JPS6352137A - Heat-developable photosensitive material with improved shelf stability of image - Google Patents

Abstract

PURPOSE:To obtain a heat-developable photosensitive material ensuring superior clearness and stability for an image and causing no stain on the image by forming a photosensitive material having photosensitive silver halide, a reducing agent, a binder and a compd. which releases isocyanato during thermal development on the support. CONSTITUTION:A photosensitive material having photosensitive silver halide, a dye providing substance, a reducing agent, a binder and a compd. (C) which releases isocyanato during heat-development on the support is formed. Any compd. having an isocyanato group protected by a substituent which is rapidly eliminated at the time of heat-development may be used as the compd. C but a compd. represented by a formula A1-X1 is preferably used. In the formula, X1 is a protected isocyanato group and A1 is a bivalent org. group, especially preferably a bivalent org. group having a bonded ethylenic unsatd. group or a bonded group having an ethylenic unsatd. group.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a heat-developable photosensitive material capable of obtaining clear images without contamination, and particularly to a reducing agent contained in the photosensitive material or a reducing agent. The present invention relates to a heat-developable photosensitive material that can provide clear images with very little contamination caused by derivatives.

[Background of the Invention] A photosensitive material (thermally developable photosensitive material) that can easily and quickly obtain an image by carrying out a dry process using heat is well known, and the photothermally developable material and image forming method thereof are disclosed in, for example, Japanese Patent Publication No. 43 (1971). -4921, No. 43-4924, Fundamentals of Photographic Engineering (Published by Corona Publishing, 1979, pp. 553-55)
5, and Research Disclosure magazine, June 1978 issue, pages 9-15 (RD-17029).

Further, in recent years, attempts have been made to develop heat-developable color photosensitive materials that produce color images using various dye-providing substances. Among these methods, the method of releasing or forming a diffusible dye through heat development and then transferring the dye to obtain a color image is preferred in terms of image stability and clarity and processing simplicity and speed. It is excellent. This transfer method heat-developable color photosensitive material and image forming method are described in, for example, JP-A-59-12431,
No. 59-159159, No. 59-181345,
No. 59-229556, No. 60-2950, No. 6
No. 1-52643, No. 61-61158, No. 61-6
No. 1157, No. 59-180550, No. 61-1
No. 32952, No. 61-139842, U.S. Patent No. 4,
595,652, 4,59.0.154 and 4
, No. 584, 267, etc.

Although the clarity and stability of images formed from heat-developable color photosensitive materials have been significantly improved in recent years, there has been a problem in that image staining occurs during image storage. However, at present, a technology for removing image stains caused by various additives, particularly reducing agents or reducing agent derivatives, contained in photothermographic materials has not yet been perfected.

[Object of the Invention] An object of the present invention is to provide a heat-developable photosensitive material in which formed images have excellent clarity and stability, and in particular, do not cause staining on the formed images.

[Structure of the Invention] An object of the present invention is to provide a heat-developable photosensitive material having on a support at least a photosensitive silver halide, a dye-providing substance, a reducing agent, a binder, and a compound that releases isocyanate during thermal development. Ta.

[Specific Structure of the Invention] The heat-developable photosensitive material of the present invention consists of a heat-developable photosensitive element and an image-receiving element. Hereinafter, the heat-developable photo-sensitive element is referred to as a heat-developable photosensitive material or simply a photosensitive material, and the image-receiving element is referred to as an image-receiving member. That's what it means.

In a heat-developable photosensitive material containing a reducing agent or reducing agent derivative, such as the photosensitive material of the present invention, excess reducing agent or reducing agent derivative that did not contribute to image formation may be contained in the photosensitive material or on the image receiving member. It is necessary to convert the reducing agent to a more stable compound in order to prevent contamination caused by its residual presence in the reactor.

In general, isocyanates are one of the highly reactive groups that react well with nucleophilic reagents, and therefore are effective as reagents for converting the reducing agent or reducing agent derivative into a more stable compound. However, isocyanates are highly reactive and therefore sensitive to moisture, resulting in poor storage stability and strong irritating odors, making them unsuitable for practical use in photosensitive materials. Based on the idea of converting isocyanates into precursors, the present inventors have discovered that the drawbacks of isocyanates can be overcome by using a compound that releases isocyanates only during thermal development.

In the compound that releases isocyanate upon heating in the present invention (hereinafter referred to as the isocyanate precursor of the present invention), the isocyanate group is protected in advance with another substituent, and the isocyanate group is immediately protected during thermal development. Any compound may be used as long as it separates from 4, but preferred is a compound represented by the following general formula CII.

General formula [I] A+ -X+ In the general formula [I], xl represents a previously protected isocyanate group, and preferable specific examples include sodium hydrogenite, phosphate, imidazole, carbodiimide, etc. , adducts with isocyanate groups, and precursors forming urethane, amine imide, hydroxamic acid, dioxazolone ring, dioxathiazole S-oxide, hydroxamic acid O-sulfonate, and the like.

One particularly preferred example is a protected form having an amine imide structure, but since amine imides usually undergo a Curtius rearrangement of N-N ylides at temperatures above about 130°C to generate isocyanate groups, the present invention is effective. It can be effectively used as an isocyanate precursor.

Another particularly preferred example is a protected form having a dioxazolone ring structure, and the dioxazolone ring is usually decarboxylated by heating.
Since it generates isocyanate groups, it can be effectively used as an isocyanate precursor in the present invention.

In the general formula [I], A1 represents a divalent organic group, but it may be an organic group of any structure as long as it can bond to etc.), cycloalkylene B (eg, cyclohexene group, etc.), arylene group (eg, phenylene group, etc.), or heterocyclic residue (eg, furylene group, etc.).

Moreover, as a more preferable compound of the compound represented by the general formula [I], a polymer having a repeating unit derived from the monomer represented by the -a formula [I] may be mentioned.

General formula [Ir1 X2-A2-Q In general formula [I[], A2 is a simple bond or 2
Although it represents a valent organic group, it may be any type of structural group as long as it can bond to x2 and Q, and examples thereof include the same akebono group as A1 in general formula [I].

Q in the general formula [I[] represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and is preferably represented by the following general formula [11].

General formula [I[] In the general formula [■1], R represents a hydrogen atom, a carboxy group, or an alkyl M (e.g., methyl group, ethyl group, etc.), and this alkyl group may have a substituent, and the substituent Examples of the group include a hydrogen atom (eg, a fluorine atom, a chlorine atom, etc.), a carboxy group, and the like. The carboxy group represented by R and the carboxy group of the substituent may form a salt. Jl and J2 each represent a divalent bonding group, and examples of the divalent bonding group include -NHC
O-1-CONH-1-COO-1-OCO-1-SC
O-1-COS-1-0-1-S-1-SO-1-8O
2- etc. Yl and Y2 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. Examples of the alkylene group include , methylene group, ethylene group, propylene group, etc., and as an arylene group,
For example, the aralkylene group is a phenylmethylene group, the alkylenearylene group is, for example, a methylenephenylene group, and the arylenealkylene group is, for example, a phenylenemethylene group. Parts 1, 11, 22, and 12 represent O or 1, respectively.

