JPH09292679A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain superior performance, such as excellent hues and fastness to light and heat and low dependence on processing conditions by incorporating at least one kind of specified coupler in one layer on one side of a support. SOLUTION: The color photographic sensitive material contains in at least one layer on the support at least one kind of coupler represented by the formula in which each of R1 and R2 is an aliphatic group; X is a heterocyclic or substituted amino or aryl group; each of R3 and R4 is an H atom or a substituent; Y is an H atom or a substituent; each of R1 and R2 is, preferably, a 1-10C, especially, 1-6C straight or branched alkyl group; each of R3 and R4 is, preferably, an aliphatic or aryl group; and the hetero ring of X is, preferably, a 5-, 6-, 7-, or 8-membered N-, O-, and/or S-containing 1-36C ring.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic material containing a novel coupler.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, an oxidized aromatic primary amine color developing agent and a coupler react with an exposed silver halide as an oxidizing agent to form indophenol and indoaniline. It is well known that dyes such as indamine, azomethine, phenoxazine, and phenazine are formed and images are formed. In this photographic method, a subtractive color method is used, and a color image is formed by yellow, magenta, and cyan dyes. Of these, phenol or naphthol couplers have been used to form cyan dye images. However, the dyes produced from these couplers have an unfavorable absorption in the green region, and therefore have a problem of deteriorating the color reproducibility, and it is strongly desired to solve this problem. .

As means for solving this problem, heterocyclic compounds described in US Pat. Nos. 4,728,598 and 4,873,183, European Patent 0249453A2 and the like have been proposed. However, these couplers have fatal defects such as low coupling activity and poor dye fastness. As couplers that overcome these problems, pyrrolotriazole-based couplers described in US Pat. No. 5,256,526 and European Patent 54300 have been proposed. These couplers are excellent in terms of hue and coupling activity. However, the light fastness of the produced dye is not always sufficient, and the light fastness is particularly poor in the low color density portion. In addition, there is a problem of "processing dependency" in which the color density is changed due to the change in composition of the processing liquid.

As a coupler that solves this problem, compounds described in US Pat. No. 5,384,236 have been proposed. These couplers solved the process dependence problem. However, the lightfastness of the resulting dye was still not at a sufficient level. Particularly, in the case of a chloro atom which is generally used as a leaving group of a coupler, photobleaching in a low concentration part is poor, which has been a substantial problem.

[0005]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide light-sensitive material containing a pyrrolotriazole-based coupler having an excellent hue and having a lightfastness.

[0006]

In order to overcome these problems, the inventor of the present invention has conducted extensive studies and found that a combination of a certain substituent at the 7-position and a certain leaving group is particularly effective in solving the problems. It was found to be effective. That is, the above object was achieved by a silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains at least one coupler represented by the following general formula (I). General formula (I)

[0007]

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(In the general formula (I), R ₁ and R ₂ represent an aliphatic group, X represents a heterocyclic group, a substituted amino group or an aryl group, and R ₃ and R ₄ represent a hydrogen atom or Represents a substituent, and Y represents a hydrogen atom or a substituent.)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention will be described below in detail. In the formula, the aliphatic group represented by R ₁ and R ₂ is, for example, a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group or a cycloalkenyl group, and more specifically, For example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, t-amyl group, t-octyl group, tridecyl group,
Represents a cyclopentyl group and a cyclohexyl group. R ₁ ,
R ₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms.

