JPH02856A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material which has a sufficiently high dye image density, high film strength and excellent sharpness by incorporating a water soluble polymer having specific repeating units. CONSTITUTION:The water soluble polymer having respectively at least >=1 kinds of the repeating units consisting of formulas I, II is incorporated into the photosensitive material. In formula I, A denotes the unit derived from the vinyl monomer having the residual coupler group which can form a dye by coupling with the oxidant of an arom. primary amine developing agent. In formula II, B is the repeating unit expressed by formula III. In formula III, R denotes a hydrogen atom, chlorine atom, etc.; Q denotes an arylene group; L denotes a divalent group; R1, R' denote a hydrogen atom, etc.; (l), (m) denote 0 or 1 which are not simultaneously 0. The silver halide color photographic sensitive material having the high dye image density and the excellent film strength and sharpness is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to novel photographic polymer couplers incorporating groups capable of crosslinking with gelatin.

(Prior art) Recently, color photographic materials have been moving toward higher image quality.
Image quality that can be viewed even when enlarged from a small format such as /10 size has been developed. However, advances in graininess and sharpness have been strongly desired.

Among these, regarding sharpness, JP-A-39-3tλg No. 2, same! Goo/goo! There is a method of emphasizing the edge effect using a DIR compound represented by No. 3J, and a method of minimizing light scattering by making the coating film thinner. It is shown in Japanese Patent Application Laid-Open No. ShojP-J62≠9 that a combined use of these means provides even greater effects.

In order to achieve thinner layers, ■ Reduce the pallast group of the coupler.

■ Reduce the amount of high-boiling organic solvents used as coupler solvents.

■ Polymerize couplers to increase the density of color-forming groups.

There are methods such as ①, however, there is a problem with coupler diffusion resistance, and ③ is difficult to reduce to an extreme due to coupler precipitation and decrease in color development, and drastic thinning cannot be expected. . Regarding (2), among polymerized couplers, latex-like couplers and those used in emulsion and dispersion are extremely thin and the film strength is weakened when the amount of gelatin is reduced to make the layer extremely thin. This method had the disadvantage that the film was easily scratched after processing.

On the other hand, polymer couplers with hydrophilic properties, such as polymer couplers in which a reactive coupler is bonded to a pre-synthesized polymer (acrylic homopolymer, p-amine styrene homopolymer, etc.) or a natural polymer compound (gelatin, etc.), are patented in the US. Tube λt g727, same λ♂yo 2311, same 2t! No. 2313, No. 21707/2, Japanese Patent Publications No. 3J-/A-3λ, No. 3667, etc., in which couplers synthesized in the form of ethylenically unsaturated monomers are Polymer couplers obtained by copolymerizing with other polymerizable monomers are described in British Patent No.
No. 201, No. 6/7, No. 3, No. 67, No. 9F636.3, No. 1
No. 1041618'. However, the aforementioned hydrophilic polymer couplers have insufficient diffusion resistance, so interlayer color mixing is likely to occur, and there are problems such as couplers flowing out into the processing solution during processing, so they are not put to practical use. Ta.

In order to solve these shortcomings, US patent tube≠2071
0? No., same≠Koisiri No. 5, Japanese Patent Publication No. 7-20573
No. 6, same j1-27/3 issue, same! ! -217'Al1
There is a water-soluble polymer coupler (for example, a hydrophilic polymer coupler having a phenolic hydroxyl group or an active methylene group) that uses a group that can be crosslinked with gelatin via a hardening agent, as disclosed in the above issue. However, since these crosslink with gelatin via a hardening agent, the crosslinking speed with gelatin is slow.
In addition, the efficiency of crosslinking couplers and gelatin through a hardening agent, such as a crosslinking reaction between couplers and gelatin, was low and the diffusion resistance was insufficient.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a water-soluble polymer coupler that has excellent diffusion resistance, provides a sufficiently high dye image density, and furthermore has a rapid crosslinking reaction with gelatin. An object of the present invention is to provide a silver halide color photographic material.

The second object is to provide a silver halide color photographic material that has strong film strength and excellent sharpness.

(Means for Solving the Problems) These objects of the present invention are based on the following general formulas (I) and (II).
A silver halide color photographic light-sensitive material is achieved, which is characterized by containing a water-soluble polymer having at least one type of repeating unit consisting of the following.

General formula (I) +A + (The person in the formula represents a unit derived from a vinyl monomer having a color coupler residue capable of forming a dye by coupling with an oxidized product of an aromatic-grade amine developer.) General Formula (n) →]I← In the formula, B is a repeating unit represented by the following (II-A).

Here, R represents a hydrogen atom, a chlorine atom, or an alkyl group.

IQ is -Co2- -CON- or an arylene group having 6 to 10 carbon atoms.

IL contains at least one -CO□--CON- bond,
a divalent group having from 3 to/or carbon atoms, or
−〇−−N −−Co −15o−3o −−8o
--3o2N- and is any divalent group having / to 72 carbon atoms.

R1 represents a hydrogen atom or a lower alkyl group having 7 to 6 carbon atoms.

R' represents a hydrogen atom or an alkyl group.

GI, m represents Q or /, but cannot be O at the same time.

A polymer coupler in which a hardening agent is incorporated as a copolymerized monomer as in the present invention is a novel coupler that has excellent diffusion resistance and has never been seen before.

A preferred example of the monomer compound represented by the general formula (1) that forms a dye by campling with the oxidized product of the aromatic-grade amine developing straw used in the present invention is represented by the general formula (III). It is something.

- Nail formula (II [) ÷ C11 IC publication - L (0 → E7 → F → Q In the formula, R represents a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and D represents -C0O-- CONR'-
1 or a substituted or unsubstituted phenyl group, and E
represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, F is -CONR'-,
-NR'C0NR'-NR'COO--NR'CO-
-0CONR'-8O□NR'-,R' represents a hydrogen atom, IA, or an unsubstituted alkyl group or aryl group. When two or more R's exist in the same molecule, they may be the same or different. D, E and R''
Examples of substituents include alkyl groups (e.g. methyl group,
ethyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), aryloxy group (e.g., fynyloxy group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, etc.), acylamino group (e.g., acetylamino group), carbamoyl group, Alkylcarbamoyl groups (e.g. methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl groups (e.g. dimethylcarbamoyl group), arylcarbamoyl groups (e.g. phenylcarbamoyl group), alkylsulfonyl groups (e.g. methylsulfonyl group), arylsulfonyl groups (e.g. phenylsulfonyl group), alkylsulfonamide group (e.g. methanesulfonamide group), arylsulfonamide group (e.g. phenylsulfonamide group), sulfamoyl group, alkylsulfamoyl group (e.g. ethylsulfamoyl group), dialkylsulfamoyl group (e.g. dimethylsulfamoyl group), alkylthio groups (e.g. methylthio group, arylthio group (e.g. phenylthio group), cyano group, nitro group, halogen atom (e.g. fluorine, chlorine, bromine, etc.), and this substituent When there are two or more, they may be the same or different.

j! , m, n represent 0 or 1, provided that l, m,
When n is 0, Q represents a cyan, magenta, and yellow dye-forming coupler residue that can camp with the oxidized product of an aromatic-grade amine developer to form a dye.

Among the color coupler residues represented by Q, cyan-forming coupler residues include phenol type (IV) (V),
Or naphthol type (■), [■] compounds (each with 1
It is preferable that the OH group at the position and the hydrogen atom other than the camping site are separated and connected to F in the general formula (m).

OI+ In the formula, R11 represents a group that can be substituted on the phenol ring or 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, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, acyloxy group, acyl group, aliphatic oxy group, aliphatic thio group, aliphatic sulfonyl group, aromatic oxy group, aromatic thio group, aromatic sulfonyl group, Examples include a sulfamoylamino group, a nitro group, and an imide group.

The number of carbon atoms in R1+ is 0 to 30.

R" is -CONR"R"-NHCOR'co-NHC
OOR” -NH3ChRI5-NHCONR13R
"or -NH3OZR"R", R13 and R
la is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (for example,
Methyl group, ethyl group, methyl group, methoxyethyl group, n
-decyl group, n-dodecyl group, n-hexadecyl group,
trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl group, 2,4-di-tert-amylphenoxypropyl group, 2,4-di-lert-amylphenoxybutyl group, etc.), aromatic group having 6 to 3 carbon atoms groups (e.g. phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group, 2-chloro-5-dodecyloxycarbonylphenyl group, etc.), heterocyclic groups having 2 to 30 carbon atoms (e.g. 2 -pyridyl group, 4
-pyridyl group, 2-)yl group, 2-thienyl group, etc.), R
Is is an aliphatic group having 1 to 30 carbon atoms (for example, a 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.), a heterocyclic group (e.g., 4-pyridyl group, quinolyl group, 2-furyl group, etc.). , piperidine ring, pyrrolidine ring, etc.), p゛ is 0-3, q' is 0-2, "
゛ and S゛ each represent an integer from 0 to 4.

X represents an oxygen atom, a sulfur atom or RI 6 N, and RI and i represent a hydrogen atom or a monovalent group.

