JPH03248153A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sensitivity and color reproduction performance by incorporating a cyan coupler to be allowed to release a residue having a water-soluble 6-hydroxy-2-pyridon-5-ylazo group or the like by coupling with the oxidation product of an aromatic primary amine color developing agent. CONSTITUTION:The cyan coupler contained in this silver halide color photographic sensitive material is represented by formula I in which R1 is an aliphatic or aromatic or heterocyclic group; Ar is an aromatic group; and X is a group to be released by coupling with the oxidation product of the aromatic primary amine color developing agent. The coupler is allowed to release the chemical residue having a water-soluble 6-hydroxy-2-pyridon-5-ylazo group, a water-soluble 2-acylaminophenylazo group, or a water-soluble 2-sulfonamidophenylazo group by coupling with the oxidation product of the aromatic primary amine color developing agent, thus permitting the obtained photosensitive material to be superior in sensitivity and color reproduction performance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a novel yellow colored cyan coupler and a silver halide color photographic material.
This invention relates to a photosensitive material containing a phenolic cyan coupler having a ureido group at the 5-position and an acyl group at the 5-position.

(Prior art) In silver halide color photographic materials, color development,
It is desired that color reproducibility is good, and processing dependence, desilvering property, and color image storage stability are also good.

As a device that relatively satisfies the above performance, US Pat.
．． No. 333.999, 4,427. Phenolic cyan couplers having a ureido group at the 2-position and an acyl group at the 5-position have been proposed in JP-A-57-204543 and JP-A-57-204544, etc., but when only these are used, the color There was a problem with reproducibility.

Therefore, it is proposed to improve color reproducibility by using these together with a yellow colored cyan coupler, as disclosed in JP-A-61-29842 and JP-A-1-197563.
It was proposed in the No. It is true that color reproducibility has been improved to some extent by these methods, but due to the low activity of these yellow colored cyan couplers, the degree of improvement in color reproducibility may not be sufficient, and when used in conjunction with magenta colored cyan couplers, the activity may be even greater. There were problems such as a drop in performance. In addition, these photosensitive materials have the problem that their photographic performance changes when they are aged for a long time or when exposed to high temperature conditions.

(Problems to be Solved by the Invention) The purpose of the present invention is, firstly, to provide a photosensitive material with high sensitivity and excellent color reproducibility, and secondly, to prevent changes in photographic performance over time from manufacture to photographing. The goal is to provide fewer sensitive materials,
The third objective is to provide a photosensitive material with excellent desilvering properties.

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

In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a cyan coupler represented by the following general formula [1], an aromatic primary amine developing agent is oxidized. The coupling reaction with the body produces water-soluble 6-hydroxy-2-pyridone-5-
A silver halide color photographic light-sensitive material containing a cyan coupler capable of releasing a compound residue containing a ylazo group, a water-soluble 2-acylaminophenylazo group, or a water-soluble 2-sulfonamidophenylazo group. .

General formula (1)) In general formula (1), R1 represents an aliphatic group, an aromatic group, or a heterocyclic group, Ar represents an aromatic group, and X represents a hydrogen atom or an aromatic primary amine developer oxidized. Represents a group that can be separated by a coupling reaction with a body.

Here, the aliphatic group refers to an aliphatic hydrocarbon group (the same applies hereinafter), and includes linear, branched, or cyclic alkyl, alkenyl, or alkynyl groups, whether substituted or unsubstituted. The aromatic group refers to a substituted or unsubstituted aryl group, which may be a fused ring.
The term "heterocycle" refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group.

R1 represents an aliphatic group having 1 to 36 carbon atoms, an aromatic group having 6 to 36 carbon atoms, or a heterocyclic group having 2 to 36 carbon atoms, preferably a tertiary alkyl group having 4 to 36 carbon atoms or a tertiary alkyl group having 7 carbon atoms.
-36 is a group represented by the following general formula [VI].

General formula (bi) 2 In the formula, R and R1 may be the same or different, and are a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, or an aliphatic group having 6 to 3 carbon atoms.
0 aromatic group, R+a represents a monovalent group, Z
represents 10--5-1-3O or 15O2-, l
represents an integer from 0 to 5! When there is a plurality of R4s, the plurality of R4s may be the same or different. Preferred substituents include R2 and R1 a straight chain or branched alkyl group having 1 to 18 carbon atoms, and R4 a halogen atom, aliphatic group, or aliphatic group. Group oxy group, carbonamide group, sulfonamide group, carboxy group, sulfo group, cyano group, hydroxyl group, carbamoyl group, sulfamoyl group, aliphatic oxycarbonyl group and aromatic sulfonyl group, and Z is 10-, respectively. I can do it.

Here, the carbon number of R4 is 0 to 30, and 2 is preferably 1 to 3.

Ar represents a substituted or unsubstituted aryl group, and may be a condensed ring. Typical substituents for Ar include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group,
C00Rs, C0R5, 50g0Rs, and R4 may be the same or different and represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R1 represents an aliphatic group, an aromatic group, or a heterocyclic group. Ar has 6 to 30 carbon atoms, and is preferably a phenyl group having the above-mentioned substituents.

X represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). However, X is a group other than a compound residue containing a water-soluble 6-hydroxy-2-pyridon-5-ylazo group, a water-soluble 2-acylaminophenylazo group, or a water-soluble 2-sulfonamidephenylazo group. It is preferable that Typical examples of coupling-off groups include halogen atoms, -OR,, 0 QCOR*, OCNHRm, aromatic groups with 6 to 30 carbon atoms, 111 0 azo groups, and coupling activity of couplers with 1 to 30 carbon atoms and nitrogen atoms. Examples include heterocyclic groups (succinimide, phthalimide, hydantoinyl, pyrazolyl, 2-benzotriazolyl, etc.) connected to this position. Here, R8 is an aliphatic group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms.
represents an aromatic group or a heterocyclic group having 2 to 30 carbon atoms.

As mentioned above, the aliphatic group in the present invention is saturated, unsaturated,
It may be substituted or unsubstituted, linear, branched, or cyclic. Typical examples include methyl, ethyl, butyl,
Cyclohexyl, allyl, propargyl, methoxyethyl, n-decyl, n-dodecyl, n-hexadecyl, trifluoromethyl, heptafluoropropyl, dodecyloxypropyl, 2,4-di-tert, t-amylphenoxypropyl, 2,4-di-tert -Includes amylphenoxybutyl, etc.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples include phenyl, tolyl, 2-tetradecyloxyphenyl, pentafluorophenyl, 2-chloro-5-dodecyloxycarbonylphenyl, 4-chlorophenyl, 4-cyanophenyl, 4-hydroxyphenyl, and the like.

In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples include 2-pyridyl group, 4-pyridyl group,
Included are 2-furyl group, 4-thienyl group, quinolinyl group, and the like.

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

Preferred examples of R1 include 1-(2,4-di-tert-amylphenoxy)amyl, 1-(2,4-di-tert-
amylphenoxy)hebutyl, t-butyl, etc.

Particularly preferable Ar examples include 4-cyanophenyl, 4-alkylsulfonylphenyl (4-methanesulfonamidophenyl, 4-propanesulfonamidophenyl, 4-
butanesulfonamide, etc.), 4-trifluoromethylphenyl and halogen-substituted phenyl (4-fluorophenyl, 4-chlorophenyl, 4-chloro-3-cyanophenyl, 3゜4-dichlorophenyl, 2,4.5-)+
J chlorophenyl, etc.).

Preferred examples of X include hydrogen atom, halogen atom, OR6
It is. R is preferably a carboxyl group, a sulfo group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkoxysulfonyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylfurfinyl group, a phosphono group, or It is a phosphonoyl group. R is preferably represented by the following general formula (A).