The substituent of R ₃ is, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an aliphatic group (eg, straight chain or branched chain alkyl group having 1 to 36 carbon atoms, aralkyl group). , An alkenyl group, an alkynyl group,
A cycloalkyl group or a cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-
Butyl, tridecyl, t-amyl, t-octyl, 2-
Methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, cyclohexyl, 3- (2,4-di-t-amylphenoxypropyl), an aryl group (an aryl group having 6 to 36 carbon atoms, for example, phenyl Four
-T-butylphenyl, 2,4-di-amylphenyl,
2,4,6-trimethylphenyl, 2-tetradecanamidophenyl, 2-methoxyphenyl), a heterocyclic group (heterocycle having 1 to 36 carbon atoms, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2 -Benzothiazolyl), cyano group, hydroxy group, carboxyl group,
Amino group, alkoxy group (a linear, branched or cyclic alkoxy group having 1 to 36 carbon atoms, for example, methoxy, ethoxy, butoxy, 2-methoxyethoxy, 2-
Dodecyloxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (an aryloxy group having 6 to 36 carbon atoms, for example, phenoxy, 4-t-butylphenoxy, 2,6, -di-t-butylphenoxy). , An acylamino group (an acylamino group having 2 to 36 carbon atoms, such as acetamide, benzamide, 2- (2,4-
Di-t-amylphenoxy) butanamide, an alkylamino group (an alkylamino group having 1 to 36 carbon atoms, such as methylamino, diethylamino, dicyclohexylamino), an anilino group (an anilino group having 6 to 36 carbon atoms, for example, Anilino, 2,6-dimethylanilino, 2
-Chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), a ureido group (a ureido group having 2 to 36 carbon atoms, for example, phenylureido, N, N-dioctylureido). ), Carbon number 1
To 36 sulfamoylamino groups (eg, N, N-dipropylsulfamoylamino), alkylthio groups having 1 to 36 carbon atoms (eg, octylthio, 3-phenoxypropylthio), arylthio groups having 6 to 36 carbon atoms (Phenylthio, 2,6-diisopropylphenylthio),
An alkoxycarbonylamino group having 2 to 36 carbon atoms (for example, methoxycarbonylamino), a sulfonamide group having 1 to 36 carbon atoms (for example, octanesulfonamide, o
-Toluenesulfonamide), a carbamoyl group having 1 to 36 carbon atoms (for example, N, N-dibutylcarbamoyl),
A sulfamoyl group having 1 to 36 carbon atoms (for example, N, N-
Dibutylsulfamoyl), a sulfonyl group having 1 to 36 carbon atoms (for example, octansulphonyl, 2,4,6-trimethylbenzenesulfonyl), an alkoxycarbonyl group having 2 to 36 carbon atoms (for example, methoxycarbonyl,
2,6-di-t-butylcyclohexyloxycarbonyl), a heterocyclic oxy group having 1 to 36 carbon atoms (for example, 1
-Phenyltetrazole-5-oxy), having 1 to 3 carbon atoms
6 acyloxy groups (eg acetoxy), 1 to 1 carbon atoms
36 carbamoyloxy groups (for example, N-phenylcarbamoyloxy), silyloxy groups (trimethylsilyloxy), imide groups having 4 to 36 carbon atoms (for example, N-
Phthalimide), a heterocyclic thio group having 1 to 36 carbon atoms (for example, 2-benzothiazolylthio, 2-pyridylthio), a sulfinyl group having 1 to 36 carbon atoms (for example, 3
Phenoxypyropyrsulfinyl), a phosphonyl group having 1 to 36 carbon atoms (for example, phenylphosphonyl), an aryloxycarbonyl group having 1 to 36 carbon atoms (for example, phenoxycarbonyl), an acyl group having 1 to 36 carbon atoms (for example, Acetyl, benzoyl) and azolyl groups (eg imidazolyl, pyrazolyl). Among these substituents, those that can be further substituted may be further substituted with the substituents listed here.

R ₃ is preferably an aliphatic group or
An aryl group. Wherein the substituents of R ₄ are the same as substituents exemplified in R _3, preferably R ₄ is hydrogen atom or an aliphatic group.

In the formula, X represents a hetero ring, a substituted amino group or an aryl group, and the hetero ring is a 5- to 8-membered ring having a nitrogen atom, an oxygen atom or a sulfur atom and having 1 to 36 carbon atoms. Are preferred. More preferably,
A 5- or 6-membered ring bonded by a nitrogen atom, of which a 6-membered ring is particularly preferred. A benzene ring or a hetero ring may be condensed with these rings. Specific examples of X include imidazole, pyrazole, triazole, lactam compound, piperidine, pyrrolidine, pyrrole, morpholine, pyrazolidine, thiazolidine, pyrazolidine and the like, preferably morpholine and piperidine, particularly preferably morpholine.

Examples of the substituent of the substituted amino group include an aliphatic group, an aryl group and a heterocyclic group. Examples of the aliphatic group include the substituents of R ₁ and R ₂ mentioned above, which are further substituted with a cyano group, an alkoxy group (for example, methoxy), an alkoxycarbonyl group, a chlorine atom, a hydroxyl group, a carboxyl group or the like. It may have been done. As the substituted amino group, disubstitution is preferable to monosubstitution.
Specific examples of the substituted amino group include a dicyanoethylamino group, a dicyclohexylamino group, a dimethoxyethylamino group and a diallylamino group. The aryl group for X is preferably one having 6 to 36 carbon atoms. Specific examples include phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl,
Methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, naphthyl and the like can be mentioned.

