JPH01250955A - Color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the increase of stain with age by incorporating at least one kind of a specified coupler and at least one kind of a specified compd. in the same layer of the sensitive material. CONSTITUTION:At least one kind of the coupler shown by formulas I and II, and at least one kind of the compd. shown by formula III are incorporated in the same layer of the sensitive material. In formulas I-III, R1 is alkyl, aryl or a heterocyclic ring group, R2 is hydrogen atom or a substituting group, X is hydrogen atom or a coupler releasing group, R is hydrogen atom, alkyl, alkenyl, alkinyl, oxyradical or hydroxyl group, A is a nonmetal atomic group necessary for forming a 5-7 membered ring. Thus, the sufficient color developability and the good color reproducibility of the sensitive material are obtd., and the increasement of the stain with age at the unexposed part of the sensitive material can be prevented.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material. The present invention relates to a photosensitive material in which an increase in density in unexposed areas is significantly suppressed.

(Prior art) Using exposed silver halide as an oxidizing agent, the oxidized aromatic primary amine color developing agent and coupler react to form indofegur, indoaniline, indamine, azomethine, phenoxazine, and phenazine. It is well known that pigments and similar pigments can be produced to form color images.

Among these, in order to form a magenta color image, 5-
Pyrazolone, cyanoacetophenone, indasilone, pyrazolobenzimidazole, and pyrazolotriazole couplers are used.

Hitherto, most of the 5-pyrazolones have been widely put into practical use and researched as magenta color image-forming couplers. However, it has been known that dyes formed from 5-pyrazolone couplers have unnecessary absorption with a yellow component near 43011m, causing color turbidity.

Pyrazolobenzimidazole bone core is described in British Patent No. 1047.612 as a magenta image forming bone core that reduces this yellow component, US Patent No. 3770.447
Indacylon osteonucleus described in U.S. Patent No. 3.
Pyrazolo[5,1-c] described in No. 725,067
-1,2,4-triazole bone cores have been proposed.

However, the magenta couplers described in these patents, when mixed into silver halide emulsions in dispersed form in hydrophilic protective colloids such as gelatin,
They may give unsatisfactory color images, have low solubility in high-boiling organic solvents, be difficult to self-regulate, have relatively low coupling activity with ordinary developers, or Some are still unsatisfactory due to extremely low light fastness.

The inventor of the present invention has searched for various new types of magenta color image couplers that do not exhibit sub-absorption near 430 nm, which is the biggest drawback in terms of hue of 5-pyrazolone couplers. High color image fastness,
We discovered the IH-pyrazolo[1,5-b]-1,2,4-triazole magenta coupler disclosed in JP-A-59-171956 and U.S. Pat. No. 4,540°654, which is easy to synthesize. Ta. These couplers have excellent color reproduction and are excellent in synthesis, and can be made into so-called 2-equivalents by introducing a leaving group into the coupling active position.
It also had the feature of being able to reduce the amount of silver used.

(Problems to be Solved by the Invention) However, these couplers have low color forming properties and are susceptible to fluctuations in the concentration of processing solution components during continuous processing (for example, they are added to the developer as an antioxidant for the color developing agent). There was a problem in that there was a large change in photographic properties due to sulfite ions, hydroxylamine derivatives, etc.).

As a means to overcome these drawbacks, the patent application
LH-pyrazolo (I, 5-b) in which the 6-position is substituted with an alkyloxy group or an aryloxy group described in No. 2712
-1,2,4-triazole and =4- and IH-pyrazolo(5,1-c) 1,2,4-triazole magenta couplers are known, but by using these couplers, color development can be improved. Although fluctuations in photographic properties during continuous processing are significantly suppressed, staining (increase in density in unexposed areas) occurs over time after processing.

Stain in silver halide color photographic materials is undesirable because it not only determines the quality of white spots in the image but also makes the color image muddy and impairs visual sharpness. Particularly in the case of reflective materials (for example, color paper), the reflection density of the stain is theoretically emphasized several times as much as the transmission density, and even a weak stain impairs image quality, which poses a big problem. As a technique for improving stain by adding a compound to a sensitive material, a technique using a compound described in JP-A-62-96944 and JP-A-62-92945 has been disclosed, but the present invention coupler did not show sufficient effect.

In addition, a technique for using hindered amines in combination with a birazolotriazole coupler is described in European Special Kitsuki No. 218゜266, in which the 6-position is substituted with an alkyloxy group, an aryloxy group, or a heterocyclic group. There are no examples, and it is not easy to infer the effects of the present invention from this example.

In this sense, it is less susceptible to processing fluctuations, and
It has been hoped that a technology to suppress the increase in stains would emerge.

Therefore, the object of the present invention is to exhibit sufficient color development and
The object of the present invention is to provide a photosensitive material that has good color reproducibility and significantly suppresses the increase in density over time in unexposed areas.

(Means for Solving the Problems) It has been found that the objects of the present invention can be achieved with the following color photosensitive materials.

A halogenated compound comprising at least one coupler represented by the following general formulas (III) and (If) and at least one compound represented by the following general formula (III) in the same layer. Silver color photographic material.

General Formula (I) In the formulas (I) and (If), R represents an alkyl group, an aryl group or a heterocyclic group, and R2 represents a hydrogen atom or a substituent. X represents a hydrogen atom or a coupling-off group.

General formula (III) In formula (III), R represents a hydrogen atom, an alkyl group, an alkynyl group, an alkynyl group, an oxy radical group, or a hydroxyl group. R3, R,, R5 and R6 may be the same or different and each represents a hydrogen atom or an alkyl group. A represents a group of nonmetallic atoms necessary to form a 5-, 6-, or 7-membered ring. Here, R3 and R4, R5 and R6, R and R3, and R3 and A may be bonded to each other to form a 5-membered or 6R ring.

Next, the magenta couplers of general formulas (III) and (II) will be explained in detail.

R is a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a trifluoromethyl group, a phenylmethyl group, a methoxyethyl group, a 2-phenoxyethyl group, a 2-methylsulfonylethyl group, a 2-hydroxyethyl group, 3,3
．． Alkyl groups such as 3-trifluoropropyl group, 2-fluoroethyl group, 2-tritetraethyl group, 2-bromoethyl group, 2-cyanoethyl group, 3-oxobutyl group, or phenyl group, 4-methylphenyl group, Aryl groups such as 4-t-butylphenyl group, 4-acylaminophenyl group, 4-halogenophenyl group, 4-alkoxyphenyl group, and 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group represents a heterocyclic group such as a group, a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group.

R2 is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, etc.), an alkyl group [e.g., a sulfonamide-substituted alkyl group (sulfonamidomethyl group, 1-sulfonamidoethyl group, 2-sulfonamidoethyl group, 1- methyl-2-sulfonamidoethyl group, 3-sulfonamidopropyl group, etc.), acylamino group-substituted alkyl group, (acylaminomethyl group, 1-acylaminoethyl group, 2-
acylaminoethyl group, 1-methyl-2-acylaminoethyl group, 3-acylaminopropyl group, etc.), sulfonamide-substituted phenylalkyl group (p-sulfonamidophenylmethyl group, 1)-sulfonamidophenylethyl group, 1-(p-sulfonamidophenyl)ethyl group,
1)-sulfonamidophenylpropyl group, etc.), acylamino-substituted phenylalkyl group (I)-acylaminophenylmethyl group, p-acylaminophenylethyl group, 1-(p-acylaminophenyl)ethyl group, p-acylamino phenylpropyl group, etc.), alkylsulfonyl-substituted alkyl groups (2-dodecylsulfonylethyl group, 1-methyl-2-pentadecylsulfonylethyl group,
octadecylsulfonylpropyl group), phenylsulfonyl-substituted alkyl group (3-(2-butyl-5-t-
octylphenylsulfonyl)propyl group, 2-(4-
unsubstituted alkyl groups such as methyl, ethyl, hexyl, dodecyl, aryl groups (such as sulfonamidophenyl, acylaminophenyl) , alkoxyphenyl groups, aryloxyphenyl groups, substituted alkylphenyl groups, sulfonamide naphthyl groups, substituted aryl groups such as acylaminophel groups, and unsubstituted aryl groups such as phenyl and naphthyl groups), heterocyclic groups (e.g. 2 -furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-penzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecylethoxy group, 2-methane group) sulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), acylamino group (e.g., acetamide group, benzamide group, tetradecaneamide group, α- (2,4-di-monoamylphenoxy)butyramide group, 7-(3-t-butyl-
4-hydroxyphenoxy)butyramide group, α-+4
．． -(4-hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g. phenylamino group, 2-chloroanilino group, 2-chloro-5-te1hladecanamitoanilino group, 2-chloro-5 -dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5-(α-(3-butyl-4-
hydroxyphenoxy) dodecanamido) anilino group,
etc.), ureido groups (e.g. phenylureido group, methylureido group, N,N dibutylureido group, etc.), sulfamoylamino groups (e.g. N,N-dipropylsulfamoylamino group, N-methyl- N-decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, octylthio group, tetrathiodecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(I-t- butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, 2-butoxy-5-t-octylphenylthio group,
3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
), alkoxycarbonylamino groups (e.g., methoxycarbonylamino groups, tetradecyloxycarbonylamino groups, etc.), sulfonamide groups (e.g., methanesulfonamide groups, hexadecanesulfonamide groups, benzenesulfonamide groups, 1)-toluene sulfonamide group, octadecane sulfonamide group, 2-methyloxy-5-t-butylhensensulfonamide group, etc.), carbamoyl group such as N-ethylcarbamoyl group, N
, N-dibutylcarbamoyl=12-yl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N15
-(2,4-di-tert-amylphenoxy)propyl)carbamoyl group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(2-dodecyloxy) ethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group) , etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), and among these, preferably an alkyl group, an aryl group, an alkylthio group, or an arylthio group. More preferably an alkyl group or an aryl group.

In particular, when the coupler is represented by the general formula (Il), when R1 is alkyl, R2 is an alkyl group, an aryl group,
Preferred examples include an alkylthio group, an arylthio group, a heterocyclic dio group, an alkoxycarbonyl group, a sulfinyl group, and a carbamoyl group.

Examples of these include sulfonamide-substituted alkyl groups (
For example, sulfonamidomethyl group, l-sulfonamidoethyl group, 2-sulfonamidoethyl group, 1-methyl-2
-sulfonamidoethyl group, 3-sulfonamidopropyl group, etc.), acylamino-substituted alkyl group (e.g., acylaminomethyl group, 1-acylaminoethyl group, 2-
acylaminoethyl group, 1-methyl-2-acylaminoethyl group, 3-acylamino 10-pyl group), sulfonamide-substituted phenylalkyl group (e.g. p-sulfonamidophenylmethyl group, p-sulfonamidophenylethyl group, 1-<1)-sulfonamidophenyl)ethyl group, 1)~sulfonamidophenylpropyl group, etc.)
, acylamino-substituted phenylalkyl group (e.g. p-acylaminophenylmethyl group, p-acylaminophenylethyl group, 1-(p-acylaminophenyl)ethyl group, p-acylaminophenylpropyl group, etc.), alkylsulfonyl-substituted alkyl group groups (2-dodecylsulfonylethyl group, 1-methyl-2-pentadecylsulfonylethyl group, octadecylsulfonylpropyl group, etc.),
phenylsulfonyl-substituted alkyl group (3-(2-butyl-5-t-octylphenylsulfonyl)propyl group,
Substituted alkyl groups such as 2-(4-dodecyloxyphenylsulfonylethyl group, etc.) and unsubstituted alkyl groups such as methyl group, ethyl group, hexyl group, dodecyl group,
In addition, substituted aryl groups such as sulfonamidophenyl group, acylaminophenyl group, alkoxyphenyl group, aryloxyphenyl group, substituted alkylphenyl group, sulfonamidoethyl group, and acylaminonaphthyl group, and anhydrous groups such as phenyl and naphthyl groups. Substituted aryl group, alkylthio group (e.g. methylthio group, octylthio group,
Tetradecylthio group, 2-phenoxyethylthio group, 3
-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g. -15= phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecyl phenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, heterocyclic thio group (e.g. 2-benzothiazolylthio group, 2,4-di-phenoxy-1,3,5-
triazole-6-thio group, 2pyridylthio group, etc.),
Examples include.

Among these, preferred are substituted alkyl groups and substituted aryl groups, and more preferred are substituted alkyl groups.

X is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxyl group, or a group connected by an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, 2.4- Dichlorobenzoyloxy group, ethoxyoxazaroyloxy group, bilbinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group group, 3-pentadecylphenokidi group,
benzyloxycarbonyloxy group, ethoxy group, 2-
cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group,
etc.), groups linked via a nitrogen atom (e.g., benzenesulfonamide group, N-ethyltoluenesulfonamide group, peptafluorobutanamide group, 2,3,4,5.6-pentafluorobenzamide group, octanesulfonamide group) group, p-cyanophenylureido group, N,N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-
Dimethyl-2,4-dioxo-3-oxazolidinyl group, 1-hensyl-ethoxy-3-hydantoynyl group, 2
N-1,1-dioxo-3(2H)-oxo-1,2-
Benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyrimidinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazole-1
-yl, 5- or 6-promohenzotriazol-1-yl, 5-methyl-1,2,3,4-tetrazol-1-yl group, benzimidazolyl group, etc.) Groups linked by a sulfur atom ( For example, phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group,
4-octanesulfonamidophenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-Z, 3,4.5
-tetrazolylthio group, 2-benzothiazolyl group, etc.)
represents.

When R1, R2 or -O-CH2CH2-1, etc.)
, a substituted or unsubstituted phenylene group (e.g. 1,4-
Represents a phenylene group, a 1,3-phenylene group, or a divalent group at an appropriate location.

When those represented by general formulas (I) and (II) are included in the vinyl monomer, the linking group in which either R1 or R2 is an alkylene group (substituted or unsubstituted alkylene group, e.g. , methylene group, ethylene group,
1,10-decylene group, CH2CH20CH2CH□-
1, etc.), phenylene group (substituted or unsubstituted phenylene group, such as 1,4-phenylene group, ), including groups formed by combining those selected from

Preferred linking groups include the following.

Note that the vinyl group may have substituents other than those shown in general 24), and preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group). represents.

Monomers, including those represented by general formulas (I) and (I[), can be copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers. You can.

Acrylic acid, α
- Chloroacrylic acid, α-alkylacrylic acid (such as methacrylic acid) and esters or amides derived from these acrylic acids (such as acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-
Ethylhexyl acrylate, ■-octyl acrylate, lauryl acrylate, methacrylate,
ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibisacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid esters , N-vinyl-
Examples include 2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymer color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers are determined by the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

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

Next, specific examples of typical magenta couplers in the present invention will be shown, but the present invention is not limited thereto.

(E) (Otsu) Lx7Luノ(/θ) (//) (/2) (/3) α (/g) (/j) (,20) (,2/) C5Hi
7(t) 12H25 -28= (Mukomashi M3 U6M
13 (koj) (to 2) -ノ) uH23 = 30 = (3o) CaH17(j) ,, -32- (3I) 08Hyo7(t) (gu0) (gugu) C8H17(t) ( ) x:y=J θ! 0 (Same for weight ratio and below) (I, t2) (Guza) = 37- (Gu9) X y=yo O: , 3'O (Jθ) f x : y=30 : 30 1 40 - (4th t) (6ri ('A) QC4H9 (!7) shi8-fil 7 (t) B (tri) mouth! 1→ =44-146 - CaJ7(t) O2 Among the couplers of the above general formulas (I) and (II), R
1 is preferably an aryl group, particularly preferably a substituted phenyl group (for example, a phenyl group substituted with an alkoxy group at the α-position).

Next, a general method for synthesizing the coupler of the present invention will be described. IH-pyrazolo[1,5”b]-1,2 when the 6th position is a hydrogen atom or an alkyl group, as described in JP-A-60-197688.
, 4-triazole is described, the couplers of the present invention (-formulas (I) and (■)) can also be synthesized basically by the same method, although the starting materials are different. The synthesis scheme is shown below. For details of other synthetic methods, see Patent Application No. 175515/1983, No. 37.
It is described on pages 50 to 50.

- To describe the formula (I [ , 1-
octadecenyl), alkynyl groups (e.g. propynyl,
4-methyl-2-pentynyl, 5-tridecyl, 1-octadecynyl), an oxy radical group, or a hydroxyl group, and particularly preferably a hydrogen atom. R3, R,
, R5 and R6 may be the same or different and each represents a hydrogen atom or an alkyl group (eg, methyl, ethyl, propyl, octyl, hexadecyl).

A represents a nonmetallic atomic group necessary to form a 5-, 6-, or 7-membered ring, such as -CH2CH2, CH2C
H2CH2, CH2CCH2.

I ○ -CH20CH2-, -CH2SO2-CH2-.

-CH20C-, -CH2-CHCH2-.

0 0R7 etc. R7 and R8 may be the same or different and each represents a hydrogen atom, an alkyl group, an acyl group, a sulfonyl group, a sulfinyl group, or an alkoxycarbonyl group. Here R3 and R,, R5 and R,, R and R3, R3
and A are bonded to each other to form a 5- or 6-membered ring (
For example, cyclopentyl, cyclohexyl, cyclohexenyl, pyranyl, piperazine, piperidine, morpholine) may be formed.

In terms of the effects of the present invention, A is preferably an atomic group forming a 5- or 6-membered ring, and more preferably an atomic group forming a piperidine ring. R3, R4, Rs.

It is preferable that at least two of and R6 are alkyl groups, more preferably R3, R<.

This is the case where all of R5 and R6 are alkyl groups.

On the other hand, R is preferably a hydrogen atom or an alkyl group,
Particularly preferred is a hydrogen atom.

A specific example of Formula (1) is shown below, but the present invention is not limited thereto.

■-15 ■-21 =60- ■-25 ■-26 ■-27 ■-28 ■-29 ■-30 ■-31 ■-32 ■-35 ■-37 ■-45 ■-46 671 ■-48 ■-52 These compounds are described in JP-A-49-53572 and JP-A-49-53572.
No. 53573, No. 49-53574, No. 49-535
No. 75, No. 49-7180, Special Publication No. 51-1420, British Special Publication No. 1,326°889, No. 1,354.31
No. 3, No. 1,410゜846, United States Special Kitsuki No. 4,268
, No. 593 and No. 4.452.884.

In addition, the amount of these compounds added is 5 to 2 to the coupler.
00 mol%, more preferably 10 to 50 mol.

Further, examples of image stabilizers that are preferably used in combination with the compound of the present invention include compounds represented by the general formula [IV] and metal complexes.

General formula [■] OR.

In the formula, R3 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group; Or represents an aryloxy group. R4, Rs, Ra
, R7 and R8 may be the same or different from each other,
Each hydrogen atom, alkyl group, alkenyl group, aryl group, acylamino group, alkylamino group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, halogen atom or -0-R
:l". Here, R3' represents a group not represented by R3. R3 and R may be combined with each other to form a 5-membered ring, a 6-membered ring, or a spiro ring.

R4 and R5 or R9 and R6 are bonded to each other to form a 5-membered ring,
A 6-membered ring or a spiro ring may be formed.

Next, R<, Rs, R,6, of general formula [IV]
R? And to describe R8 in more detail, Rh, R
s, Re, R7 and R6 may be the same or different, and each represents a hydrogen atom, an alkyl group (e.g. methyl group, 11-butyl group, n-octyl group, 5ee
-dodecyl group, L-butyl group, t-amyl group, t-hexyl group, 1-octyl group, octadecyl group, α, α
-dimethylbenzyl group, 1,1-dimethyl-4-hexyloxycarbonylbutyl group, etc.), alkenyl group (e.g. vinyl group, allyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, p-methoxyphenyl group, 2 ．．
4-t-butylphenyl group, etc.), acylamino group (e.g. acetylamino group, propionylamino group, benzamino group, etc.), alkylamino group (e.g. N-methylamino group, N,N-dimethylamino group, N,N- dimethylamino group, piperidino group, N-cyclohexylamino group, N-(t-butyl)amine group, etc.), alkylthio group (e.g. methylthio group, n-butylthio group, See
-butylthio group, -butylthio group, dodecylthio group, etc.), arylthio group (e.g. phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, n-octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g. Phenyloxycarbonyl group, naphthyloxycarbonyl group, 4-
Methoxy-2-L-butylphenoxycarbonyl group, 2
．． 4-di-t-butylphenyloxycarbonyl group, etc.), a halogen atom (e.g. chloro atom, bromine atom, etc.), or -0-R3''. Here, R3' is R3
represents a group. R1, R4 and Rs may be bonded to each other to form a 5-membered, 6-membered or spiro ring. For example, if R3 and R1 combine to form a chroman ring, a coumaran ring, or methylenedioxybenzene, R4 and R5
Alternatively, R5 and R6 may be combined with each other to form a 5-membered, 6-membered or spiro ring. For example, the result of a bond is an indane ring, a spiroindane ring, etc.

Among the compounds represented by the general formula [IV], those represented by the following general formulas [1'V-1] to [IY-5] are preferred from the viewpoint of the effects of the present invention.

General formula [IV-1] General formula [■-2 general formula [JV-3] Ichirikiken formula [■-4 general formula [115] General formula [IV'-1] to [IV-5] Among them, R3, R
3'.

R, Rs, Rs, R7 and R8 are the general formula [
]V] represents the same group. R51' to R2,' may be the same or different, and each represents a hydrogen atom, an alkyl group, or an aryl group.

Among the compounds represented by the general formulas []V-1 and [IV-5], R3 and R3' are preferably an alkyl group or an aryl group, and most preferably an alkyl group. It is preferable that R4-R6 is a hydrogen atom, an alkyl group, or an aryl group.

It is also desirable to use the compound of the present invention and a metal complex. The metal complex used in the present invention is a compound having copper, cobalt, nickel, palladium, or platinum as a central metal and having at least one organic ligand having a bidentate or more conformation. Among these, nickel is particularly preferred as the central metal.

The coordinating atom that coordinates to the central metal is preferably a nitrogen atom, a sulfur atom, an oxygen atom, or a phosphorus atom.

A particularly preferred structure of the metal complexes of the present invention is the general formula [V
-1] to [V-4].

2e General formula [V-3] Among the general formulas [V-1] to [V-4], M is copper, core 6
− Represents balt, nickel, palladium, or platinum.

R1 and R5' may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group. Here, R23 and R27 may be bonded to each other. R2 represents a hydrogen atom, an alkyl group or an aryl group. R25 and R26 may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. Here, R25 and R2G may be bonded to each other to form an aromatic ring or a 5- to 8-membered ring. R3o
and R3° represents a group represented by R25 and R26.

R28 and R2 represent an alkyl group, an aryl group, an alkylthio group, an alkoxy group, an aryloxy group, an alkylamino group, or an arylamine group. Among the substituents of general formulas [l-11 to [V-4],
The group having an alkyl moiety or an ali moiety may be further substituted with a substituent.

Xl represents a compound capable of coordinating with M (for example, pyridine, organic or inorganic amines such as triethylamine or ammonia, R20), and A represents an oxygen atom, a sulfur atom, or NRzo (herein, R).

represents a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, or an alkoxy group), A and A2 may be the same or different, each represents an oxygen atom, a sulfur atom, or -NH2, and A3 represents a hydroxyl group. group, alkoxy group, alkylthio group or -N Rl 2
0 R13o (here, R+ 201R13° may be the same or different and each represents a hydrogen atom or an alkyl group).

Among the compounds represented by general formulas [V-1] to [V-4], the compound represented by general formula [V-1] is preferable in terms of the effects of the present invention.

Specific examples of the compound represented by the general formula [IV] and the metal complex will be shown, but the invention is not limited thereto.

8-3 OCsH+t(n) υshiJs(n) 8-12 ^-13 ^-14 ^-15 ^-16 ^-17 ^-20 8-22 ^-23 ^-24 UU12t12s(n) 8-25 ^-26 ^-27 8-31 rl^-33 ^-36 8-51 ^-52 ^-54 8-56 8-57 ^-58 81117(L) aHlt (jJThese compounds are No. 3336135, No. 3432300,
No. 3573050, No. 3574627, No. 3700
No. 455, No. 3764337, No. 3935016,
No. 3982944, No. 4254216, No. 4279
990, British Patent No. 1347556, British Patent No. 20628
No. 88, No. 2066975, No. 2077455, JP-A-58-205378, JP-A-52-1.5222
No. 5, No. 53-17729, No. 5:3-20327,
No. 54-145530, No. 55-6321, No. 55
No. -21004, No. 58-24141, No. 5-10
No. 539, Special Publication No. 48-31625, No. 51-123
It can be synthesized by the method described in No. 37 and a method analogous thereto.

The compounds represented by the general formulas [■] and [V] of the present application are -
For couplers represented by up to [1], 10 to 40
It is added in an amount of 0 mol%, preferably 30 to 300 mol%.

On the other hand, the metal complex (V) of the present application is 1 to 100 mol%, preferably 3 to 100 mol%, based on the coupler represented by
It is added in an amount of 40 mol%.

The magenta coupler and the antifading agent according to the present invention are used in at least one of the photographic photosensitive layers using a high boiling point organic solvent.
It can be dispersed and contained in two hydrophilic organic colloid layers.

As a method for introducing a coupler into a silver halide emulsion layer, a known method such as that described in U.S. Pat. No. 2,322,027 is generally used.

The compound of the present invention is preferably added to the hydrophilic colloid layer of the photosensitive material at the stage of producing the photosensitive material, and usually, the compound is added to the hydrophilic colloid layer of the photosensitive material alone or in combination with a high boiling point solvent having a boiling point of 170°C or higher at atmospheric pressure or the above oil. It is prepared by dissolving it in a mixed solvent with a low boiling point solvent and emulsifying and dispersing this solution in an aqueous solution of a hydrophilic colloid such as gelatin.

Preferably, the compounds of the invention are soluble in high boiling solvents.

There is no particular restriction on the particle size of the emulsified dispersion of this high boiling point solvent, but it is preferably 0.05 μm, particularly 0.01 μm.
3μ is preferred.

Specific examples of the oil include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate), phosphate ester (diphenyl) phosphate, triphenyl phosphate, tricresyl phosphate. phate, dioctylbutyl phosphate, monophenyl-p-1-butylphenyl phosphate), citric acid esters (e.g. acetyl tributyl citrate),
Benzoic acid esters (e.g. octyl benzoate octaalkylamides (e.g. diethyl laurylamide, dibutyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, to diethyl azeley 1), trimesic acid esters (e.g. tributyl trimesate) ), compounds containing epoxy rings (for example, U.S. Tokkyo Kitsuki 4,540.
657), phenols (for example), and ethers (for example, phenoxyethanol, diethylene glycol monophenyl ether). The low boiling point solvent used as a replenishing solvent (1) is an organic solvent with a boiling point of 30°C to 150°C at atmospheric pressure, such as lower alkyl acetate such as ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate,
Examples include methanol, ethanol, secondary butyl alcohol, cyclohexanol, fluorinated alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate acetone, methyl acetone, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, chloroform, cyclohexane, etc. be able to.

In addition, instead of high boiling 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 rays can be used. The additive itself, such as an absorbent, may also serve as an oily solvent.

Latex polymers include acrylic acid, methacrylic acid and its esters (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate, etc.), acrylamide, t-butylacrylamide, methacrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate, etc.), acrylonitrile. , styrene, divinylbenzene, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters (e.g. maleic acid methyl ester), N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine. A latex polymer produced using one or more of these is used.

Examples of surfactants used in the present invention when dispersing a solution of the compound of formula (I), (II), (III) or (IV) alone or together with a coupler in an aqueous protective colloid solution include saponin , sodium alkylsulfosuccinate, sodium alkylbenzenesulfonate, and the like.

It is preferred to use anionic surfactants with sulfonic acid groups, such as the compounds described below, alone or in combination.

Na03SCHCOOCHCJ9 ■ 2H5 There are no particular restrictions on the coupler used in this color photographic material, but examples include the following.

(a) Yellow coupler Couplers represented by the following maximum (Y-1) and (Y-11).

General formula (Y-1) H2 CHs C-COCHR+ + CHy Zz (In the formula, R11 represents a substituted or unsubstituted N-phenylcarbamoyl group, and Zll represents the reaction with an oxidized product of an aromatic primary amine color developing agent. ) General formula (Y-I[) (In the formula, R11 represents a substituted or unsubstituted N-phenylcarbamoyl group, and Zll represents an oxidized product of an aromatic primary amine color developing agent. represents a group capable of leaving in the reaction, R12 represents a hydrogen atom or a substituent, and S represents 1-
Represents an integer of 5. ) - Typical chemical structures of the yellow couplers represented by (Y-1) and (Y-2) are those described in the following US patent specifications. The numbers in parentheses represent the number of columns providing detailed explanations of chemical structures.

U.S. Special Kitsuki No. 3,894,875 (I-2), 3.4
．． No. 08,194 (2-3), No. 4,404.274 (3-17), No. 4,022,620 (3-7).

No. 4,057,432 (I-4), etc.

<b> Cyan coupler Below - Coupler represented by (>I).

-Fukudai ((, -1> H Zll In the formula, R31 represents an alkyl group, a cycloalkyl group, an aryl group, an amine group, or a heterocyclic group.

R3□ represents an acylamino group or an alkyl group.

R33 does not represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. Further, R33 may be combined with R32 to form a ring. Z31 represents a hydrogen atom, a halogen atom, or a group capable of leaving in reaction with an oxidized product of an aromatic primary amine color developing agent. ) - A typical chemical structure of the cyan coupler represented by (C-1) is as described in the following US patent specification. The numbers in parentheses are
Represents the number of columns that provide detailed explanations of chemical structures.

U.S. Special Kitsuki No. 2.920.961 (I), No. 3.77
No. 2.002 (I-3), No. 3.864°-100-366 (2-6), No. 4.124.396 (2)
, No. 4.333,996 2-8), No. 4.56
No. 5.777 (3-5), No. 4, 564.

No. 586 (2-4), etc.

Each of the above couplers may form dimers or higher multimers.

Specific examples of these couplers are listed below, but it goes without saying that the present invention is not limited thereto.

-101= (Y-8) P6 (Y-11) rθ (Y-14) rθ (Y-15) l Yes 107-1 (Y-17> (Y-20) CH3 (Molecular weight 30,000) (Y-24) (C-4) (C-5) QC)I2CH2C)12cOOH \ (t)05■11 (C-7) H −1,11= (C-11) (C-19) (t)CJlt (C-26) (t)CsH+ + (C-27) (C-28) l f (C-29) 11shi! The color developer of the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

= 118- D-IN, N-'; Ethyl p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)triene D-44- (N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-[β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl- N-ethyl-N-(β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-stylaminophenylethyl)methanesulfonamide D'-8N, N-dimethyl-p-phenylenediamine D-94-amino-3 -Methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Of the above p-phenylenediamine diluents, 4-amino-3-methyl-N=ethyl-N-(β-(
methanesulfonamido)ethyltoaniline (exemplified compound D-6).

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g per 11 of the developer solution.
More preferably a concentration of about 0.5 g to about Log.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, JP-A-63-43138
Hydroxamic acids described in No. 6-3-170642, hydrazides, and hydrazides described in No. 63-4465
Phenols described in No. 7 and No. 63-58443, α-hydroxyketones and α described in No. 63-44656
- It is preferable to add aminoketones and/or various saccharides described in No. 63-36244. In addition, in combination with the above compounds, JP-A-63-4235, JP-A-63-24
No. 254, No. 63-21647, No. 63-14604
No. 0, No. 63-27841, and No. 63-25654
Monoamines described in No. 63-30845, No. 63-146040, Diamines described in No. 63-43139, No. 63-21647, and No. 63-2.
Polyamines described in No. 6655, polyamines described in No. 63-44655, nitroxy radicals described in No. 63-53551, No. 63-43140, and No. 63
- Alcohols described in No. 53549, No. 63-5665
It is preferable to use the oximes described in No. 4 and the tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in No. 349, United States Special Kitsuki 3,
The aromatic polyhydroxy compound described in No. 746,544 and the like may be contained as necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Specific examples of buffering agents include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraboron potassium acid, 0-hydroxybenzoic acid sodium (sodium salicylate), 0-hydroxybenzoic acid potassium, 5
Examples include sodium -sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention
It is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/!
It is preferably at least 0.1 mol/! ~0.
Particularly preferred is 4 mol/l.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N.

N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid , 1-hydroxyethylidene-1゜1-diphosphonic acid, N,'N'Nbi(2-hydroxyhensyl)ethylenediamine-N,N
'-Diacetic acid Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary.

The above-mentioned compounds used in the present invention have particularly remarkable effects in the case of color developing solutions that do not substantially contain benzyl alcohol.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019, and Undeveloped Patent No. 3,
813,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho 44-30074, JP-A-56-156826 and JP-A No. 52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2
, No. 494,903, No. 3,128゜182, No. 4,
No. 230,796, No. 3,253.919, Special Publication No. 4
No. 111431, U.S. Patent No. 2,482.546, 2. 596. No. 926 and 3,582,3,16
Amine compounds described in Japanese Patent Publication No. 37-16088
No. 42-25201, U.S. Patent No. 3. 128.
No. 183, Special Publication No. 4111431, No. 42-238
83 and US Pat. No. 3,532; 501, etc., 1-phenyl-3-pyrazolidones, imidazoles, etc. may be added as necessary. - In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention includes Fluorescence Et 12
5- Preferably contains internal cutting. As a fluorescent whitening agent, 4
．． Preferred are 4'-diamino-2,2'-disulfostylhene compounds. Addition amount is 0-5g/I! , preferably 0.1 g to 4 g/β.

Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. Processing time is 20 seconds ~ 5
minutes, preferably 30 seconds to 2 minutes.

It is preferable that the amount of replenishment is small, but 20
-600 ml, preferably 50-300 ml.

More preferably, it is 100 mf to 200 mf.

Next, the desilvering step in the present invention will be explained.

The desilvering process of the present invention uses a bleach-fix solution. In the present invention, the effect of the present invention becomes more significant when the process time of the desilvering step is shortened. That is, it is 6 minutes or less, more preferably 30 seconds to 4 minutes. More preferably, the time is 30 seconds to 60 seconds.

The bleach-fixing solution used in the present invention will be explained below. The bleaching agents used in the bleach-fixing solution used in the present invention include iron, cobalt, nickel, manganese, and chromium.
Complex salts can be used, especially organic acid complex salts of iron(III), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid. ) or organic acids such as citric acid, tartaric acid, and malic acid.

Among these, iron(III) aminopolycarboxylic acid complex salts are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution.

Aminopolycarboxylic acids useful for forming 88M salts include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, Examples include methyliminodiacetic acid, iminodiacetic acid, glycol ether di7minetetraacetic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron (III
) Complex salts are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric sulfate, ferric ammonium sulfate, and ferric phosphate. etc. and an aminopolycarboxylic acid chelating agent in a solution.
An iron ion complex salt may be formed. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. The amount added is 0.01 to 1.0 mol/l, preferably 0.05 to 0.50 mol/l. bleach-fix solution and/or
Alternatively, various compounds can be used as bleach accelerators in these pre-baths. For example, the US special kitsuki 3°89
3.858 Specification, German Special Kitsuki 1,290.812
specification, JP-A-51-95630, -129- publication, Research Disclosure No. 17129 (
Compounds having a mercapto group or disulfide bond described in JP-B No. 1978-8506, JP-A No. 52-20832, JP-A No. 53-32735,
US Patent 3. 706. Thiourea compounds described in No. 561, etc., or halides such as iodine and bromide ions are preferred because they have excellent bleaching blades.

In addition, the bleach-fix solution used in the present invention contains bromide (
Rehalogenating agents such as potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide) may be included. . If necessary, one or more inorganic substances having pH buffering ability such as boric acid, borax, sodium mechborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fix solution according to the present invention is preferably a known fixing agent, ie, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate. Also,
A special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. 11
The amount of fixer per mol is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH of the bleach-fix solution of the present invention is 3.5 to 65, more preferably 4 to 5.5. In order to adjust these pH values, various organic and inorganic acids, bases and buffers can be used. For example, acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, propionic acid, citric acid, etc., and alkalis include sodium hydroxide, potassium hydroxide, aqueous ammonia, various amines, etc., but are not limited to these.

If the pH is higher than the present invention, the desilvering property and image stability will be poor, and if it is lower, the liquid stability will deteriorate and the leucoization of the cyan dye will become noticeable.

Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and fixing solution in the present invention contain sulfites (e.g., sodium nitrite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, etc.) as preservatives. (e.g., potassium metabisulfite, etc.), metabisulfites (e.g., potassium metabisulfite, potassium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.50 mol/β, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

The silver halide color photographic light-sensitive material used in the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, followed by washing with water and/or stabilizing treatment.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
nalof the 5ociety of Moti
on Picture and Television
Engineers) Volume 64, P, 248-253
(May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multistage countercurrent method, the amount of washing water can be greatly reduced, for example, by 0.54 water per 1% of the photosensitive material! -11' or less is possible, but the increased residence time of water in the tank by 7f causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. As a solution to such problems in processing the color photosensitive material of the present invention, the patent application No. 1986-
The method for reducing calcium and magnesium described in No. 131632 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542, chlorinated sodium isocyanurate described in JP-A No. 61-120145, and chlorine-based disinfectants described in Japanese Patent Application No. 60-105487. Hensitriazole, copper ions, etc. by Hiroshi Horiguchi, ``Chemistry of antibacterial and antifungal agents'', Hygiene Technology Gold Wire, ``Sterilization, sterilization, and antifungal technology of microorganisms''
It is also possible to use the fungicides described in ``Encyclopedia of Antibacterial and Antifungal Agents,'' published by Kinshi, Nikki, Japan.

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8.

The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 1 hour at 15 to 45°C.
0 minutes, preferably in the range of 30 seconds to 5 minutes at 25-40°C.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound represented by formalin, or a film suitable for stabilizing the dye.
Examples include buffering agents and ammonium compounds for adjusting to H. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step,
No. 8543, No. 58-14834, No. 59-184343
No. 60-220345, No. 60-238832, 6
No. 0-239784, No. 60-239749, 61-4
All known methods described in No. 054, No. 61118749, etc. can be used.

In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. As an example of this, the overflow of the washing water reduced by the multi-stage countercurrent method is made to flow into the bleach-fixing bath which is the previous bath, and the bleach-fixing bath is replenished with concentrated liquid.
One example is to reduce the amount of waste liquid.

The color photographic light-sensitive material of the present invention can be applied to, for example, color paper, color reversal paper, color direct positive light-sensitive material, color positive film, color negative film, color reversal film, etc., but in particular, it can be applied to color paper, color reversal paper, etc. Common use is preferred.

The silver halide emulsion of the light-sensitive material used in the present invention may be of any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride. For example, when performing rapid processing or low replenishment processing such as the color paper, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and more preferably a silver chloride content of 80 to 80%. Particularly preferred is 100 mol%. In addition, when high sensitivity is required and it is necessary to suppress fog during production, storage, and/or processing, silver chlorobromide emulsions containing 50 mol% or more of silver bromide or Silver iodide emulsions (which may contain up to 3 mol % of silver iodide) are preferred, and more preferably 70 mol % or more. Color photosensitive materials for photography include silver iodobromide,
Silver chloroiodobromide is preferred, where the silver iodide content is between 3 and 15
Mol% is preferred.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multi-phase structure such as a bonded structure, or may have some kind of structure rather than having a uniform phase throughout the grain. is preferred, and a double structure is particularly preferred. Moreover, they may be mixed.

The average grain size distribution of the silver halide grains used in the present invention may be narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size ratio) is within 20%, particularly preferably,
It is preferred to use so-called fractional silver halide emulsions of up to 15% in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a fluctuation rate) in the same layer or in a separate layer.
Can be applied. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the halogenated root particles used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
It may have a crystalline form or a coexistence of these crystals, or it may have an irregular shape such as a spherical shape.
It may have a crystalline form (gu jar), or it may have a composite form of these crystal forms.

Furthermore, the shape of the silver halide grains is particularly preferably cubic or tetradecahedral.

Further, the silver halide grains may be tabular grains, and in particular, an emulsion is used in which tabular grains having a length/thickness ratio of 5 to 8 or 8 or more account for 50% or more of the total projected area of the grains. You can. An emulsion consisting of a mixture of these various crystal forms may also be used.

These various emulsions may be either a surface latent image type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is published in "Research Disclosure" magazine (RESEARCH DISCLO3IIR).
E) vol, 176ItemNb, 17643 (I,
It can be prepared using the method described in Section II, ■) (I978, 12).

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are described in Research Disclosure, Vol. 176, Teeth 17643 (I9
78, December) and Volume 187, No. 18716
(November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two ``Research Disclosure 1'' publications, and the descriptions are shown in the table below.

Additive type RD17643 RD18716
1 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity increasing agent
Same as above 3 Spectral sensitizers pages 23-24 Page 648 right column 4 Super sensitizers Page 649 right column 5 Brightening agents page 24 7 Capillaries - page 25 8 Organic) carrier
Page 25 - 14,0- 10 Ultraviolet absorber 11 Anti-stain agent Page 25 right column Page 650 left to right 12 Dye image stabilizer Page 25 13 Hardener Page 26 Page 651 left column 1
4 Binder page 26 Same as above 15 Plasticizer, lubricant page 27 650 right column-1
41-Example 1 A multilayer silver halide photosensitive material 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.

(1st layer coating solution adjustment) Yellow coupler (ExY-1) and (ExY-2)
) 10.2g each, 9. h and color image stabilizer (Cpd-
1) Add and dissolve 27.2 cc of ethyl acetate and 7.7 cc (8.0 g) of high boiling point solvent (Solvl) to 4.4 g, and dissolve this solution into 185 cc of a 10% geladine aqueous solution containing 8 CC of 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed.

This emulsified dispersion and emulsions EMI and EM2 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. The coating liquids for the second to seventh layer phases were also prepared in the same manner as the coating liquid for the first layer. ]-oxy-3,5-dichloro-8-1-riazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, (Cpd-2) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (ε/shoulder 2). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminated paper (the polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye.) -th layer (blue-sensitive layer) sensitizing dye (monodisperse spectrally sensitized with ExS-1>) Silver chlorobromide emulsion (EMI)...Monodispersed silver bromide emulsion (EM2) spectrally sensitized with 0.13 sensitizing dye (ExS-1>)...013 gelatin
...186 yellow coupler (E xY -1) -0,44 yellow coupler (E xY -2) -0,39 color stabilizer (
Cpd-1)...0.19 solvent (So
lv -1) -0,35 Second layer (color mixture prevention layer) Gelatin ・099 Color mixture prevention layer (Cpd-3) ...0.08 Third layer (green sensitive layer) Sensitizing dye (ExS-2,3 ) Monodisperse silver chlorobromide emulsion (E M 3 ) spectrally sensitized with...0.
Monodisperse silver chlorobromide emulsion (EM4) spectrally sensitized with 05 sensitizing dye (ExS-2,3>)...
0.11 gelatin...1
80 magenta coupler (ExM -1) ・=0
．． 39 color image stabilizer (Cpd-5)...
・0.01 color image stabilizer (Cpd-6)
...0,04 solvent (Solv-2)
・・0.12 solvent (Solv-3)
-0,25 Fourth layer (ultraviolet absorbing layer) Gelatin'...1.60 Ultraviolet absorber (Cpd -7/ Cpd -8/ Cpd
-9-3/2/6: weight ratio)...0.
70 color mixing inhibitor (Cpd-10>...
0.05 solvent (Solv-4)
・-0,27 Fifth layer (red-sensitive layer) Monodisperse silver chlorobromide emulsion (EM 5') spectrally analyzed with sensitizing dye (ExS-4,5) ...0
．． 07 Monodisperse silver chlorobromide emulsion (EM6) spectrally sensitized with sensitizing dye (ExS-4,5)...0
．． 16 Gelatin...0.
92 cyan coupler (ExC-1) -0,
32 color image stabilizer (Cpd-8/Cpd-9/Cpd-1
2-3/4/2: weight ratio) ...0.1
7 Polymer for dispersion (Cpd-11)...0
．． 28 solvent (Solv-2)
=-0,20 6th layer (ultraviolet absorbing layer) Gelatin...0.54 ultraviolet absorber (Cpd -7/ Cpd -9/ Cpd
-12=115/3: Weight ratio...0.2
1 solvent (Solv -2) -0
,08 Seventh layer (protective layer) Gelatin...1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 1
7%)...0.17 Liquid paraffin...0.03 In addition, at this time, as the irradiation prevention dye, Cpd-13
, Cpd-14 was used. Further, in each layer, Alkanol X C (Dupont), sodium alkylbenzenesulfonate, succinic acid ester, and Megafac F-120 (manufactured by Dainippon Ink) were used as emulsifying dispersant coating aids. As a stabilizer for silver halide, Cp
d-15 and Cpd-16 were used.

Details of the emulsion used are as follows.

Emulsion base Shape Particle size Br content Coefficient of variation (mo1
%> EMI cube 1.0 80 0.08
EM2 Cube 0.75 80 0.07
EM3 Cube 0.5 83 0.09
EM4 Cube 0.4 83 0.1O
EM5 Cube 0.5 73 0.09
EM6 Cube 0.4 73 0.10
Next, in the third layer of the light-sensitive material, the compound represented by the general formula (I) of the present invention is added to the coupler by an additional 30%.
A photosensitive material was prepared in the same manner except that M01% was added.

The structural formula of the monster used is as follows.

xY-1 xY-2 ExC-1 0H death! xS-1 So, IN (C2H5).

6X10-' mol/Ag mol xS-2 5o3NH(C21(,).

4×10-’ mol/Ag mol xS-3 ■ SO, HN (C2H5).

8 x 10-' mol/Ag mol x S-4 1,8 x 10-1 mol/Hg mol pd-1 pd-2 pd-3 H ll pd-5 rθ pd-6 pd-7 pd-9 CI) (I-10 0H H Cpd-11 Cpd-12 Solv-1 dibutyl phthalate 5olv-2) Refrigerated h phosphate 5olv-3)
Lioctyl phosphate 5olv-4) Linyl phosphate pd-13 001I I II II
Ipd-14 O Cpd-15 Cpd-16 The above photosensitive material was exposed through an optical wedge and then processed in the following steps.

41! Color development
38℃ 1 minute 40 seconds bleach fixing 30
～34℃ 1 minute 00 seconds ■ 30～34℃
Rinse for 20 seconds■ 30-34℃
Rinse for 20 seconds ■ Dry for 20 seconds at 30-34℃ 50 seconds at 70-80℃ (Rinse ■
→■ A 3-tank countercurrent system was adopted. 〉The composition of each treatment liquid is as follows.

Kuji moxibustion water
800z1 diethylenetriaminepentaacetic acid 1
,0g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0g Nitrilotriacetic acid 2.0° Benzyl alcohol 16111 Diethylene glycol 1011 Sodium sulfite 2.0g Potassium bromide
0.5g potassium carbonate
30g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.5g hydroxylamine sulfate 3.0g optical brightener (
WHITEX4B.

(manufactured by Sumitomo Chemical) Add 1.5° water to 1000z/pH (2
5℃) 10.251 塾 1
Decoy water
400l ammonium thiosulfate (70%) 2
00z1 Sodium sulfite 20
g Ethylenediaminetetraacetic acid iron(II[) ammonium 60g Ethylenediaminetetraacetic acid thorium acetate 10g Add water to 1000
℃) 7.0
0 length 2 pieces ion exchange water (calcium, magnesium 3 p each)
pm or less) Photographic properties were evaluated using three items: gradation, maximum density (D max), and minimum density (D 5in). The gradation was expressed as the difference in density from the sensitivity point to the point where the logarithm of the exposure (IogE) increased by 0.5. Also, after measuring the yellow reflection density of the unexposed area at this time, it was heated to 60°C and 15%RH for 9
After being left for 0 days, the yellow reflection density of the unexposed area was measured again to show the increase in staining from immediately after treatment.

The results are shown in Table 1.

Comparative Compound (R-1) As is clear from Table 1, when processed using the photosensitive material of the present invention, not only the dependence on sulfite ion concentration is extremely small, but also the staining over time after processing is It can be seen that the increase in Further, the effect of suppressing staining over time after this treatment was more remarkable than when the image stabilizers represented by general formulas (IV) to (V) were added.

Example 2 On a paper support laminated on both sides with polyethylene 1,
A multilayer silver halide photosensitive material having the layer structure shown below was prepared. The coating solution was prepared as follows.

(Preparation of 1st layer coating solution) Yellow coupler (ExY-1) 19.1 Fi each and color image stabilizer (Cpd -1>4.4 g, ethyl acetate 27.2 cc and high boiling point solvent (Solv-1) 7.
7'ec (8,0H) was added and dissolved, and this solution was diluted to 10%
1 containing 8 cc of sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of 0% gelatin aqueous solution. This emulsified dispersion and emulsions EM7 and EM8 are mixed and dissolved, and the gelatin concentration is adjusted to have the following composition to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1-oxy-3,5-dichloro-8-triazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, (Cpd-2) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The number is the coating amount (Fl/z2)
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminated paper (white pigment (T i O2) on the polyethylene on the first layer side
Contains blue dye. ) Layer (blue-sensitive layer) Monodispersed silver chlorobromide emulsion (EM7) spectrally sensitized with a sensitizing dye (EMS-1) Spectral sensitized with a 0.15 sensitizing dye (ExS-1>) Sensitized monodisperse silver chlorobromide emulsion (EMS) -, O, +5 gelatin...186 yellow color 7" (ExY -1,) -0.82 color stabilizer (Cpcl-1,) -・、0.1
9 solvent (Solv -1>-
0.35 Fifth layer (color mixing prevention layer) Gelatin...0.99 Color mixing prevention agent (Cpd -3> -0.08 Fifth layer (green sensitive layer) Spectral enhancement with sensitizing dye (ExS-2,3) Sensitized monodispersed silver chlorobromide emulsion (E M 9 )...0.
Monodisperse silver chlorobromide emulsion (E M 10 ) -0, spectrally sensitized with 12 sensitizing dye (ExS-2,3)
24 gelatin...124 magenta coupler (ExM -1) -0,39 color image stabilizer (Cpd-4> -0,25 color image stabilizer (Cpd-5) -0,12 solvent (Solv -2) - 0,2
5 Fourth layer (ultraviolet absorption layer) Gelatin'...160 ultraviolet absorber (Cpd -6/Cpd 7/C1+d
-8-3/2/6・weight ratio)...0
70 color mixing inhibitor (Cpd -9> -0
,05 solvent (Solv-3) −
0.42 Fifth layer (red sensitive layer) Monodisperse silver chlorobromide emulsion (EM-11) spectrally sensitized with sensitizing dye (ExS-4,5)...0.07 sensitizing dye (ExS-4,5) -4,5) Monodisperse silver chlorobromide emulsion spectrally sensitized (EM-1,2)...0.16 gelatin...0.92 cyan coupler (ExC-1) -0,15 cyan coupler (EXC-2) -0,18 color image stabilizer (Cpd -7/ Cpd 8/ Cpd -1
0-3/4/2: weight ratio) ...0.1
7 Polymer for dispersion (Cpd-11,)...
0.14 solvent (Solv1)
-0,20 6th layer (ultraviolet absorbing layer) Gelatin...0.54 ultraviolet absorber (Cpd 6 / Cpd 8 / C
pd -10=], 15/3: weight ratio)...
・0.21 solvent (Solv-4)
・=0.08 Seventh layer (protective layer) Gelatin ・I, acrylic modified copolymer of 33 polyvinyl alcohol ° (degree of modification 1
7%)...0.17 Liquid paraffin...0.03 At this time, as the irradiation prevention dye, Cpd-12, Cp
d-13 was used. Further, each layer contained Alkanol XC (Dupon Co., Ltd.), sodium alkylbenzenesulfonate, succinate ester, and MaHefacxF-120 (Dainippon Ink Co., Ltd.) as an emulsifying dispersant coating aid.
was used. As a stabilizer for silver halide, Cpd −
14, Cpd-15 was used.

Details of the emulsion used are as follows.

Emulsion base Shape Particle size Br content Coefficient of variation (mo
l$) EN7 Cube 1.1 1.0 0.
1OEM8 Cube 0.8 1.0
0.1 OEM9 Cube 0.45 1.5
0.09EMIO cube 0.34 1.
5 0.09EMII Cube 0.45
1.5 0.09EM12 Cube 0.3
4 1.6 0.10 Coefficient of variation - standard deviation/average size The structural formula of the compound used is as follows.

xY-1 xM-1 xC-1 Cpd-1 Cpd-2 Cpd-3 I Cpd-4 ExS-I ExS-2 ExS-3 ExS-4 1,8X10-' mol/gf, le xS-5 pd -7 H pd-9 l pd-11 pd-12 pd-13 CDd-14 SH 8olv-1 dibutyl phthalate 5olv-2 trioctyl phosphate 5olv-31
Helinonyl phosphate Sol Sea 4 Tricresyl phosphate After imagewise exposure of the above light-sensitive material, continuous processing (running test) is carried out using a paper processing machine until twice the tank capacity for color development is refilled in the following processing steps. ) was carried out.

En 1 coffin 1 play - 1 circle 1 tank capacity color development 35°C 45 seconds 161zz 17β
Bleach fixing 30-36℃ 45 seconds 161zN
17f rinse■ 30-37℃ 20 seconds -
101 Rinse■ 30-37℃ 20 seconds -1
01 Rinse■ 30~37℃ 20 seconds -10
1 rinse■ 30-37℃ 30 seconds 248xl
101 Drying at 70 to 80°C for 60 seconds per shoulder of photosensitive material (4 tanks for rinsing from ■ to ■). The composition of each processing solution is as follows.

Crab ni ni ni rishi suma shi
Multi-) 631j Night - Hemori 4th Night - Wednesday
800*f 80
0R1 Ethylenediamine-N,N,N,N- Tetramethylenephosphonic acid 1.5g1.5g Triethylenediamine (I,4-diazabicyclo[2,2,2]octane) 5.0g5.0H Sodium chloride 1.48 -Potassium carbonate 25g25゜N-ethyl-N-
(β-methanesulfonamidoethyl)-3 1-medyl-4-aminoaniline sulfate 5.0g7.0gdiethylhydroxylamine 4.2Fle, o.

Fluorescent brightener (4,4'-diaminosubenzene type) Add 2.0g2.5 water to 1000x11000zfpl+(2
5℃) 10.05 10.45U
(Tank fluid and refill fluid are the same) Water 4
00xl ammonium thiosulfate (70%>1
00a+1 sodium sulfite 17g
Ethylenediaminetetraacetic acid iron(III) Ammonia l\ 55g Ethylenediaminetetraacetic acid I/Lium acetate 5g Ammonium bromide 40g
□□□□□□”i□□□Add water
1000*1pH (25℃)
, 5.40 Fire Department (tank fluid and refill fluid are the same) Ion exchange water (3 pl each of calcium and magnesium
m or less) Next, the magenta coupler in the third layer of the above photosensitive material was changed as shown in Table 2, and the general formula (III
) was further added to the coupler in an amount of 30 mol.
A photosensitive material similar to the above photosensitive material was prepared except that % was added.

Photographic properties and increase in stain over time after processing were determined in the same manner as in Example 1.

The results are shown in Table 2.

As is clear from Table 2, it can be seen that the photosensitive materials of the present invention not only exhibit small changes in photographic properties during continuous processing, but also significantly control the increase in staining over time after processing.

Example 3 A photosensitive material was prepared by sequentially coating a first layer (lowest layer) to a seventh layer (top layer) on a double-sided polyethylene laminated paper treated with corona discharge processing. The coating liquid for each layer was prepared as follows. The unit of coating amount is 7 m2. However, for silver halide emulsions, the amount is calculated in terms of silver. The details of the structural formulas of the couplers, color image stabilizers, etc. used in the coating solution will be described later.

The coating liquid for the first layer is prepared as follows. That is, 200 g of yellow coupler, 93.3 g of anti-fading agent.
, high boiling point solvent (p) 101? and solvent (q)5y,
After heating and dissolving the mixture to which 6001N of ethyl acetate was added as a co-solvent at 60°C, it was dissolved in a 5% geladine aqueous solution 3,300 shoulder β containing a 5% aqueous solution 330 of Alkanol B (trade name, alkylnaphthalene sulfonate, manufactured by DuPont). Mixed. Next, this liquid was emulsified using a colloid mill to prepare a color dispersion. From this dispersion, ethyl acetate was distilled off under reduced pressure, and the sensitizing dye for the blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4
- A coating solution was prepared by adding 1,400 g of the triazole-added emulsion (containing 96.7 g of Ag and 170 g of gelatin) and further adding 2,600 g of a 10% aqueous gelatin solution.

Support Paper support laminated on both sides with polyethylene 1st layer (blue sensitive layer) Silver chlorobromide emulsion (silver bromide 80 mo1%)...29
0 Yellow coupler...600 Anti-fading agent (r)...280 Solvent (p)...30 Solvent (q)...15 Gelatin...1800 2nd
Layer (color mixing prevention layer) Silver bromide emulsion (after heating grain size 0.05 microns) Silver...1
0 Color mixing prevention agent (s)...5
5 Solvent (I))...
30 solvent (q)...
15 gelatin...80
0 Third layer (green sensitive layer) Silver chlorobromide emulsion (silver bromide 70mo1%)...30
5 Magenta coupler...670 Antifading agent (I)...150 Compound of the present invention (III-38)...
30 Anti-fading agent (u)...
10 solvent (p)...2
00 solvent (q)...
10 gelatin...140
04th layer (color mixing prevention layer) Color mixing prevention agent (s)...65
Ultraviolet absorber (n)...450
Ultraviolet absorber (0) ...230
Solvent (p)...50
Solvent (q)...50
Gelatin...1700 5th layer (red sensitive layer) Silver chlorobromide emulsion (silver bromide 70mo I%)...
210 cyan coupler...38
0 Anti-fading agent b)...250
Solvent (p)...160
Solvent (q)...10
0 gelatin...1800
6th layer (ultraviolet absorbing layer) ultraviolet absorber (n)...26
0 UV absorber (0)...
70 solvent (p)...3
00 solvent (q)...
100 gelatin...70
0 7th layer (protective layer) Gelatin...620n:
2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole o: 2- <2-hydroxy-3,5-di-tert
-butylphenyl)benzotriazole p Nidi(2-ethylhexyl) phthalate q Nidibutyl phthalate r: 2,5-di-tert-amylphenyl-3,5-
17 Fugee tert-butyl hydroxybenzoate s:2.
5-tert-octylhydroquinone: 1.
4-di-tert-amyl-2,5-dioctyloxybenzene The following were used as sensitizing dyes in each emulsion layer.

Blue-sensitive emulsion layer: Anhydro-5-methoxy-5°-methyl-3,3-disulfoprobylselenacyanine hydroxide Green-sensitive emulsion layer: Anhydro-9-ethyl-5,5°-diphenyl-3,3°- Disulfoethyl oxacarpocyanine hydroxide red-sensitive emulsion layer: 3,3°-diethyl-5-methoxy-9
,9'-(2,2-dimethyl-1,3-propano)thiadicarpocyanine iodide.The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3,4-triazole In addition, the following were used as irradiation-preventing dyes.

4-(3-carboxy-5-hydroxy-4-(3-carboxy-5-oxo-1-(4-sulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl) Benzenesulfonate dipotassium salt N,N'-(4,8-dihydroxy-9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt , 1,2-bis(vinylsulfonyl) as a hardening agent
Ethane was used. Couplers and anti-fade agents used (
I+) is as follows.

Yellow coupler Magenta coupler Cyan coupler Y Molar ratio 1:1 Antifading agent (U) Shi++3 Ut13 After treatment, the same operations as in Example 1 were carried out, and the same effects as in Example 1 were obtained.

Example 4 A color photographic material was prepared by coating a paper support laminated on both sides with polyethylene and two layers starting from the next layer. The polyethylene coating side of the first layer contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amounts in g/z2 units are shown below.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (antihalation layer) Black colloidal silver...0.10 Gelatin...2.00 2nd layer
Layer (Low sensitivity red sensitive layer) Silver iodobromide spectrally sensitized with red sensitizing dye (ExS-1, 2) (silver iodide 3.5 mol%, average grain size 0.5μ)
...0,15 gelatin ...1.00 cyan coupler (EXC-1) ...0.30 antifading agent (Cpd-1,2,3> ...0,15 coupler solvent (Solv-1) ,2) ...0
．． 06 Third layer (high sensitivity red sensitive layer) Silver iodobromide spectrally sensitized with red sensitizing dye (ExS-1, 2) (silver iodide 8.0 mol%, average grain size 0.7μ)
...0.11 Gelatin ...0.50 Cyan coupler (ExC-1) ...0.10 Antifading agent (Cpd -1,2,3) ...0.
05' coupler solvent (Solv-1,2)
-0,04 4th layer (intermediate layer) Yellow colloidal silver...0.02
Gelatin...1.00 Color mixing prevention agent (Cpd-4)...0.0
8 Color mixing inhibitor solvent (Solv-3,4> ・=0
．． 16 polymer latex (Cpd-5)...
・0.10 5th layer (low sensitivity green sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye (ExS-3) (silver iodide 25 mol%, average grain size 0.4μ)...・
0.20 Gelatin...070 Magenta coupler (ExM-1>...0.40 Anti-fading agent (Cpd-6)...005 Anti-fading agent (Cpd-7)...0.0
5 Anti-fading agent (Cpd-8)...0
02 Compound of the present invention (I-38>...
006 coupler solvent (Solv-3, “i5
=・0.15 6th layer (high sensitivity green sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye (ExS-3) (silver iodide 3.5 mol%, average grain size 0.9μ )・・
・020 Gelatin ...0.70 Magenta coupler (ExM -1> = 0.40
Antifading agent (Cpd-6)...00
5 Anti-fading agent (Cpd-7>...0
．． 05 Anti-fading agent (Cpcl-8) ・
...0.02 Compound of the present invention (I[l-38)
...0.06 coupler solvent (Solv-3,
5) ...0.15 7th layer (yellow filter layer) Yellow colloidal silver ...0.20
Gelatin...Yumi 00 Color mixing prevention agent (Cpd-4)...0.06 Color mixing prevention agent solvent (Solv-3, 5)...-0
, 15 polymer latex (C11d-5)...
・010 8th layer (low sensitivity blue sensitive layer) Silver iodobromide spectrally sensitized with blue sensitizing dye (ExS-4) (silver iodide 25 mol%, average grain size 0.5μ)...
015 Gelatin...0.50 Yellow coupler (ExY-1)...0.2
0 Stain inhibitor (Cpd-8)...00
01 coupler solvent (Solv-2) -0
, 05 9th layer (high sensitivity blue sensitive layer) Silver iodobromide spectrally sensitized with blue sensitizing dye (ExS-4) (silver iodide 2.5 mol%, average grain size 1.4 μ)...
・020 Gelatin...0.50 Yellow coupler (ExY 1)...0.
20 stain prevention] 4 two agents (Cpd-8) ・
・・0001 coupler solvent (Solv-2)
・=0.05 10th layer (ultraviolet absorbing layer) Gelatin...1.50 Ultraviolet absorber (Cpd-9, 1, 3)...1.
00 color mixing prevention agent (Cpd-10)...
・008 UV absorber solvent (Solv-2> ・
...030 anti-irradiation dye (Cpd-11>
...004 Irradiation prevention stain (Cpd-12
)...004 11th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.2
μ) ...007 Geladin ...1.00 Gelatin hardening agent (I-1-], ) ...017
ExS-1 ExS-2 ExS-3 ExS-4 -1,88-,, - Cpd-1 Cpd-2 O Cpd-3 Cpd-4 Polyethyl acrylate-I Cpd-a Cpd-8 -18! l- Cpd-10 ll ll Cpd-11 Cpd-12 xC-1 Shi! xN-1 xY-1 5olv-1 di(2-ethylhexyl) phthalate olv-2 trinonyl phosphate olv-3 tricresyl phosphate olv-4 dibutyl phthalate.

olv-5 Trioctyl phosphate] 12-bis(vinylsulfonylacetamido)ethane After exposing the silver halide color photographic light-sensitive material prepared as above, the liquid was processed using an automatic processor in the manner described below. When the treatment was carried out until the cumulative replenishment amount reached three times the tank capacity, the same effect as in Example 1 was obtained.

Heat] 1 hour Temperature Mother I dust member - □ Supplementary vine - First development 75 seconds 38℃ 81 330zffi
/m2 First flush (I) 45 horns 33 horns 5 horns First flush (2) 45 horns 33 nol 5 horns
5000 horns Reversal exposure 15 horns 1001ux Color development 135 horns 38℃ 15/ 33
0xl/Ya2 [J wash 45 horns 33 horns 5 horns 1000 horns bleach-fix (I') 60 horns 38 horns
7 Nono 71A White fixing (2) 60 Horn 38 Horn 7 Nono 22
0 horns third flush (I) 45 horns 33 horns 5 horns third flush (2) 45 horns 33 horns 5 horns third flush (3) 45 horns 33 horns 5 horns 5000 horns l-45
Here, the first water washing and the third water washing were each carried out by a countercurrent water washing method. That is, the washing water is passed through the first washing 2), the overflow is led to the first washing (I), the washing water is allowed to flow through the third washing (3), and the overflow is led to the third washing (2), The overflow of the third water wash (2) is transferred to the third water wash (I
).

The composition of each treatment liquid was as follows.

Nitrilo-N,N,N-trimethylene 10! ? 1
．． 0y Phosphonic acid pentasodium salt diethylenetriamine pentaacetic acid 3.0g 3.0
95su1 helium salt potassium sulfite 30.0g 30.
0g potassium thiocyanate 1.2g 1
．． 2g potassium carbonate, 35.0y 35.0FI hydroquinone monosulfonic acid 25. Og 25.0g
Potassium 18 1-phenyl-4-hydroxymethyl 2.0g 2
．． oI? -4-Methyl-3-pyrazolidone potassium bromide 0.5g...
... Potassium iodide 5. Ozg
・・・・・・One size L for water------------
−−−−−−−−−−−−−−−−−1−ri paddy;, g
, , ---19-0 pH 9,609,70 The pH was adjusted with hydrochloric acid or potassium hydroxide.

Color development - present - 1 -------------------------Mother - j night -,, J
LIL Hensyl Alcohol 15. OgZ
18.0zf diethylene glycol 12.
Oz/ 14.0z13.6-cythia 1,8-octane 0.20g 0259-diol pentasodium salt Sodium sulfite 2.0y 2.
5y hydroxylamine sulfate 3.01?
3.6@Example 5 A multilayer color photosensitive material having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

(Layer structure) The composition of each layer is shown below. The number represents the amount of application per shoulder 2 with 9. For silver halide emulsions and colloidal silver, the coated amount in terms of silver is expressed as 2, and for spectral sensitizing dyes, the amount added per mole of silver halide is expressed in moles.

Support polyethylene laminate paper [The polyethylene on the E1 layer side contains a white pigment (TiOz) and a bluish dye (ulmarine blue)] E1 layer internal latent image type direct positive core/shell silver bromide emulsion 0.26 spectral sensitizing dye (ExS 5-1) 1.0xlO-'
Spectral sensitizing dye (ExS 5-2) 6.1x
lO-5 Gelatin 1.11
Cyan coupler (Ex CC-1> 0.2
1 cyan coupler (Ex CC-2) 0.
26 Ultraviolet absorber (ExU V-1)
0.17 solvent (ExS -1)
0.23 Development control agent (ExG C-1)
0.02 Stabilizer (ExA-1)
0.006 Nucleation accelerator (E xZ S -1
) 3.0xlO-' nucleating agent (E x
Z K -1) 8.0xlO-' E2 layer gelatin 1.41 Color mixing inhibitor (ExK B -1) 0.09 Solvent (ExS -1) 0.10 Solvent (ExS -2) 0.10th E3 layer internal latent image type direct positive core/shell silver bromide emulsion 0.23 Spectral sensitizing dye (E xS S-3) 3.0xlO
-' Gelatin 1.05 Magenta coupler (ExM C-1) 0.16 Color image stabilizer (ExS A-1) 0.2
0 Compound of the present invention (I[[-38) 0.
03 solvent (ExS-3) 0.2
5 Development regulator (ExG C-1) 0.
02 Stabilizer (ExA-1>0
．． 006 Nucleation accelerator (ExZ S -1>
2.7xlO nucleating agent (E xZ K
-1) 1.4 x 10-5 E4 layer gelatin 0.47 color mixing inhibitor (ExK B -1) 0.03 solvent (ExS-1) 0.03 solvent
(E xS -2) 0.03th E
5-layer colloidal silver 0.09 Gelatin 0.49 Color mixing prevention agent (
E x K B -1) 0.03 solvent
(Ex S −1) 0.03 solvent
(EMS-2>0.03 E6
Layer 7E same as Layer 84 Internal latent image type direct positive core/shell silver bromide emulsion 0.40 Spectral sensitizing dye (ExS S -3> 4.2xlO
-' Gelatin 2.1 Yellow coupler (ExY C-1) 0.51 Solvent (ExS -2) 0.20
Solvent (Exs -4) 0.2
0 Development regulator (ExG C-1) 0.
06 Stabilizer (ExA-1>0
．． 001 Nucleation accelerator (ExZ S-1)
5.0xlO-nucleating agent (EXZ K
-1) 1.2xlO-' E8th layer gelatin 0.54 Ultraviolet absorber (E x U V -2) 0.21 Solvent (Ex S -4) 0.08
E9th layer gelatin 128 Acrylic of polyvinyl alcohol 0.17 Modified copolymer (denaturation degree 17%) Liquid paraffin 0.05 Latex particles of 0.03 polymethyl methacrylate (
Average particle size: 2.8μ steel) 81st layer gelatin 8.70 B2 layer Same as 89th layer In addition to the above composition, each layer contains gelatin hardening agent ExGK-1
and surfactant were added.

Compounds used to prepare the samples (ExCC-1) Cyan coupler (ExMC-1) Magenta coupler (ExYC-1) Yellow coupler (ExKB-1) Color mixing inhibitor ll II (ExGC-1) Development regulator l ( ExA 1) Stabilizer 4-hydroxy-5,6-)rimethylene-1,3,3a
.

7-thitrazaindene (ExZS-1) nucleation promoter 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride (ExZK-
1) Nucleating agent 6-nitoxythiocarponylamine, no 2-methyl-1
- 5:8:9 mixture of propargylquinolinium trifluoromethanesulfonate (ExGK-1) gelatin hardener 1-oxy-3,5-dichloro-3-) riazine sodium salt (ExUV-1) ultraviolet absorber Weight ratio) (ExUV-2) Ultraviolet absorber 2:9/8 mixture (weight ratio) of the above (I>, (2>, (3)) (ExS^-1) Color image stabilizer (ExS-1) Solvent (ExS-2) Solvent (ExSS-1) Spectral sensitizing dye <ExSS-2> Spectral sensitizing dye (ExSS-3) Spectral sensitizing dye (ExSS-4) Spectral sensitizing dye The above sensitive material is subjected to the following processing steps. When treated with Example 1,
A similar effect was obtained.

Processing step A: Color development 1 minute 30 seconds 38℃ 3001□1
/M2 bleach fixing 40 seconds 35℃ 300
11/WA2 water washing■ 40 seconds 30-36℃
Washing ■ 40 seconds 30-36℃ Washing ■
15 seconds 320i+4/m2 drying
30 seconds 75~80℃ Rinse water replenishment method:
A so-called countercurrent replenishment method was adopted in which the overflow liquid of the washing bath (■) was refilled into the washing bath (2) and the overflow liquid of the washing bath (2) was led to the washing bath (2). At this time, since the carry-in of the photosensitive material from the pre-bath was 35 zl/m2, the replenishment magnification was 9.1 times.

[Color developer]

m-1F■ [Ethylenediaminetetrakis 0.59 0.51
1 methylene phosphonate diethylene glycol 8.0g13.0g
Benzyl alcohol 12.0. 18.5
g Sodium bromide 0.79 - Sodium chloride 0.5. -Sodium sulfite z, o9 2.51? N
, N-diethylhydroxylamine 3.594.51?
Triethylenediamine (I,4-3,5g4.5ydiazabicyclo(2,2,2)octane)3-methyl-4-
Amino-N-ethyl-5,598,01FN-(β-methanesulfonamidoethyl)-aniline potassium carbonate
30.0g 30.0g゛
Add sruben, 1.0-i, and Kerr pure water.
1000 Shoulder β 1000++1pH1
0,5010,90 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

−,−,−,,,,,,−,,,,,,,−,,,,−
---,,,-,-,,,-,,,,,,,,, U-liquid-
Self 10 Night □ - Ammonium Thiosulfate 1
00g Sodium bisulfite 21.0g
Ethylenediaminetetraacid iron acetate Ill) 50.
0g ammonium dihydrate ethylenediaminetetraacetic acid disodium uno
10001□111 H6,3 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water]

Mother solution-replenisher without using pure water〉 Here, pure water refers to tap water in which the concentration of all cations other than hydrogen ions and all anions other than hydroxide ions in tap water has been removed to lppm or less by ion exchange treatment. be.

Example 6 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.

First layer coating solution preparation Yellow coupler (ExY) 19. ]y and color image stabilizer (Cpd-1) 4.4i? and color image stabilizer (Cp
d-7) Add and dissolve 27.2 cc of ethyl acetate and a solvent (Solv-3>8.2y) to 0.7 g, and dissolve this solution in 8 ml of 10% sodium dodecylhensensulfonate.
10% aqueous gelatin solution containing C], emulsify and disperse in 8.5 cc. - A force-field silver bromide emulsion (cubic, average grain size 088 μ, coefficient of variation of grain size distribution 008, containing 0.2 mol% silver bromide on the grain surface as a proportion of the whole grain) has an increase in blue sensitivity shown in the table. A yellow sensitized product was prepared by adding 2.0xlO-' mol of each sensitizing dye per mol of silver, followed by yellow sensitization.

The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The ceradine curing agent in each layer is 1-oxy-3
, 5-cyclo-5-1-riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (2.0 x 10-” moles each per mole of silver halide)
Green-sensitive emulsion layers (4.OX 10-" moles each per mole of silver halide) and <7.Ox 1.0-5 moles per mole of silver halide)
Red-sensitive emulsion layer (0.9x 10-' mole per mole of silver halide)
For the red-sensitive emulsion layer, the following compounds were added at 2.6 x 10-' moles per mole of silver halide.

5-mercaptotetrazole to 1 silver halide each
8.5xlO-5 mole per mole, 7.7X 10-'
mol, 2,'5xlO-' mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (layer structure) The composition of each layer is shown below. The number is the coating amount (FI/i2)
represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti02) and a blue dye (ulmarine)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion 0.30 gelatin
1.86 yellow coupler (E
xY) 0.82 color image stabilizer (Cpd -1>
0.19 solvent (Solv-3)
0.35 color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (
Solv -1) 0.16 solvent (
Solv -4> 0.08 Fifth layer (green sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ and 0.39μ mixed at 3 to 3 (Ag molar ratio), grain The coefficient of variation of the size distribution is 0.10 and 0.08, respectively.
, each contains 0.8 mol % of AgBr locally on the particle surface as a proportion of the whole particle) 0.12 Gelatin 7 1.24-213 ~ Magenta coupler (ExM) 0.20
Color image stabilizer (Cpd-3) Q, 15 Color image stabilizer (III-1) 0.02 Color image stabilizer (I-31>0.03 Solvent (S
olv-2) 0.54 Fourth layer (ultraviolet absorption layer) Gelatin 1,58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (
Cpd-5) 0.05 Solvent (Solv
-5) 0.24 fifth layer (redness N) Silver chlorobromide emulsion (cubic, average grain size of 0.58μ and 0.45μ mixed at 1.4 (Ag molar ratio),
The coefficient of variation of particle size distribution is 0.09 and 0.1, respectively.
1. AHBr・0.6 mol% each as a proportion of the whole particle
localized on the particle surface) 0.23
Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-10) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (S o
lv -6) 0.15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpcl-5) 0.02 Solvent (S
olv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Polyvinyl alcohol 0.17 Acrylic modified copolymer Modification degree 17%) Liquid paraffin
0.03 (ExY) Yellow coupler (ExC) Cyan coupler CN R= C2H5,C, Ho H C! 2.4.4 (weight ratio) (Cpd-1) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-5) Color mixture inhibitor H (Cpd-6) Color image stabilizer C ( It9(t) n+1 C4L(t) ll C+ll5(t) 24.4 mixture (weight ratio) (cpd-7) Color image stabilizer average molecular weight 60,000 (Cpd-10) (UV-1) Ultraviolet absorber CsH1+(t) 01 C, Its(t) n+1 C+l1s(t) 4-2,4 mixture (weight ratio) (Solv-1) Solvent (Solv-2) 2.1 mixture of solvent (volume ratio) ( Solv-3) Solvent (Solv-4) Solvent (Solv-5) Solvent C00C81L.

" (CH2)e □ C00C, 11,.

(Solv-6) Solvent The same light-sensitive material except that in the third green-sensitive layer of the above light-sensitive material, the compound of the present invention was added in an amount of 10 mol% based on the coupler, and an image stabilizer was further added as shown in Table 3. was prepared and processed in the following processing steps.

Processing process〉 Temperature〉 Processing time〉 Color development
35℃ 45 seconds bleach fixing 35℃
45 seconds washing■ 35℃ 30 seconds washing■ 35℃ 30 seconds washing■
35℃ 30 seconds drying 75℃
60 seconds color developer water
800*ffi ethylene diamino-N, N, N', N
'-3.0g tetramethylenephosphonic acid triethanolamino 8. O3 Sodium chloride 1.4g Potassium carbonate 251? N-ethyl-N-(β-methanesulfone 5.0g amidoethyl)
-3-Methyl-4-amine aniline sulfate N,N-bis(carboxymethyl>hydrazine 5.0g)
Fluorescent brightener (WHITEX4B, manufactured by Sumitomo Chemical) 1.09 Add water to 1000xi'pH (
25℃) 10.051
t1 phlegm water
700w, ammonium monothiosulfate solution (700i+/
1) 100xi ammonium sulfite
18g ethylenediaminetetraacetic acid ferric ammonium dihydrate 55゜ethylenediaminetetraacetic acid disodium salt 39 ammonium bromide
4h acetic acid
8! ? Add water 1
000zlpH (25°C) 5.5 Washing liquid Tap water was treated with an ion exchange resin to reduce calcium and magnesium levels to 3 ppm or less.

(The electrical conductivity at 25° C. was 5 μs/cz.) Immediately after the treatment, the yellow reflection density (stin) of the unexposed area was measured, and then the sample was left at 80° C. and 15% RH for 20 days.

Therefore, the yellow reflection density of the exposed area was measured again to determine the rise in stain immediately after processing. The results are shown in Table 3.

As is clear from Table 3, when the compound of the present invention is used, the increase in stain over time after treatment is significantly suppressed. Moreover, this suppressing effect is expressed by the −formula [I1
1], this is particularly noticeable in the case of R=H (61-
1 and 61-6K, 6M and 6L, and 6N), and when various image stabilizers were used in combination, it was more noticeable. Incidentally, when the compound of the present invention and the compound represented by the general formula [■-5] were used in combination, the most remarkable improvement effect on the suppression of staining was exhibited.

(Effect of the invention) By containing the specific magenta coupler represented by general 2〇) or (II) according to the present invention and the compound of general formula (lI[) in the same layer, sufficient coloring property and good color can be obtained. Reproducibility is obtained, and furthermore, the increase in staining over time in unexposed areas can be significantly suppressed.

Agent: Patent Attorney (8107) Kiyotaka Sasaki (
3 others)

Claims (1)

[Claims] At least one coupler represented by the following general formulas (I) and (II) and at least one compound represented by the following general formula (III) are contained in the same layer. Characteristic silver halide color photographic material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formulas (I) and (II), R_1 is an alkyl group, an aryl group, or It represents a heterocyclic group, and R_2 represents a hydrogen atom or a substituent. X represents a hydrogen atom or a coupling-off group. General formula (III) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In formula (III), R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an oxy radical group, and a hydroxyl group. R_3, R_4, R_5, and R_6
may be the same or different and represent a hydrogen atom and an alkyl group, respectively. A represents a group of nonmetallic atoms necessary to form a 5-, 6-, or 7-membered ring. Here R_3 and R_4, R_5 and R_6, R and R_3,
R_3 and A are each bonded to each other to form a 5- or 6-membered
It may also form a membered ring.