JPS6298352A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having good stability of dye and good sensitivity by incorporating a specific magenta coupler and a specific high boiling point organic solvent to a silver halide emulsion layer. CONSTITUTION:The titled material contains the pyrazolotriazole type magenta coupler shown by formula I wherein R1 and R2 are each a hydrogen atom or a group capable of binding to the pyrazolotriazole ring via a secondary or a tertiary carbon atom, at least one of R1 and R2 is -NHSO2- group. The high boiling point organic solvent is shown by formula II wherein R3, R4 and R5 are each an alkyl or a cycloalkyl, an alkenyl or an aryl group, the total carbon numbers contained in said groups are 12-60. The titled material is obtd. by incorporating the magenta coupler shown by formula I and the high boiling point organic solvent shown by formula II to the silver halide emulsion layer. Thus, the titled material having improved color density, stability of dye and color reproducibility is obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic material having improved color development, color image fastness to light, and color reproducibility. It relates to color photographic materials.

(Prior art) Compared to conventional 5-pyrazolone, pyrazoloazole type couplers are suitable for color photosensitivity because the spectral absorption of the dye obtained by coupling with the oxidized form of paraphenyldiamine has less unnecessary absorption around 430 nm. Various proposals have been made with the aim of improving the color reproduction of materials.

Previously, U.S. Patent Nos. 3.061.432 and 3.369.
Pyrazolobenzimidazole skeleton known as No. 897,
IH-pyrazoloC3,2-C)(1,2,4]) lyazole skeleton known from U.S. Pat. No. 3.725.067; more recently IH-imidazo[ 1,2-b) Pyrazole skeleton, IH-pyrazolo (1
.

However, a photosensitive material in which this pyrazoloazole magenta coupler is dispersed in a silver halide emulsion layer using a high-boiling organic solvent has low color development, and the transmission or reflection absorption spectrum of the film or photographic paper does not necessarily have a tail on the long wavelength side. The problems were that the sharpness was not good, the color reproducibility was not sufficiently improved, and the light fastness of the color image was also not sufficient.

(Problems to be Solved by the Invention) The azomethine dyes derived from pyrazoloazole couplers with these skeletons certainly have little unnecessary absorption near 430 nm, and have a sharp cutoff on the long wavelength side, which is favorable for color reproduction. However, it is not always possible to use it in color photographic light-sensitive materials because it does not necessarily have good stability on the long wavelength side, has a slow coupling rate with the oxidized form of the developing agent, and has low light fastness of the color image produced. It was still unsatisfactory.

(Objective of the present invention) Therefore, the object of the present invention is to improve the color development property by increasing the coupling rate with the oxidized form of the developing agent, and to improve the fastness of the produced color image.
In particular, it is an object of the present invention to provide a silver halide color light-sensitive material using a pyrazoloazole coupler which has improved light fastness and can further increase sensitivity.

(Means for Solving the Problem) The object of the above is to provide a silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support, in which the silver halide emulsion layer contains , the following general formula C
A silver halide color photographic light-sensitive material characterized in that at least one pyrazoloazole magenta coupler represented by I) is co-dispersed with at least one high-boiling point solvent represented by the following general formula [■]. achieved by.

General Formula CI] In the formula, R1 and R2 represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. R
, , R2 or X may form a dimer or more multimer. Here, at least one of R1 and R2 represents a group bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom, and furthermore, at least one of R1 and R2 represents -N)Is○2- A group having one or more groups. However, when R1 is a tertiary alkyl group or when R2 is bonded to the pyrazolotriazole ring through a secondary carbon atom, R2 is not a substituted aralkyl group.

In the general formula [I], the multimer means one having two or more groups represented by the general formula [I] in one molecule, and includes bis-forms and polymer couplers. Here, the polymer coupler is a monomer having a moiety represented by the general formula [1] (preferably one having a vinyl group,
A homopolymer consisting only of vinyl monomer (hereinafter referred to as vinyl monomer) may be used, or a copolymer may be prepared together with a non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic-grade amine developer.

General formula [■] ○ R30-P-OR2 ■ 0R1 In the formula, R3, R4 and R9 are each an alkyl group,
Represents a substituted alkyl group, cycloalkyl group, substituted cycloalkyl group, alkenyl group, substituted alkenyl group, aryl group or substituted aryl group. However, the total number of carbon atoms in the groups represented by R3, R- and R5 is 12 to 6.
It is 0. Here, R3, R, and R5 are never all tolyl groups.

The pyrazolotriazole coupler represented by the general formula m will be explained in detail below.

In the general formula [I], the substituents R1 and R2 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups, aryloxy groups, heterocyclic okyne groups, acyloxy groups, carbamoyloxy groups ,
Silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, IJ-ruthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxy It represents a carbonylamide group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and at least one of R9 or R2 is a secondary or tertiary group. represents a group bonded to the pyrazoloazole ring via a carbon atom of the same class, and furthermore, at least one of R1 or R2 has one or more -NH3O7- groups.

However, when R1 is a tertiary alkyl group, or R2 is 2
R2 is not a substituted aralkyl group when attached to the pyrazolotriazole ring at a carbon atom. In the general formula [I], X represents a hydrogen atom, a halogen atom, a carboxy group, or a group that is capable of coupling off by bonding to a carbon at a coupling position via an oxygen atom, a nitrogen atom, a sulfur atom, or the like. The case where R,, R2 or X becomes a divalent group and forms a bis body is also included. Also,
When the moiety represented by the general formula [1] is present in the vinyl monomer, R1 or R2 represents a simple bond or a connecting group, and the moiety represented by the general formula [I] and the vinyl group are connected through this. Join.

More specifically, R1 and R2 are hydrogen atoms, halogen atoms (e.g., chlorine atoms, bromine atoms, etc.), alkyl groups (
For example, methyl group, propyl group, hexyl group, trifluoromethyl group, tridecyl group, 3-(2,4-di-t-
amylphenoxy)propyl group, 2-dodecyloxyethyl group, 3-phenoisyprobyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g. phenyl group, 4-t -Butylphenyl L 2,4-di-t-amylphenyl group, 4-
tetradecaneamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g., methoxy group, ethoxy group, 2-methquinethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (
For example, phenoxy group, 2-methylphenoxy group, 4-
t-butylphenoxy group, etc.), heterocyclic oxy group (e.g., 2-benzimidazolyloxy group, etc.), acyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (e.g., N -phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g.,
dodenylsulfonyloxy group, etc.), acylamide 7 group (
For example, acetamido group, benzamide group, tetradecanamide group, α-(2,4-di-t-amylphenoxy)butyramide group, γ-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α-(4-di-t-amylphenoxy)butyramide group, -(4-hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g. phenylamino group, 2
-chloroanilino group, 2-chloro-5-tetradecanamideanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5-(α-(3-t- butyl-4-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g. phenylureido group, methylureido group,
N,N-dibutylureido group, etc.), imide group (e.g., N-succinimide group, 3-penzylhydantoynyl group, 4-(2-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamino groups (e.g., N, N
-dipropylsulfamoylamino group, N-methyl-N
-decylsulfamoylamino group, etc.), alkylthio groups (e.g., methylthio group, octylthio group, tetratercylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group) groups, etc.>, arylthio groups (e.g., phenylthio group, 2-butoxy-5-t-octylphenylthio L 3-pencudecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.) , heterocyclic thio group (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group, 2, 4-di-tert-butylphenoxylponylamino group, etc.), sulfonamide group, (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide Lp-)luenesulfonamide group, occudecanesulfonamide group,
2-methyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group, (e.g., N-ethylcarcamoyl JiLN, N-cyphthylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group) , N-methyl-N-dodecylcarbamoyl group, N-(3
-(2,4-di-tert-amylphenoxy)propyl)carbamoyl group, etc.), acyl group (e.g., acetyl group, (2,4-di-tert-amylphenoquine)acetyl group, benzoyl group, etc.), Sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(2-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N -diethylsulfamoyl group, etc.)
, sulfonyl group (e.g., methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g., eva, octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group ( for example,
methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.)
, aryloxycarbonyl group (eg, phenyloxycarbonyl group, 3-pentadecyphenyloxycarbonyl group, etc.).

At least one of R or R2 is secondary or 3
represents a group bonded to the pyrazoloazole ring through a carbon atom of the same class. To explain these groups in detail, they include isopropyl group, t-butyl group, 1-hexyl group, cyclohexyl group, adamantyl group, ■-ethoxyisopropyl group, 1-hexyl group, cyclohexyl group, adamantyl group,
-phenoquine-1,1-dimethylmethyl group, α,α-dimethylbenzyl group, α,α-dimethylphenylethyl group, α-ethylbenzyl group, 1-ethyl-1[:4-(2
-butoxy-5-tert-octylbenzenesulfonamido) phenylcomethyl group, ■-methyl-2- [:
4- (4-dodecyl otone benzenesulfonamide)
phenyl]ethyl group, 1-methyl-2-(2-octyloxy-5-tert-octylbenzenesulfonamido)ethyl group, 111-dimethyl-2-(2-octyloxy-5-tert-octylbenzenesulfonamido)ethyl group, 1-methyl-2-[2-octyloxy-5-(2-octyloxy-5-tert-octylbenzenesulfonamide)benzenesulfonamide]ethyl group, 1-ethyl-2-(2-dodecyloxy- 5-
tert-octylbenzenesulfonamido)ethyl group, 1-(2-hydroxyethyl)-2-(α-C3-(
2-octyloxy-5-tert-octylbenzenesulfonamido)phenoxy] dodecanamido)ethyl group, etc.

To explain in detail about X,
Acetoxy group, propanoyloxy group, benzoyloxy group, 2,4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfone Amidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2- phenoxyethoxy group, 5-phenyltetrazolyloxy group, 2-benzothousazolyloxy group, etc.), groups linked through nitrogen atoms (
For example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, hepkufluorobutanamide group,
2.3,4,5.6-pentafluorobenzamide group,
Octanesulfonamide group, p-cyanophenylureido group, N,N-diethylsulfamoylamide 7 groups, 1-
Piperidyl group, 5,5-dimethyl-2,4-dioxo-
3-oxazolidinyl M, l-benzyl-ethoxy-3
-hydantoinyl group, 2N-1,1-dioxo-3(2
H)-oxo 1,2-benzisothiazolyl group, 2-
Oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,
4-) Riazol-1-yl, 5- or 6-promobenzotriazol-1-yl, 5-methyl-1,2,
3,4-) lyazol-1-yl group, benzimidazolyl L3-benzyl-1-hydantoynyl group, ■-benzy-5-hexadecyloxy-3-hyguntoynyl group,
5-methyl-1-tetrazolyl group, 4-methoxyphenylazo L 4-pivaloylaminophenylazo group, 2-
(Hydroxy-4-propanoylphenylazo group, etc.) Groups linked by a sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group) 4-octanesulfonamidophenylthio group, 2
-butoxyphenylthio L2-(2-hexanesulfonylethyl)-5-tert-octylphenylthio group,
Benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3
, 4,5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-f-ophenylthio L
2-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio group, etc.).

When R,, R2 or ethylethylene group, 1,10-decylene group, -CH2CH2-0CH2CH2-1, etc.), substituted or unsubstituted phenyl 7M (9'llt, 1, 4-
Phenylene Ll.

Examples include 3-phenylene group, -N)ICO-R7-CONH- group (R' represents a substituted or unsubstituted alkylene group or phenylene group), and the like.

When the linking group represented by R1 or R2 in the vinyl monomer is represented by the general formula (1'l), the linking group represented by R1 or R2 is an alkylene group (substituted or unsubstituted alkylene group, such as a methylene group, an ethylene group, , 1-methylethylene group, 1
．． 10-decylene group, -Cl(2CH20CH2CH2
-1, etc.), phenylene group (substituted or unsubstituted phenylene group, such as 1.1phenylene L1.3-phenylene group, CH3Cβ CH, Cβ -CONH-1-〇-1-〇C○- and aral ( 1' Includes groups formed by combining those selected from the following.

Note that the vinyl group in the vinyl monomer may have a substituent other than those represented by the general formula [). Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α
- Chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl Acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, l5O-butyl acrylate, 2-ethylhexyl acrylate 1. n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy meccrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, meccrylonitrinobe, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyl toluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (
(e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester/l/, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-
Examples include vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Examples of couplers included in the present invention are shown below, but the invention is not limited thereto.

[111CI OCH, Cll2fJ1. SO, C1l.

Shisl111roILノU
LIL113 (M, -10) CM, -
+:++8. ．． /CI! \N/'N11 CM -13) CI+.

DC, l+, (M-183 CHI'- C, 111(1) -(-CH-CH,-)-ET-+CH,-C÷1゜
C1l.

COOC1Its CHs< M −
31) cns■ ÷I:H-CL+i-←CI+,-C÷1゜CHfN
11SO*CHs The total number of carbon atoms of the substituents represented by R3, R, and R5 in the above general formula [■] is 12 to 60, but if it is outside this range, the improvement effect aimed at by the present invention will not be achieved. This is because the amount decreases. Furthermore, if the total number of carbon atoms exceeds 60, the ability to dissolve the coupler decreases and the coupler may precipitate, which is not preferable. In general formula (II), the alkyl group represented by R3, R4 or R5 may be a straight chain alkyl group or a branched alkyl group, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group. group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. The cycloalkyl group represented is, for example, a cyclopentyl group or a cyclohexyl group. The aryl group represented by R: l, R4 or R3 is a phenyl group, a naphthyl group, etc., and an alkenyl group such as a haftenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, a dodecenyl group, an octadecenyl group, etc. . These alkyl groups, cycloalkyl groups, aryl groups and alkenyl groups may have one or more substituents, and examples of substituents for alkyl groups, cycloalkyl groups and alkenyl groups include halogen atoms (e.g. fluorine atoms). atom, chlorine atom, etc.), alkoxy group (e.g. methoxy group, ethoxy group, butoxy group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), aryloxy group (e.g. phenoxy group, etc.), alkenyl group, alkoxycarbonyl group Examples of substituents for the aryl group include alkyl groups in addition to those listed as substituents for the alkyl group, cycloalkyl group, and alkenyl group.Preferably R3,
R4 and Rs are a 2-ethylhexyl group, a 7-methyloctyl group, a cyclohexyl group, a phenyl group, an isopropylphenyl group, a straight-chain alkyl group having 8 to 18 carbon atoms, and the like. Furthermore, R3, R4'Js and R9 are never all tolyl groups.

In the present invention, a high boiling point organic solvent refers to an organic solvent having a boiling point of 175° C. or higher at 1 atm.

In the present invention, the amount of the high boiling point organic solvent represented by general formula [II] may be any amount depending on the type and usage amount of the magenta coupler represented by general formula CI], but the weight ratio The high boiling point organic solvent/magenta coupler ratio is preferably 0.05 to 20. Furthermore, the high-boiling point organic solvent according to the present invention represented by the general formula CII) can be used in combination with other conventionally known high-boiling point organic solvents to the extent that the object of the present invention can be achieved. Examples of these high boiling point organic solvents include phthalate ester solvents such as dibutyl phthalate and di-2-ethylhexyl phthalate;
, amide solvents such as N-diethyldodecanamide, fatty acid ester solvents, benzoic acid ester solvents, 2.5-
Examples include phenolic solvents such as di-tert-amylphenol and ether solvents such as dihexadecyl ether.

Specific examples of the high boiling point organic solvent represented by the general formula [■] are shown below, but the invention is not limited thereto.

(P'-1> 0=P fOC, H, -n).

(P-2') (P-3) ○=P←0CsH+*n)+ (P-6) 0=P (-Oc, Hg-n> ¥0CH2CHC,H,).

? C= H5 (P-7) 0= P (-OCaHI7-n)j (P-8) (P-11> 〇 Two P -←○ C,lgo19 n)+(P
-13) 0=P←0CIOH2I n)s (P-15) ′″″′I>0(CH2), CH(CH3)2]2(P
-16) (P-17> 0 ”” P (OC12) (2, n) 3 (P-18) (P-19>(P-21> 0= P (-OC14H29-n)t(1”- 22) 0 = P (OCIS H31n)3(P-23) 0=P-←○C16H33n)s (P-24) ○=PfOCH=CHC,6H,,)3(P-25> 〇-P fcl( , CH20C,H,).

(P-26) 0=P fCH2CH-CH2Cj? )+(P'-2
7) 0=PfCH,CI(CH,CI)3 ■ (P-28) ○ (C,H,O-+2P-0(C)I2→TO-PyonOC
,H9)2On=4 or 6 (P-29> (1”31) n=1.2 or 3 (P-33) (P-35) CH2Cto1=CH2 (P-36) (P-37) The magenta coupler and high boiling point organic solvent according to the present invention can be dispersed and contained in at least one hydrophilic organic colloid layer constituting the photographic light-sensitive layer.

As a method for introducing a coupler into a silver halide emulsion layer, a known method such as that described in US Pat. No. 2,322,027 is generally used.

The high boiling point organic solvent used in the present invention generally has very good solubility for the coupler of the present invention, but there are cases where the coupler is insufficiently dissolved due to the small coupler solvent/coupler ratio. For example, a coupler solvent such as a phthalate coupler solvent can be used in combination. Further, in the present invention, before dissolving the coupler in the coupler solvent, an organic solvent having a boiling point of about 30 to 150°C,
For example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isophthyl ketone, β-22-armed xyethyl acetate, methyl cellosolve acetate, etc. may be present.

Even when a coupler dissolved in a coupler solvent is introduced into a silver halide emulsion layer by these methods, for example, Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-599
The dispersion method using a polymer described in the specification of No. 43 can also be used in combination.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it can also be introduced into the hydrophilic colloid as an alkaline aqueous solution.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Book Press, published in 1964).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver chlorobromide.

Particularly preferred is silver chlorobromide containing from 20 mol % to 100 mol % silver bromide.

The average grain size of silver halide grains in photographic emulsions (the grain size is the grain diameter in the case of spherical or approximately spherical grains, and the average length in the case of cubic grains, expressed as an average based on the projected area) is particularly important. Although not, it is preferably 2μ or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion layer may have a regular crystal structure such as a cube or hexagonal, or may have an irregular crystal structure such as a spherical shape or a plate shape, or may have an irregular crystal structure such as a spherical shape or a plate shape. It may be a composite form of the crystal form. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particle.

The photographic emulsions used in the present invention are "Chemistry and Physics of Photography" by P. Grafkide (Paul Montel Publishing, 1967) and "Photographic Emulsion Chemistry" by C.F. Daaffin (Published by Focal Press, 1966). , V.L., Zelikman et al. “
“Production and Coating of Photographic Emulsions” (Focal Press, 196
4th year > (P, Glafki-des, Chimie
et Physique Photography
ue” ((Paul Mantel, (1967
) ), G.F., Duffin,
”Photo-graphic Emulsion
Chemistry” ((Focal Press
.

(1966) ), V. L., Zelikman e.
tal, ”Making and Coating
Photographic Bmulsion” ((
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 type of simultaneous mixing method, a method of keeping I) Ag in the liquid phase in which silver halide is produced, ie, 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.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, H. Freezer Pigeon ``Basic Silver Halide Photographic Processing'' (Academic Fairark, Inc.,
(Published in 1968) (H, Fr1eser, 'Die
Grundlagender Photography
schen ProzessemitSilver-h
Alogeniden “(Akadem isch
eVarlagsgesellshaft, 1968
), pages 675 to 734 can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g. stannous salts, amines); , hydrazine derivatives, formamidine sulfinic acid, silane compounds): Noble metal compounds (e.g. kumquat salt, pt
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as , Ir, and Pd can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, in the order of azole, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazole neck, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amine triazoles. benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, especially 1-phenyl-5-mercaptotetrazole, etc., mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds such as oxadorinthion; azaindenes, e.g. Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a).

7) Tetraazaindene), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification fraction, adhesion prevention and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.

The photographic emulsions used in the present invention may be spectrally enhanced with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus,
Selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, snawati, indolenine nucleus , benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyryl compounds substituted with a nitrogen-containing heterocyclic group, for example, U.S. Pat.
No. 721), aromatic organic acid formaldehyde complexes (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. The present invention also lends itself to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the edge-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material prepared using the present invention has the general formula [I]
Along with the coupler represented by, other dye-forming couplers,
That is, a compound that develops color by oxidative coupling with an aromatic primary amine developer (eg, phenylene diamine derivative, aminophenol derivative, etc.) may be used in the color development process. For example, as magenta couplers, 5-pyrazolon coupler, pyrazolonbenzimidazole coupler, pyrazolo C5,1-C) (1
, 2, 4) There are triazole couplers, pyrazolopyrazole couplers, pyrazolotetrazole couplers, open chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides)
, etc., and examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are desirably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, there are also colorless DI couplers in which the product of the coupling reaction is colorless and releases a development inhibitor.
It may also contain an R coupling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. Further, the light-sensitive material may contain a coupler or a compound that releases a development accelerator upon development.

The coupler of the present invention and the couplers described above can be used in combination of two or more types in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. Of course you can.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde, etc.), N-methylol compounds (
dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-5-)lyazine, 1,3-vinylsulfonyl- (2-propatur, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-8-triazine, etc.), mucohalogens M (mucochloric acid, mucophenoxychloroic acid, etc.), etc. may be used alone or in combination. I can do it.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted, such as by cationic polymers.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., as described in U.S. Pat. Nos. 3,314,794 and 3,352°681), ), benzophenone compounds (for example, those described in JP-A-46-2784)
, cinnamate ester compounds (e.g. U.S. Pat. No. 3,705)
．． No. 805, those described in No. 3,707,375),
Butadiene compounds (e.g. U.S. Pat. No. 4,045,229)
(as described in US Pat. No. 3,700,455) or benzoxidol compounds (such as those described in U.S. Pat. No. 3,700,455). UV-absorbing couplers (e.g. α-naphthol cyan dye-forming couplers),
A UV-absorbing polymer or the like may also be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

Photographic processing of layers comprising photographic emulsions made using the present invention includes, for example, Research Disclosure No. 176 No. 2
Any of the known methods and known treatment liquids as described on pages 8 to 30 can be applied. The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or higher than 50°C.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known general aromatic amine developer, such as phenylenediamines (e.g. 4-
Amino-N, N-dinitylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, F. A. Mason, "Photographic Chemistry" (
Published by Focal Press) (1966) ((L,,
F. A. Mason “Photograh
ic Processing Chemistry (
Focal Press) (1966) No. 22 of J.
6-229, U.S. Pat. No. 2,193,015, 2.
592,364, JP-A-48-64933, etc. may be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. etc. can be included. Also, if necessary, a preservative such as a water softener, hydroxylamine,
Organic solvents such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents, antioxidants. It may also contain agents.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (■), chromium (■), and copper (II), peracids, quinones, nitrone compounds, and the like are used.

For example, ferricyanide, dichromate, organic complex salts of iron(II) or cobalt(III), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1°3-diamino-2-propatoltetraacetic acid, etc. Alternatively, complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitrosophenols can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (I [I] Sodium and iron ethylenediaminetetraacetate (I[I] ammonium are particularly useful. Iron ethylenediaminetetraacetate (II)
I) Complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

The color photographic emulsion layer forming the dye image layer according to the present invention is coated on a flexible support such as plastic film, paper, or cloth commonly used in photographic light-sensitive materials. Useful flexible supports include films of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers (e.g. polyethylene, polypropylene), etc. Paper coated or laminated with The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light.

When these supports are used for reflective materials, it is preferable to add a white pigment to the support or laminate layer. White pigments include titanium dioxide, barium sulfate,
Examples include zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, titanium phosphate, etc., and titanium dioxide, barium sulfate, and zinc oxide are particularly useful.

The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsions and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

When these supports are used in reflective materials, a parent colloid layer containing white pigment at high density may be further provided between the support and the emulsion layer to improve the whiteness and sharpness of the photographic image. can.

In the reflective material having the magenta coupler of the present invention, a paper support laminated with a polymer is often used as the support, but if a synthetic resin film kneaded with a white pigment is used, smoothness, gloss, sharpness, In addition to improving the degree of
This method is particularly preferable because photographic images with particularly excellent detection and depiction of dark areas can be obtained. In this case, the synthetic resin film raw material is
Polyethylene terephthalate and cellulose acetate are particularly useful as white pigments, and barium sulfate and titanium oxide are particularly useful.

After development and drying, the photographic material of the present invention can be laminated with a plastic film on the front and back sides. Plastic films for lamination include polyolefin,
Examples include polyester, polyacrylic acid esteroboriacetate vinylinopeboristyrene, butadiene-styrene copolymer, polycarbonate, and particularly useful are polyethylene terephthalate, a copolymer of vinyl alcohol and ethylene, polyethylene, and the like.

(Effects of the Invention) According to the present invention, it is possible to obtain a silver halide photographic material with enhanced development activity using a pyrazoloazole magenta coupler. Furthermore, according to the present invention, a silver halide color photographic light-sensitive material is obtained which forms a magenta color image of an excellent hue with a sharp edge of absorption on the long wavelength side and has improved reproducibility and color image fastness.

(Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1 Exemplary coupler (M-1o) was used as a magenta coupler, and 62 g of this coupler was added with exemplary compound (P-5).
13.2 g and 20 ml of ethyl acetate were added, dissolved by heating at 60°C, and added to 100 mβ of an aqueous solution containing 10 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate to obtain a fine emulsified dispersion by a mechanical method. . Silver chlorobromide emulsion 1 consisting of 80 mol% of Br in the total amount of this emulsified dispersion
00 g (containing 6.55 g Ag) plus 2% 2.4-dihydroxy-6-chloro-5- as hardener.
) Add 10mβ of riazine sodium salt and apply.
A sample was prepared by coating the sample on a paper support laminated with polyethylene on both sides so that the coating weight was 180 mg/m+, and providing a gelatin layer on top of this coated layer. This is sample 1
shall be.

Next, in place of the above-mentioned exemplified compound (P-5), exemplified compounds (P-8), (P-12>, (P-25), (P-32
, n=1), (P-40) and (P-42) were used to prepare samples in the same manner. These samples are called sample 2,
3, 4.5.6 and 7. Furthermore, exemplified compounds (P-5
), Sample 8 was prepared by using dibutyl phthalate as a comparative high-boiling organic solvent.

On the other hand, as a magenta coupler, the above-mentioned exemplary coupler (M
-10), Sample 9 was prepared using the following comparative coupler and using exemplified compound (P-5) as the solvent.

Comparison coupler (A.

C5H1(t) These samples 1 to 9 were subjected to a wet exposure of 10,100 OC and treated with the following processing solution.

Developer benzyl alcohol 15 ml diethylene triamine pentaacetic acid 5 g KBr
O,4gNa2SOs
5 gNazCO:+
30 g Hydroxyamine sulfate 2 g 4-amino-3-methyl-N=β-(methanesulfonamide) Ethylaniline 3/2 H2SO4 H, 04.5 g Make up to 1000 ml with water pH 10.1 Bleach-fix ammonium thiosulfate (70 wt %) 50mj2 Na2303 5 gNa
(Fe (EDTA)) 40 gED
TA 4g water 10
pH 6.8 to 00 ml Process Temperature Time Developing solution 33°C 3 minutes 30 seconds Bleach-fixing solution 33°C 1 minute 30 seconds Water Washing 28-35°C 3 minutes The results obtained by carrying out the above treatment are shown in the following table.

From the above results, the combination of the coupler and high boiling point organic solvent of the present invention has high sensitivity and density near the maximum density (shoulder density) in terms of photographic properties, and conventional photographic properties are poor and use is difficult. It was found that the process was dramatically improved, and also showed excellent performance with no fogging.

It has also been found that the color image obtained by color development has a clear magenta hue with a low absorption density on the long wavelength side due to the characteristics of the coupler of the present invention and the use of the high boiling point organic solvent of the present invention.

Next, these samples were subjected to a 20-day fading test using a fluorescent lamp fading device (1.5 million lux), and the results shown in the following table were obtained.

The above results indicate that the combination of the coupler and high-boiling organic solvent of the present invention has excellent color image fastness to light, and also exhibits excellent performance without staining, which is said to be caused by decomposition of the coupler. Recognize.

Example 2 6.62 g of the exemplified coupler (M-10) and 13.2 g of the exemplified compound (P-6) as a high-boiling organic solvent.

A coating solution was prepared according to the method described in Example 1 using 25 ml of ethyl acetate. Then, the exemplary coupler (M
A coating solution was prepared in the same manner as above using 9.56 g of -11), 19.1 g of (P-36), and 30 rr+j7 of ethyl acetate. Furthermore, the comparative coupler shown in Example 1 (A
A coating solution was prepared in the same manner as in Example 1 using 6.45 g of dibutyl phthalate) and 12.9 g of dibutyl phthalate as a high-boiling organic solvent.

Using these coating solutions prepared above, the first layer (lowest layer) to the seventh layer (top layer) as shown in the attached table were coated on a support whose both sides were laminated with polyethylene, and color photographic exposure was performed. Materials 11, 12, and 13 were created.

The coating solution for each emulsion layer was prepared according to the method of the example.

B-
A G-R3 color separation filter was attached, and exposure and processing were performed in the same manner as in Example 1.

In this way (of each sample asked (P-6), (
The color images of samples 11 and 12 using P-36) have higher sensitivity than sample 13, and as shown in Example 1, the density and gradation of the shoulder in the high density area are high, and the density of the fogged area is low. The hue was bright and saturated.

*a 2-(2-hydroxy-3,5-di-Lcrt
-7milphenik)benzotriazole*b 2-(2-hydroxy/-3,5-ditert
-7mil7 enyl)benzotriazole*Cno(2-ethylhex/l)phthalate*d dibutyl phthalate*C2-pentafluorobenzamide-4-chloro-5
-(2-(2,4-noteri-amylphenoquine)
-3-Methylbutyramidophenol*f 2,4-dichloro-3-ethyl-6-[γ-2
．． 4-tert-amyl)butylamide] phenol NJ-10>, (P-6)), [(M-
11), I P-36)) and [(Comparative coupler (A)), [dibutyl phthalate]]*j 1
．． 4-di-tert-amylu-2,5-dioctyloxy/benzene*k 2,2'-methylenebis(4-methyl-6-t
ert-butylphenol *1 α-piparol-α-(3-benzyl-1-hydantoynyl-2-oo-5-
rt-amylphenoxy/)butylamide]acetanilide The following were also used as sensitizing dyes for each emulsion layer.

Blue-sensitive emulsion layer; anhydro-5-methquine-5'-methyl-3,3'-disulfopropyl selenacyanine hydroxy F (2.5XIO-4 per mole of silver halide)
mol) edge-sensitive emulsion layer; anhydro-9-ethyl-5,5
'-Diphenyl-3,3'-disulfoethyloxacarbonanine hydroxide/do (2X10-4 mol per 1 mol of silver halide) Red-sensitive emulsion layer; 3,3'-diethyl-5-methquine-9
,9'-(2,2-dimethyl 1,3-propano)thiadicarpocyanine iodide (2x per mole of silver halide)
Example 3 As a coupler, 7.61 g of the exemplary coupler (M-1) was mixed with the exemplary compound (P-8>15.2 g, 20 ml of ethyl acetate)
was added and heated to 60°C to dissolve. Add this to gelatin 1
0g1 dodecylbenzenesulfonic acid) IJum1.
A fine emulsified dispersion was prepared by a mechanical method by adding it to 100 mβ of an aqueous solution containing Og.
00 g (containing Ag6.55) and 2% 2,4-dihydroxy-6-chloro-5-triazine sodium trilam salt I Qmj! as hardener. was added and coated on a triacetate clear base so that the coating silver was 600 mg/solution, and a gelatin layer was provided as a protective layer on top of this coated layer to prepare a sample. This is designated as sample 21.

Next, the exemplified compound (P-8) was converted into the exemplified compound (P-39).
A sample was prepared using the same method instead.

This is designated as sample 22. Also, exemplary coupler (M-1)
was replaced with (M-29), and to this 9.71 g, 19.4 g of the exemplified compound (P-8) and 19.4 g of (p-39) were added.
and 20rr+j of ethyl acetate to each! A sample was prepared in the same manner as above. These will be referred to as samples 23 and 24.

Furthermore, a sample was prepared in exactly the same manner as described above, using the comparative coupler (A) used in Example 1 as the magenta coupler and using the exemplified compound (P-8> as the high boiling point organic solvent). .This is designated as sample 25.

These samples 21 to 25 were subjected to wedge exposure of 200 CMS and treated with the following processing solution.

1 Color development 36.7℃ 3 minutes 00 seconds 2 Stop
Stop 27℃ 40 seconds 3 Wash with water 27
℃ 40 seconds 4 First fixing 27℃
40 seconds 5 Wash with water 27℃ 40 seconds 6 Prompt
Temperature 27℃ 40 seconds 7 Bleach 27
℃ 40 seconds 8 Wash with water 27℃
40 seconds 9 Second fixing 27℃
40 seconds 10 Water wash 27℃ 1 minute OO seconds 1
1 Stable 27°C 10 seconds Color developer Composition Sodium sulfite 4.35g 4-amino-3-methyl-N.

N-diethylaniline 2.95g Sodium carbonate 17.10g Potassium bromide
Add 1.72g water
1βp810.5 Stop solution composition Sulfuric acid (6N) 50ml Add water 11p81.0 First and second fixer composition Ammonium thiosulfate 60g Sodium sulfite 2.5g Sodium bisulfite 10.3g Potassium iodide
Add 0.5g water
1β pH 5.8 Promoting liquid composition Sodium pyrosulfite 3.3g Glacial acetic acid
5. QmlBA-1 (KODAK persulfate bleach accelerator) 3.3gEDT
Add 0.5g of A.4 sodium salt and water.
1βp84.0 Bleach solution composition Sodium persulfate 33.0g Sodium chloride 15.0g Sodium dihydrogen phosphate 7.0g Phosphoric acid (85%)
Add 2.5ml water
1 pp82.3 Stable liquid composition Formalin (37%) Add 15.0 ml of water lβ The results obtained are shown in Table 3.

Table 3 * Relative value of to (E value) that gives a density of fog +10 based on sample number 25 (comparative coupler A).

*Indicates the slope in the concentration range of 0.5 to 1.5 in characteristic IflIa.

These results clearly show that the use of the pyrazolotriazole of the present invention and the high boiling point organic 18 soot of the present invention clearly improves photographic properties.

Example 4 A color photographic material was prepared by coating the following layers 1 to 11 in multiple layers on a paper support laminated on both sides with polyethylene. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amounts in g/m' are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

111! (Antihalation layer) Black colloidal silver ... 0.01 Gelatin ... 0.2 Second layer (low-sensitivity red-sensitivity layer) Iodor odor spectrally sensitized with red sensitizing dyes (*5 and *4) Silver emulsion (silver iodide 3.5 mol%, average grain size 0.7μ)
...Silver 0.15 gelatin
... 1.0 cyan coupler (*3) ...
0.30 Anti-fading agent (*2) ... 0.1
5 coupler solvent (*18 and *1)...0.06 3rd
Layer (high sensitivity red sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (*5 and 4) (silver iodide 8.0 mol%, average grain size 0.7μ)
...Silver 0.10 gelatin
... 0,50 cyan coupler (*3) ...
0.10 Anti-fading agent (*2) ... 0
．． 05 coupler solvent (*18 and *l)... 0.02
4th layer (middle layer) Yellow colloidal silver ---0,02 gelatin
... 1. C0 color mixing prevention agent (*14
) ... 0.08 color mixing inhibitor solvent (*13
) ... 0.16 polymer latex (*6)
...0.40 Fifth layer (low sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with a green sensitizing dye (*12>) (silver iodide 2.5 mol%, average grain size 0.40) 4μ)
...Silver 0.20 gelatin
... 0.70 magenta coupler (*11) ...
・0.40 anti-fading agent A (*10)...
0. C5 anti-fading agent B (*9) ... 0.
05 Anti-fading agent C (*8) ... 0.02
Coupler solvent (*18) ... 0.40 No. 6
Layer (high sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) (silver iodide 3.5 mol%, average grain size 0.9μ)
...Silver 0.20 gelatin
... 0.70 magenta coupler (*11) ・
・・・ 0.40 Anti-fading agent A (*10) ・・・
0. C5 anti-fading agent B (*9) ... 0
．． 05 Anti-fading agent C (*8) ... 0.0
2 coupler solvent ($18) ... 0.40 7th layer (yellow filter single layer) yellow colloid)'! ...-0,20 gelatin ... 1. C0 color mixing prevention agent (*
14)...0. C6 color mixture inhibitor solvent (*13) ... 0.24 8th layer (low sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (*16) (silver iodide 2. 5 mol%, average particle size 0.5μ)
...Silver 0.15 gelatin
... 0.50 yellow coupler (*15)
... 0,20 coupler solvent (*18) ・
...0.05 9th layer (high sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (*16) (silver iodide 2.5 mo%, average grain size 1.4μ) )
...Silver 0.20 gelatin
... 0.50 yellow coupler (*15) ...
・0.20 coupler solvent (*18)...
0.05 10th layer (ultraviolet absorption layer) Gelatin... 1.50 Ultraviolet absorber (*19)... 1.0 Ultraviolet absorber solvent (*18)... 0.30 Color mixing inhibitor (* 17)
... 0.08 Round 41 (protective layer) Gelatin ... 1.0 The compounds used here are as follows: *1 Dioctyl phthalate *2 2-(2-hydroxy-3-sec -butyl-5
-t-buf-ruphenyl)benzotriazole*3 2-(α-2,4-di-t-amylphenoxy)
butylamido)-4,6-dichloro-5-ethylphenol*4 5,5'-dichloro-3,3'-di(3-sulfobutyl)-9-ethylthiacarbonylcyanine Na salt*5 Triethylammonium-3-C2 -(2-(3
-(3-sulfopropyl)naphtho (1゜2-d)thiazolin-2-ylidenemethyl-1-butenyl)-3-
Naphtho(1,2-d)thiazolino]propanesulfonate*6 Polyethyl acrylate*7 Trioctyl phosphate*3 2.4-di-t-hexylhydroquinone*9 Di(2-hydroxy-3-t-butyl-5 -methylphenyl)methane*10 3,3.3',3'-tetramethyl-5°6.
5',6'-tetrapropoxy-1゜1'-bisspiroindane *11 Comparative coupler (A) shown in Example 1 *12
5.5'-diphenyl-9-ethyl-3゜3'-disulfopropyloxacarbocyanine Na salt *13 Phosphoric acid-o-cresyl ester *142.4
-di-t-octylhydroquinone *15 α-pivaloyl-α-[:(2,4-dioxo-1-benzyl-
5-ethoxyhydantoin-3-yl)-2-chloro-
5-[α-(2,4-di-t-amylphenoxy)butanamine]acetanilide*16 triethylammonium 3-(2-(3-benzylrhodanin-5-ylidene)-3-pensoxazolinyl)propanesulfonate *172.4-di-5ec-octylhydroquinone *18 dibutyl phthalate *195-chloro-2-(2-hydroxy-3-t-butyl-5-t-octyl)phenylbenztriazole Each layer contains a gelatin hardener. 1. 4-bis(vinylsulfonylacetamido)ethane and a surfactant were added.

The sample prepared as described above was designated as sample number 31, and was used as a sample for comparison from now on.

Next, the process was carried out in the same manner as Sample 31 except that the magenta coupler (M-1) of the present invention was used in the following fifth layer (low sensitivity green sensitive layer) and sixth layer (high sensitivity green sensitive layer). After adjustment, sample 32 was prepared.

5th layer (low green sensitivity layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12> (silver iodide 2.5 mol%, average grain size 0.4 μ)
...Silver 0.10 gelatin
... 0,70 magenta coupler (M-1) ・
・・・ 0.59 Anti-fading agent A (*10) ・・・
0.07 Anti-fading agent B (*9) ... 0
．． 02 coupler solvent (*18) ... 0.5
9 6th layer (highly sensitive green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) Silver iodide 3.5 mol%, average grain size 0.9μ)
...Silver 0.10 gelatin
... 0.70 magenta coupler (M-1) ...
・0.59 Anti-fading agent A (*10)...
0.07 Anti-fading agent B (*9) ... 0.0
2 coupler solvent (*18) ... 0.59 Next, the magenta coupler (M-1) of the present invention and the exemplary compound (P-10) of the present invention are shown in the fifth layer (low-sensitivity green-sensitive layer). )
Sample 33 was prepared in the same manner as Sample 31 except that it was used for the sixth layer (high sensitivity green sensitive layer).

5th layer (low green sensitivity layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12> (silver iodide 2.5 mol%, average grain size 0.4 μ)
...Silver 0.10 gelatin
... 0.70 Mazenk coupler (M-1>
... 0.59 anti-fading agent Δ (*10) ...
・0.07 anti-fading agent B (*9)...
0.02 coupler solvent (P-10>...0.5
9 6th layer (highly sensitive green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) (silver iodide 3.5 mol%, average grain size 0.9 μ)
...Silver 0.10 gelatin
... 0.70 magenta coupler (M-1)
... 0.59 fox color inhibitor A (*10) ・
... 0.07 anti-fading agent B (*9) ...
0.02 Coupler solvent (P-10)...0.
59 These materials 31 to 33 were subjected to wedge exposure according to a conventional method and then subjected to the following development treatment. The results are shown in Table 4.

The concentration was measured using Fuji FSD103.

[Processing process]

First development (black and white development) 38℃ Bi 15” water
Washing 38℃ 1"30" Reverse exposure 100 Lux or more 1" or more Color development 38℃ 2'15" Water washing
38℃ 45” bleach fixing 38℃ 2’00” water washing
38°C 2° 15” [Processing solution composition] First developer Nitrilo-N,N,N-)tumethylenephosphonic acid, pentasodium salt 0.6g Diethylenetriaminepentaacetic acid, pentasodium salt 4.0g Potassium sulfite 30.0g Potassium thiocyanate 1.2g Potassium carbonate
35.0g Hydroquinone monosulfonate potassium salt 25.0g Diethylene glycol 15.0ml ■ ml Neil 4-
Hydroxymethyl-4-methyl-3-pyrazolidone 2.0g Potassium bromide 0.5g Potassium iodide
Add 5.0mg water
1! (pH 9,70) Color developer Benzyl alcohol 15.0ml Diethylene glycol 12.0ml 13.6-cythia 1.8-octanediol 0.2g Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 0.5g Diethylenetriamine Pentaacetic acid/pentasodium salt 2.0g Sodium sulfite 2.0g Potassium carbonate
25.0g hydroxylamine sulfate 3.0g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g potassium bromide 0.5g potassium iodide
Add 1.0mg water
1 β(p) 110.40) Bleach-fix solution 2-mercapto-1,3,4-triazole 1. Og ethylenediaminetetraacetic acid disodium trihydrate 5. Og ethylenediaminetetraacetic acid/Fe(III)/ammonium hydrate 80.0g
Sodium sulfite 15.0g Lithium thiosulfate (700g/,!' liquid) 160.
0ml glacial acetic acid 5.9ml
Add water to 1p (pH 6,5
0) Table 4 * Magenta concentration residual rate after irradiation with xenon light (100,000 Lux) for 12 days ※※ [Yellow stain density after 60°C, 70% R1+, 6iJ] - [Yellow stain density of Freno/U] Top As can be seen from the table, Sample 33 using the coupler of the present invention and the high boiling point organic solvent of the present invention exhibits excellent color density and color image stability, and is free from stains that impair image quality. It is clear that the incidence is also low. Moreover, the obtained color image showed a bright magenta color with high color saturation.

Example 5 Next, Sample 41 was prepared by applying the first to twelfth layers on the triacetate film base in the following order.

1st layer; antihalation layer UV absorber 5-chloro-2-(2-hydroxy-3,
15 g of 5-di-t-butylphenyl)-28-benzotriazole, 30 g of 2-(2-hydroxy-5-t-butylphenyl)-28-benzotriazole, 2-(
35 g of 2-hydroxy-3-sec-butyl-5-t-butylphenyl)-2H-benzo) IJ azole, and dodecyl 5-(N,N-diethylamino)-2
-benzenesulfonyl-2,4-pencudienoate 1
00 g, 200 ml of tricresyl phosphate, 200 ml of ethyl acetate, 20 g of sodium dodecylbenzenesulfonate, and an aqueous 10% gelatin solution with high speed stirring (hereinafter referred to as emulsion (a)). mixed with silver, water, and coating aids;
The coating was applied so that the dry film thickness was 2μ.

2nd layer: gelatin intermediate layer 2.5-di-t-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate, and the resulting mixture was stirred at high speed with 1 kg of a 10% gelatin aqueous solution. 10 2 kg of material (referred to as b)
% gelatin and applied to a dry film thickness of 1 μm.

3rd layer: low-sensitivity red-sensitive emulsion layer 100 g of 2-(heptafluorobutyramide)-5-(2'-(2", 4"'-di-monoaminophenoxy)butyramide)-phenol, which is a cyan coupler, Tricresyl phosphate 100CC and ethyl acetate 10
Emulsion obtained by dissolving in 0 cc and stirring at high speed with 1 kg of 10% gelatin aqueous solution (hereinafter referred to as emulsion (C)) 5
00 g was mixed with 1 kg of red-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, iodine content was 4 mol %) and coated to a dry film thickness of 1 μm. (Silver amount 0.5g
/m') 4th layer: Highly sensitive red-sensitive emulsion layer The emulsion (C) was mixed with 1 kg of red-sensitive silver iodobromide emulsion (70 g of silver).
, 60 g of gelatin, and an iodine content of 2.5 mol %) was mixed and coated to a dry film thickness of 2.5 μm. (I
Amount: 0, 8 g/m') Fifth layer: 1 kg of intermediate layer emulsion (b) was mixed with 1 kg of 10% gelatin, and coated to a dry film thickness of 1 μm.

6th layer: low-sensitivity blue-sensitive emulsion layer An emulsion obtained in the same manner as the emulsion of the 3rd layer except that a magenta coupler was used instead of the cyan coupler and di-2-ethylhexyl phthalate (hereinafter referred to as Emulsion (d
)) and 1 kg of green-sensitive silver iodobromide emulsion (
The mixture contained 70 g of silver and 60 g of gelatin (with an iodine content of 3 mol %) and was coated to a dry film thickness of 2.0 μm. (Silver amount: 0.7 g/m'') 7th layer: Highly sensitive green-sensitive emulsion layer 1000 g of emulsion (d) was mixed with 1 kg of green-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, the iodine content was 2.5 mol%) and coated to give a dry film thickness of 2.0 μm. (silver fine 0.7 g/m') 8th layer: Gelatin intermediate layer emulsion (b) 1 kg was mixed with 10% gelatin. Mix to 1 kg,
The coating was applied to a dry film thickness of 0.5 μm.

Ninth layer: yellow filter A yellow emulsion containing colloidal silver was coated to a dry film thickness of 1 μm.

10th layer: low-sensitivity blue-sensitivity emulsion layer with yellow coupler instead of cyan coupler
An emulsion obtained in the same manner as the third layer emulsion (hereinafter referred to as Emulsion (e)
1000 g of the emulsion was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, iodine content was 2.5 mol %) and coated to a dry film thickness of 1.5 μm. (Silver amount: 0.6 g/m') 11th layer: Highly sensitive blue-sensitive emulsion layer Emulsion (e) 1000 g was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (tji: 70 g, gelatin: 60 g, iodine content: 2 .5 mol %) and coated to a dry film thickness of 3 μm. (Silver 11.1 g/m') 12th layer; Second protective layer emulsion (a) was mixed with 10% gelatin, water, and a coating aid, and coated to a dry film thickness of 2 μm.

13th layer: Fine grain emulsion covered with the surface of the first protective layer (grain size 0106μ,
A 10% gelatin aqueous solution containing 1 mol % silver iodobromide emulsion) was coated to give a silver coating i.i. of 0.1 g/m' and a dry film thickness of 0.8 μm.

A gelatin hardener 1,4-bis(vinylsulfonylacetamido)ethane and a surfactant were added to each layer, respectively.

Next, Sample 42 was prepared in the same manner as Sample 4I, except that the magenta coupler (M-28) of the present invention was used in the following 6th low green sensitivity layer and 7th high green sensitivity layer. It was created.

6th layer: low green sensitivity layer Emulsify an emulsion obtained in the same manner as the emulsion of the 3rd layer (hereinafter referred to as emulsion <r>) except that the magenta coupler of the present invention (M-28> was used) The mixture was mixed with 500 g of a silver iodobromide emulsion (containing 35 g of silver and 30 g of gelatin, and the iodine content was 3 mol %) for the green-sensitive layer in an amount equal to the mole of substance (d), and coated to give a dry film thickness of 2.aμ.

(Amount of silver 0.35 g/m') 7th layer: Highly sensitive green sensitive layer Emulsion (d) and emulsion (f) in an equimolar amount were mixed with 500 g of green sensitive silver iodobromide emulsion (35 g of silver, 30 g of gelatin). iodine content is 2.5 mol%), and the dry film thickness is 2.0μ.
It was applied so that (Amount of silver 0.35 g/m') Next, the same as the emulsion of the third layer was used except that the magenta coupler (M-28) of the present invention and the high boiling point organic solvent (P-8) of the present invention were used. The emulsion obtained (hereinafter referred to as emulsion (g))
That's what it means. ) was used in place of the emulsion (f) of Sample 42 to prepare a sample, designated as Sample 43.

These samples 41 to 43 were subjected to wedge exposure according to a conventional method and then subjected to the following development treatment, and the results are shown in Table 5.

The concentration was measured using Fuji FSD-103.

Processing process Time Temperature First development 6 minutes 38℃ water washing
2 minutes 7 reversals
2 minutes Color development 6 minutes
〃 Adjustment 2 minutes 〃 Drifting
White 6 minutes〃、Fixed
4 minutes/l Wash with water 4 minutes Stable
Dry for 1 minute at room temperature. The composition of the processing solution used is as follows.

No.-Developer water 70
3ml Nitrilo-N,N,N-h Tumethylenephosphonic acid pentasodium salt 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (-hydrate)
30g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2g potassium silver bromide 2.5g potassium thiocyanate 1.2g potassium silver iodide (0.1%
Solution) Add 2ml water
l OOOml inverted liquid water 7
00ml nitrilo-N,N,N-)tumethylenephosphonic acid pentasodium salt 3g stannous chloride (trihydrate) Igp-aminophenol 0.1g sodium hydroxide
8g glacial acetic acid
Add 15ml water 100
0ml color developer water 70
0ml Nitrilo-N,N,N-)tumethylenephosphonic acid pentasodium salt 3g Sodium sulfite 7g Sodium triphosphate (dodecahydrate) 36g Potassium bromide
1g potassium iodide (0.1% solution)
9Qml sodium hydroxide
3g Citrazic acid 1.
5g N-ethyl-N-(β-mectunsulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11g 3.6-cythiaoctane-1.8-diol 1g water Add 1000ml Adjustment liquid water 70
0ml sodium sulfite 12g sodium ethylenediaminetetraacetate (trihydrate) 8g thioglycerin Q, 4ml glacial acetic acid
Add 3ml water
1000ml bleach solution water 800
g Sodium ethylenediaminetetraacetate (trihydrate) 2g Iron ethylenediaminetetraacetate (II [>Ammonium (trihydrate)) 120g Potassium bromide 100g Add water to 1000ml fixer water 8
0 Qml Sodium Thiosulfate 80.0
gSodium sulfite 5.0gSodium bisulfite 5.0gAdd water
I Q 0ml stable liquid water 8
0 Qml formalin (37 tons%) 5
．． Qml Fuji Drywel (Fuji Film Co., Ltd. surfactant) Add 5.0ml water and add 100 Qm1 Table 5 * Xenon light (100,000 Lux) Magenta 6 degree residual rate after 4 days of irradiation ※※ [60℃, 70% RH, yellow stain concentration after 4 weeks] - [yellow stain concentration of Freno/:] From the results in the above table, sample 43 using the coupler of the present invention and the high boiling point organic solvent of the present invention has good color development. It shows the concentration and the possibility of reducing the amount of silver. It also has excellent color image stability and causes little staining, which is very advantageous for printing materials in conjunction with the previous embodiments. Furthermore, the obtained magenta color image showed a vivid hue with high saturation.

〔Effect of the invention〕

As described above, according to the present invention, color density, color image fastness, and color reproducibility are improved, the amount of silver can be reduced, and a silver halide color photographic material with less staining can be obtained. .

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer provided on a support, wherein the silver halide emulsion layer contains a compound represented by the following general formula [I]. At least one type of magenta coupler represented by the following general formula [
1. A silver halide color photographic material characterized in that it is co-dispersed with at least one high-boiling point organic solvent represented by [II]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a group that can be separated by reaction. R_1, R_2 or X may form a dimer or more multimer. Here, at least one of R_1 and R_2 represents a group bonded to the pyrazoloazole ring via a secondary or tertiary carbon atom, and further, R_1
At least one of R_2 and R_2 is a group having one or more -NHSO_2- groups. However, when R_1 is a tertiary alkyl group or when R_2 is bonded to the pyrazolotriazole ring through a secondary carbon atom, R_2 is not a substituted aralkyl group. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ [In the formula, R_3, R_4 and R_5 are an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkenyl group, a substituted alkenyl group, respectively. , represents an aryl group or a substituted aryl group. However, R_3,
The total number of carbon atoms in the groups represented by R_4 and R_5 is 12 to 60. Here, R_3, R_4 and R_5 are not all tolyl groups. ]