JP2002107880A - Dye-forming coupler and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye-forming coupler which is superior in color developing property and producible at a low price, in particular a yellow coupler, and to provide a silver halide color photographic sensitive material containing the coupler. SOLUTION: The dye-forming coupler is represented by formula (I) (where W is an N-containing heterocyclic group; Z is substituted aryl; X and Y are each =O, =S or =N-R and R is a substituent). A silver halide photographic sensitive material containing the coupler is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dye-forming coupler and a silver halide color photographic light-sensitive material containing the coupler.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material obtained by a subtractive color method, a color image is formed by three primary color dyes of yellow, magenta and cyan. In the current color photographic method using a p-phenylenediamine-based color developing agent, a β-acylacetic anilide-based compound is used as a yellow coupler. However, the hue of the yellow dye obtained from these couplers is reddish, and it is difficult to obtain a highly pure yellow dye,
In addition, the obtained dye has a small molecular extinction coefficient, requires a large amount of couplers and silver halides to obtain a desired color density, and increases the film thickness of the photosensitive material. However, there is a problem in that Furthermore, the obtained dye is easily decomposed under high-temperature and high-humidity conditions, and it has been strongly desired to further improve the image storability after the development processing.

In order to solve these problems, acyl groups and anilide groups have been improved, and recently, 1-alkylcyclopropanecarbonylacetic acid anilide compounds described in JP-A-4-21842 and JP-A-5-218402 have been disclosed. -11,
No. 416 has been proposed as a coupler obtained by improving a conventional acylacetate anilide-based compound. Dyes produced from these couplers have been improved in hue and molecular extinction coefficient than conventional ones, but are not yet sufficient in terms of image storability, and as the structure becomes complicated, coupler cost increases, There was a problem practically. Research Disclosure Item
m9939 (p. 74, 1972) and JP-A-52-297.
148070 describes a coupler having a 2,4-oxazolidinedione structure. However, the dyes produced from these couplers are not satisfactory in terms of both hue and molecular extinction coefficient in solving the problems of the conventional ones.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dye-forming coupler, particularly a yellow coupler, which overcomes the above-mentioned problems and has excellent coloring properties and can be produced at low cost. Another object of the present invention is to provide a silver halide color photographic light-sensitive material.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by a dye-forming coupler represented by the following formula (I). That is, the present invention provides (1) a dye-forming coupler represented by the following general formula (I).

[0006]

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In the general formula (I), W represents a nitrogen-containing heterocyclic group, and Z represents a substituted aryl group. X and Y each independently represent = O, = S or = NR. Here, R represents a substituent. (2) A silver halide color photographic material comprising at least one of the dye-forming couplers represented by formula (I).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The dye-forming coupler of the present invention is described in detail below. In the general formula (I), W represents a nitrogen-containing heterocyclic group, and the heterocyclic group is a ring-constituting atom (an atom forming a ring itself, and even if a hydrogen atom or a substituent is present on the ring, These are not included as ring-constituting atoms), and are preferably nitrogen-containing heterocyclic groups having at least one nitrogen atom as a ring-constituting atom, which is composed of a nitrogen atom, an oxygen atom, a sulfur atom, and a carbon atom. The nitrogen-containing heterocyclic group may be substituted with a substituent, and may be further condensed with a benzene ring, an alicyclic ring, a heterocyclic ring, or the like. The number of ring members (when condensed with a benzene ring, an alicyclic ring, a heterocyclic ring or the like, the number of ring members by a method in which the condensed ring portion is not counted as the number of ring members) is preferably 3 to 8 members, and more preferably 5 members. ~ 6
And particularly preferably 5 members.

The nitrogen-containing heterocyclic group may have a saturated or unsaturated ring moiety. In the case of an unsaturated ring, it may be an aromatic ring. It is preferably a saturated ring or an aromatic ring (heteroaromatic ring), particularly preferably an aromatic ring (heteroaromatic ring), and especially a 5-membered aromatic ring (heteroaromatic ring). The nitrogen-containing heterocyclic group preferably has 0 to 60 carbon atoms.
To 50 are more preferable, and 3 to 40 are particularly preferable. Further, the ring-constituting atom is preferably selected from a nitrogen atom and a carbon atom, and in this case, the number of nitrogen atoms is preferably 1 or 2.

Examples of the nitrogen-containing heterocyclic group include 1-pyrrolidinyl, 1-pyrrolyl, 2-pyrrolyl, pyrrolyl, imidazolyl, 1-imidazolyl, pyrazolyl, 3-, 4- or 5- Pyrazolyl group, indolizinyl group, benzimidazolyl group, 1H-indazolyl group, 1-indolinyl group, indolyl group, 2-indolyl group, 3-indolyl group and the like. Of these, 1
-A pyrrolyl group, a 2-pyrrolyl group, a pyrrolyl group, a benzimidazolyl group, a 1H-indazolyl group, a 1-indolinyl group, an indolyl group, a 2-indolyl group, and a 3-indolyl group are preferred, and a 2-pyrrolyl group and a 3-pyrrolyl group are preferred. , 1
-An indolinyl group, a 2-indolyl group and a 3-indolyl group are more preferred, and a 1-indolinyl group and a 3-indolyl group are still more preferred.

Examples of the substituent which the nitrogen-containing heterocyclic group may have include, for example, a halogen atom (for example, a chlorine atom, a bromine atom and a fluorine atom), an alkyl group (having 1 to 60 carbon atoms, for example, methyl, ethyl, Propyl, iso-butyl, t-
Butyl, t-octyl, 1-ethylhexyl, nonyl,
Cyclohexyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl), alkenyl group (2 to 60 carbon atoms, for example, vinyl, allyl, oleyl), cycloalkyl group (5 to 60 carbon atoms, for example, cyclopentyl, cyclohexyl) , 4-t-butylcyclohexyl, 1-indanyl, cyclododecyl), an aryl group (6 to 60 carbon atoms, for example, phenyl, p-tolyl, naphthyl), an acylamino group (2 to 60 carbon atoms, for example, acetylamino, n-butanamide, octanoylamino, 2-hexyldecaneamide, 2- (2 ′,
4'-di-t-amylphenoxy) butanamide, benzoylamino, nicotinamide), sulfonamide group (1 to 60 carbon atoms, for example, methanesulfonamide, octanesulfonamide, benzenesulfonamide), ureide group (2 carbon atoms) -60, for example, decylaminocarbonylamino, di-n-octylaminocarbonylamino),

Urethane groups (2 to 60 carbon atoms, for example, dodecyloxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino), and alkoxy groups (1 to 60 carbon atoms, for example, methoxy, ethoxy, butoxy, n- Octyloxy, hexadecyloxy, methoxyethoxy), aryloxy group (6 to 60 carbon atoms, for example, phenoxy, 2,4-di-t-)
Amylphenoxy, 4-t-octylphenoxy, naphthoxy), alkylthio group (having 1 to 60 carbon atoms, for example,
Methylthio, ethylthio, butylthio, hexadecylthio), an arylthio group (6 to 60 carbon atoms, for example, phenylthio, 4-todecyloxyphenylthio), an acyl group (1 to 60 carbon atoms, for example, acetyl, benzoyl,
Butanoyl, dodecanoyl), sulfonyl group (1 carbon atom)
~ 60. For example, methanesulfonyl, butanesulfonyl, toluenesulfonyl), cyano group, carbamoyl group (1 to 60 carbon atoms, for example, N, N-dicyclohexylcarbamoyl),

Sulfamoyl group (0 to 60 carbon atoms, for example, N, N-dimethylsulfamoyl), hydroxy group, sulfo group, carboxyl group, nitro group, alkylamino group (1 to 60 carbon atoms, for example, methylamino) , Diethylamino, octylamino, octadecylamino),
An arylamino group (6 to 60 carbon atoms; for example, phenylamino, naphthylamino, N-methyl-N-phenylamino), a heterocyclic group (0 to 60 carbon atoms, preferably a nitrogen atom Those selected from an oxygen atom and a sulfur atom, which further contain a carbon atom as a ring-constituting atom in addition to a hetero atom, are more preferably 3 to 8, and more preferably 5 to 6 ring members.
And acyloxy groups (carbon 1 to 60; for example, formyloxy, acetyloxy, myristoyloxy, benzoyloxy) and the like.

