JPH0690488B2 - Thermal development color photosensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-developable color light-sensitive material capable of obtaining a high maximum density and having less fog. .

[Prior art]

The method in which the development process for obtaining a color image is performed by dry heat treatment has many advantages in comparison with the conventional wet method in terms of processing time, cost, and concern about pollution. Therefore, many proposals have been made in recent years regarding such a heat-developable color light-sensitive material, for example, JP-A-57-1798.
40, 57-186744, 57-198458, 57-207250
No. 58-40551, No. 58-58543, No. 58-79247, JP-A No. 59-12431, No. 59-22049, and Japanese Patent Application No. 57-17.
9236, 57-229671, 57-229674, 57-2296
No. 75, No. 58-33363, No. 58-33364, No. 58-34083
No. 58-116537, 58-123533, 58-1490.
There are 46 and 58-149047.

The basic constitution of the heat-developable color light-sensitive material according to these prior proposals consists of a light-sensitive element and an image-receiving element, and the light-sensitive element basically comprises an organic silver salt, a photosensitive silver halide, a developer (reducing agent),
It comprises a dye-providing compound and a binder. That is, light information is given to the photosensitive silver halide by imagewise exposure, and in thermal development, dissolution physical development according to the light information is performed between the organic silver salt and the photosensitive silver halide under the action of the developer. The developed or unacted developer reacts with the dye-donor compound to release or form the image-forming dye. The image forming dye obtained by heat development is transferred to an image receiving element to form an image.

Among the above organic silver salts, a silver salt of benzotriazole or a derivative thereof (hereinafter referred to as benzotriazole-based silver salt) has high solubility and physical developability, and is not limited to a hydrophobic binder but to a hydrophilic binder. Is also suitable for a heat-developable color light-sensitive material, because the heat-development temperature can be made higher than that of other silver salts, and thermal transfer of the image-forming dye is advantageous. Is.

However, when trying to obtain a sufficiently high maximum concentration,
There is a drawback that fogging is large. It is difficult to greatly reduce the fog even by using an ordinary antifoggant for a silver halide photosensitive material or a known antifoggant for a photothermographic material.

[Purpose of the present invention]

Therefore, an object of the present invention is to provide a heat-developable color light-sensitive material capable of obtaining a high maximum density and having less fog.

[Structure of Invention]

The present inventors have conducted extensive studies to achieve the above object, and as a result, at least (a) photosensitive silver halide,
(B) benzotriazole-based organic silver salt, (c) developer,
In a photothermographic color photosensitive material having at least one photothermographic layer containing (d) a dye-donor compound and (e) a binder, at least one layer of the photothermographic layer is:
The benzotriazole-based organic silver salt 1 may be a benzotriazole having benzotriazole having at least one hydrophilic group selected from a hydroxy group, a carboxy group, a sulfo group, a carbamoyl group or a sulfamoyl group as a substituent on a benzene ring.
It has been found to be achieved by a heat-developable color light-sensitive material characterized by containing 0.01 to 2 mol per mol.

It should be noted that Japanese Patent Publication No. 57-27445 describes that an unsubstituted or lower alkyl, halogen- or nitro-substituted benzotriazole is added, but these unsubstituted or hydrophobic benzotriazoles are effective in reducing fog. However, the use of a large amount may rather lower the maximum concentration. The benzotriazole having a hydrophilic group of the present invention is excellent in reducing only fog without causing a decrease in maximum concentration.

Specific examples of the benzotriazole having a hydrophilic group used in the present invention are shown below.

(1) 4-hydroxybenzotriazole (2) 5-hydroxybenzotriazole (3) 4-sulfobenzotriazole (4) 5-sulfobenzotriazole (5) 4-carboxybenzotriazole (6) 5-carboxybenzotriazole (7) ) 5-carbamoylbenzotriazole (8) 4-sulfamoylbenzotriazole (9) 5-carboxy-6-hydroxybenzotriazole (10) 5-carboxy-7-sulfobenzotriazole (11) 4-hydroxy-5-sulfo Benzotriazole (12) 4-hydroxy-7-sulfobenzotriazole (13) 5,6-dicarboxybenzotriazole (14) 4,6-dihydroxybenzotriazole (15) 4-hydroxy-5-chlorobenzotriazole (16) 4-hydroxy-5 Methylbenzotriazole (17) 4-hydroxy-5-methoxybenzotriazole (18) 4-hydroxy-5-nitrobenzotriazole (19) 4-hydroxy-5-cyanobenzotriazole (20) 4-hydroxy-5-aminobenzo Triazole (21) 4-Hydroxy-5-acetamidobenzotriazole (22) 4-Hydroxy-5-hydroxycarbonylmethoxybenzotriazole (23) 4-Hydroxy-5-carboxymethylbenzotriazole (24) 4-Hydroxy-5-phenyl Benzotriazole (25) 4-sulfo-5-chlorobenzotriazole (26) 4-sulfo-5-methylbenzotriazole (27) 4-sulfo-5-methoxybenzotriazole (28) 4-sulfo-5-cyanobenzotriazole (29) 4-sul Phosphoro-5-aminobenzotriazole (30) 4-sulfo-5-acetamido benzotriazole (31) 4-hydroxy-5-carboxybenzotriazole (32) 4-sulfo-5-phenylbenzotriazole (33) 4-sulfo- 5-Methoxy-6-chlorobenzotriazole (34) 4-sulfo-5-chloro-6-carboxybenzotriazole (35) 4-carboxy-5-chlorobenzotriazole (36) 4-carboxy-5-methylbenzotriazole (36) 37) 4-carboxy-5-nitrobenzotriazole (38) 4-carboxy-5-aminobenzotriazole (39) 4-carboxy-5-methoxybenzotriazole (40) 4-carboxy-5-acetamidobenzotriazole (41) 4-carboxy-5-phenylbenzotriazo (42) 4-Carboxy-5-methyl-7-sulfobenzotriazole (43) 4,6-disulfobenzotriazole (44) 4-sulfo-6-chlorobenzotriazole The benzotriazole having these hydrophilic groups is benzotriazole. 0.01 mol to 2 mol is added to 1 mol of the triazole organic silver salt. Regarding the addition of benzotriazole having a hydrophilic group, it may be the same as or different from the benzotriazoles constituting the benzotriazole-based organic silver salt, but preferable. Further, benzotriazole having a hydrophilic group is
They may be added alone or in combination of two or more.

