JPS6355547A - Color developing solution for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color developing soln. contg. a preservative harmless to the human body and easy to handle and inhibiting the lowering of the maximum density of a dye even after storage for a long period by combinedly using a specified hydrazine deriv. and a specified alkanolamine deriv. CONSTITUTION:This color developing soln. contains at least one kind of compd. represented by formula I and at least one kind of compd. represented by formula II. In the formula I, R1 is H, carbamoyl or the like, R2 is H, alkyl, aryl or the like, R3 is H, alkyl, aryl or the like and l=0 or 1. In the formula II, R4 is 2-6C hydroxyalkyl and each of R5 and R6 is H, 1-6C alkyl, 2-6C hydroxyalkyl or the like.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a color developing solution for silver halide color photographic R light-sensitive materials, and more specifically, to a silver halide color developer using a preservative to replace hydroxylamine, which is harmful to the human body and is a highly toxic substance. This invention relates to a color developing solution for color photographic materials. BACKGROUND OF THE INVENTION In color development, exposed silver halide is reduced to silver, and at the same time, an oxidized aromatic primary amine developing agent reacts with a coupler to form a dye. During this process, halogen ions generated by silver halide orphans are eluted into the developer and accumulate. Additionally, components such as heavy metal ions contained in other processing solutions are also carried into the color developing solution and accumulated therein by so-called pack contamination. The color developing solution used for such color development includes: Usually, sulfite or a water-soluble salt of ithite and hydroxylamine is added as a preservative (anti-oxidizing agent) to increase its preservation. Among these, as in the former, when sulfite is used alone, fogging occurs significantly over time, so by using a combination of sulfite m-salt and water-soluble salt of hydroxylamine as in the latter, it is possible to preserve the developer solution. Efforts have been made to significantly increase constancy and to reduce the occurrence of fog caused by aged developers. However, hydroxylamine has the following disadvantages. That is, firstly, it has been reported that hydroxylamine is harmful to the human body [for example, P, G-Stech-e
r,'The Merck Index An
Encyclopedia of Chera-
ical and DrugsJ (The Merck Index An Encyclopedia of Chemicals and Drugs) 8th, Ed, (1953
Year)]. Secondly, even with the Toxic Substances I & 1 Regulations, in order to handle and sell hydroxylamine salts, it is necessary to register as a general distributor of poisonous and deleterious substances and to establish a handler, which makes handling extremely inconvenient. However, it was difficult to handle, especially when amateur photographers processed it at home because it was dangerous. Thirdly, hydroxylamine is a kind of black and white developer and has silver developing properties with respect to silver halide. For this reason, the utilization efficiency of silver halide in silver halide color photographic light-sensitive materials is poor, and in order to obtain the desired dye density, it is necessary to use more silver halide and coupler in the light-sensitive material Neo, making it economical. This makes them extremely disadvantageous. Furthermore, fourthly, when hydroxylamine is mixed with heavy metal ions (e.g. iron ions, copper ions, etc.) in the color developing solution, it decomposes into ammonia, which causes fogging on color photosensitive materials and improves photographic performance. Zero-color developing solutions, which have the disadvantage of having negative effects on The amount of heavy metal ions accumulated in the color developer is increasing. For this reason, the fourth problem, ``occurrence of fog'' caused by the decomposition of hydroxylamine, is becoming more severe. Therefore, when color photo processing and color copying using a color development method are carried out in stores (so-called minilabs) in the future, there is a strong desire to develop a preservative that can replace hydroxylamine due to pollution concerns. . As preservatives to replace hydroxylamine, 2-anilinoethanol and dihydroxyalkenes have been proposed in US Pat. No. 3,823,017 and US Pat. No. 3,615,503, respectively. However, all of these compounds are unstable in themselves and have no preservative effect in color developing solutions. On the other hand, sucrose is known as a preservative in developing solutions (for black-and-white photography) containing heydroquinone or N-alkyl-p-aminophenol as a developing agent; Color developing solutions containing amines as developing agents have little effect as preservatives. Furthermore, ascorbic acid and its derivatives are known as preservatives for black-and-white photographic developers and color developers, but they have the disadvantage of inhibiting color development and causing a significant decrease in color density; Inferior to amines. Furthermore, α-hydroxy aromatic alcohols described in JP-A No. 52-7779, hydroxamic acid compounds described in JP-A-52-27638, and α-described in JP-A No. 52-143020.
Aminocarbonyl compounds and monosaccharides described in No. 52-102727, and amino m derivatives described in No. 52-140324 are disclosed. However, when monosaccharides and amino acid derivatives are used in large quantities,
Although it shows considerable stability at room temperature, it does not decompose due to heat and has the property of not being a pollution hazard. D-glucosamine and hydrochloride are known as typical α-aminocarbonyl compounds, but this compound has poorer preservability than hydroxylamine. Hydroxamic acid compounds have the same level of stability as hydroxylamine, but have the drawback of high cost. Therefore, in order to solve the above-mentioned drawbacks and provide a preservative that can replace hydroxylamine, the present inventor investigated hydrazine, which is conventionally known as a photographic additive to be included in light-sensitive materials, and found that hydroxylamine Compared to the standard, the preservability was extremely insufficient or the solubility was poor, or even if the preservability was present, the silver developability was too strong and the color development efficiency was extremely low, making it very difficult to put it into practical use. Therefore, the present inventor conducted repeated research on such hydrazine derivatives and found that a specific hydrazine derivative exhibits considerably high stability and also shows little decrease in coloring efficiency. However, further studies by the present inventors have revealed that the maximum dye concentration of color developing solutions containing this hydrazine derivative decreases when stored over time. [Objective of the Invention] The object of the present invention is to solve the above-mentioned drawbacks and to provide a coloring agent that contains a preservative that is harmless to the human body and easy to handle, and that suppresses a decrease in the maximum pigment concentration even after long-term storage. The purpose is to provide a developer. [Means for Solving the Problems] The color developing solution for silver halide color photographic materials of the present invention which achieves the above object comprises at least one compound represented by the general formula [A] and a compound represented by the general formula [B]. It is characterized by containing at least one of the compounds shown below. General formula [A] 1'1. -NH-+N+-1ZR. [Wherein, n represents a hydrogen atom, a carbamoyl group, an aryl group, an alkyl group, an acyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a heterocyclic group, and R2 represents a hydrogen atom, an alkyl group, an aryl group, represents an alkoxy group, aryloxy group, hydroxy group, heterocyclic group, amino group, or hydrazino group, Rz represents a hydrogen atom, an alkyl group, or an aryl group, standing is 0 or l, and when 1 is 0, 2 is -co-, -c-, -3O,-. When the sentence is 1, Z represents -co-, -c-, -so, -, and R is synonymous with R3. ] General formula [B] [wherein R4 is a hydroxyalkyl group having 2 to 6 carbon atoms,
R5 and It are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group, or a formula number; represents an alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms] [Function of the Invention] Hydrazine has been known as a photographic additive for light-sensitive materials, but for example, hydrazine derivatives of the following types are disclosed in U.S. Patent No. 3,227. , No. 552, JP-A No. 55-5.21120, No. 55-90940, No. 56-67843, No. 5
No. 3-211921, No. 53-20932, No. 60-
As described in No. 140340, it has been mainly added to photosensitive materials, used in ultra-high contrast forming methods in photolithography, or directly used as a fogging agent for positives. Also, in US Pat. No. 3,141,771, certain hydrazine derivatives were used as aldehyde scavengers in a reversal process. However, according to research conducted by the present inventor, it has been found that certain hydrazine derivatives exhibit high stability. However, it has been found that this hydrazine derivative causes a problem in that a color developing solution containing the hydrazine derivative decreases in concentration when stored over time. This is probably because hydrazine and certain tumor derivatives decompose during storage, and the concentration decreases due to the decomposition products. In order to solve these problems, the present inventors have found that by using a combination of a specific hydrazine derivative and an alkanolamine derivative, the problem of concentration reduction thought to be caused by the above-mentioned decomposition products can be solved. Alkanolamine derivatives. For example, U.S. Patent No. 3,823,017 describes that it can be used as an antioxidant in color developing solutions, but it has not been found that the combination use with hydrazine derivatives has the effect of preventing the concentration from decreasing during storage over time. It was truly surprising. Furthermore, if a hydroxylamine derivative is used in conjunction with the present invention, the stability will be synergistically improved. However, it was found that the effect of ffi< is observed in that it also suppresses the occurrence of staining, which is considered to be due to insufficient decolorization of the iAI dye. [1i! rJI(7)4IJl&] The present invention will be explained in detail below. First, the general formula [A] will be explained. The carbamoyl group represented by (1) includes a number of substituted groups, such as carbamoyl group, N,N-dimethylcarbamoyl group, N-methylcarbamoyl group, N,N-tetramethylenecarbamoyl group, etc. . Examples of the aryl group represented by R1 include substituted groups, such as phenyl group, p-methoxyphenyl group, p-
Aminophenyl group, p- and dorazinophenyl group, 0-aminophenyl group, p-sulfophenyl group, 2.5-disulfophenyl group, p-tolyl group, p-sulfamoylphenyl group, p-carboxyphenyl group and p-guanidinophenyl group. The alkyl group represented by R1 includes linear, branched, and cyclic groups, such as methyl group, ethyl group, isobutyl group, pentyl group, cyclopentyl group, and cyclohexyl group, and these alkyl groups include substituents. The substituent also includes those having a substituent (1) such as a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom)
, hydroxyl group, carboxyl group, alkoxycarbonyl group (e.g. ethoxycarbonyl group), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group), alkoxy group (e.g. methoxy group, ethoxy group, butoxy group), sulfo group, Alkylsulfonyl group (
For example, methanesulfonyl group, ethanesulfonyl group), sulfamoyl group (for example, sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group),
Amino groups (e.g. amino group, dimethylamino group), piperidino group, morpholino group, amide group (e.g. acetylamide group, benzoylamide group), vinyl group, aryl group (e.g. phenyl group, p-dimethylaminophenyl group, p- sulfophenyl group), ammonium group (e.g. metamethylammonium group, metaethylammonium group)
, a phosphonium group (eg, triphenylphosphonium group), and the like. The acyl group represented by R1 includes aliphatic and aromatic groups, such as acetyl group, propionyl group, benzoyl group, p-sulfobenzoyl group, p-N,N-dimethylaminobenzoyl group, p-carboxybenzoyl group, ■−
Examples include various groups such as hydroxybenzoyl group. The sulfamoyl group represented by R includes groups having a 2I substituent, such as a sulfamoyl group, an M,N-dimethylsulfamoyl group, and a morpholinosulfonyl group. Examples of the alkylsulfonyl group represented by R1 include methanesulfonyl group and benzylsulfonyl group, and examples of the arylsulfonyl group represented by R1 include benzenesulfonyl group, p-toluenesulfonyl group, p-
Examples include various groups such as carboxybenzenesulfonyl group. The heterocyclic group represented by R1 includes saturated and unsaturated groups, such as furyl group and chenyl group. Pyridyl group, sulfopyridyl group, pyrimidyl group. Various groups such as an imidazolyl group and a benzothiazolyl group can be mentioned. Next, the alkyl group, aryl group, and heterocyclic group represented by R2 have the same meaning as the alkyl group, aryl group, and heterocyclic group represented by R+, and include those having the same substituent as the W1 substituent in R8. The alkoxy group represented by R1 includes those having a substituent, such as methoxy group, ethoxy group, 2
-hydroxyethoxy group, tosulfoproboxy group, and the like. The aryloxy group represented by R3 includes those having a substituent, such as a phenoxy group. The amino group represented by R3 includes those having a substituent, such as an amino group, a methylamino group, an anilino group, and a p-aminocarbamide anilino group. Next, the alkyl group and aryl group represented by R2 have the same meaning as the alkyl group and aryl group represented by R1, and include those having the same substituents as R1. Specific compounds of the hydrazine derivatives used in the present invention are shown below, but the present invention is not limited to these compounds. [Exemplary Compounds] (1) N13. NHCNL・HCl2(2')
N)1. NHCNHNH*(3) NH! N.H.
CNHffi NH (4) NH,N! ICNHCl! . (9) l0CI1. CI(,-NON)It
OsNa N HCl2 These compounds are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate, and the like. The above compounds may be added alone to the color developing solution, or
It is also possible to add more than one species in combination. The amount added is preferably from 0.1 g to SOg per color developer, more preferably from 0.3 g to 30 g. Next, in the color developing solution of the present invention, those used in combination with the hydrazine conductor represented by the general formula [A] are those of the general formula [A].
B] is an alkanolamine derivative represented by [B]. In particular, in the compound represented by the general formula [B], R4 is a hydroxyalkyl group having 2 to 4 carbon atoms, R% and R6 are each an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 2 to 4 carbon atoms, respectively.
Those showing a hydroxyalkyl group of 4 are preferred. Preferred specific examples of the compound represented by the general formula [B] are as follows. Ethanolamine, jetanolamine, triethanolamine, di-isopropanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2-propanol, 3-diethylamino-1-propatur, 3-dimethylamino-
1-propanol, isopropylaminoethanol, 3
-Amino-1-propatol, 2-amino-2-methyl-1,3-propanediol, ethylenecyamine titritesbrobanol, benzyljetanolamine, 2-
Amino-2-(hydroxymethyl)-1,:I-propanediol. Among these, ethanolamine and jetanolamine are preferred, and ethanolamine is particularly preferred. The above compounds may be added alone to the color developing solution, or
It is also possible to add a combination of s or more. The amount added is preferably 0.1 g to 50 g, more preferably 0.3 g to 30 g per color developer li. It is preferable that a hydroxylamine derivative represented by the following general formula [C] is used in combination with the color developing solution of the present invention.
The combined use of these compounds not only synergistically improves the preservation property but also suppresses the occurrence of staining, which is considered to be caused by insufficient decolorization of the so-called AI dye. General formula [C] In general formula [C], Ry and Ra are hydrogen atoms, or carbon a
1 to 5 alkyl groups, including those having a substituent, provided that Ry and R8 are not hydrogen atoms at the same time. Examples of substituents include sulfonic acid groups, hydroxy groups, alkoxy groups (methoxy, ethoxy, propyloxy, etc.), carboxy groups, amino groups, etc., and these are described, for example, in U.S. Patent No. 287.125, Same 3,
Examples include hydroxylamines described in No. 293,034 and No. 3,287,124. Among the compounds represented by the general formula [C], preferred are those in which one of Rt and Ra is a hydrogen atom and the other is a lower alkyl group. Preferred specific exemplary compounds represented by the general formula [C] are shown below. (1) CH3-Nil-0H (2) C,)1%-NH-011 (3) 1so-C,tl, -NH-0)1(')
CJy-NH-OH (5) 110-CHt-NH-OH (6) C
113-0-C,11,-NH-OH(7) jlo
-C,H,-NH-OH(8)! 100cmC,O
, -N11-011(9) 1103s-C2H4-
NH-011 (10) Hall-Cillb-Nu-
Oll('1) Ca11%-0-C*ll4-Nto0
ft(12) 110-C,11,-0-Ctl14-
Nil-OH These compounds are usually hydrochlorides, sulfates,
It is used in the form of salts such as p-toluenesulfonate, oxalate, phosphate, and acetate. The concentration of the compound represented by the above general formula [C] in the color developer is usually 1, for example, preferably from 0.1 g/l to 50 g/ml, more preferably from 0.3 g/l to 30 g/ml, Particularly preferred is 0.5 g/l to 20 g/liter. Furthermore, two or more of the above compounds may be used in combination. The mixing ratio of the compound represented by the general formula [A] and the compound represented by the general formula [B] is preferably 1:IQO to 50:1, more preferably 1:58 to 25:1. Compounds that can be used in the color developing solution of the present invention include sulfites in addition to the compounds represented by the general formula [A], [B], or [C]. Examples of sulfites include sodium sulfite, potassium sulfite, and bisulfite f! Examples include sodium acid, potassium bisulfite, etc., and the amount added is 2 x 10-' moles or more, preferably 5 x 10-' moles or more per 11 color developing solutions.
The color developing agent used in the color developing solution of the present invention is p-phenylenediamine type having a water-soluble group. The compounds are preferable from the viewpoint of obtaining the effects of the present invention. p-phenylenediamine compounds having a water-soluble group are
Compared to p-phenylenediamine compounds that do not have a water-soluble group such as N,N-diethyl-p-phenylenediamine, it does not contaminate photosensitive materials and has the advantage of not causing skin irritation. In particular, in the present invention, the object of the present invention can be effectively achieved by combining the compound represented by the general formula [A] and the compound represented by the general formula [B]. 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. -(CIl, -(:II!0H1 -(CIl, 1.-NH9O*-(C11, -CH
3゜-(C11,), -0-(C112) 1l-C1
1,. -(C111CI+20)nc*Htm++ (II and n each represent an integer greater than or equal to 0, ), -CO
Preferred examples include OH group and -5O,11 group. Specific examples of color developing agents preferably used in the present invention are shown below. [Example color developing agent] MHL 10) H\/CH, C0OH NH3 11) C mountain\/(C)ltcH*0)tcHsN)In 12) C mountain\/(CIl, CH, 0) ICH. The above color developing agent is usually used in the form of a salt such as hydrochloride, sulfate, p-toluenesulfonate, etc., and is usually used in the range of I x 10-' to 2 x 10-mol per 12 color developing solution. However, from the viewpoint of rapid processing, 1.5 x 10-' to 2 x 10 per color developer
-' molar range is more preferred. The color developer of the present invention may contain the following developer components in addition to the above components. Examples of alkaline agents include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, silicates, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. alone or in combination. It can be used. In addition, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borates are used for purposes such as preparation needs or to increase ionic strength. Something will happen. Additionally, inorganic and organic antifoggants can be added as necessary. Yet again. A development accelerator can also be used if necessary. As a development accelerator, U.S. Patent No. 2.648,6
No. 04, No. 3,871,247, 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, 2,577.127, and 7-ionic compounds such as polyethylene glycol and its derivatives, polythioethers described in Japanese Patent Publication No. 44-9504, and organic solvents described in Japanese Patent Publication No. 44-9509. and organic amines such as ethanolamine, ethylenediamine, jetanolamine, and triethanolamine. Benzyl alcohol, also described in U.S. Pat. No. 2.304.1125. In addition to phenethyl alcohol, examples include acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, and ammonia. Furthermore, the color developing solution of the present invention may optionally contain ethylene glycol, methyl selonlube, methanol, acetone, dimethylformamide, β-cyclodextrin, and others such as Japanese Patent Publication Nos. 47-33378 and 44-9509.
Organic solvents described in each publication can be used to increase the solubility of the developing agent. Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include 1, 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. .01 g to log/JL is preferable. In addition, if necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor-releasing coupler (so-called DIR coupler), a development inhibitor-releasing compound, etc. are added. can do. Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multilayer effect accelerator can be used. It is preferable to use a triazylstilbene fluorescent brightener in the color developing solution of the present invention, and as the triazylstilbene fluorescent brightener, a compound represented by the following general formula CI] is preferably used. General formula [I] In the formula, X1++ X12 + Yll and Y,! each represents a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (e.g., methoxy, ethoxy, methoxyethoxy, etc.), an aryloxy group (e.g., phenoxy, p-sulfophenoxy, etc.), an alkyl group (e.g., methyl, ethyl, etc.) ). Aryl group (e.g. phenyl 1.methoxyphenyl etc.)
, amino group, alkylamino group (e.g. methylamino,
ethylamino, pro-ruamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di(
β-hydroxyethyl)amino, β-sulfoethylamino, N-(β-sulfoethyl)-N'-methylamino,
N-(β-hydroxyethyl-N'-methylamino, etc.)
, arylamino groups (e.g. anilino, o+, m+, p
-sulfoanilino, 0-lm-, p-chloroanilino,
o-1m-1p-toluidino, o-1m-1p-carboxyanilino, 0-lm-, p-hydroxyanilino,
0M representing sulfonaphthylamino, 0-1m-1p-aminoanilino, olm-, p-anilino, etc.) is a hydrogen atom, sodium. Represents potassium, ammonium or lithium. Specifically, the following compounds may be mentioned, but the invention is not limited thereto. Below is the margin [Exemplary compounds] OOH OOH. %-J'1 w Z These triadylstilbene-based brighteners are 1For example, Chemical Industry Association Line "Fluorescent Brighteners" (published in August 1976)8
It can be synthesized by the usual method described on page 1. These triadylstilbene type brighteners are preferably used in an amount of 0.2 to 20 g, particularly preferably 0.4 to 10 g, per color developer of the present invention. The color developing solution used in the present invention has the following general formula (K-1
), (K-11), and (K-1[[) It is preferable to contain a chelating agent represented by [[]. General formula (K-1) A-COOM general formula CK-I
f) B-PO8MM1-1 In the formula, A and B each represent a -valent group or atom, and may be an inorganic substance or an organic substance. D represents an aromatic ring or a heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom. The general formula (K-1), (K-11) or (K-III)
The chelating agent represented by ) has the following general formula (K-mV) to (
It is a compound represented by any one of K-XV). General formula (K-N) Mslhlosm+General formula (K-V) Mn, + Pn, Osl+”
General formula (K-VJ) A, -R, -2-1? ,
-COOH cycloalkylene group, phenylene group, -Rt
o R? -1-R-r"o R, OR - or -Rq
Z represents Rq-, Z is >N-R7-As or >NAi
, R3 to R7 each represent a substituted or unsubstituted alkylene\ group, and A and ~A are each a hydrogen atom, -OH, -
Co. M or -POaMt, M represents a hydrogen atom or an alkali metal atom, and is an integer of 3 to 6, nl is 2 to 20
represents an integer. General formula [K-■) RJ(CHtPOsM*) *In the formula, R@ is a lower alkyl group, an aryl group, an aralkyl group, or an enriched 6-membered ring group [10H, -OR or - as a substituent]
〇〇〇M], M represents a hydrogen atom or an alkali metal atom. Bt Bt Bs In the formula, R0 to R11 are each a hydrogen atom, OH, lower alkyl (unsubstituted or as a substituent 10H, -C00M or -
P OsM t), B, -B
s is each hydrogen atom, -〇H, -COOM, -POs
(M)* or -N (J)*, where J is a hydrogen atom, a lower alkyl group, C1)(,0)(or -POaMt
, M represents a hydrogen atom or an alkali metal, and n and 1 each represent 0 or 1. General formula (K-X) 9M! ? ,,-P-0-OR,. In the formula, R12 and R1 each represent a hydrogen atom, an alkali metal atom, an alkyl group of 01 to CI2, an alkenyl group of C8 to C1t, or a cyclic alkyl group. In the formula, R + 4 Cr - Ct * (7) 7 k Kill group, C
, -C1, alkoxy group, CI'-C1! monoalkylamino group / dialkylamino group of K-C* to CI*,
Amino group, allyloxy group of CI-CI4, C* ~ Ct
%Q represents the arylamino group and amyloxy group of 4
1 to Q are each an alkoxy group of -OH, C, NO,,
-0MI (M+ represents a cation), an amino group, a morpholino group, a cyclic amino group, an alkylamino group, a dialkylamino group, an arylamino group, or an alkyloxy group. General formula (K-Xll) represents a halogen atom, a sulfonic acid group, a substituted or unsubstituted phenyl group. R□, RjaxR1+ and Ryu each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. n represents an integer of 1 to 3. Rlg may be the same or different. RIM is preferably a sulfonic acid group. Or represents a sulfo group. General formula (K-XV) In the formula, R1° and R3° are each a hydrogen atom, a phosphoric acid group, a carboxylic acid group, -CH*C0OH, -'CHtPOsH1
or a salt thereof, X represents a hydroxyl group or a salt thereof, and W8, Z+ and Y+ each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a salt thereof , represents an alkoxy group or an alkyl group. Also ~3 is 0 or 1. n= is an integer from 1 to 4,! , is l or 2, p is an integer of 0 to 3, Q+ is 0 to
Represents an integer of 2. Specific examples of the chelating agent represented by the general formula (K-TV: l to (K-XV) T: h) include the following: [Exemplary chelating agent] (1) Na5PaO0t (2) Na5P
sO*(3) H, P, Ot (4) Hs
PsOl(5) Na5PaO0 C stomach. (27) (2g) PO
8H! PO, H1 (29)
(IQ)CHmPOaHt
POJt(37)
(3g) C-Ha CCoon PO-H! 1':)! . CHmPOaHt CH＊OH
0H (JH CHl POJ. OH ml, 0.P-C-PO3)1゜, / ” %- CtBs H (80). HOCHzCH(O)ri -CIItOP (ONa
)-HOCH-CHxOP (OR)t HOCH*CHg op (ONa) CHl0R 10-CHt-CB-CHt-OP (OB)*ut HJ-CHtCH*-0-P (OR)*HJ-Coo
-P-(Owa. (72). ■sc COOP (OH)* CJsOP 0CJs H O 1!11 COOHCool CHtPOsFlat CH*COONa C1(*C00NaC1(,C
00I+ In the present invention, general formulas (K-IV), (K-V), (
K-■]6[K-■), (K-IK), (K-■] or (K-XV) It is more effective to use a chelating agent represented by the general formula [K- -■], [K
-■] Alternatively, a chelating agent represented by (K-XV) is used. In the present invention, particularly preferred are chelating agents (6) and (7). (14), (19), (31), (44), (81),
The method is to use a chelating agent represented by (82), (9G), (94) or (99). Two or more of these chelating agents can also be used in combination. The above general formulas (K-1) to (K-Il) used in the present invention
The chelating agent shown in either l) is a color developer IQ.
It is preferable to add in the range of txlo-'mol-1 mol per txlo-'mol, more preferably 2X10-4 to lXl0°
It can be added in an amount of 1 mol, more preferably 5 mol.
xl (I' to 5 x 10-" moles). Each component of the above color developing solution can be prepared by sequentially adding and stirring to a certain amount of water. In this case, the solubility in water Low-level components can be added by mixing them with the above-mentioned organic solvents such as triethanolamine.More generally, multiple components that can coexist stably are added in a concentrated aqueous solution or in a solid state in a small container. The color developing solution of the present invention can be obtained by adding a previously prepared solution to water and stirring to obtain the color developing solution of the present invention.The color developing solution of the present invention can be used in any pH range, but from the viewpoint of rapid processing, pH 5 to It is preferably p) 12.0, more preferably p) 19.8 to 12.0, particularly preferably p) 1O60 to 11.5. The processing temperature for color development using the color developer of the present invention is: 3
The temperature is preferably 0°C or higher and 50°C or lower, and the higher the temperature. It is preferable because it enables quick processing in a short time, but there is also the problem that the retention property tends to deteriorate, so it is more preferable to use
The temperature is preferably from ℃ to 45℃. After color development using the color developing solution of the present invention, processing is performed with a processing solution having a fixing ability, but if the processing solution having a fixing ability is a fixing solution, a bleaching treatment is performed before that. As the bleaching agent used in the bleach solution or bleach-fix solution used in the bleaching step, metal complex salts of 11 acids are preferably used. The metal complex salt has the effect of oxidizing the metallic silver generated during development and converting it into silver halide, and at the same time coloring the uncolored part of the color former, and its structure is based on aminopolycarboxylic acid, oxalic acid, citric acid, etc. It is made by coordinating metal ions such as iron, cobalt, and copper with an organic acid. 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 are alkali metal salts. It may be an ammonium salt or a water-soluble amine salt. Specific representative examples of these include the following. Ill Ethylenediaminetetraacetic acid

[2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N' -
) acetic acid

[41 Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [81 Cyclohexanediaminetetraacetic acid [71 Iminodiacetic acid] [8] Dihydroxyethyl glycine citric acid (or tartaric acid) 19) Ethyl ether diamine tetraacetic acid 0]
glycol ether amine tetraacetic acid

[11] Ethylenediaminetetrapropionic acid

[12] Phenylenediaminetetraacetic acid

[13] Ethylenediaminetetraacetic acid disodium salt

[14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt

[151 Ethylenediaminetetraacetic acid tetrasodium salt [181 Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediaminetetraacetic acid sodium salt [17] Ethylenediaminetetraacetic acid sodium salt]
Propylene diamine tetraacetic acid sodium salt [19] 2) Lilotriacetic acid sodium salt 120]
Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and may also contain various additives. As additives, in particular alkali halides or ammonium halides. For example, it is desirable to contain rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, metal salts, and chelating agents.
pH buffering agents such as salts, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions can be added as appropriate. Further, the fixing solution and the bleach-fixing solution include xam ammonium,
Sulfites such as potassium sulfite, ii.sodium sulfite, ammonium metasulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
pH1 consisting of various salts such as sodium bicarbonate, potassium carbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
It can contain one or more kinds of i-shock agents. When processing is carried out while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) contains thiosulfur M11! , may contain thiocyanate or sulfite, etc.
These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In order to increase the activity of the bleaching solution and the bleach-fixing agent, air or oxygen may be blown into the bleach-fixing bath and the bleach-fixing replenisher storage tank, or a suitable oxidizing agent may be used. 1. For example, hydrogen perhydrogen, bromate, persulfate, etc. may be added as appropriate. The pH of the bleach-fix solution preferably used in the present invention is 3.0.
~S, O is preferred, and the range is more preferably 4.0 to 8.0. In addition, in washing with water after bleach-fixing or processing with a water-washing substitute stabilizing solution, IR may be recovered by a known method from a processing solution containing a soluble tII complex salt such as a fixing solution and a bleach-fixing solution. For example, electrolysis ( Buddhist temple patent 2,299,
687), precipitation method (Japanese Unexamined Patent Publication No. 52-73037, German Special Fraud No. 2,331,220), ion exchange method (Unexamined Japanese Patent Publication No. 52-73037),
No. 1-17114, German Patent No. 2,548,237) and metal li conversion method (British Patent No. 1,353,805) can be effectively used. After color development using the color developer of the present invention. After bleaching and constant H (or bleach-fixing) treatment, stabilization treatment may be performed without washing with water, or washing with water and subsequent stabilization treatment may be performed.In addition to the above steps, hardening, neutralization, Typical examples of preferred processing methods include the following steps, in which known auxiliary steps may be added as necessary, such as black-and-white development, reversal, and washing with a small amount of water. (1) Color development, bleaching, fixing → washing with water (2) Coloring development → bleaching, fixing → washing with a small amount of water, washing with water (3) Coloring development → bleaching feet → washing → stable (4) Color development, bleaching, fixing → stable (5) Color development → bleach fixing → first stability → second stability (8)
Color development → washing with water (or stable) → bleach-fixing → washing with water (also stable) (7) Color development → stop → bleach-fixing → washing with water (also stable to stable) (8) Color development → bleaching → washing with water → feet Young → Washing with water → Stable (9 colors) Color development → Bleaching → Fixing → Washing with water → Stable (10) Color development → Bleach pass, minimum water wash, fixation → 1st stable → 2nd stable (11) Color development → Bleach → Wash with a small amount of water → Constant S → Wash with a small amount of water →
Washing with water → stable 02) Color development → bleaching → wearing → stable (] 3) Color development → stop → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → washing with water Stable Color positive film, color positive paper, color reversal film for slides, color reversal film for movies,
Color reversal film for TV 1 Applicable to color photosensitive materials such as reversal color paper. There are no particular limitations on the light-sensitive material processed with the color developing solution of the present invention.9 For example, the crystals of silver halide grains may be normal crystals, twin crystals, or other crystals, with [1-0,0] 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 or phase structure (core-shell type) in which the inside and outside are different. In addition, these silver halides may be of a type in which a latent image is mainly formed on the surface or in a type in which a latent image is formed inside one grain. (see Japanese Patent Application No. 59-170070). The silver halide grains mentioned above are preferably substantially monodisperse, and may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method. Incidentally, since the particle size distribution of the monodisperse emulsion is almost a normal distribution, the standard deviation can be easily determined. From this, the relational expression It is as follows. In the case of spherical silver halide grains, the 1 grain size is the diameter thereof, and in the case of grains other than 1 sphere, it is calculated by converting to a sphere with the same area. The above-mentioned silver halide may be obtained by preparing seed grains by an acidic method and then growing them by an ammonia method, which has a high growth rate, to a predetermined size. When growing silver halide grains, the pH in the reaction vessel,
pjlg etc., for example, JP-A-54-48
It is preferable to sequentially and simultaneously implant and mix silver ions and l\ride ions in amounts commensurate with the growth rate of silver I\Rolodide grains as disclosed in No. 521. These silver halide emulsions are composed of activated gelatin; sulfur sensitizers such as T & yellow sensitizers such as 7lylthiocarbamide, thiourea, °cystine; selenium sensitizers; reduction sensitizers such as stannous salts, dioxide, etc. Thiourea, polyamines, etc.; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc., or such as ruthenium, palladium, platinum, rhodium Ms sensitizers are water-soluble salts such as , iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate and sodium chloroparadate (these types can be used as sensitizers or fog suppressants depending on the amount) etc.) alone or in appropriate combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). Good too. The silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing heterocyclic compound having at least one hydroxytetrazaindene and mercapto group is added. At least one kind may be contained. Silver halide is optically prepared by adding a sensitizing dye in an amount of 5 x 1G-8 to 3 x 10-3 mol per mol of silver rhodanide in order to impart photosensitivity to the desired wavelength range. Various sensitizing dyes may be used for sensitization, and each sensitizing dye may be used alone or in combination of two or more. In addition, in the light-sensitive material to which the present invention can be applied, a red-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer each contain a coupler, that is, a dye formed by reacting with an oxidized product of a color developing agent. It is preferable to use a compound containing a compound capable of forming . Yellow couplers that can be used include closed ketomethylene compounds, active point -〇-aryl substituted couplers called so-called two-equivalent couplers, active point -〇-acyl substituted couplers, active point substituted couplers with hydantoin compounds, and active point substituted couplers with urazole compounds. Couplers and active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers. Active point -0-sulfonyl substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Patent No. 2,875,0
No. 57, No. 3,2E15,508, No. 3,408,1
No. 94, No. 3,551,155, No. 3,582,32
No. 2, No. 3,725.072, No. 3,891,445
No., West German Patent No. 1,547,868, West German Application Publication No. 2,
No. 2111.917, No. 2,281,381, No. 2,
414,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133,
No. 4B-73147, No. 51-102636, No. 5
No. 0-6341, No. 50-123342, No. 50-1
No. 30442, No. 51-21827, No. 50-876
No. 50, No. 52-82424, No. 52-115219
No. 58-95346, etc. can be mentioned. Magenta couplers that can be used include pyrazolone,
Examples include pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds. These magenta couplers are similar to the yellow couplers 4
Specific examples of magenta couplers that can be used include not only equivalent type couplers but also 2-equivalent type couplers, such as U.S. Pat. No. 2,800,788 and U.S. Pat.
No. 3,0132,853, No. 3,127.2H, No. 3,311,478, No. 3,419.391,
No. 3,519,429, No. 3,558,319, No. 3,582,322, No. 3,815,506, No. 3
, No. 834,908, No. 3,891,445, West German Patent No. 1,810,484, West German Patent Application (OL S)
No. 2,408,685, No. 2,417,945,
No. 2,418,959, No. 2,424,487, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826/1982, No. 52-58922, No. 49-129538. No. 49-74027, No. 50-159336, No. 5
No. 2-42121, No. 49-74028, No. 50-6
No. 0233, No. 51-26541, No. 53-5512
No. 2, Japanese Patent Application No. 110943/1987, and the like. Examples of cyan couplers that can be used include phenolic and naphthol couplers. These cyan couplers may be not only 4-equivalent type couplers like the yellow couplers but also 2-equivalent type couplers. Specific examples of cyan couplers that can be used include U.S. Pat. Nos. 2,389,929 and 2,434. ,27
No. 2, No. 2,474,293, No. 2,521,908
No. 2,895,8211, No. 3,034.882
No. 3,311,478, No. 3,458.315, No. 3,478,563, No. 3,583,971,
No. 3,591,383, No. 3,787,411, No. 3,772,002, No. 3,933,494, No. 4
, No. 004,929, West German Patent Application (OLS) 2.41
No. 4,830, No. 2,454,329, Japanese Unexamined Patent Publication No. 1973-
No. 59838, No. 51-26034, No. 48-505
No. 5, No. 51-146827, No. 52-69624, No. 52-90932, No. 58-95346, and Japanese Patent Publication No. 11572-1972. A coupler such as a colored magenta or colored cyan coupler or a polymer coupler may be used in combination in the silver halide emulsion layer and other photographic materials. -193611, and regarding the polymer coupler, the patent application filed in 1983 by the applicant.
-172151 can be referred to. Although the amount of the coupler added is not limited, it is preferably IX10-3 to 5 mol, more preferably 1X10-2 to 5X10-1 mol per mol of silver. The silver halide color photographic light-sensitive material to which the present invention can be applied may contain various other photographic additives. Agents, color stain inhibitors, optical brighteners, one-color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. Hydrophilic colloids used to prepare emulsions in silver halide color photographic materials include gelatin,
Derivatives of gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, seishin powder derivatives, polyvinyl alcohol, polyvinylimidazole, polyacrylamide, etc., singly or in combination. Synthesis of polymers, hydrophilic polymers, and any other polymers are included. Supports for silver halide color photographic light-sensitive materials include reflective supports and transparent supports such as baryta paper and polyethylene-coated paper, and these supports are appropriately selected depending on the intended use of the light-sensitive material. In the light-sensitive material to which the present invention can be applied, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and various layers such as a filter layer, anti-curl layer, anti-curl layer, anti-halation layer, etc. can be used in appropriate combination as a constituent layer. Hydrophilic colloids that can be used in the emulsion layer as described above can be similarly used as a binder in these structures 1 and layers, and can also be contained in the emulsion layer as described above. Various photographic additives can be included. AI is used in photosensitive materials to improve so-called sharpness and adjust sensitivity.
Dyes can be used, but stains are likely to occur when AI dyes are used, especially those of the following general formula [AI-II, F
This is likely to occur when AI dyes shown in AI-Ill, [Al-ml, or [AI-IVI] are contained. Therefore, in the present invention, even when the above-mentioned dyes are used, staining is less likely to occur. General formula (Ar-rl In the formula, Rf, Rf+, Rf2. Rf3. Rf
s and Rfs are hydrogen atoms; halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom); hydroxy group: alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (methyl group,
ethyl group, propyl group); alkoxy group (e.g. methoxy group, ethoxy group, propoxy group)'; -503M
or -NHCH2SlhM group, is a one-member cation, and is an alkali metal (e.g., sodium atom, potassium atom); ammonium, organic ammonium salt (e.g., pyridium, piperidinium, triethylammonium,
triethanolamine), etc. Representative specific examples of the compound represented by the general formula [AI-II] are shown below, but the present invention is not limited thereto. [Exemplary Compounds] Cl-5> ONHCHtSOJa General Formula [Al-11] In the formula, Rfa and Rfs' each represent a hydrogen atom, or an optionally substituted alkyl group, aryl group, or heterocyclic group, and an aryl group Examples include 4-sulfophenyl group, 4-(δ-sulfobutyl)phenyl group, 3-sulfophenyl group, 2.5-disulfophenyl group, 3.5-disulfophenyl group, 6°8-disulfo-2
-naphthyl group, 4,8-disulfo-2-naphthyl group, 3
．． 5-dicarboxyphenyl group, 4-dicarboxyphenyl group, etc., and this aryl group can be a sulfo group, a sulfoalkyl group, a carboxy group, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, etc.), or a halogen atom. (for example, a chlorine atom, a bromine atom, etc.), an alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group, an ethoxy group, etc.), or a phenoxy group. The sulfo group may be bonded to an aryl group via a divalent organic group. For example, 4-(4-sulfophenoxy)phenyl group, 4-(2-sulfoethyl)phenyl group, co(sulfomethylamino) Examples include phenyl group, 4-(2-sulfoethoxy)phenyl group, and the like. The alkyl groups represented by Rfa and nfs may be linear, monobranched or cyclic, preferably having 1 to 1 carbon atoms.
