JPS6289962A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the resistance to light, heat and moisture and to prevent yellow staining by using a bisphenol type compound, a branched alkyl ester of phosphoric acid and a chlorotriazine compound. CONSTITUTION:This silver halide color photographic sensitive material contains a coupler of 3-aniline-4-(2-alkoxyarylthio)-5-pyrazolone type and compounds represented by formulae I-III. In formula I, each of R1-R4 is 1-18C alkyl, the total number of C atoms in R1-R4 is <=32, X is a simple bonding radical, O, S, sulfonyl or (a) and R5 is H or 1-10C alkyl. In formula II, each of R6-R8 is >=8C branched alkyl and the total number of C atoms in R6-R8 is 24-40. In formula III, R9 is Cl, hydroxy, -OM (M is a univalent metallic atom), -NR'R'' (each of R' and R'' is H, alkyl or the like) or -NHCOR''' (R''' is H, alkyl or the like) and R10 is R9 except Cl. The magenta coupler which releases 2- alkoxyarylmercaptan has preferably a substituted anilino group at the 3-position of 1-aryl-5-pyrazolone.

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 2-equivalent magenta coupler of the 3-anili/-4-(2-flucoquinarylthio)-5-pyrazolone type is stable and stain-resistant. This invention relates to a silver halide color photographic film and material in which the occurrence of oxidation is prevented. [Prior Art 1] Conventionally, when a silver halide color photographic light-sensitive material is imagewise exposed and color-developed, an oxidized product of an aromatic primary amine developing agent and a color former undergo a coupling reaction, resulting in the formation of, for example, indophenol. It is well known that dyes such as , indoaniline, ingmin, azomethine, 7e/xanone, 7enanone, and similar pigments are produced and color images are formed. In such photographic methods, a subtractive color method is usually used to reproduce colors, and IT sensibilities,
In the green-sensitive and red-sensitive photosensitive silver halide emulsion layers,
A color halogenated photosensitive material is used which contains color formers that are related to the respective residual colors, that is, couplers that develop colors of yellow, magenta and cyan. Couplers used to form the yellow image include, for example, acylaceto-7nilide couplers, and couplers for magenta image J& include, for example, pyrazolone, virazolobenzimigzole,
Pyrazolotriazole or ingzolone couplers are known, and as a coupler for forming a cyan image, for example, a phenol or 7-tole coupler is generally used. It is desired that the dye image thus obtained does not change color or fade even when exposed to light for one hour. In addition, uncolored areas of silver halide color photographic light-sensitive materials (hereinafter referred to as color processed 1 materials) may turn yellow due to exposure to heat, humidity, etc.
(hereinafter referred to as Y-stin) is desirable. That is, it is desired that the screen has good color tone retention. In particular, in the case of magenta couplers, the Y-stain due to uncolored areas and fading due to uncolored image areas are extremely large compared to yellow couplers and cyan couplers.
This is often a problem. Couplers that are widely used to form magenta dyes are the 5-pyrazolones. In addition to the main absorption near 55 Onm, the dyes formed from these couplers have a wavelength of 43 nm.
The major problem is that it has sub-absorption near 0 nm. Various studies have been conducted to solve this problem. In particular, 5-pyrazolones 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. Patent No. 2,343,703 and British Patent No. 1,059,99.
It is stated in No. 4. However, the major drawbacks of this magenta dye are that the color fastness of J'4T is extremely poor, and the Y-
Sting is a big point. 5-, commonly used in color photographic materials
Pyrazolones are 4-equivalent couplers. That is, when reacting with an aromatic primary amine developing agent, it is theoretically necessary to use 4 moles of silver halide as an oxidizing agent for development. On the other hand, 5-pyrazolones substituted at the 4-position with a group that can be separated by a coupling reaction with the oxidized form of a developing agent require only 2 moles of silver halide to be developed, and the so-called It is a 2-hit 11t coupler. Two-equivalent acid couplers are also superior to four-equivalent couplers in terms of color development efficiency. Bi-oxidation of a 5-pyrazolone type magenta coupler has long been proposed as a step for reducing the amount of silver halide required for development and increasing color development efficiency. However, U.S. Patent Nos. 3,419,391 and 3,926.
5-pyrazolones are removed by IBI, which is disclosed in U.S. Pat. 5-pyrazolones have no merits because the synthesis process is good and the coupler price is high, the amount of silver halide is reduced, and the amount of coupler used is extremely small.Additionally, some compounds are bistable or have problems with developing agents. It has drawbacks such as a slow coupling rate with the oxidant. On the other hand, 5-pyrazolones have 7
A compound with a heterocyclic thio group and an arylthio group in which the J group was introduced is disclosed in U.S. Patent No. 3,227,554, and a compound with 7 thiocyan groups is disclosed in U.S. Pat. No. 3,214,43.
Compounds having a notiocarbamate group in No. 7 are disclosed in U.S. Pat. No. 4,032,346. These compounds have the advantage that they can be synthesized in most cases in one step from the corresponding 4 quasi-pyrazolones, but when added to color photographic materials, the processing time of JIJ! Applications have always been limited, such as the mercapto compound released into the solution inhibiting development, and the compound being unstable. JP-A No. 57-35858 describes 3-anilino-4-o-substituted 7lylthio-5-pyrazolones which are advantageous in terms of side absorption and synthesis, and JP-A No. 57-20403
No. 7 uses a combination of a 3-anili/-4-(2-alfoxyarylthio)-5-vilazobin type coupler and an antifading agent (tetraalkoxyvining compound) to prevent fading and discoloration of the white background (Y- Techniques have been disclosed to prevent this. However, due to its effect, 4 is sufficient in an atmosphere of heat or humidity. That is, if a dye image is stored at still high temperatures, fading may occur at 115 locations (so-called dark fading), and yellowing (Y-stain) may occur in the undamaged portions of the Zara'Q-11 material. It is not possible to prevent That is, there is a strong desire to develop a color photographic material that produces magenta dye images that are more robust against heat, humidity, and humidity, and that has virtually no occurrence of Y-stin.

[Purpose of the invention]

The purpose of the present inventors is to create a 3-anili/-4-(2-flucoxy77northio)-5-pyrazolone with improved fastness in accordance with stress, heat, and temperature, and in which the generation of Y-stin is prevented. An object of the present invention is to provide a color photographic IT material containing a type coupler. Margin below

[Structure of the invention]

In order to achieve the above object [1], the present inventors mainly investigated antioxidants related to dye images, high boiling point solvents, and hard V agents that have less influence on hygroscopicity, and found that By using a compound of the type compound, a branched alkyl phosphate ester, and a riazine type compound, unexpectedly good results were obtained, and the present invention was completed. That is, the above object is a 3-anili/-4-(2-flufquinarylthio)-5 pyrazolone type coupler, j: a compound represented by the general formula [1], 1, a compound represented by the general formula [1], 1
1] Compound V1: This was achieved using a color true material containing a compound represented by the following general formula [l■]. In the formula, R1, R2, R1 and l are carbon atoms 1-
The total number of carbon atoms in 18 noal 4 gHt', R, , R2,1(, on vR, is: (2 and above, and X is +
11 bond, N1 elementary f-1 sulfonylno, 5 or -4-CII-)-n, Iri1. is the number of carbon atoms

【the law of nature. It is an alkyl group of 1 to 10, and 11 is an integer of 1 to 3. However, when fl is 2 to 3, each [(, may be the same or 5゛4. General formula [11] O2N2 [1, .0-11=0 OR. In the formula, [ [Ri and Ro are each carbon h;
C - represents an alkyl group having a number of 8 or more, n - may be the same or different, and the total number of carbon atoms in the three groups is 24 to 40. Below is the general formula Cm) It. In the formula, H is a chlorine source r, a hydroxy group, an alkyl group,
Alkoxy group, alkylthio group, -0M group (M represents a monovalent metal atom), -NI<'L<'' group (R' and R
"represents a hydrogen atom, alkyl J1 (or an aryl group) or -N II COF , F<, , excludes the chlorine source r-<R1
, is synonymous with . Hereinafter, the present invention will be specifically explained in detail. The magenta coupler that separates 2-flucoquinarylmer butane used in the present invention is preferably one having a 1n-substituted anilino group at the 3-position of the 1-7 aryl-5-pyrazolone, and in particular is represented by the following general formula (IV). Those represented are preferred. Ar In the group, A represents a phenyl group substituted with at least one halogen atom, an alkyl group, an alkoxy group, a 7-rucoquine carbonyl group, or a sia-7 group, RII is an alkyl group, and R12 is a hydrogen atom r , represents a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, or an aryl group, l is an integer of 1 to 4. , alkoxy group, acylamide 7 group, sulfonamide group, sulfamoyl group, carbamoyl group, noacylamino group, alfkyldicarbonyllkoxysulfonyl group, aryloxysulfonyl group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, alkoxycarbonyl It represents an amine 7 group, an alkylureido group, an acyl group, a nido c+ group, a carboxy group, or a trifluoromethyl group. To describe Ar in more detail, 1 to `` is a substituted 7 enyl J, (a 1n substituted As a group, a halogen atom (e.g. chlorine atom, lA element f, fluorine paper r-, etc.), carbon atom number 1
~22 alkyl 1''; (e.g. methyl group, butyl group, dodenyl group, etc.), flucoquine group having 1 to 22 carbon atoms ((for example, ethyl group, ethquine group, octyloxy J, (, 1 !Decyloquine group, etc.) are preferable.The alkyl group represented by R , , c is a carbon atom having a carbon number of 1.
