JPH08272061A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a method for processing the silver halide photographic sensitive material restrained from the occurrence of stains on the reverse side of the photosensitive material in the case of reducing a replenishing amount of a stabilizing processing solution following a fixing solution by using the fixing solution containing a specified compound. CONSTITUTION: The silver halide photographic sensitive material is processed by this processing method comprising at least a process using the fixing solution containing the compound represented by formula I and the stabilizing process stabilizing it immediately after the end of the fixing process by using the stabilizing solution containing substantially no formaldehyde. In formulae I and II, Q1 is an atomic group necessary to form an N-containing hetero ring including that condensed with an unsaturated 5- or 6-membered ring; R1 is an H or alkali metal atom; and Q' is same as Q1 . The addition of the compound of formula I in the fixing solution permits the concentration of a thiosulfate necessary for completing the fixing reaction to be reduced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a silver halide photographic light-sensitive material, and more particularly to a method of processing a silver halide photographic light-sensitive material effective for reducing the amount of photographic processing waste liquid.

[0002]

2. Description of the Related Art In combination with the recent movement of environmental protection,
Since the Treaty of London was signed, it has become difficult for Japan to dump photographic wastewater into the ocean from January 1, 1996. For this reason, photo manufacturers have made efforts to reduce the amount of photographic processing waste liquid to the utmost.

By the way, the C-41RA processing by Eastman Kodak Co., which is the most widely used color negative film processing process in the minilab at present, consists of 4 steps, and the replenishment amount of each step is 135 size 24 sheets. Color development process-23 ml, bleaching process-5 ml, fixing process-per line
The amount of waste liquid from the stable treatment process is the largest, with 33 ml and the stable treatment process-40 ml. Therefore, it is desired to reduce the replenishment amount of the stabilizing solution.

However, if the amount of replenishment of the stabilizing solution is simply reduced, the fixing agent such as thiosulfate in the fixing solution which is the pre-bath is attached to the photosensitive material to be treated and brought into the stabilizing solution. Since a large amount is accumulated on the back surface of the photosensitive material to be processed, stains may occur on the back surface of the processed photosensitive material, appear on an image at the time of printing, and lose a commercial value. In addition, the renewal rate of the stabilizing solution itself decreases due to the reduction of the replenishment amount, and the time during which the air is subjected to air oxidation becomes relatively long, which causes a problem that sulfurization failure easily occurs. Furthermore, in the stabilizing solution for a color negative film, formaldehyde is usually added in order to block the active sites of the unreacted magenta coupler in the light-sensitive material and improve the stain in the unexposed area during storage with time and the fading of the dye image. The formaldehyde, which has been added, reacts with the sulfite brought in together with the thiosulfate from the fixing solution to form an adduct, which not only has the original effect of improving the dye preservability but also accelerates the sulfidation. It causes a serious problem of being lost.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and a first object thereof is to reduce the replenishing amount of the stabilizing solution following the fixing solution when the back surface of the photosensitive material is reduced. Another object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material in which the occurrence of stains is suppressed. The second purpose is
(EN) It is intended to provide a processing method of a silver halide photographic light-sensitive material, which has improved storage stability of a stable processing solution and can be stably processed for a long period of time. A third object is to provide a processing method of a silver halide photographic light-sensitive material, which enables reduction of waste liquid for photographic processing and is suitable from the viewpoint of global environment protection. For other purposes,
It will be self-evident in the following text.

[0006]

The above object of the present invention is to carry out a fixing treatment step using a fixing solution containing a compound represented by the general formula (1) and a stabilizing treatment immediately after the fixing treatment is completed. A method for processing a silver halide photographic light-sensitive material having at least a stabilizing step using a stabilizing solution containing substantially no formaldehyde, the replenishing solution of the fixing solution containing thiosulfate, and the replenishing solution of the stabilizing solution. Contains at least one of the compounds represented by the general formulas (F-1) to (F-13), ammonium thiosulfate is 70 mol% or less in the thiosulfate, and general formula (1) fixing process having the step of using a fixing solution containing a compound represented by, and the performs fixing processing is completed immediately after, stabilizing processing solution substantially stable processing replenishing amount is not more than the photosensitive material 1 m ² per 900ml of Having at least,
And, at least a part of the stabilizing solution is added to the fixing solution.

That is, the inventors of the present invention include the compound represented by the general formula (1) (hereinafter, also referred to as the compound of the present invention) in the fixing solution, so as to complete the fixing reaction. It was found that it is possible to reduce the thiosulfate concentration, and further, that formaldehyde, which reacts with sulfite, is not substantially used in the stabilizing solution, so that backside stains and sulfurization of the photosensitive material to be processed can be prevented. The present inventors have found that the replenishing amount of the stabilizing solution can be reduced without causing the occurrence, and have reached the present invention.

Conventionally, a method of adding a heterocyclic compound having a mercapto group to a processing solution has been known. For example, a method of adding it to a fixing solution as described in JP-A 1-261640. , A method of adding to a pre-bath of a bleaching solution as described in JP-A-54-52534, and a method of adding to a bleach-fixing solution as described in British Patent No. 1,138,842. However, these do not describe any formaldehyde-containing stabilizing treatment liquid to be subsequently treated, and do not recall the technical idea of the present invention.

The present invention will be described in detail below.

The present invention is a system in which the stabilization treatment is carried out immediately after the fixing treatment, and the first essential requirement is that the fixing solution contains the compound represented by the general formula (1).

Specific examples of the compound represented by the general formula (1) in the present invention are shown below, but the invention is not limited thereto.

[0012]

[Chemical 11]

[0013]

[Chemical 12]

[0014]

[Chemical 13]

[0015]

Embedded image

Among the above compounds, the compounds preferably used for the purpose of the present invention are (1-9), (1-10),
(1-13) and (1-31) are mentioned, and (1-10) and (1-13) are particularly preferable.

In the present invention, it is contained in the fixer,
The total weight of the compound of the general formula (1) is preferably 0.02% by weight or more and 5% by weight or less, more preferably 0.1% by weight or more and 2% by weight or less, based on the weight of thiosulfate.

Further, the second essential requirement of the present invention is that the stabilizing solution does not substantially contain formaldehyde. By the processing which combines these two requirements, the problems of backside smearing and sulfidation of the photosensitive material to be processed are greatly improved. For the purpose of blocking the active sites of the unreacted magenta coupler, the stabilizing solution preferably contains at least one selected from the compounds represented by the above formulas (F-1) to (F-13).

