JPH0689012A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material high in sensitivity and superior in processing stability and good in the storage stability of the raw photosensitive material in the lapse of time. CONSTITUTION:The silver halide color photographic sensitive material contains a coupler represented by formula I and a compound represented by formula II, and in formulae I and II, R1 is a monovalent group except H; Q is an atomic group necessary to form a 3-5 membered hydrocarbon ring or such a heterocyclic group having at least one of N, S, O, and P atoms in the ring together with the C atom; R2 is H, alkyl, alkoxy, aryloxy, amino, or halogen; R3 is a group substitutable on the benzene ring; Y is H or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent; R11 is alkyl, alkenyl, or aryl; and each of R2 and R3 is H, alkyl, alkenyl, or aryl, the total C number of R11, R12, and R13 is >=10.

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 particularly to a silver halide color photographic light-sensitive material having high sensitivity and excellent raw storability and processing stability.

[0002]

BACKGROUND OF THE INVENTION Couplers used in silver halide color photographic light-sensitive materials (hereinafter, also simply referred to as color light-sensitive materials) are conventional four-color couplers that require four molecules of silver to form one molecule of dye. In place of the equivalent coupler, silver for forming one molecule of dye by introducing an appropriate substituent at the coupling position (active site) of the coupler which reacts with the oxide of the developing agent is formed by 2 atoms. I made it 2
Equal couplers are becoming more popular.

In recent years, the demand for couplers has become more and more severe with the progress of color light-sensitive materials. For example, in addition to photographic characteristics, color developability, raw storability and processing stability, the solubility of the coupler itself in a solvent, Further improvements in dispersion stability have been strongly desired.

Among these, as an example of a yellow coupler having good color reproducibility and high color development and having improved light resistance, an anilide described in, for example, JP-A-63-123047. Introduce an alkoxy group at the 2-position of the
A yellow coupler having an acylamino group introduced at the 5-position is disclosed. However, the coupler is essentially p
It has a high Ka and has not reached a satisfactory level in terms of color development.

Further, the coupler is not excellent in solubility in a low boiling point solvent such as ethyl acetate or a high boiling point solvent such as dibutyl phthalate, and a large amount of solvent must be used for dispersion. It has a defect that precipitation easily occurs in the above solvent over time.

In recent years, under the production conditions for thinning a color light-sensitive material, which has been strongly aimed at, such defects are remarkably emphasized, and it has become clear that they become a major obstacle to practical use.

Conventionally, as a means for improving the color developability, it has been known to introduce a hetero atom into the acyl moiety of the acetanilide mother nucleus, for example, Research Disclosure (RD) 15737, JP-B-49. -17734, JP-A-5
0-130442, U.S. Pat.No. 3,778,277 and the like disclose introducing an oxygen or sulfur atom as a hetero atom to improve the color developability, but the technique also satisfies recent demands for high color developability. It hasn't arrived yet.

Further, US Pat. No. 5,118,599 discloses a novel yellow coupler having a dioxane cyclic structure in the molecule. The coupler has a feature of being excellent in solubility in an organic solvent and dispersion stability in the solvent, but it has not reached a satisfactory level in terms of color forming property.

Further, it was found that the light resistance was inferior to that of the conventional type coupler, and further improvement was strongly desired.

[0010]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and excellent processing stability.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material which has a good storability in raw storage over time. Other objects will be apparent from the following specification.

[0012]

The above objects of the present invention have been achieved by the following.

That is, in a silver halide color photographic light-sensitive material having a silver halide emulsion layer comprising a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support, at least one of the blue-sensitive layers has the following general composition. A silver halide color photographic light-sensitive material containing at least one coupler represented by the formula [Y-I] and at least one non-color forming compound represented by the following general formula [A-1].

[0014]

[Chemical 3]

(In the formula, R ₁ represents a monovalent substituent excluding a hydrogen atom, Q forms a 3- to 5-membered hydrocarbon ring with C, or is selected from N, S, O and P. Represents a non-metal atom group necessary for forming a 3- to 5-membered heterocycle containing at least one hetero atom in the ring, R ₂ represents a hydrogen atom,
Represents an alkyl group, an alkoxy group, an aryloxy group, an amino group or a halogen atom, R ₃ represents a group capable of substituting on the benzene ring, Y represents a hydrogen atom, or an aromatic primary amine developer oxidant; Represents a group capable of splitting off by the coupling reaction of. )

[0016]

[Chemical 4]

(In the formula, R ₁₁ represents an alkyl group, an alkenyl group or an aryl group, and R ₁₂ and R ₁₃ represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, respectively.
However, the total number of carbon atoms of R ₁₁ , R ₁₂ and R ₁₃ is 10 or more. ) Hereinafter, the present invention will be described in detail.

In the general formula [Y-I] of the present invention, R ₁ is a monovalent substituent except hydrogen, and Q is a 3- to 5-membered hydrocarbon ring together with C or at least one N, S, O, R ₂ is a hydrogen atom, a halogen atom (F, Cl, Br, I), a non-metal atom group necessary for forming a 3- to 5-membered heterocycle containing a heteroatom selected from P in the ring, Alkoxy group, aryloxy group, alkyl group or amino group, R ₃ is a group capable of substituting on the benzene ring, Y is a hydrogen atom or an aromatic primary amine developing agent is eliminated by a coupling reaction. It represents a possible group (hereinafter referred to as a leaving group).

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, sulfamoylanomyl 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 the formula [Y-I] is or contains an alkyl group, the alkyl group may be linear, branched or cyclic, unless otherwise specified.
Alkyl groups which may be substituted or may contain unsaturated bonds (eg 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-I] is an aryl group or contains an aryl group, the aryl group may be an optionally substituted monocyclic or condensed-ring aryl group (unless otherwise specified). For example phenyl, 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) is meant.

When the substituent in the formula [Y-I] is a heterocyclic group or contains a heterocyclic group, the heterocyclic group is selected from O, N, S, P, Se and Te unless otherwise specified. And a 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing at least one hetero atom 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
-Imidazolidinedione-3-yl).

The substituents preferably used in the formula [YI] will be described below.

In the formula [Y-I], R ₁ is preferably a halogen atom, a cyano group, or a monovalent group having 1 to 30 total carbon atoms (hereinafter abbreviated as C number) which may be substituted (for example, C number). An alkyl group, an alkoxy group) or a monovalent group having 6 to 30 carbon atoms (eg, an aryl group, an aryloxy group), and the substituent thereof is, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group. , Carbonamide group, sulfonamide group, and acyl group.

In the formula [Y-I], Q is preferably C and has a C number of 3 which may be substituted on any of 3 to 5 members.
~ 30 hydrocarbon rings or at least one N, S, O,
It represents a group of non-metallic atoms necessary for forming a heterocycle having a C number of 2 to 30 containing a heteroatom selected from P in the ring. Also,
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 a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, an oxetane ring, an oxolane ring, a 1,3-dioxolane ring, a thietane ring, a thiolane ring and a 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 [Y-I], R ₂ is preferably a halogen atom, an optionally substituted alkoxy group having 1 to 30 C atoms, an aryloxy group having 6 to 30 C atoms, or an alkyl group having 1 to 30 C atoms. Represents a group or an amino group having 0 to 30 carbon atoms, and examples of the substituent thereof include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In the formula [Y-I], R ₃ is preferably a halogen atom, an optionally substituted alkyl group having 1 to 30 C atoms,
An aryl group having a C number of 6 to 30, an alkoxy group having a C number of 1 to 30,
C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C1-30 carbonamido group, C1-30 sulfonamide group, C1-30 carbamoyl group, C Number 0 to 30 sulfamoyl group, C number 1 to
30 alkyl sulfonyl group, C 6-30 aryl sulfonyl group, C 1-30 ureido group, C 0-30 sulfamoylanomyl group, C 2-30 alkoxycarbonylamino group, C number 1 to 30 heterocyclic groups, C1 to C30 acyl groups, C1 to C30 alkylsulfonyloxy groups, and C6 to C30 arylsulfonylkioxy groups, the substituents of which are halogen, for example. Atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic 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 An acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group.

