JPH03127048A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the generation of the unnecessary fogging at the time of long-term preservation of the photosensitive material by incorporating specific hydrophilic colloidal layers and at least one kind of photographic couplers into the photosensitive material. CONSTITUTION:The hydrophilic colloidal layers contg. the dispersion of the fine crystals of at least one kind of the compds. selected from a group consisting of formula I, etc., and the photographic couplers expressed by formula II are incorporated into the layers constituting the photosensitive material. In the formula I, A denotes an acidic nucleus; R denotes a hydrogen atom, alkyl group; R1, R2 denote an alkyl group, aryl group, acyl group, sulfonyl group. In the formula II, R<a1> denotes a hydrogen atom, substituent; X<a1> denotes a hydrogen atom, etc.; Za to Zc denote methine substd. methine, =N-, -NH-. The fogging at the time of the long-term preservation generated when colloidal silver is used and the degradation in sensitivity are decreased in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Scope of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material.

(Prior art) In silver halide photographic light-sensitive materials, it is well known to provide a light absorption filter, a layer that absorbs light of a specific wavelength for the purpose of preventing Halley silane or adjusting sensitivity. The yellow filter layer is placed closer to the support than the light-sensitive layer and farther from the support than the other color-sensitive layers. This is a method to cut the inherent sensitivity of the green and red light-sensitive emulsions, or to create a yellow filter layer closer to the support than the light-sensitive emulsion layer. The method of providing an antihalation layer on the near side to prevent unnecessary light scattering is currently the most commonly used method.From a practical standpoint, fine particles of colloidal silver are usually used for these light absorption layers. However, these colloidal silver particles may have side effects such as causing harmful fog in the adjacent emulsion layer, increasing fog during storage of the photosensitive material, and further reducing the desilvering rate. In order to prevent these harmful fogs, the method disclosed in Japanese Patent Application Laid-open No. 62-324601 is known.
It was necessary to reduce the amount of antifogging agent as described in JP-A-1-219743, or to introduce an intermediate layer mainly composed of gelatin between the yellow filter layer and the emulsion layer to prevent fogging. The addition of these antifogging agents has the major disadvantage of reducing sensitivity, and the method of introducing an intermediate layer increases the thickening of the emulsion layer, reducing sharpness, and further increases the number of coated layers, which increases manufacturing costs. It had the major drawback of inviting

In order to improve this point, attempts have been made to use organic dyes in the filter layer instead of colloidal silver, as described in the patents listed below. When these dyes are used, harmful fogging can be removed, but the ability to decolorize the sensitive material is poor, unnecessary absorption remains after processing, resulting in an increase in Dmin, and dyes are not fixed sufficiently in specific layers, resulting in storage problems. However, many efforts have been made to obtain a dye that satisfies both the properties of decolorizing the dye and fixing it in a specific layer.

For example, US Pat. No. 2,548,564 discloses a method in which a dissociated anionic dye and a hydrophilic polymer having an opposite charge are co-existed together as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. 4,124,386
No. 3. No. 625°694, etc.

In addition, methods for applying two colors to a specific layer using solid dyes insoluble in water are disclosed in JP-A-56-12639, JP-A-5-155350, JP-A-8B-155351, JP-A-663-27838, JP-A-63-197943; Special Fraud No. 15.601, No. 274.7234 No. 276.566, No. 299,43
No. 5, World P'18B104794, etc. It has become possible to improve the desilvering speed without affecting photographic properties by using the dyes described in these books, but it is still not at that level and a method that can further shorten the time is desired. It was rare.

On the other hand, in recent years, there has been a remarkable improvement in the image turbidity of silver halide color photosensitive materials, and color reproducibility has also improved dramatically8.
Color formers are the major factors governing color reproducibility.
It is common to use a color coupler containing three types of color couplers that produce yellow, magenta, and cyan colors when coupled with the oxidized product of an aromatic-grade amine color-forming crude drug.

Among these, magenta couplers having a 5-pyrazolone skeleton and magenta couplers having a pyrazoloazole skeleton are known as typical magenta couplers.
The pyrazolotriazole magenta coupler described in No. 067 forms an azomethine dye with little side absorption that is harmful to color reproduction in the vicinity of 430 nm, so it is preferable for color reproduction. This is preferable in that it is less likely to occur.

[Intelligence to be solved by the invention B) However, various analyzes revealed that the introduction of these pyrazoloazole-based magenta couplers has a major drawback in that harmful fogging increases during long-term storage compared to pyrazolone-based magenta couplers. As a result, it became clear that this increase in fog was particularly noticeable when colloidal silver was used as the light absorption layer. These fogs can be alleviated by adding a large amount of the above-mentioned antifogging agent or by introducing an intermediate layer mainly made of gelatin, but side effects such as a decrease in sensitivity and sharpness are significant.

Therefore, the first object of the present invention is to suppress the occurrence of unnecessary fogging during long-term storage of a photosensitive material using a pyrazoloazole coupler and colloidal silver in the light absorption layer. A second object of the present invention is to provide a light-sensitive material with improved storage stability and sharpness without requiring an intermediate layer provided adjacent to a colloidal silver layer when a pyrazolotriazole coupler is used.

(Means for Solving the Problem) As a result of intensive research, the present inventor found that the object of the present invention can be achieved by the following means.

That is, in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one layer constituting the light-sensitive material has the following general formula (I).
A hydrophilic colloid layer containing a microcrystalline dispersion of at least one compound selected from the group consisting of ~(VI) ~ (Vl), and at least one layer of at least one photographic coupler represented by the following general formula (A). A silver halide color photographic material comprising:

Rh General formula (III) A''Ll -(Lt -Ls) --A' General formula (I
V) A-(Ll-Lm)o, s+aB General formula (Vl) (In the formula, A and A' may be the same or different, each represents an acidic nucleus, B represents a basic nucleus, X and Y may be the same or different, and each represents an electron-withdrawing group, R
represents a hydrogen atom or an alkyl group, R and R8 each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R1 and R may be linked to form a 5- or 6-membered ring.

R1 and R6 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group, or a halogen atom, and R4 and R1 each represent a hydrogen atom, or R1 and R4 or R8 and Rs are linked to form a 5- or 6-membered ring. Ll, Lx and L3 each represent a methine group, representing a group of nonmetallic atoms necessary for forming the metal.

m represents 0 or 1, n and q represent each kO11 or 2, p represents O or 1, when p is 0, R3 represents a hydroxy group or a carboxyl group, and R4 and R, represent a hydrogen atom B' represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group.

However, the compounds represented by general formulas (I) to (VI) or Vl) have a pKa in the range of 4 to 11 in a mixed solution of water and ethanol in a volume ratio of 1 to 1 in one molecule. It has at least one dissociable group. ) First, general formula (I
) to (VI) to Vl) will be explained in detail.

The acidic nucleus represented by A or A' is preferably 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, inoxazolidinone, barbylic acid, thiobarbital acid, indandione, pyrazolo Represents pyridine or hydroxypyridone.

The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole or virol.

Examples of heterocycles of B' include pyrrole, indole,
Thiophene, furan, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine,
phenoxazine, indoline, thiazole, pyridine,
These include pyridazine, thiadiazine, biran, thiobilane, oxadiazole, benzoquinolidine, thiadiazole, pyrrolothiazole, pyrrolopyridazine, and tetrazole.