The above substituent which the nitrogen-containing heterocyclic group may have may be further substituted with a substituent. Among the substituents that the nitrogen-containing heterocyclic group may have, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group When it is a group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, examples of the substituent which these groups may have include, for example, an alkyl group, a cycloalkyl group, an aryl group, an acylamino group, a ureido group, a urethane group, and an alkoxy group. , An aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfonyl group, a cyano group, a carbamoyl group, and a sulfamoyl group.

Among the substituents which the nitrogen-containing heterocyclic group may have, preferred are an alkyl group, an aryl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group and a cyano group. .

In the general formula (I), X and Y each independently represent ＯO, ＳS or ＮN—R, preferably ＝ O or ＮN—R, more preferably ＝ O. is there.

R represents a substituent. Examples of the substituent include an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, an acyl group, and an aryl group. Examples include an oxycarbonyl group, an alkoxycarbonyl group, and a carbamoyl group.

More specifically, R is an alkyl group [linear,
Represents a branched or cyclic substituted or unsubstituted alkyl group.
An 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),
A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably substituted with 5 to 30 carbon atoms) Or an unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptane-2-yl, bicyclo [ 2,
2,2] octan-3-yl), and a tricyclo structure having more ring structures. An alkyl partial structure in a substituent described below (for example, an alkyl partial structure in an alkylthio group) also means an alkyl partial structure having such a concept. An alkenyl group [which represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group; An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted 3 to 30 carbon atoms); A cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, for example, 2-
Cyclopenten-1-yl, 2-cyclohexen-1-
Yl), a 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] oct-2-en-4-yl)], alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group, aryl group (preferably Is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 or 6-membered substituted or A monovalent group obtained by removing one hydrogen atom from an unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2
-Pyrimidinyl, 2-benzothiazolyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example,
Acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxy Carbonyl,
o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted alkoxycarbonyl groups, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably having 1 carbon atom)
To 30 substituted or unsubstituted carbamoyl, such as carbamoyl, N-methylcarbamoyl, N, N-
Dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl). Among the above functional groups, those having a hydrogen atom may be removed, and further substituted with the above group. Examples of such a functional group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples include methylsulfonylaminocarbonyl, p
-Methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, benzoylaminosulfonyl groups. R is preferably an alkyl group or an aryl group, and most preferably an aryl group among the above substituents.

Z represents a substituted aryl group, preferably having 6 to 60 carbon atoms, wherein the aryl group has a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), and an alkenyl group (a cycloalkyl group). Alkenyl group, 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 alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino Group, Alkyl or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group,
Alkyl and aryl sulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups,
Examples include a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

Hereinafter, the substituent of the substituted aryl group will be described in more detail. The substituent of the substituted aryl group represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. Alkyl group (preferably having 1 to 30 carbon atoms)
Alkyl groups such as methyl, ethyl, n-propyl,
Isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl group (preferably having 3 carbon atoms)
To 30 substituted or unsubstituted cycloalkyl groups such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms, This is a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptane-2-yl and bicyclo [2,2,2] octane-3-. Yl), and a tricyclo structure having more ring structures. An alkyl partial structure in a substituent described below (for example, an alkyl partial structure in an alkylthio group) also means an alkyl partial structure having such a concept. Alkenyl group [linear, branched,
Represents a cyclic substituted or unsubstituted alkenyl group. An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted 3 to 30 carbon atoms); A cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a bicycloalkenyl group (A substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [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 carbon number 6 to 30 substituted or unsubstituted aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5 or 6-membered substituted or unsubstituted). A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and more preferably 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, hydroxyl group, nitro group, carboxyl 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), 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),
A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms) Group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, 6 to 30 carbon atoms) A substituted or unsubstituted arylcarbonyloxy group (for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy),
A carbamoyloxy group (preferably having 1 to 30 carbon atoms)
Substituted or unsubstituted carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octyl Carbamoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms)
A substituted or unsubstituted alkoxycarbonyloxy group,
For example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, Phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, and 6 carbon atoms) To 30 substituted or unsubstituted anilino groups, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, having 1 to 3 carbon atoms) A substituted or 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), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylamino Carbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably 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, mn-octyloxy, phenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, , Sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfones having 1 to 30 carbon atoms) Nylamino, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), A mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably having 6 carbon atoms)
To 30 substituted or unsubstituted arylthio, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, , 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), 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), sulfo group, alkyl and arylsulfinyl group (preferably having 1 to 30 carbon atoms) Or an unsubstituted alkylsulfinyl group, 6 to 30 substituted or unsubstituted arylsulfinyl groups, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably having 1 to 30 substituted or unsubstituted alkylsulfonyl groups, 6 to 30 substituted or unsubstituted arylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl Groups (preferably formyl groups, substituted or unsubstituted alkylcarbonyl groups having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl groups having 7 to 30 carbon atoms, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, Benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl group (preferably substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitro Phenoxycarbonyl, 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 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 arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms) For example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazole-2
-Ylazo), imide group (preferably N-succinimide, N-phthalimido), phosphino group (preferably substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methyl) Phenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, 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 having 2 to 30 carbon atoms); A substituted or unsubstituted phosphinylamino group, for example, Dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl) . Among the above functional groups, those having a hydrogen atom may be removed, and further substituted with the above group. Examples of such a functional group include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups. Preferred are a halogen atom, an alkyl group, an aryl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, a sulfonyl group, an alkoxy group, and an aryloxy group. Z
Is a phenyl group in which at least a halogen atom or an alkoxy group is substituted at the 2-position (the phenyl group may further have a substituent at the 3- to 6-positions, and particularly preferably has a substituent at the 5-position. Is preferred.

The coupler of the present invention represented by the above general formula may form a dimer or higher multimer via W, R or Z, or may be bonded to a polymer chain. .
Hereinafter, specific examples of the coupler of the present invention are shown, but the present invention is not limited thereto. In the following formulas, -ph is a phenyl group (-C ₆ H _5).

[0022]

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[0023]

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[0024]

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[0025]

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The couplers of the present invention are novel dye-forming couplers, which can be synthesized from inexpensive raw materials in a relatively short time. A specific synthesis example is shown below.

Synthesis Example 1 Synthesis of Coupler (1) Coupler (1) was synthesized by the following route.

[0028]

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Synthesis of Compound (T-3) Compound (T-1), 26.0 g (0.13 mol) and compound (T-3)
2) 64.0 g (0.12 mol) of dimethylformamide 17
After dissolving in 0 ml, 31 g of dicyclohexylcarbodiimide dissolved in 50 ml of dimethylformamide was added thereto.
(0.15 mol) was added dropwise. After stirring at room temperature for 3 hours,
3 ml of acetic acid and 12 ml of methanol were added to the reaction system,
Stirred for an additional 30 minutes. The precipitated dicyclohexylurea was removed by filtration, 500 ml of methanol was added to the filtrate, the mixture was heated to 50 ° C., 12 ml of water was added, and the mixture was allowed to cool at room temperature. The precipitated crystals were collected by filtration and recrystallized from 150 ml of methanol to obtain 73 g of a compound (T-3) (yield: 82%).
%) As white crystals.

