JP2003172994A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity and little residual color after processing and less liable to variation of photographic properties after continuous processing. <P>SOLUTION: The silver halide photographic sensitive material contains a combination of a methine dye of formula (I) and a specified pyrazoloazole coupler or a specified phenol coupler. In the formula, X<SP>1</SP>and X<SP>2</SP>are each O, S, Se, Te, N or C; Y<SP>1</SP>is a furan ring, pyrrole ring or a thiophene ring; Y<SP>2</SP>is a group of atoms required to form a benzene ring or a 5- or 6-membered unsaturated heterocycle which may be condensed with another 5- or 6-membered carbon ring or heterocycle or may have a substituent; R<SP>1</SP>and R<SP>2</SP>are each an optionally substituted alkyl or aryl or an optionally substituted heterocyclic group; L<SP>1</SP>-L<SP>3</SP>are each methine; n<SP>1</SP>is 0 or 1; M<SP>1</SP>is a counter ion; and m<SP>1</SP>is a numeral of ≥0 required to neutralize electric charges in each molecule. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. More specifically, it relates to a silver halide photographic light-sensitive material having high sensitivity, less residual color after processing, and less variation in photographic properties after continuous processing.

[0002]

2. Description of the Related Art Conventionally, great efforts have been made to increase the sensitivity of silver halide photographic light-sensitive materials and reduce the residual color after processing. Sensitizing dyes used for spectral sensitization are known to have a great influence on the performance of silver halide photographic light-sensitive materials. Regarding sensitizing dyes, slight differences in structure have a great influence on photographic performance such as sensitivity, fog, storage stability, and residual color after processing (residual color). Also, two or more sensitizing dyes are used in combination. However, it has been difficult to predict the effect in advance, and many researchers have synthesized many sensitizing dyes and used many sensitizing dyes together. I have been making efforts to investigate the photographic performance by examining. However, at present, it is still impossible to predict the photographic performance.
For the above reasons, there has been a demand for a technique for sensitizing silver halide grains with high sensitivity and without causing adverse effects such as fog and residual color.

To shift the absorption maximum of the sensitizing dye to a longer wavelength, it has been widely used to use a naphthazole nucleus in which a benzene ring is condensed with a benzoazole nucleus. However, while the amount of dye added has increased due to the strong demand for high sensitivity in recent years, it has also been necessary to respond to the speeding up of photographic processing and the reduction of processing waste liquid to address environmental problems. It is becoming impossible to meet such requirements with dyes having high hydrophobicity. The inventors of the present invention, in Japanese Patent Application No. 2000-124612, a sensitizing dye in which a specific heterocyclic ring-condensed azole nucleus is used in place of a naphthazole nucleus is more sensitive than a naphthazole-type dye, and has a residual color. It discloses that there are few. However, in principle, such a dye accumulates a large amount in the treatment liquid after the treatment, and therefore, it has become clear that the photographic properties are easily changed in a tired treatment liquid.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide light-sensitive material having high sensitivity, less residual color after processing, and less variation in photographic property after continuous processing.

[0005]

As a result of intensive studies, the object of the present invention could be achieved by the following means. That is,

(1) A silver halide photographic light-sensitive material containing at least one methine dye represented by the following general formula (I) and at least one coupler represented by the following general formula (X). material. General formula (I)

[0007]

[Chemical 4]

In the formula (I), X ¹ and X ² represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom and a carbon atom. Y ¹ represents a furan ring, a pyrrole ring, or a thiophene ring which may be condensed with another 5- or 6-membered carbon ring or heterocycle or may have a substituent. Y ² represents an atom group necessary for forming a benzene ring or a 5- or 6-membered unsaturated heterocycle, and may have a substituent even if condensed with another 5- or 6-membered carbocycle or heterocycle. You may have. The bond between the two carbon atoms fused to Y ¹ and Y ² may be a single bond or a double bond.
R ¹ and R ² represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. L ¹ , L ² and L ³
Each represent a methine group, and n ¹ represents 0 or 1.
M ¹ represents a counter ion, and m ¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule. General formula (X)

[0009]

[Chemical 5]

In formula (X), Z ¹ and Z ² represent -C (Q ³ ) = or -N =, Q ¹ and Q ³ represent a hydrogen atom or a monovalent substituent, and Q ² represents hydrogen. Represents an atom or a coupling leaving group. Q ¹ , Q ² or Q ³ may be a divalent group to bond with a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer.

(2) In a silver halide photographic light-sensitive material containing at least one silver halide photographic emulsion layer on a support, at least one methine dye represented by the general formula (I) and the following general A silver halide photographic light-sensitive material comprising at least one coupler represented by formula (XX). General formula (XX)

[0012]

[Chemical 6]

In formula (XX), Q ⁵ represents a substituted or unsubstituted aryl group, and Q ⁶ represents a substituted or unsubstituted alkyl group. Q ⁷ represents a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent.

(3) The methine dye represented by the general formula (I) in (1) or (2) is represented by the following general formula (I)
The silver halide photographic light-sensitive material as described in (1) or (2) above, which is represented by I), (III), (IV) or (V). General formula (II)

[0015]

[Chemical 7]

In the formula (II), Y ¹¹ represents an oxygen atom, a sulfur atom or NR ¹³ , and R ¹³ represents a hydrogen atom or an alkyl group. V ¹⁵ and V ¹⁶ represent a hydrogen atom or a monovalent substituent. X ¹¹ and X ¹² represent an oxygen atom or a sulfur atom. R ¹¹ and R ¹² represent an alkyl group substituted with an acid group. V ¹¹ , V ¹² , V ¹³ and V ¹⁴ represent a hydrogen atom or a monovalent substituent. M ¹¹ represents a counter ion, and m ¹¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule. General formula (III)

[0017]

[Chemical 8]

In the formula (III), Y ²¹ represents an oxygen atom, a sulfur atom or NR ²³ , and R ²³ represents a hydrogen atom or an alkyl group. V ²⁵ and V ²⁶ represent a hydrogen atom or a monovalent substituent. X ²¹ and X ²² represent an oxygen atom or a sulfur atom. R ²¹ and R ²² represent an alkyl group substituted with an acid group. V ²¹ , V ²² , V ²³ and V ²⁴ are hydrogen atoms or 1
Represents a valent substituent. M ²¹ represents a counter ion, and m ²¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule. General formula (IV)

[0019]

[Chemical 9]

In the formula (IV), Y ³¹ represents an oxygen atom, a sulfur atom or NR ³³ , and R ³³ represents a hydrogen atom or an alkyl group. V ³⁵ and V ³⁶ represent a hydrogen atom or a monovalent substituent. X ³¹ and X ³² represent an oxygen atom or a sulfur atom. R ³¹ and R ³² represent an alkyl group substituted with an acid group. A ³¹ represents a methyl group, an ethyl group or a propyl group, and V ³¹ , V ³² , V ³³ and V ³⁴ represent a hydrogen atom or a monovalent substituent. M ³¹ represents a counter ion, and m ³¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule. General formula (V)

[0021]

[Chemical 10]

In the formula (V), Y ⁴¹ represents an oxygen atom, a sulfur atom or NR ⁴³ , and R ⁴³ represents a hydrogen atom or an alkyl group. V ⁴⁵ and V ⁴⁶ represent a hydrogen atom or a monovalent substituent. X ⁴¹ and X ⁴² represent an oxygen atom or a sulfur atom. R ⁴¹ and R ⁴² represent an alkyl group substituted with an acid group. A ⁴¹ represents a methyl group, an ethyl group or a propyl group, and V ⁴¹ , V ⁴² , V ⁴³ and V ⁴⁴ represent a hydrogen atom or a monovalent substituent. M ⁴¹ represents a counter ion, and m ⁴¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.

(4) The above general formula (II) in (3)
One of R ¹¹ and R ¹² of the methine dye represented by is a carboxyl group, a —CONHSO ₂ — group, a —SO ₂ NHCO— group,
CONHCO- group, -SO ₂ NHSO ₂ - alkyl group which group is substituted, the silver halide photographic material as described in (3), wherein the other is an alkyl group substituted by a sulfo group. (5) In the methine dye represented by the general formula (II) in (4), Y ¹¹ is a sulfur atom, V ¹⁵ is a halogen atom, and V ^{16 is}
Is a hydrogen atom, the silver halide photographic light-sensitive material as described in (4) above.

(6) The general formula (II
One of R ²¹ and R ²² of the methine dye represented by I) is a carboxyl group, a —CONHSO ₂ — group, or a —SO ₂ NHCO—
Group, -CONHCO- group, -SO ₂ NHSO ₂ - alkyl group which group is substituted, the silver halide photographic according to the above (3), wherein the other is an alkyl group substituted by a sulfo group Photosensitive material. (7) In the methine dye represented by the general formula (III) in (6), Y ²¹ is a sulfur atom, V ²⁵ is a halogen atom, and V is V.
²⁶ is a hydrogen atom, The silver halide photographic light-sensitive material as described in (6) above.

(8) The above general formula (IV) in (3)
One of R ³¹ and R ³² of the methine dye represented by is a carboxyl group, a —CONHSO ₂ — group, a —SO ₂ NHCO— group,
CONHCO- group, -SO ₂ NHSO ₂ - alkyl group which group is substituted, the silver halide photographic material as described in (3), wherein the other is an alkyl group substituted by a sulfo group. (9) In the methine dye represented by the general formula (IV) in (8), Y ³¹ is a sulfur atom, V ³⁵ is a halogen atom, and V ^{36 is}
Is a hydrogen atom, the silver halide photographic light-sensitive material as described in (8) above.

(10) One of R ⁴¹ and R ⁴² of the methine dye represented by the general formula (V) in (3) is one of a carboxyl group, a —CONHSO ₂ — group and a —SO ₂ NHCO—.
Group, -CONHCO- group, -SO ₂ NHSO ₂ - alkyl group which group is substituted, the silver halide photographic according to the above (3), wherein the other is an alkyl group substituted by a sulfo group Photosensitive material. (11) In the methine dye represented by the general formula (V) in (10), Y ⁴¹ is a sulfur atom, V ⁴⁵ is a halogen atom,
V ⁴⁶ is a hydrogen atom, The silver halide photographic light-sensitive material as described in (10) above.

(12) The halogenation described in the above (1), wherein the coupler represented by the above general formula (X) in (1) is represented by the following general formula (XI) or (XII). Silver photographic light-sensitive material. General formula (XI)

[0028]

[Chemical 11]

In formula (XI), Q ¹¹ represents an alkyl group, and Q ^11
12 represents a hydrogen atom or a halogen atom, and Q ¹³ represents -SO.
_It represents a substituent containing 2-. General formula (XII)

[0030]

[Chemical 12]

In the formula (XII), Q ²¹ represents an alkyl group,
Q ²² represents a hydrogen atom or a halogen atom, and Q ²³ represents -S
It represents a substituent containing O ₂ —.

(13) In the silver halide photographic light-sensitive material described in (1) above, which contains at least one silver halide photographic emulsion layer on a support, the above-mentioned general formula (II),
(III), (IV) or (V) at least one kind of methine dye and at least one coupler represented by the general formula (XII) are contained in (1) above. Silver halide photographic light-sensitive material. (14) In the silver halide photographic light-sensitive material described in (13) above, (R ¹¹ , R ²¹ , R of the methine dye represented by the general formula (II), (III), (IV) or (V) is used. ³¹ or R ⁴¹ ) and one of (R ¹² , R ²² , R ³² or R ⁴² ) is a carboxyl group, a —CONHSO ₂ — group, a —SO ₂ NHC.
O- group, -CONHCO- group, -SO ₂ NHSO ₂ - group is an alkyl group substituted, other halogenated according to the above (13), characterized in that an alkyl group substituted by a sulfo group Silver photographic light-sensitive material. (15) In the silver halide photographic light-sensitive material described in (14) above, (Y ¹¹ , Y ²¹ , Y of the methine dye represented by the general formula (II), (III), (IV) or (V) is used. ³¹ or Y ⁴¹ ) is a sulfur atom, (V ¹⁵ , V ²⁵ , V ³⁵ or V ⁴⁵ ) is a halogen atom, and (V ¹⁶ , V ²⁶ , V ³⁶ or V ⁴⁶ ) is a hydrogen atom. (14)
The silver halide photographic light-sensitive material described in. (16) The silver halide photographic light-sensitive material as described in (2) above, which comprises at least one silver halide photographic emulsion layer on a support, wherein the general formulas (II), (III) and (I
V) or at least one methine dye represented by (V)
The silver halide photographic light-sensitive material described in (2) above, which contains at least one kind of coupler and at least one coupler represented by the general formula (XX). (17) In the silver halide photographic light-sensitive material described in (16) above, (R ¹¹ , R ²¹ , R of the methine dye represented by the general formula (II), (III), (IV) or (V) is used. ³¹ or R ⁴¹ ) and one of (R ¹² , R ²² , R ³² or R ⁴² ) is a carboxyl group, a —CONHSO ₂ — group, a —SO ₂ NHC.
O- group, -CONHCO- group, -SO ₂ NHSO ₂ - group is an alkyl group substituted, other halogenated according to the above (16), characterized in that an alkyl group substituted by a sulfo group Silver photographic light-sensitive material. (18) In the silver halide photographic light-sensitive material described in (17) above, (Y ¹¹ , Y ²¹ , Y of the methine dye represented by the general formula (II), (III), (IV) or (V) is used. ³¹ or Y ⁴¹ ) is a sulfur atom, (V ¹⁵ , V ²⁵ , V ³⁵ or V ⁴⁵ ) is a halogen atom, and (V ¹⁶ , V ²⁶ , V ³⁶ or V ⁴⁶ ) is a hydrogen atom. (16)
The silver halide photographic light-sensitive material described in.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, the groups used in the present invention will be described in detail.

In the present invention, when a specific moiety is referred to as a "group", the moiety is substituted with one or more (up to the maximum possible number) of substituents, even if the moiety is not itself substituted. Means that it may be. For example, "alkyl group" means a substituted or unsubstituted alkyl group. Further, the substituent that can be used in the compound of the present invention includes any substituent regardless of the presence or absence of substitution.

