JP2001281819A - Silver halide photographic sensitive material and method for producing azo dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in hue and having a high molecular extinction coefficient and good shelf stability, and an easy method for producing an azo dye. SOLUTION: The silver halide photographic sensitive material contains at least one coupler of formula (I) (where Z is a group of carbon and/or nitrogen atoms forming a 5 or 6-membered aromatic ring together with N-C; R is a substituent; (m) is 0 or an integer of 1-4; X is carbonyl, methylene which may have a substituent or >C=N-Rn; Rn is a substituent; and Y is H or a substituent) and the method for producing an azo dye uses a compound of the formula (I).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material containing a coupler which forms a heterocyclic azo dye by a coupling reaction with an oxidized form of a developing agent. Further, the present invention relates to a method for producing a heterocyclic azo dye which can be produced by the above reaction.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material obtained by a subtractive color method (hereinafter sometimes simply referred to as "light-sensitive material"), a color image is formed by three primary colors 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 hue. In addition, a large amount of coupler and silver halide are required, and there is a problem that the sharpness of a color image obtained by the increase of the film thickness of the light-sensitive material may be reduced. Further, the dye is easily decomposed under high-temperature and high-humidity conditions, and there is a problem in image storability after development processing, and improvement is desired.

In order to solve these problems, acyl groups and anilide groups have been improved. Recently, as a coupler obtained by improving a conventional acylacetic acid anilide system, a coupler described in Japanese Patent Application Laid-Open No. H4-218042 has been disclosed. -Alkylcyclopropanecarbonylacetic acid anilide-based compounds and
A cyclic malondiamide-type coupler described in JP-A-11416 has been proposed. Dyes produced from these couplers were improved in hue and molecular extinction coefficient compared to conventional ones, but they were still insufficient in terms of image storability, and the cost of couplers increased due to the complicated structure. There is a problem in practice.

As a yellow coupler for forming an azo dye having a high extinction coefficient, instead of the existing coupler for forming an azomethine dye, a benzoisoxazolone-based compound described in British Patent No. 778,089 or a British Patent No. An indazole compound described in 875,470 has been proposed. However, the dye derived from the coupler has not been practically used because it has an essential problem that the absorption becomes longer due to intramolecular hydrogen bonding at neutral. Similarly, as a yellow coupler which forms an azo dye having a high absorption coefficient, there is a compound described in JP-A-10-148921. However, the coupler was not practical because it had a problem that the pKa was high and the coupling activity was insufficient, and if the pKa was lowered to increase the activity, the hue deteriorated. In addition, development of a simple method for producing an azo dye,
In particular, a method for producing an azo dye using a coupler has been required.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a light-sensitive material by adding a coupler which gives a dye having an excellent hue, a large molecular extinction coefficient and a good storage stability to a light-sensitive material. Another object of the present invention is to provide a silver halide color photographic material having excellent sharpness and color image fastness. Another object of the present invention is to provide a simple method for producing an azo dye having a high molecular extinction coefficient and excellent hue and storage stability.

[0006]

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 compound represented by the following general formula (I). That is, the present invention

<1> A silver halide photographic material comprising at least one kind of coupler represented by the following general formula (I).

[0008]

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In the formula, Z represents an atomic group consisting of a carbon atom and / or a nitrogen atom which forms a 5- to 6-membered aromatic ring together with NC. R represents a substituent, and when a plurality of Rs are present, they may be the same or different and may be bonded to each other to form a ring. m represents 0 or an integer of 1 to 4. X represents a carbonyl group, a methylene group which may have a substituent or a> C = N-Rn group. Here, Rn represents a substituent. Y represents a hydrogen atom or a substituent.

<2> The silver halide photographic light-sensitive material according to <1>, wherein X in the coupler represented by formula (I) is a carbonyl group. <3> The silver halide photographic material according to <1>, wherein in the coupler represented by the general formula (I), Y is an alkyl group, an aryl group, or a heterocyclic group. <4> The coupler represented by the general formula (I) is a compound represented by the following general formulas (II), (III), (IV), (V), (VI), and (VI).
At least one of the couplers represented by I) or (VIII)
<1> The silver halide photographic material as described in <1>, which is a seed.

[0011]

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In the formula, R represents a substituent, and when a plurality of Rs are present, they may be the same or different;
These may be combined with each other to form a ring. m represents 0 or an integer of 1 to 3. X is a carbonyl group,
A methylene group which may have a substituent or> C = N-Rn
Represents a group. Here, Rn represents a substituent. Y represents a hydrogen atom or a substituent.

<5> A method for producing an azo dye, characterized by using a compound represented by the following general formula (I).

[0014]

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In the formula, Z represents an atom group consisting of a carbon atom and / or a nitrogen atom which forms a 5- to 6-membered aromatic ring together with NC. R represents a substituent, and when a plurality of Rs are present, they may be the same or different and may be bonded to each other to form a ring. m represents 0 or an integer of 1 to 4. X represents a carbonyl group, a methylene group which may have a substituent or a> C = N-Rn group. Here, Rn represents a substituent. Y represents a hydrogen atom or a substituent.

<6> The method for producing an azo dye according to <5>, wherein the compound represented by the general formula (I) and a p-phenylenediamine derivative are used.

[0017]

DETAILED DESCRIPTION OF THE INVENTION (Silver halide photographic material) The silver halide photographic material of the present invention has the following general formula (I):
(In the present application, also referred to as a coupler).

[0018]

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In the formula, Z represents an atomic group consisting of a carbon atom and / or a nitrogen atom which forms a 5- to 6-membered aromatic ring together with NC. R represents a substituent, and when a plurality of Rs are present, they may be the same or different and may be bonded to each other to form a ring. m represents 0 or an integer of 1 to 4. X represents a carbonyl group, a methylene group which may have a substituent or a> C = N-Rn group. Here, Rn represents a substituent. Y represents a hydrogen atom or a substituent.

In the above general formula (I), Z and N-
Examples of the 5- to 6-membered aromatic ring formed by C include:
Pyrrole ring, pyrazole ring, imidazole ring, 1,2,2
3-triazole ring, 1,2,4-triazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring,
Indole ring, isoindole ring, benzimidazole ring, quinoline ring, isoquinoline ring and the like. The expression “Z represents an atom group consisting of a carbon atom and / or a nitrogen atom that forms a 5- to 6-membered aromatic ring together with N—C” means a constituent atom of a ring skeleton of the atom group. And includes a hydrogen atom substituting this atom.

In the general formula (I), R represents a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an 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 group, amino Groups (including an alkylamino group, an arylamino group or a heterocyclic amino group), an acylamino group, an aminocarbonylamino group,
An alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl and arylsulfinyl group, Alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups,
Examples include carbamoyl, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups.

When a plurality of Rs are present (when m is any of 2 to 4), they may be the same or different from each other, and these may be bonded to each other. A ring may be formed. When two or more Rs are bonded to each other to form a ring, the ring is preferably a 5- or 6-membered saturated or unsaturated ring, and is a ring fused to a ring formed by Z and N-C. The above-described substituent represented by R may be further substituted with a substituent, and examples of the substituent include the above-described groups.

In the general formula (I), X represents a carbonyl group, an optionally substituted methylene group or> C = N
Represents an -Rn group, particularly preferably a carbonyl group.
In the case of a methylene group, an unsubstituted methylene group is preferred. When X is> C = N-Rn, Rn is the same substituent as described above for R. Rn is preferably an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group, and more preferably an alkyl group or an aryl group.

In the general formula (I), Y represents a hydrogen atom or a substituent. Examples of the case where Y is a substituent include the same substituents as those described above for R.
Y is preferably an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group, an aryl group or a heterocyclic group.

Hereinafter, the compound represented by formula (I) will be described in more detail. Examples of the compound represented by the general formula (I), which incorporates a heterocyclic ring as a preferable example of a 5- to 6-membered aromatic ring formed by Z and NC, include the following general formula (II): (III), (IV),
Compounds represented by (V), (VI), (VII) and (VIII) can be mentioned.

[0026]

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The general formulas (II), (III), (IV),
In (V), (VI), (VII) and (VIII), X, R,
And Y both represent the same as defined in the general formula (I). M represents 0 or an integer of 1 to 3. Among them, the compounds represented by the general formulas (III), (V), (VII) and (VIII) are preferable, and the compounds represented by the general formula (VIII) are most preferable.

In the general formula (I), when R, Rn and Y are substituents, the substituent may be a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (linear or A branched or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, -Cyanoethyl, 2-ethylhexyl),
Cycloalkyl group [preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, and a polycycloalkyl group such as a bicycloalkyl group ( Preferably, it is a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), And a group having a polycyclic structure such as a tricycloalkyl group. Preferred are a monocyclic cycloalkyl group and a bicycloalkyl group, and a monocyclic cycloalkyl group is particularly preferred. ],

An alkenyl group [a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, for example, vinyl, allyl,
Prenyl, geranyl, oleyl) and cycloalkenyl groups (preferably substituted or unsubstituted cycloalkenyl groups having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl and 2-cyclohexen-1-yl). And a polycycloalkenyl group, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, for example, bicyclo [2,2,1] hept-2-ene-1-) Yl, bicyclo [2,2,2] oct-2-en-4-yl)] or a tricyclic alkenyl group. Preferred are a monocyclic cycloalkenyl group and a bicycloalkenyl group, and a monocyclic cycloalkenyl group is particularly preferred. Alkynyl group (preferably having 2 to 30 carbon atoms)
Substituted or unsubstituted alkynyl groups such as ethynyl, propargyl, trimethylsilylethynyl),

An aryl group (preferably having 6 to 30 carbon atoms)
A substituted or unsubstituted aryl group such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-
Hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group, more preferably
A ring-constituting atom is a heterocyclic group selected from a carbon atom, a nitrogen atom and a sulfur atom, and having at least one heteroatom of a nitrogen atom, an oxygen atom and a sulfur atom; 30 5- or 6-membered aromatic heterocyclic groups. For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group,

An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example,
Methoxy, ethoxy, isopropoxy, t-butoxy,
n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), 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, and the heterocyclic portion is preferably the heterocyclic portion described in the above heterocyclic group, for example, 1-phenyltetrazol-5-oxy, 2- Tetrahydropyranyloxy),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy group Acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethyl Carbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n
-Octylaminocarbonyloxy, Nn-octylcarbamoyloxy, N-phenylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, methoxycarbonyloxy ,
Ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably having 7 to 30 carbon atoms)
A substituted or unsubstituted aryloxycarbonyloxy group such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 30 carbon atoms or a heterocyclic amino group having 0 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N −
1,3,5-triazin-2-ylamino), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 6 to 30 carbon atoms) Arylcarbonylamino group, 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) Groups, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, 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),

Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxy Carbonylamino), 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 alkylsulfonylamino groups having 1 to 30 carbon atoms, 6 to 3 carbon atoms)
0 is a substituted or unsubstituted arylsulfonylamino group, for example, 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, for example, methylthio, ethylthio, n-hexadecylthio);
An arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably substituted with 2 to 30 carbon atoms) Or an unsubstituted heterocyclic thio group, and the heterocyclic portion is preferably the heterocyclic portion described for the aforementioned heterocyclic group, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), 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), a sulfo group,

Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, Phenylsulfinyl,
p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, for example, methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), 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, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably substituted or unsubstituted aryloxy having 7 to 30 carbon atoms) Carbo In group, for example, phenoxycarbonyl, o- chlorophenoxy carbonyl, m- nitrophenoxy carbonyl, p-t-butyl-phenoxycarbonyl),

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably A substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl,
N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), an aryl or heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms), A substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocyclic portion is preferably the heterocyclic portion described for the aforementioned heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1 , 3,4-thiadiazol-2-ylazo), imide group (preferably,
A substituted or unsubstituted imide group having 2 to 30 carbon atoms,
For example, N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group ( Preferably, it has 2 to 30 carbon atoms.
A substituted or unsubstituted phosphinyl group such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinyl An amino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms such as dimethoxyphosphinylamino and dimethylaminophosphinylamino); a silyl group (preferably having 3 to 30 carbon atoms); 30 substituted or unsubstituted silyl groups, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

Of 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,
Examples include an arylsulfonylaminocarbonyl group, and specific examples include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl.

Further, adjacent Rs may be bonded to each other to form a ring, preferably a 5- or 6-membered saturated or unsaturated ring, which is an alicyclic, aromatic or heterocyclic ring. May be, for example, a benzene ring, a furan ring, a thiophene ring, a cyclopentane ring, a cyclohexane ring,
Further, two Rs may be bonded to each other to form a methylenedioxy group, which may be bonded to a ring formed by Z and NC.

The ring formed by combining each of these groups or a plurality of Rs may be further substituted with a substituent (for example, the groups exemplified for R). Further, the total number of carbon atoms of Y, R, and a plurality of R and Rn is preferably 2 to 50, more preferably 8 to 45, and still more preferably 15 to 40. On the other hand, any one of Y, R, and a plurality of R and Rn has 1 to 30, preferably 6 to 30, more preferably 8 to 30, and most preferably 10 to 25 carbon atoms. Among these groups, preferred are an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cyano group, an acylamino group, an alkoxycarbonyl group, and carbamoyl. Group, sulfamoyl group, alkylamino group or arylamino group.

In the present invention, among the compounds represented by the above general formula (I), preferred specific examples ((1) to (3)
9)) is shown below, but the present invention is not limited to these.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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In the following description, when citing the compounds of the exemplified compounds shown above, the “compound (X)” or the “compound (X)” is used by using the parenthesized number (X) attached to each exemplified compound. It will be indicated as “coupler (X)”.

Hereinafter, specific examples of the synthesis of the compound represented by formula (I) will be described. Synthesis Example 1: Synthesis of Compound (39) Compound (39) can be synthesized by the following route.

[0051]

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To 44 ml of concentrated sulfuric acid, 6.1 g of sodium nitrite was added over 20 minutes while cooling with water, followed by stirring for 10 minutes.
After heating to 70 ° C. to completely dissolve sodium nitrite, the mixture was ice-cooled. This solution was treated with 12.8 g of 3-amino-5-phenyl-1,2,4-triazole in acetic acid 14
0 ml to the solution dissolved in 0 ml under ice cooling over 20 minutes,
The mixture was stirred for 30 minutes under ice cooling to prepare a solution of the compound (A). 10.9 g of 3,5-dimethylanisole was dissolved in 200 ml of methanol, and the solution of the compound (A) prepared above was added to this solution with stirring under ice-cooling over 30 minutes. After reacting with stirring for 30 minutes under ice cooling, water and ethyl acetate were added for extraction, and the organic layer was washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was crystallized from a mixed solvent of ethyl acetate and hexane to obtain 15.5 g of a compound (B).

Next, 13.8 g of the compound (B) and
6.3 g of potassium carbonate was added to tetrahydrofuran (TH
F) 300 ml, 200 ml EtOH and 3 water
The mixture was dissolved in 00 ml of a mixed solvent, and 15.7 g of sodium hydrosulfite was added at room temperature. After stirring at room temperature for 10 minutes, 15.7 g of sodium hydrosulfite was further added. After stirring at room temperature for 15 minutes, sodium hydrosulfite 1
5.7 g and potassium carbonate 0.6 g were added.
After reacting at room temperature for 30 minutes, the solvent was distilled off under reduced pressure,
Ethyl acetate, hexane and water were added and the mixture was stirred, and the precipitated crystals were separated by filtration to obtain 11.6 g of compound (D).

Next, 9.3 g of the compound (D) was added to 300 ml of dimethylacetamide (DMAC) and THF.
The solution was dissolved in 300 ml of a mixed solvent, and a solution of 4.2 g of triphosgene dissolved in 100 ml of THF was added thereto over 13 minutes under ice-cooling. After reacting under ice-cooling for 30 minutes, water and ethyl acetate were added for extraction, and the organic layer was washed with diluted hydrochloric acid and saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography.
0.71 g of 9) was obtained.

Synthesis Example 2: Synthesis of Compound (18) Compound (18) can be synthesized by the following route.

[0056]

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9.8 g of 2,4,5-trichloroaniline
Was dissolved in a mixed solution of 13 ml of concentrated hydrochloric acid and 39 ml of ice water, and 3.8 g of sodium nitrite was added to 19 ml of water under ice-cooling.
Was added dropwise, and the mixture was stirred for 1 hour under ice cooling to prepare a solution of compound (D). 9.9 g of 4,5-diphenylimidazole was dissolved in 300 ml of methanol, and a solution of 8.4 g of sodium hydroxide dissolved in 10 ml of water was added. The solution of the compound (D) prepared above was added to this solution over 30 minutes while stirring under ice cooling. After stirring for 30 minutes under ice-cooling, the mixture was neutralized by adding aqueous hydrochloric acid, extracted with ethyl acetate, and the organic layer was washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and crystallized from a mixed solvent of THF, ethyl acetate and hexane to obtain 13.0 g of compound (E).

Then, 7.7 g of the compound (E) was added to THF
100 ml, EtOH 50 ml, and water 50 ml
And a solution of 7.8 g of sodium hydrosulfite dissolved in 50 ml of water was added dropwise at 40 ° C. over 10 minutes. After reacting at 40 ° C. for 30 minutes, water and ethyl acetate were added for extraction, and the organic layer was washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallized from a mixed solvent of ethyl acetate and hexane to obtain 6.4 g of compound (F).

Next, 2.1 g of triphosgene was added to THF.
The compound was dissolved in 300 ml, and 3.9 g of the compound (F) was added over 10 minutes while cooling with water. More triethylamine
7.0 ml was added dropwise over 10 minutes under water cooling. 3 at room temperature
After reacting for 0 minutes, 50 ml of water was added and stirred for 30 minutes. Water and ethyl acetate were added for extraction, and the organic layer was washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was crystallized from a mixed solvent of ethyl acetate and hexane to obtain 1.9 g of Exemplified Compound (18).

The silver halide photographic light-sensitive material of the present invention comprises at least one light-sensitive layer formed on a support, and at least one of the light-sensitive layers contains a coupler represented by formula (I). I do. The coupler can be contained in a hydrophilic colloid layer comprising a usual gelatin binder. The silver halide photographic light-sensitive material of the present invention comprises at least each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer (photosensitive layer) on a support. It can be constituted by coating one layer, but the order may be 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 having sensitivity in each wavelength range and a coupler that forms a dye having a complementary color relationship with light to be exposed, thereby performing color reproduction by the subtractive color method. be able to. However, the photosensitive emulsion layer and the color hue of the coupler may not have the above correspondence.

The coupler represented by the general formula (I) is
Any 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. The coupler represented by the general formula (1) is useful mainly as a yellow coupler or a magenta coupler when combined with a color developing agent such as a p-phenylenediamine, and is particularly useful as a yellow coupler. Therefore, when the silver halide photographic light-sensitive material of the present invention uses p-phenylenediamines as a color developing agent, the coupler represented by the general formula (I) is contained in a yellow or magenta color-forming layer. It is particularly preferable that the compound be contained in a layer for yellow coloring. Further, the coupler represented by the general formula (I) is useful as a dye-forming coupler which gives dyes of various hues even in a system using a color developing agent other than p-phenylenediamines.

In the silver halide photographic light-sensitive material of the present invention
And the coupler is 1 × 1 per mole of silver halide.
0^-3１1 mol is preferable, and 2 × 10^-3~ 3x
10 ^-1More preferably, it is added in molar.

The coupler can be introduced into the light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination), and emulsified and dispersed in an aqueous gelatin solution to form a silver halide. An oil-in-water dispersion method to be added to the 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-5-32353.
No. 9, 5-323541, 6-258803,
Nos. 8-262662, and U.S. Pat. No. 2,322,027. 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 and West German Patent Application (OLS).
Nos. 2,541,274, 2,541,230, JP-B-53-41091 and European Patent Publication No. 029104.
No. PCT International Publication No. WO88 / 0072.
No. 3 and JP-A-5-150420. 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 point organic solvent having a boiling point of 175 ° C. or higher at normal pressure include phthalic acid esters such as dibutyl phthalate, dicyclohexyl phthalate,
2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-tert-amylphenyl) phthalate,
Bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate], phosphoric acid or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate),
Benzoic acid esters (eg, 2-ethylhexyl benzoate, dodecyl benzoate, 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 (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N, N
-Dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene), and chlorinated paraffins. In particular, phosphoric esters and
The hydrogen donating compounds described in JP-A-258803 and JP-A-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 emulsified dispersion may be used, if necessary, from the viewpoint of improving the stability over time during storage in the state of the emulsified dispersion, suppressing the change in photographic performance and improving the stability over time in the final coating composition 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 from 0.001 to 1.0 μm, more preferably from 0.05 to 0.30 μm, and most preferably from 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, problems such as a decrease in the coloring efficiency of the coupler and deterioration of the glossiness of the surface of the photosensitive material are likely to occur.If the size is too small, the viscosity of the dispersion increases. , It becomes difficult to handle during manufacture.

The amount of the lipophilic fine particle dispersion comprising the coupler to be used in the dispersion medium is preferably 2 to 0.1, more preferably 1.0 to 1.0 in terms of mass ratio to the dispersion medium 1.
0.2. Here, a typical dispersion medium is, for example, gelatin, and a hydrophilic polymer such as polyvinyl alcohol. In the lipophilic fine particle dispersion,
Various compounds can be contained 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 (E).
G) with polyester or NDCA, terephthalic acid and EG
A material in which an information recording layer such as a magnetic layer is provided on polyester or the like is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

A more preferred reflective support that can be used in the present invention is one having a polyolefin layer having micropores on a paper substrate on which a silver halide emulsion layer is provided. The polyolefin layer may be composed 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 (for example, polypropylene, polyethylene) and can be placed on a paper substrate. Those made of polyolefin (for example, polypropylene or polyethylene) having micropores on the near side are more preferable. The density of these multilayers or single polyolefin layers located between the paper substrate and the photographic component layers is 0,1.
40 to 1.0 g / ml, preferably 0.50 to 1.0 g / ml.
-0.70 g / ml is more preferred. The thickness of the multilayer or one polyolefin layer located between the paper substrate and the photographic constituent layer is preferably from 10 to 100 μm, more preferably from 15 to 70 μm. The ratio of the thickness of the polyolefin layer to the thickness of the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.5.

It is also preferable to provide a polyolefin layer on the opposite side (back surface) of the paper substrate from the photographic component layer, from the viewpoint of increasing the rigidity of the reflective support. In this case, the polyolefin layer on the back surface has a matte surface. Preferred is polyethylene or polypropylene, and more preferred is polypropylene. The polyolefin layer on the back side 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 above-mentioned reflection support, a preferred embodiment relating to a polyolefin layer provided on a paper substrate is described in JP-A-10-333.
No. 277, No. 10-333278, No. 11-5251
Nos. 3 and 11-65024, and EP0
No. 88,065, and the examples described in EP 088,066.

Further, 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, more preferably 0.001 to 0.5% by mass, based on the resin.

The reflective support may be a transmissive support or the above-described reflective support provided with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

As a support used in the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment for a display was provided on the support having a silver halide emulsion layer. 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.

The light-sensitive material according to the present invention may be coated with a hydrophilic colloid layer for the purpose of improving the sharpness of an image, etc., in accordance with EP-A-0,337,490 A2, Nos. 27 to 40.
By the treatment described on page 76, a decolorizable dye (especially an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, or the dye is added to the water-resistant resin layer of the support. 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated with dihydric or tetravalent alcohols (eg, trimethylolethane)
It is preferable to include them.

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). Further, dyes described in European Patent EP 0819977 are preferably added to the light-sensitive material of 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-5-12732.
No. 4, No. 5-127325, No. 5-216185, etc. are preferable.

In the present invention, a colored layer that can be decolorized by treatment can be used instead of or in combination with the water-soluble dye. The colored layer may be disposed directly in contact with the emulsion layer, or may be disposed 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 the lower layer of the emulsion layer which forms the same primary color as the colored color (on the side of the support).
It is preferably installed in 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 which 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
It is preferable that the optical density value at the wavelength having the highest optical density in the visible light region of 700 nm or the wavelength of the scanning exposure light source used in the case of scanning exposure is 0.2 to 3.0. More preferably 0.5 or more and 2.5 or less,
In particular, it is preferably 0.8 or more and 2.0 or less.

For forming a colored layer, a conventionally known method can be applied. For example, dyes described in JP-A-2-282244, page 3, right upper column to page 8, and dyes described in JP-A-3-282244.
No. 7793, page 3, upper right column to page 11, lower left column, a method in which 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. Of adsorbing on a fine particle such as silver halide and fixing it in a layer;
No. 544, which uses colloidal silver. 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-
No. 308244, pages 4-13.
Further, for example, a method of mordanting an anionic dye into a cationic polymer is described in JP-A-2-84637, pp. 18-26. The preparation of colloidal silver as a light absorber is described in US Pat. No. 2,688,60.
Nos. 1 and 3,459,563.
Among these methods, a method of containing a fine powder dye,
A method using colloidal silver is 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} planes (these grains have a rounded apex and a higher 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 for use in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsions and the like are 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 preferably comprises 0.1 to 5 mol% of the total silver constituting the silver halide grains in the present invention, and preferably 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, hexaammineiridium (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, metal compounds having at least four cyano ligands, such as iron, ruthenium, osmium, and rhenium, are particularly preferable in that they further increase the high illuminance sensitivity and suppress the 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.
It is preferably from 10 ^-9 to 10 ^-2 mol per mol.

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 grain 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 (the 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 may contain various compounds or their precursors for the purpose of preventing fog 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 described in JP-A-62-2.
Those described on page 39 to page 72 of JP-A-15272 are preferably used. Further, EP0447647
5-arylamino-1,2,2 described in
3,4-Thiatriazole compounds (the aryl residue has at least one electron-withdrawing group) are also preferably used.

In the present invention, the hydroxamic acid derivatives described in JP-A-11-109576 and JP-A-11-327 are disclosed in JP-A-11-109576 in order to enhance the storage stability of the silver halide emulsion.
No. 094, a cyclic ketone having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group (particularly those represented by the general formula (S1), paragraphs 0036 to 0071) Can be incorporated in the specification of the present application.) And sulfo-substituted catechols and hydroquinones (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5) described in JP-A-11-143011. -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 formula (I) in JP-A-11-102045.
The water-soluble reducing agents represented by (III) to (III) are 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,
Spectral sensitizing dyes used for spectral sensitization in the red region include:
For example, Heterocyclic compounds-Cyanin by FM Harmer
e dyes and related compounds (John Wiley & Sons [N
ew York, London], published in 1964). As specific examples of compounds and spectral sensitization methods, those described in JP-A-62-215272, page 22, upper right column to page 38, are preferably used. In particular, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, JP-A-3-13-1
The spectral sensitizing dyes described in JP-A-23340 are stable,
It is very preferable from the viewpoint of the strength of adsorption, the temperature dependency of exposure, and the like.

The preferred range of the addition amount of the spectral sensitizing dye is wide depending on the case, and is preferably in the range of 0.5 × 10 ^-6 mol to 1.0 × 10 ^-2 mol per mol of silver halide. More preferably, 1.0 × 10 ⁻⁶ mol to 5.
The range is 0 × 10 ⁻³ mol.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. As for 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. Compounds used for chemical sensitization are described in JP-A-62-215272, No. 1
Those described in the lower right column of page 8 to the upper right column of page 22 are preferably used. Among them, it is particularly preferable that the metal is subjected to gold sensitization. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed using a laser beam or the like can be further reduced. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanate, gold thiosulfate, and gold sulfide colloid can be used. A preferred range of the addition amount of these compounds is
In a wide range depending on the case, 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ per mol of silver halide.
１1 × 10 ^-4 mol. In the present invention, gold sensitization may be combined with other sensitization methods, for example, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or 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, the silver halide photographic light-sensitive material of the present invention may have a different layer constitution.

For example, when the coupler represented by the general formula (I) is used as a yellow coupler, the silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support. If the yellow coupler-containing layer contains silver halide tabular grains, the yellow coupler-containing layer may be located farther from the support than at least one of the magenta coupler-containing silver halide emulsion layer or the cyan coupler-containing silver halide emulsion layer. Preferably, it is coated. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the yellow-coupler-containing silver halide emulsion layer is located farthest from the support than the other silver halide emulsion layers. Preferably, it is coated. 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, JP-A-4-75055 and JP-A-9-114035
As described in JP-A-10-246940 and U.S. Pat. No. 5,576,159, a coupler layer containing no silver halide emulsion is provided adjacent to the silver halide emulsion layer. It is also preferable to form a coloring 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
Nos. 15,272, JP-A-2-33144 and those described in EP 0,355,660 A2, particularly those described in EP 0,355,660 A2 are preferably used. Can be Further, JP-A-5-34889 and JP-A-4-359249.
Nos. 4-313375, 4-270344, 5-66527, 4-34548, 4-145
No. 433, No. 2-854, No. 1-158431, No. 2-90145, No. 3-194439, No. 2-93
Nos. 641 and EP 0520457A2.
The silver halide color photographic light-sensitive material described in the specification and the processing method thereof are also preferable.

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 structure and the coating pH of the photosensitive material, those described in the patents in Tables 1 and 2 below can be particularly preferably applied.

[0093]

[Table 1]

[0094]

[Table 2]

The cyan, magenta and yellow couplers which can be used in combination in the present invention include, for example, JP-A-62-215272, page 91, upper right column, lines 4 to 1;
Line 21 of the upper left column of page 21, line 14 of the upper right column of page 3 of JP-A-2-33144 to line 18 of the upper left column of page 18, and line 6 of the upper right column of page 30 to line 11 of the lower right column of page 30. And EP0355,6
60A2, page 4, lines 15-27, page 5, 3
Lines 0-28, last line, page 45, lines 29-31, 4
The couplers described on page 7, line 23 to page 63, line 50 are also useful. In the present invention, it is preferable to add a compound represented by formulas (II) and (III) of WO-98 / 33760 and a formula (D) of JP-A-10-221825.

In the silver halide photographic light-sensitive material of the present invention, the coupler represented by formula (I) may be used alone or in combination with other couplers. When the coupler is a yellow coupler, other yellow couplers that may be used in combination include, in addition to the compounds described in the above table, a 3- to 5-membered cyclic group in an acyl group described in European Patent EP0447969A1. Acylacetamide type yellow coupler having a structure, EP 0482552
No. 5,118,599. A malondianilide-type yellow coupler having a cyclic structure described in A1.
An acylacetamide-type yellow coupler having a dioxane structure described in the specification is preferably used.
Among them, the acyl group is 1-alkylcyclopropane-
It is particularly preferable to use an acylacetamide type yellow coupler, which is a 1-carbonyl group, or a malondianilide type yellow coupler in which one of the anilides forms an indoline ring.

In the silver halide photographic light-sensitive material of the present invention, it is preferable to use a phenol-based or naphthol-based cyan coupler or a heterocyclic coupler as the cyan coupler. As the phenolic coupler, other than those described in the above table, for example, JP-A-10-33
A cyan coupler represented by the general formula (ADF) described in JP-A-3297 is preferred. Further, the 2,5-diacylaminophenol coupler described in U.S. Pat. No. 5,888,716 with improved hue and fastness is preferably used.

The heterocyclic couplers described in European Patent EP 0 488 248 and EP 0 491 197 A
A pyrroloazole type cyan coupler described in the specification 1,
U.S. Pat. Nos. 4,873,183 and 4,916,0
Pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in JP-A-51-51, particularly JP-A-8-171185, JP-A-8-31360, and JP-A-8-31360.
It is also preferable to use a pyrazoloazole-type cyan coupler having a carbamoyl group at the 6-position described in each of JP-A-339060. Among these cyan couplers, a pyrroloazole-based cyan coupler represented by the general formula (I) described in JP-A-11-282138 is particularly preferred. The present invention, including the couplers (1) to (47), is applied as it is to the present application, and is preferably incorporated as a part of the specification of the present application.

In addition to the diphenylimidazole-based cyan couplers described in JP-A-2-33144, 3-hydroxypyridine-based cyan couplers described in European Patent No. EP 0333185A2 (including 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-based cyan coupler (among others, coupler examples 3, which are listed as specific examples,
8, 34 are particularly preferred), EP 0 456 622
It can also 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.

In the silver halide photographic light-sensitive material of the present invention, as the magenta coupler, there can be used a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler as described in the known documents in the above table.
Above all, Japanese Patent Application Laid-Open No.
No. 65245, 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.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-5246
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-147254 and 6-position as described in European Patent Nos. 226,849A and 294,785A. It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group. In particular, as the magenta coupler, a pyrazoloazole coupler represented by the general formula (MI) described in JP-A-8-122984 is preferable, and paragraph numbers 0009 to 0026 of the patent are applied to the present application as they are. Is incorporated as part of the specification. In addition to this, European Patent Nos. 854384 and 8
Pyrazoloazole couplers having a sterically hindered group at both the 3-position and the 6-position described in 84640 are also preferably used.

Similar to the coupler of the present invention represented by the general formula (I), the magenta or cyan coupler also
Impregnating a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of a high boiling organic solvent as described in Tables 1 and 2 above, or a water-insoluble and organic solvent It is preferable to dissolve together with a solvent-soluble polymer and emulsify and disperse in a hydrophilic colloid aqueous solution. A water-insoluble and organic solvent-soluble polymer which can be preferably used is disclosed in US Pat.
7,449, columns 7 to 15 and International Publication WO
Homopolymers or copolymers described on pages 12 to 30 of JP 88/00723. 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 order to suppress the blix discoloration (defective recoloring) by the bleaching solution or the bleach-fixing solution, JP-A-8-62797 and JP-A-9-9-197 are incorporated in the hydrophilic colloid layer.
It is preferable to use the polymers described in JP-A-71240 and JP-A-9-329861.

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 /
No. 33760, U.S. Pat. No. 4,923,787, etc., phenidone and hydrazine compounds described in
No. 2,496,637, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, when increasing the pH of the developer to speed up the development, German Patent No. 1918786A1 and European Patent No. 83962 are used.
3A1, European Patent 842975A1, German Patent 1
No. 9806846 A1 and French Patent No. 2760460
It is also preferable to use the redox compound described in A1 or the like.

In the present invention, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as an ultraviolet absorber. For example, the compounds described in the following patents can be used. JP-A-46-3335, 55
-152776, JP-A-5-197074, and 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.

Examples of the anti-fading agent and the hue adjusting agent other than those described in the above table which can be used in the present invention include JP-A-11-25.
No. 8748, a vinyl compound represented by the general formula (II), an oxygen-nitrogen bond-containing or alkoxy-substituted aniline derivative represented by the general formula (III), and a vinyl aniline derivative represented by the general formula (IV) Diffusible phenidone derivatives, non-diffusible carboxylic acids represented by the general formula (V), non-diffusible arylcarbamoyl derivatives represented by the general formula (VI), arylamide derivatives represented by the general formula (VII), Formula (VII
The cyclic imide derivative represented by I) can be mentioned, and any of them can be preferably used.

As a binder or a protective colloid which can be used in the silver halide photographic material according to the present invention, it is advantageous to use gelatin, but other hydrophilic colloids may be used alone or together with gelatin. Can be. Preferred gelatins are iron, copper,
Heavy metals contained as impurities, such as zinc and manganese,
It is preferably at most 5 ppm, more preferably at most 3 ppm. The amount of calcium contained in the photosensitive material is
Preferably 20 mg / m ² or less, more preferably 10 m / m ²
g / m ² or less, 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, Japanese Patent Application Laid-Open No.
It is preferable to add a bactericidal / antifungal agent as described in JP-A-271247. Further, the coating pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 7.0.
6.5.

The silver halide photographic 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 usual 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. For the cathode ray tube used for image exposure, various luminous bodies that emit light in a spectral region are used as necessary. 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
The phosphor is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, violet, 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 which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, A plurality of color image signals may be input to the cathode ray 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 improving image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic emission light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and 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, or a second harmonic generation light source (SHG) in which a semiconductor laser or 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.

In the case of using such a scanning exposure light source,
Maximum spectral sensitivity wavelength of the silver halide photographic light-sensitive material of the present invention
Can be set arbitrarily according to the wavelength of the scanning exposure light source used.
Can be Using a semiconductor laser as the excitation light source
Laser or semiconductor laser and nonlinear optical crystal
In the SHG light source obtained in combination, the laser oscillation wave
Since the length can be halved, blue light and green light can be obtained. Obedience
Therefore, the spectral sensitivity maximum of the light-sensitive material is 3 blue, green, and red.
It is possible to have it in two wavelength ranges. like this
The exposure time in the scanning exposure is such that the pixel density is 400 dpi.
Define pixel size as exposure time
And a preferable exposure time is 10 ^-FourLess than a second, more preferred
Or 10^-6Seconds or less.

The preferred scanning exposure method applicable to the present invention is described in detail in the patents listed in the above table. To process the light-sensitive material of the present invention, see
JP-A-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9;
The processing materials and processing methods described in the upper left column of the page, line 17 to the lower right column of page 18, line 20 can be preferably applied. As the preservative used in the 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 rapid processing suitability. 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 processing using the silver halide photographic light-sensitive material of the present invention, the color development time is preferably 60 seconds or less, more preferably 50 seconds or more and 6 seconds or more, and still more preferably 30 seconds or less and 6 seconds or more. . Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and still more preferably 30 seconds or less and 6 seconds or more. The washing or stabilization time is preferably 150 seconds or less,
More preferably, it is 130 seconds or less and 6 seconds or more.

As a method for developing the photosensitive material of the present invention after exposure, there are a conventional method of developing with a developer containing an alkali agent and a developing agent, and a method of incorporating a developing agent into the photosensitive material and using an alkaline solution containing no developing agent. In addition to a wet method such as a method of developing with an activator liquid, a thermal developing method without using a processing liquid can be used. In particular, since the activator method does not contain a developing agent in the processing liquid, it is easy to manage and handle the processing liquid, and is a preferable method from the viewpoint of environmental protection 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 are preferable.

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 liquid containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152699 is preferably used. In the activator method, desilvering is usually performed after processing with an activator solution.However, in the image amplification processing method using a low silver content photosensitive material, desilvering is omitted, and simple processing such as washing with water or stabilization is performed. Method 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.

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

When the silver halide photographic light-sensitive 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, European Patent EP0
As described in 789270A1 and EP0789480A1, before giving 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 complete dry system for heat development without using any water. These systems are described in JP-A-6-35118, JP-A-6-17528, and JP-A-56-35528.
146133, 60-119557, JP-A-1-
There is a detailed description in each gazette of 161236.

In the present invention, the silver halide photographic light-sensitive material is not limited to a light-sensitive material for forming a color image.
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, the light-sensitive materials described in JP-A-11-7109 are preferred. In particular, the description in paragraphs 007-0087 of JP-A-11-7109 is described. 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 in paragraphs 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.

(Method for Producing Azo Dye) The method for producing an azo dye of the present invention is characterized by using the coupler represented by the general formula (I). The compound represented by the general formula (I) is useful for synthesizing an azo dye. More specifically, p-phenylenediamine derivatives, especially N,
An azo dye can be easily obtained by a coupling reaction with an oxidized N-disubstituted-p-phenylenediamine derivative. Thereby, without passing through a diazo coupling reaction by a diazonium salt which is complicated in operation,
There is an advantage that an azo dye can be produced. That is, as shown in the following formula, the dye represented by the general formula (D) is easily produced in one step by the compound represented by the general formula (I) and the compound represented by the general formula (A). be able to.

[0121]

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In the above reaction, first, the hydrogen atom of the nitrogen atom to which X—N (Y) — of the compound represented by the general formula (I) is dissociated, and this portion is represented by the general formula (A): After the compound to be oxidized by the oxidizing agent is subjected to a coupling reaction with an oxidized product, the XN (Y) moiety is eliminated to give an azo dye of the general formula (D). The reaction which can be used in the method for producing an azo dye of the present invention includes the step of reacting an oxidized form of the compound represented by the general formula (A) with the above-mentioned nitrogen atom, and opening the five-membered ring in this reaction. And X—N (Y) ^— or X—N (Y) — bonded to a nitrogen atom contained in the ring represented by Z.
It is characterized in that H separates from the nitrogen atom. Dye represented by the obtained formula (D), the X-N (Y) ^- by or the X-N (Y) -H is separated from the nitrogen atom, the performance of the dye in each stage Has improved.

Here, in the general formula (D), R ₀ , R ₁
And R ₂ independently represent a substituent, and n represents an integer of 0, 1-4. R, Z and m have the same meanings as in each of formulas (I). Examples of the substituent represented by R ₀ , R ₁ and R ₂ include the groups defined by R in the general formula (I). R
₀ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,
Represents a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms or a halogen atom, and R ₁ and R ₂ are preferably 1 carbon atoms;
~ 30 substituted or unsubstituted alkyl groups or 6 to 6 carbon atoms
30 substituted or unsubstituted aryl groups. n is preferably 0 or 1.

More preferably, R ₀ is an unsubstituted alkyl group having 1 to 4 carbon atoms, and R ₁ and R ₂ are a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. As the substituent, a hydroxyl group and a methanesulfonylamino group are preferable. Particularly preferably, R ₀ is a methyl group, R ₁ is an ethyl group,
And R ₂ is a β-methanesulfonamidoethyl group or β
-Hydroxyethyl group.

The azo dye represented by the general formula (D) may be a coupler represented by the general formula (I) and a p-phenylenediamine derivative represented by the general formula (A), as described in Examples below. Can be easily synthesized by dissolving in a solvent and adding an oxidizing agent to this solution. Incidentally, R _0, R ₁ and R ₂ in the general formula (A) R _0, are each synonymous with R ₁ and R ₂ in the general formula (D).

The solvent used in the production process can be used irrespective of polarity or non-polarity as long as it can dissolve the compound represented by the general formula (I) and the compound represented by the general formula (A). . For example, chloroform, ethyl acetate, ethanol, N, N-dimethylformamide and the like can be mentioned.
The amount of the compound represented by the general formula (A) to the compound represented by the general formula (I) is 0.1 to 10 in a molar ratio, preferably 0.5 to 5, and more preferably 0.8. ~
1.5. The base is sodium carbonate, potassium carbonate,
Sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like are used. The amount of the base to be used is, in addition to the amount required to dissociate the compound represented by the general formula (I), and when the compound represented by the general formula (A) is a salt, the base is further added. Use the amount needed to remove The oxidizing agent can be any oxidizing agent,
Examples include persulfate, manganese dioxide, silver halide, ferric chloride and the like. The reaction temperature is generally -10
To 100 ° C, preferably room temperature to 80 ° C, more preferably room temperature to 50 ° C.

The dyes (exemplary compounds D-1 to D-4) represented by the general formula (D) which can be produced by the method for producing an azo dye of the present invention are illustrated below. Is not limited.

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[0129]

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[0131]

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. <Comparative Example 1> Preparation of Comparative Dye (CD-1) Comparative coupler (C-1) shown below: 0.85 g, N-
Ethyl-N- (β-methanesulfonamidoethyl) -3
Liquid obtained by dissolving 1.45 g of ammonium persulfate in 10 ml of water in a mixture of -methyl-4-aminoaniline sulfate: 0.80 g, sodium carbonate: 3.75 g, ethyl acetate: 60 ml, and water: 50 ml Was slowly added under stirring at room temperature. After stirring for 1 hour, the ethyl acetate layer was separated and purified by silica gel chromatography to obtain a comparative dye (CD-1) which is a yellow azomethine dye for comparison described below.

[0132]

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2. Preparation of Emulsified Dispersion of Comparative Coupler (C-1) 0.88 g of Comparative Coupler (C-1) and 2.6 g of tricresyl phosphate were dissolved by heating in 10 ml of ethyl acetate (this was used as an oil phase liquid). . Separately, gelatin: 4.2
g was added to 25 ml of water at room temperature, and 4
The mixture was heated to 0 ° C. and completely dissolved. While maintaining the gelatin aqueous solution at about 40 ° C., 3 ml of a 5% aqueous solution of sodium dodecylbenzenesulfonate and the oil phase solution prepared above were added, and the mixture was emulsified and dispersed using a homogenizer to emulsify and disperse the comparative coupler (C-1). Was prepared.

3. Preparation of Comparative Photosensitive Material Using the obtained emulsified dispersion of the comparative coupler (C-1), a coating solution having the following composition was prepared, and a coupler of 1 mmol / m 2 was formed on a polyethylene-laminated paper having an undercoat layer.
^The coating liquid was applied so as to be ² . Further, gelatin was applied thereon as a protective layer so as to have a concentration of ² g / m ² to prepare Sample 201 as a comparative photosensitive material.

(Composition of Coating Solution) Emulsion: 13 g of silver chlorobromide (cubic particles based on silver chloride, with a total of 0.3 mol% of silver bromide locally contained 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.) ・ 10% gelatin 28 g ・ Comparative coupler described above 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

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<Examples 1 to 4> Preparation of Dyes (D-1) to (D-4) In "1. Preparation of Comparative Dye (CD-1)" of Comparative Example 1, the above-mentioned exemplary couplers of the present invention are used instead of the comparative coupler (C-1). Dye D, which is an azomethine dye obtained from the coupler of the present invention, in the same manner as in Comparative Example 1 except that (1), coupler (2), coupler (29), and coupler (18) were used, respectively. −
1 (using coupler (1)), D-2 (using coupler (2)), D-3 (coupler (29)
) And D-4 (using coupler (18)).

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[0139] 2. Preparation of Emulsified Dispersion of Couplers (1), (2), (29) and (18) In Comparative Example 1, "2. Preparation of Emulsified Dispersion of Comparative Coupler (C-1)" The coupler according to the present invention was prepared in the same manner as in Comparative Example 1, except that the above-mentioned exemplified coupler (1), coupler (2), coupler (29), and coupler (18) according to the present invention were used instead of 1). Was prepared.

3. Preparation of the photosensitive material of the present invention In "3. Preparation of comparative photosensitive material" in Comparative Example 1, the above-mentioned exemplified couplers (1) and (2) of the present invention were used instead of the emulsified dispersion of the comparative coupler (C-1). ), Samples 202 (using coupler (1)) and Samples 203 as photosensitive materials of the invention in the same manner as in Comparative Example 1 except that the emulsified dispersions of (29) and (18) were used.
(Using the coupler (2)), Sample 204 (using the coupler (29)), and Sample 205 (using the coupler (18)) were produced.

<Measurement of Molecular Absorption Coefficient> The comparative dye (CD-1) and the dyes (D-1) to (D-4) obtained in the above comparative examples and examples are as follows. And the molecular extinction coefficient was measured. Comparative dye (CD-
1) Any of dyes (D-1) to (D-4) 1.5 m
g in a 100 ml volumetric flask, and ethyl acetate: 1
After adding and dissolving 00 ml and diluting with ethyl acetate, sample solution 101 (using the comparative dye (CD-1)), sample solution 102 (using the dye (D-1)), sample solution 1
03 (using dye (D-2)), sample solution 104
(Using dye (D-3)) and sample solution 10
No. 5 (using dye (D-4)) was prepared.

The obtained sample solutions 101 to 105 were applied to a thickness of 1
The sample was placed in a quartz cell having a size of 5 cm, and the visible absorption spectrum was measured with an ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation to calculate the molecular extinction coefficient. The molecular extinction coefficients are shown in Table 3 below.

[0143]

[Table 3]

From Table 3 below, it was found that the dye obtained from the coupler in the present invention had a larger molecular extinction coefficient than the dye obtained from the comparative coupler. Due to the large molecular extinction coefficient of the dye obtained from the coupler in the present invention, it is possible to obtain a thinner layer and the same concentration as before. This means that in a silver halide photographic light-sensitive material using the coupler, color reproducibility and sharpness of an obtained image are improved.

<Color Image Fastness Evaluation Test> For the samples 201 to 205 obtained in the above comparative examples and examples,
A color image fastness evaluation test was performed as follows. First, each sample was exposed to wedges with white light, and subjected to a color development process by the following processing steps.

(Processing Step) Step Temperature Time Color Development 38.5 ° C. 45 seconds Bleach-fix 30-36 ° C. 45 seconds Stable 30-37 ° C. 20 seconds Stable 30-37 ° C. 20 seconds Stable 30-37 ° C. 20 seconds Dry 85 ° C 70 seconds

In each of the steps of color development, bleach-fixing, stabilization, stabilization and stabilization, the processing was carried out by immersion in the following processing solutions under the above conditions. (Color developing solution in the color developing step)-800 ml of water-0.1 g of dimethylpolysiloxane-based surfactant (silicone KF351A / manufactured by Shin-Etsu Chemical Co., Ltd.)-11.6 g of triethanolamine-4.0 g of ethylenediaminetetraacetic acid-4, 0.5 g of sodium 5-dihydroxybenzene-1,3-disulfonate 10.0 g of potassium chloride 0.040 g of potassium bromide A 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 5.0 g potassium carbonate 26.3 Water was added 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 iron (III) ammonium 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 water is added to 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 6.0

(Stabilization-stabilizing solution in process) ・ Chlorinated sodium isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

Each of the processed samples developed yellow color,
Samples 202 to 205 of the photosensitive material of the present invention had sharper hues than the sample 201 of the comparative photosensitive material. Next, a light-fading test was performed on each of Samples 201 to 205 that had been subjected to the color development processing, using a Xe light source of 100,000 lux, for 14 days of irradiation (5 hours light / 1 hour dark intermittent irradiation). Was. The color development density of each sample before and after the photofading test was measured using a Fuji Photo Film TCD type densitometer,
The ratio (residual rate:%) of the color density after the light fading test to the color density before the light fading test was calculated, and this was used as an evaluation index for color image fastness. The results are shown in Table 4 below.

[0151]

[Table 4]

As is clear from the results shown in Table 4, the light-sensitive material of the present invention is excellent in light fastness.

<Example 5> A corona discharge treatment was applied to the surface of a support obtained by coating both sides of a paper with a polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Samples (001) of the silver halide color photographic light-sensitive material having the following layer constitution were prepared by sequentially coating the layers from the photographic constituent layer to the seventh layer. 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), 8 g of color image stabilizer (Cpd-1), 4 g of color image stabilizer (Cpd-2), color image stabilizer (Cpd-
3) 8 g was dissolved in 23 g of a solvent (Solv-1) and 80 ml of ethyl acetate, and this solution was emulsified in 220 g of a 23.5% by weight aqueous gelatin solution containing 4 g of sodium dodecylbenzenesulfonate using a high-speed stirring emulsifier (dissolver). It was dispersed and water was added to prepare 900 g of emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.72 μm and small-size emulsion A having an average grain size of 0.60 μm (silver molar ratio). 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the surface of silver chloride-based grains in each size emulsion). This emulsion contains the following red-sensitive sensitizing dyes A, B and C per mol of silver halide, 1.4 × 10 ^-4 mol for large-size emulsion and 1.4 × 10 ^-4 mol for small-size emulsion, respectively. 1.7 × 10 ^-4 mol is added. The 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.

(Preparation of Coating Solutions for Second to Seventh Layers) Second Layer to
The coating solution for the seventh layer was prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-oxy-3,
5-Dichloro-s-triazine sodium salt was used.
Ab-1, Ab-2, Ab-3 and Ab
-4, each having a total amount of 15.0 mg / m ² , 60.0 m
g / m ² , 5.0 mg / m ² and 10.0 mg / m ²
Was added so that

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The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.

-Blue-sensitive emulsion layer

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

Green sensitive emulsion layer

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(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^-FiveMole of sensitizing dye F per mole of silver halide.
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for size emulsion^-FourMole was added. )

-Red-sensitive emulsion layer

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(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. )

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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.

Further, 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 (the amount in parentheses indicates the coating amount).

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The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. (Support) Polyethylene resin laminated paper [White pigment (TiO ₂ ;
Content 16% by mass, ZnO; content 4% by mass) and a fluorescent whitening agent (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) The variation coefficients of the grain size distributions are 0.08 and 0.10, respectively. Each emulsion contains 0.3 mol% of silver bromide localized on a part of the grain surface based on silver chloride. 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 preventing layer)) Gelatin 0.99 Color mixture inhibitor (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-sized emulsion B having an average grain size of 0.45 μm and small-sized emulsion B having an average grain size of 0.35 μm) The variation coefficients of the grain size distributions are 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide is contained locally on 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 absorber (UV-4) 0.03 UV 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) 2 color 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 preventing layer)) Gelatin 0.71 Color mixture inhibitor (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-sized emulsion C having an average grain size of 0.50 μm and small-sized emulsion C of 0.41 μm) The variation coefficients of the grain size distribution are 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide is 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) 0.05 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) 0.0. 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 (ultraviolet absorbing layer)) Gelatin 0.66 Ultraviolet absorbing agent (UV-1) 0.19 Ultraviolet absorbing agent (UV-2) 0.06 Ultraviolet absorbing agent (UV-3) 0.06 UV absorber (UV-4) 0.05 UV absorber (UV-5) 0.08 UV 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, 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 with the comparative coupler (C-1) used in Comparative Example 1 described above. A photosensitive material 301 was prepared in exactly the same manner except that the molar amount was replaced. Example 1
Light-sensitive materials (302) to (305) were prepared in exactly the same manner except that the couplers (1), (2), (18) and (29) used in Nos. 1 to 4 were respectively replaced by the same molar amount. The average particle size of each of the cyan coupler-containing lipophilic fine particle dispersions prepared here was 0.10 to 0.1.
It was in the range of 20 μm.

The above light-sensitive 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 to twice the capacity of the color developing tank 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. 6 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-Potassium bromide 0.040 g 0.010 g 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 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 Flufinic 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 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher] Dechlorinated sodium isocyanurate 0.02 g 0.02 g 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 × sec (lux · sec) with an exposure time of 0.1 second. Separately, scanning exposures shown below were performed on each photosensitive material. JP-A-8-162 for scanning exposure
No. 38, the scanning exposure apparatus shown in FIG. 1 was used. As a 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) and combining the semiconductor laser with SHG. The amount of R light was modulated using an external modulator, reflected by a rotating polyhedron, and scanning-exposed to a sample moving perpendicular to the scanning direction. This 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 photographic materials performed in Comparative Example 1 and Examples 1 to 4 was performed. As a result, it was confirmed that all of the couplers of the present invention had high coloring properties and were excellent in hue and fastness.

<Example 6> ExY-2 and ExY-3 in the 13th and 14th layers of Sample 101 of JP-A-11-305396 were all changed to equimolar amounts to the coupler (1) of the present invention. Only different photosensitive materials were manufactured.
Exposure and development were performed by the method described in Example 1 of JP-A-305396 and evaluation was performed by the method described in the example of the present application. As a result, the same results as in Example 1 of the present application were obtained.

<Example 7> In Example 1 of JP-A-11-84601, the thirteenth layer and the first
A light-sensitive material was prepared in which the couplers C-5, C-6 and C-10 of the four layers and the couplers C-6 and C-10 of the fifteenth layer were all changed in equimolar amounts to the coupler (1) of the present invention. Then, exposure and development were performed by the method described in Example 1 of JP-A-11-84601, and evaluation was performed by the method described in the example of the present application. As a result, the same results as in Example 1 of the present application were obtained.

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According to the present invention, by adding a coupler which gives a dye having an excellent hue, a large molecular extinction coefficient and a good storage stability to a light-sensitive material, excellent color reproducibility and sharpness can be obtained. A silver halide color photographic light-sensitive material having good color image fastness can be provided. Another object of the present invention is to provide a simple method for producing an azo dye having a high molecular absorption coefficient and excellent hue and storage stability.

Claims (6)

[Claims] 1. A silver halide photographic material comprising at least one coupler represented by the following general formula (I). Embedded image (In the formula, Z represents an atomic group consisting of a carbon atom and / or a nitrogen atom which forms a 5- to 6-membered aromatic ring together with N—C. R represents a substituent, and when there are a plurality of Rs, May be the same or different, and may be mutually bonded to form a ring, m represents 0 or an integer of 1 to 4. X has a carbonyl group or a substituent Represents a methylene group or> C = N-Rn group, Rn represents a substituent, and Y represents a hydrogen atom or a substituent.) 2. The silver halide photographic material according to claim 1, wherein X in the coupler represented by formula (I) is a carbonyl group. 3. The silver halide photographic material according to claim 1, wherein Y in the coupler represented by the general formula (I) is an alkyl group, an aryl group or a heterocyclic group. 4. The coupler represented by the general formula (I) is a compound represented by the following general formulas (II), (III), (IV), (V) and (V)
2. The silver halide photographic material according to claim 1, which is at least one kind of coupler represented by I), (VII) or (VIII). Embedded image (In the formula, R represents a substituent, and when a plurality of Rs are present, they may be the same or different, and may be bonded to each other to form a ring. Or represents an integer of 1 to 3. X represents a carbonyl group, a methylene group which may have a substituent, or> C = N-Rn group.
Here, Rn represents a substituent. Y represents a hydrogen atom or a substituent. ) 5. A method for producing an azo dye, comprising using a compound represented by the following general formula (I). Embedded image (In the formula, Z represents an atomic group consisting of a carbon atom and / or a nitrogen atom which forms a 5- to 6-membered aromatic ring together with N—C. R represents a substituent, and when there are a plurality of Rs, May be the same or different, and may be mutually bonded to form a ring, m represents 0 or an integer of 1 to 4. X has a carbonyl group or a substituent Represents a methylene group or> C = N-Rn group, wherein Rn represents a substituent, and Y represents a hydrogen atom or a substituent.) 6. The compound represented by the general formula (I) and p
The method for producing an azo dye according to claim 5, wherein a phenylenediamine derivative is used.