JPS62129851A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To prevent the heat fog of the titled material due to a heat development by incorporating a 1H-pyrazolo[3,2-C]-S-triazole compd. having a cleavable group at 7 position of the triazole compd. to at least one kind of the silver halide emulsion layer. CONSTITUTION:The 1H-pyrazolo[3,2,-C]-S-triazole compd. which has the cleavable group at 7 position of the triazole compd. is used as the coloring matter affording substance. Said triazole compd. comprises all of said triazole compd. having the cleavable group at 7 position of the triazole compd. Said coloring matter affording substance shown by the formula is a magenta coloring matter affording substance, and is in a passive state in the emulsion layer before the heat development, and is an anti-diffusible compd., and also is a compd. capable of forming the diffusible magenta coloring matter by a coupling reaction in the heat-development. Thus, the titled compd. having an improved heat fog and a less color turbidity and capable of giving a clear image is obtd.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a heat-developable photosensitive material. More specifically, the present invention relates to a heat-developable photosensitive material containing a novel dye-providing substance, which has improved thermal fogging during heat development. [Background of the Invention] In recent years, various heat-developable photosensitive materials have been developed in which the developing step can be performed by heat treatment. Regarding such heat-developable photosensitive materials, for example,
No. 4921 and No. 43-4924 contain the description of organic silver salt, silver halide, and reducing agent h ＼ 龜斯氧性AI! M? Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods. For example, U.S. Patent Nos. 3,531,286 and 3,7
No. 61.210 and No. 3.764.328 disclose a thermal color photosensitive material in which a color image is formed by a reaction between an oxidized product of an aromatic primary amine developing agent and a coupler. ing. Also, Research Disclosure i? No. 15108 and No. 15127 disclose a heat-developable color photosensitive material in which a color image is formed by a reaction between an oxidized product of a sulfonamide phenol or sulfonamide aniline derivative developing agent and a coupler. However, these methods have the problem that the reduced silver image and the color image are simultaneously generated in the exposed area after the hot mass treatment, resulting in the color image becoming cloudy. In addition, as a method to solve this problem, there is a method of removing the silver image by liquid processing or transferring only the dye to another layer, for example, an image receiving sheet having an image receiving layer.
A method that distinguishes between unreacted substances and dyes and transfers only the dyes. A heat-developable color photosensitive material has been disclosed in which an imino group is released in an exposed area by heat development using a silver salt, and a color image is formed on an image-receiving layer as a transfer paper using a solvent.However, this method However, it is difficult to suppress the release of dye in areas that are not exposed to light, and it is difficult to obtain clear color images. 52-1058
No. 22, Publication No. 56-50328, U.S. Patent No. 4,
No. 235,957, Research Disclosure No. 14448, Research Disclosure No. 15227, Research Disclosure No. 18137, etc. disclose heat-developable color photosensitive materials in which a positive color image is formed by a heat-sensitive silver dye bleaching method. However, this method requires extra steps and photographic construction materials, such as stacking and heating sheets containing activators to speed up the bleaching of the dyes, and the resulting color images do not survive long-term storage. Another problem is that it is gradually reduced and bleached by coexisting free silver and the like. Also, U.S. Patent No. 3.180.732@, U.S. Patent No. 3,98
5,565 and 4,022,617
This book and Research Disclosure No. 12533 disclose a thermal color photosensitive material that forms a color image using a leuco dye. However, this method has the problem that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage. Furthermore, JP-A-57-179840 discloses a thermal color photosensitive material in which a color image is formed using a dye-releasing aid and a reducing dye-providing substance that releases a diffusible dye. However, in this method, it is essential to use a dye release aid, and this dye release aid is a so-called base or a precursor of a base. As described above, the technique using a base or a base precursor has the problem that in a heat-developable photosensitive material using an organic silver salt oxidizing agent, the presence of the base increases fog and lowers the maximum density. Furthermore, JP-A-57-186744 and JP-A No. 58-12
No. 3533 and Publication No. 58-149046 disclose heat-developable color photosensitive materials that release or form diffusible dyes by heat development to obtain transferred color images. However, in the exemplary compounds described in these publications and specifications, the production efficiency of diffusible dyes during thermal development is low, and the maximum density of the transferred image to the image-receiving layer (DmaX
) or fog (Dmin) becomes large. [Object of the Invention] Accordingly, an object of the present invention is to provide a heat-developable photosensitive material containing a novel dye-providing substance and exhibiting improved thermal fog during heat development. Another object of the present invention is to provide a photothermographic material capable of producing clear images without color turbidity. Still another object of the present invention is to provide a dye-providing material that has high diffusible dye production efficiency during thermal development and is capable of obtaining transferred images with less fog at high temperatures.
and L-/lF1-[Structure of the Invention] The above object of the present invention is to provide a 1-day-
This is achieved using a heat-developable photosensitive material containing a pyrazolo[3,2-C1-8-triazole compound. [Specific configuration 1 of the invention] Having a leaving group at the 7-position used in the present invention,
The 1H-pyrazolo[3,2-CI-8-triazole compound is a compound used as a dye-providing substance in the present invention, and if it has a leaving group at the 7-position, all 1H-pyrazolo[3,2-CI-8-triazole compounds]
It includes di-pyrazolo[3°2-CI-8-triazole compounds, and may have any substituents, for example, at the 3- and 6-positions. The 1-day-virazoO[3,2-CI-8-triazole compound having an M-removable group at the 7-position, which is preferably used in the present invention, is represented by the following general formula [I]. General formula [I] In the formula, X represents a group that can be eliminated during a coupling reaction, and R1 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, respectively. , represents an acylamino group, a ureido group or a heterocyclic residue. In general formula [I], R1 and R2 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, a ureido group, or a heterocyclic residue; group, aryl group, alkoxy group, aryloxy group,
The amino group, acylamino group, ureido group and heterocyclic residue each include those having a substituent. Examples of the halogen atom represented by R1 and R2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by R1 and R2 may be linear or branched, such as a methyl group, an ethyl group,

[
-butyl group, octyl group, undecyl group, etc. Examples of the aryl group represented by R1 and R2 include a phenyl group, and examples of the alkoxy group represented by R+ and R2 and 1' include a methoxy group, a propoxy group, a pentadecyloxy group, and the like. Further, examples of the aryloxy group represented by R1 and R2 include phenyloxy group and phenyl group, and examples of the amino group represented by R1 and R2 include unsubstituted amino group,
Examples include alkylamino groups (eg, methylamino group, ethylamino group, diethylamino group, etc.), phenylamino M (eg, anilino group, etc.). Furthermore, the acylamino group represented by R1 and R2 includes an alkino♂Ybonylamino group (e.g., methylcarbonylamino group, ethylcarbonylamino group, etc.), an arylcarbonylamino group (e.g., phenylcarbonylamino group, etc.)
