JPH09325464A - Heat development color sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve discrimination and color reproducibility without affecting other photographic properties adversely. SOLUTION: In a heat development color sensitive material in which at least two layers or more of sensitive emulsion layers containing at least sensitive silver halide, binder, coupler, and main developer are applied on a support body, each layer is applied in such a manner that it has spectral sensitivity in different wavelength regions, and at least one layer of an intermediate layer which is substantially non-sensitive is provided each between sensitive emulsion layers, a coupler which is coupled with the main developer but does not form a color image substantially is contained at least one layer of the intermediate layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-development color light-sensitive material excellent in image discrimination and color reproducibility.

[0002]

2. Description of the Related Art A photographic method using silver halide has been used most widely since it has superior photographic characteristics such as sensitivity and gradation control as compared with other photographic methods such as electrophotography and diazo photography. I have been. In particular, since the best image quality is obtained for color hard copy, it has been studied more vigorously these days.

[0003] In recent years, image forming processing methods for photosensitive materials using silver halide have been simplified from conventional wet processing to instant photographic systems incorporating a developing solution, and dry thermal development processing by heating or the like. Systems have been developed that can rapidly obtain images. Regarding the heat-developable light-sensitive material, "Basics of photographic engineering (non-silver salt photography), published by Corona Publishing Co., Ltd., 1982," p.242, describes its contents. It is still an image forming method. Recently, as photothermographic color light-sensitive materials, products such as Pictrography and Pictrostat have been sold by Fuji Photo Film Co., Ltd. In the above-described simple and rapid processing method, a color image is formed using a redox coloring material to which a preformed die is connected. As a color image forming method for a photographic light-sensitive material, a method utilizing a coupling reaction between a coupler and an oxidized product of a color developing agent is the most general method, and a heat-developable color light-sensitive material employing this method is also disclosed in US Pat. ，
Many ideas have been filed such as 761,270, 4,021,240, and JP-A-59-231539.

The inventors of the present invention have also studied the above-mentioned coupling type photothermographic material, but when a color photosensitive material having a multi-layer structure containing a developing agent is prepared, the oxidized form of the developing agent is different from other photosensitive materials. The problem of moving to a layer arises. When the oxidant of the developing agent moves to another photosensitive layer and undergoes a coupling reaction there, a dye is produced in the layer that should not develop color, and this color turbidity impairs the color reproducibility of the image. become. In the prior art, in order to avoid this, a method is widely known in which a non-photosensitive intermediate layer is provided between adjacent photosensitive layers to deactivate an oxidized product of a developing agent by a chemical reaction in the intermediate layer. ing. As a concrete method of this, firstly, a different type of reducing agent is contained in the intermediate layer,
A method is known in which an oxidized product of a developing agent is returned to the original developing agent by a cross oxidation reaction with this. However, in this method, the developing agent is regenerated and the silver is developed again, so that the consumption of the base increases. In the processing mode considered in the present invention, the amount of bases is finite, and thus the consumption of bases due to crosstalk reduces the Dmax of the image. Therefore, it was found that this method is difficult to adopt. As another method, there is known a technique of introducing into the intermediate layer a coupler which forms a substantially colorless compound by a coupling reaction with an oxidized product of a developing agent. As such a compound, for example, there is a method in which a non-releasable substituent is introduced into the site of the leaving group of a usual coupler, and examples of the coupler having such a substituent introduced are described in JP-A- 49-84439. However, when such a coupler is used in the system of the present invention,
It was found that a sufficient effect of preventing color mixing cannot be obtained.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-developable color light-sensitive material having a high maximum density, excellent discrimination and color reproducibility.

[0006]

The objects of the present invention have been achieved by the following heat-developable color light-sensitive material.

1) At least two photosensitive emulsion layers containing at least a photosensitive silver halide, a binder, a coupler and a developing agent are coated on a support, and each has a spectral sensitivity in a different wavelength region. And a heat-developable color photosensitive material having at least one substantially non-photosensitive intermediate layer between each photosensitive emulsion layer,
A heat-developable color light-sensitive material, characterized in that at least one of the intermediate layers contains a coupler which is capable of coupling with an oxidized product of the developing agent but does not substantially form a color image.

2) At least two light-sensitive emulsion layers containing at least light-sensitive silver halide, a binder, a coupler and a developing agent are coated on a support, each having a spectral sensitivity in a different wavelength region. And a heat-developable color photosensitive material having at least one substantially non-photosensitive intermediate layer between each photosensitive emulsion layer,
The coupler contained in the photosensitive emulsion layer is a 4-equivalent coupler, and the developing agent is represented by the following general formulas (1) and (2).
Or a compound represented by (3), wherein at least one of the intermediate layers contains a 2-equivalent coupler, which is a photothermographic material. General formula (1)

[0009]

[Chemical 6]

General formula (2)

[0011]

[Chemical 7]

General formula (3)

[0013]

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In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, and an aryloxy group. , Alkylthio, arylthio, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryloxy Represents a carbonyl group, an alkylcarbonyl group, an arylcarbonyl group or an acyloxy group, and R ₅ represents an alkyl group, an aryl group or a heterocyclic group. Z represents an atomic group forming an aromatic ring (including a heteroaromatic ring), and when Z is a benzene ring, the total value of the Hammett constants (σ) of the substituents is 1 or more. R ₆ represents an alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or a tertiary nitrogen atom (alkyl-substituted). R ₇ and R
₈ represents a hydrogen atom or a substituent, and R ₇ and R ₈
May combine with each other to form a double bond or a ring.

3) At least two light-sensitive emulsion layers containing at least light-sensitive silver halide, a binder, a coupler and a developing agent are coated on a support, each having a spectral sensitivity in a different wavelength region. And a heat-developable color photosensitive material having at least one substantially non-photosensitive intermediate layer between each photosensitive emulsion layer,
The coupler contained in the photosensitive emulsion layer is a 2-equivalent coupler, the developing agent is a compound represented by the following general formula (4) or (5), and at least one intermediate layer contains 4 A heat-developable color light-sensitive material containing an equivalent coupler. General formula (9)

[0016]

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General formula (5)

[0018]

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In the formula, R _{5 to} R ₈ , X and Z are the same as in the general formula (2) or (3), respectively.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The final aim of the technique of the present invention is to prevent the oxidized product of the developing agent from diffusing into the layers between the photosensitive emulsion layers,
It is to prevent color mixing reaction. In the present invention, for the purpose of softening the gradation of an image and improving the granularity, a layer containing silver halide grains having the same spectral sensitivity but different grain sizes is divided into several layers. It is also possible to apply the same over and over to form one photosensitive emulsion layer. In the present invention, an intermediate layer is provided between the light-sensitive emulsion layers, and a coupler which causes a coupling reaction with the oxidized product of the developing agent used in the present invention but does not develop color is contained therein.

The developing agent preferably used in the present invention is
It has the feature of having a leaving group at the coupling site. Therefore, for example, in the developing agents of the general formulas (1) to (3), a color image is formed with the 4-equivalent coupler but not with the 2-equivalent coupler. In this case, the general formula (1)
In the light-sensitive material system using the developing agent of (3) to (3), the addition of a 2-equivalent coupler to the intermediate layer can efficiently achieve the purpose of preventing color mixing. On the contrary, the developing agents represented by the general formulas (4) and (5) form a color image only with the two-equivalent coupler. Therefore,
In the photosensitive material system using the developing agent of the general formulas (4) and (5),
It is effective to use a 4-equivalent coupler in the intermediate layer.

The compounds represented by the general formula (1) are compounds collectively called sulfonamidephenol.

In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom (eg, chloro atom, bromine atom), a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, isopropyl group, n-butyl group, t -Butyl group), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, xylyl group), a substituted or unsubstituted alkylcarbonamide group (eg, acetylamino group, propionylamino group, butyroylamino group), substituted Or an unsubstituted arylcarbonamide group (eg, benzoylamino group), a substituted or unsubstituted alkylsulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group), a substituted or unsubstituted arylsulfonamide group (eg, benzenesulfonyl) Amino group, toluenesulfonylamino group), substituted or unsubstituted Xy group (eg methoxy group, ethoxy group, butoxy group), substituted or unsubstituted aryloxy group (eg phenoxy group), substituted or unsubstituted alkylthio group (eg methylthio group, ethylthio group, butylthio group), substituted or unsubstituted Substituted arylthio group (eg phenylthio group, tolylthio group), substituted or unsubstituted alkylcarbamoyl group (eg methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group) Group), a substituted or unsubstituted arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, substituted or unsubstituted A substituted alkylsulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group,
Piperidylsulfamoyl group, morpholylsulfamoyl group), substituted or unsubstituted arylsulfamoyl group (eg, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group) Moyl group), sulfamoyl group, cyano group, substituted or unsubstituted alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
A substituted or unsubstituted arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p
-Toluenesulfonyl group), a substituted or unsubstituted alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), a substituted or unsubstituted aryloxycarbonyl group (eg, phenoxycarbonyl group), a substituted or unsubstituted Alkylcarbonyl group (eg, acetyl group, propionyl group, butyroyl group), substituted or unsubstituted arylcarbonyl group (eg, benzoyl group, alkylbenzoyl group), or substituted or unsubstituted acyloxy group (eg, acetyloxy group,
(Propionyloxy group, butyroyloxy group).
Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. The Hammett substituent constant of R ₁ ~R ₄ (σ
The sum of the values) is preferably 0 or more. R ₅ is a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group, stearyl group), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, xylyl group). Group, 4-methoxyphenyl group, dodecylphenyl group, chlorophenyl group, trichlorophenyl group, nitrochlorophenyl group, triisopropylphenyl group, 4-dodecyloxyphenyl group,
3,5-di- (methoxycarbonyl) group) or a substituted or unsubstituted heterocyclic group (eg pyridyl group).

The compound represented by the general formula (2) is a compound generically called sulfonylhydrazine. The compound represented by the general formula (4) is a compound generally called carbamoylhydrazine.

In the formula, Z represents an atomic group forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable. In the case of a benzene ring, as the substituent, an alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), a halogen atom (eg, chloro group, bromine group), an alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group,
Ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, Alkylsulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group) An arylsulfamoyl group (for example, a phenylsulfamoyl group, a methylphenylsulfamoyl group, an ethylphenylsulfamoyl group, a benzylphenylsulfamoyl group), Amamoyl group, cyano group, alkylsulfonyl group (eg methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (eg methoxycarbonyl group) , Ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (eg phenoxycarbonyl group), alkylcarbonyl group (eg acetyl group, propionyl group, butyroyl group), arylcarbonyl group (eg benzoyl group, alkylbenzoyl group), etc. However, the sum of the Hammett substituent constants (σ value) of the above substituents is preferably 1 or more.