When RI' represents a monovalent group, examples of RI6 include aliphatic groups having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, butyl group, methoxyethyl group, benzyl group, etc.) and 6 to 30 carbon atoms;
30 aromatic groups (e.g., phenyl group, tolyl group, etc.),
Heterocyclic groups having 2 to 30 carbon atoms (e.g., 2-pyri, zyl, 2-pyrimidyl, etc.), carbonamide groups having 1 to 30 carbon atoms (e.g., formamide, acetamido, N
-methylacetamide group, benzamide group, etc.), sulfonamide group having 1 to 30 carbon atoms (e.g. methanesulfonamide group, toluenesulfonamide group, 4-chlorobenzenesulfonamide group, etc.), imide group having 4 to 3 o carbon atoms ( For example, succinimide group, etc.), OR”-3
R+t-COR"-CONR"R"-COCO
R"-〇〇〇〇NR"R"-COOR'Drop-COC
OOR' ”S O2R”-S OtOR”
-S OxN R17R” and N RI't RI l
can be mentioned. R1 here? and R11 may be the same or different, and each represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (for example, a methyl group, an ethyl group,
butyl group, dodecyl group, methoxyethyl group, trifluoromethyl group, hepfluorobrovir group, etc.), carbon number 6
~3o aromatic groups (e.g. phenyl, tolyl, 4-
chlorophenyl group, pentafluorophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group, etc.) or a complex I having 2 to 30 carbon atoms! R17 represents one group (e.g. 4-pyridyl group, 3-pyridyl group, 2-furyl group, etc.)
and R'' are bonded to each other to form a heterocyclic ring (e.g. morpholino group,
pyrrolidino group, etc.).

R1? Examples include the substituents shown in R17 and R11 excluding hydrogen atoms.

Zl represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Examples of groups that can be separated include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, atoms, etc.), carbon number 1~
30 aliphatic oxy groups (e.g., methoxy group, ethoxy group, 2-hydroxyethoxy group, carboxymethyloxy group, 3-carboxypropyloxy group, 2-methoxyethoxycarbamoylmethyloxy group, 2-methanesulfonylethoxy group, -carboxymethylthioethoxy group, triazolylmethyloxy group, etc.), carbon number 6-30
aromatic oxy group (e.g., phenoxy group, 4-hydroxyphenoxy group, 2-acetamidophenoxy L2
, 4-dibenzenesulfonamidophenoxy group, 4-phenylazophenoxy group, etc.), C2-C30 heterocyclic oxy group (e.g., 4-pyridyloxy group, l-phenyl-5-tetrazolyloxy group, etc.) ), aliphatic thio group having 1 to 30 carbon atoms (e.g., dodecylthio group, etc.), 6 carbon atoms
~30 aromatic thio groups (e.g., 4-dodecylphenylthio group, etc.), heterocyclic thio groups having 2 to 30 carbon atoms (()1, e.g., 4-pyridylthio group, l-phenyltetrazole-5
-ylthio group, etc.), acyloxy group having 2 to 30 carbon atoms (
(e.g., acetoxy group, benzoyloxy group, lauroyloxy group, etc.), carbon amide group having 1 to 30 carbon atoms (e.g., dichloroacetylamide group, trifluoroacetamide group, heptafluorobutanamide group, pentafluorobenzamide group, etc.), carbon A sulfonamide group having 1 to 30 carbon atoms (for example, a methanesulfonamide group, a toluene sulfonamide group, etc.), an aromatic azo group having 6 to 30 carbon atoms (
For example, phenylazo group, 4-chlorophenylazo group,
4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, etc.), aliphatic oxycarbonyloxy group having tti to 30 carbon atoms (e.g., ethoxycarbonyloxy group, dodecyloxycarbonyloxy group, etc.), carbon number 6
-30 aromatic oxycarbonyloxy groups (e.g. phenoxycarbonyloxy groups, etc.), carbon atoms 1-30 carbamoyloxy groups (e.g. methylcarbamoyloxy groups, dodecylcarbamoyloxy groups, phenylcarpathyloxy groups, etc.), carbon Examples include a heterocyclic group having a number of 1 to 30 and having a nitrogen atom connected to the active position of the coupler (for example, a succinimide group, a phthalimide group, a hydantoinyl group, a pyrazolyl group, a 2-benzotriazolyl group, etc.). can.

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, trienesulfonamide group, etc.).

R1! Preferred examples include carbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, decyloxypropyl group, dodecyloxypropyl group, 2,4-di Examples include tart-amylphenoxyprobyl group, 2,4-di-tert-amylphenoxybutyl group, and the like.

Preferred as X is R”NC, and further RI
& is preferably -COR" (e.g. formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl group, p-chlorobenzoyl group, etc.), -COOR" (e.g. methoxycarbonyl group, ethoxycarbonyl group,
butoxycarbonyl group, dodecyloxycarbonyl group,
(methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.), -3O,R" (e.g., methanesulfonyl group, ethanesulfonyl group, methanesulfonyl group, hexadecanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, p-chlorobenzenesulfonyl group, etc.)
, -CONR"R1" (N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbamoyl group, 3. 4-dichlorophenylcarbamoyl group, 4-methanesulfonylphenylcarbamoyl group, etc.), 5OzNR
It is a group represented by "R" (for example, N, N-'; J-tylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-dipropylsulfamoyl group, etc.). R1
More particularly preferred among 6 are -COR''-
COOR" and -8OtR".

2+ Particularly preferred groups include hydrogen atom, halogen atom,
They are an aliphatic oxy group, an aromatic oxy group, a heterocyclic thio group, and an aromatic azo group.

Couplers represented by general formulas (IV), (V), and (Vl) are two molecules that are bonded to each other via a divalent or more polyvalent linking group in the substituents R'', RI!, X, or 2+. In this case, the number of carbon atoms shown in each substituent is not limited to this.

The eight magenta color-forming couplers include the general formula %) and the remaining coupler 1 (Ar, z!) represented by [■].
, Rte, , Rsx, the general formula (
III).

General formula [■] -Fun2 (IX) General formula In the general formula, Ar represents a well-known type of substituent at the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a zm alkyl group (e.g., a fluorocarbon Haloalkyl like alkyl,
cyanoalkyl, benzylalkyl, etc.), aryl group or substituted aryl group [Substituents 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 group (e.g., methoxycarbonyl group, etc.), acylamino group (e.g., acetylamino group), carbamoyl group, alkylcarbamoyl group (e.g., methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl group (
(e.g. dimethylcarbamoyl), carbamoyl (e.g. phenylcarbamoyl), alkylsulfonyl (e.g. methylsulfonyl), sulfonyl! (e.g. phenylsulfonyl group), alkylsulfonamide group (e.g. methanesulfonamide group), irisulfonamide group (e.g. dinylsulfonamide group), sulfamoyl group, alkylsulfamoyl group (e.g. ethylsulfamoyl group). group), dialkylsulfamoyl group (e.g. dimethylsulfamoyl group), alkylthio group (e.g. methylthio group, arylthio group (
For example, the substituents include a cyano group, a nitro group, and a halogen atom (1; for example, fluorine, chlorine, bromine, etc.), and when two or more of these substituents are present, they may be the same or different.

Particularly preferred examples of IA and I include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group. ], heterocyclic groups (e.g. triazole,
thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole, etc.).

R20 is unsubstituted or substituted! Represents a negative anilino group, acylamino group (e.g. alkylcarbonamide group, phenylcarbonamide group, alkoxycarbonamide group, phenyloxycarbonamide group), ureido group (e.g. alkylureido group, phenylureido group), and as a substituent for these is a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), a straight chain or branched alkyl group (e.g. methyl group, t-butyl group, octyl group, tetradecyl group, etc.), an alkoxy group (e.g. methoxy group) , ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group), acylamino group (e.g., acetamido group, benzamide group, butanamide group, octanamide group, tetradecaneamide group, α-(2゜-diter
L-amylphenoxy)acetamide group, α-2,4-
tert-amylphenoxy)butyramide group,
α-(3-pentadecylphenoxy)hexanamide group, α-(4-hydroxy-5-Lert-butylphenoxy)tetradecanamide group, 2-oxo-pyrrolidin-1-yl group, 2-oxo-5-tetradecyl pyrrolidin-1-yl group, N-methyl-tetradecanamide group), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, ethylsulfonamide group, p-)luenesulfonamide group, octanesulfonamide group! -1p-dodecylbenzenesulfonamide group, N-methyl-tetradecanesulfonamide group, etc.),
Sulfamoyl group (e.g., sulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group,
N, N-dimethylsulfamoyl group, NN-dimethylsulfamoyl group, N-hexadecylsulfamoyl group,
N-(3-(dodecyloxy)-propyl]sulfamoyl M, N-(4-(2,4-diLert-amylphenoxy)butylcarbamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc.), Carbamoyl group (
For example, N-methylcarbamoyl group, N-butylcarbamoyl L N-octadecylcarbamoyl group, N-(4-
(2,4-di-tert-amylphenoxy)butylcarbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc.), diacylamino group (N-succinimide group, N-phthalimide group, 2,5-dioxo-1 -oxazolidini)t,&,3-dodecyl-2,5-'; ox/-1=hydantoynyl group, 3-(N-acetyl-N
-dodecylamine) succinimide group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, tetradecyloxysulfonyl group, benzyloxycarbonyl group, etc.), alkoxysulfonyl Z (fA, e.g., methoxysulfonyl group, butoxysulfonyl group, octyloxy sulfonyl group, tetradecyloxysulfonyl group), aryloxysulfonyl group (e.g. phenoxysulfonyl group, p-methylfuninoxysulfonyl group,
24-';-tert-amylfuninoxysulfonyl group, etc.), alkanesulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, octanesulfonyl group,
2-ethylhexylsulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl a (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-di-tert-amylphenoxy)ethylthio group, etc.), arylthio group (e.g., phenylthio group, p-)lylthio group, etc.), alkyloxycarbonylamino group (e.g., methoxycarbonyl amino group, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), alkylureido group (e.g., N-methylureido group, N,N-dimethylureido group, N-methyl-N- dodecylureido group, N-hexadecylureido group, N,N-dioctadecylureido group), acyl group (e.g., acetyl group, benzoyl group,
(octadecanoyl group, p-dodecanamidobenzoyl group, etc.), nitro group, carboxyl group, sulfo group, hydroxy group, or trichloromethyl group.

However, among the above i1r and substituents, those defined as alkyl groups have 1 to 36 carbon atoms, and those defined as aryl groups have 6 to 38 carbon atoms.

Rzl, Ro, Ras, R", His, Ras, R2'
rR1, R1, R3@, R3+ and R”L! each h
In addition to water HH atoms and hydroxyl groups, unsubstituted or substituted alkyl groups (preferably those with 1 to 20 carbon atoms)
For example, methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, etc.), aryl group (preferably one with 6 to 20 carbon atoms), 0 examples/L, c, fynyl group, 4 (-]゛Teterphenyl group, 2,4-di [
-amylphenyl group, 4-methoxyphenyl group, etc.), alkoxy group (preferably one having 1 to 20 carbon atoms, such as methoxy group, ethoxy group, butoxy group, etc.), oryloxy group (preferably one having 6 carbon atoms) ~20 things, e.g.
phenoxy group, naphthoxy group), heterocyclic group (e.g. 2-furyl group, 2-thienyl group, 2-pyrimidinyl group,
2-benzothiazolyl group, etc.), alkylamino group (preferably one with 1 to 20 carbon atoms, such as methylamino group, diethylamino group, t-butylamino group, etc.), acylamino group (preferably one with 2 to 20 carbon atoms) ,for example,
acetylamino group, propylamide group, benzamide group, etc.), anilino group (e.g. phenylamino group, 2-chloroaniliso group, etc.), alkoxycarbonyl group (preferably one with 2 to 20 carbon atoms), e.g. methoxycarbonyl group, butoxycarbonyl group group, 2-ethylhexyloxycarbonyl group, etc.), alkylcarbonyl group (preferably one with 2 to 20 carbon atoms, e.g., acetyl group, butylcarbonyl group, cyclohexylcarbonyl group, etc.), arylcarbonyl group (e.g., preferably C7-2o, benzoyl group, 4-t-butylbenzoyl group, etc.)
, an alkylthio group (preferably one having 1 to 20 carbon atoms)
For example, methylthio group, octylthio group, 2-phenoxyethylthio group), arylthio group (preferably one with 6 to 20 carbon atoms, e.g. phenylthio group, 2-butoxy-3-t-octylphenylthio group, etc.), carbamoyl A group (preferably one having 1 to 20 carbon atoms).

For example, N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-methyl-N-butylcarbamoyl group, etc.), sulfamoyl group (preferably one having up to 20 carbon atoms), N, N-
diethylsulfamoyl group, N,N-dipropylsulfamoyl group, etc.) or sulfonamide group (preferably one having 1 to 20 carbon atoms, such as methanesulfonamide group,
(benzenesulfonamide group, p-toluenesulfonamide group, etc.).

Z! represents a hydrogen atom or a group that can be separated by a camping reaction with an oxidized product of an aromatic primary amine developing herbal drug. Examples of groups that can be separated include a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an oxygen atom, Coupling-off group to be linked (e.g. acetoxy group, propanoyloxy group, benzoyloxy group, ethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenokyloxy group, 4-titanesulfone Amidophenoxy group, α-naphthoxy group, 4-cyanoxyl group, 4-methanesulfonamide-phenoxy group, α-naphthoxy group, 3-pencudecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-ethoxyethoxy group, 5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), campling leaving groups linked via a nitrogen atom (e.g. 491G
Those described in No. M Sho 57-189538, specifically benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2
, 3,4,5.6-pentafluorobenzamide group, octanesulfonamide group, p-dianophenylureido group, N,N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2 ,4-dioxo-3
-oxazolidinyl group, l-benzyl-5-ethoxy-
3-hydantoinyl group, 2-oxo-1゜2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group,
3.5-diethyl-1,2゜4-triazol-1-yl group, 5- or 6-bromobenzotriazole-l-
yl group, 5-methyl-1,2,3,4-triazole-
1-yl group, benzimidazolyl group, etc.), coupling-off groups linked via a sulfur atom (e.g., phenylthio 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 group, 2-benzothiazozolyl group, etc.). Preferably, the detachable group is a halogen atom, a phenoxy group, or a coupling-off group connected via a nitrogen atom, and particularly preferably a halogen atom, a phenoxy group, a pyrazolyl group, an imidazolyl group, or a triazolyl group.

Yellow color-forming coupler residues include those of the acylacetanilide type, especially the piparoylacetanilide type (XR
/), benzoylacetanilide type [X■], [XVI
) is preferred.

In the formula, R33, R34, R35 and R are each a hydrogen atom or a well-known substituent of a yellow color-forming coupler residue, such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, an aliphatic amide. group, alkylsulfamoyl group,
Alkylsulfona is a do group, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group, arylsulfamoyl group, arylsulfonamide group, arylureido group, sulfo group , nitro group, cyano group, thiocyano group, etc., and these substituents may be the same or different.

The free bond in the formula is linked to the polymer tin via a D or E or F linking group.

Z3 is represented by a hydrogen atom or the following general formula CXVII), [W, ○■], or (XX).

() R37 [X■] R37 represents an optionally substituted aryl group or heterocyclic group.

Represents the nonmetallic atoms required to form .

Among the general formulas (:XX), preferred are CXX
I) to ■α■].

R and R are hydrogen atoms, halogen atoms, force/l/:i
represents an acid ester group, an amine group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocyclic group, and these groups may be the same or different.

0 YN The group, aralkyl group or acyl group, W2 represents an oxygen or sulfur atom.

G is a group that can be separated by a coupling reaction with an oxidized color developing agent, and can be represented by the following general formulas (XXIV) and [XXV].

General formula [◇■] General formula (XXV) *
represents the bonding position to the active position of the coupler, and Jl is
represents an oxygen atom or a sulfur atom, J2 represents a nonmetallic atom group necessary to form an aryl ring or a heterocycle, and J3 is necessary to form a Y-membered or t-membered heterocycle together with a nitrogen atom. represents a group of nonmetallic atoms. These rings may further be fused with an aryl ring or a heterocycle.

G represented by the general formula CXXIV) may be a divalent group derived from an aryloxy group, an oxacylyloxy group, a chroman-lyoxy group, a tetrazolyloxy group, an arylthio group, etc. ] Examples of G represented by include urazole group, hydantoin group, tetrazolone group, triazole group, diazole group, succinimide group, saccharin group, pyridone group, pyridazone group, oxazolidinedione group, thiosilydinedione group, etc. Preferably, it is a divalent group derived from an aryoloxy group, a urazole group, a hydantoin group, a tetrazolone group, or a pyrazole group.

The group G represented by the general formulas [XXIV) and [: XXV:] can further have a substituent, and examples of the substituent include an alkyl group, an aral group, an aralkylene group, a halogen atom, an alkoxy group, Hydroxy group, nitro group,
Examples include an amino group, a carboxylic acid ester group, a carboxylic acid group, and a sulfonic acid group.

Representative examples of monomeric couplers that provide repeating units (coupler units) represented by general formula [1] are shown below, but the invention is not limited thereto.

MC-I CH.

MC-4 CH.

CH1 mouth C MC-5 ~IC-6 CH3 L-C υH MC-7 MC-8 CH.

C-9 C) It”’CO ” C-10 C-15 CH2-CH Hs HI-C NIICOCJt 0C11 C-12 C-14 C-18 C-19 υ11 l MC-21 MC22CH3 C11, Tomi C MC-28 MC-24 Hs MC-25 MC-29 C1l.

MC-31 MC-32 MC-38 MC-39 H Hs MC-35 MC-37 MC-40 MC-41 0OCHs COOCI(-C8z AC-42 MC-44 MC-≠g MC-Geta MC-t.

MC-≠yo MC-Hirot MC-≠7 MC-j / MC-12 MC-3,3 M　C-zgu MC-5r MC-rt MC-A.

M　C-j　7 CC-5 r　C-zri MC-63 MC-4≠ MC-A! AIC-A B MC-67 MC-7r MC-7j C-7j≠ MC-, <7 MC-70 C-7O/ MC-7j MC-77 MC-7,1' MC-72 Mc-t.

MC-♂GlNl-1SilJ substitute MU to 52 sho (JU=Uti2M
C-J'/MC-r,? MC-r 7 MC-rr MC-J'riN1((, ○(1-1=(fi2) Next, general formula (II) will be described in detail.

General Formula (n) In the formula, R represents a hydrogen atom, a chlorine atom, or an alkyl group (eg, methyl group, ethyl group, butyl group, n-hexane group), and among these, a hydrogen atom or a methyl group is particularly preferred.

R' represents a hydrogen atom or an alkyl group (preferably one having 7 to 10 carbon atoms, such as a methyl group or a decyl group).

IQ is either -Co□--CON- or an arylene group having 70 carbon atoms. Q includes the following groups.

Among these, -CO2C0NH-L is a divalent group containing at least one -Co2- -CON- bond and having 3 to 75 carbon atoms, or -0 - -N- -Co - -so - -5o2--5
Any divalent group containing at least one o3- bond and having 1 to 72 carbon atoms. (However, R1 represents the same as described above.) L includes the following groups.

-CH2Co□CH2- -CH2CO2CH2CH2 -CH2CH2CO2CH2CH2 +CH2+CO2CH2CH2 +CH2+-CO2CH2CH2 -CH2NHCOCH2 -C) (NHCO2H2CH2 +CH2+NHCOCH2CH2 +CH2+NH COCH2CH2 +CH2+NHCOCH2CH2 -CH20CH2 -CHCH0CH2CH2CH2- -COCH2CH2 -CHCOCH2CH2 -3OCR2CH2- -CH25OCH2CH2 -8O2CH2CH2 -8O2CH2CH2SO□CH2CH2- 5O3C
H2CH2CH2 -803CH2CO2CH2CH12 -8O3CH2CH2CO2CH2CH2-3o2NH
C) 12C) 12CO□CH2C) 12--NHCON
HC)12CH2 -CH2NHCONHCH2CH2 -NHCO2CH2CH2 -CH2NHCO□CH2CH2 L is an object of the present invention, for example, to provide a diffusion-resistant photographic polymer, or to make a photographic additive having a nucleophilic group diffusion-resistant, The material is arbitrarily selected depending on whether it is used as a hardening agent or the like.

Representative examples of unsaturated monomers that provide the repeating unit represented by the general formula (n) of the present invention are shown below, but the present invention is not limited thereto.

[-7 CH=CH Next, in the present invention, it is better to introduce a non-color-forming ethylene-like monomer that does not couple with the oxidized product of the aromatic-grade amine developer as a copolymerization monomer to improve solubility and compatibility with the hardening agent. Very preferred in terms of reactivity. For example, acrylic acid, acrylic ester, methacrylic acid, methacrylic esters, crotonic acid, crotonic esters, vinyl ester, maleic acid, maleic diester, fumaric acid, fumaric diester, itaconic acid, itaconic diester, acrylamide. , methacrylamides, vinyl ethers, styrenes, etc.

These acids may be salts of alkali metals (eg, Na, etc.) or ammonium ions.

More specific examples of these monomers include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 3-acryloylpropanesulfonic acid, acetoacetoxyethyl acrylate, and acetoxy acrylate. Examples include ethyl acrylate, phenyl acrylate, λ-methoxy acrylate, λ-ethoxy acrylate, 2-(j-methoxyethoxy)ethyl acrylate, and the like. Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t
ert-butyl methacrylate, cyclohexyl methacrylate, co-hydroxyethyl methacrylate,! −
Examples include ethoxyethyl methacrylate. Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, vinyl benzoate, and the like. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include diethyl itaconate, dimethyl itaconate, dibutyl itaconate, and the like. Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, isopropylacrylamide, n-butylacrylamide, hydroxymethylacrylamide, diacetone acrylamide, acryloylmorpholine, acrylide-methylpropanesulfonic acid, and the like. Examples of methacrylamide include methyl methacrylamide, ether methacrylamide, n-butyl methacrylamide, tert-
Examples include butylmethacrylamide, -monomethoxymethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, and the like.

Examples of the vinyl ethers include methyl vinyl ether, phthyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and dimethylaminoethyl vinyl ether. Styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, etherstyrene, inpropylstyrene, methylstyrene, chloromethylstyrene, methoxystyrene,
Examples include butoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, vinylbenzoic acid methyl ester, comethylsterene, styrene sulfonic acid, styrene sulfinic acid, and hinyl benzoic acid.

Examples of other monomers include allyl compounds (e.g. rh
vinyl ketones (eg, methyl vinyl ketone, etc.), vinyl heterocyclic compounds (eg, vinyl pyridine), glycidyl esters (eg, glycidyl acrylate, etc.), unsaturated nitriles (eg, acrylonitrile, etc.).

Among these monomers, those with high hydrophilicity are particularly preferred. Two or more of these monomers may be used in combination.

Examples of combinations when two or more are used together include potassium styrene sulfinate and sodium acrylamide-λ-methylpropanesulfonate, acetoacetoxyethyl methacrylate and sorta 3-acryloylpropanesulfonic acid, and acrylamide-λ-methylpropanesulfone. Examples include sodium acid, sodium acrylate, sodium 3-acryloylpropanesulfonate, butyl acrylate, and sodium styrenesulfonate.

Next, specific examples of the polymer cassillator used in the present invention are shown below, but the invention is not limited thereto.

The numerical values in the structural formulas shown below represent molar ratios.

Y-/ Y-, 2 entering 1-/ Hennie-2 (JUl-13 -J M-/J' +Wl-13 C-76 shi0~)iUH(,,:)1-(,:l(2 '\♂ (,'02(:H2CH2SO3Na) In the polymer coupler of the present invention, the general formula (I), (
It) Molar ratio of coupler part (A) and hardener part (B) in K, coated Ag1t, coated gelatin amount, pH of coated emulsion
1. It can be arbitrarily changed depending on the viscosity, etc. Preferably (A); tori! %, (B);j~! It is 0%.

The amount of the coupler added per gelate can also be varied at will. Normally, the hardener part (B) is 10 oy of dry gelatin! A range from X10'' equivalents to j×/θ equivalents is used.

When a non-color-forming copolymerized monomer is used as the third component,
The ratio can be varied depending on the concentration of the coupler added and the method of adding the coupler. Preferably it is j~rijwt%.

In the case of an emulsion layer, the amount of the polymer coupler of the present invention added is such that the molar ratio of coated silver amount (mol) to coupler 8(A) is l-200, preferably j~100. It is advantageous in terms of photographic performance.

What is the molecular weight of the polymer Cp of the present invention? ×70~l×707
is preferred. If the molecular weight is too small, the polymer will not move easily, and if the molecular weight is too large, it may cause problems in coating. More preferably /×10′~, 2×10
It is 6.

The synthesis of the water-soluble polymer coupler of the present invention includes a polymerization initiator,
Tokukai Sho is the best polymerization solvent! r-/202!2, Tokukai Sho!
1/≠jri≠gu, JP-A-5G-2//7j51f? 5
Kaishojg-2211332, Tokukaishojter≠Kojda3,
Tokukai Shojter/7/966, Tokukai Shojtar 221.23
2. JP-A-60-36732 and JP-A-60-36732 and JP-A-60-36732 and JP-A-60-36732
It is carried out using the compound described in sr.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc.
o It is possible to go up to 0c or more, but usually 30'C-/, 0
Polymerizes in the range of 0'C.

Synthesis example/Synthesis of water-soluble polymer coupler Y-// Coupler monomer MC-vs 13y in a 3oOml Mitsuro flask
Hardener %/7-1-//jiE, N-acryloyl-ε-amino-n-caproic acid sodium salt/λ and DMF/AO ml were mixed, heated to 00C under a nitrogen stream, and dimethyl azobisisobutyrate o, l/
One liter of gold was added to the DMF solution of ly, and polymerization was started. 3
After polymerization for a period of time, the mixture was cooled and reprecipitated with 10,100 O acetone. After filtration and drying 23. /7 polymer coupler Y
−// was obtained. This polymer was determined by alkaline titration.
g, 0 wt% of coupler monomer units were contained.

Synthesis Example 2 Synthesis of Water-Soluble Polymer Coupler Y-/- Coupler monomers MC-19/7F, hard, l-agent monomers II-//y in a 3 ooml three-tube flask.

200 ml of 61% DMF of sodium acrylate was mixed and heated to RO 0C under a nitrogen stream, and a solution of dimethyl azobisinbutyrate O, geta, [) MF] was added to initiate polymerization. After 3 hours of polymerization, cool and use Sanko Pure Chemical's dialysis membrane! Dialysis was performed on OFT C-gj for 3 days. 2fi PoIJ by freeze drying? -Coupler Y-
I got 72. This polymer was determined to be A2W1 by alkaline titration.
% coupler monomer units.

Water-soluble in the present invention means that the obtained polymer coupler is 1
．． It means that it is soluble in water at 0 wt% or more, preferably 1
It is preferable for manufacturing purposes that it dissolves in water at QwL% or more.

