JP2002318442A - Dye forming coupler, silver halide photographic sensitive material, and azomethine dye compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high activity dye forming coupler giving a dye having an excellent hue and good storage stability, a silver halide photographic sensitive material having superior color reproducibility and good color image fastness, and a dye having an excellent hue and good storage stability. SOLUTION: The dye forming coupler is represented by formula (I), the silver halide photographic sensitive material contains the coupler and the azomethine dye is represented by formula (II). In the formulae, Q is a residue forming an N-containing 6-membered ring together with -N-C=N-; L is a divalent linking group; R1 is a substituent; X is aryl; and Y is H or a group which can be released by coupling reaction with the oxidized body of a developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye-forming coupler which forms an azomethine dye by a coupling reaction with an oxidized form of a developing agent, and a silver halide photographic material containing the coupler. Further, the present invention relates to an azomethine dye compound 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 a color photographic method using a current p-phenylenediamine-based color developing agent, an acylacetic acid anilide-based compound is used as a yellow coupler. However, the hue of the yellow dye obtained from these couplers is reddish due to poor absorption on the long wavelength side of the absorption, and it is difficult to obtain a yellow hue of high purity, and the molecular extinction coefficient of the dye is also high. Is small, requires a large amount of coupler and silver halide to obtain a desired color density, and has a problem that the sharpness of the obtained color image may be reduced due to an increase in the thickness of the photosensitive material. Was. Further, the dye is easily decomposed under high-temperature and high-humidity conditions or under light irradiation conditions, and there is a problem in image storability after development processing.

In order to solve these problems, an acyl group and an anilide group have been improved. Recently, a coupler obtained by improving a conventional acyl acetate anilide system is described in JP-A-4-218,042. 1-alkylcyclopropanecarbonylacetic acid anilide type compound
Cyclomalondiamide type couplers described in JP-A-1141616, European Patent Nos. 954870A1 and 953
No. 871A1, No. 955872A1, No. 9538
No. 73A1, No. 953874A1, No. 95387
Pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic anilide couplers described in No. 5A1, etc. have been proposed. Dyes produced from these couplers have been improved in hue and molecular extinction coefficient compared to conventional ones, but are still insufficient in terms of image storability, and because the structure is complicated, the synthesis route is long,
Coupler cost increased, and there was a problem in practice.
In addition, U.S. Pat. No. 5,455,149 and the like have proposed an anilide acetate coupler to which an N-alkyl-4-pyrimidone is bonded, but the color density is low, and the light fastness of the formed dye is insufficient. These improvements have been desired.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a highly active dye-forming coupler which provides a dye having excellent hue and good storage stability and which can be produced in a short process at low cost. Another object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent color reproducibility and sharpness and excellent color image fastness by being added to the light-sensitive material. Another object of the present invention is to provide an azomethine dye excellent in hue and storage stability.

[0005]

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

[0006]

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In the formula, Q is nitrogen-containing together with -NC = N-part.
Represents a residue forming a 6-membered ring. L is a divalent linking group
R₁Represents a substituent. X represents an aryl group. Y is
For coupling reaction with hydrogen atom or oxidized developing agent
Represents a group capable of leaving more. However, -LR₁Is archi
Group, alkenyl group, alkynyl group, aryl group
And -LR₁Is Q and -NC = N-part
Bonds with the nitrogen atom of the nitrogen-containing 6-membered ring formed by
An atom cannot be a heterocyclic group linked by a carbon atom.
No. (2) The dye-forming coupler represented by the general formula (I)
Wherein Q is a residue forming a 4-pyrimidone ring.
The dye-forming coupler according to item (1), which is characterized in that
You. (3) The dye-forming coupler represented by the general formula (I)
Where Q is -C (-R _Two) = C (-R_Three) -CO-
(R_Two, R_ThreeAre bonded to each other to form -C = C-
Groups forming a 5- to 7-membered ring, or each independently water
(1) represents an element atom or a substituent)
The dye-forming coupler described in 1. above. (4) The dye-forming coupler represented by the general formula (I)
Where Q is -C (-R _Two) = C (-R_Three)-CO-
Represented by R_Two, R_ThreeAre bonded to each other together with -C = C-
Characterized by being a group forming a benzene ring (1)
The dye-forming coupler described in the above item. (5) The dye-forming coupler represented by the general formula (I)
Where Q is -C (-R _Two) = C (-R_Three)-CO-
Represented by R_Two, R_ThreeAre bonded to each other together with -C = C-
When the group forms a benzene ring,
Electron withdrawing property of Hammett's substituent constant σp value larger than 0
Characterized by having at least one substituent of
The dye-forming coupler according to item (1). (6) The dye-forming coupler represented by the general formula (I)
Where Q is -C (-R _Two) = C (-R_Three)-CO-
Represented by R_Two, R_ThreeAre bonded to each other together with -C = C-
Item (1), which is a group forming a heterocycle.
The dye-forming coupler described in 1. above. (7) a dye-forming coupler represented by the following general formula (I)
Halogenation characterized by containing at least one kind
It is a silver photographic light-sensitive material.

[0008]

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Wherein Q is nitrogen-containing together with -NC-N-part
Represents a residue forming a 6-membered ring. L is a divalent linking group
R₁Represents a substituent. X represents an aryl group. Y is
For coupling reaction with hydrogen atom or oxidized developing agent
Represents a group capable of leaving more. However, -LR₁Is archi
Group, alkenyl group, alkynyl group, aryl group
And -LR₁Is Q and -NC = N-part
Bonds with the nitrogen atom of the nitrogen-containing 6-membered ring formed by
An atom cannot be a heterocyclic group linked by a carbon atom.
No. (8) The dye-forming coupler represented by the general formula (I)
Wherein Q is a residue forming a 4-pyrimidone ring.
The silver halide photographic light-sensitive material according to the item (7), wherein
Material. (9) The dye-forming coupler represented by the general formula (I)
Where Q is -C (-R _Two) = C (-R_Three)-CO-
(R_Two, R_ThreeAre bonded to each other to form a -C = C-
Groups forming a 5- to 7-membered ring, or each independently
(Representing a hydrogen atom or a substituent) (7)
The silver halide photographic light-sensitive material described in the above section. (10) Dye-forming coupler represented by formula (I)
In the formula, Q is -C (-R_Two) = C (-R_Three)-CO-
And R_Two, R_ThreeAre bonded to each other to form a -C = C-
Is a group that forms a benzene ring
(7) A silver halide photographic material as described in the above item. (11) A dye-forming coupler represented by the general formula (I)
In the formula, Q is -C (-R_Two) = C (-R_Three)-CO-
And R_Two, R_ThreeAre bonded to each other to form a -C = C-
A group forming a benzene ring on the benzene ring
The electron withdrawal with Hammett's substituent constant σp value larger than 0
Characterized by having at least one functional substituent
(7) A silver halide photographic material as described in the above item. (12) Dye-forming coupler represented by formula (I)
In the formula, Q is -C (-R_Two) = C (-R_Three)-CO-
And R_Two, R_ThreeAre bonded to each other to form a -C = C-
Characterized in that the group forms a heterocycle (7)
The silver halide photographic light-sensitive material described in the above section. (13) Azomethine dye represented by the following general formula (II)
It is a compound.