In the general formula (F-1), R _{11 to} R ₁₆ are
Each represents a hydrogen atom or a monovalent organic group, and examples of the monovalent organic group include an alkyl group, an aryl group, an alkenyl group,
Examples thereof include aralkyl group, amino group, alkoxy group, hydroxy group, acyl group, sulfonyl group, alkylthio group, arylthio group, heterocyclic residue, carbamoyl group, sulfamoyl group and alkylamino group.

These monovalent organic groups are substituents (for example,
Examples thereof include a hydroxy group, an acyl group, a sulfonyl group, a halogen atom, an amino group and a carboxy group, and a hydroxy group and a halogen atom are preferable. ) Can be included. The total carbon number of the substituents represented by R _{11 to} R ₁₆ is preferably 10 or less.

A group of R ₁₁ , R ₁₃ and R ₁₅ and R ₁₂ , R ₁₄ and R
_{The 16} groups may be the same or different, but it is preferred that one of either group is a hydrogen atom.

Specific examples of the compound represented by formula (F-1) are shown below, but the invention is not limited thereto.

[0023]

[Chemical 15]

[0024]

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[0025]

[Chemical 17]

The triazine compound represented by the general formula (F-1) is preferably used in an amount of 0.05 to 50 g, more preferably 0.1 to 20 g, per liter of the treatment liquid.
Range.

General formula (F-2), (F-3) or (F-
Specific examples of the methylol compound represented by 4) include:
The following compounds may be mentioned.

(F-2-1) dimethylol urea (F-2-2) trimethylol urea (F-3-1) trimethylol melamine (F-3-2) tetramethylol melamine (F-3-3) penta Methylol melamine (F-3-4) Hexamethylol melamine (F-4-1) Dimethylol guanidine (F-4-2) Methylol guanidine (F-4-3) Trimethylol guanidine These compounds are added per 1 l of the treatment liquid. It is preferably used in the range of 0.05 to 20 g, more preferably 0.1 to 10
It is in the range of g.

In the general formulas (F-5) and (F-6), the electron-withdrawing groups represented by V ₁ and W ₁ are Hammett's σ _p value (Lange'a Handbook of Chemistry 12th
ed. Vol.3, C. Hansch & A. Leo, Substituent Constants
for Correlation Analysis in Chemistry and Biology
(Jone Wiley & Sons, New York 1979)) is a positive group, specifically, an acyl group (for example,
Acetyl, benzoyl, monochloroacetyl, etc.), alkoxycarbonyl groups (eg, ethoxycarbonyl, methoxyethoxycarbonyl, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl, p-chlorophenoxycarbonyl, etc.), carbamoyl Group (eg, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, N-phenylcarbamoyl, etc.), cyano group, alkylsulfonyl group (eg, methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl group (eg, , Benzenesulfonyl, p-toluenesulfonyl, etc.), sulfamoyl groups (eg, sulfamoyl, N-methylsulfamoyl, N, N-pentamethylenesulfamoyl, etc.) and the like.

Examples of the group represented by Y ₁ which can be removed by hydrolysis include a trialkyl-substituted silyl group (eg, trimethylsilyl group) and an acyl group (eg, acetyl, benzoyl, monochloroacetyl, trichloroacetyl group). , Sulfate groups, aminocarbonyl groups (eg, groups such as N, N-dimethylcarbonyl, N-methylcarbonyl, N-phenylcarbonyl, etc.), sulfonate groups (eg, methanesulfonate, benzenesulfonate, p-toluenesulfonate, etc.) Group) and the like.

5 formed with a nitrogen atom represented by Z
A 6-membered or 6-membered nitrogen-containing heterocycle is [C ₁ N ₄ ],
[C ₂ N ₃ ], [C ₃ N ₂ ], [C ₄ N], [C ₂ N ₄ ],
[C ₃ N ₃ ], [C ₄ N ₂ ], [C ₅ N], [C ₂ N ₂ O],
[C ₃ NO], [C ₃ N ₂ O], [C ₄ NO], [C ₂ N
₂ S], [C ₃ NS], [C ₃ N ₂ S], [C ₂ N ₂ Se],
[C ₃ NSe], [C ₄ NSe], [C ₃ NTe] and other monocycles having an elemental structure, [C ₃ N ₂ -C ₆ ] and [C ₄ N-
_{C 6], [C 4 N} -C 3 N 2], [C 3 N 2 -C 3 N 2], [C
_{3 NS-C 6], [} C 5 N-C 5 N], [C 5 N-C 6],
Examples thereof include condensed rings having an elemental constitution such as [C ₄ N ₂ -C ₆ ], and these rings include, for example, alkyl groups (for example, groups such as methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, and sulfopropyl). ), An aryl group (eg,
Phenyl, groups such as p-methoxyphenyl), hydroxy groups, alkoxy groups (eg, groups such as methoxy, ethoxy, methoxyethoxy), aryloxy groups (eg, groups such as phenoxy, p-carboxyphenyl, etc.), carboxy groups, Sulfo group, alkoxycarbonyl group (eg, groups such as methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), amino group (eg, N, N-dimethylamino, N-ethylamino, N) -Groups such as phenylamino), acylamide (eg, groups such as acetamide, benzamide), carbamoyl groups (eg, groups such as carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl), sulfonamide groups (eg, Groups such as methanesulfonamide, benzenesulfonamide) Sulfamoyl group (for example, a group such as N-ethylsulfamoyl, N, N-dimethylsulfamoyl), an alkylsulfonyl group (for example, a group such as methanesulfonyl and ethanesulfonyl), an arylsulfonyl group (for example, benzenesulfonyl, A group such as p-toluenesulfonyl) or an acyl group (for example, a group such as acetyl or benzoyl) may be included as a substituent.

In the general formula (F-5), the 5- or 6-membered nitrogen-containing heterocycle which can be formed via V ₁ and W ₁ , which are divalent electron-withdrawing groups, is as follows. The thing represented by Formula (F-5-a) is mentioned.

[0033]

Embedded image

In the above formula, V ₁ and W ₁ are -CO- and -C, respectively.
OO -, - SO -, - it represents SO ₂ or -CS- group, Z ₅ is V ₁ and W ₁
Represents a non-metal atom group necessary for forming a 5-membered or 6-membered monocyclic ring or a condensed ring by combining with.

The 5- or 6-membered monocyclic or condensed ring formed by Z ₅ may have a substituent, for example, an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfo). Groups such as propyl), aryl groups (eg, groups such as phenyl and p-methoxyphenyl), hydroxy groups, alkoxy groups (eg, groups such as methoxy, ethoxy, methoxyethoxy), aryloxy groups (eg, phenoxy, p) -Groups such as carboxyphenyl), carboxy groups, sulfo groups, alkoxycarbonyl groups (eg, groups such as methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl group), amino groups (eg, N, N-dimethylamino, N-ethylamino, N-phenylamino, etc. groups), acylamide groups (eg. , Acetamido, benzamide, etc.), carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.) , A sulfamoyl group (eg, N-ethylsulfamoyl, N, N-
A group such as dimethylsulfamoyl), an alkylsulfonyl group (for example, a group such as methanesulfonyl and ethanesulfonyl), an arylsulfonyl group (for example, a group such as benzenesulfonyl and p-toluenesulfonyl), an acyl group (for example, acetyl, Groups such as benzoyl).

Specific examples of the compounds represented by formulas (F-5) and (F-6) are shown below, but the invention is not limited thereto.

[0037]

[Chemical 19]

[0038]

Embedded image

[0039]

[Chemical 21]

The addition amount of the compounds represented by the general formulas (F-5) and (F-6) is about 0.01 to 20 g per liter of the treatment liquid,
It is preferably 0.03 to 15 g, more preferably 0.05 to 10 g.

In the general formula (F-7), the aliphatic groups represented by R ₃₁ , R ₃₂ and R ₃₃ include saturated alkyl groups (eg, unsubstituted alkyl groups such as methyl, ethyl and butyl, and Substituted alkyl groups such as benzyl, carboxymethyl, hydroxymethyl, methoxyethyl, etc., unsaturated alkyl groups (eg, allyl, 2-butenyl, etc.), cyclic alkyl groups (eg, cyclopentyl, cyclohexyl, etc.) ) And the like.

The aryl group represented by R ₃₁ , R ₃₂ and R ₃₃ includes substituted and unsubstituted aryl groups, and examples of the substituent include an alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl). , Groups such as sulfopropyl), aryl groups (eg, groups such as phenyl and p-methoxyphenyl), hydroxy groups, alkoxy groups (eg, groups such as methoxy, ethoxy, methoxyethoxy),
Aryloxy group (eg, phenoxy, p-carboxyphenyl, etc. group), carboxy group, sulfo group, alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.) ), An amino group (for example, a group such as N, N-dimethylamino, N-ethylamino, N-phenylamino, etc.), an acylamide group (for example, a group such as acetamide, benzamide, etc.), a carbamoyl group (for example, carbamoyl, N- Groups such as methylcarbamoyl, N, N-tetramethylenecarbamoyl), sulfonamide groups (eg, groups such as methanesulfonamide, benzenesulfonamide), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dimethyl) Groups such as sulfamoyl), alkylsulfonyl groups (eg, Groups such as tansulfonyl and ethanesulfonyl), arylsulfonyl groups (eg,
Groups such as benzenesulfonyl, p-toluenesulfonyl),
Examples thereof include an acyl group (for example, a group such as acetyl and benzoyl).

The ring formed by combining R ₃₂ and R ₃₃ is 5 to 8
Membered heterocycles, some of which have carbon atoms replaced by heteroatoms.

R ₃₁ is preferably a hydrogen atom.

Examples of the compound represented by formula (F-7) are shown below, but the invention is not limited thereto.

[0046]

[Chemical formula 22]

The addition amount of the compound represented by the general formula (F-7) is about 0.01 to 20 g, preferably 0.03, per liter of the treatment liquid.
~ 15 g, especially 0.05-10 g.

In the general formulas (F-8) to (F-10),
The aliphatic hydrocarbon group represented by R ₃₅ , R ₃₆ and Z ₃ is a saturated alkyl group (for example, an unsubstituted alkyl group such as methyl, ethyl and butyl and carboxymethyl, methoxymethyl, methoxyethyl and hydroxyethyl). , A substituted alkyl group such as benzyl), an unsaturated alkyl group (for example, a group such as allyl and 2-butenyl), and a cyclic alkyl group (for example, a group such as cyclopentyl and cyclohexyl). The aryl group represented by R ₃₆ and Z ₃ may be substituted, and examples thereof include an alkyl group (a group such as methyl, ethyl, methoxyethyl, benzyl, carboxymethyl and sulfopropyl) and an aryl group (eg, phenyl, p -Groups such as methoxyphenyl), hydroxy groups, alkoxy groups (eg, groups such as methoxy, ethoxy, methoxyethoxy), aryloxy groups (eg, groups such as phenoxy, p-carboxyphenyl, etc.), carboxy groups, sulfo groups, Alkoxycarbonyl groups (eg, groups such as methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl group, etc.), amino groups (eg, N, N-dimethylamino, N-ethylamino, N-phenylamino) Groups, etc.), acylamido groups (eg, groups such as acetamide, benzamide, etc. , A carbamoyl group (e.g., carbamoyl, N- methylcarbamoyl, N, N- tetramethylene carbamoyl, etc.), a sulfonamido group (e.g., methanesulfonamido, groups such as benzene sulfonamido), sulfamoyl group (e.g., N-
Groups such as ethylsulfamoyl, N, N-diethylsulfamoyl, etc.), alkylsulfonyl groups (eg, groups such as methanesulfonyl, ethanesulfonyl, etc.), arylsulfonyl groups (eg, groups such as benzenesulfonyl, p-toluenesulfonyl, etc.) ) And acyl groups (for example, groups such as acetyl and benzoyl).

Examples of the group represented by V ₂ , W ₂ , Y ₂ and Z ₃ which is eliminated by hydrolysis are, for example, an acyl group (for example, a group such as acetyl, benzoyl, trifluoroacetyl and monochloroacetyl), Examples thereof include a trialkylsilyl group (eg, trimethylsilyl group and the like).

The ring formed by combining R ₃₆ with Z ₃ is 5 to
It also includes an 8-membered saturated ring or a condensed ring in which a part of the bonding carbon chain is substituted with another heteroatom. Specific examples thereof include rings such as 1,2-dioxanecyclopentane, m-dioxane, trioxane, tetraoxane and benzdioxolane.