When such a substituent is represented by W, the substituent represented by W may be any one, and is not particularly limited, and examples thereof include a halogen atom, an alkyl group [(including a cyclic alkyl group), and , An alkenyl group (including a cyclic alkenyl group), and an alkynyl group. ], Aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group , Alkyl and aryl sulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and aryl sulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, ari Group, oxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group (also called phosphono group) , Silyl group, hydrazino group, ureido group, boronic acid group, phosphato group, sulfato group, and other known substituents.

More specifically, W is a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [[representing a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms 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, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably , A substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1.2.
2] heptan-2-yl, bicyclo [2.2.2] octane-3-yl), and a tricyclo structure having many ring structures. The alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group) represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms such as vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted C 3 to 30 carbon atom, or An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond). A group, for example, bicyclo [2.2.1] hept-2-en-1-yl, bicyclo 2.2.2] is intended to encompass oct-2-en-4-yl). ],
Alkynyl group (preferably substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group)], aryl group (preferably substituted or unsubstituted aryl group having 6 to 30 carbon atoms) , Phenyl, p-tolyl, naphthyl,
m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, monovalent with one hydrogen atom removed) And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1 A cationic heterocyclic group such as -methyl-2-pyridinio or 1-methyl-2-quinolinio may be used),
Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy,
Ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy). , 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy),
Silyloxy group (preferably silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy group (preferably substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms) Group, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and 6 to 30 carbon atoms) A substituted or unsubstituted arylcarbonyloxy group, for example formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy),
Carbamoyloxy group (preferably having 1 to 30 carbon atoms)
A substituted or unsubstituted carbamoyloxy group, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, N-n-octyl Carbamoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms)
A substituted or unsubstituted alkoxycarbonyloxy group,
For example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, Phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, carbon number 6) To 30 substituted or unsubstituted anilino groups, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), ammonio groups (preferably ammonio groups, substituted with 1 to 30 carbon atoms). Or an unsubstituted alkyl, aryl, or heterocyclic-substituted ammonio group, for example, trimethylammonio, triethylammonio, diphenylmethylammonio), an acylamino group (preferably a formylamino group, a substituent having 1 to 30 carbon atoms) Or an unsubstituted alkylcarbonylamino group, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5
-Tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N , N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino groups (preferably having 2 to 30 carbon atoms).
A substituted or unsubstituted alkoxycarbonylamino group,
For example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably substituted or unsubstituted with 7 to 30 carbon atoms). Substituted aryloxycarbonylamino groups, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxy) phenoxycarbonylamino), sulfamoylamino groups (preferably substituted with 0 to 30 carbon atoms) Or an unsubstituted sulfamoylamino group, for example, sulfamoylamino, N,
N-dimethylaminosulfonylamino, N-n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkanesulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted carbon atoms having 6 to 30 carbon atoms). Substituted arylsulfonylamino, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5
-Trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), a mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), an arylthio group ( Preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio, a heterocyclic thio group (preferably a substituted or unsubstituted heteroaryl having 2 to 30 carbon atoms). Ring thio group, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio, sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl). , N- (3-dodeci Propyl) sulfamoyl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N-
(N′-phenylcarbamoyl) sulfamoyl), a sulfo group, an alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, For example, methylsulfinyl,
Ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkanesulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p
-Methylphenylsulfonyl), 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, or an alkylcarbonyl group having 4 to 30 carbon atoms) A heterocyclic carbonyl group bonded to a carbonyl group at a substituted or unsubstituted carbon atom, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-
Pyridylcarbonyl, 2-furylcarbonyl), aryloxycarbonyl group (preferably having from 7 to 30 carbon atoms)
A substituted or unsubstituted aryloxycarbonyl group,
For example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt
-Butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl,
n-octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-).
Di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted carbon atoms having 3 to 30 carbon atoms) Heterocyclic azo groups such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide groups (preferably N
-Succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably, 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, a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino). , Dimethylaminophosphinylamino), a phospho group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), a hydrazino group ( Preferably, a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, for example, trimethylhydrazino, a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, for example, N, N).
-Dimethylureido).

Further, two Ws jointly form a ring (aromatic or non-aromatic hydrocarbon ring or hetero ring.
It can be further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, quinoline ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring,
Pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, carbazole ring, phenanthridine ring, Examples thereof include an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiine ring, a phenothiazine ring and a phenazine ring. It is also possible to adopt a structure in which) is condensed.

Among the above substituents W, having a hydrogen atom
Those that have been stripped of this and further substituted with the above groups
May be. Examples of such substituents include -CONH
SO ₂-Group (sulfonylcarbamoyl group, carbonyls
Rufamoyl group), -CONHCO- group (carbonyl
Luvamoyl group), -SO₂NHSO₂-Group (sulfonyl
Sulfamoyl group). More specifically,
An alkylcarbonylaminosulfonyl group (eg
Cylaminosulfonyl), arylcarbonylaminos
Rufonyl group (for example, benzoylaminosulfonyl)
Group), alkanesulfonylaminocarbonyl group (eg,
Methylsulfonylaminocarbonyl), Aryls
Rufonylaminocarbonyl group (for example, p-methylphene)
Nylsulfonylaminocarbonyl).

Next, the methine dye represented by formula (I) of the present invention will be described in detail.

X ¹ and X ² represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom and a carbon atom. The nitrogen atom can be preferably represented by -N (Rx)-and the carbon atom can be preferably represented by -C (Ry) (Rz)-. The above W) is preferably an alkyl group, an aryl group, or a heterocyclic group similar to R, and more preferably an alkyl group. Each of X ¹ and X ² is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom or a sulfur atom.

Y ¹ represents a furan ring, a pyrrole ring, or a thiophene ring which may be condensed with another 5- or 6-membered carbon ring or heterocycle or may have a substituent. In addition,
The bond between the two carbon atoms fused to Y ¹ may be a single bond or a double bond, but is preferably a double bond. Y ¹ can also form a condensed ring with another 5- or 6-membered carbon ring or heterocycle, but it is preferable that the third condensed ring does not exist. Y ¹ is preferably a thiophene ring. The substituent of Y ¹ may be any, but examples thereof include W described above. Preferably, an alkyl group (eg methyl), an aryl group (eg phenyl), an aromatic heterocyclic group (eg 1-pyrrolyl), an alkoxy group (eg methoxy), an alkylthio group (eg methylthio), a cyano group, an acyl group (eg Acetyl),
An alkoxycarbonyl group (eg methoxycarbonyl), a halogen atom (eg fluorine, chlorine, bromine, iodine), more preferably a methyl group, a methoxy group,
A cyano group and a halogen atom are more preferable, a halogen atom is more preferable, a fluorine atom, a chlorine atom and a bromine atom are particularly preferable, and a chlorine atom is most preferable. Particularly when Y ¹ is a thiophene ring, it preferably has a halogen substituent, and the substituent is preferably a chlorine or bromine atom, and most preferably a chlorine atom.

Y ² represents an atomic group necessary for forming a benzene ring or a 5- or 6-membered unsaturated heterocycle, and is substituted even if condensed with another 5- or 6-membered carbocycle or heterocycle. It may have a group. The bond between the two carbon atoms fused with Y ² may be a single bond or a double bond, but is preferably a double bond. The 5-membered unsaturated heterocycle formed by Y ² includes a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a furan ring,
Oxazole ring, isoxazole ring, thiophene ring,
Thiazole ring, isothiazole ring, thiadiazole ring,
A selenophene ring, a selenazole ring, an isoselenazole ring, a tellurophen ring, a tellurazole ring, an isotellurazole ring and the like, and a 6-membered unsaturated heterocycle such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyran ring and a thiopyran ring. And further condensed with another 5- or 6-membered carbocycle or heterocycle to form, for example, an indole ring,
A benzofuran ring, a benzothiophene ring, or a thienothiophene ring can be formed, but it is preferable that the third condensed ring does not exist. Y ² is preferably a benzene ring, a pyrrole ring, a furan ring or a thiophene ring, particularly preferably a benzene ring, a furan ring or a pyrrole ring, and most preferably a benzene ring. The substituent of Y ² may be any, but examples thereof include W described above. Preferably, an alkyl group (eg methyl), an aryl group (eg phenyl), an aromatic heterocyclic group (eg 1-pyrrolyl),
Alkoxy group (eg methoxy), alkylthio group (eg methylthio), cyano group, acyl group (eg acetyl), alkoxycarbonyl group (eg methoxycarbonyl), halogen atom (eg fluorine, chlorine, bromine, iodine), and more preferably Is a methyl group, a methoxy group, a cyano group or a halogen atom, more preferably a halogen atom, particularly preferably a fluorine, chlorine or bromine atom, and most preferably a chlorine atom.

R ¹ and R ² represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. At least one of R ¹ and R ² is preferably an alkyl group substituted with an acid group, and more preferably both R ¹ and R ² are alkyl groups substituted with an acid group.

Here, the acid group will be described. The acid group is a group having a dissociative proton. Specifically, for example, a sulfo group, a carboxyl group, a sulfato group, -CO
NHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group (sulfonylsulfamoyl group), sulfonamide group, sulfamoyl group, phosphato group , Phosphono group, boronic acid group, phenolic hydroxyl group, etc., and their pKa and surrounding pH
In some cases, a group capable of dissociating a proton may be mentioned. For example, a proton-dissociable acidic group capable of dissociating 90% or more between pH 5 and 11 is preferable. In the methine dye represented by the general formula (I), a preferable one as the “alkyl group substituted with an acid group” represented by R ¹ or R ² can be represented as follows in the form of formula.

[0045]

[Chemical 13]

Qa represents a linking group (preferably a divalent linking group) necessary for forming an alkyl group. Ra, Rb, R
c and Rd each represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclyloxy group, or an amino group.

Qa may be any linking group as long as it satisfies the above requirements, but is preferably an atom or atomic group containing at least one of carbon atom, nitrogen atom, sulfur atom and oxygen atom. Preferably an alkylene group (eg methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group (eg ethenylene, propenylene), an alkynylene group (eg ethynylene, propynylene),
Amide group, ester group, sulfamide group, sulfonate group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N
(Wa)-(Wa represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include W described above),
0 carbon atoms composed of one or more of
It represents a connecting group having 10 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 5 carbon atoms.

The above-mentioned linking group may further have the above-mentioned substituent represented by W, and may also contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle). Good. However, it is more preferable that these linking groups do not contain a hetero atom. Further, it is more preferable that it is not substituted with the above-mentioned substituent represented by W.

More preferably, Qa is an alkylene group having 1 to 5 carbon atoms (eg methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group having 2 to 5 carbon atoms (eg ethenylene, And a alkynylene group having 2 or more and 5 or less carbon atoms (for example, ethynylene or propynylene), or a divalent linking group having 1 or more and 5 or less carbon atoms. Particularly preferred is an alkylene group having 1 to 5 carbon atoms (preferably methylene, ethylene, trimethylene, tetramethylene).

When T ¹ is a sulfo group, Qa is more preferably ethylene, trimethylene, tetramethylene,
Methyl trimethylene, particularly preferably trimethylene. When Xa is a carboxyl group, Qa is more preferably methylene, ethylene or trimethylene, and particularly preferably methylene. T ¹ is -CONH
SO ₂ Ra, SO ₂ NHCORb, CONHCORc, SO ₂
In the case of NHSO ₂ Rd, Qa is more preferably methylene, ethylene or trimethylene, and particularly preferably methylene.

Ra, Rb, Rc, and Rd represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclyloxy group, or an amino group, and the following groups are preferable. For example, 1 to 1 carbon atoms
8, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, unsubstituted alkyl group (eg, methyl, ethyl, propyl, butyl), 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and Preferably, it is a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and preferably 2 to 18 carbon atoms, more preferably 3 carbon atoms).
1 to 10, particularly preferably an unsaturated hydrocarbon group having 3 to 5 carbon atoms (for example, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group) is also included in the substituted alkyl group. ), Carbon number 6 to 2
A substituted or unsubstituted aryl group having 0, preferably 6 to 15, more preferably 6 to 10 carbon atoms (eg, phenyl, naphthyl, p-carboxyphenyl, p-
Nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), substituted with 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 4 to 6 carbon atoms. A heterocyclic group (eg pyridyl, 5-methylpyridyl, thienyl,
Furyl, morpholino, tetrahydrofurfuryl), an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-hydroxyethoxy, 2-phenylethoxy), carbon number 6 To 20, preferably 6 to 1 carbon atoms
2, more preferably an aryloxy group having 6 to 10 carbon atoms (for example, phenoxy, p-methylphenoxy, p-
Chlorophenoxy, naphthoxy), carbon number 1 to 20,
Preferably, it is a heterocyclyloxy group having 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms (meaning an oxy group substituted with a heterocyclic group. For example, 2-thienyloxy, 2-morpholinooxy) and an amino group. Carbon 0
To 20, preferably 0 to 12, and more preferably 0 to 8 carbon amino groups (eg, amino, methylamino, dimethylamino, ethylamino, diethylamino, hydroxyethylamino, benzylamino, anilino, diphenylamino, Ring-forming morpholino and pyrrolidino). In addition to these,
May be substituted. More preferably, a methyl group,
An ethyl group and a hydroxyethyl group are preferred, and a methyl group is particularly preferred.

In the acid group, for example, a carboxyl group and a dissociative nitrogen atom are not dissociated (CO
OH, NH), the dissociated form (COO ⁻ ,
N ^-) may either be written in. In reality, the dye may be in a dissociated state or a non-dissociated state depending on the environment in which the dye is placed, such as pH. When a cation is present as a counter ion, for example, (COO ^- Na ⁺ ), (N ^- Na ⁺ )
It may be written as. (COOH), (N
H), but if the counterion cation compound is considered to be a proton, it can also be expressed as (COO ⁻ H ⁺ ) or (N ⁻ H ⁺ ).

In the methine dye represented by formula (I), it is particularly preferable that at least one of R ¹ and R ² is an alkyl group substituted with an acid group other than a sulfo group, and most preferably R 1 ^{One of 1} and R ² is an alkyl group substituted with an acid group other than a sulfo group, and the other is an alkyl group substituted with a sulfo group. Above,
The alkyl group having a sulfo group is preferably a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group or a 2-sulfoethyl group, and more preferably 3-
It is a sulfopropyl group. At this time, the alkyl group substituted with an acid group other than the sulfo group is preferably a carboxyl group, a -CONHSO ₂ -group, a -SO ₂ NHCO- group, or-.
CONHCO- group, -SO ₂ NHSO ₂ - alkyl group which group is substituted, especially preferably carboxymethyl group,
It is a methanesulfonylcarbamoylmethyl group.

