JPH01142632A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a novel polymeric coupler having improved sharpness of color image by incorporating a specified polymeric coupler and a compd. which forms no dye by a reaction with an oxidized body of an aromatic primary amine type developing agent into a same silver halide emulsion layer. CONSTITUTION:At least one kind of polymeric couplers synthesized by a reaction using a chain transfer agent having 0.01-50 chain transfer constant, and at least one kind of compds. which forms no dye by a reaction with an oxidized body of an aromatic primary amine type developing agent are incorporated into a same silver halide emulsion layer. Among said polymeric couplers, oleophilic polymeric couplers are expressed by formula I, wherein E is a univalent group; A is a recurrent unit derived from an ethylenic unsaturated monomer having a coupler residue; B is a recurrent unit derived from a copolymerizable ethylenic unsatd. monomer; X is a univalent group; each x and y is a content of each recurrent unit in the polymeric coupler. By this constitution, the sharpness of a color image is improved using a novel coupler exhibiting high color developing property.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention contains a novel color image-forming coupler capable of coupling with an oxidized product of an aromatic primary amine developer, and provides a halogenated color image-forming coupler with excellent image quality. This invention relates to silver color photographic materials.

(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, and phenoxazine. , phenazine and similar dyes are known to form color images. In this system, a subtractive color method is usually used for color reproduction, forming images in yellow, magenta, and cyan, which are complementary colors to silver halide emulsions that are selectively sensitive to blue, green, and red, respectively. agent is used.

In recent years, with the spread of small cameras, such as disk cameras and /10 size cameras, the screen size of photographic film has become smaller. On the other hand, since consumers are increasingly demanding final images of high quality, comprehensive improvements in color reproduction, sharpness, graininess, storage stability, etc., are desired for photographic materials.

By the way, in multilayer color photosensitive materials, color mixing can be reduced and
For better color reproduction it is necessary to fix each coupler in separate layers.

Many methods are known for making this coupler diffusion resistant.

One method is to introduce long-chain aliphatic groups into the molecules of low-molecular couplers to prevent diffusion. Since the coupler produced by this method is immiscible with an aqueous gelatin solution, it is necessary to solubilize it in an alkali and add it to the gelatin solution, or to dissolve it in a high boiling point organic solvent and emulsify and disperse it in an aqueous gelatin solution.

Such color couplers require a large amount of gelatin because they cause crystal precipitation in the emulsion or soften the emulsion layer when a high boiling point organic solvent is used.
As a result, this results in the opposite of the desire to make the emulsion layer thinner.

Another way to introduce couplers into each separate layer is to
This method utilizes a polymer coupler latex obtained by polymerizing monomeric couplers.

Adding these polymeric couplers to hydrophilic colloid compositions in latex form has many advantages over other methods.

First, since the hydrophobic material is made into latex, the strength of the formed film will not deteriorate, and since latex can contain a high concentration of coupler units, it is easy to make a high concentration coupler into an emulsion. It can contain
Moreover, since the increase in viscosity is small, the film can be made thinner and the sharpness can be improved.

Furthermore, since it is non-migration, there is no color mixing, and precipitation of the coupler in the emulsion film is less likely.

Examples of such addition of polymeric couplers to gelatin silver halide emulsions in the form of latex include US Pat. Ko≠7.4
No. 4g, U.S. Patent No. 3,4tJ/, ♂20 describes its manufacturing method and μ equivalent magenta polymer coupler latex.
West German Patent Tsutsuko, 72! , Jri No. 7 and U.S. Patent No. 3. Copolymerized latexes with competitive couplers for 2t, ≠ 3 are described in U.S. Patent No. 3,767, ≠ 72 and Research Disclosure.
cyan polymer coupler latex is described in ure) 2/7 koz (i ri♂ko year).

However, although polymer couplers have the above-mentioned excellent characteristics, they also have the following problems that need to be improved.

t Relatively high molecular weight (more than number average molecular weight iooθO)
Polymer couplers have sufficient non-migration properties, but their coupling reactivity is poor, resulting in low sensitivity, gradation, and dye density of the resulting dye.

When the content of coupler units (the content of repeating units having coupler residues) in the dipolymer coupler increases, the color development per unit weight (of coupler units) decreases significantly.

3. On the other hand, polymer couplers with lower molecular weights increase the dye concentration, but are insufficient in terms of non-migration, resulting in color mixing and decreased sensitivity.

If high color development can be maintained using a polymer with a high coupler unit content, it would be possible to make the photosensitive film thinner because it would be necessary to incorporate only a small amount of coupler in the emulsion at a higher concentration, resulting in sharper images. Since it becomes possible to significantly improve sharpness, improving color development in polymers with a high coupler unit content is one of M's important challenges.

In addition, multilayer color photosensitive materials in which polymer couplers are added to silver halide emulsions have the disadvantage of worsening the graininess of the resulting images or deteriorating the storage stability of latent images after exposure. .

Among these, regarding graininess, for example, for the deterioration of graininess due to the use of λ equivalent magenta polymer Cassiller,
As described in JP-A-12-77≠//2-, it is disclosed that improvements can be made by using in combination a compound that does not react with the oxidized product of an aromatic primary amine developer to form a dye. ing.

However, even these systems have not been able to meet the demand for improvement in the deterioration of the storage stability of latent images after exposure due to the use of polymer couplers. Achieving both this and graininess improvement is another seven important issues.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide color photographic light-sensitive material in which the sharpness of color images is improved using a novel coupler that has a high coupler unit content and exhibits high color development. The goal is to provide the following.

A third object of the present invention is to provide a silver halide photographic material in which the sharpness of a color image is improved by a novel polymeric soler, and deterioration in graininess is improved.

A third object of the invention is to provide novel polymeric couplers that
An object of the present invention is to provide a silver halide photographic material with improved sharpness of color images and excellent latent image storage stability.

(Means for Solving the Problems) An object of the present invention is to combine at least one polymer coupler synthesized through a polymerization reaction using a chain transfer agent with a chain transfer constant of 0.01 to 50 and an aromatic At least one compound that does not react with an oxidized form of a primary amine developer to form a dye
This was achieved by a silver halide photographic light-sensitive material, which is characterized in that it contains a silver halide seed and a silver halide emulsion layer in the same silver halide emulsion layer.

The continuous transfer constant used in the present invention is 0.01~! Among polymer couplers synthesized through a polymerization reaction using a chain transfer reaction of O, lipophilic polymer couplers have the following general formula [P
].

General formula [P] +B to E represents a heptavalent group, preferably a heptavalent group having ♂ or more carbon atoms. A represents a repeating unit derived from an ethylenically unsaturated monomer having a coupler residue capable of coupling with an oxidized form of an aromatic primary amine developer to form a dye. B represents a repeating unit derived from a copolymerizable ethylenically unsaturated monomer. X
represents a monovalent group. x and y are the content of each repeating unit in the polymer coupler, and the weight ratio of X and y (X:y)
10:? 0 to 100:0.

The compound represented by the general formula CPI of the present invention will be explained in more detail.

As mentioned above, A is a repeating unit having a coupler residue that can couple with an oxidized product of an aromatic primary amine developer to form a dye, and is a monomer represented by the following general formula [■] Induced from the body.

General formula ([) R嘗CH,=CL L(-L・÷, (-L・÷7Q) In the formula, R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (RZ is a hydrogen atom, and an alkyl group having 1 to 4 carbon atoms) Alkyl group or carbon number 1-
6), -COO-1-NHC
O-5-OCO-1 represents hydrogen, hydroxyl, halogen atom, or substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy),
(same as above), L2 represents a linking group connecting Ll and Q, m represents O or 1, n represents O or 1, and Q is coupled to an oxidized aromatic primary amine developer. represents a coupler residue that can be converted into a dye.

Specifically, the linking group represented by L2 is +X'+J'
-X"÷p(-J2-X'+q-(-J"-)
-, -1-.

Jl, J2, J3 may be the same or different, -
〇〇-1-SO, -5-CON-(R' is a hydrogen atom, an alkyl group (1 to 6 carbon atoms), a substituted alkyl group (1 to 6 carbon atoms), -3o□N-(R'S ■ is the same meaning as above), -N-Rh- (R5 is the same meaning as above, R
6 is an alkylene group having 1 to about 4 carbon atoms), R5R? -N-R' -N- (R', R' are the same as above, R7
represents a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms), or a substituted alkyl group (having 1 to 6 carbon atoms). ), -0-1RS
R? l -5-1-N-CO-N- (R', R' are the above and RS
R? (same meaning), -N-3o□-N- (R', R' have the same meaning as above), -COO-1-OCO-1-NCO□-s (R5 has the same meaning as above), -NGO-(R ' is synonymous with the above).

x', x2, and x' may be the same or different and represent an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, an aralkylene group, or a substituted aralkylene group.

p, q, r and S represent 0 or 1.

In the above general formula [■], XI, Xz, and X:I may be the same or different (representing an unsubstituted or substituted alkylene group, aralkylene group, or phenylene group having 1 to 10 carbon atoms) , the alkylene group may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, and examples of the aralkylene group include benzylidene and phenylene groups. Examples include p-phenylene, m-phenylene, and methylphenylene.

Substituents for the alkylene group, aralkylene group, or phenylene group represented by Xl5X2,
A group represented by R'' (R11 represents alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, substituted aralkyl; L-NH3O□R1 (R8 is the same as above),
-3OR8 (R' has the same meaning as above), -3o, R8 (R1
1 has the same meaning as above), -COR'(R" has the same meaning as above), -COR'(R" has the same meaning as above)
0 may be the same or different and represent a hydrogen atom, alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, substituted aralkyl), an amino group (which may be substituted with alkyl), a hydroxyl group, or a hydrolyzable group. Examples include groups that form a hydroxyl group. When there are two or more of these substituents, they may be the same or different from each other.

Examples of substituents for the above-mentioned substituted alkyl group, substituted alkoxy group, substituted phenyl group, and substituted aralkyl group include hydroxyl group, nitro group, alkoxy group having 1 to about 4 carbon atoms, -N
ISO1R” (R” has the same meaning as above), -NHCOR
Group represented by ll (R11 and RI6 have the same meaning as above)
, -3ot R'(R' has the same meaning as above), -CO
Examples include Rs (R1' has the same meaning as above), a halogen atom, a cyano group, an amino group (which may be substituted with alkyl), and the like.

Next, among the color coupler residues represented by Q in general formula (1), cyan color forming coupler residues are of the phenol type (III, [■]) represented by the following general formula.
or naphthol type CI [[], (IV) (hydrogen atoms other than the hydrogen atom of each hydroxyl group are separated and linked to -(-L'-h-+LZ-)-0) are preferred.

H (R")Q-Z' In the formula, R1 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, Aromatic group, heterocyclic group, carbonamide 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,
Examples include an aromatic thio group, an aromatic sulfonyl group, a sulfamoylamine group, a nitro group, and an imide group.

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

R" is -CONR"R", -NHCORI4, -NHC
OOR+', -NH3Ot RI6, -NHCONR"
R" or -NISO, RI4R", and RI4 and RIS represent a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (e.g., methyl, ethyl, butyl, methoxyethyl, n-decyl, n-dodecyl, n-hexadecyl , trifluoromethyl, heptafluoropropyl, dodecyloxypropyl, 2゜4-di-tert-amylphenoxypropyl, 2゜4-di-tert-amylphenoxybutyl), aromatic groups having 6 to 30 carbon atoms (e.g. phenyl, tolyl, 2-tetradecyloxyphenyl, pentafluorophenyl, 2-chloro-5-dodecyloxycarbonylphenyl), heterocyclic groups having 2 to 30 carbon atoms (e.g., 2-pyridyl, 4-pyridyl, 2- furyl, 2-thienyl), R1- is an aliphatic group having 1 to 30 carbon atoms (e.g. methyl, ethyl, butyl, dodecyl, hexadecyl), an aromatic group having 6 to 30 carbon atoms (e.g. evaphenyl, tolyl, 4-chlorophenyl, naphthyl), a heterocyclic group (e.g. 4-pyridyl, quinolyl, 2-furyl).

R14 and RIS may be bonded to each other to form a heterocycle (eg, morpholine ring, piperidine ring, pyrrolidine ring). r' represents O-3, S' represents O-2, and q' and r' each represent an integer of 0-4.

X4 represents an oxygen atom, an ionic atom or R”NC,
R17 represents a hydrogen atom or a monovalent group.

When RI7 represents a monovalent group, R1? Examples include aliphatic groups having 1 to 30 carbon atoms (e.g. methyl, ethyl, butyl, methoxyethyl, benzyl), aromatic groups having 6 to 30 carbon atoms (e.g. phenyl, tolyl), and aliphatic groups having 2 to 30 carbon atoms (e.g. phenyl, tolyl). heterocyclic groups (e.g. 2-pyridyl, 2-pyrimidyl),
Carbon amide groups having 1 to 30 carbon atoms (e.g. formamide, acetamide, N-methylacetamide, benzamide), sulfonamide groups having 1 to 30 carbon atoms (e.g. methanesulfonamide, toluenesulfonamide, 4
-chlorobenzenesulfonamide), imide group having 4 to 30 carbon atoms (e.g. succinimide), -〇RIB, 5R
II+, -COR", -CONR"Rth, -COCOR
", -COCONR"R1', -COOR20, -CO
COOR", -3o, R", -3O□ 0R20, -3
O□NR111RI9 and -NR"R" may be mentioned. Here, R'' and R19 may be the same or different, and each represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (for example, methyl, ethyl, butyl, dodecyl, methoxyethyl, trifluoromethyl, heptafluoromethyl, propyl), aromatic groups with 16 to 30 carbon atoms (e.g. phenyl, tolyl, 4-chlorophenyl, pentafluorophenyl, 4-cyanophenyl, 4-hydroxyphenyl) or heterocyclic groups with 2 to 30 carbon atoms (e.g. 4-pyridyl). ,
3-pyridyl, 2-furyl).

R111 and RI9 may be bonded to each other to form a heterocycle (eg, morpholino, pyrrolidino).

Examples of Rto include the substituents shown in <RIS and R19 excluding the hydrogen atom.

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 leave include halogen atoms (e.g. fluorine,
chlorine, bromine, iodine), aliphatic oxy groups having 1 to 30 carbon atoms (e.g., methoxy, ethoxy, 2-hydroxyethoxy, carboxymethyloxy, 3-carboxypropyloxy, 2-methoxyethoxycarbamoylmethyloxy, 2-methane) sulfonylethoxy, 2-carboxymethylthioethoxy, triazolylmethyloxy), aromatic oxy groups having 6 to 30 carbon atoms (e.g., phenoxy,
4-hydroxyphenoxy, 2-acetamidophenoxy, 2,4-dibenzenesulfonamidophenoxy, 4
-phenylazophenoxy), heterocyclic oxy groups having 2 to 30 carbon atoms (e.g., 4-pyridyloxy, 1-phenyl-5-tetrazolyloxy), aliphatic oxy groups having 1 to 30 carbon atoms (e.g., dodecylthio), aromatic thio group having 6 to 30 carbon atoms (e.g. 4-dodecylphenylthio), heterocyclic thio group having 2 to 30 carbon atoms (e.g. 4-pyridylthio, 1-phenyltetrazol-5-ylthio), carbon Acyloxy group having 2 to 30 carbon atoms (e.g. acetoxy, benzoyloxy, lauroyloxy), carbonamide group having 1 to 30 carbon atoms (e.g. dichloroacetylamide, trifluoroacetamide, heptafluorobutanamide, pentafluorobenzamide), carbon number 1 to 30 sulfonamide groups (e.g. methanesulfonamide, toluenesulfonamide), aromatic azo groups having 6 to 30 carbon atoms (e.g. phenylazo, 4-chlorophenylazo, 4
-methoxyphenylazo, 4-pivaloylaminophenylazo), aliphatic oxycarbonyloxy group having 1 to 30 carbon atoms (e.g., ethoxycarbonyloxy, dodecyloxycarbonyloxy), aromatic oxycarbonyl group having 6 to 30 carbon atoms Oxy group (e.g. phenoxycarbonyloxy), carbamoyloxy group having 1 to 30 carbon atoms (
For example, methylcarbamoyloxy, dodecylcarbamoyloxy, phenylcarbamoyloxy), carbon number 1
~30 and a heterocyclic group that is continuous to the active position of the coupler with a nitrogen atom (e.g., succinimide 1, phthalimide, hydantoinyl, pyrazolyl, 2-penzotriazolyl)
etc. can be mentioned.

Y' represents an atomic group necessary to form a 5- to 7-membered ring together with the carbon atoms to which it is bonded. represents R# alone or in combination. R" and R" each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an arylcarbonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, or a cyano group.

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

Preferred examples of R++ include halogen atoms (e.g., fluorine, chlorine, bromine, etc.), aliphatic groups (e.g., methyl, ethyl, isopropyl), carbonamide groups (e.g., acetamide, benzamide), sulfonamide groups (e.g., methanesulfonamide, toluenesulfonamide), etc.

Preferred R12 is -CONR14R'', examples of which include carbamoyl, ethylcarbamoyl, morpholinocarbonyl, dodecylcarbamoyl, hexadecylcarbamoyl, decyloxypropyl, dodecyloxypropyl, 2,4-di-tert-amylphenoxypropyl, 2.4-di-tert-amylphenoxybutyl.

X4 is preferably RI 7 N, and R17 is -COR" (for example,
formyl, acetyl, trifluoroacetyl, chloroacetyl, benzoyl, pentafluorobenzoyl, p
-chlorobenzoyl), -COOR" (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, methoxyethoxycarbonyl, phenoxycarbonyl), -3○z R" (
For example, methanesulfonyl, ethanesulfonyl, butanesulfonyl, hexadecanesulfonyl, henzenesulfonyl, toluenesulfonyl, P-chlorobenzenesulfonyl), -CONR"R" (N.

N~dimethylcarbamoyl, N,N-diethylcarbamoyl, N,N-dibutylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, 4-cyanophenylcarbamoyl, 3.4-dichlorophenylcarbamoyl,
4-methanesulfonylphenylcarbamoyl), -SO
□NR"RI9 (e.g., N,N-dimethylsulfamoyl, N.

N-diethylsulfamoyl, N,N-dipropylsulfamoyl). More particularly preferred among R'7 is -COR''.

-COOR1@ and -3O2R''.

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 RII, R'2
, X4 or Zl may be a two-membered or more-membered multimer that is 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-mentioned substituents is not limited to this.

The magenta color-forming coupler residue is -C2 (Vl)
, [■], [■], CDI'), [X], (XI) and (XI) coupler residues (Ar, Z2, R
In the case of general formula [v] connected to +L'+L2÷7 at any part of 21 to Rff3, it is more preferable that R2+
This is the case of direct linkage to the replacement position of . ).

Z" H Z2 H 2" H z" H zZ R11z Z' H where Ar is a well-known type of substituent in the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituted alkyl group (e.g. fluoroalkyl haloalkyl, such as
cyanoalkyl, benzylalkyl, etc.), aryl group or substituted aryl group (substituents include alkyl groups (e.g. methyl, ethyl), alkoxy groups (e.g. methoxy, ethoxy), aryloxy groups (e.g. phenyloxy), alkoxycarbonyl groups ( methylsulfonyl), acylamino groups (e.g. acetylamino), carbamoyl groups, alkylcarbamoyl groups (e.g. methylcarbamoyl, ethylcarbamoyl), dialkylcarbamoyl groups (e.g. dimethylcarbamoyl), carbamoyl groups (e.g. phenylcarbamoyl), Alkylsulfonyl groups (e.g. methylsulfonyl), arylsulfonyl groups (e.g. phenylsulfonyl), alkylsulfonamide groups (e.g. methanesulfonamide),
Arylsulfonamide groups (e.g. phenylsulfonamide), sulfamoyl, alkylsulfamoyl groups (
(e.g. ethylsulfamoyl), dialkylsulfamoyl groups (e.g. dimethylsulfamoyl), alkylthio groups (e.g. methylthio), arylthio groups (e.g. phenylthio), cyano groups, nitro groups, halogen atoms (e.g. fluorine, chlorine, bromine, etc.) ), and when there are two or more substituents, they may be the same or different. Particularly preferred substituents 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.).

R2- is an unsubstituted or substituted anilino group, an acylamino group (e.g. alkylcarbonamide, phenylcarbonamide, alkoxycarbonamide, phenyloxycarbonamide), ureido group (e.g. alkylureido,
phenylureido), and these substituents include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), straight chain and branched alkyl groups (e.g. methyl, L-butyl,
octyl, tetradecyl), alkoxy groups (e.g. methoxy, ethoxy, 2-ethylhexyloxy, tetradecyloxy, etc.), acylamino groups (e.g. acetamide, benzamide, butanamide, octanamide,
Tetradecanamide, α-(2,4-di-tert~amylphenoxy)acetamide, α-(2,4-di-tert~amylphenoxy)acetamide, α-(2,4-di-tert~amylphenoxy)acetamide
er t-amylphenoxy)butyramide, α-(3
-pentadecylphenoxy)hexanamide, α-(4
-hydroxy-3-tert-butylphenoxy)tetradecanamide, 2-oxo-pyrrolidin-1-yl,
2-oxo-5-tetradecylpyrrolisif-1-yl,
N-methyl, tetradecanamide), sulfonamide groups (e.g. methanesulfonamide, benzenesulfonamide, ethylsulfonamide, p-toluenesulfonamide, octanesulfonamide, p-dodecylbenzenesulfonamide, N-methyl -tetradecanesulfonamide), sulfamoyl group [e.g. sulfamoyl,
N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N,N-dimethylsulfamoyl, N-hexadecylsulfamoyl, N
-(3'-(dodecyloxy)-propyl]sulfamoyl, N-(4-(2,4-di-tert-amylphenoxy)butylcarbamoyl, N-methyl-N-tetradecylsulfamoyl, etc.), carbamoyl group (e.g. N-methylcarbamoyl, N-butylcarbamoyl,
N-octadecylcarbamoyl, N-(4-(2゜4-
tert-amylphenoxy)butylcarbamoyl, N-methyl-N-tetradecylcarbamoyl), diacylamino group (N-succinimide, N-phthalimide, 2.5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5 -dioxo-1-hydantoynyl, 3-
(N-acetyl-N-dodecylamino)succinimide), alkoxycarbonyl groups (e.g. methoxycarbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), alkoxysulfonyl groups (e.g. methoxysulfonyl, butoxysulfonyl, octyloxysulfonyl, tetradecyl oxysulfonyl), OK-
p-methylphenoxysulfonyl group (e.g., phenoxysulfonyl, p-methylphenoxysulfonyl,
rt-amylphenoxysulfonyl, etc.), alkanesulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl), arylsulfonyl groups (e.g., benzenesulfonyl, 4-nonylbenzenesulfonyl), Alkylthio groups (e.g. methylthio,
ethylthio, hexylthio, benzylthio, tetradecylthio, 2-(2,4-di-tert-amylphenoxy)ethylthio, etc.), arylthio groups (e.g. phenylthio, p-)lylthio), alkyloxycarbonylamino groups (e.g. methoxycarbonyl amino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino), alkylureido groups (e.g., N-methylureido, N, N
-dimethylureido, N-methyl-N-dodecylureido, N-hexadecylureido, N,N-dioctadecylureido), acyl groups (e.g. acetyl, benzoyl, octadecanoyl, p-dodecanamidobenzoyl), nitro groups , carboxyl group, sulfo group, hydroxy group or trichloromethyl group.

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

R", R", RNA, Rzs4z6, R17, R28,
R29, R30SR31, R3! and R33 are each a hydrogen atom, a hydroxyl group, and an unsubstituted or substituted alkyl group (preferably one with 1 to 20 carbon atoms, such as methyl, propyl, t-butyl, trifluoromethyl, tridecyl, etc.), Aryl groups (preferably those with 6 to 20 carbon atoms, such as phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-methoxyphenyl), heterocyclic groups (such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl),
Alkylamino group (preferably one with 1 to 20 carbon atoms).

For example, methylamino, diethylamino, t-butylamino), acylamino groups (preferably those with 2 to 20 carbon atoms, e.g. acetylamino, propylamide, benzamide), anilino groups (e.g. phenylamino, 2-
chloroanilino), alkoxycarbonyl group (preferably one with 2 to 20 carbon atoms; for example, methoxycarbonyl, butoxycarbonyl, 2-ethylhexyloxycarbonyl), alkylcarbonyl group (preferably one with 2 to 20 carbon atoms),
~20 things. For example, acetyl, butyl carbonyl,
cyclohexylcarbonyl), arylcarbonyl group (
For example, preferably one having 7 to 20 carbon atoms. benzoyl, 4-t-butylbenzoyl), alkylthio groups (preferably those with 1 to 20 carbon atoms, e.g. methylthio, octylthio, 2-phenoxyethylthio), arylthio groups (preferably those with 6 to 20 carbon atoms, e.g. phenylthio, 2-butoxy-5-octylphenylthio), carbamoyl group (preferably one with 1 to 20 carbon atoms. For example, N-ethylcarbamoyl group, N,N-dibutylcarbamoyl, N-methyl-N-butyl carbamoyl), sulfamoyl group (preferably up to 20 carbon atoms, such as N-ethylsulfamoyl, N,N-diethylsulfamoyl, N,N-dipropylsulfamoyl) or sulfonamide group (preferably carbon Numbers 1-20
thing. For example, it represents methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide).

Z2 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Examples of groups that can leave include halogen atoms (e.g., chlorine, bromine), campling leaving groups linked via oxygen atoms (e.g., acetoxy, propanoyloxy, hendiyloxy,
Ethoxyoxaroyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxyl, 4-titanesulfonamidophenoxy, α-naphthoxy, 4-cyanoxyl, 4-methanesulfonamide-phenoxy, α-naphthoxy, 3- Pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-
cyanoethoxy, pencyloxy, 2-phenethyloxy, 2-phenoxy-ethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), campling leaving groups linked via a nitrogen atom (e.g. 9
9437, specifically benzenesulfonamide, N-ethyltoluenesulfonamide,
Heptafluorobutanamide, 2゜3.4,5.6-pentafluorobenzamide, octane sulfonamide,
P-cyanophenylureido, N,N-diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl-
2,4-dioxo-3-oxazolidinyl, 1-benzyl-5-ethoxy-3-hydantoynyl, 2-oxo-
1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-1,2°4-triazol-1-yl, 5- or 6-promohenzotriazol-1-yl, 5-methyl-1 , 2,3,4-1-riazol-1-yl, benzimidazolyl), coupling-off groups linked via a sulfur atom (e.g. phenylthio,
2-carboxyphenylthio, 2-methoxy-5-octylphenylthio, 4-methanesulfonylphenylthio, 4-octanesulfonamidophenylthio, benzylthio, 2-cyanoethylthio, 5-phenyl-2,3,
4,5-tetrazolylthio, 2-benzothiazolyl). Preferably, the detachable group is a halogen atom, a coupling-off group linked via an oxygen atom, or a coupling-off group linked via a nitrogen atom, and particularly preferably an aryloxy group, a chlorine atom, a pyrazolyl group, an imidazolyl group, or a triazolyl group. It is the basis.

The yellow color-forming coupler residue is preferably of the acylacetanilide type, particularly the pivaloylacetanilide type [■], benzoylacetanilide type [2], or [stand] represented by the following general 2 (free in the general formula At the bond part, connect to (-L'+T+L"÷,)R"
``IRJ4 R3'' In the formula, R34, R'', R36 and R37 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 alkoxy Carbamoyl group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group,
Alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamido group, arylsulfamoyl group, arylsulfonamide group, arylureido group, carboxy group, sulfo group, nitro group, cyano group, thiocyano These substituents may be the same or different.

Z3 is represented by a hydrogen atom or the following general formula (XVI, [kan], [ton] or [kan]).

OR3B (E) R311 represents an optionally substituted aryl group or heterocyclic group.

R39 and R40 are each hydrogen atom, halogen atom, carboxylic acid ester group, amino group, alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted phenyl group or represents a heterocycle, and these groups may be the same or different.

0~〆N)0 '゛WJ-''''' (劃■ Represents a nonmetallic atom required to form a 5- or 6-membered ring.

Among the general formulas, [XINII] to (XINII) are preferred.

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

Preferred examples of the ethylenically unsaturated monomer providing the repeating unit represented by B include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (such as methacrylic acid), and esters or esters derived from these acrylic acids. Amides (e.g. acrylamide, methacrylamide, n-butylacrylamide, L-butylacrylamide, 2-methoxyethylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butylacrylate, L-butylacrylamide, 1so-butyl acrylate, 2-ethylhexyl acrylate, n
-Octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, β-alkoxyethyl (meth)acrylate (e.g. 2-methoxyethyl acrylate,
2-methoxyethyl methacrylate, 2-methquinethyl acrylate, 2-ethoxyethyl acrylate,
2-ethoxyethyl methacrylate, 2-butoxyethyl acrylate, 2-n-propyloxyethyl methacrylate, 2-(2-methoxy)ethoxyethyl acrylate, etc.), β-sulfonamidoethyl (meth)acrylate, β-carbonamidoethyl (Meth)acrylates, β-alkoxyethyl acrylamides (alkoxy groups may further contain multiple substituted alkoxy groups), β-sulfonamidoethyl acrylamides, β-
carbonamide ethyl acrylamide, etc.), vinyl esters (e.g. vinyl acetate, vinyl laurate), acrylonitrile, methacrylatetrile, dienes (e.g. butadiene, isoprene), aromatic vinyl compounds (e.g. styrene, divinylbenzene and its derivatives, e.g. vinyltoluene) , vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid,
Vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine, ethylene, propylene, 1-butene , isobutine'l<.

Further, B may be a repeating unit derived from an ethylenically unsaturated monomer that is bonded directly to the binder or via a hardening agent.

Examples of such ethylenically unsaturated monomers include the following.

CH2=CH cCH3 ■ CH2=C? scH3 CH2=C CH2=CH CH2=CH C0NHcH2CH2α: CH2CCH3CH2=CH Group C0NHCH2NHCOCH2CH2SO2CH2CH
2αH3 cH2-C cH2-cH C02CH2CH20COCH2CH25O2CH2C
H21SO2CH2CH2SO2CH2CH2BrCH
3. One or more of the ethylenically unsaturated monomers used here can also be used together.

Examples include ethyl acrylate and n-butyl acrylate, n-butyl acrylate and styrene, n-butyl acrylate and t-butylacrylamide, and no-methoxyethyl methacrylate and potassium styrene sulfinate.

Particularly preferred compounds among the compounds represented by the general formula [I] are shown below.

R1 represents a hydrogen atom or a methyl group, and L is -CONH
-1-COO-1-OCO-1 represents /, and n represents O or l. L is expressed as (-xl+, 11) (21 children J2- 802-1-CONH-1-8
O2NH-1-NHCO-1-NH8O2-1-〇-1
-NHC0NH-1-S-1-COO-1-OCO-1
-NHCOO-1-OCONH-, X, X
, X may be the same or different, and represent an alkylene group (carbon number/~μ), an arylene group, or a substituted arylene group, and pl qX r and S represent O or/.

Among B, particularly preferred are acrylic esters, methacrylic esters, acrylic amides,
It is an ethylenically unsaturated monomer that can be bonded to methacrylic acid amides, maleic esters, styrenes, and binders directly or through a hardening agent.

In the general formula [P], E preferably represents a monovalent group having at least one carbon number, for example, the following general formula (XXI[[
].

General formula [XX■] E1+Y← El includes an alkyl group having 2 or more carbon atoms, a substituted alkyl group, a substituted aryl group, a substituted naphthyl group, and the like.

Examples of substituents that may be further substituted on these groups include halogen atoms, cyan groups, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, -NHCO
R46 (R46 represents an alkyl group, substituted alkyl group, phenyl group, substituted phenyl group, aralkyl group), -
NH3O2R46 (R46 has the same meaning as above), -COOR
(R has the same meaning as above), -0COR46 (R46 has the same meaning as above), -8OR"R48 may be the same or different, hydrogen atom, alkyl group, substituted alkyl group, phenyl group, substituted phenyl group, aralkyl group , a substituted aralkyl group), an amino group (which may be substituted with an alkyl group), a hydroxyl group, and a group that forms a hydroxyl group by hydrolysis.

Examples of substituents for the alkyl group, substituted alkoxy group, substituted phenyl group, and substituted aralkyl group include hydroxyl group, alkoxy group with carbon number/~about μ, -NH8O2R46
(R46 has the same meaning as above), -NHCOR46 (R46 has the same meaning as above), -COOR46 (R46 has the same meaning as above), -0COR46 (R" has the same meaning as above), 5O2R46 (R46 has the same meaning as above), -COR46 (
R46 has the same meaning as above), . . . a rogen atom, a cyano group, an amino group (which may be substituted with an alkyl group), and the like.

Preferred examples of El are shown below, but the invention is not limited thereto.

C8H17+ Cl0H21+ Cl2H25+
C14H29+ C15H31+ C16
H33-SCl8H37+ C20H41-・
C31H63-・C8H170CCH2-, Cl2
H250CCH2-.

C18H370CCH2-・C2H50CC
HC12H25・II
111C16H33SO2NHCH2CH2-.

C8HFCONHCH2CH2-, C13H27CO
NHCH2CH2-.

C15H3□C0NHCH2CH2-, C17H35C
ONHCH2CH2-.

2MS 12H25 ■ C) (3CONCH2CH2-, Cl2H25NHCH
2CH2-.

c16H33NHcH2cH2-, Cl2H25NHC
OCH2-.

C Engineering 8H37NHCOCH2-.

C7H15COOCH2CH2-, C1□H23COO
CH2CH2-.

C□7H35COOCH2CH2CH2-, Cl2H2
5SO3CH2CH2-.

Cl2H25' Cl2H25NHCOCH2-, C16H33NHCO
CH2-.

C engineering,)I23CONH+CH2CH2N-)l-cc
H2cH2-C16H33NHCCH2- 〇General formula CXXm), Y is -8-1-8O-1
-so2- and p is 0 or /.

In the general formula [P], X is preferably a hydrogen atom,...
Represents a rogen atom (FXα, BrX I).

Next, we will give representative examples of monomeric couplers that provide a coupler residue having a coupler residue that can be coupled to an aromatic primary amine developer represented by the general formula [I], which is a color forming part, to form a dye. shown, but not limited to.

Moreover, one type of each monomer coupler may be used, or several types may be used.

0!硼NHOC, Fff 00) Ctl z = CIl
0H00CH,=CH CH,=C)I 0HCH.

Js Oω NHCOOC4H9 (iso) 09) CH3 CH2=C (branch) 0H
Rui1 CI.

■ l1 Hi CH, = Written by CH (32) CHi=CH ■ CH2=CH C11zGHzCN CI (35) CI(,=CH Hff CI C1l□=C1 C0NHCHzCHz0 C)12 = CHCtl x I C)! ,=CHCH3 CI(3 Ctlz-CCH3 CH2=CHl CH2=C-CH3 Hi CH2=C to H3[;ffi C113 CHgo ■ N CH, = CH 噌しt SO□ ■ (jg) CH3 (!j) U4+LM 3 (!t) Ha (!r) (!ri) (tO) (t/) α The first method for synthesizing the coalescent coupler is to carry out a polymerization reaction using a carbon chain transfer agent having a prime number or more. Preferred examples of chain transfer agents used in this polymerization are listed below. , but is not limited to this.

C3H17SH・CtoH21SH・C12H25
SH・C14H29SH・C15H31SHI C
16H33SH.

Cl8H37SH, C20H41SH, C31H63S
H+C16H33SO2NHCH2CH2SH.

C3H17CONHCH2CH2SH, C13H27C
ONHCH2CH2SH.

C15H31CONHCH2CH2SH, CFH35
CONHCH2CH2SH.

21″i5 C12H25 CH3CONCH2CH25H, (42H25NHCH
2CH2SH.

C16H33NHCH2CH2SH, Cl2H25NH
COCH2SH.

CI, 3H37NHCOCH2SH.

(JUgM17(nJ, (JU12
M25.

CH3C3H7 C1oH2, CHOH2C6H13cHoH1H3CH
3 C14H27CHOH, C17H35CHOH.

CJCH2Cα℃, □H25, ■CH2Cα)C12H
25゜Br2HCα)C16H33,zcH2COCK
4BH37.

Engineering CH2Cα) C16H33, Br2CHCα”12H
251Ct3CCOOC16H33 Another method for synthesizing polymeric couplers terminated with groups of 2 or more carbon atoms, which are preferred compounds of the lipophilic polymeric couplers used in the present invention, is to react with a nucleophile or an electrophile to form a covalent bond. A polymer coupler obtained using a chain transfer agent having a functional group capable of producing It's a method.

Chain transfer agents used in this synthesis method are listed below, but are not limited thereto.

HOCH2CH2SH, HOCH2CH2CH2SR.

NH2CH2CH2SH,)ICH2COOCH3・H
(?7.

H ICH2COOH, QICH2COOH, BrCH2C
0OH.

ICH2COOCH3 Furthermore, preferred examples of the nucleophile or electrophile used in this synthesis method are shown below, but are not limited thereto.

C3H11COOH, C7H15COBr, Cg
H1gCOC/! .

C11H23CO(IJ, C13H27COC1
, C15H31COQ! rC17H35COBr,
(4H17SO3H, (40H21SO2α.

Cl2H250H・C14H290H, Cl8H37
0HrC8H17NF(2・C1(IH210H・
Cl2H25NH2・C16H33NH2, C6H13
Br, Cl2H25Br.

In the polymer coupler obtained through the polymerization reaction using the chain transfer agent used in the present invention, in addition to the compound represented by the general formula (P), compounds represented by the following general formulas [XX■] and [xX■] are also included. The amount of the compound is about 0.

/ to about 20 wt%.

General formula [: XXIV ”] E(-A+-+BSE (E% AXB% X% V has the same meaning as above)
General formula [XXv] I+Ase+BsuX (A, B, x, y, and X have the same meanings as above.

(2) represents a group derived from a radical generated by decomposition of a polymerization initiator. ) Also, Takayuki Otsu, [Radical Polymerization N) jp.

As described in /Co3-127 (Kagaku Doujin, /7/year), in addition to the above general formulas [XX■] and [XX■], chain transfer to monomers and transfer to polymerization solvents are also possible. The compound derived from chain transfer corresponds to the chain transfer ability of the monomer solvent,
Each exists.

General formula synthesized using a chain transfer agent as in the present invention [
The polymer represented by [■] is a telomer.
It is called.

Regarding telomers, see “Oligomers” edited by Makoto Okawara et al.
(Kodansha Enteifuku, /ri 7) p, 10~
A detailed explanation is given in 30.

The method for synthesizing the telomer coupler used in the present invention differs from ordinary radical polymerization in that it uses a chain transfer agent having a carbon number of gram or more. In this case, polymerization is initiated and continued via radicals transferred to the chain transfer agent, and a polymer is produced by further chain transfer to the transfer agent.

Chain transfer agents to be used include carboxylic acids and their esters, alcohols, thiols, ethers, aldehydes, ketones, halogenated hydrocarbons, fatty acid chlorides, halogenated carboxylic acids, etc. be. Among these, halogen-containing compounds and thiols are particularly preferred.

These chain transfer agents are described, for example, in J.

Polymer Handbook by Brandrup et al.
John Willie and Sons) (Polyme
rHandbook, (John Wiley &amp;
5ons)) ■-j7~10, written by Takayuki Inuzu
Radical Polymerization (1) J (Kagaku Doujin, / 1971) No. 12
As described in 1-2, the chain transfer reaction activity varies widely from large to small, so the amount added depends on the type of chain transfer agent and polymerization conditions (polymerization concentration, polymerization temperature, initiator Depending on the amount (e.g., amount), it may be used in large amounts, or it may be only about 1 mol/mole per monomer.

The lipophilic telomeric coupler of the present invention is synthesized by using a polymerization initiator,
As a polymerization solvent, JP-A No. 4-jj≠3, JP-A No. 7-
Tage 7! Ko issue, Tokukai Akira! 7-/7t031, JP-A-1
7-201tOJlr, Tokukai Sho! No. l-217411, Tokukai Sho! No. l-10731, Tokukai Sho! ? −≠February issue, Tokukaisho! r-/≠jri≠sign, JP-A-Shoj? -Hiroko J'
≠It is carried out using the compound described in No. 3.

Further, when synthesizing the telomer coupler of the present invention, a polymerization initiator having a carbon number of -0 or more is preferably used.

By using this initiator, the general formula [XX■], [
XXv], it is possible to increase the planar diffusion resistance of the polymer.

Examples of preferred polymerization initiators are shown below.

The H3CH3 I H3CH3 C0□H23C-0-0-CC11H23 polymerization initiator is used in an amount of about 0.01 to about 10 molar based on the monomer, preferably 0.01-λ, O molar.

The polymerization temperature must be set in relation to the molecular weight of the telomer to be produced, the type of initiator, etc.
It is possible to go up to O0C or more, but usually 3o'C to 10O0
Polymerizes within the range of C. For telomer synthesis, higher temperatures are better, preferably in the range of about 70-100C.

The reaction between the polymer coupler obtained in the presence of a chain transfer agent and a nucleophile or electrophile is carried out under various conditions depending on the combination of functional groups involved in the reaction.

For example, when acid chloride is used as an electrophilic reagent and the polymer terminal is an amine group, the reaction temperature is -1000 to 0°C, preferably -100C to room temperature. Bases such as triethylamine and pyridine are also preferably used.

In the telomer coupler obtained in the present invention, at the time the polymerization reaction is completed, a small amount of the chain transfer agent used in the polymerization reaction remains unreacted. If mercabutanes, which are preferably used as chain transfer agents, remain in the telomer coupler, even a small amount may adversely affect the fogging sensitivity of unexposed areas.

In contrast, after completion of the polymerization reaction using a chain transfer agent or after reaction with a nucleophilic (or electrophilic) reagent, additional ethylenically unsaturated monomers (e.g., coupler monomers, or non-chromogenic monomers) are added. The remaining mercaptan can be rendered harmless by adding a mercaptan (mercaptan) and performing the polymerization reaction again, or by adding an oxidizing agent.

Among these methods, particularly preferred is a method in which a non-color-forming monomer (for example, acrylic acid, acrylamide, etc.) that provides a water-soluble polymer is added, polymerized again, and reprecipitated in water or extracted with water.

According to this method, only mercaptan can be effectively removed from the eyelids without impairing the properties of the telomer coupler.

"Lipophilicity" in the compound of the present invention represented by the general formula [P] refers to its solubility in distilled water! % by weight or less.

The ratio of the coloring part in the telomer coupler represented by the general formula [1] is usually 10~! % by weight is desirable, but from the viewpoint of color reproducibility, color development, and stability, λO to 0% by weight is preferable. In this case, the equivalent molecular weight (grams of polymer containing 1 mole of monomeric coupler) is approximately 200-≠000, but is not limited thereto.

In addition, the number average molecular weight of the telomer coupler of the present invention is approximately ! from the viewpoint of color development and sensitivity. OO to about 10,000 is preferred, particularly preferably about 200 to about 1,000.

Among the lipophilic polymer couplers used in the present invention, examples of those obtained using a chain transfer agent having several carbon atoms or more are shown in Table 1.
Shown below.

The main structure of the coupler after polymerization, for example T-7, is as follows.

Monomer coupler content 50. l, Wt. Number average molecular weight 2ro.

Synthesis of Synthesis Example T-/ (copolymer of monomer coupler (1) and butyl acrylate)! -Acrylamideco, μm dichloro-3-methylphenol (monomer coupler (1)) 71g1 Butyl acrylatene. 2gS n-dodecyl mercaptan 2.
3g and N,N-dimethylacetamide 200
Transfer ml to a JOOml Mitsuro flask and place under nitrogen stream for 7 days.
! The mixture was heated to 0C and stirred. Dimethyl azobisisobutyrate 0.
N,N-dimethylacetamide solution containing 3g 1
0 ml was added to start polymerization. After reacting for j hours, the temperature of the reaction solution was lowered to 7°C. Jml of an N,N-dimethylacetamide solution containing 0.7 g of acrylic acid rg1 dimethyl azobisisobutyrate was added, and the mixture was further heated and stirred for ≠ hours.

After the reaction, the cooled reaction solution was poured into water 31, and the precipitated solid was filtered out and further washed thoroughly with water. The telomer coupler (T-/) was prepared by drying the solid under reduced pressure under heat. I got 3g.

This telomer coupler has a coupler unit of monomer coupler (1) in the polymer by chlorine analysis! It was confirmed that the content was 7.3% by weight.

The number average molecular weight by GPC was sroo.

The chain transfer constant to n-dodecylmercaptan used in this synthesis was calculated by the method described below.

75 g of monomeric coupler (1), 2.3 g of n-dodecylmercaptan and 200 g of N,N-dimethylacetamide
ml was placed in a 300 ml Mitsuro flask, and heated and stirred at 7!0C under a nitrogen stream. Dimethyl azobisisobutyrate 0
．． 10 ml of a N,N-dimethylacetamide solution containing 3 g was added to initiate polymerization. At predetermined intervals, the reaction solution IO'rrJ was extracted, and a methanol solution/ml containing 10 mg of hydroquinone was added to the extracted sample to stop the polymerization. The residual monomeric coupler and residual chain transfer agent in this sample were quantified by gel, e-meation chromatography, and gas chromatography, respectively, and log [monomer coupler], log[
chain transfer agent] and linear regression,
Chain transfer constant 3. I got j.

Next, among the lipophilic polymer couplers used in the present invention, a polymer obtained using a chain transfer agent having a functional group capable of reacting with a nucleophile or an electrophile to form a covalent bond and a covalent bond are used. Examples of polymeric couplers obtained by reaction with a nuclear reagent or an electrophile are shown in the table.

The main structure of the resulting coupler, for example T-2/, is as follows.

α Synthesis example Synthesis of telomer coupler T-,2/! -Acrylamide-2,II-dichloro-3-methylphenol (monomer coupler (1)) 30g 1 t-butylacrylamide 20g, 2-aminoethanethiol λ, Og and N,N-dimethylacetamide 200g
Transfer rJ to JOOml Mitsuro 7 Lasco and place under nitrogen stream.
The mixture was heated and stirred at 0C. Dimethyl azobisisobutyrate O9
N containing ≠g.

10 ml of N-dimethylacetamide solution was added to initiate polymerization.

! After reacting for an hour, the reaction solution was cooled with water for 2 to 3 hours.
Cooled to °C. While cooling with water and stirring, myristic acid chloride (CxaHz7coct) was slowly added dropwise.

After the dropwise addition was completed, stirring was continued for an additional 7 hours at room temperature.

Further, 10 g of acrylic acid was added to the obtained telomer coupler solution, and the mixture was heated and stirred to 'C under a nitrogen stream.

N, containing 0.1 g of dimethyl azobisisobutyrate.

Add jml of N-dimethylacetamide solution and add 3 ml of N-dimethylacetamide solution.
The mixture was heated and stirred for hours.

After the reaction, the cooled reaction solution was poured into two volumes of water, and the precipitated solid was filtered out and washed thoroughly with water.

By drying this solid under reduced pressure and moderate heat, ≠t, ♂g of telomer coupler T-2/ was obtained.

A chlorine analysis revealed that the telomer coupler contained ≠3% by weight of the coupler units of monomer coupler (1) in the polymer.

The number average molecular weight by GPC was 2t00.

The chain transfer constant used in the present invention is 0. O/~! Among polymer couplers synthesized through O chain transfer reaction, hydrophilic polymer couplers are mixtures of various polymers, but most of them have the following general formula % Formula % General formula [Q] E2+A+- +B1SX B2 represents a heptavalent group having 2 or more carbon atoms and originating from a radical moiety generated by chain transfer to a chain transfer agent.

A is the same as above. B represents a repeating unit derived from a copolymerizable ethylenically unsaturated monomer. X is the same as above. XSy is the content of each repeating unit in the polymer coupler, and the weight ratio of X and y (x:y) is 10;
~100:O.

The compound represented by the general formula [Q] will be explained in more detail.

A is the same as above.

Preferred examples of the ethylenically unsaturated monomer providing the repeating unit represented by B1 include acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, crotonic acid, crotonic esters, vinyl esters, maleic acid, etc. Examples include acids, maleic acid diesters, fumaric acid, fumaric diesters, itaconic acid, itaconic diesters, acrylamides, methacrylamides, vinyl ethers, styrenes, and the like. These acids may be alkali metal (eg, Na, etc.) or ammonium salts.

More specific examples of these monomers include acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, inpropyl acrylate, n-butyl acrylate, 3-7 acryloyl pro/ξ sulfonic acid, and acetoacetoxyethyl. Acrylate, acetoxyethyl acrylate, phenyl acrylate, no-methoxy acrylate, no-ethoxy acrylate 1.2-(2-methoxyethoxy)ethyl acrylate, and the like. Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n
-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, no-hydroxyethyl methacrylate,
Examples include λ-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. Acrylamides include acrylamide, methylacrylamide, ethyl acrylamide, isozolobyl acrylamide, n-butylacrylamide,
Examples include hydroxymethyl acrylamide, diacetone acrylamide, acryloylmorpholine, acrylamide no methylpropanesulfonic acid, and the like. Methacrylamides include methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, ter
Examples include t-butylmethacrylamide, no-methoxymethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like. Styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, inopropylstyrene, methylstyrene, chloromethylstyrene, methoxystyrene,
Examples include methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, vinylbenzoic e-methyl ester, no-methylstyrene, styrene sulfonic acid, and vinylbenzoic acid.

Examples of other monomers include allyl compounds (such as allyl acetate), vinyl ketones (such as methyl vinyl ketone), and vinyl heterocyclic compounds (such as vinyl pyridine).
, unsaturated compounds (e.g. acrylonitrile, etc.)
.

Among these monomers, those with high hydrophilicity are particularly preferred.

Further, Bl may be a repeating unit derived from an ethylenically unsaturated monomer that is bonded to the binder directly or via a hardening agent.

Specific examples of this ethylenically unsaturated monomer are the same as those mentioned above.

Furthermore, Bl may be a repeating unit derived from an ethylenically unsaturated monomer containing a group that promotes micelle formation in the polymer coupler.

Preferred examples of such ethylenically unsaturated monomers are shown below, but the invention is not limited thereto.

CH3 CH2=CH C00C2H4Rf CH3 CH2=C C00C2H4NH5OzC8F 17CH2=CH CONHC2H40C2H4Rf CH2-CH CooC2H4NHCoC8FH3 CH2=CO COOC2H40CC8F'17 CI(2=CHO I I+ Co0C2H40CC2H4COOC2H4RfCH2
=CH ■ Co0C16H33 CH3 CH2-C ■ CONHC 8H37 CH3 E2 represents a heptavalent group derived from a radical moiety generated by chain transfer to a chain transfer agent.

E2 may be the radical moiety itself generated by chain transfer to the chain transfer agent, or it may be a radical moiety itself generated by chain transfer to a chain transfer agent, or it may be a radical moiety generated by chain transfer to a chain transfer agent, or it may be a radical moiety itself that is generated by chain transfer to a chain transfer agent, or it may be a radical moiety generated by chain transfer to a chain transfer agent, or it may be a radical moiety itself that is generated by chain transfer to a chain transfer agent, or it may be a radical moiety generated by chain transfer to a chain transfer agent, or it may be a radical moiety itself that is generated by chain transfer to a chain transfer agent.Also, as mentioned above for the oil-soluble polymer, E2 may be a radical moiety generated by chain transfer to a chain transfer agent. It may also be a group formed by the reaction of

2 carbon atoms used to obtain the water-soluble polymer of the present invention
Preferred examples of the above chain transfer agents are shown below, but are not limited thereto.

C2H55H, C3H75H, C4H95H.

BrCH2COOCH3, cgca2cα)C2H5.

ICH2COOCH3 In addition, the chain immobilizer (chain transfer agent with carbon number r or more, chain transfer agent having a group capable of reacting with a nucleophilic or >electronic reagent) mentioned in the oil-soluble polymer section, all water-soluble polymers. It is preferably used to obtain L.

Furthermore, as the chain transfer agent used in the water-soluble polymer of the present invention, a chain transfer agent having a group that is bonded to the binder directly or via a binder is often used.

Examples of these compounds are shown below, but are not limited thereto.

αCH2CH25O2CH2CONHCH2CH2SH
CH2=CH-8O2CH2CH2CONHCH2CH
2SH5HCH2CH2COOCH2CH2CN Furthermore, as the chain transfer agent used to obtain the polymer of the present invention, those containing a group that promotes the formation of a micelle structure are also preferably used.

Specific examples of preferable chain transfer agents for obtaining the polymer of the present invention that easily form a micelle structure are listed below, but the invention is not limited thereto.

C3F17CH2CH2S-H RfCH2CH2α:CH25-H I3 (However, Rf indicates CnF2n+1, n=A,!.

Average value for 10,/2 mixture? , jlLL. Rf described below also has the same meaning. ) RfCH2CH2S-H C8F17CONHCH2CH2S-HC8F17SO
2NHcH2CH2S-HC6F13CH2CH2S-
H 08F, 7CH2CH2SCH2CH2S-HC12F
25CH2C) (20CH2CH2S-HCBF 17
5O2NCH2CH2S-H direct 3H7 C6F13CH2CH20CCH2S-HI3 C3F17SO21'1JHC2H4NHC2H4NH
8O2C8H17C=0 Book H2SH C8F F502N-C2H4 Anti-CH25H■ CH2CH20CC8F07 C8H170C-CH-8)1 C8H170C-CH2 〇The "hydrophilicity" of the compound represented by the general formula [Q] means that it is diluted with distilled water at room temperature. Couplers that are soluble or obtained by polymerization reactions using monomers or chain transfer agents that promote micelle formation! This refers to the ability to stably emulsify and finely disperse in distilled water at a concentration of 1 or higher.

Examples of the hydrophilic polymer Kab2- used in the present invention are summarized in Table 3, but are not limited thereto.

Synthesis Example Copolymerization polymer coupler of α-piparoyl-α-(l/l-acrylamidophenoxy)-N-(s,!-dichlorophenyl)acetamide and non-acrylamide-comethylpropanesulfonate sodium coupler (TW
-2/') 22.0 g of coupler monomer (≠r), 20.0 g of sodium 2-acrylamido-2-methylpropanesulfonate.
OgX n-butyl mercaptanco.

A mixture of 200 mL of Og1 dimethylformamide was ro
Pour into an OmL Mitsuro flask and stir for 70 minutes in a nitrogen stream.
Heated to 0C.

Dimethyl azobisisobutyrate as a polymerization initiator! oomg
Polymerization was started by adding 10 mL of a dimethylformamide solution containing .

After polymerizing for 3 hours, the polymerization solution was cooled, 300 mL of water was added, dialysis was performed for 3 days, and TW-2/
j! , 3g was obtained.

Chlorine analysis revealed that this polymer contains coupler monomer units! ,! It was found that it contains %.

Compounds that do not react with the oxidized form of a developing agent to form a dye (hereinafter referred to as "ND compounds") that can be used in the present invention include A) at least 1
A strong electron donor (ED) capable of donating two electrons, B)
There are colorless couplers that perform a coupling reaction with T+.

A preferred ED compound has a partial structure represented by the following general formula.

Z'-(C=C)-Z5 CXX■:] 1n where n is an integer of /~μ, preferably/or z
4 and 25 are each independently -0H1-NH2, -N
Represents HR49, NR50R51, -NH8O2R52. R49 represents an alkyl group, R50 and R51 represent an alkyl group, or a group of atoms that together form a nitrogen-containing heterocycle, and R52 represents an alkyl group or an aryl group. When n is /, -C=C- may represent a partial structure of a benzene ring or a 7-talene ring. The alkyl group represented by R49 and RXRXR may be substituted, and examples of the substituent include a halogen atom and an alkoxy group.

Alkyl groups include straight chain or branched ones, preferably carbon number/or! It is individual. The aryl group represented by R52 also includes those having substituents, such as evaphenyl, alkoxy-substituted phenyl, alkyl-substituted phenyl, and the like. Examples of the nitrogen-containing heterocycle formed jointly by R50 and R51 include morpholino, bi for lysine, and py for radino.

Among the EDs represented by the general formula [XX■], preferred are hydroquinone compounds, catechol compounds, 0
-Aminophenol compounds, p-aminephenol compounds.

It is desirable that the hydroquinone compound that can be used as an ED compound in the present invention has low diffusivity when incorporated into the photosensitive layer. In particular, in photosensitive materials that have two or more photosensitive units sensitive to different spectral regions in the visible spectral region, such as subtractive color photosensitive materials, hydroquinone compounds that diffuse into different spectral units are Undesirable. Such hydroquinone compounds are widely used as color mixture inhibitors or color fog inhibitors in ordinary color sensitive materials or diffusion transfer color sensitive materials.

U.S. Patent No. 7 Cor. TR No. 2,73λ, 30
No. 0, No. 3. λ≠3. Linear alkyl di-substituted hydroquinones described in Kota≠, U.S. Patent No. 732.30
No. 0, No. 3.24t,...? , 22≠ No. 3, 7
00, ≠j3, Tokukai Sho! Ko-+♂lri issue, same! The branched alkyl di-substituted hydroquinones described in Gukota T37 have a low potential and are highly active as T+ scavengers, so they are preferred hydroquinones.

U.S. Patent No. λ, 7 pieces, O! No. 3, same No. 3. ! P60,
monolinear alkylhydroquinones described in No. J70,
U.S. Pat. −
10bu 32nd issue, same! Monobranched alkylhydroquinones described in Item 0-/Jr No. 3r, JP-A-10-31
The hydroquinones described in No. A≠, U.S. Patent≠, 3 Hiroyo, Otsu/Ao No., Dohiro, Core 7, Yo33 are also included in the ED of the present invention.
It can be used as

Next, specific examples of preferable dialkylhydroquinones used in the present invention are shown.

Q-/x, t-di-n-octylhydroquinone Q-, z s, t-di-n-dodecylhydroquinone Q-, ? 2. t-di-n-octylhydroquinone Q-≠ x, t-di-t-pentadecylhydroquinone Q-s λ,! -G5ee-Dodecylhydroquinone Q -12,! -G7-Dodecylhydroquinone Q-72,! -G5ec-Octylhydroquinone Q-♂ -2! -di-t-octylhydroquinone Q-ta 2. t-di-t-octylhydroquinone A particularly preferred ED for use in the present invention has the following general formula (
XX■] and CXX■].

(In the formula, R53 is a linear or branched alkyl group having carbon number/~l♂): an alkyl ester of gallic acid;
Examples include the following:

A/ Gallic acid methyl ester A,2 Gallic acid ethyl ester A3 Gallic acid n-propyl ester A≠ Gallic acid isopropyl ester A! Gallic acid n-butyl ester A7 Gallic acid isoamyl ester A7 Gallic acid d-amyl ester Alr Gallic acid n-hexyl ester A gallic acid n-heptyl ester A10 Gallic acid n-octyl ester A// Gallic acid n-nonyl ester A
/-2 gallic acid v --7' syl ester A/3 gallic acid n-hendecyl ester A/≠ gallic acid n-dodecyl ester A/! Gallic acid n-tetradecyl ester A/4 Gallic acid n-hexadecyl ester A/4
7 Gallic acid n-octadecyl ester where H54,
R55 each represents a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heterocycle. R54 and R55 may form a ring. R54
and R55 do not take a hydrogen atom at the same time.

In the general formula CXX■, the aliphatic groups for R54 and R55 include a straight-chain or branched alkyl group, a straight-chain or branched alkenyl group, a cycloalkyl group, and a straight-chain or branched alkynyl group. .

The number of carbon atoms in the straight chain or branched alkyl group is /~3
0. Preferably /-, 20, such as methyl, ethyl, propyl, n-butyl, SeC-phthyl, t-7'
tyl, n-hexyl, 2-ethylhexyl, n-octyl, t-octyl, n-dodecyl, n-hexadecyl,
Examples include n-octadecyl, instearyl, and eicosyl.

Examples of straight-chain or branched alkenyl groups include those having 2 to 3θ carbon atoms, preferably 3 to λO, such as allyl, butynyl, prenyl, octenyl, dodecenyl, and oleyl.

Examples of the cycloalkyl group include 3- to 2-membered, preferably 7- to 7-membered groups, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclohexyl, and cyclododecyl.

Straight-chain or branched alkynyl groups include those having 3 to 30 carbon atoms, preferably 3 to λ, such as propargyl or butynyl.

Examples of the aromatic group for R54 and H include phenyl and naphthyl.

Examples of the heterocycle for H54 and R55 include thiazolyl, oxasilyl, imidazolyl, furyl, thienyl, tetrahydrofuryl, piperidyl, thiadiazolyl, oxadiazolyl, benzothiazolyl, benzoxasilyl, benzimidazolyl, and the like.

R and R form a ring with 3 to 2 members.
,Preferably! ~/2, such as ethylene, tetramethylene, hantamethylene, hexamethylene or dodecamethylene.

Furthermore, each of these groups may have a suitable substituent,
Examples of the substituent include an alkoxy group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a carboxyl group,
Examples include sulfo group, cyan group, alkyl group, alkenyl group, aryl group, alkylamino group, arylamino group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, acyl group, sulfonyl group, acyloxy group, and acylamino group.

Specific examples of the compound represented by the general formula [Ω1] are shown below, but the invention is not limited thereto.

Compound example B-/ B-co -J B-μ -t Shiku JNHl; 4 M 9 (n)-P UNM(niM2J3(JU12M25(season B-/.

B-／　／ B-/ko 0H B-／　≠ B-／Yo H B-/l.

B-/7 -7 r B-/7 B-1 to -26 (,,:(JNH(ni,t'i2)a to 1-1-(:
(JB-27 B-2r B-Kota Particularly preferred ED compounds for use in the present invention include compounds represented by the following general formula [XX■].

¥6 In the formula, R56 represents a hydrogen atom or a group that can be hydrolyzed by an alkali. Y2 is hydroxyl group □ R57 (R57
represents a hydrogen atom, a group hydrolyzable by an alkali), or a sulfonamide group.

In the formula, X5 represents a substituted or unsubstituted alkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amide group, or sulfonamide group. R58,
R59 represents the same group as X5, or a hydrogen atom, a halogen atom, a sulfo group, a carboxyl group, a substituted or unsubstituted carbamoyl group, a sulfamoyl group, an acyl group, or a sulfonyl group. R58 and R59 may jointly form a carbon ring.

The general formula [XX■] will be explained in more detail below.

In the above general formula [XX■], R56, R57 (y
Examples of the substituent (Example 2) which is a group that can be hydrolyzed by an alkali include an acetyl group, a trichloroacetyl group, an ethoxycarbonyl group, a benzoyl group, and the like.

X5 is a substituted or unsubstituted alkyl group (number of carbon atoms/~tO
0 For example, methyl group, t-butyl group, n-octyl group,
t-octyl group, 5eC-octyl group, decyl group, 3e
C-dodecyl group, goohexyloxycarbonyl-/,/
-dimethylbutyl group, 5ee-octadecyl group, t-pentadecyl group, sulfoalkyl group (e.g. l,l-dimethyl-cosulfoethyl group), carboxyalkyl group (e.g. !-carboxy is methyl group), alkoxy group (number of carbon atoms/~lO0, e.g., methoxy group, methoxyethoxy group, dobucyloxy group, etc.), aryloxy group (number of carbon atoms +-to, e.g., phenoxy group, ≠-methoxyphenoxy group), alkylthio group (number of carbon atoms/~ to
0 e.g. butylthio group, dodecylthio group), arylthio group (carbon number 6-600 e.g. phenylthio group, 2
-octyloxy-t-t-octylphenylthio group, etc.), amide group (carbon number λ to 0, e.g. acetylamino group, benzoylamino group, terbis(norhexyldecanamide) benzoylamino group, α-(,2 ,≠−
t-amylphenoxy)dutanamide group, etc.), and a sulfonamide group (carbon number/~O00, e.g., inzenesulfonamide group, Hiro-octadecyloxybenzenesulfonamide group, hexadecanesulfonamide group, etc.).

R58 and R59 are the same groups as X5, hydrogen atom, halogen atom, sulfo group, carboxyl group, substituted or unsubstituted carbamoyl group (carbon number/~100, e.g. carbamoyl group, N,N-dipropylcarbamoyl group, N -phenylcarbamoyl group), sulfamoyl group (carbon number θ to tO0, e.g. sulfamoyl group, N,N-dihexylsulfamoyl group, N-phenylsulfamoyl group, etc.), acyl group (carbon number λ to tO0, e.g. acetyl basis,
benzoyl group, 3-carboxypropanoyl group, etc.),
Sulfonyl group (number of carbon atoms/~tO0, such as methanesulfonyl group, benzenesulfonyl group, dobusyloxybenzenesulfonyl group) Table t) f. R1R59 may jointly form a carbon ring.

Y2 represents a hydroxyl group 0R57 or a sulfonamide group, and the total number of carbon atoms in X5, R58, R59, and Y2 is 10 or more.

The compound of general formula [XX■] may form a bis-form, a tris-form, an oligomer, a polymer, etc.

X5 is preferably a substituted or unsubstituted alkyl group, alkylthio group, amide group, or sulfonamide group, and more preferably a substituted or unsubstituted alkyl group or amide group.

Preferred as R56 is a hydrogen atom, R58,
R is preferably a hydrogen atom, a halogen atom, a sulfo group, an alkyl group, an alkylthio group, or a sulfonyl group, and more preferably a hydrogen atom, a halogen atom, an alkyl group, or a sulfonyl group. .

Y2 is preferably a hydroxyl group.

The compound of the general formula [XXIX:) according to the present invention is disclosed in JP-A-Sho! ! -320, 3rd issue, same! ! -! ! r/2/ issue, same!
Tarj,, 2≠No. 7, special request Akiotsu/-/, 73/.

No. 701, British Patent No. ♂/, LRR, US Patent No. 2
, 701, No. 7, etc., and a method analogous thereto.

Specific examples of the compound of the general formula [Xx■] used in the present invention are shown below, but the present invention is not limited thereto.

Q-/.

H Q-// Q-/koichi73 Q-/guH Q-/yoQ-/ottoH Q-/riQ-koO H Q-sλ Q-,23 H Q-,2guQ-λj Q-λt Q-,27 6H13 Q-2? H Q-Kota Q-3゜Q-3/ Q-3koQ-3μ Q-3! -1r H3 Q-≠0 Q-t, t / Q-≠koQ-≠3 Q-≠Hiroshi Q-≠YuQ-gut Q-≠7 Q-gr Q-Hori ND compound in the present invention A colorless coupler used as a color developing agent couples with the oxidized form of a color developing agent, but ■ remains in the leuco form; ■ a colored dye is formed once, but decomposes during development or in a post-processing bath. become colorless,
(2) This is a coupler that does not produce colored pigments in the photosensitive material layer because the colored pigments produced are soluble in water and therefore elute into the processing solution.

These colorless couplers are disclosed in the following documents. Pyrazolone, x-enzoyl acetate, as described in British Patent No./4j, /116;
Turnip 2- in which the hydrogen atom of active methylene such as benzoyl acetanilide and acetoacetanilide is substituted with a substituted alkyl or substituted allyl group; British Patent Column 1,2! Hiroshi, 2
A coupler in which the ≠-position of the pyrazolone is substituted with a methyl group, ethyl group, or cyanethyl group as described in JP-A-Sho! 10-1303/, the hi-position is substituted with an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and the 3-position is substituted with a substituted acylamide, and the coupling activity is improved. ,! −
All pyrazolone type couplers belong to the above type (■).

Furthermore, as belonging to the above ■, special public Shogu A-2,
2jt/≠, acyclic ketone type colorless DIR coupler or Tokkosho! There are cyclic ketone type colorless DIR couplers as described in /-/A/≠/, and those that belong to ■ include the couplers described in U.S. Patent Nos. There is.

The polymer coupler of the present invention may be prepared as a latex by an emulsion polymerization method, or it may be obtained as a linear polymer by a solution polymerization method and then used by emulsifying and dispersing it in an aqueous medium.

The polymer coupler of the present invention and the ND compound are preferably contained in the same silver halide emulsion layer. When there are multiple emulsion layers with different sensitivities, it may be used in any layer. Graininess is easily noticeable in the medium density range, so when there are three emulsion layers with different sensitivities, it is preferable to contain it in the medium speed layer. The polymer coupler and the ND compound may be emulsified separately or co-emulsified. Polymer couplers and NDs
The compound can be introduced into the hydrophilic colloid layer according to a conventional method.

In the present invention, the ND compound has a θ of 001 to 0.5 per mole of effective color-forming coupler residue of the polymer coupler.
molar used. The appropriate ratio depends on the relative coupling rates of both to T+, but the usual preferred range is from about 1 to about 20 moles of chromogenic coupler residue in the polymeric coupler. If the upper limit is exceeded, adverse effects such as a decrease in color density will occur, and if it is lower than the lower limit, the effect will be relatively small. Incidentally, even if the ND compound is added to a layer adjacent to the polymer coupler, such as a non-color-forming intermediate layer, there is an effect of improving graininess, but it is not as noticeable when added in the same layer.

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 iodochlorobromide, which contains about 30 mol% or less of silver iodexide. be. Particularly preferred is silver iodobromide containing from about 2 mole percent to about 25 mole percent 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 with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a polydisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD),
(December 1978), pp. 22-23, '■, Emulsion preparation and
N118716 (19
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, Glafkid
es.

Chemic et Ph1sique Pho
tographique Paul Montel
.

1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, Duffin, Photog)
rapicEmulsion Chemistry
(Focal Press+ 1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikman et al., M.
akingand C: oating Photogr
aphic Emulsion, Focal Pre
ss.

(1964) and others.

U.S. Patent Nos. 3,574,628 and 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 in Cutoff, Photographic Science and Engineering.
ence and Engineering), No. 14
Vol. 248-257 (1970): U.S. Patent No. 4,
434゜226, 4,414,310, 4,4
33.048, British Patent No. 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be --like, or it may have a layered structure in which the inside and outside have different halogen compositions, or it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as rotane silver 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 enhancement. Additives used in such processes are subject to research disclosure restrictions17.
643 and 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.

l Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity increasing agents
Same as above 4 Brightening agent page 24 8 Dye image stabilizer page 25 9 Hardening agent page 26 Page 651 left column 10
Binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column Preventive agent Various color couplers can be used in the present invention, and specific examples thereof can be found in the aforementioned Research Disclosure (
RD) No. 17643, ■-〇-G.

As a yellow coupler, for example, U.S. Patent Box 3.93
3.501, 4.022.620, 4.3
No. 26,024, No. 4.401゜752, Special Publication No. 5
B-10739, British Patent No. 1,425,020,
No. 1,476.760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
0,619, 4,351°897, European Patent Box 73,636, US Patent Box 3,061,432, 3. 725. No. 067, Research Disclosure m24220 (June 1984), JP-A-1986-
No. 33552, Research Disclosure m242
30 (June 1984), JP-A No. 60-43659,
U.S. Patent Box 4,500,630, U.S. Patent No. 4,540.6
Particularly preferred are those described in No. 54 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent Box 4°052.212.
No. 4,146,396, No. 4.228.23
No. 3, No. 4. 296. No. 200, No. 2.369
, No. 929, No. 2,801.171, No. 2,77
No. 2,162, No. 2,895,826, No. 3. ．．
No. 772.002, No. 3,758,308, No. 4
, No. 334.011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121.
No. 365A, U.S. Patent Box 3.446,622, U.S. Patent No. 4
, 333,999, 4,451.559, 4,427,767, European Patent No. 161,626A, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent Box 4,163゜670, Special Publication No. 1983
No. 39413, U.S. Patent Box 4.004. '929,
No. 4,138,258, British Patent No. 1,146,3
The one described in No. 68 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4.3'66.237 and British Patent No. 2,12.
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.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

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. 3!13- No. 4,310,61
Multi-equivalent coupler described in No. 8 etc., JP-A-60-1859
50, DIR redox compound or DIR coupler releasing coupler or D described in JP-A-62-24252 etc.
IR coupler-emitting coupler or redox, a coupler that releases a dye that recolors after separation as described in European Patent No. 173,302A, R, D, Magnetic 11449, European Patent No. 2424
1. Bleach accelerator-releasing couplers described in JP-A No. 61-201247 and the like; Gantt-releasing couplers described in U.S. Pat. No. 4,553,477 and the like.

Specific examples of color couplers that can be used in the present invention are listed below, but the invention is not limited thereto.

C-(2+ C-(31 C-+41 C+51 I C-+61 +011 CIl±T-1110C11, -CI+±
+ CII t -CI Todo, Molecular weight approximately 40,00
0 C-(71 CHs COtCmll*C-
+81 C-f9+ c-aal C-0υ N C-□□□ Kano■ Cs1l+t(L) C-Q'5 H -a41 H (+) and #■Dropυ UNI -aS C11゜+CI+! -C÷Tconau C11! -CII ÷r
C-aη 0]1 SCIhCHzCOtll C1 OH C@ll+t(t) C-θ cheerbukoNa CIl,
C11゜C-+211 0■ υ ClA＼ C-(2) C11゜C-(24) c-(25) C-(26) e C-(27) C-(2B) C-(29) C -(30) C-(31) C-(32) Ward 0CHICHICONHCH, CII□0CIIffC
-(33) C= (34) C-(35) C-(36) C-(37) C-(38) C1゜11,1 C-(39) 〼E C-(40) II β C '-(41) ■ C-(44) C-(45) I C-<46) C-(47) I C-(4B) O1+ c-(49) C-(50) C-(51) C -(53) IC-(54) c-(55) c-(56) C-(57) C-(58) C12 C-(59) C-(60) Coupler used in the present invention can be added to light-sensitive materials using various known dispersion methods.

Examples of commercial boiling point solvents used in the oil-in-water molecule lk method are described in U.S. Pat. No. 2,322.027 and others.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl chloride, Decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di[-amylphenyl) isophthalate, bis(l,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid Acid esters (trifel phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate,
dodecylhenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N-diethyldodecaneamide, N,N-diethyllaurylamide,
N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-
tert-amylphenol, etc.), aliphatic carboxylic acid esters (his(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N -dibutyl-
2-butoxyl 5-tert-octylaniline, etc.)
, hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C.
Any organic solvent having a temperature above about 160° C. or below can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat. It is written in the number etc.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of m17643, and 6 of 1B716
It is described from the right column on page 47 to the left column on page 648.

The color photographic light-sensitive material according to the present invention is described in the above-mentioned RD, pages 28-29 of 17643, and 6 of 18716.
51. Development processing can be carried out by the usual methods described in the left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3°-methyl-4-amino-N,N-diethylaniline, 3 -Methyl-4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-)luenesulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds, or It generally contains antifoggants and the like. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo [2゜2.2]
various preservatives such as octane), ethylene glycol,
Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, l-phenyl-3-pyrazolidone. Auxiliary developing agents, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriamine Pentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-1-
Rimethylenephosphonic acid, ethylenediamine-N,N.

Representative examples include N',N'-tetramethylenephosboxylic acid, ethylene diamine di(O-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-virapritones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but -a is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500 m2
It can also be less than β. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or may be carried out separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a qualitative bleaching treatment. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (Il).
Compounds of polyvalent metals such as chromium (■), copper (n), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobal (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.: persulfates: bromates; permanganates; nitrobenzenes, etc. can be used. . Among these, aminopolycarboxylic acid iron (l[l) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (m) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. ) Complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(I[I) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH is lowered. You can also do that.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059°988, JP-A No. 53-32,736, No. 53-57,831, No. 5
No. 3-37,418, No. 53-72.623, No. 53
No. -95,630, No. 53-95,631, No. 531
No. 0.4232, No. 53-124,424, No. 53-
No. 141.623, No. 53-28.426, Research Disclosure No. 17,129 (July 1978)
Compounds having a mercapto group or disulfide group as described in JP-A-50-140-129; thiazolidine derivatives described in JP-A No. 45-8,506 and JP-A-Sho 52-20,832 , No. 53-32,735, thiourea derivatives described in U.S. Pat. No. 3.706.561; West German Pat.
Iodide salt described in No. ゜235; West German Patent No. 966゜41
Polyoxyethylene compounds described in No. 0 and No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and others described in Japanese Patent Publication No. 49-42.434 and No. 49
-59,644, 53-94,927, 54-
No. 35,727, No. 55-26,506 No. 58-16
Compounds described in No. 3,940; bromide ions, etc. can be used.

Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred in the United States.
Patent No. 3,893.858, West Patent No. 1,290,81
No. 2, JP-A No. 53-95,630 are preferred, and compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium 100sulfate is the most common. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

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, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tjon Ptc, ture and Televis
ion Engineers Vol. 64, p. 248-25
3 (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. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions, magnesium, and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8.54
Chlorine-based disinfectants such as isothiazolone compounds and cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in No. 2, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, and "Microorganisms" edited by Sanitation Technology Association. It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society of Antibacterial and Antifungal Agents.

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 variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C is selected. Furthermore,
The light-sensitive 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. 57-8.543 and 58-14.8
All known methods described in No. 34 and No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342,59
No. 7 i! L! Acupuncture indo-I niline compound, same No. 3, 3
No. 42,599, Research Disclosure 14,
Schiff base-type compounds described in No. 850 and No. 15,159, aldol compounds described in No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 3-135,628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64,339 and JP-A-57-144,547.
No. 58-115.438, etc.

Various treatment liquids in the present invention are used at 10'C to 50'C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can do. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
Thermal development 1 described in No. 9-218443, No. 61-238056, European Patent No. 210,66082, etc.
It can also be applied to 8 Kozuki charges.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example / On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/m2 of silver for silver halide and colloidal silver, and the amount expressed in g/m2 for couplers, additives and gelatin. The sensitizing dye is expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver O9,2 gelatin /, 3ExM-2...
・ θ, Otsu UV-/ ... θ, 03UV-2
... o, ot UV-J ---o, oaSolv
-/... 0. /! 5olv-2-
−−0,/! 5olv-3・-・0.0! 2nd layer (middle layer) Gelatin /, 0UV-/
... 0.03ExC-μ
... 0.0 CoE x F −/
...0.00 hiro5olv-/
... 0. /S o 1 v-, 2o
, / Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgIe morti, uniform-Agl type, equivalent sphere diameter o, rμ, coefficient of variation of equivalent sphere diameter 20 inches, plate-like grain, diameter/thickness Ratio 3.0) Coated silver amount... /, - Silver iodobromide emulsion (Ag Thickness ratio/, O) Coated silver amount... o, t Gelatin i,.

E x S −/ ・・・≠×1O−
4FJxS-2...rx1o-sE
x C-/...0.0Ex
C-2・ ・ ・ O, yo 0 ExC-3・--o, o 3 ExC-Hiroshi ・ ・ ・
0.1 KoEx C-!
・ ・ ・ o, oiEx C-1 ・ ・ ・
0.03rd ≠ layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mole, core-shell ratio /: / internal high AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of sphere equivalent diameter /!chi) , plate-shaped particles, diameter/thickness ratio!, O) Coated silver amount... 0.7 Gelatin /, 0ExS-
/...EXlo-4ExS-2...
・K, 3X10-5 E x C-l= ... O01
/B x C-7... 0.02 ExC-≠... 0.0 5olv
-/ ---0,0!5olv-J
---0, Oj jth layer (intermediate layer) Gelatin ... 00ICpd
-/0. /5o
lv-/ --・0.0! Second layer (
Low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI≠molti, core-shell ratio /:/ surface height AgI type, equivalent sphere diameter 0.jμ, coefficient of variation of equivalent sphere diameter /!chi, plate-like grains, diameter / Thickness Hihiro, O) Coated silver amount... 0.3! Silver iodobromide emulsion (AgI 3 molti, uniform AgI type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 2!chi, spherical grains, diameter/thickness ratio/, O) Amount of coated silver... 0. 20 Gelatin /, 0ExS-
J ・-r×y o-4ExS-Hiroshi...J×1O-4ExS-!
.../×10-10-4Ex
... O1≠ExM-y
−・・ 0.07ExM−10… 0.02 ExY−// ・ ・ ・
0.03Solv-/
0.3Solv-p
---o, or 7th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgIII morch, core-shell ratio/;3
Internal high Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter -0%, plate-like particle, diameter/thickness ratio, o) Coated silver amount... 0. ♂ Gelatin O9! ExS-
J...-z×1O-4ExS-ti
-・-JX/o-4ExS-!
.../X/0-' 4ExM-J
l O,/ExM-ta
・ ・ ・ 0.0λExY−//
-・-o, o3ExC-2... 0
．． OJ ExM-/≠ ・・・ 0.0≠5olv
-/0.2Solv-p
---o, ol rth layer (intermediate layer) Gelatin ,,, 0-jCpd
-/ ・ ・ ・ o, or
Solv-/ ---0,02 7th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (
AgI2 morch, internal height AgI type with core-shell ratio 2: /, equivalent sphere diameter /, 0 μ, coefficient of variation of equivalent sphere diameter / jq6, plate-shaped particles, diameter / thickness ratio X, O) Coated silver amount... 0. 3! Silver iodobromide emulsion (AgLJ morch, internal high AgI type with core-shell ratio /:/, equivalent sphere diameter O1≠μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter/thickness ratio 6, O) coated silver Amount... O, CoO Gelatin... o, rExS-
3---r×1O-4 ExY-I3...O8//Ex
M-I2 --- 0.03ExM-/
≠ ... 0.105olv-/
・--0.2゜ 1st O layer (yellow filter layer) Yellow colloidal silver ... o, or gelatin 0. jcpa-λ
・ ・ ・ O013Solv-/
・--0, /jCpd-/
・ ・ ・ o, i.

1st/Layer (Low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI≠, tamolti, uniform AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter/jchi, plate-like grain, diameter /thickness ratio 7.0) Coated silver amount... 0.3 Silver iodobromide emulsion (AgIj morti, uniform AgI type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 2!, plate-like grains , diameter/thickness ratio 7.0) Coated silver amount... 0. /! Gelatin /, 4ExS-
6-・-x×to-4 EXC-/l −・・0. Ex to O
C-co... o, i.

ExC-J ・ ・ ・
0.02ExY-I3 ・
・ ・ 0.07ExY-/z
/ ,.

5olv-/ ・--o, s
.

1st co-layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 molti, internal high AgI type, equivalent sphere diameter i, oμ, coefficient of variation of equivalent sphere diameter 23%, multi-twinned plate-like grains, diameter /thickness ratio λ.

O) Coated silver amount...Olj Gelatin...0,! Ex
S-A.../X/l:)-4E
xY-/j...0.20ExY-
/J...-o, o/5olv-/
---o, /.

13th layer (1st protective layer) Gelatin 09rUV-4
to, /UV-J-...
・O9/! 5olv-/-・・0.07Sol
v-2-・-o, ot 74th layer (second protective layer) Fine grain silver bromide emulsion (AgI2 morch, uniform AgI type, equivalent sphere diameter 0.07μ)...0. j gelatin
... O3≠! Polymethyl methacrylate particle diameter/, jμ O, coH-10.
Cpd-to, rCpd
-J O,jtcpct-
♂ 0.2 Each layer contains emulsion stabilizer Cpd-3 (0,041 g/m
2) Surfactant Cpd-≠(O, 0.2 g/m2) was added as a coating aid.

Bu UV-2 UV-3sec n UV-≠ CH3CH3 UV-r 5olv-/ Tricresyl phosphate 5olv-λ Dibutyl phthalate Solv-3 Solv-≠ Cp d -/ 6H13 ■ pd-2 pd-7 pd-3 cpa- ≠ Cp d−j Cp d−
ACpd-J' C=0 Overturn H2 E x C-/ xC-2 I E x C-j S(,"l-12(,:H2UU2CH3ExC-≠ EXC-J' Ex C-! CH2 Ex C- A CH2 C(CH3)3 ExC-7 H xM-1 m=+2 yo m'=koj mol, wt, approximately +20.000 ExM-ta α xM-10 ExY-// ExM-/, 2 ExY-/ J Ex M-/ ≠ ExY-/! ExC-/A ExS-/ ExS-λ ExS-3 ExS-HiroE x S-! ExS-1゜H-/ CH2=CH-802-C )(2-CONH-CH2C
H2=CH-802-CH2-CONH-CH2=CH
-/C2H5U2ti5 Preparation of Samples 102 to //j Instead of ExM-♂ added to the third and seventh layers of Sample 101, comparative couplers, couplers of the present invention, and ND compounds as shown in Table 1 were used. Sample 101 other than quantitative addition
Created in the same way.

The ND compound was dissolved and emulsified together with the coupler before use.

The sensitivity and gradation of the obtained samples were almost the same.

Next, the RMS graininess and MTF value of these samples were measured. For more information on these, see T. H. James, ed. 1 The
Theory of PhotographicPro
It is described in detail in the cessJ edition.

Furthermore, after wedge exposure of these samples, 0C10% of 4t
The samples were stored in an RH atmosphere for 3 days and their latent image stability was compared.

The results are shown in Table/.

The development process was performed in the following steps.

Table - Processing method Step Processing time Processing temperature Color development 3 minutes/! seconds 3r 0c bleach
/minoo seconds 3r 0c bleach fixing 3min/j
Seconds 3r0c Washing (1) Dao seconds 3!0C Washing (2)/min oo seconds 3r0c Stable ≠θ seconds 3r 0c Drying
7 minutes 73 seconds 3500 Next, the composition of the treatment liquid will be described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid /,01-hydroxyethylidene-1,/-diphosphonic acid 3.0 Sodium sulfite Hiroshi, O Potassium carbonate
30.0 Potassium Bromide
/,≠potassium iodide
/,! ; mg hydroxylamine sulfate co, ≠≠-(N-ethyl-N-β-hydroxyethylamine) -λ-methylaniline sulfate μ,! Add water /, Olp H/
0, Oj (White liquid) (Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate/20.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide ioo.

Ammonium nitrate 10.0 bleach accelerator o, oor mol ammonia water (
7) /z, add oml water
/・O1pHA, 3 (bleach-fix solution) (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate ro.

Ethylenediaminetetraacetic acid disodium salt! , O sodium sulfite /2. O ammonium thiosulfate aqueous solution (70%) 0.0 ml ammonia water (27%) b. Add Oml water /, 0 l pH 7.2 (Washing liquid) Tap water to H-type strongly acidic cation exchange resin (Rohm and Haas) Water was passed through a mixed-bed column filled with Amberlite IR-/2oB) and an OH-type anion exchange resin (Amberlite IR-μ00) to reduce the concentration of calcium and magnesium ions to below jmg/l. , followed by 20 mg/l of sodium isocyanurate dichloride and sodium sulfate/! Omg/l was added.

The pH of this solution is 1. ,! -7.3 range.

(Stabilizer) (Unit: g) Formalin (37%) 2. om);3
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 ethylenediaminetetraacetic acid disodium salt o, or with water /, 0lpHj, 0-1.
As is clear from Table 0, the combination of the coupler of the present invention and the compound significantly improves the graininess sharpness and the decrease in sensitivity during latent image storage.

(Example 2) A color photographic material was prepared by coating the following layers from the first layer to the first ≠ layer on a triacetate base, and sample-Ol
And so.

(Photosensitive layer composition) The components and coating amount in units of g/m2 are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

1st/[1 (antihalation layer) Black colloidal silver...0.30 Gelatin...-, r.

UV-／・・・0.0UV
-2... 0.10 UV-J... 0010Sol
v-/...-0, 10th λ layer (intermediate layer) Gelatin... o, t.

3rd layer (low sensitivity red sensitive layer) Monodispersed silver iodobromide emulsion (AgI≠Morti, cubic, average grain size 0.jp, s/r=o, /r)...
0,! 0 ExS-/ -・-/ , ao×1O-3
ExS-2・--A, 00×70 5 gelatin
... 0. ♂0ExC-/
・-・ o, s.

ExC-2... o, i.

5olv-2---0,10 1st layer (medium-sensitivity red-sensitive layer) Monodisperse silver iodobromide emulsion (AgI=2.!molti, /monohedral, average grain size o, prμ, s/r=o , is)
・ ... o, r.

ExS−/ −−−/ , tO×1O−3Ex
S-+z・--A, 00×10-5 gelatin...i, o.

E x C-/ ... 0.3θ
ExC-2...0. /! 5olv-2---0,20th! Layer (high-sensitivity red-sensitive layer) Monodispersed silver iodobromide emulsion (Agl=, 2.J-molti, /ghedral, average grain size o, toμ 3/r=o, /j)
・ ・ ・ 0. ．． 30ExS-/
−・ −/ , tO×1O−3Ex
S-2---6,00×10-5 Gelatin...0.70EXC-
/...-0,20ExC-ko
...0.10Solv-2・-・0. /
2nd layer (middle layer) gelatin i.

Cpd-/ ・ ・ ・ 0
．． /5olv-t -・-o, o3So
lv-x ・--o, oza5OIV-j
・・−0,/2Cpd −,2・・
・0.2! 7th layer (low sensitivity green sensitive layer) Silver iodobromide emulsion (), gI = 3.0 molt, normal crystal, mixed twin crystals, average grain size 0. jp) ・ ・ ・ O, Otsu! EXS-J ---J, 30×1O-3Ex
S-a---7,5ox10-3 gelatin
... /, 50ExM-/
... OoloExM-2... 0.
2! 5olv-,2--・0.30 rth layer (high sensitivity green sensitive layer) Tabular silver iodobromide emulsion (AgI=x, rmolch, grains with a diameter/thickness ratio of 5 or more have a projected area of all grains Average particle thickness Q, /!μ)・・・・0.70 ExS-3−・i, 3o×1O−3ExS−≠
...! , 00x10-4 gelatin
... i, o.

ExM-J...Ol,! TaC
pd-j ・ ・ ・ 0.1
0Cpd-Hiro... 0.02So
lv-s ---o, or second layer (intermediate layer) Gelatin...0.10 1st O layer (yellow filter layer) Yellow 50a)' Silver ---0,10 Gelatin... /, 00Cpd −／
・ ・ ・ 0.0!5olv
−/ −・−0,03Solv−λ
・・・ 0.07Cpd-2・ ・ ・
0. IO 1st/layer (low sensitivity blue sensitive layer) Silver iodobromide emulsion (Ag I=-2, j-molti, normal crystal, mixed twin crystal, average grain size 0.7μ) ・ ・ ・ O,! ! ExS-j ... / , 00 x 10-3 gelatin ... Olli OE x Y
-/... o, r.

5olv-,2-・-o,i.

12th layer (high-sensitivity blue-sensitive layer) Tabular silver iodobromide emulsion (AgI = 2.j morch, grains with a diameter/thickness ratio of 5 or more are !Ox of the projected area of all grains, average thickness of grains O8/3μ) ・ ・ ・ / , 0
0 ExS-r ... / , 70 x 10-3 gelatin ... 2.00E x Y-
／ ・ ・ ・ ／ , θ
θ5olv-2---0,20 73rd layer (ultraviolet absorption layer) Gelatin... /,! 0UV-/
...0.0λUV-λ
... 0.0 Hiro UV-J
...0.0gCpd-s
・ ・ ・ 0. J(7Solv-/
-・-0,30Cpd-B
・ ・ ・ 0.10 1st ≠ layer (storage layer) Fine grain silver iodobromide (1 molch of silver iodide, average grain size 0.10)
0jμ) ... 0110 gelatin
... Ko, 00I(-/
... 0.30E x S -/ ExS -! E x S -3 ExS-g o3- E x S -j +.

N(C2Hs)a V-t UV-2 UV-j H2CH3 Cpd-2 Polyethyl acrylate Cpd-G H Cpd-I Cpd-A Ex C-/ (Sushi5h11 ExC-λ Ex M-/ Ex M- j H3 ExY-/S o 1v/Nidibutyl phthalate 5olv
-,! :), licresyl phosphate 5olv-3H trinonylphos 7ate H-/:/, 2-bis(hinylsulfonylacetamido)ethane sample-02~, 2coO In sample 201, 3rd to 3rd layers Added E x C
-/, F, x It was prepared in the same manner as Sample 201 except that C-2 was changed to comparative coupler A as shown in Table 2, and the coupler and compound of the present invention.

The sample obtained was 201~2/! The test was conducted in the same manner as in Example. As a result, as in Examples, only the combination of the present invention had excellent grain sharpness and less desensitization during latent image storage. In addition, Sample 2/Otsu-2.20 had extremely low color development.

The processing steps used here are as shown below.

Processing process Time Temperature 1st development Minutes 3♂0C First water washing ≠3 seconds 3♂00 Inversion! 3 seconds 00 color development
4 seconds 3♂0C bleaching 2 seconds 3r 0C bleach-fixing ≠ seconds 3r0C Second washing (1) 7 seconds 3!0C Second washing (2) 7 seconds 3r 0c The composition of each treatment solution was as follows. .

First developer nitrilo-N,N,N-trimethylenephosphonic acid j sodium salt co,og sodium sulfite 30g hydroquinone.
Potassium monosulfonate 20g Potassium carbonate 33g/-Phenyl-
≠-Methyruderhydroxymethyl-3 -Pyrazolidone 2.0g Potassium bromide 2.5g Potassium thiocyanate /,, 2g Potassium iodide
pH was adjusted with hydrochloric acid or potassium hydroxide.

First washing solution mother liquor Ethylenediaminetetramethylenephosphonic acid λ, Og Conosodium phosphate 3.0g Add pure water
1000100OH7.00 pH was adjusted with hydrochloric acid or hydroxide).

Reversal liquid nitrilo-N,N,N-)rimethylenephosphonic acid! Sodium salt 3.0g stannous chloride-water salt /, Ogp-aminophenol 0.7g sodium hydroxide
2g glacial acetic acid
16ml pHA, 00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer two trilo-N, N, N-)
Rimethylenephosphonic acid! Sodium salt 2.0g Sodium sulfite 7.0g Trisodium phosphate dihydrate 3Ag Potassium bromide /, 0g Potassium iodide Taomg Sodium hydroxide j, 0g Citrazic acid
/, 5gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-≠-amine aniline sulfate iigJ, A-dithiaoctane-/.

? -diol /, 0gpH//
, l'O pH was adjusted with hydrochloric acid or potassium hydroxide.

Bleach solution ethylenediamine ≠ acetic acid, cosodium salt, λ water salt 10. Og ethylenediamine≠acetic acid/Fe(1)/ammonium/λ water salt 120g ammonium bromide 700g ammonium nitrate
10g bleach accelerator
o, oor molar pHt, 30 pH was adjusted with hydrochloric acid or aqueous ammonia.

Ethylenediamine≠acetic acid/Fe(II[)/ammonium/l hydrate! Og ethylenediamine≠acetic acid/λ sodium salt/l hydrate salt! , Og ammonium thiosulfate 10g sodium sulfite
/2.0gpHA, OtsuO pH was adjusted with hydrochloric acid or aqueous ammonia.

The second washing solution tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-720B manufactured by Rohm and Haas) and an OH-type strongly basic anion exchange resin (Amberlite IR-720B manufactured by Rohm and Haas) IRA-≠
Water was passed through a mixed bed column packed with 00) to reduce the total ion concentration to 3 mg/l or less, followed by 20 mg/l of sodium isocyanurate dichloride and sodium sulfate/
! ; Omg/l was added.

The pH of this liquid is in the range of A, t-7,j.

Stabilizing liquid formalin (37%) r, oml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.6 ml Pure water without pH adjustment is water that has not been treated by distillation or ion exchange. The sum of all ion concentrations in
Indicates water with a concentration of ppm or less. In this experiment, pure water was created using an ion exchange resin as shown in the second washing water.

Claims (3)

[Claims] (1) At least one polymer coupler synthesized through a polymerization reaction using a chain transfer agent having a chain transfer constant of 0.01 to 50 is reacted with an oxidized product of an aromatic primary amine developer. A silver halide color photographic light-sensitive material characterized in that it contains at least one compound that does not form a dye in the same silver halide emulsion layer. (2) The silver halide color photographic material according to claim (1), wherein the polymer coupler is a lipophilic polymer coupler represented by the following general formula [P]. General formula [P] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ E represents a monovalent group with 8 or more carbon atoms. A represents a repeating unit derived from an ethylenically unsaturated monomer having a coupler residue capable of coupling with an oxidized form of an aromatic primary amine developer to form a dye. B represents a repeating unit derived from a copolymerizable ethylenically unsaturated monomer. X represents a monovalent group. x, y are the content of each repeating unit in the polymer coupler, and x and y
The weight ratio (x:y) is 10:90 to 100:0. (3) The silver halide color photographic light-sensitive material according to claim (1), wherein the polymer coupler is a water-soluble polymer coupler represented by the following general formula [Q]. General formula [Q] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ E^2 represents a monovalent group having 2 or more carbon atoms and derived from a radical moiety generated by chain transfer to a chain transfer agent. A is the same as above. B^1 represents a repeating unit derived from a copolymerizable ethylenically unsaturated monomer. X is the same as above. x and y are the content of each repeating unit in the polymer coupler, and the weight ratio of x and y (x:y) is 10:
The ratio is 90 to 100:0.