Examples of the ureido groups represented by R1 and R2 include alkylureido groups (e.g., N-methylureido group, etc.), arylureido groups (e.g., N-phenylureido group, etc.), and heterocyclic residues. As, 5
Alternatively, a 6-membered ring is preferable, such as a pyrimidinyl group, an imidazolyl group, a benzothiazolyl group, and the like. Substituents for the alkyl group, aryl group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, and heterocyclic residue represented by R1 and R2 include halogen atoms (for example, chlorine atoms, etc.), direct Chain or branched alkyl groups (e.g. methyl, ethyl, t-butyl, etc.), aryl groups (e.g. phenyl, etc.), cycloalkyl groups (e.g. cyclohexyl, etc.), alkoxy groups (e.g. methoxy, etc.), acylamino groups (e.g., acetamide groups, benzamide groups, etc.), sulfonamide groups (e.g., sulfonamide groups, methanesulfonamide groups, benzenesulfonamide groups, etc.), sulfamoyl groups (
For example, sulfamoyl group, N-ethylsulfamoyl group, N,N-dimedylsulfamoyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.) , an acyl group (for example, an acetyl group, a benzoyl group, etc.), a nitro group, a cyano group, and the like. The total number of carbon atoms in the groups represented by R+ and R2 is preferably 1 to 12, more preferably 1 to 8. In the general formula [I], during the coupling reaction, X is
It represents a removable group, preferably a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or a group represented by the following general formula [Irl]. General formula [ff] A-8 In the above general formula [Irl, A represents a bonding group containing a nitrogen atom, a sulfur atom, and an oxygen atom that can be eliminated during a coupling reaction. B represents an alkyl group, an aryl group, an alkylamino group, an arylamino group, a heterocyclic residue, a group fused to eight, or a polymer residue. In the general formula [I], the bond represented by A)
SO2-1-S-1-SO-1-8O2-1〇-1-
Atom group forming NHCO-1-N-CO-1'),
-NH3O-1-NR3802-1-NRaSO-1-
Examples include N=I'J-. (R3 here represents a halogen atom or an alkyl group, aryl group, alkoxy group, aryloxy group, etc., each of which may have a substituent). In the general formula [II], the alkyl group represented by B may be linear or branched, for example,
Examples include ethyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, eicosyl group, and the like. Examples of the aryl group represented by B include phenyl group and naphthyl group. Examples of the alkylamino group represented by B include dodecylamino group and dibutylamino group. Examples of the arylamino group represented by B include anilino group. The heterocyclic residue represented by B is preferably a 5- or 6-membered ring, and includes, for example, a pyridyl group, an imidazolyl group, a benzodeazolyl group, and the like. Examples of the group fused to A represented by B include a benzene ring and a naphthalene ring. The alkyl group, aryl JJ1 alkylamino group, arylamino group, heterocyclic residue, and the group condensed to A represented by B include those each having a substituent, and these substituents include halogen atoms (e.g. fluorine atom,
chlorine atom, bromine atom, etc.), linear or branched alkyl groups (e.g., ethyl group, t-butyl group, octyl group, undecyl group, dodecyl group, hexadecyl group, etc.), aryl group (e.g., phenyl group, etc.), alkoxy group (For example, methoxy group, propoxy group, 2-ethylhexyloxy group,
dodecyloxy group, etc.), aryloxy group (e.g., phenyloxy group, 2,4-di-t-pentylphenyloxy group, etc.), acylamino group [e.g., acetamido group,
Penzamide group, butanamide group, dodecanamide group,
α-(2゜4-di-t-acylphenoxy)acetamide group, α-(2,4-di-t-acylphenoxy)butanamide group, N-methyl-hexadodecaneamide group, etc.]
, sulfonamide group (e.g. ethanesulfonamide group,
Benzene sulfonamide group, octane sulfonamide group, p-dodecyloxybenzenesulfonamide group, N-
methyl-tetradecanesulfonamide group, etc.), sulfamoyl group (e.g., sulfamoyl group, N-ethylsulfamoyl cs, x, N-dihexylsulfamoyl group, N-tetradecylsulf7moyl group, N-tab- N-tetradecylsulfamoyl [yl group (e.g. N-methylcarbamoyl N-octylcarbamoyl group, N-hexadecylcarbamoylrubamoyl group (e.g. methoxycarbonyl group, tetradecyloxycarbonyl group, etc.), alkoxysulfonyl group (e.g. , methoxysulfonyl group, octyloxysulfonyl group, doacyloxysulfonyl group, etc.), aryloxysulfonyl group (e.g., phenoxysulfonyl group, m-dodecyloxyphenoxysulfonyl group, etc.), alkylsulfonyl group (e.g., methanesulfonyl group, ethanesulfonyl group, etc.), arylsulfonyl length (e.g., benzenesulfonyl group, p-toluenesulfonyl group, etc.), alkylthio group (e.g., methylthio group, hexylthio group, benzylthio group, etc.), arylthio group (e.g., phenylthio group,
pt-butylphenylthio group, etc.), ureido group (e.g., N-methylureido group, N-phenylureido group,
N,N-dihexylureido group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), nitro group, cyano group, carboxy group, sulfo group, hydroxy group, etc. If there are more than one, they may be the same or different. Among these substituents, organic groups or hydrophilic groups having a5 to 36 carbon atoms, particularly carboxy groups, sulfo groups, sulfonamide groups, and these groups are substituted as groups that further improve the diffusion resistance of the dye-donating substance. or a substituent with 5 carbon atoms
Substituents having ~36 Ia groups and a group comprising a hydrophilic group are preferred. Furthermore, in another preferable embodiment, 8 in the general formula [ff] represents a polymer residue. Furthermore, 1H-pyrazolo[3,
2-C]-8-1-riazole compound has the following general formula [I
It is preferable that the polymer be derived from a single O-form represented by [[] as a repeating unit. General formula [[[I In the formula, R1 and R2 are the same as defined in the above general formula [I], A is the same as defined in the above general formula [II], and R4 is a hydrogen atom, a carboxy group, or an alkyl group. It represents a group (for example, a methyl group, an ethyl group, etc.), and this alkyl group includes those having a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, etc.), a carboxy group, etc. be. The carboxy group represented by R+ and the carboxy group of the substituent may form a salt. Jl and J2 each represent a divalent bonding group, and the bonding group of 21iffi is, for example, -N
HCO-1-CONH-1-COO-1-OCO-1-
SCO-1-COS-1-0-1-S-1-SO-1-
8O2- etc. ×1 and x2 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 a phenylene group, an aralkylene group such as a phenylmethylene group, and an alkylenearylene group such as
For example, it is a methylene phenylene group, etc., and the arylene alkylene group is, for example, a phenylene methylene group. ks ff11, "1, !12, and m2 each represent O or 1. The dye-providing substance used in the present invention has the general formula [1[
In the case of a polymer having a repeating unit of a monomer represented by The copolymer may be a combination of two or more types, or may be a copolymer consisting of one or more monomers having a copolymerizable ethylenically unsaturated group. The comonomer having an ethylenically unsaturated group capable of forming a copolymer with a monomer b1 containing a coupler residue includes:
Acrylic acid esters, late methacrylic esters, vinyl esters, olefins, styrenes, crotonic esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, Examples include vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, and various unsaturated acids. More specifically, these comonomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-bubur acrylate, ta
