JPS63149649A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance the color formability of a photosensitive material and to form a color image which is fast to heat and heat and moisture by using a polymer coupler consisting of at least two kinds of repeating units. CONSTITUTION:The polymer coupler consisting of at least the repeating units expressed by formulas I and II is incorporated into the photosensitive material. In formulas, R<1>, R<2> denote H, alkyl or 1-4C, Cl;, L1 denotes -COO-, -NHCO-, -OCO-, etc.; L2 denotes a combination group connecting L1 and Q; (m), (n) denote 0, 1; Q denotes a coupler residual which can form a dye by coupling with an oxidized arom. primary amine developing soln. ; A denotes an alkylene of 1-4C; B denotes H, an alkyl of 1-6C; (x), (y) denote 10-90wt%. The polymer coupler consists of the copolymer contg. the monomer coupler having the coupler residue Q and the comonomer without having the residue Q in the above-mentioned manner.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a novel color image-forming polymer coupler capable of coupling with an oxidized product of an aromatic-grade amine developer. It is something.

(Prior art) When a silver halide color photographic material is subjected to color development after exposure, an oxidized aromatic-grade amine developer reacts with a coupler to produce indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, etc. It is known that similar dyes can be produced to form color images. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming agents, which are complementary colors, respectively. is used.

However, with multilayer color photosensitive materials, it is possible to reduce color mixture,
To improve color reproduction, it is necessary to fix each coupler in a separate layer.

There are many known methods for making couplers diffusion resistant.

One method of making couplers diffusion resistant is the use of polymeric couplers latex obtained by polymerizing monomeric couplers.

The method of adding polymeric couplers to woody colloid compositions in latex form has many advantages over other methods.

First, because the hydrophobic material is made into latex, the strength of the formed film does not deteriorate.

Also, since the latex can contain high concentrations of monomeric couplers, it is easy to incorporate high concentrations of couplers into emulsions with little increase in viscosity.

Further, since it is completely non-migration, it has the advantage that there is no color mixing and there is little precipitation of the coupler in the emulsion film.

Such polymeric couplers added to gelatin silver halide emulsions in the form of latexes are described, for example, in US Pat. No. 4,080,211 and British Patent No. 1,247,688.
No. 3,451.802, U.S. Patent No. 3,926,
No. 436, West German Patent No. 2,725,591, etc.

Also, a polymer coupler incorporating a surfactant function and added to a gelatin silver halide emulsion in the form of a polymer latex without the use of a surfactant is described in U.S. Pat. No. 3,926,436. There are some.

Further, a polymer coupler in which diffusion of the polymer coupler is prevented by introducing an active group capable of reacting with gelatin into the polymer coupler is described in Japanese Patent Application No. 165082/1982.

On the other hand, examples of improvements in color development due to copolymerization include, for example, those described in U.S. Pat. No. 4,612,278.

(Problem to be solved by the invention) However, all of the conventional silver halide color photographic materials containing polymer couplers described above have insufficient color development or are not sufficiently robust against heat and moist heat. It's hard to say, and I'm not completely satisfied.

Accordingly, one object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel polymer coupler having extremely excellent color development properties.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel polymer coupler that provides a color photograph having a color image that is robust to heat and moist heat after processing.

(Means for Solving the Problems) In view of the above circumstances, the present inventors have conducted various studies and found that one molecule structure contains at least two types of repeating units represented by the following general formula (I). It has been found that the above objectives can be achieved by using polymer couplers.

The polymer coupler used in the present invention is characterized by having a repeating unit C0NH-A-0-B which does not have the moat ability to couple with an aromatic-grade amine developer by oxidation, as shown in the general formula (I). be.

That is, the present invention provides a silver halide color photographic material characterized by containing a polymer coupler represented by the following general formula (I) and consisting of at least two types of repeating units.

(R1 and R2 in the formula represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, even if they are rotated.), -Co
o-, -NHCO- or -0CO-, L represents a linking group connecting Ll and Q, 1m represents O or l, n represents O or l, Q is an oxidized aromatic primary amine Represents a coupler residue capable of forming a dye by coupling with a developer, A represents an alkylene group having 1'-4 carbon atoms, B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X and y represents the content of each unit in the polymer coupler, X is 10 to 90% by weight, and y is 10 to 90% by weight. In addition, in the formula, Rt , Rz , R3 and B are nothing! It is meant to include not only cases in which the term is specific, but also those having substituents. ) However, the above general formula (I) does not particularly define the arrangement state of each repeating unit in the polymer.

In the polymer coupler represented by the above general formula (I), the linking group represented by R2 is specifically 1,000X lfJ
1 -
is the same as above).

Ichisei 100- (R3 has the same meaning as above), (R, R has the same meaning as above, R5 is hydrogen atom, alkyl 2
! (1 to 6 carbon atoms), 21-substituted alkyl group (1 to 6 carbon atoms)
), -0-1-5-1 definition), etc.

X, x and x3 may be the same or different,
p, q, r and S represent 0 or 1;

Examples of the substituent which may be further substituted on the linking group L2 and the substituent on the t-substituted alkyl group represented by B include a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted alkyl group, an alkoxy group, 21-substituted alkoxy group,
-NHCOR6 < R6 is an alkyl group,
substituted alkyl group, phenyl group, substituted phenyl group, aralkyl group, and substituted aralkyl group).

-NHSOR6(R6(:!Above and times A), -SOR
(R (: above), So R6R8 may be rotated or different, and is a hydrogen atom, an alkyl group,
(Synonymous with substituted alkyl group, phenyl group, l-substituted phenyl group, aralkyl group, substituted aralkyl group), amino group (which may be 21-substituted with an alkyl group), hydroxyl group, or a group that forms a hydroxyl group by hydrolysis. Can be mentioned.

Furthermore, examples of substituents for the t-substituted alkyl group, the alkoxy group, the phenyl group, and the aralkyl group in the above-mentioned t substituent include a hydroxyl group, a nitro group, and a carbon number of 1 to about 4.
alkoxy group.

-NH5O2R (R has the same meaning as F and R has the same meaning as "-"), -5o2R (R has the same meaning as above), -COR6
(R6 has the same meaning as -), a halogen atom, a cyano group, an amino group (an alkyl group may be substituted), and the like.

Next, among the color coupler residues represented by Q in the general formula (I), the cyan color-forming coupler residue is a phenol type [■] represented by the following general formula, or a naphthol type [ml, L or R2]. ) is preferred.

In the formula, R11 represents a group that can be substituted on a phenol ring or a naphthol ring, and examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxy group, a sulfo group, a cyano group, an aliphatic group, an aromatic group, a heterocyclic group, and a carboxyl group. Amide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyloxy group, acyl group, aliphatic oxy group, aliphatic thio group, aliphatic sulfonyl group, aromatic oxy group, aromatic thio group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, etc. The number of carbon atoms in R11 is 0 to 30.

+2 14 Is R is -CONRR, -NHCOR14, -NHCOOR
, -NH3O2R.

+4 15 -NHCONRR or -NHSOR"R15, RI4 and R15 are hydrogen atoms, aliphatic groups having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, butyl group, methoxyethyl group, n-decyl group, n -dodecyl group, n-hexadecyl group, trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl group, 2,4-di-t
ert-amylphenoxypropyl group, 2,4-di-t
ert-amylphenoxybutyl group, etc.), carbon number 6-3
0 aromatic group (e.g., phenyl group, tosol group, 2-tetradecyloxyphenyl group, pentafluorophenyl group, 2-chloro-5-dodecyloxycarbonylphenyl group, etc.), heterocyclic group having 2 to 30 carbon atoms (for example, 2-pyridyl group, 4-pyridyl group, 2-furyl group, 2-chenyl group, etc.), R16 is an aliphatic group having 1 to 30 carbon atoms (for example, methyl group, ethyl group, butyl group, dodecyl group) , hexadecyl group, etc.), 6 to 30 aromatic groups (e.g., phenyl group, tolyl group, 4-chlorophenyl group, naphthyl group, etc.),
Heterocyclic groups (e.g., 4-pyridyl group, quinolyl group, 2-
(furyl group, etc.). R14 and RIS may be bonded to each other to form a heterocycle (eg, 1 morpholine ring, piperidine ring, piperidine ring 5, etc.). p' is O~3
, q', and r' each represent an integer from 0 to 4.

X represents an oxygen atom, a sulfur atom or R17N:', R17 represents a hydrogen atom or a monovalent group, R17
R17 represents a monovalent group with 1 to 3 carbon atoms as an example.
0 aliphatic groups (e.g. methyl groups).

ethyl group, butyl group, methoxyethyl group, benzyl group, etc.), aromatic groups having 6 to 30 carbon atoms (e.g. phenyl group,
tolyl group, etc.), a heterocyclic group having 2 to 30 prime numbers in 1 (e.g.
2-pyridyl group, 2-pyrimidyl group, etc.), carbon number 1-3
0 carbonamide group (e.g., formamide group, acetamide group, N-methylacetamide group, benzamide group, etc.), sulfonamide group having 1 to 30 carbon atoms (e.g.,
methanesulfonamide group, toluenesulfonamide group,
4-chlorobenzenesulfonamide group, etc.), carbon number 4-
30 imide groups (e.g. succinimide group etc.),
o R18, -8R18, -COR18, Ill 1
9 - - CON RR, COCOR”.

-COCONR18R19, -COOR", -COCO
OR20, -3o R20° -NR18R19 can be cited. Here, R18 and R19 may be the same or different, and each is a hydrogen atom, a carbon atom, or
~30 aliphatic groups (e.g. methyl group, ethylnov, butyl group, dodecyl group, methoxyethyl group, trifluoromethyl group, heptafluoropropyl group, etc.), carbon number 6-3
0 aromatic groups (e.g. phenyl group, tolyl group.

4-chlorophenyl group, pentafluorophenyl group, 4
-cyanophenyl group, 4-hydroxyphenyl group, etc.) or a heterocyclic group having 2 to 30 carbon atoms (for example, 4-pyridyl group, 3-pyridyl group, 2-furyl group, etc.), R18
and R19 may be bonded to each other to form a heterocycle (eg, morpholino group, pyrrolidino group, etc.).

Examples of R20 include the substituents shown in R18 and R19 excluding hydrogen atoms.

Zl represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic 19th amine developer. Examples of groups that can be separated include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom).

'Iodine atom, etc.), aliphatic oxy group having 1 to 30 carbon atoms (
For example, methoxy group, ethoxy group, 2-hydroxyethoxy group, carboxymethyloxy group.

3-carboxypro-ruoxy group, 2-methoxyethoxycarbamoylmethyloxy group, 2-methanesulfonylethoxy group, 2-carboxymethylthioethoxy group, tosoazosolmethyloxy group, etc.), aromatic oxy group with carbon fi 6 to 30 ( For example, phenoxy group, 4-hydroxyphenoxy group, 2-acetamidophenoxy group, 2.4
-dibenzenesulfonamitophenoxy group, 4-soenyl azophenoxy group, etc.), a heterocyclic oxy group having 2 to 30 carbon atoms (for example, 4-pyridyloxy group).

1-phenyl-5-tetrazolyloxyno^kasa), aliphatic thio groups having 1 to 30 carbon atoms (e.g. dodecylthio group, etc.), aromatic thio groups having 6 to 30 carbon atoms (e.g. 4-dodecyl phenyl) thio group, etc.), ) is a heterocyclic thio group with 2 to 30 prime numbers (e.g., 4-picylthio group, l-phenyltetrazol-5-ylthio group, etc.), an acyloxy group with 2 to 30 carbon atoms (e.g., acetoxy group, benzoyloxy group, etc.), base,
lauroyloxy group, etc.), carbon amide group having 1 to 30 carbon atoms (e.g., dichloroacetyl amide group, trifluoroacetamide group, tafluorophthanamide group, pentafluorobenzamide group, etc.), carbon amide group having 1 to 30 carbon atoms
sulfonamide groups (e.g., methanesulfonamide group, toluenesulfonamide group, etc.), aromatic azo groups having 6 to 30 carbon atoms (e.g., phenylazo group, 4-chlorophenylazo group, 4-methoxyphenylazo group, 4- pivaloylaminophenylazo group, etc.), aliphatic oxycarbonyloxy group having 1S30 carbon atoms (e.g., ethoxycarbonyloxy group, dodecyloxycarbonyloxy group, etc.)
, aromatic oxycarbonyloxy group having 6 to 30 carbon atoms (
For example, phenoxycarbonyloxy group, etc.), carbon number 1
~30 carbamoyloxy groups (e.g., methylcarbamoyloxy, dodecylcarbamoyloxy).

phenylcarbamoyloxy group, etc.), a heterocyclic group (such as a phenylcarbamoyloxy group), a heterocyclic group (
Examples include succinimide group, phthalimide group, hydantoinyl group, birazolyl group, (,2-benzotriazolyl group, etc.).

Next, examples of substituents preferably used in the present invention are listed below.

Preferred examples of R11 include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), aliphatic groups (e.g., methyl, ethyl, isopropyl, etc.), carbonamide groups (e.g., acetamide, benzamide, etc.), and sulfone. These include amide groups (eg, methanesulfonamide group, toluenesulfonamide group, etc.).

Preferred examples of R12 include -CONR''R15, such as carbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, and decylcarbamoyl group.

oxybrobyl group, dodecyloxypropyl group, 2.
4-di-tert-amylphenoxypropyl group, 2,
Examples include 4-di-tert-amylphenoxybutyl group.

The preferred R is -COR18 (for example,
) ormyl group, acetyl group, trifluoroacetyl group,
Chloroacetyl group, benzoyl group.

pentafluorobenzoyl group, p-chlorobenzoyl group, etc.), -COOR20 (e.g., methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, dodecyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.), -502R (e.g. , methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexadecanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, p-chlorobenzenesulfonyl group, etc.), -CONR18R19 (N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group) group, N,N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbamoyl group, 3.4-dichlorophenylcarbamoyl group, 4-methanesulfonylphenylcarbamoyl group, etc.), -So□NRR( for example.

N,N-dimethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-dipropylsulfamoyl group, etc.). More particularly preferred among R17 are -COR18゜-COOR'' and -5O
This is a group represented by 2R20.

Preferred groups as Zl are a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, a heterocyclic thio group, and an aromatic azo group.

The coupler represented by the general formula has substituents R11゜R,
Alternatively, zl may be a dimer or a multimer of more than one bonded to each other via a divalent or more polyvalent linking group. In this case, the number of carbon atoms shown in each of the above substituents is limited to the following. isn't it.

As the magenta color forming coupler residue, the general formula [V],
Coupler residues represented by [VI], [■], [VI], [IX], [X] and [XI] (A r ,
Z2. R2'' R33 (7) IF Reka + 7) ff 1 minute Chi G-t, Hi, AL 2 Connected to cold).

where Ar is a substituent of known type in the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituted furkyl group (eg, a haloalkyl group such as fluorofurkyl).

cyanofurkyl, benzylalkyl, etc.), aryl group or substituted 7-aryl group [21! ! ! ! ! Examples of groups include alkyl groups (e.g. methyl group, ethyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, etc.), aryloxy groups (e.g. phenyloxy group etc.), alkoxycarbonyl groups (e.g. methoxycarbonyl group etc.), 7 syl7mino group (for example, 7cetyl7mino group), carbamoyl group, alkylcarbamoyl group (for example, methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl2! i (e.g. dimethylcarbamoyl group), arylcarbamoyl'&C e.g. sulfonamide group), 7-aryl sulfone 7-mido group (
For example, phenylsulfone 7 mido group).

Sulfamoyl group, alkylsulfamoyl group (eg ethylsulfamoyl group), dialkylsulfamoyl group (eg dimethylsulfamoyl group), alkylthio group (eg methylthio group).

Arylthio group (e.g. phenylthio group), cyano group,
Nitro group, halogen atom (e.g. fluorine).

2210! When there are two or more groups, they may be the same or different.

Particularly preferred substituents include a halogen atom, an alkyl group, a 7-rukoxy group, a 7-rukoxycarponyl group, and a cyano group. ], represents a heterocyclic group (eg, triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole, etc.).

R21 is unsubstituted or t-tested anilino group, acylamino 2
& (e.g. alkylcarbonamide group, phenylcarbonamide group, flukoxycarponamide group 11F)
+l) J+ -Turtle- F. f+. Two +'4? )Up.

t11! ! As a group, a halogen atom (e.g. 7-/element atom, fluorine atom, bromine atom, etc.)
, straight-chain, branched-chain alkyl groups (e.g., methyl group, t-
butyl group, octyl group, tetradecyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (e.g., acetamide group, benzamide group).

butanamide group, octaneamide group, tetradecane 7mido group, a-(2,4-jerk-amylphenoxy)acetamide group, α-(2,4-jerk-amylphenoxy)butyramide group.

α-(3-pentadecylphenoxy)hexaneamide group, α-(4-hydroxy-3-tert-butylphenoxy)tetradecane 7mido group, 2-oxo-pyrrolidin-1-yl group, 2-oxo-5-tetra Decylpyrrolidin-1-yl group. N-methyl-tetradecanamide group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, ethylsulfone 7mido X, p-) luenesulfone 7mido group, octanesulfone 7mido group, P- dodecylbenzenesulfone 7-mido group,
N-methyl-tetradecanesulfone 7-mido group, etc.), sulfamoyl group (e.g., sulfamoyl group, N-methylsulfamoyl group).

N-ethylsulfamoyl group, N,N-dimethylsulfamoyl group, N,N-dihexylsulfamoyl group, N
-hexadecylsulfγmoyl group, N-(3-(dodecyloxy)-propyl)sulfamoyl group, N-(4-
(2,4-di-tert-7milphenoxy)phthyl]
sulfamoyl group, N-methyl-N-tetradecylsulfamoyl group), carbamoyl group (e.g. N-methylcarbamoyl group, N-butylcarbamoyl M, N-octadecylcarbamoyl group, N-[4-(2,4- di-tert-amylphenoxy)butyl]carbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc.)
, di-tecylamino group (N-succinimide group, N-7 talimide group, 2,5-dioxo-1-oxazolidinyl group, 3-dodecyl-2,5-dioxo-1-hydantoinyl group, 3-(N-7 cetyl group) N-dodecyl7mino)succinimide) & etc.), flucansulfonyl group (e.g. methoxycarbonyl group).

(tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxysulfonyl group (e.g., methoxysulfonyl group, butoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), aryloxysulfonyl group (e.g., phenoxysulfonyl group) , p-methylphenoxysulfonyl g
, 2,4-di-tert-amylphenoxysulfonyl group, etc.), furkansulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, octanesulfonyl group, 2-ethylhexylsulfonyl group).

hexadecanesulfonyl group, etc.), arylsulfonyl group (e.g., benzenesulfonyl group, 4-nonylbenzenesulfonyl group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, hexylthio group, benzylthio group, tetradecylthio group, 2- (2,4-ter
(t-amylphenoxy)ethylthio group, etc.), 7lylthio group (e.g., phenylthio group, P-)lylthio group, etc.), fluoryloxycarbonyl7mino2& (e.g.,
methoxycarbonylamino group, ethyloxycarbonylamino group, benzyloxycarbonyl 7-mino group, hexadecyloxycarbonylamino group, etc.), alkylureido groups (for example, N-methylureido group, N,N-dimethylureido group).

N-methyl-N-dodecylureido group, N-hexadecylureido group, N,N-dioctadecylureido group, etc.), acyl group (for example, acetyl group, hendiyl group, octadecanoyl group, p-dodecaneamide benzoyl group) etc.), a nitro group, a carboxyl group, a sulfo group, a hydroxy group, or a trichloromethyl group.

However, the above 2t! ! i! Among the groups, those defined as alkyl groups have 1 to 36 carbon atoms, and aryl to
'p(? Sumi M 1% 141141161↓C-Q
Q #-1k.

R22, R23, R24, R2 sweet n 2b, R27
, R2g.

R'', R゜, R31, R31 and R33 are each a hydrogen atom, a hydroxyl group, or 21
An alkyl group (preferably one with 1 to 20 carbon atoms, such as a methyl group, a propyl group, a t-butyl group, a trifluoromethyl group, a tridecyl group, etc.), an aryl group (preferably one with 6 to 20 carbon atoms) 1 For example, phenyl group, 4-
t-butylphenyl group, 2.4-di-t-7mylphenyl group, 4-methoxyphenyl group, etc.), heterocyclic groups (e.g. 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group) etc.), alkylamino groups (preferably those with 1 to 20 carbon atoms, e.g., methylamine group, diethylamino group, L-butylamino group, etc.), acylamino groups (preferably those with 2 to 20 carbon atoms, e.g.,
acetylamine group, propyl 7mido group, benzamide group, etc.), anilino group (e.g. phenylamino group, 2-chloro 7 2 11 ) 7
N/M cruelty--no h+word, →(Nils t
(For example, methoxycarbonyl group, butoxycarbonyl group, 2-ethylhexyloxycarbonyl group, e.g. acetyl group, butylcarbonyl group, cyclohexylcarbonyl group, etc.), arylcarbonyl group ( For example, preferably one having 7 to 20 carbon atoms.benzoyl group, 4
-t-butylbenzoyl group, etc.), alkylthio group (preferably J & prime number 1 to 20, e.g. methylthio group,
octylthio group, 2-phenoxyethylthio group, etc.), arylthio group (preferably one with 6 to 20 carbon atoms, such as phenylthio group, 2-butoxy-51-octylphenylthio group, etc.), carbamoyl group (preferably one with carbon number 1 to 20 (for example, N-ethylcarbamoyl M.N-methyl-N-butylcarbamoyl group, etc.),
A sulfamoyl group (preferably one having up to 20 carbon atoms, such as N-ethylsulfamoyl i.N,N-diethylsulfamoyl group, N,N-dipropylsulfamoyl group, etc.) or a sulfone 7-mido group (preferably has 1 or more carbon atoms
20 things.

For example, methanesulfonamide group, benzenesulfone 7
Mido group. P-) represents a luenesulfonamide group, etc.

Z2 represents a hydrogen atom or a group that can be separated by a coupling reaction with an aromatic primary amine developing agent resistor. #
Examples of groups that can be removed include halogen atoms (e.g., fluorine atoms, bromine atoms, etc.), coupling-off groups linked with oxygen atoms (e.g., acetoxy groups, propanoyloxy groups, benzoyloxy groups, ethoxyoxaloyloxy groups, pyloxy groups, etc.). Vinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenokyl group, 4-titanesulfonamidophenoxy group, α-naphthoxy group, 4-cyanoxyl group, 4-methanesulfonamido-phenoxy group, α-naphthoxy group , 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, pencyloxy group, 2-7enethyloxy group, 2-phe/xy-ethoxy group, 5-phenyltetrazolyloxy group , 2-benzothiazolyloxy group, etc.), coupling-off groups linked via a nitrogen atom (other examples include
7-189538, A-isomers include benzenesulfonamide 1, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,
4,5.6-bentafluorobenzamide group, octane sulfonamide group, p-cyanophenylureido group, N
, N-diethylsulfamoylamino group, 1-piperidyl group, 5.5-dimethyl-2.4-dioxy-3-oxazolidinyl group, 1-benzyl-5-ethoxy-3-hydantoinyl group, 2-oxo-1 .2-dihydro-1-
Pyridinyl group, imidazolyl group, pyrazolyl group, 3.5
-Jetyl-1,2,4-tri7zol-1-yl group, 5- or 6-promopenzotri7zol-1-yl group, 5-methyl-1.2,3.4-)riazole-1
-yl group, benzimidazolyl group, etc.), io^f:L.
Frog-1 box Ko11++I Phenylthio group. 2-carboxyphenylthio group, 2-methoxy-
5-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, benzylthio group, 2-cyanoethylthio group, 5-
Phenyl-2,3,4.5-tetrazolylthio group, 2-
penzothiazolyl group, etc.). Preferably, the detachable group is a halogen atom, a coupling-leaving group linked via an oxygen atom, or a coupling-leaving group linked via a nitrogen atom, and particularly preferred.

Aryloxy group, salt 1g atom, pyrazolyl 2 & 5
These are imidazolyl group and triacrylic group.

As the yellow color-forming coupler residue, those of the acylaceto 7nilide type are preferred, particularly those of the pivaloyl 7cetanilide ffi [XII], benzoylacetanilide type [XI], and [] represented by the following general formula.

p36 34 35 3Ei In the formula, R, R, R and R37 are each a hydrogen atom or a well-known 2I radical of a yellow color-forming coupler residue, such as an alkyl group, an alkenyl group, a flukoxy group, a furkylsulfonyl group, a halogen atom, an alkoxy carbamoyl group,
Aliphatic amide group, alkylsulfamoyl group, alkylsulfone 7mide group, alkylureido group, succinimide group replacing alkyl, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamido group, arylsulfamoyl group , arylsulfonamide group, arylureido group, carboxy group, sulfo group,
Nitro group, cyano group.

It represents a thiocyano group, etc., and these substituents may be the same or different.

Z3jt water 811 childmata Jf following general formula [XV], [x
It is represented by vt 1 [XV 11 ] or [XVIIrl.

R38 represents an optionally substituted aryl group or heterocyclic group.

R3j and R40 are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, a furkyl group, a furkylthio group, a flukoxy group, a furkylsulfonyl group, a furkylsulfinyl group, or a carboxylic acid group.

It represents a sulfonic acid group, an unsubstituted or 22-substituted phenyl group, or a heterocycle, and these groups may be the same or different atoms.

General formula [XVm+ (7) water-c' [XIX] ~
[XXrl is preferred.

In the formula, R41 and R42 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group; R43, R44, and R45 each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group; W2 represents an oxygen or sulfur atom.

Among the compounds represented by the general formula [I], particularly preferred compounds are as follows.

al, R2 may be the same or different (hydrogen atom or methyl group, Ll is -CONH- or -C
OO-, 1m is 1, n is 0 or l, A
is an ethylene group, B is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxyethyl group, a methoxyethoxyethyl group, a butyl group, J,, J2. J3 may be the same or different, -CO-1-SO-, -CON
H-1-S02NH-1-NH-CO-, -NH-So
2-1-0-1-NHCONH-1-s-1-co2+
.

-0CO-1-NHCO2-'EI and 10CON)I-
Xl, Xl, and X may be the same or different and are an alkylene group (having 1 to 4 carbon atoms), an arylene group, or a substituted arylene group, and p and q.

r and S are 0 or 1.

The polymer coupler represented by the general formula [I] has the general formula [XX
II] and [XX[[I]].

Here, the monomer [XX11] can be said to be a monomer coupler, and the monomer (xxm) can be said to be a comonomer.Next, representative examples of the monomer [XXII] and [XXm] are shown, but they are not limited to these. Also mono v-[XXII
] and [XXm ] may be used one type each, or several types may be used.

Example of Sotsuma-CXXII) (I1) CH2=CH C2Hs (Is) CH2=CH (r C1f.

(I9) CH2÷C (25) C112= CI (2G) CI(2= CI( CH, CH, CN Sotsuma [bean ■] example (31) CH2=CH C0NHC2H40CH3 (32) CH2=CH C0NHC2H40C2H5 ( 33) CH2= CH CONHC2H40C3H7 (n (34) CH2=CH C0NHC, H4QC4H9(n-) (35) CH2=CH C0NHC21 (, QC2H40CH3CONHC21
(,0CJ(3 C0NHC2840CzHs CONHC2H40C3H7(no) C0NHC21(40C4H9(禰(/11) CH2=CH C0NHC28408ゝ..NHCzHb..2H5゜.1H++..H3 Obtained by general formula [I] Polymer coupler physical and In order to improve the chemical properties (e.g. solubility, stability in gelatin, etc.), monomers such as those shown below may be used in addition to the seven-mers represented by the general formulas [XXII] and [XXm]. Good, this one is mo/ -y- [XX11],
[XXm1 Similarly, one kind may be used, or several kinds may be used in combination depending on the purpose.

(44) CH2=CH C00CsHsSosNa (45) CH2=CH C0NHC2H4NHSO2CH3 (46) CH2= CH COOC2H40COC2H4COOH (47) C
H2=CHO Gate b(J2NH(,2H40CH3 CONHC2H4SO2NH2 (52) c) (2,= cl-1C0NHC2H
40(4H4NH5O2CHi(53) CH2=
CH C00C2H4NH5O2CH3 Other examples include acrylic acid 5 α-chloroacrylic acid, α-alacrylic acid (such as methacrylic acid),
Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide,
n-butylacrylamide, t-butylacryl 7mide, diacetone acrylamide, methyl acrylate, ethyl 7-acrylate, n-propyl acrylate, n-butylacrylate, t-butylacrylate.

1so-butyl acrylate, 2-ethylhexyl 7-acrylate, a-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (such as styrene and its derivatives 1 such as vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene), itaconic acid, citraconic acid, crotonic acid, Examples include, but are not limited to, vinylidene chloride, vinyl alkyl ethers (e.g., vinyl ethyl ether), maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. .

As is well known in the field of polymer couplers, the general formula [XX
Physical and/or chemical properties of the copolymer formed with a monomeric coupler corresponding to [XX[II] or any further monomers 1, e.g. solubility, binders of photographic colloidal compositions e.g. gelatin It can be selected such that its compatibility with the polymer, its flexibility, thermal stability, etc. are favorably influenced.

The polymer coupler used in the present invention may be prepared by dissolving a polymer coupler obtained by polymerizing a monomer coupler in an organic solvent and emulsifying and dispersing it in an aqueous gelatin solution in the form of latex, as described above, or It can also be made by direct emulsion polymerization (U.S. Pat.
No. 820, for emulsion polymerization, U.S. Pat.
The methods described in No. 0,211 and No. 370.952 can be used.

The polymer coupler of the present invention is synthesized using a polymerization initiator.

As a polymerization solvent, JP-A-56-5543, JP-A-57-
No. 94752, JP-A-57-176038, JP-A-5
This is carried out using the compounds described in JP-A No. 7-204038, JP-A-58-28745, JP-A-58-10738, JP-A-58-42044, and JP-A-57-29683.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc.
It is possible to polymerize at a temperature of 30°C to 100°C, but polymerization is usually carried out at a temperature of 30°C to 100°C.

The proportion of the color-forming portion corresponding to the general formula [XX11] in the copolymer coupler is usually preferably 10 to 90% by weight, but from the viewpoint of color reproducibility, color development, and stability, it is usually 20 to 8%.
0i1j1% is preferred, in which case the molecular weight (grams of polymer containing 1 mole of monomeric coupler) is about 25
The range is from 0 to 4000, but is not limited thereto.

The polymeric coupler latex of this invention is added to the silver halide emulsion layer or to a layer adjacent thereto.

The polymer coupler latex of the present invention is based on the coupler monomer, and preferably 0.01 to 0.5 moles per mole of silver when in the same layer as silver halide.
It is preferable to add 0.10 mol.

Further, when the polymer coupler latex of the present invention is used in a non-photosensitive layer, the coating amount is 0.01 g/rrf to 1
, Og/rrf, preferably 0.1 g/m'~0,
It is in the range of 5 g/rrr'.

A typical synthesis example of the polymer coupler of the present invention is shown below.

[Production method (■)] Synthesis example (I) Polymer coupler I (#polymerized polymer of monomer coupler (3) and monomer (31)) - Exemplary monomer (3) 1
After heating a mixture of 0 g, illustrative Zumer (31) log, and N,N-dimethylacetamide lo OmM to 80 ° C. with stirring in a nitrogen stream, 10 m of an ethanol solution containing 0.5 g of dimethyl azobisisoacetate was added. Polymerization started. After reacting for 5 hours, the reaction solution was cooled and water was added.
51 and filtered out the precipitated solid.

Furthermore, it was thoroughly washed with water.

This solid was pre-thermally dried under reduced pressure to obtain 19.3 g of Bommer Covlar (I).

This polymer coupler contained 50.2% of the exemplary Zumer coupler (3) component in the polymer formed from chlorine analysis.

Synthesis Example (2) Polymer coupler ■ (copolymer of exemplified monophyletic coupler (I4) and exemplified comonomer (31)) 70 g of exemplified Zuma-(I4), exemplified Zuma-(32) 3
After heating a mixture of 0 g and 500 m of N,N-dimethylacetamide to 65° C. under continuous stirring in a nitrogen stream, 20 njL of a methyl cellosolve solution containing 0.4 g of dimethyl azobisisoacetate was added to initiate polymerization. After reacting for 8 hours, the reaction solution was cooled, poured into water IfL, and the precipitated solid was filtered off.

Furthermore, it was thoroughly washed with water.

By heating and drying this solid under reduced pressure, 96.5 g of polymer coupler (n) was obtained.

This polymeric coupler contained 70.3% of the illustrative Zummer coupler (I5) component as determined by fluorine analysis.

Synthesis Examples (3) to (I5) Polymer couplers were synthesized according to the method of Synthesis Example (I) using monomeric couplers and comonomers as shown in Table 1 below. The results are shown in the same table.

(Production method (■)) Synthesis example (I6) Polymer coupler xvi (Exemplary monomer coupler (I
Copolymerization polymer of 4) and exemplified comonomer (31)) A 1.2-liter aqueous solution containing 3 g of oleyl methyl tauride was added to a 2-fL flask while stirring and passing an elementary air stream through the room.
℃, and add 2% potassium persulfate aqueous solution 3 to the aqueous solution.
After adding 0m sentence 1 example monomer coupler (I4) 20g
and 40 g of exemplified comonomer (31) in 400 m of methanol.
A solution heated and dissolved in Jl was added dropwise over 20 minutes.

After 2 hours of reaction, methanol was distilled off.

The latex formed was adjusted to pH 6+0 with cold i1N sodium hydroxide and filtered.

The latex formed had a polymer concentration of 5.2%, with 34.0% monomeric coupler in the polymer according to fluorine analysis.
It was found that component I4) was contained.

Polymer couplers were synthesized by copolymerizing monomeric couplers and comonomers as shown in Table 2 below according to the method of Synthesis Example '(ts). The results are as follows: /'/' The polymer couplers of the present invention can be used alone or in combination of two or more.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodobromide containing about 30 mol% or less of silver iodide. be. Particularly preferred is about 2
Silver iodobromide containing from mol % to about 25 mol % silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains of up to about 10 microns in projected area diameter, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention are:

For example, Research Disclosure (RD).

No. 17643 (December 1978), 22-23
Page, -1, Emulsion preparation
tion and types)” and the same No. 1
8716 (November 1979), p. 64B, "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chemic et P
h1sique PhotographiquePa
ul Montel, 196)), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Du
ffin.

Photographic Emu'1sion
Chemistry (FocalPress, 1
966) ), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (VtL, Zelikm
an et al., Making and Ca.
tingPhotographic Emulsion
, Focal Press, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), No. 14
Vol. 248-+257 (I970): U.S. Patent No. 4
, 434.226, 4,414,310, 4.433.048, 4,439,520, and British Patent No. 2,112,157. I can do something.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, it may be a single layer structure, or it may be joined by epitaxial bonding from silver halides of different compositions. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure No.
17643 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two research disclosures, and the relevant descriptions are shown in the table below.

2 Sensitivity increasing agent 3 Spectral sensitizer, pages 23-24 Page 648 right column ~ Super sensitizer
Page 649 Right column 4 Brightener 24
Page 5 Anti-fog agent Pages 24-25 Page 649 Right column and stabilizer 6 Light absorber, Pages 25-26 649 Right column ~ Filter dye 650 Left column Ultraviolet absorber 7 Stain inhibitor Page 25 Right column Page 650 Left ~ Right column 8
Dye image stabilizer page 25 9 Hardener page 26 Page 651 left column lO binder page 26 Same as above 11 Plasticizer,
nLubricant page 27 Page 650 right column 12 Coating aid 1
Table 26-27 Same surface active agent 13 Static prevention page 27 Same surface active agent Various color couplers can be used in the present invention, specific examples of which can be found in the Research Disclosure mentioned above.
It is described in the patents listed in (RD) No. 1 7643, ■-〇~G.

As a yellow coupler, for example, U.S. Pat. No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4.401.752, Special Publication No. 5
B-10739, British Patent No. 1,425,020,
Preferably, those described in Id. No. 1,476°760 and the like are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3,725,067, Research Disclosure No. 24220 (I984) June), Japanese Patent Application Publication No. 1983
-33552, Research Disclosure No.4
4230 (June 1984), JP-A-60-4365
No. 9, U.S. Patent No. 4,500,630, U.S. Patent No. 4.54
Particularly preferred are those described in No. 0,654.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396.

4,228,233, t54,296,200
No. 2,369,929, t52,8Of, 1
No. 71, No. 2,772,162, No. 2,895,
No. 826, No. 3,772,002, No. 3,758
, No. 308, No. 4.334.011, No. 4. ．． 3
No. 27,173, West German Patent Publication No. 3,329,729, European Patent No. t5121.36SA, U.S. Patent No. 3,4
No. 46,622, No. 4,333,999, No. 4,
Preferred are those described in No. 451.559, No. 4,427,767, European Patent No. 161,626A, and the like.

Colored coupler for correcting unnecessary absorption of coloring dyes, Research Disclosure No. 1764
Section 3-G, U.S. Patent No. 4.163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929
No. 4.138゜258, British Patent No. 1,146
, No. 368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent f52,12.
No. 5,570, European Patent No. 96.570, West German Patent (
The one described in Japanese Publication No. 3,234,533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat.

No. 4,612,273, British Patent No. 2. t.

2.173 etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD17643.
■-Patent listed in Section F, JP-A-57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and US Pat. No. 4,248,962.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 54,130,427, U.S. Pat.
4,338,393, i4,310,618, etc., JP-A-60-185950
Examples thereof include DIR redox compound-releasing couplers described in European Pat.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Examples of the process, effects, and latex for impregnation of latex dispersion methods include U.S. Pat. It is described in.

Suitable supports that can be used in the present invention include, for example.

The aforementioned RD, No. 17643, page 28, and the same No.
, 18716, from the right column on page 647 to the left column on page 648.

The color photographic material according to the present invention includes the above-mentioned RD, N
o, 17643, pages 28-29, and same No. 18
Development processing can be carried out by the usual methods described in 651 left column to right column of 716.

The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment.

The washing process is 2#f! It is common to use countercurrent main washing in the above tanks to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step.

(Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention has extremely excellent color development.

Further, the silver halide color photographic light-sensitive material of the present invention exhibits the remarkable effect of providing a color photograph with a color image that is robust against heat and moist heat after processing.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 Sample A was obtained by coating an emulsion layer and an auxiliary layer in the following order on a triacetyl cellulose support provided with the following layers (see Table 3 below).

17th! j; 2-(heptafluorobutyramide)-5-(2″) which is a low molecular weight cyan coupler compared to the red-sensitive emulsion layer polymer coupler;
100 g of -(2'',4''-di-t-aminophenoxy)butyramide)-phenol was added to tricresylphosphate-)-Zo.

cc and 100cc of ethyl acetate and stirred at high speed with 1kg of 10% gelatin aqueous solution to obtain 500g of emulsion.
was mixed with 1 kg of red-sensitive silver iodobromide emulsion (containing 70 g of plate and 60 g of gelatin, iodine content was 4 mol%) and coated to a dry film thickness of 2 (#1.5 g/g). .

2nd layer: Protective layer A 10% aqueous gelatin solution was applied to give a dry film thickness of 2.

Comparative polymeric cyan coupler AI 4.3g or comparative polymeric cyan coupler B (described in U.S. Pat. No. 4,612,278 (I
8) (R9=H) Compound) 1 Equimolar amounts of the polymer cyan coupler (n) or (V) of the present invention for the color forming unit portion were dissolved by heating in 60 mjL of ethyl acetate, and 15 g of gelatin and 1 part of sodium lauryl sulfate were added.
．． After adding to 300 mjl of aqueous solution containing 2 g and dispersing using a colloid mill, ethyl acetate was removed under reduced pressure,
The above polymer cyan coupler A.

Polymer cyan coupler B, polymer cyan coupler (
(2) and latex dispersion Th (a) corresponding to the polymer cyan coupler (V), respectively.

(b), (c), and (d) were obtained.

These latex dispersions were prepared in exactly the same manner as Sample A, except that instead of the emulsion of cyan coupler in Sample A, only a compound such that the mole of cyan coupler in Sample A was equal to that of the cyan coupler in Sample A was used. .

C, D and E were obtained.

These samples A to E were exposed to light and subjected to the reversal color processing described below.

The treatment steps and treatment liquid used here are as follows.

Processing process Process Time Temperature -Development 6 minutes 38℃ Washing with water 2 minutes II Reversal 2 minutes II Color development 6 minutes 1j Adjustment　　　　2 minutes　　　jj Bleaching 6 minutes 11 Fixation 4 minutes II Washing with water 4 minutes II Stable for 1 minute at room temperature.

drying The treatment liquid used had the following composition.

Dilwali Bashishui 700m
Minitosoro N,N,N-trimethylenephosphonic acid pentasodium salt 2g Sodium sulfite 20g Hydroquinone monos J lephonate potassium salt 30g Sodium carbonate (I hydrate) 30g 1-phenyl 4-methyl 4-hydroxymethyl-3 and lazolitone 2g potassium bromide 2.5g potassium iodide (0.1% solution) 2mu thioether compound (shown in Table 1) Add water 700m
Nitrilosilymethylenephosphonic acid, 6Na salt 3g Stannous chloride (dihydrate) IgP-aminophenol 0.1g Sodium hydroxide
8g glacial acetic acid
Add 15rn bunsui and add “C” l
ooomjL & EkiL (Shuseisui 700m
JL Nitrilotrimethylenephosphonic acid hexasodium salt 2g Sodium sulfite 7g Sodium triphosphate (I dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1%
solution) 90m sodium hydroxide
3g Citrazine # 1.5gN
・Ethyl-N-(β-methanesulfonamidoethyl)-3・Methyl-4-aminoaniline sulfate 11g3.6-cythiaoctane-1°8-diol 1g Add water
1000m 9°Okisato water 700m sodium sulfite 12g ethylenediamine, sodium tetraacetate (dihydrate) 8g thioglycerin 0.4m glacial acetic acid
Add 3m Bunsui
1000100O Makusui 800m Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Iron (m) ammonium ethylenediaminetetraacetate (dihydrate') 120. Og potash bromide 100.0g add water
1000m fixed smoked water 800m
Ammonium exchange thiosulfate 80.0g Sodium fEite 5.0g Sodium bisulfite 5.0g Add water
looomM Yushu Kunsui 800m
Bun Formalin (37ffii%) 5.0mM Fuji Drywell Add 5.0m Bunsui
The color purulence and color image fastness of the cyan image of the development sample obtained at 1000 m are shown in Table ffG3.

From the results in the table above, it is clear that the cyan polymer coupler of the present invention has extremely excellent color forming properties and forms color images that are robust against heat and moist heat in color photographs after processing.

Example 2 Next, a color reversal photographic material was prepared by coating 1st to 12th calendars in the following order on a triacetate film base.

First calendar: antihalation layer (gelatin layer containing black colloidal silver).

Second layer: gelatin middle layer.

2.5-di-tert-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate) and 100 cc of ethyl acetate, and 2 kg of the emulsion obtained by stirring at high speed with 1 kg of 10% gelatin aqueous solution was mixed into a non-chemically sensitized fine grain emulsion ( Grain size 0.06g, 1 mol% silver iodobromide emulsion) 1k
C1HIk0, 4 g/g mixed with 1.5 kg of 10% gelatin and coated to a dry film thickness of 2.
m').

3rd layer: low-sensitivity red-sensitive emulsion layer 2-(heptafluorobutyramide)-5-(2'-(2'', 4''-di-t-7minophenoxy)butyramide)-phenol long, which is a cyan coupler, 100cc of tricresyl phosphate and 1oO of ethyl acetate
Dissolve in cc.

500 g of the emulsion obtained by stirring at high speed with 1 kg of 10% gelatin aqueous solution was mixed with 1 kg of red-sensitive silver iodobromide emulsion (silver 70
g, gelatin (60 g, iodine content: 4 mol %) and coated to a dry film thickness of 1 #L. (Silver 0
, 5 g/rrf) 4th layer; Highly sensitive red-sensitive emulsion layer cyan coupler 2-(heptafluorobutyramide)-5-(2"-(2", 4"-di-1-7 minophenoxy)butyl 7 100 cc of tricresyl phosphate and 100 cc of ethyl acetate.
Dissolve in cc.

1000 g of an emulsion obtained by stirring at high speed with 1 kg of a 10% gelatin aqueous solution was mixed into a red-sensitive silver iodobromide emulsion 1 k [(silver 7
Contains 0g and 60g gelatin.

The iodine content is 2.5 mol%), and the dry film thickness is 2.5%.
I applied it to make a pot. (Silver io, 7 g/m') Fifth layer: Intermediate layer 2.5-di-t-octylhydroquinone.

100cc of dibutyl phthalate and 100cc of ethyl acetate
1 kg of an emulsion obtained by dissolving in 1 kg of 10% gelatin and stirring at high speed with 1 kg of an aqueous solution in 10% gelatin was mixed with 1 kg of 10% gelatin and applied to give a dry film thickness of 1 pot.

6th layer: low-sensitivity green-sensitivity emulsion layer 1, - which is magenta coupler instead of cyan coupler
(2,4,6-hlichlorophenyl)-3-(3-(2
, 4-di-t-amylphenoxyacetamido)benzamido)-5-pyrazolone was used, but 300 g of the emulsion obtained in the same manner as the emulsion of the third layer was mixed into a green-sensitive silver iodobromide emulsion. 1kg (including 70g of ffi, 60g of gelatin,
(Iodine content: 3 mol %) and coated to a dry film thickness of 1.3 g. (Silver fit0, 7 g/rrf
) 7th layer; highly green-sensitive emulsion layer 1-( which is a magenta coupler instead of a cyan coupler)
2,4,6-)lichlorophenyl)-3-(3-(2,
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 4-di(-amylphenoxyacetamide)benzamide)-5-pyrazolone was used was mixed with 1 kg of green-sensitive silver iodobromide emulsion ( (containing 270 g of I, 60 g of gelatin, and iodine content of 2.5 mol%) to form a dry film thickness of 3.5#.
It was applied so that it became L. (#! Amount 0, 8 g/rr
1') No. 8: Yellow filter A layer of yellow emulsion containing colloidal silver was coated to a dry film thickness of lμ.

9th Calendar: Low sensitivity gastric cancer emulsion layer α-(
hyeroyl)-α-(I-benzyl-5-nitoxy 3
-Hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used in the same manner as the emulsion for the third layer except that emulsion 1ooog was mixed with 1kg of blue-sensitive silver iodobromide emulsion (70g of silver). , contains 60g of gelatin.

The iodine content is 2.5 mol%), and the dry film thickness is 1.5%.
It was applied so that it was μ. (fIiwa 0.6g /
rn') T510 layer: Highly sensitive blue-sensitive emulsion layer α-(
hivaloyl)-α-(I-benzyl-5-nitoxy 3
-hydantoinyl'')-2-90rho-5-dodecyloxycarbonylacetanilide was used, but tIIJ3!
1000 g of the emulsion obtained in the same manner as the emulsion of
Boil og.

The iodine content is 2.5 mol%) and the dry film thickness is 3#.
It was applied so that it became L. (Amount of silver 1.1g/go) Eleventh calendar: 1kg of the emulsion used in the 2nd protective layer and 1kg of 10% gelatin
The mixture was mixed and applied to give a dry film thickness of 2.

12th F: Fine grain emulsion coated with one layer of wSl (grain size 0-064.
A 10% gelatin aqueous solution containing 1 mol % silver iodobromide emulsion) was coated to give a silver coating amount of 0.117 rn', a dry film thickness o, and 8 IL.

The samples prepared as described above are shown in Table 4 below as sample numbers lot.

Next, latex dispersions (b) and (c) prepared in Example 1
Samples 102, 103 and 104 were prepared in exactly the same manner as in sample lot, except that instead of the emulsion of cyan coupler in sample lot, the emulsions of cyan coupler in sample lot were used in an amount equivalent to the cyan coupler in sample 101 per unit of coupler. I got it.

Next, as shown in Table 4, comparative polymer coupler C1
4.3 g of the polymer coupler 01) of the present invention in equimolar amounts for the color forming unit portions were dissolved by heating in 60 ml of ethyl acetate, and added to 300 ml of an aqueous solution containing 15 g of gelatin and 1.2 g of sodium lauryl sulfate to form a colloid. After dispersing using a mill, ethyl acetate was removed under reduced pressure to obtain latex dispersions (e) and (f).

These latex dispersions were used in place of the emulsion of magenta coupler in sample 101 to prepare sample 10 t per unit of coupler.
Samples 105 and 106 were obtained in exactly the same manner as sample 101 except that only a value equimolar to that of the magenta coupler was used.

These samples lot 106 were exposed to light and processed in the same manner as in Example 1.

The results of comparing the color filtration and color dye fastness of the cyan and magenta images of the obtained developed samples are shown in the following table.

/<' From the results in Table 4, it is clear that the polymer coupler of Suekan 131 has excellent coloring properties and forms color images that are robust against heat and moist heat in color photographs after processing.
I am clear.

Example 3 A multilayer color photosensitive material consisting of each layer having the composition shown below on a transparent tri7cetyl cellulose film support (
301) was created.

1st Calendar: Haleshion Prevention Layer Black Colloid Ginken...φ-・o, 15g/ is an ultraviolet absorber U-1...0.08g/rn' Same L
j-2-・2nd layer of gelatin layer containing 0.12g/G; Intermediate layer 2.5-G[-pentadecylhydroquinone・・O, 18g/rn' coupler C-1・・φe fist 0.11g Gelatin layer 3rd layer containing /m': 1st red-sensitizing milk layer, -1.2g/ni' sensitizing dye! ...1.4Xlo' mol per mole of silver Sensitizing dye ■...0゜4X10' mole per mole of silver m...s, 5xto' per mole of silver Same mole ■・Poor... [4.0 x 10-4 mole coupler for 1 mole C-2-・No.・0.45g/Go coupler 〇-3---0.035g/m' force・Puller C-4 −
---Gelatin layer containing 0,018g/rn' 4th calendar: 2nd red-sensitive emulsion history 1--1.0g/rn' is a sensitizing dye!・5.2X10' for #11 mole
%le Same ■φ...1.5XIO-5 moles per 1 mole of silver m-Φ...2.1X10" moles per 1 mole of silver ■---1 per 111 moles, 5 X I O'% Lukabra-C-2---0,050g/m'coupler
C-5---0,070g/nf coupler C-3Φ
Gelatin layer containing φo, 035sr/R 5th layer: Intermediate layer 2.5-gelatin layer containing 00.08 g/rn' of pentadecyl hydroquinone 6th layer: 1st green-sensitive emulsion layer φ・Q・0.80g/rrI' Sensitizing dye V-...4.0X10' mole equivalent to 1 mole of silver ■...S, oxto-5 mole equal to 1 mole of silver ■...・1, oxlO' mole for comparison coupler A...Q, 43 g/m'' coupler for 1 mole of silver
C-7...0.13g/go coupler 〇-8---
-0-02g/rn' coupler C-4---0,0
Gelatin layer 7th layer containing 3 g/ln': 2nd green-sensitive emulsion layer Silver iodobromide Silver iodide 8 mol% Average grain size 0.8 de...0.85 g/G sensitizing dye V... ...z, 'rxto-' mole is the same for 1 mole of silver ■... βt, axto for 1 mole of silver
-5 mole same ■...7.5xlO' mole coupler per 1 mole of silver C-6...0.095g/go coupler
C-7・Fist・Gelatin layer containing 0.015g/G! R8 layer: Yellow filter single layer drum color colloidal silver...o, 08g/rn'2.5-
Gelatin layer containing di-t-pentadecylhydroquinone...0.090 g/rn' 9th layer: 1st blue-sensitive emulsion layer Average grain size 0.3 - 0.37 g/rrl' 1131 Sensitive dye 1...・φ4.4XI for 1 mole of silver
O'molar coupler 〇-9""0.71g/m' coupler C-
4---@0.05g/m' 1st O layer: 2nd blue-sensitive emulsion layer・No. 0.55g/m'#f-sensitive dye■...3.0XIO- per mole of competing silver
Gelatin layer tPIl1 layer containing 4 Molkabu 5 C9si+aaO,'23 g/m; First protective layer ultraviolet absorber U-1---0,14 g/m'
U-2... 12th gelatin layer containing 0.22g/rr1'; 2nd layer! I scrap - 0.25g/m' polymethacrylate particles (diameter 1.5p) ・・gelatin layer containing O,log/rr+' In addition to the above composition, gelatin hardener H-1 and surfactant are added to each layer. The agent was applied.

(Samples 302 to 304) Comparative coupler A contained in the 6th layer of sample 301
AjL! was used in the same manner as Sample 301, except that comparative couplers B, C, and polymer coupler (■) of the present invention were replaced by n in equal weight in order to match the film thickness. :, adjust the color temperature to 4800°K with a filter using a source,
Imagewise exposure is performed to give an exposure of jth large 20 CMS,
The following color development process was performed. The density of the treated strips was measured using a green filter (an interference filter that transmits light with a wavelength of 546 nm, manufactured by Fuji Photo Film Co., Ltd.), and the photographic performance is summarized in Table 5.

Color development processing (38℃) Color development 2 minutes 45 seconds Bleaching 6 minutes 30 seconds Water washing 2 minutes 10 seconds Fixed: i
F Wash with water for 4 minutes and 20 seconds
Stable for 3 minutes 15 seconds 1 minute 05
The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1.0g 1-hydroxyethylidene-1゜l-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide
1.4g potassium iodide 13■
g hydroxylamine sulfate f4 2,4 g4-
(N-Ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5g Add water
1.0 exchange PHIO, O' Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate
io, add 0g water
1.02PH6,0 Fixer Ethylenedi7minetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175, 0m! Add 4.6g of L sodium bisulfite water
1.0jlpH6.6 Stabilizing liquid formalin (40%) 2.0m polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) Add 0.3g water t, oif55Table 1) Fog +0.2 Relative value with sample 301 as 100, which is the reciprocal of the exposure amount that increases the density by 4 2) The slope of the straight line connecting the density of fog + 0.2 and fog + 0.7, expressed as (magenta density)/log (exposure amount) .

3) Magenta density at ICMS exposure dose Structure of compound used in Example 2 U-2 H H 0$J UfiH171tl C-6 (l CH2 = CH- 502 - CHz - CON
H(CH2)2 8HCO- CH2- SOS-
CH = CH2 sensitizing dye ■ IV C2H.

C2H.

■ ■ C2Hs patent applicant Fuji Photo Film Co., Ltd. agent Patent attorney Ii 1)
Toshi 3-ri continuation Ij 1st year (self-motivated) May 22, 1988 Commissioner of the Patent Office Kuro 1) Akio Yu Tono 1, Display of F items 1986 Patent Application No. 297373 2, Name of invention halogen Silver chemical color photographic material 3, relationship with the person making the correction Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520)
Fuji Photo Film Co., Ltd. Representative: Minoru Ohnishi 4, Agent address: 6th floor, 7th floor, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo 105, "Detailed Description of the Invention" in the specification subject to amendment Column 7, Contents of the amendment (I) In the 5th line of page 6 of the specification, “the inventors” was changed to “
The inventor has amended the following.

(2) Page 9, line 3 of the same book will be corrected.

(3) Same book, page 11, line 9 I will correct it.

(4) Line 1 O of the same page in the same book I will correct it.

(5) Same book, page 21, line 17 "-(-L1+VfL navy blue, r　-(-L　1+i-+L　?", will be corrected.

(6) Same book, page 34, line 15 no r [X [[] J
Correct it to r[X[[] -1, [XIr1-2J.

(7) In the same book, page 16, r [XI] J is replaced with “
Corrected to [Bruce] -1, [XI] -2J.

(8) The entire statement on page 35 of the same book has been amended as follows.

(9) Same book, page 40, line 11 To do.

"(I0) Correct the chemical formula of (52) on page 53 of the same book.

(I1) Correct "copolymer" in line 17 of page 56 of the same book to "polymer".

(Above) Procedural Amendment (0 citation July 22, 1988 Director General of the Patent Office Kunio Ogawa 1, Indication of the case 1985 Patent Application No. 297373 2, Name of the invention Silver halide color photographic light-sensitive material 3 , Relationship with the case of the person making the amendment Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520)
Fuji Photo Film Co., Ltd. Representative: Sho Ohnishi 4, Agent address: 6, 7th floor, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo 105, "Detailed Description of the Invention" in the specification subject to amendment Column 78 Amendment details (I) Specification, page 72, line 16 to page 73, line 3
Correct the line "The color of the present invention..." as follows.

"The silver halide color photographic material of the present invention is...

After desilvering treatment such as fixing or bleach-fixing, it is common to undergo a water washing and/or stabilization process.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application 1, and the temperature of the washing water.
It can be set over a wide range depending on the number of water washing tanks (number of stages), replenishment methods such as countercurrent or forward flow, and various other conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is as follows:
Journal of the Society of Motion Picture and Television Engineers (
Journal of the 5ociety of
Motion Picture and Te1evi
sion Engineers) Volume 64, p. 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. In addition, chlorine-based disinfectants such as inthiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use disinfectants described in , Hygiene Technology Extra Section [Sterilization, Disinfection, and Anti-Mold Technology of Microorganisms] and Japan Antibacterial and Anti-Mold Science Extra Section "Encyclopedia of Antibacterial and Antifungal Agents."

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 25 to 10 minutes.
A range of 30 seconds to 5 minutes at ~40°C is selected.

Furthermore, the photosensitive material of the present invention can be directly processed with a stabilizing solution instead of the above-mentioned washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
No. 3, No. 58-14834, No. 59-184343, No. 60-220345, No. 60-238832,
Any of the known methods described in JP 60-239784, JP 60-239749, JP 61-4054, JP 61-118749, etc. can be used. In particular, a stabilizing bath containing 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. . (2) "Example 2" in the first line of page 102 of the same book has been amended to "Example 3."

(3) Correct the structure of compound rC-3J on page 103 of the same book.

(that's all)

Claims (1)

[Scope of Claims] A silver halide color photographic material comprising a polymer coupler represented by the following general formula (I) and consisting of at least two types of repeating units. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. Represents an alkyl group with 1 to 4 carbon atoms or chlorine, and L_1 has a numerical formula, chemical formula, table, etc. (R^3 represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms), -COO-, -NHCO -or-O
represents CO-, L_2 represents a linking group connecting L_1 and Q, m represents 0 or 1, n represents 0 or 1, and Q is coupled with an oxidized aromatic primary amine developer. Represents a coupler residue capable of forming a dye, A represents an alkylene group having 1 to 4 carbon atoms, B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and x and y represent each unit in the polymer coupler. x is 10
-90% by weight, y is 10-90% by weight. )