JPH01205162A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To retard generation of residual color stain by incorporating a specified compd. into a photosensitive material and regulating a processing time to a specified time without incorporating benzyl alcohol into a color developing soln. CONSTITUTION:A compd. expressed by formula I or II is incorporated into a silver halide color photographic sensitive material, and a processing time for color development and total processing time for color development plus bleach-fix time, and washing time with water, are regulated respectively to <=25sec and <=2min, without incorporating practically benzyl alcohol into the color developing soln. In formula I, each R1 and R2 is -CN,-CFR5R6, etc., each R5 and R6 is H, F, 1-4C fluorinated alkyl; each R3 and R4 is H, aliphatic group, cycloaliphatic group, etc.; each L1-L5 is a methine group. In formula II, each Z21 and Z22 is an atom. group necessary for forming an imidazole or oxazole nucleus which may have a substituent; each R21 and R22 is an alkyl or alkenyl group which may be substituted; X21<-> is an anion. Thus, generation of residual color stain is retarded.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a method for processing a silver halide color photographic material, and more specifically, it relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, a method for processing a silver halide color photographic light-sensitive material. This invention relates to a method for processing silver color photographic materials. [Background of the Invention] In general, in order to obtain a color image by processing an imagewise exposed light-sensitive material, the generated metallic silver is desilvered after the color development process, and then washed with water, stabilized or stabilized as an alternative to water washing, etc. A processing step is provided. However, are photosensitive materials subjected to running processing in automatic developing machines installed in each laboratory?
As part of improving services for users, it is required that images be processed and returned to the user on the same day they are received, and in recent years, it has even been requested that the images be returned within a few hours of acceptance. The development of rapid processing technology is becoming increasingly urgent. As a result, the processing time, process, and temperature of the current major color vapor photosensitive materials have reached the following levels. That is, for example, the development time for color photographic paper is 8.5 minutes,
The processing temperature was 33°C, and the processing time consisted of 3 steps: color development for 3.5 minutes, bleach-fixing for 1.5 minutes, and washing with water for 3.5 minutes.
The system technology involved is U.S. Patent: I, 582,
No. 322 and OLS 2,160,87
It is disclosed in No. 2, etc. In addition, there are examples of speeding up bleaching and fixing by performing bleaching and fixing in one bath. For example, U.S. Pat. It is disclosed that processing exclusively for color photographic paper is possible. Unicolor has developed a similar rapid development process for color negatives and photographic paper (2).
9.5°C, 7-1] minutes, e.g.
Journal of Photography)”,
(January 30, 1970 issue, No. 1] p. 4). However, as the color development processing time is shortened, the occurrence of residual color stains, which are thought to be related to water-soluble dyes and sensitizing dyes, increases, and this tendency is particularly noticeable when benzyl alcohol is present. It turns out that there is something. That is, conventional color developing solutions generally contain benzyl alcohol for the purpose of promoting development. However, if bleach-fixing is performed immediately after processing with a color developing solution containing benzyl alcohol, the benzyl alcohol will adhere to the photosensitive material and be carried into the bleach-fix solution and accumulate, resulting in deterioration of the bleach-fixing ability. In particular, it was found that not only the desilvering properties were deteriorated, but also the occurrence of residual color stain was significant. Although it was thought that rapid processing would reduce the storage stability of dye images, it was surprisingly found that it has a great effect on the dark fading of dye images, especially the dark fading of magenta and cyan. [Object of the Invention] Therefore, the object of the present invention is to provide a bleach-fixing solution with less deterioration in desilvering properties, to improve photographic properties, particularly to suppress the occurrence of residual color stain, and to improve dye images obtained by processing. An object of the present invention is to provide a method for processing a silver halide color photographic material that has excellent storage stability. [Structure of the Invention] The processing method of the present invention that achieves the above object comprises the steps of color development processing, bleach-fixing processing, and water washing processing of a silver halide color photographic material having at least one silver halide emulsion layer. , the silver halide color photographic light-sensitive material contains at least one compound represented by the following general formula [A-1] or [BS-1], and the color developer used in the color development process substantially contains does not contain benzyl alcohol, the color development processing time is 25 seconds or less, and the total processing time of the color development processing time, bleach-fixing processing time, and water washing processing time is within 2 minutes. . General formula [A-1] In the formula, R and R2 are respectively -CN, -CFR,
R. -CORt, -GOOR? or -CONHRs,
R3 and R6 each represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms, and Ry
teeth. m R3 and R4 represent an alkyl group or an aryl group,
LJ, Lz, L3. each represents a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic group, or a heterocyclic group. L4 and L5
each represents a methine group, 1] and n each represent 0 or 1. General formula [BS-1] (X*+)f! t+ In the formula, 221 and Z22 each represent an imidazole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, a lysine nucleus, a benzoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a benzoimidazole nucleus, which may have a substituent. , represents an atomic group necessary to form a naphthoxazole nucleus, a 7-thiazole nucleus, a naphthoselenazole nucleus, a naphthoimidazole nucleus, or a quinoline nucleus. R21 and R22 each represent an alkyl group or an alkenyl group that may have a substituent. X2? represents an anion and I represents 0 or l. In a preferred embodiment of the present invention, (1) the amount of washing water in the washing process is 0.0% of the amount of pre-bath brought in per unit area of the photosensitive material.
(1) The silver halide emulsion contains at least gO mol% of silver chloride; (2) The color developing solution for color development processing is a hydroxylamine rust conductor represented by the general formula [I] below. Containing. [Operation of the invention] A silver halide color photographic light-sensitive material in which a silver halide emulsion containing silver chloride, particularly a light-sensitive silver halide emulsion, contains 90 mol% or more of silver chloride (hereinafter also referred to as a silver chloride light-sensitive material). can be developed more quickly than conventional color photographic materials made of silver halide emulsions containing silver bromide or silver iodide, such as silver chlorobromide, silver chloroiodobromide, or silver iodobromide emulsions. Since bromide ions and iodide ions, which inhibit the development reaction, are not accumulated in the color developing solution, it is extremely useful for rapid processing. Although the compounds represented by the general formula [A-1] or [BS-1] are known, it was a surprising discovery that the effect of preventing residual color staining was observed in relation to the treatment time. Moreover, in the case of an emulsion containing silver chloride with a silver halide content of 90 mol% or more, even if a color developing solution containing no benzyl alcohol is used, the dye image, which is comparable to that obtained when benzyl alcohol is added, is rather shortened. It has been found that it can be obtained in a short amount of time and can effectively suppress the occurrence of residual color stain. Furthermore, as a result of continued studies, the present inventors found that the silver halide emulsion has a silver chloride content of 90 mol% or more, particularly 95 mol% or more, and that the color development processing time is 25 seconds or less, especially 3 seconds to 20 seconds.