[0010]

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In the formula, Q is a nitrogen-containing compound together with -NC-N-part.
Represents a residue forming a 6-membered ring. L is a divalent linking group
R₁Represents a substituent. X represents an aryl group.
R_Five, R₆Represents a hydrogen atom or a substituent independently. R₇Is
Represents a hydrogen atom or a substituent, and n is 0 or an integer of 1 to 4
Represents a number. When n is 2 to 4, a plurality of R₇Are the same
Can be the same or different
And may be condensed. Also R₇Is R_FiveOr R₆
And may be fused together. Also, R_FiveAnd R ₆
May combine with each other to form a ring. However, -L-
R₁Is an alkyl group, an alkenyl group, an alkynyl group, an ant
And -LR₁Is Q and -N
A nitrogen atom of a nitrogen-containing 6-membered ring formed by -C = N-
The atom that bonds to the child becomes a heterocyclic group that is bonded by a carbon atom.
Never. (14) Azomethine dye represented by formula (II)
In the compound, Q is a residue forming a 4-pyrimidone ring
The azomethine color according to the item (13), wherein
Element compound. (15) Azomethine dye represented by the general formula (II)
In the compound, Q is -C (-R_Two) = C (-R_Three)-C
O- (R_Two, R_ThreeAre bonded to each other to form -C = C-
Group forming a 5- to 7-membered ring together with the
Independently represents a hydrogen atom or a substituent)
An azomethine dye compound according to the item (13). (16) Azomethine dye represented by the above general formula (II)
In the compound, Q is -C (-R_Two) = C (-R_Three) -CO
-Represented by R_Two, R_ThreeAre bonded to each other to form a -C = C-
Characterized by both groups forming a benzene ring
An azomethine dye compound according to the item (13). (17) Dyeing azomethine represented by the general formula (II)
In the compound, Q is -C (-R_Two) = C (-R_Three) -CO
-Represented by R_Two, R_ThreeAre bonded to each other to form a -C = C-
When both groups form a benzene ring, the benzene ring
Above the electron absorption, the Hammett's substituent constant σp value is greater than 0.
Characterized by having at least one attractive substituent
An azomethine dye compound according to the item (13). (18) Azomethine dye represented by the general formula (II)
In the compound, Q is -C (-R_Two) = C (-R_Three)-C
Represented by O-, R_Two, R_ThreeAre bonded to each other to form a -C = C-
Is a group that forms a heterocycle with
An azomethine dye compound according to the item (13).

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below. (Dye-Forming Coupler) The compound represented by formula (I) of the present invention (also referred to as a dye-forming coupler in the present application) will be described in detail.

[0013]

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In the formula, Q represents a residue which forms a nitrogen-containing 6-membered ring together with -N = C = N-. L is a divalent linking group, and R ₁ represents a substituent. However, -LR ₁ is not an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and -LR ₁ is a nitrogen-containing 6 formed by Q and -NC = N- moiety. The atom bonded to the nitrogen atom of the member ring does not become a heterocyclic group bonded by a carbon atom.

In the present invention, L is Q and -NC = N
The atom on L bonded to the nitrogen atom on the nitrogen-containing 6-membered ring formed by the-
A nitrogen atom, a sulfur atom, a phosphorus atom, a boron atom, etc., or a carbon atom such as -C (= O)-
L-R ₁ is an alkyl group, an alkenyl group, rather than be an alkynyl group or an aryl group, also, -L-R ₁
Does not become a heterocyclic group bonded to the nitrogen atom on the -NC = N- part by a carbon atom. )). Here, -LR ₁ is an aryl group, which means that L is an arylene group, and -L- 1
When R ₁ is a heterocyclic group, it means that L is a divalent heterocyclic group. Such divalent linking group L, such, -O -, - N (R a) -, - S -, - SO 2 - or -SO- or -C (= O) -, or combinations thereof, And the like. Preferably -O-, -N
_{(R a) -, - S} -, - SO 2 -, - C (= O) - it is. Here, Ra represents _a hydrogen atom or a substituent. The substituent in R _a, include those similar to the examples of R ₁ shown below.

Examples of R ₁ include an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group,
Cyano group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including alkylamino group and anilino group) 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, Sulfo group,
Alkyl and aryl sulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups,
Examples include a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

Here, R ₁ may be further substituted with a substituent. Examples of the substituent include a group obtained by adding a halogen atom, a hydroxyl group, or a nitro group to the groups exemplified as the above-mentioned R _1. No.

When R ₁ is substituted with a plurality of substituents, these substituents may be the same or different, and adjacent substituents may be bonded to each other to form a ring, preferably 5 It may form a 6-membered saturated or unsaturated ring. The above substituent may be further substituted with a substituent, and examples of the substituent include a group obtained by adding a halogen atom to the group described as an example of R ₁ described above.

Hereinafter, examples of R ₁ will be further described. As these substituents, an alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably having 1 to 3 carbon atoms)
0, an alkyl group such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-
Ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms,
Examples include cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, and a polycycloalkyl group such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, bicyclo [ 1,2,2] heptane-2-yl, bicyclo [2,2,2] octan-3-yl) and tricyclic alkyl groups. Preferred are a monocyclic cycloalkyl group and a bicycloalkyl group, and a monocyclic cycloalkyl group is particularly preferred. ),

Alkenyl group [a linear or branched, substituted or unsubstituted alkenyl group, preferably having 2 to 3 carbon atoms;
0, for example, vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, for example, 2-cyclopentene-
1-yl, 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-en-1-yl, bicyclo [2,
2,2] oct-2-en-4-yl)], a tricycloalkenyl group and a bicycloalkenyl group, and a monocyclic cycloalkenyl group is particularly preferred. ), An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group),

Aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl,
p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or A condensed heterocyclic group, more preferably a heterocyclic ring in which the ring-constituting atoms are selected from a carbon atom, a nitrogen atom and a sulfur atom, and which have at least one heteroatom of nitrogen, oxygen and sulfur And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-
Pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, carboxyl group,

An alkoxy group (preferably having 1 to 3 carbon atoms)
0 substituted or unsubstituted alkoxy groups such as 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, such as phenoxy,
-Methylphenoxy, 4-t-butylphenoxy, 3-
Nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably 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, wherein the heterocyclic portion is the heterocyclic group described above. The heterocyclic moiety described for the ring group is preferable, 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), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, For example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably having 7 to 3 carbon atoms)
0 substituted or unsubstituted aryloxycarbonyloxy groups 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, a heterocyclic ring having 0 to 30 carbon atoms) An amino group such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,
3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 6 to 30 carbon atoms) An amino group, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably having 1 to 30 substituted or unsubstituted aminocarbonylamino groups such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N
-Diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n -Octadecyloxycarbonylamino,
N-methyl-methoxycarbonylamino),

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 having no carbon atoms)
30 to 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably A substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms,
For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), a mercapto group,

An alkylthio group (preferably having a carbon number of 1 to
30 substituted or unsubstituted alkylthio groups, for example, methylthio, ethylthio, n-hexadecylthio), and arylthio groups (preferably substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms, for example, phenylthio,
p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic portion is the heterocyclic group described above for the heterocyclic group. A ring portion is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfoyl). Famoyl, 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, such as 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, ethyl A sulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) Yes, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably
A substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-
Chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl),

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably A substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-
Dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),
Aryl and heterocyclic azo groups (preferably having 6 to 3 carbon atoms)
0 substituted or unsubstituted arylazo group, having 3 to 3 carbon atoms
30 substituted or unsubstituted heterocyclic azo groups (the heterocyclic portion is preferably the heterocyclic portion described for the aforementioned heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4 -Thiadiazole-2
-Ylazo), an imide group (preferably having 2 to 30 carbon atoms)
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 a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

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).

Among the substituents which R ₁ may have, those having a hydrogen atom may be removed and further substituted with the above groups. Examples of such a substituent that R ₁ may further have include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Is methylsulfonylaminocarbonyl,
p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, benzoylaminosulfonyl, dodecylcarbonylaminosulfonyl, p-chlorophenylcarbonylaminosulfonyl, dodecanesulfonylaminocarbonyl, p-toluenesulfonylaminocarbonyl, p-dodecyloxy And a benzenesulfonylaminocarbonyl group.

Adjacent substituents may combine with each other to form a ring, preferably a 5- to 7-membered saturated or unsaturated ring, which is an alicyclic, aromatic or heterocyclic ring. Examples thereof include a benzene ring, a furan ring, a thiophene ring, a cyclopentane ring, and a cyclohexane ring.

The rings each of these substituents or a plurality of substituents are bonded to form one another, the further substituent (exemplified halogen atom group as R ₁ described above (e.g., chlorine atom, bromine atom, iodine atom) ), A hydroxyl group or a nitro group. The total number of carbon atoms of R ₁ is preferably 2 to 50, more preferably 8
To 45, more preferably 15 to 40. Among these R _1, preferred are an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cyano group, an acylamino group, an alkylsulfonylamino group, Alkoxycarbonyl group, carbamoyl group,
It is a sulfamoyl group, an alkylamino group or an arylamino group. When L is -N (R _a )-, the substituent in R _a has the same meaning as R ₁ described above, and the preferred range is also the same.

In the general formula (I), Q is -NC = N
Represents a residue forming a nitrogen-containing 6-membered hetero ring together with the-part.
The nitrogen-containing hetero ring is a substituted or unsubstituted hetero ring, more preferably a hetero ring group in which the ring-constituting atoms are composed of carbon atoms and nitrogen atoms, and having 2 to 4 nitrogen atoms, Preferably, it is a nitrogen-containing 6-membered heterocycle having 2 to 30 carbon atoms and having two nitrogen atoms. Q is -N
Examples of the nitrogen-containing 6-membered ring formed together with the -C = N- moiety include 4-pyrimidone, 1,3-diazine-4,6-dione,
Examples thereof include 1,3,5-triazin-2-one and 1,2,4-triazin-5-one. Q is -NC = N-
Nitrogen-containing 6-membered ring formed together with the parts may have a substituent, examples of the substituent include a halogen atom (a fluorine atom as those listed for R ₁ described above, a chlorine atom, a bromine atom, iodine Atoms), a group to which a hydroxyl group or a nitro group is added. Further, adjacent substituents may be bonded to each other to form a ring, preferably a 5- to 7-membered saturated or unsaturated ring, which may be an alicyclic ring, an aromatic ring, or a heterocyclic ring. Often, a benzene ring, a furan ring, a thiophene ring, a cyclopentane ring, and a cyclohexane ring are exemplified.

The rings each of these substituents or a plurality of substituents are bonded to form each other, a substituent (a halogen atom as those listed for R ₁ a above (fluorine atom, chlorine atom, bromine atom, iodine atom And the like), a hydroxyl group and a nitro group. Further, the total number of carbon atoms of the substituent is preferably 2 to 50, more preferably 8 to 45, and still more preferably 15 to 4
0 is preferred. Among these substituents, 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 alkyl and arylsulfonylamino group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylamino group or an arylamino group.

Preferably, Q is a residue forming a 4-pyrimidone ring. More preferably Q is -C (-R ₂₎ =
C (-R ₃₎ - it is represented by CO-. R ₂ and R ₃ are bonded to each other to form a 5- to 7-membered ring together with a —C ＝ C— moiety;
Alternatively, each independently represents a hydrogen atom or a substituent.
The ring formed by R ₂ and R ₃ together with the —C ＝ C— moiety is preferably a 5- to 7-membered alicyclic ring, aromatic ring or heterocyclic ring, for example, benzene ring, pyrazole ring, furan Ring, thiophene ring, cyclopentene ring and cyclohexene ring. More preferably, the ring is 6
A membered aromatic ring, most preferably a benzene ring.
When R _2, R ₃ represent a substituent, they may be different even in the same, halogen atom as those listed for R ₁ described above as examples of substituents (fluorine atom, chlorine atom, bromine Atom, iodine atom, etc.), hydroxyl group, nitro group, and the like.

In the dye-forming coupler represented by the formula (I), Q is represented by -C (-R ₂ ) = C (-R ₃ ) -CO-, and R ₂ and R ₃ are bonded to each other. When —C ＝ C— is a group that forms a benzene ring together with the C— moiety, it preferably has an electron-withdrawing substituent having a Hammett's substituent constant σp value larger than 0 on the benzene ring, 0-1.5
It is more preferred that the compound has an electron-withdrawing substituent. The sum of the σp values of the substituents on this benzene ring is 0
Or more, more preferably 0.40 or more, and 0.6 or more.
0 or more is more preferable, and 0.80 or more is most preferable.
Here, the sum of the σp values is preferably 3.90 or less. In addition,
Regarding Hammett's substituent constants σp and σm, for example,
Naoki Inamoto, Hammett's Rule-Structure and Reactivity-(Maruzen),
The Chemical Society of Japan, “New Experimental Chemistry Lecture 14: Synthesis and Reaction of Organic Compounds V”, p. 2605 (Maruzen), Tadao Nakatani, “Explanation of Theoretical Organic Chemistry”, p. The book is described in detail in pages (1991).

In the general formula (I), X represents an aryl group.
You. The aryl group preferably has 6 to 30 carbon atoms.
Substituted or unsubstituted aryl groups such as phenyl, na
Futyl. X may have a substituent,
Examples of the substituent include the aforementioned R ₁Of the substituent which may have
Examples include halogen atoms, hydroxyl groups,
A group to which a nitro group is added may be mentioned. X having a substituent
Preferred examples include an alkyl group, an alkenyl group,
Group, heterocyclic group, halogen atom, alkoxy group,
Reeloxy, alkylthio, arylthio,
Ano group, acylamino group, alkyl and aryl sulfo
Nilamino group, alkoxycarbonyl group, carbamoyl
Group, sulfamoyl group, alkylamino group or aryl
It is a ruamino group. Preferably an amide moiety on the aryl group
A halogen atom (for example, fluorine)
Element atom, chlorine atom), alkyl group (for example, methyl group),
Alkoxy group (for example, methoxy group, isopropyloxy
Group, dodecyloxy group), aryloxy group (for example,
(Enoxy group). More preferably
It is preferable to have a halogen atom and an alkoxy group,
It is more preferred to have an alkoxy group.
No. X is preferably a phenyl group, and the amide moiety of the phenyl group
The position that binds to the first position, at least in the second position
Those having a substituent are preferable, and the above-mentioned
Those having a substituent are more preferred.

In the general formula (I), Y represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developing agent. Examples of Y include a group leaving with a nitrogen atom, a group leaving with an oxygen atom, a group leaving with a sulfur atom, and a halogen atom (for example, a chlorine atom or a bromine atom).
Examples of the group capable of leaving at the nitrogen atom include a heterocyclic group (preferably 5 to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic (in the present application, one having 4n + 2 cyclic conjugated electrons)) An aromatic, monocyclic or condensed ring heterocyclic group, more preferably a ring-constituting atom selected from a carbon atom, a nitrogen atom and a sulfur atom, and any one of a nitrogen atom, an oxygen atom and a sulfur atom A 5- or 6-membered heterocyclic group having at least one such as succinimide, maleimide,
Phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4
-Dione, oxazolidine-2,4-dione, thiazolidine-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazoline- 5-
On, indoline-2,3-dione, 2,6-dioxypurineparabanic acid, 1,2,4-triazolidine-3,
5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-
1,3,4-thiazolidine-4-one), carbonamide group (eg, acetamide, trifluoroacetamide), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), arylazo group (eg, phenylazo, naphthylazo), carbamoylamino Groups (for example, N-methylcarbamoylazo).

Among the groups capable of leaving with a nitrogen atom, preferred are heterocyclic groups, and more preferred are aromatic heterocyclic groups having 1, 2 or 4 nitrogen atoms as ring-constituting atoms, or the following general formula: It is a heterocyclic group represented by (L). More preferably, it is a heterocyclic group represented by the general formula (L).

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In the formula, L is 5-6 together with -NC (= O)-
It represents a residue forming a nitrogen-containing hetero ring of a member ring. Examples of these are given in the description of the above heterocyclic group, and these are more preferred. Among them, L is preferably a residue forming a 5-membered nitrogen-containing heterocycle.

Examples of the group capable of leaving with an oxygen atom include an aryloxy group (eg, phenoxy, 1-naphthoxy), a heterocyclic oxy group (eg, pyridyloxy, pyrazolyloxy), an acyloxy group (eg, acetoxy, benzoyloxy), and an alkoxy group (eg, Methoxy, dodecyloxy), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbamoyloxy), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy), alkoxycarbonyloxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy) , An alkylsulfonyloxy group (eg, methanesulfonyloxy), an arylsulfonyloxy group (eg, benzenesulfonyloxy, toluenesulfonyloxy) and the like. It is below. Among the groups which are split off by an oxygen atom, preferred are an aryloxy group, an acyloxy group and a heterocyclic oxy group.

Examples of the group capable of leaving by a sulfur atom include an arylthio group (eg, phenylthio, naphthylthio), a heterocyclic thio group (eg, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxazolylthio, benzimidazolyl) Thio), alkylthio group (eg, methylthio, octylthio, hexadecylthio), alkylsulfinyl group (eg, methanesulfinyl), arylsulfinyl group (eg, benzenesulfinyl), arylsulfonyl group (eg, benzenesulfonyl), alkylsulfonyl group (eg, methanesulfonyl) Is mentioned. Among the groups which are eliminated by a sulfur atom, preferred are an arylthio group and a heterocyclic thio group, and a heterocyclic thio group is more preferred.

Y may be substituted by a substituent,
Examples of the substituent that substitutes for Y include those described above as examples of the substituent of R ₁ . Y is preferably a group leaving at a nitrogen atom, a group leaving at an oxygen atom, a group leaving at a sulfur atom, more preferably a group leaving at a nitrogen atom, further preferably a group leaving at a nitrogen atom. It is preferable in the order of the preferable groups described above. The preferred group for Y is further described below. An aromatic heterocyclic group having 1, 2 or 4 nitrogen atoms as a ring-constituting atom, or a heterocyclic group represented by formula (L) (particularly preferably, A heterocyclic group represented by (L)), a group capable of leaving with an oxygen atom (particularly preferably an aryloxy group, an acyloxy group or a heterocyclic oxy group), a group capable of leaving with a sulfur atom (preferably an arylthio group, a heterocyclic thio group) And particularly preferably a heterocyclic thio group).

Further, Y may preferably be a photographically useful group. Examples of the photographically useful group include a development inhibitor, a desilvering accelerator, a redox compound, a dye, a coupler, and the like, or a precursor thereof. More preferably, Y
Is a development inhibitor and a precursor thereof, and examples thereof include those described as a development inhibitor and a precursor thereof in JP-A-2000-17195, and preferred examples are also described as preferable among them. Is the same as

In order to immobilize the coupler in the light-sensitive material, at least one of Q, R ₁ , X and Y preferably has a total carbon number including a substituent of 8 to 50, more preferably The total carbon number is 10 or more and 40 or less.

Preferred examples of the coupler represented by formula (I) in the present invention are shown below, but the present invention is not limited thereto. It should be noted that tautomers in which a hydrogen atom is transferred onto a carbonyl group or a nitrogen-containing 6-membered ring are also included in the scope of the present invention. In the present specification, Me is methyl, Et is ethyl, Bu is butyl,
Ph represents phenyl.

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In the following description, when reference is made to the exemplified compounds (also referred to as dye-forming couplers) shown above, the parenthesized number (X) attached to each exemplified compound is used as an example. Compound (X) "or" coupler (X) ".

Specific examples of the synthesis of the compound represented by formula (I) are shown below. Synthesis Example 1: Synthesis of Exemplified Compound (11) Exemplified Compound (11) was synthesized by the following route.

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A solution of 13.7 g of anthranilic acid and 22.0 g of imino ether in 200 ml of acetonitrile was heated to 70 ° C.
And stirred for 1 hour. Ethyl acetate and water were added and the mixture was separated, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. The residue was purified by column chromatography, and then crystallized from a mixed solvent of ethyl acetate and hexane to obtain 17.5 g of a compound (A-1).

16.3 g of compound (A-1) and 4.2 g of dimethylhydrazine in 100 ml of tetrahydrofuran
Was heated and refluxed for 1 hour. Ethyl acetate and water were added, and the mixture was separated. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Crystallization from a mixed solvent of ethyl acetate and hexane gave 15.4 g of compound (A-2).

Compound (A-2) 13.8 g, 2-methoxy-5-tridecaoxycarbonylaniline 18.2 g
Was stirred for 3 hours while heating under reflux. Ethyl acetate and water were added, and the mixture was separated. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
The residue was purified by column chromatography, and then crystallized from a mixed solvent of ethyl acetate and hexane to obtain 27.1 g of the exemplary compound (11).

Synthesis Example 2: Synthesis of Exemplified Compound (1) Exemplified Compound (1) was synthesized by the following route.

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To 200 ml of a methylene chloride solution of 23.7 g of the exemplary compound (11), 50 ml of a methylene chloride solution of 6.4 g of bromine was added dropwise under ice cooling. After stirring at room temperature for 30 minutes, water was added and the mixture was separated. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. N, N-
50 ml of dimethylacetamide was added, 28 g of N-benzyl-ethoxyhydantoin and triethylamine 16.
It was added dropwise to 7 ml of a 200 ml solution of N, N-dimethylacetamide under ice-cooling. After stirring at room temperature for 2 hours, 400 g of an aqueous solution of 20 g of sodium hydroxide and ethyl acetate were added, and the mixture was separated and washed with 150 ml of 1N hydrochloric acid and 150 ml of water. After drying the organic layer over anhydrous magnesium sulfate,
The solvent was distilled off under reduced pressure. Crystallization from a mixed solvent of ethyl acetate and hexane yielded 23 g of Exemplified Compound (1).

Synthesis Example 3: Synthesis of Exemplified Compound (5) The exemplified compound (5) was synthesized by the following route.

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A solution of 23.3 g of compound (A-1) and 3.2 ml of anhydrous hydrazine in 50 ml of methyl alcohol was stirred at room temperature overnight. The crystallized product was filtered, washed with methyl alcohol, and dried to obtain 22.4 g of a compound (B-
1) was obtained.

To a solution of 20.0 g of the compound (B-1) and 12.3 g of benzoyl chloride in acetonitrile, 12.2 ml of triethylamine was added dropwise under ice-cooling. 1 at room temperature
The mixture was stirred overnight, ethyl acetate and water were added thereto, and the mixture was separated. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Crystallization from a mixed solvent of ethyl acetate and hexane gave 26.1 g of compound (B-2).

Compound (B-2) 24.6 g, 2-methoxy-5-tridecaoxycarbonylaniline 25.5 g
Was stirred for 3 hours while heating under reflux. Ethyl acetate and water were added, and the mixture was separated. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. After the residue was purified by column chromatography, ethyl acetate,
Crystallization from a mixed solvent of hexane gave 25.8 g of Exemplified Compound (5).

Synthesis Example 4: Synthesis of Exemplified Compound (3) The exemplified compound (3) was synthesized by the following route.

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50 ml of a methylene chloride solution containing 4.8 g of bromine was added dropwise to 200 ml of a methylene chloride solution containing 20.1 g of the exemplified compound (5) under ice-cooling. After stirring at room temperature for 30 minutes, water was added and the mixture was separated. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. N, N-
50 ml of dimethylacetamide was added, and the mixture was added dropwise to a solution of 12.7 g of 5,5-dimethyl-oxazolidine-2,4-dione and 12.5 ml of triethylamine in 200 ml of N, N-dimethylacetamide under ice-cooling. After stirring at room temperature for 2 hours, the mixture was stirred at 40 ° C. for 1 hour. 400 ml of an aqueous solution of 20 g of sodium hydroxide and ethyl acetate were added thereto, and the mixture was separated and washed with 150 ml of 1N hydrochloric acid and 150 ml of water. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. Crystallization from a mixed solvent of ethyl acetate and hexane gave 16.7 g of Exemplified Compound (3).

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

The dye-forming coupler represented by formula (I) may be 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). Sensitive silver halide emulsion layer)
Can also be contained. The dye-forming coupler represented by the formula (I) is useful mainly as a yellow coupler or a magenta coupler when combined with a color developing agent such as a p-phenylenediamine, and particularly useful as a yellow coupler. is there. Therefore, the silver halide photographic light-sensitive material of the present invention has p-type as a color developing agent.
When phenylenediamines are used, the dye-forming coupler represented by the above general formula (I) is preferably contained in a layer for coloring yellow couplers or magenta couplers, and is preferably contained in a layer for coloring yellow. Is particularly preferred. Further, the dye-forming 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 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-5-323439.
No. 5,323,541, No. 6-258803, No. 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) 2,541,274. , 2
No. 541,230, Japanese Patent Publication No. 53-41091 and European Patent Publication No. 029104, and the dispersion with an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723 and JP-A-5-15042.
No. 0, etc. Methacrylate-based or acrylamide-based polymers are preferred, and acrylamide-based polymers are particularly preferred in view of image fastness.