×2 in the general formula [IN represents a previously protected isocyanate group, and preferable specific examples include, for example,
Adducts of isocyanate groups with sodium bisulfite, phosphates, imidazole, carbodiimides, etc. Also, doloxamic acid, dioxazolone rings, dioxathiazole S-oxides, hydroxamic acid 〇-sulfonates, etc. are formed with urethanes, amine imides, etc. Examples include precursors that are

One particularly preferred example is a protected form having an amine imide structure, but since amine imides usually undergo a Curtius rearrangement of N-N ylides at temperatures above about 130°C to generate isocyanate groups, the present invention is effective. In particular, vinyl monomers having an amine imide structure that can be effectively used as isocyanate precursors have good storage stability, and polymers having the vinyl monomer as a constituent unit can be easily synthesized. More preferred examples of the monomer having the amine imide structure include compounds represented by general formulas [IV] and [V].

General formula [TV] General formula [V] -IIQ formula [TV], [v], R+, R2,
R3 and R4 each represent an alkyl group (eg, methyl group, ethyl group, propyl group, etc.).

Polymers having repeating units derived from monomers represented by general formula [rV] generate isocyanate groups during thermal development, and repeating units derived from monomers represented by general formula [V] The polymer having the above generates isocyanate groups protected by urethane bonds during thermal development.

Another particularly preferable example is a protected form having a dioxazolone ring structure, but since the dioxazolone ring is usually decarboxylated by heating to generate an isocyanate group, the isocyanate of the present invention is It can be effectively used as a precursor, and in particular, a monomer having a dioxazolone ring structure can be relatively easily synthesized into a polymer through radical polymerization or the like.

A more preferable example of the vinyl monomer having the dioxazolone ring structure is a compound represented by the general formula [■].

A polymer having a repeating unit derived from a monomer represented by the general formula [Vll] undergoes decarboxylation and generates isocyanate groups during thermal development.

The polymer having repeating units derived from monomers represented by the general formulas [I[], [rV], [Vl and [Vll] of the present invention has the general formulas [II], [rV]
, [Vl and [Vll] Even if it is a so-called homopolymer of repeating units consisting of only one type of monomer represented by
It may be a copolymer made of a combination of two or more monomers represented by l, or it may be a copolymer made of one or more other copolymerizable comonomers having an ethylenically unsaturated group.

The comonomer having an ethylenically unsaturated group that can form a copolymer with the monomers represented by the general formulas [I[], [rV], [Vco and [Vll] of the present invention includes:
Acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, methacrylmiates, allyl compounds, vinyl ethers Examples include vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, various unsaturated membranes, etc. Among these comonomers having an ethylenically unsaturated group, Preferred specific examples include methacrylate, methyl methacrylate, vinyl acetate, vinyl chloride, and droxypropyl methacrylate.
n-butyl acrylate, acrylonitrile, hydroxyethyl acrylate, glycidyl methacrylate, styrene, N-vinylpyrrolidone, polybutadiene, 1,
Examples include 4-cis-polyisoprene, acrylamide, methylmethacrylamide, methylmonyl ketone, methyl vinyl ether, allyl acetate, divinylbenzene, butyl crotonate, dimethyl itaconate, diethyl maleate, dimethyl fumarate, and acrylic acid.

Further, the general formula [II], [rV], CVl of the present invention
When a copolymer is formed with the monomer represented by [Vl i and the comonomer, preferably the repeating unit consisting of the monomer represented by the general formula 'III, [rV], [Vl and [Vll] is This is the case where the amount is 10 to 90% by weight of the total polymer.

The preferred molecular weight range of the polymeric isocyanate precursor compound of the present invention is s, oo as a heavy open average molecular product.
400.000 from o.

Specific representative examples of the isocyanate precursor of the present invention are listed below, but the present invention is not limited thereto.

(1) (H3x=2
Qwt%, y=30wt%, weight average molecular weight 1
0,000 x=:45wt%, :/=55vt%, weight average molecular weight 160,000 (3) cH3 C7) x=100wt% weight average molecular weight 6,000 CH3 X=30wt%, y=70wt%, weight average Molecular weight s, oo.

(P) P=-CH2-CH- COCH3 x=85wt, y=15wt%, weight average molecular weight 15,000) P=CH2CHC1- (3) CH3P = CH2-C- C00CH2CHCH3 H x = 40wt%, v = 5Qwt%, weight average molecular weight 110,000 (#JP = -CH, -CHCN-x = 4Qwt%
, Y=60 wj%, weight average molecular weight 80,00
0) CH3 P=-CH2-C- 0OCH3 CH3 -CH2-C- C00CH2CHCH3 H
=y++y2) Weight average molecular weight 10.500 ) CH3 (7) x = 100 wt%, weight molecular weight average fraction - r amount 6,900 (a) CH3 P” CHz-C- 0OCH3 x = 70 Wt, y = 30~゛t%, 1 quantum direction molecular weight 23 Synthesis of the isocyanate precursor compound of the present invention Regarding the method, detailed research has been carried out on the monomer synthesis method and polymerization method, for example, in ``Journal of Polymeric Science
lym, Sci.) 6A-1, 363 (1968
), 9 A-1, 3453 < 1971), “Macromolecules, < Macromolecules
), 1, 254 (1968), 3 (6)
, 715 (1970), and “Journal.
of Applied Polymeric Science J (
J, ADDI, Polym, Sci,), 15
, 2609 (1971), etc.

The isocyanate precursor in the present invention may be added to any layer in the heat-developable photosensitive material, but is preferably added to the silver halide emulsion layer, intermediate layer, and third layer,
More preferably, it is added to an intermediate layer and/or a protective layer, and in this case, it is best to use an isocyanate precursor polymer to prevent diffusion into each layer of the photosensitive material. Moreover, when it is added to a photosensitive material, it is also prohibited to further add it to an image-receiving member.

When the incyanate precursor in the present invention is added to an image-receiving member, the compound or a compound generated by the reaction of the compound with a contamination-causing substance such as a reducing agent will be present on the image. The compound, or the compound produced by the reaction of the compound with a contaminating substance such as a reducing agent, must be colorless and stable.Also, when added to a photosensitive material, the low molecular weight compound must be able to diffuse through each layer. As described above, it must be colorless and stable because there is a possibility that it will move to the image receiving section.

The amount of the isocyanate precursor added in the present invention is 0.1 to 500 mol% based on the amount of reducing agent contained in the light-sensitive material, calculated as inocyanate released.
is preferable, and more preferably 1 to 200 mol%.

The method of adding the isocyanate precursor in the present invention is arbitrary, for example, after dissolving it in a low boiling point solvent (methanol, ethanol, ethyl acetate, etc.) or a high boiling point solvent (dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc.). It can be used after being dispersed by ultrasonic waves, or used as an aqueous solution, or after being dispersed in a ball mill with an aqueous solution of an appropriate polymer (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.).

Hereinafter, in the margin below, the thermal phenomenon photosensitive material of the present invention basically contains one thermal mass @
The photosensitive paste contains (1) photosensitive silver halide, (2) reducing agent, (3) dye-providing substance, and (4) binder, and further contains (5) organic silver salt as necessary. is preferred. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, the heat-developable photosensitive layer is divided into two layers, and the components (1), (2), (4), and (5) are If two or more constituent layers are in a state where they can react with each other, such as by containing a dye-providing substance (3) in a heat-developable photosensitive layer on one side and a dye-providing substance (3) in a layer on the other side adjacent to this photosensitive layer, It may be contained separately.

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

The thermal phenomenon photosensitive material of the present invention has one or more heat-developable photosensitive layers on a support. In the case of color, it generally has three heat-developable photosensitive layers with different color sensitivities, and in each photosensitive layer, dyes with different hues are formed or released by heat development.

Typically, 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, but the invention is not limited to this. It is also possible to combine a near-infrared sensitive layer.

The structure of each layer can be arbitrarily selected depending on the purpose. For example, a structure in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are sequentially formed on the support, or a structure in which a blue-sensitive layer is sequentially formed on the support. layer, a green-sensitive layer, a red-sensitive layer, or sequentially on a support,
There are configurations such as a green photosensitive layer, a red photosensitive layer, and a blue photosensitive layer.

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. To coat the heat-developable photosensitive layer and these non-photosensitive layers on a support, a general silver halide photosensitive material is used. Methods similar to those used for stone preparation can be applied.

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, 5
In the case of a dye-donating substance that releases or forms a diffusible dye by coupling with an oxidized form of a reducing agent such as those disclosed in No. 9-181345 and No. 60-2950, the present invention Examples of reducing agents used in
61,270, 3.764.328 specifications,
Also RD i\o, t2146, same N 0.15
108, same N 0.15127 and JP-A-56-27
p-phenylenediamine-based and p-aminephenol-based phenomenon agents, phosphoramidophenol-based, sulfonamidophenol-based phenomenon agents described in Publication No. 132;
Sulfonamide aniline type developing agents, hydrazone type coloring agents, etc. can be used. Further, color developing agent precursors described in U.S. Pat. No. 3,342,599, U.S. Pat. can.

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) % formula % 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 represent may be closed to form a heterocycle. R3, R4.

R5 and R6 each have a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number of 1 to 30 (preferably 1 to 30) that may have a substituent. 4)
represents an alkyl group, R3 and R1 and R5 and R2 may each be ring-closed to form a heterocycle, M is an alkali metal Ii! Represents a compound containing an atom, an ammonium group, a nitrogen-containing organic base, or a quaternary nitrogen atom.

The nitrogen-containing m base in the above general formula (1) is an organic compound containing a nitrogen atom that exhibits basicity capable of forming a solid salt and a salt, and particularly important organic bases include amine compounds. Further, as the salt of the nitrogen-containing organic base, the above-mentioned organic base black isosate salts (eg, hydrochloride, 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 4111i covalent bond.

Next, preferred specific examples of reducing agents other than those shown in JP-A-56-146133 are shown below.

(R, -1) QC)l.

(R-Z) (R-3) (R-4-) (R-S) (R-et al.) (R-7) Two or more of the above reducing agents may be used at the same time. Further, it is also possible to use a black and white developing agent 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. Alternatively, in the case where only a silver image is simply obtained, 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-aminophenol, etc.), sulfonamidophenols [e.g. 4-benzenesulfone amidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dipromo 4-(
p-toluenesulfonamide) phenol, etc.], or polyhydroxybenzenes (e.g. hydroquinone, t
ert-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 naphthols such as 1,1'-dihydroxy-2,2'-
Binaphthyl, 6.6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6.6-sinitro2.
2'-dihydroxy-1,1'-binaphthyl, 4.4'
-dimethoxy-1,1'-dihydroxy-2,2'-binaphthyl, bis(2-hydroxy-1-naphthyl)methane, etc.], methylenebisphenol i [e.g. 1,1-bis(2-hydroxy-3,5- dimethylphenyl)-3
゜5.51-limethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5-di-tert-butyl) phenyl)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-humanOxy3-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 type of acidic silver salt used, and the type of other additives, etc. Usually 0.01 per mole of photosensitive silver halide
~1500 mol, preferably 0.1~20
It is 0 mole.

When the heat-developable photosensitive material of the present invention is a color type, a dye-providing substance is used.

Dye-providing substances that can be used in the present invention will be explained below. The dye-donating substance may be any substance as long as it participates in the reduction reaction of the photosensitive silver halide and/or the organic silver salt used as necessary and can form or release a diffusible dye as a function of the reaction. Depending on their reaction form, negative-working dye-donors act on a positive function (i.e., form a negative dye image when negative-working silver halide is used) and negative-acting dye-donors act on a negative function. It can be classified as a positive-working dye-donor (that is, it forms a positive dye image when negative-working silver halide is used). Negative dye-donating substances are briefly described below as release-type compounds that release a diffusible dye when oxidized.

Examples of the reducible dye-releasing compound include compounds represented by general formula (2).

General formula (2) % formula % In the formula, Car represents a reducing M-carrier (so-called carrier) that is oxidized and releases a dye upon reduction of photosensitive silver halide and/or limited salt used as necessary. And Dy
e is a diffusible dye residue.

Specific examples of the above-mentioned reducible dye-releasing compounds include JP-A-57179840, JP-A No. 58-116537, JP-A No. 59
-60434, 59-65839, 59-71
No. 046, No. 59-87450, No. 59-88730
No. 59-123837, No. 59-165054, and No. 59-15959.

As another reducing dye releasing compound, for example, general formula (3)
Examples include compounds represented by:

General formula (3) In the formula, AI and A2 each represent a hydrogen atom, a hydroxy group, or an amino group, and Dye is Dy represented by the general formula (2).
It is synonymous with e. Specific examples of the above compounds are given in JP-A-59-1
This is shown in Japanese Patent No. 24329.

As a coupled dye-releasing compound, general formula (4) is used.
Examples include compounds represented by:

General formula (4) % formula % In the formula, CD+ is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, and J is a 2!1lli bond. The bond between Cpl and J is cleaved by reaction with the oxidized form of the reducing agent. nl represents O or 1, and Dye has the same meaning as defined in general formula <2). In addition, CD1 is preferably substituted with various ballast groups in order to make the coupled dye-releasing compound non-diffusible, and the ballast group has 8 or more carbon atoms ( more preferably 12 or more) organic groups, or hydrophilic groups such as sulfo groups and carboxy groups, or 8 or more (more preferably 12 (2) or more) carbon atoms and sulfo groups,
It is a group that also has a hydrophilic group such as a carboxy group. Another particularly preferred ballast group can include polymer chains.