Synthesis of Compound (T-4) 45 g (0.059 mol) of Compound (T-3) was dissolved in 300 ml of chloroform, and 20 g (0.059 mol) of pyridium hydrobromide perbromide was added thereto with stirring. Was. After stirring at room temperature for another 2 hours, the reaction solution was washed with water and saturated saline, and the organic layer was dried over magnesium sulfate. After filtering off magnesium sulfate, chloroform was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 40 g (yield 83%) of compound (T-4) as white crystals.

Synthesis of Compound (T-5) After dissolving 3.9 g (0.048 mol) of sodium acetate in 120 ml of dimethylformamide, this was dissolved in 120 ml of methylene chloride while stirring at room temperature.
-4) 35 g (0.043 mol) was added dropwise. After further stirring at room temperature for 5 hours, 200 ml of ethyl acetate was added, and the mixture was washed with diluted hydrochloric acid and saturated saline. After drying the organic layer, ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 25 g of compound (T-5).
(73% yield) as white crystals.

Synthesis of Compound (T-6) 2 g of potassium hydroxide was dissolved in 250 ml of methanol,
While stirring at room temperature, 25 g (0.031 mol) of the compound (T-5) was added. After stirring at room temperature for 2 hours, concentrated hydrochloric acid 2.5ml
Was added, and the precipitated crystals were collected by filtration. By recrystallizing the obtained crystals with acetonitrile, compound (T-6)
22 g (yield 92%) were obtained as white crystals.

Synthesis of coupler (1) 10 g (0.013 mol) of compound (T-6) was dissolved in 70 ml of dimethylformamide, and 5.5 g of potassium carbonate was added thereto.
(0.040 mol) was added. This was cooled on ice, and 2 ml (0.016 mol) of phenyl chlorocarbonate was added dropwise while stirring. After completion of the addition, the temperature was raised to room temperature. After further stirring at room temperature for 8 hours, 100 ml of ethyl acetate was added, and the mixture was washed with diluted hydrochloric acid and saturated saline. After drying the organic layer, ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 2.4 g (yield 23%) of the objective coupler (1) as white crystals.

Synthesis Example 2: Synthesis of coupler (3) Coupler (3) was synthesized by the following route.

[0035]

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Synthesis of Compound (T-8) 20 g (0.098 mol) of Compound (T-1) and Compound (T-7)
After dissolving 30 g (0.098 mol) in 200 ml of dimethylformamide, 24 g (0.12 mol) of dicyclohexylcarbodiimide dissolved in 50 ml of dimethylformamide was added dropwise. After stirring at room temperature for 3 hours, 500 ml of chloroform was added to the reaction system, and the mixture was further stirred for 30 minutes. After removing the precipitated dicyclohexylurea by filtration, 3 ml of acetic acid and 5 ml of methanol were added to the filtrate,
After stirring for further 30 minutes, the reaction solution was washed with diluted hydrochloric acid and saturated saline. After drying the organic layer, chloroform was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain 30 g (yield 62%) of compound (T-8) as white crystals.

Synthesis of Compound (T-9) 29 g (0.059 mol) of the compound (T-8) was dissolved in 400 ml of chloroform, and 22 g (0.069 mol) of pyridium hydrobromide perbromide was added thereto with stirring. Was. After stirring at room temperature for another 1 hour, the reaction solution was washed with water and saturated saline, and the organic layer was dried over magnesium sulfate. After filtering off magnesium sulfate, chloroform was distilled off under reduced pressure.
The residue was purified by column chromatography to obtain 26 g (yield 77%) of compound (T-9) as white crystals.

Synthesis of Compound (T-10) After dissolving 4.0 g (0.049 mol) of sodium acetate in 200 ml of dimethylformamide, the compound (T-10) was dissolved in 100 ml of methylene chloride while stirring at room temperature.
-9) 25 g (0.044 mol) was added dropwise. After further stirring at room temperature for 6 hours, 200 ml of ethyl acetate was added, and the mixture was washed with diluted hydrochloric acid and saturated saline. After drying the organic layer, ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 24 g of compound (T-10).
(98% yield) as white crystals.

Compound (T-11) 24 g (0.043 mol) of compound (T-10) was suspended in 200 ml of methanol, and 6.5 ml of a 25% aqueous ammonia solution was added thereto.
Was added. After stirring for 3 hours, 7 ml of concentrated hydrochloric acid and water were added to the reaction system.
200 ml was added, and the precipitated crystals were collected by filtration and washed sequentially with water and methanol. The obtained crystals were recrystallized from acetonitrile to give 17 g of compound (T-11) (yield 78
%) As white crystals.

Synthesis of coupler (3) 15 g (0.030 mol) of the compound (T-11) was dissolved in 200 ml of N-methyl-2-pyrrolidone, and potassium carbonate was added to the solution.
2 g (0.088 mol) were added. While cooling this with ice and stirring, 7.5 ml (0.059 mol) of phenyl chlorocarbonate was added dropwise,
After completion of the dropwise addition, the temperature was raised to room temperature. After stirring at room temperature for further 8 hours, the reaction solution was poured into ice water to which 5 ml of concentrated hydrochloric acid was added, and 300 ml of ethyl acetate was added thereto, followed by stirring. The organic layer was washed with dilute hydrochloric acid and saturated saline, dried, and then, ethyl acetate was distilled off under reduced pressure. The residue was purified by column chromatography to obtain the desired coupler (3) (7.9 g, yield 50%)
Was obtained as white crystals.

Here, the color-forming reaction mechanism of the dye-forming coupler represented by formula (I) of the present invention will be described. The dye-forming coupler of the present invention represented by the general formula (I) reacts with an oxidized aromatic primary amine developing agent to form a dye by the following reaction mechanism.

Color reaction mechanism

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In the above reaction scheme, the aromatic primary
The oxidized form of the amine-based developing agent is (T⁺). What
Contact, general formula (T⁺) Is, typically, R,
R₁And R_TwoEach independently represents a substituent, n is 0,
The description will be made assuming that it represents an integer of 1 to 4. Also, Bas
e represents a base. When the dye-forming coupler (I) is a base and oxygen
Atom and hydrogen atom on carbon atom substituted by WCO- group
An anion is generated by punching out the anion (a)
Is an oxidized form of an aromatic primary amine developing agent (T⁺)
Perform ordinary coupling reaction to produce intermediate (b)
You. This intermediate (b) is subsequently reacted with a base,
Nitrogen source substituted by a carbon atom of general formula (I) by a ring reaction
(T)⁺)But
An oxygen atom is released from the substituted carbon atom, and as a result, 5
When the member ring is cleaved to remove XCY (for example, when X and Y are both oxygen
If it is an atom, CO _TwoIe, decarboxylation)
Thereby, an intermediate (c) is obtained. This intermediate (c)
A hydrogen atom is supplied from a reaction solvent such as water,
(Dye). Therefore, this dye-forming coupler has 2
It is classified as an equivalent coupler.

The silver halide color photographic light-sensitive material used in the present invention will be described below. The light-sensitive material of the present invention is a silver halide photographic light-sensitive material having at least one light-sensitive layer formed on a support, wherein at least one of the light-sensitive layers has a compound represented by the formula (I). Wherein the coupler is contained in a hydrophilic colloid layer comprising a usual gelatin binder. In general, a light-sensitive material is provided with at least one light-sensitive emulsion layer (light-sensitive layer) of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. Can be configured in any order. Further, an infrared-sensitive silver halide emulsion layer can be used instead of one of the above-mentioned photosensitive emulsion layers. These light-sensitive emulsion layers contain a silver halide emulsion that has sensitivity in each wavelength range and a coupler that forms a dye that has a complementary color relationship with the light to be exposed, so that color reproduction by the subtractive color method can be performed. Can be. However, the photosensitive emulsion layer and the color hue of the coupler may not have the above correspondence.

