JPS62121456A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material prevented from deterioration in developed cyan color density even when it is processed with a bleaching solution or bleach-fixing solution fatigued or weak in oxidizing power by incorporating a specified cyan dye forming coupler and a specified metal complex. CONSTITUTION:The silver halide color photographic sensitive material contains at least one of cyan dye forming couplers represented by formula [I] in which R1 is -CONR6R7, -NHSO2R6R7 or the like; R2 is a group substitutable at the naphthol ring; l is an integer of 0-3; R3 is a monovalent organic group; and X is H or a group to be released by the coupling reaction with the oxidation product of an aromatic primary amine color developing agent. This photographic sensitive material contains said syan coupler in an amount of 0.2-30mol% of the photosensitive silver halide, and it also contains at least one of the metal complexes represented by formulae [II]-[V] in an amount of 1-100mol%, preferably, 5-80mol% of the cyan coupler.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, in particular a silver halide color photographic material that does not develop color even when processed using a bleach or bleach-fix solution that is tired or has weak oxidizing power. The present invention relates to a silver halide color photographic light-sensitive material that does not cause a decrease in density and suppresses the occurrence of staining due to long-term dawn exposure of the light-sensitive material after processing.

(Prior art) When a silver halide photographic light-sensitive material is exposed to light and then subjected to color development, an oxidized aromatic primary amine developer and a dye-forming coupler (hereinafter referred to as coupler) react to form a color image. It is formed.

Various requirements are imposed on couplers used in recent silver halide color photographic materials. For example, it has excellent stability, excellent processing suitability, excellent color development, excellent hue of color images, robustness of color images, low cost and excellent manufacturing suitability. There is such a thing as being there.

Conventionally, phenolic couplers and naphthol couplers have been used as cyan couplers.

In particular, 1-naphthol couplers have a long-wavelength absorption maximum (λmax) of the color-forming dye produced, have low side absorption in the edge region, and are excellent in color reproduction, and many couplers with excellent color-forming properties have been found. Moreover, it is inexpensive and has excellent manufacturing suitability.
It has been widely used in color negative photosensitive materials.

However, phenolic couplers and naphthol couplers, especially 2-alkylcarbamoyl-1-naphthol couplers, which have been widely used in the past, cannot be used in the bleaching or bleach-fixing process of color development processing due to fatigue or oxidation of the bleaching or bleach-fixing solution. If the power is weak, a sufficient color image cannot be obtained. This phenomenon is believed to be due to reduction fading of the cyan dye due to ferrous ions generated during the bleaching or bleach-fixing process. Furthermore, the cyan images formed by these couplers have a drawback of low fastness.

The disadvantage of the former method is that the substituent of the carbamoyl group at the 2-position is changed from an alkyl group to an aryl group, and 2-arylcarbamoyl-1-naphthol couplers (such as those described in U.S. Pat. No. 3,488,193) are used. However, the latter drawback is still insufficient even when using this coupler, and using this coupler 100% as a cyan coupler is not necessarily preferable in terms of image preservation.

On the other hand, among the naphthol couplers, patent application No. 59-936
No. 05, No. 59-264277 and No. 59-26
The 1-naphthol coupler disclosed in No. 8135, which has a specific substituent at the 5-position, overcomes the drawbacks of the former two and has excellent performance, but it has the following drawbacks. One reason is that when photosensitive materials containing the coupler are exposed to light for a long period of time after processing, a brown coloration, so-called staining, occurs, and the other reason is that the color development is insufficient, making it difficult to use recent high-sensitivity photosensitizers. This was due to a lack of suitability for the material. In particular, the former drawback is a major problem because stain causes deterioration in color reproducibility of photosensitive materials.

(Objects of the present invention) The first object of the present invention is to provide a silver halide color photographic light-sensitive material that does not cause a decrease in cyan color density even when processed using a bleach or bleach-fix solution that is tired or has weak oxidizing power. There is a particular thing.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material in which the occurrence of staining due to long-term dawn exposure of the light-sensitive material after processing is suppressed.

(Means for Achieving the Objects) The objects of the present invention are to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support. ] and at least one metal complex represented by the following general formula [■], [■], [rV] or [V]. Achieved in photosensitive materials.

In general formula [1], R is -CONRs R, -N
HCOR,, -NHCOOR,, -NH3O□RB,
-NHCONR6R, or -NH3O2NR6R, R2 is a group that can be substituted on the naphthalene ring, l is an integer from 0 to 3, R3 is a monovalent organic group, X is a hydrogen atom or aromatic primary amine development Each represents a group that can be separated by a coupling reaction with an oxidized drug. However, R6
and R1 may be the same or different and independently represent a hydrogen atom, an aliphatic group, an aromatic group or a multi-s ring group, and R1
1 represents an aliphatic group, an aromatic group or a heterocyclic group.

When l is 2 or 3, R2 may be the same or different, or may be bonded to each other to form a ring. R
2 and R3 or R3 and X may be bonded to each other to form a ring.

Here, the aliphatic group refers to a linear, branched, or current alkyl group, alkenyl group, or alkynyl group, and may be substituted or unsubstituted. The aromatic group refers to a substituted or unsubstituted aryl group, and may be a condensed ring. The term "heterocycle" refers to a substituted or unsubstituted monocyclic or condensed ring heterogroup.

One-part formula [■] General formula (Ilff) Rs Rt R* R*
General formula (■) General formula (V) R"R" In the formula, M represents Cu, Co, Ni, Pd or Pt.

R2, R3, R4 and R5 are each a hydrogen atom, a halogen atom, a hydroxyl group, a cyan group, an alkyl group, an aryl group, or a cycloalkyl group bonded directly or indirectly to a carbon atom on the benzene ring via a divalent linking group. group, heterocyclic group, or R2 and R3, R3 and R4, or R4 and R5
represents a group of nonmetallic atoms necessary to bond with each other to form a 6-membered ring.

R8, R9 and RIQ each represent a hydrogen atom, an alkyl group or an aryl group.

R7 represents a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group.

R8 represents an alkyl group, an aryl group, or R8 and R9 or R9 and RIG represent a group of nonmetallic atoms necessary for bonding with each other to form a 5- to 8-membered ring.

Y represents a group of nonmetallic atoms necessary to form a 5-membered ring or a 6-membered ring.

The substituents in general formula [I] will be described in detail below.

R1 is -CONR6R7, NHCORa, NHCOOR
a, NH30zRs, NHC○NReRt or -
NH3O□NRs R, is shown. Rs, R7 and R
8 is an aliphatic group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms;
aromatic groups and heterocyclic groups having 2 to 30 carbon atoms.

R6 and R7 may each be a hydrogen atom.

R2 represents a group (including an atom, the same applies hereinafter) that can be substituted on the naphthalene ring, and typical examples include a halogen atom, a hydroxy group, an amino group, a carboxy group, a sulfonic acid group, a cyan group, an aliphatic group, an aromatic group, heterocyclic group, carbonamide group,
Sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group,
Examples include an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, and an imide group, and the number of carbon atoms contained in R2 is 0 to 30.

! An example of cyclic R2 when =2 is a dioxymethylene group.

R3 represents a monovalent organic group, preferably represented by the following general formula CVD).

General formula CVD R, (y), - where Y represents NH, /Co or /S02, n
represents zero or 1, R3 is a hydrogen atom, and has 1 to 3 carbon atoms
0 aliphatic group, aromatic group with 6 to 30 carbon atoms, 2 to 3 carbon atoms
30 heterocyclic groups, -OR1゜, -PO(-OR, □), , -PO-fR,,) 2
, or -5o2OR, where RIo,
Rl 1 and Rl 2 are the same as defined above for R, , R7 and R8, respectively.

may be bonded to form a nitrogen-containing heterocycle (morpholine ring, piperidine ring, pyrrolidine ring, etc.).

X represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Typical examples of coupling-off groups include halogen atom, -OR,3, -3R3-, OC
R+3, -NHCOR,3, an aromatic group having 6 to 30 carbon atoms, an azo group, a heterocyclic group having 1 to 30 carbon atoms and connected to the coupling active position of the coupler with a nitrogen atom (cono\lyric acid imide group, phthalic acid imide group, (acid imide group, hydantoinyl group, pyrazolyl group, 2-benzotriazolyl group, etc.). Here, R13 represents an aliphatic group having 1-30 carbon atoms, an aromatic group having 6-30 carbon atoms, or a heterocyclic group having 2-30 carbon atoms.

In the present invention, the aliphatic group may be saturated or unsaturated, substituted or unsubstituted, linear, branched, or cyclic,
Typical examples include methyl group, ethyl group, butyl group, cyclohexyl group, allyl group, propargyl group, methoxyethyl group, ny"yl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl group, hepta Fluoropropyl group, dodecyloxypropyl group, 2,4-di-tert-amylphenoxypropyl group, 2.4-
Di-tert-amylphenoxybutyl group, etc. are included. The aromatic group may also be substituted or unsubstituted; typical examples include phenyl, tolyl, and 2-
Included are a tetradecyloxyphenyl group, a pentafluorophenyl group, a 2-chloro-5-dodecyloxycarbonylphenyl group, a 4-chlorophenyl group, a 4-cyanophenyl group, a 4-hydroxyphenyl group, and the like.

In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples include 2-pyridyl group, 4-pyridyl group,
2-Flury group, 4-chenyl group, quinolinyl group, etc. are included.

Preferred examples of substituents of the cyan coupler represented by the general formula CI) are explained below. R1 is preferably -C0NR6Rt, and specific examples include carbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoy group, decyloxypropylcarbamoyl group, dodecyloxypropylcarbamoyl group, 2,4-di-tert-amyl group. Examples include phenoxypropylcarbamoyl group and 2,4-di-tert-amylphenoxybutylcarbamoyl group.

Regarding R2 and β, β-〇, that is, an unsubstituted one is most preferable, and R2 is next preferably a halogen atom, an aliphatic group, a carbonamide group, a sulfonamide group, etc.

Preferred R3 has the general formula CVD, where n is zero, and R
As s, -00R1o (formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl L p-chlorobenzoyl group), -000R, □ (methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.), -SO□R1゜(
(methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexadecanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, p-chlorobenzenesulfonyl group, etc.), -CONRl.

R11 (N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbamoyl group, 314-dichlorophenyl group Rubamoyl L 4-methanesulfonylphenylcarbamoyl group, etc.), -8○2NRI. R,I
(N,N-dimethylsulfamoyl group, N,N-diethylsulfamoyl group, NlN-dipropylsulfamoyl group, etc.). Particularly preferred R3 is -C00
RI2, CORro and -3O2RI2, among which -COOR+2 is more preferred.

X is preferably a hydrogen atom, a chlorine atom, an aliphatic oxy group [
For example, 2-hydroxyethoxy group, 2-chloroethoxy group, carboxymethyloxy group, 1-carboxyethoxy group, 2-methanesulfonylethoxy group, 3-carboxypropyloxy group, 2-methoxyethoxycarbamoylmethyloxy group, 1-carboxy tridecyloxy group, 2-(1-carboxytridecylthio)ethyloxy group, 2-carboxymethylthioethyloxy group, 2-methanesulfonamidoethyloxy group, etc.], aromatic oxy group [e.g. 4-acetamidophenoxy group, 2-methanesulfonamidoethyloxy group, etc.] -acetamidophenoxy group, 4-(3-carboxypropanamido)phenoxy group, etc.] and carbamoyloxy groups (e.g., ethylcarbamoyloxy group, phenylcarbamoyloxy group, etc.).

The coupler represented by the general formula CI) has substituents R,,,R
A dimer or a multimer of more than 2, R3 or In this case, the number of carbon atoms in each substituent may be outside the ranges indicated above. General formula CI)
When the coupler represented by formula forms a multimer, a typical example is a single or copolymer of an addition polymerizable ethylenically unsaturated compound (cyan color forming monomer) having a cyan dye forming coupler residue. In this case, the multimer contains repeating units of the general formula [■], and one or more types of cyan coloring repeating units represented by the general formula [■] may be contained in the multimer, and non-containing as a copolymerization component. It may also be a copolymer containing one or more color-forming ethylene-like monomers.

General formula (■) In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, A represents -CONH-1-〇00- or a substituted or unsubstituted phenylene group, and B represents a Represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, L is -CONH-1-NHCONH-
1-NHCOO-1-NHCO-1-0CONH-1-
NH-1-COO-1-OC○-1-〇〇-1-〇-1
-SO2-1-NH3○2- also represents 1t-3O2NH-. a, b, and c represent 0 or 1. Q is general formula C
Indicates a cyan coupler residue in which a hydrogen atom other than the hydrogen atom of the 1-position hydroxyl group is removed from the compound represented by I), and preferably in the compound of general formula CII, the substituent R+,
Indicates a cyan coupler residue in which one hydrogen atom is removed from R2, R3, or X.

As the multimer, a copolymer of a cyan color-forming monomer that provides a coupler unit of the general formula [■] and a non-color-forming ethylene-like monomer shown below is preferred.

Examples of non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (eg, methacrylic acid, etc.). esters or amides derived from acrylic acids such as acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butylacrylate, t- Butyl acrylate, is○-butyl acrylate, 2-
Ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate,
ethyl methacrylate, n-butyl acrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylic acid)
IJ) to aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. evavinylethyl ether) , maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine.

Particularly preferred are esters of acrylic acid, esters of methacrylic acid, and esters of maleate. Two or more types of non-color-forming ethylene-like monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above general formula [■] depends on the physical properties and/or chemical properties of the copolymer to be formed. properties, such as solubility, compatibility with the binder of the photographic colloid composition, such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The cyan polymer coupler used in the present invention is obtained by dissolving a lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the above general formula [■] in an organic solvent and adding it to an aqueous gelatin solution. It may be made by emulsifying and dispersing it in the form of latex, or it may be made directly by emulsion polymerization.

U.S. Pat.
No. 51,820, and U.S. Pat.
The methods described in No. 080,211 and No. 370.952 can be used.

Next, specific examples of couplers represented by the general formula [IJ] will be shown, but the couplers used in the present invention are not limited to these. Each of the following structural formulas % Formula % H3)3 is represented.

Specific examples of couplers represented by the general formula [E] are shown below.

FF CF! SO□Gang H (+-9) C,H.

OH1 c, ++, ocONII OH (+5o)CJsOCONH OH (iso)C411sOcONH OH CH,0CONH0(CHI)ISCIIC,2112
S0OH C,H, [lC[lNH0(CL)2SCIIC,2L
S0OII CH,502NHC1 OH CH3SO2NH0CH2CH2011Js OH1 (C2H,0) , P-Nl+ ]1 I C+, HB Low CF, C0NI (Ro(CL)2SC1lCO, II12
Ji H (■-37) C) 13SOJI+ ) H2 ■ uI+ The cyan coupler represented by the general formula [■] was filed in the patent application in 1983.
-93605, 59-264277 and 59-
It can be synthesized by the method described in No. 268135.

The cyan coupler represented by the general formula [■] is usually produced by using a high boiling point organic solvent such as phthalate esters or phosphate esters having 16 to 32 carbon atoms together with an organic solvent such as ethyl acetate as necessary. It is used by dispersing the emulsion in a medium.

The amount of cyan coupler represented by general formula [I] is:
Preferably 0.00 per mole of photosensitive silver halide
2 to 0.3 mol. In the present invention, if necessary, a known cyan coupler can be used in combination with the cyan coupler represented by the general formula [■]. In this case, the amount of the cyan coupler added includes the amount of the cyan coupler that can be used in combination.

Next, the substituents in general formulas [■] to [v] will be described in detail below.

The halogen atoms represented by R2, R', R' and R5 include fluorine, chlorine, bromine and iodine atoms.

The alkyl group represented by R2, R3, R4 and R5 is preferably an alkyl group having 1 to 19 carbon atoms,
It may be either a straight-chain alkyl group or a branched alkyl group, and may be substituted or unsubstituted. R2
, R3, R4 and R5 preferably have 6 to 14 carbon atoms, and may be substituted or unsubstituted. R2, R3, R4
The heterocyclic group represented by and R5 is preferably a 5-membered ring or a 6-membered ring, and may be substituted or unsubstituted. The cycloalkyl group represented by R2, R3, R4, and R5 is preferably a 5-membered ring group or a 6-membered ring group, and may be substituted or unsubstituted.

The 6-membered ring formed by bonding R2 and R3, R3 and R4, or R4 and R5 to each other is preferably a benzene ring, and this benzene ring may be substituted or unsubstituted, and It may also be a condensed one.

Straight or branched alkyl groups represented by R2, R3, R4 and R5 include, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group. and octadecyl group.

Examples of the aryl group represented by R2, R3, R4 and R5 include a phenyl group and a naphthyl group.

The heterocyclic group represented by R2, R3, R4 and R5 is
A 5- to 6-membered heterocyclic group containing at least one nitrogen atom, oxygen atom, or sulfur atom in the ring as a petero atom, such as a furyl group, a hydrofuryl group, a chenyl group, a pyrazolyl group, a pyrrolidyl group, Examples include a pyridyl group, an imidazolyl group, a pyrazolyl group, a quinolyl group, an indolyl group, an oxasilyl group, and a thiazolyl group.

Examples of the cycloalkyl group represented by R2, R3, R4, and R5 include a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, and a cyclohexagenyl group.

Examples of the 6-membered ring formed by bonding R2 and R3, R3 and R4, or R4 and R5 to each other include a benzene ring, a naphthalene ring, an isobenzothiophene ring, an isobenzofuran ring, an isoindoline ring, etc. can.

The alkyl group, cycloalkyl group, aryl group, or heterocyclic group represented by R2, R3, R4, and R5 above is a divalent linking group, such as an oxy group (-0-), a thio group (-s-), It may be bonded to a carbon atom on the benzene ring via an amine group, oxycarbonyl group, carbonyl group, carbamoyl group, sulfamoyl group, carbonylamino group, sulfonyl group, carbonyloxy group, or the like.

Examples of the alkyl groups represented by R2, R3, R4, and R5 bonded to carbon atoms on the benzene ring via the divalent linking group mentioned above include alkoxy groups (e.g., methoxy group, ethoxy group, butoxy group). group, propoxy group, n
-decyloxy group, n-dodecyloxy group, or n
-hexadecyloxy group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, n-decyloxycarbonyl group, or n-hexadecyloxycarbonyl group, etc.), acyl group (e.g., acetyl group, valeryl group, stearoyl group, benzoyl group or toluoyl group)
, acyloxy groups (e.g., acetoxy or hexadecylcarbonyloxy), alkylamino groups (e.g., n-butylamino, N,N-diethylamino, or N,N-didecylamino), alkylcarbamoyl groups (tato Eha, butylcarbamoyl group,
N,N-diethylcarbamoyl group, or n-dodecylcarbamoyl group), alkylsulfamoyl group (e.g., butylsulfamoyl group, N,N-diethylsulfamoyl group, or n-dodecylsulfamoyl group) ), sulfonylamino groups (e.g., methylsulfonylamino group, or butylsulfonylamino group, etc.),
Examples include a sulfonyl group (for example, mesyl group or ethanesulfonyl group), or an acylamino group (for example, acetylamino group, valerylamino group, valmitoylamino group, benzoylamino group, toluoylamino group, etc.). .

Examples of the cycloalkyl group represented by R2, R3, R4 and R5 bonded to the carbon atom on the ring of the compound of the present invention via the above-mentioned divalent linking group include cyclohexyloxy group, cyclohexyloxy group, cycloalkyl group, Examples include a xylcarbonyl group, a cyclohexyloxycarbonyl group, a cyclohexylamino group, a cyclohexenylcarbonyl group, and a cyclohexyloxy group.

Examples of aryl groups represented by R2, R3, R4, and R5 bonded to carbon atoms on the ring of the compound of the present invention via the above-mentioned divalent linking group include aryloxy groups (e.g., phenoxy groups or naphthoxy group), aryloxycarbonyl group (e.g. phenoxycarbonyl group or naphthoxycarbonyl group), acyl group (e.g. phenoxycarbonyl group or naphthoxycarbonyl group),
For example, benzoyl or naphthoyl groups), anilino groups (such as phenylamino, N-methylanilino or N-acetylanilino groups), acyloxy groups (such as benzoyloxy or toluoyloxy groups), aryloxy groups (such as benzoyloxy or toluoyloxy groups), carbamoyl group (e.g. phenylcarbamoyl group), arylsulfamoyl group (e.g. phenylsulfamoyl group),
Arylsulfonylamino group (phenylsulfonylamino group, p-tolylsulfonylamino group, etc.), arylsulfonyl group (benzenesulfonyl group, tosyl group, etc.)
, or an acylamino group (eg, benzoylamino group).

The alkyl group, aryl group, heterocyclic group, cycloalkyl group represented by R2, R3, R4, and R5 above, or the 6-membered ring formed by bonding R2 and R3, R3 and R4, or R4 and R5 to each other is , a halogen atom (such as a chlorine atom, a bromine atom or a fluorine atom), a cyano group,
Straight chain or branched alkyl groups (e.g. methyl group,
ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, or methoxyethoxyethyl), aryl (for example, phenyl, tolyl), alkoxy groups (e.g. methoxy, ethoxy, butoxy, propoxy or methoxyethoxy), aryloxy groups (e.g. phenoxy, triloxy) , naphthoxy group or methoxyphenoxy group), alkoxycarbonyl group (e.g. methoxycarbonyl group, butoxycarbonyl group or phenoxymethoxycarbonyl group etc.), Roxycarbonyl group (e.g. phenoxycarbonyl group, triloxycarbonyl group or methoxyphenoxycarbonyl group, etc.)
, acyl groups (e.g. formyl group, acetyl group, valeryl group, stearoyl group, benzoyl group, toluoyl group,
naphthoyl group or p-methoxybenzoyl group),
Acyloxy groups (e.g., acetoxy or benzyloxy groups), acylamino groups (e.g., acetamido, benzamide, or methoxyacetamide groups), anilino groups (e.g., phenylamino, N-methylanilino, N-phenylaniline), lino group, N-acetylanilino group, etc.), alkylamino groups (e.g., n-butylamino group, N,N-diethylamino group, 4-methoxy-n-butylamino group, etc.),
Carbamoyl group (e.g., n-butylcarbamoyl group or N,N-diethylcarbamoyl group) or sulfamoyl group (e.g., n-butylsulfamoyl group,
N,N-diethylsulfamoyl group, n-dodecylsulfamoyl group, or N-(4-methoxy-n-butyl)sulfamoyl group), sulfonylamino group (for example, methylsulfonylamino group, phenylsulfonylamine group) , or a methoxymethylsulfonylamino group), or a sulfonyl group (for example, a mesyl group, a tosyl group, a methoxymethanesulfonyl group, etc.).

The alkyl group represented by R6, R7, R8, R9 or RIO includes both substituted and unsubstituted alkyl groups, and may be either a straight alkyl group or a branched alkyl group. These alkyl groups preferably have 1 to 20 carbon atoms, excluding the carbon atoms in the substituent moiety, and include, for example, methyl, ethyl, propyl, butyl, hexyl, and sulfuric acid groups. , decyl group,
Examples include dodecyl group, tetradecyl group, hexadecyl group, heptadecyl group, and octadecyl group.

The aryl group represented by R6, R7, R8, R9 or RIG includes both substituted aryl groups and unsubstituted aryl groups, and preferably has 6 to 14 carbon atoms excluding the carbon atoms in the substituent part. For example,
Examples include phenyl group, tolyl group, and naphthyl group.

The nonmetallic atomic groups necessary to form the 5-membered ring or 6-membered ring represented by Y are the following (a), (b), (C), (
d) or (e) includes a nonmetallic atomic group represented by the formula.

In the formula, RIs represents a hydrogen atom or an alkyl group. R
The alkyl group represented by I5 includes both substituted alkyl groups and unsubstituted alkyl groups, and is preferably an alkyl group having 1 to 20 carbon atoms excluding the carbon atoms in the substituent part, and these are straight-chain alkyl groups, branched alkyl groups, etc. It may be any alkyl group. Specific examples of these alkyl groups are R2・
, R', R' and R5 include the same specific examples as exemplified.

Among the complexes represented by the general formula CID, [IID, [■] or [V], preferred are the following general formulas 1:II
a, ], [II b], [IIIa], [■a], [:
IVb] or (Va:].

General formula (IIa) General formula [■b] General formula Cl1la) General formula (IVa) General formula (IVb) General formula [Va] General formula [IIa:], CII bl, [I[Ia], [
:rVa] [:IVb] or [Va], particularly preferred complexes are those represented by the general formula [:II a
], [■b] or [, IIIa]. General formula C■a], [■b] or [:IIIa]
Among the complexes represented by the above, a more preferable one is one in which R2 is a hydrogen-bonded group, and at the same time R', R' or R
At least one of the groups represented by 5 is a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxy group, and R2, R'
, R', R', R' or R7, the total number of carbon atoms is at least 4.

The group capable of forming a hydrogen bond represented by R2 is an oxy group (for example, a methoxy group, an ethoxy group, a propoxy group,
Butoxy group, n-octyloxy group, 2-ethylhexyloxy group, t-t-cy group, n-dodecyloxy group, 2-hexyldecyloxy group, isostearyloxy group, benzyloxy group, piperonyloxy group , phenoxy group or trimethylsilyloxy group), thio group (e.g. methylthio group, ethylthio group, propylthio group, butylthio group, 2-ethylhexylthio group, n
-dodecylthio group, 2-hexyldecylthio group, isostearylthio group, or substituted or unsubstituted phenylthio group), carbonyl group (e.g., acetyl group, propionyl group, butyryl group, hexanoyl group, octanoyl group, stearoyl group, or benzoyl group) ), oxycarbonyl group (e.g., methoxycarbonyl group,
ethoxycarbonyl group, butoxycarbonyl group, n-decyloxycarbonyl group, stearyloxycarbonyl group or phenoxycarbonyl group), carbamoyl group (
For example, methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl group, N,N-diethylcarbamoyl group, n-dodecylcarbamoyl group or phenylcarbamoyl group, etc.), sulfamoyl group (for example, methylsulfamoyl group, N,N -diethylsulfamoyl group, butylsulfamoyl group, n-dotecylsulfamoyl group or phenylsulfamoyl group),
Sulfonyl groups (e.g. mesyl, ethanesulfonyl, benzenesulfonyl or tosyl), sulfonylamino groups (e.g. methylsulfonylamino or butylsulfonylamino), acylamino groups (e.g. acetylamino or benzoyl) amino group), carbonyloxy group (e.g., acetyloxy group, butyryloxy group, or benzoyloxy group), amino group (e.g., -NH, group, methylamino group, diethylamino group, dibutylrymino group, hexylamino group) , benzylamino group, anilino group, etc.), hydroxyl group, nitro group, cyano group, carboxylic acid group, sulfonic acid group, or halogen atom.

The compound represented by the following structural formula is the general formula [■]
, [■], [■], or [V], which are described to illustrate those which are effective in carrying out the present invention, but the present invention is not limited to these compounds. It is not something that will be done.

M-14 M-15 M-22 M-23 n-C+tHss C:H2CHx
Itt'l5s-nCAL
CJSM-32 M-33 n-CaHz n-C1Hi
+n-CsHz n-C5Hz
CHs CHsn-
CzH2s n-CzH*s
Metal complexes of general formulas [II] to [V] used in the present invention are disclosed in JP-A-53-45063, JP-A-54-62826,
No. 54-62987, No. 54-82384, No. 54
It can be synthesized by the synthesis method described in Japanese Patent No. 82836 and Japanese Patent Application No. 55-12129. The amount of the metal complex of general formulas [II,] to [V] used in the present invention is 0.0 per mole of the cyan coupler according to the present invention.
The amount is preferably 1 mol to 1 mol, more preferably 0.05 mol to 0.8 mol.

The metal complexes of the general formulas [■] to [V] used in the present invention are placed in the same layer as the layer containing the cyan coupler of the general formula [■] according to the present invention, or in a layer adjacent thereto, preferably in the same layer. added to. More preferably, general formulas [■] to [V]
It is used by co-emulsifying the metal complex and the cyan coupler of the general formula CI] and then coating it.

Various color couplers can be used in combination with the present invention, Research Disclosure, December 1978,
17643■-ri section and same, November 1979, 18
The cyan, magenta and yellow dye-forming couplers described in the patents cited in '717 are representative. These couplers can be modified by introducing a ballast group or by
It is preferable that the coupler has diffusion resistance due to multimerization of 4-equivalent coupler or more, and may be a 4-equivalent coupler or a 2-equivalent coupler. Couplers that improve graininess by moderately diffusing the generated dye, DIR couplers that release development inhibitors and the like during the coupling reaction and produce edge effects or multilayer effects, and colored couplers for color correction. can also be used.

The yellow coupler of the present invention is preferably an α-pivalol or α-benzoylacetanilide coupler that separates at an oxygen atom or a nitrogen atom. Particularly preferred embodiments of these two-equivalent couplers are U.S. Pat.
No. 08.194, No. 3.447.928, No. 3.
933.501 and US Pat. No. 4.022.620, etc., or U.S. Pat. Nos. 3, 973.968 and 4.314.
．． No. 023, JP 58-10739, JP 50-
No. 132926.

West German Application No. 2,219,917, West German Application No. 2.261
．． No. 361, No. 2.329.587 and No. 2.
A typical example is the nitrogen atom dissociative yellow coupler described in No. 433.812. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolo [5,1
-C][:1,2.4:]) lyazoles, or pyrazolo C5, as described in European Patent No. 119,860;
1-b) [1,2,41) Riazole etc. can be used. Also preferred is a magenta coupler made into two equivalents by a leaving group bonded to the coupling active position via a nitrogen atom or a sulfur atom. In addition to the cyan coupler of the present invention, a coupler that is robust against humidity and temperature can also be preferably used in combination, and a representative example thereof is U.S. Pat.
Phenolic couplers described in No. 2, etc.; JP-A No. 5
9-31953, Japanese Patent Application No. 58-42671, and Japanese Patent Application Laid-Open No. 58-133293, etc.
- Diacylaminophenol couplers: Typical examples include phenolic couplers having a phenylureido group at the 2-position and a niacylamino group at the 5-position described in U.S. Pat. No. 4,333,999 and the like.

The dye image forming couplers that can be used in combination with the above usually have 1 carbon number.
The emulsion is dispersed in an aqueous medium using a high boiling point organic solvent such as 6 to 32 phthalic esters or phosphoric esters in combination with an organic solvent such as ethyl acetate, if necessary. The standard amount of main coupler used is preferably 0.01 to 0.5 mole for yellow coupler and 0 for magenta coupler per mole of photosensitive silver halide.
．． 003 to 0.3 mol, and 0 for cyan couplers
．． 002 to 0.3 mol.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to 30 mole percent silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 25 mol % silver iodide.

The shape of the silver halide grains in the photographic emulsion is not particularly limited, and may be so-called regular grains having regular crystal bodies such as cubes, octahedrons, and tetradecahedrons, or may be spherical. It may have an irregular crystal shape, a crystal defect such as a crystal plane, or a combination thereof.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimie et Phys
ique Photographique.

Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F
, Duffin.

Photographic IEmulsi, on C
hemistry, Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman,
7 published by Calpress (V, L, Zel ikman)
etal, Making and Coating
Photographic music.

Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in ``Theory and Practice of Photography'' by C1eve, Photogra-
phy Theory and Practice
(1930), p. 131; Gutoff, Photographic Science and Engineering.
Off, Photographic Science
and Engineering) Volume 14, 248
~257 pages (1970); U.S. Patent No. 4.434.22
No. 6, No. 4,414.310, No. 4.433.048
and British Patent No. 2.112,157. The use of tabular grains has advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are detailed in U.S. Pat. No. 4,434,226 cited above. .

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Patent No. 3.505.068, U.S. Patent No. 4,44
4.877 and Japanese Patent Application No. 58-248469. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. These emulsion grains are described in U.S. Pat. No. 4,094,684, U.S. Pat.
4.459,353, British Patent No. 2,038,79
No. 2, U.S. Pat. No. 4,349.622, U.S. Patent No. 4.395
．． No. 478, No. 4,433,501, No. 4,463,
No. 087, No. 3.656.962, No. 3,852.0
No. 67, JP-A-59-162540, etc.

The photographic emulsion used in the present invention may be spectrally sensitized using known photographic sensitizing dyes. In addition, known antifoggants or stabilizers may be used for the purpose of preventing fog or stabilizing the performance of photosensitive materials during manufacture, storage, or photographic processing. U.S. Patent No. 3.954,474, U.S. Patent No. 3,982.947,
Special Publication No. 52-28660, Research Disclosure 17643 (December 1978) VIA or V
"Stabilization of Silver Halide Photographic Emulsions" by Birr, J. rM, and Birr, Focal Press.

5tabilization of Photography
phic 5ilver HalideEmulsio
ns”, Focal Press, l 974
) etc.

The light-sensitive material produced using the present invention may contain hydroquinones, aminophenols, sulfonamidophenols, etc. as a color antifogging agent or color mixing inhibitor.

The light-sensitive material of the present invention may be used in combination with an ultraviolet absorber such as benzotriazoles, typical examples of which are described in SuSearch Disclosure 24239 (June 1984).

The light-sensitive material of the present invention may also contain a water-soluble dye in the hydrophilic colloid layer for filter dyes, irradiation or antihalation purposes, and other purposes. Gelatin, modified gelatin, synthetic hydrophilic polymers, etc. can be used as the binder for the photographic light-sensitive layer or back layer of the present invention.

Furthermore, a hardening agent such as a vinyl sulfone derivative may be contained in any hydrophilic colloid layer, and a vinyl polymer containing a sulfinate salt in the side chain may be used as a hardening agent.

The photosensitive materials of the present invention contain one or more surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, promoting phenomena, increasing contrast, and sensitizing). May include.

In addition to the above-mentioned additives, the light-sensitive material of the present invention further contains various stabilizers, anti-staining agents, phenolic agents or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure 1764
3 (December 1978) and 18716 (1979)
(November 2013).

The present invention can be preferably applied to a color film for high-sensitivity photography, which has at least two emulsion layers having the same color sensitivity and different sensitivities on a support. The typical layer arrangement order is a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer in order from the support side.
It may also be an inverted layer arrangement in which a high-speed layer is sandwiched between emulsion layers having different color sensitivities.

After being processed with a developer containing an aromatic primary amine color developing agent as a main component, the light-sensitive material of the present invention is processed by bleaching and fixing, bleach-fixing, or a combination thereof in order to remove the developed silver. conduct. At this time, bleaching accelerators such as iodine ions, thioureas, thiol compounds, etc. may be used in combination, if necessary.

Washing with water is often performed after bleach-fixing or fixing, but it is convenient to use two or more tanks for countercurrent washing to save water.

Further, a multistage countercurrent stabilization treatment as described in Japanese Patent Application Laid-Open No. 57-8543 may be performed. A pH adjusting buffer or formalin may be added to this treatment. Ammonium salts are preferred additives.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 Photosensitive materials Samples 101 to 107 were prepared on a cellulose triacetate film support, each layer having the composition shown below.

The couplers and metal complexes contained in the first red-sensitive emulsion layer are summarized in Table 1.

1st layer: Red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain 0.6 μm) Silver coating amount 1.9 g/m' Sensitizing dye ■ 4.2 x 10-' per mol of silver % Sensitizing dye ■ 1.4 x 10-' molar gelatin coating amount for 1 mol of silver 1.8 g/m' Couplers and metal complexes Listed in Table 1 Coupler dispersion oil 0 il-10.4 g/m' 2nd Layer: Protective layer Gelatin layer containing polymethyl methacrylate particles (about 1.5 μm in diameter) Gelatin coating amount 1.1 g/m” In addition to the above composition, each layer contains gelatin hardener H-1 and a surfactant. Added.

Table-1 *The amount added to l-l-above is expressed in moles *2: The amount added to 1 mole of coupler is expressed in moles Compounds used to prepare the sample Sensitizing dye I: Anhydro 5,5°-dichloro -3,3
'-di(T-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye ■: Anhydro-9-ethyl-3,3°-di(T-sulfopropyl)-4,5,4 '-5'-dibenzothiacarbocyanine hydroxide triethylamine salt coupler EX-1 i 1-1 (CL = Cl1SOtCH*C0NHCIt -+
-1 After exposing the obtained samples 101 to 107 to light for sensitometry, the following development treatment [A] was performed at 38°C.

1. Color development 3 minutes 15 seconds 2. Bleaching 6 minutes 30 seconds 3. Washing with water
3 minutes 15 seconds 4, established 4
minutes 20 seconds 5, washing with water 3 minutes 15 seconds 6,
Stability 1 minute 5 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate
30.0 g potassium bromide
1.43 Hydroxylamine sulfate 2
．． 4g 4-(N-Ethyl-N-β-hydroxyethylamine) -2-methylaniline sulfate 4.5g Add water IIl Bleach solution Ammonium bromide 160゜0g Aqueous ammonia (28%) 25.0cc Ethylenediamine-tetraacetic acid Sodium iron salt 130.0g glacial acetic acid
Add 14.0cc water
11 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175. Occ Sodium Biphosphite
Add 4.6g water
IIl Stabilizer Formalin 8. After adding OCC water, 111 Next, development processing [B] was carried out in the same manner as development processing [A] except that the bleaching processing solution in development processing [A] was changed to the following processing solution formulation. This bleaching solution simulates the state in which a large amount of photosensitive material has been processed and has become fatigued.

Processing step CB) Bleach solution composition (B-1) (B-2) Pour steel wool into (B-2), seal the plug, and leave to mix Fe(III)-EDTA with Fe(II)-EDT.
After changing to A, this 100 ml was added to (B-1) and treated in the same manner as in treatment step CA), except that it was used as a bleaching solution in treatment step [B].

Concentration measurements were performed on the treated samples obtained as described above. Cyan color density 1.5 due to treatment [A]
The value obtained by dividing the cyan color density obtained in processing [B] by 1.5 at the exposure amount that yields (relative cyan color density)
are summarized in Table 2.

From Table 2, samples using the cyan coupler according to the present invention (
102 to 107) show almost no decrease in color density even when treated with a tired bleaching solution.

Next, using the developed samples subjected to the treatment [A] for Samples 101 to 107, the color image preservability was tested by exposing the coated side to light for 7 days using a fluorescent lamp fading tester (10,000 lux). I conducted a test. The results are shown in Table-3.

Table 3 △D: The yellow density of the unexposed area after 7 days of exposure to fluorescent light (10,000 lux) minus the yellow density of the unexposed area before dawn. As can be seen, the generation of yellow stain due to dawn light is large in samples 102 and 105, whereas in the samples containing the metal complex according to the present invention (103, 104,
106, 107), the occurrence of yellow stain was significantly reduced.

From the above results, the samples based on the present invention show excellent results, with no decrease in cyan color density even when treated with a tired bleaching solution (and with little light staining even after long-term exposure). It became clear that it was.

Example 2 Multilayer color photosensitive materials 201 to 207 each having the composition shown below were prepared on a cellulose triacetate support.

The coating amount of silver halide is expressed in units of silver equivalent g/m゛,
The amount of gelatin applied and the amount of oil applied for coupler dispersion are 2.
7 m@2, and the sensitizing dye and coupler are expressed in molar units per mole of silver halide in the same layer.

1st layer: Antihalation layer Black gelatin layer containing colloidal silver Gelatin coating amount 1.1 2nd layer: Intermediate layer Emulsified dispersion of 2,5-di-t-pentadecylhydroquinone and coupler EX-2 and iodobromide Silver (silver iodide 1
Gelatin layer containing (mol%, average particle size 0.07 μm) Gelatin coating amount 1.2 Power puller dispersion oil 0iL1 0.2”
0il-20,02 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide: 5 mol% Average grain size: 0.7 μm) Silver coating amount 1.6 Sensitizing dye I 4.2X10- '／／
II 1.4X10-' coupler and metal complex Gelatin coating amount listed in Table 4 1.2 Power puller dispersion oil 0il-10,3 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide = 1010 mol% average: 1.5 μm) Silver coating amount 1.9 Sensitizing dye I 3.0X10-'//
n 1.0X10-' coupler and metal complex Gelatin coating amount listed in Table 5 1.3 Force puller dispersion oil 0
ill 0.3 5th layer: Intermediate gelatin layer Gelatin coating amount 0.9 6th layer:
First green-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide: 5 mol% Average grain size: 0.8 μm) Silver coating amount 0.6 Sensitizing dye II[, 4,5X10-' // TV 1.8X10
-'h puller EX-60,071 〃EX-70,015 〃EX-80,006 Gelatin coating amount 0.5 force Puller dispersion oil 0il-10,15 7th layer: 2nd green-sensitive emulsion layer iodobromide Silver emulsion (silver iodide = 6 mol%, average grain size: 0.85 μm) Silver coating amount 1.6 Sensitizing dye I 4.0X10-'//
I'V 1.6X10-'〃
EX-90,020 〃EX-70,002 〃EX-80,001 Gelatin coating amount 1.8 Power puller dispersion oil 0il-10,45〃0il-2Q. 1 8th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide: 10 mol% Average grain size: 1.5 μm) Silver coating amount 2.1 Sensitizing dye III 3.0X10-'//
rV 1.2X10-' coupler EX-90,009 〃EX-20,001 Gelatin coating amount 2.1 Force puller dispersion oil 0il-10,7N 0i12
0.1 9th layer: Yellow filter single layer Yellow colloidal silver and 2.5-di-t- in gelatin aqueous solution
Gelatin layer containing emulsified dispersion of pentadecyl hydroquinone Gelatin coating amount 0.9 10th layer:
First blue-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide: 6 mol% Average grain size: 0.6 μm) Silver coating amount 0.4 Coupler EX-100,27 〃EX-110,005 Gelatin coating amount 1. Triple puller dispersion oil 0ill 0.3 11th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide: 10 mol% Average grain size: 1.0 μm) Silver coating amount 0.6 Coupler EX- 100,045 Gelatin coating amount 0.5 power puller dispersion oil 0il-10,05 12th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide: 10 mol% Average grain size: 1.8 μm) Silver coating amount 0.8 Sensitizing dye V 2.0X10-' coupler EX-100,036 Gelatin coating amount 0.4 Power puller dispersion oil 0il-10,1 13th layer: 1st protective layer:
Gelatin layer Gelatin coating amount 0.7 14th layer: 2nd protective layer Silver iodobromide (silver iodide 1 mol%, average particle size 0.07 μm) and polymethyl methacrylate particles (diameter approximately 1.5 μm)
Gelatin layer containing m) Gelatin coating layer 0.8 In addition to the above composition, gelatin hardening agent H-1 and a surfactant were added to each layer.

The compounds used to prepare the samples are shown below.

However, sensitizing dyes ■ and ■, coupler EX-1,0il
-L and gelatin hardening agent H-1 were the same as those used in Example 1.

Sensitizing dye m: Anhydro-9-ethyl-5,5'-dichloro-3,3'-di(T-sulfopropyl)oxacampodianine sodium salt sensitizing dye m: Anhydro-5,6,5',6 '-Tetrachloro-1,1'-diethyl-3,3'-di(β-[β-(γ-sulfopropoxy)ethoxy]ethyl)imidazolocarbocyanine hydroxide sodium salt sensitizing dye ■: Anhydro 5. 5'-dichloro-3,3
'-G(δ-sulfobutyl)thiacyanine triethylammonium salt 0i1-,j LLIUL4111 Coupler EX-2 Coupler EX-3 to I+ Coupler EX-4 H Coupler EX-5 H Coupler EX-6 CHs Coupler EX-7 l Coupler EX-8 L Coupler EX-9 Js Coupler EX-10 Coupler EX-11 The same tests as in Example 1 were conducted on the obtained samples 201 to 207. These results are summarized in Table-6.

From Table 6, samples based on the present invention (203, 204, 20
6゜207), even when treated with a tired bleach solution,
It is clear that this is an excellent product in that there is no decrease in cyan coloring density and little staining occurs even when exposed to light for a long time.

Table-6 Procedural Amendment Written January 1986 2tl-Japanese Patent Office Commissioner U? 1. Doguchi, E. 1. Indication of the case 1985 Special Revised Application No. 259809 2. Name of invention: Silver halide color photographic light-sensitive material 6. Number of inventions increased by amendment: 07. Address of amendment: Details Store No'-2 G'! , i , 2't H -17=, -ゝ 〆:\

Claims (1)

[Scope of Claims] A silver halide color photographic material having at least one silver halide emulsion layer on a support, comprising at least one cyan dye-forming coupler represented by the following general formula [I] and at least one cyan dye-forming coupler represented by the following general formula [I]. The following general formula of species [II], [I
A silver halide color photographic material containing a metal complex represented by [II], [IV] or [V]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], R_1 is -CONR_6R_7
, -NHCOOR_6, -NHCOOR_8, -NHSO
_2R_8, -NHCONR_6R_7 or -NHS
O_2NR_6R_7, R_2 is a group that can be substituted on the naphthalene ring, l is an integer from 0 to 3, R_3 is a monovalent organic group, and X is a hydrogen atom or a cup with an oxidized aromatic primary amine developer. Each represents a group that can be separated by a ring reaction. However, R_6 and R_7 may be the same or different and independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R_8 represents an aliphatic group, an aromatic group, or a heterocyclic group. When l is 2 or 3, R_2 may be the same or different, or may be bonded to each other to form a ring. R_2 and R_3 or R_3 and X may be combined with each other to form a ring. General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ Numerical formulas, chemical formulas, There are tables, etc. ▼ In the formula, M represents Cu, CO, Ni, Pd or Pt. R^2, R^3, R^4 and R^5 are each hydrogen atom, halogen atom, hydroxyl group, cyano group, direct or 2
an alkyl group, an aryl group, a cycloalkyl group indirectly bonded to a carbon atom on a benzene ring via a valent linking group;
The heterocyclic group, R^2 and R^3, R^3 and R^4, or R^4 and R^5 represent a group of nonmetallic atoms necessary for bonding with each other to form a 6-membered ring. R^6, R^9 and R^1^0 each represent a hydrogen atom, an alkyl group or an aryl group. R^7 represents a hydrogen atom, an alkyl group, an aryl group, or a hydroxyl group. R^8 is an alkyl group, an aryl group, or R^8 and R^9
Alternatively, R^9 and R^1^0 represent a group of nonmetallic atoms necessary to combine with each other to form a 5- to 8-membered ring. Y represents a group of nonmetallic atoms necessary to form a 5-membered ring or a 6-membered ring.