JP2002116518A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity, good preservability and high image quality and ensuring less residual color than a conventional one. SOLUTION: The silver halide photographic sensitive material contains an asymmetric cyanine dye having a specified thiadiazole or thiazole nucleus or the like and a specified benzazole nucleus or the like on which both two substituents at the N-positions are not sulfoalkyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material containing a specific sensitizing dye, having high sensitivity, good storability, high image quality and little residual color.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic materials, improve storage stability, and reduce residual coloring (residual color) after processing. It is known that sensitizing dyes used for spectral sensitization greatly affect the performance of silver halide photographic materials. In sensitizing dyes, slight differences in structure greatly affect photographic performance such as sensitivity, fogging, storage stability, residual color, image quality, but it is difficult to predict the effect in advance, Conventionally, many researchers have tried to synthesize many sensitizing dyes and examine their photographic performance. US Pat. No. 5,354,651 discloses a technique for reducing residual color.
Nos. 5,316,904 and 5,418,126
No. 5,464,736, etc. are known,
Neither was satisfactory enough. In German Patent No. 19,960,279A1, the residual color is improved by a specific sensitizing dye having a thiadiazole nucleus or the like, but the storage stability is not sufficient due to the presence of two sulfoalkyl groups. Also, the residual color was not sufficiently satisfactory.

Also, high aspect ratio tabular silver halide grains (hereinafter referred to as tabular grains) disclosed in US Pat. No. 5,494,789 and the like have a large surface area to volume ratio as photographic characteristics. A large amount of sensitizing dye can be adsorbed on the surface. As a result, higher color sensitization sensitivity can be obtained.

The term “aspect ratio” as used herein refers to the ratio of the diameter to the thickness of tabular grains. Further, the diameter of a tabular grain refers to the diameter of a circle having an area equal to the projected area of the grain when the emulsion is observed with a microscope or an electron microscope. The thickness is indicated by the distance between two parallel planes constituting a tabular grain.

[0005] As described above, tabular grains are advantageous for obtaining high color sensitization sensitivity. However, on the other hand, there is a problem that the preservability deteriorates due to the adsorption of a large amount of the sensitizing dye, and the residual color after the treatment tends to increase, and a solution has been desired.

For the above reasons, there has been a demand for a sensitizing dye which provides a silver halide photographic light-sensitive material having high sensitivity, good storability, high image quality and less residual color than before.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, good storability and high image quality, and having less residual color than before. .

[0008]

Means for Solving the Problems The object of the present invention has been achieved as a result of the following studies (1) to (18). (1) A silver halide photographic material comprising at least one compound represented by the following general formula (I). General formula (I)

[0009]

Embedded image

In the formula (I), X ₁ , X ₂ and X ₃ represent an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or a carbon atom. Z ₁ represents an aromatic hydrocarbon or a group of atoms necessary to form a nitrogen-containing heterocyclic ring in which the aromatic heterocyclic ring is condensed.
R ₁ and R ₂ represent an alkyl group, an aryl group, or a heterocyclic group. However, neither R ₁ nor R _{2 is a} sulfoalkyl group. V ₁ , V ₂ and V ₃ represent a hydrogen atom or a substituent. If q ₁ X ₁ 'carbon atom 2, if q ₁ nitrogen atom 1, otherwise the atomic q ₁ is 0.
If q ₁ X ₁ 'carbon atom 2, if q ₁ nitrogen atom 1, otherwise the atomic q ₁ is 0. When X ₂ is a carbon atom, q ₂ is 1, and when X ₂ is any other atom, q ₂ is 0. When X ₃ is a carbon atom, q ₃ is 1, and when X ₃ is any other atom, q ₃ is 0. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a methine group. n ₁ represents 0, 1, 2, 3, or 4. p ₁
Represents 0 or 1. M ₁ represents a charge-balancing counter ion, m ₁
Represents the number required to neutralize the molecular charge. (2) In the compound of the general formula (I) according to (1),
At least one of R ₁ and R ₂ is an alkyl group substituted by an acid group other than a sulfo group (1).
The silver halide photographic light-sensitive material as described above. (3) In the compound of the general formula (I) according to (1),
One of R ₁ and R ₂ is an alkyl group substituted with a sulfo group, and the other is an alkyl group substituted with an acid group other than a sulfo group (1) or (2).
The silver halide photographic light-sensitive material as described above. (4) The silver halide photographic material as described in (1), wherein the compound of the general formula (I) is selected from the compounds represented by the following general formula (II). General formula (II)

[0011]

Embedded image

In the formula (II), Z ₂ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or a carbon atom.
V ₄ , V ₅ , V ₆ and V ₇ represent a hydrogen atom or a substituent. However, these substituents may form a ring together. One of R ₃ and R ₄ is an alkyl group substituted with a sulfo group, and the other represents an alkyl group substituted with an acid group other than the sulfo group. X ₁ , X ₂ , X ₃ , V ₁ , V ₂ ,
V ₃ , q ₁ , q ₂ , q ₃ , L ₁ , L ₂ , L ₃ , n ₁ , M ₁ , and m ₁ have the same meanings as in the general formula (I). (5) The compound of the general formula (II) is represented by the following general formula (III)
(4) is selected from the compounds represented by
The silver halide photographic light-sensitive material as described above. General formula (III)

[0013]

Embedded image

In the formula (III), V ₁ ′, V ₂ ′ and V ₃ ′
Represents a hydrogen atom or a non-aromatic substituent. V ₄ ',
V ₅ ′, V ₆ ′ and V ₇ ′ represent a hydrogen atom or a substituent. However, V ₅ ′ and V ₆ ′ or V ₆ ′ and V ₇ ′ may together form a 5- or 6-membered ring. R ₁₀ represents a hydrogen atom or an alkyl group. When Z ₂ is a nitrogen atom, R ₁₀ represents a hydrogen atom. n ₁ ′ represents 0 or 1.
X ₁ , X ₂ , X ₃ , q ₁ , q ₂ , q ₃ , R ₃ , R ₄ , M ₁ ,
m ₁ and Z ₂ have the same meanings as in formula (II). (6) an alkyl group substituted by an acid group other than a sulfo group is
Carboxyl group, -CONHSO ₂ - group, -CONHC3H6N
O- group, -SO ₂ NHSO ₂ - silver halide photographic material according to any one of the groups is characterized in that the alkyl group substituted (2) to (5). (7) In the compound represented by the general formula (I), (II) or (III), X ₁ is a sulfur atom, X ₂ is a carbon atom, and X ₃ is a nitrogen atom or a carbon atom. The silver halide photographic light-sensitive material according to any one of (1) to (6), wherein (8) The compound represented by formula (II) or (III), wherein Z ₂ is a sulfur atom (2)
The silver halide photographic light-sensitive material according to any one of (1) to (7). (9) The compound represented by the general formula (II) or (III), wherein X ₃ is a nitrogen atom (8)
The silver halide photographic light-sensitive material described in 1. (10) The silver halide photographic material as described in (8), wherein in the compound represented by formula (II) or (III), X ₃ is a carbon atom. (11) In the compound represented by the general formula (II) or (III), V ₆ and V ₆ ′ are each a halogen atom or an aromatic group. A silver halide photographic light-sensitive material according to any one of the above. (12) In the compound represented by the general formula (II) or (III), V ₄ , V ₅ , V ₇ , V ₄ ′, V ₅ ′, and V ₇ ′ are hydrogen atoms, and V ₆ , And V ₆ ′ is a halogen atom or a phenyl group, wherein the silver halide photographic light-sensitive material according to any one of (2) to (10). (13) The compound represented by the general formula (II) or (III), wherein V ₆ and V ₇ , and V ₆ ′ and V ₇ ′ together form an aromatic ring. (2) to (1)
0) The silver halide photographic light-sensitive material according to any one of the above items. (14) In the compound represented by the general formula (II) or (III), V ₄ , V ₅ , V ₄ ′, and V ₅ ′ are hydrogen atoms, and V ₆ , V ₇ , and V ₆ ′ And V ₇ ′ together form a benzene ring (2) to (10).
A silver halide photographic material as described in any one of the above. (15) The compound represented by formula (I), (II) or (III) is J-aggregating,
4) The silver halide photographic light-sensitive material according to the above. (16) The silver halide photographic light-sensitive material according to any one of (1) to (13), wherein the silver halide photographic emulsion in the light-sensitive material is tabular grains having an aspect ratio of 2 or more and all silver halide grains in the emulsion. (1) The silver halide photographic material as described in any one of (1) to (15) above, wherein the emulsion is present in an amount of at least 50% (area). (17) The silver halide photographic light-sensitive material according to any one of (1) to (16), wherein the silver halide photographic emulsion in the light-sensitive material is selenium-sensitized.
(16) The silver halide photographic material as described in any of (16) above. (18) A photothermographic material containing at least one kind of photosensitive silver halide and a non-photosensitive organic silver salt,
General formulas (I), (II) or (II) described in (1) to (15)
A photothermographic material characterized by containing a compound represented by the formula (I), or a compound represented by the general formula (I) described in any of (1) to (15),
Containing the compound represented by (II) or (III), and (1)
(6) A photothermographic material comprising the silver halide particles according to (17).

