JPH09120129A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart superior stability to a processing soln. having fixing ability used for desilvering and to enable processing giving an image free from stains and excellent in aging stability by incorporating a specified compd. into the processing soln. and specifying the pH. SOLUTION: A sensitive material is processed by color development, desilvering and washing and/or processing with a stabilizing soln. A processing soln. having fixing ability used for the desilvering contains a compd. represented by formula I or II and has pH6.1-8.0. In the formula I, Q is a group of nonmetallic atoms required to form a hetero ring, (p) is 0 or 1 and Ma is H or a cation. In the formula II, Qb is a group of nonmetallic atoms required to form a cyclic structure, Xb is 0, S or N-Rb (Rb is H, aliphatic hydrocarbon, aryl or a heterocyclic group) and Mb is H or a cation. The processing soln. having fixing ability means a processing soln. contg. a fixing agent and it is concretely a bleaching soln. or a bleach-fixing soln.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing an image-exposed silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as a light-sensitive material) using a processing composition having a fixing ability. In particular, the present invention relates to a processing composition and a processing method that improve liquid stability and photographic properties.

[0002]

2. Description of the Related Art A light-sensitive material is exposed, developed, and then processed with a bleaching solution or a fixing solution. Thiosulfate has long been known as a fixing agent contained in the fixing solution.
In addition to sulfite as a preservative, JP-A-2-1395
It has been widely used together with aminopolycarboxylic acid and / or organic phosphonic acid and the like as described in JP-A-48-130567 and JP-A-6-130567.

It is more preferable to use a processing solution having a fixing ability in the vicinity of pH 7 since the deterioration of the solution is apt to occur when the pH of the solution is lowered and the color developability of the dye is affected. These treatment liquids react with metal ions such as calcium or magnesium contained in water or eluate from the photosensitive material used at the time of preparation, or iron or the like brought in from the bleaching liquid to generate precipitates or sludges, or It is not always possible to sufficiently satisfy all of the various problems such as coloring of the light-sensitive material and changes in photographic properties after processing, and there is room for further improvement.
Further, with respect to the photosensitive material having the magnetic recording layer described in International Publication WO90 / 04205, it has been confirmed that the magnetic information reading performance is significantly deteriorated.

[0004]

Therefore, the first object of the present invention is to provide a liquid having fixing ability (eg, fixing liquid, bleach-fixing liquid) with excellent liquid stability, and to maintain stain (eg, cyan). It is an object of the present invention to provide a method of processing a silver halide color photographic light-sensitive material excellent in stain) and stability of an image after processing (in particular, magenta). A second object is to provide a processing method which does not reduce the magnetic output even when a magnetic reading operation is performed on a photosensitive material having a magnetic recording layer.

[0005]

The present inventor found the following processing method as a result of examining the above problems. In the processing method of a silver halide color photographic light-sensitive material, which comprises color development processing, desilvering processing, washing with water and / or processing with a stabilizing solution, the processing solution having fixing ability used in the desilvering processing is represented by the following general formula (A). Alternatively, a method of processing a silver halide color photographic light-sensitive material, comprising the compound represented by (B) and having a pH of 6.1 to 8.0. General formula (A)

[0006]

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(In the formula, Q represents a group of non-metal atoms necessary for forming a heterocycle. P represents 0 or 1. Ma represents _a hydrogen atom or a cation.) General formula (B)

[0008]

[Chemical 6]

(In the formula, Q _b represents a group of non-metal atoms necessary for forming a ring structure. X _b represents an oxygen atom, a sulfur atom or N—R _b (R _b represents a hydrogen atom or an aliphatic group. Hydrocarbon radical,
Represents an aryl group or a heterocyclic group. ). M _b represents a hydrogen atom or a cation. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The inclusion of pyridine-2,6-dicarboxylic acid, which is one of the compounds represented by the general formula (A), in a processing solution having fixing ability is disclosed in JP-A-51-793.
No. 0, which describes the contamination of a light-sensitive material due to an iron chloride bleaching solution and a cyan coupler, while Kojic acid, which is one of the compounds represented by the above general formula (B), is described. It is disclosed in Research Disclosure No. 16768 (March, 1978) that the fixing solution is contained in the fixing solution, which describes a hardening solution containing an aluminum complex salt. I can't find any realization about the area.

In the present invention, the light-sensitive material is processed with a color developer, desilvered, and then washed with water and / or a stabilizer. In the desilvering process, basically, a bleaching process is performed with a processing solution having a bleaching ability, and then a fixing process is performed with a processing solution having a fixing ability. As described above, the bleaching process and the fixing process may be performed separately, or may be performed simultaneously with a bleach-fixing solution having both the bleaching ability and the fixing ability (bleach-fixing treatment).
The bleaching treatment, the fixing treatment and the bleach-fixing treatment may each be performed in one tank or two or more tanks.

The processing solution having a fixing ability in the present invention means a processing solution containing a fixing agent among the processing solutions used in the desilvering process, and specifically, a fixing solution and a bleach-fixing solution. Say. The processing solution having a bleaching ability means a processing solution containing a bleaching agent among the processing solutions used in the desilvering process, and specifically, a bleaching solution and a bleach-fixing solution. Specific examples of the desilvering process in the present invention are listed below, but the invention is not limited thereto. 1. Bleach-fix 2. Bleach-fixing 3. Bleach-bleach-fix 4. Bleach-fix-bleach-fix 5. Bleach-bleach-fix-fix 6. Bleach-bleach-fix-bleach-fix 7. Bleach-fix-fix 8. Bleach-fix-bleach-fix 9. Bleach-fix-fix 10. Bleach-fixing-bleaching Incidentally, a water washing step or the like may be provided between these treatments.

First, the compound represented by formula (A) will be described in detail. The carbon number described below is the carbon number excluding the substituent.

The heterocyclic residue formed by Q is N, O,
Or a 3- to 10-membered saturated or unsaturated heterocyclic residue containing at least one S atom, which may be a single ring or may form a condensed ring with another ring. .

The heterocyclic residue is preferably a 5- to 6-membered aromatic heterocyclic residue, more preferably a 5- to 6-membered aromatic heterocyclic residue containing a nitrogen atom,
More preferably, it is a 5- to 6-membered aromatic heterocyclic residue containing 1 to 2 nitrogen atoms.

