JPS61278854A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To improve the fastness to light and to prevent the generation of a Y-stain by light by incorporating a 3-anilino-4-(2-alkoxy arylthio)-5-pyrazolone type coupler and three kinds of specific compds. into the titled material. CONSTITUTION:This color photographic material contains the 3-anilino-4-(2- alkoxy arylthio)-5-pyrazolone type coupler as well as the compd. expressed by formula I, the compd. expressed by formula II and the compd. expressed by formula III. the anti-oxidant expressed by formula I is preferably added to an emulsion (magenta layer) contg. a magenta coupler. The UV absorbent expressed by formula II is preferably added into the layer upper than the magenta coupler-contg. layer, for example, an intermediate layer and protective layer. The high boiling solvent expressed by formula III is required to be incorporated into at least the 3-anilino-4-(2-alkoxy arylthio)-5-pyrazolone magenta coupler- contg. layer.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, the dye image obtained with a 3-anilyy-4-(2-alkoxyarylthio)-5-virazolone type 2-equivalent magenta coupler is stable and has a stain-free color. This invention relates to a silver halide color photographic material in which generation is prevented. [v! , US technology] Conventionally, by imagewise exposing a silver halide color photographic light-sensitive material and color-developing it, a coupling reaction occurs between the oxidized product of an aromatic primary amine developing agent and a color former, and for example, an indoor di/ -L, Indoaniline, Ingmin, 7
It is well known that zometine, phenoxazine, 7enazine, and similar pigments are produced to form color images. In such photographic systems, a color reproduction method using a subtractive color method is usually adopted, and color forming agents having additional colors, namely yellow and magenta, are added to blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver helodenide emulsion layers, respectively. A color silver halide photographic material containing a coupler that develops a cyan color is also used. Examples of couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, virazolobenzimigzole, pyrazolotriazole, and ingzolone. For example, 717-ol or 7-tall couplers are commonly used as couplers for forming cyan images. It is desired that the dye image obtained in this manner does not change color or fade even when exposed to light for a long time. Further, it is desirable that the uncolored areas of the silver halide color photographic material (hereinafter referred to as color photographic material) do not turn yellow (hereinafter referred to as Y-stain) when exposed to light. That is, it is desired that the screen has good color tone retention. In particular, in the case of magenta couplers, Y-staining due to light in uncolored areas and fading due to light in color image areas are much greater than in yellow couplers and cyan couplers, and thus often pose a problem. Couplers commonly used to form magenta dyes are 5-, pyrazolones. In addition to the main absorption near 550n, the dyes formed from these couplers are 43
A major problem is that it has sub-absorption near On@. Various studies have been conducted to solve this problem. In particular, 5-vilazolones having an anilino group at the 3-position have a small side absorption and are therefore particularly useful for obtaining printed color images. These techniques are described in, for example, U.S. Pat.
It is stated in No. 4. However, the major drawbacks of this magenta dye are its color tone retention, which is that the fastness of the color image to light is deceptively poor, and that the Y-stain in the uncolored area is large. On the other hand, 5-
Virazolones are 4-equivalent couplers. That is, when reacting with an aromatic primary amine developing agent, it is theoretically necessary to develop 4 moles of silver halide as an oxidizing agent. On the other hand, 5-virazolones substituted at the 4-position with a group that can be separated by a coupling reaction with the oxidized form of the developing agent require development with only 2 moles of silver halide, so-called 2 equivalents. It is a coupler. Two-equivalent couplers are also superior to four-equivalent couplers in terms of color development efficiency. As a means of reducing the amount of silver halide required for development and increasing color development efficiency, it has been proposed for a long time to make the 5-virazolone type magenta coupler into two equivalents. However, U.S. Patent Nos. 3,419,391 and 3,926.
．． 5-, which leaves off an oxygen atom, as disclosed in No. 631, etc.
Virazolones and U.S. Patent No. 4,076.533;
241,168, etc., the synthesis process is long and the price of the coupler is high, and the reduction of silver halide and halving the amount of coupler used does not have much merit. Some compounds have drawbacks such as being unstable or having a slow coupling rate with an oxidized developing agent. On the other hand, attempts were made to introduce a group that leaves the sulfur atom at the 4-position of 5-virazolones, and a compound having a heterocyclic thio group or an arylthio group was disclosed in US Pat. No. 3,227,554, and a compound having a thiocyano group is disclosed in U.S. Patent No. 3,214,437, and a compound having a dithiocarbamate group is disclosed in U.S. Patent No. 4,
No. 032,348. These compounds have the advantage that they can be synthesized in most cases in one step from the corresponding 4-equivalent pyrazolones, but when added to color photographic materials, the mercapto compounds released into the processing solution inhibit development. However, its use was extremely limited due to the instability of the compound. JP-A-57-35858 describes 3-7nilino-4-〇-substituted allylthio-5-vilazolone which is advantageous in terms of side absorption and synthesis, and JP-A-57-20403 describes
No. 7 uses a combination of 3-7nilino 4-(2-alkoxyarylthio)-5-vilazolone type coupler and an antifading agent (tetofalkoxyvining compound) to prevent fading and discoloration of the white background (Y-stain). A technique for measuring the However, it must be said that the effect is still insufficient. That is, there is a strong need for the development of color photographic materials that produce magenta dye images that are more robust to light and that are substantially free of Y-stin.

[Purpose of the invention]

The inventor's objective was to improve the fastness to light and to prevent the occurrence of Y-stin due to light.
An object of the present invention is to provide a color photographic material containing a -4-(2-alkoxyarylthio)-5-virazolone type coupler.

[Structure of the invention]

In order to achieve the above object, the present inventors investigated mainly antioxidants and ultraviolet absorbers, and found that they used a bis-7-functional compound and a specific ultraviolet absorber, and further branched as a solvent for coupler dispersion. By using an alkyl phosphate ester, an unexpected fact was obtained and the present invention was made. This was achieved using a color photographic material containing a compound represented by the general formula [1], a compound represented by the following general formula [11], and a compound represented by the following general formula [II[]. In the formula, R8, R2, R1 and R1 have 1 to 1 carbon atoms.
8 alkyl group, the total number of carbon atoms of R, R2, R1 and R3 is 32 or less, X is a simple bond, an oxygen atom, a sulfur atom, a sulfonyl group or +CH+n,
R5 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3. However, n is 2 to 3
In this case, each R3 may be the same or different. General formula (II) CIl□C82COOR. In the formula, R6 represents a hydrogen atom or a chlorine atom, and R7 is an alkyl group having 1 to 18 carbon atoms or 5 to 1 carbon atoms.
2 represents a cycloalkyl group. General formula CI[1) OR. R,0-P=0 1R8゜In the formula, R3 and R, , each represent a branched alkyl group having 8 or more carbon atoms, and may be the same or different from each other, depending on the number of carbon atoms in the three groups. The total sum is 24 to 40
It is. Hereinafter, the present invention will be specifically explained in detail. The magenta coupler used in the present invention that separates from 2-flukoxyarylmer-butane is preferably one having an anilino group substituted at the 3-position of 1-aryl-5-virazolone, and is particularly represented by the following general formula [IV]. Preferably. 8r In the formula, Ar represents a phenyl group substituted with at least ] or more halogen atoms, alkyl groups, alkoxy groups, alkoxycarbonyl groups, or cyano groups, R11 is an alkyl group, and R12 is a hydrogen atom, a halogen atom, or a hydroxy group. group, an alkyl group, an alkoxy group, and an alkyl group, and m is an integer of 1 to 4. X represents a halogen atom or an alkoxy group, R13 is a hydrogen atom, a halogen atom,
Alkyl group, alkoxy group, acylamide 7 group, sulfonamide group, sulf1 moyl group, carbamoyl group, diacylamide 7 group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, Represents an arylthio group, an alkoxycarbonylamide group, an alkylureido group, an acyl group, a nitro group, a carboxy group, or a trichloromethyl group. To explain A in more detail, Ar is a substituted phenyl group, and the substituents include a) lodene atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.), an alkyl group having 1 to 22 carbon atoms (e.g., methyl group, t-butyl group, dodecyl group, etc.), alkoxy groups having 1 to 22 carbon atoms (e.g., methoxy group, ethoxy group, octyloxy group, dodecyloxy group, etc.), etc. As the alkyl group represented by RI+, carbon Number of atoms 1-2
Examples include methyl group, propyl group, butyl group, nidoxymethyl group, hexyl group, dodecyl group, and hexadecyl group. R+1 can represent various substituents, but preferred substituents include alkyl groups having 1 to 18 carbon atoms (e.g., methyl group, butyl group, tetradecyl group, etc.), alkoxy groups (
For example, methoxy group, ethoxy group, 2-ethylhexyl group, etc.) Acylami7 group (for example, acetamide group, betuzamide group, α-(2g4-di-L-amyl727xy)
butylamide group, N-methyltetradecanamide group, etc.)
, sulfonamide group (e.g. methanesulfonamide group,
benzenesulfonamide group, octadecanesulfonamide group, etc.), sulfamoyl group (e.g. N-methylsulfamoyl group, N-(4-(2,4-not-7mil71)
/xy)butyl]sulfamoyl group, etc.), carbamoyl group (e.g., N-methylcarbamoyl group, N-methyl-N
-tetradecylcarbamoyl group, etc.), cyanuramino group (e.g., N-succinimide group, N-7 talimide group,
3-dodecyl-2f5-dioxo-1-hydantoynyl group, etc.), alkoxycarbonyl group (e.g., ethoxycarbonyl group, tetradecyloxycarbonyl group, etc.), flukoxysulfonyl! (e.g., methoxysulfonyl group, octyloxysulfonyl group, etc.), alkanesulfonyl group (e.g., methanesulfonyl group, 2-ethylhexanesulfonyl group, etc.), arylsulfonyl group (e.g., benzenesulfonyl group), alkylureido group (e.g., N, N-
trimethylureido group, N-hexadecylureido group, etc.)
, an acyl group (for example, an acetyl group, a p-dodecanamidobenzoyl group, etc.), a nitro group, a carboxy group, or a trifluoromethyl group. Examples of the halogen atom represented by There is. Next, typical coupler examples used in the present invention will be shown, but the present invention is not limited thereto. The following margin M-1 Shimi M ・-2 Shiri M -4 Shimi Cmi C Magazine Shimi Shimi M-13 Shimi Shimi Nori IJ Cmi Q is Pvl-25 Cmi C! These couplers can be synthesized by reacting a so-called 4-equivalent coupler having no substituent at the coupling active position with a thio-7-enol derivative of the corresponding coupling-off group. Next, compounds that are used in combination with the magenta coupler of the present invention and contribute to improving the light fastness of magenta dye images will be described. In the antioxidant represented by the general formula [1], RI
The alkyl group represented by tR, R, and R1 may be linear or branched, such as methyl group, ethyl group, propyl group, i-butyl group, t-butyl group, pentyl group, octyl group, dodecyl group, etc. can be mentioned. In addition to a single bond, o, s, and so2, X represents +CH+n, and specific examples of +CH+n include divalent groups such as methylene, ethylene, propylene, ethylidene, propylidene, hexylidene, and octylidene. Representative compound examples are shown below, but the present invention is not limited thereto. τ ・ 1 ' Below margin 1-□□□ 1・-2 CsH+ + L;sH+ +■ -14 ■ -15 CI+3 Shinko (-1,7

[-22 ■ -26 ■ -27 ■ -28 C is also a tree. -30 These compounds are described in U.S. Patent Nos. 2,792,428 and 2.