General formula (A) R9 [wherein, R9 and Ro. each represents a hydrogen atom or 1 or -P-, Ro and R1□ each represent hydroR1
! a xyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, or a substituted or unsubstituted amino group, l represents an integer of 1 to 6] In the general formula (A), R1 and/or When R1° is a -valent group, it is preferably an alkyl group (e.g., methyl, ethyl, n-butyl, ethoxycarbonylmethyl, benzyl, n-decyl, n-dodecyl), an aryl group (e.g., phenyl, 4-chlorophenyl, 4-chlorophenyl, -methoxyphenyl), an acyl group (e.g. acetyl, decanoyl, benzoyl, pivaloyl) or a carbamoyl group (e.g. N-ethylcarbamoyl, N-phenylcarbamoyl), and R9 and R1° are more preferably a hydrogen atom, an alkyl group or an aryl group. It is. In the general formula (1 (A)), Y is preferably -C--S-, and more preferably 10-. In the general formula (A), Ro is preferably an alkyl group, an alkoxy group, or an alkenyloxy group. group, an aryloxy group, or a substituted or unsubstituted amino group, more preferably an alkoxy group. In the general formula (A), l is preferably 1 to 1.
It is an integer of 3, more preferably 1.

R8 is most preferably represented by the following general formula (B).

General formula CB) [In the formula, RI3 and R14 each represent a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, RI
5 is a substituted or unsubstituted alkyl group, alkenyl group or aryl group.

The coupler represented by general formula (1) has substituents R+, A
In r or The range may be outside the specified range.

When the coupler represented by general formula (1) forms a multimer, a typical example is a single or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue. . In this case, the multimer contains repeating units of the general formula [■“], and the multimer contains a repeating unit of the general formula [11
] One or more types of cyan color-forming repeating units represented by the above may be contained in the multimer, even if the copolymer contains one or more non-color-forming ethylene monomers as a copolymerization component. good.

General formula [■''] In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, A represents -CONH--COO or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted phenylene group. Represents an unsubstituted alkylene group, phenylene group or aralkylene group, L is -CONH-NHCONH--NH
COO--NHCO--0CONH-NH--COO-
-0CO--CO--030w NHSOt- or -3O□NH-.

a, b, c represent O or 1. Q represents a cyan coupler residue from which a hydrogen atom other than the hydrogen atom of the 1-position hydroxyl group has been removed from the compound represented by the general formula (1).

As the multimer, a copolymer of a cyan color-forming polymer giving a coupler unit of general formula [11] and a non-color-forming ethylene-like monomer shown below is preferred.

Examples of non-chromic ethylene-like monomers that do not comb with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid), esters or amides derived from these acrylics (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-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its iis form,
for example vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene) itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic esters, N-vinyl-2- and lolidones, Examples include N-vinylpyridine and 2- and -4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more 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 general formula [1″]
The ethylenically unsaturated monomer to be copolymerized with the vinylic monomer corresponding to the copolymer may be used depending on the physical and/or chemical properties of the copolymer formed, such as solubility, binder of the photographic colloidal composition, etc. It can be selected so that its compatibility with gelatin, its softening temperature, flexibility, thermal stability, etc. are favorably influenced.

The cyan polymer coupler used in the present invention is obtained by dissolving a lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the general formula [VI] in an organic solvent in an aqueous gelatin solution. It may be made by emulsifying and dispersing it in the form of latex, or it may be made directly by emulsion polymerization.

U.S. Pat. No. 3.4 describes a method for emulsifying and dispersing lipophilic polymer couplers in an aqueous gelatin solution in the form of latex.
No. 51,820, and U.S. Pat.
The methods described in No. 080,211 and No. 3370.952 can be used.

General formula CI) Specific examples of compounds represented by As shown below, It is not limited to this.

(I 5) (■ 9) NHI; U to thl; HIL; UUtl (1 16) (1 17) (1 18) し++H+tltl (I 24) (1-25) (I 26) ■ 27) (I-28) (1-29) CH.

1'JJ (1-30) r! lI The coupler represented by the general formula (1) is used in U.S. Patent No. 4,3
33,999 and 4.427,767, JP-A-57-204543, JP-A-57-204544, JP-A-5
No. 7-204545, No. 59-198455, No. 60
-35731, 60-37557, 61-42
It can be synthesized by the synthesis method described in No. 658 and No. 61-75351.

The cyan coupler represented by the general formula [1] of the present invention is:
It is preferably added to a light-sensitive silver halide emulsion layer or a layer adjacent thereto in a light-sensitive material, and particularly preferably added to a red-sensitive emulsion layer.

Further, it is preferable to add it to the same layer as the yellow colored cyan coupler of the present invention or to an adjacent layer.

The total amount added to the photosensitive material is usually 0. O1~2.0
g/ml, preferably 0.1 to 1.2 g/ml, more preferably 0.2 to 0.8 g/rrf.

Next, the yellow colored cyan coupler of the present invention will be explained.

In the present invention, a yellow colored cyan coupler is defined as having an absorption maximum of 400 in the visible absorption region of the coupler.
A cyan coupler having a wavelength between 500 nm and 500 nm, and which forms a cyan dye having an absorption maximum between 630 nm and 750 nm in the visible absorption region by coupling with an oxidized herbal drug developed by an aromatic primary amine. .

Among the yellow colored cyan couplers of the present invention, water-soluble 6-hydroxy 2-pyridon-5-ylazo group, water-soluble 2-acylaminophenyl A cyan coupler capable of releasing a compound residue containing an azo group or a water-soluble 2-sulfonamide phenylazo group is preferably used.

The colored cyan coupler of the present invention is preferably represented by the following general formulas (CI) and (C1r).

General formula (CI) General formula (CI[) N 4 In general formulas (CI) and (CIO), Cp is a cyan coupler residue (T is bonded to its coupling position), and T is a timing group. , k is an integer of 0 or 1, and X includes N, 0, or S, so that ('r)*
represents a divalent linking group that is bonded to Q and Q represents an arylene group or a divalent heterocyclic group.

In the general formula (CI), R1 and R2 are independently a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group,
A cycloalkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, a carbonamide group, a sulfonamide group, or an alkylsulfonyl group, and R3 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, respectively. represent. However, T, X, Q, R,
, R2, or R1 contains a water-soluble group (eg, hydroxyl, carboxyl, sulfo, amino, ammoniamyl, phosphono, phosphino, hydroxysulfonyloxy).

It is common knowledge that OH)l can have the following tautomeric structure, and these tautomeric structures are also included in the structure defined by the general formula (CI) of the present invention.

(When R1 is a hydrogen atom) (When R3 is a hydrogen atom) (When Rx is a hydrogen atom) (When R3 is a hydrogen atom) In the general formula (CI[), R4 is an acyl group or a sulfonyl group, and R5 is an acyl group or a sulfonyl group. j represents a substitutable group, and j represents an integer of 0 to 4. When j is an integer of 2 or more, RS may be the same or different. However, T, X, Q, R
' or R5 contains a water-soluble group (eg, hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammoniamyl).

The compounds represented by formulas (CI) and (CII) will be explained in more detail below.

The coupler residue represented by Cp includes known cyan coupler residues (eg, phenol type, naphthol type, etc.).

A preferable example of Cp is The following general formula (Cp 1) (Cp 2) or (Cp 3) Examples include coupler residues.

General formula (Cp 1) H General formula (Cp 2) H General formula (Cp 3) R 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, when R++, R+z RIS, R+a or RIS contains a diffusion-resistant group, it means that the total number of carbon atoms is 8
40 to 40, preferably 10 to 30; otherwise, the total number of carbon atoms is preferably 15 or less. In the case of bis-type, telomer-type or polymer-type couplers, any of the above-mentioned substituents represents a divalent group and connects repeating units and the like. In this case, the range of carbon numbers may be outside the specified range.

R1+ to RIS, a and b will be explained in detail below. In the following, R41 represents an aliphatic group, an aromatic group, or a heterocyclic group, R42 represents an aromatic group or a heterocyclic group, and R41Ra4 and R45 represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. . R11 represents the same meaning as R4□.

R1! is a group having the same meaning as R41, R,, C0N- group, R
4coR4,0CON- group, R4,SO,N- group, R43Rs
Ra x N CON- group, R□o- group, R,, S-5
, haR44R4s Represents a rogen atom or R,,N- group. a is OR,
Represents ko to 3. When a is plural, a plurality of R1□ represent the same substituent or different substituents. Also each R,! may become divalent groups and connect to form a cyclic structure. Examples of divalent groups for forming a cyclic structure include R4coRaa. Here, C is an integer from 0 to 4,
d represents an integer from O to 2, respectively.

R13 represents a group having the same meaning as R41. R+a is R4
A group with the same meaning as 1, RIS is a group with the same meaning as R41, R
,,0CONH- group, R,, So, NH- group, Rs 3
N CON- group, R4zNsOzN- group, Raa
Ras Raa Ra.

R4,〇- group, R4,S- group, halogen atom or R,
, represents an N-group. When there are multiple RISs, each 43 represents the same thing or different things.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Representative examples include methyl, ethyl, propyl, isopropyl, butyl, (1)-butyl, (i)-butyl, (1)-amino, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1.1 .3.3-Tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

The aromatic group is preferably a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted naphthyl group.

A heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, preferably a 3- to 8-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom. It is.

Representative examples of heterocyclic groups include 2-pyridyl, 2-thienyl, 2-furyl, 1,3,4-thiadiazole-2
-yl, 24-dioxo-13imidazolidin-5-yl, 1.2.4-triazol-2-yl or 1-pyrazolyl.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include halogen atom, R4F〇- group, RabS- group, Ra7CON- group, R
Examples include 4FNC0- group, R,hOCONR41R411Raq group, R,, SO,N- group, RntNSOz- group, R4FR11R,, SO□- group, RnvOCO- group, R41R49 group, cyano group or nitro group. . Here R4
6 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R
4T, Ras and R49 are each an aliphatic group, an aromatic group,
Represents a heterocyclic group or a hydrogen atom. Aliphatic, aromatic or heterocyclic have the same meanings as defined above.

In general formula (Cp-1), R8 is preferably an aliphatic group or an aromatic group. In general formula (Cp-1), RI! is preferably a chloro atom, an aliphatic group or R4,CONH- group, a is preferably 1 or 2, R1 is preferably an aromatic group, R+g in general formula (Cp-2) is R,
, CONH- groups are preferred. In general formula (Cp-2), a is preferably 1. R14 is preferably an aliphatic group or an aromatic group. In general formula (Cp-3), b is preferably 0 or 1. As RI5, R,,0CONH- group, R,IC0NH- group or R4,5OzNH- group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring.

The timing group represented by T is a group whose bond with X is cleaved after the bond with Cp is cleaved by a campling reaction between the coupler and the oxidized product of the aromatic primary amine developer,
It is used for a variety of purposes, including adjusting force and knobling reactivity, stabilizing couplers, and adjusting release timing below X.

Examples of the timing group include the following known groups. In the following, *marks are bonded to Cp, **marks are bonded to X, or *marks are bonded to CP, and **marks are bonded to Q, respectively.

(T-1) (T-2) ttz (Rzs)t (T 3) (T-4) (T 5) Rg+ (T-6) CHz (T-7) 1 Ning -OC-*In the umbrella ceremony, R16 represents a group that can be substituted on the benzene ring, 1 has the same meaning as explained for R4, and R2□ represents a hydrogen atom or a substituent. L represents an integer from 0 to 4. Substituents for R2゜ and R2□ include R41% halogen atom, R430R,, S-1R
43(R44)NCO-1R4i00C-Ra3SO□
-1Ray (R44)NSO□Ra s CON (
R43)-1Ra + SO2N CR-:+)-
R4x C0-1Ra r CO0-1R4,SO-,
Nitro, R43 (R44) NC0N (R,S)-,
Cyano, R4+ OCON (Ra s )-1R4f
f○SO□R43(R44) N- R42(R44) N5Oz N (R-s)-1 or k is an integer of O or 1, but generally when k is O, that is, cp and X are directly bonded It is preferable to do so.

X is a divalent linking group bonded to (T)m or more by No or S, -O--S-10SO□--0SO□N
A heterocyclic group bonded with (T) or more by H- or N (e.g. pyrrolidine, piperidine, morpholine, piperazine,
Virol, pyrazole, imidazole, 1.2.4-)
Riazole, benzotriazole, succinimide, phthalimide, oxazolidine-24-dione, imidazolidine-2,4-dione, 1,2.4-triacylidine-
35-dione, etc.) or these groups together with alkylene groups (e.g. methylene, ethylene, propylene), cycloalkylene groups (e.g. 1,4-cyclohexylene), arylene groups (e.g. 0-phenylene, p-
phenylene), divalent heterocyclic groups (e.g. groups derived from pyridine, thiophene, etc.), -CO3O□--CO
C) --CONH 3Ch NH--3o, O--NHCONH3O, --
A linking group composed of NHCONH --NH3O, NH--NHCOO-, etc. is preferred, and X is more preferably represented by the general formula (II).

General formula (II) * X 1 (L 0- or -S-, L is an alkylene group, X2 is a single bond, -o-
-s--c.

CNH--3o□NH--NHSO,-1 Oz − 0SO.

CO- 1 OO OS O! NH- or -NH3 (ho- and m is 0
Represents an integer from ~3. The total number of carbon atoms (hereinafter referred to as C number) of X is preferably 0 to 12, more preferably 0 to 8. The most preferable value for X is 10 Hz CH20
− is.

Q represents an arylene group or a divalent heterocyclic group. When Q is an arylene group, the arylene group may have a substituent (e.g., halogen atom, hydroxyl, carboxyl, sulfo, nitro, cyano, amino, ammonium,
phosphono, phosphino, alkyl, cycloalkyl, aryl, carbonamide, sulfonamide, alkoxy, aryloxy, acyl, sulfonyl, carboxyl, carbamoyl, sulfamoyl), and the number of C is preferably 6 to 15, and more Preferably 6-10
It is. When Q is a divalent heterocyclic group, the heterocyclic group is a 3- to 8-membered, preferably 5- to 7-membered heterocyclic group containing at least one heteroatom selected from N, O, S, PSe, or Te in the ring. Monocyclic or fused ring heterocyclic groups (e.g. pyridine, thiophene, furan, pyrrole, pyrazole, imidazole, thiazole, oxazole, hendithiazole, hendioxazole, henzyfuran, benzothiophene,
1,3.4-thiadiazole, indole, quinoline, etc.), which may have a substituent (same as the substituent when Q is an arylene group), and the number of C is preferably 2-15, more preferably 2-10. Therefore, in the present invention, the most preferred (T)m-X Q- is when R+, Rz or R3 is an alkyl group, the alkyl group has an unsaturated bond, regardless of whether it is linear or branched. may contain substituents (e.g. halogen atoms,
hydroxyl, carboxyl, sulfo, phosphono, phosphine, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).

When R,, R, or R3 is a cycloalkyl group,
A cycloalkyl group is a 3- to B-membered cycloalkyl group, and even if it has a bridging group or an unsaturated bond, it may have a substituent (R, R, or R4 is an alkyl group). (same as the substituent).

When R,, R, or R3 is an aryl group, even if the aryl group is a fused ring, the substituent (R1, R2 or R
In addition to substituents when 1 is an alkyl group, there are also alkyl, cycloalkyl, and the like. ).

When R, R, or R1 is a heterocyclic group, the heterocyclic group includes at least one N, S, O, P.

3 containing a heteroatom selected from Se or Te in the ring
~8-membered (preferably 5-7 membered) monocyclic or fused ring heterocyclic group (e.g. imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), in which the substituent (R, , R, or R1 is It may have the same substituents as in the case of an aryl group).

Here, the carboxyl group may contain a carboxylade group, the sulfo group may contain a sulfonate group, the phosphino group may contain a phosphinate group, and the phosphono group may contain a phosphonate group, and in this case, the counter ion may be Li'Na", K", ammonium, etc. It is.

R1 is preferably a hydrogen atom, a carboxyl group, or a C number of 1 to
10 alkyl groups (e.g. methyl, t-butyl, sulfomethyl, 2-sulfomethyl, carboxymethyl, 2-carboxymethyl, 2-hydroxymethyl, benzyl, ethyl, isopropyl) or C6-12 aryl groups (e.g. phenyl, 4-methoxyphenyl, 4-sulfophenyl), and particularly preferably a hydrogen atom, a methyl group or a carboxyl group.

R1 is preferably a cyano group, a carboxyl group, or a C number of 1 to
10 carbamoyl groups, sulfamoyl groups with 0 to 10 carbon atoms, sulfo groups, alkyl groups with 1 to 10 carbon atoms (e.g. methyl, sulfoethyl LC sulfonyl groups (e.g. methylsulfonyl, phenylsulfonyl), 1 to 10 carbon atoms), 1 to 10 carbon atoms; ~
IO is a carbonamide group (eg, acetamide, henzamide) or a sulfonamide group having 1 to 10 carbon atoms (eg, evamethanesulfonamide, toluenesulfonamide), and particularly preferably a cyano group, a carbamoyl group, or a carboxyl group.

R3 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (e.g. methyl, sulfomethyl, carboxymethyl, 2
-sulfomethyl, 2-carboxymethyl, ethyl, n-
butyl, benzyl, 4-sulfobenzyl) or C number 6
~15 aryl groups (e.g. phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 4-methoxyphenyl, 2,4-dicarboxyphenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2.4
-disulfophenyl, 25-disulfophenyl), more preferably a C1-7 alkyl group or a C6 alkyl group
~10 aryl groups.

Specifically, R4 is an acyl group represented by the general formula (III) or a sulfonyl group represented by the general formula (TV).

General formula (I[[) General formula (IV) R++5Ch When R11 is an alkyl group, the alkyl group may be linear or branched, and may contain an unsaturated bond, and the substituent ( For example, halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano,
alkoxy, aryl, alkoxycarbonyl, amino, ammoniamyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl)
It may have.

When R31 is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group, and even if it has a bridging group or an unsaturated bond, the substituent (R
31 may have the same substituent as the alkyl group).

When R31 is an aryl group, the aryl group may be a fused ring or have a substituent (in addition to the substituent when R3 is an alkyl group, there are alkyl, cycloalkyl, etc.).

When R31 is a heterocyclic group, the heterocyclic group has at least one
N, S, 0. A 3- to 8-membered (preferably 5- to 7-membered) monocyclic or condensed ring heterocyclic group containing a beta atom selected from P, Se, or Te in the ring (e.g., imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl) and may have a substituent (same as the substituent when R3+ is an aryl group).

Here, the carboxyl group includes a carboxylade group, the sulfo group includes a sulfonate group, the phosphino group includes a phosphinate group, and the phosphono group includes a phosphonate group (in this case, the counter ion is Li゛Na'', ni', ammonium etc.

R31 is preferably an alkyl group having 1 to 10 carbon atoms (e.g. methyl, carboxymethyl, sulfoethyl, cyanoethyl), a cycloalkyl group having 5 to 8 carbon atoms (e.g. cyclohexyl, 2-carboxycyclohexyl), or a cycloalkyl group having 6 to 10 carbon atoms. Aryl group (phenyl, 1-naphthyl,
4-sulfophenyl), particularly preferably C number 1
-3 alkyl group, C6 aryl group.

R'! is a group capable of substituting , preferably an electron-donating group, particularly preferably -NR32R32 or 10R34. The preferred substitution position is the 4-position. R32, R33 and R34 are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. A ring may also be formed between Rsz and R33,
The nitrogen heterocycle formed is preferably an alicyclic one.

j represents an integer from O to 4, preferably 1 or 2, particularly preferably 1.

80 in general formulas (CI) and (CI[) below
A specific example of N'+(-" is shown below.

(Example of Cp) H CsHr + (t) C++H+v(n) H3 H (i) CJ 啼OCN (i) CaHJCN III CsH,,1) C2H (1) 2H5 Js H C,H H 0■ Js (X Example) OS, 0CHz, 0CHzCHz
OCHz CHz O, OCH2CH2CH20-〇(
CH2CHIO)2-, -0CH2CH,5OCH,C
H, NHCO-, -0CH2CH, NH30□OCHt
CHz S Oz, OCHz CHz O
C00CHz CHt CO,S CHz CON H
3CHi Coo, 0CHCONHH3 0CH! CHz OS Ot OC00CHz
CH, 0CHz CHCHzCo, HCo, H OCH! CHO, 0CHCHz O CO, HCo, H OCH, CHS-, -0CH2CHO Co, HSo, Na (Example of Q) tlzL, l'lz:) Change to U3h zt, uυ■ O3Na Specific example of the colored coupler of the present invention (YC 1) H (YC 2) H Shin2υυNa (YC-3> (YC-4) θB (YC-5) H (YC 6) H (YC-7) H (YC-8) H (YC 9) H (YC-10) (YC 11) (YC 12) H (YC 13) (YC 14) H (YC-15) H +12L, tlz and UUtl (YC 16) (YC-17) H (YC -19) 0H (YC-20) H (YC 21) H (YC-22) (YC 23) H (YC-24) (YC 25) J13-n H (YC 26) CJ+3-n 0■ υUN ( YC 27) H (YC 28) Js (YC 29) H (YC-30) (YC 31) 0■ (YC 32) H (YC-33) H C,H8 (YC-34) (YC 35) H ( YC-36) (YC 37) (YC 38) H (YC-39) 0■ (YC 40) (YC 41) H 0■ (YC 43) (YC 44) H H N11bUzL;Hs (YC-45) 0H (YC-46) H NnL,UL; It can be synthesized by a diazo coupling reaction.

The former, 6-hydroxy-2-pyridones, are described in "Heterocyclic Compounds - Pyridine and Its Derivatives - Part 3" edited by Talinsberg (Interscience Publishing, 1962).
), Journal of the American “Chemical
Society (J, As.

Chem, Soc, ) 1943, volumes 6-5, 449
Page, Journal of the Chemical Technology and Biotechnology (J, Chew, Tec.
h.

Biotechnol, ) 1986, Volume 36, 41
Page 0, Tetrahedron 1
966, Vol. 22, p. 445, Special Publication No. 61-52827, West German Patent No. 2.162,612, No. 2,349.7
No. 09, No. 2,902,486, U.S. Patent No. 3,763
．． It can be synthesized by the method described in No. 170 and the like.

The latter diazonium salts are disclosed in U.S. Pat. No. 4,004,929, U.S. Pat.
It can be synthesized by the method described in No. 61-273543 and the like. The diazocambling reaction between 6-hydroxy-2-pyridones and diazonium salts is performed using methanol,
The reaction can be carried out in a solvent such as ethanol, methylcellosolve, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dioxane, water, or a mixed solvent thereof. At this time, the bases include sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide,
Potassium hydroxide, pyridine, triethylamine, tetramethylurea, tetramethylguanidine, etc. can be used.

The reaction temperature is usually -78°C to 60°C, preferably 20°C to
The temperature is 30°C.

Examples of synthesis of the colored coupler of the present invention are shown below.

500 g of methanol was added to 125.2 g of taurine and 66 g of potassium hydroxide, heated and stirred, and 110 g of methyl cyanoacetate was added dropwise over about 1 hour.

After heating under reflux for 5 hours, it was left to stand overnight, and the precipitated crystals were filtered.
By washing with ethanol and drying, 202.6 g of crystals of compound a were obtained.

11.5 g of Kassai ±p Kassodo compound a and 3.5 g of potassium carbonate and 11 parts of water
．． 5- was added thereto, and while the mixture was heated and stirred on a steam bath, 7.8 g of ethyl acetoacetate was added dropwise, and the mixture was further stirred for 7 hours. After cooling, 9.2 M1 of hydrochloric acid was added and stirred to precipitate crystals. The mixture was filtered, washed with methanol, and dried to obtain 10.4 g of crystals of the compound.

10.1 g of compound C synthesized by the synthesis method described in US Pat. A diazonium solution was prepared by dissolving the mixture in methyl cellosolve 60 and 4.3 ml of water-cooled hydrochloric acid, and then adding dropwise a solution of 1.84 g of sodium nitrite in water. Next, 7.8 g of compound b and 8.2 g of sodium acetate were added with 60 methyl cellosolve and 2 liters of water (1T
The diazonium solution was added dropwise while stirring on ice. After the dropwise addition, the mixture was further stirred for 1 hour and then at room temperature for 2 hours, and the precipitated crystals were filtered. After washing with water and drying, the crystals were dispersed in methanol 50 (ld), heated under reflux for 1 hour, and then allowed to cool. The crystals were filtered, washed with methanol, and dried to form red crystals of the desired exemplary coupler (YC-1). 13
．． 6g was obtained. The melting point of this compound is 269-272℃ (
decomposition), and the structure was confirmed by 'HNMR spectrum, mass spectrum, and elemental analysis. The maximum absorption wavelength of this compound in methanol was 457.7 nm, the molecular extinction coefficient was 41,300, and it exhibited good dispersion absorption characteristics as a yellow colored coupler.

(Synthesis Example 2) Synthesis of Exemplary Coupler (YC-3) JP-A No. 6
To 19.2 g of the compound d synthesized by the synthesis method described in No. 2-85242, 75-N,N-dimethylformamide was added.
Add and dissolve 75 m of methyl cellosolve, stir while cooling with water, add salt #5゜6-, then add a solution of 2.5 g of sodium nitrite in water for 1 hour after the dropwise addition, and for another 1 hour at room temperature. The mixture was stirred to prepare a diazonium solution.

Methyl cellosolve 75- and water 26- were added to 1 g of compound BLO and 10.7 g of sodium acetate, and the diazonium solution was added dropwise while stirring on ice.
The mixture was further stirred at room temperature for 2 hours, and the precipitated crystals were filtered. Next, the crystals were dispersed in 200 methanol, and a solution of 2.2 g of sodium hydroxide in 1 OWd of water was added dropwise.
Stir for hours. Neutralize with concentrated hydrochloric acid, wash the precipitated crystals with water,
After washing with methanol, it was dried. The obtained crude crystals were purified using hot methanol in the same manner as in Synthesis Example 1 to obtain 14.8 g of the target exemplary coupler (YC-3).

The melting point of this compound is 246-251) (decomposition),
The structure was confirmed by HNMR spectrum, mass spectrum and elemental analysis. The maximum absorption wavelength of this compound in methanol is 457.6 nm, and the molecular absorption coefficient is 42.
700, showing good spectral absorption characteristics as a yellow colored coupler.

Kitaji 11 Deaf needle wound gland anthranilic acid 137.1g acetonitrile 600-
The mixture was heated and stirred, and 92.5 g of diketene was added dropwise over about 1 hour. After heating under reflux for 1 hour, the mixture was cooled to room temperature, and the precipitated crystals were filtered, washed with acetonitrile, and dried to obtain 200.5 g of compound e crystals.

199゜1g of clasp boat construction compound e199゜1g, ethyl cyanoacetate 89゜2g,
Add 344 g of 28% sodium methoxide to 0.0 g of methanol.
91 and reacted in an autoclave at 120°C for 8 hours. - After standing overnight, the reaction mixture was concentrated under reduced pressure, and the water was 700%
was added, and the mixture was made acidic with 230% of concentrated hydrochloric acid. The precipitated crystals were collected by filtration, and the resulting crude crystals were heated and washed with a mixed solvent of ethyl acetate and acetonitrile to obtain 152 g of compound f.

Synthesis of Exemplary Coupler (YC-28) Compound g synthesized according to the synthesis method described in U.S. Pat. No. 4,138,258, 13. ．． Dissolve Og in 40-NN-dimethylformamide, cool with water and add 4.5 ml of concentrated hydrochloric acid.
was added, and then a solution of 1.48 g of sodium nitrite in 5 m of water was added dropwise to prepare a diazonium solution. 20 d of N,N-dimethylformat and 15 ml of water were added to 8 g of sodium acetate and 20 d of N,N-dimethylformat, and the above diazonium solution was added dropwise while stirring while cooling with water. After the 6 dropwise additions, the mixture was further stirred at room temperature for 30 minutes. Acidified with hydrochloric acid, extracted with ethyl acetate, washed with water, concentrated under reduced pressure, and recrystallized the concentrate with a mixed solvent of ethyl acetate and methanol to obtain the exemplified coupler (
13 g of yellow crystals of YC-28) were obtained. This coupler (
The melting point of VC-28) is 154-6°C, and the structure is '
Confirmed by HNMR spectrum, mass spectrum and elemental analysis. The maximum absorption wavelength of this compound in methanol was 458.2 nm, the molecular extinction coefficient was 42,800, and it exhibited good spectral absorption characteristics as a yellow colored coupler.

The yellow colored cyan coupler represented by the general formula (CIO) is disclosed in Japanese Patent Publication No. 58-6939 and the general formula (CIO).
) can be synthesized by the method described in the above-mentioned patents and the like.

In the present invention, as the yellow colored cyan coupler, those represented by the general formula (CI) are particularly preferably used.

The yellow-colored cyan coupler of the present invention is preferably added to a light-sensitive silver halide emulsion layer or a layer adjacent thereto in a light-sensitive material, and is particularly preferably added to a red-sensitive hole layer. The total amount added is 0.00
5~0.30g/n? and preferably 0.02 to 0
．． 20 g/n (more preferably 0.03 to 0.15 g
/nf.

The yellow-colored cyan coupler of the present invention can be added in the same manner as ordinary couplers, as described below.

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 restrictions on the number or order of layers and non-photosensitive layers.A typical example is to prepare a plurality of silver halide emulsions with substantially the same color sensitivity but different photosensitivity on a support. A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of a layer, the light-sensitive layer being a unit light-sensitive layer having sensitivity to any of blue light, green light, and red light; In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

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

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

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange them in a keychain pattern in which the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity green-sensitive layer (Gl() / low-sensitivity blue-sensitive layer (GL) )/
High-sensitivity red-sensitive layer (R11) /low-sensitivity red-sensitive layer (R
L) or BH/BL/GL/GH/RH/RL
or Bl(/BL/G!(/GL/RL/RH
They can be installed in the following order:

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

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 color-sensitive layer, the medium emulsion layer/high-sensitivity hole layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

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

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 the photographic hole are those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin crystal planes. It may have crystal defects such as, 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 polydisperse emulsion or monodisperse emulsion.

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) No.

17643 (December 1978), pp. 22-23, “
1. Emulsion preparation
on and types)”, and Nll 18
716 (November 1979), page 64B, Issue 3
07105 (Mon. 1989), pp. 863-865, and the graphic "Physics and Chemistry of Photography", published by Beaumontel (P, GIafkides, Chemie
et Ph1sique Photography
ique, Paul Mor+tel, 1967)
, "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffin.

Photographic Emulsion Che
mistry (Focal Press1966))
, “Manufacture and Coating of Photographic Emulsions” by Zelikaman et al., published by Focal Press (V, L, Zelikaanetal
, + Making and Coating Pho
tographic Emul-sion, Foca
1 Press 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 3 or greater can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434,226, 4,414.310, 4,
433,048, 4,439, 520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. They may also be bonded with compounds other than silver halide, such as silver rhodan or lead oxide, and mixtures of particles of various crystal forms may be used.

The above-mentioned emulsions may be of the surface latent image type that forms latent images primarily on the surface, of the internal latent image type that forms inside the grains, or of the type that has latent images both on the surface and inside the grains, but negative-tone emulsions It is necessary that Among the internal latent image type emulsions, a core/shell type internal latent image type emulsion described in Jikai No. 1163-264740 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 Research Disclosure Ni1
17643, Doren 18716, and Douben 307105, and the relevant parts 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 grain surfaces as described in U.S. Pat. No. 4,082.553, U.S. Pat. No. 4,626,4
No. 98 and JP-A No. 59-214852, silver halide grains and colloidal silver covered inside the grains are used as a photosensitive silver halide hole side layer and/or a substantially non-photosensitive hydrophilic colloid layer. It can be used preferably.

Silver halide grains that have their interiors or surfaces covered are defined as - (
refers to silver halide grains that can be developed (non-imagewise). A method for preparing silver halide grains with a fogging inside or on the grain 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. As the silver halide coated inside or on the surface of the grain, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. Although there is no particular limitation on the grain size of these fogged silver halide grains,
The average particle size is preferably 0.01 to 0.75 .mu.-1, particularly 0.05 to 0.6 p.sup.-. 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 non-light-sensitive fine-grain silver halide. Non-light-sensitive fine-grain silver halide is not exposed to light during imagewise exposure to obtain a dye image, but is not exposed to light during the development process. These are fine silver halide grains that are not substantially developed and are preferably not fogged in advance.

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

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 μ- is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, before adding these 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 in advance. Colloidal silver can preferably be contained in the silver halide grain-containing layer.

The coating silver amount of the photosensitive material of the present invention is preferably 6.0 g/nf or less, and 4.5 g/nf or less. The following are most preferred.

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 order to prevent deterioration of photographic performance due to formaldehyde gas, 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 fogging agent, a development accelerator, a silver halide abrasion, or their precursors are released into the light-sensitive material of the present invention, as described in JP-A-1-106052, regardless of the amount of developed silver produced by the development process. It is preferable to contain a compound.

Dyes dispersed in the photosensitive material of the present invention by the method described in International Publication No. WO3B104794, 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 No. 17643, ■-C-C, and Questionnaire No. 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, 401, 752, No. 4.248.961, Japanese Patent Publication No. 10739/1983, British Patent No. 1,425,020, No. 1,476.76
No. 0, U.S. Patent No. 3,973,968, U.S. Patent No. 4.31
Preferred are those described in European Patent No. 4,023, European Patent No. 4.511.649, European Patent No. 249.473A, and the like.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, European Patent No. 4.351,897, European Patent No. 73.636, US Patent No. 3,061,432, European Patent No. 3725.067, Research Disclosure No. 24220 (June 1984) , JP-A-60-33
No. 552, Research Disclosure N11242
30 (June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 5
No. 5-118034, No. 60-185951, U.S. Patent No. 4.500,630, U.S. Pat.
Particularly preferred are those described in No. 795 and the like.

As the cyan coupler, various couplers including those represented by the general formula CI) of the present invention can be used in combination in the same layer or in different layers. As those cyan couplers,
U.S. Patent No. 4.052,212, U.S. Patent No. 4.146,3
No. 96, No. 4.228.233, No. 4, 296
゜No. 200, No. 2.369.929, No. 2,80
1.171, 2,772,162, 2,8
No. 95,826, No. 3,772.002, No. 3,
No. 758.308, No. 4.334.011, No. 4
, 327.173, West German Patent Publication No. 3.329.72
9, European Patent No. 121,365A, European Patent No. 249.4
No. 53A, U.S. Patent No. 3,446,622, U.S. Patent No. 4.
No. 333.999, No. 4.775,616, No. 4
．． No. 451.559, No. 4,427,767, No. 4,690,889, No. 4,254. No. 212,
Those described in JP-A-61-42658 and the like are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820; 4,080,211; 4,367.282;
No. 4,576°910, British Patent No. 2.102.
No. 137, European Patent No. 341°188A, etc.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96, 570, West German Patent (
The one described in Japanese Publication No. 3,234.533 is preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
-G section, ■-G section of NCL 307105, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 57-39413,
U.S. Patent No. 4.004,929, U.S. Patent No. 4,138.2
No. 58, UK Patent No. 1.146.368 is preferred, and the fluorescent dye released upon coupling as described in U.S. Pat. No. 4.774.181 compensates for unwanted absorption of the chromogenic dye. Couplers, U.S. Patent No. 4,
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. 777,120.

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

The development-inhibiting side-emitting DIR coupler is the aforementioned RD
17643, ■-F term and the same N [L 307105,
■-Patent listed in Section F, JP-A-57-151944
Preferred are those described in US Pat. No. 57-154234, US Pat. No. 60-184248, US Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2.131, No. 188, JP-A-59-15763
8, No. 59-170840 are preferable;
Also preferred are compounds which release a blurring agent, a development accelerator, a silver halide solvent, etc. through a redox reaction with an oxidized form of a developing agent, as described in JP-A No. 340, JP-A-144940, and JP-A-1-45687.

Other compounds that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, etc.; U.S. Pat. , DIR redox compound releasing couplers described in JP-A-60485950, JP-A-62-24252, etc., DIR coupler-releasing couplers, D'
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜30
2A, a coupler that releases a dye that becomes aftercolored after separation as described in No. 313,308A, a bleaching accelerator-releasing coupler as described in R, D, No. 11449, No. 24241, JP-A No. 61-201247, etc. U.S. Patent No. 4,555,477
Ligand-releasing coupler described in JP-A-63-75
Couplers that emit leuco dyes as described in No. 747, couplers that emit fluorescent dyes as described in U.S. Pat.

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

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

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-amylphenyl) phthalate, (2,4-di-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-
(ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid ester 1! (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides @ (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.) , alcohols or phenols (isostearyl alcohol, 2
, 4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives ( N,N-dibutyl 2-butoxy-5-4ert-octylaniline, etc.), hydrocarbons R (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

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

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are disclosed in U.S. Pat. etc. are listed.

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

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

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of NCL 17643, same Na 1871
6, page 647 right column to page 648 left column, and Net3
07105, 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 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and 16 μm or less. is particularly preferred, and the membrane swelling rate TI/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 (^, Green)
Photographic Science and Engineering (Photogr, Sci, Eng,)
, 19@, No. 2, pages 124-129, Tlzt can be measured by using a swellometer (swelling membrane) of the type described in 19@, No. 2, pp. 124-129, and Tlzt is the maximum value reached when treated with a color developer for 13 minutes and 15 seconds at 30° 90% of the swollen film thickness is the saturated film thickness,
It is defined as the time required to reach the saturated film thickness of 172 mm.

The film swelling rate T172 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 rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula = (maximum swollen film thickness - film ff)/film thickness.

The photosensitive material of the present invention has a hydrophilic colloid layer (with a total dry film thickness of 2 μm to 20 μm) on the side opposite to the side having the emulsion layer.
It is preferable to provide a bank layer (referred to as a bank layer), which contains the aforementioned light absorbers, filter dyes, ultraviolet absorbers, static inhibitors, hardeners, binders, plasticizers,
It is preferable to contain a lubricant, a coating aid, a surface active agent, 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 described in the above-mentioned RD, No. 17643, pages 28-29, and NIL 18716, No. 6.
51 left column to right column, and 88 of the same NCL 307105
Development processing can be carried out by the usual method described on pages 0 to 881.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl- 4-amino-N-ethyl-N-β
-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and sulfates thereof, Examples include hydrochloride and p-toluenesulfonate. 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.

Color developers include pH 1 buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It generally contains an inhibitor or an anti-fog agent. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers. , auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,I! -)rimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine di(0-hydroxyphenylacetic acid), and salts thereof can be mentioned as representative examples.

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

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

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

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

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

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents include organic complex salts of iron (■), such as ethylenediaminetetraacetic acid, Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc. can be used. . Among these, aminopolycarboxylic acid iron(I[) complex salts, including ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(I[[) complex salt], are useful for rapid processing and environmental pollution prevention. More preferable from this point of view, iron aminopolycarboxylate (I[[)
Complex salts are particularly useful in both bleach and bleach-fix solutions. These iron(III) aminopolycarboxylic acids
The pH of bleach or bleach-fix solutions using complex salts is usually 4.0.
~8, but it is also possible to process at an even lower pn for faster processing.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3.893.858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53404232, No. 53-124424, No. 53-141623,
53-28426, Research Disclosure N (No. 117129 (July 1978), etc., compounds having a mercapto group or disulfide group; thiazolidine derivatives described in JP-A-50-140129;
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
・No. 53-32735, U.S. Patent No. 3.706,56
Thiourea derivatives described in No. 1; West German Patent No. 1.127,
No. 715, iodide salts described in JP-A-58-16.235; West German Patent Nos. 966.410 and 2,748.43
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compound described in No. 8836; Others
No. 9-40.943, No. 49-59.644, No. 53
-94.927, 54-35.727, 55-
Compounds described in No. 26,506 and No. 58-163.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85
No. 8, West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-
Preference is given to the compounds described in No. 95.630. Furthermore, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleach accelerators may be added to light-sensitive materials. agents are particularly effective.

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

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added 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 a pH of 1
A compound having a pKa of 6.0 to 9.0, preferably imidazoles such as imidazole, l-methylimidazole, 1-ethylimidazole, and 2-methylimidazole, is added at 0.1 to 10 mol/l to adjust the temperature. It is preferable.

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

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening the agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A-62-183460, and the method described in JP-A-62-183.
No. 461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

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

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnal of the 5ociety
of Motion Picture and
It can be determined by the method described in τevision Engineers, Vol. 64, P, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents," (1986) Sankyo Publishing, Hygiene. Technical extras “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Society of Industrial Engineers, Japan Antibacterial and Antifungal Society “Encyclopedia of Antibacterial and Antifungal Agents J (
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. Examples of the dye stabilizer that can be used include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

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

In a process using an automatic processor or the like, when each of the above-mentioned processing liquids undergoes e4 condensation due to evaporation, it is preferable to correct the concentration by adding water.

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 Na14,8
Schiff base-type compounds described in No. 50 and No. 1115.159, aldol compounds described in No. 13.924, metal salt complexes described in U.S. Pat. Compounds can be mentioned.

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

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

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

Further, the silver halide photosensitive material of the present invention is disclosed in US Patent No. 4.
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in European Patent No. 9-218443, European Patent No. 61-238056, European Patent No. 210,660A2, 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 Each layer having the composition shown below was coated on a triacetyl cellulose film support provided with an undercoat layer, and photosensitive material 1 was prepared.
01 was produced.

(1) Emulsion layer/Silver iodide for plate-shaped bill 0 mol%, average aspect ratio 7
．． 0 average particle size 0.75 μ) ... 1.70 g as silver / Bo coupler (1-1) ... 0.80 g
/-* So 1 v -2-0,50g/rrf
・Gelatin...3.20 g
/ Bo (2) Protective layer・Sodium 2,4-dichloro-6-hydroxy-5-triazine...0.10 g/rrr・Gelatin...1.8 g/po (sample 10
2) Colored coupler R-1 for comparison in the emulsion layer of sample 101
Sample 1 was prepared in the same manner except that 0°080 g/nf of
02 was produced.

(Samples 103 to 110) Samples 103 to 110 were prepared by replacing R-1 in sample 102 with other couplers in equimolar amounts as shown in Table 1.

(Samples 111 to 114) Coupler (+-1) of sample 108 to (1-1)/(1-
2) (1/1), (1-6), (1-7) and (1-
Samples 111 to 114 were obtained by replacing 8) with equimolar amounts.

These samples were exposed to red light for sensitometry and subjected to the following color development process. The cyan and yellow densities of the development method samples were measured, and the cyan density (fog + 0.2
), the relative sensitivity was determined by the logarithm of the reciprocal of the exposure amount giving the density, and the color turbidity was determined by the yellow density at the density giving the cyan density 0.8.

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 ■ A countercurrent water washing method was adopted from ■ to ■. Next, the composition of each treatment liquid will be described.

The replenishment amount of the processing solution was 1,200 m for color development per one color photosensitive material, and 80 (ld) for all other processes including water washing.

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

(Color developer) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene 1.1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Mother solution Replenisher 1.0g 1.1g 2.0g 2.2g 4.0g 4.4g 30 .0g 32.0g 1.4g 0.7g 1.3■ Add hydroxylamine sulfate 4-(N-ethyl-N-β monohydroxyethylamino)-2-methylaniline sulfate 2.4g 4.5g 1.0! 2.6g 5.0g 1, On p H10,010,5 (Bleach solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium salt 120.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium nitrate 10.0g Bromide Ammonium 100. ．． 0g Bleach accelerator Add 5 x 10 molar ammonia water PH Add water (bleach-fix solution) Common to mother liquor and replenisher 6.3 1, Of Ethylenediaminetetraacetic acid ferric ammonium salt 50.0g Ethylenediaminetetraacetic acid diacetate Sodium salt 5.0゜ Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution (70% > 240at Add ammonia water pH 7.3 Add water
1! (Washing water) Calcium ion 32/1, Magnesium ion 7.
Tap water containing 3■/L was passed through a column filled with H-type strongly acidic cation exchange resin and OH-type strongly basic anion exchange resin, and calcium ion 1.2■/It and magnesium ion 0.4■ Sodium isocyanurate dichloride was added in an amount of 20 ml per liter of water treated to give a concentration of 20 ml per liter of water.

(Stable solution) Common formalin for mother solution and replenisher solution (37% w/v) 2. Od polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid di-sodium salt solution was added to pH (drying) The drying temperature was 50°C.

0.3g 0.05g Table 1 From Table 1, the samples using the yellow-colored cyan coupler of the present invention have lower color turbidity without a decrease in sensitivity and better color reproduction than samples using the coupler of the present invention. It is clear that the above is preferable.

Example 2 Sample 2 was prepared by adding 0.080 g/po of magenta colored cyan coupler ExC-2 to the emulsion layer of Samples 101 to 114.
01 to 214 were produced.

These samples were exposed and developed in the same manner as in Example 1, and the density was measured. Furthermore, the magenta density at a density that gave a cyan density of 08 was determined as the magenta color turbidity.

From Table 2, the samples using the yellow colored cyan coupler of the present invention not only have less yellow color turbidity, but even when used in conjunction with magenta colored cyan coupler, the magenta color turbidity does not decrease without reducing the masking ability. It can be seen that it is possible to provide a sensitive material with a low degree of strength.

Table 2 Example 3 Sample 301, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared on an undercoated cellulose triacetate support.

(Composition of photosensitive layer) The coating amount is expressed in g/rd units of silver for silver halide and colloidal silver, and in g/f units for coupler additives and gelatin. The amount expressed by is added to the sensitizing dye.
It is expressed as the number of moles per t mole.

1st layer (antihalation layer) Black colloidal silver 0.15 Gelatin 1.00ExM-80,
02 142 layer (middle layer) Gelatin 1,00UV-1
0,03 UV-20,06 υV-30,07 Ex F -10,004 Solv-20,07 3rd layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, internal high Agl Type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 2.5) Coated silver amount
0.40 gelatin 0.8
0ExS-11,0XIO-'ExS-23,0XIO-'Ext-31,0XIO-' ExY-140, OIE Coupler of the present invention (1-25) 0.13C Coupler of the present invention (1-26) 0.13 (Solv
-10,00'i 4th layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, internal high Agl type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal Crystal, twin mixed grain, diameter/thickness ratio 1) Coated silver amount
0.85 gelatin 1.2
6QXIO-'0XIO-'0XIO-' 0° 180 0.180 0.010 0.02() 0.060 0.035 0XID-' 0, 20 ExS-11°ExS-2 ExS-3 Coupler of the present invention ( 1-25) Coupler of the present invention (1-26) ExY-14 ExY-13 xC-2 xC-5 Pd-10 Solv-1 5th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide milk *J ( Ag1 10 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, twinned mixed particles, diameter/thickness ratio 2) Coated silver amount
0.70 Gelatin 0.
80ExS-11,0XIO-'ExS-23,0XIO-'ExS-31,0XIO"' 3゜1゜1゜ExC-20,010 ExC-30,070 EXC-50,020 ExC-60,080 Solv-10 ,15 Solv-20,08 6th layer (middle layer) Gelatin 1.0P-20
,17 Cpd-10,10 Cpd-40,17 Solv-10,05 7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 16 mol%, internal high Agl type, equivalent sphere diameter 0.3 μm, Coefficient of variation of equivalent sphere diameter 28%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 2.5)! ! ! Cloth silver amount 0.30 Gelatin 0
,40ExS-45,0XIO-'ExS-60,3X10-'ExS-52,0XIO-' ExM-90,20 ExY-130,03 ExM-80,03 Solv-10,20 8th layer (medium sensitivity green feeling Emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, internal high Agl type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin mixed grains, diameter/thickness ratio 4) Coating Silver amount
0.70 gelatin 1.0
0ExS-45,0XIO-'ExS-52,0XIO-'ExS-60,3X10-' ExM-90,25 ExM-80,03 ExM-100,015 ExY-130,04 Solv-10゜20 9th layer ( High-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl lQ mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, normal crystal, mixed twin grains, diameter/thickness Ratio 2.0) Coated silver amount 0.50 gelatin
0.80ExS-42,0XIO-'ExS-52,oxlo-'ExS-60,2X10-'ExS-73,0XIO-' ExM-110,06 ExM-120,02 ExM-80,02 Cpd-20,01 Cpd-92,0xlO-'Cpd-102,0XIO-' 5olv-10,20 Solv-20,05 10th layer (yellow filter layer) Gelatin 0.60 Yellow colloidal silver 0.05Cpd-10,
20 Solv-10,15 11th layer (low sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high Agl type,
(equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 15%, octahedral particles) Coated silver amount 0.40 Gelatin 1.00ExS-
82,0XIO-' ExY-150,90 ExY-130,09 CPd-20,01 Solv-10,30 12th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, internal high type,
Equivalent sphere diameter 1.3 μm, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 4.5) Coated silver amount 0.50 Gelatin 0
．． 60ExS-81,0XIO-' ExY-15 Cpd-2 Cpd-5 olv-1 13th layer (first protective layer) Fine grain silver iodobromide (average grain size 0° 1 mol%) Gelatin l-2 V-3 V-4 olv-3 14th layer (second protective layer) Gelatin polymethyl methacrylate particles (diameter 1.5 μm) 0.2DH-1
0,40 0 0゜0,12 0.001 0XIO-' 0,04 2゜Furthermore, to improve storage stability, processability, pressure resistance, anti-fungal and anti-bacterial properties, antistatic properties, and applicability. ,Cpd-3,C
pd-5, Cpd-6, Cpd-7, Cpd-8, P-
1, P-2, W-ISW-2, and W-3 were added.

The development process used here was carried out at 38°C under the following conditions.

1. Color development ・・・・・・・・・・・・・・・
2 minutes 45 seconds 2, bleaching...
・・6 minutes 30 seconds 3, wash with water ・・・・・・・・・・
・・・・・・ 3 minutes 15 seconds 4, established ・・・・・・
・・・・・・・・・ 6 minutes 30 seconds 5, wash with water ・・・・
・・・・・・・・・・・・ 3 minutes 15 seconds 6, stable ・
・・・・・・・・・・・・・・・ 3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4g hydroxylamine sulfate
2.4g 4-(N-Ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate 4.5g water added if bleach solution ammonium bromide 160.0g aqueous ammonia (28%) 25.0d ethylenediamine - Sodium iron tetraacetate 130g glacial acetic acid
Add 14d water
1! Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175. (Add 4.6 g of ld sodium bisulfite water
If stabilized formalin 8.0d add water 1j2 (sample 302
~307) 0.015 g/yellow colored cyan coupler R-1 for comparison was added to the third, fourth and fifth layers of sample 301.
rrf, 0.060g/nf and 0°030g/n
Sample 302 was prepared by adding f. R-1 of sample 302
Samples 303 to 307 were prepared by substituting other yellow colored cyan couplers in equal weight.

(Samples 308-310) ExC-3 and ExC of the fifth layer of samples 305-307
-6 is removed and the cyan coupler (1-1) of the present invention is replaced with 0
．． Samples 308 to 310 were prepared by adding 0.020 g/po and (1-16) at 0.130 g/po.

These samples were left for 14 days at 25° C. and 60% relative humidity (condition) and 45° C. and 60% relative humidity, and then subjected to the following color development.

Relative sensitivity was determined from the reciprocal of the exposure amount giving (fog +0.2) under conditions A and B.

Further, the color turbidity was determined by subtracting the yellow density of the unexposed area from the yellow density at an exposure amount that gave a cyan density of 2.0 under conditions.

After further exposure under conditions of 1, the following color development process was performed in the same manner except that the bleaching time was changed to 1 minute and 30 seconds, and the bleaching time was 1 minute at an exposure amount that gave a cyan density of 2° at a bleaching time of 6 minutes and 30 seconds. Cyan density was measured at 30 seconds.

From Table 3, the samples of the present invention have high sensitivity under condition A, which is the normal condition, and even under condition B, which is a forced deterioration condition as a photosensitive material storage test, there is little variation from condition A, and they have excellent storage stability. It is clear that the color turbidity is low and the color reproducibility is excellent, and even if the bleaching time is shortened, there is little difference in density from the long-time bleaching, and the desilvering property is excellent.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

UV-4: 5olv 1 Ni tricresyl phosphate olv 2: dibutyl phthalate o IV 3d Phosphate tri (2 ethylhexyl) xF 1: C* Hs 0SOs ExC 2: (i) C4F'I*0CONH ExC 4: ExC 5: ExC-6: CHCOOCH.

ExM 8: CH.

COOCa Hq ExM-11: ExY 14: ExY-15: Cpd-1: Hs C6Lff(n) Ca　L! (n) Cpd 2: ExS 1: ExS-2: C, Hl C,H.

(CHz), 5o3H-N (ci Hs)sxS 4: ExS 5: ExS-6: ExS-7: (CHz), So, Na ExS 8: H-1= CH,=CH 02 CH2 0NH CH.

CH,=CH 3O□ CH, -CONH CH.

Cpd-3: Cpd-4: H Cpd 5: Cpd pd 7 pd pd pd 0 -1 -2 Js (n)CaHqCHCHzα)QC)Iz(n)CaH
qCHCHzCOOCH3OJaJs C@F+vSOzN(CJy)CHzCOOK Copolymer of vinyl, lolidone, and vinyl alcohol (copolymerization ratio -7
0:30 [IE amount ratio J) Polyethyl acrylate (Colored Coupler-C of JP-A-61-221748 5) -2 (Colored coupler of JP-A-61-29842 6) (Colored coupler of JP-A-1 19744) -3)

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a cyan coupler represented by the following general formula [I],
Water-soluble 6-hydroxy-2-pyridone-5 is produced by a coupling reaction with an oxidized aromatic primary amine developing agent.
-Silver halide color photographic photosensitive material containing a cyan coupler capable of releasing a compound residue containing a -ylazo group, a water-soluble 2-acylaminophenylazo group, or a water-soluble 2-sulfonamidophenylazo group. material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], R_1 represents an aliphatic group, aromatic group, or heterocyclic group, Ar represents an aromatic group, and X represents a hydrogen atom or Represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer.