JPS6289049A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material which is suitable to effect a rapid processing at a high temp. and is stable for a change of a pH of a processing solution of a coloring development and makes it possible to sufficiently color by providing a protective layer contg. a reaction product obtd. by reacting previously a silver halide emulsion layer, a hardener and a hydrophilic colloidal substance to the titled material. CONSTITUTION:The protective layer contg. the reaction product obtd. by reacting previously the silver halide emulsion layer contg. a 2 equivalent yellow coupler and the hardener having >=3 functional groups in a molecule and the hydrophilic colloidal substance is provided in the title material. Namely, one or two layers of nonphotosensitized surface layers are coated on an outside of the silver halide emulsion layer which is coated leaving the most far from a substrate as the protective layer. A compd. having >=3 reactive points or active points of the inter-reaction between the molecules of the hydrophilic colloidal substance, especially a gelatin in a molecule, is used as the hardener. Thus, by providing the protective layer contg. the hardener, etc., having >=3 the functional groups in the molecule, the titled material which is suitable to the rapid processing at the high temp. and makes it possible to sufficiently color with the good stability is obtd.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a silver halide color photographic material.

In particular, the present invention relates to a silver halide color photographic light-sensitive material that exhibits excellent stability of photographic properties even during high-temperature rapid processing and exhibits stable photographic properties even against changes in the pH of a color development processing solution.

[Conventional technology]

Color light-sensitive materials (abbreviated as silver halide color photographic light-sensitive materials; the same shall apply hereinafter) are desirably processed as quickly as possible, therefore, rapid processing is possible, and photographic properties are stable even during rapid processing. There is a need for the development of color photosensitive materials.

Particularly in recent years, color photosensitive materials have undergone high-temperature rapid processing (
In general, processing at 30°C or higher) is required, and to achieve this, the stability of photographic properties during high-temperature rapid processing is required (
It has been demanded. As a means for achieving this, it is already known to use a so-called 2-equivalent type yellow coupler as the yellow coupler. A color photosensitive material using this yellow coupler exhibits stable color development, especially against temperature changes during color development processing. However, the stability of color development against changes in pH of the color development processing solution is still insufficient, and this improvement is strongly desired.

[Purpose of the invention]

An object of the present invention is to provide a color photosensitive material suitable for rapid high-temperature processing, and in particular, to provide a color photosensitive material that is stable against changes in pH of a color development processing solution and has sufficient color development. It is.

[Structure of the invention]

As a result of various studies on techniques for increasing the stability of coloring characteristics against pH fluctuations during high-temperature and rapid processing, the present inventors have discovered that at least one silver halide emulsion layer and at least one protective layer are provided on a support. In a silver halide color photographic light-sensitive material comprising a layer, a silver halide emulsion layer containing a 2-equivalent yellow coupler, a hardening agent having three or more functional groups in one molecule, and a hydrophilic colloid substance are prepared in advance. It has been found that the above object can be achieved by providing a protective layer containing a reacted material.

The configuration of the present invention will be described in more detail below.

In the color light-sensitive material of the present invention, as the 2-equivalent yellow coupler contained in the silver halide emulsion layer, for example, a coupler represented by the following general formula CI) can be preferably used.

General formula (1) In the formula, ×l represents any one of ■halogen atom, ■alkoxy group, and ■alkyl group. However, halogen atom: chlorine atom, etc. Alkoxy group: methoxy group, ethoxy group Cyclic alkyl group:
These include methyl group, ethyl group, etc.

Yl: represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent (sometimes simply referred to as a leaving component). The following groups are preferred. (1) Aryloxy group, (2) Petrocyclic oxy group, Represents an atomic group necessary to form a 5- to 6-membered ring with atoms selected from oxygen, nitrogen, and sulfur atoms.

R8: represents a group that can be substituted on the benzene ring, and n is 1 or 2
When n is 2, R1 may be the same or different.

R1 is a hydrogen atom, a halogen atom, (e.g. fluorine, chlorine, bromine, etc.), R,'COO-1R,'-N-C0-1R,'-N
-5O2-1■ 2,... jl... R+' Co-, R, ' NC0N-, etc.

R, IIR, 11 Here, R, + , R, IZ p, 11+ may be the same or different (each represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group, or a heterocyclic group).

Rt: represents an alkyl group or an aryl group. Preferably it is a tert-butyl group, a phenyl group or an 0-methoxyphenyl group.

Next, Y will be further explained. The end portion of the aryloxy group represented by Y is preferably phenyl, but this phenyl may have a substituent. Specific examples of the oryloxy group include a phenoxy group, a 4-carboxyphenyloxy group, and a 4-(4-benzyloxybenzenesulfonyl)phenyloxy group.

In addition, as a heterocyclic oxy group, for example, 1-phenyl-5
-tetrazolyloxy group, isoxasilyloxy group,
Examples include 4-pyridinyloxy group.

Next, representative examples of Yl in the general formula [■], that is, a group that can be eliminated during color development, are described below. However, Yl is not limited to the examples below.

CO□C, Il.

(2],) 0 1[ONH Next, specific representative examples of the yellow coupler used in the present invention will be shown. However, it goes without saying that the invention is not limited to the examples below.

Y-3 L Y-14 CHl sH++(Sy, , Y-31
Y-30 CO□C6Hl3 Y 34 Cz
tlsY-36C1 Y-37C,H6 Y-40(J
One type may be used alone or two or more types may be used in combination. Furthermore, a 4-equivalent yellow coupler may also be used in combination.

The amount of 2-equivalent yellow coupler added is 1fi halogenated
2X10-' to 5 moles per 41 moles, more preferably l
Xl0-'' to 1.0 mol.

Next, a hardening agent having three or more functional groups in one molecule and a hydrophilic colloid substance contained in the protective layer in the present invention will be reacted in advance in an aqueous solution state.

In the present invention, the protection is 8X! Layer refers to a non-light sensitive surface layer coated on the outside of the silver halide emulsion layer coated furthest from the support. This protective layer may consist of multiple layers, but preferably one or two layers.

In the present invention, the hardening agent having three or more functional groups in one molecule refers to a hydrophilic colloid substance used as a binder, especially one that has one reactive site with gelatin molecules or one active site that causes gelatin molecules to react with each other. It is a compound that has three or more in its molecule. Compounds that are advantageously used as such hardeners include those having an active vinyl group and those having an active halogen.

Hardeners having three or more active vinyl groups include, for example, those described in U.S. Pat. No. 3,490,911, Japanese Patent Publication No. 47
-8796, JP-A-49-24435, JP-A-51-4
Examples include compounds described in publications such as No. 4164 and No. 52-21059. Examples of hardeners containing three or more active halogens include compounds described in JP-A-53-63062 and the like. Among these, a preferred hardening agent having three or more active vinyl groups is the following general formula (
Examples include a group of compounds represented by ll-1) and a group of compounds represented by the following general formulas (ll-2) and (ll-3'l) having three or more vinylsulfonyl groups.

General formula (U4) R(COCII=(Jlz)n
In the formula, R represents an n-valent organic residue (for example, an aliphatic residue substituted with NH, a saturated heterocyclic residue), and n represents an integer of 3 or more.

General formula (II-2) X(SOCtl=CIh)
In the n' formula, X represents a no-valent organic residue (for example, an aliphatic, aromatic, alicyclic, or saturated heterocyclic residue), and no represents an integer of 3 or more.

General formula (n -3) R++ R+□ (C112= CH30z CI CI Co
A) In formula 118, one of R1+ and R1□ represents hydrogen, and the other represents hydrogen or a methyl group. A's may be the same or different and represent a divalent bonding group (for example, -NH- or -0-) or a single bond.

B represents an m-valent aliphatic residue, an aromatic residue, or a saturated heterocyclic group which may be interrupted by a nitrogen atom.

m represents an integer of 3 or 4.

On the other hand, suitable hardening agents having three or more active halogens include the following general formula (n-4) and general formula (ff-5).
Examples include partial hydrolysates of compounds having three or more active halogens among the group of compounds represented by the following and the compounds represented by the following general formula (If-6). In addition, other hardeners according to the present invention that are advantageously used in the present invention include:
For example, U.S. Patent Nos. 3,057,723 and 3,39
Examples include polymeric hardeners described in Japanese Patent No. 6,029 and No. 4,161,407.

General formula (II-4) R13R14 i C1 In the formula, R+i and RI4 are hydrogen atoms or alkyl groups, Y is an alkylene group having 2 or more carbon atoms, a cycloalkylene group, a phenylene group, a biphenylene group, a phenysineoxyphenylene group , I5 (C1lz)-+ N (CHz),, +- group (R
15 is a hydrogen atom or an alkyl group 1,1 and I is 2
or an integer of 3) or R1 and R1'7 are hydrogen atoms or alkyl groups, M2 and.

□ represents an integer of 2 or 3).

General formula (TI-5) In the formula, Raw, Raw and R1° are hydrogen atoms or alkyl groups. is an integer of 2 or 3 11. is 1 or 2
represents an integer.

General formula (n-6) In the formula, R8 is a hydrogen atom or an organic residue, and X is (ms
+n4) valent organic residue (e.g. alkylene group, phenylene group) 1, 4 is 0 or a positive integer 1. ．． 4 represents a positive integer, Ca4 + , 4≧2.

Typical specific examples of hardeners represented by formula -i [■-1] or ll-63 are listed below, but the hardener is not limited to these.
8H-I CH20CONHCOC
H=CI+2CH・=CHC0−N I(N −C0C
)l=cH2H, (ゝ\/' H-1[ CHzOCONHCOCl(=C)IzH-4C83C
(CH2SO□Ctl = CH2) 3H-5Czt
ls C(C1hSOzCH=CHz)3H-6Ca
H+? C(CHzSO□CH-Ca2)3H-7
CHz -CH5O□CH, -CH-So□CH=CH
, H-1C1l□=Cll5O□CI(z Cll
C1(□SO□CI+=C1hSO□C1l = C
1h lh CH2CCH2C1I C(CII3)2 So□
CH=CIhSOzCII=CHz 5OzCH=
C1l, CL So□C)l = C
H2I HOCCHCH5OzCH-CHz l (CHi 5OzCH=CHz SO□CH=C1h CH□==CHSOzCHz CC(CH3)zO
HSO, CII = CHz: SO□C
H=CIh [CIl□=Cll5O□CHz CC(CH:l)
z OCl1zCtlzOHSO□CR=CIh I co
.

Indigo CH2=Cll5O□CH, -C-CH-C1lzSO
□CII=CL1□I SO□CR= CH2 1 (C112= Cll5O□CI+□)3CC1! □
5OzCIIzCHzSCII□C00I+H-16(
C1t 2= Cll5O7CI+□):lCCILz
SO□C1I□C)I ZNIIC)I 2CII□5
O311)(-1,7(C1l□-CIISO□CI+
□) 3C--C)IzSOzCIIzC)lzoll
H-18 (C1lz-CIISOzCHz)3c
CHzBrH-19 (Cllz = Cll5OzCI
I□)3C-CIl□SO□CH2CH2NlICH2
C0OC2H5H-20(CI□-CH5Oz)2CH
Cl1(So□CH-CHz) 2I(-2],
C (CII□5O2CII = C1l□).

H-22C)l □ CH□=Cll5O□C1l□-CCH(SOzCI(
= CH2) t5O2CH=C11□ IL23 CH3CLl
1 CHz-CH5OzCIIz CCl1r-CH2
CC112SOZCH=CH2SO2C1l = CI
l□SO□C)I=CH2H-24CHj
CHff CH3II
1 CHz=CH3Oz CCC=C-C-C(CH,)
zsO□CH=CH□CIl, SQ□CH=C
H□ SO□CH=CH□H-25(CIlz=CI(
SOz)zC)I-cH-CIl(So□CH=CHz
)z5O2C1l = C11z H-26SO□Cll=CIh (Cll z = Cll5O□)2CIl-C-CI
l(SO2C1l = CH2) 2SO2C1l =
C11□ H-27 (C1l□=Cll5OzC11□), C-N
0□H-28 (C112=CIISO□C8□), C-
Ni+□H-29(C)12=CH5O□CH2)3C
CH20CZIISH-30 (CI+2=CH3O□C
1h) :lCNHC)IZcOOHH-31(CI(
2= Cll5O□C11z) :lCN1(CHzC
llzSOJH-32 (Cll z = C1l So
□C11□)3CC1(ZOClhC(C1(2SO□
CH=CI+□)3H-33C113C(C1l□QC
)l 2SO□Cll =CIt 2) xH-34C
(CII20CH□SO□C)I = CH2) aH
-35N(CH2C1120CI12SO2CH=CH
2) 3H-36 (CI+2=CIISO□C11z)
2CHCH(Ct(zso□C11=CIh) zH-
37(CH,=Cl1SO□CH2)3CCH2OC1
1□C(CII□SO□Cl1=CH□)3H-38S
O□C11=CI+□ H-41So□CH=CH2 H-42CI.

(CHj 2=CH3O□CHC11□C00CH2)
4CH-43CIO.

(CI□-CIISO□CIt CII□C00C11
□) 3C-CI (3-44CH:+
C1hCC1ball2=CIISO□CIl
□ClIC0NII) zc)IcsI□CH(NH
COCit CH□SO□C11= (41□)2-4
5 CH3,,-4
6CH3 CHz=CHS(h CHGHz Co NHC
1+□ C) 13 CH2 C1lz =CHSo□-Cll CHz Co
N" C1+□ C113C1h C!12=cHSOx CHCHz CONllH
-47CH3 CI (2=CH-3o□-CI-C1l□-CO-Nl
+lh CHi C1'lz I CH,=CH-5o□-CH-CH□-CO-NCH2 CIl:l CH2 Ctlz=CHSo□-CM CHz CO0H-
48CL Cth (C1l
z-CH3O□CII CII□C00CH2) 1
cNtlcOcH□Ct(SOzC1l=CHzH-4
9CH3CO:1! lH-5
0C0CI(zcIl□SO□CH=CH205OzC
H=CHz cx cpH-55
CH3 CI CβH-56C
ll3 C11:1 cx cxH-57
CI(.

0β 01CI
C1cx
czcx
C7!11-Li I CI CβH
-E CI CI
Cβ
CeC7!
l! dβH-66CH.

Cil!
CβCl
CI! 1-1-69
C,L C311rCI
CβcI! cx CI
Cj2H-73CH3Cl
CICI CICjl!
C1C1 (1 Among the hardening agents listed above, those with poor solubility in water (
(found in some vinyl sulfone hardeners), groups that react with vinyl sulfone groups (e.g. SH groups, N
l (groups, Nl+2 groups, etc.) and water-soluble groups (e.g. OH
group, cooH group, 5o3) 1 group, SO□H group, O20,
Water solubility can be imparted by reacting with a compound having (H group or a salt thereof). One or more of these vinyl sulfone group-reactive groups and water-soluble groups may be contained in the molecular structure. The water-solubility imparting compounds preferably used in the present invention are listed below.

A-1112NcOONa A-28! N5OJ A -3) ISCII zcOOH A-4HSCH, C00Na A-5t (SC) I2COOK A-5H3CHzCOOLi A -7HSCII zCHzcOOtlA-8H5C
HzC1hCOOK A-12H2NCH2C) I! 0)l A-13H2NCH2C1hO3O, HA-1411□
NCH2CH20SO3KA-15H□NCII□co
oH A -16HzNCIlzCOONa A-17CI+3NHC112COOKA-18It□
NC! l□5O3H A -19CLNIICII2SOJ A-20H2NCH2CH25O3H A-21II□NCH2CIIZS03KA -22C
H3NHCHHzC1lzSOJaA23
IN (CIl, CH, OH) lA -248N (C
HzCHzO3O3K) zA -25CH3NIIC
HzCHzCHzSOJA-27C211,NHCH
2CII□CH, CH25O3HA -28C, I+,
NHCIfzCIf2CIIzCHzSOJaA-31
HN (CHzCOO) I)z A -3311N (CHzCOOK) zA -34
H3CH2CIICI+2011OH A-35H2CH2CHC■, OH OH AJ7 CHJHC) IzCOONa To react the hardening agent (hereinafter referred to as H) and the water-solubility imparting compound (hereinafter referred to as A), a solution of H (addition of this solution of A) You can store it at room temperature or warm it up to 100 ml.

In the case of using a group that is not salted as the water-soluble 11J of A in the reaction, the water-soluble group in the reaction product may be converted into a salt form by further reacting with an alkali after the reaction. The reaction molar ratio of H and A varies depending on the number of vinylsulfonyl groups in H and the number of reactive groups in A, but in general, H having M vinylsulfonyl groups is reacted with A having one reactive group. In the case of 1 mole of H, the amount of A is 0.
The reaction is preferably carried out in a proportion of 5 to M moles, and a hardening agent having desirable properties can be obtained by reacting A in a proportion of 1 to (M-2) moles per mole of H. The desired reaction amount also varies depending on the type of reactive group in A. For example, when the reactive group is a -SH group or a =N11 group, the reaction amount as described above is desirable, but when the reactive group is an -NH2 group, In some cases, it is desirable to react the two amounts. Although the reaction product obtained by the reaction of H and A may be a single compound, it is generally not possible to obtain a product consisting only of a single compound. That is, for example, some of the vinylsulfonyl groups in (■) are annihilated by reaction with the reactive group of A, and some unreacted H or all the vinylsulfonyl groups in the molecular structure are The reaction product is often returned in the form of a mixture containing those annihilated by the reaction with the reactive groups. This is thought to be indicated by the disappearance of vinyl sulfonyl groups by reaction with reactive groups, especially those in which three or more vinyl sulfonyl groups still remain in the molecular structure, but small amounts of other reactions such as those mentioned above Even if the products are mixed together, it will not have a negative effect on their effects.Therefore, the reaction products may be isolated by chromatography, etc., if necessary, but in actual use, it is necessary to separate the reaction products. It is desirable to use the reaction product as a mixture without isolating only the main components.

The hardeners having three or more functional groups used in the present invention can be used alone or in combination.

Furthermore, in addition to the hardening agent of the present invention, a conventionally well-known bifunctional hardening agent can also be used in combination.

Examples of such hardening agents include ketone compounds such as diacetyl, dichloropentanedione, bis(2-chloroethylurea), 2-hydroxy-4,6-di-chloro-1,3,5-)riazine, U.S. Patent No. 3,288,7
No. 75, No. 2.732.303, British Patent No. 974
, 723 and No. 1,167.207, etc., compounds having reactive halogens, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3, 5-h lyazine, etc. U.S. Pat. No. 3,635.718, U.S. Pat. No. 3,232,76
No. 3, British Patent No. 994,869, U.S. Patent No. 2.7
No. 32,316, No. 2,586.168, No. 3,
No. 103,437, No. 3,117,280, No. 2
．． 983.611, 2,725,294, 2.725,295, 3.100°704, 3,091,537, 3,321,313,
Compounds such as those shown in Patent No. 3,543,292 can be used.

The hydrophilic colloid substance used as a binder in the present invention is mainly gelatin, but partially modified gelatin and the like can also be used.

Furthermore, some of the gelatin was replaced with albumin, agar, gum arabic, alginic acid, casein, 8 partially hydrolyzed cellulose HA, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyacrylic acid, polyacrylamide, imidized polyacrylamide. , polyvinylpyrrolidone and copolymers of these vinyl compounds can also be used.

An embodiment of the present invention in which a hardening agent having three or more functional groups in one molecule is reacted with gelatin or the like in advance in an aqueous solution is as follows.

The gelatin used is not particularly limited, but the reaction progresses more easily with high molecular weight and high clay gelatin than with low molecular weight and low viscosity gelatin. The reaction conditions are controlled by the reaction temperature, reaction time, and the temperature of the gelatin aqueous solution at 4 degrees Celsius depending on the type of gelatin. During the reaction, adjust the pH of the gelatin aqueous solution to neutral.
It is necessary to maintain the ease of preparation, and as a result, the progress of the reaction is delayed on the acidic side, and on the basic side of 1118 or higher, thickening and gelation occur, resulting in a decrease in free functional groups, which actually loses its ability as a hardening agent. .

Among general photographic gelatins, it is preferable to react at a gelatin aqueous solution concentration of about 12 to 20% for low viscosity gelatin, about 8 to 15% for medium viscosity gelatin, and about 6 to 12% for high viscosity gelatin. The reaction is carried out at 45 to 70°C over several minutes to several hours, but it is effective to react at around 65°C for 30 to 60 minutes. The reaction is terminated by lowering the temperature below 40° C. or by simultaneously diluting with water.

The amount of hardener used varies depending on the type of gelatin used in the reaction and the purpose of hardening, but is preferably about 0.5 to 10% (weight ratio) based on gelatin.

There is a method called seasoning as a method of accelerating the hardening of a gelatin film. In other words, the curing speed when curing gelatin etc. generally depends on humidity.
The lower the humidity, the slower the curing speed. The curing rate also depends on the temperature; the higher the temperature, the faster the curing rate. The coated and dried photosensitive material is then left in a closed container, preferably in a plastic seal, under heating, preferably at 35 to 45 DEG C., for several days, preferably 3 to 6 days. This method is called seasoning, and is generally widely used as a method for accelerating the hardening of gelatin films, and can be employed in the practice of the present invention.

In the present invention, any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used as the silver halide. can.

The silver halide grains used may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape.

In these particles, any ratio of the (1001 plane to the (111) plane) can be used. Also, they may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

In the practice of this invention, the silver halide emulsions used can be chemically sensitized by various methods.

That is, a sulfur sensitization method, a selenium aggravation method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

For example, British Patent No. 618,061, ibid., 315,7
No. 55, No. 1,396,696, Special Publication No. 1977-157
No. 48, U.S. Pat. No. 1,574,944, U.S. Pat.
No. 623,499, 1. , No. 673, 522, same 2,
No. 278,947, No. 2,399,083, No. 2,4
No. 10,689, No. 2,419,974, No. 2,44
No. 8.060, No. 2,487゜850, No. 2,518
, No. 698, No. 2.52L926, No. 2゜642.3
No. 61, No. 2,694,637, No. 2,728,66
No. 8, No. 2,739,060, No. 2,743.182
No. 2,743.183, No. 2.983.609, No. 2,983,610, No. 3,021゜215,
3,026,203, 3,297.446, 3゜297.447, 3,361,564, 3
．． 41L914, 3,554,757, 3,5
No. 65,631, No. 3,565,633, No. 3,59
No. 1,385, No. 3,656,955, No. 3.761
No. 267, No. 3,772,031, No. 3,857.7
No. 11, No. 3゜891.446, No. 3,901,71
No. 4, No. 3,904,415, No. 3,930,867
No. 3,984.249, No. 4,054,457, No. 4,067.740, Research Disclosure
No. 12008, No. 13452, No. 13654, T,
H. James, “The Theory of the Photographic Process”
he Theory of the PhotoOgra
phicProcess, ) (4th Ed, Mac
It is preferable to carry out sensitization using a chemical sensitizer or a sensitization method described in, for example, John Millan, 1977), pp. 67-76.

Furthermore, it is possible to optically sensitize to a desired wavelength range using a dye known as an exacerbating dye. Aggravating pigments may be used alone, or two or more types may be used in combination. Along with sensitizing dyes, dyes that do not themselves have spectral enhancement effects,
Or a compound that does not substantially absorb visible light,
A supersensitizer that enhances the sensitizing effect of the enhancing dye may be included in the emulsion.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiadiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these. Nuclei in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, henzoselenazole nucleus, henzimidazole nucleus nucleus, quinoline nucleus, etc. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a virazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxapridine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

Examples of useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat. No. 2,519.001, No. 2
, No. 912,329, No. 3.656,959, No. 3,
No. 672,897, No. 3.694.217, No. 4.0
No. 25,349, No. 4,046,572, British Patent 1
, No. 242.588, Special Publication No. 44-14030, No. 5
Examples include those described in No. 2-24844. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 1, No. 2゜072, No. 908, No. 2,739.149
No. 2,945,763, British Patent No. 505,979
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat. , No. 629, same 2
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in, eg, No. 776.280. Furthermore, cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in U.S. Pat. No. 2,213,995, U.S. Pat. It can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publication No. 43-4932, No. 43-4933, No. 4
No. 3-4936, No. 44-32753, No. 45-25
No. 831, No. 45-26474-1 No. 46-1162
No. 7, No. 46-18107, No. 47-8741, No. 47-11114, No. 47-25379, No. 47-
No. 37443, [item j 4R-28293, 48-
No. 38406, No. 48-38407, No. 48-384
No. 08, No. 48-41203, No. 1B-41204
No. 49-6207, No. 50-40662, No. 5
No. 3-12375, No. 54-34535, No. 55-1
No. 569, JP-A No. 50-33220, JP-A No. 50-338
No. 28, No. 50-38526, No. 51-107127
No. 51-115820, No. 51-135528, No. 51-151527, No. 52-23931, No. 52-51932, No. 52-104916, No. 52
-104917, 52-109925, 52-
No. 110618, No. 54-80118, No. 56-25
No. 728, No. 57-1483, No. 5B-10753, No. 58-91445, No. 58-153926, No. 59-114533, No. 59-116645, No. 5
No. 9416647, U.S. Patent No. 2,688,545,
2,977.229, 3,397,060, 3,506,443, 3.578.447, 3
, No. 672,898, No. 3,679゜428, No. 3,
No. 769,301, No. 3,814,609, No. 3゜8
37.862.

When carrying out the present invention, the process of chemical ripening, at the end of chemical ripening, and/or chemical After completion of ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added.

As antifoggants and stabilizers, US Patent No. 2゜713
．． No. 541, No. 2,743.180, No. 2,743.
Pentazaindenes described in U.S. Pat. No. 181, U.S. Pat. No. 2,716.062, U.S. Pat.
, 444,605, 2.756.147, 2.
No. 835,581, No. 2.852.375, Research Disclosure + - (Research Dis-
14851, triazaindenes described in U.S. Pat. No. 2.772.164, and JP-A-57-21114.
Azaindenes such as polymerized azaindenes described in U.S. Patent No. 2,131;
No. 038, No. 3,342,596, No. 3,954,4
Thiazolium salts described in U.S. Pat. No. 78, U.S. Patent No. 3.1
4, such as biryllium salts described in No. 48.067 and phosphonium salts described in Japanese Patent Publication Nos. 50-40665.
class onium salt neck; mercaptotetrazole described in U.S. Patent Nos. 2,403,927, 3.266,897, 3,708.303, and JP-A-55-135835 and JP-A-59-71047 mercaptotriazoles, mercaptodiazoles, U.S. Patent No. 2,82
mercaptothiazoles described in US Pat. No. 4,001, mercaptothiadiazoles and mercaptohenzimidazoles described in US Pat. No. 3,397,987,
Mercaptooxadiazoles described in U.S. Pat. No. 2,843,491, U.S. Pat. No. 3,364,028
Mercapto-substituted heterocyclic compounds such as mercaptothiadiazoles described in US Patent No. 3,236,6
52, catechols described in Japanese Patent Publication No. 4340256, resorcinols described in Japanese Patent Publication No. 56-44413, and polyhydroxydihenzenes such as gallic acid esters described in Japanese Patent Publication No. 43-4133; West German patent 1st
, 189,380, triazoles described in U.S. Pat. No. 3,157,509, benzenetriazoles described in U.S. Pat. No. 2,704,721, U.S. Pat. 287.135, U.S. Patent No. 3.106,4
67, U.S. Patent No. 2,27
1,229, azoles such as polymerized benztriazoles described in JP-A No. 59-90844, and U.S. Pat. No. 3,16L51.
Pyrimidines described in No. 5, U.S. Patent No. 2.751
Heterocyclic compounds such as 3-pyrazolidones described in U.S. Pat. 1379
No. 45, No. 140445, British Patent No. 1゜356.1
No. 42, U.S. Patent No. 3,575,699, U.S. Patent No. 3,64
Various inhibitor precursors described in US Pat. No. 9,267, etc.; sulfinic acids and sulfonic acid derivatives described in US Pat. No. 3,047,393; US Pat. No. 2,566.
No. 263, No. 2,839.405, No. 2.488.7
There are inorganic salts described in No. 09 and No. 2゜728.663.

The present invention can be used as a monochromatic color brightening material, but it can also be used as a multicolor color brightening material.

Multicolor color light-sensitive materials usually have dye image-forming constituent units that are sensitive to each of the three primary color regions of the spectrum, and each constituent unit is a single emulsion layer or a multilayer emulsion that is sensitive to a certain region of the spectrum. (In this case, it is preferable that the respective emulsion layers have different sensitivities) and may have layers such as, for example, a filter layer, an intermediate protective layer, and an undercoat layer. The layers of the photosensitive material, including the layers of imaging units, can be applied in various orders as is known in the art. For example, in multicolor light-sensitive materials, the silver halide emulsion containing the 2-equivalent yellow coupler of the present invention usually has blue sensitivity, but it does not necessarily have to be blue sensitive. A typical multicolor color photographic material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler, at least one having at least one magenta dye-forming coupler. a magenta dye image-forming unit consisting of two green-sensitive silver halide emulsion layers; a yellow dye image-forming unit consisting of at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler; It also consists of a material coated on a support.

In this multicolor bright light material, any 2-equivalent or 4-equivalent coupler can be used, except for the 2-equivalent yellow coupler of the present invention.

Other yellow couplers (including 4-equivalent yellow couplers) can be used in combination with the yellow coupler of the present invention, such as open-chain ketomethylene compounds, such as
A pivaloylacetanilide type yellow coupler, a hendiylacetanilide type yellow coupler, etc. may also be used. A specific example of a yellow coupler that can be used is British Patent No. 1,077.874.
No., Special Publication No. 45-40757, Japanese Patent Publication No. 47-1031
No. 47-26133, No. 48-94432, No. 50-87650, No. 51-3631, No. 52-1
No. 15219, No. 54-99433, No. 54-133
No. 329, No. 56-30127, U.S. Patent No. 2.87
No. 5.057, No. 3,253,924, No. 3,265
, No. 506, No. 3,408.194, No. 3.55L1
No. 55, No. 3,551,156, No. 3,664,84
No. 1, No. 3.725.072, No. 3,730,722
No. 3,891,445, No. 3,900,483, No. 3,929,484, No. 3,933,500,
No. 3,973,968, No. 3,990,896, No. 4,012゜259, No. 4,022,620, No. 4
, No. 029,508, No. 4゜057.432, No. 4,
No. 106.942, No. 4,133,958, No. 4,2
No. 69.936, No. 4,286.053, No. 4,30
No. 4.845, No. 4,314.023, No. 4,336
．． 327, 4, 356.

No. 258, No. 4,386,155, No. 4,401,7
This is described in No. 52, etc.

The magenta coupler is a 5-pyrazolone coupler,
Virazolohenreimidazole couplers, pyrazoloazole couplers, such as pyrazolotriazole couplers, and open-chain acylacetonitrile couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used are disclosed in Japanese Patent Application No. 58-164882 and No. 58-167.
No. 326, No. 58-206321, No. 58-2148
No. 63, No. 58-217339, No. 59-24653
No., Special Publication No. 40-6031, No. 40-6035, No. 45-40757, No. 47-27411, No. 49-
No. 37854, JP-A-50-13041, JP-A No. 51-2
No. 6541, No. 51-37646, No. 51-1058
No. 20, No. 52-42121, No. 53423129, No. 53-125835, No. 53-129035,
No. 54-48540, No. 56-29236, No. 56
-75648, 57-17950, 57-35
No. 858, No. 57-146251, No. 59-9943
No. 7, British Patent No. L252°418, US Patent No. 2.
No. 600,788, No. 3,005,712, No. 3,0
No. 62,653, No. 3,127,269, No. 3,21
4゜437, 3, 253, 924, 3,3
No. 11,476, No. 3゜419.391, No. 3,51
No. 9,429, No. 3,558,319, No. 3,582
, No. 322, No. 3,615,506, No. 3,658,
No. 544, No. 3,705,896, No. 3,725,0
No. 67, No. 3,758° No. 309, No. 3,823.15
No. 6, No. 3,834,908, No. 389L445, No. 3,907,571, No. 3,926,631,
No. 3,928,044, No. 3,935,015, No. 3,960,571, No. 4,076.533, No. 4
．． No. 133.686, 4, 237.

No. 217, No. 4.24L168, No. 4,264,72
No. 3, No. 4゜301.235, No. 4,310,623
This is what is written in the number etc.

As the cyan dye-forming coupler, naphthol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent No. 1,038,331, British Patent No. 1,543,040, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 48-59838, British Patent Publication No. 50-137137, No. 51-146828, 5
No. 3-105226, No. 54-115230, No. 56
-29235, 56-104333, 56-1
No. 26833, No. 57-133650, No. 57-15
No. 5538, No. 57-204545, No. 58-118
No. 643, No. 59-31953, No. 59-31954
No. 59-59656, No. 59-124341,
No. 59-166956, U.S. Patent No. 2,369,92
No. 9, No. 2,423,730, No. 2,434,272
No. 2,474.293, No. 2,698,794, No. 2,772,162, No. 2,801゜171,
No. 2,895,826, No. 3.253.924, No. 311.476, No. 3,458,315, No. 3
, No. 476.563, No. 3,591,383, No. 3,
No. 737,316, No. 3,758,308, No. 3,7
No. 67.411, No. 3,790,384, No. 3,88
0゜661, 3,926,634, 4,00
4, No. 929, No. 4゜009, No. 035, No. 4,01
No. 2,258, No. 4,052,212, No. 4,124
, No. 396, No. 4,134,766, No. 4,138,
No. 258, No. 4,146,396, No. 4,149,8
No. 86, 4,178°183, 4,205.99
No. 0, No. 4,254,212, No. 4゜264, 72
No. 2, No. 4,288,532, No. 4,296.199
No. 4,296,200, No. 4,299,914, No. 4,333,999, No. 4,334.011,
These are described in 4,386.155, 4,401°752, 4,427,767, etc.

In addition, in order to improve photographic characteristics, so-called combination
It can also contain couplers that form colorless dyes called couplers.

In addition to couplers, the silver halide emulsion layer contains so-called DIR substances that release phenomenon suppressors or their precursors, such as diffusive DIR substances, timing DIReA substances, or to prevent unnecessary fogging and contamination due to air oxidation of the developing agent. Hydroquinone derivatives and the like may be included to achieve this.

In addition, when carrying out the present invention, dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color capri-preventing agents, ultraviolet absorbers, fluorescent whitening agents, etc. that do not need to be adsorbed on the silver halide crystal surface may be used. Among these, various methods can be used for the hydrophobic compound, such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc., and these methods can be selected as appropriate depending on the chemical structure of the hydrophobic compound such as the coupler. can do. The oil-in-water type emulsification dispersion method can be applied using a conventionally known method for dispersing hydrophobic additives such as couplers, and usually a high-boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low-boiling point and/or water-soluble one as necessary. Dissolve in a new aqueous binder such as an aqueous gelatin solution using a surfactant, and use a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After being emulsified and dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

The ratio of high boiling point organic solvent to low boiling point organic solvent is preferably 1:0.1 to 1:50, more preferably 1:1 to 1:20.

Examples of high boiling point oils include phenol Fa"J which does not react with the oxidized form of the developing agent, phthalic acid alkyl esters, phosphoric esters, citric esters, benzoic esters,
Organic compounds having a boiling point of 150° C. or higher, such as alkylamides, fatty acid esters, and trimesic acid esters, are often used.

Examples of high-boiling organic solvents that can be used include U.S. Pat.
．． 353.262, 2,852,383, 3,
No. 554.755, No. 3,676.137, No. 3,6
No. 76.142, No. 3,700,454, No. 3,74
8゜141, 3,779,765, 3,837
, No. 863, British Patent No. 958,441, No. 1,222
, No. 753, 0L52.538.889, JP-A-47-
No. 1031, No. 49-90523, No. 50-2382
No. 3, No. 51-26037, No. 51-27921,
No. 51-27922, No. 51-26035, No. 51
-26036, 50-62632, 53-15
No. 20, No. 53-1521, No. 53-15127,
No. 54-119921, No. 54-119922, No. 55-25057, No. 55-36869, No. 56-
No. 19049, No. 56-81836, Special Publication Showa 4B-2
It is described in No. 9060, etc.

Examples of low-boiling or water-soluble organic solvents that can be used together with or in place of high-boiling solvents include those described in US Pat. No. 2,801.171 and US Pat. No. 2,949,360. Examples of low-boiling point aqueous solvents that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride,
Nitromethane, nitroethane, benzene, etc., and water-soluble organic solutions include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexane, etc. Examples include methylphosphoramide, diethylene glycol monophenyl ether, and phenoxyethanol.

Surfactants can be used as dispersing aids, such as sulfonate, alkylnaphthalene sulfonate, alkyl sulfonate, alkyl sulfate, alkyl phosphate, sulfosuccinate, and sulfonate. Anionic surfactants such as alkyl polyoxyethylene alkylphenyl ethers, steroidal saponins, nonionic surfactants such as alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkylsulfonic acids, and alkyl betaines, etc. It is preferable to use amphoteric surfactants such as, and cationic surfactants such as quaternary ammonium salts. Specific examples of these surfactants can be found in the “Surfactant Handbook” (Sangyo Tosho, 1
966) and ``Emulsifier and Emulsifier Research and Technical Data Collection'' (Kagaku Panronsha, 1978).

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the light-sensitive material of the present invention, causing color turbidity and deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

As the color antifogging agent, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. are preferable, and specific examples thereof are described in U.S. Patent Nos. 2 and 3.
No. 60.290, No. 2,336,327, No. 2゜40
3.721, 2,418,613, 2,675
, No. 314, No. 2,701,197, No. 2,704,
No. 713, No. 2,728,659, No. 2.732.3
No. 00, No. 2,735,765, No. 3,700°45
No. 3, JP-A No. 50-92988, JP-A No. 50-92989
No. 50-93928, No. 50-110337,
No. 50-156438, No. 52-146235, No. 55-95948, No. 59-5247, Special Publication No. 50
-23813 etc.

In the silver halide color photographic material of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

Examples of image stabilizers include hydroquinone derivatives, gallic derivatives, phenol derivatives and their bis forms, hydroxycoumarans and their spiro forms, hydroxychroman and their spiro forms, piperidine derivatives, aromatic amine compounds, benzodioxane derivatives, and penzdioxane derivatives. Preferred are sole derivatives, silicon atom-containing compounds, thioether compounds, and the like. As a specific example, British Patent No. 1,410,8
No. 46, JP-A-49-134326, JP-A No. 52-356
No. 33, No. 52-147434, No. 52-15063
No. 0, No. 54-145530, No. 55-6321,
No. 55-21004, No. 55424141, No. 59
-3432, 59-5246, 59-1053
No. 9, Special Publication No. 48-31625, No. 49-20973
No. 49-20974, No. 50-23813, No. 52-27534, U.S. Patent No. 2,360,290, No. 2,418,613, No. 2,675.314,
No. 2,701,197, No. 2,704,713, No. 2,710,801, No. 2,728゜659, No. 2
, 732,300, 2,735,765, 2゜816.028, 3,069,262, 3.3
36.135, 3,432.300, 3,45
No. 7,079, No. 3.573.050, No. 3,574
, No. 627, No. 3.698.909, No. 3,700°455, No. 3,764,337, No. 3.935.0
No. 16, same.

982.944, 4,013,701 boat, 4,1
No. 13,495, No. 4,120,723, No. 4,15
No. 5,765, No. 4,159,910, No. 4,254
, No. 216, No. 4,268,593, No. 4,279°990, No. 4,332,886, No. 4.360.5
No. 89, 4°430, 425, 4,452,88
Examples include No. 4.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the photosensitive material of the present invention are used to prevent capri due to discharge caused by charging of the photosensitive material by FIX rubbing, etc., and to prevent image deterioration due to UV light. It may also contain an absorbent.

As ultraviolet absorbers, benzophenone compounds (for example, JP-A-46-2784, U.S. Pat. No. 3,215,53)
No. 0, No. 3,698,907), butadiene compounds (e.g., those described in U.S. Pat. No. 4,045,229), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314, No. 794, 3,352,681
benzotriazole compounds substituted with aryl groups (e.g., Japanese Patent Publication No. 36-10466, Japanese Patent Publication No. 41-1687, Japanese Patent Publication No. 42-26187, Japanese Patent Publication No. 44-2)
No. 9620, No. 48-41572, JP-A-54-95
No. 233, No. 57-142975, U.S. Patent No. 3.2
No. 53,921, No. 3,533,794, No. 3,75
No. 4,919, No. 3,794,493, No. 4,009
, No. 038, No. 4,220,711, No. 4.323.
No. 633, Research Disclosure + - (Rese
Arch Disclosure), 22519), benzoxidol compounds (e.g., those described in U.S. Pat. No. 3,700,455), cinnamate ester compounds (e.g., U.S. Pat. No. 3,705,805).
No. 3.707,375, JP-A-52-49029
) can be used. Furthermore, U.S. Patent No. 3,499.762, Japanese Patent Application Publication No. 54-48535
You can also use those listed in this issue. UV-absorbing couplers (e.g., α-naphthol-based cyan dye-forming couplers) and UV-absorbing polymers (e.g., JP-A-58-111942, JP-A-178351, JP-A-1810)
No. 41, No. 59-19945, No. 23344, and those described in the publications) can be used. These ultraviolet absorbers may be mordanted in specific layers.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material of the present invention.

As a formalin scavenger, for example,
-87028, 57-133450, 58-1
No. 50950, U.S. Patent No. 2,895.827, No. 3
．． No. 652.278, No. 3,811,891, No. 4,
No. 003,748, No. 4.41L987, No. 4,41
No. 4,309, No. 4,418.142, No. 4,46.
4゜463, US Defense Patent No. 900.028, West German Patent No. 3,223.699, US Defense Patent No. 3,227,961
No. 3,227,962, Research Disclosure 1
Those described in No. 0133 and the like can be preferably used.

An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for.

As antistatic agents, British Patent No. 1,466.600, Research Disclosure +
Dis-closure) No. 15840, No. 162
No. 58, No. 16630, U.S. Patent No. 2,327,82
No. 8, No. 2,861.056, No. 3,206.312
No. 3,245,833, No. 3.428.451, No. 3.775,126, No. 3.963.498,
Compounds described in 4,025,342, 4,025,463, 4,025,691, 4,025,704, etc. can be preferably used.

Examples of the support used in the photosensitive material of the present invention include baryta, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acecool, polypropylene,
For example, there are polyester films such as polyethylene terreslate, polystyrene, etc., and these supports are appropriately selected depending on the purpose of use of each silver halide photographic light-sensitive material.

These supports are subjected to undercoat processing if necessary.

Various processing methods can be employed in processing the photosensitive material of the present invention, and so-called high-temperature rapid processing (usually processing at 30° C. or higher) can be employed.

The color developing solution used in the processing is, for example, an alkaline aqueous solution containing a developing agent and having a pl+ of 8 or more, preferably a pH of 9 to 12. This aromatic primary amine developing agent as a developing agent is a compound having a primary amine group on an aromatic ring and capable of developing exposed silver halide, or a precursor for forming such a compound. means the body.

The above-mentioned developing agent is typically p-phenylenediamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N=β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3- Methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N, N-diethylaniline, 4-
Amino-N, N-dimethylaniline, N-ethyl-N-
β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-
β-(β-methoxyethoxy)ethyl-3-methyl-4
-aminoaniline and their salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, etc. Moreover, various additives can be added to these color developing solutions as necessary.

The light-sensitive material of the present invention can be subjected to imagewise exposure, color development treatment, and then bleaching treatment by a conventional method.

This process may be performed simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary. Various compounds can be used as bleaching agents, and various additives including bleaching accelerators can also be added.

The present invention is realized in various forms of color photosensitive materials. One method is to process a light-sensitive material having an emulsion layer containing a diffusion-resistant coupler on a support with an alkaline developer containing an aromatic primary amine color developing agent to add a water-insoluble or diffusion-resistant dye to the emulsion layer. It is to leave it inside. In another form, a light-sensitive material having an emulsion layer containing silver halide in combination with a diffusion-resistant coupler on a support is used.
treated with an alkaline developer containing a grade amine color developing agent to form a dye that is soluble in an aqueous medium and is diffusible;
The image is transferred to an image-receiving layer made of another hydrophilic colloid. That is, it is a diffusion transfer color type.

The present invention can be applied to all kinds of color brightening materials such as color negative films, color positive films, color reversal films, and color papers.

〔Example〕

EXAMPLES The present invention will be explained in more detail with reference to Examples below. However, as a matter of course, the embodiment of the present invention is not limited to this.

Example 1 A blue-sensitive emulsion layer and a protective layer having the following composition were simultaneously coated using the slide homper method on cellulose triacetate paste of the subbing method, and a yellow coupler and a hardening layer as shown in Table 1 were coated. Twenty-four types of samples were prepared using each agent. Among each sample, 1-L 2-1.3-1... is a comparative sample that does not undergo pretreatment, that is, a step in which a hardening agent is reacted with a hydrophilic colloid substance in an aqueous solution state, and 1-2 ．．
2-2.3-2... are samples according to the present invention that were subjected to this pretreatment.

Layer 1: Blue-sensitive emulsion layer A silver iodobromide emulsion (containing 7.5 mol% silver iodide) was chemically sensitized with gold and sulfur enhancers, and 4-hydroxy-6-methyl-1,3,3a, 1.0 g of 7-chitrazaindene was added and prepared in a conventional manner to produce a blue-sensitive silver halide emulsion.

Furthermore, per mole of silver halide, 200 g of dibutyl phthalate and 600 mff1 of ethyl acetate were added to 200 g of the yellow coupler shown in Table 1, heated and dissolved, and added to a gelatin solution containing sodium triisopropylnaphthalene sulfonate and placed in a colloid mill. After emulsifying and dispersing, add the fine oil droplet dispersion from which ethyl acetate has been removed to the above emulsion,
A blue-sensitive silver halide coating solution was prepared, and the dry film thickness was 4.8.
It was applied so that it was μ.

N2: Protective layer coating liquid 100 m! 4 g of gelatin and a hardening agent as shown in Table 1 were added per layer, and the coating was applied so that the dry film thickness was 1.1 μm. The amount of gelatin at this time is 1.5 g
/ becomes m.

Snake, 7 After applying wedge exposure to each sample thus obtained, development processing was performed in the following processing steps. The γ value was measured for each sample, and the Δγ value was determined. The obtained results are also shown in Table-1. Here, the Δγ value, which is an index of processing variability, is expressed by the following formula as the variation value of T when the pH of the color developer is adjusted to 10.2 in the following processing step.

Table 1 shows samples according to the present invention (1-2, 2-2゜3-
2...) are shown in parallel with the results of the same comparative sample (1-L 2-1.3-1...) which was not subjected to pretreatment.

The processing steps described above are as follows.

This corresponds to high temperature rapid processing.

Processing process (38℃) Processing time Color development
3 minutes 15 seconds bleach, 6 minutes 30 seconds water
Wash 3 minutes 15 seconds Fix
Wash with water for 6 minutes and 30 seconds
3 minutes and 15 seconds Stabilization bath 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step was as follows.

(Color developing solution composition) (Bleach solution composition) Ice Acetic acid 10.0 ml (Fixer composition) (Stabilizing solution composition) Formalin (37% water soluble) 5.0
+yj! Development processing was performed under the above conditions.

As is clear from the results in Table 1, the samples according to the present invention had smaller fluctuations in T due to pH changes in the color developer than the comparative samples, indicating that the effects of the present invention were fully developed. I can see that it is being done.

〔Effect of the invention〕

As mentioned above, the silver halide color photographic light-sensitive material of the present invention is stable against changes in the pH of the color development processing solution;
Despite the change, the coloring property is sufficient and it is suitable for high-temperature and rapid processing.

Claims (1)

[Scope of Claims] A silver halide color photographic material having at least one silver halide emulsion layer and at least one protective layer on a support, comprising: a silver halide emulsion containing a 2-equivalent yellow coupler; silver halide color photographic photosensitive layer, and a protective layer containing a hardening agent having three or more functional groups in one molecule reacted with a hydrophilic colloid substance in advance. material.