JP2000122251A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cyan dye having excellent color developing property during developing, excellent hue and good color reproducibility by incorporating a specified pyrrole coupler and a specified N-substd. aminophenol color developing agent into a photosensitive material. SOLUTION: One layer of silver halide emulsion layers contains a dye-forming coupler expressed by formula I and a color developing agent expressed by formula II. In the formula I, each of R1, R2, R3 and R4 is hydrogen atom or a substituent having <250 formula weight, but when R4 is not hydrogen atom, R3 is -OH or -NH-Y, wherein Y is hydrogen atom, an alkyl group, aryl group, heterocyclic group, acyl group or the like, X is a group having >250 formula weight which can be released by the reaction with the oxidizing part of a color developing agent. In formula II, each of Ra, Rb, Rc and Rd is hydrogen atom or a substituent, A is a bivalent group selected from -SO2-, -P(R)(O) and -CO-, R is a substituent, and Z is an alkyl group, aryl group or heterocyclic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a heat-developable silver halide photographic material.

[0002]

2. Description of the Related Art Thermal development is known and described in, for example, "Basics of Photographic Engineering", Non-Silver Salt Photo Edition (1982, Corona Co., Ltd.), pp. 242-255, U.S. Pat. No. 4,500,626. Have been. In addition, a photothermographic material using silver halide is a photographic method that has been widely practiced since it is superior in photographic properties such as sensitivity and gradation as compared with methods such as electrophotography and diazo photography. . Many methods for obtaining a color image by thermal development using a silver halide photosensitive material have been proposed, and one of them is coupling of an oxidized developing agent with a dye-forming coupler (hereinafter sometimes simply referred to as a coupler). A color development system in which a dye image is formed by a reaction is exemplified. Regarding developing agents and couplers that can be used in this color development system, see US Pat.
No. 1,256, p-phenylenediamines reducing agents and phenol or active methylene couplers;
No. 1,270 proposes a p-aminophenol-based reducing agent, and U.S. Pat. No. 4,021,240 proposes a combination of a sulfonamide phenol-based reducing agent and a 4-equivalent coupler. However, this method has disadvantages such as printout of undeveloped silver halide remaining after processing, color development of undeveloped portions by post-development, and color smearing due to simultaneous presence of reduced silver and a color image in exposed portions. In order to solve this drawback, there has been proposed a dye transfer system in which a diffusible dye is formed by thermal development and transferred to an image receiving layer. In such a diffusion transfer type photothermographic material, there are a case where the photosensitive material has an image receiving layer capable of receiving a dye on the same support, and a case where the photosensitive material has an image receiving layer on a support different from the photosensitive material. is there. In particular, when used as a heat-developable color light-sensitive material, in order to obtain a dye image with high color purity, a dye-image-receiving layer is formed on a different support using an image-receiving material, and simultaneously or simultaneously with the formation of a diffusible dye by color development. After diffusible dye formation,
It is desirable to transfer the dye by diffusion.

[0003] As for this method, there are the following known documents. JP-B-63-36487, JP-A-5-22438
Nos. 1 and 6-83005 disclose a heat-developable photosensitive material containing a color developing agent precursor releasing p-phenylenediamine and a coupler.
Discloses a photographic material using a coupler having a polymer chain as a leaving group and releasing a diffusible dye in color development. However, the color developing agent or the precursor of the color developing agent used in these prior arts has a drawback that the dye is transferred to the image receiving layer at the time of dye transfer and causes stain during storage of the transferred image.

In addition to the above-described coupling method,
A method has been proposed in which a diffusible dye is released or formed imagewise by thermal development and transferred to the diffusible dye-fixing element. In this method, a negative dye image and a positive dye image can be obtained by changing the type of the dye-donating compound used or the type of the silver halide used. More specifically, U.S. Pat. Nos. 4,500,625, 4,483,914, 4,503,137 and 4,559,290, and JP-A-58-149,046.
Nos. 60-133,449 and 59-218,44
3, No. 61-238,056, European Patent Publication 22
0,746A2, published technical report 87-6199, European Patent Publication 210660A2, and the like. These methods generally use a compound (hereinafter, referred to as a coloring material) in which a pre-colored image forming dye (preformed dye) is made non-diffusion resistant.
A method of producing a diffusible dye as a function of silver halide development has been employed. In such a method, if a coloring material is added to the same layer as the silver halide emulsion, the sensitivity to undesired exposure is reduced due to the filtering effect of the dye portion. Therefore, in order to avoid this problem, a method is generally employed in which a colorant for image formation is added to a layer farther from the exposed surface than the silver halide emulsion layer. However, in this method, although the decrease in sensitivity due to the filter effect described above is avoided, the physical distance between the silver halide emulsion and the coloring material that generates the diffusible dye increases, so that the silver halide emulsion is developed into the coloring material. It has the inherent disadvantage of inefficiency in information transmission. Further, the cyan dye produced by these methods has a disadvantage that light fastness is weak. More recently, Japanese Patent Application Laid-Open No. 8-286
No. 340, JP-A-9-152705 and the like, an image forming method using a silver halide photographic light-sensitive material containing a hydrazine-based color developing agent and a coupler, and a European patent EP0
No. 851283A proposes a method of forming a dye image by a new coupling method, which is an image forming method using a silver halide photographic light-sensitive material containing an N-substituted aminophenol-based color developing agent and a coupler. However, in these systems, it is desired that the coloring properties be further improved.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material excellent in color development during development. Another object of the present invention is to provide a silver halide photographic light-sensitive material which provides a cyan dye having excellent hue and good color reproducibility.

[0006]

The above object has been achieved by incorporating the following specific pyrrole coupler and specific N-substituted aminophenol-based color developing agent into a light-sensitive material. (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula (1)
And a color developing agent represented by the following formula (2):

[0007]

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[0008]

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In the general formula (1), R ¹ , R ² , R ³
And R ⁴ represent a hydrogen atom or a substituent having a formula weight of less than 250. However, when R ⁴ is other than a hydrogen atom, R ³ represents —OH or —NH—Y, and Y is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group,
Represents an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or a sulfamoyl group. X has a formula weight of 250 or more and represents a group capable of leaving by reaction with an oxidized color developing agent. In the general formula (2), R ^a , R ^b , R ^c and R ^d each represent a hydrogen atom or a substituent. A is -SO ₂ -, - P
(R) represents a divalent group selected from (O)-and -CO- (R represents a substituent), and Z represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or a heterocyclic group. Represents an oxy group, an amino group or an arylamino group. (2) The silver halide photographic material as described in (1) above, wherein the silver halide photographic material is a heat-developable photographic material.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R ¹ and R
The substituent represented by ² is not particularly limited as long as it has a formula weight of less than 250. Examples of R ¹ and R ² include a hydrogen atom, a linear or branched, chain or cyclic alkyl group, a linear or branched, chain or cyclic alkenyl group, an alkynyl group,
Aryl group, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, carbonamide group, sulfonamide group,
Carbamoyl group, sulfamoyl group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, N-acylsulfamoyl group, N-
Sulfamoylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonylamino group, aryloxycarbonylamino group, amino group,
Ammonio group, cyano group, nitro group, carboxyl group,
Hydroxy group, sulfo group, mercapto group, alkylsulfinyl group, arylsulfinyl group, alkylthio group, arylthio group, ureido group, heterocyclic group (for example,
Containing at least one or more of nitrogen, oxygen and sulfur,
A 3- to 12-membered monocyclic or fused ring), a heterocyclic oxy group,
Examples include a heterocyclic thio group, an acyl group, a sulfamoylamino group, a silyl group, and a halogen atom.

