JPH061361B2 - Color photosensitive material and photothermographic material - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color light-sensitive material and a photothermographic material, and more particularly to a color light-sensitive material containing a developer precursor that efficiently releases a developer by a guanidine or amidine derivative. And a photothermographic material.

Prior art and its problems Photosensitive materials using silver halide are extremely superior in sensitivity, gradation control, etc. as compared with non-silver salt photosensitive materials such as electrophotographic methods, diazo photographic methods, and photosensitive materials using photosensitive polymers. Due to its characteristics, it is now widely used.

However, silver halide light-sensitive materials have drawbacks such as wet development, complexity and immediacy, and development of light-sensitive materials with simple and rapid processing suitability and processing system design are active. Has been done to. For example, a method of incorporating a color developing agent in a light-sensitive material and processing with an activator solution is disclosed in British Patent Nos. 998,949 and 1,374.
No. 807 and the like. In addition, as a thing aiming at speeding up by introducing a heating step in the development processing,
U.S. Pat. Nos. 3,531,286 and 3,761,270 are known. Further, many methods of incorporating a developing agent as a precursor in order to increase the stability of a color developing agent incorporated in a light-sensitive material have been proposed, and a Schiff base derivative (US Pat. No. 3,342,597, US Pat. Third
342599), glycosyl derivatives (Research Disclosure No. 13924 etc.), sulfomethyl derivatives (German Patent No. 1159758, Surance Patent No. 1444777 etc.), Phosphomethyl derivatives (German Patent No. 1200679 etc.), phthalimidoyl derivatives (German Patent No. 1200679 etc.) (British Patent No. 1069061, etc.), β-sulfonylethylurethane derivatives (JP-A No. 53-135628, etc.)
Etc. are used.

When the color developing agent is incorporated in the light-sensitive material, it is necessary to take some stabilizing means in terms of temporal stability. However, none of the above-mentioned developer precursors can achieve both stability and rapid decomposition during development. That is, a stable product has a slower release of the developing agent at the time of development and a longer image forming time. On the other hand, if the developing agent is released quickly, the developing agent is partially released during storage and fog or stain occurs.

Therefore, it is desired to provide a developer precursor that solves these problems.

II Object of the Invention An object of the present invention is to use a developer precursor which has good stability over time and a good developer release efficiency, and is excellent in preservability and S / N.
It is an object of the present invention to provide a color light-sensitive material and a photothermographic material which give a high ratio image.

III DISCLOSURE OF THE INVENTION Such an object is achieved by the present invention described below.

That is, the present invention comprises at least one of a photosensitive silver halide, a coupler capable of binding with an oxidized product of a developing agent, a hydrophilic binder and a compound represented by the following general formula (I) on a support. And a color light-sensitive material.

The second invention contains at least one of a photosensitive silver halide, a coupler capable of binding with an oxidized product of a developing agent, a hydrophilic binder and a compound represented by the following general formula (I) on a support. And a photothermographic material.

General formula (I) {In the above general formula (I), R ₁ , R ₂ , R ₃ and R
₄ is a hydrogen atom, a halogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aralkyl group, amino group,
It represents an alkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aryl group, a carbamoyl group, a sulfamoyl group, an acyl group, an acyloxy group or an alkoxycarbonyl group. Further, R ₁ and R ₂ or R ₃ and R ₄ may be linked to each other to form a ring. A is a hydroxyl group, a group that gives a hydroxyl group by the action of a nucleophile, or (Wherein R ₆ and R _{7 each} represent a hydrogen atom, or a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group or aralkyl group, and R ₆ and R ₇
May combine to form a heterocycle).

Also, A In the case of, one or both of (R ₁ and R ₆ ) and (R ₃ and R ₇ ) may be linked to form a heterocycle.

R ₅ represents a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aralkyl group or aryl group. } Specific Structure of IV Invention Hereinafter, a specific structure of the present invention will be described in detail.

The color light-sensitive material of the present invention comprises at least a light-sensitive silver halide on a support, a coupler which binds to an oxidant of a developing agent,
It contains at least one of a hydrophilic binder and a compound represented by the following general formula (I).

General formula (I) In the above general formula (I), R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom (eg a chlorine atom,
Bromine atom, fluorine atom, etc.), alkyl group (preferably alkyl group having 1 to 32 carbon atoms, for example, methyl group, ethyl group,
Octyl group, etc., alkenyl group (preferably having 2 to 2 carbon atoms)
32 alkenyl groups such as allyl group, vinyl group, crotyl group and the like, cycloalkyl group (preferably having 3 to 10 carbon atoms)
8 cycloalkyl groups such as cyclohexyl group, cyclopentyl group, and aralkyl groups (preferably having 7 carbon atoms)
-18 aralkyl groups such as benzyl group, α-methylbenzyl group, β-phenethyl group), hydroxyl group,
Amino group, substituted amino group, alkoxy group (preferably alkoxy group having 1 to 32 carbon atoms, such as methoxy group, methoxyethoxy group, butoxy group, etc.), acylamino group (preferably acylamino group having 2 to 32 carbon atoms, such as acetyl Amino group, hexanoylamino group, octanoylamino group, stearoylamino group, etc.), alkylsulfonylamino group (preferably alkylsulfonylamino group having 1 to 32 carbon atoms, for example, methylsulfonylamino group, octylsulfonylamino group, etc.), Arylsulfonylamino group (preferably arylsulfonylamino group having 6 to 18 carbon atoms, for example, phenylsulfonylamino group, p-
Chlorophenylsulfonylamino group, etc.), aryl group (eg phenyl group, naphthyl group etc.), carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, acyl group (preferably acyl group having 2 to 32 carbon atoms, eg acetyl group) , A benzoyl group), an acyloxy group (preferably an acyloxy group having 2 to 32 carbon atoms, such as an acetyloxy group, a benzoyloxy group, etc.), or an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 32 carbon atoms, such as methoxy). Carbonyl group, ethoxycarbonyl group, etc.), R
₁ and R ₂ or R ₃ and R ₄ may combine to form a ring (for example, a saturated ring formed by a trimethylene group, a tetramethylene group, etc., a naphthalene ring formed by a benzolog, etc.).

When R ₁ , R ₂ , R ₃ or R ₄ is an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group or a group containing an aliphatic hydrocarbon group such as an aralkyl group, an alkoxy group or an acylamino group, The aliphatic hydrocarbon group may be linear or branched. When R ₁ to R ₄ are a hydrogen atom, a halogen atom, or a substituent other than a hydroxyl group,
These may have one or more substituents (including a substituent atom; the same applies hereinafter) that are allowed for R ₁ to R ₄ described below, and when two or more, they may be the same or different.

Substituents allowed for R ₁ to R ₄ include an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, an acyl group, an ester group, an amide group, an imide group, and an aliphatic sulfonyl group. Group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic thio group, arylthio group, heterocyclic thio group, hydroxyl group, cyano group, carboxyl group, sulfo group, nitro group and the like.

When R ₁ to R ₄ are a substituted amino group, a substituted carbamoyl group or a substituted sulfamoyl group, the permissible substituents are the same as the permissible substituents for R ₁ to R ₄ .

Preferred examples of R ₁ , R ₂ , R ₃ and R ₄ include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an aryl group, a carbamoyl group and a substituted carbamoyl group.

A is a hydroxyl group, its precursor or In the case of a hydroxyl group precursor, it is a group which gives a hydroxyl group by the action of a nucleophile. Here, as the nucleophile, anionic reagents such as OH ⁻ , OR ⁻ , SO ₃ ²⁻ and unshared electron pairs such as primary or secondary amines, hydrazines, hydroxylamines, alcohols and thiols are used. Compounds that have.

Examples of the hydroxyl group precursor include an acyloxy group (preferably having a carbon number of 2 to 18, such as an acetoxy group and a benzoyloxy group) and an alkylsulfonyloxy group (preferably having a carbon number of 1 to 12, such as a methanesulfonyloxy group and an octylsulfonyl group). An oxy group), an arylsulfonyloxy group (preferably having a carbon number of 6 to 18, such as a phenylsulfonyloxy group), an alkoxycarbonyloxy group (preferably having a carbon number of 2 to 18, such as an ethoxycarbonyloxy group, an isobutyroyloxy group). Etc.), an aryloxycarbonyloxy group (preferably having 7 to 7 carbon atoms).
18, for example, phenoxycarbonyloxy group, etc., dialkylphosphoryloxy group (preferably having 2 to 1 carbon atoms)
6, for example, diethylphosphoryloxy group, etc., diarylphosphoryloxy group (preferably having 12 to 24 carbon atoms,
For example, diphenylphosphoryloxy group etc.) and the like.

A is In the case of, R ₆ and R ₇ are each a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 32 carbon atoms,
For example, a methyl group, an ethyl group, a dodecyl group, a methanesulfonylaminoethyl group, a hydroxyethyl group, etc.) and a substituted or unsubstituted alkenyl group (preferably having 2 to 1 carbon atoms).
8, for example, an allyl group, a cinnamyl group, etc., a substituted or unsubstituted cycloalkyl group (preferably having a carbon number of 3 to 1)
2, for example, a cyclohexyl group) or a substituted or unsubstituted aralkyl group (preferably having 7 to 18 carbon atoms, for example, benzyl group, β-phenethyl group, etc.), R ₆
And R ₇ may combine to form a heterocycle (eg, a pyrrolidine ring, a piperidine ring, a morpholine ring, etc.). Also (R
One or both of ₁ and R ₆ ) and (R ₃ and R ₇ ) may be linked to form a heterocycle (eg, a tetrahydroquinoline ring, a julolidine ring, etc.).

Preferred examples of A include a hydroxyl group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a dialkylphosphoryloxy group, a diarylphosphoryloxy group, and a dialkylamino group (wherein the alkyl group is substituted. May be used), pyrrolidino group, piperidino group, morpholino group and the like.

R ₅ is a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, methoxyethyl group, phenoxyethyl group, cyanoethyl group, dodecyloxyethyl group, etc.), alkenyl group (eg, allyl group, crotyl group, etc.), cycloalkyl Group (for example, cyclohexyl group, cyclopentyl group, 4-methyl-1-cyclohexyl group, 1-tetrahydronaphthyl group, 1-decahydronaphthyl group, etc.), aralkyl group (for example, benzyl group, p-chlorobenzyl group,
Examples thereof include p-methoxybenzyl group, β-phenethyl group, etc.) and aryl groups (phenyl group, p-tolyl group, p-chlorophenyl group, 3,5-dichlorophenyl group, 2,4-xylyl group, etc.).

Preferable examples of R ₅ include an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group, a phenyl group and a substituted phenyl group.

Specific preferred examples of the developer precursor represented by the general formula (I) are shown below, but the invention is not limited thereto.

The developing agent precursor used in the present invention is a known method, for example, a method of reacting an aniline (developing agent) with oxalyl chloride to form oxamic acid chloride, and then reacting with a corresponding alcohol or phenol, or in advance with an alcohol. Alternatively, it can be synthesized by a method of reacting a phenol with oxalyl chloride and then reacting with a corresponding aniline (developer).

The specific synthesis examples of the developer precursor used in the present invention are shown below.

Synthesis example 1. Synthesis of Exemplified Compound 1 2.73 g of ethyloxalyl chloride was added dropwise to a mixture of 7.12 g of 2,6-dichloro-4-aminophenol and 100 ml of acetonitrile under ice cooling. 5-1 after dropping
After stirring at 0 ° C for 1 hour, the produced white crystals were collected by filtration.