4, and examples thereof include ethyl group and β-sulfoethyl group. Examples of the heterocyclic group include a 2-(6-sulfo)benzthiazolyl group, a 2-(6-sulfo)benzoxasilyl group, and a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), It may have a substituent such as an alkyl group (eg, methyl group, ethyl group, etc.), an aryl group (eg, phenyl group, etc.), a carboxyl group, a sulfo group, a hydroxy group, an alkoxy group (eg, phenoxy group, etc.). Rfy and Rfy' are each a hydroxy group: carbon number 1
~4 alkoxy groups (e.g. methoxy group, ethoxy group,
isopropoxy group, n-butyl group): Substituted alkoxy group 1 For example, an alkoxy group having 1 to 4 carbon atoms substituted with a halogen atom or an alkoxy group having up to 2 carbon atoms (for example, β
-chloroethoxy group, β-methoxyethoxy group); cyano group; trifluoromethyl group; -COORfa; -
CONHRfa: -NHCORfa (Rfa is a hydrogen atom: an alkyl group, preferably an alkoxy group having 1 to 4 carbon atoms; or an aryl group 1, such as a phenyl group or a naphthyl group, and the alkyl group and aryl group have a sulfo group or Niamino group (which may have a carboxy group); n-substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms (e.g. ethylamino group, dimethylamino group, diethylamino group, di-n-butylamino group) : (Here, p and q represent integers from ! to 2, and X is FI
Ii atom, sulfur atom, -Ca1. - represents a cyclic amino group (for example, a morpholino group, a piperidino group, a piperazino group). The methine group represented by is an alkyl group of carbon a1-4 (
For example, methyl group, ethyl group, isopropyl group, tert-butyl group, etc.) or aryl group (for example, phenyl group,
tolyl group, etc.). Further, at least one of the sulfo group, sulfoalkyl group, and carboxy group of the compound is an alkali metal (eg, sodium, potassium) or an alkaline earth metal (eg, calcium, magnesium). May form salts with ammonium or organic bases (e.g. diethylamine group, triethylamine group, 1 morpholine group, pyridine group, piperidine group, etc.),
n represents 0.1 or 2, and Otori represents 0 or l. Representative specific examples of the compound represented by the general formula [AI-II] are shown below, but the present invention is not limited thereto. [Exemplary compounds] (If-1) sosx SO*K (II-2) (■-3) (n-4) (II-5) COOIIa C00Na (n-6
) SOsN* 5OJaCn-7> (II-8) (n -9) (II-10) SOlr Sol(It
-11) (II-12) SOslla 5Osl
la(II-13) (II-14) (II-15) (II-16) (■-17) (n-18) SOsK
5Us 凰 (If-19) (II-20) (■-21) SOsK SOsKCr1-22> (n-23) (ff-24) a (II-25) (n-26) (II-27) (It -28) (n-29) General formula [A I -m] In the formula, r represents an integer of 1 to 3, W represents an oxygen atom and a sulfur atom, L represents a methine group, and Rb+ to Rfxa are It represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, in which at least one m substituent is other than a hydrogen atom. Examples of the methine group represented by the general formula [AI-III] include those described above in the section of AI-III. As the alkyl group represented by Rht to Rfxs, - Rf listed in the section of the general formula [Al-11], and Rf, + ”
Examples of the alkyl group include the same alkyl groups as those of the general formula [
The various substituents introduced into the Rf, Rf, and ' groups in the section "AI-n" can be mentioned, but preferred are a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, and an alkoxycarbonyl group. , a cyano group, and a sulfonyl group. The aryl group represented by Rf□ to Rf3s is preferably a phenyl group, and the substituents introduced into this phenyl group include the general formula [Rfs and Rfs' in the section of AI-III.
Although the various substituents mentioned above can be mentioned as substituents to be introduced into the group, it is desirable to have at least one group among a sulfo group, a carboxy group, and a sulfamoyl group on this aromatic ring. The aralkyl group represented by Rf3s to Rfx4 is preferably a benzyl group or a phenethyl group, and the substituents introduced therein include the same substituents as those of the aryl group Rf3t to Rf3n described above. Examples of the heterocyclic group represented by Rfj and ~Rf34 include a pyridyl group and a pyrimidyl group,
The substituents introduced on this heterocycle include the above-mentioned R
The same substituents for the aryl group of f3* to Rf can be mentioned. Rf! The group represented by I''Rf s 4 is preferably an alkyl group or an aryl group, and furthermore, a carboxy group, a sulfo group, or a sulfamoyl group is present in the molecule of the barbylic acid and thiobarbyl group represented by the general formula [AI-m]. It is desirable to have at least one group of each group, and symmetrical ones are preferable.Representative specific examples of the compound represented by the general formula [A I-m] are shown below, but the present invention is not limited by these. [IFIJ compound CJs CtH* C4H@-!l C mountain-n(:Js-1
114k1m-R (III-7) General formula [AI-IVI In the formula, Mi represents an integer of 1 or 2, L represents a methine group, RrsI bar f8 formula [A l-l11 (F) Rf
It has the same meaning as s and Rf6', and is preferably an alkyl group or an aryl group, and the aryl group preferably has at least one sulfo group. Rfs2 has the general formula [Rf of Al-l1l, and Rfy'
All of the substituents shown in can be introduced, and preferably those selected from an alkyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, a ureido group, an acylamino group, an imide group, and a cyan group. Z2.2. and z3 represent a hydrogen atom and an alkyl group, respectively, and z2 and 2. may be the same or different, or may be combined with each other to form a ring. Examples of the alkyl group represented by Zl, L and z3 include methyl group, ethyl group, butyl group, hydroxyalkyl group (e.g. hydroxyethyl group, etc.), alkoxyalkyl group (e.g. β-ethoxyethyl group etc.), carboxyalkyl group ( For example, β-carboxyethyl group, etc.), alkoxycarbonyl alkyl group (for example, β-ethoxycarbonylethyl group, etc.), cyanoalkyl group (for example, β-diaminoethyl group, etc.), sulfoalkyl group (for example, β-sulfoethyl group, γ-sulfoethyl group, etc.), propyl group, etc.). z2 and 23 may be combined with each other to form a 5- or 6-membered ring, and specific examples include a morpholino group, a piperidino group,
Examples include pyrrolidino group. Rf represents a hydrogen atom, an alkyl group, a chlorine atom, or an alkoxy group, and examples of the alkyl group include a methoxy group and an ethoxy group. Typical specific examples of the general formula [AI-IVI are shown below,
The present invention is not limited thereby. [Exemplary Compounds] C00Xa 0sNa SOl 0slla The above general formulas [AI-I] and [AI-II]. Compounds represented by [A I-m] or [AI-IVI are disclosed in U.S. Pat. Nos. 3,575,704 and 3,247,127.
No. 3,540,887", No. 3,853,905
Specifications of each issue, JP-A-48-85130, JP-A-49-9
No. 9620, No. 59-111640, No. 59-111
It can be synthesized by the synthesis method described in each publication of No. 641-59-170838. When it is contained in a photosensitive material, it is preferably contained in a non-photosensitive hydrophilic colloid layer, and the organic/inorganic alkali salt of the above AI dye compound is dissolved in water to obtain a suitable concentration of dye, and then added to the coating solution. Then, coating may be performed using a known method. The content of these AI dye compounds is preferably 1 to 80 G+ag per rn' area of the photosensitive material, more preferably 2 to 200 M8/r.
Make it so that it becomes rf. Above ~ general formula [Al-ll, [AI-n], [AI-m]
or [Two or more compounds represented by AI-IVi may be used in combination. The photosensitive material may contain a DIR compound, and in addition to the DIR compound, it may also contain a compound that releases a development inhibitor during development; for example, as described in U.S. Pat. , No. 379.529, for West German patent! II (OLS) No. 2,417,914, @
Opening and closing No. 52-15271, No. 53-9116, No. 59
Examples include those described in No. 123838, No. 59-127038, and the like. The above DIR compound is a compound capable of releasing a development inhibitor or a development inhibitor precursor by reacting with an oxidized form of a color developing agent, and may be a non-diffusible DIR compound or a diffusible DIR compound. . Typical examples of such II'l compounds are:
A DI in which a group capable of forming a compound having a development inhibiting effect when separated from the active site is incorporated into the active site of the coupler.
There are R couplers, such as British Patent No. 935,454,
U.S. Patent No. 3,227,554, 4,095.9
No. 84, No. 4,1411.888, etc. The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor. Moreover, in the present invention, U.S. Pat.
No. 1, No. 3,958,993, No. 3,981,959
No. 4,052,213, JP-A-53-11052
9, No. 54-13333, No. 55-161237, etc., which release a development inhibitor but do not form a dye when subjected to a coupling reaction with an oxidized color developing agent. It will be done. Furthermore, JP-A-54-145135 and JP-A-56-1
When reacted with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Alternatively, the so-called timing D is a compound that releases a development inhibitor by reaction.
It may also be an IR compound. Also, JP-A No. 58-160954, No. 58-16294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
It may also be an R compound. [Effects of the Invention] According to the present invention, it is possible to provide a color developing solution containing a preservative (an antioxidant for a developing agent) that is harmless to the human body and easy to handle, instead of hydroxylamine, which is a highly toxic substance, and which is a color developing solution. The decrease in density when the solution is stored for a long period of time, i.e. the maximum concentration (Dax
), and stable photographic properties can be provided during long-term processing. [Specific Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 A color developing solution having the following composition was prepared. (Color developer) Benzyl alcohol 15 rm ethylene glycol 10 rm potassium sulfite 2. OX 100 mole Potassium bromide 10 g Sodium cyclide 0.3 g Potassium carbonate
25.0 g preservative (listed in Table 1)
5.0 g polyphosphoric acid (TPPS)
2.0 g Color developing agent [Exemplary compound 1)] 5. Og optical brightener [Exemplary compound (4)] 2. Q g Potassium hydroxide and water were added to make 11. Note that the pH was 10.20. Each color developer contains 4ppm of ferric ions and zpp of copper ions.
■ and 100pp of calcium ion■ (FeC
1x, CuS0.4H=O and CaC1* were dissolved and added) and stored at 50°C in a glass container with an air contact surface roughness of 30 cm for a developing solution with an aperture ratio of 30cm/lc1cm. After 10 days, the outside of the color developing solution (degree of coloration) was observed. However, the appearance of the solution was divided into the following five stages: →← A large amount of tar generation - H - Blackening H - Brown ratio ( (Significant discoloration) □ Almost no change 0 No change Table 1 As is clear from Table 1, regarding the storage stability of the liquid, 1. The combination of compounds of the present invention can be a sufficient substitute for hydroxylamine sulfate. It is clear that.In fact, the preservative properties are slightly improved compared to hydroxylamine.In addition, preservatives (1) of developer Nos. 15 to 17 were used as preservatives (6) and (8), respectively.
Also, the same results as No. and IS-17 were obtained for the color developing solution in which the only difference was that (11) was replaced. Example 2 On a paper support laminated with polyethylene. The following layers were sequentially coated from the support side to prepare an internal latent image type photosensitive material sample. First diane-forming red-sensitive silver halide emulsion layer cyan coupler, 2,4-cycloromethyl-8-■
α-(2,4-di-tert-amylphenoxy)butyramide]phenol 90 g, 2,5-di-te
2 g of rt-octylhydroquinone, 50 g of tricresyl phosphate, 200 g of paraffin and 5 g of ethyl acetate.
0g was mixed and dissolved, gelatin solution containing sodium dodecylbenzenesulfonate was added, and the particles were dispersed so that the average particle size was 0.5μ (according to Example 1 described in U.S. Pat. No. 2,592,250). Internal latent image type silver rhodanide emulsion (AgBr:^gc prepared by conversion method)
l = 70:30), silver amount 400 g/g,
Example of AI dye (II-10) Coating was carried out so that the amount of coupler was 2hg/g and the amount of coupler was 350mg/g. Second Calendar: Intermediate layer 100 ml of 2.5% gelatin solution containing 5 g of gray colloidal silver and 10 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate to a colloidal silver content of 400 g/m'' 3rd M=Magenta-forming green-sensitive silver halide emulsion layer Magenta coupler, 1-(2,4,6-)-lichlorophenyl)-3-(2-chloro-5-octadecylsuccinimideanilino)- 100 g of 5-pyrazolone, 2.
Mix and dissolve 5 g of 5-tert-octylhydroquinone, 50 g of Sumilizer MDP (manufactured by Sumitomo Chemical Co., Ltd.), 200 g of paraffin, 100 g of dibutyl phthalate, and 50 g of ethyl acetate, add gelatin solution containing sodium dodecylbenzenesulfonate, and adjust the average particle size. 0
．． The mixture was dispersed to a concentration of 6 pm. Internal MI image prepared in the same manner as the first layer A8 hegenated emulsion (AgBr:
AgC1=60=40) was added, ffi amount 400
mg/nf, Examples of A I dyes (n-8) 20
4th layer: yellow filter layer containing 5 g of yellow colloid* and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate. 5% gelatin solution and colloidal silver 20%
0+sg/m''. 5th layer: yellow forming blue-sensitive silver rhodanide emulsion layer yellow coupler, α-r 4-(1-benzyl-2-
7enyl-3,5-dioxo-1,2,4-)riazolidinyl-α-bivalyl-2-chloro-5-[γ-(2,
4-di-tert-amylphenoxy)butyramide]
120 g of acetanilide, 3.5 g of 2.5-di-tert-octylhydroquinone, 200 g of paraffin,
First, 100 g of Tinuvin (manufactured by Ciba Geigy), 100 g of dibutyl phthalate, and 70 ethyl acetate were mixed and dissolved, a gelatin solution containing sodium dodecylbenzenesulfonate was added, and the particles were dispersed in a layer with an average particle size of 0.9W. Silver rhodanide emulsion (AgBr: AgC = 80:20) was added to the internal latent image type prepared in the same manner as the layer, silver: 1400 g/G, coupler [400 g/
6th layer: Protective layer The gelatin amount was coated to be 200 gg/rn'. All of the above layers contained saponin as a coating aid. As an agent, sodium 2,4-dichloro-6-hydroxys-triazine was added to layers 2.4 and 6 in an amount of 0.02 g per 1 g of gelatin.The above internal latent image type photosensitive material sample After exposure through an optical wedge, it was processed in the first step. Processing process (38°C) Immersion (color developer) 8 seconds color development 120 seconds (uniform exposure of the entire surface with 1 lux light for the first 10 seconds) Bleach-fixing 80 seconds Washing with water 60 seconds Drying 80-80°C 120 seconds The composition of each processing solution is as follows. [Color developer] Color developer No. 1, 2, 10, 11 used in Example 1
, 15 to 20, which had been stored tightly sealed at 50° C. for 5 days. [v: 4 self-sufficient liquid] Pure water 550 m ethylenediaminetetraacetic acid iron (m) Ammonium salt 658 thio WL
Ammonium acid (70% aqueous solution) 85g Sodium bisulfite 10g Sodium metabiitite 2g Disodium ethylenediaminetetraacetic acid 208 Add pure water to make 11, and adjust to pl = 7.0 with aqueous ammonia or dilute sulfuric acid. The light-sensitive material was subjected to stepwise exposure using a conventional method and processed according to the method described above, and the fluctuation value of the maximum reflection density (blue density) was measured. However, the variation value of the maximum reflection density (blue density) is the value obtained by subtracting the maximum reflection density (blue density) before storage from the maximum reflection density (blue density) after storage. The results are shown in Table 2. Table 2 As is clear from Table 2, according to the present invention, the decrease in concentration over time can be suppressed. Example 3 In place of exemplified compound 1) of the color developing agent used in Example 1, exemplified compound 4) was used for 3). 11) and 12) were also investigated, but results similar to those in Tables 1 and 2 could be obtained. However, potassium sulfite was replaced with 1.5 x 1 G-'' mole, sodium iodide was added at 2.0 gl, benzyl acetate, ethylene glycol, and optical brightener were not added, and the pH
It was set as 10.03. Example 4 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 to
o, ooo, 200 parts by weight of polyethylene with a density of 0.95 and an average molecular weight of 2000. Polyethylene 2 with a density of 0.80
6 parts by weight of anatase titanium oxide
．． 8fi, 1% was added and the thickness was 0.035mm on the surface of engineered paper with a weight of 170g/g by extrusion coating method.
On the back side, a coating layer of 0.04 (1 mm) thick was formed using only polyethylene.The polyethylene coating surface of this support was pretreated by corona discharge. After that, the following layers were sequentially coated: 1st layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing #!4 mol % of bromide, the emulsion containing 350 g of gelatin per mole of silver halide. , sensitized using 1 mole of halogenated IR and 2.5X 10-' moles of the sensitizing dye (I) of the following structure (using isopropyl alcohol as solvent), dissolved and dispersed in dibutyl phthalate 2,
5-di-L-butylhydroquinone 200mg/rn'
and a yellow coupler containing [Y-1] with the following structure in an amount of 2.0 x 10-1 mol per mol of silver halide, t
Jii 30 (lag/rn'). Second layer 3001 g/nf of di-1-octylhydroquinone dissolved and dispersed in nidibutyl phthalate, 2-(2'-hydroxy-3 =, 5'-di-1-butylphenyl)benzotriazole, 2-(2''-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2''-hydroxy-3'-butyl-5 ′
A mixture of (1:1:1 :1) A gelatin layer containing 20 g/rn' is coated to give a gelatin of 1900 eg/m'. Third house: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 2 mol % of silver bromide, the emulsion containing 450 g of gelatin per mol of silver halide, having the following structure per mol of silver halide Sensitizing dye (II) 2,5- 2,5-
Di-t-butyl octahydroquinone and [M-1] having the following structure as a magenta coupler per mole of silver halide.
1. Contains 10-' moles of SX, fliM 230B/
Go, shoulder dye [11-81 was applied at 50 g/go. In addition, as an antioxidant, 2,2.4-
Trimethyl-6-lauryloxy-7-octylchroman was added in an amount of 0.30 mol per mol of coupler. 4th layer 301 g/m'' of di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2-(2'-hydroxy-3'',5''-di-t-butylphenyl)benzotriazole as a UV absorber; 2-(2'-hydroxy-5'-1-butylphenyl)benzotriazole, 2-(2''-hydroxy-3'-butyl-5'
-methylphenyl)-5-chloro-benzo-1-riazole, a mixture of 2-(2''-hydroxy-3',5''-di-t-butylphenyl)-5-chloro-benzotriazole (221.5 : 1.5 : 2) 500m
g/m', gelatin 19
00 mg/m'. 5th layer: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 83 mol% bromide.
150 mg of 2,5-di-tert-butylhydroquinone, sensitized using 2.5 x 10-' moles of a synthetic sensitizing dye (flI) and dissolved and dispersed in dibutyl phthalate.
/rn' and a cyan coupler with the following structure [C-1
] per mole of halogenated i, the amount of silver was 280 mg/n'l', and the AI dye exemplified compound [11-9] was coated at a rate of 40 g/n'l'. The sixth layer is a gelatin layer, and gelatin is coated at a concentration of 900 mg/rn'. The silver halide emulsions used in each photosensitive emulsion layer (layers 1, 3, and 5) were prepared by the method described in Japanese Patent Publication No. 7772/1983, and sodium thiosulfate was used in each case. Chemically sensitized and stabilized with 4-hydroxy-6-
Methyl-1,3,3a,7-chitrazaindene (2.5 g per mole of silver halide), bis(vinylsulfonylmethyl)ether as a hardening agent (l per Ig of gelatin)
It contained saponin as a coating aid. Sensitizing dye I Sensitizing dye ■ Sensitizing dye m [Y-1] rθ [M-13 Cσ [C-1] After exposing the color vapor prepared by the above method, the first processing step and using a processing solution are performed. Continuous processing was performed. Processing step (1) Color development 35°C 45 seconds (2)
Bleach fixing 35°C 45 seconds (3) Water washing alternative stabilization treatment 30°C 90 seconds (4) Drying 60°C to 80°C 1 minute 30 seconds Processing solution composition [Color developing tank solution] Potassium chloride 2.Og sub-VL
Potassium acid 6.5X10-''''Molar color developing agent 1) 5.0g preservative (
Table 3 tl) 5.0g triethanolamine 10.0g potassium carbonate
30.0g Ethylenediaminetetraacetic acid sodium salt 2.0g Optical brightener example (4)
Add 2.0 g of water to make a single solution, and adjust to pHIQ and I5 with potassium hydroxide and 20% sulfuric acid. [Color development replenisher] Potassium chloride 2.5g Potassium alumite '7 (SO$ solution) 7.0X10-'MoJ
L. Color developing agent 1) 8.0g preservative (see Table 3) 7.0g triethanolamine 10.0g potassium carbonate 30.0g ethylenediaminetetraacetic acid sodium salt 2.0g Add water to make 11, and add potassium hydroxide. Adjust the pH to 10.40 with 20% sulfuric acid. [Bleach-fixing tank liquid] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0g Ethylenediaminetetraacetic acid 3.8g Ammonium thiosulfate (70% solution) 100.0mu Submersible WLm7
:/Mo:- Ram (40%mWN) 27.
Adjust the pH to 5.50 with 5 mJL ammonia water or glacial acetic acid, and add water to bring the total volume to 1 sentence. [Bleach-fix replenisher] Ethylenediaminetetraacetate ferric ammonium dihydrate 70.0g Ammonium thiosulfate (70% solution) 12D, DmlL Ammonium sulfite (40% solution) 35.0sI
L-ethylenediaminetetraacetic acid 3.0g Add water to make one sentence. The pH of this solution is adjusted to 5.4 using glacial acetic acid or aqueous ammonia. [Water washing alternative stable tank liquid and replenisher] Ortho-phenylphenol 0.2g 1-hydroxyethylidene-1,l-diphosphonic acid (60% aqueous solution) 2.0g ammonia water 3.0g water to make one sentence, and ammonia water and sulfuric acid 9117.8. Fill an automatic processor with the above color developer tank solution, bleach-fix tank solution, and stability tank solution, and replenish the above color developer replenisher, bleach-fix replenisher, and stable tank solution every 3 minutes while processing the color vapor sample. A running test was performed while replenishing the liquid through a metering pump. The amount of replenishment is 220 x 220 per color vapor to the color developing tank, 220 x 220 of the bleach-fixing tank, and 25 x 25 of the washing alternative stable replenisher to the layer stabilizing tank.
0-! Replenished. The stabilization processing baths of the automatic processor are the first to third stabilization tanks in the direction of the flow of the photosensitive material, and the final tank is refilled, and the overflow liquid from the final tank is sent to the previous tank. A multi-tank countercurrent system was adopted in which the overflow liquid was allowed to flow into the previous tank. The color vapor was subjected to a running process until the total replenishment amount of the color developer was three times the capacity of the color developer tank, and then the stepwise exposed vapor sample was passed through and stored as in Example 1 (however, the aperture ratio The Eel before tar generation (preserved in a 15 c''/Jl glass container with a seal for 7 days) and the fluctuation value of the maximum reflection density (blue density) according to Example 2 were measured. The results are shown in Table 3. Table 3 As is clear from Table 3, when the preservative of the present invention was used in combination, the generation of tar was delayed and the degree of C decreased over time as well.Example 5 Sample No. 3S In each of 9 to 9, exemplified compounds of general formula [C] (1), (2), (3), (11), (13
), (17), (19),. The same experiment as in this example was carried out in exactly the same manner except that (20) or (24) was added in Sg/l. The number of days until tar appeared was extended by about one week each. Furthermore, when we measured the spectral absorption at 540nw and 640n- for the stain, which is thought to be due to defective decolorization of the AI dye, the spectral absorption decreased to less than 1 in each case compared to the sample before adding the exemplified compound of general formula [C]. became.

Claims (1)

[Scope of Claims] Color-forming silver halide color photographic light-sensitive material characterized by containing at least one compound represented by the general formula [A] and at least one compound represented by the general formula [B] developer. General Formula [A] ▲ Numerical formulas, chemical formulas, tables, etc. , R_2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, a heterocyclic group, an amino group, a hydrazino group, and R_3 represents a hydrogen atom,
represents an alkyl group or an aryl group, l is 0 or 1,
When l is 0, Z is -CO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO
＿２−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and when l is 1, Z is -CO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, -SO_2-. R has the same meaning as R_3. ] General formula [B] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R_4 is a hydroxyalkyl group with 2 to 6 carbon atoms, R_5 and R_6 are each a hydrogen atom, and 1 to 6 carbon atoms.
an alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms,
Indicates the benzyl group or the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the n of the above formula
is an integer of 1 to 6, and X and Z each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms. ]