JP2001343721A - Silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material, having high sensitivity and nearly free of a residual color after processing in rapid processing. SOLUTION: The silver halide photosensitive material contains a selenium sensitized silver halide emulsion, containing a compound of formula (I) (where Y is, e.g. a group of atoms required for forming a heterocylcle; Z1 and Z2 are each, e.g. a group of atoms required for forming an N-containing heterocycle; R is, e.g. alkyl; D is a group required for forming a methine dye; L1 and L2 are each methine: (p) is 0 or 1; M is a counter ion; and (m) is a number 0 or larger required for neutralizing electric charges in each molecule).

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 emulsion and a silver halide photographic light-sensitive material containing the emulsion. More specifically, an object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and little residual color even after rapid processing.

[0002]

2. Description of the Related Art It is known that sensitizing dyes used for spectral sensitization greatly affect the performance of silver halide photographic materials. Slight differences in the structure of sensitizing dyes have a significant effect on photographic performance such as sensitivity, fogging, storage stability, residual color (residual color) after processing, and granularity. The combined use of more than one species greatly affects photographic performance, but it is difficult to predict the effect in advance, and many researchers have synthesized many sensitizing dyes and Efforts have been made to examine the photographic performance of dyes in combination. However, it is still impossible to predict photographic performance. While high sensitivity and high image quality are required for photographs, demands for rapid photographic processing and reduction of waste liquid amount for environmental issues have been particularly strong in recent years, without causing adverse effects such as fogging and residual color. The importance of a technique for spectrally sensitizing silver halide grains with high sensitivity is increasing. Tabular grains have a large surface area to volume (specific surface area) and are preferred for spectral sensitization in that they can adsorb a large amount of sensitizing dyes, and are also effective in improving the sensitivity / granularity ratio. The residual (residual color) increases, and the problem of the residual color becomes more serious than the regular particles. On the other hand, in photographic processing, it is desired to reduce the processing time. However, if the processing time is reduced, the residual amount of the sensitizing dye used in the emulsion increases, and the problem of residual color becomes more serious. . Therefore,
A technique for reducing the residual color has been strongly desired. It is known that increasing the hydrophilicity of the sensitizing dye is effective as a means for improving the residual color.However, in general, the higher the hydrophilicity, the weaker the adsorption of the sensitizing dye to silver halide grains is. An adverse effect on photographic properties, such as a decrease in sensitivity, is unavoidable, and the effect of improving residual color is limited. Therefore, a combination of spectral sensitization with a sensitizing dye having both hydrophilicity and adsorptivity and a chemical sensitization method for efficiently improving photographic sensitivity has been required.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and little residual color even after rapid processing.

[0004]

Means for Solving the Problems The object of the present invention has been achieved as a result of the following studies (1) to (6). That is,

(1) In a silver halide photographic material containing at least one silver halide photographic emulsion layer on a support, at least one compound represented by the following general formula (I) is contained in the emulsion layer. A silver halide photographic light-sensitive material, wherein the emulsion of the emulsion layer is selenium-sensitized. General formula (I)

[0006]

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In the formula (I), Y represents a group of atoms necessary to form a heterocyclic ring or a group of atoms necessary to form a benzene ring to which a heterocyclic ring is fused; It may be condensed with a ring or may have a substituent. Z
¹ and Z ² represent an atomic group or a single bond necessary for forming a nitrogen-containing heterocyclic ring, and the nitrogen-containing heterocyclic ring has a substituent even if fused with another carbon ring or a heterocyclic ring. You may. R represents an alkyl group, an aryl group or a heterocyclic group. D represents a group necessary for forming a methine dye.
L ¹ and L ² each represent a methine group. p represents 0 or 1. M represents a counter ion, and m represents a number of 0 or more necessary to neutralize the charge in the molecule.

(2) In the general formula (I) according to the above (1), Y is a pyrrole ring, a furan ring, The silver halide photographic light-sensitive material according to the above (1), which represents an atom group necessary for forming a benzene ring in which a thiophene ring, a pyrrole ring, a furan ring, and a thiophene ring are fused.

(3) In the general formula (I) described in the above (1), a pyrrole ring, a furan ring, a pyrrole ring, a furan ring, The silver halide photographic material as described in the above item (1), which represents an atom group necessary for forming a thiophene ring.

(4) The silver halide photographic material according to the above (1), wherein the general formula (I) according to the above (1) is selected from the following general formula (II). General formula (II)

[0011]

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In the formula (II), Y ¹¹ represents an atom group necessary to form a pyrrole ring, a furan ring or a thiophene ring, or an atom group necessary to form an indole ring, a benzofuran ring or a benzothiophene ring. And may be condensed with another carbon ring or a heterocyclic ring or may have a substituent. X ¹¹ is an oxygen atom, a sulfur atom, a selenium atom or NR
Represents ¹³ . R ¹¹ , R ¹² and R ¹³ represent an alkyl group, an aryl group or a heterocyclic group. Z ¹¹ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring, and may be condensed with another carbon ring or a heterocyclic ring or may have a substituent.
L ¹¹ , L ¹² , L ¹³ , L ¹⁴ and L ¹⁵ each represent a methine group. p1 represents 0 or 1. n1 is 0, 1, 2, 3
Or represents 4. M ¹ represents a counter ion, and m 1 represents a number of 0 or more necessary for neutralizing the charge in the molecule.

(5) The silver halide photographic material as described in the above item (1), wherein the general formula (I) described in the above item (1) is selected from the following general formula (III). General formula (III)

[0014]

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In the formula (III), Y ²¹ represents an atom group necessary for forming a pyrrole ring, a furan ring and a thiophene ring;
Further, it may be condensed with another carbon ring or a heterocyclic ring or may have a substituent. X ²¹ and X ²² represent an oxygen atom, a sulfur atom, a selenium atom or NR ²³ . R ²¹ , R ²² and R ²³ represent an alkyl group, an aryl group or a heterocyclic group.
V ²¹ , V ²² , V ²³ and V ²⁴ represent a hydrogen atom or a substituent, and two adjacent substituents do not combine with each other to form a saturated or unsaturated condensed ring. L ²¹ , L ²² and L ²³ each represent a methine group. n2 is 0,1,
Represents 2, 3 or 4. M2 represents a counter ion, and m2 represents a number of 0 or more necessary to neutralize the charge in the molecule.

(6) In the emulsion layer as described in (1) to (5), 50% or more of the total projected area of silver halide grains in the emulsion is tabular grains having an aspect ratio of 2 or more. The silver halide photographic light-sensitive material according to any one of the above (1) to (5).

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below.
In the present invention, when a specific moiety is referred to as a "group", the moiety may be unsubstituted or substituted with one or more (up to the largest possible number of) substituents. Means good. 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 the substituent is V, the substituent represented by V is not particularly limited. Examples thereof include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group and a tricycloalkyl group), and an alkenyl Groups (including cycloalkenyl groups and bicycloalkenyl groups) and alkynyl groups], aryl groups, heterocyclic groups (also referred to as heterocyclic groups), cyano groups, hydroxyl groups,
Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonium group An acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, Sulfo group,
Alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinyl groups Examples thereof include a finylamino group, a phospho group, a silyl group, a hydrazino group, a ureido group, and other known substituents.

More specifically, V is a halogen atom (eg, fluorine, chlorine, bromine, iodine), an alkyl group [linear,
Represents a branched or cyclic substituted or unsubstituted alkyl group.
They include an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl,
-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 5 to 3 carbon atoms
0 substituted or unsubstituted bicycloalkyl groups, for example, bicyclo [1.2.2] heptane-2-yl, bicyclo [2.2.2] octan-3-yl), and also a tricyclo structure having many ring structures. Includes An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below includes the following alkenyl group, cycloalkenyl group, bicycloalkenyl group, alkynyl group, and the like in addition to the alkyl group having such a concept. ], An alkenyl group [which represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms). Cycloalkenyl groups such as 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl groups (substituted or unsubstituted bicycloalkenyl groups, preferably substituted or unsubstituted bicycloalkenyl having 5 to 30 carbon atoms) Groups such as bicyclo [2.2.1] hept-2-ene-
1-yl, bicyclo [2.2.2] oct-2-ene-
4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably having 6 carbon atoms)
~ 30 substituted or unsubstituted aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o
-Hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound obtained by removing one hydrogen atom from a monovalent group, More preferably, it has 3 to 30 carbon atoms.
A 5- or 6-membered aromatic heterocyclic group such as 2-furyl, 2
-Thienyl, 2-pyrimidinyl, 2-benzothiazolyl, still 1-methyl-2-pyridinio, 1-methyl-2
A cationic heterocyclic group such as quinolinio),

A cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 3 carbon atoms)
0 substituted or unsubstituted alkoxy group such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably substituted or unsubstituted having 6 to 30 carbon atoms) Aryloxy group such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy , T-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, such as 1-phenyltetrazole-5-oxy,
-Tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a carbon number of 6 to 6)
30 substituted or unsubstituted arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p
-Methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, , 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 having 7 to 7 carbon atoms)
30 substituted or unsubstituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group having 1 carbon atom)
A substituted or unsubstituted alkylamino group having from 30 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N
-Methylanilino, diphenylamino), an ammonio group (preferably an ammonio group, a substituted or unsubstituted alkyl or aryl having 1 to 30 carbon atoms, an ammonio group substituted with a heterocycle, for example, trimethylammonio, triethylammonio, diphenylmethylammonium E), an acylamino group (preferably a formylamino group, having 1 to 3 carbon atoms)
0 substituted or unsubstituted alkylcarbonylamino group, 6 to 30 carbon atoms of substituted or unsubstituted arylcarbonylamino group, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri -N-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group 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, such as methoxycarbonylamino, ethoxy Carbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methylmethoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, Phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably having 0 to 3 carbon atoms) A substituted or unsubstituted sulfamoylamino group, such as sulfamoylamino, N, N
-Dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, 6 carbon atoms)
~ 30 substituted or unsubstituted arylsulfonylamino groups such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino),

A mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably substituted or unsubstituted having 6 to 30 carbon atoms) Arylthio group, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably having 0 to 30 carbon atoms)
A substituted or unsubstituted sulfamoyl group such as N-
Ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl) , A sulfo group, an alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms 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, such as methylsulfonyl, ethylsulfonyl, Phenylsulfonyl, p
-Methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, Heterocyclic carbonyl groups linked to the carbonyl group by a substituted or unsubstituted carbon atom, such as acetyl, pivaloyl,
-Chloroacetyl, stearoyl, benzoyl, pn
-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-
Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl ), Carbamoyl group (preferably having 1 to carbon atoms)
30 substituted or unsubstituted carbamoyl groups 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 heterocyclic azo groups having 3 to 30 carbon atoms, for example, phenylazo, p-chlorophenylazo,
5-ethylthio-1,3,4-thiadiazol-2-ylazo), an 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 having 2 to 30 carbon atoms) A substituted or unsubstituted phosphinyl group,
For example, phosphinyl, dioctyloxyphosphinyl,
Diethoxyphosphinyl), a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinyl Amino 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 having 3 to 30 carbon atoms). 30
A substituted or unsubstituted silyl group such as trimethylsilyl, t-butyldimethylsilyl and 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, for example, N, N-dimethylureido).

Further, two Vs are connected to each other to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring, for example, a 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, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole ring, phenanthate Lysine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring,
And a phenothiazine ring and a phenazine ring. ) May have a condensed structure.

Among the above-mentioned substituents V, those having a hydrogen atom may be removed and further substituted with the above-mentioned substituents. Examples of such complex substituents include acylsulfamoyl groups, alkyl and arylsulfonylcarbamoyl groups. Examples include methylsulfonylcarbamoyl, p-methylphenylsulfonylcarbamoyl, acetylsulfamoyl, benzoylsulfamoyl groups.

Hereinafter, the methine dye represented by formula (I) of the present invention will be described in detail. When Y is a group of atoms necessary for forming a heterocyclic ring, the 5-membered unsaturated heterocyclic ring formed by Y is a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, a furan ring, an oxazole ring, an isoxazole ring. Ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, selenophene ring, selenazole ring, isoselenazole ring, tellurophen ring, tellurazole ring, isotellurazole ring, etc.
Examples of the membered unsaturated heterocyclic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyran ring, a thiopyran ring and the like, and further condensed with another 5- to 6-membered carbon ring or heterocyclic ring, for example, An indole ring, a benzofuran ring, a benzothiophene ring, and a thienothiophene ring can also be formed. Further, unsaturated heterocycles in which part of the double bond in these heterocycles is hydrogenated (for example, a pyrroline ring, a pyrazoline ring, an imidazoline ring, a dihydrofuran ring, an oxazoline ring, a dihydrothiophene ring, a thiazoline ring),
Alternatively, it may be a hydrogenated saturated heterocycle (for example, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, tetrahydrofuran ring, oxazolidine ring, tetrahydrothiophene ring, thiazolidine ring). When Y is an atomic group necessary to form a benzene ring to which a heterocyclic ring is fused, examples of the ring formed by Y include an indole ring, a benzofuran ring, and a benzothiophene ring.

The ring formed by Y is preferably a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring or a benzothiophene ring, more preferably a pyrrole ring, a thiophene ring or a furan ring.

The nitrogen-containing heterocyclic ring formed by Z ¹ and Z ² is preferably a 5- to 6-membered nitrogen-containing heterocyclic ring, and is preferably an oxazole ring, a thiazole ring, a selenazole ring, an imidazole ring, a 2-pyridine ring, -Pyridine ring, 3,3-dimethyl-3H-pyrrole ring. In addition to the ring represented by Y, a benzene ring, a cyclohexene ring,
A carbon ring such as a naphthalene ring or a heterocyclic ring such as a furan ring or a thiophene ring may be condensed. The nitrogen-containing heterocyclic ring formed by Z ¹ and Z ² is more preferably an oxazole ring, a thiazole ring, an imidazole ring and a 2-pyridine ring, and further preferably an oxazole ring and a thiazole ring.

The ring formed by Y and the nitrogen-containing heterocyclic ring formed by Z ¹ and Z ² may have a substituent, and the substituent represented by V is mentioned as an example. .
Preferred substituents V are the above-mentioned alkyl groups, aryl groups, aromatic heterocyclic groups, alkoxy groups, alkylthio groups, cyano groups, and halogen atoms.

The alkyl group represented by R may be unsubstituted or substituted, and has 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms.
7, particularly preferably 1 to 4 unsubstituted alkyl groups (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl) or 1 to 18 carbon atoms, preferably 1 to 4
7, particularly preferably 1-4 substituted alkyl groups ｛substituents, each substituent represented by the above-mentioned V (aryl group, unsaturated hydrocarbon group, carboxy group, sulfo group, sulfato group, cyano group, halogeno Atom (for example, fluorine, chlorine, bromine, iodine), hydroxy group, mercapto group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyl group, sulfamoyl group , A heterocyclic group, an alkylsulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, an alkylsulfonylsulfamoyl group, and the like, which may be further substituted).

The aryl group represented by R may be unsubstituted or substituted, and has 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms. Phenyl, 1-naphthyl) or a substituted aryl group having 6 to 26 carbon atoms, preferably 6 to 21 carbon atoms, and more preferably 6 to 16 carbon atoms. Alkyl and aryl groups, unsaturated hydrocarbon groups, carboxy groups, sulfo groups,
A sulfato group, a cyano group, a halogen atom (eg, fluorine, chlorine, bromine, iodine), a hydroxy group, a mercapto group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, acyl group, alkoxycarbonyl group,
An aryloxycarbonyl group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a heterocyclic group, an alkylsulfonylcarbamoyl group, an acylcarbamoyl group, an acylsulfamoyl group, an alkylsulfonylsulfamoyl group, which may be further substituted). ｝
Preferably it is a phenyl group.

The heterocyclic group represented by R may be unsubstituted or substituted, and has 1 to 20 carbon atoms, preferably 1 carbon atom.
To 15, more preferably an unsubstituted heterocyclic group having 1 to 10 carbon atoms (e.g., pyrrole, furan, thiophene), or 1 to 26 carbon atoms, preferably 1 to 21 carbon atoms, and more preferably 1 to 16 carbon atoms. Substituted heterocyclic groups {Examples of the substituent include the respective substituents represented by V above}.

R is preferably an acid group or a group having a dissociable proton, such as a carboxyl group, a sulfo group,
A phosphonic acid group, a boronic acid group, or -CONHSO _{2
-, - SO 2 NHSO 2 -} , - CONHCO -, - SO 2
NHCO- or the like is a substituted group, more preferably an alkyl group substituted by the acid group or a group having a dissociable proton, further preferably a carboxyl group, a sulfo group, an alkylsulfonylcarbamoyl group (for example, methanesulfonyl Carbonyl), an acylcarbamoyl group (eg, acetylcarbamoyl), an acylsulfamoyl group (eg, acetylsulfamoyl), a substituted alkyl group containing any of an alkylsulfonylsulfamoyl group (eg, methanesulfonylsulfamoyl). is there. Most preferably, they are a carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group.

The methine groups represented by L ¹ and L ² may have a substituent. Examples of the substituent include the substituents represented by V. p is preferably 0.

