JPH02220048A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material superior in sharpness and good in graininess by incorporating a polymer coupler having repeating units derived from a specified monomer capable of coupling with the oxidation product with an aromatic primary amine developing agent and forming a dyestuff, and a monodispersed silver halide emulsion. CONSTITUTION:The silver halide color photographic sensitive material is enhanced in graininess and sharpness by incorporating the monodispersed silver halide emulsion and the polymer coupler having repeating units derived from at least one kind of monomer capable of coupling with the oxidation product with an aromatic primary amine developing agent and forming a dyestuff, and represented by formula I in which X is -COO-, -CONR5-, or phenylene; each of Y1 and Y2 is -O-, -S-, -SO-, -SO2-, -CONR5-, or -COO; and Q is a coupler residue capable of coupling with the oxidation product with an aromatic primary amine developing agent and forming a dyestuff. The most preferable silver halide composition of grains in the monodispersed silver halide emulsion is the silver halide gains having substantially two clear layer structure composed of a rich-iodide core part and a poor-iodide shell part.

Description

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

(Prior art) Recently, color photographic materials have been progressing toward higher image quality.
Image quality that can withstand viewing even when enlarged from a small format such as 110 size has been developed. However, advances in graininess and sharpness have been strongly desired.

Regarding sharpness, methods such as DIR compounds as typified by JP-A-59-36249 and JP-A-54-145135 are used to emphasize the edge effect, and the coating film is made thin to minimize light scattering. There is a way. It is shown in JP-A-59-36249 that a combined use of these means provides even greater effects.

In order to achieve one layer, ■ Reduce the ballast group of the coupler.

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

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

There are methods such as, but with ■, there is a problem with the diffusion resistance of the coupler, and with ■, it is difficult to reduce the number to the edge due to the precipitation of the coupler and a decrease in color development, and it is not expected to form a large single layer. In , (2), the coupler can be used stably without using a high-boiling point solvent or with a small amount of a high-boiling point solvent, and a great effect of thinning the layer is expected. However, there is a desire for further improvement in the coloring properties of polymer couplers.

Further, when a polymer coupler is used to reduce gelatin and make the emulsion layer thinner, sharpness is improved, but graininess is deteriorated.

On the other hand, as a technique for improving graininess, for example,
As disclosed in No. 1-75347 and JP-A No. 61-77051, a method is known in which a monodisperse emulsion and various oil-soluble couplers are used in combination.
S graininess (T, for RMS graininess)1. Ja
+mes+'Theory of thePhotog
RAPHJC Process", 4th edition, p. 619), the improvement in visual graininess is slight, although it is improved to some extent.

As a method for improving both visual graininess and RMS graininess, as described in JP-A-59-131936, oil-soluble dye-diffusing couplers and monodispersed emulsions are used. Although it is known that the combination of these two methods has a small graininess improvement effect, the sharpness has not been improved.

(I! Problem to be Solved by the Invention) An object of the present invention is to provide a silver halide color photographic material with excellent sharpness and good graininess.

(Means for Solving the Problems) The above-mentioned object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which an aromatic primary amine developer is oxidized. It is characterized by containing a monodisperse silver halide emulsion and a polymer coupler having at least one type of repeating unit derived from a monomer represented by the following formula [I] capable of coupling with a monomer to form a dye. This was achieved using a silver halide color photographic material.

Formula (1) % Formula % represents an alkyl group of 1 to 4, R2 represents a monosubstituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R1 and R
6 represents a linear or branched alkylene group having 2 to 10 carbon atoms, X represents -C0O-CONR,- or a phenylene group, and Yl and Y represent -OS So
Represents SOg-CONR5- or -COO-. R
1 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. Q represents a coupler residue capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developer, n, m and p represent 0 or l, 9 represents 2 to 10, r represents 0 to 10.

formula[! ] The monomer represented by will be explained in more detail.

Q is R5I of the following general formulas (Cp-1) to (Cp-9)
Any part of R19, Zl to Z, and Y is represented by the formula (!
] represents a group bonded to.

In the formula, R8 is a hydrogen atom, a chlorine atom, or a carbon number general formula (
Cp-1) General formula (Cp-4) General formula (Cp-5) 2゜General formula (Cp-2) General formula (Cp-6) General formula (Cp-7) Rs+-NH-C-CI-C -N)l-Rst general formula (
Cp-3) 7+ General formula (Cp-8) ss Next, R5I of the general formulas (Cp-1) to (Cp-9)
R5Q, l, m, and p will be explained.

In the formula, R51 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and Rst and R53 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R51 preferably has 1 to 22 carbon atoms, is substituted or unsubstituted, is linear or cyclic,
It may be either. Preferred substituents for the aliphatic group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R5+ are: isopropyl,
isobutyl, tart-butyl, isoamyl, tert
-amyl, 1.1-dimethylbutyl, 1,1-dimethylhexyl, 1.1-diethylhexyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, 2-methoxyisobusropyl, 2-phenoxyisopropyl, 2-
P-tart-butylphenoxyisoprobil, α-
These are aminoisopropyl, α-(diethylamino)isopropyl, α-(succinimido)isopropyl, α-(phthalimido)isopropyl, and α-(benzenesulfonamido)isopropyl.

When Ra1s Rst or R53 represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted, and the aromatic group such as the phenyl group may be an alkyl group having 32 or less carbon atoms, an alkenyl group, an alkoxy group, It may be substituted with an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic amide group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylureido group, an alkyl-substituted succinimide group, etc. In this case, the alkyl group contains phenylene in the chain. An aromatic group such as the like may also be present. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc. The aryl group may be further substituted with one or more alkyl groups having a total of 1 to 22 carbon atoms.

R111% The phenyl group represented by RSl or R82 may further include an amino group, including one substituted with a lower alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group, a cyano group, a thiocyano group, or May be substituted with a halogen atom.

R S l % R% @ or R53 may also represent a substituent in which a phenyl group is fused with another ring, such as naphthyl, quinolyl, isoquinolyl, chromanyl, coumaranyl, and tetrahydronaphthyl; these substituents themselves It may further have a substituent.

