JPH0476541A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and to improve desilverability by incorporating a specified cyan coupler into a red-sensitive layer and a specified compd. into at least one silver halide emulsion layer. CONSTITUTION:A cyan coupler represented by formula I in incorporated into a red-sensitive layer, the percentage of a two-equiv. coupler in dyestuff forming couplers contained in the layer is regulated to >=60mol% and a compd. represented by formula II is incorporated into at least one silver halide emulsion layer. In the formula I, R1 is H, halogen, etc., R2 is a group substitutable on the naphthalene ring, R3 is a substituent, X is a group releasable by coupling with the oxidized body of an arom. prim. amine developing agent, l is an integer of 0-3 and m is 0 or 1. In the formula II, A is a residue of a coupler releasing (TIME)n-B by coupling with the oxidized body of an arom. prim. amine developing agent, TIME is a timing group releasing B after release from A and B is a group represented by one of formulae III-V (where X1 is an aliphatic group or substd. phenyl and X2 is H, an aliphatic group, alkoxy, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a silver halide color photographic light-sensitive material.

(Prior art) In recent years, silver halide photosensitive materials, especially photosensitive materials for photography, have been developed to have ultra-high sensitivity and have satisfactory sharpness, graininess, and color reproducibility even when printed at large magnifications. There is an increasing demand for photosensitive materials. As a means for improving the sharpness, there is a means for improving the sharpness by shortening the scattering path by making the light-sensitive material thinner.

On the other hand, silver halide color photographic materials undergo a series of photographic processing to form a dye image after image exposure, but in recent years the processing has become faster, for example bleach-fixing processing in which bleaching and fixing are performed in one bath. became possible. However, although these treatments can certainly shorten the processing time, there is a problem that desilvering cannot be done within this time, and it has become necessary to take measures such as making the photosensitive material to be processed thinner and improving its desilvering properties. There is.

On the other hand, there are two-equivalent couplers as image-forming couplers used in silver halide color photographic materials. If this is used, the amount of silver used can be reduced, the layer can be made thinner, and the desilvering performance can be improved.

Further, although the deterioration of sharpness in the high frequency region due to light scattering can be improved to some extent by thinning the layer, the sharpness is not sufficient.

However, if a 2-equivalent coupler is normally used, JP-A-63-
As described in No. 294560, etc., it is known that the graininess deteriorates, so when using a 2-equivalent coupler, care must be taken in selecting it, especially when using it in the red-sensitive layer. was difficult. Japanese Patent Publication No. 1-13'
No. 1558, JP-A-62-180365, JP-A No. 62-8
The use of a 2-equivalent cyan coupler is described in No. 7960, etc., but the coupler described in the patent suffers from a significant deterioration in graininess and requires improvement.

On the other hand, in order to improve the sharpness and color reproducibility of images, it is common to use development inhibitor-releasing couplers, so-called DIR couplers, and many patents have been filed heretofore. Although the DIR compounds proposed in JP-A-64-4743 and JP-A-64-15738 can certainly improve sharpness, color reproducibility, and graininess to some extent, the sharpness in the high frequency region based on light scattering is unsatisfactory. It was something.

(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 sharpness and improved desilvering properties.

(Means for Solving the Problems) The objects of the present invention have been achieved by the following color photosensitive materials.

In a silver halide color photographic material having at least one blue-sensitive emulsion layer, one green-sensitive emulsion layer, and one red-sensitive emulsion layer each on a support, the red-sensitive layer contains the following general formula [C
], the ratio of 2-equivalent couplers among the dye-forming couplers contained in the red-sensitive layer is 60% or more by mole, and at least one silver halide emulsion layer has the following general formula: A silver halide color photographic material comprising a compound represented by (1).

General formula (1) % formula %) In the formula, A represents a coupler residue that leaves -B due to the coupling reaction (TIME) with the oxidized product of the aromatic primary amine developer, and TIME is the Represents a timing group that binds to the coupling active position and releases B after being separated from A by the coupling reaction, and B represents the following general formula (
II a), (II b), (IIc), (I[d),
(II e), (Iff), (II g), (I[h)
, (IF i), (I[j), (I[k), (II n
), (IIm), (II n), (IIo) or (I
lp), and n represents an integer of 0 or l. However, when n is 0, B is directly bonded to A.

General formula (na) General formula (n b) General formula (n c) General formula (nd) General formula (Ili) General formula (nj) General formula (ne) General formula (Ilf) General formula (II k) General formula (R1) General formula (IIm) General formula (II n) General formula (n g) General formula (n h) (Group 2 General formula (R0) General formula (II p) In the formula, Xl is the number of carbon atoms Represents 1 to 4 substituted or unsubstituted aliphatic groups or substituted phenyl groups. x2 is a hydrogen atom,
Aliphatic group, halogen atom, hydroxyl group, alkoxy group, alkylthio group, alkoxycarbonyl group, acylamino group, carbamoyl group, sulfonyl group, sulfonamide group, sulfamoyl group, acyloxy group, ureido group, cyano group, nitro group, amino group , an alkoxycarbonylamino group, an aryloxycarbonyl group or an acyl group, X3 represents an oxygen atom, an ionic atom or an imino group having 4 or less carbon atoms, and m represents an integer of 1 or 2. However, the total number of carbon atoms contained in the m number of X2 is 8 or less, and when m is 2, the two X2 may be the same or different.

(R3NH)ffi In general formula [C], R is -CONR,R,, -8o
2 NR,R,, -NHCOR,, -NHCOOR,,
-NH8O,R,, -NHCONR,Rs, -NHS
O2NR,Rs is a hydrogen atom, a halogen atom, or a heterocyclic group, R2 is a group that can be substituted on a naphthalene ring, R3 is a substituent, and X is a coupling reaction with an oxidized product of an aromatic primary amine developer. 1 represents an integer of 0 to 3, and m represents an integer of 0 to 1.

However, R4 and R5 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, respectively. However, X is not a group substituted with a carboxyl group. Further, when l is plural, R2 may be the same or different, and may be bonded to each other to form a ring. R2 and R3, or R3 and X may be bonded to each other to form a ring. R1, R2, R3, or X may form a dimer or a multimer of more than two molecules bonded to each other via a divalent or more divalent group.

Each substituent in formula [C] will be explained in detail below.

R, is -CONR, R1, -8o, NR, R,, -NH
COR,, -NHCOOR,, NHCONR,R5, -NH3O□NR,R, represents a hydrogen atom, a halogen atom or a heterocyclic group.

Here, R4, R5 and R6 are each independently a hydrogen atom, 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 carbon atoms, or a heterocyclic group having from 2 to 30 carbon atoms. and any of these groups may be substituted. When R1 is a heterocyclic group, it is a C2-30 heterocyclic group and may be substituted.

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, CA
', 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, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, sulfamoylamino group, alkoxycarbonylamino group, nitro group, An imide group can be mentioned. Examples when 1=2 include a dioquinmethylene group and a trimethylene group. (R2)
The C number of 1 is 0 to 30.

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

Formula [C-1] R, (Y), In formula [C-1], Y is )NH,)CO or)SO
2, n is an integer of 0 or 1, R7 is a hydrogen atom, an alkyl group with 1 to 30 carbon atoms, an aryl group with 6 to 30 carbon atoms, C
Heterocyclic group of number 2 to 30, C02R,, -C-3R,,
, -3o,OR,. or -8o2R, o, respectively. Here, R15R9 and RIo have the same meaning as R2, R5 and R6, respectively.

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

X represents a group other than a hydrogen atom 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); typical examples of leaving groups include halogen. Atom, -OR,, -8R,, -0C
R,, -NHCOR-0CNHR,, 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- hensitriazolyl group). Here, R11 has the same meaning as R6. However, X is neither a hydrogen atom nor a group substituted with a carboxyl group.

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's propyl.

Furthermore, even if an 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-5-dodecyloxyphenyl, and 4-t-butylphenyl.

In addition, the heterocyclic group is 0. N, S, P, Se,
3-8 containing at least one heteroatom of Te in the ring
A membered monocyclic or fused ring heterocyclic group, which has a substituent (
For example, halogen atoms, carboxyl groups, hydroquine groups, nitro groups, alkyl groups, aryl groups, alkoxy groups,
aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group), and representative examples include 2-pyridyl, 4-pyridyl, -Furyl, 4-thienyl, benzotriazol-1-yl, 5-phenyltetrazole-
1-yl, benzimidazol-2-yl, 5-methylthio-1,3,4-thiadiazol-2-yl, and 5-methyl-1,3,4-oxadiazol-2-yl.

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

R1 is preferably -CONR, R, or -5o2NR4R, and specific examples include carbamoyl, N-n-butylcarbamoyl, N-n-dodecylcarbamoyl, N-(3-n-dodecyloxypropyl)carbamoyl, N-cyclo hexylcarbamoyl, N
-[3-(2,4-di-t-pentylphenoxy)propyl]carbamoyl, N-hexadecylcarbamoyl,
N-[4-(2,4-di-t-pentylphenoxy)butylcarbamoyl, N-(3-dodecyloxy-2-methylpropyl)carbamoyl, N-C3-(4-t-octylphenoxy)propyl]carbamoyl , N-hexadecyl-N-methylcarbamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N-C4-(2,
4-di-t-pentylphenoxy)butylcarbamoyl. R1 is particularly preferably -CONR, Rs.

