JPH11184056A - Color diffusion transfer silver halide sensitive material and heat developed image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an image with high sensitivity and to ensure superior sharpness, shelf stability and durability at the time of development by using a specified substrate, a specified compd. as a color developing agent and a specified two-equiv. coupler as a coupler. SOLUTION: A continuous web-shaped substrate having 4-40 μm thickness is used. A compd. represented by formula I or II is used as a color developing agent. A two-equiv. coupler having a ballast group in a releasable group and forming a diffusible dye by coupling reaction with the oxidized body of the color developing agent is used as a coupler. In the formula I, R1 -R4 are each H or a substituent, A is hydroxyl or substd. amino, X is a combining group such as -CO- or -SO-, Y2 is a divalent combining group and Z1 is a nucleophilic group capable of attacking X. In the formula II, Yk and Zk are each N or a group represented by -CR5 = (where R5 is H or a substituent), (k) is an integer of >=0 and D is a proton dissociable group or a group convertible into a cation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color diffusion transfer silver halide light-sensitive material and an image forming method using the same.

[0002]

2. Description of the Related Art In the field of silver halide photography, a so-called color diffusion transfer method for forming a color image by fixing a diffusible dye imagewise emitted from a silver halide photosensitive material to an image receiving material is a known technique. Yes, used for instant photography. Also, a color image forming method by thermal development processing is known, and a product utilizing this method is sold by Fuji Photo Film Co., Ltd. under the names of "Pictrostat" and "Pictrography". In these methods, a pre-colored image forming dye (preformed dye) is used as a coloring material, and a part of the dye is diffused in the course of silver halide development and transferred to an image receiving material to obtain an image. . However, when a preformed dye as a coloring material and a silver halide emulsion are added to the same layer, a part of the exposed light is absorbed by the coloring material, so that the silver halide emulsion absorbs light. However, there is a problem in that the sensitivity is reduced because the amount of is reduced (filter effect). Therefore, in order to avoid this problem, a so-called coupling that forms a diffusible dye from a colorless coloring material by a coupling reaction between an oxidized color developing agent generated by silver halide development and a coupler is used. Has been proposed.
That is, in the coupling system, the oxidized form of the color developing agent releases the functional compound from the coupling site of the coupler, replaces the ballast group in the coupling site, and forms a diffusible dye by the release. .

However, since the color developing agent used in the coupling is a reducing agent, it is easily oxidized by oxygen molecules in the air, and there is a problem in storage stability. In order to solve this problem, in the art, a color developing agent having excellent storage stability and capable of being incorporated in a photosensitive material is disclosed in US Pat.
1,240-p-sulfonamidophenol,
P-Aminophenylsulfamic acid described in JP-A-60-128438, sulfonylhydrazine described in JP-A-8-227131, sulfonylhydrazone described in JP-A-8-202002, European Patent 727708A1
Carbamoylhydrazine described in JP-A-8-234
No. 390, for example, has been proposed. Further, as a method for improving the storage stability of a color developing agent, a solid dispersion addition method of a 1-phenyl-3-pyrazolidinone derivative described in JP-A-2-230143 has been proposed. These p-aminophenol derivatives,
It is known that a p-phenylenediamine derivative can form a dye which gives a very good hue when used as a color developing agent. In particular, US Pat.
Sulfonamide phenols described in JP-A Nos. 1,240 and JP-A-60-128438 are compounds which are excellent in image discrimination and raw storage even when incorporated in photosensitive materials. It has been known. However, when this p-sulfonamidophenol was used as a color developing agent, it was found that the color development efficiency was extremely low in combination with a so-called 2-equivalent coupler.

Further, in the coupling system, since both the color developing agent and the coupler are colorless, there is no energy loss due to the filter effect, and the exposure sensitivity is increased, but a new problem that the sharpness is deteriorated arises. There has been a need for a technique for improving sharpness, particularly a technique for achieving both high sensitivity and sharpness.
Here, the sharpness indicates the appearance of the boundary between a colored portion and a non-colored portion. For example, good sharpness means that the boundary can be clearly distinguished.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color diffusion transfer silver halide photosensitive material capable of forming an image with high sensitivity and having excellent sharpness, storage stability and durability during development. An object of the present invention is to provide a material and a heat development image forming method using the same. Still another object of the present invention is to reduce the size of a photosensitive material and a processor for print output using the same.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that when a color developing agent represented by the following general formulas (1) and (2) is used, a color developing agent having a ballast group as a leaving group is used. Efficiently reacts with the equivalent coupler to form a diffusible dye and transfer it to the image receiving material to form a printed image with excellent discrimination. The thickness of the support of the photosensitive material is in the range of 4 μm to 40 μm. As a result, the inventors have found that the sharpness is improved, and have completed the present invention. That is, the object of the present invention has been achieved by the following means. (1) A color diffusion transfer silver halide comprising, on a support, a photosensitive material having a photosensitive layer containing at least a photosensitive silver halide emulsion, a color developing agent, a coupler and a binder, and an image receiving material having an image receiving layer containing a mordant. A photosensitive material, wherein the support of the photosensitive material has a thickness of 4 μm or more and 40 μm or more.
The following continuous web-form support, wherein the color developing agent is a compound represented by the following general formula (1) or (2), wherein the coupler has a ballast group as a leaving group, Is a two-equivalent coupler which forms a diffusible dye by a coupling reaction with an oxidized product of the above.

[0007]

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(Wherein, R _{1 to} R ₄ represent a hydrogen atom or a substituent. A represents a hydroxyl group or a substituted amino group. X
Is -CO -, - SO -, - SO 2 -, - (Q) PO-
(Q represents a monovalent group bonded to a phosphorus atom). Y ₂ represents a divalent linking group. Z ₂ is a nucleophilic group, which represents a group capable of attacking X when the present compound is oxidized. Two or more atoms or substituents arbitrarily selected from R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form a ring. )

[0009]

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(Wherein R _{1 to} R ₄ , A and X are the same as those in the general formula (1). Y _k and Z _k are nitrogen atoms or-
CR ₅ = represents a group represented by (R ₅ is a hydrogen atom or a substituent). k represents an integer of 0 or more. D represents a proton dissociable group or a group that can be a cation. R ₁ and R ₂ , R
₃ and R ₄ and two or more atoms or substituents arbitrarily selected from Y _k , Z _k , and D may be independently bonded to each other to form a ring. (2) The color diffusion transfer silver halide photosensitive material as described in (1) above, wherein the support has a metal thin film layer. (3) The color diffusion transfer silver halide photosensitive as described in (2) above, wherein an undercoating layer containing a boron compound or a silane-based compound is provided below the photosensitive layer as a layer adjacent to the metal thin film layer. Material. (4) The color diffusion transfer silver halide photosensitive material according to (2) or (3), wherein the metal thin film layer is an aluminum thin film layer. (5) After the color diffusion transfer silver halide photosensitive material according to any one of (1) to (4) is imagewise exposed, the entire coating film on the photosensitive layer surface of the photosensitive material is supported. The amount of water required for maximally swelling the entire coating film on the image receiving layer surface of an image receiving material having an image receiving layer containing at least a base and / or a base precursor and a mordant on the body is 0.1%.
The light-sensitive material and the image-receiving material are superimposed on each other and heated at a temperature of 60 ° C. to 100 ° C. for 5 seconds to 60 seconds in the presence of 1 to 1 time of water, whereby the coupler is formed imagewise. This is a heat development image forming method for forming a color image on the image receiving material by transferring the diffusible dye to the image receiving material, peeling off the photosensitive material and the image receiving material.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The color diffusion transfer silver halide light-sensitive material of the present invention (hereinafter, referred to as a light-sensitive material) has a light-sensitive layer on a support, and the light-sensitive layer includes at least a light-sensitive silver halide emulsion, Contains a developing agent, a coupler and a binder.

The support used in the light-sensitive material of the present invention comprises:
It is a continuous web, and its thickness is 4 μm or more and 40 μm or less, preferably 5 μm or more and 36 μm or less, and more preferably 6 μm or more and 25 μm or less. Conventionally, a relatively thick support having a thickness of about 100 μm or more has been used as a support for a photosensitive material. A support previously processed into a sheet may be used, or a support processed into a continuous web may be used. Is cut into a sheet when used. On the other hand, in the present invention, the continuous web-like
It is characterized in that a thin support having a thickness of 0 μm or less is used. In addition, since the support is thin, the outer diameter of the photosensitive material when it is wound up after development can be reduced, and continuous processing can be performed without cutting the sheet one by one. And the processing speed (total length of the photosensitive material processed per unit time) can be increased. When the thickness exceeds 40 μm, these effects become insufficient. On the other hand, when the thickness is less than 4 μm,
There is a disadvantage that the strength of the support itself is reduced.

The support of the present invention can have a metal thin film layer. As the metal forming the metal thin film layer, a metal having a reflectance of 0.5 or more in a smooth surface state is preferably used. Bnnford et al. Opt. So
c. Amer. Journal, Vol. 32, pp. 174 to 184 (194
2)), silver, aluminum, magnesium, and alloys thereof. Especially, aluminum and its alloy are preferable. The metal thin film layer can be formed of a metal foil (for example, one having a thickness of about 1 μm to 100 μm). Further, it can be formed as one or two or more metal vapor-deposited films obtained by a known method such as vacuum vapor deposition, sputtering, ion plating, electrodeposition, or electroless plating. Among the methods for forming a deposition film, a vacuum deposition method is more preferable.
When a metal foil is used, a support having a metal thin film layer can be obtained by laminating the metal foil on a substrate. When using a metal deposition film,
A deposited film is formed on the flattened substrate according to the method described above. For example, in the case of a vacuum evaporation method, generally, a metal is dissolved and evaporated under a reduced pressure environment, and the metal is cooled and solidified on a substrate to form an evaporation film. The thickness of the thin film at the time of forming a monomolecular film is 100 to 5 μm, preferably 200 to 1 μm, and more preferably 500 to 0.1 μm.
More preferably, it is 5 μm or less. Such a metal thin film layer can be provided on one or both sides of the substrate,
Various commercially available supports can be used as such a support. Note that an anchor layer for improving the adhesion between the substrate and the metal thin film may be provided between the substrate and the metal thin film.

By providing such a metal thin film layer having a high surface reflectance on the support of the light-sensitive material of the present invention, the utilization efficiency of light energy is increased and the sensitivity of the light-sensitive material can be remarkably increased. Further, sharpness can be improved. Further, the adhesion between the photosensitive layer and the support can be improved.

The material used for the substrate of the support is not particularly limited as long as it can withstand the processing temperature for development and the like. In general, papers, synthetic polymers (films), etc., described in the Photographic Society of Japan, "Basics of Photographic Engineering-Silver salt photography-", pages 223 to 240, published by Corona Co., Ltd. (1979). Photographic supports. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose), those containing pigments such as titanium oxide in these films, Synthetic paper laminated with polypropylene or the like, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper) and the like are used. Among these, when a metal is deposited, a synthetic polymer film suitable for this is preferably used. Further, a styrene-based polymer mainly having a syndiotactic structure can also be preferably used as the substrate.

A hydrophilic binder and an antistatic agent may be applied to the surface of the substrate opposite to the surface on which the metal thin film layer is formed. As the antistatic agent, semiconductive metal oxides such as alumina sol and tin oxide, carbon black, and other antistatic agents can be used.

In the light-sensitive material of the present invention, an undercoat layer for improving adhesion may be provided between the support and the light-sensitive layer. As the undercoat layer, a conventionally known undercoat layer can be used, but when the support of the photosensitive material of the present invention has a metal thin film layer, the support and the photosensitive layer In order to further enhance the adhesion, the undercoat layer preferably contains a boron compound or a silane compound. It is thought that the adhesion between the metal thin film layer and the photosensitive layer is further improved by the action of the boron compound or the silane compound and the hardener in the photosensitive layer. A borate is preferably used as the boron compound. Borates exist naturally in the forms represented by several chemical formulas. For example, K
_{B 5 O 8 · 4H 2 O} , Na 2 B 4 O 7 · 10H 2 O, C
aB ₂ O ₄ and Mg ₃ B ₇ O ₁₃ Cl. This diversity is based on the nature of boron, and borate is generally neutral. Examples of the silane compound include a vinyl silane compound, an acrylic silane compound, an epoxy silane compound, an amino silane compound, mercaptopropyltrimethoxysilane, chloropropyltrimethoxysilane, and the like. As the silane compound, an aminosilane compound is preferably used. In particular, when the metal thin film layer is an aluminum thin film layer, a borate and an aminosilane compound are preferably used.

The coating amount of the coating solution for the undercoat layer according to the present invention is as follows:
The solid content is 0.01 to 10 g / m ² ,
It is preferably from 5 to ¹ g / m2. Among them, the coating amount of the boron compound or the silane compound is usually 0.1
mg / m ^{2 to} 10 g / m ² , and 1 mg / m ²
It is preferably not less than 1 g / m ^{2 and not} more than 10 mg / m ^2.
It is particularly preferable that it is not less than m ^{2 and not} more than 0.5 g / m ² .

Next, the components contained in the photosensitive layer of the present invention will be described. As the color developing agent of the present invention, compounds represented by the following general formulas (1) and (2) are used.

[0020]

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[0021]

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The compounds represented by the general formulas (1) and (2) are classified into aminophenol derivatives and phenylenediamine derivatives, have the property of being excellent in raw preservability, and have a 2-equivalent gambler. It has the characteristic that it reacts efficiently with.

Specific examples of the substituent represented by R _{1 to} R ₄ include a halogen atom (for example, chloro group, bromo group), an alkyl group (for example, methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group). -Butyl group), aryl group (for example, phenyl group, tolyl group, xylyl group), carbonamido group (for example, acetylamino group, propionylamino group, butyroylamino group, benzoylamino group), sulfonamide group (for example, methanesulfonylamino group) Group, ethanesulfonylamino group, benzenesulfonylamino group,
Toluenesulfonylamino group), alkoxy group (for example, methoxy group, ethoxy group, aryloxy group (for example, phenoxy group), alkylthio group (for example, methylthio group,
Ethylthio group, butylthio group), arylthio group (for example, phenylthio group, tolylthio group), carbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group,
Dibutylcarbamoyl group, piperidinocarbamoyl group,
Morpholinocarbamoyl group, phenylcarbamoyl group,
A methylphenylcarbamoyl group, an ethylphenylcarbamoyl group, a benzylphenylcarbamoyl group), a sulfamoyl group (for example, a methylsulfamoyl group, a dimethylsulfamoyl group, an ethylsulfamoyl group, a diethylsulfamoyl group, a dibutylsulfamoyl group, Piperidinosulfamoyl group, morpholinosulfamoyl group,
Phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), cyano group, sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, phenylsulfonyl group, 4-chlorophenyl) Sulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), acyl group (for example, acetyl group, propionyl group, butyroyl) Group,
Benzoyl group, alkylbenzoyl group), ureido group (eg, methylaminocarbonamide group, diethylaminocarbonamide group), urethane group (eg, methoxycarbonamide group, butoxycarbonamide group), or acyloxy group (eg, acetyloxy group, propionyloxy group) Group, butyroyloxy group) and the like. R
Among _{1 ~R 4,} R ₂ and / or R ₄ is preferably a hydrogen atom. When A is a hydroxyl group, R _{1 to} R ₄
The sum of the Hammett constants sigma _P value is preferably made 0 or more, in the case of A is a substituted amino group total Hammett constant sigma _p value of R ₁ to R ₄ is preferably a 0 or less.
Further, two or more atoms or substituents arbitrarily selected from R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form a ring.

A represents a hydroxyl group or a substituted amino group.
Examples of the substituted amino group include a dimethylamino group, a diethylamino group, and an ethylhydroxyethylamino group. A in the general formula (2) is preferably a hydroxyl group.

X represents —CO—, —SO—, —SO ₂ —,
Represents a linking group selected from-(Q) PO-. Here, Q is a substituent that substitutes for a phosphorus atom.
_In addition to the substituents described in _{1 to} R ₄ , it may be a group represented by the following formula,

[0026]

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In the case of the general formula (1), -Y ₂ -Z ₂
And in the case of the general formula (2), − (Y _k =
Z _k ) _k -D.

Y ₂ represents a divalent linking group. The linking group, lone equal on Z ₂ are, means a group which links Z ₂ in a position such that it conveniently intramolecular nucleophilic attack on X via Y _2, in fact, determined The atoms are preferably connected so that the transition state when the nucleus group attacks nucleophilic X can form a 5- or 6-membered ring by the number of atoms.
Preferred linking groups Y ₂ include, for example, 1,2- or 1,3-alkylene groups, 1,2-cycloalkylene groups,
Examples thereof include a Z-vinylene group, a 1,2-arylene group, and a 1,8-naphthylene group.

Z ₂ represents a nucleophilic group. The nucleophilic group is capable of nucleophilic attack on a carbon atom, sulfur atom, or phosphorus atom of X after an oxidant formed by oxidizing the present compound with silver halide is coupled with a coupler, This means a group having a function of forming a dye. In this nucleophilic group, nucleophilicity is expressed by an atom having an unshared electron pair (eg, a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, a selenium atom), as is common in the field of organic chemistry. Etc.) and anionic species (eg, nitrogen anion, oxygen anion, carbon anion, sulfur anion). Examples of the nucleophilic group include a group having a partial structure or a dissociated form thereof described in the following specific examples.

[0030]

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In the general formula (2), R _{1 to} R ₄ , A and X are
This is the same as general formula (1). However, A is preferably a hydroxyl group.

Y _k and Z _k each represent a group represented by a nitrogen atom (—N ＝) or —C (R ₅ ) ＝. R ₅ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonamide group, a sulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio black, a galvamoyl group, a sulfamoyl group, a cyano group, a sulfonyl group,
Represents an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a ureido group, a urethane group, an acyloxy group, or the like. Here, as more specific examples of R _5, the same specific examples as the substituents for R _{1 to} R ₄ can be given.

K represents an integer of 0 or more;
It is preferably an integer of 0.

D represents a proton dissociable group or a group that can be a cation. After the oxidant of the compound produced by the oxidation reaction of the compound with silver halide is coupled to the coupler, the NX bond is triggered by electron transfer from D, and the substituent bound to the coupling site of the coupler. To form a dye. Specifically, after the coupling reaction, electron transfer occurs from an unshared electron pair of an atom that can be a proton-dissociated anion or cation on D toward the coupling site, and the electron transfer between X and Y _k (k =
A double bond between X and D at the time of 0)
Cleavage of the NX bond is caused, and further, a double bond is generated between the coupling site of the coupler and the N atom, and at the same time, the substituent on the coupler side is released as an anion. This series of electron transfer mechanisms results in the formation of a dye and the elimination of a substituent. Examples of atoms that can be proton-dissociated anions include an oxygen atom, a sulfur atom, a selenium atom, and a nitrogen atom or carbon atom substituted by an electron-withdrawing group or an electron-rich aromatic group (eg, an aryl group or a heteroaromatic ring group). Can be mentioned. In addition, examples of atoms that can be cations include a nitrogen atom and a sulfur atom. The proton-dissociable group is a group containing an atom that can be an anion that has undergone proton dissociation, and the group that can be a cation is a group containing an atom that can be a cation.

D is a substituent containing an atom that can trigger electron transfer as described above, and this atom can be substituted with various substituents. Examples of the substituent to be substituted on the atom include an alkyl group (for example, methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group), an aryl group (for example, phenyl group, tolyl group, xylyl group),
Carbonamido group (eg, acetylamino group, propionylamino group, butyroylamino group, benzoylamino group), sulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy Groups (eg, methoxy, ethoxy), aryloxy (eg, phenoxy), alkylthio (eg, methylthio, ethylthio, butylthio), arylthio (eg, phenylthio, tolylthio), carbamoyl (eg, methyl) Carbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidylcarbamoyl, morpholylcarbamoyl, phenylcarbamoyl, methyl Phenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), sulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidyl) Sulfamoyl, morpholylsulfamoyl, phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), cyano,
Sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl Group (for example, phenoxycarbonyl group),
An acyl group (eg, acetyl group, propionyl group, butyroyl group, benzoyl group, alkylbenzoyl group) or an acyloxy group (eg, acetyloxy group, propionyloxy group, butyroyloxy group), ureido group, urethane group, and the like can be given. D is particularly preferably an aralkyl group (particularly a benzyl group), an anilino group, a heterocyclic group, or a methylene group or a methine group substituted with an electron-withdrawing group. These groups may be substituted with a hydroxy group, an amino group, or a substituent described as R _{1 to} R ₄ .

Further, two or more atoms or substituents arbitrarily selected from R ₁ and R ₂ , R ₃ and R _4, and Y _k , Z _k and D are each independently bonded to each other to form a ring. May be.

Next, specific examples of the compounds represented by the formulas (1) and (2) are shown, but the compounds of the present invention are not limited thereto.

[0038]

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[0039]

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[0040]

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As a method for adding the color developing agents represented by the general formulas (1) and (2), first, a coupler, a color developing agent and a high-boiling organic solvent (for example, alkyl phosphate, alkyl phthalate) And the like, can be dissolved in a low-boiling organic solvent (eg, ethyl acetate, methyl ethyl ketone, etc.), dispersed in water using an emulsification dispersion method known in the art, and then added. In addition, Japanese Unexamined Patent Publication
Addition by the solid dispersion method described in 3-271339 is also possible.

The compounds represented by the general formulas (1) and (2) are preferably oil-soluble compounds when added by the emulsification dispersion method among the above-mentioned addition methods. For this purpose, it is necessary that at least one group having a ballast property is contained. The ballast group as used herein refers to an oil-solubilizing group, and is a group containing an oil-soluble partial structure having 8 to 80 carbon atoms, preferably 10 to 40 carbon atoms. For this purpose, it is preferable that any _one of R _{1 to} R ₄ , X, Y _1k , Z _1K , P, Y ₂ and Z ₂ be substituted with a ballast group having 8 or more carbon atoms. In particular, when the present compound is used for a diffusion transfer type color light-sensitive material, preferably Y _1k , Z _1K ,
It is preferable that P, Y ₂ and Z ₂ are substituted with a ballast group. In this case, the number of carbon atoms in the ballast group is preferably from 8 to 80, and more preferably from 8 to 20.

The amount of the color developing agents represented by the general formulas (1) and (2) has a wide range, but is preferably 0.01 to 100 times, more preferably 0.1 to 100 times the amount of the coupler. 1 to 10 moles is appropriate.

In the present invention, a two-equivalent coupler which forms a dye by an oxidative coupling reaction is used. The color developing agent of the present invention can form a dye by reacting with any of 4-equivalent and 2-equivalent couplers. The use of (1) makes it possible to obtain a transferred image excellent in discrimination.
Specific examples of couplers are described in Theory of the Photographic Process (4th. Ed. TH James).
s editing Macmilllan, 1977) pp. 291-3
Page 34, and pages 354 to 361, JP-A-58-12
No. 353, No. 58-149046, No. 58-1490
No. 47, No. 59-11114, No. 59-124399
Nos. 59-174835 and 59-231439
No., 59-231540, 60-12951,
Nos. 60-14242, 60-23474, 60
-66249 and the like. Examples of the coupler preferably used in the present invention are listed below.

As couplers preferably used in the present invention, there are compounds having structures represented by the following formulas (3) to (14). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

[0046]

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[0047]

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[0048]

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Formulas (3) to (6) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl, cyano, nitro or aryl group. , A heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group. R ¹⁵ is an optionally substituted alkyl group, aryl group, or heterocyclic group. In the general formula (6),
R ¹⁶ is an aryl group or a heterocyclic group which may have a substituent. Examples of the substituent which R ¹⁴ , R ¹⁵ and R ¹⁶ may have include, for example, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, cyano group, halogen atom, acylamino Group,
Sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylamino group, arylamino group, hydroxyl group,
Examples include various substituents such as a sulfo group.

In the general formulas (3) to (6), Y is a group which can be eliminated by a coupling reaction with an oxidized color developing agent and has a ballast group. Examples of Y include a carbamoyl group, a substituted methylene group (as a substituent, an aryl group, a sulfonamide group, a carbonamide group, an alkoxy group, an amino group, a hydroxyl group and the like) each having a ballast group, an acyl group, an alkoxy group, Aryloxy group,
Alkylthio group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, N-substituted heterocycle And the like. Among these, a leaving group bonded by an S atom or an O atom is particularly preferable as the leaving atom.

In the general formulas (3) to (6), R ¹⁴ and R
¹⁵ , R ¹⁴ and R ¹⁶ may combine with each other to form a ring.

Formula (7) represents a coupler called a 5-pyrazolone magenta coupler, wherein R ¹⁷ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. R ¹⁸ represents a phenyl group or a phenyl group substituted with one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group. Y is the same as in general formulas (3) to (6).

Among the 5-pyrazolone-based magenta couplers represented by the general formula (7), compounds wherein R ¹⁷ is an aryl group or an acyl group and R ¹⁸ is a phenyl group substituted by one or more halogen atoms are preferred.

Specifically, R ¹⁷ is phenyl, 2
-Chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5-
(3-octadecenyl-1-succinimide) phenyl, 2-chloro-5-octadecylsulfonamidophenyl or 2-chloro-5- [2- (4-hydroxy-
3-tert-butylphenoxy) tetradecanamido] aryl group such as phenyl, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-di-t-pentylphenoxy) acetyl, 2- (2,4-di- Acyl groups such as t-pentylphenoxy) butanoyl, benzoyl, and 3- (2,4-di-t-amylphenoxyacetoazide) benzoyl are preferred. These groups may further have a substituent, and It is preferably an organic substituent or a halogen atom connected by an atom, an oxygen atom, a nitrogen atom, or a sulfur atom. The R ^18, 2,4,6-
Trichlorophenyl, 2,5-dichlorophenyl, 2-
A substituted phenyl group such as a chlorophenyl group is preferred.

The formula (8) represents a coupler called a pyrazoloazole coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of nonmetallic atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Y is the same as in general formulas (3) to (6).

Among the pyrazoloazole-based couplers represented by the general formula (8), imidazo [1,2-] described in US Pat.
b] pyrazoles, pyrazolo [1,5-b] [1, 2, 4] triazoles described in U.S. Pat. No. 4,654,654, and pyrazolo [5,1-c] [1, 2,4] triazoles are preferable, and among these, pyrazolo [1,5-
b] [1,2,4] triazoles are preferred.

For details of the substituents of the azole ring represented by the substituents R ¹⁹ , Y and Q ³ , see, for example, US Pat. No. 4,540,654, column 2, line 41 to column 8, line 27. Are listed. Preferably, JP-A-61
Pyrazoloazole couplers having a branched alkyl group directly bonded to the 2,3 or 6-position of the pyrazolotriazole group as described in JP-A-65245.
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in
Pyrazolotriazole couplers having an alkoxy or aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 01443 is a pyrazolotriazole coupler having a carboxamide group in the molecule.

Formulas (9) and (10) are couplers called phenol couplers and naphthol couplers, respectively, wherein R ²⁰ is a hydrogen atom or —NHCOR.
_{^{72, -SO 2 NR 72 R 73}} , -NHSO 2 R 72, -NHC
^{OR 72, -NHCONR 72 R 73,} -NHSO 2 NR 72 R
Represents a group selected from ⁷³ . R ⁷² and R ⁷³ represent a hydrogen atom or a substituent. In the general formulas (9) and (10), R ²¹
Represents a substituent, i is an integer selected from 0 to 2, and j is 0
Represents an integer selected from Y is the same as in general formulas (3) to (6). ^Examples of the substituent for R ²¹ , R ⁷² , and R ⁷³ include those described above as the substituents for R ^{14 to} R ¹⁶ .

Preferable examples of the phenolic coupler represented by the general formula (9) include US Pat. No. 2,369,929.
Nos. 2,801,171, 2,772,162, 2,895,826, and 377,2002, and the like, 2-alkylamino-5-alkylphenols, U.S. Pat. No. 4334011 and No. 43
2,173,2,5-diacylaminophenols described in U.S. Pat. Nos. 3,469,956; U.S. Pat. No. 3,446,622;
And 2-phenylureido-5-acylaminophenols described in No. 7767 and the like.

A preferred example of the naphthol coupler represented by the formula (10) is described in US Pat.
No. 3, No. 4052212, No. 4146396,
Examples thereof include 2-carbamoyl-1-naphthols described in U.S. Pat. Nos. 4,228,233 and 4,296,200 and 2-carbamoyl-5-amide-1-naphthols described in U.S. Pat. No. 4,690,889.

[0061] Formula (11) to (14) are couplers called pyrrolotriazole couplers, R ^32, R
³³ and R ³⁴ represent a hydrogen atom or a substituent. Y is the same as in general formulas (3) to (6). ^R32 , ^R33 , ^R34
Examples of the substituent include those described above as the substituent of R ^{14 to} R ¹⁶ . Preferable examples of the pyrrolotriazole-based couplers represented by the general formulas (11) to (14) include EP 488248 A1 and EP 497197.
The couplers described in A1 and 545300, in which at least one of R ³² and R ³³ is an electron-withdrawing group, may be mentioned.

In addition, fused ring phenol, imidazole,
Pyrrole, 3-hydroxypyridine, active methine, 5,
Couplers having a structure such as a 5-fused heterocycle and a 5,6-fused heterocycle can be used.

As the condensed phenol coupler, couplers described in US Pat. Nos. 4,327,173, 4,564,586 and 4,904,575 can be used.

As the imidazole couplers, couplers described in US Pat. Nos. 4,818,672 and 5,051,347 can be used.

As the pyrrole-based coupler, JP-A No. 4-1 is used.
The couplers described in Nos. 88137 and 4-190347 can be used.

As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 can be used.

As active methine couplers, couplers described in US Pat. Nos. 5,104,783 and 5,162,196 can be used.

The 5,5-fused heterocyclic couplers include
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289 and pyrroleimidazole couplers described in JP-A-4-174429 can be used.

The 5,6-fused heterocyclic couplers include:
Pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, and couplers described in EP 556700 can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3819051A and 3823049, U.S. Pat. No. 329036, No. 354
No. 549A2, No. 374781A2, No. 3791
10A2, 386930A1, JP-A-63-1
No. 41055, No. 64-32260, No. 32261
JP-A-2-29747, JP-A-2-44340,
2-110555, 3-7938, 3-16
No. 0440, No. 3-172839, No. 4-17244
No. 7, 4-179949, 4-182645,
4-184337, 4-188138, 4-
Nos. 188139, 4-194847, 4-204
No. 532, No. 4-204731, No. 4-204732
The couplers described in the above publications can also be used.

Specific examples of the coupler usable in the present invention are shown below. The invention is of course not limited thereby.

[0072]

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[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

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[0077]

Embedded image

The silver halide which can be used in the present invention may be any of silver iodobromide, silver chloroiodobromide, silver bromide, silver chlorobromide, silver iodochloride and silver chloride. These compositions are selected according to the properties to be imparted to the photosensitive silver halide. For example, when high sensitivity is required as in a photographic material, a silver iodobromide emulsion is mainly used. Further, silver chloride is often used in print materials in which quickness and simplification of development processing are important.

The size of the silver halide grains constituting the photosensitive emulsion is 0.1 to 2 μm in terms of the diameter of a sphere having the same volume.
m, particularly preferably 0.2 to 1.5 μm. Further, the shape of the silver halide grains are those having a shape composed of normal crystals such as cubic, octahedral or tetradecahedral,
Those having an irregular shape such as a sphere, those having a hexagonal or rectangular flat shape, or the like can be arbitrarily used. In the photographic material, so-called high aspect ratio tabular grains having a large projected area diameter with respect to the grain thickness are preferably used for the purpose of imparting high sensitivity. Here, the aspect ratio is a value obtained by dividing the diameter of a circle equivalent to the projected area of a grain by the grain thickness.

On the other hand, particles composed of normal crystals such as cubes and octahedrons are preferably used in print materials, but particles having a high aspect ratio are preferably used for the purpose of imparting rapid developability.

For the techniques and properties of using these high aspect ratio tabular grains, see US Pat. No. 4,433,048,
Nos. 4,434,226 and 4,439,520. Further, the technology of ultra-high aspect ratio tabular grains having a grain thickness of less than 0.07 μm is disclosed in US Pat.
No. 4789, No. 5503970, No. 55097
No. 1, No. 5,536,632, European Patent No. 0699994
No. 5, No. 0699950, No. 0699948,
Nos. 0699944, 0701165, and 0699946. The high aspect ratio tabular grains described in these specifications are mainly composed of silver bromide or silver iodobromide, and the frequency of hexagonal tabular grains whose main plane is composed of (111) planes is high. Particles having such a shape generally have two twin planes parallel to the (111) plane. In order to prepare tabular grains having a high aspect ratio and a small grain thickness, it is a technical point to form the two twin planes with a narrow interval. For this purpose, it is important to control the binder concentration, temperature, pH, excess halogen ion species and the same ion concentration at the time of nucleation, and the supply rate of the reaction solution. The selective growth of the formed tabular nuclei not in the thickness direction but in the peripheral direction of the tabular plate is also a point of forming the high aspect ratio tabular grains. To this end, it is important to control the rate of addition of the reaction solution for particle growth and to select the most suitable binder as a binder in the growth process from the time of particle formation. The above specification states that gelatin having a low methionine content is advantageous for increasing the aspect ratio.

On the other hand, a technique for forming tabular grains by using high silver chloride having a high silver chloride content is also disclosed. For example, U.S. Patent Nos. 4,400,463 and 4,713,323.
No. 5,217,858 and European Patent No. 0423840.
And Japanese Patent Nos. 0647877, etc.
1) The technique of high silver chloride tabular grains having a plane as a main plane is disclosed. On the other hand, U.S. Pat. Nos. 5,264,337, 5,292,632, 5,310,635, and 52.
No. 75932, European Patent Nos. 0534395 and 06
No. 17320, International Publication WO94 / 22054, etc., show a technique of high silver chloride tabular grains having a (100) plane as a main plane. These are all techniques useful for preparing a high-sensitivity emulsion using silver chloride having excellent development speed and optical characteristics.

The silver halide grains are prepared so as to have various structures in the grains in addition to devising the above-mentioned shapes. A commonly used method is to form grains into a plurality of layers having different halogen compositions. Further, a technique of epitaxially growing crystals having different halogen compositions at the localized portions of the formed host grains is also preferably used for obtaining high sensitivity. For example, a technique is known in which a crystal having a high iodine content is epitaxially grown on a part of the surface of a host grain rich in silver bromide (at the top or ridge of the grain or on the surface). On the contrary, there is also known a technique of epitaxially growing crystals having higher solubility (for example, crystals having a higher silver chloride content) in silver bromide or silver iodobromide host grains. The latter is preferably used for imparting high sensitivity particularly to tabular grains having a small grain thickness.
Even in high silver chloride grains having a high silver chloride content, it is preferable to form a localized phase having a high silver bromide or silver iodide content inside or on the surface of the grains. In particular, it is preferable to epitaxially grow these localized phases on the vertices and ridges of the particle surface. These epitaxial crystal sites serve as effective photosensitive nucleation sites and provide high sensitivity.

For the purpose of improving the photographic characteristics of the photosensitive silver halide emulsion, it is preferable to dope a metal salt or complex salt into the grains. These compounds act as transient or permanent traps of electrons or holes in the silver halide crystal to obtain high sensitivity and high contrast, improve the illuminance dependence during exposure, or improve the exposure environment. This is useful for improving (temperature, humidity) dependence and suppressing a change in performance when pressure is applied before and after exposure. These dopants may be uniformly doped into silver halide grains, may be locally localized at specific sites inside the grains, or may be locally localized on subsurfaces or surfaces.
Various methods can be selected according to the purpose, or doping can be localized at the above-mentioned epitaxial crystal site. Preferred metals include first to third transition metal elements such as iron, ruthenium, rhodium, palladium, cadmium, rhenium, osmium, iridium and platinum, and amphoteric metal elements such as thallium and lead. These metal ions are doped in a suitable salt or complex salt form. Among these, a hexacoordinate halogeno complex or cyano complex using a halide ion or cyanide ion as a ligand is preferably used. Further, a complex having an organic ligand such as a nitrosyl ligand, a carbonyl ligand, a thiocarbonyl ligand, a dinitrogen ligand, or a bipyridyl ligand, a cyclopentadienyl ligand, a 1,2-dithioenyl ligand, or the like may be used. Can be. These techniques are disclosed in JP-A-2-236542,
No. 1-116637 and Japanese Patent Application No. 4-126629. Further, it is also preferable to dope a so-called chalcogen element divalent anion such as sulfur, selenium or tellurium. These dopants are also effective for obtaining high sensitivity and improving the dependence on exposure conditions.

The method for preparing silver halide grains in the present invention is a known method, that is, “Physics and Chemistry of Photography” by Grafkid, published by Paul Monte (P. Glafk).
ides, Chimie et Physique P
photographique, Paul Monte
1, 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GF Duffin, Photog).
raphic Emulsion Chemistr
y, Focal Press, 1966), "Production and Coating of Photographic Emulsions", by Zerikman et al., published by Focal Press (VL Zelikman et al., Maki).
ng and Coating of Photogr
aphic Emulsion, Focal Pres
s, 1964). That is, it can be prepared in various pH ranges such as an acidic method, a neutral method, and an ammonia method. In addition, as a method for supplying a water-soluble silver salt and a water-soluble halogen salt solution as a reaction solution, a one-side mixing method, a simultaneous mixing method, or the like can be used alone or in combination. Further, it is also preferable to use a controlled double jet method for controlling the addition of the reaction solution so as to keep the pAg during the reaction at a target value. Further, a method of maintaining a constant pH value during the reaction is also used. In forming the grains, a method of controlling the solubility of silver halide by changing the temperature, pH or pAg value of the system can be used, but thioethers, thioureas, rhodan salts and the like can also be used as the solvent. These examples are shown in
No. 11386, JP-A-53-144319 and the like.

The preparation of silver halide grains in the present invention is usually carried out by adding a water-soluble silver salt solution such as silver nitrate and a water-soluble silver salt solution such as an alkali halide in a solution in which a water-soluble binder such as gelatin is dissolved. Is supplied under controlled conditions. After the silver halide grains are formed, it is preferable to remove excess water-soluble salts.
This step is called a desalting or washing step, and various means are used. For example, a gelatin solution containing silver halide grains is gelled, cut into strings, and washed with cold water to remove water-soluble salts, such as the Nudel water washing method, inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactant Agent, an anionic polymer (eg, sodium polystyrene sulfonate), or a gelatin derivative (eg, an aliphatic acylated gelatin, an aromatic acylated gelatin, an aromatic carbamoylated gelatin, etc.) to aggregate the gelatin to remove excess salts. A sedimentation method for removal may be used. When the sedimentation method is used, excess salts are rapidly removed, which is preferable.

In the present invention, it is usually preferable to use a chemically sensitized silver halide emulsion. Chemical sensitization imparts high sensitivity to the prepared silver halide grains and contributes to imparting exposure condition stability and storage stability. For chemical sensitization, generally known sensitization methods can be used alone or in various combinations. As a chemical sensitization method,
Chalcogen sensitization using a sulfur, selenium or tellurium compound is preferably used. As these sensitizers, compounds that release the above-described chalcogen elements to form silver chalcogenides when added to a silver halide emulsion are used. Further, it is also preferable to use them in combination in order to obtain high sensitivity and to suppress fog. Also, gold,
A noble metal sensitization method using platinum, iridium, or the like is also preferable.
In particular, a gold sensitization method using chloroauric acid alone or in combination with a thiocyanate ion serving as a gold ligand can provide high sensitivity. When gold sensitization and chalcogen sensitization are used together, higher sensitivity can be obtained. In addition, a so-called reduction sensitization method in which a compound having an appropriate reducing property is used during grain formation to obtain a high sensitivity by introducing a reducing silver nucleus, is preferably used. A reduction sensitization method in which an alkynylamine compound having an aromatic ring is added during chemical sensitization is also preferable. When performing chemical sensitization, it is also preferable to control the reactivity of the compound by using various compounds having adsorptivity to silver halide grains. In particular, prior to chalcogen sensitization or gold sensitization, nitrogen-containing heterocyclic compounds and mercapto compounds,
A method of adding a sensitizing dye such as a cyanine or a merocyanine is particularly preferable. The reaction conditions for performing the chemical sensitization vary depending on the purpose, but the temperature is 30 ° C to 95 ° C, preferably 4 ° C.
0 ° C to 75 ° C, pH is 5.0 to 11.0, preferably 5.5 to 8.5, and pAg is 6.0 to 10.5, preferably 6.5 to 9.8. Regarding the chemical sensitization technology, JP-A-3-110555, JP-A-4-75798, JP-A-62-253159, JP-A-5-45833,
It is described in JP-A-62-40446.

In the present invention, it is preferable that the photosensitive silver halide emulsion is subjected to so-called spectral sensitization for imparting sensitivity to a desired light wavelength range. In particular, a color light-sensitive material incorporates a light-sensitive layer having photosensitivity to blue, green, and red in order to reproduce colors faithfully to the original. These sensitivities are provided by spectrally sensitizing silver halide. For spectral sensitization, a so-called spectral sensitizing dye is used, which is adsorbed on silver halide grains and has sensitivity in its own absorption wavelength range.
Examples of these dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. These examples are described in U.S. Pat. No. 4,617,257,
JP-A-180550 and JP-A-64-13546;
No. 45828, 5-45834 and the like. The spectral sensitizing dye is used alone or in combination of plural kinds of dyes. This is performed for the purpose of adjusting the wavelength distribution of spectral sensitivity and for supersensitization. With a combination of dyes exhibiting supersensitization, a sensitivity that greatly exceeds the sum of the sensitivities that can be achieved alone can be obtained. It is also preferable to use a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits a supersensitizing effect. Diaminostilbene compounds and the like can be mentioned as examples of the supersensitizer. Examples of these include US Pat. No. 3,615,564.
No. 1, JP-A-63-23145 and the like.
These spectral sensitizing dyes and supersensitizers can be added to the silver halide emulsion at any time during the preparation of the emulsion. It is added to the emulsion after chemical sensitization is completed at the time of preparation of the coating solution, added at the end of chemical sensitization, added during chemical sensitization, added before chemical sensitization, and added after grain formation is completed and before desalting. Various methods such as addition during the formation of particles or addition prior to the formation of particles can be used alone or in combination. It is preferable to add in a step before chemical sensitization in order to obtain high sensitivity. The amount of the spectral sensitizing dye or supersensitizer to be added varies depending on the shape and size of the grains or the photographic characteristics to be imparted, but is generally 10 ^-8 to 10 ^-1 mol, preferably 10 ^-5 mol per mol of silver halide. It is in the range of 10 to ² mol. These compounds can be added in a state of being dissolved in an organic solvent such as methanol or fluorine alcohol, or in a state of being dispersed in water together with a surfactant or gelatin.

It is preferable to add various stabilizers to the silver halide emulsion for the purpose of preventing fog and improving the stability during storage. Preferred stabilizers include azaindenes, triazoles, tetrazoles, nitrogen-containing heterocyclic compounds such as purines, mercaptotetrazole, mercaptotriazoles, mercaptoimidazoles, and mercapto compounds such as mercaptothiadiazole. Can be. Details of these compounds can be found in James, "Theory of Photographic Processes", published by Macmillan (TH James, The Theory of).
the Photographic Process,
Macmillan, 1977) pp. 396-399 and references cited therein. These antifoggants or stabilizers can be added to the silver halide emulsion at any time during the preparation of the emulsion. It is added to the emulsion after chemical sensitization is completed at the time of preparation of the coating solution, added at the end of chemical sensitization, added during chemical sensitization, added before chemical sensitization, and added after grain formation is completed and before desalting. Various methods such as addition during the formation of particles or addition prior to the formation of particles can be used alone or in combination. The amount of these antifoggants or stabilizers varies depending on the halogen composition and the purpose of the silver halide emulsion, generally 10 ^-6 per silver halide 1 mol to 10 ^-1 m
ol, preferably in the range of 10 ^-5 to 10 ^-2 mol.

The above-mentioned additives used in the silver halide emulsion of the present invention and known photographic additives which can be used in the photothermographic material and the dye fixing material of the present invention are described in the above-mentioned RD No. No. 17,643, No. 18,716
And Nos. 307 and 105, and the corresponding portions are summarized in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer 648, right column 3. Spectral sensitizer page 23 to 24, page 648, right column 866 to 868, strong Color sensitizer 頁 Page 649 4. Fluorescent brightener Page 24 Page 648 Right column Page 868 5. Antifoggant, Page 24-25 Page 649 Right column Page 868-870 Stabilizer 6. Light absorber, 25- Page 26 649 page right column 873 filter dye, page 650 left column UV absorber 7. Dye image 25 page 650 page left column 872 stabilizer 8. Hardener 26 page 651 left column 874-875 9. Binder Page 26 651 Left column 873-874 10. Plasticizer, Page 27 650 Right column 876 Lubricant 11. Coating aid, Page 26-27 Page 650 Right column 875-876 Surfactant 12. Static 27 Page 650 page right column pages 876-877 Inhibitor 13. Matting agent pages 878-879

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in 00,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above-mentioned organic silver salt is used in an amount of 0.01 per mole of photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

As the binder used in the present invention, a hydrophilic binder is preferably used. Examples thereof include the aforementioned RD and JP-A-64-13546, pages (71) to (7).
5) Those described on page 5 are mentioned. Specifically, transparent or translucent hydrophilic binders are preferable, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, polyvinyl alcohol. Synthetic polymer compounds such as pyrrolidone and acrylamide polymer are exemplified. Also, U.S. Pat.
No. 0,681, JP-A-62-245260, etc., ie, -COOM or -SO
₃ Homopolymers of vinyl monomers having M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumitomo Chemical Co., Ltd. Product name "Sumikagel L-5"
H ") is also used. These binders can be used in combination of two or more kinds. Particularly preferred is a combination of gelatin and the above binder, and gelatin is lime-treated gelatin, acid-treated gelatin,
What is necessary is just to select from the so-called demineralized gelatin which reduced the content of calcium etc., It is also preferable to use these in combination. In the present invention, the coating amount of the binder is preferably 0.01 g to ²⁰ g per 1 m ² , and particularly preferably 0.1 g to ²⁰ g.
It is appropriate that the amount is from 0.05 g to 10 g, and more preferably from 0.5 g to 7 g.

In the present invention, a dye-providing compound having a function of releasing or diffusing a diffusible dye imagewise may be used in combination. This type of compound can be represented by the following general formula [LI]. ((Dye) _m -Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image A difference in diffusivity of the compound represented by ((Dye) _m -Y) _n -Z corresponding to or opposite to a photosensitive silver salt having a latent image, or (Dye) _m -Y
(Dye) _m -Y and ((Dye)
_m- Y) represents a group having a property that causes a difference in diffusivity with _n- Z, m represents an integer of 1 to 5, n represents 1 or 2, and either m or n When is not 1, a plurality of Dyes may be the same or different. Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds. Is to form a diffusible dye image (negative dye image) corresponding to the development of silver halide.

Is a coupler having a diffusible dye as a leaving group and releasing a diffusible dye by reacting with an oxidized reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39,165
No. 4,443,940, U.S. Pat.
Nos. 867 and 4,483,914. Is a compound (DRR compound) that is reducible to silver halide or an organic silver salt and releases a diffusible dye when the partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. Representative examples are U.S. Pat. Nos. 3,928,312, 4,053,312, 4,055,428, 4,336,322, JP-A-59-65,839 and JP-A-59-65839. Nos. 59-69,839, 53-3,819, 51-104,343, RD
17,465, U.S. Pat. Nos. 3,725,062, 3,728,113, 3,443,939, JP-A-58-116,537 and JP-A-57-179,840.
And U.S. Pat. No. 4,500,626. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (4) described in the above-mentioned U.S. Pat. (3), (10)-(13), (16)-(19), (2
8) to (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. U.S. Pat. No. 4,639,408 Nos. 37-3.
The compounds described in column 9 are also useful. Other examples of the couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (RD Magazine, May 1978, pp. 54-58, etc.); Azo dyes used in silver dye bleaching method (US Pat. No. 4,235,9
No. 57, RD, April 1976, pages 30 to 32, etc., leuco dyes (US Pat. No. 3,985,565,
No. 4,022,617) and the like can also be used.

In the present invention, it is preferable that the color developing agent has diffusion resistance. In this case, it is necessary to promote electron transfer between the diffusion resistant color developing agent and developable silver halide. If necessary, an electron transfer agent and / or an electron transfer agent precursor can be used in combination. Particularly preferred are the aforementioned U.S. Pat. No. 5,139,919, European Patent Publication No. 418,743, and JP-A-1-138556.
No. 3,102,345 are used.
JP-A-2-230143, JP-A-2-23504
As described in No. 4, a method of stably introducing the compound into the photosensitive layer is preferably used.

Hydrophobic additives such as a dye-donating compound and an electron transfer agent can be added to a light-sensitive material in the same manner as in a color developing agent. You may make it contain as a fine particle dispersion in a binder. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, those mentioned as the surfactants described in the above-mentioned RD in JP-A-59-157636, pages (37) to (38) can be used.

In the light-sensitive material of the present invention, auxiliary layers such as a protective layer, a release layer, an undercoat layer, an intermediate layer, a back layer, and an anti-curl layer can be provided as necessary as other constituent layers.

A reducing agent can be used in the intermediate layer or the protective layer of the light-sensitive material of the present invention for various purposes such as prevention of color mixing, improvement of color reproduction, improvement of white background, and prevention of silver transfer to the dye fixing material. Specifically, European Patent Publication Nos. 524,649 and 357,040, JP-A-4-249,245, and JP-A-4-249245
Nos. 64,633 and 2-46,450,
No. 186,240 are preferably used. Japanese Patent Publication No. 3-63,733 and Japanese Patent Laid-Open No. 1-15
No. 135, No. 2-110, 557, No. 2-64,
No. 634, No. 3-43,735, European Patent Publication No. 45.
A development inhibitor releasing reducing compound as described in 1,833 is also used. In the present invention, the total amount of the reducing agent is from 0.01 to 20 mol, particularly preferably from 0.1 to 10 mol, per mol of silver.

To the light-sensitive material of the present invention, various compounds can be added for the purpose of fixing or decolorizing unnecessary dyes and coloring matters and improving the white background of the obtained image. Specifically, European Patent Publication Nos. 353,741 and 461,4
No. 16, JP-A-63-163,345 and JP-A-62-20
No. 3,158 can be used.

Various pigments and dyes can be used in the light-sensitive material for the purpose of improving color separation properties and increasing sensitivity. Specifically, the compounds described in the above-mentioned RD and European Patent No. 47
Nos. 9,167 and 502,508, JP-A-1-16
7,838, 4-343,355, 2-16
No. 8,252, JP-A-61-20,943, and EP-A-479,167, EP-A-502,508 and the compounds described in JP-A Nos. 502,508 can be used.

In the heat development image forming method of the present invention,
After transferring the diffusible dye imagewise formed by the coupler to the image receiving material, the photosensitive material and the image receiving material are peeled off to form a color image on the image receiving material. The image receiving material used in the invention has at least an image receiving layer containing at least a base and / or a base precursor and a mordant on a support.

As the support of the image receiving material of the present invention, a support that can withstand the processing temperature for development or the like is used. In general, the Photographic Society of Japan
Silver salt photography-", published by Corona Co., Ltd. (Showa 54) (2
Photographic supports such as paper and synthetic polymers (films) described on pages 23 to 240. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, furthermore Film-process synthetic paper made from polypropylene, etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass, etc. Is used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In this laminate layer,
Pigments and dyes such as titanium oxide, ultramarine blue, and carbon black can be contained as necessary. In addition, JP-A-62-253,159, pages (29) to (31), JP-A-1-61,236, pages (14) to (17), and JP-A-63-31
No. 6,848, JP-A Nos. 2-22,651, 3-5
Supports described in US Pat. No. 6,955, US Pat. No. 5,001,033 and the like can be used. The back surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or another antistatic agent. Specifically, Japanese Unexamined Patent Publication No.
The support described in JP-A-220,246 or the like can be used. The surface of the support is preferably subjected to various surface treatments or undercoating for the purpose of improving the adhesion to the hydrophilic binder.

The base and / or the base precursor is used for accelerating the image formation at the time of development. In the present invention, the base and / or the base precursor are contained in the image receiving material for the purpose of enhancing the storability of the photosensitive material. As the base, an inorganic or organic base can be used. Examples of the inorganic base include hydroxides, phosphates, carbonates, borates and organic acid salts of alkali metals or alkaline earth metals described in JP-A-62-209448, and JP-A-63-25208. Acetylide of an alkali metal or an alkaline earth metal.
Examples of the organic base include ammonia, aliphatic or aromatic amines (eg, primary amines, secondary amines, tertiary amines, polyamines, hydroxylamines, heterocyclic amines), amidines , Bis or tris or tetraamidine, guanidines, water-insoluble mono or bis or tris or tetraguanidines, and quaternary ammonium hydroxides.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement. A specific example is described in U.S. Pat.
No. 493, 4,657,848 and the like.

In addition to the above, European Patent Publication 210,660
No. 4,740,445, a combination of a compound which is capable of forming a complex with a metal ion constituting the hardly soluble metal compound (hereinafter referred to as a complex forming compound), Compounds that generate a base by electrolysis described in JP-A 61-232,451 can also be used as the base precursor. In particular, the former method is effective. It is advantageous to add the hardly soluble metal compound and the complex-forming compound separately to the light-sensitive material and the image-receiving material as described in the above patent.

As the mordant, those known in the field of photography can be used, and specific examples thereof are described in US Pat. No. 4,500,
No. 626, columns 58-59, JP-A-61-88,256, pages (32)-(41) and JP-A-1-161,236, (4)-
(7) The mordant described on page 7, US Pat. No. 4,774,162
And Nos. 4,619,883 and 4,594,308. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used.

The binder used in the image receiving material of the present invention is preferably the same hydrophilic binder as used in the photosensitive material. Further, European Patent No. 443,529
No. 3-7, and carrageenans as described in
It is preferable to use a latex having a glass transition temperature of 40 ° C. or lower as described in US Pat.

The image receiving material may be provided with auxiliary layers such as a protective layer, a release layer, an undercoat layer, an intermediate layer, a back layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

The image-receiving material of the present invention may contain an anti-fading agent. Examples of the anti-fading agent include antioxidants, ultraviolet absorbers, and certain metal complexes.
The dye image stabilizers and ultraviolet absorbers described are also useful. Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Also,
The compounds described in JP-A-61-159,644 are also effective. Examples of ultraviolet absorbers include benzotriazole-based compounds (such as U.S. Pat. No. 3,533,794), 4-thiazolidone-based compounds (such as U.S. Pat. 2,78
No. 4, etc.), and JP-A Nos. 54-48,535 and 6
There are compounds described in 2-136,641 and 61-88,256. Also, JP-A-62-260152
The UV-absorbing polymer described in the above item is also effective. Examples of metal complexes include U.S. Pat. Nos. 4,241,155 and 4,2,155.
No. 45,018, columns 3-36, 4,254,195
Nos. 3 to 8; JP-A Nos. 62-174, 741, 61;
No. 88-256, pp. 27-29, 63-199, 24
No. 8, JP-A Nos. 1-75,568 and 1-74,272
And the like. The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination. A fading preventing agent for preventing fading of the dye transferred to the image receiving material may be contained in the image receiving material in advance, or may be supplied from the photosensitive material to the image receiving material.

In the image receiving material of the present invention, a fluorescent whitening agent may be used as an image receiving fixing material. For example, K. Veenka
Compounds described in Taraman, edited by Taraman, "The Chemistry of Synthetic Dyes", Vol. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given. These fluorescent whitening agents can be used in combination with a fading inhibitor or an ultraviolet absorber. Specific examples of these anti-fading agent, ultraviolet absorber and fluorescent whitening agent are described in JP-A-62-215272 (125) to (13).
7), and JP-A-1-161,236, pages (17) to (43).

In addition, various additives can be added to the constituent layers of the light-sensitive material and the image-receiving material of the present invention.
For example, a high-boiling organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability between the photosensitive material and the image receiving material. Specifically, the RD and JP-A-62-24
No. 5,253 and the like. Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. An example is the “Modified Silicone Oil” Technical Data P issued by Shin-Etsu Silicone Co., Ltd.
6-18B, in particular, carboxy-modified silicone (trade name “X-22-371”).
0 ”) is effective. Also, JP-A-62-215,
The silicone oils described in Nos. 953 and 63-46,449 are also effective.

The hardeners used in the constituent layers of the light-sensitive material and the image-receiving material of the present invention include RD and US Pat.
8,739, column 41, 4,791,042, JP-A-59-116,655, 62-245,261
No. 61-18,942, JP-A-4-218,04
No. 4 and the like. More specifically,
Aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetaamide) ethane, etc.), N- Methylol-based hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157) can be mentioned. These hardeners consist of 1 g of applied gelatin
0.001 to 1 g, preferably 0.005 to 0.
5 g are used. The layer to be added may be any of the constituent layers of the light-sensitive material and the dye-fixing material, or may be added in two or more layers.

In the constituent layers of the light-sensitive material and the image-receiving material of the present invention, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include azoles and azaindenes described in RD 17643 (1978), pp. 24-25, and JP-A-59-1684.
No. 42, such as nitrogen-containing carboxylic acids and phosphoric acids, or mercapto compounds and metal salts thereof described in JP-A-59-111,636, and acetylene compounds described in JP-A-62-87,957. Is raised.
When a precursor is used in the present invention, it is particularly preferably used for a photosensitive silver halide emulsion layer, but it can also be used for an image receiving material.

In the constituent layers of the light-sensitive material and the image-receiving material of the present invention, coating aids, improved releasability, improved slipperiness, antistatic properties,
Various surfactants can be used for the purpose of accelerating development and the like. Specific examples of the surfactant are described in the above-mentioned RD,
173,463 and 62-183,457. Further, the constituent layers of the light-sensitive material and the image-receiving material of the present invention may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability, and the like. Representative examples of the organic fluoro compound include JP-B-57-9053, No. 8
Column 17, JP-A-61-20944, JP-A-62-13
5,826 or the like, a fluorine-based surfactant,
Or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin.

A matting agent can be used in the light-sensitive material and the image-receiving material of the present invention for the purpose of preventing adhesion and improving slipperiness. Examples of the matting agent include silicon dioxide, polyolefin, and polymethacrylate.
In addition to the compounds described on page 256 (29), JP-A Nos. 63-274,944 and 63-2 describe benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
No. 74,952. In addition, the compounds described in the above RD can be used. These matting agents may be added not only to the uppermost layer (protective layer) but also to the lower layer as needed. In addition, the constituent layers of the light-sensitive material and the image-receiving material of the present invention may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88,256, pp. (26)-(32);
No. 11,338 and Japanese Patent Publication No. 2-51,496.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the image-receiving material for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-25
No. 3,159, pages (31) to (32).

The heat-developable image forming method of the present invention is characterized in that the light-sensitive material of the present invention is used. The light-sensitive material of the present invention is exposed imagewise and then thermally developed so that the coupler is formed imagewise. After the diffusible dye to be formed is transferred to the image receiving material, the photosensitive material and the image receiving material are peeled off to form a color image on the image receiving material.

Examples of a method of exposing and recording an image on a photosensitive material include a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or a enlarger, Using a copier exposure device to scan and expose the original image through slits, etc., image information via electric signals, light emitting diodes, various lasers (laser diodes,
A method of performing scanning exposure by emitting light by using a gas laser or the like (Japanese Patent Application Laid-Open No. 2-129625, Japanese Patent Application Laid-Open No. 5-17614)
4, JP-A-5-199372, JP-A-6-1270
No. 21, etc.), a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, and exposing directly or via an optical system.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No. 4,500,626, column 56, natural light, tungsten lamp, light emitting diode, laser light source, CRT light source and the like, JP-A-2-53,37.
No. 8, No. 2-54, 672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of expressing nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate, potassium dihydrogen phosphate (K
DP), lithium iodate, BaB ₂ O _{4 and} other inorganic compounds, urea derivatives, nitroaniline derivatives,
For example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-53,462 and JP-A-62-210,4
The compound described in No. 32 is preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. In addition, the image information includes an image signal obtained from a video camera, an electronic still camera, and the like, and the Nippon Television Signal Standard (NTT).
SC), an image signal obtained by dividing an original image into a large number of pixels such as a scanner, and an image signal created by using a computer such as CG and CAD.

In the heat development of the present invention, the amount of water required for maximally swelling the entire coating film on the photosensitive layer surface of the photosensitive material and the entire coating film on the image receiving layer surface of the image receiving material is 0.1 to 1 times. In the presence of water, the light-sensitive material and the image-receiving material are overlaid at
It is performed by heating at a temperature of 100 ° C. for 5 to 60 seconds. The water mentioned here may be any water that is generally used. Specifically, distilled water, ion-exchanged water,
Tap water, well water, mineral water and the like can be used. A method in which a small amount of a preservative is added to these waters for the purpose of preventing generation of scale and decay, and circulating and filtering the water with an activated carbon filter, an ion exchange resin filter or the like is also preferably used. In the present invention, the light-sensitive material and / or the image-receiving material are bonded in a state of being swollen with water,
Heated. The state of the film at the time of swelling is unstable, and it is important to limit the amount of water to the above range in order to prevent local uneven coloring. The amount of water required for maximum swelling is determined by immersing a photosensitive or image-receiving material with a coating film to be measured in the water used, measuring the film thickness when it swells sufficiently, calculating the maximum swelling amount, and then calculating the maximum swelling amount. Can be determined by reducing the weight of An example of a method for measuring the degree of swelling is described in Photographic Science Engineering, Vol. 16, p. 449 (1972). As a method for applying water, there is a method in which a photosensitive material or an image receiving material is immersed in water and excess water is removed with a squeeze roller. However, it is preferable to apply a predetermined amount of water to the photosensitive material or the image receiving material by coating. Also, a plurality of nozzle holes for ejecting water are arranged at regular intervals in a straight line along a direction intersecting the conveying direction of the photosensitive material or the image receiving material. In particular, a method in which water is sprayed by a water applicator having an actuator for displacing water toward the surface is particularly preferable.
In addition, a method of applying water with a sponge or the like is also preferable because the apparatus is simple. The temperature of the water to be applied is 30 ° C
~ 60 ° C is preferred. Examples of a method of superposing a photosensitive material and an image receiving material are described in JP-A-62-253159.
No. 61-147,244.

As a heating method in the heat development step, a heating block, a plate, or a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared or far-infrared lamp heater, or the like is contacted. Or through a high temperature atmosphere. In the heat development processing of the present invention, any of various heat development processors can be used. For example, JP-A-59-75,24
No. 7, 59-177, 547, 59-181, 3
No. 53, No. 60-18, 951;
944, JP-A-6-130509, JP-A-6-95
338, JP-A-6-95267, JP-A-8-299
No. 55, JP-A-8-29954 and the like are preferably used. Examples of commercially available processors include “Pictrostat 100”, “Pictrostat 200”, “Pictrostat 300”, and “Pictrostat 3” manufactured by Fuji Photo Film Co., Ltd.
30, "Pictrostat 50", "Pictrography 3000", "Pictrography 200"
"0" can be used.

The light-sensitive material and / or the image-receiving material used in the present invention may have a form having a conductive heating element layer as a heating means for heat development. As the heat generating element of the present invention, those described in JP-A-61-145544 can be used.

The image obtained from the photosensitive material and the image receiving material may be used as a color proof for printing.
The method of expressing the density may be either continuous tone control, area tone control using a discontinuous density portion, or tone control combining the two. By using an LD or LED as an exposure light source, a digital signal can be output. In this way, a method of controlling an image such as the design and color of a printed matter on a CRT and outputting a color proof as a final output (DDC)
P) becomes possible. That is, DDCP is an effective means for efficiently outputting proofs in the field of color proofs. This is because a color printer has a relatively simple structure and is inexpensive, and a color printer does not require the production of a plate-making film or a printing plate (PS plate) for a color printing machine, as is well known. Yes, it is possible to easily produce a hard copy having an image formed on a sheet a plurality of times in a short time. L as an exposure light source
When using D or LED, three or more spectral sensitivities of yellow, magenta and cyan, or four spectral sensitivities of yellow, magenta, cyan and black, and two or more color materials are mixed for the purpose of obtaining a desired hue. It is preferable that the spectral sensitivity of each color obtained as described above has a peak of the spectral sensitivity at a different wavelength separated by 20 nm or more. Still another method is to obtain an image of two or more colors at one exposure wavelength when the spectral sensitivity of two or more different colors has a sensitivity difference of 10 times or more.

Next, a method of reproducing a moire or the like on a printed matter by a color printer will be described. In order to produce a printing color proof that faithfully reproduces moire or the like appearing on high-resolution printing by a low-resolution color printer, a threshold matrix is used for each of the CMYK4 halftone dot area data aj. With reference to 24, each is converted into bitmap data b'j of 48800 DPI. Next, the area ratio ci for each color is counted by simultaneously referring to the bit map data b'j in a certain range. Next, the first tristimulus value data X, Y, Z of 1600 DPI, which is the colorimetric value data for each color, which is obtained in advance, is calculated. The first tristimulus value data X, Y, and Z are subjected to anti-aliasing filter processing to obtain 400 DPI.
Of the second tristimulus value data X ′, Y ′, Z ′.
This calculation data is used as input data for the color printer.
Details are described in JP-A-8-192540.

When a color image is recorded using an output device such as a color printer, a color image having a desired color can be realized by manipulating color signals for yellow, magenta, and cyan, for example. However, since the color signal depends on the output characteristics of the output device, it is necessary to perform color conversion processing on the color signals supplied from external devices having different characteristics in consideration of the output characteristics. Therefore, a plurality of known color patches having different colors are produced using the output device, and the color patches are measured, so that, for example, a known color signal CMY of the color patch is stimulated independent of the output device. A conversion relationship for converting into a value signal XYZ (hereinafter, this conversion relationship is referred to as a “forward conversion relationship”) is obtained,
Next, a conversion relationship for converting the stimulus value signal XYZ into a color signal CMY (hereinafter, this conversion relationship is referred to as an “inverse conversion relationship”) is determined from the forward conversion relationship, and the color conversion process is performed using the inverse conversion relationship. There is a way to do it. Here, as a method of obtaining the color signal CMY from the stimulus value signal XYZ,
The following three examples are given, but the examples of the present invention are not limited thereto. 1. A tetrahedron having the stimulus value signals XYZ at four points as vertices is set, and the space of the stimulus value signal XYZ is divided by the tetrahedron, and the space of the color signal CMY is similarly divided by the tetrahedron. A color signal CMY for an arbitrary stimulus value signal XYZ in a tetrahedron to be obtained by a linear operation. 2. A method of repeatedly calculating a color signal CMY corresponding to an arbitrary stimulus value signal XYZ using the Newton method. (PHOTOGRAPHIC SCIENCE AND ENGINEERINGVolume 1
6, Number 2.March-April 1972 pp136-pp143 "Metamer
ic color matching in subtractive color photograph
3. In the color conversion method for converting a color signal from the first color system to the second color system, the color conversion method of the first color system obtained from the known real color signal of the second color system. A first step of obtaining a relationship between real color signals as a first forward conversion relationship, and a second step of approximating the first forward conversion relationship with a monotonic function and setting a virtual color signal outside an area composed of the real color signals And a third step of obtaining a relationship between the color signals of the first color system obtained from the color signals composed of the real color signals and the virtual color signals in the second color system as a second forward conversion relationship. From the second conversion relation, using the iterative operation method,
A fourth step of obtaining a relationship between color signals of a color system as an inverse conversion relationship, wherein the color signal is converted from a first color system to a second color system using the inverse conversion relationship. That is, this conversion method is a color conversion method for converting a color signal from a first color system to a second color system, and a first color signal corresponding to a known real color signal (for example, a CMY color signal) of the second color system. After the real color signals of the color system (for example, XYZ color signals) are obtained, the first forward conversion relationship between these real color signals is approximated by a monotonic function, and the virtual relationship is set outside the region constituted by the real color signals. Set the color signal.
Then, based on the second forward conversion relationship between the second color system including the real color signal and the virtual color signal and the first color system, the first color system is repeatedly calculated by the Newton method. For example, a method of obtaining an inverse conversion relationship for conversion into a system and the second color system and performing color conversion using the inverse conversion relationship can be given as an example.

Regarding the size of the image obtained by using the photothermographic material and the dye-fixing element, any of A-line, A1-A6, chrysanthemum, B-line, B1-B6, and 46-format can be used. good. Further, the size of the photothermographic material and the dye-fixing element can be any size within a range of 100 mm to 2000 mm, depending on the size.

[0127]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. (Example 1) First, a method for producing a color diffusion transfer silver halide photosensitive material of the present invention will be described.

<Preparation method of light-sensitive silver halide emulsion > Red-sensitive silver halide emulsion (1) A well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, sodium chloride in 700 ml of water ) .
5 g and 15 mg of the following chemical (A) were added thereto, and the mixture was kept at 42 ° C.), and simultaneously the solutions (I) and (II) in Table 1
Add at an equal flow rate for minutes. Then, 8 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of a dye (water 160
1.9 g of gelatin per ml, 127 m of the following pigment (a)
g, the following dye (b) 253 mg, the following dye (c) 8
mg (incubated at 35 ° C.). Two minutes later, solution (III) and solution (IV) shown in Table 1 were simultaneously added at the same flow rate for 32 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to the above aqueous solution, and the following chemical (B)
The pH was adjusted to 6.2 and the pAg to 7.8 by adding 50 mg, and 4-hydroxy-6-methyl-1,3,3a, 7 was added.
-Add tetrazaindene, then add sodium thiosulfate and chloroauric acid and optimally sensitize at 68 ° C, then add the following antifoggant (1), 80 mg of chemical (C), and 3 g of chemical (D). After the addition, the mixture was cooled. Thus, 635 g of a monodispersed cubic silver chlorobromide emulsion [red-sensitive silver halide emulsion (1)] having an average grain size of 0.21 μm was obtained.

[0130]

[Table 1]

[0131]

Embedded image

[0132]

Embedded image

Green-Sensitive Silver Halide Emulsion (2) Aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water )
Solution (I) and Solution (II) shown in Table 2 were simultaneously added at the same flow rate for 8 minutes to 15 mg of the above-mentioned drug (A) and keeping the temperature at 41 ° C.). After 10 minutes, solutions (III) and (IV) shown in Table 2 were simultaneously added at the same flow rate for 32 minutes. Also (II
One minute after the completion of the addition of the liquids (I) and (IV), a methanol solution of the dye (the following dye (d-1) 22 in 47 ml of methanol) was added.
30 including 8 mg and 57.3 mg of the following pigment (d-2)
℃) was added all at once.

After washing with water and desalting in a conventional manner, 22 g of lime-treated ossein gelatin was added to the aqueous solution, and the above-mentioned chemical (B) was added.
50 mg and 3 g of drug (D) were added to adjust the pH to 6.0 and p
Ag was adjusted to 7.1 and 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimal chemical sensitization at 60 ° C. Then, the antifoggant (1) was added, followed by cooling. Thus, a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.23 μm [green-sensitive silver halide emulsion (2)] 635
g was obtained.

[0135]

[Table 2]

[0136]

Embedded image

Blue-sensitive silver halide emulsion (3) A well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water )
And solution (I) and solution (II) shown in Table 3 were simultaneously added at a constant flow rate for 8 minutes to 15 mg of the above-mentioned chemical (A) and keeping the temperature at 46 ° C. After 10 minutes, solutions (III) and (IV) in Table 3 were simultaneously added at the same flow rate for 18 minutes. Also (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of the dye (water 9
In 5 ml of methanol and 5 ml of methanol, the following dye (e) 22
5 mg and the following dye (f) containing 225 mg and kept at 30 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to the above aqueous solution, and the above-mentioned chemical (B)
50 mg and 3 g of drug (D) were added to adjust the pH to 6.0 and p
Ag was adjusted to 7.7 and 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimal chemical sensitization at 65 ° C. Then, the antifoggant (1) was added, followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm [blue-sensitive silver halide emulsion (3)] 635
g was obtained.

[0139]

[Table 3]

[0140]

Embedded image

<Preparation method of zinc hydroxide dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethylcellulose, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin and 158.5 ml of water were mixed as a dispersant, and the mixture was dispersed for 1 hour in a mill using glass beads. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained.

<Method for Preparing Emulsified Dispersion of Coupler> Table 4
The oil phase component and the water phase component having the compositions shown in
Make a homogeneous solution at 0 ° C. The oil phase component and the aqueous phase component were combined, and in a 1-liter stainless steel container, with a dissolver equipped with a 5 cm diameter disperser, 10,000
Dispersed for 20 minutes at rpm. To this, warm water in an amount shown in Table 4 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0143]

[Table 4]

[0144]

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<Preparation of Color Diffusion Transfer Silver Halide Photosensitive Material> The thus obtained material was used to prepare a multilayered color diffusion transfer silver halide light sensitive material 10 shown in Tables 5-6.
Dry Color Diffusion Transfer Silver Halide Photosensitive Material 101 Coated on Continuous Web Supports A1, A2, A3, and E1 Having the Configurations in Tables 7 to 10 According to the Configuration of No. 1
A1, 101A2, 101A3, and 101E1 were produced.

[0146]

[Table 5]

[0147]

[Table 6]

[0148]

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[0149]

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[0150]

[Table 7]

[0151]

[Table 8]

[0152]

[Table 9]

[0153]

[Table 10]

Next, as shown in Table 11, using exactly the same composition and constitution as 101 except that the color developing agent or the coupler of each layer was changed, supports A1 and A
2, A3, E1 coated with color diffusion transfer silver halide photosensitive material 103A1, 107A1 to 109A1, 102
A2 to 109A2, 103A3, 107A3 to 109
A3, 103E1, 107E1 to 109E1 were produced.

[0155]

[Table 11]

[0156]

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Next, a method for producing an image receiving material used for forming an image on a color diffusion transfer silver halide photosensitive material by processing in combination with the above photosensitive material will be described.

<Method for Preparing Dispersion of Antistaining Agent (3)> 1 g of the antistaining agent (3), 1.2 g of the anionic surfactant (3) and 0.1 g of the anionic surfactant (4)
g is dissolved in 100 g of the high boiling organic solvent (1) at 50 ° C. by heating. Separately, after swelling 60 g of lime-processed gelatin in 300 cc of ion-exchanged water, it is dissolved at 70 ° C. and a preservative is added. After mixing both at 40 ° C., the mixture is emulsified and dispersed by an ultrasonic dispersing device. By this operation, an emulsified dispersion having an average particle size of 0.1 μm to 1 μm of the stain inhibitor (3) was obtained.

<Preparation of Image Receiving Material G101> The image receiving material G1 was prepared according to the above-mentioned dispersion and the constitutions shown in Tables 12 and 13.
01 was produced. Table 14 shows the structure of the support of the image receiving material G101.

[0160]

[Table 12]

[0161]

[Table 13]

[0162]

[Table 14]

[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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The color diffusion transfer silver halide photosensitive material is cut into a sheet having a width of 9 cm and a length of 50 m, and is wound around a 1-inch diameter roll-shaped core (feeding side) so that the coating surface faces outward. A cassette of color diffusion transfer silver halide photosensitive material (continuous web-form color diffusion transfer silver halide photosensitive material) by partially winding the tip of the color diffusion transfer silver halide photosensitive material around another winding core (winding side)
Was prepared. After that, one screen is 9cm wide and 12 long.
The color diffusion transfer silver halide light-sensitive material was passed through a B, G, R filter having a continuously changed density of 25 cm.
Exposure was carried out for 0.1 second at 00 lux. On the other hand, the image receiving material G
101 is cut to a width of 9 cm separately, and the roll is wound around a 1-inch diameter roll-shaped core (feeding side) so that the coating surface faces outward.
I rolled in just 0m. Thereafter, the leading end of the image receiving material G101 was partially wound around another winding core (winding side). The image receiving material G101 was set so that the dye fixing layer of the image receiving material G101 was placed on the side facing the outer surface of the drum heater during feeding and winding. Next, at 40 ° C. on the exposed photosensitive layer of the color diffusion transfer silver halide photosensitive material.
Fountain solution was spread at a rate of 13 ml / m ² (40% of the amount of water required for maximum swelling). Image receiving material G
At the position where 101 is in contact with the drum heater, the color diffusion transfer silver halide photosensitive material and the image receiving material G101 are bonded together so that the photosensitive layer and the dye fixing layer are evenly overlapped, and these are attached at the same speed as the rotation speed of the drum heater. While moving, the color diffusion transfer silver halide photosensitive material is
The developing process was performed by adjusting the speed and the heater temperature so that the film was heated at 83 ° C. for 30 seconds until the film 101 was peeled off. Next, the image receiving material G101 was separated from the color diffusion transfer silver halide photosensitive material at a position where the image receiving material G101 was separated from the heater drum. Continuous image receiving material G10
On 1, an image for each screen corresponding to the B, G, and R filters having continuously changed density was obtained.

The above-mentioned processing was continuously performed on a color diffusion transfer silver halide photosensitive material having 100 screens, and the relative sensitivity, adhesion, and sharpness of the obtained image were evaluated for these photosensitive materials. Here, the adhesion means the adhesion between the photosensitive layer and the support, and the better the evaluation of the adhesion, the better the durability during processing.

The relative sensitivity was evaluated by visually observing the sensitivity of each color diffusion transfer silver halide light-sensitive material, and indicated by the color diffusion transfer silver halide light-sensitive material 101A1 (in Table 15, light-sensitive material 101 and support A1). ) Is 100%. The higher the value, the higher the sensitivity.

In the evaluation of the adhesion, 1 was selected on the image receiving material G101 side.
When the film of the photosensitive layer peeled from the support of the color diffusion transfer silver halide light-sensitive material is in close contact with 10 or more of the 00 screens (a part of the film of the photosensitive layer is a color diffusion transfer silver halide light-sensitive material). Of the image receiving material G101
X): less than 10 screens out of 100 screens, Δ: no photosensitive layer adhered to image receiving material G101 side, but processed color diffusion transfer silver halide photosensitive material Was evaluated as 一部 when a part or all of the photosensitive layer was peeled off from the support, and as ◎ when no photosensitive layer was peeled at all.

In the evaluation of sharpness, a line image was printed using each of the color diffusion transfer silver halide photosensitive materials and the image receiving material G101, and the image of the image receiving material G101 was visually observed. Observed with a 10-fold microscope, those that were blurred were evaluated as ○, and those that were not blurred were evaluated as ◎. Here, “image is blurred” means a state in which the boundary between a colored portion and a non-colored portion of the line image cannot be clearly distinguished.

When the diameter of the core around which the color diffusion transfer silver halide photosensitive material is wound is 5 cm, the outer diameter (roll outer diameter) of the roll when the 50 m color diffusion transfer silver halide photosensitive material has been wound is determined. It was measured. Table 15 shows the above evaluation results.

[0180]

[Table 15]

From Table 15, it can be seen that the color developing agents represented by the above general formulas (1) and (2) of the present invention efficiently react with a 2-equivalent coupler having a ballast group as a leaving group, and exhibit diffusivity. It can be seen that a dye can be formed. On the other hand, when another sulfonamide phenol is used as the color developing agent, it can be seen that the color development efficiency is extremely low in combination with the 2-equivalent coupler and a color image cannot be obtained. Further, it can be seen that even when the color developing agent of the present invention is used, a color image cannot be obtained even when the two-equivalent coupler does not have a ballast group as a leaving group. In addition, it can be seen that by using a continuous web-shaped support having a thickness of 4 μm to 40 μm, sharpness is improved and the outer diameter of the winding can be made compact. On the other hand, when the conventional thick support is used, it can be seen that the sharpness is inferior to the extent that the image can be visually confirmed as blurred.
Further, it can be seen that the use of the support having the aluminum thin film layer on the photosensitive layer side further improved the sharpness, exposure sensitivity, and adhesion between the support and the photosensitive layer.

The prepared photosensitive material was heated at a temperature of 45 ° C.
A storability test was conducted at 80% humidity for 3 days. The results in Table 15 were reproduced, and the storability of the photographic material was good.

(Example 2) Multi-layered color diffusion transfer silver halide photosensitive material 201 having a multilayer structure described in Tables 16 to 18 below
According to the configuration of Table 1, between the cyan coloring layer of the color diffusion transfer silver halide photosensitive material 101A2 and the support A2,
Table 1 containing the boric acid compounds or silane compounds described in No. 9
Except for preparing the undercoat layer (first layer) B1 described in No. 8, the color diffusion transfer silver halide photosensitive material 201B1 is manufactured in the same procedure as the color diffusion transfer silver halide photosensitive material 101A2.
(In Table 20, the photosensitive material 201 and the undercoat layer B1 are indicated.)
Was prepared. Further, the cyan coloring layer of the color diffusion transfer silver halide photosensitive material 101A2 to 109A2 and the support A2
Color diffusion transfer silver halide photosensitive material 101A2 except that undercoat layers B1 to B5 of Tables 18 to 20 were prepared between
In the same procedure as 109A2, color diffusion transfer silver halide photosensitive materials 201B2-B3, 202B2, 203B1
~ B5, 204B2, 205B2, 206B3, 207
B1 to B5, 208B1 to B3, and 209B1 to B3 were produced. At that time, the pH of the coating solution for the layer was adjusted using sodium hydroxide or sulfuric acid.

[0184]

[Table 16]

[0185]

[Table 17]

[0186]

[Table 18]

[0187]

[Table 19]

[0188]

[Table 20]

[0189]

[Table 21]

Processing and evaluation were performed in the same manner as in Example 1. The results are shown in Table 20 above. From Table 20, it can be seen that the color diffusion transfer silver halide light-sensitive layer of the photosensitive layer is provided by providing an undercoat layer containing a boron compound or a silane compound on the lowermost layer of the color diffusion transfer silver halide light-sensitive material adjacent to the aluminum deposition support. The adhesion of the material to the support was further improved.

[0191]

According to the present invention, the use of a color developing agent represented by the above general formula (1) or (2) and a two-equivalent coupler having a ballast group as a leaving group allows the use of a diffusible compound by a coupling reaction. It is possible to provide a photosensitive material which can form a dye image, and which can form a printed image having excellent storage stability and excellent discrimination. Further, by using a thin support, the ratio of the color diffusion transfer silver halide photosensitive material per unit volume is increased, and the color diffusion transfer silver halide photosensitive material can be made compact. Further, it is possible to reduce the size of a processor for print output using the same. Further, by using a thin support having a photosensitive layer provided on an aluminum thin film layer, it is possible to improve light energy use efficiency, sensitivity, adhesion between the photosensitive layer and the support, and sharpness. Furthermore, by providing an undercoating layer containing a boric acid compound or a silane compound as a layer adjacent to the aluminum thin film layer, the adhesion between the photosensitive layer and the support can be further improved, and the durability during development can be improved. A photosensitive material having excellent properties can be provided.

Claims (5)

[Claims] 1. A color diffusion transfer halogen comprising, on a support, a photosensitive material having at least a photosensitive silver halide emulsion, a color developing agent, a photosensitive layer containing a coupler and a binder, and an image receiving material having an image receiving layer containing a mordant. A silver halide photographic material, wherein the support of the photographic material has a thickness of 4 μm or more.
A continuous web-form support having a particle size of 0 μm or less, wherein the color developing agent is a compound represented by the following general formula (1) or (2), and the coupler has a ballast group as a leaving group; A color diffusion transfer silver halide light-sensitive material, which is a two-equivalent coupler that forms a diffusible dye by a coupling reaction with an oxidized form of a base drug. Embedded image (Wherein, R _{1 to} R ₄ represent a hydrogen atom or a substituent.
A represents a hydroxyl group or a substituted amino group. X is -CO-,
_{-SO -, - SO 2 -,} - (Q) PO- (Q represents a monovalent group bonded to a phosphorus atom) represents a linking group selected from. Y ₂ represents a divalent linking group. Z ₂ is a nucleophilic group, which represents a group capable of attacking X when the present compound is oxidized. Two or more atoms or substituents arbitrarily selected from R ₁ and R ₂ and R ₃ and R ₄ may be independently bonded to each other to form a ring. ) (Wherein, R _{1 to} R ₄ , A, and X are the same as those in the general formula (1). Y _k and Z _k are a nitrogen atom or —CR ₅ = (R
₅ represents a hydrogen atom or a substituent). k represents an integer of 0 or more. D represents a proton dissociable group or a group that can be a cation. Two or more atoms or substituents arbitrarily selected from R ₁ and R ₂ , R ₃ and R ₄ and Y _k , Z _k and D may be independently bonded to each other to form a ring. ) 2. The color diffusion transfer silver halide light-sensitive material according to claim 1, wherein said support has a metal thin film layer. 3. The color diffusion transfer silver halide according to claim 2, wherein an undercoat layer containing a boron compound or a silane compound is provided below the photosensitive layer as a layer adjacent to the metal thin film layer. Photosensitive material. 4. The color diffusion transfer silver halide photosensitive material according to claim 2, wherein the metal thin film layer is an aluminum thin film layer. 5. The color diffusion transfer silver halide light-sensitive material according to claim 1, which is exposed imagewise, and then coated on the entire photosensitive layer surface of the light-sensitive material and a support film. The presence of water in an amount of 0.1 to 1 times the amount of water required for maximally swelling the entire coating layer on the image receiving layer surface of the image receiving material having at least a base and / or a base precursor and an image receiving layer containing a mordant on the body. Below, the light-sensitive material and the image-receiving material are superimposed on each other at a temperature of 60 ° C to 100 ° C for 5 seconds to
After heating for 60 seconds, the diffusible dye formed imagewise by the coupler is transferred to the image receiving material, and then the photosensitive material and the image receiving material are separated to form a color image on the image receiving material. Image forming method.