JPS62227141A - Heat developable color photosensitive material prevented from stains on white background - Google Patents

Abstract

PURPOSE:To prevent stains on the white background, especially, stains due to light and time lapse, and to obtain a color image high in density and small in fog by incorporating a specified reducing agent. CONSTITUTION:The photographic constituent layer containing at least photosensitive silver halide, the reducing agent, a dye donor, and a binder is formed on a support to compose the heat-developable color photosensitive layer. Said reducing agent is represented by the formula shown on the right in which R1 is alkyl; each of R2, R3, and R4 is H, halogen, OH, alkoxy, acylamino, sulfonamide, alkylsulfonamide, or alkyl; each of R5 and R6 is H or alkyl, but each of R3 and R5, R2 and R6, and, R5 and R6 may form a hetero ring; M is H, an alkali or alkaline earth metal atom, ammonium, or an N-containing organic base; and m is 1 or 2. Such a reducing agent can be obtained in general by converting the N,N-disubstituent of m-alkoxyaniline into nitroso-, nitro-, or diazo-product, then, subjecting it to the following reducing process to synthesize 4-N,N-disubstituted 2-alkoxyaniline, and further, reacting it with chlorosulfurinc acid, and when needed, with various kinds of bases. The reducing agent is commonly used in an amount of 0.01-1,500mol%, preferably, 0.1-200mol% of the photosensitive silver halide.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a heat-developable color photosensitive material, and in particular, it relates to a heat-developable color photosensitive material, in particular to a color image obtained by forming a dye by heat development, or a color image formed or released by heat development. The present invention relates to a heat-developable color photosensitive material that obtains a transferred image by transferring a dye.

[Background of the Invention] In recent years, heat-developable photosensitive materials whose development process can be performed by heat treatment have attracted attention as photosensitive materials.

Regarding such heat-developable photosensitive materials, for example,
No. 4921 and No. 43-4924 disclose a photosensitive material comprising an organic silver salt, silver halide, a reducing agent, and a binder, which is commercialized as dry silver by 3M Company.

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

For example, U.S. Patent Nos. 3,531,286 and 3,7
No. 61゜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 compound with a coupler, Research--j 'chair') 0-di1y-(Resea
rchD 1sclosure) 15108 and 15127, and an oxidized form of a reducing agent (hereinafter also referred to as a developer or developing agent) which is a sulfonamide phenol or sulfonamide aniline derivative described in U.S. Pat. No. 4,021,240, etc., and a coupler. As disclosed in British Patent No. 1,590,956, an organic imino silver salt having a dye moiety is used to liberate the dye in a thermal development section and a separately provided image receptor is used. A method for separating a dye image on a layer by `TL, also disclosed in Japanese Patent Application Laid-Open No. 52-1
No. 05821, No. 52-105822, No. 56-5
0328, U.S. Pat. No. 4,235,957, etc., and methods for obtaining positive dye images by silver dye bleaching methods, as well as U.S. Pat. No. 3.180.731 and U.S. Pat. No. 3.9.
No. 85.565, No. 4.022.617, No. 4.
452.883, JP-A No. 59-206831, etc., methods for obtaining dye images using leuco dyes, etc.
Various methods have been proposed.

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 new type of color image forming method using heat development, Japanese Patent Application Laid-open Nos. 57-179840 and 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.

These methods were further improved to produce a diffusible dye by oxidizing a non-diffusible reducing dye-donating substance disclosed in, for example, JP-A-58-58453 and JP-A-59-168439Q. Release method, JP-A-58-
No. 79247, No. 59-174834, No. 59-12
431@, No. 59-159159, No. 60-2950
JP-A-58-149046, JP-A No. 58-149047, JP-A No. 59-124339, JP-A-Sho 58-149046, JP-A No. 58-149047, JP-A No. 59-124339; No. 59-181345, No. 460-2950, Patent Application No. 181604/1983,
Methods using a non-diffusible compound that reacts with an oxidized developing agent to form a diffusible dye, such as those disclosed in No. 59-182506, No. 59-182507, and No. 59-272335; In, Japanese Patent Publication No. 59-15
No. 2440, No. 59-124327, No. 59-154
No. 445, No. 59-166954, etc., are non-diffusible reducing dye-donating substances that lose their ability to release diffusible dyes when oxidized, and conversely non-diffusible reducing dyes that release diffusible dyes when reduced. a method containing a color-providing substance;
etc. have been proposed.

The basic structure of a color type heat-developable photosensitive material that obtains a color image using these emitted or formed diffusive dyes is as follows:
It consists of a light-sensitive element and an image-receiving element, and the light-sensitive element basically contains a light-sensitive silver halide, a silver salt, a reducing agent, a dye-donating substance,
It consists of a binder. In the present invention, only the photosensitive element is referred to as a heat-developable color photosensitive material in a narrow sense, and the image receiving element is referred to as an image receiving member.

The above-mentioned heat-developable color photosensitive material is one in which a dye image is obtained by transferring the released or formed diffusible dye onto the image receiving layer of an image receiving member provided on the same support or another independent support. It was improved in many respects compared to previous heat-developable color photosensitive materials in terms of image sharpness, stability, etc.

However, in these heat-developable color light-sensitive materials, especially those in which a dye is released or formed by coupling with an oxidized form of a reducing agent, the developability of the reducing agent used, such as the maximum density, is insufficient, or Even if the developability is good, it has the disadvantage that the white background area is contaminated by the reducing agent or the thermal decomposition product of the reducing agent (particularly staining due to light over time).

[Object of the Invention] An object of the present invention is to provide a heat-developable color photosensitive material in which staining of white background areas (particularly staining over time due to light) is prevented.

Another object of the present invention is to provide a photothermographic color photosensitive material capable of producing color images with high density and low fog.

Still another object of the present invention is to provide a heat-developable color photosensitive material from which color images with good tone can be obtained.

Yet another object of the present invention is to provide a heat-developable color photosensitive material containing a novel reducing agent.

[Structure of the Invention] As a result of intensive studies to achieve the above object, the inventors of the present invention have discovered a heat-resistant film having a photographic constituent layer containing at least a photosensitive silver halide, a reducing agent, a dye-providing substance, and a binder on a support. In the developable color photosensitive material, the following general formula (1)
It has been found that the above objects of the present invention can be achieved by a heat-developable color photosensitive material containing a reducing agent represented by:

General formula (1) In the formula, R1 represents an alkyl group, R2, R3 and R
s each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an acyloxysulfonamide group, an alkylsulfonamide group, or an alkyl group, and R
5 and R6 each represent a hydrogen atom or an alkyl group. However, R3 and Rs, R2 and R6, and R5 and R
Each of 6 may be ring-closed to form a heterocycle. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a nitrogen-containing organic base.

m represents 1 or 2.

[Specific structure of the invention] In the general formula (1), R1 represents an alkyl group, and the alkyl group represented by R1 preferably has 1 to 30 carbon atoms, more preferably 1 to 30 carbon atoms.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, etc., including those having substituents.

Examples of substituents for the alkyl group represented by R1 include halogen atoms (e.g., fluorine atoms, chlorine atoms, etc.), alkoxy groups (e.g., methoxy groups, ethoxy groups, etc.), hydroxy groups, cyano groups, alkenyl groups (e.g., vinyl groups, allyl group, etc.), sulfonamide group, alkylsulfonamide group (e.g., methylsulfonamide group, etc.), acylamino group (VA, acetamino group, etc.), acyloxy group (
For example, methylcarbonyloxy group, etc.) can be mentioned.

R1 is preferably a methyl group or an ethyl group.

R2, R3 and R4 each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acylamimum L sulfonamide group, an alkylsulfonamide group, or an alkyl group, and examples of the halogen atom include a chlorine atom, a bromine atom, and a fluorine atom. Examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the acylamino group include an acetamino group and a butanoylamino group; and examples of the alkylsulfonamide group include, for example, methylsulfonamide. group, ethylsulfonamide group, etc., and examples of the alkyl group include
Preferably, it is an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a butyl group, and the like. R2, R3 and R
The group 1.1 represented by 4 also includes those having a substituent.

R5 and R6 represent a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 3 rA atoms.
0, more preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, etc., including those having substituents. Examples of the substituent include those listed above for the substituents of the alkyl group represented by R1. Furthermore, the groups represented by R5 and R6 may be ring-closed to form a heterocycle;
3 and R5, and the above-mentioned R2 and R6 may also be ring-closed to form a heterocycle.

R5 and R6 preferably have a total number of carbon atoms including substituents of 5 or less and are different from each other. In addition, for stable storage in photosensitive materials, R1
When is a methyl group and both R5 and R6 are unsubstituted alkyl groups having 2 or less carbon atoms, it is preferable that R5 and R6 are different alkyl groups.

M is a hydrogen atom, an alkali metal atom (e.g. lithium,
represents an atom of an alkaline earth metal (for example, an atom of calcium, strontium, barium, etc.), an ammonium group, or a nitrogen-containing organic base. Here, the nitrogen-containing organic base is an organic compound containing a basic nitrogen atom capable of forming a salt with an inorganic acid, and particularly important organic bases include amine compounds.

As chain amine compounds, primary amines, secondary amines, etc.
Examples of cyclic amine compounds include typical heterocyclic organic bases such as pyridine, quinoline, piperidine, and imidazole. In addition, hydroxylamine, hydrazine,
Compounds such as amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic M salts (eg, hydrochloride, sulfur salt, nitrate, etc.) of the organic base mentioned above are preferably used.

m represents 1 or 2.

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

Below are 4 blank spaces. 8) (R-9) (R-10) (R-11) (R-12) CxHs (R-13) (R-14) (R-15) (R-16) (R-17) (R -18) (R-19) (R-20) (R-21) (R-22) (R-23) (R-24) CH3 (R-25) (R-26) The following margins represent the reduction of the present invention The agent generally synthesizes 4-N,N-disubstituted-2-alkoxyaniline from N,N-disubstituted m-alkoxyaniline by nitration, nitration, or diazotization and subsequent reduction steps. It can be obtained by further reacting with chlorosulfonic acid and, if necessary, reacting with various bases.

Specific synthesis examples of the reducing agent of the present invention are shown below.

Synthesis of Exemplary Reducing Agent R-1 45 g of m-anidine and 110 g of 3-bromopropene were dissolved in 500 mN of acetone, 200 g of potassium carbonate was added, and the mixture was heated under reflux for 30 hours, then filtered and concentrated. The concentrated solution was distilled under reduced pressure (95° C./3 mmHg) to obtain 51 g of N,N-di-β-propenyl-m-methoxyaniline.

Combine all this with 210g of ice and 165g of concentrated hydrochloric acid. ,<! In addition to a solution of 21 g of methanol and 21 g of methanol, an aqueous solution of 19.1 g of sodium nitrite (40 vQ of water) was added dropwise to this solution at 0° C. or lower. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, and after further adding 70° of reduced iron at 20° C. or below, stirring continued for 1 hour. This reaction solution was neutralized and filtered, the filtrate was extracted with ethyl acetate, the extract was dried over magnesium sulfate, and then distilled off with ethyl acetate. This residue 30() was dissolved in 160 d of chloroform, and dimethylaniline 4071112 was added. This solution was cooled, and chlorosulfonic acid was added dropwise at a temperature of 5° C. or lower, and further stirred at room temperature for 1 hour. This reaction solution was added to 300 nN of acetonitrile, and after cooling, the crystals were filtered off.

2g of sodium hydroxide, 80,112 methanol and 41 parts water
After stirring for a while, the filtered crystals were gradually added to the solution and stirred for 30 minutes.

This reaction solution was concentrated to 1/3, cooled, and the precipitated crystals were filtered and dried to obtain the desired product (R-1) 10.4c).

The target product was identified by NMR and elemental analysis.

Elemental analysis results> Theoretical value (%) C (48,74), N (8,74'), S
(10,0) Experimental value (%) C (48,16), N (8,67>, S (9,
91") The reducing agent represented by the general formula (1) according to the present invention may be used alone or in combination of two or more,
Further, a reducing agent described below may be used in combination for the purpose of increasing consistency.

For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-tert-
butyl-p-cresol, N-methyl-〇-aminephenol, etc.), sulfonamidophenols [e.g. 4-
Benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dipromo-4-
(p-toluenesulfonamide) phenol, or polyhydroxybenzenes (e.g. hydroquinone,
tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-hydroxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxy 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.], methylenebisphenols [e.g. 1.1-
Bis(2-hydroxy-3,5-dimethylphenyl)-
3゜5.5-trimethylhexane, 1,1-bis(2-
Hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5-
tert-butylphenyl)methane, 2,6-methylenebis(2-humanOxy3-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 reducing agents can also be used alone or in combination of two or more.

The reducing agent represented by general formula (1) used in the heat-developable photosensitive material of the present invention may be used, such as the type of photosensitive silver halide, the type of organic acid silver salt used, and the type of other additives. Although it depends on the amount, it is usually in the range of 0.01 to 1500 mol, preferably 0.1 to 200 mol, per 1 mol of photosensitive silver halide.

In order to add the reducing agent represented by the general formula (1) according to the present invention to the heat-developable photosensitive material, water is mainly used as the solvent, but a low boiling point organic solvent may be used as necessary. A mixed solvent of a miscible organic solvent and water may be used, and the mixture is dissolved in the above solvent and added to the photothermographic material.

Dye-providing substances that can be used in the present invention will be explained.

As a dye-donating substance, it participates in the reduction reaction of photosensitive silver halide and/or organic silver salt used as necessary,
Any material that can form a diffusible or non-diffusible dye or release a diffusible dye as a function of the reaction may be used, but it is preferable to perform a coupling reaction with an oxidized form of a reducing agent to form a diffusible or non-diffusible dye. They are coupled dye-forming dye-donating substances that form non-diffusible dyes, or coupled dye-releasing dye-donating substances that release diffusible dyes.

A compound represented by the following general formula (2) is preferable as a coupled dye-releasing dye-donating substance that releases a diffusible dye.

General formula (2) % formula % In the formula, C11+ 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 the active point of the coupler. It is a substituted and removable divalent bonding group, and the bond between Cpl and J is cleaved by reaction with an oxidized form of a reducing agent. n represents O or 1, and Dye represents a diffusible dye residue. Also CI)+
is preferably substituted with various ballast groups in order to make the coupled dye-releasing compound non-diffusible, and ballast+j* is preferably substituted with a ballast group having 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 or more) carbon atoms and hydrophilic groups such as sulfo groups and carboxy groups. It is a group that both have. Another particularly preferred ballast group can include polymer chains.

Specific examples of the compound represented by the above general formula (2) include JP-A-57-186744 and JP-A-57-122596.
No. 57-160698, No. 59-174834, No. 57-224883, No. 59-159159,
They are described in each specification of No. 59-231540, and include, for example, the following compounds.

Dye-providing substances exemplified below As coupling dye-forming compounds that form diffusible dyes, those represented by general formula (3) are preferred.

General formula (3) % formula % In the formula, CI)2 is a morphological group (so-called coupler residue) that can react with the oxidized product of the reducing agent (coupling reaction) to form a diffusible dye, J has the same meaning as J in general formula (2), and Q represents a ballast group.

For the coupler residue represented by CI)2, the number of molecules 1 is preferably 700 or less, more preferably 500 or less, in view of the diffusibility of the dye formed.

In addition, the ballast group is preferably the same as the ballast group defined in general formula (2), 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 both 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 single m compound represented by the general formula (4).

General formula (4) % formula %) In the formula, Co1 and J have the same meanings as those cut in general formula (3), Y represents an alkylene group, an arylene group, or an aralkylene group, and is O or 1. , Z represents a divalent organic group, and L 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 (3) and (4) include JP-A-59-1243
No. 39, No. 59-181345, No. 60-295
No. 0, Japanese Patent Application No. 59-179657, No. 59-1816
No. 04, No. 59-182506, No. 59-18250
No. 7, each specification includes, for example, the following compounds.

Below are examples of dye-donating substances in the margin: OCHC, H2゜OOH ■ Polymer M-1 M-4 PM-6'O!fr% M-7 M-8 y: 50% by weight Coupling to form a non-diffusible dye As the dye-forming dye-donating substance, a compound represented by the following general formula (5) is preferable.

General formula (5) %Formula% In the formula, CD3 represents a coupler residue, and Q represents the general formula (2
), the ballast group is substituted at a point other than the active site of the coupler, and J
has the same meaning as defined in general formula (2).

Specific examples of the compound represented by general formula (5) include the following.

The following margin Hs u3t-t C-0CH2CODl-1 C-'7 More specifically, the coupler residue defined by CI)3 is preferably a group represented by the following general formula.

General formula (6) General formula (7) General formula (8
) General formula (9) General formula (10)
General formula (11) General formula (12)
General formula (13) General formula (1D) General formula (15) In the following blank formulas, R7, Ra, R9, and R1o are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, and an alkyl group. Oxycarbonyllkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amino group, alkoxy group, aryloxy group, cyano group, alkylsulfonyl group, arylsulfonyl group, ureido group,
It represents an alkylthio group, an arylthio group, a carboxy group, a sulfo group, or a heterocyclic residue, which further includes a hydroxyl group,
Carboxy group, sulfo group, alkoxy group, cyano group, nitro group, alkyl group, aryl group, aryloxy group,
It may be substituted with an acyloxy group, an acyl group, a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, or the like.

These substituents are selected depending on the purpose of Cpl, CI2, and CI3, and as described above, one of the substituents is preferably a ballast group in <CD+ and CI3, and in CI)2, it is preferable that one of the substituents is a ballast group. In order to improve the diffusivity of the substituents, the substituents are preferably selected so that the molecular weight is 700 or less, more preferably 500 or less.

These dye-providing substances may be used alone or in combination of two or more. The use ω is not limited and depends on the type of dye-providing substance, whether it is used alone or in combination of two or more types, whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more types, etc. You can decide accordingly, but for example, the usage range is 0. 005g to 50g, preferably 0.1Q to 10(J) can be used.

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 a 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, polyvinylbutyryl, polyvinylpyrrolidone, etc.).

The heat-developable photosensitive material of the present invention basically contains (1) photosensitive silver halide, (2) reducing agent, (3) dye-providing substance, and (4) binder in one heat-developable photosensitive layer. It is preferable to contain (5) an organic silver salt as necessary. 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-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, 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 compound.

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 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.

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(+ constant).

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

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

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, 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 consisting of 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.
．． 592.250, 3,206, 313, 3
, No. 317,322, No. 3,511,662, No. 3
．． No. 447,927, No. 3,761,266, No. 447,927, No. 3,761,266, No.
As described in No. 3.703.584 and No. 3.736.140, silver halide grains have higher sensitivity inside the grains than on the surface of the grains. The method for producing silver halide emulsions containing these internal latent image type silver halides is as described in the above patent, for example, by first preparing Ac+ Cff1 grains and then adding bromide or a small amount of iodide thereto. A method of adding a chemically sensitized silver halide to cause halide exchange, or a method of coating a central core of chemically sensitized silver halide with non-chemically sensitized silver halide, or a method of combining a chemically sensitized coarse grain emulsion with a chemically sensitized coarse grain emulsion. Many methods are known, such as a method in which a fine grain emulsion, either sensitized or not chemically sensitized, is mixed and the fine grain emulsion is deposited on a 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.
, 761,276, silver halide emulsions in which the grain surfaces of silver halide grains containing dopants are weakly chemically sensitized, or those described in JP-A-50-8524 and JP-A-50-38525, etc. Silver halide emulsions consisting of grains having a laminated structure, and other JP-A-52-
These include silver halide emulsions described in No. 150614 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 or fine, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.001 μm to about 1.5 μm, and more preferably about 0.001 μm to about 1.5 μm. .01 μm to about 0.5 μm.

The photosensitive silver halide emulsion prepared 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, the photosensitive silver salt-forming components are prepared using organic! ! It is also possible to form a photosensitive silver halide in a part of the organic silver salt by coexisting with the organic silver salt. The photosensitive silver salt forming component used in this WA manufacturing method is an inorganic halide, for example, a halide represented by MXn (where M is an H atom, N84
represents a group or a metal atom, X represents CQ, Br or I, n4. When tM is an H atom or an N84 group, it is 1, and when M is a metal atom, it is the valence. As for metal atoms,
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, osmium, iridium, platinum, cerium, etc. It will be done. ), halogen-containing metal complexes (e.g., K2 Pt
Cff1s, K2 Pt3rs, HALI
Cf14゜(NH4)2 Ir Cff1s,
(NH4)31r C16゜(NH4)2 Rtl C
j! s , (NH4)3Ru C15(NH4)2 R
hCI! s, (NH4)3 Rh 3r6, etc.)
, onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide,
Quaternary ammonium halides such as 3-methylthiazolium bromide, trimethylbenzylammonium bromide, quaternary phosphonium halides such as tetraethylphosphonium bromide, benzylethylmethylsulfonium bromide, and 1-ethylthiazolium bromide. tertiary sulfonium halides, etc.), halogenated hydrocarbons (e.g., iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.)
, N-halogen compound (N-chlorosuccinimide, N
-bromosuccinimide, N-bromophthalic acid imide,
N-bromoacetamide, N-iodosuccinimide,
N-bromophthalazinone, N-chlorophthalazinone, N
-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.), and other halogen-containing compounds (e.g. trichloride trichloride). phenylmethyl, triphenylmethyl bromide, 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 preferably 0.001 g to 50 g, and more preferably 0.001 g to 50 g per 1 N of support per layer. Preferably 0.19-10
It is g.

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 tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine dyes, those having a basic nucleus such as deazoline, oxazoline, viroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferred. Such nuclei include alkyl groups, alkylene groups,
It may contain a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. 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 pigments have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbylic acid nucleus, thiazolinthione nucleus, malonitrile nucleus, and pyrazolone nucleus. Good too.

These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkylulkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic I derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat. Nos. 2,933,390 and 2,937,089.
A supersensitizing additive that does not absorb visible light, such as those described in the specification of No. 1, can be used in combination.

The amount of these sensitizing dyes added is 1.times.10@-4 mol to 1 mol per mol of photosensitive silver halide or silver halide forming component. More preferably, 1X 10-4 mol to 1
X 1 0-1 mol.

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 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 bonds such as those described in various publications and specifications such as U.S. Patent Nos. 3,330,633, 3,794,496, and 4,105,451 Silver salts of acids and silver salts of carboxylic acids having heterocycles, such as silver laurate, silver myristate, silver valmitate, silver stearate, silver arachidonate, silver behenate, α-(1-phenyltetrazolethio)acetic acid silver, aromatic carboxylic acid silver, such as silver benzoate, silver phthalate, etc.
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.

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 an alkyl group of 022 or less,
More preferably, silver alkylamidobenztriazole (substituted with an alkyl group of 4 or less, such as silver methylbenztriazole, silver ethylbenztriazole, silver n-octylbenztriazole, etc.), silver alkylamide benztriazole (preferably silver alkylamide of 022 or less) silver acetamidobenztriazole, silver propionamidobenztriazole, silver 1so-butylamidebenztriazole, silver laurylamidebenztriazole, etc.), silver alkylsulfamoylbenztriazole (preferably alkyl 022 or less) Those substituted with sulfamoyl groups, such as silver 4-(N,N-diethylsulfamoyl)penztriazole, silver 4-(N-propylsulfamoyl)penztriazole, 4-(
N-octylsulfamoyl)penztriazole silver,
Silver salts of halogen-substituted benztriazoles (for example, silver 5-chlorobenztriazole, 5-bromobenztriazole, etc.) triazole silver, etc.), alkoxybenztriazole silver (preferably 022g, substituted with a lower alkoxy group, more preferably a C4 or lower alkoxy group, such as 5-methoxybenztriazole 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 4-triazole, silver 1-tetrazole, silver 3-amino-5-benzylthio-1,2,4-triazole, silver saccharin, silver phthalazinone, silver phthalimide, and other silver salts of mercapto compounds, such as 2-mercaptobenzo Oxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole 2-mercaptobenzimidazole capto-4-phenyl-1,2.4-triazole silver,
4-Hydroxy-6-methyl-1.3.

38,7-thitrazaindene silver and 5-methyl-7-
Examples include silver hydroxy-1.2.3.4.6-pentazaindene.

Other silver complex compounds with a stability constant of 4.5 to 10.0 as described in JP-A No. 52-31728, imidase as described in U.S. Pat. No. 4,168,980@Mei 18m 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 product 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, IIE mills, and the like.

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

The amount of the organic silver salt used is generally preferably 0.01 to 500 moles, more preferably 0.1 to 100 moles, per mole of photosensitive silver halide. Roughly preferably 0.
It is 3 to 30 moles.

Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural polymers such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more molecular 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 other monomers copolymerizable with vinylpyrrolidone. ). These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone,
Preferred polyvinylpyrrolidone has molecules R1,000-4
00.000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl acetates, vinyl imidazoles, (meth)acrylamides,
Examples include vinyl monomers such as vinyl carbinols and vinyl alkyl ethers, but it is preferable that polyvinylpyrrolidone accounts for at least 20% (weight %, same hereinafter) of the composition ratio. Preferred examples of darkening 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% of the total binder amount, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%.
It is preferably 10 to 80%, more preferably 10 to 80%.

The binder may contain other polymeric substances,
Gelatin and a mixture of polyvinylpyrrolidone with a molecular weight i, ooo ~ 400.000 and one or more other polymeric substances, gelatin and a molecule ffi 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, or proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Examples include natural substances. These range from 0 to 85%, preferably from 0 to 85%.
It may 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 1 f of support, preferably 0.1
g~iog.

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.

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, Ti11 paper, baryta paper and resin coated paper, and furthermore, on these supports Examples include a support coated with an electron beam curable resin composition and cured.

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 Nos. 3,347,675 and 3,667.959, Research Disclosure NO.
556, Japanese Patent Application No. 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 Examples include 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” by Yoshio Koda,
Sankyo Publishing Inc., 1984) is in the range of 0.5 to 3.0, preferably 0.7 to 2.5, particularly preferably 1.0 to 2.0, and the solubility in water at room temperature is 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 margin C (Cl), C0NH, i41° 1.4
4 or less Many compounds used as water-insoluble solid heat solvents are commercially available, and can be easily synthesized by those skilled in the art.

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 third layer, an image receiving layer of an image receiving member, etc., and are added so as to obtain the respective effects.

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

Note that even when the melting point of the water-insoluble solid thermal solvent of the present invention is higher than the thermal development temperature, the melting point is lowered by being added to the binder, so that it can be effectively used as a thermal solvent.

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

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; , described in U.S. Patent No. '3.667,959 (7) C0-1-
The melting point of lactones etc. having 8O2-1-80- group is 20
There are non-aqueous polar compounds with temperatures above ℃.

Furthermore, benzophenone derivatives described in JP-A-49-115540, JP-A-53-24B29 and JP-A-53-24B29, JP-A-53-24B29;
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. 46-6077, No. 49-5019,
49-5020, 49-91215, 4
No. 9-107727, No. 50-2524, No. 50-
No. 67132, No. 50-67641, No. 50-114
No. 217, No. 52-33722, No. 52-99813
No. 53-1020, No. 53-55115, No. 53-76020, No. 53-125014, No. 54
-156523, 54-156524, 54-
156525@, No. 54-156526, No. 55-4
No. 060, No. 55"4061, No. 55-32015, 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. No. 847.612, No. 3,782,94
No. 1, No. 4.201.582 and JP-A-57-2
No. 07244, No. 57-207245, 1iil 5
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-human xynaphthalimide, benzoxazine, naphthoxazinedione, 2.3- Dihydro-phthalazinedione, 2.3
-dihydro-1,3-oxazine-2,4-sion, oxypyridine, aminopyridine, hydroxyquinoline,
Aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4-(3H)dione, benzotriazine, mercaptotriazole, dimercabutotetrazapentalene, aminomercaptotriazole, acylaminomercaptotriazole , phthalic acid, naphthalic acid, phthalamic acid, etc., mixtures of one or more of these with imidazole compounds, and mixtures of at least one acid or acid anhydride such as phthalic acid, naphthalic acid, etc. and phthalazine compounds. Further examples include combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like.

Examples of antifoggants include those described in US Pat. No. 3,645.
Higher aliphatic compounds (e.g. behenic acid, stearic acid, etc.) described in No. 739, mercuric salts described in Japanese Patent Publication No. 11113/1983, and N-
Halogen compounds (e.g. N-halogenoacetamide, N
-halogenosuccinimide, etc.), U.S. Patent No. 3,700
, 457, mercapto compound-releasing compounds described in JP-A No. 51-50725, arylsulfonic acids (e.g. benzenesulfonic acid, etc.) described in JP-A No. 49-125016, lithium carboxylates described in JP-A No. 51-47419. salts (e.g. lithium laurate), British Patent No. 1,45
5,271, oxidizing agents (e.g. perchlorates, inorganic peroxides, persulfates, etc.) described in JP-A-50-101.019, sulfinic acids or thiosulfonic acids described in JP-A-53-19825. , 2 described in No. 51-3223
-Thiouracils, simple sulfur described in No. 51-26019, disulfide and polysulfide compounds described in No. 51-42529, No. 51-81124, and No. 55-93149, rosin described in No. 51-57435, or Diterpenes (e.g. abietic acid, pimaric acid, etc.), polymeric acids having free carboxy or sulfonic acid groups as described in US Pat. No. 51-104338, thiazolinthione as described in US Pat. No. 54-51821, U.S. Patent No. 4,137,
1,2,4-triazole or 5 described in No. 079
-Mercapto-1,2,4-triazole, 55-1
Thiosulfinate esters described in No. 40833, 1.2.3.4-thiatriazoles described in No. 55-142331, No. 59-46641, No. 59-572
33, the dihalogen compounds or trihalogen compounds described in No. 59-57234, and furthermore, No. 59-111.
Examples include thiol compounds described in No. 636.

In addition, as other antifoggants, Japanese Patent Application No. 59-565
Hydroquinone derivatives described in No. 06 (e.g., di-t
-octylhydroquinone, dodecanylhydroquinone, etc.) and hydroquinone M 8-isomer and benzotriazole mQ-isomer (e.g., 4
-sulfobenzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used in combination.

Further particularly preferred antifoggants include the polymer inhibitors described in Japanese Patent Application No. 60-262177 and the compounds having ballast groups described in Japanese Patent Application No. 60-263564.

As a silver image stabilizer, U.S. Patent No. 3.707.31
Polyhalogenated organic oxidizing agent described in No. 7 Mei 1I1m (e.g., tetrabromobutane, tribroequinaridine, etc.)
, 5-methoxycarbonylthio-1-phenyltetrazole as described in Belgian Patent No. 768.071, and monohenyl compounds as described in JP-A-50-119624 (for example, 2-bromo-2-tolylsulfonylacetamide). etc.), bromine compounds described in JP-A-50-120328 (e.g., 2-bromomethylsulfonylbenzothiazole, 2,4-bis(triprotamamethyl)-6-methyltriazine, etc.), and JP-A-53- Examples include tripro[ethanol, etc., described in No. 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. 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
Compounds called activator precursors that release basic substances by heat, such as compounds such as guanidinium trichloroacetate that release bases by decarboxylation with heat, as described in No. 5733, No. 15734, and No. 15776, etc.; Galactonamide; aldnamide compounds such as amine imides, 2-carboxycarboxamides, etc., as well as sodium phosphate base generators described in JP-A-56-130745 and JP-A-56-132332, British Patent No. 2.079. Compounds that generate amines through intramolecular nucleophilic reactions described in JP-A-59-157637, hydroxamic acid carbamates described in JP-A-59-166943, etc. No. 59-180537,
Examples include base releasing agents described in Japanese Patent No. 59-174830 and Japanese Patent No. 59-195237.

Furthermore, U.S. Patent No. 3,301,678, U.S. Pat.
．． No. 444, No. 3.824.103, No. 3.844
．． Illithiuronium compounds, S-rubamoyl derivatives of mercapto-containing compounds, and nitrogen-containing heterocyclic compounds described in RD No. 788, RD 12035, RD 18016, etc. may be used for the purpose of stabilizing images. Patent No. 3,669,670, Patent No. 4,012,260,
No. 4,060,420, No. 4,207,392,
Nitrogen-containing m called activator stabilizer and activator stabilizer precursor described in RD 15109, RD 17711, etc.
A base such as α-sulfonylacetic acid or trichloroacetate of 2-aminothiazoline, an acylhydrazine compound, etc. can be used for the purpose of accelerating development or for stabilizing the image.

Also, for example, JP-A-56-130745 and JP-A-59-2
Development may be carried out in the presence of a small amount of water as described in U.S. Pat. 3,
312,550 and the like, development may be carried out using hot steam, hot air containing moisture, or the like. Compounds that release water into heat-developable photosensitive materials, such as Japanese Patent Publication No. 44-265
Compounds containing water of crystallization as described in No. 82, such as sodium phosphate dodecahydrate and ammonium alum ditetrahydrate, 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. Regarding colloidal silica, for example, JP-A-56-109336, JP-A-53-123916, JP-A-5
It is described in No. 3-112732, No. 53-100226, etc. The amount of colloidal silica used is 0.05 to 0.05 to the binder of the layer to be mixed and coated on a dry basis.
A range of 2.0 is 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 organic fluoro compound can be used for the undercoat layer, intermediate layer, protective layer, etc.).

Regarding the fluoro compounds used in the present invention, U.S. 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. 742.680, and JP-A-46-7781, No. 48-9715, No. 49-46733, No. 49
-133023, 50-99529, 50-1
No. 1322, No. 50-160034, No. 51-431
No. 31, No. 51-129229, No. 51-10641
No. 9, No. 53-84712, No. 54-111330
No. 5e-i.

No. 9336, No. 59-30536, No. 59-4544
No. 1 and Special Publication No. 47-9303, No. 48-4313
Examples include compounds described in No. 0, 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
Alternatively, an antistatic agent can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

As the antistatic agent used in the present invention, British Patent No. 1
．． 466, No. 600, Research Disclosure t-
(Research [) 1 closure)
No. 15840, No. 16258, No. 16630, U.S. Patent No. 2,327,828, U.S. Patent No. 2,861,056
No. 3.206.312, No. 3,245,833, No. 3.428.451, No. 3.775.126,
3,963.498, 4,025,342, 4,025,463, 4,025.691, 4
, No. 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., those described in U.S. Pat. No. 3,314,794 and U.S. Pat. No. 3,352,681), benzotriazole compounds substituted with an aryl group (For example, special public relations
-10466, 41-1687, 42-26
No. 187, No. 44-29620, No. 48-41572
No., JP-A-54-95233, JP-A No. 57-142975
No. 3,253,921, U.S. Patent No. 3,533,
No. 794, No. 3.754.919, No. 3.794
．． No. 493, No. 4, No. 009.038, No. 4,220,
No. 711, No. 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. 3.70'5.805, 3.707.37
No. 5, described in JP-A No. 52-49029). Zarani, U.S. Patent No. 3.499.76
No. 2, and those described in JP-A-54-48535 can also be used. UV-absorbing couplers (e.g. α-
naphthol-based cyan dye-forming couplers), ultraviolet-absorbing polymers (for example, JP-A-58-111942, JP-A-178351, JP-A-181041, JP-A No. 59-19).
No. 945, No. 23344, and those described in the official gazette).

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive material and/or
Or non-photosensitive F! A hardening agent can be used in J (eg, undercoat layer, intermediate layer, protective layer, etc.).

Hardeners used in the present invention include aldehyde-based and aziridine-based hardeners (for example, PB Report 19.921, U.S. Pat. No. 2,950.197, U.S. Pat. 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 systems (e.g., those described in U.S. Pat.
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. 2.337.412, West German Patent No. 2)
, No. 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. 1983-54236,
No. 48-110996, U.S. Patent No. 3.539,64
No. 4, No. 3,490,911), acryloyl type (for example, Japanese Patent Application No. 48-2794)
No. 9, U.S. Pat. No. 3,640,720), carbodiimides (e.g., U.S. Pat.
．． No. 938.892, No. 4,043,818, No. 4,
061, 499, each Ming 1st edition, Special Publication Showa 46-38715
No. 49-15095), triazone series (for example, West German Patent No. 2,410,9)
No. 73, No. 2,553.915, U.S. Patent No. 3.32
5.287 and those described in JP-A-52-12722), other maleimide-based, acetylene-based, methanesulfonic acid ester-based, and N-methylol-based hardening agents are used alone or in combination. can. As a useful combination technique, for example, West German Patent No. 2.447.587
No. 2,505.746, U.S. Pat. No. 2,514,245, U.S. Patent No. 4.047.957, U.S. Pat.
No. 81, No. 3,840,370, Mei III books, JP-A No. 48-43319, No. 50-63062, No. 52
Examples include combinations described in Japanese Patent Publication No. 127329 and Japanese Patent Publication No. 48-32364.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, a polymeric hardener can be used in non-photosensitive TIJ (eg, undercoat layer, intermediate layer, protective layer, etc.).

Examples of the polymeric hardener 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. Patent No. 3.362.827, Research Disclosure No. 17333 (1978), etc., polymers having dichlorotriazine groups, U.S. Patent No. 3.623
．． Polymers having epoxy groups as described in No. 878, Research Disclosure No. 16725 (1978)
, U.S. Patent No. 4,161,417, Japanese Patent Publication No. 54-65
Examples thereof include polymers having an active vinyl group or a group that can be a precursor thereof, as described in JP-A-56-142524, and polymers having an active ester group as described in JP-A-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, poly-n-butyl acrylate, a copolymer of ethyl acrylate and acrylic acid, a copolymer of vinylidene chloride and butyl acrylate, and a copolymer of butyl acrylate and acrylic acid. Examples include copolymers, copolymers of vinyl acetate and butyl acrylate, copolymers of vinyl acetate and ethyl acrylate, copolymers 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. During use, the polymer latex has a dry weight ratio of 0.0% to the binder of the layer to which it is added.
03 to 0.5 is preferred.

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 carbonylbenzene sulfonates, alkylnafculene sulfone vi salts, alkyl sulfates, alkyl phosphates, N-acyl-N-furkyltaurines,
Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Preferably.

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 II (for example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters,
polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone),
Preferred are glycidol derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and the like.

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 include any halogenated grains such as silver chloride, tin bromide, silver iodide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. can be used. The preferred grain size of the non-photosensitive silver halide grains is about 0.
．． It is 3 μm or less.

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.
Polymers having carboxyl groups as described in No. 8 can be included.

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

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

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, antistatic agents, high boiling point solvents, antioxidants, hydroquinone derivatives, polymer latex, surfactants (including polymeric surfactants), and hardeners. Examples include film agents (including polymeric hardeners), organic silver salt particles, non-photosensitive silver halide particles, and the like.

The matting agent used in the retention process of the present invention is fine particles of an inorganic substance or a solid substance, which is incorporated into a heat-developable photosensitive material to increase the roughness of the surface of the photosensitive material and make it matte. It is something.

Methods of using matting agents to prevent adhesion that occurs during the production, storage, and use of photosensitive materials, and to prevent static electricity caused by contact, friction, and peeling between materials of the same or different types are known in the art. It is well known.

Specific examples of matting agents include silicon dioxide described in JP-A-50-46316, JP-A-53-7231, and JP-A-58.
-66937, alkali-soluble matting agents such as alkyl methacrylate/methacrylic acid copolymers described in JP-A No. 60-8894, alkali-soluble polymers having anionic groups described in JP-A-58-166341, JP-A-58-166341; Showa 58-
Combination of two or more types of fine particle powders with different Mohs hardness as described in No. 145935, combination of oil droplets and fine particle powder as described in JP-A-58-147734, and different average particle diameters as described in JP-A-59-149356 A combination of two or more types of spherical matting agents, a combination of a fluorinated surfactant and a matting agent described in JP-A-56-44411, and British Patent No. 1,055,7
No. 13, U.S. Patent No. 1,939,213, U.S. Patent No. 2,22
No. 1,873, 2,268,662@, 2.322
．． No. 037, No. 2,376.005, No. 2,391.
No. 181, No. 2,701,245, No. 2,992゜1
No. 01, same 3. (No. 179,257, No. 3,262,7
No. 82, No. 3.443,946, No. 3.516.8
No. 32, No. 3.539.344, No. 3.591,
No. 379, No. 3.754.924, No. 3.767, 4
No. 48, JP-A-49-106821, JP-A No. 57-148
Wired matting agent described in No. 35 etc., West German Patent No. 2
, 529,321, British Patent No. 760.775, British Patent No. 1.260.772, U.S. Patent No. 1,201,905
No. 2,192,241, No. 3,053.662, No. 3,062,649, No. 3,257,206,
No. 3.322,555, No. 3.353.958,
No. 3,370,951, No. 3,411,907,
3.437.484, 3.523.022, 3,615,554, 3.635.714, 3
, No. 769.020, No. 4,021,245, No. 4,
Inorganic matting agents described in 029,504, etc., or JP-A-46-7781 and JP-A-49-106821
No. 51-6017, No. 53-116143,
No. 53-100226, No. 57-14835, No. 5
No. 7-82832, No. 53-70426, No. 59-1
No. 49357, Special Publication No. 57-9053 and EP
A matting agent having physical properties such as those described in Japanese Patent No. 107,378 and the like is preferably used.

In the protective layer of the present invention, the addition m of the matting agent is i-i'
It is preferably 10 mg to 2.0 g, more preferably 20 ma to 1.0 g. It is Og. The particle size of the matting agent is 0.5
~10 μm is preferred, more preferably i.

~6 μm.

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

Examples of the slippery agent used in the FB of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, synthetic waxes, etc. Specifically, French Patent No. 2.
180,465, British Patent No. 955,061, 1
, No. 143,118, No. 1,270,578, No. 1,
320゜564, 1.320.757, JP-A-4
No. 9-5017, No. 51-141623, No. 54-1
No. 59221, 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. 3,042,522
No. 3,080,317, No. 3,082,087, No. 3,121,060, No. 3,222,178
No. 3,275.779, No. 3,489,567, No. 3,516,832, No. 3.658.573,
Those described in Japanese Patent No. 3,679,411, Japanese Patent 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 Nos. 2,353,262, 3.676, 142, 3.700.454,
Esters (e.g. phthalates, phosphoric esters, fatty acid esters, etc.), amides (e.g. fatty acid amides, (sulfonic acid amide, etc.), ethers, alcohols, paraffins, etc. ] may also contain oil droplets in which a water-insoluble oily compound is emulsified and dispersed. Additionally, these oil droplets may contain photographic additives for various purposes.