As R2 and l, 1=O, that is, unsubstituted is most preferable, and A=1 is the second most preferable. R2 is preferably a halogen atom, an alkyl group (e.g. methyl, isopropyl, t-butyl, cyclopentyl), a carbonamide group (
For example, acetamide, pivalinamide, trifluoroacetamide, benzamide), sulfonamide (eg methanesulfonamide, toluenesulfonamide) or a cyano group.

R3 is preferably h=0 in formula CC-1],
More preferably, R7 is -COR, [e.g. formyl, acetyl, trifluoroacetyl, 2-ethylhexanoyl, pivaloyl, benzoyl, pentafluorobenzoyl, 4-(2<4-di-t-pentylphenoxy)butanoyl], - COOR,. [For example, methoxycarbonyl, ethoxycarbonyl, imbutoxycarbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl, 2-methoxyethoxycarbonyl]
or -5o2R,oC e.g. methylsulfonyl, n-
butylsulfonyl, n-hexadecylsulfonyl, phenylsulfonyl, phlylsulfonyl, p-chlorophenylsulfonyl, trifluoromethylsulfonyl], and particularly preferably R7 is -COOR. It is.

m is preferably 1.

X is preferably not a carboxyl or sulfo substituted group. X is more preferably a halogen atom (preferably F, C12, Br), -OR,
, (R, is preferably an alkyl group or an aryl group)
or -3R, (R, 1 is preferably an alkyl group), and Rl is an alkyl group, an aryl group, a heterocyclic group,
Halogen atom, cyan group, hydroxyl group, nitro group,
Amine group, alkoxy group, alkylthio group, aryloxy group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, carbonamide group, sulfonamide group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoylamino group, acyloxy group, alkoxycarbonyloxy group, alkylsulfonyloxy group,
It may be substituted with an arylsulfonyloxy group, an alkoxysulfonyl group, a phosphoryl group, a phosphoryloxy group, or a phosphorylamino group.

X is particularly preferably a chlorine atom or a group represented by the following formula [C-2].

Formula [C-2] 0-R-(Z).

In the formula [:C-2], R represents a (p+1)-valent hydrocarbon group (which may contain an aromatic ring, an aliphatic ring, or an unsaturated bond), and Z represents a heterocyclic group (hensitriazolyl group). ,l,
2. 3. (excluding 4-tetrazole-5thion-1-yl group), halogen atom, cyano group, hydroxyl group,
Acyl group, alkoxy group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, carbonamido group, sulfonamido group, alkoxycarbonyl group, carbamoyl group, alkoxysulfonyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl group p represents an integer of 1 to 6, and represents a group selected from an amino group, an acyloxy group, an alkoxycarbonyloxy group, an alkylsulfonyloxy group, a phosphoryl group, a phosphoryloxy group, or a phosphorylamino group. When p is plural here, Z may be the same or different.

The number of C in the group represented by formula [C-2] is preferably 12 or less, more preferably 8 or less, particularly preferably 6 or less. Z is preferably a halogen atom, a cyano group, a hydroxyl group, an alkoxy group, an alkylsulfonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or a heterocyclic group (preferably pyrrolyl, imidazolyl, pyrazolyl, oxazolidine-2, 4-dion-3-yl, 1,3.4-1-riazolyl, tetrazolyl, hydantoinyl, succinimide-1yl). R is preferably a chain hydrocarbon group. p is preferably an integer of 1 to 3.

The coupler represented by [C] may form a dimer or a multimer of more than two molecules bonded to each other via a divalent or divalent or more divalent group in the substituent RR2, Rh or X, respectively. In this case, the number of carbon atoms in each substituent may be outside the ranges indicated above.

When the coupler represented by formula [C] forms a multimer,
An addition-polymerizable ethylenically unsaturated compound having a cyan dye-forming coupler residue (a typical example thereof is a cyan color-forming monopolymer or a copolymer thereof, and is preferably represented by formula (C-3)).

Formula [C-3) (G,), -(H,)h In formula [C-3], 01 is a repeating unit derived from a color-forming monomer and is a group represented by formula [C-4]. , Hl is a group that is a repeating unit derived from a non-chromogenic monomer, i represents a positive integer, j represents 0 or a positive integer, and gi and hi represent the weight fraction of G1 or Hj, respectively. represent. where i or j
When there is a plurality of , it means that Gi or Hi includes a plurality of types of repeating units.

Formula (C-4) In formula [C-4], R' is a hydrogen atom, and has 1 to 1 carbon atoms.
4 represents an alkyl group or a chlorine atom, and A is -CON
H--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, L is 100NH -NHCONH--NHCOO--NHCO-OCNH
--NH--COO--0CO--CO--0--8O
, --NH8O2 or -8O2NH-. a,
b and c represent integers of 0 or l. Q is a general formula [C]
represents an uncoupler residue obtained by removing one hydrogen atom from R1, R2, R3 or X of the compound represented by

Examples of non-color-forming ethylene monomers that do not couple with the oxidation products of aromatic-grade amine developers that provide repeating units Hj include acrylic acid, α-chloroacrylic 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 such as vinyltoluene, 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 kinds of the non-color-forming ethylene monomers used here can also 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. can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above formula [C-4] depends on the form of the copolymer to be formed, such as solid or liquid. 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 ceratin, its flexibility, thermal stability; It can be selected so as to favorably influence properties, coupling reactivity with oxidized developer, wave resistance in photographic colloids, etc. 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, it is preferable to mainly select lipophilic non-color-forming ethylene-like monomers (for example, acrylic esters, methacrylic esters, maleic esters, vinyl henzenes, etc.) as copolymerization components. preferable.

A lipophilic polymer coupler obtained by polymerizing a vinyl monomer to provide a coupler unit represented by the above general formula [C-4] 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, N-(1,1 dimethyl-2-
ethyl sulfonate) acrylamide, 3-sulfonate propyl acrylate, sodium styrene sulfonate, potassium styrene sulfinate, acrylamide,
It is preferable to use hydrophilic non-color-forming ethylene-like monomers such as methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, and N-vinylpyridine as a copolymerization component.

The wood-philic polymer coupler can be added to the coating solution as an aqueous solution, and can also 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 [C] and the cyan coupler represented by formula (C) are shown below.

Examples of R1 C0NH(CH2), OA -CONH(C
H2), C)-A-CONH(CH2)80C1+H
2i-n -CONH(CH2)30C+oH++-
n2H5 CONH(CH2)80CH2CHCt Ha-n
-CONHC1aH3+-nCH.

-CONHCH+ CHCH+ 0CBH2i-nCO
NH(CH2CHI O) 2 C1□Hxi-nCO
NHCH2CH20CuHu-n CONH(CH2)80CuH2on-CONH(C
H2), QC 2a-n C+282! Costume 1 C, H.

0C82CHC,H.

R1 Example of NH- example F Cf C.N. CH3 -C,F.

C4Hs~t -C, H, □-t -NHCOCH.

-NHS02 CH.

-NHCOOC,H.

-NH3O, CF.

NH3O2CI R9-n Ushi12t'i2S of example Br CH3 0CR2CH.

-0C82CC1゜ 10CH2CF3 OCH2CH2(J’ 0CH2CH2Br -0CH2CH20H -O(CH2CH20) 2H -0(CH2CH20)3H o (CH2CH20), H -O(CH2CH2CH20) 2H OCR2CHOH H -O(CH20HCHI　O)2　H o (CH, CH20), CHI H -O(CH2CH20), CH.

-0CF(CH20CH.

CH.

-NHCOOC,H,-n -NHCOOCH2CH20CH.

-NHCOOCH2CH20-A -NHCOCOCR.

CH2CN -CH2CH2CN CH.

CH,CHCN 0CR, C00CR.

0CH2COOCH2CH20CH.

-0CRCOOCR.

0CRCOOCH3 CH3 CH.

CH3 OCH2C00C12H25 OCRCOOCH.

C1□HI5 0CH2CH20CH2CH, C00C2H.

0CH2CH, C00CH.

-O(CH2), C00CH.

0CH2CH2SCH2CH20H CH.

0CH2CH2SCH2CHCH20HH -OCH,CH,So□C2H5 -OCH,CH25o2C,H.

-OCH,CH,So,CH2CH20HOCH2CH
, NHCOCH.

OCH,CH2NHCOC,H.

0CH2CH,NH302C,H.

0CH2CH20COOC2H.

-OCH, CH20SO2CH.

OCH, C0NHCH2CH20CH.

-0CH2CONHC,H8 -0CH2CH2So2NHC,H.

0CH2CCH.

0CH2CH2CCH2CH20H -OCRCOOH OCHCOOH OCH, CH, NSO, CH.

C1□82B C14H2゜ CH.

-3CH, CH20CH.

-3CH,C00C)13 -5CH2CONHC2H.

-8CH, CH20CH2CH20H Example of coupler represented by formula [C] CH,C0NH C2H50CNH OCR.

CH.

+-C,890CNH OCH, CH, OCH.

(C2H=U)2FNM Sushi? 12utJrishit'i3 2H5 ￥g Shi* Hl + U tl Shi H2 (J Shi N M Shi! j2 C1 I C1□H25 C1゜H2i OCR, CH, Cl 0CHI C00CH.

0CHCOOCH.

2H5 C i-C,H90CNH ○CH, CH, OCH.

40 (weight ratio) Number average molecular weight approximately 60 l C2H,0CNH A 35: ], 0 (weight ratio) Number average molecular weight approximately 50° average 4 A NHCOC2H5 OH x:y=70:30 (weight ratio) Number average molecular weight approximately 45° C, H, So, NH OCH, CH, OH Number average molecular weight approximately 50° C1□F(2i NH3○2CHh OCH.

NHCOCH.

Specific examples of the cyan coupler represented by formula [C] other than the above and/or methods for synthesizing these compounds are described, for example, in JP-A-50-10135, JP-A-50-17422, and JP-A-50.
-130441, 51108841, 52-1
No. 8315, No. 52-20023, No. 52-9093
No. 2, No. 54-14736, No. 54-48237,
No. 55-32071, No. 55-65957, No. 56
-1938, 56-12643, 562714
No. 7, No. 60-237448, No. 61-153640
No. 60-145557, No. 62-123157, No. 62-123158, No. 63-208042,
No. 64-31159, JP-A No. 2-6947, No. 2-
No. 6948, US Patent No. 4,690,889, European Patent No. 250.201A, West German Patent No. 3. 819.
It is described in No. 05IA and No. 3823049A.

The cyan coupler represented by the formula [C] is disclosed in Japanese Patent Application Laid-Open No. 1986-
As described in No. 269958, it is preferable to use a small amount of a high-boiling organic solvent for dispersion in order to further improve sharpness and desilvering properties.

Specifically, the weight ratio of the high boiling point organic solvent to the cyan coupler represented by formula [C] is 0.3 or less, more preferably 0.3 or less. It is 1 or less, and may be 0.

The total amount of the cyan coupler represented by formula [C] 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 %.

Next, the compound represented by the general formula (r) will be explained in detail.

In the formula, X1 is a substituted or unsubstituted aliphatic group having 1 to 4 carbon atoms (substituents include alkoxy group, alkoxycarbonyl group, hydroxyl group, acylamino group, carbamoyl group, sulfonyl group, sulfonamide group, sulfamoyl group, amino (The number of carbon atoms contained in these substituents is 3 or less), or substitution Phenyl group (substituents include hydroxyl group, alkoxycarbonyl group, anruamino group, carbamoyl group, sulfonyl group, sulfonamide group, sulfamoyl group, acyloxy group, ureido group, carfoquinol group, cyano group, nitro group, amine group, or acyl group) (The number of carbon atoms contained in these substituents is 3 or less.)

X2 is an aliphatic group, a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group,
Represents an acylamino group, carbamoyl group, sulfonyl group, sulfonamide group, sulfamoyl group, acyloxy group, ureido group, cyan group, nitro group, amino group, alkoxysulfonylamino group, aryloxycarbonyl group, or acyl group, and X3 is an oxygen atom. , represents a sulfur atom or an imino group having 4 or less carbon atoms, and m represents an integer of 1 or 2. However, the total number of carbon atoms contained in the m number of X2 is 8 or less, and when m or 2, the two X2 may be the same or different.

The "aliphatic group" of Xl and X2 indicates an aliphatic hydrocarbon group, and this group may be saturated or unsaturated,
It may also be chain, branched, or cyclic, and specifically includes alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, and alkynyl groups.

In the present invention, it is preferable to use a timing type DIR coupler in which both A and 8 residues are bonded via a TIME group where n=1.

The compound represented by general formula (I) will be described in detail below.

As the coupler residue represented by A in general formula (1), the coupling reaction with the oxidized product of an aromatic primary amine developer produces a dye (for example, yellow magenta, cyan, etc.).
and coupler residues that provide a coupling reaction product that has substantially no absorption in the visible light region.

The yellow image-forming coupler residue represented by A includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type,
Malone ester monoamide type, benzothiazolylacetate type, henzoxazolyl acetamide type, henzoxazolyl acetate type, malon diester type, henzimidazolylacetamide type or benzimidazolylacetate type coupler residue, US Pat. 841,
No. 880, a coupler residue derived from a petro ring-substituted acetamide or a petro ring-substituted acetate, or U.S. Pat. No. 3,770°446, British Patent No. 1,459,
No. 171, West German Patent (OLS) No. 2,503,099,
Coupler residues derived from acylacetamides described in Japanese Published Patent No. 50-139,738 or Research Disclosure No. 15737, or U.S. Pat.
, 046,574, and the like.

The macenta color image forming coupler residues represented by A include 5-oxo-2-pyrazoline nucleus, pyrazolo-[l,
Preferred are coupler residues having a 5-al benzimidazole nucleus, a pyrazoloimidazole nucleus, a pyrazolotriazole nucleus, a pyrazolotetrazole nucleus or a cyanoacetophenone type coupler residue.

The cyan image-forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus.

Further, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after coupling with an oxidized form of a developing agent and releasing a development inhibitor. This type of coupler residue represented by A is described in U.S. Pat.
No. 2,213, No. 4゜088.491, No. 3,632
, No. 345, No. 3.958,993 or No. 3,961
, 959, and the like.

Preferred examples of TIME in general formula (I) include the following.

(1) Groups that utilize the hemi-secure cleavage reaction, such as U.S. Pat.
No. 223, No. 59-106224 and No. 59-754
A group described in No. 75 and represented by the following general formula.

In the formula, the mark * represents the position bonded to the coupling position of A, R1 and R2 represent a hydrogen atom or a substituent, and n is 1
or 2, and when n or 2, each of the two R-1R2 may be the same or different, and any Ri, R
Two of them may be connected to form a cyclic structure. B represents a group defined in general formula (1).

(2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction. For example, timing groups as described in US Pat. No. 4,248,962.

(3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system. For example, U.S. Patent No. 4,409.323
or a group represented by the following general formula (
GB 2,096°783A).

In the formula, the mark * represents the position bonded to the coupling position of A, R8 and R4 represent a hydrogen atom or a substituent, and B
represents a group defined in general formula (, I). Examples of R, - include alkyl groups having 1 to 24 carbon atoms (e.g. methyl, ethyl, pencil, todenyl) or aryl groups having 6 to 24 carbon atoms (e.g. phenyl, 4-tetradecyloxyphenyl, 4-methoxyphenyl, 2,4,6-dolichlorophenyl, 4-nitrophenyl, 4-chlorophenyl, 2,5-chlorophenyl, 4-carboquinphenyl, p-tolyl), and examples of R4 include hydrogen atom, carbon number 1 ~24 alkyl groups (e.g. methyl, ethyl, undecyl, pentadecyl), aryl groups having 6 to 36 carbon atoms (e.g. phenyl, 4-methoxyphenyl), cyano groups, alkoxy groups having 1 to 24 carbon atoms (e.g. methoxy,
Nidokin, todenruokino), amine group having 0 to 36 carbon atoms (e.g. amine, dimethylamino, piperidino, cyhequinruamino, anilino), carphonamide group having 1 to 24 carbon atoms (e.g. acetamide, benzamide, tetradecaneamide), 1 to 24 carbon atoms sulfonamide group (
For example, methylsulfonamide, phenylsulfonamide), carboxy group, alkoxycarbonyl group having 2 to 24 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl) or 1 to 24 carbon atoms
carbamoyl groups (eg carbamoyl, dimethylcarbamoyl, pyrrolidinocarbonyl).

Examples of substituents X1, X2 and X in the groups represented by general formulas (IIa) to (IIp) are shown below.

Examples of the group X include methyl, ethyl, propyl, butyl, methoxyethyl, ethoxyethyl, isobutyl,
Allyl, dimethylaminoethyl, propalkyl, chloroethyl, methoxycarbonylmethyl, methylthioethyl, 4-hydroxyphenyl, 3-hydroquinophenyl,
4-sulfamoylphenyl, benzamide, dimethylcarbamoylphenyl, 3-sulfamoylphenyl,
4-carbamoylphenyl, 3-carbamoylphenyl,
4-dimethylaminophenyl, 3-acetamidophenyl, 4-propanamidophenyl, 4-methoxyphenyl, 2-hydroxyphenyl, 2.5-dihydroxyphenyl, 3-methoxycarbonylaminophenyl, 3-
(3-methylureido) phenyl, 3-(3-ethylureido) phenyl, 4-hydroxyethoxyphenyl group, 3-acetamido-4-methoxyphenyl group, etc.
Examples of groups for X2 (including atoms) include methyl, ethyl, benzyl, n-propyl, i-propyl, n-butyl, i-butyl, cyclohexyl, fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxy Methyl, hydroxyethyl, hydroxy, methoxy, ethoxy, butoxy, allyloxy, hensyloxy, methylthio, ethylthio, methoxycarbonyl, ethoxycarbonyl, acetamide, propanamide, butanamide, occlu, methylsulfonyl, methylsulfonamide, phenylsulfonamide, dimethylsulfa Examples of the atom or group of Examples include an oxygen atom, a sulfur atom, an imino group, a methylimino group, an ethylimino group, a propylimino group, and an arylimino group.

Among the groups represented by general formulas (I[a) to (IIp), general formulas (na), (IIp), (I[i), (■
j), (IIk) or (IIA) are preferred, and moreover, groups represented by general formulas (ITa), (IIi), (I
Particularly preferred are groups represented by ID or (II k).

Specific examples of the group represented by B in general formula (I) are shown below.

H 8O□NH2 OC82CH20H CH2CH=CH2 CH.

CH.

CH CH.

CH.

CH.

i85 CH CH, CH20H CH3 The coupler of the present invention is generally used by being mixed with the main coupler. The mixing ratio of the coupler of the present invention to the main coupler is 0. 1 mol% to 100 mol%, preferably 1
mol% to 50 mol%. The amount of the coupler of the invention relative to the silver halide used is from 0.01 mol% to 20 mol%, preferably from 0.5 mol% to 10 mol%, based on the silver halide present in the same layer or an adjacent layer.

Furthermore, the present invention is particularly effective in formula (1)
In A or the following general formula (Cp-1), (Cp-2),
(Cp-3), (Cp-4), (Cp-5), (Cp-
6), (Cp-7), (Cp-8), (Cp-9), (
Cp-10) or (Cp-11). These couplers are preferred because of their high coupling speed.

General formula (Cp-1) OO R, -C-CH-C-NH-R,2 General formula (Cp general formula General formula (Cp-2) R, -NH-C-CH-C-NH-R,.

General formula (Cp General formula (Cp-3) / R5, -C-CH 兇N evening~.

R8S General formula (Cp-7) General formula (Cp-10) H General formula (Cp-8) General formula (Cp-11) R,, -CH-R.

General Formula (Cp-9) In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group. In the above formula, R51, R5□, R53, R5Rsi, R1
6. When Ri 7, RSIN Ril, RIG or R6 contains a diffusion-resistant group, it has a total number of carbon atoms of 8 to 32,
Preferably, the carbon number is selected to be 10 to 22, and in other cases, the total number of carbon atoms is preferably 15 or less.

Next, R51 of the general formulas (Cp-1) to (Cp-11)
~R11, Cm and p will be explained.

In the formula, Ril represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R5+ and Ri3 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R51 is preferably an aliphatic hydrocarbon group having 1 to 22 carbon atoms, and may be substituted or unsubstituted, chain or cyclic, and may have one or more substituents. It may have. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amine group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as Rs + are as follows. Isopropyl group, isobutyl, tert-butyl, isoamyl, tert-amyl, 1. l-dimethylbutyl, 1.
1-dimethylhexyl, 1. l-diethylhexyl, dodecino hexadecyl, octadecyl, nclohexyl, 2-methoxyisopropyl, 2-phenoxyisopropyl, 2-ptert-butylphenoxyisopropyl, α-aminoisopropyl, α-(diethylamino)isopropyl, α-(succinimide) ) isopropyl, α-(phthalimido)isopropyl, α-(pensensesulfonamido)isopropyl.

When R5l, R5□ or R53 represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. 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., and the aryl group of these substituents In addition, the total number of carbon atoms in the part is 1 to 2.
2 may be substituted with one or more alkyl groups.

The phenyl group represented by R51, R5□ or RSH further includes an amine group, a hydroxy group, a carboxy group, including those substituted with a lower alkyl group having 1 to 6 carbon atoms,
It may be substituted with a sulfo group, nitro group, cyan group, thiocyano group or halogen atom.

Further, R j l, R52 or R may represent a phenyl group or a substituent condensed with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

When R51 represents an alkoxy group, the alkyl moiety represents a linear 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; It may be substituted with a halogen atom, an aryl group, an alkoxy group, etc.

When R5H, R5□ or R2H represents a heterocyclic group, the heterocyclic group is connected to the carbon atom of the carbonyl group of the anlu group in alpha acylacetamide or the nitrogen of the amide group through one of the carbon atoms forming the ring, respectively. Combine with atoms. Such heterocycles include thiophene, furan,
Pyran, pyrrole, pyrazole, pyridine, pyrazine,
Examples include pyrimidine, pyridazine, intolycine, imidazole, thiazole, oxazole, triazine, thiocyano group, and oxazine. These may further have a substituent on the ring.

In the general formula (Cp-3), R55 has 1 to 3 carbon atoms.
2 Preferably 1 to 22 linear or branched alkyl groups (e.g. methyl, isopropyl, tert-butyl,
hexyl, dodecyl), alkenyl groups (e.g. allyl)
, represents a cyclic alkyl group (e.g. cyclopentyl, cyclohexyl, norbornyl), an aralkyl group (e.g. benzyl, β-phenylethyl), a cyclic alkenyl group (e.g. cyclopentenyl, cyclohexenyl), and these represent a halogen atom, a nitro group, a cyan group, Aryl group, alkoxy group, aryloxy group, carboxy 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, N-arylanilino group, N-
It may be substituted with an alkylanilino group, an N-acylanilino group, a hydroxyl group, a mercapto group, or the like.

Furthermore, Rs+ may represent an aryl group (eg phenyl, α- or β-naphthyl). Aryl group is 1
It may have more than one substituent, and examples of the substituent include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyan group, an aryl group, an alkoxy group, and an aryloxy group. group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, dianrulamino group, ureido group, urethane group, sulfonamide group, heterocyclic group,
Arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group,
It may have an N-arylanilino group, an N-acylanilino group, or a hydroxyl group.

Furthermore, Ri i 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), a heterocyclic group substituted with the substituents listed above for the aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group, or It may also represent an arylthiocarbamoyl group.

In the formula, Rh+ 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 include the substituents listed for R55 above). ), aryl groups and heterocyclic groups (these are the above R
i s), alkoxycarbonyl groups (e.g. methoxycarbonyl, aethquinecarbonyl, stearyloxinecarbonyl), aryloxycarbonyl groups (e.g. phenoxycarbonyl group, naphthoquinecarbonyl group) ), aralkyloxycarbonyl groups (e.g. benzyloxycarbonyl), alkoxy groups (e.g. methoxy, ethoxy, heptadecyloxy), aryloxy groups (e.g. fenoquine, tolyloxy), alkylthio groups (e.g. ethylthio, dodecylthio), arylthio groups (e.g. Phenylthio, α
-naphthylthio), carboxyne group, acylamino group (e.g. acetylamino, 3-[(2,4-tertamylphenoxy)acetamido]benzamide), diacylamino group, N-alkylacyl amino group (e.g. N-
methylpropionamide), N-arylacylamino groups (e.g. N-phenylacetamide), ureido groups (
ureido, N-arylureido, N-alkylureido), urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino, diphenylamino, N-acetylanilino, 2-chloro-
5-tetradecanamide anilino), alkylamino groups (e.g. n-butylamino, methylamine, cyclohexylamino), cycloamino groups (e.g. piperidino, pyrrolidino), heterocyclic amino groups (e.g. 4-pyridylamino, 2-benzoxa silylamino), alkylcarbonyl groups (e.g. methylcarbonyl), arylcarbonyl groups (e.g. phenylcarbonyl), sulfonamide groups (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), a cyano group, a hydroxy group, or a sulfo group.

In the formula, Ria is a hydrogen atom or a straight or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms,
It represents an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group, which may have the substituents listed for Ri i above.

Furthermore, R 16 may represent an aryl group or a heterocyclic group, and these may have the substituents listed for Ri5 above.

R i a is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxyne group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group,
alkylamino group, dialkylamino group, anilino group,
N-arylanilino group, N-alkylanilino group, N
-It may represent an acylanilino group or a hydroxyl group.

Rh + , Rig and Rii each represent a group used in a typical 4-equivalent phenol or α-naphthol coupler; specifically, R57 is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon residue; , N-arylureido group, acylamino group, -0-R,□ or S-R,2 (however, Ra+ is an aliphatic hydrocarbon residue), and when two or more R1s exist in the same molecule Two or more R5□ 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 R5 above.

Examples of Rim and Rip include groups selected from aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues, or one of these groups may be a hydrogen atom, and substituents may be added to these groups. Including those with.

Further, R11 and R59 may jointly form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues may be either saturated or unsaturated, and may be straight-chain, branched, or
Any ring-shaped one may be used. Preferred are alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl) and alkenyl groups (eg, allyl, octenyl). Aryl groups include phenyl and naphthyl groups, and representative heterocyclic residues include pyridinyl, quinolyl, thienyl, piperidyl, and imidazolyl. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, Aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl,
Prefectures such as Morpholino can be mentioned.

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

Reo is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and an alkanecarbamoyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent, such as an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsuccinimide group. group, halogen atom, nitro group, carboxyl group, nitrile group, alkyl group, or aryl group.

R61 is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and an alkanecarbamoyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Alcoquine carbonyl group or aryloxycarbonyl group, alkylsulfonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, arylsulfonyl group, aryl group, 5- or 6-membered heterocyclic group (the hetero atom is a nitrogen atom, represents an oxygen atom, a sulfur atom (for example, a triazolyl group, an imidazolyl group, a phthalimide group, a succinimide group, a furyl group, a pyridyl group, or a benzotriazolyl group), and these are the substituents mentioned above in R6゜. It may have.

Among the above coupler residues, yellow coupler residues include R51, a t-butyl group, a substituted or unsubstituted aryl group, and Ri2 in the general formula (Cp-1).
represents a substituted or unsubstituted aryl group, and in general formula (Cp-2), R4! It is preferred that R5+ represents a substituted or unsubstituted aryl group.

Preferred macenta coupler residues are of the general formula (Cp
Rit in -3) is an acylamino group, a ureido group,
and an arylamino group, R55, or a substituted aryl group, R5I in general formula (Cp-4) represents an acylamino group, a ureido group, an arylamino group, R55, or a substituted aryl group.
When ie represents a hydrogen atom, and the general formula (Cp-
In 5) and (Cp6), R and Ri6 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) in which R5□ represents an acylamino group or ureido group at the 2nd position, an acylamino group or an alkyl group at the 5th position, and a hydrogen atom or a chlorine atom at the 6th position, and R57 in the general formula (Cp9) represents a 5 When R51 is a hydrogen atom, an acylamino group, a sulfonamide group, or an alkoxyl group, and R51 is a hydrogen atom, and R51 is a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group. It is.

Preferred colorless coupler residues have the general formula (Cp
-10), when RHt represents an acylamino group, a sulfonamide group or a sulfamoyl group, the general formula (
This is the case where R6G and R61 in Cp-11) represent an alkoxycarbonyl group.

Further, any part of R81 to R61 may form a multimer of bis or more, and a polymer of a monomer or a non-color-forming monomer having an ethylenically unsaturated group in any part of these groups may be used. It may also be a copolymer with

When the coupler residue of the present invention represents a polymer, it is a polymer derived from a monomeric coupler represented by the following general formula (Cp-12) and having a repeating unit represented by the general formula (Cp-13), or It means a copolymer with one or more non-chromogenic monomers containing at least one ethylene group that does not have the ability to couple with an oxidized form of an aromatic primary amine developing agent. Here, two or more types of monomer couplers may be simultaneously polymerized.

General formula (Cp-12) CH, = C-fA ke 7tl-A to line 26〇廿Q General formula (
Cp-13) (CH2-C) (Ake76Ake=zaA+seQ In the formula, R is a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms,
or represents a chlorine atom, A is -CONR' --N
R'C0NR'-NR'COO--COO--3o2-CO--NRC○--3o2NR'-NR'5O2--○CO--0CONR'-NR'
- or -〇-, A is -CONR'- or -C
OO-, R' represents a hydrogen atom, an aliphatic group, or an aryl group, and when there are two or more R's in the molecule, they may be the same or different. A3 has 1 to 10 carbon atoms
represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group, and the alkylene group may be linear or branched.

(Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, examples of aralkylene groups such as hengelidene, and examples of arylene groups such as phenylene and naphthylene). Any part of R1 to Rl in general formulas (Cp-1) to (Cp-11),
2) or a group bonded to (Cp-13).

i, j, and k represent 0 or l, but i, j,
and k are never 0 at the same time.

Here, substituents for the alkylene group, aralkylene group, or arylene group represented by A include an aryl group (for example, phenyl), a nitro group, a hydroxyl group, a cyano group, a sulfo group,
Alcoquine groups (e.g. methoxy), aryloxy groups (
(e.g., phenoxy), acyloxy groups (e.g., acetoquine), acylamino groups (e.g., acetylamino), sulfonamide groups (e.g., methanesulfonamide), sulfamoyl groups (e.g., methylsulfamoyl), halogen atoms (e.g., fluorine, chlorine, bromine, etc.) , a carboxyne group, a carbamoyl group (eg, methylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), and a sulfonyl group (eg, methylsulfonyl).

When there are two or more of these substituents, they may be the same or different.

(D O2 I (D NO3 H (D-10) (D (D-14) (D (D O2 (D (D (D (D (D-20) (D-22) (D-23) t Hi CH3 CH.

(D-24) NHCOCIsHxl-n (D-28) I (D-26) (D-27) (D-30) CH.

He=He (D-33) (D (D c2H.

(D-34) H2 2H5 o2NH2 0CH2 C=O Ct 89(n) H Ct He(n) These compounds of the present invention are disclosed in JP-A Nos. 54-145135, 63-37346, 56-114946, No. 57-154234, No. 58162949, No. 63
-37350, 57151944, 58-20
It can be synthesized according to the methods, literature, and patents described in No. 5150 and No. 60-218645.

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 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. 6m-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 No. 571
No. 12751, No. 62-200350, 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-sensitive layer (RH) /low-sensitivity red-sensitive layer (RL) order, or in the order of B H / B L / G L / GH / RH / RL,
Alternatively, they can be installed in the order of B H/B L/GH/GL/RL/RH.

Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of RH/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 decreases sequentially toward the support. Even in the case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, medium-sensitivity emulsion is added from the side remote from the support in the same color-sensitive layer. They may be arranged in the following order: layer/high-speed emulsion layer/low-speed emulsion layer.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

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

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

The coupler used in the red-sensitive emulsion layer has the general formula [C
Various couplers can be used without any particular limitations, except that the red-sensitive layer contains a cyan coupler represented by the following formula and the two-equivalent coupler in the entire red-sensitive layer accounts for 60% or more by mole. If the ratio of 2-equivalent couplers is above the above, the amount of silver will be reduced;
Although it is possible to make the layer thinner, the ratio of 2-equivalent couplers is preferably 80% or more, and it is more preferred that the ratio of 2-equivalent couplers is 100%.

As the cyan coupler, the cyan coupler represented by the general formula [C] of the present invention can be used in combination with other cyan couplers. In that case, U.S. Patent No. 4,05
No. 2,212, No. 4,146゜396, No. 4,228
, No. 233, No. 4,296.200, No. 2,369,
No. 929, No. 2゜801.171, No. 2,772,1
No. 62, No. 2.895,826, No. 3,772,00
No. 2, No. 3,758,308, No. 4,334,011
No. 4,327,173, West German Patent Publication No. 3゜32
9.729, European Patent No. 121.365A, U.S. Patent No. 3,446,622, European Patent No. 4,333.999,
Cyan couplers described in 4,451,559 and 4,427,767 are preferred.

As for the coupler used in the blue-sensitive layer, the 2-equivalent coupler in the entire blue-sensitive layer is preferably 60% or more by mole, and more preferably 100%. Further, examples of yellow couplers that can be used include, for example, US Pat. No. 393
No. 3501, No. 4022620, No. 432602
No. 4, No. 4401752, Special Publication No. 58-10739
British Patent No. 1425020, British Patent No. 1476760
Preferably, those described in No.

The coupler used in the green-sensitive emulsion layer preferably contains 60% or more of the 2-equivalent coupler in the green-sensitive layer as a whole, more preferably 80% or more, and even more preferably 100%. . Also used.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent No. 4,310
, No. 619, No. 4. 351. No. 897, European Patent No. 73,636, U.S. Patent No. 3,061,432,
No. 3,725,064, Research Disclosure No. 2422 (June 1984), Japanese Unexamined Patent Publication No. 1986-
No. 33552, Research Disclosure Nα24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118'034, No. 60-185951, U.S. Patent No. 4,500,630, No. 4,540.65
No. 4, No. 4,556,630, WO (PCT) 8
Particularly preferred are those described in No. 8104795 and the like.

On the other hand, JP-A-62-168155, JP-A No. 62-1518
No. 47, No. 62-180365, No. 63-31685
No. 6, No. 64-4743, JP-A-1-99046, JP-A-1-131558, etc. describe the use of a 2-equivalent cyan coupler in the red-sensitive layer;
No. 738 discloses the use of the DIR compound of the present invention, but in both cases, a large amount of silver is used (although it was desired to reduce the amount of silver used to improve sharpness and desilvering property).

However, by using the structure of the present invention, it becomes possible to reduce the amount of silver halide used in the emulsion layer, and the silver content of the light-sensitive material of the present invention is 7.6 g/rr? The following are preferable, more preferably 7. It is 0 g/rri' or less, more preferably 6.5 g/m or less.