A group having a dissociable proton having a pKacH dissociation constant (in a mixed solution with a volume ratio of water and ethanol of 1:1) in the range of 4 to II makes the dye molecule substantially water-insoluble at pH 6 or below, There are no particular restrictions on type 81 and the substitution position on the dye molecule as long as it makes the dye molecule substantially water-soluble at pH 8 or above, but preferred are carboxyl groups, sulfamoyl groups, sulfonamide groups, and hydroxyl groups. A more preferred group is a carboxyl group. The dissociable group may be substituted not only directly on the dye molecule, but also via a divalent linking group (eg, alkylene group, phenylene group).

Examples via a divalent linking group include 4-carboxyphenyl, °2-methyl-3-carboxyphenyl, 2.4
-dicarboxyphenyl, 3.5-dicarboxyphenyl, 3-carboxyphenyl, 2.5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl, 2. 4゜6-dolyhydroxyphenyl, 3-benzenesulfonamidophenyl, 4-(p-cyanobenzenesulfonamido〉phenyl, 3-hydroxyphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl,
2-hydroxy-4-carboxyphenyl, 3-methoxy-4-carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl,
2-carboxybenzyl, 3-sulfamoylphenyl, 4-sulfamoylphenyl, 2.5-disulfamoylphenyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,
Examples include 8-carboxyoctyl.

The alkyl group represented by R, R3 or R6 has 1- carbon atoms.
10 alkyl groups are preferred, and examples include groups such as methyl, ethyl, n-propyl, isoamyl, n-octyl and the like.

The alkyl group represented by R+ and Rx is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl,
n-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl> are preferred, and substituents [e.g., halogen atoms such as chlorine bromine, nitro group, cyano group, hydroxy group, carboxy group, alkoxy group (e.g., methoxy, ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, i-propoxycarbonyl), aryloxy groups (e.g. phenoxy 1&), phenyl groups, amide groups (e.g. acetylamino, methanesulfonamide), carbamoyl 1& (e.g. methyl carbamoyl, ethylcarbamoyl), sulfamoyl group (e.g. methylsulfamoyl, phenylsulfamoyl)
].

The oryl group represented by R+ or R3 is preferably a phenyl group or a naphthyl group, and the tA group [the ta group includes the groups listed as substituents of the alkyl groups represented by R1 and R8 above and the alkyl group] (e.g. methyl, ethyl). ].

The acyl group represented by R1 or R2 is preferably an acyl group having 2 to 10 carbon atoms, and includes, for example, acetyl, propionyl, n-octanoyl, n-decanoyl, imbutanoyl, benzoyl, and the like. R1 or R
Examples of the alkylsulfonyl group or arylsulfonyl group represented by 3 include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, 0
-carboxybenzenesulfonyl and the like.

The alkoxy group represented by R3 or R& has 1 to 1 carbon atoms.
0 alkoxy groups are preferred, and examples include groups such as methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, and impropoxy. Examples of the halogen atom represented by R or R6 include chlorine, bromine, and fluorine.

Examples of the ring formed by linking R1 and R4 or R8 and R1 include a julolidine ring.

Examples of the 5- or 6-membered ring formed by connecting R3 and R1 include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by LISLx or ri has a substituent (
For example, methyl, ethyl, cyano, phenyl, chlorine atoms,
hydroxypropyl).

The electron-withdrawing groups represented by X or Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted, such as acetyl, propionyl, heptanoyl, dodecanoyl, hexadecanoyl, 1-oxo-7-chloroheptyl>, arylcarbonyl group (arylcarbonyl group that may be substituted, e.g. benzoyl, 4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl)
, alkoxycarbonyl i & (an alkoxycarbonyl group that may be substituted, for example, methoxycarbonyl,
Ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl ,2
-Methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-(2-chloroethoxy)ethoxycarbonyl, 2-(2-(2-chloroethoxy)ethoxy]ethoxycarbonyl), aryloxycarbonyl group (optionally substituted aryl An oxycarbonyl group, such as phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl,
4-fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl,
2.4-di(t-amyl)phenoxycarbonyl),
Carbamoyl group (carbamoyl group that may be substituted, for example, carbamoyl group ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4 -Propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di(t-7mil)phenylcarbamoyl, 2-chloro-3-(dodecyloxycarbamoyl) ) Phenylcarbamoyl, 3-(
Hexyloxycarbonyl)phenylcarbamoyl)sulfonyl group (for example, methylsulfonyl, phenylsulfonyl), sulfamoyl1&<sulfamoyl group which may be substituted, for example, sulfamoyl, methylsulfamoyl).

Next, specific examples of dyes used in the present invention will be given.

-4 -6 -7 1-9 1-11 -13 ■-14 Hs ! -15 ! -17 -18 -19 -21 +1-2 It-3 1-4 ■-5 -6- 11-3 +11-4 ■-5 -6 -1 m-9 m-t.

l-11 11-12 ll-14 ll-16 l-17 ■-18 I-19 ■-20 ■-21 11-22 ■-24 ll-25 ll-29 1-30 m-33 ■-34 H2 Hs C*Hs V-7 mHs C*Hs V-10 mHs -12 rV-15 Cm Hs C word Hs Hs Below, specific examples of general formula (VI) are: Part B' I will show you.

■ 5 V [-6 C old COJ 1-10 ■ 1 ■-12 ■-13 The dye used in the present invention is based on international patent WO3810479.
No. 4, European Patent EPO 274723A1, No. 2
No. 76.566, No. 299,435, JP-A-52-9
No. 2716, No. 55-155350, No. 55-155
No. 351, No. 61-205934, No. 4B-6862
3, U.S. Patent No. 2,527,583, U.S. Patent No. 3,486
, No. 897, No. 3,746,539, No. 3,933°798, No. 4,130,429, No. 4,040.8
The base can be easily formed by the method described in No. 41, etc., and in accordance with that method.

In the present invention, the dye is formed into a solid fine powder dispersion for inclusion in a layer, such as a hydrophilic colloid layer, coated on a photographic element. The fine powder dispersion can be prepared by precipitating the dye in the form of a dispersion and/or in the presence of a dispersant by known comminution means, such as ball milling (ball mill, vibratory ball mill, planetary ball mill, etc.), sand milling, It can be formed by colloid ξ-ring, jet milling, roller milling, etc. In that case, a solvent (for example, water, alcohol, etc.) may be present, or alternatively, after dissolving the dye in a suitable solvent, a non-solvent of the dye can be formed. may be added to precipitate microcrystalline powder of the dye,
In that case, a dispersing surfactant may be used, or the dye may be first dissolved by controlling the pH, and then crystallized by changing the pH.

The dye particles in the dispersion have an average particle size of 10 μm or less, more preferably 2 μm or less, particularly preferably 0.5 μm.
It is more preferable that the powder be a fine powder with a particle size of 0.1 μm or less, and in some cases, a fine powder of 0.1 μm or less.

The amount of dye used in the present invention is 1~1000/
Used within the range of rrf. Preferably 5■~800■
/ It's Bo.

The dye dispersion of the present invention can be added to any layer regardless of whether it is an emulsion layer or an intermediate layer.

Particularly, it is preferable to use the colloidal silver to replace part or all of the colloidal silver normally used in the yellow filter layer and the antihalation silane layer.