Then, the crystals were dispersed in 300 ml of warm water at 50 ° C.,
After stirring for 0 minutes, the mixture was filtered, and the residue was recrystallized from acetonitrile to obtain 3.8 g of a white needle crystal of Exemplified Compound 1.
Melting point 240-242 ° C (decomposition) Synthesis example 2. Synthesis of Exemplified Compound 6 To a mixture of 8.9 g of 2-methyl-4-diethylaniline, 30 ml of dimethylacetamide and 20 ml of pyridine, under ice cooling, at 10 ° C. or below, 8.2 g of ethyloxalyl chloride.
Was dripped.

After stirring at 10 ° C for 30 minutes, the reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate solution was washed with a dilute aqueous solution of copper sulfate and then washed with water, and the ethyl acetate was distilled off under reduced pressure.
The residue was recrystallized from a mixed solvent of n-hexane / ethyl acetate to obtain 6.8 g of pale yellow crystals of Exemplified Compound 6. Melting point 85-86 ° C. The characteristic feature of the developer precursor of the present invention is that the developer is not released by water or alkali (for example, sodium hydroxide, sodium carbonate, etc.), but a specific reagent (for example, guanidine, amidine, ethylenediamine, 1, 3-propylenediamine, θ-phenylenediamine, etc.) is the first to release the developer. This property is a characteristic of oxamic acid ester, and only the ester part is hydrolyzed by water or alkali, whereas in the reaction with the above reagent, an amide bond is first formed by the reaction with the ester part, and then the intramolecular compound is formed. It is considered that the developer is released by the nucleophilic substitution reaction.

Therefore, the developer precursor of the present invention is particularly effective when combined with the above reagents.

Among the above reagents, guanidines and amidines have high release efficiency and are preferably used.

For example, a wet processing system using a processing solution containing guanidines or amidines (room temperature development), a system in which a sheet coated with guanidines or amidines is heated and developed, and a generator containing guanidines or amidines is applied. A system in which heat development is performed by superimposing it on a sheet, a system in which heat development is performed in the coexistence of a thermally decomposable base generator that generates guanidines and amidines, etc. are useful.

Since the release efficiency of the developing agent by the reaction of the developing agent precursor of the present invention with guanidines and amidines is higher in a non-aqueous medium than in an aqueous solution, a dry developing system, that is, thermal The developing system is more effective.

The application to the photothermographic material will be described in detail below.

The developer precursor of the present invention may be used alone or in combination of two or more kinds. Generally, it can be used in a range of 0.1-fold to 10-fold mol, preferably 0.2- to 3-fold mol, based on the total amount of coated silver constituting the photosensitive layer.

The developer precursor of the present invention can be incorporated into the light-sensitive material by many methods. According to a method generally known as an oil protection method, it may be dissolved in a hydrophobic oil to be emulsified and dispersed as an oil-in-water dispersion in water or in a hydrophilic colloid solution. Alternatively, it may be added as fine particles to the hydrophilic colloid solution, or the compound in the solid state may be introduced into water or the hydrophilic binder using a ball mill or the like.

The developer precursor represented by formula (I) used in the present invention may be added to any layer constituting the heat developable color light-sensitive material. Examples thereof include a photosensitive silver halide emulsion layer, a hydrophilic colloid layer, an intermediate layer and the like.

Various types of couplers are known which bond with an oxidized product of a developing agent. For example, TH James's "The theory of the
photographic process "4th Ed., 354-361 pages, Shinichi Kikuchi" Photographic Science "4th edition (Kyoritsu Publishing) 284
Any of the couplers described on page 295 and the like can be used in the present invention.

In the present invention, both a 4-equivalent coupler having a hydrogen atom at a site where it binds to an oxidized product of a developing agent and a 2-equivalent coupler substituted with a leaving group can be used. Further, a so-called Fisher dispersion type coupler having both a hydrophilic group and a hydrophobic diffusion resistant group in the coupler and an oil protect dispersion type coupler having only a hydrophobic diffusion resistant group can be used. Among couplers having anti-diffusion groups, Japanese Patent Application Laid-Open No.
Couplers having a hydrophobic ballast group in the leaving group described in JP-A-8-149046; couplers in which a leaving group described in JP-A-58-149047 and the like are linked to a polymer main chain:
U.S. Pat. No. 3,370,952: U.S. Pat. No. 3,451,820;
No. 4080211; No. 4215195; No. 4
The polymer couplers described in 409320 and the like are included. Also, British Patent No. 1330524; Japanese Patent Publication No. 48-
39165; JP-A-57-186744; 57-57.
No. 207250; No. 58-79247, etc., colored couplers containing a dye component in the leaving group are also useful in the present invention.

The couplers preferably used in the present invention are active methylene and active methine compounds, phenols, naphthols, pyrazoles and condensed pyrazole compounds, and particularly preferable ones are represented by the following general formulas (I) to (X).

In the above formula, R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, Acylamino group, alkoxyalkyl group, aryloxyalkyl group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, alkylamino group, arylamino group, acyloxy group, acyloxyalkyl group, substituted ureido group, cyano group, heterocycle Represents a substituent selected from residues, these substituents are further alkyl group, alkoxy group, halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group,
It may be substituted with a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aryl group, an aryloxy group, an aralkyl group or an acyl group. X ¹ represents a hydrogen atom or a coupling-off group, a halogen atom, an acyloxy group, a sulfonyloxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyloxy group, a dialkylcarbamoyloxy group,
Imido group, N-heterocyclic residue, pyridinium group and the like are typical examples of the coupling-off group. In addition, R ₈ , R ₉ , R
It is preferred that either ₁₀ , R ₁₁ or X ¹ be a ballast group that provides diffusion resistance, or these groups may be linked to the polymer backbone.

Diffusion resistant compounds (dye releasing couplers) that release a diffusible dye through a coupling reaction with an oxidized product of a developing agent can also be used in the present invention. Typical examples of this type of compound are the compounds listed in U.S. Pat. No. 322750. For example, one represented by the following formula (XI) can be given.

Coup-Link-Dye (XI) In the formula, Coup represents a coupler residue capable of coupling with an oxidized product of a developing agent, and preferably X is removed from the coupler represented by the general formula (I) to (X). Represents a part.

Link is bound to the active site of the Coup portion, and when the dye-releasing coupler represented by the above formula (XI) undergoes the coupling reaction with the oxidized product of the developing agent, the bond between the Coup portion and the bond is cleaved. And represents an azo group, for example, an azo group, an azoxy group, -O-, -Hg-, an alkylidene group, -S-,-.
In addition to S—S—, NHSO ₂ — and the like, the coupling-off group X ¹ described above is also useful.

Dye represents a dye or a dye precursor.

Among the dye releasing couplers represented by the above formula (XI), Coup is preferably a phenol type coupler residue, a naphthol type coupler residue or an indanone type coupler residue, and Link is an oxygen atom or a nitrogen atom.
Is bound to.

In the present invention, the coupler can be incorporated into the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid alkyl ester (for example, dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (for example, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.), citric acid ester (for example, tributyl acetyl citrate, etc.), Benzoic acid esters (eg, octyl benzoate), alkylamides (eg, diethyllaurylamide), fatty acid esters (eg, dibutoxyethyl succinate, dioctyl azelate, etc.),
High-boiling organic solvents such as trimesic acid esters (eg, tributyl trimesic acid) or low-boiling organic solvents having a boiling point of about 30 ° C. to 160 ° C., such as ethyl acetate, lower alkyl acetates such as butyl acetate, ethyl propionate, and dipropionate. It is dissolved in primary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone and the like, and then dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Also, JP-B-51-39853 and JP-A-51-5994.
A dispersion method using a polymer described in No. 3 can also be used. When the coupler is dispersed in the hydrophilic colloid, various surfactants can be used, and those surfactants are disclosed in JP-A-59-157636, (37) to (38).
The surfactants listed on the page can be used.

The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g or less based on 1 g of the coupler used.

In the present invention, a reducing substance may be used in combination in the light-sensitive material. Examples of the reducing substance include auxiliary developing agents that can be used in combination with the developing agent precursor of the present invention. The auxiliary developing agent may be diffusible or non-diffusible.

Useful auxiliary developers include alkyl-substituted hydroquinones such as hydroquinone, t-butylhydroquinone and 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and alkoxy such as methoxyhydroquinone. There are polyhydroxybenzene derivatives such as substituted hydroquinones and methylhydroxynaphthalene. Further, methyl gallate, ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N, N-di- (2-ethoxyethyl) hydroxylamine, 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl- Pyrazolidones such as 1-phenyl-3-pyrazolidone, reductones, hydroxytetronic acids, θ-such as 2-dioctylcarbamoyl-4-phenylsulfonylamino-1-naphthol
(P-) sulfonamidophenol (naphthol) and the like are useful.

The auxiliary developing agent can be used within a certain concentration range. A useful concentration range is 0.00005 times to 10 times the molar amount of the total coated silver, and a particularly useful concentration range is 0.0
The molar amount is from 01 times to 0.5 times.

In the present invention, a base or a base generator is preferably used.
The base or base generator is a compound capable of activating the development by making the system basic, or a compound having a nucleophilic property, and is extremely effective for improving the maximum density. In particular, in the present invention, the compound represented by the general formula (I) is a precursor of a developing agent, and therefore a base is essential at the time of heat development in order to remove the protecting group from the precursor and develop the developing activity. That is, in the image forming method of the present invention, the light-sensitive material is usually heat-developed in the presence of a base or a base generator.

Specifically, a base or a base generator may be added to the photosensitive material in advance, or may be supplied from the outside during heat development (for example, it may be dissolved in water and supplied). Here, the base generator includes those used in a base precursor or a base generating system described later, for example, those which react with other compounds to generate a base. When added to the light-sensitive material layer, it is advantageous to use, for example, a base precursor among base generators. The base precursor referred to here is one that releases a base upon heating. Preferred bases are as described above, specifically, guanidine, methylguanidine, 1,3-dimethylguanidine, phenylguanidine, benzylguanidine, 1,3-diphenylguanidine, acetamidine, benzamidine, ethylenediamine, θ-phenylenediamine and the like. Can be mentioned.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heating to decompose, compounds that decompose to release amines by Rossen rearrangement, Beckmann rearrangement, etc. that cause some reaction to release base by heating. Used.

Preferred base precursors include the above-mentioned organic base precursors. Examples thereof include salts with thermally decomposable organic acids such as trichloroacetic acid, trifluoroacetic acid, propiolic acid, cyanoacetic acid, sulfonylacetic acid and acetoacetic acid, and salts with 2-carboxycarboxamide described in US Pat. No. 4,088,496.

Preferred specific examples of the base precursor are shown below.

The following may be mentioned as examples of compounds that are believed to decarboxylate the acid moiety to release a base.

Examples of the trichloroacetic acid derivative include guanidine trichloroacetic acid, methylguanidine trichloroacetic acid, acetamidine trichloroacetic acid, θ-phenylenediamine trichloroacetic acid, and 1,3-dimethylguanidine trichloroacetic acid.

Other British Patent No. 998945, US Patent No. 3220
The base precursors described in JP-A No. 846 and JP-A No. 50-22625 can be used.

Other than trichloroacetic acid, US Pat.
No. 8496, 2-carboxycarboxamide derivative, US Pat. No. 4,060,420, α-sulfonyl acetate derivative, JP-A-59-180549, phenylpropiolic acid derivative, JP-A-59-1805.
The salt of a propiolic acid derivative described in No. 37 and a base can be mentioned.

Further, a base generating system in which two kinds of substances added to the light-sensitive material layer and the dye-fixing material layer are brought into contact with each other during heat development to generate a base is particularly useful in the present invention. An example of such a base generating system is a combination of a metal complexing agent and a sparingly soluble metal salt such as calcium, magnesium, aluminum, zinc or copper.

These bases or base precursors can be used in a wide range. The useful range is 50% by weight or less, more preferably 0.01% by weight to 40% by weight based on the weight of the dry coating film of the light-sensitive material.

The above bases or base precursors can of course be used not only for promoting dye image formation, but also for other purposes such as adjusting the pH value.

The components as described above constituting the photothermographic material used in the present invention can be arranged at any appropriate positions. For example, if desired, one or more of the components can be placed in one or more film layers in the photographic material. In some cases, it is desirable to include a specific amount (ratio) of the reducing agent, the image stabilizer and / or the other additive as described above in the protective layer.

The silver halide that can be used in the present invention includes silver chloride, silver bromide,
Alternatively, any of silver chlorobromide, silver chloroiodide and silver chloroiodobromide may be used.

Specifically, Japanese Patent Application No. 59-228551, pages 35 to 36.
Page, U.S. Pat. No. 4,500,626, column 50, Research
Any of the silver halide emulsions described in Disclosure, June 1978, pages 9 to 10 (RD17029) and the like can be used.

The silver halide emulsion may be used as it is without ripening, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional type light-sensitive materials. It can also be carried out in the presence of a nitrogen heterocyclic compound containing these chemical sensitizations (JP-A Nos. 58-126526 and 58-215644).
issue).

The silver halide emulsion used in the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. It is also possible to use a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. in this case,
It is necessary that the photosensitive silver halide and the organic metal salt are in contact with each other or in close proximity.

Among such organic metal salts, organic silver salts are particularly preferably used.

Examples of organic compounds that can be used to form the above organic silver salt oxidizing agent include Japanese Patent Application No. 59-228551, pp. 37-
39, U.S. Pat. No. 4,500,626, columns 52-53.
There are compounds described in the columns and the like. Also, Japanese Patent Application No. 58-2215
A silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate described in No. 35 is also useful.

The above organic silver salts are the following per mol of photosensitive silver halide:
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 50 mg to 10 g / m ² in terms of silver.
Is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, JP-A-59-180550 and JP-A-60-1
40335, Research Disclosure Magazine 197
June 2012, pp. 12-13 (RD17029), sensitizing dyes, JP-A-60-111239, and Japanese Patent Application No. 60-90.
Examples of the heat-decolorizing sensitizing dyes described in JP-A-172967 and the like.

These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion (for example, U.S. Pat. Nos. 2,933,390, 3,635,721, 3,743,510, 3,615,613 and 361).
No. 5641, No. 3617295, No. 363572
(Item No. 1).

These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after chemical ripening, and US Pat. No. 4,183,756.
No. 4225666 and before or after the nucleation of silver halide grains.

The addition amount is generally 10 ^-8 to 1 per mol of silver halide.
It is about 0 ^-2 mol.

In the present invention, an image formation accelerator can be used in the light-sensitive material. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together.

Details thereof are described in Japanese Patent Application No. 59-213978, pp. 67-71.

In the present invention, various development terminators can be used for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development.

The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof (for example, Japanese Patent Application No. 58-216928, 59-48
No. 305, No. 59-85834 or No. 59-858.
36, etc.).

Further, a compound which releases a mercapto compound by heating is also useful, for example, Japanese Patent Application Nos. 59-190173 and 59-59.
-268926, 59-246468, 60-
No. 26038, No. 60-22602, No. 60-260
No. 39, No. 60-24665, No. 60-29892
No. 59-176350.

Further, in the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 45.
No. 00626, columns 51-52.

Various antifoggants can be used in the present invention. As antifoggants, azoles, JP-A-5
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-9-168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, Japanese Patent Application No. 60-2.
The acetylene compounds described in 2867 are used.

In the present invention, the light-sensitive material may optionally contain an image toning agent. Specific examples of effective toning agents include compounds described in Japanese Patent Application No. 59-268926, pages 92 to 93.

The binder of the light-sensitive material of the present invention can be used alone or in combination. This binder may be hydrophilic. As a hydrophilic binder, a transparent or translucent hydrophilic binder is typical,
Examples include proteins such as gelatin and gelatin derivatives, cellulose derivatives, polysaccharides such as starch, natural substances such as arabic gum, and synthetic polymer substances such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers.

Other synthetic polymeric materials include dispersed vinyl compounds that are used in the form of latex and increase the dimensional stability of photographic materials.

In the present invention, the coating amount of the binder is 20 g or less per 1 m ² , preferably 10 g or less, more preferably 7 g or less.
g or less is suitable.

The ratio of the high-boiling-point organic solvent dispersed in the binder together with the hydrophobic compound such as the dye-providing substance to the binder is 1 cc or less of the solvent, preferably 0.5.
cc or less, more preferably 0.3 cc or less is suitable.

In the photographic light-sensitive material and dye-fixing material of the present invention, the photographic emulsion layer and other binder layers may contain an inorganic or organic hardener.

Specific examples of the hardener are described in Japanese Patent Application No. 59-268926, pages 94 to 95 and JP-A-59-157636 (3).
The ones described on page 8) are mentioned, and these can be used alone or in combination.

The support used for the light-sensitive material and optionally the dye-fixing material of the present invention can withstand the processing temperature. As a general support, not only glass, paper, polymer film, metal and analogues thereof are used, but also mentioned as a support on pages 95 to 96 of Japanese Patent Application No. 59-268926. Things can be used.

When the light-sensitive material used in the present invention contains a dye-providing substance that is colored, it is not so necessary to further add an anti-irradiation or anti-halation substance or various dyes to the light-sensitive material. No. 59-268926, pages 97-98 and U.S. Pat. No. 450
Filter dyes, absorbent substances, and the like described in the literature exemplified in Column 55 (Lines 41 to 52) of No. 0626 can be contained. To obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta, and cyan,
The light-sensitive element used in the present invention must have at least three silver halide emulsion layers sensitive to different spectral regions.

A typical combination of at least three photosensitive silver halide emulsion layers having photosensitivity in mutually different spectral regions is described in JP-A-59-180550.

The light-sensitive material used in the present invention may optionally have two or more emulsion layers having photosensitivity in the same spectral region depending on the sensitivity of the emulsion.

The photosensitive material used in the present invention contains various additives known as a photothermographic material, and layers other than the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, and A, if necessary.
An H layer, a peeling layer, a mat layer and the like can be contained. As various additives, Research Disclosure Magazine 1
Pages 9 to 15 of the June 1978 issue (RD1709
2), additives described in Japanese Patent Application No. 59-209563 and the like, for example, plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes, matting agents, surfactants, fluorescent whitening agents, and ultraviolet absorption. There are additives such as agents, anti-slip agents, antioxidants, and anti-fading agents.

In particular, it is common for the protective layer to contain an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and a UV absorber. The protective layer and the intermediate layer may each be composed of two or more layers.

In the intermediate layer, a reducing agent for preventing discoloration and color mixture,
A white pigment such as a UV absorber or TiO ₂ may be included. The white pigment may be added to the emulsion layer as well as the intermediate layer for the purpose of increasing the sensitivity.

The photographic element of the present invention is composed of a light-sensitive element that forms or releases a dye by heat development and, if necessary, a dye-fixing element that fixes the dye.

Particularly, in a system for forming an image by diffusion transfer of a dye, a light-sensitive element and a dye-fixing element are essential, and as a typical form, the light-sensitive element and the dye-fixing element are separately coated on two supports. The form is roughly divided into a form coated on the same support.

The relationship between the photosensitive element and the dye fixing element, the relationship with the support,
Regarding the relationship with the white reflective layer, see Japanese Patent Application No. 59-268926, pages 58 to 59, and US Pat.
The relationships described in column 7 can be applied to the present application.

A typical form in which the light-sensitive element and the dye-fixing element are coated on the same support is one in which it is not necessary to peel the light-sensitive element from the dye-fixing element after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferable embodiments include, for example, transparent support / photosensitive layer / white reflective layer / dye fixing layer, transparent support / dye fixing layer / white reflecting layer / resistive layer and the like.

Another typical embodiment in which the light-sensitive element and the dye-fixing element are coated on the same support is, for example, JP-A-56-67840.
No., Canadian Patent No. 674082, US Patent No. 3730
No. 718, there is a form in which a part or all of the light-sensitive element is peeled from the dye-fixing element, and a peeling layer is coated at an appropriate position.

The light-sensitive element or the dye-fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of dye.

In this case, the transparent or opaque heating element can be manufactured by using a conventionally known technique as a resistance heating element.

As the resistance heating element, there are a method of using a thin film of a semiconductive inorganic material and a method of using an organic thin film in which conductive fine particles are dispersed in a binder. As materials that can be used in these methods, those described in Japanese Patent Application No. 59-151815 can be used.

The dye-fixing element used in the present invention has at least one layer containing a mordant, and when the dye-fixing layer is located on the surface, a protective layer can be further provided, if necessary.

Regarding the layer constitution of the dye fixing element, the position of the binder, the additive, the mordant addition layer, etc., the description on page 62, line 9 to page 63, line 18 of Japanese Patent Application No. 59-268926 and the patent specifications cited therein. What is described in (1) is applicable to this application.

The dye fixing element used in the present invention may be provided with an auxiliary layer such as a peeling layer, a matting agent layer and an anti-curl layer in addition to the above layers.

In one or more of the above layers, a base and / or base precursor for facilitating dye transfer, a hydrophilic thermal solvent, an anti-fading agent for preventing discoloration of the dye, a UV absorber, a slip agent, a matte. Agents, antioxidants, dispersed vinyl compounds for increasing dimensional stability, optical brighteners and the like may be included. Specific examples of these additives are shown in Japanese Patent Application No. 59-
209563, pages 101-120.

The binder in the above layer is preferably hydrophilic, and is typically a transparent or semitransparent hydrophilic colloid. Specifically, the binders listed above for the photosensitive material are used.

The image receiving layer in the present invention includes a dye fixing layer used in a heat-developable color light-sensitive material, and can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferable. Here, the polymer mordant is a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic portion, a polymer having a quaternary cation group thereof, or the like.

Regarding this specific example, Japanese Patent Application No. 59-268926, 98.
-100 pages and U.S. Pat. No. 4,500,626, Nos. 57-6.
It is described in column 0.

In the present invention, the method for coating the photothermographic layer, protective layer, intermediate layer, undercoat layer, back layer and other layers is described in US Pat. No. 4,500.
The methods described in Columns 55 to 56 of No. 626 can be applied.

As a light source for image exposure for recording an image on a photothermographic material, radiation including visible light can be used,
For example, the light source described in Japanese Patent Application No. 59-268926, page 100, or US Pat. No. 4,500,626, column 56, can be used.

The heating temperature in the heat development step is from about 50 ° C. to about 250 ° C., and development is possible. Particularly, about 80 ° C. to about 180 ° C. is useful, and the heating temperature in the transfer step depends on the temperature in the heat development step. Transfer is possible in the range of room temperature, but it is more preferable that the temperature is 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step. As a heating means in the developing and / or transferring step, a heating plate, an iron, a heating roller, a heating element using carbon, titanium white or the like can be used.

Also, JP-A-59-218443 and Japanese Patent Application No. 60-79.
As described in detail in No. 709 etc., a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of a solvent such as water is also useful. In this method, the above-mentioned image formation accelerator may be contained in advance in either or both of the dye fixing material and the light-sensitive material, or may be supplied from the outside.

In the system in which the development and the transfer are performed simultaneously or continuously, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50 ° C or higher and 100 ° C or lower.

In addition, a solvent may be used to move the movable dye to the dye fixing layer.

Examples of the solvent used for accelerating the development and / or moving the movable dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (for these bases, an image is used). Those described in the section of the formation accelerator are used). Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound, etc. may be contained in the solvent.

These solvents can be used in the method of applying to the dye fixing material or the light-sensitive material or both. The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film).

The solvent (for example, water) accelerates image formation and / or dye transfer by being applied between the photosensitive layer of the photothermographic material and the dye-fixing layer of the dye-fixing material. It can also be used by being incorporated in the dye fixing material or both.

Examples of the method for applying a solvent to the photosensitive layer or the dye fixing layer include, for example, Japanese Patent Application No. 59-268926, page 101, page 9.
Line-Page 102, line 4, there is a method described.

Further, in order to promote dye transfer, a method in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is built into the photosensitive material or the dye fixing material can be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing material, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

The heating means in the transfer process is disclosed in Japanese Patent Application No. 59-26892.
No. 6, page 102, line 14 to page 103, line 11 are available. Alternatively, a layer of a conductive material such as graphite, carbon black or metal may be superposed on the dye fixing material, and an electric current may be passed through the conductive layer to directly heat the conductive layer.

Japanese Patent Application No. 59-2 describes a pressure condition and a method of applying pressure when the heat-developable photosensitive material and the dye-fixing material are superposed and brought into close contact
The method described on pages 103 to 104 of No. 68926 can be applied.

V. Specific Action and Effect of the Invention According to the present invention, since it contains at least one of the compounds represented by the general formula (I), it is a precursor of a developer having good stability over time and good developer release efficiency. By containing, the color photosensitive material and the photothermographic material which are excellent in storability and give an image having a high S / N ratio can be obtained.

VI Specific Examples of the Invention Hereinafter, the present invention will be described in more detail by showing specific examples of the invention.

Example 1 A method for making a silver iodobromide emulsion will be described.

40 g of gelatin and 26 g of KBr were dissolved in 3000 ml of water. This solution was kept at 50 ° C. and stirred. Next, silver nitrate 34
A solution of g in 200 ml of water was added to the above solution in 10 minutes.

Then, a solution prepared by dissolving 13.3 g of K in 100 ml of water was added over 2 minutes.

The pH of the silver iodobromide emulsion thus prepared is adjusted and allowed to settle,
Excess salt was removed.

Thereafter, the pH was adjusted to 6.0 to obtain a yield of 400 g of silver iodobromide emulsion.

Next, a method for preparing a benzotriazole silver emulsion will be described.

28 g of gelatin and 13.2 g of benzotriazole were added to 3 parts of water.
It was dissolved in 00 ml. This solution was kept at 40 ° C. and stirred.
To this solution, add 2 g of a solution of 17 g of silver nitrate in 100 ml of water.
Added in minutes.

The pH of this benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Then adjust the pH to 6.0,
A yield of 400 g of benzotriazole silver emulsion was obtained.

Next, a method for making a gelatin dispersion of the coupler will be described.

2-dodecylcarbamoyl-1-naphthol 10 g, succinic acid-2-ethyl-hexyl ester sodium sulfonate 0.5 g, tricresyl phosphate (TCP) 5
20 g of ethyl acetate was added and dissolved by heating.

This solution and a 10% aqueous gelatin solution were mixed by stirring and then dispersed at 10,000 RPM for 10 minutes with a high speed shearing stirrer. This dispersion is called a coupler dispersion.

Next, how to make a photosensitive material will be described.

(a) Silver iodobromide emulsion 8 g (b) Benzotriazole silver emulsion 4 g (c) 10% gelatin solution 5 g (d) Dispersion of the coupler 3.5 g (e) p = chlorophenylsulfonylacetate 10% of guanidine Water-Ethanol (1: 1) mixed solution 4 ml (f) 10% methyl cellosolve solution of compound 2 of the present invention 3 ml (g) 5% aqueous solution of octaethylene glycol nonylphenol ether 5 ml (h) water 6 ml or more (a) ~ (H) were mixed and dissolved, and then coated on a polyethylene terephthalate film with a wet film thickness of 60 µm and dried.

Further, the following composition was applied thereon as a protective layer.

(A) 10% aqueous solution of gelatin 35 g (b) p-chlorophenylsulfonylacetate 10% water-ethanol (1: 1) mixed solution of guanidine 8 ml (c) 2-ethyl-hexyl succinate 1% of sodium ester sulfonate A light-sensitive material A was prepared by coating a solution prepared by mixing 4 ml of aqueous solution (d) 56 ml of water with a wet film thickness of 25 μm and then drying.

Next, photosensitive materials B to E were prepared in the same manner as described above except that the compounds 3, 4, 6 and 7 of the present invention were used in place of the compound 2 of the present invention in (f). For comparison, a light-sensitive material F containing 4-amino-2,6-dichlorophenol F, 4
A light-sensitive material G using-(N, N-diethylamino) -2-methylaniline was prepared. The photosensitive materials A to G were dried and then imagewise exposed at 2000 lux for 10 seconds using a tungsten bulb. Then, it heated for 30 second on the hotplate heated at 140 degreeC.

As a result, a negative cyan image was obtained on the film. The cyan density of this negative image was measured by a Macbeth transmission densitometer (TD-5
Table 1 shows the results of measurement using No. 04). In addition, the data obtained by measuring the increase in fog density when exposed and developed under the same conditions as above after leaving the light-sensitive materials A to G at 40 ° C. for one week were also shown.

From the above results, the comparative compounds F and G are favorable (Dmax / Dm
in) ratio, but the stability of the photosensitive material is poor,
The compound of the present invention was shown to be stable even after storage.

Example 2 Photosensitive materials H and I were prepared by the same procedure as in Example 1 except that the same amount of the coupler having the following structure was used instead of the coupler of Example 1.

When these photosensitive materials H and I were processed in exactly the same manner as in Example 1, a yellow image was obtained for the photosensitive material H and a magenta negative image was obtained for the photosensitive material I.