Examples of the binder used in the protective MFa of the present invention include polyvinyl butyral, polyvinyl acetate, ethylcellulose, polymethylmethacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, polyethyloxazoline, polyacrylamide, gelatin, and phthalated gelatin. One or a combination of two or more synthetic or natural polymeric substances can be used.

In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (molecular weight 1 i, ooo~400.000 is preferred), polyvinyl alcohol (molecular weight 1.000~400.000),
ioo, ooo are preferred) and polyoxazoline (molecular weight 1,000 - aoo, ooo are preferred) alone or in combination of two or more of these binders are preferred, and gelatin alone or gelatin and the above polyvinylpyrrolidone, polyvinyl alcohol and polyoxazoline are preferred. Particularly preferred are binders that use hydrophilic polymers that are highly compatible with gelatin, such as the following. Gelatin is produced by lime treatment;
The gelatin may be obtained by acid treatment or ion exchange treatment, or may be ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatin.

The thickness of the protective layer of the present invention is preferably 0.05 to 5 μm, more preferably 0.1 to 1.0 μm. Keep
sm 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. One way to make the hardness of the protective layer higher than that of the photosensitive layer, that is, to control the hardness for each store, is to use a diffusion-resistant hardener. By using it in the protective layer, only the hardness of the retainer ff1l can be made higher than that of the photosensitive layer.

Polymer hardeners are known as diffusion-resistant hardeners, for example, U.S. Pat. Nos. 3.057.723 and 3.39
No. 6.029, No. 4.161.407, JP-A-58-
Hardeners described in No. 50528 and the like can be used.

Another way to control the degree of dura for each layer is to
By containing a diffusible hardener (for example, a vinyl sulfone hardener) only in the protective layer, or by making the protective layer contain more hardener than the photosensitive layer and rapidly drying after simultaneous multilayer coating, the protective layer can be hardened. After imagewise exposure, the heat-developable photosensitive material of the present invention has a hardness of usually 80°C to 200°C, preferably 100°C to 100°C.
Developing can be carried out by simply heating in a temperature range of 70° C. for 1 second to 180 seconds, preferably 1.5 seconds to 120 seconds. Transfer of the diffusible dye to the receiving Q 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, or by bringing the image receiving member into close contact with the image receiving member after heat development and heating. Alternatively, it may be transferred by supplying water and then applying heat if necessary. Moreover, you may perform preheating in the temperature range of 70 degreeC - 180 degreeC before exposure. Also, Japanese Patent Application Laid-Open No. 143338/1983, Patent Application No. 1983
As described in Japanese Patent No. 3644, the photosensitive material and the image receiving member are placed at 80° C. immediately before thermal development and transfer in order to improve their adhesion to each other.
Each may be preheated at a temperature of 0°C to 250°C.

Various exposure means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources commonly used for color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source.

As the heating means, all methods applicable to ordinary 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 Q 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. There are no particular restrictions on the heating pattern, including 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 Although continuous 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.
, 709,690 are preferably used. For example, as a polymer containing an ammonium salt, the ratio of polystyrene-N,N,N-tri-n-hexyl-N-vinyl-benzylammonium chloride is 1=4 to 4:1, preferably 1:1. be.

Examples of polymers containing tertiary amines include polyvinyl and lysine. A typical image-receiving layer for diffusion transfer is 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.
The glass transition temperature described in No. 50 etc. is 40°C 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 a receiving layer, or may themselves be used as a support.

Examples of the heat-resistant polymeric substance include molecules l 2,
000~as, ooo polystyrene, number of carbon atoms 4
Polystyrene derivatives 1 with the following substituents, polyacetals such as polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polyvinyl Fluoroethylene chloride, polyacrylonitrile, poly N, N-dimethylallylamide, polyacrylate with p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate ,
polypropyl methacrylate, polyisobutyl methacrylate, polyisobutyl methacrylate, polyter
t-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate,
Examples include polyesters such as poly-2-cyano-ethyl methacrylate and polyethylene terephthalate, polycarbonates such as polysulfone and bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. In addition, Polymer Handbook Second Edition (G.I. Brandlap, E.H. Inmarg.
Willy and Thump (Polymer Hand
book 2nd ed.

Ll, Brandrup, E, H, immerg
ut a) John W 1ley & Sons
) Synthetic polymers with glass transition temperatures below 40°C as described in publications are also 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. Examples include polyester, polyethylene terephthalate, and polycarbonate made of a combination of diphenylcarbonate, bis-p-carboxyphenokilebutane, and ethylene glycol.

These polymers may be modified. For example, cyclohexane dimetatool, isophthalic acid,
Polyethylene terephthalate using methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid, or the like as a modifier is also effective.

A particularly preferable a-receptive 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, transparent supports, opaque supports, etc. 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., and electronic Fjll containing pigments on these supports.
? ! ! Examples include a support coated with a color-curable resin composition and cured, and a support coated with a coating layer containing a pigment on these supports.

In particular, a support that is coated with an electron beam curable resin composition containing a pigment on paper and cured, or a support that has a pigment coating layer directly on the paper or an electron beam curable resin composition on the pigment 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 as an image-receiving layer, and this image-receiving layer is formed by forming a separate layer containing a receiving area on a suitable support. It may be an image-receiving element or the image-receiving layer may be a single layer that is part of a heat-developable color photographic material. If necessary, an opacifying layer (reflection layer) may be included in the light-sensitive material, such layer reflecting the desired degree of radiation, such as visible light, which can be used to observe the dye image in the image-receiving layer. It is used to make 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 in a mold 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. Further, after imagewise exposure and uniform heat development of the heat-developable color light-sensitive material, an image-receiving layer can be superimposed and heated at a temperature lower than the phenomenon temperature to transfer the dye image released or formed from the dye-providing substance.

Margin below [Communal Effects of the Invention] As explained above, in the photothermographic material of the present invention, by using a novel reducing agent, contamination of the white background area (particularly staining due to light over time) can be prevented, and It was possible to provide a heat-developable color photosensitive material that provides color images with high density, low fog, and good tone.

[Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples. ! ! You are not limited to these.

Example-1 <Preparation of organic silver salt dispersion> 5-Methibenzotriazole and silver nitrate were reacted in a water-alcohol mixed solvent, and 28.8 g of the obtained 5-methibenzotriazole and poly(N-vinylpyrrolidone) were reacted. )1
6. Og was dispersed in an alumina ball mill, the pH was adjusted to 5.5, and ZOOml was finished.

<Preparation of dye-providing substance dispersion> 35.5 g of the exemplary dye-providing substance (PM-7), 5.00 g of the following hydroquinone compound, and 0.7 g of the following development inhibitor were mixed with 200 mj of ethyl acetate! Alkanol xC (manufactured by DuPont) 5% by weight water soluble 9124ml
, phenylcarbamoylated gelatin (Rouslow Type 17819 PC) was mixed with 720 ml of an aqueous gelatin solution containing 30.5 g, dispersed with an ultrasonic homogenizer, and after distilling off ethyl acetate, adjusted to pH 5.5 and heated to 795 ml.
It was set to 1.

Hydroquinone compound inhibitor [Silver iodobromide emulsion preparation 911 at 50°C, JP-A-57-92523, JP-A-57-92523;
No. 92524 Using the mixing method shown in each specification, 20 g of ossein gelatin, 1000 ml of distilled water, and ammonia were dissolved in Solution A, and Solution B containing 11.6 g of potassium iodide and 130 g of potassium bromide and 1 silver nitrate were added. A solution C of 500a1 aqueous solution containing mol and ammonia was simultaneously added while keeping pAg and 9H constant.

Furthermore, by controlling the addition speeds of Solution B and Solution C, a core emulsion with a silver iodide content of 7 mol % and a regular hexahedral average grain size of 0.25 μm was prepared. Next, by coating a silver halide shell with a silver iodide content of 1 mol % in the same manner as described above, cores with a regular hexahedral average grain size of 0.3 μl (shell thickness 0.05 μm) are formed. /Shell type silver halide emulsion (8% monodispersity) was prepared as 7I4. The above emulsion was washed with water and desalted, yielding 700mj! I got it.

<Preparation of developer> 22.2 g of the reducing agent (R-1), 14.6 g of poly(4-vinylpyrrolidone), and 0.50 g of the following fluorine-based surfactant were dissolved in water, adjusted to pH 5.5, and heated at 250 mA.
'.

Surfactant Na○3S CHCOOCH2 (CF2CF2) mH
CH2COOCH2(CF2CF2)nH(
m, mouth = 2 or 3) <Preparation of heat-developable photosensitive material> A8! Silver salt dispersion liquid 12.51am! ,
/10 silver denride emulsion 6. Oa1, dye-providing substance dispersion liquid 3
Mix 9.8 ml and 12.5 ml of developer, and then react a hardener solution (tetra(vinylsulfonylmethyl)methane and taurine in a 1:1 (weight ratio)) and dissolve it in a 1% aqueous solution of phenylcarbamoylated gelatin. Then, Tetra (
2.5ml of vinylsulfonylmethyl (vinylsulfonylmethyl) methane (3% by weight) and 3.80g of polyethylene glycol 300 as a hot solvent were added, and the undercoat was applied to a thickness of 180μ (to). A protective layer made of a mixture of the 7-enylcarbamoylated gelatin and poly(N-vinylpyrrolidone) was coated on a polyethylene Tele 7 Tanaut film for use in a film with a silver content of 1.76 g/m2. has been established.

[Made by image receiving member-1! ! ] Polyvinyl chloride (n=11100
, Wako Tsumugi Co., Ltd.) tetrahydro 7 run solution was applied.
The amount of polyvinyl chloride applied was set to 12 g/L112.

The heat-developable photosensitive material was exposed to 1.600 cm S of light through a step unit, and together with the image receiving member was placed in a heat developing machine (developer module 277.3).
Company M! After heat development was carried out at 150° C. for 90 seconds in a vacuum cleaner, when the photosensitive material and image receiving member were peeled off, a magenta step wedge image was obtained on the polyvinyl chloride surface of the image receiving member.

The reflection density of the obtained image was measured using a densitometer [PDA-65
The maximum density (D
wax) and minimum concentration (D win) were determined.

The results are shown in Table-1.

Example 2 The same photosensitive material as in Example 1 was used except that the reducing agent (R-1) was changed to the reducing side shown in Table 1 (the amount added was equimolar to R-1). It was prepared, exposed to light and thermally developed in the same manner as in Example 1, and the density of the obtained image was measured. The results are also shown in Table-1.

Table 1 In Samples Nos. 7 and 8, the reducing agent was precipitated from the photothermographic material, resulting in uneven density.

Comparison-1, which is a comparative reducing agent used in Margin Table-1 below,
Comparison-2 and Comparison-3 are as follows.

Comparison-1 Comparison-2 Comparison-3 As is clear from the results in Table 1, compared to Comparative Samples 8 to 10 using the comparative reducing agent, Samples 1 to 7 of the present invention have no It can be seen that the maximum density was also significantly improved, and the minimum density was also kept sufficiently low. In Sample 7 of the present invention and Comparative Sample 8, some of the reducing agent was precipitated from the photothermographic material, resulting in uneven density.

Example 3 The transferred images of Examples 1 and 2 were illuminated with an a, ooow xenon lamp for 48 hours (illuminance on the image surface was 60.00
0 lux), and the reflection density with blue light of the fogged area before and after irradiation was measured. The results are shown in Table-2.

Table 2 As is clear from Table 2, in comparative sample 8, where the maximum concentration was satisfied to some extent, there was fogging caused by light over time, that is, contamination of the white background (presumed to be stain originating from thermal decomposition products of the reducing agent). However, samples 1 to 7 of the present invention
It can be seen that this is an excellent product with no contamination in the white background area.

Example-4 A photosensitive material similar to Example-1 was prepared except that the dye-providing substance in Example-1 was changed to the dye-providing substance shown in Table-3. These photosensitive materials (No. 11 to 15) were used in Example-1
Exposure was carried out in the same manner as in Example 1, and photosensitive materials Nos. 11 and 12 were subjected to heat development in the same manner as in Example-1. In addition, photosensitive materials Nos. 13 to 15 were not brought into close contact with the image receiving paper;
After thermal development at 0°C for 1 minute, E-
Bleaching and fixing were performed by 6 treatments to obtain a color image. The obtained image density is shown in Table 3.6 [E-6 Processing] Process Temperature Time 1, Coditioner - 25-40°C 2 minutes 2, Bleaching 35-38°C 6 minutes 3, Fixing 25-
40° C. 6 minutes 4 minutes Washing with water Table 3 As can be seen from the margin Table 3 below, it can be seen that the effects of the present invention can be obtained even if the type of dye-providing substance is changed.

As shown in the above examples, the heat-developable photosensitive material using the reducing agent of the present invention can provide color images with high density and low fogging, and the photosensitive material using the reducing agent of Comparison-1 can obtain color images with high density and low fogging. Significant increase in stain due to light attempted with (
It exhibits excellent properties such as greatly improving staining (presumed to be caused by thermal decomposition products of the reducing agent).

Claims (1)

[Claims] On a support, at least a photosensitive silver halide, a reducing agent,
In a heat-developable color photosensitive material having a photographic constituent layer containing a dye-providing substance and a binder, the following general formula (1
) A heat-developable color photosensitive material characterized by containing a reducing agent represented by: General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an alkyl group, and R_2, R_3, and R_4 are a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an acylamino group, and a sulfonamide group, respectively. , represents an alkylsulfonamide group or an alkyl group, and R_5 and R_6 each represent a hydrogen atom or an alkyl group. However, R_3 and R_5, R_2 and R_6, and R_5 and R_6 may each be closed to form a heterocycle. M is a hydrogen atom, an alkali metal atom,
Represents an alkaline earth metal atom, an ammonium group, or a nitrogen-containing organic base. m represents 1 or 2.