JPS6353540B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color light-sensitive material containing a 2-equivalent magenta coupler. It is necessary to use a 2-equivalent coupler in silver halide color light-sensitive materials in order to improve sharpness and developability, and a 2-equivalent magenta coupler is also disclosed in US Pat. No. 3,227,554. Among these, 4-arylthio-5-pyrazolone couplers are advantageous in terms of sensitivity and 2-equivalent weight. Although this coupler has considerably improved staining (color contamination caused by the gradual change and color development of unreacted residual couplers), it is still not sufficient. Further, the stain generated from the 4-arylthio-5-pyrazolone coupler could not be significantly prevented by conventionally known additives for preventing stain. Japanese Patent Application Laid-Open No. 55-93150 discloses a technique for whitening the white background of photographic paper using an oil-soluble dye.
This specification does not specifically disclose 4-arylthio-5-pyrazolones or any disadvantages thereof, nor does it disclose water-soluble dyes. Typical specific examples of water-soluble dyes used in the present invention are shown below. The first object of the present invention is to provide 4-arylthio-5-
The purpose is to prevent staining that occurs when using a pyrazolone 2-equivalent magenta coupler, and the second
The object of the present invention is to utilize this prevention technology to provide a color photosensitive material with excellent sharpness, high sensitivity, and almost no stain. The purpose of the present invention is to provide 2 represented by the following general formula ().
This was achieved by adding a water-soluble non-decolorizing dye having an absorption peak between 580 and 620 nm to at least one layer of a silver halide color light-sensitive material containing an equivalent magenta coupler. The water-soluble non-decolorizing dye of the present invention is an anthraquinone-based, azo-based, or phthalocyanine-based dye having a water-soluble group (for example, a carboxylic acid group, a sulfonic acid, a phosphoric acid, or a metal salt thereof such as sodium or potassium). It is something. Even if two or more types of dyes of the present invention are mixed, it is sufficient that the absorption peak at that time is between 580 and 620 nm. The dye of the present invention may be added in the form of an aqueous solution or an alkaline aqueous solution, and the amount added is 0.1 to 100 mg/m ² , preferably 1 to 10 mg/m ² . General formula () In the formula, Ar is at least one halogen atom,
Represents a phenyl group substituted with an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a cyano group, and R ¹ is a hydrogen atom, a halogen atom, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylthio group, an alkoxycarbonyl group, Represents a hydroxy group, alkyl group, alkoxy group or aryl group, m is 1 to 5
, and when m is 2 or more, R ₁ may be the same or different. Y is an acylamino group,
Represents an anilino group. Among the compounds represented by the general formula (), particularly preferred compounds can be represented by the general formula (). General formula () In the formula, Ar has the same meaning as in the general formula (), R ₂ represents an alkyl group or an aryl group, X represents a halogen atom or an alkoxy group, and R ₃ represents a hydrogen atom, a hydroxy group, or a halogen atom. , represents an alkyl group, an alkoxy group, or an aryl group, and R ₄ is a hydrogen atom, a halogen atom,
Alkyl group, alkoxy group, acylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, diacylamino group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, arylthio group,
It represents an alkyloxycarbonylamino group, an alkylureido group, an acyl group, a nitro group, a carboxy group or a trichloromethyl group. n is 1 to 4
represents an integer. To explain Ar in more detail, Ar is a substituted phenyl group, and the substituents include halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom, etc.),
Alkyl group having 1 to 22 carbon atoms (e.g. methyl group, ethyl group, tetradecyl group, t-butyl group, etc.),
Alkoxy groups having 1 to 22 carbon atoms (e.g., methoxy group, ethoxy group, octyloxy group, dodecyloxy group, etc.), alkoxycarbonyl groups having 2 to 23 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxy group) carbonyl group, etc.) or a cyano group. More specifically, X is a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), or an alkoxy group having 1 to 22 carbon atoms (for example, a methoxy group, an octyloxy group, a dodecyloxy group, etc.). To explain R ₄ in more detail, R ₄ is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom,
fluorine atom, etc.), linear or branched alkyl groups (e.g., methyl group, t-butyl group, tetradecyl group, etc.), alkoxy groups (e.g., methoxy group,
ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (e.g. acetamido group, benzamide group, butanamide group, tetradecaneamide group, α-(2,4-
di-tert-amylphenoxy)acetamide group,
α-(2,4-di-tert-amylphenoxy)butyramide group, α-(3-pentadecylphenoxy)hexanamide group, α-(4-hydroxy-
3-tert-butylphenoxy)tetradecanamide group, 2-oxo-pyrrolidin-1-yl group, 2
-oxo-5-tetradecylpyrrolidin-1-yl group, N-methyl-tetradecanamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octane sulfone group) amide group, p-dodecylbenzenesulfonamide group,
N-methyl-tetradecanesulfonamide group, etc.), sulfamoyl group (e.g., N-methylsulfamoyl group, N-hexadecylsulfamoyl group, N-[3-(dodecyloxy)-propyl])
Sulfamoyl group, N-[4-(2,4-di-tert
-aminophenoxy)butyl]sulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc.), carbamoyl group (e.g., N-methylcarbamoyl group, N-octadecylcarbamoyl group, N-[4-(2,4- di-tert-amylphenoxy)butyl]carbamoyl group, N-methyl-
N-tetradecylcarbamoyl group, etc.), diacylamino group (N-succinimide group, N-phthalimide group, 2,5-dioxo-1-oxazolidinyl group, 3-dodecyl-2,5-dioxo-1-
hydantoinyl group, 3-(N-acetyl-N-dodecylamino)succinimide group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxysulfonyl group (e.g. , methoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), aryloxysulfonyl group (e.g., phenoxysulfonyl group, 2,4-
di-tert-amylphenoxysulfonyl group, etc.), alkanesulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, 2-ethylhexanesulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl group (e.g. benzenesulfonyl group, etc.) group, 4-nonylbenzenesulfonyl group, etc.), alkylthio group (e.g., ethylthio group, hexylthio group, benzylthio group, tetradecylthio group, 2-(2,4-di-tert-amylphenoxy)ethylthio group, etc.), Arylthio groups (e.g., phenylthio group, p-tolylthio group, etc.), alkyloxycarbonylamino groups (e.g., ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), alkylureido groups ( For example, N-methylureido group, N,N-dimethylureido group, N-methyl-
N-dodecylureido group, N-hexadecylureido group, N,N-dioctadecylureido group, etc.), acyl group (for example, acetyl group, benzoyl group, octadecanoyl group, p-dodecaneamide benzoyl group, etc.) , represents a nitro group, a carboxy group or a trichloromethyl group. However, among the above substituents, those defined as alkyl groups have 1 to 36 carbon atoms, and those defined as aryl groups have 6 to 38 carbon atoms. To explain _R2 in more detail, _R2 is an alkyl group having 1 to 22 carbon atoms (e.g., methyl group, propyl group, butyl group, 2-methoxyethyl group, methoxymethyl group, hexyl group, 2-ethylhexyl group, dodecyl group). group, hexadecyl group, 2-(2,4
-di-tert-amylphenoxy)ethyl group, 2-
dodecyloxyethyl group, etc.), and an aryl group (e.g., phenyl group, α- or β-naphthyl group, 4-tolyl group, etc.). R ₃ represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, or an aryl group having the same meaning as R ₄ above. Among the couplers represented by the general formula (),
Those in which the sum of the carbon numbers of R ₂ and R ₃ is 6 or more are particularly preferred in achieving the object of the present invention. Examples of typical coupler compounds of the present invention are shown below.
This is not intended to be limiting in any way. Stain is a color turbidity caused by a chemical reaction between unreacted coupler and substances remaining in a processed sample, resulting in a colored substance. Color turbidity impairs the whiteness of photographic paper. There are various methods for measuring whiteness, but here we used the x and y values of the CIE chromaticity diagram. The CIE chromaticity diagram is described in Chapter 7, Section 3 of the new Color Science Handbook. In terms of color, it looks white when x is approximately 0.310 and y is approximately
It is around 0.328, and the closer it is to this value, the whiter it will appear. The emulsion used in the present invention is by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel (1967), Photographic by GFDuffin
Emulsion Chemistry (The Focal Press, 1966)
), Making and by VLZelikman et al.
Coating Photographic Emulsion (The Focal
Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. . It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. The couplers used in the present invention can be introduced into the silver halide emulsion layer by known methods, such as those disclosed in the US Pat.
The method described in No. 2322027 is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) etc., or boiling point approximately 30℃~
Organic solvents at 150°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After dissolving in methyl cellosolve acetate etc.,
Dispersed in hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. Example 1 Magenta coupler-1-(2,4.6-trichlorophenyl)-3-{(2-chloro-5-tetradecanamido)anilino}-4-{(2-n-butoxy-
10 g of 5-t-octyl)phenylthio}-2-pyrazolin-5-one (coupler 5) was dissolved in 20 ml of tricresyl phosphate and 20 ml of ethyl acetate, and this solution was mixed with 8 ml of a 1% aqueous sodium dodecylbenzenesulfonate solution. gelatin solution 100
g was emulsified and dispersed. Next, this emulsified dispersion was mixed with a green-sensitive silver chlorobromide emulsion (Br 50 mol %), and sodium dodecylbenzenesulfonate was added as a coating aid to obtain a coating solution for the third layer shown in Table 1. Using this coating solution, a multilayer color photosensitive material having the structure shown in Table 1 was prepared and designated as Sample A. Add dyes (2), (3), (8) and comparative dyes to the second layer.
It was dissolved in a 0.2% aqueous solution and added so that the coating amount was 5 mg/m ² . Using such a second layer, samples B and B were prepared in the same manner as sample A, respectively.
Created C, D, and E. Also, in place of the third layer coupler (5), coupler (3),
Samples F and G were prepared in the same manner as Sample B except for using a comparative coupler. These samples A to F were exposed to light at 1000 lux for 1 second through a continuous wedge and treated with the following processing solution. Developer Benzyl alcohol 15ml Diethylenetriaminepentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 5g Na ₂ CO ₃ 30g Hydroxylamine sulfate 2g 4-amino-3-methyl-N-ethyl-N-β-
(Methanesulfonamide)ethylaniline・3/
2H ₂ SO ₄・H ₂ O 4.5g Make up to 1000ml with water PH10.1 Bleach-fix ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 4g Make up to 1000ml with water PH6. 8 Processing process Temperature Time Developer 33° 3 minutes 30 seconds Bleach-fix solution 33° 1 minute 30 seconds Washing 28-35° 3 minutes

[Table] Each sample on which a dye image had been formed in this manner was irradiated with light for 4 hours at an illumination intensity of 20,000 lux using a fluorescent lamp. Using Hitachi Color Analyzer for the white background area
The x and y values of the CIE chromaticity table were determined, and the values are summarized in Table 2.

[Table] Dye

【table】

[Table] From the above table, it can be seen that the samples of the present invention have higher whiteness.

Claims (1)

[Claims] 1 A silver halide color light-sensitive material containing a 4-arylthio-5-pyrazolone 2-equivalent magenta coupler, which has at least one water-soluble non-decolorizing dye in at least one layer, and has an absorption peak of 580 to 620 nm. A silver halide color photosensitive material characterized by: