JPH0371701B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light and stain generation is prevented. . [Prior art] Conventionally, aromatic primary
The oxidized product of the amine-based color developing agent and the coloring agent undergo a coupling reaction to produce, for example, indophenol, indoaniline, indamine, azomethine,
It is well known that phenoxazine, phenazine, and pigments similar to them are produced to form color images. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional colors, namely yellow, magenta and A silver halide color photographic material containing a coupler that develops cyan color is used. Examples of couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, pyrazoloiriazole, and indazolone couplers. is known,
Furthermore, as a coupler for cyan image formation,
For example, phenolic or naphthol couplers are commonly used. It is desired that the dye image thus obtained does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity. In addition, uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) turn yellow due to light or moist heat (hereinafter referred to as Y
- A product that does not cause stains is desired. However, in the case of magenta couplers, fading of uncolored areas due to light, Y-stain due to moist heat, and color fading of dye image areas due to light is much larger than that of yellow couplers and cyan couplers, and often poses a problem. Couplers commonly used to form magenta dyes are 1,2-pyrazolo-5-ones. A major problem with the dye formed from this 1,2-pyrazolo-5-one magenta coupler is that in addition to the main absorption near 550 nm, it also has a secondary absorption near 430 nm. Various studies have been conducted. A magenta coupler having an anilino group at the 3-position of a 1,2-pyrazolo-5-one has a small side absorption and is particularly useful for obtaining a color image for printing. These techniques are described in, for example, US Patent No. 2,343,703, British Patent No. 1,059,994, and the like. However, the above-mentioned magenta coupler has the disadvantage that the image storage property, especially the fastness of the dye image to light, is extremely poor, and the Y-stain in the uncolored area is large. As another means for reducing the side absorption near 430 nm of the above magenta coupler, British patent No.
Pyrazolobenzimidazoles described in US Patent No. 1047612, indazolones described in US Patent No. 3770447, and US Pat.
Magenta couplers such as pyrazolotriazoles described in No. 1252418 and No. 1334515 have been proposed. Among these, 1H described in U.S. Patent No. 3725067, British Patent No. 1252418, and British Patent No. 1334515
The dye formed from the -pyrazolo-[3,2-C]-s-triazole coupler has a sub-absorption near 430 nm of the 1,2-triazole group having an anilino group at the 3-position.
- It is significantly smaller than dyes formed from pyrazol-5-ones and is preferred for color reproduction;
It has the advantage that the generation of Y-stain in uncolored areas is extremely small when exposed to light, heat, and humidity. However, 1H-pyrazolo-[3,2-C]
-The azomethine dye formed from the s-triazole coupler has extremely low fastness to light;
Moreover, the dyes are easily discolored by light, which significantly impairs the performance of color photographic materials, especially print-type color photographic materials, and therefore they have not been put to practical use in print-type color photographic materials. Moreover, in JP-A-59-125732, by using a 1H-pyrazolo-[3,2-C]-s-triazole type magenta coupler together with a phenol compound or a phenyl ether compound,
Techniques have been proposed to improve the light fastness of magenta dye images obtained from 1H-pyrazolo-[3,2-C]-s-triazole type magenta couplers. However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light. [Object of the invention] The present invention has been made in view of the above problems, and
A first object of the present invention is to provide a color photographic material with excellent color reproducibility and significantly improved light fastness of magenta dye images. A second object of the present invention is to provide a color photographic material having a magenta dye image that is less discolored by light. A third object of the present invention is to provide a color photographic material that is prevented from producing Y-stain in uncolored areas when exposed to light and moist heat. [Configuration of the Invention] The above object of the present invention is to provide 1-H-pyrazolo-[3,
This is achieved by a silver halide color photographic light-sensitive material containing a 2-C]-s-triazole type coupler and at least one of the compounds represented by the following general formulas [A] to [E]. General formula [A] In the formula, R ¹ represents an aliphatic group, a cycloalkyl group or an aryl group. R ² represents a hydrogen atom or the same group as R ¹ above. The piperazine ring may be substituted with an alkyl group. General formula [B] In the formula, R ³ represents the same group as R ¹ above. The morpholine ring may be substituted with an alkyl group. General formula [C] In the formula, R ⁴ represents the same group as R ¹ above. The thiamorpholine ring may be substituted with an alkyl group. General formula [D] In the formula, R ⁵ represents the same group as R ¹ above. R ⁶ represents the same group as R ² above. The imidazolidine ring may be substituted with an alkyl group. General formula [E] In the formula, R ⁷ represents the same group as R ¹ above. R ⁸ represents the same group as R ² above. The homopiperazine ring may be substituted with an alkyl group. [Specific Structure of the Invention] The 1H-pyrazolo-[3,2-C]-s-triazole type magenta coupler (hereinafter abbreviated as triazole type magenta coupler) used in the color photographic material of the present invention has the following general formula: Represented by []. General formula [] In the formula, R ₁ is a halogen atom or 1 that can be separated by a coupling reaction with an oxidized developing agent.
It represents a valent organic group, and monovalent organic groups include an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group formed with a 5- or 6-membered ring, an alkylthio group, an arylthio group, and a 5- or 6-membered ring. a heterocyclic thio group formed by or

[Formula] (However, A ₁ and A ₂ may be the same or different,
Each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and A ₁
and A ₂ cannot both be hydrogen atoms. Also,
A ₁ and A ₂ may be bonded to each other to form a 5- or 6-membered ring together with the nitrogen atom. This 5 or 6
The membered ring may further be fused with a benzene ring/heterocycle. ) can be mentioned. R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom, an alkyl group (e.g., methyl group, propyl group, t-butyl group, hexadecyl group, 2-
(2,4,6-trichlorophenyl)ethyl group,
3-(3-pentadecylphenoxy)propyl group,
3-(2,4-di-tert-amylphenoxy)propyl group, 2-[α-(3-tert-butyl-4-hydroxyphenoxy)tetradecanamidoethyl] group, etc.), aryl group (e.g., phenyl group) ,
α or β-naphthyl group, 4-methylphenyl group, 2,4,6-trichlorophenyl group, 4-
[α-(3-tert-butyl-4-hydroxyphenoxy)tetradecanamide]-2,6-dichlorophenyl group, etc.), heterocyclic groups (e.g., pyridyl group, thienyl group, quinolyl group, etc.), acylamino groups (e.g. acetylamino group, benzamide group, 3-(2,4-di-tert-amylphenoxy)
butylamide group, 3-(3-pentadecylphenoxy)butylamide group, etc.), alkylamino group (e.g., methylamino group, diethylamino group,
n-dodecylamino group, etc.), anilino group (e.g.,
phenylamino group, 2-chloro-5-tetradecanamide phenylamino group, 4-[α-(3-t-
butyl-4-hydroxyphenoxy)tetradecanamido]anilino group, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, tetradecyloxycarbonyl group, etc.), alkylthio groups (e.g., hexylthio group, dodecylthio group, etc.)
, and R ₁ and R ₂ are never hydrogen atoms at the same time. The pyrazolotriazole magenta coupler used in the present invention is disclosed in, for example, US Pat. No. 3,705,896;
No. 3725767, No. 3758309, No. 3810761, British Patent No. 1252418, British Patent No. 1334515, Special Publication No. 58-42045
No. 58-64882, No. 58-167326, No. 58
−206321, No. 58-214853, No. 58-217339,
Examples thereof include compounds described in No. 59-24653 and the like. Typical specific examples of the triazole type magenta coupler used in the present invention are shown below, but the present invention is not limited thereto. The magenta dye image stabilizers represented by the general formulas [A] to [E] used together with the triazole type magenta coupler of the present invention not only have the effect of preventing fading of magenta dye images due to light, but also have the effect of preventing fading of magenta dye images due to light. It also has an anti-discoloration effect. In the general formulas [A] to [E], R represents an aliphatic group, a cycloalkyl group, or an aryl group, and the aliphatic groups represented by R ¹ , R ³ , R ⁴ , R ⁵ and R ⁷ include: Examples include a saturated alkyl group that may have a substituent and an unsaturated alkyl group that may have a substituent. Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethenyl group, propenyl group, etc. It will be done. The cycloalkyl group represented by R ¹ , R ³ , R ⁴ , R ⁵ and R ⁷ may have 5 to 7 substituents.
Examples of the member cycloalkyl group include a cyclopentyl group and a cyclohexyl group. The aryl group represented by R ¹ , R ³ , R ⁴ , R ⁵ and R ⁷ includes a phenyl group which may have a substituent,
Represents a naphthyl group. Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R ¹ , R ³ , R ⁴ , R ⁵ and R ⁷ include alkyl group, aryl group, alkoxy group,
Examples include carbonyl group, carbamoyl group, acylamino group, sulfamoyl group, sulfonamide group, carbonyloxy group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, heterocyclic group, alkylthio group, arylthio group, etc., and these substituents include It may further have a substituent. Typical specific examples of the compounds represented by the general formulas [A] to [E] of the present invention are shown below, but the present invention is not limited thereto. Exemplary compound Among the magenta dye image stabilizers according to the present invention represented by the general formulas [A] to [E], piperazine-based compounds and homopiperazine-based compounds are particularly preferred, and more preferably, those represented by the following general formulas [] or [ ] It is a compound represented by. General formula [] General formula [] In the formula, R ₄ and R ₅ each represent a hydrogen atom, an alkyl group or an aryl group. However, R ₄ and R ₅ do not become hydrogen atoms at the same time. R ₆ to _{R 15} each represent a hydrogen atom, an alkyl group, or an aryl group. In the general formulas [] and [], R ₄ ,
R ₅ represents a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by R ₄ or R ₅ include a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group. group, octadecyl group, etc. The aryl group represented by R ₄ or R ₅ includes a phenyl group and the like. The alkyl group and aryl group represented by R ₄ or R ₅ may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and a heterocyclic group. It will be done. The total number of carbon atoms of R ₄ and R ₅ (including substituents) is preferably 6 to 40. In the general formula [] or [], R _6
-R15 each represent a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by _R6 to _R15 include a methyl group and an ethyl group. Examples of the aryl group represented by R ₆ to R ₁₅ include a phenyl group. Specific examples of the compound represented by the general formula [] or [] include the above-mentioned exemplary piperazine compounds (A-1) to (A-30) and exemplary homopiperazine compounds (E-1) to (E-12). ). Next, synthesis examples will be shown for typical magenta dye image stabilizers of the present invention represented by the above general formulas [A] to [E]. Synthesis Example 1 Synthesis of Exemplified Compound (A-2) Piperazine 9.0g and myristyl bromide
15 g of anhydrous potassium carbonate was added to 100 ml of acetone in which 55 g of potassium carbonate was dissolved, and the mixture was boiled and refluxed for 10 hours to react. After the reaction, pour the reaction solution into 500ml of water,
Extracted with 500ml of ethyl acetate. After drying the ethyl acetate layer over magnesium sulfate, the ethyl acetate was distilled off to obtain the desired product as white crystals. acetone 300
ml to give 340 g of white flaky crystals (yield
70%). Melting point 55-58℃ Synthesis Example 2 Synthesis of Exemplary Compound (B-4) 18 g of 4-morpholinoaniline was added to 100 g of ethyl acetate.
ml, 12 ml of acetic anhydride was added little by little while stirring and keeping the reaction solution at 20°C. After adding acetic anhydride, cooling on ice and filtering the precipitated crystals,
Recrystallized with ethyl acetate to obtain 16.5 g of self-colored powder crystals.
(yield 75%). Melting point: 207-210°C In the present invention, the following dye-forming couplers can be used in addition to the triazole-type magenta coupler of the present invention, namely:
In color development processing, aromatic primary amine color developing agents (e.g., phenylenediamine derivatives,
Examples of magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers. As,
Examples include acylacetamide couplers (eg, benzoylacetanilides, bivaloylacetanilides), and cyan couplers such as naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. Of course, two or more types of the above-mentioned couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. The yellow coupler used in the present invention is not particularly limited, but is preferably an α-pivaloylacetanilide coupler. Typical specific examples of yellow couplers that can be used in the present invention are listed below. These yellow couplers are disclosed in, for example, West German Publication No. 2057941, West German Publication No. 2163812, and Japanese Unexamined Patent Publication No. 1973-
No. 26133, No. 48-29432, No. 50-65231, No. 51
-3631, No. 51-50734, No. 51-102636, Japanese Patent Publication No. 51-33410, Japanese Patent Publication No. 66835, No. 48-
No. 94432, No. 49-1229, No. 49-10736, Tokukosho
52-25733, etc., and can be synthesized according to the synthetic methods described therein. In the present invention, the 1H-
The magenta coupler used in combination with the pyrazolo-[3,2-C]-s-triazole type magenta coupler is preferably a 1-phenyl-3-anilino-5-pyrazolone type coupler, and representative specific examples include: The following is given below. These magenta couplers are disclosed in, for example, US Pat. No. 3,684,514, British Patent No. 1,183,515, and Japanese Patent Publication No.
No. 6031, No. 40-6035, No. 44-15754, No. 45-
No. 40757, No. 46-19032, JP-A-50-13041,
It includes the compounds described in No. 53-129035, No. 51-37646, and No. 55-62454, and can be synthesized according to the synthesis methods described therein. The above magenta coupler is preferably used in an amount of 100 mol% or less with respect to the triazole type magenta coupler of the present invention. Furthermore, the cyan coupler used in the present invention is not particularly limited, but a phenolic cyan coupler is preferable. Typical specific examples of cyan couplers that can be used in the present invention are listed below. The above cyan coupler is, for example, US Pat.
No. 2423730, No. 2801171, JP-A-50-112038
No. 50-134644, No. 53-109630, No. 54-
No. 55380, No. 56-65134, No. 56-80045, No. 57
−155538, No. 57-204545, No. 58-98731,
59-31953, etc., and can be synthesized according to the synthetic methods described therein. The triazole type magenta coupler of the present invention and the magenta coupler, yellow coupler, and cyan coupler described above to be used in combination as necessary can be introduced into the silver halide emulsion layer by any method used in the art, such as the U.S. Pat. The method described in No. 2322027, etc. can be used. For example, phthalate alkyl polyesters (e.g., dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.), Acid esters (e.g., acetyl tributyl citrate, etc.), benzoate esters (e.g., octyl benzoate, etc.), alkylamides (e.g., diethyl laurylamide, etc.), fatty acid esters (e.g., dibutoxyethyl succinate, diethyl azelate, etc.) etc.), high boiling point organic solvents with a boiling point of about 180°C or higher, such as trimesate esters (e.g., tributyl trimethate, etc.), or low boiling point organic solvents, with a boiling point of about 30°C to 180°C, such as ethyl acetate group, butyl acetate group, etc. After dissolving in lower alkyl acetate such as ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. 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 can also be introduced into the hydrophilic colloid as an alkaline aqueous solution. In order to effectively achieve the object of the present invention, among the above-mentioned high-boiling point organic solvents, phosphoric acid ester-based or phthalate-based high-boiling point organic solvents are particularly preferred for the triazole type magenta coupler and magenta dye image of the present invention. Most preferred is when used in conjunction with a stabilizer. The phosphoric acid ester-based high-boiling organic solvent preferably used in the present invention includes triarylphosphates such as triphenyl phosphate and tricresyl phosphate, as well as others such as those described in Japanese Patent Publication No. 48-32727, JP-A-54-119921, No. 54-
Examples include phosphoric acid ester-based high-boiling organic solvents described in No. 119922, No. 55-25057, and No. 56-81836. Specific examples of preferred phosphoric acid ester high boiling point organic solvents are listed below, but the invention is not limited thereto. Next, phthalate ester compounds preferably used in the present invention are illustrated below. In the coupler photographic material of the present invention, the amount of triazole type magenta coupler added is preferably in the range of 1.5 x 10 ^-3 mol to 7.5 x 10 ^-1 mol, more preferably 1 x 10 -2 mol to 7.5 x 10 ^-1 mol per mol of silver. 5×
It is in the range of 10 ^-1 mol. The amount of the magenta dye image stabilizer represented by the general formulas [A] to [E] of the present invention used is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the triazole type magenta coupler of the present invention. ~
It is 200 mol%. In the color photographic material of the present invention, in addition to the magenta dye image stabilizer of the present invention, other magenta dye image stabilizers represented by the following general formula [V], that is, phenol compounds and phenyl ether compounds are added. Can also be used together. General formula [] In the formula, R ₁₆ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ₁₇ , R ₁₈ , R ₂₀ ,
R ₂₁ represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group or an acylamino group, and R ₁₉ represents an alkyl group, a hydroxy group, an aryl group or an alkoxy group. Further, R ₁₆ and R ₁₇ may be ring-closed with each other to form a 5- or 6-membered ring, in which case R ₁₉ represents a hydroxy group or an alkoxy group. Furthermore,
R ₁₆ and R ₁₇ may be ring-closed to form a methyleneoxy ring. Furthermore, R ₁₈ and R ₁₉ are ring-closed, and 5
A membered carbocyclic ring may be formed, in which case R ₁₆ represents an alkyl group, an aryl group or a heterocyclic group. The compound represented by the above general formula [ ] is disclosed in U.S. Patent Nos. 3935016, 3982944, and 4254216
No. 55-21004, No. 54-145530, British Patent Publication No. 2077455, No. 2062888, U.S. Patent No.
No. 3764337, No. 3432300, No. 3574627, No. 3573050, JP-A-52-152225, No. 53-20327
No. 53-17729, No. 55-6321, British Patent No.
No. 1347556, Publication No. 2066975, Special Publication No. 54-12337
No. 48-31625, U.S. Pat. No. 3,700,455, and the like. Specific examples of the compound represented by the general formula [] are shown below. The phenol compound or phenyl ether compound represented by the general formula [] is preferably 200 mol% or less based on the magenta dye image stabilizer represented by the general formulas [A] to [E] of the present invention. , more preferably in an amount of up to 140 mol %. The phenol compound and phenyl ether compound have the effect of preventing fading of the magenta dye image obtained from the triazole type magenta coupler of the present invention, but have almost no effect of preventing discoloration. Therefore, it is not preferable to use an excessive amount of the phenol compound and phenyl ether compound in the magenta dye image stabilizer of the present invention. In general, the magenta dye image obtained from the triazole type magenta coupler not only shows significant fading when exposed to light, but also undergoes significant discoloration due to light, and the color tone of the dye image changes from magenta to yellowish. The magenta dye image stabilizers represented by the general formulas [A] to [E] of the present invention are different from the conventional ones in that they can prevent fading and discoloration of the magenta dye image obtained from the triazole type magenta coupler due to light. It has effects that cannot be achieved with magenta dye image stabilizers made of phenol compounds and phenyl ether compounds. The triazole type magenta coupler of the present invention and the magenta dye image stabilizer of the present invention are preferably used in the same layer, but the stabilizer may be used in a layer adjacent to the layer in which the coupler is present. . The color photographic material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include U.S. Pat. No. 2403721,
Same No. 2418613, Same No. 2675314, Same No. 2701197,
Same No. 2704713, Same No. 278659, Same No. 2732300,
No. 2735765, JP-A No. 50-92988, No. 50-
No. 92989, No. 50-93928, No. 50-110337, No. 52
-146235, Special Publication No. 50-23813, etc. The coupler photographic material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxole dyes, hemioxonol dyes and merocyanine dyes are useful. A specific example of the dye used is British Patent No. 584609.
No. 1177429, JP-A-48-85130, JP-A No. 49-
99620, US Patent No. 49-114420, US Patent No. 52-108115, US Patent No. 2274782, US Patent No. 2533472, US Patent No.
No. 2956879, No. 3148187, No. 3177078, No. 3247127, No. 3540887, No. 3575704,
Same No. 3653905, Same No. 3718472, Same No. 4071312,
It is described in No. 4070352. The color photographic material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4
-thiazolidone compounds (e.g. U.S. Pat.
3314794, 3352681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamate ester compounds (e.g.,
Nos. 3,705,805 and 3,707,375), butadiene compounds (e.g., U.S. Pat.
4,045,229) or benzoxide compounds (eg, those described in US Pat. No. 3,700,455). moreover,
Those described in US Pat. No. 3,499,762 and Japanese Patent Application Laid-Open No. 54-48535 can also be used. An ultraviolet-absorbing coupler (for example, an α-nastol-based cyan dye-forming coupler), an ultraviolet-absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers. In the color photographic material of the present invention, it is preferable to use an ultraviolet absorber in the layer containing the coupler and magenta dye image stabilizer of the present invention or in the upper layer thereof. A layer containing separately may be provided. Generally, in the case of color photographic paper, on the support,
It is coated in a six-layer structure in the order of blue-sensitive layer, intermediate layer (1), green-sensitive layer, intermediate layer (2), red-sensitive layer, and protective layer from the side closest to the support. A seven-layer structure in which the above-mentioned ultraviolet absorbent-containing layer is specially provided between the protective layer and the protective layer has also been put into practical use. The ultraviolet absorber can also be added to the intermediate layer or each emulsion layer, but is preferably added to a layer other than the emulsion layer. Specific examples of benzotriazole compounds that are typical ultraviolet absorbers used in the color photographic material of the present invention are shown below. The above benzotriazole ultraviolet absorbers are listed in Japanese Patent Publications No. 36-10466, No. 42-26187, and No. 48-5499.
No. 48-41572, JP-A-57-142975, U.S. Pat. No. 3,754,919, and U.S. Pat. No. 4,220,711. Examples of the support according to the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent support with a reflective layer or a reflective material, glass plate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc. Examples include polyester film, polyamide film, polycarbonate film, polystyrene film, and the like. These supports are appropriately selected depending on the intended use of the color photographic material of the present invention. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating are used to coat the silver halide emulsion layer and non-photosensitive layer used in the present invention. The silver halide used in the silver halide emulsion according to the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. Includes anything that These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100] planes to [111] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. Furthermore, these silver halides may be produced by any of the neutral method, ammonia method, and acidic method, and may be produced by any of the simultaneous mixing method, forward mixing method, back mixing method, convergence method, etc. Silver halide grains manufactured by can also be applied. The silver halide emulsion according to the present invention contains sulfur sensitizers such as arylthiocarbamide, thiourea,
Also active or inactive selenium sensitizers, such as cystine, and reduction sensitizers, such as stannous salts,
Noble metal sensitizers such as polyamines, e.g. gold sensitizers,
Specifically, potassium lithiocyanate, potassium chloroaurate, 2-olosulfobenzthiazole methyl chloride, etc., or a water-soluble salt sensitizer such as ruthenium, rhodium, iridium, etc., specifically ammonium chloroparadate, Chemical sensitization can be carried out using potassium chloroplatinate, sodium chloroparadite, etc. alone or in combination as appropriate. Further, the silver halide emulsion according to the present invention can contain various known photographic additives.
For example, "Research Disclosure" 1978
It is a photographic additive as described in December, No. 17643. The silver halide according to the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the required wavelength range. Various spectral sensitizing dyes are used, and these may be used alone or in combination of two or more. Spectral sensitizing dyes advantageously used in the present invention include, for example, US Pat. No. 2,270,378;
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in the specifications of No. 2442710 and No. 2454620. The silver halide emulsion layer and the non-photosensitive layer of the color photographic material of the present invention may contain various other photographic additives. For example, use antifoggants, color stain inhibitors, optical brighteners, antistatic agents, hardeners, plasticizers, wetting agents, ultraviolet absorbers, etc. as described in Research Disclosure Magazine No. 17643. I can do it. The color photographic material of the present invention thus constructed can be subjected to various photographic processing methods for color development after exposure. A preferred color developing solution used in the present invention is one containing an aromatic primary amine color developing agent as a main component. Specific examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. Nylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, 2-amino-5-(N-ethyl-N-β- Methanesulfonamidoethyl)aminotoluene sulfate, 4-(N-
Ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-β-hydroxyethylamino)aniline, 2-amino-
Examples include 5-(N-ethyl-β-methoxyethyl)aminotoluene. These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone. Furthermore, the color developing solution generally contains an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and various additives such as an alkali metal halide such as potassium bromide, or a development regulator, For example, it may contain hydrazine acid or the like. The color photographic material of the present invention may contain the above color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. The color developing agent precursor is a compound that can generate a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include a Shugar amine reactant precursor and a urethane type precursor. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat. No. 3,342,599, U.S. Pat.
3719492, British Patent No. 803783, Japanese Patent Application Laid-open Nos. 53-135628 and 54-79035, Research Disclosure No. 15159, 12146
No. 13924. These aromatic primary amine color developing agents or their precursors need to be added in an amount that will provide sufficient color development during development. This amount varies depending on the type of photosensitive material, etc., but
Generally, the amount used is between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of photosensitive silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the above compound into a photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc., and added. It can also be added as an emulsified dispersion using a high-boiling organic solvent,
They can also be added by impregnation into latex polymers as described in US Pat. No. 14,850. The color photographic material of the present invention is usually bleached and fixed, or bleached and fixed, and washed with water after color development. Many compounds are used as bleaching agents, among them polyvalent metal compounds such as iron (), cobalt (), tin (), and especially
Complex salts of these polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Aminopolycarboxylic acids such as N-hydroxyethylethylenediaminediacetic acid, metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, or ferricyanic acids;
