JPH03218342A - Beta,gamma-unsaturated nitriles, coupler for photograph, color image forming method using the same compound and halogenated silver color photographic sensitive material containing the same compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (W is H or eliminating group which causes elimination when oxide of aromatic primary amine derivative is subjected to coupling reaction; R1 is substituent group; V is N or CR3; When V is N, R2 is substituent group and when V is CR3, at least one of R2 and R3 is electron attracting substituent group and the other is substituent group, provided that when R2 or R3 is aliphatic group or aromatic group, the other is not acyl; R1 and R2 together may form a ring). EXAMPLE:A compound expressed by formula II. USE:Cyan coupler for photograph capable of providing cyan color image reduced in subsidiary absorption and having good duplicativity and excellent fastness. PREPARATION:For example, 3-nitrobensonitrile is allowed to heat with acetonitrile in the presence of potassium tert.-butoxide to give a compound expressed by formula III, which is then made to with malononitrile and the resultant compound expressed by formula IV is reduced with iron and then subjected to a reaction with a compound expressed by formula V to provide the exemplified compound.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention provides novel β, useful for photographic color couplers, etc.
The present invention relates to γ-unsaturated nitriles and color photographic materials containing the compounds. In particular, the present invention relates to a silver halide color photographic material with improved color reproducibility by using a novel cyan coupler. (Prior art) Using exposed silver halide as an oxidizing agent, the oxidized aromatic primary amine color developing agent and coupler react to form indophenol, indoaniline, indamine,
It is well known that azomethine, phenoxazine, phenazine and similar dyes are produced to form color images. In such photographic systems, a subtractive color process is used, in which yellow, magenta and cyan dyes form a color image. (Problems to be Solved by the Invention) Among these, phenol or naphthol couplers are generally used to form cyan images. However, these couplers have a major problem in that they have unfavorable absorption in the green region, which significantly reduces color reproducibility. Various compounds have been proposed to solve this problem, but none have been satisfactory. Currently, there are no compounds that exhibit such performance. Therefore, the objects of the present invention are (1) to provide novel β, γ-unsaturated nitriles useful for photographic couplers and the like. (2) The object of the present invention is to provide a color photographic light-sensitive material containing a novel coupler that forms a dye with low side absorption and a large molecular extinction coefficient, especially a cyan coupler. (3) To provide a novel coupler with excellent coupling activity, an image forming method using the same, and a color photographic material containing the same. (4) To provide a cost-effective coupler with a small number of synthesis steps and a color photographic material containing the same. (5) To provide a color photographic material from which cyan images with excellent image fastness can be obtained. (Means for Solving the Problems) The object of the present invention is to provide β, γ represented by the following general formula (I)
This has been effectively achieved by monounsaturated nitriles, photographic color couplers, image forming methods using the same, and silver halide color photographic light-sensitive materials containing this compound. General formula (I) π H1 (wherein, W is a hydrogen atom, << represents a leaving group that leaves when this compound undergoes a coupling reaction with an oxidized product of an aromatic primary amine derivative, and R1 is represents a substituent, ■ represents a nitrogen atom or R3 1 represents -C=, when ■ represents a nitrogen atom, R. 1 R2 is a substituent, and when ■ represents -C=, R2 and R3 At least one of << represents an electron-withdrawing substituent and the other represents a substituent. However, when R2 or R represents an aliphatic group or an aromatic group, the other is an acyl group. In addition, R and R2 may be linked to each other to form a ring.> The compound of the present invention will be described in more detail below. In the general formula (I), R represents a substituent, Substituents or halogen atoms, preferably aliphatic groups having 1 to 36 carbon atoms, preferably aromatic groups having 6 to 36 carbon atoms (e.g. phenyl, naphthyl, 24-chlorophenyl), heterocyclic groups (e.g. 3-pyridyl, 2-chlorophenyl), -furyl), alkoxy groups (e.g. methoxy, 2-methoxyethoxy), aryloxy groups (e.g. 2,4' di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy)
, alkenyloxy group (e.g. 2-propenyloxy)
, amino groups (e.g. butylamino, dimethylamino, anilino, N-methylanilino), acyl groups (e.g. acetyl, benzoyl), ester groups (e.g. butoxycarbonyl, phenoxycarbonyl, acetoxy, penzoyloxy, butoxysulfonyl, toluenesulfonyloxy), Amide groups (e.g. acetylamino, ethylrbamoyl, dimethylrubamoyl, methanesulfonamide, butylsulfamoyl), sulfamide groups (e.g. dibrobylsulfamoylamino), imide groups (e.g. succinimide, hydantoinyl), ureido groups ( e.g. phenylureido, dimethylureido), aliphatic or aromatic sulfonyl groups (e.g. methanesulfonyl, phenylsulfonyl), aliphatic or aromatic thio groups (e.g. ethylthio, phenylthio), hydroxy groups, cyano groups, carboxy groups, nitro groups , a sulfo group, etc. In this specification, the term "aliphatic group" refers to a linear, branched or cyclic aliphatic hydrocarbon, such as alkyl, alkenyl,
It is meant to include saturated and unsaturated groups such as alkynyl groups. Representative examples include methyl group, ethyl group,
Butyl group, dodecyl group, octadecyl group, icocenyl group, isO-propyl group, tert-butyl group, te
rt-octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, 2-
Examples include hexadecenyl group and probargyl group. In general formula (I), when ■ represents Ichiko=, at least one of R2 and R represents an electron-absorptive substituent, and preferably the value of Hammett's substituent constant 02 is 0. ，
Represents a substituent or atom of 1O or more, more preferably represents a substituent of 0.35 or more, and even more preferably,
Represents a substituent with a value of σ2 of 0.60 or more. This σ1
The value is preferably 2 or less. The value of Hammett's substituent constant a, , referred to here is given by Hansch, C. Leo
(e.g. J. Med. Chem. 16,
1207 (1973); ibid. 20, 30
4(197?)) is preferably used. As substituents or atoms with an ap value of 0.10 or more,
Chlorine atom, bromine atom, iodine atom, substituted alkyl group (e.g. trichloromethyl, trifluoromethyl, chloromethyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluorobutyl), nitrile group, acyl group (e.g. formyl, acetyl, benzoyl), 10 carboxyl groups, substituted or unsubstituted carbamoyl groups (e.g. carbamoyl, methylcarbamoyl), alkoxycarbonyls (e.g. methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), substituted with other electron-withdrawing groups Aromatic groups (e.g. pentacrophenyl, pentafluorophenyl), heterocyclic residues (e.g. 2-
penzoxazolyl, 2-penzthiazolyl, 1-phenyl-2-penzimidazolyl, 1-tetrazolyl),
Nitro groups, azo groups (e.g. phenylazo), amino groups substituted with other electron-withdrawing groups (e.g. ditrifluoromethylamino), alkoxy groups substituted with other electron-withdrawing groups (e.g. trifluoromethoxy), alkyl Sulfonyloxy group (e.g. methanesulfonyloxy), acyloxy group (e.g. acetyloxy, penzoyloxy)
, an arylsulfonyloxy group (eg, benzenesulfonyloxy), a phosphoryl group (eg, dimethoxyphosphonyl, diphenylphosphoryl), a sulfamoyl group, a sulfonyl group (eg, 1 1 trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), and the like. Examples of substituents with an ap value of 0.35 or more include alkyl groups substituted with other electron-withdrawing groups (e.g. trifluoromethyl, barfyl butyl), nitrile groups, acyl groups (e.g. acetyl, benzoyl, formyl), Carboxyl groups, carbamoyl groups (e.g. carbamoyl, methylrubamoyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), aromatic groups substituted with other electron-withdrawing groups (
pentafluorophenyl), heterocyclic residues (e.g. 1-tetrazolyl), ditro groups, azo groups (e.g. phenylazo), amino groups substituted with other electron withdrawing groups (e.g. ditrifluoromethylamino), and other Alkoxy groups substituted with electron-withdrawing groups (e.g., trifluoromethoxy), alkylsulfonyloxy groups (e.g., methanesulfonyloxy), phosphoryl groups (e.g., dimethoxyphosphoryl, diphenylphosphoryl), 12 sulfamoyl groups, sulfonyl groups (e.g., trifluoromethoxy), lomethanesulfonyl, methanesulfonyl, benzenesulfonyl), etc. Examples of the substituent having a value of σ of 0.60 or more include a nitrile group, a nitro group, a sulfonyl group (eg, trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), and the like. Substituents when R2 or R3 is not an electron-withdrawing group include, for example, aliphatic groups (e.g. methyl, ethyl or octyl), alkoxy groups (e.g. methoxy, ethoxy,
dodecyloxy), or an amide group (e.g. acetamide, bivalylamide, or octaneamide), an aromatic group (e.g. phenyl,
4-alkoxyphenyl), a heterocyclic group (for example, 2-furyl, 2-chenyl, 2-thiazolyl). However, when R2 or R3 represents the aliphatic group and << represents the aromatic group, the other is not an acyl group. 13 Among the compounds represented by the general formula (I) in the present invention, compounds represented by the following general formula (I[) or (III) are preferred. General formula (II) W (wherein, W has the same meaning as that of general formula (I). (Both represent a methine group having an electron-withdrawing group, n represents 1 or 2, and Q represents a nonmetallic atomic group necessary to form an aromatic ring.) General formula ( Ill) 1 4 (wherein, W has the same meaning as that in general formula (I). R4
At least one of and R6 represents an electron-withdrawing substituent, and the other represents a substituent. However, R4 and R5 do not combine to form a ring. ) In the present invention, compounds represented by the general formula (Ill) are most preferred. In general formula (II), X. Y and Z are each a nitrogen atom, a methine group, or a methine group having an electron-withdrawing group, at least one of which represents a methine group having an electron-withdrawing group; When expressing 10=, Y
When represents a methine group as described above, p - When represents a methine group as described above, R6 and R may be the same or different, and may be bonded to each other to form a ring. Similarly, when Y and 2 each represent a methine group as described above, R7 and R
8 may be the same or different and may be bonded to each other to form a ring. In that case, << is preferably a fused ring, such as a benzene fused ring or a pyridine fused ring. R6, R7 and R8 are electron-withdrawing substituents, preferably representing a substituent having a value of Hammett's substituent constant σ9 of 0.10 or more, more preferably 0.35 or more, and Preferably, it represents a substituent having a value of σ2 of 0.60 or more. Examples of the substituent include the substituents listed for R2 or R3 above. In general formula (II), Q together with the bonding carbon atom or nitrogen atom is a 5-membered ring or more, preferably a 5- to 8-membered ring,
More preferably, it represents an atom or atomic group necessary to form a 5-membered ring or a 6-membered ring, and examples of the divalent group forming the ring include a divalent amino group, an ether bond, a thioether bond, an alkylene group, and an alkenylene group. , imino group, sulfonyl group, carbonyl group, etc., and these may have a substituent. Examples of the substituent here include the substituents listed for R above. Particularly preferably, Q is a thioether bond, an imino group, or a sulfonyl group. In general formula (III), at least one of R4 and R5 represents an electron-withdrawing substituent, preferably a substituent having a Hammett's substituent constant σ9 of 0.10 or more, more preferably a substituent with a Hammett's substituent constant σ9 of 0.10 or more. It represents a substituent with a value of 0.35 or more, more preferably a substituent with a value of σ1 of 0.60 or more. Examples of the substituent include the substituents listed above for R2 or Rs. When R4 or R6 represents a substituent, for example, preferably an aliphatic group having 1 to 36 carbon atoms (such as methyl, proyl, t-butyl, tridecyl, 3-(2.4-dit
-amylphenoxy)probyl, 2-dodecyloxyethyl, 3-phenoxybrobyl, cyclopentyl, benzyl, allyl, probargyl), preferably 6 to 6 carbon atoms
36 aromatic groups (e.g. phenyl, naphthyl), hetero 1
7 Ring groups (eg, 2-furyl, 2-chenyl, 2-pyrimidyl, 2-thiazolyl), and the like. R4 and R5 may be in the cis or trans position. In general formulas (1), (II), and (III), W represents a hydrogen atom or a leaving group that leaves when the coupler reacts with an oxidized product of an aromatic primary amine developing agent (hereinafter simply referred to as a "leaving group"). ), and when W represents a leaving group, the leaving group is an octarogen atom, an aromatic azo group, an oxygen
Groups that bond to aliphatic groups, aromatic groups, heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, or 18 aliphatic/aromatic or heterocyclic carbonyl groups via nitrogen, sulfur, or carbon atoms. or a heterocyclic group bonded to the coupling position with a nitrogen atom, and the aliphatic, aromatic, or heterocyclic group contained in these leaving groups may be substituted with a substituent allowed by R, and these When there are two or more substituents, they may be the same or different, and these substituents further R
1 may have a permissible substituent. The leaving group is a group that leaves when the coupler reacts with the oxidized form of the developing agent, and specific examples include halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.),
Alkoxy groups (e.g. ethoxy group, dodecyloxy group,
methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methanesulfonylethoxy group, etc.),
Aryloxy group (e.g. 4-chlorophenoxy group, 4
methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetradecanoyloxy group, penzoyloxo group, etc.), aliphatic or aromatic sulfonyloxy group (e.g., methane-
sulfonyloxy group, toluenesulfonyloxo group, etc.)
, acylamino group (e.g. dichloroacetylamino group,
aliphatic or aromatic sulfonamide group (e.g., methanesulfonamide group, p-toluenesulfonamide group, etc.), alkoxy group (e.g., ethoxycarponyloxy group, henzyloxy group, etc.), aryloxy aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, 2-carpoxyethylthio, phenylthio, tetrazolylthio, etc.), carbamoylamino groups (e.g. N-methyl a 5- or 6-membered nitrogen-containing heterocyclic group (such as an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group,
1,2-dihydro-2oxo-1-pyridyl W, etc.),
Imide group (e.g., succinimide group, hydantoinyl group, etc.), aromatic azo group (e.g., feu.nylazo group, etc.)
These groups may be further substituted with a group allowed as a substituent for R1. Furthermore, there are bis-type couplers obtained by condensing a four-dimensional coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators. The compounds of the present invention are useful as photographic color couplers, and are particularly useful as cyan couplers. Specific examples of the compounds of the present invention are shown below, but the present invention is not limited thereto. (1) (2) (3) (4) Nri 2 (5) (6) Shi support (7) (8) (9) (1 0) 0 (1 1) (1 2) (1 3) ( 1 4) CN (l 5) (1 6) (1 7) (I9) (20) (21) ■ (22) 5(Izl;+6H*ko"' (23) (2 4) (2 5) NU2 (26) (27) COCiH+z H (28) 0 (2 9) (3 0) 0 \C8HI7 (36) The compound of the present invention can be synthesized by the method shown in the Examples below. In this case, in general formula (I) The method of introducing a group corresponding to the leaving group W is as follows: ■ For the halogen atom, the coupling position of the four-equivalent coupler is halogenated; ■ For the one-leaving group, the coupling position of the four-equivalent coupler is halogenated, and the presence of a base is introduced. Method of reacting with phenolic compounds below,■
The S1 leaving group is prepared by reacting phenyl chloride, which is the leaving group of a four-equivalent coupler, in the presence or absence of a base, and the N1 leaving group is prepared by reacting the coupling position of a four-equivalent coupler with a nitrosating agent using an appropriate nitrosating agent. It can be introduced by reducing it by an appropriate method (for example, a hydrogenation method using pa-carbon as a catalyst, a chemical reduction method using stannous chloride, etc.), and then reacting it with various halides. The method of introducing such a leaving group is known per se, and is described in U.S. Pat. No. 3,894,875, U.S. Pat.
, No. 296, 199, No. 3,227,554, No. 3,
No. 476,563, No. 4,296,200, etc. can be referred to. The coupler represented by the general formula (I) of the present invention undergoes a coupling reaction with an oxidized developing agent to form a dye. This product can also be used as a cyan dye in various applications (for example, as a dye for filters, paints, inks, images and information recording or printing). When the compound of the present invention is contained in a silver halide photosensitive material as a color coupler, it is preferably contained in a light-sensitive silver halide emulsion layer, and particularly preferably contained in a red-sensitive silver halide emulsion layer. The standard amount of the color coupler of this invention used is 0.002 to 1 mole, preferably 0.1 mole to 0.5 mole, per mole of photosensitive silver halide. Further, when the coupler of the present invention is soluble in alkaline water, oil, and liquid, it can be dissolved in an alkaline aqueous solution together with a developing agent and other additives, and used for forming a dye image as so-called external development. In that case, the amount added is 0.000. 'OO05~0.05 mol, preferably << is 0.0
05 to 0.02. The coupler of the present invention can be introduced into the photosensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil-in-water dispersion method. be able to. In the oil-in-ice dispersion method, the solution is dissolved in either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, and then dissolved in water or in the presence of a surfactant. Finely decompose gelatin solution etc. into an aqueous medium. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing or ultrafiltration before use for coating. The coupler of the present invention can be applied to photosensitive materials of 7-gative working or photosensitive materials, and can be applied to photosensitive materials that undergo wet development processing or dry development processing such as heat development. This also applies to the luminescent materials applied. Specifically, it can be applied to, for example, negative color film, reversal color film, color (for boolint) paper direct positive color sensitive material, reversal color barber, heat-developable color sensitive material, color diffusion transfer light-sensitive material, and the like. Silver halides used in such sensitive materials include silver chloride, silver bromide, silver iodobromide, silver chlorobromide, and the like. Additives and materials suitable for use in color paper are typically explained below, but these can also be applied to other photosensitive materials. The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the colors are coated on the support in the above order. It is normal that
The order may be different from this. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers include
A silver halide emulsion sensitive to each wavelength range,
Pigments that have a complementary color relationship to the light they are exposed to: yellow for blue, magenta for green, and T for red.
By containing a so-called color coupler that forms a color, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above. As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [Single layer or multiple layers] Particles with a so-called layered structure in which the halogen composition is different, or
Particles with a structure that has parts with different halogen compositions in a non-layered manner inside or on the particle surface (if on the particle surface, parts with different compositions are joined to the edge, corner, or surface of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundaries between the parts that differ in halogen composition are
The boundary may be clear, or may be unclear due to the formation of wet crystals due to compositional differences, or it may be a boundary that is actively made to have a continuous structural change. Regarding the halogen composition of these salt-smelling tablet emulsions, any silver bromide/silver chloride ratio can be used. This ratio can vary over a wide range depending on the purpose, but if the silver chloride ratio is 2. % or more.Furthermore, so-called high silver chloride emulsions with a high silver chloride content are preferably used for light-sensitive materials suitable for rapid processing.The silver chloride content of these high silver chloride emulsions is 90 mol% or more is preferable《,
More preferably 95 mol% or more. Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized phase is present in the interior and/or surface of the silver halide grains in a layered or irregular manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably exceeds 20 mol%. These localized phases can be located inside the particle, or on the edges, corners, or surfaces of the particle surface, but one preferred example is one that has grown epitaxially at a part of the corner of the particle. . On the other hand, even in high silver chloride emulsions with a silver trichloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure. It is also preferable to use Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution. In such cases, the silver chloride content is 98 mol% to 10
Emulsions of nearly pure silver chloride, such as 0 mole percent, are also preferably used. Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1μ to 2μ. In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%.
Hereinafter, a so-called monodisperse material having a concentration of 15% or less is preferable. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating. The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
It is possible to use those having a (lar) crystal shape, those having an irregular (i (regular) crystal shape such as spherical or plate-like), or those having a composite shape of these. In the present invention, among these particles, particles having the above-mentioned regular crystal shape should be contained in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more. In addition to these, the average aspect ratio (circular equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used. The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chimie et Phisique Pho by es
tographique (PauTMontel, 1967), G. F. Photo by Ruffin
o-graphic Bmulsion Chemises
try (Focal Press, 1966)
:, v, L. Written by Zalikman et at I
Jacking and Coating Photogr.
aphic Bmuldion (Focal Pre
It can be manufactured using the method described in ``Ss Publishing, ■964''. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt includes the one-sided mixing method,
Any method such as a simultaneous mixing method or a combination thereof may be used. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening. Examples of compounds used include cadmium, zinc, lead,
Copper, salts such as Thalium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies widely depending on the purpose, but is preferably from 10-s to 104 moles relative to silver halide. The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization. Regarding the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by total sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used. The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good. When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. is usually used. In the present invention, the cyan coupler, magenta coupler and yellow coupler preferably used in combination have the following general formulas (C-1), (C-I[), (M-I), (M-I1)
and (Y). General formula (CI) 0 Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In this process, it is preferable to add a spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, those described by F. M. Harmer}1e
terocyclic compounds-Cyan
ine dyes. and related comp
ounds (John Wilay &S'ons
(New York, London), 1964
2013). As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272 specification, page 22, upper right column to page 38, are preferably used. The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used. General formula (C-II) 0 ■ Y2 General formula (M-I) General formula (M Old general formula (Y) In general formula (C-I) and (C-I[), R1,
R2'J6 and R4 represent a substituted or unsubstituted aliphatic, aromatic, or heterocyclic group, R3, R, and R6 represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group, and R , may represent a group of nonmetallic atoms that together with R2 form a nitrogen-containing 5- or 6-membered ring. Y1 and Y2 represent a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized form of a developing agent. n represents 0 or l. R in general formula (C-II) is preferably an aliphatic group, such as methyl group, ethyl group, proyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexyl group. Examples include methyl group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group. Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-1) are as follows. In the general formula (C-I>), preferable R1 is an allyl group or a heterocyclic group, and a halogen atom , an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or an aryl group substituted with a cyano group. Preferred. In the general formula (C-I), when R3 & Ri do not form a ring, R is preferably a l!!substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted γ alkyl group and R is preferably a hydrogen atom. In the general formula (C-If), R is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group. In the general formula (C-I1), R preferably has 2 to 2 carbon atoms.
It is a methyl group having 15 alwyl groups and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group. In general formula (C-II), Rs is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms. In general formula (C-II), preferred R6 is a hydrogen atom,
A halogen atom, with chlorine and fluorine atoms being particularly preferred. Preferred Y and Y in general formulas (C-1) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively. In general formula (M-1), R and R represent an aryl group, and R. represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y represents a hydrogen atom or a leaving group. The substituents allowed for the aryl group (preferably, phenyl group) of R7 and R are the same as the substituents allowed for the substituent R1, and when there are two or more substituents, may be the same or different. R is preferably a water atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Preferred Y3 is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, for example as described in U.S. Pat.
No. 351, 897 and International Publication W 0 88/0479
The sulfur atom detachment type as described in No. 5 is particularly preferred. In general formula (Mn), RIO represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, and is particularly preferably a halogen atom or an arylthio group. ZaSZb
and Zc represents methine, substituted methine, 2N1 or 1NH1, and one of the Za-Zb bond and the Zh-Zc bond is a double bond and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. R1. or 2 in Y4
When forming a multimer with more than 1 mer, or when Za, zb or Zc is a substituted methine, the substituted methine is
This includes the case where a multimer of more than one mer is formed. Among the birazoloazole couplers represented by the general formula (M-11), imidazo[1,2 -b) pyrazoles are preferred, US Pat. 540. Birazolo(1,5-b]I:1,2.4)}riazole described in No. 654 is particularly preferred. In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2, 3, or 6 position of the pyrazolo}IJ azole ring to create a birazolotriazole coupler, which is described in JP-A-61-65246. birazoloazole couplers containing a sulfonamide group in the molecule, birazoroazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent (Publication) No. 226 ．． It is preferred to use birazolotriazole couplers having an alkoxy group or aryloxy group at the 6-position as described in No. 849 and No. 294,785. In general formula (Y), R. represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group,
R+2 represents a hydrogen atom, a halogen atom or an alkoxy group. A represents -NIICOR,a. However, La
and Rl4 each represent an alkyl group, an aryl group or an acyl group. Y represents a leaving group. RI2 and Rl. ,R
The substituents for l4 are the same as those allowed for R, and the leaving group Y is preferably of the type that leaves at either an oxygen atom or a nitrogen atom, and is a nitrogen atom leaving type. is particularly preferred. General formula (C-1), (C old, (M- 1 >, (M-
Specific examples of couplers represented by II) and (Y) are listed below. (C-1) (C-4) (C-7) (C 14) (C 15) (C-17) (C 18) (C 19) ■ (C 20) (C-21) (C-22 ) IJUH Ko (M 1) (M 2) (M-3) (M-7) (M- 8) 1;l CH3 (Y-1) (Y 2) (Y-3) u■ (Y 4) (Y 5) (Y 6) (Y-7) (Y-8) (Y 9) The couplers represented by the above general formulas (C-1) to (Y) are silver halides constituting the photosensitive layer. The emulsion layer usually contains 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol, per mol of silver halide.In the present invention, in order to add the coupler to the photosensitive layer, Various known techniques can be applied.Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method.Coupler dispersion From things,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion. As a dispersion medium for such a coupler, the dielectric constant (25℃)
2 to 20, and a refractive index (25° C.) of 1.5 to 1.7, it is preferable to use a high molecular weight solvent and/or a water-insoluble polymer compound. As the high-boiling organic solvent for the coupler of the present invention and other couplers, high-boiling organic solvents represented by the following general formulas (A) to (E) are preferably used. General formula (A) llI, 0 M. -0-P=0 0 W3 General formula (B) M. -COO-L General formula (E) llIl-0-llI2 (wherein, W., W, and W are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group,
Represents an aryl group or a heterocyclic group, and is W1, OW
, or S-W, where n is an integer from 1 to 5, and when n is 2 or more, W may be the same or different from each other, and in general formula (E), VI. &IA2
may form a synthetic ring). The high boiling point organic solvent that can be used in the present invention also has a melting point of 100°C or less and a boiling point of 140°C, even if it is not represented by general formulas (A) to (E).
Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high boiling point organic solvent is preferably 8
The temperature is below 0°C. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher. For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4. These couplers can also be combined with loadable latex polymers (
For example, U.S. Pat. No. 4,203. No. 716) or dissolved in a water-insoluble and organic solvent-soluble polymer to emulsify and decompose into an aqueous hydrophilic colloid solution. Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W 0 88/00723 are used, and the use of acrylamide polymers is particularly preferred from the viewpoint of color image stabilization. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amine necks, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximato)nickel complex and (bis-N,N-dialkyldithiorubamato)nickel complex can also be used. Specific examples of organic antifade agents are described in the following patent specifications: Hydroquinones are covered by U.S. Patent No. 2,360,290.
No. 2, 418. No. 613, same No. 2. 700
．． No. 453, No. 2,701, No. 197, No. 2,
728. No. 659, same No. 2. 732. No. 300, No. 2, 735, 765, No. 3, 982.
No. 944, No. 4,430,425, British Patent No. 1,363. No. 921, U.S. Patent No. 2. 710,
No. 801, No. 2, 816. 028 etc., 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans are covered by U.S. Patent No. 3,432,300.
No. 3. 573. No. 050, No. 3, 574
, No. 627, No. 3, 698.909, No. 3,
No. 764,337, JP-A No. 52-152225, etc., and subiroindanes are disclosed in U.S. Pat. No. 4,360.
No. 589, p-alkoxyphenols are disclosed in U.S. Patent No. 2,735,765, British Patent No. 2,066,
No. 975, JP-A-59-10539, JP-A-57-
No. 19765, etc., and hindered phenols are disclosed in U.S. Patent No. 3, TO0. No. 455, JP-A-52-7222
No. 4, U.S. Patent No. 4,228, 235, Special Publication No. 1972
Gallic acid derivatives, methylene dioxybenzene, and aminophenols are disclosed in U.S. Pat. No. 3,457,079 and U.S. Pat. No. 4,332, respectively.
No. 886, Japanese Patent Publication No. 56-21144, etc., and hindered amines are disclosed in U.S. Pat. No. 3,336. No. 135, same No. 4. 268,593, British Patent No. 1. 326
．． No. 889, same No. 1. 354, 313, same No. 1
, 410, 846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 58-114036, Japanese Patent Publication No. 59-53846,
No. 59-78344, etc., and metal complexes are disclosed in U.S. Pat. Nos. 4,050,938 and 4,241,155.
No. 2,027,731 (No. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is better to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it. Effective. As ultraviolet absorbers, penzotriazole compounds substituted with aryl groups (eg, U.S. Pat. No. 3,533.
794), 4-thiazolidone compound (
For example, U.S. Pat. No. 3,314,794;
352. 681), penzophenone compounds (for example, those described in JP-A-46-2784),
Cinnamate ester compounds (e.g. U.S. Pat. No. 3,70
5.805, same No. 3, 707. No. 395), butadiene compounds (U.S. Pat. No. 4,045,
229), or benzoxide compounds (for example, U.S. Pat. Nos. 3,406.070, 3,677,672 and 4,271,307).
(described in No. 1) may be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler), an ultraviolet absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers. Among these, penzotriazole compounds substituted with the aforementioned aryl group are preferred. In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a virazoloazole coupler. That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent the generation of stains and other side effects due to the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler. A preferred compound (F) has a second-order reaction rate constant kt (in trioctyl phosphate at 80°C) with p-anisidine of l, Qj! /mol ・sec ~
It is a compound that reacts in the range of I X10-51 /mol·sec. Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545. When k is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented. A more preferable compound (F) can be represented by the following general formula (FI) or (Fn). General formula (FI) Rl-(A). -X General formula (Fl1> R2-C=Y1B In the formula, R,, R2 each represents an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or O. A is aromatic Represents a group that reacts with a group amine developer to form a chemical bond, X represents a group that reacts with an aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a hetero Represents a ring group, acyl group, or sulfonyl group,
Y represents a group that promotes addition of an aromatic amine developing agent to the compound of general formula (Fn). Here is the R song
SY and 12 or B may be bonded to each other to form a cyclic structure. Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction. For specific examples of compounds represented by general formulas (FI) and (FII), see JP-A-63-158545 and JP-A-6221.
13338, European Patent Publication No. 298321, European Patent Publication No. 277
Those described in specifications such as No. 589 are preferred. On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inactive and colorless compound is the following general formula (Gl ). General formula (GI) R-Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (Gl), Z is Pearson's nucleophile "CII.I
Value (R.G. Paarson, at al.,
J. ＾0. Chem. Sac. , 90, 319 (
1968)) is preferably 5 or more, or a group derived therefrom. For specific examples of the compound represented by the general formula (Gl), see European Patent Publication No. 2.55722 and JP-A-62-
No. 143048, No. 62-229145, Patent Application No. 1983
Those described in European Patent Publication No. 3-136724, European Patent Publication No. 62-214681, European Patent Publication No. 298321, European Patent Publication No. 277589, etc. are preferred. Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589. The photosensitive material produced using the present invention contains water-soluble dyes or dyes that become water-soluble through photographic processing as filter dyes in the hydrophilic colloid layer or for various purposes such as preventing irradiation and halation. You can. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, xonol dyes, hemioxonol dyes and merocyanine dyes are useful. As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964). As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. More preferred is the use of reflective supports. "Reflective support" refers to a material that enhances reflectivity to make the dye image formed in the silver halide emulsion layer clearer. Such reflective supports include titanium oxide, zinc oxide, etc. , those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as calcium carbonate or calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, Examples include polyamide film, polycarbonate film, polystyrene film, vinyl chloride resin, etc. As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is preferable, and it is also preferable to roughen the metal surface or use metal powder to make it diffusely reflective. The metal may be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface may be a metal plate, metal foil, or thin metal layer obtained by rolling, vapor deposition, plating, or the like. Among these, it is preferable to obtain the metal by vapor-depositing the metal onto another substrate. Preferably, a layer of water-resistant resin, particularly thermoplastic resin, is provided on the metal surface. It is preferable to provide an antistatic layer on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc. These supports can be appropriately selected depending on the purpose of use. As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol. The occupied area ratio (%) of white pigment fine particles per defined unit area is most typically calculated by dividing the observed area into adjacent unit areas of 5 gn x 6 gn and projecting onto that unit area. Occupied area ratio (%) of fine particles (R+)
It can be determined by measuring. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/H of the standard deviation S of R+ to the average value (R) of RI. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation S/π can be found as follows. In the present invention, the coefficient of variation of the occupied area ratio (%) of fine pigment particles is 0.15 or less, particularly 0.15 or less. 12EJ or less is preferable. If it is 0.08 or less, the dispersibility of the particles is substantially
It can be said that it is uniform. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl- 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-methoxyethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose. The color developer may contain PL buffers such as alkali metal carbonates or phosphates, development inhibitors or antifoggants such as bromide salts, iodide salts, penzimidazoles, penzothiazoles or merkabut compounds. Generally, it contains agents such as agents. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, N,
hydrazines such as N-bisulfoxymethylhydrazine, various preservatives such as phenylsemi-rubazide, triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol,
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, auxiliary developing agents such as the competing coupler 1-phenyl-3-virazolidone, tackifiers, aminopolycarboxylic acids, amino polyphosphonic acid, alkylphosphonic acid,
Various chelating agents such as phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,
N,N-}rimethylenephosphonic acid, ethylenediamine-N,N. Representative examples include N'N'-tetramethylenephosphonic acid, ethylene diamine di(0-hydroxyphenylacetic acid), and salts thereof. Further, when performing reversal processing, color development is usually performed after black and white development and reversal processing. This black and white developer may contain known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-virazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol, alone or Can be used in combination. The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than one. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is, the aperture ratio - contact area of the treatment liquid and air (cm')/capacity of the treatment liquid (cm'') The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.1. 05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, there is also a method described in Japanese Patent Application No. Method using the described movable lid, JP-A-6-3-2-1-6-050
Examples include the slit development treatment method described in No. It is preferable to reduce the aperture ratio not only in both color development and black-and-white development, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Depending on the purpose, treatment may be carried out in two continuous bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III) is used. Typical bleaching agents include organic complex salts of iron (I[ Aminobocarboxylic acids or citric acid, tartaric acid,
Complex salts such as malic acid can be used. Among these, aminobolycarboxylic acid iron (I[[) complex salts including ethylenediaminetetraacetic acid iron (I[[) complex salt] are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Additionally, aminoboricarboxylic acid iron (I[[) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminoboricarboxylic acid iron (I) complex salts is usually 4.0 to 8.0, but in order to speed up processing, the pH is lowered. You can also do that. A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, West German Pat.
No., Research Disclosure Nα17, 129
Compounds having a merkabut group or a disulfide bond described in No. (July 1978), etc.; JP-A-140-1989
Thiazolidine derivatives described in U.S. Patent No. 129; U.S. Pat.
Thiourea derivatives described in No. 706, 561; iodide salts described in JP-A-58-16235; West German Patent No. 2,
748. Polyoxyethylene compounds described in Japanese Patent Publication No. 430, polyamine compounds described in Japanese Patent Publication No. 45-8836, bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as disclosed in U.S. Pat. No. 3,893.
, No. 858, West German Patent No. 1. No. 290, 812,
Compounds described in JP-A-53-95630 are preferred. Additionally, U.S. Patent No. 4. Also preferred are the compounds described in No. 552,834. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography. Examples of fixatives include thiosulfates, thiocyanates, thioether compounds, ureas, and a large amount of iodide salts, but thiosulfates are commonly used, especially ammonium sulfates. is the most widely used. Preservatives for bleach-fix solutions include sulfites, bisulfites, and p-
}Sulfinic acids such as luenesulfinic acid or carbonyl bisulfite adducts are preferred. The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment. The amount of washing water in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the washing water temperature, the number of washing tanks (number of roles), the replenishment method such as countercurrent or forward flow, and various other conditions. can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnalof theSociety of Mot
ion Picture and Talevisio
n Bngineers Vol. 64, p. 248 ~2
53 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8542, and other benzodiazepines, IJ azoles, etc., are published by Hiroshi Horiguchi [Chemistry of Antibacterial and Antifungal]. J (1986) Sankyo Publishing, edited by Sanitation Technology Association [Microbial sterilization, sterilization, and anti-hui technology J (1982)
“Encyclopedia of Antibacterial and Antifungal Agents” edited by the Society of Industrial Engineers and the Japan Society of Antibacterial and Antifungal Research (
It is also possible to use the fungicides described in (1986). The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used. Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. . It is also possible to add various botanical agents and antifungal agents to this stabilizing bath. The bar flow liquid associated with water washing and/or stabilizing liquid replenishment can also be reused in other processes such as the desilvering process. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,
Indoaniline compounds described in No. 597, No. 3, 3
42, No. 599, Research Disclosure 14
, No. 850 and No. 15,159, aldol compounds described in No. 13,924, complexes described in U.S. Pat. Examples include urethane compounds. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
A virazolidone compound may also be incorporated therein. Typical compounds are described in JP-A Nos. 56-64339, 57-144547, and 58-115438. Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. In addition, West German Patent No. 2. 226,
770 or U.S. Pat. No. 3,674,499 using cobalt or hydrogen peroxide intensification. / / / / / 100 (Examples) Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto. Example 1 Synthesis of Exemplified Compound (1) Exemplified Compound (1) was synthesized by the following route. til1 (50) (Synthesis of intermediate step product (5o)) 7.4 g of 3-nitropenzonitrile and acetonitrile 1
0.5 mJ2 was dissolved in 30 mJ2 of anhydrous tetrahydrofuran, and 5.6 g of potassium t-butoxide was added little by little at room temperature. After the reaction solution turned dark brown, it was heated for 6 hours. After the reaction, 101 ml of ethyl acetate was added at 100 m°C and 100 mJ2 of water, and then aqueous hydrochloric acid was added, and after neutralization, the mixture was washed with water three times. After drying the ethyl acetate layer over magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 9.45 g of intermediate stage product (50). (Synthesis of Exemplary Compound (1)) 2.4 g of intermediate step product (50) and 1.2 g of malononitrile were dissolved in 10 mβ of ethanol and heated under reflux for 3 hours. After the reaction, hydrochloric acid water was added and the precipitated crystals were filtered off to obtain 3.2 g of intermediate stage product (51). The obtained (51) was reduced with iron by a conventional method, and then (52)
) to obtain the target exemplary compound (1). Table A shows the elemental analysis values of Exemplary Compound (1). Table A 102 Example 2 Synthesis of Exemplified Compound (32) Exemplified Compound (32) was synthesized by the following route. (60) (6l) (62) (62) + NCCH2CN
(32) (Synthesis of intermediate product (62)) 72.0 g of dioctylamine, 40.0 g of triethylamine.
4 g was dissolved in 300 ml of tetrahydrofuran, the reaction temperature was maintained at 10°C to 15°C, and p10 cocyanobenzoyl chloride (60) was added little by little. After the reaction, 300 ml of ethyl acetate was added and washed with water. After drying, 96.5 g of intermediate product (61) was obtained by distilling off ethyl acetate. Further, 95.7 g of (61) dissolved in 120 mI2 of acetonitrile was added dropwise to a solution of 20.8 g of 60% sodium hydroxide in 450 mβ of tetrahydrofuran under reflux. After the reaction, the mixture was neutralized with hydrochloric acid and extracted with ethyl acetate and water. After drying the ethyl acetate layer, the intermediate product (62) was removed by distillation.
06.3g was obtained. (Synthesis of Exemplified Compound (32)) Compound (62), 106.3 g and arononitrile 19.
8 g of the solution was dissolved in ethanol at 200 m°C and heated under reflux for 5 hours. After the reaction, ethanol was distilled off and 20% of ethyl acetate was added to the residue.
0 mβ and 200 mρ of water were added for extraction. After drying the ethyl acetate layer, the ethyl acetate layer was distilled off, and the residue was separated by column chromatography to obtain the desired exemplary compound (32) at 110%.
I got 4g. Melting point: 189-190°C0 10.2 Example 3 Synthesis of Exemplified Compound (38) Exemplified Compound (38) was synthesized by the following route. were synthesized to produce compounds (70), 21.6 and (71). 26.9 g was dissolved in 300 mj2 of ethanol, stirred at room temperature for 2 hours, and then stirred at 40°C to 50°C for 2 hours. After the reaction,
500 mβ of ethyl acetate was added, and the mixture was thoroughly washed with water. After drying the ethyl acetate layer, it was distilled off under reduced pressure to obtain the desired exemplary compound (3).
8) was obtained in an amount of 26.7 g. The melting point was 160°C. Exemplary compounds (2) to (4), (
6) to (10) could be synthesized. In addition, for example compounds (21) and (23), etc., J
our own f. Prabt. Band 316
, Haft 4, 105 684 (1974), JP-A-50-77366 and JP-A-50-77365, and Aust. J. Chem.
26, 2567 (1973) and the like. Example 4 A multilayer color photosensitive material having the layer structure shown below was prepared on a subbed cellulose triacetate support. The coating solution was prepared as follows. (Preparation of emulsion layer coating solution) Cyan coupler 1. 85 mmof and ethyl acetate J
Equivalent weights of Re1Qcc and tricresyl phosphate (solvent) were added to and dissolved in the cyan coupler, and this solution was emulsified and dispersed in 38 g of a 14% aqueous gelatin solution containing 3 cc of a 10% dodecylbenzene snolephonic acid solution. on the other hand,
A sulfur-sensitized silver chlorobromide emulsion (silver bromide 70.0 mol%) was prepared, and this and the pre-emulsion were mixed and dissolved to prepare a coating solution with the composition shown below. I did it. (Layer composition) The composition of each layer used in this experiment is shown below (the numbers indicate the amount of coating per hole). 106 Support Cellulose triacetate support

[Emulsion layer]

Silver chlorobromide emulsion (described above) 8. 0 mmo
! 2 couplers 1. 0+n
mo, l! Solvent (same amount as coupler coating weight) Gelatin 5.2g

[Preservation layer]

Gelatin 1.3g Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)
0.17g liquid paraffin 0
．． 03g The above photosensitive material was subjected to imagewise exposure and then processed in the following processing steps. Processing process Temperature Time Color development 33"C 3 minutes bleach fixing 3
Wash at 3°C for 2 minutes Wash at 33°C for 3 minutes The composition of the processing solution is as follows: Color developer Distilled water 80011i {10
7 Henzyl alcohol Diethylene glycol Sodium sulfite Potassium bromide Sodium bicarbonate Potassium sulfate Hydroxylamine sulfate N-ethyl-N-(β methanesulfonamidoethyl) 3-Methyl-4 aminoaniline sulfate Fluorescent brightener (WHITEX4, manufactured by Sumitomo Chemical) ) up to pH Bleach-fix solution Naru water Ammonium thiosulfate (70%) Sodium sulfite 15ml 10ml 1. 7g 0. 6g 0. 7g 31.7g 3. 0g 4. 5g 1.0g 1000ml O, 25 400rd 150d 18g 108 Ethylenediaminetetraacetic acid 55g Iron (I[I
) Ammonium ethylenenoaminetetraacetic acid 5g disodium up to 1000ifpH
Samples 101-110 were prepared using couplers as shown in Table 6.70. Note that the couplers were replaced in equimolar amounts. Table 1: 10! # Table 1 (Continued) (R l) (R 2) 110 After the development process, measure the light absorption of the highest density area, and evaluate the hue based on the maximum absorption wavelength and the magnitude of the secondary absorption given by the following formula. went. Table 2 shows the results of absorption concentration at sub-absorption magnitude=425 nm/absorption concentration at maximum absorption wavelength. As is clear from Table 2, the coupler of the present invention has little side absorption and can be said to be a coupler with excellent color reproducibility. Next, to examine the image fastness, the processed sample was left in the dark at 60°C for 3 months, then left in the dark at 60°C and 70% relative humidity for 45 days, and then exposed to a xenon lamp (95,000 lux). It was irradiated for 150 hours. In all cases, a decrease in density was observed for Samples 101 and 102, but almost no decrease in density was observed for Samples 103 to 111, indicating that the cyan coupler of the present invention is superior in image fastness. Understood. Example 5 A multilayer color photosensitive material having the layer structure shown below was prepared on a subbed cellulose triacetate support. The coating amount was adjusted as follows. (Preparation of emulsion layer coating solution) Cyan coupler 1. 8 5 mmol, 10 cc of ethyl acetate, and tricresyl phosphate (solvent) were added and dissolved in equal weights to the cyan coupler, and this 112 solution was added to 3 cc of 1O% dodecylbenzenesulfonic acid solution.
was emulsified and dispersed in 33 g of a 14% gelatin aqueous solution containing On the other hand, a sulfur-sensitized silver chlorobromide emulsion (containing 0.2 mol% silver bromide locally on the grain surface) was prepared, and this and the emulsion were mixed and dissolved to form the composition shown below. The coating solution was prepared as follows. (Layer composition) The composition of each layer used in this experiment is shown below (the numbers indicate the amount of coating per unit).Gi support laminated on both sides with polyethylene support

[Emulsion layer]

Silver chlorobromide emulsion (described above) 2. O mmo
J! Coupler 0. 5 mm
of solvent (same amount as coupler coating weight) gelatin 5.2g

[Protective layer]

Gelatin! ．． Acrylic modified copolymer of 3g polyvinyl alcohol (degree of modification 17%)
O. 17g113 Liquid paraffin 0.03g The above photosensitive material was subjected to imagewise exposure and then processed in the following processing steps. Processing process Temperature Time Color development 35'C 45 seconds bleach fixing
Rinse at 30-35°C for 45 seconds ■ Rinse at 30-35°C for 20 seconds ■ Rinse at 30-35°C for 20 seconds ■ 20 seconds at 30-35°C The composition of the processing solution is as follows: color developer water 800 d Ethylenediamine N,N,NN-tetramethylenephosphonic acid triethanolamine sodium chloride potassium carbonate N-ethyl-N-(β methanesulfonamidoethyl) 3-methyl-4 aminoanili1. 5g acid salt N,N-bis(carpoxy 5.5gmethyl)hydrazine optical brightener (WHITEX4 1.0g manufactured by Sumitomo Chemical) up to 1000mffpH
10.05 Bleach-fix solution water 400d
Ammonium thiosulfate (70%) 100d Sodium sulfite 17g Ethylenediaminetetraacetic acid 55g Iron (I[l) ammonium Ethylenediaminetetraacetic acid 5g Disodium Ammonium bromide 40gup t
o 1000dpH
6.70 Rinse with ion-exchange water (calcium and magnesium are each 115 and 3 ppm) Samples 201-2 using couplers as shown in Table 2
11 was created. Note that the couplers were replaced in equimolar amounts. Table 3 (*) When the color reproducibility and image fastness of the sample after the same treatment as in Example 4 were examined in exactly the same manner as in Example 4, the coupler of the present invention was superior to the comparative coupler. 116 Example 6 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. First layer coating solution preparation Yellow coupler (1 mix x Y) 19.1g, color image stabilizer (Cpd-1) C 4g and color image stabilizer (Cpd
-7) 0.7g of ethyl acetate 27.2CC and solvent (
Solv-1) 8.2g was added and dissolved, and this solution was
The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of sodium dodecylhenzenesulfonate. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.88 μm
The coefficient of variation of the particle size distribution of a 3:7 mixture (silver molar ratio) of 0.70 μm and 0.70 μm is 0.08 and 0.10,
Each emulsion contains 0.2 mol% silver bromide locally on the grain surface)
Add the blue-sensitive sensitizing dyes shown below at 2.0 x 10-' mol per mol of silver to the large-size emulsion, respectively.
For small size emulsions, 2.5X10-
A sample was prepared in which sulfur sensitization was carried out after adding 'mol. A first coating solution was prepared by mixing and dissolving the above-mentioned emulsified dispersion and this milk powder to have the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-okyne-3.5-dichloroS-triazine sodium salt was used. The following spectral sensitizing dyes were used in each layer. Blue-sensitive emulsion layer SO3 (El SOJ-N (CJs), (CHz) a (CL)1 SO30 SO3Nll (Czlls) 3 113 (per mole of halide tl, 2.OX10-' each for large size emulsions) moles, and 2.5X10-' moles each for small size emulsions) green-sensitive emulsion layer (per mole of silver halide, 4.OXIO-' moles for large size emulsions, and 4.OXIO-' moles for small size emulsions) is 5.6
X10-'mol) and? O■e SO3H-N(Cz}Is)s (per mole of silver halide, 7.OXIO-' mole for large size emulsions and 1.OX10-' mole for small size emulsions) Red-sensitive emulsion layer? Per mole of halogenated tl, 0.9X10-' mole for large size emulsions and 1. IXIO-' mol) To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10' 3 mol per mol of silver halide. Also, blue-sensitive milk IPI layer, green-sensitive emulsion layer, red-sensitive emulsion 12
0 layer, 1-(5-methylureidophenyl)5-mercaptotetrazole was added at 8.5X10-' mol, 7.7XIO-' mol, and 2 mol per mol of silver halide, respectively.
．． 5 x 10-' moles were added. The following dyes were added to the emulsion layer to prevent irradiation. SOJa SOsNa and? Layer composition) The composition of each layer is shown below. The number is the coating amount (g/+ff)
represents. The silver halide emulsion represents the coated amount in terms of silver. Support polyethylene laminated non-uniform paper [white pigment (T i O ■) on the polyethylene on the first layer side
and a bluish dye (ulmarine)] First layer (blue color layer) Said silver chlorobromide emulsion 0.30 gelatin
1.86 yellow coupler (E
xY) 0.82 color image stabilizer (Cpd-1)
0.19? Container (Solv-1)
0. 35 color image stabilizer (Cpd-7
) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solv.
-1) 0. 16 Solvent (Solv-4) 0.08122 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1=3 mixed proboscis of one with an average particle size of 0.55 μm and one with an average grain size of 0.39 μm) Ag molar ratio).The coefficient of variation of particle size distribution is 0.10 and 0.0.
8.Each emulsion contains 8g Bro. 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-
2) 0.03 color image stabilizer (Cpd-3)
0.15 Color image stabilizer (Cpd-4) 0
．． 02 color image stabilization (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet light
Agent (UV-1) 0.47 Color mixture prevention agent (Cpd
-5) 0.05 solvent (Solv-5)
0. 24 Fifth layer (red light layer) 123 Silver chlorobromide emulsion (cubic, average grain size 0.58p
A l:4 mixture of A
g molar ratio). The coefficient of variation of particle size distribution is 0.09 and 0.
．． Each 1L emulsion contained 0.6 mol % of AgBr locally in 6 parts of the grain surface) 0 23 Gelatin 1.34 Cyan coupler (Soane coupler) o. 6 3mmoN color image stability law (Cpd-6) 0.17 color image stability law (C
pd-7) 0.40 color image stabilizer (Cpd-8
) 0.04 Solvent (Solv-6)
0. +5 6th layer (ultraviolet absorption layer) Gelatin 0.53 ultraviolet absorber (LIV-1) 0.16 color mixture prevention agent (Cp
d-5) ' 0.02 medium (So 1
v-5) 0. 0
8 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol 12.1 (Degree of modification 17%) 0. I7 Liquid paraffin 0. 03 (E x Y) Yellow coupler C1 C! HS Cll. l: 1 mixture (molar ratio) 125 (ExM) Magenta coupler 126 (Cpd l) Color image stabilizer (Cpd 2) Color image stabilizer (cpd 3) Color image stabilizer 127 CCpd 4) Color image stabilizer ( Cpd 5) Color mixture inhibitor 0■ 128 (Cpd 6) Color image stabilizer CI (Cpd 7) Color image stabilizer - ECH. -Clh- CONHCJq (n) Average molecular weight 60,000 (Cpd 8) Color image stabilizer 0H 0H (Cpd 9) Color image stabilizer 130 (UV l) 4:2:4 mixture (weight ratio) of ultraviolet absorbers ( SOIV-1) Solvent 1] (Solv 2 )? Container (Solv 4) Solvent (Solv 5) Solvent cooc, u, (CHz) e COOCgH+ , 132 (Solv 6) Solvent? First, each sample was subjected to imagewise exposure. The exposed sample was subjected to continuous processing (running test) using a paper processing machine until twice the color development tank capacity was replenished in the next processing step. Processing Work I Arashi-Once Single Plate ■Kokyu゜Llkyu 11 color development 35'C 45 seconds 161d l7m
2 Bleach-fixing 30-35'C 45 seconds 215d
l7 N rinse ■ 30-35°C 20 seconds ■
lOl rinse ■ 30-35°C 20 seconds ■
10ffi rinse■ 30-35°C 20 seconds 35(ld 1(lffi dry 70-8
0°C 60 seconds 133 Ethylenediamine-N,N N,N-tetramethylenephosphonic acid Triethanolamine Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfuric acid Salt N,N-bis(carboxymethyl)hydrazine optical brightener (former TEX 4B Kunobun 800 800 1.5g 8.0g 1.4g 25g 2.0g 12.0g 25g 5.0g 7.0g 5.5g 7.0g Add water 1000d l000
mipH (25°c) 10.05
10.45 liters of water (tank fluid and refill fluid are the same) water
40
0d13l# Ammonium thiosulfate (70χ) 100
d Sodium sulfite 17g Iron ethylenediaminetetraacetate (Iff) Ammonium 55g Disodium ethylenediaminetetraacetate 5g Add water
1000dpH (25°c)
6.0 Kazuo Photo Fan (tank liquid and replenisher are the same) Ion-exchanged water (calcium and magnesium are each 3 ppm or less) Samples 301 to 311 were prepared using the couplers shown in Table 3. Note that the couplers were replaced in equimolar amounts. 135 Table 4 (*) A sample after the same treatment as in Example 4 was examined in the same manner as in Example 4 and Example 5, and it was found that it had superior color reproducibility and image fastness compared to the comparative coupler. Understood. 136 Example 7 On a subbed cellulose triacetate film support,
Sample I+01, which is a multilayer color luminescent material, was prepared by applying layers having the compositions shown below. (Composition of light emitting layer) The numbers corresponding to each component indicate the coating amount expressed in g/%, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, silver halide 1 in the same layer
The coating amount is expressed in moles. (Sample 40l) 1st layer (antihalation layer) Black colloidal silver Silver 0.1B gelatin 1.40 2nd layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0. l8EX-1
0.07EX −
3 0.0213゛7 EX-12 U-1 U-2 U-3 HBS-1 HBS-2 Gelatin 3N (first red-sensitive emulsion layer) Emulsion A Emulsion B Enhancing dye■ Enhancing dye■ Enhancing dye■ EX-2 EX-10 U-1 U-2 U-3 HBS-1 Gelatin 0.002 0.06 0.08 0.10 0.10 0.02 1,04 Silver 0.25 Silver 0.25 6. 9 X 10-' 1.8X10-s 3. IX10-' 0.335 0.020 0.07 0.05 0.07 0.060 0.87 138 4th NC 2nd red-sensitive emulsion layer) Emulsion G Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ EX- 2 EX-3 EX-10 U-1 U-2 U-3 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion D Sensitizing dye I Sensitizing dye■ Sensitizing dye m Eχ-3 EX-4 EX~ 2 Silver 1.0 5. IX10-' 1.4XIO-5 2.3X10-' 0.400 o. oso O. 015 0.07 0.05 0.07 1.30 Silver 1.60 5.4X10-5 1.4X10-5 2.4X10-' 0.010 0.080 0.097 139 HBS-1 HBS-2 Gelatin No. 6th layer (intermediate layer) EX-5 HBS-1 Gelatin 7th layer (first green-sensitive emulsion layer) Emulsion A Emulsion B Enhancing dye ■ Sensitizing dye ■ Intensifying dye ■ EX-6 EX-1 EX-7 EX- 8 HBS-1 HBS-3 Gelatin 0.22 0 10 1.63 0.040 0.020 0.80 Silver o. is silver 0.15 3. O x 10-5 1. OX10-'3.8X10-' 0.260 0.021 0.030 0.025 0. 100 0.010 0.63 1・10 8th Ji (second green emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 EX-7 HBS-1 HBS-3 Gelatin 9th layer (3rd green emulsion N) Emulsion E Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-13 EX-11 EX-1 HBS-1 Silver 0.45 2. IX10-5 7. OX10"'2.6XIO-' 0.094 0.01B 0.026 0.160 0.008 0.50 Silver 1.2 3.5X10-5 8.OX10-'3.OX10-' 0.015 0. 100 0.025 0.25 141 HBS-2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver EX-5 HBS-1 Gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Enhanced dye ■ Eχ-9 EX-8 HBS-1 Gelatin 12th layer (second blue emulsion N) Emulsion G Sensitizing dye■ EX-9 0.10 1.54 0.05 0.08 0.03 0.95 Silver 0 .08 Silver 0.07 Silver 0.07 3.5X10-' 0.721 0.042 0.28 1.10 0.45 2.IXlO-' 0 154 142 EX-10 HBS-1 Gelatin 13th layer (Third blue-sensitive emulsion layer) Emulsion H Enhanced dye ■ EX-9 H B S'- 1 Gelatin 14th layer (first protective layer) Emulsion I U-4 U-5 HBS-1 Gelatin 15th layer (second Protective layer) Polymethyl acrylate particles (diameter approximately 1.5 m) S-1 Gelatin 0.007 0.05 0.78 Silver 0.77 2.2X10-' 0.20 0.07 0.69 0.20 0.l1 0.17 0.05 1.00 0.54 0.20 1.20 143 In addition to the above ingredients, each layer contains gelatin hardening agent H-1, gelatin preservative/mold preservative 1,2-penz Isothiazoline-3
-one, 2-phenoxyethanol, phenethyl alcohol, and a surfactant were added. 144 145 EX ■ CI EX 2 EX-3 0H 146 EX 4 EX 5 EX 6 C6H+:+(n) 14゛z EX 7 EX-8 EX 9 CI 148 EX 10 EX l2 CI 14! j EX-1 3 U 1 U 2 U 3 CI 1 "》 (U 4 151 Sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ 152 Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ 153 Sensitizing dye ■ S J CHff ;f トI-1 ?);.-=70li- So■-CI+2-CONF!
-CIL. CI{2-C}I SO2 CL C
ONH Clh154 After the color photographic light-sensitive material 401 as described above was exposed, it was processed using an automatic processor in the manner described below (until the cumulative amount of replenishment of the developer became three times the capacity of the mother liquor tank). Table-4 Processing Method Step Processing Time Processing Temperature Replenishment If'ink Capacity Color Development 3 minutes 15 seconds 38°C 33m
ll 201 bleaching 6 minutes 30 seconds 38°C 25+11fi 40N water washing 2 minutes 10 seconds 24°C 1200ml! 20N fixation 4 minutes 20 seconds 38°C 25m3
01 water wash C1 water 1 minute 05 seconds 24℃
(2) To #6<1) a 10 j! Self-flow piping method. Washing with water (2) 1 minute 00 seconds 24°C Constant 1 minute 05 seconds 38°C Drying 4 minutes 20 seconds 55°C Replenishment amount is 35 per 1 m length of solid width Next, write down the composition of the treatment solution. (Color developing solution) 1200 dlON Ammonium 25dlOf Dry mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 j55 1-Hydroquinethylidene 1.1 Monodiphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Iodine potassium hydroxylamine sulfate 4-[N-ethyl-N-β-hydroxyethylamino] Add 2-methylaniline sulfate to pH (bleach solution) Ethylenediaminetetraacetic acid ferric sodium trihydrate Ethylenediaminetetraacetic acid di Na-Lium Chloroammonium Bromide 3.0 3.2 4.0 30.0 37.0 1,4 1.5■ 2.4 4.5 2,8 4.4 5,5 0.7 1. 0! 10.05 Mother liquor (g) 100.0 lO,0 140.0 1. OP 10. 10 Replenisher (g) 120.0 11.0 160.0 15G Ammonium nitrate Aqueous ammonia (27χ) Add water and PH (Fixer) Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Sodium bisulfite Ammonium thiosulfate aqueous solution (70χ) Water PH (stabilizing liquid) Volmarin (37%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 30.0 6.5d l. OIV. 6,0 35,0 4,Od l. O Il 5.7 Mother liquor (g) Replenishment solution (g) 0.5 0.7 7.0 8.0 5.0 5.5 170.0m 200.0af 1. O! 6.7 1.0! 6.6 Mother liquor (g) Replenisher (g) 2, Od 3.0 relative 0.3 0.45 15;″ Ethylenediaminetetraacetic acid dibasic 0.05 0.08
Add thorium salt water 1. ON 1. Oj2
pH 5.0-8.0 5.
When the cyan coupler in the red-sensitive layer of 0-8.0 sample 401 was replaced with the exemplified compound (1) of the present invention and the same treatment was performed, good photographic properties were obtained that were improved as in Examples 4 to 7. was gotten. (Reference Example) In order to investigate the basic hue of the cyan dye obtained from the coupler of the present invention, a compound obtained by a similar synthesis method (
46) (melting point 198-199°C) shown below (
The dye No. 53) was synthesized and its absorption spectrum and molecular extinction coefficient were measured. 158 Compound (53) was synthesized according to the scheme below. 400 mg of (46) and 590 mg of (54) were dissolved in 10 mj2 of ethanol, and 1 mj2 of acetic anhydride was added dropwise. After stirring for 1 hour at room temperature, 50 mβ of each of ethyl acetate and water were added, and the mixture was washed with water three times. After drying ethyl acetate over magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain compound (53). Table 5 shows the molecular absorption 159 coefficient of (53) in ethyl acetate, and FIG. 1 shows its absorption spectrum. 1-vhoII. Unit: 160 As is clear from Table 5 and Figure 1, compared to conventionally known phenols and naphthols, the coupler of the present invention provides a dye with a larger single molecule extinction coefficient and less side absorption. be able to. (Effects of the Invention) When the compound of the present invention is used, a color image with little side absorption, good color reproducibility, and excellent fastness can be obtained. In addition, as is clear from the synthesis examples, it is possible to obtain 4
It can be synthesized in a short number of steps called stenobu, and it can be said to be advantageous in terms of cost.

[Brief explanation of drawings]

FIG. 1 is an absorption spectrum diagram of a dye, where the vertical axis represents absorbance and the horizontal axis represents absorption wavelength (nm). is an absorption spectrum of a dye obtained by subjecting the compound of the present invention to a campling reaction with an oxidized form of a color developing agent, and a compound of the dye obtained by carrying out a campling reaction with an oxidized form of a color developing agent; - The line is the absorption spectrum of a dye derived from a conventional coupler. 161

Claims (1)

[Claims] (1) β, γ-unsaturated nitriles represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, W is a hydrogen atom or a leaving group that leaves when this compound undergoes a coupling reaction with an oxidized form of an aromatic primary amine derivative When V represents a nitrogen atom, R_2 is a substituent, and V is a nitrogen atom or ▲a mathematical formula, chemical formula, table, etc. There are tables, etc.▼
When R_2 and R_3 represent an electron-withdrawing substituent, the other represents a substituent. However, when R_2 or R_3 represents an aliphatic group or an aromatic group, the other is not an acyl group. Moreover, R_1 and R_2 may be mutually connected to form a ring. ) (2) β, γ represented by the following general formula (II)
-Unsaturated nitriles. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, W is a hydrogen atom or a leaving group that leaves when this compound undergoes a coupling reaction with an oxidized form of an aromatic primary amine derivative.) , X, Y and Z are each a nitrogen atom, a methine group, or a methine group having an electron-withdrawing group, and at least one of X, Y and Z represents a methine group having an electron-withdrawing group, n represents 1 or 2, and Q represents a nonmetallic atomic group necessary to form a heterocycle or aromatic ring together with a ▲numeric formula, chemical formula, table, etc.) (3) The following β, γ-unsaturated nitriles represented by general formula (III). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, W is a hydrogen atom or a leaving group that leaves when this compound undergoes a coupling reaction with an oxidized form of an aromatic primary amine derivative.) , at least one of R_4 and R_5 represents an electron-withdrawing substituent, and the other is
Represents a substituent. However, R_4 and R_5 do not form a ring. ) (4) General formula ( I
) A photographic color coupler consisting of a compound represented by (5) A silver halide color photographic material containing a compound represented by the general formula (I) according to claim (1). (6) A color image forming method comprising developing a silver halide color photographic light-sensitive material with a color developer containing an aromatic primary amine derivative in the presence of the coupler according to claim (4).