JPS61261744A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent black precipitates due to long storage of a stabilizing soln. for replacing rinse water by processing a photosensitive material with a bleach fixing soln. composed essentially of the ferric complex salt of an org. free acid specified in mol.wt., thiosulfate, and sulfite, and treating it with said rinse replacing soln. for a specified time length. CONSTITUTION:The color developed silver halide color photographic sensitive material is processed with the bleach fixing soln. composed essentially of the ferric complex salt of an org. free acid having a mol.wt. of <=280, thiosulfate, and sulfate, and treated with the stabilizing soln. for replacing rinse water for <=2min, thus permitting fine black precipitates occurring when the stabilizing soln. stays for a long period in this process to be prevented, and yellow stains and edge stains occurring when the photographic image formed by treatment with a reduced replenishing amt. of stabilizing soln. is stored for a long period to be alleviated.

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a method for processing silver halide color photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials), and in particular uses a small amount of an aqueous solution instead of a washing step that uses a large amount of water after bleach-fixing. The present invention relates to a method of processing with a water washing alternative treatment liquid. [Prior Art] In recent years, environmental conservation and water resource issues have become important in photofinishers that automatically and continuously develop photosensitive materials. It is desired to reduce or eliminate the small amount of water used for washing. For this reason, methods have been proposed to reduce the amount of washing water used in large quantities. For example, West German Patent No. 2,920.222 describes a technique for reducing the amount of washing water by configuring the washing tank in multiple stages and causing the water to flow backwards. S as the specification and technical literature
, Ro Oldwasser, “Waterflour
rate in iuuaeration-wa
st+iB of IIItionpicture
e fi1m″Jour, SMPTE, 64248-2
53. May (1955) is known. Furthermore, there is a method of omitting the water washing step and performing stabilization treatment (water washing alternative treatment) without actually performing water washing. Kaimei 57-8543, Kaimei 58
-14834, No. 58-134636, etc. The prebath for such stabilization treatment contains thiosulfate, and after the bleach-fix solution containing such thiosulfate,
Instead of washing with a large amount of washing water, pre-rinsing with a small amount of washing water as described above, multi-stage counter-current washing with a small amount of water, etc., or alternative washing processing where processing is performed while replenishing with a small amount of water, is performed. In such cases, the residence time of the treatment PV liquid used in these treatments becomes very long. As a result, fine black precipitates are more likely to form in the processing liquid due to storage over time (χ). No. 4.059
According to the specification of No. 446, there is a technique of adding a polyalkylene oxide type nonionic surfactant to a water washing bath. Furthermore, as described in JP-A No. 57-8542, there is a technique of adding isothiazoline or pentisothiazoline compounds to the washing water. However, the prevention effect is not sufficient, and there is a need for a technology that does not cause problems with retention in washing water or stabilizing treatment liquid. In addition, increasing or decreasing the replenishment amount of the water-washing alternative stabilizing solution or shortening the processing time will increase the amount of the water-washing alternative stabilizing solution and the concentration of bleach-fixing components in the final tank, resulting in yellow staining caused by long-term storage of unexposed areas of the photosensitive material. There is a lack of 7α that increases. In addition, there is a drawback that 6 contaminants remain in the unexposed areas immediately after processing.
It becomes a big problem. Furthermore, users are constantly asking for faster processing. [Object of the Invention] Accordingly, a first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which prevents black precipitate caused by storage of a water-washing substitute stabilizer over time. The second object of the present invention is to provide a silver denside color sensitizer capable of preventing an increase in yellow stain due to long-term storage of unexposed areas of a photosensitive material*1, even if the number of times for replenishing a water-washing alternative stabilizer is reduced. The purpose is to present the processing power method of Key 4. A third object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which can prevent the occurrence of white background contamination in unexposed areas as described in -1-. A fourth object of the present invention is to provide a rapid processing method for silver halide color photographic materials. [Structure of the Invention] An object of the present invention is to provide a method in which a silver halide color photographic light-sensitive material is processed with a bleach-fix solution after color development, and subsequently treated with a water-washing substitute stabilizing solution, in which the bleach-fix solution contains free acid. A silver halide containing as main components an Ariiso ferric complex salt, a thiosulfate, and a sulfite having a molecular weight of less than 280, and the processing time with the water washing substitute stabilizing solution is 2 minutes or less. This is achieved by a method for processing color photographic materials. The present invention will be explained in detail below. Conventionally, bleach-fixing (ferric acid salt is known as a bleaching agent used in liquid 6, and thiosulfate is used as a fixing agent and as a preservative! 11) using sulfate. In conventional bleach-fix solutions, ferric ethylenenoaminetetraacetic acid is used as the ferric salt of the organic acid. The reason for using ferric ethylenenoamine tetramate is to improve the desilvering properties, recoloring properties, and

[/' This is because it is preferable in terms of liquid storage stability. Therefore, a process that replaces the washing process that uses a large amount of water following treatment with a bleach-fix solution with a process using a washing substitute stabilizing solution that uses a small amount of aqueous solution bleaches ferric ethylenenoaminetetraacetic acid. It is used as a bath following the processing step with a bleach-fixing solution used as a bleach-fixing agent.In such a system, the above-mentioned water-washing alternative stabilizer has poor storage stability over time, and is used as a bath for unexposed photosensitive materials after processing. Problems have arisen in that yellow stains occur on long-term storage, and white stains are likely to occur on unfinished areas.As a result of extensive research into this problem, the inventor has discovered a surprising solution. In particular, the above technical problem is solved when an organic acid ferric salt with a free acid molecular weight of less than 280 is used as the bleaching agent in the bleach-fix solution, and the treatment time with the water washing substitute stabilizing solution is set to 2 minutes or less. That is, the effect of the present invention is that the use of the bleach of the present invention promotes the elution of components that increase yellow stain caused by storage, and that a water washing alternative stabilizer is used. Due to the short processing time, there is less leakage of white background stain preventive agents (e.g. fluorescent whitening agents), image preservation improvers, etc. added to the photosensitive materials during manufacturing or contained in the color development process due to the short processing time. It is thought that increase in yellow stain and white background contamination in unexposed areas due to storage can be prevented.Furthermore, if the organic acid ferric salt is represented by the general formula (I),
The effect of the present invention is particularly remarkable when the compound has the general formula (
Contains a compound represented by It) or V))
It has been discovered that the molecular weight of the organic acid ferric complex salt used in the present invention is 280
As the free acids below, aminopolycarboxylic acid compounds and polyphosphonic acid compounds are preferably mentioned,
Among these, the former is more preferred, and the compound represented by general formula [I] is particularly preferred. General formula (1) In the formula, A is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carbodialkyl group having 1 to 4 carbon atoms. represents. Particularly preferred A is a methyl group, a hydroxyethyl group, a carboxymethyl group, a butyl group, and a hydrogen atom. The lipolyphosphonic acid compound has H2O5P-1;, -PO3
112 (herein, B. B and B1 each represent a hydrogen atom, a hydroxy group, an alkyl group, or an amide group). Representative examples of the above-mentioned free acids are listed below, but the invention is not limited thereto. (Molecular weight in parentheses) ' (+) = )
Acetic acid (191,14) (2) Nitrilodiacetic acid propionic acid (205,17) (3) Iminodiacetic acid (193,
10) (4) 1 liter of iminodimethylene phosphone (204,98
)1 (5)N-/+/. A2,2□(+47
．． . 63) (6) Iminodipropionic acid (161,07
4)°°1″)N-(9″3-9/f/L-
7'f tv) ""/7ffl:II! (21″°p, + (8) Hydroxyethyliminodipropionic acetic acid 1 (205,10) (9) Hydroxypropyliminodiacetic acid (191,0
9) (10) Methoxyethyliminodiacetic acid (191,0
9) (11) N-(carbamoylmethyl)iminodiacetic acid (190,08) (12) Aminoethyliminodiacetic acid (179,08) (
13) β-(N-trimethylammonium)ethylimi6,17 diacetic acid cation (219,12)”] (14) Phosphonomethyliminodiacid acid (227,04)
(15) Phosphonomethyliminodiaic acid (225,04) (
16) Sulfoethyl iminodiacetic acid (241,14) (1
7) Hydroxyethyliminodiacetic acid (177,16) (
18) Dihydroxyethylglycine (163,17) (
19) DiF lyrotribrobionic acid (233,22) (2
0) Ethylenediamine diacetic acid (176, 17) (21)
Carboxyethyl iminodiacetic acid (205,08) (22
) N,N'-ethylenediaminediacetic acid (172,08)
(23) N,N'-di(hydroxyethyl)ethylenediamine, diacetic acid (264,13) (24) Ethylenediaminedipropionic acid (277,1
5) (25) Hydroxyethylethylenediaminetriacetic acid (278,26) (26) 1-hydroxyethylindene-1,1-diphosphonic acid (205,97> (27) Hydroxymethylidene diphosphonic acid (191,
96) (28) l-aminoethylidene-1,1-diphosphonic acid (203,98) (29) 1-aminopropylidene-1,1-diphosphonic acid (217,99) Second organic acid used in the present invention There are 1 type of iron complex salt and 2 types of iron complex salts.
More than one species can be used in combination. The concentration needs to be selected depending on the amount of silver in the photosensitive material to be processed and the composition of silver halide No. 11, but usually the solution used is 1
The range is preferably from 2X]O-2 to 2 mol, more preferably from 5x10-2 to 1.0 mol per g. The bleach-fix solution in the present invention uses a compound other than the above-mentioned organic acid ferric complex salt as a bleaching agent, such as a free acid with a molecular weight of 280.
1. The organic acid ferric complex salt may be contained in an amount of not more than 50 mol% of the amount before whitening,
It is preferably 10 mol% or less. The thiosulfate contained in the bleach-fix solution of the present invention is preferably an alkali metal salt or an ammonium salt, such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate. Its concentration is 5 g/Q IJJ
, -1 = within the range that can be dissolved, but preferably 70~
In the present invention, the sulfite to be contained in the bleach-fix solution includes sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, and metabisulfite. Potassium acetate, ammonium metabisulfite, hydrosulfide, grugulaldehyde sodium bisulfite,
Compounds such as sulfuric acid aldehyde (l'bisbisulfite) may be used, but any compound that releases sulfite ions may be used.''1. .1
It is preferable to contain molar IQ. The bleach-fix solution in the present invention contains -1-described ferric isoacid complex salt, thiosulfate, and sulfite as main components, which means 50 mol% or more of the total amount of bleach contained in the bleach-fix solution.
- is the above organic acid ferric complex salt, and these three
This means that additives commonly used in bleach-fix solutions may be included in addition to the seed components. That is, the white paper fixer of the present invention contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate,
Various p It M sanitizing agents such as ammonium hydroxide can be contained alone or in combination of two types. Furthermore, various optical brighteners, antifoaming agents, or surfactants may be contained. In addition, preservatives such as hydroxylamine, hydrazino, bisulfite adducts of aldehyde compounds, organic chelating agents such as ami-7 polycarboxylic acid, stabilizers such as nitro alcohol, nitrates, methanol, trimethylsulfamide, etc.
An organic solvent such as dimethyl sulfoxide can be appropriately contained. Also, JP-A-46-280, JP-A-45-8506, JP-A-46-556, Belgian Patent No. 770.910, JP-A-45-8836, JP-A-53-9854, JP-A-54-71634. Various bleach accelerators described in Japanese Patent No. 49-42349 and the like can be added. 1]] of the bleach-fix solution in the present invention is 4.0 or more -1,
preferably at pH 15, Of; J, 1
- pH 9.5 or higher”], more preferably pH 16,
It is 0 or more and 1+ It 8.5 or less. The processing temperature is 80°C or less, which is 3°C or less, preferably 5°C or more lower than the processing solution temperature in the color developing tank, but preferably 55°C or less for evaporation, etc. Use it sparingly. In the present invention, processing with bleach-fixing, followed by washing with a substitute stabilizing solution means that the concentration of the fixing solution or bleach-fixing solution in the fixing tank brought into the stabilization tank 11v does not become less than I/200. This means that if the amount is sufficient, treatments such as extremely short-time rinsing treatment using a single tank or multi-tank countercurrent system, auxiliary water washing, and washing promotion bath may be performed. In the present invention, the treatment with a water-washing substitute stabilizing solution refers to a stabilizing treatment that is performed immediately after the treatment with a bleach-fixing solution and does not substantially require a water-washing treatment, and the processing solution used for the stabilization treatment. is called a water washing alternative stabilizer, and
! ! , the girder is called a stabilizing bath or stabilizing tank. In the present invention, the stabilization treatment can be carried out in one tank or in multiple tanks without any problem, but preferably in 1vi to 4 tanks. The present invention is most effective when the amount of replenishment of the water-washing substitute stabilizing solution in the stabilizing bath is small, and the amount of replenishment is 1 to 50 times the amount brought in from the previous bath per unit area of the photographic material to be processed.
The effect of the present invention is particularly significant in the range of 2 to 20 times. The water washing substitute stabilizing solution is used to replenish a small amount of water when processing a photosensitive material, and basically only water can be used, but various compounds can also be added. Compounds that can be preferably used in the present invention include: , anti-spill agents, ammonium salts, chelating agents and metal salts. The antifungal agents preferably used in the water-washing alternative stabilizer of the present invention include hydroxybenzoic acid compounds, alkyl □,
) k 7 , inxazole compounds, propatoolamine compounds, sulfamide derivatives, and amino acid compounds. The hydroxybenzoic acid compounds include hydroxybenzoic acid and hydroxybenzoic acid ester compounds such as methyl ester, ethyl ester, butyl ester, and butyl ester, but preferably 11-butyl ester and isobutyl ester of hydroxybenzoic acid. These include esters and propyl esters, and more preferably a mixture of the three types of hydroxybenzoic acid esters. In the alkylphenol compound, the alkyl group is C1-6
A compound having an alkyl group as a substituent, preferably ortho-phenylphenol or ortho-cyclohexyphenol. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and preferably 1,2-benzisothiazolin 3-one, 2-methyl-4-thiazolin 3-one, 2-octyl-4- These are isothiazolin 3-one, 5-chloro-2-methyl-4-isothiazolin 3-one, and 2-(4-thiazolyl)benraimigzole. Specifically, birinone-based compounds include 2,6-noumethylpyridine, 2,4,6-trimethylpyridine, and sonorum-2.
-pyridinethiol-1-oxide, etc., and sonoram-pyridinethiol-1-oxide is preferred. Specific examples of the guanidine-based compound include cyclohexidine, polyhexamethylene guanidine hydrochloride, and dodecylguanidine hydrochloride, with dodecylguanidine and its salts being preferred. , 1 −/</4) system compound 11 conjugate +,:
11 /ch'v-1(butylcarbamoyl)-2-penzimidazolecarba1'4F・/+k 4
5 F'/-h-/(/4)! 1 Morpholine compounds are specifically 4-(2-
nitrobutyl)morpholine, 4-(3-nitrobutyl)
Morpholine etc. Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc., but tetraalkylphosphonium salts are preferred, and more specifically preferred compounds are tri'
-n"fftk-f) if', t., 8□,
One... , i6,)! J-7! There is nyl-nitrophenylphosphonium chloride. Specifically, quaternary ammonium compounds include benzal, l
, -U A m s 6/I 1. tsub@,, ga1. A7゜, 7゜] 1 ""°'7A□・7 tv N
tv e')'=7 A @"99・Specifically, there are dodecyldimethylbenzyl ammonium chloride, didecyldimethylammonium chloride, laurylpyridinium chloride, etc. Urea-based compounds are specifically N-(3,4 -dichloro7enyl)-N'-(4-chlorophenyl)urea, N-(3
-trifluoromethyl-4-chloro7enyl)-N'-
(4-chlorophenyl)urea and the like. Specifically, inxazole compounds are 3-hydroxy-
Examples include 5-methyl-inxazole. Propertool amine compounds include n-propertools and isopropertools, specifically I) L-2-benzylamino-1-propertool, 3-diethylamino-1-propertool, 2-dimethyl Amino-2-methyl-1-furopanol, 3-7 minnow 1-propanol,
Idopropaturamine, diisopropaturamine,
Examples include NN-dimethyl-isopropazuramine. Specifically, the sulfuramide derivative is 7-fluorinated sulfuryl yi:
)', 4-chloro-3f5-dinitrobenzenesul77
mido, sul7anilamide, acetosulfamine, sul7aviridine, sul7aguanicine, sul7athiazole, sul7adianone, sul7amelanone, sulfamethanone, sul7isoxazole, homosulfamine, sulfisomycin, sul7adianone, sul7ametisol , sulfapyranone, phthalisosulfate thiazole, succinylsulfate thiazole, and the like. A specific example of the amino acid compound is 1-lauryl-β-alanine. Among the above antifungal agents, compounds preferably used in the present invention include thiazole compounds, birinone compounds,
These are guaninone-based compounds and quaternary ammonium-based compounds. Furthermore, thiazole compounds are particularly preferred. The amount of antifungal agent added to the water washing alternative treatment solution is as follows: Water washing alternative treatment 1
The range is preferably from 0.002g to 50g, more preferably from 0.005g to 10g per liter. Preferred compounds to be added to the water-washing substitute stabilizer used in the present invention include ammonium compounds. These are co-supplied by 33 ammoniums of various inorganic organic compounds, specifically ammonium hydroxide, ammonium bromide, ammonium carbonate, Ikenita ammonium, ammonium phosphate, ammonium phosphate, Ammonium phosphite, ammonium heptadide,
Acidic ammonium heptonide, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium mizuki heptadide, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, heptadmonium 11 borate, ammonium acetate, ammonium heptanobate, Ammonium lauric tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium ethylnotiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen heptalate, ammonium hydrogen acid , ammonium thousand osulfate, ammonium diosulfate, ammonium ethylenenoaminetetraacetate, ammonium 1-hydroxyethylidene-1,1-nophosphonate, ammonium lactate, a=2 malate
3- ammonium maleate, ammonium sulfate, ammonium heptalate, ammonium picrate, ammonium birolinonenotiorubamate,
Ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2 + 4 w 6 +
rlinitrophenol ammonium, etc. These may be used alone or in combination of 2 or more L. The amount of ammonium compound added is 0.00% per 1g of stabilizer.
001 mol to 1.0 mol, preferably If,
It is in the range of 0.002 to 0.2 mol. In the present invention, the washing alternative treatment liquid preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions. What is the chelate stability constant here? ?
,”5tabilityConst a n
Meeting of Metal-ion Co+
nplexes”, TI+e C1+emical
5ociLy, 1ondon (!964), S, Cb
aberek + ^, E1Marle11 people “Or
ganic 5equesterinFi^genLs
In the present invention, the chelating agent whose chelating constant for iron ions is 81)J, l: is an organic carboxylic acid chelating agent, Examples include sulfuric acid chelating agents, organic phosphoric acid chelating agents, polyhydroxy compounds, etc.
I am confused. In the present invention (2), specific examples of compounds of the chelating agent having a chelating stability constant of 61'J, l- with ferric ions include, but are not limited to, the following compounds: Namely, ethylene, meamine diorthohydroxyphenyl acid, noaminopropane tetrar11 acid, nitrile, acetic acid, hydroxyethylethylenenoamine: acetic acid, hydroxyethylglycine, ethylenenoamine [, acetic acid, enaleno] Amine niprobionic acid, imi72-m acid, noethylenetriamine Ii' acid resistance, hydroxyethylidene 7゛. Acetic acid, noaminopropanoltetraacetic acid, 1 lance cyclohexanenoaminetetrachuic acid, ethylenenoaminetetraacetic acid, glyfur ether Noaminetetraacetic acid, 1, ethylenediaminetetrakismethylenephosphonic acid, '. Nitrilotrimethylenephosphonic acid, 1-hydroxy 1.
4. Ethylidene-1,1-diphosphonic acid, 1.
1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-1pe1. 5. Ricarboxylic acid, 1-hydroxy-1-phosphonopropane 91, -1.2.3-)licarboxylic acid, catechol-3,5-disulphic acid, birophosphate , sodium tetrapolyphosphate, and sodium hexametaphosphate, particularly preferably ^-P03H2 (in the formula, H
represents a cation such as a hydrogen atom, a sodium atom, a potassium atom, or ammonium. ^ represents inorganic or organic matter. )
It is a compound represented by, for example, 2-phospho7butane-1.2°4-tricarboxylic acid, ], 1-diphosphonoethane-2-carboxylic acid, pyrophosphoric acid, sodium tetrapolyphosphate, sodium hexametaphosphate, Sodium polyphosphate, nitrilotrimethylenephosphonic acid, ethylenenoaminetitraphosphonic acid, diethylenetriamij
"P"y""""""acid, 1-"doxyp°8lyso"'-1,1 diphosphonic acid, 1-7minoethylidene-1,1-diphosulfonic acid, 1-hydroxyethylidene-1,1 -Diphosphonic acids and their salts. The amount of the chelating agent used in the present invention is 0.01 to 508, preferably 0.05 to 201, per water washing alternative treatment. Good results can be obtained within this range. It is preferable that the water washing alternative treatment liquid in the present invention contains a metal salt in combination with the chelating agent. Such metal salts include Ba=Ca+Ce'4Co+I
r+, 1. a, Mn+N1tPb+Sn+Zn, Ti,
It is a metal salt of Zr+Mg+AQ or Sr, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, or acetate, or as a water-soluble chelating agent. The amount used is lXl0-4 to IX10-4 per stabilizer IQ.
molar range, preferably 4X 10-' to 2X
10-2 moles, more preferably 8x 10-' = lx
The range is 102 moles. Others

[The commonly known stable bath temperature machining is
Examples include optical brighteners, surfactants, organic sulfuric acid compounds, onium salts, formalin, hardeners such as chromium, and various metal salts. Any compound may be used in any combination as long as it is necessary to maintain the stability of the color photographic image and does not adversely affect the stability of the color photographic image during storage and the occurrence of precipitation. Processing temperature is 15℃~
The temperature is 60°C, preferably 20°C to 45°C. The treatment time is 2 minutes or less, and within this range, the occurrence of esso contamination is significantly improved. More preferably, the treatment time is 1 minute and 30 minutes or less. - On the other hand, if the treatment time is too short, the stabilizing effect will be insufficient, so it is desirable that the treatment time is 20 or more. In the case of multiple tank stabilization treatment, the first stage tank should be processed in a short time.
It is preferable that the treatment time in the latter stage tank is long. In particular, it is desirable to sequentially perform the treatment with a treatment time 20% to 50% longer than in the previous tank. After the stabilization treatment according to the present invention, there is no need for rinsing at all, but rinsing with a small amount of water within an extremely short period of time, surface cleaning with a draining solution containing formalin, surfactants, etc. may be performed as necessary. (arbitrary line) is possible. The method for supplying the water washing substitute stabilizing solution in the stabilization treatment process according to the present invention is that when a multilayer counter current method is used, the water washing substitute stabilizing solution in the present invention is supplied to the after bath and over 70 minutes from the front bath. Formulas (n), (m),
It is preferable to carry out the reaction in the presence of a compound represented by [IV] or (V). General formula (IT) In the formula, R, R,, R2, R,, R, and R5 are each hydrogen atom: halogen atom (e.g., chlorine atom, bromine atom, seven-stranded atom); hydroxy group; alkyl Group (1 carbon number
-4 is preferred. For example, methyl group, ethyl group, propyl group); alkoxy group (preferably 1 to 4 carbon atoms; for example, methoxy group, ethquin group, propoxy group); -
SO,M ; or -old IR' represents a 301M group. Here, R' represents an alkylene group (e.g. methylene group, ethylene group), M is a cation, hydrogen atom; alkali metal atom (e.g. sodium atom, potassium atom); ammonium, organic ammonium salt (e.g. pyridinium , piperidinium, triethylammonium, triethanolamine, etc. Typical specific examples of the compound represented by the above general formula [■] are shown below. A-1) (A-2) (A-3) (A-4) (A-5) (A-6) General formula [sum] 14, 86' In the formula, R6 and Rg' are each a hydrogen atom or Alkyl group, each optionally substituted, ary
represents an alkyl group or a heterocyclic group, and this alkyl group may be linear, branched, or cyclic, and preferably has 1 to 4 carbon atoms.
Examples thereof include ethyl group and β-sulfoethyl group. The above aryl group is, for example, a phenyl group, a naphthyl group, etc., and may be bonded to the aryl group via a sulfo group (a divalent organic group, such as a phenyleneoxy group, an alkylene group, an alkylene amide group, an alkyleneoxy group, etc.). good.),
Carboxy group, carbon, alkyl group with 1 to 5 carbon atoms (e.g., methyl group, ethyl, 1, ...), halogen atom (e.g., chlorine atom, bromine atom, etc.), alkoxy group with 1 to 5 carbon atoms ( For example, 4-sulfophenyl group, 4-(δ-sulfobutyl)phenyl group, 3- Sulfo-7enyl &, 2,5-disulfophenyl group, 3,5-disulfophenyl group, 6,8-disulfo-2-su7tyl group, 4,
8-disulfo-2-su7tyl group, 3.5-dicarboxyphenyl group, 4-carboxyphenyl i, 4-(4-sulfophenoxy)phenyl group, 4-(2-sulfoethyl)phenyl group, 3-( Examples include sulfomethylamino)phenyl group and 4-(2-sulfoethoxy)phenyl group. Examples of the -1- structural ring group include 2-(6-sulfo)benzthiazolyl group, 2-(6-sulfo)benzoxasilyl group, etc. , chlorine atom, bromine atom, etc.), alkyl group (e.g., methyl group, ethyl group, etc.), aryl group (e.g., phenyl group, etc.), carboxyl group, sulfo group, hydroxy group, alkoxy group (e.g., methoxy group, etc.), aryl It may have a substituent such as an oxy group (for example, a phenoxy group). R7 and R7' are each a hydroxy group; an alkoxy group (
The number of carbon atoms is preferably 1 to 4. For example, a methoxy group, an ethoxy group, an isopropoxy group, a 1-butoxy group); a substituted alkoxy group, such as an alkoxy group having up to 10 den atoms or an alkoxy group having up to 2 carbon atoms;
v v, '4 Sy N (etr I -9゜loethoxy group, β-methoxyethoxy group); cya 7 group;
Trifluoromethyl group; -COOR8; -CONHR. ; -NIICOR, (R8 is a hydrogen atom; carbon number 1-4
a furkyl group (preferably having 1 to 4 carbon atoms); a spanning aryl group (e.g. phenyl group, naphthyl group)
and the alkyl group and aryl group are substituted and
16], may have a sulfo group or one carboxy group as the group. ); ureido group; imi7 group; ami7 group; substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms (e.g., ethylamino group, represents an integer of dimethylamino 2, X is an oxygen atom, a sulfur atom represents a cyclic amino group (e.g., a morpholef group, a bipel 7 group, or a 7-piperazi group). The methine group represented by 1 is an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, iso-propyl group, tertiary-butyl group, etc.) or an aryl group (e.g., phenyl group, tolyl group, etc.). etc.) may be replaced. Furthermore, at least one of the sulfo group, sulfoalkyl group, and carboxy group possessed by the above heterocyclic group is an alkali metal (e.g., sodium, potassium), an alkaline earth metal (e.g., calcium, magnesium), ammonia, or an aritsuki base (e.g., diethylamine). , triethylamine, morpholine, pyridine, piperidine, etc.). n represents 0, 1 or 2, Il
l and l' each represent 0 or 1. Next, typical specific examples of the compound represented by the general formula [IT[] will be shown.
) (B-2) (B-3) (II-4,) (B-5) (B-6) (B-7) ++00c -C-C= Cl1-C-C-COOI+
(B-8) (B-9) (B-10) (B-11) (B-12) (B-13) IO (B-14) (B-15) (B=16) (B-17 ) (B-18) +j (B-19) , ] ・1 (B-20) (B-21) 1 bυ3
K SU3 (B-22) (B-23) (B-25) (1'l-26) 11・N″kc -C=C11-CII=CIl-CI
I=CIl-C-C/N”・II I
II 11 (R3-27) SO3NIIt bυ3NII4
(B-28) (II-29) General formula (IV) =47 In the formula, r represents an integer of 1 to 3, W represents an oxygen atom or a sulfur atom, ■ represents a methine group, R9- R12
each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and at least one or more of R9 to R1□ is a substituent other than a hydrogen atom. (2) As the methine group represented by -, those mentioned in the section of the general formula [rll] can be mentioned. The alkyl group represented by R8 to R12 is represented by the general formula [
The same alkyl groups as R6 and R6' mentioned in the section III) can be mentioned, and the alkyl group may have a substituent.
Examples of the substituent to be introduced into the group R6' include the various substituents listed above, but preferred are sulfo, carboxyne,
These are hydroxy, alkoxy, alkoxycarbonyl, cyano, and sulfonyl groups. The aryl group represented by R9 to R1□ is preferably a phenyl group, and the substituents introduced into this phenyl group are:
The various substituents mentioned in the section of the general formula [■] can be mentioned as substituents to be introduced into the groups R6 and R6゛. It has two groups, preferably two. The aralkyl group represented by R9-R12 is preferably a benyl group or a 7-enethyl group, and the substituents introduced into this aromatic nucleus -1- are the same as the substituents for the 7-aryl group R0 to R12 described above. I can do it. Examples of the heterocyclic group represented by R5 to R12 include pyridyl, pyrimidyl, etc., and substituents introduced into this heterocyclic ring -L include the above-mentioned R5 to R1.
It is possible to list the same substituents for the aryl group in □. [<, The group represented by ~R12 is preferably an alkyl group or an aryl group, and furthermore, carboxy, sulfo, and sulfo moyl groups are present in the molecule of barbylic acid and thiobarbylic acid represented by the general formula [IV]. It is desirable to have at least one group, and symmetrical ones are preferred. ,...Next, typical examples of the compound of the above general formula [■] will be shown, but the present invention is not limited thereto. (C'-2) (C-3) C4He -n C41Le -n(C
-4) (C-5) (C-6) C,1Is-n C4Hs
-n General formula (V) ゛Pa ni -3・;1 In the formula, Q represents an integer of 1 or 2, and ■
, represents a methyl group, and the alkyl group, aryl group, and heterocyclic group represented by R11 are R6, '1, and Ra' of the general formula [111].
It has the same meaning as , and is preferably an alkyl group or an aryl group, and the aryl group preferably has at least one sulfo group. R14 and RIs are all substituents represented by R7 and R' in the general formula Cu1l) and an alkyl group are introduced, preferably an alkyl group, a carboxyne group, an alkoxycarbonyl group, a carbamoyl group, a ureido group, 7 acylamides,
It is selected from imino groups and cyano groups. R1
The alkyl group in 4 may be linear, branched, or cyclic,
It preferably has 1 to 6 carbon atoms, and may be substituted with a hydroxy group, carboxy group, sulfo group, etc. Examples include methyl, ethyl, 1so-propyl, n-butyl, hydroxyethyl, and the like. Examples of the alkyl group of the amine 7 group substituted with a flukoxy group and an alkyl group in R8 and RIs include a methyl group, an ethyl group, a butyl group, a hydroxyalkyl group (e.g., hydroxyethyl, etc.), an alkoxyalkyl group (
(e.g., β-ethoxyethyl, etc.), carboxyalkyl groups (e.g., β-carboxyethyl, etc.), alkoxycarbonylalyl groups (e.g., β-ethoxycarbonylethyl, etc.), cyanoalkyl groups (e.g., β-cyanoethyl, etc.) , sulfoalkyl groups (eg, β-sulfoethyl, r-sulfopropyl, etc.). 1 and 16 represent a hydrogen atom, an alkyl group, a chlorine atom, or an alkoxy group, and examples of the alkyl group include methyl and ethyl, and examples of the alkoxy group include methoxy and ethoxy. Next, one representative example of a shellfish of the general formula [V] is shown, but the present invention is not limited to this. 4) (r)-5) SO5Na (]”)-6) (1”)-7) SO,K (D-8) So, Na 1- General formula CI, CIIt ], [■] or ( V
) compounds are disclosed in U.S. Patent Nos. 3,575.704 and 3,2.
No. 47.127, No. L540,887, No. 3,653
, 905, JP-A No. 48-85130, JP-A No. 49-99820, JP-A No. 59-111640, JP-A No. 59
It can be synthesized by the synthesis method described in each publication of No. 111641 and No. 59-170838. Also, general formula (Il), (II), "■" or [■]
The compound represented by may be incorporated into any layer of the silver halide emulsion layer or other hydrophilic colloid layer in the light-sensitive material. 1) Dissolving an organic or inorganic alkali salt of the compound in water, It can be added to a coating solution such as an emulsion as an aqueous dye solution of an appropriate concentration and coated by a known method to be incorporated into a light-sensitive material, preferably in the emulsion layer and its adjacent layer. The content of these compounds is 1 to 800 iog/m2 of the photosensitive material, preferably 2 to 200 [Dg/l1
Make it 12. The above general formula (n), [IIt, ], (IV) or 1
Among the compounds represented by [V], general formula (I
Particularly preferred are compounds represented by II). In addition, the photosensitive material to which the method of the present invention is applied is a combination of two or more of these compounds.
− Silver halide emulsion layer and non-light-sensitive layer (non-emulsion layer)
The silver halide emulsion includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, silver chloride iodobromide, etc. It may also be possible to use These emulsion layers and non-light-sensitive layers can contain any couplers and additives known in the photographic industry, such as yellow dye-forming couplers,
magenta dye-forming coupler, cyan dye-forming coupler,
Stabilizers, sensitizing dyes, gold compounds, high-boiling organic solvents, antifoggants, dye image fading inhibitors, color stain inhibitors, optical brighteners, antistatic agents, hardeners, surfactants, plasticizers, A wetting agent, an ultraviolet absorber, etc. can be included as appropriate. In the photographic material to which the method of the present invention is applied, constituent layers such as an emulsion layer and a non-photosensitive layer containing various photographic additives as described above may be treated by corona discharge treatment, flame treatment or It is produced by coating on a support 1- which has been subjected to ultraviolet irradiation treatment or via a subbing layer or an intermediate layer. Advantageously used supports include, for example, bary 11
Fg, &ljx and 2. □1.1. ,a. , 2. □i
1, wa 1, 1□ll1lL. ,ヮ6.ヮIt l
im If, □, 6 clear support, such as glass plate, cellulose acetic acid, etc. -j, polyester films such as cellulose nitrate or polyethylene Tele 7 Talley F, boria 2, porcelain, midfilm, polycarbonate film, polystyrene film, etc. (The silver halide emulsion layer and the non-photosensitive The majority of the layer usually contains hydrophilic 1.i.
°"()1'!'""゛6.00 Parent*n'<<>r-
j, jl・“°1”“ゞy + > + A
2+ b゛l''7') k4''t' y f' s, gelatin derivatives such as guanidized gelatin, phenylcarbamylated gelatin, heptadated gelatin, cyanoethanolated gelatin, and esterified gelatin:・1
The body is used carefully. Dura mater 1 for curing this hydrophilic colloid layer. effect
Examples of agents include chromium salts (chromium alum,
Vinegar): acid chromium, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhyguntoin, etc.), nooxane derivatives (2,3-dihydroxydioxane), etc. Active vinyl compound (1,3,5-)lyacryloyl-hexahydro-5-)ryanone, 1,3-vinylsulfonyl-2-
propatool, etc.), active halogen compounds (2,4-cyclo-6-hydroquine-5-) riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc., used alone or in combination. . Further, the present invention is particularly effective when the photosensitive material is of the so-called oil-protected type, which contains a coupler dispersed in a high-boiling organic solvent. This high boiling point organic solvent can be used as organic acid 7-mides, carbamates, esters, ketones, urea derivatives, etc., especially dimethyl 7-tally, diethyl 7-tally, di-propyl 7-tally, di-butyl 7-tally, di- -n-octyl 7-talate, diisooctyl 7-thaleate, cyamyl 7-talate, noanyl 7-talate, diisodecyl phthalate and other 7-talic acid esters, tricrennor 7-mole 7-ate, tri-7enyl 7-eth, Phosphate esters such as tri-(2-ethylhexyl 7-o-7ate), sebacate esters such as no-octyl sebacate, no-(2-ethylhexyl) sebacate, diisodecyl sebacate, glycerol tripropionate, glycerol tributyrate, etc. esters of glycerin, others, anovic acid esters, geltaric acid esters, succinic acid esters,
When using 7-7ol derivatives such as maleic acid ester, 7-malic acid ester, citric acid ester, not-tert-7milphenol, 11-octyl717ol,
The effects of the present invention are significant. For the color development in the present invention, an aromatic primary amine color developing agent is used, and the developing agent includes known ones that are widely used in various color photographic processes. These developing agents include amyl77el and p7z nylennoamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds are generally contained in an amount of about 0.1 g to 1Q of color developer.
A concentration of about 30 g is used, preferably from about 1 g to about 1.5 g per color developer. As the Ami7 phenol developer, for example, 〇-Ami7
Phenol, 1]-aminophenol, 5-7mi7-2
-oxytoluene, 2-7minor-3-oxy)/renin, 2-oxy-3-amino-1. Includes 4-methylbenzene, etc. A particularly useful aromatic primary amine color developer is N. N'
-Noalkyl-1] - It is a phenylenenoamine type compound, and the alkyl group and phenyl group may be substituted with any substituted group. Among them, examples of particularly useful compounds include N-N'-noethyl-p-phenylenenoamine hydrochloride, N-methyl-1]-phenylenecyamine hydrochloride,
, N-dimethyl 1)-phenylenecyamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-ami7aniline sulfate, N-ethyl-N-β- Hydroxyethylaminoaniline, 4-
amino-3-methyl-N,N'-noethylaniline,
Examples include 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate. In addition to the above-mentioned aromatic primary amine color developer, the color developer also contains various components normally added to color developers, such as hydroxide, l) rum, sodium carbonate, potassium carbonate, etc. Alkali agents, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of a color developing solution using an aromatic primary amine color developing agent as the color developing agent is usually from 7 to 2, and most commonly from about 10 to about 13. Further, the effects of the present invention are particularly remarkable when the photosensitive material is photographic paper and a fluorescent whitening agent is contained during color development. A preferred optical brightener is a 4,4-sifminostilbene optical brightener, and the amount added is 0.0000000000000000000000000000,000,000 per color developer. +1?
~30. The range is preferably 0.3 to I
This is within the scope of OB. Preferred examples of fluorescent brighteners are described in Japanese Patent Publication No. 57-58651. Not only the water-washing alternative stabilizing solution used in the processing method of the present invention, but also the processing solution containing soluble silver complex salts such as a fixing solution and a bleach-fixing solution can be recovered by a known method using a planer and then processed by electrolysis. Law (French Patent No. 2,299,66
7), precipitation method (described in JP-A-52-73037 and Sec. Patent No. 2,331.220 specification-1)
, the ion exchange method (described in JP-A-51-17114 and the specification of Second Patent No. 2,548.237) and the metal substitution method (described in the specification of Kasei Patent No. 1:151,805) are effectively utilized. can. The processing method of the present invention is advantageously applied to the processing of single color paper, color border paper and reversal color paper. In addition, examples of processing steps in which the present invention is particularly effective include the following (1) force and wear. (1) Color development - Bleach fixing - Water washing alternative stabilization treatment
i? '! '1, + (*m"゛1 A passage explaining the present invention in terms of examples below."
Ka1, Yut'Ll: Yo, □1oo-yo7. -5゜6 River It's not something. 1 Example-1 An experiment was conducted using the following color paper, processing liquid, and processing process. [7L/<-7<-) The following layers were sequentially coated on a polyethylene coated paper support from the support side to prepare a photosensitive material. In addition, polyethylene two 1 paper is 200 parts by weight of polyethylene with an average molecular weight of 100,000 and a density of 0.95, and an average molecular weight of 2,000 and a density of 0.80.
6.8% by weight of anatase-type nathane oxide was added to a mixture of 20 parts by weight of polyethylene and 1 part by weight was applied to the surface of a 170H/w2 paper with a thickness of 0 by extrusion coating.
．． A coating layer of 035III was formed, with only polyethylene on the back and the top. A coating layer with a thickness of 0.040 mm was provided on the polyethylene coating surface of the support surface, and a coating layer of 0.040 mm in thickness was used.
Yoo □, □101, □yo. First layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 80 mol% of silver bromide. 200 mg of 2,5-di-butylno)hydroquinone, sensitized using sensitized color probe 2.5X]O-'' mole (using isopropyl alcohol as solvent) and dissolved and dispersed in dibutyl 7-talate. / In 2 and yellow coupler a-14-(1-benzyl 27e::J and 3゜5-nooxo 1.2.4-1 riasilinol)]]
α-Vivalyl-2-chloro-5-γ-(2,4-no-monoamyl7eth/xy)butyramide 1 acetanilide contains 2 x 10-mol per 111 mol of halogenated, so that the silver amount is 330II/l112 It is coated. Di-1-octylhydroquinone 30011Ig/In2 dissolved and dispersed in 2M dibutyl phthalate, 2-(2'-hydroxy-3',5'-
No 1-butylphenyl)benzotriazole 2-(2
'-Hydroxy-5'-1-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-thi-
Butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3',5
'-not-t-butylphenyl)-5-chloro-benzolyazole mixture 200 + ng/gelatin 2000 In with a gelatin layer containing 2000 In 8/In
It is coated so that it becomes 2. Third layer: Green-sensitive silver halide emulsion J14 consisting of a silver chlorobromide emulsion containing 85 mol % of silver bromide, the emulsion containing 450.0 ml of gelatin per mol of silver halide. 2, which was sensitized using 2.5XIO' mol of a sensitizing dye having the following structure per mol of silver halide, and dissolved and dispersed in a solvent containing a 2:1 mixture of butyl heptatarate and I recrennorphos 7ate, 5-di-L-butylhydroquinone 150 In B/m2 and 1-(2,4,6-)lichlorophenyl)- as magenta coupler
Containing 1,5X 10-' mole of 3-(2-di-4-5-octadecenylsuccinimideanilide 7)-5-pyrazolone per mole of silver deaide, silver i1800B/
It is applied so that it becomes llI2. In addition, (B-22) of the exemplary compound of the general formula (r[[]) is 15 to
g/to 2. No. 47m: No-1-octylhydroquinone 30 In H/In 2 dissolved and dispersed in butyl 7-talate and 2-(2'-hydroxy-3', 5 as an ultraviolet absorber)
' -not-t-butylphenyl)benzo)l) 7sol, 2-(2'-hydroxy-5'-1-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'
-1-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3
', 5'-t-butylphenyl)-5-chloro-benzotriazole mixture (2:1.5:1.5:2)
The gelatin layer contains 500 mg/+02 of gelatin, and the amount of gelatin is 2000v1g/l112. No. 51: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide, the emulsion containing 500 g of gelatin per mol of silver halide, and having the following structure per mol of silver halide: sensitizing dye with 2.5XIO-'' moles of 2,5-no-1-butylhydroquinone III g/l dissolved and dispersed in dibutyl 7-talate and 2,4-dichloro-3 as cyan coupler. -Methyl-6-[γ-(2,
It contains 3.5 x 10-' mol of 4-noamylphenoxy)butyramide]7 ethyl per mol of silver halide, and is coated in a silver amount of 300 III g 7 m 2 . In addition, (A-1) of the exemplary compound of the general formula [■[]
was contained at 1511 Ig/w'. 6th layer: gelatin layer with gelatin amount of 1000 In B/l
112. The silver halide emulsions used in each photosensitive emulsion layer (j'th, 3rd, and 5th layers) were prepared using WI4ML and sodium thiosulfate pentahydrate, respectively, according to the method described in Japanese Patent Publication No. 7772/1972. Chemically sensitized, 4-hy2 as a stabilizer,
, droxy-6-methyl-1,3,3a,?
-tetrazaindene, bis(vinylsulfonyl methyl) ether as a hardening agent and saponin as a coating aid. After exposing the color paper produced by the above method,
Continuous processing was performed using large processing steps and processing solutions. Standard processing step, 1[11 color development 38°C 3 minutes, i:[
2] Bleach fixing 33℃ 1 minute, '], 1
[°1 Stable Here 1 Pa℃～°゛℃ Minutes”
[4] Drying 75℃~1
00'C approx. 1 min・j:'1 Processing liquid composition (color developing tank liquid) Benzine alcohol 15mQ Ethylene glycol Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride 0.2° Potassium carbonate 30.0g 3-Methyl- 4-
7 minnow N-ethyl-N-(β-methanesulfonamidoethyl)-7niline hydroxylamine sulfate
3.0g 1-hydroxyethylidene-1,1-niphosphophone RO, 4g Bitroxyethyliminodiacetic acid 5.0g Magnesium chloride, 6 water points 0.7g 1.2
-Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2g Add water to make IQ, K
Make pl-110,20 with OH and H2SO4. Color development replenisher> Bennol alcohol 20. OmQ Ethylene Glyfur 20. OmQ□゛′λ Potassium sulfite
3.0g・, し:. ψ ・、： 、ノ Potassium carbonate
30. Ogzu Hydroxylamine sulfate
4.03 Tsukasa, 3-methyl-4-amino-N-ethyl-N
-Heat i, l 11 (β-methanesulfonamidoethyl)-aniline□shi1 1i1- h l/ U″″′”-+ IJ f'>
−“°゛−″″″″″1′■ Acid

0.5g-bitroxyethyliminodiacetic acid5. Og
゛] )';zu 1 conversion"ytv>'yb-6*t1M
°・8"1.2-Dihydroxybenzene-3,5-) Nosulfonic acid disodium salt 0.3g・,1 Bleach-fix tank solution> Ferric complex salt of the chelating agent in Table-1 80gTable-1
Chelating agent 20g ammonium thiosulfate (70% dissolved) 100J ammonium sulfite (40% dissolved) 27.5. Adjust the pH to 7.1 with Q ammonium water or glacial acetic acid and add water to bring the total volume to 1Q. <Bleach-fix replenisher> 300 g of ferric complex salt of the chelating agent shown in Table 1
Chelating agent in Table 1 Adjust the pH to 6.7 with 50° potassium carbonate or glacial acetic acid, and add water to bring the total amount to IQ. <Bleach-fix replenisher B> Ammonium thiosulfate (70% dissolved) 500
WIQ ammonium sulfite (40% solution M)
250mQ Table-1 chelating agent
Adjust the pH to 5.3 with 15g ammonia or glacial acetic acid, and add water to bring the total volume to IQ. Water washing alternative stable tank liquid and replenishment liquid> 5-chloro-2
-Methyl-4-isothiazoline-3-ore
0.02g2-Methyl-4-isothiazolin-3-one 0,02゜Ethylenedifur 1.0g2-
Octyl-4-inchazolin-3-one 0.0+g 1-hydroxyethylidene-1,1-niphosphonic acid (6
0% aqueous solution) 3. oFiB
icI, (45% aqueous solution) 0
．． 65g ammonia water (ammonium hydroxide 25% aqueous solution) 3.08 Nitrilotrimethylenephosphonic acid 1.5g Water to make 19, II, So, and 011 to make 11 II 8 , O. Best for automatic developing machines! ] Fill the color developer tank solution, bleach-fix tank solution, and stable tank solution listed below, and add the color developer replenisher, bleach-fixer replenisher A, B, and stable replenisher indicated in ■- every 3 minutes while processing the color vapor. A running test was conducted while supplementing the light through the Jigaki power amplifier. The amount of replenisher is 190 companies per color paper 1 "n2 per I). The amount of replenishment to the color development tank is 190, the amount of replenishment to the bleach-fixing tank is 50 mQ each of bleach-fixing replenisher A and B, and the amount of replenishment to the stabilization treatment bath. 230m of stable replenishment solution as an alternative to washing with water!
l was replenished. Note that the stabilization bath of the automatic processor is located at the 14th f! in the direction of the flow of the photosensitive material. ~No. 341! Let the stabilizing tank be i, and 1
The tank lasted for 20 seconds, and replenishment was performed from the final tank, and the overflow from the final tank was allowed to flow into the previous tank, and this over 70-liquid was also flowed into the previous tank in a multi-tank countercurrent direction. Continuous processing is performed for each of the bleach-fixing solutions No. 1 to No. 1 using the chelating agent shown in Table 1 until the total replenishment amount of the water washing alternative stabilizing solution becomes twice the capacity of the stabilizing tank, and then the continuous processing is completed. The photographic material treated at the time was taken as a sample, and a stabilizing solution was taken from the second stabilization tank. In addition, for comparison, after continuous processing, a photosensitive material was processed by washing with running water for stabilization processing]. The photographic material after processing was stored at 80°C and 170% RH for 31-1 days in Y, Bay 9-, and the yellow stain after storage was measured using an optical densitometer PI''+A-65 (Konishiroku Photo Studio). The measurement was carried out using a blue circle (manufactured by Soko Co., Ltd.).The results are shown in Table 1.In addition, the sampled 1st + f4 water washing alternative stabilizing solution was
! l! As is clear from the results in Table 1, bleaching agents using a ferric complex salt of a chelating agent with a large molecular weight (NO
ll-No, 4), the present invention's NO, 5
- No. 10 has excellent yellow stain and liquid storage stability, and furthermore, from a comparison with No. 005 to No. 18 and above, it is extremely preferable to use the chelating agent represented by the general formula [I]. Recognize. Example-2 After continuous processing for N001 and N008 of Example-1,
The processing time of the water washing alternative stabilization treatment process is 45 seconds (1M15
seconds) 1 minute (20 seconds per tank), 1 minute 30 seconds (30 seconds per tank),
2 minutes (1 tank 40 seconds), j2 25) 31 ("6゛°"
)1v39(1M15?)h*(ts3-ttf The color par of Example-1 was processed.The white background of the unexposed part of the obtained processed color paper was analyzed for spectral reflection using a color analyzer (manufactured by Hitachi, Ltd.) Concentration')"l As is clear from the results in Table 2, the water washing alternative is stable here, 1'!"1"/2?"1
“1°・* Q 1+11 y> * r”t '72
It can be seen that the one using *n has a low reflection density on a white background and is extremely excellent.・；□! ' Example-3 °□゛ A89111 (IQNo, 1□No, 5nf
i. Table 3 shows the replenishment amount of water washing alternative replenisher for each of −Y3° and □57;・j 21 Near N L ? j
r h < 30+++Q/+. 2.60m (1/+
a2.100m<1/u2, :1 25(hQ/+a2.500IIIQ/1112.80
0J/m2. and change to 2Q/m2; As expected, continuous processing was performed, and the same experiment as Example-1, 1
was carried out to determine the yellow stain concentration. The result, j
It is shown in Table-3. -Oh, □Oh, R1m. □. 6□2,71. Ei, 4
The amount of liquid brought into the alternative stabilizing tank liquid is 30 ml (/μ2). The effect is greater when the amount is twice as large.Example-4 Example-4 Except that Exemplary Compound B-22 was removed from the third layer and Exemplary Compound A-1 from the fifth layer in the preparation of the photosensitive material of Example-1. A photosensitive material was prepared in the same manner as in Example 1. Using this photosensitive material, No. 1 and No. 1 of Example-1 were prepared.
Continuous treatment was carried out in the same manner as in 8. The 4401 spectral reflection density was measured for the white unexposed area obtained by this treatment. or,
A preserved sample was taken and yellow stain was measured. As a result, the spectral reflection density for No. 1 was (1,148), and for No. 8 was 0.119. Also, for Yellow Stain, No. 1 was 0.27, and No. 8 was 0.19. Compared with the results of Examples 1 and 2 in which the photosensitive materials contained the exemplified compounds of general formulas (■) to [V], the density difference of Yellow Stain was No., ] was 0.01, and No. , 0 in 8
．． 05, and the difference in spectral reflection density is No, 1 is "0.
It was No in 01 and 0.04 in 8. l;J, -1
The result of −V) is expressed by the general formula C■] or [V]^
-], l'1-22 is found to have an effective effect on the present invention. [Effects of the Invention] The processing method of the present invention improves the retention time of the washing substitute stabilizing solution in a processing power method in which processing with a bleach-fixing solution containing thiosulfate is followed by processing with a washing substitute stabilizing solution. This prevents the formation of fine black precipitates that occur in the dispersion.
In addition, the occurrence of yellow stain and contamination when photographic images processed by reducing the amount of replenishment of the water-washing substitute stabilizing solution when stored for a long period of time is improved.

Claims (5)

[Claims] (1) After color development of the silver halide color photographic light-sensitive material,
A method of treating with a bleach-fixing solution and subsequently treating with a water washing substitute stabilizing solution, wherein the bleach-fixing solution is mainly composed of an organic acid ferric complex salt, thiosulfate, and sulfite whose free acid has a molecular weight of less than 280. 1. A method for processing a silver halide color photographic material, characterized in that the processing time with the water-washing substitute stabilizing solution is 2 minutes or less. (2) The silver halide according to claim 1, wherein the organic acid ferric complex salt is contained in a range of 2 x 10^-^2 to 2 mol per liter of the bleach-fix solution. A method of processing color photographic materials. (3) The free acid of the above organic acid ferric salt has the following general formula [I
] The method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the compound is a compound represented by the following. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. group, or a carbosialkyl group having 1 to 4 carbon atoms.) (4) Claims 1 and 2, characterized in that the amount of replenishment of the water-washing substitute stabilizing solution is 2 to 20 times the amount brought in from the pre-bath per unit area of the photosensitive material to be processed. Or the method for processing a silver halide color photographic light-sensitive material according to item 3. (5) Claims characterized in that the silver halide color photographic light-sensitive material contains at least one compound represented by the following general formula [II], [III], [IV], or [V]. 4. A method for processing a silver halide color photographic material according to item 1, 2, 3, or 4. General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. 'SO_3M
represents. Here, R' represents an alkylene group and M represents a cationic group. ) General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. , alkoxy group, cyano group, trifluoromethyl group, -COOR_6, -CON
HR_8, -NHCOR_8, ureido group, imino group,
There are amino groups, substituted amino groups substituted with alkyl groups having 1 to 4 carbon atoms, or ▲mathematical formulas, chemical formulas, tables, etc.▼ (where p and q represent 1 or 2, and X is an oxygen atom, a sulfur atom, or -CH_2- group.) represents a cyclic amino group. R_8 represents a hydrogen atom, an alkyl group or an aryl group. L represents a methine group. n represents 0, 1 or 2. m and m' each represent 0 or 1. ) General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, r represents an integer from 1 to 3, W represents an oxygen atom or a sulfur atom, L represents a methine group, R_9~R
_1_2 each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and R_9 to R_1_
At least one of 2 is a substituent other than a hydrogen atom. ) General formula [V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, l represents an integer of 1 or 2, L represents a methine group, and R_1_3 represents an alkyl group, an aryl group, or a heterocyclic group. .R_14 and R_15 are each a hydroxy group, an alkyl group, an alkoxy group, a cyano group, a trifluoromethyl group, -COOR_8, -CONHR_8, -N
HCOR_8, ureido group, imino group, amino group, substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or -N<^[(CH_2)p]_[(CH_2)q]>
It represents a cyclic amino group represented by X (where p and q represent 1 or 2, and X represents an oxygen atom, a sulfur atom or a -CH_2- group). R_8 represents a hydrogen atom, an alkyl group or an aryl group. R_1_6 represents a hydrogen atom, an alkyl group, a chlorine atom or an alkoxy group. )