In addition, the effect of the present invention is significantly enhanced when all processing steps up to water washing are processed within a total of 2 minutes, especially from 20 seconds to 1]0 seconds, resulting in extremely high speed processing and residual color staining. The inventors have discovered the surprising fact that this method can suppress the oxidation of pigments and provide stability in dye storage. Furthermore, the present inventors have found that when the color developing solution does not substantially contain hydroxylamine but contains a hydroxylamine derivative, it is possible to achieve a high degree of optimization of the coupling rate and the development rate of silver halide. Furthermore, it has been discovered that dye storage stability can be improved by shortening the processing time, and the object of the present invention has been successfully achieved. In the present invention, the photosensitive material to be processed has the general formula [A-1] or [BS
-1]; on the other hand, the color developer does not substantially contain pencil alcohol, the color development processing time is 25 seconds or less, and It is necessary to simultaneously satisfy the requirement that the total processing time is 2 minutes or less, and even if any of the requirements is missing, the object of the present invention will not be achieved, especially if the processing time is outside the scope of the present invention. [Specific Structure of the Invention] First, the compound represented by the general formula [A-1] will be described in detail. In general formula [A-1], R8 and R2 are respectively -〇M, -CFR5R6, -(:OR?, -GOOR
? or -CONHRs, -CFRSR, and -C
The fluorinated alkyl group having 1 to 4 carbon atoms in R5 and H6 shown in ONHRs is 1, for example, difluoromethyl group, trifluoromethyl group, 1,1,2.2-
Tetra-fluoroethyl group, 1,1,2,2,3,3,
4.4-octafluorobutyl group, 1,1,2,2,3
．． Examples include 3-hexafluoropropyl group. Further, R7 of one CORy represented by R1 and R2 represents an alkyl group or an aryl group, and the alkyl group and aryl group include those having a substituent. R and R4 each represent a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic group, or a heterocyclic group, and among these, aliphatic groups include alkyl groups and alkenyl groups, and alicyclic groups include Examples include cycloalkyl groups. Furthermore, typical aromatic groups include aryl groups, such as phenyl groups and naphthyl groups. Furthermore, as the heterocyclic group, for example,
Typical examples include benzthiazolyl and benzoxacylyl groups. The aliphatic group, alicyclic group, aromatic group and heterocyclic group represented by R3 and R4 further include those having a substituent. L, 1. Lm, 1]. The methine groups represented by L4 and R include those substituted with an alkyl group or an aryl group having 1 to 4 carbon atoms. Of the above R8 and R2, -CN group, -Ch
group, -CONH2 group and -COR, group, and R? Preferred is an alkyl group. Among R3 and R4, preferred are aromatic groups, particularly preferred are 4-
These are a sulfophenyl group, a 2,5-di-sulfophenyl group, and salts thereof. Among the dyes of the present invention, those having at least one water-soluble group (eg, sulfo group, carboxyl group, and salts thereof) in the molecule are preferred. Typical examples of the dye of the present invention represented by the general formula [A-1] are shown below, but the dye of the present invention is not limited thereto. In addition to dye dye 1 exemplified above, dyes that can be effectively used in the present invention include example No. 1, (2), (3) and (7)
. (9), (15), (16), (18), (1
9), (21), (22). (24), (25), (27), (:I3),
C34), (35), (40). (1!2), (43), (44), (45),
(46), (47), (48). (49), (50), (51), (52), (
53), (54), (55). Examples include compounds represented by (58), (59), (60) and (62). The above dye of the present invention can be synthesized by the method described in Japanese Patent Application No. 8796/1983. Next, the compound represented by the general formula [BS-1] will be described in detail. The heterocyclic nucleus represented by the general formula [Bs-I] r, -ite, 221 and L2 includes imidazole nucleus, thiazole nucleus, selenazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus. A benzothiazole nucleus is preferable, a benzothiazole nucleus and a benzoselenazole nucleus are more preferable, and a benzothiazole nucleus is most preferable. The heterocyclic nucleus represented by Z2I and 222 may have a substituent, and preferred substituents include a halogen atom, a hydroxyl group, an aryl group, an alkyl group, an alkoxy group, and the like. Among the halogen atoms, a chlorine atom is particularly preferred, and as an aryl group, a phenyl group is preferred. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like, with a methyl group being preferred. As an alkoxy group, the number of carbon atoms is 1 or more
The alkoxy group of No. 4 is preferable, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and among them, a methoxy group is preferable. The alkyl group represented by R21 and R2□ is preferably a straight chain or branched alkyl group having 1 to 6 carbon atoms,
A methyl group, an ethyl group, a propyl group, an isopropyl group, etc. are preferred. These alkyl groups may be substituted, and preferred substituents include a sulfo group, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, and an alkylsulfonylamino group. The alkyl group represented by L+ and R22 is preferably an alkyl group substituted with a sulfo group or a carboxyl group.The sulfo group, carboxyl group, etc. are cations such as pyridinium ion, triethylammonium ion, or ammonium ion. , may form a salt with an inorganic cation such as sodium ion or potassium ion. When the heterocyclic nucleus represented by Z21 and/or 212 is a fused/non-fused imidazole nucleus, Rt+ or R22
The nitrogen atom to which is not bonded may have a substituent, and a preferable substituent is an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and methyl, ethyl, propyl, isopropyl and the like are preferred. These alkyl groups may be substituted, and preferred substituents include a hydroxyl group, an alkoxycarbonyl group, an alkylsulfonylamino group, and an aryl group. X2? The anion represented by is preferably chloride ion, bromide ion, iodide ion, p-)luenesulfonate ion, etc., and halide ion is preferable. In addition, when forming an inner salt, an anion may not be included, and in that case, sentence 2. represents 0. Specific examples of the sensitizing dye represented by the general formula [BS-I] are shown below, but the present invention is not limited thereto. [13S-1-1] (C1]a)ss03(CIlt)3sOall[BS
-1-2 [BS-1-3] [BS-1-4] [BS-1-5] [BS-1-6 [BS-1-7] [BS-1-8] e [BS -l-9] [BS-1-1o] [13S-1-+1] [BS-1-121 [BS-1~13] [BS-1-14] [BS-1-151 [BS-1- 16] [BS-1-171 [BS-1-18] [BS-1-19]. The above compound is generally known, and is described, for example, in Palmer, "The Soybean and Fist Related Compounder" (Interscience Publishers, New York, 1864). It can be easily synthesized by the following method. The blue-sensitive sensitizing dye used in the present invention preferably has an amount of 5 x 10-5 to 2 x 10 mol per mol of silver halide, more preferably I x 10-4 to 7 x 10
It is used in a range of -4 mol. These sensitizing dyes may be added at any time from the formation of silver halide grains to the time of coating, but it is particularly preferable to add them from the time of completion of silver halide grain formation to the time of coating. These sensitizing dyes may be dispersed in a water-miscible organic solvent without being dissolved, and the dispersion may be added to the silver halide emulsion, or in water or methanol. It may be added to the silver halide emulsion after being dissolved in a water-miscible organic solvent such as ethanol, acetone, dimethylformamide, etc. alone or in a mixture. Furthermore, the blue-sensitive sensitizing dye according to the present invention can be used in combination with other sensitizing dyes within a range that does not impair the effects of the present invention. In this case, the two sensitizing dyes may be dissolved separately and mixed before being added, or may be added as separate solutions. They may be added at intervals of . In the color developing solution used in the present invention, instead of hydroxylamine, which is conventionally used as a preservative, the general formula [I]
The compound represented by (hereinafter also referred to as the preservative of the present invention) is preferably used from the viewpoint of rapidity. General formula [I] (In the formula, R1 and R2 each represent an alkyl group or a hydrogen atom. However, both R1 and R2 are not hydrogen atoms at the same time, and R1 and R2 may form a ring. Therefore, in the present invention, it is important that hydroxylamine sulfate is not included.In the general formula [I], R1 and R2 each represent an alkyl group or a hydrogen atom that is not a hydrogen atom,
The alkyl groups represented by R1 and R2 are. They may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. The alkyl groups of R1 and R2 include those having a substituent, and R1 and R2 may be combined to form a ring. , for example, a heterocyclic ring such as piperidine or morpholine. Specific examples of the hydroxylamine compound represented by the general formula [I] include U.S. Patent Nos. 3,287,125 and 3
, No. 293,034 and No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below. These compounds of the present invention are usually free amines, hydrochlorides,
It is used in the form of sulfate, p-)luenesulfonate, oxalate, phosphate, acetate, etc. The concentration of the compound represented by the general formula [I] of the present invention in the color developing solution is usually 0.2 g/text to 50 g! , preferably 0.5g/41-30g/l, more preferably 1g/l
l~ISg/l. The compound represented by the general formula [I] of the present invention can be used in place of hydroxylamine sulfate, which has been widely used as a preservative in color developing solutions for conventional silver halide color photographic light-sensitive materials. However, among the compounds of the present invention, for example, N,N-diethylhydroxylamine is known to be used as a preservative for black and white developing agents in color developing solutions containing black and white developing agents. In the so-called external color development method, in which color photographic light-sensitive materials are developed by a reversal method using a color developing solution containing the same, there is a technique used together with phenidone (Japanese Patent Publication No. 45
-22198)). The color developer used in the present invention preferably has a sulfite concentration of 4 X 10-' mol or less per color developer, more preferably 2 X 10-' to 0 mol per unit of color developer. When the sulfite concentration in the emulsion is high, it is much more susceptible to this effect than conventionally used emulsions containing high silver bromide, causing a significant decrease in concentration. Examples of the sulfite used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like. The color developing solution used in the present invention contains at least one compound (hereinafter referred to as the chelating agent of the present invention) selected from the compound represented by the general formula [1]F and the compound represented by the general formula [ml]. It is preferable. General formula [n] '(R,)n. General formula [■koR3 General formula [■ko, [m], R,, R2, R3 and R
4 is a hydrogen atom, a halogen atom, a sulfonic acid group,
Alkyl group of carbon a1-7, -0R3, -GOOR6,
represents an integer, and each of Rs, Rs, R2 and R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, when R2 represents 10H or a hydrogen atom, R1 is a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR,. Examples of the alkyl group represented by R8, R, , R, and R4 include methyl group, ethyl group, 1so-propyl group,
Examples include n-propyl group, t-methyl group, n-phthyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, pencil group, etc. R5, R,, R7 and R
The alkyl group represented by 8 has the same meaning as above, and may further include an octyl group. Examples of the phenyl group represented by R, R, R1 and R4 include a phenyl group, a 2-hydroxyphenyl group, and a 4-aminophenyl group. Typical examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto. (II-1) 4-isopropyl-1,2-dihydroxybenzene (II-2) 1,2-dihydroxybenzene-3,5-
Disulfonic acid (II-3) 1,2.3-trihydroxybenzene-
5-carboxylic acid. (II-4) 1,2.3-trihydroxybenzene-
5-carboxymethyl ester (IT-5) 1,2. : l-trihydroxybenzene-5-carboxy-n-butyl ester (n-6) 5-t-butyl-1,2,3-trihydroxybenzene (H-7) 1,2-cyhydroxybenzene: l, 5
．． 6-trisulfonic acid (IT-8) 1,2-dihydroxybenzene-3,4,
S-)-Lis J lefonic acid (m-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (m-2) 2,3,8-trihydroxynaphthalene-
6-Sulfonic acid (III-3) 2,3-dihydroxynaphthalene-6
-Carboxylic acid (III-4) 2.3-dihydroxy-8-isopropyl-naphthalene (III-5) 2.3-dihydroxy-8-chloro-
Naphthalene-6-sulfonic acid Among the above compounds, 1,2-dihydroxybenzene-3,
Examples include 5-disulfonic acid, which can also be used as alkali metal salts such as sodium salts and potassium salts. In the present invention, the chelating agent of the present invention can be used in an amount of S+ng to 20 g per developer solution,
Preferably IOB~10g, more preferably 20mg
Good results are obtained by adding ~3g. The chelating agent of the present invention may be used alone or in combination with two
The above may be used in combination. Furthermore, aminopolyphosphonic acids such as aminotri(methylenesulfonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, Other chelating agents such as polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination. The color developing agent used in the color-forming lyophilic liquid of the present invention is as follows:
Preferred are p-phenylenediamine compounds having a water-soluble group. A p-phenylenediamine compound having a water-soluble group is
Compared to p-phenylenediamine compounds that do not have water-soluble groups such as N,N-diethyl-p-buenylenediamine,
Not only does it have the advantage of not contaminating the photosensitive material and does not cause skin irritation, but it also has the advantage that the object of the present invention can be effectively achieved by combining it with the compound represented by the general formula [I]. can be achieved. Examples of the water-soluble group include those having at least one on the amino group or benzene nucleus of the p-phenylenediamine compound, and specific examples of the water-soluble group include -(C1+2). -CH20H1 4c)12)-N830g-((:Il*)1]-CH
:+,-(C)12),-〇-(CHri,,-C)If
f, -(CH20H1)nc+++)12+m++ (
III and n each represent an integer of 0 or more. ), −
Preferred examples include COOH group, -3O, H group and the like. Specific examples of color developing agents preferably used in the present invention are shown below. [Exemplary color developing agent] NH. NH2 NH. N.H. N.H. H2 NHl NHl NHl NH. N.H. N.H. N.H. Among the color developing agents exemplified above, examples No. 1, (A-1), (A-2), and (A-2) are preferred for use in the present invention.
-3), (A-4), (A-6), (A-7) and (A
-15), particularly preferably No.
(A-1). The color developing agents mentioned above are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like. The color developing agent having a water-soluble group used in the present invention is
Normal color developer 1 x 10-2 to 2 x 10-2 per 12
It is preferable to use it in a range of 1 mole, but from the viewpoint of rapid processing, the amount per color developer is 1.5X 10-" to 2
A range of X 10-" moles is more preferable. In addition to the above components, the color developing solution of the present invention can contain the following developer components. As an alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicon Acid salts, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. may be used alone or in combination within the range that maintains the above effects, that is, the pH stabilizing effect without precipitation. Can be used in combination.In addition, due to pharmaceutical needs or for the purpose of increasing ionic strength, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium carbonate, borates, etc. Various salts can be used. Inorganic and organic antifoggants can also be added if necessary. Furthermore, development accelerators can also be used if necessary. As a development accelerator, U.S. Patent No. 2.648,6
No. 04, No. 3,671,247, Special Publication No. 44-950
Various pyridinium compounds as typified by Publication No. 3, other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate, and U.S. Pat.
, No. 533,990, No. 2.531,832, No. 2,
950,970, 2,577.147, and nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc., as described in Japanese Patent Publication No. 44-9504, and organic solvents and organic compounds as described in Japanese Patent Publication No. 44-9509. Includes amines, ethanolamine, ethylenediamine, jetanolamine, triethanolamine, etc. In addition to phenethyl alcohol described in U.S. Pat. No. 2,304,925, acetylene glycol,
Examples include methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, and amines. Benzyl alcohol is not used in the present invention, and it is preferable to eliminate the use of poorly soluble organic solvents such as the above-mentioned phenethyl alcohol in order to efficiently achieve the purpose of the present invention. Due to the long-term use of color developing solutions, tar is likely to be generated, especially during running processing using low replenishment methods, and the generation of such tar is a serious problem in that it adheres to paper photosensitive materials to be processed and significantly impairs its commercial value. This may even lead to serious malfunctions. In addition, since poorly soluble organic solvents have poor solubility in water, not only is it troublesome that a stirring device is required to prepare the single color developing solution itself, but even with the use of such a stirring device, the dissolution rate is poor. from. There is also a limit to the development accelerating effect. Furthermore, poorly soluble organic solvents reduce the biochemical oxygen demand i
The pollution load value such as (BOD) is large, and it is impossible to dispose of it in sewers or rivers.
Since there are problems such as requiring a large amount of labor and cost, it is preferable to reduce or eliminate the amount of not only benzyl alcohol but also other poorly soluble organic solvents used. Furthermore, the color developing solution of the present invention may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and others as required.
The compounds described in each publication can be used as organic solvents to increase the solubility of the developing agent. Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include, for example, N-methyl-p-aminophenol hexulfate (methol).
, phenidone, N, N''-diethyl-p-aminophenol hydrochloride, N, N, N', N'-tetramethyl-p
-Phenylenediamine hydrochloride, etc. are known, and the amount added is usually 0.01g to 1.0g/JL, which is preferred.In addition, if necessary, competitive couplers, fogging agents, colored couplers, and developing Inhibitor-releasing couplers (
So-called DIR couplers), development inhibitor releasing compounds, etc. can be added. Furthermore, other anti-stain agents and anti-sludge agents 1
Various additives such as a multilayer effect accelerator can be used. Each component of the above color developing solution can be adjusted by sequentially adding and stirring to a certain amount of water. In this case, components with low solubility in water can be added after being mixed with the above-mentioned organic solvent such as triethanolamine. More generally, a plurality of components, each of which can coexist stably, is prepared in advance in a small container in the form of a concentrated aqueous solution or in a solid state, which is then added to water and stirred. Obtainable. In the present invention, the above color developing solution can be used in any pi range, but from the viewpoint of rapid processing, pi 9.5 to 13.
The pH is preferably 0, more preferably pH 9.8-8.
12.0. The processing temperature for color development using the color developer of the present invention is 3.
The temperature should be 5°C or higher and 70°C or lower, and the higher the temperature, the more preferable it is because it enables rapid processing in a short time, but it is better not to be too high in terms of the stability of the processing solution, and the treatment should be performed at 37°C or higher and 60°C or lower. is preferred. Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is within 25 seconds. Further, it is preferable to perform the heating for a period of 20 seconds to 3 seconds in order to achieve the effects of the present invention. In the present invention, at least one compound selected from the compound represented by the general formula [I], the compound represented by the general formula [1]], and the compound represented by the general formula [ml] is used.
It is preferable to use a color developing solution containing one compound, and examples of its application include -bath processing and various other methods. For example, various processing methods can be used, such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid, but the processing steps are essentially It is preferable that the process consists of color development, pre-bleaching, washing with water (including stabilization treatment as an alternative to washing). In the present invention, it is preferable to provide a bleach-fixing step immediately after the color development treatment step in view of speed and achieving the effects of the present invention. The bleaching agent that can be used in the bleach-fix solution used in the present invention is not limited, and is preferably a metal complex salt of an organic acid. Organic acids containing iron, cobalt,
It is coordinated with metal ions such as copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be in the form of alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid

[6] Cyclohexanediaminetetraacetic acid [71iminodiacetic acid]

[8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [10]
Glycol ether amine tetraacetic acid [1]]
Ethylenediaminetetrapropionic acid [121 Phenylenediaminetetraacetic acid [13J Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt "151 Ethylenediaminetetraacetic acid tetrasodium salt [161 Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine -N-(β-oxyethyl)-N,N',N"-)-ributyric acid sodium salt [18
1 Propylene diamine tetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexane diamine tetraacetic acid sodium salt These bleaching agents are used at 5-450 g/l, more preferably at 20-250 g/u. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. Also ethylenediaminetetraacetic acid iron (m) vinegar #!
A bleach-fixing solution consisting of a bleaching agent and a large amount of a halide such as ammonium bromide other than the silver halide fixing agent, and iron ethylenediaminetetraacetate (m).
A special bleach-fix solution having a composition consisting of a combination of an acetic acid bleach and a large amount of a halide such as ammonium bromide can be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide,
Potassium iodide, ammonium iodide, etc. can also be used. The silver halide fixing agent contained in the bleach-fixing solution includes compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and the like. These fixing agents are used in an amount of 5 g/1 or more, within the range that can be dissolved, but are generally used in an amount of 70 to 250 g/text. The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH 1 buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. Also hydroxylamine,
Preservatives such as hydrazine and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, organic solvents such as methanol, dimethylsulfamide, and dimethylsulfoxide, etc., as appropriate. It can be made to contain. The bleach-fix solution used in the present invention includes Japanese Patent Publication No. 46-280, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 46-556, Belgian Patent No. 770,910, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854. , JP-A No. 54-71634 and No. 4
Various bleaching accelerators such as those described in No. 9-42349 can be added. The bleach-fixing solution is used at a pH of 4.0 or higher, but is generally used at a pH of 4.0 or higher and a pn of 9.5 or lower, preferably at a pH of 4.5 or higher and a pH of 8.5 or lower.
More specifically, the most preferable pH is 5.0 or more and 8.5 or less. The processing temperature is below 80℃. It is preferably used at a temperature of 55° C. or lower to prevent evaporation. The bleach-fixing treatment time is preferably 3 seconds to 45 seconds, more preferably 5 seconds to 30 seconds. In the present invention, water washing is performed following the color development and bleach-fixing steps, and the water washing is performed at a replenishment amount of 0.1 to 50 times the amount of prebath brought in per unit area of the photosensitive material. It is preferable for the effects of the present invention, particularly for the stabilization of dye images, when the dye is used. Hereinafter, preferred embodiments of the water washing treatment will be described. Compounds preferably used in the washing solution include chelating agents having a chelate stability constant of 8 or more with respect to iron ions, and these are preferably used to achieve the object of the present invention. Here, the chelate stability constants are L, G, 5illen
・A.E. Martell, “5tability”
Con5tants of Me-talion (
:oplexeS”, The (:hemica
l 5ociety, London (1964)
, S. Chaberek-A, E. Marte1], 'Organic Sequestering Ag
ents" means a constant generally known by Wiley (1959) etc. Chelating agents with a chelate stability constant of 8 or more for iron ions that are preferably used in the washing solution include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, etc. Examples include chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. The above-mentioned iron ion refers to ferric ion (Fe 2 *
) means. Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds: ethylenediamine diorthohydroxyphenylacetic acid, Diaminopropanolenoic acid, nitrilotalacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediamineniprobionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanollenoic acid, transcyclohexanediaminetetraacetic acid Acetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1, 2,4-)licarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,:l-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium birophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. and particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1
, 1-diphosphonic acid, etc., among which 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used. The usage amount of the above chelating agent is 0.01 to 5 per wash solution.
It is preferably 0 g, more preferably in the range of 0.05 to 20 g. Further, ammonium compounds are particularly preferred as compounds to be added to the washing liquid. These are supplied by ammonium mounds of various inorganic compounds, including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, and fluoride. Ammonium, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, tricarboxylic laurate Ammonium acid, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium Vtite, ethylenediamine Ammonium tetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate. , ammonium tartrate, ammonium thioglycolate, 2,4.6-)linitrophenol ammonium, and the like. Among these ammonium compounds, ammonium thiosulfate is particularly preferred in achieving the effects of the present invention. The amount of ammonium compound added is 1. OX 10-' or more is preferable, more preferably o-oot per liter of washing liquid
~5.0 mol, more preferably 0.002 mol
~1.0 mol. Further, it is desirable that the washing solution contains sulfite to the extent that bacteria will not be generated. The sulfite to be contained in the washing solution may be any organic or inorganic substance as long as it releases sulfite ions, but inorganic salts are preferred, and specific preferred compounds include sodium sulfite, potassium sulfite, and ammonium sulfite. , ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfide, sodium cartaraldehyde bisbisulfite, sodium cohelic aldehyde bisbisulfite, etc. It will be done. The sulfite is at least 1.0 x 10-S in the washing solution.
It is preferable to add it in an amount of mol/vertical,
More preferably 5 X 1[1-'mol/2-1, Ox
10-'mol/state. Although it may be added directly to the washing liquid, it is preferable to add it to the washing replenishment liquid. The washing liquid used in the present invention desirably contains an anti-piping agent, which can further improve sulfurization prevention and image preservability. Preferable anti-spill agents to be added to the washing solution of the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, lysine compounds, guanidine compounds,
Carbamate compounds, triazole compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds,
propatoolamine compounds, sulfamide compounds,
These are pyronone compounds and amino compounds. The benzoic acid compounds include salicylic acid, hydroxybenzoic acid, and ester compounds of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester, butyl ester, etc., but preferably n-butyl ester and isobutyl ester of hydroxybenzoic acid. ester, propyl ester, and salicylic acid, and more preferably a mixture of the three hydroxybenzoic acid esters. A phenolic compound is a compound that may have a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, an alkyl group (especially an alkyl group with an alkyl group of 01 to 6), or a phenyl group as a substituent. , preferably ortho-phenylphenol and ortho-cyclohexylphenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol, phenol and the like. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and is preferably 1,2-benzisothiazolin 3-one, 2-methyl-4-isothiazolin 3-one, or 2-octyl-4-isothiazolin. 3-one, 5-chloro-2-methyl-4-isothiacyli-3-one, 2-(4-thiazolyl)benzimidazole. Specifically, pyridine compounds include 2,6-dimethylpyridine, 2,4,6-)limethylpyridine, radium-2
-Pyridinethiol-1-oxide and the like, preferably radium-2-pyridinethiol-1-oxide. Specifically, guanidine compounds include cyclohexidine,
Examples include polyhexamethylene biguanidine hydrochloride, dodecylguanidine hydrochloride, etc., and dodecylguanidine and its salts are preferred. Specific examples of carbamate compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate. Specific examples of morpholine compounds include 4-(3-nitrobutyl)morpholine and 4-(3-nitropropyl)morpholine. Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc.
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-n-butyl-tetradecylphosphonium chlorite and triphenyl-nitrophenylphosphonium chloride. Specific examples of quaternary ammonium compounds include penzarconicum salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, and laurylpyridinium chloride. etc. Specifically, the urea-based compounds include N-(3,4-dichlorophenyl)-N''-(4-chlorophenyl)urea, N-(
Examples include 3-trifluoromethyl)-N'-(4-chlorophenyl)urea. Specific examples of isoxazole compounds include 3-hydroxy-5-methyl-isoxazole. Propatur amino compounds include lowobanols and impropaturs, specifically DL-2-benzylamino-1-propatur, 3-diethylamino-
1-propanol, 2-dimethylamino-2-methyl-
1-propatur, 3-amino-1-propatur, idopropaturamine, diisopropaturamine, N
, N-dimethyl-isopropanolamine, and the like. Specifically, the sulfamide-based compounds include O-nitrobenzenesulfamide, p-aminobenzenesulfamide, fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, and α-amino-p-toluenesulfamide. famid, sulfanilamide, acetosulfaguanidine, sulfathiazole. Examples include sulfadiazine, sulfamethacine, sulfamethacin, sulfine oxazole, homosulfamine, sulfamidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, succinylsulfathiazole, and the like. Specific examples of pyronone compounds include dehydroacetic acid and the like. A specific example of the amino acid compound is N-lauryl-β-alanine. Specific examples of triazole compounds include 2-aminotriazole, benzotriazole, and 5-methyl-benzotriazole. Among the above-mentioned anti-spill agents, compounds preferably used in the present invention are thiazole compounds, sulfamide compounds, and pyronone compounds. The amount of anti-piping agent added to the washing liquid is o, o per 1 wash liquid.
It is preferably used in a range of ot to 30 g, more preferably in a range of 0.003 to 5 g. The washing liquid in the present invention preferably contains a metal salt in combination with a chelating agent. Such metal salts include Ba, Ca, Ce,
Go, In. La, Mn, Ni, Bi, Pb, Sn, I
n, Ti, Zr, Mg, All or S, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate, or a water-soluble chelating agent. The amount used is 1 wash liquid IX
The range is from 10-' to lx 10-' moles, preferably from 4X 10-' to 2X 10-' moles. In addition to the above, aldehydes may be contained in the washing solution of the present invention. Here, aldehydes refer to compounds that accommodate aldehyde groups. Specific compounds include: l Formaldehyde 2 Acetaldehyde 3 Propionaldehyde 4 Isobutyraldehyde 5 N-Butyraldehyde 6 N-Valeraldehyde 7 Isovaleraldehyde 8 Methyl ethyl acetaldehyde 9 Trimethylacetaldehyde 10 n-hexaldehyde 1] Methyl-n-propylacetaldehyde 12
Isohexaldehyde 13 Glyoxal 14 Seventy aldehyde 15 Cohelic aldehyde 16 Glutaraldehyde 17 Acetaldehyde 18 Methylglyoxal 19 Acetoacetic aldehyde 20 Glycolaldehyde 21 Ethoxyacetaldehyde 22 Aminoacetaldehyde 23 Betainaldehyde 24 Chloral 25 Chloracetic acid Toaldehyde 26 Dichloroacetaldehyde 27 Promal 28 Dichloroacetaldehyde 29 Iodoacetaldehyde 30 α-Chlorpropionacetaldehyde 31
α-bromopropionacetaldehyde 32 Furfural can be mentioned. The above aldehydes are 0.1 to 50 g per 141 of the washing liquid.
It is preferable to contain it in the range of 0.5 to Lo
It is preferable to contain it within the range of g. Further, in the present invention, a washing liquid treated with an ion exchange resin may be used. The ptl of the washing liquid applicable to the present invention is 5.5 to 10.
As the pH adjusting agent that can be contained in the washing liquid applicable to the present invention, any commonly known alkaline agent or acidic agent can be used. The treatment temperature of the water washing treatment is preferably in the range of 15°C to 60°C, more preferably in the range of 20°C to 45°C. Furthermore, from the viewpoint of effectively achieving the object of the present invention, it is preferable that the treatment time be as short as possible. It is preferably 5 seconds to 60 seconds, most preferably 5 seconds to 50 seconds. In the case of multiple tank washing treatment, it is preferable that the front tank is processed for a short time and the rear tank is processed for a long time. In particular, it is desirable to perform the treatment sequentially with a treatment time 20% to 50% longer than in the previous tank. The method of supplying the washing liquid in the washing process that can be applied to the present invention is preferably a multi-tank countercurrent system, in which case it is preferable to supply it to the rear bath and allow it to overflow to the front bath. Of course, it is also possible to process in a single tank. can. The above compounds can be added as a concentrated liquid to the washing tank, or
Alternatively, there are various methods such as adding the above-mentioned compounds and other additives to the washing liquid supplied to the washing tank and using this as a supply liquid for the washing replenisher, but any addition method may be used. The amount of water used in the washing process of the present invention is equal to 0% of the amount of prebath (usually bleach-fix solution or fixer solution) brought in per unit area of the photosensitive material.
．． It is preferably 1 to 50 times, particularly preferably 5 to 30 times. The number of washing tanks in the washing treatment applicable to the present invention is preferably 1 to 5, particularly preferably 1 to 3, and preferably 946 or less. The silver halide grains used in the silver halide color photographic light-sensitive material applied to the present invention contain at least 90% silver chloride.
It is preferable that the silver halide grains contain mol % or more, more preferably 95 mol % or more, still more preferably 97 mol %. The silver halide emulsion containing the silver halide grains of the present invention contains silver bromide and/or silver halide as a silver halide composition in addition to silver chloride.
or silver iodide, in which case silver bromide is 10
It is not more than 1 mol %, preferably not more than 5 mol %, more preferably not more than 3 mol %, and when silver iodide is present, not more than 1 mol %, preferably not more than 0.5 mol %. Such silver halide grains consisting essentially of silver chloride may be applied to at least one silver halide emulsion layer, but preferably they are applied to all silver halide emulsion layers. The crystals of the silver halide grains used in the present invention may be normal crystals, twin crystals, or other crystals, and have [1,0,0 layer planes and [1
, 1, 1] Any ratio can be used for the plane. Furthermore,
The crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. The silver halide may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain.
No. 934 and Japanese Patent Application No. 170070/1983) may also be used. The silver halide grains used in the present invention may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method. Alternatively, for example, seed particles may be grown to a predetermined size by an acidic method and then by an ammonia method which has a high growth rate. When growing silver halide grains, control the pH, pAg, etc. in the reaction vessel,
For example, it is preferable to simultaneously implant and mix silver ions and halide ions in an amount commensurate with the growth rate of silver halide grains, as described in JP-A-54-48521. Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion. These silver halide emulsions contain active gelatin: sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers: reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.: Noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-rothio-3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, specifically ammonium chloroparadate, potassium chlorobratinate and sodium chloroparadate (these They act as sensitizers or fog suppressants depending on the amount. It may also be chemically sensitized (for example, in combination with a sensitizer). The silver halide emulsion according to the present invention is formed by chemical heating by adding a sulfur-containing compound, and has at least one kind of hydroxytetrazaindene and mercapto group before, during, or after this chemical ripening. It may also contain at least one nitrogen-containing heterocyclic compound. The silver halide used in the present invention is a sensitizing dye in an amount of, for example, 5 X 10-' to 3 X 1 per mole of silver halide in order to impart photosensitivity in a desired wavelength range.
Optical sensitization may be achieved by adding G-" moles. Various sensitizing dyes can be used, and each sensitizing dye can be used singly or in combination of two or more. The present invention A water-soluble dye or a dye (AI dye) that can be decolored with a color developing solution can be added to the photographic constituent layer of the silver halide color photographic light-sensitive material, and examples of the AI dye include oxanol dye, hemioxanol dye, Merocyanine dyes and azo dyes are used.Among them, oxanol dyes, hemioxanol dyes, merocyanine dyes, etc. are useful.The photographic couplers used in the present invention are not limited, and both 2-equivalent type and 4-equivalent type can be used. As cyan couplers, phenolic and naphthol compounds are preferred, for example, U.S. Pat. No. 2,359,929, U.S. Pat.
, No. 895,826, No. 3,253,924, No. 3.
034,892, 3,31], 476, 3,
No. 386,301, No. 3,419,390, No. 3,4
No. 58,315, No. 3.476.563, No. 3,53
1,383, etc., and methods for synthesizing these compounds are also described in the same publication. Examples of photographic magenta couplers include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indasilone-based compounds. As a pyrazolone magenta coupler, U.S. Patent No. 2,600,7
No. 88, No. 3,062,653, No. 3,127,26
No. 9, same: 1.31]. No. 476, 3.419, 39
No. 1, No. 3,519,429, No. 3,558,31
No. 8, No. 3,684,514, No. 3,888,680
No., JP-A-49-29639, JP-A No. 49-1] 1631
No. 49-129538, No. 50-13041,
Compounds described in Japanese Patent Publication Nos. 53-47187, 54-10491, and 55-30615; as pyrazolotriazole magenta couplers, US Pat.
, 247,493, and Berly Patent No. 792,525. As the diffusion-resistant colored magenta coupler, a compound in which an aryl anion is substituted at the coupling position of a colorless magenta coupler is generally used. U.S. Patent No. 2,801,171, 2.
91] No. 3,608, No. 3.005,712, No. 3,
No. 684,514, British Patent No. 937.621. Tokukai Showa 4
Examples include compounds described in No. 9-123625 and No. 49-31448. Furthermore, it is also possible to use a colored magenta coupler of the type described in U.S. Pat. No. 3,419,391, in which the dye does not easily flow out into the processing solution due to the reaction of the oxidized product of the developing agent. As photographic yellow couplers, open-chain ketomethylene compounds have conventionally been used, and generally widely used benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers can be used. Furthermore, a two-equivalent type yellow coupler in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction is also advantageously used. Examples of these are U.S. Pat. No. 2,875,057, 3.21i5
, No. 506, No. 3,664,841, No. 3,408,
No. 194, No. 3.277.155, No. 3,447.9
No. 28, No. 3,415,652, Special Publication No. 48-294
No. 32, No. 4B-68834, No. 49-10736, No. 49-122335. It is described in No. 50-28834, No. 50-132926, etc. together with the synthesis method. However, particularly useful cyan couplers include cyan couplers represented by the following general formulas [C-1] to [C-3] in order to better achieve the effects of the present invention. General formula [C-1] ■ In the formula, one of R and R1 is a hydrogen atom, the other is a linear or branched alkyl group having at least 2 to 12 carbon atoms, and X is a hydrogen atom or an aromatic group. It represents a group that can be separated by a coupling reaction with an oxidized form of a primary amino color developing agent, and R2 represents a ballast group. General formula [C-2] H General formula [C-3] 1'll+ In the formula, Y is -COR4, -C0NHCOR4 or 100NH30zRn (
However, R4 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Rs represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R4 and R5 may be combined with each other to form a 5- to 6-membered heterocycle), R3 represents a ballast group, and Z is a hydrogen atom or an oxidized product of an aromatic primary amine color developing agent. Represents a group that can be separated by a coupling reaction with The cyan coupler according to the present invention has the general formula %.The general formula [C-1] will be further explained. In the present invention, the linear or branched alkyl group having 2 to 12 carbon atoms represented by R1 and R in the general formula [C-1] is 1
For example, ethyl group, propyl group, butyl group. In general formula [C-1], the ballast group represented by R2 has a size that gives the coupler sufficient bulk to make it substantially impossible to disperse the coupler from the layer to which it is applied into other layers. Typical ballast groups have a total carbon number of 8 to 32.
Examples include an alkyl group or an aryl group, preferably having a total number of carbon atoms of 13 to 28. These alkyl groups and 7
The aryl group may have a substituent, and examples of the substituent for the aryl group include an alkyl group, an aryl group, an alkoxy group, an allyloxy group, and a carboxy group. Examples include acyl group, ester group, hydroxy group, cyano group, nitro group, carbamoyl group, carbonamido group, alkylthio group, arylthio group, sulfonyl group, sulfonamide group, sulfamoyl group, and halogen, and substituents for alkyl group include Examples include the substituents listed above for the aryl group except for the alkyl group. The preferred ballast group is the following general formula: % R33 represents an alkyl group having 1 to 12 carbon atoms, Ar represents a 7-aryl group such as a phenyl group, and even if this aryl group has a substituent, Good substituents include alkyl groups,
Examples include a hydroxy group, a halogen atom, an alkylsulfonamide group, and the most preferred is a branched alkyl group such as a t-butyl group. As is well known to those skilled in the art, the group defined by X in the general formula [C-1] that can be separated by coupling with the oxidized product of the color developing agent determines the number of equivalents of the coupler, and Typical examples that affect coupling reactivity include halogens such as chlorine and fluorine, aryloxy groups, substituted or unsubstituted flukoxy groups, acyloxy groups, sulfonamide groups, arylthio groups, heteroylthio groups, and heteroyloxy groups. group, sulfonyloxy group, carbamoyloxy group, etc. More specific examples include JP-A-50-10135, 1iii150-1
No. 20334, No. 50-130414, No. 54-48
No. 237, No. 51-146828, No. 54-1473
No. 6, No. 47-37425, No. 50-123341, No. 58-95345, Special Publication No. 48-36894,
U.S. Patent No. 3.47ft, No. 583, No. 3,737,31
Examples thereof include groups described in No. 8, No. 3,227,551, and the like. Next, 1 general formula [C-2] or [C-3 according to the present invention]
The cyan coupler shown in ] will be explained. In the general formulas [C-23 and [C-3], Y is 10OR
s, -CONHC: A group represented by OR4 or 100NHSOzRa. Here, R4 is an alkyl group, preferably an alkyl group having 11 to 20 carbon atoms (for example, methyl, ethyl, t-methyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (for example, an allyl group). , heptadecenyl group, etc.), cycloalkyl group, preferably one with a 5- to 7-membered ring (e.g., cyclohexyl, etc.)
, an aryl group (e.g., phenyl, tolyl, naphthyl, etc.), a heterocyclic group, preferably a 5- to 6-membered heterocyclic group containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms (e.g., furyl, R5 represents a hydrogen atom or a group represented by R4 e R4 and R5 are bonded to each other to form 5
~ may form a 6-membered heterocycle, in which R2 and R
Any substituent can be introduced into 3, such as 1, for example, alkyl having 1 to 1 o carbon atoms,! ! : (e.g. methyl, i-propyl, i-butyl, E-butyl, t-octyl, etc.),
Aryl groups (e.g. phenyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, P-toluenesulfonamide, etc.), sulfamoyl groups (e.g. methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl groups (e.g., methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl groups, carbamoyl groups (e.g., dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl groups (e.g., ethoxycarbonyl, phenoxycarbonyl, etc.),
Examples include acyl groups (eg, acetyl, benzoyl, etc.), heterocyclic groups (eg, pyridyl, pyrazolyl, etc.), alkoxy groups, aryloxy groups, acyloxy groups, and the like. In general formula [C-2] and general formula [C-3], R3
represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formula [C-2] and the general formula [C-3] and the cyan dye formed from the cyan coupler, preferably 0 which is an alkyl group, aryl group or heterocyclic group having 4 to 30 carbon atoms, such as a linear or branched alkyl group (e.g. t-butyl, n-octyl, t-octyl, n-dodecyl, etc.), alkenyl group, Examples include a cycloalkyl group, a 5-negative or 6-membered heterocyclic group, and the like. In the general formula [C-2] and the general formula [C-3], Z represents a hydrogen atom or a group that can be separated during the coupling reaction of the color developing agent with an oxidizing product. fluorine, etc.), substituted or unsubstituted alkoxy groups, aryloxy groups, peterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups,
Examples include sulfonamide groups, and more specific examples include U.S. Pat. No. 3,741,583 and JP-A-47-374
No. 25, Japanese Patent Publication No. 1983-36894, Japanese Patent Publication No. 1983-10
No. 135, No. 50-1] No. 7422, No. 50-1304
No. 41, No. 51-108841, No. 50-12034
No. 3, No. 52-18315, No. 53-105226, No. 54-14736, No. 54-48237, No. 5
No. 5-32071, No. 55-65957, No. 56-1
No. 938, No. 56-12643, No. 56-27147
No. 59-146050, No. 59-166956, No. 60-24547, No. 60-35731, No. 6
Examples include those described in No. 0-37557. In the present invention, the following general formulas [C-4], [C-5]
A cyan coupler represented by [C-6] or [C-6] is more preferable from the viewpoint of achieving the object of the present invention. General formula [C-4] 1]+1 General formula [C-51 n-wise general formula [C-6] 1'll+ In general formula [C-4], R34 is a substituted or unsubstituted 7-aryl group (particularly preferably is a phenyl group), and when the aryl group has a substituent, the substituent is -5
O2R37, halogen atoms (fluorine, bromine, chlorine, etc.)
, -CF3, -N02, -CM, -GORh. -100R31, -3O20R37, At least one substituent selected from -100R31, -3O20R37 is included. Here, R31 is an alkyl group, preferably a carbon number 1
~20 alkyl groups (e.g. methyl, ethyl, tert
-butyl, dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, heptadecenyl groups, etc.), cycloalkyl groups, preferably 5 to 7 carbon atoms
Represents a membered ring group (e.g. cyclohexyl, etc.), an aryl group (e.g. phenyl group, tolyl group, naphthyl group, etc.), R
38 is a hydrogen atom or a group represented by R37. A preferred compound of the cyan coupler of the present invention represented by the general formula [C-4] is one in which R37 is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyan, nitro, -5O2R39 (R39 is (alkyl group), halogen atom, and trifluoromethyl. In general formulas [C-5] and [C-6], R35, R
36 is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (such as methyl, ethyl, tert-butyl, dodecyl, etc.), or an alkenyl group, preferably having 2 carbon atoms.
~20 alkenyl groups (allyl group, oleyl group, etc.), cycloalkyl group, preferably 5- to 7-membered ring group (e.g. cyclohexyl etc.), aryl group (e.g. phenyl group, tolyl group, naphthyl group etc.), heterocyclic group (e.g. nitrogen atom,
5-6 members containing 1-4 oxygen atoms or sulfur atoms
A membered heterocycle is preferred, such as a furyl group. Examples include thienyl group and benzothiazolyl group. ) represents. Said R37, R2O and general formulas [C-5] and [C-6
An arbitrary substituent can be further introduced into R35 and R36 of the formula, and specifically, a substituent such as that which can be introduced into the general formula % R5. As a substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable. In general formulas [C-4], [C-5] and [C-6], Z and R3 have the same meanings as in general formulas [C-2] and [C-3], respectively. A preferable example of the ballast group represented by R) is a group represented by the following general formula [C-7]. General formula [C-7] In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group, K represents an integer of 0 to 4, standing represents O or 1, and when K is 2 or more, 2 or more The R groups present may be the same or different. *Flso represents a linear or branched alkylene group having 1 to 20 carbon atoms, and a substituted alkylene group such as an aryl group, and R represents a monovalent group, preferably hydrogen. atoms, halogen atoms (e.g. chromium, bromine), alkyl groups, preferably linear or branched alkyl groups having 1 to 20 carbon atoms (
For example, six groups such as methyl, t-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), aryl groups (e.g. phenyl group), heterocyclic groups (preferably nitrogen-containing heterocyclic groups), alkoxy group, preferably a straight-chain or branched alkoxy group having 1 to 20 carbon atoms (e.g. 6 groups such as methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy), aryloxy group (e.g. phenoxy group), hydro acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy group, benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably straight chain or branched furkyl group having 1 to 20 carbon atoms Carbonyl group, preferably phenoxycarbonyl group, alkylthio group, preferably carbon number 1-
20 acyl group, preferably a straight chain or branched fulkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably a straight chain or branched fulkylcarboxamide group having 1 to 20 carbon atoms, a benzenecarboxamide group, sulfonamide group,
Preferably a linear or branched alkylsulfonamide group or benzenesulfonamide group having 1 to 20 carbon atoms, a carbamoyl group, preferably a linear or branched alkylaminocarbonyl group or phenylaminocarbonyl group having 1 to 20 carbon atoms, sulfamoyl group, preferably having 1 to 20 carbon atoms
represents a linear or branched fulkylaminosulfonyl group or phenylaminosulfonyl group. The method for synthesizing the cyan couplers represented by the general formulas [C-1] to [C-3] and specific exemplified compounds are described in Japanese Patent Application No. 6
No. 1-92655, pages 76 to 124, and cyan couplers (CC-1) to (CC-28) and 98 to 12 shown in pages 81 to 85 of the same specification.
Cyan couplers (C-t) to (C-10) shown on page 3
0) is given as a specific example. Further, in order to efficiently achieve the object of the present invention, it is particularly preferable to use a cyan coupler represented by the following general formula [M-I]. General formula [M-I] In the formula, Z represents a nonmetallic atom group necessary to form a nitrogen-containing heterocycle, the ring formed by Z may have a substituent, and X is a hydrogen atom. or represents a group that can be separated by reaction with an oxidized product of a color developing agent, and R represents a hydrogen atom or a substituent. The substituent represented by R is not particularly limited, but typically includes alkyl, aryl, and anilino. Acylamino, sulfonamide, alkylthio. There are six groups such as arylthio, alkenyl, and cycloalkyl, but in addition to these, there are halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, and heterocycle. Oxy, siloxy. 6 groups of acyloxy, carbamoyloxy, amine, alkylamine, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, and spiro compound residues,
Also included are bridged hydrocarbon compound residues and the like. The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched. The aryl group represented by R is preferably a phenyl group. Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group. Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above. The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched. The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred. Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group , 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, such as 3,
4,5.8-tetrahydropyranyl-2-oxy group, 1
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1 , 3,5-triazole-6 monothio group, etc.; Siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide groups include succinimide group, 3-heptadecylsuccinimide group, phthalimide group. group, glutarimide group, etc.; spiro compound residues include spiro[3,31 hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2,2,1
]hebutan-1-yl, tricyclo[3,3°1.13
-1] Decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like. Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxycarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded with N atom, alkyloxycarbonylthio amino, aryloxycarbonylamino, carboxyl, (R1' is the same as the above R, Z' is the same as the above Z, R2' and R3' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group) , ) and the like, preferably a halogen atom, particularly a chlorine atom. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned. More specifically, what is represented by the general formula [M-Il is represented by, for example, the following general formulas [M-[1 to [M-VII]]. In the general formula [M-Ill to general formula [M-■], R
1-R8 and X have the same meanings as R above. Also, preferred among the general formulas [M-Il] are those represented by the following general formula [M-■]. General formula [M-■]! In the formula, R+, X and Z+ general formula [R in M-Il
, X and Z. Among the magenta couplers represented by the general formulas [M-■] to [M-■], particularly preferred ones are those represented by the general formula [M-■].
II]. Substituents that the ring formed by Z in general formula [M-Il and the ring formed by Zl in general formula [M-■] may have, and general formula [M-II] to general formula [
As R2-R8 in M-Vll, the general formula [M-lX
Those represented by l are preferred. General formula [M -lXl -R1-5O2-R2 In the formula, R1 represents an alkylene group, and R2 represents an alkyl group, a cycloalkyl group, or an aryl group. The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the alkylene group is straight chain or branched. The alkyl group represented by R2 is preferably a 5- to 6-membered one. In addition, when used for positive image formation, the substituent R on the heterocycle
And R1 is most preferably represented by the following general formula [M-X
It is represented by l. General formula [M-Xl 10-C- 4 In the formula, R9, RIG and R1+ each have the same meaning as R above. Further, R9, RIG and two of the R order, for example R9 and RIG, may be combined to form a consonant or unsaturated ring (for example, cycloalkane, cycloalkene, heterocycle),
Furthermore, R1] may be bonded to the chain ring to constitute a bridged hydrocarbon compound residue. Preferred specific examples of the cyan coupler include the one described on pages 15 to 31 of Japanese Patent Application No. 82-220080.
~77 compounds are mentioned. In addition to the above-mentioned typical examples of compounds according to the present invention, specific examples of compounds according to the present invention include Japanese Patent Application No. 61-9791.
Among the compounds described on pages 66 to 122 of the specification, N001-4, 8.8-17°18-24.
26~43.45~59.81~104.10Ei~1
21°123-182.Compounds shown by 184-223 can be mentioned. Also, the coupler is described in the Journal of the Chemical
Society 4 (Journal of the C
hemi-cal 5ociety), Parky
(Perkin) I (1]17?). 2047-2052, U.S. Patent No. 3,725,087,
JP-A No. 59-99437, No. 58-42045, No. 59-162548, No. 59-171956, No. 6
No. 0-33552, No. 60-43659, No. 60-1
It can be synthesized with reference to No. 72982 and No. 60-190779. The amount of the diffusion-resistant coupler used in the present invention is generally from 0.05 to 1 mole of silver in the light-sensitive silver halide emulsion layer.
It is 2.0 mol. In the present invention, in addition to the above-mentioned diffusion-resistant couplers, various kinds of I
R compounds and the like are preferably used. The silver halide color photographic material used in the present invention may contain various other photographic additives, such as antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure No. 17843. Agents, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. In the silver halide color photographic light-sensitive material used in the present invention, the woody colloid used to prepare the emulsion is preferably gelatin, and other examples include derivative gelatin,
Synthesis of single or copolymers of graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole, polyacrylamide, etc. Any hydrophilic polymer or the like is included. Supports for the silver halide color photographic material used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer, such as glass plates, cellulose acetate, cellulose nitrate, or polyethylene. Examples include polyester films such as terephthalate films, polyamide films, polycarbonate films, polystyrene films, etc., and other ordinary transparent supports may also be used, and these supports are appropriately selected depending on the intended use of the photosensitive material. Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating 4i can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Also, US Patent 2,
781,791 and 2.941.8i38 can also be used. In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, the blue-sensitive silver halide emulsion layer,
It is preferable to arrange a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. Each of these light-sensitive silver halide emulsion layers may consist of two or more layers. In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers. In these constituent layers, wood-philic colloids that can be used in the emulsion layer as described above can be similarly used as a binder, and can also be contained in the emulsion layer as described above. It can be loaded with various photographic additives. In the method for processing a silver halide color photographic light-sensitive material of the present invention, if the silver halide color photographic light-sensitive material is a light-sensitive material that is processed by a so-called internal development method containing a coupler in the light-sensitive material, color paper can be used. It can be applied to any silver halide color photographic light-sensitive material such as color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color paper. [Effects of the Invention] According to the present invention, it is possible to provide a bleach-fix solution with less deterioration in desilvering properties, suppress photographic properties, especially the occurrence of residual color stain, and improve the preservation of dye images obtained by processing. It is possible to provide a method for processing a silver 10genide color photographic material with excellent stability. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these embodiments. Example 1 A photosensitive material was prepared by sequentially coating the following layers on a polyethylene coated paper support from the support side. In addition, as polyethylene coated paper, the average molecular weight io
o, ooo, 6.8% by weight of anatase titanium oxide was added to a mixture of 200 parts by weight of polyethylene with a density of 0.95 and 20 parts by weight of polyethylene with an average molecular weight of 2,000 and a density of 0.80, and extrusion coating method Thickness 0.034v on surface of high-quality paper with weight 170g/m''
A coating layer of 0.040 II m in thickness was formed on the back surface only of polyethylene. After the polyethylene-coated surface of the support was pretreated by corona discharge. The following layers were applied in sequence. 1st layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.5 mol% of silver bromide. 1
Sensitized using 2.5x 1o-' moles of sensitizing dye (
(using isopropyl alcohol as a solvent), 200 mg of 2,5-di-t-butylhydroquinone dissolved and dispersed in dibutyl phthalate, and yellow coupler [Y-1] of the following structure per mole of halogenated m2. Contains 10-1 mole of Ox, silver fl (300 mg/
It is applied so that it becomes rn'. Second layer: 300 g/rn' of mono-octyl hydroquinone dissolved and dispersed in dibutyl phthalate. 2-(2''-hydroxy-3',5
'-di-t-butylphenyl)benzotriazole. 2-(2'-hydroxy-5'-t-butylphenyl)
Benzotriazole, 2-(2'-hydroxy-3'-
t-butyl-5'-methylphenyl)-5-chloro-benzotriazole and Z-(2'-hydroxy-3',
Mixture fs of S'-t-butylphenyl)-5-chloro-benzotriazole (1:1:l:1
) The t-luceratin layer containing 200 mg/m' of gelatin was coated to give a gelatin content of 1900 mg/m'. Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.5 mol % of steel bromide. The emulsion contains 450 g of gelatin per mol of silver halide, and the following per mol of silver halide A sensitizing dye of the structure [I] was sensitized using 2.5 x 10-' moles of 2,5-di-
[M-1] of the following structure as t-butylhydroquinone and magenta coupler is 10 per mole of silver genide.
．． It contains 5x 10-' moles and is coated to give a silver content of 230 g/m'. In addition, as an antioxidant, 2
,2.4-)dimethyl-6-lauryloxy-7-t-
0.30 mol of octylchroman was added per mol of coupler. 30 mg/m'' of di-t-octylhydroquinone dissolved and dispersed in the fourth dioctyl phthalate and 2-(2''-hydroxy-3',5''-di-butylphenyl)benzotriazole as an ultraviolet absorber; 2-(2'-hydroxy-s'-t-butylphenyl)benzotriazole, 2-(2''-hydroxy-3'-1-butyl-5
'-methylphenyl)-5'-chloro-benzotriazole and 2-(2'-hydroxy-3',5''-di-
t-Butylphenyl)-5-chloro-benzotriazole mixture (2: 1.5: 1.5: 2)5
The gelatin layer contains 00 mg/m'' of gelatin and is coated to give a gelatin of 1900+*g/rn'. Fifth layer: A red layer consisting of a silver chlorobromide emulsion containing 0.5 mol% of silver bromide. In the sensitive silver halide emulsion layer, the emulsion contains 500 g of gelatin per mole of silver halide and is sensitized using a sensitizing dye of the structure [rl]!, 5x10-S moles per mole of silver halide. , 50 mg of 2,5-di-t-butylhydroquinone dissolved and dispersed in dibutyl phthalate
/m' and the following structure as a cyan coupler: [C, -1
] per 51 moles of halogenide, and the silver content was 280 mg/rn'. Sixth layer: This is a gelatin layer, and gelatin is coated at 900 mg/ln'. The silver halide emulsions used in each of the light-sensitive emulsion layers (layers 1, 3, and 5) were prepared by the method described in Japanese Patent Publication No. 7772/1983, and were prepared using sodium thiosulfate pentahydrate. Chemically sensitized and stabilized with 4-hydroxy-6-
Methyl-1,3,3a,7-tetrazaindene (2.5 g per mole of silver halide), bis(vinylsulfonylmethyl)ether (1 g per 1 g of gelatin) as a hardening agent.
0B) and saponin as a coating aid. Sensitizing dye [I] Sensitizing dye [■] [Y-1] O [M-1] r, 0 Q [C-1] After exposing the color vapor produced by the above method, the next processing step and treatment The treatment was carried out using liquid. Processing steps (1) Color development 38°C 20 seconds (2) Bleach fixing 35°C 20 seconds (3) *Washing 30°C 1st tank 20 seconds 24
6th stitch 20 seconds (4) Drying 60℃~80℃ 30 seconds*
It is also called water washing alternative stabilization treatment. [Color development tank solution A] Benzyl alcohol 10g Ethylene glycol 10g Exemplary compound [II
-7] 00.3g potassium bromide
0.01g potassium chloride
2.3g potassium sulfite (50%
Solution) 0.5mM color developing agent (3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.0g diethylhydroxylamine (85%) S, 0g triethanol Amine 10.0g potassium carbonate
30g Ethylenediaminetetraacetic acid sodium salt 2.0g Fluorescent brightener (PK-
Conc) 2.0g of water was added to make the solution 141, and the pH was adjusted to 10.15 with potassium hydroxide or sulfuric acid. [Color developer replenisher A] Benzyl alcohol 15g Ethylene glycol 10g Potassium bromide
0.15g potassium chloride
3.0g potassium sulfite (50% solution) 1.5mJL color developing agent (3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 8.0g diethylhydroxylamine ( 85%) 7.0g triethanolamine 10.0g potassium carbonate
30g Ethylenediaminetetraacetic acid sodium salt 2.0g Fluorescent brightener (PK-
Conc) 2.5g of water was added to make one sentence, and the pH was adjusted to 10.40 with potassium hydroxide or sulfuric acid. [Otsu 1 White fixing tank liquid and replenisher] Diethylenetriaminepentaacetic acid ferric ammonium salt 60.0g Diethylenetriaminepentaacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0mJL5-amino-1,3,4-thiazole-2 - Thiol 0.5g Ammonium sulfite (40% solution) 27.5m, Q Adjust the pH to 6.50 with aqueous ammonia or glacial acetic acid, and add water to bring the total amount to IIL. [Water wash tank fluid and replenisher] Ortho-phenylphenol 1.0g 5-chloro-2-methyl-4-isothiazolin-3-one
0.02g 2-Methyl-4-isothiazolin-3-one 0.02g ethylene glycol 1.0g 2-octyl-4-isothiazolin-3-one 0
．． 01g1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3.0gB
iCjj3 (45% aqueous solution) 0.65
gMg5O, 7H*OO, 2g PVP (polyvinyl and lolidone) 1.0g
Ammonia water (ammonium hydroxide 25% aqueous solution) 2.5g Nitrilotriacetic acid trisodium salt 1.5g 1 with water!
Adjust the pH to 7.0 with aqueous ammonia and sulfuric acid. In the running process, the automatic developing machine is filled with the color developing tank solution A or the color developing solution Bft obtained by removing benzyl alcohol from the color developing tank solution A, and also with the bleach-fixing tank solution and the water washing tank solution. While processing the vapor sample, the above-mentioned color developing replenisher, bleach-fixing replenisher, and washing replenisher were replenished every 3 minutes through a metering pump. The amount to replenish the color developing tank is 1r of color paper.
18 (lsJl) per n', the amount of replenishment to the bleach tank was 220 m of bleach-fixing replenisher per 1 m', and the amount of replenishment to the washing tank was 250 m of washing replenisher per 1 m'. The washing processing baths of the developing machine are the first and second washing tanks in the direction of the flow of the photosensitive material, and the final tank is refilled, and the overflow from the final tank flows into the preceding tank. In the countercurrent method, the processing time for color development was adjusted using a speed controller.Wedge exposure was performed when the amount of color developer replenisher added to the color developer tank solution became three times the capacity of the color developer tank. Through the check sample, as an evaluation of residual color stain, the reflection density at 440 nts of a white background in an unexposed area and the reflection density after being left under direct sunlight for 1 hour are determined, and the difference is expressed as residual color stain.The reflection density is determined by spectrophotometric intensity. (manufactured by Hitachi, Ltd.). The results are listed in Table 1. Table 1 * Comparative sensitizing dye (1) ** Comparative sensitizing dye (2) CJs C1, -CHtSO As is clear from the results, compared to the comparative sensitizing dyes, the sensitizing dye of the present invention has improved residual color stain, and furthermore, by removing benzyl alcohol, the residual color stain is significantly improved. , B5-1]-5.BS-■-14 as a sensitizing dye
, B5-1]-Hl was also investigated, but the effects of the present invention were obtained. Example 2 The first, third and fifth layers of the photosensitive material of Example 1 were each coated with dyes of the present invention or comparison at a concentration of 100/rn'. The same evaluation as in Example 1 was performed by adding 50/rn' and 50/ni'. However, residual color stains due to water-soluble dyes are expressed by the spectral reflection density at 440 nm for yellow, 540 rv for magenta, and 540 nm for cyan. B5-1]-2 was used as the sensitizing dye for the first layer. The results are shown in Table 2. * Comparative dye (1) ** Comparative dye (2) *** Comparative dye (3) As is clear from the results in Table 2, AI dyes other than the present invention have a high residual color stain, and benzyl alcohol It can be seen that the presence of residual color stain further deteriorates the residual color stain. On the other hand, it can be seen that when the AI dye of the present invention is used and treated with a treatment solution that does not contain benzyl alcohol, the residual color stain is low. Note that dyes of the present invention include (33), (35), and (65).
). When (70) and (74) were also examined, the effects of the present invention were recognized. Example 3 During the processing steps of Example 1, the color development processing time and color developer were set as shown in Table 3, the sensitizing dye of the first layer in the light-sensitive material was set to B5-1]-3, and the third layer and The same evaluation as in Example 1 was carried out except that the AI dyes in the fifth layer were changed to (1G) and (48), respectively, and the maximum density of Blue was set to 100. The relative value was calculated when . However, the residual color stain represents the difference in reflection density from the reflection density immediately after treatment to the reflection density 1 hour after irradiation with direct sunlight for 440n++, and the difference from the reflection density without AI dye for 540n++ and 640n++. The results are shown in Table 3. Table 3 As is clear from the results in Table 3, when the photosensitive material of the present invention is used, residual color stain is reduced by eliminating pencil alcohol, and furthermore, dye images with sufficient density for practical use can be produced with short processing times. You can get it. Example 4 The light-sensitive material used in Example 3 was designated as the light-sensitive material (A) of the present invention, and the light-sensitive material (A) using Comparative Sensitizing Dye (1) and Comparative Dye 2.3 was used as a comparative light-sensitive material. Material (B), and after processing both of these light-sensitive materials (A) and (B) using color developer B according to the processing steps shown in Table 4, residual color stain (440 nm as a typical characteristic), desilvering property were obtained. (Measurement using fluorescent X-rays) and fading resistance after storage for 3 weeks at 60° C., 75% RH (relative humidity) was evaluated using cyan dye images. The fading rate (%) was calculated as a percentage of the cyan dye image before and after storage. The results are shown in Table 5. Table 4 * Shown as total time for 2 tanks. Table 5 As is clear from Table 5, when the processing time for one color development exceeds 25 seconds or the total processing time exceeds 2 minutes, image storage stability tends to deteriorate, and the sensitizing dye of the present invention,
It can be seen that the use of dye improves desilvering properties and residual color staining. Example 5 The magenta couplers used in Example 1 were
-1], or C-1, C-3, C-19 in the exemplified compounds shown in Japanese Patent Application No. 61-92655, pages 76 to 124.
C-30, C-58, C-76, or No. 81 of the same specification
Evaluations were carried out in the same manner as in Example 2, except that CC-2 or CC-8 in the exemplified compounds shown on pages 85 to 85 were substituted, respectively. As a result, the fading resistance of magenta was improved by about 30%, and the fading resistance of cyan was improved by 55%. [M-2] [M-3] [M-4] [M-5] ns [M-61 [M-71 [M-81 Call+70] [M-9] [M-10] [M-1] ] Example 6 Table 6 shows the silver halide emulsion in the photosensitive material used in Example 3.
Relative value when the maximum density of Blue when the same processing as in Example 1 (color development processing time 20 seconds) and color development processing at 35 ° C. 45 seconds as in Example 1 is carried out is 100. I asked for The results are shown in Table 6. Table 6 As is clear from Table 6, the silver chloride content must be at least 90 mol % in order to obtain a sufficient dye strength for practical use. Also, instead of diethylhydroxylamine in the color developer,
Examples A-2, A-3, A-18, A-21 and A-2
2, I was able to get a similar effect. Note that A-18 and A-21 had better development characteristics than diethylhydroxylamine. Patent Applicant: Konica Co., Ltd. Chief Brewer, Manager, Patent Attorney: Nobuaki Sakaguchi Chimoteta Neichisho (spontaneous) June 10, 1988 Patent Application No. 1983-30641 2 Name of the Invention Silver Halide Color Photographic Sensitivity Processing method of materials 3 Relationship with the case of the person making the amendment Applicant name (127) Konica Co., Ltd. 4 agent 160 address 160-1 Nishi-Shinjuku 7-chome, Shinjuku-ku, Tokyo 5th floor 6, Building 2 Number of inventions increased by amendment

Claims (1)

[Scope of Claims] In the step of subjecting a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer to color development treatment, bleach-fixing treatment, and water washing treatment, the silver halide color photographic light-sensitive material is as follows: General formula [A-1] or [BS-
1], the color developing solution used in the color development treatment does not substantially contain benzyl alcohol, the color development treatment time is 25 seconds or less, and the color development solution 1. A method for processing a silver halide color photographic light-sensitive material, characterized in that all processing steps including development processing time, bleach-fixing processing time and water washing processing time are within 2 minutes in total. General formula [A-1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 are -CN and -CFR, respectively.
_5R_6, -COR_7, -COOR_7 or -C
ONHR_5 is represented, R_5 and R_6 each represent a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 4 carbon atoms, and R_7 represents an alkyl group or an aryl group. R_3 and R_4 are each a hydrogen atom,
Represents an aliphatic group, an alicyclic group, an aromatic group, or a heterocyclic group. L
_1, L_2, L_3, L_4 and L_5 each represent a methine group. m and n each represent 0 or 1. General formula [BS-1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z_2_1 and Z_2_2 each represent an imidazole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, a pyridine nucleus, and a benzene nucleus, which may have a substituent. Represents an atomic group necessary to form an oxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, naphthoimidazole nucleus, or quinoline nucleus. R_2_1 and R_2_2 each represent an alkyl group or an alkenyl group that may have a substituent. X_2_1^■ represents an anion, and l_2_1 represents 0 or 1.