Furthermore, in the present invention, by using a cyan coupler represented by general formula [C] in the red-sensitive layer, the amount of silver halide used in the red-sensitive layer can be reduced, and the amount of silver halide used in the red-sensitive emulsion layer of the light-sensitive material of the present invention can be reduced. The silver halide content is preferably less than 3.1 g/m, more preferably less than 2.1 g/m in terms of silver.
Less than 8g/rd, more preferably 2.4g/rd
less than

The silver content referred to here is the content of all silver such as silver halide and metallic silver converted into silver.

There are several known methods for analyzing the silver content of photosensitive materials, and any method may be used; for example, fluorescent X-rays are convenient.

The light-sensitive material of the present invention only needs to be provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitizing layer, and a red-sensitive layer on a support. There are no particular limitations on the number and order of the layers and non-photosensitive layers. A typical example is a silver halide photographic photosensitive 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 luminous intensity. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the photosensitive layer is generally a unit photosensitive layer. A red-sensing layer, a green-bewitching layer, and a blue-sensing layer are arranged in this order from the support side. However, depending on the purpose, the above-mentioned 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 layers.

Various intermediate and other non-photosensitive 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.

The plurality of silver halogen emulsion layers constituting each position-sensitive layer are a high-density emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045.
A two-layer structure of low-speed emulsion layers 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. In addition, JP-A-57
-112751, 62200350, 62-2
As described in No. 06541, 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 (B) / high intensity green sensitive layer (GH) / low sensitivity blue sensitive layer (GL)/
High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL)
) or BH/BL/GL/G)l/PH/II
(Order of L or BH/BL/GH/GL, /RL/R)
They can be installed in the order of l.

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. 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 disposed 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 coloring layer, a medium coloring emulsion layer/high coloring emulsion layer/low coloring emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

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

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

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 10 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.

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) N.

17643 (December 1978), pp. 22-23,'
M. Emulsion preparation
on and types)'', and Nα1871
6 (November 1979), 648 pages, Dobei 3071
05 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by Glafkides, published by Paul Montell (P., Glafkides, Chemie et al.
Ph1sique Photographique+
Paul Montel+ 1967), Duffin,
"Photographic Emulsion Chemistry", published by Focal Press (G, F, D
uffinPhotographic Emulsio
n Chemistry (Focal Press1
966) ), Zelikman et al. [Production and coating of photographic emulsions], published by Focal Press (V, L, Zelikm)
anetal,, Making and Coati
ng Photographic Emulsion,
Focal Press, 1964).

U.S. Patent Box 3,574,628, U.S. Patent Box 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. L413,748 are also preferred.

Tabular grains having aspect ratios of about 3 or greater 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 Box 4
, 434,226, 4,414.310, 4,
433,048, British Patent No. 4,439.520, and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by 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 above-mentioned emulsions may be of the surface latent image type in which a latent image is formed on the surface as the king, or the internal latent image type in which the latent image is formed inside the grains, or the type in which latent images are formed both on the surface and inside the grains, but negative type emulsions may be used. It needs to be an emulsion. Among the internal latent image type emulsions, a core/shell type internal latent image type emulsion described in JP-A-63-264740 may be used. A method for preparing this core/shell type internal latent image type emulsion is described in JP-A-59-133542.

The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

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 requirements.
17643, Nα18716 and Nα30710
5, and the relevant sections are summarized in the table below.

The photosensitive material of the present invention includes grain size, grain size distribution, halogen composition, grain shape,
Two or more types of emulsions differing in at least one characteristic of sensitivity can be mixed and used in the same layer.

Silver halide grains coated with the grain surfaces described in U.S. Patent Box 4,082,553, U.S. Patent Box 4,626,4
Silver halide grains and colloidal silver with puffy interiors described in No. 98 and JP-A No. 59-214852 are preferably used in a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid layer. Can be used.

Silver halide grains with a puffed interior or surface are defined as
Refers to silver halide grains that can be developed in a non-imagewise manner. A method for preparing silver halide grains with a fogged interior or surface is described in U.S. Pat.

The silver halides forming the inner core of the core/shell type silver halide grains whose interiors are fogged may have the same halogen composition or may have different halogen compositions. Any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used as the silver halide whose inside or surface of the grain is puffed. Although there is no particular limitation on the grain size of these diffused silver halide grains,
The average particle size is preferably 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm. In addition, there are no particular limitations on the particle shape, and regular particles may be used.
It may be a polydisperse emulsion, but it may be a monodisperse emulsion (at least 95% of the weight or number of silver halide grains is ±4 of the average grain size).
0% or less) is preferable.

In the present invention, it is preferable to use ultra-photogenic fine grain silver halide. Non-photosensitive fine grain silver halide is a fine silver halide grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process. preferable.

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

The fine grain silver halide has an average grain size (average diameter equivalent to a circle of projected area) of 0. O1 to 0.5 μm is preferable, and 0.
02 to 0.2 μm 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 enhanced, nor is there any need for spectral sensitization. However, before adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound. Colloidal silver can preferably be contained in the layer containing fine silver halide grains.

The coating silver amount of the light-sensitive material of the present invention is preferably 6.0 g/rrf or less, most preferably 4.5 g/n or less.

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.

In addition, in order to prevent the deterioration of photographic performance due to formaldehyde gas, US Patent No. 4,411.987 and US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

The photosensitive material of the present invention includes U.S. Pat. No. 4,740,454, U.S. Pat.
It is preferable to contain a mercapto compound described in JP-A No. 1283551.

A compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof irrespective of the amount of developed silver produced during the development process, which is described in JP-A-1-106052, is added to the light-sensitive material of the present invention. It is preferable to contain.

Dyes dispersed in the photosensitive material of the present invention by the method described in International Publication No. 088104794, Japanese Patent Publication No. 11-502912, or EP 317,308A, U.S. Pat.
, 420,555 and JP-A-1-259358.

Various color couplers can be used in the present invention, and specific examples thereof include the aforementioned Research Disclosure 17643, ■-C-G, and Research Disclosure 307105,
■It is described in the patent described in -C-G.

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. 4.4OL752, No. 4,2
48,961, Japanese Patent Publication No. 58-10739, British Patent No. 1425.020, British Patent No. 1,476.760, U.S. Patent No. 3,973.968, British Patent No. 4.314,02
3, European Patent No. 4,511,649, European Patent No. 249.
No. 473a, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351,897, European Patent No. 73.636, US Patent No. 3,061,432, US Patent No. 3725.067, Research Disclosure Nα24220 (June 1984), JP-A-60-3
No. 3552, Research Disclosure Sou 2423
0 (June 1984), Japanese Patent Publication No. 60-43659,
No. 61-72238, No. 60-35730, No. 55
-118034, US Patent No. 60-185951, US Patent No. 4500.630, US Patent No. 4,540.654, US Patent No. 4,556,630, International Publication No.
Particularly preferred are those described in No. 5 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. 2,801171, No. 2,772,1
No. 62, No. 2.895.826, No. 3,772,
No. 002, No. 3,758,308, No. 4.334
．． 011, 4,327.173, West German Patent Publication No. 3329.729, European Patent No. 121,365A, European Patent No. 249453A, US Patent No. 3,446,62
No. 2, No. 4,333,999, No. 4,775,6
No. 16, No. 4,45], No. 559, No. 4,427
, No. 767, No. 4,690,889, No. 4.25
No. 4212, No. 4,296.199, JP-A-61-
Preferred are those described in No. 42658 and the like. Furthermore, JP-A-64-553, JP-A-64-554, JP-A-64-555
Pyrazoloazole couplers described in US Pat. No. 64-556 and imidazole couplers described in U.S. Pat.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576910, British Patent No. 2.102.1
No. 37, European Patent No. 341188A, etc.

Couplers in which 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.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Research Disclosure Nα17643, ■-C, Nα307105, ■-G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.25
No. 8, British Patent No. 1,146,368 is preferred. In addition, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during cambling, as described in U.S. Pat. No. 4,774,181, and U.S. Pat.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 77.120.

Compounds that release photographically useful residues upon force or bling can also be preferably used in the present invention.

DIR couplers that release development inhibitors are the aforementioned RD
17643, ■-F term and the same α307105, ■-
The patent described in Section F, JP-A-57-151944,
Preferred are those described in US Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and US Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
Those described in JP-A No. 2,13L188, JP-A-59-157638, and JP-A-59-170840 are preferred. Also, JP-A-60-107029, JP-A No. 60-25234
Compounds that release fogging agents, development accelerators, silver halide solvents, etc. through redox reactions with oxidized developing agents described in JP-A No. 0, JP-A-144940, and JP-A-1-45687 are also preferred.

Other compounds that can be used in the photosensitive material of the present invention include the competitive couplers described in U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redonx 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. 1733024
No. 313.308A of I? ,D.No., 11449
, No. 24241, JP-A-61-201247, etc., bleach accelerator-releasing couplers, U.S. Patent No. 4,555,4
Gantt' release coupler described in No. 77 etc., JP-A-63
Examples include couplers that release leuco dyes as described in US Pat. No. 4,774.181 and couplers that release 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, synchrohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-amyl phenyl) phthalate, bis(2,4-amyl phenyl) phthalate, (2,4-di-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), 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-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodesolbenzoate, etc.) ate, 2-ethylhexyl-p-hydroxyhenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-
(tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol trichloride, etc.) butyrate, isostearyl lactate, trioctyl sotrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), etc. Can be mentioned.

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. 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.
541.230, etc.

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

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, 64 of Nα18716
From the right column of page 7 to the left column of page 648, and the same No. 30710
5, page 879.

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 μl or less, more preferably 23 μl or less, even more preferably 18 μm or less, particularly preferably 16 μm or less. . Further, the membrane swelling rate T,/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, it can be measured by using a swellometer (swelling membrane) of the type described, and TI/□ is reached when treated with a color developer for 13 minutes and 15 seconds at 30°C. The saturated film thickness is defined as 90% of the maximum swollen film thickness, and is defined as the time until the saturated film thickness reaches 172.

The membrane swelling rate TI/□ 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 photosensitive material of the present invention has a hydrophilic colloid layer (with a total dry thickness of 2 μm to 20 μm) on the side opposite to the side having the emulsion layer.
It is preferable to provide a layer (referred to as a hack layer). This bank layer contains the aforementioned light absorbers, filter dyes, ultraviolet absorbers, static inhibitors, hardeners, binders, plasticizers,
It is preferable to contain lubricating agents, coating aids, surfactants, etc. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention is disclosed in the aforementioned RD, Koji 17643, pages 28-29, and Nα18716, 651.
Left column to right column, and question circle 3 (880 to 88 of 17105)
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 alkaline water containing an aromatic primary amine color developing agent as a main component. @'IVL. Aminophenol compounds are also useful as color developing agents, but ρ-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, 11
Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroquinethylaniline, 3-methyl-
Examples include 4-amino-~-ethyl-Nβ-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxynoethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates. It will be done. 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, hengimidazoles, hendithiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sub6M1m salt, hydrazines such as N,N-biscarboquine methylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene Organic solvents such as glycols, diethylene glycol, development accelerators such as hensyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, 1-
An auxiliary developing agent such as phenyl-3-pyrazolidone, a viscosity imparting agent, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,II~trimethylenephosphonic acid, ethylenediamine-N,N, Representative examples include N,N tetramethylene phosphonic acid, ethylene diamine di(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black-and-white developer contains known black-and-white developing agents such as dihydroxohenzenes such as hydroquinone, 3-virapritones such as 1-phenyl-3-pyrazolidone, or 7-minophenols such as N-methyl-p-aminophenol. can be used alone or 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 set to 7 or less. When reducing the amount of replenishment, it is preferable to prevent one-shot oxidation of the liquid by air 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 that it can be used in 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 treatment is usually set between 2 and 5 minutes, but the treatment time can be further shortened by using high temperature, high pH, and high concentration of color development agent.

After color development, the photographic opalescent 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 (I[ Aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (I[I) complex salts, including ethylenediaminetetraacetate iron (I[[) complex salt] and 1,3-diaminopropanetetraacetic acid iron (I[[) complex salt], are suitable for rapid processing and environmental protection. Preferable from the viewpoint of preventing contamination. In addition, iron aminopolycarboxylate (I
[I) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (I
[[) The pH of the bleaching solution or bleach-fixing solution using a complex salt is usually 4.0 to 8, but it can be processed at an even lower pif for speeding up the processing.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, 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. k17129 (July 1978), etc.; JP-A-50-140129 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
Thiourea derivatives described in West German Patent No. 1,127.7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748,430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-40.943, 49-59,644, 53-
No. 94,927, No. 54-35,727, No. 35-2
Compounds described in No. 6,506 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. 3,893,858.
No., West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-9
The compounds described in No. 5,630 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 photographic use.

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,
Hydroxyacetic acid and the like 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, combinations of thiosulfates, thiocyanates, 1,000-onythyl compounds, thiourea, etc. are 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.

In the present invention, the fixing solution or bleach-fixing solution has pHt
For the purpose of adjusting the temperature, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, -methylimidazole, 1-ethylimidazole, or 2-methylimidazole, is added at 0.1 to 10 mol/! It is preferable to add.

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°C1 is preferably 35°C to 45°C. In the preferred temperature range 22, the desilvering rate is improved and the occurrence of staining after treatment is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening 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-624834.
A method of increasing the stirring effect using the rotating means of No. 61, 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. Improved agitation: It is thought that this speeds up the supply of bleaching agent 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.

After the delineation treatment, the silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process.

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 Motion Picture and
Te1evision Engineers No. 64S
, P, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, 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, grouper terriers breed, and the resulting floating matter adheres 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
Chlorine-based disinfectants such as isothiazolone compounds, thiahesidazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing , Hygiene Technology Extra Line "Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Society of Industrial Technology, Japan Antibacterial and Antifungal Science ``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 performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. be able to. 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 other processes such as the desilvering process.

In a process using an automatic processor or the like, when each of the above-mentioned processing solutions is produced in a size of 1 m, it is preferable to add water to correct the shrinkage.

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
50 and Nα15.159, aldol compounds described in U.S. Patent No. 13.924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 3-135628.

The silver halide color light-sensitive material of the present invention may optionally contain various types of 1-phenyl-3-
It is also possible to incorporate birapritons.

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

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved.

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 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 light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is g/g for silver halide and colloidal silver.
The amount of silver expressed in rd units, for coupler additives and gelatin in g/rd units 4, and for sensitizing dyes in moles per mole of silver halide in the same layer. Ta.

1st layer: Antihalation layer black colloid l-'' silver gelatin V-1 V-2 pd-1 p d-2 olv-1 olv-2 2nd layer: Intermediate layer fine grain silver iodobromide (Ag11.0 mol% , equivalent sphere diameter 0.0
7 μm) Silver coating amount 0.15 Silver coating 1 0,20 2.20 0.11 0.20 4, OX 10-2 1.9X10-" 0.30 1.2X10-" Gelatin 1.00 EχC-4 6 ,0X10-" Cpd-32,0xlO Third layer: First red-sensitive emulsion tube silver iodobromide emulsion (Ag15.0 mol%, surface height Agl type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21 %, tabular grain, diameter/ff ratio 7.5) i! Coating amount 0.48 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μm, equivalent sphere diameter Coefficient of variation 18%, dodecahedral particles) Gelatin xS-I xS-2 Eχ5-3 EχC-I xC-3 xC-4 olv-1 Silver coating amount 0.48 1.90 4.5X10-' mol 1. 5X10-' mol 4, OX 10-5 mol 0.65 1, OX 10"2 2.3 %, internal high Agl type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.85 1.2 3, OX 10"' 1 mole, OX 10-' mole 3, OX IF5 mole 0.13 6.2 X 10-2 4.0X10-2 0.10 Gelatin xS-1 xS-2 E, xS-3 xC-1 xC-2 xC -4 olv-1 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion (Ag1 11.3 mol%, internal high Agl
Mold, equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 1.50 1.20 2゜0XIO-'Mole 6.0x1O-' Mol 2.0X10-' Mol 8.5X10-"7.3X10-" 0.12 0.12 Gelatin xS-1 xS-2 rS-3 xC-2 xC-5 So1 ■-1 olv-2 6th layer: Intermediate layer gelatin Cpd-4 olv-1 7th layer: First green emulsion layer Silver iodobromide emulsion (Ag 15.0 mol%, surface height Agl type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21 %, tabular grain, diameter/thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μm, 8.0XIO-
"1.00 8.0X10-" Coefficient of variation of equivalent sphere diameter 18%, dodecahedral particles) Silver coating amount 0.16 1.20 5.0 X 10-'mol 2.0X10-'mol 1.0XIO -'mol 0.50 0.10 3.5X10-" 0.20 3.0XIO-" Gelatin xS-4 xS-5 xS-6 xM-1 xM-2 xM-5 olv-1 olv-3 8th layer : Second green-sensitive emulsion layer silver iodobromide emulsion (AgF 2.5 mol%, internal high Agl type, equivalent sphere diameter 1.0 am, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 3. 0) Silver coating amount 0.57 Gelatin xS-4 0,45 3,5xlO-'mol Ex S-51,4X10-'mol Ex S-
9th layer Intermediate layer gelatin 0.50S o
1 v -12,0X10-" 10th layer: 3rd green-sensitive opalescent layer silver iodobromide emulsion (Ag1 11.3 mol%, inner cylinder AgI
Mold, equivalent sphere diameter 1.4 μm, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/ff ratio 6.0) Silver coating amount 1.30 Gelatin 1.20E x
S -42,0 x 10-'mol Ex S -58,
0X10-5 mol ExS -68, 0X10-5 mol Ex M -44, 5X1f12 Ex M-6t, oxto-" Ex C-24, 5 11th layer: Yellow filter layer gelatin 0.50CP
d -65,2X10-2 Solv-10,12 1271i: Intermediate layer gelatin o, 45Cpd
-30,10 13th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, average -Agl type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 25%, tabular grain, diameter /W-view ratio 7.o) Silver coating amount 0.20 Gelatin 1.00E x
S -73, oxto-'mol Ex Y -10,
60 E
Mold, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 16%, octahedral particles) Silver coating amount 0.19 Gelatin 0.35E x
S -72,0X10-'molExY-10,22S o Iv-17,0X10-''15th layer: Intermediate layer fine grain silver iodobromide (Ag 12 mol%, uniform Agl type, equivalent sphere diameter 0.13 μm ) Silver coating amount 0
．． 20 Gelatin 0.36 No. 16
Layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (Ag1 14.0 mol%, internal high Agl
Mold, equivalent sphere diameter 1.7 μm, coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 5.0) Silver coating amount 1.55 Gelatin 1.00E x
S -81,5xlO-'mol E x Y -10,
21 S o l v -17,0XIO-” 17th layer: 1st
Protective layer gelatin 1.80UV-
10,13 U V -20,21 S o l v -11,0X10-” S o l v
-21,0X10-2 18th layer: 2nd protective layer fine grain silver chloride (equivalent sphere diameter 0.07 μm) Silver coating amount
0.36 Gelatin 0.70B-1
(Diameter 1.5μm) 2.0xlO-”B-
2 (diameter L5um) 0.15W-I-I pd-7 3,0X10-” 2,OX 10-2 0.35 1.00 This E$4 includes 1,2-benzisothiazoline-3-
on (average 200 ppm relative to gelatin), n-
Butyl-P-hydroquinhendoate (approximately 1.000
ppm), and 2-phenoxyethanol (between approximately 10,000 ppm) were added. Furthermore B-4
, B-5, W-2, W-3, F-1, F-2, F3, F
-4, F-5, F-6, F-7, F-8, F-9, F-
10, F-11, F-12, F-13 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

EχC-1 (i) CJ, +0CNH xC n) I xC xM xC-4 l ExM 2 (χ-3 in West German Patent (Publication) No. 3.815.46
) ExM ExM-6 I I ExM-4 xY-1 xY pd-3 H P d-4 6HI3 pd-1 p d-5 p d-2 p d-6 pd H3 olv olv-2 olv- 3 xS-5 xS xS-7 xS xS xS xS xS n=2-4 CI (2=CH 5O Samples 102 to 109 were prepared in the same manner except that the coupler used in Example 1 and the amount added thereof, the amount of silver, and the amount of seratin were changed as shown in Table I.

These samples were exposed to white light through a pattern for MTF measurement and developed as shown below to calculate the MTF value and evaluate the sharpness of each sample. Next, these samples were uniformly exposed to white light and subjected to the following treatment, and the amount of silver remaining in the light-sensitive material was determined using fluorescent X-ray analysis for the obtained samples. The smaller the obtained value, the smaller the amount of residual silver and the better the color reproduction. These results are summarized in Table 2.

The color development process was carried out as follows at 38°C using an automatic developing machine.

Color development 2 minutes 45 seconds bleaching 1 minute bleach-fixing 3 minutes 15 seconds washing ■ 40 seconds washing ■ 1 minute stabilization 40 seconds drying (50°C) 1 minute 15 seconds In the above processing steps, washing ■ and ■ are A countercurrent water washing method was used from to ■. Next, the composition of each treatment liquid will be described.

The replenishment amount of the processing solution was 1,200 ml for color development and 800 ml for all other colors, including washing with water, per color photosensitive material.

Also, the amount of pre-bath carried into the water washing process is 5 per 1M of color photosensitive material.
It was 0m1.

(Color developer) Mother solution Replenisher diethylenetriaminepentaacetic acid 1.0g 1.1g1
-Hydroxyethylidene-1,1-diphosphonic acid 2.0g 2.2g
Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β-hydroxyethylamino) Add 2-methylaniline sulfate solution and H (Bleach solution) Common to mother solution and replenisher solution Ethylene diamine 4 Ferric acetate ammonium salt Ethylenediaminetetraacetic acid disodium salt Ammonium sulfate Ammonium bromide Bleach accelerator 4.0g 30.0g 32.0g 1.4g 0.7g 1.3■ 4.4g 4.5g 5.0g 1, OA 1.0j2 10.0 to, 05 120.0g 10.0g 10.0g 100.0g 5X10-'M Add ammonia water pH 6.3 Add water
1. Ol (bleach-fix solution) Common to mother liquor and replenisher Ethylenecyaminetetraacetic acid ferric ammonium salt 50.0g Ethylenediaminetetraacetic acid disodium salt 5.0g Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution (70%) Add 240rrl aqueous ammonia pH 7.3 Add water
1.0j2 (washing water) Calcium ion 32■/l, Magnesium ion 7.
Tap water containing 3 mg/β of calcium ions was passed through a column filled with an H-swelling acidic cation exchange resin and an OH-type strong basic anion exchange resin, and calcium ions of 1.2 μ/! , magnesium ion 0. 20 rng of sodium isocyanurate dichloride was added to the water treated at 4/1/1.

(Stabilizing solution) Common to mother solution and replenisher solution Formalin (37Nw/v) polyquine ethylene-p-mono nonylphenyl ether (Average degree of polymerization 10) Ethylenecyaminetetraacetic acid di-Na thorium salt add water pH (Drying) The drying temperature was 50°C.

m7 5g As shown in Table 2, when the cyan coupler of the present invention and the DIR compound of the present invention are used in the configuration of the present invention, a silver halide color photographic light-sensitive material having excellent sharpness and improved desilvering properties can be provided. I can do it.

Example 2 Coupler C-12 used in the third and fourth layers of sample 105 prepared in Example 1 was replaced with the exemplary compound (Example 1) described in JP-A-1-131558 and JP-A-62-180365. Samples 202 and 203 were prepared in the same manner except for the change to Example 2).

After exposing these prepared samples through a pattern for RMS measurement and performing the processing shown in Example 1, the RM of these samples was
The S value (value at a 48μ diameter aperture) was measured.

The results are shown in Table 3.

Example 2

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, one green-sensitive emulsion layer, and one red-sensitive emulsion layer each on a support, the red-sensitive layer contains the following general formula [C
], the ratio of 2-equivalent couplers among the dye-forming couplers contained in the red-sensitive layer is 60% or more by mole, and at least one silver halide emulsion layer contains the following: A silver halide color photographic material containing a compound represented by general formula (I). Formula [C] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the general formula [C], R_1 is -CONR_4R_5,
-SO_2NR_4R_5, -NHCOR_4, -NH
COOR_6, -NHSO_2R_6, -NHCONR
_4R_5, -NHSO_2NR_4R_5, hydrogen atom, halogen atom or heterocyclic group, R_2 is a group that can be substituted on a naphthalene ring, R_3 is a substituent, X is coupling with an oxidized product of an aromatic primary amine developer In the reaction-removable group, 1 represents an integer of 0 to 3, and m represents an integer of 0 to 1. 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, respectively. However, X is not a group substituted with a carboxyl group. Further, when l is plural, R_2 may be the same or different, and may be combined with 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. R_1, R_2, R_3, or X may form a dimer or a multimer of more than two molecules bonded to each other via a divalent or more divalent group. General formula (I) A-(TIME)_n-B In the formula, A represents a coupler residue that leaves (TIME)_n-B by a coupling reaction with an oxidized product of an aromatic primary amine developer, TIME represents a timing group that binds to the coupling active position of A and releases B after being separated from A due to the coupling reaction, and B represents the following general formula (IIa), (IIb), (IIc), (IId) ,(IIe),
(IIf), (IIg), (IIh), (IIi), (IIj),
Represents a group represented by (IIk), (IIl), (IIm), (IIn), (IIo) or (IIp), where n is 0 or 1
represents an integer. However, when n is 0, B is directly bonded to A. General formula (IIa) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIb) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (
IIc) ▲Mathematical formulas, chemical formulas, tables, etc.▼General formulas (IId
) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIe) ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIf) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIg) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIh) ▲ Mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIi) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIj) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIk) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General Formula (IIl) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIm) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIn) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIo) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (I
Ip) ▲There are mathematical formulas, chemical formulas, tables, etc.▼In the formula, X_1
represents a substituted or unsubstituted aliphatic group having 1 to 4 carbon atoms or a substituted phenyl group. X_2 is a hydrogen atom, an aliphatic group, a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamide group,
Represents a sulfamoyl group, acyloxy group, ureido group, cyano group, nitro group, amino group, alkoxycarbonylamino group, aryloxycarbonyl group, or acyl group, and X_3 represents an oxygen atom, an ionic atom, or an imino group having 4 or less carbon atoms. where m represents an integer of 1 or 2. However, the total number of carbon atoms included in the m number of X_2 is 8 or less, and when m is 2, the two X_2 may be the same or different.