In particular, the effect is remarkable when all the colloidal silver in the yellow filter layer is replaced with the dye dispersion of the present invention.

Furthermore, the effect is greatest when the coupler of the present invention is used in a layer adjacent to the yellow filter layer.

The compound represented by general formula (A) will be explained in detail below.

-a In formula (A), multimer means one having two or more groups represented by general formula (A) in one molecule, and bis-form and polymer couplers are also included therein. . Here, the polymer coupler is a monomer having a moiety represented by the general formula (A) (preferably one having a vinyl group,
A homopolymer consisting only of vinyl monomer (hereinafter referred to as vinyl monomer) may be used, or a copolymer may be prepared together with a non-color-forming ethylene zelkova monomer that does not couple with the oxidation product of the aromatic-grade amine developer.

The compound represented by the general formula (A) is a 5-membered ring-5-membered I! 1
It is an m-merging nitrogen heterocyclic coupler, and its color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, and has a chemical structure that is generally referred to as azapentalene. Among the couplers represented by the general formula (Al), preferred compounds are IH-I-(VI,2-b) pyrazoles, IH-
Pyrazolo (I) to (VI, 5-b) pyrazoles, IH
-pyrazolo(5,1-c)(I) to (VI,2,4))
Liazoles, IH-pyrazolo(I) to (VI,5-b
)(I) to (VI,2,4)) lyazoles, IH-pyrazolo(I) to (VI,5-d) tetrazoles and I
H-pyrazolo (I) to (VI,5-a) benzimidazoles, each having the general formula (A-13, [8-2]
, (A-3), (A-4), (A-5) and (A-6)
It is expressed as Among these, preferred compounds are (A-
1), (A-3) and (A-4]. Particularly preferred compounds are (A-3) and (A-4).

(A-1) [A-2) (A-33 (A-43 General formula (A-1) (A-63) The IA groups R1, 17m3 and R'' are each a hydrogen atom, a halogen atom, an alkyl group , aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic group,
Acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, azila a) group, anilino group, ureido group, imido group, sulfamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonyl 74 group , represents an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbamoyl group, or an aryloxycarbonyl group, and xmI is a hydrogen atom, a halogen atom,
Represents a carboxyl group, or a group that is bonded to a carbon at a coupling position via an oxygen atom, nitrogen atom, or sulfur atom, and is decoupled.

R1, Ras Q*4 or xl becomes a divalent group,
This also includes cases where a screw body is formed. In addition, the general formula (A-
When the moieties represented by 1) to (A-6) are present in the vinyl monomer, Bat-;Bas or R1 represents a simple bond or linking group, and via this, the moieties represented by the general formula (A-1
) to (A-6) are bonded to the vinyl group.

More specifically, R"R'" and R1 each represent a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom)
, alkyl groups (e.g. methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amylphenoxy)propyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2'- hexylsulfonyl-ethyl, cyclopentyl, benzyl), oryl groups (e.g. phenyl, 4-t-butylphenyl,
2.4-di-t-amylphenyl, 4-tetradecanamidophenyl), heterocyclic groups (e.g. 2-furyl, 2
-thienyl, 2-pyrimidinyl, 2-penzothiazolyl), cyano groups, alkoxy groups (e.g. methoxy, nidoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy groups (e.g. phenoxy, -methylphenoxy, 4-
t-butylphenoxy), heterocyclic oxy TE (e.g. 2-benzimidazolyloxy), acyloxy group (
For example, acetoxy, hexadecanoyloxy), carbamoyloxy groups (e.g., N-phenylcarbamoyloxy, N-ethylcarbamoyloxy), silyloxy groups (e.g., trimethylsilyloxy), sulfonyloxy groups (e.g., dodecylsulfonyloxy), azilamino groups (e.g., acedoamide, benzamide, tetradecanamide, α-(2,4-di-t-amylphenoxy)butanamide, r-(3-t-butyl-4-hydroxyphenoxy)butanamide, α-( 4-(4-
hydroxyphenylsulfonyl)phenoxy1decaneamide), anilino groups (e.g., phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2τchloro-5-(α
-(3-t-butyl-4-hydroxyphenoxy)dodecanamide)anilino), ureido groups (sidelight, phenylureido, methylureido, N,N-dibutylureido), imodo groups (e.g., N-succinimide), , 3-penzylhindantoynyl, 4-(2-ethylhexanoyl ξ])phthalimide), sulfamoylamino group (
For example, N.

N-diethylsulfamoylate), N-methyl-N-
decylsulfamoylamino), alkylthio groups (e.g. methylthio, octylthio, tetradecylthio, 2
-) Futtsuki diethylthio, 3-phenoxypropylthio, 3-(4-L-butylphenoxy)propylthio)
, arylthio groups (e.g. phenylthio, 2-butoxy-S-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), heterocyclic thio groups (e.g. 2-benzo thiazolylthio), alkoxycarbonylamino groups (e.g., methoxycarbonylamino, tetradecyloxycarbonylamino), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino, 2,4-di-Lert-butylphenoxycarbonylamino), sulfonamides groups (e.g. methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-butylbenzenesulfonamide), carbamoyl groups (e.g. N
-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N
-Methyl-N-dodecylcarbamoyl, N-(3-(2
,4-') -tart-amylphenoxy)propyl)carbamoyl), acyl groups (e.g. acetyl, (2
゜4-') -terL-amylphenoxy)acetyl, benzoyl)J 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), sulfinyl groups (e.g., octylsulfinyl, dodecylsulfinyl, phenylsulfinyl), or alkoxycarbonyl groups (
For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl group (eg, phenyloxycarbonyl, 3-pentadecyl phenyloxy-carbonyl).

XaI is a hydrogen atom, a halogen atom (for example, a chlorine atom,
bromine atom, iodine atom), carboxyl group, groups linked via oxygen atom (e.g. acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, bilbinyloxy,
Cinnamoyloxy, phenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2 -phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy)
, groups linked via a nitrogen atom (e.g., benzenesulfonamide, N-ethyltoluenesulfonamide, hepfluoroptanamide, 2.3,4.5.6-bentafluorobenzado, octanesulfonamide) de, p-cyanophenylureido, N, N-diethylsulfamoylamino, l-piperidyl, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl, 1-benzyl-ethoxy-3-hydantoinyl, 2N- 1,l-dioxo-3
(2H)-oxo-1,2-benzisothiazolyl, 2
-oxo-1,2-dihydro-1-pyridinyl, imidazolyl, -pyrazolyl, 3,5-diethyl-1,2゜4
-triazol-1-yl, 5- or 6-promobenzotriazol-1-yl, 5-methyl-1,2,3
-) Riazol-1-yl, penzimigzolyl, 3-
Benzyl-1-hydantoynyl, l-benzyl-5-hexadecyloxy-3-hydantoynyl, 5-methyl-
1-tetrazolyl, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), or groups linked via a sulfur atom (e.g., phenylthio, 2-carboxyphenylthio, 2 -methoxy-5-t-octylphenylthio,
4-methanesulfonylphenylthio, 4-octanesulfonamidophenylthio, 2-butoxyphenylthio,
2-(2-Heki.

