JPH01106055A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photography causing no color change on a white ground, even preserved for a long period or displayed after color development and bleach-fix processings of the title material by incorporating a specified coupler in at least one layer of photographic constituting layers mounted on a supporting body. CONSTITUTION:At least one layer of the photographic constituting layer mounted on the supporting body contains the coupler which has a function of allowing it to chemically inactive by chemically binding with an aromatic amine type color developing main agent. Said coupler has a sec. reaction rate constant of a range of 1.0-1.0X10<-6>l/mol.sec in the reaction of said coupler with p-anisidine and chemically binds with a residual aromatic amine type color developing main agent in pH of <=8 after the color development processing. Thus, the color photography causing no color change on the white ground, even preserved for a long period and displayed after the color development and the bleach-fix processings of said material, is obtd.

Description

Detailed Description of the Invention (Industrial Application Field) Kiwasu 1 relates to a silver halide color photographic light-sensitive material with improved storage stability, and more specifically relates to aromatic aroma present in a silver halide light-sensitive material after color development processing. The present invention relates to a silver halide color photographic light-sensitive material whose storage stability is improved by a coupler which makes a group amine color developing agent chemically inert.

(Prior Art) Silver halide color photographic light-sensitive materials consist of an oxidized product of a developer produced by imagewise exposure and development with an aromatic amine color developing agent, and a dye image-forming coupler (hereinafter referred to as coupler).
A one-dye image is formed by the reaction with. In natural color photographic materials, a combination of yellow coupler, cyan coupler and magenta coupler is usually used.

Among the processing solution components remaining in the photosensitive material after the development process, the aromatic primary amine compound as the developing agent and the compounds derived therefrom are particularly susceptible to exposure to light, heat, humidity, oxygen, etc. during long-term storage. It is known that the solidity of the image is reduced due to the influence of oxidation, and that it itself changes into a stone Buddha material due to self-coupling or interaction with coexisting substances, resulting in so-called "stain". This is a fatal drawback for color photography.

It is known that 1-aryl-3-pyrazolidone derivatives, especially their precursors, are added to the sensitive material layer for the purpose of preventing staining.
No. 258,525, No. 4゜465.762, No. 4,5
No. 22,917, JP-A No. 55-52025, No. 55-
No. 5330.

No. 57-40245, No. 57-104641, No. 5
No. 9-121328 and the like.

However, these compounds have the drawback of worsening photobleaching properties when added, and the degree of this is greater in the case of 3-alkoxycarbonyloxy-2-pyrazoline derivatives.

(Problems to be solved by the invention) As a means of solving these problems, the patent application
No. 919 discloses a method of utilizing a preservability improving compound that chemically bonds with an aromatic amine color developing agent remaining in a color photograph after processing to produce a chemically inert and substantially colorless compound. was suggested.

The present invention further develops the above-mentioned method and provides a silver halide color photosensitive material that provides a color photograph in which the white background does not discolor even when stored and displayed for a long period of time after color development, bleaching, and fixing. The purpose is to

Another object of the present invention is to provide a color photograph in which deterioration of a dye image due to residual color developing agent carried into a light-sensitive material after color development, bleaching and fixing processes is prevented.

Another purpose is to process liquids in a running state, processing liquids with a small amount of water washing or non-water washing processing liquids, and processing liquids in which a large amount of processing liquid components are brought into the photosensitive material, such as color developing liquids that do not substantially contain benzyl alcohol. Also provides a color image forming method for color photosensitive materials that prevents side effects such as image deterioration and staining caused by aromatic amine color developing agents that remain even after processing with processing liquids that place a burden on color development. It's about doing.

(Means for Solving the Problems) As a result of various studies, the present inventors have found that the purpose of the above-mentioned product is to chemically bond with the aromatic amine color developing agent remaining in the photosensitive material after color development processing. It has been found that this can be effectively achieved by incorporating a coupler into the sensitive material which chemically inactivates the developer.

That is, the present invention provides a halogen compound characterized in that at least one of the photographic layers on the support contains a coupler having a group that chemically bonds with an aromatic amine color developing agent to make it chemically inactive. The present invention provides a silver oxide color photographic material.

In the present invention, preferably the coupler is.

2 (80'C
) is in the range of 1.0 fL1 mol·sec to 1.0×1 O -611 mol·sec, and the coupler chemically bonds with the aromatic amine color developing agent remaining after the color development process under conditions of pH 8 or less.

The aromatic amine color developing agent used in the present invention includes aromatic primary and secondary amine compounds, and more specifically includes phenylene diamine compounds and aminophenol compounds. Representative examples include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, and 3-methyl-4-amino-N-ethyl. -N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methoxyethylaniline, 4-methyl-2-amino-N,N-diethylaniline, 4-methyl-2-amino-N-ethyl-N-β-methanesulfonamide aniline, 2-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-
Butylamino-N,N-diethylaniline, 3-methyl-4-acetylamino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-methanesulfonamide-N-ethyl-N-β-methane Sulfonamide ethylaniline, 3-methyl-4-benzylamino-N-ethyl-N-β-methanesulfonamide ethylaniline,
3-Methyl-cyclohexylamino-N-ethyl-N-
Methylaniline and its sulfates, hydrochlorides, phosphates, p-toluenesulfonates, tetraphenylborates, p-(t-octyl)benzenesulfonates, as well as 0-aminophenol, p- Aminophenol, 4-amino-2-methylphenol, 2-amino-3
-methylphenol, 2-amino-3-methylphenol, 2-hydroxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, F. A. Mason, "Photographic Processing Chemistry", Focal Press (1966) (1, F. A. Mason
.

”Photographic Processing
Chemistry”, FocalPress) 2
Examples include those described in pages 26 to 229, US Pat. No. 2,193.015, US Pat.

A preferred coupler having the function of chemically bonding with an aromatic amine developer to inactivate the developer in the present invention can be represented by the following general formula (I).

General formula (I) Cp+Z) 5i.

In the formula, Cp represents a coupler residue and includes dimeric, oligomeric, and polymeric couplers. Z represents a group that chemically bonds with the aromatic amine developer.

The sentence indicates an integer greater than or equal to 1, and when Z is greater than or equal to 2, Z may be the same or different.

The coupler residue represented by CP may be substituted with other substituents in addition to the substituent represented by Z. Cp may be colorless, or it is preferable that it forms a dye, and Cp reacts with an oxidized product of an aromatic amine developer to form a photographically useful group (e.g., a development inhibitor, a dye, a ligand). , bleach accelerators, etc.), but those that do not release are preferred.

Preferred examples of the coupler residue Cp include phenolic and naphthol cyan couplers;
Examples of magenta couplers include 5-pyrazolone, pyrazoloazole, indacylon, and cyanoacetyl magenta couplers, and examples of yellow couplers include α-pivaloylacetanilide and α-benzoylacetonide anilide couplers.

2 represents a group that reacts with an aromatic amine developer, and is substituted by at least one group on the coupler residue Cp.

Although Z may be a group capable of leaving during the coupling reaction with the oxidized aromatic amine developer (hereinafter referred to as a leaving group), it is preferably substituted at a position other than the coupling active position.

A more preferred coupler used in the present invention is represented by the following general formula (II).

-Ship type (n) (R, (A R2→Cp+I+3÷day, R4).

- In the boat formula (II), Cp has the same meaning as the coupler residue 15Cp in the general formula (I).

R-(-A÷-R- and R→A sum; R3-1p2
4 represents Z in the -ship formula (I) 0m and n represent an integer of 0 or more whose sum is the sentence in general formula (1), R1 is an aliphatic group, an aromatic group, or Represents a telocyclic group.

R2 and R3 represent groups connecting coupler residues Cp and A. Among these, R2 represents a group that reacts with an aromatic amine developer and leaves the group.

R4 represents a group that reacts with an aromatic amine developer and leaves the group.

A represents a group that reacts with an aromatic amine developer to form a chemical bond. p represents 1 or 0, and q is synonymous with p, but it is not necessary that p=q.

Here, R1 and R2 and R3 and R4 may be bonded to each other to form a cyclic structure.

- The six units in ship type (II) will be explained in more detail.

The aliphatic group R1 preferably has 1 to 32 carbon atoms,
It represents an aliphatic hydrocarbon, and represents a linear, branched, or cyclic alkyl group, aralkyl group, alkenyl group, or alkynyl group, and may be further substituted with a substituent.

The aromatic group R1 refers to a carbocyclic aromatic group (having 6 to 6 carbon atoms).
20 is preferred. For example, phenyl, naphthyl) and petrocyclic aromatic groups (of 4 to 10 carbon atoms or preferably 0, such as furyl, thienyl, pyrazolyl, pyridyl, indolyl), and may be monocyclic or fused ring systems ( For example, benzofuryl, phenanthridinyl) may be used. Furthermore, these aromatic rings may have a substituent.

The heterocyclic group referred to in R1 is preferably a group having a 3- to 10-membered ring structure composed of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a hydrogen atom, and the heterocyclic ring itself is a saturated ring. It may be an unsaturated ring, or it may be loosely substituted with a substituent (for example, a coumanyl group, a pyrrolidyl group, a pyrrolinyl group, a morpholinyl group).

R2 represents a group that connects the coupler residue Cp and (A), and represents a group that reacts with an aromatic amine developer and leaves, R2 represents -( A) A group that bonds with - (for example, an aminoalkylene group, an aminoarylene group, an oxyalkylene group, an oxyarylene group, a thioalkylene group, or a thioarylene group. The number of carbon atoms thereof is the same as in the case of R3 below.) is preferred.

The group connecting the coupler residues Cp and (A)q represented by R3 may be any group commonly used in the art, such as an alkylene group having 1 to 30 carbon atoms, a group having 6 carbon atoms, Arylene group having ~16, carbon number 7
Aralkylene group having ~17 carbon atoms, heterocyclene group having 3 to 10 carbon atoms, # elementary atom, sulfur atom, amino group, carbonamino group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, sulfa moylamino group, carbamoyloxy group, oxycarbonamide group, acyl group, alkoxy group, carboxy group,
It includes a sulfone group and a linking group formed by a combination of these linking groups.

R4 represents a group that reacts with an aromatic amine developer and leaves -(A
) a group bonding with - (e.g. 3- and lazolyloxy,
Examples include 3H-1,2,4-diazoline-5-oxy, aryloxy, alkoxy, alkylthio, arylthio, and substituted N-oxy, and the number of carbon atoms thereof is the same as in the case of R3. ) or a halogen atom is preferred.

A represents a group that reacts with an aromatic amine developer to form a chemical bond, and includes an atom with a low electron density. Here, L is a group bonding to R or R3, an alkylene group,
-〇-1-S-1 represents a single bond, where L' and L'' are the same or different. Here, R'' is a hydrogen atom, an aliphatic group (e.g. methyl, isobutyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), aromatic groups (
For example, phenyl, pyridyl, naphthyl), heterocyclic groups (
(e.g. piperidyl, pyranyl, furanyl, chromanyl)
, represents an acyl group (eg, acetyl, benzoyl), a sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), and the like.

Preferably, L is an alkylene group, -0-1R' and R
” may be the same or different, and R1 or L', respectively.
Of these, the group represented by R1 is particularly preferred.

Y is an aromatic amine developer represented by R in the general formula (■)
+A-) -R- and R LiaoAkuR3-1
Table 03 lists the groups that promote addition to the group to which R2 is attached: hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group,
It represents a sulfonyl group and includes the specific examples of each group exemplified in R'', and G and 03 may be bonded to each other to form a cyclic structure.

Particularly preferred Y is an oxygen atom or a sulfur atom.

Y' represents the same meaning as Y.

A more preferable example of A is -alkylene-〇-1 general formula (
When p=o in II), R2 represents a linking group that is electron-withdrawing to R1, for example R, -0S02R
2° etc. are preferred, where -0SOR' represents -R2.

In the general formula (II), when q-modulus is 0, R4 represents a group that is electron-withdrawing to R3, for example, a halogen atom, -R3-O3O2-R4°, etc. are preferable, where -o
so□-R4° represents R4.

- In the ship formula (n), q is preferably l.

More preferred couplers for use in the present invention are represented by the following general formulas (m) to -general formula (2).

General formula (m) H General formula (rV) H General formula (V) General formula (Vl) General formula (■) Yl, -Ra in ship formula (IV), R9, R9°
and R, - R1□, R1□, R and Y3 in the boat type (V), - R, Za and z in the boat type (Vl)
substituents on b and Y4. -At least one of Q and Y in the ship formula (■) (hereinafter referred to as substituents on the ship formulas (m) to (■)) is a group represented by Z in the general formula (I). do.

General formula (III) to (V
Each substituent on I is defined as follows.

R5, R8 and R9 represent an aliphatic, aromatic or heterocyclic group.

R6'R7'' R10 represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, an alkoxy group or an acylamino group.

R9° has the same meaning as a hydrogen atom or R9. r represents O or l.

R13 represents a phenyl group.

R11 has the same meaning as an acyl group or R13.

R1□ is a hydrogen atom, an aliphatic or aromatic acyl group,
Represents an aliphatic or aromatic thrulenyl group.

R14 represents a hydrogen atom or a substituent.

Za and zb are methine, substituted methine, -N= or -
Represents NH-.

Q represents a substituted N-phenylcarbamoyl group.

Yl, Y2, Y3, Y4 and Y5 represent a hydrogen atom or a leaving group.

In the general formula (III) and the -ship formula (IT), R6 and R7 and R9 and R10 may each form a 5.6- or 7-membered ring.

The substituents in the above general formulas (m) to (■) may further have a substituent, and such optionally substituted substituents include an alkyl group, an aryl group, a heterocyclic group, Alkoxy groups (e.g. methoxy, 2-methoxyethoxy, tetradecyloxy, aryloxy groups (e.g. 2
．． 4-di-tart-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 4-butanesulfonamidophenoxy), acyl groups (e.g. acetyl, benzoyl), ester groups (e.g. ethoxycarbonyl,
2.4-di-tert-amylphenoxycarbonyl,
acetoxy, benzoyloxy, butoxysulfonyl,
toluenesulfonyloxy), amide groups (e.g. acetylamino, butanesulfonamide, dodecylbenzenesulfonamide, dipropylsulfamoylamino),
Carbamoyl groups (e.g. dimethylcarbamoyl, ethylcarbamoyl), sulfamoyl groups (e.g. butylsulfamoyl), imide groups (e.g. succinimide, hydantoinyl), ureido groups (e.g. phenylureido, dimethylureido), sulfonyl groups (e.g.
(methanesulfonyl, carboxymethanesulfonyl, phenylsulfonyl), aliphatic or aromatic thio groups (e.g., butylthio, phenylthio), citroxyl groups, cyano groups, carboxyl groups, nitro groups, sulfo groups, halogen atoms, etc. Examples include groups. In addition, when two or more such substituents are present, they may be the same or different from each other.

Furthermore, FL5. R6, R7 or Yl; R8°R9,
Rlo or “2; R11, R12, R13 or Y3
; R14, substituents on Za and zb or Y4. Q or Y5 may form a dimer or more multimer.

Unless otherwise specified herein, aliphatic 2! i(
The carbon number of the alkyl group, alkoxy group, alkenyl group, etc. is preferably 1 to 22, and the carbon number of the aromatic group (aryl group, aryloxy group, etc.) is preferably 5 to 1.
It is 6.

Six groups of general formulas (m) to -general formula (2) in cases where Z does not apply will be explained in detail.

- Yl, Y2 in ship formula (III) ~ - general formula ■).
Y3. When Y4 and Y5 represent a leaving group, the leaving group is an aliphatic group, aromatic group, heterocyclic group, aliphatic/aromatic or hetero Ring sulfonyl groups, groups that bond with aliphatic/aromatic or heterocyclic carbonyl groups, halogen atoms, aromatic azo groups, etc., and aliphatic, aromatic or heterocyclic groups included in these leaving groups are ,R
5 may be substituted with the substituents allowed in R5, and when these substituents are two or more, they may be the same or different, and these substituents further have a substituent allowed in R5. You may do so.

Specific examples of coupling-off groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), alkoxy groups (e.g. ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxylpropyloxy, methylsulfonylethoxy), aryloxy groups (e.g. 4-chlorophenoxy, 4-methoxyphenoxy,
4-hydroxyphenoxy), acyloxy groups (e.g. acetoxy, tetrazocalyloxy, benzoyloxy), aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (e.g. dichloro acetylamino, heptafluorobutyrylamino), aliphatic or aromatic sulfonamide groups (e.g. methanesulfonamino,
p-toluenesulfonylamino), alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy 2!1Si (e.g. phenoxycarbonyloxy), aliphatic/aromatic or heterocyclic thio groups (e.g. ethylthio , phenylthio, tetrazolylthio), carbamoylamino groups (e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered
member nitrogen-containing heterocyclic groups (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-
2-oxo-1-pyridyl), imide groups (e.g. succinimide, hydantoinyl), aromatic azo groups (e.g. phenylazo), etc., and these groups are generally substituted with groups allowed as substituents for R5. Also, as a leaving group bonded via a carbon atom, there is a bis-type coupler obtained by condensing a four-equivalent coupler with an aldehyde or a ketone.The leaving group of the present invention is a development inhibitor,
Preferred combinations of leaving groups for each type, which may or may not contain photographically useful groups such as development accelerators, will be described later.

In general formula (III) and -ship formula (IT), R5,
Examples of aliphatic groups for R8 and R9 include methyl group, butyl group, tridecyl group, cyclohexyl group, and allyl group; examples of aryl groups include phenyl group and naphthyl group; examples of heterocyclic groups include Examples include 2-pyridyl group, 2-imidazolyl group, 2-furyl group, and 6-quinolyl group. These groups may be further substituted as described above.

- When R6 in the boat formula (m) and Rlo in the general formula (rV) are substituents that can be substituted, they may be substituted with the optional substituents described for R5.

R6 in general formula (m) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group. group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, methoxymethyl group, and the like.

In general formula (m) and -ship formula (IT), Yl and Y2 are hydrogen atoms or the above-mentioned coupling-off groups (those listed for Y1 to Y5 in -ship formula (m) to (■)). .

These leaving groups may or preferably do not contain photographically useful groups.

Preferred examples of the cyan coupler represented by the above formula (m) or (IV) are as follows.

- In the boat formula (m), preferred R5 is a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group.

In general formula (m), R6 is preferably an alkyl group having 2 to 15 carbon atoms or a methyl group having a substituent having 1 or more carbon atoms, and examples of the substituent include an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, and an alkyl group. An oxy group is preferred.

- In the boat type (III), R6 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (m), R7 is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred.

In the general formula (ff), R8 is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group,
Sulfonyl group, sulfamide group, oxycarbonyl group,
More preferably, it is an ary-)Lt group substituted with a cyano group.

When R10 and R9 do not form a ring in general formula (1'V), R9 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R10 is Preferably it is a hydrogen atom.

In general formulas (m) and (N), preferable Yl and Y2 are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In general formula (m), Yl is preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

In general formula (IV), when r=0, Y2 is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

The substituents in general formula (V) will be explained. R1 represents an acyl group or a substituted or unsubstituted phenyl group.

To explain R11 in detail, the acyl group of R11 is an aliphatic acyl group or an aromatic acyl group.

Examples include heterocyclic acyl groups, which may be substituted with the optional substituents described for R5.

The substituent in the substituted or unsubstituted phenyl group of Rtt may be any of the optional substituents described for R5. Furthermore, the number of substituents on the phenyl group is 1 to
It can take any number of 5, and each substituent may be the same or different.

R1□ particularly preferably represents a substituted phenyl group.

R1□ is a hydrogen atom, an aliphatic or aromatic acyl group,
It represents an aliphatic or aromatic sulfonyl group, and when R1□ is a substitutable substituent, it may be substituted with the optional substituent described for R5.

R1□ particularly preferably represents a hydrogen atom.

R13 represents a substituted or unsubstituted phenyl group, and has the same meaning as the substituted or unsubstituted phenyl group of R1□.

Y3 in general formula (V) each represents a hydrogen atom or a coupling-off group, examples of which include a halogen atom (e.g. fluorine atom, chlorine atom), an alkoxy group (
For example, methoxy, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, methylsulfonylethoxy), aryloxy groups (e.g., phenoxy, 4-
Methylphenoxy, 4-methoxyphenoxy, 4-t-
Butylphenoxy, 4-carboethoxyphenoxy, 4
-cyanophenoxy, 2,4-dichlorophenoxy),
Acyloxy groups (eg, acetoxy, tetrazocallyloxy), amide groups (eg, dichloroacetamide, benzenesulfonylamide, trifluoroacetamide), imide groups (eg, succinimide, phthalimide).

5,5-dimethyl-2,4-dioxoxazolidinyl, l-benzyl-5-ethoxyhydantoinyl), nitrogen heterocyclic groups (e.g. pyrazole, 4-chloropyrazole, 3,5-dimethyl- 1゜2.4-triazole-2
-yl, imidazole, 3-chloro-1,2,4-triazol-2-yl), alkylthio groups (e.g. ethylthio, dodecylthio, l-ethoxycarbonyldodecylthio, 3-phenoxypropylthio, 2-(2,4 −
tert-amylphenoxy)ethoxy), arylthio groups (e.g. phenylthio, 2-butoxy-5-
tert-octylphenylthio, 4-dodecyloxyphenylthio, 2-(2-ethoxyethoxy)-5-t
ert-octylphenylthio, 3-pentadecyl phenylthio, 3-octyloxyphenylthio, 3-(N
, N-didodecylcarbamoyl)phenylthio, 2-octyloxo-5-chloro-phenylthio), heterocyclic thio groups (e.g. 1-phenyltetrazole-5-thi, l-ethyltetrazole-5-thio, 1-dodecyl −
1,2,4-triazole-5-thio).

Among these gI groups, preferred are a hydrogen atom, an arylthio group, an alkylthio group, and a group that leaves at a nitrogen heterocyclic group, and particularly preferred are an arylthio group and a nitrogen heterocyclic group.

Among the magenta couplers represented by the general formula (V), a particularly preferred coupler is represented by the following general formula (vA).

General formula (vA) In general formula (vA), Ml is a straight chain, branched or cyclic alkyl group having 5 to 29 carbon atoms, preferably 7 to 23 carbon atoms (e.g. heptyl, nonyl, undecyl, tridecyl,
heptadecyl, 2-ethylhexyl, 2-hexyldodecyl, 4-hexylcyclohexyl, 3-pentadecylcyclohexyl, norbornyl, 7,7-dialkylnorbornyl, etc.).

M2 represents an alkoxy group having 1 to 18 carbon atoms or a halogen atom (eg, fluorine, chlorine, bromine), preferably a halogen atom.

M3 is a halogen atom (e.g. fluorine, chlorine, bromine),
In the alkyl group or alkoxy group, M4 and M5 may be the same or different, and each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group, a cyano group, nitro group or acylamino group, preferably a halogen atom.

The substituents in general formula (Vl) will be explained. R14 represents a hydrogen atom and a substituent. To explain R14 in detail, R14 represents a hydrogen atom, an aliphatic group, a U (e.g., straight chain aliphatic, aralkyl, alkynyl, cycloalkyl, cycloalkenyl), an aryl group (e.g., phenyl). , naphthyl), heterocyclic groups (e.g. 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazoyl), which are substituted with the optional substituents roughly described in R5. Examples of aliphatic groups include methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 2-methanesulfonylethyl, 3-(3-pentadecylphenoxyl)propyl, 3- (4-(2
-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido)phenyl)propyl, 2-ethoxytridecyl, cyclopentyl, 3-(2,4-di-t-amylphenoxy)propyl, and the aryl group includes Examples of 1 include phenyl, 4-t-butylphenyl, 2.4-di-t-amylphenyl%4-tetradecanamidophenyl, and examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyrimidyl, 2-
Examples include benzothiazoyl.

R14 can also be a cyano group, an alkoxy group (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy), an aryloxy group (e.g. phenoxy,
2-methylphenoxy, 4-t-butylphenoxy),
Acylamino groups (e.g. acetamide, benzamide,
Tetradecanamide, α-(2,4-di-t-amylphenoxy)butyramide, δ-(3-t-butyl-4-
hydroxyphenoxy)butyramide, α-[4-(4
-hydroxyphenylsulfonyl)phenoxy]decaneamide), anilino groups (e.g. phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5-[α
-(3-t-butyl-4-hydroxyphenoxy)dodecanamido]anilino), ureido groups (e.g. phenylureido, methylureido, N,N-dibutylureido), sulfamoylamino groups (e.g. N,N-dipro- pyrsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio groups (e.g. methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-(4
-7-butylphenoxy)propylthio), arylthio groups (e.g. phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxylphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino groups (e.g. methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide groups (e.g. methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p- toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-butylbenzenesulfonamide), carbamoyl groups (e.g. N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, N-(3-(2,4
-di-t-amylphenoxy)propyl)carbamoyl), sulfamoyl group (N-ethylsulfamoyl, N
, N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), sulfonyl group (methanesulfonyl, octanesulfonyl, benzene sulfonyl, toluenesulfonyl), alkoxycarbonyl groups (methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), peterocyclic oxy groups (e.g.
l-7enyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy groups (e.g. acetoxy), carbamoyloxy groups (e.g. N-methylcarbamoyloxy, N-phenylcarbamoyloxy),
Silyloxy groups (e.g. trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino groups (e.g. phenoxycarbonylamino), imide groups (e.g. N-succinimide, N-phthalimide,
3-octadecylsuccinimide), peterocyclic thio group (
For example, benzothiazolylthio, 2,4-diphenoxy-1,3,5-)lyazole-6-thio, 2-pyridyl), sulfinyl groups (e.g. dodecanesulfinyl, 3
-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl groups (e.g. phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl groups (e.g. phenoxycarbonyl), acyl groups (e.g. acetyl,
3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl).

Among these groups represented by R14, preferable groups include aliphatic groups, alkoxy groups, aryloxy groups, alkoxycarbonylamino groups, and carbamoylamino groups, and more preferable groups include aliphatic groups, alkoxy groups,
It is an aryloxy group.

Y4 in general formula (VI) each represents a hydrogen atom or a coupling-off group, and examples thereof are the same as those for Y3 in general formula (V).

Among these leaving groups, preferred are those that leave at a halogen atom and a mercapto group, and particularly preferred are a fluoro group, a chloro group, a bromo group, and an arylthio group.

Za and Zb in general formula (Vl) are methine, substituted methine-N
= or -NH- group. - Particularly preferable couplers among the ship type (VI) magenta couplers are as follows - ship type (VI)
VIA) to (■,).

General formula (■A) -Ship formula (■8)-
Vessel type (VIC) - Vessel type (■,) Among these, particularly preferred turnips and lars are (■B) and (
VI). In the general formula (■A), N1 and N2 may be the same or different from each other. General formula (VI)
N1 and N2 in (VIC) are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic group, an acyloxy group, a carbamoyloxy group, and a silyloxy group, respectively. , sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone It represents an amide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

R14, N1. N2 or Y4 may be a divalent group to form a bis body.

More specifically, R14, N1 and N2 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom), alkyl groups (e.g. methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4 -G-t
-amylphenoxy)propyl, allyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonyl-ethyl, cyclopentyl, benzyl), aryl groups (e.g. phenyl, 4-t-butylphenyl,
2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), heterocyclic groups (e.g. 2-furyl, 2
-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano groups, alkoxy groups (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy (e.g. phenoxy, -methylphenoxy, 4-
t-butylphenoxy), heterocyclic oxy groups (e.g.,
2-benzimidazolyloxy), acyloxy groups (e.g. acetoxy, hexadecanoyloxy), carbamoyloxy groups (e.g. N-phenylcarbamoyloxy, N-ethylcarbamoyloxy), silyloxy groups (e.g. trimethylsilyloxy), sulfonyloxy groups (e.g. dodecylsulfonyloxy), acylamino groups (e.g. acetamide, benzamide, tetradecanamide, α-(2,4-di-t-amylphenoxy)butyramide, -(3-1-butyl-4-hydroxyphenoxy) ) butyramide, α-(4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide), anilino group (e.g. phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5-dodecyl Oxycarbonylanilino, N-acetylanilino, 2-chloro-5-(α-
(3-t-butyl-4-hydroxyphenoxy)dodecanamido)anilino), ureido groups (e.g. phenylureido, methylureido, N,N-dibutylureido), imide groups (e.g. N-succinimide, 3-benzylhydan toynyl, 4-(2-ethylhexanoylamino)phthalimide), sulfamoylamino groups (e.g., N,N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio groups ( For example, methylthio.

Octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio.

3-(4-t-butylphenoxy)propylthio), arylthio groups (e.g. phenylthio, 2-butoxy-
5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), heterocyclic thio groups (e.g.
2-benzothiazolylthio), alkoxycarbonylamino groups (e.g., methoxycarbonylamino, tetradecyloxycarbonylamino), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino,
2.4-tert-butylphenoxycarbonylamino), sulfonamide groups (e.g. methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t- butylbenzenesulfonamide), carbamoyl group (e.g. N-
Ethylcarbamoyl, N,N-dibutylcarbamoyl,
N-(2-dodecyloxyethyl)carbamoyl, N-
Methyl-N-F decylcarbamoyl, N-(3-(2,
(4-di-tert-amylphenoxy)propyl)carbamoyl), acyl groups (e.g. acetyl, (2゜4-
di-tert-amylphenoxy)acetyl, benzoyl), sulfamoyl groups (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2
-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), sulfonyl groups (e.g. methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl groups (e.g. , octanesulfinyl, dodecylsulfinyl, phenylsulfinyl), alkoxycarbonyl (e.g. methoxycarbonyl, butyloxycarbonyl, dodecylcarbonyl, octadecylcarbonyl), aryloxycarbonyl (e.g. phenyloxycarbonyl, 3-pentadecyloxy-carbonyl) represents.

N1. Among these groups represented by N2, particularly preferred are an alkyl group and an aryl group.

In the general formula (■), N-phenylcarbamoyl! Q
The substituents of the phenyl group can be arbitrarily selected from the group of substituents permissible for R5, and when there are two or more substituents, they may be the same or different.

Preferred examples of Q include the following general formula (■A).

General formula (■A) (In the formula, G4 represents a halogen atom or an alkoxy group, and G5 represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent.

G6 represents an alkyl group that may have a substituent,
) Examples of substituents for G5 and G6 in general formula (■) include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, dialkylamino groups, and heterocyclic groups (e.g. N-morpholino, N-piperidino, Typical examples thereof include 2-furyl), a halogen atom, a nitro group, a hydroxy group, a carboxyl group, a sulfo group, and an alkoxycarbonyl group.

Preferred leaving groups Y5 include groups represented by the following general formulas from (■8) to (■Iρ).

General formula (■B) 07 G7 represents an optionally substituted aryl group or heterocyclic group.

General formula (■C) General formula (■,)G a
, G9 are each a hydrogen atom, a halogen atom, a carboxylic acid ester, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl represents a group or a heterocycle, and these groups may be the same or different.

It represents the general formula (■,) or a nonmetallic atom required to form a 6-membered ring.

In the general formula (vI[E), preferably (■ρ~(■1
1) is mentioned.

General formula (■F) General formula (■6) General formula (■1ρ In the formula, Glo and G1 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group, and G1□, G13 and G14 each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group, and W3 represents an oxygen or sulfur atom.

Among the methods in which the aromatic amine developer remaining in the photosensitive material after the development process and the coupler of the present invention are chemically bonded and inactivated, a typical method is a substitution reaction, which is the -ship method (n). In m=1. Taking the case of n=0 as an example, it can be expressed by reaction formula (1), and taking the case of m=01n=1 as an example, it can be expressed by reaction formula (2), but it is not limited to these. Not.

Reaction formula (1) Reaction formula (2) The general formula of the medicine is shown.

Among the couplers represented by the general formula (I) that react with the aromatic amine developer remaining in the photosensitive material after the development process, preferred are 2 (80
°C) is 1,01ltaol-sec ~1XlO-”J
The coupler is in the range of L/mol・sec, and more preferably kz (80°C) is LX 10-2JL/
mol-sec ~IX 10-51 /mol-sec
It is a coupler that is in the range of e. In general, if 2 is too large, the coupler itself becomes unstable and will react with gelatin or water and decompose.On the other hand, if 2 is too small, side effects of the aromatic amine developer remaining in the photosensitive material can be prevented. I can't.

The measurement of the second-order reaction rate constant of 1 can be performed as follows.

Dissolve p-anisidine and the coupler of the present invention in phosphoric acid trinonyl ester so that each concentration is 0.03 mol/1.Next, 10 ml of this mixed solution is heated in a constant temperature bath at 80°C to speed up the reaction. tracked by liquid chromatography,
Obtain the second-order reaction rate constant.

Representative examples of the group represented by (+A+-TR1) in general formula (n) are shown below. 6) (Any 7) (Any 8) (Any 9) (Eng. 1-101 (I. 11) -COC3H7(n' (II-121 (Eng. 1-13) (II-14) -coc1aH3-y (nl (Any 15) O (Any 16) (Any 17) (Any 18) 2 Hs (Any 20) O -COC8H17(n l (Any 21) 05H1l"") (II-22+ (Engineering 1-231 (II-24) ) (II-25) (Any26) -C(:, (tl (Engineering 1-271 (Any28) (Any29) (Any30) -5OCR H3 Below, (-+A-+) in general formula (■) The following are representative examples of R4 in the group represented by -TR4), but the present invention is not limited to these.

(Any 32) (Any 33) (Any 34) (Any 35) (Any 36) (Any 37) (Any 38) (II-391 (Any 40) (Any 41) CH3 (I Any 42) " (Eng. -431 (II-44) (Any46) (Any47) (Any48) (Any49) (Any50) (Any51) (Any53) (Any54) (Xny56) (Any57) (Eng. l-581 (II-591 (Any611 (II-621 10 (Any 71) L (II-72] (Eng. 1-731 (Any 74) (Any 75) 〇- (Any 76) (Any 77) (Any 78) (Any 79) (Any 80) (Any 81 ) (Any82) (Any83) Cλ (Inie84) (Any85) (Any86) (II-871 (Inie88) (II-891 (II-901 (II-911) 921 CO2C2H5 (Any 93) 〇- (Any 94) I2 (Any 95) (Any 96) 〇- (Any 97) (Eng. 1-981 (■Ni 99) 〇- 02CH3 (Any 100) 〇- (Any 101) S0311N(C2H5)3 (Eng 1-102') (Eny 103) (Eny 104) (Eny 105) 藝H3 (Eny 106) (Eng 1-107) (Eny 109) (Eny 110) (Eny 112) (II -113) (Any114) (Any115) (Any116) (Engineering 1-1181 (Any119) Representative examples of R4 in the group represented by (-(-A+7R4) in general formula (II) are shown below. However, it is not limited to these.

(Eng. 1-1211 C9 (I-122) Br (Eny-123) 1■ (Eny-124) (II-1251 -OSOCR (II-1261 -OSOCF (Eny-127) Below, the coupler represented by the general formula (1) Specific examples will be shown, but the invention is not limited to these.

(Il[-1) (l[-2) (I-3) ([-5) (lit-('; ) (In-7) (m-9) Q (IN-10) (III -12) (wt ratio) (III-13) (wt ratio) x#/z= 55/4015 (In-t5) (IN-16) Shi! (ml-18) H (It-21) I (Iff -22) (I-23) H Specific examples of the coupler represented by the general formula (■) are shown below, but the invention is not limited thereto.

(IV-1) H (IV-2) (IV-3) (IV-4) (IV-5) (IV-6) (IV-7a) (IV-7b) (IV-8) (IV- 9) (IV-10) (IV-11) (■-12) 0M (IV-13) fi+ (IV-14) (IV-15) n sweet (IV-16) (It'-17) (IV- 18) (wt ratio) (IV-19) (IV-21) ([V-22) (■-24) (IV-25) l-1 u-sit-t3 (L27) (IV-28) (IV -29) (IV-31) (IV-32) (IV-33) C■-34) (IV-35a) (IV-3sb) (■~36) (IV-38) (IV-40) ([ V-41) ”'C16H33S large Nbe SC, d(33”'(■-4
2) (wt ratio) (IV-43) x/y=50150 (w ratio) (TV-45) (IV-46) (IV-47) Below are specific examples of couplers represented by the general formula (Vl) However, it is not limited to these.

(V-1) (”, fl (V-4) D (V-5) U (V-6) l (V-7) (V-8) (V-10) (V-11) (
wt ratio) (V-13) (V-14) (V-15) C (V-17) (V-20) Ca (V-21) (V-22) Su (V-23) Below are the general Specific examples of Cuffrey represented by the formula (■) are shown below, but the invention is not limited thereto.

(W-1) (M-2) CI, (3 (W-4) 0'l-8) ()T-9) (Si-10) 01-tt) (■-12) Ci! (■-13) (ST-H) (■-1,5) (■ 16) 8H17 (wt ratio) (■-19) (wt ratio) (■-20) (wt ratio) (■-21) ( W-23) (M-25) (■-27) H3 (Sl-28) (■-3t) (~ff-33) (■-34) (~T-35) (W-36) (W- 37) (wt ratio) (Iff-38) ('t)-39) x/y=50150 (wt ratio) Specific examples of couplers represented by the general formula (Sl) are shown below, but are limited by these. It's not a thing.

(■-1) (■-2) (■-3) Shitt3 (■-4) C.O. Su11 (■-5) (■-7) (■-8) (■-9) (■-10) (■-11) (■-12) (■-13) (■-14) (■-15) (■-16) (■-17) O (■-18) O (■-19) H (■-20) (■-21) (■-22) (■-23) (■-24) (■-25) (■-26) (■-27) (■-28) fl (■-29) (■-30) (■-31) (■-32) Self, □H25 (■-33) (■-34) (■-35) (■-36) (■-37) Ct ()Y-38) (■-39) Engineering 0=0 (■-42) (■-43) Synthesis examples of typical compounds of the present invention are shown below.

Synthesis example 1. (Synthesis of Exemplified Compound W-3) A
BE F
c Synthesis of 4-t-octylphenyl hexadecanoate (F) 4-t-octylphenol (E) 20g (0,099
mol) to 200m of acetonitrile! , triethylamine 17d (0.12 mol) was added and dissolved, and the mixture was stirred at 0°C. To this, 32.6 g (0
, 119 mol) was added dropwise. After stirring at 25°C for 11 hours, acetonitrile was distilled off, and ethyl acetate and water were added to the residue to separate 1 liquid. The ethyl acetate layer was washed once with saturated brine, and then diluted with sodium sulfate. Glauber's salt was filtered off, ethyl acetate was distilled off, and the product was purified using column chromatography. White crystal, yield 144
g, yield 100% Synthesis of 2-hexadecanoyloxy-4-t-octyl-benzenesulfonic acid chloride (G) Hexadecanoic acid 4
-t-cutylphenyl (F) (0,090 mol)
200 ml of methylene chloride was added and dissolved, and the mixture was stirred at 0°C. To this, chlorosulfonic acid 6,58d (0,99
(mol) was added dropwise. After stirring at 25°C for 7 hours, methylene chloride was distilled off, and the residue was mixed with 120d of dimethylacetamide,
120 ml of acetonitrile was added and dissolved, and 27.6 ml (0.30 mol) of phosphorus oxychloride was added dropwise at 25°C.

311! After stirring for 30 minutes, the mixture was poured into ice water, extracted twice with chloroform, and the chloroform layer was washed once with saturated brine and dried over sodium sulfate. The Glauber's salt was filtered to remove chloroform and purified by column chromatography. Oily substance.

Yield 30.2g, yield 61.8% Synthesis of C Mixture of A and phthalhydrazide (content of A 54%) 2
Add 500 g of dimethylacetamide to dissolve 50 g (A; 0.6:1 mole) and dissolve 8280 g (0,
79 mol) was added dropwise, then triethylamine 88d (0
, 6:1 mol) was added dropwise. After stirring at 10°C for 30 minutes, 750ml of ethyl acetate and 750ml of water were added. concentrated hydrochloric acid 50
m! was added, and the insoluble matter was filtered out and the liquid was separated. 200 ml of hexane was added to the ethyl acetate layer, washed four times with 5% saturated brine, and the hexane and ethyl acetate were distilled off. This was crystallized from ethyl acetate-hexane. F) Brown crystals, yield, 1
261 go Yield 78, 4% Synthesized amount of D: Iron 7.8 g (0.14 mol), ammonium chloride 0.75 (0.014 mol), acetic acid 0.80 d
(0,014 (nyl), water 391 isopropanol 19
After heating and stirring 5 ml of the mixture for 30 minutes under reflux, CI
5 g (0,028 mol) was added and the mixture was further heated under reflux for 45 minutes. This was filtered using Celite as a filter aid, and the filtered material was washed with isopropanol. The filtrate and washing solution were combined, the isopropanol was distilled off, and the mixture was recrystallized from acetonitrile-ethyl acetate. FI brown crystals, yield 11-7 g, yield 84.5% Synthesis of Exemplary Compound VI-3 l t , o g (0,022 mol), 55 ml of tetrahydrofuran, 33 ml of dimethylacetamide,
Add 2.0d (0,024 mol) of pyridine and dissolve.
"t" 013 g (0,024-T: JL
, ) was added dropwise and stirred at 25°C for 18 hours, then tetrahydrofuran was distilled off, ethyl acetate was added, the mixture was washed 22 times with saturated brine, and dried over sodium sulfate. Glauber's salt was filtered off, ethyl acetate was distilled off, and the product was purified using column chromatography. F
I yellow solid, yield 18.0 g, yield 81.1% Synthesis Example 2
6 Synthesis of Exemplified Compound W-6 HI J K Synthesis of 3.5-dichloro-4-hydroxybenzoic acid (I) Ethyl 3.5-dichloro-4-hydroxybenzoate (H
) (manufactured by Tokyo Chemical Industry ■) 25 g (o, n mol), methanol 360 ml, potassium hydroxide 36 g (0, n mol)
64 mol) was added and dissolved, and after heating and stirring under reflux for 6 hours,
In addition to ice water, 12N hydrochloric acid was added to neutralize the mixture, and the crystals were filtered. This was recrystallized from methanol. Colorless crystal. Yield 1
3.2 g, yield 59.7% Synthesis of 4-carboxyl-2,6-dichlorophenyl carbonic acid hexadecyl ester (J) 3,5-dichloro-4-hydroxybenzoic acid (I)
19 g (0, (192 mol) of triethylamine 2
7 m [1 (0,19 mol), tetrahydrofuran 190
Add m1 and dissolve, and add this to hexadecyl chloroformate 63
m! (0.19 mol) in 320 ml of tetrahydrofuran
It was added dropwise to a solution that had been dissolved in water and heated to 0°C. After stirring at 25°C for 1 hour, 170 d of water was added and the mixture was further stirred at 25°C for 3 hours. Thereafter, ethyl acetate and water were added to separate the layers, and the ethyl acetate layer was washed once with saturated brine and dried over sodium sulfate. Glauber's salt was filtered off, ethyl acetate was distilled off, purified by column chromatography, and further recrystallized from methanol. Colorless crystals, yield 31.2 g, yield 71.3% Synthesis of Exemplary Compound 71-6 4-Carboxyl-2,6-dichlorophenyl carbonate hexadecyl ester (J) 8.4 g (0,018 mol)
Thionyl chloride 1,5m&(0,021 mol) and benzene 42d were added and dissolved in the solution, and the mixture was heated and stirred under reflux for 1 hour, and then the benzene was distilled off. D8.0g (0,01
6 moles), 40 m2 of tetrahydrofuran, 1 mol of pyridine
, 4d (0,018 mol) was added and dissolved, O″C
The mixture was added dropwise with stirring and stirred at 25°C for 24 hours.

Tetrahydrofuran was distilled off, and ethyl acetate was added to the residue, which was washed twice with saturated brine and dried over Glauber's salt. Glauber's salt was filtered off, ethyl acetate was distilled off, and the product was purified using column chromatography. Light yellow solid. Yield: 8.26 g, yield: 49.2% The coupler represented by the general formula (I) used in the present invention is preferably added to a silver halide photographic light-sensitive layer, but depending on the purpose, it may be added to a non-light-sensitive photographic layer. can be added to the layer.

Silver halide color photographic light-sensitive materials for use in the present invention include color paper, color reversal paper, color negative film, color positive film, etc., and it is particularly preferred to use color paper and color reversal paper.

The magenta coupler of the present invention and the combination couplers described below can be introduced into the light-sensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil droplet dispersion method in ice. This can be cited as an example. In the oil droplet dispersion method in ice, the boiling point is 17
After dissolving in either a high-boiling point organic solvent of 5°C or higher and a low-boiling point so-called auxiliary solvent, either alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. . Examples of high boiling point organic solvents include US Pat. It may be used for application after being removed or reduced by distillation, noodle washing or ultrafiltration.

Specific examples of high-boiling organic solvents include phthalic acid esters (e.g., dibutyl phthalate, di-37-dimethyloctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, dodecyl phthalate, etc.), phosphoric acid, Phosphonate esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.
4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), anilines (N,N-dibutyl-2-butoxy- 5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene,
(diisopropylnaphthalene, etc.), and the auxiliary solvent has a boiling point of about 30°C to about 160°C.
Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone-2-ethoxyethyl acetate, and dimethylformamide.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are described in U.S. Pat.
, No. 230, etc.

The couplers of the invention are preferably added within the light-sensitive silver halide emulsion layer. The addition amount range is 1 of silver halide.
0.002 to 0.5 mol per mole can be used, preferably 0.01 to 0.5 mol is added.

The coupler in the present invention may be used in all of the blue-sensitive layer, green-sensitive layer, and red-sensitive layer of the photosensitive material, or may be used in any two of the three layers, preferably one of the three layers.
It is preferable to use it only in the layer, and it is especially preferable to use it in the green-sensitive layer in terms of the effects of the present invention.

Further, the coupler in the present invention may be used in combination with a yellow coupler, a magenta coupler, or a cyan coupler, and in this case, the proportion of the coupler of the present invention may be arbitrary, and preferably 5 to 400% of the coupler used in combination. mol%, more preferably 10 to 50 mol%
added.

The coupler used in combination with the coupler in the present invention may have an amount of 4 equivalents or 2 equivalents relative to silver ions.

Couplers that are preferably used in combination with the couplers in the present invention are shown below.

As a phenolic cyan coupler, US patents 2 and 3
No. 69,929, No. 4,518,687, No. 4,51
There are products (including polymer couplers) that have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position, as described in No. 1,674 and No. 3,772,002, etc., and representative specific examples thereof. As for Canadian Patent 625,8
Coupler of Example 2 as described in No. 22, US Patent f:tS
Compound (1) described in No. 3,772.002, No. 4゜5
Compounds (l-4) and (I-5) described in No. 64.590
, Compound (1) described in JP-A-61-39045, (
2), (3) and (24), as described in No. 62-70846
Compound (C-2) can be mentioned.

Phenolic cyan couplers include U.S. Pat. No. 2,772,162, U.S. Pat.
, 334. There are 2,5-diacylaminophenol couplers described in No. O11, ITt14,500.635, and JP-A-59-164555, and representative examples thereof include those described in U.S. Pat. No. 2,895,826. The compound (V) described in the above, the compound described in the same No. 4,557,999 (
17), compound (2) described in No. 4,565,777
(12), the compound (4) described in No. 4,124.3.96, the compound (I-
19) etc. Examples of phenolic cyan couplers include U.S. Pat. Nos. 4,327,173, 4,564.586, and 4,430,423
Japanese Patent Application Laid-open No. 61-390441 and Patent Application No. 10022/1983
There is a compound in which a nitrogen-containing heterocycle is condensed to a phenol nucleus, as described in No. 2, and a typical example thereof is.

The coupler described in U.S. Pat. No. 4,327,173 (1
) and (3), the compound described in No. 4,564,586 (
3) and (16), compounds (1) and (3) described in 4,430°423, and the following compounds.

Other examples of phenolic cyan couplers include U.S. Pat. No. 4,333,999, U.S. Pat.
, 444,872, 4,427.767, 4,
No. 579,813, European Patent (EP) 067.689B
There are ureido couplers described in US Pat. No. 4,333,999 and coupler (1) described in U.S. Tok. ), the coupler (14) described in 4,444,872, the coupler (3) described in 4,427,767, the couplers (6) and (24) described in 4,609°619 , 4.579,813, couplers (1) and (11), European Patent (EP) 067.6
In addition to the coupler (45) and (SO) described in No. 89B1, the coupler (3) described in JP-A-61-42658,
The couplers shown below may be mentioned (C-54) (C-55) (C-56) As the magenta coupler, couplers represented by the following general formula (VI) and -ship formula (IX) are preferably used in combination. .

General formula (■) +<48 General formula<tX) In the formula, R18 represents a substituted or unsubstituted phenyl group, and R16 has the same meaning as an acyl group or R18. R1
7 represents a hydrogen atom, an aliphatic or aromatic acyl group, or an aliphatic or aromatic sulfonyl group.

R19 represents a hydrogen atom or a near substituent group. Zc and Z
d represents methine, substituted methine, =N- or -NH-. Y6 and Y7 are hydrogen atoms or the general formula (m
) to (■), where R16, R17' R
18, Y6, R19, Zc, Zb, or Y7 may form a dimer or more multimer.

Preferred specific examples of the couplers represented by the ship type (■) and the ship type (IX) are shown below, but the invention is not limited thereto.

υ (M-6) (M-9) (M-13) (M-14) C8H17+tl (M-19') (M-20) l (M-21) (M-22) (wt ratio) (M -23) (M-24) (wt ratio) Literatures describing other exemplary compounds or synthesis methods of couplers represented by general formula (VW) and general formula (IX) are listed.

The magenta coupler represented by the general formula ([) was published in Japanese Patent Application Publication No. 4
No. 9-74027, No. 49-74028, Special Publication No. 1973
-27930, US Pat. No. 53-33846, and US Pat. No. 3,519,429.

The magenta coupler represented by the general formula (IX) is disclosed in Japanese Patent Application Laid-Open No. 59-162548 and US Pat.
5,067, JP-A No. 59-171956, U.S. Pat.

As the yellow coupler, it is preferable to use a coupler represented by the following general formula (X).

General formula (X) In the formula, Y8 represents a hydrogen atom or a leaving group, R2o
represents a diffusion-resistant group having a total of 8 to 32 carbon atoms, and R21 represents a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group, or a diffusion-resistant group having a total of 8 to 32 carbon atoms.

For details on the coupler represented by general formula (X),
U.S. Pat. No. 4,622,287, line 3a15 to column 8, line 39 of the specification, and U.S. Pat. No. 4,623°616, line 1
It is described in column 4, line 50 to column 19, line 41.

Specific examples of couplers represented by general formula (X) include:
No. 37 of the aforementioned U.S. Pat. No. 4,622,287.
Compound examples (Y-1) to (Y-39) described in columns to columns 54
Among them, (Y-1) and (Y-4)
, (Y-6), (Y-7), (Y-15), (Y-21
), (Y-22), (Y-23), (Y-26).

(Y-35), (Y-36), (Y-37), (Y-3
8), (Y-39), etc. are preferred.

Further, compound examples (Y-1) to (Y-33
), among which (Y-2), (Y-7
), (Y-8), jy-12), (Y-20), (Y
-21), (Y-23), (Y-29), etc. are preferred.

Other preferable ones include US special kitsuki 3.408
, No. 194 specification, column 6 (34
), No. 8 of Specification No. 3,933,501! Compound examples (16) and (19) described in gJ, 4,046,575
Compound example (9) described in columns 7 to 8 of the specification, 4,
Compound example (1) described in columns 5 to 6a of No. 133°958 J[t, Compound example 1 described in column 5 of No. 4,401,752, and the following compounds a) to g ) can be mentioned.

A chemically inert and substantially colorless compound is chemically bonded to the oxidized aromatic amine color developer remaining after the color development process in Japanese Patent Application No. 158642/1982 into the sensitive material of the present invention. It is preferable to use the resulting storage-improving compounds in combination in order to increase the effects of the present invention, and examples of storage-improving compounds whose combined use is particularly preferred include compounds represented by the general formula (X[).

- Ship formula (XI) In the formula, M is no Ia (e.g. Li, Na, K, Ca, M
(e.g., triethylamine, methylamine, ammonia).

Here, R27 and R28 may be the same or different,
R27 and R28, each representing a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, may be bonded to each other to form a 5- to 7-membered ring."R29' R: 1O2R and R33 are the same or different. may be a hydrogen atom,
It represents an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a sulfonyl group, a ureido group, and a urethane group.

However, at least one of R29 and R3o and at least one of R3□ and R33 are hydrogen atoms. R3□ and R34 represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R3□ further represents an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, where R29, R3
o, R3, at least two groups may be bonded to each other to form a 5- to 7-membered ring, or R3□, R33, R
At least two groups of 34 are bonded to each other to form 5-7
may form a membered ring, R35 is a hydrogen atom, an aliphatic group,
represents an aromatic group or a heterocyclic group; R36 represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, an acyloxy group or a sulfonyl group; R3□ represents a hydrogen atom or a hydrolyzed vine group;

R2□, R23, R24, R25 and R26 may be the same or different, and each represents a hydrogen atom, an aliphatic group (
For example, methyl group, isopropyl group, t-butyl group, vinyl group, benzyl group, octadecyl group, cyclohexyl group), aromatic group (e.g. phenyl group, pyridyl group, naphthyl group), heterocyclic group (e.g. piperidyl group, pyranyl group) , furanyl group, chromanyl group), halogen atom (e.g. clodiyl group), alkoxycarbonyl group (e.g. methoxycarbonyl group, butoxycarbonyl group, cyclohexylcarbonyl group, octyloxycarbonyl group), aryloxycarbonyl group (e.g. phenyloxy carbonyl, naphthyloxycarbonyl group), sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group), sulfonamide group (e.g. methanesulfonamide group 1, benzenesulfonamide group), sulfamoyl group, ureido group, urethane group, carbamoyl group group, sulfo group, carboxyl group, nitro group, cyano group, alkoxy group (e.g., methoxyxalyl group, isobutoxyxalyl group, octyloxyxalyl group, penzoyloxyxalyl group), allylxalyl group (e.g., phenoxy xalyl group, naphthoxyxalyl group), sulfonyloxy group (e.g. methanesulfonyloxy group, benzenesulfonyloxy group), -P (R38)3, -P
(OR38)3 and represents a formyl group, where R3
B and R39 represent a hydrogen atom, an aliphatic group, an alkoxy group, or an aromatic group, among which, for the -502M group,
In view of the effects of the present invention, it is preferable that the sum of the values of llamset be equal to or greater than o,s.

/ / (XI-5) (XI-7) (X[-8) (XI-9) (X[-11) AN (XI-12) r (M-13) (XI-18) U U (XI-20) (X[-30) (XI-31) (XI-32) Ri Ri Ri (XI-34) ri υ (X[-38) (XI-39) (XI-41)

(XI-42) (XI-43) (XI-44). . . H3(AI-
45).

(XI-47) (XI-48) (X[-49) (XI-50) (XI-51) (υCIIHI7 (XI-53) (M-54) (XI-55) (XI-56) (X [-57) ('A-58) (X[-59) 113 Synthesis methods of these compounds are described in Japanese Patent Application No. 60-295466, No. 61-23467, No. 61-36416, No. 6
It can be synthesized by the method described in No. 1-183919, No. 61-183920, or a method analogous thereto.

If the compound represented by the general formula (X[) has a low molecular weight or is easily dissolved in water, it may be added to the processing solution and incorporated into the sensitive material during the development process. Preferably, it is added to the photosensitive material at the stage of manufacturing the photosensitive material. The latter method is usually performed by dissolving a high boiling point solvent (oil) with a boiling point of 170°C or higher at atmospheric pressure alone, a low boiling point solvent alone, or a mixed solvent of the above oil and a low boiling point solvent, and then adding gelatin, etc. to this solution. It is prepared by emulsifying and dispersing it in an aqueous solution of woody colloid. - The compound represented by the formula (X[) is preferably soluble in an organic solvent with a high Buddha point. There is no particular restriction on the particle size of the emulsified dispersion particles, but 0.05 JJ, ~ o, 5 IL is preferable, Especially 0. IIL~0.31L is preferred. In particular, from the viewpoint of the effects of the present invention, it is preferable that the compound represented by the general formula (XI) is co-emulsified with a coupler. In this case, the oil/coupler ratio is preferably 0.00 to 2.0 by weight. preferable.

The proportion of the compound represented by formula (XI) is 1xlo' to 10 mol, preferably 115 mol of 3XlO-2, per mol of coupler.

Specific examples of the oil include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl) phosphate, tricreziphthalate, dioctyl butylphthalate, etc. J lephosphate, monophenyl-p-t-butylphenyl phosphate), citric acid esters (e.g. acetyl tributyl citrate)
, benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide, dibutyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate).

diethyl azelate), trimesate esters (e.g. tributyl trimesate), compounds containing epoxy rings (
For example, compounds described in U.S. Pat. Point solvents include organic solvents with a boiling point of 30°C to 150°C at atmospheric pressure, such as lower alkyl acetates such as ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, methanol, ethanol, secondary butyl alcohol, cyclo Examples include hexanol, fluorinated alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate acetone, methyl acetone, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, chloroform, and cyclohexane.

In addition, instead of high-purity point organic solvents, not only oil-based solvents (including those that are solid at room temperature such as wax) for additives such as couplers, but also latex polymers can be used, or couplers, color mixing inhibitors, and ultraviolet The additive itself, such as an absorbent, may also serve as an oily solvent.

Latex polymers include acrylic acid, methacrylic acid, and their esters (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate, etc.), acrylamide, methacrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate, etc.),
Acrylonitrile, styrene, divinylbenzene, vinyl alkyl ethers (e.g. vinyl ethyl ether),
Manufactured using one or more of 1,000 esters such as maleic acid ester (e.g. maleic acid methyl ester), N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine, etc. Latex polymers are used.

Examples of surfactants used when dispersing a solution of the compound represented by general formula (XI) alone or together with a coupler in an aqueous protective colloid solution include saponin, sodium alkylsulfosuccinate, etc. , sodium alkylbenzenesulfonate, and the like.

The compound represented by the general formula (X[) can be used in combination with any of the yellow couplers, magenta couplers, or cyan couplers in the present invention. Among these, it is particularly preferable to use it in combination with the magenta coupler of the present invention in terms of the effects of the present invention.

The coupler used in combination with the compound represented by the general formula (X[) may have an amount of 4 equivalents or 2 equivalents relative to the silver ion, and may be in the form of a polymer or oligomer. Furthermore, the couplers used in combination may be the couplers of the present invention alone, or may be a mixture of two or more types including at least one coupler of the present invention.

The compound of the present invention may be used in combination with a known anti-fading agent, and particularly preferred anti-fading agents include (i) general formula (
Aromatic compound represented by X[I), (1i) general formula (
An amine compound represented by XI).

or (1ii) a metal complex having copper, cobalt, nickel, palladium, or platinum as the center and at least one organic ligand having a bidentate or more conformation.

General formula (X[[) In the formula, R40 is a hydrogen atom, an alkyl group, and alkyl R48 may be the same or different from each other, and each is an alkyl group,
Represents an alkenyl group, aryl group, alkoxy group, alkenoxy group, or aryloxy group. R4□, R4
□, R43, R44 and R45 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acylamino group, an alkylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group , represents a halogen atom or 10-R4o'. Here R40" is R40
R40 and R41 may be combined with each other to form a 5-membered ring, 6CL ring or spiro ring. R41 and R42 or R42 and R43 may be combined with each other to form a 5-membered ring, 6-membered ring Alternatively, a spiro ring may be formed.

General formula (凰) In the formula, R49 is a hydrogen atom, an alkyl group, an alkenyl group,
Representing an alkynyl group, acyl group, sulfonyl group, sulfinyl group, oxy radical group or hydroxyl group,
R5o, R51, R52 and R53 may be the same or different, and each is a hydrogen atom.

B, which represents an alkyl group, represents a group of nonmetallic atoms necessary to form a 5i, 6fi, or 7 negative ring.

General formula (M), general 2〇! Among the six groups in 11), the group containing even a partial alkyl, aryl or heterocycle may be further substituted with a substituent.

Representative examples of these specific compounds include the patent application 1986-
Compounds A-1 to A-60 described on pages 49 to 63 of Specification No. 233869 and other compounds listed below can be mentioned.

A-, <4t A-6! A-t Otsu A-6/ A-62 CH2=CH20C14H29(n) -The compound represented by the formula (X[[), (Xi) is 10 to 400 mol%, preferably 30
~300 mol% is added. On the other hand, the metal complex is 1 to 100 mol%, preferably 3 to 40 mol%, based on the coupler.
added.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

As other dye image stabilizers, for example, JP-A-59-1
Catechol derivatives described in No. 25732 and Japanese Patent Application Laid-Open No. 60-282159 can also be used.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer.For example, a benzotriazole compound substituted with an aryl group (for example, ), 4-thiazolidone compounds (e.g. those described in U.S. Pat. Acid ester compounds (e.g. US special Kitsuki 3,
Nos. 705,805 and 3,707,375), butadiene compounds (e.g., U.S. Pat. No. 4,045,
229) or benzoxidol compounds (for example, those described in U.S. Pat. No. 3,700,455) can be used. Ultraviolet absorbing couplers (for example, α-naphthol cyan dye-forming couplers), ultraviolet absorbing polymers, and the like may be used, and these ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include: Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other woody colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention.

The average grain size of silver halide grains in a photographic emulsion (the grain diameter for spherical or approximately spherical grains, and the ridged grain size for cubic grains).

Expressed as an average based on the projected area, ) is not particularly important, but 2
It is preferable that it is less than 1.

The grain size may be narrow or wide, but it is preferable to use a monodispersed emulsion with a variation rate of 15% or less.

The silver halide grains in the photographic emulsion layer may have a regular crystal structure such as a cube or hexagonal, or may have an irregular crystal structure such as a spherical shape or a plate shape, or may have an irregular crystal structure such as a spherical shape or a plate shape. It is preferable to use normal crystal emulsions, which may consist of a mixture of grains of various crystal forms.

Further, an emulsion may be used in which tabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface, and may be grains in which latent images are mainly formed on the surface, or grains in which latent images are mainly formed inside the grains.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, a lead salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Silver halide emulsions are usually chemically sensitized.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing the photographic area. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds such as oxadorinthion; azaindenes, e.g. Triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1°3.3a, 7) tetraazaindene), pentaazaindene, etc.: benzenethiosulfonic acid.

Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfinic acid, benzenesulfonic acid amide, and the like.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The supports used in the present invention are usually cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, polycarbonate films, which are used in photographic materials. In addition, there are laminates of these materials, thin glass films, paper 1, etc. Baryta or α-olefin polymers, especially polyethylene,
Paper coated or laminated with a polymer of α-olefin having 2 to 10 carbon atoms, such as polypropylene or ethylene butene copolymer, vinyl chloride resin containing a reflective material such as T 10 z, or paper coated with or laminated with a polymer of α-olefin having 2 to 10 carbon atoms, such as polypropylene, ethylene butene copolymer, etc., vinyl chloride resin containing a reflective material such as T 10 z, A support such as a plastic film whose surface is roughened to improve its adhesion with other polymeric substances also gives good results. Further, an ultraviolet curable resin can also be used.

These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material. It is also possible to add dyes or pigments to make it colored and transparent.

Opaque supports include those that are inherently opaque, such as paper, and
Transparent film with pigments such as dyes and titanium oxide added, or plastic films surface-treated using the method shown in Japanese Patent Publication No. 47-19068, or carbon black, dyes, etc. added to completely light-shielding films. This also includes paper or plastic film. The support is usually provided with an undercoat layer. In order to further improve the adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

The color photosensitive material applicable to the production of the color photograph of the present invention is preferably a normal color photosensitive material, particularly a color photosensitive material for printing.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing the above-mentioned aromatic primary amine color developing agent as a main component.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbalads, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane), etc. Preservatives such as Katsura preservatives, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, etc.1 Dye-forming power puller, competitive coupler, sodium boron hydrite fogging agents such as, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelates such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Agent 1 For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid.

Cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-■, 1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylene Typical examples include phosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid), and salts thereof.

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

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developers depends on the color photographic light-sensitive material being processed, but it is generally less than 3i per trn" of the light-sensitive material, and can be reduced to less than 500 by reducing the bromide ion concentration in the replenisher. When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank.Also, to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment by using measures.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a bleach-fixing treatment.

Depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include compounds of polyvalent metals such as iron (■), cobalt (■), chromium (■), and copper (■), peracids,
Quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide: dichromate: organic complex salts of iron (m) or cobalt (m), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexadiaminetetraacetic acid, methyliminodiacetic acid, Aminopolycarboxylic acids such as diaminopropynetetraacetic acid, acetic acid recall ether, diaminetetraacetic acid, or citric acid,
Complex salts of tartaric acid, malic acid, etc.: persulfates; bromates; permanganates; nitrobenzenes, etc. can be used. Of these, iron ethylenediaminetetraacetate (III
) Aminopolycarboxylic acid iron(III) including complex salts
Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron (m) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (m) complex salts is usually 5.5 to 8, but in order to speed up the processing, it can be processed at an even lower pH. .

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 US Pat. No. 3,893,858.

West German Patent Section 1,290,812, 2,059.98
No. 8, JP-A-53-32736, JP-A No. 53-57831
No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-28426, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or disulfide group as described in JP-A-50-140129; thiazolidine derivatives as described in JP-A No. 45-8506, JP-A-Sho 52-
No. 20832, No. 53-32735, U.S. Patent Section 3,
Thiourea derivatives described in West German Patent No. 1,127,715, iodide salts described in JP-A-58-16235: West German Patent No. 966.410, West German Patent No. 2,7
Polyoxyethylene compounds described in No. 48.430;
Polyamine compounds described in Japanese Patent Publication No. 45-8836: Others: Japanese Patent Publication Nos. 49-42434, 49-59644,
No. 53-94927, No. 54-35727, No. 55
Compounds described in No.-26508 and No. 58-163940; 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 in U.S. Patent Section 3.893,858.
No., West German Patent Section No. 1,290,812, JP-A-53-9
The compounds described in No. 5630 are preferred.

Furthermore, the compounds described in U.S. Pat. agents are particularly effective.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. Thiosulfates are commonly used, and ammonium thiosulfate is the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the 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 l
1tion Picture and Televis
ion Engineers Volume 64, p-248-2
53 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
A method for reducing calcium ions and magnesium ions as described in Japanese Patent Application No. 61-131632 can be found and used very effectively. Also, JP-A-57-854
Inchiazolone compounds and ibendazole compounds described in No. 2, chlorine-based disinfectants such as chlorinated sodium incyanurate, and other benzotriazoles, Hiroshi Horiguchi's ``Chemistry of Antibacterial and Antifungal Agents'', Hygiene Technology Extra Section ``Microorganisms'', etc. It is also possible to use disinfectants described in "Sterilization, Disinfection, and Life Protection Techniques" and "Encyclopedia of Antibacterial and Antibacterial Agents" by Nikki Bibakubo Shogaku Yoshin.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 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 25 to 10 minutes.
A range of 30 seconds to 5 minutes at ~40°C is selected. Furthermore, the light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543, 58-14834,
All known methods described in No. 60-220345 can be used.

Further, the water washing treatment may be followed by a further stabilization treatment, such as a stabilization bath containing formalin and a surfactant used as a final bath for color photosensitive materials for photography. Various chelating agents and anti-inflammatory agents can also be added to this stabilizing bath.

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

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, US patent m3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, thick base type compounds described in Research Disclosure No. 14850 and Research Disclosure No. 15159, Research Disclosure No. 13
Aldol compounds described in '924, U.S. Patent No. 3.71
Metal salt complex described in No. 9,492, JP-A-53-1356
Examples include the urethane compounds described in No. 28.

The silver halide color light-sensitive material of the present invention may contain various types of l-phenyl-3, if necessary, for the purpose of promoting color development.
- Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-5B-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can do. Further, for recording of photosensitive materials, a treatment using cobalt intensification or hydrogen peroxide intensification as described in Seishi-Dokki Kitsuki No. 2,226,770 or U.S. Pat. No. 3,674,499 may be carried out.

(Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention has the excellent effect of providing color photographs in which the white background does not discolor even when stored and displayed for a long period of time after color development and bleach-fixing treatments.

Furthermore, according to the silver halide color photographic light-sensitive material of the present invention, it is possible to obtain color photographs in which deterioration of dye images due to residual color developing agent carried into the light-sensitive material after color development, bleaching, and fixing processes is prevented. .

Furthermore, according to the present invention, a processing solution in which a large amount of processing solution components are brought into the photosensitive material, such as a processing solution in a running state, a processing solution with a small amount of water washing or an anhydrous washing processing solution, and a color developing solution that does not substantially contain benzyl alcohol. , or other processing liquids that place a burden on color development, to form color images on color photosensitive materials that prevent image deterioration and staining caused by residual aromatic amine color developers even when processed with processing solutions that place a burden on color development. be able to.

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

Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY) and 2-20 g of anti-fading agent (Cpd-1) were added to 27.2 cc of ethyl acetate.
Add and dissolve 7.7cc of solvent (Solv-1),
This solution was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. Separately, a silver halide emulsion (1) was prepared by adding the blue-sensitive sensitizing dye shown below in an amount of s, oxto-4 mol per mol of silver. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved, and the mixture was mixed and dissolved to obtain VIJ0 & as shown below.
A layer coating solution was prepared. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is l-oxy-3,5-dichloro-5-)
Riazine sodium salt was used.

The silver halide emulsion (1) used was prepared as follows.

(1 liquid) H2O 1000d NaC 5.5g Gelatin 25g (2 liquids) Sulfuric acid (IN) 20d (3 liquids) The following compounds (1%) 2 Suri H3 Sho H3 (4 liquids) KBr
2. 80g NaC10.34g Add H2O 140 ml (5 liquids) AgNO35g Add H2O 140ml (6 liquids) KBr 67.20g
NaC18,26g K I r C a (0,001%) 0
, add 77IlfiH2O and 320m
1 (7 liquids) A g N O: l 1
20 gNH4No2 (5 (1$)
2mfl! Add H20 to make 320 liters
The liquid) was heated to 75°C, and the liquids (2) and (3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously over a period of 9 minutes. After another 10 minutes, add (6 liquids) and (7 liquids) to 45
The simultaneous additions took 5 minutes. After 5 minutes of addition, lower the temperature and
Desalted.

Add water and dispersed gelatin to adjust the pH to 6.2, average particle size 1.01 lm, coefficient of variation (standard deviation divided by average particle size: s/d) 0.08, silver bromide 80. A monodisperse cubic silver chlorobromide emulsion of mol % was obtained. This emulsion was optimally chemically sensitized with sodium thiosulfate.

Silver chlorobromide emulsions (2) and (3) in green-sensitive and red-sensitive emulsion layers
) were also prepared in the same manner by varying the amount of chemicals, temperature, and time.

Emulsion (2) has a grain size of 0.45 ILm and a coefficient of variation of 0.
．． 07 silver bromide 80 mol%, emulsion (3) has a grain size of 0
．． It was a monodispersed cubic silver chlorobromide emulsion containing 70 mol % silver bromide and a coefficient of variation of 0.07.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer: (5.0xlO = mole per mole of emulsion) Green-sensitive emulsion layer: (4.-0xlO-' mole per mole of emulsion) and (1 per mole of fL'F1) 7.0xlO-''-1jlz
) Red-sensitive emulsion layer: (0.9xlO' mol per mol of emulsion) For the red-sensitive emulsion layer, the following compounds were added at a concentration of 2.0 x 1 O' mol per mol of silver halide.
6xlO-3 moles were added.

Further, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added in an amount of 1.2×10 mol and 1.0 mol per mol of silver halide, respectively. 1×10 −2 mol was added.

Further, for the green-sensitive emulsion layer, 1.5% of 1-(5-methylureidophenyl)-5-mercaptotetrazole was added per mole of silver halide. oxlo' moles were added.

Further, 1.0XIO-4 mol of 2-amino-5-mercapto-1,3,4-thiadiazole was added per mol of silver halide to the red-sensitive emulsion layer.

In addition, the following dyes were used as irradiation-preventing dyes.

And the composition of each layer is shown below. The number is the coating amount (g/rn')
The silver halide emulsion represents the coated amount in terms of silver.

(Layer structure) Paper support laminated on both sides with polyethylene support (the polyethylene on the first layer side contains a white pigment (T i Oz ) and a bluish dye (ulmarine blue)) Layer - (blue-sensitive layer) Silver halide Emulsion (1) 0.26 gelatin 1.2° yellow coupler (
ExY) 0.66 color image stabilizer (Cpd-1)
0.04 solvent (Solv-1)
0.26 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion (2) 0.13 Gelatin 1.90 Magenta coupler (
ExM) 0.34 color image stabilizer (Cpd-3)
0.21 stabilizer (Cpd-4)
0.01 Solvent (So 1v-2) 0.6
9 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.65 Color mixing prevention agent (Cpd
-5) 0.05 solvent (Solv-3)
0.24 Fifth layer (red-sensitive layer) Silver halide emulsion (3) 0.22 Gelatin 1.02 Cyan coupler (E
xC) 0.30 color image stabilizer (Cpd-6)
0.08 gradation part agent (Cpd-7)
0.01 polymer (cpci-s) o, 3
0 Solvent (Solv-4) 0.20 Sixth layer (UV absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.22 Solvent (So 1v-
3) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 (ExY) Yellow coupler (ExM) Magenta coupler (ExC) ) Cyan coupler (cpci-t) Color image stabilizer (Cpd-2) Color mixing inhibitor (Cpd-3) Color image stabilizer (Cpd-4) Stabilizer (Solv-1) Solvent (Solv-2) Solvent 2 :1 mixture (volume ratio) (Solv-3) solvent (Solv-4) solvent The multilayer color photographic paper thus prepared was sample No.
It was set to 1.

Next, among the above-mentioned compositions, only the magenta coupler (Ex M) of the third layer (green-sensing layer) was compared.
Sample No. 62 was prepared in place of 1). At this time, the amount of coupler was made equimolar to that of magenta coupler (ExM).

Comparative coupler (M-1) [alpha] Furthermore, samples N003 to No. 13 were prepared in the same manner by replacing the magenta coupler of the present invention.

This sample No. 1-13 was subjected to gradation exposure for sensitometry through a three-color separation filter using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 K).

The exposure at this time was carried out so that the exposure time was 0.1 seconds and the exposure amount was 250 CMS. Thereafter, the following treatment steps were performed.

However, in order to clarify the effects of the present invention, the following processing steps are such that the developing agent and other processing solution components tend to remain and stains are likely to occur.

Kiriko 1 Surprise - Nail - Homo color development
33°C 3 minutes 30 seconds Bleach fixing 33°C1
minutes 30 seconds Washing with water 20-25°C 1 minute (no stirring) Drying 50-80°C 2 minutes The components of each treatment solution are as follows.

Color developer Nitrilotriacetic acid/3Na 2.0g Benzyl alcohol 15d Diethylene glycol 1O Sodium sulfite
0.2g Potassium bromide 0.5g
Hydroxylamine sulfate 3.0g4-Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate 6.5gSodium carbonate (l hydrate) 30g water In addition
10001i (pH 10,1) Bleach-fix solution Color developing solution 400 m [l Ammonium thiosulfate (70 wtX) 150 TT1
i! Sodium sulfite 12g (E
DTA) Fe sodium 36g (EDTA)
・Add 4g of 2-sodium water
100011191 NMWI Ni'Cp H7
, 0 nits AIM The above composition solution was aerated for 1 hour and then used.

Note: The above bleach-fix solution is intended for use under adverse conditions where the composition of the solution changes due to reasons such as a color developing solution adhering to the photosensitive material during running and a large amount being carried into the bleach-fix solution.

Next, for each of the developed samples No. 1 to No. 13, one hour after the development processing, the magenta reflection density (stain) of the non-image area was measured with green light using a Fuji self-recording densitometer. After measuring, the magenta reflection density of the non-image area (
Stin) was measured in the same manner.

Table 1 shows the above results and the increase in magentastin (60 g) from 1 hour after treatment.

In Table 1, sample No. 1.2 is a comparative example, and samples No. 3 to 13 are examples of the present invention.

As is clear from the results shown in Table m1, it can be seen that when the coupler of the present invention is used, the occurrence of staining over time after treatment is significantly prevented.

Example 2 Among the compositions of samples No. 1 shown in Example 1, the cyan coupler (ExC) in the fifth layer was replaced with a comparative coupler and a cyan coupler of the present invention as shown in Table 2 below, Samples Nos. 21 to 29 were prepared.

Comparative coupler (C-1) Comparative coupler (C-2) Developed in the same manner as in Example 1, and 1 hour after developing each of the processed samples No. 21 to 29, Fuji type self-recording was carried out. After measuring the cyan reflection density (stain) of the non-image area with red light using a densitometer,
When left for 2 weeks under 70% RH condition, and when left at room temperature for 3 weeks.
After being left for several months, the cyan reflection density (stain) of the non-image area was measured again in the same manner.

Table 2 shows the above results and the increase in cyanstein (ΔDr) from 1 hour after treatment.

In Table 2, sample Nos. 21, 22, and 23 are comparative examples, and samples Nos. 24 to 29 are examples of the present invention.

From the results in Table 2, it is clear that when the coupler of the present invention is used, the occurrence of staining over time after treatment is significantly prevented.

Example 3 Of the layer structure of sample No. 1 shown in Example 1, the magenta coupler (ExM) in the third layer was used as the magenta coupler of the present invention, IV-6, and the yellow coupler in the first layer was used as the comparison coupler and IV-6. Samples Nos. 31 to 38 were prepared by replacing the yellow coupler of the present invention with the yellow coupler of the present invention.

Comparative coupler (Y-1) Um3 Comparative coupler (Y-2) Development processing was performed in the same manner as in Example 1, and the yellow stain after processing was evaluated for each of processed samples Nos. 31 to 38. .

Table 3 shows the above results and the increase in yellow stain (ΔDb) from 1 hour after treatment.

In Table 3, sample numbers 31, 32, and 33 are comparative examples, and sample numbers 34 to 38 are examples of the present invention.

From the results in Table 3, it is clear that when the coupler of the present invention is used, the occurrence of staining over time after treatment is sufficiently prevented.

Patent applicant: Fuji Photo Film Co., Ltd.
(Spontaneous) February 5, 1988 Patent Application No. 262818 of 1988 2 Name of the invention Silver halide color photographic light-sensitive material 3 Relationship with the person making the amendment Case Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd. Representative: Minoru Ohnishi 4, Agent Address: 6, 7th Floor, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo 105, "Detailed Description of the Invention" in the Specification Subject to Amendment ” Column 7, Contents of amendment (1) Next to “methyl-” in the second line of page 7 of the specification, “
4-" will be added.

(4) "And Y" in line 4 of page 18 of the same book is corrected to "and Y5 J."

(5) Add "group" next to "total bending atom" in the first line from the bottom of page 46 of the same book.

(6) Correct the chemical formula on page 55 (II-20) of the same book.

Claims (1)

[Scope of Claims] 1) At least one of the photographic layers on the support contains a coupler that has the function of chemically bonding with an aromatic amine color developing agent to make it chemically inactive. Characteristic silver halide color photographic material. 2) The coupler has a second-order reaction rate constant k_2 (80°C) with p-anisidine of 1.0 to 1.0×10^-^
The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material is in the range of 6 l/mol·sec. 3) The silver halide color photographic light-sensitive material according to claim 1, wherein the coupler chemically bonds with the aromatic amine color developing agent remaining after color development processing under conditions of pH 8 or less.