The benzotriazole having a sulfo group or a carboxy group may be in the state of a sulfonic acid group or a carboxylic acid group, or in the state of sodium salt, potassium salt, ammonium salt or the like.

(A) Photosensitive silver halide The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like. Particle size is 0.01μm-1.0μm, preferably 0.05μm
Is 0.5 μm. The shape of silver halide is regular tetrahedron,
Although there are regular octahedrons, tetrahedrons, etc., those having at least a (111) plane are preferable. Further, it may be a core-shell type in which the halogen composition is different between the inside and the outside of the grain.

The photosensitive silver halide used in the present invention is preferably chemically sensitized. Including sulfur sensitization and selenium sensitization,
You may combine the sensitization by compounds, such as gold, platinum, and palladium. Further, it may be spectrally sensitized with a spectral sensitizing dye as used in a usual silver halide color light-sensitive material.

(B) Benzotriazole Organic Silver Salt Examples of the benzotriazole silver salt include alkyl-substituted benzotriazole silver such as benzotriazole silver and methylbenzotriazole silver, and halogen such as bromobenzotriazole silver and chlorobenzotriazole silver. Substituted benzotriazole silver, for example amido-substituted benzotriazole silver such as 5-acetamidobenzotriazole silver, and British Patents 1,590,956 and 1,590,957.
No. 6-chloro-4-N-, for example N- [6-chloro-4-N-
(3,5-dichloro-4-hydroxyphenyl) imino-
1-oxo-5-methyl-2,5-cyclohexadiene-
2-yl] -5-carbamoylbenzotriazole silver salt, 2-benzotriazol-5-ylazo-4-methoxy-1-naphthol silver salt, 1-benzotriazole-
5-ylazo-2-naphthol silver salt, N-benzotriazol-5-yl-4- (4-dimethylaminophenylazo) benzoamide silver salt and the like can be mentioned.

Organic silver salts particularly useful in the present invention are disclosed in JP-A-58-118638.
No. 4,849,629, which has a hydrophilic group.

For example, 4-hydroxybenzotriazole silver, 5-hydroxybenzotriazole silver, 4-sulfobenzotriazole silver, 5-sulfobenzotriazole silver, benzotriazole silver-4-sulfonate, benzotriazole silver-5-sulfonate, benzo Silver triazol-4-sulfonate, potassium benzotriazole-5-sulfonate, ammonium benzotriazole-4-sulfonate, ammonium benzotriazole-5-sulfonate, silver 4-carboxybenzotriazole, 5-carboxybenzo Triazole silver, sodium benzotriazole-4-carboxylate, sodium benzotriazole-5-carboxylate, potassium benzotriazole-4-carboxylate,
Benzotriazole silver-5-carboxylate potassium, benzotriazole silver-4-carboxylate ammonium, benzotriazole silver-5-carboxylate ammonium, 5-
Carbamoylbenzotriazole silver, 4-sulfamoylbenzotriazole silver, 5-carboxy-6-hydroxybenzotriazole silver, 5-carboxy-7-sulfobenzotriazole silver, 4-hydroxy-5-sulfobenzotriazole silver, 4-hydroxy -7-sulfobenzotriazole silver, 5,6-dicarboxybenzotriazole silver, 4,6-dihydroxybenzotriazole silver,
4-hydroxy-5-chlorobenzotriazole silver, 4
-Hydroxy-5-methylbenzotriazole silver, 4-
Hydroxy-5-methoxybenzotriazole silver, 4-
Hydroxy-5-nitrobenzotriazole silver, 4-hydroxy-5-cyanobenzotriazole silver, 4-hydroxy-5-aminobenzotriazole silver, 4-hydroxy-5-acetamidobenzotriazole silver, 4-hydroxy-5-benzenesulfone Amidobenzotriazole silver, 4-hydroxy-5-hydroxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-
Hydroxy-5-carboxymethylbenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethylbenzotriazole silver, 4-hydroxy-5-phenylbenzotriazole silver, 4-hydroxy-5- (p-nitrophenyl) benzotriazole silver, 4-hydroxy-
5- (p-sulfophenyl) benzotriazole silver, 4
-Sulfo-5-chlorobenzotriazole silver, 4-sulfo-5-methylbenzotriazole silver, 4-sulfo-5
-Methoxybenzotriazole silver, 4-sulfo-5-cyanobenzotriazole silver, 4-sulfo-5-aminobenzotriazole silver, 4-sulfo-5-acetamidobenzotriazole silver, 4-sulfo-5-benzenesulfonamide benzotriazole Silver, 4-sulfo-5-hydroxycarbonylmethoxybenzotriazole silver, 4-
Sulfo-5-ethoxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-carboxybenzotriazole silver, 4-sulfo-5-carboxymethylbenzotriazole silver, 4-sulfo-5-ethoxycarbonylmethylbenzotriazole silver, 4-sulfo -5-Phenylbenzotriazole silver, 4-sulfo-5- (p-nitrophenyl) benzotriazole silver, 4-sulfo-5-
(P-Sulfophenyl) benzotriazole silver, 4-sulfo-5-methoxy-6-chlorobenzotriazole silver, 4-sulfo-5-chloro-6-carboxybenzotriazole silver, 4-carboxy-5-chlorobenzotriazole silver , 4-carboxy-5-methylbenzotriazole silver, 4-carboxy-5-nitrobenzotriazole silver, 4-carboxy-5-aminobenzotriazole silver, 4-carboxy-5-methoxybenzotriazole silver, 4-carboxy-5 -Acetamidobenzotriazole silver, 4-carboxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-carboxy-5-carboxymethylbenzotriazole silver, 4-carboxy-5-phenylbenzotriazole silver, 4-carboxy-5- (p -Nitro Eniru) benzotriazole silver,
4-carboxy-5-methyl-7-sulfobenzotriazole silver etc. can be mentioned. These compounds may be used alone or in combination of two or more kinds.

The isolated organic silver salt according to the present invention may be used by dispersing it in a binder for a photosensitive layer by an appropriate means. Alternatively, a silver salt may be prepared in a binder for a photosensitive layer to prepare a single salt. You may use it as it is without separating it.

The amount of the organic silver salt used is 0.05 g to 10.0 g, and preferably 0.2 g to 5.0 g per 1 m ² of the support.

(C) Developer (Reducing Agent) Examples of the developer used in the heat-developable color photosensitive element of the present invention include U.S. Pat. No. 3,531,286, U.S. Pat. No. 3,761,270 and U.S. Pat.
764,328, RD12146, 15108, 15127 and JP-A-56
-27132 and the like, p-phenylenediamine system and p
-Aminophenol-based developing agents, phosphoramidophenol-based and sulfonamidephenol-based developing agents,
Further, a hydrazone type color developing agent is disclosed in JP-A-57-186744.
JP-A-59-12431, JP-A-59-15941, Japanese Patent Application No. 57-160698
No. 58-33363, No. 58-33364 and the like can be advantageously used in the case of the thermal transfer dye-providing compound.
In this case, diffusible dyes are released or formed by oxidative coupling of the developer and these thermal transfer dye-donor compounds. The color developing agent precursors described in U.S. Pat. Nos. 3,342,599 and 3,719,492, JP-A-53-135628 and JP-A-54-79035 can also be advantageously used.

In the present invention, a sulfamic acid type developer as disclosed in JP-A-56-146133 is particularly effective.

Other color systems include, for example, JP-A-57-179840.
No. 57-102487, Japanese Patent Application No. 57-229648, 57-2296.
No. 72, No. 57-225928, etc., and these do not necessarily need to use the above-mentioned developers, and the developers described below can be used.

That is, phenols (for example, p-phenylphenol, p
-Methoxyphenol, 2,6-di-t-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamide phenols [for example, 4-benzenesulfonamidephenol, 2-benzenesulfonamidephenol, 2 , 6-Dichloro-4-benzenesulfonamidephenol, 2,6-dibromo-4- (p-toluenesulfonamide) phenol, etc.] or polyhydroxybenzenes (for example, hydroquinone, t-butylhydroquinone, 2,6-dimethyl) Hydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-
Carboxycatechol etc.), naphthols (eg α-
Naphthol, β-naphthol, 4-aminonaphthol,
4-methoxynaphthol, etc.), hydroxybinaphthyls and methylenebisnaphthols [for example, 1,1′-dihydroxy-2,2′-binaphthyl, 6,6′-dibromo-2,
2'-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2,2'-dihydroxy-1,1'-binaphthyl, 4,
4'-dimethoxy-1,1'-dihydroxy-2,2'-binaphthyl, bis (2-hydroxy-1-naphthyl) methane, etc.] methylene bisphenols [e.g. 1,1-bis (2-hydroxy-3, 5-dimethylphenyl) -3,5,5-
Trimethylhexane, 1,1-bis (2-hydroxy-3
-T-butyl-5-methylphenyl) methane, 1,1-bis (2-hydroxy-3,5-di-t-butylphenyl)
Methane, 2,6-methylenebis (2-hydroxy-3-t
-Butyl-5-methylphenyl) -4-methylphenol-α-phenyl-α, α-bis (2-hydroxy-3,
5-di-t-butylphenyl) methane, α-phenyl-
α, α-bis (2-hydroxy-3-t-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-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-di-
t-butylphenyl) propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines.

These developers may be used alone or in combination of two or more kinds. The amount of the developer used depends on the type of the organic silver salt used, the type of the photosensitive silver halide and the types of other additives, etc.
It is in the range of 0.05 mol to 10 mol, preferably 0.1 mol to
3 mol.

(D) Dye-donor compound Examples of the dye-donor compound which can be used in the heat-developable color light-sensitive material of the present invention include those disclosed in JP-A-57-179840.
57-186744, 58-116537, 58-123533, 57
-149046, Japanese Patent Application Nos. 57-122596, 57-160698, and
57-205447, 57-224883, 57-224884, 57
-229671, 57-229647, 57-225929, 58-
Examples of dye-donor compounds that can be used in the diffusion transfer type photothermographic materials described in Nos. 33363, 58-33364, 58-34083 and the like.

The dye-providing compound preferably used in the present invention is a dye-forming compound and can be represented by the following general formula (I).

In the general formula (I) Cp-X formula, Cp represents a coupler residue excluding an active hydrogen atom, and Cp represents a hydrophilic group such as a sulfo group or a carboxy group and such a hydrophilic group other than the active position. It is a coupler residue having no group contained. X represents a group capable of splitting off from the coupler during the coupling reaction, and X has at least one hydrophilic group such as a sulfo group or a carboxy group or a group containing these hydrophilic groups. Has a linear or branched alkyl group having 8 or more carbon atoms.

Examples of the coupler residue represented by Cp include those represented by the following general formulas (II) to (VII).

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom or an iodine atom), an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms). Examples thereof include groups such as methyl, ethyl, butyl, t-octyl, n-dodecyl, n-pentadecyl, cyclohexyl, and the like. Further, an aryl group such as a benzyl group or phenethyl group as an alkyl group substituted with a phenyl group. A group), a substituted or unsubstituted aryl group (eg, phenyl group, naphthyl group, tolyl group, mesityl group), an acyl group (eg, acetyl group, tetradecanoyl group, piparoyl group, substituted or unsubstituted) Benzoyl group), alkyloxycarbonyl group (eg methoxycarbonyl group, benzyloxycarbonyl group), aryloxy group Rubonyl group (eg, phenoxycarbonyl group, p-tolyloxycarbonyl group, α-naphthoxycarbonyl group), alkylsulfonyl group (eg, methylsulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group), carbamoyl group (eg, substituted or non-substituted) Substituted alkylcarbamoyl group, methylcarbamoyl group, butylcarbamoyl group, tetradecylcarbamoyl group, N-methyl-N-dodecylcarbamoyl group, optionally substituted phenoxyalkylcarbamoyl group, specifically 2,4-di-t -Phenoxybutyl-carbamoyl group, substituted or unsubstituted phenylcarbamoyl group, specifically 2-dodecyloxyphenylcarbamoyl group, etc.), substituted or unsubstituted acylamino group (for example, n-butylamide group, ularylamide group) Which may be substituted also β- phenoxyethyl amide group, phenoxy acetamide group, a substituted or unsubstituted benzamide group,
Methanesulfonamide ethylamide group, β-methoxyethylamide group), alkoxy group (preferably having a carbon number of 1 to 1)
18 alkoxy groups such as methoxy group, ethoxy group, octadecyloxy group), flufamoyl group (eg methylsulfamoyl group, n-dodecylsulfamoyl group,
It represents a substituted or unsubstituted phenylsulfamoyl group, specifically a dodecylphenylsulfamoyl group), a sulfonylamino group (for example, a methylsulfonylamino group, a tolylsulfonylamino group) or a hydroxyl group. R ₁ and R ₂ may combine with each other to form a saturated or unsaturated 5- or 6-membered ring.

R ₅ is an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, for example, methyl group, butyl group, heptadecyl group),
Substitution of an alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, for example, a methoxy group, an ethoxy group, an octadecyloxy group), an arylamino group (for example, an anilino group, further a halogen atom, an alkyl group, an amide group or an imide group) Group-substituted anilino group), a substituted or unsubstituted alkylamide group (eg, ularylamide, optionally substituted phenoxyacetamide, phenoxybutanamide group), a substituted or unsubstituted arylamide group (eg, benzamide group, further Halogen atom,
And a benzamide group substituted with an alkyl group, an alkoxy group, an amide group or the like.

Further, R ₆ , R ₇ and R ₈ are each a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom or an iodine atom), an alkyl group (preferably an alkyl group having 1 to 2 carbon atoms such as a methyl group or an ethyl group). A group such as a substituted or unsubstituted alkylamide group (eg, ularylamide group, optionally substituted phenoxyalkylamide group, eg, alkyl-substituted phenoxyacetamide group), a substituted or unsubstituted arylamide group (eg, benzoylamide group), etc. Represent.

Next, R ₉ is an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms (eg, methyl group, butyl group, octyl group), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, methoxyphenyl group)) And so on.

Further, R ₁₀ is an arylamino group (for example, an anilino group,
Further, it represents an anilino group substituted with a halogen atom, an alkyl group, an alkoxy group, an alkylamido group, an arylamido group, an imide group or the like.

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are the same as the groups represented by R ₁ and R ₂ above.

Typical examples of the dye-donor compound represented by the general formula (I) include the following compounds.

[Exemplary dye-donor compound]

The dye-donor compound used in the present invention varies depending on the photothermographic composition, coating conditions, processing method and the like, but is generally used in an amount of 0.01 to 10 mol, preferably 0.1 mol, per mol of the organic silver salt. ~ 2.0 moles.

The dye-donor compound used in the present invention is used by being contained in the photothermographic layer or other photographic constituent layers. For example, in order to include it in the photothermographic layer, it is described in U.S. Pat.No. 2,322,027 regarding the dispersion method of couplers. As described above, it can be contained by being dissolved in a high boiling point solvent. Further, in the dispersion method as described above, a low-boiling solvent may be used in combination with the high-boiling solvent, if necessary, to dissolve the dye-donor compound and allow the dye-developing compound to be contained in the photothermographic layer.

Examples of the high boiling point solvent include di-n-butyl phthalate, tricresyl phosphate, dioctyl phthalate, n-nonylphenol, and the like, and examples of the low boiling point solvent include methyl acetate and butyl propionate.
Cyclohexanol, diethylene glycol monoacetate and the like are known. These solvents may be used alone or as a mixture, and the dye-donor compound thus dissolved in the solvent may be an anionic surfactant such as alkylbenzenesulfonic acid or alkylnaphthalenesulfonic acid and / or sorbitan. It can be mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing a nonionic surfactant such as monolauric acid ester, emulsified and dispersed by a colloid mill or an ultrasonic dispersion device, and added to the photothermographic layer.

The high boiling point solvent is used in an amount that completely dissolves the dye-donor compound, but preferably it is used in an amount of 0.05 to 100 parts with respect to 1 part of the dye-donor compound.

Fisher dispersion is a preferred dispersion method other than the above. The Fischer dispersion means that a dye-providing compound having a hydrophilic component and a hydrophobic component in the same molecule is dissolved and dispersed in an alkaline aqueous solution. Upon this dissolution and dispersion, an organic solvent compatible with water is added, heated and stirred (homogenizer, ultrasonic dispersion, etc.),
Alternatively, it may be aided by a surfactant. As the alkali of the aqueous alkali solution, an inorganic base or an organic base compatible with water can be used. After the dye-donor compound is dissolved and dispersed, the pH can be adjusted if necessary. In this case, an organic or inorganic acid compatible with water can be used as the pH adjuster. The surfactant as the dispersion aid may be an anionic or nonionic surfactant, but an anionic or activator is preferred.

Note that the Fisher dispersion is sometimes called Agfar dispersion, and British Patents 455,55, 465,823, and 29
The technical contents described in No. 8,97 etc. can be referred to.

(E) Binder A hydrophilic binder is used as the binder used in the heat-developable photosensitive layer of the heat-developable color photosensitive material of the present invention, but a hydrophobic binder may be used in combination. The hydrophilic binder in the present invention means one that is soluble in water or a mixed liquid of water and an organic solvent (a solvent that is miscible with water). For example, gelatin, proteins such as gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, natural substances such as gum arabic, and effective polymers include polyvinyl acetal (preferably having an acetalization degree of 20% or less, such as polyvinyl butyral). , Polyacrylamide, polyvinylpyrrolidone, ethyl cellulose, polyvinyl alcohol (saponification ratio is 75
% Or more) is preferable, but not limited thereto. If necessary, two or more kinds may be mixed and used. Particularly, it is preferable to use a mixture of gelatin or a gelatin derivative and an organic polymer substance such as polyvinylpyrrolidone or polyvinyl alcohol. The amount of the binder is 1/10 to 10 parts by weight, preferably 1/4 to 4 parts by weight with respect to 1 part (parts by weight) of the organic silver salt for each photosensitive layer.

The binder used in each layer (hydrophilic colloid) other than the light-sensitive layer of the heat-developable color light-sensitive element of the present invention is not particularly limited, and various binders can be used. Suitable binders are hydrophilic or hydrophobic. A binder having a volatile property can be optionally used according to the purpose. For example, gelatin, gelatin derivatives, casein, casein sodium,
Proteins such as albumin, cellulose derivatives such as ethyl cellulose, polysaccharides such as dextran,
Polysaccharides such as agar, natural substances such as gum arabic and gum tragacanth, polyvinyl alcohol, polyvinylpyrrolidone, synthetic polymers such as water-soluble polyvinyl acetal, and latex-like vinyl compounds that increase the dimensional stability of photographic materials. And the following synthetic polymers may be included. Suitable synthetic polymers include U.S. Pat.
142,586, 3,193,386, 3,062,674, 3,220,8
No. 44, No. 3,287,289, No. 3,411,911. Effective polymers include water-insoluble polymers based on alkyl acrylates or methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, and the like. Suitable polymeric substances include polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate, potamethyl methacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber polyisobutylene, butadiene styrene copolymer, vinyl. Examples thereof include chloride-vinyl acetate copolymer, vinyl acetate-vinyl chloride-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose propionate, and cellulose acetate phthalate. If necessary, two or more kinds may be mixed and used.

(F) Other Additives Various additives may be added to the heat-developable color light-sensitive material of the present invention, if necessary, in addition to the above components. For example, as a development accelerator, U.S. Patent Nos. 3,220,846 and 3,531,285
No. 4,012,260, 4,060,420, 4,088,496,
The 4,207,392 Patent, or RD15733, the 15734, the alkaline release agents described in such 15776, organic acids described in JP-B-45-12700, described in U.S. Pat. No. _{3,667,959 -CO -, - SO 2 -} , -
Examples of the non-aqueous polar solvent compound having an SO-group and color tone adjusting agents include, for example, JP-A-46-4928, JP-A-46-6077 and JP-A-46-6077.
49-5019, 49-5020, 49-91215, 49-107
727, 50-2524, 50-67132, 50-67641
No. 50, No. 50-114217, No. 52-33722, No. 52-99813,
53-1020, 53-55115, 53-76020, 53-
125014, 54-156523, 54-156524, 54-15
6525, 54-156526, 55-4060, 55-4061
No. 55-32015, etc. and West German Patent No. 2,140,406,
2,147,063, 2,220,618, U.S. Patent 3,080,254,
No. 3,847,612, No. 3,782,941, No. 3,994,732, No. 4,1
Nos. 23,282, 4,201,582 and the like, which are compounds described in phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, 2,3- Dihydro-1,3-oxazine, 2,4
-Dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4- (3H)
Dione, benzotriazine, mercaptotriazole,
There are dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., and a mixture of one or more of these with an imidazole compound or at least one of an acid or acid anhydride such as phthalic acid, naphthalic acid and Examples thereof include a mixture of phthalazine compounds, and a combination of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, or the like. Further, JP-A-58-189628,
3-Amino-5-mercapto-1,2,4-triazoles and 3-acylamino-5 described in JP-A-58-193460.
-Mercapto-1,2,4-triazoles are also effective.

Further, as an antifoggant, for example, Japanese Patent Publication No. 47-11
113, JP-A-49-90118, JP-A-49-10724, JP-A-49-976
No. 13, No. 50-101019, No. 49-130720, No. 50-123331
No. 51-47419, No. 51-57435, No. 51-78227,
51-104338, 53-19825, 53-20923, 51
-50725, 51-3223, 51-42529, 51-8112
No. 4, No. 54-51821, No. 55-93149, etc., and British Patent No. 1,455,271, U.S. Patent No. 3,885,968, No. 3,700,457.
, 4,137,079, 4,138,265, West German patent 2,617,90
No. 7, etc., the mercuric salts of compounds, or oxidizing agents (for example, N-halogenoacetamide, N-halogenosuccinimide, perchloric acid and its salts, inorganic peroxides, persulfates, etc. ) Or an acid and a salt thereof (for example, sulfinic acid, lithium laurate, rosin, diterpenic acid, thiosulfonic acid, etc.), or a sulfur-containing compound (for example, a mercapto compound-releasing compound, thiouracil, disulfide, sulfur simple substance, mercapto-1). , 2,4-triazole,
Thiazoline thione, polysulfide compounds and the like), and other compounds such as oxazoline, 1,2,4-triazole and phthalimide.

As the stabilizer, a print-out preventing agent which prevents print-out after processing may be used at the same time. For example, JP-A-48-45228, JP-A-50-119624, and JP-A-50-12032 may be used.
No. 8, halogenated hydrocarbons described in the same No. 53-46020,
Specifically, tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2,4-bis (tribromomethyl) -6-methyltriazine and the like can be mentioned.

Examples of the hot solvent include urea derivatives, amide derivatives, polyethylene glycols and polyhydric alcohols.

Polyethylene glycol has a molecular weight of 200 to 10,000
0 is preferable.

Specific examples of the urea derivative include urea, thiourea, 1,3-dimethylurea, 1,3-diethylurea, diethyleneurea and 1,3.
-Diisopropylurea, 1,3-dibutylurea, 1,1-dimethylurea, 1,3-dimethoxyethylurea, 1,3-dimethylthiourea, 1,3-dibutylthiourea, tetramethylthiourea, phenylurea, tetramethylurea , Tetraethylurea, etc.

Specific examples of the amide derivative include acetamide, propionamide, n-butylamide, i-butylamide, benzamide, diacetamide, dimethylformamide, acetanilide, ethylacetamide acetate, malonamide, 2-chloropropionamide, 3-chloropropionamide, phthalimide, Succinimide, N, N-
Dimethylacetamide and the like.

Specific examples of the polyhydric alcohol include 1,6-hexanediol, D-xylitol, pentaerythritol and 1,4-
There are cyclohexanediol, 1,2-cyclohexanediol, 2,2'-dihydroquinobenzophenone, 1,5-pentanediol, 1,8-octanediol and the like.

The content of the thermal solvent in the present invention is 5% to 500%, preferably 10% to 300% of the binder amount in the photosensitive layer. The hot solvent of the present invention may be used alone or in combination of two or more.

In the present invention, as the hardener for the hydrophilic binder, a usual gelatin hardener is preferably used, and for example, the following compounds are used.

Inorganic salts such as chromium alum and chromium acetate; formalin,
Aldehydes such as glyoxal and glutaraldehyde; N-methylols such as dimethylolurea and methyloldimethylhydantoin; 2,3-butanedione, 1,2
-Ketones such as cyclopentanedione; carbamic acids such as dimethylcarbamoylpyridinium chloride; sulfonates such as trimethylenebis (methanesulfonate); sulfonyl halides such as ethylenebis (sulfonylfluoride); bis (2-chloroethyl) Urea, 2,4-dichloro-6-hydroxy-s
-Active halogens such as triazines; mucohalogen acids such as mucochloric acid, mucobromic acid, mucophenoxycyclolic acid; epoxies such as diglycidyl ether; aziridines such as triethylenemelamine, hexamethylenebis (aziridinylcarboxamide) 1-ethyl-3-
(3'-dimethylaminopropyl) carbodiimide hydrochloride; such as 1,3-bis (acryloyl) urea, divinyl ketone, diacrylamide, 1,3,5-triacryloylhexahydro-s-triazine bis (vinylsulfonyl) ether Activated olefins: polymer curing agents having functional groups such as partial esters of polyvinyl alcohol and maleic acid, and copolymers of glycidyl acrylate.

Regarding the above-mentioned curing agents, JP-A-51-78788 and JP-A-53-1
39689, 56-27135, U.S. Patents 3,843,372, 1,8
70,354, 2,080,019, 2,726,162, 2,870,01
No. 3, No. 2,983,611, No. 2,992,109, No. 3,047,394,
3,057,723, 3,103,437, 3,321,313, 3,3
25,287, 3,362,827, 3,543,292, British Patent 67
6,628, 825,544, 1,270,578, German patent 67
2,153, 1,090,427, Japanese Patent Publication No. 34-7133, 46-18
No. 72 and Research Disclosure Vol. 176, p. 26 (1978
Dec.) etc.

As a particularly preferred curing agent, U.S. Patent 3,868,257,
4,088,495, 4,134,765, 4,137,082, 4,1
61,407, JP-A-49-116154, 49-118746, 53
-57257, 53-666960, 58-50535, 47
Examples thereof include compounds having at least two vinylsulfonyl groups in the molecule, such as those described in No. -24259 and No. 49-13563.

Furthermore, U.S. Patents 3,301,678, 3,506,444, 3,
Isothiuronium stabilizer precursors described in 824,103 and 3,844,788, and U.S. Pat.
No. 4,012,260, No. 4,060,420 and the like, which may contain activator stabilizer precursors and the like.

In addition to the above components, the heat-developable color photosensitive element of the present invention may further contain various additives such as a spectral sensitizing dye, an antihalation dye, a fluorescent sensitizer, an antistatic agent, a plasticizer, and a spreader. , Coating aids and the like may be added.

The light-sensitive layer of the heat-developable color light-sensitive material of the present invention basically comprises three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, and absorbs the three primary colors of light, blue light, green light and red light, respectively. . These three layers release or form dyes corresponding to the three primary colors of yellow, magenta, and cyan by thermal development.

Basically, the blue-sensitive layer forms or releases a yellow dye, the green-sensitive layer forms a magenta dye, and the red-sensitive layer forms a cyan dye, but the combination is not necessarily limited to this combination.

The photosensitive layer may be divided into two or more layers (for example, a high sensitivity layer and a low sensitivity layer) and coated.

In addition to the photosensitive layer, the heat-developable color photosensitive element of the present invention may be provided with various photographic constituent layers such as an overcoat layer, an undercoat layer (undercoat layer), a backing layer, an intermediate layer or a filter layer according to the purpose. .

(G) Support The photosensitive layer and other photographic constituent layers of the present invention can be coated on a wide variety of supports. As the support used in the present invention, cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polyamide film, polyethylene film, polyethylene terephthalate film, plastic film such as polycarbonate film, metal such as aluminum, glass or paper. It is also possible to use baryta paper, synthetic paper, or the like.

Among these supports, those having a small thermal expansion and contraction rate are preferable.

<Structure of Image-Receiving Element> The light-sensitive element of the present invention gives a color image to the image-receiving element by imagewise exposure, development by heat treatment and thermal transfer to the image-receiving element in a stacking relationship with the light-sensitive element.

The above-mentioned image receiving element basically has a function of stopping the transfer of the imagewise distribution of the dye that has been thermally transferred and fixing it.

For example, it may be simply a layer of gelatin or other synthetic polymer, or a layer of wood pulp or other synthetic pulp fiber. Also, various mordants may be used. Further, the image receiving element may include the image receiving element on a suitable support, and the support may also serve as the image receiving element. Further, the image receiving layer (element)
May be formed on the same support as the support of the photosensitive element described above.

Further, after the dye image is transferred to the image receiving element, the image receiving element may be peeled off or may be integrated with the photosensitive layer. In addition, an opacifying layer (reflective layer) may optionally be included to reflect the desired degree of radiation, such as visible light, that may be used to view the dye image in the receiving element. It is used. The opacifying layer can include various reagents that provide the necessary reflection, such as titanium dioxide.

Examples of effective image-receiving elements (which may have a separate support or may also serve as a support) include synthetic polymer films such as polyethylene terephthalate film, polycarbonate film, polyvinyl chloride film, polyvinylidene chloride film, There are papers such as ethyl cellulose film, such as baryta paper, art paper, ivory paper, and plain paper.

In the present invention, a particularly preferable image receiving element is one having a synthetic polymer layer on a support, for example, a polyvinyl chloride layer or a polycarbonate layer provided on a baryter support, or a polyethylene terephthalate film support. Some are provided with a polyvinyl chloride layer or a polycarbonate layer. These are described in Japanese Patent Application Nos. 58-97907 and 58-128600. Further, polyvinyl chloride containing polyalkylene carbonate disclosed in JP-A-53-246, JP-A-51-88543
Nos. 52-40557, polyvinyl chloride containing silicone oil, and polyvinyl chloride having a plasticizer retained by plasma treatment are useful as the image-receiving layer of the present invention.

<Exposure and Thermal Development Means> Various exposure means can be used in the color diffusion transfer type photothermographic element of the present invention. The latent image is obtained by imagewise exposure to radiation containing visible light. Light sources commonly used for normal color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRTs and LEDs
Light rays or the like can be used as a light source.

The original drawing may be a photographic image with gradation, as well as a line image such as a drawing. Further, the printing from the original drawing may be a contact printing.

Further, the image projected by a video camera or the image information sent from a television station can be directly output to a CRT or OFT, and this image can be imaged on a photothermographic element by contact or a lens for printing.

In addition, LEDs (light-emitting diodes), which have made significant progress recently,
Are being used as exposure means and display means in various devices. It is difficult to make an LED that emits blue light effectively. In this case, to reproduce a color image, LEDs that emit green light, red light, and infrared light are used, and the layers that are sensitive to these lights are designed so as to respectively provide yellow, magenta, and cyan dyes. Good. That is, the green photosensitive layer may contain the yellow dye-donor compound, the red photosensitive layer may contain the magenta dye-donor compound, and the infrared photosensitive layer may contain the cyan dye-donor compound.

In addition to the method of directly contacting or projecting the above original image, the original image illuminated by the light source is read by the light receiving element such as a photoelectric tube or CCD, put in the memory of the computer, etc., so-called image processing to process this information as necessary. After performing the above, there is also a method of reproducing this image information on a CRT and using this as an image-like light source, or exposing three kinds of LEDs directly to emit light based on the processed information.

Thermal transfer from the photosensitive element of the present invention to the image-receiving layer (element) for thermal transfer is carried out when the photosensitive element of the present invention is thermally developed, or when it is reheated after completion of thermal development. For heating for thermal transfer, all methods applicable to ordinary photothermographic materials can be used. For example, contact with a heated block or plate, contact with a heat roller or a heat drum, pass through a high-temperature atmosphere, or use high-frequency heating, and further, in the photosensitive element of the present invention or for thermal transfer. It is also possible to provide a conductive layer in the image receiving layer (element) and utilize Joule heat generated by energization or a strong magnetic field. The heating pattern is not particularly limited, and includes a method of preheating (preheating) in advance and then heating again, at a high temperature for a short time, or at a low temperature for a long time, continuously rising, descending or repeating, and further discontinuous. Although heating is possible, a simple pattern is preferable. Further, it may be a system in which exposure and heating proceed simultaneously. Usually, the heating temperature during transfer is 80 ° C to 200 ° C, preferably 100 ° C.
The heating time is usually from 1 second to 5 minutes, preferably from 5 seconds to 3 minutes.

For thermal transfer using the photosensitive element of the present invention, it is easy to use a commercially available thermal developing machine. For example, "Image Forming 4634" (Sony Tektronix), "Developer Module 277" (3M), "Video Hard Copy Unit NWZ-301" (Japan Radio Co., Ltd.), etc. can be easily applied.

〔Example〕

Examples of the present invention will be shown below.
It is not limited to these.

Example-1 A coating solution for a heat-developable color photosensitive material containing the following components (a) to (h) was prepared.

(A) Photosensitive silver halide Silver iodobromide (AgBr: AgI = 97: 3) having an average particle size of 0.125μ formed in photographic gelatin was sensitized with sulfur to make it green-sensitive with a cyanine dye. 0.2g of the amount converted to silver.

(B) Organic silver salt An equivalent molar amount of 4-sulfobenzotriazole and silver nitrate reacted in an aqueous solution of poly (N-vinylpyrrolidone) is 0.2 g in terms of silver.

(C) Developer 0.35 g of the following developer synthesized by the method described in JP-A-56-146133.

(D) Dye donating compound 0.54 g of the following compound was dissolved in dioctyl phthalate and ethyl acetate, mixed with an aqueous gelatin solution containing dodecylbenzenesulfonic acid, and made into an oil-in-water type dispersion with a homogenizer.

(E) Binder Gelatin 0.64 including those contained in the above components
g, poly (N-vinylpyrrolidone) 1.44 g.

(F) Development accelerator (G) Thermal solvent 1,5-pentanediol 1.6g 1,3-Cyclohexanediol 0.4g (h) Gelatin hardening agent A benzotriazole compound (Table 1 below) was added to a coating solution containing a small amount of the above components in an amount of 6.0. × 10 ^-4 mol each, 37
The pH was adjusted to 5.5 at ℃ to adjust the surface tension and the viscosity, and the solution was applied onto an undercoated polyethylene terephthalate film for photography. Immediately after coating, the gel was cooled in an atmosphere of 5 ° C to 8 ° C and then dried at 30 ° C to 50 ° C.

The obtained sample was exposed to 1,600 CMS through a Ratten filter No. 99 (manufactured by Eastman Kodak Company) and a step wedge.

On the other hand, polyvinyl chloride-containing latex NIPOL G-576 (manufactured by Nippon Zeon Co., Ltd.) was coated on photographic baryta paper, and
The film was passed through an atmosphere of 0 ° C. to form a smooth film, which was used as an image receiving element for thermal transfer.

The exposed heat-developable color light-sensitive material and the image-receiving element for heat transfer were superposed on each other and subjected to a heat-development treatment at 140 ° C. for 1 minute by a developer module 277 (manufactured by 3M Co.) to quickly remove the image-receiving element. .

Table 1 shows the maximum density (Dmax) and the minimum density (Dmin) of the obtained cyan transfer image.

By adding the benzotriazole compound having a hydrophilic group of the present invention, it was possible to reduce the fog with almost no decrease in the maximum concentration.

Example-2 The same operation was performed by changing the organic silver salt in Example-1 to 5-acetamidobenzotriazole silver and benzotriazole silver.

As is clear from Table 2, the benzotriazole compound having a hydrophilic group of the present invention is excellent in the fog-reducing action against any organic silver salt of benzotriazole type.

Claims (1)

[Claims] 1. A support having at least (a) a photosensitive silver halide, (b) a benzotriazole-based organic silver salt, and (c).
In a photothermographic color photosensitive material having at least one photothermographic layer containing a developer, (d) a dye-donor compound and (e) a binder, at least one layer of the photothermographic layer is a hydroxy group or a carboxy group. , Sulfo group,
0.01 to 2 moles of benzotriazole having at least one hydrophilic group selected from a carbamoyl group or a sulfamoyl group as a substituent on a benzene ring is contained with respect to 1 mole of the benzotriazole-based organic silver salt. A heat-developable color photosensitive material.