rt-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-1~, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate , 2-chlorocyclohexyl acrylate, cyclohexyl acrylate-1, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-
and droxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxyethyl acrylate, 2-
Ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-
(2-methoxyethoxy)ethyl acrylate, 2-(
2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (additional mole 1
n=9) 1-bromo-2-methoxyethyl acrylate-1
~, 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-1, in-1-tyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N
-Phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4 -Hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate,
2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-buty-xyethyl methacrylate, 2-(
2-methoxyethoxy)ethyl methacrylate, 2-(
2-Ethoxyeth 4-cy)ethyl methacrylate, 2-
(2-Butoxyethoxy)ethyl methacrylate, ω-
Examples include methoxypolyethylene glycol methacrylate (number of moles added = 6), allyl methacrylate-1, and methacrylic acid dimethylaminoedylmethyl chloride salt. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, and t-nalycylic acid. Examples include vinyl. Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimedylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, promstyrene, and vinylbenzoic acid methyl ester. Examples include. Examples of the acid esters include butyl crotonate, hexyl crotonate, and the like. Examples of diethyl itaconate include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibdel maleate, and the like. Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of other comonomers include: Acrylamides, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyedylacrylamide, dimethylaminoedylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.: Methacrylamides, such as methacrylamide, methylmethacrylamide, Ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanethylmethacrylamide , N-(2-acetoacetoxyethyl) methacrylamide, etc.; Allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy Ethyl 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-vinyl oxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile, methacrylatrile, etc.; Polyfunctional monomers, such as divinylbenzene, methylenebisacrylamide , ethylene glycol dimethacrylate, etc. Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates such as monomethyl itaconate, monoedyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates such as monomethyl maleate, monoethyl maleate, maleic acid, etc. Acid-dried butyl, etc., laconic acid, methylene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc. :
Methacryloyloxyalkylsulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc. Niacrylamidoalkylsulfonic acids, 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-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid; acryloyloxyalkyl phosphate;
For example, acryloyloxyethyl phosphate, 3-
Acryloyloxypropyl-2-phosphate, etc.;
Methacryloxyalkyl phosphates, e.g.
Methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.: Examples include sodium 3-aryloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali metals (such as N81) or ammonium ions. Other comonomers include U.S. Patent No. 3,459.790, U.S. Patent No. 3.438.708, U.S. Pat. .613
Crosslinkable monomers described in JP-A-57-205735 and the like can be used. As an example of such a crosslinkable polymer, specifically, N-(2
-acetoacetoxyethyl)acrylamide, N-(2
-(2-7cetoacetoxyethoxy)ethyl)acrylamide and the like. In addition, when the dye-providing substance of the present invention forms a copolymer with a monomer containing a coupler residue, it is preferable that the repeating unit is contained in an amount of 10 to 90% by weight of the entire polymer, More preferably, the content is 30 to 80% by weight. The dye-donating substance of the present invention undergoes a coupling reaction with an oxidized form of a reducing agent to form a diffusible dye. In order to increase the diffusivity of the resulting dye, coupler residues R1 and R2 are selected. is preferable, and more preferably, the molecule ω of the coupler residue is 50θ or less. The dye-providing substance represented by the general formula [I] is a magenta dye-providing substance, and is immobilized in the emulsion layer in a thermal development facility. It is a diffusion-resistant compound,
It is a compound that can form a diffusible magenta dye through a coupling reaction during thermal development. In the present invention, the term "diffusivity" of the diffusible dye produced during heat development means that the dye produced from the dye-providing substance is deposited during heat development from the silver halide emulsion layer containing the dye-providing substance. It refers to the property of being able to migrate to the image-receiving layer in a superimposed relationship, and examples of the mode of this migration include, for example, the produced pigment itself melts and diffuses and transfers, and other examples include This includes cases where the dye is transferred by being dissolved in a solvent supplied near the dye, or by being heated and dissolved by a hot solvent.Furthermore, the generated dye itself is sublimable, and the generated dye is It also includes a mode in which it sublimates and vaporizes and moves to the image receiving layer of the silver halide emulsion layer. Here, the above-mentioned "sublimation property" refers to the property of changing from a solid to a gas without passing through the commonly used liquid state. It also includes the property of melting a solid to become a liquid, and then changing from this liquid to a gas.The dye-donating substance used in the present invention is 1H-pyrazolo[3,2- The 7-position (hereinafter referred to as active site) of the C1-8-triazole compound reacts with the oxidized form of the ♂7 element (color developing agent) to form a magenta dye, but at this time, the molecular weight of the magenta coupler core When the value is small (particularly preferably 500 or less), it is advantageous in terms of the diffusivity of the magenta dye. Typical specific examples of the dye-providing substance used in the present invention will be described below. It is not limited. Below, the margin U-(, 1 = ni = ○ = ~ Qm-u+.
5, 0 0 0 = 11- 1 CH. +n, ur, 10,200 m, vll, 11, l) Ol) COOH CH. m, u+, 7,000 m, 111. 5,100 O2 → CH-CH2+7- +n, u+, 4,900 m, w, 5.500 CH. ■ m, w, 5.0 (10 m0w, 7,200 C1□H2, -COOH "O = 翰
So Q
−=
Engineering Q Kushi 0] O2 In the following margin, typical synthesis examples of the dye-providing substance of the present invention are shown. A synthesis example of exemplified compound (1) is shown below. Other exemplified compounds are also synthesized through similar synthesis process steps. → [al (b) [dl Margin below [el [f] Margin below To specifically show the details of Synthesis Example 1, the above compound [
bl, [C], [d], [e], [''] and the exemplary compound (1) which is the dye-donating substance of the present invention are each synthesized through the following process steps: 1) ([a]→ Synthetic vinegar of [b co)!i! [a] (28(1,
0,206 mol) and stirring, add 20 mol of sodium nitrite (15,6 (1,0,226 mol)
Add gradually at ~25°C. After stirring as it is for 1 hour, suspended insoluble matter is filtered off, washed with water, filtered, and dried. Yield [b] 331.3g (0,190 mol),
[b] (331,3g0
．． 190 mol) and suspended while stirring.
Hydrosulfide (75g, 0,
431 mol) 300i12 aqueous solution is added dropwise. Stir as is at around 60°C for 3 hours. After cooling to about 10° C., suspended insoluble matter was filtered out, washed twice with acetonitrile on a Metsche filter, and then air-dried after flowing n-hexane. Yield [c] 17.2g (0,114 mol),
Yield 60% 3) ([C] → [d]) P-nitro-phenylsuccinic acid (27,2 (1,0,114 mol) was added to 50 ml of synthetic vinegar flft and stirred). Acetyl chloride (24, h
12.0, 342 mol) was added to perform a dehydration/ring-closing reaction. After reacting for one day, acetyl chloride was distilled off under reduced pressure, and the inside of the container was replaced with nitrogen.
Stirred for a time Wt. Then, acetic anhydride (10.5ml 12.
0.114 mol) was added thereto and reacted at room temperature for 2 hours. When the reaction solution is allowed to cool, a yellowish white solid precipitates out. This was washed with water, filtered, dried, and then recrystallized with acetonitrile. Yield [d] 24.2 g (0,0684 mol), yield 61% 4) ([d] → [e]) Synthesis During methanol 200 reduction, [d] (] 17.2 g
, 0,0684 mol), palladium chloride (2,4
0) was added to perform hydrogenation. After the reaction, it was filtered and the filtrate was vacuum dried. Synthesis of yield Wi [e] 20.4 (+ (0,0629 mol), yield 92%5) ([e] → [[]) [e] (220,
4g0,0629 mol) and pyridine (11,7n1
2.0.145 mol) was added, and methacrylic acid chloride (7 pieces, 0.0725 mol) was added dropwise at 0 to 5°C.
Stirred at 0-5°C for 1.5 hours and at room temperature for 1 hour. Filter off the suspended insoluble matter and wash thoroughly with water. Further, this is dissolved in aqueous ammonia and concentrated hydrochloric acid is added dropwise, and the precipitated solid is collected by filtration and dried. This was recrystallized from acetonitrile. Yield ω [f ] 13.1 (1 (0,0333 mol), yield 53%6) [fl → Synthesis of Exemplary Compound (1) [fl (101
J) Add acrylic fj-n-butyl (10(1),
Polymerization initiator azoisobutyronitrile 0.6g at 80℃
was added to carry out solution polymerization for 4 hours. After the reaction, the suspension was poured into 2Q water and the suspended insoluble matter was filtered out, followed by thorough washing with water. 1117i m+=÷ it i>5Th
/1) IQ! +11 (n
n') 119 mol). Yield 97.5% The above compounds [a], [b], [C], [d], [
el, [r, ] are respectively ]FD-mass spectrum'H
-N M R1[R and was identified by measuring the melting point. ! In addition, exemplified compound (1) was identified by H-NMR and gel permeation chromatography (GPC). When the dye-providing substance of the present invention is a polymer, the molecular weight is 1,500 to 10,000 in terms of weight average molecular weight (MW). is preferred. A synthesis example of Compound (34) derived from Compound [e] as a dye-providing substance of the present invention is shown below. The following margin (it ρ is 12) [el The following margin is [el (5 (], 0.01511 mol) and [Q] (55,95g0.0170 mol) in acetic acid 20
was added, and the mixture was stirred at room temperature for 2 hours.9 cloudy insoluble matter in the reaction solution was collected by filtration, washed with water, and dried. Accomplishment, Exemplary Compound (34) 6.9(] (0,0
103Tnyl) Yield 67% Exemplary compound (34) has FD-mass spectrum, 'l-1
-Nl-1-N and melting point measurement. The dye-providing substances of the present invention may be used alone or in combination of two or more. The use thereof is not limited and depends on the type of the dye-providing substance, whether it is used alone or in combination of two or more, and whether the photographic constituent layer of the heat-developable photosensitive material of the present invention is a single layer or a multilayer of two or more. For example, the amount used can be 0.005 to 10 g, preferably 0.11 to 5.0 g per m2 of support. The dye-providing substance of the present invention may be incorporated into the photographic constituent layer of the heat-developable light-sensitive material by any method. Dissolved in a mineral acid such as hydrochloric acid or 6 [etc.] after dissolving in an aqueous alkaline solution (e.g., 10% aqueous sodium chloride solution, etc.) by ultrasonic dispersion or dissolving in an alkaline aqueous solution (e.g., 10% aqueous sodium chloride solution, etc.). Alternatively, it can be used after being dispersed in a ball mill with an aqueous solution of an appropriate polymer (eg, gelatin, polyvinyl butyral, polyvinylpyrrolidone, etc.). A feature of the present invention is a heat-developable photosensitive material containing the dye-providing substance of the present invention in at least one silver halide emulsion layer. The heat-developable photosensitive material of the present invention is a photosensitive material having at least a photosensitive silver halide, a reducing agent, a binder, and, if necessary, an organic silver salt on a support. The thermal mass Q photosensitive material of the present invention contains a photosensitive silver halide together with the dye-providing substance. The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples include silver chloroiodobromide. The photosensitive silver halide is
Although it can be prepared by any method in the photographic field such as a single jet method or a double jet method, in the present invention, a photosensitive silver halide gelatin emulsion prepared according to 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. As a darning sensitization method,
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 be most preferably 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 C2, B' or I, 0 indicates an H atom, 1 when M is an NH4 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, 1A1 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., K2 Pt Cff
1s, K2PtBrs, HAuC1+
. (Nt” now)2 1 r Cff1s
, (NH,+) 3 1 r CQ
b. (NH2+)2 RIJ CJ26. (Nl-
I4) 3 RU Cfflt; (NH4)2 Rh Cff1s, (NH4)a
Rh Br s, etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cedylethyldimethylammonium bromide, 3-methyldiazolium bromite, trimedelbenzylammonium bromide), quaternary ammonium halides such as , quaternary phosphonium halides such as tetraethylphosphonium bromide, benzylethylmethylsulfonium bromide, 1-
tertiary sulfonium halides such as ethylthiazolium bromide), halogenated hydrocarbons (e.g. iodoform, bromoform, carbon tetrabromide, 2-bromo-2-
methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalate) Zinone, N-bromoacetanilide, N, N-
Dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,
4-dimethylhydantoin, etc.), other halogen-containing compounds (e.g., triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.)
etc. can be given. These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various methods, and the amount of M used is preferably 0.001 g to 5 C1 per TA2 per layer, more preferably, It is 0.1 g to 100. The heat-developable photosensitive material of the present invention may have a multilayer structure including each layer sensitive to blue light, green light, and red light, that is, a heat-developable photosensitive material, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. can. Further, the photosensitive layer of the same color can be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer). In the above case, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion to be used, respectively, can be prepared by adding various spectral sensitizing dyes to the silver halide emulsion. be able to. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, sudaryl, hemicyanine, oxonol, and the like. More preferred are those having a basic base behind the cyanine dye, such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole. Such nuclei include alkyl groups, alkylene groups,
° It may have an enamine group capable of forming a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl fused carbocyclic ring, or a multi-A 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, barbylic acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. good. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat. No. 2,933,3
A supersensitizing additive that does not absorb visible light, such as those described in the specifications of No. 90 and No. 2,937,089, can be used in combination. The amount of these sensitizing dyes added is from 1.times.10@-4 mol to 1 mol per mol of photosensitive silver halide or silver halide forming component. More preferably, 1×10-”mol to 1×
10-' moles. In the heat-developable photosensitive material of the present invention, if necessary, 1 F of organic silver is added to each layer for the purpose of improving sensitivity and developing properties.
8 can be used. Existing silver salts used in the heat-developable photosensitive material of the present invention include Japanese Patent Publications No. 43-4921, No. 44-26582, No. 45-18416, No. 45-12700, No. 45-
No. 22185, JP-A-49-52626, JP-A No. 52-3
No. 1728, No. 52-137321, No. 52-14
No. 1222, No. 53-36224 and No. 53-37
Publications such as No. 610 and U.S. Patent No. 3.330.6
No. 33, No. 3.794.496, No. 4.105.
No. 451, No. 4,123.274, No. 4.168
．． Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, palmitin Ml, silver stearin Fa, silver arachidonic acid, silver behenate, α-( Silver aromatic carboxylates such as silver 1-phenyltetrazolethio) acetate, such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-26582, No. 4
No. 5-12100, No. 45-18416, No. 45-2
No. 2185, JP-A-52-31728, JP-A No. 52-13
No. 7321, JP-A-58-118638, JP-A No. 58-1
Silver salts of imino groups such as those described in publications such as No. 18639, such as silver benzotriazole, silver 5-nitrobenzotriazole, silver 5-chlorobenzotriazole, silver 5-methoxybenzotriazole, and silver 4-sulfobenzotriazole. Silver, 4-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nidropenzimidazole silver, pyrazole silver, urazole silver, 1.2.4- triazole silver, 1
-Tetrazole silver, 3-amino-5-benzylthio-
Silver 1,2,4-triazole, silver saccharin, silver phthalazinone, silver phthalimide, etc., silver 2-mercaptobenzoxazole, silver mercaptooxadiazole,
2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-
1,2,4-triazole silver, 4-hydroxy-6-methyl-1,3,3a, 7-detrazyden silver and 5-
Methyl-7-hydroxy-1,2゜Q 7j A
S ゝ/h +F l,? ' / MltaP h<
Among the one or more organic SR salts to be used, silver salts of imino groups 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 may be used after being isolated and dispersed in a binder by an appropriate means. The silver salt may be prepared in a binder and used as is without isolation. The amount m of the modified silver salt used is preferably 0.01 to 500 mol, more preferably 0.1 mol to 100 mol, per 1 mol of photosensitive silver halide. As the reducing agent used in the thermal photosensitive material of the present invention, those commonly used in the field of thermal photosensitive materials can be used. For example, U.S. Pat.
No. 761,270, No. 3.764.328, and RD No. 12146, No. 15108
, p-phenylene diamine type and p-amine phenol type developing agents, phosphoroamide phenol type and sulfonamide phenol type developing agents, and hydrazone type color developing agents described in JP-A-56-27132 and the like. Can be mentioned. Also, U.S. Patent Nos. 3.342.599 and 3.719.492.
No., JP-A-53-135628, JP-A No. 54-79035
Color developing agent precursors and the like described in No. 1, etc. 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 [41] described in the specification of No. General formula [4] In the formula, R′″ and R6 are hydrogen atoms, or have 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent
represents an alkyl group, and R' and R6 may be ring-closed to form a heterocycle. R7, R&,? R and R are hydrogen atoms, halogen atoms, hydroxy groups,
represents an amine 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 R7 and R' and R? and R6 may each be ring-closed to form a heterocycle. M represents an alkali metal atom, an ammonium group, a nitrogen-containing 1jXA group, or a compound containing a quaternary nitrogen atom. The nitrogen-containing organic base in the above general formula [4] 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-like amine compounds include primary amines, secondary amines, and tertiary amines, and examples of cyclic amine compounds include lysine, quinoline, and typical heterocyclic organic bases. Examples include piperidine and imidazole. In addition, hydroxylamine,
Compounds such as hydrazine and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic acid salts of the organic bases (for example, i!il salts, sulfates, nitrates, 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 [41] are shown below. Below margin (R-1) (R-2) (R-3) (R-4) F3 00 Mr.
(R-20) (R-21) (R-22) (R-23) The reducing agent represented by the above general formula [4] can be prepared by a known method such as Heuben-Peil, Methoden-Organitschen. Houben-We
yl, Methoden der Organisc
hen Chemie, 3and X I/2
) It can be synthesized according to the method described on page 645. A reducing agent as described below can be used. For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-tert-
Abreu p-cresol, N-methyl-aminophenol, etc.), sulfonamide phenol V4 [e.g. 4-benzenesulfonamidofur, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2 .6-Jip D Mo 4-(t)-
Ensulfonamide) phenols, etc., as well as nobidroxybenzenes (e.g. hydroxytert-butylhydride Oquinone, 2.61diJhydro), etc.
]ζJapanese non-carboxyhydroquinone, catechol,
3-hydroxycatechol, etc.), naphthyls (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinafdyls and methylene bisphels [e.g. .1'
-dihydroxy-2,2'-binaphthyl, 6,6'-
Dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-sinitro-2,2'-dihydroxy-1
, 1'-binaphthyl, 4,4'-dimethoxy-1,1'
-dihydroxy-2,2'-binaphthyl, bis(2-hydroxy-1-naphthyl)methane, etc. 1, methylenebisphenols [e.g. 1,1-bis(2- and droxy-3
,5-dimethylphenyl)-3゜5.5-trimedelhexane, 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-1α, α-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methyl Propane, 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. It will be done. These reducing agents can be used alone or in combination of two or more. The amount of reducing agent used depends on the type of photosensitive silver halide, the type of organic acid silver salt, and the type of other additives used, but it is usually used per mole of photosensitive silver halide. It ranges from 0.01 to 1500 mol, preferably from 0.1 to 200 mol. Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural binders such as polyvinyl butyral, polyvinyl acetate, nibble cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more polymeric substances can be used in combination. In particular, it is preferable to use gelatin or its XHJ form together with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably -104249. This binder contains gelatin and a vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or It may also be a copolymer (including a kraft copolymer) of pyrrolidone and one or more other copolymerizable monomers.These polymers can be used regardless of their degree of polymerization.Polyvinyl The pyrrolidone may be substituted polyvinylpyrrolidone, with preferred polyvinylpyrrolidone having a molecular weight of 1,000 to 4.
00.000. 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. and vinyl monomers such as vinyl alkyl ethers; however, it is preferable that polyvinylpyrrolidone accounts for at least 20% (weight ω%, same hereinafter) of the composition ratio. Preferred examples of such copolymers have molecular weights of s, oo
o~400.000. The gelatin may be lime-treated or acid-treated, and may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins. In the binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90% of the total binder ω.
%, more preferably 10 to 80%
%. The binder may contain other polymeric substances,
gelatin and molecules 1 i, ooo ~ 400.000 mixture of polyvinylpyrrolidone and one or more polymeric substances of ponds, gelatin and molecules m 5,000 ~ 400,
000 vinylpyrrolidone copolymer and one or more polymeric materials. 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 7
It may be contained in an amount of 0%. Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it to stand). The amount of binder used is usually 112 to 0 per layer.
．． 051; 1 to 50 g, preferably 0.1 g to 1
0(]. The support used in the heat-developable photosensitive material of the present invention is as follows:
For example, synthetic plastic films such as polyethylene film, cellulose acetate film and polyethylene terephthalate film, polyvinyl chloride, and paper supports such as photographic base paper, printing paper, baryta paper and resin coated paper, and the above-mentioned synthetic plastic films. For example, a support body provided with a 181-layer structure may be mentioned. In particular, it is preferable that various heat solvents be added to the heat-developable photosensitive material of the present invention. The thermal solvent of the present invention may be any substance that promotes thermal development and/or thermal transfer, and is preferably solid, semi-solid, or liquid at room temperature (preferably with a boiling point of 100°C or higher at normal pressure, more preferably 150°C). above) which dissolve or melt in the binder by heating, preferably urea derivatives (e.g., dimethylurea, diethylurea, phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide, etc.), Examples thereof include polyhydric alcohols (for example, 1.5-bentanediol, 1.6-bentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), and polyethylene glycols. For a detailed example, see the patent application 1986-10.
4249. These hot solvents may be used alone or in combination for 2 seconds or more. In addition to the above-mentioned components, various additives may be added to the heat-developable photosensitive material of the present invention, if necessary. For example, as a development accelerator, U.S. Patent No. 3,220,8
No. 40, No. 3.531.285, No. 4,012,
No. 260, No. 4.060.420, No. 4.088
．． No. 496, No. 4,207.392M, device No. 15733, N (1,15?34, No. 392M)
, 15776, JP-A-56-130745, JP-A No. 56-130745
Alkali release agents such as urea and guanidium trichloroacetate described in No. 132332, etc.,
No. 12700) Uti1vi, U.S. RFF M3
．． -Go+, -8O2-, - described in No. 667,959
Non-aqueous polar solvent compounds with 8o-groups, U.S. Pat. No. 3
, 438.776, and polyalkylene glycols described in U.S. Pat. No. 3,666□477 and JP-A-51-19525. In addition, as a color toning agent, for example, JP-A-46-4928, JP-A-46-4928;
No. 6077, No. 49-5019, No. 49-5020, No. 49-91215, No. 49-107727, No. 50-2524, No. 50-67132, No. 50-6
No. 7641, No. 50-114217, No. 52-337
No. 22, No. 52-99813, No. 53-1ozo,
No. 53-55115, No. 53-76020, No. 53
-125014, 54-156523, 5
No. 4-156524, No. 54-156525, No. 54
-156526, 55-4060@, 55-40
61, West German Patent No. 55-32015, West German Patent No. 2.140.406@, West German Patent No. 2,147,063, West German Patent No. 2.220,618, US Patent No. 3.080.2
No. 54, No. 3,847.612@, No. 3,782,
No. 941, No. 3,994,732, No. 4,123
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzothiazine, naphthoxazinedione, which are compounds described in the specifications of , No. 282, No. 4,201,582, 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, mercaptotriazine, dimerkabutotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., and one of these or mixtures of phthalazine and at least one acid or acid anhydride such as phthalic acid, naphthalic acid, or an acid anhydride and a phthalazine compound; Examples include combinations. Also, JP-A-58-189628, JP-A No. 58-1934
3-amino-5-mercapto-1,2,4-triazoles and 3-acylamino-5 described in Publication No. 60
-Mercapto-1,2,4-triazoles are also effective. Furthermore, as an antifoggant, for example,
No. 7-11113, JP-A-49-90118, JP-A No. 49
-10724, 49-97613, 50-1
No. 01019, No. 49-130720, No. 50-1
No. 23331, No. 51-47419, No. 51-574
No. 35, No. 51-78227, No. 51-10433
No. 8, No. 53-19825, No. 53-20923,
No. 51-50725, No. 51-3223, No. 51
-42529, 51-81124, 54-51
Publications such as No. 821 and No. 55-93149, as well as British Patent No. 1.455,271 and U.S. Patent No. 3,885.
, No. 968, No. 3,700,457, No. 4,13
No. 7,079, No. 4.138.265, West German Patent No. 2,617,907, and other mercury salts, or oxidizing agents (for example, N- (halogenoacetamide, N-halogenosuccinimide, perchloric acid and its salts, inorganic peroxides, persulfates, etc.),
Alternatively, acids and their salts (e.g., sulfinic acid, lithium laurate, rosin, diterpene acid, thiosulfonic acid, etc.), or sulfur-containing compounds (e.g., mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur, mercapto-1, 2,4-triazole, thiazolinthione, polysulfide compounds, etc.), others,
Examples include compounds such as oxazoline, 1,2°4-triazole, and phthalimide. Furthermore, thiol (preferably a thiophenol compound) compound described in JP-A-59-111636 is also effective as another antifoggant. In addition, as other antifoggants, Japanese Patent Application No. 59-565
Hydroquinone derivatives described in No. 06 (e.g.
[-octylhydroquinone, dodecanylhydroquinone, etc.] and hydroquinone derivatives described in Japanese Patent Application No. 1983-66380 and 11 benzotriazoles (e.g., 4-octylhydroquinone, dodecanylhydroquinone, etc.)
Sulfobenzotriazole, 5-carpoxybenzotriazole, etc.) can be preferably used in combination. In addition, as a stabilizer, a printout preventive agent may also be used at the same time, especially after processing.
Halogenated hydrocarbons described in Publication No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, Examples include bromomethylsulfonylbenzodiazole and 2,4-bis(tribromomethyl)-6-methyltriazine. Also, Japanese Patent Publication No. 46-5393, Japanese Patent Publication No. 50-54329
Post-treatment may be carried out using a sulfur-containing compound as described in No. 50-77034. Furthermore, U.S. Patent No. 3,301,678;
No. 506, 444, No. 3,824.103, No. 3
, 844,788, as well as the isothiuronium-based stabilizer and precursor described in U.S. Pat.
669.1370@, No. 4,012,260, No. 4,060,420, Activator Stabilizer Precursor etc. described in Mei 111, etc. may be contained. Also, sucrose, NH4Fe (SO+), -12820
Water release agents such as
Heat development may be carried out by supplying water as in No. 132332. In addition to the above-mentioned components, the heat-developable photosensitive material of the present invention may optionally include a spectral sensitizing agent, an antihalation dye, a fluorescent brightener, a hardening agent, an antistatic agent, a plasticizer, a spreading agent, etc. Additives, coating aids, etc. are added. The heat-developable photosensitive material of the present invention includes (1) a photosensitive silver halide, (2) a reducing agent, and (3) a dye-providing substance of the present invention in a photosensitive layer which is basically one silver halide emulsion layer. ,(4)
It is preferable to contain a binder and, if necessary, (5) an organic silver salt. However, these do not necessarily need to be contained in a single emulsion layer; for example, the photosensitive layer may be divided into two layers, and the above (1)
), (2), (4), and (5) are contained in the photosensitive layer on one side, and the polymeric dye-donating substance (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 constituent layers. Further, the photosensitive layer may be divided into two or more layers, such as a high sensitivity layer and a low sensitivity layer, and may further include one or more 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. Similar to the heat-developable photosensitive layer of the present invention, coating solutions are prepared for the protective layer, intermediate layer, undercoat layer, back layer, and other photographic constituent layers, using the dipping method, air knife method, curtain coating method, or U.S. The photosensitive material can be prepared by various coating methods such as the hopper coating method described in Japanese Patent No. 3,681.294. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. The above-mentioned components used in the photographic constituent layer of the heat-developable photosensitive material of the present invention are coated on a support, and the coating thickness after drying is preferably 1 to 1,000 μm, more preferably 3 to 1,000 μm.
It is 20 μm. After the heat-developable photosensitive material of the present invention is imagewise exposed as it is,
Usually 80°C to 200°C, preferably 120°C to 170°C
In the temperature range of 1 second to 180 seconds, preferably Schiff is 1.
Color development can be achieved by simply heating for 5 seconds to 120 seconds. Further, if necessary, a water-impermeable material may be applied and developed, or preheating may be performed at a temperature in the range of 70° C. to 180° C. before exposure. Various exposure means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources commonly used for color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source. As the heating means, all methods applicable to ordinary photothermographic materials can be used, such as bringing the material into contact with a heated block or plate, contacting with a heated roller or drum, or passing it through a high-temperature atmosphere. Alternatively, it is also possible to use high frequency heating, or more specifically, 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 Joule heat generated by electricity or a strong magnetic field. There are no particular restrictions on the heating pattern, including methods of 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 repeating the heating. Although discontinuous heating is possible, a simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used. The image receiving member used in the present invention only needs to have the function of receiving the dye released or formed by thermal development, and may be a mordant used in a dye diffusion transfer type light-sensitive material or a special
The glass transition temperature described in No. 207250 etc. is 40℃
As mentioned above, it is preferable to use a heat-resistant polymeric material having a temperature of 250° C. or less. Specific examples of the mordants include nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, quaternary cationic compounds thereof, U.S. Pat. Nos. 2,548,564 and 2,48
No. 4,430, No. 3,148,061, No. 3,756
, vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Pat. No. 2,615,316, polymers containing dialkylamino groups as disclosed in U.S. Pat. Aminoguanidine derivatives, JP-A-1987
Covalently reactive polymers described in U.S. Pat. No. 3,625,694 and U.S. Pat.
No. 96, British Patent No. 1.277, 453, British Patent No. 2,01
A mordant capable of crosslinking with gelatin etc. disclosed in US Pat. No. 3,958,995, US Pat. No. 2,7
21,852 and 2,798, 063; water-insoluble mordants disclosed in JP-A-50-61228; and U.S. Pat. No. 3,788.
No. 855, West German Patent Application (OLS) No. 2,843,32
No. 0, JP-A-53-30328, JP-A No. 52-15552
No. 8, No. 53-125, No. 53-1024, No. 5
No. 4-74430, No. 54-124726, No. 55-
No. 22766, U.S. Patent No. 3,642,482,
No. 3.488.706, No. 3,557,066, No. 3.271.147, No. 3,271,148, Special Publication No. 55-29418, No. 5G-36414, No. 57
Various mordants disclosed in No. 12139, RD 12045 (1974) can be mentioned. Particularly useful mordants are polymers containing ammonium salts,
Polymer containing quaternary amino groups as described in US Pat. No. 3,709,690. Examples of polymers containing ammonium salts include polystyrene-N,N,N-1-hexyl-N-vinylbenzylammonium chloride, and the ratio of styrene and vinylbenzylammonium chloride is 1:4 to 4:1. Preferably the ratio is 1:1. A typical receiving I& layer for dye diffusion transfer is obtained by coating a polymer containing an ammonium salt mixed with gelatin on a support. As an example of the heat-resistant organic polymer substance, a molecular weight of 2.0
00' to 85,000 polystyrene, polystyrene derivatives with substituents having 4 or less carbon atoms, polyvinylcyclohexane, polyvinylbenzene, polyvinylpyrrolidone,
Polyacetals such as polyvinyl carbazolebenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichloride fluoroethylene, polyacrylonitrile, polyN. N
-dimethylacrylamide, polyacrylate with p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate-1, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl metalcrylate Polyesters such as ester, polyisobutyl methacrylate, poly tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthalate, polycarbonates such as polysulfone, bisphenol A polycarbonate, polyanhydride , polyamides, cellulose acetates, and the like. In addition, the Polymer Handbook 2nd Edition (Polymer Handbook 2nd Edition)
Handbook 2nd ed. ), G.A. Brandlap, E.H. Inmargt1i
i LJ. Brandrup, E. H. I
mmergut Jl). Ji1in・rLI,/11-, Anoba・Nobu Tani/
Also useful are synthetic polymers having a glass transition temperature of 40° C. or higher, as described in , 1 nhnwiley&sons. These polymeric substances may be used alone or in combination of two or more as a copolymer. Particularly useful polymers include cellulose acetates such as triacetate and diacetate; polyamides in combinations such as heptamethylene diamine and terephthalic acid; fluorene dipropylamine and adipic acid; hexamethylene diamine and diphenic acid; hexamethylene diamine and isophthalic acid; Examples include polyesters made by combining diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, polyethylene terephthalate, polycarbonate, and vinyl chloride. These polymers may be modified. For example, polyethylene terephthalate using cyclohexane dimetatool, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid, etc. as a modifier is also effective. Among these, particularly preferred are the
Examples include a layer made of polyvinyl chloride described in Japanese Patent Application No. 8-91907 and a layer made of polycarbonate and a plasticizer described in Japanese Patent Application No. 128600/1983. The above polymer is used by dissolving it in a suitable solvent and coating it on a support to form an image receiving layer, or by laminating a film-like image receiving layer made of the above polymer on a support, or by coating it on a support. It is also possible to constitute the receiving layer by a member (for example, a film) made of the above polymer alone (also used as an image receiving layer support). Furthermore, the image-receiving layer may be constructed by providing an opacifying layer (reflective layer) containing titanium dioxide or the like dispersed in gelatin on the receiving layer on the transparent support. In the opaque layer, a reflective color image can be obtained by viewing the transferred color image from the transparent support side of the receiving layer. Below is a blank space Example 1 Exemplary dye-providing substance (1) (weight average molecule ffl M w
= 4,800) 470+ng of ethyl acetate 2.1C
Dissolved in C. This solution was mixed into a 2.5% aqueous gelatin solution containing a surfactant.
After mixing with cc and adding water to make 6.5 cc, the mixture was dispersed with a homogenizer to obtain a dispersion of the dye-providing substance. After mixing 6.5 cc of the above dispersion with 3.5 cc of water containing 450 mg of polyvinylpyrrolidone (average molecular weight 30,000) and somg of 1.5-pentadiol, and adding 200 ma of the above exemplary reducing agent (R-3). , 1 lJH was adjusted to 5.5 with 3% citric acid. A silver iodobromide emulsion with an average grain size of 0.1 μm was added to this dispersion in an amount of 1×10 −
Add 3 mol (contains 85 ma of gelatin), add water and make 1
After finishing to 5 cc, a photosensitive layer was coated onto a polyethylene terephthalate support using a wire bar so that the dry film thickness was 8 μm. After drying the resulting light-sensitive material, a white exposure of 16,0 OOCM S was applied through a step wedge. Next, the image-receiving layer surface of the image-receiving member, in which polyvinyl chloride as the image-receiving layer material was separately coated on baryta paper, and the coated surface of the exposed photosensitive material were superimposed, and thermal development was performed at 150° C. for 1 minute to form an image. The member was peeled off to obtain a magenta transferred image on the image receiving member. The highest anti-DA of the resulting transferred image
The density (Dmax) and fog ([)o+in) are shown in the table.
Shown in 1. Comparative Example 1 In the photosensitive material of Example 1, the dye-providing substance of the present invention (
A photosensitive forest material was prepared in the same manner as in Example 1, using the following comparative polymer PM-1 in place of 1). The same heat development as in Example 1 was performed. The results are shown in Table-1. (J Niji Chokuhon° Rimmer PM-1) Table 1 As is clear from the margin table 1 below, in the heat-developable photosensitive material that does not use an organic silver salt, the sample using the dye-donating substance of the present invention has a It can be seen that D max is large and [ ) min is small even though there are fewer addition ports compared to the sample. Example 2 [Preparation of silver 4-sulfobenzotriazole] 24a-4
-Sulfobenzotriazole and 4 g of sodium hydroxide were added and dissolved in 300 vQ of ethanol-water (1:1) mixture. 201 g of 5N silver nitrate solution was added dropwise to this solution. At this time, a 5N sodium hydroxide solution was also added dropwise at the same time to maintain flN at 7-8. This solution was stirred for 1 hour at room temperature and then added with water for 400. A 4-sulfobenzotriazole silver solution containing 20% excess of 4-sulfobenzotriazole was prepared. [Preparation of photosensitive material] Dye-providing substance (l) similar to Example-1 327 mG
and 1,4-dioctylhydride 0quinone 30m. was dissolved in 2.1 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 the volume 6.5 cc, and the mixture was dispersed with a homogenizer to obtain a dispersion of the dye-providing substance. 4 vQ of the above 4-sulfobenzotriazole silver solution and 6 cc of the dye-donor dispersion were mixed, and then polyvinylpyrrolidone (average molecular weight 1,130,000) 450I1
g, pentaerythritol 120a+a, 1, 5-
After adding 420 mg of Q nopentadiol and 200 mo of the same reducing agent (R-3) used in Example 1, the pH was adjusted to 5.5 with 3% citric acid. A silver iodobromide emulsion with an average grain size of 0.05 μm was added to this dispersion in a ratio of 3 × 1 in terms of silver.
After adding 0 to 4 mol of gelatin (containing 75 ffiO of gelatin) and finishing it to 14 nQ by adding water, the photosensitive layer was coated onto a polyethylene terephthalate support using a wire bar so that the dry film thickness was 8 μm. After drying the obtained photosensitive material, a white exposure of 32.0 OOCM 3 was applied through a step wedge, and then Example-
Thermal development was performed on an image receiving member similar to Example 1 under the same conditions to obtain a magenta transferred image on the image receiving member. Maximum reflection density ([)maX) and fog (pmi) of the obtained transferred image
n) are shown in Table-2. Example 3 In the light-sensitive material of Example 2, the dye-providing substance of the present invention (
1) is an exemplary compound (1) which is a dye-providing substance shown in Table 2.
A heat-developable photosensitive material was prepared in the same manner as in Example 2 except that 0), (22), and (34) were replaced, and heat development was performed in the same manner as in Example 2 to obtain a magenta transferred image on an image-receiving member. . The results of the obtained transferred image density are also shown in Table 2. Example 4 A photosensitive material similar to that of Example 2 was prepared, except that reducing agent R-3 was replaced with reducing agents R-1 and R-9 shown in Table 2. Exposure and heat development were carried out in the same manner as in Example 2 to obtain a magenta transferred image. The results of the obtained transferred image density are shown in Table 2. Comparative Example 2 In the light-sensitive material of Example 2, the dye-providing substance (1) was added to the comparative polymer PM-1 and a light-sensitive material similar to the following was prepared and thermally developed in the same manner as in Example 2 to form a magenta color on the image receiving member. A transferred image was obtained. As is clear from the results in Margin Table 2 below, in the photothermographic material using the dye-providing substance of the present invention, sample No. 013.
In 4.5, compared to comparative samples No. 9 and 9, even though the amount added was smaller, [) max was about the same, and Q
It can be seen that (min) is extremely small and the occurrence of fog due to thermal development has been improved. In addition, among the dye-donating substances of the present invention, [)(max) is for sample No. 016 using a dye-donating substance with a relatively small molecular weight that does not have a repeating unit, and [ ) (max) is for comparison sample No. 029 using a comparative polymer, It can be seen that the image density is maintained high and the thermal fog is reduced because the D (10 in) is small and the diffusible dye production efficiency is high, and the thermal fog is reduced. Furthermore, even if the reducing agent that directly affects heat development is changed, D(1n) is low in samples No. 7 and N008, and the dye-donating substances of the present invention all have high diffusible dye production efficiency. It can be seen that thermal fog is extremely small and has been improved.

Claims (1)

[Claims] At least one silver halide emulsion layer on the support has 7
1H-pyrazolo[3,2-C
] A heat-developable photosensitive material containing an -S-triazole compound.