JP2003215764A - Silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developing agent having high developing activity and color developing property, a heat developable photosensitive material having favorable photographic performance such as sensitivity, and a method for forming an image by which fast treatment is possible and favorable picture quality is obtained. <P>SOLUTION: The color developing agent comprises a compound expressed by formula (1). In the formula, each of R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>independently represents hydrogen atom or a substituent, R<SB>4</SB>represents an alkyl group, an aryl group or a heterocyclic group, R<SB>1</SB>and R<SB>2</SB>or/and R<SB>2</SB>and R<SB>4</SB>may be coupled to each other to form a five, six or seven-member ring, Z represents a group of nonmetal atoms forming a five, six or seven-member ring with a nitrogen atom and two carbon atoms in a benzene ring, and R<SB>5</SB>represents an alkyl group, an aryl group or a heterocyclic group. However, the compound expressed by the above formula does not contain any hydroxyl group. carboxyl group or sulfo group in each of R<SB>1</SB>to R<SB>4</SB>. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a built-in color developing agent which enables a dye image to be obtained easily and quickly by heat development.

[0002]

2. Description of the Related Art A method of forming an image by heat development is disclosed in, for example, US Pat.
457,075, and D.I. Cross Tabor (K
Losterboer, “Thermal Processed Si System (Thermal Processed Si)
Lever Systems ”(Imaging Processes & Materials (Imaging P
processes and Materials) Ne
blette 8th edition, J. Sturg
e), V. Wallworth, A.
Edited by Shepp, Chapter 9, Chapter. Such a heat-developable photosensitive material as a non-photosensitive silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), and a silver reducing agent are usually dispersed in an organic binder matrix. contains. The photosensitive material is stable at room temperature, but when it is heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. To generate. This redox reaction is promoted by the catalytic action of the latent image formed by exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas turns black and contrasts with the unexposed areas, thus forming an image.

On the other hand, as a color image forming method for a photographic light-sensitive material, a method utilizing a coupling reaction between a coupler and an oxidized product of a developing agent is the most general method. Patent No. 3,761,270
No. 4,021,240, JP-A-5
No. 9-231539, No. 60-128438, and the like, and in these patents, p-
Sulfonamidophenol is used as a developing agent. Since the coupler does not have absorption in the visible region before processing, the light-sensitive material by the coupling method is advantageous in terms of sensitivity as compared with the light-sensitive material using a coloring material containing a ready-made dye. It is considered that there is an advantage that it can be used as a photographing material. However, p
In the method of incorporating sulfonamidophenol, there is a problem that a proper image cannot be obtained due to deterioration of p-sulfonamidophenol in the light-sensitive material before development processing. As a method for solving this problem, European Published Patent Nos. 1,113,316A2 and 1,113,322
A2, 1,113,323 A2, 1,113,
No. 324A2, No. 1,113,325A2, and No. 1,113,326A2 proposed a photothermographic material containing a blocked paraphenylenediamine-based developing agent and a processing method thereof. However, these photothermographic materials also do not necessarily have appropriate characteristics in terms of image forming temperature, color development efficiency, photographic sensitivity, fog and the like.

[0004]

The problem to be solved by the present invention is to provide a novel photothermographic material which uses a coupling method using a built-in color developing agent and which has good photographic performance such as sensitivity and fog. Is to provide.

[0005]

The above-mentioned objects of the present invention have been achieved by the following heat-developable silver halide color photographic light-sensitive material. <1> A silver halide color photographic light-sensitive material containing a color developing agent represented by the following formula (1). Formula (1)

[0006]

[Chemical 2]

In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a substituent, R ₄ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁ and R ₂ or / And R ₂ and R ₄ may combine with each other to form a 5-, 6- or 7-membered ring. Z represents a non-metal atom group forming a 5-membered, 6-membered or 7-membered ring with a nitrogen atom and two carbon atoms in the benzene ring. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. However, the compound represented by the formula (1) is a hydroxyl group at each of R ₁ to R _4, carboxyl group,
It does not contain any of the sulfo groups. <2> The silver halide color photographic light-sensitive material according to <1>, wherein R ₅ in the compound represented by the formula (1) is represented by the following general formula (2). Formula (2)

[0008]

[Chemical 3]

In the formula, X represents a halogen atom or a group for substituting the benzene ring via a hetero atom, R ₆ represents a substituent, and n represents an integer of 0 to 4. When n is 2 or more, two or more R ₆ may be the same or different,
Groups bonded to adjacent positions may be bonded to each other to form a 5- to 7-membered carbocycle or heterocycle. Other aspects of the present invention will be apparent from the aspects described in the following embodiments of the invention.

In the present specification, "to" is a range including numerical values described before and after it as a minimum value and a maximum value.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION [I] Photothermographic material The preferred embodiment of the silver halide color photographic material of the present invention is a photothermographic material, which comprises a color developing agent, coupler and reducible agent of the present invention on a support. Organic silver salt as a simple silver salt,
And a binder, and a layer (image forming layer) on which an image is formed by a dye formed from the color developing agent of the present invention and a coupler, and a photosensitive silver halide is contained on the image forming layer side. -Sensitive silver halide emulsion layer (photosensitive layer)
Have. Preferably, the image forming layer is a photosensitive layer.
Then, a dye image can be obtained by incorporating a compound represented by the general formula (1) and a coupler compound into the image forming layer side.

The photothermographic material of the present invention comprises at least three kinds of photosensitive silver halides which are different from each other in the light-sensitive wavelength region and / or the absorption wavelength region of the color developing agent of the general formula (1) and the dye formed from the coupler. A dye image can be obtained by providing an emulsion layer (photosensitive layer).

General formula contained in the photothermographic material of the present invention
The compound of (1) has almost no absorption in the visible region, but when heat-developed, it releases a reducing agent and contributes to the formation of a silver image, and an oxidized product of the released reducing agent is generated. . When these oxidants react with the coupler compound, a dye is formed, and an imagewise dye image corresponding to a silver image is obtained. In the present invention, the dye-donating coupler and the compound represented by the formula (1) may be contained in the photosensitive layer, but if they are in a reactive state, they may be added separately in separate layers.

(A) Color Developing Agent The compound represented by the formula (1) of the present invention will be described in detail below. R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a substituent. The substituent represented by R ₁ , R ₂ and R ₃ includes a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), alkynyl Group, aryl group, heterocyclic group, cyano group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group ( (Including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group Basis Sulfamoyl group, alkyl and arylsulfinyl group, alkyl and aryl sulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group Base,
Examples thereof include phosphinylamino group and silyl group. More specifically, a halogen atom (eg, chlorine atom, bromine atom,
(Iodine atom), an alkyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. Alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-
Octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecyl). Cyclohexyl), bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, 5 to 3 carbon atoms)
It is a monovalent group obtained by removing one hydrogen atom from a bicycloalkane of 0. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-
And a tricyclo structure having many ring structures. The alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group) also represents an alkyl group having such a concept. ], An alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Alkenyl group (preferably substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl group (preferably substituted or unsubstituted group having 3 to 30 carbon atoms) A cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms.
Cyclopenten-1-yl, 2-cyclohexene-1-
Yl), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably having 5 to 30 carbon atoms)
Is a substituted or unsubstituted bicycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example, bicyclo [2
2,1] hept-2-en-1-yl, bicyclo [2,2]
2,2] oct-2-en-4-yl)], an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group, aryl group ( Preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted group). Or unsubstituted,
A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and more preferably
It is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, nitro group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy). , Isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably having 3 to 20 carbon atoms).
A silyloxy group of, for example, trimethylsilyloxy,
t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole-5-
Oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably formyloxy group, having 2 to 3 carbon atoms)
0-substituted or unsubstituted alkylcarbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy. ), A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms,
For example, N, N-dimethylcarbamoyloxy, N, N
-Diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 3 carbon atoms).
0 substituted or unsubstituted alkoxycarbonyloxy group, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably substituted with 7 to 30 carbon atoms or An unsubstituted aryloxycarbonyloxy group, for example,
Phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, carbon number 6) To 30 substituted or unsubstituted anilino groups, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino groups (preferably formylamino groups, substituted with 1 to 30 carbon atoms). Alternatively, an unsubstituted alkylcarbonylamino group, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n.
-Octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylamino) Carbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino,
t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, Phenoxycarbonylamino, p-chlorophenoxycarbonylamino,
m-n-octyloxyphenoxycarbonylamino),
Sulfamoylamino group (preferably having 0 to 3 carbon atoms)
0 substituted or unsubstituted sulfamoylamino group, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably having a carbon number) 1 to 30 substituted or unsubstituted alkylsulfonylamino, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl Sulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably,
A substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably 6 to 30 carbon atoms)
Substituted or unsubstituted arylthio, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio, and a heterocyclic thio group (preferably having 2 to 3 carbon atoms).
0 substituted or unsubstituted heterocyclic thio group, for example, 2-benzothiazolylthio, 1-phenyltetrazole-5-
Ilthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl , N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms) , A 6 to 30 substituted or unsubstituted arylsulfinyl group, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl,
p-methylphenylsulfinyl), an alkyl and arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethyl Sulfonyl, phenylsulfonyl,
p-methylphenylsulfonyl), an acyl group (preferably formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl,
Pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl,
N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted with 6 to 30 carbon atoms). A substituted arylazo group, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, phenylazo,
p-chlorophenylazo, 5-ethylthio-1,3,4
-Thiadiazol-2-ylazo), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenyl). Phosphino, methylphenoxyphosphino), phosphinyl group (preferably having 2 to 30 carbon atoms)
A substituted or unsubstituted phosphinyl group, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), a phosphinyloxy group (preferably,
A substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy,
Dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), Examples thereof include a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

[0015] When the group represented by R ₁ to R ₃ is a group capable of being further substituted, the group represented by R ₁ to R ₃ may further have a substituent group, preferred substituents when the Represents a group having the same meaning as the substituent described for R _{1 to} R ₃ . When substituted with two or more substituents, those substituents may be the same or different.

R_FourAnd R_FiveAre an alkyl group and an aryl, respectively.
Or a heterocyclic group, and its alkyl group or aryl
Group, and a preferable range of the heterocyclic group, as described above.
R ₁~ R₃Alkyl group described in the substituent represented by
It represents a group having the same meaning as a reel group and a heterocyclic group. R_Four
Or R_FiveWhen the group represented by is a further substitutable group,
R_FourOr R_FiveThe group represented by may further have a substituent,
Preferred substituents in that case are R₁~ R₃Substituents described in
Represents a group having the same meaning as. Substituted with two or more substituents
, The substituents are the same or different
May be.

R ₁ and R ₂ , or / and R ₂ and R ₄ may combine with each other to form a 5-membered, 6-membered or 7-membered carbocycle or heterocycle.

The preferred range of the compound represented by the formula (1) will be described below. R _{1 to} R ₃ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group,
Alkyl and aryl sulfonylamino groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, cyano groups, nitro groups, sulfamoyl groups, alkylsulfonyl groups, arylsulfonyl A group and an acyloxy group are preferable, and a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkyl, and an arylsulfonylamino group, an alkoxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a cyano group, a nitro group, A sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group are more preferable. Particularly preferably, either R ₁ or R ₃ is a hydrogen atom. More preferably, R ₂ is an alkyl group or an alkoxy group.

R ₄ is preferably an alkyl group.

Z preferably forms a 1,2,3,4-tetrahydroquinone skeleton or an indoline skeleton together with the adjacent nitrogen atom, and the hydrogen atom of the hydrocarbon constituting Z may be substituted by a substituent. .

R ₅ is preferably an alkyl group or an aryl group, and more preferably a substituted phenyl group represented by the following formula (2). Formula (2)

[0022]

[Chemical 4]

In the formula, X represents a halogen atom or a group substituting for a benzene ring via a hetero atom, R ₆ represents a hydrogen atom or a substituent, and n represents an integer of 0 to 4. When n is 2 or more, two or more R _{6 s} may be the same or different, and groups bonded to adjacent positions are bonded to each other to form a 5- to 7-membered carbocycle or heterocycle. May be.

X is a halogen atom, hydroxy group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino. Group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group,
Arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, arylazo group, heterocyclic azo group, imide Groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups. For preferred ranges of these groups, see R ₁ above.
To R ₃ are the same as those described for the substituent.

X is a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, a carbamoyloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonyl group. Amino group, arylsulfonylamino group, mercapto group, alkylthio group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, and silyl group are more preferable, and halogen atom, hydroxy group, alkoxy group, acylamino group, aminocarbonylamino are more preferable. Groups, alkoxycarbonylamino groups, alkylsulfonylamino groups, and arylsulfonylamino groups.

[0026] R ₆ represents a substituent, the substituent represented by R ₆ have the same meanings of the group as the substituent described in the explanation of R ₁ to R _3.

R ₆ is a halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group. Are preferred, and a halogen atom, an alkyl group, an alkoxy group, and an acylamino group are more preferred. n is preferably an integer of 0 to 3.

In the compound represented by the formula (1), R
It is preferable that the ClogP value of the compound in which _5- SO ₂ —NH—CO— is replaced by a hydrogen atom is 3.0 or more. C
The log P value is a calculated value of the water / octanol partition coefficient of the compound, and the present inventors calculated it using Chem Draw Ultra Ver. 5.0 manufactured by Cambridge Soft Corporation.

Specific examples of the compound represented by the formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[0030]

[Chemical 5]

[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

[Chemical 8]

[0034]

[Chemical 9]

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

Next, a method for synthesizing the compound represented by the formula (1) of the present invention will be described. R ₅ —SO ₂ in formula (1)
The portion to the right of the nitrogen atom to which --NH--CO-- is bonded is a compound called tetrahydroquinoline, which is described in Chem. Ber.
54, page 1729 (published in 1921).

Synthesis Example 1 <Synthesis of Exemplified Compound DEVP-4>

Exemplified compound DEVP-4 was synthesized according to the following scheme.

[0042]

[Chemical 14]

Synthesis of INT-1B 151 g (0.800 mol) of 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline (INT-1A) manufactured by Aldrich, 269 g of sodium hydrogen carbonate (3.20 mol), and 500 ml of N-methylpyrrolidone
The mixture was heated in an oil bath at 170 ° C and stirred. 1-Bromooctane (309 g, 1.60 mol) was added dropwise over 2 hours, and then 8
Superheated stirring was continued for a period of time. After allowing to stand overnight, 1500 ml of water and 1000 ml of hexane were added for extraction, the organic layer was washed with brine and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, 0.
Distilled under reduced pressure at 39 kPa to collect the fraction at 185-195 ° C and 180 g (yield 7
4.6%) of INT-1B was obtained.

Synthesis of INT-1C 100 g (0.332 mol) of INT-1B and concentrated hydrochloric acid 8 in 300 ml of methanol
5.5 ml (0.996 mol) was added, and the mixture was cooled with a freezing agent and stirred. To this, a solution of 27.5 g (0.398 mol) of sodium nitrite dissolved in 60 ml of water was added dropwise over 20 minutes while keeping the internal temperature at 5 ° C or lower. After stirring for 2.5 hours, water 800 ml, chloroform 300 m
1 and hexane (300 ml) were added for extraction, and the extract was washed twice with a sodium hydrogen carbonate solution. Purification by silica gel column chromatography gave 92.7 g (yield 84.5%) of INT-1C.

Synthesis of INT-1D The total amount of INT-1C obtained above was dissolved in 200 ml of ethanol, and
Using an autoclave having an internal volume of 1.0 liter, hydrogenation was carried out under the conditions of hydrogen pressure of 5 MPa and room temperature in the presence of 1.0 g of a% palladium carbon catalyst. The reaction mixture was filtered through Celite and concentrated under reduced pressure to obtain 84.2 g (yield 99.4%) of INT-1D.

Synthesis of INT-1E 552 g (4.00 mol) of commercially available 1,4-dimethoxybenzene was dissolved in 1100 ml of methylene chloride, and the internal temperature of 308 ml (4.63 mol) of chlorosulfonic acid under ice cooling did not exceed 5 ° C. So that it was dripped. After the dropping, the reaction system was placed at room temperature and further stirred for 1 hour. Then 1000 ml of acetonitrile and 600 ml of DMAC (N, N-
Dimethylacetamide) was poured. Then the reaction system is at 35 ℃
The mixture was warmed up in the warm bath described above and 404 ml (4.33 mol) of phosphorus oxychloride was added dropwise at an internal temperature of 30 ° C. At this time, care was taken so that the internal temperature did not exceed 40 ° C. After dropping, the mixture was further reacted at 35 ° C. for 1 hour, and then the reaction solution was poured into ice water. Extracted with ethyl acetate,
After washing with water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 2,5-dimethobenzenesulfonyl chloride. 800 ml of a 25% aqueous ammonia solution and 3000 ml of acetonitrile were ice-cooled, and the internal temperature was kept at 5 ° C or lower and stirred. The 2,5-dimethoxenebenzenesulfonyl chloride obtained by the above-mentioned operation was added thereto in 30 divided portions. After the addition, the mixture was further reacted for 30 minutes and then poured into a mixed liquid of 800 ml of concentrated hydrochloric acid and 3500 ml of ice water under stirring. The precipitated crystals were collected by filtration, washed with water, and further washed with 500 ml of acetonitrile to obtain 827.3 g of 2,5-dimethobenzenesulfonamide as white crystals (yield 95.2%). 827.3g (3.81mol)
2,5-Dimethobenzenesulfonamide, 3000 ml of acetonitrile, and 1170 ml (8.39 mol) of triethylamine were stirred under water cooling, and 626 g (4.00 mol) of phenyl chloroformate was added dropwise so that the internal temperature did not exceed 20 ° C. did. After dropping
The reaction was carried out at 20 ° C or lower for 2 hours. After the reaction, the mixture was poured into a mixed solution of 700 ml of concentrated hydrochloric acid and 7000 ml of ice water with stirring. The precipitated crystals were collected by filtration, washed with water, and further washed with 800 ml of acetonitrile to obtain 1130 g of INT-1E as white crystals (yield 88.0
%).

Synthesis of DEVP-4 15.8 g (50.0 mmol) of INT-1D and 16.9 g (50.0 mmol) of INT-1E were added to 100 ml of acetonitrile and stirred at room temperature, and 14.0 ml (100 mmol) of triethylamine was added, The mixture was stirred at room temperature for 2 hours. 200 ml of ethyl acetate and 300 ml of water were added for extraction, and the organic layer was washed with brine. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. Acetonitrile as residue
80 ml was added and dissolved by heating, and cooled with stirring to crystallize.
The precipitated crystals were collected by filtration and washed with cold acetonitrile.
After drying, 16.3 g (yield 58%) of Exemplified Compound DEVP-4 was obtained as white crystals. Melting point: 125-128 ℃

Synthesis Example 2 <Synthesis of Exemplified Compound DEVP-5>

Exemplified compound DEVP-5 was synthesized according to the following scheme.

[0050]

[Chemical 15]

Synthesis of INT-2B 1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline (INT-1A) 87.6 g (0.500 mol) manufactured by Aldrich, sodium hydrogen carbonate 84.0 g (1.00mol), and N-methylpyrrolidone 300m
l was stirred at room temperature and 101.4 g (0.650 mol) of ethyl iodide was added. Gradually heat the oil bath to 70 ℃ and
Stir for hours. After cooling to room temperature, 800 ml of water and ethyl acetate 7
00 ml was added for extraction, and the organic layer was washed 3 times with 700 ml of water. The extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and distilled under reduced pressure to obtain 67.7 g (yield 62.3%) of INT-2B.

Synthesis of INT-2C 56.0 g (0.258 mol) of INT-2B and concentrated hydrochloric acid in 250 ml of methanol
88.5 ml (1.03 mol) was added, and the mixture was cooled with a freezing agent and stirred. To this, a solution prepared by dissolving 18.7 g (0.271 mol) of sodium nitrite in 60 ml of water was added dropwise over 1 hour. The internal temperature at this time is 7-1
It was 0 ° C. After stirring for 1 hour, water 600 ml, chloroform 40
It was extracted by adding 0 ml, and further washed twice with 400 ml of water. Hexane (300 ml) was added to the organic layer, supported on silica gel packed in a column tube without using a solvent, and purified by eluting with a mixed solvent of hexane / ethyl acetate to give 51.6 g (yield 81.3%).
Got INT-2C.

Synthesis of INT-2D The total amount of INT-2C obtained above was dissolved in 250 ml of methanol and 50 ml of tetrahydrofuran, and an autoclave having an internal volume of 1.0 liter was used in the presence of 1.0 g of 5% palladium carbon catalyst. Hydrogen was added under the conditions of hydrogen pressure of 5 MPa and room temperature. The reaction mixture was filtered through Celite and washed with methanol. INT-2D obtained by concentrating the filtrate under reduced pressure was directly used in the next step.

Synthesis of DEVP-5 The above INT-2D and 84.3 g (0.250 mol) of INT-1E were added to 500 ml of acetonitrile and 100 ml of N, N-dimethylacetamide and stirred under ice cooling, and 58.5 ml of triethylamine (0.419 mol) 2
The solution was added dropwise over a period of time and then stirred at room temperature for 3 hours. Acetic acid
Add 24 ml dropwise over 20 minutes and add 600 ml of acetonitrile and 400 ml of water.
ml was added and stirred for 1 hour. The precipitated crystals were collected by filtration, washed with a mixed solution of 200 ml of acetonitrile and 100 ml of water, and dried. The obtained crystals were recrystallized with 400 ml of ethyl acetate, and the precipitated crystals were collected by filtration and washed with 100 ml of ethyl acetate. After drying, 60.6 g (yield 60.8%) of Exemplified Compound DEVP-5 was obtained as white crystals. Melting point: 176-179 ℃

Synthesis Example 3 <Synthesis of Exemplified Compound DEVP-59>

Exemplified compound DEVP-59 was synthesized according to the following scheme.

[0057]

[Chemical 16]

Synthesis of INT-3E Commercially available p-toluenesulfonamide 85.6 g (0.500 mol), 425
ml acetonitrile and 139.5 ml triethylamine (1.
(00 mol) was cooled with ice water and stirred, and phenyl chloroformate 8
2.2 g (0.525 mol) was added dropwise over 2 hours and the reaction was continued for 1 hour. After the reaction, the mixture was poured into a mixed solution of 41.7 ml concentrated hydrochloric acid and 500 ml ice water with stirring. It was extracted with 500 ml of ethyl acetate, the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure, the residue was crystallized with hexane, and the precipitated crystals were collected by filtration. After washing with hexane and drying, INT-3E
101 g of white crystals were obtained (yield 69.3%).

Synthesis of DEVP-59 INT-1D synthesized in the same manner as in Synthesis Example 1 was mixed with 1,5-naphthalenedisulfonic acid (NDS) in acetonitrile, heated and dissolved, cooled, filtered, INT The NDS salt of -1D was synthesized and the experiments of Synthesis Examples 3 and 4 were performed using this. INT-
1D NDS salt 60.5 g (0.100 mol) was added to DMAC 300 ml and stirred under a nitrogen atmosphere, and triethylamine 27.9 ml (0.200 mol) was added.
Was added and stirred for 30 minutes. Unnecessary substances are filtered off, and a small amount of DM
Washed with AC. Stir the filtrate at room temperature under a nitrogen atmosphere and
5.0 g (0.120 mol) of INT-3E and 13.9 ml of triethylamine were added, and the mixture was stirred for 4 hours. To the reaction solution, 500 ml of water and 11.4 ml of acetic acid
Was added and extracted with 400 ml of ethyl acetate. The organic layer was washed successively with water, multi-layered water and saturated saline, and dried over anhydrous magnesium sulfate. Concentrate under reduced pressure and the residue is acetonitrile.
Crystallization was performed with 200 ml, and the precipitated crystals were collected by filtration and washed with cold acetonitrile. After drying, 34.0 g (yield 66.2%) of Exemplified Compound DEVP-58 was obtained as white crystals. Melting point: 146-148 ° C

Synthesis Example 4 <Synthesis of Exemplified Compound DEVP-36>

Exemplified compound DEVP-36 was synthesized according to the following scheme.

[0062]

[Chemical 17]

Synthesis of INT-4E 170 ml of 25% aqueous ammonia solution and 500 ml of acetonitrile were ice-cooled and stirred while keeping the internal temperature at 5 ° C. or lower. Commercially available
126 g (0.513mo) of 2,5-dichlorobenzenesulfonyl chloride
l) was added in 5 divided portions over 1 hour. After the addition, the mixture was further reacted for 30 minutes and then poured into a mixed liquid of 100 ml of concentrated hydrochloric acid and 1000 ml of ice water under stirring. The precipitated crystals were collected by filtration and washed with water. 2,5-dichlorobenzenesulfonamide dried
100 g was obtained as white crystals (yield 88%). 2,5-dichlorobenzenesulfonamide above 45.2g (0.200mol), 500ml
Of acetonitrile and 55.8 ml of triethylamine (0.400
(mol) was cooled with ice water and stirred, and phenyl chloroformate 65.8
g (0.420 mol) was added dropwise over 1 hour and the reaction was continued for 1 hour. After the reaction, the mixture was poured into a mixed solution of 5 ml of concentrated hydrochloric acid and 500 ml of ice water with stirring. The precipitated crystals are collected by filtration, washed with water and dried to INT-4E.
57.2 g of white crystals were obtained (yield 82.6%).

Synthesis of DEVP-36 Add 60.5 g (0.100 mol) of NDS salt of INT-1D to 300 ml of DMAC,
Stir in a nitrogen atmosphere and add 27.9 ml (0.200 ml) of triethylamine.
mol) was added and stirred for 30 minutes. The unwanted material was filtered off and washed with a small amount of DMAC. The filtrate was stirred at room temperature and 41.5 g (0.120 m
ol) INT-4E and 13.9 ml of triethylamine were added, and the mixture was stirred for 3 hours. The reaction mixture was extracted by adding ethyl acetate (400 ml) and water (500 ml). The organic layer was washed with water, multi-layered water, and saturated saline in this order, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 2 /
Purified in 1), the concentrated residue was crystallized from methanol. The precipitated crystals were collected by filtration and washed with cold methanol. After drying, 31.3 g (yield 55.0%) of Exemplified Compound DEVP-36 was obtained as white crystals. Melting point: 121-123 ° C

The color developing agent represented by the general formula (1) of the present invention may be used in combination of two or more kinds in the same photosensitive layer or in different photosensitive layers. You may use together. As color developing agents other than the present invention, European Published Patents 11133222, 1113323, 1113324.
No. 11, No. 1113325, No. 1113326, No. 1158358, No. 11583
No. 59, No. 1160621, No. 1164417, No. 1164418, No. 116
8071, U.S. Patent 6,319,640 B1, International Patent Publication 01/9694
No. 6, and the compounds described in No. 01/96954. Specific examples include the following developing agents.

[0066]

[Chemical 18]

[0067]

[Chemical 19]

[0068]

[Chemical 20]

[0069]

[Chemical 21]

(B) Microcrystalline Particle Dispersion In the present invention, it is preferable that a color developing agent, a thermal solvent, and other additives are contained in the light-sensitive material as a microcrystalline particle dispersion. Colloidal dispersions of microcrystalline particles of these materials can be obtained by any method of applying mechanical shear that is well known in the art.
Examples of such methods are US Pat. Nos. 2,581,414 and 2,855,156 and Canadian Patent No. 1,1.
05,761 and is incorporated herein by reference. These methods include solid particle pulverization methods such as ball mill method, pebble mill method, roller mill method, sand mill method, bead mill method, dinomill method, massup mill method and media mill method. Further, these methods include a colloid mill method, an attritor fine grinding method, a dispersion method using ultrasonic energy, and a high-speed stirring method (described in US Pat. No. 4,474,872 to Onishi et al. Incorporated by reference to this) is included. The ball mill method, the roller mill method, the media mill method, and the fine pulverization method using an attritor are preferable because they are easy to operate, easy to wash, and have good reproducibility.

Alternatively, a dispersion in which the compound exists in an amorphous physical state is prepared by a well-known method such as a colloid mill method, a homogenization method, a high speed stirring method, and a sonication method. be able to. Then, the amorphous physical state of the compound can be converted into the microcrystalline physical state by a method such as a thermal annealing method or a chemical annealing method. The thermal annealing method includes a temperature program method of circulating the amorphous compound at a temperature higher than the glass transition temperature. A preferred thermal anneal method involves circulating the dispersion over a temperature range of 17-90 ° C. This cycling step can include any sequence of temperature changes that promotes the formation of a microcrystalline phase from the remaining amorphous physical state. Typically, the duration of the high temperature interval is chosen to activate the phase formation while at the same time minimizing grain growth due to aging and collision processes. Chemical annealing methods include incubation methods with chemical agents that modify the partitioning of the compound and surfactant between the continuous and discontinuous phases of the dispersion.
Such chemical agents include hydrocarbons (hexadecane, etc.), surfactants, alcohols (butanol, pentanol, undecanol, etc.) and high-boiling organic solvents. These chemical agents can be added to the dispersion during grain formation or after grain formation. The chemical annealing method includes a method of incubating the dispersion at 17 to 90 ° C. in the presence of the chemical agent, a method of stirring the dispersion in the presence of the chemical agent, adding the chemical agent, and then adding the chemical agent. The method includes a method of slowly removing the by diafiltration method and the like.

The formation of a colloidal dispersion in an aqueous medium is
The presence of dispersing aids such as surfactants, surface active polymers and hydrophilic polymers is usually required. Such dispersion aids are described by Chari et al., US Pat. No. 5,008,179 (13-14).
Column) and US Pat. No. 5,104,776 to Bagchi and Sargeant (columns 7 to 13), which can be used appropriately.

In the present invention, the number average particle size of the microcrystalline particle dispersion is preferably 0.001 to 5 μm, more preferably 0.001 to 0.5 μm.

The photothermographic material of the present invention has a color developing agent on the same surface of the support as the photosensitive silver halide and the reducible silver salt. The addition amount of the developing agent in the present invention can be used in a wide range, but it is preferably 0.01 to 100 times by mol, and more preferably, the coupler compound.
It is 0.1 to 10 times by mole.

The color developing agent used in the present invention preferably has a water solubility of 1 g / m ³ or less, and preferably 10 ^-3 g / m ³ or less, in order to enhance the dispersion stability of the microcrystalline dispersion. More preferably,

The melting point of the color developing agent used in the present invention is preferably 80 to 300 ° C. The combination of the color developing agent and the thermal solvent is preferably compatible.
The combination of the color developing agent and the coupler is preferably incompatible.

(C) Coupler The photothermographic material of the present invention comprises
The coupler compound is provided on the same surface of the support as the photosensitive silver halide, the binder and the reducible silver salt. The coupler compound used in the present invention is a compound known as a coupler in the photographic industry, and a 2-equivalent or 4-equivalent coupler is used. Examples of photographic couplers include couplers and research disclosures having the functions described in "Conventional Color Photographic Organic Compounds" by Nobuo Furudate (Organic Synthetic Chemistry, Vol. 41, p. 439, 1983). 37038 (February 1995), pages 80-85, and pages 87-89.
Couplers detailed on the page can be used.

Examples of yellow color image forming couplers include pivaloylacetamide type, benzoylacetamide type, malon diester type, malon diamide type, dibenzoyl methane type, benzothiazolyl acetamide type, malon ester monoamide type, benzoxazolyl type. Luacetamide type, benzimidazolylacetamide type, benzothiazolylacetamide type, cycloalkylcarbonylacetamide type, indoline-2-ylacetamide type,
Quinazolin-4-one-2-ylacetamide type described in U.S. Patent No. 5,021,332, benzo-1,2, described in No. 5,021,330
4-thiadiazine-1,1-dioxide-3-ylacetamide type, couplers described in European Patent 421221A, US Pat.
Couplers described in 455, 149, couplers disclosed in European Patent Publication No. 0622673, European Patent Publication Nos. 0953871, 0953872
No. 0953873, 3-indoloylacetamide type couplers and the like.

Examples of magenta color image forming couplers include 5-pyrazolone type, 1H-pyrazolo [1,5-a] benzimidazole type, 1H-pyrazolo [5,1-c] [1,2,4] triazole type , 1H-pyrazolo [1,5-b] [1,2,4] triazole type, 1H-imidazo [1,2-b] pyrazole type, cyanoacetophenone type, active propene type described in WO93 / 01523, WO93
Enamine type described in / 075342, 1H-imidazo [1,2-b] [1,
2,4] Triazole-type coupler, US Pat. No. 4,871,652
And the couplers described in No.

Examples of cyan image forming couplers include phenol type and naphthol type, European Patent Publication 0294453.
2,5-diphenylimidazole type, 1H-pyrrolo [1,2-b] [1,2,4] triazole type, 1H-pyrrolo [2,1-
c] [1,2,4] triazole type, JP-A-4-188137 and
Pyrrole type described in 4-190347, 3-hydroxypyridine type described in JP-A-1-315736, US Pat. No. 5,164,289
Pyrrolopyrazole type described in JP-A-4-174229, Pyrrolymidazole type described in JP-A-4-17429, Pyrazolopyrimidine type described in US Pat. No. 4,950,585, Pyrrolotriazine type described in JP-A-4-204730 Couplers, couplers described in U.S. Pat.No. 4,746,602, couplers described in U.S. Pat.No. 5,104,783, couplers described in U.S. Pat.
Examples thereof include couplers described in No. 556700. Specific examples of typical coupler compounds that can be used in the present invention are shown below, but the present invention is not limited to these specific examples.

[0081]

[Chemical formula 22]

[0082]

[Chemical formula 23]

[0083]

[Chemical formula 24] CP-116 CP-117

[0084]

[Chemical 25]

[0085]

[Chemical formula 26]

[0086]

[Chemical 27]

[0087]

[Chemical 28]

[0088]

[Chemical 29]

[0089]

[Chemical 30]

[0090]

[Chemical 31]

[0091]

[Chemical 32]

[0092]

[Chemical 33]

[0093]

[Chemical 34]

The above-mentioned coupler compound can be easily synthesized by a method known in the photographic art described in the above-mentioned patent specifications relating to the coupler.

The coupler compound used in the present invention can be incorporated into the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, US Pat. Nos. 4,555,470 and 4,53
No. 6,466, No. 4,536,467, No. 4,58
7,206, 4,555,476, 4,59
A high-boiling point organic solvent such as those described in JP-B No. 9,296, JP-B No. 3-62256 and the like may be used, if necessary, at a boiling point of 50 ° C to 16 ° C.
It can be used in combination with a low boiling point organic solvent at 0 ° C. Two or more kinds of these dye donating couplers and high boiling point organic solvents can be used in combination. The amount of the high boiling point organic solvent is 10 g or less per 1 g of the hydrophobic additive used,
It is preferably 5 g or less, more preferably 1 g to 0.1 g. 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. Japanese Patent Publication No. S51-39853 and Japanese Patent Publication No. S51-59943, and a dispersion method using a polymer, and Japanese Patent Publication S62-3024.
It is also possible to use the method described in No. 2 etc. in which it is added as a fine particle dispersion. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained 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) to (3)
The surfactants listed on page 8) above in Research Disclosure can be used. Further, the phosphoric acid ester type surfactants described in Japanese Patent Application Nos. 5-204325, 6-19247 and West German Laid-Open Patent No. 1,932,299A can also be used. Further, according to a well-known solid dispersion method, the powder of the coupler compound may be dispersed in water by a ball mill, a colloid mill, a sand grinder mill, a manton golin, a microfluidizer or ultrasonic waves.

The coupler compound used in the present invention may be added to any layer on the support as long as it is on the same surface as the photosensitive silver halide and the reducible silver salt, but it is a layer containing silver halide. Alternatively, it is preferably added to the layer adjacent thereto. The amount of the coupler compound used in the present invention is preferably 0.2 to 200 mmol, more preferably 0.3 to 100 mmol, and further preferably 0.5 to 30 mmol per mol of silver. The coupler compounds may be used alone or in combination of two or more.

When the compound of the present invention is used as a photographic material, the amount of the coupler which can be used in the present invention is 0.5 to 200 mmol, preferably 2 to 100 mmol per mol of silver. used.

The photothermographic material of the present invention may contain at least one coupler composed of a compound forming a dye having maximum absorption in the non-visible region. Such a coupler preferably comprises compounds represented by the following general formulas (2) to (6).

[0099]

[Chemical 35]

In the general formula (2), R ⁸ represents a substituent, and n is 0
Represents an integer of 5 to 5, R ⁹ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R ¹⁰ represents an aryl group having a total Hammett sigma value of the substituents on the aryl group is 0.3 or more, Or a 5- to 7-membered heterocyclic group, L ¹ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent.

[0101]

[Chemical 36]

In the general formula (3), R ¹¹ represents a substituent, k represents an integer of 0 to 3, Y ¹ represents a hydroxyl group or (EWG) ₂
CH- group, EWG represents an electron-withdrawing group, Z represents a non-metal atom group which is condensed with a benzene ring to form a 5- to 7-membered nitrogen-containing heterocyclic group, L ² is a hydrogen atom or a developing agent. Represents a group capable of leaving by a reaction with an oxidant.

[0103]

[Chemical 37]

In the general formula (4), R ²¹ represents a substituent, m represents an integer of 0 to 2, R ²² and R ²³ represent a hydrogen atom or a substituent, and Y ² represents (EWG) ₂ CH. Represents a group, and L ³ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent. R
²² and R ²³ may combine to form a carbocycle.

[0105]

[Chemical 38]

In the general formula (5), R ³¹ and R ³² are an electron-withdrawing group having an Hammett sigma-para value of 0.3 or more, an aryl group,
Or a heterocyclic group, R ³³ represents a hydrogen atom or a substituent, Q represents a nitrogen atom or -C (R ³⁴ ) =, R ³⁴ represents a hydrogen atom or a substituent, L ⁴ represents a hydrogen atom or It represents a group capable of splitting off upon reaction with an oxidized product of a developing agent.

[0107]

[Chemical Formula 39]

In the general formula (6), R ⁴¹ represents a substituent, p represents an integer of 0 to 5, R ⁴² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ⁴³ represents A hydrogen atom, an acyl group, an alkyl group, an aryl group, or a heterocyclic group, R ⁴⁴ represents an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group, L ⁵ Represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent.

The compounds represented by formulas (2) to (6) are described in detail below. In the general formula (2), R
⁸ represents a substituent, specifically, a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group),
Alkenyl group (including cycloalkenyl group and bicycloalkenyl group), alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino Group, alkyl and aryl sulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl sulfinyl group, alkyl and aryl Ruhoniru group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group,
It represents a carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group and the like.

Specific examples of the substituent represented by R ⁸ include a halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.), alkyl group [linear, branched, cyclic substituted or unsubstituted alkyl Represents a group. Alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group,
Ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group,
2-cyanoethyl group, 2-ethylhexyl group, etc., cycloalkyl group (preferably substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc. ),
Bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, 5 to 5 carbon atoms
A monovalent group obtained by removing one hydrogen atom from 30 bicycloalkanes, such as bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] octane-3-yl group, etc.) , A tricyclo structure having many ring structures, an alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group, etc.)
Etc.], an alkenyl group [representing a linear, branched, or cyclic substituted or unsubstituted alkenyl group. Alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, vinyl group, allyl group, prenyl group, geranyl group, oleyl group, etc.), cycloalkenyl group (preferably having 3 to 30 carbon atoms) A substituted or unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as a 2-cyclopenten-1-yl group or 2-cyclohexene-1- Group, etc.), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, one hydrogen atom of bicycloalkene having one double bond is removed. Monovalent group such as bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-yl group, etc.)
Etc.], an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, an ethynyl group, a propargyl group, a trimethylsilylethynyl group, etc.),

Aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o-
Hexadecanoylaminophenyl group, etc.), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted heterocyclic group, that is, one obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound). A valent group, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n -Octyloxy group, 2-
Methoxyethoxy group), aryloxy group (preferably substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitro Phenoxy group,
2-tetradecanoylaminophenoxy group, etc.), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group, t-butyldimethylsilyloxy group, etc.),

Heterocyclic oxy group (preferably having 2 to 2 carbon atoms)
30 substituted or unsubstituted heterocyclic oxy groups, 1-
Phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group, etc., acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substitution having 6 to 30 carbon atoms) Or an unsubstituted arylcarbonyloxy group and the like, for example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group,
p-methoxyphenylcarbonyloxy group, etc.), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group). Group, morpholinocarbonyloxy group, N, N-di-
n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group, etc., alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group Group, t-butoxycarbonyloxy group, n-octylcarbonyloxy group, etc., aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy group. , P-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group, etc.), amino group (preferably amino group, carbon number 1 to 1)
30 substituted or unsubstituted alkylamino groups, 6 carbon atoms
~ 30 substituted or unsubstituted anilino group, for example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, etc., acylamino group (preferably formylamino group,
A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as a formylamino group, an acetylamino group, a pivaloylamino group, a lauroylamino group. A benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, etc., an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, For example, carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group, etc., alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonyl having 2 to 30 carbon atoms). An amino group, for example methoxycarbonylami Group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, etc., aryloxycarbonylamino group (preferably substituted or unsubstituted with 7 to 30 carbon atoms) A substituted aryloxycarbonylamino group, for example, phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group, etc.),

Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octyl Aminosulfonylamino group, etc.), alkyl and arylsulfonylamino groups (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, etc., For example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, etc.), mercapto group, alkylthio group (preferably having 1 to 1 carbon atoms). 30 substituted or unsubstituted alkylthio groups, for example Methylthio group, ethylthio group, n-hexadecylthio group, etc., arylthio group (preferably substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio group, p-chlorophenylthio group, m-methoxyphenylthio group Etc.), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group, etc.),

Sulfamoyl group (preferably having a carbon number of 0 to
30 substituted or unsubstituted sulfamoyl groups, for example, N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group , N-benzoylsulfamoyl group, N- (N'-phenylcarbamoyl)
Sulfamoyl group, etc.), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl Group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group, etc., alkyl and arylsulfonyl groups (preferably having 1 carbon atom)
To 30 substituted or unsubstituted alkylsulfonyl groups, 6 to 30
A substituted or unsubstituted arylsulfonyl group and the like, for example, methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, p-methylphenylsulfonyl group, etc.),
An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and the like, for example, an acetyl group, a pivaloyl group, 2- Chloroacetyl group,
Stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, etc., aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl group, o-chlorophenoxy group Carbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group, etc.),

Alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group, etc.), carbamoyl Group (preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, a carbamoyl group, an N-methylcarbamoyl group,
N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group, etc., aryl and heterocyclic azo groups (preferably substituted or unsubstituted with 6 to 30 carbon atoms) Arylazo group, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, and the like, for example, a phenylazo group, a p-chlorophenylazo group,
5-ethylthio-1,3,4-thiadiazol-2-ylazo group, etc.), imide group (preferably N-succinimido group, N-phthalimido group, etc.), phosphino group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted phosphino groups, such as dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group, etc., phosphinyl group (preferably substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms) A phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, etc., a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, For example, diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group, etc., phosphinylamino group (preferably substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example dimethoxyphosphinyl group). Luamino group, dimethylaminophosphinylamino group, etc.), silyl group (preferably charcoal) A substituted or unsubstituted silyl group having 3 to 30, such as trimethylsilyl group, t- butyl dimethyl silyl group, and a phenyl dimethylsilyl group), and the like. n represents an integer of 0 to 5.

R ⁹ is a hydrogen atom, an alkyl group, an aryl group,
Or represents a heterocyclic group, the alkyl group, the aryl group,
And the heterocyclic group represent the same groups as the alkyl group, aryl group and heterocyclic group described for the group represented by R ⁸ .

R ¹⁰ is an aryl group whose sum of Hammett sigma values of the substituents on the aryl group is 0.3 or more, or 5
~ Represents a 7-membered heterocyclic group. When R ¹⁰ represents an aryl group, a sigmapara (σ _p ) value is adopted for a substituent at an ortho position, a para position, and an position corresponding to that electronically with respect to the nitrogen atom to which R ¹⁰ is bonded, With respect to the nitrogen atom to which R ¹⁰ is bonded, a sigma-meta (σ _m ) value is adopted for the substituents at the meta position and positions corresponding thereto, and the sum of the sigma values of the respective substituents is 0.3 or more. . In this specification, C. Hansch et al., “A Survey of Hammett Su
bstituent Constants and Resonance and Field Parame
ters ", (Chem. Rev. 1991, 91, pp165-195) is adopted. When R ¹⁰ represents a heterocyclic group,
It represents the same group as the heterocyclic group described for the group represented by R ⁸ .

L ¹ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent. The group capable of splitting off upon reaction with an oxidized product of a developing agent is a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group,
Alkoxycarbonyloxy group, carbamoyloxy group, sulfonyloxy group, carbonamido group, sulfonamide group, carbamoylamino group, nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom, arylazo group, alkylthio group, arylthio group Represents a heterocyclic thio group and the like. The preferred range and specific examples of the halogen atom and the removable group are the same as those mentioned in the description of the group represented by R ⁸ . The nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom is a 5- or 6-membered aromatic nitrogen-containing heterocyclic group having 3 to 30 carbon atoms, and for example, pyrazole.
-1-yl group, imidazol-1-yl group, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl or -2-
Examples thereof include an yl group, benzotriazol-1-yl or -2-yl group, and tetrazol-1-yl group. In addition to these, L ¹ may form a bis-type coupler in which two molecules of 4-equivalent couplers are bound via an aldehyde or a ketone, and L ¹ is a development accelerator, development inhibitor, desilvering accelerator, leuco It may be a photographically useful group such as a dye or a precursor thereof.

When the groups represented by R ⁸ , R ⁹ , R ¹⁰ and L ¹ are further substitutable groups, these groups may further have a substituent, and the preferable substituent in that case is It represents a group having the same meaning as the group described for R ⁸ . When substituted with two or more substituents, those substituents may be the same or different.

In the general formula (3), R ¹¹ represents a group having the same meaning as the group explained above for R ⁸ . k represents an integer of 0 to 3. Y ¹ represents a hydroxyl group or (EWG) ₂ CH-group, and EWG
Represents an electron-withdrawing group. EWG is preferably Hammett sigma para value (σ _p ) is a substituent of 0.3 or more, a heterocyclic group, a cyano group, a nitro group, a sulfamoyl group, an alkyl and arylsulfinyl group, an alkyl and arylsulfonyl group, an acyl group, Examples thereof include an aryloxycarbonyl group, an alkoxycarbonyl group, and a carbamoyl group. Preferable ranges and specific examples of these groups are the same as those mentioned in the description of the group represented by R ⁸ . The two EWG groups may be the same or different.

In the general formula (3), Z represents a non-metal atom group which is condensed with a benzene ring to form a 5- to 7-membered nitrogen-containing heterocyclic group, and L ² is a hydrogen atom or a reaction with an oxidized product of a developing agent. Represents a group capable of splitting off, and represents the same group as L ¹ in the general formula (2).

When R ¹¹ , the EWG group, and the group represented by L ² are further substitutable groups, these groups may further have a substituent, in which case a preferable substituent is R ⁸ . It represents the same group as the explained group. When substituted with two or more substituents, those substituents may be the same or different.

In the general formula (4), R ²¹ represents a substituent, which is the same as the group described above for R ⁸ . m is 0 to 2
Represents the integer. R ²² and R ²³ represent a hydrogen atom or a substituent, and the substituent represented by R ²² and R ²³ represents the same group as the group described for R ⁸ . R ²² and R ²³ may combine to form a carbocycle. Y ² represents a (EWG) ₂ CH-group, and EWG represents a group having the same meaning as the EWG described in the general formula (3). L ³ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent, and represents a group having the same meaning as L ¹ in the general formula (2). When the group represented by R ²¹ , the EWG group, and L ³ is a further substitutable group, these groups may further have a substituent, and a preferable substituent in that case is described in R ⁸ . Represents the same group as the group. When substituted with two or more substituents, those substituents may be the same or different.

In the general formula (5), R ³¹ and R ³² represent an electron-withdrawing group, an aryl group or a heterocyclic group having a Hammett sigmapara value of 0.3 or more. When R ³¹ and / or R ³² represents an electron-withdrawing group having a Hammett sigmapara value of 0.3 or more, R ³¹ and / or R ³² is preferably a cyano group, a nitro group, a sulfamoyl group, an alkyl and arylsulfinyl group, It represents an alkyl and aryl sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group, and the preferred range and specific examples of these groups are the same as those mentioned in the description of the group represented by R ^8. is there. The aryl group or heterocyclic group represented by R ³¹ and / or R ³² represents the same group as the aryl group and heterocyclic group described for the group represented by R ⁸ .

R³³Represents a hydrogen atom or a substituent, R³³Table
The substituents are the above-mentioned R⁸The same groups described in
You Q is a nitrogen atom or -C (R³⁴) = Represents. R³⁴Is a hydrogen atom
Or represents a substituent, R³⁴The substituent represented by⁸
Represents the same group as described in. L ^FourIs hydrogen atom or developer
Represents a group capable of splitting off upon reaction with a drug oxidant, represented by the general formula
L in (2)¹Represents a group having the same meaning as. R³¹, R³²,
R³³, R³⁴, And L^FourThe group represented by is a further substitutable group
When these groups are present, these groups may further have a substituent,
Preferred substituents in some cases are R⁸The same groups described in
You If substituted with two or more substituents, it
These substituents may be the same or different.

In the general formula (6), R ⁴¹ represents a substituent, which is the same as the group described above for R ⁸ . p is 0-5
Represents the integer. R ⁴² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R ⁴³ represents a hydrogen atom, an acyl group, an alkyl group, an aryl group, or a heterocyclic group,
R ⁴⁴ is an alkylsulfonyl group, an arylsulfonyl group,
It represents an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, or a carbamoyl group. The preferred range and specific examples of these groups are the same as those mentioned in the description of the group represented by R ⁸ . L ⁵ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent, and represents the same group as L ¹ in the general formula (2). When the group represented by R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , and L ⁵ is a further substitutable group, these groups may further have a substituent, and a preferable substituent in that case Represents the same group as described for R ⁸ . When substituted with two or more substituents, those substituents may be the same or different.

Next, the preferred range of the compounds represented by formulas (2) to (6) will be described. In the general formula (2), R ⁸ is a halogen atom, a cyano group, a nitro group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group,
Sulfamoylamino group, alkyl and arylsulfonylamino group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, and phosphinyl An amino group is preferable, and a cyano group, an acylamino group, an alkyl and arylsulfonylamino group, a sulfamoyl group, an alkyl and arylsulfinyl group, an alkyl and arylsulfonyl group, and a phosphinoylamino group are more preferable. R ⁸ is a cyano group, a sulfamoyl group at the 6-position and / or the 7-position of the naphthol ring,
When it has an alkylarylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, or an arylsulfonyl group, it has an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, or phosphinoyl at the 5-position and / or 8-position of the naphthol ring. It is particularly preferable to have an amino group.

In formula (2), R ⁹ is preferably a hydrogen atom or an alkyl group, and most preferably a hydrogen atom. R ¹⁰
Is a halogen atom as a substituent, an alkyl group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an aminocarbonylamino group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkyl A phenyl group or naphthyl group having at least one group selected from a sulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and an imide group, and the sum of the sigma values of those substituents is 0.3 or more. Group, and preferably a heterocyclic group, a phenyl group or naphthyl group whose sum of sigma values of the substituents is 0.5 or more, a thiazole ring which may have a substituent, and a substituent which may have a substituent. Being a benzothiazole ring Preferred. Specific preferred examples of the group represented by R ¹⁰ are shown below, but the present invention is not limited thereto.

[0129]

[Chemical 40]

[0130]

[Chemical 41]

[0131]

[Chemical 42]

In the general formula (2), L ¹ is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy group, a carbamoyloxy group, an alkylthio group, an arylthio group, and A heterocyclic thio group is preferable, a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group,
An alkoxycarbonyloxy group and a carbamoyloxy group are more preferable.

In the general formula (3), R ¹¹ is a halogen atom, cyano group, nitro group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or aryl. A sulfonylamino group, a sulfamoyl group, an alkyl and arylsulfinyl group, an alkyl and arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, and a phosphinylamino group are preferable, and an ortho of Y ¹ is used. It is particularly preferable to have a cyano group, a sulfamoyl group, or a carbamoyl group at the position. Y ¹ is a hydroxyl group, and EWG is a cyano group, a nitro group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group (EW
G) ₂ CH- groups are preferred. The nitrogen-containing hetero ring formed by the condensation of Z with the benzene ring is preferably a 6-membered ring, and particularly preferably the case of forming a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring. L ² is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy group, a carbamoyloxy group, an alkylthio group, an arylthio group, and a heterocyclic thio group, and a hydrogen atom, A halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyloxy group, and a carbamoyloxy group are more preferable.

In the general formula (4), R ²¹ , R ²² and R ²³ are a halogen atom, a cyano group, a nitro group, an acylamino group,
Aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl Groups, alkoxycarbonyl groups, carbamoyl groups, imide groups, and phosphinylamino groups are preferred. R ²¹ is particularly preferably a cyano group, a sulfamoyl group, or a carbamoyl group positioned at the ortho position of Y ² . It is preferable that R ²² and R ²³ bond together to form a naphthalene ring together with the benzene ring having Y ² . Y ² is a hydroxyl group, or EWG is a cyano group, a nitro group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group (EWG) ₂ CH- group preferable. L ³ is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy group, a carbamoyloxy group, an alkylthio group, an arylthio group, and a heterocyclic thio group, and a hydrogen atom, A halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyloxy group, and a carbamoyloxy group are more preferable.

In formula (5), R ³¹ and R ³² are preferably an aryl group, a heterocyclic group, a cyano group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group and a carbamoyl group, An aryl group, a cyano group, an alkoxycarbonyl group, and a carbamoyl group are more preferable. R ³³ is an alkyl group, aryl group, heterocyclic group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group , A heterocyclic thio group, and a phosphinylamino group are preferable, and an amino group (including anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, and an alkylthio group. Is more preferable. Q is preferably a nitrogen atom, and —C (R ³⁴ ) = where R ³⁴ is an acyl group, an alkoxycarbonyl group, or a carbamoyl group. L ⁴ is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy group,
A carbamoyloxy group, an alkylthio group, an arylthio group, and a heterocyclic thio group are preferable, and a hydrogen atom and a halogen atom are more preferable.

In the general formula (6), R ⁴¹ is a halogen atom, cyano group, nitro group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or aryl. A sulfonylamino group, a sulfamoyl group, an alkyl and arylsulfinyl group, an alkyl and aryl sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, and a phosphinylamino group are preferable, and a cyano group and an acylamino group. More preferred are groups, alkyl and arylsulfonylamino groups, sulfamoyl groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, and phosphinoylamino groups. When R ⁴¹ has a cyano group, a sulfamoyl group, an alkylarylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, or an arylsulfonyl group at the 6-position and / or the 7-position of the naphthol ring, the 5-position of the naphthol ring and / or Or at the 8-position, an acylamino group,
It is particularly preferable to have an alkylsulfonylamino group, an arylsulfonylamino group, or a phosphinoylamino group. R ⁴² is preferably a hydrogen atom. R ⁴³ is preferably a hydrogen atom or an acyl group. R ⁴⁴ is preferably an acyl group, an alkoxycarbonyl group, and a carbamoyl group. R ⁴³ and R ⁴⁴
It is also preferable that these combine to form an imide ring. L ⁵ is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy group, a carbamoyloxy group, an alkylthio group, an arylthio group, and a heterocyclic thio group, and a hydrogen atom and a A halogen atom is more preferred.

The compounds represented by the general formulas (2) to (6) are described in JP-A Nos. 53-129036, 55-21094 and 55-21095.
No. 61-86752, No. 63-88551, JP 2000-26465,
2000-38388, 2000-44564, 2000-310841,
It can be synthesized by the method described in 2000-310842, 2000-330245, 2000-229970 and the like.

The compounds represented by the general formulas (2) to (6) used in the present invention are added to any layer on the same surface of the support as the photosensitive silver halide and the reducible silver salt. Although it may be added, it is preferably added to a layer containing silver halide or a layer adjacent thereto. General formula (2) used in the present invention
The addition amount of the compound represented by (6) is based on 1 mol of silver.
0.2 to 200 mmol is preferable, more preferably 0.3 to 100
Mmol, and more preferably 0.5 to 30 mmol. The coupler compounds may be used alone or in combination of two or more.

Specific examples of the compounds represented by the general formulas (2) to (6) of the present invention are shown below, but the present invention is not limited thereto.

[0140]

[Chemical 43]

[0141]

[Chemical 44]

[0142]

[Chemical formula 45]

[0143]

[Chemical formula 46]

[0144]

[Chemical 47]

[0145]

[Chemical 48]

[0146]

[Chemical 49]

[0147]

[Chemical 50]

[0148]

[Chemical 51]

[0149]

[Chemical 52]

[0150]

[Chemical 53]

[0151]

[Chemical 54]

[0152]

[Chemical 55]

[0153]

[Chemical 56]

[0154]

[Chemical 57]

[0155]

[Chemical 58]

[0156]

[Chemical 59]

[0157]

[Chemical 60]

[0158]

[Chemical formula 61]

[0159]

[Chemical formula 62]

Further, the following functional couplers may be used in the present invention. Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB2,125,570 and EP.
Those described in 96,873B and DE 3,234,533 are preferable. EP as a coupler to correct unwanted absorption of color forming dyes
No. 456,257A1 yellow-colored cyan coupler, EP EP yellow-colored magenta coupler, US Pat. No. 4,833,069 magenta-colored cyan coupler, US Pat. A colorless masking coupler represented by formula (A) in claim 1 of the above (in particular, the exemplified compounds on pages 36 to 45). Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: Formula described on page 11 of EP378,236A1
Compounds represented by (I) to (IV), EP436, 938A2 No. 7
Compound represented by formula (I) described on page, compound represented by formula (1) of EP 568,037A, formula (I), (II), (III) described on pages 5 to 6 of EP 440,195A2 The compound represented. Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ') on page 5 of EP 310,125A2 and compounds represented by formula (I) in claim 1 of JP-A-6-59411. Ligand releasing compound: US 4,555,478
A compound represented by LIG-X according to claim 1. Leuco dye releasing compounds: compounds 1 to 6 in columns 3 to 8 of US 4,749,641; fluorescent dye releasing compounds: compounds represented by COUP-DYE in claim 1 of US 4,774,181. Development accelerator or fogging agent releasing compound: Formula (1) of column 3, US Pat. No. 4,656,123,
Compounds represented by (2) and (3) and EP 450, 637 A2 page 75 36
ExZK-2 on the 38th line. Compounds that release a dye group only after being released: a compound represented by the formula (I) of claim 1 of US Pat. No. 4,857,447; a compound represented by the formula (1) of Japanese Patent Application No. 4-134523; ~ Formula (I) (II) described on page 6
Compound represented by formula (III), compound represented by formula (I) in claim 1 of Japanese Patent Application No. 4-325564-ligand releasing compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 Compound. It is preferred to use such a functional coupler in an amount of 0.05 to 10 times, preferably 0.1 to 5 times the molar amount of the coupler contributing to color development described above.

The melting point of the coupler used in the present invention is preferably 90 ° C. or higher. The melting point of the coupler used in the present invention is preferably higher than that of the above-mentioned thermal solvent, and more preferably higher than the development processing temperature. The combination of the coupler and hot solvent used in the present invention is preferably compatible.

(D) Hot solvent The "hot solvent" used in the present invention is a solid at ambient temperature, but shows a mixed melting point together with other components at the heat treatment temperature used or lower. It is an organic material having a function of liquefying during thermal development and promoting thermal development and thermal transfer of dyes. As the thermal solvent, a compound that can be a solvent for a developing agent, a compound having a high dielectric constant that promotes physical development of a silver salt, a compound that is compatible with a binder and has a function of swelling the binder, and the like are useful. Examples of the thermal solvent used in the present invention include U.S. Pat. Nos. 3,347,675 and 3,
667, 959, 3,438,776, 3,666,477, Research Disclosure No. 17,643, JP-A-51-19
No. 525, No. 53-24829, No. 53-60223, No. 58-118640,
58-198038, 59-229556, 59-68730, 59-8
No. 4236, No. 60-191251, No. 60-232547, No. 60-14241
No. 61, No. 61-52643, No. 62-78554, No. 62-42153, No. 62
-44737, 63-53548, 63-161446, JP 1-224
751, No. 2-863, No. 2-120739, No. 2-123354 and the like. Specifically, urea derivatives (phenylmethylurea, etc.), amide derivatives (acetamide,
Stearyl amide, p-toluamide, p-propanoyloxyethoxybenzamide, etc.), sulfonamide derivative (p-toluenesulfonamide, etc.), polyhydric alcohols (high molecular weight polyethylene glycol, etc.), etc. A material having low property can be selected and used.

[0163] water-soluble hot solvent, in order to increase the dispersion stability of the microcrystalline dispersion, is preferably 1 g / m ³ or less, more preferably 10 ^-3 g / m ³ or less. Also,
The melting point of the thermal solvent used in the present invention is preferably 90 ° C. or higher and lower than the development processing temperature. The amount of the hot solvent used is preferably 1 to 200% by mass and more preferably 5 to 50% by mass based on the amount of the binder applied. Specific examples and melting points of typical hot solvents that can be used in the present invention are shown below, but the present invention is not limited to these specific examples.

[0164]

[Chemical formula 63]

[0165]

[Chemical 64]

[0166]

[Chemical 65]

(E) Additive It is also preferable to add to the present invention a heterocyclic compound described in European Patent Publication No. 1016902 and having ClogP sufficient to improve sensitivity. In addition, JP-A-20
ClogP value described in 01-051383 is 4.75 to 9.0 triazole compounds, Clo described in JP-A-2001-051384
Purine compounds having a gP value of 2 or more and less than 7.2, JP-A-2001-05
A mercapto-1,2,4-thiadiazole or mercapto-1,2,4-oxadiazole-based compound having a ClogP value of 1 or more and less than 7.6 described in 1385, and a ClogP value described in JP-A No. 2001-051386. It is also preferable to add a tetrazole compound having a ratio of 2 or more and less than 7.8. These compounds may be added to the light-sensitive material as fine oil droplets dissolved in a high-boiling organic solvent in the same manner as other oil-soluble compounds such as color developing agents and couplers, or may be dissolved in a water-miscible solvent. May be added to the binder. Further, silver salts of these compounds may be prepared in advance and added to the light-sensitive material. In that case, a solid dispersion may be added to the light-sensitive material in addition to the above addition method. Examples of the above compound include compound X described in EP-A-1016902.

[0168]

[Chemical formula 66] Compound X described in EP-A-1016902

The addition amount of these compounds can be adjusted in a wide range to obtain the desired performance, but is on the order of about 1 × 10 ^-5 to 1 mol per mol of the silver halide emulsion. The preferred addition amount is on the order of 10 ^-3 to 10 ^-1 mol with respect to silver halide when the compound of the present invention is used in a free form or an alkali metal salt, and 10 ^-2 to 1 mol when used as a silver salt. The order of is preferable.

(F) Silver Halide Silver halide used in the photothermographic material of the invention is silver iodobromide, silver bromide, silver chlorobromide, silver iodochloride, silver chloride, or iodochlorobromide. Any of silver may be used. The size of silver halide grains is 0.1 to 2 μm, especially 0.2 in terms of the diameter of a sphere of the same volume.
˜1.5 μm is preferred. Besides being used as the above-mentioned photosensitive silver halide grains, they can be used as non-photosensitive silver halide grains because they are not chemically sensitized. The silver halide grains may have a cubic crystal shape, an octahedral shape, a tetradecahedral shape, or other normal crystal shape, or a hexagonal or rectangular tabular shape. The tabular grains have an aspect ratio, which is a value obtained by dividing the grain projected diameter by the grain thickness, of preferably 2 or more, more preferably 8 or more, still more preferably 20 or more. Such tabular grains have a projected area of 50
%, Preferably 80% or more, and more preferably 90% or more is preferably used. The thickness of these tabular grains is preferably 0.3 μm or less, more preferably 0.2 μm or less, and most preferably 0.1 μm or less.

Further, US Pat. Nos. 5,494,789 and 5,50
Particles having a particle thickness of less than 0.07 μm and a high aspect ratio described in 3,970, 5,503,971, 5,536,632 and the like can also be preferably used. Also, U.S. Pat. Nos. 4,400,463, 4,713,323,
High silver chloride tabular grains having a (111) plane as a main plane, as described in 5,217,858, and US Pat. No. 5,26.
High silver chloride tabular grains having a (100) plane as a main plane described in 4,337, 5,292,632, 5,310,635 and the like can also be preferably used. Examples of actually using these silver halide grains are disclosed in JP-A-9-274295 and JP-A-9-3190.
No. 47, No. 10-115888, No. 10-221827, etc. The silver halide grains are preferably so-called monodisperse grains having a uniform grain size distribution. The standard of monodispersity is
The coefficient of variation obtained by dividing the standard deviation of the particle size distribution by the average particle size is preferably 25% or less, more preferably 20% or less.
It is also preferable that the halogen composition is uniform among the grains. The silver halide grains used in the present invention may have a uniform halogen composition in the grain or may intentionally introduce sites having different halogen compositions. In order to obtain a particularly high sensitivity, a core and a shell with different halogen compositions are used.
Particles having a laminated structure consisting of are preferably used.
It is also preferable to intentionally introduce dislocation lines by further growing grains after introducing regions having different halogen compositions. Furthermore, it is also preferable to epitaxially bond guest crystals having different halogen compositions to the apexes or edges of the formed host particles.

It is also preferable that the inside of the silver halide grain is doped with a polyvalent transition metal ion or a polyvalent anion as an impurity. Particularly in the former case, a halogeno complex having an iron group element as a central metal, a cyano complex, an organic ligand complex and the like are preferably used.

The silver halide grains can be prepared by a known method, namely, "Graphide's Physics and Chemistry" by Graphide, published by Paul Monte (P. Glafkides, Chimie et Phisique).
Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duff)
in, Photographic Emulsion Chemistry, Focal Pres
s, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (Vl. Zelikman et a.
l. , Making and Coating of Photographic Emuls
Ion, Focal Press, 1964) and the like can be basically used. That is, it can be prepared in various pH ranges such as an acidic method, a neutral method, an ammonia method and the like. As a method for supplying the reaction solution containing a water-soluble silver salt and a water-soluble halogen salt solution, a one-side mixing method, a simultaneous mixing method, or the like can be used alone or in combination. Furthermore, it is also preferable to use a controlled double jet method in which the addition of the reaction solution is controlled so as to keep pAg during the reaction at a target value. A method of keeping the pH value constant during the reaction is also used. Upon grain formation, a method of controlling the solubility of silver halide by changing the temperature, pH or pAg value of the system can be used, but thioethers, thioureas, rhodan salts and the like can also be used as a solvent. Examples of these are
And JP-A-53-144319.

The silver halide grains are usually prepared by controlling a water-soluble silver salt solution such as silver nitrate and a water-soluble halogen salt solution such as alkali halide in an aqueous solution of a water-soluble binder such as gelatin under controlled conditions. It is done by supplying.
After forming the silver halide grains, it is preferable to remove excess water-soluble salts. For example, after gelatinizing a gelatin solution containing silver halide grains, cutting it into a string and washing the water-soluble salt with cold water, a Nudel water washing method, inorganic salts consisting of polyvalent anions (eg sodium sulfate), anionic interfaces Activator, anionic polymer (eg sodium polystyrene sulfonate), gelatin derivative (aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) are added to agglomerate gelatin to remove excess salts. You may use the sedimentation method. The precipitation method is preferable because excess salts are rapidly removed.

(G) Chemical sensitization, spectral sensitization The emulsion used in the present invention is usually chemically and spectrally sensitized.
Preferably. Chemical sensitization can be sulfur, selenium or tellurium.
Chalcogen sensitization method using gold compounds, gold, platinum, iridis
Suitable for noble metal sensitization using um, etc., or during grain formation
A reducing silver nucleus is introduced by using a compound having a moderate reducing property.
The so-called reduction sensitization method that obtains high sensitivity by
Or various combinations can be used. Spectroscopy
Sensitization is the absorption of silver halide grains and their own absorption.
Cyanine dye, merocyanine, which has sensitivity in the wavelength range
Dyes, complex cyanine dyes, complex merocyanine dyes, holo
Polar dye, hemicyanine dye, styryl dye, hemi
A so-called spectral sensitizing dye such as an oxonol dye is used alone.
Rui can be used together. Also with a supersensitizer
It is also preferable to use. Photosensitive silver halide is converted to silver
0.05 to 15g / m in total², Preferably 0.1-8 g / m²To use.
A silver halide emulsion prevents fog and is safe during storage.
Nitrogen-containing heterocyclic compounds (azaindene)
, Triazoles, tetrazoles, purines
Etc.), mercapto compounds (mercaptotetrazole
, Mercaptotriazoles, mercaptoimidazo
Various kinds of melamine, mercaptothiadiazoles, etc.)
It is preferable to add an agent. Especially included in the compound
Having an alkyl group having 5 or more carbon atoms or an aromatic ring as a substituent.
Triazoles or mercaptoazoles
Prevents fogging during image formation, and in some cases improves the developability of the exposed area
Outstanding to give high and high discrimination
Exert an effect. Specifically, US Pat. No. 5,773,560,
Hydrophobic devices described in JP-A Nos. 11-109539 and 11-119397.
An antifoggant substituted with a substituent can be used.
Add these antifoggants or stabilizers to silver halide emulsions
May be added at any time during emulsion preparation. Chemical sensitization
After finishing, when preparing the coating solution, at the end of chemical sensitization, during chemical sensitization,
Before chemical sensitization, after completion of grain formation, before desalting, during grain formation, grains
Various methods such as addition prior to formation, individually or
It can be used in combination. In addition, JP 2000-894
Combination use with the divalent metal ion described in No. 09 is also preferable. Turnip
The anti-reflective agent is a photosensitive silver halide and a reducing agent on the support.
It can be added to any layer as long as it is on the same surface as the active silver salt.
However, a layer containing a reducible silver salt or a layer adjacent to it
It is preferable to add. Antifoggant is water or suitable
It can be used by dissolving it in various organic solvents. Or already
Prepare an emulsified dispersion according to the well-known emulsified dispersion method
Can be used. Or well known
According to the microcrystalline particle dispersion method, water the antifoggant powder with water.
It can be dispersed and used in. Anti-fog
The amount of stopper or stabilizer added should be the same as that of the silver halide emulsion.
Depending on the gen composition and purpose, silver halide
Preferably about 10 per mole ^-6~Ten^-1Mol, more preferred
Kuha 10^-Five~Ten^-2It is in the molar range.

The photographic additives used in the photothermographic material described above are those described in Research Disclosure (hereinafter abbreviated as RD) No17643 (December 1978) and No18716.
(November 1979), No. 307105 (November 1989) and No. 38
The materials described in No. 957 (September 1996) can be preferably used, and the relevant parts are summarized below.

[0177] Types of additives RD17643 RD18716 RD307105 Chemical sensitizer page 23 page 648 right column page 866 Sensitivity enhancer page 648, right column Spectral sensitizer page 23-24 page 648 right column page 866-868 Supersensitizer: page 649, right column Brightener page 24 page 648 right column page 868 Antifoggant page 24 to 26 page 649 right column 868 to 870 Stabilizer Light absorber page 25-26 page 649 right column page 873 Filter dye ~ 650 page left column UV absorber Dye image stabilizer page 25 page 650 page left column page 872 Hardener 26 pages 651 pages left column 874-875 pages Binder page 26 page 651 left column page 873-874 Plasticizers and lubricants Page 27 Page 650 Right column Page 876 Coating aid page 26-27 page 650 right column 875-876 page       Surfactant Antistatic agent Page 27 Page 650 Right column Page 876-877 Matting agent pp. 878-879

(H) Reducible Silver Salt The reducible silver salt that can be used in the present invention is relatively stable to light and exposed to a photocatalyst (such as a latent image of a photosensitive silver halide). And supplying silver ions when heated to 80 ° C. or higher in the presence of a reducing agent.
Such a silver salt has a gross stability constant of 4.0 for the silver ion of the ligand.
Complexes of organic or inorganic silver salts having complex stability constants in the range of -10.0 are preferred. As the organic silver salt, a silver salt of an organic compound having a carboxyl group such as a silver salt of an aliphatic carboxylic acid or a silver salt of an aromatic carboxylic acid can be preferably used.
A silver salt which can be substituted with a halogen atom or a hydroxyl group can also be effectively used. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, and silver tartrate. , Silver furoate, silver linoleate, silver butyrate, silver camphorate, and mixtures thereof. Preferable examples of silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver benzoate, substituted silver benzoates (eg, silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, m-methylbenzoic acid). Silver, silver p-methylbenzoate, silver 2,4-dichlorobenzoate,
Acetamide silver benzoate, silver p-phenylbenzoate,
Etc.), silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitic acid, 3-carboxymethyl-4-methyl-4-thiazoline-2.
-Thion silver salts, those described in U.S. Pat. No. 3,785,830, and thioether group-containing aliphatic carboxylic acid silver salts described in U.S. Pat. No. 3,330,663. A heterocyclic skeleton containing 5 or 6 ring atoms, at least one of which is nitrogen, and the other ring atoms containing up to 2 heteroatoms selected from oxygen, sulfur and nitrogen and carbon. A silver salt of a mercapto- or thione-substituted compound having a can be also preferably used. Typical preferable examples of the heterocyclic ring skeleton are a triazole ring skeleton, an oxazole ring skeleton, a thiazole ring skeleton, a thiazoline ring skeleton, a thiazole ring skeleton, an imidazoline ring skeleton, an imidazole ring skeleton, a diazole ring skeleton, a pyridine ring skeleton, and a triazine ring. There is a skeleton. Specific preferred examples of these heterocyclic skeletons include 3-mercapto-4-phenyl-1,2,4-
Silver salt of triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2- (2-ethyl-glycolamido) benzothiazole, 5-carboxyl-1-methyl- 2-Phenyl-4-thiopyridine silver salt, mercaptotriazine silver salt, 2-mercaptobenzoxazole silver salt, 1-mercapto-5-
Alkyl-substituted tetrazole silver salt, 1-mercapto-5-phenyltetrazole silver salt described in JP-A 1-100177,
Silver salts described in U.S. Pat.No. 4,123,274 (e.g., 1,2-, 3-amino-5-benzylthio-1,2,4-triazole silver salts, etc.
Silver salt of 4-mercaptothiazole derivative), US Pat.
3- (2-carboxyethyl) -described in No. 201,678
Silver salts of thione compounds such as silver salts of 4-methyl-4-thiazoline-2-thione, 3-amino-1,2,4-described in JP-A-53-116144
Silver salt of triazoles, silver salt of substituted or unsubstituted benzotriazoles, U.S. Pat. No. 4,500,626 Nos. 52 to 53
Examples thereof include benzotriazoles described in the column and the like, silver salts of fatty acids and the like. In addition, as a preferable example of a mercapto- or thione-substituted compound containing no heterocyclic skeleton, Japanese Patent Application No.
No. 48-28221, a silver salt of thioglycolic acid such as a silver salt of S-alkylthioglycolic acid (wherein the alkyl group contains 12 to 22 carbon atoms), a dithiocarboxylic acid such as a silver salt of dithioacetic acid. Examples thereof include silver salts of acids and silver salts of thioamides. Further, a silver salt of a compound containing an imino group can be used. As preferable examples of these compounds,
There are silver salts of benzothiazole and derivatives thereof described in Japanese Patent Application Nos. 44-30270 and 45-18146, and specifically, silver salts of benzotriazole such as silver salts of methylbenzotriazole and 5-chlorobenzo. Halogen-substituted benzotriazole silver salts such as triazole silver salts, 1,2,4-triazole silver salts, 1H-tetrazole silver salts described in U.S. Pat.No. 4,220,709, imidazole and imidazole derivative silver salts, and the like. To be The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is preferably 0.01 to 10 mol, and more preferably 0.1 mol, per mol of the photosensitive silver halide.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide emulsion and the organic silver salt is preferably 0 in terms of silver.
It is 1 to ²⁰ g / m ² , and more preferably 1 to 10 g / m ² . The silver-providing substance preferably constitutes about 5 to 70% by weight of the image forming layer.

The above organic silver salt is a solution or suspension of the above organic compound or its alkali metal salt (such as Na salt, K salt, Li salt, etc.) in a sealing means for mixing liquids. It is prepared by reacting silver nitrate. Specifically, the methods described in paragraphs 19 to 21 of Japanese Patent Application No. 11-203413 and Japanese Patent Application No. 11-104187 can be used. Also,
A method of simultaneously adding the solution of the organic compound and the silver nitrate solution to the solution of the dispersant may be used. When preparing the organic silver salt,
A water-soluble dispersant can be added to the silver nitrate aqueous solution and the organic compound, the alkali metal salt solution thereof, or the reaction solution. Specific examples of the type and amount of the dispersant used here are described in paragraph No. 52 of Japanese Patent Application No. 11-115457. As a method for forming a silver salt of an organic compound, a method described in JP-A No. 1-100177 and prepared while controlling pH can be preferably used.

The organic silver salt is preferably desalted. The desalting method is not particularly limited, and known methods can be used, including centrifugal filtration, suction filtration, ultrafiltration,
Well-known filtration methods such as floc formation washing with a flocculation method can be preferably used. As the ultrafiltration method, the method described in Japanese Patent Application No. 11-115457 can be used. For the purpose of obtaining a solid dispersion of an organic silver salt having a small particle size and no aggregation, it is preferable to use a dispersion method in which an aqueous dispersion of an organic silver salt is converted into a high-speed flow and then pressure is reduced. These dispersion methods are described in Japanese Patent Application No. 11-104187, paragraph number 2.
The method described in 7 to 38 can be used.

The shape and size of the organic silver salt that can be used in the present invention are not particularly limited, but a solid fine particle dispersion having an average particle size of 0.001 to 5.0 μm is preferable. A more preferable average particle size is 0.005 to 1.0 μm.

The particle size distribution of the organic silver salt solid fine particle dispersion used in the present invention is preferably monodisperse. Specifically, the percentage (variation coefficient) of the value obtained by dividing the standard deviation of the volume-loaded average diameter by the volume-loaded average diameter is 80% or less, more preferably 50% or less, and further preferably 30% or less.
The organic silver salt solid fine particle dispersion used in the present invention comprises at least an organic silver salt and water. The proportion of the organic silver salt and water is not particularly limited, but the proportion of the organic silver salt in the whole is preferably 5 to 50% by mass, and particularly preferably 10 to 30% by mass. It is preferable to use the above-mentioned dispersion aid, but it is preferable to use the minimum amount within a range suitable for minimizing the particle size, and 0.5 to 30% by mass, particularly 1 to 15% by mass based on the organic silver salt. Is preferred.

In the present invention, a metal ion selected from Ca, Mg and Zn may be added to the non-photosensitive organic silver salt in order to prevent fogging.

The photosensitive silver halide and // in the present invention
Alternatively, reducible silver salts may be further protected against the formation of additional fog by known antifoggants, stabilizers and precursors thereof, and may be stabilized against reduced sensitivity during inventory storage. it can. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are the thiazonium salts described in U.S. Pat.Nos. 2,131,038 and 2,694,716, U.S. Pat. Azaindene described in U.S. Pat. No. 2,444,605 and U.S. Pat.
Mercury salts described in 28,663, urazole described in US Pat. No. 3,287,135, sulfocatechol described in US Pat. No. 3,235,652, oximes described in British Patent No. U.S. Pat.No. 2,839,
405 polyvalent metal salts described, U.S. Pat.No. 3,220,839 thiuronium salts, and U.S. Pat.Nos. 2,566,263 and 2,597,915 palladium, platinum and gold salts, U.S. Pat. 4,442,202 halogen-substituted organic compounds, U.S. Pat. Nos. 4,128,557 and 4,137,079, 4,138,365 and 4,459,
Triazine described in US Pat. No. 4,411,9
Phosphorus compounds described in JP-A-85-119624 and JP-A-54-58
No. 022, No. 56-70543, No. 56-99335, No. 61-129642,
62-129845, JP-A-6-208191, 7-5621, 8-1
The organic halides disclosed in 5809, US Pat. Nos. 5,340,712, 5,369,000, and 5,464,737 are mentioned.

The photothermographic material of the invention may contain a reducing agent in addition to the color developing agent. In addition to conventional photographic developers such as phenidone, hydroquinone and catechol, hindered phenol reducing agents can be mentioned as preferable examples. The reducing agent is preferably contained in an amount of 5 to 50 mol%, and more preferably 10 to 40 mol% based on 1 mol of silver on the surface having the image forming layer. The reducing agent-containing layer may be any layer on the image forming layer side of the support. When it is added to layers other than the image forming layer, it is preferable to use a large amount of 10 to 50 mol% relative to 1 mol of silver. Further, the reducing agent may be a so-called precursor designed to have an effective function only during development.

A wide range of reducing agents can be used in the photothermographic material utilizing an organic silver salt. For example,
JP-A-46-6074, 47-1238, 47-33621, 49-4
6427, 49-115540, 50-14334, 50-36110
No. 50, No. 50-147711, No. 51-32632, No. 51-1023721,
51-32324, 51-51933, 52-84727, 55-108
No. 654, No. 56-146133, No. 57-82828, No. 57-82829,
JP-A-6-3793, U.S. Pat.Nos. 3,667,9586, and 3,679,
No. 426, No. 3,751,252, No. 3,751,255, No. 3,76
1,270, 3,782,949, 3,839,048, 3,9
28,686, 5,464,738, German Patent 2,321,328,
The reducing agents disclosed in European Patent Publication No. 692,732 and the like can be used.

(I) Precursor Generally, a base is required for processing a photographic light-sensitive material, but a base is not necessarily required for the light-sensitive material of the present invention. However, a base may be used for the purpose of accelerating the development, accelerating the reaction between the color developing agent and the coupler described below, accelerating the color development of the formed dye. In the light-sensitive material of the present invention, various base supply methods can be adopted. For example, when a base generating function is given to the photosensitive material side, it can be introduced into the photosensitive material as a base precursor. Examples of such base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. This example is described in U.S. Pat. Nos. 4,514,493 and 4,657,848.

The photographic material of the present invention may contain a nucleophile or a nucleophile precursor for the purpose of accelerating the reaction between the color developing agent and the coupler. Although various nucleophilic agent precursors are known, it is convenient to use a type of precursor that produces (or releases) a base upon heating, because the nucleophilic agent is released during thermal development. As a base precursor that produces a base by heating, a thermal decomposition type (decarboxylation type) base precursor composed of a salt of a carboxylic acid and a base is typical. When the decarboxylation type base precursor is heated, the carboxyl group of the carboxylic acid undergoes a decarboxylation reaction to release the base. As the carboxylic acid, sulfonylacetic acid or propiolic acid, which is easily decarboxylated, is used. Sulfonylacetic acid and propiolic acid preferably have a group having an aromatic property (aryl group or unsaturated heterocyclic group) that promotes decarboxylation as a substituent. The base precursor of sulfonylacetate is described in JP-A-59-168441, and the base precursor of propiolate salt is described in JP-A-59-180537. The base component of the decarboxylation type base precursor is preferably an organic base, more preferably amidine, guanidine or a derivative thereof. The organic base is preferably a diacid base, a triacid base or a tetraacid base, more preferably a diacid base, and most preferably a diacid base of an amidine derivative or a guanidine derivative.

The diacid base, triacid base or tetraacid base precursor of the amidine derivative is described in JP-B-7-59545. For diacid base, triacid base or tetraacid base precursor of guanidine derivative, see Japanese Patent Publication No. 8-1032.
There is a description in No. 1. The diacid base of an amidine derivative or a guanidine derivative is (A) two amidine moieties or a guanidine moiety, (B) a substituent of the amidine moiety or a guanidine moiety, and (C) a divalent base that bonds the two amidine moieties or the guanidine moiety. It consists of a linking group. Examples of the substituent of (B) include an alkyl group (including a cycloalkyl group), an alkenyl group, an alkynyl group, an aralkyl group and a heterocyclic residue. Two or more substituents may combine to form a nitrogen-containing heterocycle. The linking group of (C) is preferably an alkylene group or a phenylene group. Examples of diacid base precursors of amidine derivatives or guanidine derivatives preferably used in the present invention are described in JP-A No. 11-231457, page 19-
BP-1 to BP-41 described on page 26, especially BP-9,
P- (phenylsulfonyl) -phenylsulfonylacetic acid salts such as BP-32, BP-35, BP-40, BP-41 are preferred.

The amount (mol) of the base precursor used is preferably 0.1 to 10 times, more preferably 0.3 to 3 times the amount (mol) of the color developing agent used. The base precursor is preferably dispersed in the form of solid fine particles.

(J) Binder The photothermographic material of the present invention comprises a photosensitive layer, a coloring layer, a protective layer,
A binder is used for the non-photosensitive layer such as the intermediate layer. As the binder, a well-known natural or synthetic resin (for example, gelatin, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, cellulose acetate,
Any one can be selected from polyolefin, polyester, polystyrene, polyacrylonitrile, polycarbonate, ultrafiltration (UF) refined SBR latex, etc.). These also include copolymers and terpolymers. If necessary, these polymers can be used in combination of two or more kinds. Such polymers are used in an amount sufficient to hold the components therein. That is, it is used within a range effective to function as a binder. The effective range can be appropriately determined by those skilled in the art. The binder of the light-sensitive material is preferably hydrophilic, and examples thereof include Research Disclosure described in the preceding paragraph and 71 to 7 of JP-A-64-13,546.
Examples include those described on page 5. Among them, gelatin and the combination of gelatin with other water-soluble binders such as polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivative, acrylamide polymer and the like are preferable. The coating amount of the binder is appropriately 1 to 25 g / m ² , preferably 3 to 20 g / m ² , and more preferably 5 to 15 g / m ² . Among them, gelatin has a mass of 50 to 10
It is used at a rate of 0%, preferably 70 to 100%.

[II] Layer Structure of Photothermographic Material The photothermographic material of the invention is usually composed of three or more photosensitive layers having different color sensitivities. Each light-sensitive layer comprises at least one silver halide emulsion layer, but typically comprises a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. At this time, it is preferable to use a grain having a larger so-called aspect ratio, which is obtained by dividing the grain projected diameter by the grain thickness, as the silver halide grain having a larger grain projected diameter. The photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. Red-sensitive layer in order from the support side,
The green-sensitive layer and the blue-sensitive layer are installed in that order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. The total thickness of the photosensitive layers is generally 2 to 40 μm, preferably 5 to 25 μm.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, facing a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange so that the photosensitivity becomes lower sequentially. In addition, JP-A-57-112751, JP-A-62-200
As described in Nos. 350, 62-206541, and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH / GL /
It can be installed in order of RL / RH. See also Sho 55-
As described in 34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive layers / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more light sensitive than the middle layer. A silver halide emulsion layer having a low photosensitivity is arranged, and the photosensitivity is gradually decreased toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / It may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. Other, high sensitivity emulsion layer /
Low-speed emulsion layer / medium-speed emulsion layer or low-speed emulsion layer /
The medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, US 4,663,271
4,705,744, 4,707,436, JP-A-62-160448,
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL and RL described in JP-A-63-89850, adjacent to or in proximity to the main photosensitive layer.

In the present invention, the silver halide, the dye-donating coupler and the color developing agent (or the precursor thereof) may be contained in the same layer, but if they are in a reactive state, they are divided into separate layers. Can also be added. For example, when the layer containing a color developing agent and the layer containing silver halide are separate layers, the storability of the light-sensitive material can be improved. The relationship between the spectral sensitivity of each layer and the hue of the coupler is arbitrary, but if a cyan coupler is used for the red photosensitive layer, a magenta coupler is used for the green photosensitive layer, and a yellow coupler is used for the blue photosensitive layer, it will be directly applied to conventional color paper, etc. Projection exposure is possible. Further, the coupler forming the dye having the maximum wavelength in the non-visible region can be used in any photosensitive layer. In the image forming method of the present invention, after thermal development, while leaving the silver halide in the photosensitive material, there are cases where image information is read by a CCD or the like,
By using a coupler having the maximum wavelength in the infrared absorption region instead of the yellow coupler in the blue photosensitive layer, the influence of the remaining silver halide on the reading load is small,
Image information with good image quality can be obtained.

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 as the uppermost layer and the lowermost layer. On the opposite side of the support, various auxiliary layers such as a back layer can be provided. These may contain the above-mentioned coupler, developing agent, and DIR, color mixing inhibitor, dye or the like. Specifically, the layer constitution as described in the above patent, the undercoat layer as described in US Pat. No. 5,051,335, and the solid pigment as described in JP-A-1-167,838 and JP-A-61-20,943. An intermediate layer having: JP-A-1-120553,
5-34884, the intermediate layer having a reducing agent and DIR compound described in 2-64634, US Pat. No. 5,017,454, 5,139,919
No. 2, JP-A-2-235044, an intermediate layer having an electron transfer agent, a protective layer having a reducing agent described in JP-A-4-249245, or a layer combining these may be provided.

In the present invention, a yellow filter layer, a magenta filter layer, and an antihalation layer can be used as the colored layer. Thereby, for example, when the photosensitive layer is provided in the order of the red photosensitive layer, the green photosensitive layer and the blue photosensitive layer from the side closest to the support, a yellow filter layer and a green photosensitive layer are provided between the blue photosensitive layer and the green photosensitive layer. A magenta filter layer may be provided between the layer and the red photosensitive layer, and a cyan filter layer (antihalation layer) may be provided between the red photosensitive layer and the support. These colored layers may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer of gelatin or the like. Further, it may be arranged on the side opposite to the support with respect to the emulsion layer.
The amount of dye used is such that the transmission density of each layer is blue,
For green and red light, 0.03-3.0, more preferably 0.1-1.0
To be used. Specifically, 0.005 to 2.0 mmol / m ² may be used, and more preferably 0.05 to 1.0 mmol / m ² , though it depends on ε and the molecular weight of the dye.

In the present invention, it is preferable to use a colored layer using a dye that can be decolorized by treatment. The fact that the dyes in the yellow filter layer and antihalation layer are decolorized or removed during development means that the amount of the dye remaining after the treatment is 1/3 or less, preferably 1/10 or less, immediately before coating. In the light-sensitive material of the present invention, two or more dyes may be mixed and used in one colored layer. For example, it is also possible to mix and use three kinds of dyes of yellow, magenta and cyan in the above antihalation layer. Specifically, the dyes described in European Patent Application EP549,489A and ExF of JP-A-7-152129.
2 to 6 dyes can be mentioned. It is also possible to use a dye having fine crystalline particles dispersed therein, as described in Japanese Patent Application No. 6-259805. It is also possible to mordant the dye with a mordant and a binder. In this case, as the mordant and dye, those known in the photographic field can be used, and US Pat. No. 4,500,626, columns 58 to 59, JP-A-61-88256, pages 32-41, and JP-A-62-2
The mordants described in JP-A No. 44043 and JP-A No. 62-244036 can be used.

A leuco dye or the like which can be decolored can be used. Specifically, a silver halide light-sensitive material containing a leuco dye previously developed with a developer of an organic acid metal salt in JP-A-1-150132. Is disclosed. The leuco dye and the developer complex react with heat or an alkaline agent to lose the color. Known leuco dyes can be used, and Moriga and Yoshida “Dyes and Chemicals” 9, page 84 (Chemical Industry Association), “New Edition Dye Handbook” page 242 (Maruzen, 1970), R. Garner “Reports on t”
he Progress of Appl. Chem ”56, 199 pages (1971),“ Dyes and chemicals ”19, pages 230 (Chemical Industry Association, 1974),“ Coloring materials ”62, 288 pages (1989),“ Dyeing industry ”32 , 208, etc. As the developer, an acidic clay-based developer, a phenol formaldehyde resin, and a metal salt of an organic acid are preferably used. As the metal salt of an organic acid, a metal salt of salicylic acid, a metal salt of phenol-salicylic acid-formaldehyde resin, a rhodan salt, a metal salt of xanthate, and the like are useful, and zinc is particularly preferable as the metal. Among the above-described color developers, oil-soluble zinc salicylates are described in U.S. Patent Nos. 3,864,146, 4,046,941 and JP-B-52.
Those described in No. -1327 and the like can be used. Further, various additives shown below can be used in combination in the present invention.

It is also possible to use a dye that decolorizes during processing in the presence of a decolorizing agent. As the dye used, a cyclic ketomethylene compound described in JP-A Nos. 11-207027 and 2000-89414, a cyanine dye described in European Patent 911693A1, a polymethine dye described in U.S. Pat. The merocyanine dyes described in -112058 and the like can be mentioned.

It is preferable that these decolorizable dyes are dispersed in the above-mentioned fine crystal particles and added to the light-sensitive material. The decolorizable dye described above may be used in a state where oil droplets dissolved in oil and / or an oil-soluble polymer are dispersed in a hydrophilic binder. As its preparation method, an emulsion dispersion method is preferable,
For example, the method described in US Pat. No. 2,322,027 can be used. In this case, US Pat.
6,466, 4,587,206, 4,555,476, 4,599,296
The high boiling point oil as described in JP-B No. 3-62256 and the like can be used in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. High boiling oil is 2
One or more species can be used in combination. Further, an oil-soluble polymer can be used in place of or in combination with oil, examples of which are described in PCT International Publication No. WO88 / 00723. The amount of high-boiling oil and / or polymer is 0.01-10 g, preferably 0.1-5 g, per 1 g of dye used.
To use.

Further, as a method of dissolving the dye in the polymer, a latex dispersion method can be used, and a specific example of the step and the latex for dipping is described in US Pat.
No. 363, West German patent application (OLS) No. 2,541,274, No. 2,541,2
No. 30, JP-B No. 53-41091, European Patent Publication No. 029104, and the like. When dispersing the dye in the hydrophilic binder, various surfactants can be used. For example, JP-A-59-157636, pages 37 to 38, known technology No. 5 (199
Issued on March 22, 1st, Aztec Co., Ltd.) The surfactants described on pages 136-138 can be used. Also, Japanese Patent Application No. 5-
No. 204325, No. 6-19247 and West German Published Patent No. 932,29
The phosphate ester type surfactant described in No. 9A can also be used. A water-soluble polymer is preferable as the hydrophilic binder in which the dye is dispersed. Examples include gelatin, proteins of gelatin derivatives, or natural compounds such as cellulose derivatives, polysaccharides such as starch, gum arabic, dextran and pullulan, and synthetic polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone and acrylamide polymers. . These water-soluble polymers may be used in combination of two or more. A combination with gelatin is particularly preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and may be used in combination.

The above-mentioned dyes decolorize during processing in the presence of a decolorizing agent. Examples of the decolorizing agent include alcohols or phenols, amines or anilines, sulfinic acids or salts thereof, sulfurous acid or salts thereof, thiosulfuric acid or salts thereof, carboxylic acids or salts thereof, hydrazines, guanidines, aminoguanidines, amidines. Kind,
Examples thereof include thiols, cyclic or chain active methylene compounds, cyclic or chain active methine compounds, and anion species generated from these compounds. Among these, preferably used are hydroxyamines, sulfinic acids, sulfurous acid, guanidines, aminoguanidines, heterocyclic thiols, cyclic or chain active methylene, and active methine compounds, and particularly preferred is guanidine. Kind,
Aminoguanidines. The above-mentioned base precursor can also be preferably used. It is considered that the above-described decoloring agent makes the dye decoloring by coming into contact with the dye during processing and nucleophilically adding to the dye molecule. Preferably, a silver halide light-sensitive material containing a dye is heated after imagewise exposure or at the same time as imagewise exposure by superposing the film surfaces in the presence of a processing member containing a decoloring agent or a decoloring agent precursor and water. After that, the both are peeled off to obtain a color image on the silver halide light-sensitive material and to erase the dye. in this case,
The density of the dye after decolorization is 1/3 or less, preferably 1/5 or less of the original density. The amount of decolorizer used is 0.1
The amount is 2-fold to 200-fold mol, preferably 0.5-fold to 100-fold mol.
Also, a reversible decolorizable dye is used, which is colored at a temperature lower than the decolorization start temperature (T), but at a temperature of T or higher, at least a part of the color is decolored and its change is reversible. ,
A method of preventing deterioration of S / N at the time of reading due to the concentration of the dye by setting the temperature at the time of reading to be the decoloring temperature (T ° C.) or higher may be used. Such a reversible dye can be prepared by using a combination of a leuco dye, a phenolic developer and a higher alcohol described in JP-B-51-44706.

The light-sensitive material contains a hardener, a surface-active agent, a photographic stabilizer, an antistatic agent, a slip agent, a matting agent, for various purposes.
Lattex, formalin scavenger, dye, UV absorber and the like can be used. Specific examples of these are described in the above-mentioned Research Disclosure and Japanese Patent Application No. 8-30103. Incidentally, examples of particularly preferable antistatic agents are ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO and M.
It is a metal oxide fine particle such as oO ₃ and V ₂ O ₅ .

In the present invention, the support for the light-sensitive material is transparent and can withstand the processing temperature. Generally speaking, “Basics of Photographic Engineering-Silver Salt Photography” edited by The Photographic Society of Japan, published by Corona Publishing Co., Ltd. (1979) (22
Examples thereof include papers described on pages 3) to (240) and photographic supports such as synthetic polymers (films). Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) and the like. Among these, a polyester containing polyethylene naphthalate as a main component is particularly preferable, and the “polyethylene naphthalate containing as a main component” polyester referred to herein means the content of naphthalene dicarboxylic acid contained in all dicarboxylic acid residues. Is preferably 50 mol% or more. The content is more preferably 60 mol% or more, and further preferably 70 mol% or more. It may be a copolymer or a polymer blend.
In the case of copolymerization, in addition to the naphthalene dicarboxylic acid unit and the ethylene glycol unit, those obtained by copolymerizing a unit such as terephthalic acid, bisphenol A, cyclohexanedimethanol are also preferable. Among these, the copolymer of terephthalic acid unit is most preferable from the viewpoint of mechanical strength and cost. Polyethylene terephthalate (PET), polyarylate (PAr), polycarbonate (PC), polycyclohexanedimethanol terephthalate (PCT), and other polyesters are preferable partners for the polymer blend, but among them, mechanical strength is preferable. PE is preferable from the viewpoint of cost
It is a polymer blend with T. Especially when heat resistance and curl characteristics are strict requirements
6-41281, 6-43581, 6-51426, 6-51437,
6-51442, Japanese Patent Application No. 4-251845, 4-231825, 4-2
No. 53545, No. 4-258828, No. 4-240122, No. 4-221538
No. 5-21625, No. 5-15926, No. 4-331928, No. 5-19
The supports described in 9704, 6-13455, 6-14666 and the like can be preferably used. A support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used. The thickness of the support is preferably 5 to 200 μm, more preferably 40 to 120 μm.

Further, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable.
Next, the undercoating method may be a single layer or two or more layers. Examples of the binder for the undercoat layer include vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, and a copolymer having a monomer selected from maleic anhydride as a starting material. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, gelatin, polyvinyl alcohol, and modified polymers thereof. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine) Etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

The dye used for film dyeing is preferably gray dyeing due to the general properties of the light-sensitive material, excellent in heat resistance in the film forming temperature range, and excellent in compatibility with polyester. Those are preferable. From this point of view, as the dye, it is possible to achieve the object by mixing commercially available dyes for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. In particular, from the viewpoint of heat resistance stability, anthraquinone dyes can be mentioned. For example, those described in JP-A-8-122970 can be preferably used.

Further, as the support, for example, JP-A-4-1462
It is preferable to record photographing information and the like using a support having a magnetic recording layer described in No. 45, No. 5-40321, No. 6-35092, No. 6-317875 and the like.

The magnetic recording layer is formed by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. Magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co-coated magnetite, C
O-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co-deposited ferromagnetic iron oxides such as Co-deposited γFe ₂ O ₃ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. The specific surface area of SBET is preferably 20 m ² / g or more, and more preferably 30 m ² / g or more. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be surface-treated with silica and / or alumina or an organic material. Further, the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent on the surface thereof as described in JP-A-6-101632. Further, magnetic particles described in JP-A-4-259911 and 5-81652 whose surface is coated with an inorganic or organic substance can also be used.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg −20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. This heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less. The heat treatment of the support may be carried out in the form of a roll, or may be carried in the form of a web while being conveyed. The surface state may be improved by imparting irregularities to the surface (for example, applying conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ ). Further, it is desirable to take measures such as giving a knurl to the end and slightly raising only the end so as to prevent the cut end of the winding core from being exposed. These heat treatments are after the support film formation, the surface treatment,
It may be carried out at any stage after coating the back layer (antistatic agent, slip agent, etc.) and after coating the undercoat layer. Preferred is after the antistatic agent is applied. An ultraviolet absorber may be kneaded into this polyester. Also, to prevent light piping,
The object can be achieved by kneading a commercially available dye or pigment for polyester, such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayaset.

Next, a film cartridge in which a light-sensitive material can be loaded will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic. Further, a patrone that rotates the spool to feed the film may be used. Further, the structure may be such that the tip of the film is housed inside the cartridge body and the tip of the film is fed to the outside from the port of the cartridge by rotating the spool shaft in the feeding direction of the film. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The above light-sensitive materials can be preferably used in the film unit with a lens described in JP-B-2-32615 and JP-B-3-39784.

The lens-fitted film unit is a unit in which a non-exposed color or monochrome photographic light-sensitive material is preliminarily loaded in a manufacturing process of a unit body provided with a photographing lens and a shutter in, for example, an injection-molded plastic housing. This unit is
Units are sent to the photo lab for development. At the developing station, the photographic film is taken out from the unit, and development and photographic print production are performed.

[III] Image Forming Method The photothermographic material of the present invention may be developed by any method, but usually the imagewise exposed photosensitive material is heated and developed. As a preferred embodiment of heat development, it is brought into contact with a heated block or plate, or brought into contact with a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared and far infrared lamp heater, or a high temperature atmosphere. There is a method of passing the inside. As a heat source for these, in addition to an ordinary electric heater or a lamp heater, a heating liquid, a dielectric material, a heater such as a microwave can be used. A preferred form of the thermal developing machine is a type in which the thermosensitive photosensitive material is brought into contact with a heat source such as a heat roller or a heat drum. As the thermal developing machine of this type, it is possible to use the thermal developing machines described in Japanese Examined Patent Publication No. 5-56499, Japanese Patent No. 684453, Japanese Unexamined Patent Publication No. 9-292695, Japanese Unexamined Patent Publication No. 9-297385, and WO95 / 30934. . In addition, as a non-contact type,
7-13294, WO97 / 28489, 97/28488 and 97/2848
The heat developing machine described in No. 7 can be used. The preferred developing temperature is 100 ° C to 350 ° C, and more preferred is 13 ° C.
The temperature is in the range of 0 ° C to 200 ° C, and the developing time is preferably 1 to 60 seconds, more preferably 3 to 30 seconds.

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

The film-shaped light-sensitive material photographed is usually separated from the cartridge or cartridge and subjected to heat development processing in a bare state. It is also preferable to perform heat development while pulling out the film, and to return the developed film to the thrust cartridge again when the development is completed to the end. Further, it is also possible to perform heat development from the outside together with the packaging container while being wound in the cartridge or cartridge.

After forming a color image by heat development, the remaining silver halide and / or developed silver may be removed.
You don't have to. Also, as a method of outputting to another material based on the image information, it may be a normal projection exposure,
Image information may be photoelectrically read by measuring the density of transmitted light, and may be output by the signal. The material to be output does not have to be a photosensitive material, for example, a sublimation type thermal recording material,
It may be an inkjet material, an electrophotographic material, a full-color direct thermal recording material, or the like. A preferred example of the image forming method of the present invention is one in which after forming a colored image by heat development, additional processing for removing residual silver halide and developed silver is not performed, and image information is applied using diffused light and a CCD image sensor. It was read photoelectrically by the measured transmission density, converted into a digital signal, and then image-processed.
For example, Pictorography 30 from Fuji Photo Film Co., Ltd.
00 is output. In this case, it is possible to quickly obtain a good print without using any processing solution used in conventional color photography. Further, in this case, since the digital signal can be arbitrarily processed and edited, the photographed image can be freely modified, deformed, processed, and output.

Another bleach-fixing step for further removing the silver halide and the developed silver remaining in the light-sensitive material after development is not essential. However, a fixing step and / or a bleaching step may be provided in order to reduce the load of reading the image information and to improve the image storability. In that case, a normal liquid treatment may be used, but it is preferable to perform a heat treatment step together with another sheet coated with a treatment agent as described in JP-A-9-258402. The heating temperature in this case is preferably 50 ° C. as in the development processing step, and particularly preferably set to the same temperature as in the development processing step.

In the present invention, after an image is obtained on a light-sensitive material, a color image is obtained on another recording material based on the information. As the method, it is preferable to photoelectrically read the image information by measuring the density of the transmitted light, convert it into a digital signal, and after image processing, output it to another recording material by the signal. The material to be output may be a sublimation type thermal recording material, a full color direct thermal recording material, an inkjet material, an electrophotographic material, etc., in addition to the photosensitive material using silver halide.

It is necessary to read the image formed on the heat-developed photosensitive material and convert it into a digital signal. A known image input device can be used for this image reading apparatus. For details of image input devices, see Takao Ando, "Basics of Digital Image Input", Corona Publishing Co., Ltd. (1998), pp. 58-98.
It is described on the page. The image input device needs to take in a huge amount of image information efficiently, and it is roughly classified into a linear sensor and an area sensor in the arrangement of minute point sensors. In the former, a large number of point sensors are arranged on a line, and it is necessary to scan either the sensitive material side or the sensor side in order to capture a planar image. Therefore, it takes a little time to read, but there is an advantage that the sensor can be manufactured at low cost. In the case of the area sensor, basically, it is possible to read without scanning the photosensitive material or the sensor. However, it costs a lot because it is fast to read but requires the use of a large sensor. These sensors can be used properly according to the purpose, and both can be used preferably.

There are electron tube types such as an image pickup tube and an image tube and solid-state image pickup systems such as CCD type and MOS type as the types of sensors.
The CCD type is particularly preferable. As a device equipped with these image input devices, commercially available digital still cameras, drum scanners, flatbed scanners, film scanners, etc. can be used, but in order to easily read high-quality images, It is preferable to use a film scanner.

A typical commercially available film scanner is a Nikon film scanner LS- which uses a linear CCD.
There are 1000, Agfa Duoscan HiD, Imacon, FlexTight Photo, etc., and Kodak RFS3570 etc. using area CCD can be preferably used. An image input device using an area CCD mounted on the frontier of Fuji Photo Film's digital printing system can also be preferably used. Furthermore, the image input device of the Frontier F350 described by Yoshio Ozawa et al., Fuji Film Research Report No. 45, pp. 35-41 realizes high-speed and high-quality reading while using a linear CCD sensor. It is particularly suitable for reading light-sensitive materials.

When reading image information on a photosensitive material by an image sensor such as CMOS or CCD, which wavelength range image is read by the combination of the light source used for reading, the color filter of the light source, and the color sensitivity of the image sensor. Can be set. As the light source used for reading, lamps such as xenon, halogen, tungsten, etc., LED, laser, etc. can be used. In order to reproduce a good color image, dyes with maximum absorption in different wavelength regions, which are formed in each color-sensitive layer, should be within ± 50 nm of the maximum absorption of 3
It is preferable to read the image information in the area and perform an appropriate calculation. Usually, a photosensitive material having a maximum absorption wavelength in the visible wavelength range and including a yellow color forming coupler, a magenta color forming coupler and a cyan color forming coupler is used, and the dye image information of each is read with blue light, green light and red light. Further, at least one of the couplers forming a dye having a maximum absorption wavelength in the visible wavelength range, by replacing the coupler forming a dye having a maximum absorption wavelength in the non-visible wavelength range, image information in the non-visible wavelength range May be read. Two or more compounds that form a dye having a maximum absorption wavelength in different invisible wavelength regions may be used. For the light source in the invisible wavelength range used for reading, a high-brightness LED is easily available, and the image sensor is preferably a CCD, which has high sensitivity in the infrared wavelength range.

The following image processing methods can be preferably used in the image forming method of the present invention. As described in JP-A-6-139323, a subject image is formed on a color negative, the image is converted into corresponding image data by a scanner or the like, and then the same color as the subject is output from the demodulated color information. An image processing system and an image processing method that can faithfully reproduce colors can be used. Further, suppressing the granularity or noise of the digitized image, and as an image processing method for emphasizing the sharpness, as described in JP-A-10-243238, sharpness-enhanced image data, smoothed image data and edge detection data. A method for performing weighting and subdivision processing on edges and noise based on, or the method described in JP-A-10-243239.
An image processing method may be used in which edge components are obtained based on the sharpness-enhanced image data and the smoothed image data, and weighting and subdivision processing are performed. Further, in order to correct the variation in color reproducibility in the final print due to the difference in the storage condition and the developing condition of the photographic material in the digital color printing system, the unexposed material of the photographic material described in JP-A-10-255037 is disclosed. After four-stage or four-color or more patches are exposed to the area, the patch density is measured after development, the look-up table and color conversion matrix necessary for correction are obtained, and the look-up table conversion and matrix operation are used to obtain the photographic image. A method of performing color correction can be used. As a method for converting the color gamut of image data, for example, Japanese Patent Laid-Open No.
-For image data represented by color signals described in No. 229502, which become a color that is visually recognized as a neutral color when the values of each component are aligned, the color signals are chromatic and achromatic. It is possible to use a method of decomposing into components and treating each separately. Further, as an image processing method for removing image quality deterioration such as aberration and reduction of peripheral light amount due to a camera lens in an image captured by a camera, there is disclosed in Japanese Patent Laid-Open No. 11-6
As described in No. 9277, a grid-shaped correction pattern for creating correction data for image deterioration is recorded on the film in advance, and after shooting, the image and the correction pattern are read with a film scanner or the like, and deterioration based on the lens of the camera is recorded. Create data to correct the factors, and use the image deterioration correction data,
An image processing method and apparatus for correcting digital image data may be used. Further, for the skin color and the blue sky, if the sharpness is emphasized too much, graininess (noise) is emphasized to give an unpleasant impression, so it is desirable to suppress the degree of sharpness enhancement for the skin color and the blue sky.
For example, in the sharpness enhancement processing using unsharp masking (USM) described in JP-A-11-103393, a method in which the USM coefficient is a function of (BA) (RA) may be used. In addition, flesh color, grass green, and blue sky are called important colors for color reproduction, and selective color reproduction processing is required. Among them, it is visually preferable to reproduce the lightness so that the skin color is bright and the blue sky is dark. As a method of reproducing an important color to a visually preferable brightness, for example, Japanese Patent Laid-Open No. 11-177
For the color signal for each pixel described in No. 835, use a coefficient such as (RG) and (RB) that takes a small value when the corresponding hue is yellow red and a large value when it is cyan blue. A conversion method may be adopted. Further, as a method of compressing a color signal, for example, as described in JP-A-11-113023, a color signal for each pixel is separated into a lightness component and a chromaticity component, and a plurality of pre-prepared chromaticity components are prepared. It is also possible to use the method of encoding the hue information by selecting the template having the most suitable numerical pattern from the hue templates.
In addition, when processing such as increasing the saturation or sharpness, it is possible to suppress the occurrence of defects such as color blindness, highlight skipping, high density area collapse, and out-of-definition data, and perform natural emphasis processing. Is the exposure density data using the characteristic curve for each color density data of the color image data described in JP-A-11-177832, and image processing including color emphasis is performed on the exposure density data.
Further, an image processing method and apparatus which uses density data as a characteristic curve can be used. Further, the image information in the region where the absorption of the dye formed in each color-sensitive layer is minimized, preferably in the infrared wavelength region, is read together, and the operation is performed in combination with the image information in the maximum absorption region of the dye. Then, it is also preferable to remove unnecessary image information such as scratches, noise, and residual developed silver on the photosensitive material. When reading the image information in the non-visible wavelength range by replacing the coupler forming the dye having the maximum absorption wavelength in the visible wavelength range with the coupler forming the dye having the maximum absorption wavelength in the non-visible wavelength range, two or more May be read in different invisible wavelength ranges. Further, unnecessary image information such as scratches, noise, and residual developed silver on the photosensitive material may be removed by using information in the visible wavelength region.