The polymer coupler of the present invention can be added to a coating solution as an aqueous solution, or can be added to a coating solution using a lower alcohol, THF.
It can also be added after being dissolved in a mixed solvent of water and an organic solvent that is miscible with water, such as acetone or ethyl acetate.

Furthermore, it may be added after being dissolved in an aqueous alkaline solution or an organic solvent rR mixture containing alkaline water, or it may be dispersed in a gelatin solution or a small amount of a surfactant may be added.

In either case, the water-soluble polymer coupler of the present invention does not take the form of oil droplets or latex in the coating solution or coating film, but it is thought that it interacts with the hydrophilic binder and is compatible with it to some extent. It will be done.

Therefore, it is thought that the membrane strength shows superior performance compared to oil-soluble (including latex-like) polymer couplers.

The polymer coupler of the present invention may be used alone as a hardening agent, or may be used as a mixture of two or more types, or may be used in combination with other known hardeners. Known hardening agents that may be used include, for example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopenkundione, bis(2-chloroethyl urea), and 2- Hydroxy-4,6-dichloro-1
, 3,5 triazine, etc. U.S. Patent No. 3.288,
No. 775, No. 2,732,303, British Patent No. 974
, 723, 1,167.207, etc., compounds containing reactive halogens, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-13,5-) riazine, and others. U.S. Patent No. 3,
No. 635.718, No. 3,232,763, compounds with reactive olefins described in British Patent No. 994,869, N-hydroxydimethylphthalimide, and other U.S. Patent No. 2.732,316 No. 2,
N-methylol compounds described in US Pat. No. 586,168 etc., isocyanates described in US Pat. No. 3.103.437 etc., US Pat. No. 3.017,28
0, aziridine compounds described in U.S. Patent No. 2,983,611, etc., acid derivatives described in U.S. Pat.
Examples include epoxy compounds described in US Pat. No. 3,091,537 and halogencarboxaldehydes such as mucochloric acid. Alternatively, inorganic compound hardeners include chrome light pan, zirconium sulfate, and the like. In addition, compounds in the form of precursors instead of the above compounds, such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic ditroalcohols, mesyloxyethylsulfonyl compounds, chloroethyl It may also be used in combination with sulfonyl compounds.

When the polymer coupler of the present invention is used in combination with another film agent, the proportion of the polymer coupler of the present invention to be used can be arbitrarily selected depending on the purpose and effect.

A compound that accelerates the hardening of gelatin can also be used together with the polymer coupler of the present invention.

For example, a polymer containing a sulfinic acid group described in JP-A-56-4141 is used as a hardening agent in combination with the polymer coupler of the present invention and a vinyl sulfone hardener.

In the manufacturing process, the gelatin that can be used with the polymer coupler of the present invention undergoes so-called alkali-treated (lime-treated) gelatin that is immersed in an alkaline bath, acid-treated gelatin that is immersed in a bath, and both treatments before gelatin extraction. This hardening agent can be used for double-soaked gelatin or enzyme-treated gelatin.Furthermore, this hardening agent can be used to heat these gelatins in a water bath or treat them with proteolytic enzymes to partially hydrolyze low-molecular-weight gelatin. It can be used.

Gelatin is advantageously used as the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the photosensitive material of the present invention, but other synthetic polymers can also be used as the binder.

When adding the polymer coupler of the present invention to a coating solution for a photosensitive emulsion layer or a non-photosensitive layer, if the polymer coupler of the present invention is left for a long time after being added, a crosslinking reaction will occur between the gelatin and the polymer coupler of the present invention, resulting in severe thickening of the coating solution. Therefore, it may be difficult to ensure good quality coating properties.

Therefore, when the polymer coupler of the present invention is added to a coating solution, it is preferably added within at least 60 minutes, preferably within 30 minutes, and particularly preferably immediately before coating.

To some extent, it is preferable for some polymer couplers to be reacted with Zehirotin before being applied.

Furthermore, it is preferable to apply the polymer coupler of the present invention as a solution in a state in which it is dissolved in a solvent, since the physical properties of the coating solution will not change. It becomes diffused, hardened, and immobilized.

In the photographic emulsion layer of the photographic window optical material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

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 may be 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 with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a thinly dispersed emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), Ih17643 (
December 1978), pp. 22-23, “1. Emulsion production (
Emulsion preparationLion and
18716 (November 1979), p. 64B, “Physics and Chemistry of Photography” by Glafkides, published by Paul Montell (P, Glafkides)
, Chemic eL Physique Photo
graphique Paul Montel, 19
67), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.

F. Duffin, Photographic E.
Mulsion Chemistry (Focal P
(Ress, 1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L.

Zelikian et al+ Making an
d Coating Photographicεmu
lsion, Focal Press+ 1964)
It can be prepared using the method described in et al.

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

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Cutoff, Photographic Sci.
ence and Engineering), No. 14
Vol. 248-257 (1970) 1 U.S. Patent No. 4,
No. 434,226, No. 4,414,310, No. 4,4
No. 33,048, No. 4,439,520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by eviaxial bonding. 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 usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure II &
117643 and the same patient 18716,
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the two Research Disclosures mentioned above, and the relevant notes are shown in the table below.

Additive type 1 Chemical IVI confusing agent 2 Sensitivity enhancer 4 Increase! 8 Anti-stain agent Dye image stabilizer Hardener Binder Plasticizer, lubricant RD17643 R1) 18716 Page 23 Page 648 Right column Same as above Page 24 Page 25 Right column Page 650 Left to right column Page 25 Page 26 Page 651 Left side 26 Page Same as above, page 27, page 650, right 1M Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
RD) Minami 17643, described in the patent described in ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, 4,022,620, 4.3
No. 26,024, No. 4,401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1.425,020,
No. 1,476.760, etc. are preferred.

As the Mazenk coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent No. 4,31
No. 0.619, No. 4,351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3. 725. No. 067, Research Disclosure & 24220 (June 1984), JP-A-60
-33552, Research Disclosure 1h2
4230 (June 1984), JP-A-60-43659
No. 4,500.630, U.S. Patent No. 4.540
Particularly preferred are those described in , No. 654, etc.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4. 296. 200, No. 2.369,
No. 929, No. 2,801゜171, No. 2,772,
No. 162, No. 2゜895.826, No. 3,772
．． No. 002, No. 3.758,308, No. 4,33
4.011, West German Patent Application No. 4,327,173, West German Patent Application No. 3,329,729, European Patent No. 121365A
No. 3,446,622, U.S. Patent No. 4.333
, No. 999, No. 4. 451. No. 559, No. 4,
427,767, European Patent Application No. 161.626A, etc. are preferred.

Colored couplers to correct unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4. No. 163゜670, Tokuko Showa 5
No. 7-39413, U.S. Patent No. 4,004,929,
Same No. 4. 138. No. 258, British Patent No. 1,146
, No. 368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include US Patent 'fJ4,366.237 and British Patent No. 2.1.
25,570, European Patent No. 96,570 and West German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.367.282, British Patent No. 2,102
, No. 173, etc.

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD17643.
Patents No. 57-151944, No. 57-154234, No. 60-184248 described in paragraphs 1 to 1,
Preferred are those described in U.S. 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. 4,130,427, U.S. Pat. , a multi-equivalent coupler described in JP-A No. 4,310,618, etc., a DIR redox compound releasing coupler described in JP-A-60-185950, etc., and a dye that recovers color after separation as described in European Patent No. 173.302A. Examples include couplers that emit light.

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

The steps, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat. etc. are listed.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of 17643 and 6 of Donan 18716
It is described from the right column on page 47 to the left column on page 648.

The color photographic material according to the present invention is described in the above-mentioned RD, No. 17643, pages 28-29, and No. 18716, No. 6.
The development process can be carried out by the usual method described between the left column of 51 and 1 of the right column.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization step after desilvering treatment such as fixing or bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (e.g., depending on the materials used, such as couplers), the application, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as countercurrent flow, parallel flow, etc., and various other factors. It can be set over a wide range depending on the conditions. this house,
The relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion.
Picture and Television Engineers (J
our own or the 5ocieLy of
MoLion Picture and Te1ev
ision Engineers>Volume 64, P, 24
8-253 (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 greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively as a solution to such problems. can. In addition, chlorine-based disinfectants such as isothiazolone 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 the disinfectants described in Sanitation Techniques Complete Volume [Microbial Sterilization, Disinfection, and Anti-Mildew Techniques], ``Encyclopedia of Antibacterial and Antifungal Agents'' edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Finally, at 15-45°C for 20 seconds-10 minutes, preferably 2
A range of 30 seconds to 5 minutes at 5-40°C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-1483
No. 4, No. 59-184343, No. 60-220345,
No. 60-238832, No. 60-239784, 60-
No. 239749, No. 61-4054, No. 61-11874
All the known methods described in No. 9 etc. can be used, especially for 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, and bismuth compounds. A stabilizing bath containing an ammonium compound or the like is preferably used.

Further, following the water washing treatment, a further stabilization treatment may be carried out; an example of this is a stabilizing bath containing formalin and a surfactant, which is used as the 11 Hiiragi bath of the 1st shadow color photosensitive material. (Example) The present invention will be explained below in detail with reference to Examples, but the present invention is not limited thereto.

EXAMPLE Sample 10 was prepared using a multilayer color pagination material υ having each layer having the composition shown below on a cellulose triacetate film coated with an undercoat υ.

(Composition of photosensitive layer) 14th (emulsion layer) Monodisperse (coefficient of variation HI) silver iodobromide emulsion (silver iodide μmole arc, average grain size o, Ip) 0.197 m2 gelatin i, o 7 m2 emulsion 21 (...CliiF).

Hydrochloride ether cellulose θ r ? ／ 、、、
2 Third layer (containing coupler 1 liter) Same silver iodobromide emulsion as the first layer o, r 7m2 coupler A-/ /, o? /m2 gelatin
/ , 097Fn2 jth layer (protective layer) Gelatin o, rt7m2 Polymethyl acrylate particles o, z? /m2 Hardener )(-7
0 protection/m2 Preparation of sample 10- to //Z Coupler A of ffcJ layer of sample 10/ f p
Sample 10/ was prepared in the same manner as sample 10/, except that the amount of coupler residue was calculated to be added in equimolar amounts to the coupler shown in sample 10/.

The water-soluble polymer coupler used in the example was 3wt%
It was made into an aqueous solution and added to the coating solution 20 minutes before coating.

0=O Samples 10/~//, 1- were partially peeled off from the peeling layer, and developed at 3t''C according to the following processing steps.

Thereafter, the ratio of the yellow density D without peeling to the yellow density D after peeling was taken as a measure of the diffusion of the acetylated coupler into other layers.

The distance results are shown in Table/. It can be seen that all the couplers of the present invention have little diffusion to other layers.

Color development 3 minutes/! Floating white for 1 minute 30 seconds Water condition 2 minutes 10 seconds Set 4 minutes, 20 seconds Washing 3 minutes/! Stable for seconds
7 minutes 03 seconds The number of treatment sets @ used in each step was as follows.

Clar developer diethylene triamine pentaceous acid 5/, 0? /
-Hydroxyethylidene/-7-diphosphonic acid 1.0? Sodium sulfite μ, O potassium carbonate
Jo, potassium bromide
/, ≠ dipotassium iodide /,
31h9 hydroxylamine sulfate 2.4t2
Goo (N-ethyl-N-β-hydroxyethelamino) Add 1λ-methylaniline sulfur salt solution and bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid disodium chloride Ammonium nitrate Add water and fix Liquid ethylene 2 F 8 F Disodium acetate Sodium sulfite Ammonium thiosulfate aqueous solution (777%) N! Sodium sulfate! 2/, 01 pH 10,.

100.0? 10.0? ito, oy 10.0? /, 01 pHt.

7.02 μ, O2 / 7, 0rnl Hiroshi, &yl Float with water i, oβHJi Ku stable α〉 Nermarin (37% w/v) j, 0m
g Polyoxyethylene-p-mo//nylphenyl ether (average degree of polymerization io) o, 3t Ethylenediaminetetracarboxylic acid disodium salt o, oty 3-chloro-1-methyl-isothiazoline - 3-70,000
, 03? Add water/l
pH O, O Wash water > Tap water
-Hirooo) was passed through a column containing mixed light at a volume ratio of 72/2, and treated with calcium and magnesium to less than /mg/l. :
/e Todoroki o, o-2y added as a reminder.

lol 厖ψ”! (Sample-〇/~λ/l) Sample P10t was prepared in the same manner as Sample 10/ except that the coupler A-/ in the third layer was replaced with Tatsu 2 as shown in Table 3.

A friend who performs similar treatment evaluations on the obtained samples. Fruit drop - Table 2 shows in Table 3.

Similar to meishidong/, regardless of the type of coupler mother nucleus,
28: It can be seen that the water-soluble polymer coupler of the invention has little diffusion to other layers.

λ0/(Comparative example) Ko 0.2 tt 103 (Invention) -0g 〃 λ OJ //, 2 0 1 // -〇 7 tt, 20! (Comparative example) JOta 〃 2 / O 〃 1// (present invention) j / , 2 '// Ko / 3 +274t 〃 Ko /! 〃Table 2 B-/B-Co-I C-/. 2 C-/woga 3 -t D-co-J N1-/ -s M-/(7 ΔL-l l jin/ri0, JO 0, θ? 0, 0ri o.ol jin6 0,09 O l λ r θ , Jl 0,3 6 o.oJ' o,o? o , o'r 10 0,09 Example 3 On a subbed cellulose triacetate film support,
A sample JO/ was prepared using a multilayer light-sensitive material having each layer having the composition shown below.

(Composition of photosensitive layer) The coating amount is 1 in total for silver halide and colloidal silver in units of 7 m of silver paste, and 2 for couplers, additives and gelatin! The amounts are expressed in m2 units, and the sensitizing dyes are expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver ・・・・・・・・・0
. l Gelatin ・・・・・・・・・
・／． 3E x? vl-ta・
・・・・・・・・・o. otUV-/
......0, OJUV-λ
・・・・・・・・・O. ObuUV-J
Mountain...o. oASolV-
/ ・・・・・・・・・0. /! S
olv-2 ・・・・・・・・・0.
/! S o l v−J −=・−
・-0, 01 2nd layer (intermediate layer) Gelatin UV-/ExC-μ Ext-/olv-t olv-2 3rd layer (low, high-richness emulsion layer) Silver iodobromide emulsion (A g Iμ mol%, Takumi-AgI type, equivalent sphere diameter O0 3 μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particle, diameter/thickness ratio 3.0) ....../, 0 ・・・・・・・・・・Q , 03 −・・・・・・・Q, 02 ・・・・・・・・・0.00≠ ・・・・・・・・・0 , / ・・・・・・・・・0.1 Coated silver amount ・・・・・・・・・/1.2 Silver iodobromide emulsion (AgIJ mol%, uniform-AgI type, equivalent sphere diameter 0°3μ, equivalent sphere diameter Coefficient of variation l 3%, spherical particles, diameter/thickness ratio/, O) Coated silver amount ・・・・・・・・・o, t・・・・・・
・・・・・・／ , θ μX10 ' jXlo 5 ・・・・・・-o , or ・・・・・・・・・-0, 10 ・・・・・・・・・0.03 ・・・・・・...O, / 2 ......-O, Ol Gelatin ExS-/ ......-ExS-2
・・・・・・・・・ ExC-/ ExC-2 ExC-J ExC-μ ExC-j G layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgIJ mol%, core shell ratio /:/ Internal cylinder AgI type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter / %, plate-shaped particle, diameter / thickness ratio!

O) Gelatin/ExS-/ExS-λ ExC-J Coated silver amount ・・・・・・・・・0.7・・・・・・
・・・・・・／ , O ・・・・・・・・・ , 3x10-'・・・・・・・・・
...2.3×10-"°"°゛°°°°・0. // ExC-7 ExC-a SolV-/ So 11° -3 3rd layer (middle layer) Gelatin ・・・・・・・・・01
ICpd-/ ・・・・・・・・・
0. /5olv-i ・・・・・・・・・
・・0. Oj th NI (low sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag I, core-shell ratio near 0, high surface AgI type, equivalent sphere diameter 0.jμ, coefficient of variation of equivalent sphere diameter 7!% , plate-shaped particles, diameter/thickness ratio...0.Oj...0.0jr...0.0!...・・・・・・0.0j Coated silver amount ・・・・・・・・・0.3!Silver iodobromide emulsion (AgIJ mol%, uniform-AgI type, equivalent sphere diameter 0°3μ, equivalent sphere diameter Coefficient of variation 2! (Sorry, spherical particles, diameter/thickness ratio 7.0) Gelatin -≠ 7th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI gmol%, internal cylinder Agl type with core-shell ratio l:3, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 2Q%, Plate-like particles, diameter/thickness ratio 3°, coated silver amount......0.20.../, O J'×10'JXlo'/X10-'... ......?y, 4t ......0.07 ......0.0.2 ......0.03 ......・・・・0.3 ・・・・・・・・・0 .01 Coated silver amount・・・・・・O0 3y, io"-'lX10-'1×10' -...-・・・0./ ・・・・--O, O, 2 ・・・・・・・・・0,03 ・・・・・・・・・0.03 ・・・・・・・・・0,0/ ・・・・・・・・・0.2 ・・・・・・・・・0 + O/ ExS-3・・・・・・・・・ ExS-g ・・・・・・...ExS
−j ・・・・・・・・・−To Ex8−
g E
MaCpd-/ ・・・・・・
...θ, 02Solv-i
・・・・・・・・・0.02 words 7 layers (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (AgIλ mol%
, core-shell ratio, internal height AgI type of 2: /, equivalent sphere diameter /; Oμ, coefficient of variation of equivalent sphere diameter /! %, plate-shaped particles, diameter/thickness ratio 6°O) Coated silver amount ・・・・・・・・・0. Jjt silver iodobromide emulsion (Ag 1.2 mol%, core shell ratio /: / internal height A g type I, equivalent sphere diameter o, t, tμ, coefficient of variation of equivalent sphere diameter 20%, plate-like grain, diameter / Thickness ratio t.

