JPH0558185B2 - - Google Patents

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, which automatically and continuously develop photosensitive materials. It is desired to reduce or eliminate the large amount of washing water used. For this reason, methods have been proposed to reduce the amount of washing water that is used in large quantities. For example, West German Patent No. 2920222 discloses a technique for increasing the amount of washing water by configuring the washing tank in small stages and causing the water to flow backwards. and technical literature SRGoldwasser, “Water flow
rate in immersion−washing of motionpicture
film “Jour.SMPTE, 64 248-253, May (1955)
It has been known. Furthermore, a method of omitting the water washing step and performing stabilization treatment (alternative treatment for water washing) without substantially performing water washing is disclosed in JP-A Nos. 57-8543, 58-14834, and 58-
It is described in Publication No. 134636, etc. The pre-bath for such stabilization treatment contains thiosulfate, and the bleach-fix solution containing such thiosulfate is followed by a small amount of rinsing water as described above, rather than a rinsing treatment with a large amount of rinsing water. When pre-rinsing with water, multi-stage counter-flow small amount rinsing water, or alternative rinsing treatment in which processing is performed while replenishing with a small amount of replenishment, the residence time of the processing liquid used in these treatments is very short. become longer. Therefore, there is a drawback that fine black precipitates are likely to form in the processing solution over time during storage. As a method of preventing sulfide precipitation in the water washing step in order to eliminate such drawbacks, there is a technique, for example, according to US Pat. No. 4,059,446, in which a polyalkylene oxide type nonionic activator is added to the water washing bath. Furthermore, as described in JP-A No. 57-8542, there is a technique of adding isothiazoline or benzinthiazoline 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, if the amount of replenishment of the flushing alternative treatment is reduced,
There is a disadvantage that the concentration of bleach-fixing components in the final bath of the water-washing alternative stabilizer increases, and yellow stains due to long-term storage of unexposed areas of the photosensitive material increase. [Object of the Invention] Therefore, the 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. A second object of the present invention is to provide a method for processing silver halide color photographic light-sensitive materials that can prevent an increase in yellow stain due to long-term storage of unexposed areas of the light-sensitive material even if the amount of water-washing substitute stabilizer replenishment is reduced. It is about providing. [Structure of the Invention] An object of the present invention is to provide a method for processing a silver halide color photographic material after color development with a bleach-fixing solution and subsequently with a water-washing substitute stabilizing solution. contains at least one compound represented by the following general formula [], [], [] or [], and the replenishment amount of the water-washing alternative stabilizer is silver halide color photographic light-sensitive material 1.
60 to 500 ml per ^m2 , and the bleach-fix solution is an organic acid ferric complex salt whose free acid has a molecular weight of less than 280;
This is achieved by a method for processing a silver halide color photographic material, which is characterized by containing thiosulfate and sulfite as main components. General formula [] [In the formula, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, a sulfo group or a -
Represents NHR′SO ₃ M. Here, R' represents an alkylene group, and M represents a cation group. ] General formula [ ] [In the formula, R ₆ and R ₆ ' each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₇
and R ₇ ' are each a hydroxy group, an alkoxy group, a cyano group, a trifluoromethyl group, -COOR ₈ , -
CONHR ₈ , -NHCOR ₈ , ureido group, imino group,
An amino group, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or

It represents a cyclic amino group represented by the formula: (where p and q represent 1 or 2, and X represents an oxygen atom, a sulfur atom or a -CH ₂ - group). _R8 is a hydrogen atom,
Represents 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 [ ] [In the formula, r represents an integer of 1 to 3, W represents an oxygen atom or a sulfur atom, L represents a methine group, and R ₉ to _{R 12} are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or represents a heterocyclic group,
At least one of R ₉ to R ₁₂ is a substituent other than a hydrogen atom. ] General formula [ ] [In the formula, l represents an integer of 1 or 2, L represents a methine group, and R ₁₃ 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 , -NHCOR ₈ , ureido group, imino group,