Preferred as the substituent of Y is a group capable of splitting off under alkaline conditions as described in, for example, JP-A-61-282844 and JP-A-56.
Examples of the substituent include a substituent which is coupled off by a reaction with an oxidized product of a developing agent as described in JP-A-133734. Preferably Y is a hydrogen atom.

Specific examples of the coupler of the present invention are shown below, but the couplers are not limited to these.

[0016]

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[0017]

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[0018]

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[0019]

[Chemical 6]

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

[Chemical 12]

The compound represented by the general formula (I) of the present invention can be prepared by a known method, for example, JP-A-5-255333.
It can be synthesized by the method described in Nos. 5-202004 and 7-48376.

Specific synthetic examples of the compound of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplified Compound (1) Exemplified Compound (1) was synthesized by the following route.

[0028]

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Synthesis of compound (b) 2,6-di-t-butyl-4-methylphenol, 17
To a solution of g (77 mmol) in 200 ml of acetonitrile at 0 ° C., trifluoroacetic anhydride, 10.6 ml (7
5 mmol) and then compound (a), 15.
6 g (60.4 mmol) was added slowly. The reaction solution was stirred at room temperature for 2 hours, then, 300 ml of water and 300 ml of ethyl acetate were added for extraction. The organic layer is layered with water, water,
Washed with saline. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain 19.6 g of (b). Synthesis of compound (c) To a solution of 19.6 g of (b) in 200 ml of ethyl acetate was added 5 ml of pyridine, and bromine was added dropwise under water cooling. After stirring for 1 hour, 300 ml of water and 300 ml of ethyl acetate were added for extraction. After extraction, the ethyl acetate layer was dried over magnesium sulfate, the solvent was evaporated, and acetonitrile was added to the residue for recrystallization. 18.0 g of (c) was obtained. Synthesis of Compound (d) Methyl cyanoacetate 2.2 g of dimethylacetamide 20
0.8 ml of sodium hydride was slowly added to the ml solution at 0 ° C., and the mixture was stirred at room temperature for 30 minutes. (Solution S) 10.0 g of (c) dissolved in 50 ml of dimethylacetamide
Was slowly added dropwise to (Solution S) under ice cooling. After stirring for 1 hour, 4 g of sodium hydroxide dissolved in 20 ml of water and 20 ml of methanol were added to the reaction solution, and the reaction temperature was adjusted to 5
The temperature was kept at 0 ° C. and the mixture was stirred for 1 hour. After the reaction, add ethyl acetate to 2
00 ml was added and neutralized with hydrochloric acid. After washing with water,
The ethyl acetate layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude compound (d). Synthesis of Exemplified Compound (1) 8.0 g of the obtained crude compound was added to dimethylacetamide 40
ml, and dissolved in 6 ml of pyridine, and at 0 ° C., 4.3 g of morpholinocarbonyl chloride was added. The mixture was stirred at room temperature for 2 hours, poured into 200 ml of diluted hydrochloric acid water, and extracted with 200 ml of ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, hexane was added to the residue, and crystallization was performed to give the exemplified compound (1).
Was obtained.

Synthesis Example 2. Synthesis of Exemplified Compound (25) In the synthesis of compound (1), 4.5 g of diallylcarbamoyl chloride was added in place of morpholinocarbonyl chloride and stirred at room temperature for 2 hours. After the reaction,
It was poured into 200 ml of diluted hydrochloric acid water and extracted with 200 ml of ethyl acetate. After drying the aerobic layer with magnesium sulfate, the solvent was distilled off under reduced pressure, hexane was added to the residue, and crystallization was performed to obtain 5.5 g of the target exemplified compound. Other compounds can be similarly synthesized.

The light-sensitive material of the present invention may have at least one layer containing the coupler of the present invention on a support,
The coupler is usually contained in a hydrophilic colloid layer consisting of a gelatin binder. A general light-sensitive material can be constructed by coating at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support. The order may be any order. An infrared-sensitive silver halide emulsion layer can also be used in place of at least one of the above-mentioned photosensitive emulsion layers. These light-sensitive emulsion layers contain a silver halide emulsion having sensitivity in each wavelength range and a coupler that forms a dye having a complementary color with the light to be exposed, so that color reproduction by the subtractive color method can be performed. Can be. However, the photosensitive emulsion layer and the hue of the coupler may not have the above correspondence. The couplers of this invention are also useful as yellow or magenta couplers,
It is particularly useful as a cyan coupler and can be incorporated in any photosensitive silver halide emulsion layer. The amount of the coupler of the present invention added to the light-sensitive material is appropriately 1 × 10 ^-3 to 1 mol, and preferably 2 × 10 ^{-3 to} 3 × 10 ^-1 mol, per mol of silver halide. When the coupler of the present invention is used as a cyan coupler, a conventional 5-pyrazolone magenta coupler or a pyrazoloazole magenta coupler is used as a magenta coupler which can be used in combination therewith, and among them, hue, image stability, and color development. In terms of properties, etc., a pyrazolotriazole coupler having a secondary or tertiary alkyl group directly bonded to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-61-65245; No. 65246, a pyrazolotriazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and a European patent. 226,84
No. 6 described in No. 9A and No. 294,785A.
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the position.

The yellow couplers that can be used in combination include conventional pivaloylacetanilide couplers and benzoylacetanilide yellow couplers, as well as acyl groups described in European Patent No. EP 0449769A1.
To an acylacetamide type yellow coupler having a 5-membered cyclic structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0482552A1, and a dioxane described in US Pat. No. 5,118,599. An acylacetamide type yellow coupler having a structure is also preferably used. Among them,
It is particularly preferable to use an acylacetamide type yellow coupler in which an acyl group is a 1-alkylcyclopropane-1-carbonyl group, or a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The coupler of the present invention can be introduced into the light-sensitive material by various known dispersion methods, but it is dissolved in a high-boiling organic solvent (a low-boiling organic solvent may be used in combination) and emulsified and dispersed in an aqueous gelatin solution to form a silver halide. An oil-in-water dispersion method of adding to an emulsion is preferably used. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the coupler can be dispersed by a polymer dispersion method, one of which is a specific example of the latex dispersion method in US Pat. No. 4,199,363.
West German Patent (OLS) No. 2,541,274, Japanese Patent Publication No. 5
No. 3-41,091 and the like. As a more preferable method, a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 723.

As the high boiling point organic solvent which can be used in the oil-in-water dispersion method, phthalic acid esters (dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, etc.), phosphoric acid or phosphonic acid esters are used. (Triphenyl phosphate, tricresyl phosphate, tri-phosphate
2-ethylhexyl, etc.), fatty acid esters (di-2-ethylhexyl succinate, tributyl citrate, etc.), benzoic esters (2-ethylhexyl benzoate, dodecyl benzoate, etc.), amides (N, N-diethyldodecane) Amides, N, N-dimethyloleinamides, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), anilines (N, N-dibutyl-2-butoxy-5-te)
rt-octylaniline, etc.), chlorinated paraffins, hydrocarbons (dodecylbenzene, diisopropylnaphthalene, etc.), carboxylic acids (2- (2,4-di-tert-
Amylphenoxy) butyric acid and the like. As an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher and 160 ° C. or lower (ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, methyl cellosolve acetate, dimethylformamide, etc.) may be used in combination. The high boiling point organic solvent is used in an amount of 0 to 10 times, preferably 0 to 4 times the weight of the coupler.

The silver halide emulsions and other materials used in the present invention, the layer structure of the light-sensitive material, and the processing methods and processing additives applied to process the light-sensitive material are described in JP-A- 62-215,272, JP-A-2-33,144, JP-A-2-854, JP-A-2-93,
Those described in No. 641, No. 3-194,539 and the like are preferably used.

In the present invention, silver bromide, silver iodobromide, silver chlorobromide, silver chloride and the like are used as the silver halide grains.
For rapid processing, it is preferable to use silver chloride, silver chlorobromide or silver chloroiodobromide grains in which 95 mol% or more is silver chloride. In particular, in the present invention, in order to further shorten the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, “containing substantially no silver iodide” means that the silver iodide content is 1
It means not more than mol%, preferably not more than 0.2 mol%. On the other hand, 0.01 to 3 mol% of the emulsion surface described in JP-A-3-84545 is used for the purpose of increasing the high illuminance sensitivity, increasing the spectral sensitization sensitivity, or increasing the stability over time of the photosensitive material. In some cases, high silver chloride grains containing silver iodide are preferably used. The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in a layered or non-layered form inside and / or on the surface of silver halide grains. The silver halide composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably 20 mol% or more.

As the compound which forms a dye by oxidative coupling with the coupler of the present invention, not only a conventional aromatic primary amine compound (for example, a phenylenedisimine color developing agent) but also European Patents 545491A1 and 565165 are used.
A1 and sulfonylhydrazine compounds and carbamoylhydrazine compounds described in Japanese Patent Application No. 7-49287 can be used. The coupler of the present invention is also preferably used in a photosensitive material for an advanced photo system having a magnetic recording layer. The coupler of the present invention can also be applied to a system for heat development using a small amount of water or a complete dry system for heat development without using water at all. These systems are disclosed in JP-A-6-35,118 and JP-A-6-35,118.
-17,528, JP-A-56-146,133, JP-A-60-119,557 and JP-A-1-161,236.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples, but of course the present invention is not limited thereto. Example 1 Using an undercoated polyethylene terephthalate support, a single-layer photosensitive material 101 for evaluation of the following layer constitution was prepared. (Preparation of Coating Solution for Emulsion Layer) 1.85 mmol of coupler, 10 ml of ethyl acetate, dibutyl phthalate (solvent) and trioctyl phosphate (solvent) were added to the coupler in an amount of 50% by weight to dissolve each coupler. This solution was emulsified and dispersed in 33 g of a 14% gelatin aqueous solution containing 3 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture of a large size emulsion having an average grain size of 0.88 μm and a small size emulsion having a grain size of 0.70 μm (silver molar ratio). The variation coefficient of grain size distribution is 0. 0
8 and 0.10. For each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the surface of grains based on silver chloride. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion and this emulsion were mixed and dissolved to prepare an emulsion layer coating solution having the following composition. In addition, 1-oxy-3,5-
Sodium dichloro-s-triazinate was used. (Layer Structure) The layer structure of the sample used in this experiment is shown below. (Numbers indicate coating weight per m ^2.)

[Support] Polyethylene terephthalate support [Emulsion layer] Silver chlorobromide emulsion (previously described) 3.0 mmol coupler (coupler described in Table A) 1.0 mmol tricresyl phosphate (50% by weight based on coupler) Trioctyl phosphate (50% by weight based on coupler) Gelatin 5.5 g [Protective layer] Gelatin 2.5 g Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.15 g Liquid paraffin 0.03 g

The structure of the comparative coupler used in this example is shown below. (Refer to the above compound examples for the structure of the coupler of the present invention.)

[0041]

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Sample 101 was prepared in the same manner as sample 101 except that the cyan coupler was replaced with the coupler shown in Table A in a 1/2 molar amount and the silver halide amount was changed to 1/2. Samples 102 to 1 in exactly the same manner
15 was produced. After gradation exposure was performed on the above sample using an optical wedge, the sample was processed using the following processing steps and processing solutions.

(Processing step) Processing step Temperature Time Color development 35 ° C 40 seconds Bleach fixing 35 ° C 60 seconds Water washing 35 ° C 120 seconds

(Composition of processing solution) [Color developer] Distilled water 800 ml Triethanolamine 8.1 g Diethylhydroxylamine 4.2 g Potassium bromide 0.05 g Sodium chloride 0.5 g Sodium hydrogen carbonate 3.9 g Sodium sulfite 0.13 g N-ethyl-N -(Β-Methanesulfonamidoethyl) -3-methyl-4-aminoaminoline sulfate 5.0 g Potassium carbonate 18.7 g Water was added to 1000 ml pH 10.15

[Bleach-fixing solution] Distilled water 400 ml Ammonium thiosulfate (700 g / l) 150 ml Sodium sulfate 18.0 g Ethylenediaminetetraacetic acid iron (III) ammonium 55.0 g Ethylenediaminetetraacetate 5.0 g Water 1000 ml pH 6.70

The red light optical density of the sample after the treatment was measured,
The maximum color density Dmax was determined. In addition, cyan density 1.0
The yellow density at the point of giving a value was measured with an X-Rite 310 densitometer (made by X-Rite Company). The lower the yellow density, the smaller the secondary absorption and the better the hue.
Next, these samples were irradiated with light for 5 days through a sharp cut filter capable of cutting about 50% at 390 nm under a 200,000 lux Xe light source (5 hours light / 1 hour dark irradiation). The red light optical density of the sample after light irradiation was measured again, and the color image residual ratio after light irradiation was determined. The residual ratio of the color image is shown in Table A as a percentage when the initial density is set to 100% by evaluating two points of the Dmax area and the low density area showing the color density of ⅕ of Dmax.

