JPH029332B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel heat-developable color photosensitive material,
More specifically, it relates to a thermocyclic image color photosensitive material that obtains an image by thermally transferring an imagewise distribution of a diffusible dye formed in a heat-developable photosensitive element to an image-receiving layer. The present invention relates to a heat-developable color photosensitive material that produces a magenta dye with good color and diffusivity, can obtain a transferred image of high density during thermal transfer, and has little fog. [Prior Art] The conventionally known color photography method using photosensitive silver halide is superior to other color photography methods in terms of photosensitivity, gradation, image preservation, etc., and is the most widely used color photography method. has been transformed into However, since this method uses wet processing for steps such as development, bleaching, fixing, and washing, processing is time-consuming and labor-intensive, and there are concerns that processing chemicals may pose a threat to the human body, or There are many problems, such as concerns about contamination of workers by treatment chemicals, and the labor and cost of waste liquid treatment. Therefore, there has been a demand for the development of a method for forming color images that allows dry processing. Black and white heat-developable photosensitive materials characterized by heat treatment in the development process have been known for a long time, and are described in, for example, Japanese Patent Publication Nos. 43-4921 and 43-4924. A photosensitive material comprising silver oxide and a developer is disclosed. Furthermore, many color heat-developable photosensitive materials are also known, to which this black-and-white photothermographic material is applied. For example, US Patent No. 3531286, US Patent No. 3761270
No. 3764328, Research Disclosure (hereinafter referred to as RD) No. 15108, No. 15127, Research Disclosure (hereinafter referred to as RD) No.
No. 12044 and No. 16479, etc., contain U.S. Patent No. 3180731 and RD No. 13443 regarding photothermographic materials containing photographic couplers and color developing agents.
and No. 14347, etc., regarding those using leuco dyes, U.S. Patent No. 4235957, RD No.
14433, same No.14448, same No.15227, same No.15776, same No.
No. 18137 and No. 19419 describe methods to which a silver dye bleaching method is applied, and U.S. Pat. . However, with these proposals regarding color heat-developable photosensitive materials, it is difficult or impossible to bleach or fix the simultaneously formed black, white, and silver images, or even if it is possible, wet processing is required. That is. Therefore, these proposals have many drawbacks, such as difficulty in obtaining clear color images and the need for complicated post-processing. As a method to improve the above-mentioned drawbacks, a heat development color photosensitive method is used, in which a diffusive or sublimable dye is released by heat development, and this dye is transferred to an image-receiving layer, thereby separating the silver image and the dye to obtain a color image. The materials are described in JP-A-57-179840, JP-A-57-186744, and JP-A-59-12431.
However, these methods, especially JP-A-57-
The methods described in No. 179840 and No. 57-186744 have the problem that the dye-providing substance is also transferred to the image-receiving layer at the same time as the dye is diffused, contaminating the image-receiving layer. If the dye-providing substance used in these products is a dye-releasing substance that releases a diffusible dye or a sublimable dye, the dye-providing substance itself is a colored compound, so contamination is particularly severe, and the dye-releasing substance is a colored compound. At times, unnecessary dyes are also transferred in addition to the formed dye image, which poses major problems such as contamination. This means that when the dye-providing substance is a dye-releasing substance, compared to the case where it is a dye-forming substance, the compound itself is colored and therefore has the disadvantage of severely contaminating the image-receiving layer. It means to have. Another problem is that when the dye-donating substance is a dye-releasing substance, compared to when it is a dye-forming substance, because the compound is colored, it becomes extremely desensitized. It also has From the above viewpoint, it can be said that dye-forming substances are preferable to dye-releasing substances as dye-providing substances used in heat-developable color light-sensitive materials. Furthermore, as pigment-forming substances, there are compounds described in, for example, JP-A-58-123533, JP-A-58-149046, and Japanese Patent Application No. 58-33364; Even if dye-forming substances are used, if the dye-forming substance itself is not sufficiently immobilized, it may cause contamination of the image-receiving layer. In this case, as long as the dye-providing substance can diffuse between layers, there is a problem that it causes color turbidity or poor color development. From the above viewpoint, it is absolutely unacceptable for the dye-providing substance to diffuse into the image-receiving layer or other layers during thermal development. Therefore, the dye-providing substance used in heat-developable color light-sensitive materials must be a sufficiently non-diffusible compound.
Particularly preferred are polymerized dye-donor materials that form diffusible dyes, such as those described in US Pat. However, the dye-providing substances described in the above specification, especially the dye-providing substances that form magenta dyes, have insufficient color development properties, making it impossible to obtain magenta dye images with high image density, and causing large fog. There were other drawbacks. [Object of the Invention] The present invention has been made in view of the above problems, and an object of the present invention is to provide a heat-developable color photosensitive material containing a novel dye-providing substance. 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. Still another object of the present invention is to provide a thermocyclic image color photosensitive material containing a magenta dye-providing substance that has high image density and low fog. [Structure of the Invention] As a result of intensive research to achieve the above object, the present inventors have developed a photographic constituent layer containing at least a photosensitive silver halide, a reducing agent, a binder, and a dye-providing substance on a support. The above object is achieved by a heat-developable color photosensitive material in which at least one of the dye-providing substances is a polymer having a repeating unit derived from a monomer represented by the following general formula []. I discovered that. General formula [] In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, X represents -CO-, and R ₁ represents an alkyl group, an aryl group, an amino group, an anilino group, an acylamino group or a ureido group. and Ar represents an aryl group or a heterocyclic residue. [Specific structure of the invention] In the general formula [ ], R ₁ is an alkyl group, an aryl group, an amino group, an anilino group,
Although it represents an acylamino group or a ureido group, these groups may have a substituent. Examples of the alkyl group represented by R ₁ include a methyl group and an ethyl group, examples of the aryl group include a phenyl group, and examples of the acylamino group include an acetylamino group, a butyrylamino group, and a benzoylamino group. etc. Substituents for the alkyl group, aryl group, amino group, anilino group, acylamino group, and ureido group include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, etc.), linear or branched alkyl groups (e.g. , methyl group, t-butyl group, etc.),
Alkoxy groups (e.g., methoxy groups, ethoxy groups, etc.), acylamino groups (e.g., acetylamino groups, benzamide groups, etc.), aryloxy groups (e.g., phenyloxy groups, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl groups, etc.), Examples include nitro group and hydroxy group. There may be two or more of these substituents, and in that case, these substituents may be the same or different. In the general formula [], Ar represents an aryl group or a heterocyclic residue;
The heterocyclic residue may have a substituent. Examples of the aryl group represented by Ar include a phenyl group, and examples of the heterocyclic residue include a pyridyl group, an imidazolyl group, and a benzothiazolyl group. Examples of substituents for the aryl group and heterocyclic residue represented by Ar include alkyl groups (e.g., methyl group, ethyl group, trifluoromethyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), aryl groups, etc. Oxy groups (e.g., phenyloxy groups, etc.), acylamino groups (e.g., acetylamino groups, etc.), carbamoyl groups (including carbamoyl groups with substituents; examples of substituted carbamoyl include methyl group substitution, ethyl group substitution, phenyl group) substituted carbamoyl, etc.), alkylsulfonyl groups (e.g., methylsulfonyl, etc.), arylsulfonyl groups (e.g., phenylsulfonyl, etc.), alkylsulfonamide groups (e.g., methanesulfonamide, etc.), arylsulfonamide groups (e.g. , phenylsulfonamide group, etc.),
A sulfamoyl group (including a sulfamoyl group having a substituent, examples of substituents for the sulfamoyl group include a methyl group, an ethyl group, a phenyl group, etc.), an alkylthio group (for example, a methylthio group, etc.), an arylthio group (for example, a phenylthio group, etc.) ), cyano group, nitro group, hydroxy group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), and there may be two or more of these substituents. The substituents may be the same or different. In the general formula [], Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and is preferably represented by the following general formula [] or []. General formula [] General formula [] In the formula, R ₂ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, a carboxyl group, or an alkoxycarbonyl group, and J represents 2
Represents a valent organic group or a simple bond, P is 2
Y represents an alkylene group or an arylene group, and this alkylene group or arylene group may have a substituent. R ₃ represents an alkylene group, and R ₄ represents a carboxy group or an alkyl group substituted with a carboxy group. m and n each represent 0 or 1. In the general formula [] or [], R ₂
represents a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, a carboxy group, or an alkoxycarbonyl group; however, as the alkyl group having 1 to 4 carbon atoms represented by _R2 , It may be a chain or branched alkyl group, such as a methyl group,
Examples include an ethyl group, an n-propyl group, an n-butyl group, and examples of substituents for this alkyl group include a carboxy group and a halogen atom. Examples of the alkoxycarbonyl group represented by R ₂ include a methoxycarbonyl group.
The carboxy group represented by R ₂ is NH ₄ , Na, K
Salts may be formed with etc. Preferably R ₂ is
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carboxy group, or an alkyl group having 1 to 4 carbon atoms substituted with a carboxy group. In the general formula [] or [], J represents a divalent organic group or a simple bond, but J
As the divalent organic group represented by, for example, -
CONH−, −COO−, −CH ₂ CONH−, −
Examples include CH ₂ COO−. J is preferably -
CONH−, −CH ₂ CONH−, is just a bond. In the general formula [] or [], the divalent organic group represented by P is, for example, -O
-, -S-, -NH-, _-SO2- , and the like. In the general formula [] or [], each Y represents an alkylene group or an arylene group which may have a substituent, but the alkylene group represented by Y may be linear or branched, and is preferably a carbon Examples of the alkylene group having 1 to 4 atoms include a methylene group, ethylene group, and propylene group. Examples of the arylene group represented by Y include a phenylene group. Substituents for the alkyl group and arylene group represented by Y include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, etc.), aryl groups (e.g., phenyl group, etc.), nitro group, hydroxyl group, cyano group, amino group, sulfo group, alkoxy group (e.g., ethoxy group, etc.), acyloxy group (e.g.,
acetoxy group, etc.), acylamino group (e.g., acetylamino group, etc.), sulfonamide group (e.g.,
methanesulfonamide group, etc.), sulfamoyl group (e.g., methylsulfamoyl group, etc.), carboxyl group, carbamoyl group (e.g., methylcarbamoyl group, etc.), alkoxycarbamoyl group (e.g., methoxycarbamoyl group, etc.), sulfonyl group (e.g. , methylsulfonyl group, etc.), ureido group, etc. There is no problem even if there are two or more of these substituents, and in that case, these substituents may be the same or different. In the general formula [], R ₃ represents an alkylene group, and examples of this alkylene group include a methylene group and an ethylene group. In the general formula [], R ₄ represents a carboxyl group or an alkyl group substituted with a carboxyl group, and this carboxyl group may form a salt. Examples of the alkyl group substituted with a carboxy group include an alkyl group having 1 to 4 carbon atoms, such as a methyl group and an ethyl group. In the general formula [] or [], m and n each represent 0 or 1, and may be combined arbitrarily. In the general formula [] or [], particularly preferably, the group represented by X is -CO-,
Furthermore, there is a case where a carboxy group is present at the β-position of -CO-. In this case, the resulting dye-providing substance has good color development and fog performance. A polymer having a repeating unit derived from the monomer of the present invention represented by the general formula [] forms a diffusible dye through a coupling reaction with an oxidized form of a reducing agent described later, which is also included in the present invention. However, in order to increase the diffusivity of the formed dye, 5-, which is a monomer of the general formula []
In pyrazolone derivatives, the molecular weight of the residue (magenta coupler core) excluding the substituent at position 4 is 700.
It is preferably 500 or less, more preferably 500 or less. Typical specific examples of the magenta dye-providing substance monomer represented by the above general formula [] used in the present invention will be described below, but the present invention is not limited thereto. Next, a specific synthesis example of the magenta dye-providing substance monomer represented by the general formula [] of the present invention will be shown. Synthesis Example 1 (Synthesis of exemplified monomer M-4) [Synthesis of intermediate] 1-phenyl-3-isobutyrylamino-4-
Synthesis of nitroso-5-pyrazolone 1-phenyl-3-isobutyrylamino-5-
24.5 g of pyrazolone was dissolved in 250 ml of acetic acid, and 10 g of sodium nitrite was added while stirring at room temperature. After stirring for 1 hour, the reaction mixture was poured into ice water, and the precipitated solid was collected to obtain 21.9 g of a reddish-orange solid, mp 199-201°C. [Synthesis of Exemplary Monomer M-4] 5.5 g of 1-phenyl-3-isobutyrylamino-4-nitroso-5-pyrazolone obtained above was dissolved in 100 ml of acetic acid, and 6.6 g of zinc was dissolved at room temperature under a nitrogen stream. was gradually added, followed by 2.5 g of itaconic anhydride. After stirring for 2 hours, the reaction product was filtered, and the filtrate was
ml of water, neutralized with sodium carbonate, and the precipitated solid was collected to obtain 5.6 g of the desired product. Synthesis Example 2 (Synthesis of Exemplary Monomer M-31) 1-phenyl-3-isobutyrylamino-4-
137 g of nitroso-5-pyrazolone was suspended in 1400 ml of ethyl alcohol, and while stirring, 1000 ml of an aqueous solution of 28.5 g of sodium hydrosulfite was added to 65
It was added dropwise at a temperature of ~70°C. After dropping, reflux for 30 minutes and add water.
1000 ml was added, cooled to room temperature, the precipitated white crystals were filtered, washed with 200 ml of water, and further washed with 200 ml of acetonitrile to give 1-phenyl-3-
115 g of isobutyrylamino-4-amino-5-pyrazolone was obtained. 26 g of the above amino compound and 22.2 g of nitrophenylsuccinic anhydride were added to 200 ml of acetic acid, reacted for 1 hour at room temperature, and the white crystals added to the water from 1 were filtered. 8.0 g of this solid was added to 100 ml of ethanol and subjected to hydrogen reduction using palladium/carbon as a catalyst, followed by filtration, concentration, and drying. The obtained solid was dissolved in 50 ml of acetonitrile and 3.5 ml of pyridine solution.
To this dissolution, 4.2 ml of methacrylic acid chloride was added dropwise while cooling with ice, and after the dropwise addition, the solution was stirred at room temperature for 1 hour. This solution was poured into 200 ml of water, 2 g of sodium carbonate was added thereto, and the mixture was stirred for 30 minutes, neutralized with dilute hydrochloric acid, and the precipitated white solid was filtered to obtain 6.4 g of the desired product. The structures of the intermediates and exemplified monomers M-4 and M-31 were confirmed by NMR, IR, and mass spectra. The polymer having repeating units derived from the monomer represented by the general formula [] of the present invention is a so-called homopolymer of repeating units composed of only one type of monomer represented by the general formula []. However, it may also be a copolymer that is a combination of two or more monomers represented by the general formula [], and further composed of one or more comonomers having an ethylenically unsaturated group that can be copolymerized. It may also be a copolymer. Examples of the comonomer having an ethylenically unsaturated group that can form a copolymer with the monomer represented by the general formula [] of the present invention include acrylic esters, methacrylic esters, vinyl esters, olefins, styrenes, Crotonate esters, itaconate diesters, maleate diesters, fumarate diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers ,
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-methoxypolyethylene 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 carproate, 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, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-butylmethacrylamide,
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, methoxy 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 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.
3459790 No. 3438708, No. 3554987, No.
Crosslinking monomers described in JP-A-57-205735, etc. can be used. Examples of such crosslinking monomers include N-(2-acetoacetoxyethyl)acrylamide, N-{2-(2-
Examples include acetoacetoxyethoxy)ethyl}acrylamide. Further, when forming a copolymer with the monomer represented by the general formula [] of the present invention and the comonomer, preferably the repeating unit consisting of the monomer represented by the general formula [] accounts for the total weight ratio. This is the case where it is contained in an amount of 10 to 90% by weight of the polymer, and more preferably 30 to 70% by weight. Generally, polymer couplers are polymerized by emulsion polymerization or solution polymerization, and the dye-coupling polymer of the present invention having a repeating unit derived from a monomer represented by the general formula [] according to the present invention is also polymerized in the same way. It can be polymerized by the following method. Regarding the emulsion polymerization method, see U.S. Patent No. 4080211 and U.S. Patent No. 3370952.
The method described in US Pat. No. 3,451,820 can be used for dispersing a lipophilic polymer in the form of a latex in an aqueous gelatin solution. 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 nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxypropylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines. Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Examples of the polymeric protective colloid include polyvinyl alcohol and hydroxyethyl cellulose. These protective colloids may be used alone as emulsifiers or in combination with other surfactants. For information on the types of these activators and their effects, 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, sodium 4,4'-azobis-4-cyanovalerate, and 2,2'-azobis(2-amidinopropane). ) Water-soluble azo compounds such as hydrochloride and hydrogen peroxide can be used. In addition, examples of lipophilic polymerization initiators 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, dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis(cyclohexanone-1-
carbonitrile), 4,4'-azobis-4-cyanovaleric acid, etc.; Examples include oxides. 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 [] of the present invention, a copolymer formed by combining two or more of the monomers, or a copolymer formed by combining two or more of the monomers 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 representative examples of the dye-providing polymer of the present invention are listed below, but the invention is not limited thereto. Exemplary dye-donating polymers A synthesis example of the dye-providing polymer of the present invention is shown below. Synthesis Example 2 Synthesis of exemplified dye-donating polymer (PM-1) 6 g of exemplified monomer (M-5) and 4 g of n-butyl acrylate were dissolved in 100 ml of dioxane, and heated to 80°C while introducing nitrogen gas. The mixture was then added to 150 mg of 2,2'-azobisisobutyronitrile and maintained at 81-83°C for an additional 5 hours. After the reaction is complete, pour the reaction solution into 500ml of water, filter out the precipitate, dry it,
The objective polymer PM-1 in the form of a white powder was obtained. Synthesis Example 3 Synthesis of exemplified dye-donating polymer (PM-2) 3 g of exemplified monomer (M-5) and vinylpyrrolidone for 7 were dissolved in 100 ml of dioxane, and heated to 80°C while introducing nitrogen gas. Then, 200 mg of 2,2'-azobisisobutyronitrile was added, and the temperature was maintained at 81-83°C for an additional 2 hours. Polymer precipitated as the reaction progressed. After the reaction was completed, the reaction mixture was cooled, and the precipitated polymer was filtered and dried to obtain the target polymer (PM-2) in the form of a white powder. The weight average molecular weight (M) of the dye-providing polymer of the present invention is preferably 1,500 to 100,000. The dye-providing polymer of the present invention may be used alone or in combination of two or more. The amount used is not limited and is determined depending on the type of the polymer, whether it is used alone or in combination of two or more, and whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more. However, for example, the amount used is
0.005g to 10g, preferably 0.05g to 5.0g per m ²
g can be used. The dye-providing polymer of the present invention can be incorporated into the photographic constituent layer of the heat-developable color light-sensitive material by any method. tricresyl phosphate, etc.), followed by long-wave dispersion, or dissolved in an alkaline aqueous solution (e.g., 10% sodium hydroxide aqueous solution, etc.), and then dissolved in mineral acid (e.g., hydrochloric acid or nitric acid, etc.). or after dispersing using a ball mill with an aqueous solution of an appropriate polymer (e.g., polyvinyl butyral, polyvinylpyrrolidone, etc.).
can be used. The heat-developable color photosensitive material of the present invention contains a photosensitive silver halide together with the dye-providing polymer of the present invention. 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 in the photographic field, such as a single-jet method or a double-jet method, but in the present invention, a conventional method for preparing a silver halide gelatin emulsion is used. The light-sensitive silver halide emulsions thus prepared 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
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 ,
( _NH4 ) _{3RhCl6 ,} ( _NH4 ) _{3RhBr6 ,} etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzyl quaternary ammonium halides such as ammonium bromide, quaternary phosphonium halides such as tetraethyl phosphonium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenation 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-bromoacetonitride, 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 0.002 mol to 10 mol per 1 mol of dye-providing substance monomer units. , more preferably 0.02 mol to 2.0 mol. The heat-developable color photosensitive material of the present invention only needs to have at least one layer containing the dye-donating polymer of the present invention. It is also possible to have a multilayer structure including a blue photosensitive layer for development, a green photosensitive layer for heat development, and a red photosensitive layer for heat development. In addition, two photosensitive layers of the same color are added.
It can also be divided into more than one layer (for example, a high-sensitivity layer and a low-sensitivity layer). 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, holobolar 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, oxazothiazolidione nucleus, barbituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too. These acidic nuclei further include alkyl groups, alkylene groups, phenyl groups,
It may be substituted with 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, supersensitizing additives that do not absorb visible light such as ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as those described in the specifications of US Pat. No. 2,933,390 and US Pat. No. 2,937,089, are used in combination. be able to. The amount of these dyes added is 1.times.10.sup. ^-4 mol to 1 mol per mol of silver halide or silver halide-forming component. More preferably, 1×10 ⁻⁴ mol to 1×
10 ^-1 mole. 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. Examples of organic silver salts used in the heat-developable color photosensitive material of the present invention include Japanese Patent Publication No. 43-4921 and Japanese Patent Publication No. 44-4921;
No. 26582, No. 45-18416, No. 45-1270, No. 45-
No. 22185, JP-A-49-52626, JP-A No. 52-31728,
No. 52-137321, No. 52-141222, No. 53-36224
No. 3330633, US Patent No. 3794496, and US Patent No. 4105451.
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, arachidone as described in the specifications of No. 4123274, No. 4168980, etc. acid silver,
Silver behenate, silver α-(1-phenyltetrazolethio)acetate, etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-26582,
No. 45-12700, No. 45-18416, No. 45-22185,
Silver salts of imino groups as described in JP-A-52-31728 and JP-A-52-137321, as well as in the specifications of JP-A-57-1065 and JP-A-57-1066, e.g. Benzotriazole silver, 5-nitrobenzotriazole silver, 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
-Silver tetrazole, silver 3-amino-5-benzylthio-1,2,4-triazole, silver saccharin, silver phthalazinone, silver phthalimide, etc., silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole Silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,
4-triazole silver, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene silver and 5-methyl-7-hydroxy-1,2,3,
Examples include 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 preferably 0.1 to 5 mol, more preferably 0.3 to 3 mol, per 1 mol of the dye-donating substance monomer unit. As the reducing agent used in the heat-developable color photosensitive material of the present invention, those commonly used in the field of heat-developable color photosensitive materials can be used, such as those disclosed in U.S. Pat. Specification, RD No. 12146, RD No. 15108, RD No.
15127 and p described in Japanese Patent Application Laid-Open No. 56-27132, etc.
- phenylenediamine type and p-aminophenol type developing agents, phosfluoramide phenolic type and sulfonamide phenolic type developing agents,
Further examples include hydrazone color developing agents. Further, color developing agent precursors and the like described in U.S. Pat. No. 3,342,599, U.S. Pat. As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula [ ] described in No. General formula [] In the formula, R ₅ and R ₆ are a hydrogen atom or a carbon atom number of 1 to 30 (preferably 1) that may have a substituent.
-4) represents an alkyl group, and R ₅ and R ₆ may be ring-closed to form a heterocycle. R ₇ , R ₈ R ₉ and
R ₁₀ is a hydrogen atom, a halogen atom, a hydroxy group,
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 ₇ and R ₅ And R ₉ and R ₆ 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 [] is an organic compound containing a nitrogen atom that exhibits basicity 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, compounds such as hydroxylamine, 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. Next, preferred specific examples of the reducing agent represented by the general formula [] are shown below. The reducing agent represented by the above general formula [] can be prepared by a known method, such as the Houben-Weyl Method.
It can be synthesized according to the method described in Organischen Chemie, Band XI/pages 2645-703. Other reducing agents as described below can also be used. For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-
p-aminophenol, etc.), sulfonamidophenols [e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4-(p-aminophenol, etc.) −
toluenesulfonamide) phenol, etc.], or polyhydroxybenzenes (e.g. hydroquinone, tert-butylhydroquinone, 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-dinitro-
2,2'-dihydroxy-1,1'-binaphthyl,
4,4'-dimethoxy-1,1'-dihydroxy-
2,2'-binaphthyl, bis(2-hydroxy-1
-naphthyl)methane, etc.], methylenebisphenols [e.g. 1,1-bis(2-hydroxy-
3,5-dimethylphenyl)-3,5,5-trimethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy- 3,5-di-tert-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tert-butyl-
5-methylphenyl)-4-methylphenol,
α-phenyl-α,α-bis(2-hydroxy-
3,5-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-tert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines. These reducing agents can be used alone or in combination of two or more. The amount of the reducing agent to be used depends on the type of photosensitive silver halide, the type of organic acid silver salt, and the type of other additives used, but it is usually based on 1 mole of dye-donating substance monomer unit. ranges from 0.05 to 10 mol, preferably
The amount is 0.1 to 5 moles. Examples of the binder used in the heat-developable color photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate,
polyvinyl alcohol, polyvinylpyrrolidone,
One or a combination of two or more synthetic or natural polymeric substances such as gelatin and phthalated gelatin 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 vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or one or two of other monomers copolymerizable with vinylpyrrolidone.
Copolymers with the above (including kraft copolymers)
It may be. These polymers can be used regardless of their degree of polymerization. The polyvinylpyrrolidone may be a substituted polyvinylpyrrolidone, with preferred polyvinylpyrrolidone having 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 accounts for 10-90%
preferably 20 to 60%
The polymer of the present invention preferably accounts for 5 to 90%, more preferably 10 to 80%. 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 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 range from 0 to 85%, preferably from 0 to 85%.
It may contain 70%. The above-mentioned vinylopyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it to stand). The amount of binder used is usually per 1 m ² of support.
The amount is 0.005g to 100g, preferably 0.01 to 40g. 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 the monomer unit of the dye-donating substance. Examples of the support used in the heat-developable color photosensitive material of the present invention include polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, photographic base paper, printing paper, baryta paper, and resin coating. Examples include paper supports such as paper. 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. 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. Patent 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., and mixtures of one or more of these with imidazole compounds, or 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, diterpene acid, neosulfonic acid, etc.), or sulfur-containing compounds (e.g.,
mercapto compound releasing compound, thiouracil,
Disulfide, 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, thiol (preferably a thiophenol compound) compound described in JP-A-59-111636 is also effective as another antifoggant. 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 Methylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-
Examples include 6-methyltriazine. 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 a substance that is solid at room temperature.
A semi-solid or liquid substance that dissolves or melts in the binder by heating, preferably a urea derivative (e.g. dimethylurea,
diethylurea, phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide, etc.),
Polyhydric alcohols (e.g. 1,5-pentanediol, 1,6-pentanediol, 1,2-cyclohexanediol, pentaerythritol,
trimethylolethane, etc.), or polyethylene glycols. 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, as an anti-fogging agent, patent application No. 59-56506
Hydroquinone derivatives (e.g. di-
t-octylhydroquinone, dodecanylhydroquinone, etc.) and hydroquinone derivatives and benzotriazole derivatives (e.g., 4-sulfobenzotriazole, 5-
carboxybenzotriazole, etc.) can be preferably used in combination. 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 stabilizer precursor described in the specifications of U.S. Pat. No. 3,824,103 and U.S. Pat. No. 3,844,788;
It may also contain an activator stabilizer breaker, etc., as described in No. 4,060,420. 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 No. 132332. The heat-developable color photosensitive material of the present invention further includes, depending on the components other than the above, 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 color photosensitive material of the present invention basically contains one photosensitive silver halide, two reducing agents, and three
It is preferable to contain a dye-donating polymer which is a magenta dye-providing substance of the present invention, a binder, and, if necessary, an organic silver salt. .
However, these do not necessarily need to be contained in a single photographic constituent layer; for example, the green-sensitive layer may be divided into two layers, and components 1, 2, 4, and 5 may be contained in one of the green-sensitive layers. The dye-donating polymer 3, which is the magenta dye-providing substance of the present invention, is contained in the other layer adjacent to this green-sensitive layer, as long as it is in a state where they can react with each other. They may be contained separately. Furthermore, the green 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 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, an intermediate layer, or a filter layer. The dye-donating polymer, which is the magenta dye-donating substance of the present invention, can be contained in the green-sensitive layer as described above, but is not limited thereto, and can be contained in other blue-sensitive layers or red-sensitive layers. It's okay. 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 layers of the heat-developable color light-sensitive material of the present invention are coated on a support,
The thickness of the coating is preferably 1 to 1000 μm after drying,
More preferably, it is 3 to 20 μm. After the heat-developable color photosensitive material of the present invention is subjected to imagewise exposure as it is, the temperature is usually 80°C to 200°C, preferably 120°C.
Color development can be achieved by simply heating for 1 second to 180 seconds, preferably 1.5 seconds, or 120 seconds at a temperature in the temperature range of .degree. C. to 170.degree. In addition, if necessary, it may be developed with a water-impermeable material in close contact with it, or it may be developed at 70% before exposure.
Preheating may be performed at a temperature range of 180°C to 180°C. Various exposure means can be used for the heat-developable color photosensitive material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. A light source commonly used for normal color printing,
For example, a tungsten lamp, a mercury lamp, a xenon lamp, a laser light source, a CRT beam, etc. can be used as the light source. 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 in advance and then reheat it, to heat it at a high temperature for a short time, or at a low temperature for a long time, continuously raising, lowering, or repeating it, and even discontinuously heating, there is a simple pattern. preferable. 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 imagewise produced by thermal ring imaging, 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.
As a particularly preferable image receiving layer, Japanese Patent Application No. 58-97907
The layer made of polyvinyl chloride described in No.
Examples include a layer made of polycarbonate and a plasticizer described in No. 58-128600. The image-receiving layer may be provided on the same support as the photographic constituent layer, in which case it may have a structure that can be peeled off from the photographic constituent layer after the dye has been transferred, or it may be provided on a separate support. There is no particular restriction on its formation, and any technique can be used. [Example] Examples of the present invention are shown below, but the embodiments of the present invention are not limited thereto. Example 1 285 mg of an exemplary dye-providing polymer (PM-1, weight average molecular weight M=4300) was dissolved in 2.8 cc of ethyl acetate. This solution was mixed with 3 cc of a 2.5% aqueous gelatin solution containing a surfactant, water was added to make 7.5 cc, and the mixture was dispersed with a homogenizer to obtain a dispersion of a dye-providing polymer. 7.5 cc of the above dispersion was mixed with 2.5 cc of water containing 450 mg of polyvinylpyrrolidone (average molecular weight 30,000) and 500 mg of 1,5-pentanediol, and after adding 200 mg of the reducing agent (R-3), 3% citric acid The pH was adjusted to 5.5 with acid. This dispersion has an average particle size of 0.1 μm.
1 x 10 ^-3 mol of silver iodobromide emulsion (containing 85 mg of gelatin) was added in terms of silver, and water was added to finish the emulsion to 15 c.c., and then it was coated on a polyethylene terephthalate support with a dry film thickness of 8 μm. A photosensitive layer was coated by applying with a wire bar so that the photosensitive layer was coated. After drying the resulting light-sensitive material, it was exposed to white light at 16,000 CMS through a step wedge. Next, the image-receiving layer surface of an image-receiving sheet on which polyvinyl chloride as an image-receiving layer material was separately coated on baryta paper and the coated surface of the exposed photosensitive material were superimposed and thermally developed at 150° C. for 1 minute to form an image-receiving sheet. was peeled off to obtain a magenta transferred image on the image-receiving sheet. Table 1 shows the maximum reflection density (Dmax) and fog (Dmin) of the obtained transferred image. Comparative Example 1 A photosensitive material was prepared in the same manner as in Example 1, except that PM-1, the dye-providing polymer, was replaced with Comparative Polymer A below, and heat developed in the same manner as in Example 1. I did it. The results are shown in Table-1.

[Table] As is clear from Table 1, in the heat-developable color photosensitive material that does not use an organic silver salt, in the test using the dye-donating polymer of the present invention, Dmax was larger and Dmin was smaller than in the comparative test. I understand. 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 to bring the pH to 7~7.
It was kept at 8. 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] The same dye-donating polymer as in Example 1 (PM-
Mix 7.5 cc of the dispersion of 1) with 4 ml of the above 4-sulfobenzotriazole silver solution, and then add 450 mg of polyvinylpyrrolidone (average molecular weight 30,000), 120 mg of polyethylene glycol (molecular weight 300), and 3-methyl-1,3,5- 420 mg of pentanetriol and the same reducing agent (R-3) used in Example 1
After adding 200 mg, the pH was adjusted to 5.5 with 3% citric acid. A silver iodobromide emulsion with an average particle size of 0.05 μm was added to this dispersion in an amount of 3×10 ^-4 mol in terms of silver (gelatin 75
After adding water to make up to 15 ml, the dry film thickness was
A photosensitive layer was coated to a thickness of 8 μm using a wire bar. The obtained photosensitive material was exposed in the same manner as in Example 1, and then thermal development was carried out on the same image-receiving sheet as in Example 1 under the same conditions to obtain a magenta transferred image on the image-receiving sheet. Table 2 shows the maximum reflection density (Dmax) and fog (Dmin) of the obtained transferred image. Example 3 A photosensitive material similar to that of Example 2 was prepared, except that the dye-donating polymer PM-1 in the photosensitive material of Example 2 was replaced with the dye-donating polymer shown in Table 2. A magenta transfer image was obtained on the image-receiving sheet by performing heat development in the same manner as described above. The results of the obtained transferred image density are also shown in Table 2. Example 4 In the photosensitive material of Example 2, reducing agents were added as shown in Table-2.
A photosensitive material similar to that in Example 2 was prepared, except that the reducing agent shown in 2 was used, and the same exposure and heat development as in Example 2 were carried out to obtain a magenta transferred image. The results of the obtained transferred image density are also shown in Table 2. Comparative Example 2 A photosensitive material similar to Example 2 was prepared, except that the dye-donating polymer PM-1 in the photosensitive material of Example 2 was replaced with the above Comparative Polymer A and the following Comparative Polymer B. A magenta transfer image was obtained on the image-receiving sheet by performing heat development in the same manner as described above. The results of the obtained transferred image density are also shown in Table 2.
Shown below.

[Table] As is clear from the results in Table 2, the heat-developable color photosensitive material of the present invention has a stable magenta transfer image with a higher maximum reflection density than the comparative sample, and further improved fogging. I was able to get Example 5 In the photosensitive layer of Example 2, the average particle size was 0.05 μm.
Coating was performed on a polyethylene terephthalate support in the same manner except that the silver iodobromide was replaced with silver iodobromide having an average grain size of 0.125 μm and a green sensitivity, and the dry film thickness was changed from 8 μm to 6 μm. There was one photosensitive layer. Next, 400 mg of Polymer 1 (CD' scavenger) shown below was dissolved in 1.2 cc of ethyl acetate, this solution was mixed with 3 c.c. of a 2.5% aqueous gelatin solution containing a surfactant, and water was added to give 6 c.c. After that, the mixture was dispersed with a homogenizer to obtain a dispersion of a dye-providing polymer. This dispersion was mixed with 450 mg of polyvinylpyrrolidone (average molecular weight 30,000), 120 mg of polyethylene glycol (molecular weight 300), and 3-methyl-1,3,5-
After mixing with 6 c.c. of an aqueous solution containing 420 mg of pentanetriol and 75 mg of gelatin and finishing with water to 15 c.c., coat the first photosensitive layer with a wire bar to a dry film thickness of 2 μm to form an intermediate layer. was painted. Next, the silver halide in the first photosensitive layer is adjusted to have an average grain size.
The same except that the emulsion of silver iodobromide with a red sensitivity of 0.125 μm (the amount added is 1×10 ^-3 mol in terms of silver) was replaced and the dye-providing polymer was replaced with Compound 1 below (amount added 500 mg). A photosensitive layer was applied to form a second photosensitive layer. The multilayer photosensitive material having the first photosensitive layer, intermediate layer, and second photosensitive layer provided on the support as described above was exposed to red light at 1600 CMS through a step wedge, and then thermally developed in the same manner as in Example 2. , peel off the image-receiving sheet, and measure the image density (Dmax and Dmin) with green light and red light for the obtained dye image.
was measured, and the results shown in Table 3 were obtained. Comparative Example 3 A photosensitive material was prepared in the same manner as in Example 5, except that the dye-donating polymer PM-1 in the first photosensitive layer was replaced with Compound 2 below, and the same procedure as in Example 4 was made. Exposure and thermal development were performed, and the results of the image density obtained are also shown in Table 3.

[Table] As is clear from the results in Table 3, in the photosensitive material layered using the dye-donating polymer of the present invention, it is thought that the dye-donating substance is immobilized compared to the comparative sample, and It can be seen that the film has an excellent property of not causing color turbidity due to migration of the dye donor to other layers to form a dye during development.

Claims (1)

[Scope of Claims] 1. A heat-developable color 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, wherein at least one of the dye-providing substances is A heat-developable color photosensitive material characterized by being a polymer having a repeating unit derived from a monomer represented by the following general formula []. General formula [] In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, X represents -CO-, and R ₁ represents an alkyl group, an aryl group, an amino group, an anilino group, an acylamino group or a ureido group. and Ar represents an aryl group or a radical ring residue.