An amino group, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or

It represents a cyclic amino group represented by the formula: (where p and q represent 1 or 2, and X represents an oxygen atom, a sulfur atom or a -CH ₂ - group). _R8 is a hydrogen atom,
Represents an alkyl group or an aryl group. R ₁₆ represents a hydrogen atom, an alkyl group, a chlorine atom or an alkoxy group. ] Hereinafter, the present invention will be explained in detail. Conventionally, organic acid ferric salts have been known as bleaching agents used in bleach-fix solutions, and ordinary bleach-fix solutions use thiosulfate as a fixing agent and sulfite as a preservative. In this method, ferric ethylenediaminetetraacetic acid is used as a ferric salt of an organic acid. The reason for using ferric ethylenediaminetetraacetate is that it is preferable in terms of desilvering properties, recoloring properties, and solution storage stability of the bleach-fix solution. Therefore, a process in which the washing process that uses a large amount of water following the bleach-fixing solution process is replaced with a process using a washing substitute stabilizing solution that uses a small amount of aqueous solution uses ferric ethylenediaminetetraacetic acid as a bleaching agent. It is used as a bath following the bleach-fix treatment step. In such a system, a problem arises in that the above-mentioned water-washing substitute stabilizer has poor storage stability over time, and yellow stains occur in unexposed areas of the processed light-sensitive material during long-term storage. As a result of intensive research into this problem, the present inventor surprisingly found that the above technical problem was solved when an organic acid ferric salt with a free acid molecular weight of less than 280 was used as a bleaching agent in a bleach-fix solution. This discovery led to the present invention. Furthermore, when the organic acid ferric salt is a compound represented by the general formula [], the effect of the present invention is particularly remarkable, and in such a system, the photosensitive material is a compound represented by the general formula [] to []. It has been found that the inclusion of the compound shown above is extremely preferable for preventing the above-mentioned yellow stain. As the free acid having a molecular weight of less than 280 in the organic acid ferric complex salt used in the present invention, aminopolycarboxylic acid compounds and polyphosphonic acid compounds are preferably mentioned, and among these, the former is more preferable, especially the general formula [] Compounds represented by are preferred. General formula [] In the formula, A represents 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 carbosial group having 1 to 4 carbon atoms. Particularly preferred A is a methyl group,
They are a hydroxyethyl group, a carboxymethyl group, a butyl group, and a hydrogen atom. For polyphosphonic acid compounds

[Formula] (where B and B ₁ each represent a hydrogen atom, a hydroxy group, an alkyl group, or an amino group) are included. Representative examples of the above-mentioned free acids are listed below, but the invention is not limited thereto. (Molecular weight in parentheses) (1) Nitrilotriacetic acid (191.14) (2) Nitrilodiacetic acid propionic acid (205.17) (3) Iminodiacetic acid (133.10) (4) Iminodimethylenephosphonic acid (204.98) (5) N-methyliminodiacetic acid Acetic acid (147.063) (6) Iminodipropionic acid (161.074) (7) N-(3,3-dimethylbutyl)iminodiacetic acid (217.12) (8) Hydroxyethyliminodipropionic acid (205.10) (9) Hydroxypropylimino Diacetic acid (191.09) (10) Methoxyethyliminodiacetic acid (191.09) (11) N-(carbamoylmethyl)iminodiacetic acid (190.08) (12) Aminoethyliminodiacetic acid (179.08) (13) β-(N-trimethyl ammonium)ethyliminodiacetic acid cation (219.12) (14) Phosphonomethyliminodiacetic acid (227.04) (15) Phosphonoethyliminodiacetic acid (241.2) (16) Sulfoethyliminodiacetic acid (241.14) (17) Hydroxyethylimino Diacetic acid (177.16) (18) Dihydroxyethylglycine (163.17) (19) Nitrilotripropionic acid (233.22) (20) Ethylenediaminediacetic acid (176.17) (21) Carboxyethyliminodiacetic acid (205.08) (22) N, N' -Ethylenediaminediacetic acid (172.08) (23) N,N'-di(hydroxyethyl)ethylenediaminediacetic acid (264.13) (24) Ethylenediaminedipropionic acid (277.15) (25) Hydroxyethylethylenediaminetriacetic acid (278.26) (26) 1-Hydroxyethylidene-1,1-diphosphonic acid (205.97) (27) Hydroxymethylidene diphosphonic acid (191.96) (28) 1-Aminoethylidene-1,1-diphosphonic acid (203.98) (29) 1-Amino Propylidene-1,1-diphosphonic acid (217.99) The organic acid ferric complex salt used in the present invention can be used alone or in combination of two or more. The concentration needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed.
The amount is preferably in the range of 2×10 ^-2 to 2 mol, more preferably 0.1 to 1.0 mol per liquid used. The bleach-fix solution in the present invention may contain, as a bleaching agent, a compound other than the above organic acid ferric complex salt, such as an organic acid ferric complex salt whose free acid has a molecular weight of 280 or more. 50 mol% of the amount
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. The concentration may be 5 g/or more, as long as it can be dissolved, but is preferably in the range of 40 to 250 g/. 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, potassium metabisulfite, ammonium metabisulfite, hydrosulfite,
Compounds such as sodium glutaraldehyde bisbisulfite and sodium succinic aldehyde bisbisulfite are mentioned, but any compound that releases sulfite ions may be used. The above sulfite is contained in the bleach-fix solution at a concentration of 1×10 ^-3 ~0.1
It is preferable to contain it in mol/mol. The bleach-fix solution in the present invention contains the organic acid ferric complex salt, thiosulfate, and sulfite as main components. This means that it is an iron complex salt, and that there is no problem in containing additives commonly used in bleach-fix solutions other than these three components. That is, the bleach-fix solution of the present invention contains various pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. They can be contained singly or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, methanol, dimethylsulfamide, dimethylsulfoxide, etc. An organic solvent or the like can be appropriately contained. Also, JP-A-46-280, JP-A-45-8506,
No. 46-556, Belgian Patent No. 770910, Tokukosho
Various bleach accelerators described in JP-A-45-8836, JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added. The pH of the bleach-fix solution used in the present invention is 4.0 or higher, preferably PH5.0 or higher and PH9.5 or higher, and more preferably PH6.0 or higher and PH8.5 or lower.
The processing temperature is 80° C. or lower, which is 3° C. or more, preferably 5° C. or more lower than the temperature of the processing solution in the color developing tank, but preferably 55° C. or lower to prevent evaporation. In the present invention, processing with bleach-fixing and then processing with a water-washing substitute stabilizing solution means that the concentration of the fixing solution or bleach-fixing solution brought into the first stabilization tank does not become 1/200 or less. This means that 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 stabilizing solution, and the treated layer is called a stabilizing bath or stable layer. In the present invention, the stabilization treatment can be carried out in one tank or in multiple tanks without any problem, but preferably one to four tanks. The present invention is most effective when the amount of water-washing substitute stabilizing solution replenished into the stabilizing bath is small, and the amount of replenishment is in the range of 2 to 20 times the amount brought in from the previous bath per unit area of the photographic material to be processed. The effects of the present invention are particularly remarkable. It is preferable that the washing water substitute stabilizer of the present invention contains an antifungal agent. Preferably used antifungal agents include hydroxybenzoic acid compounds, alkylphenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbament compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, and urea. These are compound-based compounds, isoxazole-based compounds, propanolamine-based compounds, sulfamide derivatives, and amino acid-based compounds. The hydroxybenzoic acid compounds include hydroxybenzoic acid and ester compounds of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester, butyl ester, etc., but preferably n-butyl ester, isobutyl ester, and propyl ester of hydroxybenzoic acid. It is an ester, and more preferably a mixture of the three hydroxybenzoic acid esters. Alkylphenol compounds have an alkyl group
It is a compound having a C1-6 alkyl group as a substituent, and other preferable phenolic compounds are orthophenol and orthocyclohexyphenol. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, preferably 1,
2-Benzithiazolin 3-one, 2-methyl-
4-isothiazolin 3-one, 2-octyl-4
-Isothiazolin 3-one, 5-chloro-2-methyl-4-isothiazolin 3-one, 2-(4-
thiazolyl)benzimidazole. Specific examples of pyridine compounds include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, and sodium-2-pyridinethiol-1-oxide, but preferably sodium-pyridinethiol-1-oxide.
1-oxide. Specific examples of the guanidine compound include cyclohexidine, polyhexamethylene guanidine hydrochloride, and dodecylguanidine hydrochloride, with dodecylguanidine and its salts being preferred. Carbamate compounds are specifically methyl-1
-(Butylcarbamoyl)-2-benzimidazole carbamate, methylimidazole carbamate, etc. Specifically, morpholine compounds include 4-(2-nitrobutyl)morpholine, 4-(3-nitrobutyl)
Morpholine etc. Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc., but tetraalkylphosphonium salts are preferred.More specific preferred compounds are tri-n-butyl-tetradecylphosphonium chloride, tri-phenyl/nitrophenyl. There is phosphonium chloride. Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, and alkylpyridinium salts, including dodecyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, laurylpyridinium chloride, etc. There is. Specifically, the urea-based compounds include N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl)urea, N-(3-trifluoromethyl-4-chlorophenyl)-N'-(4- chlorophenyl) urea, etc. Specific examples of isoxazole compounds include 3-hydroxy-5-methyl-isoxazole. Propanolamine compounds include n-propanols and isopropanols, and specifically,
DL-2-benzylamino-1-propanol,
3-diethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol,
Examples include 3-amino-1-propanol, isopropanol-amino, diisopropanolamine, NN-dimethyl-isopropanolamine, and the like. Sulfamide derivatives specifically include fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, sulfanilamide, acetosulfamine, sulfapyridine, sulfaguanidine, sulfathiazole, sulfadiazine,
Examples include sulfamerazine, sulfamethazine, sulfisoxazole, homosulfamine, sulfisomidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, succinylsulfathiazole, and the like. Specifically, the amino acid compound is N-lauryl-
There is β-alanine. Among the above-mentioned antifungal agents, compounds preferably used in the present invention are pyridine compounds, guanidine compounds, and quaternary ammonium compounds. The amount of the antifungal agent added to the water-washing alternative treatment solution is preferably in the range of 0.002 g to 50 g, more preferably in the range of 0.005 g to 10 g per liter of the water-washing alternative treatment. It is preferable that the water washing substitute stabilizing solution in the present invention 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? Written by L.G. Sill'en and A.E. Martell,
“Stability Constants of Metel−ion
Complexes”, The Chemical Society, London
(1964), written by S.Chaberek・AE Martell,
“Organic Sequestering Agents”, Wiley (1959)
etc. means a commonly known constant. In the present invention, examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent,
Examples include inorganic phosphoric acid chelating agents and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe ³⁺ ). In the present invention, specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include the following compounds, but are not limited thereto. Namely, ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid. , diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid,
Nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-
Diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-
Tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate are mentioned, and particularly preferred are A-PO ₃ M ₂ (wherein M is a hydrogen atom, a sodium atom, Represents a cation such as a potassium atom or ammonium. A represents an inorganic or organic group.) For example,
2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, pyrophosphoric acid, sodium tetrapolyphosphate,
Sodium hexametaphosphate, sodium polyphosphate, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, 1- Examples include hydroxyethylidene-1,1-diphosphonic acid and salts thereof. The amount of the above chelating agent used is 0.01 to 50 g, preferably 0.05 to 20 g per 1 water washing alternative.
is within the range of The water washing substitute stabilizing solution in the present invention preferably contains a metal salt in combination with the chelating agent.
Such metal salts include Ba, Ca, Ce, Co, In,
La, Mn, Ni, Pb, Sn, Zn, Ti, Zr, Mg, Al
or a metal salt of Sr, which can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate, or a water-soluble chelating agent. The amount used is 1×10 ^-4 to 1×10 ^-1 per stabilizer.
molar range, preferably 4×10 ⁻⁴ to 2×
It is in the range of 10 ^-2 mol. Other commonly known stabilizing bath additives include optical brighteners, surfactants, organic sulfur compounds, onium salts, formalin, hardeners such as chromium, and various metal salts. The amount of the compound to be added is determined by the amount necessary to maintain the pH of the stabilizing bath according to the present invention, and the amount of the compound to be added is within the range that does not adversely affect the stability of the color photographic image during storage and the occurrence of precipitation. It is okay to use it in The processing temperature during stabilization treatment is 15°C to 60°C.
℃, preferably in the range of 20℃ to 45℃. In addition, from the viewpoint of rapid processing, the shorter the treatment time, the better, but it is usually 10 minutes or less, preferably 5 minutes or less. In the case of multiple tank stabilization treatment, the earlier tanks are treated in a shorter time, and the later tanks are treated in a shorter time. Preferably, the treatment time is long. In particular, it is desirable to perform sequential processing with 20% to 50% longer processing time than in the previous tank. After the stabilization treatment according to the present invention, there is no need for any water rinsing treatment, but rinsing by rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. can be optionally performed as necessary. When the method for supplying the water-washing substitute stabilizing solution in the stabilization treatment step according to the present invention is a multilayer countercurrent method, it is preferable to supply it to the after bath and overflow from the front bath. The treatment with the water-washing substitute stabilizing solution in the present invention is carried out in the presence of the compound represented by the general formula [ ], [ ], [ ] or [ ]. General formula [] In the formula, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom; a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom); a hydroxy group; an alkyl group (having 1 to 1 carbon atoms); 4 is preferred. For example, methyl group,
ethyl group, propyl group); alkoxy group (preferably 1 to 4 carbon atoms; for example, methoxy group, ethoxy group, propoxy group); -SO ₃ M; or -
Represents the NHR′SO ₃ M 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. Representative specific examples of the compound represented by the general formula [] are shown below, but the compound is not limited thereto. (A -1) (A-2) (A-3) (A-4) (A-5) (A-6) General formula [] In the formula, R ₆ and R ₆ ' each represent a hydrogen atom or an optionally substituted alkyl group, aryl group, or heterocyclic group, and this alkyl group may be linear, branched, or cyclic, and is preferably It has 1 to 4 carbon atoms, and 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 alkyleneamino group, an alkyleneoxy group, etc.). ), carboxy group, alkyl group having 1 to 5 carbon atoms (e.g. methyl group, ethyl group), halogen atom (e.g. chlorine atom, bromine atom, etc.), alkoxy group having 1 to 5 carbon atoms (e.g. methoxy group, ethoxy group) etc.), phenoxy group, etc., for example, 4-sulfophenyl group, 4-sulfophenyl group,
-(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-carboxyphenyl group, 4-(4-sulfophenoxy)
Phenyl group, 4-(2-sulfoethyl)phenyl group, 3-(sulfomethylamino)phenyl group, 4
-(2-sulfoethoxy)phenyl group, etc. can be mentioned. Examples of the above heterocyclic group include 2-(6-sulfo)benzthiazolyl group, 2-(6-sulfo)
Examples include benzoxazolyl groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.), alkyl groups (e.g., methyl groups,
ethyl group, etc.), aryl group (e.g., phenyl group, etc.), carboxyl group, sulfo group, hydroxy group, alkoxy group (e.g., methoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.). Good too. R ₇ and R ₇ ' are each a hydroxy group; an alkoxy group (preferably having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, or a n-butoxy group); a substituted alkoxy group, such as a halogen atom or a carbon number 2 an alkoxy group having 1 to 4 carbon atoms substituted with an alkoxy group (e.g. β-chloroethoxy group, β-methoxyethoxy group); cyano group; trifluoromethyl group; -COOR ₈ ;-
CONHR ₈ ;-NHCOR ₈ (R ₈ is a hydrogen atom; an alkyl group having 1 to 4 carbon atoms (preferably 1 to 4 carbon atoms); or an aryl group, such as a phenyl group,
It represents a naphthyl group, and the alkyl group and aryl group may have a sulfo group or a carboxy group as a substituent. ); ureido group; imino group; amino group; substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms (for example, ethylamino group, dimethylamino group, diethylamino group, di-n-butylamino group); or

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereby. Reference Example 1 An experiment was conducted using the following color paper, processing liquid, and processing process. [Color Paper] The following layers were sequentially coated on a polyethylene coated paper support from the support side to prepare a photosensitive material. The polyethylene coated paper was made by adding 6.8% by weight of anatase titanium oxide to a mixture of 200 parts by weight of polyethylene with an average molecular weight of 100,000 and a density of 0.95 and 20 parts by weight of polyethylene with an average molecular weight of 2,000 and a density of 0.80, and extrusion coating. According to the law, the surface of high-quality paper with a weight of 170 g/m ² and a thickness of 0.035 mm
A coating layer with a thickness of 0.040 mm was formed on the back surface of only polyethylene. The polyethylene-coated surface of this support was pretreated by corona discharge, and then each layer was sequentially applied. 1st layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 80 mol% silver bromide, the emulsion containing 1 mol% silver halide.
Contains 350g of gelatin per mole and contains a sensitizing dye with the following structure per mole of silver halide. sensitized using 2.5×10 ^-3 mol (isopropyl alcohol as solvent) and 200 mg/m ² of 2,5-di-t-butylhydroquinone dissolved and dispersed in dibutyl phthalate and α[ as yellow coupler. 4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidyl)]α-bivalyl-2-chloro-5-[γ-(2,
4-di-t-amylphenoxy)butyramide]
Acetanilide 2x per mole of silver halide
It contains 10 ^-mol and is coated to give a silver content of 330 mg/m ² . 2nd layer: di-t dissolved and dispersed in dibutyl phthalate
-Octylhydroquinone 300mg/m ² , 2-(2'-hydroxy-3',5'-di-t) as a UV absorber
-butylphenyl)benzotriazole 2-
(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-
200 mg/m ² of a mixture of t-butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole. The gelatin layer contains 2000mg/m ² of gelatin. Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 85 mol% of silver bromide, the emulsion containing 450 g of gelatin per mol of silver halide, and having the following structure per mol of silver halide: sensitizing dye Sensitized using 2.5×10 ^-3 mol of dibutyl phthalate and tricrenyl phosphate at 2:1.
2,5-di-t dissolved and dispersed in a solvent mixed with
- Halogenated butylhydroquinone 150 mg/m ² and 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone as magenta coupler Contains 1.5×10 ^-1 mol per mol of silver,
It is coated with a silver content of 300mg/ ^m2 . In addition, (B-22) of the exemplified compound of the general formula []
was contained at a concentration of 15 mg/m ² . 4th layer: dioctyl phthalate dissolved and dispersed.
30mg/ ^m2 of t-octylhydroquinone and 2-(2'-hydroxy-3',5'-di-
t-butylphenyl)benzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-
t-Butyl-5'-methylphenyl)-5-chlorobenzotriazole and 2-(2'-hydroxy-3',5'-t-butylphenyl)-5-chloro-
Mixture of benzotriazole (2:1.5:1.5:
A gelatin layer containing 2) at 500 mg/m ² is applied so that the amount of gelatin is 2000 mg/m ² . Fifth layer: 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 2,5-di-t-sensitized using 2.5×10 ^-3 mol and dissolved and dispersed in dibutyl phthalate.
Butylhydroquinone mg/m ² and 2,4-dichloro-3-methyl-6-[γ as cyan coupler
-(2,4-diamylphenoxy)butyramide]
3.5x phenol per mole of silver halide
It contains 10 ^-1 mol of silver and is coated with a silver content of 300 mg/m ² . In addition, (A-
1) was contained at 15 mg/m ² . 6th layer: Gelatin layer coated with a gelatin amount of 1000mg/m ² . The silver halide emulsions used in each of the photosensitive emulsion layers (1st, 3rd, and 5th layers) were prepared by the method described in Japanese Patent Publication No. 46-7772, and each was prepared using sodium thiosulfate pentahydrate. Chemically sensitized and 4-hydroxy-6-methyl-1,3,3a,7 as a stabilizer
-tetrazaindene, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid. After exposing the color paper produced by the above method,
Continuous treatment was performed using the following treatment steps and treatment liquids. Standard processing steps [1] Color development 38℃ 3 minutes 30 seconds [2] Bleach-fixing 33℃ 1 minute 30 seconds [3] Stabilization 25℃~35℃ 3 minutes 25℃~35℃ 2 minutes [4] Drying 75 ℃～100℃ Approximately 2 minutes Processing liquid composition <Color developing tank liquid> Benzine alcohol 15ml Ethylene glycol Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride 0.2g Potassium carbonate 30.0g 3-Methyl-4-amino-N-ethyl -N-(β
-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (diaminostilbene derivative) 1.0 Hydroxylamine sulfate 3.0g 1-hydroxyethylidene-1,1-diphosphonic acid 0.4g Hydroxyethyliminodiacetic acid 5.0g Chloride Magnesium, hexahydrate 0.7g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2g Add water to make 1, then add KOH and H ₂ SO ₄ to PH10.20
shall be. <Color developer replenisher> Benzyl alcohol 20.0ml Ethylene glycol 20.0ml Potassium sulfite 3.0g Potassium carbonate 30.0g Hydroxylamine sulfate 4.0g 3-Methyl-4-amino-N-ethyl-N-(β
-methanesulfonamidoethyl)-aniline sulfate 7.5g Fluorescent brightener (diaminostilbene derivative) 2.5g 1-hydroxyethylidene-1,1-diphosphonic acid 0.5g hydroxyethyliminodiacetic acid 5.0g Maglucium chloride hexahydrate 0.8g 1,2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.3g Add water to make 1, and adjust the pH to 10.70 with KOH. <Bleach-fixing tank solution> 80 g of ferric complex salt of the chelating agent shown in Table 1 10 g of the chelating agent shown in Table 1 Ammonium thiosulfate (70% dissolved) 100 g Ammonium sulfite (40% dissolved) 27.5 ml Adjust pH to 7 with ammonium water or glacial acetic acid. Adjust to 1 and add water to bring the total volume to 1. <Bleach-fix replenisher> 300 g of ferric complex salt of the chelating agent shown in Table 1 20 g of the chelating agent shown in Table 1 Adjust the pH to 6.7 with potassium carbonate or glacial acetic acid, and add water to bring the total amount to 1. <Bleaching iron replenisher B> Ammonium thiosulfate (70% dissolved) 500ml Ammonium sulfite (40% dissolved) 250ml Chelating agent from Table 1 15g Adjust the pH to 5.3 with ammonia or glacial acetic acid, and add water to bring the total volume to 1. do. <Water wash alternative stable tank liquid and replenisher> 5-chloro-2-methyl-4-isothiazoline-
3-one 0.02g 2-methyl-4-isothiazolin-3-one
0.02g Ethylene dicol 1.0g 2-octyl-4-isothiazolin-3-one
0.01g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3.0g BiCl ₃ (45% aqueous solution) 0.65g ammonia water (ammonium hydroxide 25% aqueous solution)
3.0g Nitrilotrimethylenephosphonic acid 1.5g Adjust to 1 with water and adjust to PH8.0 with H ₂ SO ₄ and KOH. Fill an automatic processor with the color developing tank solution, bleach-fixing tank solution, and stable tank solution mentioned above, and replenish the above-mentioned color developing replenisher, bleach-fixing replenisher A, and B at intervals of 3 minutes while processing the color paper. A running test was performed while replenishing with fluid. The amount of replenisher is 190 ml per 1 m ² of color paper to be added to the color developing tank, and the amount of bleach-fixing replenisher A and B to be added to the bleach-fixing tank.
50 ml of each, and 190 ml of a water washing alternative stabilizing replenisher was replenished to the stabilization treatment bath. 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 replenished, and the overflow from the final tank is allowed to flow into the preceding tank. Furthermore, the multi-tank countercurrent direction was made such that this overflow liquid also flowed into the preceding tank. Continuous processing was performed on each bleach-fix solution No. 1 to No. 10 using the chelating agent shown in Table 1 until the total replenishment amount of the water washing substitute stabilizing solution became twice the capacity of the stabilizing tank. At the end of the processing, the processed photosensitive material was taken as a sample, and the second stabilization treatment was carried out.
A stabilizing solution was collected from the tank. For comparison, a photosensitive material was processed by washing with running water as stabilization treatment after continuous processing. After storing the resulting processed photosensitive material in a constant temperature and humidity chamber at 80°C and 70% RH for 3 weeks, the yellow stain was measured using the blue light of an optical densitometer PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.). did. The results are shown in Table-1. Also,
The collected stabilizing solution as an alternative to washing in the first tank was left in a beaker at room temperature, and the number of days until a black precipitate appeared was observed, and the results are shown in Table 1.

[Table] As is clear from the results in Table 1, compared to bleaching agents using ferric complex salts of chelating agents with large molecular weights (No. 1 to No. 4), No. 1 of the present invention
5 to No. 10 are extremely excellent in both yellow stain and liquid preservability, and furthermore, from a comparison of No. 5 to No. 8 and above, it is possible to use a chelating agent represented by the general formula []. It turns out that this is extremely preferable. Example 1 Using the bleach-fixing solutions No. 1, No. 5 and No. 10 of Reference Example-1, the replenishment amount of the washing alternative replenishing solution for each was 30 ml/m ² as shown in Table-2. 60ml/
m ² , 100ml/m ² , 250ml/m ² , 500ml/m ² , 800ml/
The same experiment as in Reference Example 1 was carried out by performing continuous treatment by changing the ratio of m ² and 2/m ² to determine the yellow stain concentration. The results are shown in Table-2. The amount of liquid carried from the bleach-fixing tank to the washing alternative stabilizing tank liquid due to the photosensitive material is 30 ml/
It was ^m2 .

【table】

〔Effect of the invention〕

The treatment method of the present invention prevents the formation of fine black precipitates that occur in the water washing alternative stabilizing solution when the residence time of the solution increases following treatment with a bleach-fix solution containing thiosulfate; The occurrence of yellow stain when a photographic image processed by reducing the amount of substitute stabilizer replenishment is stored for a long period of time is improved.

Claims (1)

[Scope of Claims] 1. In a method in which a silver halide color photographic light-sensitive material is color-developed and then treated with a bleach-fixing solution, and subsequently treated with a water-washing substitute stabilizer, the silver halide color photographic light-sensitive material has the following general formula: [], [],
Contains at least one of the compounds represented by [ ] or [ ], and the replenishment amount of the water-washing alternative stabilizer is 60 to 60 per m ² of the silver halide color photographic light-sensitive material.
500 ml, and the bleach-fix solution contains as main components an organic acid ferric complex salt, thiosulfate, and sulfite whose free acid has a molecular weight of less than 280. How materials are processed. General formula [] [In the formula, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, a sulfo group or a -
Represents NHR′SO ₃ M. Here, R' represents an alkylene group, and M represents a cation group. ] General formula [ ] [In the formula, R ₆ and R ₆ ' each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ₇
and R ₇ ' are each a hydroxy group, an alkoxy group, a cyano group, a trifluoromethyl group, -COOR ₈ , -
CONHR ₈ , -NHCOR ₈ , ureido group, imino group,
An amino group, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or [Formula] (where p and q represent 1 or 2, and X represents an oxygen atom, a sulfur atom, or a -CH ₂ - group) ) represents a cyclic amino group. _R8 is a hydrogen atom,
Represents 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 [ ] [In the formula, r represents an integer of 1 to 3, W represents an oxygen atom or a sulfur atom, L represents a methine group, and R ₉ to _{R 12} are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or represents a heterocyclic group,
At least one of R ₉ to R ₁₂ is a substituent other than a hydrogen atom. ] General formula [ ] [In the formula, l represents an integer of 1 or 2, L represents a methine group, and R ₁₃ 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 , -NHCOR ₈ , ureido group, imino group,
An amino group, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or [Formula] (where p and q represent 1 or 2, and X represents an oxygen atom, a sulfur atom, or a -CH ₂ - group) ) represents a cyclic amino group. _R8 is a hydrogen atom,
Represents an alkyl group or an aryl group. R ₁₆ represents a hydrogen atom, an alkyl group, a chlorine atom or an alkoxy group. ]