JPS62238554A - Heat developable photosensitive material having improved image quality - Google Patents

Abstract

PURPOSE:To obtain the title material having excellent image quality and improved max. optical density and less tendency for generating fog by incorporating a particle formed from a polymer of a coloring matter affording substance together with a high b.p. solvent to the title material, and by constituting the title material at a specific wt. ratio of the coloring matter affording substance and the high b.p. solvent. CONSTITUTION:The title material contains the particle formed from the coloring matter affording substance (the former) together with the high b.p. solvent (the latter) and has 0.05-4.0 of the wt. ratio of the latter to the former. The former is a polymer having a repeating unit derived from the monomer of the former shown by formula (1) or (2) wherein Q is an ethylenically unsatd. group, Cp1 and Cp2 are each an org. group capable of forming or releasing a diffusible coloring matter by reacting it with an oxidant of a reading agent, X is a bivalent binding group which is binded with active points of Cp1 and Cp2. (n) is 0 or 1, Dye is a residue of the diffusible coloring matter. Thus, the title material having excellent picture quality and high max. density of the image and less tendency for generating fog is obtd. by using the polymer of the coloring matter affording substance.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photographic light-sensitive material that forms an image by heat development, and more particularly to improving the image quality of a heat-developable light-sensitive material containing a dye-providing polymer. be.

BACKGROUND OF THE INVENTION In recent years, heat-developable photosensitive materials whose development process can be carried out by heat treatment have attracted attention as photosensitive materials.

Regarding such heat-developable photosensitive materials, for example,
-4921 and No. 4'3-4924 disclose a photosensitive material consisting of an organic silver salt, silver halide, a reducing agent, and a binder, which was commercialized by Dry Silver Co., Ltd. and t3M. There is.

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

For example, U.S. Pat. No. 3,531,286;
No. 761゜270 and No. 3,764,328, etc. describe a method of forming a dye image by the reaction of an oxidized product of an aromatic primary amine developing agent with a coupler, Research Disclosure (Research [ ) 1
15108 and 15127
, sulfonamide phenol or sulfonamide aniline X described in U.S. Patent No. 4,021,240, etc.
4 reducing agents (hereinafter also referred to as developer or developing agent)
A method of forming a dye image by the reaction of an oxidized form of and a coupler, as disclosed in British Patent No. 1.590.956, which uses an organic imino silver salt having a dye moiety and liberates the dye in a heat development section. A method for releasing a dye image on a separately provided image-receiving layer, and JP-A-52-105821,
52-105822, 56-50328, and U.S. Pat. No. 4,235,957, etc., a method for obtaining a positive dye image by the silver dye bleaching method, as well as U.S. Pat. No. 3,180,731. , No. 3,985,565, No. 4,022,617, No. 4,452,883
Various methods have been proposed, such as a method for obtaining a dye image using "leuco dye" disclosed in Japanese Patent Application Laid-Open No. 59-206831.

However, these proposals regarding the heat-developable color light-sensitive materials have the disadvantages that it is difficult to bleach-fix the black, white, and silver images that are formed at the same time, that it is difficult to obtain clear color images, and that it is difficult to obtain clear color images. Since these methods require post-processing, they are still unsatisfactory for practical use.

In recent years, as a color image forming method using a new type of heat treatment, Japanese Patent Laid-Open No. 57-179840 and No. 57-186 have been developed.
No. 744, No. 57-198458, No. 57-2072
No. 50, etc., disclosed a method of obtaining a color image by transferring a diffusible dye released by thermal development.

By further improving these methods, for example, a non-diffusible seedling dye-donating substance disclosed in JP-A-58-58453@, JP-A-59-168439, etc. is oxidized to make it diffusible. Method for releasing dye, JP-A-58-
No. 79247, No. 59-174834, No. 59-1
No. 2431, No. 59-159159, No. 60-295
A method of releasing a diffusible dye by coupling with an oxidized form of a developing agent as disclosed in No. 0, etc.;
JP-A-58-149046, JP-A No. 58-149047
No. 59-124339, No. 59-181345
No. 60-2950, Japanese Patent Application No. 59-181604, No. 59-182506, No. 59-182507
No. 59-272335, etc., which uses a non-diffusible compound that reacts with an oxidized developing agent to form a diffusible dye;
No. 52440, No. 59-124327, No. 59-15
No. 4445, No. 59-1669544, etc.
Methods have been proposed that include non-diffusible reducing dye-donating substances that lose their ability to release diffusible dyes when oxidized, and systems that contain non-diffusible dye-donating substances that release diffusible dyes when reduced. ing.

In the heat-developable photosensitive material, the released or formed diffusible dye is transferred onto an image-receiving layer of an image-receiving member provided on the same support or another independent support.

It produces a transferred color image, and is improved in many respects compared to previous heat-developable color photosensitive materials in terms of image sharpness, stability, etc.

The basic composition of a color-type heat-developable photosensitive material that produces a color image using these emitted or formed diffusive dyes consists of a photosensitive element and an image-receiving element, and the photosensitive element is basically made of photosensitive silver halide. , organic silver salt, reducing agent,
It consists of a dye-providing substance and a binder. In addition,
In the present invention, only the photosensitive element is referred to as a heat-developable photosensitive material in a narrow sense, and the image receiving element is referred to as an image receiving member.

A method has been proposed in which the dye-providing substance is made into a polymer to improve its molecular weight and improve its non-diffusibility to prevent color turbidity and the like.

For example, JP-A-58-149047, JP-A No. 60-2950
No. 60-222850, patent application No. 59-17965
No. 7, No. 59-181604, No. 59-182506
No. 59-182507, etc.

These dye-donor polymers are also attracting attention because of their high ability to release or form dyes, thus providing high maximum densities and low capri.

However, it has become clear that the image quality of dye images obtained with heat-developable photosensitive materials containing these dye-donor polymers is degraded, particularly in fine areas.

In a wet-type silver halide photosensitive material using an ordinary liquid developer, the dye-providing substance polymer is called a coupler polymer. ) have been proposed, but no such deterioration in image quality has been observed.

Further, it has been found that the transfer of the dye image formed or released in the photothermographic material to the image receiving member has a small contribution to the deterioration of the image quality.

This is because the light-sensitive material and the image-receiving member are directly bonded to each other, compared to normal diffusion transfer-type photosensitive materials, in which the dye image is transferred from the light-sensitive material to the image-receiving member at room temperature with a layer of alkaline viscous developer in between. Or perhaps it is because they are located extremely close together.

Therefore, such deterioration in image quality is considered to be caused by heat development (heating at high temperature) of the dye-providing material polymer, and can be said to be a drawback specific to heat-developable photosensitive materials.

Therefore, there has been a need for a heat-developable photosensitive material with good image quality that improves the drawbacks specific to the above-mentioned photothermographic materials.

[Object of the Invention] A first object of the present invention is to provide a heat-developable photosensitive material with excellent image quality using a dye-donating polymer.

A second object of the present invention is to provide a heat-developable photosensitive material that has a high maximum image density and less fog.

A third object of the present invention is to provide a heat-developable photosensitive material that has excellent dispersion stability during preparation, anti-thickening properties, and the like.

[Structure of the Invention] The object of the present invention is to provide a heat-developable photosensitive material having at least a photosensitive silver halide, a dye-donor polymer, a reducing agent, and a binder on a support, in which the dye-donor polymer is dispersed in particles together with a high-boiling point solvent. is present in the form of
．． This was achieved by setting it to 0.

[Specific Structure of the Invention] The dye-providing substance polymer used in the present invention will be explained.

In the present invention, the dye-providing substance polymer refers to the following general formula [
11, a polymer having repeating units derived from the dye-providing substance monomer shown in [2].

General formula [1] (Qmo → are organic groups that react with the oxidized form of the reducing agent to form or release a diffusible dye, X represents a divalent bonding group, and the X is bonded to the active site of CD+ and CD2, n is 0
or 1, and Dye represents a diffusible dye residue.

The weight average molecular weight of the dye-providing substance polymer used in the present invention is preferably 30,000 to 5oooooo, more preferably 100,000 to 200,000G.

In the present invention, the average molecular weight of electricity is measured by the GPC method (gel permeation chromatography method). The measurement method is shown below.

GPC: HLC-802A (manufactured by Toyo Soda) Column: T
Stel (manufactured by Toyo Soda GM) ((exclusion intraocular molecules 14 x 1011, column size 7.51
m) 1 Aqueous solvent: THF Flow m: 1 n12/min' Column temperature:
38°C Detector: UV-8 model I [(manufactured by Toyo Soda) Detection wavelength 254 nm A calibration curve was prepared using TSK standard polystyrene (manufactured by Toyo Yosoku).

In the present invention, when the monomer represented by general formula [1] or [2] remains unreacted in the dye-providing substance polymer of the present invention, this residual ω is 5% by weight of the Kindan polymer. % or less, more preferably 0.5% by weight
It is as follows. Most of the residual monomers can be measured by the above-mentioned GPC method.

The general formulas [1] and [2! , ], the ethylenically unsaturated group and the ethylenically unsaturated group-containing group represented by Q are preferably groups represented by the following general formula [3].

General formula [3] [3] In the formula, R represents a hydrogen atom, a carboxyl group, or an alkyl group (for example, a methyl group, an ethyl group, etc.), and this alkyl group includes those having a substituent. , for example, a halogen atom (eg, a fluorine atom, a chlorine atom, etc.), a carboxyl group, and the like. The carboxyl group represented by R and the carboxyl 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 -NHCO-
1-CONH-1-COO-1-OCO-1-SCO-
1-COS-1-〇-1-S-1-SO-1-3O2-
etc. Xl and x2 each represent a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include an alkylene group, an arylene group, an aralkylene group, an alkylenearylene group, and an arylenealkylene group, and the alkylene group includes: For example, methylene group, ethylene group,
Examples of arylene groups include phenylene and lene groups; examples of aralkyl groups include phenylmethylene groups; examples of alkylenearylene groups include methylenephenylene groups; Examples of the arylene alkylene group include a phenylene methylene group. K111, ff11, ri2 and m2 each represent 0 or 1. Furthermore, Cpl and CI)2 are each so-called coupler residues, and are preferably groups represented by the following general formula.

In the following margins (6) (7) Formulas [4] to [13], R1, R2, R3 and R4 are each hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amino group, alkoxy group, acyloxy group, cyano group, ureido group, alkylthio group, arylthio group, carboxyl group, sulfo group or a heterocyclic residue, and these groups further include a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, a cyano group, a nitro group, an alkyl group, an aryl group, an aryloxy group, an acyloxy group, an acyl group, and a sulfamoyl group. ,
It also includes those substituted with carbamoyl groups, imide groups, halogen atoms, etc.

These substituents are selected depending on the purpose of Cpl and CD2, and in CD2, one of the substituents is an ethylenically unsaturated group represented by Q or a group having an ethylenically unsaturated group.

In addition, as the divalent bonding group represented by X in general formulas [1] and [2], the following general formulas [14] to [38]
Those represented by are preferred.

General formula [14] General formula [15] a General formula [16] General formula [17] General formula [
18] General formula [I9]-NHCONH-
R! '-NHSO2-(C')rl General formula [addition] General formula [21]-NH302
NH-R.

"-S-Bo) Grave general formula [Z2] General formula [ru] General formula [2]
4] −N=N set [! In [4] to [22], R3 and Ro each represent a hydrogen atom or an alkyl group (for example, a methyl group, an ethyl group, etc.), and the number represents 0.1 or 2.

General formula [5] General formula [26] General formula [2]
7] General formula [A] General formula [4]
General formula [30] General formula [31] General formula [32] General formula [33] General formula [3]
4〇General formula [35] General formula [3G] General formula [
37] General formula [38] In formula [25] to formula [38], R7 is a hydrogen atom, a halogen atom,
Alkyl group, cycloalkyl group, aryl group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, alkylsulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amino group, alkoxy group, aryloxy group, Cyam L represents a ureido group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group, a heterocyclic residue, etc., and these groups further include a hydroxyl group, a carboxyl group, a sulfo group, an alkoxy group, a cyano group, a nitro group, an alkyl group. , aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, imide group, halogen atom, etc. are also included.

Dye represents a dye residue that is eliminated when CD2 reacts with an oxidized form of a reducing agent. Examples of dye residues include residues of azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, phthalocyanine dyes, etc. For example, yellow, magenta and cyan dyes have the following general formula: [39] ~
Examples include the dyes shown in [73].

(Yellow) General formula [39] General formula [40] General formula [
41] General formula [42] It,, l (hot 2 General formula [45] General formula [46] 〇 General formula [47] General formula [48] H (magenta) General formula [49] General formula [father] R3゜1′ General formula [57] General formula [58] (cyan) General formula [63] General formula [64] General formula [
65] General formula [66] General formula [67]
General formula [difficult] General formula [69]
General formula [70] General formula [71] General formula [72] General formula [73] R1 In formulas [39] to [73], R8 to R+3 are each a water atom, an alkyl group, a cycloalkyl group, an aralkyl group, Alkoxy group, aryloxy group, aryl group, acylamino group, acyl group, cyano group, water M group, arylsulfonylamino group, arylsulfonylamino group, alkylsulfonyl group, hydroxyalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, Alkoxyalkyl group, aryloxyalkyl group, nitro group, halogen atom, sulfamoyl group, N-substituted sulfamoyl group, carbamoyl group, N-Mm carbamoyl group, sulfamide group, N-substituted sulfamide group, hydroxyalkoxy group, alkoxyalkoxy group, carboxyl group,
It represents a substituent selected from an amino group, a substituted amine group, an alkylthio group, an arylthio group, a hydroxamic acid group, an imide group, a sulfo group, a phosphoric acid group, a quaternary ammonium group, a ureido group, a heterocyclic group, and the like.

Further, as another preferable dye, the following general formula [74
] and [75].

General formula [741 General formula [75] H In formulas [74] and [75], Yl is an aromatic ring in which at least one ring is composed of 5 to 7 atoms (e.g. benzene ring, naphthalene ring) or Represents the atomic group necessary to form a heterocycle (e.g. pyridine ring, pyrazole ring, pyrazolotriazole ring), and at least one adjacent position of the carbon atom bonded to the azo bond is (a
) is a nitrogen atom, or (b) is a carbon atom substituted with a nitrogen atom, an oxygen atom, or a sulfur atom, and Y2 is an aromatic ring in which at least one ring is composed of 5 to 7 atoms (e.g. G represents a chelating group (e.g. amino group, hydroxyl group, carboxyl group, alkoxy group, thioalkoxy group). RI4
and R+s have the same meaning as R6 to R13 above.

The dye residue may be in a temporarily shortened form that can be restored during thermal development or transfer.

More preferred forms of the compound represented by the general formula [1] are compounds represented by the following general formulas [76J to [81].

General formula [76] ' General formula [77] In general formula [76] and c 77 ], R1 each represents a furkyl group, an aryl group, or a heterocyclic residue including one having a substituent, and R2 and R3 are Each represents a hydrogen atom or an alkyl group, aryl group, or heterocyclic residue including those having a substituent, R4 represents a hydrogen atom or an alkyl group including those having a substituent, and X represents a hydrogen atom or an alkyl group including one having a substituent. Jl and J2 each represent a bonding group of 21i11i, and Yl represents a bonding group of 21i1[i
represents a hydrocarbon group, Y2 is -(Z2)02c○OMt
-represents a substituted divalent hydrocarbon group, zl and Z2
each represents an alkylene group, M represents a hydrogen atom, an NH4 group, or a monovalent metal atom, K, ffi, m1n+,
n2 each represents O or 1.

General formula [78] %Formula% In general formula [78], R1 represents an alkyl group,
R2 represents an alkyl group or an aryl group, R3 represents a divalent hydrocarbon group, R4 represents an alkyl group or a hydrogen atom, J represents a divalent bonding group, l represents O or 1, m represents O or 1.

General formula [79] In general formula [79], Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and 2 represents a nitrogen-containing heterocyclic residue (with polymerizable ethylene in the ring) together with the N atom. R1 represents an alkyl group, an aryl group, an alkylamino group, an acylamino group, or a ureido group, and A represents an aryl group. or represents a heterocyclic residue, and n represents 0 or 1.

General formula [80] In general formula [80], R1 is a hydrogen atom, and has 1 to 1 carbon atoms.
It represents four alkyl groups or chlorine atoms, and R2 and R3 each represent an alkylene group, an arylene group, or an aralkylene group including those having substituents, and the alkylene group may be linear or branched. X represents 100NH- or -COO-, Y represents 10-1-S-1-SO
-1-8O2-1-CON H-t: tc bar CO
O-, Ar represents a phenyl group including one having a substituent, R4 represents an unsubstituted or substituted anilino group, acylamino group or ureido group, and (l, m
and n each represent ○ or 1.

In the general formula [81], X represents an atomic group necessary to form a benzene ring or a naphthalene ring. The benzene ring or naphthalene ring formed here includes those having substituents. Y represents an oxygen atom or a sulfur atom, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, M is a hydrogen atom, an N84 group or a
Represents a valent metal atom.

Specific examples of the compound represented by the general formula [1] are shown below, but the present invention is not limited thereto.

CH Yu M-7 CH.

M-9 8-12 hll M-14 Shuuit C0
OHH Specific examples of the compound represented by the general formula [2] are shown below, but the present invention is not limited thereto.

M -16 mu(-17 8(-18) IQOH) The polymer having a repeating unit derived from a single m compound represented by the general formula [1] or [2] of the present invention is
1 of the monomers represented by the above general formula [1] or [2]
It may be a so-called homopolymer, which is a repeating unit consisting only of seeds, or it may be a copolymer that combines two or more monomers represented by the general formula [1] or [2], and it may also be a copolymer of other types. It may also be a copolymer consisting of one or more comonomers having ethylenically unsaturated groups.

Examples of the comonomer having an ethylenically unsaturated group that can form a copolymer with the monomer represented by the general formula [1] or [2] of the present invention include acrylic esters, methacrylic esters, vinyl esters, and olefins. styrenes, crotonate esters, itaconate diesters, maleate diesters, fumarate diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles Examples include polyfunctional monomers, various unsaturated acids, and the like.

More specifically, these comonomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, ter
t-Butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxy Ethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl -3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propyl methacrylate, 2-butoxyethyl acrylate, 2-(2-
methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of moles added =
9), 1-bromo-2-methoxyethyl acrylate,
Examples include 1,1-dichloro-2-ethoxyethyl acrylate.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl acrylate, 5ec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, and cyclohexyl. Methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydro furfuryl 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-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>, allyl methacrylate, methacrylic acid dimethylaminoethyl methyl chloride salt, and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc. Can be mentioned.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, promstyrene, and vinylbenzoic acid methyl ester. Can be mentioned.

Examples of crotonate esters include butyl phosphate, hexyl crotonate, and the like.

Examples of itaconic acid diesters include itacon-resistant dimedyl, diethyl itaconate, and dibdel itaconate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like.

Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Examples of other comonomers include:

Acrylamides, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.; Methacrylamides, such as methacrylamide, methylmethacrylamide, ethyl acrylamide , propyl methacrylamide, butyl methacrylamide, tert
-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide,
Dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide,
N-(2-7cetoacetoxyethyl)methacrylamide, etc.; Allyl compounds, such as furyl 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-vinyloxazolidone, N -vinyltriazole, N-vinylpyrrolidone, etc.; glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; unsaturated nitriles, such as acrylonitrile, methacrylateril, etc.; polyfunctional monomers, such as divinylbenzene, methylenebisacrylamide, such as ethylene glycol dimethacrylate.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates, such as monomethyl maleate, monoethyl maleate, maleic acid; Monobutyl acids, etc.; citraconic acid, styrene 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.; acrylamide alkylsulfonic 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 and acryloyloxyalkyl phosphate,
For example, acryloyloxyethyl phosphate, 3-
Acryloyloxypropyl-2-phosphate, etc.;
Methacryloyloxyalkyl phosphates, e.g.
Methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.: Examples include sodium 3-aryloyloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali gold (eg, Na, etc.) or ammonium ions.

Other comonomers include U.S. Patent No. 3.4
No. 59.790, No. 3.438.708, No. 3,
No. 554゜987, No. 4,215,195, No. 4
, 247,673, JP-A-57-205735, Mei IB, and the like can be used. Examples of such crosslinking monomers include:
Specific examples include N-(2-acetoacetoxyethyl)acrylamide, N-(2-(2-acetoacetoxyethoxy)ethyl)acrylamide, and the like.

Further, when forming a copolymer with the monomer represented by the general formula [1] or [2] of the present invention and the polymer, it is preferably represented by the general formula [1] or [2]. This is the case where the repeating unit consisting of a single M is contained in an amount of 10 to 90% by weight of the entire polymer, and more preferably 30 to 70% by weight of the total polymer.

Generally, the polymer coupler is polymerized by emulsion polymerization method or solution polymerization method, and has a repeating unit derived from the monomer represented by the general formula [1] or [2] according to the present invention. Material polymers can also be polymerized in a similar manner. Emulsion polymerization methods are described in U.S. Pat. 45
1,820 can be used.

These methods are also applicable 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 fixed matrix.

Examples of emulsifiers used in the emulsion polymerization method include surfactants, polymeric protective colloids, and copolymer emulsifiers. Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants known in the art.

Examples of anionic surfactants include soaps, sodium dophylbenzenesulfonate, sodium lauryl sulfate, sodium dioctylsulfosuccinate, and acid salts of nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxypropylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines.

Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Examples of the polymeric protective colloid include polyvinyl alcohol and bitroxyethyl cellulose. These protective colloids may be used alone as emulsifiers or in combination with other surfactants. For information on the types of these activators and their effects, please refer to the Belgian
Hemi-Industry X (3elQisct18Ch
emische Industrie), 28.
16-20 (1963).

In order 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 an organic solvent, and then dissolved in an aqueous gelatin solution with the help of a dispersant. Then, it is dispersed into a latex form using ultrasonic waves, a colloid mill, etc. A method of dispersing lipophilic polymers in latex form in aqueous gelatin solutions is described in US Pat. No. 3,451,820.

Possible solvents that dissolve lipophilic polymers include esters such as methyl acetate, ethyl acetate, propyl acetate, etc.
Alcohols, ketones, halogenated hydrocarbons, ethers, etc. can be used.

Moreover, these organic solvents can be used alone or in combination of two or more.

When t[a] the dye-providing substance polymer i according to the present invention, the solvent used for polymerization is preferably one that is a good solvent for the monomer and the dye-providing substance polymer to be produced, and has low reactivity with the polymerization initiator. .

Specific examples include water, toluene, alcohol (e.g. methanol, ethanol, 1so-propanol, tert-butanol, etc.), acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, dimethylformamide, dimethyl sulfoxide, acetonitrile, methylene chloride, etc. These solvents may be used alone or in combination of two or more.

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 dye-providing polymer of the present invention include those shown below.

Examples of water-soluble polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate;
4. Sodium 4'-azobis-4-cyanovalerate, 2
, 2'-azobis(2-amidinopropane) hydrochloride and other water-soluble azo compounds, and hydrogen peroxide can be used.

In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobugronitrile, 2.2'-azobis-(2,4-dimethylvaleronitrile), 2.2'-azobis-(2,4-dimethylvaleronitrile),
'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexanone-1-carbonitrile), 2,2'-azobisisocyanobutyric acid, 2゜2'-azobisisobutyric acid dimethyl, 1.1
'-Azobis(cyclohexanone-1-carbonitrile), 4.4'-Azobis-4-cyanovaleric azo compound, benzoyl peroxide, lauryl peroxide, chlorobenzyl peroxide, diisobrobyl peroxide Examples include peroxides such as dicarbonate and di(-butyl peroxide). Among these, preferred examples include benzoyl peroxide, chlorobenzyl peroxide, and lauryl peroxide.

In emulsion polymerization and solution polymerization, these polymerization initiators can be contained in a range of 0.01 to 10% by weight, preferably in a range of (1.1 to 5% by weight) based on the total monomer. can.

Furthermore, polymerization methods other than the combination method described above, such as suspension polymerization and bulk polymerization, can also be applied. That is, in the present invention, the general formula [1] or [2] of the present invention
] A dye-donating homopolymer of the monomer represented by the above, a copolymer formed by combining two or more of the monomers, or a copolymerization component of the monomer and at least one other polymerizable comonomer. and is not limited by its synthesis process.

Specific representative examples of the dye-providing substance polymer of the present invention are listed in Table 1 below, but the invention is not limited thereto.

Margin below Table-1 In Table 1, the abbreviations of comonomers are as follows.

BA: n-butyl acrylate MA: Methyl acrylate MM: Methyl acrylate EM: Ethyl methacrylate ST: Styrene The residual monomer ° is the content of unreacted dye-providing substance monomers.

Examples of polymerization of the dye-providing substance polymer of the present invention are shown below.

Polymerization Example 1 Synthesis of a copolymer dye-donating substance (P-1) of monomer M-4 and n-butyl acrylate.

The exemplary monomer (M-4) of 3()a and 200 n-butyl acrylate were dissolved in 50 (hN) dioxane, heated to 85°C while introducing nitrogen gas, and dissolved at 2°2'-azobis. Added 30010g of isobutyronitrile and heated for 5 hours.
Heated at ℃. After the reaction was completed, the reaction solution was poured into 2500 d of water, the precipitate was filtered out, and the solid content was boiled again at 500 iN.
The solution was dissolved in dioxane, poured into 2500 d of water, and the precipitate was filtered off. Dry the solid to obtain 48 g of target polymer P-1.
I got it.

Polymerization Example 2 Synthesis of a copolymer dye-donating substance (P-10) of monomer M-10 and n-butyl acrylate.

30 (+ exemplary single substance (M-10) and 20 g of n-butyl acrylate were dissolved in 250 m of dioxane,
Heat to 80°C while introducing nitrogen gas, add 500 mg of 4.4'-azobis-4-cyanovaleric acid, and heat for 5 hours.
Heated at 0°C. After the reaction is completed, the reaction solution is 2500112
of water, filtered out the precipitate, and concentrated the solid content again at 25% water.
It was dissolved in 0iN dioxane, poured into 2500 d of water, and the precipitate was filtered off. Dry the solid to obtain the desired polymer P-10.
47a was obtained.

Polymerization Example 3 Synthesis of a copolymer dye-donating substance (P-12) of monomer M-15 and methyl acrylate.

The exemplary m form (M-15) of 30a and methyl acrylate 20 (l) were dissolved in 200d of dioxane, heated to 78°C while introducing nitrogen gas, and 4°4'-azobis-4
- 500 mg of cyanovaleric acid was added and heated at 78°C for 5 hours. After the reaction was completed, the reaction solution was poured into 2000ml of water and the precipitate was filtered out.The solid content was again dissolved in 200ml of dioxane and poured into 2000i12 of water and the precipitate was filtered off.The solid was dried. Target polymer P-12-4
7g was obtained.

Polymerization Example 4 Synthesis of a copolymer dye-donating substance (P-19) of monomer M-6 and n-butyl acrylate.

30 (l) of the exemplary monomer (M-6) and 20 g of n-butyl acrylate were dissolved in 125 t12 of dimethylformamide, and heated to 85°C while introducing nitrogen gas.2.
Add 500 mg of 2'-azobisisobutyronitrile,
Heated at 85°C for 5 hours. After the reaction is completed, the reaction solution is heated to 125 ml.
Pour into 0mf water, filter the precipitate, dissolve this solid again in 125nj2 dimethylformamide,
The mixture was poured into 50 d of water and the precipitate was filtered out. The solid was dried to obtain 471J of the target polymer P-19.

Polymerization Example 5 Synthesis of a copolymer dye-donating substance (P-21) of monomer M-9 and rope tyl acrylate.

25 g of exemplary monomer (M-9) and n-butyl acrylate 25 (125 g) were dissolved in dimethylformamide, heated to 80° C. while introducing nitrogen gas, and 2.2
'-Add 500 mg of azobisisobutyronitrile,
Heated at 80°C for 5 hours. After the reaction is complete, the reaction solution is heated to 12S.
Pour into 125 ml of water, filter out the precipitate, dissolve this solid again in 125 d of dimethylformamide,
The mixture was poured into 0i12 water and the precipitate was filtered out. The solid was dried to obtain 48(+) of the target polymer P-21.

Polymerization Example 6 Synthesis of a copolymer dye-donating substance (P-17) of monomer M-4 and n-butyl acrylate.

250 exemplified monomer (M-4) and 25 g of n-butyl acrylate were dissolved in 250 m12 of dimethylformamide, heated to 80°C while introducing nitrogen gas, and 2,2'
- 500 mg of azobisisobutyronitrile was added and heated at 80°C for 5 hours. After the reaction is completed, the reaction solution is heated for 2500 d.
of water, filtered out the precipitate, and concentrated the solid content again at 25% water.
The solution was dissolved in 120ml of dimethylformamide, poured into 2500ml of water, and the precipitate was filtered off. The solid was dried to obtain 46 g of the desired polymer P-17.

Polymerization Example 7 Synthesis of a copolymer dye-donating substance (P-22) of monomer M-11 and methyl methacrylate.

The exemplary monomer (M-11) of 30Q and 20 g of methyl methacrylate were dissolved in 125 mN N,N-dimethylacetamide, heated to 78°C while introducing nitrogen gas, added with 500a+g of dimethyl azobisisobutyrate, and stirred for 5 hours. Heated at ℃. After the reaction is complete, add the reaction solution to 125011
Pour into water from step 2, filter out the precipitate, and pour this solid content into water from step 1 again.
25 dissolved in N,N'-dimethylacetamide,
The mixture was poured into 1,250 g of water and the precipitate was filtered out. The solid was dried to obtain the target polymer P-22 (48111).

Polymerization Example 8 Synthesis of copolymer chromophoric substance (P-23) of monomer M-13 and n-butyl acrylate.

20(l) of the exemplary monomer (M-13) and lobethyl acrylate 30(+) were dissolved in 170d of dimethylformamide, heated to 72°C while introducing nitrogen gas, and heated to 4.4
'-Azobis-4-cyanovaleric acid 500ma was added, 8
Heated at 72°C for an hour. After the reaction is completed, the reaction solution is heated to 170℃ (
Pour into hj2 water, filter out vcylI, dissolve this solid again in 170d dimethylformamide, and add 1
The mixture was poured into 700 mR of water and the precipitate was filtered off. The solid was dried to obtain 48 (l) of the target polymer P-23.

Polymerization Example 9 Synthesis of copolymer dye-donating substance (P-25) of monomer M-4 and methyl acrylate.

25g of exemplified monomer (M-4) and methyl acrylate 2
5 g was dissolved in 1251β dimethylformamide, heated to 65°C while introducing nitrogen gas, 500 mg of 4,4'-azobis-4-cyanovaleric acid was added, and the mixture was heated for 10 hours.
Heated at 5°C. After the reaction is completed, the reaction solution is poured into 1250 mQ of water, the precipitate is filtered off, and this solid content is again poured into 1250 mQ of water.
Dissolved in 1g of dimethylformamide, 125011g
water and filtered out the precipitate.

The solid was dried to obtain 48(+) of the target polymer P-25.

Polymerization Example 10 Synthesis of a copolymer dye-donating substance (P-26) of monomer M-10 and n-butyl acrylate.

30g of the exemplary monomer (M-10>) and 20g of n-butyl acrylate were dissolved in 125g of dimethylformamide, heated to 60°C while introducing nitrogen gas, and 2.2'
- Add 500 mg of azobisisobutyronitrile and
Heated at 60°C for an hour. After the reaction is completed, the reaction solution is heated to 1250 ml.
Pour into the water of step d, filter out the precipitate, and add this solid content again to 1
Dissolved in 25t12 dimethylformamide, 1250
It was poured into Dai water and the precipitate was filtered out. The solid was dried to obtain 46o of the target polymer P-26.

The dye-providing substance polymer of the present invention may be used alone or in combination of two or more for one color tone. The amount used is 0.050 per dye-donor polymer.
~100g (per 1*2), preferably 1.0-30
(1 (per It') can be used.

Next, the high boiling point solvent used and present in the same particles as the dye-providing substance polymer used in the present invention will be explained.

In the present invention, a high boiling point solvent is an organic solvent having a boiling point of 150°C or higher, preferably 200°C or higher, and a melting point of lower than 130°C, preferably lower than 80°C.

Examples of high boiling point solvents that can be used in the present invention include U.S. Patent No. 2,322,027 and U.S. Pat.
, No. 2,835,579, No. 3,287,134,
2.353.262, 2.852.383, 3.554.755, 3,676.137,
No. 3,676,142, No. 3,700,454, No. 3.748,141, No. 3.779.765, No. 3.837.863, British Patent No. 958.441,
No. 1,222,753, 0L32.538,889
No., JP-A-47-1031, JP-A No. 49-90523,
No. 50-23823, No. 51-26037, No. 51
-27921, 51-27922, 51-26
No. 035, No. 51-26036, No. 50-62632
No. 53-1520, No. 53-1521, No. 53-15127, No. 54-119921, No. 54
-119922@, 55-250574, 55-3
No. 6869, No. 56-19049, No. 5G-8183
No. 6, Japanese Patent Publication No. 48-29060, etc.

The high boiling point solvents preferably used in the present invention are those represented by the following general formulas [A] to [E]. and R3 are each a hydrogen atom, a straight chain, cyclic or branched alkyl group, preferably a straight chain, cyclic or branched alkyl group having 1 to 30 carbon atoms (e.g. methyl group, ethyl group, propyl group, i-propyl group) , butyl group, cyclohexyl group, shi-butyl group, shi-amyl group, hexyl group, decyl group, dodecyl group, hexadecyl group, etc.), alkoxy group, preferably an alkoxy group having 1 to 30 carbon atoms (for example, methoxy group, Ethoxy group, i-propoxy group, t-
butoxy group, etc.), aromatic group, preferably 6 carbon atoms
~30 aromatic groups (e.g. phenyl, naphthyl, etc.)
or a heterocyclic group, preferably a heterocyclic group having 4 to 30 carbon atoms (eg, furyl group, thiofuryl group, pyrazolyl group, oxazoyl group, pyridyl group, piperazyl group, indolyl group, quinolinyl group, etc.).

The linear, cyclic, or branched alkyl groups and alkoxy groups represented by R4P+, R2, and R3 include those with substituents, and examples of substituents include aromatic groups (e.g., phenyl group, p-methoxyphenyl group, .4-G t
-amylphenyl group, etc.), carbonyl group (e.g. acedel group, benzoyl group, etc.), amine group (e.g. anilino group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, etc.), aryloxy group (e.g. 2,4- Examples include di-t-amylphenoxy group, etc.), heterocyclic groups (eg, furyl group, etc.), and siamium halogen atoms (eg, fluorine atom, chlorine atom, etc.).

The aromatic groups represented by R, R+, R2 and R3 include those having substituents, such as alkyl groups (e.g. methyl group, [-butyl group, t-amyl group, etc.),
Examples include alkoxy groups (for example, methoxy group, ethoxy group, etc.), carbonyl groups (for example, methoxycarbonyl group, etc.), halogen atoms (for example, fluorine atom, chlorine atom, etc.).

The heterocyclic group represented by R, R+, R2 and R3 is
It also includes those with substituents, such as alkyl groups (e.g. methyl group, ethyl group, butyl group, etc.), aromatic groups (e.g. phenyl group, tolyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, etc.), carbonyl group (eg, methoxycarbonyl group, etc.), and halogen atom (eg, fluorine atom, chlorine atom, etc.). However, in the formula, when R is a bond between two residues, R is a simple bond, a linear, cyclic, or branched alkylene group having 1 to 30 carbon atoms (e.g., methylene group, ethylene group, propylene group). , i-butylene group, octylene group, tetradecamethylene group, cyclohexylene group, etc.), alkenylene group (IA: vinylene group, 2-butenylene group, propenylene group, cyclohexenylene group, etc.), alkynylene group (13i11: ethynylene group, etc.) etc.), number of carbon atoms 6~
There are 30 arylene groups (eg, phenylene, naphthylene, anthrylene, etc.). When R serves as a bonding site for three or more residues, R is a trivalent or higher group (e.g. -CH
2-CH-CH2+.

CH2 etc.).

Further, when R, R1, R2 and R3 have a substituent, the number of carbon atoms of the substituent is not included in the number of carbon atoms of R-R+, R2' and R3.

, 2, m, and n represent an integer from O to 6, and at least 1 degree in the same molecule represents an integer from 1 to 6.

R, R+, R2 and R3 may be the same or different.

Any two of R, R1, R2 and R3 may be combined to form a 5- to 7-membered ring.

Specific examples of the high boiling point solvent of the present invention are shown below, but the invention is not limited thereto.

Specific example corresponding to general formula [A] a-IC,H.

a-6C2H.

■ C2H.

Specific example corresponding to general formula [B] b-10H CH, -CH-Coo-C,,H,.

■ CHaCOOC,H,, (iso) CHI-OCOCl,H7゜” HOCHC00C*H+*(n)HO-C
H-COOC* Hl* (n)b -6C+ t
Hs s COOCH) CH2-C00CHtCH-C
4H* Cz H5 b-11C2H% C2Hs b-12 (CH2)s CH2-C00CH2CH-C,H.

C2Hs Below, specific examples corresponding to the general formula [C] Ct Hs Below, specific examples corresponding to the general formula [D] d-1 l-8 Specific examples corresponding to the general formula [E] e-' C2H5Ct Hs e- 6C28S Electron Cz Hs In the present invention, the presence of the dye-donating substance polymer in the form of particles together with a high-boiling point solvent means that at least the particles containing the dye-donating substance polymer contain a high-boiling point solvent. It means.

Any method can be used to form particles of the dye-donor polymer with the high boiling solvent. For example, a method in which a single dye-donating substance and a high boiling point solvent are mixed together and particles are formed by emulsification or suspension, or a method in which a dye-donating substance polymer and a high boiling point solvent are mixed in advance and a homogenizer, colloid mill, etc. A method of forming particles by adding and mixing a high-boiling point solvent dissolved in a water-miscible low-boiling point solvent to an emulsion of a dye-providing substance polymer, distilling off the low-boiling point solvent, and filling the dye-providing substance polymer. There is a method of mixing a dispersion of a high boiling point solvent and a dispersion of a high boiling point solvent and heating the mixture to coalesce the particles.

A preferred method involves the addition of a dye-donor polymer, a high-boiling solvent, and optionally a low-boiling solvent (organic solvents with a boiling point below 150°C, such as ethyl acetate, propyl acetate, butyl acetate, methyl isobutyl ketone, cyclohexanone, phenoxyethanol, etc.). mixture and
There is a method of mixing and dispersing an aqueous solution of a hydrophilic colloid containing a surfactant (e.g. gelatin, gelatin derivatives, gum arabic, sodium alginate, albumin, non-alcoholic acid, polyvinylpyrrolidone, etc.) to form an oil-in-water dispersion. .

The high-boiling solvent to dye-donor polymer @m ratio means the weight ratio of total high-boiler to total dye-donor polymer per unit area over the entire circumference provided on the support, and is usually 0. 05-4.0, preferably 0.1-2.
It is 0.

More preferably, in each layer containing the dye-donating substance polymer, the weight ratio is from 0.05 to 4.0, preferably from 0.1 to 2.0. If the weight ratio is less than 0.05, the effect of the present invention will not be observed, and if it is greater than 4.0, the physical properties of the binder will deteriorate (e.g. stickiness, cracking, dura mater discoloration, devitrification, etc.), and the image quality will deteriorate on the contrary. I'll let you.

The present invention provides for the presence of a dye-donor polymer in the form of particles together with a high-boiling solvent, and the weighting ratio of the high-boiling solvent to the dye-donor polymer within a certain limited range. It is effective. Further, the effect is remarkable in a method in which the dye formed or released in the photosensitive material by thermal development is transferred to the receiver (passive member).

Margin below [Effects of the Invention] The heat-developable photosensitive material of the present invention is excellent in that it can improve image quality while maintaining the advantages of dye-donor polymers, such as small color staining, high maximum density, and low fog. It is. It has also been found that the present invention can further increase the maximum concentration. These effects are not limited to the dye-donor polymer used to form image dyes;
This is a useful device that can also be applied to devices that emit dramatic pigments.

In the present invention, a high boiling point solvent is applied to the dye-donating polymer in order to improve image quality. However, the improvement effect achieved by this invention is completely unexpected and overcomes the drawbacks peculiar to heat-developable photosensitive materials. This is an epoch-making invention for improvement.

Furthermore, in the production of the photothermographic material of the present invention, when preparing a dispersion of the dye-providing substance polymer, it is possible to improve the degree of dispersion, improve the dispersion stability, reduce thickening due to concentration of the dispersion, and reduce the occurrence of aggregation. It also has secondary effects such as reduction.

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
It can be prepared by any method in the photographic field, such as a single jet method or a double jet method. For example, by applying the method described in JP-A-54-48521, monodisperse silver halide grains can be obtained by the double jet method while keeping I)A(l constant).

At that time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate, pH, pAo, temperature, etc. According to a further preferred embodiment, silver halide emulsions having shelled silver halide grains can be used. Silver halide grains having a shell can be obtained by sequentially growing shells on a core of silver halide grains having good monodispersity using the method described above.

The A3 dispersible silver halide emulsion as used in the present invention refers to an emulsion having a particle size distribution in which the variation in silver halide grain size contained in the emulsion is less than a certain percentage of the average grain size as shown below. say.

Since the grain size distribution of an emulsion (hereinafter referred to as a monodisperse emulsion) consisting of a group of photosensitive silver halide grains with a uniform grain morphology and small variation in grain size is almost a normal distribution, the standard deviation can be easily determined. When the width of the distribution is defined by the relational expression, the width of the distribution of the silver halide grains used in the present invention is preferably 15% or less, preferably 15% or less, and more preferably monodispersity of 10% or less. It is.

Also, for example, JP-A-58-111933, JP-A No. 58-1
No. 11934, No. 58-108526, Research Disclosure No. 22534, etc., each of which has two parallel crystal planes, and each of these crystal planes is larger than the other single crystal of this particle. It is also possible to use a silver halide emulsion comprising tabular silver halide grains having a large area and an aspect ratio, that is, a ratio of grain diameter to thickness of 5:1 or more.

Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces have not been fogged in advance can be used. For internal latent image type silver halide whose surface is not prefogged, for example, U.S. Pat.
, No. 592, 250, No. 3,206.313@, No. 3.
317.322, 3,511,662, 3, 4
47.927, 3,761,266, 3.
As described in No. 703.584 and No. 3.736.140, silver halide grains have higher sensitivity inside the grains than on the surface of the grains. A method for preparing silver halide emulsions containing these internal latent image type silver halides is, for example, first A.
A method of creating aCffi grains and then adding bromide or a small amount of iodide to it to perform halide exchange, or a method of converting a central core of chemically sensitized silver halide to a non-chemically sensitized halide. Many methods are known, including a method of coating with silver, or a method of mixing a chemically sensitized coarse grain emulsion with a chemically sensitized or non-chemically sensitized fine grain emulsion and depositing a fine grain emulsion on the coarse grain emulsion. . Also, U.S. Patent No. 3,271.157, U.S. Patent No. 3,447,
927 and 3,531,291, or silver halide emulsions having silver halide grains incorporating polyvalent metal ions, or U.S. Pat.
Silver halide emulsions in which the grain surfaces of silver halide grains containing dopants are weakly chemically sensitized as described in JP-A-50-8524 and JP-A-50-3
Silver halide emulsions consisting of grains having a stacked mts structure as described in No. 8525, etc., and other JP-A-52-156
614 and JP-A-55-127549.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include
Various methods include gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the above-mentioned photosensitive emulsion may be coarse grains or fine grains, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.001 μm to about 1.5 μm. It is 0.01 μm to about 0.5 μm.

The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention.

In the present invention, as another method for preparing photosensitive silver halide, it is also possible to make a photosensitive silver salt-forming component coexist with a wired 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 a leprosy-free halide, for example, a halide represented by M X n (where M is an H atom, N84
represents a group or a metal atom, X represents C1, Sr or I, nl and tM are H atoms, and when N84W, 1, t
When vl is a gold atom, it indicates its valence. 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, iron, cobalt, nickel, rhodium, palladium, sumilum, iridium, platinum, cerium, etc. can be given. ), halogen-containing metal complexes (for example, K2Pt
C16, 2 Pt 3rs , HAu C1+
.

(NH4)2 1r Cj! 6, (NH4)3
1r Cf1b.

(NH4)2 Ru Cff1s, (NH4)3
RU C15(NH4>2 Rh Cff1s,
(NH4)3RhSr.

etc.), onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimedylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethylphosphonium) quaternary phosphonium halides such as bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethyl deazolium bromide, etc.)
, halogenated hydrocarbons (e.g., iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds? 1 (Ni rorosuccinimide, N-bromocobalimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibuCmo4,4-dimethylhydantoin, etc.), other halogen-containing compounds (VA such as triphenylmethyl chloride, odor triphenylmethyl,
2-bromobutyric acid, 2-bromoethanol, etc.).

These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amount used is 0.001 (1 to 50 g) per layer per support 112.
It is preferable that it is, more preferably 0.1 g to 1
It is 0g.

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

In the above case, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, can be obtained by adding various spectral sensitizing dyes to the silver halide emulsion. I can do it.

Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or 4@) 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 an enamine group capable of forming a hydroxyalkyl group, a sulfoalkyl group, or 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, 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, specific sulfonic acids, etc., such as U.S. Pat. No. 2,933,
A supersensitizing additive that does not absorb visible light, such as those described in the memo of No. 390, No. 2, No. 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, 1x i O-4 mol-1
x10-i mol.

As the reducing agent used in the photothermographic material of the present invention, those commonly used in the field of photothermographic materials can be used.

The dye-providing substance used in the heat-developable photosensitive material of the present invention is, for example, JP-A-57-186744;
-79247, 58-149046, 58
-149047, 59-124339, 59-
By coupling with an oxidized form of a reducing agent as disclosed in No. 181345, No. 60-2950, etc.,
In the case of a dye-donating substance that releases or forms a diffusible dye, examples of reducing agents used in the present invention include U.S. Pat. Nos. 3,531,286 and 3,761.
, No. 270, 3,764, 328 specifications,
Also RD No. 12146, same No.

15108, N0. 15127 and Japanese Unexamined Patent Publication No. 1983
p-phenylenediamine type and p-7 minophenol type developing agents, phosphoramide phenol type, sulfonamide phenol type developing agents, sulfonamide aniline type developing agents, hydrazone type coloring agents, etc. described in Publication No. 27132. It can be used. Also, U.S. Patent Nos. 3,342,599 and 3,719,4
No. 92, JP-A-53-135628, JP-A No. 57-790
Color developing agent precursors described in No. 35 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 (1) described in No.

General formula (1) In the formula, R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent, and R1 and R2 are ring-closed. may be used to form a heterocycle. R3, R4゜R5 and R6 each have a hydrogen atom, a halogen atom, a hydroxy group, an Amim L' alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number 1 which may have a substituent.
~30 (preferably 1 to 4) alkyl groups, R
3 and R1 and R5 and R2 may each form a heterocycle by forming R11 ring. -1 represents an alkali metal source P1, 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 (1) is an organic compound containing a nitrogen atom that exhibits basicity capable of forming a salt with an inorganic salt, and an amine compound is particularly exemplified as one essential organic base. Chain amine compounds include primary amines, secondary amines, tertiary amines, etc., and cyclic amine compounds include lysine, quinoline, piperidine, etc., which are well-known examples of typical heterocyclic organic bases. , imidazole and the like. In addition, compounds such as hydroxylamine, hydrazine, and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing paid base, inorganic acid salts of organic bases such as those mentioned above (eg, salt mPA, sulfate, nitrate, etc.) are preferably used.

On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxide compounds of nitrogen compounds having a 14-valent covalent bond.

Below is a margin.Next, preferred specific examples of the reducing agent represented by the general formula (1) are shown below.

(R-5) (R=-8) C1 (R-9) (R, -10) (R, -11) (R-12) H H3 Above U.

(R-20) (R-21) (R-23) (p-2';') (p-26) (C2-λri) (R-2g) C112-pa) C carbon-3o) "( 1) The reducing agent represented by the above general formula (1) can be prepared by a known method,
For example, Heuben Peil, Menden der Organizien Hemi, Band XI/2 (1-1oube
n-Weyl, Methoden der Qrg
anischen Chemie, Band X
It can be synthesized according to the method described in I/2) pages 645-703.

Furthermore, it is also possible to use two or more of the above-mentioned reducing agents at the same time, or to use a black and white developing agent described below in combination for the purpose of increasing developability.

Further, the dye-donating substance used in the present invention is JP-A No. 57-179840, No. 58-58543, No. 5
In the case of compounds that release dyes upon oxidation, compounds that lose their ability to release dyes when oxidized, compounds that release dyes when reduced, etc., as shown in Nos. 9-152440 and 59-154445, etc. (or when simply obtaining a silver image), a developing agent as described below can also be used.

For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-tert-
butyl-p-cresol, N-methyl-p-aminephenol, etc.), sulfonamidophenols [e.g. 4-
Benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dipromo 4-
(p-toluenesulfonamide)phenol, etc.], or polyhydroxybenzenes (e.g., hydroquinone,
tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.) ), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1'-dihydroxy-2,2'
-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-dinito 0-2
．． 2'-dihydrooxy-1,1'-binaphthyl, 4.4
'-dimethoxy-1,1'-dihydroxy-2,2'
-binaphthyl, bis(2-hydroxy-1-naphthyl)
methane, etc.], methylene and sphenols [e.g. 1.1
-bis(2-hydroxy-3,5-dimethylphenyl)
-3゜5.5-trimethylhexane, 1.1-bis(2
-Hydroxy-3-tert-butyl-5-methicif 1
methane, 1,1-bis(2-hydroxy-3,5
-di(art-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tert-butyl-
5-methylphenyl)-4-methylphenol, 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 developing agents mentioned above can also be used alone or in combination of two or more.

The amount of the reducing agent used in the heat-developable photosensitive material of the present invention depends on the type of photosensitive silver halide used, the organic F
l! It! ! Although it depends on the type of salt and the type of other additives, it is usually in the range of 0.01 to 1,500 mol per mol of photosensitive silver halide, preferably 0.
．． It is 1 to 200 moles.

The binders used in the heat-developable photosensitive material of the present invention include synthetic or natural binders such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, and phthalated gelatin. One or more of these polymeric substances can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof 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 vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or a copolymer (including a graft copolymer) of vinylpyrrolidone and one or more copolymerizable monomers. ). These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone, and preferred polyvinylpyrrolidone has a molecular weight of 1.000 to 40.
It is of 0.000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid, and their alkyl esters, vinyl alcohols, vinyl acetates, vinyl imidazoles, and (meth)acrylamides. ,
Examples include vinyl monomers such as vinyl carbonols and vinyl alkyl ethers, but it is preferable that polyvinylpyrrolidone accounts for at least 20% (by weight, the same hereinafter) of the composition. Preferred examples of such copolymers are those having a molecular weight of s,ooo to 400,000.

The gelatin may be lime-treated or acid-treated, and may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins.

In the above binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90% of the total binder m.
It is preferably 10 to 80%, more preferably 10 to 80%.

The above-mentioned binder may contain other polymeric substances, such as gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and molecules. l 5,000~400
, 000 vinylpyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, proteins such as cellulose derivative conductors, and polysaccharides such as starch and gum arabic. Examples include natural substances. These range from 0 to 85%, preferably from 0 to 85%.
It may be contained in an amount of 70%.

Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it to stand).

The amount of binder used is usually 0.05 g to 50 (l) per layer per support 112, preferably o,
10-10 (l.

In addition, the binder is 0.1% per 1g of the dye-providing substance.
It is preferable to use ~10g, more preferably 0.2
It is 5 to 4 g.

Margins Below In the heat-developable photosensitive material of the present invention, various 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 photosensitive material of the present invention include those disclosed in Japanese Patent Publication Nos. 43-4921, 52626-1980, 141222-1982, 36224-1983, and 37610-1980, etc. Long-chain aliphatic carbon atoms as described in each publication and specifications of U.S. Pat. Silver salts of acids and silver salts of carboxylic acids that form heterocycles, such as silver laurate, silver myristate, silver valmitate, silver stearate, silver arachidonate, silver behenate, α-(1-phenyltetrazolthio) Silver aromatic carboxylates such as silver acetate, such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-213582,
No. 45-12700, No. 45-18416, No. 45
-22185, JP-A-52-137321, JP-A-58-118638, JP-A-58-118639, and U.S. Patent No. 4,123,274, silver salts of imino groups are be.

Examples of silver salts of imino groups include benztriazole silver. The penztriazole silver may be substituted or unsubstituted. Representative examples of substituted benztriazole silver include, for example, alkyl-substituted benztriazole silver (preferably a C22 or less alkyl group,
More preferably those substituted with an alkyl group of 04 or less, such as methylbenztriazole silver, ethylbenztriazole silver, n-octylbenztriazole silver, etc.), alkylamidobenztriazole silver (preferably substituted with an alkylamide group of 022 or less) silver acetamidobenztriazole, silver propionamidebenztriazole, silver 1so-butylamidebenztriazole, silver laurylamidebenztriazole, etc.), silver alkylsulfamoylbenztriazole (preferably silver alkylsulfamoylbenztriazole of 022 or less), Those substituted with a famoyl group, such as silver 4-(N,N-diethylsulfamoyl)penztriazole, silver 4-(N-propylsulfamoyl)penztriazole, 4-
Silver salts of halogen-substituted benztriazoles (for example, 5-chlorobenztriazole silver, 5-bromobenztriazole silver, etc.), alkoxybenztriazole silver (preferably C22 or less alkoxy group, more preferably C+ or less alkoxy group substituted, such as 5-methoxybenztriazole silver) triazole silver, 5-ethoxybenztriazole silver, etc.), 5-nitrobenztriazole silver, 5-aminobenztriazole silver, 4-
Hydroxybenztriazole silver, 5-carboxybenztriazole silver, 4-sulfobenztriazole silver,
Examples include silver 5-sulfobenztriazole.

Examples of other silver salts having an imino group include imidazole silver, benzimidazole silver, 6-nidropenzimidazole silver, pyrazole silver, urazole silver, 1,2
．． Silver salts of other mercapto compounds such as 4-triazole silver, 1-tetrazole silver, 3-amino-5-pendylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., such as 2-mercaptobenzo Silver oxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole, silver 2-mercaptobenzimidazole, silver 3-mercapto-4-phenyl-1,2,4-triazole, 4-hydroxy-6
-Methyl-1,3°38.7-thitrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4,6-
Examples include silver pentazaindene.

Other silver complex compounds with a stability constant of 4.5-10.0 as described in JP-A No. 52-31728, and imidase as described in U.S. Pat. No. 4,168,980. A silver salt of lynchion or the like is used.

Among the above organic silver salts, imino group silver salts are preferred;
Particularly preferred are silver salts of benzotriazole derivatives, more preferably 5-methylbenzotriazole and its derivatives, sulfobenzotriazole and its derivatives, and N-alkylsulfamoylbenzotriazole and its derivatives.

The right front silver salts used in the present invention may be used alone or in combination of two or more. Further, a silver salt may be prepared in a suitable binder and used as it is without isolation, or the isolated salt may be dispersed in a binder by an appropriate means and used. Dispersion methods include, but are not limited to, ball mills, Nando mills, colloid mills, vibration mills, and the like.

Generally, organic silver salts are prepared by dissolving and mixing silver nitrate and raw material compounds in water or an organic solvent, but if necessary, a binder may be added, sodium hydroxide, etc. Adding alkali to promote the dissolution of organic compounds, and also ammoniacal nitric acid! It is also effective to use a silver solution.

The amount of the organic silver salt to be used is generally preferably 0.01 mol-500 mol per mol of photosensitive silver halide, more preferably 0.1 to 100 mol. More preferably, it is 0.3 to 30 mol.

The support used in the heat-developable photosensitive material of the present invention includes:
For example, polyethylene film, cellulose acetate film and polyethylene terephthalate film, synthetic plastic films such as polyvinyl chloride, paper supports such as photographic base paper, printing paper, baryta paper and resin-coated paper, and electronic coatings on these supports. Examples include a support coated with a line-curable resin composition and cured.

Margins Below In the heat-developable photosensitive material of the present invention, and when the photosensitive material is of a transfer type and uses a receiving member, it is preferable that various heat solvents are added to the heat-developable photosensitive material and/or the image-receiving member. The thermal solvent used in the present invention is a compound that promotes thermal development and/or thermal transfer. Regarding these compounds, for example, U.S. Pat. No. 3,347,675, U.S. Pat.
56, Special @ Ill 59-47787, etc., and those particularly useful in the present invention include, for example, urea derivatives (e.g., dimethylurea, diethylurea, phenylurea, etc.). ), amide derivatives (e.g., acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1,5-bentanediol, 1,6-bentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane) etc.) or polyethylene glycols.

Among the above thermal solvents, water-insoluble solid thermal solvents described below are more preferably used.

A water-insoluble solid thermal solvent is a compound that is solid at room temperature but becomes liquid at high temperatures (60°C or higher, preferably 100°C or higher, particularly preferably 130°C or higher and 250°C or lower), and is an inorganic/organic compound. Ratio (“Organic Conceptual Diagram” Yoshio Koda,
Sankyo Publishing, 1984) is in the range of 0.5 to 3.01, preferably 0.7 to 2.5, particularly preferably 1.0 to 2.0, and the solubility in water at room temperature is 1. Refers to smaller compounds.

Specific examples of water-insoluble solid thermal solvents are shown below, but the invention is not limited thereto.

Below are examples of water-insoluble solid thermal solvents Melting point (°C) Inorganic/Organic C(Cl3)3CONH214f'1.44GCON
H2128° 1.54 HO+CONH2161° 2.25 CH3+CONH2160° 1,34CH30-C
INNHCOCHs 130° l, 31B
r+NHCOCHs 168° 1.02eN
HcOcH3113~115°, 1.34 melting point ("
c) Inorganic/organic C to HCOCONH<III>151-153'
1.54CH3CONHkNHCOCH3290'
More than 1.34GCH2CONH2156° 1.34C
H30 (CONH2164~167° 1.47 Melting point (C'I Inorganic ratio/Organic melting point (°C) Inorganic/Organic Q 802NH-c) 110° 1.13CH3-C
ζ02NHC2HaNH8OzeCH13168°
1.59 Many compounds used as water-insoluble solid heat solvents are commercially available, and in the 2M,
It is easily synthesized.

The method of adding the water-insoluble hot solvent is not particularly limited, but it may be added by grinding and dispersing it using a ball mill, sand mill, etc.
There are methods such as adding it by dissolving it in an appropriate solvent, and adding it as an oil-in-water dispersion by dissolving it in a high boiling point solvent.
It is preferable to pulverize and disperse the solid particles using a ball mill, sand mill, etc. and add them while maintaining the solid particle shape.

Layers to which the water-insoluble solid thermal solvent is added include a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image-receiving layer of an image-receiving member, and the like, so that the respective effects can be obtained.

The amount of the water-insoluble heat-humectant added is usually 10% to 500% by weight, preferably 50% to 300% by weight of the binder.

Note that even if the water-insoluble solid thermal solvent of the present invention has a melting point higher than one degree of thermal development, its addition to the binder lowers the melting point, so it can be effectively used as a thermal solvent.

The heat-developable photosensitive material of the present invention may contain various additives as required in addition to the above-mentioned components.

For example, melt formers such as acetamide and succinimide described in U.S. Pat. No. 3,438.776; compounds such as polyalkylene glycols described in U.S. Pat. No. 3,666.477 and JP-A-51-19525; , -CO-1-8O2- as described in U.S. Pat. No. 3,667.959.
There are non-aqueous polar organic compounds having a melting point of 20° C. or higher, such as lactones having 1-80- groups.

Furthermore, benzophenone derivatives described in JP-A-49-115540, JP-A-53-24829 and JP-A-53-24829;
Phenol derivatives described in No. 60223, JP-A-5
Carboxylic acids described in No. 8-118640, polyhydric alcohols described in JP-A-58-198038,
Also included are sulfamoylamide compounds described in JP-A-59-84236.

Further, a color toning agent known in heat-developable photosensitive materials may be added as a development accelerator to the photothermographic material of the present invention. As a color toning agent, for example, JP-A-46-4
No. 928, No. 4B-6077, No. 49-5019,
49-5020, 49-91215, 4
No. 9-107727, No. 50-2524, No. 50-
No. 67132, No. 50-67641, No. 50-11
No. 4217, No. 52-33722, No. 52-9981
No. 3, No. 53-1020, No. 53-55115, No. 53-76020, No. 53-125014, No. 54
-156523, 54-156524, 54
-156525, 54-156526, 55
-4060, 55-4061, 55-3201
No. 5, as well as West German Patent No. 2,140,406, West German Patent No. 2,141°063, West German Patent No. 2,220,618, U.S. Patent No. 3,847,612, West German Patent No. 3,782,
No. 941, No. 4,201,582 and JP-A-57
-207244, 57-207245, 58-
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-human xynaphthalimide, benzoxazine, naphthoxazinedione, 2,3- Dihydro-phthalazinedione, 2.3-
Dihydro-1,3-oxazine-2,4-sion, ogicipyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide,
2H-1,3-benzothiazine-2,4-(31-1)
dione, benzotriazine, mercaptotriazoletetrazabentalene, aminomercaptotriazole, acylaminomercaptotriazoles, phthalic acid,
Naphthalic acid, phthalamic acid, etc., mixtures of one or more of these with imidazole compounds, mixtures of at least one acid or acid anhydride such as phthalic acid and naphthalic acid, and phthalazine compounds; Examples include combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like.

Antifoggants include, for example, U.S. Pat. No. 3,645;
Higher aliphatic compounds (e.g. behenic acid, stearic acid, etc.) described in No. 739, Machiai [mercuric salts described in No. 47-11113, N described in JP-A-51-47419
- halogen compounds (e.g. N-halogenoacetamide,
N-halogenosuccinimide, etc.), U.S. Patent Nos. 3 and 7
00, 451, mercapto compound releasing compounds described in JP-A No. 51-50725, arylsulfones (e.g. benzenesulfonic acid, etc.) described in JP-A No. 49125016, lithium carboxylates described in JP-A No. 51-47419. salts (e.g. lithium laurate), UK Patent No. 1
, 455,271, oxidizing agents (e.g. perchlorates, inorganic peroxides, persulfates, etc.) described in JP-A-50-101,019, sulfinic acids or thiosulfones described in Shu 53-19825. Acids, 2-thiouracils described in No. 51-3223, simple sulfur described in No. 51-26019, No. 51-42529, No. 51-811
Disulfide and polysulfide compounds described in No. 24, No. 55-93149, rosins or diterpenes (e.g. abietic acid, pimaric acid, etc.) described in No. 51-57435, free carboxy groups described in No. 51-104338. or polymer acids with sulfone MW, thiazolinthione described in U.S. Pat. No. 4,138,265, JP-A-54-51821, U.S. Pat. No. 4,1
1.2.4-triazole or 5-mercapto-1.2.4-t-riazole described in No. 37.079, thiosulfinic acid esters described in No. 55-140833, and described in No. 55-142331. 1.2.3.4
-Thiatriazoles, No. 59-46641, No. 59
-57233, dihalogen compounds or trihalogen compounds described in No. 59-57234, Zarani No. 59
Examples include thiol compounds described in No.-111636.

In addition, as other antifoggants, patent application I [159-5
Hydroquinone derivatives (e.g., di-t-octylhydroquinone, dodecanylhydroquinone, etc.) described in Japanese Patent Application No. 6506 and hydroquinone derivatives and benzotriazole derivatives (e.g.,
-sulfobenzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used.

Silver image stabilizers include U.S. Pat. No. 3,707,3
Polyhalogenated organic oxidizing agents (e.g., tetrabromobutane, tribromoquinaridine, etc.) described in No. 77 Mei ms,
5 described in Belgian Patent No. 768,071 MeiwJ
-methoxycarbonylthio-1-phenyltetrazole, monohalo compounds described in JP-A-50-119624 (e.g., 2-bromo-2-tolylsulfonylacetamide, etc.), bromine compounds described in JP-A-50-120328 ( Examples include 2-bromomethylsulfonylbenzodiazole, 2,4-bis(tribromomethyl)-6-methyltriazine, etc.), and tribromoethanol described in JP-A-53-46020. Also, various monohalogenated organic antifoggants for silver halide emulsions as described in JP-A-50-119624 can be used.

Other image stabilizers include U.S. Patent M3,220;
No. 846, No. 4,082,555, No. 4,088
, No. 496, JP-A-50-22625, Research Disclosure (RD) No. 12021, RD No. 15168.
No. 15567, No. 15732, No. 1573
No. 3, No. 15734, No. 15776, etc. Compounds called activator precursors that release basic substances by heat, such as compounds such as guanidinium trichloroacetate that release bases by decarboxylation with heat, galactonamide Aldonamide compounds such as
Compounds such as amine imides and 2-carboxycarboxamides, as well as JP-A-56-130745 and JP-A-56-130745.
Sodium phosphate g group generator described in No. 132332, compound generating amine by intramolecular nucleophilic reaction described in British Patent No. 2.07, No. 480, JP-A-59-
Aldoxime carbamates described in No. 157G37, hydroxamic acid carbamates etc. described in No. 59-166943, and No. 59-180537, No. 59
Examples include base release agents described in Japanese Patent No. 174830 and No. 59-195237.

Additionally, U.S. Patent No. 3.3 (No. 11,678, U.S. Patent No. 3.50)
6.444, 3.824.103, 3.84
Illithiuronium compounds, S-rubamoyl derivatives of mercapto-containing compounds, and nitrogen-containing heterocyclic compounds described in No. 4.788, RD12G35, and RD18016 may be used for the purpose of stabilizing images, and The activator stabilizer described in U.S. Patent Nos. 3,669,670, 4,012,260, 4,060.420, 4,207.392, RD 15109, RD 17711, etc. Nitrogen-containing organic bases called activator stabilizer breakers, such as the α-sulfonylacetic acid group of 2-aminothiazoline or trichloroo #f2 salt, and acylhydrazine compounds are used to accelerate development or stabilize images, respectively. It can be used for the purpose of

Also, for example, JP-A-56-130745 and JP-A-59-2
18443, in the presence of a small amount of water, or by spraying a small amount of water before heating,
Applying a certain amount of water or supplying water, U.S. Patent No. 3
, No. 312,550, etc., hot steam or hot air containing moisture may be used for further development. In addition, compounds that release water into heat-developable photosensitive materials, such as Japanese Patent Publication No. 44-26
Compounds containing water of crystallization such as those described in No. 582, such as sodium phosphate dodecahydrate and ammonium alum diquadrate, may be incorporated into the photothermographic material.

In addition, various additives such as antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreading agents, coating aids, and the like may be used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example,
Colloidal silica can be used for the undercoat layer, intermediate layer, protective layer, etc.).

The colloidal silica used in the present invention is a colloidal solution of silicic anhydride with an average particle size of 3 to 120 mμ mainly using water as a dispersion medium, and the main component is 5i02 (silicon dioxide).
It is. Colloidal silica is described, for example, in JP-A-56'-109336, JP-A-53-123916, JP-A-53-112732, and JP-A-53-100226. The use m of colloidal silica is 0.05 in terms of dry weight ratio to the binder of the layer to be mixed and coated.
A range of 2.0 to 2.0 is preferable.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example,
Organic fluoro compounds can be used for F coating layer, intermediate layer, a-retaining layer, etc.).

Regarding organic fluoro compounds used in the present invention, US Pat. No. 3,589,906 and US Pat.
No. 3,754,924, No. 3,775.126, No. 3,850,640, West German Patent Publication No. 1,942
, No. 665, No. 1,961,638, No. 2,124,
No. 262, British Patent No. 1, 330.356, Belgian Patent No. 742.6804 and JP-A-46-7781
No. 48-9715, No. 49-46733, No. 4
No. 9-133023, No. 50-99529, No. 50-
No. 11322, No. 50-160034, No. 51-43
No. 131, No. 51-129229, No. 51-1064
No. 19, No. 53-84712, No. 54-11133
No. 0, No. 56-109336, No. 59-30536
No. 59-45441 and Special Publication No. 47-9303
No. 48-43130, No. 59-5887, etc., and these compounds can be preferably used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Or non-photosensitive! ! ! Antistatic agents can be used in (eg, undercoat, interlayer, protective layer, etc.).

As the antistatic agent used in the present invention, British Patent No. 1
．． No. 4613.600, Research Disclosure
No. 15840, No. 16258, No. 16630,
U.S. Patent No. 2.327.828, U.S. Patent No. 2,861,05
No. 6, No. 3,206.312, No. 3,245,833
No. 3.428.451, No. 3.775.126, No. 3,963.498, No. 4,025,342, No. 4,025,463, No. 4.025,691, Examples include compounds described in 4,025,704, etc., and these can be preferably used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, an ultraviolet absorber can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

As the ultraviolet absorber used in the present invention, benzophenone compounds (for example, those described in JP-A-46-2784, U.S. Pat. No. 3,215,530, and U.S. Pat. No. 3,698,907), butadiene compounds (for example, , U.S. Patent No. 4
, 045,229), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314.794j),
3, 352.681), benzotriazole compounds substituted with an aryl group (e.g.
No. 6-10466, No. 41-1687, No. 42-2
No. 6187, No. 44-29620, No. 48-4157
No. 2, JP-A-54-95233, JP-A No. 57-14297
No. 5, U.S. Patent No. 3,253,921, U.S. Patent No. 3,533
, No. 794, No. 3.754.919, No. 3.794.
No. 493, No. 4.009,038, No. 4,220,7
11@, 4.323.633@, Research Disclosure
), benzoxidol compounds (e.g., those described in U.S. Pat. No. 3,700.455), cinnamate ester compounds (e.g., U.S. Pat. No. 3,705,805, U.S. Pat. , No. 707, 375, and those described in JP-A No. 52-49029)) Listing 1
．． f can be read. Zarani, U.S. Patent No. 3.49
Those described in No. 9.762 and JP-A-54-48535 can also be used. UV-absorbing couplers (e.g., α-naphthol-based cyan dye-forming couplers),
Ultraviolet absorbing polymers (e.g., JP-A-58-111)
No. 942, No. 178351, No. 181041, No. 5
No. 9-19945, No. 23344, and those described in the official gazette).

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, a hardening agent can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

Hardening agents used in the present invention include aldehyde-based and aziridine-based hardeners (for example, PB Report 19,921, U.S. Patent No. 2,950.197, U.S. Patent No. 2,964,404).
No. 2,983,611, No. 3,271,17
Specifications of No. 5, Japanese Patent Publication No. 46-40898, Japanese Patent Application Publication No. 1973
No. 0-91315), isoxazole type (e.g., US Pat. No. 331,609 No. 9I
), epoxy systems (such as those described in U.S. Pat. No. 3,
No. 047,394, West German Patent No. 1,085,663,
Specifications of British Patent No. 1,033,518, Japanese Patent Publication No. 4
8-35495), vinyl sulfone type (for example, PB Report 19,920, West German Patent No. 1,100,942, West German Patent No. 2,337..112, West German Patent No. 2,545.722, No. 2,635,518, No. 2
．． No. 742.308, No. 2.749.260, British Patent No. 1,251,091, Japanese Patent Application No. 45-54236, No. 48-110996, U.S. Patent No. 3,539,6
44M, those described in the specifications of the same No. 3,490,911), acryloyl type (for example, Japanese Patent Application No. 1983-279)
No. 49, U.S. Pat. No. 3,640,720, ll
1l), carbodiimides (e.g., U.S. Pat. Nos. 2,938,892 and 4.043.818)
No. 4,061.499, each specification, Special Publication No. 1973-
38715, Japanese Patent Application No. 15095/1983), triazine type (for example, those described in West German Patent No. 2.
．． No. 110,973, No. 2,553.915, U.S. Patent No. 3,325,287, and JP-A-1989-1
2722), other maleimides,
Acetylene-based, methanesulfonic acid ester-based, and N-methylol-based hardeners can be used alone or in combination.

As a useful combination technique, for example, West German Patent Nos. 2 and 4
No. 47,587, No. 2,505.746, No. 2,51
4,245, the specifications of U.S. Patent No. 4.047.957, U.S. Patent No. 3.832.181, and U.S. Pat.
No. 52-127329, Special Publication No. 48-32364
Examples include combinations described in each publication of the issue. - The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, a polymer hardener can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

Examples of the polymeric hardening agent used in the present invention include polymers having aldehyde groups (e.g., acrolein copolymers, etc.) described in U.S. Pat. No. 3,396,029.
, U.S. Pat. No. 3,362,827, Research Disclosure No. 17333 (1978), etc., polymers having a dichlorotriazine group, and U.S. Pat. No. 3,623.
, 878, Research Disclosure No. 16725 (1978),
U.S. Patent No. 4,161,407, JP 54-650
Examples thereof include polymers having an active vinyl group or a group that can be a precursor thereof, as described in Japanese Patent Application Laid-open No. 56-66841, and polymers having an active ester group as described in Japanese Patent Application Laid-Open No. 56-66841.

In the heat-developable photosensitive material of the present invention, a polymer latex is used in the heat-developable photosensitive layer and/or the non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving the physical properties of the film. be able to.

Preferred specific examples of the polymer latex used in the present invention include polymethyl acrylate, polyethyl acrylate, polylobyl acrylate, a copolymer of ethyl acrylate and acrylic acid, a copolymer of nylidene chloride and butyl acrylate, and a copolymer of butyl acrylate and acrylic acid. , a copolymer of vinyl acetate and butyl acrylate, a copolymer of vinyl acetate and ethyl acrylate, a copolymer of ethyl acrylate and 2-acrylamide, and the like.

The preferred average particle size of the polymer latex is 0.02 μm
-0.2 μm. The amount of polymer latex to be used is 0.0% in dry type n ratio to the binder of the layer to which it is added.
03 to 0.5 is preferable.

In the heat-developable photosensitive material of the present invention, various surfactants are added to the heat-developable photosensitive layer and/or non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving coating properties. Agents can be used.

The surfactant used in the present invention may be any of anionic, cationic, amphoteric and nonionic surfactants.

Examples of anionic surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N
-carboxy groups, sulfo groups, such as acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Those containing an acidic group such as a phospho group, a sulfuric acid ester group, or a phosphoric acid ester group are preferred.

Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings are preferred.

Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, and amine oxides.

Examples of nonionic surfactants include saponin (steroid type), alkylene oxide derivatives (e.g., polyethylene glycol, polyethylene glycol/bolyb O pyrene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters) , polyethylene glycol sorbitan esters,
polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide additives)
, glycidol derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and the like are preferred.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, etc.) for the purpose of improving developability, improving image dye transferability, improving optical properties, etc. ,
(protective layer, etc.) may contain non-photosensitive silver halide grains.

The non-photosensitive silver halide grains used in the present invention may have any silver halide composition such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Can be used. The preferred grain size of the non-photosensitive silver halide grains is about 0.
．． It is 3 μm or less.

Further, the addition port has a diameter of 0.0% in terms of silver ω with respect to the layer to be added.
A range of 02 to 3Q/f is preferred.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (undercoat layer,
(intermediate layer, protective layer, etc.), for example, JP-A-51-10433.
It is possible to contain polymers having carboxyl groups or sulfo groups as described in No. 8.

The amount of the vinyl polymer used is preferably in the range of 0.05 to 2.0 in terms of dry co-ratio to the binder of the layer to which it is added.

The heat-developable photosensitive material of the present invention basically includes (1) photosensitive silver halide, (2) reducing agent, (3) dye-providing substance, (4) in one heat-developable photosensitive layer. 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 photographic constituent layer; for example, the heat-developable photosensitive layer may be divided into two layers, and the above-mentioned (1), (2>, '(4), (5)) Two or more components are contained in one side of the heat-developable photosensitive layer, and the other layer adjacent to this photosensitive layer contains the dye-providing substance (3), as long as they are in a state where they can react with each other. It may be contained separately in the constituent layers.

Further, the heat-developable photosensitive layer may be divided into 2 m or more, such as a high-sensitivity layer and a low-sensitivity layer, a high-density layer and a low-density layer, or the like.

The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers on a support. In the case of color, there are generally three heat-developable photosensitive layers having different color sensitivities, and each photosensitive layer forms or releases a dye having a respective hue upon heat development.

Usually, a yellow dye is used in the blue-sensitive layer, a magenta dye is used in the green-sensitive layer, and a cyan dye is used in the red-sensitive layer. ! Although the elements are combined, the combination is not limited to this. It is also possible to combine a near-infrared sensitive layer.

The configuration of each layer can be arbitrarily selected depending on the purpose, for example,
A configuration in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on the support, and a configuration in which a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer are sequentially formed on the support. Alternatively, there is a structure in which a green-sensitive layer, a red-sensitive layer, and a blue-sensitive layer are sequentially formed on the support.

In addition to the heat-developable photosensitive layer, the heat-developable photosensitive material of the present invention can be provided with non-photosensitive layers such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer 2I.

To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support, a method similar to that used for coating and preparing general silver halide photosensitive materials can be applied.

Namely, dip method, roller method, reverse roll method, air knife method, doctor blade method, spray method,
There are methods and devices for the bead method, extrusion method, stretch flow method, curtain method, etc.

Margins Below The heat-developable photosensitive material of the present invention is preferably provided with a protective layer. Hereinafter, this will be referred to as the protective layer of the present invention.

Various additives used in the photographic field can be used in the protective layer of the present invention. These additives include various matting agents, colloidal silica, slip agents, organic fluoro compounds (especially fluorine surfactants), antistatic agents, ultraviolet absorbers, high boiling point organic solvents, antioxidants, and hydroquinone dichloromethane. , polymer latex, surfactants (including polymeric surfactants), hardeners (including polymeric hardeners), organic silver salt particles, non-photosensitive silver halide particles, and the like.

The matting agent used in the protective layer of the present invention is fine particles of inorganic or organic substances that are incorporated into the photothermographic material to increase the roughness of the surface of the photosensitive material and make it matte. be.

A matting agent is used to prevent adhesion that occurs during the production, storage, and use of photosensitive materials, and to prevent contact between the same or different materials, a! Methods for preventing static buildup caused by rubbing and peeling are well known in the industry. Specific examples of matting agents include silicon dioxide described in JP-A-50-46316, alkyl methacrylate/methacrylate described in JP-A-53-7231, JP-A-58-66937, and JP-A-60-8894.
Alkali-soluble matting agents such as methacrylic acid copolymers, alkali-soluble polymers having anionic groups described in JP-A-58-166341, and two or more types of matting agents with different Mohs hardnesses as described in JP-A-58-145935. Combination of fine particle powder, combination of oil droplets and fine particle powder described in JP-A-58-147734, combination of two or more spherical matting agents with different average particle diameters as described in JP-A-59-149356, JP-A-59-149356. Showa 56
- Combination of fluorinated surfactant and matting agent described in No. 44411, British Patent No. 1,055,713, U.S. Patent No. 1,939,213, U.S. Patent No. 2,221,873,
No. 2,268,662, No. 2,322,037, No. 2,376,005, No. 2,391,181, No. 2
, No. 701, 245, No. 2.992.101, No. 3
, No. 079,257, No. 3,262.782, No. 3
．． No. 443.946, No. 3.516.832, No. 3.
No. 5391344, No. 3,591,379, No. 3
, 754,924, 3.767.448, JP-A-49-106821, JP-A-57-14835s, etc.; West German patent 2.520, 32;
1, British Patent No. 760.775, British Patent No. 1,260.7
No. 72, U.S. Patent No. 1,201,905, U.S. Patent No. 2,19
No. 2,241, No. 3,053,662, No. 3,062
, No. 649, No. 3,257,206, No. 3.322.
No. 555, No. 3.353.958, No. 3,370.9
No. 51, No. 3,411,907, No. 3.437.4
No. 84, No. 3,523,022, No. 3,615,55
No. 4, No. 3,635,714, No. 3.769.020
No. 4,021,245, No. 4,029.504, etc., or JP-A-46
-7781, 49-106821, 51-60
No. 17, No. 53-116143, No. 53-100
No. 226, No. 57-14835, No. 57-82832
No. 53-70426, No. 59-149357, Japanese Patent Publication No. 57-9053 and EP-107,3
A matting agent having physical properties such as those described in No. 78 specification etc. is preferably used.

In the f-1 layer of the present invention, the addition a of the matting agent is 112
per 10111 (+/2.0 g is preferred, more preferably 20 rAg to 1.0 g. The particle size of the matting agent is preferably 0.5 to 10 μm, more preferably 1.
It is 0 to 6 μm.

The matting agents may be used in combination of 211 or more.

Examples of the slipping agent used in the protective layer of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, synthetic waxes, etc. Specifically, French Patent Nos. 2 and 1
80,465, British Patent No. 955,061, 1.
143.118, 1,270.578, 1,3
20, 564@, No. 1,320.757, Japanese Patent Publication No. 1973
-5017, 51-141623, 54'-
No. 159221, No. 56-81841, Research Disclosure
re ) 13969, U.S. Patent No. 1,263,7
No. 22, No. 2,588.765, No. 2,739,89
No. 1, No. 3,018.178, No. 3,042,52
No. 2, No. 3,080,317, No. 3, 082.08
No. 7, No. 3,121,060, No. 3.222.1
No. 78, No. 3,295,979, No. 3.489.56
No. 7, No. 3,516,832, No. 3,658,573
No. 3,679,411, No. 3,870.521, etc. can be preferably used.

The protective layer of the present invention contains a high boiling point organic solvent (for example, U.S. Pat. No. 2,322,027, U.S. Pat.
No. 533,514, No. 2,882,157, Special Publication No. 4
No. 6-23233, British Patent No. 958.441, 1
, 222.753, U.S. Patent No. 2,353,262, U.S. Patent No. 3,676.142, U.S. Patent No. 3.700.454,
Esters (e.g., phthalate esters, phosphoric acid esters, fatty acid esters, etc.), amides (e.g., fatty acid amides, sulfonic acids, (amides, etc.), ethers, alcohols, paraffins, etc. ) may contain oil droplets in which a water-insoluble oil compound is emulsified and dispersed. Furthermore, these oil droplets may contain photographic additives for various purposes.

Examples of the binder used in the protective layer of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, BoO methyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, polyethyl oxazoline, polyacrylamide,
One or a combination of two or more synthetic or natural polymeric substances such as gelatin and phthalated gelatin can be used.

In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (preferably molecule @ 1,000 to 400,000), polyvinyl alcohol (molecular number i, oo
Preferable binders are gelatin alone or gelatin and the above-mentioned polyvinylpyrrolidone, polyvinyl alcohol and Particularly preferred is a binder containing a hydrophilic polymer having good compatibility with gelatin, such as polyoxazoline. Gelatin may be treated with lime, acid, or ion exchange, and may be ossein gelatin, big skin gelatin, hyde gelatin, or modified gelatin made by esterifying, phenylcarbamoylating, etc. The thickness of the protective layer of the invention is preferably 0.05 to 5 μm, more preferably 0.1 to 1.0 μm. The protective layer may be a single layer or may be composed of two or more layers.

In addition, in order to increase membrane strength and prevent membrane destruction,
It is also preferred that the hardness of the layer is greater than that of the photosensitive layer. One way to make the hardness of the protective layer higher than that of the photosensitive layer, that is, to control the hardness of each layer, is to use a diffusion-resistant hardener. By using a film agent in the protective layer, only the degree of hardness of the protective layer can be made greater than that of the photosensitive layer. Polymer hardeners are known as diffusion-resistant hardeners, such as those disclosed in U.S. Pat.
．． Hardeners described in No. 396.029, No. 4,161,407, JP-A No. 58-50528, etc. can be used.

Another way to control the degree of dura for each layer is to
Diffusible hardener (e.g. vinyl sulfone-based li! film agent)
The degree of hardness of the protective layer can be made greater than that of the photosensitive layer by containing it only in the protective layer or by making the content n of the protective layer higher than that of the photosensitive layer and rapidly drying it with a multilayer simultaneous coater. can.

The following margins The heat-developable photosensitive material of the present invention usually has a temperature of 80°C to 20°C after imagewise exposure.
1 at a temperature range of 0°C, preferably 100°C to 110°C.
Developing can be carried out by simply heating for 1.5 seconds to 120 seconds, preferably 1.5 seconds to 120 seconds. The transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with heat development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development;
The image may be transferred by being brought into close contact with an image receiving member after thermal development and heated, or by being brought into close contact with an image receiving member after supplying water and further heated if necessary. Also, before exposure, 70℃~180℃
Preheating may be performed within the temperature range of . Also, JP-A-60
As described in Japanese Patent Application No. 143338 and Japanese Patent Application No. 60-3644, the photosensitive material and the image receiving member are preheated at a temperature of 80°C to 250°C immediately before thermal development transfer to improve mutual adhesion. Good too.

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. Generally, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source.

As the heating means, all methods applicable to ordinary heat-developable photosensitive materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, high-frequency heating may be used, or furthermore, a conductive layer containing a conductive substance such as carbon black may be provided on the back surface of the photosensitive material of the present invention or the back surface of the image receiving member for thermal transfer, and the Joule heat generated by energization may be utilized. You can also do that. There are no particular restrictions on the heating pattern, including methods of preheating (breheating) and then reheating, heating at a high temperature for a short time, or at a low temperature for a long time, continuously increasing, decreasing, or repeating, and even discontinuously. Although heating is possible,
A simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

The image-receiving layer of the image-receiving member that can be effectively used in the present invention includes:
It is sufficient that it has the function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, for example, a polymer contained in a tertiary amine or a quaternary ammonium salt, as described in US Pat.
．． Those described in No. 709.690 are preferably used. For example, as a polymer containing an ammonium salt, the ratio of polystyrene-co-N,N,N-tri-0-hexyl-N-vinyl-benzylammonium chloride is 1:4 to 4:1, preferably 1:1. It is.

Examples of polymers containing tertiary amines include polyvinylpyridine. A typical example of diffusion transfer! As a layer,
It can be obtained by mixing a polymer containing ammonium salt, tertiary amine, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support.

Another useful dye-receiving material is JP-A-57-2072.
50, etc., the glass turning temperature is 40℃ or higher, 2
Examples include those formed of organic polymeric substances that are heat resistant to 50° C. or lower.

These polymers may be supported on a support as an image-receiving layer, or may themselves be used as a support.

Examples of the heat-resistant organic polymer substances include polystyrene, polystyrene derivatives having substituents having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene,
Polyacetals such as polyvinylpyrrolidone, polyvinylcarbazolevinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichloride fluoroethylene, polyacrylonitrile, polyN. N-dimethylallylamide, polyacrylate with p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl Polyesters such as 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 and cellulose acetates. In addition, Polymer Handbook Second Edition (G.I. Brand Wrap, E.H. Inmargattl1i) John Wiley & Sons (Polymer) Landb
ook 2nd ed, (J, Brandru
p, E.

H, I IIlmerout Jm) John Wi
Also useful are synthetic polymers with a glass transition temperature of 40° C. or less, as described in the publication by John Ley & Sons. Generally, the molecular weight of the polymer substance is 2,000 to 200.
．． 000 is useful. These polymeric substances may be used alone or in a blend of two or more types, or may be used in combination of two or more types as a copolymer.

Useful polymers include cellulose acetates such as triacetate and diacetate, polyamides in combinations such as heptamethylene diamine and terephthalic acid, fluorene propylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, and diethylene glycol. and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, polyester, polyethylene terephthalate, and polycarbonate. These polymers may be modified. For example, polyethylene terephthalate using cyclohexane dimetatool, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy4-benzenesulfonic acid, etc. as a modifier is also effective.

A particularly preferable image-receiving layer is JP-A-59-22342
Layer made of polyvinyl chloride described in No. 5 and JP-A-60
Examples include a layer made of polycarbonate and a plasticizer described in Japanese Patent No. 19138.

These polymers can also be used as a support and receiver layer (receiver member), in which case the support may be formed from a single layer or from multiple layers. It's okay.

As the support for the image receiving member, transparent supports, opaque supports, etc. may be used, but for example, films such as polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, etc. supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, and talc, baryta paper, RC paper laminated with thermoplastic resin containing pigments, cloth, glass, aluminum, etc. Metals, etc., supports on which an electron beam curable resin composition containing a pigment is coated and cured, and supports on which a coating layer containing a pigment is provided. etc.

In particular, a support with a pigment-containing electron beam curable resin composition coated and cured on paper, or a support that has a pigment coating layer directly on the paper, and an electron beam curable resin composition on the WAFl coating layer. The support coated with the composition and cured can be used as an image-receiving member as it is because the resin layer itself can be used as an image-receiving layer.

When the present invention is applied to a heat-developable color light-sensitive material, the various polymers mentioned above can be used as a mordant for a dye image and as an image-receiving layer. It may be an image receiving element or the image receiving layer may be a 1vJ layer that is part of a thread developed color photographic material. If necessary, an opacifying layer (reflection layer) may be included in the light-sensitive material, such layer providing a desired degree of tIl radiation, e.g. visible light, which can be used to observe the dye image in the receiving WA layer. It is used for reflection. The opacifying layer (anti-tJ1 layer) can contain various reagents that provide the necessary reactivity, such as titanium dioxide.

The receiver (IFm) of the receiver Q member can also be formed in a type that can be peeled off from the heat-developable photosensitive layer.For example, after imagewise exposure of the heat-developable color photosensitive material, the image-receiving layer is superimposed on the heat-developable photosensitive layer and heated uniformly. It can also be developed.Also, after imagewise exposure of a heat-developable color photosensitive material and uniform heat development, an image-receiving layer is overlaid.
It is also possible to transfer the dye image released or formed from the dye-providing substance by heating at a temperature lower than the development temperature.

Margins [Examples] Below, Examples of the present invention will be described in detail, but the present invention is not limited to these embodiments.

[Example-1] [Preparation of silver salt dispersion] 5-methylbenzotriazole and silver nitrate were reacted in a water-alcohol mixed solvent to obtain 144 g of silver methylbenzotriazole, 5-methylbenzotriazole 0.4Q, polyvinylpyrrolidone<K-30) 2
A 0 wt % aqueous solution 20 (hnQ) and 540 ij of water were dispersed in an alumina ball mill, and 200 d of the above polyvinyl and lolidone aqueous solution were added to obtain 1, OOO, Q.

[Preparation of photosensitive silver halide emulsion] Preparation of silver iodobromide emulsion at 50° C. according to JP-A-57-92523, JP-A-57-92523;
92524, 11.0 g of potassium iodide was added to solution A in which 20 g of ossein gelatin, 1000 g of distilled water, and ammonia were dissolved. l31J
and potassium bromide 130q aqueous solution 5001
8 solutions of 1Q and solution C of an aqueous solution 500112 containing 1 mol of silver nitrate and ammonia were simultaneously added while keeping the pAg and pH constant. Furthermore, by controlling the addition speed of liquid B and liquid C, silver iodide containing ff17 mol%, positive 6
Eleven core emulsions with a face shape and an average grain size of 0.25 μm were prepared.

Next, in the same manner as described above, by coating a silver halide shell with a silver iodide content of 1 mol %, regular hexahedral grains with an average diameter of 0.3 μm (shell thickness 0.05 μm) were formed. A core/shell type silver halide emulsion was prepared. (The monodispersity was 8%.) The above emulsions were washed with water and desalted to obtain a yield of 700 mQ.

Furthermore, a photosensitive silver halide emulsion was prepared using the silver halide prepared above in the following manner.

Preparation of red-sensitive silver iodobromide emulsion The above silver halide 7001124
-Hydroxy-6-methyl-1゜3a-7 tetrazaindene 0.4 g Gelatin 32 (J Sodium thioate 10 mg The following sensitizing dye methanol 1% solution 80 sulfur distilled water
1200d sensitizing dye (a) [Preparation of reducing agent solution] Reducing agent R-11 was mixed with 93.2 (1) 2Qwt% aqueous solution of polyvinylpyrrolidone (K-30> 2071R, 40vQ of 5wt% aqueous solution of the following surfactant, and The DH was adjusted to 7.0 and 600 d with water and an aqueous citric acid solution.

(Surfactant) CH2-COOC+-12 (CF2 CF2), Il-
1 (and n represents 2 or 3, respectively) [Preparation of hot solvent dispersion] 430 g of p-toluamide and polyvinylpyrrolidone (
1,410 t12 of a 1.0 wt% aqueous solution of K-90) was dispersed in a ball mill to obtain a hot solvent dispersion.

[Preparation of dye-providing substance polymer dispersion] 122 g of dye-providing substance polymer P-''18, the following hydroquinone compound 4.017, and high boiling point solvent d-2 were added in the table below.
Mix 300 g of ethyl acetate in the mold shown in 1, heat and dissolve, add 248 g of Alkanol

(manufactured by Rousslow) was mixed with 1.440 iR of gelatin aqueous solution containing 34.617, dispersed with an ultrasonic homogenizer, distilled off ethyl acetate, and then added water to obtain 1.59
0112, and 11 kinds of dispersions were obtained.

H [Preparation of heat-developable photosensitive material-1] The following coating solution was wet-ailed onto a 180 μm thick photographic transparent polyethylene terephthalate film having a subbing layer.
It was coated with a B4 thickness of 114.3 μm and dried to prepare heat-developable photosensitive materials, designated as Samples Nos. 1 to 11.

(Coating liquid composition) Organic silver salt dispersion 80.0d Red-sensitive silver halide emulsion 38.41Q Reducing agent solution 48.0ml 12 Heat solvent dispersion 94.8 (1 Dye-donor polymer dispersion 127uN Photographic geladine 10w
% aqueous solution 21.1g phenylcarbamoylated gelatin 1wt% aqueous solution 27.11g citric acid aqueous solution and water 65.3d2.4-
Dichloro-6-hydroxy 1S-triazine sodium 2.5% aqueous solution 13.3 total

512d A photothermographic material in which a dye-providing substance polymer and a high boiling point solvent were separately dispersed and added was prepared as sample No. 0.12 in the following manner.

[Preparation of heat-developable color photosensitive material-2] <Preparation of dye-providing substance polymer dispersion> 122 g of dye-providing substance polymer P-18, the hydroquinone compound 4. OQ, 200 d of ethyl acetate were mixed and dissolved by heating, and 5 w of Alkanol XC (manufactured by DuPont) was added.
t% aqueous solution 165d, photographic gelatin 17.6 (1, phenylcarbamoylated gelatin (type 17819P)
C, manufactured by Rousseau) mixed with 960 d of gelatin aqueous solution containing 23.1 g and dispersed with an ultrasonic homogenizer,
After distilling off ethyl acetate, water was added and 1. ,oeom
I named it Q.

Preparation of high boiling point solvent dispersion> Mix 61 g of high boiling point solvent d-2 and 100 g of ethyl acetate, mix and disperse with 480 g of the gelatin aqueous solution, distill off the ethyl acetate, and add water. , 530d.

In place of the dye-providing substance polymer dispersion 127- in the heat-developable color photosensitive material-1, the comparative dye-providing substance polymer dispersion 84.7d and the high boiling point solvent dispersion 42.3 were used.
A photothermographic material-1 was prepared in the same manner as photothermographic material-1 except that d was used.

[Preparation of image receiving member] Polycarbonate (molecules 125,000, L-125
0, Yojin Kasei)'s ethylene chloride solution was applied onto photographic baryta paper and dried, resulting in a polycarbonate of 15.0Q/f.
An image receiving member was made as follows.

[Evaluation of sharpness] A line image chart (a planar grid made by cutting a large number of parallel grooves at equal intervals on a gold BH film on a thin glass substrate) was brought into close contact with the coated surface of the photosensitive material, and exposed. I did it.

Combine the exposed heat-developable photosensitive material and the image receiving member, and
The transfer image obtained by heat development at 50°C for 1 minute and peeling was evaluated using Sakura Microdensitometer PD.
〜1-5 type, the response function (Modulat
ion transfer function
1 or less (referred to as MTF value) was calculated.

Table 2 below shows the MTF values at frequencies of 5 lines per 1 mm.

The larger the value, the higher the sharpness, that is, the higher the image quality.

Table 2 N...However, H/C indicates the ff1ffi ratio of the high boiling point solvent to the dye-providing substance polymer.

As is clear from Table 2, the sharpness of the high boiling point solvent compared to the dye-donating polymer is excellent in the limited ff1l ratio region of the present invention, that is, the depiction of the microscopic portion of the image is excellent. I understand that.

Further, even though only the weight ratio falls within the range of the present invention, it is seen that the sharpness of the image quality is low in comparative sample No. 12 in which the high boiling point solvent does not form particles together with the dye-donating polymer.

Samples No. 4 to 9 (invention) used normal step wedge exposure, and the maximum density of the transferred image obtained by thermal development was higher than that of the comparative samples, and the fog was at the same level. The photosensitive materials of samples No. 10 and 11 (comparative examples) had stickiness on the surface.

In addition, in the preparation of the dye-providing substance dispersion, a dispersion containing a high-boiling solvent has a lower viscosity than a dispersion containing no high-boiling solvent, so that the time required to distill off ethyl acetate is shorter. The one made by FA was convenient.

In addition, when the dye-donor polymer dispersion corresponding to sample No. 1.6.10 was left at 40°C for 10 hours, the dispersion of sample PIN No. 1 slightly flocculated, and sample No.
The turbidity of the 0.10 dispersion increased.

The former causes clogging of filters and coating failures during the production of the photosensitive material, while the latter reduces the maximum density, both of which are undesirable.

The above-mentioned problem did not occur in the dispersion of sample No. 6 of the present invention. That is, it can be seen that the dye-providing substance polymer dispersion used in the present invention has excellent dispersion stability.

Example-2 The heat-developable photosensitive materials of Sample No. 1 (comparison) of Example-1 and Sample No. 36 (invention) were subjected to exposure for sharpness evaluation in the same manner as in Example-1, and then exposed at 150°C. Only the photosensitive material was heated for 1 minute on a heat block.

Each sample was bleach-fixed (Eastman Kodak E-
6 treatment, conditioner 25℃, 2 minutes, bleach 35
6 minutes at 25°C, 6 minutes at 25°C, 4 minutes at 25°C, and
The sharpness of the dye image dried and printed on the photosensitive material was measured using a Sakura microdensitometer model PDM-5 using the transmission method.The MTF value at a frequency of 5 lines per 1 mm was 25 for sample NO31; Sample No. 016 was 60. The present invention effectively prevents sharpness deterioration at both edges of the dye during thermal development.

Example-3 Table-3 instead of high boiling point solvent d-2 in Example-1
H/C=0. except that a high boiling point solvent as shown in .
In Example 5, Samples Nos. 13 to 16 were prepared in the same manner as in the photothermographic material-1 of Example-1. These samples were subjected to the same operation as in Example-1, and the MTF values were determined. The results are shown in Table-3.

Margin Table 3 Below Table 3 clearly shows that the sharpness of the image is high no matter which high boiling point solvent is used as long as it is a high boiling point solvent preferably used in the present invention.

Example-4 Example-10 In the heat-developable photosensitive material-1, P-7 was used instead of the dye-donating polymer P-18, and α-toluenesulfonamide (Kanto Kagaku) was used instead of the heat solvent P-toluamide. The following table-4 was prepared in the same manner as in Example-1 except that
Samples 17 to 24 shown below were prepared.

These samples were thermally developed at 160°C for 30 seconds or 1
MT was performed in the same manner as in Example-1 except that the temperature was 50°C for 1 minute.
The F value was determined. The results are shown in Table 4.

Table 4 As is clear from Table 4, the present invention is effective in improving image quality even in dye-donor polymers that release dyes.

Furthermore, it can be seen that the present invention does not impair the effect of improving image quality even if the thermal development conditions vary.

Claims (1)

[Claims] In a heat-developable photosensitive material having at least a photosensitive silver halide, a dye-donor polymer, a reducing agent, and a binder on a support, the dye-donor polymer is present in the form of particles together with a high boiling point solvent, and the dye-donor A photothermographic material characterized in that the weight ratio of high boiling point solvent to substance polymer is 0.05 to 4.0.