JP2000089421A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dye image superior in color reproduction and development performance and stable against light and humidity and heat by incorporating each specified cyan and yellow couplers in red-sensitive and blue-sensitive silver halide emulsion layers. SOLUTION: The red-sensitive silver halide emulsion layer contains one of the cyan couplers represented by formulae I and II and the like and the blue-sensitive silver halide emulsion layer contains the yellow coupler represented by the formula III and in formulae I-III, each of R1 and R3 is a 1-32 C alkyl group or the like; each of R2 and R4 is a substituent; each of R22 and R23 is an electron withdrawing group having a Hammett's substituent constant σp of >=0.30; Z5 is a nonmetallic atomic group necessary for forming the azole ring the hetero atom of which is a nitrogen atom; each of X1, X2, and X5 is an H or halogen atom or a group to be released by coupling with the oxidation product of a color developing agent; R5 is an aliphatic group or the like; R6 is an aliphatic group resistant to diffusion or aromatic group; Y is an H atom or the like; and X3 is a 5- or 6-membered heterocyclic group releasable by reaction with the oxidation product of a color developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material which is excellent in color reproducibility and color-forming properties and which can provide a dye image which is stable to light, humidity and heat.

[0002]

2. Description of the Related Art In silver halide color photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials), generally used couplers include yellow couplers comprising open-chain ketomethylene compounds, pyrazolone compounds and pyrazoloazole compounds. Magenta couplers, phenolic compounds, and cyan couplers composed of naphthol compounds are known.

On the other hand, US Pat. Nos. 5,658,720 and 5,679,506 describe that pyrazolotriazole type couplers having a specific structure are useful as cyan couplers. It is particularly noteworthy that a cyanazomethine dye obtained from a pyrazolotriazole-type cyan coupler significantly improves cyan color reproducibility. The pyrroloazole type coupler described in U.S. Pat. No. 5,541,501 has the same effect. However, when these pyrazolotriazole and pyrroloazole type cyan couplers are used in a red-sensitive silver halide emulsion layer and a conventional yellow coupler is used in a blue-sensitive silver halide emulsion layer, the yellow azomethine formed after development processing is reduced. The disadvantage that the heat and humidity stability of the dye image was reduced was recognized. Furthermore, when these pyrazolotriazole and pyrroloazole type cyan couplers are used in a red-sensitive silver halide emulsion layer, and a conventional pyrazolotriazole type magenta coupler is used in a green-sensitive silver halide emulsion layer, they are formed after development processing. There was a defect that the stability of the magenta azomethine dye image to light (light fastness) was reduced.

The low heat and humidity fastness of the yellow azomethine dye image and the low light fastness of the magenta azomethine dye image significantly impair the performance of color photographic light-sensitive materials, especially print-based color photographic light-sensitive materials. Things.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to use a pyrazolotriazole or pyrroloazole type cyan coupler in a red-sensitive silver halide emulsion layer. To improve the color reproducibility of the cyan azomethine dye image, and without impairing the heat resistance and moisture resistance of the yellow azomethine dye image of the blue light-sensitive silver halide emulsion layer and the magenta color of the green light-sensitive silver halide emulsion layer. An object of the present invention is to provide a silver halide color photographic light-sensitive material which does not impair the light fastness of an azomethine dye image.

[0006]

The above object of the present invention is achieved by the following constitution.

[0007] 1. In a silver halide color photographic light-sensitive material having a photographic component layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, The blue-sensitive silver halide emulsion layer contains a cyan coupler represented by the following general formula (1A), (1B) or (1C), and the blue-sensitive silver halide emulsion layer has the following general formula (2). A silver halide color photographic light-sensitive material comprising a yellow coupler represented by the formula:

[0008]

Embedded image

[0009] (wherein the alkyl group of R ¹ and R ³ are the carbon atoms 1 may have a substituent, respectively 32, an aryl group, a heterocyclic group, .R ² represents an alkoxy group or a heterocyclic oxy and R ⁴ represents a substituent, and R ²² and R ^23.
Each Hammett's substituent constant σp of 0.30 or more electron-withdrawing groups, a non-metallic atomic group necessary for Z ⁵ form an azole ring heteroatoms is a nitrogen atom, X ^1,
X ² and X ^{5 each} represent a hydrogen atom, a halogen atom, or a group which is eliminated by a coupling reaction with an oxidized form of a color developing agent. )

[0010]

Embedded image

(Wherein, R ⁵ represents an aliphatic group and an aromatic group, and R ⁶ represents a diffusion-resistant aliphatic group and an aromatic group.)
Y represents a hydrogen atom or a substituent, and n represents an integer of 1 to 4. X ³ represents a 5- or 6-membered heterocyclic group capable of leaving by reaction with an oxidized form of the coloring agent. ) 2. In a silver halide color photographic light-sensitive material having a photographic component layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, The light-sensitive silver halide emulsion layer contains a cyan coupler represented by the above formula (1A), (1B) or (1C), and the green photosensitive silver halide emulsion layer has the following formula (11). A silver halide color photographic material comprising a magenta coupler represented by the formula:

[0012]

Embedded image

(Wherein, R ²⁰ represents a substituent, R ²¹ represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group. L represents a substituted or unsubstituted alkylene group, and J represents- CO- or -SO ₂ - .X ⁴ representing a hydrogen atom, the reaction by a group capable of being released with an oxidation product of a halogen atom, or a color developing agent, Z ⁴ which are necessary for forming a nitrogen-containing heterocycle Represents a non-metallic atomic group) 3. In a silver halide color photographic light-sensitive material having a photographic component layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, The light-sensitive silver halide emulsion layer contains a cyan coupler represented by the above formula (1A), (1B) or (1C), and the blue-sensitive silver halide emulsion layer has the formula (2). A silver halide color photographic light-sensitive material comprising a yellow coupler represented by formula (I) and a magenta coupler represented by formula (11) in the green photosensitive silver halide emulsion layer.

The present invention is attained by the above constitution. When pyrazoloazole and pyrroloazole type cyan couplers are used, the color image obtained from the conventional yellow coupler and pyrazolotriazole type magenta coupler is not affected by humidity or light. It is not clear if stability is compromised. The present inventors have searched for various yellow and magenta couplers, and have found that the above-mentioned drawbacks can be improved by a combination of the above specific couplers according to the present invention. By using the yellow coupler and the magenta coupler according to the present invention, the stability of the yellow image with respect to humidity and the light resistance of the magenta color image are improved because each is in a separate layer. Although the inference cannot be sufficiently explained by the inference, the stability of the color image can also be a large factor due to the atmosphere in the layer, the physical state, and the like. It is presumed that changes related to the concentration or movement of the affecting substance cause these effects.

