JPH0619088A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a color photographic sensitive material excellent in sharpness and which is stably preserved for a long period. CONSTITUTION:At least one silver halide emulsion layer is provided on a base, at least one layer constituting the photosensitive material contains at least one kind of acylacetamide-type yellow coupler with the acyl group shown by formula I, and at least one layer constituting the photosensitive material contains at least one kind of compd. shown by formula II. In formula I, R1 is a substituent, and Q is a nonmetallic atom group necessary to form a 6- or 5-membered heterocyclic ring including two hetero atoms with C. In formula II, A is an oxidation-reduction (redox) mother nucleus or its precursor and is an atomic group capable of releasing (Time)1X for the first time after being oxidized in development, Time is a group liberating X released from the oxidant A, X is a development retarder, L is a bivalent connecting group, G is a polarizable group, and (n), (m) and (t) are respectively 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material excellent in sharpness and storage stability.

[0002]

2. Description of the Related Art In silver halide color photographic light-sensitive materials, the development of techniques for improving image quality is an important issue. In recent years, means for achieving high image quality in a small format have been developed one after another, but it is not sufficient yet, and further technical improvement is required. On the other hand, the use of DIR compounds for improving the sharpness, particularly the edge effect, is generally performed at present, but the ones usually used are imagewise development inhibition by a coupling reaction with an oxidation product of a color developing agent. D that releases the agent and forms a coloring pigment
It is an IR coupler. However, when a DIR coupler is used, if the dye formed by the coupling reaction is different from the dye obtained from the main coupler, color turbidity occurs, which is not preferable for color reproduction. In order to prevent this, it is necessary to develop a DIR coupler having a hue equivalent to that of the yellow, magenta, and cyan main couplers, but it is also necessary to develop three types with optimal reactivity. Therefore, since the burden of development and synthesis costs is increased, a colorless DIR compound has been demanded. Colorless DIR compounds are classified into two types, a coupling type and a redox type, depending on the reaction mode with the oxidant of the color developing agent. Of these, the coupling type is Japanese Patent Publication No. 51-161.
No. 41, No. 51-16142, U.S. Pat. No. 4,226,94.
Nos. 3,3,417,223 and the like, and US Pat.
17, JP-A-49-129536 and 64-546.
And DIR hydroquinone compounds described in Japanese Patent Application No. 2-21127, etc., or JP-A-61-213847,
There are DIR hydrazide compounds described in JP-A 64-88451 and US Pat. No. 4,684,604. When the processing step is applied to a color reversal light-sensitive material composed of B / W development (first development) and color development (second development), it is preferable to release the inhibitor from the DIR compound in the first development. This is because the second development is aimed at rapidly developing all the silver halide that has not been developed in the first development, and therefore the silver development speed is extremely high. For this reason, if it is attempted to exert an imagewise effect of suppressing development in the second development, silver development is delayed and processing instability in color development is introduced, which is not preferable. Therefore, D in the first development
It is preferred to react an IR compound, but in this case B
Redox type DIR that can react with oxidized form of developing agent for W / W
It is essential to use compounds. On the other hand, as an acyl group of an acylacetanilide type coupler, there is disclosed in JP-A-47-261.
No. 33 discloses a cyclopropane-1-carbonyl group, a cyclohexane-1-carbonyl group and the like. However, these couplers were inferior in some respects, such as poor coupling reactivity, low molecular extinction coefficient of dye, and poor spectral absorption characteristics of color image. Also, U.S. Pat. No. 5,118,599 discloses dioxane carbonyl groups, but they do not necessarily have sufficient performance in terms of coupling reactivity of couplers, dark fastness of dyes, and spectral absorption characteristics. Absent.
In addition, EP 447969 discloses 3- to 5-membered cycloalkylcarbonyl groups, which was also the case.

[0003]

When a redox DIR compound is used in combination with a conventionally known yellow coupler,
There are problems that the improvement of the edge effect is extremely small and that the performance is likely to change when the photosensitive material is stored under wet heat. Therefore, the first object of the present invention is to provide a color light-sensitive material excellent in sharpness. Secondly, to provide a color light-sensitive material having excellent storage stability over time.

[0004]

The objects of the present invention have been solved by the following means. That is, in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one layer constituting the light-sensitive material has an acylacetamide type yellow represented by the following general formula (1). A silver halide color photographic light-sensitive material containing at least one coupler and further containing at least one compound represented by the following formula (F) in at least one layer constituting the light-sensitive material. General formula (1)

[0005]

[Chemical 3]

In the formula, R ₁ represents a substituent, and Q represents a 6-membered heterocycle or 5 heteroatoms together with C.
Represents a non-metal atomic group necessary for forming a heterocyclic ring of a member. General formula (F)

[0007]

[Chemical 4]

In the formula, A represents a redox mother nucleus or a precursor thereof, and represents an atomic group that allows (Time) _t X to be released only by being oxidized during photographic development processing. . Time represents a group that releases X after leaving from the oxidant of A, and X represents a development inhibitor. L represents a divalent linking group, and G represents a polarizable group. n,
m and t represent 0 or 1, respectively.

The acylacetamide type yellow of the present invention will be described in detail below. The acylacetamide type yellow coupler of the present invention is preferably the following general formula (Y)
Represented by General formula (Y)

[0010]

[Chemical 5]

In the formula, R ₁ represents a substituent, and Q represents a 6-membered heterocyclic ring or 5 heteroatoms together with C.
Represents a non-metal atomic group necessary for forming a heterocyclic ring of a member. 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 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 (eg, methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbetyl, dodecyl, hexadecyl , Allyl, 3-cyclohexenyl,
Oleyl, benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl).

When the substituent in the formula (Y) is or contains 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, unless otherwise specified, the heterocyclic group is at least one selected from O, N, S, P, Se and Te. 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 the formula (Y), Q is preferably a 6-membered heterocyclic ring 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. Alternatively, it represents a non-metal atom group necessary for forming a 5-membered heterocycle containing two heteroatoms selected from N, S, O and P in the ring.

The ring formed with Q or C may contain an unsaturated bond in the ring, and may be substituted or unsubstituted. In the case of being substituted, examples of the substituent include the same as those described for R ₃ , but even if further substituted with an oxo group (= 0), the substituents are bonded to each other to form a ring. May be. 6 that Q makes with C
Among the membered heterocycles, even more preferred is the case where the 2-position of the carbonyl-substituted carbon (β-position when viewed from the carbonyl group) is at least one heteroatom, and therefore the acyl represented by the general formula (I) More preferred groups are
It is represented by the following general formula (III).

[0019]

[Chemical 6]

In the formula, Z is a heteroatom 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. It represents a group of non-metal atoms necessary for forming a 5-membered heterocycle. R
₁ and Q have the same contents as those in formula (Y), and preferred examples are also the same.

In the formula (Y), R ₂ is preferably a halogen atom, which may be substituted, and has a C number of 1 to 30.
Alkoxy group, aryloxy group having 6 to 30 C, C
It represents an alkyl group having 1 to 30 or an amino group having 0 to 30 carbon atoms, and examples of the substituent include 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 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 1 to 30 carbon atoms.
Alkoxy group, C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C1-30 carbonamido group, C1-30 sulfonamide group, C1-30 Carbamoyl group, C number 0-3
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, alkylsulfonyl 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, aryl Oxycarbonyl group, an alkylsulfonyloxy group, 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 cuvacamoyl 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) will be 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 (eg methyl, trifluoromethyl, ethyl, isopropyl, t-butyl),
C1-C30 alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, butoxy), or C-6-2
4 aryloxy groups (eg, phenoxy group, p-tolyloxy, p-methoxyphenoxy).

R ₃ is particularly preferably a halogen atom,
It is an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and most preferably a sulfamoyl group, an alkoxycarbonyl group, a carbonamido group or a sulfonamide group.

X is particularly preferably of the formula (Y-
1), (Y-2), or (Y-3).

[0029]

[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-
NR ₇ - is a heterocyclic group which is. The C number of the heterocyclic group represented by the formula (Y-1) is 2 to 30, preferably 4 to 20,
More preferably, it is 5-16.

[0033]

[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 3
It is 0, preferably 6 to 24, more preferably 6 to 15.

[0035]

[Chemical 9]

In the formula (Y-3), W represents a nonmetal 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, and more preferably 2 to 16.

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

The coupler represented by the formula (Y) has a substituent R ₁ , Q, X or a group represented by the formula (Yb) represented by Chemical Formula 8 and is bonded to each other through a divalent or higher valent group. Multimers or higher multimers may be formed. in this case,
It may be out of the range of the number of carbon atoms shown in each of the above substituents.

[0039]

[Chemical 10]

Specific examples of each substituent in the formula (Y) are shown below.

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

Specific examples of the yellow coupler represented by the formula (Y) are shown below, but the invention is not limited thereto.

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

[0056]

[Chemical 25]

[0057]

[Chemical formula 26]

[0058]

[Chemical 27]

[0059]

[Chemical 28]

[0060]

[Chemical 29]

[0061]

[Chemical 30]

[0062]

[Chemical 31]

[0063]

[Chemical 32]

[0064]

[Chemical 33]

[0065]

[Chemical 34]

[0066]

[Chemical 35]

[0067]

[Chemical 36]

[0068]

[Chemical 37]

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.

[0070]

[Chemical 38]

Acetylated ethyl pyruvate with 2,4-pentyldiol and then hydrolyzed, 17.2 g of compound A 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 reaction mixture was further heated 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.
22.8 g of compound D was obtained. Compound 2 (22.8 g) was dissolved in methylene chloride (300 ml), and sulfuryl chloride was added under ice cooling.
67 g was added dropwise. After reacting for 30 minutes, all the solvents were distilled off under reduced pressure, and N, N'-dimethylformamide 10 was added to the residue.
0 ml, 1-benzyl-5-ethoxyhydantoin 18.
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, the product is purified by column chromatography to obtain the objective compound Y
-29 was obtained as 19.2 g oil.

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.

[0073]

[Chemical Formula 39]

The yellow coupler of the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat.
2, 027 and the like. Further, the steps of the latex dispersion method as one of the polymer dispersion methods, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,
363, West German Patent Application (OLS) No. 2,541,27
No. 4 and No. 2,541,230, PCT application number J for the dispersion method using organic solvent-soluble polymer.
P87 / 00492. Examples of the organic solvent used in the oil-in-water dispersion method include phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.) phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate). Fate), citric acid ester (eg acetyl citrate tributyl), benzoic acid ester (eg octyl benzoate), alkylamide (eg diethyl laurylamide), fatty acid ester (eg dibutoxyethyl succinate, diethyl azelate), trimesine Acid ester (eg, tributyl trimesate) or the like, or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., such as ethyl acetate,
Lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate and the like may be used in combination. The high boiling point organic solvent can be used in a weight ratio of 0 to 10.0 times, preferably 0 to 6.0 times the amount of the coupler.

Next, the compound represented by formula (F) in the present invention will be described in detail below. The redox mother nucleus represented by A follows the Kendall-Pelz rule, and includes, for example, hydroquinone, catechol, p-aminophenol, o-aminophenol, 1,2-naphthalenediol, 1,4-naphthalenediol, 1, Mention may be made of 6-naphthalenediol, 1,2-aminonaphthol, 1,4-aminonaphthol, 1,6-aminonaphthol, gallic acid ester, gallic acid amide, hydrazine, hydroxylamine, pyrazolidone or reductone. The amino group contained in these redox mother nuclei is preferably substituted with a sulfonyl group having 1 to 25 carbon atoms or an acyl group having 1 to 25 carbon atoms. Examples of the sulfonyl group include a substituted or unsubstituted aliphatic sulfonyl group and an aromatic sulfonyl group. Examples of the acyl group include a substituted or unsubstituted aliphatic acyl group and aromatic acyl group. The hydroxyl group or amino group forming the redox mother nucleus of A may be protected by a protecting group that can be deprotected during development processing. Examples of the protecting group include 1 to 25 carbon atoms.
Such as an acyl group, an alkoxycarbonyl group,
A carbamoyl group, further JP-A-59-197037,
The protecting groups described in JP-A-59-201057 can be mentioned. Further, this protecting group is, if possible, bonded to each other by the substituents of A described below, 5, 6 or 7
You may form a member ring.

In the redox mother nucleus represented by A, the substitutable position may be substituted with a substituent. Examples of these substituents are those having 25 or less carbon atoms, such as an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an amino group, an amide group,
Sulfonamide group, alkoxycarbonylamino group, ureido group, carbamoyl group, alkoxycarbonyl group,
Examples thereof include a sulfamoyl group, a sulfonyl group, a cyano group, a halogen atom, an acyl group, a carboxyl group, a sulfo group, a nitro group, a heterocyclic residue or-(L) _n- (G) _m- (Time) _t X. These substituents may be further substituted with the above-mentioned substituents. If possible, these substituents may be bonded to each other to form a saturated or unsaturated carbocycle or a saturated or unsaturated heterocycle. Preferred examples of A include hydroquinone, catechol, p-aminophenol, o-aminophenol, 1,4-naphthalenediol, 1,4-aminonaphthol, gallic acid ester, gallic acid amide, and hydrazine. A is more preferably hydroquinone, catechol, p-aminophenol, o-aminophenol or hydrazine, and most preferably hydroquinone or hydrazine.

L represents a divalent linking group, and preferably includes alkylene, alkenylene, arylene, oxyalkylene, oxyarylene, aminoalkyleneoxy, aminoalkenyleneoxy, aminoaryleneoxy and oxygen atom. G represents an acidic group, preferably (Chemical Formula 35).

[0078]

[Chemical 40]

Here, R ₁₅ is alkyl, aryl or heterocycle, and R ₁₆ has the same meaning as hydrogen atom or R ₁₅ . G
Is more preferably (Chemical formula 19), and most preferably (Chemical formula 20).

[0080]

[Chemical 41]

[0081]

[Chemical 42]

N and m are 0 or 1, and which is preferable depends on the type of A. For example, when A is hydroquinone, catechol, aminophenol, naphthalenediol, aminonaphthol or gallic acid, n = 0 is preferable, and n = m = 0 is more preferable. When A is hydrazine or hydroxylamine, n = 0, m = 1
Is preferable, and when A is pyrazolidone, n = m = 1 is preferable.

[0083] - (Time) _t -X redox mother nucleus in the formula (F) represented by A is the first time became oxidant undergoes development at cross oxidation ^- - (Time) released as _t -X Is a group that is It is preferable that Time is connected to G by a sulfur atom, a nitrogen atom, an oxygen atom or a selenium atom. Time
Represents a group capable of further releasing X, may have a timing adjusting function, and may be a coupler or redox group which further releases X upon reacting with an oxidized product of a developing agent. When Time is a group having a timing adjusting function, for example, US Pat. Nos. 4,248,962 and 4,409,323, and British Patent 2,096,783 are used.
No. 4,146,396, JP-A-51-1.
And those described in JP-A-57-56837 and the like. Time may be a combination of two or more selected from those described in these. Preferred examples of the timing control group include the following.

(1) Group Utilizing Cleavage Reaction of Hemiacetal For example, US Pat. No. 4,146,396, JP-A-60.
No. 249148 and No. 60-249149, it is a group represented by (Chemical Formula 38). Here, the * mark represents the position bonded to the left side in the general formula (F), and **
The mark represents the position bonded to the right side in the general formula (F).

[0085]

[Chemical 43]

In the formula, W is an oxygen atom, a sulfur atom or -N
(R ₆₇ )-group, R ₆₅ and R ₆₆ represent a hydrogen atom or a substituent, R ₆₇ represents a substituent, and t is 1 or 2
Represents When t is 2, two -WC (R ₆₅ ) (R ₆₆ )-represent the same or different. When R ₆₅ and R ₆₆ represent a substituent and typical examples of R ₆₇ are R
₆₉ groups, R ₆₉ CO- groups, R ₆₉ SO ₂ -groups, N (R ₆₉ ) (R ₇₀ ) C
Examples thereof include O-group and N (R ₆₉ ) (R ₇₀ ) SO ₂ -group. Here, R ₆₉ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Each of R ₆₅ , R ₆₆ and R ₆₇ represents a divalent group and is also included when they are linked to each other to form a cyclic structure. (2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,962 can be mentioned. It can be represented by

[0087]

[Chemical 44]

In the formula, * indicates a position bonded to the left side in the general formula (F), ** mark represents a position bonded to the right side in the general formula (F), Nu represents a nucleophilic group, and oxygen An atom or a sulfur atom is an example of a nucleophilic group, E represents an electrophilic group, and is a group capable of cleaving the bond with the ** mark by nucleophilic attack from Nu, and Link is Nu and E in the molecule. Represents a linking group that is sterically related so that it can undergo a nucleophilic substitution reaction. (3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, for example, US Pat. Nos. 4,409,323 or 4,4,4.
No. 21,845, and is a group represented by (Chemical Formula 40).

[0089]

[Chemical formula 45]

In the formula, * mark, ** mark, W, R ₆₅ , R ₆₆ and t have the same meanings as described for (Chemical Formula 21). (4) Group Utilizing Cleavage Reaction of Ester by Hydrolysis For example, there is (Chemical Formula 41) which is a linking group described in West German Published Patent No. 2,626,315. In the formula, * mark and ** mark have the same meaning as described for (Chemical Formula 38).

[0091]

[Chemical formula 46]

(5) Group Utilizing Iminoketal Cleavage Reaction For example, a linking group described in US Pat. No. 4,546,073, which is a group represented by the chemical formula (42).

[0093]

[Chemical 47]

In the formula, *, ** and W have the same meanings as described in (formula 38), and R ₆₈ has the same meaning as R ₆₇ . Examples of the group represented by D being a coupler or a redox group include the following. As the coupler, for example, in the case of a phenol type coupler, the one bonded to G in the general formula (F) at the oxygen atom excluding the hydrogen atom of the hydroxyl group. Also, 5
In the case of a pyrazolone type coupler, G is bonded at an oxygen atom obtained by removing a hydrogen atom from a hydroxy group of a tautomerism of 5-hydroxypyrazole. Each of these functions as a coupler only after leaving from G, reacts with the oxidized form of the developing agent, and releases X bonded to their coupling positions. (Chemical Formula 43) is mentioned as a preferable example when Time is a coupler.

[0095]

[Chemical 48]

In the formula, V ₁ and V ₂ represent a substituent,
V ₃ , V ₄ , V ₅ and V ₆ represent a nitrogen atom or a substituted or unsubstituted methine group, V ₇ represents a substituent, x represents an integer of 0 to 4, and when x is plural, V
_7's represent the same or different, and two V _7's may be linked to each other to form a ring structure. V ₈ is a -CO- group,
A —SO ₂ — group, an oxygen atom or a substituted imino group,
₉ represents a non-metal atom group for forming a 5-membered to 8-membered ring, and V ₁₀ represents a hydrogen atom or a substituent. When the group represented by Time in the general formula (F) is a redox group, it is preferably represented by (formula 44).

[0097]

[Chemical 49]

In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, at least one of k Y and Z represents a methine group having X as a substituent, and Y and Z represent a substituted or unsubstituted methine group or a nitrogen atom, and k is 1 to 3
Represents the integer (k Y and Z represent the same or different), and B represents a hydrogen atom or a group removable by an alkali. Here, the case where any two substituents of P, Y, Z, Q and B are combined into a divalent group to form a cyclic structure is also included. For example (Y = Z) _k
When forming a benzene ring, a pyridine ring, or the like.
When P and Q represent a substituted or unsubstituted imino group, it is preferably an imino group substituted with a sulfonyl group or an acyl group. At this time, P and Q are represented as in (Formula 45).

[0099]

[Chemical 50]

Here, the * mark represents the position at which the compound of formula (F) is bonded to G or the position at which it is bonded to B of formula (44), and **
The mark represents the position at which one of the (Y = Z) _k − free bonds is bonded. In the formula, the group represented by G ¹ represents an aliphatic group, an aromatic group, or a heterocyclic group. Among the groups represented by (Chemical formula 44), a particularly preferable group is (Chemical formula 46) or (Chemical formula 4)
7).

[0101]

[Chemical 51]

[0102]

[Chemical 52]

In the formula, * indicates the position of bonding with G in the general formula (F), and ** indicates the position of bonding with X. R ₆₄
Represents a substituent, and q represents an integer of 0, 1 or 3. When q is 2 or more, two or more R _64's may be the same or different, and when two R _64's are substituents on adjacent carbons, they are each a divalent group and are linked to each other to represent a cyclic structure. It also includes cases. X means a development inhibitor. Preferred examples of X include a compound having a mercapto group bonded to the heterocycle represented by (Chemical Formula 48), or a heterocyclic compound capable of forming an iminosilver represented by (Chemical Formula 49).

[0104]

[Chemical 53]

[0105]

[Chemical 54]

In the formula, Z ₁ represents a nonmetallic atom group necessary for forming a monocyclic ring or a condensed heterocycle, and Z ₂ represents N.
Represents a nonmetallic atom group necessary for forming a monocyclic ring or a condensed ring heterocycle. These heterocycles may have a substituent, and * represents a position bonded to Time. Z
_The heterocyclic ring formed by ₁ and Z ₂ is more preferably a 5-membered to 8-membered heterocyclic ring containing at least one of nitrogen, oxygen, sulfur and selenium as a hetero atom, and most preferably 5 or 6 members. It is a heterocycle of members. Examples of the heterocycle represented by Z ₁ include, for example, azoles (tetrazole, 1,2,4-triazole,
1,2,3-triazole, 1,3,4-thiadiazole, 1,3,4-oxadiazole, 1,3-thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazole, pyrrole , Pyrazole, indazole), azaindenes (terorazaindene, pentazaindene, triazaindene), azines (pyrimidine, triazine, pyrazine, pyridazine) and the like. Examples of the heterocycle represented by Z ₂ include, for example, triazoles (1,2,
4-triazole, benzotriazole, 1,2,3-
Triazole), indazole, benzimidazole,
Azaindenes (tetrazaindene, pentazaindene), tetrazole and the like can be mentioned. Examples of preferable substituents contained in the development inhibitor represented by (Chemical Formula 48) and (Chemical Formula 49) include (Chemical Formula 50).

[0107]

[Chemical 55]

Here, R ₇₇ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₈ , R ₇₉ and R ₈₀ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. When two or more R ₇₇ , R ₇₈ , R ₇₉ and R ₈₀ are present in one molecule, they may be linked to form a ring (for example, a benzene ring).
Examples of the compound represented by the formula include, for example, substituted or unsubstituted mercaptoazoles (eg 1-phenyl-5-mercaptotetrazole, 1-propyl-
5-mercaptotetrazole, 1-butyl-5-mercaptotetrazole, 2-methylthio-5-mercapto-
1,3,4-thiadiazole, 3-methyl-4-phenyl-5-mercapto-1,2,4-triazole, 1-
(4-Ethylcarbamoylphenyl) -2-mercaptoimidazole, 2-mercaptobenzoxazole, 2
-Mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2
-Phenyl-5-mercapto-1,3,4-oxadiazole, 1- {3- (3-methylureido) phenyl}
-5-mercaptotetrazole, 1- (4-nitrophenyl) -5-mercaptotetrazole, 5- (2-ethylhexanoylamino) -2-mercaptobenzimidazole, etc., substituted or unsubstituted mercaptoazaindenes (for example, , 6-methyl-4-mercapto-1,
3,3a, 7-tetraazaindene, 4,6-dimethyl-2-mercapto-1,3,3a, 7-tetraazaindene and the like), and substituted or unsubstituted mercaptopyrimidines (for example, 2-mercaptopyrimidine, 2 -Mercapto-4-methyl-6-hydroxypyrimidine) and the like. Examples of the heterocyclic compound capable of forming imino silver include substituted or unsubstituted triazoles (eg, 1,2,4-triazole, benzotriazole,
5-methylbenzotriazole, 5-nitrobenzotriazole, 5-bromobenzotriazole, 5-n-butylbenzotriazole, 5,6-dimethylbenzotriazole, etc., and substituted or unsubstituted indazoles (eg, indazole, 5-nitro) Indazole, 3-
Nitroindazole, 3-chloro-5-nitroindazole, etc.), and substituted or unsubstituted benzimidazoles (eg, 5-nitrobenzimidazole, 5,6-dichlorobenzimidazole) and the like.

Further, X deviates from Time in the general formula (F) to become a compound having a development inhibitory property, and then it causes a certain chemical reaction with the developer component to substantially inhibit the development. It may be a compound that has no property or is significantly reduced. Examples of the functional group that undergoes such a chemical reaction include an ester group, a carbonyl group, an imino group, an immonium group, a Michael addition accepting group, and an imide group. Examples of such a deactivating development inhibitor include, for example, US Pat.
477,563, JP-A-60-218644, 6
No. 0-221750, No. 60-233650, No. 61-11743, and other development inhibitor residues. Among these, those having an ester group are particularly preferable. Specifically, for example, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5.
-Mercaptotetrazole, 1- (3-maleimidophenyl) -5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,
3,4-thiadiazole, 5-nitro-3-phenoxycarbonylimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 1- (4
-Benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole , 5-
Succinimidomethylbenzotriazole, 2- {4-
Succinimidophenyl} -5-mercapto-1,3,3
4-oxadiazole, 6-phenoxycarbonyl-2
-Mercaptobenzoxazole, 2- (1-methoxycarbonylethylthio) -5-mercapto-1,3,4
-Thiadiazole, 2-butoxycarbonylmethoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 2- (N-hexylcarbamoylmethoxycarbonylmethylthio) -5-mercapto-1,3
4-thiadiazole, 5-butoxycarbonylmethoxycarbonylbenzotriazole and the like can be mentioned. Among the compounds represented by the general formula (F), the compounds represented by the following general formulas (G) and (H) are more preferable. General formula (G)

[0110]

[Chemical 56]

In the formula, R ²¹ to R ²³ are a hydrogen atom or a group capable of substituting for a hydroquinone nucleus, and P ²¹ and P ²² are a hydrogen atom or a protective group capable of being deprotected during development processing. Ti
me, X and t have the same meaning as in formula (F). General formula (H)

[0112]

[Chemical 57]

In the formula, R ³¹ represents an aryl group, a heterocyclic group, an alkyl group, an aralkyl group, an alkenyl group or an alkynyl group, and P ³¹ and P ³² are a hydrogen atom or a protective group capable of being deprotected during development processing. . G, Time, X, and t have the same meaning as in formula (F). In more detail about the general formula (G), as the substituents R ²¹ to represented by R ^23, for example, those described as a substituent A in the general formula (F) are mentioned as R ²² and R ²³ Preferably a hydrogen atom, an alkylthio group, an arylthio group, an alkoxy group,
An aryloxy group, an amide group, a sulfonamide group, an alkoxycarbonylamino group, and a ureido group are more preferable, and a hydrogen atom, an alkylthio group, an alkoxy group, an amide group, a sulfonamide group, an alkoxycarbonylamino group, and a ureido group are more preferable. R ²¹ is preferably a hydrogen atom, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group, a sulfonyl group, a cyano group, an acyl group or a heterocyclic group, more preferably a hydrogen atom, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group, a cyano group. It is a base. R ²² and R ²³ may combine together to form a ring. Examples of the protective group for P ²¹ and P ²² include those mentioned as the protective group for the hydroxyl group of A in the general formula (F), preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Hydrolyzable groups such as imidoyl group, oxazolyl group, and sulfonyl group; precursor groups utilizing the reverse Michael reaction described in US Pat. No. 4,009,029; described in US Pat. No. 4,310,612. Precursor group of the type which utilizes an anion generated after the ring-cleavage reaction of the compound as an intramolecular nucleophilic group, U.S. Pat. Nos. 3,674,478 and 3,93.
Precursor group in which the anion described in 2,480 or 3,993,661 causes electron transfer through a conjugated system to cause a cleavage reaction, US Pat. No. 4,33.
Precursor groups described in US Pat. No. 5,200,200, which cause a cleavage reaction by electron transfer of anions reacted after ring cleavage, or US Pat. Nos. 4,363,865 and 4,410,61.
Precursor groups utilizing the imidomethyl group described in No. 8 are mentioned. P ²¹ and P ²² are preferably hydrogen atoms. Preferred as X are mercaptoazoles and benzotriazoles. As mercaptoazoles, mercaptotetrazoles and 5-mercapto-
1,3,4-thiadiazoles and 5-mercapto-
1,3,4-oxadiazoles are more preferred. Most preferably, X is 5-mercapto-1,3,4-thiadiazole. Of the general formula (G), it is represented by the following general formulas (I) and (J). General formula (I)

[0114]

[Chemical 58]

General formula (J)

[0116]

[Chemical 59]

Here, R ⁴² represents an aliphatic group, an aromatic group or a heterocyclic group, and M represents (formula 38).

[0118]

[Chemical 60]

R ⁴⁴ , R ⁴⁵ and R ⁵⁴ represent a hydrogen atom, an alkyl group or an aryl group. L is a divalent linking group necessary for forming a 5-membered to 7-membered ring. R ⁴¹ and R ⁵¹
Is R ²¹ of the general formula (G) and R ⁴³ is R ²³ of the general formula (G),-
(Time) _t -X general formula (G) - (Time) is synonymous with _t -X. Furthermore, when R ⁴² is described in detail, the aliphatic group of R ⁴² is a linear, branched, or cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 30 carbon atoms. The aromatic group has 6 to 30 carbon atoms and includes a phenyl group and a naphthyl group. As the heterocycle, nitrogen, oxygen,
It is a 3- to 12-membered one containing at least one of sulfur. These may be further substituted with the groups described for the substituent of A.

The general formula (H) will be described in more detail. The arule group represented by R ³¹ has 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is a 5- to 7-membered group containing at least one of nitrogen, oxygen and sulfur, and examples thereof include furyl and pyridyl. 1 carbon as an alkyl group
To 30 and examples thereof include methyl, hexyl, octadecyl and the like. The aralkyl group has a carbon number of 7 to 30, and examples thereof include benzyl and trityl. The alkenyl group has 2 to 30 carbon atoms, and examples thereof include allyl. The alkynyl group has 2 to 30 carbon atoms, and examples thereof include propargyl. R ³¹ is preferably an aryl group, more preferably phenyl. P ³¹ and P
Examples of the protecting group for ³² include those mentioned as the protecting group for the amino group of A in the general formula (F). R ³¹ and P ³²
Is preferably a hydrogen atom. G is preferably -CO-, and X is preferably the one described in the general formula (G). R ²¹ to R ^{23 in} the general formula (G) and R ^{31 in the} general formula (H) may be substituted with a substituent. The substituent may have a so-called ballast group or a silver halide adsorbing group for imparting diffusion resistance, but it is more preferably a ballast group. When R ³¹ is a phenyl group, the substituent is preferably an electron donating group, and examples thereof include a sulfonamide group, an amide group, an alkoxy group and a ureido group. When R ²¹ , R ²² , R ²³ or R ³¹ has a ballast group, it is particularly preferable that R ²¹ , R ²² , R ²³ or R ³¹ has a polar group such as a hydroxyl group, a carboxyl group or a sulfo group in the molecule. In order to more specifically arrange the content of the present invention, specific examples of the compound represented by the general formula (F) are shown below, but the compounds usable in the present invention are not limited thereto.

[0121]

[Chemical formula 61]

[0122]

[Chemical formula 62]

[0123]

[Chemical formula 63]

[0124]

[Chemical 64]

[0125]

[Chemical 65]

[0126]

[Chemical formula 66]

[0127]

[Chemical formula 67]

[0128]

[Chemical 68]

[0129]

[Chemical 69]

[0130]

[Chemical 70]

[0131]

[Chemical 71]

[0132]

[Chemical 72]

[0133]

[Chemical formula 73]

[0134]

[Chemical 74]

[0135]

[Chemical 75]

[0136]

[Chemical 76]

[0137]

[Chemical 77]

[0138]

[Chemical 78]

[0139]

[Chemical 79]

[0140]

[Chemical 80]

[0141]

[Chemical 81]

[0142]

[Chemical formula 82]

[0143]

[Chemical 83]

[0144]

[Chemical 84]

[0145]

[Chemical 85]

[0146]

[Chemical 86]

[0147]

[Chemical 87]

[0148]

[Chemical 88]

[0149]

[Chemical 89]

[0150]

[Chemical 90]

[0151]

[Chemical Formula 91]

[0152]

[Chemical Formula 92]

The compounds represented by formula (F) of the present invention are disclosed in JP-A-49-129536 and JP-A-52-57828.
No. 60, No. 60-21044, No. 60-233642,
No. 60-233648, No. 61-18946, No. 6
1-156043, 61-213847, 61
-230135, 61-2336549, 62-
62352, 62-103639, U.S. Pat. Nos. 3,379,529, 3,620,746, 4,332,828, 4,377,634, 4,684,604. It can be synthesized according to the method described in etc. The compound represented by the general formula (F) is used in any emulsion layer,
And / or in the non-photosensitive layer. It may be added to both. The addition amount is preferably 0.001 to 0.2 mmol / m ² , and more preferably 0.01.
Is in the range of 0.1 mmol / m ² .

The yellow coupler represented by the general formula (1) of the present invention is 1.0 to 1.0 per mol of silver halide.
It can be used in a range of × 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 coupler represented by the general formula (1) of the present invention can be introduced into a 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 the fine dispersion, and the low-boiling organic solvent is substantially contained in the dry film. A method that does not remain may be used. 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 dispersion liquid of the cyan, magenta and yellow couplers in the present invention has a boiling point of 1 at a ratio represented by the following formula.
A high boiling point organic solvent having a temperature of 50 ° C. or higher can be included. 0 ≦ high boiling organic solvent (weight) / coupler (weight) ≦ 1.
0 This ratio is preferably 0.7 or less, more preferably 0.5 or less, in order to improve the sharpness and the film strength. Further, the high-boiling point organic solvent in the above formula is one which is co-emulsified.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive 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 is 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.

Monodispersed 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 is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area 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 emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

In the present invention, it is preferable to use 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 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. As the yellow couplers, in addition to those represented by the general formulas (1) and (2) of the present invention, for example, US Pat.
4,022,620, 4,326,024, 4,401,752,
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,
425,020, 1,476,760, U.S. Patent 3,973,968
No. 4,314,023, No. 4,511,649, European Patent No.
Those described in No. 249,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and International Publication WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 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.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group.
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, VII-F above.
And Patent Nos. 307105 and VII-F, JP-A-57-151944, 57-154234, 60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 are preferable. RD No.1
The bleaching accelerator releasing couplers described in 1449, 24241 and JP-A-61-201247 are effective for shortening the processing time having a bleaching ability, and in particular, the above-mentioned tabular silver halide grains. The effect is great when it is added to the photosensitive material using. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-157638, and 59-170.
Those described in No. 840 are preferable. In addition, JP-A-60-10702
No. 9, No. 60-252340, JP-A No. 1-49440, No. 1-45687
By the redox reaction with the oxidant of the developing agent described in No.
Compounds that release a fogging agent, a development accelerator, a silver halide solvent and the like are also 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 light-sensitive 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, the black and white development is usually carried out before the color development. 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 square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also 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 / l.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. 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 washing and / or stabilizing steps 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 as follows.
nd Tele-vision Engineers Volume 64, P. 248 ~ 253 (195
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, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society edited, "Antibacterial and Antifungal Encyclopedia" (1986) 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 resulting from the above washing with water and / or replenishment 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.

[0176]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 Preparation of Sample 101 A multilayer color light-sensitive material consisting of layers having the following compositions was prepared on a 127 μm-thick cellulose triacetate film support having an undercoat, to prepare Sample 101. 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 High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Finely grained silver iodobromide emulsion with a fogged surface and inside (average grain 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-3 0.05 g Coupler C-9 0.05 g High boiling point organic solvent Oil-2 0.1 g Fifth layer: Medium-sensitive 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 point 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 Eighth layer: intermediate layer Silver iodobromide milk with fogged surface and inside (Average particle 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 0.05 g Coupler C-8 0.20 g Compound Cpd-B 0.03 g 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 10th layer: Medium sensitivity 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 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.05 g 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 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling point organic solvent Oil-1 0.02 g High-boiling organic solvent Oil-2 0.02 g 12th layer: Intermediate layer Gelatin 0.6 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.07 g 13th layer: Yellow Filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Anti-color mixing agent Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 14th layer : Intermediate layer gelatin 0.6 g Fifteenth 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 0.2 g Coupler C-6 0.2 g Coupler C-10 0.4 g 16th layer: Middle speed 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 0.1 g Coupler C-10 0.1 g 17th 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 coupler C-10 0.1 g Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.04 g UV absorber U-2 0.01 g UV absorber U-3 0.03 g UV absorber U-4 0.03 g Ultraviolet absorber U-5 0.05 g Ultraviolet absorber U-6 0.05 g High boiling point 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 mg Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Copolymer of methylmethacrylate and acrylic acid 4: 6 (Average particle size 1.5 μ) 0 1 g of silicone oil 0.03g Surfactant W-1 3.0 mg Surfactant W-2 0.03g In addition to the additives of all of the composition to the emulsion layer F-
1-F-8 were added. In addition to the above composition, a gelatin hardening agent H-1 and coating and emulsifying surfactants W-3, W-4, W-5, W-6 and W-7 were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol and phenethyl alcohol were added as antiseptic and antifungal agents.

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

[0178]

[Chemical formula 93]

[0179]

[Chemical 94]

[0180]

[Chemical 95]

[0181]

[Chemical 96]

[0182]

[Chemical 97]

[0183]

[Chemical 98]

[0184]

[Chemical 99]

[0185]

[Chemical 100]

[0186]

[Chemical 101]

[0187]

[Chemical 102]

[0188]

[Chemical 103]

[0189]

[Chemical 104]

[0190]

[Chemical 105]

[0191]

[Chemical formula 106]

[0192]

[Chemical formula 107]

[0193]

[Chemical 108]

[0194]

[Chemical 109]

[0195]

[Chemical 110]

Table 8 shows the silver iodobromide emulsion used in Sample 101.

[0197]

[Table 1]

[0198]

[Table 2]

(Production of Samples 102 to 104) Sample 101
In place of the couplers added to the 15th, 16th and 17th layers, the comparative compounds shown in Table 3 and the compounds of the present invention were replaced by equimolar amounts so that the total amount would be equimolar to Sample 101. Samples 102 to 104 are similar except that
Was produced.

[0200]

[Table 3]

(Preparation of Samples 105 to 117) Sample 101
Instead of the couplers added to the fifteenth layer, the sixteenth layer and the seventeenth layer, the comparative compounds shown in Table 3 and the compound of the present invention were added in equimolar amounts so that the total amount would be equimolar to Sample 101. Samples 105 to 117 were prepared in the same manner, except that the DIR compound of the present invention was added to the intermediate layer of the second layer in an amount of 10 mg per m ² as shown in Table 3.
After cutting the obtained samples 101 to 117 into strips, the edge effect was measured. The edge effect is measured by a soft X-ray through a slit having a line width of 1 mm and 20 μm onto the sample, and the sample developed through the following processing steps is measured with a micro densitometer through a blue filter. The ratio of 20 μm / 1 mm is taken to obtain the edge effect. Value.

Treatment process Treatment process time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38 ° C. 12 l 2.2 l / m ² First water washing ² 〃 38 〃 4 〃 7.5 〃 Reverse rotation ² 〃 38 〃 4 〃 1.1 〃 Color development 6 〃 38 〃 12 〃 2.2 〃 Adjustment 2 〃 38 〃 4 〃 1.1 〃 Bleach 6 〃 38 〃 12 〃 0.22 〃 Fixed 〃 38 〃 8 〃 Flush with water 4〃 38〃 8〃 7.5〃 stability 1〃 25〃 2〃 1.1〃 The composition of each treatment solution 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

[0203]

[Chemical 111]

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 3. As is clear from Table 3, the edge effect is greatly affected only by the combination of the coupler of the present invention and the DIR compound of the present invention. Further, the obtained samples 101 to 117 were processed at 45 ° C.-8.
After storage in an atmosphere of 0% RH for 5 days, the above treatment was performed simultaneously with the room temperature storage sample. As a result, the sample of the present invention showed less decrease in sensitivity and less decrease in maximum density than the comparative sample. (Example 2) In Example 2 and Sample 201 described in JP-A-2-90151, the tenth layer coupler Cp-
N is the coupler Y-4 of the present invention, and the coupler C is the 11th layer.
substituting equimolar for p-N with coupler Y-8 of the invention,
Further, Sample A was prepared in the same manner as in Sample 201, except that 10 mg of Compound I-57 of the present invention was added to the intermediate layer of the second layer per m ² . When the same test as in Example 1 was performed on Sample A, the same results as in Example 1 were obtained, which was preferable.

(Example 3) Sample 107 described in Example 1
In, the compound I-2 was replaced with I-10, I-12, I-2.
8, I-36, I-48, I-51, I-58, I-7
Samples B, C, D, E, F, G, H, I, and J were prepared in the same manner as Sample 107, except that they were replaced with 0 and I-87. The same tests as in Example 1 were performed on Samples B to J, and the same results as in Example 1 were obtained, which was preferable.

[0207]

According to the present invention, a silver halide color photographic light-sensitive material excellent in sharpness and storage stability over time can be obtained.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 30, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

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[0002]

2. Description of the Related Art In silver halide color photographic light-sensitive materials, the development of techniques for improving image quality is an important issue. In recent years, means for achieving high image quality in a small format have been developed one after another, but it is not sufficient yet, and further technical improvement is required. On the other hand, the use of DIR compounds for improving the sharpness, particularly the edge effect, is generally performed at present, but the ones usually used are imagewise development inhibition by a coupling reaction with an oxidation product of a color developing agent. D that releases the agent and forms a coloring pigment
It is an IR coupler. However, when a DIR coupler is used, if the dye formed by the coupling reaction is different from the dye obtained from the main coupler, color turbidity occurs, which is not preferable for color reproduction. In order to prevent this, it is necessary to develop a DIR coupler having a hue equivalent to that of the yellow, magenta, and cyan main couplers, but it is also necessary to develop three types with optimal reactivity. Therefore, since the burden of development and synthesis costs is increased, a colorless DIR compound has been demanded. Colorless DIR compounds are classified into two types, a coupling type and a redox type, depending on the reaction mode with the oxidant of the color developing agent. Of these, the coupling type is Japanese Patent Publication No. 51-161.
No. 41, No. 51-16142, U.S. Pat. No. 4,226,94.
Nos. 3,3,417,223 and the like, and US Pat.
17, JP-A-49-129536 and 64-546.
And DIR hydroquinone compounds described in Japanese Patent Application No. 2-21127, etc., or JP-A-61-213847,
There are DIR hydrazide compounds described in JP-A 64-88451 and US Pat. No. 4,684,604. When the processing step is applied to a color reversal light-sensitive material composed of B / W development (first development) and color development (second development), it is preferable to release the inhibitor from the DIR compound in the first development. This is because the second development is aimed at rapidly developing all the silver halide that has not been developed in the first development, and therefore the silver development speed is extremely high. For this reason, if it is attempted to exert an imagewise effect of suppressing development in the second development, silver development is delayed and processing instability in color development is introduced, which is not preferable. Therefore, D in the first development
It is preferred to react an IR compound, but in this case B
Redox type DIR that can react with oxidized form of developing agent for W / W
It is essential to use compounds. On the other hand, as an acyl group of an acylacetanilide type coupler, there is disclosed in JP-A-47-261.
No. 33 discloses a cyclopropane-1-carbonyl group, a cyclohexane-1-carbonyl group and the like. However, these couplers are inferior in coupling reactivity, the molecular absorption coefficient of the dye is small, or the spectral absorption characteristics of the color image are inferior, and they are also inferior in the dark fastness of the dye. It does not necessarily have sufficient performance. Furthermore, in EP 447969 a 3-5 membered cycloalkylcarbonyl group is also disclosed in US Pat.
No. 8599 discloses a dioxane carbonyl group, which states that it has excellent performance in color development.

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When the substituent in the formula (Y) is a heterocyclic group or contains a heterocyclic group, unless otherwise specified, the heterocyclic group is at least one selected from O, N, S, P, Se and Te. 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-benzotriazolyl, succinimide, phthalimido, 1-benzyl-2,4-imidazolidindione-3-yl).

[Procedure 3]

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[0019]

[Chemical 6]

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

[0057]

[Chemical formula 26]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0106

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In the formula, Z ₁ represents a nonmetallic atom group necessary for forming a monocyclic ring or a condensed heterocycle, and Z ₂ represents N.
Represents a nonmetallic atom group necessary for forming a monocyclic ring or a condensed ring heterocycle. These heterocycles may have a substituent, and * represents a position bonded to Time. Z
_The heterocyclic ring formed by ₁ and Z ₂ is more preferably a 5-membered to 8-membered heterocyclic ring containing at least one of nitrogen, oxygen, sulfur and selenium as a hetero atom, and most preferably 5 or 6 members. It is a heterocycle of members. Examples of the heterocycle represented by Z ₁ include, for example, azoles (tetrazole, 1,2,4-triazole,
1,2,3-triazole, 1,3,4-thiadiazole, 1,3,4-oxadiazole, 1,3-thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazole, pyrrole , Pyrazole, indazole), azaindenes (tetrazaindene, pentazaindene, triazaindene), azines (pyrimidine, triazine, pyrazine, pyridazine) and the like. Examples of the heterocycle represented by Z ₂ include, for example, triazoles (1,2,
4-triazole, benzotriazole, 1,2,3-
Triazole), indazole, benzimidazole,
Azaindenes (tetrazaindene, pentazaindene), tetrazole and the like can be mentioned. Examples of preferable substituents contained in the development inhibitor represented by (Chemical Formula 48) and (Chemical Formula 49) include (Chemical Formula 50).

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Further, X deviates from Time in the general formula (F) to become a compound having a development inhibitory property, and then it causes a certain chemical reaction with the developer component to substantially inhibit the development. It may be a compound that has no property or is significantly reduced. Examples of the functional group that undergoes such a chemical reaction include an ester group, a carbonyl group, an imino group, an ammonium group, a Michael addition accepting group, and an imide group. Examples of such a deactivating development inhibitor include, for example, US Pat.
477,563, JP-A-60-218644, 6
No. 0-221750, No. 60-233650, No. 61-11743, and other development inhibitor residues. Among these, those having an ester group are particularly preferable. Specifically, for example, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5.
-Mercaptotetrazole, 1- (3-maleimidophenyl) -5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,
3,4-thiadiazole, 5-nitro-3-phenoxycarbonylimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 1- (4
-Benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole , 5-
Succinimidomethylbenzotriazole, 2- {4-
Succinimidophenyl} -5-mercapto-1,3,3
4-oxadiazole, 6-phenoxycarbonyl-2
-Mercaptobenzoxazole, 2- (1-methoxycarbonylethylthio) -5-mercapto-1,3,4
-Thiadiazole, 2-butoxycarbonylmethoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 2- (N-hexylcarbamoylmethoxycarbonylmethylthio) -5-mercapto-1,3
4-thiadiazole, 5-butoxycarbonylmethoxycarbonylbenzotriazole and the like can be mentioned. Among the compounds represented by the general formula (F), the compounds represented by the following general formulas (G) and (H) are more preferable. General formula (G)

[Procedure Amendment 7]

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[0129]

[Chemical 69]

[Procedure Amendment 8]

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The compounds represented by formula (F) of the present invention are disclosed in JP-A-49-129536 and JP-A-52-57828.
No. 60, No. 60-21044, No. 60-233642,
No. 60-233648, No. 61-18946, No. 6
1-156043, 61-213847, 61
-230135, 61-2336549, 62-
62352, 62-103639, U.S. Pat. Nos. 3,379,529, 3,620,746, 4,332,828, 4,377,634, 4,684,604. It can be synthesized according to the method described in etc. The compound represented by the general formula (F) is used in any emulsion layer,
And / or in the non-photosensitive layer. It may be added to both. The addition amount is preferably 0.001 to 0.2 mmol / m ² , and more preferably 0.01.
Is in the range of 0.1 mmol / m ² . General formula (F) of the present invention
The compounds represented by can be used in combination of two or more kinds.

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The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive 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 and the like as described in the specification, and contains a color mixing inhibitor as commonly used. Good. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 92.
As described in No. 3,045, a two-layer constitution of a high sensitivity emulsion layer and a low sensitivity emulsion layer can be preferably used. Normally,
It is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57-112751,
No. 62-200350, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer is provided on the side farther from the support and a high-sensitivity emulsion layer is provided on the side closer to the support. Good.
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), or BH / BL /
It can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. . 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 in the case of being composed of three layers having different sensitivities as described above, Japanese Patent Laid-Open No. 59-202464
As described in the above specification, in the same color-sensitive layer, a medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support. 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 4,705,744,
No. 4,707,436, JP-A Nos. 62-160448 and 63-89850, a main photosensitive layer such as BL, GL, RL and a donor layer (CL) having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer are mainly sensitized. It is preferably located adjacent to or in close proximity to the layers. As described above, various layer configurations according to the purpose of each photosensitive material
The sequence can be selected.

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Claims (1)

[Claims] 1. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the following acyl group is represented by the general formula (1) in at least one layer constituting the light-sensitive material. A silver halide color photographic light-sensitive material containing at least one acylacetamide type yellow coupler, and at least one compound represented by the following general formula (F) in at least one layer constituting the light-sensitive material. material. [Chemical 1] In the formula, R ₁ represents a substituent, and Q represents a nonmetallic atom group necessary for forming a 6-membered heterocycle or a 5-membered heterocycle containing 2 heteroatoms together with C. [Chemical 2] In the formula, A represents a redox mother nucleus or a precursor thereof, and represents an atomic group that allows (Time) _t X to be released only by being oxidized during photographic development processing. Time represents a group that releases X after leaving from the oxidant of A, and X represents a development inhibitor. L represents a divalent linking group, and G represents a polarizable group. n, m, and t each represent 0 or 1.