JPH052247A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photosensitive material without the color picture changed for a long period and having high-degree preservability. CONSTITUTION:At least one kind of the acylacetamide-type yellow coupler with the acyl group shown by formula I and at least one kind selected from the compds. having formula II are incorporated into this silver halide photosensitive material. In formula I, R1 is a monvalent group, Q is a nonmetallic atom group forming a heterocyclic ring, and R1 is not hydrogen atom and does not form a ring by the combination with Q. In formula II, Ra1, Ra2 and Ra3 are an aliphatic or aromatic group, Ya1, Ya2 and Ya3 are -O-, -S- and -N(Ra4)-, k m, n and q are 0 or 1, k, m, n and q are not simultaneously 1 when q=1, and k, m, and n are not simultaneously 0 when q=0.

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, and more specifically to a silver halide color photographic light-sensitive material in which fading or discoloration of a dye image finally obtained by development processing is prevented. It is about materials.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material generally has a silver halide emulsion layer which is sensitive to the three primary colors of red, green and blue, and three types of color formers (couplers) in each emulsion layer are provided in respective layers. A color image is reproduced by a so-called subtractive method, in which a color is developed in a relationship between the perceived color and the complementary color. The color image obtained by photographic processing of this silver halide color photographic light-sensitive material is composed of an azomethine dye or an indoaniline dye formed by a reaction between an oxide of an aromatic primary amine color developing agent and a coupler. It is common.

However, the color photographic light-sensitive material having such an excellent system has become insufficient to meet the customer's demand for high quality. Among them, the color-forming dye obtained from the yellow dye-forming coupler still has some problems to be overcome. First, the extinction coefficient of the coloring dye is smaller than that of the dye obtained from the magenta dye-forming coupler or the cyan dye-forming coupler.
In order to obtain the same density as magenta and cyan, many yellow couplers must be used, secondly it is not always a satisfactory hue to faithfully reproduce the color of the subject, and thirdly the coloring dye. And uncolored couplers are not stable to light and heat, and if exposed to sunlight for long periods of time or stored under high temperature and high humidity, the dye image may become discolored or discolored or the white background may be colored, resulting in deterioration of image quality. Is caused.

In order to solve these problems, attempts to improve color formation by improving couplers and adding coexisting substances such as specific phenol compounds and sulfonamide compounds have been unsuccessful.

On the other hand, it is known to use an anti-fading agent or an ultraviolet absorber as a method for improving the fastness of an image. Of these, examples of anti-fading agents include hydroquinones, hindered phenols, catechols, gallic acid esters, aminophenols, hindered amines, chromanols, indanes and phenolic hydroxyl groups of these compounds are silylated and acylated. It is known to add etherified or alkylated ethers or esters, and further metal complexes.

However, these compounds have little effect on increasing the extinction coefficient of the resulting yellow dye. Moreover, even though it has an effect on the magenta dye, it is not enough on the yellow dye, and changes the hue, causes fog, causes poor dispersion, or causes microcrystal formation after emulsion coating. There are also things.

Japanese Patent Laid-Open Nos. 63-113536 and 1-
289952, 1-284853, and JP-A-6-26
No. 3-256952 proposes a pentavalent phosphorus compound having a specific structure in order to make a dye image obtained from a yellow dye-forming coupler fast and to improve spectral absorption characteristics.

In addition, Japanese Examined Patent Publication Nos. 48-32728 and 63.
-19518, JP-A-55-67741, 61-
107150, 63-301941, JP-A-2-
12146 and JP-A-3-25437 propose a trivalent phosphorus compound having a specific structure.

Combinations of these compounds with conventionally known yellow dye-forming couplers are insufficient in the photographic characteristics, image fastness and the like as described above.

In this sense, the coupler has improved coloring properties and photographic properties, and has no adverse effect on them.
A technique for suppressing fading and discoloration of an image has been desired.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which does not discolor a color image for a long period of time and has a high storability.

Another object of the present invention is to have a sufficient effect of preventing fading or discoloration of a yellow color image without changing the hue, inhibiting the color development of the coupler or causing fog, and microcrystals after being applied. Another object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel anti-fading agent that does not cause the above phenomenon.

Another object of the present invention is that it has excellent solubility in high-boiling point organic solvents, does not produce fine crystals before and after coating, and does not adversely affect other photographic additives. An object is to provide a silver halide color photographic light-sensitive material containing an anti-fading agent.

Another object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in color development characteristics and photographic characteristics, has a strong yellow color image, and is less colored in unexposed areas.

[0015]

As a result of various investigations by the present inventors, at least one acylacetamide type yellow dye-forming coupler whose acyl group is represented by the following general formula (I) and the following general formula (a) are used. It has been found that the object of the present invention is achieved by incorporating at least one selected from the compounds represented.

[0016]

[Chemical 3] In the formula, R ₁ represents a monovalent group, and Q is 3 to 5 together with C.
Represents a non-metallic atomic group necessary for forming a 3-membered 5-membered heterocyclic ring having at least one hetero atom selected from N, S, O and P in the ring. However, R ₁ is not a hydrogen atom and does not combine with Q to form a ring.

[0017]

[Chemical 4] In the formula, R _a1 , R _a2 and R _a3 represent an aliphatic group and an aromatic group, respectively. Y _a1 , Y _a2 and Y _a3 are -0-,-
S- and -N (R _a4 ) _-are represented, and k, m, n and q are 0 or 1. Here, R _a4 represents a hydrogen atom, an aliphatic group or an aromatic group. However, when q is 1,
k, m and n are not 1 at the same time, and when q is 0, k, m and n are not 0 at the same time. R
Any two of _a1 , R _a2 and R _a3 may be bonded to form a 5- to 9-membered ring together with a phosphorus atom, in which k, m
And n may be 1 at the same time.

R _a4 may be bonded to R _a1 , R _a2 or R _a3 to form a 5- or 6-membered ring.

The term "aliphatic" as used in the present invention means linear, branched or cyclic, which may be saturated or unsaturated, such as alkyl, alkenyl, alkynyl, cycloalkyl,
Alternatively, it represents cycloalkenyl, which may further have a substituent. The aromatic mentioned in the present invention represents aryl, which may further have a substituent.

The present invention will be described in more detail below.

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

[0022]

[Chemical 5] In the formula (YY), R ₁ is a monovalent substituent except hydrogen,
Q is a 3- to 5-membered hydrocarbon ring together with C or at least 1
R ₂ is a hydrogen atom, a halogen atom (F) or a non-metal atom group necessary for forming a 3- to 5-membered heterocycle containing a heteroatom selected from N, S, O, and P in the ring. , Cl, Br,
I, the same in the following description of formula (YY). ) An alkoxy group, an aryloxy group, an alkyl group or an amino group is represented by R
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 1 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, Alkylsulfonyl group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group Examples of the leaving group include a heterocyclic group bonded to the coupling active position at a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, a halogen. There is a child.

When the substituent in formula (YY) 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 (YY) 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-pentadecylphenyl, 2,4- Di-t-pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl).

Whether the substituent in the formula (YY) is a heterocyclic group,
Or, when containing a heterocycle, unless otherwise specified, the heterocyclic group is a 3 to 8-membered substituted group containing at least one hetero atom selected from O, N, S, P, Se and Te in the ring. Optionally a monocyclic or condensed ring heterocyclic group, for example, 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1
-Imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimide, phthalimido, 1-benzyl-2,4-imidazolidindione-3-yl).

The substituents preferably used in formula (YY) are described below.

In the formula (YY), R ₁ is preferably a halogen atom, a cyano group, or a monovalent group (for example, an alkyl group) having a total carbon number (hereinafter abbreviated as C number) 1 to 30 which may be substituted. , An alkoxy group) or a C number of 6 to
30 monovalent groups (for example, an aryl group and an aryloxy group), and the substituent thereof is, for example, a halogen atom,
There are alkyl groups, alkoxy groups, nitro groups, amino groups, carbonamide groups, sulfonamide groups, and acyl groups.

In the formula (YY), Q is preferably a C number of 3 to 5 which may be substituted with C as well as any of 3 to 5 members.
30 hydrocarbon rings or at least one N, S, O, P
Represents a group of non-metal atoms required to form a heterocycle having a C number of 2 to 30 containing a heteroatom selected from Further, the ring formed by Q together with C may contain an unsaturated bond in the ring. Examples of the ring formed by Q together with C include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring, oxetane ring, oxolane ring, 1,3-dioxolane ring, thietane ring, thiolane ring, pyrrolidine. There is a ring. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group and an arylthio group.

In the formula (YY), R ₂ is preferably a halogen atom, which may be substituted, and has a C number of 1 to 3.
An alkoxy group of 0, an aryloxy group having a C number of 6 to 30,
It represents an alkyl group having a C number of 1 to 30 or an amino group having a C number of 0 to 30, and examples of the substituent thereof include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In the formula (YY), R ₃ is preferably a halogen atom, any of which may be substituted, and has a C number of 1 to 30.
Alkyl group, C6-30 aryl group, C3-3
0 alkoxy group, C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C
A carbonamido group having 1 to 30 carbon atoms, a sulfonamide group having 1 to 30 carbon atoms, a carbamoyl group having 1 to 30 carbon atoms, and 0 to C atoms
30 sulfamoyl group, C 1-30 alkylsulfonyl group, C 6-30 arylsulfonyl group, C 1-30 ureido group, C 0-30 sulfamoylamino group, C 2 30 alkoxycarbonylamino group, C 1-30 heterocyclic group, C 1-30 acyl group, C 1-30 alkylsulfonyloxy group, C 6-30 arylsulfonyloxy group, Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group and an arylsulfonyl group. , An acyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonylamino group, Sulfamoyl group, a ureido group, a cyano group, a nitro group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group.

In the formula (YY), k preferably represents an integer of 1 or 2, and the substitution position of R ₃ is

[0033]

[Chemical 6] On the other hand, the meta position or the para position is preferable.

In the formula (YY), 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 optionally substituted. It is a 5- to 7-membered monocyclic or condensed-ring heterocyclic group, and examples thereof include succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, and 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 (YY) will be described below.

R ₁ is particularly preferably a halogen atom,
It is an alkyl group and most preferably a methyl group. Q
Is particularly preferably a group of non-metal atoms forming a ring with 3 to 5 members of a ring formed with C, for example,-(CR
_{2) 2 -, - (CR} 2) 3 -, - (CR 2) 4 - a. Here, R represents a hydrogen atom, a halogen atom or an alkyl group. However, a plurality of R and CR ₂ may be the same or different.

Q is most preferably-(CR ₂ ) _2-, which forms a 3-membered ring with the C to which it is attached.

R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6 (eg methyl, trifluoromethyl, ethyl, isopropyl, t-butyl),
Alkoxy group having 1 to 8 C numbers (eg, methoxy, ethoxy, methoxyethoxy, butoxy), or 6 to 2 C numbers
4 aryloxy groups (eg, phenoxy group, p-tolyloxy, p-methoxyphenoxy), most preferably chlorine atom, methoxy group or trifluoromethyl group.

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 an alkoxy group, an alkoxycarbonyl group, a carbonamido group or a sulfonamide group.

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

[0042]

[Chemical 7] Formula (YY-1) in Z is _{-0-CR 4 (R 5)} -,
_{-S-CR 4 (R 5)} -, - NR 6 -CR 4 (R 5)
_{-, - NR 6 -NR 7 -} , - NR 6 -C (O) -, - C
_{R 4 (R 5) -CR 8} (R 9) - or -CR ₁₀ = CR
₁₁ - represents a.

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. R ₆ and R ₇ represent a hydrogen atom, an alkyl group, 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 (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

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

[0045]

[Chemical 8] In formula (YY-2), at least one of R12 and R13 is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group. , An alkylsulfonyl group, an arylsulfonyl group or an acyl group, and the other may be a hydrogen atom, 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. Formula (YY-2)
The C number of the aryloxy group represented by is 6 to 30, preferably 6 to 24, and more preferably 6 to 15.

[0046]

[Chemical 9] In formula (YY-3), W is a pyrrole ring together with N,
It represents a group of non-metal atoms necessary for forming a pyrazole ring, an imidazole ring or a traazole ring. Here, the ring represented by formula (YY-3) may have a substituent, and preferred examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group, an aryl group and an amino group. , An alkoxy group, an aryloxy group or a carbamoyl group. The C number of the heterocyclic group represented by the formula (YY-3) is 2 to 30, preferably 2 to 24,
More preferably, it is 2-16.

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

The coupler represented by the formula (YY) has substituents R ₁ , Q, X or

[0049]

[Chemical 10] In, a dimer or a multimer having a valence of 2 or more may be bonded to each other. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

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

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

[0054]

[Chemical 14]

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

[0059]

[Chemical 19]

[0060]

[Chemical 20] Specific examples of the yellow coupler represented by the formula (YY) are shown below.

[0061]

[Chemical 21]

[0062]

[Chemical formula 22]

[0063]

[Chemical formula 23]

[0064]

[Chemical formula 24]

[0065]

[Chemical 25]

[0066]

[Chemical formula 26]

[0067]

[Chemical 27]

[0068]

[Chemical 28]

[0069]

[Chemical 29]

[0070]

[Chemical 30]

[0071]

[Chemical 31]

[0072]

[Chemical 32]

[0073]

[Chemical 33] The yellow coupler of the present invention represented by the formula (YY) can be synthesized by the following synthetic route.

[0074]

[Chemical 34] Here, the compound a is a compound of J. Chem. Soc. (C), 1
968, 2548, J. Am. Chem. Soc. , 1
934, 56, 2710, Synthesis, 197.
1,258, J. Org. Chem. , 1978, 4
3, 1729, CA, 1960, 66, 18533y and the like.

Compound b is synthesized using thionyl chloride, oxalyl chloride or the like without solvent or in a solvent such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N, N-dimethylformamide, N, N-dimethylacetamide. The reaction temperature is usually -20 ° C to 150 ° C, preferably -10 ° C to 80 ° C.

The compound c is synthesized by converting ethyl acetoacetate into an anion using magnesium methoxide or the like and adding b into the anion. The reaction is carried out without solvent or using tetrahydrofuran, ethyl ether or the like, and the reaction temperature is generally -20 ° C to 60 ° C, preferably -10 ° C to 30 ° C.
Is. Compound d is synthesized by reacting compound c with ammonia as a base, aqueous NaHCO ₃ solution, aqueous sodium hydroxide solution or the like without solvent or in a solvent such as methanol, ethanol or acetonitrile. The reaction temperature is generally -20 ° C to 50 ° C, preferably -1.
It is 0 ° C to 30 ° C.

The coupler e of the present invention is synthesized by reacting the compounds d and g without a solvent. The reaction temperature is usually 100 to 150 ° C., preferably 100 to 120.
℃. When X is not H, the leaving group X is introduced after chlorination or bromination to synthesize the compound f. The coupler e of the present invention is a chloro substitution product with sulfuryl chloride, N-chlorosuccinimide, etc. in a solvent such as dichloroethane, carbon tetrachloride, chloroform, methylene chloride, tetrahydrofuran, etc., or a bromo substitution product with bromine, N-bromosuccinimide, etc. And At this time, the reaction temperature is -20
C. to 70.degree. C., preferably -10.degree. C. to 50.degree.

Then, the chloro-substituted product or the bromo-substituted product and the proton adduct of the leaving group, H-X, are combined with methylene chloride, chloroform, tetrahydrofuran, acetone, acetonitrile, dioxane, N-methylpyrrolidone, N, N'-dimethylimidazolidine. Reaction temperature -20 ° C to 150 ° C, preferably -10 ° C in a solvent such as 2-one, N, N-dimethylformamide, N, N-dimethylacetamide.
The coupler f of the present invention can be obtained by reacting at -100 ° C. At this time, triethylamine, N
-A base such as ethylmorpholine, tetramethylguanidine, potassium carbonate, sodium hydroxide or sodium hydrogen carbonate may be used.

The synthesis examples of the coupler of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplified Compound YY-25 Gotkis, D. et al. et al. Am. Chem. S
oc. 1-methylcyclopropanecarboxylic acid 25 synthesized by the method described in No. 1, 1934, 56, 2710.
g, 100 ml of methylene chloride and 1 ml of N, N-dimethylformamide, 38.1 g of oxalyl chloride was added dropwise at room temperature over 30 minutes. After dropping, the mixture was reacted at room temperature for 2 hours, and methylene chloride and excess oxalyl chloride were removed under reduced pressure of an aspirator to obtain an oily substance of 1-methylcyclopropanecarbonyl chloride.

100 ml of methanol was added dropwise to a mixture of 6 g of magnesium and 2 ml of carbon tetrachloride at room temperature over 30 minutes and then refluxed under heating for 2 hours, and then 32.6 g of ethyl 3-oxobutanoate was added over 30 minutes under reflux under heating. To do. After the dropping, the mixture is heated and refluxed for another 2 hours, and methanol is completely distilled off under reduced pressure of an aspirator. Tetrahydrofuran (100 ml) is added to the reaction product to disperse it, and 1-methylcyclopropanecarbonyl chloride obtained above is added dropwise at room temperature. After reacting for 30 minutes, the reaction solution was added with 300 ml of ethyl acetate,
After extraction with diluted sulfuric acid water and washing with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain 55.3 g of an oily product of ethyl 2- (1-methylcyclopropanecarbonyl) -3-oxobutanoate. ..

55 g of ethyl 2- (1-methylcyclopropanecarbonyl) -3-oxobutanoate, ethanol 1
60 ml of the solution is stirred at room temperature, and 60 ml of 30% aqueous ammonia is added dropwise thereto over 10 minutes. Then, the mixture is stirred for 1 hour, extracted with 300 ml of ethyl acetate, diluted hydrochloric acid, neutralized and washed with water, and the organic layer is dried over anhydrous sodium sulfate, and the solvent is distilled off (1-methylcyclopropanecarbonyl).
43 g of an ethyl acetate oil was obtained.

(1-methylcyclopropanecarbonyl)
34 g of ethyl acetate and N- (3-amino-4-chlorophenyl) -2- (2,4-di-t-pentylphenoxy)
44.5 g of butanamide is heated to reflux under an aspirator reduced pressure at an internal temperature of 100 to 120 ° C. After reacting for 4 hours, the reaction solution was purified by column chromatography with a mixed solvent of n-hexane and ethyl acetate to obtain 49 g of Exemplified Compound YY-25 as a viscous oil. The structure of the compound is MS spectrum, NMR
Confirmed by spectrum and elemental analysis. Synthesis example 2
Synthesis of Exemplified Compound YY-1 Exemplified Compound YY-25 2
2.8 g is dissolved in 300 ml of methylene chloride, and 5.4 g of sulfuryl chloride is added dropwise over 10 minutes under ice cooling. After reacting for 30 minutes, the reaction solution was washed well with water, dried over anhydrous sodium sulfate and then concentrated to obtain a chloride of Exemplified Compound YY-25. 1-
Exemplified compound Y- previously synthesized in a solution of 18.7 g of benzyl-5-ethoxyhydantoin, 11.2 ml of triethylamine and 50 ml of N, N-dimethylformamide.
25 chloride to N, N-dimethylformaldehyde 50
What was melt | dissolved in ml is dripped at room temperature over 30 minutes.

Then, after reacting at 40 ° C. for 4 hours, the reaction solution is extracted with ethyl acetate (300 ml), washed with water, washed with 2% triethylamine aqueous solution (300 ml), and then neutralized with diluted hydrochloric acid. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain an oily substance which was crystallized from a mixed solvent of n-hexane and ethyl acetate. The precipitated crystals were filtered and n-
The crystals were washed with a mixed solvent of hexane and ethyl acetate and dried to obtain 22.8 g of crystals of Exemplified Compound YY-1.

The structure of the compound was confirmed by MS spectrum, NMR spectrum and elemental analysis. The melting point is 132.
Was ~ 3 ° C.

The standard amount of the yellow dye-forming coupler having an acyl group represented by the general formula (I) used in the present invention is, based on 1 mol of silver halide in the same layer,
It is in the range of 0.001 to 1 mol, preferably 0.01
~ 0.5 mol.

The yellow dye-forming coupler having an acyl group represented by formula (I) of the present invention may be used in combination with a conventionally known coupler.

Next, the compound represented by formula (a) will be described.

The aliphatic group as R _a1 , R _a2 and R _a3 is, for example, methyl, ethyl, butyl, t-butyl, i.
It represents -butyl, 2-ethylhexyl, dodecyl, dodecyloxyethyl, benzyl, phenethyl, allyl, vinyl, and is preferably a linear or branched, substituted or unsubstituted alkyl group. The aromatic group represented by R _a1 , R _a2 and R _a3 represents, for example, phenyl, naphthyl, 4-methylphenyl, 4-methoxyphenyl or 2-methylphenyl, preferably phenyl or substituted phenyl.

Of the compounds represented by the general formula (a),
In terms of the effects of the present invention, the following general formulas (a-1) and (a-
The compounds represented by 2), (a-3) and (a-4) are preferable.

[0090]

[Chemical 35]

[0091]

[Chemical 36]

[0092]

[Chemical 37]

[0093]

[Chemical 38] In the general formula (a-1), R _a1 and n have the same meanings as defined in the general formula (a), and A represents an atom group forming a substituted or unsubstituted benzene ring. X _a1 is a single bond, a substituted or unsubstituted methylene group, —S—, —O—,
It represents-(O-, -N (R _a9 )-, -SO ₂ and -SO-. R _a9 represents a hydrogen atom, an aliphatic group or an aromatic group.

The substituent on the benzene ring represented by A may be a substitutable group, for example, an aliphatic group,
Aromatic group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, Aliphatic carbamoyl group, aromatic carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic sulfamoyl group, aromatic sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, aliphatic amino group, aromatic amino Examples thereof include a group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic thio group, an aromatic thio group, a cyano group, a nitro group, a hydroxyamino group and a halogen atom.

In this case, preferable substituents are an aliphatic group and an acylamino group, and an alkyl group is particularly preferable.

Substitution with a substituted methylene group in X _a1 means
An aliphatic group is substituted, and an alkyl group which may have a substituent is preferable.

From the viewpoint of the effect of the present invention, X _a1 is a single bond, a substituted or unsubstituted methylene group, —S—, or —O—, and particularly preferably a single bond or a substituted or unsubstituted methylene group. The case is preferred.

From the viewpoint of the effect of the present invention, R _a1 is preferably an alkyl group and a phenyl group or a substituted phenyl group,
It is more preferable in the case of a phenyl group or a substituted phenyl group, and in those cases, the case where n is 0 is most preferable.

In the general formula (a-2), R _a1 , R _a2 ,
R _a3 , n and m have the same _meaning as defined in formula (a).

From the viewpoint of the effect of the present invention, it is preferable that n and m are 1, in which case R _a2 and R _a3 are most preferably an alkyl group and an aromatic group, especially a phenyl group or a substituted phenyl group. preferable.

From the viewpoint of the effect of the present invention, R _a1 is preferably an alkyl group and a phenyl group or a substituted phenyl group, and more preferably a phenyl group or a substituted phenyl group.

In the general formula (a-3), R _a1 , k and n have the same meanings as defined in the general formula (a), and A and X _a1 are the same as those defined in the general formula (a-1). Are synonymous.

From the viewpoint of the effect of the present invention, it is preferable that R _a1 is an alkyl group and a phenyl group or a substituted phenyl group. Further, it is more preferable that k is 0 and R _a1 is a phenyl group or a substituted phenyl group. The preferred range of A and X _a1 is the same as in the case of the general formula (a-1).

In the general formula (a-4), R _a1 and k
Has the same meaning as defined in formula (a). R _a5 , R
_a6 , R _a7 and R _a8 represent a hydrogen atom or a substituent,
n _a and m _a are integers of 0, 1 and 3.

From the viewpoint of the effect of the present invention, it is preferable that R _a1 is an alkyl group, a phenyl group or a substituted phenyl group. R _a5 and R _a6 are preferably bulky substituents, for example, tertiary alkyl groups, secondary alkyl groups and substituents having 6 or more carbon atoms, particularly preferably tertiary alkyl groups.

In terms of the effect of the present invention, the general formula (a-1),
The compounds represented by (a-2) and (a-4) are preferable, and the compounds represented by general formulas (a-2) and (a-4) are particularly preferable.

The compound represented by the general formula (a) of the present invention may be used in combination with a known anti-fading agent as described below, in which case the anti-fading effect is further enhanced. Similarly, two or more compounds represented by the general formula (a) may be used in combination.

The compound of the general formula (a) of the present invention varies depending on the kind of the coupler, but it is suitable to use it in the range of 0.5 to 300 mol% with respect to the coupler used, preferably 1 to It is in the range of 200 mol%.

Representative examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

[0110]

[Chemical Formula 39]

[0111]

[Chemical 40]

[0112]

[Chemical 41]

[0113]

[Chemical 42]

[0114]

[Chemical 43]

[0115]

[Chemical 44]

[0116]

[Chemical 45]

[0117]

[Chemical 46]

[0118]

[Chemical 47]

[0119]

[Chemical 48]

[0120]

[Chemical 49]

[0121]

[Chemical 50]

[0122]

[Chemical 51]

[0123]

[Chemical 52]

[0124]

[Chemical 53] The compound represented by formula (a) of the present invention is disclosed in
3-113536, 63-256952, 61
-137150, JP-A-2-12146, JP-B-6
It can be synthesized by the method described in JP-A-3-19518, JP-A-3-25437 or the like or a method analogous thereto.

The compound represented by the general formula (a) of the present invention is preferably added to the layer containing the yellow dye-forming coupler represented by the general formula (I) of the present invention. More preferably, the compound of the general formula (a) and the yellow coupler represented by the general formula (I) coexist. Therefore, when the oil-in-water dispersion method described below is adopted, it is preferable to coemulsify the compound of the present invention and the yellow coupler rather than separately emulsifying them and adding them to the same layer.

The compound and / or color coupler of the present invention can be introduced into the light-sensitive material by various known dispersion methods. It can be usually added by an oil-in-water dispersion method known as an oil protect method. After being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or a gelatin aqueous solution may be added to a solution of the compound of the present invention and / or a color coupler containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble compound and / or color coupler of the present invention can also be dispersed by a so-called Fisher dispersion method. The low boiling point organic solvent may be removed from the compound and / or color coupler dispersion method of the present invention by a method such as distillation, washing with noodles or ultrafiltration, and then mixed with a photographic emulsion. The dispersion medium of the compound and color coupler of the present invention has a dielectric constant (25 ° C.) of 2 to
It is preferable to use a high boiling point organic solvent having a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound. The compound of the present invention is preferably used by being coemulsified with a color coupler.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. In addition, specific examples of latex for impregnating the process, effect, and impregnation of latex as one of the polymer dispersing methods are as follows.
US Patent No. 4,199,363, West German Patent Application No. (O
LS) 2,541,274 and 2,541,230
No. PCT International Publication No. WO88 / 00 for a dispersion method using an organic solvent-soluble polymer.
No. 723.

As the high boiling point organic solvent which can be used in the above oil-in-water dispersion method, phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis ( 2,4-di-t-
Amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (for example, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate,
Tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenylphosphonate), benzoic acid esters (for example, 2-ethylhexyl benzoate, 2,4-dichlorobenzoate,
Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide), alcohols or phenols (isostearyl alcohol, 2,4-di). -Tert-amylphenol), aliphatic esters (for example, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate). Rate), aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (chlorine content 10% to 80%).
Paraffins), trimesic acid esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, and the like. Further, as an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher and about 160 ° C. or lower (for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination.

The color light-sensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color fog inhibitor.

Various kinds of anti-fading agents can be used in combination with the light-sensitive material of the present invention. Hindered phenols centering on hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols and bisphenols as organic anti-fading agents for cyan, magenta and / or yellow images , Gallic acid derivatives, methylenedioxybenzenes,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent include US Pat. Nos. 2,360,290 and 2,418,613,
2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944, 4 , 430,425, British Patent No. 1,363,921
No. 2,710,801 and 2,816, US Pat.
No. 028, etc .; hydroquinones; US Pat.
Nos. 432,300, 3,573,050, 3,5
74,627, 3,698,909, 3,76
4,337, 6-hydroxychromans, 5-hydroxychromans, spirochromans described in JP-A-52-152225; U.S. Pat. No. 4,360,589.
Spiroindans described in US Pat. No. 2,735,735.
765, British Patent No. 2,066,975, JP-A-5
9-10539, p-alkoxyphenols described in JP-B-57-19765, etc .; US Pat. No. 3,70.
0,455, 4,228,235, JP-A-52-
No. 72224, Japanese Patent Publication No. 52-6623 and the like; gallic acid derivatives described in US Pat. No. 3,457,079; US Pat. No. 4,332,88.
Methylenedioxybenzenes described in No. 6; Japanese Patent Publication No. 56
-Aminophenols described in No. 21144; U.S. Pat. Nos. 3,336,135, 4,268,593, British Patents 1,326,889, 1,354,313.
No. 1,410,846, Japanese Examined Patent Publication No. 51-1420
JP-A-58-114036 and 59-53846.
No. 59-78344 and the like; hindered amines; US Pat. Nos. 4,050,938 and 4,241.
155, British Patent No. 2,027,731 (A) and the like, and the metal complexes and the like. These compounds are usually used in an amount of 5 to 10 with respect to the corresponding color coupler.
The object can be achieved by co-emulsifying 0% by weight of the coupler and adding it to the photosensitive layer.

In order to prevent the deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to the cyan coloring layer.

As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, those described in US Pat. No. 3,533,794) and a 4-thiazolidone compound (for example, US Pat. No. 3,314,794) are used. No. 3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, US Pat.
705,805 and 3,707,395), butadiene compounds (US Pat. No. 4,045,22).
9) or a benzoxazole compound (for example, US Pat. Nos. 3,406,070 and 4,27).
Those described in No. 1,307) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted in a specific layer. Among them, the benzotriazole compound substituted with the above aryl group is preferable.

To apply the present invention to multilayer silver halide color photographic light-sensitive materials, a blue-sensitive silver halide emulsion layer containing a yellow coupler and a green-sensitive silver halide emulsion layer containing a magenta coupler are provided on a support. Although at least one red-sensitive silver halide emulsion layer containing a cyan coupler and a cyan coupler can be applied in this order, the order may be different. Also, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. Color reproduction of the subtractive method is carried out by containing a silver halide emulsion having sensitivity in each wavelength range and a color coupler forming a dye having a complementary color relationship with the light to be exposed in these light-sensitive emulsion layers. be able to. However, the photosensitive emulsion layer and the hue developed by the color coupler may not have the above correspondence.

The compound of the present invention can be applied to, for example, color paper, color reversal paper, direct positive color light-sensitive material, color negative film, color positive film, color reversal film and the like. Among them, a color photosensitive material having a reflective support (for example, color paper, color reversal paper) or a color photosensitive material for forming a positive image (for example,
It is preferably applied to a direct positive color light-sensitive material, a color positive film, a color reversal film).

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and the processing method and processing addition applied for processing the light-sensitive material. Examples of the agent include the following patent publications, particularly European Patent EP 0,355,660A2 (Japanese Patent Application No.
Those described in No. 107011) are preferably used.

[0137]

[Table 1]

[0138]

[Table 2]

[0139]

[Table 3]

[0140]

[Table 4]

[0141]

[Table 5] Further, as the cyan coupler, in addition to the diphenylimidazole type cyan coupler described in JP-A-2-33144, 3 described in European Patent EP 0,333,185A2 is used.
-Hydroxypyridine-based cyan couplers (among others, couplers (42) listed as specific examples are 4-equivalent couplers having a chlorine leaving group to make them 2-equivalent, and couplers (6) and (9) are particularly preferable) and Japanese Patent Laid-Open No. 64-322
Cyclic active methylene-based cyan couplers described in No. 60 (among others, coupler examples 3 and 8 listed as specific examples,
Is particularly preferred).

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used, but especially for the purpose of rapid processing. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content substantially free of silver iodide of 90 mol% or more, further 95% or more, and particularly 98% or more.

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is added in order to improve the sharpness of an image and the like, as described in European Patent EP 0,337,490A2.
A dye decolorizable by treatment (among others, an oxonol dye) described on page 76 is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more,
It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a dihydric or tetravalent alcohol (eg, trimethylolethane).

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, a compound which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. It is possible to use a compound which chemically bonds with an oxidant of a group amine type color developing agent to form a chemically inactive and substantially colorless compound simultaneously or alone, for example, remaining in the film after storage after processing. It is preferable for preventing stains and other side effects due to the formation of color dyes by the reaction of the color developing agent or its oxidant with the coupler.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent.

As the support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable.

In exposure, US Pat. No. 4,88
It is preferable to use the band stop filter described in No. 0,726. This removes the light mixture,
Color reproducibility is significantly improved.

The light-sensitive material according to the present invention is described in Research Disclosure No. 17643, pages 28-29,
And the same No. Development can be carried out by a usual method described in the left column to the right column of page 615 of 18716. For example, a color development processing step, a desilvering processing step, and a water washing processing step are performed. In the desilvering step, instead of the bleaching step using a bleaching agent and the fixing step using a fixing solution, a bleach-fixing processing step using a bleach-fixing solution can be performed, a bleaching processing step, a fixing processing step, The bleach-fixing steps may be combined in any order. The stabilizing step may be performed instead of the washing step, or the stabilizing step may be performed after the washing step. Also, color development, bleaching, and fixing are performed in one bath.
A monobath processing step using a bath development bleach-fix processing solution can also be carried out. In combination with these processing steps, a pre-hardening step, a neutralizing step thereof, a stop-fixing step, a post-hardening step, an adjusting step, an intensifying step and the like may be performed. An optional intermediate water washing step may be provided between the above steps. In these processes, a so-called activator processing step may be performed instead of the color development processing step.

[0151]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these.

[0152]

【Example】

Example 1 16.1 g of a comparative yellow coupler Y-1 was weighed,
16.1 g of high boiling organic solvent dibutyl phthalate was added,
Further, 24 ml of ethyl acetate was added and dissolved, and this solution was emulsified and dispersed in 200 g of a 10 wt% gelatin aqueous solution containing 1.5 g of sodium dodecylbenzenesulfonate.

The total amount of this emulsified dispersion was adjusted to a high silver chloride emulsion 24.
7 g (silver 70.0 g / kg emulsion, silver bromide content 0.5 mol%), and coated on a triacetate film base having an undercoat layer so that the coated silver amount was 1.73 g / m ^2. Then, a gelatin layer was provided as a protective layer on the coating layer so that the dry film thickness was 1.0 μm to prepare Sample 101. As a gelatin hardener, 1-oxy-
3,5-Dichloro-s-triazine sodium salt was used.

In the same manner as in Sample 101, when the above emulsified dispersion was prepared, it was co-emulsified with a combination of a coupler and a color image stabilizer (addition of 100 mol% based on the coupler) as shown in Table A. Samples were prepared and applied in the same manner as sample 101 to make samples 102-153.

Each of the samples thus obtained was subjected to wedge exposure and then developed in the following processing steps.

(Processing step) (Temperature) (Time) Color development 35 ° C. 45 seconds Bleach fixing 30 to 35 ° C. 45 seconds Rinse (1) 30 to 35 ° C. 20 seconds Rinse (2) 30 to 35 ° C. 20 seconds Rinse (3) 30 to 35 ° C. for 20 seconds Drying 70 to 80 ° C. for 60 seconds The composition of each treatment liquid is as follows. (Color developer) Water 800 ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 1.5 g Potassium bromide 0.015 g Triethanolamine 8.0 g Sodium liquefied 1.4 g Potassium carbonate 25 g N-ethyl-N- (β -Methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate) 5.0 g N, N-bis (carboxymethyl) hydrazine 5.5 g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0 g Water was added. 1000 ml pH (25 ° C) 10.05. (Bleach fixer) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water added 1000 ml pH (25 ° C) 6.0. (Rinse solution) Ion-exchanged water (3 ppm or less for calcium and magnesium, respectively) Ultraviolet absorption filter manufactured by Fuji Photo Film Co., Ltd., which cuts light of 400 nm or less in each of 101 to 153 samples in which a dye image is formed in this way And was exposed for 15 days with a xenon tester (illuminance: 200,000 lux). The concentration residual rate at the initial concentration of 2.0 of each sample was obtained.

The measurement was performed with a Fuji Denshi Densitometer.

The results obtained are shown in Table A.

[0159]

[Table 6]

[0160]

[Table 7]

[0161]

[Chemical 54]

[0162]

[Chemical 55] From these results, the compound represented by the general formula (a) of the present invention is remarkably excellent in color image fastness when used in combination with the yellow dye-forming coupler having an acyl group represented by the general formula (I) of the present invention. Improvement, which was an unexpected result from the prior art.

Example 2 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and thereafter, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constitutional layers were further coated to prepare the following. A multilayer color photographic paper having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of fifth layer coating solution Cyan coupler (ExC) 32.0 g, color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-
8) To 5.0 g, 50.0 cc of ethyl acetate and 14.0 g of a solvent (Solv-6) were added and dissolved, and this solution containing 8 cc of sodium dodecylbenzenesulfonate was added.
After adding to 500 cc of 0% gelatin aqueous solution, it was emulsified and dispersed by an ultrasonic homogenizer to prepare an emulsified dispersion. On the other hand, silver chlorobromide emulsion (cube, average grain size of 0.
1: 4 mixture of 58 μm large size emulsion and 0.45 μm small size emulsion (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and 0.6 mol% of AgBr was locally contained in a part of the grain surface in each size emulsion). In this emulsion, the red-sensitizing dye E shown below was added to the emulsion of large size per mol of silver in an amount of 0.2.
9 × 10 ^-4 mol, or 1.1 × for small emulsions
10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

After coating the first layer to the fourth layer, the sixth layer and the seventh layer, a coating solution was prepared in the same manner as the fifth layer coating solution. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

In addition, Cpd-10 and Cpd-11 are provided in each layer.
The total amount is 25.0 mg / m ² and 50.0 mg / m ² , respectively.
It was added so as to be m ² .

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. (Blue sensitive emulsion layer) Sensitizing dye A

[0168]

[Chemical 56] And sensitizing dye B

[0169]

[Chemical 57] (2.0 × 10 ^-4 mol for large size emulsion and 2.5 × 10 ^-4 mol for small size emulsion per mol of silver halide) (Green-sensitive emulsion layer) Sensitization Dye C

[0170]

[Chemical 58] (Per mol of silver halide, 4.0 × 10 ⁻⁴ mol for large size emulsion, 5.6 × for small size emulsion)
10 ^-4 mol) and sensitizing dye D

[0171]

[Chemical 59] (7.0 × 10 ⁻⁵ mol for large size emulsion, 1.0 × for small size emulsion per mol of silver halide)
10 ^-5 mol) (red sensitive emulsion layer) Sensitizing dye E

[0172]

[Chemical 60] (Per mol of silver halide, 0.9 × 10 ⁻⁴ mol for large size emulsion, 1.1 × for small size emulsion)
10 ^-4 mol) was further the following compound was added per mol of silver halide 2.6 × 10 ^-3 mol.

[0173]

[Chemical formula 61] Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 8.5 × 10 ^-5 mol per mol of silver halide, respectively. 7.7 x 10 ^-4 mol, 2.5 x
10 ⁻⁴ mol was added.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively.

In order to prevent irradiation, the following dyes were added to the emulsion layer (the amount in parentheses represents the coating amount).

[0176]

[Chemical formula 62] (Layer constitution) The composition of each layer is shown below. Numbers are coating amount (g
/ M ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0 3: 8 mixture of large size emulsion of 0.88μ and small size emulsion of 0.70μ (silver molar ratio) Coefficients of variation of grain size distribution are 0.08 and 0.10, respectively, and bromide for each size emulsion (Silver 0.3 mol% is locally contained in a part of the grain surface) 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06.

Second Layer (Color Mixing Prevention Layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08.

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion with average grain size 0.55μ and small size emulsion 0.39μ (Ag molar ratio) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain in each size emulsion.) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40.

Fourth Layer (Ultraviolet Absorbing Layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24.

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having average grain size 0.58μ and small size emulsion 0.45μ (Ag molar ratio) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and 0.6 mol% of AgBr was locally contained in a part of the grain surface in each size emulsion.) 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 solvent (Solv-6) 0.14.

Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08.

Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol 0.17 (Modification degree 17%) Liquid paraffin 0.03

[0183]

[Chemical 63]

[0184]

[Chemical 64]

[0185]

[Chemical 65]

[0186]

[Chemical 66]

[0187]

[Chemical 67]

[0188]

[Chemical 68]

[0189]

[Chemical 69]

[0190]

[Chemical 70]

[0191]

[Chemical 71] First, a sensitometer (Fuji Photo Film Co., Ltd.
An FWH type, light source color temperature of 3200 ° K) was used, and gradation exposure of a three-color dispersion filter for sensitometry was performed. The exposure at this time is 250 CMS with the exposure time of 0.1 seconds.
Exposure amount.

The exposed samples were subjected to continuous processing (running test) using a paper processor using the solutions having the following processing steps and compositions until replenishment of twice the tank capacity for color development.

Treatment process Temperature Time Replenisher * Tank capacity (ml) (liter) Color development 35 ℃ 45 seconds 161 17 Bleach fixing 30-35 ℃ 45 seconds 215 17 Rinse (1) 30-35 ℃ 20 seconds -10 Rinse ( 2) 30-35 ° C 20 seconds -10 Rinse (3) 30-35 ° C 20 seconds 350 10 Dry 70-80 ° C 60 seconds * Replenishment amount per 1 m ² of light-sensitive material Rinsing is from (3) to (2), ( A tank countercurrent system from 2) to 1) was adopted.

The composition of each processing solution is as follows.

(Color Developer) Tank Solution Replenisher Water 800 ml 800 ml Ethylenediamine-N, N, N-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g Carbonic acid Potassium 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N , N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Water was added to 1000 ml 1000 ml pH (25 ° C) 10.05 10.45.

(Bleach-fixing solution) (tank solution and replenisher are the same) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Odor Ammonium chloride 40 g Water was added to 1000 ml pH (25 ° C) 6.0.

(Rinse solution) (tank solution and replenisher are the same) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less).

The sample thus obtained was designated as 1A,
Layer yellow coupler and color image stabilizer (color image stabilizer C
Other Samples 2A to 16A were prepared in the same manner as Sample 1A except that (pd-1 and Cpd-7 were additionally added) were combined and co-emulsified as shown in Table B.

The addition amount was 50 mol% based on the yellow coupler.

A color fading test was conducted on each of the samples thus formed with the dye image. To evaluate the effect of preventing discoloration, the yellow density residual rate at an initial density of 2.0 after exposure for 15 days using a xenon tester (illuminance: 200,000 Lux) was obtained. The results obtained are shown in Table B.

[0201]

[Table 8] As is clear from Table B, even in the case of a silver halide color photographic light-sensitive material having a multilayer structure, the sample of the present invention exhibits an excellent preventive effect, which is remarkably excellent as compared with the conventionally known techniques. It was something that was not attached.

Example 3 The coated sample prepared in Example 1 was exposed to light in the same manner as in Example 1,
Development processing was carried out to obtain 101 to 153 samples having a dye image formed thereon.

101 to form a dye image in this way
Density measurement of each sample of 153 was performed to examine photographic characteristics.
The photographic characteristics were evaluated at the maximum color density (Dmax), and the relative value was set to 100 for the sample without addition of the color image stabilizer.

These samples were left at 100 ° C. for 16 days. The yellow density (stain) of the unexposed area of each sample was measured, and the increase was evaluated. The measurement was carried out with a Fuji densitometer.

The results obtained are shown in Table C.

[0206]

[Table 9]

[0207]

[Table 10] From these results, when the compound represented by the general formula (a) of the present invention is used in combination with the yellow dye-forming coupler having an acyl group represented by the general formula (I) of the present invention,
The color development characteristics were not adversely affected, and the generation of stain was suppressed, and the result was remarkably excellent.

Example 4 In the color photographic light-sensitive material of Example 2 described in JP-A-1-158431, the yellow coupler in the blue-sensitive layer was replaced by a coupler YY having an acyl group represented by formula (I) of the present invention. -1, YY-3, YY-7 or YY-29
(The addition amount is replaced by 40 mol%), and the coupler and the compound a-4, a-13 of the general formula (a) of the present invention are changed.
a-24, a-31 or a-42 (addition amount is 50 mol% with respect to the coupler) was co-emulsified and added, and otherwise a sample was prepared in the same manner, exposed and developed to obtain photographic characteristics. Upon examination and a fading test, the samples of the present invention showed excellent photographic characteristics and anti-fading effect.

Example 5 Sample 101 of Example 1 described in JP-A-2-854.
The yellow coupler of the blue-sensitive layer is represented by the couplers YY-5, YY-6, YY-13 of the general formula (I) of the present invention.
YY-16, YY-17 or YY-22 (addition amount is 4
0 mol% substitution) and the coupler and the compound a-7, a-19, a-24, a of the general formula (a) of the present invention.
-30, a-49 or a-52 (addition amount is 25 mol% based on the coupler) was added after coemulsification, and the others were added to Sample 10
A sample was prepared in the same manner as in Example 1, exposed, developed, and examined for photographic characteristics, and then subjected to a fading test. The sample of the present invention showed excellent photographic characteristics and anti-fading effect.

[0210]

The silver halide color photographic light-sensitive material obtained by combining the yellow dye-forming coupler having an acyl group represented by the general formula (I) of the present invention and the compound represented by the general formula (a) of the present invention is It shows superior fastness to the conventionally known combination of silver halide color photographic light-sensitive materials.

[Procedure amendment]

[Submission date] January 17, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

Another object of the present invention is to have a sufficient effect of preventing fading or discoloration of a yellow color image without changing the hue, inhibiting the color development of the coupler or causing fog, and microcrystals after being applied. containing retraction color inhibitors, such as not to cause
It is to provide a novel silver halide color photographic light-sensitive material.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

[0022]

[Chemical 5] In the formula (YY), R ₁ is a monovalent substituent except hydrogen,
Q is a 3- to 5-membered hydrocarbon ring together with C or at least 1
R ₂ is a hydrogen atom, a halogen atom (F) or a non-metal atom group necessary for forming a 3- to 5-membered heterocycle containing a heteroatom selected from N, S, O, and P in the ring. , Cl, Br,
I, the same in the following description of formula (YY). ) An alkoxy group, an aryloxy group, an alkyl group or an amino group is represented by R
₃ is a substitutable group on the benzene ring, X is a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent (hereinafter referred to as splitting 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.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

When X represents a heterocyclic group, X is preferably optionally substituted. It is a 5- to 7-membered monocyclic or condensed-ring heterocyclic group, and examples thereof include succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, and 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. As the substituent of the aryloxy group, a halogen atom, 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, an arylsulfonyl group, or a cyano group is preferable.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046]

[Chemical 9] In formula (YY-3), W is a pyrrole ring together with N,
It represents a pyrazole ring, a non-metallic atomic group necessary for forming an imidazole ring or Application Benefits azole ring. Here, the ring represented by formula (YY-3) may have a substituent, and preferred examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group, an aryl group and an amino group. , An alkoxy group, an aryloxy group or a carbamoyl group. The C number of the heterocyclic group represented by the formula (YY-3) is 2 to 30, preferably 2 to 24,
More preferably, it is 2-16.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

[0055]

[Chemical 15]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction content]

[0058]

[Chemical 18]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

[0071]

[Chemical 31]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0104

[Correction method] Change

[Correction content]

In the general formula (a-4), R _a1 and k have the same meanings as defined in the general formula (a). R _a5
And R _a6 represents a hydrogen atom or a substituent, and R _a7
And R _a8 represents a substituent, and n _a and m _a are 0,
It is an integer of 1 to 3. When n _a and m _a are 2 or more, multiple
The numbers R _a7 and R _a8 may be the same or different.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0156

[Correction method] Change

[Correction content]

[0156] The composition of each treatment liquid is as follows. (Color developer) Water 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g Potassium bromide 0.015 g Triethanolamine 8.0 g Sodium liquor 1.4 g Potassium carbonate 25 g N- Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N, N-bis (carboxymethyl) hydrazine 5.5 g Optical brightener (WHITEX 4B, Sumitomo Chemical) 1.0 g Water was added 1000 ml pH (25 ° C) 10.05 (bleach-fixing solution) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g water was added to 1000 ml pH (25 ° C.) 6.0 (rinse solution) ion-exchanged water (calcium and magnesium were each 3 ppm or less) In each of 101 to 153 samples which formed a dye image in this manner, 400 nm It was exposed to a xenon tester (illuminance: 200,000 lux) for 15 days with a UV absorption filter manufactured by Fuji Photo Film Co., Ltd., which cuts off the following light. The concentration residual rate at the initial concentration of 2.0 of each sample was obtained.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0186

[Correction method] Change

[Correction content]

[0186]

[Chemical 66]

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0195

[Correction method] Change

[Correction content]

[0195]

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0196

[Correction method] Change

[Correction content]

(Bleach-fixing solution) (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate ( 700 g / l ) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water 1000 ml pH (25 ° C.) 6.0.

Claims (1)

Claims: 1. An acyl group comprising at least one acylacetamide type yellow dye-forming coupler represented by the following general formula (I) and at least one compound selected from the following general formula (a): A silver halide color photographic light-sensitive material comprising: [Chemical 1] (In the formula, R ₁ represents a monovalent group, and Q is 3 to
It represents a group of non-metal atoms necessary for forming a 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle having at least one heteroatom selected from N, S, O and P in the ring. However, R ₁ is not a hydrogen atom and does not combine with Q to form a ring. ) [Chemical 2] (In the formula, R _a1 , R _a2, and R _a3 represent an aliphatic group and an aromatic group, respectively. Y _a1 , Y _a2, and Y _a3 are -0-,
Represents -S- and -N (R _a4 )-, and k, m, n and q represent 0 or 1. R _a4 is a hydrogen atom,
Represents an aliphatic group and an aromatic group. However, when q is 1,
k, m and n are not 1 at the same time, and when q is 0, k, m and n are not 0 at the same time. R
Any two of _a1 , R _a2 and R _a3 may be bonded to form a 5- to 9-membered ring together with the phosphorus atom, in which case k,
m and n may be 1 at the same time. Also, R
_a4 may combine with R _a1 , R _a2 or R _a3 to form a 5- or 6-membered ring. )