As the cation represented by M, for example, hydrogen ion, alkali metal ion (for example, ions of lithium, sodium, potassium, etc.), alkaline earth metal ion (for example, ion of magnesium, calcium, etc.), ammonium ion. , Organic ammonium ions (for example, ammonium ions such as triethylammonium, tripropylammonium, tetramethylammonium, etc.), pyridinium ions and the like.

The aliphatic hydrocarbon group represented by R ₃₅ is preferably a lower alkyl group having 1 or 2 carbon atoms, and further R is
It is preferable that ₃₅ is a hydrogen atom.

Specific examples of the compounds represented by formulas (F-8) to (F-10) are shown below, but the compounds are not limited thereto.

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

The amount of the compounds represented by the general formulas (F-8) to (F-10) added is about 0.01 to 20 g, preferably 0.03 to 15 g, and more preferably 0.05 to 10 g per liter of the treatment liquid.

The salt of the compound represented by the general formula (F-11) includes inorganic acid salts such as hydrochlorides, sulfates and nitrates, organic acid salts such as phenol salts, double salts or complex salts with metal salts, Examples thereof include hydrous salts and inner salts.

The compound represented by formula (F-11) is specifically, Beilsteins: Handbuch der.
Organischen Chemie (Beilsteins Handbuch der
Organishen Chemie), Vol. 26, Vol. 26, pp. 200-212. Of these, those soluble in water are preferred in the present invention. Typical examples will be given below.

[0059]

[Chemical 25]

[0060]

[Chemical formula 26]

[0061]

[Chemical 27]

[0062]

[Chemical 28]

[0063]

[Chemical 29]

[0064]

Embedded image

[0065]

[Chemical 31]

The addition amount of the compound represented by formula (F-11) is preferably 0.1 to 20 g per liter of the treatment liquid.

In formula (F-12), Z ₄ represents an atom group necessary for forming a substituted or unsubstituted carbocycle or a substituted or unsubstituted heterocycle, and the carbocycle and the heterocycle are monocyclic rings. Or a condensed ring, and Z ₄ is preferably a substituted aromatic carbocycle or heterocycle. The substituent of Z ₄ is an aldehyde group,
Hydroxyl group, alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, etc.), aralkyl group, alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.), halogen atom,
Nitro group, sulfo group, carboxy group, amino group (eg N, N-dimethylamino, N-ethylamino, N-phenylamino etc.), hydroxyalkyl group, aryl group (eg phenyl, p-methoxyphenyl etc.) , Cyano group, aryloxy group (eg, phenoxy, p-carboxyphenyl, etc.), acyloxy group, acylamino group, sulfonamide group, sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl, etc.) ), A carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N-tetramethylenecarbamoyl, etc.) or a sulfonyl group (eg, methanesulfonyl, ethanesulfonyl,
Benzenesulfonyl, p-toluenesulfonyl, etc.) are preferred.

The carbocycle represented by Z ₄ is preferably a benzene ring, and the heterocycle represented by Z ₄ is preferably a 5- or 6-membered heterocycle. For example, the 5-membered ring is thiophene, pyrrole, Furan, thiazole,
Examples thereof include imidazole, pyrazole, succinimide, triazole and tetrazole, and examples of the 6-membered ring include pyridine, pyrimidine, triazine and thiadiazine.

Examples of the condensed ring include naphthalene, benzofuran, indole, thionaphthalene, benzimidazole, benzotriazole and quinoline.

Preferred examples of the compound represented by formula (F-12) are shown below.

[0071]

Embedded image

Exemplified compounds (F-12-1) to (F-12-5)
2) is obtained by inserting various substituents into 1 to 6 in the above formula as shown in the table below.

[0073]

[Chemical 33]

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

Among the specific examples of the compounds represented by the general formula (F-12), more preferable compounds include (F-12
-2), (F-12-3), (F-12-4), (F-12-6),
(F-12-23), (F-12-24) and (F-12-52) are mentioned, but (F-12-3) is most preferable.

The compound represented by formula (F-12) can be easily obtained as a commercial product.

The amount of the compound represented by formula (F-12) added is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, and particularly preferably 0.5 to 10 g per liter of the stabilizing solution.
It is in the range of g.

In formula (F-13), R ₅₁ , R ₅₂ and R ₅₃ are each a hydrogen atom or an optionally substituted alkyl group (eg, methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl, Hydroxyethyl, n-propyl, iso-propyl, chloromethyl, carboxyethyl etc.) or an aryl group (eg phenyl,
p-methoxyphenyl, p-hydroxyphenyl, m-sulfophenyl, m-carboxyphenyl, etc., and X is an optionally substituted nitrogen-containing heterocycle (eg, pyrrole, imidazole, piperidine, pyrazole, succinimide, triazole, tetrazole) , Thiadiazine, thiadiazoline, morpholine, piperazine, thiamorpholine, indole, indazole, benzimidazole, benzotriazole, pyrrolidine, pyrazolidine, hydantoin, urazole and the like).

Examples of the compound represented by formula (F-13) will be given below.

[0083]

[Chemical 38]

[0084]

[Chemical Formula 39]

[0085]

[Chemical 40]

[0086]

Embedded image

[0087]

Embedded image

[0088]

[Chemical 43]

Among the specific examples of the compounds represented by the general formula (F-13), more preferable compounds include (F-13-
1), (F-13-2), (F-13-3), (F-13-
8), (F-13-10), (F-13-14) (F-13-3
5), (F-13-36), (F-13-39), (F-13-4
5), (F-13-55), (F-13-60), (F-13-6)
5), (F-13-67), (F-13-68), (F-13-6
9), (F-13-72) and (F-13-74).

The compound represented by formula (F-13) can be easily obtained as a commercial product.

The addition amount of the compound represented by formula (F-13) is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, and particularly preferably 0.5 to 10 g per liter of the stabilizing solution. Is.

A preferred embodiment of the present invention is that the stabilizing solution contains a compound represented by the following general formula (2) or (3).

General formula (2) R ₅₄ —O— (R ₅₅ —O) m —X _{2 In the} formula, R ₅₄ represents a monovalent organic group, R ₅₅ represents an ethylene group,
Represents a trimethylene group or a propylene group, m is 4 to 50
Represents the integer. X ₂ represents a hydrogen atom, -SO ₃ M ₁ or -PO ₃ M _2. Here, M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom or an ammonium group.