In the formula [Y-I], the substitution position of R ₂ is

[0029]

[Chemical 5]

In the formula [Y-I], Y preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom.

When Y represents a heterocyclic group, Y is preferably an optionally substituted 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, indole, indazole, benzimidazole, benzotriazole, imidazolidine-
2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiazolidin-2-one, benzimidazoline
-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine, paraban 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, anomi group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl There is an amino group. When Y represents an aryloxy group, Y preferably has a C number of 6
It represents an aryloxy group of ˜30 and may be substituted with a group selected from the substituent group mentioned when Y 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-I] 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 whose ring formed with C forms a 3- to 5-membered hydrocarbon ring, for example,

[0034]

[Chemical 6]

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), C
An alkoxy group of the number 1 to 8 (for example, methoxy, ethoxy,
Methoxyethoxy, butoxy), or an aryloxy group having 6 to 24 C atoms (for example, phenoxy, p-tolyloxy,
p-methoxyphenoxy), most preferably a chlorine atom, a methoxy group or a trifluoromethyl group.

R ₂ 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.

Y is particularly preferably the following formula [Y-II],
It is a group represented by [Y-III] or [Y-IV].

[0038]

[Chemical 7]

Represents Where R ₄ , R ₅ , R ₈ and R ₉
Is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
R 10 represents an alkylsulfonyl group, an arylsulfonyl group or an 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 represents 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 ₈ , R ₅ and R ₉ , R ₆ and R ₇ or R ₆
And R ₅ 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-II], particularly preferable ones are those in which Z in the formula [Y-II] is

[0041]

[Chemical 8]

Is a heterocyclic group which is The C number of the heterocyclic group represented by the formula [Y-II] is 2 to 30, preferably 4 to 20,
More preferably, it is 5-16.

[0043]

[Chemical 9]

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

[0045]

[Chemical 10]

In the formula [Y-IV], W represents a nonmetal atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N. here

[0047]

[Chemical 11]

The ring represented by may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group,
An aryl group, an amino group, an alkoxy group, an aryloxy group or a carbamoyl group. The C number of the heterocyclic group represented by the formula [Y-IV] is 2 to 30, preferably 2 to 24, more preferably 2 to 16.

Y in the formula [Y-I] is most preferably a group represented by the formula [Y-II].

The coupler represented by the formula [Y-I] has a substituent R ₁ , Q, Y, or

[0051]

[Chemical 12]

In the above, a dimer or a multimer having more than one valence may be formed to 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 the yellow coupler represented by the formula [Y-I] are shown below.

[0054]

[Chemical 13]

[0055]

[Chemical 14]

[0056]

[Chemical 15]

[0057]

[Chemical 16]

[0058]

[Chemical 17]

[0059]

[Chemical 18]

[0060]

[Chemical 19]

[0061]

[Chemical 20]

[0062]

[Chemical 21]

[0063]

[Chemical formula 22]

[0064]

[Chemical formula 23]

[0065]

[Chemical formula 24]

[0066]

[Chemical 25]

The yellow coupler of the present invention represented by the formula [Y-I] can be synthesized by the following synthetic route.

[0068]

[Chemical formula 26]

Here, the compound a is the compound J. Chem. Soc. (C). 1968.
2548, J.Am.Chem.Soc, 1934, 56 , 2710, Synthesis, 1971,25
8, J.Org.Chem, 1978, 43 , 1729, CA, 1960, 66 , 18533y and the like.

Hereinafter, the compounds b, c, d, e and f can be synthesized by a conventionally known method. The synthesis examples of the coupler of the present invention are shown below.

Synthesis Example 1 Synthesis of Exemplified Compound Y-28 1-Methylcyclopropanecarboxylic acid synthesized by the method described in Gotkis, D. et al, J. Am. Chem. Soc, 1934, 56 , 2710.
25g, methylene chloride 100ml N, N-dimethylformamide 1m
38.1 g of oxalyl chloride in a mixture of l at room temperature
It dripped over 30 minutes. After the dropwise addition, 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 the mixture was heated under reflux for 2 hours and then ethyl 3-oxobutanoate 32.6
g is added dropwise with heating under reflux over 30 minutes. 2 more after dropping
After heating under reflux for a while, 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 extracted with 30 ml of ethyl acetate and diluted sulfuric acid water, washed with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to give 2- (1-methylcyclopropanecarbonyl) -3-oxobutane. 55.3 g of an oily substance of ethyl acidate was obtained.

2- (1-methylcyclopropanecarbonyl) -3
A solution of 55 g of ethyl oxobutanoate and 160 ml of ethanol was stirred at room temperature, and 60 ml of 30% aqueous ammonia was added dropwise thereto over 10 minutes. Then, stir for 1 hour and 300m of ethyl acetate
l, extracted with diluted hydrochloric acid, neutralized, washed with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated to obtain 43 g of ethyl (1-methylcyclopropanecarbonyl) ethyl acetate.

34 g of ethyl (1-methylcyclopropanecarbonyl) acetate and N- (3-amino-4-chlorophenyl) -2- (2,4-diethyl)
-t-Pentylphenoxy) butanamide 44.5g internal temperature 100 ~
Heat and reflux at 120 ° C. under reduced pressure on the aspirator. 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 Y-28 as a viscous oil. The structure of the compound is MS spectrum,
Confirmed by NMR spectrum and elemental analysis.

Synthesis Example 2 Synthesis of Exemplified Compound Y-1 22.8 g of Exemplified Compound Y-28 was dissolved in 300 ml of methylene chloride, and 5.4 g of sulfuryl chloride was added dropwise over 10 minutes under ice cooling. 30
After reacting for a minute, the reaction solution was thoroughly washed with water, dried over anhydrous sodium sulfate and then concentrated to obtain a chloride of Exemplified Compound Y-28. 1-benzyl-5-ethoxyhydantoin 18.7g, triethylamine
A solution prepared by dissolving the chloride of Exemplified Compound Y-30 synthesized above in 50 ml of N, N-dimethylformamide in a solution of 11.2 ml and 50 ml of N, N-dimethylformamide is added dropwise at room temperature over 30 minutes.

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, the solvent was evaporated, and the obtained oily substance was crystallized from a mixed solvent of n-hexane and ethyl acetate. The precipitated crystals were filtered, washed with a mixed solvent of n-hexane and ethyl acetate, and then dried to obtain 22.8 g of crystals of Exemplified compound Y-1.

The structure of the compound was confirmed by MS spectrum, NMR spectrum and elemental analysis. The melting point is 132-1.
It was 33 ° C.

The yellow coupler having an acyl group represented by formula (A) of the present invention can be used in the range of 1.0 to 1.0 × 10 ^-3 mol per mol of silver halide. It is preferably 5.0 × 10 ^{-1 to} 5.0 × 10 ^-2 mol, and more preferably 4.0 × 10 ^{-1 to} 2.0 × 10 ^-2 mol.

Two or more kinds of yellow couplers having an acyl group represented by formula (A) of the present invention can be used in combination, or other known couplers can be used in combination.

The coupler having an acyl group represented by the general formula (A) of the present invention can be introduced into a color light-sensitive material by various known dispersion methods.

In the oil-in-water dispersion method, an organic solvent having a low boiling point (eg, ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol, etc.) is used to coat a fine dispersion, and a substantially low concentration is obtained in a dry film. A method in which the boiling point organic solvent does not remain may be used. When a high-boiling organic solvent is used, any of those having a boiling point of 175 ° C. or higher at atmospheric pressure (specific examples thereof will be described later) may be used, and one kind or two or more kinds may be arbitrarily mixed and used. . The ratio of the coupler of the present invention to these high-boiling point organic solvents may be in a wide range, but is in the range of 5.0 or less by weight per 1 g of the coupler. It is preferably 0 to 0.2, and more preferably 0.01 to 1.0.

Next, the non-color forming compound represented by the general formula [A-1] according to the present invention will be explained.

The alkyl group represented by R ₁₁ , R ₁₂ and R ₁₃ preferably has 1 to 32 carbon atoms and may be linear or branched.

The alkenyl group represented by R ₁₁ , R ₁₂ and R ₁₃ preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group represented by R ₁₁ , R ₁₂ and R ₁₃ is preferably a phenyl group.

The groups represented by R ₁₁ , R ₁₂ and R ₁₃ may further have a substituent, and examples of the substituent include alkyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, cyclo Alkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino. , Alkoxycarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino,
Examples include groups such as alkoxycarbonyl and aryloxycarbonyl.

The total number of carbon atoms of R ₁₁ , R ₁₂ and R ₁₃ is 10
It is above, and preferably 12 to 36.

Typical specific examples of the non-color forming compound of the present invention are shown below, but the present invention is not limited to these compounds.

[0089]

[Chemical 27]

[0090]

[Chemical 28]

[0091]

[Chemical 29]

In the present invention, the yellow coupler represented by the general formula (hereinafter referred to as yellow coupler YI) and the non-color-forming compound represented by the general formula [A-1] (hereinafter referred to as compound A-1). Is contained in at least one of the green-sensitive silver halide emulsion layers.

Yellow coupler Y-I and compound A-1
In order to incorporate the above in the silver halide emulsion layer, a conventionally known method, for example, a known high-boiling solvent such as dibutyl phthalate, tricresyl phosphate and butyl acetate,
The yellow coupler Y-I and the compound A can be added to a mixture of low boiling point solvents such as ethyl acetate or a solvent containing only low boiling point solvents.
-1 is dissolved alone or in combination, and then mixed with an aqueous gelatin solution containing a surfactant, and then emulsion-dispersed using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser, and then an emulsion. A method of directly adding it can be adopted. Further, after the above emulsified dispersion is set, it may be shredded, washed with water, and then added to the emulsion.

In the present invention, the yellow coupler Y-I according to the present invention and the compound A-1 may be separately dispersed by the above dispersion method and added to the silver halide emulsion, but both compounds are simultaneously added. A method of dissolving, dispersing and adding to the emulsion is preferable.

The addition amount of the compound A-1 is preferably 1 g of the yellow coupler Y-I according to the present invention.
It is in the range of 0.01 g to 10 g, more preferably 0.1 g to 3.0 g. Further, the compound A-1 according to the present invention may be used alone or in combination of two or more kinds.

As the silver halide emulsion used in the light-sensitive material of the present invention, any of ordinary silver halide emulsions can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer. A coupler is used in the emulsion layer of the color photographic light-sensitive material.

Further, by coupling with a colored coupler having a color correcting effect, a competing coupler and an oxidized product of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener and a hardener. Compounds that release photographically useful fragments such as film agents, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or emulsion layers,
Dyes may be included which are bleached or bleached from the light-sensitive material during the development process. For the light-sensitive material, formalin scavenger, fluorescent whitening agent, matting agent, lubricant, image stabilizer, surfactant, color antifoggant, development accelerator,
Development retarders and bleaching accelerators can be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, a color photographic process generally known can be carried out after exposure.

[0103]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Example 1 A multi-layer color photographic light-sensitive material (Sample 101) was prepared by sequentially forming each layer having the following composition from the support side on a triacetyl cellulose film support.

1st layer: Antihalation layer (HC-1) Black colloidal silver 0.20 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.05 Colored coupler (CM-1) 0.05 High boiling point solvent (Oil-) 1) 0.20 gelatin 1.5 second layer; intermediate layer (IL-1) UV absorber (UV-1) 0.01 high boiling solvent (Oil-1) 0.01 gelatin 1.5 third layer; low sensitivity red-sensitive emulsion layer (RL) iodine Silver bromide emulsion (Em-1) 0.8 Silver iodobromide emulsion (Em-2) 0.8 Sensitizing dye (SD-1) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-2) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-3) 0.5 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 1.0 Colored cyan coupler (CC-1) 0.05 DIR compound (D-1) 0.002 High boiling point solvent (Oil-1) 0.5 Gelatin 1.5 4th layer; High sensitivity red Sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 2.0 Sensitizing dye (SD-1) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (SD-2) 2.0 × 10 ⁻⁴ (Mol / silver 1 mol) Sensitizing dye (SD-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-1) 0.25 Cyan coupler (C-2) 0.05 Colored cyan coupler (CC-1) ) 0.015 DIR compound (D-1) 0.05 High boiling point solvent (Oil-1) 0.2 Gelatin 1.5 Fifth layer; Intermediate layer (IL-2) Gelatin 0.5 Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Iodobromide Silver emulsion (Em-1) 1.3 Sensitizing dye (SD-4) 5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-5) 1 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (MA) 0.25 Magenta coupler (MB) 0.25 Colored magenta coupler (CM-1) 0.01 DIR compound (D-3) 0.02 D IR compound (D-4) 0.020 High boiling point solvent (Oil-2) 0.3 Gelatin 1.0 Seventh layer; High sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 1.3 Sensitizing dye (SD-6) ) 1.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-7) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-8) 0.5 × 10 ^-4 (mol / silver) 1 mol) Magenta coupler (MA) 0.05 Magenta coupler (MB) 0.10 Colored magenta coupler (CM-2) 0.05 DIR compound (D-3) 0.01 High boiling solvent (Oil-2) 0.2 Gelatin 1.0 Eighth layer Yellow filter layer (YC) Yellow colloidal silver 0.1 Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Oil-3) 0.1 Gelatin 0.8 9th layer; Low sensitivity blue sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (SD-10) 7 × 10 ^{− 4} (mol / silver 1 mol) Yellow coupler (EY-1) 0.5 Yellow coupler (EY-2) 0.1 DIR compound (D-2) 0.01 High boiling solvent (Oil-2) 0.3 Gelatin 1.0 10th layer; high sensitivity blue Sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.4 Silver iodobromide emulsion (Em-1) 0.4 Sensitizing dye (SD-9) 1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitization Dye (SD-10) 3 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (EY-1) 0.30 Yellow coupler (EY-2) 0.05 High boiling point solvent (Oil-2) 0.15 Gelatin 1.1 11th layer; 1 Protective layer (PRO-1) Fine grain silver iodobromide emulsion (average particle size 0.08 μm, AgI content 2 mol%) 0.4 UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.05 High boiling point solvent (Oil-1) 0.1 High boiling point solvent (Oil-3) 0.1 Formalin scavenger (HS -1) 0.5 Formalin scavenger (HS-2) 0.2 Gelatin 1.0 12th layer; 2nd protective layer (PRO-2) Surfactant (Su-1) 0.005 Alkali-soluble matting agent (average particle size 2 μm) 0.05 Poly Methyl methacrylate (average particle size 3 μm) 0.05 Sliding agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, each layer contains a coating aid Su-2, a dispersion aid Su-3, a hardener H-1 and a hardener H-1. H-2, Stabilizer ST-
1, antifoggants AF-1 and AF-2 were added.

Em-1 Average grain size 0.46 μm Average silver iodide content: 7.0 mol%, monodisperse (width of distribution: 14%) surface low silver iodide (2 mol%) containing core / shell type emulsion Em-2 Average grain size 0.30 μm Average silver iodide content 2.0 mol%, monodisperse (14% distribution) surface silver bromide-containing core / shell type emulsion Em-3 Average grain size 0.81 μm Average Silver iodide content: 7.0 mol%, monodisperse (width of distribution: 14%) surface low silver iodide (1.0 mol%)
Contained core / shell type emulsion Em-4 Average grain size 0.95 μm Average silver iodide content: 8.0 mol%, monodisperse (width of distribution: 14%) surface low silver iodide (0.
5 mol%) containing core / shell type emulsion

[0108]

[Equation 1]

[0109]

[Chemical 30]

[0110]

[Chemical 31]

[0111]

[Chemical 32]

[0112]

[Chemical 33]

[0113]

[Chemical 34]

[0114]

[Chemical 35]

[0115]

[Chemical 36]

[0116]

[Chemical 37]

Next, in the above-mentioned sample 101, the ninth layer and 1
In place of the yellow coupler YA added to the 0-layer silver halide emulsion layer, an equimolar yellow coupler was added as shown in Table 1, and Oil-2 was replaced with the non-color forming compound shown in Table 1. Samples 102 and 103 and samples 104 to 115 of the present invention were prepared.

Each of the sample Nos. 1 to 20 produced in this way
After exposing the wedge with white light for 1/100 second,
The following development processing (A) was performed.

Processing step (38 ° C.) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Each processing step The composition of the treatment liquid used in is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Potassium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter. (PH = 10.2) <Bleaching solution> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10ml Add water to make 1 liter and use ammonia water to adjust the pH.
Adjust to = 6.0.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (Konica Corporation) 7.5 ml Water is added to make 1 liter.

An optical densitometer PDA was used for the obtained processed sample.
-65 type (manufactured by Konica Corporation), sensitivity of blue-sensitive emulsion layer (reciprocal of exposure amount required to give minimum density +0.1)
Was measured. The sensitivity is shown as a relative value when the sensitivity of Sample No. 101 is 100.

Further, in order to investigate the processing variability, the sample 101
.About.115 was wedge-exposed with white light for 1/100 second, and then the pH of the color developing solution in the developing treatment (A) was 10.
The same processing was performed by changing the values to 4 and 10.0, and the variation values of gamma in the linear portion of the characteristic curve of blue density were compared. The gamma fluctuation value is pH 10 with respect to the gamma value A at pH 10.0.
It is the rate of change of the gamma value B when 4, and the value obtained from the following formula is shown. The smaller the value, the smaller the change.

Gamma fluctuation value = {(B / A) -1} × 100 Further, in order to examine the raw storability, samples 101 to 115 were left under high temperature and high humidity (55 ° C., RH 60%) for 3 days, The same wedge exposure and color development processing as described above were performed to measure the fog density of the blue sensitive layer, and the difference in fog density (ΔFog) from the sample before standing was determined.

The results are shown below.

[0127]

[Table 1]

As is clear from the results shown in Table 1, Comparative Samples 101 and 102 using the comparative yellow coupler have a relatively small processing variability but a low sensitivity, and a large fog increase in the raw storage stability. Sample 103 using the coupler of the present invention and the non-color-forming compound other than the present invention has large processing variability and is insufficient in raw storage stability.

On the other hand, the samples of the present invention using the coupler of the present invention and the non-color-forming compound of the present invention are both more sensitive than the comparative sample and have improved processing variability. .

[0130]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material having high sensitivity and improved processing variability.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a silver halide emulsion layer consisting of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support, wherein at least one of the blue-sensitive layers has the following general composition. A silver halide color photographic light-sensitive material containing at least one coupler represented by the formula [Y-I] and at least one non-color-forming compound represented by the following general formula [A-1]. material. [Chemical 1] (In the formula, R ₁ represents a monovalent substituent except a hydrogen atom, and Q 1
Is required to form a 3- to 5-membered hydrocarbon ring with C, or to form a 3- to 5-membered heterocycle containing at least one hetero atom selected from N, S, O and P in the ring. Represents a non-metallic atomic group. R ₂ is a hydrogen atom, an alkyl group,
An alkoxy group, an aryloxy group, an amino group or a halogen atom is represented, R ₃ is a group capable of substituting on the benzene ring, Y is a hydrogen atom, or coupling with an oxidized product of an aromatic primary amine developer. Represents a group capable of leaving by a reaction. ) [Chemical 2] (In the formula, R ₁₁ represents an alkyl group, an alkenyl group or an aryl group, and R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, provided that R ₁₁ ,
The total carbon number of R ₁₂ and R ₁₃ is 10 or more. )