The coupler used in the present invention is useful mainly as a yellow coupler or a magenta coupler, particularly as a yellow coupler in a conventional color light-sensitive material using a p-phenylenediamine as a color developing agent. A photosensitive emulsion layer (preferably a blue-sensitive silver halide emulsion layer or a green-sensitive silver halide emulsion layer, particularly preferably a blue-sensitive silver halide emulsion layer) can be contained. Also, p
-In a system using a color developing agent other than phenylenediamines, it is also useful as a dye-forming coupler for giving dyes of various hues. The amount of the coupler used in the present invention to the light-sensitive material is 1 × 10 5 per mol of silver halide.
^-3 to 1 mol is suitable, and more preferably 2 × 10 ^-3 to
3 × 10 ^-1 mol.

The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination), emulsified and dispersed in an aqueous gelatin solution, and halogenated. The oil-in-water dispersion method for addition to a silver emulsion is preferred. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in JP-A-5-313327 and JP-A-5-3235.
No. 39, No. 5-323541, No. 6-258803
No. 8-262662, U.S. Pat. No. 2,322,0
No. 27, etc. Further, the steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363.
No., West German Patent Application No. (OLS) 2,541,274,
No. 2,541,230, JP-B-53-41091, and European Patent Publication No. 029104.
PCT for dispersion with organic solvent soluble polymer
International Publication No. WO88 / 00723 and JP-A-5-15
No. 0420 and the like. Methacrylate-based or acrylamide-based polymers are preferred, and acrylamide-based polymers are particularly preferred in view of image fastness.

Here, the high boiling point means a boiling point of 175 ° C. or more at normal pressure. Examples of the high boiling point solvent used in the present invention are described in U.S. Pat. No. 2,322,027 and the like. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at normal pressure include phthalic acid esters such as dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, and bis (2,4-diethyl phthalate). -Tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate],
Esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate , Ji-
2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), sulfonamides (eg, N-butylbenzenesulfonamide),
Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctylazelate, glycerol tributyrate, isostearyl Lactate, trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene), chlorinated paraffins, etc. Is mentioned. In particular, phosphoric esters and
The hydrogen donating compounds described in 258803 and 8-262662 are excellent in terms of hue and can be preferably used.

In order to reduce the load on the environment,
In place of phthalates, European Patent EP-9693
It is preferable to use 20A1 and EP-969321A1, and in addition, tributyl citrate,
Pentaglycerin triester and the like. The dielectric constant of the high-boiling organic solvent varies depending on the purpose, but is preferably 2.0 to 7.0, and more preferably 3.0 to 6.0. The high-boiling organic solvent has a mass ratio of 0 to the coupler.
It is preferable to use 10 times, preferably 0 to 4 times the amount.

As the auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or more, preferably 50 ° C. to about 160 ° C. can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, and methyl ethyl ketone. ,
Examples include cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The emulsion dispersion may be used, if necessary, from the viewpoint of improving the stability over time during storage in the state of the emulsion dispersion, suppressing the change in photographic properties and improving the stability over time in the final composition for coating mixed with the emulsion. Thus, all or a part of the auxiliary solvent can be removed by a method such as vacuum distillation, noodle washing or ultrafiltration. The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.001 to 1.0 μm, more preferably 0.05 to 0.30 μm, and most preferably 0.08 to 0.20 μm. It is. Average particle size is Coulter submicron particle analyzer model N4 (Coulter Electronics)
And the like. If the average particle size of the lipophilic fine particle dispersion is large, the coloring efficiency of the coupler may be reduced, or the glossiness of the surface of the photosensitive material may be deteriorated.If the size is too small, the viscosity of the dispersion increases. , Making it difficult to handle during manufacture.

The amount of the lipophilic fine particle dispersion comprising the coupler of the present invention to be used in the dispersion medium is preferably 2 to 0.1, more preferably 1.
The range is from 0 to 0.2. Here, a typical dispersion medium is, for example, gelatin, and a hydrophilic polymer such as polyvinyl alcohol. The lipophilic fine particle dispersion can contain various compounds according to the purpose together with the coupler of the present invention.

The silver halide photographic light-sensitive material of the present invention includes:
In addition, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transparent support include transparent films such as cellulose nitrate film and polyethylene terephthalate, as well as 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG).
And a polyester of NDCA, terephthalic acid and EG, etc., provided with an information recording layer such as a magnetic layer is preferably used. The reflective support is particularly laminated with a plurality of polyethylene layers and polyester layers,
A reflective support containing a white pigment such as titanium oxide in at least one such water-resistant resin layer (laminate layer) is preferred.

A more preferred reflective support in the present invention is one having a polyolefin layer having micropores on the paper substrate on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer, preferably on the side of the silver halide emulsion layer, has no microvoids (eg polypropylene, polyethylene) and is close to the paper substrate More preferably, it is made of a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of these multilayers or polyolefin layers located between the paper substrate and the photographic component layer is between 0.40 and 0.40.
1.0 g / ml, preferably 0.50 to 0.1 g / ml.
70 g / ml is more preferred. The thickness of the multilayer or one polyolefin layer located between the paper substrate and the photographic component layer is preferably from 10 to 100 μm,
~ 70 µm is more preferred. Further, the thickness ratio of the polyolefin layer and the paper substrate is preferably 0.05 to 0.2,
0.1-0.5 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (back side) of the paper substrate from the photographic component layer in order to increase the rigidity of the reflection support. In this case, the polyolefin layer on the back side has a matte surface. Preferred is polyethylene or polypropylene, and more preferred is polypropylene. The back side polyolefin layer preferably has a thickness of 5 to 50 μm, more preferably 10 to 30 μm, and further preferably has a density of 0.7 to 1.1 g / ml. In the reflection support of the present invention, a preferred embodiment relating to a polyolefin layer provided on a paper substrate is described in JP-A-10-3.
No. 33277, No. 10-333278, No. 11-52
No. 513, No. 11-65024, EP0880065
And the examples described in EP 0 880 066.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. Further, the fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the photosensitive material. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent is used, and more preferably, a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is used. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by mass, and more preferably 0.001 to 0.5% by mass, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

As a support for use in the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment was provided on a support having a silver halide emulsion layer for a display. A support may be used. In order to further improve the sharpness, it is preferable to provide an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.35 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set the value in the range of -0.8.

In the photographic material according to the present invention, the hydrophilic colloid layer can be decolorized by the treatment described in EP 0,337,490 A2, pp. 27-76, for the purpose of improving the sharpness of the image. Dyes (among which are oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or dihydric alcohols (for example, Titanium oxide surface-treated with trimethylolethane)
The content is preferably 2% by mass or more (more preferably 14% by mass or more).

The light-sensitive material according to the present invention has a hydrophilic colloid layer for the purpose of preventing irradiation and halation and improving safelight safety, and the like. It is preferable to add the dyes described above that can be decolorized by the treatment (among others, oxonol dyes and cyanine dyes). Furthermore, dyes described in European Patent EP 0819977 are preferably added to the present invention. Some of these water-soluble dyes deteriorate color separation and safelight safety when used in an increased amount. Dyes which can be used without deteriorating color separation are described in JP-A-5-127324 and 5-1.
The water-soluble dyes described in Nos. 27325 and 5-216185 are preferred.

In the present invention, a colored layer which can be decolorized by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below (on the side of the support) the emulsion layer that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select and install only a part of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is within the wavelength range used for exposure (400 nm to 700 nm in normal printer exposure).
It is preferable that the optical density value at the wavelength having the highest optical density in the visible light region of nm and the wavelength of the scanning exposure light source used in the case of scanning exposure) is 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, particularly preferably 0.8 or more and 2.0 or less.

In order to form a colored layer, a conventionally known method can be applied. For example, Japanese Patent Application Laid-Open No. 2-282244-3
Dyes described from the upper right column of the page to page 8 and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method in which a solid fine particle dispersion is contained in a hydrophilic colloid layer, a method in which an anionic dye is mordanted to a cationic polymer, and a dye is halogenated. Examples thereof include a method of adsorbing fine particles such as silver and fixing it in a layer, and a method of using colloidal silver as described in JP-A-1-239544. As a method of dispersing the fine powder of the dye in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in 2-30824
No. 4, pp. 4-13. Also, for example,
A method of mordanting an anionic dye into a cationic polymer is described in JP-A-2-84637, pp. 18-26. For a method for preparing colloidal silver as a light absorber, see U.S. Patent Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, a method of incorporating a fine powder dye and a method of using colloidal silver are preferred.

The silver halide grains in the silver halide emulsion used in the present invention are preferably cubic or tetradecahedral crystal grains having substantially {100} faces (these grains are rounded at the apex of the grains and higher in height). Or octahedral crystal grains, or 50 of total projected area
% Or more are tabular grains having an aspect ratio of 2 or more composed of {100} planes or {111} planes. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of a particle. In the present invention, a cubic or tabular grain having a {100} plane as a principal plane or a tabular grain having a {111} plane as a principal plane is preferably applied.

As the silver halide emulsion used in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsion and the like can be used. A silver chloride or silver chlorobromide emulsion having a content of 95 mol% or more is preferable, and a silver halide emulsion having a silver chloride content of 98 mol% or more is preferable. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable because high sensitivity can be obtained and photographic performance can be stabilized.

The localized silver bromide phase is preferably formed by epitaxially growing a localized phase having a total silver bromide content of at least 10 mol% or more in the localized silver bromide phase. The silver bromide content of the silver bromide localized phase is preferably in the range of 10 to 60 mol%, most preferably in the range of 20 to 50 mol%.
The silver bromide localized phase is preferably composed of silver in an amount of 0.1 to 5 mol% of the total silver constituting the silver halide grains in the present invention, and is preferably composed of 0.3 to 4 mol% of silver. More preferably, it is constituted. In the localized phase of silver bromide, iridium (III) chloride, iridium (III) bromide,
Iridium (IV) chloride, sodium hexachloroiridate (III), hexachloroiridium (IV)
It is preferable to contain a Group VIII metal complex ion such as potassium acid, hexaammine iridium (IV) salt, trioxalatoiridium (III) salt, and trioxalatoiridium (IV) salt. The addition amount of these compounds may vary over a wide range depending on the purpose, but may be 10 to 1 mol of silver halide.
^-9 to 10 ^-2 mol is preferred.

The silver halide emulsion used in the present invention is
In the course of emulsion grain formation or physical ripening, various polyvalent metal ion impurities other than iridium can be introduced. Examples of compounds used include iron, ruthenium, osmium, rhenium, rhodium, cadmium,
Salts or complex salts of metals of Group VIII of the periodic table such as zinc, lead, copper, and thallium can be used in combination. In the present invention, a metal compound having at least four cyano ligands, such as iron, ruthenium, osmium, and rhenium, is particularly preferred in that it further enhances high illuminance sensitivity and suppresses latent image sensitization. The iridium compound has a great effect on imparting high illuminance exposure suitability. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grains, and the number average thereof is calculated) is 0.1. 1 μm to 2 μm is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide emulsion used in the present invention contains various compounds or their precursors for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are disclosed in the above-mentioned JP-A-62-2.
Those described on page 39 to page 72 of JP-A-15272 are preferably used. Furthermore, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP0447647 is also preferably used.

In the present invention, the hydroxamic acid derivatives described in JP-A-11-109576 and JP-A-11-32709 are disclosed in JP-A-11-109576 in order to enhance the storage stability of the silver halide emulsion.
Cyclic ketones having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group described in No. 4 (especially those represented by the general formula (S1), and paragraph numbers 0036 to 0071) Can be incorporated in the specification of the present application.) And sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example,
4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,
3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), and the general formulas (I) to (III) of JP-A-11-102045. The water-soluble reducing agent represented by is also preferably used in the present invention.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, FM Harmer's Heterocyclic compounds-Cyanine
dyes and related compounds (John Wiley & Sons [New
York, London], published in 1964). As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used. Particularly, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, JP-A No. 3-12 / 1991
The spectral sensitizing dye described in No. 3340 is very preferable from the viewpoints of stability, strength of adsorption, temperature dependency of exposure and the like.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be 0.5 to 0.5 mol per mol of silver halide.
The range is preferably from × 10 ^-6 mol to 1.0 × 10 ^-2 mol.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ^−3.
Range of moles.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column are preferably used. Among them, it is particularly preferable that the material is subjected to gold sensitization. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with a laser beam or the like can be further reduced. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanates, gold thiosulfates, and gold colloids can be used. The addition amount of these compounds may vary widely depending on the case, but is from 5 × 10 ^{−7 to} 5 × per mol of silver halide.
The amount is 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol. In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization using a compound other than a gold compound.

The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., and among them, a color photographic paper is preferable.
Color photographic paper has a yellow coloring silver halide emulsion layer,
It is preferable to have at least one layer each of a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer. A silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a cyan color-forming silver halide emulsion layer.

However, a different layer configuration may be adopted. The silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support, but when the yellow coupler containing layer contains silver halide tabular grains, the silver halide emulsion containing the magenta coupler may be used. It is preferable that the coating is provided at a position farther from the support than at least one of the emulsion layer and the silver halide emulsion layer containing a cyan coupler. Further, from the viewpoint of accelerating color development, desilvering, and reducing residual color by a sensitizing dye, the silver halide emulsion layer containing the yellow coupler is coated at a position farthest from the support than the other silver halide emulsion layers. Preferably, it is provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a layer at the center of the other silver halide emulsion layers, and from the viewpoint of reducing photo-fading, the cyan coupler-containing silver halide emulsion layer is preferably The lowermost layer is preferred. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, as described in JP-A-4-75055, JP-A-9-114035, JP-A-10-246940 and U.S. Pat. It is also preferable to provide a color-forming layer provided adjacent to the emulsion layer.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) used in the present invention, and the processing methods and processing additions applied for processing this light-sensitive material As the agent, JP-A-62-2
No. 15272, JP-A-2-33144, European Patent EP
No. 0,355,660 A2, particularly those described in European Patent EP 0,355,660 A2 are preferably used. Further, JP-A-5-34
No. 889, No. 4-359249, No. 4-313375
Nos. 4-270344, 5-66527, and 4
-34548, 4-145433, 2-854
Nos. 1-158431, 2-90145 and 3
Also preferred are silver halide color photographic light-sensitive materials described in, for example, JP-A-194539, JP-A-2-93641, and European Patent Publication No. 0520457A2, and a processing method thereof.

In particular, in the present invention, the above-mentioned reflective support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer of silver halide emulsion or antifoggant , Chemical sensitization method (sensitizer),
Spectral sensitization (spectral sensitizer), cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin, photosensitive materials With respect to the layer constitution and the coating pH of the photosensitive material, those described in the patents of Tables 1 and 2 can be particularly preferably applied.

[0075]

[Table 1]

[0076]

[Table 2]

The cyan, magenta and yellow couplers used in combination in the present invention are described in
JP-A-2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column last line and page 30, upper right Column 6th line to page 35, lower right column, line 11 and EP0,355,660A2
Page 4 lines 15-27, page 5 line 30-page 28 last line, page 45 lines 29-31, page 47 line 23-
The couplers described on page 63, line 50 are also useful. Also,
The present invention relates to the general formulas (II) and (III) of WO-98 / 33760 and the general formula (D) of JP-A-10-221825.
A compound represented by formula (I) may be added, which is preferable.

This will be described more specifically below. In the present invention, the coupler of the present invention may be used alone or in combination. Examples of the yellow coupler which may be used in combination with the coupler of the present invention include, in addition to the compounds described in the above table, acylacetamide type having a 3- to 5-membered cyclic structure in an acyl group described in European Patent EP0447969A1. A yellow coupler, a malondianilide-type yellow coupler having a cyclic structure described in European Patent EP0484822A1, and an acylacetamide-type yellow coupler having a dioxane structure described in US Pat. No. 5,118,599 are preferably used. Can be Among them, an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides forms an indoline ring are particularly preferably used.

In the present invention, the cyan coupler is preferably a phenol-based or naphthol-based cyan coupler or a heterocyclic coupler. Examples of phenolic couplers other than the above table include, for example, JP-A-10-33329.
No. 7 is preferably a cyan coupler represented by the general formula (ADF). Further, the 2,5-diacylaminophenol coupler described in U.S. Pat. No. 5,888,716 with improved hue and fastness is preferably used.

As heterocyclic couplers, European Patent EP
Pyrroazole type cyan couplers described in U.S. Pat. No. 4,488,248 and EP0491197A1, U.S. Pat. Nos. 4,873,183 and 4,916,051
Pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in JP-A No.
No. 71185, No. 8-31360, No. 8-3390
It is also preferable to use in combination with a pyrazoloazole-type cyan coupler having a carbamoyl group at the 6-position described in No. 60. In addition,
Of these cyan couplers, JP-A-11-2821
Particularly preferred is a pyrroloazole-based cyan coupler represented by the general formula (I) described in JP-A No. 38, paragraph No. 0 of the patent.
Descriptions of 012 to 0059 are for example cyan coupler (1) to
Including (47), it is applied to the present application as it is, and is preferably incorporated as a part of the specification of the present application.

Further, in addition to the diphenylimidazole cyan couplers described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent EP 0 333 185 A2 (among the couplers listed as specific examples) (42) 4-equivalent coupler having a chlorine leaving group to give a 2-equivalent coupler, couplers (6) and (9) are particularly preferred) and JP-A-64-322.
No. 60, the cyclic active methylene cyan coupler (among others, coupler examples 3, which are listed as specific examples,
8, 34 are particularly preferred), EP 0 422 622
It can be used in combination with a pyrrolopyrazole-type cyan coupler described in 6A1 and a pyrroleimidazole-type cyan coupler described in European Patent EP 0484909.

As the magenta coupler used in the present invention, a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler as described in the publicly known documents in the above table are used.
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245 in terms of color development and the like. Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-65246, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254, and Europe Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in A or 294,785A. In particular, magenta couplers represented by the general formula (M) described in JP-A-8-122984
Pyrazoloazole couplers represented by -I) are preferred, and paragraphs [0009] to [0026] of the patent are applied to the present application as they are and are incorporated as a part of the specification of the present application. In addition to this, European Patent Nos. 854384 and 8
Pyrazoloazole couplers having a sterically hindered group at both the 3- and 6-positions described in 84640 are also preferably used.

Like the couplers of the present invention, magenta or cyan couplers can also be used in the presence (or absence) of the high boiling organic solvents listed in the preceding table, in the presence or absence of a loadable latex polymer (eg, US Pat. No. 4,203, 716)
It is preferable to emulsify or disperse in a hydrophilic colloid aqueous solution by impregnating with water or dissolving with a water-insoluble and organic solvent-soluble polymer. Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and WO 88/00723, pages 12 to 30. The homopolymer or copolymer described above may be used. More preferably, use of a methacrylate-based or acrylamide-based polymer, particularly, an acrylamide-based polymer is preferred from the viewpoint of color image stability and the like. Further, in terms of suppressing Brix discoloration (defective color reversal) by a bleaching solution or a bleach-fixing solution, JP-A-8-62797, JP-A-9-171240 and JP-A-9-329861 disclose a hydrophilic colloid layer in a hydrophilic colloid layer. It is preferred to use the described polymers.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high-molecular-weight redox compounds described in JP-A-5-333501, WO98 / 33
No. 760, U.S. Pat. No. 4,923,787, etc .; phenidone and hydrazine compounds;
No. 37, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, the pH of the developer is increased,
In the case of speeding up development, German Patent No. 1961878
It is also preferable to use the redox compounds described in 6A1, EP 839623 A1, EP 842975 A1, German Patent 19806846 A1, French Patent 2760460 A1, and the like.

In the present invention, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as the ultraviolet absorber. For example, the compounds described in the following patents can be used. JP-A-46-3335, 55
-152776, JP-A-5-1970074, 5-
No. 232630, No. 5-307232, No. 6-211
No. 813, No. 8-53427, No. 8-234364
Nos. 8-239368, 9-31067, 1
Nos. 0-115598, 10-147577, 10
182621, German Patent 19739797A,
European Patent No. 711804A and Japanese Patent Publication No. Hei 8-5012
No. 91 and the like.

In the present invention, as a discoloration preventing agent and a hue adjusting agent other than the above, vinyl compounds represented by the general formula (II) described in JP-A-11-258748 and compounds represented by the general formula (III) A aniline derivative having an oxygen-nitrogen bond or an alkoxy-substituted aniline derivative, a diffusion-resistant phenidone derivative represented by the general formula (IV), a diffusion-resistant carboxylic acid represented by the general formula (V), a general formula (VI) Embedded image, an arylamide derivative represented by the general formula (VII), and a cyclic imide derivative represented by the general formula (VIII), all of which can be preferably used.

As a binder or protective colloid that can be used in the light-sensitive material according to the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin. As a preferred gelatin, heavy metals contained as impurities such as iron, copper, zinc, and manganese are preferably 5 ppm.
Or less, more preferably 3 ppm or less. The amount of calcium contained in the photosensitive material is preferably 20 mg.
/ M ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less. In the present invention,
In order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a bactericidal / antifungal agent as described in JP-A-63-271247. Further, the coating pH of the photosensitive material is preferably from 4.0 to 7.0, and more preferably from 4.0 to 6.5.

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, a cathode ray. A plurality of color image signals may be input to the tube to emit light from the tube surface. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a second harmonic emission light source (SHG) in which a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source is combined with a nonlinear optical crystal.
A digital scanning exposure method using monochromatic high-density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the photosensitive material of the present invention depends on the scanning used.
It can be set arbitrarily according to the wavelength of the exposure light source.
Solid-state laser using semiconductor laser as excitation light source or
Is obtained by combining a semiconductor laser and a nonlinear optical crystal.
SHG light source can halve laser oscillation wavelength
Therefore, blue light and green light can be obtained. Therefore, photosensitive material
The spectral sensitivity maximum is held in the normal three wavelength ranges of blue, green and red.
It is possible to add. In such scanning exposure
The exposure time is based on the pixel when the pixel density is 400 dpi.
If the size is defined as the exposure time, the preferred exposure
10 for time ^-FourSeconds or less, more preferably 10^-6Seconds
Below.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, the lower right column of page 26, lower right column of page 26 to the upper right column of page 34 of JP-A-2-207250, and the upper left column of page 5 of JP-A-4-97355 can be used. The processing materials and processing methods described in line 17 to page 20, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The present invention is preferably applied to light-sensitive materials having suitability for rapid processing. The color development time refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fix solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called submerged time) and the time when the photosensitive material leaves the color developing solution and is bleach-fixed in the next processing step The sum of the time during which it is transported in the air toward the bath (so-called air time) is referred to as the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath. The term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called submerged time).

In the present invention, the color development time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more.
More preferably, it is 30 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 5 seconds or less.
It is 6 seconds or more, preferably 0 second or less, more preferably 30 seconds or less. The washing or stabilization time is preferably 15 minutes.
The time is 0 second or less, more preferably 130 seconds or less and 6 seconds or more.

The method of developing the light-sensitive material of the present invention after exposure is a conventional method of developing with a developing solution containing an alkali agent and a developing agent, and a developing solution containing a developing agent incorporated in the light-sensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator liquid, a thermal development method without using a processing liquid can be used. In particular, since the activator method does not contain a developing agent in the processing solution, it is easy to manage and handle the processing solution, and is a preferable method from the viewpoint of environmental conservation because it has a small load when processing the waste liquid. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A-8-234.
No. 388, No. 9-152686, No. 9-152693
And hydrazine-type compounds described in JP-A Nos. 9-218814 and 9-160193.

Further, a developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Laid-Open
An image forming method using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

For the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, Research Disclosure Item 36544
(September 1994) Pages 536 to 541, JP-A-8
-234388 can be used.

When the photosensitive material of the present invention is exposed to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. In the present invention, as described in European Patent Nos. EP0789270A1 and EP0789480A1, before applying image information, a yellow microdot pattern may be pre-exposed in advance to control copying.

The light-sensitive material of the present invention can be preferably applied as a light-sensitive material for an advanced photo system having a magnetic recording layer. Further, the light-sensitive material of the present invention can be preferably applied to a system for heat development using a small amount of water or a completely dry system for heat development without using any water. These systems are described in JP-A-6-35118 and JP-A-6-17528,
Nos. 146,133 and 60-119557,
No. 161236 has a detailed description.

In the present invention, the silver halide photographic light-sensitive material includes not only a light-sensitive material for forming a color image but also a light-sensitive material.
The concept includes a photosensitive material that forms a monotone image including a black and white image.

When the coupler of the present invention is applied to color paper, photosensitive materials described in JP-A No. 11-7109 are preferred. Particularly, the description of paragraphs 007-0087 of JP-A No. 11-7109 is not limited. Incorporated as is as part of the specification of the present application. When the coupler of the present invention is applied to a color negative film, see JP-A-11-3.
The description of paragraph Nos. 0115 to 0217 of the specification of JP 05396 is preferably applied, and is incorporated as a part of the specification of the present application. When the coupler of the present invention is applied to a color reversal film, the description in paragraphs 0018 to 0021 of the specification of JP-A-11-84601 is preferably applied and incorporated as a part of the specification of the present application.

[0102]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 (Preparation of Sample 101) An emulsified dispersion of the comparative coupler (C-1) was prepared by the following method. Comparative coupler (C-
1), 0.88 g and tricresyl phosphate, 2.6 g
Was dissolved by heating in ethyl acetate (10 ml) (this was used as an oil phase liquid). Separately, 4.2 g of gelatin was added to
After swelling sufficiently, the mixture was heated to 40 ° C. and completely dissolved. While maintaining the gelatin aqueous solution at about 40 ° C., 3 ml of a 5% aqueous sodium dodecylbenzenesulfonate solution and the oil phase solution prepared above were added, and the mixture was emulsified and dispersed with a homogenizer to prepare an emulsified dispersion. Using this emulsified dispersion, a coating liquid having the following composition was prepared, and coated on a polyethylene laminated paper having an undercoat layer so that the coupler was 1 mmol / m ² . Further, 2 g / m ² of gelatin was coated thereon as a protective layer,
01 was produced.

[0104]

Embedded image

(Composition of Coating Solution) Emulsion: 13 g of silver chlorobromide (cubic particles based on silver chloride and having a total of 0.3 mol% of silver bromide in a part of the surface, average) Grain size 7 μm, spectral sensitization was imparted by adding sensitizing dyes A, B and C in an amount of 1.4 × 10 ^-4 mol per mol of silver halide, respectively.) 10% gelatin 28 g 22 g of emulsified dispersion of C-1) ・ 37 ml of water ・ 5 ml of 4% aqueous solution of sodium 1-hydroxy-3,5-dichloro-s-triazine

[0106]

Embedded image

(Preparation of Samples 102 to 106) Samples 102 to 106 were prepared in the same manner as Sample 101 except that the couplers of the present invention shown in Table 3 were added instead of the comparative couplers. The sample prepared as described above was subjected to wedge exposure with white light, and subjected to a color development process by the following process steps.

(Processing Step) Step Temperature Time Color development 38.5 ° C. 45 seconds Bleaching and fixing 30-36 ° C. 45 seconds Stable 30-37 ° C. 20 seconds Stable 30-37 ° C. 20 seconds Stable 30-37 ° C. 20 seconds Drying 70- 85 ° C 70 seconds

In each of the steps of color development, bleach-fixing, stabilization, stabilization and stabilization, processing was carried out by immersion in the following processing solutions under the above conditions. (Color developing solution in the color developing step) ・ Water 800 ml Dimethylpolysiloxane surfactant (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g ・ Triethanolamine 11.6 g ・ Ethylenediaminetetraacetic acid 4.0 g 4.5 Sodium dihydroxybenzene-1,3-disulfonate 0.5 g, Potassium chloride 10.0 g, Potassium bromide 0.040 g Triazinylaminostilbene-based fluorescent whitening agent (Hakkol FWA-SF / Showa Chemical Co., Ltd.) 2.5 g・ Sodium sulfite 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5 g ・ N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline ・ 3 / 2 sulfuric acid / monohydrate 5.0g Potassium carbonate 26.3g Add water 1000 ml pH (adjusted with 25 ° C. / potassium hydroxide and sulfuric acid) 10.15

(Bleach-fixing solution in the bleach-fixing step) • 800 ml of water • 47.0 g of ammonium iron (III) ethylenediaminetetraacetate • 1.4 g of ethylenediaminetetraacetic acid • 8.3 g of m-carboxymethylbenzenesulfinic acid • nitric acid (67% 16.5 g Imidazole 14.6 g Ammonium thiosulfate aqueous solution (750 g / L) 107 ml Ammonium sulfite 16.0 g Potassium metabisulfite 23.1 g Add water 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 6 .0

(Stable-Stabilizing Solution in Process)-Chlorinated sodium isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

The density of the sample after the treatment was measured by using a densitometer X-light 404 manufactured by X-Light Corporation to measure the reflection density (yellow). Table 3 summarizes the obtained results.

[0113]

[Table 3]

As is clear from Table 3, it can be seen that all couplers of the present invention have excellent coloring properties. Also,
All of the samples of the present invention were superior to the comparative sample in yellow hue.

Example 2 After a corona discharge treatment was applied to the surface of a support having both sides of a paper covered with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. A photographic constituent layer of the seventh layer was sequentially coated to prepare a sample (001) of a silver halide color photographic light-sensitive material having the following layer constitution. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of coating solution for first layer 62 g of yellow coupler (ExY), color image stabilizer (Cp
d-1) 8 g, a color image stabilizer (Cpd-2) 4 g, a color image stabilizer (Cpd-3) 8 g, and a solvent (Solv-1) 23 g
And 80 ml of ethyl acetate, and this solution is emulsified and dispersed in 220 g of a 23.5% by mass gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate using a high-speed stirring emulsifier (dissolver), and water is added to 900 g of emulsified dispersion. Preparation A was prepared. On the other hand, silver chlorobromide emulsion A (cubic, large-size emulsion A having an average grain size of 0.72 μm and 0.60 μm
m 3: 3 mixture with small size emulsion A (silver molar ratio). The coefficient of variation of the particle size distribution was 0.08 and 0.1, respectively.
0. For each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain). This emulsion contains the following blue-sensitive sensitizing dyes A, B and C per mol of silver halide, 1.4 × 10 ^-4 mol for a large-size emulsion and 1.4 × 10 ^-4 mol for a small-size emulsion, respectively. 1.7 × 10 ^-4 mol is added. Also,
Chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer so as to have the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Ab-1 and Ab-
2, Ab-3 and Ab-4 each had a total amount of 15.0.
^{mg / m 2, 60.0mg / m} 2, was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0118]

Embedded image

The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0120]

Embedded image

(Sensitizing dyes A, B and C were used in an amount of 1.4.times.
^10-4 moles, ^1.7x each for small size emulsions
10 ^-4 mol was added. Green sensitive emulsion layer

[0122]

Embedded image

(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMol of sensitizing dye F per mol of silver halide.
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for size emulsion^-FourMole was added. ) Red-sensitive emulsion layer

[0124]

Embedded image

(Sensitizing dyes G and H were converted to silver halide 1
6.0 × 1 per mole for large size emulsions
0 ^-5 mol, respectively 9.0 × 1 to the small size emulsion
0 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide. )

[0126]

Embedded image

Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mol and 5.9 × 10^-FourMole was added. Furthermore, the second
Layer, the fourth layer, the sixth layer and the seventh layer, respectively.
mg / m ^Two0.2 mg / m^Two, 0.6 mg / m^Two, 0.
1mg / m^TwoWas added so that Blue-sensitive emulsion
Layer and the green-sensitive emulsion layer.
Chill-1,3,3a, 7-tetrazaindene,
Per mole of silver halide^-FourMole, 2 × 1
0^-FourMole was added.

In the red-sensitive emulsion layer, a copolymer of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 2
(0000 to 400,000) was added at 0.05 g / m ² . In addition, 6 mg each of disodium catechol-3,5-disulfonate was added to the second, fourth and sixth layers.
/ M ² , 6 mg / m ² , and 18 mg / m ² . To prevent irradiation, the following dyes were added to the emulsion layer.

[0129]

Embedded image

[0130]

Embedded image

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content 16% by mass, ZnO; content 4% by mass) and optical brighteners (4,4'-bis (benzoxazolyl) stilbene and 4,4'-bis (5-methylbenzoxazolyl)
8/2 mixture of stilbene: content 0.05% by mass),
Including blue dye (ultramarine)

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion A (cubic, 3: 7 mixture of large-size emulsion A with an average grain size of 0.72 μm and small-size emulsion A with a 0.60 μm size (silver mole The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. ) 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0 .08 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.45 μm and small-size emulsion B having an average grain size of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorption Agent (UV-4) 0.03 Ultraviolet absorber (UV-6) 0.01 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd) -6) 0.09 Color image stabilizer (Cpd-8) 0.02 Image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large emulsion C having an average grain size of 0.50 μm and small emulsion C of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd-6) 05 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) 0.01 color Image stabilizer (Cpd-15) 0.03 Color image stabilizer (Cpd-16) ) 0.05 Color image stabilizer (Cpd-17) 0.05 Color image stabilizer (Cpd-18) 0.06 Color image stabilizer (Cpd-19) 0.06 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05 Solvent (Solv-9) 0.10

Sixth layer (UV absorbing layer) Gelatin 0.66 UV absorbing agent (UV-1) 0.19 UV absorbing agent (UV-2) 0.06 UV absorbing agent (UV-3) 0.06 UV absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.08 Ultraviolet absorber (UV-6) 0.01 Solvent (Solv-7) 0.25 Seventh layer (protective layer) Gelatin 1. 00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

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Further, except that the yellow coupler of the emulsified dispersion A for the first layer of the silver halide color photographic light-sensitive material (001) prepared as described above was replaced by the same molar amount as the above-mentioned coupler (C-1). A photosensitive material 201 was produced in exactly the same manner. Similarly, the light-sensitive materials (202) to (202) to (9) were identical to the couplers (1), (3), (5), (7) and (9) used in Example 1 except that they were each substituted in the same molar amount. (206) was produced.

The above photosensitive material (001) was treated at 25 ° C. and 55% R
After storing in H for 10 days, processed into a 127 mm wide roll, imagewise exposed using Fuji Photo Film Co., Ltd. Minilab Printer Processor PP1258AR, and replenished twice the color developing tank capacity in the following processing steps , Continuous processing (running test). Processing Step Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds - rinse (3) ** 38.0 ℃ 20 seconds - rinse (4) ** 38.0 ℃ 30 seconds 121 ml * phosphorus replenishment rate ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D per photosensitive material 1 m ² The rinsing liquid is taken out of the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml dimethylpolysiloxane-based surfactant (silicon KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g 0.1 g triethanolamine 11.6 g 11. 6g Ethylenediaminetetraacetic acid 4.0g 4.0g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5g 0.5g Potassium chloride 10.0g-Potassium bromide 0.040g 0.010g Triazinylaminostilbene 2.5g 5.0g sodium sulfite 0.1g 0.1g disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5g 11.1g N-ethyl-N- (β-methanesulfonamide ethyl ) -3-Methyl-4-amino-4-aminoaminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g Potassium carbonate 26.3 g 26.3 g Water was added to the mixture, and 1000 ml 1000 ml pH (25 ° C) / Adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 ml 800 ml ethylenediaminetetraacetic acid iron (III) ammonium 47.0 g 94.0 g ethylenediaminetetraacetic acid 1.4 g 2.8 g m-carboxymethylbenzene Sulfinic acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / L) 107 mL 214 mL Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23 .1g 46.2g Water was added to add 1000ml 1000ml pH (adjusted at 25 ° C / acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μS / cm or less) 1000 ml 1000 ml pH 6.5 6.5

Next, a sensitometer (Fuji Photo Film Co., Ltd., FWH type, light source color temperature 3200 ° K) is applied to each photosensitive material.
Was used to provide a gradation exposure with a three-color separation optical wedge for sensitometry. The exposure at this time was performed so that the exposure amount was 250 lx · sec (lux · sec) with an exposure time of 0.1 second. Separately, scanning exposures shown below were performed on each photosensitive material. JP-A-8-1
The scanning exposure apparatus of FIG. 1 of No. 6238 was used. As the light source, a 688 nm light source (G light) and a 473 nm light source (B light) were obtained by combining a semiconductor laser with a 688 nm light source (R light) using a semiconductor laser and SHG. The amount of R light was modulated using an external modulator, reflected on a rotating polyhedron, and scanned and exposed on a sample moving perpendicular to the scanning direction. The scanning exposure was performed at 400 dpi, and the average exposure time per pixel was 8 × 10 ⁻⁸ seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress a change in light amount due to temperature.

Each of the exposed samples was developed using the above-mentioned running processing solution, and the same evaluation as that for the photosensitive material performed in Example 1 was performed. As a result, it was confirmed that all of the couplers of the present invention had high coloring properties.

Example 3 Photosensitivity differing only in that ExY-2 and ExY-3 of the 13th and 14th layers of Sample 101 of JP-A-11-305396 were changed to the coupler (1) of the present invention in equimolar amounts. A material was prepared, and Example 1 of JP-A-11-305396 was used.
As described in Example 1 of the present application, it was confirmed that all of the couplers of the present invention had high coloring properties, as in Example 1 of the present invention.

Example 4 In Example 1 of JP-A-11-84601, the sample 10
The couplers C-5, C-6 and C-10 of the 13th and 14th layers of No. 7 and the C-6 and C-10 of the 15th layer were all equimolarly changed to the coupler (1) of the present invention. A photosensitive material that differs only in the above was prepared, exposed and developed by the method described in Example 1 of JP-A-11-84601, and evaluated by the method described in the example of the present application. It was confirmed that all of the couplers of the present invention had high coloring properties.

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The dye-forming coupler of the present invention provides a silver halide color photographic light-sensitive material image which is excellent in color developability, can be produced at low cost, has a high color density and excellent sharpness.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yasuhiro Shimada 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F term (reference) 2H016 BE02 BF00 BG01 4C063 AA01 BB04 CC52 DD06 EE05

Claims (2)

[Claims] 1. A dye-forming coupler represented by the following general formula (I). Embedded image In the general formula (I), W represents a nitrogen-containing heterocyclic group, and Z represents a substituted aryl group. X and Y are each independently:
Represents O, = S or = N-R. Here, R represents a substituent. 2. A silver halide color photographic material comprising at least one of the dye-forming couplers represented by formula (I).