JPH01134358A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sensitivity and the coloring property of a photosensitive material, and to obviate the mixed color by incorporating a polymerized coupler obtd. by using a specified chain transfer agent. CONSTITUTION:The silver halide color photographic sensitive material contains a lipophilic polymer coupler (such as a compd. shown by formula I) having eight or more carbon atoms., obtd. by using the chain transfer agent (such as C12H25SH) having a chain transfer constant of 0.1-20 against a monomer coupler. In the formula, E is a monovalent group coming from a radical portion generated by said chain transfer agent, A is a repeating unit derived from an ethylenic unsatd. monomer (such as a compd. shown by formula II) having a coupler residual group capable of forming a dyestuff by coupling with the oxidant of an aromatic primary amine developing agent, B is a repeating unit derived from a copolymerizable ethylenic unsatd. monomer, X is a monovalent group, (x) and (y) are each a percentage of each units.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an I silver halide color photograph containing a novel color image-forming coupler capable of coupling with an oxidized product of an aromatic primary amine developer. It relates to photosensitive 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, with a silver halide emulsion that is selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image formers that have a relationship with the extra colors, respectively. is used.

By the way, in multilayer □ color photosensitive materials, it is necessary to fix each coupler in separate layers in order to reduce color mixture and improve color reproduction.

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 soften the emulsion layer when using organic solvents that cause crystal precipitation or high boiling points in the emulsion.
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, there is a risk of deteriorating the strength of the formed film.Also, since latex can contain a high concentration of coupler units, it is easy to emulse a high concentration of coupler. can be contained in
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 polymeric couplers added to gelatin silver halide emulsions in latex form include, for example, U.S. Pat. Ko≠7.4
No. 4r, U.S. Patent No. 3,4tj/, 120 discloses the manufacturing method and amount of magenta polymer coupler latex.
West German Patent No. 2,72j,! No. 7 and U.S. Patent No. 3. Octopus ≠ 3 is a copolymerized latex with a competitive coupler, as reported in U.S. Patent No. J, '7; 7,44/J and Research Disclosure.
cyan polymer coupler latex is described in 2/7211r.

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

Z A polymer coupler having a relatively high molecular weight (number average molecular weight/0,000 or more) has sufficient non-migration properties, but has poor coupling reactivity, resulting in low sensitivity, gradation, and dye density of the resulting dye.

2 As the content of Kab2-units (the content of repeating units with coupler residues) in the polymer coupler increases, (
Color development per unit weight (of coupler unit) is significantly reduced.

3. On the other hand, a polymer coupler with a very low molecular weight increases the dye concentration, but is insufficient in terms of non-migration.
Mixed colors and decreased sensitivity occur.

If high color development could be maintained using a polymer with a high coupler unit content, it would be possible to make the sensitive material film thinner, since it would be necessary to incorporate only a small amount of coupler in the emulsion at a much higher concentration. , it is possible to significantly improve the sharpness of images, so it is an important issue to improve color development in polymers with a high coupler unit content.
It is.

Another important issue for polymer couplers is to achieve both non-migration properties and coupling reactivity.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a silver halide color photographic material with high sensitivity.

The first object of the present invention is to provide a novel 2-layer film that has high sensitivity and extremely excellent color development.

A third object of the present invention is to provide a novel coupler that has a high coupler unit content and exhibits high color development.

The first object of the present invention is to provide a silver halide color photographic material free from color mixture due to the non-migration nature of the coupler.

The purpose of the present invention! by developing a silver halide emulsion in the presence of a dispersion of the novel coupler.
An object of the present invention is to provide a method of forming a color image.

A third object of the present invention is to provide a silver halide color photographic material containing a novel coupler latex, a photographic processing method thereof, and an image forming method.

(Means for Solving the Problems) An object of the present invention is to contain a lipophilic polymer coupler, and the lipophilic polymer coupler has a carbon number of t or more, and has a chain transfer constant of 0.07 to a monomeric coupler. This has been achieved by a silver halide color photographic light-sensitive material obtained by a polymerization reaction using a chain transfer agent of 20 or less.

The lipophilic polymer couplers used in the present invention, which are synthesized by a polymerization reaction using a chain transfer agent having a carbon number of 0.7 or more and a chain transfer constant of 0.7 or more and 20 or less, have various structures. Most of it is a mixture of the following general formula % Formula % General formula [P] E is a chain transfer agent with a carbon number of r or more and a chain transfer constant for the monomeric coupler of 0.1 or more and 20 or less represents a monovalent group derived from a radical moiety generated by chain transfer to

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. xl
y is the content of each repeating unit in the polymer coupler,
The weight ratio of x and y (x:y) is 10:0 to 100:0
It is.

The compound represented by the general formula [P] 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 (1) % formula % In the formula, RI represents a hydrogen atom, an alkyl R oligoyl group having 1 to 4 carbon atoms, or a chlorine atom, and Ll represents -〇〇N-(R
"represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted alkyl group having 1 to 6 carbon atoms), -COO-1-N
HCO-1-OCO-1 represents hydrogen, hydroxyl, a halogen atom, or substituted or unsubstituted alkyl, alkoxy, acyloxy, or aryloxy), and L: is a link connecting Ll and Q. m represents O or 1, n represents 0 or 1, and Q represents a coupler residue capable of coupling with an oxidized aromatic primary amine developer to form a dye.

L! Specifically, the linking group represented by +x'÷Jl-
Brother 8±, ÷J! It is expressed as -X3÷, ÷J8±, toe.

J Nao, J Tomi, and J2 may be the same or different, -CO-2-S O! -2-CON-(R'
is a hydrogen atom, an alkyl group (1 to 6 carbon atoms), a substituted alkyl group (1 to 6 carbon atoms), -so, N- (R'R% is the same as above), -NR' - (R' has the same meaning as above, R- represents an alkylene group having 1 to about 4 carbon atoms, represents a hydrogen atom, an alkyl group (1 to 6 carbon atoms), or a substituted alkyl group (1 to 6 carbon atoms)) , -0-1Rs (R' has the same meaning as above), -NCO- (R' has the same meaning as above), and the like.

XI, xt, and XI may be the same or different,
Represents an alkylene group, substituted alkylene group, arylene group, substituted arylene group, aralkylene group, and substituted aralkylene group.

p, q, "and S represent 0 or l.

In the above general formula (1), XI, XI, and X2 may be the same or different and represent an unsubstituted or substituted alkylene group, aralkylene group, or phenylene group having 1 to 10 carbon atoms, and the alkylene group is a direct Alkylene groups, which may be chain or branched, include methylene, methylmethylene, dimethylene/ethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups include benzylidene, and phenylene groups include p- Examples include phenylene, m-phenylene, and methylphenylene.

Also, an alkylene group represented by XI, Xt, XI,
As a substituent for the aralkylene group or phenylene group,
Halogen atom, nitro group, cyano group, alkyl group, substituted alkyl group, alkoxy group, substituted alkoxy group, -NH
A group represented by CORI (R" represents alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, substituted aralkyl -), -NH3O!R" (R1 has the same meaning as above), -3OR"(R" has the same meaning as above) Same as I
, -S Os R'(R" has the same meaning as above), -COR
``(R'' may be the same or different and represents a hydrogen atom, alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, substituted aralkyl), an amino group (even if substituted with alkyl) good),
Examples include a hydroxyl group and a group that forms a hydroxyl group by hydrolysis. 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 aralkyle group include hydroxyl group, nitro group, alkoxy group having 1 to about 4 carbon atoms, -N
H3Ox R@ (R mouth has the same meaning as above), -NHCO
A group represented by R- (R. is R111 as defined above),
-3o□R"(R" has the same meaning as above), -COR"
(R- has the same meaning as above), halogen atom, cyano group,
Examples include amino groups (which may be substituted with alkyl).

Next, among the color coupler residues represented by Q in general formula (1), cyan color forming coupler residues include phenol type (II) represented by the following general formula, [V]
, or a naphthol type (Iff), [rV) compound (hydrogen atoms other than the hydrogen atom of each hydroxyl group are separated and connected to ÷L1 and Lt) are preferable.

H (U""), /l' 1IzI In the formula, R11 represents a group that can be substituted on a phenol ring or a naphthol ring, and examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxy group, a sulf* group, a cyano group, and an aliphatic group. group 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 Zoku Oki II
5. Examples include aromatic thio group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, etc. The number of carbon atoms in R11 is θ to 30.

R"!t-C0NR"R", -NHCOR", -NHC
OORlh, N1(So! RI-1-NHCO
Represents NRI4R"t or -NH3Ch R"R",
R'' and RIS are hydrogen atoms, aliphatic groups having 1 to 30 carbon atoms (e.g., methyl, ethyl, butyl, methoxyethyl, n-decyl, n-dodecyl, n-hexadecyl, trifluoromethyl, heptafluoropropyl, dodecyloxypropyl, 2゜4-di-tart-amylphenoxypropyl, 2゜4-di-tart-amylphenoxybutyl), aromatic groups having 6 to 30 carbon atoms (e.g., phenyl, tolyl, 2-tetradecyloxyphenyl) , pentafluorophenyl, 2-chloro-5-dodecyloxycarbonylphenyl), a heterocyclic group having 2 to 30 carbon atoms (e.g., 2-pyridyl, 4-pyridyl, 2-furyl, 2-thienyl), R1& is the number of carbon atoms 1 to 30 aliphatic groups (e.g. methyl, ethyl, butyl, dodecyl, hexadecyl), 6 to 30 aromatic groups (e.g. evaphenyl, tolyl, 4
-chlorophenyl, naphthyl), heterocyclic groups (e.g. 4
-pyridyl, quinolyl, 2-furyl), R14
and RIS may be bonded to each other to form a heterocycle (e.g., morpholine ring, piperidine ring, pyrrolidine ring), p' is θ~3.3' is 0~2, qo and r' are each 0 Represents an integer from ~4.

Is X4 an oxygen atom, an ionic atom or R'? R11 represents a hydrogen atom or a monovalent group.

When Rtt represents a monovalent group, examples of Rtt 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), a heterocyclic group having 2 to 30 carbon atoms (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), 0RII, 5R
II, -COR", -CONR"R", -COCOR"
, -COCONR"R", -COOR"・, -COCO
OR",-sow R"・,-5at OR",-
SOo NRI I RI l and -N RI @ RI
*Can 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, heptafluoropropyl), aromatic groups having 6 to 30 carbon atoms (e.g. phenyl, tolyl, 4-chlorophenyl,
pentafluorophenyl, 4-cyanophenyl, 4-hydroxyphenyl) or a heterocyclic group having 2 to 30 carbon atoms (
For example, 4-pyridyl, 3-pyridyl, 2-furyl).

R1- and R19 may be bonded to each other to form a heterocycle (eg, pyrrolidino, pyrrolidino).

Examples of RI include the substituents shown in <R1- and RI9 excluding the hydrogen atom.

Zl represents a hydrogen atom or a group that can be released by a cuff-pulling reaction with an oxidized aromatic primary amine developer.
chlorine, bromine, iodine), aliphatic oxy groups having 1 to 30 carbon atoms (e.g., methoxy, ethoxy, 2-hydroxyethoxy, carboxymethyloxy, 3-carboxyprooxy, 2-methoxyethoxycarbamoylmethyloxy, 2- methanesulfonylethoxy, 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, l-phenyl-5-tetrazolyloxy), aliphatic thio groups having 1 to 3.0 carbon atoms (e.g. , dodecylthio), an 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), acyloxy group having 2 to 30 carbon atoms (e.g. acetoxy, benzoyloxy, lauroyloxy), 1 to 30 carbon atoms carbonamide group (e.g. dichloroacetylamide,
trifluoroacetamide, heptafluorobutanamide, pentafluorobenzamide), sulfonamide groups having 1 to 30 carbon atoms (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 oxycarbonyloxy group having 6 to 30 carbon atoms (e.g., phenoxycarbonyloxy)
, a bamoyloxy group having 1 to 30 carbon atoms (e.g., methylcarbamoyloxy, dodecylcarbamoyloxy, phenylcarbamoyloxy), a heterocyclic group having 1 to 30 carbon atoms and having a nitrogen atom connected to the active position of the coupler (e.g., Examples include succinimide 1, phthalimide, hydantoinyl, pyrazolyl, 2-benzotriazolyl), and the like.

Y' represents an atomic group necessary to form a 5- to 7-membered ring together with the bonded carbon atom, and represents R# (2) alone or in combination; R1 and R# each independently represent a hydrogen atom, It represents 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 R11 include halogen atoms (e.g., ferene, chlorine, bromine, etc.), aliphatic groups (e.g., methyl, ethyl, isopropyl), carbonamide groups (e.g., acetamide, benzamide), sulfonamide groups (e.g., methanesulfonamide, toluenesulfonamide), etc.

Preferred are -CONR'R'', examples being carbamoyl, ethylcarbamoyl, morpholinocarbonyl, dodecylcarbamoyl, hexadecylcarbamoyl, decyloxypropyl, dodecyloxypropyl, 2,4-di-tart-amylphenoxy. Propyl, 2,4-di-tart-amylphenoxybutyl.

What is preferable as X4?RI? Further preferred as R1' are , ethoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, methoxyethoxycarbonyl, phenoxycarbonyl), -3o! R” (
For example, methanesulfonyl, ethanesulfonyl, butanesulfonyl, hexadecanesulfonyl, benzenesulfonyl, toluenesulfonyl, p-chlorobenzenesulfonyl), -CONR"R" (N.

N-dimethylcarbamoyl, N,N-diethylcarbamoyl, N,N-dibutylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, 4-cyanophenylcarbamoyl, 3.4-dichlorophenylcarbamoyl,
4-methanesulfonylphenylcarbamoyl), -S
Ox N R, "R" (e.g., N, N-dimethylsulfamoyl, N.

N-diethylsulfamoyl, N,N-dipropylsulfamoyl). More particularly preferred among R1't are groups represented by -COR'', -COOR1@ and -3o, R''.

Preferred groups as Zl are hydrogen atom, halogen atom,
They are 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 its substituents Rl l, R1
1, x4 or Zl may be a dimer or a multimer of more than 1 bonded to each other via a divalent or more polyvalent linking group. In this case, the number of carbon atoms shown in each of the above substituents is not limited to this.

The magenta color-forming coupler residues include coupler residues represented by the general formula %) and (XI) (Arszi
, ÷L' +- in any part of Rt+ to R22
In the case of general formula (V) which is linked to t-+L''÷, the more preferable case is the case where it is linked directly to the substitution position of R8-.

2 snow H is 11 z! ■ Z'' H In the formula, Ar is a well-known type of substituent at the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituted alkyl group (e.g., a haloalkyl group such as fluoroalkyl,
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), alkoxy Carbonyl groups (e.g. methoxycarbonyl), acylamino groups (e.g. acetylamino), carbamoyl groups, alkylcarbamoyl groups (e.g. methylcarbamoyl, ethylcarbamoyl), dialkylcarbamoyl groups (e.g. dimethylcarbamoyl), arylcarbamoyl 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 ( For example, phenylthio), cyano group, nitro group, halogen atom (
For example, fluorine, chlorine, bromine, etc.), and when there are two or more substituents, they may be the same or different; particularly preferred substituents include halogen atoms, alkyl groups, alkoxy groups, alkoxycarbonyl groups, and cyano groups. can be mentioned. ], represents a heterocyclic group (eg, triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole, etc.).

R11 is an unsubstituted or substituted anilino group, an acylamino group (e.g. alkylcarbonamide, phenylcarbonamide, alkoxycarbonamide, phenyloxycarbonamide), a ureido group (e.g. alkylureido,
phenylureido), and these substituents include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), linear and branched alkyl groups (e.g. methyl, t-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-tert-
amylphenoxy)acetamide, α-(2,4-di-tert-amylphenoxy)butyramide, α-(3
-pentadecylphenoxy)hexanamide, α-(4
-hydroxy-3-tart-butylphenoxy)tetradecanamide, 2-oxo-pyrrolidin-1-yl,
2-oxo-5-tetradecylpyrrolidin-1-yl,
N-methyl, tetradecanamide), sulfonamide groups (e.g. methanesulfonamide, benzenesulfonamide, ethylsulfonamide, p-toluenesulfonamide, octanesulfonamide, p-dodecylbenzenesulfonamide, N-methyl-tetradecanesulfonamide) ), sulfamoyl groups (e.g. sulfamoyl,
N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N,N-dihex,
Silsulfamoyl, N-hexadecylsulfamoyl, N-(3-(dodecyloxy)-propyl)sulfamoyl, N-(4-(2,4-di-tart-amylphenoxy)butyl)sulfamoyl, N-methyl- N-
tetradecylsulfamoyl, etc.), carbamoyl group (
For example, N-methylcarbamoyl, N-butylcarbamoyl, N-octadecylcarbamoyl, N-(4-(2°4-di-tart-amylphenoxy)butylcarbamoyl, N-methyl-N-tetradecylcarbamoyl),
Diacylamino 1 (N-succidiimide, N-phthalimide, 2,5-dioxo-1-oxazolidinyl, 3-
Dodecyl-2,5-dioxo-1-hydantoynyl, 3
-(N-7cetyl-N-dodecylamino)succidiimide), alkoxycarbonyl groups (e.g., methoxycarbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), alkoxysulfonyl groups (e.g., methoxysulfonyl, butoxysulfonyl, octyloxysulfonyl, tetra decyloxysulfonyl), aryloxysulfonyl groups (e.g., phenoxysulfonyl, p-methylphenoxysulfonyl, 2,4-di-t
ar t-amylphenoxysulfonyl, etc.), alkanesulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl), oriri-sulfonyl groups (e.g., benzenesulfonyl, 4-nonyl) benzenesulfonyl), alkylthio groups (e.g. methylthio, ethylthio, hexylthio, benzylthio, tetradecylthio, 2-(2,4-tert-amylphenoxy)ethylthio, etc.), arylthio groups (e.g.
phenylthio, p-tolylthio), alkyloxycarbonylamino groups (e.g. methoxycarbonylamino,
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), Examples include a nitro group, a carboxyl group, a sulfo group, a hydroxy group, and a 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.

Rag, R■, 2 mouths, R11, Rxi% R-fu, RZm
, R■, Rco@, R31, R3 and R33 each represent a hydrogen atom, a hydroxyl group, and an unsubstituted or substituted alkyl group (preferably one with 1 to 20 carbon atoms).
For example, methyl, propyl, t-butyl, trifluoromethyl, tridecyl, etc.), aryl groups (preferably those with 6 to 20 carbon atoms), aryl groups (preferably those with 6 to 20 carbon atoms), e.g. phenyl, 4-t-butylphenyl, 2.4-di-t- amyl phenyl, 4-methoxyphenyl), heterocyclic groups (e.g. 2-furyl, 2-
thienyl, 2-pyrimidinyl, 2-benzothiazolyl)
, alkylamino group (preferably one having 1 to 20 carbon atoms, e.g. methylamino, diethylamino, -butylamino), acylamino group (preferably one having 2 to 20 carbon atoms)
0 e.g. acetylamino, propylamide, benzamide), anilino group (e.g. phenylamino, 2
-chloroanilino), alkoxycarbonyl groups (preferably those with 2 to 20 carbon atoms, e.g., methoxycarbonyl, butoxycarbonyl, 2-ethylhexyloxycarbonyl), alkylcarbonyl groups (preferably those with 2 to 20 carbon atoms, e.g. , acetyl, butyl, carbonyl, cyclohexylcarbonyl), arylcarbonyl group (e.g., preferably one with 7 to 20 carbon atoms, benzoyl, 4-1-butylbenzoyl), alkylthio group (preferably one with 1 to 20 carbon atoms), (e.g., methylthio, octylthio, 2-phenoxyethylthio), arylthio group (preferably one with 6 to 20 carbon atoms, e.g., phenylthio, 2-butoxy-5-t-octylphenylthio), carbamoyl group (preferably carbon For example, N-ethylcarbamoyl i, N, N-dibutylcarbamoyl, N-methyl-N-butylcarbamoyl), sulfamoyl group (preferably up to 20 carbon atoms), etc. famoyl, N,N-diethylsulfamoyl, N,N-dipropylsulfamoyl) or sulfonamide group (preferably 1 to 2 carbon atoms)
0 (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide).

Z! # 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 be removed include halogen atoms (e.g., chlorine,
bromine), campling leaving groups linked via an oxygen atom (e.g. acetoxy, propanoyloxy, benzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenokidyl, 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), coupling-off groups linked via a nitrogen atom (e.g., JP-A-59 −
99437, specifically benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluorobutanamide, 2°3.4,5.6-
Pentafluorobenzamide, octanesulfonamide, 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-promobenzotriazol-1-yl, 5-methyl-1,2,3,4-)riazole-1-yl 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-penzothiazolyl). 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, or an i-midazolyl group. , is a triazolyl group.

As the yellow color-forming coupler residue, those of the acylacetanilide type are preferred, particularly those of the pivaloylacetanilide type [■], benzoylacetanilide type 0#), (XV) represented by the following general formula (freedom in the general formula Connect to +L'+--+L"± at the bond part.)
In the formula R" l N", Rh, R
55SRxh and R3' are each a hydrogen atom or a well-known substituent of a yellow color-forming coupler residue, such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, an aliphatic amide group, an alkylsulfamoyl group. group, alkylsulfonamide group, alkylureido group, alkyl-substituted succiimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group,
It represents an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, and these substituents may be the same or different.

Z3 is represented by a hydrogen atom or the following general formula [1, [dramatic], [key] or C point].

■OR'' (XVI) R31 represents an optionally substituted aryl group or heterocyclic group.

1 to 3 drops, R'' is a 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 represents a substituted phenyl group or a heterocycle, and these groups may be the same or different.

0V-′ゞ＼〆0°・,〜W′・ PA [violet] Represents a nonmetallic atom required to form a 5- or 6-membered ring.

In the general formula [violet], [double] to [double ■] are preferred.

In the formula R41, R4! R4S is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group, R44 and R4s are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group, and W2 is Represents an oxygen or sulfur atom.

Preferred examples of ethylenically unsaturated monomers providing the repeating unit represented by B include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (such as methacrylic acid), and esters derived from these acrylic acids. or amides (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, 2-methoxyethylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propylacrylate, n-butylacrylate, t-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 (for example, 2-methoxyethyl acrylate,
2-methoxyethyl methacrylate, 2-methoxyethyl 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, pyrene, , 1-butene, isobutyne and the like.

Furthermore, 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 CH3 ■ CH2-C ■ CH3 CH2-C ■ CH2-CH C00CH2CH-CH2 \1 CH2-CH CH2=CH C0NHCH2NHCOCH2CH25O2CH2CH
2(JH3 CH2=C CH2-CH ■ CO2CH2CH2α:0CH2CH25O2CH2C
H2αH3 The ethylenically unsaturated monomer used here can also be used in combination with 2s or more.

For example, ethyl acrylate and n-butyl acrylate,
These include n-butyl acrylate and styrene, n-butyl acrylate and t-butylacrylamide, comethoxyethyl methacrylate and potassium styrene sulfinate, and the like.

Among the compounds represented by the general formula (1), particularly preferred compounds are shown below.

represents O or /. L2 is -E-X''+J'-X2i +J2-X3% +J3i
Among these, the most preferable ones are:
JI J2 J3 may be the same or different;
-CO-1-SO2-1-CONH-1-8O2NH-
1-NHCO-1-NH8O2-1-〇-1-NHCO
NH-1-S-1-COO-1-OCO-1-NHCO
Represents O-1-OCONH-, X , X , X
may be the same or different and represent an alkylene group (carbon number/-), an arylene group, a substituted arylene group, and p, qX r and S represent 0 or 1.

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 CP), E represents a monovalent group derived from a radical moiety generated by chain transfer to a chain transfer agent having a carbon number of 0.1 or more and a chain transfer constant of 0.1 to 20 for the monomeric coupler. , for example, the following general formula (XXII
).

General formula (XXI[] E1→Y← El includes an alkyl group having at least the number of carbon atoms, a substituted alkyl group, a substituted aryl group, a substituted naphthyl group, etc.

Examples of substituents that may be further substituted on these groups include halogen atoms, cyano groups, alkyl groups, substituted alkyl groups, alkoxy groups, substituted alkoxy groups, -NHCO
R46 (R4' represents an alkyl group, substituted alkyl group, phenyl group, substituted phenyl group, aralkyl group), -N
H8O2R46 (R46 has the same meaning as above), -〇〇OR4
'(R4' has the same meaning as above), -0COR46 (R46
is the same as above), -8OR4'R48 may be the same or different and represents a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, an aralkyl group, a substituted aralkyl group), a mino group (alkyl (which may be substituted with a group), a hydroxyl group, and a group that forms a hydroxyl group by hydrolysis.

In addition, examples of substituents for the alkyl group, substituted alkoxy group, substituted phenyl group, and substituted aralkyl group include hydroxyl group, alkoxy group having a carbon number of 1 to about 1, -NH8O2R46
(R4' has the same meaning as above), -NHCOR" (R46 has the same meaning as above), -COOR'6 (R46 has the same meaning as above)
, -0COR"(R4' has the same meaning as above), 3() 2R46 (R46 has the same meaning as above), COR"
(R46 has the same meaning as above), a halogen 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.

C3H17-IC10H21-IC12H25-1C1
4H29-IC15H31-IC16H33-1C18
H37r C20H41+ C31H63+C16
H33SO2NHCH2CH2-.

C3H17CONHCH2CH2-, C13H27CO
NHCH2CH2-.

C,5H3□C0N)IcH2CH2-, C17H3,
C0NHCH2CH2-.

12H25 CH3CONCH2CH2-, C□2H25NHCH2
CH2-.

C16H33NHCH2CH2-, Cl2H25NHC
OCH2-.

Cl8H37NHCOCH2-.

(X,'4)(9 In the general formula (XXn), Y is -5-1-SO-1
-802-. p is O or /.

In the general formula CP), X preferably represents a hydrogen atom or a halogen atom (F, α, Br, I).

Next, typical examples of monomeric couplers that provide a coupler unit having a coupler residue capable of forming a dye by coupling with an aromatic primary amine developer represented by the general formula [I], which is a color-forming moiety, will be shown. However, it is not limited to this.

Moreover, each of these monomeric couplers may be used one type at a time, or several types may be used at a time.

+1+ CI+! -C1l 011N
HCOCffF? OD Cl1i -C11 CI II 5 l1l CI.

C, II.

I ■ NHCOOCaL(iso) (191CI+.

■ CHt Tomi C ■ C11゜ ■ CH2 CHl,=C11 ■ CHl (32) C1h-CHl ~IIL;UL;ll5 CHl-CH CHiClliCN CH.

j CH, -CHl C0NIICHzCIIxO ■ CH, - bow 11 CHl CH3 to H, E CHz”CH CH!-C-CHff L CHz-C to H, L, to C11°CHz-C1 Chain transfer used in the present invention In addition to the compound represented by the general formula CP), the polymer coupler obtained by the polymerization reaction using the following general formula [XXI[[], (XXI
The compound represented by V) is about O0/ to about 2OWt
Mixed.

General formula (XXn [) E-+A generation + BsuE (8% A% B% X% 3' has the same meaning as above) General formula (XXIV) Engineering → A generation + BkeX (A, B, , 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 (I) jp-1, 23
~/27 (Kagaku Doujin, /1971), in addition to the above general formulas [XX■] and [XX■], there are also chain transfers to monomers and chain transfers to polymerization solvents. The derived compounds exist depending on the chain transfer ability of the monomer solvent.

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

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

The polymerization reaction in a system in which a chain transfer agent is present by standing is described as follows.

Start I −+ I・■・10EX → IX+E・ Growth EM・−)−(n−/)M −1 → EMn
-tr Chain transfer EMn・+EX-E (Mn)X+E.

Stop 2E・ → E−E where I, M, and EX are the initiator, monomer, and chain transfer agent, respectively, j5, EM・ and EMn・ are propagating radicals, ■・, E(Mn) primary radicals,
The generated polymer, the chain transfer agent radical, and k represent the rate constants of the respective elephantine reactions.

That is, the reaction 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.

The chain transfer constant is defined as the ratio ktr/kp of the rate constants of chain transfer reaction and growth reaction.

In the synthesis method of the telomer coupler used in the present invention, the monomer coupler has different carbon atoms than normal radical polymerization. There is a major feature in using the above chain transfer agents.

The use of a chain transfer agent having a carbon number higher than that is necessary to prevent the telomer coupler from diffusing in the emulsion layer.
Furthermore, the fact that the chain transfer constant of the chain transfer agent represented by E-X with respect to the monomeric coupler is 001 or more and 20 or less means that the general formula CX
This is effective in reducing the amount of the compound represented by XIV].

Chain transfer agents are described, for example, in the Polymer Handbook by J. Brandrup et al., John Wiley and Sons.

(John Wiley & 5ons)] II-
r 7~/o +2, and Takayuki Otsu's "Radical Polymerization (
1) As stated on page 12r of J (Kagaku Doujin, 1st year), the chain transfer constant changes depending on the type of chain transfer agent and monomer, so the amount added depends on the purpose. It depends on the molecular weight of the telomer and the value of the chain transfer constant.

The chain transfer constant changes depending on the combination of chain transfer agent and monomer coupler, but when mercaptans are used as the chain transfer agent, the chain transfer constant is 0. This is a particularly preferable compound in that it takes a value of /~co0.

Preferred chain transfer agents used in the present invention are listed below, but are not limited thereto.

C3H17SH・Cl0H21SH+ Cl2H2
5SH+C14C14H2・C15) (31SH+
C16H33SHrC18H37SH・C20H4
1SH1C31H63SH2C16H33SO2NHC
H2CH2SH.

C3H17CONHCH2CH2SH, C13H27C
ONHCH2CH2SH.

C15H31CONHCH2CH2SH, C15H31
CONHCH2CH2SH.

C16H33NHCH2CH2SH, Cl2H25NH
COCH2SH.

Cl8H37NHCOCH2SH.

ctCH2Cα)C12H25, ICH2Cα)C12
H25rBrCH2Cα”16H33+ clcH2
cα) C18H37゜ENG CH2Cα) CI BH37,
B r 2CHCα”12H2511J 3CCOOC
16H33 The synthesis of the telomer coupler of the present invention is carried out using a polymerization initiator and a polymerization solvent as described in JP-A-61≠3 and JP-A-7-5'44.
7jJ, Tokukai Sho! 7-/7t03r, JP-A-17-J
04407 r, JP-A-11-Jr74'! , Japanese Patent Publication No. 5
r-10731, Tokukai Shoj! -4'uOa≠, JP-A-1
1-/≠! ≠≠, using the compound described in JP-A No. 2003-120003.

Further, when synthesizing the telomer carb 2- of the present invention, a polymerization initiator having 20 or more carbon atoms is preferably used.

By using this initiator, the general formula [XX■], [
XX■] The diffusion resistance of the polymer coupler can be increased.

Examples of preferred polymerization initiators are shown below.

The polymerization initiator is used in an amount of about 0.07 to about 10 molti based on the monomer, preferably o, oi to λ, Q molti.

It is better for the polymerization solvent to have a small chain transfer constant, preferably /x10-3 or less.

The polymerization temperature needs to be set in relation to the molecular weight of the telomer to be produced, the type of initiator, etc., and can range from below 0°C to above 0°C, but is usually 30'C-t.
Polymerizes in the oo'C range. For telomer synthesis, higher temperatures are better, preferably in the range of about 70-100C.

The ratio of the colored portion in the telomer coupler represented by the general formula ["l] is usually preferably 1% by weight from /Q to Preferably, the molecular weight (grams of polymer containing 1 mole of monomeric coupler) in this case is about 200-000, but is not limited thereto.

The number average molecular weight of the telomer coupler of the present invention is preferably about 100 to about 10,000, particularly preferably about 200 to about j000, from the viewpoint of color development and sensitivity.

Furthermore, mercaptans, which are chain transfer agents preferably used in the present invention, are present in the telomer coupler at approximately 0.0/-0.3% by weight even after the completion of polymerization, causing undesirable effects such as fogging and desensitization. Sometimes.

As a method for removing these mercaptans or rendering them harmless in terms of photographic performance, the following method may be used.

(1) Only the telomer coupler is recovered by precipitation in a solvent in which the telomer coupler is substantially insoluble.

(2) After completion of polymerization, new ethylenically unsaturated monomer (
By adding a compound (which may or may not contain a coupler residue) and polymerizing it again, a new telomerization reaction is carried out and the mercaptans are inactivated.

(3) Oxidation treatment converts mercaptan into substances (disulfide, sulfone, sulfoxide) that are harmless in terms of photographic performance.

Among the above three methods, method (2) is preferred from the viewpoint of the effect of reducing mercaptans and characteristics such as color development and sensitivity.

In addition, in method (2), a monomer that provides a water-soluble polymer such as acrylic acid or acrylamide is used as the ethylenically unsaturated monomer to be post-added, and after completion of post-polymerization, water reprecipitation or By performing operations such as extraction with a water/organic solvent system, only mercaptans can be efficiently removed. That is, mercaptans are excluded from the system as telomers of water-soluble polymers such as acrylic acid and acrylamide, and do not have any effect on the properties of the telomer (coupler unit content, coloring performance). therefore,
Substances harmful to photographic performance can be removed while retaining the high color development and high sensitivity properties of telomer.

Using this method, the amount of mercaptans remaining in the telomer can be reduced to a range of about tppm to 10 oppm.

The telomeric couplers of the present invention are added to the silver halide emulsion layer or its adjacent layer.

The telomeric coupler of the present invention is based on the coupler monomer, and in the case of the same layer as silver halide, the telomeric coupler is
, ooz mol to O, 5 mol preferably 0.07 to 0.1
It is better to add 0 mole.

Further, when the telomer coupler of the present invention is used in the non-photosensitive layer, the coating amount is 0.0/g/m2 to 0.0/g/m2.

0g7m2, preferably 0,/g/m2~
0,1g7m2.

In the present invention, the number average molecular weight can be calculated based on the measurement results by gel permeation chromatography (CPC method).

The measurement conditions of the GPC method are as follows.

Column: TSKgel (manufactured by Toyo Soda) G1000H
9 G2oooHB TSKgel (manufactured by Toyo Soda) G2oooHs Solvent: THF Flow rate: /ml/min Column temperature: μo'C Deichiku II -: UV-rmodel l (manufactured by Toyo Soda) TSK standard polystyrene (°Toyo (manufactured by Soda) to create a calibration curve.

The number average molecular weight is calculated from "Polymer Science Experimental Methods" edited by the Society of Polymer Science and Technology (
Calculations were made using the general method described in Tokyo Kagaku Doujin 11th year) p-co Oμ~xor, that is, the line segment method. The obtained chromatogram was divided into equally spaced chromatograms (D), the peak height of the i-th polymer species from the baseline was defined as Hi, and the peak height was determined using the following relational expression (1).

Σ1(HiD/Mi) Σ1(Hi/Mi) Therefore... Relational expression (1) Here, Ni represents the number of i-th polymer species, and Mi
It represents the molecular weight of the Fii-th polymer species (Mi can be determined from the above calibration curve).

The chain transfer constant in the present invention can be calculated by various methods. A general method is "Radical Polymerization (1) J (Kagaku Doujin 1977) I)" by Takayuki Otsu, /λ
There is a method described in A-p,/Core. That is, in the polymerization when X=100S'j=0 in the general formula [P],
This is a method of quantifying the remaining monomer coupler and remaining chain transfer agent in the reaction solution and using the following relational expression (2).

...Relational expression (2) Here, [S] represents the concentration of the remaining chain transfer agent, and [M
] represents the concentration of remaining monomeric coupler.

As is well known in the field of polymer color couplers, the general formula [
The physical and/or chemical properties of the copolymer represented by [2], such as solubility, compatibility with binders such as gelatin in photographic colloid compositions, its flexibility, and thermal stability, have a favorable influence. You can choose to receive it.

The telomer coupler of the present invention may be prepared by dissolving a coupler obtained by polymerizing a monomer coupler in an organic solvent and emulsifying and dispersing it in the form of latex in an aqueous gelatin solution.
Alternatively, it may be produced by a direct emulsion polymerization method.

A method of emulsifying and dispersing a coupler in the form of latex in an aqueous gelatin solution is described in US Patent No. 3. ≠! /, rco No. 0, U.S. patent for emulsion polymerization≠.

010.2// issue, same! , 370. The method described in No. JJ can be used.

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

Synthesis Example 1 Telomer coupler I (monomer coupler, copolymer of (1) and butyl acrylate)! - Acrylamide 29 μm dichloro-3-methylphenol (monomeric coupler (1)) 71 g 1 butyl acrylate/2 g, n-dodecylmercaptan J, jg and N, N-dimethylacetamide 200 ml JOO
ml Mitsuro flask and place under nitrogen stream.
c) The mixture was heated and stirred. 10 ml of N,N-dimethylacetamide solution containing 0.3 g of dimethyl azobisinbutyrate
1 was added to initiate polymerization. After reacting for an hour, the temperature of the reaction solution was lowered to 7,000℃. Jml of an N,N-dimethylacetamide solution containing 0.1 g of acrylic acid tg1 dimethyl azobisinbutyrate was added, and the mixture was heated and stirred for an additional μ hour.

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. By heating and drying this solid under reduced pressure, cytelomercap, --(1), 2
6.3g was obtained.

According to chlorine analysis, the telomeric coupler with the monomer coupler (1) is obtained in the polymer. It was recognized that the content was % by weight.

The number average molecular weight by GPC was -100.

The chain transfer constant of dodecyl mercaptan used in this synthesis was calculated based on the measurement results by the GPC method and gas chromatography method shown below.

Monomeric coupler (i) tzg, 2.1 g of n-dodecylmercaptan and 200 g of N,N-dimethylacetamide
Transfer ml to a 3 ooml Mitsuro flask and incubate under nitrogen stream for 7 hours.
! The mixture was heated to 0C and stirred. Dimethyl azobisinbutyrate 0.
N,N-dimethylacetamide solution containing 3g 1
0ml was added to start polymerization. 10 ml of the reaction solution was withdrawn at predetermined intervals, and a methanol solution/ml containing 10 mg of hydroquinone was added to stop the polymerization. The residual monomer coupler and residual chain transfer agent in these samples were quantified by GPC method and gas chromatography method, respectively, log [monomer coupler: l, log [: chain transfer agent] was plotted, and the above relational expression ( 2) using the chain transfer constant 3. ! I got it.

Synthesis Example - λO Telomer couplers (II) to (XX) shown in Table 1 were synthesized in the same manner as in Synthesis Example 1 (the amount of chain transfer agent was changed as needed to adjust the molecular weight).

Comparative synthesis example/ (Copolymer of monomer coupler (/μ) and butyl acrylate) Monomer coupler (l≠) 20 gs A mixture of butyl acrylate, lOg and 200 ml of ethyl acetate was heated to 7j0C under stirring in a nitrogen stream. After heating, ioml of an ethyl acetate solution containing 0.1 g of dimethyl azobisisobutyrate was added to initiate polymerization. After reacting for 5 hours, the reaction solution was cooled and directly concentrated.

The precipitated solid was heated and dried under reduced pressure to obtain 37.3 g of comparative polymer coupler (A).

This polymer coupler has 30.2 coupler units of the monomeric coupler (7μ) in the polymer formed by fluorine analysis.
It was recognized that the content was % by weight. The number average molecular weight by GPC was ≠1000.

Comparative Synthesis Example λ (Copolymer of monomer coupler (/4t) and butyl acrylate) Monomer coupler (lhiro) was prepared in the same manner as in Comparative Synthesis Example 1.
A comparative polymer coupler (B) was synthesized using 10 g of J Ogz butyl acrylate. The content of coupler units of the monomeric coupler (l≠) according to fluorine analysis is 7≠,
is weight%, and the number average molecular weight by GPC is /110
It was 00.

Comparative Synthesis Example 3 (Copolymer of monomer coupler (l≠) and butyl acrylate) Comparative polymer coupler (copolymer of monomer coupler (l≠) and butyl acrylate) C) was obtained.

Comparative polymer coupler (C) Number average molecular weight 3700 Coupler unit in polymer ≠ r, 7% by weight Comparative synthesis example (copolymer of monomer coupler (/μ) and butyl acrylate) Polymerization solvent increased by r A comparative polymer coupler (D) was obtained under the same conditions as in Comparative Synthesis Example 2, except that twice as much initiator was used.

Comparative polymer coupler (D) Number average molecular weight 300 Coupler units in polymer 73.2% by weight Comparative synthesis example (/-L21 μm 6-Dolichlorophenyl)-3-methacrylamide-≠-Virazolyluco Pyrazoline! −
Copolymer coupler of monomeric coupler (Jj) and butyl acrylate monomeric coupler (Jj) JOgs
Butyl acrylate J Og, dimethylacetamide/! After heating the Og mixture to 7!0C under stirring in a nitrogen stream, 10 ml of dimethyl azobisisobutyrate/dimethylacetamide containing Og was added to initiate polymerization.

After reacting for 5 hours, the reaction solution was cooled, poured into water 31, and the precipitated solid was filtered and washed thoroughly with water.

By heating and drying this solid under reduced pressure, 3r, zg of Comparative Example Polymer Coupler (E) was obtained.

A chlorine analysis of this polymer coupler revealed that the copolymer formed contained zo, r weight % of the coupler units of the monomeric coupler (26). The number average molecular weight by GPC was co/θθ0.

Comparative Synthesis Example t (Copolymer of monomer coupler (λt) and butyl acrylate) Monomer coupler (24) J was prepared in the same manner as in Comparative Synthesis Example 3.
(7gs) A comparative polymer coupler (F) was synthesized using 10g of butyl acrylate.

The content of coupler units according to fluorine analysis is 7! .

3% by weight, and the number average molecular weight by GPC is 1300.
It was 0.

Comparative Synthesis Example 7 (Copolymer of monomer coupler (Jj) and butyl acrylate) Comparative synthesis example except that the polymerization solvent was used μ times as much and the initiator was used 10 times as much! Comparative polymer coupler (G) under the same conditions as ゛
I got it.

Comparative polymer coupler (G) Number average molecular weight 3400 Coupler units in polymer 4 Ar, s wt% Comparative synthesis example t (Copolymer of monomer coupler (Colo) and butyl acrylate) Start with ≠ times the polymerization solvent A comparative polymer coupler (H) was obtained under the same conditions as in Comparative Synthesis Example t except that three times as much of the agent was used.

Comparative polymer coupler (H) Number average molecular weight 3100 Turnip 2-units in polymer 73. Comparative synthesis example 2 by weight
lλ (Copolymer of monomer coupler (1) and butyl acrylate) The following comparative polymer couplers (I) to (L) were synthesized under the same conditions as in Comparative Synthesis Examples/-μ.

y (1) 11. 2
4tuoo.

10 (J) to, r 3
7o.

tt (K) 7 da, ta 1zto.

lko (L) tz,y sz
o.

Comparative Synthesis Example 13~/J (/j, /4A~Copolymer of monomer coupler (μl) and butyl acrylate: ir, it~Copolymer of monomer coupler (core) and butyl acrylate) Monomer Body coupler (core) α Comparative synthesis example! (M) and (0) were synthesized under the same conditions as in Comparative Synthesis Example 6, and (N) and (P) were synthesized as comparative polymer couplers, respectively.

/J (M) (gu/) BA jO,03
6000/44 (N) (4!/) HA
! 0. IJ! TOOit (0) (core) BA ≠t, ≠ 23000/j (
P) (λ7) BA! 0. r ko2
00 Comparative Synthesis Example 17 (Copolymer of monomer coupler (l≠) and butyl acrylate) Monomer coupler (l≠)/Jgs Butyl acrylate i o g% Cohexadecanol (chain transfer constant 7× After heating a mixture of 7.7 g of 1O-3) and 200 ml of ethanol to 7!0C under stirring in a nitrogen stream, 10 ml of an ethanol solution containing o, zg of dimethyl azobisisobutyrate was added.
1 was added to initiate polymerization. After reacting for 1 hour, the reaction solution was cooled and added with water/.

! The precipitated solid was filtered and washed thoroughly with water.

By heating and drying this solid under reduced pressure, 20.1 g of comparative polymer coupler (Q) was obtained.

This polymer coupler contains the coupler unit of the monomer coupler (/see) in the polymer formed by fluorine analysis!
It was recognized that the content was % by weight. The number average molecular weight by GPC was 000.

Comparative synthesis example it (/-(λ, ≠, monotrichlorophenyl)-3-methacrylamide-goupyrazolyl-λ-pyrazoline-!-
Copolymer coupler of monomeric coupler (cot) and butyl acrylate monomeric coupler (co4) Jθg1
Butyl acrylate/7g52-hexadecanol J,
Og.

A mixture of dimethylacetamide izog was heated to 7j0C under stirring in a nitrogen stream, and then 10ml of dimethylacetamide containing dimethyl azobisisobutyrate/Og was added to initiate polymerization. After reacting for 5 hours, the reaction solution was cooled and added with water 3
1, the precipitated solid was filtered out and washed thoroughly with water. Comparative example polymer coupler (R) JA, fg was obtained by heating and drying this solid under reduced pressure.

This polymeric coupler shows that the copolymer formed by chlorine analysis has the coupler units of the monomeric coupler (at) j/, 4L.
It was recognized that the content was % by weight. The number average molecular weight by GPC is /! It was 000.

Comparative Synthesis Example 1 (copolymer of monomer coupler (1) and butyl acrylate) Monomer coupler (I) copolymer butyl acrylate/
Comparative polymer coupler (S) was synthesized using 7g52-hexadecanol J, Og under the same conditions as Comparative Synthesis Example 17.
．． 2g was synthesized.

This compound contained 7% of the coupler units of monomeric coupler (1) according to chlorine analysis, and the number average molecular weight according to GPC was 000.

Comparative synthesis example λO (Copolymer coupler of monomer coupler (λ7) and butyl acrylate) Monomer coupler (core) CoOg, butyl acrylate/
7g, rhohexadecanol J, Og, comparative polymer coupler (T) was prepared under the same conditions as in Comparative Synthesis Example tr.
, 2g was synthesized.

This compound is suitable for chlorine analysis, monomeric coupler (core)
It contained 10.1% of coupler units, and the number average molecular weight by GPC was OOOO.

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, containing about 30 mol% or less of silver iodide. . 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 may be a composite form thereof.

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

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Magnetic 17643
(December 1978), pp. 22-23-''+, Emulslon preparation and
types)', and N118716 (19
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafkld)
es.

Chemical at Ph1sique Pho
Lographique Paul Montel
.

1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, P. Uffin, Photogr.
aphicEmulsion Chemistry
(Focal Press+ 1 9 6 6
), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zelikma
Making and Coating
Photographic Emulsion, F
ocal Press.

(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.
engineering), 1st
4@, pp. 248-257 (1970); U.S. Patent No. 4
, 434°226, 4,414,310, 4,
433.048, 4,439.520 and British Patent No. 2.112,157. : The crystal structure may be --like, the inside and outside may have different halogen compositions, it may have a layered structure, or silver halides of 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 sensitization. Additives used in such processes are listed in Research Disclosure Magnetics 17.
643 and Na1B716, 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.

Additive type RD17643 RD18716
1 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity increasing agent
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 prevention scraping Various color couplers can be used in the present invention, and specific examples thereof can be found in the aforementioned Research Disclosure (
RD) 17643, ■-C to G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
3.501, 4.022.620, 4.3
No. 26,024, No. 4.401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1.425.020,
Same 1st. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
0.619, European Patent No. 4,351°897, European Patent No. 73.636, U.S. Patent No. 3,061,432,
No. 3,725.067, Research Disclosure N124220 (June 1984), JP-A-60-
No. 33552, Research Disclosure Na24
230 (June 1984), JP-A-60-43659, U.S. Patent No. 4.500.630, U.S. Patent No. 4.540.
Particularly preferred are those described in No. 654 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 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. 2.7162, No. 2.895,826, No. 3.
．． No. 772,002, No. 3.758,308, No. 4,334.011, No. 4,327,173, West German Patent Publication No. 3.329.729, European Patent No. 121
．． No. 365A, U.S. Patent No. 3. 446. No. 622,
4.333.999, 4.451.559, 4.427.767, European Patent No. 161.62
Those described in No. 6A etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure-17643.
- Section G, U.S. Patent No. 4.163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4. 138. No. 258, British Patent No. 1.146.
The one described in No. 368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, EP 96,570 and DE 3,234,533 are 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 camping can also be preferably used in the present invention. DIR couplers that release 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 anti-glare material of the present invention include the competitive couplers described in U.S. Pat. No. 4,130,427, etc.; 338. 3 “93, same 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 couplers releasing couplers or redox, couplers which release i-colored dyes after separation as described in EP 173.302A, R, D, Na 11449, EP 242
Examples include bleach accelerator-releasing couplers described in No. 41, JP-A No. 61-201247, and Gantt-releasing couplers described in U.S. Pat. No. 4,553,477.

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

C-(11 C-(2) C-+31 C-141 C-151 j C-+61 j Molecular weight: Approximately 40.000 C-(71 C-+81 C-+91 C-Q@ -aO I C-(2) H Cs1l+v(t) -aS OH C-a leak C-(to) OH LiJL;4tlqυshiυNl+ C-Q・ C1l.

C-A B ■ SCHgCHtCOtH -am OH )υ1lla C- (to) -am R υ C.B.

\ C- (to) ■ CH.

c-(24) C-(25) c-(26) I C-(27) C-(2B) C-(29) C-(30) C-(31) C-(32) i1 0CHmCHtCONHCHzCIIgOCHsC-(
33) N=N C-(34) c-(35) C-(36)! C-(38) C+eH 1 C-(39) View j C-(40) C-(41) H C-(44) C-(45) I C-(46) H C-(47) I C -(4B) C-(49) C-(50) C-(51) c-(53) j C-(54) C-(55) C-(56) -t, ++1teC-( 57) C-(58) II3 C-(59) C-(60) The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2.322.027 and the like.

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 M (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,l-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, tryptoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetra decylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4
-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters'R (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-
2-butoxy-5-tert-octylaniline, etc.)
, hydrocarbon II (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C or higher.
An organic solvent having a temperature of 160°C or higher 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 process steps, effects, and latex for impregnation can be found in U.S. Pat. No. 4,199.363, O.L.S. etc. are listed.

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
It is described on page 28 of D, N117643, and from the right column of page 647 to the left column of page 648 of question mark 18716.

The color photographic material according to the present invention is described in the above-mentioned RD, Arashi 17643, pages 28-29, and 18716, 6
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, typical examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3-diethylaniline, and 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 slowing agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, and fogging agents such as sodium boron hydride. , an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, various calcinates such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, for example, Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, ■-hydroxyethyl') f'7
-1.1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-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-pyrazolidones 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 it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

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 separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■) and cobalt (I).
Compounds of polyvalent metals such as II), chromium (■), and copper (II), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminoacetic acid. Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron(II)t, including ethylenediaminetetraacetic acid iron(III)tit salt! Salts and persulfates are preferred from the standpoint of rapid processing and prevention of environmental pollution, and aminopolycarboxylic acid iron (mal) 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 (III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. can.

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;
, No. 290,812, No. 2,059°988, JP-A-53-32.736, No. 53-57,831, No. 5
No. 3-37,418, No. 53-72,623, No. 53
-95,630, 53-95,631, 53-
No. 10.4232, No. 53-124.424, No. 53
-141.623, No. 53-28.426, Research Disclosure Magnetic No. 17,129 (July 1978), etc. Compounds having a mercapto group or disulfide group; JP-A-50-140.129 Thiazolidine derivatives described in JP-B No. 45-8,506, JP-A No. 52-20,832, JP-A No. 53-32,735,
Thiourea derivatives 4 as described in U.S. Pat. No. 3,706,561
Body: Nishi-Kokutoku 1 Ya No. 1,127,715, Japanese Patent Application Publication No. 1983-
Iodide salts described in West German Patent No. 16゜235; polyoxyethylene compounds described in West German Patent No. 966゜410 and West German Patent No. 2,748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; No. 49-42.434, No. 49-59,644, No. 53-94.927, No. 5
No. 4-35,727, No. 55-26,506 No. 5B-
Compounds described in No. 163,940; bromide ions, etc. can be used.

Among these, compounds having a mercapto group or a disulfide group are preferable because they have a large promoting effect, and are particularly preferred in the US.
Patent No. 3,893,858, West Patent No. 1,290.81
No. 2, JP-A No. 53-95,630 is preferable, and the compounds described in U.S. Pat. No. 4,552,834 are also preferable. 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, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfite, Tn sulfite 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
tion Picture and Televisi
onEngineers No. 64@, P, 248-253
(May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8.542
Chlorine-based disinfectants such as inchiazolone compounds, cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, Sanitary technology complete volume "Sterilization of microorganisms" It is also possible to use the disinfectants described in "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japanese 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 be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15-45°C, preferably 30 seconds to 5 minutes at 25-40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8,543 and 58-14.
All known methods described in No. 834 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. .

It is also possible to add various botanical agents and antifungal agents 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. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3.342.59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
No. 15,159 and the Schiff base type compound described in the same No. 15,159,
Aldol compounds described in U.S. Patent No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 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.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226.770 or U.S. Patent No. 3
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in US Patent No. 4.
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.660A2, etc. (Example) The present invention will be explained in detail by Examples below. is not limited to these.

Example/A color photographic material was prepared by coating the following layers from the first layer to the first ≠ layer on a triacetate base.

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

1st layer (antihalation layer) Black colloidal silver...0. JO gelatin...Co, 20UV-/
... o, orUV-x
-・・o, t.

UV-J　　　　　　　　--・o, t.

5olv-7...-o,i.

2nd layer (intermediate layer) Gelatin...0.20 3rd layer (low sensitivity red-sensitive layer) Monodisperse silver iodobromide emulsion (AgIu morch, cubic, average grain size 0.3μ, a/r=0. /the law of nature· · ·
0. jO EXS-/ ・ ・ ・/ , 1l-OX
lo-3ExS-,2・・・J, 00×10−5
Gelatin... o, t.

Coupler (PI) o, 3So of the present invention
lv-ko ... 00o3rd μ layer (medium-sensitivity red-sensitive layer) Monodisperse silver iodobromide emulsion (AgIJ, j morch, /≠hedral,
Average particle size O, 4tZμ, s/r=o, iz)
... 0. joEXS-/ ・・
・/ , tOXlo-3ExS-2...J , 0OX
10-5 gelatin... ・/, 0
0 Coupler (IV) of the present invention... o, 4tz
Solv-x--0. Orth! Layer (high-sensitivity red-sensitive layer) Monodisperse silver iodobromide emulsion (AgI=, z, j morti, /≠hedron, average grain size 0.60μ, S/r=o, tr)
... o, z.

ExS-t --・t , &oxlo-3Ex
S-2 --- 6.00X10-5 gelatin... 0.70 Coupler of the present invention (■)... 0.3 Solv-co
・-・ 0.0J layer (middle layer) Gelatin /・0Cpd-
/o,tSolv
-i --・ o, ozSolv-2-
・・ o, or Solv-J --・ 0. /koCpd
-2 ・ ・ ・ 0.2J 7th
Layer (Low sensitivity green sensitive layer) Silver iodobromide emulsion (AgI=j, O mole, normal crystal, mixed twin crystal, average grain size 0.3μ) ・ ・ ・ 0. tj ExS-3...-3,3oxlo-3 ExS-4.../ , 10X/ 0-3 gelatin
... /,jOExM-/
--・ 0.10ExM-2... O6λj Solv-x ・ ・ ・
0. jOth layer (high sensitivity green sensitive layer) Tabular silver iodobromide emulsion (AgI = J, j morch, grains with a diameter/thickness ratio of 1 or more account for 101% of the projected area of all grains, average thickness of grains o , ijμ)・・・0.7 Q ExS-3・--t , go×1O-3ExS-Hiroshi
...j, 00X10-4 gelatin
... /, 00ExM-J
... O, kojCpd-j ・
・ ・ 0.10Cpd-da
・ ・ ・ 0.02Solv-2... O0O! 2nd layer (middle layer) Gelatin...0. ．． 10th 1st O
Layer (yellow filter layer) Yellow colloid) Silver... 0.10 Gelatin layer... /, 00Cpd
-/ ・ ・ ・ o, ozS
olv-/ ・-・ 0.0J5ol
v−x --・0.07
Cpd-2・・・o,i.

1st/layer (low sensitivity blue sensitive layer) Silver iodobromide emulsion (AgI = 2.! Morch, normal crystal, mixed twin crystals, average grain size 0.7μ) ・ ・ ・ 0.22 ExS-1・-- / , OO×/ 0-3 gelatin
... 0. ri0ExY-t
-・-o, z.

5olv-x　　　　　　　... o, t.

1st co-layer (high sensitivity blue-sensitive layer) Tabular silver iodobromide emulsion (AgI = 2.j morti, grains with a diameter/thickness ratio of 3 or more are jO% of the projected area of all grains, average thickness of grains 0./Jμ)・・・i,o.

ExS-z.../, yo×1o-3 gelatin...2.00ExY-71
・-t, o.

5olv-2...Oo-〇 13th layer (ultraviolet absorption layer) Gelatin... /,! 0UV-
/ ... 0.0λUV-2・
・・ 0.0≠ UV-J −・−o, o4tCp
d-j ・ ・ ・ 0. J.O.
8olv-/ ・-・ 0. JOCp
d-4・・・0.10 First layer (protective layer) Fine grain silver iodobromide (1 molten silver iodide, average grain size 0.10)
0jμ) ... 0.70 gelatin
... Ko, 0θH-/
... 0.30E x S-/ τ ExS-2 ExS-J ExS-HiroOa- ExS-j 10N(C2H5)3 V-t V-2 (t)04H9 UV-3 Cpd-i Cpd -Copolyethyl acrylate Cpd-J CH3 Cpd-g Cpd-j Cpd-j ExM-/α ExM-1
;) Linonyl phosphate H-/:I, 2-bis(vinylsulfonylacetamido)ethane Next, sample 10/3rd layer, 3rd layer, 3rd layer! The inventive coupler HV) added to the layer is combined with the inventive coupler (V), (
M), (■), (■), and comparative synthesis example coupler (
Replace A), (B), (Q), (C), and (D) so that the amount of coupler applied (mol/m2) is the same,
Samples 10λ to 110 were created.

The material was prepared as described above and processed according to the silver nine halide color photographic light-sensitive material process.

Processing process Time Temperature 1st development Minutes Jr 0C Water Washing Cominutes jff'c Reversal Cominent jr'c Color development 2 minutes jr'c Adjustment 2 minutes 3r 0c Bleach Minutes 3r 0c Fixing
The composition of each treatment liquid was as follows.

Nitrilo-N,N,N-)limethylenephosphonic acid, j sodium salt 2.0g Sodium sulfite 30g Hydroquinone,
Potassium monosulfonate log potassium carbonate 33g1-phenyl-
P-Methyl-Hydroxymethyl-3 Pyrazolidone λ, og Potassium bromide ko, tg Potassium thiocyanate /,, 2g Potassium iodide
λ, omgpHta, t.

pH was adjusted with hydrochloric acid or potassium hydroxide.

Nitrilo-N,N,N-trimethylenephosphonic acid
! Sodium salt J, OK stannous chloride cohydrate salt
/, Ogp-aminone enol
0.1g sodium hydroxide
rg glacial acetic acid /jmll
pHt, 00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer nitrilo-N,N,N-trimethylenephosphonic acid! Sodium salt K, og Sodium sulfite 7.0g Trisodium phosphate dodecahydrate jug Potassium bromide /, 0g Potassium iodide TAomg Sodium hydroxide J, 0g Citrazic acid
/, 1 g N-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-≠-aminoaniline sulfate 11 g 3.6-cythiaoctane-l.

t-diol /, 0gpH //,
rO pH was adjusted with hydrochloric acid or potassium hydroxide.

Ethylenediamineproacetic acid, cosodium salt, cohydrate r, og sodium sulfite /2g/-thioglycerin 00ml pH was adjusted with hydrochloric acid or sodium hydroxide.

Bleach solution Ethylenediamine≠acetic acid, cosodium salt, cohydrate salt, Ogethylenediamine≠acetic acid, Fe ([1), ammonium, cohydrate salt 720g potassium bromide 100g ammonium nitrate 10gpH was adjusted with hydrochloric acid or sodium hydroxide.

Fixer Sodium sulfite J, 0g Sodium bisulfite R, og Add water
1000m100Ot, tO pH was adjusted with hydrochloric acid or aqueous ammonia.

Stabilizing liquid formalin (37ch)! , Oml・
Polyoxyethylene-p-mo)/nylphenyl ether (average degree of polymerization/(7) 0.1 ml water was added to 1000 ml without pH adjustment. The density and relative sensitivity of the cyan image of these processed samples were measured.

The obtained results are summarized in Table 2 K.

As is clear from Table 2, the samples containing the telomer couplers of the present invention exhibited significantly high color development regardless of the coupler unit content, and the comparative couplers (conventional polymer couplers and those with a chain transfer constant of o, A significant increase in sensitivity is observed compared to couplers using chain transfer agents outside the i-λO range.

Example 2 On a subbed cellulose triacetate film support,
A sample λO/, which is a multilayer color photosensitive material having each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is determined by the amount 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 number of moles of sensitive dyes is expressed per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver...0.2 gelatin/3ExM-ta
・-・ o,otUV-/
・ ・ ・ 0.0JUV-2・
・ ・ 0.01 0V-3・ ・ ・ o,ot Solv-/ ・ ・ -o,
tzSolv-x ・--17
,/J-8olv-j ・--
0, 0, second layer (middle layer) gelatin /, 0UV-t
-・-o, o3ExC-Hiroshi
... 0.0 CoExF-/
・-・0.00 hiro5olv-/
0. /5olv-20,/ 3rd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgIu morch, uniform-Agl type, equivalent sphere diameter 0.2 μ, coefficient of variation of equivalent sphere diameter 0.01, plate-like Grain, diameter/thickness ratio 3.0) Coated silver amount... /, 2 Silver iodobromide emulsion (AgIJ Morch, uniform-Agl type, equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter / Yochi, Spherical particles, diameter/thickness ratio/, 0) Coated silver amount...Q, Otsu gelatin.../, OE x
S −/ ...≠X1O-4ExS-
x...-jXlo-5E x C-/
... o, orExC-2...
o,z.

EXC-J...0.03ExC
-da ... o, iλE x C-j
... 0.0/EXC-r
・--0,0! μth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgIJ morch, internal high AgI type with core-shell ratio 1:1, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter / 1%, plate shape Particles, diameter/thickness ratio!, O) Coated silver amount... 0.7 Gelatin /, 0ExS-
/ ...JXlo-4EXS-1・
・・2 , JXlo-5 ExC-1---o, /1 ExC-7・ ・ ・ 0.0j ExC-a ---o, o
tSolv-/ ・--o, o
jSolv−j −・−0,
Or jth layer (middle layer) Gelatin...0. jtCpd
-/0. /5olv-
/ ・-・ 0.0! Layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgIa morti, core-shell ratio /:l surface height AgI type, equivalent sphere diameter O, jμ, coefficient of variation of equivalent sphere diameter /!q &, plate-like Particles, diameter/thickness ratio, o) Coated silver amount... 0.3! Silver iodobromide emulsion (AgIj morti, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter ko, spherical grains, diameter/thickness ratio t, o) Coated silver amount... O, CoO Gelatin /, 0ExS-
3・--jXlo-4 ExS-Hiroshi...-3×1O-4 ExS-j...-/X10-4
Coupler (XI) of the present invention... o, aEX
M-1-・・0.07 ExM-10・・-0,02 ExY-//・・0.0JSOI
V-10,7 Solv-a
-Fist -o, or 7th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag I 4μ morch, core-shell ratio/
:3 internal height AgI type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particle, diameter/thickness ratio! , O) Coated silver amount... o, r Gelatin 0... Q, 3ExS
-j...jX/1)-4EXS-
F...jXlo-4E x S
-1.../"X10-4 Coupler of the present invention (XI)
... 0.1ExM-ta
・・ 0.02ExY−//
・--0,0JExC-2・--0,0J ExM-/ ≠ ・ ・ ・
O, Oda5olv-10,2 Solv-p --・・
0.0/rth layer (intermediate layer) Gelatin... 00ICpd-
/ ・ ・ ・ 0.0 evening 5
olv-/ ・-・ o, o-th layer (
Donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (A
gIJ molti, internal high AgI type of core-shell ratio Conil,
Equivalent sphere diameter, /, 0μ, coefficient of variation of equivalent sphere diameter /j1g, plate-shaped particles, diameter/thickness ratio 4.0) Coated silver amount... 0. Jj Silver iodobromide emulsion (AgI2 molti, core-shell ratio /:l internal high AgI type, equivalent sphere diameter O, aμ, coefficient of variation of equivalent sphere diameter 2014, plate-like grain, diameter/thickness ratio & , 0) Coated silver Amount... 0.20 Gelatin 0. jExS-
3・---rxto-4 ExY-/J --・0. //EXM
-I2...0.0JExM-/≠
... 0.10Solv-/
・--0,20 1st θ layer (yellow filter layer yellow colloidal silver...0.02 gelatin o, rCpd-x
... o, /3Solv-/
... (7, /JCpd-/
---0,10 11th layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI, ! molar range, uniform AgI type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter /j H, plate-like grains, diameter/thickness ratio 7.0) 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 Jjchi, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount... 0. /! Gelatin /, 4ExS-
4・-・1x10-4 ExC-I4 ・-・0.0jExC
-2... 0.10 ExC-J...-0,02ExY-
/J ---θ, 07ExY-lj
/,.

5olv-/ ・--0,20 No. 7.2
Layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgIio morti, internal high Agl type, equivalent sphere diameter /, 0μ, coefficient of variation of equivalent sphere diameter 2'S, multi-twinned plate-like grains, diameter / Thickness ratio.

O) Coated silver amount...Q,! gelatin
0.2ExS-1...-/
x10-4 ExY-tz -・-o, 2゜ExY-
/J...0.0/5olv-/
... 0.10 73rd layer (first protective layer) Gelatin ... 01tUV-Hiroshi 0. /UV-t
... 0. /jSolv-/
・-・ 0.0/5olv-,2... 0.0
/ 1st ≠ layer (second protective layer) Fine grain silver bromide emulsion (AgI comolti, uniform AgI type, equivalent sphere diameter 0.07μ)...Q,! gelatin
... 0. μ! Polymethyl methacrylate particle diameter 1. ! μ... O, Ko H-t... O0 HiroCp
d-IO,j Cpd-J...00jCpd
-r... O, Co In addition to the above components, each layer contains an emulsion stabilizer cpti-J (0,04
4g/m2) surfactant Cp d -II (0,02
g/m2) was added as a coating aid.

UV-/ UV-2 Uv-da UV-r Solv-/ Tricresyl phosphate 5O1v-27 Diptyl talate Solv-J Solv-≠ Cpd-/ 6H13 cpa-Cpd-7 H Cpd-J Utt Cpd-da Cpd- 4 H2 Ex C-/ExC-ko0M WM2L:M2C:υ2(H3 ExC-gH ExC-1 ExC-j divination H2 ExC-buR H2 C(CHa)s ExC-7 0H ExY-2 ExY-// ExY-/CoExY-/J EXM-/ HiroExY-/j ExC-/1 O)T EXS-/ ExS-CoExS-J EXS-≠ ExS-r ExS -t -t gxF-/ 1, ;2Mg';2f15 Next, the coupler of the present invention ('A) added to the 7th layer and the 7th layer of sample-O/ was added to the coupler of the present invention (Xll), the polymer turnip of the comparative synthesis example, y-(E), (G), (R), (
As shown in Table 3 in F) and (H), sample -
〇Co-Co07 was created.

The color photographic material as described above was exposed with a continuous wedge and then processed in the manner described below.

Table - Processing method Step Processing time Processing temperature Color development 3 minutes! seconds 3r 0c bleach
minutes 30 seconds 3r 0c water washing 2 minutes 70
Sec 4A'C Fixation μ min 0 sec 3r'c Washing (1) 7 min 03 sec 4!0C Washing (2) 2 min/Q sec 2≠0C Stable 7 min 03 sec 3r'c Drying ≠ minutes O seconds zr 0c Next, the composition of the treatment liquid will be described.

(Color development PK) (Unit g) Diethylenetriaminepentaacetic acid /, O7-hydroxyethylidene- /, /-diphosphonic acid 3.0 Sodium sulfite Hiroshi, 0 Potassium carbonate
! 0.0 potassium bromide
/, 4C potassium iodide
i, zmg hydroxylamine sulfate
2. Hirohiro-(N-ethyl-N-β-hydroxyethylamine) monomethylaniline sulfate Hirohiro! Add water /, 01pHto, o
z (Bleach Solution) (Units: g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 14Ao.

Ammonium nitrate 30.0 Ammonia water (7 pieces) A, add 1ml water
/, 01 pH 4,0 (Fixer) (Unit g) Ethylenediaminetetraacetic acid disodium salt o, r Sodium sulfite 7.0 Sodium bisulfite! , O ammonium thiosulfate aqueous solution (yo%) tyo, om1 Add water /, 01 pH, 7 (stabilizing solution) (unit g) Formalin (s7qb) 2. oml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization io) o, s ethylenediaminetetraacetic acid disodium salt 0.0! Add water /, 01 pHz, o-r,.

The density and relative sensitivity of the magenta color images of these processed samples were measured.

The obtained results are summarized in Table 3.

From the results in Table 3, the telomer coupler of the present invention has higher sensitivity than the comparative couplers (conventional polymer couplers and couplers using a chain transfer agent with a chain transfer constant outside the range of 0.1-20). It is clear that the gradation is hard and the color density is high.

(Example 3) A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

27. Prepare the coating solution for the first layer by adding 7 g of yellow coupler (EXY) and an anti-fading agent (Cpd-/)≠,≠og to ethyl acetate. ．． 2c
c and 7.7 cc of solvent (Solv-/) were added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate rcc t-containing trlO%-L' latin aqueous solution/
It was emulsified and dispersed in r j cc. On the other hand, silver chlorobromide emulsion (
The blue-sensitive sensitizing dye shown below was added to silver bromide (to, o mol %, containing Ag 70 g/Kg) at pj, O x 10 - per mol of silver.
A sample containing 4 moles was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to obtain the composition shown below.
A layer coating solution was prepared. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is l-oxy-3,! -Dichloro8-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (i per mole of silver halide) z, ox 7 (7
-4 mol) green-sensitive emulsion layer (μ per mol of silver halide, OX/Q-4 mol) and (l per mol of silver halide) 7. o x i o-
5 mol) red-sensitive emulsion layer (po, yxio-4 mol per mol of silver halide)
To the red-sensitive emulsion layer, the following compound was added in an amount of λ, ≦X10 −3 mol per mol of silver halide.

Furthermore, t-(r-methylureidophenyl)-! - mercaptotetrazole per mole of silver halide, 0x70-6 mole, 3°<1)X/0-S mole, /
, Ox/0-5-E:.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, ≠-hydroxy-6-methyl-/, J, Ja, and 7-titrazaindene were added at 1.0% per mole of silver halide, respectively. Ko x 10-2
mol, /, /X10-2 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2), and the silver halide emulsion represents the coating amount in terms of silver.

Support Paper support laminated on both sides with polyethylene [The polyethylene on the first layer side contains a white pigment (T i O2) and a bluish dye (ulmarine)] The second layer (
Blue-sensitive layer) C (ff Silver Genide Emulsion (Br:tO1%) o, sr
Gelatin 1. IJ yellow coupler (EXY) o, r3 color image stabilizer (Cpd-/) 0. /Solv-
/) 0.3j Second layer (color mixture prevention layer) Gelatin O-Tata color mixture prevention agent (cpa-2) o, or third layer (green-sensitive layer) Silver halide emulsion (Br:rO%) 0. / Tagelatin 1. Co3 mazen p coupler (ExM) 0.21 color image stabilizer (Cpd-
j) 0.01 color image stabilizer (cpa-ta)
o,ot stain inhibitor (Cpd-10)
o, tz solvent (Solv-1) 0
．． 27 Fourth layer (ultraviolet absorbing layer) Gelatin /, jl Ultraviolet absorber (UV-/) o, o7 (Uv-co)
Q, 3θ (UV-j) 0. Kota color mixing prevention agent (Cpd-4) 0.0! solvent(
Solv-2) O1λ≠5th layer (red-sensitive layer) Silver halide emulsion (Br) O, cono gelatin 7.3 Cyan coupler of the present invention (1) o, Jr color image stabilizer (Cpd- 7
) 0. /7 solvent (Solv-/)
0.23 Sixth layer (ultraviolet absorption layer) Gelatin 0. rJ ultraviolet absorber (UV-/) o, o, 2 (UV
-ko) o, l.

(UV-J) 0, Dr solvent (Sol
v-2). , 0゜ Seventh layer (protective layer) Gelatin /, 33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification / 7) o, / 7 Liquid paraffin 0.03 (EXY) Yellow coupler (EXM) Magenta coupler (Cpd -/) Color image stabilizer (Cpd-J) Color mixture prevention agent (Cpd-J) Color image stabilizer (Cpd-J) Color mixture prevention agent (Cpd-7) Color image stabilizer! :t:Remixture (weight ratio) (cpci-2) Color image stabilizer (Cpd-10) Anti-staining agent C4H9C4H.

\/ (UV-/) Ultraviolet absorber (Uv-2) Ultraviolet absorber (UV-J) Ultraviolet absorber (Solv-/) Solvent (Solv-2) Solvent (Solv-≠) l:2 mixture of solvents ( Capacity Ratio) A silver halide emulsion for a non-reactive emulsion layer was prepared as follows.

(/liquid) (coliquid) Sulfuric acid (/N) 2occ (3
Liquid) The following silver halide solvent (/'4) J
ccH3 H3 (Da liquid) (J liquid) (Liquid) (7 liquid) (L liquid) was heated to 7j0C, and (2 liquid) and (3 liquid) were added. Thereafter, (liquid 4) and (liquid !) were simultaneously added over a period of minutes. After another 70 minutes, (6 liquids) and (7 liquids)
Hiroshi! They were added simultaneously over a period of minutes. After 3 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust the pH to
Coefficient of variation (standard deviation divided by average particle size: s/d) 0
．． A monodisperse cubic silver chlorobromide emulsion of 10 molt of silver bromide was obtained. Sodium thiosulfate was added to this emulsion to perform optimal chemical sensitization.

Silver halide emulsions for the green-sensitive emulsion layer and the red-sensitive emulsion layer were also prepared in the same manner as above by varying the amount of chemicals, temperature, and time.

The average grain size, coefficient of variation, and halogen composition of the silver halide emulsions in the blue-sensitive, green-sensitive and red-sensitive emulsion layers are shown in the table below.

The cyan coupler in the j-th layer of Sample 3oi was replaced with couplers (n), (II[) of the present invention and comparative compound examples (I), (
Apply coupler to J), (S), (K), and (L) as shown in the table! Samples 302 to 301 were prepared in the same manner as sample 30/, except that they were replaced so that the (mol/m2) was the same.

These samples were passed through a continuous wedge, exposed to light, and then subjected to color development using the processing steps described below.

Developer Nitrilotriacetic acid/jNa salt Co,og Benzyl alcohol 11ml Diethylene glycol 10ml Na 2 S O3
J, Og KBr O,jg hydroxylamine sulfate j, Og Hiro-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl)-p-phenylenediamine sulfate z, o gN a2
CO3 (/water salt) Add 3og water/
(pH 10, /) bleach-fix ammonium thiosulfate <7wt%) ijomlNa
2 S O3/ j g NH4 (Fe (EDTA) ) j!g
EDTA-2Na Add 4'g water to make /l (pH increase) Process temperature Time Developer 33°C 3 minutes 30 seconds Bleach-fix solution 33°C 1 minute 30 seconds Water Washing λt~3r0c J revolution Drying The results of measuring the cyanide concentration of the treated samples are summarized in Table 1.

From the results in Table 1, it can be seen that the samples containing the telomer coupler of the present invention have a higher It is clear that it shows remarkable high color development and also has high sensitivity.

(Example Hiroshi) Of the layer structure shown in Example 3, the magenta coupler (EXM) in the third layer was replaced with the couplers (XIV) and (X
V), (XM), (X■) and comparative coupler (M),
Except for replacing (N), (T), (0), and (P), and adding color image stabilizers and anti-stain agents as shown in the table below,
Assuming exactly the same as Example 3 (sample 30/), sample≠0/-
1702 was created. Coupler coating amount (mol/m2) is the same as EXM.

Pass these samples through an optical wedge.1. After exposure, color development was performed in the same manner as in Example 3. The results of measuring the magenta density of these treated samples are summarized in Table 3.

From the results in Table 3, it can be seen that the samples containing the telomer coupler of the present invention are comparative Kabutsu (conventional polymer couplers and couplers using a chain transfer agent with a chain transfer constant outside the range of 0./-coO). It shows remarkable high color development compared to
And it is clear that the sensitivity is high.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1, Incident Indication: Showa tλ Year Sign Application No. 2 Octopus! Tata No. 2, Name of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Table of patent applicants Subject of the amendment Column 5 of "Detailed Description of the Invention" of the specification, Description of the contents of the amendment The description in the "Detailed Description of the Invention" section is amended as follows.

1) Line 3 of page 1 "G, oto, co// issue, waiting for the United States" "Hiroshi, oro, 2ii4!, UK waiting" and correct it.

2) Page 2, line 1 [ "of " ” and correct it.

3) bottom line of taP page " and correct it.

4) Page 10, line 7, "(-X1MoJ'-X"+p(-J2-X"+q+J3
-) 8".

5) Page io, line l [R5 18OzN-J “R5 18OzN-J and correct it.

6) Number 7! page/line " ” and correct it.

7) Page 77, line z "ion atom" "Sulfur atom" and correct it.

8) IE Co/Page Buddhist pilgrimage “-N- R “” “-N- 7J and correct it.

9) No./page/! row "7 elements" "Fluorine" and correct it.

lo) 2nd ≠ page as line After "Concatenate" "." Insert.

11) The λth page l! Correct “N-methyl, tetradecanamide” in the second line to “N-methylnato-2-decaneamide”.

12) Delete "≠-titanium sulfur...~μm cyanoxyl," in the 2nd and 3rd lines of page j4c.

1g) 3rd! Change "/, 2, J, Hiro-triazole" to "/, ko," on the first row of the page.
J, 4cm Tetrazole”.

14) Page 35, bottom line r　c　xm　),'' r (Xm), (XI[I’),” and correct it.

15) 3rd page 1st line r CXIV ), CXV ml J to r (XIV
), I:X]V':l, CXV ), [:XV':IJ
and correct it.

16) No. ≠ 7) i/7th line "Chain transfer constant" "The chain transfer constant is" and correct it.

17) Shine the grass zf〒8 and correct it.

18) Page 35, bottom line and correct it.

19) Page 72, line l “E(Mn)XJ rE(-M-)nXJ and correct it.

20) Between the 73rd line and the lth line on page 7-2, add “-2EM
Insert n-→E-eM-)-1, EJ.

21) Page 72, line 16 “E(Mn)XJ "E+M+-nX" and correct it.

22) Page 73, line 7 After “more than or equal to the number of carbons” Insert all "with a chain transfer constant of 0.1 or more and 20 or less."

23) In line 71jE, “General formula [XX■], [XXV) J t” General formula C
XXIV) J.

24) Page 27, line 1 ” and correct it.

25) Number 6 on page 6 "7×l0-3" “/xIO3J and correct it.

26) Page 103, line "Rotan silver" "Roda/@" and correct it.

27) The structural formula of compound C-(to) on page 12≠ is [ ” and correct it.

2B) 1st J! The structural formula of compound C-1 on page `` ” and correct it.

29) No. ity page ” Insert.

no) Page 72, table 3, footnote (3) “to CMSJt- "I CMS" and correct it.

31) The 7th line of Table 3 on the 1st reference page is corrected to "2-hexadecanol /X1O-3J".

32) No. 2/6 page! Notes column for sample 'l-07 in the table
Insert "Comparative Example".

1.Display of the incident Showa tco year special application No. 2121?2
No. 20 Title of the invention Silver halide power 2 - Photographic light-sensitive materials 3 Relationship with the case of the person making the amendment Patent applicant The description in the "Detailed Description of the Invention" column is amended as follows.

(1) 1st/2nd line from the bottom of the page "Phenylene group" "Arylene group" and correct it.

(2) Page 12! row "Phenylene group" "Arylene group" and correct it.

(3) Page 12, line 2 "Phenylene group" "Arylene group" and correct it.

(4) Page 17, line O r　SRI”　J r-8R18J and correct it.

(5) Page 0, line 10 [l~JOJt- [2~JOJ and correct it.

(6) Page 0, line 1 [t~30J [7~j17J and correct it.

(7) 2nd line from directly below to Hiroyukime "Ethylsulfonamide" "Ethanesulfonamide" and correct it.

(8) Page V7, line 20 r　(XX[)　J r　(X)I’l　J and correct it.

(9) 4th ct page 2nd line r (XXI) J r　(XXI’:]　J and correct it.

Kan No. 1091g Compound C- (The structural formula of 11 is “ and correct it.

all alE/ P$ Page, right below, line J [) Insert “reciprocal” before “logarithm”.

Claims (1)

[Claims] The lipophilic polymer coupler is obtained by polymerization using a chain transfer agent having a carbon number of 8 or more and a chain transfer constant of 0.1 to 20 with respect to the monomeric coupler. A silver halide color photographic material characterized in that it is a silver halide color photographic material.