JPH0679144B2 - Thermal development color diffusion transfer photosensitive material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a heat development color diffusion transfer method and a multilayer type heat development color photosensitive element suitable for carrying out the method, and in particular, it is free from color turbidity and diffusibility. The present invention relates to a multi-layer type heat development color diffusion transfer light-sensitive material having a good balance of diffusion of dyes from each layer.

[Prior art]

A heat-developable color light-sensitive material for transferring a diffusible dye released by heat development to obtain a color image is disclosed in JP-A-57-179840.
No. 57-186744, No. 57-198458, No. 57-207250, and No. 59-12431, and also in Japanese Patent Application No. 57-229649 by the present inventors. ing.

In these techniques, a dye-providing substance having a diffusible dye in the same molecule releases the diffusible dye by a heat development reaction of an organic silver salt and transfers it to an image receiving layer to obtain a color image.

On the other hand, Japanese Patent Application Nos. 57-229671 and 58-33 by the present inventors.
No. 363 and No. 58-33364, the technology is to form a heat-diffusible dye by reacting a colorless or light-colored dye-donor substance with an oxidant of a color developing agent generated by a heat development reaction of an organic silver salt. It is then transferred to the image receiving layer to form a color image.

In order to obtain a multicolor image by using the above-mentioned method, a multilayer structure is generally adopted in accordance with a conventional color light-sensitive material.

For example, in a diffusion transfer light-sensitive material for printing, as in silver halide color photographic paper, a blue light-sensitive layer containing a yellow coupler in the lowermost layer, a line light-sensitive layer containing a magenta coupler in the lower layer, and a cyan coupler in the uppermost layer are contained. A red photosensitive layer is provided.

For example, in the case of Ektaflex (trade name, manufactured by Eastman Kodak Company) as a practical product, the lowermost layer is a red photosensitive layer that releases a cyan dye, and then a green photosensitive layer that releases a magenta dye is overcoated. A blue photosensitive layer that emits a yellow dye is provided on the above, an intermediate layer for preventing color turbidity is provided between each layer, and a yellow-filter layer is provided between the blue photosensitive layer and the green photosensitive layer. ing.

As described above, for full-color development of the photothermographic material, it is important to prevent color turbidity between the layers as described above, and usually between the blue photosensitive layer, the green photosensitive layer and the red photosensitive layer. Color turbidity is suppressed by including the intermediate layer.

However, in order to sufficiently suppress color turbidity, the diffusion or release property formed by increasing the film thickness of each intermediate layer or increasing the content of a diffusion-resistant polymer (eg gelatin) against the oxidant of the color developing agent. Transferability of the dye to the image receiving layer will be reduced.

Further, it has been known that hydroquinones and catechols are used to prevent color turbidity in conventional photography, but a satisfactory technology for preventing color turbidity is not known in photothermographic materials. . For example, alkylhydroquinones, which are usually used in conventional silver halide emulsions, are strong reducing agents,
It acts as a developer in the heat-developable photosensitive material, which is not preferable in terms of photographic characteristics.

(Object of the invention) Accordingly, an object of the present invention is to provide a multi-layer type heat development color diffusion transfer photosensitive material in which color turbidity is prevented and transferability from the bottom layer is improved, and a color developing agent during heat development. Another object of the present invention is to provide a multi-layer type heat-developable color light-sensitive material containing the oxidant scavenger which is highly reactive with the oxidant and is sufficiently nondiffusible.

(Structure of the Invention) The above-mentioned object of the present invention comprises a photosensitive silver halide, an organic silver salt, a dye-providing substance capable of forming a diffusible dye by heat development and a binder, and In a heat-development color diffusion transfer light-sensitive material having at least two light-sensitive layers on a support, each of which has different chromaticity and hue of the formed dye from each other, each of the above-mentioned color sensitivity and hue of the formed dye. And at least one of the polymer couplers represented by the following general formula (1) capable of reacting with an oxidant of a color developing agent to immobilize the oxidant between at least two photosensitive layers. A heat-developable color diffusion transfer light-sensitive material characterized by having a substantially light-insensitive intermediate layer contained therein.

The polymer coupler according to the present invention is a polymer having an internal cyan, magenta or yellow coupler used in ordinary silver halide color light-sensitive materials in its side chain or skeleton. Examples of the coupler include active methylene compounds such as open-chain ketomethylene compounds, pyrazolone compounds and pyrazolotriazole compounds, active methine compounds such as phenol and naphthol derivatives, and so-called 2-equivalent couplers having a leaving group at their active sites. .

These polymer couplers must be immobilized in the binder of the interlayer according to the invention, non-diffusible and immobile after reaction with the oxidized color developing agent. Therefore, the sites other than the active site substituents must be polymerized.

The polymer coupler used here may have a size sufficient to make these polymer couplers non-diffusible in the constituent layers of the light-sensitive material according to the present invention, and usually has a molecular weight of 1000 or more, preferably 2000 or more, more preferably 5000.
Those which are the above groups are selected. These polymer couplers may be either hydrophilic or hydrophobic, with hydrophobic being particularly preferred. In the case of a hydrophilic polymer coupler, it can be dissolved in the binder solution as it is. When it is a hydrophobic polymer coupler, it is dissolved in an organic solvent and then used in combination with a high boiling point solvent (hydrophobic organic solvent having a boiling point of 200 ° C or higher) or without a high boiling point solvent using an ultrasonic disperser, a colloid mill or various homogenizers. It is possible to carry out mechanical dispersion, or to synthesize the polymer coupler itself in the form of a latex and mix it as it is.

Examples of polymer couplers preferably used in the present invention include British Patents 880,206, 967,503, and 995,363.
No. 1,104,658 No. 1,247,688, U.S. Patent 3,451,82
0, 4,207,109, 4,080,211 and JP-A-55-85549.
Various issues are listed. Among them, hydrophilic polymer couplers have a low solubility in water, have a problem of compatibility with gelatin and other water-soluble polymers, or have a drawback that the viscosity of the solution is greatly increased. Therefore, hydrophobic polymer couplers are more preferable.

The polymer coupler used in the present invention may have any structure as long as it is substantially non-diffusible in the binder as described above, but typical examples thereof are as follows. There is a copolymer of a non-color forming ethylenically unsaturated monomer and an oxidation product of an aromatic primary amine color developing agent and a hydrophobic monomer coupler capable of forming a dye by coupling.

It is possible to change the ratio of the mono coupler to the non-color forming ethylenic mono monomer by 5 to 100% by weight of the monomer coupler.
0 to 70% by weight is preferred. Two or more kinds of non-color-forming ethylenic monocycles may be used. Further, these polymer couplers may be in the form of latex, and mechanical dispersion can be omitted when the polymer coupler latex is used.

Acrylic acid, methacrylic acid, α-chloroacrylic acid that imparts hydrophobicity as the non-color-forming ethylenically unsaturated monomer,
Acrylic acids such as α-alacrylic acid, esters or amides derived from acrylic acids such as t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-butyl methacrylate , 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate and lauryl methacrylate, vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate, acrylonitrile, methacrylonitrile, aromatic vinyl compounds such as styrene and its derivatives, For example, vinyl toluene, divinyl benzene, vinyl acetophenone, vinyl alkyl ethers such as vinyl ethyl ether, male Acid ester and the like.

Particularly preferred are acrylic acid ester, methacrylic acid ester, and maleic acid ester.

Further, as a substance that imparts hydrophilicity, acrylic acid, methacrylic acid, sulfopropyl acrylate containing a hydrophilic group,
Acrylic acid-N-2-sulfo-1,1-dimethylamide,
p-sulfostyrene etc. are mentioned.

Further, the hydrophobic monomer coupler capable of forming a dye by coupling with the oxidation product of the aromatic primary amine developer is represented by the following general formula (1).

General formula (1) In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or chlorine, and X represents -CONH-, -NHCONH.
-, - NHCOO -, - COO -, - SO 2 -, - CO-, or -O
Represents -CONH-, or -COO-, A represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, or an unsubstituted or substituted phenylene group, and the alkylene group may be linear or branched. May be. (For example, methylene, methylmethylene, dimethylmethylene dimethylene, trimethylene, dimethylmethylene, etc.) Q is a cyan dye-forming coupler residue, a magenta dye-forming coupler residue and a cyan dye-forming coupler residue capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developing agent. Represents a yellow dye-forming coupler residue.

m and n represent 0 or 1.

Here, the substituent of the alkylene group or phenylene group represented by A is an aryl group (for example, a phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (for example, a methoxy group), an aryloxy group (for example, a phenoxy group). ), An acyloxy group (for example, an acetoxy group),
Acylamino group (eg, methanesulfonamide group), sulfamoyl group (eg, methylsulfamoyl group), halogen atom (eg, fluorine, chlorine, bromine, etc.), carboxy group, carbamoyl group (eg, methylcarbamoyl group), alkoxycarbonyl group ( For example, a methoxycarbonyl group and the like, and a sulfonyl group (eg, methylsulfonyl group) can be mentioned. When there are two or more substituents, they may be the same or different.

Among the dye-forming coupler residues represented by Q, the cyan dye-forming coupler residue is preferably one of the following phenol type (C ₁ ) or naphthol type (C ₂ ).

In the formula, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, an aliphatic amide group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an aryl group. It represents a lucarbamoyl group, an arylamide group, an arylsulfamoyl group, an arylsulfonamide group or an arylureido group, and when there are two or more substituents, they may be the same or different.

Z ₁ represents a hydrogen atom, a halogen atom, a sulfo group, an acyloxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, a furylthio group or a heterocyclic thio group, and these groups further include an aryl group (for example, Phenyl group), nitro group, hydroxyl group, cyano group, sulfo group,
Alkoxy group (eg methoxy group), aryloxy group (eg phenoxy group), acyloxy group (eg acetoxy group), acylamino group (eg acetylamino group), sulfonamide group (eg methanesulfonamide group), sulfamoyl group (eg methyl) Sulfamoyl group), halogen atom (eg fluorine, chlorine, bromine), carboxy group, carbamoyl group (eg methylcarbamoyl group), alkoxycarbonyl group (eg methoxycarbonyl group), sulfonyl group (eg methylsulfonyl group) May be substituted with a substituent such as.

The magenta dye-forming coupler residue is preferably a pyrazolone or indazolone type (M ₁ ) one, for example In the formula, R ₂ is a substituent of a well-known type at the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituted alkyl group (for example, haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl, etc.), an aryl group,
Substituted aryl group [As a substituent, an alkyl group (eg, methyl group, ethyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, etc.), an aryloxy group (eg, phenyloxy group, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl group) Etc.), acylamino group (eg acetylamino group), carbamoyl group, alkylcarbamoyl group (eg methylcarbamoyl group, ethylcarbonyl group etc.), dialkylcarbamoyl group (eg dimethylcarbamoyl group), arylcarbamoyl group (eg phenylcarbamoyl group) , An alkylsulfonyl group (eg, methylsulfonyl group), an arylsulfonyl group (eg, phenylsulfonyl group), an alkylsulfonamide group (eg, methanesulfonamide group), an arylsulfonamide group ( In example phenylalanine sulphonamide groups),
Sulfamoyl group, alkylsulfamoyl group (eg ethylsulfamoyl group), dialkylsulfamoyl group (eg dimethylsulfamoyl group), alkylthio group (eg methylthio group), arylthio group (eg phenylthio group), cyano group, Nitro group, halogen atom (for example, fluorine, chlorine, bromine, etc.)], and when there are two or more substituents, they may be the same or different.

Particularly preferred substituents include a halogen atom, an alkyne group, an alkoxy group, an alkoxycarbonyl group and a cyano group.

Z ₂ represents a leaving group bonded to the coupling position with a hydrogen atom, an oxygen atom, a nitrogen atom or a sulfur atom, and when Z ₂ is bonded to the coupling position with an oxygen atom, a nitrogen atom or a sulfur atom, , These atoms are bonded to an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group or a heterocyclic group (wherein the alkyl group, the aryl group and the heterocyclic group are the above-mentioned R ₂ may have a group represented as a substituent of the aryl group of ₂ ), and in the case of a nitrogen atom, a group capable of forming a 5-membered or 6-membered ring containing the nitrogen atom to form a leaving group. Also means. (For example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, etc.).

The yellow dye-forming coupler residue is preferably an acylacetanilide type one, particularly a bivaloylacetanilide type (Y ₁ ) benzoylacetanilide type (Y ₂ ) or (Y ₃ ).

In the formula, R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom or a well-known substituent of a yellow dye-forming coupler residue such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, Aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group,
It represents an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, etc., and these substituents may be the same or different.

Z ₃ is a hydrogen atom or one represented by the following general formula (2), (3), (4) or (5).

R ₇ represents an optionally substituted aryl group or heterocyclic group.

R ₈ and R ₉ are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group or a heterocyclic group. Represents a ring and these groups may be the same or different.

W ₁ in the formula Represents a non-metal atom required to form a 4-membered ring, 5-membered ring or 6-membered ring.

Of the general formula (5), (6) to (8) are preferable.

In the formula, R ₁₀ and R ₁₁ are each a hydrogen atom, an alkyl group, an aryloxy group or a hydroxy group, and R ₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group,
Or, an acyl group and W ₂ represents an oxygen atom or a sulfur atom.

Examples of monomer couplers to be copolymerized in the present invention are various documents such as Belgian Patents 584,494, 602,516 and 669,
971, British Patent 967,503, 1,130,581, 1,247,6
88, 1,269,355, U.S. Patents 3,356,656, 3,767,
It is seen in No. 412.

The following are typical examples.

The polymer coupler or polymer coupler latex used in the present invention can be synthesized by a known method described in the above-mentioned literature or JP-A-58-42044. To give a representative example The above shows only a typical example of the solution polymerization type,
It is not limited to these and may be a latex polymer coupler.

In a preferred embodiment of the constitution of the present invention, for example, a red light-sensitive layer comprising a red-sensitive silver halide, an organic silver salt and a cyan dye-donating substance on a paper support, and a compound according to the present invention thereon. An intermediate layer containing a green light-sensitive silver halide, an organic silver salt, a green light-sensitive layer containing a magenta dye-donor, and an intermediate layer containing the compound according to the present invention and a yellow filter layer. And a blue light-sensitive layer composed of a blue-sensitive silver halide, an organic silver salt and a yellow dye-donating substance, which are applied in this order.
If necessary, in addition to these, a reducing agent, a development accelerator, a color toning agent, a thermal antifoggant, a thermal solvent, etc. may be added to these constituent layers formed in the multi-layer type heat development color diffusion transfer photosensitive material of the present invention. An agent is preferably added. The scavenger (polymer coupler) of the oxidized color developing agent according to the present invention may be added not only in the intermediate layer but also in each photosensitive layer. When a yellow filter layer is provided in the constituent layer, the layer may contain the scavenger.

A preferred embodiment of the present invention is a photosensitive layer image-receiving layer integrated type having an image-receiving layer on a support and one or more photosensitive layers on the layer, wherein the image-receiving layer is separate from the photosensitive element. A type that is composed of independently formed image receiving elements and is placed in a contact surface relationship at least during diffusion transfer (the image receiving layer may be a so-called support-use type), and is observed as it is. Examples thereof include a photosensitive layer and an image receiving layer separated from the photosensitive element.

Next, the present invention will be described in detail in order.

The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples thereof include silver chloroiodobromide. The photosensitive silver halide is
It can be prepared by any method known in the photographic art, such as a single jet method or a double jet method. In the present invention, a photosensitive silver halide prepared according to a conventional method for preparing a silver halide gelatin emulsion is used. Emulsions give favorable results.

The photosensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Examples of the sensitizing method include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the above light-sensitive emulsion may be coarse particles or fine particles, but the preferred grain size is about 0.001 to about 1.5 μm, and more preferably about 0.01 μm.
Is about 0.5 μm.

The photosensitive silver halide is preferably subjected to a sensitizing treatment such as chemical sensitization or spectral sensitization in a gelatin solution and then mixed with the binder of the present invention, that is, a silver halide gelatin emulsion is used. It is preferred to use the silver halide sensitized by doing in the binder of the present invention.

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

As another method for preparing photosensitive silver halide, a photosensitive silver salt forming component may be allowed to coexist with an organic silver salt to form photosensitive silver halide on a part of the organic silver salt. As the photosensitive silver salt forming component used in this preparation method, an inorganic halide, for example, a halide represented by MXn (wherein M represents an H atom, an NH ₄ group or a metal atom, and X represents C
l, Br or 1, n represents the valence when M is an H atom, NH ₄ is 1 and M is a metal atom. As a metal atom,
Lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium,
Strontium, barium, zinc, cadmium, mercury,
Aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, cerium, etc. To be ), A halogen-containing metal complex (eg, K ₂ PtCl ₆ , K ₂ Pt
Br ₆ , HA _u Cl ₄ , (NH ₄ ) ₂ IrCl ₆ , (NH ₄ ) ₃ IrCl ₆ , (NH ₄ ) ₂ Ru
Cl ₆ , (NH ₄ ) ₃ RuCl ₆ , (NH ₄ ) ₃ RhCl ₆ , (NH ₄ ) ₃ RhBr
₆ etc.), onium halides (eg tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylazolium bromide, quaternary ammonium halides such as trimethylbenzylammonium bromide, tetraethylphosphonium bromide, etc. Quaternary phosphonium halides, benzylethylmethyl bromide, tertiary sulfonium halides such as 1-ethylthiazolium bromide, etc., halogenated hydrocarbons (eg iodoform, bromoform, carbon tetrabromide, 2-bromo-2) -Methylpropane, etc., N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-yo) Dosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide,
N-bromo-N-methylbenzenesulfonamide, 1,3
-Dibromo-4,4-dimethylhydantoin, etc.), other halogen-containing compounds (for example, triphenylmethyl chloride,
Triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.) and the like.

These photosensitive silver halide and photosensitive silver salt forming component can be used in combination in various methods, and the amount used is 0.001 to 1.0 mol, preferably 0.01 to 0.3 mol, per mol of the organic silver salt. .

Further, the heat-developable color photosensitive element used in the present invention contains blue light,
Each layer having sensitivity to green light and red light, that is, a heat-developable blue photosensitive layer, a heat-developable green photosensitive layer, and a heat-developable red photosensitive layer can have a multilayer structure. -Sensitive silver halide emulsion, green-sensitive silver halide emulsion and red-sensitive silver halide emulsion can be obtained by adding various spectral sensitizing dyes to the above-mentioned silver halide emulsion.

Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, phoroboler cyanine, styryl,
Examples include hemicyanine and oxonol. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferable. Such a nucleus may have an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group, or an enamine group capable of forming a condensed carbocyclic or heterocyclic ring. .
Further, it may be anti-antipodal or non-antipodal and may have an alkyl group, a phenyl group, an enamine group or a heterocyclic substituent in the methine chain or polymethine chain.

The merocyanine dye may be, for example, a thiohydantoin nucleus, a rhodanine nucleus, an oxazolidinedione nucleus in addition to the above basic nucleus,
It may have an acidic nucleus such as a thiazolidinedione nucleus, a barbituric acid nucleus, a thiazolinthione nucleus, a malononitrile nucleus and a pyrazolone nucleus. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivative,
Azaindene cadmium salt, organic sulfonic acid, etc. can be used in combination with a supersensitizing additive which does not absorb visible light as described in, for example, US Pat. Nos. 2,933,390 and 2,937,089.

The addition amount of these dyes is 1 × 10 ^-4 mol to 1 mol, and more preferably 1 × 10 ^-4 mol to 1 × 10 ^-1 mol per mol of silver halide or a silver halide-forming component.

Examples of the organic silver salt used in the heat-developable color photosensitive element of the present invention include JP-B Nos. 43-4924, 44-26582 and 45-184.
16, 45-12700, 45-22185 and JP-A-49-52
No. 626, No. 52-31728, No. 52-13731, No. 52-141222
No. 53-36224, No. 53-37610, U.S. Pat.
No. 3, 4,168,980 and the like, silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver barmitate, silver stearate, silver arachidonate, silver behenate, etc., and aromatic carboxylic acids. Silver, for example, silver benzoate, silver phthalate, etc., or a silver salt having an imino group, for example, benztriazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., a silver salt of a compound having a mercapto group or a thione group, for example 2-mercaptoben Two oxazole silver, mercapto oxadiazole silver, mercapto benzthiazole silver, 2-mercapto benzimidazole silver, 3-mercapto-phenyl-1,2,4-triazole silver, and other 4-hydroxy-6-methyl-1, 3,3a, 7-tetrazaindene silver, 5-methyl-7-hydroxy-1,2,3,
4,6-heptazainten silver and the like can be mentioned. Research Disclosure 16966, 16907, British Patent 1,590,956
No. 1,590,957, and silver compounds as described in No. 1,590,957 can also be used. Among them, for example, a silver salt having an imino group such as benztriazole silver super silver is preferable, and examples of the benztriazole silver salt include alkyl-substituted benztriazole silver such as methylbenztriazole silver, for example, bromobenztriazole silver and chlorobenz. Halogen-substituted benztriazole silver such as triazole silver, amide-substituted benztriazole silver such as 5-acetamidobenztriazole silver, and British Patent 1,590,956.
No. 1,590,957, such as N- [6-
Chloro-4-N (3,5-dichloro-4-hydroxyphenyl) imino-1-oxo-5-methyl-2,5-cyclohexadien-2-yl] -5-carbamoylbenztriazole silver salt, 2-benz Triazol-5-ylazo-4-methoxy-1-naphthol silver salt, 1-Benztriazol-5-ylazo-2-naphthol silver salt, N-
Examples thereof include benztriazol-5-yl-4- (4-dimethylaminophenylazo) benzamide silver salt.

Further, nitrobenztriazoles represented by the following general formula (9) and benztriazoles represented by the following general formula (10) can be advantageously used.

General formula (9) In the formula, R ₁₅ represents a nitro group, R ₁₆ and R ₁₇ may be the same or different and each is a halogen atom (for example, chlorine,
Bromine, iodine), hydroxy group, sulfo group or salt thereof (eg sodium salt, potassium salt, ammonium salt), carboxy group or salt thereof (eg sodium salt, potassium salt, ammonium salt), nitro group, cyano group, or each A carbamoyl group which may have a substituent, a sulfamoyl group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group), an alkoxy group (for example, a methoxy group,
An ethoxy group), an aryl group (for example, a phenyl group), or an amino group, r is 0 to 2, and s is an integer of 0 to 1. Examples of the substituent of the carbamoyl group include a methyl group, an ethyl group, an acetyl group, and the like,
Examples of the substituent of the sulfamoyl group include a methyl group, ethyl group and acetyl group, examples of the substituent of the alkyl group include a carboxy group and ethoxycarbonyl group, and examples of the substituent of an aryl group include a sulfo group. , A nitro group and the like, examples of the substituent of the alkoxy group include a carboxy group and an ethoxycarbonyl group, and examples of the substituent of the amino group include an acetyl group, a methanesulfonyl group and a hydroxy group.

The compound represented by the general formula (9) is a silver salt of a benzotriazole derivative having at least one nitro group, and specific examples thereof include the following compounds.

For example, 4-nitrobenzotriazole silver, 5-nitrobenzotriazole silver, 5-nitro-6-chlorobenzotriazole silver, 5-nitro-6-methylbenzotriazole silver, 5-nitro-6-methoxybenzotriazole silver, 5 -Nitro-7-phenylbenzotriazole silver, 4-hydroxy-5-nitrobenzotriazole silver, 4-hydroxy-7-nitrobenzotriazole silver, 4-hydroxy-5,7-dinitrobenzotriazole silver, 4-hydroxy-5 -Nitro-6-chlorobenzotriazole silver, 4-hydroxy-5-nitro-6-methylbenzotriazole silver, 4-sulfo-6-nitrobenzotriazole silver, 4-carboxy-6-nitrobenzotriazole silver, 5-carboxy -6-Nitrobenzotriazole silver, 4-cal Moyl-6-nitrobenzotriazole silver, 4-sulfofamoyl-6-nitrobenzotriazole silver, 5-carboxymethyl-6-nitrobenzotriazole silver, 5-hydroxycarbonylmethoxy-6-nitrobenzotriazole silver, 5-nitro -7-Cyanobenzotriazole silver, 5-amino-6-
Nitrobenzotriazole silver, 5-nitro-7- (p-
Nitrophenyl) benzotriazole silver, 5,7-dinitro-6-methylbenzotriazole silver, 5,7-dinitro-6-chlorpenzotriazole silver, 5,7-dinitro-
Examples thereof include 6-methoxybenzotriazole silver.

General formula (10) In the formula, R ₁₈ may have a hydroxy group, a sulfo group or a salt thereof (eg sodium salt, potassium salt, ammonium salt), a carboxy group or a salt thereof (eg sodium salt, potassium salt, ammonium salt), or a substituent. Represents a good carbamoyl group and a sulfamoyl group which may have a substituent, and R ₁₉ is a halogen atom (eg, base, bromine, iodine), a hydroxy group, a sulfo group or a salt thereof (eg, sodium salt, potassium salt, ammonium salt). ), A carboxy group or a salt thereof (for example, sodium salt, potassium salt,
Ammonium salt), a nitro group, a cyano group, or an alkyl group which may have a substituent (for example, a methyl group,
Ethyl group, propyl group), aryl group (eg phenyl group), alkoxy group (eg methoxy group, ethoxy group)
Or represents an amino group, p represents 1 or 2, and q represents an integer of 0 to 2.

Further, examples of the substituent of the carbamoyl group for R ₁₈ include a methyl group, ethyl group and acetyl group, and examples of the substituent of the sulfamoyl group include a methyl group, ethyl group and acetyl group. it can. Further, as the substituent of the alkyl group in R _19, for example, a carboxy group, an ethoxycarbonyl group, etc., and as the substituent of the aryl group, for example, a sulfo group, a nitro group, etc.
Examples of the substituent of the alkoxy group include a carboxy group and an ethoxycarbonyl group, and examples of the substituent of the amino group include an acetyl group, a methanesulfonyl group and a hydroxy group.

The following compounds may be mentioned as specific examples of the organic silver salt represented by the general formula (10).

For example, 4-hydroxybenzotriazole silver, 5-hydroxybenzotriazole silver, 4-sulfobenzotriazole silver, 5-sulfobenzotriazole silver, benzotriazole silver-4-sulfonate, benzotriazole silver-5-sulfonate, Benzotriazole silver-4-sulfonate, potassium benzotriazole-5-sulfonate, ammonium benzotriazole-4-sulfonate, ammonium benzotriazole-5-sulfonate, silver 4-carboxybenzotriazole, 5-carboxy Benzotriazole silver, benzotriazole silver-4-carboxylate sodium, benzotriazole silver-5-carboxylate sodium, benzotriazole silver-4-carboxylate potassium,
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.

A method for preparing the organic silver salt according to the present invention will be described later, but the organic silver salt according to the present invention may be isolated and used in a binder for a photosensitive layer by a suitable means. Alternatively, the silver salt may be prepared in the binder for the photosensitive layer and used as it is without isolation.

The amount of the organic silver salt used is 0.05 g to 10.0 g, and preferably 0.2 g to 2.0 g per 1 m ² of the support.

Examples of the reducing agent used in the heat-developable color photosensitive element of the present invention include U.S. Pat. Nos. 3,531,286, 3,761,270 and
3,764,328, Research Disclosure 12146, same
15108, 15127 and p-described in JP-A-56-27132
Phenylenediamine-based and p-aminophenol-based developing agents, phosphoroamidophenol-based and sulfonamidephenol-based developing agents, and hydrazone-type color developing agents are disclosed in JP-A-57-186744, 59-12431, and 57- 487
No. 65, No. 59-15941, Japanese Patent Application No. 58-33363, No. 58-3336.
In the case of the thermal transfer dye-providing substance described in No. 4 etc., it can be advantageously used. In this case, diffusible dyes are released or formed by the oxidative coupling of reducing agents with these thermal transfer dye-providing substances. Also U.S. Pat.No. 3,342,599,
Color developing agent precursors described in JP-A-3,719,492, JP-A-53-135628 and JP-A-54-79035, etc. can also be advantageously used.

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 it is not always necessary to use the above-mentioned reducing agent, and a reducing agent as 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-benzozenesulfonamidephenol, 2,6-dibromo -4- (p-toluenesulfonamide) phenol and the like] or polyhydroxybenzenes (for example, hydroquinone, t-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3
-Carboxycatechol, etc.), naphthols (eg α
-Naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylenebisnaphthols [eg 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.], methylenebisphenol [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 reducing agents may be used alone or in combination of two or more. The amount of the reducing agent used depends on the type of organic silver salt used, the type of photosensitive silver halide and the types of other additives, etc., but is usually 0 per mole of organic silver salt.
It is in the range of 05 mol to 10 mol, preferably 0.1 mol to 3 mol.
It is a mole.

A hydrophilic binder is used as the binder in the heat-developable photosensitive layer of the heat-developable color photosensitive element of the present invention, but a hydrophobic binder may be used in combination. The hydrophilic binder in the present invention means one soluble in water or a mixed liquid of water and an organic solvent. For example, proteins such as gelatin and gelatin derivatives, cellulose derivatives, polysaccharides such as textran, 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 (preferably having a saponification rate of 75% or more) and the like, but not limited to these. 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. The amount of the binder is 1/10 to 10 parts by weight, preferably 1/4 to 4 parts by weight, based on 1 part of the organic silver salt in each photosensitive layer.

The dye-providing substance of the present invention may be of any type such as a dye-releasing type by reaction, a dye-forming type, or the like, for example, JP-A-57-179840, 57-186744, and 57-12431. Japanese Patent Application Nos. 57-224883, 57-224884, 57-205447
No. 57, No. 57-225928, No. 57-229648, No. 57-229672
No. 58-33363, No. 58-33364 and the like, it is possible to use the dye-donor substances, particularly preferably, described in Japanese Patent Application No. 58-33363 and 58-33364. It is a dye-providing substance having a hydrophilic group. Such a dye-providing substance is substantially immobilized in the hydrophilic binder system even during thermal development, and therefore, color turbidity due to diffusion of the dye-providing substance between layers does not occur.

The dye-donor materials described above release or form imagewise heat-diffusible dyes as a result of thermal development, and the released or formed dyes are diffused and transferred to the image-receiving element.

As the dye-providing substance used in the present invention, for example, a compound capable of forming or releasing a dye by a coupling reaction with an oxidized product of a color developing agent produced by thermal development can be used. The residue is represented by, for example, the following general formulas (11) to (16).

General formula (11) General formula (12) General formula (13) General formula (14) General formula (15) General formula (16) In the formula, R _{20 to} R ₂₅ represent a substituent, and R ₂₀ , R ₂₁ , R ₂₂ and R
₂₅ is a hydrogen atom, a halogen atom (preferably a fluorine atom,
Chlorine atom or bromine atom), alkyl group (preferably alkyl group having 3 or less carbon atoms or fluorine-substituted alkyl group), aryl group (preferably phenyl group), alkoxy group (preferably alkoxy group having 3 or less carbon atoms), amino Group, an alkyl group-substituted amino group (preferably an alkyl-substituted amino group in which the total number of carbon atoms in the alkyl group is 6 or less), a cyano group or a nitro group, and R ₂₁ and R ₂₂ are bonded to each other to form a 5- to 6-membered group. To form a carbocycle or heterocycle (preferably condensed with a phenol ring to form a naphthol ring or a quinsonol ring), R ₂₃ is an alkyl group (preferably an alkyl group having 3 or less carbon atoms) or an aryl group (preferably A phenyl group), R ₂₄ represents an electron-withdrawing group (preferably a phenyl group), X ₁ is a group capable of leaving from the coupler by a coupling reaction, When the dye-donor is a dye-releasing type, the X ₁ moiety may include a dye moiety, and when the dye-donor is a dye-forming type, a suitable active site substituent is present on the X ₁ moiety. May be included. Further, whether the dye-donating substance is a dye-forming type or a dye-releasing type, a hydrophilic group (eg, sulfo group, carboxy group, sulfonamide group, etc.) is contained in the coupler residue or active site substituent portion. It is possible, and Japanese Patent Application No. 57-
Nos. 229671, 58-33364 and 58-109293, which are particularly preferably used in the present invention in addition to the above-mentioned examples.

The amount of the dye-providing substance used in the present invention is not limited and is generally 0.01 to 10 mol, preferably 0.1 to 1 mol per mol of the organic silver salt.
Used in the range of up to 2.0 mol.

The dye-donor substance preferably used in the present invention forms a dye by a coupling reaction with a color developing agent as a reducing agent, releases a dye by a coupling reaction, or releases a dye by an oxidation or reduction reaction, or An image-wise heat-diffusible dye is released or formed due to a change to a non-releasing substance, and the dye is thermally diffused and transferred to the image receiving layer. In the binder of the light-sensitive element of the present invention, the dye, together with the action of the heat solvent, is extremely well transferred by heat and gives a sufficient density in a short time, and in the case of multiple layers, it is sufficiently transferred even from the lowermost layer.

Various additives can be added to the diffusion transfer type heat-developable color photosensitive element of the present invention, if necessary, in addition to the above respective parts. For example, as a development accelerator, U.S. Pat.
No., No. 3,531,285, No. 4,012,260, No. 4,060,420,
No. 4,088,496, No. 4,207,392 or RD15733, No. 1573
4, alkali release agents described in 15776, etc., Japanese Patent Publication No. 45-
Organic acid described in 12700, -CO described in U.S. Patent 3,667,959
_{-, - SO 2 -, -} SO- non-aqueous polar solvent a compound having a group and as the color tone adjusting agent, for example, JP 46-4928
No. 46, No. 46-6077, No. 49-5019, No. 49-5020, No. 49
-91215, 49-107727, 50-2524, 50-671
No. 32, No. 50-67641, No. 50-114217, No. 52-33722
No. 52-99813, No. 53-1020, No. 53-55115,
53-76020, 53-125014, 54-156523, 54
-156524, 54-156525, 54-156526, 55-
No. 4060, No. 55-4061, No. 55-32015 and West German Patent Nos. 2,140,406, No. 2,147,063, No. 2,220,618, U.S. Patent Nos. 3,080,254, No. 3,847,612, No. 3,782,941,
No. 3,994,732, No. 4,123,282, No. 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,
Isocarbostyril, sulfonamide, 2H-1,3-benzothiazine-2,4- (3H) dione, benzotriazine,
There are mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., and a mixture of one or more of these with an imidazole compound or at least an acid or acid anhydride such as phthalic acid, naphthalic acid. A mixture of one and a phthalazine compound, further phthalazine and maleic acid, itaconic acid,
Examples thereof include a combination of quinolinic acid, gentisic acid and the like. Further, 3-amino-5-mercapto-1,2,4-triazoles and 3-acylamino-5-mercapto-1,2,4 described in JP-A Nos. 58-189628 and 58-193460 are disclosed.
-Triazoles are also effective.

Further, as an anti-caprying agent, 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,
51-104339, 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.

In addition, as a stabilizer, a print-out preventing agent after treatment may be used at the same time. For example, JP-A-48-45228 and JP-A-50-22828 may be used.
-119624, No. 50-120328, No. 53-46020 and the like halogenated hydrocarbons, 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.

The thermal solvent used in the present invention may be any substance that promotes thermal development and / or thermal transfer, but is preferably a solid, a semi-solid or a liquid at room temperature and is dissolved in the binder of the photosensitive layer by heating or Is a substance that melts,
Preferred examples include urea derivatives, amide derivatives, polyethylene glycols and polyhydric alcohols, and these thermal solvents may be used alone or in combination of two or more.
It is preferable that these thermal solvents not only improve the transferability of the dye, but also improve the developability and the release or formability of the dye. The melting point of the thermal solvent of the present invention need not be below the thermal development temperature, and may be a liquid at room temperature.

Next, the thermal solvent preferably used in the present invention will be described.

As the urea derivative, those represented by the following general formula (17) are preferable.

General formula (17) In the formula, Z is an oxygen atom or a sulfur atom, R ₂₆ , R ₂₇ , R ₂₈ and R _29.
May be the same or different and each represents a hydrogen atom or a substituted or unsubstituted alkyl group having 12 or less carbon atoms (R ₂₆ and R ₂₇
And R ₂₈ and R ₂₉ may combine to form a ring) or a substituted or unsubstituted aryl group having 12 or less carbon atoms.

As the amide derivative, those represented by the following general formula (18) are preferable.

General formula (18) In the formula, R ₃₀ represents a substituted or unsubstituted alkyl group having 12 or less carbon atoms or a substituted or unsubstituted aryl group having 12 or less carbon atoms, R ₃₁ and R ₃₂ may be the same or different, Represents a hydrogen atom, a substituted or unsubstituted alkyl group having 6 or less carbon atoms, a substituted or unsubstituted aryl group or acyl group having 6 or less carbon atoms (6 or less carbon atoms), and R ₃₀ and R ₃₁
May combine with each other to form a ring. Polyethylene glycols having a molecular weight of 150 to 10,000 are preferable.

For polyhydric alcohols, the total number of carbon atoms is 12 or less,
A cyclic or chain-like (which may be substituted with a halogen atom, an alkoxy group, an acyl group or the like) alcohol having 2 to 6 hydroxy groups 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, tetramethylurine , Tetraethylurea, etc.

Specific examples of the amide derivative include acetamide, propionamide, n-butylamide, i-butylamide, benzamide, diacetamide, dimethylformamide, acetanilide, ethylacetamide acetate, 2-chloropropionamide, 3-chloropropionamide,
Examples include phthalimide, succinimide, and N, N-dimethylacetamide.

Specific examples of the polyhydric alcohol include 1,6-hexanediol, dixylitol, pentaerythritol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 2,2'-dihydroxybenzophenone, 1,8-octanediol. Etc.

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.

The hot solvent used in the present invention may be contained by providing a hot solvent supply.

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

In addition to the photosensitive layer and the scavenger layer, the color diffusion transfer type photosensitive element according to the present invention may be provided with various photographic constituent layers such as an overcoat polymer layer, an undercoat layer, a backing layer or an intermediate layer according to the purpose. .

The photosensitive layer and other photographic constituent layers according to the present invention are coated on a wide variety of supports. Examples of the support used in the present invention include plastic films such as cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polyethylene film, polyethylene terephthalate film, and polycarbonate film, and metals such as glass, paper and aluminum. Also, baryta paper, resin coated paper, and water resistant paper can be used.

The photosensitive layer and other constituent layers contained in the photosensitive element of the present invention are each prepared by preparing a coating solution, and various methods such as a dipping method, an air knife method, a curtain coating method or a hopper coating method described in U.S. Pat. It can be prepared by a coating method. Furthermore, if desired, two or more layers can be coated simultaneously by the method described in US Pat. No. 2,761,791 and British Patent No. 837,095.

The light-sensitive element according to the present invention gives a color image to the image-receiving layer by imagewise exposure, development by heat treatment and thermal transfer to an image-receiving layer in surface contact with the light-sensitive element.

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

Further, the image receiving layer may be arranged and configured in any of the forms of the above-described embodiments of the present invention.

Further, the image-receiving layer used in the present invention may be formed of a substance that receives a diffusible dye released or formed by thermal development, and may be a mordant or a mordant used in a diffusion transfer type photosensitive material.
The glass transition temperature described in 57-207250, etc. is 40 ° C or higher.
It is preferably formed of a heat-resistant organic polymer material having a temperature of 250 ° C. or lower.

As specific examples of the mordant, nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, and quaternary cationic compounds thereof are widely known, and these can be effectively used in the present invention. .

U.S. Patents 2,548,564, 2,484,430, 3,148,061
No. 3,756,814 disclose vinyl pyridine polymers and vinyl pyridinium cationic polymers.

US Pat. No. 2,675,316 discloses the use of polymers containing dialkylamino groups as mordants.

U.S. Pat. No. 2,882,156 discloses aminoguanidine derivatives.

U.S. Patents 3,625,694, 3,859,096, British Patent 1,277,
Nos. 453 and 2,011,012 disclose a mordant capable of crosslinking with gelatin and the like.

US Pat. Nos. 3,958,995, 2,721,852 and 2,798,063 disclose aqueous sol type mordants.

Further, JP-A-50-61228 discloses a water-insoluble mordant.

Others, U.S. Pat. Nos. 3,709,690 and 3,788,855, West German Patent Application (OLS) 2,843,320, JP-A-53-30328 and 52
-155528, 53-125, 53-1024, 54-74430
No. 54-124726. No. 55-22766, U.S. Pat.
No. 82, No. 3,488,706, No. 3,557,066, No. 3,271,147
No. 3,271,148, Japanese Patent Publication No. 55-29418, 56-36414
No. 57-12139, RD12045 (1974), various mordants are disclosed.

Examples of the heat-resistant organic polymer substance include a molecular weight of 2000 to
85000 polystyrene, polystyrene derivatives having C4 or less substituents, polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinylalcohol, polyvinylformal, polyvinylbutyral and other polyacetals, polyvinyl chloride , Chlorinated polyethylene, polytrifluoroethylene, polyacrylonitrile, poly-N, N-dimethylallylamide, polyacrylate having p-cyanophenyl group, bentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate , Polymethylmethacrylate, polyethylmethacrylate, polypropylmethacrylate, polyisopropylmethacrylate, polyisoeptylmethacrylate, poly-tert- Chill methacrylate,
Examples thereof include polyesters such as polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate and polyethylene terephthalate, polysulfones, polycarbonates such as bisphenol A polycarbonate, polyanhydrides, polyamides and cellulose acetates. Also, Polymer Handbook 2nd cd. (J, Brandru
Synthetic polymers having a glass transition temperature of 40 ° C. or lower described in John Wiley & Sons, p., EHImmergut) are also useful. These polymer substances may be used alone or in combination of two or more and used as a copolymer.

Particularly useful polymers include cellulose acetate such as triacetate and diacetate, terephthalic acid with heptamethylenediamine, fluorenedipropylpropylamine and adipic acid, hexamethylenediamine and diphenic acid,
Examples thereof include polyamides in the combination of hexamethylenediamine and isophthalic acid, polyesters in the combination of diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, polyethylene terephthalate, and polycarbonate. These polymers may be modified. For example, cyclohexanedimethanol, isophthalic acid, methoxypolyethylene-glycol, 1,2
Polyethylene terephthalate using a modifier such as -dicarbomethoxy-4-benzenesulfonic acid is also effective.

These polymers may be coated on another support such as paper, glass, metal or the like to form an image receiving layer, or may be formed into a film sheet so as to have a function as a support by itself. May be. When these polymers are used as a support, the support may be formed of a single layer or multiple layers. The white reflective layer may be formed by having a part or layer containing titanium white in or on the outside of the support. The compound used as the mordant may be used alone or as a mixture with another polymer, which is coated on an appropriate support.

Various exposing 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. Generally, a light source used for ordinary color printing, for example, a tungsten lamp, a mercury lamp, a xenon lamp, a laser beam, a CRT beam 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.

It is also possible to directly output the image projected by a video camera or the like or the image information sent from a television station to a CRT or FOT and form an image on the photothermographic element by contact or a lens for printing.

In addition, LEDs (light-emitting diodes) that have made great 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 contains a yellow dye-donor and the red photosensitive layer contains a magenta dye-donor.
Further, the infrared-sensitive layer may contain a cyan dye-donor substance.

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., and this information is processed as necessary. Then, there is also a method of reproducing this image information on a CRT and using it as an image-like light source, or directly exposing three types of LEDs based on the processed information.

The relationship between the light-sensitive element of the present invention and the image-receiving layer used in combination with the light-sensitive element has already been described in the embodiments, but will be described in more detail. (1) When the photographic constituent layers of the light-sensitive element of the present invention are subjected to thermal development. And (2) the image receiving layer is directly or indirectly attached to the photographic constituent layer of the light-sensitive element of the present invention during thermal transfer after thermal development. And (3) an image receiving layer is integrally provided on the photographic constituent layers of the photosensitive element of the present invention, and imagewise exposure and heat development are carried out through the image receiving layer. It can be in any of the following formats: The image receiving layer is peeled off after thermal transfer, and It may be of any type in which the image receiving layer is not peeled off after thermal transfer.

In the present invention, the thermal transfer means that the dye is sublimated, vaporized, evaporated, melted by heat or dissolved by a solvent, and diffused and transferred.

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. As the 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. Usually, the heating temperature during transfer is 80 ° C to 200 ° C, preferably 80 ° C.
The heating time is usually 1 second to 1 minute, preferably 1 second to 40 seconds.

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), “(Japan Radio Co., Ltd.) and the like can be easily applied.

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

Example 1 22.7 g of benztriazole silver and 400 ml of methyl alcohol,
500 ml of an 8% polyvinyl alcohol (Gothenol AL-02 manufactured by Nippon Synthetic Chemical Industry) aqueous solution was added and dispersed by a ball mill for 24 hours.

Next, 28 ml of silver iodobromide emulsion (5 mol% of silver iodide, containing 60 g of gelatin and 353 mol of silver a in a cube having an average diameter of 0.1 μm and containing 3 mol of silver in 1 kg of emulsion) sensitized red-sensitive while stirring this dispersion liquid. Was added. Furthermore, P-amino-N, N-diethylaniline 8.3
The following structural couplers 3 as g and cyan dye forming couplers
0 g of DES (diethylhexyl sulfosuccinate) 5
% Aqueous solution 5 ml and gelatin 100 ml of a 5% aqueous solution was mixed and added to a pulverized and dispersed product by a ball mill. Further, 9 ml of a 2% methanol solution of 3-amino-4-allyl-5-mercaptotriazole and 50 g of acetamide were added and well stirred. The coating solution thus prepared was coated and dried on a gelatin subbed (3 μm dry film thickness) polyethylene terephthalate base (silver content: 5.2 g).
/ dm ² ).

Then, an intermediate layer was coated and dried by coating a 4% aqueous solution of polyvinyl alcohol on the surface so that the wet film thickness was 55 μm.

Then, according to the formulation of the first layer, a green-sensitive silver halide having the same composition was added in place of the red-sensitive silver halide, and the same composition was used except that a coupler having the following structure was used to obtain a wet film thickness of 55μ. Coating and dry This is referred to as Sample 1.

Ultrasonic dispersion was carried out by dissolving 3.6 g of di-t-octylhydroquinone in 5 ml of dibutyl phthalate 15 ml of ethyl acetate and adding 10 ml of 5% alkanol XC (manufactured by DuPont) aqueous solution to 40 ml of 5% gelatin aqueous solution. did. Then, the same sample as sample 1 was prepared, except that it was mixed with 9 ml of a 4% polyvinyl alcohol aqueous solution, and this was replaced with the intermediate layer of sample 1 and applied and dried so that the wet film thickness was 55 μm.

Then 1- (2,4,6-trichlorophenyl) -3-
(2'-chloro-5'-palmitoylamide anilino)
Sample 3 was prepared by replacing 3.1 g of -5-pyrazilone with di-t-octylhydroquinone. Subsequently, the same samples were prepared as Samples 4, 5 and 6 except that 1.86 g, 2.27 g and 1.98 g of the exemplified polymer couplers 2, 6 and 7, respectively, were replaced with the di-t-octylhydroquinone of Comparative Sample 2.

Also, a polymer coupler latex synthesized according to the synthesis method described in US Pat. No. 4,080,211 (Example 8) 25 ml (latex polymer concentration: 9.6%) was mixed with 1000 ml of a 4% polyvinyl alcohol aqueous solution, and the intermediate layer of Sample-2 was replaced with the intermediate layer coated so as to have a wet thickness of 55 μm.

Separately, a 5% solution of polyvinyl chloride in tetrahydrofuran (containing 10% by weight of dibutyl phthalate with respect to the polymer) was added to 1.2% of polyvinyl chloride per 1 m ² on photographic baryta paper.
An image receiving paper was prepared by coating so as to give 0 g.

Each of Samples 1, 2, 3, 4, 5 and 6 was exposed to red light through a step wedge and then contacted with the image receiving paper and the coated surfaces thereof and developed at 160 ° C. for 1 minute. Table 1 shows the results of measuring the red density and the green density at the highest density part.

As described above, it can be seen that the present invention using the polymer coupler is extremely improved in color turbidity.

Next, Table 2 shows the results obtained by exposing the film through a step wedge with flash light and developing it in the same manner.

As described above, in the present invention using a polymer coupler, color turbidity is greatly improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kimie Hoshino 1 Sakura-cho, Hino-shi, Tokyo Photograph by Konishi Roku Photo Co., Ltd. Yoshio Sugano (56) Reference JP-A-50-137537 (JP, A) Special Kai 60-119555 (JP, A) JP 60-133449 (JP, A)

Claims (1)

[Claims] 1. A photosensitive silver halide, an organic silver salt, a dye-providing substance capable of forming a diffusible dye by heat development and a binder, and the color sensitivity of the photosensitive silver halide and the formed dye. In a heat-development color diffusion transfer light-sensitive material having at least two light-sensitive layers each having a different hue from each other on a support, the color sensitivity and the hue of a produced dye are at least two different. A substantially non-photosensitive layer containing between at least one polymer coupler represented by the following general formula (1) capable of reacting with an oxidant of a color developing agent to immobilize the oxidant between the light-sensitive layers of the layers. A heat-developable color diffusion transfer light-sensitive material characterized by having a positive intermediate layer. General formula (1) [In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and X represents -CONH-, -NH.
CONH -, - NHCOO -, - COO -, - SO 2 -, - CO-, or -O- and represents Y represents -CONH-, or -COO- and represents,
A is an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms,
Alternatively, it represents an unsubstituted or substituted phenylene group, and the alkylene group may be linear or branched. Q represents a cyan dye-forming coupler residue, a magenta dye-forming coupler residue and a yellow dye-forming coupler residue capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developing agent. m and n represent 0 or 1. ]