[0224]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 Preparation of Highly Sensitive Silver Halide Emulsion 0.37 g of gelatin having an average molecular weight of 15000, 0.37 g of oxidized gelatin and 930 ml of distilled water containing 0.7 g of potassium bromide were placed in a reaction vessel. The temperature was raised to 38 ° C. While stirring vigorously to this solution, 30 ml of an aqueous solution containing 0.34 g of silver nitrate and 0.24 g of
And 30 ml of an aqueous solution containing potassium bromide were added in 20 seconds. After the addition was completed, the temperature of the reaction solution was raised to 75 ° C. after being kept at 40 ° C. for 1 minute. After adding 27.0 g of gelatin modified with amino acid trimellitic acid together with 200 ml of distilled water, 2
100 ml of an aqueous solution containing 3.36 g of silver nitrate and 80 ml of an aqueous solution containing 16.37 g of potassium bromide were added while accelerating the flow rate.
Added over minutes. Then containing 83.2 g of silver nitrate 2
A 50 ml aqueous solution and an aqueous solution containing potassium iodide and potassium bromide in a molar ratio of 3:97 (concentration of potassium bromide: 26% by mass) were added, while the flow rate was accelerated and the silver potential of the reaction solution was saturated. To -50 mV for 60 minutes. An additional 75 ml of an aqueous solution containing 18.7 g of silver nitrate and 21.9
A mass% potassium bromide aqueous solution was added over 10 minutes so that the silver potential of the reaction solution was 0 mV with respect to the saturated calomel electrode. After keeping the temperature at 75 ° C for 1 minute after the addition,
The temperature of the reaction solution was lowered to 40 ° C. Then 10.5 g p-
The pH of the reaction solution was adjusted to 9.0 by adding 100 ml of an aqueous solution containing sodium iodoacetamidebenzenesulfonate monohydrate. Then 50 ml of an aqueous solution containing 4.3 g of sodium sulfite was added. After the addition was completed, the temperature of the reaction solution was raised to 55 ° C. after maintaining at 40 ° C. for 3 minutes. After adjusting the pH of the reaction solution to 5.8, 0.8 mg of sodium benzenethiosulfinate, 0.04 mg of potassium hexachloroiridium (IV) ate and 5.5 g of potassium bromide were added, and the mixture was kept at 55 ° C for 1 minute, and then further added. 180 ml aqueous solution containing 44.3 g silver nitrate and 34.0 g
And 160 ml of an aqueous solution containing 8.9 mg of potassium hexacyanoferrate (II) were added over 30 minutes. The temperature was lowered, and desalting was performed according to a standard method. After desalting, gelatin was added to 7% by mass and pH was adjusted to 6.
Adjusted to 2.

The obtained emulsion was an emulsion composed of hexagonal tabular grains having an average grain size of 1.15 μm represented by a diameter corresponding to a sphere, an average grain thickness of 0.12 μm and an average aspect ratio of 24.0.
This emulsion was designated as Emulsion A-1.

Emulsion A-1 was prepared by changing the amounts of silver nitrate and potassium bromide added at the beginning of grain formation, and changing the number of nuclei formed, so that the average grain size represented by the diameter corresponding to a sphere was 0.
75μm, average particle thickness 0.11μm, average aspect ratio 14.0
Emulsion A-2 consisting of hexagonal tabular grains, and an average grain size expressed by the diameter of a sphere of 0.52 μm, an average grain thickness of 0.09 μ
An emulsion A-3 consisting of hexagonal tabular grains having an m and an average aspect ratio of 11.3 was prepared. However, hexachloroiridium (I
V) Potassium and potassium hexacyanoferrate (II) were added in inverse proportion to the volume of the particle, and the amount of sodium p-iodoacetamidebenzenesulfonate monohydrate was changed in proportion to the circumference of the particle. It was

To Emulsion A-1, 5.6 ml of potassium iodide 1% by mass
After adding the aqueous solution at 40 ° C., 8.2 × 10 ⁻⁴ mol / mol Ag of the following spectral sensitizing dye, compound 1, potassium thiocyanate, chloroauric acid, sodium thiosulfate and mono (pentafluorophenyl) diphenylphosphine selenide Was added for spectral sensitization and chemical sensitization. After the chemical sensitization was completed, the stabilizer S was added. At this time, the amount of the chemical sensitizer was adjusted to optimize the degree of chemical sensitization of the emulsion. The structures of the spectral sensitizing dye, compound 1 and stabilizer S are shown below.

[0229]

[Chemical formula 67]

The blue-sensitive emulsion thus prepared was designated as A-1b. Similarly, each emulsion was spectrally and chemically sensitized to prepare Emulsions A-2b and A-3b. However, the addition amount of the spectral sensitizing dye was changed according to the surface area of silver halide grains in each emulsion. Also, the amount of each chemical used for chemical sensitization was adjusted so that the degree of chemical sensitization of each emulsion was optimal.

Similarly, by changing the spectral sensitizing dye to the following spectral sensitizing dye, green-sensitive emulsions A-1g, A-2g and A-3g, and red-sensitive emulsions A-1r, A-2r and A-3r. Was prepared.

[0232]

[Chemical 68]

[0233]

[Chemical 69]

(Preparation of 1-phenyl-5-mercaptotetrazole silver salt) 431 g of lime-processed gelatin and 65
69 ml of distilled water was added. Next, 320 g of 1-phenyl-5-mercaptotetrazole was mixed with 2044 ml of distilled water and 790 g of a 2.5 M sodium hydroxide aqueous solution to prepare a solution B. Solution B and nitric acid or sodium hydroxide as needed were added to the mixture in the reaction vessel to adjust pAg 7.25 and pH 8.00. To the above reaction vessel, under strong stirring, 3200 ml of 0.54 M silver nitrate aqueous solution was added at a rate of 250 cc / min, and at the same time, the solution B was controlled to keep the pAg of the reaction solution at 7.25, and the solution was placed in the vicinity of the stirrer. Was added. After the addition was completed, the mixture was concentrated by performing ultrafiltration to obtain a dispersion containing fine particles of silver salt of 1-phenyl-5-mercaptotetrazole. <Preparation method of benzotriazole silver> 0.34 g of benzotriazole, 0.24 g of sodium hydroxide and 25 g of phthalated gelatin were dissolved in 700 ml of water, kept at 60 ° C and stirred. Next, a solution of 3.4 g of benzotriazole and 1.2 g of sodium hydroxide in 150 ml of water and a solution of 5 g of silver nitrate in 150 ml of water were simultaneously added to the above solution in the vicinity of the stirrer in 4 minutes. . After stirring for 5 minutes, a solution of 3.4 g of benzotriazole and 1.2 g of sodium hydroxide dissolved in 150 ml of water and a solution of 5 g of silver nitrate dissolved in 150 ml of water were simultaneously added within 6 minutes to the vicinity of the stirrer in the solution. did. By adjusting the pH of this emulsion, the emulsion is allowed to settle,
Excess salt was removed. Then adjust the pH to 6.0 and
70 g of benzotriazole silver emulsion was obtained.

<Solid fine particle dispersion of base precursor
Preparation of (a)> 64 g of base precursor compound BP-35, 28 g of diphenyl sulfone and 10 g of Demol N (Kao Corporation)
(Made by Surfactant) is mixed with 220 ml of distilled water, and the mixture is dispersed in beads using a sand mill (1/4 Gallon Sand Grinder Mill, manufactured by AIMEX Co., Ltd.), and the average particle diameter is 0.
2 μm solid precursor dispersion of base precursor compound
(a) was obtained.

<Preparation of Dye Solid Fine Particle Dispersion> 9.6 g of a cyanine dye compound and 5.8 g of sodium p-dodecylbenzenesulfonate were mixed with 305 ml of distilled water, and the mixture was sand-milled (1/4 Gallon Sand Grinder Mill). Beads were dispersed using IMEX Co., Ltd. to obtain a dye solid fine particle dispersion having an average particle diameter of 0.2 μm. The structures of the base precursor compound BP-35 and the cyanine dye compound are shown below.

[Chemical 70]

[Chemical 71]

<Preparation of Support> In preparing a light-sensitive material, preparation of a support, an undercoat layer, an antistatic layer (back first layer), a magnetic recording layer (back second layer), and a back third layer were prepared. The coating was carried out as follows.

(1) Preparation of Support The support used in this example was prepared by the following method. 100 parts by weight of polyethylene-2,6-naphthalenedicarboxylate (PEN) and Tinuvin P.326 as an ultraviolet absorber
(Made by Ciba-Geigy) 2 parts by mass are uniformly mixed, melted at 300 ° C., extruded from a T-die, and longitudinally stretched 3.3 times at 140 ° C., then 4.0 times Laterally stretched and heat set at 250 ℃ for 6 seconds to a thickness of 90μm.
Got a PEN film. The PEN film contains blue dye, magenta dye, and yellow dye (I-1, I-4, I-6, I-24, I-2 described in Public Technical Report No. 94-6023).
6, I-27, II-5) was added in an appropriate amount. Furthermore, diameter 30c
It was wound around a stainless steel core of m and given a thermal history of 110 ° C. for 48 hours to obtain a support with less curl.

(2) Coating of Undercoat Layer Both sides of the PEN support were subjected to glow treatment as follows.
Four rod-shaped electrodes having a diameter of 2 cm and a length of 40 cm were fixed at 10 cm intervals on an insulating plate in a vacuum tank. At this time, the film was set to run at a distance of 15 cm from the electrodes.
Also, a heating roll with a temperature controller of 50 cm diameter was installed in front of the electrode, and the film was placed on this heating roll for 3/4
It was set to make circumferential contact. A biaxially stretched film having a thickness of 90 μm and a width of 30 cm was run and heated with a heating roll so that the temperature of the film surface between the heating roll and the electrode zone was 115 ° C. Then, this film was conveyed at a speed of 15 cm / sec and subjected to glow treatment.

[0240] The pressure in the vacuum chamber is 26.5 Pa,
The partial pressure of H ₂ O was 75%. Discharge frequency is 30kHz, output 2500
The treatment was performed at a W and a treatment intensity of 0.5 k · V · A · min / m ² . The vacuum glow discharge electrode was in accordance with the method described in JP-A-7-3056.

An undercoat layer having the following formulation was provided on one side (emulsion side) of the glow-treated PEN support. Dry film thickness is 0.02μ
Designed to be m. The drying temperature was 115 ° C. for 3 minutes.

[0242] Gelatin 83 parts by mass Water 291 parts by mass Salicylic acid 18 parts by mass Aerosil R972 (Nippon Aerosil Co., Ltd., colloidal silica) 1 part by mass Methanol 6900 parts by mass n-Propanol 830 parts by mass Polyamide-epichlorohydrin resin described in JP-A-51-3619 25 parts by mass

(3) Coating of antistatic layer (back first layer) 40 parts by mass of SN-100 (conductive fine particles manufactured by Ishihara Sangyo Co., Ltd.)
After roughly dispersing with a stirrer while adding a 1N sodium hydroxide aqueous solution to a mixed solution of 60 parts by mass of water, the resulting mixture was dispersed with a horizontal sand mill to disperse conductive particles having an average particle size of 0.06 μm (pH = 7.0) got.

On a PEN support surface-treated with a coating solution having the following composition (back side), a coating amount of conductive fine particles of 270 mg /
It was applied so as to be m ² . The drying conditions were 115 ° C. and 3 minutes.

[0245] SN-100 (manufactured by Ishihara Sangyo Co., Ltd., conductive particles) 270 parts by mass 23 parts by weight of gelatin Leodol TW-L120 ・ (Kao Co., Ltd., surfactant) 6 parts by mass Denacol EX-521 (Nagase Kasei Co., Ltd., hardener) 9 parts by mass Water 5000 parts by mass

(4) Coated magnetic particles for magnetic recording layer (back second layer) CSF-4085V2 (manufactured by Toda Kogyo Co., Ltd., γ-Fe ₂ O ₃ coated with Co) was coated with magnetic particles. 16% by weight of X-12
Surface treatment was performed using -641 (silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.).

A coating solution having the following composition was placed on the back first layer,
The coating amount of CSF-4085V2 treated with silane coupling agent is 62
It was applied so as to be mg / m ² . The method of dispersing the magnetic particles and the abrasive was in accordance with the method disclosed in JP-A-6-35092. The drying condition was 115 ° C. for 1 minute.

[0248] Diacetyl cellulose (binder) 1140 parts by mass X-12-641 treated CSF-4085V2 (magnetic particles) 62 parts by mass AKP-50 (Alumina, abrasive, manufactured by Sumitomo Chemical Co., Ltd.) 40 parts by mass Millionate MR-400 (Nippon Polyurethane Co., Ltd., hardener) 71 parts by mass Cyclohexanone 12000 parts by mass Methyl ethyl ketone 12000 parts by mass

An increase in DB color density of the magnetic recording layer by X-light (blue filter) is about 0.1, a saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, a coercive force of 7.3 × 10 ⁴ A / m, And the squareness ratio was 65%.

(5) Coating of third back layer A third back layer was coated on the side of the magnetic recording layer of the photosensitive material. A wax (1-2) having the following structure is emulsified and dispersed in water using a high-pressure homogenizer, the concentration is 10% by mass, and the weight average diameter is 0.25 μm.
A wax aqueous dispersion of was obtained. Wax (1-2) nC
₁₇ H ₃₅ COOC ₄₀ H ₈₁ -n

A coating solution having the following composition was coated on the magnetic recording layer (back second layer) so that the coating amount of wax would be 27 mg / m ² . The drying condition was 115 ° C. for 1 minute.

[0252]   270 parts by mass of the above wax aqueous dispersion (10% by mass)   Pure water 176 parts by mass   Ethanol 7123 parts by mass   Cyclohexanone 841 parts by mass

(Preparation of Emulsion Dispersion Containing Coupler)
60% of 8.95 g of yellow coupler (CPY-1), 0.90 g of development accelerator (X), 4.54 g of high boiling point organic solvent (e), 4.54 g of high boiling point organic solvent (f) and 50.0 ml of ethyl acetate. Mixed at ° C.
The obtained solution was mixed with 200 g of an aqueous solution in which 18.0 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and emulsified and dispersed for 20 minutes at 10,000 rotations using a dissolver stirrer. Then, distilled water was added so that the total amount would be 300 g, and the mixture was mixed at 2000 rpm for 10 minutes. 8.
An emulsion was prepared in the same manner by changing the yellow coupler (CPY-1) of 95 g to the yellow coupler (CPY-2) of 8.95 g.
The structures of the yellow couplers (CPY-1), (CPY-2), the development accelerator (X), the high boiling point organic solvent (e) and the high boiling point organic solvent (f) are shown below.

[0254]

[Chemical 72]

Then, a dispersion of magenta coupler and cyan coupler was similarly prepared. 4.68g magenta coupler (CPM-1), 2.38g magenta coupler (CPM-2), 0.7
1g development accelerator (X), 7.52g high boiling organic solvent (e) and 3
8.0 ml of ethyl acetate was mixed at 60 ° C. 1 solution obtained
2.2 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were mixed in 150 g of an aqueous solution,
Using a dissolver stirrer, the mixture was emulsified and dispersed at 10,000 rpm for 20 minutes. Then, distilled water was added so that the total amount would be 300 g, and the mixture was mixed at 2000 rpm for 10 minutes. 4.68g magenta coupler (CPM-1) and 2.38g magenta coupler (CPM-2)
4.68g magenta coupler (CPM-3) and 2.38g respectively
A magenta coupler (CPM-2) was used to prepare an emulsion in the same manner. Magenta coupler (CPM-1), (CPM-2) and
The structure of (CPM-3) is shown below.

[0256]

[Chemical formula 73]

7.32 g of cyan coupler (CPC-1), 3.10 g of cyan coupler (CPC-2), 1.04 g of development accelerator (X), 11.
62 g of high boiling organic solvent (e) and 38.0 ml of ethyl acetate at 60 ° C
Mixed in. The obtained solution was mixed with 150 g of an aqueous solution in which 12.2 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and emulsified and dispersed for 20 minutes at 10,000 rotations using a dissolver stirrer. Then, distilled water was added so that the total amount would be 300 g, and the mixture was mixed at 2000 rpm for 10 minutes. Replace the 7.32g cyan coupler (CPC-1) and 3.10g cyan coupler (CPC-2) with 7.32g cyan coupler (CPC-3) and 3.10g cyan coupler (CPC-4) respectively. An emulsion was prepared. Cyan coupler (CPC-1),
The structures of (CPC-2), (CPC-3) and (CPC-4) are shown below.

[0258]

[Chemical 74]

(Preparation of Solid Dispersion of Built-in Developing Agent) A microcrystalline dispersion of built-in developing agent DEVP-1X was prepared by the following method. 50 g of the built-in developing agent DEVP-1X and 30 g of modified polyvinyl alcohol (Kuraray Co., Ltd. Poval MP203) 10 mass% aqueous solution, 1.0 g of Arch Chemicals Surfactant 10G and 1
00 g of water was added and mixed well to form a slurry. This slurry is sent by a diaphragm pump and the average diameter is 0.5m.
Horizontal sand mill (UVM-
2: After being dispersed in IMEX Co., Ltd. for 6 hours, water was added to the mixture to prepare a target compound having a concentration of 10% by mass to obtain a dispersion of the target compound. The particles contained in the thus obtained dispersion of the target compound had a median diameter of 0.50 μm and a maximum particle diameter of 1.5 μm or less. The obtained dispersion of the target compound was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign matters such as dust and stored. Immediately before use, it was filtered again with a polypropylene filter having a pore size of 10 μm.

Dispersions were prepared for DEVP-2X, DEVP-3X, DEVP-4X, and the color developing agent of the present invention in the same manner as above. still,
DEVP-1X is a compound D-28 described in European Published Patent 1113326A2, DEVP-2X is a compound D-28 described in European Published Patent 1113322A2, DEVP-3X is a European Published Patent 1113.
Compound D-10 and DEVP-4X described in 322A2 are disclosed in JP-A-2002-11652.
It is the compound described in No. 1.

[0261]

[Chemical 75]

Further, as a filter layer and an antihalation layer, a dispersion of a dye which is decolored by heating for coloring the intermediate layer was prepared.

<Preparation of Dye Dispersion for Yellow Filter (YH) Layer> 10 g of leuco dye (L1), 40 g of stearyl alcohol and 10 g of developer (SD-1) were mixed with 200 ml of ethyl acetate to obtain The obtained solution was dissolved with 2.0 g of surfactant (r) 6
Mix with 00g of aqueous solution and 100 using a dissolver stirrer.
It was emulsified and dispersed at 00 rpm for 20 minutes. Then under nitrogen stream
The mixture was stirred at 50 ° C. for 30 minutes to remove ethyl acetate, 30 g of lime-processed gelatin was added, distilled water was added so that the total amount became 750 g, and the mixture was mixed at 2000 rpm for 10 minutes.

The leuco dye (L1) was changed to a leuco dye (L2) and a leuco dye (L3), respectively, to prepare a magenta filter (MF) dye dispersion and an antihalation (AH) dye dispersion, respectively. The structures of the developer (SD-1), leuco dye (L1), leuco dye (L2) and leuco dye (L3) are shown below.

[0265]

[Chemical 76]

[0266]

[Chemical 77]

Using these emulsions, light-sensitive material samples 101 and 102 for multilayer color heat development shown in Tables 1 and 2 were prepared. The structures of the additives shown in Tables 1 and 2 are shown below.

(Unit is parts by mass)

[Table 1]

[Table 2] (Continued from Table 1)

[0269]

[Chemical 78]

[Chemical 79]

Photosensitive material sample 103 was prepared in the same manner except that the DEVP-1X of the photosensitive material sample 101 was replaced with a double molar amount of DEVP-2X, DEVP-3X and the color developing agent of the present invention shown in Table 2. ~ 109 were produced.

Further, the DEVP-1X of the photosensitive material sample 102 is
Two times the molar amount of the color developing agent of the present invention shown in Table 2, and DE
Photosensitive material sample 1 in the same manner except that it was replaced with VP-4X
10-114 were produced.

A method for obtaining ISO sensitivity by cutting a sample piece from each of these photosensitive material samples 101 to 114 (ANSI
According to PH 2.27), 1/100 second exposure was performed with a white light source 500lux through a continuous optical wedge. After exposure,
Using a heat drum, heat development was performed at 150 ° C. for 20 seconds. The density is measured, and the color development is determined by the color density of the maximum exposed area.
Discrimination was evaluated from the difference in density between the unexposed area and the maximum exposed area, and five-level evaluation was performed for each color of yellow, magenta, and cyan. The obtained results are shown in Table 2. Furthermore, each sample was placed in an atmosphere of 50 ° C. and 50% RH.
After storage for 1 week, exposure and heat development were performed in the same manner, and the results of evaluation of discrimination are shown in Table 2. The larger the evaluation value, the better the performance.

[0273]

[Table 3]

The samples using the built-in developing agent of the present invention (Samples 103 to 106 and 109 to 113) were
Not only excellent in discrimination, but 50 ℃ 5
It was found that the excellent performance that the discrimination after storage for 1 week at 0% RH hardly changed was exhibited.

The ClogP value of the compound released from the built-in developing agent used in this example (corresponding to the compound of the formula (1) in which R ₅ —SO ₂ —NH—CO— is a hydrogen atom) is shown below. .

[0276]

[Chemical 80]

Photosensitive material samples 101 to 114 were cut into 135 negative film size, perforated and loaded into a camera to photograph a person and a Macbeth chart. The image on the photosensitive material that has been heat-developed by the above method is read by the digital image reading device Frontier SP-1000 (manufactured by Fuji Photo Film Co., Ltd.), and after image processing on the workstation, the photothermographic printer (PICTROGRAPHY3000 , Fuji Photo Film Co., Ltd.)
It was output with.

Samples 101 and 103-109 were read at room temperature,
Samples 102 and 110 to 114 were read while sending warm air to the surface of the photosensitive material with a dryer at the time of reading so that the film surface temperature was 60 to 70 ° C. Using the Macbeth chart in the image, color correction processing for increasing color saturation while maintaining color reproduction by digital signal processing was performed, and when the color developing agent of the present invention was used (photosensitive material samples 103 to 106, 109 ~ 1
13), excellent in color density, sensitivity and discrimination, and prints with high saturation were obtained.

Example 2 A silver halide emulsion composed of high silver chloride tabular grains was prepared according to the method described in Examples of US Pat. No. 5,840,475. 1.48 g of sodium iodochloride (100) tabular emulsion emulsion To a reaction vessel, 1.48 g of sodium chloride, 0.28 g of potassium iodide, 38.8 g of oxidized lime-processed gelatin and distilled water were added to 4.5 liters and kept at 35 ° C. . 4M containing 0.32g / l mercuric chloride in this solution under strong stirring
The silver nitrate aqueous solution (1) and the 4M sodium chloride aqueous solution were added at a rate of 21 ml / min for 30 seconds to form nuclei. Immediately thereafter, a 9.1 liter solution containing 0.39 g / liter sodium chloride and 0.12 g / liter potassium iodide was added and held for 8 minutes. Subsequently, the above solution 1 was added under the conditions shown in the table below to form silver halide grains. At this time, make sure that the pCl of the reaction solution becomes 2.2 at the same time.
A 4M aqueous solution of sodium chloride was added in a controlled manner. Initial flow rate of particle growth Final flow rate Addition time I 14 ml / min 14 ml / min 5 min II 14 ml / min 42 ml / min 52 min At the end of the above particle growth stage II, 4 M sodium chloride aqueous solution was added at 14 ml / min for 5 min. Add and hold for 30 minutes. Then, Solution 1 was added at a rate of 14 ml / min for 5 minutes, followed by the addition of 70 ml of an aqueous solution containing 5.25 g of potassium iodide, which was kept for 20 minutes, and then Solution 1 was added at a rate of 14 ml / min for 8 minutes. It was added for 2 minutes, and at the same time, a 4M sodium chloride aqueous solution was controlled and added so that the pCl of the system became 2.2. At this time, potassium hexacyanoruthenate was contained in the aqueous sodium chloride solution at a concentration of 3 × 10 ^-5 mol based on the total silver halide. After the particle formation was completed, sedimentation, washing with water, and desalting were performed according to a standard method. The resulting emulsion was tabular grains having an average diameter of circles equivalent to the projected area of 0.56 μm and an average grain thickness of 0.09 μm, and (10
The tabular grains having the (0) plane as the principal plane were contained in a proportion of 70% or more of the total projected area of the silver halide grains. This emulsion was designated as emulsion u.

Next, by controlling the temperature and time for grain formation, tabular grains having an average diameter of circles equivalent to the projected area of 1.60 μm and an average grain thickness of 0.114 μm were obtained.
An emulsion m was prepared which contained tabular grains having a plane as the main plane at a ratio of 70% or more of the total projected area of silver halide grains. Furthermore, by controlling the temperature and time of grain formation, tabular grains having an average diameter of circles equivalent to the projected area of 2.90 μm and an average grain thickness of 0.121 μm and having the (100) plane as the main plane An emulsion o containing tabular grains having a ratio of 70% or more of the total projected area of silver halide grains was prepared.
These emulsions were chemically and spectrally sensitized in the same manner as in Example 1 to prepare blue-, green- and red-sensitive emulsions, and blue-sensitized emulsions o-b, m-b and u-b, Green sensitized emulsions o-g, m-g and u-
g, and red sensitized emulsions o-r, m-r and u-r were obtained. Emulsions A-1b, A-2b, A-3b of the light-sensitive material samples 101 to 114 of Example 1,
A-1g, A-2g, A-3g, A-1r, A-2r, and A-3r are respectively blue-sensitized emulsions o-b, m-b and u-b, and green-sensitized emulsion o-g. , M-g
And u-g, and red-sensitized emulsions o-r, m-r, and u-r were used to prepare light-sensitive materials 201 to 214. When these light-sensitive materials, Samples 201 to 214, were exposed and heat-developed in the same manner as in Example 1, when the color developing agent of the present invention was used (light-sensitive material samples 203 to 206, 209 to 213), color turbidity was observed. A highly saturated print with less color was obtained.

Example 3 A silver iodochloride (111) tabular emulsion reactor was charged with 9.3 g of sodium chloride, 2.84 g of 7-azaindole, and 80 g of lime-processed bone gelatin and distilled water.
It was 3.9 liters and kept at 50 ° C. After adjusting the pH of the solution to 5.5, add 2M silver nitrate aqueous solution to 8m of this solution under strong stirring.
It was added for 36 seconds at an addition rate of 1 / min to form nuclei. Immediately thereafter, an aqueous silver nitrate solution was added under the conditions shown in the table below to form silver halide grains. At the same time, pCl of the reaction solution
A 4M sodium chloride aqueous solution was controlled and added so that the ratio became 1.5. Grain growth Silver nitrate solution Initial flow rate Final flow rate Addition time I 2M 8ml / min 16ml / min 2.8min II 4M 8ml / min 30ml / min 15min III 4M 30ml / min 30ml / min 14min 1 min after the end of the grain growth stage, 23% of 4M silver nitrate solution
Addition was performed for 2.4 minutes at an addition rate of ml / min. At the same time the system pCl
An aqueous solution containing 3.6 M of sodium chloride and 0.4 M of potassium iodide was controlled and added so that the ratio became 1.5. At this time, potassium hexacyanoruthenate was contained in the sodium chloride / potassium iodide aqueous solution at a concentration of 3 × 10 ^-5 mol based on the total silver halide. After the particle formation was completed, sedimentation, washing with water, and desalting were performed according to a standard method. The obtained emulsion was a tabular grain having an average diameter of circles equivalent to the projected area of 0.86 μm and an average grain thickness of 0.10 μm, and the tabular grains having (111) faces as main planes were halogenated. The content was 70% or more of the total projected area of silver halide grains. This emulsion was designated as emulsion u '.

Next, by adjusting the temperature and time for grain formation, tabular grains having an average diameter of circles equivalent to the projected area of 1.58 μm and an average grain thickness of 0.119 μm, and (111 ) 70% of the total projected area of tabular grains whose main plane is
Emulsion m'containing the above ratio was prepared. Furthermore,
By adjusting the temperature and time of grain formation, the average circle diameter equivalent to the projected area is 2.85 μm, and the average grain thickness is 0.131.
An emulsion o'containing tabular grains each having a grain size of .mu.m and having a main plane of (111) plane in an amount of 70% or more of the total projected area of silver halide grains was prepared. These emulsions were chemically and spectrally sensitized in the same manner as in Example 1 to prepare blue-, green- and red-sensitive emulsions, and blue-sensitized emulsion o'-
b, m'-b and u'-b, green sensitized emulsions o'-g, m'-g and u'-g, and red sensitized emulsions o'-r, m'-r and u'-r. Got Emulsions A-1b and A- of the light-sensitive material samples 101 to 114 of Example 1
2b, A-3b, A-1g, A-2g, A-3g, A-1r, A-2r and A-3r,
Blue sensitized emulsions o'-b, m'-b and u'-b, green sensitized emulsions o'-g, m'-g and u'-g, and red sensitized emulsion o ', respectively.
Photosensitive materials 301 to 314 in which -r, m'-r and u'-r were replaced were prepared. These photosensitive materials, Samples 301 to 314, were used in Example 1.
In the same manner as described above, when exposure and heat development processing were performed, when the color developing agent of the present invention was used (photosensitive material samples 303 to 30).
6, 309-313), and prints with little color turbidity and high saturation were obtained.

(Example 4) A photosensitive material sample 103 prepared in the same manner as in Example 1 was photographed and heat-developed in the same manner as in Example 1, and then, using a scanner LS-4000 (manufactured by Nikon Corporation), BGR was performed. Read information and IR information. After image processing on the workstation, it was output with a thermal development printer (PICTROGRAPHY3000, Fuji Photo Film Co., Ltd.). A print 103a obtained by image processing using only BGR information, and a print 103b obtained by image processing using IR information in addition to BGR information
When compared with 103a, 103b has less image defects such as scratches, less color turbidity and higher saturation, and an image with less granular deterioration caused by color correction calculation was obtained.

(Example 5) (Preparation of emulsified dispersion containing non-visible wavelength region coupler) 5.91 g of coupler ((1) -37), 3.04 g of coupler ((5))
-4), 0.90 g of development accelerator (X), 4.54 g of high boiling organic solvent (e), and 50.0 ml of ethyl acetate were mixed at 60 ° C. The obtained solution was mixed with 200 g of an aqueous solution in which 18.0 g of lime-processed gelatin and 0.8 g of sodium dodecylbenzenesulfonate were dissolved, and the mixture was mixed with a dissolver stirrer at 10000.
It was emulsified and dispersed by rotating for 20 minutes. Then, distilled water was added so that the total amount would be 300 g, and the mixture was mixed at 2000 rpm for 10 minutes.
The coupler ((1) -37) and coupler ((5) -4) were changed to 5.91 g coupler ((1) -1) and 3.04 g ((3) -1) and emulsion made

Emulsion of coupler CPY-1 and emulsion of coupler CPY-2 of light-sensitive material samples 103, 203, and 303 were respectively mixed with equal weight of coupler ((1) -37) and coupler ((5) -4). ) And the couplers ((1) -1) and ((3) -1) were replaced by the emulsions of Samples 401 and 4 having the same constitution.
02 and 403 were created.

These photosensitive material samples 401 to 403 and Example 1
The photosensitive material sample 103 prepared in 1. was exposed and heat-developed in the same manner as in Example 1. On processed photosensitive material 103
The B, G, and R image information was read with a digital image reader Frontier SP-1000. Furthermore, among the color filters installed in the light source of Frontier SP-1000,
The blue light transmitting filter was changed to an IR filter having a central wavelength of 800 nm and a rectangular wave transmission characteristic of a wavelength region of ± 50 nm, and G, R, and IR image information on the photosensitive material samples 401 to 403 was read. . At this time, from the light source of the reading optical system
The heat ray absorption filter installed between the CCD and 900nm
The filter was changed to absorb the above wavelengths. Using G, R, and IR image information on the processed photosensitive material samples 401 to 403, after image processing on the workstation, output with a heat development printer (PICTROGRAPHY3000, Fuji Photo Film Co., Ltd.) As in the case of using the BGR image information of the material sample 103, a print with less color turbidity and high saturation was obtained.

[0287] Furthermore, the blue LED of the scanner LS-4000 (manufactured by Nikon Corp.) is replaced by the LED of maximum wavelength 780 nm (Nichia Corporation
(Manufactured by K.K.) and read the information of G, R, IR1 (780 nm), and IR2 (about 900 nm) formed on the processed photosensitive material samples 401 to 403. After image processing on the workstation,
When printed with a thermal development printer (PICTROGRAPHY3000, manufactured by Fuji Photo Film Co., Ltd.), prints with no scratches, low color turbidity and high saturation were obtained.

[0288]

As described in detail above, the color-developing agent of the present invention realizes a high color-developing density without increasing fog, especially in the heat-developing method, and further has high sensitivity and high color-mixing. Since it can form a color image with color saturation,
It is extremely useful as a silver halide color photographic light-sensitive material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03C 7/46 G03C 7/46 (72) Inventor Masaaki Tsukase 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd. In-house (72) Inventor Kazuhiko Matsumoto 210 Nakanuma, Minamiashigara City, Kanagawa Fuji Photo Film Co., Ltd. F-term (reference) 2H016 AA00 BD00 BJ00 2H023 AA00 CD00 CD06 CE00 2H123 AB00 AB03 AB13 AB22 AB28 BB00 BB11 BB32 BC00 BC11 CB00 CB03

Claims (12)

[Claims] 1. A silver halide color photographic light-sensitive material containing a color developing agent represented by the following formula (1). Formula (1) In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a substituent, R ₄ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁ and R ₂ or / and R ₂ and R ₄ may combine with each other to form a 5-, 6- or 7-membered ring. Z represents a non-metal atom group forming a 5-membered, 6-membered or 7-membered ring with a nitrogen atom and two carbon atoms in the benzene ring. R ₅ represents an alkyl group, an aryl group, or a heterocyclic group. However, the compound represented by the formula (1) is R ₁ ~
Each of R ₄ contains neither a hydroxyl group, a carboxyl group nor a sulfo group. 2. R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, nitro group, alkoxy group, aryl. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, Sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group,
Heterocyclic thio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and aryl sulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group ,
The silver halide color photographic light-sensitive material according to claim 1, which represents a phosphinyloxy group, a phosphinylamino group, or a silyl group. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one of R ₁ and R ₂ represents a hydrogen atom. 4. The silver halide color photographic light-sensitive material according to claim 1, wherein R ₂ represents an alkyl group or an alkoxy group. 5. The silver halide color photographic light-sensitive material according to claim 1, wherein R ₄ represents an alkyl group. 6. The silver halide color photographic light-sensitive material according to claim 1, wherein the light-sensitive material is a photothermographic material. 7. A silver halide color photographic light-sensitive material according to claim 6, which comprises the color developing agent, a dye image-forming coupler, an organic silver salt as a reducible silver salt, and a binder on a support. material. 8. The silver halide color photographic light-sensitive material according to claim 1, which has an image forming layer containing the color developing agent and a dye image forming coupler on a support. 9. The silver halide color photographic light-sensitive material according to claim 8, wherein the image forming layer contains a photosensitive silver halide. 10. The silver halide color photographic light-sensitive material according to claim 6, which contains the color developing agent and a thermal solvent as a fine crystalline fine particle dispersion. 11. R ₅ in the compound represented by formula (1)
The silver halide color photographic light-sensitive material according to claim 1, wherein a compound obtained by substituting -SO ₂ -NH-CO- with a hydrogen atom has a ClogP value of 3.0 or more. 12. The silver halide color photographic light-sensitive material according to claim 7, wherein the dye image-forming coupler is a compound which forms a dye having maximum absorption in the non-visible region.