M in the general formula (I) 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. Whether a dye is a cation, an anion, or has a net ionic charge depends on its substituents and the environment (such as pH) in the solution. 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, 1,8-diazabicyclo [5.4.0] -7-undecenium ion). The anion may be either an inorganic anion or an organic anion, such as a halide anion (eg, fluoride ion, chloride ion, bromide ion, iodide ion), or a substituted aryl sulfonate ion (eg, p-ion). Toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion, aryldisulfonic acid ion (for example, 1,3-benzenesulfonic acid ion,
1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion,
Examples include picrate ion, acetate ion, and trifluoromethanesulfonic acid ion. In addition, other dyes having an opposite charge to the ionic polymer or dye may be used. Preferred cations are sodium ion, potassium ion, triethylammonium ion, tetraethylammonium ion, pyridinium ion, ethylpyridinium ion, methylpyridinium ion. Preferred anions are perchlorate, iodide, bromide, substituted arylsulfonate (eg p.
-Toluenesulfonate ion). m represents a number of 0 or more necessary to balance the charges, and is 0 when an internal salt is formed. It is preferably a number from 0 to 4.

D is a group necessary to form a methine dye, and any methine dye can be formed by D. Preferably, cyanine dye, merocyanine dye, rhodacyanine dye, trinuclear merocyanine dye, Examples include a nuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. For more information on these dyes, see FM Hemer's Heterocyclic Compounds-
Cyanine Dyes and Related Compounds, '' John Wiley &
Sons-New York, London, 1964, D.
M. Sturmer, Heterocyclic Compounds-Special topics
in heterocyclicchemistry ", Chapter 18, Section 14,
482-515 and the like. Preferred general formulas of the dyes include the general formulas described in U.S. Pat. No. 5,994,051, columns 32-36, and US Pat.
No. 236, columns 30 to 34. The general formulas of cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in US Pat. No. 5,340,694 No. 21.
(XI), (XII), and (XIII) in columns 22 to 22 (however, the number of n ₁₂ , n ₁₅ , n ₁₇ , and n ₁₈ is not limited;
An integer greater than or equal to 4 (preferably 4 or less) is preferred. Preferred are cyanine, merocyanine and rhodacyanine dyes, and more preferred are cyanine dyes.

In the general formula (I), when a cyanine dye is formed by D, it can be represented by a resonance formula such as the following general formula (I '). General formula (I ')

[0038]

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Preferred forms of the compound represented by formula (I) will be more specifically exemplified. More preferably, the compound of the general formula (I) is selected from the following general formulas (a) to (l).

[0040]

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In the formula, D, R, M and m have the same meanings as those in formula (I), and X ¹ is an oxygen atom, sulfur atom, selenium atom or NR ¹ (R ¹ is an alkyl group, an aryl group X ² represents an oxygen atom, a sulfur atom or N 2
R ² (R ² is an alkyl group, an aryl group or a heterocyclic group). Further, the benzene ring and the heterocyclic ring in the formula may be substituted with each substituent represented by V, and may be condensed with another carbon ring or a heterocyclic ring. Among these, preferred are (a) to (i), and more preferred are (a) to (a).
(F), more preferably (a) to (c), and particularly preferably (a) or (c).

More preferably, the methine dye represented by the general formula (I) is selected from the group consisting of the following general formulas (IA), (IB) and (I)
C) and (ID). General formula (IA)

[0043]

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In the formula (IA), Y, R, Z ¹ , Z ² , L ¹ , L
^2, p is as defined for formula ^{(I), L 3 1,} L 32, L 33, L
³⁴ and L ³⁵ represent a methine group. p3 represents 0 or 1. n3 represents 0, 1, 2, 3 or 4. Y ³¹ is 5
It represents an atomic group necessary for forming a 6-membered nitrogen-containing heterocyclic ring. Further, another carbon ring or a heterocyclic ring may be condensed or may have a substituent. M3 represents a counter ion, and m3 represents a number from 0 to 4 required to neutralize the charge of the molecule. R ³¹ represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. General formula (IB)

[0045]

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In the formula (IB), Y, R, Z ¹ , Z ² , L ¹ , L
^2, p is as defined for formula (I), L ^{4 1} and L ⁴² each represents a methine group. n4 represents 0, 1, 2, 3 or 4. Y
⁴¹ represents an atom group necessary for forming an acidic nucleus, and may be condensed with another carbon ring or a heterocyclic ring or may have a substituent. M4 represents a counter ion, and m4 represents a number from 0 to 4 required to neutralize the charge of the molecule. General formula (IC)

[0047]

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In the formula (IC), Y, R, Z ¹ , Z ² , L ¹ , L
^2, p is as defined for formula ^{(I), L 5 1,} L 52, L 53, L
⁵⁴ , L ⁵⁵ , L ⁵⁶ and L ⁵⁷ represent a methine group. p5 is 0
Or represents 1. n51 and n52 represent 0, 1, 2, 3 or 4. Y ⁵¹ and Y ⁵² each represent an atomic group necessary for forming a 5- to 6-membered nitrogen-containing heterocyclic ring, and may have a substituent. However yet another carbocyclic or heterocyclic ring to Y ⁵² may be condensed. M ⁵ represents a counter ion, m5
Represents a number of 0 or more and 4 or less necessary for neutralizing the electric charge of the molecule. R ⁵¹ and R ⁵² represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. General formula (ID)

[0049]

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In the formula (ID), Y, R, Z ¹ , Z ² , L ¹ , L
^2, p is as defined for formula ^{(I), L 6 1,} L 62, L 63, L
⁶⁴ , L ⁶⁵ , L ⁶⁶ and L ⁶⁷ represent a methine group. p6 is 0
Or represents 1. n61 and n62 represent 0, 1, 2, 3 or 4. Y ⁶¹ and Y ⁶² represent an atomic group necessary for forming a 5- to 6-membered nitrogen-containing heterocyclic ring, and may have a substituent. However yet another carbocyclic or heterocyclic ring to Y ⁶² may be condensed. M ⁶ represents a counter ion, m 6
Represents a number of 0 or more and 4 or less necessary for neutralizing the electric charge of the molecule. R ⁶¹ and R ⁶² represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group.

Formulas (IA), (IB), (IC) and
Y in (ID)³¹, Y⁵²And Y⁶²5 to 6 members represented by
Is a further 5- or 6-membered carbon ring or
It may be condensed with a heterocyclic ring. Benzene as a carbon ring
Heterocycles such as rings, naphthalene rings, etc.
A phen ring, etc., but the fused ring is a carbocyclic ring
And more preferably a benzene ring. Ingredient
Physically, it is mentioned as an example of Z11 in the following general formula (II).
A 5- to 6-membered nitrogen-containing heterocycle (system) is preferred, and specific examples are given below.
U.S. Pat. No. 5,340,694, columns 23-24.
Z₁₁, Z₁₂, Z ₁₃, Z₁₄And Z₁₆As an example of
And similar ones.

Y ⁴¹ represents a group of atoms necessary for forming an acyclic or cyclic acidic nucleus, and can take the form of an acidic nucleus of any general merocyanine dye. Next to the methine chain linking the position of the Y ⁴¹ are a thiocarbonyl group or a carbonyl group in a preferred form. The acidic nucleus referred to here is, for example, “The Theory of the Photo” edited by TH James.
Graphic Process ", 4th edition, published by MacMillan Publishing, 1977, p. 198. Specifically, U.S. Patent Nos. 3,567,719 and 3,57
5,869, 3,804,634, 3,8
No. 37,862, No. 4,002,480, No. 4,
925,777 and JP-A-3-167546. The acidic nucleus is preferable when it forms a 5- to 6-membered nitrogen-containing heterocyclic ring composed of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms.

2-pyrazolin-5-one, pyrazolidin-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5-one ,
2-thiooxazoline-2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, Isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3-oxo Indazolinium, 5,
7-dioxo-6,7-dihydrothiazolo [3,2-
a] pyrimidine, cyclohexane-1,3-dione,
3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, pyrido [ 1,2-a] pyrimidine-
1,3-dione, pyrazolo [1,5-b] quinazolone,
Pyrazolo [1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-
2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1-dioxide, 3-dicyanomethylene-2,3-dihydrobenzo [d] thiophene-
1,1-dioxide nuclei; and nuclei having an exomethylene structure in which the carbonyl group or thiocarbonyl group forming these nuclei is substituted with an active methylene position of an active methylene compound having a structure such as ketomethylene or cyanomethylene.

[0054] Preferably hydantoin as Y ^41, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thio-oxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine -
2,4-dithione, barbituric acid and 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 2-thiobarbitic acid Tool acid. Particularly preferred are 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine and barbituric acid.

[0055] 5-6 formed by Y ⁵¹ and Y ⁶¹
The membered nitrogen-containing heterocyclic ring is obtained by removing an oxo group or a thioxo group from the heterocyclic ring represented by Y41. Preferably hydantoin, 2 or 4-thiohydantoin,
2-oxazolin-5-one, 2-thiooxazoline-
2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarbituric acid obtained by removing an oxo group or a thioxo group, more preferably Is hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, 2-
A thiobarbituric acid obtained by removing an oxo group or a thioxo group, particularly preferably 2 or 4-thiohydantoin, 2-oxazoline-5-one, or rhodanine obtained by removing an oxo group or a thioxo group. .

[0056] ^{R 31, R 51, R 52} , R 61, R 62 and (if it exists and R ⁴¹⁾ nitrogen atoms on substituents acidic nucleus Y ⁴¹ is a substituted or unsubstituted respectively, an alkyl group , An aryl group, or a heterocyclic group, and the groups exemplified as R in the methine dye of the general formula (I) are preferable. R ³¹ ,
Of these, R ⁴¹ , R ⁵¹ , R ⁵² , R ⁶¹ , and R ⁶² are preferably a substituted or unsubstituted alkyl group, and more preferably an alkyl group substituted with an acid group or a group having a dissociable proton. More preferably a carboxyl group, a sulfo group or _{-CONHSO 2, -, - SO 2} NHSO
_{2 -, - CONHCO -, -} SO 2 NHCO- substituted alkyl groups containing any one of, particularly preferably,
A carboxymethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, or a methanesulfonylcarbamoylmethyl group.

L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ , L ⁴¹ , L
⁴² , ^L51 , ^L52 , ^L53 , ^L54 , ^L55 , ^L56 , ^L57 ,
L ⁶¹ , L ⁶² , L ⁶³ , L ⁶⁴ , L ⁶⁵ , L ⁶⁶ and L ⁶⁷ each independently represent a methine group. These methine groups may have a substituent, and examples of the substituent include the substituents represented by V. Further, a ring may be formed with another methine group, or Y ³¹ , Y ⁴¹ , Y ⁵¹ , Y ⁵² , Y ⁶¹ , Y
It can also form a ring with ⁶² . L ¹ , L ² , L ³⁴ ,
L ³⁵ , L ⁵⁶ , L ⁵⁷ , L ⁶⁶ and L ⁶⁷ are preferably
It is an unsubstituted methine group.

N3, n4, n51, n52, n61 and n62 represent 0, 1, 2, 3 or 4, and when the number is 2 or more, the methine group is repeated but need not be the same. n3, n4, n
51 and n62 are preferably 0, 1, 2, 3;
More preferably, it is 0, 1, 2 and particularly preferably 0
Or 1. n52 and n61 are preferably 0 or 1, and more preferably 0.

P3, p5 and p6 each independently represent 0 or 1. Preferably it is 0.

M ³ , M ⁴ , M ⁵ and M ⁶ each represent a counter ion, and are preferably the same as the above-mentioned M. m3, m4, m
5, m6 represents a number of 0 or more necessary to neutralize the charge in the molecule, and is 0 when an internal salt is formed. It is preferably a number from 0 to 4.

The methine dye represented by the general formula (I) is particularly preferably a cyanine dye (IA) among the general formulas (IA), (IB), (IC) and (ID),
(IA) is preferably represented by the general formula (II). Hereinafter, the dye represented by Formula (II) will be described in detail.

In the general formula (II), Y ¹¹ represents an atom group necessary for forming a pyrrole ring, a furan ring or a thiophene ring, or an atomic group necessary for forming an indole ring, a benzofuran ring or a benzothiophene ring. Which may be condensed with another carbon ring or a heterocyclic ring or may have a substituent, but it is preferable that no other condensed ring is present. The ring formed by Y11 is particularly preferably a pyrrole ring, a furan ring or a thiophene ring.

X ¹¹ represents an oxygen atom, a sulfur atom, a selenium atom or NR ^13, and represents an oxygen atom, a sulfur atom or NR ¹³
And particularly preferably an oxygen atom or a sulfur atom.

The nitrogen-containing heterocyclic ring formed by Z ¹¹ may be condensed with a carbon ring such as a benzene ring, a cyclohexene ring or a naphthalene ring or a heterocyclic ring such as a furan ring or a thiophene ring. Is preferably a carbocyclic ring, more preferably a benzene ring. The nitrogen-containing heterocyclic ring formed by Z11 is preferably a thiazoline ring, a thiazole ring, a benzothiazole ring, an oxazoline ring, an oxazole ring, a benzoxazole ring, a selenazoline ring, a selenazole ring, a benzoselenazole ring, a tellurazoline ring, a tellurazole ring, Benzotellurazole ring, 3,3-dialkylindolenine ring (for example, 3,3-dimethylindolenine), imidazoline ring, imidazole ring, benzimidazole ring, isoxazole ring, isothiazole ring, pyrazole ring, 2-pyridine ring, 4-pyridine ring, 2-quinoline ring, 4-quinoline ring, 1-isoquinoline ring, 3-
Examples include an isoquinoline ring, an imidazo [4,5-b] quinoxalin ring, an oxadiazole ring, a thiadiazole ring, a tetrazole ring, a pyrimidine ring, and a ring obtained by condensing a benzene ring with the above ring. More preferred are a benzoxazole ring, a benzothiazole ring, a benzimidazole ring and a quinoline ring, and still more preferred are a benzoxazole ring and a benzothiazole ring. These may be substituted by the respective substituents represented by V described above. Specific examples include those similar to the examples of Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ and Z ₁₆ in U.S. Pat. No. 5,340,694, columns 23 to 24.

R¹¹, R¹², R¹³An alkyl group represented by
Examples of the aryl group and the heterocyclic group include the methyl group represented by the general formula (I).
Examples of the groups described for R in the dye include:
R¹¹, R¹²Preferably has an acid group or a dissociable proton.
Is a substituted alkyl group, more preferably
Carboxyl group, sulfo group, or -CONHSO _Two
-, -SO_TwoNHSO_Two-, -CONHCO-, -SO_Two
NHCO- is a substituted alkyl group containing any of
And particularly preferably a 2-sulfoethyl group, a 3-sulfoethyl group.
Propyl group, 3-sulfobutyl group, 4-sulfobutyl
Group, carboxymethyl group or methanesulfonylcarba
Moylmethyl group. R¹³Is preferably unsubstituted alkyl
Especially a methyl group or an ethyl group.
preferable.

The methine groups represented by L ¹¹ , L ¹² , L ¹³ , L ¹⁴ and L ¹⁵ may be unsubstituted or substituted, and examples of the substituent include those represented by V. L ¹⁴ , L
¹⁵ is preferably both unsubstituted methine groups.

N1 represents 0, 1, 2, 3 or 4;
In the above case, the methine group is repeated, but need not be the same. It is preferably 0, 1, 2, 3, more preferably 0, 1, 2, and even more preferably 0 or 1. p1 represents 0 or 1, and is preferably 0.

Examples of M ¹ include the respective ions described for M in the methine dye of the general formula (I).
Particularly, it is preferably a cation. Preferred cations are sodium, potassium, triethylammonium, pyridinium, N-ethylpyridinium. m1 represents a number of 0 or more necessary for neutralizing an intramolecular charge, and is 0 when an intramolecular salt is formed. Preferably it is 0, 1, 2, or 3.

The methine dye represented by the general formula (II) is preferably further represented by the general formula (III). Hereinafter, the dye represented by Formula (III) will be described in detail.

In the general formula (III), Y^{twenty one}Formed by
Ring is selected from a pyrrole ring, a furan ring, and a thiophene ring.
You. Y^{twenty one}The direction of condensation of the ring formed by is arbitrary,
Taking the case of the thiophene ring as an example, the sulfur of the thiophene ring
The atom is X to the fused carbon-carbon bond^{twenty one}On the same side as
Thieno [3,2-d] azole type (of the above general formula (c)
Type) or X ^{twenty one}Thieno [2,3-
d] azole type (type of the above general formula (a)), thiol
Thieno [3,4-d] azo fused at the 3- and 4-positions of the benzene ring
Of the general formula (type of the general formula (b))
Is preferred. Long wavelength spectral absorption is required as a sensitizing dye
In particular, the type of the general formula (a) is preferable.
Further, it may have a substituent on the ring formed by Y21.
Preferably, each substituent represented by V is a substituent.
No. The substituent may be an alkyl group (eg, methyl),
Reel groups (eg, phenyl), aromatic heterocyclic groups (eg,
1-pyrrolyl), an alkoxy group (for example, methoxy),
Alkylthio group (eg methylthio), cyano group, halogen
Atom (for example, fluorine, chlorine, bromine, iodine)
And more preferably a halogen atom.
Is preferably a chlorine atom or a bromine atom.

X ²¹ and X ²² represent an oxygen atom, a sulfur atom, a selenium atom or NR ²³ , preferably an oxygen atom, a sulfur atom or NR ²³ , more preferably an oxygen atom or a sulfur atom. It is preferably a sulfur atom.

R^{twenty one}, R^{twenty two}, R^{twenty three}An alkyl group represented by
Examples of the aryl group and the heterocyclic group include the methyl group represented by the general formula (I).
Examples of the groups described for R in the dye include:
R^{twenty one}, R^{twenty two}Preferably has an acid group or a dissociable proton.
Is a substituted alkyl group, more preferably
Carboxyl group, sulfo group, or -CONHSO _Two
-, -SO_TwoNHSO_Two-, -CONHCO-, -SO_Two
NHCO- is a substituted alkyl group containing any of
And particularly preferably a 2-sulfoethyl group, a 3-sulfoethyl group.
Propyl group, 3-sulfobutyl group, 4-sulfobutyl
Group, carboxymethyl group or methanesulfonylcarba
Moylmethyl group. More preferably, R^{twenty one}, R^{twenty two}
Is a 2-sulfoethyl group, 3-sulfopro
Pill group, 3-sulfobutyl group or 4-sulfobutyl group
And the other is a carboxymethyl group or a methanes group.
It is a rufonylcarbamoylmethyl group. R^{twenty three}Is preferably
Is an unsubstituted alkyl group, and is a methyl group or an ethyl group.
It is particularly preferred that there is.

The substituents represented by V ²¹ , V ²² , V ²³ , and V ²⁴ include the substituents represented by V, and two adjacent substituents are connected to each other to form a saturated or unsaturated group. It does not form a saturated fused ring. V ²¹ and V ²⁴ are preferably hydrogen atoms, and V ²² and V ²³ are each a hydrogen atom or an alkyl group (eg, methyl), an aryl group (eg, phenyl), an aromatic heterocyclic group (eg, 1-pyrrolyl), an alkoxy group. Group (eg, methoxy), alkylthio group (eg, methylthio), cyano group, halogen atom (eg, fluorine,
(Chlorine, bromine, iodine). V ²³ is more preferably a hydrogen atom, and V ²² is more preferably a halogen atom, particularly preferably a chlorine atom or a bromine atom.

L^{twenty one}, L^{twenty two}, L^{twenty three}No methine group represented by
May be substituted or substituted, and the substituent is
Each substituent represented by V is mentioned. n2 is 0,1,
Represents 2, 3 or 4, when 2 or more, the methine group is repeated
But need not be the same. Preferably 0,1,
2,3, more preferably 0,1,2,
Is preferably 0 or 1. When n2 is 0, L^{twenty one}Is
It is preferably an unsubstituted methine group. When n2 is 1,
L ^{twenty two}Is a methine group substituted with an unsubstituted alkyl group;^{twenty one},
L^{twenty three}Is preferably an unsubstituted methine group;^{twenty two}Is special
Is a methyl-substituted methine or ethyl-substituted methine group
Is preferred.

Examples of M ² include the ions described for M in the methine dye of the general formula (I).
Particularly, it is preferably a cation. Preferred cations are sodium, potassium, triethylammonium, pyridinium, N-ethylpyridinium. m2 represents a number of 0 or more necessary for neutralizing an intramolecular charge, and is 0 when an intramolecular salt is formed. Preferably it is 0, 1, 2, or 3.

The compound of the formula (I), which is preferable in the silver halide emulsion of the present invention, will be described below more specifically.

When used in the red-sensitive emulsion layer, the compound of the general formula (I) is represented by the general formula (III), and X ²¹ and X ²²
Is an oxygen atom, the other is a sulfur atom, Y ²¹ is a pyrrole ring, a furan ring or a thiophene ring substituted with a halogen atom, and R ²¹ and R ²² are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoyl. an alkyl group, n2 is 1, L ^21, L ²³ are unsubstituted methine groups, L ²² is a methyl substituted methine group or an ethyl substituted methine ^{group, V 21, V 23, V} 24 is a hydrogen atom , V ²² are an alkyl group (eg, methyl), an alkoxy group (eg, methoxy), an alkylthio group (eg, methylthio), a cyano group, a halogen atom (eg, fluorine, chlorine,
Bromine, iodine), more preferably a halogen atom,
M ² is an organic or inorganic monovalent cation, and m 2 is 0
Or it is preferably 1.

When used in a green-sensitive emulsion layer, the compound of the general formula (I) is represented by the general formula (III), and X ²¹ and X ²²
Are both oxygen atoms, Y ²¹ is a pyrrole ring, a furan ring or a thiophene ring substituted with a chlorine atom or a bromine atom, and R ²¹ and R ²² are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group. There, n2 is 1, L ^21, L ²³ are unsubstituted methine groups, L ²² is a methyl substituted methine group or an ethyl substituted methine ^{group, V 21, V 23, V} 24 represents a hydrogen atom, V
²² is an alkyl group (eg, methyl), an aryl group (eg, phenyl), an aromatic heterocyclic group (eg, 2-thienyl),
An alkoxy group (eg, methoxy), an alkylthio group (eg, methylthio), a cyano group, a halogen atom (eg, fluorine, chlorine, bromine, iodine), more preferably a halogen atom, and M ² is an organic or inorganic monovalent cation And m2 is preferably 0 or 1.

When used in a blue-sensitive emulsion layer, the compound of the general formula (I) is represented by the general formula (III), and X ²¹ and X ²²
Are both sulfur atoms, Y ²¹ is a thiophene ring substituted with a halogen atom, R ²¹ and R ²² are a sulfoalkyl group, a carboxyalkyl group or an alkylsulfonylcarbamoylalkyl group, n2 is 0, ²¹ is an unsubstituted methine group, V ²¹ , V ²³ , and V ²⁴ are hydrogen atoms, and V ²² is an alkyl group (eg, methyl), an alkoxy group (eg, methoxy), an alkylthio group (eg, methylthio), a cyano group, A halogen atom (for example, fluorine, chlorine, bromine, iodine), more preferably a halogen atom, particularly preferably a chlorine atom or a bromine atom, M2 is an organic or inorganic monovalent cation, and m2 is 0 or 1. Preferably, there is.

Specific examples of the compounds of the general formula (I) of the present invention (including the compounds of the general formulas (II) and (III) as subordinate concepts) are shown below, but the present invention is limited thereby. Do not mean. Other than the following, Japanese Patent Application 2000-124
612 can be selected from the methine dyes S-1 to S-95.

[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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The compounds of the present invention represented by the general formula (I) (including the compounds of the lower concept) are described in "Heteroc" by FM Hamer.
yclic Compounds-Cyanine Dyes and Related Compound
s ", John Wiley & Sons-New York, London,
1964, DMSturmer, Heterocyclic Compound
s-Special topics in heterocyclic chemistry, 1st
Chapter 8, Section 14, Pages 482-515, John Wiley & S
ons-New York, London, 1977, Rod
d's Chemistry of Carbon Compounds '' 2nd Ed.vol.IV,
part B, 1977, Chapter 15, Chapters 369-422, E
It can be synthesized based on the method described in lsevier Science Publishing Company Inc., New York, and the like.

Two or more compounds of the formula (I) of the present invention may be used in the same emulsion. General formula (I) of the present invention
May be used in combination with other sensitizing dyes other than the present invention in the same emulsion. 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 FMHame
r, Heterocyclic Compounds-Cyanine Dyes and Relat
ed Compounds ", John Wiley & Sons, New York, London, 1964, DMSturmer," Heteroc
yclic Compounds-Special topics in heterocyclic che
mistry, "Chapter 18, Section 14, Pages 482 to 515. As a general formula of a preferred dye,
U.S. Pat. No. 5,994,051, pages 32 to 44,
And sensitizing dyes represented by the general formulas described in JP-A-5,747,236, pages 30 to 39, and specific examples. Also, preferred cyanine dyes, merocyanine dyes,
The general formula for rhodacyanine dyes is described in US Pat.
No. 694, columns 21-22 (XI), (XII), (XIII)
(However, the number of n ₁₂ , n ₁₅ , n ₁₇ , and n ₁₈ is not limited, and is an integer of 0 or more (preferably 4 or less)).

One of these sensitizing dyes which can be used in combination may be used, or two or more of them may be used.
Particularly, those having an effect of supersensitization are preferable, and typical examples thereof are U.S. Patent Nos. 2,688,545 and 2,972.
No. 7,229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,
Nos. 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,303,377,
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
7,803, JP-B-43-49336, 53-1
2375, JP-A-52-110618 and JP-A-52-1
No. 09925 and the like.

In addition to the sensitizing dye, the emulsion may contain a dye having no spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Supersensitizers useful in 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. 664, No. 3,615,613, No. 3,61
No. 5,632, No. 3,615,641, No. 4,5
Nos. 96,767, 4,945,038 and 4,
965,182, 4,965,182, 2,933,390, 3,635,721, 3,743,510, 617,295, No. 3,635,721 and the like, and the method described in the above-mentioned patent is also preferable as to its use.

Next, the silver halide photographic emulsion and the silver halide photographic material of the present invention will be described in detail. The timing at which the methine dye of the general formula (I) used in the present invention (and other sensitizing dyes and supersensitizers) is added to the silver halide emulsion of the present invention has been useful. It may be during any of the emulsion preparation steps that have been recognized. For example, U.S. Pat. No. 2,735,766
No. 3,628,960 and 4,183,75
6, No. 4,225,666, JP-A-58-184.
142, 60-196749, etc., the stage before silver halide grain formation and / or desalting, during and / or after desalting and before the start of chemical ripening. As disclosed in JP-A-58-113920, the timing of addition at any time before or immediately after chemical ripening, during the process, or after the chemical ripening and before coating, before the emulsion is coated. May be done. No. 4,225,666;
As disclosed in JP-A-8-7629 and the like, the same compound may be used alone or in combination with a compound having a different structure, for example, by dividing the compound into a particle formation step and a chemical ripening step or after completion of chemical ripening, The compound may be added in portions such as before aging or during the process and after completion, or may be added while changing the type of compound to be added and the combination of compounds.

The amount of the methine dye used in the present invention (the same applies to other sensitizing dyes and supersensitizers) depends on the shape and size of the silver halide grains. 1 × 10 ^-6 to 8 × 1 per mole
It can be used in 0 ^-3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol per mol of silver halide, and is preferably 7.5. An addition amount of × 10 ^{−6 to} 1.5 × 10 ⁻³ mol is more preferable.

The methine dye (and other sensitizing dyes and supersensitizers) used in the present invention 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 coexisted. Also,
Ultrasound can also be used for lysis. As a method for adding this 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, US Pat. No. 3,822,1
As described in No. 35, a compound is dissolved in a surfactant,
A method of adding the solution to an emulsion, JP-A-51-7462.
4, a method of dissolving with a compound that causes a red shift and adding the solution to an emulsion;
As described in JP-A-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, the method described in U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287, and 3,429,835 may be used for addition to the emulsion. .

The organic solvent for dissolving the methine dye used in the present invention includes, for example, methyl alcohol, ethyl alcohol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, benzyl alcohol, fluorine alcohol, methyl cellosolve , Acetone, pyridine or a mixed solvent thereof.

When dissolving the methine dye of the present invention in water, the above-mentioned organic solvents, or a mixed solvent thereof, it is preferable to add a base. The base may be either an organic base or an inorganic base, and examples thereof include amine derivatives (eg, triethylamine, triethanolamine), pyridine derivatives, sodium hydroxide, potassium hydroxide, sodium acetate, and potassium acetate. As a preferable dissolving method, a method in which a dye is added to a mixed solvent of water and methanol, and further, triethylamine in an equimolar amount to the dye is added.

In the silver halide emulsion used in the present invention, the silver halide grains may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride, silver chloroiodobromide and the like. For use in color photographic paper, for example, a silver chlorobromide emulsion is preferable for the purpose of speeding up and simplifying the processing, and 95 mol% or more of silver chlorobromide emulsion is silver chloride. Certain silver chloride, silver chlorobromide, or silver chloroiodobromide can be preferably used. In particular, silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used to speed up the development processing time. Further, silver iodobromide emulsions are preferred for use in color photography films (negative and reversal), and silver iodobromide emulsions are preferably 95%.
Silver bromide, silver iodobromide, or silver chloroiodobromide in which at least mol% is silver bromide can be preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1. ２2 μm is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, octahedral or tetradecahedral, or irregular crystals such as spherical or tabular. It may have a shape or a mixture thereof. In the present invention, among these, 50% or more of the particles having the regular crystal form,
The content is preferably 70% or more, more preferably 90% or more.

The emulsion used in the present invention is described in P. Glafkides, "C.
himie et Phisique Photographique "(Paul Montel, 1967), GFDuffin," Photographic Emuls
ion Chemistry "(Focal Press, 1966), V.
Making and coating Photographic by L. Zelikman et al
Emulsion "(Focal Press, 1964) and the like. That is, any method such as an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide salt includes a one-sided mixing method, a double-sided mixing method, and a combination thereof. A method may be used. A method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the emulsion used in the present invention, the aspect ratio is at least 2 (preferably at most 1000), preferably at least 50%, more preferably at least 70%, particularly preferably at least 80% of the total projected area of the silver halide grains in the emulsion. ) Are preferable, and the aspect ratio is more preferably from 4 to 1,000, further preferably from 6 to 500, and particularly preferably from 8 to 300. For example, tabular grains of silver chlorobromide are preferably used for color printing paper, and tabular grains of silver iodobromide are preferably used for color photographic film.

In general, tabular grains are tabular having two parallel faces, and thus “thickness” is represented by the distance between two parallel faces constituting the tabular grains. The diameter of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain in an electron micrograph, and the diameter / thickness ratio is called an aspect ratio.

The silver chlorobromide tabular grains for use in color photographic paper will be described in detail. The silver chloride content is preferably 80 mol% or more, more preferably 95% or more. . Further, the silver chlorobromide particles preferably comprise a core portion and a shell portion (outermost layer) containing more iodide than the core portion. It is preferable that 90% or more of the core portion is silver chloride. The core portion may be composed of two or more portions having different halogen compositions. The shell part is preferably 50% or less of the total particle volume,
Particularly preferably, it is 0% or less. The silver iodide content of the shell part is preferably 0.5 to 13 mol%,
It is particularly preferred that it is 1 to 6 mol%. The content of silver iodide in all grains is preferably 0.1 to 5 mol%,
〜2 mol% or less is particularly preferred. The silver iodide content of the core is preferably at most 1 mol%, particularly preferably 0%. The silver bromide content may be different between the core part and the shell part. The silver bromide content is 0 based on the total silver.
-20 mol% is preferable, and 0.1-5 mol% is particularly preferable. The diameter of the high silver chloride tabular grains is preferably from 0.2 to
1.0 μm. The thickness is 0.2 μm or less, preferably 0.15 μm or less, and particularly preferably 0.1 μm or less. Further, the aspect ratio is preferably 3 to 20,
More preferably, it is 5 to 15. The particle size distribution of the high silver chloride tabular grains may be polydisperse or monodisperse, but is more preferably monodisperse. The dispersion coefficient of the particle size is preferably 5 to 25%, particularly preferably 5 to 20%. The dispersion coefficient of the particle thickness is also preferably 5 to 25%, particularly preferably 5 to 15%.

A crystal habit controlling agent is used to form the {111} plane as the outer surface in the high silver chloride tabular grains used for color printing paper. The formation of tabular grains is achieved by generating two parallel twin planes, and the formation of twin planes depends on temperature, dispersion medium (gelatin), halogen concentration, etc., so these appropriate conditions are set. Must. When a crystal habit controlling agent is present during nucleation, the gelatin concentration is preferably 0.1 to 10%. The chloride concentration is 0.01 mol / liter or more, preferably 0.0
3 mol / liter or more. Japanese Patent Laid-Open No. 2000-2915 discloses a crystal habit controlling agent specifically used and a method for forming {111} high silver chloride tabular grains using the same.
No. 6 can be used.

The tabular grains may be tabular grains having {100} planes as main planes. The shape of the main plane is a right-angled parallelogram or a triangular to pentagonal shape in which one corner of the right-angled parallelogram is missing (a missing shape is a side having the corner as a vertex and the corner as the corner) A right-angled triangular portion formed by the above) or the missing portion exists in two or more and four or less.
To an octagonal shape. A method for forming tabular silver halide emulsion grains having a {100} major plane is described in, for example,
No. 301129, No. 6-347929, No. 9-340
No. 45, No. 9-96881, No. 8-122954,
No. 9-189977.

In silver iodobromide tabular grains used in color photography films, silver iodobromide, silver iodochloride, or chloroiodide containing 30 mol% or less of silver iodide as a halogen composition. Silver halide is preferred. Particularly preferred is silver iodobromide or silver iodochlorobromide containing 2 to 10 mol% of silver iodide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less.
Mol% or less, or 0 mol%. The diameter of the silver iodobromide tabular grains is preferably 0.3 to 5.0 μm. The thickness of the tabular grains is preferably 0.05 to 0.5 μm. The aspect ratio of the tabular grains is preferably 4 to 50, more preferably 5 to 30, and still more preferably 6 to 25.

The silver halide emulsion used in the present invention is usually chemically sensitized. As a chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. No. 2,448,06)
0, 3,320,069), iridium, platinum,
Sensitization method using metals such as rhodium and palladium (for example, US Pat. Nos. 2,448,060 and 2,566,245)
No. 2,566,263), a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. No. 2,222,264).
), A selenium sensitization using a selenium compound, a tellurium sensitization using a tellurium compound, or a reduction sensitization method using tin salts, thiourea dioxide, polyamine or the like (for example, U.S. Pat. Nos. 2,487,850 and 2,518). , 698 and 2,521, 925). These sensitization methods can be used alone or in combination. In the present invention, it is more preferable to use selenium sensitization, sulfur sensitization, and gold sensitization in combination.

The silver halide emulsion used in the present invention is preferably chemically sensitized with a selenium sensitizer. In the present invention, at least the selenium-sensitized emulsion containing the compound of the formula (I) is preferably used. It must be contained in one silver halide emulsion layer. As the selenium sensitizer, a selenium compound disclosed in a conventionally known patent can be used. That is, the emulsion is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include, for example, U.S. Pat. Nos. 3,297,446 and 3,297,448.
No., JP-B-43-13489, and JP-A-44-15748
No., JP-A-4-25832, JP-A-4-109240,
4-147250, 4-271341, 5-
No. 40324, No. 5-224332, No. 5-2243
Nos. 33, 5-11385, 6-43576, 6-75328, 6-175258, 6-17
Nos. 5259, 6-180478, 6-20818
It is preferable to use the compounds described in JP-A Nos. 4 and 6-208186. Specific labile selenium sensitizers include:
Isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas (eg, N, N-dimethylselenourea, N-
Acetyl-N, N ', N'-trimethylselenourea, N
-Trifluoroacetyl-N, N ′, N′-trimethylselenourea), selenoketones, selenoamides (eg, N, N-dimethylselenobenzamide, N, N-diethylselenobenzamide), dicarbamoylselenides (eg, Bis (N, N-dimethylcarbamoyl) selenide), bis (alkoxycarbonyl) selenide (for example, bis (n-butoxycarbonyl) selenide, bis (benzyloxycarbonyl) selenide), and triselenane (for example, 2,4,6) -Tris (p-methoxyphenyl) triselenane), diselenides, polyselenides, selenium sulfide, selenocarboxylic acids (eg, 2-selenopropionic acid, 2-selenobutyric acid), selenoesters (eg, p-methoxyselenobenzoic acid O-
Isopropyl ester, p-methoxyselenobenzoic acid
Se- (3′-oxocyclohexyl) ester), diacyl selenides (for example, bis (2,6-dimethoxybenzoyl) selenide, bis (2,4-dimethoxybenzoyl) selenide, bis (3-chloro-2,6-dimethoxybenzoyl) ) Selenides), selenophosphates (e.g., tri-p-tolylselenophosphate), phosphine selenides (e.g., triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide), selenophosphinic esters, selenophosphonic acid Esters and colloidal metal selenium. Preferably, phosphine selenides, selenoamides, dicarbamoyl selenides, bis (alkoxycarbonyl) selenides, and selenoesters are used.

The preferred types of unstable selenium compounds have been described above, but these are not limiting. 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.

The 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. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, those of the following general formulas (V) and (VI) are preferably used.

[0115]

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In the formula, Q ¹ and Q ² may be the same or different and each has a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms (eg, vinyl, propenyl),
A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms (eg, benzyl, phenethyl); a substituted or unsubstituted aryl group having 6 to 30 carbon atoms (eg, phenyl, pentafluorophenyl, p-chlorophenyl, m-nitrophenyl, p-octylsulfamoylphenyl, 1-
Naphthyl), a substituted or unsubstituted Hajime Tamaki having from 1 to 30 carbon atoms (for example, pyridyl, thienyl, furyl, ^{imidazolyl), - NR a R b,} -OR c, represents a -SR ^d. R ^a ,
R ^b , R ^c , and R ^d may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and includes the same examples as in Q ¹ . However, ^Ra and ^Rb are a hydrogen atom or a substituted or unsubstituted acyl group having 1 to 30 carbon atoms (for example, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, p-nitrobenzoyl, 1-naphthoyl,
4-trifluoromethylbenzoyl).
Among the compounds represented by the general formula (V), preferred are N, N-dialkylselenourea, N, N, N′-trialkyl-N′-acylselenourea, tetraalkylselenourea, and N, N-dialkyl -Arylselenoamide,
N-alkyl and N-aryl-arylselenoamides, specifically, the following compounds.

[0117]

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[0118]

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In the formula, Q ³ , Q ⁴ and Q ⁵ may be the same or different and include a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, iodine), a substituted or unsubstituted C 1-30 carbon atom. Alkyl groups (eg, methyl, ethyl, t-
Butyl, adamantyl, t-octyl), having 2 to 3 carbon atoms
0 substituted or unsubstituted alkenyl groups (for example, vinyl and propenyl), 7 to 30 carbon atoms of a substituted or unsubstituted aralkyl group (for example, benzyl and phenethyl), and 6 to 30 carbon atoms of a substituted or unsubstituted aryl group ( For example, phenyl, pentafluorophenyl, p-chlorophenyl, m-nitrophenyl, p-octylsulfamoylphenyl, 1-naphthyl), a substituted or unsubstituted heterocyclic group having 1 to 30 carbon atoms (eg, pyridyl, thienyl,
Furyl, ^{imidazolyl), - NR e R f,} -OR g, -S
R ^h represents —SeR ⁱ . R ^e , R ^f , R ^g , R ^h , and R
ⁱ may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group,
Similar examples and Q ³ can be mentioned. Among the compounds represented by the general formula (VI), preferred are a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate, and specific examples include the following compounds. .

[0120]

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In addition, it can be preferably selected from selenium compounds 1 to 40 of JP-A-11-15115. More preferably, it is a compound of the above general formula (VI), and further preferably a triarylphosphine selenide or a triarylselenophosphate.

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 type, and two or more of the above-mentioned 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 for chemical ripening when using a selenium sensitizer is preferably 45 ° C. or higher. More preferably 50 to 8
0 ° C. pAg and pH are arbitrary. For example, p
The effect of the present invention can be obtained in a wide range of H from 4 to 9.

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

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

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 types of photosensitive materials to which the present invention is applied, such as additives such as color couplers and photographic photosensitive material additives, and the processing of photosensitive materials, are described in JP-A-10-239789, column 65, line 3 to Column 73, line 13, etc. can be applied.

In the silver halide photographic light-sensitive material of the present invention,
Although the various additives described above are used, other various additives can be used according to 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 summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column-996 right-998 right Super strong 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

Emulsions used in the present invention, techniques such as layer arrangement which can be used in photographic light-sensitive materials using the emulsions, functional couplers such as silver halide emulsions, dye-forming couplers, DIR couplers, and various additives And development processing are described in EP 0 565 096 A1 (1.
(Published October 13, 993) and the patents cited therein. The following is a list of each item and the corresponding descriptions.

[0129] 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

[0132]

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

Example 1 (Preparation of silver bromide octahedral emulsion (emulsion A and emulsion B) and silver bromide tabular emulsion (emulsion C and emulsion D))
00 ml, 25 g of deionized bone gelatin, 15 ml of a 50% aqueous NH ₄ NO ₃ solution and 7.5 ml of a 25% aqueous NH ₃ solution were added, and the mixture was kept at 50 ° C., stirred well, and mixed with 750 ml of a 1N aqueous AgNO ₃ solution and 1 mol / mol. L KBr
The aqueous solution was added in 50 minutes, and the silver potential during the reaction was set to -40 mV.
Kept. 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 95 g of deionized bone gelatin and 430 water
pH 6.5 at 50 ° C., and pAg8.
After adjustment to 3, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to obtain the optimum sensitivity.
Aged at 5 ° C. for 50 minutes. This emulsion was designated as emulsion A. Further, 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 as Emulsion B.

6.4 g of KBr and 6.2 g of low molecular weight gelatin having an average molecular weight of 15,000 or less are dissolved in 1.2 liters of water, and 8.1 ml of a 16.4% aqueous solution of AgNO ₃ and 23 7.2 ml of a 0.5% aqueous KBr solution
Was added by the 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.
370 ml of an aqueous solution and a 20% aqueous KBr solution were added over 10 minutes while keeping the silver potential at -20 mV, and 1
After physical ripening for minutes, the temperature was lowered to 35 ° C. Thus, a monodispersed pure silver bromide tabular emulsion (specific gravity: 1.15) having an average projected area diameter of 2.32 μm, a thickness of 0.09 μm, and a diameter variation coefficient of 15.1% was obtained. Thereafter, soluble salts were removed by the coagulation sedimentation method. The temperature was again maintained at 40 ° C.
6 g, 10 ml of a 1 mol / L aqueous solution of sodium hydroxide, 167 ml of water, and 1.66 ml of 35% phenoxyethanol were added to adjust the pAg to 8.3 and the pH 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 C. Further, 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 as Emulsion D.

The emulsion obtained as described above was added to the dyes shown in Table 1 while maintaining the temperature at 50 ° C., and the mixture was stirred for 30 minutes, and further stirred at 60 ° C. for 60 minutes. A gelatin hardener and a coating aid were added to the obtained emulsion, and the emulsion was simultaneously coated with a gelatin protective layer on a cellulose acetate film support so that the coated silver amount was 3.0 g silver / m ^2. And samples 101 to 112 were obtained. The resulting film was exposed to a tungsten bulb (color temperature 2854K) for 1 second through a continuous wedge color filter. Fuji gelatin filter SC-46 for minus blue exposure that excites the dye side as a color filter (manufactured by FUJIFILM Corporation)
The light having a wavelength of 460 nm or less was shielded by using, 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.

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 developed and other processed films were measured for optical density with a Fuji automatic densitometer.
Sample 1 is the reciprocal of the amount of light required to give an optical density of 2.
The relative values are shown assuming that the sensitivity of 01 is 100. Table 1 shows the results.

[0139]

[Table 1]

[0140]

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As is clear from Table 1, the emulsions further selenium-sensitized using the compound represented by the general formula (I) of the present invention were prepared by spectral sensitization with the dyes of Comparative Examples and sulfur sensitization. High sensitivity and low fog (low residual color) as compared with the emulsion prepared. The tendency is more remarkable in tabular grains than in octahedral grains.
As described above, only when the compound of the general formula (I) of the present invention and selenium sensitization are used simultaneously, an emulsion having a specific high sensitivity and low residual color can be obtained. Was found to be more remarkable.

Example 2 A tabular silver iodobromide emulsion was prepared in the same manner as in Emulsion D of Example 5 of JP-A-8-29904. This emulsion is selenium sensitized. The multilayer color photosensitive material is described in Example 5 of JP-A-8-29904.
Was prepared in the same manner according to Sample 101. The sensitizing dye added to the fifth layer was sensitizing dye S-2 instead of ExS-1, 2, and 3.
(5.0 × 10 ^-4 mol / Agmol) or sensitizing dye I-33 (5.0 × 1
0 ^-4 mol / Agmol), and these were designated as Sample 201 and Sample 202, respectively. In order to examine the sensitivity of the sample thus obtained, the light of a Fuji FW type sensitometer (Fuji Photo Film Co., Ltd.) was passed through an optical wedge and a red filter.
Exposure was performed for 100 seconds, and color development was performed using the same processing steps and processing solution as in Example 1 of JP-A-8-29904, and cyan density was measured. The sensitivity was indicated by a relative value of fog density + 0.2. For the residual color, the cyan density after processing of the blank sample without the sensitizing dye was used as a reference (0). as a result,
The sample 202 of the present invention was 133, which was a high sensitivity, while the sensitivity of the comparative sample 201 was 100 (reference). Sample 2
The residual color (cyan stain) after the treatment of No. 02 was 0.025, which was extremely small as compared with 0.094 of Sample 201. As described above, it can be seen that, even in a negative color photosensitive material, a photosensitive material having high sensitivity and low residual color can be obtained by the structure of the present invention.

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Example 3 Emulsion 1 of Example 1 of JP-A-7-92601 was changed from a silver potential of +65 mV to +115 mV in the second double jet.
And the spectral sensitizing dye was changed to sensitizing dye S-3 (8 × 1
0 ^-4 mol / Agmol) or sensitizing dye I-30 of the present invention (8 × 10
^-4 mol / Agmol), and these emulsions were designated as emulsions J and K, respectively.
Further, an emulsion chemically sensitized with potassium thiocyanate, chloroauric acid, pentafluorophenyl-diphenylphosphine selenide and sodium thiosulfate instead of potassium thiocyanate, chloroauric acid and sodium thiosulfate in the above emulsion was prepared. And emulsions L and M, respectively.
And The multilayer color photosensitive material was prepared in the same manner as in Sample 4 of Example 4 of JP-A-7-92601. JP 7-9260
Sample 301, Sample 302, Sample 303 and Sample 304 were prepared by changing the emulsion 1 of the ninth layer of Sample 401 of Example 4 of Example 1 to Emulsion J, Emulsion K, Emulsion L or Emulsion M. The sample thus obtained was evaluated for sensitivity. JP
Magenta density was measured by exposure for 1/50 second and color reversal development as in Example 4 of 7-92601. The sensitivity was determined by calculating the reciprocal of the amount of exposure required to give a density of +0.2 of the minimum density obtained by giving sufficient exposure.
The values are shown as relative values with the sensitivity of 1 being 100. For the residual color, the magenta density after processing of the blank sample without the sensitizing dye was used as a reference (0). As a result, the sample 302 and the sample 30
3. The sensitivity of sample 304 is 110, 123, and 15 respectively.
5, indicating that the sample 304 of the present invention was specifically highly sensitive. The remaining colors (magenta stain) of the sample 301, the sample 302, the sample 303, and the sample 304 are 0.084, respectively.
The values were 0.035, 0.093, and 0.044. Sample 304 using the sensitizing dye of the general formula (I) of the present invention also had a small residual color after processing. As described above, also in the reversal color light-sensitive material, it can be understood that a light-sensitive material having high sensitivity and low residual color can be obtained by the structure of the present invention.

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According to the constitution of the present invention, it is possible to obtain a silver halide photographic material having high sensitivity and little residual color even after rapid processing.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one silver halide photographic emulsion layer on a support, wherein said emulsion layer contains at least one compound represented by the following general formula (I). And a selenium-sensitized emulsion in the emulsion layer. General formula (I) In the formula (I), Y is a group of atoms necessary to form a heterocyclic ring,
Alternatively, it represents an atom group necessary for forming a benzene ring in which a heterocyclic ring is condensed, and may be condensed with another carbon ring or a heterocyclic ring or may have a substituent. Z ¹ and Z ² each represent an atomic group or a single bond necessary for forming a nitrogen-containing heterocyclic ring, and the nitrogen-containing heterocyclic ring has a substituent even when fused with another carbon ring or a heterocyclic ring. May be. R represents an alkyl group, an aryl group or a heterocyclic group. D represents a group necessary for forming a methine dye. L ¹ and L ²
Each represents a methine group. p represents 0 or 1. M
Represents a counter ion, and m represents a number of 0 or more necessary to neutralize the charge in the molecule. 2. In the general formula (I) according to claim 1,
Y forms a pyrrole ring, a furan ring, a thiophene ring, or a pyrrole ring, a furan ring, or a benzene ring condensed with a thiophene ring, which may be condensed with another carbon ring or a heterocyclic ring or may have a substituent. 2. A silver halide photographic light-sensitive material according to claim 1, which represents an atomic group necessary for the formation. 3. The silver halide photographic material according to claim 1, wherein the general formula (I) according to claim 1 is selected from the following general formula (II). General formula (II) In the formula (II), Y ¹¹ represents a group of atoms necessary to form a pyrrole ring, a furan ring, a thiophene ring, or an indole ring;
It represents an atomic group necessary for forming a benzofuran ring or a benzothiophene ring, and may be condensed with another carbon ring or a heterocyclic ring or may have a substituent. X ¹¹ represents an oxygen atom, a sulfur atom, a selenium atom or NR ¹³ . R ¹¹ ,
R ¹² and R ¹³ represent an alkyl group, an aryl group or a heterocyclic group. Z ¹¹ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring, and may be condensed with another carbon ring or a heterocyclic ring or may have a substituent. L ¹¹ , L ¹² ,
L ¹³ , L ¹⁴ and L ¹⁵ each represent a methine group. p1
Represents 0 or 1. n1 represents 0, 1, 2, 3, or 4. M ¹ represents a counter ion, and m 1 represents a number of 0 or more necessary for neutralizing the charge in the molecule. 4. A silver halide photographic material according to claim 1, wherein the general formula (I) according to claim 1 is selected from the following general formula (III). General formula (III) In the formula (III), Y ²¹ represents an atom group necessary for forming a pyrrole ring, a furan ring, and a thiophene ring, and further has a substituent even if condensed with another carbon ring or a heterocyclic ring. Is also good. X ²¹ and X ²² represent an oxygen atom, a sulfur atom, a selenium atom or NR ²³ . R ²¹ , R ²² and R ²³ represent an alkyl group, an aryl group or a heterocyclic group. V ^21, V ^22, V
²³ and V ²⁴ represent a hydrogen atom or a substituent, and two adjacent substituents do not combine with each other to form a saturated or unsaturated condensed ring. L ²¹ , L ²² and L ²³ each represent a methine group. n2 represents 0, 1, 2, 3 or 4. M ² represents a counter ion, and m ² represents a number of 0 or more necessary to neutralize the charge in the molecule. 5. The emulsion layer according to claim 1, wherein
5. The silver halide photographic light-sensitive material according to claim 1, wherein 50% or more of the total projected area of the silver halide grains in the emulsion is tabular grains having an aspect ratio of 2 or more.