[0047]

[Table 1]

As is clear from Table A, Samples 102 to 115 are superior in hue to Sample 101. However, Samples 102 to 104 have poor light fastness in the low density portion, and are clearly inferior to Comparative Sample 101. On the other hand, the coupler of the present invention is obviously excellent in hue, but it is clear that it is excellent in light fastness particularly in a low density portion.

Next, the samples 101 to 115 were exposed and processed in the same manner as above, and then stored at 100 ° C. for 10 days to evaluate the residual ratio of the color image at the maximum color density. The results are shown in Table B.

[0050]

[Table 2]

From Table B, it is obvious that Samples 105 to 115 using the coupler of the present invention are superior in heat fastness to Sample 101 using the comparative coupler Ex-1, but the corresponding chlorine atom releasing couplers. Sample 10 using
It can be seen that the robustness is further improved for Nos. 2 and 104.

Example 2 On the surface of a paper support laminated on both sides with polyethylene, a corona discharge treatment was applied, and then a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic printing paper (201) having the layer structure shown in was prepared. The coating solution was prepared as follows. Preparation of Fifth Layer Coating Solution 10 g of cyan coupler (ExC-1) was mixed with a solvent (Sol).
v-6) 4 g, solvent (Solv-8) 10 g, color image stabilizer (Cpd-6) 2 g, color image stabilizer (Cpd-8) 4
g, a solvent color image stabilizer (Cpd-13) 8 g and ethyl acetate 50 ml, and this solution was dissolved in a surfactant (Cpd-
12) Emulsion C having an average particle size of 0.15μ when emulsified and dispersed in 400 g of a 12% gelatin aqueous solution containing 1.2 g
Was prepared. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C having a grain size of 0.41 μm (silver molar ratio). Coefficient of variation of grain size distribution is 0.09 and 0.11, respectively, and 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride for each size emulsion). In this emulsion, the red sensitizing dyes G and H shown below were respectively added to the large-sized emulsion C per mol of silver in an amount of 5.0 ×.
10 ⁻⁵ mol, and to the small size emulsion C, 8.0 × 10 ⁻⁵ mol was added. Further, the additive X was added in an amount of 2.6 × 10 ⁻³ per mol of silver halide. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion C and this silver chlorobromide emulsion C
And were mixed and dissolved, and a fifth layer coating solution was prepared so as to have the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to seventh layers were prepared in the same manner as the coating solution for the fifth layer. These coating solutions are prepared 1
It was applied in 5 minutes. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, AS-1, AS-2, AS-3 are provided in each layer.
And AS-4, each having a total amount of 15.0 mg / m ² ,
6.0 mg / m ² , 5.0 mg / m ² and 10.0 mg
/ M ² .

[0054]

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The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0056]

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(Large size milk per mol of silver halide)
1.4 × 10 ^-FourMole, small
1.7 × 10^-FourMolar addition
did. Green sensitive emulsion layer

[0058]

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(Sensitizing dye D per mol of silver halide, 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, Also,
Sensitizing dye E per mol of silver halide was 4.0 × 10 ⁻⁵ mol for large-sized emulsion, 7.0 × 10 ⁻⁵ mol for small-sized emulsion, and sensitizing dye. F per mol of silver halide is 2.0 for large emulsions.
× 10 ^-4 mol, or 2.8 × 1 for small emulsions
^0-4 moles were added. ) Red-sensitive emulsion layer

[0060]

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(5.0 × 10 ^-5 mol each for large size emulsion and 8.0 × 10 ^-5 mol each for small size emulsion per mol of silver halide) Further, the following compounds are added per mol of silver halide: 2.
6 × 10 ⁻³ mol was added.

[0062]

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Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × 10 ⁻ per mol of silver halide. ⁴ mol, 1.0 x 10 ^-3
Mol and 5.9 × 10 ⁻⁴ mol. Furthermore, the second layer,
0.2 mg / m 2 for each of the 4th, 6th and 7th layers
² , 0.2 mg / m ² , 0.6 mg / m ² , 0.1 mg
/ M ² was added. In addition, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively.

As the irradiation-inhibiting water-soluble dye, the following compounds were added separately in the second, fourth and sixth layers.

[0065]

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(Layer constitution) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coated amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ content 15% by weight) and bluish dye (ultra-blue)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (cubic, 3: 7 mixture of large size emulsion A having an average grain size of 0.88 μm and small size emulsion A of 0.70 μm (silver mole: The coefficients of variation of the grain size distribution are 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride. ) 0.26 gelatin 1.4 yellow coupler (ExY) 0.64 color image stabilizer (Cpd-1) 0.078 color image stabilizer (Cpd-2) 0.038 color image stabilizer (Cpd-3) 0 0.085 Color image stabilizer (Cpd-5) 0.020 Color image stabilizer (Cpd-9) 0.005 Solvent (Solv-1) 0.11 Solvent (Solv-6) 0.11

Second Layer (Color Mixing Prevention Layer) Gelatin 1.0 Color mixing inhibitor (Cpd-4) 0.11 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22 Solvent (Solv-3) 0.08 Solvent (Solv-7) 0.01 Ultraviolet absorber (UV-B) 0.07

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having average grain size 0.55 μm and small size emulsion B having 0.39 μm (silver molar ratio) The variation coefficients of the grain size distribution are 0.10 and 0.08, respectively.Each size emulsion contained 0.7 mol% of silver bromide locally on a part of the grain surface based on silver chloride. 0.11 Gelatin 1.3 Magenta coupler (ExM) 0.13 UV absorber (UV-A) 0.12 Color image stabilizer (Cpd-2) 0.010 Color image stabilizer (Cpd-5) 0. 020 Color image stabilizer (Cpd-6) 0.010 Color image stabilizer (Cpd-7) 0.080 Color image stabilizer (Cpd-8) 0.030 Color image stabilizer (Cpd-10) 0.002 Solvent (Solv-3) 0.15 Solvent (Solv-4) 0.2 The solvent (Solv-5) 0.11

Fourth Layer (Color Mixing Prevention Layer) Gelatin 1.0 Color mixing inhibitor (Cpd-4) 0.20 Solvent (Solv-1) 0.03 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.04 Solvent (Solv-7) 0.01 Ultraviolet absorber (UV-B) 0.04

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having average grain size 0.50 μm and small size emulsion 0.41 μm (silver molar ratio)) The variation coefficients of the grain size distribution were 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride. 0.085 Gelatin 0.99 Cyan coupler (Ex-1) 0.15 Solvent (Solv-6) 0.06 Solvent (Solv-8) 0.15 Color image stabilizer (Cpd-6) 0.03 color Image stabilizer (Cpd-8) 0.06 Color image stabilizer (Cpd-13) 0.12

Sixth Layer (UV Absorbing Layer) Gelatin 0.63 UV Absorber (UV-C) 0.35 Color Image Stabilizer (Cpd-7) 0.050 Solvent (Solv-9) 0.050

Seventh layer (protective layer) Acid-treated gelatin 1.0 Polyvinyl alcohol acrylic modified copolymer 0.043 (Modification degree 17%) Liquid paraffin 0.018 Surfactant (Cpd-11) 0.026

[0074]

[Chemical 21]

[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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Except for changing the composition of the fifth layer, the photosensitive material 201 prepared as described above was prepared in the same manner as described above.
Photosensitive materials 202 to 210 were prepared. In making these changes, the coupler of the general formula [I] was changed in an equimolar amount. Further, the average particle size of the coupler-containing lipophilic fine particles prepared when these samples were prepared was 0.13 to 0.
It was in the range of 15 μm. The coated sample thus obtained was stored at room temperature for 14 days and then evaluated as described below.

First, the light-sensitive material 204 is coated with about 30 times the silver amount.
After imagewise exposure such that 100% of the color is developed, the color developer is used in a tank volume of 2% by the following processing steps using a paper processor.
Continuous processing was performed until the double amount was replenished.

Treatment Step Temperature Time Replenishment Amount Tank Capacity Color Development 38.5 ° C. 45 sec 73 ml 500 ml Bleach-fix 30-35 ° C. 45 sec 60 ml 500 ml Rinse 30-35 ° C. 20 sec ----- 500 ml Rinse 30-35 ° C. 20 sec --- 500 ml Rinse 30-35 ° C. 20 seconds 370 ml 500 ml Dry 70-80 ° C. 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (rinse is a 3-tank counter-current system to →)

The composition of each processing liquid is as follows. Color developer Tank solution Replenishment amount Water 700ml 700ml Sodium triisopropylene (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 3.0g 3.0g 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5 g 0.5 g triethanolamine 12.0 g 12.0 g potassium chloride 6.5 g-potassium bromide 0.03 g-potassium carbonate 27.0 g 27.0 g optical brightener (WHITEX 4, manufactured by Sumitomo Chemical) 1. 0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Diethyl hydroxylamine 1.0 g 1.0 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10.0 g 13.0 g N-ethyl-N- (β- methanesulfonic amidoethyl) -3-methyl-4 - Aminoani Adding emission sulfate 5.0 g 11.5 g Water 1000ml 1000ml pH (25 ℃) 10.0 11.0

Bleach-fixing solution (same as tank solution and replenisher) Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Nitric acid (67) %) 30 g water was added to 1000 ml pH (25 ° C.) (with acetic acid and aqueous ammonia) 4.8

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

Next, each sample was subjected to gradation exposure with a three-color separation optical wedge for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). . The exposure at this time was performed such that the exposure amount was 250 CMS with an exposure time of 0.1 second. The exposed sample was treated with the running liquid described above using a paper processor.

100,000 lux X for each sample after treatment
The color image fastness was evaluated under the conditions of e light source (5 hours light / 1 hour dark intermittent irradiation) for 14 days and 100 ° C. for 14 days. Evaluation of light fastness is 2 with initial density of 2.0 and 0.5
In terms of heat fastness, the initial concentration was 2.0. The results are shown in Table C. Regarding the heat fastness, the change in the amount of coloring in the white background portion was measured by the blue optical density, and is also shown in Table C as ΔDmin.

[0090]

[Table 3]

From Table C, Samples 205 to 210 using the coupler of the present invention have a particularly high heat fastness to Sample 201, and light fastness to Samples 202 to 204 in addition to light fastness. It can be seen that it is superior in terms of points and has a clear advantage in total performance.

Example 3 Samples 301 to 310 were prepared in exactly the same manner as Samples 201 to 210 except that the composition of the first layer of Samples 201 to 210 in Example 2 was changed as follows.

[0093]

[Table 4]

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The same evaluation as in Example 2 was carried out on the above sample, and it was found that the light-sensitive material using the coupler of the present invention had the same hue, light fastness and light-sensitive property as those shown in Example 2.
It was revealed that it was excellent in terms of heat fastness.

Example 4 The same sample 401 as the sample 101 of Example 1 of JP-A-6-3779 was prepared. Also, in the sample 401,
Samples 402 to 410 were prepared in exactly the same manner as Sample 501, except that the coupler C-3 of the 5th and 6th layers was replaced with the coupler shown in Table D in an equimolar amount.

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The sample prepared as described above was imagewise exposed and subjected to the developing treatment described in Example 1 of the above-mentioned JP-A-6-3779.

After the above treatment, the color image fastness was evaluated for each sample under the conditions of 100,000 lux Xe light source (5 hours light / 1 hour dark intermittent irradiation) for 10 days and 100 ° C. for 14 days. The light fastness was evaluated at initial concentrations of 2.0 and 0.5.
The heat fastness was performed at an initial concentration of 2.0. The results are shown in Table D.

[0100]

[Table 5]

From Table D, Samples 405 to 410 using the coupler of the present invention are particularly fast to the sample 401 in terms of heat fastness, and Samples 402 to 404 are light fast in a low density portion. It can be seen that the total performance is clearly superior.

Example 5 No. 2 of the sample 101 of Example 1 of JP-A-6-208196
Cyan coupler used for the 1st and 3rd layers

[0103]

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The couplers (1), (2), and
Samples 601 to 605 were prepared in the same manner except that (4), (8) and (25) were replaced with equimolar amounts. Photosensitizer (FWH type, light source color temperature 32
00K, manufactured by Fuji Photo Film Co., Ltd., 250
After the exposure for CMS and sensitometry for 1 second, the treatment described in Example 1 of JP-A-6-208196 was performed.
Further, a cyan coupler used in the third layer of the sample 101 of Example 1 of JP-A-6-118546

[0105]

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The couplers (1), (2), and
Samples 506 to 510 were prepared in the same manner except that (4), (18) or (25) was replaced with an equimolar amount. Each sample was exposed and developed by the method described in Example 4 of JP-A-6-118546 to prepare a color proof. When the above sample was evaluated in exactly the same manner as in Example 2, the light-sensitive material using the coupler of the present invention showed the same hue, light fastness, heat fastness and processing dependence as those shown in Example 2. It has become clear that

[0107]

The color photographic light-sensitive material of the present invention has a hue,
Excellent light fastness and heat fastness, and low processing dependence.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains at least one coupler represented by the following general formula (I). General formula (I) (In the general formula (I), R ₁ and R ₂ represent an aliphatic group,
X represents a heterocyclic group, a substituted amino group or an aryl group, R ₃ and R ₄ represent a hydrogen atom or a substituent,
Y represents a hydrogen atom or a substituent. )