Here, the high boiling point means a boiling point of 175 ° C. or more at normal pressure. Examples of the high boiling point solvent used in the present invention are described in U.S. Pat. No. 2,322,027 and the like. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at normal pressure include phthalic acid esters such as dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, and bis (2,4-diethyl phthalate). -Tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate],
Esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate ,
2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone), sulfonamides (eg, N-butylbenzenesulfonamide),
Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctylazelate, glycerol tributyrate, isostearyl Lactate, trioctyl citrate), aniline derivatives (such as N, N-dibutyl-2-butoxy-5-tert-octylaniline),
Hydrocarbons (eg, paraffin, dodecylbenzene,
Diisopropylnaphthalene), chlorinated paraffins and the like. In particular, phosphate esters and JP-A-6-258
The hydrogen donating compounds described in JP-A Nos. 803 and 8-262662 are excellent in terms of hue and can be preferably used.

In order to reduce the load on the environment,
Instead 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. or more and about 160 ° C. or less can be used. ,
Examples include cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The emulsion dispersion may be used, if necessary, from the viewpoint of improving the stability over time during storage in the state of the emulsion dispersion, suppressing the change in photographic performance and improving the stability over time of 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 distillation under reduced pressure, washing with noodles or ultrafiltration. The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.001 to 1.0 μm, more preferably 0.05 to 0.30 μm, and most preferably 0.08 to 0.20 μm. It is. Average particle size is Coulter Submicron Particle Analyzer model N4 (Coulter Electronics)
And the like. If the average particle size of the lipophilic fine particle dispersion is large, 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. , Making it difficult to handle during manufacture.

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

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

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

It is also preferable to provide a polyolefin layer on the opposite side (back side) of the above-mentioned paper base from the photographic constituent layer in order to increase the rigidity of the reflective support. In this case, the polyolefin layer on the back side has a matte surface. Polyethylene or polypropylene is preferred, and polypropylene is more preferred. 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 reflection support of the present invention, a preferred embodiment relating to a polyolefin layer provided on a paper substrate is described in JP-A-10-3.
No. 33277, No. 10-333278, No. 11-52
No. 513, No. 11-65024, EP0880065
And the examples described in EP 0 880 066.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. 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 a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

Further, as a support used for the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment was provided on a support having a silver halide emulsion layer for a display. A support may be used. In order to further improve the sharpness, it is preferable to coat 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 can be decolorized on the hydrophilic colloid layer by the processing described in EP 0,337,490 A2, pp. 27-76, for the purpose of improving the sharpness of the image. Dyes (particularly oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, and dihydric alcohols (for example, Titanium oxide surface-treated with trimethylolethane)
The content is preferably 2% by mass or more (more preferably 14% by mass or more).

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

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

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

The silver halide grains in the silver halide emulsion used in the present invention are preferably cubic or tetradecahedral crystal grains having substantially {100} planes (these grains have rounded apexes and 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 used in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsion 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 since high sensitivity can be obtained and photographic performance can be stabilized.

The localized silver bromide phase is preferably formed by epitaxially growing a localized phase having a total silver bromide content of at least 10 mol% or more in the localized silver bromide phase. The silver bromide content of the silver bromide localized phase is preferably in the range of 10 to 60 mol%, most preferably in the range of 20 to 50 mol%.
The silver bromide localized phase is preferably composed of silver in an amount of 0.1 to 5 mol% of the total silver constituting the silver halide grains in the present invention, and is preferably composed of 0.3 to 4 mol% of silver. More preferably, it is constituted. In the localized phase of silver bromide, iridium (III) chloride, iridium (III) bromide,
Iridium (IV) chloride, sodium hexachloroiridate (III), hexachloroiridium (IV)
It is preferable to contain a Group VIII metal complex ion such as potassium acid, 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, a metal compound having at least four cyano ligands, such as iron, ruthenium, osmium, and rhenium, is particularly preferred in that it further enhances high illuminance sensitivity and suppresses latent image sensitization. In addition, the iridium compound has a great effect on imparting high illuminance exposure suitability. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide.

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

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

In the present invention, a hydroxamic acid derivative described in JP-A-11-109576 and a hydroxamic acid derivative described in JP-A-11-32709 are described in order to enhance the storage stability of the silver halide emulsion.
Cyclic ketones having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group described in No. 4 (especially those represented by the general formula (S1), paragraphs 0036 to 0071) Can be incorporated in the specification of the present application.) And sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example,
4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,
3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), and the general formulas (I) to (III) of JP-A-11-102045. A hydroxylamine represented by the general formula (A) in U.S. Pat. No. 5,556,741 (column 56, U.S. Pat. No. 5,556,741). Eleventh
The description in column 22, line is preferably applied also in the present application, and is incorporated as a part of the specification of the present application).

The spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, FMHarmer's Heterocyclic compounds-Cyanine d
yes andrelated compounds (John Wiley & Sons [New Y
ork, London], 1964). As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used. Particularly, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, JP-A-3-123
The spectral sensitizing dye described in JP-A-340 is very preferable from the viewpoints of stability, strength of adsorption, temperature dependency of exposure and the like.

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

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column, are preferably used. Among them, it is particularly preferable that the 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. The addition amount of these compounds may vary widely depending on the case, but is from 5 × 10 ^{−7 to} 5 × per mol of silver halide.
The amount is 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol. In the present invention, gold sensitization may be combined with other sensitization methods, 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, a different layer configuration may be adopted. For example, when the coupler represented by the general formula (I) functions as a yellow coupler,
The silver coupler emulsion layer containing the yellow coupler may be arranged at any position on the support. It is preferable that the coating is provided at a position farther from the support than at least one of the silver emulsion layer and the cyan coupler-containing silver halide emulsion layer. From the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the silver halide emulsion layer containing the yellow coupler is coated at a position farthest from the support than the other silver halide emulsion layers. Preferably, it is provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a layer at the center of the other silver halide emulsion layers, and from the viewpoint of reducing photo-fading, the cyan coupler-containing silver halide emulsion layer is preferably The lowermost layer is preferred. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, JP-A-4-75055 and JP-A-9-114035
No. 10-246940, U.S. Pat.
No. 159, etc., 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 arrangements, etc.) used in the present invention, and the processing methods and processing additions applied for processing this light-sensitive material As the agent, JP-A-62-2
No. 15272, JP-A-2-33144, European Patent EP
No. 0,355,660 A2, particularly those described in European Patent EP 0,355,660 A2 are preferably used. Further, JP-A-5-34
No. 889, No. 4-359249, No. 4-313375
Nos. 4-270344, 5-66527, and 4
-34548, 4-145433, 2-854
Nos. 1-158431, 2-90145 and 3
Also preferred are silver halide color photographic light-sensitive materials described in, for example, JP-A-194539, JP-A-2-93641, and European Patent Publication No. 0520457A2, and a processing method thereof.

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

[0105]

[Table 1]

[0106]

[Table 2]

The cyan, magenta and yellow couplers used in combination in the present invention are described in
JP-A-2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column last line and page 30, upper right Lines 6 to 35, lower right column, line 11 and EP 0355,660A2, page 4, lines 15 to 27, page 5, line 30 to page 28, last line, page 45, lines 29 to 31 Eye, page 47, lines 23-6
The couplers described on page 3, line 50 are also useful. Further, the present invention relates to the general formulas (II) and (II) of WO98 / 33760.
I), a compound represented by formula (D) of JP-A-10-221825 may be added, which is preferable.

In the silver halide photographic light-sensitive material of the present invention, the dye-forming coupler represented by formula (I) may be used alone or in combination. 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, a malondianilide-type yellow coupler having a cyclic structure described in European Patent EP 0482552A1, European Patent No. 954870A1,
Pyrrole-2 or 3- described in Nos. 953831A1, 953832A1, 953833A1, 953874A1, 9553875A1, and the like.
Yl or indole-2 or 3-ylcarbonylacetic anilide based couplers, U.S. Pat. No. 5,118,59
An acylacetamide-type yellow coupler having a dioxane structure described in JP-A No. 9 is preferably used. Among them, an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides forms an indoline ring are particularly preferably used in combination.

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

The heterocyclic couplers described in European Patent EP
Pyrroazole type cyan couplers described in US Pat. No. 4,488,248 and EP 0491197 A1, US Pat.
Pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in JP-A No.
Nos. 71185, 8-31360, 8-3390
It is also preferable to use in combination with a pyrazoloazole-type cyan coupler having a carbamoyl group at the 6-position described in No. 60. In addition,
Of these cyan couplers, JP-A-11-2821
Particularly preferred are pyrroloazole-based cyan couplers represented by the general formula (I) described in JP-A No. 38;
Descriptions of 012 to 0059 are for example cyan couplers (1) to
Including (47), it is applied to the present application as it is, and is preferably incorporated as a part of the specification of the present application.

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

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

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

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

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

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

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

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

In the case where 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 cathode ray is exposed. A plurality of color image signals may be input to the tube to emit light from the tube surface. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for 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) in which a solid-state laser using a semiconductor laser as an excitation light source is combined with a nonlinear optical crystal.
A digital scanning exposure method using monochromatic high-density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

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

The preferred scanning exposure method applicable to the present invention is described in detail in the publications listed in the above table. Further, for processing the light-sensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5 upper left column The processing materials and processing methods described in the 17th line to the 20th line on the lower right column on page 18 can be preferably applied. As the preservative used in this developer, compounds described in the publications listed in the above table are preferably used.

The present invention is preferably applied to a photosensitive material having suitability for rapid processing. The color development time refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fix solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called in-solution 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 (the 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 in-solution time).

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

The photosensitive material of the present invention can be developed after exposure by a conventional method of developing with a developing solution containing an alkaline agent and a developing agent, an alkaline solution containing a developing agent incorporated in the photosensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator solution such as a method described above, a thermal developing method without using a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because the developing agent is not contained in the processing solution, so that the processing solution can be easily managed and handled, and the load at the time of processing the waste solution is small. 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 the hydrazine-type compounds described in JP-A Nos. 9-218814 and 9-160193 are preferable.

Further, a development 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 used is also 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, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photographing is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, Research Disclosure Item 36544
(September 1994) Pages 536 to 541, JP-A-8
No. 234388 can be used.

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

The photosensitive material of the present invention can be preferably applied as a photosensitive 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 and JP-A-6-17528,
146133, 60-119557, JP-A-1-
No. 161236 has a detailed description.

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 material described in JP-A-11-7109 is preferred. Particularly, 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 of paragraphs 0018 to 0021 in the specification of JP-A-11-84601 is preferably applied and incorporated as a part of the specification of the present application.

(Azomethine Dye) Next, the compound represented by the general formula (II) of the present invention (also referred to as azomethine dye in the present application) will be described in detail.

[0133]

Embedded image

In the general formula (II), R ₁ , Q, L, X
Represents the same one as in the general formula (I). Further, the same as those in the general formula (I) are preferable.

In the general formula (II), R ₅ and R ₆ independently represent a hydrogen atom or a substituent. R ₇ represents a hydrogen atom or a substituent, and n represents 0 or an integer of 1 to 4. R ₅ ,
When R ₆ and R ₇ represent a substituent, examples of the substituent include groups described above as examples of R ₁ to which a halogen atom has been added. When n is 2 to 4, R ₇ may be the same or different, and may be bonded to each other and condensed. R ₇ may be bonded to R ₅ or R ₆ to form a condensed ring. R ₅ and R ₆ may be bonded to each other to form a ring (preferably a 5- to 6-membered ring, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring). .

R ₇ is preferably a hydrogen atom, having 1 to 3 carbon atoms.
0 substituted or unsubstituted alkyl group, 1 to 30 carbon atoms of a substituted or unsubstituted alkenyl group, 6 to 30 carbon atoms of a substituted or unsubstituted aryl group, 1 to 30 carbon atoms of a substituted or unsubstituted alkoxy group Group, halogen atom or 1 to 30 carbon atoms
Is a substituted or unsubstituted acylamino group, more preferably a hydrogen atom or an alkyl group. More preferably, R
₇ is preferably a methyl group ortho to the azomethine nitrogen.

R ₅ and R ₆ are preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. More preferably, it is an alkyl group, and still more preferably, one of R ₅ and R ₆ is an ethyl group, and the other is a 2-hydroxyethyl group or a 2-hydroxyethyl group.
-A methanesulfonamidoethyl group.

Preferred specific examples of the azomethine dye represented by formula (II) in the present invention are shown below.
The present invention is not limited to these.

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

The compound represented by the general formula (II) of the present invention comprises a compound represented by the general formula (I) of the present invention and a phenylenediamine-based developing agent, particularly, N, N-disubstituted-p-phenylenediamine. It can be synthesized by performing a coupling reaction with an oxidized derivative. The general formula (I) of the present invention
Can also be synthesized by reacting a compound represented by the formula wherein Y is a hydrogen atom with a 4-nitrosoaniline-based compound. Specific examples of the synthesis method will be shown in the examples below, but the present invention is not limited to the examples.

The azomethine dye compound of the present invention can be used in many applications in terms of its excellent hue and fastness. In particular, it is effective for inks and dyes, but is effective for dyes for images, for example, dyes for inks for ink jet printers, but is useful as dyes for color photography.

[0146]

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 Examples 1 and 2> Preparation of Comparative Dye (CD-1) The following comparative coupler (C-1): 0.85 g, N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate: 0.1. 80 g, sodium carbonate: 3.75 g, THF: 60 ml, and water,
Ammonium persulfate: 1.4 in 50 ml of mixture
A solution prepared by dissolving 5 g of water in 10 ml of water was gradually added at room temperature with stirring. After stirring for 1 hour, the THF layer was separated and purified by silica gel chromatography to obtain a comparative dye (CD-1), which is a yellow azomethine dye for comparison below.

[0148]

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[0149] 2. Preparation of Comparative Dye (CD-2) The following comparative coupler (C-2) (US Pat. No. 5,455,514)
Compound (2) described in No. 9): 0.73 g, N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate: 0.80 g, sodium carbonate: 3. 75 g, THF: 60 ml and water,
Ammonium persulfate: 1.4 in 50 ml of mixture
A solution prepared by dissolving 5 g of water in 10 ml of water was gradually added at room temperature with stirring. After stirring at 60 ° C. for 10 minutes, the THF layer was separated and purified by silica gel chromatography.
The following comparative dye (CD-2), which is a yellow azomethine dye for comparison, was obtained.

[0150]

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<Examples 1 to 4> Preparation of Dyes (D-1) to (D-4) In "Preparation of Comparative Dye (CD-2)" of Comparative Example 2,
In the same manner as in Comparative Example 2 except that the above-mentioned exemplified coupler (4), coupler (18), coupler (20) and coupler (36) in the present invention were used instead of the comparative coupler (C-2). The following dye D-1 is an azomethine dye obtained from the dye-forming coupler of the present invention.
(Using coupler (4)), D-2 (using coupler (18)), D-3 (using coupler (20)), D-4 (using coupler (36)) ) Were synthesized.

[0152]

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<Dye acid fading test> Comparative Examples 1 and 2
And comparative dyes (CD-1) obtained in Examples 1 to 4.
Acid fading tests were performed on (CD-2) and dyes (D-1) to (D-4) as follows. Comparative dyes (CD-1) to (CD-2), dye (D
1.0 mg of any of -1) to (D-4) in NMP
(Purity 99% for synthesis of 1-methyl-2-pyrrolidinone peptide) was dissolved in 15 ml, and sample solution 101 (using comparative dye (CD-1)) and sample solution 102 (using comparative dye (CD-2)) Sample solution 103 (using dye (D-1)), sample solution 104 (using dye (D-2)), sample solution 105 (using dye (D-1))
-3)) and the sample solution 106 (dye (D
-4) was prepared.

0.49 g of boric acid and 1N aqueous solution of acetic acid 8
ml of a 1N aqueous phosphoric acid solution prepared in a 200 ml volumetric flask (Britton-Robinson buffer solution,
From now on B. R. (Abbreviated as buffer A solution) was added with phosphoric acid, the pH was adjusted to 1.15, and kept at a constant temperature of 60 ° C. This buffer solution was prepared from the previously prepared sample solutions 101 to 10
6 was added until the total volume became 25 ml, and the visible absorption spectra immediately after preparation and after 4 hours of constant temperature storage at 60 ° C. were measured with an ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation. The respective absorbance at the wavelength was calculated. The ratio of the concentration (residual rate:%) was calculated from the ratio of the absorbance of the sample before the acid fading test to the absorbance of the sample after the acid fading test, and this was used as an index for evaluating the fastness of the dye to acid. Table 3 shows the results.

[0155]

[Table 3]

As is clear from Table 3, the dye obtained from the dye-forming coupler of the present invention has remarkably excellent fastness to acids.

<Comparative Example 3> 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 sodium dodecylbenzenesulfonate solution and the oil phase solution prepared above were added, and the mixture was emulsified and dispersed with a homogenizer to prepare an emulsified dispersion.

[0158] 2. Preparation of Comparative Light-Sensitive Material A coating solution having the following composition was prepared using the obtained emulsified dispersion of the comparative coupler (C-1), and silver halide in terms of silver was formed on a polyethylene laminated paper having an undercoat layer. 0.33 mmol / m ² emulsion, 1 mmol coupler
/ M ² . Further, gelatin was applied thereon as a protective layer so as to have a concentration of ² g / m ² , thereby preparing a 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 total silver bromide locally contained in a part of the surface.) Average grain size: 60 μm, and sensitizing dyes A, B, and C were added in an amount of 1.4 × 10 ⁻⁴ mol per mol of silver halide to give spectral sensitization.) ・ 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

[0160]

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<Comparative Example 4> Preparation of Emulsified Dispersion of Comparative Coupler (C-2) In Comparative Example 3, “1. Preparation of emulsified dispersion of comparative coupler (C-1)”, comparative coupler (C-1) was used instead of comparative coupler (C-1). C-2) (U.S. Pat. No. 545514)
An emulsified dispersion of a comparative coupler (C-2) was prepared in the same manner as in Comparative Example 3 except that Compound (2) described in No. 9 was used.

[0162] 2. Preparation of Comparative Photosensitive Material In Comparative Example 3, "2. Preparation of Comparative Photosensitive Material", the comparative coupler (C-2) (US Pat. No. 5,455,149) was used instead of the emulsified dispersion of the comparative coupler (C-1). Sample 202 as a comparative photosensitive material in the same manner as in Comparative Example 3 except that an emulsified dispersion of the compound (2)) described in
Was prepared.

<Examples 5 to 8> Coupler (4),
Preparation of Emulsified Dispersions of (18), (20) and (36) In Comparative Example 3, "1. Preparation of Emulsified Dispersion of Comparative Coupler (C-1)" in place of Comparative Coupler (C-1) And the coupler (4), the coupler (18), the coupler (20), and the coupler (36) according to the present invention.
In the same manner as in Comparative Example 3 except that each was used, an emulsified dispersion of the coupler in the present invention was prepared.

[0164] 2. Preparation of the photosensitive material of the present invention In "2. Preparation of comparative photosensitive material" of Comparative Example 3, the above-mentioned exemplified couplers (4) and (18) of the present invention were used instead of the emulsified dispersion of the comparative coupler (C-1). ), (20)
In the same manner as in Comparative Example 3 except that the emulsified dispersions of (36) and (36) were used, Samples 203 (using coupler (4)) and Samples 204 as photosensitive materials of the invention were used.
A sample (using the coupler (18)), a sample 205 (using the coupler (20)), and a sample 206 (using the coupler (36)) were produced.

<Color Image Fastness Evaluation Test> Comparative Example 3
4 and Samples 201 to 20 obtained in Examples 5 to 8
6 was subjected to a color image fastness evaluation test as described below. 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 Drying 70- 85 ° C 70 seconds

The respective steps of color development, bleach-fixing, stabilization, stabilization and stabilization were carried out by immersion in the following processing solutions under the above conditions. (Color developer in the color developing step)-Water 800 ml-Dimethyl polysiloxane surfactant (silicone KF351A / trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 g-Triethanolamine 11.6 g-Ethylenediaminetetraacetic acid 4.0 g・ Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5g ・ Potassium chloride 10.0g ・ Potassium bromide 0.040g ・ Triazinylaminostilbene-based fluorescent whitening agent (Hakkol FWA-SF / trade name) 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 Lithium 26.3 g-Add water to 1000 ml pH (adjusted with potassium hydroxide and sulfuric acid at 25 ° C) 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 / liter) 107 ml-ammonium sulfite 16.0 g-potassium metabisulfite 23.1 g-water added to 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) ) 6.0

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

Each of the processed samples developed yellow color,
Samples 203 to 206 containing the coupler of the present invention have a Dmax.
Was high. This means that only a small amount of coupler is required to obtain the same density, and the improvement in sharpness by reducing the film thickness is improved. Samples 203 to 206 containing the coupler of the present invention had high yellow color purity and clear hue.

Next, each of the samples 201 to 206 subjected to the color development processing was irradiated with light of 100,000 lux Xe for 14 days (intermittent irradiation of 5 hours light / 1 hour dark) under the condition of color image light fastness. The sex was evaluated. Sample 20
Samples 1 to 206 were subjected to a wet heat fading test at 80 ° C. and a relative humidity of 80%. The color density of each sample before and after the light fading test and the wet heat fading test was measured with a TCD type densitometer manufactured by Fuji Photo Film Co., Ltd. ) Was calculated and used as an evaluation index of color image fastness. Table 4 shows these results.
Shown in

[0172]

[Table 4]

As is evident from Table 4, the light-sensitive material of the present invention has high color development, excellent light fastness, and excellent wet heat fastness. In addition, according to this result,
It can be seen that the azomethine dye of the present invention is excellent in light fastness and wet heat fastness.

Example 9 After a corona discharge treatment was applied to the surface of a support obtained by coating both sides of a paper with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. The photographic constituent layer of the seventh layer was sequentially coated to prepare a sample (001) of a silver halide color photographic light-sensitive material having the following layer constitution. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of coating solution for first layer 62 g of yellow coupler (ExY), color image stabilizer (Cp
d-1) 8 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 8 g, color image stabilizer (Cpd-8) 2
g of solvent (Solv-1) 23 g and ethyl acetate 80 m
1 g of a 23.5% by weight aqueous gelatin solution containing 4 g of sodium dodecylbenzenesulfonate.
In 0 g, the mixture was emulsified and dispersed by a high-speed stirring emulsifier (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, average grain size 0.72
μm large size emulsion A and 0.60 μm small size emulsion A
3: 7 mixture (silver molar ratio). The coefficient of variation of the particle size distribution was 0.08 and 0.10. For each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain). In this emulsion, blue-sensitive sensitizing dyes A, B and C shown below were added to silver halide 1
Per mole, 1.4 × 1 for large size emulsions
^0-4 moles, 1.7 × 1 each for small size emulsions
^0-4 moles are 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 Solution for Second Layer to Seventh Layer) 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 .

[0177]

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

[0179]

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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

[0181]

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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

[0183]

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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.

[0185]

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Further, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × 10 5 per mol of silver halide. ^-4 mol, 1.0 × 10 ^-3
Mol and 5.9 × 10 ^-4 mol. Further, each of the second, fourth, sixth and seventh layers also has 0.2
mg / m ² , 0.2 mg / m ² , 0.6 mg / m ² , 0.
It was added so as to be 1 mg / m ² . Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol per mol of silver halide. 2x1
^0-4 moles were added.

