JPH02223947A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color development property and image preservable property by incorporating respectively specific couplers into the 1st, and 2nd and 3rd photosensitive layers on a substrate. CONSTITUTION:This photosensitive material has at least three kinds of the photosensitive layers which are different in color sensitivity from each other on the substrate. The material contains at least one kind of the couplers expressed by formula I in the 1st photosensitive layer, the couplers expressed by formula II in the 2nd photosensitive layer and the couplers expressed by formula III in the 3rd layer. In the formulas, R11 to R13 respectively denote a hydrogen atom or alkyl group; R14 denotes an halogen atom or alkoxy group; Z11, Z21, Z31 denote a hydrogen atom or a group or atom which is eliminated at the time of a coupling reaction with the oxidant of an arom. primary amine color developing agent. R21 denotes a hydrogen or group which can be substd.; Z22 to Z24 respectively denote -NH-; R31 denotes an alkyl group, aryl group, etc.; R32 denotes an acyl amino group, alkyl group; R33 denotes a hydrogen atom, halogen atom, etc. The color development property and the image preserv able property are improved in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a multilayer silver halide color light-sensitive material, and more specifically, it relates to a novel multilayer silver halide color light-sensitive material that has good color development, improved image storage stability, and does not disrupt color balance. The present invention relates to a multilayer silver halide color light-sensitive material (hereinafter referred to as a light-sensitive material) containing a combination of couplers.

(Background technology) Silver halide color sensitive materials are selectively spectrally sensitized.
For example, in so-called color photographic paper (hereinafter referred to as color paper) in which a photosensitive layer consisting of a silver halide emulsion layer is coated on a support in a multilayer structure, a red-sensitive emulsion layer is usually applied in order from the exposed side. A green-sensitive emulsion layer and a blue-sensitive emulsion layer are coated, and between each photosensitive layer, an intermediate layer for color mixing prevention and UV absorption, a protective layer, etc. are provided.

In addition, in a so-called color positive film, a green-sensitive emulsion layer, a red-sensitive emulsion layer, and a blue-sensitive emulsion layer are generally coated in order from the opposite side of the support, that is, the side to be exposed. Color negative films have a wide variety of layer arrangements, and are generally coated in the order of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer from the exposed side. In light-sensitive materials having two or more different emulsion layers, there are also some light-sensitive materials in which emulsion layers with different color sensitivities are arranged between the emulsion layers, and a bleachable yellow filter layer, an intermediate layer, a protective layer, etc. inserted.

In order to form a color photographic image, three color photographic couplers of yellow, magenta and cyan are contained in the photosensitive layer, and the exposed light-sensitive material is subjected to color development processing using a so-called color developing agent. The oxidized product of the aromatic primary amine undergoes a coupling reaction with the coupler to give a color-forming element, and the coupling rate at this time is as high as possible to give a high color density within a limited development time.
It is preferable that the coloring dye has good coloring property. Furthermore, the coloring dye is required to be a bright cyan, magenta, and yellow color with little side absorption and to provide a color photographic image with good color reproducibility.

On the other hand, the formed color photographic images are required to have good storage stability under various conditions. In order to meet this requirement, the fading or discoloring speed of chromophores of different hues must be slow, and the fading speed must be as uniform as possible over the entire image density, so that the color balance of the remaining dye image does not change. is important.

(Issues to be solved by the invention!!l) In conventional photosensitive materials, especially color paper, the yellow dye image deteriorates rapidly due to long-term fading due to the effects of light, humidity, and heat. (Improvement is strongly desired.

Conventionally, color development has been poor if the color does not fade, and therefore there has been a demand for a new combination of couplers that has good color development and excellent image storage stability.

In order to partially solve these problems, various couplers, particularly combinations of yellow, magenta and cyan couplers, have been proposed.

For example, JP-A-55-38576 (U.S. Pat. No. 4.26)
6.019), No. 57-200037, No. 59-5
No. 7238, No. 60-205446, No. 61-404
No. 7, U.S. Patent No. 4. 607. No. 002, Japanese Patent Publication No. 6
No. 2-166339, No. 62173464, No. 63
No. 167361, U.S. Patent No. 4.748,100, U.S. Pat.
An example is described in No. 6150136.

However, with these coupler combinations, the coloring properties of the yellow coupler are insufficient, and furthermore, the color balance of cyan, magenta, and yellow may fluctuate because the yellow pigment part fades significantly due to deterioration due to light or heat. However, it has not yet been completely resolved.

The present invention aims to solve the above-mentioned problems at the same time. More specifically, it is an object of the present invention to provide good color development and improved image storage stability, and in particular, to provide a dark image for a long period of time. The object of the present invention is to provide a multilayer silver halide color photographic light-sensitive material whose color balance does not change either in the dark or under daylight. In particular, the object of the present invention is to provide a multilayer silver halide color photographic light-sensitive material whose color images do not fade even when stored under severe conditions under dawn light.

(Problem R for Solving Problems) The above aspects of the present invention are directed to a silver halide color photographic light-sensitive material having at least three kinds of light-sensitive layers having mutually different color sensitivities on a support. The following general formula (
Contains at least one coupler represented by [),
The second photosensitive layer contains at least one coupler represented by the following general formula (IN), and the third photosensitive layer further contains at least one coupler represented by the following general formula (TIN). This was effectively achieved using a silver halide color photographic light-sensitive material characterized by the following characteristics.

General formula (I) Including cases where it is part of an aromatic ring.

General formula (I [I) General formula (IN) In the specifications of the present application, an alkyl group (alkyl residue), an aryl group (aryl residue), an amino group (amino residue),
Heterocyclic groups or heterocyclic groups (residues thereof), sulfonyl groups (sulfonyl residues), sulfinyl groups, etc. are each used to include those further substituted with substituents.

General formula (I) will be explained in detail.

In the formula, R11, R11 and RIm each represent a hydrogen atom or an alkyl group.Although the alkyl group may be a substituted alkyl group, an unsubstituted alkyl group is preferable, such as a straight chain alkyl group (for example, methyl, ethyl, propyl, butyl). , hexyl, octyl, decyl, dodecyl, tetradecyl), branched alkyl groups (e.g. 1.3.3-)dimethylbutyl, 3,5°5-trimethylhexyl, 2-ethylhexyl, t-butyl, i-propyl, 1 .3.5.
5-tetramethyloctyl, 2.3.5-)rifthyl-
5-ethyldecyl, l-methyl-3-ethylhexyl,
1.1,3.3-Tetramethylbutyl, l.

1-dimethylbutyl, 1.1-dimethylpropyl, 1.
1-dimethylhexyl, 1. l-diethylhexyl).

At least two of Ro, Rlm, and Rlm are alkyl groups, at least one of which is a branched alkyl group, and the total number of carbon atoms of the alkyl groups represented by R3, R1, and Rts is 12 to 36. Among them, 14 to 26 pieces are preferable.

Rlm represents a halogen atom (e.g. chlorine, fluorine, bromine) 2 or an alkoxy group (e.g. methoxy, ethoxy), and a chlorine atom is particularly preferred *ZII is a hydrogen atom or a coupling reaction with an aromatic primary amine oxidant It represents a group or atom that can be separated, and specific examples thereof are the same as 211 described in detail later, but a group represented by the following general formula (A) or (B) is preferable.

General formula (A) 0-Rr (In the formula, R represents an aryl group or a heterocyclic group) General formula (B) (In the formula, 2. is a non-containing compound necessary to form a 4- to 6-membered ring. In the above general formula (A), R9 is a phenyl group monosubstituted with at least one electron-withdrawing group (for example, U.S. Pat.
933,501) is more preferable, and in general formula (B), zl is a group of nonmetallic atoms necessary to form a 5- to 6-membered ring, and is preferably a 5- or 6-membered ring. Specific examples are represented by the following general formulas (■) to (IX).

