JPH0619087A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To control the balance of decolorization between yellow and magenta color images and to improve preservation property of color images by incorporating specified couplers into each of blue-sensitive layer and green-sensitive layer. CONSTITUTION:The blue-sensitive layer contains at least one kind of acylacetoamide type yellow dye-producing coupler having an acyl group expressed by formula I. The green-sensitive layer contains at least one kind of magenta dye-producing coupler expressed by formula II. In formula I, R1 is a substituent and Q represents nonmetal atoms necessary to form a six- member heterocyclic ring with C or five-member heterocyclic ring including two hetero atoms. In formula II, R1 is a hydrogen atom or substituent, and Z represents nonmetal atoms necessary to form a five-member azole ring including 2-4 nitrogen atoms. This azole ring may have substituents (including a condensed ring), and X is a hydrogen atom or a group which can be detached by the coupling reaction with the oxidant of a developing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a color photographic light-sensitive material containing a novel yellow coupler and a pyrazolotriazole coupler having a specific structure.

[0002]

The formation of a dye image in a silver halide color photographic light-sensitive material usually involves reducing the silver halide grains in the silver halide color photographic light-sensitive material exposed to an aromatic primary amine color developing agent. It is oxidized at this time, and this oxidant is subjected to a coupling reaction with a coupler previously contained in the silver halide color photographic light-sensitive material. In a silver halide color photographic light-sensitive material, three types of couplers that form dyes of yellow, magenta and cyan are usually used in order to reproduce colors by a subtractive color method. Among these, regarding the yellow coupler, an acylacetanilide type coupler having an active methylene (methine) group is generally known (TH James, “The Theory of the Photographic.
Process, 4th edition, p. 354). These couplers have drawbacks such as a low extinction coefficient, poor color image storability, especially dark storability, and broad spectral absorption and poor color reproducibility. Further, as a coupler similar to the yellow coupler of the present invention, for example, U.S. Pat. Nos. 4,149,886 and 4,09
Malondianilide yellow couplers described in 5,984, 4,477,563 and British Patent 1,204,680 are known, but these couplers have further low color image storability. It was a problem. In addition, the spectral absorption is broad and there is a skirt at the long-wave end, causing a problem in color reproducibility. Further, U.S. Pat. No. 5,118,599 discloses a dioxane carbonyl-based yellow coupler, which does not have sufficient performance in terms of the reactivity of the coupler, the dark fastness of the dye, and the spectral absorption characteristics. Absent. European Patent No. 447969 discloses a 3-5 membered cycloalkylcarbonyl group and a 3-5 membered heterocyclic carbonyl group, which was also the case. In recent years, attention has been focused on improving the hue of magenta color by using a pyrazoloazole-based magenta coupler instead of the 5-pyrazolone type coupler which has been used as a magenta coupler. The dye produced by the reaction between these couplers and the oxidation product of the color developing agent has a small amount of side absorption harmful to color reproduction, and thus can broaden the color reproduction range. For these couplers, see, for example, US Pat.
725,067, 4,942,117, JP-A-60-172982, 63-231347 and 6
No. 3-291058 and others. In addition, these couplers show superior performance in the dark preservation of images as compared with the conventional pyrazolone type couplers.

[0003]

However, the combination of the conventional yellow coupler and the pyrazoloazole-based magenta coupler improves the dark storage stability of the magenta color image, but the dark storage stability of the yellow color image is poor. On the contrary, it was a problem because the balance was lost. Furthermore, when the fading behavior in the portion where only yellow color is developed is examined, a new problem has emerged that magenta is mixed in the yellow portion as the yellow color image fades. Therefore,
An object of the present invention is to provide a color photographic light-sensitive material in which the color fading balance of yellow and magenta color images is adjusted by using a pyrazolotriazole type coupler and the color image storability is improved in practical use. Another object of the present invention is to provide a color photographic light-sensitive material in which the color mixture of magenta color due to the fading of the yellow colored portion when a pyrazolotriazole coupler is used is improved.

[0004]

As a result of earnest studies, the present inventors have found that the above-mentioned problems can be achieved by the silver halide color photographic light-sensitive material of the following means. That is, in a silver halide color photographic light-sensitive material having at least one blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support, an acyl group in the blue-sensitive layer is represented by the following general formula (1). A silver halide color photographic light-sensitive material containing at least one acetamide-type yellow dye-forming coupler and at least one magenta dye-forming coupler represented by the following general formula [M] in the green-sensitive layer. General formula (1)

[0005]

[Chemical 3]

In the formula, R ₁ represents a substituent, Q represents a 6-membered heterocycle together with C, or 5 containing two heteroatoms.
Represents a group of non-metal atoms necessary to form a member heterocycle. General formula [M]

[0007]

[Chemical 4]

In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

The general formula (1) in the present invention will be described in detail below.

The acylacetamide type yellow coupler of the present invention is preferably represented by the following general formula (Y). General formula (Y)

[0011]

[Chemical 5]

In the formula, R ₁ represents a substituent, Q represents a 6-membered heterocycle together with C, or 5 containing two heteroatoms.
Represents a group of non-metal atoms necessary to form a member heterocycle. R ₂ is a hydrogen atom or a halogen atom (F, Cl, Br,
I. The same applies to the description of the formula (Y) below. ), An alkoxy group, an aryloxy group, an alkyl group or an amino group,
₃ is a substitutable group on the benzene ring, X is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidation product of an aromatic primary amine developing agent (hereinafter referred to as leaving group), and k is 0.
Represents an integer of 4 respectively. However, when k is plural, plural R ₃ may be the same or different.

Examples of R ₃ are halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, There are alkylsulfonyl groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, alkoxysulfonyl groups, nitro groups, heterocyclic groups, cyano groups, acyl groups, acyloxy groups, alkylsulfonyloxy groups, arylsulfonyloxy groups, Examples of the leaving group include a heterocyclic group bonded to the coupling active position with a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, and a halogen atom.

When the substituent in the formula (Y) is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cyclic, unless otherwise specified. An alkyl group which may contain an unsaturated bond (for example, methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, Allyl, 3-cyclohexenyl,
Oleyl, benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl).

When the substituent in the formula (Y) is an aryl group or includes an aryl group, the aryl group may be a monocyclic or condensed ring aryl group which may be substituted (eg, phenyl, unless otherwise specified). 1-naphthyl, p-tolyl, o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecyl Phenyl,
2,4-di-t-pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl).

When the substituent in the formula (Y) is a heterocyclic group or contains a heterocyclic group, the heterocyclic group is at least 1 selected from O, N, S, P, Se and Te unless otherwise specified. Optionally substituted 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing 4 heteroatoms in the ring (for example, 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1
-Imidazolyl, 1-benzotriazolyl, 2-benzotriariazolyl, succinimide, phthalimide, 1
-Benzyl-2,4-imidazolidindione-3-yl).

The substituents preferably used in formula (Y) will be described below. In the formula (Y), R ₁ is preferably a halogen atom, a cyano group, or the total number of carbon atoms which may be substituted (hereinafter abbreviated as C number) 1 to 30.
Is an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, or a monovalent group having 6 to 30 C atoms (for example, an aryl group or an aryloxy group), and the substituent thereof is, for example, a halogen atom, an alkyl group or an alkoxy group. Base,
There are nitro group, amino group, carbonamido group, sulfonamide group, and acyl group. R ₁ may be a so-called ballast group. R ₁ may combine with Q to form a bicyclo ring. In formula (Y), Q is preferably a 6-membered heterocycle having 2 to 30 C atoms, which contains at least one heteroatom selected from N, S, O and P together with C in the ring, or N , S, O, and P represent a group of non-metal atoms necessary to form a 5-membered heterocycle containing two heteroatoms selected from the group. Further, the ring formed by Q together with C may contain an unsaturated bond in the ring, and may be substituted or unsubstituted. When it is substituted, examples of the substituent are the same as those described for R ₃ , but they may be further substituted with an oxo group. Also,
The substituents may be bonded to each other to form a ring. Among the 6-membered heterocyclic ring formed by Q together with C, even more preferable is a case where twice the carbonyl-substituted carbon (β-position as viewed from carbonyl) is at least one heteroatom, and therefore the general formula ( The more preferable acyl group represented by 1) is represented by the following general formula (III). General formula (III)

[0018]

[Chemical 6]

In the formula, Z is a hetero atom selected from O, S, N and P, R ₁ represents a substituent, and Q includes C and Z together with a 6-membered heterocycle or two heteroatoms. Represents a group of non-metal atoms necessary for forming a heterocyclic ring of a member. R
₁ and Q have the same contents as those in formula (Y), and preferred examples are also the same. R in formula (Y)
₂ is preferably a halogen atom, any of which may be substituted, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or C
Represents an amino group of the number 0 to 30, and as a substituent thereof,
For example, there are a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In the formula (Y), R ₃ is preferably a halogen atom, any of which may be substituted, an alkyl group having 1 to 30 C atoms, an aryl group having 6 to 30 C atoms, or 1 to 30 C atoms.
Alkoxy group, C 2-30 alkoxycarbonyl group, C 7-30 aryloxycarbonyl group, C 1-30 carbonamido group, C 0-30 sulfonamide group, C 1-30 Carbamoyl group, C number 1-3
0 sulfamoyl group, C 1-30 alkylsulfonyl group, C 6-30 arylsulfonyl group, C 1
To 30 ureido group, C number 0 to 30 sulfamoylamino group, C number 2 to 30 alkoxycarbonylamino group, C number 1 to 30 heterocyclic group, C number 1 to 30 acyl group, C number It represents an alkylsulfonyloxy group of 1 to 30 or an arylsulfonyloxy group of 6 to 30 carbon atoms, and the substituent thereof is, for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a hetero group. Ring oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfo group

Nyl group, arylsulfonyl group, acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino group, ureido group, cyano group,
Nitro group, acyloxy group, alkoxycarbonyl group,
There are an aryloxycarbonyl group, an alkylsulfonyloxy group, and an arylsulfonyloxy group.

In the formula (Y), k preferably represents an integer of 1 or 2, and the substitution position of R ₃ is preferably meta or para to the acylacetamide group. In formula (Y), X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom.

When X represents a heterocyclic group, X is preferably a 5- to 7-membered monocyclic or condensed-ring heterocyclic group which may be substituted, and examples thereof include succinimide, maleinimide and phthalimide. , Diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole,
Benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidine-
2-one, oxazolidin-2-one, thiazolidine-
2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2
-Pyrrolin-5-one, 2-imidazolin-5-one,
Indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5
-Dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone-2-pyrazone, 2-amino-1,
3,4-thiazolidine, 2-imino-1,3,4-thiazolidin-4-one and the like, and these heterocycles may be substituted. Examples of the substituents of these heterocycles include halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, sulfo group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyl group. Sulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl group There is an amino group. When X represents an aryloxy group, X preferably has a C number of 6
It represents an aryloxy group of 30 to 30 and may be substituted with a group selected from the substituent group mentioned when X is a heterocycle. Examples of the substituent of the aryloxy group include a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group and an arylsulfonyl group. A group or a cyano group is preferable.

Substituents particularly preferably used in formula (Y) are described below. R ₁ is particularly preferably a halogen atom, an alkyl group, an alkoxy group or an alkylthio group, and most preferably a methyl group, an ethyl group or a methoxy group.

R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6, (for example, methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), an alkoxy group having a C number of 1 to 30. (Eg methoxy,
Ethoxy, methoxyethoxy, butoxy), or an aryloxy group having a C number of 6 to 24 (for example, phenoxy group, p
-Tolyloxy, p-methoxyphenoxy). R
₃ is particularly preferably a halogen atom, an alkoxy group,
It is an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, most preferably a sulfamoyl group, an alkoxycarbonyl group, a carbonamide group or a sulfonamide group.

X is particularly preferably Chemical formula 7, Chemical formula 8 and Chemical formula 9
Formula (Y-1), (Y-2), or (Y-3) described in
Is a group represented by.

[0027]

[Chemical 7]

In the formula (Y-1), Z is --O--CR ₄ (R
_{5) -, - S-CR} 4 (R 5) -, NR 6 -CR 4 (R 5) -, -
_{NR 6 -NR 7 -, NR 6} -C (O) -, - CR 4 (R 5)
-CR ₈ (R ₉₎ - or CR ₁₀ = CR ₁₁ - represent.

Here, R ₄ , R ₅ , R ₈ and R ₉ are hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group or amino group. the stands, R ₆ and R ₇ are a hydrogen atom, an alkyl group,
It represents an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ or R
₄ and R ₈ may combine with each other to form a ring (for example, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by the formula (Y-1), particularly preferable one is Z in the formula (Y-1).
_{CR 4 (R 5) -,} NR 6 -CR 4 (R 5) or -NR ₆ -N
A heterocyclic group which is R ₇ —. The C number of the heterocyclic group represented by the formula (Y-1) is 2 to 30, preferably 4 to 20, and more preferably 5 to 16.

[0031]

[Chemical 8]

In the formula (Y-2), at least one of R ₁₂ and R ₁₃ is a halogen atom, a cyano group, a nitro group,
A group selected from a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and the other is a hydrogen atom, It may be an alkyl group or an alkoxy group. R ₁₄ represents a group having the same meaning as R ₁₂ or R _13, and m represents an integer of 0-2. Expression (Y
The C number of the aryloxy group represented by -2) is 6 to 30.
It is preferably 6 to 24, more preferably 6 to 15.

[0033]

[Chemical 9]

In the formula (Y-3), W represents a non-metal atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N.
Here, the ring represented by the formula (Y-3) may have a substituent, and examples of the substituent are preferably a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group, an aryl group, It is an amino group, an alkoxy group, an aryloxy group or a carbamoyl group. Formula (Y-
The C number of the heterocyclic group represented by 3) is 2 to 30, preferably 2 to 24, more preferably 2 to 16.

X is most preferably a group represented by the formula (Y-1).

The coupler represented by the formula (Y) is a dimer having a substituent R ₁ , Q, X or a group represented by the formula Yb) represented by the chemical formula 10 and bonded to each other through a divalent or higher valent group. It may form a body or multimers. in this case,
It may be out of the range of the number of carbon atoms shown in each of the above substituents.

[0037]

[Chemical 10]

Chemical formulas 11 to 21 show specific examples of each substituent in the formula (Y).

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

[0047]

[Chemical 19]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

Chemical formulas 22 to 38 show specific examples of the yellow coupler represented by the formula (Y).

[0051]

[Chemical formula 22]

[0052]

[Chemical formula 23]

[0053]

[Chemical formula 24]

[0054]

[Chemical 25]

[0055]

[Chemical formula 26]

[0056]

[Chemical 27]

[0057]

[Chemical 28]

[0058]

[Chemical 29]

[0059]

[Chemical 30]

[0060]

[Chemical 31]

[0061]

[Chemical 32]

[0062]

[Chemical 33]

[0063]

[Chemical 34]

[0064]

[Chemical 35]

[0065]

[Chemical 36]

[0066]

[Chemical 37]

[0067]

[Chemical 38]

The synthesis examples of the coupler of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplified Compound Y-29 Exemplified Compound Y-29 was synthesized by the following scheme.

[0069]

[Chemical Formula 39]

After acetalizing ethyl pyruvate with 2,4-pentyldiol, 17.2 g of compound A obtained by hydrolysis was dissolved in 50 ml of methylene chloride and 1 ml of N, N'-dimethylformamide. Then, under ice cooling, 10.5 ml of oxalyl chloride was added dropwise. After stirring at room temperature for 1 hour, all the solvents were distilled off under reduced pressure to obtain a carboxylic acid chloride of compound A. To 2.4 g of active magnesium, 40 ml of methanol was added dropwise to magnesium methoxide, and 13.1 g of ethyl 3-oxobutanoate was added, and the mixture was refluxed for 2 hours. After the methanol was distilled off under reduced pressure, the carboxylic acid chloride of the compound A was added dropwise with 50 ml of THF and the mixture was refluxed for 30 minutes. After post-treatment by a conventional method, by column chromatography,
The compound B was obtained as an oily product (17.1 g). Compound B was added to a solution of 100 ml of ethanol and 20 ml of aqueous ammonia (30%) and stirred at 50 ° C for 30 minutes. Post-treatment was carried out by a conventional method to give an oily product of β-keto ester (Compound C) at 13.8
g was obtained. Compound C 13.8 g and 2,4-dichloro-5
21.3 g of dodecyloxycarbonylaniline were heated at 120 ° C. without solvent. After 1 hour, the mixture was further heated and reacted under reduced pressure for 1 hour, and then the reaction product was purified by column chromatography with a mixed solvent of n-hexane and ethyl acetate to obtain 22.8 g of compound D. Compound D (22.8 g) was dissolved in methylene chloride (300 ml), and sulfuryl chloride (5.67 g) was added dropwise under ice cooling. After the reaction for 30 minutes, all the solvents were distilled off under reduced pressure, and N, N'-dimethylformamide (100 ml) and 1-benzyl-5-ethoxyhydantoin 1 were added.
8.7 g and triethylamine 12 ml were added, and the mixture was reacted at 40 ° C. for 2 hours. After post-treatment by a conventional method, purification by column chromatography was performed to obtain 19.2 g of the objective compound Y-29 as an oily substance.

Synthesis Example 2 Synthesis of Exemplified Compound Y-10 Compound E was used in place of Compound A used in the synthesis of Exemplified Compound Y-29, and 2-in place of 2,4-dichloro-5-dodecyloxycarbonylaniline. Chloro-5
Exemplified compound Y-10 was obtained in the same manner except that-[2- (2,4-di-t-amylphenoxy) butanoic acid amide] aniline was used.

[0072]

[Chemical 40]

Next, the general formula [M] in the present invention will be described in detail. In the formula [M], R ₁ represents a hydrogen atom or a substituent. Z is 5 containing 2 to 4 nitrogen atoms
Represents a group of non-metal atoms necessary to form a member azole ring, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. Hereinafter, the coupler will be described in detail. Among the coupler skeletons represented by the formula [M], 1H-imidazo (1,2-b) is preferable.
Pyrazole, 1H-pyrazolo (1,5-b] [1,2,
4] Triazole, 1H-pyrazolo (5,1-c]
[1,2,4] triazole, 1H-pyrazolo (1,5
-D] tetrazole and 1H-pyrazolo (1,5-
a] benzimidazole, each of the formula [M-
I], [M-II], [M-III], [M-IV] and [MV].

[0074]

[Chemical 41]

Among the coupler skeletons represented by the formula [M], among the above skeletons, [M-II] and [M-III]
Is preferred. Further, it is most preferable to use the coupler represented by the formula [M-III]. The substituents R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , n and X in these formulas will be described in detail.

R ₁ , R ₂ and X will be described in detail. R ₁ is hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group. , Ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyl Oxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
It represents a phosphonyl group, an aryloxycarbonyl group, an acyl group or an azolyl group, and R ₁ may be a divalent group to form a bis form.

More specifically, R ₁ is each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). Group, alkynyl group,
A cycloalkyl group or a cycloalkenyl group, more specifically,
For example, methyl, ethyl, propyl, isopropyl, t-
Butyl, tridecyl, 2-methanesulfonylethyl, 3
-(3-Pentadecylphenoxy) propyl, 3- {4
-{2- [4- (4-hydroxyphenylsulfonyl)
Phenoxy] dodecanamide} phenyl} propyl, 2
-Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (e.g. phenyl, 4-t-butylphenyl, 2,4-di-t-). Amylphenyl, 4-
Tetradecanamidophenyl), a heterocyclic group (for example,
2-furyl, 2-cenyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example,
Methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), an aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-). Butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl), an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino A group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- {α- (3-
t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoyl) Amino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-)
t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-
Butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (for example, N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N
-Diethylsulfamoyl), a sulfonyl group (for example,
Methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy) , 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), an acyloxy group (for example, acetoxy). A carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryl Oxy carbonylamino group (e.g., phenoxycarbonylamino), an imido group (e.g., N- succinimido, N- phthalimido, 3
-Octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-
Pyridylthio), a sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl,
3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, Benzoyl, 4-dodecyloxybenzoyl) and an azolyl group (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl). Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁ is alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group, urethane group,
An acylamino group can be mentioned. R ₂ has the same meaning as the substituent exemplified for R ₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, or carbamoyl. A group or an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group or an arylthio group.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. The splitting-off group is specifically described as a halogen atom, an alkoxy group, an aryloxy group or an acyloxy group. Group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5-membered or 6-membered group There are a nitrogen heterocyclic group, an imide group, an arylazo group and the like, and these groups may be further substituted with a group acceptable as the substituent for R ₁ . More specifically, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), an aryloxy group ( For example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy,
4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy group (for example,
Methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (eg, dichloroacetylamino, heptafluorobutyrylamino), an alkyl or aryl sulfonamide group (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino). An alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (eg, phenoxycarbonyloxy), an alkyl, aryl or heterocyclic thio group (eg, dodecylthio, 1-carboxydodecylthio, Phenylthio,
2-butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5-membered or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, Pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide group (for example, succinimide, hydantoinyl), arylazo group (for example, phenylazo, 4-
Methoxyphenylazo) and the like. In addition to these, X may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. X is a development inhibitor,
It may contain a photographically useful group such as a development accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom.

The coupler represented by the general formula [M] in the present invention is preferably added to the green-sensitive emulsion layer, but may be added to the non-photosensitive intermediate layer. The addition amount is generally 0.001 mol to 2 mol, preferably 0.01 mol to 0.5 mol per 1 mol of silver in the emulsion layer. When used in the non-photosensitive layer, the addition amount per unit area is the same as that in the emulsion layer. Next, a general method for synthesizing the coupler of the present invention will be described. 1H-pyrazolo [5,1-c] -1,2,4 represented by the general formula [M]
-Synthesis of triazole skeleton is described in US Patent 3,725,06
No. 7, Japanese Patent Publication No. 47-27, 411, No. 48-30, 8
95, JP-A-54-145,135, Research Disclosure 12443, J. Chem. Soc. Perkin.
It can be synthesized by the method described in I. page 2047 (1977) and the like. Further, it can be synthesized according to the method described in JP-A-2-134354. A general method for introducing a coupling-off group will be described. (1) Method of introducing halogen atom

[0081]

[Chemical 42]

Halogenation of the coupling active position is carried out by halogenating 4 equivalents of bromine, N-bromosuccinimide, sulfuryl chloride, or N-chlorosuccinimide with 1 equivalent of coupler (A) in an inert solvent such as dichloromethane. It can be easily obtained by acting an agent or the like. (2) Method of connecting oxygen atoms (a) Substitution of halogen atom of coupler having halogen atom at coupling active position by phenoxy group

[0083]

[Chemical 43]

The halogenated compound (B) was converted to dimethylformamide (DMF), dimethylsulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), N-.
In an aprotic polar solvent such as methyl-2-pyrrolidone, suitable R ₅ —OM, (R ₅ —O) ₂ M ′ or (R ₅ —O) ₃ M ″ (R ₅ represents an aryl group, M,
(M 'and M "represent monovalent, divalent and trivalent metal ions, respectively), to give (C) in which an aryloxy group is introduced at the intended coupling active position. Preferably, the halogenated compound (B) is added in an equivalent to 50 times amount (weight) of the above solvent and an equivalent to 20 times amount (molar ratio) of a suitable sodium or potassium salt of phenol at 50 ° C to 150 ° C. It is desirable to react at a temperature, and in this reaction, addition of a quaternary ammonium salt such as tetrabutylammonium bromide or an alkali metal halide such as cesium bromide may accelerate the reaction. 1H-pyrazolo [5,1-c] -1, after introducing an aryloxy group into the active methylene of ketonitrile,
A method for forming a 2,4-triazole skeleton.

[0085]

[Chemical 44]

The halogenated compound (E) obtained by treating 3-oxonitrile (D) with a halogenating agent such as bromine or sulfuryl chloride in an inert solvent such as dichloromethane is appropriately prepared in the presence of a tertiary amine. The aryloxy compound (F) can be obtained by treating with R ₅ —OH or with a metal salt such as R ₅ —OM described in (1) above. Aminopyrazole obtained by reacting this with foamed water hydrazine in a solvent such as ethanol, a diazonium salt is synthesized using sodium nitrite or isoamyl nitrite and an acid (for example, hydrochloric acid or sulfuric acid), and this diazonium salt is When treated with a reducing agent such as stannous chloride, sodium sulfite, or sodium hydrosulfite, a hydrazinopyrazole body (H)
Is obtained. The target coupler can be synthesized from this (H) form according to the above-mentioned skeleton synthesis method. 3-oxonitrile (D) is described in U.S. Pat. No. 4,411,753, German Patent Publication DE 3,209,472 and Synthes.
It can be synthesized by the method described in is, 472 (1977) and the like.

(3) Method for Linking Sulfur Atoms A coupler in which an aromatic mercapto or heterocyclic mercapto group is substituted at the 7-position is a method described in US Pat. No. 3,227,554, that is, an aryl mercaptan, a heterocyclic mercaptan and a compound thereof. It can be synthesized by dissolving the corresponding disulfide in a halogenated hydrocarbon solvent and adding chlorine or sulfuryl chloride as a sulfenyl chloride to a 4-equivalent coupler dissolved in an aprotic solvent.
As a method for introducing an alkylmercapto group at the 7-position, a method described in US Pat. No. 4,264,723, that is, introducing a mercapto group at the coupling active position of a coupler,
A method of allowing a halide to act on this mercapto group and S-
A method of synthesizing in one step with (alkylthio) isothiourea or a hydrochloride (or bromine hydrochloride) is effective.

(4) Method of connecting nitrogen atoms (a) Method of introducing an amino group into the coupling active position and modifying the amino group. The introduction of an amino group into the coupling active position is carried out by the method shown in US Pat. No. 3,419,391, that is, by nitrosating the coupling active position and reducing it by a suitable method, and modifying the resulting amino compound. It can be easily obtained. Further, by coupling a diazonium salt derived from, for example, aniline anthranilic acid, and sulfanilic acid to the coupling active position to obtain an azo dye, which is then reduced with a suitable reducing agent such as hydrosanphyto soda. It can be easily obtained by modifying the obtained amino compound. (b) A method in which a halogen atom is introduced at the coupling active position and the halogen atom is replaced with an R ₈ (R ₉ ) N-group.
R ₈ or R ₉ is an alkyl group, an aryl group, a heterocyclic group, and R ₈ and R ₉ are a nitrogen heterocyclic group which may bond with each other to form a 5- or 6-membered ring with a nitrogen atom; ₈ (R ₉ ) N- and the halogen-substituted compound (B) are dissolved in an alcoholic solvent aprotic polar solvent, a halogenated hydrocarbon solvent, or the like in the temperature range of 0 ° C to 180 ° C, and the presence of a suitable base is present. It can be obtained by reacting under. Specific examples of the compound represented by the general formula [M] of the present invention are shown below, but the invention is not limited thereto.

[0089]

[Chemical formula 45]

[0090]

[Chemical formula 46]

[0091]

[Chemical 47]

[0092]

[Chemical 48]

[0093]

[Chemical 49]

[0094]

[Chemical 50]

[0095]

[Chemical 51]

[0096]

[Chemical 52]

[0097]

[Chemical 53]

[0098]

[Chemical 54]

[0099]

[Chemical 55]

[0100]

[Chemical 56]

[0101]

[Chemical 57]

[0102]

[Chemical 58]

[0103]

[Chemical 59]

[0104]

[Chemical 60]

[0105]

[Chemical formula 61]

[0106]

[Chemical formula 62]

[0107]

[Chemical formula 63]

[0108]

[Chemical 64]

[0109]

[Chemical 65]

[0110]

[Chemical formula 66]

[0111]

[Chemical formula 67]

[0112]

[Chemical 68]

[0113]

[Chemical 69]

[0114]

[Chemical 70]

[0115]

[Chemical 71]

[0116]

[Chemical 72]

[0117]

[Chemical formula 73]

[0118]

[Chemical 74]

The yellow coupler represented by the general formula (1) of the present invention is 1.0-1.mol per mol of silver halide.
It can be used in the range of 0 × 10 ⁻³ mol. It is preferably 5.0 × 10 ^{−1 to} 2.0 × 10 ⁻² mol, and more preferably 4.0 × 10 ^{−1 to} 5.0 × 10 ⁻² mol. The yellow coupler represented by the general formula (1) of the present invention may be used in combination of two or more kinds, or may be used in combination with other known couplers. The same applies to the coupler represented by the general formula [M]. The couplers represented by formulas (1) and [M] of the present invention can be introduced into the color light-sensitive material by various known dispersion methods. In the oil-in-water dispersion method, a low-boiling organic solvent (for example, ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol, etc.) is used to apply a fine dispersion, and a substantially low-boiling organic solvent is applied in a dry film. May not remain. When a high-boiling organic solvent is used, any of those having a boiling point of 175 ° C. or higher under normal pressure may be used, and one kind or two or more kinds may be arbitrarily mixed and used. The ratio of the coupler of the present invention to these high boiling point organic solvents can be in a wide range, but is in the range of 5.0 or less by weight per 1 g of the coupler. Preferably 0-2.
It is 0, and more preferably in the range of 0.01 to 1.0. Further, the latex dispersion method described below can also be applied. Furthermore, it can be used as a mixture or coexistence with various couplers and compounds described later.

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as usual. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably have a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63936
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,70
5,744, 4,707,436, JP-A-62-160448, 6
3- 89850, it is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, RL, adjacent to or in proximity to the main photosensitive layer. . As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o.17643 (December 1978), pp. 22-23, "I. Emulsion production (Emu
lsion preparation and types) ”, and the same No.18716
(November 1979), p. 648, ibid. No. 307105 (November 1989), 863.
-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et P
hisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF D
uffin, Photographic Emulsion Chemistry (Focal Pres
s, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used for the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or number of silver halide grains is within ± 40% of the average grain size). (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer: page 649, right column 4. Whitening agent: page 24, page 647, right column 868, page 5, fogging prevention, page 24-25, page 649, right column, page 868-870, stabilizer, light absorber, 25- Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 pages 10. Binder page 26 651 pages left column 873 to 874 pages 11. Plasticizer, page 27 650 pages right column 876 lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitors 14. matting agents, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Examples of the yellow coupler include those represented by the general formula (1) of the present invention, for example, U.S. Pat. Nos. 3,933,501 and 4,022,620.
Nos. 4,326,024, 4,401,752, 4,24
No. 8,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760, U.S. Patent No. 3,973,968, No.
4,314,023, 4,511,649, European Patent 249,473
Those described in No. A, etc. are preferable. Magenta couplers include those represented by the general formula [M] of the present invention.
Pyrazolone-based and pyrazoloazole-based compounds are preferable, and U.S. Pat.Nos. 4,310,619, 4,351,897, EP 73,636, U.S. Pat. No. 3,061,432, and 3,72.
5,067, Research Disclosure No. 24220 (19
June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659,
61-72238, 60-35730, 55-118034, 60-1
85951, U.S. Pat.Nos. 4,500,630 and 4,540,654
No. 4,556,630, International Publication WO88 / 04795, 91/0
Those described in 1984 etc. are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
2,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137 and European Patent No. 341,188A.
As couplers in which the colored dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) No. 3,234,533 are preferable. Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, and No. 307105, VII-G.
, U.S. Pat.No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat.Nos. 4,004,929, 4,138,258, and British Patent 1,1.
Those described in No. 46,368 are preferable. In addition, US patent
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,774,181,
It is also preferred to use the couplers described in U.S. Pat. No. 4,777,120 which have as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, Item VII-F and No. 30710.
5, patents described in paragraph VII-F, JP-A-57-151944
Issue 57-154234, Issue 60-184248, Issue 63-37346,
Those described in U.S. Pat. No. 63-37350, U.S. Pat. Nos. 4,248,962, and 4,782,012 are preferable. RD No. 11449, 2424
1, the bleaching accelerator releasing coupler described in JP-A-61-201247 is effective for shortening the processing time having a bleaching ability, and in particular, the above-mentioned tabular silver halide grain-sensitive photosensitive material is used. The effect is great when added to the material.
Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140 and
Those described in 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferable. In addition, JP-A-60-107029,
Nos. 60-252340, JP-A-1-44940, and a compound that releases a fogging agent, a development accelerator, a silver halide solvent, etc. by a redox reaction with an oxidant of a developing agent described in JP-A 1-45687 preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after separation described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, 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. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photog
r.Sci.Eng.), No. 19, No. 2, pages 124 to 129 can be measured by using a swellometer (swelling meter) of the type described, and T _1/2 is 30 ° C. in a color developer. , 90% of the maximum swollen film thickness reached after treatment for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is 150-500
% Is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N diethylaniline and 3-methyl-4-amino-N-. Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose. The color developer is an alkali metal carbonate,
It contains a pH buffer such as borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. It is common. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene- 1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Representative examples include ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, and JP-A-53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July 1978), etc .; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715, West German Patent
Iodide salts described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294
The sulfinic acid compounds described in No. 769A are preferable. Furthermore,
For the purpose of stabilizing the solution, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution. In the present invention, the fixer or the bleach-fixer has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
It is preferable to add 1 to 10 mol / liter.

The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers Volume 64, P. 248-253 (1955)
May May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986) Sankyo Publishing, Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used. PH of washing water in the processing of the light-sensitive material of the present invention
Is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. In addition, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
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 accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure Nos. 14,850 and No. 15,159, aldol compounds described in No. 13,924, U.S. Pat.No. 3,719,492. Metal salt complexes described, JP-A-53-135
The urethane compound described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-(-3-phenyl-3-phenyl-3- (cyclohexyl) -3- (phenyl-3-phenyl-3-methyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3- (3-phenyl-3-phenyl-3- (3-phenyl-3- (phenyl-phenyl--3-one-
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-58-115438 and the like. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, the silver halide light-sensitive material of the present invention includes U.S. Pat. No. 4,500,626, JP-A-60-133449, JP-A-59-218443, and JP-A-61-238056.
It can also be applied to the photothermographic material described in European Patent No. 210,660A2.

[0138]

EXAMPLES The present invention will now be specifically described with reference to examples, but the invention is not limited thereto. Example 1

Preparation of Sample 101 Sample 101 was prepared by preparing a multi-layer color light-sensitive material having the following compositions on a cellulose triacetate film support having a thickness of 127 μm and having an undercoat. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use. First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g UV absorber U-4 0.1 g Ultraviolet absorber U-6 0.1 g High boiling point organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-D 5 mg Compound Cpd-L 5 mg Compound Cpd-M 3 mg High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Fine grained silver iodobromide emulsion with the surface and inside fogged (average particle size) 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g

Fourth Layer: Low Sensitivity Red Sensitive Emulsion Layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-30 .05 g Coupler C-9 0.05 g Compound Cpd-D 10 mg High boiling point organic solvent Oil-2 0.1 g Fifth layer: medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0 .8 g coupler C-1 0.2 g coupler C-2 0.05 g coupler C-3 0.2 g coupler C-9 0.05 g high boiling organic solvent Oil-2 0.1 g sixth layer: high sensitivity red-sensitive emulsion layer. Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Coupler C-9 0.1 g Additive P-1 0.1 g

Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-K 2.6 mg UV absorber U-1 0.1 g UV absorber U-6 0.1 g Dye D -1 0.02 g Compound Cpd-D 5 mg Compound Cpd-L 5 mg Compound Cpd-M 5 mg Eighth layer: intermediate layer Silver iodobromide emulsion fogged on the surface and inside (average grain size 0.06 μm, coefficient of variation 16) %, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 1.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-N 0.1 g Color mixing inhibitor Cpd-A 0.1 g 9th layer: low Sensitivity Green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-4 0.05 g Coupler C-7 0.25 g Compound Cpd-B 0. 03g Compound Cpd- D 10 mg Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling organic solvent Oil-1 0.1 g High boiling organic solvent Oil-2 0.1 g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.3 g Compound Cpd-B 0 0.03g compound Cpd-E 0.02g compound Cpd-F 0.02g compound Cpd-G 0.05g compound Cpd-H 0.05g high boiling organic solvent Oil-2 0.01g 11th layer: high-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.4 g Coupler C-7 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02g Compound Cpd-H 0.02g High boiling point organic solvent Oil-1 0.02g High boiling point organic solvent Oil-2 0.02g 12th layer: Intermediate layer Keratin 0.6g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.07 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Dye E-2 microcrystalline solid dispersion Material 0.05 g 14th layer: Intermediate layer Gelatin 0.6 g 15th layer: Low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.3g Coupler C-6 0.3g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.3 g Seventeenth layer: High Sensitivity Blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0.6 g Eighteenth layer: First protective layer gelatin 0.7 g Ultraviolet absorber U-10. 04g UV absorber U-2 0.01g UV absorber U-3 0.03g UV absorber U-4 0.03g UV absorber U-5 0.05g UV absorber U-6 0.05g High boiling organic solvent Oil-1 0.02 g Formalin scavenger Cpd-C 0.2 g Cpd-I 0.4 g Dye D-3 0.05 g Compound Cpd-N 0.02 g

19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer : Third protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μ) 0.1 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.1 g Silicone oil 0 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. Furthermore, in each layer,
In addition to the above composition, gelatin hardener H-1 and surfactants for coating and emulsifying W-3, W-4, W-5, W-6, W-
7 was added.

Further, as antiseptic and antifungal agents, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol were added.

[0148]

[Table 1]

[0149]

[Table 2]

The structures of the compounds used in Sample 101 are shown below.

[0151]

[Chemical 75]

[0152]

[Chemical 76]

[0153]

[Chemical 77]

[0154]

[Chemical 78]

[0155]

[Chemical 79]

[0156]

[Chemical 80]

[0157]

[Chemical 81]

[0158]

[Chemical formula 82]

[0159]

[Chemical 83]

[0160]

[Chemical 84]

[0161]

[Chemical 85]

[0162]

[Chemical 86]

[0163]

[Chemical 87]

[0164]

[Chemical 88]

[0165]

[Chemical 89]

[0166]

[Chemical 90]

[0167]

[Chemical Formula 91]

[0168]

[Chemical Formula 92]

[0169]

[Chemical formula 93]

Preparation of Samples 102 to 118 Table 10 shows instead of the couplers C-4, C-7, C-5 and C-6 added to the 9th to 11th layers and the 15th to 17th layers of Sample 101. Samples 102 to 118 were prepared in the same manner as Sample 101, except that the comparative compound and the compound of the present invention were replaced by the same mole number as the total mole number of the coupler added to the layer. Table 10 shows a list of couplers used.

[0171]

[Table 3]

The obtained samples 101 to 118 were cut into strips by a conventional method, exposed to white light and exposed through a yellow filter, and then subjected to the following developing treatment. As a result, strips that developed a gray color and strips that developed a single yellow color were obtained. 8 of these strips
After storage under conditions of 0 ° C. and 70% RH for 3 weeks, the density was measured, and the fading behavior of yellow and magenta under high temperature and high humidity conditions and the degree of magenta color mixing in the yellow colored portion were evaluated.

[0173]

[Table 4]

Treatment process Treatment process time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38 ° C. 12 liters 2.2 liter / m ² First water washing ² 〃 38 〃 4 〃 7.5 〃 Reverse rotation ² 〃 38 〃 4 〃 1 １ 〃 Color development 6 〃 38 〃 12 〃 2.2 〃 Adjust 2 〃 38 〃 4 〃 1.1 〃 Bleach 6 〃 38 〃 12 〃 0.22 〃 Fixed 〃 4 〃 38 〃 8 〃 〃 2nd water washing 4〃 38〃 8〃 7.5〃 stability 1〃 25〃 2〃 1.1〃 The composition of each treatment liquid was as follows. Black-and-white development Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Hydroquinone potassium monosulfonate 20 g 20 g Potassium carbonate 33 g 33 g 1-phenyl-4- Methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g 2.0 g potassium bromide 2.5 g 1.4 g potassium thiocyanate 1.2 g 1.2 g potassium iodide 2.0 mg-water was added 1000 ml 1000 ml pH 9. 60 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide. Inversion solution Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephos Same as mother liquor 5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide. Color developer Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate 12-hydrate 36 g 36 g Potassium bromide 1.0 g-potassium iodide 90 mg-sodium hydroxide 3.0 g 3.0 g citrazinic acid 1.5 g 1.5 g N-ethyl- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 11 g 11 g 3,6-dithia-1,8-octanediol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 The pH was adjusted with hydrochloric acid or potassium hydroxide. Adjustment liquid Mother liquor Replenishing liquid Ethylenediaminetetraacetic acid-2 sodium salt Same as mother liquor-Dihydrate 8.0 g Sodium sulfite 12 g 1-Thioglycerin 0.4 ml Sorbitan ester 0.1 g

[0175]

[Chemical 94]

Water was added to 1000 ml pH 6.20 The pH was adjusted with hydrochloric acid or sodium hydroxide. Bleaching solution Mother liquor Replenishing solution Ethylenediaminetetraacetic acid ・ Disodium salt ・ Dihydrate 2.0g 4.0g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ Dihydrate 120g 240g Potassium bromide 100g 200g Ammonium nitrate 10g 20g Add water 1000 ml 1000 ml pH 5.70 5.50 The pH was adjusted with hydrochloric acid or sodium hydroxide. Fixing solution Mother liquor Replenisher Ammonium thiosulfate 8.0 g The same sodium sulphite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia. Stabilizer Mother liquor Replenisher Formalin (37%) 5.0 ml Same as mother liquor Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5 ml Water added 1000 ml Without pH adjustment

The results are shown in Table 4. From Table 1, the samples of the present invention are excellent in image fastness of magenta and yellow color images and well balanced. Further, it can be seen that magenta is extremely rarely mixed in the color image of yellow single color. Example 2 Example 2 and sample 2 described in JP-A-2-90151
No. 01, couplers added to the sixth to eighth layers, Cp-
The coupler Y of the present invention instead of the coupler M-4 in which I is added to the coupler M-4 of the present invention in the 10th and 11th layers, Cp-L.
Sample A was prepared in the same manner as Sample 201 except that the equimolar ratio was changed to −8. The sample A was subjected to the same treatment as that of the example and the same test as that of the example 1 was conducted, and the same preferable result was obtained.

Example 3 The color photographic light-sensitive material of Example 2 described in JP-A-1-158431, and in the examples, the couplers EXM-11 and 12 of the sixth and seventh layers were used as the coupler M- of the present invention. 5
Replacing 6 to equimolar, couplers EX of 11th and 12th layers
Sample B was prepared in the same manner except that Y-1 was replaced with 0.7 times the mol of the coupler Y-11 of the present invention. These samples were developed according to the examples and tested for color image fastness according to the invention. As a result, the same results as in Example 1 were obtained. Example 4 Sample No. 1 of Example 1 described in JP-A-2-90145 and couplers EXM-1, 2 of the sixth and seventh layers,
Sample 3 was replaced with the coupler M-13 of the present invention in an equimolar amount, and the couplers XY-1, 2 of the 11th and 12th layers were replaced with 0.9 times the molar amount of the coupler Y-37 of the present invention. C was produced. These samples were developed according to the examples and tested for color image fastness according to the invention. As a result, the same results as in Example 1 were obtained. Example 5 The yellow coupler EXY of the sample 214 of Example 2 described in JP-A-2-139544 is used as the coupler Y of the present invention.
Sample D was prepared in the same manner, except that the equimolar amount was replaced with -53 and the magenta coupler EXM was replaced with the coupler M-52 of the present invention in an equimolar amount. These samples were developed according to the examples and tested for color image fastness according to the invention.
As a result, the same results as in Example 1 were obtained.

[0179]

According to the present invention, it is possible to obtain a color light-sensitive material having a good fading balance of yellow and magenta images, improved color image storability and improved color mixture of magenta.

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[Procedure amendment]

[Submission date] April 12, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

The substituents preferably used in formula (Y) will be described below. In the formula (Y), R ₁ is preferably a halogen atom, a cyano group, or the total number of carbon atoms which may be substituted (hereinafter abbreviated as C number) 1 to 30.
Is an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, or a monovalent group having 6 to 30 C atoms (for example, an aryl group or an aryloxy group), and the substituent thereof is, for example, a halogen atom, an alkyl group or an alkoxy group. Base,
There are nitro group, amino group, carbonamido group, sulfonamide group, and acyl group. R ₁ may be a so-called ballast group. R ₁ may combine with Q to form a bicyclo ring. In formula (Y), Q is preferably a 6-membered heterocycle having 2 to 30 C atoms, which contains at least one heteroatom selected from N, S, O and P together with C in the ring, or N , S, O, and P represent a group of non-metal atoms necessary to form a 5-membered heterocycle containing two heteroatoms selected from the group. Further, the ring formed by Q together with C may contain an unsaturated bond in the ring, and may be substituted or unsubstituted. When it is substituted, examples of the substituent are the same as those described for R ₃ , but they may be further substituted with an oxo group. Also,
The substituents may be bonded to each other to form a ring. Among the 6-membered heterocycles formed by Q together with C, even more preferable is the case where the 2-position of the carbonyl-substituted carbon (β-position as viewed from carbonyl) is at least one heteroatom, and therefore the general formula ( The more preferable acyl group represented by 1) is represented by the following general formula (III). General formula (III)

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0099

[Correction method] Change

[Correction content]

[0099]

[Chemical 55]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0101

[Correction method] Change

[Correction content]

[0101]

[Chemical 57]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0105

[Correction method] Change

[Correction content]

[0105]

[Chemical formula 61]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction content]

[0106]

[Chemical formula 62]

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support, wherein the blue-sensitive layer has an acyl group represented by the following general formula (1). A silver halide color containing at least one acylacetamide type yellow dye-forming coupler represented by the formula (1) and at least one magenta dye-forming coupler represented by the following general formula (M) in the green-sensitive layer. Photographic material. General formula (1) In the formula, R ₁ represents a substituent, and Q represents a non-metal atom group necessary for forming a 6-membered heterocycle with C or a 5-membered heterocycle containing two heteroatoms. General formula [M] In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.