Specific examples of the heterocyclic residue include, for example, 2
-Pyrrolidinyl, 3-pyrrolidinyl, 2-piperidinyl, 3-piperidyl, 4-piperidyl, 2-piperazinyl, 2-morpholinyl, 3-morpholinyl, 2-thienyl, 2-furyl, 3-furyl, 2-pyrrolyl, 3-
Pyrrolyl, 2-imidazolyl, 4-imidazolyl, 3-
Pyrazolyl, 4-pyrazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 3- (1,2,4-triazolyl), 4- (1,2,3) -Triazolyl), 2- (1,
3,5-triazinyl), 3- (1,2,4-triazinyl), 5- (1,2,4-triazinyl), 6-
(1,2,4-triazinyl), 2-indolyl, 3-
Indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7
-Indazolyl, 2-purinyl, 6-purinyl, 8-purinyl, 2- (1,3,4-thiadiazolyl), 2-
(1,3,4-oxadiazolyl), 2-quinolyl, 3
-Quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-phthalazinyl,
5-phthalazinyl, 6-phthalazinyl, 2-naphthyridinyl, 3-naphthyridinyl, 4-naphthyridinyl, 2-
Quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-
Quinazolinyl, 3-cinnolinyl, 4-cinnolinyl,
5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl, 2-pteridinyl, 4-pteridinyl, 6-pteridinyl, 7-pteridinyl, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4
-Acridinyl, 9-acridinyl, 2- (1,10-
Phenanthrolinyl), 3- (1,10-phenanthrolinyl), 4- (1,10-phenanthrolinyl), 5
-(1,10-phenanthrolinyl), 1-phenazinyl, 2-phenazinyl, 5-tetrazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2- Examples thereof include thiazolidyl, 4-thiazolidyl and 5-thiazolidinyl.

The heterocyclic residue is preferably 2-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 2-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 3- (1,2,4-triazolyl). , 4- (1,
2,3-triazolyl), 2- (1,3,5-triazinyl), 3- (1,2,4-triazinyl), 5-
(1,2,4-triazinyl), 6- (1,2,4-triazinyl), 2-indolyl, 3-indazolyl, 7
-Indazolyl, 2-purinyl, 6-purinyl, 8-purinyl, 2- (1,3,4-thiadiazolyl), 2-
(1,3,4-oxadiazolyl), 2-quinolyl, 8
-Quinolyl, 1-phthalazinyl, 2-quinoxalinyl,
5-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 8-quinazolinyl, 3-cinnolinyl, 8-cinnolinyl, 2- (1,10-phenanthrolinyl), 5
-Tetrazolyl, 2-thiazolyl, 4-thiazolyl, 2
-Oxazolyl and 4-oxazolyl, more preferably 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 2-pyridyl, 2-pyrazinyl, 2-indolyl, 3-indazolyl, 7-indazolyl, 2- (1,
3,4-thiadiazolyl), 2- (1,3,4-oxadiazolyl), 2-quinolyl, 8-quinolyl, 2-thiazolyl, 4-thiazolyl, 2-oxazolyl, 4-oxazolyl, and more preferably 2 -Imidazolyl,
4-imidazolyl, 2-pyridyl, 2-quinolyl, 8-
Quinolyl, particularly preferably 2-imidazolyl,
4-Imidazolyl, 2-pyridyl, 2-quinolyl, with 2-pyridyl being most preferred.

The heterocyclic residue is (CH ₂ ) _p CO ₂ Ma
In addition to the above, it may have a substituent, and examples of the substituent include an alkyl group (preferably having a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, and particularly preferably an alkyl group having a carbon number of 1 to 3). And, for example, methyl, ethyl, etc.), an aralkyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, particularly preferably 7 carbon atoms).
~ 11 aralkyl groups, such as phenylmethyl,
Phenylethyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 2 carbon atoms
6, particularly preferably an alkenyl group having 2 to 4 carbon atoms, and examples thereof include allyl and the like. ), An alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 carbon atoms).
To 6, particularly preferably an alkynyl group having 2 to 4 carbon atoms, and examples thereof include propargyl and the like. ), An aryl group (preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 10 carbon atoms, and examples thereof include phenyl and p-methylphenyl). Amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 carbon atoms)
~ 6 amino groups, such as amino, methylamino,
Examples thereof include dimethylamino and diethylamino. ),
An alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methoxy, ethoxy, etc.) and an aryloxy group (preferably Is carbon number 6-1
2, more preferably an aryloxy group having 6 to 10 carbon atoms, particularly preferably 6 to 8 carbon atoms, and examples thereof include phenyloxy and the like. ), An acyl group (preferably having a carbon number of 1 to 12, more preferably a carbon number of 2 to 10, particularly preferably a carbon number of 2 to 8 and examples thereof include acetyl), and an alkoxycarbonyl group (preferably). Has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms,
Particularly preferred is an alkoxycarbonyl group having 2 to 8 carbon atoms, such as methoxycarbonyl. ), An acyloxy group (preferably having 1 to 12 carbon atoms,
It is more preferably an acyloxy group having 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include acetoxy. ), An acylamino group (preferably having 1 carbon atom)
-10, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, and examples thereof include acetylamino. ), A sulfonylamino group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms,
Particularly preferred is a sulfonylamino group having 1 to 4 carbon atoms, and examples thereof include methanesulfonylamino. ), A sulfamoyl group (preferably having a carbon number of 0 to 1)
It is 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 a C1-10, more preferably a C1-6, particularly preferably a C1-4 carbamoyl group such as carbamoyl or methylcarbamoyl), and an alkylthio group. (Preferably an alkylthio group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, and examples thereof include methylthio and ethylthio.), An arylthio group (preferably having carbon atoms). 6 to 20, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms such as an arylthio group, for example, phenylthio, etc.), a sulfonyl group (preferably 1 to 8 carbon atoms, more preferably carbon atoms). 1 to 6, particularly preferably a sulfonyl group having 1 to 4 carbon atoms, and examples thereof include methanesulfonyl and the like.),
A sulfinyl group (preferably a sulfinyl group having 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 4 carbon atoms, such as methanesulfinyl, etc.), a ureido group, a hydroxy group, Examples include a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a mercapto group, and a heterocyclic group (eg, imidazolyl, pyridyl).

These substituents may be further substituted.
When there are two or more substituents, they may be the same or different. The substituent is preferably an alkyl group, an amino group, an alkoxy group, a carboxyl group, a hydroxy group, a halogen atom, a cyano group, a nitro group, a mercapto group, and more preferably an alkyl group, an amino group, an alkoxy group, or a carboxyl group. , A hydroxy group, and a halogen atom, more preferably an amino group, a carboxyl group, and a hydroxy group, and particularly preferably a carboxyl group.

P represents 0 or 1, and is preferably 0. The cation represented by Ma is an organic or inorganic cation such as an alkali metal ion (eg Li ⁺ ,
Na ⁺ , K ⁺ , Cs ⁺ etc.), alkaline earth metal ions (eg Ca ²⁺ , Mg ²⁺ etc.), ammonium (eg ammonium, tetraethylammonium), pyridinium, phosphonium (eg tetrabutylphosphonium, tetraphenylphosphonium etc.) etc. Is mentioned.

Among the compounds represented by the general formula (A), the compounds represented by the following general formula (Aa) are preferable. General formula (A-a)

[0022]

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(In the formula, p and Ma have the same meanings as those in formula (A), and Q ¹ represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle.)

The nitrogen-containing heterocyclic residue formed by Q ¹ is
A 3- to 10-membered saturated or unsaturated heterocyclic residue containing at least one nitrogen atom, which may be a single ring or may form a condensed ring with another ring. .

The nitrogen-containing heterocyclic residue is preferably 5
It is a 5- to 6-membered nitrogen-containing aromatic heterocyclic residue, more preferably a 5- to 6-membered nitrogen-containing aromatic heterocyclic residue containing 1 to 2 nitrogen atoms.

Specific examples of the nitrogen-containing heterocyclic residue include 2-pyrrolidinyl, 3-pyrrolidinyl, 2-piperidinyl, 3-piperidyl, 4-piperidyl, 2-piperazinyl, 2-morpholinyl, 3-morpholinyl, 2
-Pyrrolyl, 3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 4-pyrazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 3- ( 1,
2,4-triazolyl), 4- (1,2,3-triazolyl), 2- (1,3,5-triazinyl), 3-
(1,2,4-triazinyl), 5- (1,2,4-triazinyl), 6- (1,2,4-triazinyl), 2
-Indolyl, 3-indolyl, 4-indolyl, 5-
Indolyl, 6-indolyl, 7-indolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6
-Indazolyl, 7-indazolyl, 2-purinyl, 6
-Purinyl, 8-purinyl, 2- (1,3,4-thiadiazolyl), 2- (1,3,4-oxadiazolyl),
2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1
-Phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 2-naphthyridinyl, 3-naphthyridinyl, 4-naphthyridinyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl , 7-
Quinazolinyl, 8-quinazolinyl, 3-cinnolinyl,
4-cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl, 2-pteridinyl, 4-pteridinyl, 6-pteridinyl, 7-pteridinyl, 1-acridinyl, 2-acridinyl, 3
-Acridinyl, 4-acridinyl, 9-acridinyl, 2- (1,10-phenanthrolinyl), 3-
(1,10-phenanthrolinyl), 4- (1,10-
Phenanthrolinyl), 5- (1,10-phenanthrolinyl), 1-phenazinyl, 2-phenazinyl, 5-
Tetrazolyl, 2-thiazolyl, 4-thiazolyl, 5-
Thiazolyl, 2-oxazolyl, 4-oxazolyl, 5
-Oxazolyl, 2-thiazolidyl, 4-thiazolidyl and 5-thiazolidinyl are mentioned, and preferably 2-
Pyrrolyl, 2-imidazolyl, 4-imidazolyl, 3-
Pyrazolyl, 2-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 3- (1,2,4-triazolyl), 4-
(1,2,3-triazolyl), 2- (1,3,5-triazinyl), 3- (1,2,4-triazinyl), 5
-(1,2,4-triazinyl), 6- (1,2,4-
Triazinyl), 2-indolyl, 3-indazolyl,
7-indazolyl, 2-purinyl, 6-purinyl, 8-
Purinyl, 2- (1,3,4-thiadiazolyl), 2-
(1,3,4-oxadiazolyl), 2-quinolyl, 8
-Quinolyl, 1-phthalazinyl, 2-quinoxalinyl,
5-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 8-quinazolinyl, 3-cinnolinyl, 8-cinnolinyl, 2- (1,10-phenanthrolinyl), 5
-Tetrazolyl, 2-thiazolyl, 4-thiazolyl, 2
-Oxazolyl and 4-oxazolyl, more preferably 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 2-pyridyl, 2-pyrazinyl, 2-indolyl, 3-indazolyl, 7-indazolyl, 2- (1,
3,4-thiadiazolyl), 2- (1,3,4-oxadiazolyl), 2-quinolyl, 8-quinolyl, 2-thiazolyl, 4-thiazolyl, 2-oxazolyl, 4-oxazolyl, and more preferably 2 -Imidazolyl,
4-imidazolyl, 2-pyridyl, 2-quinolyl, 8-
Quinolyl, particularly preferably 2-imidazolyl,
4-Imidazolyl, 2-pyridyl, 2-quinolyl, with 2-pyridyl being most preferred.

The nitrogen-containing heterocyclic residue is (CH ₂ ) _p CO
₂ Ma may have a substituent in addition to Ma, and as the substituent,
What was mentioned as a substituent of the heterocyclic group formed by Q in General formula (A) can be applied, and a preferable substitution machine is also the same.

P and Ma have the same meanings as those in formula (A), and the preferred ranges are also the same. In addition, the general formula (A-
Among the compounds represented by a), the compounds represented by the following general formula (Ab) are preferable. General formula (Ab)

[0029]

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(Wherein Ma has the same meaning as in formula (A). Q ² is a 5- or 6-membered nitrogen-containing heterocyclic group,
It may be substituted with an alkyl group, amino group, alkoxy group, carboxyl group, hydroxy group, halogen atom, cyano group, nitro group, or mercapto group. )

Among the compounds represented by the general formula (Ab), more preferred are the compounds represented by the following general formula (Ac). General formula (A-c)

[0032]

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(In the formula, Ma has the same meaning as that in formula (A). Q ³ represents an atomic group necessary for forming a pyridine ring or an imidazole ring, and is an alkyl group, an amino group, an alkoxy group or a carboxyl group. Group, hydroxy group, halogen atom, cyano group, nitro group, or mercapto group may be substituted.)

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

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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The above compounds may be used in the form of ammonium salts, alkali metal salts and the like. The compound represented by the above general formula (A) is Organic Syntheses C.
It can be synthesized according to the method described in the Collective Volume 3, page 740 and the like, or a commercially available product can be used. Among the above-exemplified compounds, preferable compounds are (A-6), (A-7), (A-8) and (A-1).
3), (A-14), (A-20), (A-22),
(A-29) and (A-49) are mentioned, and particularly (A-
7) is preferred.

Next, the compound represented by formula (B) will be described in detail. The ring structure formed by Q _b is C,
4 to 1 containing at least one of N, O or S atoms
It is a 0-membered saturated or unsaturated ring, which may be a single ring or may form a condensed ring with another ring. Q
_The ring structure formed by _b is preferably a 5- to 7-membered unsaturated ring, more preferably a 5- or 6-membered unsaturated ring.

Specific examples of the ring structure formed by Q _b include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclopentadiene,
1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-cycloheptadiene, 1,5-cycloheptadiene, 1,3,5-cycloheptatriene, 2H
-Pyran, 4H-pyran, 2H-chromene, 4H-chromene, 2H-pyrrole, 3H-pyrrole, 2-pyrroline, 3-pyrazoline, 3H-indole, 4H-quinolidine, 2H-furo [3,2-b] pyran , 2,3-dihydrofuran, 2,5-dihydrofuran, 3,4-dihydro-2H-pyran, 5,6-dihydro-2H-pyran,
5H-thiophene, 1,2-dihydropyridine, 1,4
-Dihydropyridine, 2H-thiopyran, 4H-thiopyran, 3,4-dihydro-2H-thiopyran, 5,6-
Dihydro-2H-thiopyran can be mentioned, preferably cyclopentene, cyclohexene, 2H-pyran, 4H-.
Pyran, 2H-chromene, 4H-chromene, 1,2-dihydropyridine, 1,4-dihydropyridine, more preferably 2H-pyran, 4H-pyran, 1,2-dihydropyridine, 1,4-dihydropyridine, and Preferred is 2H-pyran, 4H-pyran, and particularly preferred is 4H-pyran. The ring formed by Q _b may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 1 carbon atoms). 4 and examples thereof include methyl and ethyl), an alkenyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, for example vinyl and allyl). ), An alkynyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, for example, propargyl), and an aryl group (preferably carbon). C6-12, more preferably C6-10, especially preferably C6-
8 and examples thereof include phenyl and p-methylphenyl. ), An alkoxy group (preferably having 1 to 8 carbon atoms,
More preferably 1 to 6 carbon atoms, particularly preferably 1 carbon atom
To 4, and examples thereof include methoxy and ethoxy. ), An aryloxy group (preferably having 6 to 1 carbon atoms)
2, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms, such as phenyloxy. ), An acyl group (preferably having 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 8 carbon atoms).
And examples thereof include acetyl. ), An alkoxycarbonyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include methoxycarbonyl), an acyloxy group (preferably having carbon atoms). 1 to 12, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include acetoxy) and an acylamino group (preferably 1 to 10 carbon atoms, more preferably 2 carbon atoms). 6, particularly preferably having 2 to 4 carbon atoms, and examples thereof include acetylamino.), A sulfonylamino group (preferably having 1 to 10 carbon atoms, more preferably 1 carbon atom).
To 6, particularly preferably C1 to C4, and examples thereof include methanesulfonylamino. ), A sulfamoyl group (preferably having a carbon number of 0 to 10, more preferably a carbon number of 0 to 6, particularly preferably a carbon number of 0 to 4, and examples thereof include sulfamoyl and methylsulfamoyl) and a carbamoyl group (preferably Has 1 to 10 carbon atoms,
More preferably 1 to 6 carbon atoms, particularly preferably 1 carbon atom
To 4 and examples thereof include carbamoyl and methylcarbamoyl. ), An alkylthio group (preferably having a carbon number of 1 to 8, more preferably a carbon number of 1 to 6, particularly preferably a carbon number of 1 to 4, and examples thereof include methylthio and ethylthio), a sulfonyl group (preferably having a carbon number). 1 to
8, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, and examples thereof include methanesulfonyl. ), A sulfinyl group (preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 8 carbon atoms).
4 and examples thereof include methanesulfinyl. ), A hydroxy group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group, a carboxy group, a nitro group, and a heterocyclic group (for example, imidazolyl and pyridyl). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. The substituent is preferably a substituted or unsubstituted alkyl group, a hydroxy group or a carboxy group, more preferably a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group or a carboxy group.

X _b is an oxygen atom, a sulfur atom or NR
_b (R _b represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group). The aliphatic hydrocarbon group represented by R _b is a linear, branched or cyclic alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 1 carbon atoms).
0, more preferably 1 to 8), an alkenyl group (preferably having 2 to 12, more preferably 2 to 10, and still more preferably 2 to 7), an alkynyl group (preferably having 2 to 2 carbon atoms).
12, more preferably 2 to 10, even more preferably 2
7), and may have a substituent.

As the substituent, for example, the examples of the substituent which the ring formed by Q _b may have can be applied. R
The substituent of the aliphatic hydrocarbon group represented by _b 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 _b is preferably an alkyl group, more preferably a chain alkyl group, and further preferably methyl, ethyl, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, hydroxy. Methyl, 2-hydroxyethyl, methoxymethyl and sulfomethyl, particularly preferably methyl, ethyl and hydroxymethyl.

The aryl group represented by R _b 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 _b may have a substituent, and as the substituent, the examples given as the substituent which the ring formed by Q _b may have can be applied. The substituent of the aryl group represented by R _b is preferably an alkyl group, an alkoxy group, a carboxy group, a hydroxy group or a sulfo group, and more preferably an alkyl group, an alkoxy group, a carboxy group or a hydroxy group.

Specific examples of the aryl group represented by R _b include phenyl, 4-methylphenyl, 2-carboxyphenyl, 4-carboxyphenyl and 4-methoxyphenyl.

The heterocyclic group represented by R _b 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 heterocyclic group, more preferably a 5- to 6-membered heterocyclic group containing a nitrogen atom, and further preferably 5 to 6 containing a 1- to 2-atom nitrogen atom. Is a heterocyclic group of members. Specific examples of the heterocyclic group include, for example, thienyl, furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, thiazolyl, oxazolyl,
1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-
Indolyl, indolyl, 1H-indazolyl, purinyl, 4H-quinolidinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl,
Isochromanyl, chromanyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, tetrazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, benztriazolyl, and benztriazolyl. Pyrrolidinyl, piperidyl, imidazolyl, pyridyl.

The heterocyclic group represented by R _b may have a substituent, and examples of the substituent include the examples of the substituent which the ring formed by Q _b may have. R _b
The substituent of the hetero group represented by is preferably an alkyl group, an alkoxy group, a carboxy group, a hydroxy group or a sulfo group, and more preferably an alkyl group, an alkoxy group, a carboxy group or a hydroxy group. X _b is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

The cation represented by M _b is an organic or inorganic cation, for example, an alkali metal (Li ⁺ , N
a ⁺ , K ⁺ , Cs ^+, etc., alkaline earth metal (M
g ²⁺ , Ca ^2+, etc.), ammonium (ammonium, trimethylammonium, triethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 1,2-ethanediammonium, etc.), pyridinium, imidazolium, phosphonium (tetrabutyl) Phosphonium and the like). M
_b is preferably a hydrogen atom, an alkali metal or ammonium, more preferably a hydrogen atom.

Among the compounds represented by the general formula (B), the compounds represented by the general formula (Ba) are preferable. General formula (Ba)

[0052]

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(In the formula, X _b and M _b have the same meanings as those in formula (B), respectively, and the preferred ranges are also the same. Q _b1 represents a non-metal atom necessary for forming a ring structure. R _b1 represents a hydrogen atom, a carboxy group, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group.) The ring structure formed by Q _b1 is a C, N, O, or S atom. It is a 4- to 10-membered unsaturated ring containing at least one, and these may be a single ring or may form a condensed ring with another ring. The ring structure formed by Q _b is preferably a 5- to 7-membered unsaturated ring, more preferably a 5- or 6-membered unsaturated ring.

Specific examples of the ring structure formed by Q _b1 include cyclobutene, cyclopentene, cyclohexene,
Cycloheptene, cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-
Cycloheptadiene, 1,5-cycloheptadiene,
1,3,5-cycloheptatriene, 2H-pyran, 4
H-pyran, 2H-chromene, 4H-chromene, 2H-
Pyrrole, 3H-pyrrole, 2-pyrroline, 3-pyrazoline, 3H-indole, 4H-quinolidine, 2H-furo [3,2-b] pyran, 2,3-dihydrofuran,
2,5-dihydrofuran, 3,4-dihydro-2H-pyran, 5,6-dihydro-2H-pyran, 5H-thiophene, 1,2-dihydropyridine, 1,4-dihydropyridine, 2H-thiopyran, 4H-thiopyran , 3, 4
-Dihydro-2H-thiopyran, 5,6-dihydro-2
H-thiopyran is mentioned, preferably cyclopentene, cyclohexene, 2H-pyran, 4H-pyran, 2
H-chromene, 4H-chromene, 1,2-dihydropyridine and 1,4-dihydropyridine, more preferably 2H-pyran, 4H-pyran, 1,2-dihydropyridine and 1,4-dihydropyridine, and further preferably It is 2H-pyran, 4H-pyran, and particularly preferably 4H-pyran. The ring formed by Q _b1 may have a substituent. As the substituent, for example, those mentioned as the substituent of the ring formed by Q _b can be applied.

The aliphatic hydrocarbon group, aryl group and heterocyclic group represented by R _b1 have the same meanings as those of R _b in formula (B), and the preferred ranges are also the same.
R _b1 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, hydroxymethyl and 2-hydroxyethyl, particularly preferably hydrogen atom, methyl, ethyl and hydroxymethyl.

Among the compounds represented by the general formula (Ba), the compounds represented by the general formula (Bb) are preferable. General formula (Bb)

[0057]

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(In the formula, X _b , M _b and R _b1 have the same _{meanings as} those in the general formula (Ba), respectively, and the preferred ranges are also the same. R _b2 and R _b3 are represented by the general formula ( B-
It has the same meaning as R _b1 in a) and the preferred range is also the same. R _b2 and R _b3 may be linked to each other to form a ring. Y _b is an oxygen atom, a sulfur atom, SO, SO ₂ ,
N—R _y (R _y has the same meaning as R _b in formula (B), and the preferred range is also the same), preferably an oxygen atom, a sulfur atom, and N—R _y . More preferably, it is an oxygen atom. )

Of the compounds represented by the general formula (Bb), more preferred are the compounds represented by the general formula (Bc). General formula (B-c)

[0060]

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(In the formula, M _b , R _b1 , R _b2 , and R _b3 have the same _{meanings as} those in the general formula (Bb), respectively, and a preferable range is also the same.) In the general formula (B), Of the compounds shown, those having 4 to 20 total carbon atoms are preferable, and those having 5 to 14 carbon atoms are more preferable.

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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The above compound may be a conjugated isomer thereof if possible. As the compound represented by the general formula (B) of the present invention, commercially available compounds may be used, and for example, “Journal of the American Chemical Society” Vol. 67, page 2276 (1945) (J.
ownnal of the American Ch
electronic Society Vol. 67,227
6 (1945)), 68, 2744 (1946).
, 69, 2908 (1947), and the like.

Of the above-exemplified compounds, preferred are (B-1), (B-2), (B-3), (B-5),
(B-21), (B-39), (B-40), (B-4
1), (B-42) and (B-43) are mentioned, and more preferably (B-2), (B-3) and (B-5).

The compound represented by the general formula (A) or (B) of the present invention is
It is preferable to contain 0.001 to 0.3 mol, and
More preferably 005 to 0.2 mol, 0.01 to 0.1
5 mol is particularly preferred. In the present invention, the effect is exhibited when the pH of the processing solution having fixing ability is 6.1 to 8.0. Outside this range, the stability of the liquid is reduced, and turbidity may occur. The range of pH 6.4 to 7.7 is particularly preferred. Further, in the present invention, the compound represented by the general formula (A) or (B) is preferably added to a processing solution having a bleaching ability, and the addition amount at that time is a processing amount having a fixing ability. The same range as that of the liquid is preferable. In the present invention, the compounds represented by formula (A) or (B) may be used alone or in combination of two or more kinds. The replenishing amount of the processing solution having fixing ability in the present invention is 100 to 1000 ml, preferably 150 to 7 per m ² of the light-sensitive material.
00 ml, especially 200 to 600 ml is preferred.

In the processing solution having fixing ability, a sulfite (eg sodium sulfite, potassium sulfite,
Ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (eg sodium acetaldehyde sodium bisulfite, particularly preferably compounds described in JP-A-3-158848) or JP-A-1.
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. Furthermore, for the purpose of stabilizing the processing liquid,
In addition to the compound of the present invention, various aminopolycarboxylic acids,
A chelating agent such as organic phosphonic acids may be added. Preferred chelating agents to be added include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediamine-N, In addition to N, N ′, N′-tetraacetic acid, diethylenetriaminepentaacetic acid, trans-1,2-cyclohexanediamine-N, N, N ′, N′-tetraacetic acid and 1,2-propylenediaminetetraacetic acid, the present invention Examples thereof include compounds represented by the general formula (I) or the general formula (II).

The compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied to the processing solution having fixing ability. In particular, in order to improve the fixing speed and the homeostasis, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having fixing ability. Preferably. Further, it is also preferable to use the sulfinic acid described in JP-A-1-224762, in addition to p-toluenesulfinate, from the viewpoint of improving the preservability.

The processing solution having a bleaching ability has a pH value of the solution.
It is also preferable to add a buffering agent in order to keep constant.
For example, monobasic acids such as acetic acid and glycolic acid, succinic acid,
Malonic acid, maleic acid, polybasic acids such as citric acid, phosphates, imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
N-allylmorpholine, N-benzoylpiperazine and the like can be mentioned.

Examples of the bleaching agent contained in the processing solution having a bleaching ability include inorganic oxidants such as red blood salt, ferric chloride, dichromate, persulfate, bromate and hydrogen peroxide. Although organic acid iron (III) complex salts are known, in the present invention, organic acid iron (III) complex salts are preferable from the viewpoints of environmental protection, handling safety, corrosiveness of metals and the like.

Examples of the organic acid iron (III) complex salt contained in the bleaching treatment solution used in the present invention include ethylenediamine-N, N, N ', N'-tetraacetic acid, diethylenetriaminepentaacetic acid, trans- Iron (III), an organic acid such as 1,2-cyclohexanediamine-N, N, N ′, N′-tetraacetic acid, N-methyliminodiacetic acid, N- (hydroxyethyl) iminodiacetic acid, glycol etherdiaminetetraacetic acid Complex salt, 1,3-propanediamine-N, N, N ', N'-
JP-A-4-1217 including iron (III) tetraacetate complex salts
No. 39, page 4, lower right column to page 5, upper left column, bleaching agent, carbamoyl bleaching agent described in EP-A-461413, heterocyclic ring described in JP-A-4-174432. Bleaching agents described in European Patent Publication No. 520457, including a bleaching agent having N- (2-carboxyphenyl) iminodiacetic acid iron (III) complex salt, and ethylenediamine-N- (2-carboxyphenyl) -N. ，
Bleaching agents described in European Patent Publication No. 530828 including N ', N'-iron (III) triacetate complex salts, N, N'.
European Patent Publication No. 567 including -bis- (1,2-dicarboxyethyl) ethylenediamine iron (III) complex salts
Bleach, N- (1-carboxy-
Europe, including the N- (1-carboxyethyl) iminodiacetic acid iron (III) complex salts, which are bleaching agents described in EP-A-588289, including iron (III) 2-phenylethyl) aspartate complexes. Patent Publication No. 591934
In addition to the bleaching agent described in Japanese Patent Publication No. 50147
Bleach described in JP-A-9, European Patent Publication No. 461670
The bleaching agent described in Japanese Patent Publication No. 430000, the bleaching agent described in European Patent Publication No. 430000, and the aminopolycarboxylic acid iron (III) complex salt described on page (11) of JP-A-3-144446 are preferably used. Particularly, an iron (III) complex salt of a compound represented by the following general formula (I) or (II) is more preferably used. General formula (I)

[0080]

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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)

[0082]

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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, 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, 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.

Preferred specific 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 represent organic or inorganic cations, such as 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)

[0096]

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(In the formula, L₁And 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 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 can be 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 are a straight-chain or branched alkylene group having 2 to 8 carbon atoms (for example, ethylene, propylene, trimethylene), and 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.

[0102]

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[0103]

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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 atom in the molecule, at least one asymmetric carbon atom is preferably 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. In the treatment method of the present invention, the compound represented by the general formula (I) is preferable from the viewpoint of not reducing the magnetic output. 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.

[0106]

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[0107]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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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) (Jornal of Inorganic and Nuclear
Chemistry Vol. 35,523 (1973)), Swiss Patent 561504, German Patent 3912551A1,
No. 3,939,755 A1, No. 3,939,756 A1, No. 5-265159, No. 6-59422 (Exemplified Compounds I-42, I-43, I-46, I-52, I-5.
The method for synthesizing the L-form of 3 is described in Synthesis Examples 1, 2, 3, 4, and 6. ), No. 6-95319 (exemplified compounds I-8, I)
-11, I-37, I-38, and I-40 L-form synthesis methods are described in Synthesis Examples 2 to 6), and 6-161054.
No. 6-161065, "Helvetica Kimika Akda", Vol. 38, page 2038 (1955) (Helvetica
Chimica Acta, 38, 2038 (1955)) (A method for synthesizing the L-form of Exemplified Compound I-54 is described), "Journal of American Chemical Society", No. 7
Volume 4, page 1942 (1952) (Jornal of American C
hemical Society, 74, 1942 (195
2)) (A method for synthesizing a D, L mixture of Exemplified Compound I-15 is described) and the like.

The compounds represented by the following general formula (Ib) represented by the compounds I-15 and I-54 include, for example, aspartic acids or glutamic acids and acrylic acid derivatives or acrylonitrile derivatives as shown below. Can be synthesized by a method involving addition reaction.
(When an acrylonitrile derivative is used, it is necessary to hydrolyze N- (2-cyanoalkyl) -amino acids generated by the addition reaction.) General formula (Ib)

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(In the formula, R and R ¹ are aliphatic hydrocarbon groups,
It represents an aryl group, a heterocyclic group or a hydrogen atom. n is 1
Or represents 2. M ₁ , M _a1 and M _a2 each represent a hydrogen atom or a cation. )

[0126]

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(In the formula, R and R ¹ are aliphatic hydrocarbon groups,
It represents an aryl group, a heterocyclic group or a hydrogen atom. n is 1
Or represents 2. M ₁ , M _a1 , M _a2 , M _b1 , M _b2 , M _b3 ,
M _c1 and M _c2 have the same meaning and each represent a hydrogen atom or a cation. (However, M _b1 , M _b2 , M _b3 , M _c1 and M
_c2 is excluding primary and secondary ammonium)))

R, R¹Aliphatic hydrocarbon group, aryl
The group and the heterocyclic group are R of the general formula (I). ₁With those listed in
It is synonymous. R, R¹As an aliphatic hydrocarbon group, hydrogen
Atoms are preferred and hydrogen atoms are particularly preferred. M₁, M_a1
And M_a2Is synonymous with that of general formula (Ia),
The same applies to the preferable range.

There are no particular restrictions on the raw materials aspartic acids and glutamic acids, and industrially available ones can be used. These are metal salts (for example, alkali metal salts (Li salt, Na salt, K salt, Rb salt, Cs salt, etc.),
Alkaline earth metal salts (eg Ca salt, Mg salt, Ba salt etc.), transition metal salts (eg Zn salt etc.), tertiary ammonium salts (eg triethylammonium salt etc.), 4
It may be a primary ammonium salt (eg, tetrabutylammonium salt, etc.), a pyridinium salt, or the like, and of course, a free acid. Further, these shapes may be any form such as solid, slurry and aqueous solution. Further, these asymmetric carbon moieties may be either D-form, L-form or a mixture, but L-form is preferred.

The acrylic acid derivative and acrylonitrile derivative which are the raw materials are not particularly limited, and those commercially available can be used. The amount of the acrylic acid derivative or acrylonitrile derivative used in the reaction is 0.5 to 5 mol, preferably 0.7 to 3 mol, relative to 1 mol of the amino acid.
It is particularly preferably in the range of 0.9 to 1.5 mol.

When the acrylic acid derivative or the acrylonitrile derivative is added to the aspartic acid or glutamic acid, the addition reaction is preferably carried out under alkaline conditions. Examples of the base used in the reaction include alkali metal hydroxides (eg lithium hydroxide, sodium hydroxide, potassium hydroxide, vidium hydroxide, etc.), alkaline earth metal hydroxides (eg calcium hydroxide, Barium hydroxide, etc., alkali metal salts (eg sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, sodium pyrophosphate) , Sodium borate, sodium aluminate, sodium silicate, etc., tertiary amines (eg, trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine, etc.), pyridines (eg, pyridine, 4-picoline,
2,6-lutidine), quaternary ammonium hydroxide compounds (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, cetyltrimethylammonium hydroxide) , Cetylpyridinium hydroxide, etc.), metal alkoxides (eg, sodium methoxide, sodium ethoxide, potassium ethoxide, potassium t-butoxide, etc.) and the like. These bases may be used alone or in any ratio. The base used is preferably an alkali metal hydroxide, an alkali metal salt,
Metal alkoxides, more preferably alkali metal hydroxides.

The solvent used in the reaction in the method of the present invention is not limited as long as it does not participate in the reaction, but water or an organic solvent can be used. Examples of the organic solvent include alcohols (eg, methanol, ethanol, 2-
Propanol, n-butanol etc.), ketones (eg acetone, methyl ethyl ketone etc.), esters (eg methyl acetate, ethyl acetate, butyl acetate etc.), aliphatic hydrocarbons (eg n-pentane, n-hexane, cyclohexane etc.) ), Aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.), ethers (eg, diethyl ether, tetrahydrofuran, dioxane, etc.), acetonitrile, etc. The solvent is preferably water, methanol, ethanol, 2-propanol,
Acetonitrile is tetrahydrofuran or dioxane, more preferably water, methanol, ethanol or 2-
Propanol is preferred, and water is particularly preferred. Also,
The above solvents can be mixed and used, and the ratio thereof is arbitrary.

The reaction temperature of the addition reaction varies depending on the starting materials, the reaction concentration, the reaction scale, etc., but when an acrylic acid derivative is used, it is usually 0 to 140 ° C., more preferably 20 to 120 ° C., further preferably 30. ~ 11
It is in the range of 0 ° C. When an acrylonitrile derivative is used, it is usually preferably 0 to 120 ° C, more preferably 10
To 100 ° C, more preferably 20 to 80 ° C.

The reaction time of the addition reaction depends on the reaction raw materials,
Although it varies depending on the reaction temperature, the reaction concentration, the reaction scale, etc., when the acrylic acid derivative is used, it is usually within 10 hours, preferably within 6 hours, more preferably within 4 hours. When an acrylonitrile derivative is used, it is usually within 5 hours, preferably within 3 hours, more preferably within 1 hour. The order of mixing the raw materials is not particularly limited, but as a typical procedure, a solvent is added to the amino acid and a base is further added. A method such as adding an acrylic acid derivative or an acrylonitrile derivative to this solution is used.

The amount of the solvent during the addition reaction varies depending on the starting materials, the reaction temperature, the reaction scale, etc., but is 1 to 15 times the weight of the amino acids, preferably 0.9 to 10 times, and more preferably the amount. The amount is 1 to 5 times, more preferably 1 to 3 times.

The hydrolysis of the nitrile compound, which is an addition reaction product when an acrylonitrile derivative is used, may be carried out under either acidic conditions or basic conditions.
General methods described in 14 (II), p947-950 (Maruzen), Experimental Chemistry Course (4th edition), 22, p12-13 (Maruzen), etc. can be used. At this time, the addition reaction product N
As the-(2-cyanoalkyl) -amino acid, an isolated one may be used, or hydrolysis may be carried out as it is without isolation. Examples of the acid used in the acid hydrolysis include mineral acids (for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc.), organic acids (for example, acetic acid, oxalic acid, glycolic acid, succinic acid, tartaric acid, etc.), Mineral acids, especially hydrochloric acid and sulfuric acid, are preferred. Examples of the base used in the alkali hydrolysis include ammonia in addition to those shown above as the base used in the addition reaction, and preferably an alkali metal hydroxide, an alkali metal salt or a metal alkoxide. ,
More preferably, it is an alkali metal hydroxide.

Commercially available acids and bases may be used for the hydrolysis of nitrile, and the form may be any form such as solid, slurry and aqueous solution. The amount of acid or base used is usually in the range of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, and more preferably 1 to 3 equivalents relative to the cyano machine. As the solvent to be used, those mentioned as the addition reaction conditions can be applied, and the preferable range is also the same.

The reaction temperature for the hydrolysis of nitrile varies depending on the starting materials, the reaction temperature, the reaction concentration, the reaction scale, etc., but is usually in the range of 20 to 120 ° C., preferably 2
The temperature is in the range of 0 to 100 ° C, more preferably 30 to 100 ° C. The reaction time is the reaction raw material, the reaction temperature, the reaction concentration,
Although it depends on the reaction scale and the like, it is usually within 5 hours, preferably within 3 hours, and more preferably within 2 hours.

The conditions for the hydrolysis reaction of the nitrile are:
1 to 3 equivalents of hydrochloric acid, sulfuric acid or hydroxide of an alkali metal with respect to the cyano group is used in an aqueous solvent of 30 to 100.
It is particularly preferable to carry out the treatment within a range of 0 ° C. within 2 hours.

As the conditions for the addition reaction, when an acrylic acid derivative is used, an alkali metal hydroxide is used as a base, water is used as a solvent in an amount 1 to 3 times the amount of amino acids, and a reaction time of 30 to
A method of performing the treatment at 110 ° C. within 4 hours is particularly preferable. When an acrylonitrile derivative is used, an alkali metal hydroxide is used as the base, and 1 to 1 of the amino acids is used as the solvent.
A method of using 3 times the amount of water and in the range of 20 to 80 ° C. within 1 hour is particularly preferable.

In the liquid after completion of the reaction, the compound represented by the general formula (Ib) is present as a salt, but the reaction liquid is cooled or concentrated. It can be isolated as a glassy solid or as crystals. It is also possible to adjust the concentration of the reaction liquid directly or by an operation such as concentration and use it for preparing a photographic processing liquid or the like. In addition, the compound represented by the general formula (Ib) can also be isolated as a free acid by adjusting the pH of the reaction solution in the previous period. Examples of the acid used for pH adjustment include mineral acids (eg, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, etc.), organic acids (eg, acetic acid, oxalic acid, glycolic acid, succinic acid, tartaric acid, etc.). Hydrochloric acid and sulfuric acid are particularly preferable. Examples of the base used for pH adjustment include ammonia in addition to those shown above as the base used for the addition reaction, but alkali metal hydroxides, alkali metal salts, metal alkoxides, and ammonia are preferable, and alkali metal water is used. Oxide and ammonia are particularly preferred. An example of a specific synthesis method will be described below.

Production Method of Compound I-54 (Acrylic Acid Method) 4 to 58.4 g (3.97 mol) of L-aspartic acid
50 g of water was added, and 1025.6 g (12.3) of 48 wt% sodium hydroxide aqueous solution was slowly added while cooling and stirring.
1 mol) was added. Furthermore, 315.0 g (4.37 mol) of acrylic acid was added while cooling and stirring so that the temperature did not exceed 70 ° C. (At this time, the solvent water in the system is L-
It is present 1.71 times as much as disodium aspartate. ) After heating under reflux for 3 hours with stirring, 36% by weight hydrochloric acid was added with stirring to 60 ° C. or lower until pH 2 was reached. The mixture was cooled to room temperature with stirring, and after 2 hours, the produced white crystals were washed with water and acetone, and then dried under reduced pressure to give Compound I-54 (560.0 g, 2.73 mol).
Obtained. Yield 68.8%