[0094]

[Chemical 44]

In the formula, R ₅₆ is a hydrogen atom, a hydroxyl group,
Lower alkyl group, alkoxy group,

[0096]

Embedded image

R ₅₇ , R ₅₈ and R ₅₉ each represent a hydrogen atom or a lower alkyl group (preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group or a propyl group). , R ₅₇ , R ₅₈ and R ₅₉ may be the same or different. l _{1 to} l ₃ each represent 0 or an integer of 1 to 30, and p, q ₁ and q ₂ each represent 0 or 1.
Represents an integer of ~ 30. X ₃ and X ₄ are ethylene group, trimethylene group,

[0098]

Embedded image

Represents

The compound of the general formula (2) will be further described. In the formula, R ₅₄ is a monovalent organic group, for example, an alkyl group having 4 to 30 carbon atoms, preferably 6 to 20 carbon atoms (eg, hexyl, heptyl). , Octyl, nonyl, decyl, undecyl or dodecyl), or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent of the aryl group is preferably an alkyl group having 3 to 12 carbon atoms. The group is propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl and the like. Examples of the aryl group include phenyl, tolyl, xynyl, diphenyl or naphthyl,
Preferred is phenyl or tolyl. The position at which the alkyl group is bonded to the aryl group may be any of the ortho, meta and para positions. R ₅₅ represents an optionally substituted ethylene group or an optionally substituted trimethylene group, and m is 4 to
Represents an integer of 50. X ₂ is a hydrogen atom, —SO ₃ M ₁ or —PO ₃ M ₂
And M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom (Na, K or Li, etc.) or NH ₄ .

Specific examples of compounds represented by the general formula (2) are shown below.

[0102]

[Chemical 47]

[0103]

Embedded image

The compound represented by the general formula (2) can be used in the stabilizing solution in an amount of 0.1 to 40 g, preferably 0.3 to 20 g, per liter.

Next, specific examples of the compound represented by the general formula (3) will be shown.

[0106]

[Chemical 49]

[0107]

Embedded image

[0108]

[Chemical 51]

[0109]

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The amount of the water-soluble organic siloxane compound having a polyoxyalkylene group added is such that the stabilizing solution 1
When used in a range of 0.01 to 20 g per liter, it exerts a good effect, and particularly exerts an effect of preventing precipitation and scratches.

These water-soluble organic siloxane compounds are disclosed, for example, in JP-A-47-18333, JP-B-55-51172, JP-B-51-37538, JP-A-49-62128 and US Pat. It is a general water-soluble organosiloxane compound as described in the specification of No. 3,545,970.

These water-soluble organic siloxane compounds are U
It can be generally obtained from CC (Union Carbide Co.), Shin-Etsu Chemical Co., Ltd., etc.

Examples of the silver halide of the light-sensitive material to be processed include silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodide and the like. In order to exert the effect of the present invention, it is photographed. The silver iodide photographic light-sensitive material is preferably a silver iodide photographic light-sensitive material having a silver iodide content of 5 mol% or more of silver halide and a relatively high silver iodide content.

The fixing solution according to the present invention contains a so-called fixing agent.

As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt, for example, potassium thiosulfate, sodium thiosulfate, thiosulfate such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanic acid. Examples thereof include thiocyanates such as ammonium, thiourea thioethers and the like, but thiosulfates are preferable from the viewpoint that the effects of the present invention can be fully exhibited, and more preferably thiosulfates among thiosulfates. Ammonium sulfate is 70 mol% or less. The ratio of ammonium thiosulfate in this thiosulfate is
It is preferably 50 mol% or less, and particularly preferably 20 mol% or less.

In addition to these fixing agents, further fixing solutions include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide. A pH buffer consisting of various salts such as, alkylamines, polyethylene oxides and the like which are known to be added to a fixing solution can be appropriately added.

The fixing agent is used in an amount of 0.1 mol or more per liter of the processing liquid, preferably in the range of 0.6 to 4 mol, particularly preferably in the range of 0.9 to 3.0 mol, and particularly preferably.
It is used in the range of 1.1 to 2.0 mol.

In the present invention, air or oxygen may be blown in the treatment bath and the treatment replenisher storage tank to increase the activity of the treatment liquid, if desired, or a suitable oxidizing agent such as peroxide may be used. Hydrogen, bromate, persulfate and the like may be added appropriately.

The pH of the fixing solution of the present invention is preferably 4-8.
Used in the range of.

The fixing solution of the present invention can contain a sulfite and a sulfite-releasing compound, and the compounds include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, and metabisulfite. Examples thereof include potassium, sodium metabisulfite, and ammonium metabisulfite. Further, sodium formaldehyde bisulfite, sodium acetaldehyde bisulfite, sodium propionaldehyde bisulfite, sodium butyraldehyde bisulfite, sodium succinate aldehyde bisulfite, glutaraldehyde sodium bisulfite, β-methylglutaraldehyde bis sodium bisulfite, maleic acid. Dialdehyde bis sodium bisulfite and the like can also be used.

These sulfites and sulfite-releasing compounds are used as sulfurous acid in an amount of 0.1 mol or more, preferably 0.12 to 0.55 mol / l, more preferably 0.15 to 0.50 mol / l, per liter of the fixing solution.
1, especially in the range 0.20 to 0.40 mol / l.

The tank for fixing processing in the present invention may be one tank or a plurality of processing tanks.

The time until the photosensitive material comes into contact with the stabilizing solution in the stabilizing process immediately after the fixing process is preferably 7 seconds or less, more preferably 5 seconds or less, and further 1 to 3
Seconds are preferred.

The number of stabilizing tanks may be one, but the number of tanks can be increased up to about 2 to 10, and the replenishment amount of the stabilizing solution can be reduced by increasing the number of tanks. Considering downsizing of the developing machine, about 2 to 6 tanks are preferable. The replenisher may be replenished in several places, but preferably it is replenished to a subsequent tank in view of the processing flow of the light-sensitive material and its overflow (the tanks are communicated with each other by a pipe located below the liquid surface). In such a case, it is preferable to adopt a system in which the solution flows through the pipe) into the previous tank of the tank, that is, a countercurrent system (multistage countercurrent system), and a cascade system is included in one of them. More preferably, in the stabilizing tank of two or more tanks, the last stabilizing tank is supplemented with the replenishing solution, and the overflow solution is sequentially transferred and poured into the preceding tank.

By only incorporating the compound represented by the general formula (1) of the present invention into the fixing solution, the replenishing amount of the stabilizing solution is greatly reduced to about 900 ml or less per 1 m ^{2 of the} light-sensitive material to be processed. However, by further processing with the above-mentioned constitution, the effect of the present invention can be obtained with a replenishing amount of the stabilizing solution of 50 to 800 ml per 1 m ^{2 of the} light-sensitive material to be processed, and the effect of the present invention is fully exhibited. From this point of view, the preferable amount of the replenisher is 100 to 650 ml, and further 150 to 500 ml.

In the present invention, the amount of replenisher liquid can be further reduced by introducing the processing liquid pumped out from the stabilizing tank into the fixing liquid in the fixing processing step.

Specific processing steps of the processing method according to the present invention include (1) color development → bleaching → fixing → stable, (2)
Color development → bleaching → fixing → 1st stability → 2nd stability, (3) color development → bleaching → bleach-fixing → fixing → 1st stability → 2nd stability.

[0128]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A Konica Color Negative Film Super DD100 (manufactured by Konica Corp.) was used for actual exposure exposure with a camera for 20 days, and a stable replenisher having a volume twice that of the stable tank tank. The running process was carried out until was replenished. The steps and conditions of the running treatment are shown below.

Processing step Processing time Processing temperature (° C) Replenishment amount (ml / light-sensitive material 1 m ² ) Color development 3 minutes 15 seconds 38 625 Bleaching 45 seconds 37 250 Fixed 1 minute 30 seconds 37 900 Stability 60 seconds 37 600 Dry 60 seconds 70-However, there are 2 fixing tanks and counter current (45 seconds, 2
Counter current (15 seconds, 4 seconds)
Tank). The crossover time of each process is 3
Seconds

The composition of the treatment liquid used is shown below.

<< Color Developer >> Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 4 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 4.8 g Potassium hydroxide 1.2 g Add water to make 1 liter, and adjust to pH 10.06 with potassium hydroxide or 50% sulfuric acid.

<< Color Development Replenisher >> Potassium carbonate 40 g Sodium hydrogen carbonate 3 g Potassium sulfite 7 g Sodium bromide 0.5 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) Aniline sulfate 6.0 g Potassium hydroxide 2 g Add water to make 1 liter, and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

<< Bleaching Solution and Bleaching Replenishing Solution >> 1,3-Propanediaminetetraacetic acid ferric ammonium salt 150 g Ammonium bromide 100 g Water is added to make 1 l, and the pH is adjusted to 5.2 with aqueous ammonia or glacial acetic acid.

<< Fixing Solution and Fixing Replenisher >> Ammonium thiosulfate Described in Table 1 Additives (described in Table 1) Described in Table 1 Ammonium sulfite 10 g Ethylenediaminetetraacetic acid disodium 5 g Water was added to make 1 l, and acetic acid and ammonia water were added. Adjust to pH 8.0 using.

<< Stabilizer and Stable Replenisher >> Exemplified Compound 2-5 1 ml Exemplified Compound 3-3 0.2 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g Additives (listed in Table 1) Table The water described in 1 was added to make 1 liter, and the pH was adjusted to 7.0 with aqueous ammonia and 50% sulfuric acid.

The amount of ammonium thiosulfate added and the additives in the fixer and fixer replenisher were changed as shown in Table 1, and at the same time, the additives in the stabilizer and the fixer replenisher were also changed as shown in Table 1. The running process was performed by changing.

After the running process was completed, the state of dirt on the back surface of the film and the state of the second tank in the stabilizing tank were observed. The amount of residual silver in the unexposed area of the processed film was measured by the fluorescent X-ray method. The results are shown in Table 1.

[0139]

[Table 1]

Here, formalin is an approximately 37% aqueous solution of formaldehyde, and the evaluation criteria are as follows.

<Evaluation of Backside Stain of Film> ◯: No backside stain is observed Δ: Some backside stain is observed ×: Backside is clearly seen, which is a practical problem level.

<< Evaluation of the condition of the second stable tank >>: No abnormality is observed in the second tank. △: Some stains are observed in the second tank. ×: Sulfur is clearly observed in the second tank. This is a practical problem level.

Further, when the amount of residual silver in the unexposed area is 3 mg / dm ² or less, there is no actual damage on the product.

Example 2 In the following, the addition amount in the silver halide photographic light-sensitive material is shown in g per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

On the triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material sample.

<< Photosensitive Material Sample >> First Layer: Antihalation Layer (HC-1) Black Colloidal Silver 0.22 Ultraviolet Absorber (UV-1) 0.20 Colored Coupler (CM-1) 0.05 Colored Coupler (CM-2)
0.05 High boiling point solvent (Oil-1)
0.20 Gelatin 1.3 Second layer: Intermediate layer (IL-1) Ultraviolet absorber (UV-1) 0.01 High boiling point solvent (Oil-1) 0.01 Gelatin 1.3 Third layer: Low sensitivity red-sensitive emulsion layer (RL) Iodine Silver bromide emulsion (Em-1) 1.0 Silver iodobromide emulsion (Em-2) 0.5 Sensitizing dye (S-1) 2.5 × 10 ⁻⁴ mol / silver 1 mol Sensitizing dye (S-2) 2.5 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S-3) 0.5 × 10 ^-4 mol / silver 1 mol Cyan coupler (C-4〃) 1.2 Cyan coupler (C-2〃) 0.06 Colored cyan coupler (CC-1) ) 0.05 DIR compound (D-1) 0.002 High boiling point solvent (Oil-1) 0.5 Gelatin 1.3 Fourth layer: high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 2.0 Sensitizing dye (S -1) 2.0 × 10 ^-4 mol / 1 mol of silver sensitizing dye (S-2) 2.0 × 10 -4 mol / 1 mol of silver sensitizing dye (S-3) 0.1 × 10 -4 mol / silver model Cyan coupler (C-1〃) 0.15 Cyan coupler (C-2〃) 0.018 Cyan coupler (C-3〃) 1.15 Colored cyan coupler (CC-1) 0.015 DIR compound (D-2) 0.05 High boiling point solvent (Oil- 1) 0.5 gelatin 1.2 Fifth layer: intermediate layer (IL-2) gelatin 0.4 Sixth layer: low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.9 Sensitizing dye (S-4) 5.0 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S-5) 1.0 × 10 ^-4 mol / silver 1 mol Magenta coupler (M-1〃) 0.3 Magenta coupler (M-2〃) 0.2 Colored magenta coupler ( CM-1) 0.05 DIR compound (D-3) 0.015 DIR compound (D-4) 0.020 High boiling point solvent (Oil-2) 0.5 Gelatin 1.0 7th layer: Intermediate layer (IL-3) Gelatin 0.8 High boiling point solvent (Oil) -1) 0.2 8th layer: high-sensitivity green-sensitive emulsion layer ( H) Silver iodobromide emulsion (Em-3) 1.2 Sensitizing dye (S-6) 1.5 × 10 -4 mol / 1 mol of silver Sensitizing dye (S-7) 2.5 × 10 -4 mol / 1 mol of silver up Sensitizing dye (S-8) 0.5 × 10 ^-4 mol / silver 1 mol Magenta coupler (M-2〃) 0.06 Magenta coupler (M-3〃) 0.18 Colored magenta coupler (CM-2) 0.05 DIR compound (D-3) ) 0.01 High boiling point solvent (Oil-3) 0.5 Gelatin 1.0 9th layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Oil-3) 0.1 Gelatin 0.8 10th Layer: Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-10) 7.0 × 10 ^-4 mol / silver 1 Mole Yellow coupler (Y-1〃) 0.6 Yellow coupler (Y-2〃) 0.12 DIR compound (D-2) 0.01 High boiling point Medium (Oil-3) 0.15 Gelatin 1.0 11th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.45 Silver iodobromide emulsion (Em-1) 0.20 Sensitizing dye (S- 9) 1.0 × 10 ^-4 mol / silver 1 mol Sensitizing dye (S-10) 3.0 × 10 ^-4 mol / silver 1 mol Yellow coupler (Y-1〃) 0.36 Yellow coupler (Y-2〃) 0.06 High boiling point Solvent (Oil-3) 0.07 Gelatin 1.1 12th layer: 1st protective layer (Pro-1) Fine grain silver iodobromide emulsion (average particle size 0.08μ, AgI 2 mol%) 0.4 UV absorber (UV-1) 0.10 UV Absorbent (UV-2) 0.05 High boiling point solvent (Oil-1) 0.1 High boiling point solvent (Oil-4) 0.1 Formalin scavenger (HS-1) 0.5 Formalin scavenger (HS-2) 0.2 Gelatin 1.0 13th layer: 2nd Protective layer (Pro-2) Surfactant (Su-1) 0.005 Alkali-soluble mat (Average particle size 2μ) 0.10 Cyan dye (AIC-1) 0.005 Magenta dye (AIM-1) 0.01 Sliding agent (WAX-1) 0.04 Gelatin 0.8 In addition to this, coating aid Su-2 and dispersion are added to each layer. Auxiliary agent Su-3, hardeners H-1 and H-2, antifungal agent DI-1,
Stabilizer Stab-1, antifoggants AF-1 and AF-
2 was added. The emulsions used are as follows.

Em-1: Average grain size 0.46μ, average silver iodide content 7.5% Monodisperse surface low silver iodide-containing emulsion Em-2: Average grain size 0.32μ, average silver iodide content 2.0 % Monodisperse emulsion of uniform composition Em-3: average grain size 0.78μ, average silver iodide content 6.0% Monodisperse surface low silver iodide-containing emulsion Em-4: average grain size 0.95μ, average Silver iodide content 8.0% Monodisperse surface low silver iodide content type emulsions Em-1, Em-3 and Em-4 are disclosed in JP-A-60-138538.
No. 61-245151, and it is a silver iodide emulsion mainly having an octahedron having a multilayer structure. Also, E
In all of m-1 to Em-4, the average value of (particle size) / (particle thickness) is 1.0, and the width of particle distribution is 14, 10, 12 and 12% (variation coefficient), respectively. Met.

[0148]

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[0149]

[Chemical 54]

[0150]

[Chemical 55]

[0151]

[Chemical 56]

[0152]

[Chemical 57]

[0153]

Embedded image

[0154]

Embedded image

[0155]

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[0156]

[Chemical formula 61]

[0157]

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[0158]

[Chemical formula 63]

The following experiment was conducted using the obtained film sample.

Formalin (5 ml / l) in the stabilizing solution and the stabilizing replenishing solution used in Experiment No. 1-5 of Example 1 was changed as shown in Table 2, and the other experiments were conducted in the same manner.

At the same time, the treated film was stored in the dark at 75 ° C. and 10% RH for 10 days, and the difference in yellow transmission density (yellow stain density) between the unexposed areas before and after storage was measured.

The results are shown in Table 2.

[0163]

[Table 2]

Accordingly, the above general formulas (F-1) to (F
It is understood that the use of the compound represented by -13) in combination in the stabilizing solution improves the generation of yellow stain in the unexposed area during storage over time.

Example 3 Sodium thiosulfate was appropriately mixed while keeping the total number of moles of ammonium thiosulfate added in the fixer and fixer replenisher used in Experiment Nos. 1-4 of Example 1 as appropriate, and Table 3 The experiment was carried out in the same manner except that the ammonium content (mol%) in the thiosulfate was changed to that shown in. Further, the state of odor of the fixing tank liquid at the end of running was examined. Table 3
Shown in

[0166]

[Table 3]

<Evaluation of odor> ◯: Almost no odor Δ: Slight ammonia odor X: Clearly ammonia odor, and odor in the vicinity The larger the number X, the stronger the odor.

From Table 3, the effect of the present invention can be obtained when the ammonium salt content of thiosulfate in the fixer and fixer replenisher is 70 mol% or less (particularly 50 mol% or less, especially 20 mol% or less). It can be seen that not only the performance is good, but also the odor is improved and the working environment is improved.

Example 4 In Experiment No. 1-7 of Example 1, 450 ml per 1 m ^{2 of} film was transferred from the stabilizing tank closest to the fixing tank among the four stabilizing tanks to the immediately preceding fixing tank with a bellows pump. When the running test was conducted, the fixing replenisher was concentrated twice as much, and the concentrated fixing replenisher was replenished in the ^second 450 ml fixing treatment tank per 1 m ² of film. The residual silver amount at the end of the running was 0, and improvement in fixing performance was confirmed. Other properties were the same as the conditions in Example 1, and it was further confirmed that the total amount of photographic waste liquid generated during this treatment was reduced by about 21%.

From the above, by using a part or all of the stabilizing bath of the present invention as the fixing bath, not only the effects of the present invention can be exhibited more favorably, but also the total amount of photographic waste liquid can be reduced. I understand.

Example 5 Instead of the compound (1-10) in the fixing solution and the compound (F-1-16) in the stabilizing solution used in Experiment No. 2-3 of Example 2, the results are shown in Table 4. The experiment was conducted in the same manner as in Example 1 except that the compound of Example 1 was added. The results are shown in Table 4.

[0172]

[Table 4]

This also shows the superiority of using the compound of the present invention in the fixing solution and performing the processing substantially without using formaldehyde in the stabilizing solution.

Example 6 In Experiment No. 1-6 of Example 1, except that the formulations of the fixing solution and the fixing replenishing solution were changed as follows, and the replenishing amount of the stabilizing solution was changed as shown in Table 5. Performed the same experiment to evaluate the stain on the back surface of the film.

<< Fixing Solution and Fixing Replenishing Solution >> Ammonium thiosulfate 380 g Ammonium sulfite 15 g Diethyleneamine pentasodium acetate 2 g Water is added to make 1 l, and pH is adjusted to 7.5 with acetic acid and aqueous ammonia.

The results are shown in Table 5.

[0177]

[Table 5]

Next, in Experiment No. 1-6 of Example 1, the same as in Example 6 except that the replenishing amount of the stabilizing solution was changed as shown in Table 6 without changing the prescriptions of the fixing solution and the fixing replenishing solution. Table 6 shows the result of the experiment.

[0179]

[Table 6]

Comparing the results in Tables 5 and 6, the effect of the present invention is remarkably exhibited when the replenishing amount of the stabilizing solution is 900 ml / m ² or less in the present invention, 50 to 800 ml / m ² , and further 100 to 100 ml / m ² . 650 ml / m
It turns out that the range of ² is more advantageous.

[0181]

According to the present invention, the replenishing amount of the stabilizing solution can be reduced and the photographic processing waste solution can be reduced without causing the back surface of the photosensitive material to be processed and the sulfurization of the stabilizing solution. In addition, it is possible to provide stable processing over a long period of time, and it is possible to provide a processing method of a silver halide photographic light-sensitive material that is suitable from the viewpoint of global environment protection.

Claims (7)

[Claims] 1. A fixing treatment step using a fixing solution containing a compound represented by the following general formula (1), and a stabilizing treatment immediately after completion of the fixing treatment to obtain a stabilizing treatment solution containing substantially no formaldehyde. A method of processing a silver halide photographic light-sensitive material, which comprises at least a stabilizing process to be used. Embedded image 2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the replenisher for the fixing solution contains thiosulfate. 3. The replenisher for the stabilizing solution contains at least one of the compounds represented by the following general formulas (F-1) to (F-13). A method for processing a silver halide photographic light-sensitive material as described above. Embedded image [In the formula, R _{11 to} R ₁₆ each represent a hydrogen atom or a monovalent organic group. ] [Chemical 3] [In the formula, R _{21 to} R ₂₃ each represent a hydrogen atom or a methylol group. ] [Chemical 4] [In the formula, V ₁ and W ₁ represent an electron-withdrawing group, and V ₁ and W ₁
And W ₁ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocycle. Y ₁ represents a hydrogen atom or a group capable of leaving by hydrolysis. Z represents a nonmetallic atom group necessary for forming a monocyclic ring or a condensed nitrogen-containing heterocycle with a nitrogen atom. ] [Chemical 5] [In the formula, R ₃₁ represents a hydrogen atom or an aliphatic group, R ₃₂ and R ₃₃ each represent an aliphatic group or an aryl group, and R ₃₂ and R ₃₃
May combine with each other to form a ring. Z ₁ and Z ₂ are each an oxygen atom, a sulfur atom or -N (R ₃₄₎ - represents a. However, Z ₁ and Z ₂ are not oxygen atoms or —N (R ₃₄ ) — at the same time. R ₃₄ represents a hydrogen atom, a hydroxy group, an aliphatic group or an aryl group. ] [Chemical 6] [In the formula, R ₃₅ represents a hydrogen atom or an aliphatic hydrocarbon group,
V ₂ represents a group capable of leaving by hydrolysis, M represents a cation, W ₂ and Y ₂ each represent a hydrogen atom or a group capable of leaving by hydrolysis, n represents an integer of 1 to 10, and Z represents Z. ₃
Represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a group capable of leaving by hydrolysis, and R ₃₆ represents an aliphatic hydrocarbon group or an aryl group. Z ₃ may combine with R ₃₆ to form a ring. ] [Chemical 7] Wherein, A ₁ to A ₄ is a hydrogen atom, an alkyl group, an alkenyl group, pyridyl group. l represents 0 or 1. ] [Chemical 8] [In the formula, Z ₄ represents an atomic group necessary for forming a hydrocarbon ring or a hetero ring, X represents an aldehyde group, and (Wherein R ₄₁ and R ₄₂ each represent a lower alkyl group), and n represents an integer of 1 to 4. ] [Chemical 10] [In the formula, R _{51 to} R ₅₃ each represent a hydrogen atom, an alkyl group or an aryl group, and X represents a nitrogen-containing heterocyclic group. ] 4. Ammonium thiosulfate in thiosulfate
The method for processing a silver halide photographic light-sensitive material according to claim 2 or 3, wherein the content is 70 mol% or less. 5. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein at least a part of the stabilizing solution is added to the fixing solution. 6. A fixing process comprising a step of using a fixing solution containing the compound represented by the general formula (1), and immediately after the completion of the fixing process, the stabilizing solution is substantially replenished in a photosensitive material. A method of processing a silver halide photographic light-sensitive material, which comprises at least a stabilizing treatment of 900 ml or less per 1 m ² . 7. The method of processing a silver halide photographic light-sensitive material according to claim 6, wherein at least a part of the stabilizing solution is added to the fixing solution.