The compound represented by the general formula (3) is a compound generally called sulfonylhydrazone. The compound represented by the general formula (5) is a compound generally called carbamoylhydrazone.

In the formula, R ₆ represents a substituted or unsubstituted alkyl group (for example, a methyl group or an ethyl group). X represents an oxygen atom, a sulfur atom, a selenium atom or a tertiary nitrogen atom (alkyl-substituted), and an alkyl-substituted tertiary nitrogen atom is preferable. R ₇ and R ₈ each represent a hydrogen atom or a substituent, and R ₇ and R ₈ may bond to each other to form a double bond or a ring (for example, a benzene ring or a pyridine ring). Preferable examples of the substituents of R ₇ and R ₈ include groups other than the hydrogen atom of R _{1 to} R ₄ .

Specific examples of the compounds represented by the general formulas (1) to (5) are shown below, but the compounds of the present invention are of course not limited thereto.

[0029]

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[0030]

[Chemical 12]

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

[Chemical 21]

[0040]

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The above compounds can be synthesized by generally known methods. The simple synthesis routes are listed below.

[0042]

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[0043]

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[0044]

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In the present invention, the dye-donating compound is a compound (coupler) which forms a dye by an oxidative coupling reaction. In the present invention, as the coupler, a 4-equivalent coupler and a 2-equivalent coupler are selectively used depending on the type of the main drug. First, a 4-equivalent coupler is used for the developing agents of the general formulas (1) to (3). General formula (1)-
In the developing agent of (3), the coupling site is substituted by a sulfonyl group, and at the time of coupling, the sulfonyl group is sulfinic acid and is released, so that the leaving group on the coupler side must be released as a cation. It is. Therefore, a color is developed by reacting with a 4-equivalent coupler capable of releasing a proton as a leaving group at the time of coupling, but in the case of a 2-equivalent coupler having an anion as a leaving group, a reaction occurs but no color is produced. On the contrary, a 2-equivalent coupler is used for the developing agents of the general formulas (4) and (5). In the developing agents of the general formulas (4) and (5), the coupling site is substituted with a carbamoyl group, and the hydrogen atom on the nitrogen atom is released as a proton during coupling,
This is because the leaving group on the coupler side must be released as an anion. For this reason, at the time of coupling, a 2-equivalent coupler capable of releasing an anion as a leaving group reacts to develop a color, but in the case of a 4-equivalent coupler having a leaving group as a proton, it reacts but does not develop a color. Specific examples of the coupler include 4 equivalent and 2 equivalent both in theory of the photography process (4th. Ed. TH
Edited by James Macmilllan, 1977) 29
Pages 1 to 334 and 354 to 361, JP-A-5
8-12353, 58-149046, 58-
149047, 59-11114, 59-12
No. 4399, No. 59-174835, No. 59-231
No. 539, No. 59-231540, No. 60-2951
No. 60-14242, No. 60-23474, No. 60-66249 and the like.

Examples of couplers preferably used in the present invention are listed below.

The couplers preferably used in the present invention include compounds having the structures represented by the following general formulas (6) to (17). These are compounds generally called active methylene, pyrazolone, pyrazoloazole, phenol, and naphthol, respectively, and are compounds known in the art.

[0048]

[Chemical formula 26]

[0049]

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[0050]

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The general formulas (6) to (9) represent couplers called active methylene couplers, in which R ₂₄ represents a substituted or unsubstituted acyl group, cyano group, nitro group, substituted or unsubstituted group. Aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, carbamoyl group, sulfamoyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted Is an arylsulfonyl group.

In the general formulas (6) to (9), R ₂₅ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. In the general formula (9), R ₂₆ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. R ₂₄ , R ₂₅ ,
Examples of the substituent that R ₂₆ may have include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a cyano group, a halogen atom, an acylamino group, a sulfonamide group, Carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylamino group,
Various substituents such as an arylamino group, a hydroxyl group, and a sulfo group can be given. Preferred examples of R ₂₄ include a substituted or unsubstituted acyl group, a cyano group, a carbamoyl group, and a substituted or unsubstituted alkoxycarbonyl group.

In the general formulas (6) to (9), Y is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a developing agent. As an example of Y, a group which acts as an anionic leaving group of a 2-equivalent coupler includes a halogen atom (eg chlorine, bromine), an alkoxy group (eg methoxy group, ethoxyalkyl group (eg ethoxymethyl group, ethoxyethyl group, ethoxy group). Isopropyl group,
Ethoxy-n-butyl group, ethoxy-t-butyl group),
An aryloxy group (for example, a phenoxy group, a 4-cyanophenoxy group, a 4-alkoxycarbonylphenyl group),
Alkylthio group (eg, methylthio group, ethylthio group,
Butylthio group), arylthio group (eg phenylthio group, tolylthio group), alkylcarbamoyl group (eg methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), Arylcarbamoyl group (eg phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (eg methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group) Moyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group),
Arylsulfamoyl group (eg, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, Ethanesulfonyl group), arylsulfonyl group (for example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkylcarbonyloxy group (for example, acetyloxy group, propionyloxy group, butyroyloxy group), arylcarbonyloxy group ( Examples thereof include a benzoyloxy group, a toluyloxy group, an anisyloxy group) and a nitrogen-containing heterocyclic group (eg, imidazolyl group, benzotriazolyl group).

The group acting as the cationic leaving group of the 4-equivalent coupler includes a hydrogen atom, a formyl group,
A carbamoyl group, a methylene group having a substituent (as a substituent, an aryl group, a sulfamoyl group, a carbamoyl group, an alkoxy group, an amino group, a hydroxyl group, etc.), an acyl group,
And a sulfonyl group.

In the general formulas (6) to (9), R ₂₄ and R
₂₅ , R ₂₄ and R ₂₆ may combine with each other to form a ring.

The general formula (10) represents a coupler called a 5-pyrazolone type magenta coupler, in which R ₂₇ represents a substituted or unsubstituted alkyl group, aryl group, acyl group or carbamoyl group. R ₂₈ is a phenyl group,
Alternatively, it represents a phenyl group substituted with one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups or acylamino groups. Y is the same as in general formulas (6) to (9).

Among the 5-pyrazolone magenta couplers represented by the general formula (10), those in which R ₂₇ is an aryl group or an acyl group and R ₂₈ is a phenyl group substituted by one or more halogen atoms are preferred.

To describe these preferred groups in detail, R ₂₇ 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-t-butylphenoxy) tetradecanamido] aryl group such as phenyl, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-
Di-t-pentylphenoxy) acetyl, 2- (2,4
Acyl group such as -di-t-pentylphenoxy) butanoyl, benzoyl, 3- (2,4-di-t-amylphenoxyacetoazide) benzoyl, and these groups may further have a substituent; They are organic substituents or halogen atoms connected by carbon, oxygen, nitrogen or sulfur atoms.

R ₂₈ is 2,4,6-trichlorophenyl,
Substituted phenyl groups such as 2,5-dichlorophenyl and 2-chlorophenyl groups are preferred.

The formula (11) represents a coupler called a pyrazoloazole coupler, wherein R ₂₉ represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group 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 (6) to (9).

Among the pyrazoloazole-based couplers represented by the general formula (11), imidazo [1,2- (2-)] described in US Pat.
b] pyrazoles, pyrazolo [1,5-b] [1,2,4] triazoles described in US Pat. No. 450654, and pyrazolo [5,1-c] [1, described in US Pat. No. 3725067. 2,4] triazoles are preferable, and in view of light fastness, pyrazolo [1,5-
b] [1,2,4] triazoles are preferred.

For details of the substituents on the azole ring represented by the substituents R ₂₉ , Y and Z, see, for example, US Pat.
No. 40654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-6
Pyrazoloazole couplers in which a branched alkyl group is directly bonded to the 2-, 3- or 6-position of the pyrazolotriazole group as described in JP-A-5245, and a sulfonamide group in the molecule described in JP-A-61-65245 A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
9457 or 63-307453, pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position, and Japanese Patent Application No. 1-222.
No. 79 is a pyrazolotriazole coupler having a carbonamide group in the molecule.

The general formulas (12) and (13) are couplers called phenol couplers and naphthol couplers, respectively, wherein R ₃₀ is a hydrogen atom or --NHCO.
_{R 32, -SO 2 NR 32 R} 33, -NHSO 2 R 32, -NH
COR _32, -NHCONR ₃₂ R ₃₃ , -NHSO ₂ NR ₃₂
It represents a group selected from R _33. R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. In the general formulas (12) and (13),
R ₃₁ represents a substituent, l is an integer selected from 0 to 2, m
Represents an integer selected from 0 to 4. Y is the same as in general formulas (6) to (9). As R _{31 to} R ₃₃ , those mentioned as the substituents of R _{24 to} R ₂₆ can be mentioned.

Preferable examples of the phenolic coupler represented by the general formula (12) include US Pat.
No. 9, 2801171, 2772162,
Nos. 2895826 and 3772002, 2-alkylamino-5-alkylphenols,
U.S. Patent Nos. 2,772,162 and 3,758,308;
No. 4126396, No. 4334011, No. 4
327173, West German Patent Publication No. 3329729, 2,5-diacylaminophenols described in JP-A-59-166956, etc .; U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559 and 44,559.
And 2-phenylureido-5-acylaminophenols described in US Pat.

Preferred examples of the naphthol coupler represented by the general formula (13) include US Pat. No. 2,474,293.
2-carbamoyl-1-naphthols described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200 and U.S. Pat.
And 2-carbamoyl-5-amido-1-naphthol described in JP-A-690889.

Formulas (14) to (17) are couplers called pyrrolotriazoles, and R ₄₂ , R _{43 and} R ₄₄ each represent a hydrogen atom or a substituent. Y is the same as in general formulas (6) to (9). _Examples of the substituent for R ₄₂ , R _{43, and} R ₄₄ include those described above as the substituent for R _{24 to} R ₂₆ . Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas (14) to (17) include EP 488248 A1 and EP 497197 A1.
No. 545300, and couplers in which at least one of R ₄₂ and R ₄₃ is an electron-withdrawing group.

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 fused phenol couplers, those described in US Pat. Nos. 4,327,173, 4,564,586 and 4,904,575 can be used.

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

The pyrrole coupler is disclosed in
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, couplers described in EP 556700, and the like can be used.

In the present invention, in addition to the couplers described above, West German Patent Nos. 3819051A and 3823049, US Pat. Nos. 4,840,883, 5,024,930, 5,051,347, 4,481,268, and EP 304856A2. 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 that can be used in the present invention are shown below. As described above, the 4-equivalent coupler is used for image formation in combination with the compounds of the general formulas (1) to (3) as a developing agent. On the contrary, when the compounds represented by the general formulas (4) and (5) are used as the developing agent, they can be used as a color mixing inhibitor. The 2-equivalent coupler is used for image formation in combination with the compounds of the general formulas (4) and (5) as a developing agent. On the contrary, when the compounds represented by the general formulas (1) to (3) are used as the developing agent, they can be used as a color mixing inhibitor. The present invention is of course not limited by the following compound examples.

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[Chemical formula 61]

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As the method for adding the developing agent and the coupler, first, the coupler, the developing agent and the high boiling point organic solvent (eg, alkyl phosphate ester, phthalic acid alkyl ester, etc.) are mixed to obtain a low boiling point organic solvent (eg ethyl acetate, It can be added after being dissolved in methyl ethyl ketone) and dispersed in water using an emulsion dispersion method known in the art. Further, addition by the solid dispersion method described in JP-A-63-271339 is also possible.

The addition amount of the coupler in the emulsion layer depends on its molar absorption coefficient (ε), but in order to obtain an image density of 1.0 or more in reflection density, ε of the dye formed by coupling is 5000. In the case of a coupler of about ~ 500,000,
The coating amount is about 0.001 to 100 mmol / m ² , preferably 0.01 to 10 mmol / m ² , and more preferably about 0.05 to 5 mmol / m ² .

The addition amount of the developing agent has a wide range, but it is preferably 0.01 to 100 mole times, more preferably 0.1 to 10 mole times with respect to the coupler.

The addition amount of the coupler in the intermediate layer used for preventing color mixing is 0.001 to 100 mol times, more preferably 0.05 to 50 mol times, relative to the total developing agent.

The color light-sensitive material of the present invention basically has a photosensitive silver halide, a coupler as a dye-donating compound, a reducing agent and a binder on a support, and further, if necessary, an organometallic hydrochloric acid. Agents and the like can be included. These components are often added to the same layer, but if they can react, they can be added separately to separate layers.

In the present invention, at least two photosensitive emulsion layers are coated on a support, and a substantially non-photosensitive intermediate layer is provided between each emulsion layer. Have spectral sensitivities in different wavelength ranges. yellow,
In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. For example, blue-sensitive layer, green-sensitive layer and red-sensitive layer
Layers, green-sensitive layers, red-sensitive layers, infrared-sensitive layers and the like. Each of the light-sensitive layers can take various arrangement orders known in ordinary color light-sensitive materials. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

In addition to the photosensitive layer and the intermediate layer, the photosensitive material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an antihalation layer and a back layer. Further, various filter dyes can be added to improve color separation.

Generally, a base is required for processing a photographic light-sensitive material, but various base-supplying methods can be adopted in the light-sensitive material of the present invention. For example, when a base generating function is imparted to the light-sensitive material side, it can be introduced into the light-sensitive material as a base precursor. Examples of such a 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. For this example, see US Pat. Nos. 4,514,493 and 46,463.
No. 57848 and the like.

Further, in the case of using a form in which a light-sensitive material and a processing sheet are superposed and processed, a method of introducing a base or a base precursor into the processing sheet can also be used. As the base in this case, an organic base such as an amine derivative can be used in addition to the inorganic base.

Further, a reaction in which a base precursor is contained in each of the light-sensitive material side and the processed sheet side to generate a base by a reaction between the two can be used. Examples of such a two-agent reaction type base generation method include a method based on a reaction between a poorly soluble basic metal salt and a chelating agent and a method based on a reaction between a nucleophilic agent and an epoxy compound. This example is described in JP-A-63-198050 and the like. In this case, heating may be performed with a small amount of solvent (such as water) contained between the photosensitive material and the processing sheet. The method for applying the solvent will be described later. As the solvent, a polar liquid, particularly water, is preferred.

As the support for the light-sensitive material of the present invention, those known in the art, particularly for heat-developable light-sensitive materials, can be used. Examples of such a support include a paper support laminated with polyethylene, a polyester support represented by polyethylene terephthalate and polyethylene naphthalate, and the like. An example of such a support is disclosed in JP-A-63-18986.
No. 0 has a detailed description.

As the support of the light-sensitive material of the present invention, in addition to those mentioned above, a support obtained by stretching a styrene polymer having a syndiotactic structure can also be preferably used. This polymer support is similar to that described above,
It may be a homopolymer or a copolymer. Such a polymer support is described in detail in Japanese Patent Application No. 7-45079.

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodisperse or polydisperse.
As described in JP-A Nos. 7,743 and 4-223,463, a method of mixing monodispersed emulsions and adjusting gradation is preferably used. The particle size is 0.1-2 μm, especially 0.2-
1.5 μm is preferable. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other.
Specifically, US Pat. No. 4,500,626 No. 50
No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,029 (1
No. 17,643 (December 1978)
Nos. 18,716 (November 11, 1979)
No. 307, 105 (November 1989)
Mon.) pp.863-865, JP-A-62-253,159.
No. 64-13,546, JP-A-2-236,54
No. 6, No. 3-110, 555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (F. Glafk)
ides, Chemie et Phisique Photographique, Paul Mont
el, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsio).
n Chemistry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VL Zelikman et al., Making and Coating Photog).
Raphic Emulsion, Focal Press, 1964) and the like can be used.

In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting to remove excess salt. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly added to the particles, or may be localized inside or on the surface of the particles. Specifically, the emulsions described in JP-A-2-236542, JP-A-1-116637, JP-A-5-181246 and the like are preferably used.

In the step of forming grains of the light-sensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a 4-substituted thioether compound or JP-B No. 47-1 is used.
An organic thioether derivative described in 1,386 or a sulfur-containing compound described in JP-A-53-144319 can be used.

For other conditions, see Graphide, "Physics and Chemistry of Photography," published by Paul Montell (F. G.
lafkides, Chemie et Phisique photographique, Paul
Montel, 1967), Duffin's "Emulsion Chemistry", Focal Press (GFDuffin, Photographic Emul)
sion Chemistry, Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikman et al., published by Focal Press (VL Zelikman et al., Making and Coating Phot).
For example, reference may be made to descriptions such as ographic Emulsion, Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. A back mixing method in which the grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount, and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142,329 and JP-A-55-158). 124, U.S. Pat. No. 3,650,757). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is between 2.2 and 8.5, more preferably between 2.5 and 7.5.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, gold, platinum, and the like, which are known for an emulsion for a normal type light-sensitive material, are used. A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-11055).
No. 5, No. 5-241267, etc.). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833, JP-A-62-40,
The method described in No. 446 can also be used. The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and pAg is preferably 6.0 to 1.
It is 0.5, and more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to provide the photosensitive silver halide used in the present invention with green-sensitive, red-sensitive and infrared-sensitive color sensitivities, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat.
617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615, 641 and those described in JP-A-63-23, 145). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after the nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The addition amount is generally from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

The additives used in such steps and known photographic additives which can be used in the light-sensitive material and the processing sheet of the present invention are described in RD No. 17,643 and RD No. 1 above.
8, 715 and No. 307, 105, and the corresponding parts are summarized in the table below.

Types of additives RD17643 RD18716 RD307105 1. 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right column 866-868, super sensitizer ~ page 649, right column 4. Optical brightener page 24 page 648 right column page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer. 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, 頁 650, left column, ultraviolet absorbers. 7. Dye image stabilizer page 25 650 page left column page 872 Hardener, page 26, page 651, left column, pages 874-875 9. Binder page 26 page 651 left column pages 873-874 10. Plasticizer, lubricant page 27 page 650 right column page 876 11. Coating aid, page 26-27 page 650 right column pages 875-876 Surfactant 12. 12. Static prevention, page 27, page 650, right column, pages 876-877. Matting agent 878-879

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13 / 1988.
No. 546, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, and examples thereof include proteins such as gelatin and gelatin derivatives or cellulose derivatives, starch, gum arabic,
Examples include natural compounds such as polysaccharides such as dextran and pullulan, and synthetic high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer. Also, U.S. Pat. No. 4,960,681,
No. 2-245260, etc., ie, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a vinyl monomer or another vinyl Copolymers with monomers (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are also used. These binders can be used in combination of two or more. Particularly, a combination of gelatin and the above binder is preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide emulsion. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in 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 organic silver salt is 0.01 mol per mol 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. In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used. Specific compounds preferably used are described in US Pat. No. 4,500,626, Nos. 51 to 51.
It is described in column 52. In addition, Japanese Patent Application No. 6-20633.
Compounds capable of fixing silver halide as described in No. 1 can also be used.

As the hardener used in the constituent layers of the light-sensitive material, Research Disclosure, US Pat. No. 4,678,739, column 41, 4,791,042 is cited.
JP-A-59-116,655 and JP-A-62-245,
No. 261, No. 61-18, 942, JP-A-4-21
Hardening agents described in JP-A-8,044 and the like can be mentioned. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), an N-methylol-based hardening agent (such as dimethylol urea), or a polymer hardening agent (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.001 g per g of gelatin applied.
5 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.
It may be added in layers or more.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the light-sensitive material. Specific examples thereof include the aforementioned Research Disclosure, US Pat. No. 5,089,378.
Nos. 4,500,627 and 4,614,702
No., JP-A-64-13546, pages (7) to (9),
(57)-(71) and (81)-(97), U.S. Pat. Nos. 4,775,610 and 4,626,500.
No. 4,983,494, JP-A-62-174,7
No. 47, 62-239, 148, 63-264,
747, JP-A-1-150,135, 2-11
0,557, 2-178,650, RD17,6
43 (1978), pages (24) to (25). These compounds are available in 5 moles per mole of silver.
X 10 ^-6 to 1 x 10 ^-1 mol is preferred, and 1 x 10
^-5 to 1 × 10 ^-2 mol is preferably used.

Various surfactants can be used in the constituent layers of the light-sensitive material for the purposes of coating aid, improvement of releasability, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of surfactants are described in Research Disclosure,
2-173,463 and 62-183,457. The constituent layers of the photothermographic material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Typical examples of the organic fluoro compound include fluorine-containing surfactants and fluorine oils described in JP-B-57-9053, columns 8 to 17, JP-A-61-29444, JP-A-62-135826 and the like. The hydrophobic fluorine compound such as the oily fluorine-based compound or the solid fluorine compound resin such as tetrafluoroethylene resin.

The light-sensitive material is provided with an anti-adhesion property, an improved sliding property,
A matting agent can be used for the purpose of making a matte surface or the like. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
No. 29, benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
No. 952. In addition, the compounds described in the above Research Disclosure can be used. These matting agents can 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 may contain a heat solvent, an antifoaming agent, a germicide / antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3-11,338, and JP-B-2-51,496.

In the present invention, an image forming accelerator can be used in the light-sensitive material. The image formation accelerator has a function of accelerating a redox reaction between a silver salt oxidizing agent and a reducing agent, accelerating a dye formation reaction, and the like. From a physicochemical function, a base or a base precursor, a nucleophilic compound, It is classified into a boiling organic solvent (oil), a thermal solvent, a surfactant, a compound having an interaction with silver or silver ions, and the like. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40.

In the present invention, various development stoppers can be used in the photothermographic material for the purpose of always obtaining a constant image against variations in the processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples 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-62-253159 (3.
It is described on pages 1) to (32).

As a method of exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person with a camera or the like, a method of exposing through a reversal film or a negative film with a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a light emitting diode for image information via an electric signal, various lasers (laser diode,
A method of performing scanning exposure by emitting light from a gas laser or the like (Japanese Unexamined Patent Application Publication No. 2-129625, 5-176144).
No. 5, No. 5-199372, No. 6-127021, etc.), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, or directly or through an optical system. Exposure method.

As a light source for recording an image on a photosensitive material,
As described above, natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., US Pat. No. 4,500,626, column 56, JP-A-2-53,37.
The light sources and exposure methods described in No. 8 and 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 is composed of 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-61-53462 and JP-A-62-121032.
The compounds described in (1) are 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 (NTS).
A television signal represented by C), 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 represented by CG and CAD can be used.

When the light-sensitive material of the present invention is processed by heat development, it may have a form having a conductive heating element layer as a heating means for heat development. In this case, the heat generating element described in JP-A-61-145544 can be used. The heating temperature in the thermal development process is about 80 ° C to 18 ° C.
0 ° C. and the heating time is 0.1 seconds to 60 seconds.

As a heating method in the developing step, a heated block or plate is brought into contact, 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 brought into contact. Alternatively, there is a method of passing through a high temperature atmosphere. A method of superposing a photosensitive material and a processing sheet is described in JP-A-62-253,159 and JP-A-61-147,244.
(27) can be applied.

The present invention will be described in detail below with reference to examples.

[0154]

【Example】

Example 1 <Preparation Method of Photosensitive Silver Halide Emulsion> Well stirred gelatin aqueous solution (inactive gelatin 3 in 1000 ml of water).
0 g, potassium bromide 2 g) and ammonia
Add ammonium nitrate as a solvent and keep the temperature at 75 ° C.
To this, 1,000 ml of an aqueous solution containing 1 mol of silver nitrate and 1000 ml of an aqueous solution containing 1 mol of potassium bromide and 0.03 mol of potassium iodide were simultaneously added over 78 minutes. After washing with water and desalting, the mixture was redispersed by adding inert gelatin to obtain a sphere equivalent diameter of 0.1.
A silver iodobromide emulsion having an iodine content of 3 .mu.% Of 76 .mu.m was prepared. Equivalent sphere diameter is model TA of Coulter Counter
Measured at -II. Potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to the above emulsion at 56 ° C. for optimum chemical sensitization. Sensitizing dyes corresponding to the respective spectral sensitivities were added to the emulsion at the time of preparing the coating solution to give color sensitivity.

<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 in a mill using glass beads for 1 hour. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained.

<Preparation Method of Emulsified Dispersion of Coupler> Table 1
The oil phase component and the water phase component having the compositions shown in
Make a uniform solution at 0 ° C. Combine the oil phase component and the water phase component in a 1 liter stainless steel container with a dissolver equipped with a disperser with a diameter of 5 cm to 10,000 r
dispersed for 20 minutes at pm. To this, warm water in the amount shown in Table 1 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.

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[Table 1]

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Using the materials thus obtained, heat-developable color photosensitive materials 101 having a multilayer structure shown in Tables 2 and 3 were produced.

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[Table 2]

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[Table 3]

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[0165]

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Further, the processing material R having the contents shown in Tables 4 and 5
-1 was produced.

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[Table 4]

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[Table 5]

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[Table 6]

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[Chemical 76]

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Next, as shown in Table 7, a light-sensitive material having exactly the same composition as 101 except that the coupler and the developing agent in each layer were changed so as to be replaced by an equimolar amount relative to 101 and the material was added to the intermediate layer. 102-120 were produced respectively. The light-sensitive materials 101 to 120 thus produced were exposed for 0.01 seconds at 2500 lux through B, G, R and gray filters having continuously changed densities. 15 ml / m ² of 40 ° C. hot water was applied to the exposed light-sensitive material surface, and the treated sheet and each other were superposed on each other, and then heat-developed at 83 ° C. for 30 seconds using a heat drum. When the image-receiving material was peeled off after the treatment, cyan, magenta, yellow and gray color images were clearly obtained corresponding to the filter exposed on the side of the light-sensitive material. Immediately after the treatment, the densities of Dmax of each monochromatic exposed portion and Dmin of the white background portion of this sample were measured with X-ri.
Table 8 shows the results of measurement with a te densitometer.

[0173]

[Table 7]

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[0175]

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[0176]

[Table 8]

Summarizing the results in Table 8, first, in Comparative Example Samples 101 to 108, color turbidity due to color mixture is recognized in the image. Further, in the samples (109 to 112) in which the reducing agent was added to the intermediate layer, the color mixture was reduced, but a decrease in Dmax was observed. On the other hand, the sample of the present invention (1
13 to 120), color mixture is reduced while Dmax is maintained. From the above, the effect of the present invention is clear.

Example 2 Next, a heat-developable color photosensitive material 201 having a multilayer structure shown in Tables 9 and 10 was produced.

[0179]

[Table 9]

[0180]

[Table 10]

[0181]

Embedded image

[0182]

Embedded image

Next, as shown in Table 11, except that the coupler and the developing agent in each layer were replaced so as to have an equimolar amount with respect to 201 and the material was added to the intermediate layer,
Photosensitive materials 202 to 220 having exactly the same composition as the above were prepared. Photosensitive materials 201 to 220 thus produced
Was continuously exposed for 0.01 seconds at 2500 lux through B, G, R, and gray filters of varying densities. 15 ml / m ² of 40 ° C. hot water was applied to the exposed light-sensitive material surface, and the treated sheet and each other were superposed on each other, and then heat-developed at 83 ° C. for 30 seconds using a heat drum. When the image-receiving material was peeled off after the treatment, cyan, magenta, yellow and gray color images were clearly obtained corresponding to the filter exposed on the side of the light-sensitive material. Immediately after the treatment, the densities of Dmax of each monochromatic exposed portion and Dmin of the white background portion of this sample were measured with X-r.
Table 12 shows the results measured by the ite densitometer.

[0184]

[Table 11]

[0185]

[Chemical formula 82]

[0186]

[Chemical 83]

[0187]

[Table 12]

To summarize the results in Table 12, first, in Comparative Example Samples 201 to 208, as in the case of 101, color turbidity due to color mixing is observed in the image. Further, in the samples (209 to 212) in which the reducing agent was added to the intermediate layer, the color mixture was reduced, but a decrease in Dmax was observed. On the other hand, in the samples (213 to 220) of the present invention, color mixture is reduced while Dmax is maintained. The effects of the present invention are clear from this embodiment.

[0189]

The color mixture can be reduced while keeping the maximum color density high.

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[Procedure amendment]

[Submission date] September 25, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction contents]

The couplers preferably used in the present invention include compounds having the structures represented by the following general formulas (6) to (17). Each of these is a compound known in the art.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction item name] 0053

[Correction method] Change

[Correction contents]

In the general formulas (6) to (9), Y is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a developing agent. Examples of Y include a halogen atom (for example, chlorine and bromine), an alkoxy group (for example, methoxy group, ethoxy group), an aryloxy group (for example, phenoxy group, 4- Cyanophenoxy group, 4-alkoxycarbonylphenyl group), alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, tolylthio group), alkylcarbamoyl group (for example, methylcarbamoyl group,
Dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group) A carbamoyl group, an alkylsulfamoyl group (for example, a methylsulfamoyl group, a dimethylsulfamoyl group, an ethylsulfamoyl group, a diethylsulfamoyl group, a dibutylsulfamoyl group, a piperidylsulfamoyl group,
Morpholylsulfamoyl group), arylsulfamoyl group (eg, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkyl Sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (for example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkylcarbonyloxy group (for example, acetyloxy group,
Examples thereof include a propionyloxy group, a butyroyloxy group), an arylcarbonyloxy group (eg, a benzoyloxy group, a toluyloxy group, an anisyloxy group), a nitrogen-containing heterocyclic group (eg, an imidazolyl group, a benzotriazolyl group).

Claims (3)

[Claims] 1. At least two photosensitive emulsion layers containing at least a photosensitive silver halide, a binder, a coupler and a developing agent are coated on a support,
A heat-developable color light-sensitive material having spectral sensitivity in different wavelength regions and having at least one substantially non-photosensitive intermediate layer between each photosensitive emulsion layer, wherein at least one intermediate layer is provided. A heat-developable color light-sensitive material, which further comprises a coupler which is coupled to the oxidized product of the developing agent but does not substantially form a color image. 2. At least two photosensitive emulsion layers containing at least a photosensitive silver halide, a binder, a coupler and a developing agent are coated on a support,
A heat-developable color light-sensitive material having spectral sensitivity in different wavelength regions and having at least one substantially non-photosensitive intermediate layer between each light-sensitive emulsion layer, which is included in the light-sensitive emulsion layer. The coupler is a 4-equivalent coupler, and the developing agent is a compound represented by the following general formula (1), (2) or (3), and a 2-equivalent coupler is provided in at least one layer of the intermediate layer. A heat-developable color light-sensitive material characterized by containing. General formula (1) General formula (2) General formula (3) In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. An arylthio group, an alkylcarbamoyl group, an arylcarbamoyl group, a carbamoyl group,
Alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylcarbonyl group,
Represents an arylcarbonyl group or an acyloxy group;
₅ represents an alkyl group, an aryl group or a heterocyclic group. Z
Represents an atomic group forming an aromatic ring (including a heteroaromatic ring), and when Z is a benzene ring, the total value of the Hammett constants (σ) of the substituents is 1 or more. R ₆ represents an alkyl group. X is an oxygen atom, a sulfur atom, a selenium atom or 3
Represents a primary nitrogen atom (alkyl-substituted). R ₇ and R ₈ each represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring. 3. At least two photosensitive emulsion layers containing at least a photosensitive silver halide, a binder, a coupler and a developing agent are coated on a support,
A heat-developable color light-sensitive material having spectral sensitivity in different wavelength regions and having at least one substantially non-photosensitive intermediate layer between each light-sensitive emulsion layer, which is included in the light-sensitive emulsion layer. The coupler is a 2-equivalent coupler, and the developing agent is represented by the following general formula (4) or (5)
A heat-developable color light-sensitive material, which is a compound represented by the formula (1) and contains at least one 4-layer coupler in the intermediate layer. General formula (4) General formula (5) In the formula, R _{5 to} R ₈ , X and Z are each represented by the general formula (2) or (3).
In each case.