[0015]

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

In the present invention, when a particular moiety is referred to as a "group", the moiety is substituted with one or more (up to the maximum number of possible) substituents, even if the moiety is not itself substituted. Means that you can. For example, “alkyl group” means a substituted or unsubstituted alkyl group. The substituents that can be used in the compounds of the present invention include any substituents, regardless of whether they are substituted.

Assuming that such a substituent is W, the substituent represented by W may be any substituent and is not particularly limited. Examples thereof include a halogen atom, an alkyl group [(cycloalkyl group, bicycloalkyl group, A tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl 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), ammonium group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group , Alkyl and arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclic thio, sulfamoyl, sulfo, alkyl and arylsulfinyl, alkyl and arylsulfonyl, acyl, arylo Xycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group (also called phosphono group), silyl Examples include a group, a hydrazino group, a ureido group, a boronic acid group, a phosphato group, a sulfato group, and other known substituents.

More specifically, W is a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom),
Alkyl group [[represents 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 having 5 to 30 carbon atoms) A substituted or unsubstituted bicycloalkyl group, that is, having 5 to 3 carbon atoms
This is a monovalent group obtained by removing one hydrogen atom from a bicycloalkane of 0. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-
Yl) and a tricyclo structure having more ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. And an alkenyl group [which represents a linear, branched or cyclic substituted or unsubstituted alkenyl group.
They are alkenyl groups (preferably having 2 to 30 carbon atoms).
A substituted or unsubstituted alkenyl group such as vinyl,
Allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent 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 (substituted or unsubstituted bicycloalkenyl group, preferably substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, ie, bicycloalkene having one double bond) It is a monovalent group with one hydrogen atom removed.
For example, bicyclo [2,2,1] hept-2-ene-1
-Yl, bicyclo [2,2,2] oct-2-ene-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 having 6 to 30 carbon atoms) Aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic groups); A monovalent group obtained by removing one hydrogen atom from a ring compound, 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-methyl-2-
A cationic heterocyclic group such as pyridinio and 1-methyl-2-quinolinio may be used. ), A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyl) Oxy, 2-methoxyethoxy), aryloxy group (preferably having 6 carbon atoms)
To 30 substituted or unsubstituted aryloxy groups, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably carbon number A silyloxy group having 3 to 20, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 3 carbon atoms);
0 substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkyl having 2 to 30 carbon atoms) A carbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, 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, phenoxy Carbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted having 6 to 30 carbon atoms) A substituted anilino group, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), an ammonio group (preferably an ammonio group, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, aryl, An ammonium group substituted with a heterocyclic ring, for example, trimethylammonio, triethylammonio, diphenylmethylammonio), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, With 6 to 30 carbon atoms A substituted or unsubstituted arylcarbonylamino group, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), 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 group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino,
Ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-
Methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn- Octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N −
n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methyl Sulfonylamino,
Butylsulfonylamino, phenylsulfonylamino,
2,3,5-trichlorophenylsulfonylamino, p
-Methylphenylsulfonylamino), a mercapto group,
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio,
Ethylthio, n-hexadecylthio), an arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably carbon number 2 to 30 substituted or unsubstituted heterocyclic thio groups, for example, 2-benzothiazolylthio,
1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N , N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl,
N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl having 6 to 30 carbon atoms) Groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p
-Methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl) Phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon atom Number 4 to 3
A heterocyclic carbonyl group bonded to the carbonyl group at 0 substituted or unsubstituted carbon atoms, for example, acetyl,
Pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl,
2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxy) Carbonyl, p
-T-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), carbamoyl Groups (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as 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 having 3 to 30 carbon atoms) Substituted heterocyclic azo groups, for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N
Succinimide, N-phthalimido), 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 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, such as trimethylhydrazino, a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, such as N, N
-Dimethylureido).

Further, two Ws together form a ring (an aromatic or non-aromatic hydrocarbon ring or a heterocyclic ring. These 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, quinoline ring , A phthalazine ring,
Naphthyridine ring, quinoxaline ring, quinoxazoline ring,
A quinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring, and a phenazine ring. ) May have a condensed structure.

Among the above-mentioned substituents W, those having a hydrogen atom may be removed and further substituted with the above-mentioned groups. Examples of such substituents include -CONHS
O ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), and the like. More specifically, an alkylcarbonylaminosulfonyl group (eg, acetylaminosulfonyl), an arylcarbonylaminosulfonyl group (eg, benzoylaminosulfonyl group),
Examples thereof include an alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl) and an arylsulfonylaminocarbonyl group (for example, p-methylphenylsulfonylaminocarbonyl).

Z ₁ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring in which an aromatic hydrocarbon or an aromatic heterocyclic ring is condensed, and preferably represents an aromatic hydrocarbon or an aromatic heterocyclic ring. It represents an atomic group necessary for forming a condensed 5- or 6-membered nitrogen-containing heterocyclic ring.

An aromatic hydrocarbon condensed in Z ₁ ,
Or as an aromatic heterocycle, any of which may be
They 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, 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, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring Quinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxatiin ring, phenothiazine ring, phenazine ring. Preferably, a benzene ring, a naphthalene ring, a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring, a benzothiophene ring, more preferably a benzene ring, a naphthalene ring, and most preferably a naphthalene ring .

In Z ₁ , the nitrogen-containing heterocycle includes thiazole nucleus, oxazole nucleus, selenazole nucleus, tellurazole nucleus, pyrrole nucleus, imidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, oxadiazole nucleus, thiadiazole nucleus, pyrimidine Although nuclei and the like can be mentioned, preferably a thiazole nucleus, an oxazole nucleus, a selenazole nucleus, a tellurazole nucleus, a pyrrole nucleus, an imidazole nucleus, more preferably a thiazole nucleus, an oxazole nucleus,
An imidazole nucleus, particularly preferably a thiazole nucleus or an oxazole nucleus, and most preferably a thiazole nucleus.

The aromatic hydrocarbon represented by Z ₁ or the nitrogen-containing heterocyclic ring in which the aromatic heterocyclic ring is condensed may be substituted with a substituent (for example, the aforementioned W).

Specific examples of the heterocyclic ring formed by Z ₁ are described in US Pat. No. 5,340,694, Nos. 23-24.
Among the examples of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , and Z _{16 in} the column, those satisfying the necessary conditions for Z ₁ can be mentioned.

R ₁ and R ₂ are each an alkyl group, an aryl group, or a heterocyclic group. However, neither R ₁ nor R _{2 is a} sulfoalkyl group. As the alkyl group, the aryl group, and the heterocyclic group, specifically, for example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atoms 1 to 18, preferably 1 to 7, particularly preferably 1 to 7.
To 4 substituted alkyl groups {for example, the aforementioned W
And an alkyl group substituted with In particular, the above-described alkyl group having an acid group is preferable. Preferably, an aralkyl group (e.g., benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (e.g., an allyl group, a vinyl group, that is, a substituted alkyl group also includes an alkenyl group and an alkynyl group), hydroxy Alkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (eg, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (eg, 2-methoxy Ethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl) ,
Aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), acyloxyalkyl group (eg, 2-acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoyl Alkyl group (for example, N, N-dimethylsulfamoylmethyl), sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl,
4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3 -Sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylalkyl groups (eg, methanesulfonylcarbamoylmethyl) Group), an acylcarbamoylalkyl group (eg, acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (eg, acetylsulfamoylmethyl group), an alkylsulfonylsulfamoylalkyl group (eg, methanesulfonylsulfamoylmethyl) Group)}, 6 to 20 carbon atoms,
It is preferably an unsubstituted aryl group having 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (for example, phenyl group or naphthyl group), 6 to 20 carbon atoms, preferably 6 carbon atoms.
To 10, and more preferably a substituted aryl group having 6 to 8 carbon atoms (for example, the above-mentioned W-substituted aryl group as an example of the substituent. Specific examples include p-methoxyphenyl group and p-methylphenyl An unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (eg, 2-furyl group, 2-thienyl group). 2,2-pyridyl group, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl,
-Oxazolyl, 2-thiazolyl, 2-pyridazyl, 2
-Pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl), having 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms
0, more preferably a substituted heterocyclic group having 4 to 8 carbon atoms (for example, the above-mentioned W-substituted heterocyclic group as an example of a substituent; specifically, a 5-methyl-2-thienyl group, 4-methoxy-2 -Pyridyl group etc.).

[0027] R _1, and preferably as R _2, R _1, and at least one of R ₂ is the case that the acid groups other than a sulfo group which is an alkyl group substituted. More preferably, _one of R ₁ and R ₂ is an alkyl group substituted with a sulfo group, and the other is an alkyl group substituted with an acid group other than the sulfo group.

The alkyl group substituted by an acid group other than the sulfo group at this time is preferably a carboxyl group, -CO
NHSO ₂ — group, —CONHCO— group, —SO ₂ NHSO
_2- is a substituted alkyl group.

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.
More preferably, it is a 3-sulfopropyl group. Particularly preferred as the alkyl group having an acid group other than the sulfo group are a carboxymethyl group and a methanesulfonylcarbamoylmethyl group.

Here, the acid group will be described. An acid group is a group having a dissociable proton. Specifically, for example, a sulfo group, a carboxyl group, a sulfato group, -CO
NHSO ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), a sulfonamido group, a sulfamoyl group, a phosphato group , Phosphono groups, boronic acid groups, phenolic hydroxyl groups, etc.
Some groups include groups from which protons are dissociated. For example, a proton dissociable acidic group capable of dissociating 90% or more between pH 5 and 11 is preferable. As the alkyl group having an acid group, those exemplified above as specific examples are preferably used. More preferred are a 3-sulfopropyl group, 4
-A sulfobutyl group, a 3-sulfobutyl group, a 2-sulfoethyl group, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a methanesulfonylcarbamoylmethyl group.

Sulfo group, carboxyl group, -CONHS
Preferred examples of the alkyl group substituted with an O ₂ — group, a —CONHCO— group, and a —SO ₂ NHSO ₂ — group can be expressed as follows in the form of a formula.

[0032]

Embedded image

Qa represents a linking group (preferably a divalent linking group) necessary for R ₁ or R ₂ to form an alkyl group. R _a , R _b , R _c and R _d 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 composed of an atom or an atomic group containing at least one of carbon, nitrogen, sulfur and oxygen. Preferably, an alkylene group (eg, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group (eg, ethinylene, propynylene), an amide group, an ester group, and a sulfonamide Group, sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Va)-(V
a represents a hydrogen atom or a monovalent substituent. The above-mentioned W is mentioned as a monovalent substituent. ), One or more of which have 0 to 10 carbon atoms;
It preferably represents a linking group having 1 to 5 carbon atoms.

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

More preferably, the alkylene group has 1 to 5 carbon atoms (eg, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyl trimethylene), and the alkenylene group has 2 to 5 carbon atoms (eg, ethenylene, propenylene). And an alkynylene group having 2 or more and 5 or less carbon atoms (eg, ethynylene, propynylene), which is a divalent linking group having 1 or more and 5 or less carbon atoms. Particularly preferred are alkylene groups having 1 to 5 carbon atoms (preferably methylene, ethylene, trimethylene, and tetramethylene).

When Xa is a sulfo group, Qa is more preferably ethylene, trimethylene, tetramethylene or methyltrimethylene, and particularly preferably trimethylene. When Xa is a carboxyl group, Qa is more preferably methylene, ethylene, or trimethylene, and particularly preferably methylene. Xa is -CON
For HSO ₂ Ra, SO ₂ NHCORb, CONHCORc, SO ₂ NHSO ₂ Rd,
Qa is more preferably methylene, ethylene or trimethylene, and particularly preferably methylene.

R _a , R _b , R _c , and R _{d each} represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclyloxy group, or an amino group.

For example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl,
Butyl), a substituted alkyl group having 1 to 18, preferably 1 to 10, more preferably 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, Further, here, an unsaturated hydrocarbon group having preferably 2 to 18 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 5 carbon atoms (eg, a vinyl group, an ethynyl group, a 1-cyclohexenyl group, a benzylidine) Group, benzylidene group) is also included in the substituted alkyl group.), A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms (eg, Phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl,
3,5-dichlorophenyl, p-cyanophenyl, m-
Fluorophenyl, p-tolyl),

An optionally substituted heterocyclic group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl) )

An alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-hydroxyethoxy, 2-phenylethoxy), 6 to 20 carbon atoms, preferably An aryloxy group having 6 to 12, more preferably 6 to 10 carbon atoms (eg, phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy), 1 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably Represents a heterocyclyloxy group having 3 to 10 carbon atoms (an oxy group substituted with a heterocyclic group; for example, 2-thienyloxy or 2-morpholinooxy), and an amino group having 0 to 20 carbon atoms, preferably 0 carbon atoms. To 12, more preferably an amino group having 0 to 8 carbon atoms (eg, amino, methylamino, Methylamino, ethylamino, diethylamino, hydroxyethylamino, benzylamino, anilino, diphenylamino, morpholino forming a ring, pyrrolidino) can be mentioned. In addition,
The aforementioned W may be substituted.

More preferably, a methyl group, an ethyl group,
It is a hydroxyethyl group, particularly preferably a methyl group.

In the acid group, for example, a carboxyl group, a dissociable nitrogen atom, etc. may be represented in a non-dissociated form (CO ₂ H) or (NH), or in a dissociated form (CO ₂ ⁻ )
(N ^-) may be either be written in. Actually, the dissociation state or the non-dissociation state occurs depending on the environment such as pH where the dye is placed. When a cation is present as a counter ion, for example, (CO ₂ ⁻ , Na ⁺ ), (N ⁻ , Na ⁺ )
May be written. In the non-dissociated state, (CO ₂ H), (NH
), But when the cation compound of the counter ion is considered to be a proton, it can also be described as (CO ₂ ⁻ , H ⁺ ) or (N ⁻ , H ⁺ ).

X₁, X_Two, And X_ThreeIs an oxygen atom, a sulfur atom
Represents a selenium atom, a nitrogen atom, or a carbon atom.
X₁, X_Two, And X_ThreeIs preferably X₁Is a sulfur atom
Yes, X _TwoIs a carbon atom and X_ThreeIs a nitrogen atom or carbon
This is the case when it is an atom. V₁, V_Two, And V_ThreeIs a hydrogen source
Represents a substituent or a substituent. Where V₁, V_Two, And V_ThreeIs
They cannot combine with each other to form an aromatic ring.
No. Examples of the substituent include the aforementioned W. V
₁, V_Two, And V_ThreeIs preferably a hydrogen atom, or
An aromatic substituent, more preferably a hydrogen atom, carbon
It is a substituted or unsubstituted alkyl group of Formulas 1 to 4. X₁But
Q for carbon atom₁Is 2, in the case of a nitrogen atom q₁Is 1, it
Q for atoms other than₁Is 0. X_TwoIs a carbon atom
q_TwoIs 1, otherwise q_TwoIs 0. X_ThreeBut
Q for carbon atom_ThreeIs 1, otherwise q_ThreeIs 0
It is. q₁Is 2 when V₁Are repeated but are identical
Need not be.

L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each independently represent a methine group. The methine groups represented by L _{1 to} L ₅ may have a substituent, and examples of the substituent include the aforementioned W. For example, substituted or unsubstituted carbon atoms of 1 to 1
5, preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl,
-Carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, o-
Carboxyphenyl), a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, N, N-dimethylbarbituric acid group), a halogen atom (Eg, chlorine, bromine, iodine, fluorine), an alkoxy group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methoxy, ethoxy), and 0 to 15 carbon atoms, preferably Is an amino group having 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms (eg, methylamino, N,
N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), an alkylthio group having 1 to 15, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, methylthio, ethylthio) , Having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
2, more preferably an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like. It may also form a ring with another methine group, or another group (for example, Z ₁ , Z ₂ , R ₁ , R _2, etc.)
And may form a ring together.

L ₄ and L ₅ are preferably unsubstituted methine groups.

N ₁ represents 0, ₁ , 2, 3 or 4. It is preferably 0, 1, 2, 3, and more preferably 0,
1, 2, particularly preferably 0, 1 and most preferably 1. When n ₁ is 2 or more, the methine group is repeated but need not be the same.

When n ₁ is 0, L ₃ is preferably an unsubstituted methine group. When n ₁ is 1, L ₁ and L ₃ are preferably unsubstituted methine groups, and L ₄ is preferably an unsubstituted methine group or an alkyl-substituted methine group.

P ₁ represents 0 or 1. Preferably it is 0.

M ₁ is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Typical cations include inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, and 1,8-diazabicyclo [5.4.0] -7-undecenium ion. The anion may be either an inorganic anion or an organic anion, and may be a halogen anion (for example, a fluorine ion, a chloride ion, an iodine ion), a substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-toluene ion). Chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,
3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoro ion Borate ion, picrate ion,
An acetate ion and a trifluoromethanesulfonic acid ion are mentioned. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. Moreover, CO ₂ ^-, SO
₃ ^- is, when having a proton as a counter ion CO
_It can also be described as ₂ H or SO ₃ H.

M ₁ represents a number of 0 or more necessary to balance the charges, preferably a number of 0 to 4, more preferably a number of 0 to 1, when a salt is formed in the molecule. Is 0.

Z ₂ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom (NR ₁₁ ), or a carbon atom (CR
₁₂ R ₁₃ ). Here, R ₁₁ , R ₁₂ , and R ₁₃ are a hydrogen atom or a substituent (for example, the aforementioned W), and are preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Examples of the alkyl group, the aryl group, and the heterocyclic group include the same as those described above for R ₁ and R ₂ . More preferably, it is an alkyl group.

Z ₂ is preferably an oxygen atom, a sulfur atom or a nitrogen atom, more preferably an oxygen atom or a sulfur atom, and particularly preferably a sulfur atom.

V ₄ , V ₅ , V ₆ and V ₇ represent a hydrogen atom or a substituent. However, these substituents may form a ring together. For example, the aforementioned W (for example, a hydrogen atom, an alkyl group, an aromatic group, a halogen atom, an acylamino group, a carbamoyl group, a carboxyl group, an alkoxy group, or a ring formation) can be mentioned.

As V ₄ , V ₅ , V ₆ and V ₇ , it is preferable to form the following ring (1) or to substitute the halogen atom or aromatic group (2).

(1) When forming a ring. It is preferred that V ₆ and V ₇ , or V ₅ and V ₆ together form a ring, more preferably V ₆ and V ₇ together form a ring . The ring is preferably a 5- or 6-membered ring, and more preferably an aromatic ring. Note that V ₆ and V ₇
There is V _4, V ₅ when forming the aromatic ring in cooperation preferably a hydrogen atom, if V ₅ and V ₆ is to form an aromatic ring jointly V _4, V ₇ is Hydrogen atoms are preferred.

The aromatic ring may be either an aromatic hydrocarbon or an aromatic heterocyclic ring, and these 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, 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, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene Ring, phenoxathiin ring, phenothiazine ring, phenazine ring. Preferred are a benzene ring, a pyrrole ring, a furan ring, and a thiophene ring, and more preferred is a benzene ring. The above aromatic ring may be further substituted with a substituent (for example, the above-mentioned substituent W). However, it is preferable that the above aromatic ring is unsubstituted. (2) When a halogen atom or an aromatic group is substituted. It is preferred that V ₆ is a halogen atom or an aromatic group. In this case, V ₄ , V ₅ and V ₇ are preferably hydrogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom, a bromine atom and an iodine atom. Examples of the aromatic group include a hydrocarbon aromatic group and a heteroaromatic group. These are groups having a polycyclic fused ring in which a hydrocarbon aromatic ring and a heteroaromatic ring are fused together, or a polycyclic fused ring structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are combined. Is also good. As the aromatic ring contained in the aromatic group, preferably, benzene, naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, india Lysine, indole, benzofuran, benzothiophene, isobenzofuran, quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthroline, thianthrene, chromene, xanthene, phenoxatiin, phenothiazine, phenazine, etc. Is mentioned. More preferably, benzene, pyrrole, furan,
Thiophene, particularly preferably benzene (that is, a phenyl group). The above-mentioned aromatic group may be further substituted by a substituent (for example, the aforementioned substituent W). However, it is preferable that the above aromatic group is unsubstituted.

V ₁ ′, V ₂ ′ and V ₃ ′ are a hydrogen atom,
Or a non-aromatic substituent. However, V ₁ ′, V ₂ ′, and V ₃ ′ do not combine with each other to form an aromatic ring. Examples of the substituent include the aforementioned W. More preferred are a hydrogen atom and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and particularly preferred are a hydrogen atom and a methyl group.

V_Four’, V_Five’, V₆’And V₇’Is hydrogen
Represents an atom or a substituent. Where V _Five’And V₆’Or V
₆’And V₇′ Together form a 5- or 6-membered ring
good. V_Four’, V_Five’, V₆’And V₇’
V_Four, V_Five, V₆, And V₇Similar to (eg, hydrogen
Atom, alkyl group, aromatic group, halogen atom, acyl group
Mino group, carbamoyl group, carboxyl group, alkoxy
Group or ring formation), and the same is preferable.

R ₁₀ represents a hydrogen atom or an alkyl group. When Z ₂ is a nitrogen atom, R ₁₀ represents a hydrogen atom. The alkyl group may be substituted or unsubstituted, but is preferably an unsubstituted alkyl group, more preferably a methyl group, an ethyl group, or a propyl group, and particularly preferably an ethyl group.

N ₁ ′ represents 0 or 1, and preferably 1
It is.

One of R ₃ and R ₄ is an alkyl group substituted by a sulfo group, and the other represents an alkyl group substituted by an acid group other than the sulfo group.

Preferred R ₃ and R ₄ are those described above.
_1, and it is similar to the preferred case described in R _2. That is, as the alkyl group substituted by an acid group other than a sulfo group, a carboxyl group, a -CONHSO ₂ -group,
-CONHCO- group, -SO ₂ NHSO ₂ - alkyl group which group is substituted.

In the 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,
More preferably, it is a 3-sulfopropyl group. Particularly preferred as the alkyl group having an acid group other than the sulfo group are a carboxymethyl group and a methanesulfonylcarbamoylmethyl group.

Next, specific examples of the compound (sensitizing dye) represented by the general formula (I), (II) or (III) described in detail in the description of the embodiments of the invention will be shown below. Of course, the present invention is not limited to these.

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

The dye of the present invention is FM Hammer.
(FMHarmer), Heterocyclic Compounds
Cyanine soybeans and related compounds
(Heterocyclic Compounds-Cyanine Dyes and Related C
ompounds) ", John Willy and Sons
n Wiley & Sons)-New York, London, 1
964, DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (H
eterocyclic Compounds-Special topics in heterocycl
ic chemistry ", Chapter 18, Section 14, 482-515, John Wiley and Sons (John Wi
ley & Sons)-New York, London, 197
7th year, "Rodd's Chemistry of Carbon Compounds"
2nd.Ed.vol.IV, partB, 1977, Chapter 15, Chapter 369
422, Elsevier Science Public
Company Inc. (Elsevier Science Publishing Com
pany Inc.), New York, German patent 19,96
It can be synthesized based on the method described in Japanese Patent No. 0,279A1.

In the present invention, not only the sensitizing dye of the present invention but also other sensitizing dyes other than the present invention may be used or used in combination. Preferred examples of the dye used include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, a tetranuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FMHarmer, Heterocyclic Compounds-Cyanine Soybeans and Related.
Compounds (Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds), John Wiley & Sons-New York,
London, 1964, D.M.
M. Sturmer), Heterocyclic Compounds-Special topics in Heterocyclic Compounds-Special topics i
n heterocyclic chemistry) ", Chapter 18, Section 14,
Nos. 482 to 515. Preferred dyes include US Pat. No. 5,994,051 No. 32
And sensitizing dyes represented by the general formulas and specific examples described in US Pat. No. 5,747,236, pages 30 to 39. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in U.S. Pat. No. 5,340,694, columns 21 to 22, (XI),
(XII), (XIII) (where n1
The number of 2, n15, n17, and n18 is not limited and is an integer of 0 or more (preferably 4 or less). ).

Although these sensitizing dyes may be used alone,
Two or more types may be used, and two or more types (often used for supersensitization) are described in U.S. Pat. No. 2,688,5.
No. 45, No. 2,977,229, No. 3,397,06
No. 0, 3,522,052, 3,527,641
No. 3,617,293 and 3,628,964
No. 3,666,480, 3,672,898
No. 3,679,428 and 3,303,377
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,707
No. 1,344,281 and 1,507,8
No. 03, JP-B-43-49336, JP-B-53-1237
5, JP-A-52-110618 and JP-A-52-11099.
No. 25, etc.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Supersensitizers useful for spectral sensitization in the present invention (for example, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts) And combinations of supersensitizers and sensitizing dyes are described, for example, in US Pat. No. 3,511,66.
No. 4, No. 3,615,613, No. 3,615,632
Nos. 3,615,641, 4,596,767
Nos. 4,945,038 and 4,965,182
Nos. 4,965,182 and 2,933,390
Nos. 3,635,721 and 3,743,510
Nos. 3,617,295, 3,635,721, etc., and the method described in the above-mentioned patents is preferred for the use thereof.

It has been recognized that the timing at which the sensitizing dye of the present invention (and other sensitizing dyes and supersensitizers) is added to the silver halide emulsion of the present invention has been useful. During the preparation of the emulsion. For example, US Pat. Nos. 2,735,766 and 3,6
28,960, 4,183,756, 4,22
5,666, JP-A-58-184142, 60-
As disclosed in, for example, Japanese Patent No. 196749, the stage before silver halide grain formation step and / or before desalting, the period during and / or after desalting and before the start of chemical ripening,
As disclosed in JP-A-58-113920 and the like, any time during or immediately before chemical ripening, during a process, or after chemical ripening and before coating, the emulsion may be added at any time before the coating. May be. Also, U.S. Pat.
As disclosed in US Pat. No. 5,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step and during the chemical ripening step or during the chemical ripening step. It may be added separately after completion, or before or after chemical ripening or during the process and after completion, and may be added by changing the kind of compound and compound combination to be added separately. May be.

The addition amount of the sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) differs depending on the shape and size of silver halide grains, and any addition amount may be used. Is preferably 1 × 10 ^-8 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol, per mol of silver halide.
× can be used in 10 ^-6 to 8 × 10 ^-3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, 2 × 10 ^{−6 to} 3 × 3 per mol of silver halide.
An addition amount of 5 × 10 ⁻³ mol is preferable, and 7.5 × 10 ⁻⁶ to
An addition amount of 1.5 × 10 ⁻³ mol is more preferred.

The sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) can be directly dispersed in an emulsion. These can be first dissolved in an appropriate solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be made to coexist. Also, ultrasonic waves can be used for dissolution. As a method for adding the compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. As described in JP-B-46-24185, and a method of dispersing in a water-soluble solvent and adding this dispersion to the emulsion, described in U.S. Pat. No. 3,822,135. A method of dissolving a compound in a surfactant and adding the solution to an emulsion, and dissolving using a compound that causes a red shift as described in JP-A-51-74624, and dissolving the solution in the emulsion. As described in JP-A-50-80826, a method in which a compound is dissolved in an acid substantially free of water and the solution is added to an emulsion is used. In addition, US Pat.
No. 2,343, No. 3,342,605, No. 2,99
Nos. 6,287, 3,429,835 and the like can also be used.

In the present invention, the photographic emulsion which controls the photosensitive mechanism includes any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride and silver chloride as silver halide. It may be used, but a stronger adsorption structure can be constructed by containing iodine having a halogen composition on the outermost surface of the emulsion of 0.1 mol% or more, more preferably 1 mol% or more, and particularly preferably 5 mol% or more. The particle size distribution may be wide or narrow, but narrower is more preferable. The silver halide grains of a photographic emulsion are those having regular crystals such as cubic, octahedral, tetradecahedral, or rhombic dodecahedron, or irregular such as spherical, plate-like, etc. (Irregular) crystal form,
It may have a higher-order plane ((hkl) plane) or a mixture of grains of these crystal forms, but is preferably a tabular grain, and the tabular grain will be described in detail below. For particles with higher planes, see Journal of I
See pages 247 to 254 of Maging Science, Vol. 30 (1986). Further, the silver halide photographic emulsion used in the present invention may contain the above-mentioned silver halide grains singly or in combination.
The silver halide grains may have different phases between the inside and the surface layer, may have a multiphase structure having a bonding structure, may have a localized phase on the grain surface, or may have a uniform grain as a whole. It may consist of phases. They may be mixed. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside a grain.

In the present invention, tabular silver halide grains having a halogen composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and silver iodochloride are preferably used. The tabular grains preferably have a main surface of (100) or (111). Tabular grains having a (111) major surface, hereinafter referred to as (111) tabular, usually have triangular or hexagonal faces. Generally, the more uniform the distribution, the higher the proportion of tabular grains having more hexagonal faces. The hexagonal monodispersed flat plate is described in Japanese Patent Publication No. 5-61205.

Tabular grains having a (100) plane as a main surface,
The (100) flat plate also has a rectangular or square shape. In this emulsion, grains having an adjacent side ratio of less than 5: 1 are called tabular grains. In silver chloride or tabular grains containing a large amount of silver chloride, (100) tabular grains originally have higher stability on the main surface than (111) tabular grains. In the case of a (111) flat plate, it is necessary to stabilize the (111) main surface.
-80660, JP-A-9-80656 and U.S. Pat. No. 5,298,388.

The silver chloride or the (111) flat plate having a high silver chloride content used in the present invention is disclosed in the following patents. U.S. Patent No. 4,414,306, U.S. Patent No. 4,400,463, U.S. Patent No. 4,713,323
No. 4,783,398; U.S. Pat.
No. 491, U.S. Pat. No. 4,983,508, U.S. Pat.
No. 804621, US Pat. No. 5,389,509, US Pat. No. 5,217,858, US Pat. No. 5,460,934.

The high silver bromide (111) tabular grains used in the present invention are described in the following patents. U.S. Pat. No. 4,425,425, U.S. Pat. No. 4,425,426,
U.S. Pat. No. 4,443,426; U.S. Pat. No. 4,439,520
No. 4,414,310; U.S. Pat.
048, U.S. Pat. No. 4,647,528, U.S. Pat.
No. 6,650,012, U.S. Pat. No. 4,672,027, U.S. Pat. No. 4,678,745, U.S. Pat. No. 4,684,607,
U.S. Pat. No. 4,593,964, U.S. Pat.
6, U.S. Pat. No. 4,722,886, U.S. Pat.
5617, U.S. Patent No. 4,755,456, U.S. Patent No. 4,806,461, U.S. Patent No. 4,801,522, U.S. Patent No. 4,835,322, U.S. Patent No. 4,839,268,
U.S. Pat. No. 4,914,014, U.S. Pat.
5, U.S. Pat. No. 4,977,074, U.S. Pat.
No. 5,350, U.S. Pat. No. 5,061,609, U.S. Pat. No. 5,061,616, U.S. Pat. No. 5,068,173, U.S. Pat. No. 5,132,203, U.S. Pat.
No. 5,334,469, U.S. Pat.
No. 495, US Pat. No. 5,358,840, US Pat.
372927.

The (100) flat plate used in the present invention is described in the following patents. US Patent No. 43
No. 86156, US Pat. No. 5,275,930, US Pat. No. 5,292,632, US Pat. No. 5,314,798, US Pat. No. 5,320,938, US Pat. No. 5,319,635.
No. 5,356,764, European Patent No. 5699.
No. 71, EP 737887, JP-A-6-308
648, JP-A-9-5911.

The silver halide emulsion used in the present invention has a higher surface area / absorbing sensitizing dye disclosed in the present invention.
Tabular silver halide grains having a high volume ratio are preferred, and the aspect ratio is preferably 2 or more, more preferably 5 or more, and particularly preferably 8 or more. There is no particular upper limit,
Preferably it is 1000 or less, more preferably 500 or less. The thickness of the tabular grains is preferably less than 0.2 μm, more preferably less than 0.1 μm, even more preferably less than 0.07 μm.

Here, for example, when the aspect ratio is 2 or more and 10
The phrase "not more than 00" means that silver halide grains having an aspect ratio (equivalent circle diameter of silver halide grains / grain thickness) of 2 or more and 1000 or less exist in an emulsion of 50% or more of the projected area of all silver halide grains. Means that. Preferably, 7
Emulsions having 0% or more, particularly preferably 85% or more.

The following techniques are applied to prepare such thin tabular grains having a high aspect ratio. The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain are 100 to 50% of all grains.
(Number), more preferably 10
0 to 70%, particularly preferably 100 to 90%
Occupy.

If the ratio is less than 50%, it is not preferable from the viewpoint of homogeneity between particles.

In the present invention, when the ratio of the particles containing dislocation lines and the number of dislocation lines are obtained, it is preferable to obtain the dislocation lines directly by observing at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives ;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci.
Photo. Japan. No. 16. P30 (196
Enzyme-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used. The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid.
The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the whole grain and a method of doping only the core part or only the shell part of the grain can be selected. For example, Mg, Ca, Sr, Ba, Al,
Sc, Y, La, Cr, Mn, Fe, Co, Ni, C
u, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b and Bi can be used. These metals can be added in the form of ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, or salts that can be dissolved at the time of particle formation, such as six-coordinate complex salts and four-coordinate complex salts. For example,
CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (N
O ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (C
N) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrC
_{l 6, (NH 4) 3} RhCl 6, K 4 Ru (CN) 6 and the like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

It is preferable that the metal compound is added after being dissolved in water or a suitable organic solvent such as methanol or acetone. To stabilize the solution, a method of adding an aqueous solution of hydrogen halide (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. Further, if necessary, an acid or an alkali may be added. The metal compound can be added to the reaction vessel before the formation of the particles or during the formation of the particles. A water-soluble silver salt (eg, AgNO ₃ ) or an aqueous alkali halide solution (eg, NaCl, K)
(Br, KI) and continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization at any step in the production of a silver halide emulsion. Can be applied. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred. One of the chemical sensitizations that can be preferably performed in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described by TH James, The Photographic Process, Fourth Edition, Macmillan. Published by the company
1977, (TH James, The Theo)
ry of the Photographic Pr
ocess, 4th ed, Macmillan, 19
77) can be carried out using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, 6 June 1975.
Moon, 13452, U.S. Patent Nos. 2,642,361, 3,297,446, and 3,772,031,
Nos. 3,857,711 and 3,901,714,
Nos. 4,266,018 and 3,904,4
No. 15 and pAg 5-10, pH 5-8 and temperature 30-30 as described in GB 1,315,755.
At 80 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ P
dCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li
₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate. As sulfur sensitizers, hypo, thiourea-based compounds, rhodanine-based compounds and US Pat. No. 3,857,711
Nos. 4,266,018 and 4,054
No. 457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. As useful chemical sensitization aids, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the course of chemical sensitization are used. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,4,
No. 11,914, No. 3,554,757;
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × per mol of silver halide.
10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5
× 10 ^-7 mol. The preferred range of the palladium compound is from 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is 5 × 10
^-2 to 1 × 10 ^-6 . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1
The amount is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol per mol, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol. Selenium sensitization is a preferred sensitization method for the emulsion of the present invention.

As the selenium sensitizer, selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a temperature of not lower than ℃ for a certain period of time. Examples of unstable selenium compounds include, for example,
No. 15748, Japanese Patent Publication No. 43-13489,
It is preferable to use the compounds described in JP-A-25832 and JP-A-4-109240. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, and colloidal metal selenium. Can be

The preferred types of unstable selenium compounds have been described above, but these are not limitative. Skilled artisans say that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the organic part of the selenium sensitizer molecule is not important. It is generally understood that selenium has no role except to carry it in an unstable form in the emulsion. In the present invention, an unstable selenium compound having such a broad concept is advantageously used.

Non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-34.
No. 492 and JP-B-52-34491 are used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof.

Of these selenium compounds, those of the general formulas (VII) and (VIII) described in JP-A-11-15115 are preferably used. These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent and added during chemical sensitization. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and two or more kinds of the above selenium sensitizers can be used in combination. It is preferable to use a combination of an unstable selenium compound and a non-unstable selenium compound.
The amount of the selenium sensitizer to be added varies depending on the activity of the selenium sensitizer to be used, the type and size of silver halide, the ripening temperature and the time, and is preferably 1 × / mol of silver halide in the emulsion. It is at least 10 ^-8 mol. More preferably, it is 1 × 10 ^{−7 to} 5 × 10 ⁻⁵ mol. The temperature of chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher. More preferably, it is 50 to 80 ° C. pAg and pH are arbitrary. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9.

It is sometimes preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in an atmosphere of a low pAg of pAg 1 to 7 called silver ripening, or a method of pH 8 to 10 called high pH ripening. Either a method of growing or ripening in a high pH atmosphere of 11 can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. Examples of the reduction sensitizer include stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-7 to 10 ^-3 mol per mol of silver halide. The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle growth is preferable. Further, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer several times as the grains grow, or to add them continuously for a long time.

During the production process of the emulsion of the present invention, an acid for silver is used.
It is preferable to use an agent. The oxidizing agent for silver is
Has the effect of converting to silver ions by acting on metallic silver
Refers to a compound. Especially the formation process of silver halide grains and
Extremely small silver particles by-produced during chemical sensitization
Is a compound that can be converted into a silver ion. here
The silver ions generated in, for example, silver halide, sulfide
May form silver salts that are hardly soluble in water such as silver and silver selenide.
And may form a silver salt easily soluble in water such as silver nitrate.
No. The oxidizing agent for silver can be inorganic or organic.
There may be. As the inorganic oxidizing agent, for example, Ozo
Hydrogen peroxide and its adducts (eg, NaBO)_Two
・ H_TwoO_Two・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two, Na_FourP_Two
O₇・ 2H_TwoO_Two, 2Na_TwoSO_Four・ H_TwoO_Two・ 2H_TwoO), pe
Leuoxy acid salt (for example, K_TwoS_TwoO₈, K_TwoC_TwoO₆, K_TwoP_Two
O₈), Peroxy complex compounds (eg, K_Two[Ti (O
_Two) C_TwoO _Four] ・ 3H_TwoO, 4K_TwoSO_Four・ Ti (O_Two) OH
・ SO_Four・ 2H_TwoO, Na_Three[VO (O_Two) (C_TwoH_Four)_Two]
・ 6H_TwoO), permanganate (eg, KMnO)_Four),
Chromate (eg, K_TwoCr_TwoO₇ Oxygen acid like)
Salts, halogen elements such as iodine and bromine, perhalates
(Eg, potassium periodate), high valent metal salts
(Eg potassium hexacyanoferrate) and thio
There are sulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates, and organic oxidizing agents such as quinones.
It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting both methods. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) known as antifoggants or stabilizers, such as titraazaindenes and pentaazaindenes;
Many compounds can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,947,
Those described in JP-B-52-28660 can be used. One of the preferred compounds is disclosed in JP-A-63-21.
2932. Antifoggants and stabilizers can be used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The silver halide emulsion prepared according to the present invention can be used for both color photographic materials and black-and-white photographic materials. Color photographic light-sensitive materials include color photographic paper, color photographic films, color reversal films, color instant films, and black-and-white photographic light-sensitive materials include general photographic films, X-ray films, medical diagnostic films, and printing photographic materials. Films and the like can be mentioned.

In the field of medical diagnostic films and films for printed light-sensitive materials, exposure can be efficiently performed by a laser imagesetter or laser imager. The technology in these fields is described in Japanese Patent Application Laid-Open No. 7-28.
7,337, JP-A-4-335342, JP-A-5
-313,289, JP-A-8-122,954, JP-A-8-292,512 and the like.

Further, a photothermographic material can be preferably used. In this case, the storage stability is particularly excellent. For example, a catalytically active amount of a photocatalyst (eg, silver halide), a reducing agent, a reducible silver salt (eg, an organic silver salt),
Materials having a photosensitive layer in which a color tone agent for controlling the color tone of silver is dispersed in a binder matrix as necessary are known. These are described, for example, in U.S. Pat. No. 3,152,904, U.S. Pat. No. 3,457,075, U.S. Pat. , 1
1-30832, 11-84574, 11-65021, 11-109547
No. 11-125880, No. 11-129629, No. 11-133536
No. 11-133539, No. 11-133542, No. 11-133543, No. 11-
Nos. 223898, 11-352627, 6-130607, 6-332134, 6-332136, 6-3
No. 47970, No. 7-261354, Japanese Patent Application 2000-
No. 89436, and the like.

For the preparation of the photographic emulsion used in the present invention, column 63, line 36 to column 65, line 2 of JP-A-10-239789 can be applied. The additives such as color couplers, photographic light-sensitive material additives, etc., the types of light-sensitive materials to which the present invention is applied, the processing of light-sensitive materials, etc. are described in JP-A-10-239789, column 65, line 3 to Column 73, line 13 is applicable.

In the silver halide photographic light-sensitive material of the present invention,
Although the various additives described above are used, various other additives can be used depending on the purpose. These additives are described in more detail in Research Disclosure, Item 1
7643 (December 1978), Item 18716 (November 1979), and Item 308119 (December 1989), and the corresponding portions are shown in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 Sensitizer page 649 right column 4 Brightener 24 page 998 right 5 Antifoggant 24-25 page 649 right column 998 right-1000 right and stabilizer 6 Light absorber, fill 25-26 page 649 right column 1003 left to 1003 right tar, UV absorber page 650 left column 7 Stain inhibitor 25 page right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardener 26 page 651 left column 1004 right 1005 left to 1006 right Same as above 1003 right to 1004 right 11 Plasticizer, lubricant page 27 650 page right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 same 1005 left to 1006 left Surfactant 13 Antistatic agent Page 27 Same as above 1006 right to 1007 left 14 Matting agent 1008 left to 1009 left

Techniques such as layer arrangement which can be used in the emulsion of the present invention and photographic light-sensitive materials using the emulsion, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives, etc. And development processing are described in EP 056596 A1 (1993).
And published patents cited therein. The following is a list of each item and the corresponding descriptions.

[0114] 1. 1. Layer structure: page 61, lines 23 to 35, line 41 to page 62, line 14 2. Intermediate layer: page 61, lines 36 to 40 3. Multilayer effect imparting layer: page 62, lines 15 to 18 4. Silver halide composition: page 62, lines 21 to 25 5. Silver halide grain habit: page 62, lines 26 to 30 6. Silver halide grain size: page 62, lines 31 to 34 7. Emulsion production method: page 62, lines 35 to 40 8. Silver halide grain size distribution: page 62, lines 41 to 42 Tabular grains: page 62, lines 43 to 46 10. 10. Internal structure of particle: page 62, lines 47 to 53 11. Emulsion latent image formation type: page 62, line 54 to page 63, line 5 12. Physical ripening and chemical sensitization of emulsion: page 63, lines 6-9. 13. Mixed use of emulsion: page 63, lines 10-13. 14. Fogged emulsion: page 63, lines 14 to 31 Non-light-sensitive emulsion: page 63, lines 32 to 43 Silver coating amount: 63 pages 49-50 lines

17. Formaldehyde scavenger: page 64, lines 54 to 57 18. Mercapto antifoggant: page 65, lines 1 and 2 19. Release agent such as fogging agent: page 65, lines 3-7 20. Dye: page 65, lines 7 to 10 21. General color couplers: page 65, lines 11 to 13 Yellow, magenta and cyan couplers: page 65, lines 14-25 23. Polymer coupler: page 65, lines 26-28 24. Diffusible dye-forming coupler: page 65, lines 29-31 25. Colored coupler: page 65, lines 32-38 26. Functional couplers in general: p. 65, lines 39-44 27. Bleach accelerator releasing coupler: page 65, lines 45-48 28. Development accelerator releasing coupler: page 65, lines 49 to 53 29. Other DIR couplers: page 65, line 54 to page 66, line 4 Coupler dispersion method: page 66, lines 5-28

31. Preservatives / fungicides: page 66, lines 29-33 32. Type of photosensitive material: page 66, lines 34-36 33. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, line 1 34. Back layer: page 67, lines 3-8 35. Overall development processing: page 67, lines 9 to 11 Developer and developer: page 67, lines 12-30 37. Developer additive: page 67, lines 31 to 44 38. Inversion processing: page 67, lines 45 to 56 39. Processing solution opening ratio: page 67, line 57 to page 68, line 12 Developing time: page 68, lines 13 to 15 41. Bleaching / fixing / bleaching / fixing: page 68, line 16 to page 69, line 31 Automatic developing machine: page 69, lines 32 to 40 43. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18 Processing solution replenishment and reuse: page 70, lines 19 to 23 45. Built-in photosensitive material for developer: Page 70, lines 24 to 33 46. Developing temperature: page 70, lines 34-38 47. Use for film with lens: 70 pages 39-41

The method of exposing the silver halide photographic light-sensitive material of the present invention will be described. Exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, laser, LED, and CRT can be used. Further, exposure may be performed by light emitted from a phosphor excited by an electron beam, X-ray, γ (gamma) ray, α (alpha) ray, or the like.

In the present invention, a laser light source may be preferably used. Examples of laser light include lasers using helium-neon gas, argon gas, krypton gas, carbon dioxide gas, etc. as a laser oscillation medium, lasers using solids such as ruby and cadmium as an oscillation medium, other liquid lasers, semiconductor lasers, and the like. is there. Unlike laser light used for ordinary illumination, these laser lights are coherent light with a single frequency and the same phase and sharp direction, so halogen light for exposing them as a light source is used. Silver photographic light-sensitive materials need to have spectral characteristics that match the emission wavelength of the laser used. Among the above lasers, a semiconductor laser is preferably used.

[0119]

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

Example 1 A silver halide color negative photosensitive material having the same structure as that of the sample 104 of Example 1 of JP-A-11-305369 was prepared. However, instead of ExS-9 and 10 of the 13th layer (low-sensitivity blue photosensitive layer) and ExS-9 of the 14th layer (high-sensitivity blue photosensitive layer),
Samples 11 to 12 using the sensitizing dyes described in Table 1 were produced.

[0121]

[Table 1]

SS-1 and SS-2 in Table 1 have the following structures.

[0123]

Embedded image

Each of the samples thus prepared was subjected to continuous wedge exposure with white light, developed in the same manner as in Example 1 of JP-A-11-305369, and then the yellow density was measured. The sensitivity was relatively evaluated by the reciprocal of the exposure amount giving a density 0.2 higher than the minimum value (fog) of the yellow density. (These values were defined as fresh sensitivity. Sample 11 was designated as 100.) H. After storage for 90 hours, exposure and processing were similarly performed to evaluate the sensitivity. (These are referred to as sensitivities after storage.) Further, the image quality was evaluated relative to ×. Further, the remaining color is 400 nm to 470 nm.
The relative evaluation was made with × from the absorption in the region of. From the results of Samples 11 and 12 in Table 1, Sample 12 using the dye of the present invention was used.
Indicates that the sample has higher sensitivity than the comparative sample 11, has less decrease in sensitivity after storage, and has excellent image quality. further,
Less residual color.

The above image quality was evaluated based on the granularity. For the evaluation of the graininess, a color temperature of 3200 ° K was used as a light source for the sample of each experiment No. through a pattern for measuring the RMS value.
The samples exposed using a halogen lamp described above were subjected to photographic processing such as the above-mentioned development, and these samples were measured with a microdensitometer (measurement aperture diameter: 48 μm) to obtain an RMS value, which was relatively evaluated as ○.

Next, ExS-4, 5, 6, 7 of the ninth layer (low-sensitivity green photosensitive layer) of the silver halide color negative photosensitive material having the same structure as that of the sample 104 of Example 1 of JP-A-11-305369. ,
ExS-4, 7, the tenth layer (medium-speed green photosensitive layer)
8, Sample 21 using a sensitizing dye described in Table 2 in place of ExS-4, 7, and 8 of the eleventh layer (high-sensitivity green-sensitive layer)
No. 22 was produced.

[0127]

[Table 2]

SS-3, SS-4 and SS-5 in Table 2 have the following structures.

[0129]

Embedded image

Each of the samples thus prepared was exposed and processed in the same manner as the samples in Table 1, and the sensitivity, fog, sensitivity after storage, and image quality were evaluated. (However, with the samples in Table 1, the sensitivity was evaluated by measuring the magenta density, and the residual color was evaluated by 47
The difference is that the absorption was performed from 0 nm to 525 nm. From the results of Samples 21 and 22 in Table 2, it can be seen that Sample 22 using the dye of the present invention has higher sensitivity, less decrease in sensitivity after storage, and better image quality than Comparative Sample 21. Furthermore, there is little residual color.

Next, the ExS-1, 2, 3, and 4th layers of the fourth layer (low-sensitivity red photosensitive layer) of the silver halide color negative photosensitive material having the same structure as that of the sample 104 of Example 1 of JP-A-11-305369 were used. The sensitizing dyes shown in Table 3 were used in place of ExS-1, 2, and 3 of the five layers (medium-sensitivity red-sensitive layer) and ExS-1, 2, and 3 of the sixth layer (high-sensitivity red-sensitive layer). Samples 31 and 32 were prepared.

[0132]

[Table 3]

SS-6, SS-7 and SS-8 in Table 3 have the following structures.

[0134]

Embedded image

Each of the samples thus prepared was exposed and processed in the same manner as the samples in Table 1, and the sensitivity, fog, sensitivity after storage, and image quality were evaluated. (However, with the samples in Table 1, the sensitivity was evaluated by measuring the cyan density, and the residual color was evaluated by 525.
The difference is that it was performed from the absorption between nm and 680 nm. )

From the results of Samples 31 and 32 in Table 3, it is clear that Sample 32 using the dye of the present invention has higher sensitivity, less decrease in sensitivity after storage, and superior image quality as compared with Comparative Sample 31. I understand. Furthermore, there is little residual color.

As described above, the dyes SS-1, SS-4 and SS-6, which are compared with the dyes of the present invention in Tables 1, 2 and 3, have two sulfoalkyl groups as N-substituents. There is a problem in that the sensitivity is not sufficient, and particularly the sensitivity is significantly reduced after storage.
Also, the image quality is not sufficient. On the other hand, the dyes (20), (10), and (1) having a specific N-position substituent of the present invention.
Found that not only the sensitivity was high, but also, surprisingly, the decrease in sensitivity after storage was remarkably small, and the image quality was high. In addition, the comparative dye has less residual color than the conventional dye, but the residual color of the dye of the present invention is further improved.

As described above, it has been found that the dye having a specific N-position substituent of the present invention is specifically excellent.

Example 2 Preparation of a silver bromide octahedral emulsion (emulsion A) and a silver bromide tabular emulsion (emulsion B, emulsion C, emulsion D, and emulsion E). 1000 ml of water in a reaction vessel, deionized bone gelatin 25
g, 15 ml of a 50% aqueous solution of NH ₄ NO ₃ and 7.5 ml of a 25% aqueous solution of NH ₃ were added, kept at 50 ° C., stirred well, and mixed with 750 ml of a 1N aqueous solution of silver nitrate and 1 mol / l.
Was added in 50 minutes to keep the silver potential during the reaction at -40 mV. The obtained silver bromide particles were octahedral and had a sphere equivalent diameter of 0.846 ± 0.036 μm.
The temperature of the emulsion was lowered, a copolymer of isobutene and monosodium maleate was added as a flocculant, and the emulsion was washed by settling and desalted. Then, deionized bone gelatin 9
After adding 5 g and 430 ml of water and adjusting to pH 6.5 and pAg 8.3 at 50 ° C., potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to obtain optimum sensitivity, and aging was performed at 55 ° C. for 50 minutes. did. This emulsion was designated as emulsion A.

Potassium bromide 6.4 in 1.2 liters of water
g and low molecular weight gelatin having an average molecular weight of 15,000 or less6.
While dissolving 2 g and keeping the temperature at 30 ° C., 8.1 ml of a 16.4% aqueous silver nitrate solution and 7.2 ml of a 23.5% aqueous potassium bromide solution were added by a double jet method over 10 seconds. Next, an aqueous solution of 11.7% gelatin was further added, the temperature was raised to 75 ° C., and the mixture was aged for 40 minutes. Then, 370 ml of a 32.2% aqueous solution of silver nitrate and a 20% aqueous solution of potassium bromide were brought to a silver potential of −20 mV. The temperature was lowered to 35 ° C. after physical ripening for 1 minute. Thus, the average projected area diameter is 2.32 μm, and the thickness is 0.0
9 μm (aspect ratio 25.8), diameter variation coefficient 1
A 5.1% monodispersed pure silver bromide tabular emulsion (specific gravity: 1.15) was obtained. Thereafter, soluble salts were removed by the coagulation sedimentation method.
The temperature was again maintained at 40 ° C., and 45.6 g of gelatin and 1 mo
10 ml of 1 / l aqueous sodium hydroxide solution, 167 ml of water, and 35% phenoxyethanol in 1.
66 ml was added, pAg was adjusted to 8.3, and pH was adjusted to 6.20. This emulsion was ripened at 55 ° C. for 50 minutes by adding potassium thiocyanate, chloroauric acid and sodium thiosulfate to obtain the optimum sensitivity. This emulsion was designated as emulsion B.

An emulsion chemically sensitized with potassium thiocyanate, chloroauric acid, pentafluorophenyl-diphenylphosphine selenide and sodium thiosulfate instead of potassium thiocyanate, chloroauric acid and sodium thiosulfate was used. And

In the preparation of the emulsion B, the silver potential was adjusted to obtain a monodispersion having an average projected area diameter of 1.56 μm, a thickness of 0.625 μm (aspect ratio 2.5), and a diameter variation coefficient of 15.1%. Pure silver bromide tabular emulsion (specific gravity: 1.1
6), and further processed and chemically sensitized in the same manner to obtain emulsion D
And

In the preparation of Emulsion B, the silver potential was adjusted to obtain a monodispersion having an average projected area diameter of 2.12 μm, a thickness of 0.341 μm (aspect ratio 6.2), and a diameter variation coefficient of 15.0%. Pure silver bromide tabular emulsion (specific gravity: 1.1
6), and further processed and chemically sensitized in the same manner to obtain Emulsion E
And

Further, in adjusting the emulsion B, by adjusting the silver potential, the average projected area diameter was 2.36 μm,
Monodisperse pure silver bromide tabular emulsion having a thickness of 0.274 μm (aspect ratio 8.6) and a coefficient of variation of diameter of 15.1% (specific gravity 1.
15) was obtained and further processed and chemically sensitized in the same manner to prepare Emulsion F.

While the emulsion thus obtained was kept at 50 ° C., the dyes shown in Table 4 were added thereto and stirred for 60 minutes.

Further, a gelatin hardener and a coating aid were added to the obtained emulsion, and a gelatin protective layer was formed on a cellulose acetate film support so that the coated silver amount was 3.0 g-Ag / m ^2. At the same time. The obtained film sample (fresh sample) was exposed to a tungsten bulb (color temperature: 2854K) through a continuous wedge color filter for 1 second. Fuji gelatin filter SC for minus blue exposure that excites the dye side as a color filter
Using -40 (manufactured by FUJIFILM Corporation), the light of 400 nm or less was blocked, and the sample was irradiated. The exposed sample was developed at 20 ° C. for 10 minutes using the following surface developer MAA-1. Next, the following fixing was performed, followed by washing with water and drying. Further, the above film sample was subjected to 60 ° C., 80 ° C.
% R. H. After storage for 60 hours (sample after storage), exposure and treatment were performed in the same manner as described above.

Surface developer MAA-1 Metol 2.5 g L-ascorbic acid 10 g Nabox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g Water is added to 1 liter pH 9.8

Fixing solution formulation Ammonium thiosulfate 170 g Sodium sulfite (anhydrous) 15 g Boric acid 7 g Glacial acetic acid 15 ml Potassium alum 20 g Ethylenediaminetetraacetic acid 0.1 g Tartaric acid 3.5 g Add water and 1 liter

The optical density of the film sample subjected to development and other processing was measured by a Fuji automatic densitometer.
The reciprocal of the amount of light required to give an optical density of 0.2 was evaluated, and the sensitivity of each sample after storage was indicated by a relative value when the sensitivity of each fresh sample was taken as 100.

[0150]

[Table 4]

From the results shown in Table 4, it can be seen that the sample using the dye of the present invention shows less decrease in sensitivity after storage than the sample using the comparative dye. Further, the sensitivity of the comparative dye after storage was lower than that of the octahedral emulsion in comparison with the octahedral emulsion in which D, E, F and
It can be seen that the sensitivity decrease is larger at B, and the degree of the decrease is greater as the aspect ratio becomes higher (especially, the aspect ratio is 8 or more). On the contrary, surprisingly, the sensitivity of the dye of the present invention after storage was smaller in the tabular emulsions D, E, F and B than in the octahedral emulsion A, and the degree was higher. It can be seen that the larger the aspect ratio (especially, the aspect ratio is 8 or more), the larger. Furthermore, surprisingly, when the emulsions B and C are compared, it can be seen that the selenium-sensitized emulsion C improves the storage stability more remarkably. In addition, the sample 41 of this invention-
At 56, both the comparative sensitizing dye, SS-6, and the sensitizing dye of the present invention form a J-aggregate having a maximum at approximately 620 nm and exhibit a spectral sensitivity distribution similar to the absorption,
The sensitizing dye of the present invention showed a sharper absorption than the comparative dye.

As described above, it has been found that the dye having a specific N-position substituent of the present invention is specifically excellent in preservability as compared with the dye having two sulfoalkyl groups at the N-position for comparison. Was.

Example 3 Instead of Comparative Dye A of Example 1 of JP-A-2000-98525, (SS-6) and (1) were used, and the storage stability was evaluated at 60 ° C. and 80% R.C. H. The evaluation was performed in exactly the same manner except that the evaluation was performed for 100 hours. As a result, the sensitivity of the sample of (SS-6) after storage was 58 with respect to the freshness of 100, whereas the sensitivity of the sample (1) after storage was freshness of 100. It turned out that it was 81 which was excellent with respect to time.

Example 4 In the same manner as in Examples 1 and 2, the reduction in sensitivity after storage was compared with the system of the color reversal light-sensitive material of Example 1 of JP-A-7-92601 and JP-A-11-160828. No. 347,944, Japanese Patent Application No. 11-89.
No. 801 of the instant photographic material of Example 1;
Japanese Patent Application Laid-Open No. H8-292512
X-ray sensitive material system of Example 1 of JP-A-122954
Example 5 of 000-122206, Japanese Patent Application 2000-89
No. 436 and Example 1 of JP-A-6-130607. As a result, as in Examples 1 and 2, the sensitizing dye of the present invention showed little decrease in sensitivity after storage.

[0155]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having high sensitivity, good storability and high image quality, and having less residual color than before.

Claims (8)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one compound represented by the following general formula (I). General formula (I) In the formula (I), X ₁ , X ₂ and X ₃ represent an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or a carbon atom. Z ₁
Represents an atomic group necessary for forming an aromatic hydrocarbon or a nitrogen-containing heterocyclic ring in which an aromatic heterocyclic ring is condensed. R ₁ and R ₂ represent an alkyl group, an aryl group, or a heterocyclic group.
However, neither R ₁ nor R _{2 is a} sulfoalkyl group. V ₁ , V ₂ and V ₃ represent a hydrogen atom or a substituent. Q ₁ is 2 when X ₁ is a carbon atom, q when X ₁ is a nitrogen atom
₁ is 1 and q ₁ is 0 for other atoms. When X ₂ is a carbon atom, q ₂ is 1, and when X ₂ is any other atom, q ₂ is 0. When X ₃ is a carbon atom, q ₃ is 1, and when X ₃ is any other atom, q ₃ is 0. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ represent a methine group. n ₁ represents 0, 1, 2, 3, or 4.
p ₁ represents 0 or 1. M ₁ represents a charge balancing counter ion;
m ₁ represents the number necessary to neutralize the molecular charge. 2. The compound of the formula (I) according to claim ₁ , wherein at least one of R ₁ and R ₂ is an alkyl group substituted by an acid group other than a sulfo group. Item 1. A silver halide photographic material according to item 1. 3. The compound of the general formula (I) according to claim ₁ , wherein _one of R ₁ and R ₂ is an alkyl group substituted by a sulfo group, and the other is an acid group other than a sulfo group. 3. The silver halide photographic material according to claim 1, wherein the photographic material is a substituted alkyl group. 4. The compound of the general formula (I)
2. The silver halide photographic material according to claim 1, wherein the material is selected from the compounds represented by I). General formula (II) In the formula (II), Z ₂ represents an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, or a carbon atom. _{V 4, V 5, V 6} ,
And V ₇ represent a hydrogen atom or a substituent. However, these substituents may form a ring together. R ₃ and R ₄
Among them, one is an alkyl group substituted by a sulfo group,
The other represents an alkyl group substituted by an acid group other than a sulfo group. X ₁ , X ₂ , X ₃ , V ₁ , V ₂ , V ₃ , q ₁ , q ₂ ,
q ₃ , L ₁ , L ₂ , L ₃ , n ₁ , M ₁ , and m ₁ have the same meanings as in the general formula (I). 5. The silver halide photographic material according to claim 4, wherein the compound of the general formula (II) is selected from the compounds represented by the following general formula (III). General formula (III) In the formula (III), V ₁ ′, V ₂ ′ and V ₃ ′ are a hydrogen atom,
Or a non-aromatic substituent. V ₄ ′, V ₅ ′, V ₆ ′, and V ₇ ′ represent a hydrogen atom or a substituent. However, V ₅ '
And V ₆ ′, or V ₆ ′ and V ₇ ′ together form 5 members or 6 members
A member ring may be formed. R ₁₀ represents a hydrogen atom or an alkyl group. When Z ₂ is a nitrogen atom, R ₁₀ represents a hydrogen atom. n ₁ ′ represents 0 or 1. X ₁ , X ₂ , X ₃ ,
q ₁ , q ₂ , q ₃ , R ₃ , R ₄ , M ₁ , m ₁ , and Z ₂ are represented by the general formula (I
Synonymous with I). 6. The compound represented by the general formula (I), (II) or (III) is J-aggregating.
5. The silver halide photographic light-sensitive material according to any one of 5. 7. The silver halide photographic material according to claim 1, wherein the silver halide photographic emulsion in the photographic material is tabular grains having an aspect ratio of 2 or more and all silver halide grains in the emulsion. The silver halide photographic light-sensitive material according to any one of claims 1 to 6, wherein the emulsion contains 50% or more (area) of the emulsion. 8. The silver halide photographic material according to claim 1, wherein the silver halide photographic emulsion in the photographic material is selenium-sensitized.
7. A silver halide photographic light-sensitive material according to any one of items 1 to 7,