JPH0535858B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a heat-developable photosensitive material. For more information,
The present invention relates to a heat-developable photosensitive material that forms an image by transferring a dye formed by heat development. More specifically, the present invention relates to a heat-developable photosensitive material from which a heat-developable diffusion transfer image is obtained from a novel reducing dye-imparting substance that releases a diffusible dye upon heat development. [Background of the Invention] Photography using photosensitive silver halide is superior to other photographic methods in terms of photosensitivity, gradation, image preservation, etc., and is the most widely put into practical use. However, since this method uses wet processing for processing steps such as development, fixing, and water washing, processing is time-consuming and labor-intensive, and there are concerns that the processing chemicals may affect the human body, or the processing room and work area may be affected. There are many problems, such as concerns about contamination of people by the above-mentioned chemicals, and further consideration of pollution caused by waste liquid. Therefore, it has been desired to develop a photosensitive material that uses photosensitive silver halide and can be dry processed. Many proposals have been made regarding the above-mentioned dry processing photographic method, and among them, heat-developable photosensitive materials in which the developing step can be carried out by heat treatment are attracting attention as photosensitive materials that meet the above-mentioned requirements. Such heat-developable photosensitive materials are described in, for example, Japanese Patent Publication Nos. 43-4921 and 43-4924, which disclose photosensitive materials comprising an organic silver salt, silver halide, and a reducing agent. Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods. For example, U.S. Pat. No. 3,531,286, U.S. Pat. No. 3,761,270, and U.S. Pat. No. 3,764,328 disclose thermal development in which a color image is formed by the reaction of an oxidized product of an aromatic primary amine developing agent with a coupler. A color photosensitive material is disclosed. Further, Research Disclosure No. 15108 and No. 15127 disclose a heat-developable color photosensitive material in which a color image is formed by the reaction of an oxidized product of a sulfonamide phenol or sulfonamide aniline derivative developing agent with a coupler. has been done. However, in these methods, after heat development,
Since a reduced silver image and a color image are simultaneously generated in the exposed area, there is a problem that the color image becomes cloudy. In addition,
To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as an image receiving sheet having an image receiving layer. The problem is that it is not easy to transfer. In addition, using an organic imino silver salt having a dye part in Research Disclosure No. 16966, the imino group is liberated in the exposed area by heat development, and a color image is transferred onto the image-receiving layer as a transfer paper using a solvent. A heat-developable color photosensitive material is disclosed. However, this method has the problem that it is difficult to suppress the release of dye in areas not exposed to light, and it is not possible to obtain clear color images. Also, JP-A-52-105821, JP-A No. 52-105822,
Publications No. 56-50328, U.S. Patent No. 4235957, Research Disclosure No. 14448,
No. 15227 and No. 18137, etc., disclose heat-developable color photosensitive materials in which a positive color image is formed by a heat-sensitive silver dye bleaching method. However, this method requires extra steps and photographic construction materials, such as stacking and heating sheets containing activators to speed up the bleaching of the dyes, and the resulting color images do not survive long-term storage. Another problem is that it is gradually reduced and bleached by coexisting free silver and the like. Further, in the specifications of U.S. Patent No. 3180732, U.S. Patent No. 3985565, and U.S. Patent No. 4022617, as well as Research Disclosure No. 12533, heat-developable color photosensitive materials are disclosed that utilize leuco dyes to form color images. ing. However, this method has the problem that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage. Furthermore, JP-A-57-179840 and JP-A-58-
No. 58543, JP-A-59-168439, JP-A-59-
No. 1805505 and the like disclose heat-developable color photosensitive materials in which a dye image is formed using a reducing dye-providing substance that releases a diffusible dye. However, the dye-imparting substances described in this publication cannot be said to have sufficient immobility in heat-developable light-sensitive materials, with unreacted dye-imparting substances remaining in the emulsion layer, and in particular, they cannot be said to have sufficient immobility in terms of immobility, especially in terms of diffusion. When the dye is transferred using a solvent, especially a hot solvent, without substantially using water, the dye-providing substance itself is transferred, resulting in fogging or the transfer of two or more different tones. A heat-developable light-sensitive material having a multilayer structure using a dye-providing substance has a disadvantage in that color turbidity occurs. [Object of the Invention] An object of the present invention is to provide a heat-developable photosensitive material containing a novel reducing dye-providing substance to solve the problems of the above-mentioned dye-providing substances. Another object of the present invention is to provide a photothermographic material capable of producing images with less fog. Still another object of the present invention is to provide a heat-developable color photosensitive material that can produce clear color images with little color turbidity. [Summary of the Invention] The above object of the present invention is to provide a heat-developable photosensitive material having a photographic constituent layer containing at least a photosensitive silver halide, a reducing agent, a binder, and a dye-providing substance on a support. This can be achieved by using a photothermographic material which is a polymer having at least one repeating unit derived from a monomer represented by the following general formula (1). General formula (1) Q-X-SO ₂ -Dye In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and X represents an oxidizable acyclic, carbocyclic or heterocyclic group. represents the substrate of
Dye represents a dye residue for image formation. [Specific Structure of the Invention] In the general formula (1), Q represents a group having an ethylenically unsaturated group or an elethinically unsaturated group, and is preferably represented by the following general formula (2). General formula (2) In the formula, R ₂ represents a hydrogen atom, a carboxy group, or an alkyl group (e.g., methyl group, ethyl group, etc.), and this alkyl group may have a substituent,
Examples of the substituent include a halogen atom (eg, a fluorine atom, a chlorine atom, etc.), a carboxy group, and the like. The carboxy group represented by R ₂ and the carboxy group of the substituent may form a salt. J ₁ and J ₂ each represent a divalent bonding group, and examples of the divalent bonding group include -NHCO-, -
CONH−, −COO−, −OCO−, −SCO−, −COS
-, -O-, -S-, -SO-, _-SO2- , and the like.
X ₁ and X ₂ each represent a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include an alkylene group, an arylene group, an aralkylene group, an alkylenearylene group, and an arylenealkylene group. , for example, a methylene group, an ethylene group, a propylene group, etc., an example of an arylene group is a phenylene group, an example of an aralkylene group is a phenylmethylene group, and an example of an alkylene arylene group is, for example, a methylene group. Examples of the arylene alkylene group include a phenylene group, and an example of the arylene alkylene group is a phenylene group. l ₁ , m ₁ , l ₂ and m ₂ each represent 0 or 1. In the above general formula, X represents an oxidizable acyclic, carbocyclic or heterocyclic substrate, and preferred groups represented by QX- are represented by the following general formula (3), ( 4) or (5). General formula (3) General formula (4) General formula (5) In the general formulas (3) and (4), W represents an atomic group necessary to form a benzene ring or a naphthalene ring which may have a substituent on the ring. In general formulas (3), (4), and (5), R ₃ , R ₄ and R ₅
are a hydrogen atom, an alkyl group, an aryl group, and
Alkoxy group, aryloxy group, aralkyl group, acyl group, acylamino group, alkylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxyalkyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, cyano group, alkylthio group, Represents an arylthio group or a halogen atom, and these groups can further include an alkyl group, an aryl group, an alkoxy group,
It may be substituted with a hydroxyl group, nitro group, acylamino group, carbamoyl group, sulfamoyl group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, ureido group, etc., and further one of R ₃ , R ₄ , R ₅ is a group represented by Q or Q
It is a group substituted with a group represented by In the general formula (1), the image-forming dye residue represented by Dye includes, for example, azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, etc. Examples include residues. Further, as specific examples of the image-forming dye residue represented by Dye, preferably used yellow, magenta and cyan image-forming dyes are represented by the following general formulas (6) to (40). (Yellow) General formula (6) General formula (7) General formula (8) General formula (9) General formula (10) General formula〓 General formula (12) General formula (13) General formula (14) General formula (15) (Magenta) General formula (16) General formula (17) General formula (18) General formula (19) General formula (20) General formula (21) General formula (22) General formula (23) General formula (24) General formula (25) General formula (26) General formula (27) (Cyan) General formula (28) General formula (29) General formula (30) General formula (31) General formula (32) General formula (33) General formula (34) General formula (35) General formula (36) General formula (37) General formula (38) General formula (39) General formula (40) In the formula, R ₆ to _{R 11} are a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group,
Acyl group, cyano group, hydroxyl group, alkylsulfonylamino group, arylsulfonylamino group, alkylsulfonyl group, hydroxyalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group, aryloxyalkyl group, nitro group, halogen atom, Sulfamoyl group, N-substituted sulfamoyl group, carbamoyl group, N-substituted carbamoyl group, sulfamide group,
N-substituted sulfamide group, hydroxyalkoxy group, alkoxyalkoxy group, carboxyl group,
It represents a substituent selected from an amino group, a substituted amino group, an alkylthio group, an arylthio group, a hydroxamic acid group, an imide group, a sulfo group, a phosphoric acid group, a quaternary ammonium group, a ureido group, a heterocyclic group, and the like. Furthermore, another preferable dye includes a chelatable dye represented by the following general formula. General formula (41) General formula (42) In the formula, Y ₁ is an aromatic ring (e.g. benzene ring, naphthalene ring) or a heterocyclic ring (e.g. pyridine ring, pyrazole ring, pyrazolotriazole ring) in which at least one ring is composed of 5 to 7 atoms.
represents the atomic group necessary to form the azo bond, and at least one adjacent position of the carbon atom bonded to the azo bond.
is (a) a nitrogen atom, or (b) a carbon atom substituted with a nitrogen atom, an oxygen atom, or a sulfur atom;
_Y2 forms an aromatic ring (e.g. benzene ring, naphthalene ring) or a heterocycle (e.g. pyridine ring, pyrazole ring, pyrazolotriazole ring) in which at least one ring is composed of 5 to 7 atoms. G represents a chelating group (eg, amino group, hydroxyl group, carboxy group, alkoxy group, thioalkoxy group). R ₁₂ and R ₁₃ have the same meanings as R ₆ to _{R 11} above. In the general formula (1) of the present invention, Q-X
Specific examples of the dye-releasing group represented by are shown below. (1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) Specific examples of the monomer represented by general formula (1) of the present invention are shown below. Exemplary monomer (m-1) (m-2) (m-3) (m-4) (m-5) (m-6) (m-7) (m-8) (m-9) (m-10) (m-11) (m-12) A specific synthesis example of the monomer of the present invention is shown below. Synthesis of exemplified monomer (m-1) 1-hydroxy-4-amino-2-naphthoic acid
22.7g was dissolved in 50ml of pyridine and 400ml of dimethylacetamide, and 41.8g of 1-phenyl-3-cyano-4-(2-methoxy-5-chlorosulfonylphenyl)azo-5-pyrazolone was added little by little under ice cooling. After further stirring at room temperature for 30 minutes, the reaction solution was poured into diluted hydrochloric acid solution, and the orange precipitate (intermediate) that had precipitated was collected by filtration. Yield: 52g. Add 29.2 g of this intermediate to 200 ml of dioxane and add 8.8 g of m-methacryloylaminoaniline.
and 10.3 g of dicyclohexylcarbodiimide were added, stirred at room temperature for 2 hours, and filtered. Add filtrate to 1 part water
The orange precipitate that precipitated was collected by filtration and recrystallized using methyl cellosolve to obtain 24.5 g of the desired product. The same method can be used for the other exemplified monomers m-2 to m-12 based on the synthesis method for m-1 above. The polymer having repeating units derived from the monomer represented by the general formula [1] is a so-called homopolymer of repeating units consisting of only one type of monomer represented by the general formula [1]. It may also be a copolymer combining two or more types of monomers represented by the general formula [1],
Furthermore, it may be a copolymer comprising one or more other copolymerizable comonomers having ethylenically unsaturated groups. Examples of the comonomer having an ethylenically unsaturated group that can form a copolymer with the monomer represented by the general formula [1] of the present invention include acrylic esters, methacrylic esters, vinyl esters, olefins, and styrenes. , crotonate esters, itaconate diesters, maleate diesters, fumarate diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polytubular functional monomer,
Examples include various unsaturated acids. More specifically, these comonomers include 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 (number of moles added = 9) 1 -bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like. 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-hydroxy Butyl 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-ethoxypolyethylene glycol methacrylate (additional mole number n = 6), allyl methacrylate, methacrylic acid dimethylaminoethylmethyl chloride salt, etc. can be mentioned. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc. can be mentioned. Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene,
1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-
Dimethyl butadiene and the like can be mentioned. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene,
Examples include chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, and vinylbenzoic acid methyl ester. Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like. Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate,
Examples include dibutyl itaconate. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of other comonomers include: Acrylamides, e.g. acrylamide,
Methylacrylamide, ethyl acrylamide,
Propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2- acetoacetoxyethyl) acrylamide, etc.; Methacrylamides, such as methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide,
Cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, N-(2-acetoacetoxy ethyl)
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 such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc. ; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile, methacrylonitrile, etc.; Multifunctional monomers, such as divinylbenzene, methylene bisacrylamide, ethylene glycol dimethacrylate, etc. Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates such as monomethyl maleate, monoethyl maleate, maleic acid, etc. monobutyl acid, etc.;
Citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; methacryloyloxyalkylsulfonic acid, such as , methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkylsulfonic acid,
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, for example 2-methacrylamido-2 -methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-
methacrylamide-2-methylbutanesulfonic acid, etc.; acryloyloxyalkyl phosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, Examples include 3-methacryloyloxypropyl-2-phosphate and the like; sodium 3-aryloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Additionally, other comonomers include U.S. Pat.
No. 3459790, No. 3438708, No. 3554987, No. 4215195, No. 4247673, JP-A-57-205735
Crosslinkable monomers described in the specification of the above publication and the like can be used. Examples of such crosslinking monomers include N-(2-acetoacetoxyethyl)acrylamide, N-{2-(2
-acetoacetoxyethoxy)ethyl}acrylamide, and the like. In addition, when a copolymer is formed with the monomer represented by the general formula [1] of the present invention and the comonomer, preferably the repeating unit consisting of the monomer represented by the general formula [1] is The content is preferably 10 to 90% by weight, more preferably 30 to 70% by weight of the total polymer. Generally, polymer couplers are polymerized by emulsion polymerization or solution polymerization, and the dye-imparting polymer of the present invention having a repeating unit derived from the monomer represented by the general formula [1] according to the present invention is also polymerized by emulsion polymerization or solution polymerization. It can be polymerized in a similar manner. Regarding the emulsion polymerization method, U.S. Patent No. 4080211;
The method described in US Pat. No. 3,370,952 and US Pat. No. 3,451,820 for dispersing a lipophilic polymer in an aqueous gelatin solution in the form of a latex can be used. These methods can also be applied to the formation of homopolymers and copolymers; in the latter case the comonomer may be a liquid comonomer, which in the case of emulsion polymerization normally also acts as a solvent for the immobilized monomer. . Examples of emulsifiers used in the emulsion polymerization method include surfactants, polymeric protective colloids, and copolymer emulsifiers. Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants known in the art. Examples of anionic activators include soaps, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium dioctylsulfosuccinate, sulfates of nonionic activators, and the like. Examples of nonionic surfactants include polyoxyethylene nylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxypropylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines. Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Examples of the polymeric protective colloid include polyvinyl alcohol and hydroxyethyl cellulose. These protective colloids may be used alone as emulsifiers or in combination with other surfactants. For information on the types of these activators and their effects, see Belgische
Chemische Industrie, 28, 16-20 (1963). In order to disperse a lipophilic polymer synthesized by a solution polymerization method or the like in the form of a latex in an aqueous gelatin solution, the lipophilic polymer is first dissolved in an organic solvent, and then dissolved in an aqueous gelatin solution with the help of a dispersant. Then, it is dispersed into a latex using ultrasonic waves, a colloid mill, etc. A method for dispersing lipophilic polymers in aqueous gelatin solutions in latex form is described in US Pat. No. 3,451,820. As the organic solvent for dissolving the lipophilic polymer, esters such as methyl acetate, ethyl acetate, propyl acetate, etc., alcohols, ketones, halogenated hydrocarbons, ethers, etc. can be used.
Moreover, these organic solvents can be used alone or in combination of two or more. In producing the dye-providing polymer according to the present invention, the solvent used for polymerization is a good solvent for the monomer and the produced dye-providing polymer,
It is desirable that the reactivity with the polymerization initiator is low. Specifically, water, toluene, alcohol (e.g. methanol, ethanol, iso-propanol, tert
-butanol, etc.), acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, dimethyl formamide, dimethyl sulfoxide, acetonitrile, methylene chloride, etc. These solvents may be used alone or in combination of two or more. good. The polymerization temperature needs to take into account the type of polymerization initiator and the type of solvent used, but it is usually 30 to 120℃.
is within the range of Examples of the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the dye-providing polymer of the present invention include those shown below. Examples of water-soluble polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, 4,4'-azobis-4-cyano(sodium valerate, 2,2'-azobis(2-amidino) water-soluble azo compounds such as propane) hydrochloride,
Hydrogen peroxide can be used. In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis(4- methoxy-2,4-dimethylvaleronitrile), 1,1'-
Azobis(cyclohexanone-1-carbonitrile), 2,2'-azobisisocyanobutyric acid, 2,
Dimethyl 2'-azobisisobutyrate, 1,1'-azobis(cyclohexanone-1-carbonitrile),
Azo compounds such as 4,4'-azobis-4-cyanovaleric acid, benzezoyl peroxide, lauryl peroxide, chlorobenzyl peroxide,
Diisopropyl peroxydicarbonate, di-
Examples include peroxides such as t-butyl peroxide. Among these, the preferred ones are:
Examples include benzoyl peroxide, chlorobenzyl peroxide, and lauryl peroxide. These polymerization initiators can be contained in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of monomers in emulsion polymerization and solution polymerization. Furthermore, polymerization methods other than the above-mentioned polymerization methods, such as suspension polymerization and bulk polymerization, can also be applied. That is, in the present invention, a dye-donating homopolymer of the monomer represented by the general formula [1] of the present invention, a copolymer formed by combining two or more of the monomers, or the monomer and other monomers It includes all copolymers comprising at least one polymerizable comonomer as a copolymerization component, and is not limited by the synthesis process. Specific examples of the dye-donating polymer that is the dye-donating substance of the present invention are shown in Table 1 below. Table-1 Monomer Comonomer
Composition ratio (monomer/comonomer) P-1 m-1 BA 5/5 P-2 m-1 BA 3/7 P-3 m-1 EA 5/5 P-4 m-2 St 4/6 P -5 m-4 BA 4/6 P-6 m-6 BA 5/5 P-7 m-8 BMA 4/6 P-8 m-10 BA 5/5 P-9 m-11 BA 5/5 P -10 m-11 MA 3/7 P-11 m-12 BA 4/6 P-12 m-12 OA 6/4 However, in Table-1, the abbreviations for comonomers represent the following. BA: Butyl acrylate EA: Ethyl acrylate St: Styrene BMA: Butyl methacrylate MA: Methyl acrylate OA: n-octyl acrylate Specific synthesis examples of the dye-donating polymer, which is the dye-donating substance of the present invention, are shown below. Synthesis example 2 Synthesis of exemplified polymer P-1 10 g of exemplified monomer (m-1) and butyl acrylate
10g was added to 200ml of dioxane and heated to 80-20°C while passing nitrogen gas. Maintain this temperature and add 300 mg of 2,2-azobisisobutyronitrile.
was added and reacted for 4 hours. After the reaction is complete, the reaction solution
Pour into 1.5 ml of water, filter and dry the precipitate, dissolve in 200 ml of dimethylformamide, and add again.
The precipitate was filtered and dried to obtain the desired dye-providing polymer P-1. The weight average molecular weight (M) of the dye-providing polymer of the present invention is preferably 3,000 or more, more preferably 4,000 to 200,000. The other dye-providing polymers P-2 to P-12 can be similarly synthesized based on the synthesis method for P-1 above. The heat-developable photosensitive material of the present invention contains photosensitive silver halide together with the dye-providing substance. Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The photosensitive silver halide can be prepared by any method used in the photographic field, such as a single jet method or a double jet method, but in the present invention, a conventional silver halide gelatin emulsion preparation method is used. Light-sensitive silver halide emulsions containing light-sensitive silver halides prepared accordingly give favorable results. The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The silver halide in the above-mentioned photosensitive emulsion may be coarse grain or fine grain, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.01 μm to about 1.5 μm. It is approximately 0.5 μm. The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention. In the present invention, as another method for preparing photosensitive silver halide, it is also possible to allow a photosensitive silver salt-forming component to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt. . The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, an _NH4 group, or a metal atom, and X represents Cl, Br). or represents I,
n indicates 1 when M is an H atom or an NH ₄ group, and indicates the valence when M is a metal atom. As a 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,
Examples include iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, and cerium. ), halogen-containing metal complexes (e.g.
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 (NH ₄ ) ₃ RuCl ₆ ,
(NH ₄ ) ₂ RhCl ₆ (NH ₄ ) ₃ RhBr ₆ , etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide) 4 like
ammonium halides, quaternary phosphonium halides such as tetraethyl phosphonium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g. iodoform , bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide,
N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo- 4,4-dimethylhydantoin, etc.), and other halogen-containing compounds (for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.). These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various methods, and the amount used is 0.001 g per m ² per layer.
It is preferable that it is ~50g, more preferably,
It is 0.1g to 10g. The heat-developable photosensitive material of the present invention has blue light, green light,
It is also possible to have a multilayer structure including each layer having sensitivity to red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. In addition, two or more photosensitive layers of the same color (for example, a high-sensitivity layer and a low-sensitivity layer)
It can also be divided into two parts. In the above cases, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, are prepared by adding various spectral sensitizing dyes to the silver halide emulsion. Obtainable. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine pigments, thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole,
Those having a basic core such as imidazole are more preferred. Such a nucleus may contain 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 fused carbocyclic or heterocyclic ring. good. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent. In addition to the above-mentioned basic nucleus, merocyanine dyes have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too. 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 derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as US Pat. No. 2,933,390,
A supersensitizing additive that does not absorb visible light, such as those described in the specification of No. 2937089, can be used in combination. The amount of these sensitizing dyes added is 1×10 ^-4 per mole of photosensitive silver halide or silver halide forming component.
mol to 1 mol. More preferably, 1×10 ⁻⁴
mole to 1×10 ⁻¹ mole. In the heat-developable photosensitive material of the present invention, various organic silver salts can be used, if necessary, in order to increase sensitivity and developability. Examples of organic silver salts used in the heat-developable photosensitive material of the present invention include Japanese Patent Publication Nos. 43-4921 and 44-26582;
No. 45-18416, No. 45-12700, No. 45-22185,
JP-A-49-52626, JP-A No. 52-31728, JP-A No. 52-
Publications such as No. 137321, No. 52-141222, No. 53-36224, and No. 53-37610, as well as U.S. Patent No.
Silver salts of fatty acid carboxylic acids such as silver laurate and silver myristate as described in the specifications of No. 3330633, No. 3794496, No. 4105451, No. 4123274, No. 4168980, etc. , silver palmitate, silver stearate, silver arachidonate, silver behenate, silver α-(1-phenyltetrazolthio)acetate, etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc. −26582 No. 45
-12700, 45-18416, 45-22185, JP-A-52-31728, JP-A-52-137321, JP-A-58-
Silver salts of imino groups such as those described in publications such as No. 118638 and No. 58-118639, such as silver benzotriazole, silver 5-nitrobenzotriazole,
5-chlorobenzotriazole silver, 5-methoxybenzotriazole silver, 4-sulfobenzotriazole silver, 4-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver,
benzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazole silver, 1,
2,4-triazole silver, 1H-tetrazole silver,
3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver,
Silver phthalimide, etc. Silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole, silver 2-mercaptobenzimidazole, silver 3-mercapto-4-phenyl-1,2,4-triazole,
4-hydroxy-6-methyl-1,3,3a,7
-tetrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver. Among the above organic silver salts, imino group silver salts are preferred, and silver salts of benzotriazole derivatives are particularly preferred, and silver salts of sulfobenzotriazole derivatives are particularly preferred. The organic silver salts used in the present invention may be used alone or in combination of two or more, and isolated ones may be used by dispersing them in a binder by appropriate means, or they may be used in a suitable form. The silver salt may be prepared in a binder and used as is without isolation. The amount of the organic silver salt used is 1 photosensitive silver halide.
Preferably, it is 0.01 to 500 mol per mol,
More preferably, it is 0.1 mol to 100 mol. The reducing agent used in the heat-developable photosensitive material of the present invention is oxidized by silver halide and/or organic silver salt, and the oxidized product of the reducing agent is a substrate (hereinafter also referred to as carrier) represented by X in the dye-donating substance. It is a so-called auxiliary developer, which can be used depending on the type of carrier used in the dye-donating substance of the present invention, or can be used for cross-oxidation together with the dye-donating substance of the present invention. Any reducing agent may be used as long as it is compatible. Useful reducing agents include, for example, phenidone (1
-phenyl-3-pyrazolidone), dimezone (1
pyrazolidones such as -phenyl-4,4-dimethyl-3-pyrazolidone), 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, aminophenols such as N-methylaminophenol, hydroquinone, ter- Hydroquinones such as butylhydroquinone, 2,5-dimethylhydroquinone, chlorohydroquinone, methoxyhydroquinone, N,N-diethyl-P-phenylenediamine, N,N,N,N-tetramethyl-P-phenylenediamine, etc. Examples include P-phenylene diamines, ascorbic acids, and reducing agents represented by the following general formula (43). General formula (43) In the formula, R ₃ and R ₄ are hydrogen atoms, or have 1 to 30 carbon atoms (preferably 1 carbon atom), which may have a substituent.
-4) represents an alkyl group, and R ₃ and R ₄ may be ring-closed to form a heterocycle. R ₅ , R ₆ , R ₇ and R ₈ are hydrogen atoms, halogen atoms, hydroxy groups,
Represents an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent, and R ₅ and R ₃ And R ₇ and R ₄ may each be ring-closed to form a heterocycle. M represents an alkali metal atom, an ammonium group, a nitrogen-containing organic base, or a compound containing a quaternary nitrogen atom. The nitrogen-containing organic base in the above general formula (43) is an organic compound containing a basic nitrogen atom capable of forming a salt with an inorganic acid, and particularly important organic bases include amine compounds. As chain amine compounds, primary amines, secondary amines,
Typical examples of cyclic amine compounds include pyridine, quinoline, piperidine, and imidazole, which are typical examples of heterocyclic organic bases. In addition, hydroxyamine,
Compounds such as hydrazine and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic acid salts of the organic base (eg, hydrochloride, sulfate, nitrate, etc.) as described above are preferably used. On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxides of nitrogen compounds having a tetravalent covalent bond. In the heat-developable photosensitive material of the present invention, it is preferable to use a dye release aid. The dye release aid is a compound that acts nucleophilically on the oxidized dye-donating substance to promote the release of the dye, and is preferably a base or a base precursor. The base is preferably an organic base, especially amines (such as dialkylamine, trialmylamine, hydroxylamine, fatty acid polyamine,
N-alkylaniline derivatives, N-hydroxyaniline derivatives, etc.) are preferred. As the base precursor, salts of carboxylic acids (eg, trichloroacetic acid, trifluoroacetic acid) and organic bases (eg, guanidine, piperidine, morpholine, toluidine, 2-picoline) are preferred, and guanidine trichloroacetic acid is particularly preferred. Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural polymers such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more molecular substances can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in Japanese Patent Application No. 104249/1982. This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or a copolymer (including a graft copolymer) of vinylpyrrolidone and one or more monomers copolymerizable with vinylpyrrolidone. It may be hot. These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone,
Preferred polyvinylpyrrolidone has a molecular weight of 1000~
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 imidazoles, (meth)acrylamides, and vinyl carbinols. , vinyl monomers such as vinyl alkyl ethers, etc., but it is preferable that polyvinylpyrrolidone accounts for at least 20% (weight %, same hereinafter) of the composition ratio. Preferred examples of such copolymers have a molecular weight of
5,000 to 400,000. Gelatin may be treated with lime or acid, and may be ossein gelatin, pitgskin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins. In the above binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%, more preferably 10 to 80% of the total binder amount. %. The binder may contain other polymeric substances, such as gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and a polymer with a molecular weight of 5,000 to 400,000.
A mixture of the vinyl pyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances that may be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, or proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Examples include natural substances. These range from 0 to 85%, preferably from 0 to 85%.
It may contain 70%. Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it naturally). The amount of binder used is usually 0.05g to 50g per square ^meter per layer, preferably 0.1g to 10g.
It is g. Examples of the support used in the heat-developable photosensitive material of the present invention include polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, and photographic base paper, printing paper, baryta paper, and resin coated paper. Examples include paper supports such as , and supports prepared by providing the above-mentioned synthetic plastic film with a reflective layer. In particular, it is preferable that various heat solvents be added to the heat-developable photosensitive material of the present invention. The thermal solvent of the present invention may be any substance that promotes thermal development and/or thermal transfer, and is preferably solid, semi-solid, or liquid at room temperature (preferably, with a boiling point of 100°C at normal pressure).
A substance that dissolves or melts in the binder by heating (preferably 150°C or higher), preferably a urea derivative (for example,
dimethylurea, diethylurea, phenylurea, etc.), amide derivatives (e.g. acetamide,
benzamide, etc.), polyhydric alcohols (e.g.
1,5-pentanediol, 1,6-bentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.),
Or polyethylene glycols can be mentioned. A detailed example is described in Japanese Patent Application No. 58-104249. These thermal solvents may be used alone or in combination of two or more. In addition to the above-mentioned components, various additives may be added to the heat-developable photosensitive material of the present invention, if necessary. For example, as a development accelerator, US Pat.
No. 3220840, No. 3531285, No. 4012260, No. 4060420, No. 4088496, No. 4207392, RD No. 15733, No. 15734, No. 15776,
Alkali release agents such as urea and guanidium trichloroacetate described in JP-A-56-130745 and JP-A-56-132332, organic acids as described in JP-A-45-12700, - as described in U.S. Pat. No. 3,667,959 CO−,−
Non-aqueous polar solvent compounds having SO ₂ -, -SO- groups, melt formers described in U.S. Pat. No. 3,438,776, polyalkylene glycols described in U.S. Pat. . In addition, as a color toning agent, for example, JP-A No. 46-4928,
No. 46-6077, No. 49-5019, No. 49-5020, No. 49
−91215, No. 49-107727, No. 50-2524, No.
No. 50-67132, No. 50-67641, No. 50-114217,
No. 52-33722, No. 52-99813, No. 53-1020,
No. 53-55115, No. 53-76020, No. 53-125014
No. 54-156523, No. 54-156524, No. 54-
No. 156525, No. 54-156526, No. 55-4060, No. 55
Publications such as -4061 and 55-32015, as well as West German Patent Nos. 2140406, 2147063, 2220618,
U.S. Patent No. 3080254, U.S. Patent No. 3847612, U.S. Patent No.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, which is a compound described in the specifications of No. 3782941, No. 3994732, No. 4123282, No. 4201582, etc. , 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, phthalic acid, naphthalic acid, phthalamic acid, etc., mixtures of one or more of these with imidazole compounds, and phthalic acid, naphthalic acid, etc. Examples include mixtures of at least one acid or acid anhydride and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like. Also, JP-A-58-189628, JP-A No. 58-189628,
3-amino-5-mercapto-1,2,4-triazoles and 3-acylamino-5-mercapto-1,2,4-triazoles described in Japanese Patent No. 193460 are also effective. Furthermore, as antifoggants, for example,
Special Publication No. 11113, No. 49-90118, No. 49-
No. 10724, No. 49-97613, No. 50-101019, No. 49
-130720, 50-123331, 51-47419,
No. 51-57435, No. 51-78227, No. 51-104338
No. 53-19825, No. 53-20923, No. 51-
No. 50725, No. 51-3223, No. 51-42529, No. 51-
Publications such as No. 81124, No. 54-51821, and No. 55-93149, as well as British Patent No. 1455271 and US Patent No.
3885968, 3700457, 4137079, 4138265, and West German Patent No. 2617907, or oxidizing agents (for example, N-halogen acetamide,
N-halogenosuccinimide, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), or
Acids and their salts (e.g., sulfuric acid, lithium laurate, rosin, diterpenic acid, thiosulfonic acid, etc.), or sulfur-containing compounds (e.g.,
mercapto compound releasing compound, thiouracil,
Disulfinic acid, simple sulfur, mercapto-1,
2,4-triazole, thiazolinthione, polysulfide compound, etc.), others, oxazoline,
Examples include compounds such as 1,2,4-triazole and phthalimide. Furthermore, as another antifoggant, thiol (preferably a thiophenol compound) compound described in JP-A-59-111636 is also effective. In addition, as an anti-fogging agent, Japanese Patent Application No. 59-56506
Hydroquinone derivatives (e.g. di-
(t-octylhydroquinone, dodecanylhydroquinone, etc.) or the hydroquinone derivatives described in Japanese Patent Application No. 59-66380 and benzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used. In addition, as a stabilizer, a printout preventive agent may be used at the same time, especially after processing.
No. 45228, No. 50-119624, No. 50-120328, No. 45228, No. 50-119624, No. 50-120328, No.
Halogenated hydrocarbons described in Publication No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromo Examples include methylsulfonylbenzothiazole and 2,4-bis(tribromomethyl)-6-methyltriazine. Also, JP-A-46-5393, JP-A-50-54329,
Post-treatment may be carried out using a sulfur-containing compound as described in each publication of No. 50-77034. Furthermore, U.S. Patent No. 3301678, U.S. Patent No. 3506444
The isothiuronium-based stabilizer precursor described in the specifications of No. 3,824,103, and No. 3844788, as well as U.S. Pat.
It may contain the activator stabilizer precursor described in the specification of the same No. 4060420 and the like. In addition, a water release agent such as sucrose, NH ₄ Fe (SO ₄ ) _{2.12H 2} O, etc. may be used.
Heat development may be carried out by supplying water as in JP 132332. In addition to the above-mentioned components, the heat-developable photosensitive material of the present invention may further include a spectral sensitizing dye, an antihalation dye, a fluorescent brightener, a hardening agent, an antistatic agent,
Various additives such as plasticizers and spreading agents, coating aids, etc. are added. The heat-developable photosensitive material of the present invention basically includes (1) photosensitive silver halide, (2) reducing agent, (3) in one photosensitive layer.
Dye-donor substance, (4) binder, and if necessary
(5) It is preferable to contain an organic silver salt. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, two photosensitive layers may be included.
The components (1), (2), (4), and (5) are contained in one photosensitive layer, and the dye-providing substance (3) is contained in the other layer adjacent to this photosensitive layer. ) may be contained separately in two or more photographic constituent layers as long as they are in a state where they can react with each other. Further, the photosensitive layer may be divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, and may further include one or more other photosensitive layers having different color sensitivities. It may also have various photographic constituent layers such as an overcoat layer, an undercoat layer, a backing layer, and an intermediate layer. Similar to the heat-developable photosensitive layer of the present invention, coating solutions are prepared for the protective layer, intermediate layer, undercoat layer, back layer, and other photographic constituent layers, using the dipping method, air knife method, curtain coating method, or Patent No.
Photosensitive materials can be prepared by various coating methods such as the hopper coating method described in No. 3681294. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. The above-mentioned components used in the photographic constituent layer of the photothermographic material of the present invention are coated on a support, and the coating thickness after drying is preferably 1 to 1000 μm, more preferably 3 to 20 μm. After the heat-developable photosensitive material of the present invention is imagewise exposed as it is, it is usually 80°C to 200°C, preferably 120°C to
Color development can be carried out by simply heating in a temperature range of 170° C. for 1 second to 180 seconds, preferably 1.5 seconds to 120 seconds. In addition, if necessary, it may be developed with a water-impermeable material in close contact with it, or it may be heated at 70°C to 70°C before exposure.
Preheating may be performed in the temperature range of 180°C. Various exposure means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. Light sources commonly used for regular color printing, such as tungsten lamps, mercury lamps, xenon lamps,
Laser beams, CRT beams, etc. can be used as light sources. As the heating means, all methods applicable to ordinary photothermographic materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, it is also possible to use high frequency heating, or furthermore, to provide a conductive layer in the photosensitive material of the present invention or in the image receiving layer (element) for thermal transfer, and to utilize the Joule heat generated by electricity or a strong magnetic field. The heating pattern is not particularly limited;
Although it is possible to preheat the temperature in advance and then reheat it, continuously raise, lower, or repeat heating at a high temperature for a short time, or at a low temperature for a long time, or even discontinuously, it is not easy. A pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used. In the present invention, the photographic constituent layer is imagewise exposed,
As the image-receiving layer that receives the diffusible dye that is imagewise generated by heat development, those commonly used in this field can be used, such as paper, cloth,
Although plastics and the like can be used, it is preferable to use a support provided with an image-receiving layer containing a mordant or a compound having dye-receiving ability. A particularly preferred image-receiving layer is one containing a mordant, and a polymer mordant is particularly preferred. Examples of polymer mordants that can be used in the present invention include polymers containing a quaternary amino group as described in U.S. Pat. Examples include covalently bonded reactive polymers described in JP-A-54-137333. [Specific Examples of the Invention] Examples of the present invention are shown below, but the embodiments of the present invention are not limited thereto. Example 1 7.4 g of Exemplified Polymer P-1 and 7.4 g of tricresyl phosphate (TCP) were heated and dissolved in 30 ml of ethyl acetate. Mix this solution with 30 ml of 5% gelatin aqueous solution containing surfactant, add water and
ml and then dispersed with a homogenizer to obtain a dispersion of the dye-providing polymer. 14 ml of the above dispersion was mixed with 7.0 ml of water containing 500 mg of polyvinylpyrrolidone (average molecular weight 30,000), 500 mg of polyethylene glycol (molecular weight 400), and 400 mg of 3-methylpentane-1,3,5-triol. ,4-dimethyl-3-
After adding 0.3 ml of a 10% methanol solution of pyrazolitone and 0.4 ml of a 10% ethanol solution of guanidine trichloroacetic acid, 2.5 x 10 ^-3 mol of silver iodobromide emulsion with an average grain size of 0.1 μm was added, Add water to 30ml
After finishing, a photosensitive layer was coated on a polyethylene terephthalate support using a wire bar to a dry film thickness of 8 μm, thereby obtaining photothermographic material sample No. 1. 16000CMS after drying the obtained photosensitive material sample No. 1
A white exposure of 200 mL was applied through the step wedge. Next, 250 ml of 10 g of poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) {the ratio of methyl acrylate to vinylbenzylammonium chloride is 1:1} was placed on baryta paper as an image receiving member. A mixture of 50 g of gelatin and 50 g of polyvinylpyrrolidone dissolved in water was coated and dried to a dry film thickness of 10 μm to obtain an image receiving member. The image-receiving layer surface of the image-receiving member and the photosensitive layer forming surface of the exposed photosensitive material sample No. 1 were superimposed, heat development was performed at 150° C. for 30 seconds, and the layers were peeled off to obtain a yellow transferred image on the image-receiving layer surface. . Table 2 shows the maximum reflection density (Dmax) and fog of the obtained transferred image. Example 2 [Preparation of silver 4-sulfobenzotriazole] 24 g of 4-sulfobenzotriazole and 4 g
of sodium hydroxide in ethanol-water (1:1)
It was added to 300 ml of the mixed solution and dissolved. 20 ml of 5N silver nitrate solution was added dropwise to this solution. At this time, 5N sodium hydroxide solution was also added dropwise at the same time to bring the pH to 7-8.
maintained. This solution was stirred at room temperature for 1 hour and then made up to 400 ml with water to prepare a 4-sulfobenzotriazole silver solution containing 20% excess of 4-sulfobenzotriazole. [Preparation of photosensitive material] Dispersion of dye-providing polymer P-1 of Example 1
Mix 8 ml of the above 4-sulfobenzotriazole silver solution with 12 ml, and add water containing 500 mg of polyvinylpyrrolidone (average molecular weight 30,000), 500 mg of polyethylene glycol (molecular weight 400), and 400 mg of 3-methylpentane-1,3,5-triol. 5ml
1-phenyl-4,4-dimethyl-
0.3 ml of 10% methanol solution of 3-pyrazolidone, 0.4 ml of 10% ethanol solution of guanidine trichloroacetic acid
ml was added and the pH was adjusted to 6.0 with 3% citric acid.
To this dispersion, 6 x 10 ^-4 mol of silver iodobromide emulsion with an average particle size of 0.1 μm was added in terms of silver, and water was added to 30 ml.
After finishing, a photosensitive layer was coated onto a polyethylene terephthalate support using a wire bar to a dry film thickness of 8 μm, thereby obtaining photothermographic material sample No. 2. After drying the obtained photosensitive material sample No. 2,
After a white exposure of 16,000 CMS was applied through a step wedge, thermal development was carried out on the same image receiving member as in Example 1 under the same conditions to obtain a yellow transferred image on the surface of the image receiving layer. Table 2 shows the maximum reflection density (Dmax) and fog (Dmin) of the obtained transferred image. Example 3 The photosensitive material of Example 2 was the same as Example 2 except that the dye-providing polymer P-1 was replaced with dye-providing polymers P-3, P-6, and P-7 shown in Table 1. Similar photosensitive material samples Nos. 3 to 5 were prepared and thermally developed in the same manner as in Example 2 to obtain transferred images of each dye on the surface of the image-receiving layer. The results of the obtained transferred image density are also shown in Table 2. Comparative Example 1 Photosensitive material samples No. 6 and 7 were prepared in the same manner as in Example 2 except that the dye-donating polymer P-1 in the photosensitive material of Example 2 was replaced with the following comparative compounds A and B. A transfer image of the dye was obtained on the surface of the image-receiving layer by carrying out heat development in the same manner as described above. The results of the transferred image density are shown in Table 2. (A) (B)

[Table] As is clear from the results in Table 2, the heat-developable photosensitive material samples (No. 1 to 1) using the dye-providing substance of the present invention
In 5), a sample using a comparative dye-adding substance (No.
6 and 7), the dye-providing substance was immobilized well, and contamination due to migration of the dye-providing substance itself to the image-receiving layer was reduced. Example 4 A photosensitive layer was prepared on a polyethylene terephthalate support in the same manner as in Example 2, except that the silver iodobromide having an average grain size of 0.1 μm was replaced with silver iodobromide having an average grain size of 0.125 μm and having green sensitivity. This was applied to form the first photosensitive layer. Next, 10 c.c. of 5% gelatin aqueous solution, 500 mg of polyvinylpyrrolidone (average molecular weight 30,000), 400 mg of polyethylene glycol (molecular weight 400) and 400 mg of 3-methylpentane-1,3,5-triol were mixed, and 15 c.c. After finishing, an intermediate layer was coated on the first photosensitive layer using a wire bar so as to have a dry film thickness of 2 μm. Next, silver halide in the first photosensitive layer is adjusted to an average grain size.
Silver iodobromide having a red sensitivity of 0.125 μm (the amount added is 1×10 ^-3 mol in terms of silver) was replaced with a dye-providing polymer of P-6 (the amount added was equimolar to P-1). ) was used as the second photosensitive layer to obtain heat-developable photosensitive material sample No. 8. Multilayer photosensitive material sample No. 8, in which the first photosensitive layer, intermediate layer, and second photosensitive layer were provided on the support as described above, was exposed to green light at 1600 CMS through a step wedge.
After red exposure and white exposure, heat development was performed in the same manner as in Example 2, and the image receiving member was peeled off. Dmax and Dmin) were measured. The results are shown in Table 3 below. Comparative Example 2 In the photosensitive material of Example 4, the dye-donating polymer P-1 in the first photosensitive layer was compared with Comparative Compound A used in Comparative Example 1, and the dye-donating polymer P-6 in the second photosensitive layer was compared. Example 4 except that compound B was used.
A photosensitive material sample No. 9 similar to the above was prepared, and exposed and thermally developed in the same manner as in Example 4. The results of the image density obtained are also shown in Table 3.

[Table] As is clear from the results in Table 3, photosensitive material sample No. 8 layered using the dye-donating substance of the present invention
Compared to comparative sample No. 9, the dye-donating substance is immobilized, so there is not only no contamination caused by the movement of the dye-donating substance itself to the image-receiving layer, but also color turbidity caused by movement to other layers. It can be seen that it has an excellent property of not causing any nuisance.

Claims (1)

[Claims] 1. At least photosensitive silver halide on a support,
In a heat-developable photosensitive material having a photographic constituent layer containing a reducing agent, a binder and a dye-providing substance,
At least one of the dye-donating substances has the following general formula:
A photothermographic material characterized in that it is a polymer having a repeating unit derived from the monomer represented by (1). General formula (1) Q-X-SO ₂ -Dye In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and X represents an oxidizable acyclic, carbocyclic or heterocyclic group. It represents a cyclic substrate, and Dye represents an image-forming dye residue.