Dichromate and the like may be used alone or in appropriate combinations. Typical examples of the above aminopolycarbic acid include the following. Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Ethyl etherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid Ethylenediaminetetraacetic acid disodium salt Diethylenetriaminepentaacetic acid pentasodium salt Nitrilotriacetic acid sodium salt Bleaching solution contains various additives along with the above bleaching agents. It may also contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. As in the case of the above-mentioned bleaching solution, various other additives such as PH buffers, fluorescent brighteners, antifoaming agents, surfactants,
Preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained. Examples of silver halide fixing agents include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiourea, and thioether, which react with silver halide and are water-soluble. Mention may be made of compounds that form silver salts. [Specific Effects of the Invention] According to the color photographic material containing the triazole polar magenta coupler of the present invention and the magenta dye image stabilizer represented by the general formulas [A] to [E], conventional The fastness of magenta color development, which has low fastness to humidity, is improved. Specifically, discoloration and fading to light, and generation of Y-stain in uncolored areas to light and moist heat are well prevented. [Specific Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 On a paper support laminated on both sides with polyethylene, gelatin (15.0 mg/100 cm ² ) and the magenta coupler MC-8 (6.0 mg/100 cm ² ) were mixed with 2,5-di-
tert-octylhydroquinone (0.8mg/ ^100cm2 )
After dissolving and emulsifying and dispersing the mixture, it was mixed with a silver chlorobromide emulsion (silver bromide 80 mol %, coated silver amount 3.8 mg/100 cm ² ), coated, and dried to obtain Sample 1. A magenta dye developer stabilizer was added to the above sample 1,
Sample 2 was obtained in which the PH-13 and the magenta coupler were added in an equimolar amount. The magenta coupler of Sample 1 was replaced with the triazole type magenta coupler of the present invention (PC-10), (PC-
Samples 3, 6, and 9 were obtained in the same manner except that they were replaced with (PC-11) and (PC-12), respectively. In the above samples 3, 6 and 9, PH-13 was added as the magenta dye image stabilizer in equimolar amount to the coupler to obtain samples 4, 7 and 10, respectively. Furthermore, in place of PH-13, the magenta dye image stabilizer A-1 of the present invention was added in equimolar amounts to the coupler to obtain Samples 5, 8, and 11, respectively. The sample obtained above was exposed to light through an optical wedge according to a conventional method, and then processed in the following steps. [Processing process] Processing temperature Processing time Color development 33°C 3 minutes 30 seconds Bleach-fixing 33°C 1 minute 30 seconds Washing 33°C 3 minutes Drying 50-80°C 2 minutes The components of each processing solution are as follows. [Color developer] Benzyl alcohol 12ml Diethylene glycol 10ml Potassium carbonate 25g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxylamine sulfate 2.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
Add 4.5g water to make 1, and adjust the pH to 10.2 with NaOH. [Bleach-fix solution] Ammonium thiosulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to 1 and adjust the pH to 6.7-6.8. The concentrations of Samples 1 to 11 treated above were measured using a densitometer (model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions. Each of the above-treated samples was exposed to a xenon fade meter for 8 days to examine the light fastness of the dye image and the Y-stain in the uncolored area.
It was left in a high temperature, high humidity atmosphere of RH for 14 days, and the moisture resistance of the dye image and the Y-stain in the uncolored area were examined. The results obtained are shown in Table 1. However, the evaluation of each item of light fastness and moisture fastness of the dye image is as follows. [Residual rate] Percentage of dye remaining after light and moisture resistance tests for initial density 1.0. [YS] From the concentration of Y-stain after light resistance and moisture resistance tests,
Value obtained by subtracting the Y-stain concentration before light and moisture resistance tests. [Degree of discoloration] The value obtained by subtracting (yellow density) / (magenta density) before the light fastness test from (yellow density) / (magenta density) after the light fastness test at an initial density of 1.0. This means that the color tends to change to a yellowish tinge.

【table】

[Table] As is clear from Table 1, Samples 3, 6, and 9 prepared using the coupler of the present invention are different from the conventional 4-equivalent type 3-anilino-1,2-pyrazolo-5
-Compared to Sample 1 made using an on-type coupler, it is clear that YS is extremely unlikely to occur in the light fastness and humidity tests; You can see that the color changes and fades. Samples 4, 7, and 10 were prepared by using the coupler of the present invention in combination with the well-known magenta dye image stabilizer PH-13, which certainly prevented the dye image from fading due to light. is significantly improved, but discoloration cannot be improved. On the other hand, in samples 5, 8, and 11 prepared using the coupler and dye image stabilizer of the present invention, light, heat,
It can be seen that the resistance test against humidity shows that the color change and fading of the dye image is small, and that Y-stain is hardly generated in the uncolored areas. This could not be achieved with the conventional combination of a 4-equivalent type 3-anilino-1,2-pyrazolo-5-one type coupler and a dye image stabilizer (Sample 2). Example 2 Samples 12 to 34 were prepared by coating the coupler and magenta dye image stabilizer combinations shown in Table 2 in exactly the same manner as in Example 1. Samples 12-34 were processed as described in Example 1. Furthermore, these samples were subjected to a light resistance test and a moisture resistance test in the same manner as in Example 1, and the results shown in Table 2 were obtained.

【table】

[Table] As is clear from Table 2, the magenta dye image stabilizer of the present invention is used in combination with the conventionally used 4-equivalent type 3-anilino-1,2-pyrazolo-5-one type coupler. (Samples -12, 13,
14, 16) and when a conventionally commonly used magenta dye image stabilizer was used in combination with the coupler of the present invention (Samples-18, 19, 20, 21), discoloration, fading, and uncolored areas were observed in the light fastness test. It can be seen that it is not possible to improve all of the YS in the humidity test and the YS in the moisture resistance test, and that all of the above-mentioned improvements can be achieved only by using the coupler of the present invention in combination with the magenta dye image stabilizer of the present invention. In particular, among the magenta dye image stabilizers of the present invention, those represented by the general formula [] or [] exhibit even more excellent effects. Example 3 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and Sample 35 was obtained. 1st layer: blue-sensitive silver halide emulsion layer α-pivaloyl-α- as a yellow coupler
(2,4-dioxo-1-benzylimidazolidin-3-yl)-2-chloro-5-[γ-(2,4
-di-t-amylphenoxy)butyramide] acetanilide at 6.8 mg/100 cm ² , blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver: 3.2
mg/100cm ² , 3.5mg/di-octyl phthalate
100cm ² and gelatin was coated at a coating amount of 13.5mg/100cm ² . 2nd layer: middle layer 2,5,-di-t-octylhydroquinone
0.5mg/ ^100cm2 , di-nonyl phthalate 0.5mg/100cm2
100cm ² and gelatin was coated at 9.0mg/100cm ² . Third layer: green-sensitive silver halide emulsion layer: 3.5 mg/100 cm ² of the magenta coupler PC-10,
Blue-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) was converted to silver at 2.5 mg/100 cm ² , di-octyl phthalate was 3.0 mg/100 cm ² and gelatin was 12.0 mg/100
It was coated so that it was cm ² . 4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-sec
-butyl-5-t-butylphenyl)benzotriazole 7.0mg/100cm ² , dibutyl phthalate
6.0mg/ ^100cm2 , 2,5-di-t-octylhydroquinone 0.5mg/ ^100cm2 and gelatin 12.0
It was coated so that it was mg/100cm ² . 5th layer: Red-sensitive silver halide emulsion layer 2-[α-(2,4-di-
t-bentylphenoxy)butanamide]-4,
4.2mg/6-dichloro-5-ethylphenol
100cm ² , tri-2-ethylhexyl phosphate 3.5mg/100cm ² and gelatin 11.5mg/100cm ²
It was painted to look like this. 6th layer: Protective layer Gelatin was coated at 8.0 mg/100 cm ² . In the above sample 35, the dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3,
Multilayer samples 36 to 44 were prepared, exposed and treated in the same manner as in Example 1, and then subjected to a light fastness test (irradiated with a xenon fademeter for 15 days). The results are also shown in Table 3.

【table】

[Table] From this result, the dye image stabilizer of the present invention is
The triazole type magenta coupler of the present invention is effective in stabilizing dye images, and the effect becomes greater as the amount added increases. Further, Samples 36 to 44 showed extremely small discoloration of the dye images in the light fastness test compared to Sample 35. Furthermore, it can be seen that in the samples of the present invention, discoloration and fading of the magenta dye are extremely small, the overall color balance with the yellow and cyan couplers as a color photographic material is good, and the color reproducibility is extremely good.

Claims (1)

[Scope of Claims] It is characterized by containing a 1-H-pyrazolo-[3,2-C]-s-triazole type coupler and at least one of the compounds represented by the following general formulas [A] to [E]. Silver halide color photographic light-sensitive material: General formula [A] In the formula, R ¹ represents an aliphatic group, a cycloalkyl group or an aryl group. R ² represents a hydrogen atom or the same group as R ¹ above. The piperazine ring may be substituted with an alkyl group. General formula [B] In the formula, R ³ represents the same group as R ¹ above. The morpholine ring may be substituted with an alkyl group. General formula [C] In the formula, R ⁴ represents the same group as R ¹ above. The thiamorpholine ring may be substituted with an alkyl group. General formula [D] In the formula, R ⁵ represents the same group as R ¹ above. R ⁶ represents the same group as R ² above. The imidazolidine ring may be substituted with an alkyl group. General formula [E] In the formula, R ⁷ represents the same group as R ¹ above. R ⁸ represents the same group as R ² above. The homopiperazine ring may be substituted with an alkyl group.