Represents a nonmetallic atom required to form a membered ring or a 6-membered ring.

More preferable specific examples of general formula (IX) are the following formulas (X) to
(Xn).

(■) (■) In the formula, Ry+,
R, yo + RII * R@* each represents a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amide group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, It represents an unsubstituted or substituted phenyl group or a heterocyclic group, and these groups may be the same or different.

K1.3 In the formula, R9゜7. R1゜8 each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group; R1113+ R1゜4 and R9゜ each represent a hydrogen atom, an alkyl group, an aryl group,
It represents an aralkyl group or an acyl group, and W1□ represents an oxygen or sulfur atom.

Couplers of formula -C may form dimers or higher multimers.

General formula (n) will be explained in detail.

In the general formula (II), R21 represents a hydrogen atom or a substituent, 2□ represents a hydrogen atom or a group or atom that can be separated in the reaction with the oxidized product of the Hong Kong primary amine color developing agent, and Z KM ＋Z! 3fl and Zz4 represent -C= -N- or -NH-, and one of the 2□-Z0 bond and the Ztx Zt* bond
elm-Zzg where one is a double bond and the other is a single bond
The case where is a carbon-carbon double bond includes the case where it is a part of an aromatic ring.

In general formula (I2), R□ is preferably a hydrogen atom,
Halogen atoms, alkyl groups, aryl groups, hetero! ! !
group, cyano group, alkoxy group, aryoloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl or aryloxycarbonyl group.

To explain these substituents in more detail, R□ is a hydrogen atom, a halogen atom (e.g., chlorine, bromine), an alkyl group (e.g., methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3-(2 ,4-di-t-
amylphenoxy)propyl, allyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonylethyl, cyclopentyl, benzyl), aryl6 (e.g. phenyl, 4-t-butylphenyl, 2
．． 4-di-t-amylphenyl, 4-tetradecanamidophenyl), heterocyclic groups (e.g. 2furyl, 2-thienyl, 2-pyrimidinyl, 2benzothiazolyl), cyano groups, alkoxy groups (e.g. methoxy, ethoxy,
2-methoxyethoxy, 2-dodecyloxyethoxy,
2-methanesulfonyle] xy), aryloxy groups (e.g., phenoxy, 2-methylphenoxy, 4t~
butylphenoxy), heterocyclic oxy groups (e.g. 2-
benzimidazolyloxy), acyloxy groups (e.g. ace[xy, hexadecanoyloxy), carbamoyloxy groups (e.g. N-phenylcarbamoyloxy, N-ethylcarbamoyloxy), silyloxy groups (e.g. trimethylsilyloxy), sulfonyl Oxy group (e.g. dodecylsulfonyloxy), acylamino group (e.g. acetamide, benzimide, tetradecanamide, α-(2,4-di-t-amylphenoxy)butyramide, γ-(3-t-butyl-4-hydroxyphenoxy) ) butyramide, α-(4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide)
, anilino group (e.g. phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamideanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5(α- (3-
t-butyl-4-hydroxyphenoxy) dodecanamido) anilino), ureido groups (e.g. phenylureido, methylureido, N,N-dibutylureido),
imide groups (e.g. N-succinimide, 3-penzylhydantoynyl, 4-(2-ethylhexanoylamino)phthalimide), sulfamoylamino groups (e.g.
N, N-dipropylsulfamoylamino, N-methyl-
N-decylsulfamoylamino), alkylthio group (
For example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-(4-butylphenoxy)propylthio), arylthio groups (e.g. phenylthio, 2-butoxy-5-t- Octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-
tetradecaneamidophenylthio), heterocyclic thio group (
For example, 2-benzothiazolylthio), alkoxycarbonylamino groups (for example, methoxycarbonylamino,
tetradecylcarbonylamino), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino, 2,4-di-tart-butylphenoxycarbonylamino), sulfonamide groups (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p -) luenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-butylbenzenesulfonamide), carbamoyl group (e.g. N
-Ethylcarbamoyl, N.

N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, N-(3-(2,4-di-tart-amylphenoxy)propyl)carbamoyl), acyl group (e.g. , acetyl group, (2,4-di-tart-amylphenoxy)acetyl, benzoyl), sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl) ) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N,N-diethylsulfamoyl), sulfonyl groups (e.g. methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl, 2-butoxy-5-tert-octyl) phenylsulfonyl)
, sulfinyl groups (e.g. octanesulfinyl, dodecylsulfinyl, phenylsulfinyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, butyloxycarbonyl, dodecylcarbonyl, octadecylcarbonyl) or aryloxycarbonyl groups (e.g. phenyloxycarbonyl, 3-pentadecylcarbonyl). decyloxy-carbonyl).

Z*l represents a hydrogen atom or a group or atom that can be separated in the reaction with the oxidized product of an aromatic primary amine color developing agent; examples thereof include a halogen atom (e.g.
fluorine, chlorine, bromine), alkoxy groups (e.g. dodecyloxy, dodecyloxycarbonylmethoxy, methoxycarbamoylmethoxy, carboxypropyloxy,
methanesulfonyloxy), aryloxy groups (e.g. 4-methylphenoxy, 4-tart-butylphenoxy, 4-methoxyphenoxy, 4-methanesulfonylphenoxy, 4-(4-benzyloxyphenylsulfonyl)phenoxy), acyloxy groups ( For example, acetoxy, tetrazokayloxy, benzoyloxy)
, sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy), amide groups (e.g.
dichloroacetylamino, methanesulfonylamino, trihonylphosphonamide), alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy), aliphatic, or Aromatic thio groups (e.g., phenylthio, dodecylthio, benzylthio, 2-butoxy-5-ter
't-octylphenylthio, 2,5-di-octyloxyphenylthio 1,2-(2-ethoxyethoxy)-
5-jerk-octylphenylthio, tetrazolylthio), imido groups (e.g. succinimide, hydantoynyl, 2,4-dioxoxazolidin-3-yl, 3
-benzyl-4-ethoxyhydantoin-1-yl),
N-heterocycle (e.g. 1-pyrazolyl, 1-benzotriazolyl, 5-chloro-1,2,4-triazole-1
-il) etc.

R11 or zg+ of general formula (II) may form a dimer or more multimer.

General formula (I) will be explained in detail.

In the general formula (III), R□ is an alkyl group having 1 to 32 carbon atoms, such as a methyl group, a butyl group, a tridecyl group, a cyclohexyl group, an allyl group, and an example of an aryl group is a phenyl group or a naphthyl group. Examples of the heterocyclic group include 2-pyridyl group,
Examples include 2-furyl group.

When R31 is an amino group, a phenyl-substituted amino group which may have a substituent is particularly preferred.

Rs+ can further include an alkyl group, an aryl group, an alkyl or aryloxy group (e.g. methoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,4-di-terc-amylphenoxy, 3-tert-butyl-4-hydroxyphenyloxy) , naphthyloxy),
Carboxy group, alkyl or arylcarbonyl group (
For example, acetyl, tetradecanoyl, benzoyl),
Alkyl or aryloxycarbonyl groups (e.g.
methoxycarbonyl, phenoxycarbonyl), acyloxy groups (e.g. acetyl, benzoyloxy), sulfamoyl groups (e.g. N-ethylsulfamoyl,
N~octadecylsulfamoyl), carbamoyl group (
For example, N-ethylcarbamoyl, N-methyl-dodecylcarbamoyl), sulfonamide groups (e.g. methanesulfonamide, benzenesulfonamide), acylamino groups (e.g. acetylamino, benzamide, ethoxycarbonylamino, phenylaminocarbonylamino),・Imide group (e.g. succinimide, hydantoinyl), sulfonyl group (e.g. methanesulfonyl)
'1 selected from , hydroxyl group, cyano group, 21, halogen atom (e.g. chlorine, bromine, fluorine)
It may be substituted with one substituent.