Preferred examples of R ¹ and R ² include:
A hydrogen atom, a linear or branched, chain or cyclic alkyl group having 1 to 10 carbon atoms (for example, trifluoromethyl, methyl, ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl) , Cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, etc.), linear or branched, chain or cyclic alkenyl group having 2 to 10 carbon atoms (eg, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), carbon number 2-10
Alkynyl group (eg, ethynyl, 1-propynyl, etc.), aryl group having 6-14 carbon atoms (eg, phenyl, naphthyl, etc.), acyloxy group having 1-10 carbon atoms (eg, acetoxy, benzoyloxy, etc.), carbon 2 to 10 alkoxycarbonyloxy groups (for example, methoxycarbonyloxy group, 2-methoxyethoxycarbonyloxy group and the like), and 7 to 14 carbon atoms of aryloxycarbonyloxy group (for example, phenoxycarbonyloxy group and the like) 12 carbamoyloxy groups (eg, N, N-dimethylcarbamoyloxy and the like),
A carbonamide group having 1 to 12 carbon atoms (for example, formamide, N-methylacetamide, acetamido, N-methylformamide, benzamide, etc.);
Sulfonamide groups (eg, methanesulfonamide,
Benzenesulfonamide, p-toluenesulfonamide, etc.), a carbamoyl group having 1 to 10 carbon atoms (for example, N-
Methylcarbamoyl, N, N-diethylcarbamoyl,
N-mesylcarbamoyl and the like, and a sulfamoyl group having 0 to 10 carbon atoms (for example, N-butylsulfamoyl, N,
N-diethylsulfamoyl, N-methyl-N- (4-
Methoxyphenyl) sulfamoyl, etc.), having 1 to 1 carbon atoms
0 alkoxy groups (for example, methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy, etc.), aryloxy groups having 6 to 14 carbon atoms (for example, phenoxy, 4-methoxyphenoxy, naphthoxy, etc.),
An aryloxycarbonyl group having 7 to 14 carbon atoms (e.g., phenoxycarbonyl, naphthoxycarbonyl, etc.), an alkoxycarbonyl group having 2 to 10 carbon atoms (e.g., methoxycarbonyl, t-butoxycarbonyl, etc.), N-acylsulfamoyl group (for example, N-ethylsulfamoyl, N-benzoylsulfamoyl, etc.), C-C12 N-sulfamoylcarbamoyl group (for example, N-methanesulfonylcarbamoyl group) An alkylsulfonyl group having 1 to 10 carbon atoms (e.g., methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, etc.),
4 arylsulfonyl groups (e.g., benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), C2-10 alkoxycarbonylamino groups (e.g., ethoxycarbonylamino, etc.), and C7-14 carbon atoms Aryloxycarbonylamino group (for example, phenoxycarbonylamino, naphthoxycarbonylamino, etc.), amino group having 0 to 10 carbon atoms (for example, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), carbon number of 3 to 12 ammonio groups (eg, trimethylammonio group, dimethylbenzylammonio group, etc.) cyano group, nitro group, carboxyl group, hydroxy group, sulfo group, mercapto group, alkylsulfinyl group having 1 to 10 carbon atoms (eg, An arylsulfinyl group having 6 to 14 carbon atoms (eg, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl, etc.), an alkylthio group having 1 to 10 carbon atoms (eg, methylthio, octylthio, Cyclohexylthio, etc.), an arylthio group having 6 to 14 carbon atoms (e.g., phenylthio, naphthylthio, etc.), a ureido group having 1 to 13 carbon atoms (e.g., 3-methylureido, 3,3-dimethylureido, 1,3-diphenyl) A heterocyclic group having 2 to 15 carbon atoms (e.g., a heteroatom such as a 3- to 12-membered monocyclic or condensed ring containing at least one or more of nitrogen, oxygen, sulfur and the like; Furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl Morpholino, 2
-Quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), heterocyclic oxy group (for example, pyridyloxy, pyrazolyloxy, etc.), heterocyclic thio group (for example, tetrazolylthio, 1,3,4-
Thiadiazolylthio, 1,3,4-oxadiazolylthio, benzimidazolylthio, etc.), an acyl group having 1 to 12 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), a sulfone having 0 to 10 carbon atoms Famoylamino group (eg, N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), silyl group having 3 to 12 carbon atoms (eg, trimethylsilyl, dimethyl-t-butylsilyl, etc.), halogen atom (eg, , A fluorine atom,
Chlorine atom, bromine atom, etc.). The above substituents may further have a substituent, and examples of the substituent include the substituents mentioned here.

The substituent represented by R ³ may have a formula weight of less than 250. Examples of R ³ include a hydrogen atom, a linear or branched, chain or cyclic alkyl group, a linear or branched, chain or cyclic alkenyl group, an alkynyl group, an aryl group, an acyloxy group, an alkoxycarbonyloxy group, Aryloxycarbonyloxy group, carbamoyloxy group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, N-acylsulfamoyl group, N- Sulfamoylcarbamoyl group, alkylsulfonyl group,
Arylsulfonyl group, alkoxycarbonylamino group, aryloxycarbonylamino group, amino group, ammonium group, cyano group, nitro group, carboxyl group, hydroxy group, sulfo group, mercapto group, alkylsulfinyl group, arylsulfinyl group, alkylthio group,
An arylthio group, a ureido group, a heterocyclic group (for example, containing at least one or more of nitrogen, oxygen and sulfur,
A 12-membered monocyclic or condensed ring), a heterocyclic oxy group, a heterocyclic thio group, an acyl group, a sulfamoylamino group, a silyl group, and a halogen atom. However, when R ⁴ is other than a hydrogen atom, R ³ represents —OH or —NH—Y;
Is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group,
Represents an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group.

Preferred examples of R ³ include a hydrogen atom, a linear or branched, chain or cyclic alkyl group having 1 to 10 carbon atoms (for example, trifluoromethyl, methyl,
Ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, etc.), linear or branched, chain or cyclic alkenyl having 2 to 10 carbon atoms Groups (eg, vinyl, 1-methylvinyl,
C2-C10 alkynyl group (e.g., ethynyl, 1-propynyl, etc.), C6-C14 aryl group (e.g., phenyl, naphthyl, etc.), C1-C10. Acyloxy group (for example, acetoxy, benzoyloxy and the like), alkoxycarbonyloxy group having 2 to 10 carbon atoms (for example, methoxycarbonyloxy group, 2-methoxyethoxycarbonyloxy group and the like), aryloxycarbonyloxy having 7 to 14 carbon atoms Group (e.g., phenoxycarbonyloxy group), a carbamoyloxy group having 1 to 12 carbon atoms (e.g., N, N-dimethylcarbamoyloxy), a carbonamide group having 1 to 12 carbon atoms (e.g., formamide,
N-methylacetamide, acetamide, N-methylformamide, benzamide, etc.), a sulfonamide group having 1 to 10 carbon atoms (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.),
A carbamoyl group having 1 to 10 carbon atoms (eg, N-methylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl, etc.), a sulfamoyl group having 0 to 10 carbon atoms (eg, N-butylsulfamoyl, N , N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) sulfamoyl, etc.), an alkoxy group having 1 to 10 carbon atoms (eg, methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy, etc.) ), An aryloxy group having 6 to 14 carbon atoms (e.g., phenoxy, 4-methoxyphenoxy, naphthoxy, etc.), an aryloxycarbonyl group having 7 to 14 carbon atoms (e.g., phenoxycarbonyl, naphthoxycarbonyl, etc.), 2 carbon atoms To 10 alkoxycarbonyl groups (e.g., methoxycarbonyl, t-butyl) Alkoxycarbonyl, etc.), 1 carbon atoms
A 12-N-acylsulfamoyl group (eg, N-ethylsulfamoyl, N-benzoylsulfamoyl, etc.), a C1-C12 N-sulfamoylcarbamoyl group (eg, an N-methanesulfonylcarbamoyl group) ), An alkylsulfonyl group having 1 to 10 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, etc.), and an arylsulfonyl group having 6 to 14 carbon atoms (eg, benzenesulfonyl, p-toluenesulfonyl, -Phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 10 carbon atoms (eg, ethoxycarbonylamino), an aryloxycarbonylamino group having 7 to 14 carbon atoms (eg, phenoxycarbonylamino, naphthoxycarbonylamino, etc.) ), Carbon number 0 10 amino groups (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), an ammonio group having 3 to 12 carbon atoms (eg, a trimethylammonio group, a dimethylbenzylammonio group, etc.), a cyano group, and nitro Group,
Carboxyl group, hydroxy group, sulfo group, mercapto group, alkylsulfinyl group having 1 to 10 carbon atoms (for example, methanesulfinyl, octanesulfinyl and the like),
An arylsulfinyl group having 6 to 14 carbon atoms (for example, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl and the like), an alkylthio group having 1 to 10 carbon atoms (for example, methylthio, octylthio,
Cyclohexylthio, etc.), an arylthio group having 6 to 14 carbon atoms (e.g., phenylthio, naphthylthio, etc.), a ureido group having 1 to 13 carbon atoms (e.g., 3-methylureide, 3,3-dimethylureide, 1,3-diphenyl) Ureido, etc.) and a heterocyclic group having 2 to 15 carbon atoms (for example, a heteroatom such as a 3- to 12-membered monocyclic or condensed ring containing at least one or more of nitrogen, oxygen, sulfur and the like; -Furyl, 2-pyranyl, 2-pyridyl, 2-
Thienyl, 2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl,
2-benzoxazolyl, etc.), heterocyclic oxy group (for example, pyridyloxy, pyrazolyloxy, etc.), heterocyclic thio group (for example, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxa Diazolylthio, benzimidazolylthio, etc.), an acyl group having 1 to 12 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), a sulfamoylamino group having 0 to 10 carbon atoms (eg, N-butylsulfur Moylamino, N-phenylsulfamoylamino, etc.), a silyl group having 3 to 12 carbon atoms (eg, trimethylsilyl, dimethyl-t-butylsilyl, etc.), and a halogen atom (eg, fluorine, chlorine, bromine, etc.). No. The above substituents may further have a substituent, and examples of the substituent include the substituents mentioned here.

Preferred specific examples of Y include a hydrogen atom,
A linear or branched, chain or cyclic alkyl group having 1 to 10 carbon atoms (for example, trifluoromethyl, methyl, ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl Octyl, 2-ethylhexyl, etc.), an aryl group having 6 to 14 carbon atoms (eg, phenyl, naphthyl, etc.), and a heterocyclic group having 2 to 15 carbon atoms (hetero atoms include, for example, nitrogen, oxygen, sulfur and the like). A 3- to 12-membered monocyclic or condensed ring containing at least one or more, such as 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino,
-Quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), having 1 to 12 carbon atoms
(E.g., acetyl, benzoyl, trifluoroacetyl, etc.), an alkylsulfonyl group having 1 to 10 carbon atoms (e.g., methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, etc.), and a carbon number of 6 to 1
4 arylsulfonyl groups (e.g., benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), C2-C10 alkoxycarbonyl groups (e.g., methoxycarbonyl, t-butoxycarbonyl, etc.), 7 carbon atoms To 14 aryloxycarbonyl groups (eg, phenoxycarbonyl, naphthoxycarbonyl, etc.), carbamoyl groups having 1 to 10 carbon atoms (eg, N-methylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl, etc.), carbon Number 0
To 10 sulfamoyl groups (for example, N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) sulfamoyl and the like)
Is mentioned. The above substituents may further have a substituent, and examples of the substituent include the substituents described for R ¹ and R ² .

The substituent represented by R ⁴ is not particularly limited as long as it has a formula weight of less than 250. Examples of R ⁴ include a hydrogen atom, a linear or branched, chain or cyclic alkyl group, a linear or branched, chain or cyclic alkenyl group, an alkynyl group, an aryl group, an acyloxy group, a carbamoyl group, and a sulfamoyl group. , An aryloxycarbonyl group,
Examples include an alkoxycarbonyl group, an N-acylsulfamoyl group, an N-sulfamoylcarbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic group, an acyl group, and a silyl group.

Preferred examples of R ⁴ include a hydrogen atom, a linear or branched, chain or cyclic alkyl group having 1 to 10 carbon atoms (for example, trifluoromethyl, methyl,
Ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, etc.), linear or branched, chain or cyclic alkenyl having 2 to 10 carbon atoms Groups (eg, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), alkynyl groups having 2 to 10 carbon atoms (eg, ethynyl, 1-propynyl, etc.), and aryl groups having 6 to 14 carbon atoms (eg, phenyl , Naphthyl, etc.), an acyloxy group having 1 to 10 carbon atoms (eg, acetoxy, benzoyloxy, etc.), a carbamoyl group having 1 to 10 carbon atoms (eg, N-methylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl) Etc.), a sulfamoyl group having 0 to 10 carbon atoms (for example, N-butylsulfa Yl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) sulfamoyl, etc.), an aryloxycarbonyl group having 7 to 14 carbon atoms (eg, phenoxycarbonyl, naphthoxycarbonyl, etc.), carbon number 2 to 10 alkoxycarbonyl groups (for example, methoxycarbonyl, t
-Butoxycarbonyl, etc.), an N acyl-sulfamoyl group having 1 to 12 carbon atoms (eg, N-ethylsulfamoyl, N-benzoylsulfamoyl, etc.),
2 N-sulfamoylcarbamoyl groups (for example, N-
Methanesulfonylcarbamoyl group), having 1 to 1 carbon atoms
0 alkylsulfonyl groups (e.g., methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, etc.) and arylsulfonyl groups having 6 to 14 carbon atoms (e.g., benzenesulfonyl, p-toluenesulfonyl,
-Phenylsulfonylphenylsulfonyl, etc.), a heterocyclic group having 2 to 15 carbon atoms (for example, containing at least one or more of nitrogen, oxygen and sulfur as a hetero atom, 3
And a 12-membered monocyclic or condensed ring such as 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl,
Imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), an acyl group having 1 to 12 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), 3 carbon atoms To 12 silyl groups (for example, trimethylsilyl, dimethyl-t-butylsilyl and the like). The above substituents may further have a substituent, and examples of the substituent include the substituents described for R ¹ and R ² .

The number of carbon atoms of the substituent represented by R ¹ , R ² , R ³ and R ⁴ is preferably 15 or less, more preferably 14 or less, and even more preferably 9 or less.
Further, the formula weight is preferably less than 250, more preferably 220 or less, and further preferably 180 or less. In order that the dye formed by the reaction between the color developing agent and the coupler in the present invention has sufficient diffusibility, the total number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ should be 1 or more and 30 or less. It is preferably from 1 to 24, more preferably from 1 to 20.

The group represented by X (a group capable of leaving by reaction with an oxidized form of a color developing agent) has a formula weight of 250
Above, represents an organic group bonded to the pyrrole ring by a nitrogen atom, an oxygen atom or a sulfur atom, for example, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxy group, a carbamoyloxy group, an aryloxycarbonyloxy group, an alkoxy group Carbonyloxy group, arylthio group, heterocyclic thio group, alkylthio group, alkylsulfonyloxy group, arylsulfonyloxy group, carbonamide group, sulfonamide group, alkylsulfonyl group,
Examples include an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a nitrogen-containing heterocyclic group linked by a nitrogen atom, an arylazo group, and a carbamoylamino group.

Preferred examples thereof include an aryloxy group (eg, phenoxy, 1-naphthoxy, etc.), a heterocyclic oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), an acyloxy group (eg, acetoxy, benzoyloxy, etc.), An alkoxy group (eg, dodecyloxy etc.), a carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy etc.), an aryloxycarbonyloxy group (eg,
Phenoxycarbonyloxy, etc.), alkoxycarbonyloxy groups (eg, dodecyloxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), heterocyclic thio groups (eg, tetrazolylthio, 1,3,4- Thiadiazolylthio, 1,3,4-oxadiazolylthio, benzimidazolylthio, etc.), alkylthio group (for example,
Hexadecylthio), an alkylsulfonyloxy group (eg, hexadecanesulfonyloxy, etc.), an arylsulfonyloxy group (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), a carbonamide group (eg, acetamide, etc.), a sulfonamide group (eg, , Hexadecanesulfonamide, benzenesulfonamide, etc.) alkylsulfonyl group (eg, hexadecansulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.), alkylsulfinyl group (eg, hexadecanesulfinyl, etc.), arylsulfinyl group (For example, benzenesulfinyl and the like), a nitrogen-containing heterocyclic group bonded by a nitrogen atom (a hetero atom is nitrogen,
A saturated or unsaturated 5- to 7-membered monocyclic or condensed ring containing at least one oxygen, sulfur or the like, for example, succinimide, maleimide, phthalimide,
Diglycolimide, pyrazole, imidazole, 1,
2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidin-2-one, Oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one,
Benzoxazolin-2-one, benzothiazoline-2
-One, 2-pyrrolin-5-one, 2-imidazoline-
5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-
Pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,3
4-thiazolidine-4-one and the like; an arylazo group (for example, phenylazo and naphthylazo); a carbamoylamino group (for example, N-hexadecylcarbamoylamino). X may be substituted by a substituent, and examples of the substituent that substitutes X include the examples of the substituent described for R ¹ . The total number of carbon atoms contained in X is preferably from 6 to 50, more preferably from 8 to 40, most preferably from 10 to 30. X
Are preferably an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, and a carbamoyloxy group, and more preferably an aryloxy group, a heterocyclic oxy group, an alkoxycarbonyloxy group, and carbamoyl. An oxy group.

In the general formula (2), R ^a , R ^b , R ^c and R
Preferred examples of ^d are the same as those exemplified for R ³ in formula (1). However, R ^a and R ^c are preferably a group other than a hydrogen atom, and R ^b and R ^d are preferably a hydrogen atom.

In the general formula (2), A is -SO _2- , -P
(R) is a divalent group selected from (O)-and -CO-, and R represents a substituent. R is preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an aryloxy group. Alternatively, it is a group of the general formula (2) except for -AZ. These groups may further have a substituent,
Preferred examples thereof include those exemplified for R ^{3 in} the general formula (1). Z represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, or an arylamino group, and when these groups are bonded to A, a 3- to 8-membered ring is formed. Those having a group that can be formed are more preferable, and examples of the group that can bond to A include an amide group, a carbamoyl group, a hydroxyl group, a sulfamoyl group, and a sulfonamide group. General formula (2)
A preferred specific example of the compound represented by the above-mentioned European Patent E
It is the same as D-1 to D-38 described in P0851283A.

Next, the coupler represented by the general formula (1) will be specifically described, but the scope of the present invention is not limited to these specific examples.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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Next, a general method for synthesizing the compound of the present invention will be described. Representative examples of the compounds used in the present invention are shown below. Other compounds can be synthesized in the same manner as in the following examples.

Synthesis Example 1 Synthesis of Exemplified Coupler (20) The coupler was synthesized according to the following synthesis route.

[0032]

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1-1. Synthesis of Compound A-1 215.1 g (1 mol) of α-bromophenylacetic acid was dissolved in 1 L of methylene chloride, and dimethylformamide (DM
F) 0.6 ml was added, and 130 ml of oxalyl chloride (1.5 mol
l) was added dropwise. After reacting at room temperature for 2 hours, the solvent and the remaining oxalyl chloride were distilled off under reduced pressure. The thus obtained α-bromophenylacetic acid chloride was dropped into 1 L of methanol over 30 minutes with stirring under ice cooling. After stirring at room temperature for 1 hour, the mixture was extracted with ethyl acetate, washed with a 1N aqueous solution of potassium carbonate and saturated saline, and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 216.7 g (0.946 mol) of compound Al as a colorless oil. Yield 94.6%. 1-2. Synthesis of Compound A-2 p-methanesulfonamidobenzoylacetonitrile 2
1.5 g (90.0 mmol) was dissolved in 150 ml of dimethylacetamide (DMAc), and 1,1,3,3-tetramethylguanidine (TM
G) 22.6 ml (180 mmol) was added dropwise over 15 minutes. After stirring for 10 minutes under ice-cooling, Compound A-12
While stirring 8.9 g (126 mmol) under ice cooling, 30
Dropped over minutes. After stirring at 10 ° C. for 1 hour, the mixture was extracted with ethyl acetate, washed with diluted hydrochloric acid and saturated saline,
It was dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was eluted with ethyl acetate / hexane =
The mixture was purified by silica gel chromatography using a 1/2 mixed solution to obtain 20.7 g (53.6 mmol) of compound A-2 as a pale yellow oil. Yield 59.4%. 1-3. Synthesis of Exemplified Coupler (20) 11.7 g (30.0 mmol) of compound A-2 was added to DM
Ac dissolved in 15 ml of Ac and 5.8 g of ammonium carbonate
(60.0 mmol) at 120 ° C. while stirring.
For 1 hour. The mixture was extracted with ethyl acetate, washed with diluted hydrochloric acid and saturated saline, and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain a crude compound A-3. This was dissolved in 20 ml of pyridine, and Compound A was added.
-4 7.84 g (20.0 mmol) was added dropwise over 10 minutes while stirring at room temperature. The mixture was further stirred at 50 ° C. for 1 hour, extracted with ethyl acetate, washed with diluted hydrochloric acid and saturated saline, and dried over anhydrous magnesium sulfate. After filtration,
The solvent was distilled off under reduced pressure, and the residue was eluted with ethyl acetate / ethyl acetate.
After purification by silica gel chromatography using a hexane = 1/1 mixed solution, crystallization was performed from a methylene chloride / hexane mixed solution to obtain 3.35 g (4.73 mmol) of the exemplified coupler (20) as white crystals. Was. Yield 2
3.6%.

Synthesis Example 2 Synthesis of Exemplified Compound (24) The compound was synthesized by the following synthetic route.

[0035]

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2-1. Synthesis of Compound B-1 15.0 g of m-nitrobenzoylacetonitrile (7
8.9 mmol) was dissolved in 60 ml of DMAc, and while stirring under ice cooling, 12.9 ml of TMG (103 mmol) was dissolved.
l) was added dropwise over 15 minutes. After stirring for 10 minutes under ice-cooling, the compound methyl 2-bromopropionate (11.4 ml) was added.
(103 mmol) was added dropwise over 30 minutes while stirring under ice cooling. After stirring at 5 ° C. for 7 hours, the mixture was extracted with ethyl acetate, washed with diluted hydrochloric acid and saturated saline, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure,
The residue was purified by silica gel chromatography using a mixed solution of ethyl acetate / hexane = 1/2 as an eluent to obtain 3.6 g (13.2 mmol) of a compound B-1 as a pale yellow oil. Yield 16.7%. 2-2. Synthesis of Compound B-2 3.7 g (65.9 mmol) of reduced iron and 0.35 g (6.59 mmol) of ammonium chloride were diffused in a mixed solution of 40 ml of isopropyl alcohol and 4 ml of water to obtain a solution of 30.
Heat to reflux for a minute. To this, 3.6 g of compound B-1 (1
3.2 mmol), and the mixture is further heated under reflux for 6 hours and filtered while hot using celite. After the solvent was distilled off under reduced pressure, the residue was dissolved in 15 ml of DMAc, and 1.0 ml (13.2 mmol) of methanesulfonyl chloride and 1.2 ml (14.5 mmol) of pyridine were added, followed by stirring at room temperature. The mixture was extracted with ethyl acetate, washed with diluted hydrochloric acid and saturated saline, and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography using a mixed solution of ethyl acetate / hexane = 1/2 as an eluent to obtain 2.2 g (7.53 mmol).
1) Compound B-2 was obtained as a pale yellow oil. Yield 5
7.1%. 2-3. Synthesis of Exemplified Coupler (24) Compound B-2 (2.2 g, 7.53 mmol) was added to DMA
c. Dissolve in 4 ml and add ammonium carbonate l. 4g (1
5. lmmol) and add 1 at 120 ° C. with stirring.
Reacted for hours. After cooling to room temperature, DMAc 10m
1 to which n-hexadecyl chloroformate 2.3 was added.
g (7.53 mmol), pyridine 0.67 ml (8.
28 mmol) was added. After stirring at room temperature for 1 hour, the mixture was extracted with ethyl acetate, washed with diluted hydrochloric acid and saturated saline,
It was dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was eluted with ethyl acetate / hexane =
After purification by silica gel chromatography using a 1/3 mixed solution, crystallization was performed from an ethyl acetate / hexane mixed solution to obtain 1.38 g (2.47 mmol) of the exemplified coupler (24) as white crystals. Yield 32.8%.

The coupler of the present invention is used together with a color developing agent represented by the general formula (2) which forms a dye by an oxidative coupling reaction. The amount of the coupler used in the present invention depends on the molar extinction coefficient (ε) of the dye to be formed.
The dye formed by coupling has an ε of 5,000 to 50.
In the case of a coupler of about 0000, 0.00
About 1 to 100 mmol / m ² , preferably 0.01 to
10 mmol / m ² , more preferably about 0.05 to 5 mmol / m ² is suitable.

The addition amount of the color developing agent of the present invention is as follows.
0.01 to 100 times, preferably 0.1 to 100 times the coupler.
It is 1 to 10 times, more preferably 0.2 to 5 times. Two or more couplers can be used in combination.

The color light-sensitive material of the present invention basically has a photosensitive silver halide emulsion and a binder in addition to a coupler and a color developing agent of the present invention on a support. In the case of the material, an organic metal salt oxidizing agent, a dye-providing compound (which may also serve as a reducing agent as described later) and the like can be further contained as necessary. These components are often added to the same layer, but they can also be added in separate layers. For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering. The reducing agent is preferably incorporated in the photothermographic material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination. . For example, JP-A-59-180,550, JP-A-64-13,546,
No. 62-253,159, European Patent Publication No. 479,1.
No. 67, etc., a combination of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer, a red-sensitive layer, an infrared-sensitive layer (1), an infrared ray There is a combination of the photosensitive layer (2) and the like. Each photosensitive layer can have various arrangement orders known for a conventional type color photosensitive material. Further, each of these photosensitive layers may be divided into two or more layers as necessary, as described in JP-A-1-252954. In the photothermographic material, various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer may be provided between the silver halide emulsion layers and the uppermost layer and the lowermost layer. Often, various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer constitution described in the above patent, an undercoat layer as described in US Pat. No. 5,051,335, JP-A-1-167,838, JP-A-61
Intermediate layer having a solid pigment as described in JP-A-20-943, JP-A-1-129553, and JP-A-5-34,884.
And DIR as described in JP-A-2-64,634.
Interlayer with compound, US Pat. No. 5,017,454
No. 5,139,919 and JP-A-2-23504.
4, an intermediate layer having an electron transfer agent as described in
It is possible to provide a protective layer having a reducing agent or a layer obtained by combining them, as described in JP-A-249,245. The support has an antistatic function and a surface resistivity of 10 ¹² Ω
-It is preferable to design so as to be not more than cm.

Next, the silver halide emulsion used in the photothermographic material will be described in detail. The silver halide emulsion that can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. The silver halide emulsion used in the present invention may be 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 light fogging. Further, a so-called core-shell emulsion in which the inside and the surface of the grain have different phases may be used, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodisperse or polydisperse, and is disclosed in JP-A-1-167,743,
-223,463, monodisperse emulsion was mixed,
A method of adjusting the gradation is preferably used. The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habits of silver halide grains are those having regular crystals such as cubic, octahedral, and tetrahedral;
Those having crystal defects such as twin planes, or composites thereof or any other materials may be used. Specifically, US Pat. No. 4,500,626, column 50, 4,628,0 U.S. Pat.
No. 21, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17, 029 (1978), No. 1
7, 643 (December 1978), pp. 22-23, ibid.
18, 716 (November 1979), p. 648, ibid.
307, 105 (November 1989) 863-865
Page, JP-A-62-253,159, 64-13,5
No. 46, JP-A-2-236546, JP-A-3-110,
555, and Grafkid, "Physics and Chemistry of Photography",
Published by Paul Monte (P. Glafkides, Chemie et Phisique P
hotographique, Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin, published by Focal Press (GFDuffin, Phot)
ographic Emulsion Chemistry, Focal Press, 1966),
"Manufacture and Coating of Photographic Emulsions", by Zelikman et al., Published by Focal Press (VLZelikman et al., Making and Coating).
Any of silver halide emulsions prepared by the method described in Photographic Emulsion, Focal Press, 1964) can be used.

In the process of preparing the photosensitive silver halide emulsion of the present invention, it is preferable to perform so-called desalting for removing excess salt. As a means for this, a Nudel water washing method in which gelatin is gelled may be used, and inorganic salts composed of polyvalent anions (for example, sodium sulfate), an anionic surfactant, and an anionic polymer (for example, polystyrene sulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. 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 amount of addition 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 contained in the particles, or may be localized inside or on the surface of the particles. Specifically, the emulsions described in JP-A Nos. 2-236542, 1-116,637 and 5-181,246 are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, ammonia, a 4-substituted thioether compound or JP-B-47-1
Organic thioether derivatives described in 1,386 or sulfur-containing compounds described in JP-A-53-144,319 can be used.

Other conditions are described in the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Mont
el, 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chemis)
try, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZelikman
et al., Making and Coating Photographic Emulsion, F
ocal 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. An inverse mixing method in which 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 speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329 and JP-A-55-158, JP-A-55-142329). No. 124, U.S. Pat. No. 3,650,75
No. 7). 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 2.3 and 8.5, more preferably between 2.5 and 7.5.

The photosensitive 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 conventional photosensitive 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, JP-A-5-241,267). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of chemical sensitization.
Specifically, Japanese Patent Application Laid-Open Nos. 5-45,833 and
No. 40,446 can be used. The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.
0 to 10.5, 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 impart green, red and infrared sensitivity to the photosensitive silver halide used in the present invention, 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. 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.
Sensitizing dyes described in JP-A-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 which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615, 641, and JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after 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 a step and known photographic additives which can be used in the photothermographic material and the dye fixing material of the present invention are described in RD Nos. 17, 643 and RD No.
No. 18, 716 and No. 307, 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 23-24, page 648, right column 866-868, 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 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

As the binder for the constituent layers of the photothermographic material and the dye fixing material, hydrophilic binders are preferably used. Examples thereof include those described in the aforementioned Research Disclosure and JP-A-64-13546, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferred, 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, Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. No. 4,960,681.
No. superabsorbent polymers described in JP-A-62-245,260, etc., i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer each other vinyl monomers having Alternatively, a copolymer with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more kinds. In particular, 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. Is also preferred.

In the case of employing a system in which a small amount of water is supplied to perform thermal development, the use of the above superabsorbent polymer makes it possible to quickly absorb water. When a superabsorbent polymer is used in the dye-fixing layer or its protective layer separately from the present invention, it is possible to prevent the dye from being re-transferred from the dye-fixing element to another after transfer. In the present invention, the coating amount of the binder is 20 g per 1 m ^2.
Or less, especially 10 g or less, more preferably 7 to 0.5 g
Is appropriate.

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 reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used. U.S. Pat. No. 4,500,626 is an example of a reducing agent used in the present invention.
Nos. 49-50, 4, 839, 272, 4,
330,617, 4,590,152, 5,0
17,454,5,139,919, JP-A-60
Nos. 140, 335, pages (17) to (18), ibid.
-40,245, 56-138,736, 59
-178,458, 59-53,831, 59
-182,449, 59-182,450, 6
Nos. 0-119,555, 60-128,436, 60-128,439, 60-198,540,
No. 60-181,742, No. 61-259,253
Nos. 62-201,434 and 62-244,04
Nos. 4, 62-131, 253, 62-131, 2
No. 56, No. 63-10, 151, No. 64-13, 54
No. 6, pages (40) to (57), JP-A-1-120,5
No. 53, No. 2-32, 338, No. 2-35, 451
Nos. 2-234, 158 and 3-160, 443
And reducing agent precursors described in EP-A-220,746 at pages 78 to 96 and the like. Various combinations of reducing agents, such as those disclosed in U.S. Pat. No. 3,039,869, can also be used.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be used, if necessary, to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. Particularly preferably, said US Patent No. 5,139,
919, European Patent Publication No. 418,743,
Nos. 138,556 and 3-102,345 are used. Also, a method of stably introducing a compound into a layer as described in JP-A-2-230143 or JP-A-2-23504 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one that does not substantially move in the layer of the light-sensitive material among the reducing agents described above, and is preferably a hydroquinone, Sulfonamidophenols, sulfonamidonaphthols, JP-A-53-110827, U.S. Pat.
2,487, 5,026,634 and 4,83
Compounds described as electron donors in JP-A No. 9,272 and dye-donating compounds having diffusion resistance and reducibility described below are mentioned. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used.

Further, the above-mentioned reducing agent can be used in the intermediate layer and the protective layer 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 357,04
No. 0, JP-A-4-249,245, JP-A-2-64,63
3, JP-A-2-46,450 and JP-A-63-186,2.
The reducing agent described in No. 40 is preferably used. JP-B 3-63,733, JP-A-1-150,135, JP-A-2-110,557, JP-A-2-64,634, JP-A-3-63,733
43,735 and EP-A-451,833 may also be 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.

In the present invention, silver can be used as an image-forming substance in addition to the dye-donating substance. When silver ions are reduced to silver under high-temperature conditions, a dye-donating compound which generates or releases a mobile dye in response to this reaction or vice versa may be used. Examples of the dye-donating compound that can be used in the present invention include compounds having a function of releasing or diffusing a diffusible dye in an image-like manner. 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, and released (Dye) _m -Y and ((Dy)
e) _m- Y) _n- Z represents a group having a property which causes a difference in diffusibility, m represents an integer of 1 to 5, n represents 1 or 2, and m represents Either one
When not, 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.

Compounds that have a diffusible dye as a leaving group and release a diffusible dye upon reaction with an oxidized reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39,165,
U.S. Pat. Nos. 3,443,940 and 4,474,86
No. 7, No. 4,483,914 and the like. Is reducible to silver halides or organic silver salts,
A compound that releases a diffusible dye when the partner is reduced (DRR
Compound). 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. A representative example is U.S. Pat.
8,312, 4,053,312, 4,05
Nos. 5,428 and 4,336,322,
Nos. 65,839, 59-69,839, 53-
3,819, 51-104,343, RD17,
465, U.S. Pat. Nos. 3,725,062 and 3,7
Nos. 28,113 and 3,443,939;
-116,537, 57-179,840 and U.S. Pat. No. 4,500,626. DR
Specific examples of the R compound include the aforementioned U.S. Pat.
Compounds described in Columns 22 to 44 of U.S. Pat. ) ~
(19), (28) to (30), (33) to (35),
(38) to (40) and (42) to (64) are preferable.
The compounds described in U.S. Pat. No. 4,639,408, columns 37 to 39 are also useful. In addition, as the above-mentioned couplers and dye-donating compounds other than the general formula [LI],
Dye silver compounds in which an organic silver salt and a dye are combined (Research Disclosure Magazine, May 1978, pp. 54-58, etc.), and azo dyes used in the heat-developed silver dye bleaching method (US Pat. No. 4,235,957) Research Disclosure Magazine, April 1976, pp. 30-32, etc., and leuco dyes (US Pat. Nos. 3,985,565, 4,02).
2,617) can also be used.

A hydrophobic additive such as a dye-donating compound and a diffusion-resistant reducing agent can be introduced into a layer of a photothermographic material by a known method such as the method described in US Pat. No. 2,322,027. it can. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476, and 4,464. High-boiling organic solvents such as those described in 599,296, JP-B-3-62256 and the like can be used, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C. These dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, etc.
More than one species can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-donating compound used. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. Also, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 and JP-A-62-30
No. 242 or the like and a method of adding it in the form of a fine particle dispersion can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636, (37)-
On page (38), those mentioned as the surfactants described in the aforementioned Research Disclosure can be used. 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.
No. 51 to 52 in the description.

In a system for forming an image by diffusion transfer of a dye, an unnecessary dye or coloring matter is fixed or made colorless in the constituent layers of the photothermographic material of the present invention, thereby improving the white background of the obtained image. Various compounds can be added. Specifically, European Patent Publication No. 353,74
Nos. 1, 461, 416 and JP-A-63-163345.
And JP-A-62-203158 can be used.

Various pigments and dyes can be used in the constituent layers of the photothermographic material of the present invention for the purpose of improving color separation and increasing sensitivity. Specifically, the compounds described in Research Disclosure and EP-A-479,1 are disclosed.
Nos. 67 and 502,508, JP-A-1-1677838.
Nos. 4-343355 and 2-168252, JP-A-61-20943, and EP-A-479,16.
Nos. 7, 502, 508 and the like can be used.

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with the photothermographic material. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or may be in the form of being coated on the same support as the photosensitive material. The relationship between the photosensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention. The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the field of photography can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59;
No. 88,256, pages (32) to (41) and JP-A No. 1-16123.
No. 6, pages (4) to (7), mordants described in U.S. Pat.
74,162, 4,619,883, 4,59
No. 4,308 and the like. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used. The binder used in the dye fixing material of the present invention is preferably the above-mentioned hydrophilic binder. In addition, European Patent No. 44
No. 3,529, a combination of carrageenans and a glass transition temperature of 40 as described in JP-B-3-74,820.
It is preferable to use a latex having a temperature of not more than ℃. Protective layer, release layer,
An auxiliary layer such as an undercoat layer, an intermediate layer, a back layer, and an anti-curl layer can be provided. It is particularly useful to provide a protective layer.

In the constituent layers of the photothermographic material and the dye-fixing material, a high-boiling organic solvent can be used as a plasticizer, a sliding agent, or an agent for improving the releasability between the photosensitive material and the dye-fixing material. Specifically, there are those described in the above-mentioned Research Disclosure and JP-A-62-245253. 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. As examples thereof, various modified silicone oils, particularly carboxy-modified silicone (trade name: X-22-3710) described in Technical Data P6-18B issued by Shin-Etsu Silicone Co., Ltd. are effective. Also, silicone oils described in JP-A Nos. 62-215953 and 63-46449 are effective.

An anti-fading agent may be used in the photothermographic material or the dye fixing material. Examples of the anti-fading agent include antioxidants, ultraviolet absorbers, and certain metal complexes. Dye image stabilizers and ultraviolet absorbers described in Research Disclosure are also useful. Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Also, Japanese Unexamined Patent Publication No.
The compounds described in -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. 2,784), and JP-A Nos. 54-48,535 and 62-1.
36, 641 and 61-88, 256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective. Examples of metal complexes include U.S. Pat. Nos. 4,241,155 and 4,245.
No. 018, columns 3-36, No. 4,254,195, No. 3
Columns 8 to 8, JP-A-62-174,741 and JP-A-61-8
8, 256, pp. 27-29, 63-199,
248, JP-A-1-75,568 and 1-74,2
No. 72 and the like.

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing material in advance, or the dye may be supplied from outside such as a photothermographic material or a transfer solvent described later. It may be supplied to the fixing material. The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination.

A fluorescent whitening agent may be used in the photothermographic material or the dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside such as a photothermographic material or a transfer solvent. For example, K. Veenka
Compounds described in Taraman, "The Chemistry of Synthetic Dyes", Vol. V, Chapter 8, JP-A No. 61-143752, etc. 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. The fluorescent whitening agent can be used in combination with a fading inhibitor or an ultraviolet absorber. Specific examples of these anti-fading agents, ultraviolet absorbers, and optical brighteners include:
It is described in JP-A-62-215,272, pages (125) to (137), and JP-A-1-161,236, pages (17) to (43).

Examples of the hardening agent used in the constituent layers of the photothermographic material and the dye fixing material include the above-mentioned Research Disclosure, US Pat. No. 4,678,739, column 41, 4,791,042, 1984-116,655
Nos. 62-245,261 and 61-18,942
And hardening agents described in JP-A-4-218,044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetaamide)) Ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A-62-234,1).
No. 57 etc.). These hardeners are used in an amount of 0.001 to 1 per gram of gelatin applied.
g, preferably 0.005 to 0.5 g. 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 photothermographic material and the dye fixing material, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-16844.
Nitrogen-containing carboxylic acids and phosphoric acids described in No. 2, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957. When a precursor is used in the present invention, it is particularly preferably used for the photosensitive silver halide emulsion layer as described above, but it can also be used for a dye fixing material. When these compounds are not precursors, 5 × 10 ^-6 to 1 / mol of silver
× 10 ^-1 mol is preferable, and 1 × 10 ^-5 to 1 × 10
^-2 mol is preferably used. More preferred amounts of the precursor are as described above.

The constituent layers of the photothermographic material and the dye-fixing material include 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 Research Disclosure, JP-A-62-173463, and JP-A-62-173463.
183,457. The constituent layers of the photothermographic material and the dye fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, and improving releasability. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-209.
No. 44, 62-135826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as a fluorine oil or a solid fluorine compound resin such as an ethylene tetrafluoride resin described in, for example, No. 62-135826. No.

A matting agent can be used in the photothermographic material and the dye fixing material for the purpose of preventing adhesion and improving slipperiness. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
JP-A Nos. 63-274944 and 63-27, in addition to the compounds described on page 256 (29), benzoguanamine resin beads, polycarbonate resin beads and AS resin beads.
No. 4952. Other research
The compounds described in the disclosure can be used. These matting agents may be added not only to the uppermost layer (protective layer) but also to a lower layer as needed. In addition, the constituent layers of the photothermographic material and the dye fixing material may contain a thermal 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, (26)-
(32), JP-A-3-11,338, JP-B-2-51,
496, etc.

In the present invention, an image formation accelerator can be used in the photothermographic material and / or the dye fixing material. Examples of the image formation accelerator include a redox reaction between a silver salt oxidizing agent and a reducing agent, promotion of a reaction such as formation of a dye from a dye-providing substance or decomposition of the dye or release of a diffusible dye, and photothermographic exposure. It has the function of promoting the transfer of the dye from the material layer to the dye fixing layer, and from the physicochemical function, a base or base precursor, a nucleophilic compound, a high-boiling organic solvent (oil), a thermal solvent, a surfactant , Silver, or compounds that interact with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. For details of these, see U.S. Pat. No. 4,678,739, 38-40.
Column. 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, and the like. Specific examples thereof are described in U.S. Patent Nos. 4,514,493 and 4,657,848.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, a method in which a base and / or a base precursor is contained in the dye-fixing material is preferable from the viewpoint of improving the storage stability of the photothermographic material. . In addition to the above,
EP 210,660, U.S. Pat. No. 4,74
No. 0,445, and combinations of compounds which are capable of forming a complex with metal ions constituting the hardly soluble metal compound (referred to as complex forming compounds), and JP-A No. 61-232,451. Compounds that generate a base by electrolysis described in (1) 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 photothermographic material and the dye fixing material as described in the above patent.

In the present invention, various development stopping agents can be used in the photothermographic material and / or the dye fixing 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 more details, see
2-253, 159, pages (31) to (32).

In the present invention, as a support for the photothermographic material or the dye fixing material, a support that can withstand the processing temperature is used. In general, papers and synthetic polymers (films) described in The Photographic Society of Japan, "Basics of Photonic Engineering-Silver Halide Photography", Corona Co., Ltd. (1979), pp. 223-240. And other photographic supports. In particular,
Polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg, triacetylcellulose), or films containing pigments such as titanium oxide, and polypropylene. Film-processed synthetic paper, 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 and the like are used. These can be used alone,
It can also be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene. The laminate layer may contain pigments and dyes such as titanium oxide, ultramarine blue, and carbon black as necessary. In addition, JP-A-62-253159 (29)-
Page (31), JP-A-1-61,236 (14)-(17), JP-A-63-316,848, JP-A-2-22,651
No. 3-56,955, U.S. Pat. No. 5,001,0.
The support described in No. 33 or 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, a support described in JP-A-63-220,246 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.

As a method of exposing and recording an image on a photothermographic material, for example, a method of directly photographing a landscape or a person using a camera or the like, or a method of exposing through a reversal film or a negative film using a printer or a enlarger. Method, using a copier exposure device to scan and expose the original image through slits, etc., and scanning and exposing image information by emitting light-emitting diodes and various lasers (laser diodes, gas lasers, etc.) via electric signals (Japanese Unexamined Patent Publication No. 2-129625, Japanese Unexamined Patent Publication No.
No. 6,144, No. 5-199,372, No. 6-12
7,021, 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 photothermographic material, as described above, US Pat. Kaihei 2-53,
No. 378 and 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 and potassium dihydrogen phosphate (KDP). ), Inorganic compounds represented by lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide such as 3-methyl-4-nitropyridine-N-oxide (POM) Oxide derivatives, 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. Further, the image information includes an image signal obtained from a video camera, an electronic still camera, etc.
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.

The photothermographic material and / or the dye-fixing material of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of the dye. The heat generating element in this case is described in JP-A-61-14.
No. 5,544 and the like can be used. The heating temperature in the heat development step is about 50 ° C. to 250 ° C., and particularly about 60 ° C. to 180 ° C. is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the case of the latter, the heating temperature in the transfer step can be transferred within the range of the temperature in the heat development step to room temperature.
Up to lower temperatures are preferred.

Although the transfer of the dye is caused only by heat,
Solvents may be used to promote dye transfer. Also,
U.S. Pat. Nos. 4,704,345 and 4,740,44
No. 5, JP-A-61-238,056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. In this method, the heating temperature is preferably not lower than 50 ° C. and not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably from 50C to 100C. Examples of the solvent used for accelerating the development and / or for diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases are described in the section of the image formation accelerator). Described are used), a low-boiling solvent or a mixed solution of a low-boiling solvent and water or the basic aqueous solution. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent. Water is preferably used as a solvent used in these steps of thermal development and diffusion transfer, and any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photothermographic material and the dye fixing material of the present invention, water may be used up or circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144,354 and JP-A-63-144,355.
No. 62-38,460, JP-A-3-210,55.
The device described in the item or water may be used.

These solvents can be applied to the photothermographic material, the dye fixing material, or both. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. As a method of applying this water,
For example, Japanese Patent Application Laid-Open No. 62-253,159, p.
The methods described in JP-A-3-85,544 and JP-A-10-26,818 are preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in advance in the photothermographic material and / or dye fixing element in the form of a hydrate. The temperature of the water to be applied is 30 ° to 60 ° C. as described in JP-A-63-85,544 and the like.
Is fine. In particular, it is useful to raise the temperature to 45 ° C. or higher for the purpose of preventing the propagation of various bacteria in water.

In order to promote the dye transfer, a system in which a hydrophilic heat solvent which is solid at room temperature and dissolves at a high temperature is incorporated in the photothermographic material and / or the dye fixing material can be adopted. The layer to be incorporated may be any of a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but is preferably a dye fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

As a heating method in the development and / or transfer step, a heating block, a plate, a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared and far infrared lamp heater may be used. For example, or by passing through a high-temperature atmosphere. The method described in JP-A-62-253,159 and JP-A-61-147,244, page 27, can be applied to the method of superposing the photothermographic material and the dye fixing material.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
Nos. 5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, JP-A-6-130,509, 6
Nos. 95 and 338 and 6-95 and 267 are preferably used. Further, as a commercially available device, a Pictrostat 100, a Pictrostat 200, a Pictography 3000, a Pictography 2000, or the like manufactured by Fuji Photo Film Co., Ltd. can be used.

When the image obtained by the photothermographic material and the dye fixing element is used as a color proof for printing, the method of expressing the density is to use continuous tone control or use a portion having discontinuous density. Either of the above-described area gradation control and the gradation control combining the two may be used. By using an LD or LED as an exposure light source, a digital signal can be output. As a result, it is possible to use a method (DDCP) 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. 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 configuration 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, a hard copy having an image formed on a sheet can be easily created a plurality of times in a short time. When an LD or LED is used as an exposure light source, two or more kinds of yellow, magenta, and cyan spectral sensitivities, or four spectral sensitivities of yellow, magenta, cyan, and black, and a desired hue are obtained. The spectral sensitivities of the respective colors obtained by mixing the color materials preferably have peaks of the spectral sensitivities at different wavelengths separated by 20 nm or more. As a further alternative, if the spectral sensitivities of two or more different colors have a sensitivity difference of 10 times or more, 1
There is also a method of obtaining images of two or more colors at one exposure wavelength.

Next, a method of reproducing a moire or the like on a printed material by a color printer will be described. In order to create a printing color proof that faithfully reproduces moire and 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.
(The above is described in detail in JP-A-8-192540.)

When recording a color image using an output device such as a color printer, it is possible to realize a color image having a desired color by manipulating, for example, color signals for yellow, magenta, and cyan. 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 created 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 signal 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 in which a color signal CMY corresponding to an arbitrary stimulus value signal XYZ is repeatedly calculated using the Newton method. (PHOTOGRAPHIC SCIENCE AND ENGINEERING Volume 1
6, Number 2.March-April 1972 pp136-pp143 "Metamer
ic color matching in subtractive color photograph
y "). 3. In a color conversion method for converting a color signal from a first color system to a second color system, the color conversion method of the first color system obtained from a 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 consisting 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 the relationship between the color signals of the color system as the inverse conversion relationship.
A method of converting from a color system to a second color system. 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 and the first color system consisting of the real color signal and the virtual color signal, the first color system is repeatedly calculated by the Newton method. For example, a method of obtaining an inverse conversion relationship for conversion into the 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-format, A1-A6, chrysanthemum, B-format, 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 in the range of 100 mm to 2000 mm depending on the size. The photothermographic material and the dye-fixing element may be supplied in a roll or sheet form, and it is also possible to use one of them in a roll form and one in a sheet form.

Hereinafter, the effects of the present invention will be described in detail with reference to examples.

[0087]

EXAMPLES Example 1 An image receiving element R101 having the structure shown in Tables 1 and 2 was manufactured.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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Next, how to make a photosensitive element will be described. First, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer] Solution (I) having the composition shown in Table 4 was added to the well-stirred aqueous solution having the composition shown in Table 3 at an equal flow rate for 9 minutes. , And (II)
The solution was added at an equal flow rate for 9 minutes and 10 seconds from 10 seconds before the addition of solution (I). 36 minutes later, (III) having the composition shown in Table 4
Solution (IV) at the same time as solution (III)
It was added at an equal flow rate for 5 minutes. After washing with water and desalting (using a precipitant a at pH 4.0) using a conventional method, 880 g of lime-treated ossein gelatin was added to adjust the pH to 6.0. 0.8 g and trimethylthiourea 32 mg were added, and the mixture was optimally chemically sensitized at 60 ° C. for 71 minutes, and then 4-hydroxy-6-methyl-1,3,3a, 7-
2.6 g of tetrazaindene, 3.2 g of dye (a), KB
After 5.1 g of r and 2.6 g of a stabilizer described later were sequentially added, the mixture was cooled. Thus, an average particle size of 0.35
As a result, 28.1 kg of a monodisperse cubic silver chlorobromide emulsion having a particle size of μm was obtained.

[0101]

[Table 3]

[0102]

[Table 4]

[0103]

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Photosensitive silver halide emulsion (2) [for green-sensitive emulsion layer] Solution (I) and solution (II) having the composition shown in Table 6 were simultaneously added to a well-stirred aqueous solution having the composition shown in Table 5. Add at an equal flow rate for minutes. Five minutes later, the solution (III) having the composition shown in Table 6 and the solution (I)
V) The solution was added simultaneously at an equal flow rate for 32 minutes. Also, (II
After completion of the addition of solution I) and solution (IV), methanol solution 6 of the dye
0 ml (360 mg of pigment (b1) and 73 mg of pigment (b2).
4 mg). After washing with water and desalting (using a precipitant (a) at a pH of 4.0) according to a conventional method, 22 g of lime-treated ossein gelatin was added, and p
After adjusting the H to 6.0 and the pAg to 7.6, 1.8 mg of sodium thiosulfate and 4-hydroxy-6-methyl-
After adding 180 mg of 1,3,3a, 7-tetrazaindene and optimally sensitizing at 60 ° C., an antifoggant (1)
After adding 90 mg, it was cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 6 having an average grain size of 0.30 μm was prepared.
35 g were obtained.

[0105]

[Table 5]

[0106]

[Table 6]

[0107]

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Photosensitive silver halide emulsion (3) [for blue-sensitive emulsion layer] Solution (I) and solution (II) having the composition shown in Table 8 were added to a well-stirred aqueous solution having the composition shown in Table 7; II) Add the solution and add 10
Seconds later, solution (I) was added over 30 minutes each. Two minutes after the completion of the addition of the solution (I), the solution (V) was added,
Five minutes after the completion of the addition of the liquid (II), the liquid (IV) was added.
0 seconds later, solution (III), solution (III) 27 minutes and 50 seconds, (I
V) Solution was added over 28 minutes. After washing with water and desalting (using a precipitant (b) at a pH of 3.9) in the usual manner,
1230 g of lime-processed ossein gelatin and compound (b)
After adding 2.8 mg to adjust the pH to 6.1 and the pAg to 8.4, 24.9 mg of sodium thiosulfate was added and optimally sensitized at 60 ° C., and then the dye (c) 13.1 was added.
g and 118 ml of compound (c) were successively added and then cooled. The halogenated grains of the obtained emulsion are potato-like grains, the average grain size is 0.53 μm, and the yield is 30700 g.
Met.

[0109]

[Table 7]

[0110]

[Table 8]

[0111]

Embedded image

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

A yellow coupler, a magenta coupler, a cyan coupler, and a gelatin dispersion of a developing agent were each prepared as shown in Table 9. That is, each oil phase component is
Heat and dissolve at 0 ° C to make a uniform solution.
The aqueous phase component heated to ° C. was added and stirred and mixed, and then dispersed with a homogenizer for 10 minutes at 10,000 rpm. Water was added thereto and stirred to obtain a uniform dispersion.

[0114]

[Table 9]

Gelatin dispersions of antifoggants and reducing agents were prepared according to the recipe in Table 10. That is, the oil phase component is heated and dissolved at about 60 ° C., and the aqueous phase component heated to about 60 ° C. is added to the solution, and the mixture is stirred and mixed.
For 1 minute at 10,000 rpm to obtain a uniform dispersion.

[0116]

[Table 10]

A dispersion of polymer latex (a) was prepared according to the recipe in Table 11. That is, an anionic surfactant was added over 10 minutes while stirring a mixture of the polymer latex (a), surfactant and water in the amounts shown in Table 11 to obtain a uniform dispersion. Further, the obtained dispersion was treated with an ultra-loca module (Asahi Kasei ultra-loca module: ACV).
Using -3050), dilution and concentration with water were repeated to prepare a dispersion having a salt concentration of 1/9.

[0118]

[Table 11]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 12. That is, after mixing and dissolving each component, the mixture is mixed with glass beads having an average particle size of 0.75 mm using a mill.
Dispersed for minutes. Further, the glass beads were separated and removed to obtain a uniform dispersion.

[0120]

[Table 12]

Next, a method for preparing a gelatin dispersion of a matting agent added to the protective layer will be described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, followed by high-speed stirring and dispersion. Subsequently, methylene chloride was removed using a vacuum desolvation apparatus to obtain a uniform dispersion having an average particle size of 4.3 μm.

[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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Using the above, photosensitive elements 101 shown in Tables 13 and 14 were produced.

[0128]

[Table 13]

[0129]

[Table 14]

Next, as a comparative example, photosensitive element 1 was prepared in the same manner as photosensitive element 101 except that the developing agent and the coupler in the cyan layer of the dispersion in Table 9 were changed to dye donor (a).
02 was made. Next, photosensitive elements 103 to 116 were prepared in the same manner as the photosensitive element 101, except that the coupler and the developing agent of the present invention were changed as shown in Table 15. The photosensitive element and the image receiving element were subjected to image output at a heating condition of 80 degrees and 30 seconds by using a Pictrostat 330 manufactured by Fuji Photo Film Co., Ltd. The output image was a clear color image.を The maximum density and the minimum density of the cyan
The measurement was carried out using a reflection densitometer X-lite 304 manufactured by E Company.に 関 し て Regarding light fading, under fluorescent light 17000 lux, 30
The densities after standing for days were measured, and the percentage of the ratio with the densities immediately after the treatment was shown as the fading rate. Fading rate = (density after standing for 30 days) / (density immediately after treatment) ×
Table 15 shows the results. As is clear from Table 15, when the compound of the present invention was used, photographic properties and image fastness were excellent.

[0131]

[Table 15]

[0132]

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(Example 2) A method of manufacturing a photosensitive element will be described. First, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [Emulsion for Fifth Layer (680 nm Sensitive Layer)] Solution (I) having the composition shown in Table 17 and (II) in the well-stirred aqueous solution having the composition shown in Table 16 ) Solution was added simultaneously over 13 minutes, and 10 minutes later, (II) having the composition shown in Table 17
Solution I) and solution (IV) were added over 33 minutes.

[0135]

[Table 16]

[0136]

[Table 17]

[0137]

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Further, 13 minutes after the start of the addition of the solution (III), 27
Aqueous solution containing 0.350% of sensitizing dye over 1 minute
50 cc was added.

After washing with water and desalting (using a precipitant a at a pH of 4.1) according to a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and the pAg to 7.9. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for chemical sensitization are as shown in Table 18. The yield of the obtained emulsion was 630 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.20 μm.

[0140]

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[0141]

[Table 18]

[0142]

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[0143]

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Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] A well-stirred aqueous solution having the composition shown in Table 19 was mixed with the solution (I) having the composition shown in Table 20 and (II). ) Solution was added simultaneously over 18 minutes, and 10 minutes later, solution (III) and solution (IV) having the composition shown in Table 20 were added over 24 minutes.

[0145]

[Table 19]

[0146]

[Table 20]

Lime-treated ossein gelatin (calcium content: 150 PPM) after washing with water and desalting (using a precipitant b at a pH of 3.9) and decalcifying in a conventional manner.
22 g), redisperse at 40 ° C., add 0.39 g of 4-hydroxy-6-methyl-1,3,3a, -7-tetrazaindene, adjust the pH to 5.9 and the pAg to 7 .
Adjusted to 8. Then, 70% using the chemicals shown in Table 21
Chemically sensitized at ℃. At the end of the chemical sensitization, the sensitizing dye was added as a methanol solution (a solution having a composition shown in Table 22). Further, after the chemical sensitization, the temperature was lowered to 40 ° C., and 200 g of a gelatin dispersion of a stabilizer described later was added thereto. The yield of the obtained emulsion was 938 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm. The emulsion for the 750 nm photosensitive layer had a J-band type spectral sensitivity.

[0148]

[Table 21]

[0149]

[Table 22]

[0150]

Embedded image

Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Photosensitive Layer)] Solution (I) having the composition shown in Table 24 and (II) in the well-stirred aqueous solution having the composition shown in Table 23 ) Solution was added simultaneously over 18 minutes, and 10 minutes later, solution (III) and solution (IV) having the composition shown in Table 24 were added over 24 minutes.

[0152]

[Table 23]

[0153]

[Table 24]

After washing with water and desalting (using a precipitant a at a pH of 3.8) in the usual manner, 22 g of lime-treated ossein gelatin was added to adjust the pH to 7.4 and the pAg to 7.8. After adjustment, chemical sensitization was performed at 60 ° C. The compounds used for chemical sensitization are as shown in Table 25. The yield of the obtained emulsion was 680 g, a monodispersed cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.32 μm.

[0155]

[Table 25]

A method for preparing a gelatin dispersion of colloidal silver will be described.

The solution having the composition shown in Table 27 was added to the well-stirred aqueous solution having the composition shown in Table 26 over 24 minutes. Thereafter, the precipitate was washed with water using a precipitant a, and 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. The average particle size is 0.02 μm and the yield is 512 g
Met. (Dispersion containing 2% silver and 6.8% gelatin)

[0158]

[Table 26]

[0159]

[Table 27]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

A yellow coupler, a magenta coupler, a cyan coupler, and a gelatin dispersion of a developing agent were prepared according to the formulations shown in Table 28, respectively. That is, each oil phase component is heated and dissolved at about 70 ° C. to form a uniform solution.
The aqueous phase component heated to 0 ° C. was added, and the mixture was stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. Water was added thereto and stirred to obtain a uniform dispersion.

[0162]

[Table 28]

[0163]

Embedded image

Gelatin dispersions of antifoggants and reducing agents were prepared according to the recipe in Table 29. That is, the oil phase component is heated and dissolved at about 60 ° C., and the aqueous phase component heated to about 60 ° C. is added to the solution, and the mixture is stirred and mixed.
For 1 minute at 10,000 rpm to obtain a uniform dispersion.

[0165]

[Table 29]

A gelatin dispersion of the reducing agent was prepared according to the recipe in Table 30. That is, the oil phase component is heated and dissolved at about 60 ° C., and the aqueous phase component heated to about 60 ° C. is added to the solution,
After stirring and mixing, use a homogenizer for 10 minutes, 10,000
Dispersed at rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using an organic solvent removal device under reduced pressure.

[0167]

[Table 30]

A dispersion of the polymer latex (a) was prepared according to the recipe in Table 31. That is, an anionic surfactant was added over 10 minutes while stirring a mixture of the polymer latex (a), surfactant and water in the amounts shown in Table 31 to obtain a uniform dispersion. Further, the obtained dispersion was treated with an ultra-loca module (Asahi Kasei ultra-loca module: ACV).
Using -3050), dilution and concentration with water were repeated to prepare a dispersion having a salt concentration of 1/9.

[0169]

[Table 31]

A gelatin dispersion of the stabilizer was prepared according to the recipe in Table 32. That is, the oil phase component is dissolved at room temperature,
An aqueous phase component heated to about 40 ° C. is added to this solution, and the mixture is stirred and mixed. Then, the mixture is homogenized for 10 minutes at 10,000 rpm.
Was dispersed. Water was added thereto and stirred to obtain a uniform dispersion.

[0171]

[Table 32]

[0172]

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A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 33. That is, after mixing and dissolving each component, the mixture is mixed with glass beads having an average particle size of 0.75 mm using a mill.
Dispersed for minutes. Further, the glass beads were separated and removed to obtain a uniform dispersion.

[0174]

[Table 33]

Next, a method for preparing a gelatin dispersion of a matting agent added to the protective layer will be described. A solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, followed by high-speed stirring and dispersion. Subsequently, methylene chloride was removed using a vacuum desolvation apparatus to obtain a uniform dispersion having an average particle size of 4.3 μm.

[0176]

Embedded image

[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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Using the above, photosensitive elements 201 shown in Tables 34 and 35 were prepared.

[0193]

[Table 34]

[0194]

[Table 35]

Next, as a comparative example, a photosensitive element 202 was prepared in the same manner as the photosensitive element 201 except that the cyan coupler and the developing agent in the dispersion shown in Table 28 were changed to the dye-providing compound (a). Next, photosensitive elements 203 to 216 were prepared in the same manner as the photosensitive element 201 except that the coupler and the developing agent of the present invention were changed as shown in Table 36. Using each of the photosensitive elements and the image receiving element R101, a digital color printer FUJIX PICTROGRAPHY PG-3000 manufactured by Fuji Photo Film Co., Ltd. was heated to 83 ° C.
Image output was performed in 35 seconds. The output image was a clear color image.を The maximum density and the minimum density of the cyan part are determined by a reflection densitometer X-lite3 manufactured by X-lite.
04.光 Regarding photo-fading, a transparent film having an ultraviolet absorbing layer was superimposed on the film surface of the image receiving material, and the film was subjected to Atlas C.I. After irradiating the color image with xenon (100,000 lux) for 10 days using a l65 weatherometer, the density was measured again, and the percentage of the ratio with the density immediately after the treatment was shown as the fading rate. Fading rate = (density after standing for 30 days) / (density immediately after treatment) ×
Table 36 shows the results. As is clear from Table 36, when the compound of the present invention was used, it was found that the compound had excellent color development and image fastness.

[0196]

[Table 36]

[0197]

According to the present invention, the problems of the conventional silver halide photographic light-sensitive material can be solved, and in particular, a silver halide photographic light-sensitive material excellent in color development and light fastness can be provided. .

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tohru Harada 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (72) Inventor Makoto Suzuki 210 Nakanakanuma Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd. (72) Inventor Hideaki Naruse 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide, characterized in that at least one of the silver halide emulsion layers contains a dye-forming coupler represented by the following general formula (1) and a color developing agent represented by the following general formula (2). Photosensitive material. Embedded image Embedded image In the general formula (1), R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom or a substituent having a formula weight of less than 250. Where R
^{When 4} is other than a hydrogen atom, R ³ is -OH or -NH-Y
And Y represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or a sulfamoyl group. X has a formula weight of 250 or more and represents a group capable of leaving by reaction with an oxidized color developing agent. In the general formula (2), R ^a , R ^b , R ^c and R ^d each represent a hydrogen atom or a substituent. A is _{-SO 2 -, - P (R} ) (O) - and represents a divalent group selected from -CO- (the R represents a substituent), Z represents an alkyl group, an aryl group, a heterocyclic group, Represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group or an arylamino group. 2. The silver halide photographic material according to claim 1, wherein said silver halide photographic material is a heat-developable photographic material.