(sulfonylethyl)-5-tart-octylphenylthio, benzylthio, 2-cyanoethylthio, l-
Ethoxycarbonyltridecylthio, 5-7 enyl-2
．． 3.4.5-tetrazolylthio, 2-benzothiazolylthio, 2-dodecylthio-5-thiophenylthio, 2
-phenyl-3-dodecyl-1,2,4-)riazolyl-5-thio).

When Rsl Hs3 R4 or xl becomes a divalent group to form a bis body, this divalent group can be described in more detail as a substituted or unsubstituted alkylene group (for example,
Methylene, ethylene, 1. to-decylene, -CHIC
H! -α-CH, CH, -, etc.), substituted or unsubstituted phenylene groups (e.g. 1,4-phenylene, 1,3-
Phenylene (R-5 represents a substituted or unsubstituted alkylene group or phenylene group).

Hat Ras or R1 when those represented by general formulas (A-1) to (A-63) are present in the vinyl monomer
The linking group represented by 14 is an alkylene group (iltI4
or an unsubstituted fullkylene group, such as methylene, ethylene, l, 10-decylene, -CH*CHxOCHz
CHt-, etc.), phenylene groups (substituted or unsubstituted phenylene groups, such as 1,4-phenylene, 1,3-phenylene, -o--oco-, and aralkylene groups (such as CI), .

The vinyl group in the vinyl monomer has the general formula (A-1
Preferred substituents, including those having vA groups other than those represented by ) to (A-6), are hydrogen atoms, chlorine atoms, or lower alkyl groups having 1 to 4 carbon atoms.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (for example, methacrylic acid, etc.) and amides or esters derived from these acrylic acids (for example, acrylamide, n-butylacrylamide, t-butylacrylamide, rylamide, diacetone acrylacrylate) methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-
ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl, laurate)
, acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid,
Maleic anhydride, maleic ester, N-vinyl-2
-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. It also includes the case where 2f11I or more of the non-color-forming ethylenically unsaturated monomer used herein is used together.

Compound examples and synthesis methods of couplers represented by the general formulas (A-1) to (A-6) above are described in the documents listed below.

The compound of general formula (A-1) is disclosed in JP-A No. 59-162548.
The compound of general formula (A-2) is disclosed in JP-A-60-43
No. 659, etc., the compound of formula -8 (A-3) was published in Japanese Patent Publication No. 47
-27411, etc., compounds of general formula (A-4) are described in JP-A-59-171956 and JP-A-60-172982, etc., compounds of general formula (A-5) are described in JP-A-60-335, etc.
No. 52, etc., and the compound of general formula (A-63) is described in U.S. Pat. No. 3,061.432, etc., respectively.

Also, JP-A-58-42045, JP-A No. 59-21485
No. 4, No. 59-177553, No. 59-177554
The highly color-forming ballast groups described in No. 59-177557 and the like have the above general formulas (A-1) to (A-6
) applies to any of the compounds.

Specific examples of the pyrazoloazole coupler used in the present invention are shown below, but the invention is not limited thereto.

(A-13-1 (A-1)-2 (A-1)-3 (A-63-1 (A-6)-2 (A-2)-1 (A-3) -12 (A- 4)-19 X: Y -40: 60 (Mo # ratio) X: Y-
50:50 (mole ratio) These couplers are generally added in an amount of 2X10-' moles to 5X10-' moles, preferably 1X10-' moles to 5X10-' moles per 111 moles in the emulsion layer.

Two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

Here, the emulsion layer is preferably a green-sensitive emulsion layer comprising silver bromide, silver iodobromide, iodochlorobromide, or silver iodochloride emulsion.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular restrictions on the number or order of layers and non-photosensitive layers.A typical example is to prepare a plurality of silver halide emulsions with substantially the same color sensitivity but different photosensitivity on a support. A silver halide photographic light-sensitive material having at least one light-sensitive layer, the light-sensitive layer being a unit light-sensitive layer sensitive to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

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

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

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer structure can be preferably used0
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (B) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer ( GL)/
High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL)
) or BH/BL/GL/GH/R1(/RL
or Bl(/BL/Gll/GL/RL/RH
They can be installed in the following order:

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

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4.705.744, No. 4,707,
No. 436, JP-A-62-160448, JP-A No. 63-89
BL, GL, I? described in the specification of No. 580? A multilayer effect donor layer with a different spectral sensitivity distribution from the main photosensitive layer such as L (
CL) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 corons or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) NIX17643
(I)-(VI December 978), pp. 22-23,'
1. Emulsion preparation
ion and types)”, and the same N11
18716 (I) - (VI November 979), 6
48 pages, graphic "Physics and Chemistry of Photography", published by Beaumontel (P, Glafkides, Chemie
at Ph1sique Photograph-i
que, Paul Montel+ 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G
, F, Duffin+Photographic E
Mulsion Chemistry (Focal
Press+1966)), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L,
Zelikmanet aloMaking and
Coating Photographic Emul
-sion, Focal Press+ 1964)
It can be prepared using the method described in et al.

U.S. Patent Nos. 3,574,628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1.413.748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), No. 14 @ pp. 248-257 (I)-(VI970); U.S. Pat.
No. 4,433.048, No. 4,439.520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in Research Disclosure H1l.
It is described in L17643 and NIL 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Addition 1 plate U to 7 ratio t l Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25, right column Page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant page 27 Page 650 right column 12PI! Fabric aids, pages 26-27, page 650, right column, surfactant 13, static, page 27, same.
．． It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) 81117643, ■-C-C.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, 4.022.620, 4.3
No. 26,024, No. 4.401.752, No. 4.
248.961, Japanese Patent Publication No. 5B-10739, British Patent No. 1.425.020, British Patent No. 1,476.760, U.S. Patent No. 3.973,968, British Patent No. 4.314,
No. 023, No. 4.511,649, European Patent No. 24
9.473A, etc. are preferred.

As the 7-zenta coupler other than the present invention, 5-pyrazolone compounds are preferred, and are disclosed in U.S. Pat. No. 4,310°619.
No. 4.351.897, European Patent No. 73,63
No. 6, U.S. Patent No. 3.061.432, Japanese Patent Application Publication No. 1986-
No. 35730, No. 55-118034, No. 60-18
Particularly preferred are those described in No. 5951, US Pat. No. 4,556,630, and International Publication No. 8,810,4795.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052.212.
No. 4.146.396, No. 4.228.23
No. 3, No. 4,296.200, No. 2.369.9
No. 29, No. 2.801.171, No. 2.772.
No. 162, No. 2.895.826, No. 3.772
．． No. 002, No. 3.758,308, No. 4,33
4.011, 4.327,173, West German Patent Publication No. 3゜329,729, European Patent No. 121.365
No. A, No. 249°453A, U.S. Patent No. 3.446
．． No. 622, No. 4,333.999, No. 4.77
5.616, 4.451.559, 4.4
No. 27,767, No. 4,690.889, No. 4.
Preferred are those described in No. 254.212, No. 4.296.199, and JP-A-61-42658.

Colored couplers for correcting unnecessary absorption of coloring dyes are recommended in Research Disclosure 17643.
- Section G, U.S. Patent No. 4.163.670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.258, British Patent No. 1.146.36
No. 8 is preferred, and also US Pat. No. 4.7
No. 74,181, which uses a fluorescent dye released during coupling to correct unnecessary absorption of coloring dyes, and U.S. Pat. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96.570 and German Patent Publication No. 3.234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in U.S. Pat. No. 63-37346, U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. , DIR redox compound releasing couplers, DIR coupler releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc.,
DIR Coupler-Releasing Redox Compound or DIR Redofux-Releasing Redox Compound, European Patent No. 173゜3
R, D, N[L 114
49, No. 24241, bleach accelerator-releasing couplers described in JP-A No. 61-201247, etc., U.S. Pat. No. 4,553
, No. 477, etc.;
Couplers that emit leuco dyes as described in US Pat. No. 3-75,747, and couplers that emit fluorescent dyes as described in U.S. Pat. No. 4,774,181.

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

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

The boiling point at normal pressure used in the oil-in-water dispersion method is 175"
Specific examples of high boiling point i solvents of C or higher include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-monoamyl phenyl)); phthalate, bis(2,4-di-t-amyl phenyl) isophthalate, bis(I) to (VI,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, triclepropyl phosphate, etc.) dilyphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridodecylphosphate,
(tryptoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-ρ-hydroxybenzoate, etc.), amides (N,N-diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.)
, alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters M (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate) ,
trioctyl citrate, etc.), aniline derivatives (N,
N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50"C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include 2-ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
2-phenoxyethanol, 2-(4-thiazolyl)
It is preferable to add various preservatives or fungicides such as benzimidazole.

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

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Na 17643 and N1118 of the same
716, from the right column on page 647 to the left column on page 648.

In the photosensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 20 μm or less, and film swelling The speed T, 73 is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the film thickness measured at 25°C and 55% relative humidity (2 days), and the film swelling rate T, /! can be measured according to techniques known in the art, e.g., by Green et al.
+ It can be measured by using a swellometer (swelling membrane) of the type described in Volume 19, No. 2, pages 124-129, and the TI/! The saturated film thickness is 90% of the maximum swelling film thickness reached when treated with a color developer at 30°C for 3 minutes and 15 seconds.
It is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling rate T178 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above conditions, using the formula = (maximum swollen film thickness -
It can be calculated according to (film thickness)/film thickness.

The color photographic light-sensitive material according to the present invention is described in the above-mentioned RD, Ishi 17643, pages 28-29, and the same Ni 118716.
615, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, although phenolic compounds are also useful, p-phenylenecyagon compounds are preferably used, and a representative example thereof is 3-methyl-4-amino-N,N-diethylaniline. , 3-methyl-4-amino-N-ethyl-N-
β-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-7-mainly-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or anticapri agents such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity imparting agents. agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various calcinants such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylinodiacetic acid, l-hydroxyethylidene- 1,1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid) and their Salt can be cited as a representative example.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-7ξnophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

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

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

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

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (I[[), peracids, quinones, nitro compounds, etc.6 Typical bleaching agents include organic complex salts of iron (I[[), e.g. Aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyl chlorine acetic acid a, 1,3-cyamino-propanehydroacetic acid, glycol ether diaminetetraacetic acid, or citric acid, tartaric acid, malic acid, etc. Complex salts of , etc. can be used. Among these, aminopolycarboxylic acid iron (III) $1 salts, including ethylenecyaminetetraacetic acid iron (I[[) complex salt and 1,3-diaminopropane tetraacetic acid iron (II) complex salt, are suitable for rapid processing and environmental protection. Aminopolycarboxylic acid iron (Ill) complex salts, which are preferable from the viewpoint of preventing staining, are particularly useful in both bleaching solutions and bleach-fixing solutions. pH of bleach solution or bleach-fix solution using these aminopolycarboxylic acid iron (III) ti salts
is usually 4.0 to 8, but it is also possible to process at an even lower pH for speeding up the process.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-12623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group as described in Research Disclosure No. 17129 (I) to (VI July 978), etc.; Thiazolidine instantaneous conductor described in No. 50-140129; Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20
No. 832, No. 53-32735, U.S. Patent No. 3,70
Thiourea derivatives described in No. 6.561; West German Patent No. 1.
127.715, iodide salts described in JP-A-58-16.235; West German Patent No. 966.410, JP-A-16-235
Polyoxyethylene compound 111 described in No. 8.430 [
i Polyamine compounds described in Japanese Patent Publication No. 45-8836; other Japanese Patent Publications Nos. 49-42.434 and 49-59.64
No. 4, No. 53-94.927, No. 54-35.727
No. 55-26.506, No. 58-163.940
Compounds described in this issue; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in US Pat.
No. 893,858, West German Patent No. 1.290.812,
The compounds described in JP-A No. 53-95,630 are preferred, and the compounds described in U.S. Pat. No. 4,552,834 are also preferred; these bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

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

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C to 5°C.
0''C1 is preferably 35° C. to 45° C. In the preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering process, it is preferable that the stirring be as strong as possible.A specific method for strengthening the stirring is the treatment on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461. A method of colliding liquid jets, a method of increasing the stirring effect using a rotating means as described in JP-A No. 62-183461, and a method of moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid. , a method of improving the stirring effect by creating turbulence on the surface of the emulsion, and a method of increasing the circulation flow rate of the entire processing liquid. Such agitation enhancement means include bleaching solutions,
It is effective in both bleach-fixing solutions and fixing solutions. Improved agitation speeds up the supply of bleach and fixing agent into the emulsion film,
It is thought that this increases the derailment speed as a result. Also,
The agitation improvement means described above are more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material transporting means described in JP-A No. 191259/1983. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urn-al of the 5ociety of
Motion Picture and Te1e-v
ision Engineers Volume 64, P, 24
It can be determined by the method described in 8-253 (I)-(VI May 955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (I) - (VI 986) Sankyo Publishing, Hygiene Technology Complete Edition “Microbial sterilization, sterilization, and anti-mildew technology J (I
) to (VI982), "Encyclopedia of Bacterial and Antifungal Agents" (I) to (VI986), edited by the Society of Industrial Technology and the Japan Antibacterial and Antifungal Society, can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is in the range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 5B-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out. For example, a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photosensitive materials for printing, is carried out. Examples of dye stabilizers that can be mentioned include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

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

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3.342.59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14.850
Ship base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal salt complex described in No. 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may contain various types of l-phenyl-3, if necessary, for the purpose of promoting color development.
- Pyrazolidones may be incorporated.

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

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

Also, 1 of photosensitive materials! West German Patent No. 2, 22 for ff silver
6.770 or U.S. Pat. No. 3,674,499 using cobalt or hydrogen peroxide intensification.

Also, the halogenation of the present invention! ! The photosensitive material is U.S. Patent No. 4
．． The present invention can also be applied to the heat-developable photosensitive materials described in JP-A No. 500,626, JP-A No. 60-133449, JP-A No. 59-218443, JP-A No. 61-238056, and European Patent No. 210.660A2.

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

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each function indicate the coating amount expressed in g/nf units, and for silver halide, it indicates the coating amount in terms of silver. However, for sensitizing dyes, the coating amount in the same layer halogenated a
The coating amount is expressed in moles relative to Ct moles.

(Sample 101) 1st layer (antihalation layer) Black colloid m m o, ts gelatin 1.40 2nd layer (
Intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.18E
-16,07 EX-30,02 EX-12 U-1 -2 -3 B5-1 B5-2 Gelatin third layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye I Sensitizing dye ■ Enhancement Dye Sensitive ■EX-2 EX-1゜-1-2-3) (BS-1 Gelatin 0.002 0.06 0.08 0.10 0.10 0.02 1.04 Silver 0.25 it!I O,25 6,9X10''1.8X10-'3,1X10-' 0.335 0.020 0.07 0.05 0.07 o, os.

0987 4th layer (second red emulsion layer) Emulsion G Sensitizing dye! Sensitizing dye H Sensitizing dye■ EX-2 EX-3 EX-10 -1 -2 υ−3 gelatin 5th layer (3rd red-sensitive emulsion layer) emulsion Sensitizing dye I Sensitizing dye■ Sensitizing dye■ EX-3 EX-4 EX-2 Silver 1.0 5, lX1O-' 1.4 x 10-' 2.3X10~4 0.400 0.050 0.015 0.07 0.05 0.07 1.30 Silver 1.60 5.4XIO-' 1.4X10-' 2-4XlO-' 0.010 0.080 0.097 )IBS-1 B5-2 gelatin 6th layer (middle layer) EX-5 B5-1 gelatin 7th layer (first green emulsion layer) Emulsion A Emulsion B Sensitizing dye V Sensitizing dye■ Sensitizing dye■ EX-5 EX-1 EX-7 EX-13 B5-1 B5-3 gelatin 0.22 0.10 1.63 0.040 0.020 0.80 1! l　　　0.15 1M 0.15 3.0X10-' 1.0X10-' 3.8X1G-' 0.260 0.021 0.030 0.025 0.100 0.010 0.63 8th layer (second green emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye■ Sensitizing dye■ EX-6 EX-8 EX-7 B5-1 B5-3 gelatin 9th layer (3rd green emulsion layer) Emulsion E Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-33 EX-11 EX-1 B5-1 Silver 0.45 2, lX10-' ? ,0X10-' 2.6XIO-' 0.094 0.018 0.026 0.160 0.008 0.50 Silver 1.2 3.5XIO-' 8.0X10-' 3.0XIO-' 0.015 0.100 0.025 0.25 HBS-2 gelatin 10th layer (Yellow Fino Letter layer) yellow colloidal silver X-5 B5-4 gelatin No. 11N (1st blue-sensitive emulsion II) Emulsion A Emulsion B Emulsion F Sensitizing dye■ X-9 X-8 B5-1 gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye■ X-9 0,10 1,54 Silver 0.05 0.08 0.03 0.95 0.08 0.07 Silver 0.07 3.5xlO-' 0.721 0.042 0.28 1.10 Silver Silver Silver 0.45 2.1X10-' 0.154 X-10 B5-1 gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye■ X-9 B5-1 gelatin 14th layer (1st protective layer) Emulsion ■ l-4 -5 B5-1 gelatin 15th layer (second protective layer) polymethyl acrylate particles (Diameter approximately 1.5μm) -1 gelatin 0.007 0.05 0.78 Silver 0.77 2.2X10-' 0.20 0.07 0.69 0.20 0.11 0.17 0.05 1.00 0.54 0.20 1.20 In addition to the above-mentioned duties, each layer has gelatin hardener H-1 and a surfactant were added.

EX-1 EX-2 EX-3 0M EX-4 EX-5 EX-6 EX"-7 EX-8 EX-9 EX-10 EX-12 C mountain (3) ρ EX-13 U-1 -2 - 3-4 Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ S-1 -1 Shi II snow tuyere n-'JJ wealth-tllll wealth-shi υ question-L
, Preparation of I+Full Sample 102 In Sample 101, the colloidal silver in the 10th yellow filter layer was removed, and 0.2% of Comparative Compound A was added instead.
It was produced in the same manner as Sample 101 except that 5 gm was added.

Preparation of Sample 103 In Sample 101, dye dispersion S-1 of the present invention was used instead of yellow colloidal silver in the 10th layer, and the amount of dye added was 0.23.
Sample 101 was prepared in the same manner as Sample 101, except that the sample was added so that the amount of

Preparation of samples 104 to 108 In sample 103, dye dispersion 3-2 was used instead of dye dispersion S-1.
Samples were prepared in the same manner as Sample 103 except that S-6 to S-6 were added to each sample.

Preparation of Sample 109 In Sample 103, dye dispersion S-7 was used instead of the black colloidal silver added to the first layer, and the total amount of dye added was 0.
It was prepared in the same manner as Sample 103, except that the amount of addition was 26 g/m2.

Preparation of Samples 110 to 118 Samples except that the magenta coupler EX-6 added to the 7th to 9th layers on days 101 to 10 was removed and instead the magenta coupler of the present invention (A-43-1 was added in equal moles) It was produced in the same manner as Nos. 101 to 109.

Next, a method for preparing the dye dispersion used in the present invention will be described.

Preparation method of fine powder dye dispersion S-1 The dye was dispersed in a vibrating ball mill by the following method.

Water (21.7 ml) and 3 mL of 5% aqueous solution of p-octylphenoxyethoxyethanesulfonic acid sodium 5% aqueous solution of p-octylphenoxypoly(degree of polymerization 10) oxyethylene ether 0. 5g of the dye of the present invention (I-1) 1. OOg and 500 ml of zirconium oxide beads (1 mm in diameter) were added and the contents were dispersed for 2 hours. The vibrating ball mill used was a BO type manufactured by Chuo Kakosei.

The contents were taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were filtered to obtain a dye gelatin dispersion.

Dispersions 5-2 (dye n-5) and 5-3 were prepared in a similar manner.
(dye lll-13), 5-4 (dye ■-6), 5-5
(Dye v-2) and 5-6 (Dye Vl-13) were obtained.

8-7 was prepared by mixing dye I[[-34 and I-4 in a weight ratio of 1:1.

Comparative Compound A (Compound described in JP-A No. 62-32460) After cutting the obtained samples 101 to 118 into strips, the samples were heated at 35°C at 8°C.
It was stored for one month under 0% RH conditions. After storage, the sample was exposed to wedge light using a conventional method and was then processed in the following process along with the sample stored at room temperature to remove the remaining color of the dye, or t=y.
The q variation was investigated.

The results are shown in Table 1. ml, when the magenta coupler of the present invention is used, the fog further increases during long-term storage, whereas when the dye of the present 9 invention is used, there is little residual color and the fog during long-term storage is reduced. I know that there is.

Furthermore, the coupler of the present invention (A-43-1 to (A-4)-1
When similar evaluations were made by substituting equimolar amounts of 5 to 5, the same effects as *1 were obtained.

Processing process *Replenishment amount: per 1m length of photosensitive material with a width of 351m.