As a combination of R ¹ and R ² , one is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and the other is a 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group, 2
-A sulfoethyl group, and more preferably one is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group and the other is a 3-sulfopropyl group.

L ¹ , L ² and L ³ each represent a methine group, which may be unsubstituted or substituted by a substituent (for example, W described above), but preferable substituents are an aryl group and an unsubstituted group. Saturated hydrocarbon group, carboxy group, sulfo group, sulfato group, cyano group, halogen atom (eg, fluorine, chlorine, bromine, iodine), hydroxy group, mercapto group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group , An alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkanesulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, an alkanesulfonylsulfamoyl group, and the like. n ¹ represents 0 or 1. When n ¹ is 0, L ¹ is preferably an unsubstituted methine group, and n ¹
When 1 is 1, L ¹ and L ³ are preferably unsubstituted methine groups, L ² is preferably a methine group substituted with an unsubstituted alkyl group (eg, methyl, ethyl, propyl), and L ² is further Preferred is a methine group in which an ethyl group is substituted.

M ¹ represents a counterion and is included in the formula to indicate the presence of a cation or anion when necessary to neutralize the ionic charge of the dye. Whether a dye is a cation, an anion, or has a net ionic charge depends on its substituents and the environment in solution (pH, etc.). Typical cations are inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg calcium ion), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0] -7-undecenium ion) can be mentioned. The anion may be either an inorganic anion or an organic anion, a halide anion (eg, fluoride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (eg p- Toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion,
2,6-naphthalenedisulfonate ion), alkylsulfate ion (for example, methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Is mentioned. In addition, ionic polymers or other dyes having an opposite charge to the dye may be used. Preferred cations are sodium ion, potassium ion, triethylammonium ion,
Tetraethylammonium ion, pyridinium ion, ethylpyridinium ion, and methylpyridinium ion. Preferred anions are perchlorate ion, iodide ion, bromide ion and substituted aryl sulfonate ion (eg p-toluene sulfonate ion).
m ¹ represents a number of 0 or more required to balance the charge,
It is 0 when forming an intramolecular salt. The number is preferably 0 or more and 4 or less.

The methine dye represented by the general formula (I) is more preferably represented by the general formula (II), (III), (IV) or (V).

In the general formula (II), Y ¹¹ represents an oxygen atom, a sulfur atom or NR ¹³ , and R ¹³ is a hydrogen atom, an unsubstituted alkyl group, or a substituted alkyl group (for example, W described above is substituted). Alkyl group). The substituent of the substituted alkyl group is preferably a substituent having a higher hydrophilicity than an iodine atom, more preferably the same as a chlorine atom, or a substituent having a higher hydrophilicity, and particularly preferably the same as a fluorine atom. , An alkyl group substituted with a more hydrophilic substituent. R ¹³ is more preferably a hydrogen atom or an unsubstituted alkyl group, and particularly preferably a hydrogen atom or a methyl group. Y ¹¹ is particularly preferably a sulfur atom. X ¹¹ and X ¹² represent an oxygen atom or a sulfur atom, at least one of which is preferably a sulfur atom, and both of which are preferably sulfur atoms.

V¹¹, V¹², V¹³, V¹⁴, V¹⁵And V¹⁶
Represents a hydrogen atom or a monovalent substituent, V¹¹, V¹², V
¹³And V¹⁴Of two adjacent substituents or V¹⁵When
V¹⁶Link together to form a saturated or unsaturated fused ring
However, it is preferable not to form a condensed ring. One price
Examples of the substituent of W include the aforementioned W, and preferably
Alkyl groups (eg methyl), aryl groups (eg phenol)
Nyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), ar
Coxy group (eg methoxy), alkylthio group (eg
Methylthio), cyano groups, acyl groups (eg acetyl
), An alkoxycarbonyl group (eg methoxycarbo)
Nil), halogen atoms (eg fluorine, chlorine, bromine, yo
Arsenic), more preferably methyl group, methoxy
A group, a cyano group, a halogen atom, and more preferably
Halogen atom, particularly preferably fluorine, chlorine, odor
Elemental atom, most preferably chlorine atom. V¹¹,
V¹²And V ¹⁴Is preferably a hydrogen atom. Y¹¹Is a sulfur atom
If V¹⁵And V¹⁶At least one of the halogen atoms (for example,
Fluorine, chlorine, bromine, iodine)
And more preferably V¹⁶Is a hydrogen atom, V¹⁵Is fluorine,
Chlorine and bromine atoms, particularly preferably chlorine atom.

R¹¹And R¹²Is an alkyl substituted with an acid group
Group represented by R, but preferably R ¹As with the acid group
R is a substituted alkyl group¹¹And R¹²Less of
One is an alkyl group substituted with an acid group other than a sulfo group
And more preferably R¹¹And R¹²One
One other than sulfo group (preferably carboxyl group or
Alkanes substituted with a lucansulfonylcarbamoyl group)
Is an alkyl group substituted with a sulfo group and the other is an alkyl group
In some cases. In addition, the alkyl substituted with these acid groups
Specific examples and preferable combinations of the kill group are the above R groups.¹The theory
It is the same as the one revealed. More preferably, R¹¹And
And R¹²One of which is a carboxymethyl group or methanesulfo
It is particularly preferable when it is a nylcarbamoylmethyl group.
Actually, R¹¹Is a carboxymethyl group or methanesulfo
When it is a nylcarbamoylmethyl group, R¹²Is 3
-A case of a sulfopropyl group. M¹¹Is a counterion
Represents m¹¹Is necessary to neutralize the charge in the molecule
Represents a number of 0 or more,¹, M¹Similar to
You can M¹¹Is particularly preferably a cation
More preferably, the preferred cations are sodium, potassium and potassium.
Liethylammonium, pyridinium, N-ethylpyri
It is Zinium.

In the general formula (III), Y ²¹ represents an oxygen atom, a sulfur atom or N—R ²³ , and R ²³ is a hydrogen atom, an unsubstituted alkyl group or a substituted alkyl group (for example, W described above is substituted). Alkyl group). The substituent of the substituted alkyl group is preferably a substituent having a higher hydrophilicity than an iodine atom, more preferably the same as a chlorine atom, or a substituent having a higher hydrophilicity, and particularly preferably the same as a fluorine atom. , An alkyl group substituted with a more hydrophilic substituent. R ²³ is more preferably a hydrogen atom or an unsubstituted alkyl group, and particularly preferably a hydrogen atom or a methyl group. Y ²¹ is particularly preferably a sulfur atom. X ²¹ and X ^{22 each} represent an oxygen atom or a sulfur atom, at least one of which is preferably a sulfur atom, and both of which are preferably sulfur atoms.

V^{twenty one}, V^{twenty two}, V^{twenty three}, V^{twenty four}, V^{twenty five}And V²⁶
Represents a hydrogen atom or a monovalent substituent, V^{twenty one}, V^{twenty two}, V
^{twenty three}And V^{twenty four}Of two adjacent substituents or V^{twenty five}When
V²⁶Link together to form a saturated or unsaturated fused ring
However, it is preferable not to form a condensed ring. One price
Examples of the substituent of W include the aforementioned W, and preferably
Alkyl groups (eg methyl), aryl groups (eg phenol)
Nyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), ar
Coxy group (eg methoxy), alkylthio group (eg
Methylthio), cyano groups, acyl groups (eg acetyl
), An alkoxycarbonyl group (eg methoxycarbo)
Nil), halogen atoms (eg fluorine, chlorine, bromine, yo
Arsenic), more preferably methyl group, methoxy
A group, a cyano group, a halogen atom, and more preferably
Halogen atom, particularly preferably fluorine, chlorine, odor
Elemental atom, most preferably chlorine atom. V^{twenty one},
V^{twenty two}And V ^{twenty four}Is preferably a hydrogen atom. Y^{twenty one}Is a sulfur atom
If V^{twenty five}And V²⁶At least one of the halogen atoms (for example,
Fluorine, chlorine, bromine, iodine)
And more preferably V²⁶Is a hydrogen atom, V^{twenty five}Is fluorine,
Chlorine and bromine atoms, particularly preferably chlorine atom.

R^{twenty one}And R^{twenty two}Is an alkyl substituted with an acid group
Group represented by R, but preferably R ¹As with the acid group
R is a substituted alkyl group^{twenty one}And R^{twenty two}Less of
One is an alkyl group substituted with an acid group other than a sulfo group
And more preferably R^{twenty one}And R^{twenty two}One
One other than sulfo group (preferably carboxyl group or
Alkanes substituted with a lucansulfonylcarbamoyl group)
Is an alkyl group substituted with a sulfo group and the other is an alkyl group
In some cases. In addition, the alkyl substituted with these acid groups
Specific examples and preferable combinations of the kill group are the above R groups.¹The theory
It is the same as the one revealed. More preferably, R^{twenty one}And
And R^{twenty two}One of which is a carboxymethyl group or methanesulfo
It is particularly preferable when it is a nylcarbamoylmethyl group.
Actually, R^{twenty one}Is a carboxymethyl group or methanesulfo
When it is a nylcarbamoylmethyl group, R^{twenty two}Is 3
-A case of a sulfopropyl group. M^{twenty one}Is a counterion
Represents m^{twenty one}Is necessary to neutralize the charge in the molecule
Represents a number of 0 or more,¹, M¹Similar to
You can M^{twenty one}Is particularly preferably a cation
More preferably, the preferred cations are sodium, potassium and potassium.
Liethylammonium, pyridinium, N-ethylpyri
It is Zinium.

In the general formula (IV), Y ³¹ represents an oxygen atom, a sulfur atom or NR ³³ , and R ³³ is a hydrogen atom, an unsubstituted alkyl group, or a substituted alkyl group (for example, W described above is substituted). Alkyl group). The substituent of the substituted alkyl group is preferably a substituent having a higher hydrophilicity than an iodine atom, more preferably the same as a chlorine atom, or a substituent having a higher hydrophilicity, and particularly preferably the same as a fluorine atom. , An alkyl group substituted with a more hydrophilic substituent. R ³³ is more preferably a hydrogen atom or an unsubstituted alkyl group, and particularly preferably a hydrogen atom or a methyl group. Y ³¹ is particularly preferably a sulfur atom. X ³¹ and X ³² represent an oxygen atom or a sulfur atom, at least one of which is preferably a sulfur atom, and both of which are preferably sulfur atoms.

V³¹, V³², V³³, V³⁴, V³⁵And V³⁶
Represents a hydrogen atom or a monovalent substituent, V³¹, V³², V
³³And V³⁴Of two adjacent substituents or V³⁵When
V³⁶Link together to form a saturated or unsaturated fused ring
However, it is preferable not to form a condensed ring. One price
Examples of the substituent of W include the aforementioned W, and preferably
Alkyl groups (eg methyl), aryl groups (eg phenol)
Nyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), ar
Coxy group (eg methoxy), alkylthio group (eg
Methylthio), cyano groups, acyl groups (eg acetyl
), An alkoxycarbonyl group (eg methoxycarbo)
Nil), halogen atoms (eg fluorine, chlorine, bromine, yo
Arsenic), more preferably methyl group, methoxy
A group, a cyano group, a halogen atom, and more preferably
Halogen atom, particularly preferably fluorine, chlorine, odor
Elemental atom, most preferably chlorine atom. V³¹,
V³²And V ³⁴Is preferably a hydrogen atom. Y³¹Is a sulfur atom
If V³⁵And V³⁶At least one of the halogen atoms (for example,
Fluorine, chlorine, bromine, iodine)
And more preferably V³⁶Is a hydrogen atom, V³⁵Is fluorine,
Chlorine and bromine atoms, particularly preferably chlorine atom.

R³¹And R³²Is an alkyl substituted with an acid group
Group represented by R, but preferably R ¹As with the acid group
R is a substituted alkyl group³¹And R³²Less of
One is an alkyl group substituted with an acid group other than a sulfo group
And more preferably R³¹And R³²One
One other than sulfo group (preferably carboxyl group or
Alkanes substituted with a lucansulfonylcarbamoyl group)
Is an alkyl group substituted with a sulfo group and the other is an alkyl group
In some cases. In addition, the alkyl substituted with these acid groups
Specific examples and preferable combinations of the kill group are the above R groups.¹The theory
It is the same as the one revealed. More preferably, R³¹And
And R³²One of which is a carboxymethyl group or methanesulfo
It is particularly preferable when it is a nylcarbamoylmethyl group.
Actually, R³¹Is a carboxymethyl group or methanesulfo
When it is a nylcarbamoylmethyl group, R³²Is 3
-A case of a sulfopropyl group. M³¹Is a counterion
Represents m³¹Is necessary to neutralize the charge in the molecule
Represents a number of 0 or more,¹, M¹Similar to
You can M³¹Is particularly preferably a cation
More preferably, the preferred cations are sodium, potassium and potassium.
Liethylammonium, pyridinium, N-ethylpyri
It is Zinium.

In the general formula (V), Y ⁴¹ represents an oxygen atom, a sulfur atom or NR ⁴³ , and R ⁴³ is a hydrogen atom, an unsubstituted alkyl group, or a substituted alkyl group (for example, W described above is substituted). Alkyl group). The substituent of the substituted alkyl group is preferably a substituent having a higher hydrophilicity than an iodine atom, more preferably the same as a chlorine atom, or a substituent having a higher hydrophilicity, and particularly preferably the same as a fluorine atom. , An alkyl group substituted with a more hydrophilic substituent. R ⁴³ is more preferably a hydrogen atom or an unsubstituted alkyl group, and particularly preferably a hydrogen atom or a methyl group. Y ⁴¹ is particularly preferably a sulfur atom. X ⁴¹ and X ⁴² represent an oxygen atom or a sulfur atom, at least one of which is preferably a sulfur atom, and both of which are preferably sulfur atoms.

V⁴¹, V⁴², V⁴³, V⁴⁴, V⁴⁵And V⁴⁶
Represents a hydrogen atom or a monovalent substituent, V⁴¹, V⁴², V
⁴³And V⁴⁴Of two adjacent substituents or V⁴⁵When
V⁴⁶Link together to form a saturated or unsaturated fused ring
However, it is preferable not to form a condensed ring. One price
Examples of the substituent of W include the aforementioned W, and preferably
Alkyl groups (eg methyl), aryl groups (eg phenol)
Nyl), an aromatic heterocyclic group (for example, 1-pyrrolyl), ar
Coxy group (eg methoxy), alkylthio group (eg
Methylthio), cyano groups, acyl groups (eg acetyl
), An alkoxycarbonyl group (eg methoxycarbo)
Nil), halogen atoms (eg fluorine, chlorine, bromine, yo
Arsenic), more preferably methyl group, methoxy
A group, a cyano group, a halogen atom, and more preferably
Halogen atom, particularly preferably fluorine, chlorine, odor
Elemental atom, most preferably chlorine atom. V⁴¹,
V⁴²And V ⁴⁴Is preferably a hydrogen atom. Y⁴¹Is a sulfur atom
If V⁴⁵And V⁴⁶At least one of the halogen atoms (for example,
Fluorine, chlorine, bromine, iodine)
And more preferably V⁴⁶Is a hydrogen atom, V⁴⁵Is fluorine,
Chlorine and bromine atoms, particularly preferably chlorine atom.

R⁴¹And R⁴²Is an alkyl substituted with an acid group
Group represented by R, but preferably R ¹As with the acid group
R is a substituted alkyl group⁴¹And R⁴²Less of
One is an alkyl group substituted with an acid group other than a sulfo group
And more preferably R⁴¹And R⁴²One
One other than sulfo group (preferably carboxyl group or
Alkanes substituted with a lucansulfonylcarbamoyl group)
Is an alkyl group substituted with a sulfo group and the other is an alkyl group
In some cases. In addition, the alkyl substituted with these acid groups
Specific examples and preferable combinations of the kill group are the above R groups.¹The theory
It is the same as the one revealed. More preferably, R⁴¹And
And R⁴²One of which is a carboxymethyl group or methanesulfo
It is particularly preferable when it is a nylcarbamoylmethyl group.
Actually, R⁴¹Is a carboxymethyl group or methanesulfo
When it is a nylcarbamoylmethyl group, R⁴²Is 3
-A case of a sulfopropyl group. M⁴¹Is a counterion
Represents m⁴¹Is necessary to neutralize the charge in the molecule
Represents a number of 0 or more,¹, M¹Similar to
You can M⁴¹Is particularly preferably a cation
More preferably, the preferred cations are sodium, potassium and potassium.
Liethylammonium, pyridinium, N-ethylpyri
It is Zinium.

When the dye of the general formula (I) is used in the blue-sensitive emulsion layer, it is selected from the general formula (II) or (III),
More preferred are dyes of general formula (II). X ¹¹ , X ¹² and Y ¹¹
(X ²¹ , X ²² and Y ²¹ ) are both sulfur atoms, and V
It is preferable that ¹⁵ (V ²⁵ ) is a chlorine atom or a bromine atom, and V ¹⁶ (V ²⁶ ) is a hydrogen atom. V ¹¹ , V ¹² , V ¹⁴ (V
²¹ , V ²² and V ²⁴ are hydrogen atoms, and V ¹³ (V ²³ ) is an alkyl group (eg methyl), an alkoxy group (eg methoxy), an alkylthio group (eg methylthio), a cyano group, an acyl group (eg acetyl). ), An alkoxycarbonyl group (for example, methoxycarbonyl), a halogen atom (for example, fluorine, chlorine, bromine, iodine), and more preferably a methyl group, a methoxy group, a cyano group,
An acetyl group, a methoxycarbonyl group and a halogen atom are preferred, a halogen atom is particularly preferred, and a fluorine atom and a chlorine atom are most preferred. R ¹¹ and R ¹² (R ²¹ and R
²² ) It is preferred that one is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group and the other is a 3-sulfopropyl group, and particularly preferred is R
^{This is the case where 11} (R ²¹ ) is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group and R ¹² (R ²² ) is a 3-sulfopropyl group. It is preferable that M ¹¹ (M ²¹ ) is an organic or inorganic monovalent cation, and m ¹¹ (m ²¹ ) is 0 or 1.

When the dye of the general formula (I) is used in the green-sensitive emulsion layer, the dye of the general formula (IV) or (V) (A ³¹ (A ⁴¹ )
Is preferably an ethyl group) and has the general formula (IV)
Are more preferable. Y ³¹ (Y ⁴¹ ) is a sulfur atom, X ³¹ and X ³² (X ⁴¹ and X ⁴² ) are both oxygen atoms, V ³⁵ (V ⁴⁵ ) is a chlorine atom or a bromine atom, and V ³⁶ (V
⁴⁶ ) is preferably a hydrogen atom. V ³¹ , V ³² , V
³⁴ (V ⁴¹ , V ⁴² , V ⁴⁴ ) is a hydrogen atom, and V
³³ (V ⁴³ ) is an alkyl group (eg methyl), an alkoxy group (eg methoxy), an alkylthio group (eg methylthio), a cyano group, an acyl group (eg acetyl), an alkoxycarbonyl group (eg methoxycarbonyl), a halogen atom (eg (Fluorine, chlorine, bromine, iodine) are preferable, methyl group, methoxy group, cyano group, acetyl group, methoxycarbonyl group and halogen atom are more preferable, halogen atom is particularly preferable, and fluorine is most preferable. Atom and chlorine atom. R ³¹
It is preferred that one of R and R ³² (R ⁴¹ and R ⁴² ) is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group and the other is a 3-sulfopropyl group, and particularly preferred is R ³¹ (R ⁴¹ ). Carboxymethyl group or methanesulfonylcarbamoylmethyl group, R
^This is the case where ³² (R ⁴² ) is a 3-sulfopropyl group.
M ³¹ (M ⁴¹ ) is an organic or inorganic monovalent cation, and m ³¹ (m ⁴¹ ) is preferably 0 or 1.

When the dye of the general formula (I) is used in the red-sensitive emulsion layer, the dye of the general formula (IV) or (V) (A ³¹ (A ⁴¹ )
Is preferably an ethyl group) and has the general formula (IV)
Are more preferable. Y ³¹ (Y ⁴¹ ) is a sulfur atom, one of X ³¹ and X ³² (X ⁴¹ and X ⁴² ) is an oxygen atom, the other is a sulfur atom, and V ³⁵ (V ⁴⁵ ) is a chlorine atom or a bromine atom, V ³⁶ (V ⁴⁶ ) is preferably a hydrogen atom.
V ³¹ , V ³² and V ³⁴ (V ⁴¹ , V ⁴² and V ⁴⁴ ) are hydrogen atoms, and V ³³ (V ⁴³ ) is an alkyl group (eg methyl), an alkoxy group (eg methoxy), an alkylthio group (eg methylthio). ), A cyano group, an acyl group (eg acetyl), an alkoxycarbonyl group (eg methoxycarbonyl), a halogen atom (eg fluorine, chlorine, bromine, iodine), and more preferably a methyl group, a methoxy group, a cyano group. , Acetyl group, methoxycarbonyl group and halogen atom, particularly preferably halogen atom, most preferably fluorine atom and chlorine atom. One of R ³¹ and R ³² (R ⁴¹ and R ⁴² ) is preferably a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and the other is preferably a 3-sulfopropyl group, and particularly preferably R ³¹ (R ⁴¹ ) Is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group,
This is the case where R ³² (R ⁴² ) is a 3-sulfopropyl group. M ³¹ (M ⁴¹ ) is an organic or inorganic monovalent cation, and m ³¹ (m ⁴¹ ) is preferably 0 or 1.

The general formulas (I), (II), and
Specific examples of the methine dyes represented by (III), (IV) and (V) are shown below, but the present invention is not limited thereto.

[0074]

[Chemical 14]

[0075]

[Chemical 15]

[0076]

[Chemical 16]

[0077]

[Chemical 17]

[0078]

[Chemical 18]

[0079]

[Chemical 19]

[0080]

[Chemical 20]

[0081]

[Chemical 21]

[0082]

[Chemical formula 22]

[0083]

[Chemical formula 23]

[0084]

[Chemical formula 24]

[0085]

[Chemical 25]

[0086]

[Chemical formula 26]

General formulas (I) and (I used in the present invention
The methine dyes I), (III), (IV) and (V) can be synthesized based on the methods described in the following documents. a) FM Hamer "Heterocyclic Compounds-Cyanine dy"
es and related compounds "(John Wiley & Sons)
New York, London, 1964), b) DMSturmer, "Heterocyclic Compounds-Special"
topics in heterocyclic chemistry ", Chapter 8, Chapter 4
Pp. 482-515 (John Wiley & Sons, Inc.-New York, London, 1977), c) "Rodd's Chemistry of Carbon Compounds", second.
Edition, Volume 4, Part B, Chapter 15, Pages 369-422 (Elsevier Science Publishing Company Inc.-New York, 1977).

The general formulas (I), (II) and (II
For the synthesis of the heterocycle as a raw material for the methine dye represented by I), (IV) and (V), see Bulletin de la
Societe Chimique de France, pp. II-150 (198
0 years), Journal of Heterocyclic Chemistry, 16: 1563 (1979) and the like.

The general formulas (I), (II) and (II of the present invention
The methine dyes represented by I), (IV) and (V) can be contained in the silver halide emulsion of the present invention by dispersing them directly in the emulsion, or by water, methanol, ethanol. , Propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy It may be added to the emulsion by dissolving it in a solvent such as -2-propanol or N, N-dimethylformamide alone or in a mixed solvent.

Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent and the solution is dispersed in water or a hydrophilic colloid. To add to the emulsion, JP-B-46-2418
No. 5, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding the dispersion to an emulsion, JP-B-44-23389 and 44-27.
No. 555, No. 57-22091, etc., a method in which a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is coexisted to form an aqueous solution and the solution is added to the emulsion. U.S. Pat. Nos. 3,822,135, 4,
As described in Japanese Patent Application No. 006,026, a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant into an emulsion, JP-A-53-102733.
No. 58-105141, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, as described in JP-A-51-74624, Dissolve the dye with a compound that
It is also possible to use a method of adding the solution into the emulsion.
Ultrasonic waves can also be used for dissolution.

General formulas (I), (II) and (II of the present invention
The timing of adding the methine dyes represented by I), (IV) and (V) to the silver halide emulsion of the present invention is during any step of emulsion preparation which has been found to be useful so far. May be. For example, US Pat. No. 2,735,76
No. 6, No. 3,628,960, No. 4,183,7
56, No. 4,225,666, JP-A-58-18.
No. 4142, No. 60-196749, etc., the chemical ripening is performed before the grain formation step of silver halide and / or before desalting, during the desalting step and / or after desalting. Before the start, JP-A-58-11
As disclosed in the specification such as 3920, it may be added at any time or step immediately before chemical ripening or during the step, or after the chemical ripening and before the emulsion is coated. Also, U.S. Pat. No. 4,225,6
66, JP-A-58-7629 and the like, the same compound alone or in combination with a compound having a different structure, for example, during the grain formation step and the chemical ripening step or chemically. It may be added in divided portions such as after completion of aging or before or after chemical aging or after completion of the process. May be.

General formulas (I), (II) and (II of the present invention
The amount of the methine dye represented by I), (IV) and (V) varies depending on the shape and size of the silver halide grains, but is preferably 0.1 to 4 mmol per mol of silver halide, more preferably Is 0.2 to 2.5 mmol and may be used in combination with other sensitizing dyes.

In the present invention, the general formulas (I), (II),
Other than the methine dyes represented by (III), (IV) and (V), other sensitizing dyes may be used. A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,9.
77,229, 3,397,060, 3,
No. 522,052, No. 3,527,641, No. 3,617,293, No. 3,628,964, No. 3,666,480, No. 3,672,898,
No. 3,679,428, No. 3,703,377
No. 3,769,301, No. 3,814,60
No. 9, No. 3,837,862, No. 4,026,7
07, British Patents 1,344,281 and 1,5
07,803, Japanese Examined Patent Publication Nos. 43-4936, 53-1
2375, JP-A Nos. 52-110618 and 52-1.
No. 09925.

The coupler represented by formula (X) is described in detail below. In the general formula (X), the multimer means a compound having two or more groups represented by the general formula (X) in one molecule, and includes a bis form and a polymer coupler. Here, the polymer coupler has the general formula (X)
A homopolymer composed of a monomer having a portion represented by (preferably having a vinyl group) may be used, or a homopolymer composed of a non-color-forming ethylene-like monomer that does not couple with an oxidized product of an aromatic primary amine developing agent. It may be made of polymerized polymer.

