

The sulfamoyl group represented by R _{5 to} R ₈ may have a substituent, for example, an N-propylsulfamoyl group,
N, N-diethylsulfamoyl group, N- (2-pentadecyloxyethyl) sulfamoyl group, N-ethyl-N
Examples include -dodecylsulfamoyl group and N-phenylsulfamoyl group.

The amino group represented by R _{5 to} R ₈ may have a substituent, for example, an ethylamino group, a methylethylamino group,
Examples thereof include a cycloalkylamino group, an anilino group, an m-chloroanilino group, a 3-pentadecyloxycarbonylanilino group, and a 2-chloro-5-hexadecanamide anilino group.

Examples of the sulfonyl group represented by R _{5 to} R ₈ include an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group, and an arylsulfonyl group such as a phenylsulfonyl group and a p-toluenesulfonyl group.

The ureido group represented by R _{5 to} R ₈ is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group) and the like, and examples thereof include N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group,
Np-tolyl ureido group etc. are mentioned.

The sulfamoylamino group represented by R _{5 to} R ₈ includes
It may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., for example, an N, N-dibutylsulfamoylamino group, an N-methylsulfamoylamino group,
Examples thereof include N-phenylsulfamoylamino group.

Examples of the sulfonyloxy group represented by R _{5 to} R ₈ include an alkylsulfonyloxy group such as a methylsulfonyloxy group and a dodecylsulfonyloxy group, an arylsulfonyloxy group such as a phenylsulfonyloxy group and a p-toluenesulfonyloxy group. Is mentioned.

Examples of the sulfonamide group represented by R _{5 to} R ₈ include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specific examples thereof include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The alkylthio group represented by R _{5 to} R ₈ may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group and a 3-phenoxypropylthio group.

The arylthio group represented by R _{5 to} R ₈ may further have a substituent, for example, a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2 Examples include -carboxyphenylthio group and p-acetaminophenylthio group.

The imide group represented by R _{5 to} R ₈ may be an open chain type or a cyclic type, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, or a phthalimide group. Group, glutarimide group and the like.

The heterocyclic group represented by R _{5 to} R ₈ is preferably a 5- to 7-membered heterocyclic group, which may be substituted or condensed. Specifically, 2-furyl group, 2-thienyl group, 2
Examples include -pyrimidinyl group and 2-benzothiazolyl group.

In the general formula (2), at least one of R ₅ , R ₆ and R ₇ and R ₈ in the general formula (3) are the above-mentioned ballast group, and R ₂ in the general formula (1) is It may be a ballast group. Here, the ballast group of the present invention refers to an organic group having a molecular size and shape that transforms the cyan coupler into a non-diffusible state in a photothermographic material having the cyan coupler during thermal development. means.
A typical example of the ballast group is an organic group having a total number of carbon atoms of 8 to 40 (more preferably 12 to 30),
Another preferred ballast group is a polymer residue.

When the ballast group is a polymer residue, the cyan coupler represented by the general formula (1) is a polymer having a repeating unit derived from a monomer substituted with an ethylenically unsaturated group or a group having an ethylenically unsaturated group. It is a cyan coupler.

As the ethylenically unsaturated group or a group having an ethylenically unsaturated group, a group represented by the following general formula (4) is preferable.

General formula (4) In the formula, R ₉ represents a hydrogen atom, a carboxy group or an alkyl group (for example, a methyl group, an ethyl group, etc.), and the alkyl group includes those having a substituent.
For example, a halogen atom (eg, fluorine atom, chlorine atom, etc.), a carboxy group, etc. The carboxy group represented by R ₉ and the carboxy group of the substituent may form a salt.

J ₁ and J ₂ each represent a divalent linking group, and examples of the divalent linking group include —NHCO—, —CONH—, —COO.
-, -OCO-, -SCO-, -COS-, -O-, -S-, -S
O -, -, and the like - SO _2. X ₁ and X ₂ each represent a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include:
Examples of the alkylene group, an arylene group, an aralkylene group, an alkylenearylene group or an arylenealkylene group, examples of the alkylene group include a methylene group, an ethylene group and a propylene group, and examples of the arylene group include a phenylene group. The aralkylene group is a phenylmethylene group or the like, the alkylenearylene group is, for example, a methylenephenylene group or the like, and the arylenealkylene group is, for example, a phenylenemethylene group or the like. l ₁ , m ₁ , l ₂ and m ₂ each represent 0 or 1.

When the cyan coupler of the present invention is a polymer coupler, even if it is a so-called homopolymer of a repeating unit consisting of only one type of monomer coupler, it can be used as a monomeric coupler.
The copolymer may be a combination of two or more kinds, and may be a copolymer composed of at least one other comonomer having a copolymerizable ethylenically unsaturated group.

As the comonomer having an ethylenically unsaturated group capable of forming a copolymer with the cyan coupler monomer of the present invention, acrylic acid esters, methacrylic acid esters,
Vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters Examples thereof include unsaturated nitriles, polyfunctional monomers, various unsaturated acids and the like.

Further, when the cyan coupler of the present invention is a polymer formed of a coupler monomer and another monomer, the repeating unit of the cyan coupler monomer of the present invention is preferably 10% by weight of the total polymer. ˜90% by weight, and more preferably 30 to 70% by weight.

Typical representative examples of the cyan coupler represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto.

Exemplified compound And butyl acrylate (hereinafter referred to as BA) copolymer composition ratio = coupler / BA = 6/4 weight average molecular weight (▲ ▼) = 24,600 Copolymer of BA and BA Composition ratio = Coupler / BA = 5/5 ▲ ▼ ＝ 19,500 And ethyl acrylate (hereinafter referred to as EA) copolymer composition ratio = coupler / EA = 6/4 ▲ ▼ = 16,800 Copolymer of BA and BA Composition ratio = Coupler / BA = 7/3 ▲ ▼ = 21,200 Copolymer of BA and BA Composition ratio = Coupler / BA = 4/6 ▲ ▼ ＝ 12,900 Copolymer of BA and BA Composition ratio = Coupler / BA = 5/5 ▲ ▼ ＝ 18,300 Copolymer of styrene and styrene (hereinafter referred to as St) Composition ratio = Coupler / St = 5/5 ▲ ▼ = 9,800 Copolymer of BA and BA Composition ratio = Coupler / BA = 5/5 ▲ ▼ = 35,600 Copolymer of BA and BA Composition ratio = Coupler / BA = 7/3 ▲ ▼ = 16,700 A typical synthesis example of the cyan coupler represented by the general formula (1) of the present invention will be shown.

Synthesis Example-1 Synthesis of Exemplified Compound C-1 14.3 g of 2-amino-4,6-dichloro-5-methylphenol hydrochloride was added to a mixed solvent of 150 ml of acetonitrile and 30 ml of pyridine, and 27.5 g of dodeca was added with stirring. After adding noyl chloride dropwise and stirring at room temperature for 3 hours, the reaction solution was cooled with ice water.
It was added to 500 ml and the precipitate was filtered off. This solid was added to 200 ml of water containing 15 g of potassium hydroxide, stirred for 1 hour at room temperature, then poured into 200 ml of water containing 24 ml of concentrated hydrochloric acid, and the precipitated crystals were separated by filtration.

22.2 g of the crystals were dispersed in 150 ml of acetic acid, 5.2 g of sodium nitrite solution (28 ml of water) was added dropwise at about 20 ° C., and the mixture was stirred for 2 hours.
This reaction solution was added to 600 ml of water, and the precipitated crystals were filtered off,
After drying, 20.0 g of 2-dodecanoylamino-5-methyl-6-chloroquinone was obtained. 20.0 g of this quinone compound was added to 100 ml of ethanol, and hydrogen reduction was performed using palladium-carbon (hereinafter abbreviated as Pa / C) as a catalyst. After completion of the reduction, the solution was filtered to concentrate 40 ml of the filtrate, and 150 ml of acetone was added to this concentrated solution.
9 g of potassium carbonate and 7.5 g of benzyl bromide were added, and the mixture was refluxed for 7 hours under a nitrogen stream. This reaction solution is filtered and concentrated (about 50 m
l) After that, 300 ml of water was added, the precipitated solid was separated by filtration, further suspended in acetonitrile and separated by filtration to obtain 2-methyl-3-chloro-4-benzylhydroxy-5-dodecanoylaminophenol (19.3 g). It was

16.5 g of the above-mentioned phenol derivative, 5.6 g of ethyl bromoacetate
And 8.0 g of potassium carbonate in 100 ml of acetone,
Heated to reflux for hours. The reaction solution was filtered and then concentrated, dissolved in 100 ml of ethanol, hydrogen-reduced using Pa / C as a catalyst, the reaction solution was concentrated to 50 ml, and water containing 1.5 g of sodium hydroxide was added.
ml was added, and the mixture was stirred at room temperature for 6 hours and then neutralized with hydrochloric acid to obtain 12.2 g of precipitated crystals (target product).

Synthesis Example-2 Synthesis of Exemplified Compound C-11 27.4 g of (2-chloro-3-methyl-4-hydroxy-5-acetylamino) phenoxyacetic acid obtained in the same manner as in Synthesis Example-1 was added to 100 ml of methanol and 100 ml of water. , And 12 g of sodium hydroxide were added, and the mixture was heated under reflux for 5 hours and neutralized with hydrochloric acid to precipitate crystals [(2-chloro-3-methyl-
4-Hydroxy-5-amino) phenoxyacetic acid] 22.4 g
Got

This compound was reacted with methacrylic acid chloride in the same manner as in Synthesis Example-1 to obtain 21.8 g of (2-chloro-3-methyl-4-hydroxy-5-methacryloylamino) phenoxyacetic acid (coupler monomer).

150 g of the above coupler monomer 18 g and butyl acrylate 12 g
In dioxane (1), heated to 82 ° C to 84 ° C under a nitrogen stream, kept at this temperature, added 600 mg of 2,2'-azobisisobutyronitrile and reacted for 2 hours, and further added 300 mg of 2,2
2'-Azobisisobutyronitrile was added and reacted for 2 hours. After the reaction was completed, the reaction solution was poured into water (1), the precipitate was separated by filtration and dried, the solid was redissolved in 200 ml of dioxane, added to 1.2 l of water for reprecipitation, and the solid was separated by filtration and dried to obtain the desired product. Got

The coupler of the present invention may be used alone or in combination of two or more. The amount used is not limited, and depends on the type of coupler, single use or use of two or more kinds in combination, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or two or more layers. It can be decided, but for example, the usage amount is 1
0.005 g to 10 g, preferably 0.1 g to 5.0 g can be used per m ² .

The method of incorporating the coupler used in the present invention into the photographic constituent layer of the heat-developable color light-sensitive material is arbitrary, and examples thereof include low-boiling point solvents (methanol, ethanol, ethyl acetate, etc.) or high-boiling point solvents (dibutyl phthalate, dioctyl phthalate, tricret). Dispersed in ultrasonic waves or dissolved in an alkaline aqueous solution (eg, 10% sodium hydroxide solution) and then neutralized with a mineral acid (eg, hydrochloric acid or nitric acid). It can be used after being used or dispersed with an aqueous solution of an appropriate polymer (for example, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill.

The heat-developable color light-sensitive material of the present invention contains a light-sensitive silver halide together with the above-mentioned coupler.

The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples thereof include silver chloroiodobromide. The photosensitive silver halide is
Although it can be prepared by any method such as a single jet method and a double jet method in the field of photographic technology, in the present invention, a photosensitive silver halide prepared according to a usual method for preparing a silver halide gelatin emulsion is used. A light-sensitive silver halide emulsion containing the same gives favorable results.

The photosensitive silver halide emulsion may be chemically sensitized by any method in the photographic art. As such a sensitizing method,
Various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization and reduction sensitization can be used.

The silver halide in the above light-sensitive emulsion may be coarse particles or fine particles, but the preferable grain size is about 0.001 μm to about 1.5 μm, and more preferably about 0.01 μm to about 0.01 μm. It is about 0.5 μm.

The light-sensitive silver halide emulsion prepared as described above can be most preferably applied to the heat-developable light-sensitive layer which is a constituent layer of the light-sensitive material of the present invention.

In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with an organic silver salt described below to form photosensitive silver halide on a part of the organic silver salt. . As the photosensitive silver salt forming component used in this preparation method, an inorganic halide, for example, a halide represented by MXn (wherein M represents an H atom, an NH ₄ group or a metal atom, and X represents Cl, Br Or I, n
Indicates 1 when M is an H atom or an NH ₄ group, and its valence when M is a metal atom. As the metal atom, lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium,
Barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, Examples include iridium, platinum and cerium. ), A halogen-containing metal complex (for example, K ₂ PtCl ₆ , K ₂ PtBr ₆ , HAuCl ₄ , (N
H ₄ ) ₂ IrCl ₆ , (NH ₄ ) ₃ IrCl ₆ , (NH ₄ ) ₂ RuCl ₆ , (NH ₄ ) ₃ RuCl ₆ ,
(NH ₄ ) ₃ RhCl ₆ , (NH ₄ ) ₃ RhBr _6, etc.), onium halides (eg, tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium) Quaternary ammonium halides such as bromide, quaternary phosphonium halides such as tetraethylphosphonium bromide, benzylethylmethylsulfonium bromide, tertiary sulfonium halides such as 1-ethylthiazolium bromide, etc.), halogenated carbonization Hydrogen (for example, iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compound (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthale) Acid imide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfone Amide, 1,3-dibromo-4,4-dimethylhydantoin, etc.) and other halogen-containing compounds (eg triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.) You can

These photosensitive silver halide and photosensitive silver salt-forming component can be used in combination in various methods, and the amount used is
It is preferably 0.001 g to 50 g, and more preferably 0.1 g to 10 g per 1 m ² per layer.

The heat-developable color light-sensitive material of the present invention has a multi-layered structure as each layer having sensitivity to blue light, green light and red light, that is, a heat-development blue photosensitive layer, a heat-development green photosensitive layer, and a heat-development red photosensitive layer. You can also do it. Further, the photosensitive layer of the same color may be divided into two or more layers (for example, a high sensitivity layer and a low sensitivity layer).

In the above case, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion and red-sensitive silver halide emulsion used in each case are obtained by adding various spectral sensitizing dyes to the silver halide emulsion. You can

Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol and the like. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferable. Such a nucleus may have an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group or an enamine group capable of forming a condensed carbocyclic or heterocyclic ring. Good. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, a phenyl group, an enamine group or a heterocyclic substituent.

The merocyanine dye has, in addition to the basic nucleus, an acidic nucleus such as a thiohydantoin nucleus, a rhodanin nucleus, an oxazolidione nucleus, a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazoline thione nucleus, a malononitrile nucleus, and a pyrazolone nucleus. Good. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivative,
Azaindene cadmium salt, organic sulfonic acid and the like, for example, supersensitizing additives which do not absorb visible light as described in the specifications of US Pat. Nos. 2,933,390 and 2,937,089 can be used in combination.

The addition amount of these dyes is 1 × 10 ⁻⁴ to 1 mol per mol of silver halide or a silver halide-forming component. More preferably, it is 1 × 10 ^-4 mol to 1 × 10 ^-1 mol.

In the heat-developable color light-sensitive material of the present invention, various organic silver salts can be used, if desired, for the purpose of increasing sensitivity and improving developability.

Examples of the organic silver salt used in the heat-developable color light-sensitive material of the present invention include JP-B Nos. 43-4921, 44-26582 and 45-18416.
No. 45-12700, No. 45-22185, JP-A-49-52626,
52-31728, 52-137321, 52-141222, 53-3
6224 and the respective publications such as 53-37610 and U.S. Pat.Nos. 3,330,633, 3,794,496, and 4,105,451,
No. 4,123,274, silver salts of aliphatic carboxylic acids as described in each specification such as No. 4,168,980, for example, silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate. , Silver behenate, silver α- (1-phenyltetrazolethio) acetate, etc., and silver aromatic carboxylates such as silver benzoate, silver phthalate, etc.
6582, 45-12700, 45-18416, 45-22185,
JP-A-52-31728, JP-A-52-137321, JP-A-58-118638
No. 58-118639 and the like, silver salts of imino groups as described in, for example, benzotriazole silver, 5-nitrobenzotriazole silver, 5-chlorobenzotriazole silver, 5-methoxybenzotriazole silver, 4-sulfobenzotriazole silver, 4-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazole silver, 1, 2,4-triazole silver, 1
H-tetrazole silver, 3-amino-5-benzylthio-
1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., other 2-mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-
Mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,
4-triazole silver, 4-hydroxy-6-methyl-1,
Examples include silver 3,3a, 7-tetrazaindene and silver 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene. Among the above organic silver salts, the silver salt of imino group is preferable, the silver salt of benzotriazole derivative is more preferable, and the silver salt of sulfobenzotriazole derivative is more preferable.

The organic silver salt used in the present invention may be used alone or in combination of two or more kinds, and the isolated silver salt may be dispersed in a binder by a suitable means before use. The silver salt may be prepared in a binder and used as it is without isolation.

The amount of the organic silver salt used is 1 mol of photosensitive silver halide.
It is preferably 0.01 to 500 mol, more preferably
It is 0.1 mol to 100 mol.

The reducing agent used in the heat-developable color light-sensitive material of the present invention is
What is usually used in the field of heat-developable color light-sensitive materials can be used, for example, U.S. Pat.
No. 3,761,270, No. 3,764,328, RD No. 12
No. 146, No. 15108, No. 15127, and p-phenylenediamine-based and p-aminophenol-based developing agents, phosphoroamidophenol-based and sulfonamidephenol-based developing agents described in JP-A-56-27132 and the like. Further, hydrazone type color developing agents can be mentioned. Also, U.S. Pat.Nos. 3,342,599 and 3,719,492, JP-A-53-1356
No. 28, No. 54-79035 and the like, color developing agent precursors and the like can also be advantageously used.

Particularly preferred reducing agents include reducing agents represented by the following general formula (5) described in JP-A-56-146133.

General formula (5) In the formula, R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group having 1 to 30 (preferably 1 to 4) carbon atoms which may have a substituent, and R ₁₀ and R ₁₁ are ring-closed. A heterocycle may be formed. R ₁₂ , R ₁₃ R ₁₄ and R ₁₅ are each a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamide group, a sulfonamide group, an alkylsulfonamide group or a carbon atom which may have a substituent. To 30 (preferably 1 to 4) alkyl groups, R ₁₂ and R ₁₀ and R
₁₄ and R ₁₁ may each be closed to form a heterocycle.
M represents a compound containing an alkali metal atom, an ammonium group, a nitrogen-containing organic base or a quaternary nitrogen atom.

The nitrogen-containing organic base in the above general formula (5) is an organic compound containing a nitrogen atom showing basicity capable of forming a salt with an inorganic acid, and an amine compound is mentioned as a particularly important organic base. Primary amines, secondary amines, tertiary amines, and the like are used as chain amine compounds, and pyridine, quinoline, and piperidine, which are prominent examples of typical heterocyclic organic bases, are used as cyclic amine compounds. , Imidazole and the like. In addition, compounds such as hydroxylamine, hydrazine and amidine are also useful as chain amines. As the salt of the nitrogen-containing organic base, the inorganic acid salt of the above-mentioned organic base (for example, hydrochloride, sulfate, nitrate, etc.) is preferably used.

On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts and hydroxides of nitrogen compounds having a tetravalent covalent bond.

Next, preferable specific examples of the reducing agent represented by the general formula (5) are shown below.

The reducing agent represented by the general formula (5) can be obtained by a known method,
For example, Hoyben Bale, Mesodden del Organischen Chemie, band XI / 2 (Houben-Weyl, Methode
Nerder Organischen Chemie, Band XI / 2) 645-703.

Other reducing agents such as those described below can also be used.

For example, phenols (for example, p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamide phenols [for example, 4-benzene Sulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4- (p-toluenesulfonamido) phenol, etc.], or polyhydroxybenzenes (eg, Hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc., naphthols (for example, α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphtho). Le acids), hydroxy binaphthyls and methylene bis naphthols [e.g.
1,1'-dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,
6-dinitro-2,2'-dihydroxy-1,1'-binaphthyl, 4,4'-dimethoxy-1,1'-dihydroxy-2,2 '
-Binaphthyl, bis (2-hydroxy-1-naphthyl)
Methane, etc.], methylenebisphenols [eg 1,1-
Bis (2-hydroxy-3,5-dimethylphenyl) -3,
5,5-trimethylhexane, 1,1-bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, 1,
1-bis (2-hydroxy-3,5-di-tert-butylphenyl) methane, 2,6-methylenebis (2-hydroxy-
3-tert-butyl-5-methylphenyl) -4-methylphenol, α-phenyl-α, α-bis (2-hydroxy-3,5-di-tert-butylphenyl) methane, α-
Phenyl-α, α-bis (2-hydroxy-3-tert-
Butyl-5-methylphenyl) methane, 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1,5,5-tetrakis (2-hydroxy-3,5
-Dimethylphenyl) -2,4-ethylpentane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methyl-5-ter
t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-di-tert-butylphenyl) propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones and paraphenylenediamines Is mentioned.

These reducing agents may be used alone or in combination of two or more. The amount of the reducing agent used depends on the type of the photosensitive silver halide used, the type of the organic acid silver salt and the type of other additives, but is usually 0.01 per 1 mol of the photosensitive silver halide. The range is ˜1500 mol, preferably 0.1-200 mol.

As the binder used in the heat-developable color light-sensitive material of the present invention, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, phthalated gelatin, etc. One or a combination of two or more polymer substances can be used. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binders described in Japanese Patent Application No. 58-104249.

This binder contains gelatin and a vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone which is a homopolymer of vinylpyrrolidone, or a copolymer (including a graft copolymer) with one or more other monomers copolymerizable with vinylpyrrolidone. ) May be sufficient. These polymers can be used regardless of their degree of polymerization. The polyvinylpyrrolidone may be a substituted polyvinylpyrrolidone, preferred polyvinylpyrrolidone having a molecular weight of 1,000 to 400,000. Other monomers copolymerizable with vinylpyrrolidone include (meth) acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinylimidazoles, (meth) acrylamides, vinylcarbinols. , Vinyl-based monomers such as vinyl alkyl ethers, etc.,
It is preferable that at least 20% (% by weight, hereinafter the same) of the composition ratio is polyvinylpyrrolidone. Preferred examples of such copolymers have a molecular weight of 5,000 to 400,000.

The gelatin may be lime-treated or acid-treated, and may be ossein gelatin, pigskin gelatin, hide gelatin or modified gelatin obtained by esterification or phenylcarbamoylation thereof.

In the above binder, gelatin is preferably 10 to 90% of the total amount of binder, more preferably 20
-60%, polyvinylpyrrolidone is preferably 5-90%, more preferably 10-80%.

The binder may contain other polymeric substances,
Mixture of gelatin and polyvinylpyrrolidone having a molecular weight of 1,000 to 400,000 with one or more other polymeric substances, and mixture of gelatin and vinylpyrrolidone copolymer having a molecular weight of 5,000 to 400,000 with one or more other polymeric substances. Is preferred. Other polymer substances used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol,
Examples thereof include proteins such as polyethylene glycol ester and cellulose derivatives, and natural substances such as polysaccharides such as starch and gum arabic. These 0-85
%, Preferably 0-70%.

The vinylpyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable that the vinylpyrrolidone polymer is coated on the support and then crosslinked (including the case where the crosslinking reaction is allowed to stand by itself).

The amount of binder used is usually 0.05 per 1 m ² per layer.
It is g to 50 g, preferably 0.1 g to 10 g. Further, the binder is preferably used in an amount of 0.1 to 10 g, more preferably 0.25 to 4 g, based on 1 g of the coupler of the present invention.

Examples of the support used in the heat-developable color light-sensitive material of the present invention include polyethylene films, cellulose acetate films and polyethylene terephthalate films, synthetic plastic films such as polyvinyl chloride, photographic base paper, printing paper, baryta paper and resin coat. Examples thereof include paper supports such as paper, and supports in which a reflective layer is provided on the above synthetic plastic film.

In particular, various heat solvents are preferably added to the heat-developable color light-sensitive material of the present invention. The thermal solvent of the present invention may be a substance that promotes thermal development and / or thermal transfer, preferably a solid, a semi-solid or a liquid at room temperature (preferably a boiling point of 100 ° C. or higher at atmospheric pressure, more preferably 150 ° C.).
The above) is a substance which dissolves or melts in a binder when heated, and is preferably a urea derivative (eg, dimethylurea, diethylurea, phenylurea, etc.), an amide derivative (eg, acetamide, benzamide, etc.), Examples thereof include polyhydric alcohols (for example, 1,5-pentanediol, 1,6-pentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.) and polyethylene glycols. A detailed specific example is described in Japanese Patent Application No. 58-104249. These hot solvents may be used alone or in combination of two or more.

Various additives can be added to the heat-developable color light-sensitive material of the present invention, if necessary, in addition to the above components. For example, as a development accelerator, U.S. Patent Nos. 3,220,840 and 3,5
31,285, 4,012,260, 4,060,420, 4,
No. 088,496, No. 4,207,392 specifications, RD No. 15733, No.
No. 15734, No. 15776, JP-A-56-130745, 56-1323
Urea as described in No. 32 and the like, alkali-releasing agent such as guanidinium trichloroacetate, organic acids described in JP-B-45-12700, described in U.S. Pat. No. _{3,667,959 -CO -, - SO 2 -} ,
Non-aqueous polar solvates having --SO-- groups, U.S. Pat.
Melt former described in 438,776, U.S. Pat.No. 3,666,4
77 and polyalkylene glycols described in JP-A-51-19525. Further, as a color tone agent, for example, JP-A-46
-4928, 46-6077, 49-5019, 49-5020,
49-91215, 49-107727, 50-2524, 50-67132
No. 50, No. 50-67641, No. 50-114217, No. 52-33722, No. 5
2-99813, 53-1020, 53-55115, 53-76020
No. 53, No. 53-125014, No. 54-156523, No. 54-156524,
54-156525, 54-156526, 55-4060, 55-40
No. 61, No. 55-32015, etc. and West German Patent No. 2,140,
No. 406, No. 2,147,063, No. 2,220,618, U.S. Patent No.
No. 3,080,254, No. 3,847,612, No. 3,782,941, No. 3,994,732, No. 4,123,282, No. 4,201,582 Phthalazinone, which is a compound described in each specification,
Phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, 2,3-
Dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyril, sulfonamide, 2H-1,
There are 3-benzothiazine-2,4- (3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., and one or more of these and an imidazole compound A mixture of at least one of an acid or an acid anhydride such as phthalic acid and naphthalic acid and a phthalazine compound, and a combination of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid and the like. it can. Also, JP-A-58-189628 and JP-A-58-193460
3-amino-5-mercapto-1,
2,4-triazoles and 3-acylamino-5-mercapto-1,2,4-triazoles are also effective.

Further, as the antifoggant, for example, Japanese Patent Publication No.
-11113, JP-A-49-90118, 49-10724, 49-976
No. 13, No. 50-101019, No. 49-130720, No. 50-123331
No. 51, No. 51-47419, No. 51-57435, No. 51-78227, No. 51
-104338, 53-19825, 53-20923, 51-50725
No. 51, No. 51-3223, No. 51-42529, No. 51-81124, No. 54-
Publications such as 51821 and 55-93149, as well as British Patent No.
1,455,271, U.S. Pat.Nos. 3,885,968, 3,700,457
No. 4,137,079, No. 4,138,265, West German Patent No. 2,
No. 617, 907, a mercuric salt which is a compound described in each specification, or an oxidizing agent (for example, N-halogenoacetamide, N-halogenosuccinimide, perchloric acid and salts thereof, inorganic peroxides, Persulfate, etc.), or acid and salts thereof (eg, sulfinic acid, lithium laurate, rosin, diterpenic acid, thiosulfonic acid, etc.), or sulfur-containing compounds (eg, mercapto compound-releasing compound, thiouracil, disulfide, sulfur) Single,
Mercapto-1,2,4-triazole, thiazoline thione, polysulfide compound and the like), and other compounds such as oxazoline, 1,2,4-triazole and phthalimide. As another antifoggant, JP-A-59-1
The thiol (preferably thiophenol compound) compounds described in 11636 are also effective.

Examples of the antifoggant include hydroquinone derivatives described in Japanese Patent Application No. 59-56506 (for example, di-t-octylhydroquinone, dodecanylhydroquinone, etc.) and Japanese Patent Application No. 59-56506.
The combined use of the hydroquinone derivative described in -66380 and benzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used.

In addition, a printout preventing agent after treatment may be used as a stabilizer at the same time, and examples thereof include JP-A-48-45228 and JP-A-50-1.
No. 19624, No. 50-120328, No. 53-46020 and the like halogenated hydrocarbons, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo- 2-tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2,4-bis (tribromomethyl) -6-methyltriazine and the like can be mentioned.

Also, Japanese Patent Publication No. 46-5393, Japanese Patent Laid-Open Nos. 50-54329, 50-770.
Post-treatment may be carried out using a sulfur-containing compound as described in JP-A No. 34-34.

Furthermore, U.S. Pat.Nos. 3,301,678 and 3,506,444,
No. 3,824,103, No. 3,844,788 isothiuronium stabilizer stabilizer precursor described in each specification, also U.S. Patent Nos. 3,669,670, 4,012,260, 4,060,4
The activator stabilizer precursor described in the specification of No. 20 and the like may be contained.

Further, a water-releasing agent such as sucrose or NH ₄ Fe (SO ₄ ) ₂ .12H ₂ O may be used. Further, as in JP-A-56-132332, water is supplied to carry out heat development. Good.

In addition to the above components, the heat-developable color light-sensitive material of the present invention may further contain various agents such as a spectral sensitizing dye, an antihalation dye, a fluorescent brightening agent, a hardener, an antistatic agent, a plasticizer, and a spreader. Additives and coating aids are added.

The heat-developable color light-sensitive material of the present invention basically comprises (1) a photosensitive silver halide, (2) a reducing agent, (3) and the coupler of the present invention, (4) a binder and (5) in the same layer.
Contains an organic silver salt. However, these do not necessarily have to be contained in a single photographic constituent layer. For example, the photosensitive layer is divided into two layers, and the above (1), (2), (4), (5)
Two or more photographs as long as they are capable of reacting with each other, for example, the component (1) is contained in the photosensitive layer on one side, and the coupler (3) of the present invention is contained in the layer on the other side adjacent to the photosensitive layer. It may be contained in the constituent layers separately.

In addition, the color-sensitive layer is, for example, a high-sensitivity layer and a low-sensitivity layer
It may be divided into layers or more, and may further have one or more photosensitive layers having different color sensitivities, or may be an overcoat layer, an undercoat layer, a backing layer, an intermediate layer, or It may have various photographic constituent layers such as a filter layer.

Similar to the heat-developable photosensitive layer of the present invention, a coating solution is prepared for each of the protective layer, the intermediate layer, the undercoat layer, the back layer, and the other photographic constituent layers, and the dipping method, the air knife method, the curtain coating method or the US method is used. The photosensitive material can be prepared by various coating methods such as the hopper coating method described in Japanese Patent No. 3,681,294.

Furthermore, if desired, two or more layers can be coated simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.

The above components used in the photographic constituent layers of the heat-developable color light-sensitive material of the present invention are coated on a support, and the thickness of the coating is
After drying, it is preferably 1 to 1,000 μm, more preferably 3 to 2
It is 0 μm.

The heat-developable color light-sensitive material of the present invention is, after imagewise exposure as it is, usually in the temperature range of 80 ° C to 200 ° C, preferably 120 ° C to 170 ° C, for 1 second to 180 seconds, preferably for 1.5 seconds to 120 seconds.
Color development is achieved simply by heating for a second. Further, if necessary, a water-impermeable material may be brought into close contact with the surface for development, or preheating may be carried out at a temperature range of 70 ° C. to 180 ° C. before exposure.

Various exposing means can be used for the heat-developable color light-sensitive material of the present invention. The latent image is obtained by imagewise exposure to radiation containing visible light. Light sources commonly used for normal color printing, such as tungsten lamps,
A mercury lamp, a xenon lamp, a laser beam, a CRT beam, etc. can be used as a light source.

As the heating means, all methods applicable to ordinary photothermographic materials can be used, for example, contact with a heated block or plate, contact with a heat roller or a heat drum, or passage through a high temperature atmosphere. Alternatively, high frequency heating may be used, or a conductive layer may be provided in the light-sensitive material of the present invention or in the image transfer layer (element) for thermal transfer, and Joule heat generated by energization or a strong magnetic field may be used. The heating pattern is not particularly limited, and includes a method of preheating (preheating) in advance and then reheating, and continuously rising, lowering or repeating at a high temperature for a short time or at a low temperature for a long time. Can be discontinuously heated, but a simple pattern is preferable. Further, it may be a system in which exposure and heating proceed simultaneously.

In the heat-developable light-sensitive material of the present invention, it is subjected to bleaching and a fixing bath after heat-development in order to remove a silver image simultaneously generated, or it is processed in a fixing bath or JP-A-59-136733, US Pat.
No. 4,124,387, the bleaching and fixing may be carried out by superposing it on the bleaching and fixing sheet.

[Examples] Examples of the present invention will be shown below, but the embodiments of the present invention are not limited thereto.

Example-1 Exemplified Compound 1 420 mg, 1,4-dioctylhydroquinone
5 mg, ethyl acetate 1.3 ml and dioctyl terephthalate 0.
5 g were mixed and dissolved by heating. This solution contains a surfactant
After mixing with 6 cc of 2.5% gelatin aqueous solution and adding water to 13 cc, the mixture was dispersed with a homogenizer to obtain a coupler dispersion.

6.5cc of the above dispersion is mixed with 3.5mg of water containing 150mg of gelatin, 300mg of polyvinylpyrrolidone (average molecular weight 30,000), 3-methylpentane-1,3,5-triol (200mg) and polyethylene glycol (average molecular weight 300). 200 mg of a reducing agent (R-11) was added, and 4 ml of a 4-sulfobenzotriazole silver solution prepared by the following method was added to add p.
H was set to 5.5. To this dispersion, a silver iodobromide emulsion having an average particle size of 0.05 μm was added in an amount of 3 × 10 ^-4 mol in terms of silver (gelatin 75 mg).
Then, after adding water to make 16 ml, the photosensitive layer was coated on a baryta paper with a wire bar so that the dry film thickness was 7.5 μm, and photosensitive material sample No. 1 was obtained. .

The obtained photosensitive material sample No. 1 was dried, exposed to white light of 32000 CMS through a step wedge, and then heat-developed at 150 ° C. for 1 minute to obtain a cyan image. Table 1 shows the image densities of the obtained images with respect to red light.

[Preparation of 4-sulfobenzotriazole silver] 24 g of 4-sulfobenzotriazole and 4 g of sodium hydroxide were added to and dissolved in 300 ml of an ethanol-water (1: 1) mixed solution. 20 ml of 5N silver nitrate solution was added dropwise to this solution. At this time, 5N sodium hydroxide solution was also added dropwise at the same time to maintain the pH at 7-8. The solution was stirred for 1 hour at room temperature and then made up to 400 ml with water to prepare a 4-sulfobenzotriazole silver solution containing 4-sulfobenzotriazole in a 20% excess.

Comparative Example Photosensitive material samples Nos. 2 and 3 were prepared in the same manner as in Example-1, except that the Exemplified Compound 1 of Example-1 was replaced with the following couplers (A) and (B). The same heat development as in 1 was performed to obtain a cyan image.

The results are shown in Table-1.

As is clear from the results shown in Table 1, the light-sensitive material sample using the cyan coupler of the present invention is a good cyan dye having a larger maximum density and a smaller fog by heat development than the sample using the comparative cyan coupler. It can be seen that an image is obtained.

Example-2 Photosensitive Material Sample Nos. 4 to 4 were carried out in the same manner as in Example-1 except that the exemplified compound 1 of Example-1 was changed to the coupler shown in Table-2.
8 was prepared and subjected to the same exposure and heat development as in Example-1 to obtain a cyan image shown in Table-2.

Example-3 The photosensitive material after heat development of Example-2 (Sample Nos. 4 to 6) was processed by Eastman Kodak Company E-6 described below (Sample).
No. 4'to 6 '), the photosensitive material (Sample Nos. 7 and 8) was treated with Eastman Kodak ECN-2 (Sample Nos. 7' and 8 ').
By bleaching and fixing, a clear cyan image was obtained. The image density of the obtained image with respect to red light is shown in Table 2.

[E-6 treatment] Process temperature time 1. Conditioner 25-40 ℃ 2 minutes 2. Bleach 35-38 ℃ 6 minutes 3. Fixing 25-40 ℃ 6 minutes 4. Water washing 4 minutes [ECN-2 treatment] Process temperature time 1. Pre-bath 27 ℃ 30 seconds 2. Bleach 27 ℃ 3 minutes 3. Washing 1 minute 4. Fixing 25-40 ℃ 5 minutes 5. Washing 2 minutes As is clear from the results in Table 2, it is found that a good cyan dye image with high color density and low fog can be obtained even if the type of the cyan coupler of the present invention is changed or the processing method is changed. .

Claims (1)

[Claims] 1. A photothermographic material comprising at least a photosensitive silver halide, an organic silver salt, a reducing agent, a binder and a coupler represented by the following general formula (1) on a support. General formula (1) [Wherein Z represents an atomic group necessary for forming a benzene ring or a naphthalene ring, R ₁ represents an alkyl group or a hydrogen atom, R ₂ represents a hydrogen atom, an aliphatic group or an aromatic group, R 2 ₃ and R ₄ each represent a hydrogen atom or a substituent, a represents an integer of 1 or 2, and when a is 2, R ₃ may be the same or different. b represents an integer of 1 or 2 when a benzene ring is formed by Z,
When Z forms a naphthalene ring, b represents an integer of 1 to 6, and when b is 2 to 6, R ₄ may be the same or different. However, in R ₂ , R ₃ and R ₄ , all are not hydrogen atoms, and at least one substituent is a ballast group. ]