JPS6338935A - Heat developable photosensitive material containing novel cyan dye providing substance - Google Patents

Abstract

PURPOSE:To obtain a high density cyan dye image having little fog by using a specified compd. or a polymer derived from the compd. as one of dye providing substances. CONSTITUTION:When a photographic constituent layer contg. photosensitive silver halide, a reducing agent, dye providing substances and a binder is formed on a support, a compd. represented by formula I or a polymer derived from the compd. is used as at least one of the dye providing substances. In the formula I, R<1> is a univalent org. group, R<2> is 2-6C alkyl, R<3> is H or a univalent org. group, X is H or halogen, Y is O or S and M is H, -NH4 or a univalent metal atom. Thus, a clear image can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a heat-developable photosensitive material that forms an image by heat development, and particularly relates to a heat-developable photosensitive material containing a novel cyan dye-providing substance that allows a cyan dye image to be formed by heat development. It relates to photosensitive materials for development.

[Background of the Invention] In recent years, heat-developable photosensitive materials whose development process can be performed by heat treatment have attracted attention as photosensitive materials.

Regarding such heat-developable photosensitive materials, for example,
No. 4921 and No. 43-4924 disclose a photosensitive material comprising an organic silver salt, silver halide, a reducing agent, and a binder, which is commercialized as dry silver by 3M Company.

Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods.

For example, U.S. Patent No. 3.531.286, U.S. Pat.
61゜270@ and No. 3,764,328, etc., a method of forming a dye image by the reaction of an oxidized product of an aromatic primary amine developing agent with a coupler, Research Disclosure t- (Research[11s
closure) 15108 and 15127,
A dye image is formed by the reaction of a coupler with an oxidized form of a reducing agent (hereinafter also referred to as a developer or developing agent), which is a sulfonamide phenol or sulfonamide aniline derivative described in U.S. Pat. No. 4,021,240, etc. As disclosed in British Patent No. 1,590,956, Akebono imino silver salt having a dye part is used, the dye is liberated in a heat development part, and a dye image is formed on a separately provided receiving layer. The method of separating the
Methods for obtaining positive dye images by silver dye bleaching methods disclosed in US Pat. No. 3,985,565, No. 4,022,617, No. 4,452,883,
Various methods have been proposed, including a method for obtaining a dye image using a leuco dye disclosed in Japanese Patent Application Laid-Open No. 59-206831.

However, these proposals regarding the above-mentioned thermal phenomenon color photosensitive materials have problems such as the difficulty in bleach-fixing the black and white silver images that are formed at the same time, the difficulty in obtaining clear color images, and the complicated process. Since these methods require post-processing, they are still unsatisfactory for practical use.

In recent years, as a new type of color image forming method using heat development, Japanese Patent Application Laid-open Nos. 57-179840 and 57-186 have been developed.
No. 744, No. 57-198458, No. 57-2072
No. 50, etc., disclosed a method of obtaining a color image by transferring a diffusible dye released by thermal development.

Then, by making rough improvements to these methods, for example, a non-diffusible reducible dye-donating substance disclosed in JP-A-58-58453 and JP-A-59-168439 is oxidized to provide a diffusible dye. Method for releasing dye, JP-A-58-
No. 79247, No. 59-174.834, No. 59-1
No. 2431, No. 59-159159, No. 60-295
A method of releasing a diffusible dye by coupling with an oxidized form of a developing agent as disclosed in No. 0, etc.;
JP-A-58-149046, JP-A No. 58-149047
No. 59-124339, No. 59-181345
No. 60-2950, Japanese Patent Application No. 59-181604, No. 59-182506, No. 59-182507
No. 59-272335, etc., which uses a non-diffusible compound that reacts with an oxidized developing agent to form a diffusible dye;
No. 52440, No. 59-124327, No. 59-15
Disclosed in No. 4445, No. 59-166954, etc.
Methods have been proposed that include non-diffusible reducing dye-donating substances that lose their ability to release diffusible dyes when oxidized, and systems that contain non-diffusible dye-donating substances that release diffusible dyes when reduced. ing.

The above heat-developable photosensitive material is one in which a dye image is obtained by transferring the released or formed diffusible dye onto an image receiving layer of an image receiving member provided on the same support or another independent support. In terms of image sharpness, stability, etc., it was improved in many respects compared to previous heat-developable color photosensitive materials.

Among these heat-developable color photosensitive materials, those that form a dye through a coupling reaction with an oxidized form of a developing agent are particularly susceptible to problems such as the S/N ratio (maximum density/fog ratio) of the resulting color image and storage. It is preferable in terms of properties and is also excellent in that it does not require a base or its precursor.

The compounds described in JP-A-60-179739 and JP-A-61-61158 are used as dye-providing substances for forming cyan dye images by the coupling method.
Although it has an excellent N ratio, when the compounds described in these specifications are used, the cyan dye formed is decomposed by the heat during thermal development and/or the coexisting reducing agent, resulting in the apparent dye formation. Efficiency tends to be low and staining may occur due to decomposition products, and improvements to these problems have been desired.

[Object of the Invention 1] Therefore, the object of the present invention is to solve the problems that the above-mentioned cyan dye-providing substances have.

That is, an object of the present invention is to provide a heat-developable photosensitive material containing a novel cyan dye-providing substance.

Another object of the present invention is to provide a photothermographic material capable of producing clear images.

Still another object of the present invention is to provide a photothermographic material containing a cyan dye-providing substance that forms a cyan dye that is less likely to be decomposed by heat and/or a coexisting reducing agent during thermal development.

Still another object of the present invention is to provide a heat-developable photosensitive material containing a cyan dye-providing substance capable of obtaining color images with high density and less fog.

[Structure of the Invention] As a result of intensive research to achieve the above object, the present inventors have developed a heat-developable photographic layer having a photographic constituent layer containing at least a photosensitive silver halide, a reducing agent, a dye-providing substance, and a binder on a support. The above object of the present invention can be achieved by a color photosensitive material in which at least one of the dye-providing substances is a compound represented by the following general formula (1) or a polymer derived from the compound. I found it.

000M (wherein R1 represents a monovalent organic group, R2 represents an alkyl group having 2 to 6 carbon atoms, R3 represents a hydrogen atom or an organic group, X represents a hydrogen atom or a halogen atom, (Y represents an oxygen atom or a sulfur atom, and M represents a hydrogen atom, an NH4 group, or a monovalent metal atom.) [Specific constitution of the present invention] In the heat-developable photosensitive material of the present invention, the formed dye may be transferred to form a color image on the image-receiving element (transfer type), or a color image may be formed in the photographic constituent layer in which the dye-providing substance of the present invention is present without being transferred (non-transfer type). However, a transfer type is more preferable from the viewpoint of ease of separation from the silver image formed during thermal development.

In the heat-developable photosensitive material of the present invention, at least one of the dye-providing substances is a compound represented by the general formula (1) or a polymer derived from the compound, and in this specification, these are collectively referred to as: It is referred to as the cyan dye-donating substance of the present invention.

The cyan dye-providing substance of the present invention will be explained below.

In the general formula [1], R1 represents a monovalent organic group, preferably an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkylamino group, a dialkylamino group, or an arylamino group. represent. These groups generally include alkoxy groups, cyano groups,
Nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, sulfo group, carboxy group, acylamino group, alkylamino group, alkylsulfonylamim L arylsulfonylamim L sulfa It may be substituted with one or more substituents such as a moylamino group, an imide group, and a halogen atom.

When the heat-developable photosensitive material of the present invention is of the above-mentioned transfer type, R
The total number of carbon atoms in the organic groups represented by 1 is preferably 12 or less (more preferably 8 or less). Further, when the heat-developable photosensitive material is a non-transfer type, the organic group represented by R1 is an organic ballast group having a molecular size and shape that can be immobilized when the compound represented by the general formula (1) is thermally developed. It is desirable that Preferred organic ballast groups are organic groups having a total number of carbon atoms of 12 or more, and in particular organic groups having a total number of carbon atoms of 12 or more and having at least one hydrophilic group such as a sulfo group or a carboxy group as a substituent. is preferred.

Yet other particularly preferred organic ballast groups include polymeric residues.

When the organic ballast group is a polymer residue, it is a polymer having repeating units derived from a monolayer body represented by the following general formula (2).

General formula (2) % formula % In the formula, R2, R3, X, Y and M have the same meanings as R2, R3, Represents a group having an ethylenically unsaturated group.

In the general formula (1), X represents a hydrogen atom or a halogen atom, and the halogen atom is preferably a chlorine atom or a fluorine atom.

In the general formula (1), R2 is an alkyl group having 2 to 6 carbon atoms (e.g. ethyl group, n-propyl group, i-
Propyl group, n-butyl group, tert-butyl group, n-
(pentyl group, n-hexyl group), particularly preferably ethyl group.

In the general formula (1), Y represents an oxygen atom or a sulfur atom, and is particularly preferably an oxygen atom.

In the above formula (1), R3 represents a hydrogen atom or a -valent organic group, and the -valent a group is preferably an alkyl group, a cycloaluel group, an alkenyl group, an aryl group, and an aralkyl group. can be mentioned. These groups may further include one of the substituents, such as an alkoxy group, an acylamino group, an alkylamino group, a sulfamoylcarboxy group, an alkylsulfonylaminolylsulfonylamino group, a sulfamoylamino group, an imide group, and a halogen atom. or more may be substituted.

When the heat-developable photosensitive material of the present invention is of the above-mentioned transfer type, R
The organic group represented by 3 is preferably a ballast group having a molecular size and shape that can immobilize the compound represented by formula (1) during thermal development.

Preferred ballast groups are organic groups having a total number of carbon atoms of 12 or more, and more preferably organic groups having one or more hydrophilic groups such as sulfo groups or carboxy groups as I substituents and having a total number of carbon atoms of 12 or more. The right of more than or equal to is a base.

Still other particularly preferred ballast groups include polymeric residues.

When the ballast group is a polymer residue, the cyan dye-providing substance of the present invention is represented by the following one-stage formula (3): I! The cyan dye-providing substance is a polymer having a repeating unit derived from a polymer, and is most preferred as the cyan dye-providing substance of the present invention.

General formula (3) % formula % In the formula, R', R2, X, Y and M have the same meanings as R1, R2, X, Y and M in general formula (1), and Q2 is an ethylenically unsaturated group or Represents a group having an ethylenically unsaturated group.

In the general formulas (2) and (3), Ql and Q2 represent an ethylenically unsaturated group or a group having an ethylenically unsaturated group, but preferably the following general formula % formula % General formula (4) In the formula, Zl and Z2 represent a 2filfi hydrocarbon group, Jl and J2 represent a divalent bonding group, R+ represents a hydrogen atom or an alkyl group, ln1, lI12, nl
and R2 each represent an integer of O or 1.

In the general formula (4), zl and z2 represent a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include an alkylene group (e.g., medilene group, ethylene group,
propylene group, etc.), arylene group (e.g., phenylene group, etc.), aralkylene group (e.g., phenylmethylene group, etc.), alkylenearylene group (e.g., methylenephenylene group, ethylenephenylene group, etc.), arylene alkylene group (e.g., phenylenemethylene group, etc.) group, phenylene ethylene group, etc.).

In the general formula (4), Jl and O2 represent a divalent bonding group, and examples of the divalent bonding group include, for example, -NH
CO-1-CONH-1-NH8O2-1-8O2NH
-1 -NHCOCH2-1-CH2C0NH-1-0-1-
S-1-CO-1-8O2-1-〇〇〇-1-OCO-
etc.

The divalent bonding group of Jl and O2 is preferably -NHCO
-1-NHCOCH2-1 or -○C〇-.

In the general formula (4), R4 represents a hydrogen atom or an alkyl group, and the alkyl group has 1 to 4 carbon atoms.
An alkyl group (eg, methyl group, ethyl group, n-propyl group, lobethyl group) is preferable, and a methyl group is particularly preferable.

The polymer having a repeating unit derived from the monomer represented by the above general formula (2) or (3) of the present invention may contain only one type of monomer represented by the above general formula (2) or (3). It may be a so-called homopolymer of repeating units consisting of, or a copolymer combining two or more types of monomers represented by the general formula (2) or (3),
Furthermore, it may be a copolymer comprising one or more comonomers having an ethylenically unsaturated group that can be copolymerized.

Examples of the comonomer having an ethylenically unsaturated group that can form a copolymer with the monomer represented by the general formula (1) or (2) of the present invention include acrylic esters, methacrylic esters, vinyl esters, and olefins. styrenes, crotonate esters, itaconate diesters, maleate diesters, fumarate diesters, - acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters Examples include unsaturated nitriles, polyfunctional monomers, and various unsaturated acids.

More specifically, these comonomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, ter
t-Butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanethyl acrylate, 2- Acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2- Dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-(2-
methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (additional mole number n = 9
) 1-bromo-2-methoxyethyl acrylate, 1.
Examples include 1-dichloro-2-ethoxyethyl acrylate.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, low-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate,
amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-
Phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate (~, furfuryl methacrylate, tetrahydrofurfuryl methacrylate)
1~, phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
Triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate , 2-butoxyethyl methacrylate, 2-(2
-methoxystyrene)ethyl methacrylate, 2-(2
-ethoxyethoxy)ethyl methacrylate, 2-(2
-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles added, n=6), allyl methacrylate, dimethylamine methacrylate ethylmethyl chloride salt, and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc. Can be mentioned.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, 2,3-dimethylbutadiene, and the like.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dimethylstyrene, bromustyrene, and vinylbenzoic acid methyl ester. Can be mentioned.

Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like.

Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Examples of other comonomers include:

Acrylamides, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyethylacrylamide, dimethylamineethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.; Methacrylamides, such as methacrylamide, methylmethacrylamide, ethylmethacrylamide amide, propyl methacrylamide, butyl methacrylamide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanethylmethacrylamide , N-(2-acetoacetoxyethyl) methacrylamide, etc.; Allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy Ethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N-vinyl oxazolidone, N -vinyltriazole, N-vinylpyrrolidone, etc.; glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; unsaturated nitriles, such as acrylonitrile, methacrylateryl, etc.; polyfunctional monomers, such as divinylbenzene, methylenebisacrylamide, such as ethylene glycol dimethacrylate.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates, such as monomethyl maleate, monoethyl maleate, maleic acid; Monobutyl acids, etc.; silaconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, polysulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.;
Methacryloyloxyalkylsulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkylsulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2 -Methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.: methacrylamide alkylsulfonic acid, such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, Niacryloyloxyalkyl phosphates such as 2-methacrylamido-2-methylbutanesulfonic acid,
For example, acryloyloxyethyl phosphate, 3-
Acryloyloxypropyl-2-phosphate etc.:
Methacryloyloxyalkyl phosphates, e.g.
Methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.: Examples include sodium 3-aryloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali metals (eg, Na, Ni, etc.) or ammonium ions. Further, other comonomers include U.S. Patent No. 3.459.790;
3,438.708, 3,554,987, 4,215.195, 4.247.673
Crosslinkable monomers described in JP-A-57-205735 and the like can be used. An example of such a crosslinking monomer is specifically N-(2
-acetoacetoxyethyl)acrylamide, N-(2
-(2-acetoacetoxyethoxy)ethyl)acrylamide and the like.

Further, when forming a copolymer with the monomer represented by the general formula (2) or (3) of the present invention and the comonomer, preferably the monomer represented by the general formula (2) or (3) is used. This is the case where the repeating unit consisting of is contained in an amount of 10 to 90% by weight of the entire polymer, and more preferably 30 to 70% by weight of the entire polymer.

Generally, the polymer coupler is polymerized by an emulsion polymerization method or a solution polymerization method, and has a repeating unit derived from a monomer represented by the general formula (2) or (3) according to the present invention. Material polymers can also be polymerized in a similar manner. Emulsion polymerization methods are described in U.S. Pat. 45
1.820 can be used.

These methods can also be applied to the formation of homopolymers and copolymers; in the latter case the comonomer may be a liquid comonomer, which in the case of 7L polymerization normally also acts as a solvent for the immobilized monomer. do.

Examples of emulsifiers used in the emulsion polymerization method include surfactants, polymeric protective colloids, and copolymer emulsifiers. Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants known in the art.

Examples of anionic activators include soaps, sodium dodecylbenzenesulfonate, sodium lauryl sulfate,
Examples include sodium dioctyl sulfosuccinate and sulfates of nonionic surfactants.

Examples of nonionic activators include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene rubicune monolaurate, polyoxyethylene-polyoxypropylene block copolymer, and the like. Further, examples of cationic activators include alkylpyridium salts, tertiary amine necks, and the like.

Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Further, examples of the polymeric protective colloid include polyvinyl alcohol, droxyethyl cellulose, and the like. These protective colloids may be used alone as emulsifiers or in combination with other surfactants. For information on the types of these activators and their effects, please refer to the Bergische Industrie.
emische Industry, 2816-2
0 (1963).

In order to disperse a lipophilic polymer synthesized by a solution polymerization method in the form of a latex in an aqueous gelatin solution, the lipophilic polymer is first dissolved in an organic solvent, and then dissolved in an aqueous gelatin solution with the help of a dispersant. Then, it is dispersed into a latex form using ultrasonic waves, a colloid mill, etc. A method of dispersing lipophilic polymers in latex form in aqueous gelatin solutions is described in US Pat. No. 3,451,820@.

Examples of organic solvents that dissolve lipophilic polymers include esters such as methyl acetate, ethyl acetate, propyl acetate, etc.
Alcohols, ketones, halogenated hydrocarbons, ethers, etc. can be used.

Further, these R-containing solvents can be used alone or in combination of two or more.

In producing the dye-providing polymer according to the present invention, the solvent used in the polymerization is preferably one that is a good solvent for the monomer and the dye-providing polymer to be produced, and has low reactivity with the polymerization initiator. Specifically, water, (ruene, alcohol (e.g. methanol, ethanol, 1so-propanol, tert-butanol, etc.), acetone, methyl ethyl ketone, tetrahydrofuran, dioxane,
Examples include ethyl acetate, dimethylformamide, dimethyl sulfoxide, acetonitrile, methylene chloride, and the like, and these male media may be used alone or in combination of two or more.

Although it is necessary to consider the polymerization temperature, such as the type of polymerization initiator and the type of solvent used, the polymerization temperature is usually 30 to 120°C.

Examples of the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the dye-providing polymer of the present invention include those shown below.

Examples of water-soluble polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate, and potassium persulfate;
．． Sodium 4'-azobis-4-cyanovalerate, 2,
Water-soluble azo compounds such as 2'-azobis(2-amidinopropane) hydrochloride and hydrogen peroxide can be used.

In addition, examples of lipophilic intermediate initiators used in the solution polymerization method include azobisisobutyronitrile, 2.2'-azobis-(2,4-dimethylvaleronitrile), 2.2'-azobis-(2,4-dimethylvaleronitrile),
'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 11'-azobis(cyclohexanone-1
-carbonitrile), 2.2'-azobisincyanobutyric acid, 2゜2'-7 dimethyl zobisisoacetate, 1.1'-
Azobis (cyclohexanone-1-carbonitrile),
4. Azo compounds such as 4'-azobis-4-cyanovaleric acid, peroxides such as benzoyl peroxide, lauryl peroxide, chlorobenzyl peroxide, diisobrobyl peroxide, di-t-butyl peroxide, etc. Examples include oxides. Among these, preferred ones include benzoyl peroxide, chlorobenzyl peroxide, and lauryl peroxide.

These polymerization initiators can be contained in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of monomers in emulsion polymerization and solution polymerization.

Furthermore, polymerization methods other than the combination method described above, such as suspension polymerization and bulk polymerization, can also be applied. That is,
In the present invention, the general formula (2) or (3) of the present invention
) A dye-donating homopolymer of the monomer represented by (), a copolymer obtained by combining two or more of the monomers, or a copolymer consisting of the monomer and at least one other polymerizable comonomer as a copolymerization component. It includes all copolymers and is not limited by their synthesis process.

Specific examples (excluding polymer types) of the cyan dye-providing substance represented by general formula (1) of the present invention are shown in Table 1 below.
Shown below.

Below) “White tノ;222.

Next, specific examples of the cyan dye-providing substance monomer represented by general formula (2) of the present invention are shown in Table 2 below.

Next, specific examples of the cyan dye-providing substance represented by the general formula (3) of the present invention are shown in Table 3 below. Specific examples of cyan dye-providing substance polymers are shown in Table 4 below. 711. -5. .

Below 1. Steaming at 1° C. A specific method for synthesizing the cyan dye-providing substance of the present invention is shown below.

Synthesis Example Intermediate (1): Synthesis of 2-ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol WMW 48.5 g of 2-amino-4,6-dichloro-5-ethyl-phenol was dissolved in acetonitrile. The mixture was dissolved in a solution consisting of 20 (hR) and 501 g of pyridine, and 25 g of acetyl chloride was added dropwise to this solution. After refluxing for 1 hour (solid precipitation), it was poured into 300 g of water and the solid was filtered out.

This solid was added to a water/methanol solution containing 10° of sodium hydroxide and stirred for a while.

This solution was neutralized by adding ice-cooled dilute hydrochloric acid, and the precipitated crystals were filtered off.

The crystals were added to cold acetonitrile, stirred for a while, separated, washed with cold acetonitrile, and dried.
40o 2-acetylamino-4゜6-cyclo-5-
Crude crystals of ethylphenol were obtained.

Add 39.3 (l) of this crude crystal to 40 (h12) of acetic acid,
Disperse and cool to 10° C. with stirring. Add 70T112 of water containing 14.59% of sodium nitrite to this solution.
The mixture was added dropwise at a temperature below .degree. C. and further stirred at 20.degree. C. for 1 hour.

This reaction solution was heated to 1500. In addition to the water in Q, the precipitated yellow crystals were filtered out, washed with water and dried, and 29 g of 2-
Crude crystals of acetylamino-5-ethyl-6-chloroquinone were obtained.

The entire amount of the crude crystals was dissolved in ethanol-tetrahydrofuran solution 4001112 and subjected to hydrogen reduction using carbon-palladium as a catalyst. Filter and concentrate the reaction solution, add acetone 3
Added to 00d. To this acetone solution was added 30 g of potassium carbonate and 16.2 i12 of benzyl bromide under a nitrogen stream.
and refluxed for 8 hours while stirring. Filter the reaction solution,
After concentration, the precipitated solid was washed with water and recrystallized from acetonitrile to obtain 32.3 (l) of 2-ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol.

Intermediate (2): Dissolve 32 J of 2-ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol and 18.4 J of ethyl α-bromoacetate in 6001 J2 of acetone, and further add 60 g of potassium carbonate. The reaction solution was filtered and concentrated, and then dissolved in an ethanol-tetrahydrofuran solution, and subjected to hydrogen reduction using carbon-palladium as a catalyst.After filtering and concentrating this reaction solution, 7. It was added to a solution consisting of 10011Q of water containing 5Q of sodium hydroxide and 200% of ethanol, and after stirring for a while, it was placed in the apparatus overnight.Next, the reaction solution was poured into dilute hydrochloric acid to neutralize it, and the precipitated 2-ethyl-3- Crude crystals of chloro-4-hydroxy-5-acetylaminophenoxyacetic acid were obtained.The crude crystals were mixed with ethanol 30011
It was added to a mixed solution of Q and concentrated sulfuric acid 30vQ, refluxed, and after cooling, the precipitated crystals were filtered to obtain 2-ethyl-3-chloro-4.
-Hydroxy-5-aminophenoxyacetic acid salt I! 14.2 (l) of i salt was obtained.

Synthesis of Exemplified Compound C-1 7 g of 2-ethyl-3-chloro-4-hydroxy-5-aminophenoxyacetic acid hydrochloride was added to 100 ml of acetonitrile.
In addition to the mixed solution of pyridine 6tj2 and pyridine 6tj2, 7.6 g of stearic acid chloride was added dropwise. After refluxing for 1 hour, it was cooled and the precipitated crystals were filtered out, washed with cold acetonitrile, and dried to obtain the desired product. Ta.

Synthesis of Exemplified Compound C-5 6.4 g of 2-ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol and ethyl α-brompalmitate a, og were dissolved in acetone 15 (h12),
8 g of potassium carbonate was added, and the mixture was refluxed for 5 hours while stirring. After filtering and concentrating this reaction solution, ethanol 2001R was added.
In addition, hydrogen reduction was performed using carbon-palladium as a catalyst, followed by filtration, 50 d of water containing 2 g of sodium hydroxide was added, and the mixture was stirred for 5 hours. The reaction solution was poured into diluted hydrochloric acid 200-d, and the precipitated solid was filtered off and recrystallized from acetonitrile to obtain 8.8 g of the desired product.

Synthesis of exemplified monomer C-16 Using 2-ethyl-3-chloro-4-hydroxy-5-aminophenoxyacetic acid hydrochloride and methacrylic acid in place of stearic acid chloride, the rest was the synthesis example ( 3) is the same as 11, and the object is 37 1ql.

Synthesis of onychocyst C-23 128 g of 2-ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol and α-promo T-(
ρ-2i~lophenyl)-ethyl butyrate (13,9i; 1) was dissolved in 300 g of acetone, 16 g of potassium carbonate was added, and the mixture was allowed to flow for 8 hours. This reaction solution was filtered and concentrated, ethanol 2501R was added, and the resulting brown solid was filtered off, and this solid was recrystallized with acetonitrile to obtain white crystals. This entire set of crystals was dissolved in ethanol and carbon-
Hydrogen reduction was performed using palladium as a catalyst. After the reaction is complete, the reaction solution is filtered, the filtrate is condensed to 100tR, 50vf of water containing 3.5g of sodium hydroxide is added, and after stirring at the lowest temperature for 5 hours, it is neutralized with dilute sulfuric acid to precipitate white. Solid (α−[
(2-ethyl-3-chloro-4-hydroxy-5-acetylaminophenoxy]-7-(+1-aminophenyl)butyric acid) was filtered off.

This intermediate 81.30 was dissolved in a mixed solution of acetonitrile 80112 and 157 g of pyridine, cooled to below 15°C, and a solution of 23 kb of methacrylic acid chloride in acetonitrile (10112) was added dropwise, followed by stirring at room temperature for 2 hours. did. The reaction solution was poured into water, the precipitated solid was filtered out, and recrystallized with acetonitrile to obtain 7.6 g of the target product. The structures of the above intermediate and synthetic compound were determined by NMR.
and confirmed by FD-mass spectrum.

Synthesis of Exemplified Compound PC-1 15 g of Exemplified Monomer C-16 obtained above and 15 g of rope tyl acrylate were dissolved in 150 g of dioxane and heated to 80 to 81° C. while introducing nitrogen gas. While maintaining this temperature, 600 mg of 2.2'-azobisisobutyronitrile was added and reacted for 4 hours. After the reaction was completed, the reaction solution was poured into 12 pieces of ice water, and the precipitated solid was filtered off and dried. This solid was redissolved in dioxane 10 (hN), the dioxane solution was poured into ice water of 12, and the solid precipitated again was filtered and dried to obtain the desired polymer pc-1:26.
I got g.

Synthesis of Exemplified Compound PC-6 Exemplified Monomer C-23:15q and n obtained above
- Dissolve butyl acrylate 10Q in dimethylformamide of 125% and add 84 to 85% of dimethylformamide while introducing nitrogen gas.
℃, maintained this temperature, added 250 mg of 2,2'-azobisisobutyronitrile, reacted for 2 hours, and then added 250 mg of 2,2'-azobisisobutyronitrile.
mg was added and reacted for 2 hours. After the reaction was completed, the reaction solution was poured into ice water in Step 11, and the precipitated solid was filtered off and dried.

This solid was redissolved in dimethylformamide i o o , p, the dimethylformamide solution was poured into ice water in Step 11, and the precipitated solid was filtered off and dried to prepare the desired polymer.These dye-providing substances were used alone. or two or more may be used. When two or more dye-providing substances are used, two or more dye-providing substances represented by the general formula (1) of the present invention may be used.
It may be used in combination with a cyan dye-providing substance other than the cyan dye-providing substance of the present invention, such as the cyan dye-providing substance described in No.-61158.

The amount used is not limited, and depends on the type of dye-providing substance, whether it is used alone or in combination, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more types. It may be determined accordingly, but for example, the amount used is O,oo5g to 509 per 1112, preferably 0.1g to 10
g can be used.

The dye-providing substance used in the present invention can be incorporated into the photothermographic layer of the heat-developable photosensitive material using any method. phthalate, tricresyl phosphate, etc.) and then dispersed with fan-sonic waves or dissolved in an alkaline aqueous solution (e.g., l”
After dissolving in a 10% aqueous KM sodium trilam solution, etc., it can be neutralized with a mineral acid (e.g., hydrochloric acid or nitric acid, etc.), or
or an aqueous solution of a suitable polymer (e.g. gelatin,
It can be used after being dispersed together with polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill.

Lilly-7 Photosensitive silver halides used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples include silver chloroiodobromide. The photosensitive silver halide is
It can be prepared by any method in the photographic field, such as a single jet method or a double jet method. For example, by applying the method described in JP-A-54-48521, monodisperse silver halide grains can be obtained by the double jet method while keeping I)A(l constant).

In this case, highly monodisperse silver halide emulsions can be obtained by carefully selecting the addition rate as a function of time, l) H, DIJ, temperature, etc. According to a particularly preferred embodiment, silver halide emulsions having shelled silver halide grains can be used. Silver halide grains having shells can be obtained by sequentially growing shells on a core of silver halide grains having good monodispersity using the method described above.

The monodisperse silver halide emulsion used in the present invention refers to an emulsion having a particle size distribution in which the variation in the silver halide grain size contained in the emulsion is less than a certain percentage of the average grain size as shown below. .

Since the grain size distribution of an emulsion (hereinafter referred to as a monodisperse emulsion) consisting of a group of photosensitive silver halide grains with a uniform grain morphology and small variation in grain size is almost a normal distribution, the standard deviation can be easily determined. The width of the distribution of the silver halide grains involved is preferably 15% or less, more preferably monodispersity of 10% or less.

Also, for example, JP-A No. 58-111933, 5g-1
No. 11934, No. 58-108526, Research Disclosure No. t-22534, etc., it has two parallel crystal planes, and each of these crystal planes is different from other units of this particle. It is also possible to use a silver halide emulsion consisting of tabular silver halide grains having a larger area than the crystals and an aspect ratio, that is, a ratio of M diameter to thickness of the grains of 5:1 or more.

Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces have not been fogged in advance can be used. For internal latent image type silver halide whose surface is not prefogged, for example, U.S. Pat.
, No. 592, 250, No. 3.206.313, No. 3
, No. 317,322, No. 3,511,662, No. 3
．． No. 447,927, No. 3,761,266, No. 447,927, No. 3,761,266, No.
As described in Nos. 3,703,584 and 3.736.140, silver halide grains have higher sensitivity inside the grains than on the surface of the grains. The method for producing silver halide emulsions containing these internal latent image type silver halides is as described in the above patent, for example, by first preparing AaCffi grains and then adding bromide or a small amount of iodide thereto. A method in which the central core of chemically sensitized silver halide is coated with un-chemically sensitized silver halide, or a method in which chemically sensitized coarse grain emulsion and chemically sensitized A number of methods are known in which a fine grain emulsion, either sensitized or not chemically sensitized, is mixed and the fine grain emulsion is deposited on a coarse grain emulsion. Also, U.S. Patent No. 3,271,157, U.S. Patent No. 3.4
No. 47.927 and No. 3.531.291, silver halide emulsions having silver halide grains containing polyvalent gold ions, or U.S. Pat.
Silver halide emulsions whose grain surfaces are weakly chemically sensitized containing silver halide grains containing dopants as described in JP-A-50-8524 and JP-A-50-8524 and JP-A-50-8524.
Silver halide emulsions consisting of grains having a layered structure as described in JP-A No. 0-38525, etc., and other JP-A-52-1
These include silver halide emulsions described in No. 56614 and JP-A-55-127549.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include
Various methods include gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the above-mentioned photosensitive emulsion may have coarse or fine grains, but the preferred grain size is about 0.001 μm to about 1.5 μl, more preferably about 0.001 μm to about 1.5 μl, and more preferably about 0.001 μm to about 1.5 μl. .01 μm to about 0.5 μl.

The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive 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 the right eye silver salt described below, and photosensitive silver halide may be formed in a part of the photosensitive silver salt. can. The photosensitive silver salt forming component used in this preparation method is a non-freezing halide, for example, a halide represented by MXn (where M represents an H atom, NH+ group or a metal atom, and X represents a C2,3r or I, n is 1 when M is an H atom or NH4 group, and the valence when M is a metal atom.Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper,
Gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium,
Examples include germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, and cerium. )
, halogen-containing metal complexes (e.g., K2 PtCff1s
, to 2 Pt 3rs , HAU C1+.

(NH4)2 Ir Cj2s, (NH4)3 I
rC1to.

(NH4)2 Ru Cff1s (NH4)3 R
u Cff1s.

(NH4>2 Rh C16(NH4>3 Rh Br
), onium halides (e.g., tetrameglyammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzyl ammonium bromide, quaternary ammonium halides, tetraethylphosph) quaternary phosphonium halides such as onium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g. iodoform,
bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinic acid) imide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4- dimethylhydantoin, etc.), and other halogen-containing compounds (for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.).

These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amounts used are -
It is preferable that it is o, oo1a to 50q, more preferably o, ig to 10 q per M per support 1f.
It is g.

The heat-developable photosensitive material of the present invention has a multilayer structure including each layer sensitive to blue light, green light, and red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, a heat-developable red-sensitive layer, and a heat-developable red-sensitive layer. It is also possible to do this. Further, the same color photosensitive layer can 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, respectively, can be obtained by adding various spectral sensitizing dyes to the silver halide emulsion. Can be done.

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 preferred. Such nuclei include alkyl groups, alkylene groups,
It may have an enamine group capable of forming a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl fused carbocyclic or heterocyclic ring. 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.

In addition to the above-mentioned basic nucleus, merocyanine dyes may have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbylic acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. good.

These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkylulkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat.
A supersensitizing additive that does not absorb visible light as described in the specification of 9@ may be used in combination.

The amount of these sensitizing dyes added is 1.times.10' mol to 1 mol per mol of photosensitive silver halide or silver halide forming component. More preferably, 1×10→mol to 1×1
0" mole.

More''￥!'Na1 ζko1.

3hlII In the heat-developable photosensitive material of the present invention, various types of silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability.

Examples of organic silver salts used in the heat-developable photosensitive material of the present invention include those disclosed in Japanese Patent Publication Nos. 43-4921, 52626-1980, 141222-1982, 36224-1983, and 37610-1980, etc. Publications and U.S. Patent Nos. 3,330,633 and 3,794,49
Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having heterocycles, such as silver laurate, as described in the specifications of No. 6 and No. 4,105,451, etc.
silver myristate, silver valmitate, silver stearate, silver arachidonate, silver behenate, silver α-(1-phenyltetrazolethio)acetate, silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc. Kosho 44-26582
No. 45-12700, No. 45-18416, No. 45-22185, JP-A-52-137321, JP-A-58-118638, JP-A-5G-118639,
There are silver salts of imino groups described in various publications such as US Pat. No. 4,123,274.

Examples of silver salts of imino groups include penttriazole silver. The benztriazole silver may be substituted or unsubstituted. Typical examples of substituted silver benztriazole include, for example, alkyl-substituted silver benztriazole (preferably an alkyl group of 022 or less,
Silver alkylamide benztriazole (preferably substituted with an alkyl group of C22 or less, such as silver methylbenztriazole, silver ethylbenztriazole, silver 0-octylbenztriazole, etc.), preferably silver substituted with an alkyl group of C22 or less. Substituted ones, such as silver acetamidobenztriazole, silver propionamidebenztriazole, silver 1so-butylamidobenztriazole, silver laurylamidebenztriazole, etc.), silver alkylsulfamoylbenztriazole (preferably silver alkylsulfamoylbenztriazole of C22 or less) those substituted with a moyl group, such as silver 4-(N,N-diethylsulfamoyl)penztriazole, silver 4-(N-propylsulfamoyl)penztriazole, silver 4-(N,N-diethylsulfamoyl)penztriazole,
Silver salts of halogen-substituted benztriazoles (e.g., 5-chlorobenztriazole, silver 5-bromobenztriazole, etc.), alkoxybenztriazole (preferably substituted with a C22 or less alkoxy group, more preferably a C+ or less alkoxy group, such as 5-methoxybenztriazole), triazole silver, 5-ethoxybenztriazole silver, etc.), 5-nitrobenztriazole silver, 5-aminobenztriazole silver, 4-
Hydroxybenztriazole silver, 5-carboxybenztriazole silver, 4-sulfobenztriazole silver,
Examples include silver 5-sulfobenztriazole.

Examples of other silver salts having an imino group include imidazole tin, benzimidazole silver, 6-nidropenzimidazole silver, pyrazole silver, urazole silver, 1,2
．． Silver salts of other mercapto compounds such as 4-triazole silver, 1-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., such as 2-mercaptobenzo Silver oxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole, silver 2-mercaptobenzimidazolecapto-4-phenyl-1.2.4-)-riazole, silver 4-hydroxy-6-methyl-1.3.

3a,7-thitrazaindene silver and 5-methyl-7-
Examples include silver hydroxy-1,2,3,4,6-pentazaindene.

Other silver complex compounds having a stability constant of 4.5 to 10.0 as described in JP-A No. 52-31728, and imidase as described in U.S. Pat. No. 4,168,980. A silver salt of lynchion or the like is used.

Among the above-mentioned silver salts, imino group silver salts are preferred;
Particularly preferred are silver salts of benzotriazole derivatives, more preferably 5-methylbenzotriazole and its derivatives, sulfobenzotriazole and its derivatives, and N-alkylsulfamoylbenzotriazole and its derivatives.

The organic silver salts used in the present invention may be used alone or in combination of two or more. Further, the silver salt may be stiffened in a suitable binder and used as it is without being isolated, or the isolated product may be dispersed in a binder by an appropriate means and used. Dispersion methods include, but are not limited to, ball mills, sand mills, colloid mills, vibration mills, and the like.

In addition, the manufacturing method for organic silver salts is generally a method of dissolving and mixing silver nitrate and raw material Nada compounds in water or an organic solvent, but if necessary, a binder may be added or hydroxylated. It is also effective to add an alkali such as sodium to promote dissolution of organic compounds, or to use an ammoniacal silver nitrate solution.

The amount of the organic silver salt used is generally preferably 0.01 to 500 moles, more preferably 0.1 to 100 moles, per mole of photosensitive silver halide. Roughly preferably 0.
It is 3 to 30 moles.

As the reducing agent used in the photothermographic material of the invention, those commonly used in the field of photothermographic materials can be used.

The dye-providing substance used in the heat-developable photosensitive material of the present invention is, for example, JP-A-57-186744;
-79247, 58-149046, 5g
-149047, 59-124339, 5
In the case of a dye-donating substance that releases or forms a diffusible dye by coupling with an oxidized form of a reducing agent such as those disclosed in No. 9-181345 and No. 60-2950, the present invention Examples of reducing agents used in
61, No. 270, No. 3,764.328, and RD No. 12146, No. 0.15.
108, same N 0.15127 and JP-A-56-27
p-phenyl diamine type and p-aminophenol type developing agents, phosphoroamide phenol type and sulfonamide phenol type developing agents, as described in Publication No. 132;
Sulfonamide aniline type developing agents, hydrazone type color developing agents, etc. can be used. Also, U.S. Patent No. 3.342.599, U.S. Patent No. 3.719, I! '12
No., Time 11f153-135628, No.57-79
+13! It can be used in the 11th edition of "Brecurly", the main story of color development, which is written and published in issue i, etc.

1! As a preferable reducing agent for P, Tamaki Il! (5G-1
Examples include reducing agents represented by the following general formula (!;) described in No. 46433.

General formula (r,) 11,' 几0 In the formula, R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 30 (preferably 1 to 4) carbon atoms and having a substituent. , R1 and R2 are ring-opened to form a complex M i
ft may be formed. R3, R”.

R5 and R6 each have a hydrogen atom, a halogen atom, a droxy group, an amine group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number of 1 to 30 (preferably 1) which may have a substituent. ~4)
represents an alkyl group, and R3 and R1 and R5 and R2 may each be closed to form a heterocycle. M represents an alkali metal atom, an ammonium group, a nitrogen-containing organic base, or a compound containing a quaternary nitrogen atom.

The nitrogen-containing organic base in the general formula (5) is a compound containing a basic nitrogen atom capable of forming a solid salt and a particularly important nitrogen-containing base, such as an amine compound. Examples of chain-like amine compounds include primary amines, secondary amines, and tertiary amines; examples of cyclic amine compounds include lysine, quinoline, Examples include piperidine and imidazole. In addition, compounds such as hydroxylamine, hydrazine, and amidine are also useful as chain amines. Salts of nitrogen-containing organic bases include the above-mentioned non-y1'fII salts of vi1 bases (e.g. hydrochloride,
sulfates, nitrates, etc.) are preferably used.

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

-sj-M Margin below.

・--d rule) τ, represented by the above general formula (S), and preferable specific examples of the two radicals represented by '- are shown below.

(R-5) (R-8) C no (R-9) (R-10) (R-11) (R-12) H CH.

C, H4N HCOCH3 (R-20) (R-21) CH.

(R-22) (R-23) N1-24) (R-25) (R-26) (R27) (R-28) (R-29) (R-30) Represented by the above general formula (S) The reducing agent used can be prepared by a known method,
For example, Houben Peil, Mesosden der Organitsien Hemi, Band XI/2 (Houben
-Weyl, Methoden der Oraan
ischen Chemie, Band X I
/ 2 > pages 645-703.

Furthermore, it is also possible to use two or more of the above-mentioned reducing agents at the same time, or to use a black and white developing agent described below in combination for the purpose of increasing developability.

Further, the dye-donating substance used in the present invention is JP-A No. 57-179840, No. 58-58543, No. 5
In the case of compounds that release dyes upon oxidation, compounds that lose their ability to release dyes when oxidized, compounds that release dyes when reduced, etc. as shown in Nos. 9-152440 and 59-154445, etc. Alternatively, in the case where only a silver image is simply obtained, a developing agent as described below can also be used.

For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-tert-
butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamidophenols [e.g. 4-
Benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2.6-diproT--4
-(D-toluenesulfonamido)phenol, etc.], or polyhydroxybenzenes (e.g., hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, tert-butylhydroquinone, carboxyhydroquinone, catechol, 3-butylhydroquinone, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthol [e.g. 1,1'-dihydroxy-2,2'
-binaphthyl, 6.6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-sinitro2.2'-dihydroxy-1,1'-binaphthyl, 4.
4'-dimethoxy-1,1'-dihydroxy-2,2'
-binaphthyl, bis(2-hydroxy-1-naphthyl)
methane, etc.], methylene and sphenols [e.g. 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-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-tert-butylphenyl)
propane, 2,2-bis(4-hydroxy-3,5-di-tert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines.

These developing agents mentioned above can also be used alone or in combination of two or more.

The amount of the reducing agent used in the heat-developable photosensitive material of the present invention depends on the type of photosensitive silver halide, the type of silver silicate used, and the type of other additives, etc. Usually 0.01 per mole of photosensitive silver halide
-1500 mol, preferably 0.1-20
It is 0 mole.

Shino III Co. J Examples of the binder used in the heat-developable photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or a combination of two or more synthetic or natural polymeric substances can be used. In particular, it is preferable to use gelatin or a derivative thereof together with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in JP-A-59-229556.

This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or a copolymer (including a graft copolymer) of vinylpyrrolidone and one or more other monomers copolymerizable with vinylpyrrolidone. ). These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinyl and lolidone, and preferred polyvinylpyrrolidone has a molecular weight of 1.000 to ao
o, ooo's. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl acetates, vinyl imidazoles, (meth)acrylamides,
Examples include vinyl monomers such as vinyl carbinols and vinyl alkyl ethers, but it is preferable that polyvinylpyrrolidone accounts for at least 20% (weight %, same hereinafter) of the composition ratio. 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, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins.

In the above binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90% of the total binder.
It is preferably 10 to 80%, more preferably 10 to 80%.

The binder may contain other polymeric substances,
Gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400.000 and one or more other polymeric substances, gelatin and molecules m s, ooo to 400.0
A mixture of the vinylpyrrolidone polymer No. 00 and one or more other polymeric substances is preferred. Other polymeric substances used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral,
Examples include polyethylene glycol, polyethylene glycol ester, or proteins such as cellulose derivatives, and natural substances such as polysaccharides such as starch and gum arabic. These are 0-85%, preferably 0-70%
May be included.

Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it to stand).

The amount of the binder used is usually from o, osg to 50Q per layer per support 11, preferably 0.1g.
~109.

Furthermore, the binder is 0.00% per 1 g of the dye-providing substance.
It is preferable to use 1 to 10 g, more preferably 0.
It is 25-4g.

-P;
For example, polyethylene film, cellulose acetate film and polyethylene terephthalate film, synthetic plastic films such as polyvinyl chloride, paper supports such as photographic base paper, printing paper, baryta paper and resin-coated paper; Electron beam curable resin composition The heat-developable photosensitive material of the present invention, and when the photosensitive material is of a transfer type and uses an image receiving member, the photothermographic material and/or
Alternatively, it is preferable that various heat solvents be added to the image receiving member. The thermal solvent used in the present invention is a compound that promotes thermal development and/or thermal transfer. These compounds are described, for example, in U.S. Pat. No. 3,347,675.
No. 3.867, 959, Research Disclosure No. 17643 (XI [), Jikai [59-
229556, Special Rat Wa59-47787, etc., and those particularly useful in the present invention include, for example, urea derivatives (e.g., dimethylurea, diethylurea, phenylurea, etc.) , amide derivatives (e.g., acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1.5-bentanediol, 1.6-bentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or Examples include polyethylene glycols.

Among the above thermal solvents, water-insoluble solid thermal solvents described below are more preferably used.

A water-insoluble solid thermal solvent is a compound that is solid at room temperature but becomes liquid at high temperatures (60'C or higher, preferably 100°C or higher, particularly preferably 130'C or higher and 250°C or lower), and is an inorganic/ The organic ratio (“Yoshio Koda,” Sankyo Publishing, 1984) is in the range of 0.5 to 3.0, preferably 0.7 to 2.5, particularly preferably 10 to 2.0. A compound whose solubility in water at room temperature is 1.
Refers to smaller compounds.

Specific examples of water-insoluble solid thermal solvents are shown below, but the invention is not limited thereto.

More than 2" voice ↓ to 2. Examples of water-insoluble heat solvent melting point (°C) Pipe property/'IA property C (x) 3 CON 82 1.41'
1. ．． 4 □−1○−CON+(2128°
1.5tHO min C0N82 161° 2.2
5cH3-C-CONH2160' 1.34CI
(30÷NHCOCH3130° 131B r (y
NHCOCHs 168° 102 (ΣNHC
OCH3113~115° 1.34 Melting point C) Inorganic/Organic Cl4xOC-C0NHz 164~167°
147 °C
8° 159 Many compounds used as water-insoluble solid heat solvents are commercially available, and can be easily synthesized by those skilled in the art.

The method of adding the water-insoluble hot solvent is not particularly limited, but it may be added by grinding and dispersing it using a ball mill, sand mill, etc.
There are methods such as adding it by dissolving it in an appropriate solvent, and adding it as an oil-in-water dispersion by dissolving it in a high boiling point solvent.
It is preferable to pulverize and disperse the solid particles using a ball mill, sand mill, etc. and add them while maintaining the solid particle shape.

Layers to which the water-insoluble solid thermal solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image-receiving layer of an image-receiving member, and the like, so that the respective effects can be obtained.

The amount of the water-insoluble heat solvent added is usually 10% to 500% by weight, preferably 50% by weight to 300% by weight, based on the amount of the binder.

Note that even when the melting point of the water-insoluble solid thermal solvent of the present invention is higher than the thermal development temperature, the melting point is lowered by being added to the binder, so that it can be effectively used as a thermal solvent.

The photothermographic material of the present invention may contain various additives in addition to the above-mentioned components, if necessary.

For example, melt formers such as acetamide and succinimide described in U.S. Pat. No. 3,438,776; compounds such as polyalkylene glycols described in U.S. Pat. No. 3,666.477 and JP-A-51-19525; , -C〇-1-8O2- described in U.S. Pat. No. 3,667.959
Examples include nonaqueous polar organic compounds having a melting point of 20° C. or higher, such as lactones having a 1-8o group.

Benzophenone derivatives described in Zarani JP-A-49-115540, JP-A-53-24829, JP-A-53-
Phenol derivatives described in No. 60223, JP-A-5
Carboxylic acids described in No. 8-118640, polyhydric alcohols described in JP-A-58-198038,
Also included are sulfamoylamide compounds described in JP-A-59-84236.

Further, a color toning agent known in heat-developable photosensitive materials may be added as a development accelerator to the photothermographic material of the present invention. As a color toning agent, for example, JP-A-46-4
No. 928, No. 46-6077, No. 49-5019,
49-5020, 49-91215, 4
No. 9-107727, No. 50-2524, No. 50-6
No. 7132, No. 50-67641, No. 50-1142
No. 17, No. 52-33722, No. 52-99813, No. 53-1020, No. 53-55115, Shu 5
No. 3-76020, No. 53-125014, No. 54-
No. 156523, No. 54-156524, No. 54-
No. 156525, No. 54-156526, No. 55-
No. 4060, No. 55-4061, No. 55-32015
Publications such as No. 2,140,406 and West German Patent No. 2,140,406,
Same No. 2,141゜063, Same No. 2.220.618,
U.S. Patent No. 3,847,612, U.S. Patent No. 3,782,9
No. 41, No. 4,201,582 and JP-A-57-
No. 207/244, No. 57-207245, No. 5a-
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-, which are compounds described in specifications such as IA9628 and IA58-19354.1. Phthalazinedione, 2.3-
Dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide,
2H-1,3-benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimerkabutotetrazabentalene, aminomercaptotriazole, acylaminomercaptotriazoles, phthalic acid, naphthalic acid, phthalamic acid, etc. and mixtures of one or more of these with imidazole compounds, mixtures of at least one acid or acid anhydride such as phthalic acid and naphthalic acid and phthalazine compounds, and furthermore mixtures of phthalazine and maleic acid and itacon. Examples include combinations of acids, quinolinic acid, gentisic acid, and the like.

As an antifoggant, for example, US Patent No. 3,645.
Higher aliphatic compounds (e.g. behenic acid, stearic acid, etc.) described in No. 739, mercuric salts described in Japanese Patent Publication No. 11113/1983, and N-
Halogen compounds (e.g. N-halogenoacetamide, N
-halogenosuccinimide, etc.), US Patent 3.700
．． 457, mercapto compound-releasing compounds described in JP-A No. 51-50725, arylsulfonic acids (e.g. benzenesulfonic acid, etc.) described in JP-A No. 49-125016, lithium carboxylic acid salts described in JP-A No. 51-47419. (e.g. lithium laurate), UK r5￥f permit No. 1,
455,271, oxidizing agents (e.g. perchlorates, inorganic peroxides, persulfates, etc.) described in JP-A No. 50-101,019, sulfinic acids or thiosulfonic acids described in JP-A-53-19825. , 2-thiouracils described in No. 51-3223, simple sulfur described in No. 51-26019, No. 51-42529, No. 51-8112
No. 4, disulfide and polysulfide compounds described in No. 55-93149, rosin or diterpenes (e.g. abietic acid,
pimaric acid, etc.), polymer acids having free carboxyl groups or sulfonic acid groups as described in JP-A No. 51-1043.38, thiazolinthione as described in U.S. Pat. No. 4,138,265, JP-A-54-51821 No. 4, for U.S. patents.
1,2,4-triazole or 5-mercapto-1,2,4-triazole described in No. 137.079, thiosulfinic acid esters described in No. 55-140B33, 1 described in No. 55-142331 .2.3.4
-Thiatriazoles, No. 59-46641, No. 59
-57233, dihalogen compounds or trihalogen compounds described in No. 59-57234, Zarani No. 59
Examples include thiol compounds described in No.-111636.

In addition, as other antifoggants, Japanese Patent Application No. 59-565
Hydroquinone derivatives described in No. 06 (for example, G.C.
-octylhydroquinone, dodecanylhydroquinone, etc.) or the hydroquinone derivatives described in Japanese Patent Application No. 59-66380, and pencitriazole derivatives (e.g., 4-sulfobenzotriazole, 5-carboxybenzotriazole, etc.) are preferably used in combination. can.

Other particularly preferred antifoggants include inhibitors having a hydrophilic group as described in Japanese Patent Application No. 60-218169, polymer inhibitors described in Japanese Patent Application No. 60-262177 and special antifoggants. Compounds having a ballast group described in Japanese Patent No. 60-263564 can be mentioned.

As an ocular image stabilizer, U.S. Patent No. 3.707.37
Polyhalogenated silicate oxidizing agents described in No. 7 Mei III (e.g., tetrabromobutane, tribromoquinaridine, etc.)
, 5- described in Belgian Patent No. 768.071.
methoxycarbonylthio-1-phenyltetrazole,
Monohalo compounds described in JP-A-50-119624 (
For example, 2-bromo-2-tolylsulfonylacetamide, etc.), bromine compounds described in JP-A-50-120328 (for example, 2-bromomethylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-6- methyltriazine, etc.), and tribromoethanol described in JP-A-53-46020. Also, JP-A-5
Various monohalogenated organic antifoggants for silver halide emulsions such as those described in Japanese Patent No. 0-119624 can be used.

Other image stabilizers include U.S. Pat. No. 3,220;
No. 846, No. 4,082,555, No. 4,088
, No. 496, JP-A-50-22625, Research Disclosure (RD) No. 12021, 15
No. 168, No. 15567, No. 15732, No. 1
Compounds called activator precursors that release basic substances by heat, such as compounds such as guanidinium trichloroacetate that release bases by decarboxylation with heat, as described in No. 5733, No. 15734, and No. 15776, etc.; Galactonamide; aldnamide compounds such as amine imides, 2-carboxycarboxamides, etc., as well as sodium phosphate base generators described in JP-A-56-430745 and JP-A-56-132332, British Patent No. 2.079. Compounds that generate amines through intramolecular nucleophilic reactions described in JP-A-59-157637, hydroxamic acid carbamates described in JP-A-59-166943, etc. 59-180537@,
Examples include base releasing agents described in Japanese Patent No. 59-174830 and Japanese Patent No. 59-195237.

Furthermore, U.S. Patent No. 3.301, No. 678, No. 3.50
6.444, 3.824.103, 3.84
4,788, RD1203S, RD18016, etc., iridium compounds, S-rubamoyl derivatives of mercapto compounds, and nitrogen-containing heterocyclic compounds may be used for the purpose of stabilizing images, and The activator stabilizer described in U.S. Patent Nos. 3,669.670, 4,012,260, 4,060,420, 4.207.392, RD 15109, RD 17711, etc. and a nitrogen-containing organic base called an activator stabilizer precursor, such as α-sulfonylacetate or trichloroacetate of 2-aminothiazoline and an acylhydrazine compound, respectively, are used for the purpose of accelerating development or stabilizing the image. You can do that.

Also, for example, JP-A-56-130745 and JP-A-59-2
Development may be carried out in the presence of a small amount of water as described in U.S. Pat. 3,
312,550 and the like, development may be carried out using hot steam, hot air containing moisture, or the like. Also, compounds that release water into heat-developable photosensitive materials, such as Japanese Patent Publication No. 44-26
Compounds containing water of crystallization such as those described in No. 582, such as sodium phosphate dodecahydrate and ammonium alum diquadrate, may be incorporated into the photothermographic material.

In addition, various additives such as antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreading agents, coating aids, and the like may be used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example,
Colloidal silica can be used for the undercoat layer, intermediate layer, protective layer, etc.).

The colloidal silica used in the present invention is a colloidal solution of silicic anhydride with an average particle size of 3 to 12011 μm mainly using water as a dispersion medium, and the main component is 5iCh (silicon dioxide). Colloidal silica is described, for example, in JP-A-56-109336, JP-A-53-123916, JP-A-53-112732, and JP-A-53-100226. The colloidal silica used has a dry weight ratio of 0.05 to the binder of the layer to be mixed and applied.
A range of 2.0 to 2.0 is preferable.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example,
An organic fluoro compound can be used for the undercoat layer, intermediate layer, protective layer, etc.

The organic fluorocompounds used in the present invention are described in US Patent No. 3. , No. 589.906, 3.666, 47
No. 8, No. 3.754.924, No. 3.775.1
No. 26, No. 3.850.640, West German Patent Publication No. 1
, 942, No. 665, No. 1.961.638, No. 2.124.262, British Patent No. 1.330.356
Belgian Patent No. 742,680 and Japanese Unexamined Patent Publication No. 1973
-7781, 48-9715, 49-4673
No. 3, No. 49-133023, No. 50-99529, No. 50-11322, No. 50-160034, No. 51-43131, No. 51-129229, No. 51
-106419, 53-84712, 54-
No. 111330, No. 56-109336, No. 59-
No. 30536, No. 59-45441 and Special Publication No. 4
No. 7-9303, No. 48-43130, No. 59-58
Examples include compounds described in No. 87, etc., and these compounds can be preferably used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, an antistatic agent can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

As the antistatic agent used in the present invention, British patent tube 1
．． 466, No. 600, Research Disclosure t-
(Research 1)isclosure)
15840, 16258, 16630, U.S. Patent Nos. 2,327,828, 2,861,056, 3.206.312, 3.245.833,
No. 3,428,451, No. 3.775. i26 issue,
3.9635498, A, 025.342, 4.025. ．． No. 163, 4, 025.691
No. 4.025.704, etc., and these can be preferably used.

The thermal phenomenon photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, an ultraviolet absorber can be used in a non-photosensitive layer (eg, lower layer II, intermediate layer, protective layer, etc.).

Examples of the ultraviolet absorber used in the present invention include benzophenone compounds (for example, those described in JP-A-46-2784, U.S. Pat. No. 3,215,530, and U.S. Pat. , US Patent Tube 4
．． 045.229), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352.681), benzotriazole compounds substituted with aryl groups [ For example,
-10466, 41-1687, 42-26
No. 187, No. 44-29620, No. 4g-41572
No., JP-A-54-95233, JP-A No. 57-142975
No. 3,253.921, U.S. Patent No. 3,533,
No. 794, No. 3.754.919, No. 3.794
．． No. 493, No. 4, No. 009.038, No. 4,220
, No. 711, No. 4,323,633, Research Disclosure (ResearchQ 1sclos)
ure ) 22519], benzoxidol compounds (e.g.
55), cinnamate ester compounds (for example, U.S. Pat. No. 3,705,805, U.S. Pat. No. 3,707.
No. 375 and JP-A No. 52-49029). Zarani, U.S. Patent No. 3,499.
762 and JP-A-54-48535 can also be used. UV-absorbing couplers (e.g.
α-naphthol cyan dye-forming couplers) and ultraviolet-absorbing polymers (e.g., JP-A-58-11194
No. 2, No. 178351, No. 181041, No. 59-
No. 19945, No. 23344, and those described in the official gazette).

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, a hardening agent can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

Hardening agents used in the present invention include aldehyde-based and aziridine-based hardeners (for example, PB Report 19,921, U.S. Pat. No. 2,950,197, U.S. Pat. No. 2,964,404)
No. 2,983,611, No. 3,271,17
Specifications of No. 5, Japanese Patent Publication No. 46-40898, Japanese Patent Application Publication No. 1973
No. 0-91315), isoxazole-based compounds, for example, U.S. Pat.
), epoxy systems (e.g., those described in U.S. Patent No. 3,0
47,394, West German Patent No. 1,085,663, British Patent No. 1,033,518, Japanese Patent Publication No. 1973
-35495), vinyl sulfone type (e.g. PB Report 19.920, West German Patent No. 1)
, No. 100,942, No. 2,337,412, No. 2,
No. 545,722, No. 2,635,518, No. 2.7
No. 42.308, No. 2.749.260, British Patent No. 1,251,091, Japanese Patent Application No. 45-54236, No. 48-110996, U.S. Patent No. 3, 539.644
No. 3,490,911), acryloyl type (for example, Japanese Patent Application No. 1983-27949)
No. 3,640,720), carbodiimides (for example, those described in U.S. Pat.
No. 938.892, No. 4.043.818, No. 4.0
61, 499, Japanese Patent Publication No. 46-38715, and Japanese Patent Application No. 15095/1982)
, triazine series (e.g. West German Patent No. 2.410.97)
No. 3, No. 2,553.915, U.S. Patent No. 3,325
, No. 287, JP-A-52-12722
In addition, maleimide-based, acetylene-based, methanesulfonic acid ester-based, and N-methylol-based hardening agents can be used alone or in combination. As a useful combination technique, for example, West German Patent No. 2,447,5
No. 87, No. 2.5051746, No. 2,514,24
No. 5, U.S. Patent No. 4,047,957, U.S. Patent No. 3,832
, No. 181, specification 1 of No. 3.840.370, JP-A-48-43319, No. 50-63082, No. 52
Examples include combinations described in Japanese Patent Publication No. 127329 and Japanese Patent Publication No. 48-32364.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, a polymer hardener can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

Examples of the polymeric hardening agent used in the present invention include polymers having aldehyde groups (e.g., acrolein copolymers, etc.) described in U.S. Pat. No. 3,396,029.
, U.S. Patent No. 3.362.827, Research Disclosure No. 17333 (1978), etc., polymers having dichlorotriazine groups, U.S. Patent No. 3.623
．． Polymers having epoxy groups as described in No. 878, Research Disclosure No. 16725 (1978)
, U.S. Patent No. 4,161,407, Japanese Patent Publication No. 54-65
Examples thereof include polymers having an active vinyl group or a group that can be a precursor thereof, as described in JP-A No. 033 and JP-A-56-142524, and polymers having an active ester group as described in JP-A-58-66841.

In the heat-developable photosensitive material of the present invention, a polymer latex is used in the heat-developable photosensitive layer and/or the non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving the physical properties of the film. be able to.

Preferred specific examples of the polymer latex used in the present invention include polymethyl acrylate, polyethyl acrylate, polylobyl acrylate, a copolymer of ethyl acrylate and acrylic acid, a copolymer of nylidene chloride and butyl acrylate, and a copolymer of butyl acrylate and acrylic acid. Examples include copolymers, copolymers of vinyl acetate and butyl acrylate, copolymers of vinyl acetate and ethyl acrylate, copolymers of ethyl acrylate and 2-acrylamide, and the like.

The preferred average particle size of the polymer latex is 0.02 μm
~0.2 μm. The amount of polymer latex used is 0.0 on a dry weight basis with respect to the binder of the added layer.
3 to 0.5 is preferred.

The heat-developable photosensitive material of the present invention has various types of heat-developable photosensitive layers and/or non-photosensitive layers (e.g., undercoat layer, intermediate layer, retention layer, etc.) for the purpose of improving coating properties. surfactants can be used.

The surfactant used in the present invention may be any of anionic, cationic, amphoteric and nonionic surfactants.

Examples of anionic surfactants include alkylcarbonylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl phosphates, alkyl phosphates, N-acyl-N-alkyltaurines,
Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, and vA acid ester groups, such as sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, and polyoxyethylene alkyl phosphates Preferably.

Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings are preferred.

Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, and amine oxides.

Examples of nonionic surfactants include saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene gellicol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters). , polyethylene glycol sorbitan esters,
polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone),
Glycidol derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglyceridone, fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc.) are preferred.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, etc.) for the purpose of improving developability, improving image dye transferability, improving optical properties, etc. ,
(protective layer, etc.) may contain non-photosensitive silver halide grains.

The non-photosensitive silver halide grains used in the present invention may have any silver halide composition such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Can be used. The preferred grain size of the non-photosensitive silver halide grains is about 0.
, 3 μm or less.

Further, the amount added is preferably in the range of 0.02 to 3 g/]' in terms of ff1ffi with respect to the layer to be added.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (undercoat layer,
(intermediate layer, protective layer, etc.), for example, JP-A-51-10433.
Vinyl polymers having carboxyl groups or sulfo groups as described in No. 8 can be included.

The vinyl polymer is preferably used in a dry weight ratio of 0.05 to 2.0 relative to the binder of the layer to be added.

The following i-orientation +1':,=beat ξ The heat-developable photosensitive material of the present invention basically includes (1) photosensitive silver halide, (2) reducing agent, (3) in one heat-developable photosensitive layer. ) A dye-providing substance, (4) a binder, and, if necessary, (5) a Nada silver salt. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, the heat-developable photosensitive layer is divided into two layers, and the components (1), (2), (4), and (5) are Two or more compositions can be used as long as they are in a state where they can react with each other, such as containing the dye-providing substance (3) in the heat-developable photosensitive layer on the 10,000-side side and the dye-providing substance (3) in the layer on the other side adjacent to this photosensitive layer. It may be contained in separate layers.

Further, the heat-developable photosensitive layer may be divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, a high-density layer and a low-density layer, or the like.

The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers on a support. In the case of color, the -1 branch has three heat-developable photosensitive layers with different color sensitivities, and in each photosensitive layer, dyes with different hues are formed or released by heat development.

Typically, a yellow dye is used in the blue-sensitive layer, a magenta dye is used in the green-sensitive layer, and a cyan dye is used in the red-sensitive layer, but the invention is not limited to this. It is also possible to combine a near-infrared sensitive layer.

The structure of each layer can be arbitrarily selected depending on the purpose. For example, a structure in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on the support, or a structure in which a blue-sensitive layer is sequentially formed on the support. layer, a green-sensitive layer, a red-sensitive layer, or sequentially on a support,
There are configurations such as a green photosensitive layer, a red photosensitive layer, and a blue photosensitive layer.

In addition to the heat-developable photosensitive layer, the heat-developable photosensitive material of the present invention can be provided with non-photosensitive layers such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer. To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support, a method similar to that used for coating and preparing general silver halide photosensitive materials can be applied.

Namely, dip method, roller method, reverse roll method, air knife method, doctor blade method, spray method,
There are methods and devices for the bead method, extrusion method, stretch flow method, curtain method, etc.

The heat-developable photosensitive material of the present invention usually has a temperature of 80°C to 20°C after imagewise exposure.
1 at a temperature range of 0°C, preferably 100°C to 110°C.
Developing can be carried out by simply heating for 1.5 seconds to 120 seconds, preferably 1.5 seconds to 120 seconds. The transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with heat development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development;
Image received after heat development.

Transfer may be performed by bringing the material into close contact with the member and heating it, or by supplying water and then bringing the material into close contact with the member and further heating if necessary. Further, preheating may be performed in a temperature range of 70° C. to 180° C. before exposure. Also, JP-A-60-143338
As described in Japanese Patent Application No. 60-3644, the photosensitive material and the image-receiving member may be preheated at a temperature of 80° C. to 250° C. immediately before thermal development transfer in order to improve their mutual adhesion. .

Various exposure means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. Generally, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source.

As the heating means, all methods applicable to ordinary heat-developable photosensitive materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, high-frequency heating may be used, or further, an S conductive layer containing a conductive substance such as carbon black may be provided on the back surface of the photosensitive material of the present invention or the back surface of the image receiving member for thermal transfer, and the Joule heat generated by energization may be utilized. You can also. There are no particular restrictions on the heating pattern, including methods of preheating (breheating) and then reheating, heating at high temperatures for short periods of time, or at low temperatures for long periods of time, continuously raising, lowering, or repeating, and even heating without heating. Although continuous heating is possible,
A simple pattern is preferred. Furthermore, if the heat-developable photosensitive material of Riki's invention, in which exposure and heating proceed simultaneously, is a so-called transfer-type photosensitive material that forms a color image by transfer,
An image receiving member is used.

Hereinafter, the image-receiving layer of the image-receiving member that can be effectively used in the present invention includes:
It is sufficient that it has the function of accepting the dye in the heat-developable photosensitive layer released or formed by thermal imaging, for example, a polymer contained in a tertiary amine or a quaternary ammonium salt, as described in US Pat.
．． 709. Those described in '690 are preferably used. For example, as a polymer containing an ammonium salt, the ratio of polystyrene-N,N,N-tri-n-hexyl-N-vinyl-benzylammonium chloride is 1=4 to 4:1, preferably 1:1. be.

Examples of polymers containing tertiary amines include polyvinylpyridine. A typical image-receiving layer for diffusion transfer is obtained by mixing a polymer containing ammonium salt, tertiary amine, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support.

Another useful dye-receiving material is JP-A-57-2072.
The glass transition temperature described in No. 50 etc. is 40°C or higher, 2
Examples include those formed from a heat-resistant, stubby polymeric substance of 50° C. or less.

These polymers may be supported on a support as an image-receiving layer, or may themselves be used as a support.

Examples of the heat-resistant polymeric substances include polystyrene, polystyrene derivatives having a conversion group having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene,
Polyacetals such as polyvinylpyrrolidone, polyvinylcarbazolevinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichlorinated fluoroethylene, polyacrylonitrile, polyN,N-dimethylallylamide, p-cyanophenyl polyacrylates with pentachlorophenyl and 2,4-dichlorophenyl groups, polyacrylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polycyclo Examples include polyesters such as xyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, and polyethylene terephthalate, polycarbonates such as polysulfone, bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. In addition, Polymer Handbook Second Edition (G.I. Brand Wrap, E.H. Inmargatsut), John Wiley & Sons (Polymer) (andb
ook 2ncl ed. (J, Brandru
p, E.

H. John Wil
Also useful are synthetic polymers with a glass transition temperature of 40° C. or lower, as described in the publication (Ey & Sons). - The molecular weight of the polymer substance in the shell is 2,000 to 200.
, 000 is useful. These polymeric substances may be used alone or in a blend of two or more types, or may be used in combination of two or more types as a copolymer.

Useful polymers may include cellulose acetate, such as triacetate, diacetate, heptamethylene diamine and terephthalic acid, fluororange, and many others.

As the support for the image-receiving member, any material such as a transparent support or an opaque support may be used. Supports containing pigments such as titanium oxide, barium 5A acid, calcium carbonate, talc, etc., baryta paper, RC paper laminated with thermoplastic resin containing pigments on paper, fabrics, glasses, Supports made of metals such as aluminum, cum, etc., and supports made by coating and curing electron beam curable resin compositions containing pigments on these supports, and coating layers containing pigments on these supports. Examples include a support provided with.

In particular, a support that is coated with an electron beam curable resin composition containing a pigment on paper and cured, or a support that has a pigment coating layer directly on the paper or an electron beam curable resin composition on the pigment coating layer. The support coated with the composition and cured can be used as it is as an image receiving member since the resin layer itself can be used as a receiving layer.

Polyamides made from combinations such as propylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, polyesters made from combinations such as diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, polyethylene terephthalate, Polycarbonate is an example. These polymers may be modified. For example, polyethylene terephthalate using cyclohexane dimetatool, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy4-benzenesulfonic acid, etc. as a modifier is also effective.

A particularly preferable image-receiving layer is JP-A-59-22342
Layer made of polyvinyl chloride described in No. 5 and JP-A-60
Examples include a layer made of polycarbonate and a plasticizer described in Japanese Patent No. 19138.

These polymers can also be used as a support and an image-receiving layer (image-receiving member), in which case the support may be formed from a single layer, or the present invention can be applied to heat-developable color photosensitive materials. As a mordant for dye images, various polymers of the prior art can be used as the receiving pJi layer, but this receiving layer may also be a separate receiving element comprising the receiving layer on a suitable support. The image-receiving layer may be a single layer that is part of a heat-developable color photographic material. If necessary, an opacifying layer (reflection layer) may be included in the light-sensitive material, such layer reflecting the desired degree of radiation, such as visible light, which can be used to observe the dye image in the image-receiving layer. It is used to make The opacifying layer (reflective layer) can contain various reagents that provide the necessary reflection, such as titanium dioxide.

The image-receiving layer of the image-receiving member can also be formed into a type that can be peeled off from the heat-developable photosensitive layer. For example, after imagewise exposure of a heat-developable color photosensitive material, an image-receiving layer can be superimposed on the heat-developable photosensitive layer and uniformly heat-developed. Further, after the heat-developable color photosensitive material is subjected to imagewise exposure and uniform heat development, an image-receiving layer is overlaid and heated at a lower temperature than the development temperature, and the dye released or formed from the dye-providing substance is protected. Preferably, a layer is provided. Hereinafter, this will be referred to as the protective layer of the present invention.

Various additives used in the photographic field can be used in the protective layer of the present invention. The additives include various matting agents, colloidal silica, slipping agents, organic fluoro compounds (especially fluorosurfactants), antistatic agents, ultraviolet absorbers, high boiling point organic solvents, antioxidants, hydroquinone derivatives, Examples include polymer latex, surfactants (including polymeric surfactants), hardeners (including polymeric hardeners), filtered silver salt particles, and non-photosensitive silver halide particles.

The matting agent used in the protective layer of the present invention is fine particles of inorganic or organic substances that are incorporated into the photothermographic material to increase the roughness of the surface of the photosensitive material and make it matte. be.

A method of using a matting agent to prevent adhesion that occurs during the production, storage, and use of photosensitive materials, and to prevent static electricity caused by contact, friction, and peeling between materials of the same or different types is as follows: Well known in the industry. Specific examples of the matting agent include silicon chloride described in JP-A-50-46316, JP-A-53-7231 and JP-A-5L66937,
Alkali-soluble matting agents such as alkyl methacrylate/methacrylic acid copolymers described in JP-A No. 60-8894, alkali-soluble polymers having anionic groups described in JP-A-58-166341, JP-A-58-145935 A combination of two or more types of fine particle powders with different Mohs hardnesses, a combination of oil droplets and fine particle powders as described in JP-A-58-147734, two types with different average particle sizes as described in JP-A-59-149356 Combination of the above spherical matting agents, JP-A-56-4
The combination of a fluorinated surfactant and a matting agent described in No. 4411, British Patent No. 1.055.713, U.S. Patent No. 1,939,213, U.S. Patent No. 2,221,873, U.S. Pat.
2.268.662, 2.322.037, 2.376, 005, 2.391.181,
No. 2,701,245, No. 2.992,101,
No. 3,079,257, No. 3,262,782,
3.443.946, 3,516,832, 3,539,344, 3.591, 379, 3.754.924, 3.7671448, JP-A-49 - Organic matting agent described in No. 106821, No. 57-14835, etc., West German Patent No. 2.529.32
No. 1, British Patent No. 760.775, 1.1.260,
No. 772, U.S. Patent No. 1,201,905, 2.
No. 192,241, j permit 3, No. 053.662, same 3
．． 062.649 No. 1, 3, 25L 2O2M,
No. 3,322,555, No. 3,353.958, No. 3,370,951, No. 3,411,907, No. 3
, No. 437,484, No. 3.523.022, No. 3
, No. 615,554, No. 3,635.714, No. 3
, No. 769.020, No. 4,021,245, No. 769.020, No. 4,021,245, No.
4.029.504, etc., or JP-A-46-7781 and JP-A-49-106.
No. 821, No. 51-6017, No. 53-116143
No. 53-100226, No. 57-14835,
No. 57-82832, No. 53-70426, No. 5
Matting agents having physical properties such as those described in Japanese Patent Publication No. 9-149357, Japanese Patent Publication No. 57-9053, and Hini EP-107,378 are preferably used.

In the protective layer of the present invention, the addition m of the matting agent is preferably '+ Om (1/2.0 g, more preferably 20II1 g to 1.0 g per 1 f). The particle size of the matting agent is 0.5 to 10 μm. Preferably, more preferably 10-6
It is μm.

The matting agents may be used in combination of two or more.

Examples of the slipping agent used in the protective layer of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, and synthetic waxes.
No. 80,465, British Patent No. 955.061, 1,
No. 143,118, No. 1,270,578, No. 1,3
No. 20.564, No. 1,320,757, Japanese Unexamined Patent Publication No. 1973
-5017, 51-141623, 54-1
No. 59221, No. 56-81841, Research Disclosure t-(Research[)isclos
ure ) 13969, U.S. Patent No. 1,263.
No. 722, No. 2.588.765, No. 2.739.8
No. 91, No. 3,018.178, No. 3,042.5
No. 22, No. 3,080,317, No. 3, 082.0
No. 87, No. 3,121,060, No. 3.222.
No. 178, No. 3,295,979, No. 3.489.5
No. 67, No. 3,516,832, No. 3,658,57
No. 3, No. 3,679,411, No. 3.870.521
Those described in No. 1, etc. can be preferably used.

The protective layer of the present invention contains a high boiling point organic solvent (for example, U.S. Pat. No. 2,322,027, U.S. Pat.
, No. 533,514, No. 2,882,157, Japanese Patent Publication No. 46-23233, British Patent No. 958,441, No. 1,222.753, US Patent No. 2,353,262
No. 3,676, M2 No. 3,700,454,
Esters (e.g. phthalates, phosphoric esters, fatty acid esters, etc.), amides (e.g. fatty acid amides, (such as sulfonated amides), ethers, alcohols, and paraffins. ) may contain oil droplets in which a water-insoluble oil compound is emulsified and dispersed. Furthermore, these oil droplets may contain photographic additives for various purposes.

Binders used in the protective layer of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, polyethyl oxazoline, polyacrylamide,
One or more synthetic or natural polymeric proboscises such as gelatin and phthalated gelatin can be used in combination.

In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (molecular weight preferably 1,000 to 400,000), polyvinyl alcohol (molecular weight i, ooo to 1
00.000 is preferred) and polyoxazoline (molecular weight i, preferably ooo to 800.000) alone or in combination of two or more of these binders are preferred, and gelatin alone or gelatin and the above polyvinylpyrrolidone, polyvinyl alcohol and polyoxazoline are preferred. Particularly preferred are binders that use hydrophilic polymers that are highly compatible with gelatin, such as the following. Gelatin may be treated with lime, acid, or ion exchange, and may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins.

The thickness of the protective layer of the present invention is preferably 0.05 to 5 μm, more preferably 0.1 to 1.0 μm. The protective layer may be a single layer or may be composed of two or more layers.

Further, in order to increase film strength and prevent film destruction, it is also preferable that the hardness of the protective layer is greater than that of the photosensitive layer. How to make the degree of hardness of the protective layer greater than that of the photosensitive layer, that is, 1 @ 5! One way to control the film hardness is to use a diffusion-resistant hardener.By using a diffusion-resistant hardener in the protective layer, the hardness of the protective layer can be controlled only by the hardness of the photosensitive layer. Can be made larger.

Polymer hardeners are known as diffusion-resistant hardeners, and are disclosed in U.S. Pat. Nos. 3.057.723 and 3.39.
No. 6.029, No. 4,161,407, JP-A-58-
Hardeners described in No. 50528 and the like can be used.

Another way to control the degree of dura for each layer is to
Preserves diffusible hardeners (e.g. Nilsulfone hardeners)! The hardness of the protective layer can be made thicker than that of the photosensitive layer by containing it in only one layer or by making the content of the protective layer higher than that of the photosensitive layer and quickly drying it after simultaneous multilayer coating.
can.

[Effects of the Invention] By containing the cyan dye-providing substance of the present invention, the heat-developable photosensitive material of the present invention is less likely to be decomposed by heat and/or a coexisting reducing agent during thermal development, and is highly concentrated. A cyan dye image with less fog can be obtained.

Of course, the cyan dye image formed in the heat-developable photosensitive material of the present invention is a clear image.

Examples of the present invention are shown below, but the present invention is not limited thereto.

Example-1 [Preparation of silver iodobromide emulsion] At 50°C, JP-A No. 57-92523, No. 57-
92524, an aqueous solution containing 11.60 g of potassium iodide and 131 g of potassium bromide in solution A in which ossein gelatin 20a, 100 g of distilled water, Q and ammonia were dissolved, An aqueous solution containing 500 g of solution B, 1 mol of silver nitrate, and ammonia
Solution C of 11I2 was added at the same time while keeping the DAQ constant. The shape and size of emulsion grains to be adjusted are pH, l)A
! :1 and by controlling the addition rates of liquids B and C. In this way, a core emulsion with a silver iodide content of 7 mol %, regular octahedral grains, and an average grain size of 0.25 μm was prepared. Next, in the same manner as above, a core/shell type silver halide emulsion with a regular octahedral shape and an average grain size of 0.3 μm was obtained by coating a silver halide shell with a silver iodide content of 1 mol %. Prepared.

(The monodispersity was 9%.) The emulsion thus prepared was washed with water and desalted. The yield of the emulsion was Boo, (1.

Furthermore, a photosensitive silver iodobromide emulsion was prepared from the silver iodobromide emulsion prepared above in the following manner.

a) Preparation of red-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 700d4-hydroxy-6-methyl-1°3.3a,7-titrazaindene 0.4ggelatin 3213Sodium thiosulfate 10mgThe following sensitizing dye methanol 1% Liquid 301g distilled water
1200,41 SojI! ! Wood (a) 1]) Preparation of green-sensitive silver iodobromide emulsion Said silver iodobromide emulsion 700d1-hydroxy-6 1 ml 1° 3.38.7-''ytra 1f inde'/0.A
Q geladin 32g Sodium thiosulfate 10mg
U Knorr 1% liquid 80112 distilled; distilled water

1200dj Sosensitizing dye (1)) C) Preparation of 1-sensitizing iodobromide polishing agent Jna silver iodobromide polishing agent 700-1
+2t↓-Hydroxy-6-Mejiru 1°3.3a 7. - Detrazaindene 0.4g Geratin
32 lithium ion + 1% methanol solution of the following sensitizing dye 80d distilled water
1200 iL2 Dust-sensitive dye <c> [Right modified silver salt dispersion] 5-methylbenzotriazole and silver nitrate were reacted in a water-alcohol mixed solvent, and 28°8 g of 5-methylbenzotriazole silver and poly( 33 g of N-vinylpyrrolidone) [,0(1, and 4-sulfobenzotriazyl sodium 1-lium salt L) was dispersed in an alumina ball mill to give a pI of 2001 g to 15.5.

[Preparation of dye-providing substance dispersion] Exemplary dye-providing substance PC-6-99,2 (5.0 g of 1,2,4-di(1) octylhydroquinone and 1.0 g of the following antifoggant were mixed with 30 (l) of ethyl acetate. Dissolved in Alkanol
Q and 26.4 g of photographic gelatin and phenylcarbamoylated gelatin (Rouslow, type 17819P C
> 34.6 (1440111 gelatin aqueous solution containing l
2 and dispersed with an ultrasonic homogenizer, the ethyl acetate was distilled off, and the pH was adjusted to 5.5 to 1590d.

[Preparation of reducing agent liquid J] Illustrated reducing agent R-11:93.2! J was dissolved in a solution consisting of 20% aqueous solution of polyvinyl gorolidon (K-30) 2 (2) 7 Tsuru and the following surfactant 5% aqueous solution 'Fi40112 to 4, and water and an aqueous citric acid solution were added. pH7
, 0 reducing agent liquid 600 yen is 17.

Preparation of surfactant hot solvent dispersion> p-1-Ramide 430 (J polyvinypyroton)
, K-30)'s 1.0 crime? 6 aqueous solution 1.4IO,f
i was mixed and dispersed in a ball mill to obtain a liquid in the hot solvent portion 11.

[Formation of heat development 8 photosensitive material (Trial No. 1)] 1+7 Undercoat layer 180 μm transparent polyethylene terephthalate film for photocopying, on the r shim, the above silver iodobromide emulsion, A coating liquid having the following composition was prepared using a large silver-filled dispersion liquid, a Q element donor', a dispersion liquid 5, a reducing agent solution, and a heat-screening agent 11 parts (liquid). This was applied and dried to produce a heat-developable photosensitive material (sample No. 1).

(Coating liquid composition) Organic silver salt dispersion 641ρ Red-sensitive silver iodobromide emulsion i 30.7mg Reducing agent liquid 38.4d Heat solvent dispersion
94.8nQ dye-providing substance dispersion 101% photographic gelatin 10%
Aqueous solution 21. hQ phenylcarbamoylated gelatin 10% aqueous solution 27.7t+β
Citric acid aqueous solution and water (1) adjusted to H5.5) 8'Jv
Q2.4-dichloro-6-hydroxy-3-triazine sodium 2.5% aqueous solution 13.3111
2 total 480
[Preparation of image receiving member] Polycarbonate (Molecular weight 25,000.1-1250
, Teijin Kasei) was applied onto photographic baryta paper and dried to form a polycarbonate of 15. O(J/
An image-receiving member was manufactured so as to have a size of 12.

[Evaluation of Photosensitive Material] The photosensitive material obtained by the above method was exposed to red light of 8000 MS through a step wedge.

Next, the polycarbonate-coated surface of the image receiving member and the photosensitive layer surface of the exposed photosensitive material were overlapped, and 150
Thermal development was carried out at 90°C for 90 seconds, and when the image receiving member was peeled off, a cyan transferred image was obtained on the image receiving member. The maximum reflection density (Qmax) and fog (Dmin) of the obtained cyan image are shown in Table 5 below.

The same photosensitive material as Sample N011 except that the dye-providing substance in Sample No.
Samples Nos. 12 to 6) were prepared. In addition, as a comparative light-sensitive material, Sample No. 011 was used except that the dye-providing substance in Sample No.
The same photosensitive materials as No. 11 (Samples Nos. 007 to 9) were produced.

Note that the amount m of the dye-providing substance added is the same amount (same mole m) as the amount of the dye-donating substance added in Test II No. 1 in all cases.

These samples (Samples No. 2 to 9) were exposed to light and thermally developed in the same manner as Sample No. 1 to obtain a cyan transfer image on the image receiving member. [)maxtj of these images
and [)min are shown in Table-5.

(A) (B) COOHUL 3 (C) In addition, in the dye-providing substances C-9, 0-11 and (C), 1 to licresyl phosphate (
Half of the dye-donor substance was used.

Table 5 As is clear from the following formula-5, in sample No. 027 using the dye-donor substance <A), [ ) max is very low due to the low dye-forming ability of the dye-donor substance.

In addition, sample No. using the dye-donating substance (B) or <C)
, 8 and 9, a part of the formed dye is decomposed by heat, resulting in a decrease in Dmax.

On the other hand, in samples Nos. 1 to 6 using the cyan dye-donating substance of the present invention, [) max is high and Dm
A transferred image with low in is obtained. That is, Samples Nos. 1 to 6 according to the present invention have a high pigment-forming ability and are less likely to be decomposed by heat or a coexisting reducing agent, resulting in a high maximum reflection density (Q+++ax) and a low fog (Dmin). ) can be obtained.

Example-2 Preparation of dye-providing substance dispersion> Exemplary dye-providing substance C-3: 73. Oa, 36.5 g of tricresyl phosphate, 2,4-di(1)octylhydroquinone s, og, and 10 g of the antifoggant described in Example-1 were dissolved in 300 g of ethyl acetate, and alkanol XC ( DuPont) 5 Kotan% aqueous solution 2481/l and a gelatin aqueous solution 144 (ld) containing 346q of photographic gelatin and dispersed with an ultrasonic homogenizer, and after distilling off ethyl acetate, 11 H6,0
I finished it in t590d.

A coating solution having the following composition was coated on photographic baryta paper to a wet film thickness of 80 μm and dried.
, 10) were prepared.

(Coating liquid composition) Ariiso silver salt dispersion liquid (as described in Example-1) 641g Red-sensitive silver halide emulsion liquid (as described in Example-1) 30.712 Reducing agent liquid (as described in Example-1) 38.4d Hot solvent dispersion (as described in Example-1) 75.8.4 The above dye-providing substance dispersion 1041g Photographic gelatin 10% by weight aqueous solution 60d Citric acid aqueous solution and water (11H6 , adjusted to 0) 93.81 L 2.5% aqueous solution of sodium 4-dichloro-6-hydroxy-3-1 heliazine 13.3 d total
480d, the same photosensitive material (sample No. 11
-13) were produced. Sample 1 was used as a comparative light-sensitive material except that the dye-providing substance was replaced with (D) and (E) shown below.
The same photosensitive materials as Sample No. 0 (Samples No. 014 to 15) were prepared.

The obtained photosensitive material (sample Nos. 10 to 15) was exposed to red light at 8000 M S through a step wedge, and then a polyethylene terephthalate base was placed on the surface of the photosensitive material and thermally developed at 145° C. for 90 seconds. I did it. [) max and D m of the obtained cyan image
in is shown in the following formula-6.

(D) Cノ (E) ○CH,C○OH ,? As is clear from Table 6, the light-sensitive material of the present invention has a higher [) raa of cyan dye image than the comparative light-sensitive material.
x is high. This is sample No. according to the present invention.

This is probably because the cyan dye-providing substance of the present invention is less likely to be decomposed by heat or a coexisting reducing agent.

Example 4 The coating solution described in Example 1 was wetted onto a 180 μm thick photographic transparent polyester terephthalate film having an undercoat layer! It was coated to a thickness of 65 μm and dried to form a first photosensitive layer.

A first intermediate layer having the following composition was coated on the first photosensitive layer.

Gelatin 0.613/1'
Polyvinylpyrrolidone 0.30/v' The following compound (CD' scavenger) 0.2g Methylbenztriazole silver 0.6 (1 p-t-ruamide 1.0 (J/'m22.4-dichloro-6-hydroxy-3- triazine sodium 1 cum 20II 1g/
, tCD' Scavenge V-CR2 A silver iodobromide emulsion was prepared on the first intermediate layer by replacing the dye-providing substance of Example-1 with the following magenta dye-providing substance @-1
Example-1 except that the green-sensitive silver iodobromide emulsion described in .
A coating solution having the same composition as above was applied to a wet film thickness of 5 μm to form a second photosensitive layer.

On the second photosensitive layer, a second intermediate layer having a composition obtained by adding the following yellow filter dye (0.2 g/l') to the composition of the first intermediate layer was coated.

Further, on the second intermediate layer, a silver iodobromide emulsion was prepared by replacing the dye-providing substance in Example 1 with the following yellow dye-providing substance.
A coating solution having the same composition as in Example 1 except that the blue-sensitive silver iodobromide emulsion described in Flag Example 1 was used was coated to a wet film thickness of 75 μm to form a third photosensitive layer.

Further, on the third photosensitive layer, a coating W! of the following composition is applied. The layers were coated to obtain a multilayer photosensitive material (Sample No. 0.16).

Gelatin 0.28 (1/m'
Polyvinylpyrrolidone 0.140/1'S
iO20,36s/f Saffron 1.013/*'p
- Toluamide 0.42 (1/f) In addition, the cyan dye-providing substance (B) in the first layer of the above-mentioned multilayer photosensitive material was used as the comparative dye-providing substance (B) described in C-9 and Example-2.
Multilayer photosensitive materials (Samples Nos. 17 and 18), which were the same as Sample No. 16 except that .

Each of the obtained photosensitive material samples No. 16 to 18 was
Transfer densities ([) maX and [) of cyan, magenta, and yellow dyes, respectively, exposed to 0 CMS red light, green light, and blue light, and without heat developability similar to Example-1.
m1n) was measured. The results are shown in Table 7 above.

Table 7 As is clear from Table 7 above, the photosensitive material of the present invention has a higher [) max of the cyan dye image than the comparative photosensitive material. This effect is greater than that in Example 1. This is because the photosensitive material of this example is of a so-called multi-layer type, so the diffusion time of the dye-donating substance in the photosensitive layer is long, and the dye is decomposed due to contact between the dye-donating substance and the reducing agent present in other layers. It is presumed that this is because more thermal decomposition of the cyan dye occurs in the comparative photographic material than in the optical material of the present invention using the cyan dye-donating substance of the present invention.

In addition, as is clear from Table 7 above, sample No.
In samples No. 17, color mixture presumably caused by diffusion of the cyan dye into other layers occurred, and it can be seen that sample No. 16 is more effective in terms of the immobility of the dye donor.

Claims (1)

[Scope of Claims] A heat-developable photosensitive material having a photographic constituent layer containing at least a photosensitive silver halide, a reducing agent, a dye-providing substance, and a binder on a support, wherein at least one of the dye-providing substances is one of the following general compounds. A photothermographic material characterized by being a compound represented by formula (1) or a polymer derived from the compound. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents a monovalent organic group, R^2 represents an alkyl group having 2 to 6 carbon atoms, and R^ 3 represents a hydrogen atom or a monovalent organic group, X represents a hydrogen atom or a halogen atom, Y represents an oxygen atom or a sulfur atom, and M represents a hydrogen atom, an NH_4 group, or a monovalent metal atom. )