JPH01302249A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the title material with excellent optical durability and color reproducibility by incorporating a pyrazoloazole type magenta coupler shown by the formula in the silver halide emulsion or its adjacent layer contd. in the photosensitive material. CONSTITUTION:The pyrazoloazole type magenta coupler shown by formula I is incorporated in the emulsion or its adjacent layer mounted on a supporting body. The couplers shown by formulas II and III are excluded from the coupler shown by formula I. In formula II, X is halogen atom, R<11> is a substd. or an unsubstd. alkyl group, R<12> is alkyl group having a substituting group (wherein the substituting group is excluded aryl group directly bound with alkyl group). In formula III, X is halogen atom, R<11> and R<12> are each a substd. or an unsubstd. alkyl group. At least one of the groups R<11> and R<12> is a branched alkyl group including the meanings of the groups R<1>, R<2> and R<3>, R<1> is a substd. or an unsubstd. alkyl group, R<2> and R<3> are each hydrogen atom or a substituting group, one of the groups R<2> and R<3> is a substituting group. Thus, an azomethine dye with the excellent photodurability is formed, and the photodurability and the color reproducibility of a color image are improved.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved color image light fastness. It is something.

(Prior art) When a silver halide color photographic light-sensitive material is color-developed, the oxidized aromatic-amine color developing agent and coupler react to produce indophenol, indoaniline, indamine, azomethine, and phenoxazine. It is well known that , phenazine and similar dyes are produced and color images are formed. Among these, 5-pyrazolone, cyanoacetophenone, indashilon, pyrazolobenzimidazole, and pyrazolotriazole couplers are used to form a magenta image.

Hitherto, most of the magenta color image-forming couplers that have been put into practical use and have been extensively researched are 5-pyrazolones. Dyes formed from 5-pyrazolone couplers have excellent fastness to heat and light, but 430
It has a yellow component due to unnecessary absorption near nm,
This was known to be a cause of color turbidity.

The pyrazolobenzimidazole skeleton has long been described in British Patent No. 1,047,612 as a magenta image-forming coupler skeleton that reduces this yellow component, and U.S. Patent No. 3
, 770,447 or the IH-
Pyrazolo [5, Nitan) (1,2,4) triazole skeleton has been proposed. Additionally, 1) i-imidazo(
1,2-b) Pyrazole skeleton, European Patent No. 119,86
IH-pyrazolo (1,5-1 year) described in No. 0 (
1,2,4) Triazole skeleton, RD 24220
IH-pyrazolo (1
, 5-d) Tetrazole skeleton and RD 24230
(June 1984) LH-pyrazolo (1,
5-b) Pyrazole skeleton etc. were proposed.

Among these, US Patent No. 3,725,067, British Patent No. 1
．． 252,418, IH-pyrazolo(5,1-c)(1,2,4
) Triazole coupler, European Patent No. 119.741
IH-imidazo(j,2-b) pyrazole couplers described in European Patent No. 119,860, IH-pyrazolo[1,5-亙)(1,2°4] triazole couplers described in , RD 24220 (June 1984) and RD 24230 (1984).
The magenta dye formed from the IH-pyrazolo [1°5-top] pyrazole coupler described in June 2013 has excellent absorption with no unnecessary absorption in the visible region in solvents such as ethyl acetate and dibutyl phthalate. Show characteristics.

However, among these couplers, azomethine dyes formed from IH-pyrazolo[5,1-technical] (1,2,4) triazole couplers have extremely low fastness to light, and are difficult to use in color photographic materials, especially in prints. This significantly deteriorated the performance of color photographic materials. Furthermore, the light fastness of azomethine dyes formed from other pyrazoloazole magenta couplers is insufficient for use in color photographic materials, particularly print-type color photographic materials.

(Problems to be Solved by the Invention) The first object of the present invention is to use a pyrazoloazole magenta coupler that produces an azomethine dye with excellent light fastness, thereby producing a halogen dye with improved color image fastness to light. An object of the present invention is to provide a silver oxide color photographic material.

A second object of the present invention is to provide a silver halide color photographic material with improved color image light fastness and improved brown color reproducibility.

(Means for Solving the Problems) The above object 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. This was achieved by a silver halide color photographic light-sensitive material characterized by containing a pyrazoloazole magenta coupler represented by the following general formula (1).

General formula (1) (wherein (A) represents a pyrazoloazole magenta coupler residue, R1 represents an alkyl group, R2 and R
3 represents a hydrogen atom or a substituent, but R2 and R3 are not both hydrogen atoms. n represents 1.2 or 3. From the coupler of formula (1), the following (V) and (Vl
) except for couplers represented by

(However, in the formula [■], X is a halogen atom, and R11
is a substituted or unsubstituted alkyl group, R'' is an alkyl group having a substituent (however, excluding an aryl group directly bonded to the alkyl group as a substituent), and in formula (VI),
X is a halogen atom, R1 is a substituted or unsubstituted alkyl group, RI2 is a substituted or unsubstituted alkyl group, and in formulas (V) and (VI), R11 and R1□ are -C-I?” (R' represents a substituted or unsubstituted alkyl group, R2 and R3 represent a hydrogen atom or a substituent, and the number of R2 and R3 (both one is a substituent)
A branched alkyl group represented by the general formula (V)
Polymer couplers are excluded from magenta couplers. )] Specifically, the pyrazoloazole magenta coupler of the present invention is represented by general formula (n).

General formula [■] [In the formula, X represents a hydrogen atom or a coupling-off group.

it R4 represents a hydrogen atom, an alkali group represented by -C-R" or other substituent. Z-1Zb and Zc are methine, substituted methine, methylene, substituted methylene,
=N- or -NH-, Z.

One of the Zb bond and the 2b-2c bond is a double bond, and the other is a single bond. 2. ．． When 2b or Zc is substituted methine or substituted methylene, the substituent is -C-R
is an alkyl group represented by 2 or another substituent. Among the tA groups and R4 placed on carbon atoms other than the coupling active position, at least one of the R+ groups is an alkyl group represented by -C-R2. Furthermore, a dimer or higher polymer may be formed by X, R' or a substituent on a carbon atom. ] In general 2 (n), multimer means one having two or more groups represented by general formula (n) in one molecule, and also includes bis forms and polymer couplers. . Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula (Ill) (preferably one having an ethylenically unsaturated group, hereinafter referred to as vinyl monomer), or an aromatic - Copolymers may be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of grade amine developers.

Among the pyrazoloazole magenta couplers represented by the general formula (11), preferred ones are the following - general formula (I[I
), [■], (V), (Vl) or [■].

(I[[)CrV)
(V) (Vl) [■
] In the general formula CI[[) and (TV), R1, R'
At least one of the substituents represented by 2 and R13 is an alkyl group represented by -C-R''.

In general formula [■] and (Vl), R11 and R
At least one of the substituents represented by r2! ? 1 In the general formula CV), X is a halogen atom, RII is a substituted or unsubstituted alkyl group, and RI2 is an alkyl group having a substituent (provided that an alkyl group directly bonded to the alkyl group as a substituent) Couplers (excluding polymer couplers) that are (excluding groups) are excluded from the pyrazoloazole magenta couplers represented by the general formula [■]. Also,
In the Fm formula (Vl), a coupler in which X is a halogen atom, R'' is a substituted or unsubstituted alkyl group, and Rlz is a substituted or unsubstituted alkyl group is a pyrazolo compound represented by the -S formula (II). Excluded from azole magenta couplers.

In the general formula [■], R is an alkyl group represented by -C-R''.

Next, the alkyl group represented by -C-R'' will be explained in detail.

R1 may be a straight chain alkyl group or a branched alkyl group, for example, a methyl group, ethyl group, propyl group, methyl group, pentyl group, hexyl group, heptyl 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,
These include eicosyl group, cyclopentyl group, cyclohexyl group, etc.

These alkyl groups may have one or more substituents, such as halogen atoms (e.g. fluorine atom, chlorine atom, etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, etc.). group, 2,2-dimethylpropyl group, n-butyl group, t-butyl group, trifluoromethyl group, tridecyl group, 3-(2,4-di-t-amylphenoxy)propyl group, allyl group, 2- dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), alkenyl group (e.g., vinyl group, etc.), alkynyl group (e.g., 1-propynyl group, etc.) ), aryl group (
For example, phenyl group, 4-butylphenyl group, 2,
4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, hydroxyl group, alkoxy group (e.g., methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-
methanesulfonyl ethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4
-t-butylphenoxy group, etc.), heterocyclic oxy group (
For example, 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., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamide group, benzamide group, etc.) group, tetradecanamide group, α-(2,4-di[-amylphenoxy)butyramide group, r-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α-(4-(4-
(hydroxyphenylsulfonyl) phenoxy) decanamide group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group) , N-acetylanilino group, 2-
Chloro-5-(α-(3-butyl-4-hydroxyphenoxy)dodecanamido)anilino group, etc.), amino group (e.g. ethylamino group, dimethylamino group, methyloctylamino 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 group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, Octylthio group, tetradecylthio group, 2-
phenoxyethylthio group, 3-phenoxyprobylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g. phenylthio group,
2-butoxy-5-t-octylphenylthio group, 3-
pentadecyl phenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.)
, heterocyclic thio groups (e.g., 2-hendithiazolylthio group, etc.), alkoxycarbonylamino groups (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino group, etc.) carbonylamino group, 2,4-
tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methoxy- 5-t-butylbenzenesulfonamide group, etc.), carboxyl group,
Carbamoyl group (e.g., N-ethylcarbamoyl group,
N, N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-(3-(2,4-diter)
t-amylphenoxy)propyl)carbamoyl group, etc.), acyl group (e.g., acetyl group, (2,4-di-L)
er t-amylphenoxy)acetyl group, penzoyl group, etc.), sulfamoyl group (e.g. eva, 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. octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group,
octadecylcarbonyl group, etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group, 3-
pentadecyloxy-carbonyl group, etc.). R2 and R3 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, silyloxy groups, sulfonyloxy group, acylamino group, anilino group, amino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, peterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone It represents an amide group, a carboxyl group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. More specifically, R2 and R3 are hydrogen atoms, halogen atoms (e.g. fluorine atoms, chlorine atoms,
etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, 2,2-dimethylpropyl group, n-butyl group,
t-butyl group, trifluoromethyl group, tridecyl group,
3-(2,4-di-t-amylphenoxy)propyl group, allyl group, 2-dodecyloxyethyl group, 3-phenoxyprobyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc. ), aryl group (
For example, phenyl group, 4-t-butylphenyl group, 2,
4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-hendithiazolyl group, etc.), cyano group, hydroxyl group, alkoxy group (e.g., methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-
methanesulfonyl ethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4
-t-butylphenoxy group, etc.), heterocyclic oxy group (
For example, 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., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamide group, benzamide group, etc.) group, tetradecanamide group, α-(2,4-di-t-amylphenoxy)butyramide group, r-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α-(4-(4-
hydroxyphenylsulfonyl) phenoxy) decanamide group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group) N-acetylanilino group, 2-
chloro-5-(α-(3-t-butyl-4-hydroxyphenoxy)dodecanamido)anilino group, etc.), amino group (e.g. ethylamino group, dimethylamino group, methyloctylamino group, etc.), ureido group (e.g. phenylureido group, methylureido group, N,N-dibutylureido group, etc.), imide group (e.g. N-succinimide group, 3-penzylhydantoinyl L4-(2-ethylhexanoylamino)phthalimide groups, etc.), sulfamoylamino groups (e.g., N,N-dipropylsulfamoylamino groups, N-methyl-N-decylsulfamoylamino groups, etc.), alkylthio groups (e.g., methylthio groups, octylthio groups) , tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group,
), 2-ruthio group (e.g., phenylthio group, 2-
5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), heterocyclic thio group (e.g., 2-benzothiazolylthio group) ,
), alkoxycarbonylamino groups (e.g., methoxycarbonylamino groups, tetradecyloxycarbonylamino groups, etc.), aryloxycarbonylamino groups (
For example, phenoxycarbonylamino group, 2,4-di-tert-butylphenoxycarbonylamino group, etc.)
, sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methoxy-5-t-butylbenzenesulfonamide group, etc.) , carboxyl group, carbamoyl group (e.g., N-ethylcarbamoyl group, N, N
-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-(3-(2,4-diter t-
amylphenoxy)propyl)carbamoyl group, etc.),
Acyl group (e.g., acetyl group, (2,4-diter)
t-amylphenoxy)acetyl group, benzoyl group,
etc.), sulfamoyl groups (e.g., N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group,
N-(2-F7'syloxyethyl)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. octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group) ,etc),
Alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), Roxycarbonyl group (e.g., phenyloxycarbonyl group, 3
-pentadecyloxy-carbonyl group, etc.).

In general formulas (III) and (IV'l), RI+,
Among the substituents represented by R'' and R'3, p+ is preferably one represented by R2 and R3 described above.

In general formulas (V) and (Vl), R1+ and R
Among the substituents represented by IK, those other than the alkyl group represented by "-C-R" are preferably aryl groups, alkoxy groups, aryloxy groups, etc. represented by R2 and R3 described above. be.

In the general formulas (I[[), (IV), (V), (Vl) and [■], Groups linked via oxygen atoms (e.g., acetoxy group, bilopanoyloxy group, benzoyloxy group, 2.4
-dichlorobenzoyloxy group, ethoxyoxaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2
-phenethyloxy group, 2-phenoxyethoxy group, 5
-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), groups linked via nitrogen atoms (e.g., benzenesulfonamide group, N-ethyltoluenesulfonamide group, peptafluorobutanamide group, 2-benzothiazolyloxy group, etc.),゜3.4
, 5.6-pentafluorobenzamide group, octane sulfonamide group, p-cyanophenylureido group, N,
N-diethylsulfamoylamine group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl group, 1-benzyl-ethoxy-3-hydantoynyl group, 2N-1,1-dioxo- 3(2H)-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-)
Riazol-1-yl group, henzimitazolyl group, 3”
Niazyl-1-hydantoynyl group, 1-benzyl-5-
hexadecyloxy-3-hydantoynyl group, 5-methyl-1-tetrazolyl group, etc.), arylazo group (e.g. 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-naphthylazo group, 3- Methyl-
4-hydroxyphenylazo 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 group, 2-(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-thiophenylthio group, 2-phenyl-3-dodecyl-1,2,4-triazole-5-
thio group, etc.).

In the coupler of general formula (I[l), R12 and R1
3 may be bonded to form a 5- to 7-membered ring that is not an aromatic ring.

In the coupler of general formula (IV), RIt and RI3
may be combined to form a 5- to 7-membered saturated ring, unsaturated ring, or aromatic ring.

When R1, R1, R'1 or X becomes a divalent group to form a bis body, preferably Rl l, R12, RI3
is a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, 1,10-decylene group, -CIlzC
Ilz-0-CHzCllz-, etc.), substituted or unsubstituted phenylene groups (e.g. 1,4-phenylene group, 1
．． 3-phenylene group, -NHCO-R"-CONH-, etc. (R14 represents a substituted or unsubstituted alkylene group or phenylene group, for example, CHl, -NHCOCllzCHzCON) I-, -NHCO
CH2CCHzCONH-L (R14 represents a substituted or unsubstituted alkylene group; CH
3 COCHl, etc.), and X represents the above monovalent group converted into a divalent group at an appropriate position.

R11, R12, R'3, The linking group represented by is an alkylene group (substituted or unsubstituted alkylene group, for example, methylene group, ethylene group, l
, 10-decylene group, -CH, CIIzOCHzCHz
-, etc.), phenylene group (substituted or unsubstituted phenylene group, such as 1.4-phenylene group, 1.3-phenylene group, -HCO-2-CONH-1-〇-1~0CO- and Aralkylene (Cl), etc.).

Preferred linking groups include the following.

-CON+1-CH, C112N11CO~, -CH,
CII□0-Cf1zCFlz-N! (CO-2,
The ethylenically unsaturated group in vinyl alone has the general formula (III
), (■), (V), (VI) or [■] may have substituents, and preferred substituents are hydrogen atoms, chlorine atoms, or lower alkyl groups having 1 to 4 carbon atoms. (eg methyl group, ethyl group).

General formula (II), (IV), (V), [VT) or [
(2) The monomers containing the arrearates may be copolymerized with the oxidation products of bitter-aromatic-grade amine developers and non-chromogenic ethylene-like monomers that do not cuff pull.

Acrylic acid, α
-chloroacrylic acid, alpha-alacrylic 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, iso-)゛thyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic vinyl compounds (e.g. styrene and its derivatives) , vinyltoluene, divinylbenzene (1. vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, dinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N -vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler Latinx is particularly preferred.

Among couplers represented by general formulas (I [I], (IV), [V], (Vl) and [■], particularly preferred are general formulas (III), (TV), (Vl) and [■ ]
Among them, the most preferred one is the one represented by the general formula (Vl), especially from the viewpoint of the hue and storage stability of the chromophore.

Examples of compounds and synthesis methods of couplers represented by general formulas (I[[), (IV), [v], (VT) and [■] are as follows:
It is described in the documents listed below.

-1 For the coupler represented by the formula (I[l), see European Patent No. 119,741, for the coupler represented by the general formula (IV), see JP-A-60-43659, and for the coupler represented by the general formula (V). Regarding couplers that can be used, see U.S. Patent Nos. 3.705.896 and 3,725,067, etc.
The coupler represented by the general formula (Vl) is described in European Patent No. 119,860, and the coupler represented by the general formula [■] is described in JP-A-60-33552.

Specific examples of typical magenta couplers and ethylenically unsaturated monomers thereof according to the present invention will be shown, but the invention is not limited thereto.

(M-1) C11+ (M-2) (M-3) CHl (M-4) (M-5) (M-6) (M-7) L (M-8) Shil (M-9) (M-10) (M-11) (M-12) (M-13) (S + 1 gono less H (M-14) (M-15) ■ tHs (M-18) (M-19) (M-201 (M-22) (M-23) -N (M-24) (M-25) (M-27) X: y-45: 55 (Weight ratio, same below) (M-28) x:y=sO:50 (M-31) (M-35) (M-36) (M-37) C1l.

[ NHCOCI! +12° (M-38) 1”lL (M-39) ? 11° (M-40) CH3 (M-41) CeIll(t) (M-42) (M-43) (M-44) (M-45) (M-46) CH3 (M-471 NHCOC+Jtt (M-50) C1l.

(M-51) CH.

Shitsu, H word + (L) (M-52) ShillS (M-53) CM-54> Synthesis reference example (synthesis of reference coupler (M-16)) (M
-16) (1) 4-Methyl-3-oxopentanonitrile (A)
Synthesis of tetrahydrofuran 800mj! The mixture was stirred at room temperature under a nitrogen stream, and sodium hydride (dispersed in oil, content 60%) was added thereto. This stake? The IA solution was heated on a steam bath to a reflux state, and a mixture of 102 g of methyl 2-methylpropionate and 45.2 g of acetonitrile was added dropwise thereto over 2 hours, and reflux was continued for an additional 6 hours. After cooling, 50 ml of ethanol was added and after stirring, the solvent was distilled off under reduced pressure. Dissolve the residue in water 11 and 300III
! Washed twice with bexane. Approximately 80ml of concentrated sulfuric acid in the water layer
was added to make it slightly acidic, then extracted with ether (300w
l x 3) Shita. After drying the ether solution over anhydrous magnesium sulfate, the ether was distilled off, and the remaining pale yellow oil was distilled off under reduced pressure (132,5-134,5℃/4
8＠Hg) L, te, 47.9g (43%) of 4-
Methyl-3-oxopentanonitrile (A) was obtained.

Nuclear magnetic resonance spectrum (CDCl,) δ (ppm)
3.58 (211, S), 2.80 (1B, m)
, 1.17 (6H, d, J = 6.9Hz) (2) Synthesis of 5-amino-3-(1-methylethyl)pyrazole (B) 4-Methyl-3-oxopentanonitrile (A) It was dissolved in 140 mN of ethanol and stirred at room temperature. to this,
After adding 15.7 g of hydrazine hydrate and stirring at room temperature for 1 hour, the mixture was heated under reflux for 5 hours.

After distilling off the solvent under reduced pressure, vacuum distillation (133-15
3°C 10,06㎽-11g) and 33.3g (8
7%) of 5-amino-3-(1-methylethyl)pyrazole (B) was obtained.

Nuclear magnetic resonance spectrum <coc 7! , ) δ (ppm)
6.03 (3H, Br), 5.34 (LH, S)
, 2.83 (Ill, m), 1.17 (6H, d
, J=6.911z)(316-(1-methylethyl)-2-(3-(4-nitrophenyl)propyl)pyrazolo[1°5-b)(1,2,4))lyazole (C)
Synthesis of 5-amino-3-(1-methylethyl)pyrazole 12
．． 5 g to methanol 4 Qm12? Understand, 4-
(p~nitrophenyl)butynimidate methyl hydrochloride 2
5.9 g was added and stirred at room temperature for 2 hours.

To this, 6.95 g of hydroxylamine hydrochloride and 28%
Sodium methoxide methanol? 1fz 19.
A methanol solution of 3 g to 8 methanol hydroxylamine was added, and the mixture was allowed to stand at room temperature overnight. After evaporating the solvent under reduced pressure, the residue was added to water and extracted with ethyl acetate. This :f layer was dried over anhydrous magnesium sulfate and then concentrated. Dilute the residue with tetrahydrofuran 200n+j
! 12.0 mj2 of triethylamine was added thereto, and the mixture was stirred in a water bath. To this, 16.0 g of p-)luenesulfonic acid chloride was slowly added, the water bath was removed, and the mixture was stirred for 1 hour. Insoluble materials were removed by filtration, and the filtrate was concentrated.

Pour the residue into methanol 600n+j! and heated under reflux for 3 hours.

After methanol was distilled off under reduced pressure, the mixture was poured into 1.0 ρ of water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residue was separated by silica gel column chromatography (eluent: chloroform-ethyl acetate = 5:1).

After concentrating the eluate containing target substance C, the residue was recrystallized from ethyl acetate to obtain 6.2 g (20%) of 6-(1-methylethyl')-2-(3-(4-nitrophenyl)). Propyl) pyrazolo[1,5-b](1,2,4) triazole (C) as pale yellow crystals (mp188-189℃)
obtained as.

Elemental analysis 0% H% N% calculated value 6
1.33 6.11 22.35 Measured value 61.
10 6.00 22.01 Nuclear magnetic resonance spectrum (CDCl v DMSOd6) δ (ppm) 1
2.7(1)1. br), 8.12(211,d,
J=9.0Hz), 7.44 (211,d, J=
9.0Hz), 5.45(Ill, S), 3.2-
2.7 (5H, m), 2.15 (2H, m), 1.
26 (6H, d, J=6.911z)+41 2-
(3-(4-aminophenyl)propyl)-6-(1-
methylethyl) pyrazolo[1,5-b) (1,2,4)
Synthesis of triazole (C) 6.7 g of reduced iron, 0.53 g of ammonium chloride, and 0.57 mn of acetic acid were added to a mixed solvent of 40 mff of 2-propanol and 8 mff of water, and the mixture was heated on a steam bath to bring it to a reflux state. . To this was added 21 g of nitro C6, and reflux was continued for 30 minutes. Sodium hydroxide l, 3.0 g to 30 g of water
nj! A solution dissolved in was added and stirred, and then filtered to remove insoluble matter. 100mjl of water to the filtrate! and 5 ml of acetic acid
was added and stirred, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain 5.37 g (95V6) of an amino compound as slightly orange crystals (mpl 43, 5-144.5°C). .

(5) Synthesis of coupler (M-16) Acetonitrile 30IIll and N,N-dimethylacetamide l 0c
05.04 g of the amino compound was added to a mixed solvent of al, and the mixture was heated and stirred on a steam bath. To this, 2-(2,4-di-amylphenoxy)hexanoyl chloride 6,86
g was added dropwise, and heating was continued for an additional 10 minutes. The reaction mixture was poured into 150 IIll of water and extracted with ethyl acetate. After drying the organic layer over anhydrous magnesium sulfate,
Concentrated. This residue was dissolved in 200II11 of methylene chloride, 2.16 g of N-chlorosuccinimide was added, and the mixture was stirred at room temperature for 10 minutes. Add this reaction mixture to 200 s of water.
After washing with +1 three times, it was dried over anhydrous magnesium sulfate. ? After 1 km, the residue was purified by silica gel column chromatography (eluent: chloroform-ethyl acetate-50
= 1), and the eluate was concentrated to dryness to give 10.0 g (9
0%) (M-16) was obtained as a pale yellow powder.

Elemental analysis 0% H% N% calculated value 7
0.40 8.39 10.80 Measured value 70.
15 B, 37 10.57 Nuclear magnetic resonance spectrum (CDC1,) δ (ppm) 12.22 (1) 1. S), 7.
99(l)l, S), 7.3-6.6(7)1.
m), 4.73 (IH, t, J=4.8Hz), 3.
16(1)1. m), 2.8-2.6 (411, s)
, 2.2-1. H3O11,m), 1.0-0.5(
9H, a+) 5-amino-3-t-butylpyrazole (A) 13.9
g to 200mj of acetonitrile! and stirred at room temperature. To this solution, 23.8 g of methyl m-nitropenzimidate hydrochloride (B) was added as a solid, and stirring was continued for 4 hours at room temperature, and crystals were precipitated from the reaction system. The crystals were collected by filtration, washed with acetonitrile, and dried.
g (98.2%) of amidine compound (C) was obtained.

100 Ill of methanol was added to 28.8 g of amidine compound (C) obtained by the above method, and the mixture was stirred at room temperature. After dissolving 7.4 g of hydroxylamine hydrochloride in 75 tlll of methanol and neutralizing it by adding SM 28 21.5o11,
A methanol solution of hydroxylamine, from which precipitated common salt had been removed by filtration, was added to the methanol solution of amidine, and the mixture was stirred at room temperature for 5 hours. Add this reaction solution to 1 500+
When poured into al water under stirring, a hartz-like substance precipitated. After water was removed, acetonitrile was added to this hartz-like substance and the mixture was stirred at room temperature, resulting in crystallization. The crystals were collected by filtration, washed with acetonitrile, and dried. 20.0g (74.1%
) was obtained.

100n+7! of dimethylacetamide was added to 20.0g of the amidoxime compound (D) obtained by the above method. was added and stirred at room temperature. Add paratoluenesulfonyl chloride 12 to this solution.
．． 6 g was added, and then 5.3 mj2 of pyridine was slowly added dropwise. After stirring at room temperature for 1 hour, 1 1/2 ounces of water was added to the reaction solution.
000mjl! When added, a hartz-like substance precipitated. After removing water, methanol 15
0 ml was added, and the mixture was heated and stirred. Pyridine 5.
3n+42 was added dropwise, and the mixture was heated and stirred for 1.5 hours. When this reaction solution was cooled with water, crystals precipitated and were collected by filtration. When this crystal is washed with methanol and dried, it yields 9.5 g.
(50.5%) of 5-t-butyl-2-(3-nitrophenyl)-LH-pyrazolo-(1,5-b)-1,2°4-triazole (F) was obtained.

10g of reduced iron, 0.5g of ammonium chloride, 1.5' of water
ml, isoproper tool 75mj! After heating and stirring for 30 minutes, the 6-t-butyl-
2-(3-nitrophenyl)-1H-pyrazolo-(1,
9.5 g of 5-b)-1,2,4-) lyazole was added in several portions. After heating and stirring for 2 and a half hours, the mixture was filtered while hot to remove insoluble matter. The filtrate was concentrated to dryness under reduced pressure to give 2-(3-aminophenyl)-6-t-butyl-I
H-pyrazolo-(1,5-b)-1,2,4-)riazole (G) was obtained.

2-(3-aminophenyl)-6-t obtained by the above method
-butyl-IH-pyrazolo-(1,5-b)-1,2,
4-) Lyazole (G) with dimethylacetamide 501
1 and stirred at room temperature.

To this solution was added 16.5 g of 2-octyloxy-5-t-octylbenzenesulfonyl chloride (H), and then 3.3 ml of pyridine was added dropwise. After stirring this solution at room temperature for 4 hours, 500 n/! of water was added to the reaction solution. , ethyl acetate 300nj! was added and extracted. After washing this ethyl acetate layer with water and drying it with anhydrous magnesium sulfate,
Ethyl acetate was distilled off under reduced pressure. When acetonitrile was added to the residue, crystals were precipitated. The crystals were collected by filtration, washed with acetonitrile, and dried to give 17.3 g (81
, 7%)
4-triazole (1) was obtained.

6-[-butyl-2-・(3-=(2-
octyloxy-5-t-octyl)benzenesulfonamidophenyl) -10-pyrazolo-(1,5-b)
12.7 g of -1,2,4-triazole (1) was dissolved in 100 L of chloroform and stirred at room temperature. To this solution, 2.67 g of N-chlorosuccinimide was added in several portions. After stirring for 1 hour, the reaction solution was washed with water.

After drying this chloroform solution over anhydrous magnesium sulfate, chloroform was distilled off under reduced pressure.

The residue was crystallized by adding ethyl acetate and further recrystallized from ethyl acetate for purification. 12.4g (92.5%) of 5
-t-butyl-7-chloro-2-(3-(2-octyloxy-5-t-octyl)benzenesulfonamidophenyl)-18-virazolo-(1,5-b)-1,2,
4-1-Riazole (M-40) was obtained. Melting point 194~
The temperature was 195°C.

(Synthesis Examples 2 and 3) 7-chloro-2-(3-(
2-octyloxy-5-t-octyl)benzenesulfonamidophenyl)-6-i-propyl-IH-pyrazolo-(1,5-b)-1゜2.4-1-riazole(
M-39) was synthesized.

The melting point was 184-185°C.

Similarly, 7-chloro-6-cyclohexyl-2
-(3-(2-octyloxy-5-t-octyl)benzenesulfonamidophenyl)-1H-pyrazolo-(
1,5-b)-1,2,4-triazole (M-54)
I got it. The melting point was 178-179°C.

The magenta coupler of the present invention and the combination couplers described below can be introduced into the light-sensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil droplet dispersion method in ice. This can be cited as an example.

In the oil-in-water dispersion method, a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point are dissolved in a liquid solution or a mixture of both, and then water is dissolved in the presence of a surfactant. Or finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Patent No. 2.32.
Representative examples are given in the following sections starting with No. 2.027. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (e.g., dibutyl phthalate, di-37-dimethyloctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tribrezyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecaneamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2
．． 4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline 14<N, N-
diptyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbon N (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), etc.
In addition, as an auxiliary solvent, the boiling point is about 30° to about 160°.
Organic solvents such as "C" can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are disclosed in U.S. Pat.
, No. 230, etc.

The couplers of the invention are preferably added within the light-sensitive silver halide emulsion layer. The addition amount range is 1 of silver halide.
per mole, 0. OO3-0.5 mole can be used, 0
．． The range of 0 O5 to 0.3 mol can be preferably used for color photographic materials, and the range of 0.1 to 0.5 mol is suitable for color paper.

In addition to the magenta coupler of the present invention, conventional color couplers can be used in combination with the color photosensitive material of the present invention. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of cyan, magenta and yellow couplers that can be used in the present invention are RD 17643 (19
(December 1978) ■ = Section D, described in the patent cited in 18717 (November 1979).

Preferably, these couplers have ballast groups or are polymerized and diffusion resistant. It is preferable that the coupling position is substituted with a leaving group rather than a hydrogen atom.6 Coupler, colored coupler, colorless coupler, or color-forming coupler in which the coloring element has appropriate diffusivity, or development inhibition due to campling reaction. Couplers that release agents or development accelerators can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2.875.057 and No. 3
, 265.506, etc. 2-equivalent yellow couplers can be preferably used in the present invention, and are described in U.S. Pat.
Oxygen atom separation type yellow couplers described in Japanese Patent No. 3,933,501 and No. 4,401,752, Japanese Patent Publication No. 5B-10739, and U.S. Patent No. 4.02
No. 2,620, No. 4,326,024, RD180
53 (April 1979), British Patent No. 1.425.02
No. 0, West German Application No. 2,219,917, West German Application No. 2,
Typical examples include the nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 261,361, 2,329,587, and 2,433.812.

α-pivaloylacetanilide couplers are characterized by the fastness of color-forming dyes, while α-henzoylacetanilide couplers are characterized by good color-forming properties.

Examples of magenta couplers that can be used in the present invention include oil-protected indazolo or cyanoacetyl couplers, preferably 5-pyrazolone couplers. The 5-pyrazolone coupler is preferably one in which the 3-position is substituted with a -ruamino group or an acylamino group from the viewpoint of the hue and color development rate of the color dye, and typical examples thereof are:
U.S. Patent No. 2,311,082, U.S. Patent No. 2,343,7
No. 03, No. 2.600,788, No. 2,908,
No. 573, No. 3,062,653, No. 3.152
, No. 896 and No. 3,936,015. 2-equivalent 5-pyrazolone couplers are preferred, with the leaving group being an elemental leaving group as described in U.S. Pat. No. 4,310,619 or U.S. Pat. No. 4,351.
, 897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 has high color reactivity.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, preferably the naphthol-based couplers described in U.S. Pat. No. 2,474,293 and U.S. Pat.
No. 2,212, No. 4,146.396, No. 4,2
Typical examples include highly active 2-equivalent naphthol couplers of the oxygen atom elimination type described in Japanese Patent No. 28,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat.
, No. 423.730, No. 2,772.162, and No. 2,895,826.

Cyan couplers that are temperature and temperature robust are preferably used in the present invention, typical examples being the phenolic cyan couplers described in U.S. Pat. No. 3,772,002, U.S. Pat. No. 2,772,162; Same No. 3.758
, No. 308, No. 4,126,396, No. 4.33
No. 4.011, No. 4.327.173, West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 1983-4267
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 3,446,622.
No. 4,333,999, No. 4,451.55
These include phenolic couplers having a phenylureido group at the 2-position and a sialamino group at the 5-position, which are described in No. 9 and No. 4,427,767.

The coupler of the present invention and the couplers mentioned above can be used in combination of two or more types in the same layer, or the same compound can be added to two or more different layers in order to satisfy the characteristics required for the photonic material. , of course it doesn't matter.

In order to correct unnecessary absorption in the short wavelength region of the magenta and cyan coupler chromophores, it is preferable to use a colored coupler in combination with the color photosensitive material for photographing. U.S. Patent No. 4,163,670 and Japanese Patent Publication No. 57-39
Yellow-colored magenta couplers such as those described in US Pat. No. 4,004,929 and US Pat. No. 4,138,2
Typical examples include the magenta-colored cyan couplers described in No. 58 and British Patent No. 1,146,368.

The color coupler that can be used in combination may also form a dimer or more polymer. Typical examples of polymerized couplers are U.S. Pat. Nos. 3.451,820 and 4.080,211.
listed in the number. Examples of polymerized magenta couplers are described in British Patent No. 2.102.173 and US Pat. No. 4,367,282.

In addition, the graininess can be improved by using a chromophore diffusing coupler, and such couplers are described in U.S. Pat.
Examples of magenta couplers are found in EP 66.237 and UK Patent No. 2.125.570, and in European Patent No. 96.
No. 873 and West German Patent Publication (OLS) 3,324,5
33) describes specific examples of yellow, magenta, and cyan.

As the binder or protective colloid that can be used in the emulsion layer or intermediate 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.

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.

The average grain size of silver halide grains in a photographic emulsion (the grain size is the grain diameter for spherical or approximately spherical grains, and the edge length for cubic grains, expressed as an average based on the projected area) is Although not particularly limited, it is preferably 3μ or less.

The particle size distribution may be narrow (or wide).

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a hexagonal, or may have a spherical or hexagonal shape.
The particles may have an irregular crystal structure such as a plate shape, or may be a composite of these crystal forms, or may consist of a mixture of particles of various crystal 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 the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is P, Glafkides.
Written by Chimie et F'hysique Photo
ographique (published by Paul Monte1, 1967) Photo by G.F. Uffin
graphicEmulsionChemistry
(The Focal Press, 1966)
Maki, V.L., Zelikman et al.
ng and coatingphotography
c E+mulsion (The Focal Pr
It can be adjusted using the method described in ``Ess Publishing Co., Ltd., 1964''. That is, any of the acidic method, neutral method, and ammonia method may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

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 produced from silver halide is kept constant, ie, the 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 allowed to coexist.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, see, for example, Il, Frleser, ed.
DieGrundlagender Photogr
aphischen Prozesse m1tS
Her-halogenrden” (Akadem)
ischeVerlagsgeselleshafL,
1968), pages 675-734, can be used.

sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing agents (e.g., stannous salts, amines); hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., gold complex salts, Pt, I
A noble metal aggravation method using complex salts of metals of group (I) of the periodic table such as r, Pd, etc. 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. Namely, azoles such as hendithiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazole M (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines: thioketo compounds, such as oxadorinthion; azaindenes, such as triazoles; Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. A number of compounds known as antifoggants or stabilizers can be added, such as.

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 water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, heminanine 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.

These sensitizing dyes may be used alone or in combination, and combinations of enhancing 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,
For example, the emulsion may contain a substance exhibiting supersensitization.
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635.
No. 721), aromatic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

A multilayer natural color photographic material usually has 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 green-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 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, active vinyl compounds (1,3°5-triacryloyl-hexahydro-3-triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s -triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

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 of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Patent No. 3.533,7
No. 94, No. 4,236,013, Special Publication No. 51-654
Aryl group-substituted benzotriazoles described in U.S. Patent No. 0 and European Patent No. 57,160;
Butadines described in No. 99, U.S. Patent No. 3,70
5.805 and 3.707,375; benzophenones described in U.S. Patent No. 3,215,530 and British Patent No. 1,321.355; Polymer compounds having ultraviolet absorbing residues such as those described in No. 3,761,272 and No. 4,431,726 can be used. U.S. Patent Nos. 3,499,762 and 3,700,4
Ultraviolet absorbing fluorescent brighteners described in No. 55 may also be used. A typical example of a UV absorber is RD 24239
(June 1984), etc.

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. Hyde is a known anti-fading agent.

Examples include quinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

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 as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose acetate, sululose acetate butyrate, polystyrene, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers (e.g. polyethylene, polypropylene). ) etc. are coated or laminated. 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 dioxide, 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 for reflective materials, a hydrophilic colloid layer containing a high density of white pigment may be further provided between the support and the emulsion layer to improve the whiteness and detail 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, and detailed In addition to improving the degree of
This is particularly preferable since it provides photographic images with particularly excellent saturation and depiction of dark areas. 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.

In addition to the above, various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, antistatic agents, developing agents, etc., may be added to the color photographic material of the present invention as necessary. An example of this can be found in Research Disclosure 176'43.

Furthermore, depending on the case, a fine-grain silver halide emulsion having substantially no photosensitivity (for example, silver chloride, silver bromide, or chloride with an average grain size of 0.20 μm or less) may be included in the silver halide emulsion layer or other hydrophilic colloid layer. A silver oxide emulsion) may also be added.

The color developing solution that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As a color developing agent, 4-amino-N, N-diethylaniline, 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-
Typical examples include methyl-N-ethyl-N-β-methoxyethylaniline.

The color developer may contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers,
Fogging agents such as sodium boron hydride, l-
Auxiliary developers such as phenyl-3-virapritone, tackifying agents, polycarboxylic acid chelating agents as described in U.S. Pat. No. 4,083,723, OLS 2,62
It may also contain antioxidants such as those described in No. 2,950.

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. As a bleaching agent, for example, iron (Ill.
), compounds of polyvalent metals such as cobalt (■), chromium (■), copper (U), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron (In) or cobalt (I[I), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Aminopolycarboxylic acids such as 1.3-diamino-2-propatoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, manganates; nitrosophenols, and the like can be used.

Of these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, and ammonium iron(nl) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron(I[I) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

It may be washed with water after color development or bleach-fixing treatment.

Color development can be carried out at any temperature between 18°C and 55°C. Color development is preferably carried out at 30°C or higher, particularly preferably at 35°C or higher. The development time is preferably as short as about 3 minutes to about 1 minute. Liquid replenishment is preferred for continuous development processing, with 330c per square meter of processing area.
Replenish the liquid with 160 cc to 160 cc, preferably 100 cc or less. The amount of benzyl alcohol in the developer is 5 ml.
/e or less is preferable. Bleach fixing is from 18℃ to 50℃.
Although it can be carried out at any temperature of 30°C or higher, it is preferably 30°C or higher.

When the temperature is 35°C or higher, the processing time can be reduced to 1 minute or less, and the amount of liquid replenishment can be reduced. The time required for washing with water after color development or bleach-fixing is usually 3 minutes or less, and washing can be done within 1 minute using a stabilizing bath.

Colored pigments not only deteriorate due to light, heat, or temperature, but also deteriorate and fade due to mold during storage. Cyan images are particularly susceptible to severe deterioration due to mold, so it is preferable to use a mold preventive agent. Specific examples of antifungal agents are disclosed in JP-A-57-15724.
2-thiazolylbenzimidazoles as described in 4. The antifungal agent may be incorporated into the photosensitive material.
It may be added externally during the development processing step, and it can be added at any step if it coexists with the processed photosensitive material.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 As a coupler, 10 g of comparative coupler A was added with 14.2 g of tricresyl phosphate and 2011e of ethyl acetate, and the mixture was heated to 60° C. to dissolve. Add this to 10g of gelatin,
100m7 of an aqueous solution containing 1.0g of sodium dodecylhenzenesulfonate! A fine emulsified dispersion was obtained by a mechanical method. The total amount of this emulsified dispersion was changed to 100 g of silver chlorobromide emulsion (Ag
6.55) and 2% 2.5% as hardener.
10 ak1 of 4-dihydroxy-6-chloro-s-triazine sodium salt was added and coated on a triacetate clear base so that the coated silver amount was 600 cm/2, and a gelatin layer was provided as a protective layer on top of this coated layer. A sample was prepared using the same method.This will be referred to as comparative sample A.

Comparison coupler A Next, compare coupler A (M-39) and (M-40)
A sample was prepared in the same manner as above, substituting an equimolar amount for . These are designated as samples (1-1) and (+-2).

These samples were subjected to a wedge exposure of 500 CMS and processed with the following processing solution.

■, Color development 35℃ 2'30''
2. Bleach-fixing 1'30"3. Washing with water 3'00"p Ranizu W Vermilion Triethanolamine 8.1g Diethylhydroxylamine 4.2g Potassium Bromide (KBr) 0.6g Sodium Sulfite 0.13g N-Ethyl- N-(β-Methanesul 5.0ghonamidoethyl)-3-methyl-4-aminoaniline sulfate Sodium bicarbonate (Na) ICO:+)
3.9g potassium carbonate (K2CO2)
Adjust pH to 11 with 18.7g water 10.25 Main water set 1 Withdraw water 4
00m eAmmonium 1000sulfate (70χ)
toom e sodium sulfite
17g ethylenediaminetetraacetic acid iron(III)
55g ammonium ethylenediaminetetraacetic acid disodium 5g ammonium bromide 40g Add water
10001 pH 6.0 The obtained color image was exposed to light using a xenon fading test ff1B (100,000 lux) to conduct a fastness test of the magenta dye image. The results are shown in Table 1.

The results in Table 1 show that by using the coupler of the present invention,
This clearly shows that the effect of improving color image fastness can be found.

Reference Example 1 As a coupler, 8.9 g of compound (M-16) was mixed with 181Il of tri(2-ethylhexyl)phosphate!
, add 25ml of ethyl acetate and heat to dissolve gelatin.
0g, sodium dodecylbenzenesulfonate 1.0g
A fine emulsified dispersion of the above coupler was obtained by adding the coupler to 10 o III of an aqueous solution containing the coupler and stirring at high speed. The total amount of this emulsified dispersion was converted into silver chlorobromide emulsion 10 containing 50 mol% of Br.
In addition to 0g (containing 6.5g of Ag), 101al of 2% 2.4-dihydroxy-6-chloro-3-triazine sodium salt was added as a hardening agent to achieve a silver coating weight of 200g.
A sample was prepared by coating it on a paper support laminated with polyethylene on both sides so as to give a gelatin layer on both sides of the coating so as to give a gelatin layer of 100 mg/n.This will be used as a sample.

Next, coupler M-16 was added to reference compound (M-17) 9.1
Sample B was prepared according to the method used to prepare Sample A by replacing sample A with g.

(M-17) Furthermore, compound 8.9 shown below as a comparative coupler
Sample C (comparative sample) was similarly prepared according to the method described above.

(Comparative Compound) These three samples were subjected to 7-degree exposure at 100 OC, M, and S, and were processed with the following processing solution to obtain various magenta colored images.

Developer benzyl alcohol 15mff diethylenetriaminepentaacetic acid 5gKBr
O,4gNa, 5035g Na2CO330g Hydroxyamine sulfate 2g4-amino-3-methyl-N-β-(methanesulfonamide) Ethylaniline・3/2 H□SO4・H2O4,
Adjust to 1000+++A' with 5g water pH10,
1 Bleaching room liquid ammonium 1000 sulfate (70wtχ) 150
n+t'NazSOt
5 gNa (Fe(EDTA))
40 g EDTA
Make 1000 mff with 4 g water pi
6.8 Processing process temperature Time Developing solution 33°C 3 minutes 30 seconds Bleach-fix solution
Wash with water at 33℃ for 1 minute and 30 seconds 28
~35°C for 3 minutes The magenta images of each sample thus obtained were clear and highly saturated. When the photographic characteristics of these color images were measured, the following results were obtained.

Table 1 Photographic characteristic values* Relative value of the reciprocal of the exposure amount that gives the density of (fog + 0.5). The comparison sample was used as the standard (100).

As a result, it was found that the coupler (M-16) exhibited excellent characteristics in terms of gradation and maximum density, although the sensitivity was approximately the same.

Reference Example 2 Samples A, B, and C prepared in Reference Example 1 were subjected to the same processing as described in Reference Example I to obtain a magenta color image.

One part of these samples was heated at a high temperature of 70°C for 7 days, and the other part was heated at 60°C and 90% high temperature and high humidity for 6 days.
For the other part, a U filter that cuts U light with a wavelength shorter than 390 r+m was attached to the front of the sample, and the sample was exposed to light in a xenon fading tester (100,000 lux) for 7 days, and the magenta dye image was solidified. A sex test was conducted. The results are shown in Table ■.

From Table 2, it was found that the coupler (M-16) has excellent color image fastness even under high temperature conditions of 100°C and 60°C, 90% R, H, high temperature and high humidity. What is remarkable is that it has particularly good fastness to light.

Furthermore, no staining due to residual coupler was observed in any of the fading tests.

Reference Example 3 As described in Table ■, the first layer (bottom layer) to the seventh layer (top layer) were coated on a paper support laminated with polyethylene on both sides, and color photographic materials E, F, I created G.

The composition of the coating solution containing the emulsified dispersion and emulsion of the magenta coupler used in the third layer was prepared and coated in accordance with Reference Example 1.

*1 Yellow coupler α-pivaloyl-α-(2,4-dioxo-5,5'-
dimethyloxazolidin-3-yl)-2-chloro-5
-[α-(2,4-di-tert-pentylphenoxy)butanamide] acetanilide *2 Solvent dioctyl butyl phosphate *3 Color mixing inhibitor 2.5-dioctyl hydroquinone *4 Solvent dibutyl phthalate *5 Magenta coupler sample E (M-16 ), Sample F (M-17), Sample G Comparative compound of Reference Example 1 *6 Solvent tri(2-ethylhexyl) phosphate *7 Ultraviolet absorber 2-(2-hydroxy-3-sec-butyl-5ter
t-Butylphenyl)benzotriazole *8 Cyan coupler 2-[α-(2,4-di-tert-pentylphenoxy)butanamide)-4,6-dichloro-5-methylphenol B for these samples E, F, and G A three-color separation filter of -GR was attached, and the same exposure and color development treatments as in Example 1 were performed.

The obtained color image was exposed to light for 4 weeks using a fluorescent lamp fading tester (1.5 million lux), and a fastness test of the magenta dye image was conducted. The results are shown in Table ■ (yellow stain is shown in parentheses). Table ■ Based on the color image fastness results, couplers (M-16) and (M-17)
It has become clear that the chromogenic images obtained from this method have excellent fastness to light. It was also found that the remaining coupler did not exhibit any adverse effect on the chromophoric dye due to light.

Reference Example 4 As a coupler, 7.1 g of coupler (M-16) was mixed with 14.2 g of tricresyl phosphate and 20 g of ethyl acetate.
IIle was added and heated to 60°C to dissolve.

This was added to 100 IIll 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. The entire amount of this emulsified dispersion was added to 100 g of a silver chlorobromide emulsion (including A[6,55) containing 90 mol% of Br,
2% of 2゜4-dihydroxy-6-chloro-5-) riazine sodium salt 10Il11 was added as a hardening agent and coated on a triacetate clear base so that the coated silver amount was 600μ/d. A sample was prepared by providing a gelatin layer on top of the layer with a protective layer. This is designated as sample H.

Next, replace coupler (M-16) with (M-29), add 19.2 g of the high boiling point organic solvent to this 9.6 g,
20 mj of ethyl acetate for each! A sample was prepared in the same manner as above. This is designated as sample (■).

(M-29) Furthermore, a sample was prepared in exactly the same manner as described above, using the comparative compound used in Reference Example 1 as the magenta coupler and using the same solvent as the high-boiling organic solvent. This is designated as sample J.

These samples H to J were subjected to a wedge exposure of 200 CMS and then 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 fixation 27℃ 40 seconds 5 Water
Washing 27℃ 40 seconds6 Acceleration 27℃ 40 seconds7 Bleaching 27℃ 40
Second 8 Wash with water 27℃ 4
0 seconds 9 Second fixing 27℃ 40 seconds 10
Wash with water 27℃ 1 minute 00 seconds 11 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 1.72g Add water
BpH10.5 Stop solution composition Sulfuric acid (6N) 50n+/
Add water 11 pH 1.0 First and second fixer composition Ammonium thiosulfate 60g Sodium sulfite 2.5g Sodium hydrogen sulfite 10.3 g Potassium iodide
Add 0.5g water
17! pH 5.8 Promoting liquid composition Sodium pyrosulfite 3.3g Glacial acetic acid 5. OmffP B
A-1 (KODAK persulfate bleach accelerator) 3.3gE
DTA tetrasodium salt 0.5g Add water 11pH 4.0 Bleach solution composition Sodium persulfate 33.0g Sodium chloride 15.0g Sodium dihydrogen phosphate 7.0g Phosphoric acid (85%)
2.5m7! add water
11pl+ 2.3 Stable liquid composition Formalin (37%) Add 15.0ml water and lI! The obtained color image was exposed to light for 4 weeks using a fluorescent lamp fading tester (1.5 million lux) to test the fastness of the magenta dye image.

The results are shown in Table ■ (yellow stain is shown in parentheses).

Table V Color image fastness From the results in the above table, coupler (M-16) or (M-29)
By using this, it was possible to clearly find an improvement effect on color image light fastness.

Reference Example 5 A color photographic material was prepared by coating a paper support laminated on both sides with polyethylene in layers from the following 1st layer to 11N. 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/, 1 unit are shown below.

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

1st layer (antihalation layer) Black colloidal silver... o,
oi gelatin ・・・・・・ 0
．． 2 Second layer (low sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (*5 and *4) (silver iodide 3.5 mol%, average grain size 0.7μ)
・・・・・・! 10.15 Gelatin
・・・・・・ 1.0 cyan coupler (*3) ・・・・・・ 0.30 anti-fading agent (*2) ・・・・・・ 0.08 anti-fading agent (*8) ・・・...0.04 Coupler solvent (*18 and *1) ...0.06
Anti-fading agent (*9) ・・・・・・ 0.0
3 Third 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. IQ gelatin
・・・・・・ 0.50 Cyan coupler (*3) ・・・・・・ 0.10 Anti-fading agent (*2) ・・・・・・ 0.03 Anti-fading agent (*8) ・・・...0.01 Anti-fading agent (*9) ...0.01 Coupler solvent (*18 and *1) ...0.02
4th layer (middle layer) Yellow colloid i 艮 ・・・・・・ 0
,02 Gelatin ・・・・・・
1. OO color mixing inhibitor (* l 4)...
... 0.08 color mixture prevention agent (*13) ・
...0.16 polymer latex (*6)
・・・・・・ 0,40 5th layer (low sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) (silver iodide 2.5 mol%, average grain size 0.4μ)
・・・・・・
...ilo, 20 gelatin...
...0.70 magenta coupler (*11)
・・・・・・ 0.40 Anti-fading agent A (*10)
...0.10 coupler solvent (*18)
...0.40 6th layer (high sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green enhancing dye (+12) (silver iodide 3.5 mol%, average grain size 0) .9 μ)
・・・・・・
・i艮0,20 gelatin...
... 0゜70 Mazenk coupler (+11) ・
・・・・・・ 0.40 Anti-fading agent A (+10)
・・・・・・ 0.10 coupler solvent (+18)
・・・・・・ 0.40 7th layer (yellow filter layer) Yellow colloid)'iM ・・・・−0,
20 Gelatin 1
．． 00 Color mixing prevention agent (+14) ・・・・・・
0.06 Color mixing prevention agent 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 grain size 0.5 μ )
・・・・・・
・i艮0.15 gelatin...
... 0.50 yellow coupler (+15) ・
...0.20 coupler? Capacity (+18)
・・・・・・ 0.05 9th layer (high-frequency blue-lighting layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (+16) (silver iodide 2.5 mol%, average grain Size 1.4μ)
・・・・・・Silver 0.20 gelatin
・・・・・・ 0゜50 yellow coupler (+15) ・・・・・・ 0.20 coupler solvent (*18) ・・・・・・ 0.05 1st
O layer (ultraviolet absorption layer) Gelatin 1.5
0 UV absorber (+19) ・・・・・・ 1
．． 0 UV absorber solvent (+18) ・・・・・・
0.30 Color mixing prevention agent (+17) ・・・・・・
・0.08 11th layer (protective layer) Gelatin 1.0
The compounds used here are as follows: *1 Dioctyl phthalate *2 2-(2-hydroxy-3-sec-butyl-5
-t--butylphenyl)benzotriazole*3 2-(α-2,4-di-L-amylphenoxy)
butylamido)-4,6-dichloro-5-ethylphenol + 45,5'-dichloro-3,3'-di(3-sulfobutyl)-9-ethylthiacarbonyl cyanine Na salt *5 Triethylammonium-3-(2- +2- (
3-(3-sulfopropyl)naphtho(1,2-d)thiazoline-2-indenmethyl]-1-butenyl) -3
-naphtho(1,2-d)thiazolino]propanesulfonate*6 Polyethyl acrylate*85-chloro-2-(2-hydroxy-3-ter
t-Butyl-5tert-butylphenyl)hensitriazole*9 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole+10 3,3.3',3'-tetramethyl-5°6.
5',6'-tetrapropoxy-1゜1'-bisspiroindane+11 Comparative compound shown in Reference Example 1+125,5'
-Diphenyl-9-ethyl-3゜3'-disulfopropyloxacarbocyanine Na salt + 13-phosphoric acid-〇-cresyl ester +14 2. '4-G[-octylhydroquinone*
15 α-pivaloyl-α-C (2,4-dioxo-
1-benzyl-5-ethoxyhydantoin-3-yl)
-2-chloro-5-[α-(2,4-di-t-amylphenoxy)butaneaminocoacetanilide + 16 triethylammonium 3-[2-(3-benzylrhodanin-5-ylidene)-3-henzuoxa Zolinyl] propane sulfonate +17 2. 4-di5ec-octylhydroquinone +18 phosphoric acid trioctyl ester*195-chloro-2-(2-hydroxy-3-t-7'thyl-5-t
-octyl)phenylbenztriazole A gelatin hardener 1,4-bis(vinylsulfonylacetamido)ethane and a surfactant were added to each layer.

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

Next, the magenta coupler (M-16) was prepared in the same manner as for the sample, except that the magenta coupler (M-16) was used in the fifth layer (low-sensitivity green-sensing layer) and the sixth layer (high-sensitivity green-sensing layer) shown below. A sample was created.

5th layer (low green sensitivity N) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) (silver iodide 2.5 mol%, average grain size 0.4 μ)
・Old...Silver 0.10 gelatin
・Old... 0.70 magenta coupler (
M-16) - Old... 0.50 anti-fading agent A (*
]o) ...... 0.07 coupler solvent (*18) ...... 0.59 6th layer (highly sensitive green sensitive layer) Spectral sensitized with green sensitizing dye ($12) Silver iodobromide emulsion (silver iodide 3.5 mol%, average grain size 0.9 tt)
) -----vAo, 10 gelatin 0.70 magenta coupler (M-16) 0.
50 Anti-fading agent A ($10) ・・・・・・
0.07 coupler solvent (*18)...
・0.59 Next, the magenta coupler of the present invention (M-29
) was used for the following fifth layer (low-sensitivity green-sensing IJ) and sixth layer (high-sensitivity green-sensing layer), to prepare sample M in the same manner as in the sample.

5th layer (low green sensitivity layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) (silver iodide 2.5 mol%, average grain size 0.4μ)
・・・・・・Silver 0. IO gelatin
・・・・・・ 0.70 Magenta coupler (M~29) ・・・・・・ 0.59 Anti-fading agent A(*]O) ・・・・・・ 0,09
Coupler as a container ($18) ・・・・・・ 0
．． 47 6th layer (highly sensitive green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (*12) (iodination!! 3.5 mol%, average grain size 0.9
μ )
...S 0.10 gelatin
・・・・・・ 0.70 magenta coupler (M-
29) ...0.59 Anti-fading agent A (*
10) ...... 0.09 Coupler solvent (*18) ...... 0.47 After wedge exposure of these samples to ~M according to a conventional method,
The results of the following development treatments are shown in Table -■.

The concentration was measured using Fuji FSD-103.

[Processing process]

First development (black and white development) 38℃ 1'15'' water
Wash 38℃ 1'30"
Reverse exposure 100 Lux or more 1" or more color development 38℃ 2'15" water wash
38℃ 45" bleach fixing 38℃ 2"OO" water washing
38℃ 2'15" [Treatment liquid composition] Flea nail nitrilo-N, N, N-) lytyrenephosphonic acid, pentasodium salt 0.6 g Diethylenetriaminepentaacetic acid, pentasodium salt 4.0 g Potassium sulfite 30 .0 g potassium thiocyanate 1.2 g potassium carbonate
35.0 g hydroquinone monosulfonate potassium salt 25.0 g diethylene glycol 15.0 mj21-phenyl 4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0 g potassium bromide 0.5.

Potassium iodide 5.0 ■ Add water 11 (pH 9,70) Benzyl alcohol 15.0ml
Diethylene glycol 12.0m e
3.6-Sithia 1.8-octanediol 0.2 g Nitrilo-N,N,N-1-lytylenephosphonic acid, pentasodium, salt 0.5 g Diethylenetriaminepentaacetic acid, pentasodium salt 2.0 g Sodium sulfite 2.0 g potassium carbonate 25.0 g hydroxylamine sulfate 3.0 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl=4-aminoaniline sulfate 5.0 g potassium bromide 0. 5g potassium iodide 1. On/2 Add water
1p (pH 10,40) 2-mercapto-1,3,4-triazole 1. Og ethylenediamine tetratetradic acid disodium trihydrate 5. Og ethylenediamine tetratetradic acid Fe(III) ammonium hydrate salt
80.0 g sodium sulfite
15.0 g sodium thiosulfate (700 g
/ R liquid) 160.0ml! glacial acetic acid
5. Qm7! add water
1x (pH 6,50) Coupler (M-16) or (
It is clear that samples using M-29) and M have excellent color image light stability and have low occurrence of staining that impairs image quality. Moreover, the obtained color image showed a bright magenta color with high color saturation.

Reference Example 6 Next, Sample N was prepared by applying the first to 121st materials on a triacetate film base in the following order.

1st layer; antihalation layer UV absorber 5-chloro-2-(2-hydroxy-3,
15 g of 5-t-butylphenyl)-2H-benzotriazole, 30 g of 2-(2-hydroxy-5-t-butylphenyl)-28-benzotriazole, 2-(2-hydroxy-3-5ec-butyl-5- 35 g of t-butylphenyl)-2H-hensitriazole, and 100 g of dodecyl 5-(N,N-diethylamino)-2-benzenesulfonyl-2,4-pentagenoate! −
, tricresyl phosphate 200ml, ethyl acetate 2
00mj! , sodium dodecylhenzenesulfonate 2
An emulsion obtained by stirring 0g of 10% gelatin aqueous solution at high speed (hereinafter referred to as emulsion + al), 10% gelatin,
It was mixed with black colloidal silver, water, and a coating aid, and coated to a dry film thickness of 1 μm.

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 emulsion was stirred at high speed with 1 kg of a 10% gelatin aqueous solution ( Hereinafter, emulsification + JIyJ (referred to as bl) 2
kg was mixed with 1.5 kg of 10% gelatin and applied to a dry film thickness of lμ.

Third layer: low-sensitivity red-sensitive emulsion layer 100 g of 2-(heptafluorobutyramide)-5-+2'-(2'',4''-di-t-aminophenoxy)butyramide)-phenol, which is a cyan coupler,
100 cc of tricresyl phosphate and 1 ml of ethyl acetate
00 cc and stirred at high speed with 1 kg of a 10% gelatin aqueous solution (hereinafter referred to as emulsion (C1')), 500 g of an emulsion (hereinafter referred to as emulsion (C1')) was mixed with 1 kg of a red-sensitive silver iodobromide emulsion (1 kg of a 10% gelatin aqueous solution).
g, gelatin (60 g, iodine content: 4 mol %)) and coated to a dry film thickness of 1 μm. (Silver 5t
0.5 g/m) 4th layer; high window red-sensitive emulsion layer Emulsion (C1 is red-sensitive silver iodobromide emulsion 1 kg (silver 70 g
, gelatin (60 g, iodine content: 2.5 mol%) and coated to a dry film thickness of 2.5 μm. (
S coating amount: 0.8 g/m) Fifth layer: Intermediate layer emulsion (bl kg) was mixed with 1 kg of 10% gelatin and coated to a dry film thickness of lμ.

6th layer: Low green-sensitive emulsion layer An emulsion obtained in the same manner as the emulsion of the 3rd layer except that the comparative compound shown in Reference Example 1 was used as a magenta coupler instead of the cyan coupler (hereinafter, emulsion layer). 300 g of a green-sensitive silver iodobromide emulsion (70 g of silver
, gelatin (60 g, iodine content: 3 mol %) and coated to a dry film thickness of 2.0/J. (
Silver 10.7 g/-? ) 7th layer: high window green-sensitive emulsion layer Emulsion + dl l 000 g is mixed with 1 kg of green-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, iodine content is 2.5 mol%), The coating was applied to a dry film thickness of 2.0 μm. (Silver amount: 0.7 g/n () 8th layer; 1 kg of gelatin intermediate layer emulsion (b) was mixed with 1 kg of 10% gelatin, and coated to a dry film thickness of 0.5 μm.

Ninth layer: Yellow filter layer An emulsion containing yellow colloidal silver was coated to a dry film thickness of lμ.

10th layer; low-sensitivity blue-sensitivity emulsion layer
(pivaloyl)-α-(1-benzyl-5-ethoxy-
An emulsion obtained in the same manner as the emulsion for the third layer except that 3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used (hereinafter referred to as emulsion tel) was mixed with blue-sensitive iodine. Silver emulsion 1kg (Silver 7
(60 g of gelatin, iodine content: 2.5 mol %) and coated to a dry film thickness of 1.5 μm. (Silver N O, 6 g/tri) 11th layer: Highly sensitive blue-sensitive emulsion layer 1000 g of the emulsion tel was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin, with an iodine content of 2.5 (mol%) and coated to a dry film thickness of 3 μm. (!Amount: 1.1 g/m) Twelfth layer: Second protective layer Emulsion (al) was mixed with 10% gelatin, water, and 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 0.06μ,
A 10% aqueous gelatin solution containing 1 mol % silver iodobromide emulsion was coated to give a silver coating amount 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.

Next, add the magenta coupler (M-16) to the sixth section shown below.
Sample O was prepared in the same manner as Sample N except that it was used for the low green sensitivity layer and the seventh high green color layer.

6th layer; low anger green layer Emulsion obtained in the same manner as the emulsion of the 3rd layer except that magenta coupler (M-16) was used (hereinafter, emulsion
) was mixed with an emulsion (equimolar to dl, 500 g of silver iodobromide emulsion for the green-sensitive layer (containing 35 g of silver, 308 gelatin, and iodine content of 3 mol %) to give a dry film thickness of 2.0 μm. (Silver amount: 0.35 g/m) 7th layer: High-window green-sensitive layer emulsion (dl and equimolar emulsion (fl) were mixed with 500 g of green-sensitive silver iodobromide emulsion (35 g of silver, 30 g of gelatin) including,
The iodine content is 2.5 mol%) and the dry film thickness is 2.0.
It was applied so that it was μ. (i length 0.35 g/m'
) Next, an emulsion (hereinafter referred to as emulsion (g+)) obtained in the same manner as the emulsion of the third layer except that a magenta coupler (M-29) was used was mixed with the emulsion of sample 0 (fl's emulsion). A sample was prepared as a substitute and designated as sample P.

These samples N to P were exposed in a conventional manner and then developed as described below. The results are shown in Table 1.

The concentration was measured using Fuji FSD-103.

Processing process Step Time Temperature First development 6 minutes 38℃ Water washing 2 minutes ~
Transfer 2 minutes color development 6 minutes adjustment 2 minutes...Bleach 6 minutes fixation 4 minutes - water
Washing Stable for 4 minutes 1 minute Dry at room temperature The composition of the processing solution used is as follows.

Sakuji Tsukai blood water
700m 7! Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 2g Sodium sulfite 20g Hydroquinone monolphonate 30g Sodium carbonate (-hydrate) 3
0g l-phenyl-4-methyl-4-hydroxymethyl-3= vilazuridone 2g potassium silver bromide 2.5g potassium thiocyanate 1.2g potassium iodide (
0.1%? Yong? Night) Add 2mβ water
1000m 1 inversion Harukasui
700m I! Nitrilo-N,N,N-1-lytyrenephosphonic acid pentasodium salt 3g stannous chloride (dihydrate) Igp-aminophenol O, 1g sodium hydroxide
8g glacial acetic acid
15m/! add water
1000ml!衾计廀1斂水
100m! ! Nitrilo N, N, N-1 rimethylenephosphonic acid pentasodium salt 3g Sodium sulfite 7g Sodium tertiary phosphate (dodecahydrate) 36g Potassium bromide
1g potassium iodide (0.1% solution)
90ml! Sodium hydroxide
3g Citrazic acid 1
．． 5gN-ethyl-N-(β-methanesulfonamidoethyl) ~3-methyl-aminoaniline sulfate 11 g3.6-
Cythiaoctane-1.8-diol Add 1g water 1000m E side 1 hill water
7oom 1 Sodium sulfite
12 g Sodium ethylenediaminetetraacetate (trihydrate) 8 g 1,000-glycerin 0.4 ml glacial acetic acid
3ml! Add water to 100 ml
0IIle Kanwata Tatsumizu
800 g Sodium ethylenediaminetetraacetate (trihydrate) 2g Iron ethylenediaminetetraacetate (I[l) Ammonium (trihydrate) 120 g Potassium bromide 100g Add water and remove 1000ml of water.
800ml sodium thiosulfate 8
0.0 g sodium sulfite 5.
0g Sodium Bisulfite Add 5.0g Water 1000 Shine Shiki Namizu
800ml formalin (37% by weight)
5.0mj! Fuji Drywell (surfactant manufactured by Fuji Photo Film ■) 5. Ont! From the results of 1000 m or more with water added, samples O and P using the coupler (M-16) showed good color density, excellent color image stability, and little staining. Together with this, it is very advantageous for printing materials.

Furthermore, the obtained magenta color image showed a vivid hue with high saturation.

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support, the following general formula [I] is present in the silver halide emulsion layer or its adjacent layer. A silver halide color photographic material containing a pyrazoloazole magenta coupler represented by: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, [A] represents a pyrazoloazole magenta coupler residue. R^1 represents an alkyl group, R^2 and R^3 represent a hydrogen atom or a substituent, but R^2
and R^3 are never both hydrogen atoms. n is 1,
Represents 2 or 3. From the coupler of formula [I], the following [
Excluding couplers represented by [V] and [VI]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ [V] [VI] (However, in the formula [V], X is a halogen atom, and R^1
^1 is a substituted or unsubstituted alkyl group, R^1^2 is an alkyl group having a substituent (excluding an aryl group directly bonded to the alkyl group as a substituent), and has the formula [
VI], X is a halogen atom, R^1^1 is a substituted or unsubstituted alkyl group, R^1^2 is a substituted or unsubstituted alkyl group, and in formulas [V] and [VI], , R_1_
1 and at least one of R_1_2 has a mathematical formula, chemical formula, table, etc.▼ (R^1 represents a substituted or unsubstituted alkyl group, R^2 and R^3 represent a hydrogen atom or a substituent, R^ 2 and R^3 is a substituent), and is a branched alkyl group represented by the general formula [V
] Polymer couplers are excluded from magenta couplers. )
]