Rsz represents an acylamino group or an alkyl group.

The acylamino group includes an unsubstituted acylamino group (e.g., acetamide, n-tetradecanamide, n-tridecanamide) and a substituted acylamino group. As a specific example of the substituent of the substituted acylamino group, a phenoxy group is preferred; You can leave it there. rr! Specific examples of substituents for substituted phenoxy groups include alkyl groups (e.g. methyl, ethyl, n-hexadecyl, t-amyl), halogen atoms (e.g. chlorine atom, fluorine atom), alkoxy groups (e.g. methoxy, ethoxy), cyano groups. , aryloxy groups (e.g. phenoxy), acylamino groups (e.g. methanesulfonamide, acetamide L'), imide groups (
Examples include succinimide, n-octadecylsuccinimide), sulfamoyl group (eg, N-ethylsulfamoyl, n-octadecylsulfamoyl), alkoxycarbonyl group (eg, ethoxycarbonyl), sulfonyl (eg, methylsulfonyl), and hydroxyl group.

The alkyl group preferably represents an unsubstituted alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, n-propyl, t-butyl, t-octyl).

R5'J is a hydrogen atom, a halogen atom (for example, a chlorine atom,
bromine atom, fluorine atom), alkyl group (e.g. methyl,
ethyl), alkoxy groups (e.g. methoxy, ethoxy)
, or an amide group (eg, acetamide, methanesulfonamide).

R3! may be combined with R33 to form a 1,5 or 6R ring.

Z)l represents a hydrogen atom or a coupling-off group, such as a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom), an alkoxy group (e.g. dodecyloxy, methoxycarbamoylmethoxy, carboxypropyl oxy, methylsulfonylethoxy), oryloxy groups (e.g., 4-chlorophenoxy, 4-
methoxyphenoxy), acyloxy groups (e.g. acetoxy, tetrazocallyoxy, benzoyloxy)
, sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy), amide groups (e.g.
dichloroacetylamino, methanesulfonylamino, toluenesulfonylamino), alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, penzyloxycarbonyloxy), aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy), aliphatic or aromatic thio groups (e.g. phenylthio, tetrazolylthio), imide groups (e.g. succinimide,
hydantoinyl), N-heterocycle (eg, 1-pyrazolyl, 1-penztriazolyl), and the like.

Rjl or Ro in general formula (I) may form a dimer or a multimer.

A more preferable magenta coupler of formula (II) is the following general formula (IV), and a more preferable cyan coupler of the general formula (IV) is the following general formula (V) or (
Vl).

General formula (IV) In the formula, z41 represents a hydrogen atom, a halogen atom, an aryloxy group, or an arylthio group, Rat represents an alkyl group, an alkoxy group, or an aryloxy group, and
41 represents an alkylene group, an arylene group, or an aralkylene group, and X48 represents an -NH3Og- group or ~NHC-
Ram represents an aryl group or an alkyl group.

The alkyl group represented by R4I includes an unsubstituted alkyl group (e.g., methyl, ethyl, t-butyl) and a substituted alkyl group. Substituents of the substituted alkyl group include an alkoxy group (e.g., methoxy, ethoxy), an aryl group (e.g., phenyl). , p-chlorophenyl, m-)lysocanamidophenyl). The alkoxy group represented by R4 includes unsubstituted alkoxy groups (eg, methoxy, ethoxy) and substituted alkoxy groups. Examples of the substituents of the substituted alkoxy group include the substituents listed above for the alkyl group.

The aryl group of the aryloxy group represented by R41 includes an unsubstituted aryloxy group (for example, phenoxy) and a substituted aryloxy group. Specific examples of the substituents are alkyl groups (e.g. methyl), alkoxy groups (e.g. methoxy), hydroxyl groups, halogen atoms (e.g. chlorine atoms)
Examples include amide groups (eg, acetamide, methanesulfonamide), and the like. As the aryloxy group, a phenoxy group substituted with an alkoxy group at the 0-position is particularly preferred.

R4+ is particularly preferably an alkyl group having 4 or less carbon atoms, such as a methyl group, ethyl group, i-propyl group, or t-butyl group.

X4t is an alkylene group (e.g. methylene, ethylene, l-methylethylene, 2-methylethylene, 2-methylpropylene, 1,1-dimethylethylene, 2,2-
dimethylpropylene) arylene M (eg, tL; I' phenylene, 2-chlorophenylene, 2-t-7' tylphenylene) aralkylene groups (eg, phenythylene), among which branched alkylene groups are preferred.

The aryl group represented by R11 includes a phenyl group and a substituted phenyl group. Examples of the substituent include substitutable groups such as an alkyl group, an alkoxy group, a halogen atom, a sulfonamide group, a sulfamoyl group, an acylamido group, an alkoxycarbonyl group, a hydroxy group, and a cyano group.

The alkyl group represented by R41 is an alkyl group having 1 to 36 carbon atoms (for example, methyl, ethyl, propyl, butyl, octyl, decyl, pentadecyl), which may be further substituted with a substituent. Examples include substituted or unsubstituted phenoxy groups (e.g. 2,4-di-t-amylphenoxy, 2-chloro-4-t-amylphenoxy, 4-t-amylphenoxy, 2,4-di-t-octylphenoxy) can be mentioned.

General formula (V) During the ceremony, R5 represents an alkyl group having 1 to 15 carbon atoms.

Rs! represents an unsubstituted alkyl group having 1 to 32 carbon atoms or an aryloxy-substituted alkyl group having 7 to 32 carbon atoms.

The alkyl group having 1 to 15 carbon atoms represented by R'il may be either a straight chain or a branched alkyl group, and specific examples thereof include methyl group, ethyl group, n-propyl group, t-butyl group, n-decyl group, etc. can be mentioned.

The unsubstituted alkyl group having 1 to 32 carbon atoms represented by R8I may be either a straight chain or a branched alkyl group, and specific examples thereof include a pentadecyl group, n-dodecyl group, n-tetradecyl group, n-decyl group, n-) Examples include lysosyl group, 2-ethylhexyl group, 1-stearyl group, 1-ethyl group, and 1°3.6,8.8-pentamethylnonyl group. The aryl group of the aryloxy-substituted alkyl group includes a phenyl group and a substituted phenyl group, and specific examples of the substituent include a halogen atom (e.g., chlorine atom, etc.), an alkyl group (e.g., t, -amyl, t-octyl, methyl, ethyl). ), amide groups (eg, acetamide, methanesulfonamide), cyano groups, hydroxyl groups, alkoxy groups (eg, methoxy, ethoxy), and the like.

General Formula (Vl) In the formula, R41 represents an aryl group (for example, phenyl), and this aryl group may be substituted.

Specific examples of the substituent include the substituent of the substituted phenyl group shown by Rag in the general formula (IV).

R1 has the same meaning as Rs in general formula (V).

R11 is a hydrogen atom, an alkyl group, or C-N at the 0-position
Here are the nonmetallic atoms necessary to form a 5- or 6-membered ring with the H- carbon atom.

The nonmetallic atom group represented by R43 is an alkylene group, a(I
~1) When forming a 5- or 6-membered ring with I3 1b , R1 is not present.