In the red-sensitive emulsion layer, a copolymer of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 2
(0000 to 400,000) was added at 0.05 g / m ² . Also, disodium catechol-3,5-disulfonate and 2,6-bishydroxyamino-4-diethylamino-1,3,5 were added to the second, fourth and sixth layers.
A mixture of triazines (9: 1 molar ratio)
mg / m ² , 6 mg / m ² and 18 mg / m ² . To prevent irradiation, the following dyes were added to the emulsion layer.

[0188]

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[0189]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content 16% by mass, ZnO; content 4% by mass) and 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 (silver mole The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. ) 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0 0.08 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.23

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

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B with an average grain size of 0.45 μm and small-size emulsion B of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-1) 0.05 Ultraviolet absorber (UV-2) 0.03 Ultraviolet absorber (UV-3) 0.02 Ultraviolet absorption Agent (UV-4) 0.03 Ultraviolet absorber (UV-6) 0.01 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Stabilizer (Cpd-6) ) 0.09 color image stabilizer (Cpd-8) 0.02 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 prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color mixture prevention assistant (Cpd-5) 0.013 Stabilizer (Cpd-6) 0.10 Color mixture prevention Agent (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 (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.05 Stabilizer (Cpd-6) 0.05 Mixed color Inhibitor (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) 0.01 Color image stabilizer (Cpd-15) 0.03 Color image stabilizer (Cpd-16) 0.05 Color image stabilizer (Cpd-17) 0.05 Color image stabilizer (Cpd-18) 0.06 Color image stabilizer (Cpd-19) 0.06 Solvent (Solv-5) 0.15 Solvent (Solv) -8) 0.05 Solvent (Solv-9) 0.10

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

[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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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. Comparative Example 2
A photosensitive material 302 was prepared in exactly the same manner except that the same coupler was used in place of the comparative coupler (C-2). The couplers (4), (6), (7), (18), (20) and (36), including the dye-forming couplers used in Examples 1 to 4, were replaced with the same molar amounts, respectively, at all. Similarly, photosensitive materials (303) to (308) of the present invention were produced. The average particle size of each of the yellow coupler-containing lipophilic fine particle dispersions prepared here was 0.1%.
It was in the range of 0 to 0.20 μm. The above photosensitive material (00
1) After storing at 25 ° C. and 55% RH for 10 days, 127 mm
Processing into a roll of width, imagewise exposure using Fuji Photo Film Co., Ltd. minilab printer processor PP1258AR, and continuous processing (running test) until replenishing twice the color developing tank capacity in the following processing steps
Was done. Processing Step Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds - rinse (3) ** 38.0 ℃ 20 seconds - rinse (4) ** 38.0 ℃ 30 seconds 121 ml * phosphorus replenishment rate ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D per photosensitive material 1 m ² The rinsing liquid is taken out of the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

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

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

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

Next, a sensitometer (Fuji Photo Film Co., Ltd., FWH type, light source color temperature 3200 ° K) is applied to each photosensitive material.
Was used to provide a gradation exposure with a three-color separation optical wedge for sensitometry. The exposure at this time was performed so that the exposure amount was 250 lx · sec (lux · sec) with an exposure time of 0.1 second. Separately, scanning exposures shown below were performed on each photosensitive material. JP-A-8-1
The scanning exposure apparatus of FIG. 1 of No. 6238 was used. The light source is a 688 nm light source (R light) using a semiconductor laser and 532 nm by combining the semiconductor laser with SHG.
(G light) and a 473 nm light source (B light) were obtained. R
The amount of light was modulated using an external modulator, reflected on a rotating polyhedron, and scanned and exposed on a sample moving perpendicular to the scanning direction. This scanning exposure was performed at 400 dpi, and 1
The average exposure time per pixel was 8 × 10 ^-8 seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress a change in light amount due to temperature.

Each of the exposed samples was developed using the above-mentioned running processing solution, and the same evaluation as that for the photosensitive materials performed in Comparative Examples 3 and 4 and Examples 5 to 8 was performed. As a result, it was confirmed that all the light-sensitive materials containing the dye-forming coupler of the present invention had high color developability, and were excellent in hue and fastness.

Example 10 Except that the ExY-2 and ExY-3 of the 13th and 14th layers of Sample 101 of JP-A-11-305396 were all equimolarly changed to the dye-forming coupler (4) of the present invention. A different photosensitive material was prepared, exposed and developed by the method described in Example 1 of JP-A-11-305396, and evaluated by the method described in the example of the present application. The result was similar to that of Example 5 of the present application. I got

Example 11 In Example 1 of JP-A-11-84601, the sample 10
The couplers C-5, C-6 and C-10 of the 13th and 14th layers of the No. 7 and the C-6 and C-10 of the 15th layer are all equimolar to the dye-forming coupler (1) of the present invention. A light-sensitive material different from the above-described light-sensitive material was produced by the method described in JP-A-11-846.
The film was exposed and developed by the method described in Example 1 of No. 01 and evaluated by the method described in the example of the present application. As a result, the same result as that of Example 5 of the present application was obtained.

[0215]

Since the coupler of the present invention is a highly active coupler, it can provide a dye having a high color density, an excellent hue, and a good storage stability. The coupler can be added to a light-sensitive material. Accordingly, a silver halide photographic material having excellent color reproducibility and good color image fastness can be provided. Furthermore, an azomethine dye excellent in hue and storage stability can be provided.

Claims (6)

[Claims] 1. A dye-forming coupler represented by the following general formula (I). Embedded image In the formula, Q represents a residue that forms a nitrogen-containing 6-membered ring together with -NC = N-. L is a divalent linking group, and R ₁ represents a substituent. X represents an aryl group. Y represents a hydrogen atom or a group which can be removed by a coupling reaction with an oxidized developing agent. However, -LR ₁ is not an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and -LR ₁ is a nitrogen-containing 6 formed by Q and -NC = N- moiety. The atom bonded to the nitrogen atom of the member ring does not become a heterocyclic group bonded by a carbon atom. 2. The dye-forming coupler according to claim 1, wherein in the dye-forming coupler represented by formula (I), Q is a residue forming a 4-pyrimidone ring. 3. A silver halide photographic material comprising at least one dye-forming coupler represented by the following formula (I). Embedded image In the formula, Q represents a residue that forms a nitrogen-containing 6-membered ring together with -NC = N-. L is a divalent linking group, and R ₁ represents a substituent. X represents an aryl group. Y represents a hydrogen atom or a group which can be removed by a coupling reaction with an oxidized developing agent. However, -LR ₁ is not an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and -LR ₁ is a nitrogen-containing 6 formed by Q and -NC = N- moiety. The atom bonded to the nitrogen atom of the member ring does not become a heterocyclic group bonded by a carbon atom. 4. The silver halide photographic light-sensitive material according to claim 3, wherein in the dye-forming coupler represented by formula (I), Q is a residue forming a 4-pyrimidone ring. . 5. An azomethine represented by the following general formula (II):
Dye compound. Embedded imageIn the formula, Q forms a nitrogen-containing 6-membered ring together with -NC = N- moiety.
Represents the residue to be used. L is a divalent linking group;₁Is replaced
Represents a group. X represents an aryl group. R_Five, R₆Is independently water
Represents an atom or a substituent. R₇Is a hydrogen atom or substitution
And n represents 0 or an integer of 1 to 4. n is 2
When 4, a plurality of R₇Are the same but different
May be bonded to each other and
Good. Also R₇Is R_FiveOr R₆With each other
It may be ringed. Also, R_FiveAnd R ₆Are connected to each other
May be formed. However, -LR₁Is an alkyl group,
Alkenyl, alkynyl and aryl
And -LR₁But by Q and -NC = N-part
The atom bonded to the nitrogen atom of the 6-membered nitrogen-containing ring formed by
It does not result in a heterocyclic group linked by a carbon atom. 6. The azomethine dye compound according to claim 5, wherein in the azomethine dye compound represented by the general formula (II), Q is a residue forming a 4-pyrimidone ring.