JP2004170923A - Silver halide color photographic sensitive material and cyanine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having high sensitivity and little residual color and hardly affected by a variation in processing parameters in rapid processing. <P>SOLUTION: The silver halide color photographic sensitive material has one or more blue-sensitive silver halide emulsion layers, wherein silver halide grains in the emulsion layers consist of cubic or tetradecahedral grains having a silver chloride content of ≥90%, containing 0.05-1.00 mol% silver iodide, having a silver iodide-containing phase formed in a position corresponding to 85% to 100% of grain volume measured from an inside of each grain, and having ä100} faces of ≤0.6 μm as a side length of a cube, and spectral sensitization is carried out with at least one dye of formula (I), wherein Y is a thiophene ring, a furan ring or a pyrrole ring; V is a substituent; n is a number of 0-4; R<SP>1</SP>and R<SP>2</SP>are each substituted or unsubstituted alkyl, aryl or a heterocyclic group; M is a counter ion; and m is a number of ≥0 required to neutralize electric charges in each molecule. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a cyanine compound and a silver halide color photographic light-sensitive material. Specifically, the cyanine compound and the cyanine compound are suitable for rapid processing and have high sensitivity and little change in gradation or fog due to processing solution fluctuation. The present invention relates to the silver halide color photographic material used.

In color photography, a photosensitive material having a dye-forming coupler and a silver halide emulsion on a support is developed with an aromatic primary amine color developing agent to produce an oxidized form of the developing agent and a dye-forming coupler. It is well known that a high-quality color print can be obtained by a method of obtaining a dye-formed image by the reaction of
However, in recent years, as other color printing methods, the ink-jet method, the sublimation type method, color xerography, and the like have been advanced as the respective technologies, and are being recognized as color printing methods, such as improving the photographic image quality. Therefore, this silver halide color photographic system has the greatest features of high image quality, high productivity, and high image robustness, making it easier to produce higher quality and higher quality photos. In addition, it is eager to provide it at a lower cost.
The light-sensitive material containing the current high silver chloride emulsion is usually processed with a color development time of 45 seconds and a total processing time of about 4 minutes. (For example, color processing CP-45X manufactured by Fuji Photo Film Co., Ltd.). Compared to the processing times of the other color printing methods shown above, the processing system for high silver chloride color print materials is not satisfactory and quick. Speeding up the processing also leads to an improvement in productivity, and a further speedup (ultra-rapid processing) of the total processing time of the high silver chloride color print material is desired, and many studies have been made.

In sensitizing dyes used for spectral sensitization, slight structural differences greatly affect photographic performance such as sensitivity, covering, storage stability, and residual color after processing (residual color). Development of a sensitizing dye capable of spectrally sensitizing silver halide grains with high sensitivity without causing adverse effects such as covering and residual color is essential for the high silver chloride color print material.
However, while increasing the amount of dye added due to the recent strong demand for higher sensitivity, it is necessary to respond to the speeding up of photographic processing as described above and the reduction of processing waste liquids to cope with environmental problems. Conventional dyes cannot meet such demands.

Examples of using a cyanine compound having a basic nucleus different from the conventional one as a sensitizing dye include the following.
(1) A silver halide photographic light-sensitive material comprising a silver halide emulsion layer containing a monomethine cyanine dye having a thienothiazole or thienoselenazole nucleus and silver halide grains which are substantially silver chloride (see Patent Document 1) .
(2) A methine dye having an azole mother nucleus condensed with a 5-membered or 6-membered heterocyclic ring, tabular silver halide grains having an aspect ratio of 2.0 or more, or normal silver halide having an average grain size of 3.0 μm or less Contains silver halide emulsion (see Patent Document 2).
(3) A silver halide photographic light-sensitive material containing a sensitizing dye having an azole nucleus condensed with a specific heterocycle (see Patent Document 3).
However, using only the sensitizing dyes described in these documents has resulted in insufficient performance in terms of both rapid processing suitability and sensitivity required for color print materials, and further improvements on the emulsion side are necessary.

  As a response to rapid processing on the emulsion side, it is effective to increase the development speed by using small-sized high silver chloride grains, but it is well known in the industry that sensitivity is also reduced at the same time. . As a countermeasure, a number of techniques for improving the sensitivity by introducing iodide into a high silver chloride emulsion have been disclosed in recent years (see, for example, Patent Documents 4 and 5). However, only the techniques described in these patent documents do not provide sufficiently satisfactory performance in terms of sensitivity, fog, gradation, and the like in rapid processing.

A combination of a methine dye having an azole nucleus fused with a specific heterocycle and a silver iodochloride cubic emulsion is also disclosed (see Patent Document 6). There has been no discussion about the effect of the size of the particles on the photographic performance, and the present invention has been constructed by conducting detailed studies here.
Japanese Patent No. 2791499 JP 2000-63690 A JP 2002-23295 A US Pat. No. 5,726,005 US Pat. No. 5,736,310 JP 2001-343722 A

  The subject of the present invention is a silver halide which is fast in development even in digital exposure such as laser scanning exposure, has high sensitivity and low residual color even in rapid processing, and has little gradation change and fog increase due to processing factor variation. The object is to provide a color light-sensitive material.

  The object of the present invention has been achieved by the following <1> to <13> as a result of intensive studies. That is,

<1> In a silver halide color photographic material having at least one yellow-colored blue-sensitive silver halide emulsion layer on a support, the silver halide grains in the yellow-colored blue-sensitive silver halide emulsion layer are silver chloride. Contains at least 90% and contains 0.05 to 1.00 mol% of silver iodide, and the silver iodide-containing phase is measured from the inside of the grain at any position from 85% to 100% of the grain volume. Spectral sensitization by at least one of the dyes that are formed of cubic or tetrahedral crystal grains having a {100} face with a cube side length of 0.6 μm or less and represented by the following general formula (I) A silver halide color photographic light-sensitive material characterized by the above.
Formula (I)

In formula (I), Y represents an optionally substituted thiophene ring, furan ring, or pyrrole ring, and the bond between two carbon atoms to which Y is condensed is a single bond. Or a double bond. V represents a substituent, and n represents a number of 0 or more and 4 or less. R ¹ and R ² represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. M represents a counter ion, and m represents a number of 0 or more necessary for neutralizing the charge in the molecule.

<2> In the silver halide color photographic light-sensitive material according to <1>, the silver halide grains in the yellow-colored blue-sensitive silver halide emulsion layer contain silver bromide (preferably 0.1 to 7 mol%). The silver bromide-containing phase is formed from 50% to 100% of the grain volume as measured from the inside of the grain and at any position inside the silver iodide-containing phase. 1> A silver halide color photographic light-sensitive material as described above.

<3> In the silver halide color photographic material of the above <1> or <2>, the dye represented by the general formula (I) is a cyanine compound represented by the following general formula (II) or general formula (III) The silver halide color photographic light-sensitive material as described in <1> or <2> above, wherein
Formula (II)

In formula (II), one of R ³ and R ⁴ represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ¹ and V ² represent a hydrogen atom or a monovalent substituent. M ¹ represents a counter ion, and m ¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.
General formula (III)

In formula (III), one of R ⁵ and R ⁶ represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ³ and V ⁴ represent a hydrogen atom or a monovalent substituent. M ² represents a counter ion, and m ² represents a number of 0 or more necessary for neutralizing the charge in the molecule.

<4> In the silver halide color photographic light-sensitive material of <1>, <2> or <3>, the silver halide grains in the yellow-colored blue-sensitive silver halide emulsion layer contain an iridium complex. The silver halide color photographic light-sensitive material according to <1>, <2> or <3>.

<5> In the silver halide color photographic light-sensitive material according to <1>, <2>, <3> or <4>, the silver halide emulsion in the yellow-colored blue-sensitive silver halide emulsion layer is gold sensitized. The silver halide color photographic light-sensitive material as described in <1>, <2>, <3> or <4> above.

<6> The silver halide color photographic light-sensitive material according to <5>, wherein the silver halide grains in the yellow-colored blue-sensitive silver halide emulsion layer are sulfur-sensitized or selenium-sensitized. <5> The silver halide color photographic light-sensitive material described in <5>.

<7> In the cyanine compound represented by the general formula (II), one of R ³ and R ⁴ is carboxymethyl group or methanesulfonylcarbamoylmethyl group, the other is 2-sulfoethyl group, 3-sulfopropyl group, 4- V ¹ and V ² are each selected from a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, and an alkoxycarbonyl group. A cyanine compound characterized by being selected.

<8> In the cyanine compound represented by the general formula (II), one of R ³ and R ⁴ is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, the other is a 3-sulfopropyl group, and V ² is hydrogen. A cyanine compound, which is an atom, and V ¹ is selected from a hydrogen atom, a halogen atom, a cyano group, and a methoxy group.

<9> In the cyanine compound represented by the general formula (III), one of R ⁵ and R ⁶ is carboxymethyl group or methanesulfonylcarbamoylmethyl group, the other is 2-sulfoethyl group, 3-sulfopropyl group, 4- V ³ and V ⁴ are each selected from a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, and an alkoxycarbonyl group. A cyanine compound characterized by being selected.

<10> In the cyanine compound represented by the general formula (III), one of R ⁵ and R ⁶ is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, the other is a 3-sulfopropyl group, and V ⁴ is hydrogen. A cyanine compound, which is an atom, and V ³ is selected from a hydrogen atom, a halogen atom, a cyano group, and a methoxy group.

<11> The silver halide color photographic light-sensitive material according to <1> or <2>, wherein the yellow color-developing blue-sensitive silver halide emulsion layer contains a compound represented by the following general formula (IV): The silver halide color photographic light-sensitive material as described in <1> or <2> above.
Formula (IV)

In formula (IV), Ch represents an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. A represents an atomic group forming an aromatic ring in which two or more benzene rings and / or heterocycles are condensed. Z represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, or a residue (cyanine dye residue) necessary for constituting a cyanine dye as a whole molecule. R ⁷ represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. M ⁷ represents a counter ion, and m ⁷ represents a number of 0 or more necessary for neutralizing the charge in the molecule.

<12> In the silver halide color photographic light-sensitive material of <11>, the compound represented by the general formula (IV) is represented by the following general formula (V). Silver halide color photographic material.
General formula (V)

In Formula (V), Z ⁸ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a residue necessary for constituting a monomethine cyanine dye as a whole molecule. R ⁸ represents a substituted or unsubstituted alkyl group. M ⁸ represents a counter ion, and m ⁸ represents a number of 0 or more necessary for neutralizing the charge in the molecule.
<13> In the silver halide color photographic light-sensitive material according to <11> or <12>, the compound represented by the general formula (V) is represented by the following general formula (VI): The silver halide color photographic light-sensitive material according to 11> or <12>.
General formula (VI)

In formula (VI), Ch ⁹ represents an oxygen atom or a sulfur atom. R ⁹ and R ¹⁰ represent a substituted or unsubstituted alkyl group. V ⁹ and V ¹⁰ represent a hydrogen atom or a monovalent substituent. M ⁹ represents a counter ion, and m ⁹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.

  According to the present invention, it is possible to obtain a silver halide color light-sensitive material which has high development progress even in digital exposure such as laser scanning exposure, high sensitivity and low residual color even in rapid processing, and excellent processing factor variation. In particular, a silver halide color photographic light-sensitive material suitable for color printing can be obtained.

  First, groups used in the present invention will be described in detail.

  In the present invention, when a specific moiety is referred to as a “group”, the moiety may be unsubstituted or substituted with one or more (up to the maximum possible) substituents. Means good. For example, “alkyl group” means a substituted or unsubstituted alkyl group. The substituent that can be used in the compound of the present invention may be any substituent.

  When such a substituent is W, the substituent represented by W is not particularly limited, and examples thereof include a halogen atom, an alkyl group (including a cyclic alkyl group), and an alkenyl group. (Including cyclic alkenyl groups), alkynyl groups], aryl groups, heterocyclic groups (also referred to as heterocyclic groups), cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, Aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group , Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfa Ylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, Alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group (also called phosphono group), silyl group, hydrazino group Ureido group, boronic acid group, phosphato group, sulfato group, and other known substituents.

More specifically, W represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkyl group [[a linear, branched or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, such as bicyclo [1.2.2] heptan-2-yl, bicyclo [2.2.2] octane-3-yl), a tricyclo structure having more ring structures It is intended to encompass such. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below represents an alkyl group having such a concept, but further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2.2.1] hept-2-en-1-yl, bicyclo 2.2.2] is intended to encompass oct-2-en-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 a substituted or unsubstituted group having 6 to 30 carbon atoms) Aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted, aromatic or non-aromatic heterocycles) A monovalent group obtained by removing one hydrogen atom from a ring compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl and 2-thienyl. 2-pyrimidinyl, 2-benzothiazolyl, such as 1-methyl-2-pyridinio, 1-methyl-2-quinolinio A cationic heterocyclic group), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, iso Propoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4- t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy A group (preferably a substituent of 2 to 30 carbon atoms) Is an unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms) A substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably having a carbon number) 1 to 30 substituted or unsubstituted carbamoyloxy groups such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, N n-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy) ), An aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyl Oxy), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or 2 carbon atoms) 30 substituted or unsubstituted heterocyclic amino groups such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), ammonio groups (preferably ammonio groups, C 1-30 substituents) Or an unsubstituted alkyl, aryl, or heterocyclic substituted ammonio group, for example, trimethylammonio, triethylammonio, diphenylmethylammonio), an acylamino group (preferably a formylamino group, a C 1-30 substituent or Unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n- Octyloxyfe Rucarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, Morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, Noxycarbonylamino, p-chlorophenoxycarbonylamino, m- (n-octyloxy) phenoxycarbonylamino), sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms) For example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkanesulfonylamino having 1 to 30 carbon atoms) Substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonyl Amino), a mercapto group, an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms). A substituted arylthio such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms such as 2-benzothiazolyl Ruthio, 1-phenyltetrazol-5-ylthio), sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl N, N-dimethylsulfamoyl, -Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl having 1 to 30 carbon atoms) Groups, substituted or unsubstituted arylsulfinyl groups of 6 to 30 such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or substituted with 1 to 30 carbon atoms) An unsubstituted alkanesulfonyl group, a 6-30 substituted or unsubstituted arylsulfonyl group, such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably formi 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, and a carbonyl group bonded with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms Heterocyclic carbonyl groups such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryloxycarbonyl groups (preferably A substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably Carbon number To 30 substituted or unsubstituted alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl groups (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, For example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably having 6 to 30 carbon atoms) Substituted or unsubstituted arylazo groups, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo) Imide groups (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group ( Preferably, the substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably substituted having 2 to 30 carbon atoms) Or an unsubstituted phosphinyloxy group such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms) An amino group, for example dimethoxyphosphinylamino, Methylaminophosphinylamino), phospho group, silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), hydrazino group (preferably Is a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, such as trimethylhydrazino), a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, such as N, N-dimethylureido), Represents.

  In addition, two Ws can be combined 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 or 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, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, carbazole ring, phenanthridine ring, acridine ring, Phenanthroline ring, Ntoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) Can also take a fused structure.

Among the above-mentioned substituents W, those having a hydrogen atom may be substituted with the above groups after removing this. Examples of such substituents include a —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group (sulfonylsulfamoyl group). ).
More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkanesulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

Next, the methine dye represented by formula (I) of the present invention will be described in detail.
Y is a thiophene ring, a furan ring or a pyrrole ring, preferably a thiophene ring. There are three ways of condensing the ring represented by Y and the thiazole ring. For example, in the case of a thiophene condensed ring, a thieno [2,3-d] thiazole ring or a thieno [3,2-d] thiazole ring is formed. The case is preferred, in which case the bond between two carbon atoms that are condensed is a double bond. Among these, it is more preferable to form a thieno [2,3-d] thiazole ring.
Any substituent may be used as Y, and examples thereof include the aforementioned W. Preferred substituents include alkyl groups (eg methyl), alkoxy groups (eg methoxy), alkylthio groups (eg methylthio), cyano groups, acyl groups (eg acetyl), alkoxycarbonyl groups (eg methoxycarbonyl), halogen atoms (eg fluorine Chlorine, bromine, iodine), more preferably a methyl group, a methoxy group, a cyano group, or a halogen atom, still more preferably a halogen atom, and particularly preferably a fluorine, chlorine, or bromine atom. It is most preferable in terms of residual color performance and spectral absorption characteristics.

The substituent represented by V may be any, and examples thereof include the aforementioned W. Preferred substituents include alkoxy groups (eg methoxy), alkylthio groups (eg methylthio), cyano groups, acyl groups (eg acetyl), alkoxycarbonyl groups (eg methoxycarbonyl), hydroxy groups, carboxyl groups, halogen atoms (eg fluorine, Chlorine, bromine, iodine), more preferably a methoxy group, a cyano group, and a halogen atom, still more preferably a halogen atom (especially chlorine, bromine atom), and most preferably a bromine atom.
n represents a number of 0 or more and 4 or less, preferably 0 or 1, and more preferably 1.

The alkyl group represented by R ¹ and R ² in the general formula (I) may be unsubstituted or substituted, and is an unsubstituted alkyl having 1 to 18, preferably 1 to 7, particularly preferably 1 to 4 carbon atoms. Groups (eg methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups of 1 to 18, preferably 1 to 7, particularly preferably 1 to 4 carbon atoms {substituents For example, an aryl group having 6 to 12 carbon atoms (for example, phenyl, p-chlorophenyl, p-tolyl), an unsaturated hydrocarbon group having 2 to 6 carbon atoms (for example, vinyl), a carboxy group, a sulfo group, a sulfato group, a cyano group Halogen atoms (eg fluorine, chlorine, bromine, iodine), hydroxy groups, mercapto groups, alkoxy groups having 1 to 7 carbon atoms (eg Methoxy, ethoxy, 2-methoxyethoxy, benzyloxy), aryloxy group having 6 to 12 carbon atoms (for example, phenoxy, 1-naphthoxy), alkylthio group having 1 to 7 carbon atoms (for example, methylthio), arylthio having 6 to 12 carbon atoms A group (for example, phenylthio, 1-naphthylthio), an acyl group having 1 to 7 carbon atoms (for example, acetyl, benzoyl), an alkoxycarbonyl group having 2 to 8 carbon atoms (for example, ethoxycarbonyl, benzyloxycarbonyl), a group having 7 to 13 carbon atoms An aryloxycarbonyl group (for example, phenoxycarbonyl), an acyloxy group having 1 to 8 carbon atoms (for example, acetyloxy), a carbamoyl group (for example, morpholinocarbonyl), a sulfamoyl group (for example, N, N-dimethylsulfamoyl), a heterocyclic group ( For example, tetrahydr Furyl), alkanesulfonylcarbamoyl group (eg methanesulfonylcarbamoyl), acylcarbamoyl group (eg acetylcarbamoyl), acylsulfamoyl group (eg acetylsulfamoyl), alkanesulfonylsulfamoyl group (eg methanesulfonylsulfamoyl) Etc.}.

The aryl group represented by R ¹ and R ² in the general formula (I) may be unsubstituted or substituted, and has 6 to 26 carbon atoms, preferably 6 to 21 carbon atoms, more preferably 6 to 16 carbon atoms. Substituted or unsubstituted aryl groups of {the substituents are the substituents described in the description of the substituted alkyl group (aryl group, unsaturated hydrocarbon group, carboxy group, sulfo group, sulfato group, cyano group, halogen Atom (eg fluorine, chlorine, bromine, iodine), hydroxy group, mercapto group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyl group, sulfamoyl group , Heterocyclic group, alkanesulfonylcarbamoyl group, acylcarbamoyl group, acylsulfamoyl Group, alkanesulfonylsulfamoyl group, etc.) or alkyl group (which may be substituted), for example, phenyl, 1-naphthyl, etc.}, preferably a phenyl group.

The heterocyclic group represented by R ¹ and R ² in the general formula (I) may be unsubstituted or substituted, and has 1 to 26 carbon atoms, preferably 1 to 21 carbon atoms, more preferably 1 to carbon atoms. 16 substituted or unsubstituted heterocyclic groups {substituents are the substituents described in the description of the substituted alkyl group (aryl group, unsaturated hydrocarbon group, carboxy group, sulfo group, sulfato group, cyano group). , Halogen atoms (eg fluorine, chlorine, bromine, iodine), hydroxy groups, mercapto groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, carbamoyl groups, Sulfamoyl group, heterocyclic group, alkanesulfonylcarbamoyl group, acylcarbamoyl group, acylsulfamoyl group, An alkanesulfonylsulfamoyl group) or an alkyl group (which may be substituted), for example, pyrrole, furan, thiophene, etc.}.

R ¹ and R ^{2 in} formula (I) are preferably substituted or unsubstituted alkyl groups having 18 or less carbon atoms, and more preferably both are alkyl groups substituted with an acid group. More preferably, ^one of R ¹ and R ² represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group.

Here, the acid group will be described. An acid group is a group having a dissociable proton.
Specifically, for example, sulfo group, carboxyl group, sulfato group, —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ — group ( Sulfonylsulfamoyl groups), sulfonamido groups, sulfamoyl groups, phosphato groups, phosphono groups, boronic acid groups, phenolic hydroxyl groups, and the like, groups that can dissociate protons depending on the pKa and the surrounding pH. For example, a proton dissociable acidic group capable of dissociating 90% or more between pH 5-11 is preferable.
In the cyanine compound represented by the general formula (I), what is preferable as the “alkyl group substituted with an acid group” represented by R ¹ or R ² can be expressed as follows.

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

  Qa may be any linking group as long as it satisfies the above requirements, but preferably consists of an atom or atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group (for example, ethenylene, propenylene), an alkynylene group (for example, ethynylene, propynylene), an amide group, an ester group, a sulfoamide Group, sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Wa)-(Wa represents a hydrogen atom or a monovalent substituent. Monovalent substitution. As the group, the above-mentioned W can be mentioned.)), Or a combination of one or more carbon atoms of 0 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms. Represents a group.

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

  More preferably, Qa is an alkylene group having 1 to 5 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, methyltrimethylene), an alkenylene group having 2 to 5 carbon atoms (for example, ethenylene, propenylene), It is a divalent linking group having 1 to 5 carbon atoms constituted by combining one or more alkynylene groups having 2 to 5 carbon atoms (for example, ethynylene and propynylene). Particularly preferred is an alkylene group having 1 to 5 carbon atoms (preferably methylene, ethylene, trimethylene, tetramethylene).

When T ¹ is a sulfo group, Qa is more preferably ethylene, trimethylene, tetramethylene, or methyltrimethylene, and particularly preferably trimethylene. When Xa is a carboxyl group, Qa is more preferably methylene, ethylene or trimethylene, and particularly preferably methylene.
T ¹ is _{-CONHSO 2 Ra, SO 2 NHCORb,} CONHCORc, in the case of SO ₂ NHSO ₂ Rd, and more preferably as Qa methylene, ethylene, trimethylene, particularly preferably methylene.

Ra, Rb, Rc and Rd each represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclyloxy group, or an amino group.
For example, an unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), 1 to 18 carbon atoms, preferably carbon A substituted alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms [hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and preferably 2 to 18 carbon atoms, More preferably, an unsaturated hydrocarbon group having 3 to 10 carbon atoms, particularly preferably 3 to 5 carbon atoms (for example, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidine group, benzylidene group) is also included in the substituted alkyl group I will say], C6-20, preferably C6-15, more preferably charcoal A substituted or unsubstituted aryl group of 6 to 10 (for example, phenyl, naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), carbon An optionally substituted heterocyclic group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (for example, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl), An alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-hydroxyethoxy, 2-phenylethoxy), 6 to 20 carbon atoms, preferably 6 to carbon atoms 12, more preferably an aryloxy group having 6 to 10 carbon atoms (eg phenoxy, p -Methylphenoxy, p-chlorophenoxy, naphthoxy), a heterocyclyloxy group having 1 to 20, preferably 3 to 12, and more preferably 3 to 10 carbon atoms (meaning an oxy group substituted by a heterocyclic group) For example, 2-thienyloxy, 2-morpholinooxy), amino group is an amino group having 0 to 20, preferably 0 to 12, more preferably 0 to 8 carbon atoms (for example, amino, methylamino, Dimethylamino, ethylamino, diethylamino, hydroxyethylamino, benzylamino, anilino, diphenylamino, ring-formed morpholino, pyrrolidino). Furthermore, the above-described W may be substituted for these.
More preferred are a methyl group, an ethyl group, and a hydroxyethyl group, and particularly preferred is a methyl group.

In addition, in the acid group, for example, a carboxyl group, a dissociative nitrogen atom, and the like may be expressed in a non-dissociated form (COOH, NH) or in a dissociated form (COO ⁻ , N ⁻ ). But you can. Actually, it may be in a dissociated state or a non-dissociated state depending on the environment such as pH where the dye is placed.
When a cation is present as a counter ion, for example, it may be expressed as (COO ⁻ Na ⁺ ) or (N ⁻ Na ⁺ ). In the non-dissociated state, they are expressed as (COOH) and (NH). However, if the counter ion cation compound is considered as a proton, it can also be expressed as (COO ⁻ H ⁺ ) and (N ⁻ H ⁺ ).

In the cyanine compound represented by the general formula (I), ^one of R ¹ and R ² is an alkyl group substituted with an acid group other than a sulfo group, and the other is an alkyl group substituted with a sulfo group. Particularly preferred, the alkyl group having a sulfo group is preferably a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group, or a 2-sulfoethyl group, and more preferably a 3-sulfopropyl group. An alkyl group substituted with an acid group other than a sulfo group is preferably an alkyl group substituted with a carboxyl group, a —CONHSO ₂ — group, a —SO ₂ NHCO— group, a —CONHCO— group, or a —SO ₂ NHSO ₂ — group. Particularly preferred are a carboxymethyl group and a methanesulfonylcarbamoylmethyl group.

In the cyanine compound represented by general formula (I), M represents a counter ion, and when necessary to neutralize the ionic charge of the dye, in the formula to indicate the presence of a cation or an anion. Is included. Whether a dye is a cation, an anion, or has a net ionic charge depends on its substituents and the environment in solution (such as pH). Typical inorganic cations include hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions, etc. Tetramethylammonium cation, tetrabutylammonium cation, benzyltrimethylammonium cation, octadecyltrimethylammonium cation, triethylammonium cation, N, N-diisopropylethylammonium cation, tris (2-hydroxyethyl) ammonium cation, pyridinium cation, ethylpyridinium cation, Quinolinium cation, 2,4-dimethylimidazolium cation, 1,8-diazabicyclo [5.4.0] -7-unde Cation, 1,1,3,3-tetramethyl guanidinium cations, such as N- methyl-morpholinium cation. 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), substituted aryl sulfonate ion (eg p- Toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion), aryl disulfonic acid ion (for example, 1,3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl Examples thereof include sulfate ions (for example, methyl sulfate ions), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroborate ions, picrate ions, acetate ions, and trifluoromethanesulfonate ions. Furthermore, an ionic polymer or another dye having a charge opposite to that of the dye may be used.

M is preferably a cation, and particularly preferably an organic cation. Preferred cations are triethylammonium cation, N, N-diisopropylethylammonium cation, tris (2-hydroxyethyl) ammonium cation, pyridinium cation, ethylpyridinium cation, methylpyridinium cation, 1,8-diazabicyclo [5.4.0]. ] -7-undecenium cation, 1,1,3,3-tetramethylguanidinium cation, N-methylmorpholinium cation.
m represents a number of 0 or more necessary for balancing the electric charge, and is 0 when an inner salt is formed. Preferably 0 or 1.

Next, the methine dyes represented by the general formulas (II) and (III) of the present invention will be described in detail.
In the cyanine compounds represented by the general formula (II) and the general formula (III), one of R ³ and R ⁴ (R ⁵ and R ⁶ ) is an alkyl group substituted with an acid group other than a sulfo group, and the other Is an alkyl group substituted with a sulfo group, but the above-mentioned alkyl group having a sulfo group is preferably a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group, or a 2-sulfoethyl group, and more preferably Is a 3-sulfopropyl group. An alkyl group substituted with an acid group other than a sulfo group is preferably an alkyl group substituted with a carboxyl group, a —CONHSO ₂ — group, a —SO ₂ NHCO— group, a —CONHCO— group, or a —SO ₂ NHSO ₂ — group. Particularly preferred are a carboxymethyl group and a methanesulfonylcarbamoylmethyl group.

As a combination of R ³ and R ⁴ (R ⁵ and R ⁶ ), one is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and the other is a 2-sulfoethyl group, a 3-sulfopropyl group, or a 4-sulfobutyl group. Or it is a case where it is a 3-sulfobutyl group, More preferably, one is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group, and the other is a case where it is a 3-sulfopropyl group. Most preferred is when R ³ (R ⁵ ) is a carboxymethyl group or a methanesulfonylcarbamoylmethyl group and R ⁴ (R ⁶ ) is a 3-sulfopropyl group.

In the cyanine compounds represented by general formula (II) and general formula (III), V ¹ and V ² (V ³ and V ⁴ ) each represent a hydrogen atom or a monovalent substituent, and the two substituents are Although they may be linked to form a saturated or unsaturated condensed ring, it is preferable not to form a condensed ring, and V ² (V ⁴ ) is preferably a hydrogen atom. Examples of the monovalent substituent include the aforementioned W, but preferably a hydroxy group, a carboxyl group, an alkoxy group (for example, methoxy), an alkylthio group (for example, methylthio), a cyano group, an acyl group (for example, acetyl), or an alkoxycarbonyl group. (For example, methoxycarbonyl) and a halogen atom (for example, fluorine, chlorine, bromine, iodine), more preferably a methoxy group, a cyano group, and a halogen atom, still more preferably a halogen atom, and particularly preferably a chlorine atom or bromine An atom, most preferably a bromine atom.

In the cyanine compounds represented by the general formula (II) and the general formula (III), M ¹ (M ² ) each represents a counter ion, and m ¹ (m ² ) is each 0 or more necessary for balancing electric charges. In the case of forming an inner salt, it is 0. 0 or 1 is preferable, and 0 is particularly preferable.
When M ¹ (m ² ) is 1 or more, M ¹ (M ² ) is preferably a cation, particularly an organic cation. ) Ammonium cation, pyridinium cation, ethylpyridinium cation, methylpyridinium cation, 1,8-diazabicyclo [5.4.0] -7-undecenium cation, 1,1,3,3-tetramethylguanidinium cation, N-methylmorpholinium cation is mentioned.

  Specific examples of the cyanine compounds represented by the general formula (I), general formula (II) and general formula (III) of the present invention are shown below, but the present invention is not limited thereby. In addition to the cyanine compounds listed below, for example, among the compounds listed in JP-A-2002-23295, the general formula (I), the general formula (II) and the general formula (III) of the present invention Any of the corresponding compounds can be preferably used.

The cyanine compounds represented by general formula (I), general formula (II) and general formula (III) used in the present invention can be synthesized based on the methods described in the following documents.
a) FMHamer, “Heterocyclic Compounds-Cyanine dyes and related compounds” (John Wiley & Sons-New York, London, 1964),
b) DMSturmer, “Heterocyclic Compounds-Special topics in cyclic chemistry”, Chapter 8, Section 4, 482-515 (John Wiley & Sons-New York, London, 1977)
c) "Rodd's Chemistry of Carbon Compounds", 2nd edition, volume 4, part B, chapter 15, pages 369-422 (Elsevier Science Publishing Company Inc.-New York) 1977)

  The synthesis of the heterocyclic ring used as a raw material for the cyanine compounds represented by the general formula (I), general formula (II) and general formula (III) of the present invention is described in, for example, “Buretan de la Sochete Simic de・ France (Bulletin de la Societe Chimique de France) ”, II-150 (1980) and“ Journal of Heterocyclic Chemistry ”, 16: 1563 (1979) References in the literature can be consulted. Furthermore, the synthesis method disclosed by the present inventors in JP-A-2002-145886 can be used particularly effectively.

  In order to incorporate the cyanine compounds represented by the general formula (I), general formula (II) and general formula (III) of the present invention into the silver halide emulsion of the present invention, they are dispersed directly in the emulsion. Or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3 A solvent such as -methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide or the like may be dissolved in a mixed solvent and added to the emulsion.

  Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is dispersed in an emulsion. As described in JP-B-46-24185, etc., in which a water-insoluble dye is dispersed in a water-soluble solvent without dissolving it, and this dispersion is added to the emulsion. As described in US Pat. Nos. 23389, 44-27555, and 57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is allowed to coexist to form an aqueous solution. Emulsions prepared by adding a surfactant to the aqueous solution or colloidal dispersion as described in US Pat. Nos. 3,822,135 and 4,006,026. Method of adding in, JP As described in JP-A-3-102733 and JP-A-58-105141, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, as described in JP-A-51-74624 Alternatively, a method of dissolving a dye using a compound that shifts red and adding the solution to an emulsion can be used.

  When the cyanine compound of the present invention does not have a counter ion, a base is added when the cyanine compound is dissolved in water, methanol, or a mixed solvent of both, but the pKa is 6.6 to 9.0. It is preferable to add a base having a pKa of 7.0 or more and 8.0 or less. Examples of specific bases (pKa values in parentheses) are as follows.

  Triethanolamine (7.76), 3-cyanopropylamine (7.80), 1,1,1-tris (hydroxymethyl) methylamine (8.30), imidazole (6.99), 1-methylimidazole (6.95), 2,4-dimethylimidazole (8.36), morpholine (8.50), N-methylmorpholine (7.38), N-ethylmorpholine (7.67), 2,4-dimethyl Pyridine (6.99), 2,4,6-trimethylpyridine (7.43)

Although it can be heated at a temperature up to the boiling point of the solvent during dissolution, it is preferably dissolved at 60 ° C. or lower (preferably 0 ° C. or higher), more preferably 50 ° C. or lower. Moreover, performing ultrasonic irradiation at the time of dissolution is an effective means for performing dissolution quickly.
As a preferable dissolution method, a method of adding a dye to water, methanol, or a mixed solvent of water and methanol, and further adding an equimolar to small excess triethanolamine solution with the dye can be mentioned.
The solution in which the dye is dissolved is preferably added immediately to the emulsion. However, when the solution is stored, it is kept at 30 ° C. or less, preferably 20 ° C. or less until use. At this time, since the solubility of the dye is lowered by cooling and precipitation may occur, the solution concentration needs to be equal to or lower than the saturation solubility of the dye at the temperature during storage. The pigment concentration in the preferred solution is 0.2 to 10% by mass, more preferably 0.4 to 5% by mass.

  The time when the cyanine compounds represented by the general formula (I), general formula (II) and general formula (III) of the present invention are added to the silver halide emulsion of the present invention has been found to be useful so far. It may be during any process of preparing the emulsion. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, JP-A-58-184142, 60- As disclosed in specifications such as No. 196749, the silver halide grain formation step and / or the time before desalting, during the desalting step and / or after the desalting to the start of chemical ripening, As disclosed in the specification of Japanese Patent Application Laid-Open No. 58-11939, etc., it is added at any time before the emulsion is coated immediately before chemical ripening, during the process, or after the chemical ripening. May be. Further, as disclosed in the specifications of US Pat. No. 4,225,666 and JP-A-58-7629, the same compound can be used alone or in combination with compounds of different structures, for example, to form particles. Compounds and compounds that may be added separately in the process and during chemical ripening process or after completion of chemical ripening, or divided before or during chemical ripening or after completion of chemical ripening. It may be added by changing the combination type.

  The amount of the cyanine compound represented by the general formula (I), general formula (II) and general formula (III) of the present invention varies depending on the shape and size of the silver halide grains, but is 0 per mole of silver halide. .05 to 4 mmol is preferable, more preferably 0.1 to 2.5 mmol, and it may be used in combination with other sensitizing dyes.

  In the present invention, other sensitizing dyes may be used in addition to the cyanine compounds represented by the general formula (I), general formula (II) and general formula (III). Preferred examples of the sensitizing dye include cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, allopolar dyes, hemicyanine dyes, and styryl dyes. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FMHarmer, “Heterocyclic Compounds-Cyanine Dyes and Related Compounds,” John Willie &・ John Wiley & Sons-New York, London, 1964, DMSturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Special topics in repeating chemistry), Chapter 18, Section 14, 482-515, John Wiley & Sons-New York, London, 1977, "Rods Chemistry of Carbon Compounds (Rodd's Chemistry of Carbon Compounds) 2nd.E d. vol. IV, part B, 1977, Chapter 15, pages 369 to 422, published by Elsevier Science Publishing Company Inc., New York, and the like.

Furthermore, RD 17643, pages 23 to 24, RD 18716, page 648, right column to page 649, right column, RD308119, page 996, right column to page 998, right column, European Patent No. 056596A1, page 65, lines 7 to 10 What is described in, can be used preferably. Also, U.S. Pat. No. 5,747,236 (especially pages 30-39), U.S. Pat. No. 5,340,694 (especially pages 21-60, provided that (XI), (XII), (XIII) 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). The sensitizing dyes shown in the specific examples can also be preferably used.
In addition, sensitizing dyes described in JP-A Nos. 2002-23295 and 2001-343722 can also be preferably used.

  A combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925.

Next, the compound represented by formula (IV) of the present invention will be described in detail.
In the compound represented by the general formula (IV), Ch represents an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom.
A represents an atomic group forming an aromatic ring in which two or more benzene rings and / or heterocycles are condensed. Examples of typical rings include a naphthalene ring system, an anthracene ring system, a phenanthrene ring system, and a naphthacene ring system. Pyrene ring system, indole ring system, isoindole ring system, benzo [b] furan ring system, benzo [b] thiophene ring system, quinoline ring system, isoquinoline ring system, quinazoline ring system, quinoxaline ring system, phthalazine ring system, And carbazole ring system, acridine ring system, phenanthridine ring system, phenanthroline ring system, phenazine ring system, phenoxazine ring system, and phenothiazine ring system. A ring system consisting only of a benzene ring is preferred, and a naphthalene ring system is particularly preferred.

As the substituted or unsubstituted alkyl group, aryl group and heterocyclic group represented by Z and R ⁷ , the same alkyl group and aryl as those mentioned as preferred examples of R ¹ and R ² in formula (I) Groups and heterocyclic groups. In addition, when Z represents a basic nucleus (for example, 3-alkylbenzothiazoline-2-ylidenemethyl) linked through an odd number of methine groups, the compound of the general formula (IV) may represent a cyanine dye as a whole molecule. it can. Z is preferably a hydrogen atom, an alkyl group, or a cyanine dye residue, and R ⁷ is an alkyl group.
In the compound represented by the general formula (IV), M ⁷ represents a counter ion, and examples thereof include the same as M in the general formula (I). Preferred cations for M ⁷ include inorganic cations such as sodium cation and potassium cation, and organic cations such as triethylammonium cation, pyridinium cation and ethylpyridinium cation. Examples of the anion include chloride anion, bromide anion, iodide anion, perchlorate anion, tosylate anion, mesylate anion and the like. m ⁷ represents a number of 0 or more necessary for balancing the electric charge, and 0 when forming an inner salt. Preferably 0 or 1.

Of the compounds of the general formula (IV), a compound represented by the general formula (V) is particularly preferable.
In the formula (V), Z ⁸ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a residue necessary for constituting a monomethine cyanine dye as a whole molecule, preferably a hydrogen atom, a methyl group, or an ethyl group And a monomethine cyanine dye residue, particularly preferably a 3-alkylbenzothiazoline-2-ylidenemethyl group which may have a substituent.
R ⁸ represents a substituted or unsubstituted alkyl group, preferably a methyl group, an ethyl group, a sulfoalkyl group (eg, sulfopropyl), or a carboxyalkyl group (eg, carboxymethyl group).
M ⁸ represents a counter ion, preferably an anion when Z ⁸ is a hydrogen atom or a substituted or unsubstituted alkyl group, and a cation when Z ⁸ is a monomethine cyanine dye residue. Preferable ion species include the ions mentioned as examples of M ⁷ . m ⁸ represents a number of 0 or more necessary for neutralizing the charge in the molecule, and 0 when forming an inner salt. Preferably 0 or 1.

Further, among the compounds of the general formula (V), a monomethine cyanine compound represented by the general formula (VI) is particularly preferable.
In formula (VI), Ch ⁹ represents an oxygen atom or a sulfur atom, preferably a sulfur atom.
R ⁹ and R ¹⁰ represent a substituted or unsubstituted alkyl group, preferably a substituted or unsubstituted alkyl group having 8 or less carbon atoms, more preferably both of R ¹ and R ^{2 in} the general formula (I). An alkyl group substituted with an acid group as defined in the description. Particularly preferably, a sulfoalkyl group (for example, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl, 2-sulfoethyl), a carboxyalkyl group (for example, carboxymethyl), a —CONHSO ₂ — group, a —SO ₂ NHCO— group, or —CONHCO - group, -SO ₂ NHSO ₂ - alkyl group which group is substituted (e.g. methanesulfonyl carbamoylmethyl methyl). Most preferably, R ⁹ is a sulfopropyl group. R ¹⁰ is most preferably selected from a sulfopropyl group, a carboxymethyl group, and a methanesulfonylcarbamoylmethyl group.
In the cyanine compound represented by the formula (IV), V ⁹ and V ¹⁰ represent a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent include the aforementioned W, but preferably a hydroxy group, a carboxyl A group, an alkoxy group (for example, methoxy), an alkylthio group (for example, methylthio), a cyano group, an acyl group (for example, acetyl), an alkoxycarbonyl group (for example, methoxycarbonyl), a halogen atom (for example, fluorine, chlorine, bromine, iodine), More preferred are a methoxy group, a cyano group and a halogen atom, still more preferred is a halogen atom, particularly preferred is a chlorine atom or a bromine atom, and most preferred is a chlorine atom. V ¹⁰ is preferably a hydrogen atom.
M ⁹ represents a counter ion, and is preferably a cation. Preferred ionic species include organic cations such as triethylammonium cation. m ⁹ represents a number of 0 or more necessary for neutralizing the charge in the molecule, and 0 when forming an inner salt. Preferably 0 or 1.

  Specific examples of the compounds represented by general formula (IV), general formula (V) and general formula (VI) of the present invention are shown below, but the present invention is not limited thereby.

The cyanine compound represented by the general formula (IV) used in the present invention is synthesized based on the method described in the literature in the same manner as the compounds of the general formula (I), general formula (II) and general formula (III). be able to.
In order to incorporate the compounds represented by the general formula (IV), general formula (V) and general formula (VI) of the present invention into the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion. Alternatively, it may be dissolved in a solvent such as water, methanol, ethanol, propanol, acetone, N, N-dimethylformamide or a mixed solvent and added to the emulsion. Further, like the compounds of general formula (I), general formula (II) and general formula (III), they can be added to the emulsion as a dispersion.
As a preferable dissolution method, a method of adding a compound to water, methanol, or a mixed solvent of water and methanol can be exemplified. The solution is preferably added immediately to the emulsion, but when the solution is stored, it is kept at 30 ° C. or lower, preferably 20 ° C. or lower until use. At this time, since the solubility of the compound is lowered by cooling and precipitation may occur, the solution concentration needs to be equal to or lower than the saturated solubility of the compound at the temperature during storage. The compound concentration in the preferred solution is 0.2 to 10% by mass, more preferably 0.4 to 5% by mass.

  The time when the compounds represented by the general formula (IV), general formula (V) and general formula (VI) of the present invention are added to the silver halide emulsion of the present invention has been recognized as useful so far. The cyanine compound represented by the general formula (I), the general formula (II) and the general formula (III) is preferably added after being added to the emulsion. The amount of the compound represented by the general formula (IV), general formula (V), or general formula (VI) of the present invention varies depending on the shape and size of the silver halide grains, but is about 0.00 per mole of silver halide. 005 to 0.4 mmol is preferable, and 0.01 to 0.25 mmol is more preferable.

Hereinafter, the silver halide emulsion will be described in detail.
In the present invention, the yellow dye-forming coupler-containing silver halide emulsion in the light-sensitive material layer contains specific silver halide grains. As for the particle shape, cubic having substantially {100} faces or tetradecahedral crystal particles (these particles may have rounded vertices and may have higher-order faces). A cubic particle having a {100} plane is substantially defined by six {100} crystal planes, and the corners and edges of the particle may show some roundness for aging, The crystal planes other than the six {100} crystal planes indicate no crystal plane that can be confirmed. The tetrahedral crystal grains refer to grains that satisfy the relative direction and spacing of the cubic grains and are at least partially demarcated by {100} crystal planes. May be shown, for example, having three pairs of equally spaced parallel {100} crystal faces and eight {111} crystal faces. The particle size is required to be 0.6 μm or less (preferably 0.1 μm or more and 0.6 μm or less) in terms of a cubic conversion side length, more preferably 0.15 μm or more and 0.55 μm or less, and more preferably 0.2 μm or more. Most preferably, it is 0.5 μm or less.

  The silver halide emulsion of other silver halide emulsion layers (magenta dye-forming coupler-containing silver halide emulsion layer and cyan dye-forming coupler-containing silver halide emulsion layer) is not particularly limited in terms of grain shape, but substantially { Cubic or tetrahedral crystal grains having 100} planes (they may have rounded particle vertices and may have higher-order planes), octahedral crystal lattices, principal planes of {100} planes Or it is preferable that it consists of a tabular grain of aspect ratio 2 or more which consists of {111} face. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. For tabular grains whose main surface is {100} face or {111} face, reference can be made to columns 33 (P7) to P840 (P8) of JP-A No. 2000-352794. The particle size is preferably 0.15 μm or more and 0.55 μm or less, more preferably 0.2 μm or more and 0.5 μm or less in terms of a cubic conversion side length.

  The cube side length is represented by the length of one side when a volume equal to the volume of each particle is converted into a cube, and in this specification, the cube side length means the same meaning. The emulsion of the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation system number of the cubic conversion side length of all the particles of the present invention is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. The coefficient of variation of the cubic conversion side length is expressed as a percentage of the average side length of the standard deviation of one side of the cubic conversion side length of each particle. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.

  The silver halide emulsion of the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all the grains be silver halide grains defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.

  As the silver halide emulsion used in the present invention, an emulsion containing silver halide grains having a specific silver halide content is used. In particular, in the case of a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, silver chloride is used. The content must be 90 mol% or more. From the viewpoint of rapid processability, the silver chloride content is preferably 93 mol% or more, and more preferably 95 mol% or more. The silver bromide content is preferably 0.1 to 7 mol%, particularly preferably 0.5 to 5.0 mol%, since the silver bromide content is hard and excellent in latent image stability. The silver iodide content is 0.05 to 1.00 mol%, preferably 0.07 to 0.70 mol%, and preferably 0.10 to 0.0. 50 mol% is particularly preferred. The specific silver halide grains of the present invention are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above-described halogen composition (preferably, a combination of preferred contents, particularly preferred combinations).

  The specific silver halide grains in the silver halide emulsion of the present invention preferably have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a site where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. In addition, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and each silver bromide or silver iodide content may be different, but at least one each. It is necessary to have a contained phase of

  It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide emulsion of the present invention is layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or a silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide-containing phase.

  When the silver halide emulsion of the present invention contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered manner so as to have a silver bromide concentration maximum inside the grain. Further, when the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.

  The silver halide emulsion of the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In that case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same location or at different locations in the grain, but it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are in different locations from the viewpoint of facilitating control of grain formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so that the silver iodide-containing phase tends to be formed in the vicinity of the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention such as high sensitivity and high contrast is such that a silver bromide-containing phase or a silver iodide-containing phase is formed inside the grain. There is a possibility that the silver chloride content will be reduced more than necessary, and the rapid processability may be impaired. Therefore, in order to aggregate these functions for controlling photographic action close to the surface within the grain, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent. From these points, in the present invention, the silver bromide-containing phase is formed at any position of 50% to 100% of the grain volume, as measured from the inside of the grain, and the silver iodide-containing phase is 85% to 100% of the grain volume. % Is preferably formed at any position. Further, the silver bromide-containing phase may be formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase may be formed at any position from 90% to 100% of the grain volume. Further preferred.
Localizing the silver iodide-containing phase in the vicinity of the grain surface in this way is also preferable from the viewpoint of improving the adsorptivity of the sensitizing dye. Only when the halogen distribution of the emulsion is in such a case, preferable photographic performance is exhibited.

  Introducing bromide or iodide ions to contain silver bromide or silver iodide in the silver halide emulsion of the present invention can be carried out by adding a bromide salt or iodide salt solution alone, Along with the addition of the chloride salt solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can be used.

The addition of the bromide salt or iodide salt solution may be concentrated at one time of grain formation or may be performed over a certain period. The position of introducing iodide ions into the high chloride emulsion is limited in obtaining a high-sensitivity and low-coating emulsion. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution should be added from outside of 85% of the particle volume. Also, the addition of the iodide salt solution should preferably be completed inside 98% of the particle volume, most preferably inside 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, so that an emulsion with higher sensitivity and lower covering can be obtained.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.

The silver halide crystal grains of the silver halide emulsion of the present invention preferably contain an iridium compound (complex). As the iridium compound, a 6-coordination complex having 6 ligands and having iridium as a central metal is preferable because it can be uniformly incorporated into a silver halide crystal. As a preferred embodiment of the iridium compound used in the present invention, a hexacoordinate complex having iridium as a central metal having Cl, Br or I as a ligand is preferred, and all six ligands are Cl, Br or More preferred is a hexacoordination complex consisting of I and iridium as a central metal. In this case, Cl, Br, or I may be mixed in the hexacoordination complex. It is particularly preferable that the hexacoordination complex having iridium as a central metal having Cl, Br, or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high-contrast gradation at high illumination exposure.
The iridium complex may contain ligands other than Cl, Br, and I. As the inorganic ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrous acid It is preferable to use ions, water, ammonia, nitrosyl ions, or thionitrosyl ions, and preferred organic ligands are linear compounds having 5 or less carbon atoms in the main chain and / or 5-membered rings or 6-membered rings. The heterocyclic compound of these can be mentioned. More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, pyrazine, and ligands having these compounds as a basic skeleton and a substituent introduced thereto are also preferable.

When the above iridium complex forms a salt with a cation, it is preferable that the iridium complex is easily dissolved in water as the counter cation. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. These iridium complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, and may be added in an amount of 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol. Most preferred.
Preferred iridium complexes include K ₂ [IrCl ₆ ] and K ₂ [Ir (5-methylthiazole) Cl ₅ ].

  In the present invention, the above-mentioned iridium complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or to other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the iridium complex is previously incorporated in the grains and to incorporate them in the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

  When these complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but they are disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to be present only in the particle surface layer, and it is also preferable to add a layer containing only the complex inside the particle and not containing the complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but a hexacoordinate complex having iridium as a central metal in which all six ligands are Cl, Br or I has a maximum silver bromide concentration. It is preferable to make it contain in a part.

  In the present invention, in addition to iridium, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. The ligand is preferably the same as the above iridium complex, and is preferably coordinated to any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc. Is also preferably used in one complex molecule.

The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. This is because gold sensitization can increase the sensitivity of the emulsion, and can reduce variations in photographic performance when scanning exposure is performed with laser light or the like. For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.
The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol, per mol of silver halide. is there.

Colloidal gold sulfide can also be used, and the manufacturing method thereof is “Research Disclosure”, 37154, “Solid State Ionics” Vol. 79, pp. 60-66. 1995, "Comptes Rendus hebdomadaire des Seances de l'Academie des Sciences, Serie B", Vol. 263, p. 1328 1966. The above "Research Disclosure" describes a method using thiocyanate ions in the production of colloidal gold sulfide, but thioether compounds such as methionine and thiodiethanol can be used instead.
Various sizes of colloidal gold sulfide can be used, those having an average particle size of 50 nm or less are preferred, average particle size of 10 nm or less is more preferred, and average particle size of 3 nm or less is more preferred. The composition of the colloidal gold sulfide may also Au ₂ S _1, may be of Au ₂ S ₁ ~Au ₂ S ₂ in such sulfur excess composition, sulfur excess composition is preferred. Au ₂ S _1.1 ~Au ₂ S _1.8 is more preferred. The amount of gold sulfide added may vary widely depending on the case, but 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol of gold atom per mol of silver halide. Is a mole.

  In the present invention, the above gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization or noble metal sensitization using other than gold compounds. . It is particularly preferable to combine with sulfur sensitization and selenium sensitization.

  To the silver halide emulsion of the present invention, various compounds or precursors thereof may be added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Can do. Specific examples of these compounds are preferably those described on pages 39 to 72 of JP-A-62-215272. Further, 5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residue has at least one electron-withdrawing group) described in EP 0447647 are also preferably used.

  In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A No. 11-109576 and the carbonyl group described in JP-A No. 11-327094 are adjacent to both amino groups. Cyclic ketones having a double bond substituted with a group or a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the specification of the present application); The sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4- Dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid , 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 5,556) No. 741, the fourth column, line 56 to the eleventh column, line 22 is preferably applied to the present application, and is incorporated as part of the present application specification), JP-A-11-102045. The water-soluble reducing agents represented by the general formulas (I) to (III) are also preferably used in the present invention.

  The silver halide color photographic light-sensitive material of the present invention is a silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler on a support. Among them, at least one layer contains a silver halide emulsion spectrally sensitized with the dye (cyanine compound) of the present invention. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler functions as a yellow coloring layer. The photosensitive material of the present invention may have a magenta coloring layer, a cyan coloring layer, a hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a coloring layer as described below, if desired, in addition to the yellow coloring layer.

Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention.
For example, as the photographic support, a transmissive support or a reflective support can be used. As the transmissive support, transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), NDCA, terephthalic acid and EG are used. A polyester or the like provided with an information recording layer such as a magnetic layer is preferably used. As the reflective support, a reflective support that is laminated with a plurality of polyethylene layers or polyester layers and contains a white pigment such as titanium oxide in at least one layer of such a water-resistant resin layer (laminate layer) is preferable.

Further, it is preferable that the water-resistant resin layer contains a fluorescent brightening agent. Further, a hydrophilic colloid layer containing the fluorescent brightening agent in a dispersed manner may be separately formed. As the optical brightener, benzoxazole-based, coumarin-based, and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent whitening agents are more preferable. Although the usage-amount is not specifically limited, Preferably it is 1-100 mg / m < ² >. The mixing ratio in the case of mixing with a water-resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass with respect to the resin.

  In the light-sensitive material of the present invention, a dye which can be decolored by processing as described in pages 27 to 76 of European Patent EP0,337,490A2 is applied to a hydrophilic colloid layer for the purpose of improving the sharpness of an image. Among them, oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or divalent to tetravalent alcohols (for example, trimethylolethane) are added to the water-resistant resin layer of the support. It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of the titanium oxide surface-treated with.

In the light-sensitive material of the present invention, the processing described in pages 27 to 76 of European Patent EP0337490A2 is applied to the hydrophilic colloid layer for the purpose of preventing irradiation and halation or improving the safety light safety. It is preferable to add a decolorizable dye (in particular, an oxonol dye or a cyanine dye). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As a dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.
Further, a colored layer that can be decolored by treatment in place of the water-soluble dye or in combination with the water-soluble dye is also used. The colored layer that can be decolored by processing may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a processing color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

  The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., among which it is preferably used as a color photographic paper. The color photographic paper preferably has at least one yellow color-developing silver halide emulsion layer, magenta color-developing silver halide emulsion layer, and cyan color-developing silver halide emulsion layer. The silver halide emulsion layer is a yellow color forming silver halide emulsion layer, a magenta color forming silver halide emulsion layer, and a cyan color forming silver halide emulsion layer in order from the support. However, a different layer structure may be used. The yellow color developing silver halide emulsion layer is preferably the yellow color developing blue-sensitive silver halide emulsion layer of the present invention.

  As silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied in the present invention, as well as processing methods and processing additives applied to process this photosensitive material, Disclosed in JP-A-62-215272, JP-A-2-33144, European Patent EP0,355,660A2, and particularly described in European Patent EP0,355,660A2. Are preferably used. Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433. No. 2-854, No. 1-158431, No. 2-90145, No. 3-194539, No. 2-93641, EP-A-0520457A2, and the like. A silver halide color photographic light-sensitive material and a processing method thereof are also preferable.

  In particular, in the present invention, the above-mentioned reflective support, silver halide emulsion, further different metal ion species doped in silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical enhancement, Sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (coloring) As for the layer), gelatin type, layer structure of the photosensitive material, and coating pH of the photosensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applied.

Other examples of cyan, magenta and yellow couplers used in the present invention include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144. Page 3, upper right column, line 14 to page 18, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11 and page 0, line 15 to 27 of EP0355,660A2. Couplers described in the 5th line, 5th page, 30th line to 28th page, 45th page, 29th line to 31st line, 47th page, 23rd line to 63rd page, 50th line are also useful.
In the present invention, compounds represented by the general formulas (II) and (III) of International Publication WO-98 / 33760 and the general formula (D) of JP-A-10-221825 may be added. .

As the cyan dye-forming coupler, a pyrrolotriazole coupler is preferably used. A coupler represented by the general formula (I) or (II) of JP-A-5-313324 and a general formula of JP-A-6-347960 ( The couplers represented by I) and the exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole type cyan couplers described in European Patent EP 0488248 and European Patent EP 0491197A1, 2,5-diacylamino described in US Pat. No. 5,888,716. Phenol coupler, pyrazoloazole type cyan coupler having an electron-withdrawing group and a hydrogen-bonding group at the 6-position described in U.S. Pat. Nos. 4,873,183 and 4,916,051, Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A-8-171185, JP-A-8-31360, and JP-A-8-339060 are also preferred.
In addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine cyan coupler described in European Patent EP 0333185A2 (particularly, coupler (42) listed as a specific example) A 4-equivalent coupler having a chlorine leaving group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene-based cyan couplers described in JP-A 64-32260 (among others) (Examples of couplers 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole type cyan couplers described in EP 0456226A1, and pyrroloimidazole type cyan couplers described in EP 0484909 are used. You can also.
Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. Couplers (1) to (47) are preferred.

  As the magenta dye-forming couplers, 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers as described in the publicly known documents in the above table are used. Among them, in terms of hue, image stability, color developability and the like. A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly connected to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-61-65245, JP-A-61-65246 Pyrazoloazole couplers containing a sulfonamide group in the molecule as described, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent No. 226 , 849A and 294,785A as described in the 6th position. Use of pyrazoloazole couplers having a group or an aryloxy group. In particular, as the magenta coupler, a pyrazoloazole coupler represented by the general formula (MI) described in JP-A-8-122984 is preferable, and paragraph numbers 0009 to 0026 of the patent are preferable. In addition to this, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in EP 854384 and EP 844640 are also preferably used.

  As yellow dye-forming couplers, in addition to the compounds described in the above table, acylacetamide-type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in European Patent EP 0447969A1, European Patent EP 0482552A1 Malondianilide type yellow coupler having the cyclic structure described in European Patent Nos. 935870A1, 953871A1, 953872A1, 953873A1, and 953874A1 Pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide couplers described in US Pat. No. 5,118,599, US Pat. No. 5,118,599, etc. Acylacetoa having a dioxane structure De type yellow couplers are preferably used. Among them, the use of an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring is particularly preferred. Moreover, the compound represented by the following general formula (S) can be used preferably.

In the general formula (S), R ¹¹ , R ¹² and R ¹³ each independently represent a substituent. n ¹ represents an integer of 0 or more and 5 or less, and when n ¹ is 2 or more, the plurality of R ¹² may be the same or different, and may be bonded to each other to form a ring. n ² represents an integer of 0 or more and 4 or less, and when n ² is 2 or more, the plurality of R ¹³ may be the same or different, and may be bonded to each other to form a ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer.

In the general formula (S), R ¹¹ represents a substituent other than a hydrogen atom. Examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, and a cyano group. Group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group) Anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group Group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, Examples thereof include an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

R ¹² represents a substituent other than a hydrogen atom. Examples of this substituent include those listed above as examples of the substituent for R ¹¹ . Preferably R ¹² is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkyl group (eg, methyl, isopropyl), aryl group (eg, phenyl, naphthyl), alkoxy group (eg, methoxy, isopropyloxy), aryloxy group (Eg phenoxy), acyloxy group (eg acetyloxy), amino group (eg dimethylamino, morpholino), acylamino group (eg acetamido), sulfonamide group (eg methanesulfonamide, benzenesulfonamide), alkoxycarbonyl group (eg methoxy Carbonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), carbamoyl group (for example, N-methylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (for example, N-methyls) Famoyl, N, N-diethylsulfamoyl), alkylsulfonyl group (for example, methanesulfonyl), arylsulfonyl group (for example, benzenesulfonyl), alkylthio group (for example, methylthio, dodecylthio), arylthio group (for example, phenylthio, naphthylthio), cyano group , Carboxyl group and sulfo group. In addition, it is preferable that at least one R ¹² is located in the ortho position with respect to the —CONH— group, and R ¹² in the ortho position is preferably a halogen atom, an alkoxy group, an aryloxy group, an alkyl group, an alkylthio group or An arylthio group, more preferably an alkylthio group or an arylthio group, still more preferably an alkylthio group (preferably a primary alkylthio group or a tertiary alkylthio group, more preferably a primary alkylthio group, still more preferably a β-position A primary alkylthio group branched by a 2-ethylhexylthio group. Furthermore, at least one R2 is at the ortho position with respect to said -CONH- group preferably having a para-position with yet another R ¹² in the ortho position, R ¹² in the para position alkyl group ( A tertiary alkyl group, more preferably a t-butyl group, is more preferable. Most preferably, R ¹² is a 2-ethylhexylthio group at the 2-position and a t-butyl group at the 5-position with respect to the —CONH— group.
The total carbon number of R ¹² is preferably from 0 to 60, more preferably from 0 to 50, and still more preferably from 0 to 40.

n ¹ represents an integer of 0 or more and 5 or less, and when n ¹ is 2 or more, the plurality of R ¹² may be the same or different, and may be bonded to each other to form a ring. N ¹ is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and most preferably 2.

R ¹³ represents a substituent other than a hydrogen atom. Examples of this substituent include those listed above as examples of the substituent for R ¹¹ . Preferably R ¹³ is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkyl group (eg, methyl, isopropyl), aryl group (eg, phenyl, naphthyl), alkoxy group (eg, methoxy, isopropyloxy), aryloxy group (Eg phenoxy), acyloxy group (eg acetyloxy), amino group (eg dimethylamino, morpholino), acylamino group (eg acetamido), sulfonamide group (eg methanesulfonamide, benzenesulfonamide), alkoxycarbonyl group (eg methoxy Carbonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), carbamoyl group (for example, N-methylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (for example, N-methyls) Famoiru, N, N-diethyl-sulfamoyl), an alkylsulfonyl group (e.g. methanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl), a cyano group, a carboxyl group, a sulfo group.
n ² represents an integer of 0 or more and 4 or less, and when n ² is 2 or more, the plurality of R ¹³ may be the same or different, and may be bonded to each other to form a ring.

X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developer. In the present invention, X is preferably a group that can be removed by a coupling reaction with an oxidized developer.
Examples of the group in which X is a group capable of leaving by a coupling reaction with an oxidized developer include a group leaving by a nitrogen atom, a group leaving by an oxygen atom, a group leaving by a sulfur atom, a halogen atom (for example, a chlorine atom) , Bromine atom) and the like.
The group leaving from the nitrogen atom is a heterocyclic group (preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic (in the present specification, means having 4n + 2 cyclic conjugated electrons). Or a non-aromatic, monocyclic or condensed heterocyclic group, more preferably a ring-constituting atom is selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom, and a nitrogen atom, an oxygen atom and a sulfur atom. A 5- or 6-membered heterocyclic group having at least one heteroatom such as succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2, 4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole Imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazoline-2-one, 2-pyrroline-5 ON, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidin + one-3,5-dione, 2-pyridone, 4-pyridone 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidin-4-one), carbonamide group (for example, acetamide, trifluoroacetamide), sulfonamide group (for example, methanesulfonamide) , Benzenesulfonamido), arylazo groups (eg phenylazo, naphthylazo), carbamoylamino (Such as N- methylcarbamoyl amino) and the like.

  Of the groups leaving by a nitrogen atom, preferred are heterocyclic groups, and more preferred are aromatic heterocyclic groups having 1, 2, 3 or 4 nitrogen atoms as ring-constituting atoms, or the following general formula ( L) is a heterocyclic group represented.

In the formula, L represents a residue which forms a 5- to 6-membered nitrogen-containing heterocycle together with -NC (= O)-.
These exemplifications are given in the description of the heterocyclic group, and these are more preferable. Among these, L is preferably a residue that forms a 5-membered nitrogen-containing heterocycle.

  Of the groups leaving by a nitrogen atom, more preferred are imidazolidine-2,4-dione, oxazolidine-2,4-dione, imidazole and pyrazole, which may have a substituent. Most preferred is a 5,5-dimethyloxazolidine-2,4-dione-3-yl group.

Examples of the group capable of leaving with an oxygen atom include aryloxy groups (eg, phenoxy, 1-naphthoxy), heterocyclic oxy groups (eg, pyridyloxy, pyrazolyloxy), acyloxy groups (eg, acetoxy, benzoyloxy), alkoxy groups (eg, methoxy, dodecyl). Oxy), carbamoyloxy group (for example, N, N-diethylcarbamoyloxy, morpholinocarbamoyloxy), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), alkoxycarbonyloxy group (for example, methoxycarbonyloxy, ethoxycarbonyloxy), alkylsulfonyl Examples thereof include an oxy group (for example, methanesulfonyloxy) and an arylsulfonyloxy group (for example, benzenesulfonyloxy, toluenesulfonyloxy).
Of the groups leaving by an oxygen atom, preferred are an aryloxy group, an acyloxy group, and a heterocyclic oxy group.

Examples of the group that leaves with a sulfur atom include an arylthio group (for example, phenylthio, naphthylthio), a heterocyclic thio group (for example, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxazolylthio, benzimidazolylthio), Examples include alkylthio groups (for example, methylthio, octylthio, hexadecylthio), alkylsulfinyl groups (for example, methanesulfinyl), arylsulfinyl groups (for example, benzenesulfinyl), arylsulfonyl groups (for example, benzenesulfonyl), alkylsulfonyl groups (for example, methanesulfonyl), and the like. .
Of the groups leaving with a sulfur atom, preferred are an arylthio group and a heterocyclic thio group, with a heterocyclic thio group being more preferred.

X may be substituted with a substituent, and examples of the substituent for substituting X include those listed as examples of the substituent for R ¹¹ described above.
X is preferably a group leaving by a nitrogen atom, a group leaving by an oxygen atom, or a group leaving by a sulfur atom, more preferably a group leaving by a nitrogen atom, and more preferably a group leaving by a nitrogen atom. Are preferred in the order of the preferred groups mentioned above.
X may be a photographically useful group. Examples of the photographically useful group include development inhibitors, desilvering accelerators, redox compounds, dyes, couplers, and the like, or precursors thereof.
These couplers can be used alone or in combination.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in International Publication WO98 / 33760, US Pat. No. 4,923,787, etc. White couplers described in JP-A-5-249637, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, in the case of increasing the pH of the developer to speed up development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 180686846A1 And redox compounds described in French Patent No. 2760460A1 and the like are also preferably used.

  In the present invention, it is preferable to use a compound having a triazine skeleton with a high molar extinction coefficient as an ultraviolet absorber, and for example, compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or non-photosensitive. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, and 8- No. 53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. The compounds described in the specification of 19739797A, European Patent No. 711804A and JP-A-8-501291 can be used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or in combination with gelatin. As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

  In the present invention, an antibacterial / antifungal agent as described in JP-A-63-271247 is added in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.

Total Coating amount of gelatin photographic constituent layers constituting layer in the present invention is preferably not more than 3 g / m ² or more 6 g / m ^2, and more preferably 3 g / m ² or more 5 g / m ² or less. Further, even in the case of ultra-rapid processing, in order to satisfy development progress, fixing bleachability and residual color, the film thickness of the entire photographic constituent layer is preferably 3 μm to 7.5 μm, and further 3 μm to 6. It is preferable that it is 5 micrometers. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed.
Coated silver amount in the present invention, more preferably is preferably ^{0.2g / m 2 ~0.5g / m 2} , a ^{0.2g / m 2 ~0.45g / m 2} , 0.2g and most preferably / m ² ~0.40g / m ^2.

In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The photosensitive material of the present invention can form an image by an exposure process in which light is irradiated according to image information and a development process in which the photosensitive material irradiated with light is developed.
The photosensitive material of the present invention is suitable for a scanning exposure system using a cathode ray (CRT) in addition to being used in a printing system using a normal negative printer. The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy.

  When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor exhibiting light emission in a plurality of spectral regions, a plurality of colors are exposed at the same time, that is, a plurality of colors are applied to the cathode ray tube. It is also possible to emit light from the tube surface by inputting a color image signal. A method of sequentially inputting image signals for each color to cause each color to emit light sequentially and exposing through a film that cuts the colors other than that color (surface sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.

The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) using a combination of a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.
When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ⁻⁴ seconds or less, more preferably 10 ⁻⁶ seconds or less.
The silver halide color photographic light-sensitive material of the present invention is preferably imagewise exposed with a blue laser coherent light having an emission wavelength of 420 nm to 460 nm. Among blue lasers, it is particularly preferable to use a blue semiconductor laser.

  The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known documents. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. , An exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950, and a digital photo print including a remote diagnostic system described in JP-A-10-210206 And a photo print system including an image recording apparatus described in Japanese Patent Application No. 10-159187.

  In the processing of the photosensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column. The processing materials and processing methods described in the 17th line to the 18th page, lower right column, 20th line are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.

The present invention is applied as a light-sensitive material having rapid processing suitability. The color development time is 28 seconds or less, preferably 6 seconds or more and 25 seconds or less, more preferably 6 seconds or more and 20 seconds or less. Similarly, the bleach-fixing time is preferably 30 seconds or shorter, more preferably 6 seconds or longer and 25 seconds or shorter, more preferably 6 seconds or longer and 20 seconds or shorter. The washing time or stabilization time is preferably 60 seconds or shorter, more preferably 6 seconds or longer and 40 seconds or shorter.
The color development time refers to the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leaves the color developer for bleaching and fixing in the next processing step. The total of both the time during which air is conveyed toward the bath (so-called air time) is referred to as color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.

  The light-sensitive material of the present invention can be developed after exposure using a conventional developing method containing an alkali agent and a developing agent, an activator such as an alkaline solution containing the developing agent in the photosensitive material and not containing the developing agent. In addition to a wet method such as a method of developing with a beta solution, a thermal development method that does not use a processing solution can be used.

  Further, a developing method in which the amount of silver applied to the photosensitive material is reduced and image amplification processing (compensation processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695 is preferably used.

  For the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, those described in “Research Disclosure” Item 36544 (September 1994), pages 536 to 541 and JP-A-8-234388 can be used.

  In addition to the rapid processing described above, the light-sensitive material of the present invention may be processed in the manner described in JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355. The processing material and the processing method described in the fifth page, upper left column, line 17 to page 18, lower right column, line 20 can be preferably applied. As the preservative used in the developer, compounds described in the patents listed in Table 1 below are preferably used.

  Typically, Fuji Photo Film minilab "PP350", CP48S chemical is used as the processing agent, and the photosensitive material sample is subjected to imagewise exposure from an average density of negative film, and the color developer replenisher capacity is the color developer tank capacity. There is one that performs processing with a processing solution that has been subjected to continuous processing until doubled.

  The chemical of the treating agent may be CP45X, CP47L manufactured by Fuji Photo Film Co., Ltd., RA-100, RA-4 manufactured by Eastman Kodak Co., etc.

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

[Synthesis of compounds]
(Synthesis of Compound II-2)
2-Methylthieno [2,3-d] thiazole was synthesized according to the description in Example 3 of JP-A-2002-145886.
18.6 g of 2-methylthieno [2,3-d] thiazole, 25.0 g of bromoacetic acid and 20 ml of m-cresol were mixed, and the mixture was heated and stirred at 120 ° C. for 4 hours. The temperature was lowered to 80 ° C., 100 ml of acetone was added and refluxed for 1 hour. After cooling, the white precipitate was separated by filtration, washed with acetone, and powder of 3-carboxymethyl-2-methylthieno [2,3-d] thiazolium bromide 2 g was obtained.
5.9 g of the above compound, 14.7 g of 3- (5-bromo-2-sulfopropylthio-3-benzothiazolio) propanesulfonate and 120 ml of acetonitrile were added, and the mixture was heated and stirred at 60 ° C. When 22.4 ml of triethylamine was added and heated for 1 hour, a yellow precipitate was formed. The precipitate was filtered off with ice cooling and washed with acetonitrile to obtain 12.5 g of a yellow powder. It melt | dissolved in the mixed solvent of 120 ml of methanol and 20 ml of water, when 50 ml of triethylamine was added, precipitation occurred and this was separated by filtration. Further, this precipitate was dissolved in a mixed solvent of 110 ml of methanol and 110 ml of water, and 11 ml of acetic acid was added to form a precipitate, which was filtered and washed with acetone to obtain 9.3 g of II-2 yellow powder. ^The structure was confirmed by ¹ H-NMR and FAB-MS. λ max (MeOH) = 440.0 nm (ε6.87 × 10 ⁴ ).

(Synthesis of Compound III-1)
2-Methylthieno [3,2-d] thiazole was synthesized by heating and refluxing 3-acetylamino-2-bromothiophene with phosphorus pentasulfide in toluene.
18.6 g of 2-methylthieno [3,2-d] thiazole, 25.0 g of bromoacetic acid, and 20 ml of m-cresol were mixed, and the mixture was heated and stirred at 120 ° C. for 4 hours. The temperature was lowered to 80 ° C., 100 ml of acetone was added and refluxed for 1 hour. After cooling, the white precipitate was separated by filtration, washed with acetone, and powder of 3-carboxymethyl-2-methylthieno [3,2-d] thiazolium bromide 5 g was obtained.
5.9 g of the above compound, 14.7 g of 3- (5-bromo-2-sulfopropylthio-3-benzothiazolio) propanesulfonate and 120 ml of acetonitrile were added, and the mixture was heated and stirred at 60 ° C. When 22.4 ml of triethylamine was added and heated for 1 hour, a yellow precipitate was formed. The precipitate was filtered off with ice cooling and washed with acetonitrile to obtain 10.3 g of a yellow powder. It was dissolved in a mixed solvent of 100 ml of methanol and 15 ml of water, and 35 ml of triethylamine was added to form a precipitate, which was filtered off. Further, this precipitate was dissolved in a mixed solvent of 90 ml of methanol and 90 ml of water, and 9 ml of acetic acid was added to form a precipitate, which was filtered and washed with acetone to obtain 8.2 g of III-1 yellow powder. ^The structure was confirmed by ¹ H-NMR and FAB-MS. [lambda] max (MeOH) = 432.0 nm ([epsilon] 6.15 * 10 < ⁴ >).

[Preparation of emulsion]
(Preparation of emulsions B-10 to 16) Comparative example: Silver chlorobromide cube 0.46 μm
High silver chloride cubic particles were prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added to a stirred gelatin aqueous solution and mixed. However, from the time when the addition of silver nitrate is 80% to 90%, potassium bromide is added in an amount of 2 mol% per mol of the finished silver halide, and 90% from the time when addition of silver nitrate is 80%. To this point, K ₄ [Ru (CN) ₆ ] was added. Further, K ₂ [IrCl ₆ ] is added from the time point when the addition of silver nitrate is 83% to 88%, and K ₂ [Ir (5-methylthiazole) Cl ₅ is added from the time point when the addition of silver nitrate is 90% to 95%. ] Was added. The obtained emulsion was desalted and then re-dispersed with gelatin. The obtained grain was a cubic emulsion surrounded by six parallel {100} planes and having a cube side length of 0.46 μm and a coefficient of variation of 9.5%.

This emulsion was dissolved at 40 ° C., and sensitizing dye Dye-1 was added at 4 × 10 ⁻⁴ mol per mol of silver halide and sodium benzenethiosulfonate was added at 2 × 10 ⁻⁵ mol per mol of silver halide. , Sodium thiosulfate pentahydrate as a sulfur sensitizer and bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate as a gold sensitizer Aged to be optimal. Further, 2.7 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole per mol of silver halide and 2.7 of 1- (5-methylureidophenyl) -5-mercaptotetrazole per mol of silver halide. × 10 ⁻⁴ mol was added, and 2.7 × 10 ⁻³ mol of potassium bromide was added per mol of silver halide. The emulsion thus obtained was designated as Emulsion B-11.

Further, emulsions B-11 to B-16 differed from emulsion B-11 only in that the sensitizing dye Dye-1 added at the time of post-ripening was changed to the sensitizing dye shown in Table 2. The emulsion to which no sensitizing dye was added was designated as Emulsion B-10.
(Preparation of emulsions B-20 to 26) Comparative example: silver iodobromochloride cube 0.62 μm
High silver chloride cubic particles were prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added to a stirred gelatin aqueous solution and mixed. However, from the time when the addition of silver nitrate is 80% to 90%, potassium bromide is added in an amount of 2 mol% per mol of the finished silver halide, and 90% from the time when addition of silver nitrate is 80%. To this point, K ₄ [Ru (CN) ₆ ] was added. In addition, K ₂ [IrCl ₆ ] was added from the time point when the addition of silver nitrate was 83% to the time point of 88%, and when the addition of silver nitrate was completed 90%, an aqueous potassium iodide solution was obtained. An amount of 0.24 mol% was added with vigorous mixing, and K ₂ [Ir (5-methylthiazole) Cl ₅ ] was added from the point of 90% to 95% of the addition of silver nitrate.
The obtained emulsion was desalted and then re-dispersed with gelatin. The obtained grains were a cubic emulsion surrounded by six parallel {100} planes and having a cube side length of 0.62 μm and a coefficient of variation of 8.9%.

This emulsion was dissolved at 40 ° C., and sensitizing dye Dye-1 was added at 4 × 10 ⁻⁴ mol per mol of silver halide and sodium benzenethiosulfonate was added at 2 × 10 ⁻⁵ mol per mol of silver halide. , Sodium thiosulfate pentahydrate as a sulfur sensitizer and bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate as a gold sensitizer Aged to be optimal. Further, 1-phenyl-5-mercaptotetrazole was 2.7 × 10 ⁻⁴ mole per mole of silver halide and 2.7 × per mole of 1- (5-methylureidophenyl) -5-mercaptotetrazole silver halide. 10 ⁻⁴ mol was added, and 2.7 × 10 ⁻³ mol of potassium bromide was added per mol of silver halide. The emulsion thus obtained was designated as Emulsion B-21.

  Emulsions B-21 to B-26 differed from emulsions B-21 except that the sensitizing dye Dye-1 added at the time of post-ripening was changed to the sensitizing dyes shown in Table 2. An emulsion to which no sensitizing dye was added was designated as Emulsion B-20.

(Preparation of emulsion B-30 to 39) Silver iodobromochloride cube 0.46 μm
Emulsion B-11 means that when 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added with vigorous mixing in an amount that would result in an I content of 0.24 mol% per mole of the finished silver halide. Except for the above, an emulsion was prepared in the same manner as Emulsion B-11. The obtained grain was a cubic silver chloroiodobromide emulsion surrounded by six parallel {100} planes and having a cube side length of 0.46 μm and a coefficient of variation of 9.5%. Emulsion B-31 was obtained. The distribution of iodide ion concentration in the depth direction shows that, according to the etching / TOF-SIMS method, iodide ions ooze out toward the particle surface, have a gradual concentration maximum on the outermost surface, and concentration toward the inside. Was decaying.

Emulsions B-31 to B-39 were different from the emulsion B-31 only in that the sensitizing dye Dye-1 added at the time of post-ripening was changed to the sensitizing dye shown in Table 2. An emulsion to which no sensitizing dye was added was designated as Emulsion B-30.
(Preparation of emulsion B-40 to 46) Comparative example: Silver iodobromochloride cube 0.46 μm
Emulsion B-11 means that when 70% of the addition of silver nitrate was completed, an aqueous solution of potassium iodide was added with vigorous mixing in an amount of 0.24 mol% per mol of the finished silver halide. Except for the above, an emulsion was prepared in the same manner as Emulsion B-11. The obtained grain was a cubic silver chloroiodobromide emulsion surrounded by six parallel {100} faces and having a cube side length of 0.46 μm and a coefficient of variation of 9.5%. Emulsion B-41 was obtained.

  Furthermore, emulsions B-41 differed in that the sensitizing dye Dye-1 added at the time of post-ripening was changed to the sensitizing dyes shown in Table 2, and were designated as emulsions B-42 to B-46, respectively. An emulsion to which no sensitizing dye was added was designated as Emulsion B-40.

(Preparation of emulsions B-50 to 56) Comparative example: {100} silver iodobromochloride flat plate 0.46 μm
At a constant temperature of 27 ° C., silver nitrate and sodium chloride were simultaneously added to the stirred gelatin aqueous solution with vigorous stirring. Further, potassium bromide was vigorously mixed in an amount of 0.46 mol% per mol of the finished silver halide. While adding. Further, silver nitrate and sodium chloride were added simultaneously. The temperature was raised to 75 ° C. and optimally ripened, and silver nitrate and sodium chloride were added as a growth process to grow the desired particle size. At this time, when 90% of the addition of silver nitrate was completed, an amount of I amounting to 0.24 mol% per 1 mol of the finished silver halide aqueous solution was added with vigorous mixing. From 80% to 90%, potassium bromide was added in vigorous mixing in an amount of 2 mole% per mole of finished silver halide.
Also, K ₄ [Ru (CN) ₆ ] is added from the time point when the addition of silver nitrate is 80% to 90%, and K ₂ [IrCl ₆ ] is added from the time point when the addition of silver nitrate is 83% to 88%. Added. Further, K ₂ [Ir (5-methylthiazole) Cl ₅ ] was added from 90% to 95% when silver nitrate was added. Thereafter, the obtained emulsion was desalted and then re-dispersed with gelatin.

  A part of the emulsion was collected, and an electron micrograph (TEM image) of a replica of the grain was observed. According to it, 95.1% of the projected area meter of all silver halide grains is tabular grains having a {100} plane as the main plane, with an average grain size of 0.90 μm, an average grain thickness of 0.150 μm, and an average aspect. The particles had a ratio of 6.1, an average adjacent side ratio of 1.12, and a cubic conversion side length of 0.46 μm.

This emulsion was dissolved at 40 ° C., and sensitizing dye Dye-1 was added at 4 × 10 ⁻⁴ mol per mol of silver halide and sodium benzenethiosulfonate was added at 2 × 10 ⁻⁵ mol per mol of silver halide. , Sodium thiosulfate pentahydrate as a sulfur sensitizer and bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate as a gold sensitizer Aged to be optimal. Further, 1-phenyl-5-mercaptotetrazole was 2.7 × 10 ⁻⁴ mole per mole of silver halide and 2.7 × per mole of 1- (5-methylureidophenyl) -5-mercaptotetrazole silver halide. 10 ⁻⁴ mol was added, and 2.7 × 10 ⁻³ mol of potassium bromide was added per mol of silver halide. The emulsion thus obtained was designated as Emulsion B-51.

  Furthermore, emulsions B-51 were changed to emulsion B-52 to B-56, respectively, except that the sensitizing dye Dye-1 added at the time of post-ripening was changed to the sensitizing dye shown in Table 2. The emulsion to which no sensitizing dye was added was designated as Emulsion B-50.

(Preparation of emulsion G-1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, K ₄ [Ru (CN) ₆ ] was added from the time when the addition of silver nitrate was 80% to 90%. Potassium bromide (4 mol% per mole of finished silver halide) was added from the 80% to 100% addition of silver nitrate. When the addition of silver nitrate was completed 90%, potassium iodide (0.2 mol% per mol of the finished silver halide) was added. K ₂ [Ir (5-methylthiazole) Cl ₅ ] was added from the point when the addition of silver nitrate was 92% to the point when it was 95%. Further, K ₂ [Ir (H ₂ O) Cl ₅ ] was added from the time when the addition of silver nitrate was 92% to the time when it was 98%. The obtained emulsion was desalted and then re-dispersed with gelatin. 2 × 10 ⁻⁵ mol of sodium benzenethiosulfonate is added to this emulsion per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and bis (1,4,5- Trimethyl-1,2,4-triazolium-3-thiolate) aurate (I) tetrafluoroborate was used for optimal aging. Further, sensitizing dye Dye-2 is 6 × 10 ⁻⁴ mol per mol of silver halide, 1-phenyl-5-mercaptotetrazole is 2 × 10 ⁻⁴ mol per mol of silver halide, 1- (5-methylureido Phenyl) -5-mercaptotetrazole was added at 8 × 10 ⁻⁴ mole per mole of silver halide and potassium bromide was added at 7 × 10 ⁻³ mole per mole of silver halide. The emulsion thus obtained was designated as Emulsion G-1.

(Preparation of emulsion R-1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, K ₄ [Ru (CN) ₆ ] was added from the time when the addition of silver nitrate was 80% to 90%. Potassium bromide (4.3 mol% per mol of the finished silver halide) was added from the 80% to 100% addition of silver nitrate. When 90% of the addition of silver nitrate was completed, potassium iodide (0.15 mol% per mol of the finished silver halide) was added. K ₂ [Ir (5-methylthiazole) Cl ₅ ] was added from the point when the addition of silver nitrate was 92% to the point when it was 95%.
Further, K ₂ [Ir (H ₂ O) Cl ₅ ] was added from the time when the addition of silver nitrate was 92% to the time when it was 98%. The obtained emulsion was desalted and then re-dispersed with gelatin. 2 × 10 ⁻⁵ mol of sodium benzenethiosulfonate is added to this emulsion per mol of silver halide, sodium thiosulfate pentahydrate as a sulfur sensitizer and bis (1,4,5- Trimethyl-1,2,4-triazolium-3-thiolate) aurate (I) tetrafluoroborate was used for optimal aging. Further sensitizing dye Dye-6 per mol of silver halide per 2 × 10 ^-4 mol, 1-phenyl-5-mercaptotetrazole per mol of silver halide 2 × 10 ^-4 mol, 1- (5-methylureidophenyl ) -5-mercaptotetrazole 8 × 10 ⁻⁴ mole per mole of silver halide, compound-1 1 × 10 ⁻³ mole per mole of silver halide and potassium bromide 7 × 10 5 mole per mole of silver halide ^-3 mol was added. The emulsion thus obtained was designated as Emulsion R-1.

[Preparation of silver halide color photographic material]
After the corona discharge treatment is applied to the surface of the support formed by coating both sides of the paper with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate is provided. The layers were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows.

First layer coating solution preparation 57 g of yellow coupler (ExY-1), 7 g of color image stabilizer (Cpd-1), 4 g of color image stabilizer (Cpd-2), 7 g of color image stabilizer (Cpd-3), color image 2 g of stabilizer (Cpd-8) was dissolved in 21 g of solvent (Solv-1) and 80 ml of ethyl acetate, and this liquid was stirred and emulsified in 220 g of 23.5% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate. Emulsified and dispersed with (dissolver), and water was added to prepare 900 g of emulsified dispersion A.
On the other hand, the emulsified dispersion A and the emulsion B-11 were mixed and dissolved, and a first layer coating solution was prepared so as to have the composition described later. The emulsion coating amount indicates the silver coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As gelatin hardeners for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt H-1, H-2, and H-3 were used. Also, Ab-1 to each layer, Ab-2, Ab-3 , and Ab-4 to the total amount of each ^{15.0mg / m 2, 60.0mg / m} 2, 5.0mg / m 2 and 10.0 mg / m It added so that it might become ² .

Further, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, at 1.0 × 10 ⁻³ mol and 5.9 × 10 ⁻⁴ mol per mol of silver halide. . Further, the second layer, in the fourth layer and the sixth layer of 1-phenyl-5-mercaptotetrazole, respectively 0.2 mg / m ^2, so that 0.2 mg / m ² and 0.6 mg / m ² Added.
0.05 g / m ^{2 of} copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer. Further, the second layer was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support Polyethylene resin laminated paper [White pigment (TiO ₂ ; content 16 mass%, ZnO; content 4 mass%) and fluorescent whitening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene, containing 0.03% by mass) and containing a bluish dye (ultraviolet)]
First layer (blue sensitive emulsion layer)
Emulsion B-11 0.19
Gelatin 1.00
Yellow coupler (ExY-1) 0.46
Color image stabilizer (Cpd-1) 0.06
Color image stabilizer (Cpd-2) 0.03
Color image stabilizer (Cpd-3) 0.06
Color image stabilizer (Cpd-8) 0.02
Solvent (Solv-1) 0.17

Second layer (color mixing prevention layer)
Gelatin 0.50
Color mixing inhibitor (Cpd-4) 0.05
Color image stabilizer (Cpd-5) 0.01
Color image stabilizer (Cpd-6) 0.06
Color image stabilizer (Cpd-7) 0.01
Solvent (Solv-1) 0.03
Solvent (Solv-2) 0.11

Third layer (green sensitive emulsion layer)
Emulsion G-1 0.12
Gelatin 1.36
Magenta coupler (ExM-1) 0.15
Ultraviolet absorber (UV-A) 0.14
Color image stabilizer (Cpd-2) 0.02
Color image stabilizer (Cpd-4) 0.002
Color image stabilizer (Cpd-6) 0.09
Color image stabilizer (Cpd-8) 0.02
Color image stabilizer (Cpd-9) 0.03
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-11) 0.0001
Solvent (Solv-3) 0.11
Solvent (Solv-4) 0.22
Solvent (Solv-5) 0.20

Fourth layer (color mixing prevention layer)
Gelatin 0.36
Color mixing prevention layer (Cpd-4) 0.03
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (Cpd-7) 0.004
Solvent (Solv-1) 0.02
Solvent (Solv-2) 0.08

5th layer (red-sensitive emulsion layer)
Emulsion R-1 0.10
Gelatin 1.11
Cyan coupler (ExC-1) 0.13
Cyan coupler (ExC-2) 0.016
Cyan coupler (ExC-3) 0.008
Cyan coupler (ExC-4) 0.006
Color image stabilizer (Cpd-1) 0.05
Color image stabilizer (Cpd-6) 0.06
Color image stabilizer (Cpd-7) 0.02
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-14) 0.01
Color image stabilizer (Cpd-15) 0.12
Color image stabilizer (Cpd-16) 0.03
Color image stabilizer (Cpd-17) 0.09
Color image stabilizer (Cpd-18) 0.07
Solvent (Solv-5) 0.15
Solvent (Solv-8) 0.05

Sixth layer (UV absorbing layer)
Gelatin 0.46
Ultraviolet absorber (UV-B) 0.45
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.25
Seventh layer (protective layer)
Gelatin 1.00
Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.01

  The sample obtained as described above was designated as Sample S (11). Samples S (11) were prepared in the same manner as the samples in which the emulsions in the blue-sensitive emulsion layer were changed as shown in Table 2, and designated as Samples S (10) to S (56).

(Evaluation 1: Sensitivity and residual color)
In order to examine the photographic characteristics of these samples, the following experiment was conducted.
Each coated sample is left in an atmosphere of 25 ° C. and 30% RH, and in that environment, using a high-illuminance exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.) for gray color sensitometry For 10 ^-6 seconds high intensity gradation exposure. The exposed sample was subjected to [color development processing a] shown below 10 seconds after exposure.

The processing steps are shown below.
[Color development processing a]
The above photosensitive material sample is processed into a 127 mm width roll, and image-wise exposure is performed on the photosensitive material sample from a negative film having an average density using an experimental processing device modified from Fuji Photo Film's minilab printer processor PP350. Continuous processing (running test) was performed until the volume of the color developer replenisher used in the following processing steps was 0.5 times the volume of the color developer tank.

Processing temperature Temperature Time Replenishment amount ^*
Color development 45.0 ℃ 16 seconds 45ml
Bleach fixing 40.0 ℃ 16 seconds 35ml
Rinse 1 40.0 ° C 8 seconds-
Rinse 2 40.0 ° C 8 seconds-
Rinse 3 ** 40.0 ° C 8 seconds-
Rinse 4 38.0 ° C 8 seconds 121ml
Drying 80.0 ° C. 16 seconds (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material ** Fuji Photo Film Co., Ltd. Rinse Screening System RC50D is attached to Rinse (3), and rinse liquid is taken out from Rinse (3) To the reverse osmosis module (RC50D). The permeated water sent in the tank is supplied to the rinse, and the concentrate is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. The rinsing was a 4-tank countercurrent system from (1) to (4).

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800ml water 600ml
Optical brightening agent (FL-1) 5.0 g 8.5 g
Triisopropanolamine 8.8g 8.8g
Sodium p-toluenesulfonate 20.0 g 20.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.50g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5 g 14.5 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydride 10.0 g 22.0 g
Potassium carbonate 26.3g 26.3g
Add water to make 1000ml 1000ml
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.35 12.6

[Bleaching Fixer] [Tank Solution] [Replenisher]
800ml water 800ml
Ammonium thiosulfate (750 g / ml)
107ml 214ml
Succinic acid 29.5g 59.0g
Ethylenediaminetetraacetic acid iron (III) ammonium
47.0g 94.0g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 17.5g 35.0g
Imidazole 14.6g 29.2g
Ammonium sulfite 16.0 g 32.0 g
Potassium metabisulfite 23.1g 46.2g
Add water to make 1000ml 1000ml
pH (adjusted with 25 ° C, nitric acid and aqueous ammonia) 6.00 6.00

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000ml 1000ml
pH (25 ° C.) 6.5 6.5

The yellow color density of each sample after the treatment was measured to obtain a characteristic curve of 10 ⁻⁶ seconds high illumination exposure. Sensitivity was defined as the reciprocal of the exposure amount giving a color density 1.0 higher than the minimum color density.
The sensitivity when the sample S (11) was exposed at 25 ° C. and 30% RH and processed in [color development processing a] was set to 100, and the relative sensitivities thereof are shown in Table 3.

  From the lowest yellow color density of the unexposed areas after the processing of the samples S (11) to S (56) prepared in the evaluation 1, the respective dye blank samples S (10), S (20), S (30) The residual color of the sensitizing dye was evaluated by subtracting the lowest yellow color density of the unexposed area after the processing of S, S (40) and S (50). The results are shown in Table 3. A smaller value indicates less residual color of the sensitizing dye.

(Evaluation 2: Processing solution fluctuation stability)
Further, in order to investigate the stability of the processing solution fluctuation, [color development processing b] and [color development processing c] are carried out with respect to [color development processing a] in which only the replenishment amount of the color developer is ± 15%. It was.
First, using a high-illuminance exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.) with a sample left sufficiently in an atmosphere of 25 ° C. and 30% RH in its environment, 10 ⁻ for gray color sensitometry. ^{A 6} second high intensity gradation exposure was given. Next, the exposed sample was subjected to the following [color development processing b] and [color development processing c].

[Color development processing b] means that the replenishment amount of color development is 1 with respect to [color development processing a].
The treatment recipe is shown below with a different treatment recipe only by an increase of 5%.
Processing temperature Temperature Time Replenishment amount ^*
Color development 45.0 ℃ 16 seconds 51.8ml
Bleach fixing 40.0 ℃ 16 seconds 35ml
Rinse 1 40.0 ° C 8 seconds-
Rinse 2 40.0 ° C 8 seconds-
Rinse 3 ** 40.0 ° C 8 seconds-
Rinse 4 38.0 ° C 8 seconds 121ml
Drying 80.0 ° C 16 seconds

[Color development processing c] means that the replenishment amount of color development is 1 with respect to [color development processing a].
Only a 5% reduction resulted in a different treatment recipe. The treatment recipe is shown below.
Processing temperature Temperature Time Replenishment amount ^*
Color development 45.0 ℃ 16 seconds 38.3ml
Bleach fixing 40.0 ℃ 16 seconds 35ml
Rinse 1 40.0 ° C 8 seconds-
Rinse 2 40.0 ° C 8 seconds-
Rinse 3 ** 40.0 ° C 8 seconds-
Rinse 4 38.0 ° C 8 seconds 121ml
Drying 80.0 ° C 16 seconds

The yellow color density of each sample after each treatment was measured to obtain a characteristic curve. Here, the gradation (γ) is defined as the logarithm of the difference between the reciprocal of the exposure amount between the point giving the color density of minimum color density +1.4 and the point giving the color density of minimum color density +2.0. The gradation variation rate Δγ = (γ _(b) / γ _(c) ) between the gradation (γ) when the color development processing b is processed and the gradation (γ) when the color development processing c is processed. Table 3 shows. The closer the value of Δγ is to 1.0, the smaller the effect on processing fluctuation.

As is apparent from the results in Table 3, samples S (11) to S (16) of the silver chlorobromide emulsion and S (41) to S (46) in which a silver iodide phase was formed inside the grains were dye adsorption. May be weak and has extremely low sensitivity. All the silver iodobromochloride emulsion samples in which the silver iodide-containing phase is formed at a position of 90% from the inside are highly sensitive, but large-sized grains S (21) to S (26) and S of tabular grains are used. In (51) to S (56), the change of the gradation with respect to the processing liquid fluctuation is too large. The samples S (32) to S (39) of the present invention have higher sensitivity and less residual color than the sample S (31) using the dye Dye-1 of the comparative example, and also change the gradation even when the processing solution varies. And a stable print density can be obtained.
Among the cyanine compounds of the general formula (I) of the present invention, the cyanine compounds represented by the general formula (II) and the general formula (III) showed the most excellent performance (samples S (32) to S (37)). ).

Images were formed by laser scanning exposure using samples S (11) to S (56).
As a laser light source, a YAG solid-state laser (oscillation wavelength 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength 808.5 nm) as an excitation light source was converted into a wavelength of 473 nm using a LiNbO ₃ SHG crystal having an inverted domain structure, and a semiconductor. A YVO ₄ solid-state laser (oscillation wavelength 1064 nm) using a laser GaAlAs (oscillation wavelength 808.7 nm) as an excitation light source was converted to 532 nm using a LiNbO ₃ SHG crystal having an inverted domain structure, and AlGaInP (oscillation wavelength about 680 nm). : Matsushita Densen type No. LN9R20). The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by the polygon mirror so that the sample can be sequentially scanned and exposed. Variation in the amount of light due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter was 80 μm, the scanning pitch was 42.3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds.
When the coated samples S (11) to S (56) were evaluated in the same manner as in Example 1 by replacing the sensitometer with the laser scanning exposure, the sample of the present invention was highly sensitive as in the result of Example 1. It was found to be an emulsion with little residual color and little dependence on processing solution variations, and was suitable for image formation using laser scanning exposure.

(Preparation of blue-sensitive layer emulsion B-H1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, from 85% to 95% addition of silver nitrate, potassium bromide was added in an amount of 1.5 mol% per mole of finished silver halide, and the addition of silver nitrate was 80%. From ₄ % to 90%, K ₄ [Fe (CN) ₆ ] is 4 × 10 ⁻⁶ mol / silver mol, K ₄ [Ru (CN) ₆ ] is 6 × 10 ⁻⁶ mol / silver mol, K ₂ [Ir (5-methylthiazole) Cl ₅ ] is 5 × 10 ⁻⁸ mol / silver mol, K ₂ [RhBr ₅ (H ₂ O)] is 3 × 10 ⁻⁹ mol / silver mol and K ₂ [OsCl ₅ ( NO)] was added in increments of 4 × 10 ⁻⁹ mol / silver mol. Further, when the addition of silver nitrate was 92% to 98%, K ₂ [IrCl ₅ (H ₂ O)] was 8 × 10 ⁻⁶ mol / silver mol and K [IrCl ₅ (H ₂ O) ₂ ] was 1 × 10 ^-6 mol / silver mol was added. Further, when 90% of the addition of silver nitrate was completed, the potassium iodide solution was added with vigorous stirring so that the amount of iodine per mole of the finished silver halide was 0.27 mol%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.54 μm and a coefficient of variation of 8.5%. This emulsion was subjected to precipitation desalting treatment, and gelatin, compounds Ab-1, Ab-2, Ab-3 and calcium nitrate were added and redispersed.

The redispersed emulsion was dissolved at 40 ° C., 2 × 10 ⁻⁵ mol / silver mol of sodium benzenethiosulfonate, 2 × 10 ⁻⁶ mol / silver mol of triethylthiourea as a sulfur sensitizer, and gold sensitizer. As a result, Compound 2 was added at 3 × 10 ⁻⁵ mol / silver mol, and the mixture was aged so that post-ripening was optimized. Then, 1 × (5-methylureidophenyl) -5-mercaptotetrazole was 2 × 10 ⁻⁴ mol / silver mol, Compound-3 was 8 × 10 ⁻⁶ mol / silver mol, and Compound-4 was 1 × 10 ^−5. Mole / silver mole and 2 × 10 ⁻³ mole / silver mole of potassium bromide were added. Further, spectral sensitization was performed by adding 6 × 10 ⁻⁴ mol / silver mol of sensitizing dye II-2 of the present invention as a sensitizing dye during the emulsion preparation process. The emulsion thus obtained was named Emulsion B-H1.

(Preparation of blue-sensitive layer emulsion B-L1)
In the preparation of Emulsion B-H1, except that the temperature and rate of addition of silver nitrate and sodium chloride were changed and mixed, and the amount of various metal complexes added during the addition of silver nitrate and sodium chloride was changed. Emulsion grains were obtained in the same manner. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.34 μm and a coefficient of variation of 9.5%. After redispersing this emulsion, Emulsion B-L1 was prepared in the same manner except that the amount of various compounds added was changed from B-H1.

(Preparation of blue-sensitive emulsions B-H2 and B-L2)
Emulsions B-H2 and Emulsions were prepared in the same manner as in the preparation of Emulsions B-H1 and B-L1, except that a potassium iodide solution was added so that the amount of iodide was 0.10 mol% per mol of the finished silver halide. B-L2 was prepared.

(Preparation of blue-sensitive emulsions B-H3 and B-L3)
Emulsions B-H3 and Emulsions were prepared in the same manner as in the preparation of Emulsions B-H1 and B-L1, except that a potassium iodide solution was added so that the amount of iodine was 0.45 mol% per mol of the finished silver halide. B-L3 was prepared.

(Preparation of green-sensitive layer emulsion GH)
Emulsion grains were prepared using the same method as that for preparing the blue-sensitive emulsion. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.48 μm and a coefficient of variation of 8.0%. This emulsion was subjected to precipitation desalting and redispersion.

  This emulsion was dissolved at 40 ° C. and sodium benzenethiosulfonate, p-glutaramide phenyl disulfide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (bis (1,4,5-trimethyl) as a gold sensitizer. -1,2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) was added and ripened to optimize post-ripening. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-3 and potassium bromide were added. Further, spectral sensitization was performed by adding Dye-2 to Dye-5 as sensitizing dyes during the emulsion preparation process. The emulsion thus obtained was named Emulsion GH.

(Preparation of green-sensitive layer emulsion GL)
In the preparation of emulsion GH, except that the temperature and rate of addition of silver nitrate and sodium chloride are changed simultaneously and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride are changed. Emulsion grains were obtained in the same manner. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.25 μm and a coefficient of variation of 9.8%. After redispersion of this emulsion, Emulsion GL was prepared in the same manner except that the amount of various compounds added was changed from that of Emulsion GH.

(Preparation of emulsion RH for red-sensitive layer)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, the amount of potassium bromide was added in an amount of 2.5 mol% per mol of the finished silver halide from the time when the addition of silver nitrate was 65% to 90%, and the addition of silver nitrate was 70%. % To 85% from K ₄ [Fe (CN) ₆ ], K ₄ [Ru (CN) ₆ ], K ₂ [Ir (5-methylthiazole) Cl ₅ ], K ₃ [RhBr ₆ ] and K ₂ [RuCl ₅ (NO)] was added. Further, K ₂ [IrCl ₅ (H ₂ O)] was added when the addition of silver nitrate was 85% to 98%. Further, when 88% of the addition of silver nitrate was completed, the potassium iodide solution was added with vigorous stirring so that the amount of iodine was 0.15 mol% per mol of the finished silver halide. The obtained emulsion grains were monodispersed cubic silver iodobromochloride emulsion grains having a cube side length of 0.39 μm and a coefficient of variation of 10%. The obtained emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C., and sensitizing dye Dye-6, compound-1, triethylthiourea as sulfur sensitizer and compound-2 as gold sensitizer were added, and ripened so that post-ripening was optimized. did. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-3 and compound-4 were added. The emulsion thus obtained was named Emulsion RH.

(Preparation of emulsion RL for red-sensitive layer)
In the preparation of emulsion RH, except that the temperature and rate of addition of silver nitrate and sodium chloride are mixed and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride are changed. Emulsion grains were obtained in the same manner. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.29 μm and a coefficient of variation of 9.9%. This emulsion was subjected to precipitation desalting treatment and redispersion, and then emulsion RL was prepared in the same manner except that the amount of various compounds added was changed from that of emulsion RH.

Preparation of first layer coating solution 34.0 g of yellow coupler (ExY-2), 1.0 g of color image stabilizer (Cpd-1), 1.0 g of color image stabilizer (Cpd-2), color image stabilizer (Cpd- 8) 8.0 g, color image stabilizer (Cpd-18) 1.0 g, color image stabilizer (Cpd-19) 2.0 g, color image stabilizer (Cpd-20) 15.0 g, color image stabilizer ( Cpd-21) 1.0 g, color image stabilizer (Cpd-23) 15 g, additive (ExC-5) 0.1 g, color image stabilizer (UV-3) 1.0 g and solvent (Solv-4) 23 g , 4 g of solvent (Solv-6), 23 g of solvent (Solv-13) and 60 ml of ethyl acetate, this solution was dissolved in 270 g of a 20% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate and a high-speed stirring emulsifier (dissolver). Emulsified and dispersed with water and added 9 00 g of emulsified dispersion A was prepared.
On the other hand, the emulsified dispersion A and the emulsions B-H1 and B-L1 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. Further, the total amount Ab-1, Ab-2 to each layer, and Ab-3, respectively is 15.0 mg / m ^2, was added to a 60.0 mg / m ² and 5.0 mg / m ^2.

In addition, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the second layer, the fourth layer, and the sixth layer, respectively, at 0.25 mg / m ² , 0.15 mg / m ² , 0.6 mg / was added such that the m ^2.
Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, at 1 × per mole of silver halide. 10 ⁻⁴ mol, 2 × 10 ⁻⁴ , and 5 × 10 ⁻⁵ mol were added.
Further, 0.05 g / m ² of a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer.
Furthermore the second layer, was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2.
In addition, sodium polystyrene sulfonate was added to each layer as necessary to adjust the viscosity of the coating solution.
In order to prevent irradiation, the following dyes were added so as to have the following coating amounts.

Dye (D-1) 2 mg / m ²
Dye (D-2) 2 mg / m ²
Dye (D-3) 24 mg / m ²
Dye (D-4) 3 mg / m ²

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support Polyethylene resin-laminated paper [white pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass) and polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by mass) and bluish dye (ultraviolet, content 0.30% by mass). The amount of polyethylene resin is 29.2 g / m ² ]
First layer (blue sensitive emulsion layer)
Silver iodobromochloride emulsion (gold-sulfur sensitized cube, 6: 4 mixture of large size emulsion B-H1 and small size emulsion B-L1 (silver molar ratio))
0.16
Gelatin 1.32
Yellow coupler (ExY-2) 0.34
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.08
Color image stabilizer (Cpd-18) 0.01
Color image stabilizer (Cpd-19) 0.02
Color image stabilizer (Cpd-20) 0.15
Color image stabilizer (Cpd-21) 0.01
Additive (ExC-5) 0.001
Color image stabilizer (UV-3) 0.01
Solvent (Solv-4) 0.23
Solvent (Solv-6) 0.04
Solvent (Solv-13) 0.23

Second layer (color mixing prevention layer)
Gelatin 0.78
Color mixing inhibitor (Cpd-24) 0.05
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (Cpd-7) 0.006
Color image stabilizer (Cpd-12) 0.01
Color image stabilizer (UV-C) 0.06
Solvent (Solv-1) 0.06
Solvent (Solv-10) 0.06
Solvent (Solv-5) 0.07
Solvent (Solv-12) 0.07

Third layer (green sensitive emulsion layer)
Silver iodobromochloride emulsion (gold-sulfur sensitized cube, 7: 3 mixture of large size emulsion GH and small size emulsion GL (silver molar ratio))
0.12
Gelatin 0.95
Magenta coupler (ExM-2) 0.12
UV absorber (UV-C) 0.03
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-20) 0.01
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.12
Solvent (Solv-6) 0.05
Solvent (Solv-13) 0.16

Fourth layer (color mixing prevention layer)
Gelatin 0.65
Color mixing inhibitor (Cpd-24) 0.045
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.04
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-12) 0.008
Color image stabilizer (UV-C) 0.05
Solvent (Solv-1) 0.05
Solvent (Solv-10) 0.05
Solvent (Solv-5) 0.06
Solvent (Solv-12) 0.06

5th layer (red-sensitive emulsion layer)
Silver iodobromochloride emulsion (gold-sulfur sensitized cube, 3: 7 mixture of large size emulsion RH and small size emulsion RL (silver molar ratio))
0.10
Gelatin 1.11
Cyan coupler (ExC-5) 0.11
Cyan coupler (ExC-2) 0.01
Cyan coupler (ExC-4) 0.04
Color image stabilizer (Cpd-1) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.18
Color image stabilizer (Cpd-16) 0.002
Color image stabilizer (Cpd-17) 0.001
Color image stabilizer (Cpd-18) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-9) 0.10
Solvent (Solv-5) 0.19

Sixth layer (UV absorbing layer)
Gelatin 0.34
Ultraviolet absorber (UV-D) 0.24
Compound (S1-4) 0.0015
Solvent (Solv-11) 0.11
Seventh layer (protective layer)
Gelatin 0.82
Additive (Cpd-22) 0.03
Liquid paraffin 0.02
Surfactant (Cpd-25) 0.02

A coated sample 101 was produced as described above. Similar to the preparation of emulsions B-H1 and B-L1 in the first layer with respect to sample 101, except that the compounds shown in Table 4 were added in the amounts shown in Table 4 instead of adding sensitizing dye II-2. Thus, samples 102 to 126 were produced.
Also, instead of using emulsions B-H1 and B-L1 in the first layer for sample 101, B-H2 and B-L2, B-H3 and B-L3, and adding sensitizing dye II-2 Samples 201, 202, 301, and 302 were prepared in the same manner except that the compounds shown in Table 4 were added in the amounts shown in Table 4.
Each sample was subjected to the following evaluation after being stored for 7 days at 25 ° C. and 60% relative humidity after the photosensitive material was applied.

  The above photosensitive material 101 was processed into a roll having a width of 127 mm, and a standard photographic image was exposed on the photosensitive material using an experimental processing device in which Digital Minilab Frontier 350 (manufactured by Fuji Photo Film Co., Ltd.) was modified. Thereafter, continuous processing (running test) was performed until the volume of the color developer replenisher used in the following processing steps was 1.5 times the volume of the color developer tank.

Process D
The treatment using the following running treatment liquid was designated as treatment D.

Processing temperature Temperature Time Replenishment amount ^*
Color development 38.5 ° C 45 seconds 45 ml
Bleach fixing 38.0 ° C 45 seconds 35 ml
Rinse 1 38.0 ° C. 20 seconds −
Rinse 2 38.0 ° C 20 seconds-
Rinse 3 ** 38.0 ° C 20 seconds-
Rinse 4 ** 38.0 ° C 20 seconds 121ml
Dry 80 ° C
(note)
* Replenishment amount per 1 m ^{2 of} photosensitive material ** A rinsing screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is attached to the rinsing 3, and the rinsing liquid is taken out from the rinsing 3 and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. The rinsing was a 4-tank counterflow system from 1 to 4. The tank capacity of each processing step was 400 ml, and continuous processing was performed so that the color developer replenisher was 0.5 times the tank capacity over one day.

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800ml water 800ml
Optical brightener (FL-2) 2.2g 5.1g
Optical brightener (FL-3) 0.35 g 1.75 g
Triisopropanolamine 8.8g 8.8g
Polyethylene glycol average molecular weight 300 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.20g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5 g 14.0 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydride 4.8 g 14.0 g
Potassium carbonate 26.3g 26.3g
Add water to make 1000ml 1000ml
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.15 12.40

[Bleaching Fixer] [Tank Solution] [Replenisher]
800ml water 800ml
Ammonium thiosulfate (750 g / L) 107 ml 214 ml
m-Carboxybenzenesulfinic acid 8.3 g 16.5 g
Ethylenediamine tetraammonium iron (III) acetate 47.0 g 94.0 g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 16.5g 33.0g
Imidazole 14.6g 29.2g
Ammonium sulfite 16.0 g 32.0 g
Potassium metabisulfite 23.1g 46.2g
Add water to make 1000ml 1000ml
pH (adjusted with nitric acid and aqueous ammonia at 25 ° C.) 6.5 6.5

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5μS / cm or less) 1000ml 1000ml
pH (25 ° C.) 6.5 6.5

  Further, in order to examine the influence of the development time variation on the photographic performance, a processing in which only the color development in the processing step D was extended from 45 seconds to 90 seconds was defined as a processing step E.

Sample 101 was subjected to gradation exposure with blue light by an experimental processing apparatus in which the above-mentioned digital minilab frontier 350 (manufactured by Fuji Photo Film Co., Ltd.) was modified, and processing step D was performed using the above-described processing solution. The yellow density of the sample 101 after the treatment was measured to obtain a characteristic curve corresponding to the blue sensitive layer. The density (Dmin (Y)) of the unexposed part of the characteristic curve was determined, and the exposure amount (E) giving a density of Dmin + 1.5 was determined. In addition, Dmin (Y) ′ of the sample 101 which had been subjected to additional water washing for 1 hour in flowing water at 40 ° C. and dried was measured.
Except for using the samples 102 to 126, 201, 202, 301, 302 instead of the sample 101, the density (Dmin (Y)), exposure amount (E), and Dmin (Y) ′ of the unexposed portion are the same as described above. Got.
In order to compare the sensitivity of each sample, the relative value of the 1 / E value of each sample when the 1 / E value of the sample 101 was 100 was taken as the sensitivity. If the sensitivity is greater than 100, it indicates a higher sensitivity than the sample 101, and if it is less than 100, it indicates a lower sensitivity. Dmin (Y) indicates that the smaller the value, the less colored white background. Further, in order to evaluate the residual color of the sample, a value of Dmin (Y) −Dmin (Y) ′ was obtained and used as ΔDmin. The smaller ΔDmin, the smaller the remaining color.
Furthermore, the same evaluation was performed in the processing step E for each sample.
Table 4 below shows the emulsion in each sample first layer, the added compounds, and the experimental results.

As can be seen from Table 4, the sample 101 showed good performance in normal 45-second development, but the density of the unexposed area significantly increased as the development time increased. This phenomenon occurs in any of the samples (samples 118, 121, and 124) using the compound of the general formula (I) of the present invention, and becomes more prominent as the silver iodide content in the emulsion is larger as in the sample 301. is there.
In contrast, by using a small amount of the compound of the general formula (IV) of the present invention in combination with the compound of the general formula (I) of the present invention, the white background coloring by development is improved without adversely affecting the sensitivity and residual color. I understand that

Claims (9)

In a silver halide color photographic light-sensitive material having at least one yellow-colored blue-sensitive silver halide emulsion layer on a support, the silver halide grains in the yellow-colored blue-sensitive silver halide emulsion layer have a silver chloride content of 90. % Or more and 0.05 to 1.00 mol% of silver iodide, and a silver iodide-containing phase is formed at any position from 85% to 100% of the grain volume as measured from the inside of the grain. The cubic side length is 0.6 μm or less of cubic or tetrahedral crystal grains, and is spectrally sensitized by at least one dye represented by the following general formula (I) A silver halide color photographic light-sensitive material characterized by the above.
Formula (I)

In formula (I), Y represents an optionally substituted thiophene ring, furan ring, or pyrrole ring, and the bond between two carbon atoms to which Y is condensed is a single bond. Or a double bond. V represents a substituent, and n represents a number of 0 or more and 4 or less. R ¹ and R ² represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. M represents a counter ion, and m represents a number of 0 or more necessary for neutralizing the charge in the molecule. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide grains in the yellow-colored blue-sensitive silver halide emulsion layer contain 0.1 to 7 mol% of silver bromide, and the silver bromide-containing phase is 2. The silver halide color according to claim 1, wherein the silver halide color is formed at any position inside the silver iodide-containing phase in 50 to 100% of the grain volume as measured from the inside of the grain. Photosensitive material. The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the dye represented by the general formula (I) is a cyanine compound represented by the following general formula (II) or general formula (III). The silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that
Formula (II)

In formula (II), one of R ³ and R ⁴ represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ¹ and V ² represent a hydrogen atom or a monovalent substituent. M ¹ represents a counter ion, and m ¹ represents a number of 0 or more necessary for neutralizing the charge in the molecule.
General formula (III)

In formula (III), one of R ⁵ and R ⁶ represents an alkyl group substituted with an acid group other than a sulfo group, and the other represents an alkyl group substituted with a sulfo group. V ³ and V ⁴ represent a hydrogen atom or a monovalent substituent. M ² represents a counter ion, and m ² represents a number of 0 or more necessary for neutralizing the charge in the molecule. The silver halide color photographic light-sensitive material according to claim 1, 2 or 3, wherein the silver halide grains in the yellow color developing blue-sensitive silver halide emulsion layer contain an iridium complex. The silver halide color photographic light-sensitive material according to claim 1, 2 or 3. 5. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide emulsion in the yellow color developing blue-sensitive silver halide emulsion layer is gold sensitized. The silver halide color photographic light-sensitive material according to claim 1, claim 2, claim 3, or claim 4. In the cyanine compound represented by the general formula (II), one of R ³ and R ⁴ is carboxymethyl group or methanesulfonylcarbamoylmethyl group, and the other is 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group or It is selected from any of 3-sulfobutyl groups, and V ¹ and V ² are selected from a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, or an alkoxycarbonyl group. A featured cyanine compound. In the cyanine compound represented by the general formula (III), R ⁵
And one of R ⁶ is selected from carboxymethyl group or methanesulfonylcarbamoylmethyl group, the other is selected from 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group and 3-sulfobutyl group, and V ³ and V 6 ⁴ is a cyanine compound, wherein ⁴ is selected from a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, or an alkoxycarbonyl group. 3. The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the yellow color developing blue-sensitive silver halide emulsion layer contains a compound represented by the following general formula (IV): Item 6. A silver halide color photographic material according to any one of Items 1 to 5.
Formula (IV)

In formula (IV), Ch represents an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. A represents an atomic group forming an aromatic ring in which two or more benzene rings and / or heterocycles are condensed. Z represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, or a residue necessary for constituting a cyanine dye as a whole molecule. R ⁷ represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. M ⁷ represents a counter ion, and m ⁷ represents a number of 0 or more necessary for neutralizing the charge in the molecule. 9. The silver halide color photographic material according to claim 8, wherein the compound represented by the general formula (IV) is represented by the following general formula (V). Photosensitive material.
General formula (V)

In Formula (V), Z ⁸ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a residue necessary for constituting a monomethine cyanine dye as a whole molecule. R ⁸ represents a substituted or unsubstituted alkyl group. M ⁸ represents a counter ion, and m ⁸ represents a number of 0 or more necessary for neutralizing the charge in the molecule.