JPS6315246A - Heat developable color photosensitive material which can form sharp image - Google Patents

Abstract

PURPOSE:To prevent the generation of contamination on a formed image by incorporating a polymer contg. <=20% component having <=2,000mol.wt. and having at least a group which forms a Schiff base at the time of heat development into a titled material. CONSTITUTION:The polymer contg. <=20% component having <=2,000mol.wt. and having at least the group which forms the Schiff base at the time of heat development is incorporated into the titled material. The effect of decreasing the contamination is obtd. if the content of the component having <=2,000mol.wt. is preferably <=10%, more preferably <=5%. The weight average mol.wt. of the polymer is preferably 3,000-500,000. The group which forms the Schiff base at the time of heat development is preferably a group which forms the Schiff base by reacting quickly with the compd. having an amino group at 80-200 deg.C, and is more particularly preferably an aldehyde group. The sharp transferred image which does not generate the image contamination is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a thermochromic color photosensitive material capable of obtaining clear images, and in particular, to a thermochromic color photosensitive material capable of obtaining clear images. The present invention relates to a heat-developable color photosensitive material that can produce clear images with very little contamination.

BACKGROUND OF THE INVENTION In recent years, thermal phenomenon photosensitive materials that can be subjected to heat treatment in the developing process have been attracting attention as photosensitive materials.

Regarding such thermal phenomenon 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 thermal phenomenon photosensitive materials and obtain color images by various methods.

For example, U.S. Patent No. 3,53L286, ! ,7
61゜270 and 3.764.328, etc., a method for forming a dye image by the reaction of an oxidized product of an aromatic first-handling amine developing agent with a coupler, Research Disclosure v- (Research D 1
sc-1osure) 15108 and 151
27, a dye is produced by the reaction of a coupler with an oxidized form of a sulfonamide phenol or sulfonamide aniline derivative (hereinafter also referred to as a developer or developer) as described in U.S. Patent No. 4,021.240. A method for forming an image, as disclosed in British Patent No. 1.590.956, uses an organic imino silver salt having a dye part, releases the dye in a heat development part, and forms a dye image on a separately provided image receiving m. A method of releasing
No. 52-105822, No. 56-50328,
A method for obtaining a positive dye image by a silver dye bleaching method disclosed in U.S. Pat. No. 4,235,957, etc., as well as U.S. Pat.
No. 4,022.617, No. 4.452.88
Various methods have been proposed, such as the method of obtaining a dye image using a leuco dye disclosed in No. 3 and Japanese Patent Application Laid-Open No. 59-206831.

However, these proposals regarding the heat-developable color light-sensitive materials have the disadvantages that it is difficult to bleach-fix the black, white, and silver images that are formed at the same time, that it is difficult to obtain clear color images, and that it is difficult to obtain clear color images. 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. 57-20
No. 7250, etc., disclosed a method of obtaining a color image by transferring a diffusible dye released by a thermal phenomenon.

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. 59-174834, 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
No. 4445, No. 59166954, etc., are non-diffusible reducing dye-donating substances that lose the ability to release diffusible dyes when oxidized, and conversely, non-diffusible reducing dye-donating substances that release diffusible dyes when reduced. a method containing a dye-donating substance;
etc. have been proposed.

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 a passive 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.

Although the clarity and stability of images formed from heat-developable color photosensitive materials have been significantly improved in recent years, it has been difficult to solve the problem of image staining, especially staining during image storage. Among these, it has been an important issue to eliminate image stains caused by various additives, particularly reducing agents or reducing agent derivatives, contained in heat-developable color photosensitive materials.

[Object of the Invention] An object of the present invention is to provide a heat-developable color photosensitive material that provides excellent clarity and stability of formed images, and in particular does not cause staining on the formed images.

[Constitution of the Invention] The above-mentioned object of the present invention is to provide a heat-developable color photosensitive material having a heat-developable photosensitive layer containing at least a photosensitive silver halide, a dye-providing substance, a reducing agent, and a binder on a support. This can be achieved by using a heat-developable color photosensitive material which contains 20% or less of a component of 2,000 or less, and which contains at least a polymer having a group that generates a Schiff base during thermal development.

It is known that aldehyde group-containing compounds and certain ketone compounds usually react with amino group-containing compounds to form Schiff bases. The present inventors focused on a reaction that induces a Schiff base from an amino group-containing reducing agent during thermal development as a means to capture a reducing agent that is assumed to be a cause of image staining.

However, the Schiff base produced by this reaction is
Since the Schiff base itself is usually colored yellow, the presence of the Schiff base on an image causes significant yellow staining. The inventors
In particular, in order to utilize this reaction in a diffusion transfer type heat-developable color photosensitive material, a means for capturing an amino group-containing reducing agent in the photosensitive material and preventing the generated Schiff base from migrating onto the transferred image is provided. As a result, we investigated the polymerization of compounds that have groups that generate Schiff bases during thermal development.

As expected, the yellow stain on the transferred image was significantly reduced. However, if a large amount of low molecular weight components exist in a polymer that has a group that generates a Schiff base during thermal development, a yellow compound that is a Schiff base generated from these low molecular weight components will migrate onto the transferred image, causing contamination. It will be recognized as. In this research, we found that by using a polymer with a low content of this low molecular weight component, it is possible to obtain clear transferred images without image staining.

20% of components with molecular m2000 or less used in the present invention
Polymers (hereinafter referred to as the polymers of the present invention) which have at least a group that forms a Schiff base upon thermal development have a molecular ffi of 20t) or less, and have at least a group that forms a Schiff base during thermal development.
If it is 0% or less, a contamination reduction effect is recognized, but preferably the component with a molecular weight of 2,000 or less is 10% or less, and more preferably the component with a molecular weight of 2,000 or less is 5%.
It is as follows. Moreover, the weight average molecular weight of the polymer of the present invention is preferably 3,000 to 500,000. The molecular weight used in the present invention is measured by GPC method (gel permeation chromatography: borisdylene conversion).

The group that the polymer of the present invention has that generates a Schiff base during thermal development is preferably a group that reacts with a compound having an amino group at 80°C to 200°C and quickly generates a Schiff base, such as Among them, an aldehyde group and a carbonyl group, particularly preferably an aldehyde group.

The group that the polymer of the present invention has that forms a Schiff base during thermal development may be protected in advance with another substituent.

The polymer of the present invention may be a homopolymer, a copolymer, a terpolymer, or a polymer of four or more types of repeating units. It is sufficient if there is a group that generates a Schiff base during thermal development, but in order to expect a large contamination reduction effect with a small amount of addition, the proportion of groups that generate a Schiff base during thermal development in the polymer is The larger the value, the more preferable it is, and the proportion of the group that forms a Schiff base during thermal development in the equivalent molecular weight of the polymer is preferably 8% or more, more preferably 15% or more.
% or more.

One of the preferred forms of the polymer of the present invention is that one of the repeating units constituting the polymer has at least a group that generates a Schiff base during thermal development, and more preferably has the following general formula, [■]. The monomer represented.

In the general formula [Eco It is a group that generates a Schiff base, such as an aldehyde group or a carbonyl group, with an aldehyde group being particularly preferred.

In the general formula [E], n represents an integer of 1 or more, and A represents an organic group, but any organic group may have any structure as long as it can pack with X and Q, such as an alkyl group, a cyclo Examples include alkyl groups, aryl groups, and heterocyclic groups.

The alkyl group may be linear or branched, such as methyl group, ethyl group, rhopropyl group, n-butyl group, t-
Examples include butyl groups, and those having substituents are also included. Examples of the cycloalkyl group include cyclohexyl group, cyclopentyl group, cyclohebutyl group, etc.
This also includes those that revise the redemption basis. As an aryl group,
Examples include phenyl group, naphthyl group, etc. Substituent 8
It also includes those who have. Examples of the polycyclic group include a pyridyl group, a furyl group, a benzoxazole group, a dioxolane group, and a morpholinyl group, including those having substituents.

These substituents include, for example, eight atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, etc.), aryl groups (e.g., phenyl group, etc.).
, Arco;1-shimcIfA! -oxy group, ethoxy group, etc.), acyl group (e.g. acetyl group, benzoyl group, etc.), acylamino group (e.g. acetamido group, etc.), carbonyloxy group (e.g. a!?1-oxy group, etc.), and these When there are two or more substituents, they may be the same or different.

Q in general formula [I] does not represent an ethylenically unsaturated group or a group having an ethylenically unsaturated group, but is preferably represented by the following general formula [1].

General formula [1 [] In the formula, R is a hydrogen atom, a carboxy group, or an alkyl group (
For example, methyl group, ethyl group, etc.), and this alkyl group also includes those with T5v substituents, and the substituents include:
For example, halogen atoms (for example, fluorine atoms, chlorine atoms, etc.), carboxy groups, etc. The carboxy group represented by R and the carboxy group of the substituent may form a salt. Jl and J2 each represent a divalent bonding group, and examples of the divalent bonding group include -NHCO-1-CO
NH-1-COO-1-〇C0-1-CO-1-SCO
-1-COS-1-0-1-S-1-8〇-1-8O2
- etc. (1) and (2) each represent a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include an alkylene group, an arylene group, an aralkylene group, an alkylenearylene group, and an arylenealkylene group. is, for example, a methylene group, an ethylene group, a propylene group, etc., an example of an arylene group is a phenylene group, and an example of an aralkylene group is
Examples of the alkylenearylene group include a methylenephenylene group, and examples of the arylenealkylene group include a phenylenemethylene group.

k, it, ffl+, f12. m2 represents O or 1, respectively.

Comonomers that can form the polymers of the present invention include:
Acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, Examples include vinyl heterocyclic compounds, glycidyl esters, 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, cyanoethyl acrylate, 2-acetoxy Ethyl 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-methoxybutyl 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 (number of moles added 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, lopropyl methacrylate, isopropyl methacrylate-1-1n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclo to hexyl methacrylate 1, benzyl methacrylate
1-, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3
-Phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate , dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-ahythoxyethyl methacrylate, 2-acetoacetoxyethyl meccrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2 -butoxyethyl methacrylate, 2-(
2-methoxyethoxy)ethyl methacrylate, 2-(
2-ethoxyethoxy)ethyl methacrylate, 2-(
Examples include 2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mole number n = 6), amyl methacrylate, and dimethylaminoethyl methacrylate methyl chloride salt. .

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate 1-, vinyl isobutyrate, vinyl caprony 1-, vinyl chloroacetate, vinyl me-1-xyacetate, vinyl phenyl acetate, donyl benzoate, Examples include vinyl salicylate.

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, dichlorostyrene, bromstyrene, vinylbenzoic acid methyl ester, etc. 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 such relaxing comonomers include the following.

Acrylamides, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tart-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyethylacrylamide, dimethylamineethylacrylamide, phenylacrylamide, diethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.: Methacrylamides, such as methacrylamide, methylmethacrylamide, ethylmethacrylamide amide, propyl methacrylamide, butyl methacrylamide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, bitroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, 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, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Nyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl Ketones, etc.; Vinyl heterocyclic compounds, such as vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate-1. unsaturated nitriles, such as acrylonitrile, methacrylonitrile, etc.; polyfunctional monomers, such as divinylbenzene, methylene bisacrylamide, ethylene glycol dimethacrylate, etc.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates, such as monomethyl itaconate, monobutyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates, such as maleic M
E-methyl, monoethyl maleate, monoethyl maleate, etc.; citraconic acid, methylene sulfonic acid, vinylbenzyl sulfonic acid, nylsulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxymethylsulfonic acid, acryloyloxy Propylsulfonic acid, etc.; Methacryloyloxyalkylsulfonic acid, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; Acrylamidoalkylsulfonic acid,
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, for example 2-methacrylamido-2 -methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid; acryloyloxyalkyl phosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxyethyl phosphate, 2-phosphate, etc.; Methacryloyloxyalkyl phosphate, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.: Sodium 3-arylokydi-2-hydroxypropanesulfonate having two hydrophilic groups, etc. can be mentioned. These acids may be salts of alkali metals (eg, Na, etc.) or ammonium ions. Other comonomers include U.S. Patent No. 3.459.790, U.S. Patent No. 3.438.708, U.S. Pat. .673 issue,
Crosslinking monomers described in JP-A-57-205735 and the like can be used. Examples of such crosslinking monomers include N-(2-acetoacetoxyethyl)acrylamide, N-(2-(
Generally, polymers are polymerized by emulsion polymerization or solution polymerization, and the polymers of the present invention having 2-acetoacetoxyethoxy)ethyl)ac can also be polymerized by a similar method. Milk (U.S. Patent No. 4.0 regarding the larva method
No. 80211, No. 3.370.952, and U.S. Pat. No. 3,451,820 for dispersing lipophilic polymers in the form of latex in aqueous geladine solutions. Can be done.

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

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 sulfur M salts of nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxypropylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines.

Further, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Examples of the polymeric protective colloid include polyvinyl alcohol and hydroxyethyl cellulose. These protective colloids may be used as emulsifiers or in combination with surfactants. For information on the types of these active agents and their effects, see Belgisc.
heChemische I Mustrie, 2
8.16-20 (+963).

In order to disperse a lipophilic polymer synthesized by a solution polymerization method etc. in the form of a latex in an aqueous solution of gelatin, the lipophilic polymer is first dissolved in an organic solvent, and then the dispersant f'' is added to an aqueous gelatin solution. Ultrasound,
Disperse into a raax shape using a colloid mill or the like. Parent a
U.S. Pat. No. 3,454,820 discloses a method for dispersing II polymers in latex form in an aqueous geladin solution.
listed in the number.

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

Moreover, these stone gate solvents can be used alone or in combination of two or more types.

In producing the polymer of the present invention, the solvent used for polymerization is preferably one that is a good solvent for the monomer and the resulting polymer and has low reactivity with the polymerization initiator. Specific examples include water, toluene, alcohol (e.g. methanol, ethanol, 15O-propanol, tert-butanol, etc.), acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, dimethylformamide, dimethyl sulfoxide, acetonitrile, methylene chloride, etc. These solvents may be used alone or in combination of two or more.

Although it is necessary to consider the type of polymerization initiator, the type of solvent used, etc., the polymerization temperature is usually in the range of 30 to 120°C.

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

Examples of water-soluble polymerization initiators include potassium persulfate, ammonium persulfate, and sodium persulfate. !
Acid salts, water-soluble azo compounds such as sodium 4.4'-azobis-4-cyanovalerate and 2.2'-azobis(2-amidinopropane) hydrochloride, and hydrogen peroxide can be used.

In addition, among the polymerization precipitants used in solution polymerization methods, for example, azobisisobutyronitrile, 2.2'-
Azobis-(2,4-dimethylvaleronitrile), 2.
2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1.1'-azobis(cyclohexanone-1-carbonitrile), 2.2'-azobisisocyanoacetic acid, 2.2' -dimethyl azobisisobutyrate, 1
．． Azo compounds such as 1'-an'bis(cyclohexanone-1-carbonitrile), 4,4'-azobis-4-cyano citrate, benzoyl peroxide, lauryl peroxide, chlorobenzyl baroside, diisopropylene Examples include peroxides such as peroxydicarbonate and di-t-butyl peroxide.

Preferred among these include benzoyl peroxide, chloropencyl peroxide, and lauryl peroxide.

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

Furthermore, polymerization methods other than the above-mentioned polymerization methods, such as suspension polymerization and bulk polymerization, can also be applied. That is,
In the present invention, a homopolymer of a monomer having a group that generates a Schiff base during thermal development, a copolymer formed by combining two or more of the monomers, or a copolymer of the monomer and a small amount of other monomers (in both cases, one type of monomer) is used. It includes all copolymers consisting of a polymerizable comonomer as a copolymerization component, and is not limited by the synthesis process.

Specific representative examples of the polymer of the present invention will be listed below, but the invention is not limited thereto.

x = 20wt% 0-4% y = 80wt% n-8% P-(5) x -55wt% n = 1.5%y-15wt
% Z=20wt% P-(6) P-(7) P-(8) x=20wt% n=2% y=8wt% P-(9) y=25wt% P-(10) Polymer of the present invention is the emulsion layer, intermediate, should be, Ho3 FIJ
The compound may be added to any layer of the light-sensitive material, or may be added to two or more layers, but is preferably added to the middle eight layers and/or the protective layer.

The amount of the polymer of the present invention added is preferably 01 to 500 mol%, more preferably 1 to 200 mol%, based on the amount of reducing agent contained in the photosensitive material.

The polymer of the present invention may be incorporated into the photographic constituent layer of the heat-developable color light-sensitive material by any method. For example, a low boiling point solvent (
After dissolving in a high boiling point solvent (dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc.) (methanol, ethanol, ethyl acetate, etc.) or an aqueous alkaline solution (e.g. 10% aqueous solution of storum hydroxide, etc.) After dissolving in water, it is used after being neutralized with mineral acid (e.g. hydrochloric acid or nitric acid).
It can be used after being dispersed in a ball mill with an aqueous solution of a suitable polymer (for example, polyvinyl butyral, polyvinylpyrrolidone, etc.).

As the reducing agent used in the photothermographic material of the present 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, 5g of JP-A-57-186744,
-79247, 58-149046, 58-1
No. 49047, No. 59-124339, No. 59-
In the case of a dye-donating substance that releases or forms a diffusible dye by coupling with an oxidized form of a 19-element agent as disclosed in No. 181345, No. 60-2950, etc., it is included in the present invention. The reducing agent used is
For example, U.S. Patent Nos. 3,531,286 and 3,76
1,270, 3.764.328, and RD No. 72146, RD No. 151
08, same No. 15127 and JP-A-56-271
p-phenylenediamine series and p-phenylene diamines described in Publication No. 32
- An amine phenol type developing agent, a phosphoramidophenol type developing agent, a sulfonamide phenol type developing agent, a sulfonamide aniline type developing agent, a hydrazone type color developing agent, etc. can be used. Also, Yonemasa 1 Patent No. 3.342.599, Patent No. 3.71, No. 492,
It is also possible to advantageously use the color development imitation main mulberry curry described in JP-A-53-135628 and JP-A-57-79035.

As a particularly preferable reducing agent, JP-A Ill 56-141
Examples include reducing agents represented by the following general formula (1) described in No. i 133.

General formula (1-R5 几6 In the formula, R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) which may have a substituent, and R1 R2 and R2 may be ringed with rr1 to form a heterocycle.R3,17゛1゜1 or 5 and R
6 is a hydrogen atom, a halogen atom, a hydrogen atom, an amino group, an alkoxy group, an acylamide group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number of 1 to 30 (preferably 1 to 30) 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 above general formula (1) is a compound containing a nitrogen atom that exhibits basicity capable of producing a salt-free salt, and particularly important organic bases include amine compounds. Chain amine compounds include primary amines, secondary amines, tertiary amines, etc., and cyclic amine compounds include lysine, quinoline, piperidine, etc., which are well-known examples of typical heterocyclic organic bases. , imidazole and the like. This hydroxylamine,
Compounds such as hydrazine and amidine are also useful as chain amines. Salts of nitrogen-containing organic bases include inorganic salts of the above-mentioned specific bases (for example, hydrochloride, sulfur salt!
2 salts, 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.

Preferred specific examples of the reducing agent represented by the general formula (1) are shown below.

(R-5) (R-8) (R-9) CH.

(R-10) (R-11) (R-12) H CH.

C1H, NHCOCH.

(R-20) (R-21) CH.

(R-22) (R-23) (R-24) (R-25) (R-26) (R-27) lJl;M.

(R-28) (1'L-29) (R-30) :C,L- The reducing agent represented by the above general formula (1) can be prepared by a known method,
For example, Houben Peil, Mesometan der Organitsien Hemi, Band XI/2 (Houben
-Weyl, Methoden der Oroan
ischen Chemie, Band X I
/2) It can be synthesized according to the method described on 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 of simply obtaining a silver image, a developing agent as described below which forms a Schiff base with the polymer of the present invention can also be used.

For example, aminophenols (e.g. p-aminophenol, etc.), sulfonamidophenols [e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6 -dipromo4-(
p-toluenesulfonamide) phenol, etc. 1, hydrazones, and paraphenylenediamines.

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

Furthermore, it can be used in combination with a common developing agent, such as phenols (such as p-phenylphenol, p-methoxyphenol, 2,6-sheet phenol, etc.).
ert-butyl-p-cresol, etc.), polyhydroxybenzenes (e.g., hydroquinone, tert-butylhydroquinone, 2゜6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g., α 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 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, and pyrazolones.

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 used, the type of Nada acid silver salt seed stone, and other additives. , usually 0.01 per mole of photosensitive silver halide
-1500 mol, preferably 0.1-20
It is 0 mole.

When the heat-developable photosensitive material of the present invention is a color type, a dye-providing substance is used.

Dye-providing substances that can be used in the present invention will be explained below. The dye-donating substance may be any substance that participates in the reduction reaction of the photosensitive silver halide and/or the right eye silver salt used as necessary, and that can form or release a diffusible dye as a function of the reaction. Depending on their reaction form, negative-acting dye-donors act on a positive function (i.e., form a negative dye image when negative-working silver halide is used) and positive-acting substances act on a negative function. It can be classified as a dye-providing substance (that is, it forms a positive dye image when negative-working silver halide is used). Negative dye-donating substances are roughly classified as follows.

Margin below Releases a diffusible dye when oxidized Release type compound Formation type compound proboscis The respective dye-donating substances will be further explained.

Examples of the reducible dye-releasing compound include compounds represented by general formula (2).

General formula (2) % formula % In the formula, Car is a reducing substrate (so-called carrier) that is oxidized and releases a dye upon reduction of photosensitive silver halide and/or organic silver salt used as necessary. , Dy
e is a diffusible dye residue.

Specific examples of the above-mentioned reducing dye-releasing compounds include JP-A-57-179840, JP-A-58-116537, and JP-A No. 58-116537.
No. 9-60434, No. 59-65839, No. 59-7
No. 1046, No. 59-87450, No. 59-8873
No. 0, No. 59-123837, No. 59-165054
No. 59-165055, for example, the following compounds are mentioned.

The following is an example of a dye-donating substance in the margin.
Examples include compounds represented by:

General formula (3) A.

In the formula (2), A1 and A2 each represent a hydrogen atom, a hydroxy group, or an amino group, and Dye is Dye represented by the general formula (2).
is synonymous with Specific examples of the above compounds are given in JP-A-59-12
This is shown in Japanese Patent No. 4329.

As a coupled dye-releasing compound, general formula (4) is used.
Examples include compounds represented by:

General formula (4) % formula % In the formula, CD+ is a clear group (also called a coupler group) that can react with the oxidized form of a reducing agent to release a diffusible dye, and J is a two-stroke coupler group. The bond between Cpl and J is cleaved by reaction with the oxidized form of the reducing agent.nl
represents O or 1, and Dye has the same meaning as defined in general formula (2). In addition, Cp+ is preferably substituted with various ballast groups in order to make the coupled dye-releasing compound non-diffusible, and the ballast group has 8 or more carbon atoms (
more preferably 12 or more) or sulfo groups,
It is a hydrophilic group such as a carboxy group, or a group having both 8@ or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group. Another particularly preferred ballast group can include polymer chains.

Specific examples of the compound represented by the above general formula (4) include JP-A-57-186744 and JP-A-57-122596.
No. 57-160698, No. 59-174834, No. 57-224883, No. 59-159159,
No. 59-231540@described for each specification, examples of which include the following compounds.

Exemplary dye-providing substance ○
Examples include compounds represented by:

General formula (5) % formula %) In the formula, C1)2 is a group (so-called coupler residue) that can react with the oxidized form of the reducing agent (coupling reaction) to form a diffusible dye. , F represents a divalent bonding group, and B represents a ballast group.

The coupler residue represented by CD2 preferably has a molecular weight of 700 or less for the sake of diffusibility of the dye formed.
More preferably it is 500 or less.

Further, the ballast group is preferably the same as the ballast group defined in general formula (4), and particularly has 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group. Groups having both are preferred, and polymer chains are more preferred.

The coupled dye-forming compound having a polymer chain is preferably a polymer having a repeating unit derived from a monomer represented by general formula (6).

General formula (6) % formula %) In the formula, C112 and F have the same meaning as defined in general formula (5), Y represents an alkylene group, an arylene group, or an aralkylene group, and l represents ○ or 1. Representation, Z is 2
L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupled dye-forming compounds represented by general formulas (5) and (6) include JP-A-59-1243
No. 39, No. 59-181345, No. 60-295
No. 0, Japanese Patent Application No. 59-179657, No. 59-1816
No. 04, No. 59-182506, No. 59-18250
It is described in each specification of No. 7, etc., and the following compounds are mentioned, for example.

Margin below Exemplary dye-donor substances OCRCr<Ht* OOH polymer PM-1 x: 80% by weight y:zoiitchi M-2 x: 50i1E quantity Y: 50i quantity PM-3C output M-4 x: 40i1U quantity y: 60% by weight 1vi-5 M x:60i[ii% Y:40! tc% M-6 M x: 50% by weight y: 50% by weight M-7 x: 50% by weight y:50Xli:% M-8 NI(COCH.

M x : 50% by weight
To explain in more detail the coupler fortress founded on + or CI2, groups represented by the following general formula are preferred.

General formula (7) General formula (8) General formula (9
) General formula (10) General formula (11)
General formula (12) General formula (13)
General formula (14) General formula (15)
General formula (16), where R7, R8, R9 and R1G are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an alkylsulfonyl group. group, arylsulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amine group, alkoxy group, aryloxy group, cyano group, alkylsulfonyl group, arylsulfonyl group, ureido group, alkylthio group, arylthio group, carboxy group, sulfo group or a heterocyclic residue, which further includes a hydroxyl group, a carboxy group, a sulfo group,
Alkoxy group, Siam L nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group,
It may be substituted with a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, or the like.

These substituents are selected depending on the purpose of CI)1 and CI2, and as mentioned above, in <Cp+, one of the substituents is preferably a ballast group, and in C1)2, it is preferable to In order to increase sex, the molecular weight is 700.
Hereinafter, the number of substituents is preferably selected to be 500 or less.

As a positive dye-donating substance, for example, the following general formula (1
There is an oxidizable dye-releasing compound represented by 7).

General formula (17) In the formula, Wl represents a collection of atoms necessary to form a quinone ring (which may have a substituent on this ring),
R1+ represents an alkyl group or a hydrogen atom, and E is -N-
C+R13+- (in the formula, R12 represents an alkyl group or a hydrogen atom, R+3 represents an oxygen atom or -N-) or -8O2-, r represents O or 1, Dye
has the same meaning as defined in general formula (2). Specific examples of this compound are JP-A-59-166954 and JP-A-59-166954;
It is described in specifications such as No. 154445, and includes, for example, the following compounds.

Margin below , Jμ7 mine CH.

■ Star OCH.

■ As another positive dye-donor substance, the following general formula (18) is used.
There are compounds that lose their dye-releasing ability when oxidized, such as the compound represented by:

Ro I-1 In the formula, W2 represents a group of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R''
, r, 'E, and Dye are synonymous with those defined in general formula (17). A specific example of this compound is JP-A No. 5
It is described in specifications such as No. 9-124327 and No. 59-152440, and includes, for example, the following compounds.

Here, child margin (,lnee・ Exemplary dye-donor substances ■ OCH.

[Phase] As another positive dye-providing substance, the following general formula (
Examples include compounds represented by 19).

General formula (19) In the above formula, W2, R11, Dye are general formula (18)
It has the same meaning as defined in .

Specific examples of this compound are described in JP-A-59-154445, etc., and include the following compounds.

Exemplary dye-providing substances ■ ■ General formulas (2), (3), (4), (17) (18
) and (1), the residues of the diffusible dye represented by Dye will be roughly detailed. The residue of the diffusible dye preferably has a molecular weight of 800 or less, more preferably 600 or less, due to the diffusivity of the dye;
Examples include residues such as azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes.

These residual dye bases may be in a temporary short wave form that can be multicolored during thermal development or transfer. In addition, these dye residues are used for the purpose of increasing the light resistance of images, for example, in
Chelatable dye residues described in No. 48765 and No. 59-124337 are also preferred.

These dye-providing substances may be used alone or in combination of two or more. The use m is not limited and depends on the type of dye-providing substance, whether it is used alone or in combination of two or more, 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, etc. Although it may be determined accordingly, for example, the amount of H to be used can be from 0.00 g to 50 g, preferably from 0.1 g to 100 g per 1 f.

The dye-providing substance used in the present invention can be incorporated into the photographic constituent layer of the heat-developable light-sensitive material by any method. (tricresyl phosphate, etc.) and then subjected to ultrasonic dispersion, or dissolved in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.) and then neutralized with a mineral acid (e.g., hydrochloric acid or nitric acid, etc.). Alternatively, it can be used after being dispersed in a ball mill with an aqueous solution of a suitable polymer (eg, gelatin, polyvinyl butyral, polyvinyl and lolidone, etc.).

The 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 a double jet method while keeping pAg constant. In this case, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the addition rate as a function of time, pH, pAg, temperature, etc. According to a more preferred embodiment, a silver halide emulsion having silver halide grains having a shell can be used. Silver halide grains having a shell can be obtained by sequentially growing shells on a well-monodispersed silver halide grain as a core using the method described above. A monodisperse silver halide emulsion is one having a particle size distribution in which the variation in the size of silver halide grains contained in the emulsion is less than a certain ratio with respect to 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 powder grains with a uniform grain shape 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-58-111933, JP-A No. 58-1
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 grain diameter to thickness of 5=1 or more.

In general, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces have not been fogged in advance can be used in the present invention. For internal latent image type silver halide whose surface is not prefogged, for example, U.S. Pat.
, No. 592, 250, No. 3,206, No. 313, No. 3
, No. 3111322, No. 3,511,682, 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, first AOCff1 grains are prepared, and then bromide or a small amount of iodide is added thereto. A method in which the central core of chemically sensitized silver halide is coated with silver halide that has not been chemically sensitized,
Alternatively, many methods are known, such as a method in which a chemically sensitized coarse grain emulsion is mixed with a chemically sensitized or non-chemically sensitized fine grain emulsion, and a fine grain emulsion is deposited on the coarse grain emulsion.

Also, U.S. Patent Nos. 3,271,157 and 3,44
7,927 and 3,531,291, or silver halide emulsions having silver halide grains incorporating polyvalent metal 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.
Silver halide emulsions consisting of grains having a laminated VLI structure as described in JP-A No. 38525, etc., and other JP-A-52-
These include silver halide emulsions described in No. 156614 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 be coarse or fine, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.001 μm to about 1.5 μm, and more preferably about 0.001 μm to about 1.5 μm. .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, it is also possible to allow a photosensitive silver salt-forming component to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt. . The photosensitive W4 salt-forming component used in this vA@ method is an inorganic halide, for example, a halide represented by MXn (where M is an H atom, NH4
group or a gold R atom, and X is Cff1. Represents Br or ■, n is 1 when M is an H atom or an NH4 group, and M
When is a metal atom, it indicates its valence. Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium,
Examples include thallium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, and cerium. ), 88 halogen-containing gold HAs (for example, K2
Pt Cj! s, K2 Pt Sr s, H
ALI Cf! 4゜(NH4)2 Ir Cff1
s, (NH4)3 1r C4! s.

(NH4)2 RU C/! 6. (NH4)a
R11Cj! s.

(NH4)2 Rh C4! s, (NH4)3 Rh
13rs, etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium 70mite, 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, etc.) , 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalimide) Radinone, 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 at the time of use, the amount is 0.001i; 1 to 50 g per layer per 1f of support.
It is preferable that it is, more preferably 0, 10 to 1
It is 0g.

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 edge-sensitive layer, and a heat-developable red-sensitive layer. You can also do that. 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 stomach-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, viroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferred. Such nuclei include alkyl groups, alkylene groups,
It may contain a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group or an enamine group capable of forming a 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 basic nucleus, the merocyanine dye may have an acidic nucleus such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidione nucleus, a thiazolidinedione nucleus, a barbylic acid group, a thiazolinthione nucleus, a malononitrile nucleus, or a pyrazolone nucleus. .

These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination.

Furthermore, ascorbic Ml conductors, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat. No. 2.933.3
A supersensitizing additive that does not absorb visible light as described in the specification of No. 90, No. 2, 937.089@, etc. can be used in combination.

The addition of these sensitizing dyes 1 is from 1.times.10@-4 mol to 1 mol per mol of photosensitive silver halide or silver halide-forming component. More preferably, 1X10-mol to 1Xl
0" mole.

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

Examples of the 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, 147222-1982, 36224-1982, and 37610-1980, etc. Long-chain aliphatic carboxylic acids as described in each publication and in the specifications of U.S. Patent No. 3.330.633, U.S. Pat. Silver salts of carboxylic acids having heterocycles, such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, silver α-(1-phenyltetrazolthio)acetate etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-26582, No. 4
No. 5-12700, No. 45-18416, No. 45-2
No. 2185, JP-A-5Z-T373ZT@, JP-A-Sho 58
There are silver salts of imino groups described in publications such as No. 11FF638, No. 58-118639, and US Pat. No. 4,123,274.

Examples of silver salts of imino groups include benztriazole silver. The penztriazole silver may be substituted or unsubstituted. Representative examples of substituted benztriazole silver include, for example, alkyl-substituted benztriazole silver (preferably an alkyl group of 022 or less,
More preferably those substituted with an alkyl group of C+ or less, such as methylbenztriazole silver, ethylbenztriazole silver, n-octylbenztriazole silver, etc.), alkylamidobenztriazole silver (preferably substituted with an alkylamide group of 022 or less) silver acetamidobenztriazole, silver propionamidebenztriazole, silver 1so-butylamidebenztriazole, silver laurylamidebenztriazole, etc.), silver alkylsulfamoylbenztriazole (preferably alkylsulfamoyl having C22 or less) Those substituted with groups, such as 4-(N,N-diethylsulfamoyl)benztriazole, 4-(N-propylsulfamoyl)benztriazole!, 4-<N
-octylsulfamoyl)benttriazole silver, 4
-(N-decylsulfamoyl)penztriazole silver, 5-(N-octylsulfamoyl)penztriazole silver, etc.), m-salts of halogen-substituted penztriazoles (e.g. 5-chloropenztriazole silver, 5-bromobenztriazole, etc.) triazole silver, etc.), alkoxypenztriazole silver (preferably C22 substituted with an alkoxy group below C, more preferably 04 or less alkoxy group, such as 5-methoxybenztriazole silver, 5-ethoxybenztriazole silver, etc.) , 5-nitrobenztriazole silver, 5-aminopenztriazole silver, 4-hydroxybenztriazole silver, 5-carboxybenztriazole silver, 4-sulfobenztriazole silver, 5
-silver sulfobenztriazole, and the like.

Examples of other silver salts having an imino group include imidazole silver, benzimidazole silver, 6-nidropenzimidazole silver, pyrazole silver, urazole silver, 1.2
．． Silver salts of other mercapto compounds such as 4-triazole silver, 1H-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., such as 2-mercaptobenzoxazole Silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,4-triazole silver, 4-hydroxy-6
-Methyl-1,3゜3a, 7-chitrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4,6-
Examples include silver pentazaindene.

Other silver complex compounds with a stability constant of 4.5-10.0 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 Il-containing silver salts, imino group silver salts are preferred, and silver salts of benzotriazole derivatives are particularly preferred, and 5-methylbenzotriazole and its derivatives, sulfobenzotriazole and its derivatives, N-alkyl sulf 7 moylbenzo Triazoles and their derivatives are preferred.

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

In addition, the GL manufacturing method for organic silver salts is generally a method of dissolving and mixing silver nitrate and raw material organic compounds in water or an organic solvent, but if necessary, a binder may be added or
It is also effective to add an alkali such as sodium hydroxide to promote dissolution of the organic compound, or to use an ammoniacal silver nitrate 2 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. More preferably 0.
It is 3 to 30 moles.

Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural polymers such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more molecular substances can be used in combination. 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. The polyvinylpyrrolidone may be substituted polyvinylpyrrolidone, and preferred polyvinylpyrrolidone has a molecular weight of i, ooo to
400.000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, 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% of the composition ratio (heavy ring %, the same applies hereinafter). Preferred examples of such copolymers are those whose molecular groups are s, ooo to aoo, ooo.

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

The binder may contain other polymeric substances,
Gelatin and a mixture of polyvinyl with a molecular weight of 1,000 to 400,000, lolidone and one or more other polymeric substances, gelatin and a molecular weight of 5,000 to 400,000
A mixture of 0 vinylpyrrolidone copolymer 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 5o (J, preferably 0, 1
+1 to 10Q.

In addition, the binder is 0.1% per 1g of the dye-providing substance.
-109 is preferably used, and more preferably, the support used in the heat-developable photosensitive material of the present invention includes, for example, polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, and photographic raw material. Examples include paper supports such as printing paper, baryta paper, and resin coated paper, and supports obtained by coating and curing an electron beam curable resin composition on these supports.

Margins Below In 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, it is preferable that various heat solvents are added to the heat-developable photo-sensitive material 6 and/or the image-receiving member. The thermal solvent used in the present invention is a compound that promotes thermal development and/or thermal transfer. Regarding these compounds, for example, U.S. Pat. No. 3,347.675, U.S. Pat.
56, Japanese Patent Application No. 59-47787, etc., and those particularly useful in the present invention include, for example, urea rust conductors (e.g., dimethylurea, diethylurea, phenylurea). ), amide derivatives (e.g., acetamide, benzamide, etc.),
Examples include polyhydric alcohols (eg, 1,5-bentanediol, 1,6-bentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), and polyethylene glycols.

Among the above thermal solvents, water-insoluble solid thermal solvents described below are used in various ways.

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/organic compound. ratio (“Organic Conceptual Diagram” by Yoshio Koda,
Sankyo Shuppan ■, 1984) is in the range of 0.5 to 3.0, preferably 0.7 to 2.5, and particularly preferably 1.0 to 2.0, and has a 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.

The following is a blank space. Examples of water-insoluble solid thermal solvents Melting point (°C) Inorganic/Organic CCCI) 3CONH214f 1.44eN
HcOc83113~115° 134 Melting point (C) Inorganic/Organic melting point (°C) NoytL/Organic melting point (°C) Inorganic/Organic<I)-802NH-! JJ) 110° 1
13 (H3C breeding ChNHCzHaNH8Ch-/!J:
j) -CH3168° 159 Many of the compounds used as water-impure solid thermal solvents are commercially available,
Moreover, it 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.

The layers to which the water-insoluble solid thermal solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, and a receiver of an image receiving member.
It is added and used so that the effect of each layer etc. can be obtained.

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

Incidentally, 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 following margin is 3 dimensions.- 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; , -C0-1-8O2- as described in U.S. Pat. No. 3,667,959.
There are non-aqueous polar organic compounds having a melting point of 20° C. or higher, such as lactone having 1-SO-U.

Furthermore, benzophenone derivatives described in JP-A-49-115540, JP-A-53-24829 and JP-A-53-24829;
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 for colors and preparations, for example, JP-A-46-
4928, 46-6077, 49-5019, 49-5020, 49-91215, 49-91215,
No. 49-101727, No. 50-2524, No. 50-
No. 67132, No. 5047641, No. 50-114
No. 217, No. 52-33722, No. 52-99813
No. 53-1020, No. 53-55115, No. 53-76020, No. 53-125014, No. 54
-156523, 54-156524, 54-
No. 156525, No. 54-156526, No. 55-4
Publications such as No. 060, No. 55-4061, No. 55-32015, West German Patent No. 2,140,406, West German Patent No. 2,141゜063, West German Patent No. 2,220,618, U.S. Patent No. 3, No. 847,612, No. 3.7132.9
No. 41, No. 4.201.582 and JP-A-57-
No. 207244, No. 57-207245, No. 58-1
89628%, each Mei III such as No. 58-193541
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-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, mercaptotriazoletotetrazabentalene, aminomercaptotriazole, acylaminomercaptotriazoles, phthalic acid,
Naphthalic acid, phthalamic acid, etc., a mixture of one or more of these with an imidazole compound, a mixture of at least one acid or acid anhydride such as phthalic acid, naphthalic acid, etc. and a phthalazine compound; Examples include combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like.

As antifoggants, for example, U.S. Pat. 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, N- described in Japanese Patent Publication No. 47419/1983
Halogen compounds (e.g. N-halogenoacetamide, N
-herogenosuccinimide, etc.), U.S. Patent No. 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, carboxyl-resistant compounds described in JP-A No. 51-47419@. Dium salts (e.g. lithium laurate), British IIF No. 1,
455,271@, special IRI[5 0 - IQ 1
, 019'? t 2. 'IE') Oxidizing agent (V/
4. For example, perchlorates, inorganic peroxides, persulfates, etc.), 5.
Sulfinic acids or thiosulfonic acids described in No. 3-19825, 2-thiouracils described in No. 51-3223, simple sulfur described in No. 51-26019@,
No. 51-42529, No. 51-81124, No. 55
Disulfide and polysulfide compounds described in No. 93149, rosin or diterpenes (e.g. abietic acid, pimaric acid, etc.) described in No. 51-57435
, a polymeric acid having a free carboxyl group or a sulfonic acid group as described in US Pat. No. 51-104338, thiazolinthione as described in US Pat.
JP 54-51821M, U.S. Patent No. 4,137.
1.2.4-triazole or 5-mercapto-1.2.4-triazole described in 079@, 55-
Thiosulfinate esters described in 140833@,
1.2.3.4-thiatriazoles described in No. 55-142331, No. 59-46f341, No. 59-5
Dihalogen compounds or trihalogen compounds described in No. 7233, No. 59-57234, and No. 59-1
No. 14636 lists two diol compounds.

In addition, as other antifoggants, Japanese Patent Application No. 59-565
Examples of the hydroquinone derivatives described in No. 06 include G[
A combination of benzotriazole derivatives (e.g., 4-sulfobenzotriazole, 5-carpogysybenzotriazole, etc.) with hydroquinone derivatives described in Japanese Patent Application No. 59-66380 is preferably used. be able to.

Still another particularly preferred antifoggant is the inhibitor having a wood-philic group described in Japanese Patent Application No. 60-218169. (Polymer inhibitors described in No. 60-262177 and Japanese Patent Application No. 60-2635)
Examples include compounds having a ballast group described in No. 64.

As a silver image stabilizer, U.S. Patent No. 3.707.37
Polyhalogenated organic oxidizing agent described in No. 7 specification (e.g., te-1-labromobutane, tribroequinaridine, etc.),
Belgian Patent No. 7t38,071 @ 5- described in the specification
Methoxycarbonylthio-1-7 to lutetrazole, mono to 〇 compounds described in JP-A 'J, No. 450-119624 (e.g., 2-bromo-2-1 to lylsulfonylacetamide, etc.), JP-A-50-420328 Bromine compounds (PA, for example, 2-bromomethylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-6
-methyltriazine, etc.), and JP-A-53-46020
Examples include tripro-7 ethanol, which is described in No. Also, various heptanohalogenated organic antifoggants for silver halide emulsions as described in JP-A-50-119624 can be used.

Other image stabilizers include U.S. Pat. No. 3.220;
No. 846, No. 4.082.555, No. 4.088.4
No. 96, Japanese Patent Publication No. 50-22625, Research Disclosure (RD) No. 12021, No. 15168, No. 15567, No. 15732, No. 15733@,
Compounds that release basic substances by the heat generated by the activator precursor described in Nos. 15734 and 15776, for example, compounds such as guanidinium trichloroacetate-1 that release j:AM by decarboxylation with heat. , aldobumide compounds such as galactonamide, amine imides, compounds such as 2-carboxylated polycypamide, and JP-A-56-130745, JP-A-56-13
A sodium phosphate base generator described in No. 2332, a compound that generates a di-amine in an intramolecular nucleophilic reaction described in British Patent No. 2,079,480, JP-A-59-1
Aldoxime carbamates described in No. 57637,
Hydroxamic acid carbamates etc. described in No. 59-166943, and No. 59-180537, No. 59
Examples include base release agents described in Japanese Patent No. 174830 and No. 59-195237.

Furthermore, U.S. Patent No. 3,301,678, U.S. Pat.
．． No. 444, No. 3,824,103, No. 3,844
, 788, RD 12035, RD 18016, etc., the S-rubamoyl derivatives of mercapto-containing compounds, Ab nitrogen-containing multicyclic compounds, may be used for the purpose of stabilizing images, and furthermore, is U.S. Patent No. 3.669.670@, U.S. Patent No. 4,012,260
Nitrogen-containing organic bases called activator stabilizers and activator stability breakers, such as 2- α-sulfonylacetate or trichloroacetic acid M salt of 7-minothiazoline and an acylhydrazine compound can be used for the purpose of accelerating development or for stabilizing the image, respectively.

Also, for example, JP-A-56-130745 and JP-A-59-2
The phenomenon may occur in the presence of a small amount of water as described in US Pat. 3.
312.550 etc.&l! As described above, development may be carried out using hot water vapor or heat containing moisture.Also, compounds that release water into the heat-developable photosensitive material, such as the
Compounds containing water of crystallization such as those described in No. 4-26582, such as phosphoric acid! - Lithium 12 hydrate, ammonium chloride, and the like may be contained in the heat-developable photosensitive material.

In addition, various additives and coating aids such as antihalation dye R1, optical brightener, hardener, antistatic agent, plasticizer, and spreading agent may be used.

In the heat-developable photosensitive material of the present invention, colloidal silica is added to the heat-developable photosensitive layer and/or non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving film properties. Can be used.

The colloidal silica used in the present invention is a colloidal solution of silicic anhydride with an average particle size of 3 to 120 mμ mainly using water as a dispersion medium, and the main component is 5iCh (silicon dioxide).
It is. Regarding colloidal silica, for example, JP-A-56-10933G, JP-A-53-123916, JP-A-5
It is described in No. 3-112732, No. 53-100226, etc. The amount of colloidal silica used is 0.05 to 0.05 to the binder of the layer to be mixed and coated in terms of dry weight ratio.
A range of 2.0 is preferred.

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

Regarding the organic fluoro compounds used in the present invention, US Pat.
No. 3,754,924 Tan, No. 3.775.126, lff113,850,640, West German Patent Publication No. 1
．． No. 942.665, No. 1,961,638, No. 2.
No. 124.262, British Patent No. 1.330.356;
Helgie:! r, 1742,680@Tonbi ni JP-A-4
G-7781, 48-9715, 49-467
No. 33, No. 49-133023, No. 50-99529
No. 50-11322, No. 50-160034,
No. 51-43131, No. 51-129229@, No. 5
No. 1-106419, No. 53-84712, No. 54-
No. 111330, No. 56-109336, No. 59-3
No. 0536, No. 59-45441 and Special Publication No. 1977-
No. 9303, No. 4g-43130, No. 59-5887
Examples include compounds described in @, etc., and these are preferred.
/ can be used frequently.

The heat-developable photosensitive material of the present invention includes thermal phenomenon photosensitive W and/or
Alternatively, an antistatic agent can be used in the non-photosensitive FI (eg, undercoat layer, intermediate layer, protective layer rj).

The antistatic agent used in the present invention is described in British Patent No.
, 466, No. 1300, Research Disclosure p.
-(Research + Q 1 closure
) No. 15840, No. 16258, No. 16630,
U.S. Patent No. 2.327.828, U.S. Patent No. 2.861.05
No. 6, No. 3.206.312, No. 3,245,833
No. 3,428,451, No. 3.775.126, No. 3.963.498, No. 4,025,342, No. II, No. 025,463, No. 4.025,691
Examples include compounds described in No. 1, No. 1, No. 025,704, etc., and these can be preferably used.

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

As the ultraviolet absorber used in the present invention, benzophenone compounds (for example, JP-A-46-2784, U.S. Pat.
3,275,530, 3,698,907), butadiene compounds (e.g., those described in Iceberg Patent No. 4,045,229), 4-thiazolidone compounds (e.g., U.S. Pat. Same 4
No. 2-26187, No. 44-29620, No. 48-4
No. 1572, JP-A-54-95233, JP-A No. 57-14
No. 2975, U.S. Pat. No. 3,253. ! i21 issue, same 3
．． 533, 794, 3.754.919, 3.
No. 794.493, No. 4.009,038, No. 4,
No. 220,711, No. 4,323,633, Research Disclosure (r< eseillrcll
22519 J1 benzoxidol compounds (e.g. those described in U.S. Pat. No. 3.7 (10,455)), cinnamate ester compounds (15iii, e.g. U.S. Pat. No. 3.705)
．． No. 805, No. 3,707,375, Special Y71 1977
-49029).

Furthermore, U.S. Patent No. 3.499.762, Japanese Patent Application Publication No. 1983
-48535 can also be used. UV-absorbing couplers (e.g. cyan dye-forming couplers based on σ-naphthol) and UV-absorbing polymers (e.g. cyan dye-forming couplers based on σ-naphthol)
For example, JP-A IM (5g-111!342, 178
No. 351, No. 181041, No. 59-19945,
23344@, the one described in the official gazette), etc.

In the thermal phenomenon photosensitive material t1 of the present invention, an rjJi1M agent can be used in the heat-developable photosensitive layer and/or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

Hardening agents used in the present invention include aldehyde-based, aziridine-based (for example, PB Rev-1 to 19,921, US InfN Wf No. 2, 9!10, 197,
ff' 2.964.40/1, 2,983,
No. 611, No. 3,271.175, those described in Japanese Patent Publication No. 40898/1988, and Japanese Patent Application Laid-Open No. 91315/1982), isoogizazole series (for example, U.S. Pat. No. 14, No. 331, b) described in item No. 609,
Epoxy systems (e.g. U.S. Pat. No. 3,047,394,
West German Patent No. 1,085,663, British Patent No. 1. +
+33. ,” + Specifications of No. 18, Special Publication No. 4B-3
5495), vinyl sulfone type (
For example, PB Report 19,920, West German Patent No. 1.1
No. 00.942, No. 2,337,412, No. 2.54
No. 5.722, No. 2,635,518, No. 2,742
, No. 308, No. 2.749.260, British Patent q
No. 1,251,091, Patent Application No. 45-54236, No. 48-110996, U.S. Patent No. 3,539.6
44 and 3.490.911), acryloyl type (for example, Japanese Patent Application No. 48-279)
No. 49, U.S. Pat. No. 3,640.720, each item 14), carbodiimide type (e.g., U.S. Pat. No. 2,938,892, U.S. Pat. No. 4,043,818, U.S. Pat. No. 4, No. 061.499 gnhas, equity 11346-
3871! Publication No. I, Patent Application No. 197-15 (No. 195)
F No. 2,410,973, 2.5! i31 No. 15, U.S. Patent No. 3.325.287, JP-A-1
(6 described in Publication No. 52-12722), other maleimide-based, acetylene-based, methanesulfonic acid ester-based, and N-medyrol-based 1ilFJ agents are used alone or in combination.
Can be used together. Useful ζ! For example, West German VI Permit No. 2.447.!+87, West German VI Permit No. 2..'1. , 3.832.
Specifications of No. 181, No. 3,840,370, JP-A No. 48-43319, No. 50-63062, No. 52-
Examples include combinations described in Japanese Patent Publications No. 127329 and Japanese Patent Publication No. 48-32364.

In the heat-developable photosensitive material of the present invention, a polymer hardener can be used in the heat-developable photosensitive and/or non-photosensitive layers (eg, undercoat layer, intermediate layer, protective layer, etc.).

Examples of the polymeric hardener used in the present invention include the polymers described in U.S. Pat. No. 3.3G2.827, Relichi Descrozi+! 17333j3 (1078) <r'I11 Triazine-based polymer described in
Polymer with ebony 1st double base, Lileach Discloge P 16725r4 (197J), US special: '[No.
No. 033, same! 16142524 @ Activated 111 vinyl film or its precursor as described in publications, etc. 4F? Ll
Polymers with J3 J: and JP-A-56-6 (i8
Examples include polymers having active ester groups as described in Japanese Patent No. 41.

The heat-developable photosensitive material of the present invention includes a thermal phenomenon photosensitive layer J3 and/or a non-photosensitive layer (for example, F coating layer, intermediate layer, Polymer latex can be used for <q>.

Preferred specific examples of the polymer latex used in the present invention include poly-superior acrylate-1, poly-propylene-acrylate-1, poly-11-butyl acrylate-1, polymers of nibble acrylate-1 and acrylic acid, 71 Poly7- of Vinylidene Chloride and V-Cirno/Crylyl-1-, Polymer of Butilno-7Crylyl-1-Doj' Acrylic Acid, ^
copolymer to vinyl monate fluorophore 1,
Examples include a =1 polymer of vinyl acetate and edyl acrylate 1-, and a copoly 7-W of polyurethane acrylate 1- and 2-7 acrylphamide.

Preferred 511 average particle size of polymer latex1. LOy
f+2 μm to 0.2 μm. The dry weight ratio of the polymer latex is preferably 0.03 to 0.05 in relation to the binder of the layer to which it is added.

The heat developable photosensitive layer 90 F'l of the present invention has a photosensitive layer of heat developable photosensitive layer 163 and/or J1'' (for example, an undercoat layer, an intermediate layer, a protective layer, etc)
Various surfactants can be used.

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

Examples of anionic surfactants include alkylcarbonylbenne sulfone M salt, alkylnophthalene sulfone WJ, g1 alkyl sulfate esters, alkylphosphorus esters, N-acyl-N-alkyl Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, such as taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Those containing an acidic group such as a 4W1 ester group are preferred.

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

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 saponin (steroid type), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/bolyb O pyrene glycol condensate, 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),
Preferred are glycidol derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid Nisdels of polyhydric alcohols, alkyl esters of sugars, and the like.

The heat-developable photosensitive material of the present invention includes a heat-sensitive layer and/or a non-photosensitive layer (for example, a T1 intermediate layer, a protective Layer 7) may contain non-photosensitive silver halide grains.

The non-photosensitive silver halide grains used in the present invention include those having any silver halide composition such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Can be used. The preferred grain size of the non-photosensitive silver halide grains is about 0.
．． It costs less than 3μ.

Moreover, for addition, it is preferable that the range of 0.02 to 3Q/v' is 1114f low for the layer to be added.

The heat-developable photosensitive material of the present invention includes a thermal phenomenon 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 used preferably has a dry ratio of 11 [1] in the range of 0.05 to 2.0 with respect to the binder of the layer to which it is added.

The heat-developable photosensitive material of the present invention basically contains (1) a photosensitive silver halide, (2) a reducing agent, (3) a dye-providing substance, and (4) a binder in one thermal phenomenon photosensitive layer. Contains, and if necessary, (5) filming r! It is preferable to contain an i salt. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, a heat-developable photosensitive layer 211! Divided into (1), (2), (4), (5) above.
Two or more components are contained in one heat-developable photosensitive layer and a dye-providing substance (3) is contained in the other layer adjacent to this photosensitive layer, as long as they are in a state where they can react with each other. It may be contained separately in the constituent layers.

Further, the heat-developable photosensitive layer may be divided into two or more layers, such as a high-sensitivity yX 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, it generally 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.

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 in addition to the above-mentioned photothermographic material. To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support, a general silver halide photosensitive material is coated with mF.
Methods similar to those used for Alu can be applied.

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

The following margins 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 170°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;
The image may be transferred by being brought into close contact with an image receiving member after thermal development and heated, or by being brought into close contact with an image receiving member after supplying water and further heated if necessary. Also, before exposure, 70℃~180℃
Preheating may be carried out within the temperature range. Also, JP-A-60
As described in Japanese Patent Application No. 143338 and Japanese Patent Application No. 60-3644, the photosensitive material and the image receiving member are preheated at a temperature of 80°C to 250°C immediately before thermal development transfer to improve mutual adhesion. Good too.

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 furthermore, a 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 do that. There are no particular restrictions on the heating pattern, including a method of preheating and then reheating, a method of heating at a high temperature for a short time, or a low temperature for a long time, continuously increasing, decreasing, or repeating, and Although discontinuous heating is possible,
A simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

The receiving p layer of the receiving member that is effectively used in the present invention is as follows:
It is sufficient that the polymer has the ability to accept the dye in the heat-developable photosensitive layer released or formed by heat development.
．． Those described in No. 709.690 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.
Examples include those made of a heat-resistant organic polymer substance having a glass transition temperature of 40° C. or more and 250° C. or less, as described in No. 50.

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 organic polymer substances include polystyrene, polystyrene derivatives having an exchange group having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene,
Polyacetals such as polyvinylpyrrolidone, polyvinylcarbazolevinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichloride fluoroethylene, polyacrylonitrile, polyN. N-dimethylallylamide, polyacrylate with p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl Polyesters such as methacrylate, poly tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthalate, polycarbonates such as polysulfone, bisphenol A polycarbonate, polyanhydride, polyamides and cellulose acetates. In addition, Polymer Handboo, Second Edition (edited by G.I. Brandrup and E.H. Inmargat), John Willy & Sons (Polya+er Handboo)
k 2nd ed. (J, Brandrup
, E.

@, lmmergut Q) John
Also useful are synthetic polymers with a glass transition temperature of 40° C. or less, as described in the Wiley & Sons publication. Generally, the molecular weight of the polymer substance is 2,000 to 2.
00,000 is useful. These polymeric substances are
It may be used alone or in a blend of two or more types, or two or more types may be used in combination.
A combination of two or more species may be used as a copolymer.

Useful polymers include cellulose acetates such as triacetate and diacetate, polyamides in combinations such as heptamethylene diamine and terephthalic acid, fluorene propylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, and diethylene glycol. Examples include polyester, polyethylene terephthalate, and polycarbonate made of a combination of bis-p-carboxyphenoxybutane, ethylene glycol, and diphenylcarbonate.

These polymers may be modified. For example, cyclohexane dimetatool, isophthalic acid,
Polyethylene terephthalate using methoxypolyethylene glycol, 1,2-dicarbomethoxy-4=benzenesulfonic acid, or the like 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 from multiple layers. good.

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 sulfate, calcium carbonate, and talc, baryta paper, RC paper laminated with thermoplastic resin containing pigments, cloth, glass, aluminum, etc. Also, supports in which an electron beam curable resin composition containing a pigment is coated and cured on these supports, and supports in which a coating layer containing a pigment is provided on these supports. Examples include the body.

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

*When the invention is applied to a heat-developable color light-sensitive material, the various polymers mentioned above can be used as a mordant for a dye image as an image-receiving layer; It may be an image-receiving element or 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 a certain amount of radiation, such as visible light, that can be used to observe the dye image in the receiver. It is used to make The opacifying layer (reflective layer) can contain various reagents to 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. Furthermore, after imagewise exposure and uniform heating of the heat-developable color light-sensitive material, an image-receiving layer can be placed on top of the material and heated at a lower temperature than the phenomenon temperature to transfer the dye image released or formed from the dye-providing substance.

Hereinafter, the photothermographic material of the present invention is preferably provided with a protective layer. Hereinafter, various additives used in the photographic field can be used in the protective layer of the present invention, referred to as the protection layer II of the present invention. The additives include various matting agents, colloidal silica, slipping agents, right-eye fluoro compounds (especially fluorine surfactants), antistatic agents, ultraviolet absorbers, high boiling point three solvents, antioxidants, and hydroquinone MTa. , polymer latex, surfactants (including polymeric surfactants)
, hardeners (including polymer hardeners), right-handed silver salt grains, non-photosensitive silver halide grains, and the like.

The matting agent used in the protective layer of the present invention is a fine particle of an inorganic substance or an organic substance, which is added to a heat-developable photosensitive material to increase the roughness of the surface of the photosensitive material and make it matte. be.

Methods using matting agents to prevent adhesion that occurs during manufacturing, storage, and use of photosensitive materials, and to prevent static electricity caused by contact, friction, and debonding between materials of the same or different types are currently available. Well known in the industry. Specific examples of matting agents include silicon dioxide described in JP-A-50-46316, JP-A-53-7231, JP-A-58-66937,
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. Pat. No. 1,939,213, U.S. Pat. No. 2,221,873,
2.268.662, 2.322.037, 2.376.005, 2.391.181, 2,701,245, 2.992,101, 3, No. 079,257, No. 3,262.782,
3.443.946, 3,516,832, 3.539.344, 3,591,379, 3
, 754,924, 3,767, 448, JP-A-49-106821, JP-A-57-14835, etc.; West German Patent No. 2,529.32
1, British Patent No. 760.775, British Patent No. 1.260.7
No. 72, U.S. Patent No. 1,201,905, U.S. Patent No. 2,19
No. 2,241, No. 3, 053.662, No. 3.06
2.649, 3,257,206, 3,32
No. 2,555, No. 3.353.958, No. 3,370
, No. 951, No. 3,411,907, No. 3.437.
No. 484, No. 3.523.022, No. 3,615.5
No. 54, No. 3,635.714, No. 3.769,02
No. 0, No. 4,021,245, No. 4.029.5
Inorganic matting agents described in JP-A-46-7781, JP-A-49-106821, and JP-A-51
-6017, 53-116143, 53-
No. 100226, No. 57-14835, No. 57-82
No. 832, No. 53-70426, No. 59-1493
No. 57, Special Publication No. 57-9053 and EP-10
A matting agent having physical properties such as those described in No. 7,378 Mei 1B1 and the like is preferably used.

In the protective layer of the present invention, the addition m of the matting agent is preferably 10 mg/2.0 g per 1f, more preferably 2.0 g/1f.
It is 0 mq to 1.09. The particle size of the matting agent is 0.5-1
It is preferably 0 μm, more preferably 1.0 to 6 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, synthetic waxes, etc. Specifically, French Patent Nos. 2 and 1
No. 80,465, British Patent No. 955,061, No. 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
re ) 13969, U.S. Patent No. 1,263,7
No. 22, No. 2,588.765, No. 2,739,89
No. 1, No. 3,018.178, No. 3.042.52
No. 2, No. 3,080,317, No. 3, 082.08
No. 7, No. 3,121,060, No. 3,222,1
No. 78, No. 3.295.979, No. 3.489.56
No. 7, No. 3.516.832, No. 3.658.573
No. 3,679,411, No. 3,870.521, 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, Special Publication No. 4
No. 6-23233, British Patent No. 958.441, 1
．． No. 222.753, Red Seal Patent No. 2,353,262, No. 3,676, 142, No. 3,700,454,
Esters (e.g. phthalates, phosphoric esters, fatty acid esters, etc.), amides (e.g. fatty acid amides, (sulfonic acid amide, etc.), ethers, alcohols, paraffins, etc. ) may also contain oil droplets that are an emulsified fraction of a water-insoluble oily compound. 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 a combination of two or more synthetic or natural polymeric substances such as gelatin and phthalated gelatin can be used.

In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (preferably molecule 1 i, ooo ~ 400.000), polyvinyl alcohol (molecular weight 1.000 ~ 400.000),
100.000) and polyoxazoline (preferably 1,000 to 800.000 molecular weight) 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 poly Particularly preferred is a binder that uses a hydrophilic polymer with good compatibility with gelatin such as oxazoline. Gelatin is produced by lime treatment;
The gelatin may be subjected to acid treatment or ion exchange treatment, or may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatin.

The thickness of the protective layer of the present invention is preferably 0.05 to 5 μm, more preferably 0.1 to 1.0 μl. 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. One way to make the hardness of the protective layer higher than that of the photosensitive layer, that is, to control the hardness of each layer, is to use a diffusion-resistant hardener. By using it in the protective layer, only the degree of hardness of the protective layer can be made greater than that of the photosensitive layer. Polymer hardeners are known as diffusion-resistant hardeners.
For example, US Pat. No. 3.057.723, US Pat. No. 3.396.
No. 029, No. 4,161,407, JP-A-58-50
Hardeners described in No. 528 and the like can be used.

Another way to control the degree of dura for each layer is to
A diffusible hardener (for example, a vinyl sulfone hardener) is contained only in the protective layer, or the protective layer contains more m than the photosensitive layer, and after simultaneous multilayer coating, rapid drying allows for protection. The hardness of the layer can be greater than that of the photosensitive layer.

Below is Kinpaku 1. A [Effects of the Invention] The heat-developable color photosensitive material of the present invention can remove image stains caused by various additives, particularly reducing agents or reducing agent derivatives, contained in photosensitive materials, and can reduce the formation of The sharpness and stability of the image are significantly improved.

[Examples] Specific examples of the present invention will be described below, but the present invention is not limited thereto.

Example-1 Preparation of wired silver salt dispersion> 288 g of 5-methylbenzotriazole obtained by reacting 5-methylbenzotriazole and silver nitrate in a water-alcohol mixed solvent and poly(N-vinylpyrrolidone) ) 16.0g was dispersed in an alumina ball mill, and the pH
It was set to 5,5 and 20th12.

[Preparation of silver iodobromide emulsion] At 50°C, JP-A-57-92523;
An aqueous solution s containing 11.6 g of potassium iodide and 130 g of potassium bromide in solution A prepared by dissolving 20 g of ossein gelatin, 1000 g of distilled water and ammonia using the mixing and stirring method shown in Specification 4 of No. 92524. o o, 1
1) A (l and f) simultaneously with solution B and solution C of an aqueous solution 500112 containing 1 mol of silver nitrate and ammonia.
The H was added while keeping it constant. Furthermore, by controlling the addition speed of liquid B and liquid C, silver iodide content of 87 mol%, positive 6
A core emulsion with a face shape and an average grain size of 0.25 μm was subjected to ':A splitting. Next, in the same manner as above, silver iodide containing ■1 mol%
By coating the shell of silver halide, a regular hexahedron,
A core/shell type silver halide emulsion having an average grain size of 0.3 μm (shell thickness of 0.05 μm) was prepared. (The monodispersity was 8%.) The above emulsion was washed with water and desalted to collect the fibrils.
I got 700d.

Furthermore, the silver iodobromide emulsion prepared above was treated as follows.
Red-sensitive, green-sensitive and blue-sensitive silver halide emulsions were prepared.

a) Preparation of red-sensitive silver iodobromide emulsion The above-mentioned silver iodobromide emulsion 700. 124
-Hydroxy-6-methyl-1゜3.3a, 7-titrapindene 0.4g
z 32g Thio-drinking cherium 10m long IHq feeling below! 2 times methanol 1% solution 8 () 1g distilled water
12001 (! Sensitizing dye (a) b) Preparation of green-sensitive silver iodobromide fl, silver iodobromide emulsion 7001124-Human .4g gelatin 32 (1 tin sodium sulfate 1 farRg sensitizing dye below)
1% methanol solution 801g distilled water
1200i12 or less Margin sensitizing dye (1'') C) Preparation of blue-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 7001 (24-
Hydroxy-6-methyl-1゜3.3a, 7-tetra 1f indene o 4g geladine 32 g Sodium thiosulfate IOm The following sensitizing dye Methanol 1% solution 80% Distilled water 1
・2(lQd sensitizing dye (C) <Dye-providing substance dispersion> Exemplary polymeric dye-providing substance (PM-2) 39.4(1
, 113 and the following hydroquinone compound were dissolved in 1 boule of acetic acid and 200 vQ, and alkanol XC (
1241 g of 5 mm% aqueous solution (manufactured by DuPont 7), phenylcarbamoyl 1-hygelatin (Rouslow, type 178)
19P C) 30. ! Pyrazine aqueous solution containing ig 72
After mixing with 01fi and dispersing with an ultrasonic generator, and distilling off the ebul acetate, it was converted into I) l-15,5.
It was set to 951ρ.

Hyde [1, quinone compound, 1, and (reducing agent) liquid] Reducing agent (R-11) 23.3 (1, 110 g of the following development accelerator 4, poly(N-vinylpyrrolidone) 14.
6g, 050g of the following fluorosurfactant dissolved in water,
I adjusted the pH to 5.5 and added 2501R.

Development is carried out using a surfactant (m, n = 2 or 3) as a heat-developable photosensitive material> [Preparation of emulsion layer 1 Paid silver salt dispersion 12.51p, silver iodobromide emulsion 6.00p, dye-providing substance Dispersion liquid 39. Ih12, reducing agent dispersion +
2.51, mix 1:1 (1:1) of hardening agent solution (Te1-ra(vinylsulfonylmethyl)methane and taurine)
Phenyl carbamoylation 5721
% aqueous solution, tetoxy(vinylsulfonylmethyl)methane is triple debt % to 4! So dirty. ) to 2.
501 (, polyethylene glycol 30 (as a heat solvent)
+ (Kanto Kagaku) @ s, 80a was added, and on the undercoated polyethylene terephthalate 1 film with a thickness of 180 μm, 1.70 g/l of silver m and a reducing agent were added. It was applied at a weight of 0.76g/2+.

[Creation of protective layer] Gelatin, phenylcarbamoylated gelatin and poly(N
A coating solution prepared by adding the polymer P-(1) of the present invention to a mixed solution of the above-mentioned hardener and the above-mentioned hardener is coated on the emulsion layer, and the total gelatin loading ffr 2.8 (1/f
, a protective layer a having an amount of poly(N-vinylpyrrolidone) of 1.4 g and a P -(1) of 0.1170/i' was provided, and the photosensitive material was designated as A.

Similarly, P-(1)0,11 of A is placed on the emulsion layer.
Protective layers b, c, d in which the polymer of the present invention and comparative polymer were added as shown in Table 1 instead of L (]/1'
, e, f, g, h are -, photosensitive materials PIB, C1D, E
, F, G, and H were created.

Kayamapu Table 1 Next, the following image receiving member was created.

<Image receiving member> Polyvinyl chloride (n=1.10
A tetrahydrofuran solution of 0.0 and Wako FrA Pharmaceuticals was applied so that the ratio of polyvinyl chloride was 12 (1/f).

Samples A to H of the heat-developable photosensitive materials obtained were exposed to 1,600 C, M, and S through a step wedge, and together with the image-receiving member, they were placed in a heat-developer (developer).
After thermal development transfer was performed at 150°C for 1 minute using a module 277.3M Co., Ltd., the photosensitive material and the image-receiving member were quickly peeled off. The image was obtained.

The reflection density of the 1q photoden was measured using a densitometer (PDA-65, Konishiroku Photo Industry (solid mounting)), and the maximum temperature (Qmax
) and fog density ([)min) are shown in Table 2.

At the same time, the reflection density was determined in the same way for the white part of the negative sample (q), and the white part was further illuminated with xenon light using a xenon fade meter, and the generated contamination concentration was calculated as expected. The 1 concentration at the time point was measured. The results are shown in Table 2.

From the above results, the occurrence of contamination after xenon irradiation is large in H, in which no additives were added to the Wi-retention layer, and in F and G, in which comparison polymers ■ and ■ were added, no contamination due to xenon irradiation was observed. , there is a lot of original yellow pollution. In contrast, polymers P-(1), (2), (6) of the present invention,
A, B%C, and DlE using (9) have less yellow staining and less staining after xenon irradiation. In general, it was found that the original yellow stain was smaller when there were fewer components with molecular weights less than 2,000.

Example 2 The following reducing agent (a) was used instead of the reducing agent used in Example 1.
An emulsion layer was prepared in exactly the same manner except that M O,6(16(3/-1/) was formed, and the above-mentioned retaining fIQa, d, r, and h were provided on the emulsion layer, and each photosensitive material was L J, L was prepared and treated in exactly the same manner as in Example 1, and then the reflection density was measured.The results are shown in Table 3.

Reducing agent (A) From the above results, even when reducing agent (A) was used, I and J using polymers P-(1) and (6) of the present invention had little yellow staining and the The occurrence of contamination was also low, and the effect of contamination removal was observed.

Example 3 A multilayer photosensitive material having the structure shown in Table 4 was prepared. Further, a gelatin protective layer was provided on this photosensitive material to obtain a photosensitive material M. However, the gelatin of the protective layer is 0.42<
It was set to 1/n'.

Furthermore, in the photosensitive material M, the protective layer and the intermediate layer have Table 5
Anti-staining agent S C-1 Jl ratio) Filter dye YF-1 C11° Heat solvent S-1 Polyethylene glycol (average molecular weight l 300) Table 5 The above-mentioned tip material After treating 1, N, and P in exactly the same manner as in Example 1, 1 degree of tanning was determined as ml+, and from the results shown in the table, sample N using the polymer of the present invention was also found to be a multilayer sample. There is little yellow staining (and there is little staining after xenon irradiation. In other words, it was found that the polymer of the present invention has a stain removal effect even in a multilayer system.

Patent applicant Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Miyao Ichinose, 51 years old, 2 years old Bottom: J6-1

Claims (1)

[Claims] In a heat-developable color photosensitive material having a heat-developable photosensitive layer containing at least a photosensitive silver halide, a dye-providing substance, a reducing agent, and a binder on a support, the molecular weight is 20.
1. A heat-developable color photosensitive material, characterized in that the content of a component of 00 or less is 20% or less, and the material contains a polymer having at least a group that generates a Schiff base during thermal development.