Hereinafter, the present invention will be described in detail.

In the general formulas (1A) and (1B), examples of the alkyl group represented by R ¹ and R ³ include linear, branched and cyclic alkyl groups having 1 to 32 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopentyl group, and a cyclohexyl group. These cycloalkyl groups may be further substituted with other substituents.

The aryl group represented by R ¹ and R ³ includes an alkyl group, an alkoxy group, an amide group, a phenyl group which may have a substituent such as a halogen atom, a naphthyl group, and the like. Examples of the heterocyclic group represented by R ¹ and R ³ include a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrrolyl group, a pyrazinyl group, and a pyrimidinyl group. Substituents such as an alkyl group, an alkoxy group and a halogen atom may be substituted. In the general formulas (1A) and (1B), examples of the alkyloxy group represented by R ¹ and R ³ include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group. No. Examples of the heterocyclic oxy group represented by R ¹ and R ³ include a pyridyloxy group, a thiazolyloxy group, an oxazolyloxy group, an imidazolyloxy group, a furyloxy group, a pyrrolyloxy group, a pyrazinyloxy group, and a pyrimidinyloxy group. These heterocyclic groups may be substituted with a substituent such as an alkyl group, an alkoxy group, or a halogen atom.

In the general formulas (1A) and (1B), the substituent represented by R ² and R ⁴ is an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, Pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, etc., halogen atom (eg, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (Eg, methoxy, ethoxy, pentyloxy, octyloxy, dodecyloxy, etc.) An alkoxycarbonyl group (for example,
A methyloxycarbonyl group, an ethyloxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group, etc.), an aryloxycarbonyl group (for example,
Phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (for example, methylsulfonylamino group, ethylsulfonylamino group, hexylsulfonylamino group, cyclohexylsulfonylamino group,
Dodecylaminosulfonylamino group, sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, etc.), ureido group (eg, methylureido group, pentylureido) Group, cyclohexylureido group, dodecylureido group, etc.), acyl group (eg, acetyl group, ethylcarbonyl group, cyclohexylcarbonyl group, phenylcarbonyl group, pyridylcarbonyl group, etc.), carbamoyl group (eg, aminocarbonyl group, methylaminocarbonyl) Group, ethylaminocarbonyl group, dimethylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), amide group (for example, methylcarbonylamino group, Bonylamino group, ethylcarbonylamino group, dodecylcarbonylamino group, etc.), sulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, dodecylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethyldimethyl Amino group, 2-pyridylamino group, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group and the like, and these groups may be further substituted by the above substituents.

In general formulas (1A) and (1B), R
Among the substituents of ² and R ^4, a phenyl group is particularly preferred, and this phenyl group may be substituted with the substituents described above.

X in the general formulas (1A) and (1B)
¹ and X ² represent a hydrogen atom, a halogen atom or a group which is separated by a coupling reaction with an oxidized form of a color developing agent,
Examples of the halogen atom include a chlorine atom and a bromine atom. Examples of the group which is eliminated by coupling reaction with an oxidized form of the color developing agent include alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, and allyloxycarbonyl. Oxy, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle linked by N atom, alkyloxycarbonylamino, aryloxycarbonylamino , Carboxyl, and the like. Preferred examples of X ¹ and X ^{2 in} the general formulas (1A) and (1B) are a hydrogen atom or a halogen atom, particularly a chlorine atom.

In the general formula (1C), Z ⁵
Is a group of nonmetallic atoms necessary for forming an azole ring in which a hetero atom is a nitrogen atom, R ²² and R ²³ are each an electron-withdrawing group having a Hammett's substituent constant σp of 0.30 or more, and X ⁵ Represents a hydrogen atom or a group which undergoes a coupling reaction with an oxidized form of a color developing agent to be released.

The azole ring formed by Z ⁵ includes the following.

[0023]

Embedded image

In the formula, R ²⁶ , R ²⁷ and R ²⁸ represent a hydrogen atom or a substituent, and m represents an integer of 0-4. The above Z ⁵ -2 as Z ^5, Z ⁵ -3 are preferred, Z ⁵ -2 are especially preferred. R ²⁶ , R ²⁷ and R ²⁸ represent a hydrogen atom or a substituent, and the substituent is an aryl group (preferably having 6 to 6 carbon atoms).
30, for example, phenyl, m-acetylaminophenyl, p-methoxyphenyl), an alkyl group (preferably having 1 to 30 carbon atoms, for example, methyl, trifluoromethyl, ethyl, isopropyl, heptafluoropropyl,
t-butyl, n-octyl, n-dodecyl), cyano group, formyl group, acyl group (preferably having 1 to 3 carbon atoms)
0, for example, acetyl, pivaloyl, benzoyl, furoyl, 2-pyridinecarbonyl), a carbamoyl group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl, n-
Octylcarbamoyl), an aliphatic oxycarbonyl group (preferably having 1 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, diphenylmethylcarbonyl), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, for example, Phenoxycarbonyl, p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl, o-methoxyphenoxycarbonyl), formylamino group, acylamino group (preferably an alkylcarbonylamino group having 1 to 30 carbon atoms, such as acetylamino, propionylamino , Cyanoacetylamino), preferably having 7 to 7 carbon atoms
30 arylcarbonylamino groups (e.g., benzoylamino, p-tolylamino, pentafluorobenzoylamino, m-methoxybenzoylamino), preferably a C 4-30 hetenylcarbonylamino group;
(E.g., 2-pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino)], an aliphatic oxycarbonylamino group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, methoxyethoxycarbonylamino), An aryloxycarbonylamino group (preferably having 7 to 7 carbon atoms)
30, for example, phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino), a sulfonamide group (preferably having 1 to 3 carbon atoms)
0, for example, metasulfonamide, benzenesulfonamide, p-toluenesulfonamide), ureide group (preferably having 1 to 30 carbon atoms, for example, methylureide, dimethylureide, p-cyanophenylureide), sulfamoylamino group (Preferably having 1 to 30 carbon atoms, for example, methylaminosulfonylamino, ethylaminosulfonylamino, anilinosulfonylamino), an unsubstituted amino group, an alkylamino group (preferably having 1 to 30 carbon atoms,
For example, methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino), an arylamino group (preferably having 6 to 30 carbon atoms, for example, anilino), an alkoxy group (preferably having 1 to 30 carbon atoms, for example, Methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy, n-dodecyloxy), aryloxy group (preferably having 6 to 30 carbon atoms, for example, phenoxy, m-chlorophenoxy, p-methoxyphenoxy, o-methoxyphenoxy) ), A heteryloxy group (preferably having 3 to 30 carbon atoms, for example, tetrahydropyranyloxy, 3-pyridyloxy, 2- (1,3-benzimidazolyl) oxy), an alkylthio group (preferably having 1 to 30 carbon atoms, for example, methylthio) , Ethylthio, n
-Butylthio, t-butylthio), an arylthio group (preferably having 6 to 30 carbon atoms, for example, phenylthio), a heterylthio group (preferably having 3 to 30 carbon atoms, for example, 2
-Pyridylthio, 2- (1,3-benzimidazolyl)
Thio, 1-hexadecyl-1,2,3,4-tetrazolyl-5-thio, 1- (3-N-octadecylcarbamoyl) phenyl-1,2,3,4-tetrazolyl-5-thio), heterocyclic group (Preferably having 3 to 30 carbon atoms, for example, 2-benzoxazolyl, 2-benzothiazolyl,
1-phenyl-2-benzimidazolyl, 5-chloro-
1-tetrazolyl, 1-pyrrolyl, 2-furanyl, 2-
Pyridyl, 3-pyridyl), halogen atom (fluorine, chlorine, bromine), hydroxy group, nitro group, sulfamoyl group (preferably having 0 to 30 carbon atoms, for example, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl) , N, N-dipropylsulfamoyl), a sulfonyl group (preferably having 1 to 30 carbon atoms, for example, methanesulfonyl, benzenesulfonyl, toluenesulfonyl, trifluoromethanesulfonyl, difluoromethanesulfonyl), an acyloxy group (preferably having 1 carbon atom) ~ 30,
For example, formyloxy, acetyloxy, benzoyloxy), carbamoyloxy group (preferably having 1 carbon atom)
To 30, for example, methylcarbamoyloxy, diethylcarbamoyloxy), an imide group (preferably having 4 carbon atoms).
To 30, for example, succinimide, phthalimide), a sulfinyl group (preferably having 1 to 30, for example, diethylaminosulfinyl), a phosphoryl group (preferably having 0 to 30, for example, dimethoxyphosphoryl, diphenylphosphoryl), carboxyl A phosphono group. These groups may have similar substituents when possible. As R ²⁶ and R ²⁷ , an alkyl group and an aryl group are preferable. As R ²⁶ and R ²⁷ , an aryl group is more preferable, and an aryl group substituted with an alkoxy group, an acylamino group, a sulfonamide group, an alkyl group, or the like is still more preferable. In the general formula (1C), R ²² and R ²³ are electron-withdrawing groups having a Hammett's substituent constant σp value of 0.30 or more. The upper limit is an electron-withdrawing group having a σp value of 1.0 or less. Hammett's rule was published in 1935 in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. The substituent constants determined by the Hammett's rule include a σp value and a σm value, and these values are described in many general books. A. Dean ed. "Lange's H
andbook of Chemistry "No. 12
Edition, 1979 (McGraw-Hill) and "Chemical Area Special Edition", No. 122, pp. 96-103, 1979 (Nankodo). In the present invention,
R ²² and R ²³ are defined by Hammett's substituent constant σp value, but in the sense that the Hammett's substituent constant σp value described in these publications is limited only to already known substituents. Even if the Hammett's substituent constant σp value is not described in the literature and is unknown, if it is a substituent included in the above range when measured based on the Hammett rule, the Hammett referred to by R ²² and R ²³ Has a substituent constant σp value of 0.
It is included in 30 or more electron-withdrawing groups. To describe R ²² and R ²³ in detail, examples of the electron-withdrawing group having a σp value of 0.30 or more include an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), and a carbamoyl group ( For example, carbamoyl, N-ethylcarbamoyl, N-phenylcarbamoyl, N, N
-Dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N- (4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-di-t -Amylphenoxy) propyl @ carbamoyl), an aliphatic oxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, ter
t-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), cyano group, nitro group, sulfinyl group (for example,
3-phenoxypropylsulfinyl, 3-pentadecylphenylsulfinyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy),
Sulfamoyl groups (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N
-Dodecylsulfamoyl, N, N-diethylsulfamoyl), an alkyl group substituted with at least three or more fluorine atoms (eg, trifluoromethane, heptafluoropropane), a perfluoroaryl group (eg, pentafluoro Phenyl) and the like. Typical σp values of electron-withdrawing groups having a σp value of 0.30 or more include a cyano group (0.66), a nitro group (0.78),
Trifluoromethyl group (0.54), carboxyl group (0.45), acetyl group (0.50), benzoyl group (0.43), trifluoromethanesulfonyl group (0.
92), a methanesulfonyl group (0.72), a benzenesulfonyl group (0.70), and a methanesulfinyl group (0.
49), carbamoyl group (0.36), methoxycarbonyl group (0.45), ethoxycarbonyl group (0.4
5), phenoxycarbonyl group (0.44), pyrazolyl group (0.37), methanesulfonyloxy group (0.3
6), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57), pentafluorophenyl group (0.41) and the like. In the general formula (1C),
R ²² and R ²³ are each a cyano group, an acyl group, a carbamoyl group, an aliphatic oxycarbonyl group or an aryloxycarbonyl group preferably, R ²² is a cyano group, R ²³
Is more preferably a group represented by —CO—OR ²⁹ (R ²⁹ represents an aliphatic group or an aryl group). R ²⁹
Is particularly preferably a branched alkyl group or a cyclic alkyl group.

In the general formula (1C), X ⁵ represents a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine), or a group which undergoes a coupling reaction with an oxidized form of a color developing agent (hereinafter referred to as “elimination”). Group "). As the leaving group,
Alkoxy group (for example, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), aryloxy group (for example, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy group (for example, , Acetoxy, tetradecanoyloxy, benzoyloxy), a sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (eg, dichloroacetylamino, heptafluorobutyrylamino), a sulfonamide group (eg, methane Sulfonamide, p-toluenesulfonamide), aliphatic oxycarbonyloxy group (for example, ethoxycarbonyloxy, benzylcarbonyloxy),
An aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), an alkylthio group (for example, carboxymethylthio), an arylthio group (for example, 2-butoxy-5-tert-octylphenylthio), a heterocyclic thio group (for example, terrazolylthio), Carbamoylamino group (for example, N-methylcarbamoylamino, N
-Phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-
2-oxo-1-pyridyl), imide group (eg, succinimide, hydantoinyl), aromatic azo group (eg, phenylazo), sulfinyl group (eg, 2-butoxy-5-tert-octylphenylsulfinyl), sulfonyl group ( For example, 2-butoxy-5-te
rt-octylphenylsulfonyl) and the like. X ⁵ is preferably a halogen atom, an arylthio group or a carbamoyloxy group. In the coupler residue formed by leaving the leaving group X ⁵ from the coupler represented by the general formula (1C), R ²² , R ²³ or Z
R ^26, R ²⁷ or a method other than R ²⁸ is polymerized in ^5, for example, to form a dimer or more multimer linked in normal bond such as homopolymer or co had a polymer chain A polymer may be formed. Typical examples of the homopolymer or copolymer having a high molecular chain include homopolymers or copolymers of the above-mentioned addition polymer having a coupler residue and an ethylenically unsaturated compound. In this case, at least one type of the color-forming repeating unit having the coupler residue may be contained in the polymer, and non-color-forming properties such as acrylates, methacrylates, and maleates may be used as copolymer components. It may be a copolymer containing one or more of the above ethylenic monomers.

Specific examples of the general formulas (1A), (1B) and (1C) are shown below, but the present invention is not limited to these. No. 5,658,72.
No. 0, No. 5,679,506, JP-A-5-10038
No. 0 describes specific examples and synthesis examples of these couplers, but does not disclose any examples used in combination with the yellow coupler of the present invention or the magenta coupler of the present invention.

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

Next, as the aliphatic group represented by R ⁵ in the general formula (2), a linear or branched alkyl group, and a cyclic alkyl group such as methyl, ethyl, isopropyl, t -Butyl group, n-dodecyl group, 1-hexylnonyl group, cyclopropyl group, cyclohexyl group and the like. The alkyl group represented by R ⁵ may further have a substituent, and the substituent includes:
For example, a halogen atom (eg, chlorine atom, bromine atom, etc.), an aryl group (eg, phenyl group, pt-octylphenyl group, etc.), an alkoxy group (eg, methoxy group, etc.), an aryloxy group (eg, 2 , 4-di-t-
An amylphenoxy group, a sulfonyl group (eg, a methanesulfonyl group), an acylamino group (eg, an acetylamino group, a benzoylamino group, etc.), a sulfonylamino group (eg, an n-dodecanesulfonylamino group, etc.),
And a hydroxy group.

In the general formula (2), examples of the aromatic group represented by R ⁵ include aryl groups having 6 to 14 carbon atoms (for example, phenyl group, 1-naphthyl group and 9-anthranyl group). Can be The aryl group represented by R ⁵ may further have a substituent, for example, an amino group (eg, dimethylamino group, anilino group, etc.), a cyano group, a nitro group, an alkylthio group (eg, methylthio group) Group), R ⁵ in the general formula (2)
And a substituent having the same meaning as that of the alkyl group represented by R ⁵ in the general formula (2).

R ⁵ is preferably an alkyl group, more preferably a branched alkyl group, and particularly preferably a t-butyl group.

In the general formula (2), the aliphatic group represented by R ⁶ represented by R ⁶ is preferably a linear or branched alkyl group having 8 to 21 carbon atoms, for example, 2-ethylhexyl group, isotridecyl group. Group, hexadecyl group or octadecyl group. Further, the alkyl group of the diffusion-resistant group represented by R ⁶ may have a structure via a functional group in the middle, for example, as represented by the following general formula (4).

In the formula (4) -JLR ⁷ , J is a linear or branched alkylene group having 1 to 20 carbon atoms, for example, a methylene group, a 1,2-ethylene group, a dimethylmethylene group. R ⁷ represents a linear or branched alkyl group having 1 to 20 carbon atoms, for example, a group having the same meaning as the alkyl group represented by R ⁵ in the general formula (2). .

L is -O-, -O-CO-, -O-SO ₂
-, - CO -, - CO -O -, - CO-N (R 8) -,
^{-CO-N (R 8) -SO} 2 -, - N (R 8) -, - N
_{^{(R 8) -SO 2 -,}} - N (R 8) -CON (R 9) -, -
^{N (R 8) -CO-O} -, - S (O) m -, - S (O) m
-N (R ⁸⁾ -, or _{-S (O) m -N (R} 8) -C
Wherein R ⁸ and R ⁹ represent a hydrogen atom or a group having the same meaning as the alkyl group or aryl group represented by R ⁵ in the formula (2); Represents an integer from to 2). R ⁷ and J may be bonded to each other to form a cyclic structure. The alkyl group represented by R ⁷ may further have a substituent. In this case, examples of the substituent include a substituent of the alkyl group represented by R ⁵ in the general formula (2). Represents a group having the same meaning.

Examples of the diffusion-resistant aromatic represented by R ⁶ in the general formula (2) include groups having the same meaning as the aryl group represented by R ⁵ in the general formula (2). Can be The aryl group represented by R ⁶ may further have a substituent. In this case, examples of the substituent include a group having the same meaning as the aryl group represented by R ⁵ in formula (2). Is mentioned. Among these substituents of the aryl group represented by R ⁶ , a linear or branched alkyl group having 4 to 10 carbon atoms is preferable. In the general formula (2), R ⁶ is preferably a diffusion-resistant aliphatic group, and particularly preferably a straight-chain alkyl group having 8 to 21 carbon atoms.

In the general formula (2), Y represents a substituent, and specifically, Y is a general formula (1A) or (1)
A substituent as defined for R ² and R ⁴ in B),
n is preferably 1. In the above general formula (2), Y
As a chlorine atom, an alkyl group (for example, a methyl group,
Preferred are an ethyl group, an octyl group, etc., an alkoxy group (eg, a methoxy group, an ethoxy group, an isopropoxy group, etc.), an amide group (eg, an acetamido group, a butylcarbonylamino group, an octylcarbonylamino group, etc.).

In the above general formula (2), X ³ is preferably a nitrogen-containing heterocyclic ring which can be eliminated at the time of coupling with the oxidized form of the coloring agent, and is represented by the following general formula (4).

[0044]

Embedded image

In the general formula (4), Z represents a group of nonmetallic atoms necessary for forming a 5- to 6-membered heterocyclic group together with a nitrogen atom. Examples of the atomic group necessary for forming a non-metallic atomic group, for example, a substituted or unsubstituted methylene and methine, -CO -, - N (R 10) - (R 10 is a hydrogen atom, an alkyl group, Represents a cycloalkyl group, an aryl group or a heterocyclic group.), -N =, -O-, and -S
(O) _m- (m represents an integer from 0 to 2) and the like. In the present invention, the nitrogen-containing heterocyclic group X ³ represented by the general formula (4) is represented by the following general formulas (5), (6), (7),
It is represented by (8), (9) or (10).

[0046]

Embedded image

The above general formulas (5), (6), (7),
In (8) or (9), R ¹¹ , R ¹² and R ¹³
Represents a group that can be substituted on the nitrogen-containing heterocyclic ring, and includes, for example, groups having the same meanings as the groups exemplified as the substituents of the alkyl group and the aryl group represented by R ⁵ in Formula (2). Can be. In the general formula (9), R ¹⁴ represents, for example, a group having the same meaning as the alkyl group and the aryl group represented by R ⁵ in the general formula (2);
Further, a carbonyl group (for example, an alkylcarbonyl group such as an acetyl group and a trifluoroacetylpivaloyl group, a benzoyl group, a pentafluorobenzoyl group, a 3,5-di-
arylcarbonyl groups such as t-butyl-4-hydroxybenzoyl group, etc.) and sulfonyl groups (eg, alkylsulfonyl groups such as methanesulfonyl group, trifluoromethanesulfonyl group, and arylsulfonyl groups such as p-toluenesulfonyl group), etc. Represents In the general formulas (8) and (9), Z ¹ represents —N (R ¹⁵ ) — (R
¹⁵ represents a group having the same meaning as R ¹⁰ of the group Z in the formula (4)), —O—, or —S (O) _k — (k is 0 to 2)
Represents an integer).

In the general formula (10), Z ² represents -N
(R ¹⁶ )-(R ¹⁶ is a group represented by R in the general formula (4)
Represents the same group as ¹⁰ ), or represents -O-.

In the general formula (10), Z ³ represents -N
(R ¹⁷ )-(R ¹⁷ is a group represented by R in group Z in formula (4).
Represents the same meaning as ¹⁰ ), or —C (R ¹⁸ ) (R ¹⁹ ) —
(R ¹⁸ and R ¹⁹ are a hydrogen atom or the above general formula (2)
Represents a group having the same meaning as the group exemplified as the substituent for the alkyl group and the aryl group represented by R ⁵ ).

In the present invention, the nitrogen-containing heterocyclic group X ³ represented by the formula (4) is particularly preferably a group represented by the above formula (10). The two-equivalent yellow coupler represented by the general formula (2) may be bonded at any of the substituents to form a bis-form, a tris-form, a tetrakis-form, or a polymer-form.

Next, typical specific examples of the bi-equivalent yellow coupler represented by formula (2) used in the present invention will be shown, but the present invention is not limited by these.

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

The yellow coupler of the present invention represented by the general formula (2) can be easily synthesized by a conventionally known method. The typical synthesis examples of the present invention are shown below.

Synthesis Example 1 The exemplified coupler (Y-11) was synthesized according to the following scheme.

[0057]

Embedded image

1) Synthesis of Intermediate (11a) 144 g (1 mol) of 2-amino-4-chlorophenol was dispersed in 900 ml of 2-butanol,
At 0 ° C., 103 g (1.01 mol) of acetic anhydride was added dropwise with stirring. After the completion of the dropwise addition, the reaction is further performed at 40 ° C. for 1.5 hours. After completion of the reaction, 42 g of sodium hydroxide (1.05
Mol) and 262 g (1.05 mol) of dodecyl bromide
, And the mixture is reacted under heating and stirring at 85 ± 5 ° C for 9 hours. Thereafter, the reaction solution is left to cool, washed with water and twice with a 10% aqueous sodium hydrogen carbonate solution, and the organic layer is concentrated under reduced pressure. Further, the obtained residue is recrystallized from 600 ml of ethanol to obtain 326 g of the intermediate (11a) (yield: 92%).

2) Synthesis of intermediate (11b) 320 g (0.9 mol) of intermediate (11a) in 900 ml
Of methanol and 55 ml of water, and 176 g (2 mol) of concentrated sulfuric acid is added dropwise. After the completion of the dropwise addition, the reaction is carried out for 4 hours under reflux. Thereafter, the reaction solvent was recovered under reduced pressure,
1.3 liters of toluene and 28% aqueous sodium carbonate solution are added to the residue, and the organic layer is extracted. In addition, 28%
Once with aqueous sodium carbonate solution and three times with saline,
When the organic layer is azeotropically dehydrated, a toluene solution of the intermediate (11b) is obtained.

3) Synthesis of Intermediate (11d) To a solution of the above intermediate (11b) in toluene was added 150 g.
(0.9 mol) of (11c) is added, and the mixture is reacted for 12 hours while heating and refluxing while distilling off generated methanol to obtain a toluene solution of the intermediate (11d).

4) Synthesis of Intermediate (11e) Further, 121 g (0.9 mol) of sulfuryl chloride is added dropwise at about 40 ° C. to a toluene solution of this intermediate (11d). After the completion of the dropwise addition, the mixture is reacted at the same temperature for 2 hours. After the completion of the reaction, the reaction solvent is recovered under reduced pressure to obtain an intermediate (11e).

5) Synthesis of Illustrative Coupler (Y-11) The intermediate (11e) was dissolved in 1.1 liter of acetone,
222 g (1.2 mol) of benzylhydantoin and 162 g (1.2 mol) of potassium carbonate are added, and the mixture is heated and refluxed for 5 hours. After completion of the reaction, acetone was distilled off under reduced pressure, and 1.1 liter of ethyl acetate and 400 ml of water were added to extract an organic layer. Further, the organic layer is washed twice with a 10% aqueous solution of sodium carbonate, once with dilute sulfuric acid and three times with brine, and the organic layer is concentrated under reduced pressure. The resulting residue was treated with 2-propanol
The crystals were recrystallized in 1 liter, and the target coupler (Y-1)
518 g (yield 92%) of 1) was obtained. Melting point 63-64
° C. The structure of the exemplified coupler (Y-11) is NM
It was confirmed by R, IR and mass spectrum.

Synthesis Example 2 An exemplified coupler (Y-12) was synthesized according to the following scheme.

[0064]

Embedded image

1) Synthesis of Intermediate (12c) 34.8 g (0.22 mol) of (12a) and 79.2 g
(0.20 mol) of (12b) was reacted in 300 ml of xylene while heating and refluxing for 3.5 hours while distilling off generated methanol. After completion of the reaction, the solvent was recovered under reduced pressure, and the residue was recrystallized from 300 ml of ethanol to obtain 91.8 g of intermediate (12c) (88% yield).

2) Synthesis of Intermediate (12d) 60 g (0.115 mol) of Intermediate (12c) was added to 300
Dissolve in ethyl acetate and slowly add dropwise at about 30 ° C. 9.24 ml (0.115 mol) of sulfuryl chloride.
After the completion of the dropwise addition, the mixture was stirred at the same temperature for about 1 hour, and then the solvent was recovered, whereby 65.6 g of the intermediate (12d) was obtained.
(Yield 103%) was obtained. Intermediate (12d) was used in the next step without further purification.

3) Synthesis of Illustrative Coupler (Y-12) Intermediate (12d) (15 g, 26.9 mmol) was dissolved in acetone (45 ml), and potassium carbonate (4.83 g, 34.34).
9 mmol) and 4.51 g (34.9 mmol) of (12e) were added and reacted under heating and reflux for 4 hours. After completion of the dropwise addition, ethyl acetate and water were added thereto, and the organic layer was extracted. The organic layer was further washed with dilute hydrochloric acid and then with water three times. Thereafter, the solvent was recovered under reduced pressure, and the residue was recrystallized with a mixed solvent of 50 ml of ethanol and 10 ml of ethyl acetate to obtain 14.7 g (yield 84%) of an exemplified coupler (Y-12). The structure of the exemplified coupler (Y-12) was confirmed by NMR, IR and mass spectrum.

Illustrative couplers (Y-11) and (Y-12)
Other exemplary couplers were synthesized according to the above synthesis examples, starting from the corresponding raw materials.

Next, in the general formula (11), examples of the substituent represented by R ²⁰ include a linear or branched alkyl group, and a cyclic alkyl group (for example, methyl, ethyl, isopropyl, t- Butyl group, n-dodecyl group, 1-hexylnonyl group, cyclopropyl group, cyclohexyl group, etc., alkenyl group (eg, vinyl group, allyl group), alkynyl group (eg, propargyl group, etc.), aryl group (eg, Phenyl group, naphthyl group, etc.), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group , A pyrazolyl group, a tetrazolyl group, etc.), a halogen atom (for example, a chlorine atom, a bromine atom, Atom, such as a fluorine atom), an alkoxy group (e.g., methoxy group, ethoxy group, propyloxy group, a pentyloxy group, cyclopentyloxy group,
Hexyloxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group, etc., aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyl) Oxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc., aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group) Butylsulfonylamino, hexylsulfonylamino, cyclohexylsulfonylamino, octylsulfonylamino, dodecylsulfonylamino, phenylsulfonylamino, etc.), Famoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthyl Aminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2 -Pyridylaminoureido group, etc.), acyl group (eg, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbony) Group, octyl group, 2-ethylhexyl group,
Dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc., acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group) Carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group,
Pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc., amide group (for example, Methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino Group, naphthylcarbonylamino group, etc.), sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group) Group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino) Group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group,
Examples thereof include a nitro group, a sulfo group, a carboxyl group, and a hydroxyl group, and these groups may be further substituted by the above substituents. Among these, for example, alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, Preferred are groups such as acyloxy, amino, alkylamino, ureido, alkoxycarbonyl, aryloxycarbonyl, carbonyl and the like, more preferred are alkyl groups, and particularly preferred are (t) -butyl groups.

In the general formula (11), R ²¹ represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group. The alkyl group represented by R ²¹ has 1 carbon atom.
-32 are preferable, for example, a methyl group, an ethyl group,
Representative examples thereof include a propyl group, an isopropyl group, a (t) butyl group, a hexyl group, an octyl group, a hexadecyl group, and a 2-ethylhexyl group.

When the alkyl group represented by R ²¹ has a substituent, examples of the substituent include the same groups as those of R ²⁰ in formula (11).

The cycloalkyl group represented by R ²¹ preferably has 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 2-methylcyclopropyl group and an adamantyl group. No.

When the cycloalkyl group represented by R ²¹ has a substituent, the substituent is represented by the general formula (1)
It includes the same groups as R ²⁰ in 1).

The aryl group represented by R ²¹ has a carbon number of 6 to
14 are preferred, and typical examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
When the aryl group represented by R ²¹ has a substituent, examples of the substituent include the same groups as those of R ²⁰ in Formula (11).

In the general formula (11), L represents a substituted or unsubstituted alkylene group. Examples of the alkylene group represented by L include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group.

When the alkylene group represented by L has a substituent, examples of the substituent include the same groups as those for R ²⁰ in formula (11).

Hereinafter, typical specific examples of the alkylene group represented by L are shown, but L is not limited thereto.

[0078]

Embedded image

In the above formula (11), L is preferably a substituted or unsubstituted ethylene group, and particularly preferably,
It is an unsubstituted ethylene group.

In the general formula (11), J represents —CO
- or -SO ₂ - represents a.

In the general formula (11), X ⁴ represents a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom or the like), or a group capable of leaving by reaction with an oxidized form of a color developing agent, for example, alkoxy , Aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, arylcarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy,
Alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, heterocyclic ring bonded with an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, etc. Is a halogen atom, particularly preferably a chlorine atom.

In the general formula (11), examples of the nitrogen-containing heterocyclic ring formed by Z ⁴ include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Of these, a triazole ring is preferred.

In the general formula (11), preferred skeletons are the following (11A) and (11B), and particularly preferred is (11A).

[0084]

Embedded image

Hereinafter, typical specific examples of the magenta coupler represented by the general formula (11) of the present invention will be shown, but the present invention is not limited thereto.

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

The coupler used in the present invention can be used in an amount of usually 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 to 8 × 10 ^-1 mol per mol of silver halide.

The cyan coupler used in the red-sensitive silver halide emulsion layer of the present invention can be used in combination with another type of cyan coupler, and the yellow coupler used in the blue-sensitive silver halide emulsion layer of the present invention can be used. Can also be used in combination with other yellow couplers.

The couplers used in the present invention include the methods and techniques used in conventional dye-forming couplers.
The same applies.

The coupler according to the present invention can be used as a material for forming a color photograph by any coloring method, and specific examples thereof include an external coloring method and an internal coloring method. When an external color developing method is used, the coupler according to the present invention can be used by dissolving it in an aqueous alkali solution or an organic solvent (eg, alcohol) and adding it to a developing solution.

When the coupler according to the present invention is used as a material for forming a color photograph by an internal color developing method, the coupler is contained in a photographic light-sensitive material. Typically, a method in which a coupler is blended with a silver halide emulsion and this emulsion is coated on a support to form a color photographic light-sensitive material is preferably used.

The present invention can be used for color photographic light-sensitive materials such as color negative and positive films and color photographic paper.

The light-sensitive material of the present invention such as the color photographic paper may be of a single color or a multicolor. The multicolor light-sensitive material is prepared such that each structural unit is sensitive to a certain region of the spectrum, for example, usually corresponding to each of the three primary color regions of the spectrum, a blue-sensitive silver halide emulsion layer, It comprises a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. The constituent layers of the light-sensitive material including the respective layers of the image forming constituent units may be composed of a plurality of constituent layers, and may be arranged in various orders as known in the art.

A typical multicolor photosensitive material has at least one photosensitive material.
Cyan dye image forming unit comprising at least one red-sensitive silver halide emulsion layer containing two cyan couplers, magenta dye image forming unit comprising at least one green-sensitive silver halide emulsion layer, at least one blue-sensitive halogen It comprises a yellow dye image forming structural unit comprising a silver halide emulsion layer supported on a support.

The coupler may be incorporated into the emulsion according to a conventionally known method. For example, tricresyl phosphate, a high boiling solvent having a boiling point of 175 ° C. or more such as dibutyl phthalate or a low boiling solvent such as butyl acetate or butyl propionate alone or, if necessary, a coupler alone in a mixture thereof. Alternatively, after dissolution in combination, the mixture is mixed with a gelatin aqueous solution containing a surfactant, emulsified by a high-speed rotation mixer or a colloid mill or the like, and then added to silver halide to prepare a silver halide emulsion.

The silver halide preferably used in the present invention includes silver chloride, silver chlorobromide, silver bromide and silver chloroiodobromide. Also, a combination mixture such as a mixture thereof may be used. That is, when a silver halide emulsion is used for color photographic paper, particularly fast developability is required. Therefore, the halogen composition of the silver halide preferably contains a chlorine atom, and is preferably silver chloride, at least 1% chloride. Silver chlorobromide or silver chloroiodobromide containing silver is preferred.

The silver halide is chemically sensitized by a conventional method. In addition, optical sensitization can be performed in a so-called wavelength range.

The silver halide emulsion is used to prevent fog during the production, storage, or photographic processing of a light-sensitive material, and / or
Alternatively, a compound known as an antifoggant or stabilizer in the photographic industry can be added for the purpose of keeping photographic performance stable.

In the color photographic light-sensitive material of the present invention, a color fogging inhibitor, a dye image stabilizer, an ultraviolet light inhibitor, an antistatic agent, a matting agent, a surfactant and the like which are usually used for light-sensitive materials can be used. .

These are described, for example, in Research Disclosure (Research Disclosure).
e) The description in volume 176, pages 22 to 31 (December 1978) can be referred to.

The color photographic light-sensitive material of the present invention can form an image by performing a color development process known in the art.

The color photographic light-sensitive material of the present invention may contain a color developing agent in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof, and may be processed by an alkaline activating bath.

The color photographic light-sensitive material of the present invention is subjected to color development, bleaching and fixing. The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

[0108]

EXAMPLE 1 Polyethylene having a titanium oxide and each layer having the following structure was formed on a support obtained by laminating polyethylene on one side of a paper support and laminating polyethylene containing titanium oxide on the other side. This was applied on the side of the layer to prepare a multilayer silver halide photographic material, Sample 1. The coating solution was prepared as described below.

First layer coating solution Comparative yellow coupler (Y-1 ') 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, added Agent (HQ-1) 0.67
g, 60 ml of ethyl acetate in 6.67 g of anti-irradiation dye (AI-3) and high boiling organic solvent (DNP)
To dissolve the solution, and add 20% surfactant (SU-
1) A 10% gelatin aqueous solution containing 7.0 ml 220
The resulting mixture was emulsified and dispersed in the mixture using an ultrasonic homogenizer to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer. Further, the second layer and the fourth layer are used as hardeners.
(H-1) was added to the layer and (H-2) was added to the seventh layer. Surfactants (SU-2), (SU-
3) was added to adjust the surface tension. With regard to the amount of addition of silver halide photographic light-sensitive material is shown in particular in grams per 1 m ² unless otherwise noted. The layer configuration is as shown in the following table. The structure of the material used is also shown below.

[0112]

[Table 1]

[0113]

[Table 2]

(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
The following (solution A) and (solution B) were added in 1000 ml of a 2% aqueous gelatin solution kept at a temperature of pAg = 6.5 and pH = 3.0.
Over 30 minutes while controlling at the same time.
Solution) and (Solution D) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.
For control of pAg, a control liquid having the following composition was used. The composition of the control solution is a mixed halide salt aqueous solution composed of sodium chloride and potassium bromide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentration of the control solution is A
0.1 mol / l when mixing the liquid and the liquid B, and 1 mol / l when mixing the liquid C and the liquid D.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Silver nitrate 10 g Add water 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water 600 ml (Solution D) Silver nitrate 300 g Water was added and 600 ml was added. After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. Average particle size 0.85μ
m, coefficient of variation (S / R) = 0.07, silver chloride content 9
A 9.5 mol% monodispersed cubic emulsion EMP-1 was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 10 ^-4 mol / mol AgX Sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle diameter was 0.4.
A monodispersed cubic emulsion EMP-2 having a thickness of 3 μm, a coefficient of variation (S / R) = 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compound was used for EMP-2.
Chemical ripening was performed at 5 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Method for Preparing Red-Sensitive Silver Halide Emulsion) (Solution A) and (B)
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodispersed cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation (S / R) = 0.08, and a silver chloride content of 99.5 mol% was obtained.

EMP-3 was prepared by using the following compound.
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX coefficient of variation is calculated standard deviation (S) and an average particle diameter (R), S = _{[Σ (R i -R) 2 /} Σn i ] 1/2 R _i represents a particle size, n _i is the particle Represents the number of particles whose diameter is R _i .

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

Next, the comparative cyan couplers (C-1 ') and (C-2') used in the fifth layer of Sample 1 were identified as Nos. Couplers 2 to 15 (the amount of addition is the same as the total number of moles of the comparative couplers (C-1 ') and (C-2'))
And the comparative yellow coupler (Y-1 ') used in the first layer was replaced with No. 3 in Table 3. 1, No. 3 and No. 3 Except for using Sample No. 11, Samples 2 to 15 were prepared in place of the yellow couplers shown in Table 3. Each of the samples 1 to 15 obtained above was subjected to a wedge exposure according to a conventional method, and then subjected to a developing process in the following developing process.

(Development Processing Step) Processing Step Temperature Time Color Development 35.0 ± 0.3 ° C. 45 seconds Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30 ° C. to 34 ° C. 90 seconds Drying 60 ° C. ８０80 ° C. for 60 seconds The composition of the processing solution used in each processing step is as follows.

(Color developing solution) Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1. 0 g ethylenediaminetetraacetic acid 1.0 g catechol-3,5-disulfonic acid disodium salt 1.0 g diethylene glycol 10 g 3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 4 0.5 g Fluorescent whitening agent (4,4-diaminostilbenesulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1 l, and the pH is adjusted to 10.10.

(Bleach-fixing solution) Ethylenediaminetetraacetate ferric ammonium ferric ammonium dihydrate 60.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 100.0 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water In addition, the total volume is adjusted to 1 l and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

(Stabilizing Solution) 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1 1,1-diphosphonic acid 2.0 g o-phenylphenol sodium 1.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) 3.0 g fluorescent whitening agent (4,4'-diaminostilbenesulfonic acid derivative) 1 Add 0.5 g water to make the total volume 1 liter and adjust to pH 7.0 with sulfuric acid or potassium hydroxide.

For the samples 1 to 15 processed above,
The maximum concentration (Dmax) was measured using a densitometer (model KD-7 manufactured by Konica Corporation), and each of the treated samples was allowed to stand in a high-temperature, high-humidity (85 ° C., 60% RH) atmosphere for 21 days. The heat and moisture resistance of the yellow dye image was measured.

However, the heat resistance and moisture resistance of the dye image are represented by the percentage of the dye remaining after the heat resistance and humidity resistance test with respect to the initial density of 1.0. Table 3 shows the results.

The samples 1 to 15 were evaluated for color reproducibility by the following method.

First, a color negative film (Konica Color LV-400: manufactured by Konica Corporation) and a camera (Konica FT)
-1 MOTOR: manufactured by Konica Corporation) and a color checker manufactured by Macbeth Co., Ltd. was photographed. Subsequently, color negative development processing (CNK-4: manufactured by Konica Corporation) was performed, and the obtained negative image was converted to a Konica Color Printer CL-P2000.
(Manufactured by Konica Corporation). 1 to 15
Was printed to a size of 82 mm × 117 mm, and a practical print was obtained in the same manner as described above.

The printer conditions at the time of printing were set for each sample so that the gray on the color checker became gray on the print.

The obtained practical prints were visually evaluated for color reproducibility and black background. The results are summarized in Table 3.

[0141]

[Table 3]

From Table 3, it was found that the present invention was made by combining the present invention in which the cyan coupler of the present invention was incorporated in the red-sensitive silver halide emulsion layer and the yellow coupler of the present invention was incorporated in the blue-sensitive silver halide emulsion layer. Sample No. 4-1
0 and No. In the case of 12 to 15, it can be seen that all of the color developability, color reproducibility, black background, and heat and moisture resistance of the yellow dye image can be cleared.

Example 2 Samples 16 to 30 were produced under the same conditions as in Example 1 by using a combination of a cyan coupler and a magenta coupler as shown in Table 4 below. However, as a yellow coupler, the comparative yellow coupler (Y-1 ') used in Example 1 was used as a sample. Development and evaluation were performed under the same conditions as in Example 1. Table 4 shows the results of the evaluation.

[0144]

[Table 4]

From Table 4, it can be seen that the composition was prepared by combining the present invention in which the cyan coupler of the present invention was incorporated in the red-sensitive silver halide emulsion layer and the magenta coupler of the present invention was incorporated in the green-sensitive silver halide emulsion layer. Sample No. 19 ~
25 and no. In the case of 27-30, color development, color reproducibility,
It can be seen that all of the black background and the light resistance of the magenta dye image can be cleared.

Example 3 C-1 of the present invention as a cyan coupler in a red-sensitive silver halide emulsion layer, M-2 of the present invention as a magenta coupler in a green-sensitive silver halide emulsion layer, blue-sensitive silver halide A sample was prepared using Y-1 of the present invention as a yellow coupler in the emulsion layer, and developed and evaluated under the same conditions as in Example 1. As a result, all the dye images had excellent color developability and color reproducibility. With no problem, heat resistance of yellow image
Excellent results were also obtained in terms of moisture resistance and light fastness of a magenta image.

[0147]

EFFECT OF THE INVENTION The combination of a specific azole type cyan coupler, a specific yellow coupler comprising an open-chain ketomethylene compound and a specific pyrazolotriazole type magenta coupler provides excellent color reproducibility, good color development, and high humidity. Thus, a silver halide color photographic light-sensitive material capable of obtaining a dye image stable to light, heat and light can be obtained.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic component layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. Wherein the red-sensitive silver halide emulsion layer contains a cyan coupler represented by the following general formula (1A), (1B) or (1C), and the blue-sensitive silver halide emulsion layer has the following general formula: A silver halide color photographic material comprising a yellow coupler represented by the formula (2). Embedded image [Wherein, R ¹ and R ³ each may be an alkyl group having 1 to 32 carbon atoms, an aryl group, a heterocyclic group,
Represents an alkoxy group or a heterocyclic oxy. R ² and R ⁴ each represent a substituent. R ²² and R ²³ each represent an electron-withdrawing group having a Hammett's substituent constant σp of 0.30 or more;
Z ⁵ is a group of nonmetallic atoms necessary for forming an azole ring in which a hetero atom is a nitrogen atom, and X ¹ , X ² and X ⁵ are a hydrogen atom, a halogen atom, or a coupling with an oxidized form of a color developing agent. Each represents a group which leaves upon reaction. ] [Wherein, R ⁵ represents an aliphatic group and an aromatic group, and R ⁶ represents a diffusion-resistant aliphatic group and an aromatic group. Y represents a hydrogen atom or a substituent, and n represents an integer of 1 to 4. X ³ is 5 or 6 which can be removed by reaction with the oxidized form of the coloring agent.
Represents a membered heterocyclic group. ] 2. A silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. Wherein the red-sensitive silver halide emulsion layer contains a cyan coupler represented by the general formula (1A), (1B) or (1C), and the green-sensitive silver halide emulsion layer has the following general formula: A silver halide color photographic material comprising a magenta coupler represented by the formula (11). Embedded image [In the formula, R ²⁰ represents a substituent, and R ²¹ represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group. L represents a substituted or unsubstituted alkylene group, J represents -CO- or -SO ₂ - represents a. X ⁴ represents a hydrogen atom, a halogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent, and Z ⁴ represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring. 3. A silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. Wherein the red-sensitive silver halide emulsion layer contains a cyan coupler represented by the general formula (1A), (1B) or (1C), and the blue-sensitive silver halide emulsion layer contains A silver halide color comprising a yellow coupler represented by the formula (2) and a magenta coupler represented by the formula (11) in the green-sensitive silver halide emulsion layer. Photosensitive material.