O) Coated silver amount gelatin ExS-j ... ExY-/3 E・・・・・・0.20 ・・・・・・・・・0.3 ・・・・・・・・・ lX10-' ・・・・・・・・・0.//・...
・・・・・・Q, 03 ・・・・・・・・・0. IO ・・・・・・・・・O, O Coulter layer) ・・・・・・・・・0, 0!・・・・・・・・・O,!・・・・・・・・・O3/3 ・・・・・・・・・O, 10 Kure // layer (low S degree IS emulsion layer) Silver iodobromide emulsion (AgI≠, !mol%, Uniform A g I type, solid diameter 0.7μ, coefficient of variation of equivalent sphere diameter 73%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount Silver iodobromide emulsion (AgI/j mol% , uniform AgI type, equivalent sphere diameter 0, jμ, coefficient of variation of sphere diameter 2!%, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount gelatin ExS-Otsu...・ExC-/l ExY-t3 ExY-/j Solv-/ 72nd layer (high sensitivity blue emulsion exposure) ・・・・・・・・・0.3 ・・・・・・・・・o, iz・・・・・・・・・／,t λX/ 0-' ・・・・・・・・・O, Oj ・・・・・・・・・0.07 ・・・・・・・・・l,! ......O, +20 Silver iodobromide emulsion (A2110 mol%, internal chamber AgI type, equivalent sphere diameter /, 0μ, coefficient of variation of equivalent sphere diameter coj%, multi-twinned plate-like grains, Diameter / strain ratio 2.0) Coated silver amount Gelatin ExS-A ExY-/j EXY-/J Solv-/ 13th layer (1st protective layer) Gelatin V-u V-t Solv-i Solv-2 1g1 (Second protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent to sphere...0, !...0, !lX10 -' ・・・・・・・・・O、KO O ・・・・・・・・・0,0/ ・・・・・・・・・0 、 / O ・・・・・・ −・O ,♂ ・・・・・・・・・0 , / ・・・・・・・・・O, / ! ・・・・・・・・・0 , O/ ・・・・・・・・・0. 0/diameter 0.07μ) ・・・・・・・・・01! Gelatin ・・・・・・・・・004
t, t polymethyl methacrylate particle diameter 1. ! μ・・・・・・・・・0.2
H-/・・・・・・・・・o,
4tCpd-j...0 old...
・0. ICpd-μ・・・・・・・・・
...o,! V-2 UV-J In addition to the above components, each layer contains an emulsion stabilizer Cpd-3 (
0.04t? /m2) surfactant Cpd-t,t(o,
ory/m2) as a coating aid.

Compound Cpd-t(o,z?/m2) ~C under the ground plane
pd-t(0,!?/m2)f was added.

UV-G UV-t Bu x/y=7/J (weight ratio) U　V　-t epa-/ ol V-/ tricresyl phosphate olv-2 dibutyl phthalate epa-1 ol -J epa-J epa-II ol ■ -G (t)C5)il, OOH Cpd-t Cpd-1 ExC / ExC-r H ExC C(CH3)5 E x C-J H ExC-Hiroshi ExC-7 H To Ex8! m = , 2j m'=-Jj iol, wt, approx. ao, oo.

E x M-ta ExY-/J ExλI-ta ExY-// To Ex 8-/ko ExY-it H COOC2H5 ExS-/ Ex S-G ExS-r ExS-J Ex　S-3 ExS-A (CH2), 5u3Na (CH2) 4 illusions.

(CH2) 4So3Na H-/xF-i Sample 302-3 Small Preparation In Sample 30/, the high boiling point organic solvent of the 1st/layer and 72nd layer was removed, and instead of the coupler ExY-7z, the It was prepared in the same manner as Sample 30/, except that the amount of coupler residue was dispersed and added to the coupler so that the amount of the coupler residue was equimolar to that of EXY-7l.

Coupler ExY-/A added to samples 302-30≠
, ExY-/7, ExY-/J' are couplers shown below.

All water-soluble polymer couplers were added to the emulsion layer as j w t % aqueous solutions.

The obtained sample JO/~3/l was exposed to green light using a wedge and then subjected to the following development treatment.

The density of the resulting sample was measured and the yellow density of the magenta coloring layer was evaluated, which was used as a measure of coupler diffusion from the blue-sensitive layer to the green-sensitive layer.

OAlso, to measure the strength of the emulsion film, sample 30/~3/6
The Vickers hardness (in this case, a Knoop indenter was used) was measured using a Terasawa microhardness meter (Model MM-2). Regarding Vickers hardness, D.

The Physical Meani by Tabor
ngof engineering and 5
clutchHardness, Br1tish J
our own of Applied Physics
, Volume 7, page 2tO (/ri!6).

The results are shown in Table≠.

When an oil-soluble coupler is used, color mixing due to diffusion into other layers is not observed, but the film has a drawback of low strength.

On the other hand, when a known water-soluble polymer coupler is used, the film strength is increased, but color mixing due to diffusion to other layers is large, so that it cannot be put to practical use.

However, it can be seen that when the coupler of the present invention is used, the diffusion resistance is greatly improved and the film strength is high.

Color development 3 minutes/! Seconds 3g"C Bleach 30 seconds Bleach fixing 7 minutes 30 seconds Rinse 1 minute≠0 seconds Stable ≠θ seconds The processing solution composition used in each step was as follows.

Color developer diethylenetriaminepentavinegar e 1. op/-hydroxyethylidene-/,/-diphosphonic acid λ, oy sodium sulfite ≠, 0 potassium carbonate
30.0y potassium bromide
1. Add potassium iodide hydroquinylamine sulfate q-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate solution Bleach solution> Ammonium bromide ethylenediamine μ Ferric ammonium acetate salt ethylenediamine≠ Acetic acid λ sodium salt Ammonium nitrate Bleach accelerator Ammonia water Add water Bleach-fix solution> 7.3M9 2.7 tags,! ri/,01 pH10,.

100 ta / , 209 io, oy 10.0j) 2.Oy /7. Oml ／　　　l pH4,j ammonium bromide Ethylenediamineμ ferric acetate ammonium salt Ethylenediamine ≠ Conate acetate lium salt ammonium nitrate sodium sulfite Ammonium thiosulfate aqueous solution (7(1)%) ammonia water add water Rinse liquid> Ethylenediamineproacetic acid λna Tori ram ±1 add water with sodium hydroxide Stabilizer Formalin (≠0%) polyquine ethylene-p-mo to, oy ! 0.07 j, 0ri j, Oy /+2.0ri 2 ≠ 0m1 10.0tnl ／　　　l pH7, J Geta / pH Ko .

Oml Tunonylphenyl ether (average degree of polymerization about 10) Add water and prepare EXY-/A Other than this, sample preparation, evaluation, and evaluation were performed in the same manner as in Example 3.

The same effect as that of Example 3 was observed.

Processing process> Color development 3 minutes/! Seconds 3r″C bleaching foot care
1 min oo seconds 〃Water washing 1 minute 4tQ seconds 〃Stable
t, go seconds 〃ku color phenomenon 1st liquid〉 diethylenetriamine 3 vinegar K / ,'? /-Hydroquinethylidene-/,/-diphosphonic acid 2.02 Sodium sulfite, potassium carbonate
30.02 Potassium Bromide
/, 4tf potassium iodide /
, J7n9 hydroxylamine sulfate 2.41
9μ=(N-Ethyl-N-β-hydroxyethylamine)-2-methylaniline sulfate μ, 3. Add water; /EpH 10.o.

Bleach-fix solution> Ethylene diamine µ acetic acid ferrous ammonium salt go, oy etele/diamine chloride acetic acid λ sodium rum salt
10, 0? Whitening accelerator /
J2 Sodium sulfite /2.0? Ammonium thiosulfate aqueous solution, shallow (7 (7%), : zaomt water plus /l ammonia water (2!%) pH 7, f water condition water > tap water iH type strongly acidic cationic father conversion resin (Roam & Haas Amberlite JR-/20B) and OH type strong basic anion exchange resin (Amberlite IRA-
≠oo) was passed through a column containing mixed light at a volume ratio of /:/, treated to reduce both calcium and magnesium to less than 7 μ/l, and then added sodium binomial incyanurate at 0.0.29/l. It was used as

Stabilizing liquid> Formalin (37% w/v) j, 0 Gopolyoxine ethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraferoic acid disodium salt o, o3 Add water
1lpHl,.

Example! on a subbed cellulose triacetate film support.
A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared, and 4 samples were prepared.

7th layer: antihalation layer black colloidal silver 0.2 j f/m
2 Ultraviolet absorber U-/Ultraviolet absorber U-2 Ultraviolet field absorber U-J High boiling, controllable 5olv-j 0.04t? Gelatin layer containing /m2 0, / ta/m2 0, l ta/m2 0.0 / cc/m 2 (dry film thickness! μ) 2nd layer: Intermediate layer compound 7) CpdC, 0:0! f/m2 compound /
-,' 0, 0! 9/m 2 High boiling point page side melt 5go 01~'-1 0,0! cc/m2 gelatin layer (dry film: thickness/μ) 3rd F @: 1st red-sensitive emulsion layer Silver bromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-1 (average grain size 0 , 3μ, AgI content gmol%) Silver amount...0. ! 97m2 Coupler F-/0. j 97m2 coupler F-1 □, 0! t/m2 Compound I
-r,! x 10 ta/m2 High boiling point organic solvent 5olv-7 0,/2 cc/m 2 Gelatin layer (dry film thickness/μ) 4th, r@: 1st, 2nd emulsion, color-prohibited S −／
Silver bromide emulsion fractionally enriched with and S-, 2 (average grain size o, tμ, AgI content 3 mol%) Coupler F-/Coupler F-2 I-r high-base point solvent S Silver amount...O6♂ 7/m2 0, j j 17m 2 0, /u? / m2 / Gelatin layer containing solvent 5olv-/dye D-, 2 O0/CC/m2 0.0.2ri/tn2 (dry film thickness/μ) Strand ≦ layer: first green-sensitive emulsion layer sensitizing dye S-, ? and S-t, t< Containing silver iodobromide emulsion (average grain size 0.3 μm, AgI content gmol%) Silver amount...o,'y 97m2 Turnip 5- F-j O,2017m2 Coupler F- t o, iof/m2 High boiling point growth loss @ taste 5olv-1 Gelatin layer containing 0.26 cc/m2 (dry film thickness/μ) 7th layer Nihoki - green sensitive emulsion Noi increase!S dye S-3 and 3-4t -, containing silver iodobromide emulsion (average grain size o, t μm, AgI content λ.

3 mol%) Silver amount...0.7 Ta/m2 Coupler F-4t o, 10y7m2 Coupler F-t o, 10y/m2 High boiling point organic bath medium 5olv-j 0.0jCC/m2 Dye D-J O, 0! Gelatin layer containing 97 m2 (dry film thickness λ, 3 μ) ♂ layer: intermediate layer compound cpctc O, Oj? /m2 High boiling point organic solvent 5olv-,2 (7,7cc/m2 Gelatin layer containing dye D-u., 0/9/m2 (dry film thickness/μ) 2nd layer: Yellow filter layer Yellow colloid Silver .,/?/m2 Compound CpdCOlo, 297m2 Compound CpdB (same as Example/) 0.0317m2 High boiling point organic solvent Oi 1-10, o<tcc/m2
Gelatin layer containing (dry film thickness/μ) 10th layer: First sensitizing emulsion layer Sensitizing dye 5-jy < Containing tabular silver iodobromide emulsion (average grain size/, 3 μm1 Average aspect ratio r1 Ag content λ
Mol%) Silver amount...0. &17m" Coupler F-to,t ta/m2 High boiling point solvent 5olv-1 0,/CC/m2 Totally containing gelatin layer (dried thickness 7.3μ) 11th section: 2nd
Blue 8 emulsion layer Tabular silver iodobromide emulsion containing sensitizing dye S-2 (average grain size 7.0 μm1, average aspect ratio/λ, AgI content 1
Mol%) Silver l.../,/97m2 Coupler F-1/ 0.2 ta/m2 High boiling point organic solvent So I v' -10, +23cc/m2 Dye D-j O,02f/Tn Contains 2 Gelatin 1it (dry film 1 thickness 3μ) 72nd layer: 1 liter
Protective layer UV absorber U-/0,0.29/m2 UV absorber (J-j O, jλji'/7
712 Ultraviolet absorber U-j O, OJ f /
Gelatin layer containing m2 high boiling point organic solvent 5olv-2 0,2,1' cc/m2 (dry film thickness - μ) 13th layer 2nd Co-holding layer Fine grain silver iodobromide emulsion silver covered with a bitter surface Amount...0. /te/m2 (Iodine content 1 mol%, average particle size 0°0zμ) Polymethyl methacrylate particles (average particle size/.

In addition to the above-mentioned composition, a gelatin hardening agent H-/ (same as that in the implementation foi) and a surfactant were added to the gelatin layer (dry film thickness - 0 Jμ) containing 3μ).

The compounds used to prepare the samples are shown below.

F-? -CH (J?1 S-/ -r -J (CH2)3SO3S(CH2)3SO3SHN (C2H5)3D-! 03K for SO3 tJ3K D-HiroD- for SO3, and 5olv- of high boiling point organic solvent i and ko are the same as those used in Example.

Processing process Time Temperature 1 minute Jt"C - 1 minute (= 7 minutes 1 minute 1 minute color development 1 minute training - minute floating)
White Otubun Arrival
μ minute
μmin/l 〈 7 min.
The following composition is used for the hot treatment liquid.

No.-Developer water 70
0 gonitrile N, N, N-) rimethylene phosphonate pentatrirum salt 12 Sodium sulfite, 2o2 hydroquinone monosulfonate
3 o2 Sodium carbonate (-hydrate) /-Phenyl-a-methyl-μ-Hydrodimethyl-3 Bilasoliton Potassium bromide Potassium thiocyanate Potassium iodide (0.7% ρ solution) Add water and invert and lick. Nitrilo-N, N, N-) rimethylene unsulfonic acid/pentnatrirum stannous chloride (dihydrate) p-aminephenol sodium hydroxide Add glacial acetic acid water and color developer water 30? λ 2 2.32 1, Kota, 2 shoulders l/000go00m1 L/2/jml/ooOml 00m1 Nitrilo-N,N,N-)rimethylenephosphonic acid/pentatrirum salt Sodium sulfite Sodium tertiary phosphate ( /Mizugaki) Potassium bromide Potassium iodide (007% bath solution) Sodium hydroxide Citrazate N-ethyl-N-(!-methanesulfonamide ether)- 3-Methane-aminoanili/・Sulfuric acid 3, Budithiaoctane-7°! - Add all water to adjust the solution y 7 t 3 t ? / 2 ri07n1 /,! 2 / / 1 / 2 1ooor1g Water 7' Omg Sodium sulfite/, 2y Sodium ethylenediaminetetraacetate (dihydrate) Add thiman glycerin ice water and ζ White Sodium ethylenediaminetetraacetate (dihydrate) Etele/ Diamine iron tetradate (1) Ammonium (dihydrate) Add potassium bromide water to fix fixing solution Water Sodium thiosulfate Sodium bisulfite Add water to stabilize solution ♂ 20, u ml ml / 000 go ♂ ooWLg λ ta1,! 0! P 100 ta/ 000 me ♂ OOπC ♂ o, oy jt, 0? ! , 01 ooomt water 10
θC formalin (37% by weight)! , Om
l Fuji Drywell (surface activator manufactured by Fuji Film@)! , O door and add water 1000m1 sample 0.2
~1710 Preparation In Sample 1/-0/, the high boiling point organic solvent of the 1st O layer and 1st/layer was removed, and the number of coupler residues was changed to the coupler shown in Tatsu 3 instead of coupler F-&. The sample was prepared with the target as sample≠07, except that it was added so that the amount was equimolar to g.

All water-soluble polymer couplers were added to the emulsion layer as twt% aqueous solutions.

The obtained sample was cut into a size of 110/~φ/ O't" half cabinet and processed in the following processing steps without exposure. At this time, the amount of first developer was 100 ml per half cabinet/sheet. And so.

The first developed t1.6 types obtained here were concentrated and analyzed using a liquid chromatograph (Shimadzu LC-JA model) to dissolve the solution; methanol/water = t♂//, 2, triethylamine 0.0 j %, pH=7, 0. iQ fatigue length 2
90nm, column TSK-Gel ODS-roT
M) Quantified. The amount shown is 1 amount suspended in Tatsu JK 1st developer. It can be seen that the uninvented water-soluble polymer coupler has a small amount of outflow and is stable even when it is passed through the entire processing sequence.

Furthermore, when the entire Vinokase hardness was measured in the same manner as in Example 3, the results were almost the same as in Example 3.

From the above results, is it possible to create a color photographic light-sensitive material that has sufficient strength by using the coupler of the present invention and has extremely low diffusion of the coupler into the processed Lg and instep? I was able to get it.

1, tO/(comparative example) 4' 0. 2 // 4’ OJ // Hiro　O≠　　　　/l ≠or (present invention) 4’ 0 6 tt IfO'7... Ll, O? q-o’7 tt A-/ A-co -J Y-μ 'r'-tt ゝ(-(2- τ-13 2! Ko and liri patent application Fuji Photo Film Co., Ltd.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material characterized by containing a water-soluble polymer having at least one type of repeating unit each of the following general formulas (I) and (II). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A is derived from a vinyl monomer having a color coupler residue that can couple with an oxidized product of an aromatic primary amine developer to form a dye. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, B is a repeating unit represented by the following (II-A).) General formula (II-A) ▲ There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R represents a hydrogen atom, a chlorine atom, or an alkyl group. Q is -CO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
or an arylene group having 6 to 10 carbon atoms. L
is -CO_2-, ▲ has a mathematical formula, chemical formula, table, etc. ▼ is a divalent group containing at least one bond and has 3 to 15 carbon atoms, or -O-, ▲ has a mathematical formula, chemical formula, table, etc. Yes▼, -CO-, -SO-, -SO_2-,
-SO_3-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Represents a divalent group containing at least one bond and having 1 to 12 carbon atoms. R_1 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. R' represents a hydrogen atom or an alkyl group. l and m represent 0 or 1, but are never 0 at the same time.