Z¹, Z²Is -C (Q³) = Or −N =
One is -N = and the other is -C (Q³) =
Preferably there is. More preferably Z²Is -N =
R, Z ¹Is -C (Q³) =

Q ¹ and Q ³ are alkyl groups (preferably linear or branched alkyl groups having 1 to 32 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 1-octyl. , Tridecyl), a cycloalkyl group (preferably a cycloalkyl group having a carbon number of 3 to 32, for example, cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group (preferably having a carbon number of 2 to 2).
32 alkenyl groups, such as vinyl, allyl, 3-
Buten-1-yl), aryl group (preferably having 6 carbon atoms)
To 32 aryl groups, for example, phenyl, 1-naphthyl, 2-naphthyl, heterocyclic group (preferably having 1 carbon atom).
~ 32, a 5- to 8-membered heterocyclic group, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzo. Triazol-2-yl), cyano group, halogen atom (for example, fluorine, chlorine,
Bromine), hydroxyl group, nitro group, carboxyl group,
An alkoxy group (preferably an alkoxy group having 1 to 32 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2
-Butoxy, isopropoxy, t-butoxy, dodecyloxy), cycloalkyloxy group (preferably cycloalkyloxy group having 3 to 32 carbon atoms, for example, cyclopentyloxy, cyclohexyloxy), aryloxy group (preferably having carbon number) 6-32 aryloxy groups, for example, phenoxy, 2-naphthoxy), heterocyclic oxy groups (preferably C 1-32 heterocyclic oxy groups, for example, 1-phenyltetrazole-5-oxy, 2- Tetrahydropyranyloxy, 2-furyloxy), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, for example, trimethylsilyloxy, t
-Butyldimethylsilyloxy, diphenylmethyloxy), an acyloxy group (preferably an acyloxy group having 2 to 32 carbon atoms, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably having 2 carbon atoms). To 32 alkoxycarbonyloxy groups, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy), cycloalkylcarbonyloxy groups (preferably having 4 carbon atoms).
To 32 cycloalkylcarbonyloxy groups, for example, cyclohexylcarbonyloxy), aryloxycarbonyloxy groups (preferably aryloxycarbonyloxy groups having 7 to 32 carbon atoms, for example, phenoxycarbonyloxy), carbamoyloxy groups (preferably Is a carbamoyloxy group having 1 to 32 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), sulfamoyloxy (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, for example, , N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkanesulfonyloxy group (preferably an alkanesulfonyloxy group having 1 to 32 carbon atoms, for example, methanesulfonyloxy, hexadecanesulfonyloxy). ), An arenesulfonyloxy group (preferably an arenesulfonyloxy group having 6 to 32 carbon atoms, for example, benzenesulfonyloxy), an acyl group (preferably an acyl group having 1 to 32 carbon atoms, for example, formyl, acetyl, pivaloyl). , Benzoyl, tetradecanoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 32 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl), a cycloalkyloxycarbonyl group (preferably having 4 to 4 carbon atoms). 32 groups, for example,
Cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably a group having 7 to 32 carbon atoms, for example, phenoxycarbonyl), a carbamoyl group (preferably a carbamoyl group having 1 to 32 carbon atoms, for example, carbamoyl, N, N-). Dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl), an amino group (preferably an amino group having a carbon number of 32 or less, for example, amino, methylamino, N, N-dioctylamino, tetradecylamino, Octadecylamino), anilino group (preferably anilino group having 6 to 32 carbon atoms, for example, anilino, N-methylanilino), heterocyclic amino group (preferably heterocyclic amino group having 1 to 32 carbon atoms, for example, 4 -Pyridylamino), carbonamide group (preferably charcoal With a group of number 2 to 32, for example,
Acetamide, benzamide, tetradecanamide),
Ureido group (preferably a ureido group having 1 to 32 carbon atoms, for example, ureido, N, N-dimethylureido, N
-Phenylureido), imide group (preferably having 1 carbon atom)
An imide group of 0 or less, for example, N-succinimide, N
-Phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 32 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino), an aryloxycarbonylamino group. (Preferably a group having 7 to 32 carbon atoms,
For example, phenoxycarbonylamino), a sulfonamide group (preferably a sulfonamide group having 1 to 32 carbon atoms, for example, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide), a sulfamoylamino group (preferably Is a sulfamoylamino group having 1 to 32 carbon atoms, for example, N, N
-Dipropylsulfamoylamino, N-ethyl-N-
Dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, for example, phenylazo),
Alkylthio group (preferably an alkylthio group having 1 to 32 carbon atoms such as ethylthio and octylthio), arylthio group (preferably a group having 6 to 32 carbon atoms such as phenylthio), heterocyclic thio group (preferably having carbon number) 1 to 32 heterocyclic thio groups, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), alkanesulfinyl groups (preferably alkylsulfinyl groups having 1 to 32 carbon atoms, for example, Dodecanesulfinyl), arenesulfinyl group (preferably an arenesulfinyl group having 6 to 32 carbon atoms, for example, benzenesulfinyl), an alkanesulfonyl group (preferably an alkylsulfonyl group having 1 to 32 carbon atoms, for example, methanesulfonyl, octane Sulfonyl), arene sulfonyl (Preferably having a carbon number of 6 to 3
2 arenesulfonyl groups, for example, benzenesulfonyl, 1-naphthalenesulfonyl), sulfamoyl groups (preferably sulfamoyl groups having 32 or less carbon atoms, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N). -Dodecylsulfamoyl), a sulfo group, and a phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl).

Q ² represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent. Specifically, the removable group is a halogen atom, an alkoxy group, an aryloxy group,
It represents an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, a carbonamido group, a sulfonamide group, a carbamoylamino group, a heterocyclic group, an arylazo group, an alkylthio group, an arylthio group, a heterocyclic thio group and the like. The preferred range and specific examples of these groups are the same as those mentioned in the description of the groups represented by Q ¹ and Q ³ .
In addition to these, Q ² is 2 via an aldehyde or ketone.
It may be a bis-type coupler in which a 4-equivalent coupler of the molecule is bonded, and Q ² may be a photographically useful group such as a development accelerator, a development inhibitor, a desilvering accelerator or a leuco dye or a precursor thereof. .

The groups represented by Q ¹ , Q ² and Q ³ may further have a substituent, and preferable substituents are a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group and a hetero group. Ring group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy Group, sulfamoyloxy group,
Alkanesulfonyloxy group, arenesulfonyloxy group, carboxyl group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamide group, alkoxy Carbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfinyl group, sulfo group, alkanesulfonyl group, arenesulfonyl group , Sulfamoyl group, and phosphonyl group.

The coupler represented by the general formula (X) may form a dimer or higher polymer or polymer with the substituents Q ¹ , Q ² and Q ³ .

Q ¹ is preferably a secondary or tertiary alkyl group (eg, isopropyl group, cyclopropyl group, t-group).
Butyl group, 1-methylcyclopropyl group, etc.), more preferably a tertiary alkyl group, and particularly preferably t
A butyl group.

Q ³ is preferably an alkyl group having 1 to 32 carbon atoms or an aryl group having 6 to 32 carbon atoms, and further has a substituent (for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, Nitro group, alkoxy group, aryloxy group, carboxyl group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, alkoxycarbonylamino group, aryl Oxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfinyl group, sulfo group, alkanesulfonyl group, arenesulfonyl group, sulfamoyl group or phosphine Preferably has a group). In particular, it is preferable that the substituent include a sulfonamide group containing —SO ₂ —, a sulfamoylamino group, a sulfo group, an alkanesulfonyl group, an arenesulfonyl group, or the like as a substituent.

Q ² is a hydrogen atom or a coupling leaving group, and the leaving group is preferably a chlorine atom, a bromine atom, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a heterocyclic group, A chlorine atom or an aryloxy group is more preferable, and a chlorine atom is most preferable.

A more preferable form of the coupler represented by formula (X) is represented by formula (XI) or (XII).

In formula (XI), Q ¹¹ represents an alkyl group,
A secondary or tertiary alkyl group (eg isopropyl group,
(A cyclopropyl group, a t-butyl group, a 1-methylcyclopropyl group, etc.) are preferable, a tertiary alkyl group is more preferable, and a t-butyl group is particularly preferable. Q ¹² represents a hydrogen atom or a halogen atom, and the halogen atom is preferably a chlorine atom or a bromine atom, and most preferably a chlorine atom. Q ¹³ represents a substituent containing —SO ₂ —, a sulfonamide group, a sulfamoylamino group,
An alkyl group having 1 to 32 carbon atoms or an aryl group having 6 to 32 carbon atoms, which contains an alkanesulfonyl group, an arenesulfonyl group or the like as a substituent, is preferable.

In formula (XII), Q ²¹ represents an alkyl group, but a secondary or tertiary alkyl group (eg, isopropyl group, cyclopropyl group, t-butyl group, 1-methylcyclopropyl group, etc.) is preferable. , More preferably a tertiary alkyl group, and particularly preferably a t-butyl group. Q
²² represents a hydrogen atom or a halogen atom, and the halogen atom is preferably a chlorine atom or a bromine atom, and most preferably a chlorine atom. Q ²³ is -SO ₂ - represents a substituent containing a sulfonamido group, a sulfamoylamino group, an alkanesulfonyl group, or an alkyl group having 1 to 32 carbon atoms such as arene sulfonyl group is contained as a substituent An aryl group having 6 to 32 carbon atoms is preferable. Most preferred as the coupler of the general formula (X) is the form of the general formula (XII).

Specific examples of the coupler represented by formula (X), (XI) or (XII) which can be used in the present invention are shown below, but the present invention is not limited thereto. In addition to the following, magenta couplers M-1 to M-30 described in JP-A-8-109334 or JP-A-9-109334
-185156 Magenta couplers M-1 to M-
You can also choose from 40.

[0107]

[Chemical 27]

[0108]

[Chemical 28]

[0109]

[Chemical 29]

[0110]

[Chemical 30]

[0111]

[Chemical 31]

[0112]

[Chemical 32]

[0113]

[Chemical 33]

[0114]

[Chemical 34]

[0115]

[Chemical 35]

[0116] Formula (X), (XI) or the addition amount of the coupler represented by (XII) is 3 × 10 ^- a ⁵ to 3 × 10 ^-3 mol / m ² is suitable, preferably 3 × 10 ^{-4 to} 2 x 10
^-3 mol / m ² . General formula (X), (XI) or (XI
The coupler represented by I) is used as a magenta coupler. A 5-pyrazolone-based magenta coupler as described in a known document in the table below is also used, but among them, a coupler represented by the general formula (X), (XI) or (XII) is used in view of processing dependence. Preferably.

The coupler represented by formula (XX) is described in detail below.

In the coupler represented by formula (XX), Q ⁵ represents a substituted or unsubstituted aryl group. It is preferably a substituted aryl group, and examples of the substituent at this time include the above-described substituent W, a chlorine atom, a methoxy group,
A t-butyl group is preferred. Among them, chlorine atom 1 as Q ⁵
Particularly preferred are phenyl groups substituted by one or two.
Q ⁶ represents a substituted or unsubstituted alkyl group. It is preferably a substituted alkyl group, and examples of the substituent at this time include the above-mentioned substituent W. Particularly, Q ⁶ is preferably a 1-substituted alkyl group, and an aryloxy group or an arylsulfonyl group is most preferably used as the substituent at the 1-position. Q ⁷ represents a hydrogen atom, a halogen atom, an alkoxy group or an alkyl group, and preferably a hydrogen atom.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent, and examples of the group include a halogen atom (fluorine, chlorine, bromine, etc.), an alkoxy group (ethoxy, methoxycarbonylmethoxy, Carboxypropyloxy, methanesulfonylethoxy, perfluoropropoxy, etc.), aryloxy group (4-carboxyphenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy, 4-methanesulfonyl-3-carboxyphenoxy, 2-methanesulfonyl-4. -Acetylsulfamoylphenoxy, etc.), acyloxy group (acetoxy, benzoyloxy, etc.), sulfonyloxy group (methanesulfonyloxy, benzenesulfonyloxy, etc.), acylamino group (heptafluorobutyrylamino, etc.), sulfonamide group (meth) Sulfonamide, etc.), alkoxycarbonyloxy group (ethoxycarbonyloxy, etc.), carbamoyloxy group (diethylcarbamoyloxy, piperidinocarbonyloxy, morpholinocarbonyloxy, diallylcarbamoyloxy, bisdicyanoethylcarbamoyloxy, etc.), alkylthio group ( 2-carboxyethylthio, etc.), an arylthio group (2-octyloxy-5-t-octylphenylthio, 2- (2,4
-Di-t-amylphenoxy) butyrylaminophenylthio etc.), heterocyclic thio group (1-phenyltetrazolylthio, 2-benzimidazolylthio etc.), heterocyclic oxy group (2-pyridyloxy, 5-nitro- 2-pyridyloxy, etc.), a 5- or 6-membered nitrogen-containing heterocyclic group (1-triazolyl, 1-imidazolyl, 1-pyrazolyl, 5-chloro-1-tetrazolyl, 1-benzotriazolyl, 2
-Phenylcarbamoyl-1-imidazolyl, 5,5-
Dimethylhydantoin-3-yl, 1-benzylhydantoin-3-yl, 5,5-dimethyloxazolidine-
2,4-dione-3-yl, purine, etc.), azo group (4-
Methoxyphenylazo, 4-pivaloylaminophenylazo, etc.) and the like.

In the general formula (XX), the substituent X is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyloxy group or a carbamoyloxy group, and particularly preferably a halogen atom, especially a chlorine atom. is there.

The coupler represented by the general formula (XX) is
A dimer or higher multimer may be formed through Q ⁵ , Q ⁶ and Q ^7, and may be bound to a polymer chain.

Specific examples of the coupler represented by formula (XX) and preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0123]

[Chemical 36]

[0124]

[Chemical 37]

The addition amount of the coupler represented by the general formula (XX) is appropriately 2 × 10 ^{-5 to} 5 × 10 ^-3 mol / m ² ,
The preferable addition amount is 2 × 10 ^{−4 to} 3 × 10 ⁻³ mol / m ² . The coupler represented by formula (XX) is used as a cyan coupler. Examples of cyan couplers that can be used in combination with the cyan coupler or used in a magenta coupler-containing photosensitive material include diphenylimidazole-based cyan couplers described in JP-A-2-33144, EP0333385A2.
3-Hydroxypyridine cyan couplers described in the specification (of the couplers (42) listed as specific examples among them)
Equivalent couplers having a chlorine leaving group to make them two equivalents, couplers (6) and (9) are particularly preferable) and JP-A-64-
Cyclic active methylene cyan couplers described in JP 32260 (Coupler Examples 3, 8, 34 listed as specific examples are particularly preferable), EP 0456226A.
Examples thereof include a pyrrolopyrazole type cyan coupler and a pyrroloimidazole type cyan coupler described in EP0484904.

As the yellow coupler, in addition to the compounds shown in the table below, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in the acyl group described in EP0447969A1, EP0482552A1.
The malondianilide type yellow couplers having a cyclic structure described in JP-A No. 1994, and the acylacetamide type yellow couplers having a dioxane structure described in US Pat. No. 5,118,599 are preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

Cyan, magenta or yellow couplers are impregnated with a rollable latex polymer (eg US Pat. No. 4,203,716) in the presence (or absence) of high boiling organic solvents as described in the table below. Alternatively, it is preferably dissolved with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Examples of water-insoluble and organic solvent-soluble polymers that can be preferably used include the homopolymers or copolymers described on pages 12 to 30 of US Pat. No. 4,857,449. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

For the light-sensitive material relating to the present invention, it is preferable to use a color image storability improving compound as described in EP0277589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler or a pyrrolotriazole coupler. That is, the compound in the aforementioned patent specification which chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or after the color development processing It is possible to use the compounds in the above-mentioned patents, alone or simultaneously, which chemically bond with the oxidant of the residual aromatic amine color developing agent to form a chemically inert and substantially colorless compound. It is preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction between the coupler and the residual color developing agent in the film during storage after the processing.

In the silver halide photographic light-sensitive material of the present invention, the silver halide grains include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, silver chloroiodobromide and the like. For example, for color photographic paper, a silver chlorobromide emulsion is preferable for the purpose of speeding up and simplifying the processing. For these silver chlorobromide emulsions, silver chloride, silver chlorobromide, or silver chloroiodobromide in which 95 mol% or more is silver chloride can be preferably used.

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

The shape of silver halide grains contained in a photographic emulsion has a regular crystal form such as a cube, octahedron or tetradecahedron, and an irregular crystal such as a sphere or a plate. It may have a shape or a mixture thereof. In the present invention, 50% or more of the particles having the above-mentioned regular crystal form are used among these,
The content is preferably 70% or more, more preferably 90% or more. In addition to this, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can be preferably used.

The emulsion used in the present invention is described by P. Glafkides in "C
himie et Phisique Photographique "(Paul Montel, 1967), GF Duffin," Photographic Emuls "
ion Chemistry "(Focal Press, 1966), V.
Making and coating Photographi by L. Zelikman et al
c Emulsion ”(Focal Press, 1964) and the like. That is, any method such as an acidic method, a neutral method or an ammonia method may be used, and as a method for reacting a soluble silver salt and a soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. Any method may be used. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The silver halide emulsion used in the present invention is
It is usually chemically sensitized. The chemical sensitization method includes chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-215272, page 18, lower right column to 22.
Those described in the upper right column of the page are preferably used.

The silver halide emulsion used in the present invention contains various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. It can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Further EP 0447647
5-Arylamino-1,2,3,4-
A thiatriazole compound (having at least one electron-withdrawing group in the aryl residue) is also preferably used.

The silver halide emulsion prepared according to the present invention can be used in both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials. Examples of the color photographic light-sensitive material include color paper, color photographic film, color reversal film, and black-and-white photographic light-sensitive material include X-ray film, general photographic film, and printing light-sensitive material film.

Regarding various techniques and inorganic / organic materials which can be used for the silver halide photographic light-sensitive material of the present invention, Research Disclosure No. 308
119 (1989) and 37038 (1995) can be used.

In addition to this, more specifically, for example,
Techniques and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following section of EP 436938A2 and the patents cited below.

[0138]     Item This location 1) Layer structure, page 146, line 34 to page 147, line 25 2) Silver halide emulsion, page 147, line 26 to page 148, line 12 3) Yellow coupler page 137, line 35 to page 146, line 33, line 14                         Page 9, lines 21-23 4) Magenta Coupler, page 149, lines 24 to 28; European Patent 421                         453A1, page 3, line 5 to page 25, line 55 5) Cyan coupler, page 149, lines 29-33; EP 432                         804A2, page 3, line 28 to page 40, line 2 6) Polymer coupler, page 149, lines 34-38; European Patent 435                         334A2, page 113, line 39 to page 123                         37th line 7) Colored coupler, page 53, line 42 to page 137, line 34, 149                         Page 39th line to 45th line 8) Other functionality Page 7, line 1 to page 53, line 41; page 149 46     Coupler line to page 150, line 3; EP 435334.                       Page 3, Line 1 to Page 29, Line 50, Line A2 9) Preservative, page 150, lines 25-28 10) Formalin, page 149, lines 15-17       Scavenger 11) Other additives, page 153, lines 38-47; European Patent 421                       No. 453A1, page 75, line 21 to page 84, line 56 12) Dispersion method Page 150, lines 4 to 24 13) Support, page 150, lines 32 to 34 14) Film thickness and film physical properties, page 150, lines 35 to 49 15) Color development step, page 150, line 50 to page 151, line 47 16) Desilvering process, page 151, line 48 to page 152, line 53 17) Automatic processor, page 152, line 54 to page 153, line 2 18) Washing / stabilization process, page 153, lines 3 to 37

In the light-sensitive material of the present invention, it is also preferable to color the hydrophilic colloid layer for the purpose of preventing irradiation or halation and improving safety of safelight. Examples of the water-soluble dye that can be used as such a coloring substance include dyes that can be decolorized by treatment (especially oxonol dyes and cyanine dyes) described on pages 27 to 76 of EP 0337490A. In such coloring, the coloring substance diffuses regardless of the position where the coloring substance is added, and spreads over the entire photosensitive material constituent layer.

[0140]

EXAMPLES The present invention will be specifically described below with reference to examples, but the invention is not limited thereto.

Example 1 (Preparation of Sample) After performing corona discharge treatment on both sides of a support obtained by coating both sides of paper with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Further, the photographic constituent layers of the first to seventh layers were sequentially applied to prepare a sample 101 of a silver halide color photographic light-sensitive material having the following layer constitution. The coating liquid for each photographic constituent layer was prepared as follows.

Preparation of Fifth Layer Coating Solution Cyan coupler (ExC) 300 g, color image stabilizer (Cp
d-1) 250 g, color image stabilizer (Cpd-9) 10 g,
Color image stabilizer (Cpd-10) 10 g, color image stabilizer (Cp-10
d-12) 20 g, ultraviolet absorber (UV-1) 14 g,
50g UV absorber (UV-2), UV absorber (UV
-3) 40 g and ultraviolet absorber (UV-4) 60 g
230 g of a solvent (Solv-6) and ethyl acetate 3
This was dissolved in 50 ml, and this liquid was emulsified and dispersed in 6500 g of a 10% gelatin aqueous solution containing 200 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion C. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C having a grain size of 0.41 μm (silver molar ratio). Coefficient of variation of grain size distribution is , 0.09 and 0.11, respectively. For each size emulsion, 0.5 mol% of silver bromide was locally contained in a part of the surface of the grain based on silver chloride) was prepared. In this emulsion, the red sensitizing dyes G and H shown below were added to the large-sized emulsion C in an amount of 6.0 × per mol of silver.
10 ⁻⁵ mol, and 9.0 × 10 ⁻⁵ mol were added to the small size emulsion C, respectively. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a coating solution for the fifth layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. In addition, Ab-1, Ab-2, Ab-3 and Ab-4 are respectively contained in each layer in a total amount of 15.0 mg / m ² , 60.0 mg / m ² ,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0144]

[Chemical 38]

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

[0146]

[Chemical Formula 39]

(Sensitizing dyes A, B and C are silver halides)
1.4 for large emulsions per mole
× 10^-Four1.7 for mol and small size emulsions
× 10 ^-FourMol added. ) Green sensitive emulsion layer

[0148]

[Chemical 40]

(Sensitizing dye D per mol of silver halide was 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and Sensitizing dye E per mol of silver halide was 4.0 × 10 ⁻⁵ mol for large size emulsion and 7.0 for small size emulsion.
^{X10 -5} mol, and sensitizing dye F per mol of silver halide is 2.0 x 10 ^-4 mol for large size emulsion and 2.8 x 10 ^-4 mol for small size emulsion. Was added. ) Red-sensitive emulsion layer

[0150]

[Chemical 41]

(Sensitizing dyes G and H per mole of silver halide: [each] 6.0 for a large-sized emulsion)
× 10 ^-5 ] mol, and for small size emulsions, 9.
0 × 10 ⁻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.

[0152]

[Chemical 42]

Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
For the red-sensitive emulsion layer, 1- (3-methylureidophenyl)
) -5-mercaptotetrazole, respectively.
3.3 x 10 per mol of silver halide^-FourMole, 1.0 × 10
^-3Molar and 5.9 x 10^-FourMol added. In addition,
The second layer, the fourth layer, the sixth layer, and the seventh layer each have 0.
2 mg / m ², 0.2 mg / m², 0.6 mg / m²,
0.1 mg / m²Was added. Also, blue sensitivity
4-hydroxy-6 for the emulsion layer and the green-sensitive emulsion layer
-Methyl-1,3,3a, 7-tetrazaindene
1 x 10 per mol of silver halide^-FourMole, 2x
10^-FourMol added. In addition, methacrylic acid is added to the red-sensitive emulsion layer.
Copolymer of acid and butyl acrylate (mass ratio 1: 1, average
Molecular weight 200000-400000) 0.05 g / m
²Was added. In addition, the second, fourth and sixth layers are
Cole-3,5-disulfonate disodium respectively
6 mg / m², 6 mg / m², 6 mg / m²So that
Was added. Also, to prevent irradiation, emulsion
Add the following dyes (the amount in parentheses represents the coating amount) to the layer
It was

[0154]

[Chemical 43]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support polyethylene resin laminated paper [white pigment (TiO ₂ ; polyethylene resin on the first layer side;
Content 16 wt%, ZnO; content of 4 wt%) and a fluorescent brightener (4,4 ^'- bis (benzoxazolyl) stilbene and ^4,4' - bis (5-methyl-benzoxazolyl)
8: 2 mixture of stilbenes: content 0.05% by mass),
Including bluish dye (ultra-blue)]

[0156] First layer (blue sensitive emulsion layer)   Silver chlorobromide emulsion A (cubic, large size emulsion A having an average grain size of 0.72 μm and 0 ． 3: 7 Mixture with 60 μm Small Size Emulsion A (silver molar ratio). Particle size distribution The coefficients of variation are 0.08 and 0.10. 0.3 mol silver bromide for each size emulsion % Was locally contained in a part of the surface of the grain based on silver chloride. )                                                             0.26   Gelatin 1.35   Yellow coupler (ExY) 0.62   Color image stabilizer (Cpd-1) 0.08   Color image stabilizer (Cpd-2) 0.04   Color image stabilizer (Cpd-3) 0.08   Solvent (Solv-1) 0.23

[0157] Second layer (color mixing prevention layer)   Gelatin 0.99   Color mixing inhibitor (Cpd-4) 0.09   Color image stabilizer (Cpd-5) 0.018   Color image stabilizer (Cpd-6) 0.13   Color image stabilizer (Cpd-7) 0.01   Solvent (Solv-1) 0.06   Solvent (Solv-2) 0.22

[0158] Third layer (green sensitive emulsion layer)   Silver chlorobromide emulsion B (cubic, large size emulsion B having an average grain size of 0.45 μm and 0 ． 1: 3 mixture with 35 μm small size emulsion B (silver molar ratio). Particle size distribution The coefficients of variation are 0.10 and 0.08, respectively. 0.4 mol silver bromide for each size emulsion % Was locally contained in a part of the surface of the grain based on silver chloride. )                                                           0.14   Gelatin 1.36   Magenta coupler (ExM) 0.15   UV absorber (UV-1) 0.05   Ultraviolet absorber (UV-2) 0.03   Ultraviolet absorber (UV-3) 0.02   Ultraviolet absorber (UV-4) 0.04   Color image stabilizer (Cpd-2) 0.02   Color image stabilizer (Cpd-4) 0.002   Color image stabilizer (Cpd-6) 0.09   Color image stabilizer (Cpd-8) 0.02   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

[0159] Fourth layer (color mixing prevention layer)   Gelatin 0.71   Color mixing inhibitor (Cpd-4) 0.06   Color image stabilizer (Cpd-5) 0.013   Color image stabilizer (Cpd-6) 0.10   Color image stabilizer (Cpd-7) 0.007   Solvent (Solv-1) 0.04   Solvent (Solv-2) 0.16

[0160] Fifth layer (red sensitive emulsion layer)   Silver chlorobromide emulsion C (cubic, large size emulsion C having an average grain size of 0.50 μm and 0 ． 1: 4 mixture with 41 μm small size emulsion C (silver molar ratio). Particle size distribution The coefficients of variation are 0.09 and 0.11. 0.5 mol silver bromide for each size emulsion % Was locally contained in a part of the surface of the grain based on silver chloride. )                                                             0.20   Gelatin 1.11.   Cyan coupler (ExC) 0.30   Ultraviolet absorber (UV-1) 0.14   UV absorber (UV-2) 0.05   Ultraviolet absorber (UV-3) 0.04   Ultraviolet absorber (UV-4) 0.06   Color image stabilizer (Cpd-1) 0.25   Color image stabilizer (Cpd-9) 0.01   Color image stabilizer (Cpd-10) 0.01   Color image stabilizer (Cpd-12) 0.02   Solvent (Solv-6) 0.23

[0161] Sixth layer (UV absorption layer)   Gelatin 0.66   Ultraviolet absorber (UV-1) 0.19   Ultraviolet absorber (UV-2) 0.06   Ultraviolet absorber (UV-3) 0.06   UV absorber (UV-4) 0.05   Ultraviolet absorber (UV-5) 0.09   Solvent (Solv-7) 0.25

[0162] Seventh layer (protective layer)   Gelatin 1.00   Acrylic modified copolymer of polyvinyl alcohol (modification degree 17%) 0.04   Liquid paraffin 0.02   Surfactant (Cpd-13) 0.01

[0163]

[Chemical 44]

[0164]

[Chemical formula 45]

[0165]

[Chemical formula 46]

[0166]

[Chemical 47]

[0167]

[Chemical 48]

[0168]

[Chemical 49]

[0169]

[Chemical 50]

Further, with respect to the silver halide color photographic light-sensitive material 101 prepared as described above, the sensitizing dye A used in the first layer (blue-sensitive emulsion layer) was equimolar with the sensitizing dye shown in Table 1. Substituted samples 102 to 109 and sample 100 without addition of sensitizing dye A were prepared. Sample 101
~ 109 each third layer magenta coupler ExM
Samples 201 to 209 and 3 in the same manner except that the couplers shown in Table 1 were replaced so that the maximum color density was the same.
01-309 and 401-409 were created. 1 for each sample
It was processed into a roll having a width of 27 mm.

(Evaluation of residual color of dye) Sample 100 prepared
109, 201-209, 301-309, 401-4
For sample 09, continuous processing (running test) was performed in the following processing steps at a rate of 25% for fog by white exposure and 75% for unexposed sample using separate color developing solutions until replenishment was performed twice as much as the color developing tank capacity. ) Was performed (running treatment liquids 100 to 109, 201 to 209,
301-309, 401-409).

Processing Step Temperature Time Replenishment Amount ^* Color Development 38.5 ° C. 45 seconds 45 ml Bleaching Fixing 38.0 ° C. 45 seconds 35 ml Rinse (1) 38.0 ° C. 20 seconds-Rinse (2) 38.0 ℃ 20 seconds-Rinse (3) ** 38.0 ° C 20 seconds-Rinse (4) ** 38.0 ° C 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Fuji Photo Film phosphorus screening system RC50D is installed in the rinse (3), the rinse solution is taken out from the rinse (3), and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the same 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 water permeated into the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was controlled and circulated for 10 hours a day. (Rinsing was performed from the tank countercurrent system from (1) to (4).)

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] 800 ml water 800 ml Dimethylpolysiloxane-based surfactant 0.1g 0.1g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Triethanolamine 11.6g 11.6g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate                                     0.5g 0.5g Potassium chloride 10.0g- Potassium bromide 0.040g 0.010g Triazinylaminostilbene fluorescent 2.5g 5.0g   Whitening agent (Hakkor FWA-SF / Showa Kagaku) Sodium sulfite 0.1g 0.1g N, N-bis (sulfonatoethyl) hydroxylamine disodium salt                                     8.5g 11.1g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-a   Minoaniline ・ 3/2 sulfuric acid ・ monohydrate                                     5.0 g 15.7 g Potassium carbonate 26.3g 26.3g Add water 1000 ml 1000 ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                   10.15 12.50

[0174] [Bleach fixer] [Tank solution] [Replenisher] 800 ml water 800 ml Ethylenediaminetetraacetate Iron (III) ammonium                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g m-carboxymethylbenzenesulfinic acid                                     8.3g 16.5g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium thiosulfate (750 g / l)                         107.0 ml 214.0 ml Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted with 25 ° C / acetic acid and ammonia)                                     6.0 6.0

[0175] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μs / cm or less)                             1000 ml 1000 ml pH 6.5 6.5

Using a sensitometer, samples 100 to 10 for 1/100 seconds through a color separation filter and gradation wedge.
9, 201-209, 301-309, 401-409
Was exposed to light, and then developed with a corresponding running processing solution, and sensitometry was performed. Further, the yellow density (Dy) of the unexposed portion of the obtained sample was measured. The density difference from the yellow density (Dy ⁰ ) in Sample 100 is the residual color of the sensitizing dye used. The smaller the density difference, the smaller the residual color.

[0177]

[Table 1]

As is clear from Table 1, the sample in which the methine dye of the general formula (I) of the present invention is used in combination with the coupler of the general formula (X) has a high sensitivity, and the residual color after processing is suppressed to a low level. You can see that it is done.

(Evaluation of Processing Dependency) Prepared Sample 101
~ 109, 201-209, 301-309, 401-
For each of the 409 samples, a 25% white exposed fog sample with different developers, an unexposed sample 7
Continuous running was carried out at the rate of 5% under the same conditions as in the residual color evaluation to obtain respective running processing liquids. Before and after the continuous treatment, the following sensitometry was performed using samples having the same numbers as the samples used for the respective continuous treatments. Using a sensitometer, 1 / through a color separation filter and gradation wedge
After exposing each sample for 100 seconds, development processing was performed with a fresh developing solution and a corresponding running processing solution. 1. Magenta density of each sample when processed with the fresh developer before continuous processing
At an exposure amount giving 0, the magenta density (Dm) at the time of development processing using each running processing solution was measured. This density change (ΔDm = Dm−2.0) is determined, and the larger the negative value, the greater the fluctuation in photographic property due to continuous processing.

As is clear from Table 1, when the methine dye of the general formula (I) of the present invention was used, the photographic fluctuation of the magenta color density after continuous processing was the magenta of the general formula (X) of the present invention. It is kept small by using it in combination with a coupler. Especially when the coupler of the general formula (XII) is used, the fluctuation in photographic property is minimized.

Example 2 Preparation of Sample 501 Preparation of Triacetyl Cellulose Film Triacetyl cellulose was dissolved in dichloromethane / methanol = 92/8 (mass ratio) by an ordinary solution casting method (13% by mass). ), A plasticizer triphenyl phosphate and biphenyl diphenyl phosphate were added at a mass ratio of 2: 1 so that the total amount was 14% with respect to triacetyl cellulose, and the mixture was prepared by the band method. The thickness of the support after drying was 97 μm.

Content of Undercoat Layer The following undercoat was applied to both surfaces of the above triacetyl cellulose film. The numbers represent the mass contained per 1.0 liter of the undercoat liquid. In addition, before applying the undercoat,
Corona discharge treatment was applied to both sides. Gelatin 10.0 g Salicylic acid 0.5 g Glycerin 4.0 g Acetone 700 ml Methanol 200 ml Dichloromethane 80 ml Formaldehyde 0.1 mg Water was added to 1.0 liter

Coating of Back Layer The back layer shown below was coated on one surface of the undercoated support. First layer Binder: Acid-treated gelatin (isoelectric point 9.0) 1.00 g Polymer latex P-2 (average particle size 0.1 μm) 0.13 g Polymer latex: P-3 (average particle size 0.2 μm) 0.23 g UV absorber U-1 0.030g UV absorber U-3 0.010g UV absorber U-4 0.020g High boiling organic solvent Oil-2 0.030g Surfactant W-3 0.010g Surfactant W-6 3.0mg

[0184] Second layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.10 g         Polymer latex: P-3 (average particle size 0.2 μm) 0.11 g         UV absorber U-1 0.030g         UV absorber U-3 0.010g         UV absorber U-4 0.020 g         High boiling organic solvent Oil-2 0.030g         Surfactant W-3 0.010g         Surfactant W-6 3.0mg         Dye D-2 0.10g         Dye D-10 0.12g         Potassium sulfate 0.25g         Calcium chloride 0.5mg         Sodium hydroxide 0.03g

[0185] 3rd layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.30 g         Surfactant W-3 0.020g         Potassium sulfate 0.30g         Sodium hydroxide 0.03g

[0186]   4th layer Binder: Lime-treated gelatin (isoelectric point 5.4) 1.15g         1: 9 copolymer of methacrylic acid and methyl methacrylate             (Average particle size 2.0 μm) 0.040 g         6: 4 copolymer of methacrylic acid and methyl methacrylate             (Average particle size 2.0 μm) 0.030 g         Surfactant W-3 0.060g         Surfactant W-2 7.0mg         Hardener H-1 0.23g

Coating of Photosensitive Emulsion Layer The following photosensitive emulsion layer was coated on the side opposite to the side coated with the back layer to give Sample 501. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.25g 2.40 g gelatin UV absorber U-1 0.15g UV absorber U-3 0.15g UV absorber U-4 0.10g UV absorber U-5 0.10g High boiling organic solvent Oil-1 0.10 g High boiling organic solvent Oil-2 0.10 g High boiling organic solvent Oil-5 0.010 g Dye D-4 1.0mg Dye D-8 2.5mg Microcrystalline solid dispersion of Dye E-1 0.05 g

Second layer: intermediate layer Gelatin 0.50g Compound Cpd-A 0.2 mg Compound Cpd-K 3.0 mg Compound Cpd-M 0.030 g UV absorber U-6 6.0mg High boiling organic solvent Oil-3 0.010g High boiling organic solvent Oil-4 0.010 g High boiling organic solvent Oil-7 2.0 mg Dye D-7 4.0mg

[0190] Third layer: Middle layer       Yellow colloidal silver 0.020g       Silver iodobromide emulsion whose surface and inside have been previously covered       (Cube, average silver iodide content 1%, average sphere-equivalent grain size 0.06 μm)                                     Silver amount 0.010g       Gelatin 0.60 g       Compound Cpd-D 0.020 g       High boiling organic solvent Oil-3 0.010g       High boiling organic solvent Oil-8 0.010 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.10g Emulsion B Silver amount 0.15g Emulsion C Silver amount 0.15g Gelatin 0.80g Coupler Cp-1 0.15g Coupler Cp-2 7.0mg Coupler Cp-10 3.0mg Coupler Cp-11 2.0mg UV absorber U-3 0.010g Compound Cpd-I 0.020 g Compound Cpd-D 3.0 mg Compound Cpd-J 2.0 mg High boiling organic solvent Oil-10 0.030 g Additive P-1 5.0 mg

Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion C Silver amount 0.15g Emulsion D Silver amount 0.15g Gelatin 0.70 g Coupler Cp-1 0.15g Coupler Cp-2 7.0mg Coupler Cp-10 3.0mg Compound Cpd-D 3.0 mg UV absorber U-3 0.010g High boiling organic solvent Oil-10 0.030 g Additive P-1 7.0 mg

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion E Silver amount 0.15g Emulsion F Silver amount 0.20g 1.50 g gelatin Coupler Cp-1 0.60g Coupler Cp-2 0.015g Coupler Cp-3 0.030g Coupler Cp-10 5.0 mg UV absorber U-1 0.010g UV absorber U-2 0.010 g High boiling organic solvent Oil-6 0.030g High boiling organic solvent Oil-9 0.020 g High boiling organic solvent Oil-10 0.050 g Compound Cpd-D 5.0 mg Compound Cpd-K 1.0 mg Compound Cpd-F 0.030 g Compound Cpd-L 1.0 mg Additive P-1 0.010g Additive P-4 0.030g

Seventh layer: intermediate layer Gelatin 0.70 g Additive P-2 0.10g Dye D-5 0.020 g Dye D-9 6.0mg Compound Cpd-I 0.010 g Compound Cpd-M 0.040 g Compound Cpd-O 3.0 mg Compound Cpd-P 5.0 mg High boiling organic solvent Oil-6 0.050g

Eighth layer: intermediate layer Yellow colloidal silver Silver amount 0.020g Gelatin 1.00g Additive P-2 0.05g UV absorber U-1 0.010g UV absorber U-3 0.010g Compound Cpd-A 0.050 g Compound Cpd-D 0.030 g Compound Cpd-M 0.050 g High boiling organic solvent Oil-3 0.010g High boiling organic solvent Oil-6 0.050g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion G Silver amount 0.25g Emulsion H Silver amount 0.30g Emulsion I Silver amount 0.25g 1.30 g gelatin Coupler Cp-4 0.20g Coupler Cp-5 0.050g Coupler Cp-6 0.020g Compound Cpd-A 5.0 mg Compound Cpd-B 0.030 g Compound Cpd-D 5.0 mg Compound Cpd-G 2.5mg Compound Cpd-F 0.010 g Compound Cpd-K 2.0 mg UV absorber U-6 5.0 mg High boiling organic solvent Oil-2 0.25g Additive P-1 5.0 mg

[0197] 10th layer: Medium sensitivity green sensitive emulsion layer       Emulsion I Silver amount 0.30g       Emulsion J Silver amount 0.30g       Silver bromide emulsion covered inside (cube, sphere-equivalent average particle diameter 0.11 μm)                                   Silver amount 3.0mg       Gelatin 0.70 g       Coupler Cp-4 0.25g       Coupler Cp-5 0.050g       Coupler Cp-6 0.020g       Compound Cpd-A 5.0 mg       Compound Cpd-B 0.030 g       Compound Cpd-F 0.010 g       Compound Cpd-G 2.0 mg       High boiling organic solvent Oil-2 0.20g       High boiling organic solvent Oil-9 0.050g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion K Silver amount 0.40g Gelatin 0.80g Coupler Cp-4 0.30g Coupler Cp-5 0.080g Coupler Cp-7 0.050g Compound Cpd-A 5.0 mg Compound Cpd-B 0.030 g Compound Cpd-F 0.010 g High boiling organic solvent Oil-2 0.20g High boiling organic solvent Oil-9 0.050g

Twelfth layer: yellow filter layer Yellow colloidal silver Silver amount 0.010g Gelatin 1.0g Compound Cpd-C 0.010 g Compound Cpd-M 0.10 g High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-6 0.10 g Microcrystalline solid dispersion of Dye E-2 0.20 g

Thirteenth layer: intermediate layer Gelatin 0.40g Compound Cpd-Q 0.20 g Dye D-6 3.0mg

Fourteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.15g Emulsion M Silver amount 0.20g Emulsion N Silver amount 0.10g Gelatin 0.80g Coupler Cp-8 0.020g Coupler Cp-9 0.30g Coupler Cp-10 5.0 mg Compound Cpd-B 0.10 g Compound Cpd-I 8.0 mg Compound Cpd-K 1.0 mg Compound Cpd-M 0.010 g UV absorber U-6 0.010 g High boiling organic solvent Oil-2 0.010 g

[0202] Fifteenth layer: Medium sensitivity blue-sensitive emulsion layer       Emulsion N Silver amount 0.20g       Emulsion O Silver amount 0.20g       Silver bromide emulsion covered inside (cube, sphere-equivalent average particle diameter 0.11 μm)                                   Silver amount 3.0mg       Gelatin 0.80g       Coupler Cp-8 0.020g       Coupler Cp-9 0.25g       Coupler Cp-10 0.010g       Compound Cpd-B 0.10 g       Compound Cpd-E 0.030 g       Compound Cpd-N 2.0 mg       High boiling organic solvent Oil-2 0.010 g

Sixteenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion P Silver amount 0.20g Emulsion Q Silver amount 0.25g Gelatin 2.00g Coupler Cp-3 5.0mg Coupler Cp-8 0.10g Coupler Cp-9 1.00g Coupler Cp-10 0.020g High boiling organic solvent Oil-2 0.10 g High boiling organic solvent Oil-3 0.020g UV absorber U-6 0.10g Compound Cpd-B 0.20 g Compound Cpd-N 5.0 mg

Seventeenth layer: First protective layer Gelatin 1.00g UV absorber U-1 0.15g UV absorber U-2 0.050g UV absorber U-5 0.20g Compound Cpd-O 5.0 mg Compound Cpd-A 0.030 g Compound Cpd-H 0.20 g Dye D-1 8.0mg Dye D-2 0.010g Dye D-3 0.010g High boiling organic solvent Oil-3 0.10 g

[0205] 18th layer: 2nd protective layer       Colloidal silver Silver amount 2.5 mg       Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%)                                   Silver amount 0.10g       Gelatin 0.80g       UV absorber U-1 0.030g       UV absorber U-6 0.030g       High boiling organic solvent Oil-3 0.010g

[0206] 19th layer: 3rd protective layer       Gelatin 1.00g       Polymethylmethacrylate (average particle size 1.5 μm)                                           0.10 g       6: 4 copolymer of methyl methacrylate and methacrylic acid         (Average particle size 1.5 μm) 0.15 g       Silicone oil SO-1 0.20g       Surfactant W-1 3.0mg       Surfactant W-2 8.0 mg       Surfactant W-3 0.040g       Surfactant W-7 0.015g

In addition to the above composition, additives F-1 to F-9 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

[0208]

[Table 2]

[0209]

[Table 3]

[0210]

[Table 4]

[0211]

[Chemical 51]

[0212]

[Chemical 52]

[0213]

[Chemical 53]

[0214]

[Chemical 54]

[0215]

[Chemical 55]

[0216]

[Chemical 56]

[0217]

[Chemical 57]

[0218]

[Chemical 58]

[0219]

[Chemical 59]

[0220]

[Chemical 60]

[0221]

[Chemical formula 61]

[0222]

[Chemical formula 62]

[0223]

[Chemical formula 63]

[0224]

[Chemical 64]

[0225]

[Chemical 65]

[0226]

[Chemical formula 66]

[0227]

[Chemical formula 67]

[0228]

[Chemical 68]

Preparation of Dispersion of Organic Solid Disperse Dye (Preparation of Dispersion of Dye E-1) A wet cake of Dye E-1 (270 g as a net amount of E-1) was mixed with P manufactured by BASF.
100 g of luronic F88 (ethylene oxide-propylene oxide block copolymer) and water were added and stirred to make 4000 g. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Visco Mill (UVM-2) manufactured by IMEX Co., Ltd., and the slurry was passed through the slurry at a peripheral speed of about 10 m / sec and a discharge rate of 0.51 / min to obtain 2
Crushed for hours. The beads were filtered off, water was added to dilute to a dye concentration of 3% and then heated at 90 ° C. for 10 hours for stabilization. The average particle size of the obtained dye fine particles is 0.30.
The particle size distribution is wide (particle size standard deviation x 100).
/ Average particle size) was 20%.

(Preparation of Solid Dispersion of Dye E-2)
270 g of water and W-4 were added to 1400 g of a wet cake of E-2 containing 0% by mass and stirred to obtain a slurry having an E-2 concentration of 40% by mass. Next, crusher, IMEX Co., Ltd.
Ultra Visco Mill (UVM-2) manufactured by Japan has an average particle size of 0.5
1700 ml of mm zirconia beads were filled, and the slurry was crushed for 8 hours at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 liter / min to obtain a solid fine particle dispersion of E-2. This was diluted with ion-exchanged water to 20% by mass to obtain a solid fine particle dispersion. Average particle size is 0.15 μm
Met.

(Samples 500, 502 to 506, 601 to
Preparation of 606, 701 to 706, and 801 to 806) Sensitizing dye Sen− of emulsions A to F used in Sample 501
Samples 502 to 506 were prepared by replacing 8 with an equimolar amount of dye as shown in Table 5, and a dye blank sample 500 was prepared by removing both dyes. Samples 501 to 50
6 magenta couplers Cp-4 and Cp-5 were replaced by the couplers of Table 5 so that the maximum color densities would be the same, and samples 601 to 606, 701 to 706 and 801
806 was created. The sample piece thus obtained is 1/1
After white exposure was performed through a gray wedge with an exposure time of 00 seconds and an exposure amount of 20 CMS, sensitometry was performed by the following processing steps. The dye blank sample 5 was obtained from the magenta density of stain of the sample piece after the further treatment.
The residual color was evaluated by subtracting the concentration of magenta stain of 00. The stain concentration was measured with a density measuring device manufactured by X-RITE, status A.

In this example, the following development processing steps were performed. During processing, the unexposed sample and the completely exposed sample were in a ratio of 1: 1 and the replenishment amount was 4% of the tank volume.
A running process was performed until the number of times doubled, and then a process for evaluation was performed. Treatment process time Temperature Tank capacity Replenishment amount 6 minutes 38 ° C 37 liters 2200 ml / m ² First washing 2 minutes 38 ° C 16 liters 4000 ml / m ² Inversion 2 minutes 38 ° C 17 liters 1100 ml / m ² Color development Development 6 minutes 38 ° C 30 liters 2200 ml / m ² Pre-bleaching 2 minutes 38 ° C 19 liters 1100 ml / m ² Bleaching 6 minutes 38 ° C 30 liters 220 ml / m ² Settling 4 minutes 38 ° C 29 liters 1100 ml / m 2 ² Second washing 4 minutes 38 ° C 35 liters 4000 ml / m ² Final rinse 1 minute 25 ° C 19 liters 1100 ml / m ²

The composition of each processing liquid was as follows. [First developer] [Tank liquid] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt 1.5g 1.5g   Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0g 2.0g   Sodium sulfite 30g 30g   Hydroquinone / potassium monosulfonate 20g 20g   Potassium carbonate 15g 20g   Potassium bicarbonate 12g 15g   1-phenyl-4-methyl-4-hydroxymethyl     -3-Pyrazolidone 2.5g 3.0g   Potassium bromide 2.5g 1.4g   Potassium thiocyanate 1.2g 1.2g   Potassium iodide 2.0 mg-   Diethylene glycol 13g 15g Add water 1000 ml 1000 ml     pH 9.60 9.60     The pH was adjusted with sulfuric acid or potassium hydroxide.

[0234] [Reversal liquid] [Tank liquid] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid tank liquid ・ Same as 3.0g of 5 sodium salt   Stannous chloride / dihydrate 1.0 g   p-aminophenol 0.1g   Sodium hydroxide 8.0g   Glacial acetic acid 15 ml   1000 ml with water     pH 6.00     The pH was adjusted with acetic acid or sodium hydroxide.

[0235] [Color developer] [Tank solution] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid   ・ 5 sodium salt 2.0g 2.0g   Sodium sulfite 7.0g 7.0g   Trisodium phosphate dodecahydrate 36g 36g   Potassium bromide 1.0 g −   Potassium iodide 90mg-   Sodium hydroxide 12.0g 12.0g   Citrazine acid 0.5g 0.5g   N-ethyl-N- (β-methanesulfonamidoethyl)     -3-Methyl-4-aminoaniline ・ 3/2 sulfuric acid ・     1 water salt 10g 10g   3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Add water 1000 ml 1000 ml   pH 11.80 12.00     The pH was adjusted with sulfuric acid or potassium hydroxide.

[0236] [Pre-bleaching] [Tank solution] [Replenisher]   Ethylenediamine tetraacetic acid / sodium salt / dihydrate 8.0g 8.0g   Sodium sulfite 6.0g 8.0g   1-thioglycerol 0.4g 0.4g   Formaldehyde sodium bisulfite adduct 30g 35g   Add water 1000 ml 1000 ml pH 6.30 6.10     The pH was adjusted with acetic acid or sodium hydroxide.

[0237] [Bleaching solution] [Tank solution] [Replenisher] Ethylenediamine tetraacetic acid / sodium salt / dihydrate 2.0 g 4.0 g   Ethylenediaminetetraacetic acid-Fe (III) -Ammonium     ・ Dihydrate 120g 240g   Potassium bromide 100g 200g   Ammonium nitrate 10g 20g   Add water 1000 ml 1000 ml pH 5.70 5.50     The pH was adjusted with nitric acid or sodium hydroxide.

[0238] [Fixer] [Tank] [Replenisher] Ammonium thiosulfate 80g Same as tank liquid Sodium sulfite 5.0g 〃   Sodium bisulfite 5.0g 〃   Add water to 1000 ml 〃     pH 6.60     The pH was adjusted with acetic acid or aqueous ammonia.

[0239] [Stabilizer] [Tank liquid] [Replenisher]   1,2-benzisothiazolin-3-one 0.02g 0.03g   Polyoxyethylene-p-monononylphenyl ether     (Average degree of polymerization 10) 0.3g 0.3g   Polymaleic acid (average molecular weight 2,000) 0.1g 0.15g   Add water 1000 ml 1000 ml     pH 7.0 7.0

In the developing step, each bath continuously circulates and stirs the liquid, and further, on the lower surface of each tank, a foam tube having small holes of 0.3 mm in diameter at 1 cm intervals is arranged. Nitrogen gas was continuously bubbled and stirred.

(Evaluation of Processing Dependency) Prepared Sample 501
~ 506, 601-606, 701-706, 801-
For each of 806, the unexposed sample and the one completely exposed to light were continuously processed under the same conditions as in the residual color evaluation using different developing solutions at a ratio of 1: 1 to obtain respective running processing solutions. Before and after the continuous treatment, the following sensitometry was performed using samples having the same numbers as the samples used for the respective continuous treatments. Each sample was exposed for 1/100 seconds through a color separation filter and a gradation wedge using a sensitometer, and then developed with a fresh developing solution and a corresponding running processing solution. At the exposure amount giving a magenta density of 2.0 of each sample when processed with the fresh developer before continuous processing, the magenta density (Dm when developed with each running processing solution) ) Was measured. This density change (ΔDm = Dm−2.0) is determined, and the larger the negative value, the greater the fluctuation in photographic property due to continuous processing.

Table 5 below shows the evaluation results of sensitometry, residual color, and photographic variation due to continuous processing. The relative sensitivity of the red-sensitive layer was compared based on the relative exposure amount from the lowest density to 1.0 higher.

[0243]

[Table 5]

As is clear from the results shown in Table 5, by using the methine dye of the general formula (I) of the present invention, a sensitive material having less residual color and high sensitivity can be obtained. The fluctuation of the magenta color density at that time could be suppressed by using the magenta coupler of the general formula (X).

Example 3 (Preparation of Samples) Samples 101 to 109 prepared in Example 1
Samples 901 to 909, 1001-1 in the same manner except that the cyan coupler ExC of the fifth layer of each of the above was replaced by the coupler shown in Table 6 so that the maximum color density was the same.
009 was created. Each sample was processed into a roll having a width of 127 mm.

(Evaluation of residual color of dye) Sample 100 prepared
109, 901 to 909, and 1001 to 1009, the color developing tanks in the processing steps described in Example 1 at a ratio of 25% fog sample by white exposure and 75% unexposed sample using different color developing solutions. 2 of capacity
Continuous processing (running test) was performed until double replenishment (running processing solutions 100 to 109, 901 to 90).
9, 1001 to 1009).

Using a sensitometer, samples 100 to 10 for 1/100 seconds through a color separation filter and a gradation wedge.
After exposing 9, 901 to 909 and 1001 to 1009, development processing was performed with a corresponding running processing solution, and sensitometry was performed. Further, the yellow density (Dy) of the unexposed portion of the obtained sample was measured. Sample 1
The density difference from the yellow density (Dy ⁰ ) in 00 is the residual color of the sensitizing dye used. The smaller the density difference, the smaller the residual color.

[0248]

[Table 6]

As is clear from Table 6, the sample in which the methine dye of the general formula (I) of the present invention was used in combination with the coupler of the general formula (XX) had high sensitivity and the residual color after processing was suppressed to a low level. You can see that it is done.

(Evaluation of Processing Dependency) Prepared Sample 101
.About.109, 901 to 909, and 1001 to 1009, continuous processing was performed under the same conditions as the residual color evaluation at a ratio of 25% of the fog sample by white exposure and 75% of the unexposed sample using different developers. Each running treatment liquid was obtained. Before and after the continuous treatment, the following sensitometry was performed using samples having the same numbers as the samples used for the respective continuous treatments. Using a sensitometer, 1/100 seconds through the color separation filter and gradation wedge,
After each sample was exposed, it was developed with a fresh developing solution and a corresponding running processing solution. At the exposure amount that gives a cyan density of 2.0 of each sample when processed with the fresh developing solution before continuous processing, the cyan density (Dc ) Was measured. This density change (ΔDc = Dc−2.0) is determined, and the larger the negative value, the greater the fluctuation in photographic property due to continuous processing.

As is clear from Table 6, when the methine dye of the general formula (I) of the present invention is used, the photographic variation of the cyan color density after continuous processing is the cyan of the general formula (XX) of the present invention. It is kept small by using it in combination with a coupler.

[0252]

According to the constitution of the present invention, a silver halide photographic light-sensitive material having high sensitivity, less residual color and less variation in photographic properties after continuous processing can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09B 23/00 C09B 23/00 M

Claims (2)

[Claims] 1. In a silver halide photographic light-sensitive material containing at least one silver halide photographic emulsion layer on a support, at least one methine dye represented by the following general formula (I) and the following general formula: A silver halide photographic light-sensitive material comprising at least one coupler represented by (X). General formula (I) In formula (I), X ¹ and X ² represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom or a carbon atom. Y ¹
Is a furan ring or a pyrrole ring which may be condensed with another 5- or 6-membered carbocycle or heterocycle, or which may have a substituent,
Alternatively, it represents a thiophene ring. Y ² represents an atom group necessary for forming a benzene ring or a 5- or 6-membered unsaturated heterocycle, and may have a substituent even if condensed with another 5- or 6-membered carbocycle or heterocycle. You may have. In addition, the bond between the two carbon atoms fused to Y ¹ and Y ² is 1
It may be a heavy bond or a double bond. R ¹ and R ² represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. L ¹ , L ² and L ³ each represent a methine group, and n ¹ represents 0 or 1. M ¹ represents a counter ion, and m ¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule. General formula (X) In the formula (X), Z ¹ and Z ² represent —C (Q ³ ) ═ or —N═, Q ¹ and Q ³ represent a hydrogen atom or a monovalent substituent,
Q ² represents a hydrogen atom or a coupling leaving group. Q ¹ ,
Q ² or Q ³ may be a divalent group and may combine with a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. 2. A silver halide photographic light-sensitive material containing at least one silver halide photographic emulsion layer on a support, and at least one methine dye represented by the general formula (I) and the following general formula: A silver halide photographic light-sensitive material comprising at least one coupler represented by (XX). General formula (XX) In formula (XX), Q ⁵ is a substituted or unsubstituted aryl group, Q ⁶
Represents a substituted or unsubstituted alkyl group. Q ⁷ represents a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent.