JPH0611809A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color developing property and rigidity of color images by incorporating an acylacetoamide coupler having sepcified acyl groups and a specified coupler into the photosensitive material. CONSTITUTION:This photosensitive material contains an acylacetoamide coupler having an acyl group expressed by formula I and a coupler expressed by formula II or III. In formula I, R1 is a substituent, Q is nonmetal atoms to form a six-member heteroring with C or five-member hetero ring including two hetero atoms. In formula II, R1 is -CONR4R5, -SO2NR4R5, etc., R2 is a group which can be substituted with a naphthalene ring, K is an integer 0-3, R3 is a substituent, X is a hydrogen atom or a group which can be released by the coupling reaction with the oxidant of an aromatic primary amine developing agent, and R4 and R5 are hydrogen atoms, alkyl groups, aryl groups, etc. In formula III, R<1> is an alkyl group, aryl group or heterocyclic group, R<2> is an aryl group, Z is a hydrogen atom or a group which is released by coupling.

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, which gives a particularly high color forming property.
The present invention relates to a silver halide color photographic light-sensitive material excellent in color image fastness, storability of a light-sensitive material with time, and stability of color development processing.

[0002]

As a yellow coupler for forming a color photographic image, an acylacetanilide coupler represented by benzoylacetanilide coupler and pivaloylacetanilide coupler is generally used. However, the molecular extinction coefficient of the color-forming dye obtained from these couplers is relatively low as compared with that of the color-forming dye obtained from the cyan coupler or magenta coupler, so that the color density is low, and therefore the coating amount per unit area of the light-sensitive material is low. There was a serious problem that I had to do a lot. Furthermore, it is not possible to satisfy all of these, such as coupling activity, hue, and color image fastness, and there has been a strong demand for the development of a yellow coupler having these properties.

On the other hand, as an acyl group of an acylacetanilide type coupler, US Pat. No. 3,265,506 has been used.
In addition to the pivaloyl group, No. 7,7-dimethylnorbornane-1-carbonyl group, 1-methylcyclohexane-
1-carbonyl group refers to cyclopropane-1-carbonyl group and cyclohexane-1 in JP-A-47-26133.
A carbonyl group is presented. However, these couplers have drawbacks in that they are inferior in the coupling reaction activity, the molecular absorption coefficient of the coloring dye is low, the spectral absorption characteristics of the color image are inferior, or the robustness of the color image is inferior. Had.

Further, in European Patent 447,969A, a 1-substituted-cycloalkane (or heterocycle) -1-carbonyl group consisting of an optionally substituted 3- to 5-membered hydrocarbon ring or heterocycle is disclosed. An acylacetamide-type coupler having a is disclosed. Certainly, these couplers have been improved in color developability, hue and color image fastness, but they are not yet satisfactory. In addition, other properties such as stability of color development processing and storability of the light-sensitive material with time are not sufficient, and further development is desired. Further, U.S. Pat. No. 5,118,599 describes a part of the present invention 1-
Acyl acetanilide couplers with substituted-dioxane-1-carbonyl groups have been proposed. This type of coupler is recognized to have improved color forming property and hue as compared with the conventional pivaloyl acetanilide coupler, but as with the above-mentioned problems, the problems of storage stability and color development processing stability of the light-sensitive material must be solved. I knew it was.

On the other hand, phenol and naphthol couplers are well known as cyan couplers. Regarding the phenol-based and naphthol-based couplers, examples of the phenol-based coupler include 2-acylamino-5-alkylphenol type, 2,5-diacylaminophenol type, 2-ureido-5-acylamino type, and the like. Is 2-carbamoyl-
Typical examples are 1-naphthol type couplers and amide group-containing couplers at the 5-position. Specific examples of these couplers include U.S. Pat. Nos. 2,369,929 and 2,801,171.
No. 2, No. 2,895,826, No. 3,772,00
No. 2, No. 4,052,212, No. 4,146,3
No. 96, No. 4,228, 233, No. 4,296,
No. 200, No. 2,772, 162, No. 3,75
No. 8,308, No. 4,334,011, West German Patent Publication No. 3,329,729, European Patent Publication No. 1
21,365, U.S. Pat. Nos. 4,327,173, 3,446,622, 4,333,999,
No. 4,427,767, No. 4,451,559
No. 4,775,616, European Patent Publication No. 2
71,323-271,325, U.S. Pat. No. 4,69
No. 0,889, No. 4,254,212, No. 4,2
Examples thereof include couplers described in JP-A No. 96,199 and JP-A No. 61-42658. However, the performance required for the cyan coupler, for example, the activity of the coupling reaction with the oxidized aromatic primary amine color developer, the molecular absorption coefficient of the dye to be formed, the spectral absorption maximum wavelength, the green light on the short wavelength side, Absorption density in the blue light region, change in hue due to color density, etc .; heat and humidity of color dye image, fastness to light, leuco formation of color dye in reducing atmosphere, stability of color dye such as change of hue over time Properties; storage stability of photographic material over time; and processing stability associated with compositional changes in color development processing; The method of use is still being developed.

[0006]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color forming property and color image fastness. The second object is to provide a silver halide color photographic light-sensitive material which is excellent in the storage stability of the light-sensitive material. A third object is to provide a silver halide color photographic light-sensitive material excellent in processing stability in color development processing.

[0007]

The above-mentioned objects can be achieved by the silver halide color photographic light-sensitive material described below. That is, in a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, an acylacetamide type coupler represented by the general formula (I) whose acyl group is represented by the following chemical formula 4 is used. A silver halide color photographic light-sensitive material containing a coupler represented by the following general formula (II) or the following general formula (III). General formula (I)

[0008]

[Chemical 4]

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. General formula (II)

[0010]

[Chemical 5]

In the formula, R ₁ is --CONR ₄ R ₅ , --SO _{2
NR 4 R 5, -NHCOR 4,} -NHCOOR 6, -N
HSO ₂ R ₆ , -NHCONR ₄ R ₅ or -NHSO
₂ NR ₄ R ₅ , R ₂ is a group capable of substituting on a naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, and X is a hydrogen atom or an aromatic primary amine developer oxidant. Represents a group capable of leaving by a coupling reaction with. However, R ₄ and R ₅ may be the same or different and each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₆ represents an alkyl group, an aryl group or a heterocyclic group. When k is plural, R _{2 s} may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring. In addition, a dimer or a multimer of R ₁ , R ₂ , R ₃ or X which is bonded to each other via a divalent or divalent or higher valent group may be formed. General formula (III)

[0012]

[Chemical 6]

In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, R ² represents an aryl group, and Z represents a hydrogen atom or a coupling-off group.

The present invention will be described in detail below.

First, the acylacetamide type yellow coupler of the present invention in which the acyl group is represented by the general formula (I) will be described in detail. The acylacetamide type yellow coupler of the present invention is preferably represented by the general formula (Y) shown below.

[0016]

[Chemical 7]

In the formula, R ₁ represents a substituent, Q represents a 6-membered heterocycle together with C or a non-metal atom group necessary for forming a 5-membered heterocycle containing 2 heteroatoms, and R ₂ is a hydrogen atom, 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 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 (for example, methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, Allyl, 3-cyclohexenyl,
Oleyl, benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl).

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

When the substituent in 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 Cs, which contains at least one heteroatom selected from N, S, O and P together with C in the ring. Alternatively, it represents a group of nonmetallic atoms necessary for forming a 5-membered heterocycle containing two heteroatoms selected from N, S, O and P in the ring. The ring formed by Q together with C may contain an unsaturated bond in the ring, and may be substituted or unsubstituted. When it is substituted, the substituent is R
_The same as those described for ₃ can be mentioned, but they may be further substituted with an oxo group (= 0), or the substituents may be bonded to each other to form a ring. Among the 6-membered heterocycles which Q forms with C, even more preferred is when twice the carbonyl-substituted carbon (β position relative to the carbonyl group) is at least one heteroatom, thus More preferable acyl group represented by formula (I) is represented by the following general formula (I-1). General formula (I-1)

[0024]

[Chemical 8]

In the formula, Z is a heteroatom selected from O, S, N and P, R ₁ is a substituent, Q is C,
5 containing two 6-membered heterocycles or heteroatoms with Z
Represents a group of non-metal atoms necessary for forming a heterocyclic ring of a member. R ₁ and Q have the same contents as those in formula (Y), and preferred examples are also the same.

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 C atoms, an aryl group having 6 to 30 C atoms, or 1 to 30 C 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 with respect to the acylacetamide group. In formula (Y), X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom.

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

Substituents particularly preferably used in formula (Y) 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, (for example, methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), an alkoxy group having a C number of 1 to 30. (Eg methoxy,
Ethoxy, methoxyethoxy, butoxy), or an aryloxy group having a C number of 6 to 24 (for example, phenoxy group, p
-Tolyloxy, p-methoxyphenoxy).

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

X is particularly preferably represented by the formula (Y-1), (Y-2) or (Y-
It is a group represented by 3).

[0034]

[Chemical 9]

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 -N
A heterocyclic group which is R ₆ —NR ₇ —. The heterocyclic group represented by formula (Y-1) has a C number of 2 to 30, preferably 4 to.
20 and more preferably 5 to 16.

[0038]

[Chemical 10]

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

[0040]

[Chemical 11]

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

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

The coupler represented by the formula (Y) is bonded to each other through a divalent or higher valent group in the substituents R ₁ , Q, X or the group represented by the formula (Yb) represented by the chemical formula 12. Two
Multimers or higher multimers may be formed. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

[0044]

[Chemical 12]

Specific examples of each substituent in the formula (Y) are shown below in Chemical formulas 13 to 23.

[0046]

[Chemical 13]

[0047]

[Chemical 14]

[0048]

[Chemical 15]

[0049]

[Chemical 16]

[0050]

[Chemical 17]

[0051]

[Chemical 18]

[0052]

[Chemical 19]

[0053]

[Chemical 20]

[0054]

[Chemical 21]

[0055]

[Chemical formula 22]

[0056]

[Chemical formula 23]

Chemical formulas 24 to 39 show specific examples of the yellow coupler represented by the formula (Y).

[0058]

[Chemical formula 24]

[0059]

[Chemical 25]

[0060]

[Chemical formula 26]

[0061]

[Chemical 27]

[0062]

[Chemical 28]

[0063]

[Chemical 29]

[0064]

[Chemical 30]

[0065]

[Chemical 31]

[0066]

[Chemical 32]

[0067]

[Chemical 33]

[0068]

[Chemical 34]

[0069]

[Chemical 35]

[0070]

[Chemical 36]

[0071]

[Chemical 37]

[0072]

[Chemical 38]

[0073]

[Chemical Formula 39]

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.

[0075]

[Chemical 40]

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

Synthesis Example 2 Synthesis of Exemplified Compound Y-10 Compound E was used in place of Compound A used in the synthesis of Exemplified Compound Y-29, and 2-, instead 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.

[0078]

[Chemical 41]

In the present invention, the acyl group has the general formula (I)
The acylacetamide type coupler represented by can be used in any of the layers constituting the silver halide color photographic light-sensitive material. When it is used as the main coupler of the yellow coupler, it is preferably used in the blue-sensitive silver halide emulsion layer or the adjacent non-photosensitive layer. When the coupler releases a photographically useful group or a precursor thereof, it is used in a silver halide photosensitive layer or a non-photosensitive layer depending on the purpose. In the present invention, the acylacetamide type couplers having an acyl group represented by the general formula (I) may be used in combination of two or more kinds, or may be divided and added in two or more layers. It can also be used in combination with other known couplers. The amount of the acylacetamide type coupler of which the acyl group of the present invention is represented by the general formula (I) is 1
It is in the range of 2.0 to 1.0 × 10 ⁻³ mol per mol. It is preferably in the range of 1.0 to 5.0 × 10 ⁻³ mol. More preferably, it is in the range of 5.0 × 10 ^{-1 to} 1.0 × 10 ^-2 mol. When used for the non-photosensitive layer, 1.
The coating amount is in the range of 0 to 1.0 × 10 ⁻³ g / m ² . The range is preferably 5.0 × 10 ^{−1 to} 2.0 × 10 ⁻³ g / m ² , and more preferably 2.0 × 10 ^{−1 to} 5.0 × 10 ^−3.
It is in the range of g / m ² .

The acylacetamide type coupler having an acyl group of the present invention represented by the general formula (I) can be introduced into a light-sensitive material by various known dispersion methods. In the oil-in-water dispersion method, which is one of the known dispersion methods, one or two or more kinds of high-boiling point organic solvents described below can be arbitrarily mixed and used. The ratio of the coupler of the present invention to the high boiling point organic solvent used may be in a wide range, but the weight ratio is preferably 5.0 or less per 1 g of the coupler. More preferably, the weight ratio is in the range of 1.0 × 10 ^{-2 to} 1.0. Further, a latex dispersion method or a solid dispersion method described later can also be applied. Furthermore, it can be used by mixing or coexisting with various couplers and compounds described later.

In the present invention, the acyl group has the general formula (I)
The acylacetamide type coupler represented by the formula (1), when introduced into the same light-sensitive material as the coupler represented by the general formula (II) or the general formula (III) described later, gives high color forming property and is excellent in color image fastness Is a coupler exhibiting excellent storage stability over time and stability in color development processing.

Next, the compound represented by the general formula (II) will be described in detail. R ₁ is -CONR ₄ R ₅ , -S
_{O 2 NR 4 R 5, -NHCOR} 4, NHCOOR 6, -
NHSO ₂ R ₆ , -NHCONR ₄ R ₅ or -NHS
Representing O ₂ NR ₄ R ₅ , R ₄ R ₅ and R ₆ are each independently an alkyl group having 1 to 30 total carbon atoms (hereinafter referred to as C number), an aryl group having 6 to 30 C atoms, or 2 to C numbers. Thirty
Represents a heterocyclic group. R ₄ and R ₅ may also be hydrogen atoms.

R ₂ represents a group capable of substituting on a naphthalene ring (including an atom; the same applies hereinafter), and representative examples thereof include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carbonyl group, an amino group and a sulfo group. , Cyano group, alkyl group, aryl group, heterocyclic group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, Examples thereof include an alkylsulfonyl group, an arylsulfonyl group, a sulfamoylamino group, an alkoxycarbonylamino group, a nitro group and an imide group. Examples of when k = 2 include a dioxymethylene group and a trimethylene group.
The C number of (R ₂ ) _k is 0 to 30.

R ₃ represents a substituent, preferably represented by the following formula (II-1). Formula (II-1) R ₇ (Y) _m − In formula (II-1), Y is>NH,> CO or> SO.
₂ , m is an integer of 0 or 1, R ₇ is a hydrogen atom, a C 1-30 alkyl group, a C 6-30 aryl group, C
Number 2 to 30 heterocyclic group, -COR ₈

[0085]

[Chemical 42]

Or —SO ₂ R ₁₀ respectively. Here, R ₈ , R ₉ and R ₁₀ have the same meanings as R ₄ , R ₅ and R ₆ , respectively. In R ₁ or R ₇ , -N
R _{4 and} R ₅ of R ₄ R ₅ and R ₈ and R ₉ of —NR ₈ R ₉ may be bonded to each other to form a nitrogen-containing heterocycle (eg, pyrrolidine ring, piperidine ring, morpholine ring).

X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent (referred to as a leaving group; including a leaving atom; the same applies hereinafter), and a typical example of the leaving group. As a halogen atom,

[0088]

[Chemical 43]

A thiocyanate group and a heterocyclic group having a C number of 1 to 30 and bonded to a coupling active position at a nitrogen atom (eg, succinimide group, phthalimido group, pyrazolyl group, hydantoinyl group, 2-benzotriazolyl group) are used. Can be mentioned. Here, R ₁₁ has the same meaning as R ₆ .

In the above, the alkyl group may be linear, branched or cyclic, and may have a substituent (eg halogen atom, hydroxyl group, aryl group, heterocyclic group) even if it contains an unsaturated bond. , An alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group, an acyl group), and representative examples include methyl, isopropyl, isobutyl, t-butyl, 2- Ethylhexyl, cyclohexyl, n-dodecyl, n-hexadecyl, 2-methoxyethyl, benzyl, trifluoromethyl, 3-dodecyloxypropyl, 3- (2,4-di-
There is t-pentylphenoxy) propyl.

Even if the aryl group is a condensed ring (for example, a naphthyl group), a substituent (for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
A cyano group, an acyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group), phenyl as a representative example,
Tolyl, pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2
-Tetradecyloxyphenyl, 2-chloro-5-dodecyloxyphenyl, 4-t-butylphenyl.

The heterocyclic group is O, N, S, P, Se, T
a 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one hetero atom of e in the ring, which is a substituent (for example, a halogen atom, a carboxyl group, a hydroxyl group,
Nitro group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group), As typical examples, 2-pyridyl, 4-pyridyl, 2-furyl, 4-thienyl, benzotriazol-1-yl, 5-phenyltetrazole-
There are 1-yl, 5-methylthio-1,3,4-thiadiazol-2-yl and 5-methyl-1,3,4-oxadiazol-2-yl.

Examples of preferable substituents in the present invention will be described below. R ₁ is -CONR ₄ R ₅ or -SO
₂ NR ₄ R ₅ is preferable, and specific examples include carbamoyl,
N-n-butylcarbamoyl, Nn-dodecylcarbamoyl, N- (3-n-dodecyloxypropyl) carbamoyl, N-cyclohexylcarbamoyl, N- [3
-(2,4-di-t-pentylphenoxy) propyl]
Carbamoyl, N-hexadecylcarbamoyl, N-
[4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl, N- (3-dodecyloxy-2-methylpropyl) carbamoyl, N- [3- (4-t-octylphenoxy) propyl] carbamoyl , N-hexadecyl-N-methylcarbamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N- [4- (2,
4-di-t-pentylphenoxy) butyl] sulfamoyl. R ₁ is particularly preferably -CONR ₄ R ₅ .

As R ₂ and k, k = 0, that is, unsubstituted one is most preferable, and then k = 1 is preferable. R ₂ is preferably a halogen atom, an alkyl group (eg, methyl,
It is isopropyl, t-butyl, cyclopentyl), a carbonamide group (eg acetamide, pivalinamide, trifluoroacetamide, benzamide), a sulfonamide (eg methanesulfonamide, toluenesulfonamide) or a cyano group.

R ₃ is preferably m in formula (II-1).
= 0, more preferably R ₇ is —COR ₈ [eg formyl, acetyl, trifluoroacetyl, 2-
Ethylhexanoyl, pivaloyl, benzoyl, pentafluorobenzoyl, 4- (2,4-di-t-pentylphenoxy) butanoyl], -COOR ₁₀ [eg methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, 2-ethylhexyloxycarbonyl, n-
Dodecyloxycarbonyl, 2-methoxyethoxycarbonyl] or —SO ₂ R ₁₀ [eg methylsulfonyl, n-butylsulfonyl, n-hexadecylsulfonyl, phenylsulfonyl, p-tolylsulfonyl, p-
Chlorophenylsulfonyl, trifluoromethylsulfonyl], and particularly preferably R ₇ is —COOR ₁₀ .

X is preferably a hydrogen atom, a halogen atom,
-OR ₁₁ [eg ethoxy, 2-hydroxyethoxy,
2-methoxyethoxy, 2- (2-hydroxyethoxy) ethoxy, 2-methylsulfonylethoxy, ethoxycarbonylmethoxy, carboxymethoxy, 3-carboxypropoxy, N- (2-methoxyethyl) carbamoylmethoxy, 1-carboxytridecyloxy. Two
An alkoxy group such as methanesulfonamidoethoxy, 2- (carboxymethylthio) ethoxy, 2- (1-carboxytridecylthio] ethoxy, eg 4-cyanophenoxy, 4-carboxyphenoxy, 4-methoxyphenoxy, 4-t -Octylphenoxy, 4-nitrophenoxy, 4- (3-carboxypropanamide)
Phenoxy, aryloxy groups such as 4-acetamidophenoxy group] or -SR ₁₁ [eg carboxymethylthio, 2-carboxymethylthio, 2-methoxyethylthio, ethoxycarbonylmethylthio, 2,3-dihydroxypropylthio, 2- (N An alkylthio group such as -N-dimethylamino) ethylthio, such as 4-carboxyphenylthio, 4-methoxyphenylthio, 4
An arylthio group such as-(3-carboxypropanamide) phenylthio], and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an alkylthio group.

The coupler represented by the general formula (II) may form a bis form in the substituents R ₁ , R ₂ , R ₃ or X, each of which is bonded to each other via a divalent or divalent or more divalent group. Multimers or higher multimers may be formed. In this case, the carbon number range shown in each of the above substituents may be out of the range. When the coupler represented by the general formula (II) forms a multimer, an addition-polymerizable ethylenically unsaturated compound having a cyan dye-forming coupler residue (a homopolymer or a copolymer of a cyan color-forming monomer is a typical example, preferably . equation represented by the formula (II-2) is (II-2) - (G i) gi - (H j) hj - in formula (II-2) G _i is a repeating unit derived from the color forming monomers Is a group represented by formula (II-3), H _j is a repeating unit derived from a non-color-forming monomer and is a group represented by formula (II-3), i is a positive integer, and j is Represents 0 or a positive integer, and gi and hi respectively represent the weight fraction of G _I or H _j , where when i or j is plural, G _i or H _j contains plural kinds of repeating units. Formula (II-3)

[0098]

[Chemical 44]

In the formula (II-3), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A
Represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, and B represents a divalent group having carbon atoms below both such as a substituted or unsubstituted alkylene group, a phenylene group or an oxydialkylene group. And L is-
CONH-, -NHCONH-, -NHCOO-, -N
HCO-, -OCONH-, -NH-, -COO-,-
OCO -, - CO -, - O -, - SO 2 -, NHSO 2
-, or represents a -SO ₂ NH-. a, b, and c represent an integer of 0 or 1. Q represents a cyan coupler residue obtained by removing one hydrogen atom from R ₁ , R ₂ , R ₃ or X of the compound represented by the general formula (II).

Examples of the non-color-forming ethylene type monomer which does not couple with the oxidation product of the aromatic primary amine developing agent which gives the repeating unit H _j include acrylic acid, α-chloroacrylic acid and α-alkylacrylic acid. Amides or esters derived from these acrylic acids (eg, methacrylic acid) (eg, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methac And β-hydroxyethyl methacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinyl). Acetophenone and sulfostyrene), itacone loss, citraconic acid,
Examples include crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine.

Particularly preferred are acrylic acid ester, methacrylic acid ester and maleic acid ester. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above formula (II-3) is in the form of the copolymer to be formed, for example, solid. , Liquid, micelles and physical and / or chemical substances such as solubility (solubility in water or organic solvents), compatibility with photographic colloid composition binders such as gelatin, its flexibility , Thermal stability, coupling reactivity with an oxidized product of a developing agent, and diffusion resistance in a photographic colloid can be favorably influenced. These copolymers may be random copolymers or copolymers having a specific sequence (for example, block copolymer, alternating copolymer).

The number average molecular weight of the cyan polymer coupler used in the present invention is usually on the order of thousands to millions, but oligomeric polymer couplers having a number of 5000 or less can also be used. The cyan polymer coupler used in the present invention is an organic solvent (for example, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone,
Whether it is a lipophilic polymer soluble in dibutyl phthalate or tricresyl phosphate) or a hydrophilic polymer miscible with a hydrocolloid such as gelatin aqueous solution, it has a structure and properties capable of forming micelles in the hydrocolloid. It may be a polymer.

In order to obtain a lipophilic polymer coupler soluble in an organic solvent, a lipophilic non-color-forming ethylenic monomer (eg acrylic acid ester, methacrylic acid ester, maleic acid ester, vinylbenzenes, etc.) is mainly used as a copolymerization component. Is preferred. The general formula (II-
It may be prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl-type monomer giving a coupler unit represented by 3) in an organic solvent and emulsifying and dispersing it in an aqueous gelatin solution in the form of latex. It may be prepared by an emulsion polymerization method.

A method of emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and an emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,3. 370,952
The method described in the publication can be used. Alternatively, in order to obtain a neutral or alkaline water-soluble hydrophilic polymer coupler, N- (1,1-dimethyl-2-sulfonateethyl) acrylamide, 3-sulfonatepropylacrylate, sodium styrenesulfonate, Styrene potassium sulfinate, acrylamide,
It is preferable to use a hydrophilic non-color forming ethylene-like monomer such as methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylpyridine, etc. as the copolymer component.

The hydrophilic polymer coupler can be added to the coating solution as an aqueous solution, and an organic solvent miscible with water such as lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone, ethyl lactate, dimethylformamide and dimethylacetamide. It can also be dissolved in a mixed solvent of water and water and added. Furthermore, it may be added after being dissolved in an alkaline aqueous solution or an organic solvent containing alkaline water. Also, a small amount of surfactant may be added.

Specific examples of each substituent in the formula (II) and the cyan coupler represented by the formula (II) are shown below.

Examples of R ₁

[Chemical formula 45]

[0109]

[Chemical formula 46]

[0110]

[Chemical 47]

[0111]

[Chemical 48]

Examples of R ₂

[Chemical 49]

Examples of R ₃ NH-

[Chemical 50]

[0114]

[Chemical 51]

[0115]

[Chemical 52]

[0116]

[Chemical 53]

[0117]

[Chemical 54]

Example of X

[Chemical 55]

[0119]

[Chemical 56]

[0120]

[Chemical 57]

[0121]

[Chemical 58]

Specific examples of the cyan coupler represented by the general formula (II)

[Chemical 59]

[0123]

[Chemical 60]

[0124]

[Chemical formula 61]

[0125]

[Chemical formula 62]

[0126]

[Chemical formula 63]

[0127]

[Chemical 64]

[0128]

[Chemical 65]

[0129]

[Chemical formula 66]

Specific examples of the cyan coupler represented by the formula (II) other than the above and / or a method for synthesizing these compounds are described in, for example, US Pat. No. 4,690,889, JP-A-60.
-237448, 61-153640, 61-
No. 145557, No. 63-208042, No. 64-3
1159 and West German Patent No. 3823049A. The cyan coupler represented by the formula (II) is
As described in JP-A-62-269958,
It is preferable to use a small amount of a high boiling point organic solvent for dispersion in order to further improve the sharpness and desilvering property.

Specifically, the high boiling point organic solvent is used in a weight ratio of 0.3 or less, more preferably 0.1 or less, relative to the cyan coupler represented by the formula (II). The cyan coupler represented by the formula (II) is preferably used in combination of two or more kinds. When the same color sensitivity is divided into two or more layers having different sensitivities, a 2-equivalent cyan coupler is used in the highest sensitivity layer. It is preferable to use a 4-equivalent cyan coupler in the lowest sensitivity layer. It is preferable to use either or both of the same color-sensitive layers other than those.

Next, the phenol cyan coupler represented by formula (III) will be described in detail below. In the general formula (III), R ¹ is an optionally substituted linear, branched or cyclic alkyl group having 1 to 36 (preferably 4 to 30) total carbon atoms (hereinafter referred to as C number),
An optionally substituted aryl group having a C number of 6 to 36 (preferably 12 to 30) or a C number of 2 to 36 (preferably 1)
2 to 30) is represented. Here, the heterocyclic group represents a 5 to 7-membered optionally condensed heterocyclic group having at least one hetero atom selected from N, O, S, P, Se and Te in the ring, and examples As 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 4-pyrimidyl,
There are 2-imidazolyl, 4-quinolyl and the like. Examples of the substituent of R ¹ include a halogen atom, a cyano group, a nitro group,
Carboxyl group, sulfo group, alkyl group, aryl group,
Heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, acyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, imide group, amino Group, ureido group, alkoxylcarbonylamino group or sulfamoylamino group (hereinafter referred to as substituent group A),
Examples of preferable substituents are an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group or an imido group.

In the general formula (III), R ² has a C number of 6 to 36.
It represents an aryl group (preferably 6 to 15) and may be substituted with a substituent selected from the above-mentioned Substituent group A or may be a condensed ring. Here, as a preferable substituent, a halogen atom (F, Cl, Br, I), a cyano group, a nitro group, an acyl group (eg, acetyl, benzoyl), an alkyl group (eg, methyl, t-butyl, trifluoromethyl, trichloro). Methyl), alkoxy groups (eg methoxy, ethoxy, butoxy, trifluoromethoxy), alkylsulfonyl groups (eg methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl groups (eg phenylsulfonyl, p-tolylsulfonyl, p). -Chlorophenylsulfonyl), an alkoxycarbonyl group (eg methoxycarbonyl, butoxycarbonyl), a sulfonamide group (eg methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), Bamoiru group (e.g. N, N- dimethylcarbamoyl, N- phenylcarbamoyl), or a sulfamoyl group (e.g. N, N
-Diethylsulfamoyl, N-phenylsulfamoyl). R ³ is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group, and more preferably 4-cyano. Phenyl, 4-cyano-3-halogenophenyl, 3-cyano-4-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3-alkoxyphenyl, 3-alkoxy- 4-alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4-halogenophenyl, 3,4,5-trihalogenophenyl, 3,4-dicyanophenyl, 3-cyano-4,5-dihalogenophenyl, 4- Trifluoromethylphenyl or 3-sulfon A Dofeniru, particularly preferably 4-cyanophenyl, 3-cyano -
4-halogenophenyl, 4-cyano-3-halogenophenyl, 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula (III), Z represents a hydrogen atom or a coupling-off group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Examples of coupling-off groups include halogen atoms, sulfo groups,
An alkoxy group having a C number of 1 to 36 (preferably 1 to 24),
An aryloxy group having a C number of 6 to 36 (preferably 6 to 24), an acyloxy group having a C number of 2 to 36 (preferably 2 to 24), an alkylsulfonyl group having a C number of 1 to 36 (preferably 1 to 24), Arylsulfonyl group having a C number of 6 to 36 (preferably 6 to 24), C number of 1 to 36 (preferably 2 to)
24) alkylthio group, C number of 6 to 36 (preferably 6)
To 24) arylthio group, C number of 4 to 36 (preferably 4 to 24) imide group, C number of 1 to 36 (preferably 1 to 36)
24) a carbamoyloxy group or a heterocyclic group bonded to the coupling active position with a nitrogen atom having a C number of 1 to 36 (preferably 2 to 24) (eg pyrazolyl, imidazolyl,
1,2,4-triazol-1-yl, tetrazolyl)
There is. Here, the following groups are the alkoxy groups A
It may be substituted with a substituent selected from Z is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group thio group, and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an aryloxy group.

Specific examples of R ¹ , R ² and Z in the general formula (III) are shown below.

Examples of R ¹

[Chemical formula 67]

[0137]

[Chemical 68]

[0138]

[Chemical 69]

[0139]

[Chemical 70]

[0140]

[Chemical 71]

[0141]

[Chemical 72]

[0142]

[Chemical formula 73]

Examples of R ²

[Chemical 74]

[0144]

[Chemical 75]

Example of Z

[Chemical 76]

[0146]

[Chemical 77]

[0147]

[Chemical 78]

[0148]

[Chemical 79]

Specific examples of the cyan coupler represented by formula (III) are shown below. However, A to Z and a to f are
7, chemical formula 68, chemical formula 69, chemical formula 70, chemical formula 71, chemical formula 72, chemical formula 73
It is a serial number of a specific example of R ¹ in.

[0150]

[Table 1]

[0151]

[Table 2]

[0152]

[Table 3]

[0153]

[Table 4]

[0154]

[Table 5]

The cyan coupler represented by the general formula (III) is described in, for example, JP-A-56-65134 and JP-A-61-2757.
No. 63-159848, No. 63-161450.
No. 63-161451, JP-A No. 1-254956.
No. 4,923,791, and US Pat. No. 4,923,791.

In the present invention, the cyan coupler represented by the general formula (I) and the general formula (II) or the general formula
A cyan coupler represented by formula (III) is used in combination, and the formula (I) and the formula (II) or the formula (III) are used in combination.
Can be arbitrarily set. That is, the general formula (I): the general formula (II) or (III) is 99.9: 0.1-0.1:
It can be taken at a ratio of 99.9 (molar ratio). The ratio of the general formula (I) / total cyan coupler is preferably 30 mol% or more, more preferably 50 mol% or more, and the upper limit thereof is 9%.
It is 9.9 mol%. In the present invention, the total amount of the coupler represented by the general formula (I) and the general formula (II) or the general formula (III) in the photosensitive material is 1 mol of silver halide when used in the photosensitive layer. The range is 1 × 10 ^{−3 to} 2 mol per unit. It is preferably in the range of 1 × 10 ^-2 to 1 mol, and more preferably in the range of 2 × 10 ^{-2 to} 0.5 mol. When used in the non-photosensitive layer, it is in the range of 1 × 10 ⁻³ to 1 mol per mol of silver halide in the adjacent photosensitive layer. The amount is preferably 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 5 × 10 ⁻³ to 2 × 10 ⁻¹ mol. General formula (I) and general formula (II) or general formula (II
The total coating amount of the coupler represented by I) is in the range of 1 × 10 ^{−3 to 3} g / m ² per layer. Preferably 5x
10 ^{−3 to 1} g / m ² , more preferably 1 × 10 ⁻² to
It is in the range of 5 × 10 ⁻¹ g / m ² .

The coupler represented by the general formula (III) of the present invention can be introduced into the light-sensitive material by any known dispersion method, but the oil-in-water dispersion method described below is preferably used. The method of adding the used dispersion is preferred.

In the present invention, the coupler represented by the general formula (II) or the general formula (III) can be used in any of the layers constituting the light-sensitive material, but is preferably a red-sensitive emulsion layer or a layer thereof. Adjacent non-photosensitive layer.
Two or more kinds of the couplers represented by the general formula (II) or the general formula (III) of the present invention can be used in combination, and can be divided and added in two or more layers. Further, it can be used in combination with other known couplers. In the case of a photosensitive silver halide emulsion layer, the total amount of the coupler represented by formula (II) or formula (III) of the present invention is 2.0 to 1.0 × 10 ⁻ per mol of silver halide. It is in the range of ³ moles. It is preferably in the range of 1.0 to 5.0 × 10 ⁻³ mol, and more preferably in the range of 5.0 × 10 ^{−1 to} 1.0 × 10 ⁻² mol. When used for the non-photosensitive layer, 1.0 to 1.
The coating amount is in the range of 0 × 10 ⁻³ g / m ² . It is preferably in the range of 5.0 × 10 ^{−1 to} 2.0 × 10 ⁻³ g / m ² ,
More preferably 2.0 × 10 ^{−1 to} 5.0 × 10 ⁻³ g / m ²
Is the range. When the coupler represented by the general formula (II) and the coupler represented by the general formula (III) are used together in the same layer, the ratio can be arbitrarily set according to the intended performance of the photographic material. When used in the same layer, favorable results can be obtained, for example, in improving color image fastness.

In the present invention, the coupler represented by the general formula (II) or the general formula (III) is used in the same light-sensitive material as the acylacetamide type coupler in which the acyl group is represented by the general formula (I). The sensitivity of the photographic property of the light-sensitive material can be increased, and the color image fastness of the three colors of cyan, magenta and yellow can be fastened in a well-balanced manner. In particular, the processing stability of color development processing can be improved and the storability of the light-sensitive material with time can be improved. further,
The layer containing an acylacetamide type coupler whose acyl group is represented by the general formula (I) has the general formula (II) or the general formula
By containing a small amount of the coupler represented by (III), a unique effect of significantly improving color image fastness is exhibited. The content of 10 mol% or less is sufficient, and 5% mol% or less is also preferable. The lower limit is approximately 1 x 10
^-2 mol%.

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

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

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

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used for the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface 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 a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically 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. Brightening agent: page 24, page 647, right column 868, fogging prevention 24: 25, page 649, right column 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 10. Binder 26 pages 651 left column 873 to 874 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, inhibitor 14. matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Examples of the yellow coupler include, in addition to the acylacetamide type couplers in which the acyl group is represented by the general formula (I), US Pat.
3,933,501, 4,022,620, 4,326,024,
No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-1073
9, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,
Those described in No. 649, European Patent Nos. 249,473A, No. 447,969A and the like can be used in combination as necessary.

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. As the cyan coupler, the above general formula (I
In addition to the coupler represented by I) or (III), U.S. Pat.Nos. 4,052,212, 4,146,396, and 4,228,233.
No. 4,296,200, 2,369,929, 2,801,
171, No. 2,772,162, No. 2,895,826, No. 3,
772,002, 3,758,308, 4,334,011, 4,327,173, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A, U.S. Patent 3,44
No. 6,622, No. 4,333,999, No. 4,775,616, No.
4,451,559, 4,427,767, 4,690,889,
No. 4,254,212, No. 4,296,199, JP-A-61-42
The couplers described in No. 658 and the like can be used if necessary. Further, JP-A-64-553, 64-554, 64-
It is also possible to use the pyrazoloazole couplers described in US Pat. Nos. 555 and 64-556 and the imidazole couplers described in US Pat. No. 4,818,672. Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409,320.
No. 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent No. 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
Nos. 1,146,368 and JP-A-3-223750 are preferred. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181, and US Pat.
It is also preferable to use a coupler having a dye precursor group as a leaving group capable of forming a dye by reacting with a developing agent described in No. 7,120. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD 17643, VII-F and Nos. 307105 and VII-F, JP-A-57-151944 and 57-154234.
Nos. 60-184248, 63-37346, 63-37350, U.S. Patents 4,248,962, 4,782,012, European Patent 482,5.
Those described in No. 52A are preferable. RD No. 11449, same
The bleaching accelerator releasing coupler described in JP-A No. 24241 and JP-A No. 61-201247 is effective for shortening the processing time having a bleaching ability, and in particular, the above-mentioned tabular silver halide grain-sensitive photosensitive material is used. The effect is great when added to the material. As couplers that release a nucleating agent or a development accelerator imagewise during development, those described in British Patents 2,097,140 and 2,131,188 and JP-A-59-157638 and 59-170840 are preferable. Further, JP-A-60-107029,
Compounds that release a fogging agent, a development accelerator, a silver halide solvent, etc. by a redox reaction with an oxidant of a developing agent described in JP-A-60-252340, JP-A-1-44940, and JP-A 1-45687. Is 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 photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

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

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N diethylaniline and 3-methyl-4-amino-N-. Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, 4-amino-3-
Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl- N-
(2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Methyl-N- (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N -Ethyl -N-
(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxy Pentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl ) Aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochlorides Alternatively, p-toluenesulfonate may be used.
Among these, especially 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 4-amino-3-methyl-
N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonate or sulfuric acid Salt is preferred. Two or more of these compounds can be used in combination depending on the purpose. Color developers include alkaline metal carbonates, borates or phosphates.
It is common to include a pH buffer, 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. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agent, aminopolycarboxylic acid,
Aminopolyphosphonic 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, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and them Can be mentioned as a representative example.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. 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 for 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 washed with water and / or stabilized after the desilvering treatment. 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 accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure Nos. 14,850 and No. 15,159, aldol compounds described in No. 13,924, U.S. Pat.No. 3,719,492. Metal salt complexes described, JP-A-53-135
The urethane compound described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-(-3-phenyl-3-phenyl-3- (cyclohexyl) -3- (phenyl-3-phenyl-3-methyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3- (3-phenyl-3-phenyl-3- (3-phenyl-3- (phenyl-phenyl--3-one-
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-58-115438 and the like. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

The silver halide color photographic light-sensitive material of the present invention is more likely to exhibit effects when applied to a lens-fitted film unit described in JP-B-2-32615, JP-B-3-39784 and the like. It is valid.

[0180]

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 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: gelatin hardener ExS: amount sensitizing dye coating amount which represents the amount for silver halide and colloidal silver were represented in units of g / m ² of silver and coupler, for additives and gelatin in the unit of g / m ² For the sensitizing dye, the number of moles per mole of silver halide in the same layer is shown.

First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 1.90 ExM-1 2.0 × 10 ^-2 HBS-1 3.0 × 10 ^-2

Second layer (intermediate layer) Gelatin 2.10 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 4.0 × 10 ^-3 HBS-2 7.0 × 10 ^-2

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.15 Emulsion B Silver 0.25 Gelatin 1.50 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 IIC- 7 0.21 ExC-2 3.0 x 10 ^-2 ExC-4 1.0 x 10 ^-2 HBS-1 7.0 x 10 ^-3

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion C Silver 0.25 Emulsion D Silver 0.45 Gelatin 2.00 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 IIC- 7 0.33 ExC-1 8.0 × 10 ^-2 ExC-4 1.5 × 10 ^-2 ExY-3 2.0 × 10 ^-2 ExY-2 1.0 × 10 ^-2 Cpd-10 1.0 × 10 ^-4 HBS-1 0.10

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 0.60 Gelatin 1.60 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 III C-1 7.0 × 10 ^-2 II C-34 8.0 x 10 ^-2 ExC-3 0.8 x 10 ^-2 ExC-4 1.5 x 10 ^-2 HBS-1 0.15 HBS-2 8.0 x 10 ^-2

Sixth Layer (Intermediate Layer) Gelatin 1.10 P-2 0.17 Cpd-1 0.10 Cpd-4 0.17 HBS-1 5.0 × 10 ^-2

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion F Silver 0.10 Emulsion G Silver 0.15 Gelatin 0.50 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 0.3 × 10 ^-4 ExM- ^{1 3.0 × 10 -2 ExM-2} 0.20 ExY-1 1.0 × 10 -2 ExY-3 2.0 × 10 -2 Cpd-11 7.0 × 10 -3 HBS-1 0.20

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion H Silver 0.55 Gelatin 1.00 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 3.0 × 10 ^-5 ExM-1 3.0 × 10 ^{-2 ExM-2 0.25 ExM-3} 1.5 × 10 -2 ExY-1 2.0 × 10 -2 ExY-3 2.0 × 10 -2 Cpd-11 9.0 × 10 -3 HBS-1 0.20

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion I Silver 0.45 Gelatin 0.90 ExS-4 2.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 2.0 × 10 ^-5 ExS-7 3.0 × 10 ^-4 ExM-1 1.0 x 10 ^-2 ExM-4 3.9 x 10 ^-2 ExM-5 2.6 x 10 ^-2 Cpd-2 1.0 x 10 ^-2 Cpd-9 2.0 x 10 ^-4 Cpd-10 2.0 x 10 ^-4 HBS-1 0.20 HBS-2 5.0 × 10 ^-2

10th layer (yellow filter layer) Gelatin 0.90 Yellow colloid 5.0 × 10 ^-2 Cpd-1 0.20 HBS-1 0.15

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion J Silver 0.10 Emulsion K Silver 0.20 Gelatin 1.00 ExS-8 2.0 × 10 ^-4 Comparative coupler (1) 0.83 ExY-1 2.0 × 10 ^-2 ExY-3 4.0 × 10 ^-2 IIC-10 2.0 × 10 ^-2 Cpd-2 1.0 × 10 ^-2 HBS-1 0.30 HBS-4 0.15

Twelfth layer (high-sensitivity blue emulsion layer) Emulsion L Silver 0.40 Gelatin 0.60 ExS-8 1.0 × 10 ^-4 Comparative coupler (1) 0.11 ExY-3 1.0 × 10 ^-2 Cpd-2 1.0 × 10 ^-3 HBS-1 4.0 x 10 ^-2 HBS-3 2.0 x 10 ^-2

Thirteenth Layer (First Protective Layer) Fine grain silver iodobromide (average particle size 0.07 μm, AgI 1 mol%) 0.20 Gelatin 0.80 UV-2 0.10 UV-3 0.10 UV-4 0.20 HBS-3 4.0 × 10 ^-2 P-3 9.0 x 10 ^-2

14th layer (second protective layer) Gelatin 0.90 B-1 (diameter 1.5 μm) 0.10 B-2 (diameter 1.5 μm) 0.10 B-3 2.0 × 10 ^-2 H-1 0.40

Furthermore, storability, processability, pressure resistance, anti-mold and
In order to improve antibacterial properties, antistatic properties, and coating properties, the following Cpd-3, Cpd-5 to Cpd-8, P-
1, P-2, W-1 to W-3 were added. In addition to the above, B-4, F-1 to F-11, an iron salt, a lead salt, a gold salt, a platinum salt, an iridium salt, and a rhodium salt are appropriately contained in each layer. Next, a list of emulsions used in the present invention and the chemical structural formulas or chemical names of the compounds are shown below.

[0197]

[Table 6]

[0198]

[Table 7]

In Tables 6 and 7, (1) each emulsion was reduction-sensitized at the time of grain preparation with thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Each emulsion was subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-2-237450. There is. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-2-237450 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0200]

[Chemical 80]

[0201]

[Chemical 81]

[0202]

[Chemical formula 82]

[0203]

[Chemical 83]

[0204]

[Chemical 84]

[0205]

[Chemical 85]

[0206]

[Chemical 86]

[0207]

[Chemical 87]

[0208]

[Chemical 88]

[0209]

[Chemical 89]

[0210]

[Chemical 90]

[0211]

[Chemical Formula 91]

[0212]

[Chemical Formula 92]

[0213]

[Chemical formula 93]

[0214]

[Chemical 94]

Then, the following samples were prepared. (Samples 102 to 110) Similarly, the eleventh layer of Sample 101,
A sample was prepared by substituting the comparative coupler (1) used in the twelfth blue-sensitive emulsion layer with an acylacetamide type coupler of the present invention whose acyl group is represented by the general formula (I) in an equimolar amount as shown in Table 8. did.

The samples 101 to 110 thus produced were subjected to the following color development processing, and the following performances were examined. (1) Photographic (sensitivity) gradation exposure of white light (color temperature of light source 4800 ° K)
After the color development processing, the density was measured, and the logarithm of the reciprocal of the exposure amount giving the density of the minimum density + 0.2 was obtained from the characteristic curve of the yellow density, and this was taken as the sensitivity, and the difference (ΔS ₁ ) Was calculated. (2) Storability of sensitive material Two sets of each sample were prepared, one set was 5 ° C and relative humidity was 30
% For 7 days, the other set under the conditions of 40 ° C. and 80% relative humidity for 7 days, and these two sets of samples are exposed to the same light as in the above (1) for color development. Then, the sensitivity was determined by the same method. With respect to these sensitivities, the difference (ΔS ₂ ) from the sample stored under the conditions of 40 ° C. and 80% relative humidity was determined with reference to the value of the sample stored under the conditions of 5 ° C. and 30% relative humidity.

(3) Color image fastness After densitometry of samples subjected to color development processing by applying gradation exposure of white light, these samples were tested at 60 ° C. and relative humidity of 7
After storing under 0% condition for 30 days, the concentration was measured again. Read the yellow density at the same exposure amount point after the test at the exposure amount point that gives the yellow density of the minimum density +1.5 before the test start, and divide the value obtained by subtracting the minimum density from the yellow density by 1.5. The percentage of the value obtained was calculated.

The color development processing carried out to examine the above performance is shown below. Incidentally, the processing of the sample for examining the performance was carried out after the running treatment was carried out until the sample which had been separately subjected to the imagewise exposure was replenished by the amount of 3 times the capacity of the color developing tank. The processing steps and the composition of the processing liquid are shown.

(Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 10 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixed 50 seconds 38.0 ℃ 420 ml 5 liters Water wash 30 seconds 38.0 ℃ 980 ml 3.5 liters Stability (1) 20 seconds 38.0 ℃ −3 liters Stability (2) 20 seconds 38.0 ℃ 560 mls 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 1 m ² of light-sensitive material The stabilizing solution is a countercurrent system from (2) to (1), and the overflow solution of washing water is all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the washing process were each per 1 m ² of the light-sensitive material. They were 65 ml, 50 ml, 50 ml and 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphospho 3.3 3.3 Acid sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-diaminopropane tetraacetate ferric iron ammo 130 195 ammonium monohydrate ammonium bromide 70 105 ammonium nitrate 14 21 hydroxyacetic acid 50 75 acetic acid 40 60 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (P
H7.0)

(Fixing solution) Tank solution (g) Replenishing solution (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution 280 ml 840 ml (700 g / l) Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 1.0 liter 1.0 liter pH by adding water [Prepared with ammonia water and acetic acid] 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizer) Common to tank liquid and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) Disodium ethylenediaminetetraacetate Salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The results obtained are summarized in Table 8.

[0227]

[Table 8]

From the results shown in Table 8, the acyl group is represented by the general formula (I).
The yellow color images of Samples 102 to 110 using the acylacetamide type coupler represented by the formula (1) and the coupler represented by the general formula (II) or the general formula (III) give high sensitivity, and the storability and color image fastness of the light-sensitive material are high. It is clear that when compared with the comparative sample 101, it is excellent.

The coupler IIC-10 used in the eleventh blue-sensitive emulsion layer was prepared as IIC-7, IIIC-6, IIIC-14.
The same result can be obtained by substituting an equimolar amount with the above and the fastness of the yellow color image is examined, and the fastness of the color image can be improved.

Example 2 Based on the sample 101 manufactured in Example 1, the third layer to the fifth layer are used.
Cyan coupler IIC-7, I used in the red-sensitive emulsion layer
IIC-1 and IIC-34 are represented by the general formula (II) or (II of the present invention.
Samples 201 to 205 were prepared by substituting the coupler represented by I) with equimolar amounts as shown in Table 9.
Sample 206 was prepared by replacing the comparative couplers (2) and (3) shown in Chemical formula 95. Next, the sample 105 manufactured in Example 1
Sample 2 as in Samples 201 to 206
07-212 was produced.

With respect to these prepared samples, the sensitivity, the storability of the light-sensitive material and the color image fastness of the cyan image were examined in the same manner as in Example 1. The results are shown in Table 9.

[0232]

[Chemical 95]

[0233]

[Table 9]

From the results shown in Table 9, sample 105 in which the acylacetamide type coupler of the present invention represented by the general formula (I) and the coupler represented by the general formula (II) or the general formula (III) were used, It can be seen that 207 to 211 have a slight improvement in sensitivity when compared with the comparative samples 101 and 201 to 205, and have the effect of improving the storability and color image fastness of the light-sensitive material. The use of couplers (2) and (3) used as comparative couplers for cyan couplers represented by the general formula (II) or (III) is effective in terms of sensitivity, storability of photosensitive material, and color image fastness. The inferiority can be known from the comparison between the sample 212 and the samples 105 and 207 to 211. Further, the combination of the comparative couplers (2) and (3) with the acylacetamide type coupler of the present invention in which the acyl group is represented by the general formula (I) has a small effect of improving the above-mentioned various properties. ~ 21
1. It can be known from the mutual comparison between the sample 206 and the samples 101 and 201 to 205. Furthermore, the fastness of the magenta color image in this example was examined by the same method.
Or, a value of 97 was obtained. From this result, it is understood that the sample having the constitution of the present invention provides a well-balanced and robust color image storability of three colors.

Example 3 Using the samples 101 to 110 prepared in Example 1 and the samples 201 to 212 prepared in Example 2, the amount of potassium bromide in the color developing solution of the color development process used in Example 1 was measured. The amount of tank liquid is 1.4g to 2.0g, and the replenisher is 0.4g.
Was set to 0 g, the replenishment rate was 300 ml / m ² , the color development processing temperature was 40.0 ° C., and the same exposure as in Example 1 was applied to perform processing. This process is called process B, and the process of the first embodiment is called process A. The samples obtained by carrying out the treatment B were processed in the same manner as in (1) of Example 1 to obtain the sensitivity for yellow density for samples 101-112 and the sensitivity for cyan density for samples 201-212. The sensitivity difference (ΔS _AB ) from the treatment B was calculated based on A.

Next, as Process C, the amount of potassium bromide in the color developing solution was set to 3.0 g for the tank solution and 0 g for the replenishing solution, and the color developing agent 2-methyl-4- [N-ethyl-N- (β −
The amount of hydroxyethyl) amino] aniline sulfate was adjusted to 6.0 g for the tank liquid and 10.5 g for the replenisher, the replenishment amount was 200 ml / m ^2, and the processing temperature for color development was 40.0 ° C. The same treatment was carried out, the sensitivity was obtained by the same method, and the sensitivity difference (ΔS _AC ) from the treatment C was calculated on the basis of the treatment A.

Process D is color developing agent 2-methyl-4-
[N-ethyl-N- (β-hydroxyethyl) amino]
The aniline sulfate was replaced with 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline sulfate in an equimolar amount, and the color development time was shortened to 2 minutes and 30 seconds. Similarly, the sensitivity was obtained, and the difference from the treatment D was calculated using the treatment A as a reference. These results are shown in Table 1.
It shows in 0.

[0238]

[Table 10]

From the results shown in Table 10, yellow of Samples 102 to 110 using the acylacetamide type coupler having the acyl group of the present invention represented by the general formula (I) and the coupler represented by the general formula (II) or (III). It is clear that the sensitivity of the color image and the sensitivity of the cyan color images of Samples 207 to 211 have a small fluctuation range of the sensitivity as compared with other comparative samples.
It can be seen that good photographic performance can be obtained even when the low replenishment amount processing of the color developing solution is carried out as in Examples C and C. Further, it can be seen that good results can be obtained even when the processing in which the color developing agent is changed is carried out. In the comparative sample,
It was found that, when the difference in sensitivity was extended and the developing processing time was extended to obtain a sensitivity almost equal to that of the processing A, the fog was remarkably increased and the gradation was softened.

Example 4 Samples 102, 104, 106 and 10 produced in Example 1
8 and the samples 207, 209 and 210 produced in Example 2.
7 kinds of samples were examined in Japanese Examined Japanese Patent Publication No. 2-32615 and Japanese Examined Publication 3-3
A film unit with a lens was produced according to the method described in 9784. These seven types of lens-equipped film units were used to photograph various subjects under the same conditions, and were subjected to the color development processing of processing D used in Example 3 to obtain color negatives, all of which were good color negative images. Also, using these color negatives, Fuji Minilab Champion, printer processor FA-140 (manufactured by Fuji Photo Film Co., Ltd.) was used to print on Fuji Color Paper, Super FA, Type II (color development at this time was C
P-43FA was used), but good color prints could be obtained.

Example 5 Japanese Patent Application Laid-Open No. 2-854, Example 1, and Sample 101 were prepared according to the method described. This is designated as Sample 501. next,
The coupler C-1 of the third and fourth layers of the red-sensitive emulsion layer is IIIC-34 of the present invention, the coupler C-2 is IIIC-36, and
The fifth layer couplers C-6 and C-8 are replaced with IIIC-37 and III
C-33 is replaced with an equimolar amount, and the couplers (C-5, C-7) of the 12th and 13th layers of the blue-sensitive emulsion layer are substituted with an acylacetamide represented by the formula (I) in which the acyl group of the present invention is represented. Type coupler (Y-25, Y-2), (Y-5
5, Y-9), (Y-52, Y-8) and (Y-10 /
(Y-53 = 1/1, Y-29 / Y-8 = 1/2, each molar ratio), and the coupler C-8 of the 13th layer was replaced with IIIC-34, IIIC-36, IIIC-. 42,
Sample 502 with the same molar amount as IIIC-37
505 was produced.

The samples 501 to 505 thus produced were subjected to white gradation exposure and then subjected to the color development processing described in the same Example 1. When the yellow and cyan densities of the obtained color image were examined, Sample 50 satisfying the constitution of the present invention was obtained.
Nos. 2 to 505 showed good color development and high sensitivity. When the temporal stability of these samples was examined under the same conditions as in Example 1, it was found that samples 502 to 505 exhibited excellent stability. It was also confirmed that the color image fastness also showed good results.

[0243]

In the silver halide color photographic light-sensitive material, the acylacetamide type coupler in which the acyl group of the present invention is represented by the general formula (I) and the general formula (II) or (II)
By using the coupler represented by I), high color-developing property is imparted, the storability of the light-sensitive material over time and the color image fastness are excellent,
It is possible to provide a silver halide color photographic light-sensitive material having excellent stability in color development processing.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the acyl group is an acylacetamide represented by the following general formula (I). Type silver halide color photographic light-sensitive material containing a type coupler and a coupler represented by the general formula (II) represented by the following chemical formula 2 or the general formula (III) represented by the following chemical formula 3. . General formula (I) In the formula, R ₁ represents a substituent, and Q represents a non-metal atom group necessary for forming a 6-membered heterocycle or a 5-membered heterocycle containing 2 heteroatoms together with C. General formula (II) In the formula, R ₁ is —CONR ₄ R ₅ , —SO ₂ NR ₄ R ₅ ,
-NHCOR ₄ , -NHCOOR ₆ , -NHSO
₂ R _6, -NHCONR ₄ R ₅ or -NHSO ₂ NR
₄ R ₅ , R ₂ is a group capable of substituting on the naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, X is a hydrogen atom or an aromatic primary amine developer oxidant. Respective groups that can be separated by a coupling reaction are shown. However, R
₄ and R ₅ may be the same or different and each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₆
Represents an alkyl group, an aryl group or a heterocyclic group. k
When _two or more are present, R _2's may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring.
In addition, a dimer or a multimer of R ₁ , R ₂ , R ₃ or X which is bonded to each other via a divalent or divalent or higher valent group may be formed. General formula (III): In the formula, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, R ² represents an aryl group, and Z represents a hydrogen atom or a coupling-off group.