JPS62169158A - Thermally developable color photosensitive material - Google Patents

Abstract

PURPOSE:To improve the color developability of a thermally developable color photosensitive material and to prevent fogging by incorporating a specified magenta coupler into the photosensitive material. CONSTITUTION:A magenta coupler represented by formula I (where Z is a group of atoms required to form a heterocyclic residue contg. N together with N, R1 is alkyl, aryl, alkylamino, anilino, acylamino or ureido, R2 is aryl or a heterocyclic residue and at least one between R1 and R2 is a ballast group or a group having a ballast group as a substituent) is incorporated into a thermally developable color photosensitive material having at least one thermally developable photosensitive layer on the support. When the magenta coupler represented by the formula I is monomer having an ethylenic unsatd. group or a group having an ethylenic unsatd. group as a substituent and is used as a copolymer of the monomer with other comonomer, the amount of the monomeric repeating units of the magenta coupler is preferably regulated to 10-90wt%, especially 30-70wt% of the amount of the copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a heat-developable color photosensitive material that forms an image by a thermal phenomenon, and specifically relates to a magenta coupler suitable for heat development that can form a dye image by heat development. The present invention relates to a heat-developable color photosensitive material containing the present invention.

['f of invention! 4 Kei J In recent years, heat-developable photosensitive materials that can be heat-treated in the development and processing steps have been attracting attention.

Regarding such heat-developable photosensitive materials, for example,
-4921@ and No. 43-4924 disclose a photosensitive material comprising an organic silver salt, silver halide, and an i-ball base agent.

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

For example, U.S. Patent No. 3,531.28G, U.S. Pat.
No. 61.210 and No. 3,764,328, etc.
Akiraff1l: yy in g? A thermal color photosensitive material is disclosed in which a color image is formed by a reaction between a 6/lXlX primary myamine developing main compound and a coupler.

Furthermore, Research Disclosure No. 15108 and No. 15127 discloses a heat-developable color photosensitive material in which a color image is formed by the reaction of a coupler with an oxidized product of sulfonamide phenol or sulfonamide aniline. has been done.

However, the magenta couplers used in the heat-developable color photosensitive materials disclosed in these publications, especially the 2 equim magenta couplers used to increase silver utilization efficiency, have significantly poor color development. Otherwise, it had the disadvantage of extremely high fog.

[Object of the Invention] An object of the present invention is to provide a magenta coupler for a heat-developable color photosensitive material that has good color development and less fog, and a heat-developable color photosensitive material 1'N having the coupler.

[Structure of the Invention] The above object of the present invention is to provide a heat-developable color photosensitive material containing a magenta coupler represented by the following general formula (1) in a heat-developable color photosensitive material having at least one heat-developable photosensitive layer on a support. This can be achieved using color photosensitive materials.

General formula (1) [In the formula, 2 represents an atomic group necessary to form a nitrogen-containing heterocyclic residue together with the N atom, and R1 is an alkyl group, an aryl group, an alkylamino group, an anilino group, an acylamino group, or It represents a ureido group, and R2 represents an aryl group or a heterocyclic residue. However, at least one of R+ and R2 is substituted with a ballast group or a ballast group. ] [Specific structure of the invention] In the general formula (1), Z represents an atomic group necessary to form a nitrogen-containing heterocyclic residue together with the N atom, but this nitrogen-containing heterocyclic residue further comprises: A fused ring may be formed with another carbocyclic ring (eg, benzene ring, etc.) or a heterocyclic residue. The nitrogen-containing heterocyclic residue is particularly preferably one having a carbonyl group adjacent to the nitrogen atom, such as a succinimide residue or a phthalimide residue. The nitrogen-containing heterocyclic residues include those having substituents, such as alkyl groups (e.g., methyl group, ethyl group, etc.), aryl groups (e.g., phenyl group).
, alkoxy group (e.g., methoxy group, ethoxy group, etc.)
, a nitro group, a sulfamoyl group (eg, diethylsulfamoyl group), a halogen atom (eg, chlorine, fluorine), and the like.

In the general formula (1), R1 represents an alkyl group, an aryl group, an alkylamino group, an anilino group, an acylamino group, or a ureido group; The ureido groups each include those having e Pj+ Jl, and examples of these substituents include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, etc.)
, linear or branched alkyl groups (e.g., methyl group, ethyl group, [-butyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), acylamino groups (1
For example, acetamido group, benzamide group, etc.), aryloxy group (e.g., phenyloxy group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, etc.), nitro group, hydroxy! There may be two or more of these substituents, and when there are two or more, they may be the same or different.

In the general formula (1), R2 is an aryl group or ?
! The aryl group represented by R2, which represents a dicyclic residue, includes, for example, a phenyl group, and the heterocyclic residue includes, for example, a pyridyl group, an imidazolyl group, a benzothiazolyl group, etc. .

The aryl group and heterocyclic residue represented by R2 each include a substituent, and these substitutions include, for example, H [1 atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.) , J even if it has a substituent, an alkyl group (
For example, methyl group, ethyl group, trifluoromethyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), aryl group (e.g., phenyloxy), acylamino group (e.g., acetylamino base'@)
, carbamoyl u (Fj Ii includes carbamoyl group, examples of substituents include methyl group, ethyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, etc.), arylsulfonyl group (for example, phenylsulfonyl group, etc.) groups, etc.), alkylsulfonamide groups (e.g., methanesulfonamide groups, etc.), arylsulfonamide groups (e.g., phenylsulfonamide groups, etc.), sulfamoyl groups (including substituted sulfamoyl groups, and substituents include, for example, methyl groups). , ethyl group, phenyl group, etc.),
Alkylthio group (e.g., methylthio, etc.), arylene group (e.g., phenylbu J13, etc.), cyano group, 21
・0 group, hydroxy u, etc. are mentioned, and these positions 1rA
There may be two or more u's, and when there are two or more u's, they may be the same or different.

In general formula (1), at least one of R1 and R2 is a ballast group or a group substituted with a ballast group. Here, the ballast group of the present invention refers to a damaged compound having a molecular size and shape that makes the magenta coupler non-diffusible in the heat-developable color light-sensitive material containing the magenta coupler during heat development. means. As a typical example of a ballast group, the total number of carbon atoms is 8 to 40 UA.
(more preferably 12 to 30 groups), and other particularly preferred ballast groups are polymer residues 1, -.

When the ballast group is a polymer residue, the magenta coupler represented by general formula (1) has a repeating unit derived from a monomer substituted with an ethylenically unsaturated group or a group having ethylenically unsaturated lT133. It is a useful polymer mappin coupler.

The ethylenically unsaturated group or ethylenically unsaturated group is preferably a group represented by the following general formula (2).

General formula (2) CH2=C-+Jl←→X1 Soup→J2 Masugan Sushi, 4
ml In the formula, R3 represents a hydrogen atom, a carboxy group, or an alkyl group (for example, a methyl group, an ethyl group, etc.), and this alkyl group also includes those having a substituent.
Examples include halogen atoms (eg, fluorine atoms, chlorine atoms, etc.), carboxy groups, etc. (The carboxy group represented by lR3 and the carboxy group of the substituent may form a salt.

Jl and J2 each represent a divalent bonding group, and examples of the divalent bonding group include -NHGO-1-CON
H-1-COO-1-OCO-1-SCO-1-COS
-1-0-1-S-1-SO-1-8O2-, etc.

×1 and ×2 each represent a divalent hydrocarbon group,
Examples of the divalent hydrocarbon group include an alkylene group, an arylene group, an aralkylene group, an alkylenearylene group, and an arylenealkylene group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and an arylene group. Examples of the group include phenylene group, etc., examples of the aralkylene group include phenylmethylene group, and examples of the alkylene arylene group.
For example, it is a methylene phenylene group, and the arylene alkylene group is, for example, a phenylene methylene group. Ri+, lIl+, Q2, m2 are each O
Or represents 1.

When the magenta coupler of the present invention is a polymer coupler, even if it is a so-called homopolymer of a repeating unit consisting of only one type of monomer coupler, it may contain more than two types of monomer couplers. F) It may be a copolymer, and II! ! It may also be a copolymer consisting of one or more comotours having an ethylenically unsaturated group that can be combined with i17.

A copolymer formed with the single M magenta coupler of the present invention and having the above-mentioned ethylenically unsaturated group [as the copolymer, acrylic esters, nucleic acid esters, vinyl nitrides, olefins, styrene fur r1,
Crotonate esters, itaconate diesters, maleate diesters, fumarate diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ethers, vinyl hetero-W1 ring compounds, glycidyl esters, unsaturated nitrites, Examples include functional monomers and various unsaturated acids.

To be more specific about these comonomers, the acrylic esters include mebru acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, ter
t-butyl acryle-1., amyl acrylate, hexyl acryle-1-12-ethylhexyl acrylate, octyl acryle-1., tert-octyl acryle-1-12-chloroethyl acrylate, 2-bromoethyl acrylate, 4-Chlorobutyl acrylate-1.
, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2
-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl 7 acrylate 1, tetrahydrofurfuryl 7 acrylate, phenyl acrylate, 5
-Hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutal acrylate, 2-ethoxyethyl acrylate-1~, 2-iso-propoxy acrylate, 2-bromoethyl Acrylate, 2-(2-methoxyethoxy)ethyl acrylate-1-
12-(2-butoxyethoxy)ethyl acrylate,
ω-Methoxypolyethylene glycol acrylate 1-(
Addition mole an=9) 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of nuccrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, Schiff O hexyl methacrylate, benzyl methacrylate-1.
, chlorobenzyl methacrylate, octyl methacrylate], sulfopropyl methacrylate, N-ethyl-
N-phenylaminoethyl methacrylate-1, 2-(3
-phenylpropyl 714=cy) nibble methacrylate, dimylaminophenoxyethyl methacrylate-1,
Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate-1, naphdyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate-1-11 to lyethylene glycol monomethacrylate, dipropylene glycol mono Methacrylate-1・,
2-methoxybutyl methacrylate, 3-methoxybutyl methacrylate, 2-aceto 4-dimethyl methacrylate 1-12-acetoacet 1-xyethyl 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 (number of moles added n-6), amyl Examples include acrylate, methacrylic acidified dimethylaminoethylmethyl chloride salt, and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl petyray 1-, vinyl isobutyrate, vinyl caprony], vinyl chloroahite-1, vinyl methoxya f! Art, vinyl phenyl ahitate, Ωffr positive vinyl, vinyl nalycylate, etc. are popular.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-1tene, 1-pentene,
331-hibinyl, JTA-ized vinylidene, isoprene, chlorobrene, bucdiene, 2,3-diethylbutadiene, and the like.

Styrenes include, for example, styrene, meboulstyrene, dimethylstyrene, [-rimeblestyrene, ethylstyrene, isoprobylstyrene, chloroethylstyrene, metho4cisstyrene, acetogystyrene, chlorstyrene, dichlorostyrene, Examples include promsdylene and vinylbenzoic acid methyl ester.

Examples of croton t, i esters include butyl crotonate, butyl crotonate, and the like.

Examples of diethyl itaconate include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of maleic acid diesters include diethyl maleate, dimebble 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, tart-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, human Oximebruacrylamide,
Methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide; methacrylamides, such as methacrylamide, methylmethacrylamide, ethyl Methacrylamide, propylmethacrylamide, butylmethacrylamide, [-butylmethacrylamide, cyclohexylacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, diethylacrylamide, diethyl Acrylamide, β-cyanoethymethacrylamide, N-(2-acetyl-acetyl-nitethyl)methacrylamide, etc.: Allyl compounds, such as allyl acetate, allyl turnipate, allyl laurate,
Allyl AnQ, etc.; Vinyl needles, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl sulfonic acid, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl Ketones, etc.; Vinyl heterocyclic compounds, such as vinylpyridine, N-vinylimidazole, N-vinyl Agisazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Saturated nitriles, such as acrylonitrile, methacrylate trile, etc.; polyfunctional t-mers
1 For example, divinylbenzene, styrene bisacrylamide, ethylene glycol dimethacrylate, etc.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; heptanoalkyl maleate, such as monomethyl maleate, monoethyl maleate, maleic acid; Acid L-butyl, etc. ditraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonate, acryloyl oxybu [■Bilsulfonic acid]
Methacryloyloxyallesulfonic acid, such as meccryloyloxymebrusulfonic acid, methacryloyloxymethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; Acrylamidoalkylsulfonic acid, such as 2-acrylamido-2-methylethanesulfonic acid, 2- Acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; Methacrylamide alkylsulfonic acid, such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methyl propanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloyloxyalkyl phosphate,
For example, acryloyloxyethyl phosphate-1-13
-acryloyloxypropyl-2-phosphate-1-, etc.; methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl 2-phosphate, etc.:
Examples include sodium 3-allyloxy-2-hydroxypropanesulfonate, which has two hydrophilic groups. These acids may be alkaline (eg, Na, etc.) or salts of ammonium ions. Further, other comonomers include U.S. Pat. No. 3,459,790
No. 3,438.708, No. 3,554,98
No. 7, No. 4.215.195, No. 4,247,6
Crosslinkable monomers described in JP-A No. 73, JP-A No. 57-20573, etc. can be used. Examples of such crosslinking monomers include N-
(2-7cetoacetoxyethyl)acrylamide, N-
(2-(2-7cetoacetoxyethoxy)ethyl)acrylamide and the like can be mentioned.

The magenta coupler represented by the general formula (1) of the present invention is a monomer substituted with an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and is a copolymer with another comonomer. In the case of a copolymer, the monomer content of the magenta coupler is 30 to 7011%.

Generally, polymer couplers are polymerized by emulsion polymerization or solution polymerization, and when the magenta coupler of the present invention is a polymer, the magenta coupler can also be polymerized by the same method. Regarding the emulsion polymerization method, U.S. Patent No. 4
．． No. 0130,211, No. 3.370,952,
Further, regarding a method of dispersing a lipophilic polymer in the form of a latex in an aqueous gelatin solution, US Pat. No. 3,451,
The method described in No. 820 can be used.

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

Emulsifiers used in the emulsion polymerization method include surfactants, polymeric protective fluids, 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 dioctyl sulfosuccinate, nonionic activator sulfur! Examples include salt.

Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, and boriogidi].

Examples include a tyrene-polyoxypropylene block copolymer. Further, examples of cationic activators include alkylpyridium salts, tertiary amine shorteners, and the like.

Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Further, examples of the polymeric protective colloid include polyvinyl alcohol, human O-oxyethylcellulose, and the like. These protective colloids may be used alone as emulsifiers or in combination with other surfactants. Regarding the types of these activators and their effects, please refer to Bergische Chemische x-Industrie (3clgische Ch.
28.113
-20 (1963).

To disperse a lipophilic polymer synthesized by a solution polymerization method in the form of a latex in an aqueous gelatin solution, the lipophilic polymer is first dissolved in a clear solvent, and then dissolved in an aqueous gelatin solution with the help of a dispersant. Then, it is dispersed into latex using ultrasonic waves and a colloid mill. A method of dispersing a lipophilic polymer in the form of a latex in an aqueous solution of olefin is described in Yoneda Special Edition No. 3.451.820.

As the organic solvent for dissolving the lipophilic polymer, esters such as methyl acetate, ethyl acetate, propyl 61-ate, etc., alcohols, carbons, 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 magenta polymer coupler of the present invention, the solvent used for polymerization is preferably a solvent that is a good R11 medium for the monomer and the produced magenta polymer coupler and has low reactivity with the polymerization initiator. Specifically, water, l
- toluene, alcohol (e.g. methanol, ethanol, 1so-propanol, tert-butanol, etc.),
Examples include acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, dimethylborumamide, dimethyl sulfoxide, acetonyl-lyl, methylene chloride, etc., and these solvents can be used alone or in a mixture of two or more. You may.

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 magenta polymer coupler of the present invention include those shown below.

Examples of water-soluble polymerization initiators include potassium persulfate, ammonium persulfate, and perIII! tr! Use perw&m salts such as IJ sodium, water-soluble azo compounds such as sodium 4,4'-azobis-4-cyanovalerate, 2,2'-azobis(2-amidinopropane) hydrochloride, and hydrogen peroxide. I can do it.

In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobutyronitrile, 2.2'-azobis-(2,4-dimethylvaleronitrile), 2.2
' -azobis(4-methoxy-2,4-dimethylvaleronitrile), 1.1'-azobis(cyclohexanone-1-carbonitrile), 2.2' -azobisisocyanobutyric acid, 2.2'- Dimethyl azobisisobutyrate, 1.
1'-azobis(cyclohexanone-1-carbonitrile), 4,4'-azobis-4-cyano azo compound of ancient grass, benzoyl peroxide, lauryl peroxide, [] lobenzyl peroxide, Examples include peroxides such as diisopropylberoxydicarbonate and di-t-butyl peroxide. Among these, preferred are benzoyl peroxide,
Examples include chlorobenzyl peroxide and lauryl peroxide.

These polymerization initiators are used in an amount of 0.01 to 10mff1% based on the total a of seven polymers in emulsion polymerization and solution polymerization.
It can be contained in a range of, preferably 0.1 to 5 [i%].

Furthermore, polymerization methods other than the above-mentioned polymerization methods, such as suspension polymerization and bulk polymerization, can also be applied.

Typical specific examples of the magenta coupler represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto.

To Exemplified Compound-I
A typical synthesis example of the magenta coupler represented by the general formula (1) of the present invention will be shown below.

Synthesis Example-1 Synthesis of Exemplified Compound M-3 1-phenyl-3-amino-5-pyrazolone, 35(l
was added to a mixed solvent of 300 g of acetonitrile and 20 g of acetonitrile, and a mixed solution of α-(2,4-di-tert-pentylphenoxy) chloride 70a and 2001 g of acetonitrile was added dropwise with stirring, followed by further 1 hour. The mixture was heated to reflux.

This reaction solution was cooled, and the precipitated solid was filtered off and dried.

47.713 of this solid was added to 200 g of acetic acid, and while stirring, 8 g of internitrous soda was added at below 25° C., and the mixture was stirred roughly for 2 hours at air temperature. This reaction solution was added to 600*(l) of water, and the precipitated solid was filtered off.
After dissolving Q in acetic acid 2501 and gradually adding 1G and 5 (J) of northern lead, it was further stirred for 30 minutes and the reaction solution was filtered.
After stirring for 2 hours, the mixture was filtered, the filtrate was poured into water from Step 12, and the precipitated solid was filtered off and recrystallized with Acetocol 1-Ryl to obtain the desired product 21.20.

Synthesis Example 2 Synthesis of Exemplified Compound M-15 (1) Synthesis of Coupler Monomer Using 1-phenyl-3-amino-5-pyrazolone as a starting material, 1-phenyl-3 was synthesized with methacrylic acid chloride in the same manner as in Synthesis Example 1. The amino group at the 3-position of -amino-5-pyrazolone was acylated, and a coupler monomer was further synthesized by nitration, reduction, and imidization reactions in the same manner as in Synthesis Example-1.

(2) Synthesis of polymer 6 g of the coupler monomer constructed above and 40 butyl acrylate were dissolved in 5 (h + 12) dimethylformamide, maintained at 80 to 82 °C under a nitrogen stream, and 200 a + g of 2,2-azobisisobutylene Nitrile 2 times at 2 hour intervals
The mixture was added twice and reacted for 4 hours.

After the reaction was completed, the reaction solution was poured into 5002 water, and the precipitated solid was filtered off and dried to obtain 9.2 g of the desired polymer.

The couplers of the present invention may be used alone or in combination of two or more. The usage thereof is not limited, and depends on the type of coupler, 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 layers. For example, the usage amount is 1.
0.005 per 12 (1 to 10 g 1 preferably 0.1
0 to 5.0 g can be used.

The method of incorporating the coupler used in the present invention into the photographic component of the heat-developable color light-sensitive material is arbitrary. Mineral acid (V
A: For example, it can be used after being neutralized by applying weight or drying, or after being dispersed with an appropriate polymer aqueous solution (e.g., gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill. .

The heat-developable color photosensitive material of the present invention contains photosensitive silver halide together with the coupler.

The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples include additive bromide m. 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 a conventional method for preparing a 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 or fine, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.001 μm to about 1.5 μm, and more preferably about 0.001 μm to about 1.5 μm. .01 μm to about 0.5 μm.

The photosensitive silver halide emulsion prepared by WJ 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 manufacturing method is a sterile halide, for example, a halide represented by MXn (where M represents an H atom, an NH4 group, or a metal atom, and X represents (/!, Br or ■, n is 1 when M is an H atom or an N84 group, and the valence when M is a metal atom.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, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium,
Examples include iron, Kobal 1~, nickel, rhodium, palladium, osmium, iridium, platinum, and cerium. ), halogen-containing gold m1 body (for example, K2 Pt C1
6, 2 Pt 3rs, HAtl C14゜(N
H4)2 Ir C1s, (NHq)31r (,C
6゜(NH4)2 RU C16, (NHq)a R
(IC1a.

(NH4)a Rh C4! s, (NH4)3 Rh
3rs, etc.), onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimedelphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethylphosph) quaternary sulfonium halides such as onium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g. iodoform, bromoform, tetrabromide, etc.), carbon, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromo phthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.), Other halogen-containing compounds (
Examples include triphenylmethyl chloride, triphenylmethyl bromide, 2-bromo (ffi! acid, 2-bromoethanol, etc.).

These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various methods, and the m used is 0.001 (preferably 1 to 50 g, more preferably 1 to 50 g) to 112 per layer. is 0.1g~10
It is g.

The thermal 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 green-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable green-sensitive layer. You can also write. Further, the same color photosensitive pattern can be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity β layer).

In the above case, the stomach-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 have a hydroxyalkyl group, a sulfoargyl group, or an enamine group capable of forming a carboxyalkyl 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 may have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbyl nucleation, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. good.

These acidic nuclei further include alkyl groups, alkylene groups, phenyl groups, carboxyalkyl groups, hydroxyalkyl groups, alkogylalkyl groups,
It may be replaced with an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic mM conductors, azaindene cadmium salts, arideno sulfonic acids, etc., such as U.S. Patent No. 2,
A supersensitizing additive that does not absorb visible light, such as those described in the specifications of No. 933,390 and No. 2,937,089, can be used in combination.

The addition m of these dyes is from 1.times.10@-4 mole to 1 mole per mole of silver halide or silver halide-forming component.

More preferably, I X 10-4 mol to 1×10″
It is 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 Nos. 43-4921 and 44-26582.
No. 45-18416, No. 45-12700, No. 45-22185, JP-A-49-52 (i26, No. 52-31728, No. 52-137321, No. 52)
-141222, 53-36224 and 53
Publications such as -37610 and U.S. Patent Nos. 3 and 3
No. 30, 633, No. 3,794,496, No. 4
, No. 105, 451, No. 4, No. 123, 274,
Silver salts of aliphatic carboxylic acids, such as silver laurate, silver myristate, silver valmidate, stearin rl, as described in the specifications of the same No. 4, IO2,980, etc.
Silver aromatic carboxylates, such as silver i, silver arachidonic acid, behen MWi, silver α-(1-phenyltetrazolthio) acetate, such as benzoic acid! 2 silver, silver phthalate, etc., Japanese Patent Publications No. 44-26582, No. 45-12700, No. 45-
No. 18416, No. 45-22185, JP-A-52-3
No. 1728, No. 52-137321, JP-A-58-1
Silver salts of imino groups such as those described in publications such as No. 18638 and No. 58-118639, such as silver benzotriazole, silver 5-nitrobenzotriazole, silver 5-chlorobenzotriazole, silver 5-methoxybenzotriazole , 4-sulfobenzotriazole silver, 4-hydroxybenzotriazole silver 1,5-aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nidropenzimidazole silver, pyrazole silver, urazole silver ,1,
2.4-triazole silver, 1H-tetrazole silver, 3-
Silver amino-5-pendylthio-1,2,4-triazole, silver saccharin, silver phthalazinone, silver phthalimide, etc., silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazoleimidazol-1,2 .4. - triazole silver, 4-hydroxy-6-methyl-1.3.3a. 7-detrazaindene silver and 5-methyl-7-hydroxy-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 sulfobenzo-1-lyazole 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 to be used is preferably 0.01 to 500 mol, more preferably 0.1 to 100 mol, per 1 mol 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. 3.764132
No. 8 each Mei Ii [specifications, and R D No. 1214
6, same No.

15108, N0. 15127 and Japanese Unexamined Patent Publication No. 1983
Examples include p-phenylenediamine-based and p-aminephenol-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-53-135628,
The color developing agent precursor described in Japanese Patent No. 54-79035 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 (3) described in Specification No. 4.

General formula (3) In the formula, R4 and R5 represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) which may have a substituent, and R4 and R5 are ring-closed. may be used to form a heterocycle. Rs, R7R8 and R9 each have a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number of 1 to 30 (preferably 1 to 30 carbon atoms, which may have a substituent). 1 to 4) represents an alkyl group,
R6 and R4 and R8 and R5 may each be ring-closed to form a heterocycle. M represents an alkali excess 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 (3) has no t1M
It is an organic compound containing a basic nitrogen atom that can form a salt with a salt, and an especially important □ base includes an amine compound. Examples of amine compounds include primary amines, secondary amines, tertiary amines, etc., and examples of cyclic amine compounds include typical heterocyclic organic bases such as pyridine, quinoline, etc. Examples include piperidine and imidazole. In addition, hydroxylamine,
Compounds such as hydrazine and amidine are also useful as chain amines. As the salt of the nitrogen-containing base, inorganic acid salts of organic bases (eg, hydrochlorides, sulfates, nitrates, etc.) as mentioned 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 (3) are shown below.

The following margins are (R-1) (R-2) (R-3) (R-4) (R-7) (R-8). 6 (R-9) H3 (R-10) (R-11) (R-12) (R-15) (R-16) (R-17) (R-18) (R-19) (R- 20) (R-21) (R-22) (R-23) The reducing agent represented by the above general formula (3) can be prepared by a known method,
For example, Heuben Peil, Methoden der Organizien Hemi, Band XI/2 (1-1ouben
-Weyl, Methoden der Ora
Anischen Chen+ie, Band
XI/2) It can be synthesized according to the method described on pages 645-703.

Other reducing agents as described below can also be used.

For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-tert-
butyl-p-cresol, N-methyl-〇-aminophenol, etc.), sulfonamide butinols [e.g. 4-
Benzenesulfonamidophenol, 2-penpinesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2.6-dipromo 4-
(1)-Toluenesulfonamide)phenol''3],
or polyhydroxybenpines (e.g., hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g., α-naphthol, β- naphthol, 4-aminonaphthol, 4-methoxyphel, etc.), hydroxybinaphthyls J3 and methylene bisnaphthols [e.g. 1,1'-dihydroxy-2,2
' - Binaphthyl, 6.6' - Jib mouth U-2,2' -
dihydroxy-1,1'- and naphthyl, 6,6-sinitro-2,2'-dihydroxy-1,1'-binaphthyl,
4.4'-dimeI xy-1,1'-dihydroxy-2
, 2'-binaphthyl, bis(2-hydroxy-1-naphthyl)methane, etc.], methylene-sphenols [e.g. 1.1-bis(2-hydroxy-3,5-diethylphenyl)-3゜5.5- 1-limethylhexane, 1.1-
Bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5-di-tart-butylphenyl)methane, 2
．． 6-meblenpis (2-hydroxy-3-tert-
Butyl-5-methylphenyl)-4-medylphenol, 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 reducing agent to be used depends on the type of photosensitive silver halide, the type of organic silver halide used, and the type of other additives, but it is usually 1 mole of photosensitive silver halide. The amount ranges from 0.01 to 1500 mol, preferably from 081 to 200 mol.

Examples of the binder used in the heat-developable color photosensitive material 1 of the present invention include polyvinyl butyral, poly[vinyl, ethylcellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpylene]ridone, gelatin, and phthalated gelatin. One or a combination of two or more synthetic or natural polymeric substances can be used. In particular, gelatin or
It is preferable to use the G-form together with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in JP-A-59-229556.

This binder includes gelatin and vinylpyrrolidone polymer. The vinyl pyrrolidone polymer may be polyvinyl pyrrolidone, which is a mono-m polymer of vinyl and lolidone, or a co-m polymer (graft copolymer) with vinyl pyrrolidone and one or more other monomers copolymerizable with vinyl pyrrolidone. ) may be included. These polymers can be used regardless of their degree of polymerization. The polyvinylpyrrolidone may be substituted polyvinylpyrrolidone, and preferred polyvinylpyrrolidone has a molecular m1.000 to 40
It is of 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-based hexamers such as vinyl alkyl ethers, but it is preferable that polyvinylpyrrolidone accounts for at least 20% (by weight, the same hereinafter) of the composition.

A preferred example of such a copolymer has molecules 5,000
~400.000 ra.

Gelatin is lime! l! The gelatin may be obtained by X-chemical treatment or acid treatment, and may be ossein gelatin, piggesgin pyratin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatin.

In the above binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and polyvinylpyrrolidone accounts for 5 to 90% of the total binder.
It is preferably 90%, more preferably 10-8
It is 0%.

The binder may contain other polymeric substances,
Gelatin and a mixture of polyvinylpyrrolidone with molecules ε 1,000 to 400,000 and one or more other polymeric substances, gelatin and molecules m 5,000 to 400,0
A mixture of the vinylpyrrolidone copolymer of No. 00 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, and proteins such as cellulose gB and polysaccharides such as starch and gum arabic. Natural substances such as These range from 0 to 85%, preferably from 0 to 85%.
It may be contained in an amount of 70%.

The above-mentioned vinylpyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after spreading it on a support (including the case where the crosslinking reaction progresses by being allowed to stand).

The amount of binder used is usually 0.05 g to 50 (l) per 1 m' per layer, preferably 0.1 g to 1 m'.
0 (l). Furthermore, the binder is preferably used in the range of 0.1 to 10 (l) for the coupler 19 of the present invention,
More preferably, it is 0.25 to 4 g.

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,
Also included are paper supports such as 7-page base paper, printing paper, baryta paper and resin-coated paper, and supports in which the above-mentioned synthetic plastic film is provided with a reflective layer.

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 is preferably solid, semi-solid, or liquid at room temperature, and preferably has a boiling point of 1 at normal pressure.
00°C or higher, more preferably 150°C or higher) and is a substance that dissolves or melts in the binder, preferably urea m4 (for example, diethylurea, diethylurea, phenyl urea, etc.), amide derivatives (e.g., acetamide, benzamide, etc.)
, polyhydric alcohols (e.g., 1.5-pencundiol, 1.6-pentanediol, 1.2-cyclohexanediol, pentaerythryl, 1-rimedylolethane, etc.), or polyallene glycol Examples include: For a detailed example, see Japanese Patent Application Laid-Open No. 59-22955.
It is stated in No. 6. 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 as required. For example, as a developing accelerator, U.S. Pat.
No. 4,060,420, No. 4,088.49
6@, No. 4,207,392, each specification III, RD
No, 15733, same N 0.15734, same N
0.15776, JP-A No. 56-130745, No. 5
Alkali release agents such as urea and guanidium 1 to dichloroacetate described in No. 6-132332, etc.;
5-12700, U.S. Pat. No. 3,667
．． Non-aqueous polar solvent compound having -Go-, -8O2+, -5o- groups described in No. 959, U.S. Pat. No. 3,438
．． Melt former-1 described in No. 776 Yoneda Patent No. 3.6
66,477, and polyalkylene glycols described in JP-A-51-19525. In addition, as a color toning agent, for example, JP-A No. 46-4928, JP-A No. 46-6077
No. 49-5019, No. 49-5020, No. 49
-91215, 49-107727, 50-2
No. 524, No. 50-67132, No. 50-67641
No. 50-114217@, No. 52-33722,
No. 52-99813, No. 53-1020, No. 53-
No. 55115, No. 53-7 [No. 3020, No. 53-1
No. 25014, No. 54-156523, No. 54-1
No. 56524, No. 54-156525, No. 54-
No. 15652G, No. 55-40GO, No. 55-406
Publications such as No. 1 and No. 55-32015, as well as West German Patent Nos. 2,140.406 and 2.147.063,
No. 2,220,618, U.S. Patent No. 3.080.25
No. 4, No. 3.847.612, No. 3.782.9
No. 41, No. 3,994,732, No. 4.123.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, def-1-oxazine diane, 2゜3-dihydro-phthalazinedione, 2,3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl sulfonamide, 2H-1
．． 3-pensive azine = 2,4- (3H) dione, benzo-1-lyazine, mercaptotriazolene, phthalic acid, naphthalic acid, phthalamic acid, etc., and a mixture of one or more of these with an imidazole compound, Also, 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. I can raise a hat.

Also, JP-A-58-189628, JP-A No. 58-193
3-amino-5-mercapto-1°2,4-triazoles and 3-acylamino-5-mercapto-1,2,4-triazoles described and published in Japanese Patent No. 460 are also effective.

Furthermore, as an antifoggant, for example,
No. 711N3, Special Dfl Drl 49-901113
Q, Q49-10724, Q49-7613, Q50-101019, Q4! ]-130720, 50-123331, 51-47419, 51
-57435, 51-78227, 51-10
No. 4338, No. 53-19825, No. 53-2092
No. 3, No. 51-50725, No. 51-3223, No. 51-42529, No. 51-81124, No. 54-
No. 51821, Kasa No. 55-93149, as well as British Patent No. 1.455,271 and U.S. Patent No. 3.8.
No. 85.968, No. 3.700,457, No. 4.
137.079, 4.138.265, and West German Patent No. 2,617,907, or oxidizing agents (such as rIA, N- Halogenoacetamide, N-halogenosuccinimide, peroxylic acid and its salts, sterile perfl? compound,
persulfates, etc.), or acids and their salts (e.g., sulfinic acid, lithium laurate, rosin, diterpene acid, thiosulfone C), or sulfur-containing compounds (e.g., mercap 1-releasing compounds, Uracil, disulfide, simple sulfur, mercapto-1,2,4
= triazole, thiazolinthione, polysulfide compounds, etc.), and other compounds such as oxazoline, 1,2°4-1 to lyazole, and phthalimide. Furthermore, as another antifoggant, JP-A-59-111G36
The thiol (preferably diphenol compound) compounds described in the above are also effective.

In addition, as an antifoggant, hydroquinone MQ form (for example, G [-
Hydroquinone derivatives described in Japanese Patent Application No. 59-6G380 and benzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used.

The patent application filed by the present inventors in Japanese Patent Application No. 6O-2F32177 and No. 130-263564
The polymer inhibitor and ballasting inhibitor described in ':j are particularly preferred antifoggants in the heat-developable color photosensitive material of the present invention.

In addition, as a stabilizer, a printout preventive agent may be used at the same time, especially after processing, for example, in Japanese Patent Application Laid-Open No. 111048-452.
No. 28, No. 50-119624, No. 50-120
328, 53-46020, etc., specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide,
2-tribromomethylsulfonylbenzothiazole, 2
．． Examples include 4-bis(tribromomethyl)-6-methyltriazine.

Mana Special Publication No. 1972-5393, JP 50-54329
A post-treatment may be carried out using a sulfur-containing compound as described in No. 50-77034.

In particular, U.S. Patent No. 3,301,078;
50G, No. 444, No. 3.824.103, and No. 3.8,14,788, as well as U.S. Patent No. 3,669.670, No. 4,012,260, No. 4.0 (Specification IM of No. 30,420).

Also, sucrose, NH4Fe (SO4)2 ・12
A water release agent such as 820 may be used, or heat development may be carried out by supplying water as in JP-A-56-132332.

In addition to the above-mentioned components, the heat-developable color photosensitive OH of the present invention further includes spectral enhancement 1'31, antihalation dye, optical brightener, hardener, antistatic agent, plasticizer,
Various additives such as spreading agents, coating aids, etc. are added.

The heat-developable color photosensitive material of the present invention basically contains (1) photosensitive silver halide, (2) a reducing agent, (3) and the coupler of the present invention, and (4) a binder in the same layer. (5) Contains 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 above-mentioned (1), (2), and (4)
, (5) is contained in the photosensitive layer on one side, and the coupler (3) of the present invention is contained in the layer on the other side adjacent to this photosensitive layer.
If they are in a state where they can react with each other, they may be contained separately in two or more photographic development layers.

In addition, the color photosensitive layer may be divided into two layers, such as a high-sensitivity layer and a low-sensitivity layer.
It may be divided into more than one layer, and may have one or more photosensitive layers with roughly different color sensitivities,
It may have various photographic compositions such as an overcoat layer, an undercoat layer, a backing layer, an intermediate layer, or a filter layer.

Similar to the heat-developable photosensitive material of the present invention, the 4L intermediate layer, the undercoat,
For the back layer and other photographic components, respective coating solutions are prepared, and various coating methods such as dipping method, air knife method, curtain coating method, or hopper coating method described in U.S. Pat. No. 3,681.294 are applied. A photosensitive material can be created by the method.

Further, if necessary, see US Pat. No. 2,1e1. yq1 and British Time: 5 No. 837. Two or more coats can be applied simultaneously by the method described in No. 5.

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 μm, more preferably 3 to 20 μm.

The color photoreceptor 1'+1 of the present invention is subjected to imagewise exposure as it is, and then the temperature is usually 80°C to 200°C, preferably 120°C.
Color development is carried out by heating at a temperature range of 170 DEG C. for 1 second to 180 seconds, preferably 1.5 seconds to 120 seconds. In addition, if necessary, it may be developed with a water-impermeable film in close contact with it, or it may be heated at 70°C to 18°C before exposure.
Preheating may be performed in the temperature range of 0°C.

Various exposure means can be used for the heat-developable color photosensitive material according to the present invention. The latent image is formed by imagewise exposure to radiation, including visible light. In general, light sources used for conventional color printing, such as tungsten lamps, mercury vapor lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source. I can do it.

As the heating means, all methods applicable to ordinary heat-developable photosensitive materials can be used, such as contacting with a heated plotter or plate, contacting with a heated roller or drum, or passing through a high-temperature atmosphere. Alternatively, high frequency heating may be used, or furthermore, a conductive layer 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, such as preheating (preheating) and then reheating, heating at a high temperature for a short period of time, or at a low temperature for a long period of time, continuously raising, lowering, or changing the direction. Although discontinuous heating is possible, a simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

In the heat-developable photosensitive material 11 of the present invention, in order to remove the silver image generated at the same time, the photothermographic material 11 is treated with a bleaching bath or a fixing bath after heat development, or JP-A-59-136733, U.S. Pat.
．． Bleaching and fixing may be carried out by separately processing the bleaching and fixing sheets as described in No. 124.398 and No. 4.124.387.

[Examples] Examples of the present invention are not shown below, but the embodiments of the present invention are not limited thereto.

Example-1 Coupler 570m (+,
1.

4-Dioctylhydroquinone% moSrIIP ethyl 1.3d and dioctyl terephthalate 0.50 were mixed and dissolved by heating. This solution contains 2.5 ml of surfactant.
% gelatin aqueous solution and add water to make 13c.
After c, it was dispersed with a homogenizer to obtain a coupler dispersion (q).

Add 6.5 cc of the above dispersion to 150 mg of gelatin and 300 mg of gelatin.
m.

of polyvinylpyrrolidone (average molecular weight 30,000>,
3-Methylpentane-1,3,5-1-lyal 200
mg and polyethylene glycol (average molecular weight 300)
Exemplary i1 base agent (R-11>
200 ml+ was added, and 4 volumes of each solution of 4-sulfobenzotriazole prepared by the method shown below were added to adjust pl-1 to 5.5. This dispersion has an average particle size of 0.1
Add 3 x 10-4 mol of silver iodobromide emulsion (containing 75 m0 of pyratine) of 2 μm silver iodobromide emulsion and add water to make 161 g.
1 moxibustion finished with a dry film thickness of 1.5 μm on baryta paper
A photosensitive layer was coated by coating with a Y-V-bar so that the photosensitive material sample (sample no.

1) is 14.

After drying the obtained photosensitive material sample (sample No. 1), 8.
After applying white exposure of 0OOCM S through a step wedge, heat development was performed at 150° C. for 1 minute to obtain a magenta image. The image density of the obtained image with respect to green light is not shown in Table 1.

[Preparation of silver 4-sulfobenzotriazole 124 g of 4
-Sulfobenzotriazole and 4 ml of sodium hydroxide were added and dissolved in 30 h!2 of an ethanol-water (1:1) mixture.To this solution was added 20 ml of 5N 6FI acid silver solution.
was dripped. At this time, a 5N sodium hydroxide solution was also added dropwise at the same time to maintain I)H at 7-8. Add this solution to 1
After stirring at room temperature for an hour, add water to 400 ml and raise to 4-
A 4-sulfobenzotriazole silver solution containing 20% excess of sulfobenzotriazole was prepared.

Example 2 The same sample as Example 1 (sample 1
1N0.2) was prepared and subjected to the same exposure, bleaching, and fixing as in Example 1. The results are shown in Table-1.

The couplers of the exemplary compound (M-15) of development inhibitor Example-2 are shown below.
Light-sensitive material samples Pt (samples Nos. 003 to 6) were prepared in the same manner as in Example 2, except that the coupler shown in Example 1 was used. In addition, as a comparative example, photosensitive material samples (try-on No. 7 to 8 )
was created.

These samples Nos. 11 and 3 to 8 were subjected to the same exposure and heat development as in Example 1, and the magenta images shown in Table 1 were obtained.

Comparative coupler A Comparative coupler B I For photosensitive material samples No. 4.5 and 7, dioctyl athalate was used as a high boiling point solvent in order to protect and disperse the coupler in oil.

Example-4 Photosensitive material 11 after heat development of Examples-1 to 3 (Test No. 11
, 1.2.3.5.7.8> as described below by Eastman Kodak? JE-6 treatment (sample no.

1', 2', 3', 5', 7', 8').
.

6'), bleaching and fixing were carried out, respectively, and a clear magenta image was obtained. Table 1 shows the image densities of the densified magenta images with respect to green light.

[E-6 Process II'] 1 kneading Temperature: 1, conditioner: 25-40℃ 2 minutes, bleaching
35-38℃ 6 minutes 3, constant
Wash at 25-40℃ for 6 minutes and 4 minutes.
4 minutes [ECN-2 treatment temperature time 1,
Brevas 27℃ 30 seconds 2,'a
White 27℃ 3 minutes 3
, water washing 1 minute 4, fixation 25-40℃ 5 minutes 5, water washing 2 minutes Example-5 The organic normal salt dispersion was removed from the coating solution of Example-2 and replaced with 10% ethanol containing guanidine trichloroacetic acid. Liquid 0. /l
Add 4d of aqueous solution containing vQ and adjust the pH of Coating No. 11 to 6.5.
The same coating solution as in Example 2 was prepared except for the above, and it was applied onto baryta paper so that the dry film thickness was 7.5 μm, and dried to prepare a photosensitive material sample (sample No. 9). −
Perform the same exposure and development processing as in 2, D maxl,
49, a magenta image of D m1n0.12 was obtained.

Margin Table 1 Below: From the results shown in Table 1, it can be seen that in the light-sensitive materials using the coupler of the present invention, Q max is large and D
min is small, and the comparative coupler either has a lower density or has a larger force (IX). Even if the light-sensitive material does not contain an organic silver salt, the density will be lower in the light-sensitive material using the coupler of the present invention. and the fog is small.

Example-6 Example-1 except that the silver halide in Example-1 was replaced with silver halide having green sensitivity and an average grain size of 0.12 μm.
A coating solution using the same coupler (M-15) as in Example 1 was applied onto baryta paper using a wire bar so that the dry film thickness was 7.5 μm to form a first @ optical layer. On this first photosensitive layer, 1,4-dioctylhydroquinone 20no+
10 cc of 4% gelatin solution [contains 200 mg of polyethylene glycol (average molecular m 300)].

] was coated with a wire bar so that the dry film thickness was 211 m, and an intermediate opening was provided.

Change the coupler to the cyan coupler below on this intermediate layer,
Silver halide with red sensitivity (ffi
No. 1 except that it was changed to ω, 9 x 10-4 mole in terms of silver)! The same residence as S. Mitsuhiro was painted and a second Kanko residence was built.

The cyan coupler was further coated with 10 cc of 4% gelatin solution on the second rJiA light port so that the dry film thickness was 2 μm to form a protective layer.

After drying the obtained photosensitive 440,000 1 test (11 (Test 11N0.10)), red exposure, green exposure and white exposure of 8,000 CM S were applied, followed by bleaching and fixing at 0% in the same manner as in Example-2. After that, D max and [) w by red light and green light
The concentration of in was determined. The results are shown in Table-2.

Example-7 I'1113 photodermal coupler (M-15) of Example-6
The same photosensitive material sample (sample No. 11) as in Example 6 was prepared except that (M-3) was used instead of (M-3). Obtained sample N0
．． After drying No. 11, the same exposure, heat development, bleaching, and fixing as in Example-6 were carried out, and D max was obtained using red light and green light.
and the concentration of Q win was determined.

The results are shown in Table-2.

Margins below As shown in Samples No. 10 of Example 6 and Sample No. 0111 of Example 7, polymer couplers are more preferable in multilayer photosensitive materials because they cause no color mixing due to movement of the polymer couplers themselves.

Claims (1)

[Scope of Claims] A heat-developable color photosensitive material having at least one heat-developable photosensitive layer on a support, which contains a magenta coupler represented by the following general formula (1). photosensitive material. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, Z represents the atomic group necessary to form a nitrogen-containing heterocyclic residue together with the N atom, and R_1 is an alkyl group, an aryl group, It represents an alkylamino group, anilino group, an acylamino group or a ureido group, and R_2 represents an aryl group or a heterocyclic residue. However, at least one of R_1 and R_2 is substituted with a ballast group or a ballast group. ]