Specific examples of the compound represented by the above general formula (4) include JP-A-57-186744 and JP-A-57-122596.
No. 57-160698, No. 59-17483
No. 4, No. 57-224883, No. 59-15915
No. 9, No. 59-231540 Specification i.

As the coupling dye-forming compound, general formula (5) is used.
Examples include compounds represented by:

General formula (5) %Formula %(8) In the formula, C1)2 is a specific group (so-called coupler residue) that can react with the oxidized product of the reducing agent (coupling reaction) to form a diffusible dye. ), F represents a divalent bonding group, and B represents a ballast group.

The coupler residue represented by CD2 preferably has a molecular weight of 700 or less for the sake of diffusibility of the dye formed.
More preferably it is 500 or less.

Further, the ballast group is preferably the same as the ballast group defined in general formula (4), and particularly has 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group. Groups having the same group are preferred, and polymer chains are more preferred.

The coupled dye-forming compound having a polymer chain is preferably a polymer having a repeating unit derived from a monomer represented by general formula (6).

General formula (6) % formula %) In the formula, C1)2 and F have the same meanings as defined in general formula (5), Y represents an alkylene group, an arylene group, or an aralkylene group, and 2 is 0 or 1 and Z is 2
represents a valent organic group, and represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupled dye-forming compounds represented by general formulas (5) and (6) include JP-A-59-12.1
No. 339, No. 59-181345, No. 60-29
No. 50, Japanese Patent Application No. 59-179657, No. 59-181
No. 604, No. 59-182506, No. 59-1825
No. 07, each Mei 1B1, etc., and include, for example, the following compounds.

bomber M-1 M-4 CH1 M-5 0Hx: 60% by weight M-7 CH.

y: 50% by weight PM-8 PM-9 M-10 In the above general formulas (4), (5) and (6), C
More specifically, the five couplers represented by pl or Cpt are preferably groups represented by the following general formula.

General formula (7) General formula (8) General formula (9
) General formula (10) General formula (11)
General formula (12) General formula (13)
General formula (14) General formula (15)
General formula (16) R9U In the formula, R7, R8, R9 and R10 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group , arylsulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amine L alkoxy group, aryloxy group, cyam L alkylsulfonyl group, arylsulfonyl group, ureido group, alkylthio group, arylthio group, carboxy group, sulfo group or heterocycle represents a residue,
These are further substituted with hydroxyl group, carboxy group, sulfo group, alkoxy group, cyano group, nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, imide group, halogen atom, etc. may have been done.

These substituents are selected depending on the purpose of Cp+ and CI)2, and as mentioned above, in Cp+, one of the substituents is preferably a ballast group, and in Cp2, it is preferable to improve the diffusivity of the dye formed. In order to increase the molecular weight, it is preferable to select substituents so that the molecular type is 700 or less, more preferably 500 or less.

The positive dye-donating substance ζ is, for example, the following general formula (1
There is an oxidizable dye-releasing compound represented by 7).

General formula (17) In the formula, Wl represents a collection of atoms necessary to form a quinone ring (which may have a substituent on this ring),
RI+ represents an alkyl group or a hydrogen atom, E is -N-C-+RI3← (in the formula, R12 represents an alkyl group or a hydrogen atom, RI3 represents an oxygen atom or I2 represents -N-) or -302 -, “is O
or 1, and Dye has the same meaning as defined in general formula (2). A specific example of this compound is JP-A-59-1
It is described in specification m of No. 66954, No. 59-1511445, etc.

As another positive dye-donor substance, the following general formula (18) is used.
There are compounds that lose their dye-releasing ability when oxidized, such as the compound represented by:

General formula (18) In the formula, W2 is a benzene ring (with a substituent on the ring to form - (which may be present) (this represents a necessary group of atoms,
R", r, E, and Dye have the same meanings as defined in general formula (17). Specific examples of this compound are described in the specifications of JP-A-59-124327 and JP-A-59-152440, etc. ing.

Still another positive dye-providing substance is expressed by the following general formula (
Examples include compounds represented by 19).

General formula (19) In the above formula, w2, R", oyc, general formula (18
) has the same meaning as defined in ).

A specific example of this compound is JP-A No. 11359-154.145
It is written in @ etc.

The above general formulas (2), (3), (4), (17) (18
) and (1), the residue of the diffusible dye represented by Dye will be explained in further detail. As the residue of the diffusible dye, it is preferable that the molecule m is 800 or less, more preferably 600 or less, for the sake of the diffusibility of the dye, and azo dye,
Examples include residual bases such as azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. These dye residues (y) may be in a temporary short-wave form that can be multicolored during heat development or transfer.
The present rateable dye residues described in No. 9-48765 and No. 59-124337 are also preferred.

These dye-providing substances may be used alone or in combination of two or more. The amount used is not limited, and depends on the type of dye-providing substance, whether it is used alone, 7) one or two or more types are used in combination,
Alternatively, the photographic constituent layer of the light-sensitive material of the present invention is a single layer or two layers.
The amount to be used may be determined depending on whether the layer is multilayered or not, but for example, the amount to be used may be 0.050 to 50 g, preferably 0.1 g to 10 g per 112 o.

The dye-providing substance used in the present invention can be incorporated into the photographic constituent layer of the heat-developable light-sensitive material using any method. Cresyl phosphate, etc.) and then subjected to ultrasonic dispersion, or dissolved in an alkaline aqueous solution (e.g., 10% sodium hydroxide aqueous solution, etc.) and then neutralized with mineral acid (e.g., hydrochloric acid or nitric acid, etc.). Alternatively, it can be used after being dispersed in a ball mill with an aqueous solution of an appropriate polymer (eg, gelatin, polyvinyl butyral, polyvinylpyrrolidone, etc.).

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. According to a further preferred embodiment, silver halide emulsions having shelled silver halide grains can be used.

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
, No. 447.927, No. 3.761.266, No. 447.927, No. 3.761.266, No.
As described in No. 3.703.584, No. 3.736.140, etc., this silver halide grain has a higher sensitivity inside the grain than the surface sensitivity of the silver halide grain. Also, U.S. Patent Nos. 3.271,157 and 3.447.
927 and 3,531, 291, or silver halide emulsions having silver halide grains incorporating polyvalent metal ions, or U.S. Pat.
A silver halide emulsion containing a dopant described in Japanese Patent Publication No. 1,276, in which the grain surface of the silver halide grains is weakly sensitized, or JP-A-50-8524 and JP-A-50-8524.
Silver halide emulsion consisting of grains having a product structure as described in No. 38525 etc., Sonoike JP-A-52-156
644 and JP-A No. 55-127549.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art.

The silver halide in the above-mentioned photosensitive emulsion may be coarse grains or fine grains, but the preferred grain size is approximately 0.00 μm to approximately 1.5 μm, more preferably approximately 0.00 μm to approximately 1.5 μm in diameter. .01 μm to about 0.05 μm.

In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with an organic silver salt described below, and photosensitive silver halide may be formed in a part of the silver salt. can.

These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amounts used are -
O,oo 1g to 50g for 1-12 supports per i
It is preferable that it is, more preferably 0.1 g to 1
It is 0g.

Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like.

The added color of these sensitizing dyes is from 1.times.10@-4 mole to 1 mole per mole of photosensitive silver halide or silver halide forming component. More preferably, 1X10-mol to 1X1
It is 0-1 mole.

In the heat-developable photosensitive material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving phenomenon properties.

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 carboxylic acids as described in each publication and the specifications of U.S. Patent No. 3.330.633, U.S. Patent No. 3.794.496, U.S. Patent No. 4.105.451, etc. Silver salts of carboxylic acids having heterocycles, such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, silver α-(1-phenyltetrazolthio)acetate etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-26582, No. 4
No. 5-12700, No. 45-18416, No. 45-2
No. 2185, JP-A-52-137321, JP-A-58
There are silver salts of imino groups described in publications such as No.-118638, No. 58-118639, and U.S. Pat. No. 4,123,274.

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 organic 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, sand mills, colloid mills, video mills, and the like.

In addition, the method for preparing organic silver salts is to dissolve and mix silver 1iIII acid and raw material organic compounds in water or a paid solvent, but if necessary, a binder may be added or water may be added. It is also effective to add an alkali such as sodium oxide to promote dissolution of the organic compound, or to use an ammoniacal silver nitrate solution.

The amount of the organic silver salt to be used is usually 0.01 to 500 mol, more preferably 0.1 to 100 mol, per 1 mol of photosensitive silver halide. More preferably 03
~30 moles.

Binders used in the heat-developable photosensitive materials of the invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, and gelatin such as phthalated gelatin. Derivatives, cellulose arede protein, starch,
One or a combination of two or more synthetic or natural polymeric substances such as natural substances such as polysaccharides such as gum arabic can be used. In particular, it is preferable to use gelatin or a derivative thereof together with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol. It is a mixed binder with (including copolymers with).

The amount of binder used is usually 0, o per 1f of support.
sg to 50t), preferably 0.1g to +og.

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.

Supports used in the heat-developable photosensitive material of the present invention include, for example, polyethylene film, cellulose film, polyethylene film, and synthetic plastic films such as polyvinyl chloride. , paper supports such as photographic base paper, stamp paper, baryta paper and resin coated paper, as well as the use of these supports.
Examples include a support obtained by coating and curing an electronic tlA curable resin composition.

When the photothermographic material of the present invention and the photosensitive material are of a transfer type and an image receiving member is used, various heat solvents are preferably added to the photothermographic 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. These compounds are described in, for example, U.S. Patent No. 3.347.675, U.S. Pat.
9556, No. 59-68730, No. 59-84236
No. 60-191251, No. 60-23254
No. 7, No. 60-14241, No. 61-52643,
Japanese Patent Application No. 60-218768, No. 60-181965, No. 60-184637, etc., U.S. Patent No. 3.438.
No. 776, No. 3.666, No. 477, No. 3.667, 9
No. 59, JP-A No. 54-19525, JP-A No. 53-2482
9, No. 53-60223, No. 58-118640, and No. 58-198038, examples of which are particularly useful in the present invention include urine iK conductors. (e.g., dimethylurea, diethylurea, phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide, etc.), sulfonamide derivatives (e.g., benzenesulfonamide, α-
toluenesulfonamide, etc.), polyhydric alcohols (e.g., 1.5-bentanediol, 1°6-hexanediol, 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 wireless/poor. A compound having a modification ratio ("Organic Conceptual Diagram" by Yoshio Koda, Sankyo Shuppan, 1984) in the range of 05 to 3,01, preferably 0.7 to 25, particularly preferably 1.0 to 2.0. be.

Specific examples of the above-mentioned hydrothermal solvents are described in, for example, Japanese Patent Application No. 60-278331 and No. 60-28082.1.

The heat solvent is added in such a way that the effects of the photosensitive silver halide emulsion layer, intermediate layer, protective layer, image receiving layer of an image receiving member, etc. can be obtained.

Addition 1 of hot solvent is usually 10% to 50% by weight of the binder amount.
0% by weight, preferably 30% by weight to 1% to 200% by weight.

B2 f' margin under.

The thermal phenomenon photosensitive material of the present invention may contain various additives in addition to the above-mentioned components, if necessary.

For example, melt formers such as 7 pitamide and succinimide described in U.S. Pat. No. 3.438.776; The compound -CO-1-8O2- described in U.S. Pat. No. 3,667,959
Examples include nonaqueous polar organic compounds having a melting point of 20° C. or higher, such as lactones having a 1-8o group.

Benzophenone derivatives described in Zarani JP-A-49-115540, JP-A-53-24829, JP-A-53-
Recorded in No. 60223! phenol derivatives described in JP-A No. 58-118640, polycystic alcohols described in JP-A No. 58-198038, sulfamoylamide described in JP-A No. 59-84236. Compounds etc. can also be mentioned.

Further, a color toning agent known in heat-developable light-sensitive materials may be added as a development accelerator to the heat-developable light-sensitive material of the present invention. Examples of color toning agents include phthalazinone,
Phthalimide, bilasicone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2゜3-dihydro-phthalazinedione, 2
．． 3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2) 1-1,3-benzothiazine-2,4-( 3
H) dione, benzotriazine, mercaptotriazolene, aminomercaptotriazole, acylaminomercaptotriazole, phthalic acid, naphthalic acid,
phthalamic acid, 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, and furthermore phthalazine and maleic acids. Examples include combinations of acids, itaconic acid, quinolinic acid, gentisic acid, and the like.

Other development accelerators include compounds described in JP-A-59-177550 and JP-A-59-111636. Further, a development accelerator releasing compound described in JP-A-59-280881 can be used.

As antifoggants, for example, U.S. Pat. No. 3.545,
Higher aliphatic compounds described in No. 739, Special Publication No. 1973-
Mercury salt described in No. 11113, JP-A-51-474
N-halogen heptacompound described in U.S. Patent No. 3,
700, 457, mercapto compound-releasing compounds described in JP-A No. 51-50725, arylsulfonic acids described in JP-A No. 49-12501 et al., JP-A No. 54-47,119.
Lithium carboxylic acid salt described in British Patent Nos. 1 and 4
55,271, the oxidizing agents described in JP-A-50-101,019, the sulfinic acids or thiosulfonic acids described in JP-A-53-19825, the 2-thiouracils described in JP-A-51-3223, the oxidizing agents described in JP-A-50-101,019; Simple sulfur described in No. 26019, No. 51-42529, No. 51-8
Disulfide and polysulfide compounds described in No. 112.1, No. 55-93149, No. 51-57435
Rosin or diterpenes described in No. 51-10
Polymeric acids with free carboxyl or sulfo]/acid groups as described in U.S. Pat. No. 4,138,
Thiazolinthione described in No. 265, JP-A-54-51
No. 821, as described in U.S. Pat. No. 4,137,079.
．． 2.4-triazole or 5-mercapto-1,
2,4-triazole, thiosulfinic acid esters described in JP-A-55-140833, JP-A No. 55-1423
1,2,3,4-thiatriazoles described in No. 31,
No. 59-46641, No. 59-57233, No. 59
Examples thereof include dihalogen compounds or trihalogen compounds described in Japanese Patent No. 57234, and thiol compounds described in Japanese Patent No. 59-111636.

In addition, as other antifoggants, Japanese Patent Application No. 59-565
It can be preferably used in combination with the hydroquinone derivative described in No. 06.

Further particularly preferred antifoggants include the inhibitors having hydrophilic groups described in Japanese Patent Application No. 60-218169, the polymer inhibitors described in Japanese Patent Application No. 60-262177, and the polymer inhibitors described in Japanese Patent Application No. 60-262177. Inhibitor compounds having a ballast group as described in No. 60-263564 may be mentioned.

Silver image stabilizers include U.S. FI Permit No. 3.707.
377, the polyhalogenated oxidizing agent described in Belgian Patent No. 768,071 Mei 1 [5-
methoxycarbonylthio-1-phenyltetrazole,
Monohalo compounds described in JP-A-50-119624,
Examples include the bromine compound described in JP-A-5L120328, and the tribromoethanol described in JP-A-53-46020. Various monohalogenated antifoggants for upper limit halogen emulsions described in JP-A-50-119624 can also be used.

Other image stabilizers include U.S. Pat. No. 3,220;
No. 846, No. 4.082.555, No. 4.088
．． No. 496, JP-A-50-22625, Research Disclosure (RD) No. 12021, 15
No. 168, No. 15567, No. 15732, No. 1
5733, 15734, 15776, etc. Compounds called Activate Precursors that release basic substances by heat, such as compounds such as guanidinium trichloroacetate that release bases by decarboxylation with heat. , aldnamide compounds such as galactonamide, amine imides, compounds such as 2-carboxycarboxamide, sodium phosphate base generators described in JP-A-56-130745 and JP-A-56-132332, British Patent No. 2 Compounds that generate amines through intramolecular nucleophilic reactions described in JP-A-59-157637, hydroxamic acid carbamates, etc. described in JP-A No. 166943, and aldoxime carbamates described in JP-A No. 59-180537. No. 59-1748
Examples include base release agents described in No. 30 and No. 59-195237.

Furthermore, U.S. Patent No. 3,301,678, 3,50
No. 6, 444, No. 3, 824, 103, No. 3
, 844, No. 788, RD No. 1203S, 18
Illithiuronium compounds, S-rubamoyl derivatives of mercapto-containing compounds, and nitrogen-containing heterocyclic compounds described in No. 016 etc. may be used for the purpose of stabilizing images,
Furthermore, U.S. Patent No. 3,669,670;
No. 012, 260, No. 4,060,420, No. 012, 260, No. 4,060,420, No.
4, 207, 392, RD 15109, RD 17711, etc., nitrogen-containing paid bases called activator stabilizers and activator stabilizer precursors, such as α-sulfonylacetate or trichloroacetate of 2-aminothiazoline and acylhydrazine. Compounds and the like can be used for the purpose of accelerating development and for the purpose of stabilizing images.

Also, for example, JP-A-56-130745 and JP-A-59-2
48-143, it may be developed in the presence of a small amount of water, or it may be sprayed with water before heating, or
U.S. Patent No. 3
．． The phenomenon may also be caused by hot steam, hot air containing moisture, etc., as described in No. 312, No. 550. In addition, compounds that release water into heat-developable photosensitive materials, such as Japanese Patent Publication No. 44
- Compounds containing water of crystallization as described in No. 26582,
For example, gJ acid sodium sodium dodecahydrate, ammonium alum diquadrate, etc. may be included in the thermal phenomenon light-sensitive 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.

In the heat-developable photosensitive material of the present invention, colloidal silica may be used in the thermal phenomenon photosensitive layer and/or the non-photosensitive layer (e.g., undercoat, intermediate layer, layer, etc.) for the purpose of improving the physical properties of the film. Can be done.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example,
Undercoat layer, intermediate layer, protection i! An organic fluoro compound can be used for the layer, etc.).

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

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.).

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.).

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.).

In the heat-developable photosensitive material of the present invention, a polymer latex is added to 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. Can be used.

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 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, ,
(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 with an upper salt limit, 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.

In addition, the amount of added water is 000 in terms of the amount of water added to the added layer.
A range of 2 to 3 g/v' 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.
Vinyl polymers having carboxyl groups or sulfo groups as described in No. 8 can be included.

The amount of the vinyl polymer to be used is in the range of 0.05 to 20 in dry weight ratio to the binder of the layer to be added.It is preferable to provide a protective layer in the photothermographic material of the present invention.

Various additives used in the photographic field can be used in the protective layer. The additives include various matting agents, colloidal silica, slipping agents, organic fluoro compounds (
In particular, fluorine-based surfactants), antistatic agents, ultraviolet absorbers, high-boiling pyogenic agents, antioxidants, hydroquinone derivatives, polymer latex, surfactants (including polymeric surfactants), and hardening agents. (including polymer hardener), Yugeigin+
Examples include jA grains, non-photosensitive silver halide grains, and the like.

The binders used in 1) and 3 include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone,
One or a combination of two or more synthetic or natural polymeric substances, such as polyethylenic episacillin, polyacrylamide, gelatin, and phthalated gelatin, can be used.

The thickness of the protective layer 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.

Further, in order to increase film strength and prevent film destruction, it is also preferable that the hardness of the protective layer is greater than that of the photosensitive layer. Safe! ! One way to make the hardness of a layer higher than that of the photosensitive layer, that is, to control the hardness of each layer, is to use a diffusion-resistant hardener, which protects the diffusion-resistant hardener. Protect by using it as a layer! ! Only the hardness of the layer can be greater than that of the photosensitive layer.

Another way to control the degree of dura at each store is to
Diffusible hardening agents (e.g. vinyl sulfone-based li!peritoneal agents)
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 of the protective layer higher than that of the photosensitive layer and quickly drying it after simultaneous multilayer coating. .

The image-receiving layer of the image-receiving member that can be effectively used in the present invention includes:
It only needs to have the ability to accept the dye in the heat-developable photosensitive layer released or formed by heat development, such as a polymer contained in a tertiary amine or quaternary ammonium salt, as described in US Pat.
．． Those described in No. 709.690 are preferably used. Another useful dye-receiving substance is JP-A-57
The glass transition temperature described in -207250 etc. is 40
Examples include those formed from a heat-resistant filtration polymeric substance at a temperature of .degree. C. or higher and 250.degree. C. or lower.

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

In addition, Polymer Handbook Second Edition (edited by G.I. Brandrup and E.H. Inmargatsu), John Wiley & Sons (Polywe
r Handbook 2nd ed, (j.

3randrup, E, H, Immergut
1m) John Wiley & Sons)
Synthetic polymers with glass transition temperatures below 40° C. that are described in publications are also useful.

Generally, the number of molecules of the polymer substance is 2.000.
~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.

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 an image-receiving layer (image-receiving member), in which case the support may be formed from a single layer or from multiple layers. good.

As the support for the image-receiving member, any material such as a transparent support or an opaque support may be used. 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, electronic I! containing pigments on paper! A support coated with a curable resin composition and cured, or a support coated directly on paper or with a pigment coated layer, and an electron beam curable resin composition coated and cured on the pigment coated layer. Since the resin layer itself can be used as an image receiving layer, it can be used as it is as an image receiving member.

When the present invention is applied to a heat-developable color light-sensitive material, the various polymers described above can be used as a mordant for a dye image and as an image-receiving layer. It may be a separate receiving element or it may be a single layer in which the image receiving layer is part of a heat-developable color photographic material. If necessary, an opacifying layer (reflective or non-reflective) can be included in the light-sensitive material, and such a layer transmits the desired degree of radiation, e.g. visible light, which can be used to observe the dye image in the image-receiving layer. It is used for reflection. The opacifying layer (reflective layer) can contain various reagents that provide the necessary reflection, such as titanium dioxide.

The image-receiving layer of the image-receiving member can also be formed into a type that can be peeled off from the heat-developable photosensitive layer. For example, after imagewise exposure of a heat-developable color photosensitive material, an image-receiving layer can be superimposed on the heat-developable photosensitive layer and uniformly heat-developed. In addition, heat-developable color photosensitive materials@
After exposure to light and uniform heat development, an image-receiving layer may be superimposed and heated at a temperature lower than the development temperature to transfer the dye image released or formed from the dye-providing substance.

The thermal phenomenon light-sensitive material of the present invention is usually imagewise exposed at 80°C to 20°C.
1 at a temperature range of 0°C, preferably 100°C to 170°C.
It is developed by simply heating for between seconds and 180'C, preferably between 15 seconds and 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;
After the thermal phenomenon, the image may be transferred by being placed on the image receiving member and heated, or by being brought into close contact with the image receiving member after supplying water and further heating if necessary. Also, before exposure, 70℃~・180℃
The photosensitive material and the image receiving member may be preheated in the temperature range of 1.5C.Also, as described in Japanese Patent Application Laid-Open No. 6L143338 and Japanese Patent Application No. 60-3644, the photosensitive material and the image receiving member may be heated in order to improve their mutual adhesion. Preheating may be performed at a temperature of 80° C. to 250° C. immediately before development and transfer.

Various exposure means can be used for the photothermographic material according to the present invention.

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 high temperatures for short periods of time, or at low temperatures for long periods of time, continuously raising, lowering, or repeating, and even heating without heating. Although continuous heating is possible,
A simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

10: Screen [Effect of the invention 1] In the present invention, cyanate, which existed in the foot in the form of a precursor during raw storage, is released for the first time during a thermal phenomenon, stabilizing the reducing agent or reducing agent derivative, which is a contaminating factor, and rendering it harmless. It is possible to obtain clear images with no contamination due to the fact that they are opaque, and this clarity is maintained even after storage. In addition, polymer type isocyanate precursors are particularly effective in the present invention because they are less likely to move between layers in a thermally sensitive material or to be transferred to an image receiving member.

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

Example 1 Preparation of silver iodobromide emulsion> At 50°C, JP-A-57-92523;
92524@ Using the mixed j party d shown in the specification,
20 g of ossein gelatin, 1,000 g of distilled water. , I2 and ammonia dissolved (,), potassium iodide 1
Aqueous solution 5 containing 16 g and 131 g of potassium bromide
00vI2 of solution (B) and solution (C) of 500v of an aqueous solution containing 1 mol of silver nitrate and ammonia were simultaneously combined with I)A.
(1 was added while keeping it constant. The shape and size of the emulsion grains to be prepared were adjusted by adjusting the addition rate of DH, !1.l and the B and C solutions if, II III. In this way, Forensic silver content 7 mol%, regular octahedron, average grain size 02
A 5 μm core emulsion was prepared.

Next, in the same manner as above, a core/shell type silver halide emulsion with a regular octahedral shape and an average grain size of 0.3 μm was obtained by coating a silver halide shell with a silver iodide content of 1 mol %. Prepared. (The monodispersity was 9%.) The emulsion thus prepared was washed with water and desalted. The endotherm of the emulsion was 800 yen.

Furthermore, a photosensitive silver iodobromide emulsion was prepared from the silver iodobromide prepared above in the following manner.

a) Preparation of red-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 700. ρ4-Hydroxy-6-methyl-1゜3.3a,7-tetrazaindene o4g Gelatin 32g Sodium thiosulfate 10mg Sensitizing dye below (a) 1% methanol solution 8012 Distilled water
1,200d sensitizing dye (a) b) Preparation of green-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 7001824-
Hydroxy-6-methyl-1゜3.3a,7-tetrazai',/den 01g Gelatin 32g Sodium thiosulfate +Omg Sensitizing dye below (b) 1% methanol solution 801 Di-distilled water
1.20 (L+&sensitizing dye (b) C) Preparation of blue-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 70 (hR4-hydroxy-6-methyl-1°3.3a, 7-tetrazaindene 0 .4g Gelatin 32 (1 Sodium thiosulfate 10mg The following sensitizing dyes (
C) Methanol 1% solution 801g Distilled water 1,200n Sensitizing dye (C
) <Preparation of a silver salt dispersion> 128.8q of 5-methylbenzotriazole obtained by reacting 5-methylbenzotriazole and 40ml in a water-alcohol mixed solvent, and poly(N- Vinylpyrrolidone) ie, og, and 4-sulfobenzotriazole sodium g 4 , 33 g were dispersed in an alumina ball mill and made into OH 5,5 to give 2001 g.

Preparation of dye-providing substance dispersion> Exemplary polymeric dye-providing substance (PM 2 ) 39.4 g
, and the following hydroquinone compounds s and og were dissolved in 200 d of ethyl acetate, and a 5% by weight aqueous solution of Alkanol
After mixing with gelatin aqueous solution 72 (h12) containing g and dispersing with an ultrasonic homogenizer, and distilling off ethyl acetate,
The pH was adjusted to 5.5 to give 7951β.

Preparation of reducing agent solution of hydroquinone compound H> 23.3 g of the following reducing agent (i), the following development accelerator 1.
10g, poly(N-vinylpyrrolidone) 14.6s,
Dissolve 0.50 g of the following fluorine-based surfactant in water, 1)
8 5.5 and 250 tl12.

Reducing agent (i) CH.

Phenomenon promoter CH2Cl-1= CH2 Surfactant CH2CC00CH2(CF2CF2)nH(, n=2
or 3) Preparation of heat-developable photosensitive material> (Emulsion layer) Organic silver salt dispersion 12.5tR1 red-sensitive silver iodobromide emulsion 6.
001, 39.81+2 of the dye-providing substance dispersion, 12.5 of the reducing agent solution, and further added 1 of the hardening agent solution (tetra(vinylsulfonylmethyl)methane and taurine).
:1 (ill ratio) and dissolved in a 1% aqueous solution of phenylcarbamoylated gelatin so that tetra(vinylsulfonylmethyl)methane was 3% by weight)
After adding 2.50t12 of polyethylene glycol 300 (Kanto Kagaku) as a hot solvent, 1.700/f of silver 1 was deposited on a photographic polyethylene terephthalate film with a thickness of 180μ which had been undercoated. And the transition agent was applied so that it was 0.761 J/f.

(Retention rJ layer) Gelatin, phenylcarbamoylated gelatin, and poly(
A coating solution is prepared by adding an aqueous solution of polyvinylpyrrolidone and the isocyanate precursor compound (3a) of the present invention dispersed in a ball mill to a mixed solution of N-vinylpyrrolidone) and a hardening agent similar to that used in creating the emulsion layer. coated on the emulsion layer and attached with gelatin at 12.8 p/v;
1.4 g of poly(N-vinylpyrrolidone) and
Isocyanate precursor compound (3a) 0.1
A protective layer a was provided so that the weight was 74 g/f, and the photosensitive material was designated as A.

Similarly, on the emulsion layer, instead of 0.174 g/v' of the isocyanate precursor compound (3a) of A, the isocyanate precursor compound of the present invention and the comparative compound were added as shown in Table 1. Added protective rJ layers S, c, d, e, f, g, h were provided, and photosensitive material B, CS
D, E, F, G, and H were created.

Salt 2゛Margin τ・°8 Table 1 Comparative compound (1) CH3 CO Preparation of image receiving member> Ethylene chloride + fJ solution of polycarbonate (Yojin Kasei Panlite L-1250) was applied on photographic baryta paper to form a polycarbonate sheet. was set to 12 g/y.

The heat-developable photosensitive material was exposed to 1,600 C, M, S through a step wedge.
After heat development was carried out at 150° C. for 1 minute at 7.3M Co., Ltd., a yellow step wedge negative image was obtained on the photosensitive material and the polycarbonate surface of the image receiving member. In addition, the heat-developable photosensitive material was heated at 50° C. and at a relative humidity of 80%.
A sample left in the atmosphere for 24 hours was exposed and developed in the same manner to obtain a negative image. Measure the reflection density of the white background part of the obtained negative image in the same way, then irradiate the same white background part with xenon light using a xenon fade meter, and measure the reflection density when the generated contamination concentration reaches the maximum. was measured. The results are shown in Table 2.

From the above results, sample G, in which no isocyanate precursor compound was added to the sample G, caused a large amount of contamination after xenon irradiation, and sample H, in which comparative compound (i) was added, showed a large amount of contamination after xenon irradiation. l)! The effect of reducing the occurrence of subsequent contamination is very small. On the other hand, A, B, C, D, E, and F to which the isocyanate precursor compound of the present invention was added can sufficiently reduce the occurrence of contamination after xenon irradiation. Moreover, in the sample after being left at 50°C and 80% conditions, the isocyanate precursor of the present invention showed no decrease in its stain reduction ability.
Comparative compound (i) showed a further decrease in stain reduction ability, indicating that the isocyanate precursor of the present invention is stable even when stored at high temperature and high humidity.

Among the samples using the isocyanate precursor compound of the present invention, it was found that the occurrence of contamination was particularly reduced in A, 81C, and E.

Example 2 In place of the reducing agent used in Example 1, an exemplary reducing agent (R-
An emulsion layer was prepared in the same manner as in the heat-developable photosensitive material of Example 1, except that 3> was added to 0.696 g/l', and protective layers S, cSg, and h were provided thereon, and photosensitive Material 1.
J, and L were prepared and treated in exactly the same manner as in Example 1 using the passive member of Example 1, and then the anti-DI concentration was measured. From the results in Table 3 and above, even when the reducing agent (R-3) was used, samples I and J used xenon using the isocyanate precursor compounds (3A) and (6) of the present invention. It was found that the occurrence of contamination after irradiation was reduced.

Example 3 A heat-developable photosensitive material shown in Table 4 was designated as Sample M, and photosensitive materials containing isocyanate precursor compounds shown in Table 5 as protective B and intermediate layer were designated as Samples N and S.

Using the image receiving member of Example 1, the photosensitive materials M, N, and S were
After processing in exactly the same manner as in Example 1, the reflection density was measured. The results are shown in Table 6.

From the above results, it was found that even in the case of multilayer photosensitive materials, sample N using the isocyanate precursor compound (3a) of the great invention reduces the occurrence of contamination.

CD' Scavenger C-1 H3 Y-filter dye (weight ratio) S-1 polyethylene glycol (average molecular weight 300) Patent applicant Konishi Roku Photo Industry Co., Ltd. Procedure 7 City Registration (Voluntary) December 88, 1988 1. Incident Indication of 1985 Hand-held Application No. 196707 2, Title of the invention: Photothermographic material with improved image storage property 3, Relationship with the person making the amendment case: Special r [Applicant's address: 1-chome Nishi-Shinjuku, Shinjuku-ku, Tokyo 26 number 2 name
(127> Representative Director of Roku Konishi Photo Industry Co., Ltd.
Fukute 4, Agent 102 Address 1-18 Kudan Kita 4-chome, Chiyoda-ku, Tokyo Kudan-Rosaka Building? The Detailed Description of the Invention in column 6 of ``3. Detailed Description of the Invention'' in Chapter 8, 263-9524, Akira 11I Store, in the details of the amendment, is amended as follows.

(1) Table 2 on page 93 of Mei III is corrected as shown in Attachment 1.

(2) Table 3 on page 96 of Mei Ill is corrected as shown in Attachment 2.

(3) On page 97, lines 4 and 5 of the specification, the statement "...was found to be reduced." It was found that the reduction effect was maintained.''

(4) Table 6 on page 101 of the Ming Wl is corrected as shown in (Attachment 3).

(5) On page 102 of the specification, lines 3 and 4, [... was found to be reduced. It was found that this effect was maintained even when stored at high temperature and high humidity. ” he corrected.

that's all

Claims (2)

[Claims] (1) A heat-developable photosensitive material comprising, on a support, at least a photosensitive silver halide, a dye-providing substance, a reducing agent, a binder, and a compound that releases isocyanate during thermal development. (2) Claim No. 1, characterized in that the compound that releases isocyanate during thermal development is a polymer compound.
1) The heat-developable photosensitive material described in item 1).