The above alkylene group may be straight or branched, or may be an alkylene group containing a cyclic alkyl group.

Next, specific examples of compounds of general formulas (I) to (II) will be given.

To the second ball,” Yu said, standing still. CHs (I-!5) CHl CH.

CHs CH.

CH.

CH.

(■ CH7 Hs CH3 CH3 Hs Hs H3 (Summer-19) Hs Hs Hs Hs (I (■ 2 days) ([I-2) (■ (n-4) Hff Hs Hs CH3CH3 (■ (■ (I1-7) (II-9) (II-14) (■ (II-16) １■muυ (II-11) (II-13) (II-17) (■ (■ (n-25) Hs 111% (II (II-24) ([11 (III-16) (Ill-18) xHS (III-11) (III-12) (II-13) (II-14) (III-19) (It-22) (t noshi 511++ (■ (m (Ill-30) (■ CalL) (■ H3 H3 CM.

H3 The couplers represented by the above general 2N), (II) and (III) are usually present in the range of 0.1 to 1.0 mol per mol of silver halide in the silver halide emulsion layer constituting the photosensitive layer. It is preferably contained in a range of 0.1 to 0.5 mol. Also, general formula (I), (n) or (■),
The molar ratio between each coupler is usually about 1.
:0.2-1.5: Although the range is often 0.5-1.5, it is possible to design sensitive materials outside this range.

The coupler represented by the general formula (I) used in the present invention can be easily synthesized by referring to US Pat. No. 4.266.019.

The coupler represented by the general formula (II) used in the present invention is disclosed in JP-A No. 59-162548, No. 59-171956, No. 60-33552, No. 60-43659, and U.S. Patent No. 3,061,432. , No. 3,369,897, No. 3,725,067, and the like.

The coupler represented by the general formula (■) used in the present invention is
JP 56-80045, JP 59-31935, JP 59-121332, JP 59124341, JP 60
It can be easily synthesized by referring to No.-205446 and the like.

The color photographic light-sensitive material of the present invention has first and second layers on a support.
and a blue-sensitive silver halide emulsion layer as a third photosensitive layer,
It can be constructed by coating at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer. In general color photographic paper, the layers are usually coated on the support in the order listed above, but they may be coated in a different order. can be used in place of at least one of the emulsion layers described above. These photosensitive emulsion layers contain silver halide emulsions that are sensitive to each wavelength range, and dyes that are complementary colors to the light to which they are exposed - yellow for blue, magenta for green, and cyan for red. By containing a so-called color coupler, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

When the photosensitive material of the present invention is used as a color photographic paper, the silver halide emulsion used is preferably one consisting of silver chlorobromide or 1-silver chloride, which does not substantially contain silver iodide. . Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2
Refers to mol% or less.

Furthermore, in the case where the photosensitive material of the present invention is a negative film for photography, a color reversal photosensitive material, or a photosensitive material using a direct positive emulsion, silver bromide and silver iodobromide can also be preferably used in addition to the above-mentioned silver halide. . The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [-layer or multiple layers] Particles with a so-called layered structure in which the halogen composition is different, or structures having parts with different halogen compositions in a non-layered manner inside or on the surface of the particle (if on the surface of the particle, Particles having a structure in which portions of different compositions are joined on the edges, corners, or surfaces of the substrate can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use one of the latter than grains with a uniform structure, and it is also preferable from the viewpoint of pressure resistance, when the silver halide grains have the above-mentioned structure. Even if the boundaries between parts with different halogen compositions are clear boundaries,
It may be possible to form a mixed crystal due to a difference in composition and have an unclear boundary, or it may be one that has a continuous structural change.

Regarding the halogen composition of silver chlorobromide bills, any lI bromide
/silver chloride ratio can be used.

Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Further, so-called high silver chloride emulsions having a high silver chloride content are preferably used for light-sensitive materials suitable for rapid processing.The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more.
A silver chlorobromide emulsion having a silver chlorobromide content of 98 to 99.9 mol 2 is more preferable, with a silver chlorobromide content of 98 to 99.9 mol 2 being more preferable, since it has high sensitivity and little fog.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized layer is provided inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above.

The halogen composition of the localized layer preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. And these local layers are
It can be inside the particle, on the edges, corners or faces of the particle surface. One preferred example is one in which part of the corner of the particle is epitaxially grown.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In the case of this birch, its silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1μ to 2μ.

In addition, their particle size distribution is preferably a so-called monodisperse one with a variation coefficient @ (standard deviation of particle size divided by average particle size) 2 (l or less, preferably 15% or less; in this case, a wide For the purpose of obtaining latitude, it is also preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply heavy N coating.

The silver halide grains contained in photographic emulsions are formed in regular shapes such as cubes, tetradecahedrons, or octahedrons.
(lay) those having a crystal shape, those having an irregular crystal shape such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P, Glafkid
osauthorrchemie et Ph1slque Ph
otographlque J (PaulMon L
el Publishing, 1967) s G, F, Du
ufin AuthorPhotographc Emul
sior+ Chemistry J (FocalP
rsss, 1966), V.L., Zelikm.
ari at al rMaking and Coa
ting Photographic Hmulsio
It can be solidified using the method described in, for example, Focal Press (1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. A method in which particles are formed in an atmosphere containing excess silver ions (
A so-called back mixing method) can also be used. As one type of simultaneous mixing method, p, A in the liquid phase in which silver halide is produced
It is also possible to use a method of keeping g constant, ie, the so-called Chondrold double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably from 10@-9 to 10@-8 mol relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. It is preferable to add an absorbing dye-spectral sensitizing dye. Examples of the spectral sensitizing dye used in this case include rHe by F. H. Harsher.
terocyclic compounds-Cyan
ine dyes and related co+
mpoundsJ (JohnWlley &
5oz [New York+ Lonaon
1-1964) can be mentioned. Examples of specific compounds are described in the above-mentioned JP-A-62
-215272 Publication Specification, pages 2 and 2, upper right column to 3
The one described on page 8 is preferably used.

Various compounds or their precursors may be added to the silver halide emulsion used in the present invention for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance. be able to. These are commonly called photographic stabilizers. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface, or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain, and the emulsion layer is formed as an emulsion dispersion. It can be contained in Preferably, a high boiling point am solvent represented by the following formula (A) or E) is used.

Formula (B) W l -CO0-Wt Formula (D) WI W鵞\/ (In the formula, W, , W, and W are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, Represents an aryl group or a heterocyclic group, W pot is W, ,
represents OWI or S-W, where n is an integer from 1 to 5, and when n is 2 or more, W may be the same or different from each other, and in general formula (E), W and Wl are may form a fused ring).

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right a-14
Other types of high-boiling organic solvents that can be effectively used in the couplers of the present invention described in the upper right column of page 4 include N,N-dialkylaniline derivatives. Among these, those in which an alkoxy group is bonded to the ortho position of the N,N-dialkylamino group are preferred, and specific examples include the following compounds.

Formula % Formula % This type of high-boiling organic solvent is useful for preventing magentastin from forming over time on the white background of color prints after processing, and also for preventing fog during development. The amount used is 10 mol% to 500 per coupler.
Mol% is common, preferably 20mol%-30
There is a range of 0 mol%.

These couplers can also be synthesized with rhodapul latex polymers (
For example, U.S. Patent No. 4. 203. No. 716) or dissolved in a water-insoluble but organic solvent-soluble polymer to emulsify and disperse in an aqueous hydrophilic colloid solution.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO3B100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

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

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as organic antifading agents for cyan, magenta and/or yellow images, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, gold yA complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are disclosed in U.S. Patent No. 2,360.290,
Same No. 2,418.613, Same No. 2.700.453, Same No. 2,701,197, Same No. 2.728,659
No. 2. 732. No. 300, No. 2,735,
No. 765, No. 3,982.944, No. 4.430
．． 425, British Patent No. 1.363,921, U.S. Patent No. 2,710.801, U.S. Pat. U.S. Patent No. 3°432.
No. 300, No. 3.573,050, No. 3,574
, No. 627, No. 3. 698. No. 909, same No. 3,
No. 764,337, JP-A No. 52-152225, spiroindanes are described in U.S. Pat. No. 4,360,589, and p-alkoxyphenols are described in U.S. Pat. No. 2,73.
No. 5.765, British Patent No. 2.066.975, Japanese Patent Application Laid-Open No. 10539/1982, and Japanese Patent Publication No. 19765/1983, etc. Hindered phenols are described in US Patent No. 3.700.
No. 455, JP-A-52-72224, U.S. Patent No. 4.
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3,457.079 and U.S. Pat. 56-21144
Hindered amines are disclosed in U.S. Patent No. 3.336.
No. 135, No. 4.268,593, British Patent No. 1
．． 32. No. 889, same No. 1. Ether and ester derivatives of phenolic hydroxyl groups are described in Japanese Patent Publications No. 354.313, No. 1,410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 114036-1988, No. 59-53846, Japanese Patent Publication No. 54178344, etc. U.S. Patent No. 4.155.765
No. 4,174.220, No. 4.254.21
No. 6, No. 4,264,720, Japanese Unexamined Patent Publication No. 1983-145
No. 530, No. 55-6321, No. 5B-105147
No. 59-10539, Japanese Patent Publication No. 57-37856, U.S. Patent No. 4,279,990, Japanese Patent Publication No. 53-32
No. 63, etc., and metal complexes are disclosed in U.S. Patent No. 4.050,93.
No. 8, No. 4,241゜155, British Patent No. 2,02
7,731 (A), etc., respectively.

The purpose of these compounds can be achieved by co-emulsifying them with the couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the respective color couplers. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer.

Among the above antifading agents, spiroindanes, hindered amines, and the like are particularly preferred.

In the present invention, it is preferable to use the following compounds together with the above-mentioned couplers, and it is particularly preferable to use them in combination with pyrazoloazole couplers.

That is, a compound (Q) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (R) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (Q) has a second-order reaction rate constant km (in trioctyl phosphate at 80°C) with p-anisidine of l, Q j /+*ol·se
c~I X 1 G-'j/■0!・It is a compound that reacts in the range of sec. Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When k is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k8 is smaller than this range, the reaction with the remaining aromatic amine developing agent is slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

A more preferable compound (Q) can be represented by the following general formula (QI) or (Qn).

General formula (Ql) Rt -(A)n-X General formula (QI[) R1-C-Y In the formula, Rt and Rt each represent an aliphatic group, an aromatic group, or a heterocyclic group, and n is 1 or 0, A represents a group that reacts with an aromatic amine developer to form a chemical bond, X represents a group that reacts with the aromatic amine developer and leaves, B is a hydrogen atom, represents an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (Qll); Here Rt and X
1Y and R3 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by the general formulas (QI[),
No. 3338, Patent Application No. 158342-1982, Patent Application No. 1983
Those described in specifications such as No.-18439 are preferred.

On the other hand, a more preferable compound (R) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound is the following general formula (R1 ).

General formula (R1) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and 2 is a nucleophilic group or a nucleophilic group that is decomposed in a photosensitive material to release a nucleophilic group. In the compound represented by the group R, 2 is Pearson's nucleophilicity "CHmI value (
R, G, Pearson+at al, +J, ^-,
Chss+, Soc,, 90. 319 (I
A group in which 96B)) is 5 or more, or a group derived therefrom is preferred.

For specific examples of the compound represented by the general formula (Rf), see European Patent Publication No. 255722, Japanese Patent Application Laid-open No. 1430-1983.
No. 48, No. 62-229145, patent application No. 63-184
No. 39, No. 63-136724, No. 62-21468
1, No. 62-158342, etc. are preferred.

Further, details of the combination of the above-mentioned compound (R) and compound (Q) are described in European Patent Publication No. 277589.

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

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

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the gelatin production method can be found in "The Macromolecular Chemistry of Gelatin" by Arly Vuais. Academic Press.

(published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The ``reflective support j'' used in the present invention refers to one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films, vinyl chloride resins, and the like, and these supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white interstitial fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 6 μm x 6 μm and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (Ri) of fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the S/K of H Todoroki's Horror Recitation 3 for Ri's Taira PJIII (R). The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s/R can be found as follows.

In the present invention, the coefficient of variation of the occupied area ratio (%) of pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. When O,OS or less, the dispersibility of the particles is substantially uniform. ” can be said.

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.

D-I N,N-diethyl-p-phenylenediamine D-3 2-amino-5-diethylaminotoluene 2-amino-5-(N-ethyl-N-laurylamino) Toluene 4-[N-ethyl-N- (β-hydroxyethyl)aminocoaniline 2-methyl-4-[N-ethyl-N- (β-hydroxyethyl)aminocoaniline 4-amino-3-methyl-N-ethyl-N-[β-(methane) sulfonamide) ethyl-aniline N-(2-amino-5-diethylaminophenylethyl) methanesulfonamide N. N-dimethyl-p-phenylenediamine 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline D-11 4-amino -3-methyl-N-ethyl-
Among the above-mentioned -phenylenediamine derivatives, N-β-butoxyethylaniline is particularly preferably 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 I)-) luenesulfonates. The amount of the aromatic-grade developing agent used is preferably about 0.1 g to about 20 g per 11 of the developer solution.
, more preferably about 0.

The concentration is from 5g to about 10g.

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.

However, when benzyl alcohol is removed for the purpose of reducing pollution load, etc., it is preferable not to substantially contain sulfite ions in order to improve the color development of the color developer, and in such a system, the effect of the present invention is is particularly remarkable. "Substantially not containing" as used herein means 0.5 g of sodium sulfite equivalent per 11 color developing solutions.
Below, preferably 0.2 g/j or less, more preferably,
It does not contain it at all.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines and hydrazides described in No. 61-170756, and hydrazides described in No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61-1811741, and/or No. 61-1
It is preferable to add the various 11 cheeks described in No. 80616. In addition, in combination with the above compounds, patent application No. 14782/1986
No. 3, No. 61-166674, No. 61-165621
Monoamines described in No. 61-164515, No. 61-170789, and No. 61-168159, No. 61-173595, No. 61-164515,
Diamines described in No. 61-186560, etc., No. 61
-165621 and the polyamines described in No. 61-169789, the polyamines described in No. 61-188619, the nitroxy radicals described in No. 61-197760, No. 61-186561, and No. 61-19741.
It is preferable to use alcohols described in No. 9, oximes described in No. 61-198987, and tertiary amines described in No. 61-265149.

Other preservatives include various types of gold 111i described in JP-A-57-44148 and JP-A-57-53749, salicylic acids as described in JP-A-59-180588, and JP-A-54.
Alkanolamines described in No.-3532, JP-A-56
-94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, etc., may be contained as necessary. Particularly preferred is the addition of alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, or aromatic polyhydroxy compounds.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11oO, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffering agents. Examples of the buffering agents include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylene salt, alanine salt, aminobutyrate, 2-amino-
2-methyl-1,3-7'lovandiol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are
It has excellent buffering ability in the high pH range of 9.0 or higher, and does not cause any negative effects on photographic performance (fogging, etc.) even when added to color developers.
It is particularly preferable to use these buffers because they have the advantages of being free from oxidation and being inexpensive.

Specific examples of these buffers include thorium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and boric acid. 6 um of sodium, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (1 um of sodium salicylate), potassium O-hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
Examples include sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0. 1 mole/
It is preferably 1 or more, especially 0.1 mol #==0
．． Particularly preferred is 4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-1-rimethylenephosphonic acid, ethylenediamine-N,N.

N',N'-tetramethylene sulfonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1, 2,
4-1-ricarboxylic acid, l-hydroxyethylidene-1
, 1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these quenching 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. Benzyl alcohol can be used as a typical color development accelerator. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining.

"Substantially" as used herein means that it contains less than 2 mi per 1.4 of the developer, preferably not at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813.247, 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, 3. 128゜No. 182, 4.
No. 230.796, No. 3,253.919, Special Publication No. 4
1'-11431, U.S. Pat. No. 2.482.546, U.S. Pat. 596. No. 926 and 3,582,34
Amine compounds described in No. 6 etc., Japanese Patent Publication No. 37-1608
No. 8, No. 42-25201, U.S. Patent No. 3. 128
．． No. 183, Special Publication No. 41-11431, No. 42-2
Polyalkylene oxides such as those disclosed in US Pat. No. 3,883 and US Pat. No. 3,532,501, l-phenyl-3-pyrazolidones, imidazoles, etc. may be added as necessary.

In the present invention, any anti-capri agent can be added as required. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic anti-capri agents include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent.
Diamino-2,21-disulfostilbene compounds are preferred, the amount added is 0 to 5 g/j, preferably 0.1 g to 4
g/l.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic 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. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although it is preferable that the amount of replenishment be small, 20 to 600 mj per ml of photosensitive material is appropriate, preferably 50 to 300 mj! It is. More preferably 60mJ! ~200mJ! , most preferably 60m
f-150mj! It is.

Next, the all process in the present invention will be explained. .

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.

The bleaching solution, bleach-fixing solution, and fixing solution used in the present invention will be explained below.

As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular organic complex salts of iron (I) (e.g., aminopolymers such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) can be used. complex salts with carboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates;
Hydrogen peroxide and the like are preferred.

Among these, organic complex salts of iron (I) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution, and aminopolycarboxylic acids, aminopolyphosphonic acids, or aminopolyphosphonic acids useful for forming complex salts of iron (I) The organic phosphonic acids or their salts are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether. Diaminetetraacetic acid, etc. can be mentioned. These compounds may be sodium, potassium, lithium or ammonium salts,
Among these compounds, iron(I) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid 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 nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. In addition, a chelating agent can be used as a second
It may be used in excess to form an iron ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/J.

Preferably it is 0.05 to 0.50 mol/E.

Bleach solution, bleach constant 11 solution and/or these pre-baths include:
Various compounds can be used as bleach accelerators0
For example, U.S. Pat.
9ri No. 630, Research Disclosure No. 17
Compounds having a mercapto group or disulfide bond as described in No. 129 (July 1978 issue), and
No. 8506, JP-A-52-20832, JP-A No. 53-32
Thiourea compounds described in No. 735 and US Pat. No. 3,706.561, or halides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g., potassium chloride, sulfurium chloride, ammonium chloride). ) or iodides (e.g. ammonium iodide) or iodides (e.g.
A rehalogenating agent such as ammonium iodide) may be included.

If necessary, one or more inorganic substances having pHI properties such as borax, sodium metaborate, acetic acid, sulfur 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-fixing solution or fixing solution according to the present invention is a known fixing agent, i.e., a periosulfate such as sodium periosulfate or ammonium thiosulfate; or a thiocyanate such as sodium thiocyanate or ammonium thiocyanate. ; ethylene bisthioglycolic acid, 3,6-cythia 1
, 8-octanediol, etc., and water-soluble silver halide solubilizers such as thioureas, and these can be used alone or in combination of 211 or more. In addition, 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.In the present invention, thiosulfate It is particularly preferred to use ammonium thiosulfate salts. The amount of fixing agent per Iz is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 10.
9 is particularly preferred.

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 sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, bisulfite, etc.) as preservatives. potassium, etc.), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0 in terms of sulfite ion.
It is preferable to contain 2=0.05 mol/l, more preferably 0.04 to 0.40 mol/l! It is.

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, a mild ionic agent, a fluorescent whitening agent, a chelating agent, an antifoaming agent, an antifungal agent, etc. 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 multi-stage countercurrent method was determined by the Journal of the Society of Picture and Television Engineers.
alof the 5ociety of M
tion Picture and Television
sion [Inglnears) 64th T! ,L2
4B-253 (May 1955 issue) by the method described in
Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.51/11 or less per 1/1 photosensitive material, and the effect of the present invention is remarkable. As a result of the increased residence time, problems such as bacteria propagation and the adhesion of generated floating substances to the photosensitive material occur.As a solution to such problems in the processing of color photosensitive materials of the present invention, the patent application No. 1983- The method for reducing calcium and magnesium described in No. 131632 can be used very blindly. In addition, isothiazolone compounds and thiabendazoles described in JP-A-57-8542;
Chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 1-120145, patent application No. 105487-1987
Benzotriazole, copper ion, etc. written by Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal agents", Hygiene Technology Golden Wire "Sterilization of microorganisms, sterilization, and antifungal technology", Japan Antibacterial and Antifungal Science Gold Wire "Antibiotics" It is also possible to use fungicides listed in the "Encyclopedia of Antifungal Agents".

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

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 such as 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, a surfactant, a fluorescent brightener, and a hardening agent may also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without going through a water washing step, JP-A-57-
No. 1543, No. 5B-14834, No. 60-220345
Any of the known methods described in No. 1, etc. can be used.

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

In the present invention, a so-called rinsing solution is also used as a washing solution or a stabilizing solution used after the desilvering treatment.

The pH of the water washing step or stabilization step of the present invention is 4 to 10, preferably 5 to B. Temperature depends on the use of photosensitive materials.
Although various settings can be made depending on the characteristics, the temperature is generally 15 to 45°C, preferably 20 to 40°C.

Although the time can be set arbitrarily, a shorter time is desirable from the viewpoint of reducing processing time, preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduction in emissions, ease of handling, etc.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or 1z or less per photosensitive material Id, preferably 500m! It is as follows. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to flow the overflow of washing water reduced by a multi-stage countercurrent system into the bleach-fix bath of the 70-year bath, and replenish the bleach-fix bath with concentrated liquid to reduce the amount of waste liquid.

The total process time of the desilvering step, water washing and stabilization step of the present invention is 2 minutes or less, preferably 30 seconds' to 1 minute and 30 seconds. The total time here refers to the time from when the silver halide color photographic light-sensitive material comes into contact with the first bath in the desilvering process until it comes out of the final bath in the water washing or stabilization process.
Air time for intermediate travel is included.

Here, "the sum of the processing times of desilvering treatment, water washing treatment, and stabilization treatment is 2 minutes or less" refers to the treatments performed before the desilvering treatment and drying process (more specifically, the water washing and/or stabilization treatment). For example, the sum of the processing times such as (1) desilvering-water washing (2) desilvering-stabilization (2) desilvering-water washing-stabilization (2) is two minutes or less.

Next, the present invention will be explained in detail based on examples.

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

No.-N coating liquid! 19.1 g of gI yellow coupler (ExY) and 4.4 g of color image stabilizer (Cpa-1) and (Cpd-7) 8
g to 27.2 cc of ethyl acetate and solvent (SOIV
Add and dissolve 4゜Ig each of 3) and (Solv-5), and add 8% of this solution to 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing cc. On the other hand, silver chlorobromide emulsion (silver bromide so, o mol%
, cubic; average particle size 0.85μ, coefficient of variation 0.0
8 and mso, o% bromide, cube, average particle size 0.62 μ, coefficient of variation 0.07, mixed at a ratio of 1:3 (Ag molar ratio)) were sulfur-sensitized. , the blue-sensitive sensitizing dye shown below was added at 5.0×10− per mole of silver.
'Mole addition was prepared.

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 Nth layer. The geladine hardening agent in each layer is 1-oxy-3
, 5-dichloro-5-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (4.0X10-' mole per mole of silver halide) and (7.0X10-' mole per mole of halide)
Red-sensitive emulsion layer SO,- (5.0XlO-' mol per mol of silver halide) (
For the red-sensitive emulsion layer, the following ° compounds were added to the halogenated a
2.6 x 10-'' moles were added per t mole.

1.2 x 10-'' mole and 1.IXIG-rich mole were added.

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

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added at 4.0 x 10 -mol and 3.0 x 104 mol per mole of halogenated il, respectively. 1.0X1
G-' mole or 2-methyl-5-t-octylhydroquinone, respectively, per 111 moles of halogenation.
"Mole, 2 x 10-! mole, 2 x l〇-rich mole were added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene was added per mole of silver halide and (layer structure) The composition of each layer is shown below. , the numbers represent the coating amount (g/d), and the silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Till) and a bluish dye (ulmarine)] -th layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr: 80 mol%) 0 .26 gelatin
1.83 yellow coupler (E
xY) 0.83 color image stabilizer (Cpd-1)
0.19I (Cpd-7)
0.08 solvent (Solv-3)
0.18' (Solv-6) 0.
18 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-6) 0.08 Solvent (Sol
v-1) 0.16# (Solv-4
) 0.08 Fifth layer (green-sensitive layer) Silver chlorobromide emulsion (AgBr 90 mol%, cubic, average grain size 0.47μ, coefficient of variation 0.12, Ag
Br90 mol%, cubic, average particle size 0.36tt
, and those with a coefficient of variation of 0.09 are mixed at a ratio of l=1 (Ag molar ratio)) 0.16 Gelatin 1.79 Magenta coupler (ExM) 0.22 Color image stabilizer (Cp
d-3) 0.20I (Cpd-8
) 0.03# (Cpd-4)
0.011 (Cpd-9)
0.04 Solvent (Solv-2) 0
．． 65 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (C
pd-5) 0.05 solvent (Solv-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (AgBr7G mol%, cubic, average grain size 0.49#, coefficient of variation 0.08, AgB
r 7 Q mole %, cubic, average particle size 0.34μ
, with a coefficient of variation of 0.10, mixed at a ratio of 1:2 (Ag molar ratio)') 0.23
Gelatin 1.34 Cyan coupler (ExC) 0.30 Color image stabilizer (
Cpd-6) 0.17 color image stabilizer (Cp
d-7) 0.40 solvent (Solv-6)
0.20 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (
Cpd-5) 0.02 Solvent (Solv-5
) 0.08 Seventh N (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 (Cpd-1) Color image stabilizer (Cpd-3 ) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixture inhibitor H (Cpd-6) Color image stabilizer (Cpd-8) Color image stabilizer (Cpd-9) Color image stabilizer (UV-1) 2:4 mixture of ultraviolet absorbers (weight ratio) (Cpd-7) Color image stabilizer -← CH3 -CH→] C0N) IC4Hv (t) Average molecular weight 80° (Solv-4) Solvent ( Solv-1) Solvent (SOIV-2) Solvent (Solv-5) Solvent COOCs Ht.

■ (CHJs COOCs Ha.

(Solv-(i) medium 2:1 mixture (weight ratio) of (3o 1 v-3) Solvent yellow coupler (I-4), magenta coupler (n-4>, cyan coupler (!l-1), Represent each.

(Ex　x　C) (E x Y) is the above-mentioned example coupler (ExM) is the above-mentioned example coupler is the above-mentioned example coupler The sample thus obtained was designated as 100.

Next, as shown in Table 1, the first layer of yellow coupler,
Samples 101 to 121 were similarly prepared by changing the magenta coupler in the third layer and the cyan coupler in the fifth layer.

Comparative Yellow Coupler YR-1 YR YR-5 YR YR-3 YR YR YR YR-9 The above photosensitive material was exposed through an optical wedge and then processed in the following steps.

Color development 38℃ 1 minute 40 seconds Bleach constant 11
30-34℃ 1 minute 00 seconds rinse 0 30-34℃
Rinse for 20 seconds 0 30-34℃ 20
Rinse for 20 seconds @ 30-34℃ Dry for 20 seconds 70
~80°C for 50 seconds (3-tank countercurrent flow from rinsing ■ to ■) The composition of each treatment liquid is as follows.

Tachitachi Nibikigyo Gansui 800m
l diethylenetriaminepentaacetic acid 1.0 g l-hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0 g nitrilotriacetic acid 2.0 g triethylenediamine (l,4-diazabicyclo(2,2,2)oftane) 5.0 g Potassium bromide 0.5g Potassium carbonate
30g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoanilinosulfate 5.5g diethylhydroxylamine 4.0g Fluorescent whitening M (UV I
TEX-CK Chiba Gaigi 1.5 Add water 1000mjp100
0°C) 10.251 liters 1 Water ammonium thiosulfate (70%) Sodium ethylenediaminetetraacetic acid sulfite 11: Add (III) ammonium ethylenediaminetetraacetic acid dinatrilum water 00mj 200m7 0g 0g 10001nl pH (25°C) 7, 00 Yuei = (mark ion exchange water (calcium, magnesium 3pp each)
(m or less) For each sample having a colored dye image formed by the above method, the maximum density of each color, optical storage property, and implicit storage property were tested as described in (a) and (b) below.

(a) Light storage property Xenon fade meter 8.5 x 10' lux irradiated for 6 days (b) Implicit storage property at 100℃, no humidification, 5 days It is expressed as a percentage (%) of the concentration (D).

The results are shown in Table 2.

, as is clear from Table 2, the samples of the present invention (l00~
112) are samples using comparative couplers (I13-121)
) compared to image color balance and light preservation,
It was found that it showed excellent performance in terms of implicit preservation.

Table 1: Example 2 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. ! ! ! The cloth solution was prepared as follows.

19.1 g of yellow coupler (ExY-2), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd
-7) 0.7g of ethyl acetate 27.2 and solvent (S
olv-3) 8.2g was added and dissolved, and this solution was diluted to 10%
1 containing 8 cc of sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 18.5 cc of a 0% aqueous gelatin solution. On the other hand, a lump silver bromide emulsion (a 3=7 mixture of one with a cubic average grain size of 0.88μ and one with a cubic average grain size of 0°70μ (silver molar ratio) 0
The coefficient of variation of particle size distribution is 0.08 and 0.08. IO5, each emulsion contains 0.2 mol% of silver bromide locally on the grain surface) and the blue-sensitive sensitizing dye shown below was added to 11!1 mol of silver bromide (localized on the grain surface). -4 mol, and for small size emulsions, 2.5 x 10
-' mol was added and then sulfur sensitized.

The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first 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 gelatin hardening agent for each layer is 1-oxy-3゜5-
Dichloro-3-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer to form a green-sensitive emulsion layer.

Blue sensitive emulsion layer and red sensitive emulsion layer xto-'moles, 2.5X10-'moles were added.

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

For the red-sensitive emulsion layer, the following compounds are halogenated.
2.6 x 10-'' moles were added per 11 moles.

In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer with halogenated l! B per mole, 5 x 10-'+-l, 7.7 (layer structure) The composition of each layer is shown below, the numbers represent the coating amount (g/d), the silver halide emulsion is the coating amount in terms of silver. represents.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOi) and a bluish dye (ulmarine blue)] No.-N (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 color image stabilizer ( Cpd-1) 0.19 Solvent (Sol
v-3) 0.35 color image stabilizer (Cpd
-7) 0.06 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Sol
v-1) 0.16 solvent (Solv-4
) 0.08 Fifth layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.55 μm and one with an average grain size of 0.39 μm (Ag mol)
ratio) 0 The coefficient of variation of particle size distribution is 0.10 and 0.08
, each emulsion contained 0.8 mol% of AgBr locally on the grain surface) 0.12 Gelatin 1.24 Magenta coupler (ExM-Z) 0.14 Color image stabilizer (
Cpd-3) 0.15 color image stabilizer (If
f-1) 0.02 color image stabilizer (Cp
d-31) 0.03 solvent (Solv-2)
0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (
Cpd-5) 0.05 Solvent (Solv-
5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture of one with an average grain size of 0.58μ and one with an average grain size of 0.45μ (Ag mol)
The coefficient of variation of particle size distribution is 0.09 and 0.11
, each emulsion contained 6 mol % of AgBr O locally on a part of the grain surface) 0.23 Gelatin 1.34 Color image stabilizer (
Cpd-(i) Color image stabilizer (Cpd-0) Color image stabilizer (Cpd-'?) Solvent (Solv-6) Sixth Tri (ultraviolet absorbing layer) Gelatin ultraviolet absorber (υV-1) ? It color inhibitor CCpd-5) Solvent (Solv-5) Seventh layer (protective layer) Acrylic modification of gelatin polyvinyl alcohol 11: Eutectic coalescence (!R modification 17% Liquid paraffin 1, 33 0, 17 0, 03 (Cpd-1) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd, -5) Color mixing inhibitor (Cpd-6) Color image stabilizer (Cpd-8) Color image stabilizer (UV-1 ) 2:, 4:4 mixture (weight ratio) of ultraviolet absorber (Cpd-7) Color image stabilizer -← CH Snow-CH-11 CON HCaHw (n) 4:2:4 mixture of average molecular weight 60° ( Weight ratio) (SOIV-1) Solvent (Solv-5) solution C00C* HIt (CHx)s COOCm H1? (SOIV-2) Solvent (Solv-6) solution 2:1 mixture (volume ratio) Yellow coupler (EXY -2) is the above-mentioned example coupler 4), (SOIV-3) solvent magenta coupler (ExM-2) is the above-mentioned example coupler (
II-3), and the cyan coupler (ExC-2) is the above-mentioned exemplary coupler (S.

1v-4) 2% by weight of each of solvents (II-30), (III-31) and (!If-3)
: represents a 4:4 mixture, respectively.

The sample thus obtained was designated as 200.

Next, as shown in Table 3, the first layer yellow coupler,
Samples 201 to 214 were similarly prepared by changing the magenta coupler in the third layer and the cyan coupler in the fifth layer. Note that the coupler described in Example 1 was used as the comparative coupler.

After imagewise exposure of the above photosensitive material, using a paper processing machine,
Continuous processing (running test) was performed until twice the capacity of the color development tank was replenished in the following processing steps.

IJL Tomo 1 left 1 Kori 1 color development 35℃ 45 seconds 161ml 1
71 Bleach-fixing 30-36℃ 45 seconds 218m I
t IT l-rinse■, 30-37℃ 30 seconds
□ 101 Rinse■ 30-37℃ 30 seconds □
10ffi rinse■ 30-37℃ 30 seconds 3
60 ml 101 Drying 70-80° C. 60 seconds Per 1rd photosensitive material (3 tank countercurrent method was used for rinsing ①-②) The composition of each processing solution is as follows.

Left-standing Nirigami phlegm”? Oni Plate Dog Tatsumizu
80 抛1 800m1
Ethylenediamine-N,N.

N', N'-Tetramethinephosphonic acid 3-0g 3.0g;/-N, N-shiflffll 5. Og
6.0g Triethanolamine 10g
Sodium chloride 1.4g Potassium carbonate 25g N-ethyl-N-(β-methanesulfonamidoethyl)-3 monomethyl-4-aminoaniline sulfate 5.0g Fluorescent brightener (WHITEX 4 manufactured by Sumitomo Chemical ■) 1.0 Water Add and pH (25℃) 1000 m 1 10.05 0 g 5 g 7.0 g 2.0 000 m 1 10.45 Iron(II+) acetate Ammonium ethylenediaminetetraacetic acid disodium 400mj! 00m7 7g 5g g Add ammonium bromide water to pH (25℃) 0g 000m4 5, 40 Ichimoshi j11C tank liquid and replenisher are the same) Ion exchange water (calcium, magnesium each 3 ppm or less) Formed by the above method For each sample having a colored dye image, the maximum density of each color, optical storage stability, and implicit storage stability were measured under the same conditions as in Example 1.

The results are shown in Table 4.

As is clear from Table 4, the samples of the present invention (200 to 2
07) is a sample using a comparative coupler (208-214)
It was found that the image showed superior performance in terms of color balance, optical storage stability, and implicit storage stability when compared to the previous version.

(Effects of the Invention) According to the present invention, the multilayer silver halide color photographic photosensitive material has good color development properties and improved image storage stability, and in particular, the color balance does not change over a long period of time either in the dark or in the dawn light. materials can be obtained.

Claims (1)

[Scope of Claims] A color photographic light-sensitive material having at least three light-sensitive silver halide emulsion layers having mutually different color sensitivities on a support, wherein the first light-sensitive layer contains a coupler represented by the following general formula (I). The second photosensitive layer contains at least one coupler represented by the following general formula (II), and the third photosensitive layer contains at least one coupler represented by the following general formula (III). A silver halide color photographic material characterized by containing at least one silver halide. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_1, R_1_2 and R_1_3 each represent a hydrogen atom or an alkyl group, but R_1_1, R_
At least two of 1_2 and R_1_3 are alkyl groups, at least one of which is a branched alkyl group, and the total number of carbon atoms of the groups represented by R_1_1, R_1_2 and R_1_3 is 12 to 36,
R_1_4 represents a halogen atom or an alkoxy group,
Z_1_1 represents a hydrogen atom or a group or atom that can be separated by a coupling reaction with an oxidized aromatic primary amine. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_2_1 represents a hydrogen atom or a substitutable group, and Z_2_1 represents a hydrogen atom or a reaction with an oxidized product of an aromatic primary amine color developing agent. represents a group or atom that can be separated from Z_2_2, Z_2_3 and Z_
2_4 each has ▲mathematical formula, chemical formula, table, etc.▼, -N
= or -NH-, one of the Z_2_4-Z_2_3 bond and the Z_2_3-Z_2_2 bond is a double bond, and the other is a single bond. Z_2_3-Z_2_2
The case where is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. General formula (III) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_3_1 represents an alkyl group, aryl group, amino group, or heterocyclic group, R_3_2 represents an acylamino group or an alkyl group, R_3_3 is a hydrogen atom, It represents a halogen atom, an alkyl group, an alkoxy group, or an amide group, and R_3_2 and R_3_3 may be combined to form a 5- or 6-membered ring. Z_3_1 represents a hydrogen atom or a group or atom that can be separated in reaction with an oxidized product of an aromatic primary amine color developing agent.