(Color developer) Mother solution (g) Replenisher (g) Hydroxyethyl 5.0 6.0 Noniacetic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxyluan sulfate 4-[N-ethyl-N -β-Hydroxyethyl acetate) -2- Add methylaniline sulfate solution to pH (bleach tf) 1.3-cyaminopropanetetraacetic acid ferric complex salt 1.3-cyaminopropanetetraacetic acid 5.0 4 .0 30.0 37.0 1.3 1.2N 2.0 3.6 0.5 1.0X10-"i31.3X10"tt&1.02 1, Of 10.00 10.15 Mother liquor (g) Replenisher (g) 130 190 3.0 4.0 Ammonium bromide acetate Ammonium nitrate Add water and adjust pH with acetic acid and ammonia (fixer) l-Hydroxyethyridane-1,1-diphosphonic acid Ethylenediamine tetranoic acid disodium salt Sulfite Sodium bisulfite Sodium ammonium thiosulfate aqueous solution (700g/j!) Rodan ammonium thiourea 3.6-cythia 1°5 0 0 1.0 It pH 4,3 20 0 0 1, Oll pl! 3.5 Mother liquor (g) Replenisher (g) 5.0 7.0 0.5 0.7 10.0 8.0 12.0 10.0 170, Od 200.0d 100.0 150.0 3.0 3.0 5・Q 5. 0 8-Octanediol Add water and ammonium acetate to pH (Stable solution) Mother liquor, replenisher Common formalin (37X) 5-chloro-2-methyl-4-isothiazolin=3-one 2-methyl-4- Isothiazolin 3-one surfactant 1, Oj! 1.2-6.0 ■ 3.0+ag 1, Ol Add ethylene glycol water 1, Ol H 5,0-7,0 Example 2 Preparation of sample 201 Undercoat A multilayer color photosensitive material consisting of the following layers was prepared on a cellulose triacetate film support having a thickness of 127 μm and designated as sample 201.The numbers represent the amounts added per pot. The effects are not limited to the described uses.

1st layer: Antihalation layer Black colloidal silver 0.25g Gelatin 1.9g Ultraviolet absorber U-1
0.04g Ultraviolet absorber U-20, tg Ultraviolet absorber U-30, 1g Ultraviolet 1 absorber U-60, Ig High boiling point organic solvent 0i1-10.1g 2nd layer: Intermediate layer gelatin 0.40g Compound C
pd-010mg High boiling point organic solvent 0il-340mg 3rd layer: Fine grain silver iodobromide emulsion (average grain size 0.06 μm, Ag r content 1 mol%) covered with intermediate layer Silver W
0.05 g Gelatin 0.4 g 4th layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.4 μm, Agl content 4.5 I:1 mixture of mol % monodisperse cubes and monodisperse cubes with average particle size 0.3 μm and Agl content 4.5 mol %) Silver amount 0.4 g Gelatin 0.8 g Coupler C
-10,20g Coupler C-90,05g High-boiling organic solvent Oil -20,10g 5th layer: Medium red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (Monodispersed cubic with average particle size 0.5 μm and Agl content 4 mol%) iI amount 0.4 g gelatin
0.8g Coupler C-10.2g Coupler C-20.05g Coupler C-30.2g High-boiling organic solvent oi1-2 o, 1g 6th layer: High sensitivity red-sensitive emulsion layer sensitizing dyes S-1 and S- Silver iodobromide emulsion spectrally sensitized with 2 (monodisperse twin grains with average grain size 0.7 μm and Agl content 2 mol%) Silver amount 0.4 g Gelatin 1.1 g Coupler C
-30.7g Coupler C-10.3g 7th layer: Intermediate layer gelatin 0.6g Dye D-1
0.02g 8th layer: Silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μm, Ag
1 content 0.3:el%) 0.02g gelatin
1.0g Color mixing prevention agent Cpd-A
0.2g 9th layer: Low-sensitivity green-sensitive emulsion layer A silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size 0.4 μm, Agl content 4.5 mol%). (1:1 mixture of dispersed cubes and monodispersed cubes with an average particle size of 0.2 μm and an Agl content of 4.5 mol%)
IIO, 5g gelatin
0.5g Coupler C-40, 20g Coupler C-70, Log Compound Cpd-80, 03g Compound Cpd-E O, 02g Compound Cpd-FO O, 02g Compound Cpd
-G O, 02g compound Cpd-HO
,02g High boiling point organic solvent 0i1-10.1g High boiling point organic solvent 0i1-20.1g 10th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (Monodisperse cubes with average particle size of 0.5 μm and Agl content of 3 mol%)! Ii amount 0.4g gelatin
0.6g Coupler C-40,2g Coupler C-70,1g Compound Cpd-80,03g Compound Cpd-E0.1g Compound Cpd-F0.1g Compound Cpd-G O,05g Compound Cpd-HO,05g High-boiling organic solvent ○1f-20.01g 11th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size in terms of spheres 0.6 μm, AgI content 1 .3 mol%, monodispersed flat plate with an average diameter/thickness of 7)
Silver amount 0.5g gelatin
1.0g Coupler C-40,6g Coupler C-70,2g Compound Cpd-B 0008g Compound Cpd-E O,02g Compound Cpd
-F O, 02g Compound Cpd-G
O,02g Compound Cpd-H0,02
g High boiling point organic solvent 0il-10,02g High boiling point m solvent Of + -20,02g 12th layer: Intermediate layer gelatin 0.6g Dye D-2
0.05g 13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.1g gelatin
1. 1g color mixing inhibitor CPd-
A 0101g 14th layer: Intermediate layer gelatin 0.6g 15th layer:
Low-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
1:1 mixture of monodisperse cubes with an average particle size of 0.4 μm and an Agl content of 3 mol % and monodisperse cubes with an average particle size of 0.2 μm and an Agl content of 3 mol %) Amount of silver 0.6 g Gelatin 0.8 g Coupler C
-50.6g High-boiling organic solvent Oil -20.02g 16th layer: Medium-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
(Monodispersed cube with average particle size 0.5 μm and Agl content 2 mol%) I amount 0.4 g gelatin
0.9g Coupler C-50.3g Coupler C-60.3g High-boiling point a solvent 0il-20.02g 17th layer: Highly sensitive blue-sensitive emulsion layer Sensitized with sensitizing dyes S-5 and S-6 Silver iodobromide emulsion (
Average particle diameter in terms of spheres: 0.7 μm, Agl content: 1.5 mol%
, tabular grains with an average diameter/thickness value of 7>
Silver amount 0.4g gelatin
1.2g Coupler C-60.7g High boiling point organic solvent 0i1-20.1g 18th layer: 1st protective layer gelatin 0.7g Ultraviolet All
1&Agent U-10.04g Ultraviolet absorber U-30.03g Ultraviolet absorber U-40.03g Ultraviolet absorber U-50.05g Ultraviolet absorber U-60.05g 11 solvents with high boiling points Of! -10,02g Formalin scavenger - Cpd-C0,8g Dye D-30,05g 19th layer: Fine grain silver iodobromide emulsion covered with second protective layer (average grain size 0°06μ
m, Agl content 1 mol%) II amount 0.1 g gelatin
0.4g 20th layer: Third protective layer gelatin 0.4g polymethyl methacrylate (average particle size 1.5 μm) 0.1 g 4:6 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5 μm) 0.1g silicone oil 0.03g surfactant w-13.0
■ In addition to the &ll above precepts, each layer contains gelatin hardening agent H-
1 and a surfactant for coating and emulsification were added.

This means that the emulsion used here has monodispersity and a coefficient of variation of 20% or less.

-t -2 -3 H H il -4 -5 -6 -7 9 H 0i 1-1 Dibutyl phthalate 11-2 Tricresyl phosphate pd-A H Pd-8 Pd-C pd-D 0[+ pd- E pd-F -1 -2 υ-3 υ-4 -5 U-6 -1 -2 -3 -4 -5 SOsHN(Ct[1sh -6- -2 -3 -1 CIIm-CHSChCBzCONHCHxCH*-I
CIISOxCIlxCONHCIIm-1 Bs Sample 201 prepared by the above method has a gray density of 1.
5, and continuous processing was carried out using a hanging hanger type automatic developing machine according to the following steps.

The processing amount was determined to be the amount until the cumulative replenishment amount of the black and white developer became three times the capacity of the black and white developer tank.

[Processing process]

Processing process Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38”C12ffi 2.2ffi/n
f First water wash 2I 38J 4I 7.5 1
Reversal 21 38# 4# 1. I
I color development 6-38# 12-2.2#
Adjustment 2 #38I4 #1.1- Bleach 6 l 38I 121
O, 22jF fixation 4 minutes 38℃ 8j! 1
．． 1f/bo second water washing 4jF 381 8- 7.
5 l stable 1# 25# 21 1
．． 1 # The composition of each treatment solution was as follows.

Meng Yali statue Mother liquor replenisher Nitrilo-N, N, N- trimethylene phosphone Acid/pentasodium salt sodium sulfite hydroquinone monos Potassium sulfonate potassium carbonate l-phenyl-4-methy Ru-4-hydroxyme Chil-3-pyrazolide hmm potassium bromide potassium thiocyanate potassium iodide 2.0g 0g 0g 3g 2.0g 2.5g 1.2 g 2.0mg 2.0g 0g 0g 3g 2.0g 1.4g 1.2g add water 1000d 1000d P.H. 9,609,60 PH was adjusted with hydrochloric acid or potassium hydroxide.

Nitrilo-N, N.

− 3.0g to mother liquor trimethylene phosphone Acid/pentasodium salt Tin chloride dihydrate p-Atonophenol Sodium hydroxide glacial acetic acid add water P.H. PH is hydrochloric acid or hydroxide Looking forward to seeing you Nitrilo-N, N, N- trimethylene phosphone Acid/pentasodium salt sodium sulfite Trisodium phosphate 12 water salt potassium bromide potassium iodide Sodium hydroxide same i,og 0.1g g 5- 1000+d 6.00 Adjusted with thorium.

Mother liquor replenisher 2.0g 2.0g 7.0g 7.Og 6g 6g 1.0g 90■ 3.0g 3.0g Citrazic acid N-ethyl-(β-meta) sulfonamidoethyl )-3-methyl-4 1Ajunoaniline sulfate salt 3.6-Shichia 1.8- octanediol add water P.H. PH is hydrochloric acid or potassium hydroxide 1.5g 1g 1.5 g 1g 1.0g 1.0 g 1000d 1000ad 11.80 12.00 Adjusted with ram.

Ethylenediaminetetraacetic acid ・Disodium salt ・2 water salt sodium sulfite ! -thioglycerin Sorbitan ester* add water 8.0g for mother liquor same 2g 0.4d 0.1g 000af , l(6,20 pH was adjusted with hydrochloric acid or sodium hydroxide.

2. Standing mother liquor Replenisher ethylenediaminetetraacetic acid 2.0g 4.0g・
Disodium salt/dihydrate ethylenediaminetetraacetic acid 120 g 240
g・Fe (I[[) ・Ammonium・potassium dichlorobromide 100 g 20
0 g ammonium nitrate 10 g 2
0g pH 5,705,50 pH was adjusted with hydrochloric acid or sodium hydroxide.

Fixed amount mother liquor Replenisher ammonium thiosulfate 8.0g Sodium sulfite 5.0g Add the same sodium bisulfite 5.0g water to the mother liquor
1000dp H6,60 pH was adjusted with hydrochloric acid or aqueous ammonia.

Chising bean formalin (37χ) Polyoxyethylene-p-monononylphenyl ethyl 10) Add water and H Sorbitan ester* Mother liquor Replenisher 5,0d Mother liquor 0,5m Same 1000a+ffi No adjustment (w+x+y+z-20 ) Preparation of sample 202 A sample 202 was prepared in the same manner as sample 201 except that the intermediate layer of the 12th layer was removed.

Preparation of Sample 203 In Sample 202, the yellow colloidal silver added to the 13th layer was removed and replaced with dye dispersion S-1 used in Example 1.
Sample 202 was prepared in the same manner as Sample 202 except that the amount of dye added was 0.23 g/nf.

Preparation of Samples 204 to 208 Samples were prepared in the same manner as Sample 203 except that S-2 to S-6 were added in equal weights instead of S-1.

Preparation of Samples 209 to 216 In place of couplers C-4 and C-7 added to the 9th to 11th layers in Samples 201 to 208, couplers (A-4)-14 of the present invention were added to C-4 and C-4. 0 of the total number of moles of 7
．． It was produced in the same manner as Samples 201 to 208 except that 65 times the molar amount was added.

After cutting the obtained samples 201 to 216, the MTF value of the green sensitive layer was evaluated for sharpness evaluation, and the long-term storage stability was evaluated in the same manner as in Example 1. The treatments used are as described below.

The obtained results are shown in Table 2. As is clear from Table 2, even if the dye and coupler of the present invention are combined, the sensitivity decreases during long-term storage and the maximum density decreases (
It can be seen that there is little amount of fog (which is thought to be caused by fog build-up during the first development) and that the sharpness is high.

Furthermore, when the color reproducibility of Samples 201 to 216 was evaluated, it was confirmed that the color saturation mainly from orange to pink was greatly improved in the samples using the coupler of the present invention.

(Effects of the Invention) As shown above, it can be seen that when the dye of the present invention is combined with the coupler of the present invention, fogging and loss of sensitivity during long-term storage that occur when colloidal silver is used can be significantly reduced. This is a huge effect that could not have been predicted until now.

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one layer constituting the light-sensitive material has the following general formula (I) to
A hydrophilic colloid layer containing a microcrystalline dispersion of at least one compound selected from the group consisting of (VI), and at least one layer containing at least one kind of photographic coupler represented by the following general formula (A). A silver halide color photographic light-sensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (III) A=L_1−(L_2−L_3)_n−
A' General formula (IV) A=(L_1-L_2)_2_-_q
= B General formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A and A' may be the same or different, and each B represents an acidic nucleus, B represents a basic nucleus, X and Y may be the same or different, and each represents an electron-withdrawing group.R
represents a hydrogen atom or an alkyl group, R_1 and R_2 each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R_1 and R_2 may be linked to form a 5- or 6-membered ring. R_2 and R_6 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group, or a halogen atom, and R_4 and R_5 each represent a hydrogen atom or R_1
represents a group of nonmetallic atoms necessary for R_4 or R_2 and R_5 to connect to form a 5- or 6-membered ring. L_1,
L_2 and L_3 each represent a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2, p represents 0 or 1, when p is 0, R_3 represents a hydroxy group or a carboxyl group, and R_4 and R_
5 represents a hydrogen atom. B' represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group. However, the compounds represented by general formulas (I) to (VI) have dissociative properties that have a pKa in the range of 4 to 11 in a mixed solution with a volume ratio of water and ethanol in one molecule of 1:1. It has at least one group. ) General formula [A] In general formula [A], R^a^1 represents a hydrogen atom or a substituent, and X^a^1 represents a hydrogen atom or coupling with an oxidized aromatic primary amine developer. Represents a group that can be separated by reaction. Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and the Za-Zb bond and Z
One of the b-Zc bonds is a double bond and the other is a single bond. The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, R^a^
1 or X^a^1 to form a dimer or more multimer is also included. Furthermore, when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer.