JPH0367255A - Transfer type heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a transfer type heat-developable color photosensitive material high in transfer image density, small in color turbidity, and not changed in image density even by delicate temperature change at the time of heat development coupler with a dye doner comprised of a polymer derived from a specified monomer. CONSTITUTION:This color photosensitive material formed on support comprises at least photosensitive silver halide, a reducing agent, a dye donor, and a binder, and this dye donor is a polymer derived from a monomer represented by formula I in which each of R<1> and R<2> is alkyl or aryl; Q is an ethylenically unsaturated group or a group having it. X is a divalent bonding group; and (n) is 0 or 1. The dye donor of the polymer reacts with the oxidation product of a reducing agent to form a hydrophobic dye, thus permitting the obtained transfer type heat-developable color photosensitive material to be high in transferred image density, small in turbidity due to color mixing, and not changed in image density even by delicate temperature change.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transfer type heat-developable color photosensitive material. In particular, the present invention can form a color image with high transferred image density, little color turbidity, no change in image density at all even with slight temperature changes during thermal development, and very little contamination of the white background of the image. The present invention provides a transfer type heat-developable color photosensitive material containing a novel dye-providing substance.

[Conventional technology]

2. Description of the Related Art In recent years, heat-developable photosensitive materials whose development process can be performed by heat treatment have been attracting attention as photosensitive materials.

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

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

For example, U.S. Pat. No. 3,531,286, U.S. Pat.
No. 61゜270 and No. 3,764,328, etc. describe a method for forming a dye image by the reaction of an oxidized product of an aromatic primary amine developing agent with a coupler, Research 1 Discloge + ( Research Disc
15108 and 15127, U.S. Patent No. 4,021,240, etc., and a coupler and an oxidized form of a reducing agent (hereinafter also referred to as developer or developing agent) which is a sulfonamide phenol or sulfonamide aniline derivative. A method of forming a dye image by reaction with a dye, as disclosed in British Patent No. 1,590,956, uses an organic imino silver salt having a dye moiety, liberates the dye in a heat development section, and separates the dye image. A method for separating a dye image on an image-receiving layer is also disclosed in JP-A-52105821, JP-A-52105-821, JP-A-56-50328, US Pat. No. 4,235,957, etc. Disclosed method of obtaining positive dye images by silver dye bleaching method, further disclosed in U.S. Pat. No. 3,180.731;
No. 85.565, No. 11,022,617, No. 4
, 452,883 specifications, JP-A-59-20683
Various methods have been proposed, such as the method of obtaining a dye image using a leuco dye disclosed in Publication No. 1 and the like.

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. 57-2072
No. 50, etc., discloses a method of obtaining a color image by transferring a diffusible dye released by heat development.

Furthermore, by further improving these methods, for example,
8-58453, 59-12432, etc., a system in which a non-diffusible reducing dye-donating substance is oxidized to release a diffusible dye, JP-A-58-
No. 79247, No. 59-174834, No. 59-12
No. 431, No. 59-159159, No. 60-2950
A system in which a diffusible dye is released by campling with an oxidized form of a developing agent as disclosed in specification publications, etc., JP-A-58-149046, JP-A-58-14904
No. 7, No. 59-124339, No. 59-181345
Developing agents such as those disclosed in Japanese Patent Application No. 59-181604, Japanese Patent Application No. 59-182506, Japanese Patent Application No. 59-182507, Japanese Patent Application No. 59-272335, etc. A method using a non-diffusible compound that reacts with an oxidant of 1989 to form a diffusible dye, and furthermore, JP-A-59-152440 and JP-A-59-124327.
No. 59-154445, No. 59-166954, etc., are non-diffusible reducing dye-donating substances that lose their ability to release diffusible dyes when oxidized, and conversely, A method containing a non-diffusible dye-donating substance that releases a dye has been proposed.

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

However, the dye-providing substances described in the above-mentioned publications cannot be said to sufficiently prevent the dye-providing substance from moving between layers during multilayer coating or thermal development, and color turbidity tends to occur.

On the other hand, JP-A-60-2950, JP-A No. 61-1774
No. 51, No. 62-92941, and No. 62-92942 disclose a method using a polymer (hereinafter referred to as a dye-donating substance polymer) as a dye-donating substance. However, the heat-developable light-sensitive materials using the dye-providing substance polymers described in the above-mentioned publications still have insufficient color development and transferability of the produced dyes, and transfer images with high density and low fog have not yet been obtained.

Also, JP-A-61-59336 and JP-A No. 61-148447
The coupler described in No. 6,227,9333 has also been improved in dye transferability and color turbidity, but there is no evidence of any improvement in the development temperature dependence of image density or white background.

[Purpose of the invention]

The present invention is intended to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a transfer-type heat-developable color photosensitive material that provides a transferred image with high density and less color turbidity. Another object of the present invention is to provide a transfer-type heat-developable color photosensitive material in which image density does not change at all even with slight temperature changes during heat development, and furthermore, staining of the white background area of the image is extremely small.

[Structure of the invention]

The object of the present invention is to provide a transfer type heat-developable color photographic material having at least a photosensitive silver halide, a reducing agent, a dye-providing substance, and a binder on a support, wherein the dye-providing substance is represented by the following general formula (1). This was achieved using a transfer-type heat-developable color photosensitive material, which is characterized by being a polymer derived from the monomers shown above.

General formula (1) %formula% () In the formula, 1 represents an alkyl group or an aryl group.

R2 represents an alkyl group or an aryl group.

Preferably R2 is an aryl group.

Q represents an ethylenically unsaturated group or a group containing an ethylenically unsaturated group.

X represents a divalent linking group. X is preferably a divalent alkyl group, a divalent aryl group, a 5- to 6-membered heterocyclic group, a carbonyl group, or a thiocarbonyl group.

Particularly preferred are an aryl group and a carbonyl group.

The dye-donating substance, which is a polymer, generally reacts with an oxidized form of a reducing agent to form a hydrophobic dye.

With the above structure, a transfer type heat-developable color photosensitive material that achieves the object of the present invention can be obtained.

As a result of detailed studies on the image quality of transferred images obtained using heat-developable color light-sensitive materials, the present inventors have discovered that the substituent group bonded to the active site of the coupler of the dye-providing substance polymer has a significant effect on developability, color development, or the generated dye. It has been found that there is a close correlation between the transferability of .

The present invention will be further explained below.

In the present invention, the dye-providing substance according to the present invention, which is a polymer derived from a monomer represented by general formula (1), is
It reacts with an oxidized form of a reducing agent to form a generally hydrophobic dye.

Below, the general formula (1) and the polymer derived therefrom will be explained in detail.

In general formula (1), R1 represents an alkyl group or an aryl group. Specific examples of R1 include diluted alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, phenyl groups, and naphthyl groups.

The alkyl group represented by R1 in general formula (1) is preferably one having 1 to 32 carbon atoms, and an alkenyl group,
The alkynyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group and cycloalkenyl group preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. Further, the alkyl group, alkenyl group or alkynyl group may be linear or branched. In addition, these alkyl groups, etc. may include substituents such as aryl, cyano, halogen atom, cycloalkyl, cycloalkenyl, and others such as acyl, carboxy, carbamoyl, alkoxycarbonyl, etc.
Those substituted via a carbonyl group such as aryloxycarbonyl, and those substituted via a hetero atom, specifically those substituted via an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxy, acyloxy, carbamoyloxy, etc. those substituted through, nitro, amino
(including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide,
(such as ureido, which is substituted via a nitrogen atom, and alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, which are substituted via a sulfur atom).

Specifically, for example, a methyl group, an ethyl group, an isopropyl group, a pentadecyl group, a -hexylnonyl group, a 2-chloro-t-butyl group, a trifluoromethyl group, a 3-methoxypropyl group, a methanesulfonylethyl group, 2.4-
Examples include di-t-pentylphenoxymethyl group, 3-m-butanesulfonaminophenoxyprobyl group, allyl group, cyclopentyl group, and cyclohexyl group.

The aryl group represented by R1 is preferably a phenyl group, and this aryl group has a substituent (for example, a halogen atom, a cyano group, an alkyl group, an alkoxy group, an acylamino group,
(short sulfoa) group, etc.). Specifically, phenyl group, 0chlorophenyl group, 2,4-di-t-
Examples include pentylphenyl group, 4-hexadecyloxyphenyl group, 4-acetamidophenyl group, and 4-dodecylsulfoadanno group.

In general formula (1), R2 represents an alkyl group or an aryl group. These groups represented by R2 include the above R1
The same groups as explained above can be mentioned.

In general formula (1), the divalent bonding group bonded to the active site of the coupler represented by X is preferably one represented by the following general formulas (3) to (29).

General formula (3) General formula (4) General formula (11) General formula (12) 3 4 General formula (5) General formula (6) 3 -0-CH+ CH, 丑0 (-CHCl! 20-h- 0OH General formula (7) General formula (8) 3 - NlIC0+ O→7 - N)ICONH 4 General formula (9) General formula (10) 3 - NH30□C→1 -NH5O□N11- 4 General formula (13) %Formula% General formula (14) -5-CIl + CIl□→T 0OH General formula (15) In formulas (3) to (15), R3 and R4 are each a hydrogen atom or an alkyl group (e.g. methyl group, ethyl group) etc)
, represents an aryl group (eg, phenyl group, naphthyl group, etc.), and these groups may further have a substituent.

n represents an integer of 0 to 4.

General formula (16) General formula (17) General formula (24) General formula (25) General formula (18) General formula (19) General formula (26) General formula (27) General formula (20) General formula (21) General formula (28) General formula (29) General formula (22) General formula (23) 2 1 In formulas (16) to (29), R5 is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an aryl group, respectively. group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amino group, alkoxy group,
It represents an aryloxy group, a cyano group, a ureido group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group, or a heterocyclic residue, and these groups can further be expressed as a hydroxyl group, a carboxy group, a sulfo group, an alkoxy group, a cyano group, a nitro group, etc. It also includes those substituted with a group, an alkyl group, an aryl group, an aryloxy group, an acyloxy group, an acyl group, a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, etc.

In the general formula (1), the ethylenically unsaturated group represented by Q or the group having an ethylenically unsaturated group is preferably a group represented by the following general formula (30).

General formula (30) where R is a hydrogen atom, a carboxy group or an alkyl group (
For example, a methyl group, an ethyl group, etc.), and this alkyl group also includes those having a substituent, such as a halogen atom (for example, a fluorine atom, a chlorine atom, etc.).
, carboxy group, 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 -NIICO--CONH--C
OOoco--5co--cos--o--5--so
--so□-, etc. X+ and X2 each represent a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include:
Examples of the alkylene group, arylene group, aralkylene group, alkylenearylene group, and arylenealkylene group include methylene group, ethylene group, propylene group, etc., and examples of the arylene group include phenylene group, etc. Examples of the aralkylene group include a phenylmethylene group, examples of the alkylenearylene group include a methylenephenylene group, and examples of the arylenealkylene group include a phenylenemethylene group.

k % (11, m I , l I , m t each represent O or l.

In addition, in order to have good dye transferability, the general formula (1
) of the coupler represented by (X), substituents other than l-Q preferably have 8 or less carbon atoms, and (X)fi-
The total number of carbon atoms in substituents other than Q is preferably 15 or less.

The polymer having a repeating unit derived from the monomer represented by the general formula (1) of the present invention is a polymer having a repeating unit derived from the monomer represented by the general formula (1).
) Even if it is a so-called homopolymer of a repeating unit consisting of only one type of monomer represented by the above general formula (1), or a copolymer combining two or more types of monomers represented by the above general formula (1). It may also be a copolymer comprising one or more comonomers having other copolymerizable ethylenically unsaturated groups.

Examples of the comonomer having an ethylenically unsaturated group that can form a copolymer with the monomer represented by the general formula (1) of the present invention include acrylic esters, methacrylic esters, vinyl esters, olefins, and styrene. kind,
Crotonate esters, itaconate diesters, maleate diesters, fumarate diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters,
Examples of unsaturated monomers include unsaturated monomers, 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-l-, benzyl acrylate, methoxyhensyl 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 (additional mole number n=
9), 1-bromo-2-methoxyethyl acrylate,
Examples include 1,1-dichloro-2-ethoxyethyl acrylate.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate, agol methacrylate, methyl acrylate, Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylacunophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate,
Phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate , 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, '1-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate , 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of added moles n =
6), allyl methacrylate, dimethylagonoethyl methacrylate methyl chloride salt, and the like.

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

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

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, and dibutyl maleate.

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

Examples of other comonomers include the following. That is, acrylamides, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, hensylacrylamide, hydroxymethylacrylamide,
Methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.; Methacrylamides, such as methacrylamide, methylmethacrylamide, ethylmethacrylamide amide, propyl methacrylamide, butyl methacrylamide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-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, methoxy Ethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl/7-), phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N- Vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile, methacrylonitrile, etc.; Polyfunctional monomers, such as divinylhene. Zane, methylene bisacrylamide, ethylene glycol dimethacrylate, etc. can be mentioned.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates such as monomethyl maleate, monoethyl maleate, maleic acid, etc. Citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.: methacryloyloxyalkyl Sulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc. Niacrylamidoalkylsulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid , 2-methacrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acids, such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, etc.
Methacrylamide-2-methylbutylsulfonic acid, etc.; Acryloyloxyalkyl phosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.; Methacryloyloxyalkyl phosphates, such as,
Examples include methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, and the like; sodium 3-aryloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali metals (e.g., Na, K, etc.) or ammonium ions.Additional comonomers include those described in U.S. Pat.
, No. 790, No. 3,438,708, No. 3,55
No. 4,987, No. 4,215,195, No. 4,2
47.673, JP-A-57-205735, and the like can be used. Specific examples of such crosslinkable monomers include N-(2-acetoacetoxyethyl)acrylamide, N-(2-(2-acetoacetoxyethoxy)ethyl)acrylamide, and the like.

Furthermore, when forming a copolymer with the monomer represented by the general formula (1) of the present invention and the comonomer, preferably the repeating units consisting of the monomer represented by the general formula (1) are The content is preferably 10 to 90% by weight, more preferably 30 to 70% by weight of the total polymer.

-i-wise, the polymer coupler is polymerized by an emulsion polymerization method or a solution polymerization method, and the dye-providing substance polymer of the present invention has repeating units derived from the monomer represented by the general formula (1) according to the present invention. Can be mixed in a similar manner. Regarding the emulsion polymerization method, U.S. Patent No. 4,08
No. 0,211, No. 3,370,952, and U.S. Pat. No. 3,451,820 for dispersing lipophilic polymers in latex form in aqueous gelatin solutions. Can be used.

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

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 uralyl sulfate, sodium dioctylsulfosuccinate, sulfates of nonionic activators, and the like.

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.

Furthermore, 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 alone as emulsifiers or in combination with other surfactants. For information on the types of these activators and their effects, please refer to Belgische Chemische Industrie.
ischeIndusLrie), 28.16-20
(1963).

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

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

Further, these organic solvents can be used alone or in combination of two or more.

In producing the dye-providing substance polymer according to the present invention, the solvent used in the polymerization is preferably a good solvent for the monomer and the produced dye-providing substance polymer, and has low reactivity with the polymerization opening agent. Specific examples include water, toluene, alcohol (e.g. methanol, ethanol, 1so-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 dye-providing polymer of the present invention include those shown below.

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

In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2.2'-azobis-(2,4-dimethylvaleronitrile),
'-Azobis(4-methoxy2,4-dimethylvaleronyl), 1.1'Azobis(cyclohexanone-
1-carbonitrile), 2.2'-azobisisocyanoacetic acid, dimethyl 2°2'-azobisisobutyrate, 1. l′
-Azobis(cyclohexanone-1-carbonitrile)
, azo compounds such as 4,4'-azobis-4-cyanovaleric acid, peroxides such as benzoyl peroxide, lauryl peroxide, chlorobenzyl peroxide, diisobrobyl peroxide, di-t-butyl peroxide, etc. etc. can be mentioned. Among these, preferred are benzoyl peroxide, chlorobenzyl peroxide, lauryl peroxide and the like.

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

Furthermore, polymerization methods other than those described above, such as suspension polymerization and bulk polymerization, can also be applied. That is, in the present invention, a dye-donating homopolymer of the monomer represented by the general formula (1) of the present invention, a copolymer formed by combining two or more of the monomers, or the monomer and other monomers It includes all copolymers comprising at least one polymerizable comonomer as a copolymerization component, and is not limited by the bottom process.

Furthermore, the weight average molecular weight of the polymer having repeating units derived from the jIL polymer represented by the general formula (1) is preferably 10,000-1,000,000, more preferably 50,000. ~2,000,0
It is 00.

In the present invention, the weight average molecular weight is measured by GPC method (gel permeation chromatography method). The measurement method is shown below.

GPC: HLC-802A (manufactured by Toyo Soda) Column:
TSK gel (manufactured by Toyo Soda) MH (exclusion limit molecular weight 4 x 101') 1 wood (column dimensions ?, 51 (manufactured by Toyo Soda) Detection wavelength: 254 nm A calibration curve was prepared using TSK standard polystyrene (manufactured by Toyo Soda).

In the present invention, when the monomer represented by general formula (1) remains unreacted in the polymer of the present invention, the remaining amount is preferably 5% by weight or less of the completely destroyed polymer, and more preferably. is 0.5% by weight or less. The remaining amount of such monomers can also be measured by the above-mentioned GPC method.

Specific examples of the dye-providing substance according to the present invention, which is a polymer derived from a monomer represented by general formula (1), are listed below. However, it goes without saying that the dye-providing substances that can be used in the present invention are not limited to the examples below.

The monomer represented by the general formula (1) is a group having an ethylenically unsaturated group or a group into which an ethylenically unsaturated group can be introduced by halogenating the corresponding 4-equivalent coupler. (or its precursor) with a nucleophilic reagent in the presence of a base, and optionally, further introducing an ethylenically unsaturated group.

An example of synthesis of a dye-providing substance derived from the monomer represented by general formula (1) is shown below.

Synthesis Example (Exemplary Compound Y-l) 53 g of the monomer of the compound according to the present invention and 13 g of n-butyl acrylate were dissolved in 500 - of dimethylformacide, and heated to 75°C while degassing with Nff1 (nitrogen) gas. did. While passing Nt gas into the solution, 600 μl of abbisisobutyronitrile was added and reacted at about 80° C. for 4 hours. Add the reaction solution to water and separate the precipitated solid by filtration.
After drying, 50 g of Y-1 was obtained (yield 76%).

The heat-developable color photosensitive material of the present invention contains, as a dye-providing substance, at least one dye-providing substance according to the present invention, which is a polymer.

The heat-developable color photosensitive material of the present invention may contain other dye-providing substances as appropriate.

Dye-providing substances that can be used in combination are described below.

For example, JP-A-62-44737, JP-A-62-12985
No. 2, US Pat.
The leuco dye described in US Pat. Diffusible dye-donating substances that form or release dyes are preferably used, and in particular compounds that form diffusible dyes by campling reaction are preferably used.

Diffusible dye-providing substances that can be used in combination will be explained below. The diffusible dye-donor substance may be one that is capable of forming or releasing a diffusible dye as a function of the reduction reaction of the photosensitive silver halide and/or the organic silver salt used if necessary. Depending on their reaction form, they can be classified into negative-type dye-donating substances and positive-type dye-donating substances.

As a negative dye-donating substance, for example, U.S. Pat.
No. 63,079, No. 4,439.513, JP-A-59
-60434, 59-65839, 59-71
No. 046, No. 59-87450, No. 59-88730
Examples include reducible dye-releasing compounds described in the specifications of No. 59-123837, No. 59-124329, No. 59-165054, and No. 59-164055.

Other negative dye-providing substances include, for example, U.S. Pat.
, 474, No. 867, JP-A-59-12431,
No. 59-48765, No. 59-174834, No. 5
No. 9-776642, No. 59-159159, No. 59
Examples include coupled dye-releasing compounds described in specifications such as No. 231040.

Another particularly preferred negative-tone dye-providing substance of the Campling dye-forming compound is one represented by the following general formula (a).

General formula (A) Cp-←J←----→B) In the formula, Cp is an organic group (coupler residue) that can react with the oxidized form of the reducing agent (campling reaction) to form a diffusible dye. J represents a divalent bonding group bonded to the active position that reacts with the oxidized form of the reducing agent, and B represents a ballast group. Here, the ballast group is a group that substantially prevents the dye-providing substance from diffusing during heat development processing, and includes groups that exhibit this effect depending on the nature of the molecule (such as a sulfo group),
The coupler residue represented by Cp, which is a group that exhibits its effect depending on its size (such as a group with a large number of carbon atoms), has a molecular weight of 700 or less in order to improve the diffusibility of the dye formed. It is preferably 500 or less, and more preferably 500 or less.

The ballast group preferably has 8 or more carbon atoms, more preferably 12 or more carbon atoms, and even more preferably a group that is a polymer chain.

The campling dye-forming compound having a group as a polymer chain is preferably one having a polymer chain having a repeating unit derived from a monomer represented by general formula (b) as the above group.

General formula (B) Cp-(-J-H-Y+T-(Y-(L)) In the formula, cp,
J has the same meaning as defined in general formula (a), Y represents an alkylene group, arylene group or aralkylene group, l represents O or l, Z represents a divalent organic group,
L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of coupling dye-forming compounds represented by general formulas (a) and (b) include JP-A-59-124339
No. 59-181345, No. 60-2950, No. 6157943, No. 61-59336, etc.,
U.S. Pat. No. 4,631.251, U.S. Pat. No. 4,650,748
No. 4,656.124, and in particular, U.S. Pat. No. 4,656.124,
U.S. Patent Nos. 4,631,251 and 4,650,74
The polymer type dye-providing substances described in each specification of No. 8 are preferred.

As a positive dye-donating substance, for example, JP-A-59-
No. 55430, No. 59-165054, No. 59-15
No. 4445, No. 59-766954, No. 59-116
No. 655, No. 59-124327, No. 59-1524
Examples include compounds described in publications such as No. 40.

These dye-providing substances may be used alone or in combination of two or more kinds. The amount used is not limited and depends on the type of dye-providing substance, whether it is used alone or in combination, and 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. For example, the amount to be used is 0.005 to 50 g per 1 kg, preferably 0.00 g per 1 kg.
It can be used in amounts of 1 g to Log.

The dye-providing substance used in the present invention can be incorporated into the photographic constituent layer of the heat-developable light-sensitive material using any method. , tricresyl phosphate, etc.).
Either by emulsifying and dispersing it, or by dissolving it in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.) and then neutralizing it with an acid (e.g., citric acid or nitric acid, etc.).
or an aqueous solution of a suitable polymer (e.g. gelatin,
It can be used after being solidly dispersed in polyvinyl butyral, polyvinyl pyrrolidone, etc.).

Next, the photosensitive silver halide used in the present invention will be described. Any silver halide can be used, and examples thereof include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, and silver iodobromide. The photosensitive silver halide can be prepared by any method commonly used in the photographic art.

Furthermore, it is possible to use emulsions containing grains with a multilayer structure in which the halogen composition of the grains differs on the surface and inside. For example, core/shell type silver halide grains in which the halogen composition changes in a step-like manner. , or silver halide emulsions having continuously varied grains can be used.

In addition, the shape of photosensitive silver halide is cubic, spherical, 8
It is possible to use materials that have a clear crystal habit, such as a hedron, dodecahedron, and tetradecahedron, or those that do not. This type of silver halide is described in JP-A-60-215948.

Also, for example, JP-A-58-111933, JP-A No. 5841
No. 1934, No. 58-108526, Research Disclosure No. 22534, etc., and each of these crystal planes has a crystal surface that is larger than the other single crystal of this particle. It is also possible to use a silver halide emulsion containing tabular silver halide grains having a large area and an aspect ratio, that is, a ratio of grain diameter to thickness of 5=1 or more.

Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces have not been fogged in advance can be used. For internal latent image type silver halide whose surface is not prefogged, for example, U.S. Pat.
, No. 592, 250, No. 3,206, No. 313, No. 3,
No. 317,322, No. 3,511.622, No. 3, 4
No. 47.927, No. 3,761,266, No. 3,70
It is described in each specification such as No. 3,584 and No. 3,736.140.

Internal latent image type silver halide grains whose surfaces are not fogged in advance are silver halide grains in which the sensitivity inside the grain is higher than the sensitivity on the surface of the silver halide grain, as described in the above specifications. be. Also, U.S. Patent No. 3,271,15
No. 7, No. 3,447,927 and No. 3,531,
Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in US Pat. No. 291, or silver halide emulsions containing dopants as described in U.S. Pat. Silver halide emulsion with weakly chemically sensitized grain surfaces, or JP-A-50-852
Silver halide emulsions comprising grains having a laminated structure as described in publications such as No. 4 and No. 50-38525, and other publications such as JP-A-52-156614 and JP-A-55-127.
Silver halide emulsions such as those described in No. 549 can be used.

The silver halide in the above-mentioned photosensitive emulsion may have coarse or fine grains, but the preferred grain size is about 0.005 μm to about 1.5 μm, more preferably about 0.005 μm to about 1.5 μm. .01 μm-o, s μm.

In the present invention, as another method for preparing photosensitive silver halide, it is also possible to allow a photosensitive root salt form rfcrli component to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt. .

These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various ways, and the amount used is preferably 0.001 g to 50 g per 1 d of support per layer. More preferably, it is 0.1 to 10 g.

The light-sensitive silver halide emulsion may be chemically sensitized by any method in the photographic art.

Further, the photosensitive silver halide emulsion used can be spectral sensitized using a known spectral sensitizing dye to impart sensitivity to blue, green, red, and near-infrared light.

Typical spectral sensitizing dyes that can be used include, for example, cyanine, merocyanine, complex (that is, trinuclear or tetranuclear) cyanine, holobola-cyanine,
Examples include styryl, hegocyanine, oxonol, and the like.

The preferred amount of these sensitizing dyes to be added is lXl0- per mole of photosensitive silver halide or silver halide forming component.
h mole - 1 mole. More preferably, I Xl0-
'~lXl0-' mole.

The sensitizing dye may be added at any stage of the preparation of the silver halide emulsion. That is, it may be carried out at any time, such as when silver halide grains are formed, when soluble salts are removed, before the start of chemical sensitization, during chemical sensitization, or after the end of chemical sensitization.

In the heat-developable photosensitive material of the present invention, it is preferable to use various organic silver salts, if necessary, for the purpose of increasing sensitivity and improving developability.

Examples of organic silver salts that can be used in the heat-developable photosensitive material of the present invention include JP-A Nos. 53-4921 and 49-5262.
No. 6, No. 52-141222, No. 53-36224, No. 53-37626, and No. 53-37610, as well as U.S. Patent No. 3,330,633, No. 3,794,496, Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having heterocycles, such as silver behenate, α-( 1-phenyltetrazolethio)silver acetate, etc., and Japanese Patent Publication No. 1982-26582, No. 45-
No. 12700, No. 45-18416 No. 45-2218
No. 5, JP-A-52-137321, JP-A No. 58-1186
No. 38, No. 58-118639, U.S. Patent No. 4,12
There are silver salts of imino groups described in various publications such as No. 3,274.

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

The organic silver salts used in the present invention may be used alone or in combination of two or more, or the silver salts may be prepared in a suitable binder and used as they are without isolation.
The isolated product may be used after being dispersed in a binder by an appropriate means. Examples of dispersion means include, but are not limited to, ball mills, sand mills, colloid mills, vibration mills, and the like.

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

The heat-developable color light-sensitive material of the present invention has a reducing agent (in this specification, reducing agent breaker is also included in the reducing agent).

Examples of reducing agents that can be used in the present invention include U.S. Pat. Nos. 3,531,286 and 3,761,27
No. 0, the specifications of No. 3,764,328, and RD (
Research Disclosure) Aim 12146, Same 11
h15108゜Double 15127 and JP-A-56-271
No. 32, U.S. Pat. No. 3,342,599. No. 3,719.492 Specifications, JP-A-53-1356
p- described in each publication such as No. 28 and No. 57-79035.
Phenyl diamine type and p-aminophenol type developing agents, phosphoramidophenol type, sulfonamide aniline type developing agents, hydrazone type color developing agents and their precursors, or phenols, sulfonamide phenols, or polyhydroxybenzenes. , naphthols, hydroxybinaphthyls and methylene bisnaphthols, methylene bisphenols, ascorbic acid, 3-pyrazolidones, and pyrazolones can be used.

Further, the dye-donating substance may also serve as a reducing agent.

As a particularly preferable reducing agent, JP-A-56-146133
N-(p-
N.

N-dialkyl) phenylsulfamate can be mentioned.

Two or more types of reducing agents may be used at the same time.

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 organic acid silver salt, the type of other additives, etc., and is not necessarily constant. The amount is generally preferably from 0.01 to 1,500 mol, more preferably from 0.1 to 200 mol, per mol of photosensitive silver halide.

Binders that can be used in the heat-developable photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate,
These include ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives, proteins, starch, synthetic leather such as gum arabic, or natural polymeric substances. These can be used alone or in combination of two or more. In particular, it is preferable to use gelatin or a derivative thereof together with a wood-loving polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably to use a mixed binder of gelatin and polyvinylpyrrolidone described in JP-A-59-229556. It is to use.

The preferred amount of binder used is usually 0.05 g to 50 g per 1 support, more preferably 0.2 g.
~20g.

In addition, the binder is 0.1% per 1g of the dye-providing substance.
It is preferable to use ~10g, more preferably 0.2
~5g.

The heat-developable photosensitive material of the present invention can be obtained by forming a photographic constituent layer on a support, and examples of the support that can be used here include polyethylene film, cellulose acetate film, polyethylene terephthalate film, and polyethylene terephthalate film. Synthetic plastic films such as vinyl chloride, paper supports such as photographic base paper, printing paper, baryta paper and resin coated paper, and supports obtained by coating and curing electron beam curable resin compositions on these supports. Examples include the body.

In the heat-developable photosensitive material of the present invention, and when the photosensitive material is of a transfer type and an image-receiving member is used, it is preferable that various thermal solvents are added to the heat-developable photo-sensitive material and/or the image-receiving member.
The thermal solvent is a compound that is liquid during thermal development and promotes thermal development and/or thermal transfer. These compounds include, for example, US Pat. No. 3,347,675. No. 3
, No. 667.959, RD (Research, Tisfroger) Na17643 (X I [), JP-A-59-2
No. 29556, No. 59-68730, No. 59-842
No. 36, No. 60-191251, No. 60-23254
No. 7, No. 60-14241, No. 61-52643,
No. 62-78554, No. 62-42153, No. 62
-4213 publications, etc., U.S. Patent No. 3.438,776
No. 3.666477, No. 3,667.959, specifications, JP-A-51-19525, No. 53-2482.
9, No. 53-60223, No. 58-118640, and No. 53-19825, examples of which are particularly useful in carrying out the present invention include: , for example, urea derivatives (e.g., dimethylurea, diethylurea, phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide, p-toluamide, etc.), sulfonamide derivatives (e.g., benzenesulfonamide, α-toluenesulfonamide, etc.), Examples include polyhydric alcohols (for example, 1,6-hexanediol, 1,2-cyclohexanediol, pentaerythritol, etc.) or polyethylene glycols.

Among the above thermal solvents, water-insoluble solid thermal solvents are particularly preferably used.

Specific examples of the above-mentioned water-soluble heat solvent include, for example, JP-A-62
- No. 136645, No. 62-139549, No. 63-
Some of them are described in Japanese Patent Application No. 53548, Japanese Patent Application No. 63-205228, and Japanese Patent Application No. 63-54113.

Examples of the layer to which a heat solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving layer of an image receiving member, etc., and the heat solvent is added to each layer so as to obtain an effect depending on each layer.

The preferred addition amount of the heat solvent is usually 10% to 500% by weight of the binder amount, more preferably 30% to 200% by weight.
Weight%.

The organic silver salt and the thermal solvent may be dispersed in the same dispersion liquid, and the same binder, dispersion medium, and dispersion device as used for producing each dispersion liquid can be used.

In addition to the above-mentioned components, the photothermographic material of the present invention may contain various additives, such as a development accelerator, an antifoggant, and a base precursor, as required.

As development accelerators, compounds described in JP-A-59-177550, JP-A-59-111636, and JP-A-59-124333 are used, as well as compounds described in JP-A-61-159642 and JP-A-62-203908. The development accelerator-releasing compounds described above or metal ions having an electronegativity of 4 or more as described in Japanese Patent Application No. 104645/1988 can also be used.

Anti-capri agents include, for example, U.S. Pat. No. 3,645.
Higher fatty acids described in specification No. 739, Japanese Patent Publication No. 4
Second mercury salt described in Publication No. 7-11113, JP-A-51
-N-halogen compound described in Publication No. 47419, U.S. Patent No. 3,700,457, JP-A-51-50
Mercapto compound releasing compound described in Publication No. 725,
Aryl sulfonic acids described in JP 49-125016, carboxylic acid lithium salts described in JP 51-47419, British Patent No. 1,455,271, and JP-A-50-101,019. The oxidizing agent described in 53
Sulfinic acids or thiosulfonic acids described in Japanese Patent Publication No. 19825, 2-thiouracils described in Japanese Publication No. 51-3223, simple sulfur described in Japanese Publication No. 51-26019, No. 51-42529, No. 51-81124, 5
Disulfide and polysulfide compounds described in Publication No. 5-93149, rosins or diterpenes described in Publication No. 51-57435, polymer acids having free carboxyl groups or sulfonic acid groups described in Publication No. 51-104338, US Pat. Thiazolinthione described in Patent No. 4,138,265, JP-A-54-5182
1,2,4-triazole or 5-mercapto-1,2,4-)riazole described in US Pat. No. 4,137.079, JP-A-55-14088
Thiosulfinate esters described in No. 3, No. 55-1
1,2゜3.4-thiatriazoles described in Publication No. 42331, No. 59-46641, No. 59-57233
No., dihalogen compounds or trihalogen compounds described in Publication No. 59-57234, and furthermore, No. 59-111.
Thiol compound described in Publication No. 636, No. 60-198
Hydroquinone derivatives described in Publication No. 540, 60-
Examples include the combined use of a hydroquinone derivative and a benzotriazole derivative described in Japanese Patent No. 227255.

Still another particularly preferred antifoggant is disclosed in JP-A No. 6
2 to 78554, polymer inhibitors described in JP-A-62-121452, and ballast-group-containing inhibitors described in JP-A-62-123456. Can be mentioned.

Furthermore, colorless couplers described in Japanese Patent Application No. 62-320599 are also preferably used.

Examples of base precursors include compounds that release basic substances by decarboxylation upon heating (e.g., guanidinium trichloroacetate), compounds that decompose by reactions such as intramolecular and nuclear substitution reactions, and release amines, etc. For example, Japanese Patent Application Publication No. 56-130745, Japanese Patent Application Publication No. 56-132332, British Patent No. 2,079,480, U.S. Patent No. 4,0
60.420 specification, JP-A-59-157637,
No. 59-166943, No. 59-180537, No. 59-174830, No. 59-195237, No. 6
Examples include base releasing agents described in JP2-108249, JP62-174745, and the like.

In addition, various additives used in heat-developable photosensitive materials as necessary, such as antihalation dyes, fluorescent brighteners, hardeners, antistatic agents, plasticizers, spreading agents, capping agents, and surfactants. , an anti-fading agent, etc., which are specifically described in RD (Research Disclosure) magazine vol.

170. June 1978 No. 17029, JP-A-62-
It is described in Publication No. 135825 and the like.

These various additives may be added not only to the photosensitive layer but also to non-photosensitive layers such as an intermediate layer, a protective layer, or a backing layer.

The heat-developable photosensitive material of the present invention contains (Al-photosensitive silver halide, (b) a dye-providing substance, (Cl binder, and FDL reducing agent). It may further contain (e) organic silver as necessary. Preferably, these may basically be contained in one heat-developable photosensitive layer, but they do not necessarily need to be contained in a single photographic constituent layer. For example, the heat-developable photosensitive layer may be divided into two layers, Said (al, (C1, (el.

The component (d) may be contained in one heat-developable photosensitive layer and the dye-providing substance (b) may be contained in the other layer adjacent to this photosensitive layer, in a state where they can react with each other. If necessary, it may be contained in two or more constituent layers.

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

The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers. In the case of full-color photosensitive materials,
Generally, it 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.

Usually, 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 combination is not limited to this, and it is also possible to combine a near-infrared sensitive layer. It is.

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 a support, or a blue-sensitive layer is sequentially formed on a support. , a green-sensitive layer, a red-sensitive layer, or a green-sensitive layer, a red-sensitive layer, and a blue-sensitive layer sequentially on the support.

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

The heat-developable photosensitive material of the present invention can be exposed to light using an appropriate light source, and examples of the exposure light source include a tungsten lamp,
Various types such as halogen lamps, xenon lamps, mercury lamps, cathode ray tube flying spots, light emitting diodes, lasers (e.g. gas lasers, YAG lasers, dye lasers, semiconductor lasers, etc.), CRT light sources, and FOT can be used singly or in combination. It can be used as Semiconductor laser and second harmonic generating element (SHG element)
etc. can also be used. In addition, electron beams, X-rays,
Exposure may be performed using light emitted from a phosphor excited by T-rays, α-rays, or the like. Exposure times include not only exposure times of 1/1000 seconds to 1 second that are normally used with cameras, but also exposures shorter than 1/1000 seconds, such as exposures of 1/10 to 1/10" seconds using xenon flash lamps and cathode ray tubes. If necessary, the spectral composition of the light used for exposure can be adjusted with a color filter.The light-sensitive material of the present invention can be used for scanner exposure using a laser or the like.

The heat-developable photosensitive material of the present invention usually preferably has a
Development can be carried out by simply heating at a temperature range of 0° C. to 200° C., more preferably 100° C. to 170° C., preferably 1 second to 180 seconds, more preferably 1.5 seconds to 120 seconds. 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, or by bringing the image-receiving member into close contact with the image-receiving member after heat development. Alternatively, the transfer may be performed by supplying ice and then applying heat if necessary, or preheating may be performed in a temperature range of 70° C. to 180° C. before exposure. Also, JP-A-60-143
As described in No. 338 and No. 61-162041, the photosensitive material and the image receiving member may be preheated at a temperature of 80°C to 250°C immediately before thermal development transfer to improve mutual adhesion. good.

Various heating means can be used for the heat-developable photosensitive material of the present invention.

As the heating means, any method that can be applied 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, or passing through a high-temperature atmosphere. 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, and methods such as preheating and then reheating, continuous heating at a high temperature for a short time, or heating at a low temperature for a long time, continuously increasing the temperature, etc. Although it is also possible to lower the exposure rate or to repeat the process, and discontinuous heating is also possible, a simple pattern is preferable, and a method in which exposure and heating proceed simultaneously may also be used.

The heat-developable color photosensitive material of the present invention is of a transfer type. In this case, the image-receiving layer that can be effectively used in the image-receiving member may be one having the function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, such as a tertiary amine Alternatively, a polymer containing a quaternary ammonium salt described in US Pat. No. 3,709,690 is preferably used. Typical image-receiving layers for diffusion transfer include those obtained by mixing a polymer containing ammonium salt, tertiary atom, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support. As another useful dye-receiving material, JP-A-5
Examples include those formed from heat-resistant organic polymeric substances having a glass transition temperature of 40° C. or higher and 250° C. or lower, as described in Japanese Patent Publication No. 7-207250.

The binder used in the image-receiving layer is preferably a hydrophobic binder.

The polymer for forming the image-receiving layer may be supported on a support as an image-receiving layer, or may itself be used as a support.

Regarding polymers, "Polymer Handbook, Second Edition" (edited by Joy Brandrup and E.H. Inmargat), published by John Willi and Sons (Polymer Iranbook 2nd
ed, (J, [1randrup, E, Il, Im
(edited by mergut) John W'1ley & 5o
Also useful are synthetic polymers with a glass transition temperature of 40°C or higher, as described in NS). - For boat fishing, a molecular weight of 2,000 to 200,000 is useful for the polymeric substance.

These polymeric substances may be used alone or in a blend of two or more thereof, or may be used in combination of two or more as a copolymer.

A particularly preferable image-receiving layer is JP-A-59-22342
Examples include a layer more powerful than polyvinyl chloride described in Japanese Patent No. 5, and a layer made of polycarbonate and a plasticizer described in JP-A-6049138.

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, and examples thereof include films of polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, and supports thereof. Supports containing pigments such as titanium oxygen, barium sulfate, calcium carbonate, and talc, baryta paper, resin coated paper laminated with thermoplastic resin containing pigments on paper, fabrics, glasses, metals such as aluminum, supports on which an electron beam curable resin composition containing pigments is coated and cured, and coating layers containing pigments are provided on these supports. Examples include supports such as Furthermore, various coated papers such as the cast coated paper described in JP-A-62-283333 are also useful as supports.

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

Appropriate additives, such as various known additives, can be added to the image receiving member. Examples of such additives include ultraviolet absorbers, image stabilizers, development accelerators, antifoggants, pHgFl adjusters (various acids and acid precursors, bases and base precursors, etc.), and thermal solvents. can be mentioned.

Typical examples of ultraviolet absorbers include benzotriazole compounds and benzophenone compounds. Examples of image stabilizers include hindered amine type, hindered phenol type, dialkoxybenzene type, chroman type, indane type, thioether type,
Examples include hydroquinone-based compounds, chlorine-substituted s-triazine-based compounds, and the like. The development accelerator and antifoggant can be appropriately selected from compounds added to heat-developable photosensitive materials.

The heat-developable photosensitive material of the present invention is published in RD (Research Disclosure Magazine) No. 15108, JP-A-57-1984.
No. 58, No. 57-207250, No. 61-80148
The photothermographic material may be a so-called monosheet type photothermographic material in which a photosensitive layer and an image-receiving layer are formed on the same support, as described in the above publication.

The heat-developable photosensitive material of the present invention is preferably provided with a protective layer.

Various additives used in the photographic field can be used in the protective layer. The additives include various matting agents, colloidal silica, slipping agents, organic fluoro compounds (especially fluorine surfactants), antistatic agents, ultraviolet absorbers,
High-boiling organic solvents, antioxidants, hydroquinone derivatives,
Polymer Latinx, surfactant (including polymeric surfactant), hardener (including polymeric hardener), organic silver salt particles, non-photosensitive silver halide particles, antifoggant, development accelerator agents, etc.

Regarding these additives, please refer to RD (Research Disclosure Magazine) Vol. 170. June 1978 N1
No. 17029 and JP-A-62-135825.

In the present invention, the dye formed by reacting with the oxidized product of the reducing agent is hydrophobic, and in particular, the inorganic value/organic value of the dye is 1.2.
It is preferable that the hydrophobicity is less than 100%. Note that inorganic value and organic value are in the field of chemistry 11.719 (19
This is a concept for predicting the properties of compounds described in 57).

Margin 1' below [Examples] Specific examples of the present invention will be described below. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 In this example, a silver iodobromide emulsion, a dispersion of an organic silver salt and a heat solvent, a dye-providing substance dispersion, and a reducing agent dispersion were prepared as follows, and these were used to heat the A developable color photosensitive material was prepared. Further, an image receiving member was prepared as described below.

■ Preparation of silver iodobromide emulsion At 50°C, JP-A-57-92523;
Using the mixer shown in Publication No. 92524, 20 g of ossein gelatin, 1000 g of distilled water, and ammonia were dissolved in solution (A) containing 11.6 g of potassium iodide and 131 g of potassium bromide. (B
) 500 ml of liquid, water containing 1 mole of silver nitrate and ammonia? 500 ml of solution (C) was added at the same time while keeping the pAg constant.

The shape and size of the emulsion grains to be prepared were adjusted by controlling pHlpAg and the addition rates of solutions (B) and (C). In this way, a core emulsion with a silver iodide content of 7 mol %, regular octahedral grains, and an average grain size of 0.25 μm was prepared.

Next, a core/shell type silver halide emulsion with a regular octahedral shape and an average grain size of 0.3 μm was prepared by coating a silver halide shell with a silver iodide content of 1 mol % in the same manner as above. (*Dispersibility was 9%). The emulsion thus prepared was washed with water and desalted.

■ Preparation of photosensitive silver halide dispersion The following components were added to 100 ml of the silver iodobromide emulsion prepared as described above, and chemical sensitization and spectral sensitization were performed, resulting in red sensitivity, green sensitivity, and blue sensitivity. Each photosensitive silver halide emulsion dispersion was prepared.

(a) Preparation of red-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 700 rn1
4-Hydroxy-6-methyl-1゜3.3a,7-chitrazaindene 0.4 g Gelatin 32 g Sodium thiosulfate 10 mg Sensitizing dyes below (a) 1% methanol solution Distilled water Sensitizing dyes (a) 80 - 1200 ml (b) Preparation of green-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 70-4-hydroxy-6-methyl-1 3,3a,7-titrazaindene 0.4 g Gelatin 32 g Sodium thiosulfate 10 mg Below Sensitizing dye (b) 1% methanol solution 0 ml Water sensitizing dye (b) 1200 ml (c) Preparation of blue-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 700-4-hydroxy-6-methyl- 1 33a,? - Tetrazaindene 0.4 g Gelatin 32 g Sodium thiosulfate 10 [lW The following sensitizing dye (
C) 1% methanol solution 80 - Karatsu water sensitizing dye (C) 1200 ml ■ Dispersion of organic silver and thermal solvent A dispersion of organic silver salt and thermal solvent was prepared based on the following recipe.

Prescription Hens Tria Sole I 60.5 g
Heat solvent-8 (see below) 346 g Polyvinylpyrrolidone (10%) 446ml
Dilute to 2000 g with water.

After dispersing in an alumina ball bowl, the pH was adjusted to 5.5 with a 10% aqueous citric acid solution to prepare a dispersion of organic silver salt and thermal solvent.

Heat) Container-A ■ Preparation of dispersion of compound Y-l according to the present invention Compound Y
-130.1g, 0.024g of the following inhibitor-B, 3.6g of the following Nukahenger C, and 15g of tricresyl phosphate to 100mf of C-F acid edyl? Mix 360 mN of gelatin aqueous solution containing 5% by weight of alkanol XC and 36 g of aqueous solution 160-1 photographic gelatin.
After dispersing with an ultrasonic homogenizer and distilling off ethyl acetate, the mixture was adjusted to 1,200 ml to obtain a dispersion of a dye-providing substance.

Inhibitor - (B) Scanner (C) Green-sensitive silver halide 0.49 Ag polyvinylpyrrolidone 0.2g Inhibitor -
B 0.7 ■Benztriazole-1 1.0g gelatin
2.8g hot solvent-A
4.5 g tricresyl phosphate
0.65 g reducing agent (precursor) - (D
) (below) 0.6 g scavenger (C)
0.08 g of the reducing agent (precursor) (D) was added to the coating solution in which each dispersion was mixed immediately before coating.

Reducing agent (precursor) -(D) ■ Preparation of photosensitive material-1 Using the above dispersion liquid on a 180 μm thick transparent polyethylene terephthalate film coated with latex undercoat, each composition was coated with the following amount per support lr+ ( The photosensitive material-1 was prepared by coating and drying the photosensitive material.

Compound (Y-1') 0.64
6. Preparation of image-receiving member An image-receiving member was prepared by coating a polyvinyl chloride layer (image-receiving layer) containing the following compound on photographic baryta paper. In addition,
The amount of polyvinyl chloride applied was 12 g per 1M of support.

Cl Table 1 ■ Development temperature 150℃ )10C112CII25C112CI123C112
CI+2011 0.2 g/po Photosensitive materials-2 to 10 were prepared in the same manner as photosensitive material 1, except that the dye-providing substance in photosensitive material 1 was changed to the dye-providing substance of the present invention or a comparative compound shown in Table 1.

Each of the obtained photosensitive materials was exposed to light at 800 CMS through a step wafer, and the image-receiving materials were superimposed and thermally developed for 70 seconds at each temperature shown in Table 1. Table 1 shows the minimum density (fog) and maximum density of the obtained image.

Below margin C・ ■ Development temperature 155℃ Development temperature 145℃ comparative compound I CI! 3 +C112C)7 +Cll□-C11, 斤CI(3 (x=50% by weight.

y-50% by weight) 113 -(-CI+□ C-)-+CH.

C8→7 (X=50% by weight.

y = 50% by weight) As shown in Table 1, the photosensitive materials 1 to 6 using the dye-providing substance of the present invention can obtain magenta images with high maximum density and low fog, but the photosensitive materials using the comparative compound In this case, a sufficient maximum density cannot be obtained and fog is also high.

Furthermore, when the developing temperature is changed, the maximum density and minimum density of the photosensitive material of the present invention hardly change;
It can be seen that in the comparative light-sensitive materials, fog increases significantly as the development temperature increases, and maximum density decreases significantly as the development temperature decreases.

Example-2 Color multilayer photosensitive material 11 was prepared as shown in Table 2.

Margin below 824 Filter dye Polymer dye-donor substance (1) Bar CI+□ C-)y + C11□ C1l→7 (x=50% by weight y=50% by weight> Polymer dye-donor substance (2) lh Photosensitive material section Light-sensitive materials-12 to 17 were prepared in the same manner except that the dye-providing substance in the blue-sensitive layer of Example No. 11 was changed to the dye-providing substance of the present invention or the comparative compound shown in Table 3.

After exposing each of the prepared photosensitive materials to 1600 cMs of blue light through a stencil, the photosensitive materials were exposed to blue light at 1600 cMs through a stencil.
Heat development was performed at 150° C. for 2 minutes using a module 277 (3M Company). Thereafter, the photosensitive material and the image receiving member were quickly peeled off, and the image densities (maximum density Dma and minimum density Dmin) of the obtained color images were measured using each of blue light, green light, and red light. Similarly, each light-sensitive material was exposed to green light and red light, and the color images obtained by development in the same manner were subjected to density measurements using blue light, green light, and red light, respectively. The results are shown in Table-2.

As is clear from Table 3 below, the sample using the dye-donating substance of the present invention has less color turbidity than the comparative sample, and exhibits excellent properties in which the dye-donating substance is sufficiently immobilized. I understand.

〔Effect of the invention〕

As described above, the transfer-type heat-developable color photosensitive material of the present invention is a transfer-type heat-developable color photosensitive material in which the obtained transferred image has a high density and has little color turbidity. This has the advantage that the image density does not change at all even with slight temperature changes, and there is also very little contamination of the white background of the image.

Procedural amendment 1, Indication of case 1999 patent side No. 204232 2, Title of invention Transfer type heat-developable color photosensitive material 3, Person making amendment Relationship to case Patent applicant address 1-chome Nishi-Shinjuku, Shinjuku-ku, Tokyo 26 No. 2 Name (
127) Konica Co., Ltd. Dia Palace Nibancho 506

Claims (1)

[Scope of Claims] 1. A transfer type heat-developable color photographic material having at least a photosensitive silver halide, a reducing agent, a dye-providing substance, and a binder on a support, wherein the dye-providing substance is represented by the following general formula (1). A transfer type heat-developable color photosensitive material characterized by being a polymer derived from a monomer represented by: General formula (1) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 represents an alkyl group or an aryl group. R^2 represents an alkyl group or an aryl group. Q represents an ethylenically unsaturated group or a group containing an ethylenically unsaturated group. X represents a divalent linking group. n is 0 or 1.