JPH03212641A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the color reproducibility and graininess of a sensitive material and the shelf stability in a frozen state by incorporating a specified cyan coupler, a specified yellow colored magenta coupler and a prescribed amt. of a high b.p. org. solvent into a red-sesitive emulsion layer. CONSTITUTION:A cyan coupler represented by formula I and a yellow colored magenta coupler such as a compd. represented by formula IV are incorporated into one or more red-sensitive emulsion layers of a sensitive material and a high b.p. org. solvent is further incorporated into the emulsion layers in >=0.3 weight ratio to all the couplers contained in the emulsion layers. In the formula I, R1 is -CONR4R5, -SO2NR4R5, etc., each of R2 and R3 is a substituent, each of R4 and R5 is H, alkyl, etc., l is 0-3 and X is H or a releasable group. A compd. having a group represented by formula II as R1 in the formula I, 0 as l, a group represented by formula III as R3 and H as X may be used as the cyan coupler represented by the formula I.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, particularly a halogenated silver halide color photographic material having excellent color reproducibility, graininess, sharpness, and frozen storage stability. This invention relates to silver color photographic materials.

(Prior Art) It is well known that when a silver halide photographic material is exposed to light and then subjected to color development, an oxidized aromatic-amine developer reacts with a dye-forming coupler, resulting in a color image. It is being

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

For example, acylacetanilide or benzoylmethane couplers are used to form yellow images.
To form a magenta color image, mainly pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indacylon couplers are used, and to form a cyan color image, mainly phenolic couplers such as phenols and naphthols are used. .

By the way, especially for cyan and magenta images,
It has a drawback that it has a sub-absorption on the shorter wavelength side than the main absorption part, and this sub-absorption deteriorates the color reproducibility of the photosensitive material.

To improve this, a masking technique using colored couplers has been developed. (U.S. Patent No. 242805
Regarding colored cyan couplers for masking to correct side absorption of cyan images, see US Pat. No. 3,481,741, US Pat. No. 3,459,552, etc.
U.S. Patent No. 3,583,971, U.S. Patent No. 245,516
No. 9 and US Pat. No. 3,034,892, etc., but the masking properties were insufficient. Therefore, an improvement has been made (Japanese Patent Publication No. 37019/1983) in which a colored cyan coupler having main absorption in the blue region, a colored cyan coupler having main absorption in the green region, and a colorless cyan coupler are used in combination.

Furthermore, regarding the application of colored couplers to colorless cyan couplers with excellent light fastness, Japanese Patent Application Laid-Open No. 61-22174
No. 8, JP-A No. 62-3253, etc.

Incidentally, in recent years, silver halide photosensitive materials, especially photosensitive materials for photographic use, have been developed using ultra-high-sensitivity photosensitive materials such as 15O1600 film, 110, and magnification materials suitable for cameras with small formats such as disks. There is a growing demand for window materials that have high image quality (graininess and sharpness) that can be used for printing at large magnifications.

However, when these characteristics are taken into consideration, the masking technology described above does not work! (graininess, sharpness) is small,
There has been a long-awaited technology that has excellent color reproducibility and can also improve graininess and sharpness.

Furthermore, in recent years, there has been an increase in the number of cases in which photosensitive materials are kept at freezing temperatures during transportation and storage, and it has been desired to improve image quality deterioration caused by this.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide color photographic material that has excellent color reproducibility, graininess, sharpness, and frozen storage stability.

(Means for Solving the Problems) The object of the present invention is to provide (11) a silver halide color photographic light-sensitive material having at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on each support; One red-sensitive emulsion layer contains a cyan coupler represented by the following formula [I], the emulsion layer contains at least one yellow-colored magenta coupler, and the emulsion layer further contains a high boiling point organic solvent. A silver halide color photographic light-sensitive material containing at most 0.3 of the coupler in weight ratio based on the total amount of the coupler.

Formula (1) In formula (T), R+ is -CONR,R,, sot
NR, R5, -NHCOR,, -NHCOOR,, -N
H3O□ R4, NHCONR, R5 or -NH3O
z Coupling reaction between NR4R5, R2 is a group that can be substituted on the naphthalene ring, 2 is an integer of 0 to 3, R4 is a substituent, and X is a hydrogen atom or an oxidized aromatic primary amine developer represents a group capable of leaving, respectively. However, R4 and R3 may be the same or different and independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R6 represents an alkyl group, an aryl group, or a heterocyclic group. ! When there is a plurality of R2's, R2's may be the same or different, or may be bonded to each other to form a ring. R2 and R3, or R1 and X may be bonded to each other to form a ring. Furthermore, R+, Rt, R3, or X may form a dimer or a multimer of more than 2 valent molecules bonded to each other via a divalent or divalent or higher valent group.

Each substituent in formula (1) will be described in detail below.

R1 is -CONR4R5, So□NR,R,, NHCO
R4, -NHCOORl, -NH3O! R.

-NHCON Ra Rs or -NH3OaNR4
R5 represents R5, and Ra, Rs and R6 each independently represent an alkyl group having a total number of carbon atoms (hereinafter referred to as the number of C) from 1 to 30, an aryl group having from 6 to 30 C, or a heterocyclic group having from 2 to 30 C. . R4 and R1 may also be hydrogen atoms.

R2 represents a group (including atoms; the same applies hereinafter) that can be substituted on the naphthalene ring, and representative examples include halogen atoms (F, Cj
! , Br, I), hydroxyl group, carboxyl group, amino group, sulfo group, cyano group, alkyl group, aryl group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group , an acyloxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoylamino group, an alkoxycarbonylamino group, a nitro group, and an imido group. i! ,=2, examples include dioxymethylene group and trimethylene group. CR,＞
The C number of l is 0 to 30.

R3 represents a substituent, preferably represented by the following formula [Cl3].

2 (C1) Rt (Y) yo In formula (C-1), Y is >NH, >co or >s
o, m is an integer of 0 or l, R7 is a hydrogen atom, C
Alkyl group having 1 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms,
C2-30 heterocyclic group, -COR, 90tRo. , II C-5R,. , SO□OR, or -3o,R,. respectively. Here R3, R
7 and R111 have the same meaning as R4, Rs and R4, respectively.

9 may be bonded to form a nitrogen-containing heterocycle (eg, pyrrolidine ring, piperidine ring, morpholine ring).

X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer (referred to as a leaving group; it includes a leaving atom; the same applies hereinafter); representative examples of leaving groups include halogen; Atom, -CR111S R+ I,
OCR+ +, -NHCOR.

1 NHC3R11, -0COR,, -0CNHR,,.

II II I
Io 0 0 thiocyanate group, a heterocyclic group having 1 to 30 carbon atoms and bonded to the coupling active position with a nitrogen atom (e.g. succinimide group,
Phthalimide group, pyrazolyl group, hydantoinyl group, 2
-benzotriazolyl group). Here, R11 has the same meaning as R4.

In the above, the alkyl group may be linear, branched, or cyclic, and even if it contains an unsaturated bond, it may have a substituent (e.g., halogen atom, hydroxyl group, aryl group, heterocyclic group, alkoxy group). , aryloxy group,
(alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, acyloxy group, acyl group), typical examples include methyl, isopropyl,
Isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, n-dodecyl, n-hexadecyl, 2-methoxyethyl, benzyl, trifluoromethyl, 3-dodecyloxypropyl, 3-(2,4-di-t-pentylphenoxy) ) There is propyl.

Furthermore, even if the aryl group is a condensed ring (for example, a naphthyl group), a substituent (for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbonamide group,
sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group); representative examples include phenyl, tolyl, pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, and 4-cyanophenyl. , 2-tetradecyloxyphenyl, 2-chloro-5dodecyloxyphenyl, and 4-t-butylphenyl.

In addition, the heterocyclic group is 0. N, S, P, Se, T
A 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one heteroatom of e in the ring, and containing a substituent (e.g., a halogen atom, a carboxyl group, a hydroxyl group,
nitro group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group), Representative examples include 2-pyridyl, 4-pyridyl, 2-furyl, 4-thienyl, benzotriazol-1-yl, 5-phenyltetrazol-1
-yl, 5-methylthio-1,3,4thiadiazole-
2-yl, 5-methyl-1°3.4-oxadiazol-2-yl.

Preferred examples of substituents in the present invention will be explained below.

R7 is preferably -CONR, Rs or S02 NR4R5, and specific examples include carbamoyl, N-n-butylcarbamoyl, Nn-dodecylcarbamoyl, N(3-n-dodecyloxypropyl)carbamoyl, N-cyclohexylcarbamoyl, N −(
3-(2,4-di-pentylphenoxy)propyl]
Carbamoyl, N-hexadecylcarbamoyl, N-(
4(2,4-di-t-pentylphenoxy)butylcarbamoyl, N-(3-dodecyloxy2-methylpropyl)carbamoyl, N-[3(4-t-octylphenoxy)propyl]carbamoyl, N-hexadecyl- N
-Methylcarbamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N-(4-(2,4-di-t-
Pentylphenoxy)butylcarbamoyl. R1
is particularly preferably -CONR,R.

R2,! as! =0, ie, no substitution, is most preferred, followed by ff1 =1. Rz is preferably a halogen atom, an alkyl group (e.g. methyl, isopropyl, L-butyl, cyclopentyl), a carbonamide group (e.g. acetamide, pivalinamide, trifluoroacetamide, henzamide), a sulfonamide (e.g. methanesulfonamide, toluenesulfonamide) )
Or a cyano group.

R1 is preferably m=0 in formula (C-1),
More preferably, R7 is -cORs C such as formyl, acetyl, trifluoroacetyl, 2-ethylhexanoyl, pivaloyl, benzoyl, pentafluorobenzoyl, 4-(24-di-t-pentylphenoxy)butanoyl], GOOR+o [e.g. methoxy carbonyl, ethoxycarbonyl, isobutoxycarbonyl,
2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl, 2-methoxyethoxycarbonyl] or -3OZRIO (e.g. methylsulfonyl, n-butylsulfonyl, n-hexadecylsulfonyl, phenylsulfonyl, p-tolylsulfonyl, p-chlorophenyl) sulfonyl, trifluoromethylsulfonyl], and particularly preferably R7 is -COOR, .

X is preferably a hydrogen atom, a halogen atom, OR++ (e.g. ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-(2-hydroxyethoxy)ethoxy,
2-methylsulfonylethoxy, ethoxycarbonylmethoxy, carboxymethoxy, 3-carboxypropoxy, N(2-methoxyethyl)carbamoylmethoxy,
■-Alkoxy groups such as carboxytridecyloxy, 2-methanesulfonamidoethoxy, 2-(carboxymethylthio)ethoxy, 2-(1-carboxytridecylthio)ethoxy, e.g. 4-cyanophenoxy, 4
-carboxyphenoxy, 4-methoxyphenoxy, 4
-t-octylphenoxy, 4-nitrophenoxy, 4
-(3carboxypropanamido)phenoxy, 4-acetamidophenoxy group] or -3R++ (e.g. carboxymethylthio, 2-
Alkylthio groups such as carboxymethylthio, 2-methoxyethylthio, ethoxycarbonylmethylthio, 23-dihydroxypropylthio, 2-(N,N dimethylamino)ethylthio, e.g. 4-carboxyphenylthio, 4methoxyphenylthio, 4- (3-carboxypropanamide) arylthio group such as phenylthio]
and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an alkylthio group.

The coupler represented by the general formula CI) has substituents R1Rz,
R3 or X may form a dimer or a multimer of more than two molecules, each of which is bonded to each other via a divalent or more than divalent group. In this case, the number of carbon atoms in each substituent may be outside the ranges indicated above.

When the coupler represented by the general formula [I] forms a multimer, an addition-polymerizable ethylenically unsaturated compound having a cyan dye-forming coupler residue (a typical example is a cyan color-forming monomer alone or a copolymer, and is preferred) is the formula (C-2)
It is expressed as

Formula (C-2) (Gi), i □ (H4)h, Formula (C-2)
01 is a repeating unit derived from a color-forming monomer and is a group represented by formula (C-3), and H
J is a group which is a repeating unit derived from a non-chromogenic upper molecule, i is a positive integer, j is 0 or a positive integer, and gi and hi are G□ or H, respectively.
represents the weight fraction of j. Here, when i or j is plural, it means that Gi or H4 includes plural types of repeating units.

Formula (C-3) In formula [C-3], R is a hydrogen atom and has 1 to 4 carbon atoms.
represents an alkyl group or a chlorine atom, and A is -CONH
--Coo- or a substituted or unsubstituted phenylene group, B represents a divalent group having carbon atoms at both ends such as a substituted or unsubstituted alkylene group, phenylene group, or oxydialkylene group, and L -CONH NHCONH--NHCOO--NHCO-OCONH
--NH--COO--0COCO--0--5o,-
-NH5O.

Or it represents -3O,NH-. a, b, and c represent integers of 0 or 1. Q represents a cyan coupler residue obtained by removing one hydrogen atom from R,, R,, R3 or X of the compound represented by the general formula CI).

Examples of non-color-forming ethylene type monomers that do not couple with the oxidation product of the aromatic-grade amine developer that provide the repeating unit Hj include acrylic acid, α-rolyroacrylic acid, α-
Alkyl acrylic acids (e.g. methacrylic acid, etc.) Amides or esters derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n- Propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-
octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxyethyl methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl Compound(
For example, styrene and its derivatives (e.g. evavinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (
(e.g. vinyl ethyl ether), maleic acid ester,
Examples include N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and -4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more types of non-color-forming ethylene monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. are used. can.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the formula [C3] may be in the form of the copolymer to be formed, such as solid, liquid, Micellar and physical and/or chemical properties, such as solubility (solubility in water or organic solvents)
, compatibility with the binder of the photographic colloid composition, such as gelatin, its flexibility, thermal stability, coupling reactivity with oxidized developer, diffusion resistance in the photographic colloid, etc. are favorably influenced. You can choose. These copolymers may be random copolymers or copolymers with a specific sequence (for example, block copolymers, alternating copolymers).

The number average molecular weight of the cyan polymer coupler used in the present invention is usually on the order of several thousand to several million, but
Polymer couplers in the form of oligomers of 0 or less can also be utilized.

The cyan polymer coupler used in the present invention may be a lipophilic polymer soluble in organic solvents (e.g. ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate) or a hydrophilic colloid such as an aqueous gelatin solution. It may be a hydrophilic polymer that is miscible with the colloid, or a polymer that has a structure and properties that allow it to form micelles in a hydrophilic colloid.

In order to obtain a lipophilic polymer coupler soluble in organic solvents, a lipophilic non-color-forming ethylene-like monomer (for example, acrylic ester, methacrylic ester, maleic ester, vinylbenzenes, etc.) should be selected as the copolymerization component. is preferred.

A lipophilic polymer coupler obtained by polymerizing a vinyl monomer to provide a coupler unit represented by the general formula (C-3) is dissolved in an organic solvent and then emulsified and dispersed in the form of latex in an aqueous gelatin solution. Alternatively, it may be produced by direct emulsion polymerization.

U.S. Pat.
No. 51,820, and U.S. Pat.
The methods described in No. 080,211 and No. 370.952 can be used.

In addition, in order to obtain a hydrophilic polymer coupler soluble in neutral or alkaline water, I'm-(1,1-dimethyl-2-sulfonatoethyl)acrylamide, 3-sulfonatopropyl acrylate, styrene sulfonic acid Sodium, potassium styrene sulfinate, acrylamide, methacrylamide, acrylic acid, methacrylic acid,
It is preferable to use a hydrophilic non-chromic ethylene-like polymer such as N-vinylpyrrolidone or N-vinylpyridine as a copolymerization component.

Hydrophilic polymer couplers can be added to coating solutions as aqueous solutions, and can be added to lower alcohols, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone,
It can also be added by being dissolved in a mixed solvent of water and a water-miscible organic solvent such as ethyl lactate, dimethylformamide, dimethylacetamide. Furthermore, it may be added after being dissolved in an alkaline aqueous solution or an alkaline water-containing organic solvent. Additionally, a small amount of surfactant may be added.

Specific examples of each substituent in formula (1) and the cyan coupler represented by formula [I] are shown below.

Example of R1 -CONH(CH,)30-A -CONH
(CH,), C1-ACON H (CHz) s○Cl
2Hzs-n C0NH (CHri 30CHHzr
nC,H.

C0NH(CHz)s 0CHz CHC-Hs-n
C0NHC+bH3rnHs CONHCH2CHCHHz C12H2S-nCONH
(CH2CHz O)z C+zHzs-nCONHC
Hz CHz OC+zHzs-nCONH(CHz)
z QCl, H-q-nCONH(CH2)3 QC1
+HzrnSo,NH(CH,)3QC,,H,,-
Example of nR2 F I N CH.

F3 C4R9-t C8H+t-t NHCOCH.

NH30, CH.

NHCOOC-Hs Examples of R, NH- -NHSO□CF.

NH30,C,H9 -NF(COOC4fR-n -NHCOOCH2cHt　0CHffzHs -NHCOOCH,CHC,H.

NHCOOC+2Hzs-n -NHC○OCH, CHI 0-A NHCOCOCH3 Example of X C2H5 -0CR,CH,0H -OCH, cHz soz CH3 0(CHz　CHz○)2H -OCR, Co○H -O(CH,h　C00H OCH,COOC2H6 0CH,CH,SCH,C00H -OCH, CHI 5CHCOOH OCR, CH, OCR.

-OCH, CH2NH30□CHs CH.

5CHCO○H 3CH2cooct H.

-5 cHz CH,OH Other couplers j-Ca H90CONH i-C4H,0CONH i-c4H9ocoNH Number average molecular weight approximately 60°00 -51 2 H x:y=10:30 Number average molecular weight approximately 55°00 CH3CH3 Chill group, cm l"1174 is -CCH, CCH3
represents CH3CH3.

Other specific examples of cyan couplers represented by formula [I] and/or methods for synthesizing these compounds are described in, for example, U.S. Pat. No. 63-208042, No. 64-31159, and West German Patent No. 3823049A.

The cyan coupler represented by 2
As described in No. 269958, it is preferable to use a small amount of a high boiling point organic solvent for dispersion in order to further improve sharpness and desilvering properties.

Specifically, the high boiling point organic solvent is used in a weight ratio of 0.3 or less, more preferably 0.1 or less, to the cyan coupler represented by formula (I).

The total amount of the cyan coupler represented by formula [I] is 30 mol% or more, preferably 50 mol% or more of the total cyan coupler.
It is at least mol %, more preferably at least 70 mol %, even more preferably at least 90 mol %.

It is preferable to use two or more cyan couplers represented by formula [I] in combination, and when the same color-sensitive layer is divided into two or more layers with different sensitivities, a 2-equivalent cyan coupler is used in the highest sensitivity layer. It is preferable to use a 4-equivalent cyan coupler in the lowest sensitivity layer. For the same color-sensitive layers other than these, it is preferable to use either one or both.

Yellow colored magenta coupler has the following general formula ([)
It is preferable that

Next, the colored magenta coupler represented by the general formula (n) will be described.

General formula (n) Ar where Ar represents an unsubstituted or substituted phenyl group,
Rol represents a substituent, and R1□ represents an aromatic group or a heterocyclic group substituted with either a hydroxyl group or a carboxyl group.

Next, details of preferred substituents will be described below.

Ar represents an unsubstituted or substituted phenyl group, and examples of substituents include alkyl groups (e.g. methyl, ethyl), alkoxy groups (e.g. methoxy, ethoxy), aryloxy groups (e.g. phenyloxy), alkoxycarbonyl groups (
methoxycarbonyl), acylamino groups (e.g. acetylamino), carbamoyl groups, alkylcarbamoyl groups (e.g. methylcarbamoyl, ethylcarbonyl), dialkylcarbamoyl groups (e.g. dimethylcarbamoyl), arylcarbamoyl groups (e.g. phenylcarbamoyl), alkylsulfonyl groups ( (e.g. evamethylsulfonyl), arylsulfonyl groups (e.g. evaphenylsulfonyl), alkylsulfonamide groups (e.g. methanesulfonamide), arylsulfonamide groups (e.g. phenylsulfonamide), sulfamoyl groups, alkylsulfamoyl groups (e.g. ethylsulfonamide), famoile),
Dialkylsulfamoyl groups (e.g. dimethylsulfamoyl), alkylthio groups (e.g. methylthio), arylthio groups (e.g. phenylthio), cyano groups, nitro groups, halogen atoms (e.g. fluorine, chlorine, bromine), and this substituent If there are two or more, 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.

In the formula, R1+ is a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (these groups are the substituents listed for Ar above) ), aryl groups and heterocyclic groups (these may have the above A
r), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, stearyloxycarbonyl), aryloxycarbonyl groups (e.g. phenoxycarbonyl,
naphthoxycarbonyl), aralkyloxycarbonyl groups (e.g. penzyloquine carbonyl), alkoxy groups (e.g. methoxy, ethoyne, heptadecyloxy),
Aryloxy groups (e.g. phenoxy, tolyloxy)
, alkylthio groups (e.g. ethylthio, dodecylthio)
, arylthio group (e.g. phenylthio, α-naphthylthio), carboxy group, acylamino group (e.g. acetylamino, 3-((2,4-di-tertamylphenoxy)acetamido]benzamide), diacylamino group, N-alkylacylamino group (e.g. N-methylpropionamide), N-arylacylamino groups (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 (e.g. alkylsulfonamide, arylsulfonamide) , carbamoyl group (e.g. ethylcarbamoyl, dimethylcarbamoyl, N-methyl-phenylcarbamoyl, N-
phenylcarbamoyl, etc.), sulfamoyl groups (e.g. N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N-alkyl-N-ori-lsulfamoyl LN).

N-dialkylsulfamoyl), a cyano group, a hydroxy group, a mercapto group, a halogen atom, or a sulfo group.

In general formula (n), it is particularly preferable that R31 is an anilino group, an acylamino group, or an arylureido group, and Ar is an aryl group in which at least one ortho position is substituted with an atom other than hydrogen. .

When R1□ in general formula (It) represents an aromatic group, it preferably represents a phenyl group or an α- or β-naphthyl group. Preferred examples of substituents other than hydroxyl or carboxyl groups are as follows: alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, cyclic alkenyl group, halogen atom, alkoxy group, aryloxy group, aryloxy group, Acylamino group, nitro group, cyano group, aryl group, alkoxycarbonyl group, aryoloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group , arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, dialkylamino group, anilino group, alkylamino group, diphenylamino group, N-acylanilino group, sulfamoylamino group, heterocyclicoxy group, or acyloxy group be.

Furthermore, when R and □ represent a heterocyclic group, it represents a 4- to 7-membered heterocyclic group containing at least one nitrogen atom, oxygen atom, or sulfur atom as a hetero atom, or a fused heterocyclic group thereof, such as pyridyl. , quinolyl, furyl, imidazolyl, 1. 2. 4 triazolyl, pyrazolyl,
Examples include thiadiazolyl, oxadiazolyl, benzimidazolyl, and the like, and these groups may have the substituents listed above when R3 is an aryl group.

RI! A particularly preferred example is a phenyl group having at least one hydroxyl group as a substituent.

At this time, as a substituent other than the hydroxyl group, the above RI2
When is a phenyl group, it may further have the substituents listed above.

Preferred specific examples of the yellow colored magenta coupler are listed below, but the invention is not limited to these.

-1 -2 -3 -4 M! I Shio 0 1 1 -1 Shi! H -16 -17 Shi! 8 9 20 I The above colored coupler is disclosed in JP-A-61-189538.
It is described in.

The yellow colored magenta coupler of the present invention is preferably added to the same layer as the colorless cyan coupler.

When the colored magenta coupler of the present invention is added to the same layer as the colorless cyan coupler, it is 0.1 to 20 mol, preferably 0.1 to 20 mol, relative to the colorless cyan coupler. It is preferable to add 5 mol to 10 mol.

Two or more colored magenta couplers of the present invention may be used in combination. It can also be used in combination with colored magenta couplers other than those of the present invention.

In order to realize the object of the present invention more effectively, it is preferable to use a compound represented by the following general formula (I[[) as a magenta colored coupler.

General formula (I[[) In the formula, RZI represents an aromatic group or a heterocyclic group, and R2□
represents a group that can be substituted on the naphthol ring. AB-N=N
-D represents a cambling leaving group, and A is a reaction between the oxidized color developing agent and the coupler of general formula (II[), and the bond between A and the carbon atom at the campling active position of this coupler is cleaved. B represents a divalent aromatic group or a heterocyclic group, D represents an aromatic group or a heterocyclic group, and n represents an integer of 0 to 4.

In addition, at least one of the groups represented by A, B and D in general formula (III) has a sulfo group as a substituent,
It has carboxyl groups, their alkali metal salts, ammonium salts, alkylamine salts, and pyridinium salts. By having such a water-soluble group, A-B-N=N-
The cambling-leaving group represented by D flows out into the developer after being released from the coupler residue.

Examples of the aromatic group represented by R2 include substituted or unsubstituted aromatic groups having 6 to 30 carbon atoms. In addition, as a heterocyclic group, the number of carbon atoms in the heterocyclic residue is 2 to 3.
Examples include 0 substituted or unsubstituted heterocyclic groups, and the heteroatoms in the heterocycle include N, O.

S, Se, etc., preferably a nitrogen-containing unsaturated heterocycle.

R2□ represents a group (including an atom, the same applies hereinafter) that can be substituted on the naphthol ring, and typical examples include a halogen atom, hydroxy group, amino group, carboxyl group, sulfonic acid group, cyano group, aromatic group, and heterocyclic group. , carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group,
Examples include aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, etc.
The number of carbon atoms contained in this Rat is 0 to 30. Examples of cyclic R1 when there are two Ro groups include a dioxymethylene group. The aliphatic group herein refers to an aliphatic hydrocarbon group including alkyl, alkenyl, and alkynyl groups, and may have conventional substituents.

The magenta colored cyan coupler represented by formula (DI) is preferably a magenta colored cyan coupler represented by general formula (IV).

In the formula, Rzt, A, B and n are synonymous with formula (1),
At least one of R23 and R27 is R31,OR
31, S Rs+, OCR2111 00 (here, Rffl represents a straight chain or branched alkyl group having 3 to 24 carbon atoms), R4, R5 and R6 are a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, or Represents an alkoxy group. R represents an alkyl group having 1 to 3 carbon atoms. M represents a hydrogen atom or □ m-valent cation.

Here, preferably n=o, and specific examples of maze, ntakara-do cyan couplers represented by general formula (IV) are illustrated below.

11[-(1) ■ (2) ■ (3) 111-(4) ■- (5) ■- (6) ■ (7) ■- (8) ■- (9) ■ (10) If-( II) 1[[-(12) 1[1-(13) If-(14) ■ (15) ■ (16) III-(17) III-(18) III-(19) III-(20) ) υ, Na UjNa ■ (21) ■ (22) III-(23) I[1-(24) ■ (25) ■ (26) Ill-(27) ■ (28) ■ (29) These couplers are It is described in Japanese Patent Application Laid-Open No. 63-23152.

In the present invention, magenta colored cyan couplers other than the magenta cyan coupler represented by the above general formula (fir) can be used, and as these magenta colored cyan couplers, those represented by the following general formula (V) are preferable.

General formula (V) H In the formula, Rzs represents an aliphatic group or an alicyclic group, Rt& represents a group that can be substituted on the naphthol ring, and n is 0 to 4.
represents an integer. A-B-N=N-D represents a coupling-off group and is the same as that shown in general formula (III).

Next, specific examples of the magenta colored cyan coupler represented by the general formula (V) are shown below.

(V-1) (V-2) (CHz) z (V-3) 0)I (CHz) z (V 4) H (V-5) (V 6) H 5υ3Na 03Na (■ 7) 0) ( ■ 8) (V-9) H (V 10) (V-11) 0 ■ (V 12) (V 13) H The magenta colored cyan coupler represented by the above general formula (V) is disclosed in, for example, U.S. Pat. , No. 004.929,
4.138,258 and British Patent No. 1.14
6.368.

In addition to the above couplers, magenta colored cyan couplers such as those represented by the general formula (n[) can also be used.

The high boiling point organic solvent referred to in the present invention refers to normal pressure (760 molHg).
) and has a boiling point of 175°C or higher.

Examples of high-boiling organic solvents used in conjunction with the coupler represented by general formula [I] include phosphoric acid esters (triphenyl phosphate, tricresyl phosphate, octyl diphenyl phosphate, tri-2-ethylhexyl phosphate, tri-n- xyl phosphate, tri-1 so-nonyl phosphate, tricyclohexyl phosphate, tryptoxyethyl phosphate, tri-2
-chloroethyl phosphate, etc.), benzoic acid esters (2-ethylhexyl benzoate, 2-ethylhexyl 2,4-dichlorobenzoate, etc.), fatty acid esters lj (di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, etc.), amides (N,
N-diethyldodecanamide, N-tetradecylpyrrolidone, etc.), dialkylaniline M (2-butoxy-5-
tert-octyl-N, N-dibutylaniline, etc.),
Chlorinated paraffins (paraffins with a chlorine content of 10% to 80%), phenols (2°5-tert-
amylphenol, 2,5-di-tert-hexyl-
4-methoxyphenol, p-hydroxybenzoic acid 2-
ethylhexyl, etc.) phthalate esters [(dibutyl phthalate, dicyclohexyl phthalate, didodecyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), but phosphoric esters and phthalic esters are particularly preferred.

The amount of the high-boiling organic solvent used in the present invention is determined based on the total weight of the couplers contained in one layer, and is at most 0.3 g per 1 g of the coupler. Deterioration of sharpness becomes a problem. The amount used is preferably 0.15 g per 1 g of coupler, more preferably 0.05 g, and even more preferably 0.01 g.
or less, and may be Og.

The total weight of couplers in this case refers to the total weight of all couplers contained in the silver halide emulsion layer containing at least one cyan coupler represented by the general formula [I].

The silver halide emulsion layer containing the cyan coupler is preferably red-sensitive and is composed of two or more layers with different sensitivities, each layer containing at least one type of general formula [I
It is more preferable to contain a cyan coupler represented by the following.

Further, it is preferable that at least one layer of the above-mentioned layer composed of two or more layers having red sensitivity and different sensitivities contains two or more types of cyan couplers represented by the general formula [I]. The cyan coupler represented by I) is 2
It is preferable that the layer containing at least one species does not contain a high boiling point organic solvent. The addition amount of the cyan coupler represented by the general formula [1) within the applicable range of the present invention (high boiling point organic solvent/coupler ratio at most 0.3) is usually 1.0XIO to 5 mol/
M to 3.0XIO-”mol/I, preferably 5,
Ox 10-' mol/rd naishi 1, 5 x 1
It is in the range of 0-3 mol/bo.

When the same color-sensitive silver halide emulsion layer is divided into two or more layers having different sensitivities, the present invention is preferably applied to layers other than the highest sensitivity layer.

In the present invention, the ratio of organic component to binder is 0.
It is preferably between 2 and 1.0, particularly preferably between 0.2 and 1.0.
It is between 0.8. If it exceeds 0.8, the emulsion may be altered if the coupler diffuses between the eyebrows, high-boiling organic solvents seep out, the film peels off during high-temperature processing, or the emulsion film becomes part of the processing machine. Make it easier. In addition, bulges may occur at interfaces with other layers. If it is less than 0.2, the amount of binder increases, resulting in delayed development and deterioration of sharpness, which is undesirable.

The ratio of organic component amount and binder is determined as follows. The organic component is an organic compound that does not dissolve in water by 5 wt% or more, such as couplers, colored couplers, development inhibitor-releasing couplers, and high-boiling organic solvents.The binder is often gelatin, but synthetic polymers may also be used. If used together, add them together as a binder.

Each ratio is expressed by weight and the ratio is taken. Polymer couplers are counted as organic components.

When the red-sensitive silver halide emulsion layer has a two-layer structure, the ratio of the magenta colored cyan coupler to the total cyan coupler in the high-speed layer is preferably in the range of 0 mol % to 20 mol %, and that in the low-speed layer is 5 mol %. Mol%~
It is preferably in the range of 40 mol%. In addition, in the case of a three-layer structure, the ratio of magenta colored cyan coupler to the total cyan coupler in the highest sensitivity layer is 0 mol % to 20 mol %.
Preferably, the amount is in the range of mol %, and it is preferably in the range of 0 mol % to 30 mol % in the medium sensitivity layer and 3 mol % to 50 mol % in the low sensitivity layer. Furthermore, the molar fraction of the magenta colored cyan coupler of the present invention with respect to the total amount of cyan coupler in the entire red-sensitive emulsion layer is 1 to 20%.
It is preferable that it is in the range of .

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 above-mentioned installation order may be reversed, or the installation order 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 above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 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 configuration can be preferably used.

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. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., 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 (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /High sensitivity red photosensitive layer (R) /Low sensitivity red photosensitive layer (RL)
), or BH/BL/GL/GH/RH/RL, or BH/BL/GH/GL/RL/RH.

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 H/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/G)I/RH may be arranged in this order from the farthest side from the support. You can also do it.

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 in which a silver halide emulsion layer with a low density is disposed and is composed of 3Ns having different photosensitivity, the photosensitivity of which is sequentially lowered 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, a medium-temperature emulsion layer/high-speed emulsion layer/low-speed emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, the layers may be arranged in the following order: low-sensitivity emulsion layer/medium-sensitivity emulsion layer/high-sensitivity emulsion layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4,705,744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

As described above, the layer structure and arrangement of various types can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic window optical material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. be. Particularly preferred is silver iodobromide or silver 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, 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) Nα17643
(December 1978), pp. 22-23, '■, Emulsion preparation and
307105 (198
November 9th, pages 863-865, and graphics “
"Physics and Chemistry of Photography", published by Beaumontel (P, GIa
fkides, Chemie et Ph1siqu
e Photographique, Paul Mo
ntel+ 1967), “Photographic Emulsion Chemistry” by Duffin
, Published by Focal Press (G, F, Duffin.

Photographic Emulsion Che
mistry (Focal Press.

1966)), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikm)
anetal, + Making and Coati
ng Photographic Emulsion+
Focal Press+ 1964).

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

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), 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 listed in Research Disclosure 811.
17643, No. 18716, and Nα30
7105, and the relevant parts are summarized in the table below. In the present invention, it is preferred to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a silver halide fine grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process, and is preferably not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, and preferably 0.01 to 0.5 μm.
02 to 0.2μ is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole compound, an azaindene compound, a hendithiazolium compound, a mercapto compound, or a zinc compound.

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

Gu! In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Patent No. 4,411.987 and US Pat.
, 435.503, which is capable of reacting with formaldehyde to immobilize it, is preferably added to the photoluminescent material.

Various color couplers can be used in the present invention, specific examples of which are listed in Research Disclosure N.
α17643, ■-C-C1 and Nα307105
, ■-C-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4.401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476.760, U.S. Patent No. 3,973,968, No. 4.314,
No. 023, No. 4,511,649, European Patent No. 24
9.473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3,725,067, Research Disclosure Nα24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure Nα24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4500.630, No. 4,540,654, No. 4,556,630 No., International Publication-088104
Particularly preferred are those described in No. 795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4,052.212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4,296,200, No. 2,369,9
No. 29, No. 2,801.171, No. 2,772.
No. 162, No. 2,895.826, No. 3,772
, No. 002, No. 3.758.308, No. 4.33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3329, 729, European Patent No. 121.365A
No. 249453A, U.S. Patent No. 3.446.6
No. 22, No. 4,333,999, No. 4,775.
No. 616, No. 4,451,559, No. 4.427
, No. 767, No. 4,690,889, No. 4,25
4゜212, 4,296,199, JP-A-61
−． Preferred are those described in No. 42658 and the like.

Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820; 4,080,211; 4,367.282;
No. 4.576°910, British Patent No. 2,102,
No. 137, European Patent No. 341188A, etc.

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.

In addition, couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling described in U.S. Pat. No. 4,774,181 and U.S. Pat. No. 4,777.12
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with the developing agent described in No. 0 to form a dye.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the previously described RD 1764
3. Patent described in ■-F section and Nα307105, ■F section, JP-A-57-151944, JP-A-57-1
No. 54234, No. 60-184248, No. 63-37
No. 346, No. 63-37350, U.S. Patent No. 4,248
, No. 962 and No. 4,782°012 are 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 compounds that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, etc., U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing couplers, DIR coupler releasing couplers, DI described in JP-A-6224252 etc.
R coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173°302
No. A, a coupler that releases a dye that recolors after separation as described in No. 313,308A, R, D, Nα11449,
No. 24241, bleach accelerator releasing coupler described in JP-A-61-201247, etc., U.S. Patent No. 4,555,47
Ligand releasing coupler described in No. 7 etc., JP-A-63-7
Couplers that emit leuco dyes as described in US Pat. No. 5,747, couplers that emit fluorescent dyes as described in US Pat.

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

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

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl) phthalate, bis(2,4-di-t-amyl phenyl) phthalate, esters of phosphoric or phosphonic acids (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-ethylhexyl benzoate,
dodecylhenzoate, 2-ethylhexyl-ρ-hydroxybenzoate, etc.), amides 11 ((N,N-diethyldodecanamide, N,N diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols ( Isostearyl alcohol, 2.4
-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (his(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N -dibutyl 2-
butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. has been done.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941
-dimethylphenol, 2-phenoxyethanol, 2
It is preferable to add various preservatives or antifungal agents such as -(4thiazolyl)benzimidazole.

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

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Nα17643, 647 of Nα18716
It is described from the right column of pages to the left column of page 648, and on page 879 of Na307105.

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 preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and particularly preferably 16 μm or less. . Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness was measured at 25°C and 55% relative humidity (2
The membrane swelling rate TI/□ means the membrane thickness measured in days).
It can be measured according to techniques known in the art. For example, Knee Green (A, Green)
Photogr, Sci, Eng, et al.
, Vol. 19, No. 2, pp. 124-129, T,7! The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30° C. for 13 minutes and 15 seconds, and is defined as the time required to reach the saturated film thickness of 172.

Membrane swelling rate T1/! 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 material according to the present invention includes the above-mentioned RD, N
α17643, pages 28-29, Nα18716, 65
1 left column to right column, and accompanying 307105 880 to 88
It can be developed by the usual method described on page 1.

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- 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 and hydrochlorides Alternatively, p-toluenesulfonate and the like can be mentioned. Among these, 3-methyl-4-amino-N-ethyl-
Nβ-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various chelating agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminetetraacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1 , 1-diphosphonic acid, nitrilo-N,N,N-1-rimethylenephosphonic acid, ethylenediamine-N,N,N,N tetramethylenephosphonic acid, ethylenediamine di(0-hydroxyphenylacetic acid) and their salts. This can be cited as an example.

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

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but -i is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 50 (
It can also be less than ld. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (I[[), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (III), such as aminopolymer salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (III) complex salts, including ethylenediaminetetraacetic acid iron (I [I) complex salt and 1,3-diaminopropane tetraacetate iron (II [) complex salt], are useful for rapid processing and environmental pollution prevention. Iron aminopolycarboxylate (1
) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (III
) The pH of the bleach or bleach-fix solution using complex salts is usually 4.
0-8, but lower pH for faster processing
It can also be processed with

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. Nα17129 (July 1978), etc.; Thiazolidine derivatives described in No.
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3,706.561
West German Patent No. L127,71
No. 5, iodide salts described in JP-A-58-16,235;
Polyoxyethylene compounds described in West German Patent No. 966,410 and West German Patent No. 2,748,430;
Polyamine compound lid described in No. 836 and other JP-A-49-
No. 40,943, No. 49-59.644, No. 53-9
No. 4,927, No. 54-35.727, No. 55-26
, No. 506, the compound described in No. 58-163.940;
Bromide ion 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.
．． Compounds described in No. 630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening the agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460, and the method described in JP-A-62-183.
A method of increasing the stirring effect using a rotating means as described in No. 461, and further improving the stirring effect by moving the photosensitive material without bringing the wiper blade provided in the liquid into contact with the emulsion surface and creating turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

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
Urnal of the 5ociety of M
tion Picture and Te1evis
ion Engineers Vol. 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 effectively used. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technical information [Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Industrial Technology Association, Japan Antibacterial and Antifungal Research Institute “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in (1986).

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 treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out. For example, a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for a color photosensitive material for photographing, may be further carried out. can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

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.

During processing using an automatic processor or the like, each of the above processing solutions evaporates into i! In the case of condensation, it is preferable to add water to correct the concentration.

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 Nα14,8
Schiff base-type compounds described in No. 50 and No. 15.159, aldol compounds described in No. 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, JP-A No. 5
Examples include urethane compounds described in No. 3-135628.

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

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10"C to 50°C. Usually, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate the processing and shorten the processing time. Or, conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Pat.
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. 210.66OA2, and the like.

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

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/nf units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 101) 1st layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 2nd layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.1SE
-10,07 EX-30,15 Dye ■ 0.25 Silver 0.25 6.9X10-'1.8X10-' 3, lX10-' 0.335 0.040 0.87 Silver 1.2 5, lX10-' 1.4X10-5 Sensitizing dye■ -2 X-8 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion sensitizing dye I Sensitizing dye ■ Enhanced dye ■ X-5 B5-1 Gelatin 7th layer (first green emulsion layer) Emulsion A 2.3X10-' 0.400 0.040 1.30 Silver 1.80 5.4 X 10-5 1.4 X 10 -5 2.4X10-' 0.030 0.180 0.22 0.10 1.63 0.040 0.020 0.80 Silver 0.15 Emulsion B Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ -6 X-1 X-7 X-8 B5-1 B5-3 8th gelatin layer (second green emulsion layer) Emulsion C Enhancing dye■ Sensitizing dye■ Sensitizing dye■ X-6 X-8 X- 7 B5-1 Silver 0,15 3.0X10-'1.0X10-'3.8X10-' 0.260 0.021 0.030 0.025 0.100 0.010 0.63 Silver 0.40 2, lX10-'7.0X10-'2.6X10-' 0.094 0.018 0.026 0.160 B5-3 Gelatin 9th layer (third green-sensitive emulsion layer) Emulsion E Enhancing dye ■ Sensitizing dye ■ Enhancement Sensitive dye ■ X-13 E X -11 X-1 B5-1 B5-2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver A 0.008 0.50 Silver 1.0 3.5X10-'8.0X10-'3.0X10-' 0.015 o, io.

O,025 0,25 0,10 1,54 Silver 0.05 0.08 0.03 0.95 Silver 0.08 Emulsion B Emulsion F Enhancement dye ■ X-9 X-8 B5-1 Gelatin 12th layer ( 2nd blue emulsion layer) Emulsion G Sensitizing dye ■ X-9 X-10 B5-1 Gelatin 13th layer (3rd blue emulsion layer) Emulsion H Enhanced dye ■ 07 Silver 0.07 3.5X10-' 0.721 0.042 0.28 1.10 Silver 0.45 2, lX10-' 0.154 0.007 0.05 0.78 Silver 0.72 2.2X10 -' 0.20 0.07 0.69 14th layer (first protective layer) Emulsion■ Silver 0.20U-
40,11 U-50,17 HB S -10,05 Gelatin 1.00 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 am) 0.5
43-1 0.20 Gelatin 1.20 In addition to the above ingredients, each layer contains gelatin hardening agent H-1, gelatin preservative/moldproofing agent 1.2-benzisothiaprin-3-one,
2-phenoxyethanol, phenethyl alcohol and a surfactant were added.

X l I X 2 (Example coupler C-7) H X-3 H X 4 X X CJ+3(n) X X X-9 I EX-12 C1 EX 3 -3 I -4 -5 B.S. to licresyl phosphate Di-n-butyl phthalate Sensitizing dye■ Exacerbating pigment■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ r14. .

-1 CH,=CH3O□-CHz CONFI CHzCH2=CH5o2CHz C0NHCHz (Preparation of Sample 102) EX-14 was added to the third layer and fourth layer of Sample 101 as shown in Table 1. After silver wedge exposure, the following development process was performed, and the coating amount of each layer was adjusted so that the obtained characteristic curve had the same gradation as the characteristic curve of sample 101. (EX-14 is the compound of JP-A No. 61-221748, Example 1) (Preparation of Sample 103) M-1 was added to the third and fourth layers of Sample 101 as shown in Table 1, and Sample 102 Similarly, the amount of each layer applied was adjusted to match the gradation.

(Preparation of Samples 104 and 105) HBS-1 was added to the third and fourth layers of Sample 103 in the amounts shown in Table 1. In addition, the amount of gelatin was increased so that the ratio of gelatin to the total amount of high boiling point organic solvent and coupler was constant so as not to deteriorate the film quality.

The obtained samples 101 to 105 were exposed to uniform green light and blue light, and after imagewise exposure with red light, they were developed as shown below, and the density was measured. As a result, the characteristic curve shown in Figure 1 was obtained. was gotten. Here, ΔD6 represents the value obtained by subtracting the magenta density of the exposed area (point B) where the red-sensitive emulsion layer gives a cyan color image density of 2.0 from the magenta density of the unexposed area (point A). ΔD represents the same value for yellow density. ΔDa, ΔD, color reproducibility (color turbidity)
was used as a scale. The results obtained are shown in Table 1.

Processing method Process color development bleached white Water washing Fixed arrival Wash with water (1) Tasik capacity 01 40i! 01 0ffi 10! Processing temperature Replenishment amount 38°C331d 38°C25d 24°C1200d 38°C25 24°C (2) # towards (1) Flow piping method.

200d 5IIfl processing time 3 minutes 15 seconds 6 minutes 30 seconds 2 minutes 10 seconds 4 minutes 20 seconds 1 minute 05 seconds Wash with water (2) 1 minute 00 seconds 24°C Stable 1 minute 05 seconds 38°C Drying 4 minutes 20 seconds 55°C Replenishment amount is 35cm per 1m length Next, the composition of the treatment liquid will be described.

10! 10I! (color developer) diethylenetriamine pentaacetic acid ■-Hydroxyethyl ten-1,1-diho Sulfonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfur acid salt 4-(N-ethyl-N -β-hydroxye thylamino)-2 Methylaniline sulfate add water pH (bleach solution) Mother liquor (g) 1.0 3.0 4.0 30.0 1.4 1.5 mg 2.4 4.5 1.0! 10.05 Replenisher (g) 37.0 1.0! 10.10 Mother liquor (g) Replenisher (g) Ethylenediaminetetravinegar Sodium ferric acid trihydrate salt Ethylenediaminetetravinegar acid disodium salt ammonium bromide ammonium nitrate Ammonia water (27χ) add water pH (Fixer) Ethylenediaminetetravinegar acid disodium salt sodium sulfite sodium bisulfite ammonium thiosulfate Aqueous solution (70χ) add water ioo,.

10.0 140.0 30.0 6.5m 1.OR 6,0 Mother liquor (g) 0.5 7.0 5.0 170.0 m 1, O1 120,0 11.0 160,0 35,0 4.Od l. Ol 5.7 Replenisher (g) 0.7 8.0 5.5 200.0 m 1.OI! .

pH 6°76.6 (stable solution) Mother liquor (g) Replenisher solution (g) Formalin (37χ) 2. Od 3
．． O1d polyoxyethylene-0,30,45 p-monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 Add 0.08 acid disodium salt water 1. Op, 1.0ffip
H5,0-8,05,0-8,0 These samples were then passed through a stepped wedge for RMS granularity measurement and subjected to the above treatment to achieve a density of 1.0 above the magenta fog density using a 48μ diameter aperture. The RMS was measured. The results obtained are shown in Table 1.

In addition, after storing these samples at -35°C for 7 days, they were exposed to a silver wedge for sensitometry at the same time as those stored at room temperature, the above-mentioned processing was performed, characteristic curves were obtained, and the cyan color image density during frozen storage was determined. We investigated the changes.

Furthermore, the MTF value was measured as a measure of sharpness. Measurement of MTF value is based on The Theory of Pho.
tographic Process 3rd ed.
(Mies, published by Matsuku Millan). The measurement results for cyan are shown in Table 1 for sample 101.
It is shown as a value when 100.

As is clear from Table 1, when comparing Samples 101 to 105, Sample 103 according to the present invention not only has an improvement effect on color reproduction compared to Sample 101 as well as Sample 102, but also has a higher granularity than Sample 102. It can be seen that it has excellent properties and freeze storage stability. In addition, samples 103 to 10
As can be seen from the comparison of No. 5, it was also clear that the sharpness could be improved by setting the A value to 0.3 or less.

Example 2 On a subbed cellulose triacetate film support,
Sample 201, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the photosensitive layer) The coating amount is expressed in g/rrf of silver for silver halide and colloidal silver, and the amount expressed in g/rrr for coupler additives and gelatin. The number of moles of the dye is expressed per mole of silver halide in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

U■: Ultraviolet absorber, S OI vi high boiling point organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler ExY
; Yellow coupler, Cpd; Additive 1st layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.0ExM-60
,2 UV-10,03 UV-20,06 UV-30,07 Solv-10,3 Solv-20,08 ExF-10,01 ExF-20・01 ExF-30,005 Cp d -60,001 2nd layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 30%, tabular grains , diameter/thickness ratio 3.0) Coated silver amount 0.35 Silver iodobromide emulsion (Ag1 6 mol%, core shell ratio 2:l
internal high Agl type, equivalent sphere diameter 0.45 μm, coefficient of variation of equivalent sphere diameter 23%, plate-shaped particles, diameter/thickness ratio 2.0) Coated silver amount 0.18 Gelatin 0.76E x
S -12,2xlO-' Ex S-21,3X10-' Ex S -52,2X10-' Ex S -74,0xlO-6 ExC-10,16 Ex C-20,03 Ex C- 30,009 3rd layer (mid-sensitivity red-sensitivity emulsion layer) tJfL modified WA emulsion (A g I 6 mol %, Koala x), internal high Ag I type with a ratio of 2:1, equivalent sphere diameter 0.65
μm, coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter/thickness ratio 2.0) Gelatin xS-I xS-2 xS-5 xS-7 xC-1 Coated silver amount 0.81 1.25 2. 9X10 1.7X10 2.9X10 5.2X10 0.39 E x C-20,01 1[[-(4)
0.12 4th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 19.3 mol%, core shell ratio 3:
4:2 multi-structured particles, Agl content from inside to 24.0
．． 6 mol%, equivalent sphere diameter 0.75 μm, coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter/thickness ratio 2.5) Gelatin xS-I xS-2 EχS-5 xS-7 xC-I olv -I olv-2 Cpd-7 5th layer (intermediate layer) Amount of gelatin coated silver 1.5 1.4 1.9X10-'1.2X10-' 1.9 X 10-'8.0X10-" 0.17 0.08 0.20 4.6X10-' 0.6 Cpd-10,1 Polyethyl acrylate latex 0.08So
lv-10,08 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, uniform Agl type, equivalent sphere diameter 0.33 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like) Particles, diameter/thickness ratio 2.0) Coated silver amount 0.19 Gelatin 70.43 Ex M-50 Ex M-50 ,17 Ex M-70,03 Ex Y -80,01 Solv-10,06 Solv-40,01 7th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, uniform Agl type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter/W-view ratio 4.0) Coated silver amount 0.26 Gelatin 0.57E x
S -31,9X10-' Ex S-46,7X10-' Ex S-51,3X10-' Ex M-50,16 ExM-70,04 Ex Y -80,04 Solv-] 0.13So
lv-40.01 8th layer (high sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 8.8 mol%, silver amount ratio 3:/4
:2 multilayer structure particles, AgI content 24 moles from inside,
0 mol, 3 mol%, equivalent sphere diameter 0.75 μm, coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter/thickness ratio 1.6) Coated silver amount 0.5 Gelatin 0.6E x
S -45,2X10"' xS-5 xS-8 xM-5 xM-6 xY-8 xC-1 xC-4 olv-1 olv-2 olv-4 p d-7 p d-8 9th layer (intermediate layer) gelatin pd-1 polyethyl acrylate latex olv-1 UV'-4 V-5 10th layer (layer effect on red anger layer 1 Xl0-'0.3X10-' 0.08 0.03 0.02 0 .01 0.01 0.23 0.05 0.01 1XIO-' 0.01 0.6 0.04 0.05 0.02 0.03 0.04 Donor layer) Silver iodobromide emulsion (Ag1 8 mol %, core shell ratio 2:1
internal high Agl type, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.67 Silver iodobromide emulsion (Ag1 4 mol%) , uniform Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.20 Gelatin 0.9E x
S-35,6X10-' ExM -100,18 Solv-10,28 Solv-60,03 11th layer (yellow filter layer) Yellow colloidal silver 0.06 Gelatin 0.8Cpd-20
,13 Solv-10,13 Cpd-10.07 Cpd-60,002 H-10,13 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag14.5 mol%, uniform-AgI type , equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount 0.47 Silver iodobromide emulsion (AgI 3 mol%, uniform-AgI type) , equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount 0.26 Gelatin 2.2E x S
-69,5X10-' ExC-10,14 ExC-40,03 ExY-90,17 ExY-111,09 Solv-10,54 13th layer (middle layer) Gelatin 0.4ExY-1
20,20 Solv-10,19 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, internal high AgI type,
Equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount 0.
4 Gelatin 0.5ExS-
6txto-' Ex Y-90,01 ExY-110,20 Ex C-10,01 Solv-10,10 15th layer (first protective layer) Fine grain silver iodobromide emulsion (Ag1 2 mol%, uniform Agl type, equivalent sphere diameter 0.07 um) Coated silver amount 0.12 Gelatin 0.7 U V
-40,11 UV -50,16 Solv-50,02 H-10,13 Cpd-50,10 Polyethyl acrylate latex 0.09 No. 16
Layer (Second Protective Layer) Fine-grain silver iodobromide emulsion (Ag1 2 mol%, uniform-Agl type, equivalent sphere diameter 0.07 pm) Coated silver amount 0.36 Gelatin 0.85 polymethyl methacrylate particles (Diameter 1.5μm) 0.2Cp
d -40,04 W-40,02 H-10,17 In addition to the above components, each layer contains an emulsion stabilizer Cp d
-3 (0.07 g/bo), surfactant W-1 (0°00
6g/m"), W-2 (0.33g/m"),
W-3 (0.10 g/m2) was added as a coating aid and emulsifying dispersant.

In addition, in order to mainly improve anti-fungal and anti-bacterial properties,
-Benzisothiazolin-3-one, 2-phenoxyethanol, and phenethyl alcohol were added.

V-1 H V 0 ■ U■ H (t)CaHq V X: y=70:30 (ivt%) V-5 o lv tricresyl phosphate olv-2 dibutyl phthalate o IV trihexyl phosphate ExF-1 N　(CzHs)　z ExF CH.

CH3 C2H50SOρ xS xS xS xS xS xS xS-7 (CHz) 3SO3H-N (CJs)! xS xC 1 (Example coupler C 7) CH xC ExC-3 (Example coupler ■ (4)) xM-5 xM xM 0 xY-9 Hz xY-11 pd 6HI3 pd-2 U Pd H pd Pd L ■ pd-6 p d-7 pct CH,=C)I SO□-CHz C0NHCHt CH,=CH 5IJz CHt C0NHCHz2H5 (n) CJ, C) lcHzcOOcHz (n) C, 1l
qCHCHZCOOCH3O3Na2H5 C,F,,So□N(CJ7)CHzCOOK(Sample 2
02) The second and third layers of sample 201 were coated with EX-
No. 14 was added as shown in Table 2, and the coating amount of each layer was adjusted to match the gradation of sample 201.

(Preparation of sample 203) M was added to the second and third layers of sample 201 in the same way as sample 202.
-1 was added as shown in Table 2, and the coating amount of each layer was adjusted to match the gradation.

(Preparation of Samples 204 and 205) HBS-1 was added to the second and third layers of Sample 203 in the amounts shown in Table 2. In addition, the amount of gelatin was increased so that the ratio of gelatin to the total amount of high boiling point organic solvent and coupler was constant so as not to deteriorate the film quality.

These samples 201 to 205 were treated with Δ
Dc and ΔD were determined. The results obtained are shown in Table 2.

Furthermore, the frozen storage stability was also examined in the same manner as in Example 1.

Next, for magenta and cyan, as a measure of sharpness,
The MTF value was measured. The measurement of MTF value is
theory of Photographic Pro
The method described in cess 3rdedd (published by Matsuku Millan, written by Mies) was followed. The results are shown in Table 2 for sample 20.
It is shown as a value when 1 is set as 100.

Furthermore, the RMS granularity of these samples was measured in the same manner as in Example 1. For magenta, 1 from fog density
．． 0 RMS value at high concentration, sample 201 to 100
It is shown in Table 2 as follows.

As is clear from Table 2, the samples of the present invention are excellent in color reproducibility, graininess, sharpness, and cryopreservability.

Implementation fN3 Colorless cyan coupler C-7 in the second and third layers of Example 2
Sample 301 was prepared by replacing CU-1 with the following CU-1. When the spectral absorption peak of the cyan color image of sample 301 was measured, the absorption peak had a large concentration dependence, the color reproducibility differed depending on the color density, and the color fidelity was lower than that of sample 203.

It also required the addition of a high boiling organic solvent and an increase in the amount of gelatin. The sharpness was also worse than that of sample 203.

U-1 Example 4 Colorless cyan coupler C-7 in the second and third layers of Example 2
When carried out in the same manner as in Example 2 by replacing C-3 and C-4 with yellow colored magenta coupler and M-1 with M2 and M-20, the same result as in Example 2 was obtained. Trend results were obtained.

(Effects of the Invention) As explained above, according to the present invention, it is possible to obtain a color photographic material that has excellent color reproducibility, improved graininess and sharpness, and excellent freeze storage stability.

[Brief explanation of drawings]

FIG. 1 shows characteristic curves for uniform green, blue, and red imagewise exposures.

Claims (2)

[Claims] (1) In a silver halide color photographic material having at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support, at least one red-sensitive emulsion layer is represented by the following formula [I]. and at least one yellow-colored magenta coupler in the emulsion layer, and further contains a high-boiling organic solvent in a weight ratio of at most 0 to the total amount of couplers contained in the emulsion layer. A silver halide color photographic material characterized by containing .3. Formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula [I], R_1 is -CONR_4R_5, -S
O_2NR_4R_5, -NHCOR_4, -NHCO
OR_6, -NHSO_2R_6, -NHCONR_4
R_5 or -NHSO_2NR_4R_5, R_2
is a group that can be substituted on the naphthalene ring, l is an integer from 0 to 3, R_3 is a substituent, and X is a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. respectively. However, R_4 and R_
5 may be the same or different and independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R_6 represents an alkyl group, an aryl group or a heterocyclic group. When l is plural, R_2 may be the same or different, or may be bonded to each other to form a ring. R_2 and R_3 or R_3 and X may be combined with each other to form a ring. In addition, R_1, R_2, R_3, or X may form a dimer or a multimer of more than two valent molecules bonded to each other via a divalent or more divalent group. (2) The silver halide color photographic material according to claim 1, wherein the emulsion layer further contains at least one magenta colored coupler.