The results are shown below.

From these results, the compounds of the present invention have good S values not only for cyan couplers but also for yellow and magenta couplers.
It was found that / N was given and a stable light-sensitive material was given.

Example 3 A dispersion was prepared from the coupler dispersion of Example 1 as follows.

Dye-donor substance of the following structure 10 g, 0.5 g of succinic acid-2-ethyl-hexyl ester sulfonic acid soda and 4 g of tri-cresyl phosphate (TCP) were weighed, and 20 ml of cyclohexanone was added and dissolved by heating. This solution and 10% gelatin aqueous solution 1
After stirring and mixing 00 g, 10 minutes with a homogenizer, 10
Dispersing at 000 RPM made a dispersion of dye-donor material.

A light-sensitive material J was prepared in the same manner as in Example 1 except that this dispersion of the dye-providing substance was used and the wet coating thickness was 30 μm. Comparative compound instead of the compound (2) of the present invention in photosensitive material J A light-sensitive material K was prepared in exactly the same manner except that was used.

Next, how to make the dye fixing material will be described.

10 g of poly (methyl acrylate-co-N, N, N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate to vinylbenzylammonium chloride 1: 1) was dissolved in 180 ml of water to obtain 10
% Lime-treated gelatin 100 g and homogeneously mixed with 20 ml of a 4% aqueous solution of 1,4-bis (2 ', 3'-epoxypropoxy) butane. This mixed solution was uniformly applied on a paper support laminated with polyethylene in which titanium dioxide was dispersed to a wet film thickness of 90 μm. After drying this sample, it is used as a dye fixing material having a mordant tank.

The above light-sensitive materials J and K were imagewise exposed at 2000 lux for 10 seconds using a tungsten bulb. Then 14
Heated uniformly on a heat block heated to 0 ° C. for 30 seconds.

Next, the dye fixing material was immersed in water, and the film surface of the wet dye fixing material and the film surfaces of the photosensitive coating materials A and B which had been subjected to the heat treatment were superposed so as to be in contact with each other. Then 8
After heating for 6 seconds on a heat block at 0 ° C., the dye-fixing material was peeled off from the light-sensitive material to obtain a negative magenta dye on the dye-fixing material. The results of measuring the density of this negative image with respect to green light using a Macbeth reflection densitometer (RD519) and the increase in the fog density after leaving the photosensitive material at 40 ° C. for 1 week are shown below.

It was found that the comparative compound impairs the stability of the light-sensitive material even in the image dye transfer system as in this example, whereas the compound of the present invention gives stable results.

Example 4 Instead of the dye-donor substance of Example 3, a dye-donor substance having the following structure A light-sensitive material O was prepared using the light-sensitive material N and the comparative compound in exactly the same manner as in Example 3 except that 10 g was used and the wet film thickness was 60 μm.

This light-sensitive material was imagewise exposed at 2000 lux for 10 seconds using a tungsten bulb and then heated for 60 seconds on a heat block heated to 180 ° C. After the photosensitive material was cooled to room temperature, the coating material on the polyethylene terephthalate film was physically peeled off to obtain a negative magenta image on the film. The increase in fog density after the photosensitive material was aged for 1 week at 40 ° C. is shown below.

From the above results, it was shown that the light-sensitive material using the compound of the present invention has excellent stability even in the thermal transfer system of the hydrophobic dye as in this example.

Continuation of the front page (56) Reference JP 61-53634 (JP, A) JP 58-95338 (JP, A) JP 60-230134 (JP, A) JP 62-178246 (JP , A) JP-A-57-138630 (JP, A) JP-B 1-15054 (JP, B2) JP-B 3-62257 (JP, B2) US Pat. No. 3342597 (US, A)

Claims (2)

[Claims] 1. A support comprising at least one of a photosensitive silver halide, a coupler capable of binding with an oxidized product of a developer, a hydrophilic binder and a compound represented by the following general formula (I). A color light-sensitive material characterized by. General formula (I) {In the above general formula (I), R ₁ , R ₂ , R ₃ and R
₄ is a hydrogen atom, a halogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aralkyl group, amino group,
It represents an alkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aryl group, a carbamoyl group, a sulfamoyl group, an acyl group, an acyloxy group or an alkoxycarbonyl group. Further, R ₁ and R ₂ or R ₃ and R ₄ may be linked to each other to form a ring. A is a hydroxyl group, a group that gives a hydroxyl group by the action of a nucleophile, or (Here, R ₆ and R ₇ each represent a hydrogen atom, or a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group or aralkyl group, and R ₆ and R ₇
May combine to form a heterocycle). Also, A In the case of, one or both of (R ₁ and R ₆ ) and (R ₃ and R ₇ ) may be linked to form a heterocycle. R ₅ represents a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aralkyl group or aryl group. } 2. A support containing at least one of a photosensitive silver halide, a coupler capable of binding with an oxidized product of a developing agent, a hydrophilic binder and a compound represented by the following general formula (I). A photothermographic material characterized by: General formula (I) {In the above general formula (I), R ₁ , R ₂ , R ₃ and R
₄ is a hydrogen atom, a halogen atom, a hydroxyl group, or a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aralkyl group, amino group,
It represents an alkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aryl group, a carbamoyl group, a sulfamoyl group, an acyl group, an acyloxy group or an alkoxycarbonyl group. Further, R ₁ and R ₂ or R ₃ and R ₄ may be linked to each other to form a ring. A is a hydroxyl group, a group that gives a hydroxyl group by the action of a nucleophile, or (Here, R ₆ and R ₇ each represent a hydrogen atom, or a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group or aralkyl group, and R ₆ and R ₇
May combine to form a heterocycle). Also, A In the case of, one or both of (R ₁ and R ₆ ) and (R ₃ and R ₇ ) may be linked to form a heterocycle. R ₅ represents a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aralkyl group or aryl group. }