JPH0682204B2 - Photothermographic material containing a novel cyan dye-donor - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photothermographic material capable of forming an image by heat development, and more particularly to a heat-sensitive photosensitive material containing a novel cyan dye-donor substance capable of forming a cyan dye image by heat development. The present invention relates to a photosensitive material.

BACKGROUND OF THE INVENTION In recent years, a photothermographic material capable of performing a developing step by heat treatment has been attracting attention as a photosensitive material.

For such a photothermographic material, for example, Japanese Patent Publication No. 43-4
Nos. 921 and 43-4924 disclose the light-sensitive material comprising an organic silver salt, silver halide, a reducing agent and a binder, which is commercialized by 3M Company as dry silver.

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

For example, in U.S. Pat. Nos. 3,531,286, 3,761,270 and 3,764,328, etc., a method of forming a dye image by reacting an oxidized product of an aromatic primary amine developing agent with a coupler, Research. Disclosure (Re
search disclosure) 15108 and 15127, US Patent No.
A method of forming a dye image by reacting an oxidant of a reducing agent (hereinafter, also referred to as a developer and a developing agent) which is a sulfonamidephenol or a sulfonamideaniline derivative described in 4,021,240 with a coupler, British Patent No. 1,
As disclosed in Japanese Patent No. 590,956, a method of using an organic imino silver salt having a dye portion to release the dye in the heat developing portion to release the dye image on a separately provided image receiving layer, and JP
No. 52-105821, No. 52-105822, No. 56-50328, a method for obtaining a positive dye image by the silver dye bleaching method disclosed in US Pat. No. 4,235,957, and US Pat.
No. 3, No. 3,985,565, No. 4,022,617, No. 4,452,88
Various methods have been proposed, such as a method for obtaining a dye image using the leuco dye disclosed in JP-A No. 3 and JP-A-59-206831.

However, these proposals relating to the above heat-developable color light-sensitive material make it difficult to bleach-fix a black-and-white silver image formed at the same time, and it is difficult to obtain a clear color image, and more complicated It was not yet satisfactory for practical use because it required post-treatment.

In recent years, as a color image forming method by a new type of heat development, JP-A-57-179840, 57-186744 and 57-198 have been proposed.
No. 458, No. 57-207250 and the like, a method of transferring a diffusible dye released by heat development to obtain a color image was disclosed.

Then, by further improving these methods, for example, a non-diffusible reducing dye-providing substance disclosed in JP-A Nos. 58-58453 and 59-168439 is oxidized to form a diffusible dye. Method of releasing the gas, JP-A-58-79247 and 59-17483
No. 4, No. 59-12431, No. 59-159159, No. 60-2950, a method of releasing a diffusible dye by coupling with an oxidant of a developing agent as disclosed in JP-A- Sho 58
-149046, 58-149047, 59-124339, 59-1813
No. 45, No. 60-2950, Japanese Patent Application No. 59-181604, No. 59-182506
No. 59-182507, No. 59-272335 and the like, a method using a non-diffusible compound which reacts with an oxidized product of a developing agent to form a diffusible dye, and further, JP 59-1
52440, 59-124327, 59-154445, 59-166954
Containing a non-diffusible reducing dye-donor substance that loses its ability to release a diffusible dye by oxidation, and a non-diffusible dye-donor substance that releases a diffusible dye when reduced. A method to do so has been proposed.

The photothermographic material is a material for obtaining a dye image by transferring the released or formed diffusible dye onto an image-receiving layer of an image-receiving member provided on the same support or on another independent support. In view of the sharpness and stability of the image, it has been improved in many points as compared with the conventional heat-developable color photosensitive materials.

Among these heat-developable color light-sensitive materials, the one that forms a dye by a coupling reaction with an oxidant of a developing agent is particularly suitable for the S / N ratio (maximum density / fog ratio) of the obtained color image and storage. It is preferable in terms of properties and is also excellent in that it does not require a base or its precursor.

Examples of dye-donor substances for forming a cyan dye image by a coupling method are JP-A-60-179739 and JP-A-61-61.
The compound described in No. 158 is excellent in terms of the S / N ratio of a color image, but the cyan dye formed by using the compound described in these specifications can be treated with heat and / or coexistence during heat development. It tends to be decomposed by the reducing agent to reduce the apparent dye formation efficiency, and stains may be generated due to the decomposed product, and improvement of these problems has been demanded.

[Object of the Invention] Therefore, the present invention is intended to solve the problems of the above-described cyan dye-donor substances.

That is, an object of the present invention is to provide a photothermographic material containing a novel cyan dye-donating substance.

Another object of the present invention is to provide a photothermographic material capable of obtaining a clear image.

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

Still another object of the present invention is to provide a photothermographic material containing a cyan dye-donor which can provide a color image with high density and less fog.

[Structure of the Invention] The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, thermal development having a photographic constituent layer containing at least a photosensitive silver halide, a reducing agent, a dye-donor and a binder on a support. In the color light-sensitive material, the above object of the present invention can be achieved by a photothermographic material in which at least one of the dye-donor substances is a compound represented by the following general formula (1) or a polymer derived from the compound. I found it.

General formula (1) (In the formula, R ¹ represents a monovalent organic group, and R ² has ² carbon atoms.
To 6 alkyl groups, R ³ represents a hydrogen atom or an organic group, X represents a hydrogen atom or a halogen atom, Y represents an oxygen atom or a sulfur atom, M represents a hydrogen atom, an NH ₄ group or Represents a monovalent metal atom. [Specific Structure of the Present Invention] In the photothermographic material of the present invention, the formed dye may be transferred to form a color image on the image receiving element (transfer type), or without transfer. A color image may be formed (non-transfer type) in the photographic constituent layer in which the dye-donating substance of the present invention is present, but the transfer type is used because it is easy to separate from the silver image formed during thermal development. Is more preferable.

In the photothermographic material of the present invention, at least one of the dye-donor substances is a compound represented by the general formula (1) or a polymer derived from the compound. In the present specification, these are collectively referred to as It is called the cyan dye-donor of the present invention.

The cyan dye-donor material of the invention is described below.

In the above general formula [1], R ¹ represents a monovalent organic group, preferably an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkylamino group, a dialkylamino group or an arylamino group. Represents Further, these groups are further alkoxy groups, cyano groups,
Nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, sulfo group, carboxy group, acylamino group, alkylamino group, alkylsulfonylamino group,
One or two of substituents such as arylsulfonylamino group, sulfamoylamino group, imide group and halogen atom
It may be replaced by one or more.

When the photothermographic material of the present invention is the above-mentioned transfer type, R ¹
The total number of carbon atoms of the organic group represented by is preferably
It is 12 or less (more preferably 8 or less). When the photothermographic material is of a non-transfer type, the organic group represented by R ¹ is an organic ballast having a molecular size and shape capable of being immobilized when the compound represented by the general formula (1) is thermally developed. It is desirable that it is a group. A preferred organic ballast group is an organic group having a total of 12 or more carbon atoms, and further having an organic group having a total of 12 or more carbon atoms having at least one hydrophilic group such as a sulfo group or a carboxy group as a substituent. preferable.

Yet another particularly preferred organic ballast group includes polymer residues.

When the organic ballast group is a polymer residue, the cyan dye-donating substance of the present invention is a polymer having a repeating unit derived from a monomer represented by the following general formula (2).

General formula (2) In the formula, R ² , R ³ , X, Y and M are R ^{2 of} the general formula (1),
It has the same meaning as R ³ , X, Y and M, and Q ₁ represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

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

In the general formula (1), R ² is an alkyl group having 2 to 6 carbon atoms (for example, ethyl group, n-propyl group, i-propyl group, n-butyl group, tert-butyl group, n-pentyl group). , N-hexyl group), with an ethyl group being particularly preferred.

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

In the general formula (1), R ³ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group. Can be mentioned. Further, these groups further include, for example, an alkoxy group, an acylamino group, an alkylamino group, a sulfamoyl group, a carbamoyl group, a carboxy group, an alkylsulfonylamino group, an arylsulfonylamino group, a sulfamoylamino group,
It may be substituted with one or more substituents such as an imide group and a halogen atom.

When the photothermographic material of the present invention is the above-mentioned transfer type, R ₃
The organic group represented by is preferably a ballast group having a molecular size and shape capable of immobilizing the compound represented by the general formula (1) during thermal development. The preferred ballast group is an organic group having a total of 12 or more carbon atoms, and more preferably a total of 12 or more carbon atoms having at least one hydrophilic group such as a sulfo group or a carboxy group as a substituent. It is an organic group.

Yet another particularly preferred ballast group is a polymer residue.

When the ballast group is a polymer residue, the cyan dye-donating substance of the present invention is a polymer having a repeating unit derived from a monomer represented by the following general formula (3), and is most suitable as the cyan dye-donating substance of the present invention. preferable.

General formula (3) In the formula, R ¹ , R ² , X, Y and M are R ¹ , R ² in the general formula (1),
It has the same meaning as X, Y and M, and Q ₂ represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

In the above general formulas (2) and (3), Q ₁ and Q ₂ each represent an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and are preferably represented by the following general formula (4).

General formula (4) In the formula, Z ₁ and Z ₂ represent a divalent hydrocarbon group, and J ₁ and J ₂
Represents a divalent linking group, R ⁴ represents a hydrogen atom or an alkyl group, and m ₁ , m ₂ , n ₁ and n ₂ each represent an integer of 0 or 1.

In the general formula (4), Z ₁ and Z ₂ represent a divalent hydrocarbon group, and the divalent hydrocarbon group is, for example, an alkylene group (eg, methylene group, ethylene group, propylene group, etc.). , Arylene group (eg, phenylene group), aralkylene group (eg, phenylmethylene group, etc.), alkylenearylene group (eg, methylenephenylene group, ethylenephenylene group, etc.), arylenealkylene group (eg, phenylenemethylene group, phenyleneethylene group) Groups, etc.) and the like.

In the general formula (4), J ₁ and J ₂ each represent a divalent linking group. Examples of the divalent linking group include —NHCO—,
_{-CONH -, - NHSO 2 -,} - SO 2 NH -, - NHCOCH 2 -, CH 2 CO
NH -, - O -, - S -, - CO -, - SO 2 -, - COO -, -
OCO- and the like can be mentioned.

The divalent linking group for J ₁ and J ₂ is preferably —NHCO—, —NH
COCH ₂ − or −OCO−.

In the general formula (4), R ⁴ represents a hydrogen atom or an alkyl group, and the alkyl group is an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-butyl group). ) Is preferable, and a methyl group is particularly preferable.

The polymer having a repeating unit derived from the monomer represented by the general formula (2) or (3) of the present invention is only one kind of the monomer represented by the general formula (2) or (3). May be a so-called homopolymer of the repeating unit consisting of or a copolymer in which two or more kinds of the monomers represented by the general formula (2) or (3) are combined,
Further, it may be a copolymer composed of at least one other comonomer having a copolymerizable ethylenically unsaturated group.

Examples of the comonomer having an ethylenically unsaturated group capable of forming a copolymer with the monomer represented by the general formula (1) or (2) of the present invention include acrylic acid esters, methacrylic acid esters, vinyl esters, olefins. , Styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters , Unsaturated nitriles, polyfunctional monomers, various unsaturated acids and the like.

More specific examples of these comonomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-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-acetoxyethyl acrylate, dimethylaminoethyl acrylate , Benzyl acrylate,
Methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3
-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 mol number n = 9) 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-
2-ethoxyethyl acrylate etc. are mentioned.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl Methacrylate, 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-acetoxyethyl methacrylate, 2 -Acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-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 (additional mol number n = 6) ),
Examples thereof include allyl methacrylate, methacrylic acid dimethylaminoethylmethyl chloride salt and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate and the like. Can be mentioned.

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

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, promstyrene, and vinylbenzoic acid methyl ester. Is mentioned.

Examples of crotonic acid esters include butyl crotonic acid, hexyl crotonic acid, and the like.

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

Examples of other comonomers include:

Acrylamides, for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethyl. Acrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl)
Acrylamide, etc .; Methacrylamides, for example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-
Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, 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 .; vinyl ketone acid, for example, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc .; vinyl heterocyclic compound, for example, vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl. Triazole, N-vinylpyrrolidone, etc .; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc .; Unsaturated nitriles, such as acetic acid Rironitoriru and methacrylonitrile; polyfunctional monomers, such as divinyl benzene, methylene bisacrylamide, ethylene glycol dimethacrylate.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc .; Monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate, malein Acid monobutyl etc .; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid; methacryloyloxyalkyl Sulfonic acids such as methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid and the like; Krill amide alkylsulfonic acid,
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid and the like; methacrylamide alkylsulfonic acid, for example, 2-methacrylamide-2. -Methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc .; acryloyloxyalkyl phosphate,
For example, acryloyloxyethyl phosphate, 3-
Acryloyloxypropyl-2-phosphate etc .;
Methacryloyloxyalkyl phosphates, for example
Methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate and the like; 3-allyloxy-2-hydroxypropane sulfonate sodium having two hydrophilic groups and the like can be mentioned. These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions. Still other comonomers include U.S. Patent Nos. 3,459,790 and 3,438,708.
Issue No. 3,554,987, No. 4,215,195, No. 4,247,67
The cross-linkable monomers described in JP-A No. 3 and JP-A-57-205735, etc. can be used. Specific examples of such a crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide and N- {2- (2-
Acetoacetoxy ethoxy) ethyl} acrylamide etc. can be mentioned.

When a copolymer is formed from the monomer represented by the general formula (2) or (3) of the present invention and the comonomer, the monomer represented by the general formula (2) or (3) is preferable. When the repeating unit consisting of 10 to 90% by weight of the total polymer is contained in a weight ratio, more preferably
This is the case when 30 to 70% by weight is contained.

Generally, the polymer coupler is polymerized by an emulsion polymerization method or a solution polymerization method and has a dye-donating agent of the present invention having a repeating unit derived from the monomer represented by the general formula (2) or (3) of the present invention. Material polymers can also be polymerized in a similar manner. Regarding the emulsion polymerization method, the method described in U.S. Pat.Nos. 4,080,211 and 3,370,952, and the method described in U.S. Pat.No. 3,451,820 for dispersing the lipophilic polymer in the form of a latex in an aqueous gelatin solution are used. be able to.

These methods can also be applied to the formation of homopolymers and copolymers, in the latter case the comonomers should be liquid comonomers and, in the case of emulsion polymerization, also act normally as a solvent for the fixed monomers. .

Examples of the emulsifier used in the emulsion polymerization method include a surfactant, a polymeric protective colloid, and a copolymer emulsifier. Examples of the surfactant include anionic activators, nonionic activators, cationic activators and amphoteric activators known in the art.

Examples of anion activators include soaps, sodium dodecylbenzene sulfonate, sodium lauryl sulfate,
Examples thereof include sodium dioctyl sulfosuccinate and sulfates of nonionic activators.

Examples of the nonionic activator include polyoxyethylene nonylphenyl ether, polyoxyethylene stearic acid ester, polyoxyethylene sorbitan monolauric acid ester, polyoxyethylene-polyoxypropylene block copolymer and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines.

Examples of amphoteric activators include dimethylalkyl betaines, alkylglycines and the like. Examples of the polymer protective colloid include polyvinyl alcohol and hydroxyethyl cellulose. These protective colloids may be used alone as an emulsifying agent, or may be used in combination with other surfactants. The types of these activators and their effects are described in the Belgische Chemische Indurie.
strie, 28, 16-20 (1963).

To disperse the lipophilic polymer synthesized by the solution polymerization method in the aqueous gelatin solution in the form of latex, first dissolve the lipophilic polymer in an organic solvent, and then add it to the aqueous gelatin solution with the aid of a dispersant. Then, it is dispersed into a latex by ultrasonic waves, a colloid mill or the like. A method of dispersing a lipophilic polymer in aqueous gelatin in the form of a latex is described in US Pat. No. 3,451,820.
Examples of the organic solvent that dissolves the lipophilic polymer include esters such as methyl acetate, ethyl acetate and propyl acetate.
Alcohols, ketones, halogenated hydrocarbons, ethers and the like can be used. Further, these organic solvents can be used alone or in combination of two or more kinds.

In producing the dye-donor polymer according to the present invention, the solvent used for polymerization is preferably a good solvent for the monomer and the dye-donor polymer to be produced, and has low reactivity with the polymerization initiator. Specifically, water, toluene, alcohol (for example, methanol, ethanol, iso-propanol, tert-butanol, etc.), acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, dimethylformamide, dimethyl sulfoxide,
Examples include acetonitrile and methylene chloride,
You may use these solvent individually or in mixture of 2 or more types.

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 the solution polymerization method of the dye-donating polymer of the present invention include the following.

As the water-soluble polymerization initiator, for example, potassium persulfate, ammonium persulfate, persulfates such as sodium persulfate,
4,4'-azobis-4-cyanovalerate sodium, 2,2 '
-A water-soluble azo compound such as azobis (2-amidinopropane) hydrochloride and hydrogen peroxide can be used.

Examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile) and 2,2'-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexanone-1-carbonitrile), 2,2'-azobisisocyanobutyric acid, 2,2 '
-Dimethyl azobisisobutyrate, 1,1'-azobis (cyclohexanone-1-carbonitrile), azo compounds such as 4,4'-azobis-4-cyanovaleric acid, benzoyl peroxide, lauryl peroxide, chlorobenzyl peroxide, Examples thereof include peroxides such as diisopropyl peroxydyl carbonate and di-t-butyl peroxide. Of these, the preferred one is
Examples thereof include benzoyl peroxide, chlorobenzyl peroxide, lauryl peroxide and the like.

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

Furthermore, a polymerization method other than the above-mentioned polymerization method, for example, a suspension polymerization method or a bulk polymerization method can be applied. That is,
In the present invention, a dye-donating homopolymer of the monomer represented by the general formula (2) or (3) of the present invention,
It includes all copolymers which are a combination of two or more kinds of the monomers or copolymers which are a copolymerization component of the monomers and at least one other polymerizable comonomer,
The synthesis process is not limited.

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

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

Next, specific examples of the cyan dye-donating substance monomer represented by the general formula (3) of the present invention are shown in Table 3 below.

Specific examples of the cyan dye-donor polymer of the present invention are shown in Table 4 below.

The specific method for synthesizing the cyan dye-donating substance of the present invention is shown below.

Synthesis Example Intermediate (1): Synthesis of 2-ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol 28.5 g of 2-amino-4,6-dichloro-5-ethyl-phenol hydrochloride, 200 ml of acetonitrile and 50 pyridine
It was dissolved in a solution consisting of 1 ml and 25 ml of acetyl chloride was added dropwise to this solution. After refluxing for 1 hour (solid deposition), 30
It was poured into 0 ml of water and the solid was filtered off. This solid was added to a water / methanol solution containing 10 g of sodium hydroxide and stirred for a while.

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

The crystals were added to cold acetonitrile and stirred for a while, then separated, washed with cold acetonitrile and dried,
40 g of crude crystals of 2-acetylamino-4,6-cygrol-5-ethylphenol were obtained.

39.3 g of this crude crystal was added to 400 ml of acetic acid, dispersed, and cooled to 10 ° C. with stirring. Sodium nitrite in this solution 1
70 ml of water containing 4.5 g was added dropwise at 10 ° C or lower, and at 20 ° C 1
Stir for hours. This reaction solution was added to 1500 ml of water, and the precipitated yellow crystals were filtered off, washed with water and dried to give 29 g.
To obtain crude crystals of 2-acetylamino-5-ethyl-6-chloroquinone.

The total amount of the crude crystals was dissolved in 400 ml of an ethanol-tetrahydrofuran solution, and hydrogen-reduced using carbon-palladium as a catalyst. The reaction solution was filtered, concentrated, and added to 300 ml of acetone. In this acetone solution, under a nitrogen stream, potassium carbonate 30
g and 16.2 ml of benzyl bromide, and refluxed for 8 hours with stirring. The reaction solution was filtered and concentrated, and the precipitated solid was washed with water and recrystallized from acetonitrile to obtain 22.3 g of 2-ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol.

Intermediate (2): 2-Ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol (32 g) and ethyl α-bromoacetate (18.4 g) were dissolved in 600 ml of acetone, and 60 g of potassium carbonate was further added, followed by stirring. While refluxing for 6 hours. The reaction solution was filtered and concentrated, then dissolved in an ethanol-tetrahydrofuran solution, and hydrogen-reduced using carbon-palladium as a catalyst. After filtering and concentrating the reaction solution,
Water 100 ml containing 7.5 g of sodium hydroxide and ethanol 200
It was added to the solution consisting of 10 ml and stirred for a while and then left overnight. Next, the reaction solution is poured into dilute hydrochloric acid to be neutralized and deposited 2.
Crude crystals of -ethyl-3-chloro-4-hydroxy-5-acetylaminophenoxyacetic acid were obtained. The crude crystals were added to a mixed solution of 300 ml of ethanol and 30 ml of concentrated sulfuric acid, refluxed, cooled, and the precipitated crystals were filtered off to give 14.2 g of hydrochloride of 2-ethyl-3-chloro-4-hydroxy-5-aminophenoxyacetic acid. Got

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

Synthesis of Exemplified Compound C-5 2-Ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol 6.4 g and ethyl α-bromopalmitate 8.0 g were dissolved in acetone 150 ml, and potassium carbonate 8 g was added, Refluxed for 5 hours with stirring. The reaction solution was filtered, concentrated, added to 200 ml of ethanol, hydrogen-reduced with carbon-palladium as a catalyst, filtered, and added with 50 ml of water containing 2 g of sodium hydroxide, and stirred for 5 hours. The reaction solution was poured into 200 ml of diluted hydrochloric acid and the precipitated solid was filtered off and recrystallized from acetonitrile to obtain 8.8 g of the desired product.

Synthesis of Exemplified Monomer C-16 Using 2-ethyl-3-chloro-4-hydroxy-5-aminophenoxyacetic acid hydrochloride, methacrylic acid was used in place of stearic acid chloride, and the other synthetic examples ( The target product was obtained in the same manner as in 3).

Synthesis of Exemplified Monomer C-23 2-Ethyl-3-chloro-4-benzyloxy-5-acetylaminophenol 12.8 g and α-bromo-γ- (p
-Nitrophenyl) -ethyl butyrate 13.9 g acetone 300 ml
, Potassium carbonate (16 g) was added, and the mixture was refluxed for 8 hours.
The reaction solution was filtered and concentrated, 250 ml of ethanol was added, the obtained brown solid was filtered off, and this solid was recrystallized from acetonitrile to obtain white crystals. The whole amount of this crystal was dissolved in ethanol and hydrogen-reduced using carbon-palladium as a catalyst. After the reaction is complete, the reaction solution is filtered, the filtrate is concentrated to 100 ml, and 50 ml of water containing 3.5 g of sodium hydroxide is added,
After stirring at room temperature for 5 hours, the mixture was neutralized with diluted sulfuric acid and precipitated to give a white solid {α-[(2-ethyl-3-chloro-4-hydroxy-5-acetylaminophenoxy] -γ- (p-aminophenyl). Butyric acid} was filtered off.

81.3 g of this intermediate was added to 80 ml of acetonitrile and 15 ml of pyridine.
The mixture was dissolved in a mixed solution of and, cooled to 15 ° C. or lower, and a solution of 2.3 ml of methacrylic acid chloride in acetonitrile (10 ml) was added dropwise, followed by stirring at room temperature for 2 hours. The reaction solution was poured into water, the precipitated solid was filtered off, and recrystallized from acetonitrile to obtain 7.6 g of the desired product. The structures of the above intermediates and synthetic example compounds were determined by NMR and FD-mass spectroscopy. confirmed.

Synthesis of Exemplified Compound PC-1 Dissolve 15 g of Exemplified Monomer C-16 obtained above and 15 g of n-butyl acrylate in 150 ml of dioxane,
The mixture was heated to 80 to 81 ° C. while introducing nitrogen gas, and while maintaining this temperature, 600 mg of 2,2′-azobisisobutyronitrile was added and the reaction was carried out for 4 hours. After completion of the reaction, the reaction solution was poured into 1 ice water, and the precipitated solid was separated by filtration and dried. This solid was redissolved in 100 ml of dioxane and 1 part of dioxane solution was added.
Was poured into ice water, and the solid precipitated again was separated by filtration and dried to obtain the target polymer PC-1: 26 g.

Synthesis of Exemplified Compound PC-6: 15 g of Exemplified Monomer C-23 obtained above and 10 g of n-butyl acrylate were dissolved in 125 ml of dimethylformamide and heated to 84 to 85 ° C. while introducing nitrogen gas, Maintaining this temperature, 2,2'-azobisisobutyronitrile 2
50 mg was added and the reaction was carried out for 2 hours. Further, 250 mg of 2,2'-azobisisobutyronitrile was added and the reaction was carried out for 2 hours.
After completion of the reaction, the reaction solution was poured into 1 of ice water, and the precipitated solid was separated by filtration and dried. This solid is dimethylformamide
It was redissolved in 100 ml, and the dimethylformamide solution was added to 1 of ice water, and the precipitated solid was filtered off and dried to obtain the target polymer PC-6: 23 g.

These dye-donor substances may be used alone or in combination of two or more. When two or more dye-providing substances are used, two or more dye-providing substances represented by the general formula (1) of the present invention may be used. For example, they are described in JP-A-60-179739 and JP-A-61-61158. You may use together with cyan dye donors other than the cyan dye donor of this invention, such as a cyan dye donor.

The amount used is not limited, depending on the type of the dye-donating substance, a single use or a combination use of two or more kinds, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or two or more kinds of multilayers. may be determined according but, for example the amount used 1 m ² per
0.005 g to 50 g, preferably 0.1 g to 10 g can be used.

The method for incorporating the dye-donor substance used in the present invention into the photographic constituent layer of the photothermographic material is arbitrary and includes, for example, a low-boiling point solvent (methanol, ethanol, ethyl acetate, etc.) or a high-boiling point solvent (dibutyl phthalate, dioctyl phthalate, tritium). Cresyl phosphate, etc.) and then ultrasonically dispersed or dissolved in an alkaline aqueous solution (eg, 10% sodium hydroxide solution), and then neutralized with a mineral acid (eg, hydrochloric acid or nitric acid). It can be used after being used or after being dispersed with a suitable polymer aqueous solution (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill.

The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples thereof include silver chloroiodobromide. The photosensitive silver halide is
It can be prepared by any method such as a single jet method and a double jet method in the field of photographic technology. For example, by applying the method described in JP-A-54-48521, pA
Monodisperse silver halide grains can be obtained by the double jet method while keeping g constant. At that time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of the addition rate, pH, pAg, temperature and the like. According to a further preferred embodiment, a silver halide emulsion having silver halide grains having a shell can be used. The silver halide grains having a shell can be obtained by using the above-described method and using a silver halide grain having good monodispersity as a core and sequentially growing a shell on the core.

The monodisperse silver halide emulsion referred to in the present invention means one in which the variation in the size of silver halide grains contained in the emulsion has a grain size distribution of a certain ratio or less 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 grains in which the photosensitive silver halide grains have a uniform grain morphology and a small variation in grain size, a standard deviation is easily obtained, Relational expression When the breadth of the distribution is defined by, the breadth of the silver halide grains used in the present invention is preferably 15% or less, more preferably 10% or less. .

In addition, for example, JP-A-58-111933, JP-A-58-111934 and JP-A-58-111934.
-108526, Research Disclosure 22534, etc., having two parallel crystal faces,
And, each of these crystal faces is a grain having a larger area than the other single crystal of this grain, and its aspect ratio, that is, the ratio of the diameter of the grain to the thickness of the tabular silver halide grain of 5: 1 or more, It is also possible to use a silver halide emulsion consisting of

Further, in the present invention, a silver halide emulsion containing an internal latent image type silver halide grain whose surface is not previously fogged can be used. For internal latent image type silver halide in which the surface is not previously fogged, for example, U.S. Pat.
592,250, 3,206,313, 3,317,322, 3,511,6
No. 62, No. 3,447,927, No. 3,761,266, No. 3,703,584
No. 3,736,140, etc., the silver halide has a higher sensitivity inside the grain than at the surface of the grain. The method for producing a silver halide emulsion containing these internal latent image type silver halides is as described in the above-mentioned patent, for example, by first preparing AgCl grains and then adding bromide or a mixture thereof with a small amount of iodide. Addition for halide exchange, or coating of chemically sensitized silver halide central nucleus with unsensitized silver halide, or chemical sensitization with chemically sensitized coarse grain emulsion Alternatively, many methods such as a method of mixing fine grain emulsions not chemically sensitized and depositing the fine grain emulsion on the coarse grain emulsion are known. In addition, U.S. Pat.
No. 3,447,927 and No. 3,531,291, silver halide emulsions having silver halide grains containing polyvalent metal ions, or halogenated compounds containing a dopant described in U.S. Pat.No. 3,761,276. A silver halide emulsion in which the grain surfaces of silver grains are weakly chemically sensitized, or a silver halide emulsion comprising grains having a laminated structure described in JP-A Nos. 50-8524 and 50-38525, and other special features. Examples thereof include silver halide emulsions described in JP-A-52-156614 and JP-A-55-127549.

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

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

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

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

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

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

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

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

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

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

In the photothermographic 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 salt used in the photothermographic material of the present invention include JP-B-43-4921, JP-A-49-52626, and JP-A-52-141222.
No. 53-36224, No. 53-37610, etc., and U.S. Pat.Nos. 3,330,633, 3,794,496, and 4,10
Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocycle such as those described in each specification such as 5,451, such as silver laurate, silver myristate, silver palmitate, and stearin. Aromatic carboxylic acid silver, such as silver acid salt, silver arachidonic acid, silver behenate, α- (1-phenyltetrazolethio) acetic acid silver, for example, silver benzoate, silver phthalate, etc. 12700, 45-18416
No. 45-22185, JP-A-52-137321, JP-A-58-1186
No. 38, No. 58-118639, U.S. Pat. No. 4,123,274 and the like, there are silver salts of imino groups.

Examples of the silver salt of an imino group include benztriazole silver. The benztriazole silver may be substituted or unsubstituted. Representative examples of substituted benztriazole silver include, for example, alkyl-substituted benztriazole silver (preferably one substituted with an alkyl group having C ₂₂ or less, more preferably C ₄ or less,
For example, methylbenztriazole silver, ethylbenztriazole silver, n-octylbenztriazole silver, etc.),
Alkylamidobenztriazole silver (preferably C ₂₂
Those substituted with the following alkylamide groups, for example, acetamide benztriazole silver, propionamide benztriazole silver, iso-butylamide benztriazole silver, lauryl amide benztriazole silver, etc.),
Alkylsulfamoylbenztriazole silver (preferably substituted with an alkylsulfamoyl group having a C ₂₂ or less, for example, 4- (N, N-diethylsulfamoyl)
Benztriazole silver, 4- (N-propylsulfamoyl) benztriazole silver, 4- (N-octylsulfamoyl) benztriazole, 4- (N-decylsulfamoyl) benztriazole silver, 5- (N- Octylsulfamoyl) benztriazole silver, etc.), silver salts of halogen-substituted benztriazoles (eg 5-chlorobenztriazole silver, 5-bromobenztriazole silver etc.), alkoxybenztriazole silver (preferably C ₂₂ or less alkoxy groups) , More preferably those substituted with an alkoxy group having C ₄ or less, for example, 5-methoxybenztriazole silver, 5-ethoxybenztriazole silver, etc.), 5-nitrobenztriazole silver, 5-aminobenztriazole silver, 4-hydroxy. Benztriazole silver, 5-carbo Examples include xybenztriazole silver, 4-sulfobenztriazole silver, 5-sulfobenztriazole silver, and the like.

Examples of other silver salts having an imino group include imidazole silver, benzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazole silver, 1,2,4
-Triazole silver, 1H-tetrazole silver, 3-amino-
Silver salts of other mercapto compounds such as silver 5-benzylthio-1,2,4-triazole, silver saccharin, silver phthalazinone, and silver phthalimide, for example, silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, and silver 2-mercaptobenzothiazole. , 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,4
-Triazole silver, 4-hydroxy-6-methyl-1,3,
3a, 7-Tetrazaindene silver, 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver and the like can be mentioned.

In addition, a silver complex compound having a stability constant of 4.5-10.0 as described in JP-A-52-31728, a silver salt of imidazoline thione as described in U.S. Pat. No. 4,168,980, and the like are used.

Among the above organic silver salts, silver salts of imino groups are preferable,
Particularly, a silver salt of a benzotriazole derivative, more preferably 5-methylbenzotriazole and its derivative, sulfobenzotriazole and its derivative, N-alkylsulfamoylbenzotriazole and its derivative are preferable.

The organic silver salt used in the present invention may be used alone or in combination of two or more kinds. The silver salt may be prepared in a suitable binder and used as it is without isolation, or the isolated product may be dispersed in the binder by a suitable means before use. Examples of the dispersing method include, but are not limited to, a ball mill, a sand mill, a colloid mill and a vibration mill.

Further, the method for preparing the organic silver salt is generally a method in which silver nitrate and a raw material organic compound are dissolved and mixed in water or an organic solvent, but a binder may be added if necessary, or sodium hydroxide or the like may be added. It is also effective to add an alkali to accelerate the dissolution of the organic compound or to use an ammoniacal silver nitrate solution.

The amount of the organic silver salt used is usually preferably 0.01 to 500 mol, and more preferably 0.1 to 1 mol, per 1 mol of the photosensitive silver halide.
~ 100 mol. More preferably, it is 0.3 to 30 mol.

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.

Dye-donor substances used in the photothermographic material of the present invention, for example, JP-A-57-186744, 58-79247,
58-149046, 58-149047, 59-124339, 59-
No. 181345, No. 60-2950 and the like, by coupling with an oxidant of a reducing agent as disclosed in, a dye-donating substance that releases or forms a diffusible dye,
Examples of the reducing agent used in the present invention include US Pat.
No. 3,531,286, No. 3,761,270, No. 3,764,328, each specification, RD No. 12146, No. 15108, No. 15127 and p-phenylenediamine system described in JP-A-56-27132 and A p-aminophenol-based developing agent, a phosphoramidophenol-based developing agent, a sulfonamidephenol-based developing agent, a sulfonamideaniline-based developing agent, and a hydrazone-based color developing agent can be used. Also, U.S. Pat.Nos. 3,342,599 and 3,719,492, JP
The color developing agent precursors described in JP-A-53-135628 and JP-A-57-79035 can also be used advantageously.

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

General formula (5) In the formula, R ¹ and R ² represent a hydrogen atom or an optionally substituted alkyl group having 1 to 30 carbon atoms (preferably 1 to 4), and R ¹ and R ² are ring-closed. A heterocycle may be formed. R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamide group, a sulfonamide group, an alkylsulfonamide group or the number of carbon atoms which may have a substituent. It represents an alkyl group of 1 to 30 (preferably 1 to 4), and R ³ and R ¹ and R ⁵ and R ² may each be ring-closed to form a heterocycle. M represents a compound containing an alkali metal atom, an ammonium group, a nitrogen-containing organic base or a quaternary nitrogen atom.

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

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

Next, preferred specific examples of the ring former represented by the general formula (5) are shown below.

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

Furthermore, even if two or more reducing agents are used at the same time, it is also possible to use the black-and-white developing agents described below together for the purpose of improving the developability.

Further, the dye-donor substances used in the present invention include JP-A-57-179840, JP-A-58-58543, JP-A-59-152440, and JP-A-59-1.
In the case of compounds that release dyes by oxidation as shown in 54445, compounds that lose dye releasing ability by oxidation, compounds that release dyes by reduction (or simply obtain only silver image) In the case), a developing agent as described below can also be used.

For example, phenols (for example, p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamide phenols [for example, 4-benzene Sulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4- (p-toluenesulfonamido) phenol, etc.], or polyhydroxybenzenes (eg, Hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc., naphthols (for example, α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphtho). Le etc.), hydroxy binaphthyls and methylene bis naphthols [e.g.
1,1'-dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,
6'-dinitro-2,2'-dihydroxy-1,1'-binaphthyl, 4,4'-dimethoxy-1,1'-dihydroxy-2,
2′-binaphthyl, bis (2-hydroxy-1-naphthyl) methane, etc.], methylenebisphenols [eg 1,
1-bis (2-hydroxy-3,5-dimethylphenyl)-
3,5,5-trimethylhexane, 1,1-bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane,
1,1-bis (2-hydroxy-3,5-di-tert-butylphenyl) methane, 2,6-methylenebis (2-hydroxy-3-tert-butyl-5-methylphenyl) -4-methylphenol, α-phenyl-α, α-bis (2-hydroxy-3-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 and the like], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones and paraphenylenediamines.

These developing agents may be used alone or in combination of two or more.

The amount of the reducing agent used in the photothermographic material of the invention depends on the type of the photosensitive silver halide used, the type of the organic acid silver salt, the type of other additives, etc. Is 0.01 to 15 per mol of photosensitive silver halide.
The amount is in the range of 00 mol, preferably 0.1 to 200 mol.

As the binder used in the photothermographic material of the present invention, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, phthalated gelatin, etc. One or a combination of two or more molecular substances can be used. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binders described in JP-A-59-229556.

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

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

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

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

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

The amount of the binder used is usually 0.05 g to 50 g, and preferably 0.1 g to 10 g per 1 m ^{2 of the} support.

Further, the binder is 0.1 to 10 g per 1 g of the dye-donor substance.
It is preferably used, and more preferably 0.25 to 4 g.

The support used in the photothermographic material of the present invention includes
For example, polyethylene film, cellulose acetate film and polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, photographic base paper, printing paper, paper for baryta paper and resin-coated paper, and electronic materials on these supports. Examples thereof include a support coated with and cured by a linear curable resin composition.

When the photothermographic material of the present invention, and further when the photosensitive material is a transfer type and an image receiving member is used, it is preferable to add various thermal solvents to the photothermographic material 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. For these compounds, for example, U.S. Patent Nos. 3,347,675 and 3,667,959.
Issue, Research Disclosure No.17643 (XII),
Organic compounds having a polarity as described in JP-A-59-229556, Japanese Patent Application No. 59-47787 and the like can be mentioned. Particularly useful compounds in the present invention include, for example, urea derivatives (for example, dimethylurea and diethyl). Urea, phenylurea, etc.),
Amide derivatives (eg, acetamide, benzamide, etc.), polyhydric alcohols (eg, 1,5-pentanediol, 1,6-pentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or polyethylene Examples thereof include glycols.

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

The water-insoluble solid thermal solvent is a solid at room temperature, but at a high temperature (60 ° C or higher, preferably 100 ° C or higher, particularly preferably 130 ° C or higher).
It is a compound that turns into a liquid at temperatures above ℃ and below 250 ℃, and has an inorganic / organic ratio ("organic conceptual diagram" Yoshio Koda, Sankyo Publishing Co., Ltd., 1984) of 0.5 to 3.0, preferably 0.7 to 2.5, especially It is preferably a compound in the range of 1.0 to 2.0 and has a solubility in water at room temperature of less than 1.

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

Many of the compounds used as the water-insoluble solid hot solvent are commercially available and can be easily synthesized by those skilled in the art.

The addition method of the water-insoluble hot solvent is not particularly limited, but a method of pulverizing and dispersing with a ball mill, a sand mill or the like,
There are a method of dissolving in a suitable solvent and adding, a method of dissolving in a high boiling point solvent and adding as an oil-in-water dispersion, and the like.
It is preferable to pulverize and disperse with a ball mill, a sand mill or the like, and add while maintaining the shape of the solid particles.

As the layer to which the water-insoluble solid thermal solvent is added, it is added so as to obtain the respective effects of a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving layer of an image receiving member and the like.

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

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

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

For example, acetamide described in U.S. Pat.No. 3,438,776, melt formers such as succinimide, U.S. Pat.
No. 477, compounds such as polyalkylene glycols described in JP-A-51-19525, -C described in U.S. Pat.
_{O -, - SO 2 -,} - SO- melting point of the lactone or the like 20 having a group
There are non-aqueous polar organic compounds having a temperature of ℃ or more.

Further, benzophenone derivatives described in JP-A-49-115540, phenol derivatives described in JP-A-53-24829 and JP-A-53-60223, carboxylic acids described in JP-A-58-118640, and The polyhydric alcohols described in JP-A-58-198038 and the sulfamoylamide compounds described in JP-A-59-84236 are also included.

What is known as a toning agent in the photothermographic material may be added to the photothermographic material of the present invention as a development accelerator. As the color tone adjusting agent, for example, JP-A-46-4928 is used.
No. 46, No. 46-6077, No. 49-5019, No. 49-5020, No. 49-91
No. 215, No. 49-107727, No. 50-2524, No. 50-67132,
50-67641, 50-114217, 52-33722, 52-99
813, 53-1020, 53-55115, 53-76020, and
53-125014, 54-156523, 54-156524, 54-15
6525, 54-156526, 55-4060, 55-4061,
55-32015, etc. and West German Patent No. 2,140,406
No. 2,141,063, No. 2,220,618, U.S. Pat.
7,612, 3,782,941, 4,201,582 and JP-A-57-207244, 57-207245, 58-189628, 5
Compounds described in each specification such as 8-193541, 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, mercaptotriazole, dimercaptotetrazapentalene , Aminomercaptotriazole, acylaminomercaptotriazoles, phthalic acid, naphthalic acid, phthalamic acid, etc., and a mixture of one or more of these with an imidazole compound, or an acid or acid anhydride such as phthalic acid, naphthalic acid, etc. Examples thereof include a mixture of at least one of the above compounds and a phthalazine compound, and further, a combination of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, or the like.

Examples of the antifoggant include higher aliphatic compounds (for example, behenic acid, stearic acid, etc.) described in U.S. Pat. No. 3,645,739, mercuric salts described in JP-B-47-11113, JP-A-51-47419. N-halogen compounds (for example, N
-Halogenoacetamide, N-halogenosuccinimide, etc.), mercapto compound-releasing compounds described in U.S. Pat. Acid, etc.), carboxylic acid lithium salts described in JP-A-51-47419 (for example, lithium laurate), British Patent No. 1,455,271,
Oxidizing agents described in JP-A-50-101,019 (for example, perchlorates, inorganic peroxides, persulfates, etc.), sulfinic acids or thiosulfonic acids described in JP-A-53-19825, 51-322
2-thiouracils described in No. 3, sulfur alone described in No. 51-26019, No. 51-42529, No. 51-81124, No. 55-931
Disulfide and polysulfide compounds described in No. 49, rosins or diterpenes described in No. 51-57435 (for example, abietic acid, pimaric acid, etc.), free carboxyl group or sulfonic acid group described in No. 51-104338 Polymeric acid, thiazoline thione described in U.S. Pat. No. 4,138,265, JP-A-54-51821, U.S. Pat.
1,2,4-triazole or 5-mercapto-1,2,4-triazole described in No. 9, thiosulfinic acid esters described in No. 55-140833, 1,2 described in No. 55-142331 ,
3,4-thiatriazoles, 59-46641, 59-57233
No. 59-57234, and dihalogen compounds or trihalogen compounds, and the thiol compounds described in No. 59-111636.

Other antifoggants include hydroquinone derivatives described in Japanese Patent Application No. 59-56506 (for example, di-t-octylhydroquinone, dodecanylhydroquinone, etc.) and hydroquinone derivatives described in Japanese Patent Application No. 59-66380. And a benzotriazole derivative (for example, 4-sulfobenzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used in combination.

As another particularly preferable antifoggant, Japanese Patent Application No.
Inhibitors having a hydrophilic group described in 60-218169, polymer inhibitors described in Japanese Patent Application No. 60-262177 and compounds having a ballast group described in Japanese Patent Application No. 60-263564. To be

Examples of the silver image stabilizer include polyhalogenated organic oxidants described in U.S. Pat.No. 3,707,377 (e.g., tetrabromobutane, tribromoquinaridine, etc.), and Belgian patent No. 768,071. Methoxycarbonylthio-1-phenyltetrazole, monohalo compounds described in JP-A-50-119624 (for example, 2-bromo-2-tolylsulfonylacetamide, etc.), bromine compounds described in JP-A-50-120328 (for example, , 2-bromomethylsulfonylbenzothiazole, 2,4-bis (tribromomethyl) -6-methyltriazine, etc.), and JP-A-53-46020.
And tribromoethanol, etc. Various monohalogenated organic antifoggants for silver halide emulsions described in JP-A-50-119624 can be used.

Other image stabilizers include US Pat.
No. 4,082,555, No. 4,088,496, JP-A-50-22625
Research Disclosure (RD) 12021, 151
No. 68, No. 15567, No. 15732, No. 15733, No. 15734,
A compound called activator precursor described in JP-A-15776, which releases a basic substance by heat,
For example, compounds such as guanidinium trichloroacetate which decarboxylate by heat to release a base, aldonamide compounds such as galactonamide, amine imides, compounds such as 2-carboxycarboxamide, and JP-A-56-130745.
No. 56-132332, sodium phosphate base generators, compounds generating an amine by an intramolecular nucleophilic reaction described in British Patent 2,079,480, JP-A-59-157637.
Aldoxime carbamates described in No. 59-16694
Examples thereof include hydroxamic acid carbamates described in No. 3, and base releasing agents described in Nos. 59-180537, 59-174830, 59-195237 and the like.

Furthermore, U.S. Pat.Nos. 3,301,678, 3,506,444 and 3,82
No. 4,103, No. 3,844,788, RD12035, No. 18016, etc., irithiuronium compounds, s-carbamoyl derivatives of mercapto-containing compounds and nitrogen-containing heterocyclic compounds may be used for the purpose of stabilizing an image. , Further U.S. Pat.Nos. 3,669,670, 4,012,260, 4,060,420,
Nos. 4,207,392, RD15109, RD17711, etc., nitrogen-containing organic bases called activator stabilizers and activator stabilizer precursors, for example, α-sulfonylacetic acid salts or trichloroacetic acid salts of 2-aminothiazoline and acylhydrazine compounds, etc., respectively. It can be used for the purpose of accelerating development and for stabilizing the image.

Further, for example, the development may be carried out in the presence of a small amount of water as described in JP-A-56-130745 and 59-218443, or a small amount of water may be sprayed before heating or a fixed amount. May be applied to supply water, or as described in U.S. Pat. No. 3,312,550, development may be performed with hot steam or hot air containing moisture. Also, a compound that releases water into the photothermographic material,
For example, a compound containing water of crystallization as described in JP-B-44-26582, for example, sodium phosphate dodecahydrate, ammonium alum 24-hydrate, etc. may be contained in the photothermographic material.

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

In the photothermographic material of the present invention, colloidal silica is used in the photothermographic layer and / or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving the physical properties of the film. it can.

The colloidal silica used in the present invention is a colloidal solution of silicic acid anhydride mainly having water as a dispersion medium and having an average particle size of 3 to 120 mμ, and its main component is SiO ₂ (silicon dioxide). Regarding colloidal silica, for example, JP-A-56-109336
No. 53-123916, No. 53-112732, No. 53-100226, etc. The amount of colloidal silica used is 0.05 by dry weight ratio to the binder of the layer to be mixed and applied.
The range of to 2.0 is preferable.

In the photothermographic material of the present invention, an organic fluoro compound is used in the photothermographic layer and / or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving the physical properties of the film. You can

Regarding the organic fluoro compound used in the present invention, U.S. Pat. Nos. 3,589,906, 3,666,478 and 3,754,924 are cited.
, 3,775,126, 3,850,640, West German Patent Publication No. 1,
942,665, 1,961,638, 2,124,262, British Patent 1,330,356, Belgian Patent 742,680 and JP
46-7781, 48-9715, 49-46733, 49-133023
No. 50, No. 50-99529, No. 50-11322, No. 50-160034, No. 5
1-43131, 51-129229, 51-106419, 53-8471
No. 2, No. 54-111330, No. 56-109336, No. 59-30536,
59-45441 and Japanese Patent Publications 47-9303, 48-43130,
The compounds described in No. 59-5887 and the like can be mentioned, and these compounds can be preferably used.

The photothermographic material of the present invention comprises a photothermographic layer and / or
Alternatively, an antistatic agent can be used in the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

As the antistatic agent used in the present invention, British Patent No. 1,
466,600, Research Disclosure (Research
Disclosure) 15840, 16258, 16630, U.S. Patents 2,327,828, 2,861,056, 3,206,312,
3,245,833, 3,428,451, 3,775,126, 3,96
3,498, 4,025,342, 4,025,463, 4,025,691
No. 4,025,704 and the like, and these can be preferably used.

The photothermographic material of the present invention comprises a photothermographic layer and / or
Alternatively, an ultraviolet absorber can be used in the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

Examples of the ultraviolet absorber used in the present invention include benzophenone compounds (for example, JP-A-46-2784 and US Pat.
5,530, 3,698,907), butadiene compounds (e.g., those described in U.S. Pat.No. 4,045,229), 4-thiazolidone compounds (e.g., U.S. Pat.
Nos. 314,794 and 3,352,681), benzotriazole compounds substituted with an aryl group [eg, Japanese Patent Publication No.
36-10466, 41-1687, 42-26187, 44-29620
No. 48-41572, JP-A-54-95233, 57-142975.
U.S. Pat.Nos. 3,253,921, 3,533,794 and 3,754,
919, 3,794,493, 4,009,038, 4,220,711
No. 4,323,633, Research Disclosure (R
esearch Disclosure) 22519], benzooxide compounds (for example, those described in U.S. Pat. No. 3,700,455), cinnamic acid ester compounds (for example, U.S. Pat. Nos. 3,705,805, 3,707,375, JP-A-52-52). 49029
Those described in No.). Further, those described in US Pat. No. 3,499,762 and JP-A-54-48535 can also be used. UV-absorbing couplers (for example, α-naphthol type cyan dye forming couplers),
UV absorbing polymers (see, for example, JP-A-58-111942)
No. 178351, No. 181041, No. 59-19945, No. 23344
No., those described in the gazette).

The photothermographic material of the present invention comprises a photothermographic layer and / or
Alternatively, a hardener can be used in the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

Examples of the hardener used in the present invention include aldehyde-based and aziridine-based (for example, PB Report 19,921, US Pat.
950,197, 2,964,404, 2,983,611, and
Each specification of 3,271,175, JP-B-46-40898, JP-A-50-
91315), isoxazole-based (e.g., those described in U.S. Pat.No. 331,609), epoxy-based (e.g., U.S. Pat.No. 3,047,394, West German patent 1,085,663, British patent 1,033,518). Nos. 4 to 35495), vinyl sulfone type (for example, PB Report 19,920, West German Patent No. 1,10).
0,942, 2,337,412, 2,545,722, 2,635,518
No. 2,742,308, No. 2,749,260, British Patent No. 1,251,
091, Japanese Patent Application Nos. 45-54236 and 48-110996, U.S. Patent No.
3,539,644, those described in each specification of the same 3,490,911), acryloyl type (for example, Japanese Patent Application No. 48-27949, U.S. Pat.No. 3,640,720 described in each specification), carbodiimide type (for example, U.S. Patent Nos. 2,938,892 and 4,0
43,818 and 4,061,499 specifications, Japanese Patent Publication No. 46-38715
Japanese Patent Application Publication No. 49-15095), triazines (for example, West German Patent Nos. 2,410,973 and 2,553,9).
No. 15, U.S. Pat.No. 3,325,287, JP-A-52-12
No. 722) and other maleimide-based, acetylene-based, methanesulfonic acid ester-based, and N-methylol-based hardeners can be used alone or in combination. As a useful combination technique, for example, West German Patent No. 2,447,587
No. 2,505,746, No. 2,514,245, U.S. Pat.No. 4,047,
No. 957, No. 3,832,181, each specification of the same 3,840,370, JP-A-48-43319, 50-63062, 52-127329, the combination described in JP-B 48-32364. To be

The photothermographic material of the present invention comprises a photothermographic layer and / or
Alternatively, a polymer hardener can be used in the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

Examples of the polymer hardener used in the present invention include, for example, polymers having an aldehyde group described in US Pat. No. 3,396,029 (for example, acrolein copolymers),
362,827, Research Disclosure 17333 (19
78) and the like, polymers having a dichlorotriazine group, US Pat. No. 3,623,878, which has an epoxy group, Research Disclosure 16725 (1)
978), U.S. Pat.No. 4,161,407, JP-A-54-65033,
Polymers having an active vinyl group or a group that can be a precursor thereof, as described in JP-A-56-142524,
Examples thereof include polymers having an active ester group described in JP-A-56-66841.

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

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

The preferred average particle size of the polymer latex is 0.02 μm to 0.
It is 2 μm. The amount of the polymer latex used is preferably 0.03 to 0.5 as a dry weight ratio with respect to the binder of the layer to be added.

The photothermographic material of the present invention has various surface-active properties in the photothermographic layer and / or the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer) for the purpose of improving coatability. Agents can be used.

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

Examples of the anionic surfactant include alkyl carboxylates, alkyl sulfonates, alkyne benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N
-Acyl-N-alkyl taurates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc., carboxy groups, sulfo groups,
Those containing an acidic group such as a phospho group, a sulfuric acid ester group and a phosphoric acid ester group are preferred.

Examples of the cationic surfactant include alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing an aliphatic or heterocycle are preferable.

As the amphoteric surfactant, for example, amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides and the like are preferable.

Examples of nonionic surfactants include saponins (steroidal), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene). Glycol sorbitan esters,
Polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone),
Glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars and the like are preferable.

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

The non-photosensitive silver halide grains used in the present invention have 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 is 3 μm or less. Further, the addition amount is preferably in the range of 0.02 to 3 g / m ^{2 in} terms of silver amount with respect to the layer to be added.

In the photothermographic material of the present invention, for the purpose of improving the physical properties of the film, the photothermographic layer and / or the non-photosensitive layer (undercoat layer, intermediate layer, protective layer, etc.) may be, for example, disclosed in JP-A-51-104338. The vinyl polymer having a carboxyl group or a sulfo group described in the above publication can be contained.

The amount of the vinyl polymer used is preferably in the range of 0.05 to 2.0 in dry weight ratio with respect to the binder of the layer to be added.

The photothermographic material of the present invention basically comprises (1) a photosensitive silver halide, (2) a reducing agent, (3) a dye-providing substance, and (4) a binder in one photothermographic layer. Contains,
Further, it is preferable to contain (5) an organic silver salt, if necessary. However, these do not necessarily have to be contained in a single photographic constituent layer.
The layers (1), (2), (4), and (5) are contained in the heat-developable photosensitive layer on one side, and the dye-donor substance is added to the layer on the other side adjacent to the photosensitive layer. As long as they can react with each other, such as containing (3), they may be contained separately in two or more constituent layers.

The heat-developable photosensitive layer may be divided into two or more layers such as a high-sensitivity layer and a low-sensitivity layer and a high-concentration layer and a low-concentration layer.

The photothermographic material of the invention has one or more photothermographic layers on a support. In the case of color, it generally has three heat-developable photosensitive layers having different color sensitivities, and in each photosensitive layer, dyes having different hues are formed or released by heat development. Usually, a yellow dye is combined with the blue photosensitive layer, a magenta dye is combined with the green photosensitive layer, and a cyan dye is combined with the red photosensitive layer, but the combination is not limited thereto. It is also possible to combine a near-infrared photosensitive layer.

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

The photothermographic material of the invention may be provided with a non-photosensitive layer 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 photothermographic layer.
For coating the heat-developable photosensitive layer and these non-photosensitive layers on a support, the same methods as those used for coating and preparing a general silver halide photosensitive material can be applied.

That is, there are methods and devices in the dip method, roller method, reverse roll method, air knife method, doctor blade method, spray method, bead method, extrusion method, stretch flow method, curtain method and the like.

The photothermographic material of the present invention usually has a temperature of 80 to 200 after imagewise exposure.
℃, preferably in the temperature range of 100 ℃ ~ 170 ℃ 1 second ~ 18
It is developed only by heating at 0 ° C., preferably for 1.5 seconds to 120 seconds. The transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with the 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 the heat-development. Alternatively, the transfer may be performed by supplying water and then closely contacting the same and then heating it if necessary. Moreover, you may perform a pre-heating in the temperature range of 70 degreeC-180 degreeC before exposure. Also, JP-A-60-143338 and Japanese Patent Application No. 60-36
As described in No. 44, the photosensitive material and the image receiving member are heated to 80 ° C. to 250 ° C. immediately before heat development transfer in order to enhance mutual adhesion.
Each may be preheated at a temperature of ° C.

Various exposing means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation containing visible light. Generally, a light source used for ordinary color printing, for example, a tungsten lamp, a mercury lamp, a xenon lamp, a laser beam, a CRT beam or the like can be used as the light source.

As the heating means, all methods applicable to ordinary photothermographic materials can be used, for example, contact with a heated block or plate, contact with a heat roller or a heat drum, or passage through a high temperature atmosphere. Alternatively, high-frequency heating is used, or further, a conductive layer containing a conductive substance such as carbon black is provided on the back surface of the photosensitive material of the present invention or the back surface of the image transfer member for thermal transfer, and Joule heat generated by energization is used. You can also The heating pattern is not particularly limited, and it includes a method of preheating (preheating) in advance and then heating again, rising at a high temperature for a short time or at a low temperature for a long time, continuously rising, descending or repeating, and further discontinuous. It can be heated,
A simple pattern is preferred. Further, it may be a system in which exposure and heating proceed simultaneously.

When the photothermographic material of the present invention is a so-called transfer type photosensitive material which forms a color image by transfer, an image receiving member is used.

The image receiving layer of the image receiving member effectively used in the present invention,
It is sufficient that it has a function of receiving the dye in the photothermographic layer which is released or formed by heat development, and is a polymer containing a tertiary amine or a quaternary ammonium salt.
Those described in No. 709,690 are preferably used. For example, as a polymer containing an ammonium salt, a ratio of polystyrene-co-N, N, N-tri-n-hexyl-N-vinyl-benzylammonium chloride is 1: 4 to.
It is 4: 1 and preferably 1: 1. Examples of polymers containing tertiary amines include polyvinyl pyridine and the like. A typical image-receiving layer for diffusion transfer can be obtained by mixing a polymer containing an ammonium salt, a tertiary amine or the like with gelatin, polyvinyl alcohol or the like and coating the mixture on a support. Another useful dye receiving substance is JP-A-57-207250.
And the like, which are formed of a heat-resistant organic polymer substance having a glass transition temperature of 40 ° C. or higher and 250 ° C. or lower.

These polymers may be carried on a support as an image receiving layer, or may be used as a support itself.

Examples of the heat-resistant organic polymer substance include polystyrene, polystyrene derivatives having a substituent having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole,
Polyacetals such as polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrifluoroethylene, polyacrylonitrile, poly-N, N-dimethylallylamide, p-cyanophenyl group , Polyacrylate having pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate, polymethylmethacrylate, polyethylmethacrylate, polypropylmethacrylate, polyisopropylmethacrylate, polyisobutylmethacrylate, poly-tert-butylmethacrylate, polycyclohexyl Methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthale Examples thereof include polyesters such as polyester, polystyrene, polycarbonates such as bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. In addition, Polymer Handbook Second Edition (edited by Jay Brand Wrap, EH Inmargat) John Willy & Sand {Polymer Ha
ndbook 2nd ed. (J, Brandrup, EHImmergut) John Wi
ley & Sons} glass transition temperature of 40 ℃
The following synthetic polymers are also useful. Generally, 2,000 to 200,000 is useful as the molecular weight of the polymer substance. These polymer substances may be used alone or in combination of two or more kinds, or may be used in combination of two or more kinds as a copolymer.

Useful polymers may be formed by cellulose acetates such as triacetate, diacetate, heptamethylenediamine and terephthalic acid, fluorange or multiple layers.

As the support for the image-receiving member, any support such as a transparent support or an opaque support may be used. For example, a film of polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypropylene or the like and the support thereof may be used. Supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, talc, baryta paper, RC paper laminated with a thermoplastic resin containing pigment on paper, cloth, glass, aluminum, etc. Metals, etc., or a support obtained by coating and curing an electron beam curable resin composition containing a pigment on these supports, and a support provided with a coating layer containing a pigment on these supports. Etc.

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

Polyamide with a combination of propylamine and adipic acid, hexamethylenediamine and diphenic acid, hexamethylenediamine and isophthalic acid, polyester with a combination of diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, polyethylene terephthalate , And polycarbonate. These polymers may be modified. For example, polyethylene terephthalate using cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid or the like as a modifier is also effective.

Particularly preferred image-receiving layers include the layer made of polyvinyl chloride described in JP-A-59-223425 and the layer made of polycarbonate and a plasticizer described in JP-A-60-19138.

These polymers can also be used as an image receiving layer (image receiving member) which also serves as a support. At that time, the support may be formed of a single layer, and the present invention is applied to a heat developable color light-sensitive material. When used as a mordant for dye images, the various polymers described above can be used as the image-receiving layer, which may be a separate image-receiving element comprising the image-receiving layer on a suitable support. May be a single layer which is part of a heat developable color photographic material. If desired, an opaque layer (reflective layer) can be included in the light-sensitive material, which layer reflects the desired degree of radiation, such as visible light, that can be used to observe the dye image in the image-receiving layer. It is used to The opacifying layer (reflecting layer) can contain various reagents which provide the necessary reflection, for example titanium dioxide.

The image-receiving layer of the image-receiving member can be formed in a mold which is peeled off from the photothermographic layer. For example, after imagewise exposure of a heat-developable color light-sensitive material, an image-receiving layer may be superposed on the heat-developable light-sensitive layer and uniformly heated and developed. It is also possible to transfer the dye image released or formed from the dye-donor substance by superimposing image-receiving layers after imagewise exposure of the heat-developable color light-sensitive material and uniform heat development, and heating at a temperature lower than the development temperature.

The photothermographic material of the invention is preferably provided with a protective layer. Hereinafter, it is referred to as the protective layer of the present invention.

Various additives used in the field of photography can be used in the protective layer of the present invention. Examples of the additive include various matting agents, colloidal silica, sliding agents, organic fluoro compounds (particularly fluorine-based surfactants), antistatic agents, ultraviolet absorbers, high boiling organic solvents, antioxidants, hydroquinone derivatives, polymers. Examples thereof include latex, surfactants (including polymer surfactants), hardeners (including polymer hardeners), organic silver salt particles, non-photosensitive silver halide particles, 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 contained in the photothermographic material to increase the roughness of the surface of the photosensitive material to form a so-called matte. is there. A method of using a matting agent to prevent adhesion that occurs during production, storage, use, etc. of a light-sensitive material, and to prevent charging caused by contact, friction, or peeling between the same or different substances is known in the art. Is well known in. Specific examples of the matting agent include JP-A-50-46316
Silicon dioxide described in JP-A-53-7231 and JP-A-58-66937.
Alkali-soluble matting agents such as alkyl methacrylate / methacrylic acid copolymers described in JP-A No. 60-8894,
An alkali-soluble polymer having an anionic group described in JP-A-58-166341, a combination of two or more kinds of fine particle powders having different Mohs hardness described in JP-A-58-145935, and JP-A-58-147734.
Combination of oil droplets and fine particle powder described in JP-A-59-149356, combination of two or more spherical matting agents described in JP-A-59-149356, and fluorinated surfactant described in JP-A-56-44411. Combined use of matting agents, and British Patent No. 1,055,713, U.S. Patent Nos. 1,939,213, 2,221,873, 2,268,662, 2,3
22,037, 2,376,005, 2,391,181, 2,701,24
No. 5, No. 2,992,101, No. 3,079,257, No. 3,262,782,
No. 3,443,946, No. 3,516,832, No. 3,539,344, No. 3,5
91,379, 3,754,924, 3,767,448, JP-A-49-1
06821, organic matting agents described in 57-14835, West German Patent 2,529,321, British Patent 760,775, 1,
260,772, U.S. Pat.Nos. 1,201,905 and 2,192,241,
3,053,662, 3,062,649, 3,257,206, 3,3
No. 22,555, No. 3,353,958, No. 3,370,951, No. 3,411,90
No. 7, No. 3,437,484, No. 3,523,022, No. 3,615,554,
No. 3,635,714, No. 3,769,020, No. 4,021,245, No. 4,0
Inorganic matting agents described in JP-A-29-504, JP-A-46-7781, JP-A-49-106821, JP-A-51-6017, and JP-A-53-11.
6143, 53-100226, 57-14835, 57-82832
No. 53-70426, No. 59-149357, JP-B No. 57-9053, EP-107,378, and the like, matting agents having physical properties are preferably used.

In the protective layer of the present invention, the amount of the matting agent added is preferably 10 mg / 2.0 g, and more preferably ²⁰ mg to 1.0 g per 1 m ² . The particle size of the matting agent is preferably 0.5 to 10 μm, more preferably 1.0 to 6 μm.

You may use the said matting agent in combination of 2 or more type.

Examples of the sliding agent used in the protective layer of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, synthetic waxes, and the like, specifically, French Patent No. 2,180,
465, British Patent Nos. 955,061, 1,143,118, 1,27
0,578, 1,320,564, 1,320,757, JP-A-49-50
No. 17, No. 51-141623, No. 54-159221, No. 56-81841,
Research Disclosur
e) 13969, U.S. Pat.Nos. 1,263,722, 2,588,765,
No. 2,739,891, No. 3,018,178, No. 3,042,522, No. 3,0
80,317, 3,082,087, 3,121,060, 3,222,17
No. 8, No. 3,295,979, No. 3,489,567, No. 3,516,832,
Those described in No. 3,658,573, No. 3,679,411, No. 3,870,521 and the like can be preferably used.

The protective layer of the present invention includes a high-boiling organic solvent (e.g., U.S. Pat.Nos. 2,322,027 and 2,533,514) for the purpose of improving film adhesion and brittleness, or improving slip properties.
No. 2,882,157, Japanese Examined Patent Publication No. 46-23233, British Patent No. 95
8,441, 1,222,753, U.S. Pat.No. 2,353,262,
3,676,142, 3,700,454, JP-A-50-82078, 51
-27921, 51-141623 and the like (for example, phthalic acid esters, phosphoric acid esters, fatty acid esters, etc.), amides (for example, fatty acid amides, sulfonic acid amides, etc.), ethers, alcohols And paraffins. ), Which may be emulsified and dispersed with an oily compound insoluble in water. Further, these oil droplets may contain a photographic additive according to various purposes.

Examples of the binder used in the protective layer of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethylmethacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, polyethyloxazoline, polyacrylamide, gelatin and phthalated gelatin. 1 or 2 or more synthetic or natural polymer substances can be used in combination.

In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (molecular weight 1,000 to 400,000 is preferable), polyvinyl alcohol (molecular weight 1,000 to 100,000 is preferable)
And, polyoxazoline (molecular weight of 1,000 to 800,000 is preferable) and a binder of two or more kinds thereof are preferable, and gelatin alone or gelatin and hydrophilicity having good compatibility with gelatin such as polyvinylpyrrolidone, polyvinyl alcohol and polyoxazoline. A binder in which a polymer is used in combination is particularly preferable. The gelatin may be lime-treated, acid-treated, or ion-exchanged, and may be ossein gelatin, pigskin gelatin, hide gelatin, or modified gelatin obtained by esterification or phenylcarbamoylation thereof.

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

Further, for the purpose of increasing the film strength and preventing the film destruction, it is also preferable to make the hardness of the protective layer larger than that of the photosensitive layer. As a method of increasing the hardness of the protective layer to be larger than that of the photosensitive layer, that is, a method of controlling the hardness of each layer, there is a method of using a diffusion resistant hardener. By using the protective layer, only the hardness of the protective layer can be made higher than that of the photosensitive layer. Polymeric hardeners are known as diffusion-resistant hardeners,
For example, U.S. Patents 3,057,723, 3,396,029, 4,161,
Hardeners described in JP-A No. 407 and JP-A No. 58-50528 can be used.

As another method of controlling the dura degree for each layer,
Diffusible hardener (for example, vinyl sulfone hardener) is contained only in the protective layer, or the protective layer content is larger than that of the photosensitive layer, and simultaneous drying after multi-layer coating protects The hardness of the layer can be made larger than that of the photosensitive layer.

[Advantages of the Invention] The photothermographic material of the present invention contains the cyan dye-donating substance of the present invention, and thus is less likely to be decomposed by heat and / or a coexisting reducing agent at the time of thermal development, and at a high concentration. A cyan dye image with less fog can be obtained.

Of course, the cyan dye image formed in the photothermographic material of the invention is a clear image.

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

Example-1 [Preparation of silver iodobromide emulsion] At 50 ° C., 20 g of ossein gelatin and 1000 ml of distilled water and ammonia were mixed using the mixing and stirring described in JP-A Nos. 57-92523 and 57-92524. An aqueous solution containing 11.6 g of potassium iodide and 131 g of potassium bromide in solution A in which is dissolved 500
B solution of 1 ml and 1 mol of silver nitrate and 500 ml of an aqueous solution containing ammonia were simultaneously added while keeping pAg constant. The shape and size of the emulsion grains to be adjusted are pH, pAg and B
It was adjusted by controlling the addition rates of the liquid and the liquid C. In this way, the silver iodide content is 7 mol%, the octahedron is the average grain size.
A 0.25 μm core emulsion was prepared. Then, a core / shell type silver halide emulsion having a regular octahedron and an average grain size of 0.3 μm is prepared by coating a silver halide shell having a silver iodide content of 1 mol% in the same manner as described above. did. (The monodispersity was 9%.) The emulsion thus prepared was washed with water,
Desalted. The emulsion yield was 800 ml.

Further, a photosensitive silver iodobromide emulsion was prepared from the silver iodobromide emulsion prepared above as follows.

a) Preparation of a red-sensitive silver iodobromide emulsion 700 ml of the above silver iodobromide emulsion 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.4 g gelatin 32 g sodium thiosulfate 10 mg The following sensitizing dye methanol 1% liquid 80ml distilled water 1200ml Sensitizing dye (a) b) Preparation of a green-sensitive silver iodobromide emulsion 700 ml of the above silver iodobromide emulsion 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.4 g gelatin 32 g sodium thiosulfate 10 mg The following sensitizing dye methanol 1% liquid 80 ml distilled water 1200 ml Sensitizing dye (b) c) Preparation of blue-sensitive silver iodobromide emulsion 700 ml of the above-mentioned silver iodobromide emulsion 4-hydroxy-6-methyl-1,3,3a7, -tetrazaindene 0.4 g gelatin 32 g sodium thiosulfate 10 mg Sensitizing dye Methanol 1 % Liquid 80 ml distilled water 1200 ml Sensitizing dye (c) [Organic Silver Salt Dispersion] 2-Methylbenzotriazole and silver nitrate were reacted in a water-alcohol mixed solvent to obtain 28.8 g of 5-methylbenzotriazole silver, 16.0 g of poly (N-vinylpyrrolidone), and 1.33 g of 4-sulfobenzotriazole sodium salt was dispersed in an alumina ball mill to adjust the pH to 5.5 to 200 ml.

[Preparation of Dye-Donating Substance Dispersion Liquid] Exemplified dye-donating substance PC-6: 99.2 g, 2,4-di (t) octylhydroquinone 5.0 g and 1.0 g of the following antifoggant were dissolved in 300 ml of ethyl acetate, and alkanol XC ( (Made by DuPont)
248 ml of 5% by weight aqueous solution, 26.4 g of photographic gelatin and phenylcarbamoylated gelatin (Type 1781, Luslow Co.)
9PC) and 1440 ml of an aqueous gelatin solution containing 34.6 g of the mixture were dispersed with an ultrasonic homogenizer, the ethyl acetate was distilled off, and the pH was adjusted to 5.5 to 1590 ml.

Antifoggant [Preparation of reducing agent liquid] Exemplified reducing agent R-11: 93.2 g was added to polyvinylpyrrolidone (K
-30) was dissolved in a solution of 207 ml of a 20% by weight aqueous solution and 40 ml of the following 5% by weight aqueous solution of a surfactant, and water and a citric acid aqueous solution were added to obtain 600 ml of a reducing agent solution having a pH of 7.0.

Surfactant <Preparation of hot solvent dispersion> 430 g of p-toluamide and polyvinylpyrrodone (K-30)
1.410 ml of 1.0 wt% aqueous solution was mixed and dispersed by a ball mill to obtain a hot solvent dispersion.

[Preparation of Photothermographic Material (Sample No. 1)] On a 180 μm thick transparent polyethylene terephthalate film for photography having an undercoat layer, the above silver iodobromide emulsion,
A photothermographic material (Sample No. 1) was prepared by coating a coating liquid having the following composition prepared using an organic silver salt dispersion liquid, a dye-donor substance dispersion liquid, a reducing agent solution, and a thermal solvent dispersion liquid at a wet film thickness of 110 μm and drying. ) Was produced.

(Coating liquid composition) Organic silver salt dispersion liquid 64 ml Red-sensitive silver iodobromide emulsion liquid 30.7 ml Reducing agent liquid 38.4 ml Hot solvent dispersion liquid 94.8 ml Dye donor dispersion liquid 101 ml Photographic gelatin 10% by weight aqueous solution 21.1 ml Phenylcarbamoylation Gelatin 10% by weight aqueous solution 27.7 ml Citric acid aqueous solution and water (adjusted to pH 5.5) 89 ml 2,4-Dichloro-6-hydroxy-s-triazine sodium 2.5% aqueous solution 13.3 ml Total 480 [Preparation of image receiving member] Polycarbonate (molecular weight 25,000, L-1250, Teijin Kasei's) ethylene chloride solution applied on photographic baryta paper,
After drying, an image receiving member was prepared such that the polycarbonate content was 15.0 g / m ² .

[Evaluation of Light-sensitive Material] The light-sensitive material obtained by the above method was exposed to 800 CMS in red through a step wedge.

Then, the polycarbonate coated surface of the image receiving member and the photosensitive layer surface of the exposed photosensitive material are overlapped with each other, and the temperature is 150 ° C.
After 90 minutes of thermal development and peeling off the image receiving member, a cyan transfer image was obtained on the image receiving member. Maximum reflection density (Dmax) and fog (Dmin) of the obtained cyan image
Is shown in Table 5 below.

A light-sensitive material (Sample No. 2) similar to Sample No. 1 except that the dye-providing substance of Sample No. 1 was replaced with the dye-providing substance shown in Table 5 below.
~ 6) were produced. Further, as a comparative light-sensitive material, the dye-providing substance of Sample No. 1 is shown below as dye-providing substances (A) and (B).
Alternatively, the same photosensitive materials (Sample Nos. 7 to 9) as Sample No. 1 were prepared except that (C) was used. The amount of the dye-donor substance was the same as the amount of the dye-donor substance of Sample No. 1 (same molar amount).

These samples (Sample Nos. 2 to 9) were subjected to the same exposure and heat development as in Sample No. 1 to obtain a cyan transfer image on the image receiving member. The Dmax and Dmin of these images are shown in Table-5.

For the dye-donor substances C-9, C-11 and (C), tricresyl phosphate (half the weight of the dye-donor substance) was used as the high boiling solvent in the dispersion.

As is clear from Table 5 above, in sample No. 7 using the dye-donor substance (A), Dmax is extremely low because the dye-forming ability of the dye-donor substance is low. In addition, a dye-donating substance (B)
Alternatively, in Sample Nos. 8 and 9 using (C), it is presumed that Dmax is lowered because a part of the formed dye is decomposed by heat.

On the other hand, in Sample Nos. 1 to 6 using the cyan dye-donating substance of the present invention, transfer images having high Dmax and low Dmin can be obtained. That is, in Sample Nos. 1 to 6 according to the present invention, the maximum reflection density (Dma
It is possible to obtain a transferred image with high x) and low fog (Dmin).

Example-2 <Preparation of Dye Donor Dispersion Liquid> Exemplified dye donor C-3: 73.0 g, tricresyl phosphate 36.5 g, 2,4-di (t) octylhydroquinone 5.0 g
And 1.0 g of the antifoggant described in Example-1 with ethyl acetate.
It was dissolved in 300 ml, mixed with 248 ml of 5 wt% aqueous solution of Alkanol XC (manufactured by DuPont) and 1440 ml of gelatin aqueous solution containing 34.6 g of photographic gelatin, dispersed with an ultrasonic homogenizer, and distilled to remove ethyl acetate, and then pH was adjusted to 6. 0 to 1590 ml
Finished.

A photothermographic material (Sample No. 1) was prepared by coating a coating solution having the following composition on a photographic baryter paper with a wet film thickness of 80 μm and drying it.
0) was prepared.

(Coating liquid composition) Organic silver salt dispersion liquid (described in Example-1) 64 ml Red-sensitive silver halide emulsion liquid (described in Example-1) 30.7 ml Reducing agent liquid (described in Example-1) 38.4 ml Hot solvent dispersion (described in Example 1) 75.8 ml Dye-donor dispersion 104 ml Photographic gelatin 10% by weight aqueous solution 60 ml Citric acid aqueous solution and water (adjusted to pH 6.0) 93.8 ml 2,4-Dichloro-6-hydroxy-s-triazine sodium 2.5% aqueous solution 13.3 ml Total 480 ml In the same manner, the dye-donor substance C-3 of sample No. 10 is shown in Table-6. The same photosensitive material (Sample Nos. 11 to 1) except that the donor material C-3 was used in the same molar amount)
3) was produced. In addition, as the comparative light-sensitive material, light-sensitive materials (Sample Nos. 14 to 15) same as Sample 10 were prepared except that the dye-providing substance was changed to (D) and (E) shown below.

The obtained light-sensitive materials (Sample Nos. 10 to 15) were exposed to a red color of 800 CMS through a step wedge, a polyethylene terephthalate base was overlaid on the light-sensitive material surface, and heat development was performed at 145 ° C. for 90 seconds. Table 6 below shows Dmax and Dmin of the obtained cyan image.

As is clear from Table 6 above, the light-sensitive material of the present invention has a higher Dmax of the cyan dye image than the light-sensitive material of the comparison.
This is considered to be because in Sample Nos. 10 to 13 according to the present invention, the cyan dye-donating substance of the present invention is less likely to be decomposed by heat or a coexisting reducing agent.

Example-4 On a 180-μm thick transparent polyester terephthalate film having a subbing layer, the coating solution described in Example-1 was applied at a wet film thickness of 65 μm and dried to form a first photosensitive layer. .

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

Gelatin 0.6g / m ² Polyvinylpyrrolidone 0.3g / m ^{2 The following} compound (CD 'scavenger) 0.2g Methylbenztriazole silver 0.6g p-Toluamide 1.0g / m ² 2,4-Dichloro-6-hydroxy-s-triazine sodium 20mg / m ² CD ′ scavenger On the first intermediate layer, the dye-donor substance of Example-1 was replaced with the following magenta dye-donor substance, and the silver iodobromide agent was replaced with the green-sensitive silver iodobromide emulsion described in Example-1. A coating solution having the same composition as in Example-1 was applied to a wet film thickness of 45 μm to form a second photosensitive layer.

A second intermediate layer having a composition obtained by adding the following yellow filter dye (0.2 g / m ² ) to the composition of the first intermediate layer was coated on the second photosensitive layer.

Further, on the second intermediate layer, the dye-donor substance of Example-1 was replaced with the following yellow dye-donor substance, and the silver iodobromide emulsion was replaced with the blue-sensitive silver iodobromide emulsion described in Example-1. Was coated with a coating solution having the same composition as in Example 1 to a wet film thickness of 75 μm to form a third photosensitive layer.

Further, a protective layer having the following composition was coated on the third photosensitive layer to obtain a multilayer photosensitive material (Sample No. 16).

Gelatin 0.28 g / m ² Polyvinylpyrrolidone 0.14 g / m ² SiO ₂ 0.36 g / m ₂ Saffron 1.0 g / m ₂ p-toluamide 0.42 g / m ² Also, the cyan dye-donor substance of the first layer of the above-mentioned multilayer photosensitive material is C -9 and the comparative dye-donor (B) described in Example-2.
Multilayer photosensitive material (Sample No. 16)
17 and 18) were prepared.

The obtained photosensitive material sample Nos. 16 to 18 were exposed to 800 CMS of red light, green light, and blue light, respectively, and heat development was performed in the same manner as in Example 1, and the transfer densities of cyan, magenta, and yellow dyes ( Dmax and Dmin) were measured. The results are shown in Table 7 below.

As is clear from Table 7 above, the light-sensitive material of the present invention has higher cyan dye image Dmax than that of the comparative light-sensitive material. And, such an effect is larger than that in the first embodiment.
This is because the light-sensitive material of this example is a so-called multi-layer type, so that the diffusion time of the dye-donor substance in the light-sensitive layer is long, and the dye-decomposition is decomposed by contact with the reducing agent present in another layer. It is presumed that in the comparative light-sensitive material, a larger amount of cyan dye is thermally decomposed than in the light-sensitive material of the present invention using the cyan dye-donor of the present invention.

Further, as is clear from Table 7 above, Sample No. 1 using the compound represented by the general formula (1) as a dye-donor substance
In No. 7, color mixing that is presumed to be due to diffusion of the cyan dye to the other layer occurs, and from the viewpoint of the immobility of the dye-donor substance,
It can be seen that a sample using a polymer derived from the compound represented by the general formula (3) as the dye-donor substance like Sample No. 16 is more preferable.

Claims (1)

[Claims] 1. In a photothermographic material having a photographic constituent layer containing at least a photosensitive silver halide, a reducing agent, a dye-donor substance and a binder on a support, at least one of the dye-donor substances is represented by the following general formula: A photothermographic material comprising a compound represented by (1) or a polymer derived from the compound. General formula (1) (In the formula, R ¹ represents a monovalent organic group, and R ² has ² carbon atoms.
To 6 alkyl groups, R ³ represents a hydrogen atom or a monovalent organic group, X represents a hydrogen atom or a halogen atom, Y represents an oxygen atom or a sulfur atom, M represents a hydrogen atom, NH. Represents a _4- group or monovalent metal atom. )