JPH09166854A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To process a silver halide photographic sensitive material without causing dyeing even in the case of continuous processing by incorporating a specified compd. into a bleaching soln. SOLUTION: When an imagewise exposed silver halide color photo-graphic sensitive material is color-developed and processed with a bleaching soln. contg. a complex salt of iron (III) aminopoly-carboxylate, a compd. represented by the formula R-(SO2 M)n is incorporated into the bleaching soln. In the formula, R is alkyl, alkenyl, aralkyl, cycloalkyl, aryl or a heterocyclic group, M is a cation and (n) is 1 or 2. Dyeing can be suppressed especially in the case of slight replenishment or in the case where the processing soln. is repeatedly used after regeneration.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a processing method in which dyeing of an oxide of a developing agent is suppressed on a light-sensitive processing material.

[0002]

2. Description of the Related Art In photographic processing, there are two major flows of shortening (accelerating) the processing time and reducing the amount of waste liquid, and it is required to achieve both of them. 1,3-Propanediamine tetraacetate, which is a bleaching agent with a stronger oxidizing power, replaces ethylenediaminetetraacetic acid iron (III) complex salt, which has been widely used as a bleaching agent in the accelerating process, especially in the bleaching process. (III) The use of complex salts has made it possible to increase the bleaching speed. Further, conventionally, as a method for reducing the amount of processing waste liquid, a low replenishment method for replenishing a concentrated processing liquid with a small amount, and a recycling method particularly for a bleaching solution are well known. In the bleaching process using the aminopolycarboxylic acid iron (III) complex salt as a bleaching agent, if the replenishment amount is reduced and continuous processing is performed or the overflow solution is regenerated and reused, the developer solution component in the bleaching solution is It was found to be colored by being oxidized by the bleaching agent. This coloring is a phenomenon in which a developing agent in a developing solution is brought into a bleaching solution by a processed light-sensitive material and is oxidized, and soaks into the light-sensitive material during processing and is colored. Due to this coloring, the processed light-sensitive material causes an increase in Dmin concentration and an increase in stain, resulting in a lower execution sensitivity, and in the case of a negative film, there are problems such that it is difficult to set conditions for printing. This phenomenon is hereinafter referred to as dyeing. Dyeing also occurred in a bleaching solution using a conventional ethylenediaminetetrairon (III) acetate complex salt, but it became more remarkable by using 1,3-propanediaminetetrairon (III) acetate complex salt having strong oxidizing power. became. It was also found that the smaller the replenishment amount of the bleaching solution, the more remarkable it was. The conventional technique for suppressing dyeing is W
Aromatic polyhydroxy compounds described in O87 / 04534, and JP-A-3-223757 and 3-24005.
The method using the surfactant described in No. 4 is known, but in any case, when the bleaching solution was used, the effect was not seen and the problem could not be solved.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a processing solution and a processing method in which coloring components are not dyed even when continuous processing is carried out in the processing of silver halide photographic light-sensitive materials. To do.

[0004]

The present invention can be solved by the following method. 1. A method of treating an imagewise exposed silver halide color photographic light-sensitive material with a bleaching solution containing an aminopolycarboxylic acid iron (III) complex salt after color development, wherein the bleaching solution contains a compound represented by the following formula (S): A method for processing a silver halide photographic light-sensitive material, which comprises:

[0005]

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[0006] 2. The replenishing amount of the bleaching solution is 1
The treatment method according to 1, wherein the amount is 600 ml or less per m ² . 3. The bleaching solution is replenished with a bleach replenishing solution, and an overflow solution of the bleaching solution generated by the replenishment is stored outside the bleaching tank,
A bleach regenerator is added to the stored overflow liquor, and the bleach replenisher is used again as a bleach replenisher.
The processing method described in 1. 4.1 to 3, wherein the bleaching solution contains a dicarboxylic acid compound. In 5.4, a treatment method characterized by containing a dicarboxylic acid represented by the following general formula (D) and a salt thereof: General formula (D) HOOC-L-COOH (wherein L is a C1 to C4 Represents a saturated or unsaturated aliphatic group.)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION First, the present invention is characterized by using a sulfinic acid compound represented by the following general formula (S).

[0008]

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It is already known to add sulfinic acid to a processing solution. For example, in JP-A No. 1-230039, sulfinic acid is added to at least one of the processing steps during processing containing an aromatic primary amine color developing agent. Although there is a description of a treatment method including that, it is described that it may be contained in the bleaching solution, but there is no description of adding sulfinic acid to the bleaching solution itself, and a dyeing phenomenon which is a problem in the present invention is also described. Not not. Although it is described in the above specification that the effect is remarkable when the time of the desilvering step is shortened, in the present invention, since the effect of the invention is more remarkable when the bleaching time is longer, the reference to dyeing is also mentioned. However, it is a description of objects and effects different from the present invention. The compound represented by formula (S) will be described in detail. R is a substituted or unsubstituted alkyl group (methyl group, ethyl group, n-propyl group, hydroxyethyl group, sulfoethyl group, carboxyethyl group, methoxyethyl group, etc.), substituted or unsubstituted alkenyl group (allyl group, Butenyl group,
Etc.), a substituted or unsubstituted aralkyl group (benzyl group, phenethyl group, 4-carboxyphenylmethyl group,
3-sulfophenylmethyl group, etc.), substituted or unsubstituted cycloalkyl group (cyclohexyl group, etc.), substituted or unsubstituted aryl group (phenyl group, 4-methylphenyl group, naphthyl group, 3-carboxyphenyl group) ,
4-methoxyphenyl group, 3-sulfophenyl group, 4-
Carboxymethoxyphenyl group, 3-carboxymethoxyphenyl group, 4-carboxyethoxyphenyl group, 4
-Sulfoethoxyphenyl group, 4-carboxymethylphenyl group, 4- (N-carboxymethyl-N-methyl)
Phenyl group, etc.) or a substituted or unsubstituted heterocyclic group (pyridyl group, furyl group, thienyl group, pyrazolyl group, indolyl group, etc.). M represents a cation,
For example, hydrogen atom, alkali metal, alkaline earth metal,
Examples thereof include nitrogen-containing organic bases and ammonium groups. Alkali metals such as Na, K and Li, alkaline earth metals such as Ca and Ba, nitrogen-containing organic bases such as usual amines capable of forming a salt with sulfinic acid, and ammonium groups such as unsubstituted ammonium groups , Tetramethylammonium group, and the like.

When the group represented by R in the general formula (S) has a substituent, examples thereof include a nitro group,
Halogen atom (base atom, bromine atom, etc.), cyano group,
Alkyl group (methyl group, ethyl group, propyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, dimethylaminoethyl group, etc.), aryl group (phenyl group, naphthyl group, carboxyphenyl) Group, sulfophenyl group,
Alkenyl group (allyl group, butenyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), acyl group (acetyl group, benzoyl group) Group,
Carbamoyl group (unsubstituted carbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, etc.), carbonamide group (acetamido group, benzamide group) , Etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group,
), Acyloxy group (acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (methanesulfonyloxy group, etc.), ureido group (unsubstituted ureido group,
Etc.), thioureido group (unsubstituted thioureido group, methylthioureido group, etc.), carboxylic acid or salt thereof, sulfonic acid or salt thereof, hydroxy group, alkoxy group (methoxy group, ethoxy group, carboxyethoxy group, carboxymethoxy group, Sulfoethoxy group, sulfopropyloxy group, etc.), alkylthio group (methylthio group, carboxymethylthio group, sulfoethylthio group, etc.), amino group (unsubstituted amino group, dimethylamino group, N-carboxyethyl-N-methyl) Amino group, etc.).

Specific examples of the compound represented by formula (S) are given below.

[0012]

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[0013]

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[0014]

[Chemical 6]

Among these, S-2, S-4, S-7, S
-11 is preferred, and S-7 is particularly preferred. A suitable amount of these compounds is 0.0 to 1 liter of bleaching solution.
05-0.1 mol, preferably 0.01-0.08 mol 0.015-0.05 mol. A plurality of them may be used in combination. The bleaching solution of the present invention will be described in detail. In the present invention, various bleaching agents can be used in the bleaching solution.
For example, hydrogen peroxide, persulfate, red blood salt, dichromate, iron chloride, iron (III) complex aminopolycarboxylate, and the like. Of these, preferred are aminopolycarboxylic acid iron (III) complex salts, and particularly preferred aminopolycarboxylic acids are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′. , N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, nitrilo-N-2-carboxy-N, N
-Diacetic acid, N- (2-acetamido) iminodiacetic acid,
1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol-N, N, N ',
N'-tetramethylenephosphonic acid, ethylenediamine-N,
Examples thereof include N, N ', N'-tetramethylenephosphonic acid and 1,3-propylenediamine-N, N, N', N'-tetramethylenephosphonic acid. Among the above, 1,3-diaminopropanetetraacetic acid, nitrilo-N-2-carboxy-N, N-diacetic acid, N- (2-acetamido) iminodiacetic acid and ethylenediaminetetraacetic acid are particularly preferable. Most preferred is 1,3-diaminopropanetetraacetic acid.
Among these, iron (III) complex salts of compounds represented by the following general formula (I) or (II) are more preferably used. General formula (I)

[0016]

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(In the formula, R ₁ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. L ₁ and L ₂
Each represents an alkylene group. M ₁ and M ₂ each represent a hydrogen atom or a cation. ) General formula (II)

[0018]

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(In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, a hydroxy group or a carboxy group. T and u are respectively Each represents 0 or 1. W represents a divalent linking group containing a carbon atom, and M ₂₁ , M ₂₂ , M _23, and M ₂₄ each represent a hydrogen atom or a cation.)

Next, the compound represented by formula (I) will be described in detail. The number of carbon atoms described below is the number of carbon atoms excluding the substituent.

The aliphatic hydrocarbon group represented by R ₁ is a linear, branched or cyclic alkyl group (preferably having 1 carbon atom).
-12, more preferably 1-10, still more preferably 1-
8), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, further preferably 2 to 7 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 carbon atoms).
10 to 10, more preferably 2 to 7), and may have a substituent.

As the substituent, for example, an aryl group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms,
Particularly preferably, it has 6 to 8 carbon atoms, such as phenyl,
p-methylphenyl. ), An alkoxy group (preferably having 1 to 8 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably having 1 to 4 carbon atoms, for example, methoxy and ethoxy. ), An aryloxy group (preferably having 6 to 12 carbon atoms, more preferably having 6 to 1 carbon atoms)
0, particularly preferably 6 to 8 carbon atoms, such as phenyloxy. ), An acyl group (preferably having 1 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably having 2 to 8 carbon atoms, for example, acetyl), and an alkoxycarbonyl group (preferably having 2 carbon atoms).
-12, more preferably 2-10 carbon atoms, particularly preferably 2-8 carbon atoms, such as methoxycarbonyl. ), An acyloxy group (preferably having 1 to 1 carbon atoms)
12, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, acetoxy. ), An acylamino group (preferably having 1 to 10 carbon atoms,
More preferably 2 to 6 carbon atoms, particularly preferably 2 carbon atoms
To 4, for example, acetylamino. ),
Sulfonylamino group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms)
And for example, methanesulfonylamino. ), A sulfamoyl group (preferably having a carbon number of 0 to 1)
It has 0, more preferably 0 to 6 carbon atoms, and particularly preferably 0 to 4 carbon atoms, and examples thereof include sulfamoyl and methylsulfamoyl. ), A carbamoyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, for example, carbamoyl,
Methylcarbamoyl is mentioned. ), Alkylthio group (preferably having 1 to 8 carbon atoms, more preferably 1 to 8 carbon atoms)
6, particularly preferably having 1 to 4 carbon atoms, such as methylthio and ethylthio. ), A sulfonyl group (preferably having 1 to 8 carbon atoms, more preferably having 1 to 6 carbon atoms,
Particularly preferably, it has 1 to 4 carbon atoms, for example, methanesulfonyl. ), A sulfinyl group (preferably having 1 to 8 carbon atoms, more preferably having 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, for example, methanesulfinyl), a hydroxy group, a halogen atom (eg, fluorine) Atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxy group, nitro group, and heterocyclic group (for example, imidazolyl, pyridyl). These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

The substituent of the aliphatic hydrocarbon group represented by R ₁ is preferably an alkoxy group, a carboxy group, a hydroxy group or a sulfo group, and more preferably a carboxy group or a hydroxy group. The aliphatic hydrocarbon group represented by R ₁ is preferably an alkyl group, more preferably a linear alkyl group, and still more preferably methyl, ethyl, carboxymethyl, 1-carboxyethyl,
Carboxyethyl, 1,2-dicarboxyethyl, 1-
Carboxy-2-hydroxyethyl, 2-carboxy-
2-hydroxyethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-sulfoethyl, 1-carboxypropyl, 1-carboxybutyl, 1,3-dicarboxypropyl, 1-carboxy-2- (4-imidazolyl) ethyl, 1-carboxy-2-phenylethyl, 1-carboxy-3-methylthiopropyl, 2-carbamoyl-
1-carboxyethyl, 4-imidazolylmethyl, particularly preferably methyl, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 1,2-dicarboxyethyl, 1-carboxy-2-hydroxyethyl, 2-carboxy. 2-hydroxyethyl, 2-hydroxyethyl, 1-carboxypropyl, 1-carboxybutyl, 1,3-dicarboxypropyl, 1-carboxy-2-phenylethyl, 1-carboxy-3-methylthiopropyl.

The aryl group represented by R ₁ is preferably a monocyclic or bicyclic aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl, etc.), and more preferably phenyl having 6 to 15 carbon atoms. Group, more preferably 6 to 1
It is a phenyl group of 0. The aryl group represented by R ₁ may have a substituent. Examples of the substituent include those exemplified as the substituent of the aliphatic hydrocarbon represented by R ₁ and an alkyl group (preferably having 1 carbon atom). To 8, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methyl and ethyl.), An alkenyl group (preferably 2 to 8 carbon atoms, more preferably 2 carbon atoms). To 6, particularly preferably 2 to 4 carbon atoms, for example, vinyl and allyl.), Alkynyl group (preferably 2 carbon atoms)
-8, more preferably 2-6 carbon atoms, particularly preferably 2-4 carbon atoms, such as propargyl. ).

The substituent of the aryl group represented by R ₁ is preferably an alkyl group, an alkoxy group, a hydroxy group or a sulfo group, and more preferably an alkyl group, a carboxy group or a hydroxy group. Specific examples of the aryl group represented by R ₁ include 2-carboxyphenyl and 2-
Carboxymethoxyphenyl is mentioned.

The heterocyclic group represented by R ₁ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one N, O or S atom, which may be a monocyclic ring. However, it may form a condensed ring with another ring. The heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, more preferably a 5- to 6-membered aromatic heterocyclic group containing a nitrogen atom, and further preferably a nitrogen atom having 1 to 2 atoms. And a 5- or 6-membered aromatic heterocyclic group. Specific examples of the heterocyclic group include, for example, pyrrolidinyl, piperidyl, piperazinyl, imidazolyl, pyrazolyl, pyridyl, and quinolyl, and preferably imidazolyl and pyridyl.

The heterocyclic group represented by R ₁ may have a substituent, and examples of the substituent include those listed as the substituent of the aliphatic hydrocarbon represented by R ₁ and an alkyl group (preferably Has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, and examples thereof include methyl and ethyl.), An alkenyl group (preferably 2 to 8 carbon atoms, more preferably). Has 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, and examples thereof include vinyl and allyl), an alkynyl group (preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably). Has 2 to 4 carbon atoms
And, for example, propargyl. ).

The substituent of the heterocyclic group represented by R ₁ is preferably an alkyl group, an alkoxy group, a hydroxy group or a sulfo group, and more preferably an alkyl group, a carboxy group or a hydroxy group. R ₁ is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom, methyl, ethyl, 1-carboxyethyl, 2-carboxyethyl, hydroxyethyl or 2-carboxy-2-hydroxyethyl. And particularly preferably a hydrogen atom.

The alkylene groups represented by L ₁ and L ₂ may be the same or different from each other, and may be linear, branched or cyclic. Further, it may have a substituent, and examples of the substituent include, in addition to those described as the substituent of the aliphatic hydrocarbon represented by R ₁ , an alkenyl group (preferably having 2 to 8 carbon atoms, more preferably Number 2
6, particularly preferably having 2 to 4 carbon atoms, for example, vinyl and allyl. ), An alkynyl group (preferably having 2 to 8 carbon atoms, more preferably having 2 to 6 carbon atoms, particularly preferably having 2 to 4 carbon atoms, and examples thereof include propargyl). As the substituent of the alkylene group represented by L ₁ and L ₂ , an aryl group,
They are an alkoxy group, a hydroxy group, a carboxy group and a sulfo group, and more preferably an aryl group, a carboxy group and a hydroxy group. The alkylene group represented by L ₁ and L ₂ is preferably an alkylene group having 1 carbon atom.
To 6, more preferably 1 to 4 carbon atoms, still more preferably substituted or unsubstituted methylene or ethylene.

Specific preferred examples of the alkylene group include:
For example, methylene, ethylene, trimethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1,2-cyclohexylene, 1-carboxymethylene, carboxymethylmethylene, carboxyethylmethylene, hydroxymethylmethylene, 2-hydroxy Ethylmethylene, carbamoylmethylmethylene,
Phenylmethylene, benzylmethylene, 4-imidazolylmethylmethylene, 2-methylthioethylmethylene, and more preferably methylene, ethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethyl. Methylene, carboxyethylmethylene, hydroxymethylmethylene, benzylmethylene, 4-imidazolylmethylmethylene, 2-methylthioethylmethylene, and more preferably methylene, ethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethylmethylene, hydroxymethylmethylene and benzylmethylene.

The cations represented by M ₁ and M ₂ are organic or inorganic cations, and include, for example, alkali metals (Li ⁺ , Na ⁺ , K ⁺ , Cs ^+, etc.), alkaline earth metals (Mg ²⁺ , Ca ²⁺ ), ammonium (ammonium, trimethylammonium, triethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 1,2-ethanediammonium, etc.), pyridinium, imidazolium, phosphonium (tetrabutylphosphonium, etc.) Can be mentioned. M ₁ and M ₂ are preferably alkali metals and ammonium, and more preferably Na ⁺ , K ⁺ , N
H ₄ ⁺ . Among the compounds represented by the general formula (I),
Preferred is a compound represented by the general formula (Ia). General formula (Ia)

[0032]

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(Where L is₁And M₁Are general
It is synonymous with those in formula (I), and
The same applies to the box. M_a1And M_a2Is represented by the general formula (I)
M_TwoIs synonymous with In formula (Ia), L is more preferably₁Is replaced
Or unsubstituted methylene or ethylene;₁,
M_a1, M_a2Is hydrogen atom, alkali metal, ammonium
In either case, more preferably, L₁Is replaced
Or unsubstituted methylene, M₁, M_a1, M_a2Is hydrogen
Atomic, alkali metal, or ammonium
Yes, particularly preferably L₁Is the total carbon number including the substituent
Is 1-10 substituted or unsubstituted methylene;
M₁, M_a1, M_a2Is a hydrogen atom, Na⁺, K ⁺, NH_Four ⁺
This is one of the cases.

Next, the compound represented by the general formula (II) will be described in detail. The aliphatic hydrocarbon group, aryl group and heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each an aliphatic hydrocarbon group represented by R ₁ in the general formula (I), an aryl group, It has the same meaning as the heterocyclic group, and the preferred range is also the same. R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom. t and u each represent 0 or 1, and are preferably 1.

The divalent linking group represented by W is preferably represented by the following general formula (W). The general formula ^{(W) - (W 1 -D} ) v - (W 2) w -

In the formula, W ¹ and W ² may be the same or different, and may be a linear or branched alkylene group having 2 to 8 carbon atoms (eg ethylene, propylene, trimethylene), or 5 to 10 carbon atoms. Cycloalkylene group (for example, 1,2-cyclohexylene), an arylene group having 6 to 10 carbon atoms (for example, o-phenylene), an aralkylene group having 7 to 10 carbon atoms (for example, o-xylenyl), and a divalent nitrogen-containing hetero group. Represents a ring group or a carbonyl group. The divalent nitrogen-containing heterocyclic group is preferably a 5 or 6-membered heteroatom is nitrogen, which is linked to a W1 and W ² at such Tonaria' carbon atoms imidazolyl group. D represents -O-, -S-, -N (Rw)-. Rw
Is a hydrogen atom or a carbon number which may be substituted with a carboxyl group, a phosphono group, a hydroxy group or a sulfo group.
8 alkyl groups (eg methyl) or 6 to 1 carbon atoms
Represents an aryl group of 0 (eg phenyl). As W ₁ and W ₂ , an alkylene group having 2 to 4 carbon atoms is preferable.

V represents an integer of 0 to 3, and v is 2 or 3.
Then W ¹ -D may be the same or different. v is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0. w represents an integer of 1 to 3, and when w is 2 or 3, W2 may be the same or different.
w is preferably 1 or 2. Examples of W include the following.

[0038]

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[0039]

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More preferably, W is ethylene, propylene, trimethylene or 2,2-dimethyltrimethylene, and ethylene or trimethylene is particularly preferable.
M ₂₁ , M ₂₂ , M ₂₃ , and M ₂₄ each represent a hydrogen atom or a cation, and these are M ₁ and M in the general formula (I).
Synonymous with ₂ . Among the compounds represented by the general formula (II), those in which R ₂₂ and R ₂₄ are hydrogen atoms, and t and u are preferably 1, and more preferably R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are hydrogen Atom and t and u are 1. General formula (II)
More preferably, among the compounds represented by R ₂₁ , R ₂₂ ,
R ₂₃ and R ₂₄ are hydrogen atoms, t and u are 1, W is ethylene, M
₂₁ , M ₂₂ , M ₂₃ , and M ₂₄ are hydrogen atoms, Na ⁺ , K ⁺ , NH
Selected from ₄ ⁺ , R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are hydrogen atoms, t and u are 1, W is trimethylene, M ₂₁ ,
M ₂₂ , M ₂₃ , and M ₂₄ are hydrogen atoms, Na ⁺ , K ⁺ , NH ₄ ⁺
It was chosen from.

When the compound represented by the general formula (I) or (II) has an asymmetric carbon in the molecule, it is preferable that at least one asymmetric carbon is L-form. Further, when the compound has two or more asymmetric carbon atoms, it is preferable that the number of L-structures in the asymmetric carbon part is large. Specific examples of the compound represented by formula (I) or (II) are shown below, but the invention is not limited thereto. In the compounds, the description of L indicates that the asymmetric carbon moiety of the description part is the L-form, and the description of the asymmetric carbon part indicates the D, L mixture.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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The above compound may be one in which the hydrogen atom of the carboxy group becomes a cation. In this case, the cation has the same meaning as defined for the cations represented by M ₁ and M ₂ in the general formula (I).

The compound represented by the general formula (I) of the present invention is described in, for example, "Journal of in Organic and Nuclear Chemistry" Vol.
Page (1973) (Journal of Inorg)
anic and Nuclear Chemistr
y Vol. 35,523 (1973)), Swiss Patent No. 561504, German Patent No. 3912551A1.
Issue No. 3939755A1 Issue No. 3939756A1
JP-A-5-265159 and JP-A-6-59422 (exemplified compounds I-42, I-43, I-46, I-5.
2, L-body synthesis method of I-53 is Synthesis Examples 1, 2, 3, 4, 6
It is described in. ), 6-95319 (L of Exemplified Compounds I-8, I-11, I-37, I-38, I-40).
Body synthesis methods are described in Synthesis Examples 2 to 6), 6-1.
It can be synthesized according to the method described in No. 61054, No. 6-161065 or the like.

Further, the compound represented by the general formula (II) is
For example, JP-A-63-199295 and JP-A-3-173.
No. 857, "Bulletin of the Chemical Society of Japan," Vol. 46, p. 884 (197).
3 years) (Bulletin of Chemical S
ociety of Japan Vol. 46,84
4 (1973)), "Inorganic Chemistry," Vol. 7, page 2405 (1968) (Inorgan).
ic Chemistry Vol. 7,2405 (1
968)) (A method for synthesizing the L, L form of Exemplified Compound II-15 is described.) And the like.

In the present invention, the iron (III) complex salt of the compound represented by the general formula (I) or (II) may be added in advance as an iron (III) complex salt, or may be added in a solution. , A compound represented by the general formula (I) or (II) and iron (I
II) A salt (for example, iron (III) nitrate, ferric chloride, etc.) may be allowed to coexist to form a complex in the treatment liquid. The compounds represented by formula (I) or (II) in the present invention may be used alone or in combination of two or more kinds. In the present invention, the compound represented by the general formula (I) or (II) is used in an amount necessary for complexing iron (III) ions (for example,
The amount may be a slight excess of 0.5 mol, 1-fold mol, 2-fold mol, etc., relative to the iron (III) ion, and when it is in excess, it is usually in the range of 0.01 to 15 mol%. Is preferred.

The organic acid iron (III) complex salt contained in the bleaching treatment solution of the present invention may be used as an alkali metal salt or an ammonium salt. As the alkali metal salt, a lithium salt, a sodium salt, a potassium salt, and the like, and as the ammonium salt, an ammonium salt, a tetraethylammonium salt, and the like can be given.In the present invention, the ammonium ion concentration in the processing solution having the bleaching ability is 0-0.
It is preferably 4 mol / l, particularly preferably 0 to 0.2 mol / l. In the present invention, the above-mentioned iron complex salts of organic acids may be used alone or in combination of two or more as a bleaching agent. In the present invention, it is preferable that the bleaching solution contains a dicarboxylic acid. The dicarboxylic acid compound means a saturated dicarboxylic acid having two carboxyl groups in one molecule, an unsaturated dicarboxylic acid, an aromatic carboxylic acid, and an alkali metal salt or ammonium salt thereof. In the present invention, dicarboxylic acids represented by the following general formula (D) and salts thereof are preferred. General formula (D) HOOC-L-COOH (In the formula, L represents a saturated or unsaturated aliphatic group having 1 to 4 carbon atoms.) The preferable addition amount is 0.1 mol to 1 liter of the bleaching solution.
The amount is 1.5 mol, more preferably 0.3 mol to 1.2 mol. Examples of preferable dicarboxylic acids are shown below, but the present invention is not limited thereto. Examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, phthalic acid, diglycolic acid, aspartic acid and glutamic acid. Among these, particularly preferable are malonic acid, succinic acid, glutaric acid, and maleic acid, and it is preferable to use a combination of two or more kinds thereof, and it is particularly preferable to use two kinds of succinic acid and maleic acid in combination. . The bleaching solution constituting the present invention contains, in addition to the bleaching agent and the above compounds, a bromide such as potassium bromide, sodium bromide, ammonium bromide or a chloride such as potassium chloride, sodium chloride or ammonium chloride. An agent can be included. A plurality of rehalogenating agents may be used in combination. The concentration of the rehalogenating agent is 0.1 to 2 mol, preferably 0.2 to 1.5 mol, per liter of the bleaching solution. In addition, salts such as nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, and sodium phosphate may be added. Further, a bleaching accelerator may be used in the bleaching solution of the present invention. Examples of bleaching accelerators include US Pat. No. 3,893,858,
British Patent No. 1,138,842, JP-A-53-141
No. 623, No. 53-95631, No. 54-52534.
Various mercapto compounds described in JP-A-53-95
No. 630, a disulfide compound described in JP-B-45-8
Nos. 506 and 49-42349, isothiourea derivatives described in JP-A-53-94927, thiazolidine derivatives described in JP-B-53-9854, and thioamides described in JP-A-42349. Compound,
The dithiocarbamate salts described in JP-A-55-26506 can be used. The bleaching solution of the present invention preferably contains at least one of 1,2-benzisothiazolin-3-one or its derivative.
Specific examples of these compounds are shown below, but the invention is not limited thereto.

1,2-benzisothiazolin-3-one, 2-methyl-1,2-benzisothiazolin-3-one
On, 2-ethyl-1,2-benzisothiazoline-3
-One, 2- (n-propyl) -1,2-benzisothiazolin-3-one, 2- (n-butyl) -1,2-benzisothiazolin-3-one, 2- (sec-butyl) -1 , 2-benzisothiazolin-3-one, 2-
(T-Butyl) -1,2-benzisothiazoline-3-
On, 2-methoxy-1,2-benzisothiazoline-
3-one, 2-ethoxy-1,2-benzisothiazolin-3-one, 2- (n-propyloxy) -1,2-
Benzisothiazolin-3-one, 2- (n-butyloxy) 1,2-benzisothiazolin-3-one, 5-
Chloro-1,2-benzisothiazolin-3-one, 5
-Methyl-1,2-benzisothiazolin-3-one,
6-Ethoxy-1,2-benzisothiazolin-3-one, 6-cyano-1,2-benzisothiazolin-3-one
On, 5-nitro-1,2-benzisothiazoline-3
-ON.

The addition amount of these compounds is preferably 0.001 to 1 g, more preferably 0.01 to 0.5 g, and particularly preferably 0.1 to 1 g per liter of the bleaching solution.
02-0.2 g is preferred. These compounds may be added in the form of salts, or two or more kinds may be used in combination.

The replenisher for the solution having a bleaching ability basically contains the concentrations of the respective components calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant. C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (processing tank liquid) C _P : Consumed during processing the concentration of component V _1: amount of replenisher having bleaching ability for the light-sensitive material of 1m _² (ml) V ^2: amount carried from previous bath by the photographic material of 1 m ² (m
l)

In the present invention, the amount of bleach used is 0.0
It is suitably contained in an amount of from 0.05 to 3.0 mol / l, preferably from 0.02 to 2.0 mol / l, and particularly preferably from 0.05 to 1.50 mol / l. The pH of the liquid is suitably 3.0 to 7.0, preferably 3.5 to 6.0, and particularly preferably 4.0 to 5.
The range is 5. As the pH adjuster, organic and inorganic acids and alkalis can be used, but it is preferable to adjust the amounts of acetic acid, nitric acid, sodium hydroxide, potassium hydroxide, ammonia and the above-mentioned dicarboxylic acids. In the present invention, the effect of the present invention becomes more remarkable as the bleaching process time is longer, but an appropriate treatment time is 40 seconds to 10 seconds.
Minutes, preferably 1 minute 30 seconds to 8 minutes, particularly preferably 2 minutes to 7 minutes. In the present invention, when the bleaching solution is continuously processed by replenishment, the pH value of the bleaching replenisher is preferably set to be about 0.1 to 1.0 lower than that of the bleaching solution. It is also preferable to use a replenisher made by regenerating the overflow for this replenishment.
Next, the regeneration of the overflow of the bleaching solution in the present invention will be described. In the bleaching treatment of the present invention, the effect of the present invention becomes remarkable when a bleach replenisher is prepared by adding a bleach regenerant to the overflow, and the resulting bleach replenisher is used as the replenisher. First, the processing tank is replenished in accordance with the processing amount of the photosensitive material, and the overflow liquid corresponding to the replenishing amount is discharged from the bleaching tank. Overflow
It may be pumped out by a pump or the like, but this can be easily done by providing a notch or hole in the upper part of the bleaching tank. This overflow liquid is once stored in a tank outside the bleaching tank, and is processed in a batch at a place where a certain amount is stored. In the bleaching solution, the developed silver obtained by reducing the silver halide in the photosensitive material with a developing agent in a developing bath is oxidized to silver ions using an oxidizing agent called a bleaching agent. At this time, the bleach is reduced by an amount equivalent to the oxidized silver. During regeneration, the reduced bleach is introduced into the bleaching solution and oxidized by oxygen in the air to return to the original bleach. This aeration step can be performed directly on the processing tank. Any means known in the art can be used for aeration, such as blowing air into a liquid having bleaching ability or absorbing air using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Regarding aeration, Eastman
Z-121, Uusing Process, issued by Kodak Company
C-41 3rd edition (1982), BL-1 to BL-2
The contents described on the page can be used. The operation of regenerating the bleaching solution overflow can be performed by adding the above-described bleaching solution regenerant to the aerated overflow solution, and can be used as a replenisher.
In this case, the amount of the bleaching solution regenerant solution is preferably 0.05 to 0.1 times, more preferably 0.06 to 0.09 times the overflow solution amount of the bleaching solution. If the amount is too small, the amount of the liquid may be reduced due to concentration or the like, or the components of the developer may be relatively large, resulting in crystallization and precipitation. On the other hand, if the amount is too large, the amount of liquid will increase at the time of regeneration, and the merit of reducing the waste liquid by regenerating the overflow liquid will be lost.

In the bleaching step liquid, it is generally known that when ammonium salts in the formulation are accumulated in rivers and lakes, they eutrophicate the water quality and affect the environment. In the present invention, the ammonium salt can be replaced with an alkali metal salt. Specifically, it is preferable to use sodium salt, potassium salt, potassium bromide, sodium bromide, potassium nitrate, sodium nitrate, and the like of a ferric organic acid complex salt instead of each ammonium salt. Also,
Ammonia water used for pH adjustment is preferably changed to potassium hydroxide or sodium hydroxide. Heretofore, ammonium salts have been used in a solution having bleaching ability for a major reason to increase the bleaching speed.
However, in a system containing a bleaching accelerator as in the present invention, a sufficient rate can be obtained even with an alkali metal salt, so that there is no problem with a salt other than an ammonium salt.

Next, other processes used in the present invention will be sequentially described. Preferred processing steps in the present invention are as follows, but not limited thereto. Color development-bleach-fix-wash-stable-dry Color development-bleach-bleach-fix-fix-wash-stable-dry Color develop-bleach-bleach-fix-wash-stable-dry Color-bleach-wash-fix-wash -Stable-Drying In the above treatment step, washing with water in the step before stabilization can be omitted. It is also possible to omit the final stabilizing bath. The light-sensitive material applicable to the present invention may be any color light-sensitive material, but is preferably a color negative film or a color reversal film. When the color reversal photosensitive material is processed, black-and-white development, reversal exposure or processing using a reversal bath and, if necessary, washing with water are performed prior to the above steps.

Regarding the processing liquid used for the processing of the color negative film or the color reversal film, see Japanese Patent Application Laid-Open No.
No. 34887, the description from column 81, line 8 to column 93, line 17 can be cited. Particularly, as a color developing solution, JP-A-3-15849 and JP-A-3-174152.
A liquid containing a hydroxylamine having a substituent described in JP-A No. 6-1980 as a preservative is preferable, and a liquid containing hydroxylamine having a sulfoalkyl group as a substituent is particularly preferable. Further, those containing diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and 4,5-dihydrobenzene-1,3-disulfonic acid as a chelating agent are preferred. The replenisher of the color developing solution has a bromide ion concentration of 0.0 from the viewpoint of reducing the replenishment amount.
It is preferable that the concentration is reduced to not more than 04 mol / l, and particularly preferable that the bromide ion concentration is not more than 0.002 mol / l. Preferred examples of these color developing solutions include Process CN- manufactured by Fuji Photo Film Co., Ltd.
16X, CN-16Q, and CN-16FA color developing solutions and color developing replenishers, and the process CR-56P color developing solutions and color developing replenishers.

In the processing of the present invention, the color developing solution is preferably replenished with a color developing replenishing solution. The color developing replenisher contains a compound contained in the color developing solution. The role of the color developing replenisher is to control the concentration of the compound eluted from the photosensitive material by the processing of the photosensitive material or the replenishment of the compound to the color developing solution, which is reduced by deterioration over time in an automatic processor, and vice versa. In this case, the developing performance is kept constant. Therefore, the former compound has a higher concentration than the color developing tank solution, and the latter compound has a lower concentration. The former compound is a color developing agent or a preservative, and the replenisher contains 1.1 to 2 of a tank solution.
Double amount is included. The latter compound is a development inhibitor typified by a halide (for example, potassium bromide). The replenisher contains 0 to 0.6 times the amount of the tank solution. The concentration of the halide in the replenisher is usually 0.006 mol / l or less, but the lower the replenishment, the lower the concentration needs to be. Compounds that hardly change in concentration due to processing or aging are usually contained at approximately the same concentration as the color developing tank solution. Examples of this are chelating agents and buffers. Furthermore, the pH of the color developing replenisher is to prevent the pH of the tank solution from decreasing due to the processing.
Make it about 0.05-0.5 higher than the tank liquid. This p
The difference in H also needs to be increased as the amount of replenishment decreases. The replenishment amount of the color developing solution is 3000 ml per 1 m ² of the photosensitive material.
It is carried out as follows, but preferably from 100 ml to 1500 ml, most preferably from 100 ml to 600 ml.

The processing temperature in the color developing solution is suitably 20 to 55 ° C, preferably 30 to 50 ° C. The processing time is suitably from 20 seconds to 5 minutes, preferably from 30 seconds to 3 minutes and 30 seconds, and more preferably from 1 minute to 3 minutes and 20 seconds. Further, the color developing bath may be divided into two or more baths as necessary, and a color developing replenisher may be replenished from the first bath or the last bath to shorten the developing time and further reduce the replenishing amount. The color developing solution is to increase the activity of the used color developing solution by subjecting the used color developing solution to an anion exchange resin or electrodialysis, or by adding a processing chemical called a regenerating agent, that is, to regenerate and use the developing solution again. Can be done. In this case, the regeneration rate (the ratio of the overflow solution in the replenisher)
Is preferably 50% or more, particularly preferably 70% or more. In the process using the color developing solution regeneration, an overflow solution of the color developing solution is regenerated and then used as a color developing replenisher.
As a regeneration method, it is preferable to use an anion exchange resin. Particularly preferred anion exchange resin compositions and resin regeneration methods include those described in DIAION Manual (I) (14th edition, 1986) issued by Mitsubishi Kasei Co., Ltd. Among the anion exchange resins, JP-A-2-952 and JP-A-1-2811
The resin having the composition described in No. 52 is preferred.

In the present invention, the light-sensitive material that has been processed with the bleaching solution is processed with a processing solution having fixing ability. The processing solution having fixing ability here is specifically a fixing solution and a bleach-fixing solution. In the step of processing with the bleach-fix solution after bleaching with the bleach solution, the bleaching agent of the bleach solution and the bleach-fix solution may be the same or different. After the bleaching process with the bleaching solution, a washing step may be performed during the processing with the bleach-fixing solution.

The processing solution having fixing ability contains a fixing agent. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate; thiocyanates (rodane salts) such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate; And thioethers. Among them, it is preferable to use ammonium thiosulfate. The amount of the fixing agent is from 0.3 to 3 mol, preferably from 0.5 to 2 mol, per liter of a processing solution having a fixing ability. Further, from the viewpoint of promoting fixing, the thiosulfate may be selected from the ammonium thiocyanate (rhodanammonium), thiourea, thioether (for example, 3,6-dithia-1,8-octanediol), and thiosulfonic acid (for example, ammonium methanethiosulfonate). )
It is also preferable to use in combination. Among them, it is most preferable to use a combination of a thiosulfate and a thiocyanate or a combination of a thiosulfate and a thiosulfonate. In particular, a combination of ammonium thiosulfate and ammonium methanethiosulfonate is preferred. The amount of these compounds used in combination is preferably 0.01 to 1 mol, preferably 0.1 to 0.5 mol, per liter of processing solution having fixing ability. In the case of thiocyanic acid, The use of 1 to 3 moles can greatly enhance the fixing promoting effect. When thiosulfonic acid is used, it is preferable to use a sulfinic acid described later in combination.

In the processing solution having fixing ability, a sulfite (eg sodium sulfite, potassium sulfite,
Ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (for example, sodium acetaldehyde bisulfite, particularly preferably a compound described in Japanese Patent Application No. 1-298935) or
And a sulfinic acid compound described in US Pat. Furthermore, various fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained. Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having a fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediamine Examples thereof include tetraacetic acid, 1,2-propylenediaminetetraacetic acid, and 1,3-diaminopropanetetraacetic acid. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,3-diaminopropanetetraacetic acid and ethylenediaminetetraacetic acid are particularly preferred. The chelating agent is added in an amount of 0.01 to 0.3 mol, preferably 0.03 to 0.3 mol per liter of the treatment liquid.
0.2 mol. The pH of the fixing solution is preferably from 5 to 9, and more preferably from 6 to 8. In the bleach-fixing solution, it is preferably from 4.0 to 7.0, more preferably from 5.0 to 6.5. In order to adjust the processing solution having fixing ability to such a pH range, and as a buffer,
It is preferable to contain a compound having a pKa in the range of 6.0 to 9.0. These compounds include imidazole,
Imidazoles such as 2-methyl-imidazole are preferred. These compounds are preferably used in an amount of 0.1 to 10 mol, preferably 0.2 to 3 mol, per liter of the processing solution.

The bleach-fixing solution may further contain a compound which can be contained in the bleaching solution described above. In the present invention, the bleach-fix solution at the start of processing (start solution)
Is prepared by dissolving the compound used in the above-mentioned bleach-fixing solution in water, but may be prepared by mixing separately prepared bleaching solution and fixing solution in appropriate amounts. When the replenishment method is adopted, the replenishment amount of the fixing solution or the bleach-fixing solution is 1 m of the photosensitive material.
^The amount per 100 is preferably 100 to 3000 ml, more preferably 300 to 1800 ml. The replenishment of the bleach-fixing solution may be carried out as a bleach-fixing replenisher.
As described in JP-A-143755 and Japanese Patent Application No. 2-216389, an overflow of a bleaching solution and a fixing solution may be used. Further, in the present invention, the total processing time of the processing having fixing ability is 0.5 to 5 minutes, preferably 1.5 to 4
Min, particularly preferably 2 to 3.5 min. In the processing liquid having fixing ability of the present invention, the processing temperature is 25 to 50 ° C.,
It is preferably 35 to 45 ° C.

The processing solution having fixing ability of the present invention can be subjected to silver recovery by a known method, and a regenerating solution subjected to such silver recovery can be used. The fixing solution is preferably used as the solution having a fixing ability when performing silver recovery. Examples of the silver recovery method include an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, and German Patent No. 2,331,220), and an ion exchange method. (Japanese Patent Laid-Open No. 5
1-17114, German Patent No. 2,548,237) and a metal substitution method (UK Patent No. 1,353,805) are effective. These silver recovery methods are preferably performed in-line from the tank liquid, because the rapid processing suitability is further improved. Among these methods, it is preferable to carry out the electrolysis method by an in-line method, and the concentration of silver in the liquid having fixing ability at this time may be kept at 3 g / liter or less, preferably 1 g / liter or less. .. Further, when such silver recovery is carried out, the replenishing amount of the liquid having fixing ability can be further reduced, and it is 10 per 1 m ^{2 of} the light-sensitive material.
0-300 ml is preferred.

In the present invention, after the bleach-fixing or fixing step, or between the bleaching step and the step having the fixing ability, treatment steps such as washing and stabilization which are generally carried out can be carried out. It is also possible to use a simple treatment method in which after the treatment with the treatment liquid having the ability, the stabilizing treatment is carried out without substantially washing with water. In particular, in the case where silver is recovered in a step having a fixing ability, it is preferable that a treatment step such as washing with water, rinsing and stabilization is provided before the step having a fixing ability. The washing water used in the washing step can contain various surfactants in order to prevent unevenness of water droplets when the processed photosensitive material is dried. These surfactants include polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant Agent, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric surfactant However, since the ionic surfactant may combine with various ions mixed in with the treatment to form an insoluble substance, it is preferable to use a nonionic surfactant, particularly, alkylphenol ethylene oxide addition. Are preferred. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water may contain various antibacterial agents and fungicides in order to prevent water stains and molds on the processed light-sensitive material. Examples of these antibacterial and antifungal agents are disclosed in
Nos. 157244 and 58-105145, thiazolylbenzimidazole compounds, isothiazolone compounds described in JP-A-57-8542, and chlorophenol compounds represented by trichlorophenol. Compound, bromophenol compound,
Quaternary represented by organic tin and organic zinc compounds, thiocyanic acid and isothiocyanic acid compounds, acid amide compounds, diazine and triazine compounds, thiourea compounds, benzotriazole alkylguanidine compounds, and benzalkonium chloride Ammonium salts, antibiotics typified by penicillin, etc., Journal Antibact. Antifung. Agents Vol 1. N
o.5, p. 207 to 223 (1983) may be used in combination of one or more. In addition, JP-A-48-
Various fungicides described in No. 83820 can also be used. Further, it is preferable to contain various chelating agents.
Preferred compounds of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, and diethylenetriamine-N, N, N ', N'-. Organic phosphonic acids such as tetramethylene phosphonic acid, or EP 3451
And a hydrolyzate of the maleic anhydride polymer described in 72A1. Further, it is preferable that a preservative which can be contained in the fixing solution or the bleach-fixing solution is contained in the washing water.

The stabilizing solution used in the stabilizing step is a processing solution for stabilizing the dye image. For example, pH 3-6
Aldehyde (eg, formalin)
Although a liquid containing the same can be used, the stabilizing liquid preferably used in the present invention will be described below. In the present invention, it is preferable that the stabilizing solution contains substantially no formaldehyde. The term "substantially free of formaldehyde" means that the total of free formaldehyde and its hydrate is 0.003 / liter of the stabilizing solution.
Represents mol or less. By using such a stabilizer,
Dispersion of formaldehyde vapor during processing can be suppressed. In this case, for the purpose of stabilizing the magenta dye, it is preferable that the formaldehyde releasing compound is present in a stabilizing solution, a bleaching solution, or a pre-bath thereof (for example, a preparation bath).

Preferred compounds as the formaldehyde-releasing compound are hexamethylenetetramine and its derivatives, formaldehyde bisulfite adducts, azolylmethylamines and N-methylol compounds. In addition to stabilizing the magenta dye, these preferable compounds suppress the generation of yellow stain over time. Hexamethylenetetramine and its derivatives are described in "Beilsteins Handbuch der Organishen Chemie", Vol. II, Vol. 26, pp. 200-P.212. Can be used, and hexamethylenetetramine is particularly preferred. Further, as the formaldehyde bisulfite addition product, sodium formaldehyde bisulfite is preferable.

As the azolylmethylamine, an azole selected from triazole, pyrazole and imidazole, and three compounds of piperazine, morpholine, amine selected from 4-hydroxyethylpiperidine and 4-hydroxypiperidine, and formaldehyde are reacted. What is obtained by this is preferable. Of these, in particular, N, N'-bis (1,2,4-triazole-
1-ylmethyl) piperazine and N, N'-bis (pyrazol-1-ylmethyl) piperazine are preferred. As the N-methylol compound, an N-methylol compound of pyrazole and its derivative, an N-methylol compound of triazole and its derivative, and an N-methylol compound of urazole and its derivative are particularly preferable. These N
Specific examples of the methylol compound include: 1-hydroxymethylpyrazole 1-hydroxymethyltriazole 1-hydroxymethylurazole Among them, the most preferable is 1-hydroxymethylpyrazole. The N-methylol compound can be easily synthesized by reacting an amine compound having no methylol group with formaldehyde or paraformaldehyde.

Of the above formaldehyde-releasing compounds,
Particularly preferred are hexamethylenetetramine, formaldehyde sodium bisulfite, and the preferred azolylmethylamine and N-methylol compounds. Among them, N, N′-bis (1,2,4-triazol-1-ylmethyl) piperazine and N, N′-bis (pyrazol-1-ylmethyl) piperazine are most preferred. When using the above azolylmethylamine or N-methylol compound, it is preferable to coexist an amine compound such as triazole or pyrazole in the treatment solution.
The coexistence of a 0-fold molar concentration is preferred. The preferred amount of the formaldehyde releasing compound to be added is 0.003 to 0.2 mol, preferably 0.005 to 0.5 mol per liter of the treatment liquid.
05 mol. Two or more of these formaldehyde releasing compounds may be used in combination in the bath.

The stabilizing solution may contain all compounds that can be added to the washing water. In addition, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, and fluorescent whitening may be added as necessary. Agents, hardeners, alkanolamines described in US Pat. No. 4,786,583, and the like can be used. In addition, the washing step and the stabilizing step are preferably performed in a multi-stage countercurrent system.
~ 4 stages are preferred. The replenishment amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area. Tap water can be used as the water used in the washing step or the stabilizing step, but water, deionized to a Ca or Mg concentration of 5 mg / liter or less with an ion exchange resin, halogen, halogen,
It is preferable to use water sterilized by an ultraviolet germicidal lamp or the like. In addition, the water for correcting the evaporation of each treatment liquid may be tap water, but is preferably deionized water or sterilized water preferably used in the above-mentioned washing step or stabilization step. Is good. Developer, bleach, bleach-fix,
In order to correct the concentration by evaporation not only of the fixing solution but also of other processing solutions, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher. Evaporation correction can be performed by the method described in Hatsumei Kyokai Giho 94-4992, page 1, right column, line 26 to page 3, left column, line 28. Further, the amount of waste liquid can also be reduced by using a method in which the overflow solution in the water washing step or the stabilization step flows into a bath having a fixing ability, which is a pre-bath.
A commercially available developing apparatus for carrying out the present invention can be used. An example of a preferred development processing apparatus for carrying out the present invention is FP2 manufactured by Fuji Photo Film Co., Ltd.
30B, FP350, FP360B, FP560B, F
P900, FNCP900, FNCP900II, FNC
P900III, FNCP600II, FNCP300II,
HM-55S, H8-440 manufactured by Noritz Koki Co., Ltd.
W-4, HM-60R, HR4-8360, US HOP
Examples include HOPE138 and HOPE2409V manufactured by E company. For the stirring method and material of the development processor,
Those described in JP-A-4-130432 are preferable.

Next, a preferred silver halide color photographic light-sensitive material for the processing of the present invention will be described. The silver halide color photographic light-sensitive material to which the present invention is preferably applicable includes a color negative film coated with a silver iodobromide emulsion and a color reversal film, and a color negative film is particularly preferable, and a magnetic recording on the support is particularly preferable. Those having layers are preferred.

Next, a light-sensitive material having a magnetic recording layer which is preferably processed in the present invention will be described. The magnetic recording layer is formed by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support, and the magnetic particles include a ferromagnetic iron oxide such as γFe ₂ O ₃ or Co. Adhered γ
Fe ₂ O ₃ , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like are used. Among them, such as Co-coated γFe ₂ O ₃
Co-coated ferromagnetic iron oxide is preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably
3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, particularly preferably 4.0
× 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. Also, Japanese Patent Laid-Open No. 4-25
Magnetic particles described in 9911 and 5-81652 whose surface is coated with an inorganic or organic substance can also be used.

The binder used for the magnetic particles includes the thermoplastic resins, thermosetting resins, radiation-curable resins, reactive resins, acids, alkalis or biodegradable polymers described in JP-A-4-219569, and natural products. Coalescence (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The glass transition temperature Tg of the above resin is -40 ° C to 300 ° C, and the weight average molecular weight is 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohols (for example, Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane), and polyisocyanates formed by condensation of these isocyanates, and the like, which are described in, for example, JP-A-6-59357.

As a method of dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill or an annular type mill is preferable, and a combination thereof is also preferable, as in the method described in JP-A-6-35092. Dispersant described in JP-A-5-088283,
Other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably 0.01~ 2g / m ^2,
More preferably, it is 0.02 to 0.5 g / m ² . The magnetic recording layer used in the present invention can be provided on the back surface of the photographic support by coating or printing and provided in the entire surface or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

The magnetic recording layer may have functions such as improvement of lubricity, curl control, antistatic, adhesion prevention and head polishing, or another functional layer may be provided to impart these functions. Alternatively, at least one kind of particles is preferably a non-spherical inorganic particle abrasive having a Mohs hardness of 5 or more. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
4, 5,229,259, 5,215,874 and EP 466,130.

The light-sensitive material processed in the present invention is preferably a light-sensitive material for photographing, and its support is preferably polyester. Institute of Invention; 1994.3.15.). The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Particularly preferred among them is polyethylene 2,
It is 6-naphthalate. Average molecular weight range is about 5,000
Or 200,000. The polyester of the present invention has a Tg of 50.
C. or higher, more preferably 90.degree. C. or higher.

Next, the polyester support has a Tg of 40 ° C. or higher and lower than Tg, more preferably Tg−, in order to prevent the curling tendency.
Heat treatment is performed at 20 ° C. or higher and lower than Tg. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. Surface irregularities may be imparted (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. In order to prevent light piping, the purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the light-sensitive material used in the present invention,
In order to bond the support and the light-sensitive material constituting layer, it is preferable to perform a surface treatment. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. In the undercoat layer, gelatin hardeners such as chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, and active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) And the like, epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

An antistatic agent is preferably used in the light-sensitive material used in the present invention. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. Most preferred are, ZnO as antistatic _{agents, TiO 2, SnO 2, Al} 2 O 3, In
The volume resistivity of at least one selected from ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ and V ₂ O ₅ is 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. Some particle size 0.001 ~ 1.0μ
m crystalline metal oxides or their composite oxides (Sb,
P, B, In, S, Si, C, etc.) fine particles, and further, sol-like metal oxides or fine particles of a composite oxide thereof. The addition amount to the photographic material, 5 to 500 mg / m ² is preferably particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is from 1/300 to 100/1.
And more preferably 1/100 to 100/5.

Further, it is preferable that the light-sensitive material has slipperiness. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. The preferred sliding property is the dynamic friction coefficient.
It is 0.25 or less and 0.01 or more. The measurement at this time represents the value when transported at a rate of 60 cm / min with respect to a stainless ball having a diameter of 5 mm (25 ° C, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane. And polymethylphenylsiloxane. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

Further, it is preferable that the light-sensitive material has a matting agent. The matting agent may be on either the emulsion side or the back side, but is preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate /
Methacrylic acid = 9/1 or 5/5 (molar ratio)), and polystyrene particles are preferred. The particle size is preferably 0.8 to 10 μm,
It is preferable that the particle size distribution is narrow, and the average particle size is 0.9 to
It is preferable that 90% or more of the total number of particles be contained within 1.1 times. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)) ,
Polystyrene particles (0.25 μm), colloidal silica (0.
03 μm).

The light-sensitive material used in the present invention is described in JP-A No. 4/1992.
No. 125558, page 14, upper left column, first row to eighteenth
The one described in the lower left column, line 11 of the page is preferred. In particular, a silver halide emulsion having an average silver iodide content of 3 to 2 is preferred.
A silver iodobromide emulsion of 0 mol% is preferable, and a tabular grain having an aspect ratio of 5 or more or a double structure grain having a different halogen composition between the inside and the outside is preferable. Further, the inside and outside may have a clear layered structure. The aspect ratio is particularly preferably from 5 to 20, and more preferably from 6 to 12. In addition, U.S. Pat.
The monodisperse emulsion described in 55394 is also preferable. The photosensitive material used in the present invention has an average particle size of 0.02 to 0.2.
It is preferable to have a layer containing a non-photosensitive fine grain silver halide having a thickness of μm. The fine grain silver halide is preferably silver bromide containing 0.5 to 10 mol% of silver iodide.

The additives used in the light-sensitive material used in the present invention are described below. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Super sensitizer, page 649, right column 4. Brightener 24 page 647, right column page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873 to 874 7. Plasticizers, page 27, page 650, right Column 876 Lubricant 8. Coating aid, pages 26 to 27 Page 650 Right column 875 to 876 Surfactant 9. Static 27 page 650 650 Right column 876 to 877 Inhibitor 10. Mast agent 878 to 879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); A-4 -6 of EP 456,257
3 (p. 134), A-4 -73, -75 (p. 139); M-4, -6 in EP 486,965
(Page 26), M-7 (page 27); EP-571,959A M-45 (page 19);
5-204106 (M-1) (page 6); JP-A-4-362631, paragraph 0237 M-
twenty two. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

Examples of couplers in which the color forming dye has a suitable diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred.

Next, a container for storing a light-sensitive material (patrone) processed by the method of the present invention will be described. The main material of the patrone used may be a metal or a synthetic plastic, but is preferably a plastic material such as polystyrene, polyethylene, polypropylene, polyphenyl ether or the like. The patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations, betaine-based surfactants and polymers can be preferably used. These antistatic patrones are disclosed in JP-A-1-312537,
1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same as the current 135 size, and it is effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to reduce the size of the camera. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

The patrone may be one in which the spool is rotated to feed the film, or the film tip is housed in the patrone body and the spool tip is rotated in the film feeding direction so that the film tip comes out from the port portion of the patrone. It may be a structure for sending to. These are disclosed in US Pat. Nos. 4,834,306, 5,226,613 and 5,296,887. The developed photosensitive material can be stored again in the patrone. In this case, the patrone used may be the same as the photosensitive material before processing or may be different. An example of a specific film format is FUJIFILM ADV issued by Fuji Photo Film Co., Ltd.
As described on pages 3 to 5 of ANCED PHOTO SYSTEM LAB SYSTEM GUIDE, a photosensitive material with a film width of 24 mm and a magnetic recording function is stored in a small plastic cartridge. preferable.

In addition, the contents described in JP-A-4-62543, page 6, upper right column, line 17 to page 10, upper right column, line 17 can be preferably applied to the light-sensitive material used in the present invention. Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of reacting with formaldehyde described in JP-A Nos. 11,987 and 4,435,503 to the light-sensitive material by immobilization. The photosensitive material of the present invention is disclosed in JP-A-60-107029 and JP-A-60-2523.
No. 40, JP-A-1-44940, JP-A-1-4568
Compounds which release a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of the developing agent described in No. 7, etc. can be contained. U.S. Pat. No. 4,740,454;
No. 5,39, U.S. Pat. No. 4,788,132;
It is preferable to contain a mercapto compound described in 283551 or the like.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
52. A compound capable of releasing a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing described in 52 or the like. Dyes dispersed in the light-sensitive material used in the present invention by the method described in International Publication No. WO88 / 04794, JP-A-1-502912, European Patent EP
No. 0317308A2, U.S. Pat. No. 4,420,555.
And the dyes described in JP-A No. 1-259358 can be preferably contained.

The photographic material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-272.
No. 248 and JP-A-1-80941.
2-benzisothiazolin-3-one, n-butyl, p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives or fungicides such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

Specific examples of preferable light-sensitive materials to which the present invention is applied are listed below. Fujicolor SUPER G100 manufactured by Fuji Photo Film Co., Ltd. FUJICOLOR SUPER G200 〃 FUJICOLOR SUPER G400 〃 FUJICOLOR SUPER HG1600 写 FUJICOLOR REALA 〃 FUJICOLOR FULL COLOR Super800 〃 FUJICOLA 160 Professional NS 〃 FUJICOLA 160 Professional L East Kodak Super Gold 200 〃 Kodak Gold 400 〃 Kodak Gold 1600 〃 Kodak Ector 25 〃 Kodak Ector 100 〃 Kodak Ector 1000 〃 Vericolor III Professional Film Type S 〃 Vericolor III Professional Film Type L Konica Color Super DD manufactured by Konica Corporation 00 〃 like Konica Color Super DD200 〃 Konica Color XG400 〃 Konica color GX3200, etc. Eastman Kodak Company C-41 processing and Fuji Photo Film Co. CN-16 processing capable photosensitive material is preferably used.

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EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 On a subbed cellulose triacetate film support,
A multilayer color photographic light-sensitive material having the following layers was prepared. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 x 10 ^-2 HBS-4 5.0 x 10 ^-2 Gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property, W-1 to W-3, B-4 to B- are appropriately added to each layer. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

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[Table 1]

In Table 1, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

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The above-mentioned light-sensitive material was prepared according to the JIS standard “JIS K-
7519 (1982) "was cut into a size of a 135-type film as Sample 101. Sample 10
Imagewise exposure was performed on No. 1 and continuous treatment was carried out according to the treatment liquid formulation shown below until the total replenishing amount of the bleaching liquid reached 6000 ml. During the bleaching process, 500 ml / min of air was supplied from the bottom of the tank through a diffuser during processing.

Treatment Process Process Treatment Time Treatment Temperature Replenishment Amount * Tank Capacity (° C) (ml) (liter) Color development 3 minutes 15 seconds 38.0 630 2 Bleach 3 minutes 00 seconds 38.0 715 2 Washing with water (1) 30 seconds 38.0 430 2 Settled 3 minutes 00 seconds 38.0 430 2 Washed with water (2) 1 minute 00 seconds 38.0 770 2 Stabilized 30 seconds 38.0 570 2 Dry 3 minutes 50 * Replenishment amount is photosensitive Quantity per 1 m ^{2 of} material The washing (1) is divided into 2 tanks and the washing (2) is divided into 3 tanks, which is a countercurrent system from the back side to the front side. The amount brought from each process to the next process is 60 ml per 1 m ² of photosensitive material.
It was. The crossover time is 3 seconds in each case, and this time is included in the processing time of the previous step. The composition of the treatment liquid is shown below.

(Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.2 1.2 1-Hydroxyethylidene-1,1-2.7 3.3 Diphosphonic acid Caustic potassium 1.72 1.9 Sodium sulfite 3.84 4.8 Sodium bicarbonate 1.8-potassium carbonate 31.7 39.0 Potassium bromide 1.4 0.37 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.5 3.1 Below Compound 0.044 −

[0143]

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2-Methyl-4- [N-ethyl-N-4.7 5.9 (β-hydroxyethyl) amino] aniline sulphate Water was added to 1.0 liter 1.0 liter pH 10.05 10 .15 (bleaching solution) mother liquor (g) replenisher (g) bleaching agent (listed in Table 2) (listed in Table 2) 1.1 times dicarboxylic acid of mother liquor (listed in Table 2) (listed in Table 2) mother liquor Ammonium bromide 52 58 Ammonium nitrate 11 13 Compound of general formula (S) (described in Table 2) 0.02 mol 0.023 mol Water added 1.0 liter 1.0 liter pH [ammonia water Adjust with] 5.0 5.0

(Fixer) Mother liquor (g) Replenisher (g) Ammonium sulfite 21 23 Ammonium thiosulfate aqueous solution 288 320 ml (750 g / liter) Ethylenediaminetetraacetic acid 0.6 0.68 Water was added 1.0 liter 1.0 Liter pH [adjusted with aqueous ammonia and acetic acid] 6.8 6.8

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and a mixed bed column filled with an OH type strongly basic anion exchange resin (Amberlite IRA-400) to reduce the calcium and magnesium ion concentrations to 3
mg / L or less, followed by 20 mg / L of sodium diisocyanurate and 15 mg of sodium sulfate.
0 mg / liter was added. The pH of this solution is 6.5-
It was in the range of 7.5. (Stabilizing solution and stable replenishing solution) (unit g) Triazole 1.5 N, N'-bis (1,2,4-triazo-0.5-l-1-ylmethyl) piperazine p-toluenesulfinic acid 0.05 sodium poly Oxyethylene-p-monononyl 0.2 phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water is added to add 1.0 liter pH 8.0

[0147]

[Table 2]

Sample 101 processed with a new solution of CN-16X of Fuji Photo Film Co., Ltd. (hereinafter referred to as processed photosensitive material)
It was created. During continuous processing, cumulative replenishment amount is 1000m
The processed light-sensitive material was processed for each l (the processed light-sensitive material is referred to as a dye-sensitive material). The transmission density was measured using a photographic densitometer FSD103 manufactured by Fuji Photo Film Co., Ltd., and the degree of first-come-first-served basis was compared using (concentration of dyeing sensitive material)-(concentration of processed photosensitive material) as an index. The results are shown in Table 3.

[0149]

[Table 3]

As shown in Table 3, according to the measures of the present invention, when the compound represented by the general formula (S) is present in the bleaching solution, dyeing on the light-sensitive material is suppressed. Example 2 In Example 1, the treatment was carried out by changing the replenishing amount of the bleaching solution as shown in Table 4. Further, the composition of the bleaching solution was changed as shown in Table 4 according to the replenishing amount, and further continuous treatment was carried out with the combination of the levels of the compound of the present invention with and without S-7. The treatment was carried out until the accumulated bleach replenishment amount reached 6000 ml. During the continuous processing, the same processed photosensitive material as in Example 1 was processed at a cumulative replenishing amount of 1000 ml, and the transmission density was measured and compared in the same manner as in Example 1. The results are shown in Table 5.
Other processes were performed in the same manner as in Example 1.

[0151]

[Table 4]

[0152]

[Table 5]

As shown above, it can be seen that the effect of suppressing the occurrence of dyeing is greater by using the compound of the present invention when the replenishment amount is reduced.

Example 3 A photosensitive material sample 102 was prepared by applying the photosensitive layer described in Example 1 of the present invention to a support and back layer of the photosensitive material prepared as follows.

1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co.) as an ultraviolet absorber, 300 ° C.
After being melted at, it was extruded from a T-die, stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-fixed at 250 ° C for 6 seconds to form a 90 μm thick PEN.
I got a film. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in the official gazette number 94-6023). 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of Undercoat Layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione were formed on each side. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ^₂ 0.012g / m _2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, a bar coater used), provided with a subbing layer hotter side at the time of stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle diameter of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005 g / m ²
And resorcinol. 3-2) Coating of magnetic recording layer 3-poly (degree of polymerization: 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area: 43 m ² / g; Long axis 0.14μm, single axis 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with silicon oxide aluminum oxide with 2% by weight of iron oxide) 0.06g / m ² diacetyl cellulose 1.2 g / m ² (dispersion of the iron oxide was carried out using an open kneader and a sand _{mill), C 2 H 5 C (} CH 2 OCONH-C 6 H 3 (CH 3) NCO) as a curing agent ₃
0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone as a solvent,
A magnetic recording layer having a thickness of 1.2 μm was obtained. Abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as matting agents, respectively
It was added to 10 mg / m ² . Drying was carried out at 115 ° C for 6 minutes.
° C). X- write saturation magnetization moment of the magnetic recording layer of the D color density increment of about 0.1 of ^B, also the magnetic recording layer is 4.2 emu / g, coercive force 7.3 × 10 ⁴ A / m, the squareness ratio in (blue filter) Was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ C
OOC ₄₀ H ₈₁ (compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
(Compound b, 9 mg / m ² ) mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1/1)
The mixture was melted at 105 ° C. in water, and dispersed by pouring into propylene monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone (average particle size: 0.01 μm) and then added. As a matting agent, silica particles (0.3 μm) and abrasive 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide (0.15 μm) coated with 15% by weight) are each 15 mg / m ² . And dried at 115.
C. for 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer had a dynamic friction coefficient of 0.06 (stainless steel hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a dynamic friction coefficient of 0.12 between the emulsion surface and the sliding layer which will be described later. .

The sample 102 prepared as described above is set to 24 mm
The sheet is cut into a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. 32 sets of these two sets
U.S. Pat. No. 5,296,887
It was housed in a plastic film cartridge described in Figs.

For this sample 102, the head gap 5
The camera was mounted on a camera having a magnetic recording device made of a permalloy material having a number of turns of 50 μm, and digital saturation recording and photographing at a recording wavelength of 50 μm were performed. Samples 102 and a Captured those given imagewise exposure to the sample 101 at an area ratio 1: 50 m per day with a processing solution and a processing method described below so that 1 ²
Each time, continuous processing was performed until the cumulative total of the replenishment amount of the bleaching solution became 50 times the tank capacity. In the bleaching step, regeneration of the overflow solution was performed 100 liters at a time. In the regeneration method, as shown in the chart of FIG. 1, the bleaching replenisher 2 is replenished from the replenishing tank 1 to the bleaching solution 3 in the bleaching tank 4, and the overflow solution 6 from the bleaching tank 4 is stored in the stock tank 5. .
Here, air 8 is blown into the overflow liquid 6 accumulated by the air pump 7 for 4 hours every time 100 liters are accumulated. Thereafter, 8 liters of a bleaching solution regenerator 13 described below was added to prepare a replenishing replenishing solution, and this solution was used as a bleaching replenishing solution for the next time and the treatment was continued.

Treatment Process Process Treatment Time Treatment Temperature Replenishment Amount * Tank Capacity (° C) (ml) (liter) Color Development 3 min 15 sec 38.0 630 195 Bleach 3 min 00 sec 38.0 715 180 Wash with water (1) 30 seconds 38.0 430 90 Settled 3 minutes 00 seconds 38.0 430 180 Water wash (2) 1 minute 00 seconds 38.0 770 90 Stability 30 seconds 38.0 570 45 Dry 3 minutes 50 * Replenishment amount is photosensitive Quantity per 1 m ^{2 of} material The washing (1) is divided into 2 tanks and the washing (2) is divided into 3 tanks, which is a countercurrent system from the back side to the front side. The amount brought from each process to the next process is 60 ml per 1 m ² of photosensitive material.
It was. The crossover time is 3 seconds in each case, and this time is included in the processing time of the previous step. The composition of the treatment liquid is shown below.

The same color developing solution, fixing solution, stabilizing solution, and washing water as in Example 1 were used for the mother liquor replenishing solution. (Start bleach replenisher) 1,3-diaminopropane tetrairon (III) acetate ammonium monohydrate 35 g Maleic acid 33 g Succinic acid 36 g Ammonium nitrate 7 g Potassium bromide 60 g Table 6 Table 6 Add water 1.0 Liter pH [adjusted with ammonia water] 4.9 (start tank liquid) The start replenisher was diluted 1.1 times and adjusted to pH 5.0 with ammonia water for use. (Bleach regenerant) (g) 1,3-diaminopropane tetrairon (III) acetate ammonium monohydrate 62 g Maleic acid 56 g Succinic acid 60 g Ammonium nitrate 14 g Potassium bromide 80 g Table 6 Table 6 with water 1 0.0 liter pH [adjusted with ammonia water] 3.8 A sample 101 (hereinafter referred to as a processed light-sensitive material) treated with a new solution of CN-16X of Fuji Photo Film Co., Ltd. was prepared.
During the continuous processing, the processed light-sensitive material was processed at a cumulative replenishment amount of 1000 ml (the processed light-sensitive material is referred to as a dye-sensitive material). The transmission density is measured by Fuji Photo Film Co., Ltd. photo densitometer FS
D103 was used for measurement, and the degree of first-come-first-served basis was compared using (concentration of dye-sensitized material)-(concentration of treated photosensitive material) as an index. The results are shown in Table 6.

[0163]

[Table 6]

The effect of inhibiting the dyeing of the compound of the present invention is particularly effectively exhibited when the bleaching solution is regenerated and used.

[0165]

As described above, when the compound of the general formula (S) of the present invention is used, especially when the replenishing amount is small or when the solution is regenerated for repeated use, the effect of suppressing dyeing is exerted. is there.

[Brief description of the drawings]

FIG. 1 shows a flowchart for regenerating an overflow of a bleaching solution of the present invention and using it as a replenisher.

[Explanation of Codes] Refill tank 2. Replenisher 3. Bleach 4. Bleaching tank 5. Stock tank 6. Overflow liquid 7. Air pump 8. Air 9. Piping 10. Air blowing 11. Stirrer 12. Piping to replenishment tank 13. Bleaching liquid regenerant

Claims (5)

[Claims] 1. An iron (III) aminopolycarboxylate after color development of an imagewise exposed silver halide color photographic light-sensitive material.
A method for processing a silver halide photographic light-sensitive material, characterized in that the bleaching solution containing a complex salt contains a compound represented by the following formula (S). Embedded image 2. The processing method according to claim 1, wherein the replenishing amount when replenishing the bleaching solution is 600 ml or less per 1 m ^{2 of the} light-sensitive material. 3. The bleaching solution is replenished with a bleaching replenishing solution, an overflow solution of the bleaching solution generated by the replenishment is stored outside the bleaching tank, and a bleaching solution regenerant is added to the stored overflowing solution to replenish the bleaching solution again. The treatment method according to claim 1, wherein the treatment method is used as a liquid. 4. The method according to claim 1, wherein
A processing method characterized in that the bleaching solution contains a dicarboxylic acid compound. 5. The treatment method according to claim 4, wherein the dicarboxylic acid represented by the following general formula (D) and a salt thereof are included. General formula (D) HOOC-L-COOH (wherein L is carbon It represents a saturated or unsaturated aliphatic group of the numbers 1 to 4.)