．． No. 796,445, No. 2,841.619, Japanese Patent Publication No. 16539-1972, Japanese Patent Publication No. 6338-1983, Journal of the Chemical Society (J, C
hew, Soc, ), 243 pages. It can be synthesized according to the method described in 1954 et al. In the ultraviolet absorber represented by the general formula [II],
The alkyl group represented by R2 may be linear or branched, and preferably has 1 to 12 carbon atoms. Specifically, a methyl group, an ethyl group, an i-butyl group, a pentyl group,
Examples include 2-ethylhexyl group and dodecyl group. R
The cycloalkyl group represented by t has carbon atoms rlL5-7
Among them, a cyclobentyl group or a cyclohexyl group is preferable. Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereto. General formula (II) H \゛ 2NOR2H. II-] II CH. 11-2 CQ CH. U-3HC, lI. 11-4 CQ C2H5n
-51(C,lI. 11-8 CQ C4H. 11-7 H+ -C-HeIt -8 rule
i-C, II. 17-9 Hj-CstL +■-10 is
t-Cs1L+11-13 11
C,lI,. ll-14CQ C,H,. n-15HCH2CHC4) 1゜Book 2H5 II-17Hi''CI 0)121 1T-18HC, □H25 These compounds are so-7zo-formed 0-nitroaniline as described in JP-A-57-142975. Alternatively, an azo dye obtained by coupling with p-chloro-0-nitro7nilinto-2-(3-butyl-4-hydroxyphenyl)propionic acid is reduced and ring-closed with zinc in an alkaline solution, and further with an alcohol. It can be synthesized by esterification. In the high boiling point solvent represented by the general formula CI [], R
Examples of the branched furkyl group represented by R9 and R10 include 2-ethylhexyl group, t-octyl group, 3.5
．． Examples thereof include 5-)limethylhexyl group, 3°6.6-)limethylhebutyl group, and 2.4.6.6-titramethylhexyl group. Specific compound examples of branched alkyl phosphates are shown below, but the present invention is not limited thereto. // de\, is ('7 extra, self\, two)' ■Rom-7 ■～8 ■-10 ■-11 These compounds are
Phosphorus and its compounds J (J, R, Van Waze
r；Pbospl+orus and it's Co
It can be synthesized by the reaction of phosphorus oxychloride and an aliphatic branched alcohol, as described in vol. 2, p. 1221. In the color photographic material of the present invention, the amount of the 3-7nilino-4-(2-alkoxyarylthio)-5-virazolone type coupler added is 1°5×lO per mole of silver.
The range is preferably from -7.5X10-' moles, more preferably from 1X10-2 to 5X10-' moles. The antioxidant represented by the general formula [I] is preferably added to the emulsion layer containing the magenta coupler (magenta layer), but may be added to other layers, especially layers adjacent to the magenta layer. When adding, dissolve the coupler together with a high boiling point solvent and, if necessary, a low boiling point solvent.
It is preferable to disperse the compound and add it to the silver halide emulsion.Since it is substantially colorless, the amount of the compound added is not particularly limited, but it is sufficient if it is present in an amount of about 15 g per mole of the dye formed by color development. It is preferably 5 to 300% by weight, more preferably 10 to 1% by weight, based on the commonly used 3-anilino-4-(2-alkoxyarylthio)-5-virazolone type coupler mainly for economic reasons.
00% by weight. The UV absorber represented by the general formula (n) is preferably added to a layer above the magenta coupler-containing layer, particularly to a non-photosensitive layer, such as an intermediate layer or a protective layer. The amount added depends on the type of high boiling point solvent and/or low boiling point solvent that dissolves the compound, but is generally 0.10 to 112
1. OOg is suitable. The high boiling point solvent represented by the general formula [■] is at least 3-7
Nilino 4-(2-alkoxyarylthio)-5-virazolone is required to be included in the magenta coupler-containing layer, but it can also be used in other emulsion layers, non-photosensitive layers, etc. It can be used in any proportion to the above magenta coupler, but preferably 5 to 1000% by weight.
is used, particularly preferably from 10 to 200% by weight. The color photographic material of the present invention can be, for example, a color film, a positive film, or a color photographic paper, but the effect of the method of the present invention is particularly effective when using a color photographic paper that is intended for direct viewing. It is demonstrated. The color photographic materials of the present invention, including this color photographic paper, may be for monochromatic use. In the case of multicolor photographic materials, for subtractive color reproduction, the photographic couplers are usually supported by a silver lodenide emulsion layer containing magenta, yellow and cyan couplers and a non-light-sensitive layer. It has a structure in which layers are laminated in an appropriate number and order on the body, but the number and order of layers may be changed as appropriate depending on the important performance and purpose of use. 7/1. \Hereinafter, the silver halide fL agent of the present invention includes silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride in ordinary silver halide emulsions. Any used can be used. The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method.The grains may be grown all at once, or they may be grown by forming seed grains. It may be allowed to grow a certain length later. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. This method may also be performed by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and V/or pAg in the mixing pot, taking into consideration the critical growth rate of silver halide crystals. As a result, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, the halogen composition of the grains may be changed using the Humbage method.1°Silver halide emulsions can be manufactured by changing the grain size of the silver halide grains using a silver halide solvent as needed. ,
Particle shape, particle size distribution and particle growth rate can be controlled. During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, ilinium salts (including complex salts), ronium salts (including complex salts), and iron salts ( By adding metal ions using at least one selected from fR salts), these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere. , reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research D 1s
Closure (hereinafter abbreviated as RD)) No. 17643, Section (2) may be used. The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide it differs between the inside of the grain and the surface layer. The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain. The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the 11001 plane to the i 111.1 plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. Silver halide emulsions having any grain size distribution may be used. The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions. Silver halide emulsions can be chemically sensitized by conventional methods. Namely, sulfur sensitization method, Senn sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex melonanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are used. The most useful pigments are cyanine pigments, merocyanine pigments,
and a complex merocyanine pigment. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added. It is advantageous to use gelatin as the binding agent (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention can be hardened by using one or more hardeners that crosslink the pine goo (or protective colloid) molecules and increase the film strength. can. The hardening agent can be added to the processing solution in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD No. 1.7643, section (■) A. A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer can be contained in the photographic emulsion layer or other wood-philic colloid layer of a light-sensitive material for the purpose of improving dimensional stability. The emulsion layer of the light-sensitive material undergoes a coupling reaction with an oxidized form of an aromatic fIfJ primary amine developer (for example, a p-7 22-diamine derivative or an amino-7 ether derivative) during color development processing. Dye-forming couplers are used that form dyes. The dye-forming couplers are typically selected for each emulsion layer so that a dye is formed that absorbs light in the emulsion layer's light-sensitive spectrum, with the blue-sensitive emulsion layer containing a dye-forming coupler. , a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers can act as development inhibitors, development accelerators, bleach accelerators, developers,
Includes compounds that release seven photographically useful fragments such as silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers. be done. Colorless couplers (also referred to as competitive couplers) which undergo a cambling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes can also be used in combination with dye-forming couplers. As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. As magenta dye-forming couplers, 5-pizzolone couplers, pyrazolobenzimidazole-based cab 2-5-[7sil7cetonitrile couplers, ingzolone-based couplers, etc.] other than those of the present invention can be used together with the couplers of the present invention. As cyan dye-forming couplers, phenol or 7-tole couplers are generally used. Among dye-forming couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. that do not need to be adsorbed on the surface of silver halide crystals, hydrophobic compounds can be used by solid dispersion method, Dispersion can be carried out using various methods such as a latex dispersion method and an oil-in-water emulsion dispersion method, which can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, a method known in the United States for dispersing hydrophobic additives such as couplers can be applied. Usually, a high-boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low-boiling point and a low-boiling point organic solvent as necessary. /or Dissolved in combination with a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-knot mixer, or ultrasonic device. After emulsification and dispersion, a step of removing the low-boiling organic solvent may be added after or simultaneously with the dispersion, which can be added to the desired hydrophilic colloid liquid. Examples of high boiling point solvents include 7-ether tA conductors that do not react with the oxidized form of the developing agent, 7-tar acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid modified esters. An organic solvent having a boiling point of 150° C. or higher is used. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate,
Examples include butyl acetate, butanol, chloroform, Ui tetrachloride, nitromethane, nitroethane, benzene, etc. Water-soluble organic solvents include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile. , dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, noethyleneglyfur monophenyl ether,
Examples include 7e7xyethanol and the like. When dye-forming couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, hydrophilic colloids can be used as alkaline aqueous solutions. It also ends with introducing it inside. Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used. The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable. The color anti-capri agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer. In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material. When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer V/or other hydrophilic colloid layer of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD 17
The compound is a compound described in Section XXI, B-D of No. 643, and the development retardant is a compound described in Section Xxr, E of No. 17643. black and white developing agents for development acceleration and other purposes, and/or
Or you may use the breaker sir. The emulsion layer of the light-sensitive material contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, 1,000-onythyl compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, and urea for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also include derivatives, imiguzole derivatives, and the like. A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in section 1 of RD 17643. The photosensitive material includes one layer of filter, /) anti-ray layer,
Auxiliary layers such as anti-irradiation layers may be provided. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process. Such dyes include oxonol dyes, hemioxo-7
Examples include -al dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added to prevent photosensitive materials from sticking together. A lubricant can be added to the photosensitive material to reduce sliding friction. An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 X■. The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be coated with coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (promotion of development, high contrast, sensitization, etc.). The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper, synthetic paper, semi-synthetic materials such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of synthetic polymers, flexible supports made of these films with reflective layers, glass, metals, ceramics, and the like. After applying corona discharge, ultraviolet irradiation, flame treatment, etc. to the surface of the support as necessary, the wood-philic colloid layer of the photosensitive material can be applied directly or to improve the adhesion, antistatic property, dimensional stability, and resistance of the support surface. Abrasion resistance, hardness, /% ration prevention, friction properties,
and/or may be coated via an undercoat layer of IN or higher to improve other properties. When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, hardeners (such as hardeners that are so reactive that they may cause gelation before coating if added to the coating solution in advance) should be mixed immediately before coating using a static mixer, etc. As a coating method, extrusion coating and curtain footing, which can coat two or more layers at the same time, are most useful, but packet coating is also used depending on the purpose. can be arbitrarily selected.To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleaching solution and the process using a fixing solution. In addition, a bleach-fixing process can be carried out using a one-bath bleach-fix solution, or color development, bleaching, and fixing can be carried out in one bath.
A more bath processing step using a bath development bleach-fix processing solution can also be carried out. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator treatment process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using a 7 activator solution, or a 7 activator solution may be used for the more pass treatment. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as a final step, either a water washing process, a water washing process or a stabilization process.) - Color development process -
Bleaching process Fixed fixing process/Color development process - Bleach-fixing process/Pre-hardening process - Color developing process - Stop fixing process - Water washing process - Bleaching process Constant fixing process - Washing process - Post-hardening process/Color development process - Water washing process - Supplementary color development process - Stop process First bleaching process Constant fixation process/Activator process - Bleach-fixing process/Activator process - Bleaching Treatment process Constant fixation treatment process/Morebath treatment process]-゛・Hereinafter, the lower margin treatment liquid temperature is usually selected in the range of io'c to 65"C, but it may be set to a temperature exceeding 65"C. Preferably. The color developer is generally an alkaline aqueous solution containing a color developing agent.The color developing agent is an aromatic primary amine color developing agent, and is an aromatic primary amine color developing agent. These color developing agents can be used as salts of organic and inorganic acids, such as salts, 8!acids, sulfates, p-)luenesulfonates, sulfites, etc. Salts, oxalates, benzenesulfonates, etc. can be used. These compounds are generally used at a concentration of preferably about 0.1 to 15%, more preferably 1 to 15% per q of color developer.
．． Use at a concentration of Examples of the above-mentioned ami/phenol-based developers include 0-ami 77 el, p-ami/7 el, 5-7 el/-
These include 2-hydroxytoluene, 2-7mi/=3-hydroxytoluene, 2-hydroxy-3-ami/-1,4-tumethylbenzene, and the like. Particularly useful primary aromatic amine color developers include N, N
- a noalkyl-p-phenynoamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, particularly useful examples include N,N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N-methyl-p-phenylenediamine hydrochloride.
-Phenylenenoamine hydrochloride, N,N-noethyl p-
Phenylenenoamine t[salt, 2-amino/-5-(N-ethyl-N-dodecylamino)toluene, N-ethyl-N
-β-methanesulfonamidoethyl-3-methyl-4-
Aminoaniline sulfate, N-yutyl-N-β-hydroxyethylamide 7aniline, 4-7-7-3-methyl-N
, N-noethylaniline, 4-7mi/-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Can be made with toluene sulfonate. Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials. In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline g<7 activator solution instead of a color developer. The color developing solution may contain an alkaline agent commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. additives such as benyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. good. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide, and trimethylsulfoxide can be appropriately contained. The pH of the color developer is usually 7 or higher, preferably about 9.
~13. In addition, the color developing solution used in the present invention may optionally contain antioxidants such as noethylhydroxyamine, tetronic acid, tetronimide, 2-anili7ethyl, nohydroxyacetone, aromatic secondary alcohol, Hydroxamic acid, pentose or hexose, pyroprole-1.
3-methyl ether etc. may be contained. In the color developing solution, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, 7-polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1-nophosphonic acid,
Amino/tri(methylenephosphonic acid) or 7-polyphosphonic acid such as ethylenenoamine titralinic acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phospho7butane-1.2.4-)licarboxylic acid, etc. Examples include phosphonocarboxylic acids, polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid, and polyhydroxy compounds. The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately. As a bleaching agent, a metal complex salt of an organic acid is used, for example, an organic acid such as polycarboxylic acid, polycarboxylic acid, oxalic acid, citric acid, etc., coordinated with metal ions such as iron, cobalt, copper, etc. is used. . Among the above organic acids, the most preferred organic acids include polycarboxylic acids and amide/polycarboxylic acids. Specific examples of these include ethylenenoaminetitraacetic acid, diethylenetriaminepentaacetic acid, and ethylenediamine-N-(β-oxyethyl)-
N. N', N'-) diacetic acid, propylenenoamine thitraacetic acid, nitrilotriacetic acid, cyclohexanoamine thitraacetic acid, imi-7 diacetic acid, nohydrodoxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol Examples include etherdiaminetetraacetic acid, ethylenenoaminetetraprobionic acid, and phenylenediaminetetraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are preferably used in amounts of 5 to 450 g/e, more preferably 20 to 250 g/l. In addition to the above bleaching agents, the bleaching solution may contain a sulfite salt as a preservative, if necessary. In addition, the bleaching solution is ethylenenoaminetitraacetate (I).
II) A liquid containing a complex salt bleaching agent and a large amount of a halide such as ammonium bromide may be used. Examples of the halides include ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, and bromide).
17um, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. The bleaching solution used in the present invention includes Japanese Patent Publication Nos. 46-280, 45-8506, 46-556, Belly Patent No. 770,910, 45-8836, and 53-9854. , JP-A No. 54-71634 and No. 4
Various bleaching accelerators such as those described in No. 9-42349 can be added. The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
, 0 to 9.5, preferably 4.5 to 8.0, and most preferably 5.0 to 7.0. A fixing solution having a commonly used composition cannot be used. Examples of fixing agents include compounds that react with silver halide to form water-soluble complex salts, such as those used in conventional fixing processes, such as thiosulfates such as potassium periosulfate, sodium thiosulfate, and ammonium thiosulfate, and thiocyanic acid. Typical examples include potassium, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount of 70 to 250 g/1 or more, but it is generally used in an amount of 70 to 250 g/1. A part of the fixing agent 5 can be contained in the bleaching solution, or conversely, a part of the bleaching agent can also be contained in the fixing solution. In addition, the bleaching solution and fixing solution contain boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffering agents such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydranone, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, hardeners such as water-soluble aluminum salts, Organic solvents such as methanol, trimethylsulfamide, dimethylsulfoxide, etc. can be appropriately contained. The fixer is used at a pH of 3.0 or higher, but generally has a pH of 46.
5 to 10 is used, preferably 5 to 9.5 is used, most preferably 6 to 9. As the bleaching agent used in the bleach-fixing solution, there can be mentioned the metal complex salts of organic acids described in the above bleaching process, and the preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenenoamine ferric acetate (I[[) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, A special bleach-fix solution containing a large amount of a halide such as ammonium may also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used. Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH 41 buffer and other additives that can be contained in the V bleach-fixing solution are the same as in the fixing process described above. The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5. The following is Kurano Shiro-1/ [Specific effects of the invention] The 3-anilyy-4-(2-alkoxyarylthio)-5-virazolone type coupler of the present invention and the general formula [I
According to a color photographic material containing a dye image stabilizer represented by the formula [II], an ultraviolet absorber represented by the general formula [II], and a high boiling point solvent represented by the general formula A magenta dye image can be obtained that has excellent storage stability, specifically, fastness to light, and is free from staining.

【Example】

EXAMPLES Hereinafter, the present invention will be specifically explained 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, the following layers were sequentially coated from the support side to create a multicolor photographic material (sample 1) (the amount added is 1-2 unless otherwise specified). (Silver halide emulsions are shown in terms of silver.) Layer 1 Blue-sensitive emulsion layer 0.40 g of a blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol %) and 1.0. A blue-sensitive emulsion layer containing 0.65 g of yellow coupler (Y-1) dissolved in dibutyl 7 grade. Layer 2 Middle layer■. 5. an intermediate layer containing gelatin. Layer 3 Green sensitive emulsion layer 0.20. green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%), 0.4 g of high boiling point solvent (exemplified compound In-1)
0,30 g of magenta coupler (exemplary coupler M-7) dissolved in 0,15. A green-sensitive emulsion layer containing exemplified compound l-1). Layer 4 Intermediate layer Intermediate layer containing 2.0 g of gelatin and 0.2 g of UV absorber (exemplified compound 1-14) dissolved in 60111+ butyl 7-talate. 1! I5 Red-sensitive emulsion layer 0,40. A red-sensitive emulsion layer containing a cyan coupler (C-1). Layer 6: Intermediate layer containing 1.5 g of gelatin (dissolved in 7200 mg of dibutyl 7 tallate). Next, the magenta coupler in layer (3) in sample 1, compounds of general formula (1) and general formula (I[[), and further N(
Samples 2 to 6 were prepared in the same manner except that the compounds of general formula (n) in layer (4) and layer (6) were changed as shown in Table 1. After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was carried out in the following steps. [Processing process] Processing temperature Processing time Color development
Bleach and fix at 33°C for 3 minutes and 30 seconds 33
℃ Wash with water for 1 minute 30 seconds 33℃
3 divisions Drying 50-80℃
The components of each 2-minute treatment solution are as follows. [Color developer] Bennol alcohol 12nQ. Diethylene glycol 10aQ Potassium carbonate 25g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxylamine sulfate
2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami/7-niline sulfate 4.5 g water was added to make a mixture, and the pH was adjusted to 10.2 with Nao H. [Bleach constant I solution] Ammonium 100sulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65° Add water to bring IQ to pH 6.7
Adjusted to ~6.8. The treated sample was exposed to xenon for 100 hours using a xenon fade meter, and the concentration after exposure (D) and the concentration before exposure (Do) were measured using a Sakura color densitometer PD-6 (manufactured by Konishiroku Photo Industry Co., Ltd.). magenta dye residual rate (D/D oX
100:D o = 2.0) was measured with green light, and the Y stain increase (D-Do) on a white background (unexposed area) was measured with blue light. The results are shown in Table 1. Compound A All Compound B Compound C Compound E (CH3(CH2)tO) 3P=0 Compound F O Compound G Compound H Tricresol phosphate From the results in Table 1, the light resistance of the magenta dye image and Y
- It is clear that only Samples 1 to 3 according to the present invention fully satisfy both stain prevention properties. Example, 2 Compound 1-1 in layer (3) of sample 1 in Example 1 was replaced with I-5, l-16, and compound ■-14 in layer (4) and layer (6) was replaced with ■- Samples were prepared in exactly the same manner except that Sample No. 10 and ■-17 were used, and the same treatment and exposure test as in Example 1 was conducted, and as a result, good results similar to Sample 1 were obtained.

Claims (1)

[Claims] 3-anilino-4-(2-alkoxyarylthio)-
A silver halide color photograph comprising a 5-virazolone type coupler and a compound represented by the following general formula [I], a compound represented by the following general formula [II], and a compound represented by the following general formula [III] photosensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3 and R_4 are alkyl groups having 1 to 18 carbon atoms,
and the total number of carbon atoms of R_4 is 32 or less, and
is a simple bond, an oxygen atom, a sulfur atom, a sulfonyl group, or ▲a mathematical formula, a chemical formula, a table, etc.▼, and R_5 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
n is an integer from 1 to 3. However, when n is 2 to 3, each R_5 may be the same or different. ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_6 represents a hydrogen atom or a chlorine atom, and R_
7 represents an alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms. [In the formula, R_5, R_9 and R_1_0 each represent a branched alkyl group having 8 or more carbon atoms, and may be the same or different from each other, The total number of carbon atoms in the group is 2
It is 4-40. ]