When RSI represents an alkoxy group, the alkyl moiety represents a straight or branched alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, and these are halogen It may be substituted with an atom, an aryl group, an alkoxy group, etc.

When RS l % R % t or Rss represents a heterocyclic group, the heterocyclic group is a carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or of the amide group, respectively, through one of the carbon atoms forming the ring. Combines with nitrogen atoms. Such heterocycles include thiophene,
Furan, biran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine 9, pyridazino, indolizine, imidazole, thiazole, oxazole, triazine,
Examples include thiadiazine and oxazine. These may further have a substituent on the ring.

In the general formula (Cp-3), RaS is 3 from carbon @l
2, preferably 1 to 22 linear or branched alkyl groups (e.g. methyl, isopropyl, tert-butyl, hexyl, dodecyl), alkenyl groups (e.g. allyl), cyclic alkyl groups (e.g. cyclopentyl, cyclohexyl, norbornyl), It represents an aralkyl group (e.g. benzyl, β-phenylethyl), a cyclic alkenyl group (e.g. cyclopentenyl, cyclohexenyl), and these represent /'% rogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxyl group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group,
Acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, It may be substituted with an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxyl group, a mercapto group, or the like.

Furthermore, RSS may represent an aryl group (e.g. phenyl, α- or β-naphthyl), and the aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, Cyclic alkyl group, aralkyl group, cyclic alkenyl group, halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group , acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, hetero m group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkyl Anilino group, N-
An arylanilino group, an N-acylanilino group, a hydroxyl group, etc. may also be present.

Furthermore, Rss is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a petro atom, or a fused heterocyclic group, such as pyridyl, quinolyl, furyl, benzothiazolyl, oxasilyl, imidazolyl, naphthoxacylyl), heterocyclic groups, aliphatic or aromatic acyl groups, alkylsulfonyl groups, arylsulfonyl groups, alkylcarbamoyl groups, arylcarbamoyl groups, alkylthiocarbamoyl groups substituted with the substituents listed for the aryl groups above. Alternatively, an arylthiocarbamoyl group may be added.

In the formula, R%4 is a hydrogen atom, 1 to 32, preferably 1 to 22, linear or branched alkyl, anikenyl, cyclic alkyl, aralkyl, cyclic alkenyl group (these groups include the substituents listed for Rss above) ), aryl groups and heterocyclic groups (which may have the substituents listed above for Rss), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, stearyloxycarbonyl), aryloxycarbonyl groups (e.g. phenoxycarbonyl, naphthoxycarbonyl), aralkyloxycarbonyl groups (e.g. bunzyloxycarbonyl), alkoxy groups (e.g. methoxy, ethoxy, heptadecyloxy), aryloxy groups (e.g. phenoxy, tolyloxy), alkylthio groups (e.g. ethylthio, dodecylthio), arylthio groups (e.g. phenylthio, α-naphthylthio)
, carboxyl group, acylamino group (e.g. acetylamino, 3-((2,4-di-tart-amylphenoxy)acetamido]benzamide), diacylamino group,
N-alkyl acylamino group (e.g. N-methylpropionamide), N-aryl acylamino group (e.g. N
~phenylacetamide), ureido groups (e.g. ureido, N-arylureido, N-alkylureido),
Urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino, diphenylamino, N-acetylanilino, 2-chloro-5-tetradecanamidoanilino), alkylamino group (e.g. n
-butylamino, methylamino, cyclohexylamino), cycloamino groups (e.g. piperidino, pyrrolidino)
, heterocyclic amino groups (e.g. 4-pyridylamino, 2-benzoxasilylamino), alkylcarbonyl groups (e.g. methylcarbonyl), arylcarbonyl groups (e.g. phenylcarbonyl), sulfonamide groups (g4 e.g. alkylsulfonamide, arylsulfonamide) ),
Carbamoyl groups (e.g. ethylcarbamoyl, dimethylcarbamoyl, N-methyl-phenylcarbamoyl, N
-phenylcarbamoyl), sulfamoyl groups (e.g. N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N-alkyl-N-arylsulfamoyl, N,N-diarylsulfamoyl) moyl), a cyano group, a hydroxyl group, or a sulfo group.

In the formula, R5 represents a hydrogen atom or a linear or branched alkyl/L/M group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group; It may have the substituents listed for R55 above.

R1& may also be an aryl group or a heterocyclic group (which may have the substituents listed for Rss above).

R represents a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a sialamino group, and an ureido group. , urethane group, sulfonamido group, arylsulfonyl group, alkylsulfonyl group, tri-ruthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-
An arylanilino group, an N-alkylanilino group, an N-acylanilino group or a hydroxyl group may be present.

R1, F? ss and R5 each represent a group used in a conventional 4-equivalent phenol or α-naphthol coupler, and specifically, R57 is a hydrogen atom,
Examples include halogen atoms, alkoxycarbonylamino groups, aliphatic hydrocarbon residues, N-arylureido groups, acylamino groups, -0Rat or -s-Rag (where R1 is an aliphatic hydrocarbon residue), and 2 or more R
5? When present, two or more R1, may be different groups, and the aliphatic hydrocarbon residues include those having substituents.

Further, when these substituents include an aryl group, the aryl group may have the substituents listed for Rss above.

Examples of R21 and Rss include groups selected from aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues, or one of these groups may be a hydrogen atom, and these groups may have substituents. including those with
Furthermore, Ra1l and R5Q may jointly form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues may be either saturated or unsaturated, and may be linear, branched, or
It can be any cyclic group, and is preferably an alkyl group (e.g. methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl), an alkenyl group (e.g. allyl, octenyl). Aryl groups include phenyl and naphthyl groups, and representative heterocyclic residues include polygroups such as pyridinyl, quinolyl, thienyl, piperidyl, and imidazolyl. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxyl, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, Examples include multiple groups such as aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino.

2 represents an integer of 1 to 4, m represents an integer of 1 to 3, and p represents an integer of 1 to 5.

Among the above coupler residues, as the yellow coupler residue, in the general formula (Cp-1), R8I is a t-butyl group or a substituted or unsubstituted aryol group, RS! is a substituted or unsubstituted aryl group, and in general formula (Cp-2), R8I and RS3 are preferably substituted or unsubstituted aryl groups.

Preferred magenta coupler residues are of the general formula (Cp
-3), when R84 represents an acylamino group, a ureido group, or an arylamino group, and Rss represents a substituted aryl group, R84 in general formula (Cp-4) represents an acylamino group, a ureido group, or an arylamino group, R5&
represents a hydrogen atom, and the general formula (Cp-5)
In (Cp6), R54 and Rsa represent a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, or cyclic alkenyl group.

Preferred cyan coupler residues have the general formula (Cp
-7) where Rs represents an acylamino group or ureido group at the 2-position, an acylamino group or alkyl group at the 5-position, and a hydrogen atom or a chlorine atom at the 6-position, and R5 in the formula -1 (Cp-9). ．． is a hydrogen atom at the 5-position, an acylamino group, a sulfonamide group, or an alkoxycarbonyl group, R8I is a hydrogen atom, and RS is a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group. This is a case of expressing

In the polymer coupler used in the present invention, the general formula (
Cp-1) to (Cp-9) 2. −2° and Y will be explained in detail below.

Zl represents a hydrogen atom, a halogen atom, a sulfo group, an acyloxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an alkylthio group, or a heterocyclic thio group, and these groups further include an aryl group ( (e.g. phenyl), nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. methoxy), aryloxy group (e.g. phenoxy), acyloxy group (e.g. acetoxy), acylamino group (e.g. acetylamino), sulfonamide group ( (e.g. methanesulfonamide), sulfamoyl groups (e.g. methylsulfamoyl), halogen atoms (e.g. fluorine, chlorine, bromine), carboxyl groups, carbamoyl groups (e.g. methylcarbamoyl), alkoxycarbonyl groups (e.g. methoxycarbonyl), sulfonyl groups (e.g. For example, it may be substituted with a substituent such as methylsulfonyl).

Z8 and Y represent a leaving group bonded to the coupling position with a hydrogen atom, oxygen atom, nitrogen atom or sulfur atom, and Z! and when Y is bonded to the coupling position with an oxygen atom, nitrogen atom or sulfur atom, these atoms are an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group,
In the case of a nitrogen atom, it also refers to a group that is bonded to an arylcarbonyl group or a heterocyclic group and, in the case of a nitrogen atom, can form a 5- or 6-membered ring containing the nitrogen atom and become a leaving group (for example, imidazolyl, pyrazolyl, , triazolyl, tetrazolyl).

The above alkyl group, aryl group, and heterocyclic group may have a substituent, and specifically, an alkyl group (e.g., methyl, ethyl), an alkoxy group (e.g., methoxy, ethoxy), an aryloxy group (e.g., phenyloxy), alkoxycarbonyl groups (e.g. methoxycarbonyl),
Acylamino (e.g. acetylamino), carbamoyl group, alkylcarbamoyl group (e.g. methylcarbamoyl, ethylcarbamoyl), dialkylcarbamoyl group (e.g. dimethylcarbamoyl), arylcarbamoyl group (e.g. phenylcarbamoyl), alkylsulfonyl group (e.g. methylsulfonyl), aryl Sulfonyl 1 & (e.g. phenylsulfonyl), alkylsulfonamide groups (e.g. methanesulfonamide), arylsulfonamide groups (e.g. phenylsulfonamide)
, sulfamoyl group, alkylsulfamoyl group (e.g. ethylsulfamoyl), dialkylsulfamoyl group (e.g. dimethylsulfamoyl), alkylthio group (e.g. methylthio), arylthio group (e.g. phenylthio), cyano group, nitro and halogen atoms (eg, fluorine, chlorine, and bromine), and when there are two or more substituents, they may be the same or different.

Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group.

Preferred groups for Z include groups that bond to the coupling site via a nitrogen atom or sulfur atom, and preferable groups for Y include groups that bond to the coupling site via a chlorine atom, an oxygen atom, a nitrogen atom, or a sulfur atom. This is the basis for

Z is a hydrogen atom or the following general formula (R-1), (R-2)
, (R-3), or (R-4).

In the formula Wl, R& represents an optionally substituted aryl group or heterocyclic group.

It represents a nonmetallic atom required to form a 4-membered ring, a 5-membered ring, or a 6-membered ring.

Among the general formulas (R-4), (R-5
) to (R-1).

R64 and RAS are each hydrogen atom, halogen atom, carboxylic acid ester group, amino group, alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted phenyl It represents a group or a heterocycle, and these groups may be the same or different.

(R-5) (R-6) Cp-2) CH*C In the formula, Rhs Rh't represents a hydrogen atom, an alkylaryl group, an alkoxy group, an ataloxy group, or a hydroxyl group, respectively, R 68, R49 and Ry. Each hydrogen atom, alkyl group, aryl group, aralkyl group,
or an acyl group, W represents an oxygen or sulfur atom.

Next, typical coupler monomers are shown below, but are not limited to these.

Cp-3) CP-1) Cp-4) Cp-6) Cp-7) I Cp CP-14) Cp-L L) Cp-12) Cp-16) CH.

H Cp-17) CI(.

CH2 0■ Cp-18) Cp-19) Cp-22) Hs Cp-24) Next, as a non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing reagent, acrylic acid , α-chloroacrylic acid, α-alkylacrylic acid (e.g. acrylic acid, methacrylic acid), and esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, t-butylacrylamide, methyl acrylate, methyl Methacrylate, ethyl acrylate, low propyl acrylate, l5O-propyl acrylate, n-butyl acrylate, low-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, low octyl acrylate, lauryl acrylate ζ~ and methylenebisacrylamide), vinyl esters (e.g. vinyl acetate, vinyl propionate, and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds, (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone) ), vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2-
and 4-vinylpyridine. Particularly preferred are acrylic esters, methacrylic esters, and maleic esters.

Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. For example, n-butyl acrylate and divinylbenzene, styrene and methacrylic acid, n-butyl acrylate and methacrylic acid, etc. can be used.

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

Polymer coupler latex can be obtained by simply extracting a lipophilic polymer coupler made by polymerizing coupler monomers, then redissolving it in an organic solvent and dispersing it in the form of latex, or by dispersing it in the form of a latex. Solutions of oil-based polymer couplers may be dispersed directly in latex form,
Alternatively, a polymer coupler latex prepared by an emulsion polymerization method or a layered polymer coupler latex may be directly added to the gelatin silver halide emulsion.

The proportion of the coloring part in the polymer coupler is usually 5 to 5.
80% by weight is desirable, but 20 to 70% by weight is particularly preferred in terms of color reproducibility, color development and stability. In this case, the equivalent molecular weight (grams of polymer containing 1 mol of coupler monomer) is approximately 250 to 4000, but is not limited thereto.

The polymeric coupler latex contains 0.005 mole to 0.5 mole per mole of coupler monomer,
Preferably 0. It is preferable to add 1 to 0.05 mol of O.

There are two methods for synthesizing coupler polymers: 1) the emulsion weight method and 2) the solution weight method. can get. The method for producing these polymers and the method for adding them to emulsions are disclosed in i) U.S. Pat.
No. 1,820, if) JP-A-62-42652.

The compositions of polymer couplers synthesized according to these patents are shown in Tables 1-3.

Synthesis Example (1) A mixture of 20.0 g of mer-p-〇m exemplary coupler (Cp-3), methoxyethyl acrylate 2Q, Og, and 200 ae of ethyl acetate was placed in a 500 d Mituro flask and stirred in a nitrogen stream. The mixture was heated to 70°C.

Dimethyl azobisinbutyrate 400af as a polymerization initiator
Polymerization was started by adding 10 ml of an ethyl acetate solution containing .

After polymerizing for 3 hours, the polymerization solution was cooled, poured into a No. 12 eggplant-shaped flask, and ethyl acetate was distilled off under reduced pressure to obtain P-1.
47.9g was obtained.

P-1 contained 50.6% repeating units of the exemplary coupler (P-3) according to elemental analysis.

The polymer couplers according to the present invention may be used in combination of two or more types, or may be used in combination with polymer couplers other than the present invention or conventional couplers other than polymers.

The monodisperse emulsion of the present invention is an emulsion having a grain size distribution in which the coefficient of variation S/r regarding the grain size of silver halide grains is 0.25 or less. Here, r is the average particle size and S is the standard deviation regarding the particle size. That is, the grain size of each emulsion grain is r
i and the number is ni, the average particle diameter r is defined as Σni·rk Σn+, and its standard deviation S is defined as.

In the present invention, the individual grain size refers to the silver halide emulsion described in T. H. James et al.
The Theory of the Photographic Process
otographicProcess) 3rd edition 36-4
3, published by Macmillan (1966), with a diameter equivalent to the projected area corresponding to the area projected when photographed using a method well known in the art (usually using an electron microscope), as described in be. Here, the projected equivalent diameter of a silver halide grain is defined as the diameter of a circle equal to the projected area of the silver halide grain, as shown in the above-mentioned book.

Therefore, the shape of the silver halide grains is other than spherical (for example, cubic, octahedral, dodecahedral, tabular, potato-shaped, etc.)
In this case, it is also possible to obtain the average particle diameter r and its deviation S as described above.

The coefficient of variation related to the grain size of silver halide grains is 0.25
It is not more than 0.20, more preferably not more than 0.15.

There is no particular restriction on the size of silver halide grains, but 0.4
It is preferable that it is μm to 5 μm, and more preferably 0.6 μm.
It is preferably 1.0 μm to 2.5 μm, particularly 1.0 μm to 2.5 μm.

The shapes of silver halide grains are hexahedral, octahedral, dodecahedral,
It may have a regular crystal shape such as a tetradecahedron (normal crystal grain), or it may have an irregular crystal shape such as a spherical, potato-shaped, or tabular shape. Particularly preferably, it has a regular crystal grain. be.

In the case of normal crystal grains, particles having 50% or more of (111) planes are particularly preferred, even in the case of irregular crystal shapes (111)
Particles with a surface area of 50% or more are particularly good, (111)
The surface area ratio can be determined by the Kubelka-Munk dye adsorption method. This is because dyes are preferentially adsorbed to either the (111) plane or the (100) plane, and the association state of the dye on the (111) plane and the association state of the dye on the (100) plane are spectrally different. select. The surface ratio of the (111) plane can be determined by adding such a dye to an emulsion and carefully examining the spectra with respect to the amount of dye added. For details on the dye adsorption method described above, reference can be made to Tadaaki Tani, "Nihonka Jizume", p. 942- (1984).

The halogen composition of the silver halide grains preferably contains 60 mol% or more of silver bromide, and 10 mol% or less of silver chloride, and more preferably 2 mol% to 40 mol% of silver iodide.
Particularly preferred are grains containing 5 mol% to 20 mol% of silver iodide. It is preferable that the halogen composition distribution between particles is uniform.

The most preferable halogen composition of the monodisperse pore-side particles used in the present invention is a particle having substantially two distinct layered structures consisting of a core portion of a high iodine layer and a shell portion of a low iodine layer. This layered structure particle will be explained below.

A portion of the core is high iodine silver halide, and the iodine content is preferably between 10 mol % and the solid solubility limit of 45 mol %.

Preferably it is 10 to 45 mol%, more preferably 15 to 40 mol%.

The silver halide other than silver iodide in a part of the core may be either silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high.

The composition of the outermost layer is silver halide containing 5 mol% or less of silver iodide, more preferably silver halide containing 2 mol% or less of silver iodide.

The silver halide other than silver iodide in the outermost layer may be silver chloride, silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high.

The clear layered structure mentioned here can be determined by an X-ray diffraction method. An example of applying X-ray diffraction to silver halide grains can be found in H. Hirsch's Journal of Photographic Science.
graphic 5science) 1st OS (196
2), page 129 onwards. When the lattice constant is determined by the halogen composition, the black condition (2dsi
A diffraction peak occurs at a diffraction angle that satisfies nθ−nλ).

Regarding the measurement method of X-ray diffraction, see Basic Analytical Chemistry Course 24 “X
It is described in detail in books such as ``Radio Analysis'' (Benmuro Publishing) and ``X-ray Diffraction Guide'' (Rigaku Denki Co., Ltd.). The standard measurement method uses Cu- as a target and uses β-rays as a radiation source for Cu (tube voltage 40 KV, tube current 60 mA).
This is a method for determining the diffraction curve of the (220) plane of silver halide. In order to improve the imm carrier disassembly part, the width of the slit (divergent slit, light receiving slit, etc.), the time constant of the device,
It is necessary to appropriately select the scanning speed and recording speed of the goniometer and confirm the measurement accuracy using a standard sample such as silicon.

When the emulsion grains have two distinct layered structures, two peaks are generated in the diffraction curve due to the diffraction maximum due to the silver halide in the high iodine layer and the diffraction maximum due to the silver halide in the low iodine layer.

The diffraction angle (2θ) is essentially two distinct layered structures.
When the curve of diffraction intensity versus diffraction angle of the (220) plane of silver halide was obtained using β rays for Cu in the range of 38° to 42a, high iodine containing 10 to 45 mol% silver iodide was obtained. Two diffraction maxima, a diffraction peak corresponding to the layer and a diffraction peak corresponding to the low iodine layer containing 5 mol% or less silver iodide,
There is one minimum in between, and the diffraction intensity corresponding to the high iodine layer is 1/10 to 3/1 of the diffraction intensity of the peak corresponding to the low iodine layer.
More preferably, the diffraction intensity ratio is 115 to 3/1, especially l/
This is a case of 3 to 3/1.

As an emulsion having substantially two distinct layered structures,
More preferably, the minimum diffraction intensity between the two peaks is 2.
90% of the weakest diffraction maxima (peaks)
It is preferable that it is below.

More preferably 80% or less, particularly preferably 6
It is 0% or less. The method of decomposing a diffraction curve made up of two diffraction components is well known, and is explained in, for example, Experimental Physics Course 11 Lattice Defects (Benshi Publishing).

It is also useful to assume that the curve is a function such as a Callas function or a Lorentz function and to analyze it using a curve analyzer manufactured by Ou Pont.

Even in the case of an emulsion in which two types of grains with different halogen compositions coexist and do not have a clear layered structure, two peaks appear in the X-ray diffraction.

In order to judge whether a silver halide emulsion has a layered structure or an emulsion in which two types of silver halide grains coexist as described above, in addition to the XIIA diffraction method, EPM
Method A (Electron-Probe Micro.

This is possible by using the Analyzer method).

In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and an electron beam is irradiated. Elemental analysis of extremely small parts can be determined by X-ray analysis using electron beam excitation.

By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each particle.

By confirming the halogen composition of at least 50 grains by the EPMA method, it can be determined whether the emulsion has a layered structure or not.

In an emulsion having a layered structure, it is preferable that the code content between grains is more uniform.

When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is 50% or less, further 35% or less,
In particular, it is preferably 20% or less.

To obtain favorable photographic properties in emulsions consisting of silver halide grains with a well-defined layered structure, the high-iodide silver halide of the core must be well covered by the low-iodide shell silver halide. Although the shell thickness varies depending on the particle size, it is desirable that large particles of 1.0 μm or more be covered with a shell thickness of 0.1 μm or more, and small particles of less than 1,071 m be covered with a shell thickness of 0.05 μm or more. In order to obtain an emulsion with a clear layered structure, the ratio of silver in the shell part to the core part is preferably in the range of 115 to 5, more preferably 115 to 3, and particularly 115 to 2. preferable.

When a silver halide grain has substantially two distinct layered structures, it means that there are substantially two regions with different halogen compositions within the grain, with the center side of the grain being the core region and the surface side being the core region. Explained as a shell.

Substantially, the two are the core part and the third region (other than the shell part).
For example, this means that there may be a layer between the central core portion and the outermost shell portion.

However, even if such a third region exists, when an X-ray diffraction pattern is obtained as described above, two peaks (two peaks corresponding to a high iodine portion and a low iodine portion) are obtained.
This means that it may exist within a range that does not substantially affect the shape of the .

The same applies when the third region exists inside the core portion.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

For cough intermediate layer, JP-A-61-43748 and JP-A-59-1
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included.
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (B) / high-sensitivity green-sensitive layer (G) / low-sensitivity green-sensitive layer (GL)/
High-sensitivity red-sensitive layer (li) I) / low-sensitivity red-sensitive layer [
+? L) or B11/BL/GL/G11/[
1) 1/1iLO order or BH/BL/GH/GL/
They can be installed in the order of RL/R1i, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of 11/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is arranged, and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, the medium-speed emulsion layer/high-speed emulsion 71/low-speed emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

Preferred silver halides other than the monodisperse emulsions of this invention contained in the photographic emulsion layer are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred are silver iodobromide or iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

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

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

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) k17643 (
December 1978), pp. 22-23, '1. Emulsion manufacturing (
[Emulsion preparation and
1B716 (19
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafki
des, Chemic et Ph1sique P
photograph-ique, Paul Mont
el+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, DuffxnlPho)
tographic Emulsion Chemises
try (Focal Press+1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, ZsliSvanet al,
, Making and Coating Photo
graphic EvAul-sion+ Foca
1 Press+ 1964).

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, 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 be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

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

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

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

Masugai plate I plate ■H company L etc. lj l Chemical sensitizer 2 Sensitivity enhancer 3 Spectral sensitizer, super sensitizer 4 Brightener 5 Anti-fogging agent and stabilizer 6 Light absorber, filter Dyes, UV absorbers, stain inhibitors, dyes, image stabilizers, hardeners, binders, plasticizers, lubricants, coating aids, surfactants, 13 static inhibitors, and formaldehynes, pages 23-24, page 23, page 24, pages 24-25, page 649, right. Column - pages 25-26 Page 649 Right column - Page 650 Left column Page 25 Right column Page 25 Page 26 Page 26 Page 27 Page 26-27 Page 27 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Page 650 Left ~Right column, page 651, left column, same as above, page 650, right column, right column, page 650Ji It is preferable to add a compound that can be reacted and immobilized to the photosensitive material.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Section 17643, ■-C-C.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4.022.620, No. 4.3
No. 26,024, No. 4,401,752, No. 4,
248.961, Japanese Patent Publication No. 5B-10739, British Patent No. 1.425,020, British Patent No. 1,476.760, U.S. Patent No. 3,973.968, British Patent No. 4.314.
No. 023, No. 4.511.649, European Patent No. 24
No. 9,473A, 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, US Patent No. 3.061.432, US Patent No. 3.725,067, Research Disclosure Volume 24220 (June 1984) month), Japanese Patent Application Publication No. 1973-
No. 33552, Research Disclosure Ni12
4230 (June 1984), JP-A-60-4365
No. 9, No. 61-72238, No. 60-35730,
No. 55-118034, No. 60-185951, U.S. Patent No. 4.500.630, U.S. Pat. No. 4.540,65
No. 4, No. 4,556.630, International Publication WO3B1
Particularly preferred are those described in No. 04795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,21
No. 2, No. 4,146,396, No. 4.228,2
No. 33, No. 4.296.200, No. 2,369.
No. 929, No. 2.801.171, No. 2.772
．． No. 162, No. 2,895.826, No. 3,77
2.002, 3,758.308, 4.3
No. 34.011, No. 4.327,173, West German Patent Publication No. 3329.729, European Patent No. 121,365
No. A, No. 249°453A, U.S. Patent No. 3,446
, No. 622, No. 4.333,999, No. 4,77
No. 5,616, No. 4,451.559, No. 4,4
No. 27,767, No. 4.690,889, No. 4
, 254.

No. 212, No. 4,296.199, JP-A-61-4
Those described in No. 2658 and the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are specified in Research Disclosure T17643.
- Section G, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.258, British Patent No. 1.146,36
The one described in No. 8 is preferred. Also, U.S. Patent No. 4.7
74.181, which corrects unnecessary absorption of color-forming dyes by means of fluorescent dyes released during coupling; and couplers that can react with developing agents to form dyes, as described in U.S. Pat. No. 4,777,120. It is also preferred to use couplers having a dye breaker group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96.570 and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576910, British Patent No. 2,102,1
It is described in No. 73, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler emitting before development inhibition is the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4.248,96
No. 2, No. 4°782.012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097,140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, JP-A-62-24252, etc., the DIR coupler-releasing couplers,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
Couplers that release dyes that give aftercolor after separation as described in No. 02A, R, D, N1111449, 24241, bleach accelerator-releasing couplers as described in JP-A No. 61-201247, etc., U.S. Patent No. 4,553,477 Gantt-emitting couplers described in JP-A-63-75747, leuco dye-releasing couplers described in US Pat.
Examples include couplers that emit fluorescent dyes as described in No. 181.

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

C-+21 C-+51 l , C-+61 I molecular weight Approximately 40. QOQ C-[3) C-+41 C-+71 C-(81 C-+91 C-α1 -Q1 C-(b) H C-(i~ H (1) #l1ILll; LINII -I C- (to) H C@81(t) C-Q@ C1l.

C-(5) H 5CLCLCO! )l C-(to) C-aS H C-(2) H Cl1゜C-(to) C-(ro) 0)l C-(24) C-(25) C-(26) C-( 27) C-(30) C-(31) I C-(28) C-<29) C-(32) C-(33) i1 H H 0011□CToCON+1cLcItOclliC-
(34) C-(35) C-(38) C-(39) C-(40) I H C-(41) C-(36) c-(37) i1 C-(44) C-(45 ) J C-(46) H C-(50) c-(51) C-(47) C-(48) C-(49) c-(53) C-(54) H CI! C-(55) C-(5B) c-(59) C-(57) C-(5B) 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 (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-1-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid Esters W4 (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.)
, benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.
4-di-tart-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2
-butoxy-54ert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C.
Any organic solvent having a temperature above about 160° C. or below can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation are disclosed in U.S. Pat. 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 vapor.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of 17643, and the same No. 1871
6, from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 28 μm or less, and the film swelling rate is TI/! is preferably 30 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T can be measured according to a method known in the art. , Green et al., Photographic Science and Engineering (Photogr, Sci, Eng,) + Volume 19, 2
It can be measured by using a swellometer (swelling membrane) of the type described in No., pp. 124-129, and TI/□ is the maximum swelling membrane reached when treated with a color developer at 30°C for 3 minutes and 15 seconds. 90% of the thickness is taken as the saturated film thickness, and this T, I of 78
I! It is defined as the time required to reach I thickness.

The membrane swelling rate T1/8 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above, according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic light-sensitive material according to the present invention can be developed by the conventional method described in the above-mentioned RD, pages 28-29 of Magnetics 17643, and pages 615, left column to right column, of Na18716.

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 crude drug as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts and p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developers may contain pH 1 buffers such as alkali metal carbonates, borates or phosphates, development inhibiting agents such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds, or fogging agents. It generally contains an inhibitor. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo(2,2,2)
various preservatives such as octane), ethylene glycol,
Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, l-phenyl-3-pyrazolidone. Auxiliary developing agents such as viscosity imparting agents, various oxidizing agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N,
N-tetramethylenephosphonic acid, ethylene glycol (
Representative examples include O-hydroxyphenylacetic acid) and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-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 -i is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
It can also be made less than 1d. When reducing the amount of replenishment, it is preferable to reduce the contact area with the air in the processing tank to prevent evaporation of the solution and air oxidation, and also to use means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

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. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. Examples of bleaching agents include iron (■), Kobal) (I
Compounds of polyvalent metals such as II), chromium (IV), and w4(I[), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate: iron(1) or cobal) (m) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. . Among these, iron(III) aminopolycarboxylate including ethylenediaminetetraacetic acid ([[[) complex salts] 1! Salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(I[I) complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron (I [ You can also do that.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290.812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. N1117129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832, Japanese Patent Publication No. 53-32735, U.S. Patent No. 3,706,56
Thiourea derivatives described in No. 1; West German Patent No. 1,127.
No. 715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748,43
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compound described in No. 8836; Other JP-A No. 4
No. 9-42.434, No. 49-59.644, No. 53
-94,927, 54-35,727, 55-
Compounds described in No. 26.506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85.
No. 8, West Patent No. 1290.812, JP-A-53-95
Preferred are the compounds described in US Pat. No. 4,552,830. These bleach accelerators may be added to the light-sensitive material, and 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 the most commonly used, and ammonium thiosulfate is the most common. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is optimally subjected to a water washing and/or stabilization process 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
urnal of the 5ociety of )
lotion Picture and Te1evi
sion Engineers Volume 64, P, 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of color photosensitive materials of the present invention, as a solution to these problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial It is also possible to use the disinfectants described in ``Disinfection, Sterilization, and Anti-Mildew Techniques'' and ``Encyclopedia of Antibacterial and Antifungal Agents'' by Japan Antibacterial and Antifungal Science Kinsen.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range 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 processing, time-opening vIA57-8
No. 543, No. 58-14834, No. 60-22034
All known methods described in No. 5 can be used.

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

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

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in 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 the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1=phenyl-3
- Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
It is described in No. 144547 and No. 58-H5438.

The various processing liquids 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. This makes it possible to improve the image quality and the stability of the processing solution by lowering the temperature.

In addition, West German Patent No. 2.226.7 due to the nodal line of the photosensitive material
70 or U.S. Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in European Patent No. 9-218443, European Patent No. 61-238056, and European Patent No. 210,66082.

(Margin below) Example Monodispersed emulsion J was prepared as follows.

First, a 1N aqueous gelatin solution containing 0.01 mol of potassium bromide and 0.7 mol of ammonia was placed in a reaction vessel, and while maintaining the temperature at 55°C, 500 d of an aqueous solution containing 0.27 mol of silver nitrate was added to the reaction vessel. and 500 cc of an aqueous solution containing 0.24 mol of potassium bromide and 0.043 mol of potassium iodide were simultaneously added over 30 minutes, and during the addition, halogen ions were added to silver ions at 0.2 g/j! It was added while adjusting the amount to be in excess. Then, after neutralizing the ammonia using acid,
Furthermore, 500 CC of an aqueous solution containing 0.62 mol of silver nitrate, 500 CC of an aqueous solution containing 0.71 mol of potassium bromide, and 0.01 mol of potassium iodide were simultaneously added for 30 minutes, and during the addition, halogen ions were converted into silver ions. 0.2g/j!
It was added while adjusting the amount to be in excess. The average grain size of this emulsion was 0.50 μm.

Agl content was 5.5% and S/r was 0.12.

Next, in the above emulsion preparation method, the temperature was kept at 70°C, and the initial potassium bromide 0.24 mol was changed to 0°222 mol, and the added potassium 0.043 mol was changed to 0°061 mol. Monodisperse emulsion K was prepared.

The average grain size of this emulsion was 0.80 μm, and the Agl content was 8.
0%, S/r was 0.14.

A polydisperse emulsion for comparison was prepared as follows.

First, 0.3 mol of potassium bromide, 0.03 mol of potassium iodide
A gelatin aqueous solution containing 6 mol was placed in a reaction vessel, and 50
To this was added an aqueous solution containing 1.3 mol of silver nitrate, 1.1 mol of potassium bromide, and 0.04 mol of potassium iodide while keeping the temperature at ℃.
An aqueous solution containing 2 mol was added simultaneously over a period of 40 minutes.

The average grain size of this emulsion was 0.60 μm, and the Agl content was 6.
0%, S/r was 0.22.

Furthermore, in the emulsion preparation method, the temperature was changed to 65°C, potassium bromide was added to 1.074 mol, and potassium iodide was added to 0.07 mol.
A polydisperse emulsion M was prepared in the same manner except that the amount was changed to 0.061 mol. The average grain size of this emulsion was 0.84 Um, Ag
The I content was 8.2% and S/r was 0.25.

Monodisperse emulsions J and K and polydisperse emulsions M were all post-ripened to the optimum point by a known method.

The following samples 101 to 106 were prepared using the monodisperse emulsion and polydisperse emulsion prepared as described above.

on a subbed cellulose trisaucetate film support.
Sample 101, which is a multilayer color photosensitive material, was prepared by layer-coating each layer with the composition shown below (Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/rrf unit. For silver halide, the coating amount is shown in terms of silver; however, for sensitizing dyes, the coating amount is shown in moles per mole of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloid II 110.18 Gelatin 1.40 Second layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.1SEX-1
0,07 EX-30,02 EX-120,002 U-10,06 U-20,08 U-30,10 HBS-10,10 HBS-20,02 Gelatin 1.04 3rd layer (
1st red-sensitive emulsion layer) Emulsion A Root 0.25 Emulsion B
Silver 0.25 Sensitizing dye 1
6.9X10 bow sensitizing dye n
i, 5xio-S sensitizing dye III
3. lXl0-'EX-20,335 EX-10 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion C Sensitizing dye I Sensitizing dye■ Sensitizing dye■ X-2 X-3 X-10 Gelatin 5th layer (Third red emulsion layer) Emulsion sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ X-3 X-4 X-2 5B-1 0,020 0,87 12m1.0 5, lXl0-'! , 4XIO-5 2,3X10-' 0.400 0.050 0.015 1,30 it! 1.60 5.4X10-S 1, 4X10-' 2, 4 X 10'-' 0.010 0.080 0.097 0, 22 5B-2 Gelatin 6th layer (intermediate layer) Gelatin 7th layer (first green emulsion N) Polydisperse emulsion sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ X-6 X-1 X-7 X-8 B5-1 B5-3 Gelatin 8th layer (Second green-sensitive emulsion layer) Polydisperse emulsion M 0,10 1,63 0.040 0, 020 0,80 ifO,32 3,2X10-'1.0XIO-' 4, lX10-' 0.280 0. 022 0.030 0.025 0.140 0.011 0,70 mo, 44 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ X-6 X-8 X-7 B5-1 B5-3 Seratin 9th layer (Third green-sensitive emulsion layer) Emulsion E Sensitizing dye ■ Enhancing dye ■ Sensitizing dye ■ X-13 Eχ-11 ' 0.092 0.016 0.024 0, lO mouth, 008 0, 55! 11.2 3, 5X10-% 8.0X10-! 1 3, 0XIO-' 0.015 0.100 0.025 0, 25 0, 10 1, 54 10th layer (Yellow filter N) Yellow colloid 11 Daughter 0.0SE
X-50,08 1 (BS-10,03 Gelatin 0.95 11th layer (first blue-sensitive emulsion layer) Emulsion A iIo, 08 Milk splitting B
Silver 0.07 emulsion F
#I0.07 sensitizing dye■
3.5X10-'EX-90,721 EX-80,042 HBS-10,28 Gelatin 1.10 No. 12
Layer (second blue-sensitive emulsion layer) Emulsion C silver o, 45 Sensitizing dye ■ 2. lXl0-'EX-
90,154 已X-100,007 HBS-10,05 Gelatin 0.78 13th layer (third blue emulsion layer) Emulsion HiiO,77 Sensitizing dye■ 2.2X10-'EX-
90,20 HBS-10,07 Gelatin 0.69 14th layer (first protective layer) Emulsion I Silver 0. 5tJ-
40,11 U-5, '0.17 HBS-1 0.05 Gelatin 1.00 15th layer (second protective layer) Polymethyl acrylate particles (diameter 1.5 μm) 0.543-1
0.20 gelatin
1.20 In addition to the above ingredients, gelatin hardener H-1 and a surfactant were added to each layer.

EX-1 EX-2 H EX-3 H EX-7 EX-8 EX-9 I EX-4 0■ EX-5 CJ 1. (n) EX-6 EX-10 EX-12 C,H,O3Oρ EX-13 Shil (uJL+4r19 Sensitizing dye! Sensitizing dye ■ Sensitizing dye ■ V-5 BS Tricresyl phosphate di-n-butyl phthalate Aggravating dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ S-1 ■ Ms CH! Dried CHSO! CHI-CONHCHxCH*
=CHFAt Cl1t C0NHCHt (Sample 1
02 to 106) Instead of coupler EX-6 in the 7th and 8th layers of sample 101, the couplers shown in Table 1 were added in molar ratios such that the coloring density was approximately equal, and also high The amount of the boiling point organic solvent HBS-1 was reduced to 3/4, and the amount of gelatin was determined and added so that the ratio of ((coupler) + (HBSl))/gelatin was constant, and a polydisperse emulsion was prepared. Sample 10 except that monodisperse emulsion JSK was used instead.
Samples 102 to 106 were prepared in the same manner as in Example 1.

Graininess of the sample created in this way (RMS graininess)
, the sharpness was evaluated. These evaluation methods were performed as follows.

(RMS (Root Mean 5quare)
) as determined by the law. Determination of graininess by the RMS method is well known among those skilled in the art, but 'Photograph
jcSciences and Engineering
J VOI 19 i Nn4 (1975) p.
rRMsGranuslallLy at 235-238;
Deter+5nation of Just n
The story is written under the title "OticeablediHerence".

[Sharpness]

After the sample was exposed with a pattern for MTF measurement, it was processed through the processing steps shown below to measure MTF.

These results are summarized in Table 2.

Processing process 1 Processing time Processing temperature 3 minutes 15 seconds 38°C 1 minute OO seconds 38°C 3 minutes 15 seconds 38°C 40 seconds 35°C 1 minute OO seconds 35°C 40 seconds 38℃ 1 minute 15 seconds 55℃ Process color development bleached white bleach fixing Washing with water (1) Washing with water (2) stability Inui san Next, the composition of the treatment liquid will be described.

(Color developer) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene (Unit g) 1.0 1.1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N- β-Hydroxyethylamino)-2 Add monomethylaniline sulfate and H (Bleach solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium chloride Ammonium bromide Ammonium nitrate Bleach accelerator 4.5 1. 01 10.05 (Unit: g) 120.0 10,0 100.0 10,0 0.005 Mol ammonia water (27%) Add water (bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonia water dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite ammonium thiosulfate aqueous solution (70%) Ammonium water (27%) Add water and H Water is passed through a hotbed column filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400) to remove calcium and magnesium. Treat the ion concentration to 3■/2 or less, and then add 20m# of sodium isocyanurate dichloride! and 150 mg/j2 of sodium sulfate were added.

The pH of this solution is in the range of 6.5-7.5.

(Unit g) (Stabilized liquid) Formalin (37%) Polyoxyethylene-p-monononylphenyl ether (average weight 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0E pH 5,0-8 ，
0 0,3 2,〇- As is clear from Table 2, the samples of the present invention have excellent sharpness and improved RMS graininess.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer on a support, which is capable of forming a dye by coupling with an oxidized form of an aromatic primary amine developer. A silver halide color photographic light-sensitive material characterized by containing a monodisperse silver halide emulsion and a polymer coupler having at least one type of repeating unit derived from a monomer represented by the following formula [I]. Formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 is a hydrogen atom, a chlorine atom, or a carbon number of 1 to 4
represents an alkyl group, R_2 represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, R_3 and R_
4 represents a linear or branched alkylene group having 2 to 10 carbon atoms. X represents -COO-, -CONR_5- or a phenylene group, Y_1 and Y_2 are -O-, -S
-, -SO-, -SO_2-, -CONR_5- or -COO-. R_5 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. Q represents a coupler residue capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developer. n, m and p are 0 or 1
, q represents 2 to 10, and r represents 0 to 10.