-22 groups are praised, and specific examples include methyl, (, propyl group, butyl Jll;, ethynchyl methyl group, henyl j.!:, totyl), (, hexatecyl Jll, etc.). Examples of the halogen atom containing 12"C include chlorine atom, bromine atom, fluorine atom, etc., and the alkyl group and C include, for example, methyl group, ethyl group, isopropyl group, thiobyl group, E-amyl group, 1-octyl group, etc. are mentioned, and the alkoxy group includes, for example, methquine group, ethoxy group, butoxy group, pentyloxy group, 2-ethylhexyloquine group, decyloxy group, etc. Also, as the aryl group, is, for example, a phenyl group, a naphthyl group, etc. R. can represent a substituent of type S, but preferable substituents include an alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an E-acyl group). , tetradecyl group'''P), alkoxyjI!i (e.g. methoxy group, etkyne group, 2-ethylhexyl group, etc.) acylami/Ls (e.g. acetamide group, betuzamide group, α-(2., 1-no L-7)
(mil72/xy)butyramide group, N-methyltetradecanamide group, etc.), sulfonamide 7J (for example, methanesulfonamide group, benzenesulfonamide group,
Octadecanesulfonamide group? ? ), and rufamoyl group (for example, N-methylsul7amoylno, !li, N
-[:4-(2.・1-not-7mil7e7quin)butyl]SulfT-moyl! l (etc.), h le t (Moyle J
．． ti (e.g., N-methylcarbamoyl method, N-methyl-N-tetradecyl group, etc.), noanruami/1Ili (e.g., N-succinimide group, N~7 thalimide group, 3-doyne-2゜5-nooxo-1-hyguntoynyl) ), alkoxycarbonyl groups (e.g., ethoxycarbonyl group, tetradecyl-A dicarbonyl group, etc.), alkoxysulfonyl groups (e.g., methoxysulfonyl group, octyloxysulfonyl group, etc.), alkanesulfonyl groups (e.g., methanesulfonyl J, (,2 -ethylhexane sulfonyl group, etc.), 7-arylsulfonyl-ureido M (for example, N,N-methylureido M),
(, N-hexadecylureido group, etc.), anru group (e.g. acetyl group, p-dodecanamidobenzoyl J old hP
), 2) (7 groups, carboxyne group or 1 fluoromethyl group, etc.) Examples of the halogen atom r- represented by X include chlorine atom f, bromine atom -, fluorine atom T-, etc. Examples of the alkoxy group include alkoxy groups having carbon atoms r & 1 to 22 (for example, methoxy group, octyloxy group, dodecyl group, etc.). The present invention is not limited to this invention. The following margin)' jJ ゛)' Cview jJ ゛[ke-G M -7 CviewCviewQ CViewT' M-20 Four rules Q "Q r1 C-view Q ■' u M-31 ShimI These couplers are a so-called 4-equivalent coupler that has no substituent at the coupling active position and a thiophenol derivative with a corresponding coupling-off group. Next, a compound that is used in combination with the magenta coupler of the present invention and contributes to improving the fastness of magenta dye images will be explained. In the bisphenol represented by the general formula [1],
l'<1. The alkyl group represented by R2, R3 and R4 may be linear or branched, and examples include methyl group, ethyl group, propyl group, i-butyl group, t-butyl group, pentyl group, octyl group, dodecyl group, etc. be able to. X is a single bond, 0, S, SO2, +CIt -) -I
11(., but as a specific example of +CII÷11, for example, ノR
. Examples include divalent groups such as tyrene, ethylene, propylene, ethylidene, propylidene, hexylidene, and octylidene. Representative compound examples are shown below, but the present invention is not limited thereto. Margin below Ljlq(t) C4119(L)! -3 C111,, C1H,. [-5 C411s C, It. 0i1 011 ]-10 I-17 ]-18 CIl, C11゜]-22 1-2:1 I-25 '1-27 These compounds are described in U.S. Pat.
．． No. 796.445, No. 2,841,619, Special Publication No. 18539 of 1972, Special Publication No. 18539 of 1972, Special Publication No. IJII No. 6338 of 1977,
Journal of the Chemical Society (J
, Cbe+s, Soc, ), 243 pages. It can be synthesized according to the method described in 1954 et al. In the branched alkyl phos7ate represented by the general formula CI+3, examples of the branched alkyl group represented by R, R, and R6 include a 2-ethylhexyl group, and a 2-ethylhexyl group.
Octyl group, 3,5.5) Limethylhexyl group, 3
．． 6. G-) Limethylheptyl group, 2.4.6, G-
Examples include tetramethylhexyl group. Examples of cross-section compounds of branched alkyl phosphatides are shown below, but the present invention is not limited thereto. Yarn below! '1 l-10 ■-11 +1-12 These compounds are known as
It can be synthesized by the reaction of phosphorus oxychloride with an aliphatic branched alcohol, as described in "Phophorus and Its Compounds", Foil Vol. 2, 1221. The alkyl groups represented by R1 and R3 of the chlorotriazine hardener represented by the general formula (In) are, for example, methyl, ethyl, butyl, etc., and the alkoxy groups represented by these include methoxy, ethoxy, etc. group, butoxy group, etc. Also, as a specific example of -NR'R'', -NH□
, -NHCH,, -NHC211, etc., -N Summer IC0R
As an example of Jl for -, -N1 is 9, and M in the 10M group represented by R1,1 is, for example, a sodium atom, a potassium atom, etc. Typical specific examples of chlorotrianone represented by the general formula [II[] are listed below, but the present invention is not limited thereto. (!ll-1> (I[l-2)(!
l! -3><III-4) (
In-5) (III-13)0(:
II3
u, u. (ffl-9) (III-1
0) (Ill-11) (1
'[l-12) (III-1: () For these chlorotriazine hardeners, ν1 is US 1.
3,645.74: (No., Special Publication No. 47-6151
No. 51-9 G (No. 17, Japanese Unexamined Patent Publication No. 1822-1983)
No. 0, No. 51 78788, No. 52-G O612
No. 52-128130, No. 52-130326, No. 56-1043, etc., and any of them can be used as appropriate. In the color photographic material of the present invention, the 3-aniline/-
The amount of 4-(2-alkoxyarylthio)-5=pyrazolone type coupler added is 1.5×1 per mole of silver.
The range is preferably from 0-' to 7.5X10-1 mol, more preferably from 1X10-' to 5X10-' mol. In the general formula [I], suphenol is the emulsion Jl containing the magenta coupler ( It is preferable to add the coupler to the magenta layer), but it may also be added to other layers, especially the layer adjacent to the magenta layer.When adding the coupler, use a high boiling point solvent together with a low boiling point solvent if necessary. It is preferable to dissolve and 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 about 15.0% per mole of the dye formed by color development processing. It is sufficient if it exists, and 3-7ni/-4-(2-
It is preferably 5 to 30011%, more preferably 10 to 100%, based on the alkoxyarylthio)-5-pyrazolone type Kabufu. The branched alkyl phosphate represented by the general formula [■] must be included at least in the 3-anilino-4-(2-alkoxyarylthio)-5-pyrazolone magenta coupler-containing layer, but in other emulsion layers and non-emulsion layers. Photosensitive J
r4′! ? It can also be used for. It can be used in any ratio to the magenta coupler, but preferably 5 to 1000% by weight, particularly preferably 1
It is 0 to 200% by weight. The chlorotrianone hardener represented by the general formula [[1] usually diffuses over the entire circumference of the coated layer, so at least one or more chlorotrianone hardeners are used from the width of the emulsion layer or auxiliary layer according to the present invention. Just select and add Wj. The addition is dissolved in water or alcohol (e.g. methyl alcohol, ethyl alcohol, etc.) and added in an amount of 0.5 to 100 B per 1 g of gelatin.
, preferably 2 to 50+H. The addition method may be either a batch method or an in-line method. The color photographic materials of the invention can be, for example, Colorne and Bottfilm, as well as color photographic papers, but especially direct! The effects of the method of the present invention are effectively exhibited when color photographic paper intended for viewing is used. 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, a silver halide emulsion layer containing magenta, yellow and cyan couplers as photographic couplers and a non-light-sensitive layer are usually provided on the support for subtractive color reproduction. Although it has a laminated structure with an appropriate number of layers and layer order,
The number of layers and the order of layers may be changed as appropriate depending on the important performance and purpose of use. The silver halide emulsion of the present invention includes any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used. Halogenatedffl1. The Muharodan Jibutsu candy used for shaving may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. 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. Furthermore, while considering the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them to a mixing pot while controlling 1]1 (and/or p A 8). Good. By this method, silver halide grains with a regular crystal shape and a nearly uniform grain size can be obtained. Even if the halogen composition of the grains is changed using the Convernoyon method after growth, the silver halide grain size is even smaller than 1°. The grain size, grain shape, grain size distribution, and grain growth rate of the silver halide grains -F- can be controlled in the emulsion by using a silver halide agent as necessary during the production of the emulsion.Halogen During the process of grain formation and/or growth, silveride grains contain cadmium salts, zinc salts, lead salts, krillum salts, ilinium salts (combining complex salts), σnotum salts (combining complex salts), and iron. Metal ions are added using at least one kind selected from salts (including complex salts), and metal ions are added inside the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere. The silver halide emulsion may be free of unstable soluble salts after the growth of silver halide grains is completed, or may be left containing them. When removing the salts, use a research paper polisher (Research+D
1sclosure (hereinafter abbreviated as RD)) No. 17643, item (2). 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 composition differs between the inside of the grain and the surface layer. The silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a 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 +1001 plane to the 11111 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. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
Noble metal sensitization methods using gold and other precious metal compounds, etc.
Can be used alone or in combination. Silver halide emulsions are made using dyes known as sensitizing dyes in the photographic industry, and 9 sensitizing dyes that can be optically sensitized to a desired wavelength range may be used alone, but 21 or more may be used in combination. It may also be used. 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 merocyanine dyes, pho-polar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are used. Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex melonanine pigment. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Or Photo 1 ↓ Preventing fog during processing 11-1 or Photo 1
1 In order to keep the performance stable, fogging is commonly used in the photographic industry during chemical ripening, at the end of chemical ripening, and/or by the time silver halide 7L is applied after chemical ripening. Compounds known as inhibitors or stabilizers can be added.Binders (or protective colloids) for silver halide 7L cutting
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose conductors, and synthetic hydrophilic polymer substances such as single or copolymers can also be used. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention may be hardened to 11Q by using one or more hardeners that increase the film strength of binder (or protective colloid) molecules. I can do it. Where is the hardener? I! It is possible to add the photosensitive material in an amount that can harden the solution so that there is no need to add a hardening agent to the solution.
It is also possible to add one hardener to the processing solution. A plasticizer can be added to the silver halide emulsion layer and/or other wood-philic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred 1ffl agents are the compounds described in RD 17643, section X11.8. A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer can be contained in the photographic 7L agent layer and other hydrophilic colloid layers of the light-sensitive material for the purpose of improving dimensional stability. The emulsion layer of the light-sensitive material contains a dye that undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p7z nylene diamine derivative, ami-7 phenol derivative, etc.) to form a dye during color development processing. Forming couplers are used. The dye-forming couplers are selected for each emulsion layer so that a dye is formed that absorbs the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming coupler is selected for the blue-sensitive emulsion layer. 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. A colorless coupler (also called a competitive coupler) which undergoes a camping reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler. As the yellow dye-forming coupler, known azila-7toanilide couplers can be preferably used. Among these, benzoylaceto-7nilide and pivaloylacetanilide compounds are advantageous. As magenta dye-forming couplers, 5-pyrazolone couplers, virazolobenlimigzole couplers, open-chain acylacetonitrile couplers, ingzolone couplers, etc. other than those of the present invention can be used together with the couplers of the present invention. Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Among dye-forming couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, fluorescent whitening agents, etc. that do not need to be adsorbed on the surface of silver halide crystals, hydrophobic compounds can be prepared by solid dispersion method, Ute-Nku large dispersion method, oil-in-water type! The dispersion can be carried out using various methods such as the 7L 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 type 'IIL dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers are applied, and the boiling point is usually about 150.
Dissolve in a high boiling point organic solvent above °C in combination with a low boiling point and/or water-soluble organic solvent if necessary, and add a surfactant to a hydrophilic binder such as gelatin aqueous solution using a stirrer or homogenizer. After dispersing to 1.7 L using a dispersion means such as a colloid mill, a 70-nof mixer, or an ultrasonic device, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion. High boiling, r:, i, solvents include phenol pollutants that do not react with the oxidation method of the developing agent, 7-tar acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters A low-boiling point or water-soluble organic solvent can be used with or in place of a high-boiling, low-boiling solvent. Examples of organic solvents include ethyl acetate, propyl acetate-F, butyl acetate, butyl, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc., and water-soluble organic solvents include acetone, methyl in butyl ketone, etc. , β-nitoquine ethyl acetate,
Methquin glycol 7 cete 11 methanol, ethyl/-
Examples include acetonitrile, nooxane, trimethylformamide, trimethyl sulfoxide, hexamethylphosphoric triamide, noethylene glycol mo7 phenyl ether, When forming couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. contain acid groups such as carboxylic acids and sulfonic acids, hydrophilic colloids can be used as alkaline aqueous solutions. Anionic surfactants can also be used as dispersion aids when a hydrophobic compound is dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using mechanical or ultrasonic waves. agent, /
Ionic surfactants, cationic surfactants and amphoteric surfactants can be used. The oxidation 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 anticapri agent can be used to prevent graininess from forming. The color fog prevention II agent may be contained in the 7L agent layer itself, or may be contained in the intermediate layer provided between adjacent emulsions/f. 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 retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. Notekyl compound is preferably used as a development accelerator! ,tRD
The compound is a compound described in Section XXI B-D of No. 17643, and the development retardant is a compound described in Section XXI KCE of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes. The emulsion layer of a photosensitive material increases sensitivity by 1, increases contrast,
Alternatively, polyfulkylene oxide or other derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imiguzole derivatives, etc. may be included for the purpose of speeding up development. For light-sensitive materials, a fluorescent whitening agent can be used to emphasize the whiteness of the white background and to make the coloration of the white background less noticeable.9 A compound that can be preferably used as a fluorescent whitening agent is RD No. 17G43. It is also mentioned in Section V. The photosensitive material may be provided with an auxiliary J (η) such as a filter layer, a halation layer, a 1F layer of iranoacisin, etc. In these layers and/or in the 7L removal layer, there are substances that may flow out from the photosensitive material during development. (or) may contain a dye that is whitened. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes and the like. - A matting agent can be added to the silver halide emulsion 8'l and/or other hydrophilic colloid layer of the photosensitive material for the purpose of reducing the gloss of the photosensitive material, improving the ease of writing, preventing the photosensitive materials from sticking together, etc. . 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 where the emulsion of the support is not laminated.
It may be used for protective colloids 1vI other than delamination. 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, boriflopyrene,
Flexible reflective supports such as paper laminated with ethylene/butene Kyoden), synthetic paper, semi-synthesis or synthesis of cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of polymers, flexible supports made of these films with reflective layers, plastics, metals, ceramics, and the like. The hydrophilic floid layer of the photosensitive material can be applied directly or after applying corona discharge, ultraviolet irradiation, flame treatment, etc. to the surface of the support as necessary, or to improve the adhesion, antistatic properties, dimensional stability, and abrasion resistance of the support surface. The coating may be coated through one or more subbing layers to improve properties such as hardness, haley silane resistance, friction properties, and tF/or other properties. When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, hardeners, which have FF+ reactivity and may cause gelation before coating if added to the coating solution in advance, should be mixed directly into the coating rttf using a static mixer etc. is preferable. As for the coating method, 2 (Extrulamin coating and curtain coating, which can simultaneously coat layers north of the width, are particularly useful, but 1) Bakent coating is also used depending on the situation. C can be selected arbitrarily.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 monobath processing step using a bath development bleach-fix processing solution can also be carried out. In combination with these processing steps, an m1 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 treatment step, an activator treatment step may be performed in which a color development-IE drug or its precursor is contained in the material and the development treatment is performed with a 7 activator solution, or a monobath treatment may be used. Activator treatment can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process or a stabilization process.) Color development process - bleaching process Constant coloring process 2nd process - Color development process - bleaching Fixing process/Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process/Color development process - Washing process - Supplementary color development process - Stop process -) Nii White Process Jl [Process Constant fixation process / Activator process - Bleach-fix process / Activator process - Bleach process Constant fixation process / Monobath process - [The temperature of the treatment solution is usually selected within the range of 10°C to 65°C, but it may be set to a temperature exceeding 65°C. Preferably 2
Processed at 5°C to 45°C. The color developing solution consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is a YH group primary amine color developing agent, including amino 7-ether derivatives and 11-phenylenenoamine derivatives. These color developing agents can be used as salts of FF substitute acids and non-present acids; for example, salts (phosphoric acid, sulfuric acid, Ma&p), luenesulfonate, sulfite, oxalate, benzenesulfonate, etc. Can be used. These compounds are generally present in a color developer in an amount of about 0.1 to 15 g, more preferably about 1 to 15 g.
Use at a concentration of 15 bis. - Examples of the amino/phenol developer described in 0-
Amino 7 E/-L, IJ-7 M/7 E/-L, 5-Ami 7-2-Hydroxytoluene, 2-Ami/-3-Hydroxy Toluene, 2-Hydroxy-3=7 Minnow 1.4 ~
Contains trimethylbenzene, etc. Particularly useful primary aromatic amine color developers include N,
It is an N-nofurkyl-p-7 enynoamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N,N-tumethyl-p-phenylenediamine hydrochloride, N-methyl-p-
7-enylenenoamine W salt, N,N-noethyl p-phenylenediamine salt FI[,2-amino-5-(N-ethyl-N-dodecyl 7mino)toluene, N-ethyl-N
-β-methanesulfonamidoethyl-3-methyl-4-
ami/aniline sulfate, N-ethyl-N-β-hydroxyethyl ami/7niline, 4-ami 7-3-methyl-N
, N-noethylaniline, 4-7 minnow N-(2-71
4diethyl)-N-ethyl-3-methyl7niline-U-
) luenesulfonate and the like. 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 solution (activator solution) instead of a color developing solution. The color developing solution may contain alkaline additives commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax, and various other additives. additives such as benol alcohol, alkali metal halide, such as potassium bromide or potassium chloride, or development regulators such as citranonic acid, and preservatives such as hydroxylamine or sulfites. Additionally, various antifoaming agents and surfactants, as well as organic solvents such as methanol, trimethylformamide, and trimethylsulfoxide, etc., may be appropriately contained. Color developer 1. +IT is usually 7 or more, preferably about 9-13. The color developing solution used in the present invention may optionally contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-aniso/ethanol, nohydroxyacetone, aromatic difurfur, hydroxamic acid, and pentose. Also 1 hexose, pyrogallol-1
, 3-methyl ether, etc. may be contained. In the color developing solution, species/(
A chelating agent can be used in combination. For example, aminopolycarboxylic acids such as ethylenenoaminetetraacetic acid and noethylenetriaminepentamethic acid, (f) phosphonic acids such as 1-hydroquinethylene-1,1-nophosphonic acid, (methylenephosphonic acid) or 7-polyphosphonic acid such as ethylenenoamine titraphosphoric acid, oxycarboxylic acid such as citric acid or glufunic acid, phospho/carboxylic acid such as 2-phospho/butane to 1,2,4-tricarboxylic acid Acids, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, polyhydroxy compounds, etc. The bleaching process may be carried out simultaneously with the fixing process as described in 11.I, or may be carried out separately. Good. As a bleaching agent, a metal complex salt of an organic acid is used, for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, citric acid, etc., coordinated with metal ions such as iron, cobalt, copper, etc. Among the above organic acids, the most preferred organic acids include polycarboxylic acids or amide/polycarboxylic acids. Examples of these are ethylenenoaminethitraacetic acid, noethylenetriaminebentaacetic acid, ethylenenoaminebentaacetic acid, and ethylenenoaminethitraacetic acid. Amine-N-(β-oxyethyl)
-N. N',N'-triacetic acid, propylenenoamine thitraacetic acid, nitrilotrim, acid, cyclohexanoamine thitraacetic acid, iminonoacetic acid, nohydroxyethylglycine N! (or tartarite Nl), ethyl ethernoamine tetraacetic acid, glycol ether diamine tetraacetic acid,
Examples include ethylenenoaminetetrabrobionic acid and phenylenenoaminetitraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are preferably used at 5-450 g/l, more preferably 20-250 g/l. For the bleaching solution: In addition to the bleaching agents as described in ijf, a solution containing sulfite as a preservative can be used if necessary. Further, the bleaching solution may be a solution containing an ethylenenoamine titraacetate iron (T[I) complex salt bleaching agent and a large amount of a halide such as ammonium bromide added thereto. In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium hydroxide, rum, potassium bromide, sodium iodide, potassium iodide, and Ammonium chloride and the like can also be used. Bleaching solutions include JP-A No. 46-280 and JP-A No. 45-85.
No. 06, No. 4G-550, Belly Patent No. 770,91
No. 0, Special Publication No. 45-8836, No. 53-9854,
Various bleach accelerators described in JP-A-54-71634 and JP-A-49-42349 can be added. )↑The pH of the white liquor is used at 2.0 or higher, but generally it is used at 4.0-9.5, preferably 4.5-8.
．． It is most preferably used at 0, more preferably from 5.0 to 7.0. A fixer having a commonly used composition can be used. As a fixing agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, or potassium thiocyanate, which is used in ordinary fixing processing, may be used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount that is s/1 or more and can be dissolved, but for the shell it is used in an amount of 70 to 250 g/l. Incidentally, a part of the fixing agent 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, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. Il buffer
It can be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants may be contained. In addition, 17 of hydroxylamine, hydranone, and aldehyde compounds
i 11i, preservatives such as sulfuric acid adducts, organic chelating agents such as aminopolycarboxylic acids, or nitro alcohols,
Stabilizers such as nitrates, hardeners such as water-soluble aluminum salts, organic solvents such as methanol, trimethylsulfamide, trimethylsulfoxide, and the like can be appropriately contained. The fixer is used at +3113.0 or higher, generally from 4.5 to 10, preferably at 5=9.5, and most preferably at 6.-9. Examples of the whitening agent (used in the bleach-fixing solution) include metal complex salts of organic acids described in the -[-) knee whitening treatment process, and preferred compounds and concentrations added to the treatment solution are also suitable for the bleaching treatment described above. It is the same as in the process. Bleach fixing solution
A 3+1 solution containing l', sulfate is applied. Further, a small amount of an ethyleneno'amine iron tetraacetate (1) complex salt bleach and another halide such as ammonium bromide of the above-mentioned silver halide fixing agent is added to fix the white paper (consisting of the composition r:). Or conversely, a special bleach-fixing solution containing a large amount of a halide such as ammonium bromide can be used.The halogenated substances include ammonium bromide, hydrochloric acid, Hydrobromic acid, lithium bromide, chloride, potassium bromide, iodide, potassium iodide, ammonia iodide, etc. can also be used as bleach-fix solutions. Examples of the silver halide fixing agent that can be included in the fixing process include the fixing agents described in the above fixing treatment process. The additives are the same as in the fixing step 111j described in -.) The pH of the blank fixer is used at 4.0 or higher, but generally it is 5.0 to 9.5 (heavily used). , preferably 6.0
~8.5, most preferably 6.5-8.5.

〔Example〕

The present invention will be explained in more detail by showing specific examples below, but the embodiments of the present invention are not limited thereto. Example 1 30 g of the magenta coupler of the general formula ([V) of the present invention] and 5 g of the compound of the general formula [1] were added to the compound 4 of the general formula CI []
After dissolving in a mixed solvent of 0 mQ and 100 mQ of ethyl acetate, adding this solution to a 5% gelanan aqueous solution containing sodium dodecylbenzenesulfonate, dispersing with a homogenizer (trowel) and dispersing the resulting dispersion with a green-sensitive salt. Silver bromide emulsion 5
00g (containing 30g of H), and a coating aid was added thereto to prepare a coating liquid. This coating solution was then coated onto a polyethylene-coated paper support, and two layers were further applied onto this coating layer.
．． -(2'-Hydroxy-31,51-cy-7-milphenyl)benzotriazole, gelatin, and 1 g of gelatin using a compound of general formula [111] as a spreading agent and a hardening agent.
A coating solution containing 0.02G per coat was applied to form a protective film. At this time, 2-(2'-hydroxy-3'*5'-
7-t-7 milphenyl) benzotriazole is 5+B
/da+2, gelatin was coated so as to have an adjunct of 15wg/Ja+' to create a monochromatic color photographic material (sample N
o, 5-9). Similarly, a sample without the addition of general formula [I] compound, general formula C
11) or samples using comparative compounds instead of the compound of general formula [1[1] were prepared (Sample Nos. 1 to 4). Below is the margin '1 (comparative compound) nl -13 COCII"CH2
After performing a test for sensitometry using a mold), the following process J+u was performed. Base treatment process (treatment temperature and treatment time) treatment process
Processing temperature Process I11! Time color original image 32.8
Bleach fixing at °C for 3 minutes and 30 seconds at 32.8 °C 1
Wash with water for 30 seconds at 32.8°C for 3 minutes and 30 seconds.
The place used in the above treatment step J'l! l (i composition is as follows, (Color developer composition) 4-amino/-:)-nonal-N-ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate g Bennol alcohol 15ml 1l
Hexa/Sodium phosphoric acid 7m 2.5
g Anhydrous 111 (sodium sulfate L
8.5H diS conversion

0.7■ Central potassium 0.5H sand
+ II 10, ii to 3! ! J Adjust. () Prefectural fixing tank liquid) Ethylenenoaminetetraacetic acid iron ammonium old, Og Ethylenecyaminetetraacetic acid diammonium dihydrate
5. Og ammonium thiosulfate 124,51 (sodium metabisulfite 13.5Fi anhydrous sodium sulfite 2.7g to make 1Q. After treatment, the light resistance, moist heat resistance, and increase in Y-stin due to storage of the obtained sample was measured in the following manner: [1. Likelihood test (fading rate measurement)] % fading when the dye image formed on each sample was exposed to 1174 sunlight for 500 hours using an underglass outdoor exposure table. (Do D X100: Do initial concentration (1,0)
O I) The density after fading was measured. [Y-Stain Test] Each sample was stored in a constant temperature bath at 77° C. without humidification for 2 () days. Preservation 11: The difference (increase density) in the 17 color likelihood radiance of the white part of each sample afterward was measured. [Moist and heat resistance test T!J, (fading rate measurement)] Dye image formed on each sample Discoloration l (Do-D
00: Do initial concentration (+, , (, )), O concentration after fading) was measured. These results are shown in Table 1. As is clear from Table 1, 3-anilino-4-(2-flucoquinarylthio)-5-pyrazolone! 11! In the sample using a coupler, general formula [1, general formula rt
By using l+ and the compound of the general formula [1111], the likelihood, moist heat resistance, and stain resistance of the dye image were improved. Samples 15.7.8 and 9 were tested when I-2, l-3, I-4, and -22 were used instead of l-1 in samples 5.7, 1, and 9. Similar results were obtained. Example 2 On a paper support laminated on both sides with polyethylene, the following first layer (bottom) t! J) to the seventh layer (uppermost layer) were sequentially applied to prepare color photographic materials (Sample Nos. 10 to 19). The following are 77 (additional compounds) 8-1 ll ^-2 H ^-3 Δ-4 and 11. , -(SO3SO:+Na) One layer of the coating liquid for the first layer was prepared as follows. That is, the yellow coupler 1()Og shown in Table 1 was mixed with Nobutyl 7Tale) (DBP) 116.7. Q and 200 mQ of ethyl acetate, and this solution was dissolved in 800 g of a 10% aqueous gelatin solution containing 80 mQ of a 1% aqueous solution of dodecylbenzenesulfonm.
This emulsified dispersion was then mixed with a blue-sensitive silver chlorobromide emulsion (80% Br) 1450H (containing 66.7 g of Ag) to prepare a coating solution. Coating liquids for other scraps were prepared in the same manner. The hardener for the three layers is 2.4-7chloro6-hydroxy-S-trianone.
Sodium salt was used. The following dyes were used as the iranoacetan-preventing dyes for each 7L cutter X4. Is the margin green sensitivity below? L agent layer; Red-sensitive 7L agent waste The obtained sample is exposed to light? It was exposed to white light through PA and a green filter, developed in the same manner as in Example 1, and measured in the same manner as in Example 1 for roundness, heat-and-moisture resistance, and Y-stin. The results are shown in Table 2. It is clear from Table 2 below) that the 3-anilino-4-(2-flucoxyarylthio)-5-pyrazolone type coupler was used in the 7γ light-sensitive material sample. By using the compounds of general formula [111 and general formula III] in combination, the likelihood of magenta color images, the moist heat resistance, and the Y-stain resistance of the light-sensitive material were improved.

Claims (1)

[Claims] 3-anilino-4-(2-alkoxyarylthio)-
A silver halide color photograph comprising a 5-pyrazolone type coupler, 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] ▲ Numerical formulas, chemical formulas, tables, etc. The total number of carbon atoms in the group is 24~
It is 40. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc.
), -NR'R'' group (R' and R
"represents a hydrogen atom, an alkyl group, or an aryl group, respectively) or -NHCOR'"(R'" represents a hydrogen atom,
represents each group (representing an alkyl group or an aryl group), R
_1_0 has the same meaning as R_9 excluding the chlorine atom. ]