JPS62129850A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of preventing a color turbidity and having an improved transfer property by providing an intermediate layer which contains 2 equivalent cyan polymer coupler having a repeating unit derived from a monomer shown by a specific formula between at least two layers of the photosensitive layer. CONSTITUTION:The titled material comprises at least two layers of the photosensitive layers which contain at least photosensitive silver halide, a reducing agent, a coloring matter affording substance capable of forming a diffusible coloring matter due to the heat development and a binder, and which have different combinations of a photosensitivity of the photosensitive silver halide and a hue of the formed coloring matter having the dispersibility with each other, and provided with a substrate. And the intermediate layer has substantially nonphotosensitivity and contains two equivalent cyan polymer coupler having the repeating unit derived from the monomer shown by the formula, and also capable of converting an oxidant to a passive state by reacting it with the oxidant of the reducing agent. Said intermediate layer is provided between said photosensitive layers, thereby obtaining the titled material having the improved transferring property of the image coming from the lowest layer of the photosensitive layers and also having a high reactivity for the oxidant of the color developing agent and contg. the oxidant scavenger.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a heat-developable color photosensitive material that forms a color image by transferring a dye formed by heat development, and in particular, a material that is free from color turbidity and has a good diffusion balance of diffusible dyes from each layer. This invention relates to an excellent heat-developable color photosensitive material. [Prior art] The conventionally known photographic method using photosensitive silver halide is superior to other photographic methods in terms of photosensitivity, gradation, image preservation, etc., and has been the most widely put into practical use. It is a photographic method. 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 chemicals mentioned above, and 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 demands. Regarding such heat-developable photosensitive materials, for example,
This is described in Japanese Patent No. 4921 and No. 43-4924, and discloses a photosensitive material 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, a heat-developable color photosensitive material that obtains a color image by transferring a diffusible dye released by heat development was published in Japanese Patent Laid-Open No. 57
-179840, 57-186744, 57-
No. 198458, No. 57-207250 and No. 59-
No. 12431, etc., and is also described in Japanese Patent Application No. 57-229649 filed by the present inventors. In these techniques, a dye-providing substance having a diffusible dye in the same molecule releases the diffusible dye through a heat development reaction of an organic silver salt and transfers the diffusible dye to an image-receiving layer to obtain a color image. On the other hand, the technology described in Japanese Patent Application No. 57-229671, No. 58-33363, and No. 58-33364 by the present inventors is that a colorless or light-colored dye-providing substance is a thermal development reaction of an organic silver salt. A heat-diffusible dye is formed by reacting with the oxidized product of the color developing agent produced by the process, and is transferred to an image-receiving layer to form a color image. In order to obtain a multicolor image using the above-described method, a multilayer structure is generally adopted, similar to conventional color photosensitive materials. For example, in a diffusion transfer photosensitive material for printing, the bottom layer is a blue photosensitive layer containing a yellow coupler, followed by a green photosensitive layer containing a magenta coupler, and the top layer is a cyan coupler. A red-sensitive layer is provided. To take an example of a practical product, in the case of Eftaflex (trade name, manufactured by Eastman Kodak Company), the bottom layer is a red photosensitive layer that emits a cyan dye, followed by a green photosensitive layer that emits a magenta dye. A blue photosensitive layer that emits a yellow dye is further provided on top, an intermediate layer is provided between each layer to prevent color turbidity, and a yellow filter layer is provided between the blue photosensitive layer and the green photosensitive layer. It is provided. As mentioned above, in order to make full-color heat-developable photosensitive materials, it is important to prevent color turbidity between each layer, and usually between the blue, green, and red photosensitive layers. By adding an intermediate layer to the surface, color muddiness is suppressed. However, in order to sufficiently suppress color turbidity, it is possible to increase the thickness of each intermediate layer or increase the number of polymers (such as gelatin) that can diffuse against the oxidized product of the color developing agent, thereby preventing release or formation. The transferability of the diffused dye to the image-receiving layer deteriorates. Although it has been known to use hydroquinones and catechols to prevent color clouding in conventional photography, no satisfactory technique for preventing color clouding is known for heat-developable photosensitive materials. For example, alkylhydroquinones such as those normally used in conventional silver halide emulsions are strong reducing agents and act as developers in heat-developable light-sensitive materials, which is unfavorable in terms of photographic properties. A multi-layer heat-developable color diffusion transfer photosensitive material which prevents color turbidity and has improved transferability from the bottom layer is disclosed in a patent application filed in 1983.
-86660 Mei II Mini, which contains an oxidant scavenger that is highly reactive with the oxidant of the color developing agent during thermal development and sufficiently non-diffuses the oxidant. The present invention provides a multilayer heat-developable color photosensitive material. However, the oxidant scavenger may have an unfavorable effect on the photographic properties of heat-developable color light-sensitive materials, and has the disadvantage that it decomposes the cyan dye produced from the cyan dye-donating substance, causing fading development. have. (Object of the Invention) Therefore, the first object of the present invention is to provide a heat-developable color photosensitive material in which color turbidity is prevented and transferability from a quantized layer is improved. A second object of the present invention is to provide a heat-developable color photosensitive material containing an oxidant scavenger that is highly reactive with the oxidant of a color developing agent during thermal development and sufficiently non-diffuses the oxidant. It is to provide. Furthermore, a third object of the present invention is to provide a novel scavenger for oxidized color developing agents that does not adversely affect the photographic properties of heat-developable color light-sensitive materials, and in particular does not cause cyan fading caused by cyan dye decomposition. An object of the present invention is to provide a heat-developable color photosensitive material containing: [Structure of the Invention] The above object of the present invention is to contain on a support at least a photosensitive silver halide, a reducing agent, a dye donor substance capable of producing a diffusible dye by heat development, and a binder; At least two photosensitive layers having different combinations of color sensitivity of silver halide and hue of the generated diffusive dye are provided.
In the heat-developable color photosensitive material having layers, a monomer represented by the following general formula (1) capable of reacting with the oxidized form of the reducing agent to immobilize the oxidized form between the at least 21!1 photosensitive layers. This was accomplished by providing a heat-developable color photographic material having a substantially non-photosensitive interlayer containing a 2-equivalent cyan polymer coupler having repeating units derived from. General formula (1) % formula % In the formula, R1 represents a hydrogen atom, a halogen atom, or an organic group, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and X represents an oxygen atom or a sulfur atom. , and Y represents an atomic group necessary to form a benzene ring or a naphthalene ring. [Specific Structure of the Invention] In the general formula (1), examples of the halogen atom represented by R1 include a chlorine atom, a fluorine atom, a bromine atom, and the like. In the general formula (1), the organic group represented by R1 is preferably an organic group having 1 to 36 carbon atoms, such as an alkyl group (for example, a methyl group, an ethyl group,

[-butyl group, etc.), aryl group (e.g., phenyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), alkylthio group (e.g., ethylthio group, etc.), allylthio group group (e.g., phenylthio group), acylamino group (e.g., acetylamino group, etc.), sulfonyl group (e.g., sulfamide group), alkoxycarbonyl group (e.g., ethoxycarbonyl group), or heterocyclic group M (e.g., pyridyl group, imidazolyl group, etc.)
can be mentioned. These organic groups represented by R; may have a substituent. Examples of these substituents include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups that may have substituents (e.g., methyl group, ethyl group,
trifluoromethyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), aryloxy group (e.g., phenyloxy group, etc.), acylamino group (e.g., acetylamino group, etc.), carbamoyl group (substituted carbamoyl group, etc.). Substituents include, for example, methyl group, ethyl group, phenyl group, etc.), alkylsulfonyl group (for example,
methylsulfonyl group, etc., arylsulfonyl group (e.g., phenylsulfonyl group, etc.), alkylsulfonamide group (e.g., methanesulfonamide group, etc.), arylsulfonamide group (e.g., phenylsulfonamide group, etc.), sulfamoyl group (substituted sulfamoyl group, etc.) containing a group;
As a substituent, for example, a methyl group, an ethyl group, a phenyl group, etc.), an alkylthio group (for example, a methylthio group, etc.)
, arylthio group (e.g., phenylthio group, etc.), cyam L nitro group, human0oxy group, etc., and there may be two or more of these substituents, and when there are two or more, they may be the same. May be different. In the general formula (1), Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, preferably a heterocycle having an ethylenically unsaturated group at the end or a group represented by the following general formula (2). It will be done. General formula (2) In the formula, R2 represents a hydrogen atom, a carboxy group, or an alkyl group (for example, a methyl group, an ethyl group, etc.), and this alkyl group may have a substituent, and as a Milk group,
Examples include halogen atoms (eg, fluorine atoms, chlorine atoms, etc.), carboxy groups, and the like. The carboxy group represented by R2 and the carboxy group of the fil substituent may form a salt. Jl and Jl each represent a divalent bonding group, and examples of the divalent bonding group include -NHC
O-1-CONH-1-COO-1-OCO-1-CO
-1-SCO-1-COS-1-0-1-S-1-SO
-1-S O2-, etc. V7 and ■2 each represent a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include an alkylene group, an arylene group, an aralkylene group, an alkylenearylene group, and an arylenealkylene group. For example, methylene group, ethylene group, propylene group, etc.
Examples of arylene groups include phenylene groups, examples of aralkylene groups include phenylmethylene groups, examples of alkylenearylene groups include methylenephenylene groups, and examples of arylenealkylene groups include phenylenemethylene groups. These are the basics. k,
J+, l+, and 1.12 each represent O or 1. In the general formula (1), X represents an oxygen atom or a sulfur atom that can be separated during the coupling reaction. In the general formula (1), Y represents an atomic group necessary to form a benzene ring or a naphthalene ring, and the formed benzene ring or naphthalene ring is preferably represented by the following general formula (3). General formula (3) In the formula, R, R4 and R5 are each an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an acylamino group, an alkoxyalkyl group ,
Aryloxyalkyl group, alkoxycarbonyloxy group, alkoxycarbonylamino group, alkoxycarbonyl group, carbamoylno group, alkylamino LL dialkylamino group, arylamino group, cycloalkylamino group, siam L nitro group, alkyloxyalkyl group, alkylsulfonyl group,
Arylsulfonyl group, water II, ureido group, sulfur 7
Represents a substituent selected from a moylamino group, an alkylsulfonyloxy group, an arylsulfonylamino group, an alkylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclic residue, an imide group, and a halogen atom, or a hydrogen atom. Furthermore, these substituents include hydroxyl group, alkoxy group, cyan group, nitro group, alkyl group, alkoxy group,
Aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, sulfo group,
It may be substituted with a carboxyl group, an acylamino group, an alkylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a sulfamoylami/I, an imide group, or a halogen atom. Furthermore, R3 and R+ may be combined to form a carbocyclic ring. In general formula (3), R3, R1 and R,5- are preferably an alkyl group, an aryl group, an alkoxy group,
A cyano group, an aryloxy group, an acyloxy group, an acyl group, an acylami LL alkylami LL dialkyl amimu L ureido group, a yakuchigen atom or a hydrogen atom, and particularly preferably R3 is a halogen atom (more preferably a chlorine atom). Also (fluorine atom) is also 4j hydrogen atom,
R+ is an alkyl group, and R5 is an acylamine / group. Typical specific examples of the single compound represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto. Below are the example monomers in the margin OOH OOH OOH ■ OOH ooh C00mu (SC) ict OOH OOH ool-1 QC) ic city CH2C0INk12 OOH oon 0OH OCHOCsH. OOH A typical synthetic route of the monomer represented by general formula (1) of the present invention is shown. 0 in parentheses represents the molecular weight (example of singular #C-1) (e) (228,5) (b) (234
)(C) (213,5)
(dλ (215,5) (e) (305,5)-11111111-------1------
---------------ge) (447,5)
(g) (357,5) (h) (285,5)
(C-1) (353,5)(a
) → (b) → (c) → (d) → (e) is a patent application filed in 1984-3.
It can be synthesized by the method described in Tomimini's No. 5238 specification. [(e) → (f) → (g)] (e) (10q, 0.0327 mol) and (i) (8,
0 (], 00.0360 mol was dissolved in 1 soJ of acetone, 12 (l) of potassium carbonate was added, and after refluxing for 6 hours, it was filtered and the filtrate was concentrated. To this I condensate was added 200 m of ethanol, il ! and hydrogenated using Pd/c as a catalyst, filtered and concentrated, and the obtained solid was recrystallized with acetonitrile to obtain the target product as a white powder. Yield (Q) 9.90 ( 0,0278 mol) Yield 85% [(Q)→(h)] (g) (9,5o, 0.0266 mol) was dissolved in a solution containing ethanol 40-1 water 20 tJl! and sodium hydroxide 6 g, After refluxing for 8 hours and stirring, it was poured into dilute hydrochloric acid and the acidic precipitated solid was collected by filtration and recrystallized from acetonitrile. Yield (h) 5,4o (0,01'89 mol)
Yield: 71% [(h)-P(C-1)] (h) (5,0Q 10.0175 mol) was dissolved in 20 IIL of acetonitrile, and pyridine (Liar K. 0
．． 0201 mol) is added. At 5°C, methacrylic acid chloride (21I, 0.0201 mol') was added dropwise. The mixture was stirred as it was for 1 hour, and then roughly stirred for 1 hour at room temperature. 2
1) H4 by adding concentrated hydrochloric acid to 50 water
The precipitated solid was collected by filtration and recrystallized from acetonitrile. Yield (C1) 3.2rJ (0,0094 mol)
Yield: 52% Synthesized compound has FD-mass spectrum, NMR1
Fixed by 1R and melting point measurements. The following margin: A polymer having a repeating unit derived from a monomer represented by the above general formula (1) of the present invention is a polymer having a repeating unit derived from a monomer represented by the above general formula (1). It may be a so-called homopolymer or a copolymer combining 2p1 monomers represented by the general formula (1) above, and furthermore, it may be a copolymer of a single 2p1 polymer represented by the general formula (1), and may also be a copolymer of a comonomer having an ethylenically unsaturated group that can be copolymerized. It may also be a copolymer consisting of more than one species. 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. , crotonic acid ester. Itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, monyl ketones, hynyl heterocyclic compounds, glycidyl esters, unsaturated nitriles,
Examples include polyfunctional monomers and various unsaturated acids. More specifically, these comonomers include methyl acrylate, ethyl acrylate, n-70 pylacrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, ter
t-Butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, ゛cyanoethyl acrylate, 2- 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-human O-oxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-(
2-methoxyethoxy)ethyl acrylate, 2-(2
-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of moles added n
-9) 1-70mo 2-methoxyethyl acrylate,
-1,1-dichloro-2-ethoxyethyl acrylate and the like. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, low-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and 5ec-butyl methacrylate. tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy) Ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2- and droxyethyl 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-is
o-Propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol Examples include methacrylate (additional mole number n-6), allyl methacrylate, and methacrylic acid dimethylaminoethylmethyl chloride salt. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc. Can be mentioned. Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, 2,3-dimethylbutadiene, and the like. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, vinylbenzoin-methyl ester, etc. can be mentioned. Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like. Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of other comonomers include: Acrylamides, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.: Methacrylamides, such as methacrylamide, methylmethacrylamide, ethylmethacrylamide amide, propylmethacrylamide, butylmethacrylamide, ter
t-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, N-(2-7cetoacetoxyethyl)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 ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone etc.: Vinyl heterocyclic compounds, such as vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles polyfunctional monomers such as divinylbenzene, methylenebisacrylamide, ethylene glycol dimethacrylate, etc. Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, heptanoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleate, such as monomethyl maleate, monoethyl maleate, maleic acid, etc. Acrylic acid monobutyl etc. ditraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; methacryloyloxyalkylsulfonic acid acids, such as niacrylamide alkyl sulfonic acids, such as methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropylsulfonic acid;
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.: Methacrylamide alkylsulfonic acid, for example, 2-methacrylamido-2 - methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloyloxyalkyl phosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2 - Phosphates, etc.: Methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.: Examples include sodium 3-allyloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali gold II (eg, Na, etc.) or ammonium ions. Further, other comonomers include U.S. Patent No. 3,459,790;
No. 3,438,708, No. 3,554,987, No. 4,215.195, No. 4,247,673
It is possible to use the crosslinking materials described in JP-A No. 57-205735, Akira Ill., and the like. Examples of such cross-linking monomers include N-
(2-acetoacetoxyethyl)acrylamide, N
/2-(2-acetoacetoxydiethoxy)ethyl)
Examples include acrylamide. Further, when a copolymer is formed by the monomer represented by the general formula (1) of the present invention and the comonomer, preferably the repeating units consisting of the monomer represented by the general formula (1) are at a ratio of 1tIl. 10-90% by weight of total polymer
It is a case where it is contained, and more preferably a case where it is contained in an amount of 30 to 70% by weight. Generally, polymer couplers are polymerized by an emulsion polymerization method or a solution polymerization method, and the cyan polymer coupler of the present invention having a repeating unit derived from a monomer represented by the general formula (I>) according to the present invention is also polymerized by an emulsion polymerization method or a solution polymerization method. The emulsion polymerization method is described in U.S. Pat.
No. 80211, No. 3,370,952, and U.S. Pat. No. 3,451,820 for dispersing lipophilic polymers in latex form in aqueous gelatin solutions. I can do it. 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,
Examples include sodium dioctyl sulfosuccinate and sulfates of nonionic surfactants. Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxypropylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines. Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Examples of the polymeric protective colloid include polyvinyl alcohol and hydroxyethylcellulose. These protective colloids may be used alone as emulsifiers or in combination with other surfactants. For information on the types of these active agents and their effects, see 3 elgisc.
he chersische industrie,
28.16-20 (1963). In order to disperse a lipophilic polymer synthesized by a solution polymerization method etc. 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 aid of a fractionating agent.

[The product is then dispersed into latex using ultrasonic waves, a colloid mill, etc. Lipophilic polymer and gelatin water? A method of dispersing it in latex form in liquid No. 17 is described in U.S. Pat. No. 3,451,820. Examples of organic solvents that dissolve lipophilic polymers include esters such as methyl acetate, ethyl acetate, propyl acetate, etc.
Alcohols, ketones, halogenated hydrocarbons, ethers, etc. can be used. Further, these i-solvents can be used alone or in combination of two or more. In producing the cyan polymer coupler according to the present invention, the solvent used in the polymerization is preferably one that is a good solvent for the monomer and the cyan polymer coupler to be produced and has low reactivity with the polymerization initiator. Specifically, water, toluene, alcohol (e.g. methanol, ethanol, 1s
o-propanol, tert-butanol, etc.), acetone, methyl ethyl ketone, dihydrofuran, dioxane, ethyl acetate, dimethyl formamide, dimethyl sulfoxide, acetonitrile, methylene chloride, etc. These solvents may be used alone or in combination with You may use a mixture of more than one species. Although it is necessary to consider the type of polymerization initiator, the type of solvent used, etc., the polymerization temperature is usually in the range of 30 to 120°C. Examples of the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the cyan polymer coupler of the present invention include those shown below. Examples of water-soluble polymerization initiators include perIII salts such as potassium perilate, ammonium persulfate, and sodium perlIM, sodium 4,4'-7zobis-4-cyanovalerate, and 2,2'-azobis(2- Water-soluble azo compounds such as (amidinopropane) hydrochloride and hydrogen peroxide can be used. In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisiso1thyronitrile, 2.2'-azobis-(2,4-dimethylvaleronitrile), 2.2'-azobis-(2,4-dimethylvaleronitrile),
'-azobis(4-methoxy-2,4-dimethylvaleronitrile>, 1,1'-azobis(cyclohexanone-
1-carbonitrile), 2.2'-azobisisocyano w1 acid, 2.2'-dimethyl azobisisobutyrate, 1,
Azo compounds such as 1'-azopis (cyclohexanone-1-carbonitrile), 4,4'-azobis-4-cyanovaleric acid, benzoyl peroxide, lauryl peroxide, chlorobenzyl peroxide, diisobrobyl peroxide Examples include peroxides such as carbonate and di-t-butyl peroxide. Among these, preferred are benzoyl peroxide, chlorobenzyl peroxide, lauryl peroxide and the like. These polymerization initiators can be contained in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total 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 homopolymer of the monomer represented by the general formula (I) of the present invention, a copolymer formed by combining two or more of the monomers, or a monomer of the monomer and at least one other
It includes all copolymers made of a species of polymerizable comonomer as a copolymerization component, and is not limited by the synthesis process. Specific representative examples of the cyan polymer coupler of the present invention will be listed below, but the invention is not limited thereto. Evening 1. Cyan polymer coupler (PC-1) C0OHMw= 12500 ()'C-2,1 (PC-3) C00C2H5 C,00HMW= 9500 (PC-4) Jis C00f( (PC-53 H3 0OI-1 (PC- 6) (PC-7) !V1w=10500 (PC-8) lyiw==12υO0 Below, a specific synthesis example of the cyan polymer coupler of the present invention is shown. , at 80°C. Said exemplary monomer (1) (5(1), acrylic acid -
Butyl (5 g) was added, and a polymerization initiator azobisisobutyronitrile <A IBN> (0,2a) was added to carry out solution polymerization. After 2 hours, more AIBN (0,1
c+) was added and reacted for 2 hours. Thereafter, it was poured into 1% saline solution and the suspended and insoluble matter was filtered off. Further, it was washed with water and dried, and the exemplified cyan polymer coupler (PC-1)
> obtained. Yield 1 9.4 (1, yield 94% White powder solid weight average molecule fliMw = 12,500 Residual monomer 0% Coupler content m 49% The molecular layer of the cyan polymer coupler of the present invention is a fallen average molecule! (M') ll) is preferably 1,500 to 100,000.The cyan polymer coupler of the present invention may be used alone or in combination of two or more.The amount used is not limited, and depends on the type of polymer, For example, the amount used is preferably 0.0005g to 2017, more preferably 0.01g to 5g based on the support 1112-. The cyan polymer coupler of the present invention can be incorporated into the photographic constituent layer of a heat-developable color light-sensitive material by any method. , tricresyl phosphate, etc.) and then subjected to ultrasonic dispersion, or after dissolving in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.),
Use it after neutralizing it with a mineral acid (e.g., hydrochloric acid or nitric acid), or after dispersing it in a ball mill with an aqueous solution of an appropriate polymer (e.g., polyvinyl butyral, polyvinyl pyrrolidone, etc.). I can do it. In the present invention, the repeatable 2-functional Russian polymer coupler derived from the monomer represented by the general formula (1) used as a reducing agent oxidized scavenger is a conventional silver halide color light-sensitive material. It is a polymer having a 2-equivalent coupler having a 5pI52 group in the active site of an active methylene compound such as a phenol compound or a naphthol compound in its side chain or backbone. The 2-equivalent cyan polymer coupler used here may have a size sufficient to non-diffuse the 2-equivalent cyan polymer coupler within the constituent layers of the photosensitive material of the present invention, and usually has a molecular weight of 1000 or more. , preferably 2000 or more, more preferably 5000 or more. These divalent cyan polymer couplers may be either hydrophilic or hydrophobic. In the case of a hydrophilic 2-equivalent cyan polymer coupler, it can be directly dissolved in the binder solution. In addition, in the case of a hydrophobic 2-equivalent cyan polymer coupler, after dissolving it in an organic solvent, it can be used in combination with a high-boiling point solvent (hydrophobic organic solvent with a boiling point of 200°C or higher) or without a high-boiling point solvent, using an ultrasonic dispersion machine, and colloid. Mechanical dispersion can be carried out using a mill or various homogenizers, or the 2-equivalent cyan polymer coupler itself can be synthesized in the form of a latex, and this can be mixed as is. As the 2-equivalent cyan polymer coupler preferably used in the present invention, for example, those listed in JP-A-58-211756 and the like can be used. Among these, hydrophilic polymer couplers have low solubility in water, etc.
Additionally, hydrophobic polymer couplers are more preferred because they have problems with compatibility with gelatin and other water-soluble polymers, and also have drawbacks such as greatly increasing the viscosity of the solution. The 2 equim cyan polymer coupler used in the present invention is:
The above-mentioned substances are substantially non-diffusible in the binder, and typical examples include the above-mentioned non-color-forming ethylenically unsaturated monomer and aromatic primary amine. Examples include copolymers with hydrophobic monomeric couplers that can couple with oxidized color developing agents to form dyes. Dye-providing substances that can be used in the present invention will be explained below. The dye-donating substance may be any substance as long as it participates in the reduction reaction of the photosensitive silver halide and/or the organic silver salt used as necessary and can form or release a diffusible dye as a function of the reaction. Depending on their reaction form, negative-acting dye-donors act on a positive function (i.e., form a negative dye image when negative-working silver halide is used) and positive-acting substances act on a negative function. It can be classified as a dye-providing substance (that is, it forms a positive dye image when negative-working silver halide is used). Negative dye-donating substances are further classified as follows. The dye-providing substances of each of the release-type compounds and formation-type compounds that release a diffusible dye when whitened are described below. Examples of the reducible dye-releasing compound include compounds represented by general formula (4). General formula (4) % formula % In the formula, Car is a reducing substrate (so-called carrier) that is oxidized and releases a dye upon reduction of the photosensitive silver halide and/or the organic silver salt used as necessary. , Dy
e is a diffusible dye residue. Specific examples of the above-mentioned reducing dye-releasing compounds include JP-A-57179840, JP-A No. 5g-116537, JP-A No. 59
-60434, 59-65839@, 59-71
No. 046, No. 59-87450, No. 59-88730
No. 59-123837, No. 59-165054, No. 59-165055, etc.
Examples include the following compounds. Below, examples of reducing dye-releasing compounds according to the margins include, for example, general formula (5).
Examples include compounds represented by: General formula (5-A! In the formula, A1% Ax each represents a hydrogen atom, a hydroxy group, or an amino group, and is synonymous with Dye shown in Dye tri general formula (4). One example of the above compound is It is shown in JP-A No. 59-124329. As the coupling dye releasing type compound, the general formula ((I
) The compound shown by is oxidized. General formula (6) % Formula % In the formula, CPt is a group (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, and B is a divalent group. is a bonding group, and the bond between CPt and B is cleaved by the reaction with the oxidized form of the reducing agent. n represents O or 1, and Dye has the same meaning as defined in general formula (4). In addition, Cpt is preferably substituted with various ballast groups in order to make the coupled dye-releasing compound non-diffusible, and the ballast group has 8 or more carbon atoms depending on the form of the photosensitive material used. (more preferably 12 or more) organic groups, or hydrophilic groups such as sulfo groups or carboxy groups, or 8 or more (more preferably 1)
2 or more carbon atoms] and a hydrophilic group such as a sulfo group or a carboxy group ring. Another particularly preferred ballast group can include polymer chains. Specific examples of the compound represented by the above general formula (6) include %1 No. 57-186744, No. 57-122596
No. 57-160698, No. 59-174834, No. 57-224883, No. 59-159159, and Japanese Patent Application No. 59-104901, for example, the following compounds are Can be mentioned. Exemplary dye-donor substance ■ OCR. (2) Examples of coupling dye-forming compounds include compounds represented by general formula (7). General formula (7) % formula %) In the formula, CPt is an organic group (coupling reaction) that can form a diffusive dye with the oxidant on the reducing side (coupling reaction).
D represents a divalent bonding group, and T represents a ballast group.The coupler residue represented by C20 must have a molecular weight of 700 or less due to the diffusivity of the dye formed. is preferable,
More preferably, the fi is less than 500. In addition, the ballast group is preferably the same as the ballast group defined in general formula (6), particularly 8 or more (preferably 12 or more) carbon atoms and a hydrophilic a group such as a sulfo group or a carboxy group. A group having both is preferred, and a polymer chain is even more preferred. As the coupling dye-forming compound having a polymer chain, a polymer having a silicate level at W*a from the monomer represented by the general formula (8) is preferable. General formula (8) Cp, +D-) (G\Z±±L) In the formula, CPt and D have the same meanings as defined in general formula (7), and G is an alkylene group, arylene group, or aralkylene 2 represents a divalent organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group. - Specific examples of coupling dye-forming compounds used in general formulas (7) and (8) include %1 1987-12433
No. 9, Publications No. 59-181345, and Patent Application No. 1983-
No. 109293, No. 59-179657, No. 59-1
No. 81604, No. 59-182506, No. 59-18
Examples of the compounds described in the specifications of No. 2507 include the following compounds. Exemplary color collection donor negative 0 CHC14H29 OOH ■ tsHss Polymer ■ Hs C city C00) ( [F] H3 ■ ◎ Hs (i-mountain y: 40% by weight?) I'' General formula (6), (7) above and (8), Cp
More specifically, the coupler h group defined by 1 or ClOs is preferably a group represented by the following general formula. General formula (9) General formula αυ
General formula (2) General formula (2)
General formula (b) 7 Rs General formula (f) - Mosquito 2 general formula a
In the general formula a, R8% R7, R1 and crow are respectively ice field atom, halogen atom, alkyl group, cycloalkyl group, aryl group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, aryl Represents a sulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amino group, alkoxy group, aryloxy group, cyan group, ureido group, alkylthio group, arylthio group, carboxy group, sulfo group, or a group to which Furthermore, hydroxyl group, carboxy group, sulfo group, alkoxy group, cyano group,
It may be substituted with a nitro group, an alkyl group, an aryl group, an aryloxy group, an acyloxy group, an acyl group, a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, or the like. . These substituents are selected depending on the purpose of Cpt and Cpz, and as mentioned above, in <CPt, one of the t substituents is preferably a ballast group, and in CI) In order to increase the molecular weight, it is preferable to select multiple groups so that the molecular weight is 700 or less, more preferably 500 or less. Examples of positive color patch-providing substances include oxidizable dye-releasing compounds represented by the following general formula (to). General formula (to) In the formula, Wl represents a V-centered atom forming a quinone ring (even if it has a substituent on this ring), and RIO represents an alkyl group or hydrogen ) represents 18O2-, r represents 0 or 1, Dye
has the same meaning as defined in general formula (4). Specific examples of this compound are JP-A-59-166954 and JP-A-59-166954;
For example, the following compounds are described in publications such as No. 154445. Exemplary Synthetic Donor Substance ■ H3 [Phase] QC)is Another positive dye-donating substance is a compound that loses its dye-releasing ability when oxidized, such as a compound represented by the following general formula. H in the formula represents a collection of atoms necessary to form benzene I (which may have a substituent on the ring), and R10
, E, I Dye have the same meaning as defined in the general formula (to). A specific example of this compound is JP-A-59-124
For example, the following compounds are described in publications such as No. 329 and No. 59-154445. Illustrative Dye Examples QC)is Still another positive dye-donor substance, the following general formula Q
Examples include compounds represented by 1). General formula Q1) In the above formula, Peng and Rhos Dye have the same meanings as those defined in the general formula. Specific examples of this compound are described in JP-A-59-154445, etc. 9
, for example, the following compounds have the following general formulas (4), (5), (6), (19), (2
The residue of the diffusible dye represented by Dye in 0) and (21) will be explained in further detail. The residue of the diffusible dye preferably has a molecular weight of 800 or less, more preferably 600 or less, for the sake of the diffusibility of the dye;
Examples include residues such as azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. These dye residues may be in a temporary short-waveform form that allows multiple colors during thermal development or transfer. In addition, these dye residues are used for the purpose of increasing the light resistance of images, for example, in
Chelatable dye residues described in No. 48765 and No. 59-124337 are also preferred. These dye-providing substances may be used alone or in combination of two or more. The amount used is not limited, and depends on the type of dye-providing substance, whether it is used alone or in combination, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more layers. It may be determined accordingly, but for example, the usage may be from 0.000 to 509 per ml, preferably from 0.000 to 509 per ml. I1 to 1 og can be used. The dye-providing substance used in the present invention can be incorporated into the photographic constituent layer of the heat-developable color light-sensitive material using any method. tricresyl phosphate, etc.),
Ultrasonic dispersion or alkaline aqueous solution (e.g.
Dissolve in a 10% aqueous solution of sodium hydroxide, etc.) and then neutralize with a mineral acid (e.g., hydrochloric acid or nitric acid, etc.).
or an aqueous solution of a suitable polymer (e.g. gelatin,
It can be used after being dispersed together with polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill. The heat-developable color photosensitive material of the present invention contains a photosensitive silver halide together with the compound of the present invention and the dye-providing substance. The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples include silver chloroiodobromide. The photosensitive silver halide is
Although it can be prepared by any method in the photographic field such as a single jet method or a double jet method, in the present invention, a photosensitive silver halide gelatin emulsion prepared according to method I11 of a conventional silver halide gelatin emulsion is used. A light-sensitive silver halide emulsion containing 0.05 to 1.5 g gives 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 include gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The silver halide in the above-mentioned photosensitive emulsion may be coarse grains or fine grains, but the preferred grain size is approximately 0.00 μm to approximately 1.5 μm, more preferably approximately 0.00 μm to approximately 1.5 μm in diameter. .01 μm to about 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 ll production method is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, NH4 group, or a metal atom, and X represents Cff1.Br or ■
When M is an H atom or NH41, n represents 1, and when M is a metal atom, n represents the valence thereof. Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, and lead. , antimony, bismuth,
Chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium,
Examples include osmium, iridium, platinum, and cerium. ), halogen-containing metal complexes (e.g., K2 Pt C
J! (,,K2 Pt B'6 , HAu CA. (NH) rrcu , (NH4)B Ird. 42, 6 (NH/,,)2 RLI G, (, (NH4
>3 Ru Cff1g. Otsu (NH4)3 Rh CjQ4, (NH4>3 R
h BrfS etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide,
4 such as trimethylbenzylammonium bromide
grade ammonium halides, quaternary phosphonium halides such as tetraethylphosphonium bromide,
Tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g., iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylbutane, etc.) , N-halogen compound 1i (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 (e.g., triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.)
etc. can be given. These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amount used is preferably 0.00113 to 50 g per layer, more preferably, 0.1g~10g
It is. The heat-developable color photosensitive material of the present invention has a multilayer structure including each layer sensitive to blue light, green light, and red light, that is, a heat-developable red-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. You can also. Further, the same color photosensitive layer can be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer). In the above case, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, can be obtained by adding various spectral sensitizing dyes to the silver halide emulsion. I can do it. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, viroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferred. Such nuclei include alkyl groups, alkylene groups,
It may contain a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, a phenyl group, an enamine group, or a heterocyclic substituent. In addition to the above-mentioned basic nucleus, merocyanine dyes include, for example, thiohydantoin nucleus, rhodanine nucleus, and oxazotool M @
, a thiazolinthione nucleus, a malononitrile nucleus, and an acidic nucleus such as a pyrazolone nucleus. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat. No. 2,933,390, U.S. Pat.
A supersensitizing additive that does not absorb visible light, such as those described in Specification 1 of No. 937,089, can be used in combination. The amount of these dyes added is from 10' mole to 1 mole of I x per mole of silver halide or silver halide forming component. More preferably, from 1 x 10"" moles to 1 x 10
~′mol. In the heat-developable color photosensitive material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability. Materials used in the heat-developable color photosensitive material of the present invention! 1m Salt Tot, T Ha, Special Publication No. 43-4921, No. 44-2
No. 6582, No. 45-18416, No. 45-1270
No. 0, No. 45-22185, JP-A No. 49-52626
No. 52-31728, No. 52-137321,
Publications such as No. 52-141222, No. 53-36224, and No. 53-37610, and U.S. Patent No. 3
．． No. 330,633, No. 3,794,496, No. 4,105,451, No. 4.123,274, No. 4,1ea, qao, etc. silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver valmitate, silver stearate,
Silver aromatic carboxylates such as silver arachidonic acid, silver behenate, silver α-(1-phenyltetrazolethio)acetate, etc., such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-2658
No. 2, No. 45-12700, No. 45-18416,
45-22185@, JP-A-52-31728, JP-A-52-137321, JP-A-58-118638,
Silver salts of imino groups, such as silver benzotriazole, 5
-Nitrobenzotriazole silver, 5-chlorobenzotriazole silver, 5-methoxybenzotriazole silver, 4-
Sulfobenzotriazole 14-hydroxybenzotriazole silver, 5-7Q nobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nidropenzimidazole silver,
Pyrazole silver, urazole silver, 1,2,41-riazole silver, 1H-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver,
Silver phthalazinone, silver phthalimide, etc., silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole, silver 2-mercaptobenzimidazole, 3-mercapto-4-7
enyl-1.2.4-triazole silver, 4-hydroxy-6-methyl-1,3,38,7-chitrazaindene silver and 5-methyl-7-hydrooxy-1,2,3,4,
Examples include 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 preferably 0.01 to 500 moles, more preferably 0.1 to 100 moles, per mole of photosensitive silver halide. The reducing agent used in the heat-developable color photosensitive material of the present invention is
Those commonly used in the field of heat-developable color photosensitive materials can be used; for example, those disclosed in U.S. Pat. No. 3,531,286
No. 3,761,270, No. 3,764.32
No. 8 specifications, and R D No. 12146,
Same No. 15108, No. 15127, and JP-A No. 15127
Examples thereof include p-phenylenediamine-based and p-7 minophenol-based developing agents, phosphoramidophenol-based and sulfonamidophenol-based developing agents, and hydrazone-based color developing agents described in Publication No. 27132 and the like. Also, U.S. Patent No. 3,342,599;
No. 719,492, JP-A No. 53-135628, No. 5
Color developing agent precursors described in No. 4-79035 and the like can also be advantageously used. As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula (22) described in No. In the formula, RI3 and R14 are hydrogen atoms, or have 1 to 30 carbon atoms (preferably 1 to 4), which may have a substituent.
represents an alkyl group, and R/3 and R74 may be ring-closed to form a heterocycle. R/, r, R/lR/'7 and Rlg are hydrogen atoms, halogen atoms, hydroxy groups, amino groups, alkoxy groups, acylamido groups, sulfonamide groups, alkylsulfonamide groups, or carbon atoms that may have substituents represents an alkyl group having 1 to 30 atoms (preferably 1 to 4), Rlr and R13 and R/'7 and J,
, 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 general formula (22) 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. Examples of chain amine compounds include primary amines, secondary amines, and tertiary amines, and examples of cyclic amine compounds include pyridine, quinoline, and piperidine, which are well-known examples of typical heterocyclic organic bases. , imidazole and the like. In addition, hydroxylamine,
Compounds such as hydrazine and amidine are also useful as chain amines. As the salt of the nitrogen-containing organic base, non-silicate salts of the organic bases mentioned above (eg, salt 11!! salt, sulfate, nitrate, etc.) are preferably used. Examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxides of nitrogen compounds having a tetravalent covalent bond. Margins below Next, preferred specific examples of the reducing agent represented by the general formula □□□ are shown below. (R-1) (R-2) (R-3) City C (R-4) Fs (R-5) (R-63 (R-7) (R-8) L (R-9) Hs (R-10) (R-11) (R-12) (R-13) H3 (R-14) (R-15) (R-16) (R-17) (R-18) (R-19 ) (R-20) (R-21) (R-22) IH5 (R-23) The reducing agent represented by the above general formula (22) can be prepared by a known method such as Houben-Weyl, Method
ender Organischen Chele
, Band X I/2, pp. 645-703. Other reducing agents as described below may also be used. For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-tert-
butyl-p-cresol, N-methyl-〇-aminophenol, etc.), sulfonamidophenols [e.g. 4-
Benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dipromo 4-
(p-toluenesulfonamide) phenol, or polyhydroxybenzenes (e.g. hydroquinone,
tert-butyl bidroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol) etc.), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1'-dihydroxy-2,2'
-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-sinitro2
, 2'-dihydroxy-1,1'-binaphthyl, 4.4
'-dimethoxy-1,1'-dihydroxy-2,2'-
binaphthyl, bis(2-hydroxy-1-naphthyl)methane, etc.], methylene-sphenols [e.g. 1.1-
Bis(2-hydroxy-3,5-dimethylphenyl)-
3゜5.5-trimethylhexane, 1.1-bis(2-
Hydroxy-3-t13rt-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-7
enyl-α, α-bis(2-hydroxy-3,5-di-tert-butylphenyl)methane, 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-tart)
-butylphenyl)propane, etc.], ascorbic acids,
Examples include 3-pyrazolidones, pyrazolones, hydrazones and paraphenylenediamines. These reducing agents can be used alone or in combination of two or more. The amount of reducing agent used depends on the type of photosensitive silver halide used, the type of FJ1 acid silver salt, and the types of other additives, but it is usually based on 1 mole of photosensitive silver halide. It ranges from 0.01 to 1500 mol, preferably from 0.1 to 200 mol. Binders used in the heat-developable color photosensitive material of the present invention include synthetic or natural binders such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, and phthalated gelatin. One or a combination of two or more polymeric 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 binder described in Japanese Patent Application No. 104249/1982. This binder includes gelatin and vinylpyrrolidone polymer. The vinyl pyrrolidone polymer may be polyvinyl and lolidone, which are homopolymers of vinyl pyrrolidone, or a copolymer of vinyl pyrrolidone and one or more other monomers copolymerizable (including kraft copolymers). ). These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone, and preferred polyvinylpyrrolidone has a molecular weight of 1.000 to 40.
0,000. 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. ,
Examples include vinyl monomers such as vinyl alkyl ethers, but it is preferable that polyvinylpyrrolidone accounts for at least 20% (weight %, same hereinafter) of the composition ratio. A preferred example of such a copolymer is that the molecule m is s, ooo
~400,000. The gelatin may be lime-treated or acid-treated, and may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins. In the above binder, gelatin preferably accounts for 10 to 90% of the total binder amount, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%.
It is preferably 10 to 80%, more preferably 10 to 80%. The binder may contain other polymeric substances,
Gelatin and molecules II 1,000-400,0001
7) Mixture of polyvinylpyrrolidone and one or more other polymeric substances, gelatin and molecules m s, ooo~4
A mixture of 00,000 vinylpyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances that can 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 may be contained in an amount of 0 to 85%, preferably 0 to 70%. Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to apply it onto a support and then crosslink it (including the case where the crosslinking reaction progresses by being left to stand). The amount of binder used is usually o, osg to 50 g per 1 m'' per layer, preferably o, ig to 50 g.
It is 10Q. Further, the binder is preferably used in an amount of 0.1 to 10 g, more preferably 0.25 to 4 g, per 1 g of one unit of the dye-providing substance monomer. Supports used in the heat-developable color photosensitive material of the present invention include, for example, polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic films such as polyvinyl chloride, photographic base paper, printing paper, baryta paper, and resin coating. Examples include a paper support such as paper, a support formed by providing a reflective layer on the above-mentioned synthetic plastic film, and the like. In particular, it is preferable that various heat solvents be added to the heat-developable color 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 or higher at normal pressure, more preferably 15°C).
0° C. or higher) and dissolves or melts in the binder by heating, preferably a urea derivative (e.g., dimethylurea, diethylurea, etc.):
leurea, etc.), amide derivatives (e.g., acetamide,
benzamide, etc.), polyhydric alcohols (e.g., 1,5
-bentanediol, 1,6-bentanediol, 1.
2-cyclohexanediol, pentaerythritol,
trimethylolethane, etc.), or polyethylene glycols. For a detailed example, see the patent application of 1983.
-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 color photosensitive material of the present invention, if necessary. For example, as a development accelerator, U.S. Pat.
No. 4,060,420, No. 4,088,49
6%, Transcript No. 4,207,392, RD N
o, 15733, No. o, 15734, No. 01
15776, JP-A-56-130745, JP-A No. 56-1
Alkali releasing agents such as urea and guanidium trichloroacetate described in No. 32332, etc., Japanese Patent Publication No. 1986-12
Organic acids described in '700, U.S. Pat. No. 3,667.959
Non-aqueous polar solvent compound having -co-, -802-, -5o- groups described in US Pat. No. 3,438,776
Meltformer-1 described in US Pat. No. 3,6G6,4
There are polyalkylene glycols described in No. 77 and JP-A-51-19525. In addition, as a color toning agent, for example, JP-A No. 46-4928, JP-A No. 4B-6077, JP-A No. 4
No. 9-5019, No. 49-5020, No. 49-912
No. 15, No. 49-107727, No. 50-2524
No. 50-67132, No. 50-67641@, No. 50-114217, No. 52-33722, No. 52
-99813, 53-1020, 53-55
No. 115, No. 53-76020, No. 53-1250
No. 14, No. 54-156523, No. 54-1565
No. 24, No. 54-156525, No. 541565
Publications such as No. 26, No. 55-4060, No. 55-4061, No. 55-32015, and West German Patent Nos. 2 and 1
No. 40,406, No. 2,147.063, No. 2,2
20,618, Unopened Patent No. 3,080,254, Patent No. 3,847,612, Patent No. 3,782,941,
Compounds such as phthalazinone, phthalimide, pyrazolone, quinazolinone, and N-hydroxy compounds described in the specifications of the same No. 3,994,732, the same No. 4,123,282, and the same No. 4,201.582, etc. naphthalimide,
Benzoxazine, naphthoxazinedione, 2゜3-
Dihydro-phthalazinedione, 2,3-dihydro-1,
3-oxazine-2,4-dione, oxypyridine, aminopyridine, human O-oxyquinoline, aminoquinoline,
Isocarbostyryl, sulfonamide, 2H-1,3-
These include benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimerkabutotetrazabentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., and the combination of one or more of these with an imidazole compound Examples include mixtures, mixtures of at least one acid or acid anhydride such as phthalic acid and naphthalic acid, and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, etc. . Also, JP-A-58-189028, JP-A-58-19346
3-amino-5-mercapto- described in Publication No. 0
1゜2.4-triazoles, 3-acylamino-5=
Mercap 1--1.2.4-triazoles are also effective. Furthermore, as an antifoggant, for example,
No. 7-11113, JP-A-49-90118, JP-A No. 49
-10724, 49-976i3, 50-1
No. 01019, No. 49-130120, No. 50-1
No. 23331, No. 51-47419, No. 51-574
No. 35, No. 51-78227, No. 51-104338
No. 53-19825, No. 53-20923, No. 51-50725, No. 51-3223, No. 51-
No. 42529, No. 51-81124, No. 54-518
Publications such as No. 21 and No. 55-93149, as well as British Patent No. 1.455,271, U.S. Patent No. 3,885,
No. 968, No. 3,700,457, No. 4,137
, No. 079, No. 4,138,265@, West German Patent No. 2
, 617,907, etc. [11] or oxidizing agents (e.g., N-halogenoacetamide, N-halogenosuccinimide, perchloric acid and its salts, inorganic peroxides, persulfates, etc.),
Alternatively, acids and their salts (e.g., sulfinic acid, lithium laurate, rosin, diterpene acid, thiosulfonic acid, etc.), or sulfur-containing compounds (e.g., mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur, mercapto-1, 2,4-triazole, thiazolinthione, polysulfide compounds, etc.), others,
Examples include compounds such as oxazoline, 1,2°4-triazole, and phthalimide. Furthermore, thiol (preferably a thiophenol compound) compound described in JP-A-59-111636 is also effective as another antifoggant. In addition, as other antifoggants, Japanese Patent Application No. 59-565
Hydroquinone derivatives described in No. 06 (e.g.
Hydroquinone derivatives such as t-octylhydroquinone, dodecanylhydroquinone, etc. and benzotriazole derivatives (for example, 4-
Sulfobenzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used in combination. In addition, as a stabilizer, a printout preventive agent may be used at the same time, especially after processing, for example, as disclosed in JP-A-48-45228, JP-A-50-119624, and JP-A-5G-120328.
Halogenated hydrocarbons described in No. 53-46020, specifically tetrabromobutane, tripromonitor seal, 2-bromo-2-tolylacetamide, 2
-Bromo-2-tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2.4-
Examples include bis(tribromomethyl)-6-methyltriazine. Also, Japanese Patent Publication No. 46-5393, Japanese Patent Publication No. 50-54329
Post-treatment may be carried out using a sulfur-containing compound as described in No. 50-77034. Furthermore, U.S. Patent No. 3,301,678;
506.444, 3,824.103, 3
, 844,788, as well as the isothiuronium-based stabilizer precursor described in U.S. Patent No. 3,6
No. 69,670, No. 4,012,260, No. 4,
It may contain the activator stabilizer precursor described in 060,420 and the like. In addition, sucrose, N Ht4- Fe(S 04 )2
- A water release agent such as 12H20 may be used, and furthermore, water may be supplied and heat development may be carried out as in JP-A-56-132332. In addition to the above-mentioned components, the heat-developable color photosensitive material of the present invention may further include various components such as a spectral sensitizer, an antihalation dye, a fluorescent brightener, a hardener, an antistatic agent, a plasticizer, and a spreading agent. Additives, coating aids, etc. are added. The heat-developable color photosensitive material of the present invention basically includes (1) photosensitive silver halide, (2) reducing agent, (
It is preferable to contain 3) a dye-providing substance, (4) a binder, and, if necessary, (5) an organic silver salt. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, the photosensitive layer may be divided into two layers, and the components (1), (2), (4), and (5) may be added to one layer. If the dye-providing substance (3) is contained in one side photosensitive layer and the other layer adjacent to this photosensitive layer contains the dye-providing substance (3), it is divided into two or more photographic constituent layers as long as they can react with each other. It may also be included. 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. As a preferred embodiment of the structure of the present invention, for example, red-sensitive silver halide, a reducing agent, an organic silver salt,
A red photosensitive layer consisting of a cyan dye-donating substance, an intermediate layer containing the compound according to the present invention thereon, and a green photosensitive layer consisting of a green-sensitive silver halide, a reducing agent, an organic silver salt, and a magenta dye-providing substance, Furthermore, thereon is an intermediate layer containing the compound according to the present invention, and blue-sensitive silver halide, a reducing agent, an organic silver salt, with or without a yellow filter layer.
An example is a gastric photosensitive layer made of a yellow dye-donating substance, which is coated in this order. If necessary, additives such as a development accelerator, a color toning agent, a thermal anticapsulant, and a thermal solvent may be added to these constituent layers of the multilayer heat-developable color diffusion transfer photosensitive material of the present invention. Preferably, it is added. Further, the scavenger (polymer coupler) of the oxidized color developing agent according to the present invention may be added not only to the intermediate layer but also to each photosensitive layer. Furthermore, when a single layer of yellow filter is provided in the constituent layers, the scavenger may be contained in this layer. A preferred embodiment of the present invention is a photosensitive layer integrated type having an image receiving layer on a support and one or more photosensitive layers on the layer, in which the image receiving layer is different from the photosensitive element. A mold that is configured as image receiving elements formed separately and is placed in contact with each other at least during diffusion transfer (the image receiving layer may also serve as a so-called support) and is observed as it is; Examples include a combination of a photosensitive layer and an image-receiving layer, which are separated from the photosensitive element. 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 U.S. The photosensitive material can be prepared by various coating methods such as the hopper coating method described in Japanese Patent No. 3,881.294. 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 layers of the heat-developable color light-sensitive material of the present invention are coated on a support, and the coating thickness is as follows:
After drying, the thickness is preferably 1 to 1,000 microns, more preferably 3 to 20 microns. The heat-developable color photosensitive material of the present invention can be used as it is in the image III!
After exposure to light, the temperature is usually 80°C to 200°C, preferably 120°C.
Color development is carried out by simply heating in a temperature range of -170°C for 1 second to 180 seconds r1, 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 180°C before exposure.
Preheating may be performed in the temperature range of °C. Various exposure means can be used for the heat-developable color photosensitive material according to the present invention. The latent image is radiation OA$ that includes visible light.
1 imagewise exposure. Generally, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source. As the heating means, all methods applicable to ordinary heat-developable photosensitive materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, high frequency heating may be used, or furthermore, a conductive layer may be provided in the photosensitive material of the present invention or in the image receiving layer (element) for thermal transfer, and Joule heat generated by electricity or a strong magnetic field may be utilized. There are no particular restrictions on the heating pattern, including preheating and then reheating, continuous rising, falling, or repeated heating at a high temperature for a short time, or at a low temperature for a long time, Although discontinuous heating is also possible, a simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used. The image receiving member used in the present invention only needs to have the function of receiving the dye released or formed by thermal development, and may be a mordant used in dye diffusion transfer type light-sensitive materials or JP-A-57-2
It is preferable to use a heat-resistant organic polymer material having a glass transition temperature of 40° C. or higher and 250° C. or lower as described in Japanese Patent No. 07250 or the like. Specific examples of the mordants include nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, quaternary cationic compounds thereof, U.S. Pat. Nos. 2,548,564 and 2,48
No. 4,430, No. 3,148,061, No. 3,756
, 814; vinylpyridine and vinylpyridinium cationic polymers disclosed in U.S. Patent No. 2,675,316; polymers containing dialkylamino groups disclosed in U.S. Pat. Aminoguanidine derivatives, JP-A-1987
Covalently reactive polymers described in US Pat.
! JQ, British Patent No. 1,277.453, British Patent No. 2,0
No. 11,012, a mordant capable of crosslinking with gelatin, etc.; U.S. Pat. No. 3,958,995;
721,852 and 2,798.063; water-insoluble mordants disclosed in JP-A-50-61228; and U.S. Patent No. 3,788.
, No. 855, West German patent comparison! 11 (OLS) No. 2,843
, No. 320, JP-A-53-30328, JP-A No. 52-15
No. 5528, No. 53-125, No. 53-1024, No. 54-74430, No. 54-124726, No. 55-22766, U.S. Patent No. 3,642.482, No. 3,488,706 , 3,557,066
No. 3.271,147, No. 3,271,148, Special Publication No. 55-29418, No. 56-36414,
Various mordants disclosed in No. 57-12139 and RD 12045 (1974) can be mentioned. Particularly useful mordants are polymers containing ammonium salts,
A polymer containing quaternary amino groups as described in US Pat. No. 3,709,690. Examples of polymers containing ammonium salts include polystyrene-N,N,N-tri-n-hexyl-N-vinylbenzylammonium chloride, and the ratio of styrene and vinylbenzylammonium chloride is 1:4 to 4:1; Preferably the ratio is 1:1. A typical image-receiving layer for dye diffusion transfer is obtained by coating a polymer containing an ammonium salt mixed with gelatin on a support. An example of the heat-resistant organic polymer substance is the molecule f! i
Polystyrene having a carbon number of 2,000 to 85,000, polystyrene derivatives having substituents having 4 or less carbon atoms, polyacetals such as polyvinylcyclohexane, polyvinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral. , polyvinyl chloride, chlorinated polyethylene, polytrichloride fluoroethylene,
Polyacrylonitrile, poly N, N-dimethylacrylamide, polyacrylate with p-cyanophenyl, pentachlorophenyl and 2,4-dichlorophenyl groups, polyacrylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, poly Isopropyl metal acrylate, polyisobutyl methacrylate, poly tert
- Polyesters such as butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyanoethyl metagelylate, polyethylene terephthalate, polysulfone,
Examples include polycarbonates such as sphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. Also, Po1ya+
er Handbook 2nd ed. (J, Brandrup, E, H, Iimer
gut Illi J 01ln Wi IeV & S O
Synthetic polymers having a glass transition temperature of 40° C. or higher, described in NS Publishing, are also useful. These polymeric substances are
They may be used alone or in combination of two or more as a copolymer. Particularly useful polymers include cellulose acetates such as triacetate and diacetate; polyamides in combinations such as heptamethylene diamine and terephthalic acid; fluorene dipropylamine and adipic acid; hexamethylene diamine and diphenic acid; hexamethylene diamine and isophthalic acid; Examples include polyesters made by combining diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, polyethylene terephthalate, polycarbonate, and vinyl chloride. These polymers may be modified. For example, polyethylene terephthalate using cyclohexane dimetatool, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy4-benzenesulfonic acid, etc. as a modifier is also effective. Among these, particularly preferred are the
Examples include a layer made of polyvinyl chloride as described in Japanese Patent Application No. 8-97907, and a layer made of polycarbonate and a plasticizer as described in Japanese Patent Application No. 128600/1982. The above polymer is used by dissolving it in a suitable solvent and coating it on a support to form an image receiving layer, or by laminating a film-like image receiving layer made of the above polymer on a support, or by coating it on a support. It is also possible to constitute the image-receiving layer by a member (for example, a film) made of the above-mentioned polymer alone (also used as an image-receiving layer support). Furthermore, the image-receiving layer may be constructed by providing an opaque layer (reflective layer) containing titanium dioxide or the like dispersed in gelatin on the image-receiving layer on a transparent support. This opaque layer provides a reflective color image when the transferred color image is viewed from the transparent support side of the image-receiving layer. In the following margin [Examples] Examples of the present invention are shown below, but the embodiments of the present invention are not limited to these. Example 1 Methyl alcohol 4 to benzotriazole silver 22.7Q
0oIIl elephant, 8% polyvinyl alcohol (Gohsenol AL-02 manufactured by Nippon Gosei Kagaku) aqueous solution 500+g f/
, and dispersed in a ball mill for 24 hours. Next, while stirring this dispersion, a silver halide emulsion (silver iodobromide emulsion with a silver iodide content of 5 mol%) sensitized to red was prepared.
, 60g of gelatin and average particle size of 0.1μ in 1kg of emulsion
containing 353 moles of silver containing m cubic silver particles) 2sIl
lλ was added to obtain a photosensitive dispersion. Further, 8.3 g of Exemplified Reducing Agent (R-1) as a reducing agent and the Exemplified Dye-Providing Substance 05 as a cyan dye-providing substance.
．． 64Q was dissolved in ethyl acetate 252-. This solution was mixed with a 2.5% gelatin aqueous solution 2eod containing a surfactant, water was added to make the solution 780-, and the mixture was dispersed with a homogenizer to obtain a dispersion of the dye-providing substance. This was combined with the photosensitive dispersion liquid to prepare a coating liquid. The coating solution prepared in this manner was coated and dried on a polyethylene terephthalate base coated with gelatin (3μ dry film thickness) (silver 15.21g/dra2), and then a 4% polyvinyl alcohol aqueous solution was applied on top of this with a wet coating of 111g/dra2.
1! An intermediate layer was applied and dried to a thickness of 55 μm. Next, in the same manner as above, except that green-sensitive silver halide of the same composition was used in place of red-sensitive silver halide according to the recipe of the first layer, and the exemplified dye-donor substance @ was used as the dye-donor substance, Again, the coating was coated and dried to a wet film thickness of 55 μm to obtain heat-developable photosensitive material sample 1. In place of the intermediate layer of Sample 1, 2.04 g of the following cyan polymer coupler was added to 5d of dibutyl phthalate, i5
m, 2 ml of ethyl acetate and 10 IIlλ of 5% aqueous alkanol XC (Dupont) aqueous solution added,
Ultrasonic dispersion in a 5% aqueous gelatin solution of Q, followed by 911. A sample 2 was prepared in the same manner as sample 1 except that a coating solution mixed with a 4% aqueous solution of polyvinyl alcohol was applied and dried to a wet film thickness of 55 μm to form an intermediate layer. Cyan Polymer Coupler Next, in place of the cyan polymer coupler used in the interlayer of Sample 2, illustrative 2-equivalent cyan polymer couplers (PC-1) and (PC-2) were each added at 3.92 (+
Samples 3 and 4 were obtained in the same manner except that both were used. In addition, an exemplary cyan polymer coupler (PC
-1> latex (latex polymer concentration 9.6%)
using 5 od of 4% polyvinyl alcohol water mm
Sample 5 is a sample obtained by replacing the intermediate layer of Sample-2 with an intermediate layer coated with 1oood and m and a wet aS thickness of 55 μl.
And so. Separately, a 5% solution of polyvinyl chloride in tetrahydrofuran (containing 10% by weight of dibutyl phthalate based on the polymer) was applied onto photographic baryta paper so that the amount of polyvinyl chloride was 1.20 (l) per 1 m''. Receiving paper was prepared. Samples 1.2.3.4 and 5 were each exposed to red light through a step wedge, and then the receiving paper and the coated surface were brought into close contact and developed at 160°C for 1 minute. The results of measuring red density and green density are
Shown in the table. Margin Table 1 (Red Light Exposure) As described above, in the samples of the present invention using the 2-equivalent cyan polymer coupler of the present invention in the intermediate layer, color turbidity is greatly improved. Then, it was reversely exposed to green light through a step wedge and developed in the same manner, and the results of green density and red density at the highest density area are shown in Table 2. Margin Table 2 (Green Light Exposure) As described above, in the samples of the present invention in which the 2-equivalent cyan polymer coupler of the present invention was used in the intermediate layer, color staining was greatly improved. Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural amendment (voluntary) March 19, 1985

Claims (1)

[Claims] On a support, at least a photosensitive silver halide, a reducing agent,
A photosensitive layer containing a dye-providing substance and a binder capable of producing a diffusible dye by heat development, and having different combinations of the color sensitivity of the photosensitive silver halide and the hue of the produced diffusible dye. In a heat-developable color photosensitive material having at least two layers, a unit represented by the following general formula (1) capable of reacting with an oxidant of the reducing agent to immobilize the oxidant is present between the at least two photosensitive layers. 1. A heat-developable color photosensitive material comprising a substantially non-photosensitive intermediate layer containing a 2-equivalent cyan polymer coupler having a repeating unit derived from a polymer. General formula (1) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents a hydrogen atom, a halogen atom, or an organic group, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, X represents an oxygen atom or a sulfur atom, and Y represents an atomic group necessary to form a benzene ring or a naphthalene ring.