Production Method of Compound I-54 (Acrylonitrile Method) L-aspartic acid (520 g) was added to 700 g (5.26 mol).
Add 44 g of water and slowly cool to 44% by weight with stirring.
956.4 g (10.52 mol) of aqueous sodium hydroxide solution was added. (At this time, the solvent water in the system is L-
It is present 1.34 times as much as disodium aspartate. ) After cooling to 30 ° C., 310 g (5.84 mol) of acrylonitrile were added with stirring. The initially heterogeneous reaction liquid gradually became homogeneous as the reaction progressed, and the liquid temperature rose to about 45 ° C. After 30 minutes, the addition reaction was quantitatively completed. (Confirmed by ¹ H NMR.) 366.7% by weight aqueous sodium hydroxide solution (616.7 g) was added to the reaction solution.
(5.55 mol) was added, and the mixture was heated and stirred at 75 to 85 ° C. for 30 minutes, and then it was confirmed by ¹ H NMR that the desired sodium salt was quantitatively produced. 3 in this reaction solution
PH 6 while cooling 6% by weight hydrochloric acid to 60 ° C or lower with stirring
Until it became. Cool to room temperature with stirring,
After 2 hours, the white crystals formed were washed with water and acetone, and then dried under reduced pressure to give compound I-54 (887.0 g).
(4.32 mol) was obtained. Yield 82.2%

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, as the bleaching agent, in addition to the iron (III) complex salt of the compound represented by the general formula (I) or (II), for example, ethylenediamine-N, N, N ', N'-tetraacetic acid, Diethylenetriaminepentaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, 1,3-propanediamine-N, N,
Iron (III) complex salts of known compounds such as N ′, N′-tetraacetic acid and inorganic oxidizing agents such as red blood salts, persulfates, hydrogen peroxide, and bromates can be used in combination, but in the present invention, From the viewpoint of environmental protection and safety in handling, among all the bleaching agents, the compound represented by the general formula (I) or (II) is 70 to 70%.
It is preferably 100 mol%, and further 80 to 1
It is preferably used in an amount of 00 mol%, particularly 100 mol%.

In the present invention, the amount of the compound represented by the general formula (I) or (II) is appropriately in the range of 0.003 to 3.00 mol / liter, and 0.02 to 2.00 mol / liter. The range is preferable, and more preferably 0.05 to 1.
It is in the range of 100 mol / liter, and particularly 0.08-
The range of 0.5 mol / liter is preferable, but when the above-mentioned inorganic oxidizing agent is used in combination, the total concentration of iron (III) complex salt is preferably 0.005-0.030 mol / liter.

In the present invention, it is preferable that the bleaching solution contains a pH buffering agent, and in particular, an organic acid having a low odor such as glycolic acid, succinic acid, maleic acid, malonic acid and glutaric acid. Are preferred, and glycolic acid, malonic acid, and succinic acid are particularly preferred. The concentration of these buffers is preferably in the range of 0 to 3 mol / liter, particularly 0.2 to 1.5 mol / liter.

The pH of the processing solution having the bleaching ability of the present invention
Is preferably 3.0 to 7.0, particularly preferably in the range of pH 3.5 to 5.0 in the bleaching solution, and particularly preferably in the range of pH 4.0 to 6.5 in the bleach-fixing solution. . In a pH range higher than these ranges, there is a concern that the liquid stability will decrease, and in a low pH range, there will be a concern that stain will increase and precipitation will occur. To achieve this pH,
In the present invention, it is preferable to add the above-mentioned organic acid as a buffer agent. The alkaline agent used for pH adjustment is preferably ammonia water, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, or the like. In order to adjust the pH of the bleaching treatment solution of the present invention to the above-mentioned pH, the above-mentioned alkaline agent and known acid (inorganic acid
Organic acids) can be used.

The treatment with the solution having the bleaching ability of the present invention is preferably carried out immediately after color development, but in the case of reversal treatment, it may be carried out through an adjusting bath (which may be a bleaching accelerating bath) or the like. It is common to do so. These adjusting baths may contain an image stabilizer described later. In the present invention, in addition to the bleaching agent, the liquid having bleaching ability is disclosed in
Rehalogenating agents, pH buffering agents and known additives, aminopolycarboxylic acids, organic phosphonic acids, etc. described on page (12) of 144444 can be used. As the rehalogenating agents, sodium bromide and bromide can be used. It is preferable to use potassium, ammonium bromide, potassium chloride or the like, and the content thereof is preferably 0.1 to 1.5 mol, and more preferably 0.1 to 1.0 mol, per 1 liter of the bleaching solution. It is preferably 0.1 to 0.8 or less.

In the present invention, it is preferable to use a nitric compound such as ammonium nitrate or sodium nitrate in the liquid having a bleaching ability. In the present invention, the concentration of the nitric acid compound in 1 liter of the bleaching solution is preferably 0 to 0.3 mol, more preferably 0 to 0.2 mol. Usually, a nitric acid compound such as ammonium nitrate or sodium nitrate is added to prevent corrosion of stainless steel, but in the present invention, even if the amount of nitric acid compound is small, corrosion is unlikely to occur and desilvering is good.

The replenishing amount of the bleaching solution is 1 m ² of the light-sensitive material.
30 to 600 ml is preferable, and more preferably 5
It is 0 to 400 ml. In the case of treating with a bleaching solution, the treatment time is preferably 7 minutes or less, particularly preferably 10 seconds to 5 seconds.
Minutes, most preferably 15 seconds to 3 minutes.

In the present invention, the replenisher for the processing solution having bleaching ability and the processing solution having fixing ability may be liquid or solid (powder, granule, tablet). It is preferable to use a polyethylene glycol-based surfactant, which also serves as a binder. To solidify the photographic processing agent, JP-A-4-29136 discloses.
No. 4-85535, No. 4-85536, No. 4-88533, No. 4-85534, and No. 4
As described in JP-A-172341, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is sprayed on the surface of the temporarily molded photographic processing agent. As a result, any means such as forming a coating layer can be adopted. A method for producing a tablet processing agent is described in, for example, JP-A-51-61837 and JP-A-5-61837.
No. 4-155038, No. 52-88025,
It can be produced by the general method described in British Patent No. 1213808, and the granule treating agent is described in, for example, Japanese Patent Laid-Open No.
It can be manufactured by a general method described in JP-A-109042, JP-A-2-109043, JP-A-3-39735, JP-A-3-39739 and the like. Furthermore, the powder processing agent can be produced by a general method as described in, for example, JP-A-54-133332, British Patents 725892, 729862 and 3733861.

When the replenisher for the processing solution having a bleaching ability and the processing solution having a fixing ability is composed of a liquid, it may be one solution or a plurality of solutions containing different components, but the storage space of the replenishing agent and the preparation of the solution From the viewpoint of operability at the time, 1 solution or 2
A liquid is preferable, and one liquid is particularly preferable. At this time, the specific gravity of the replenisher is preferably in the range of 1.0 to 5 times, more preferably 1.5 to 3 times that of the replenisher.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 minute to 1
It is 2 minutes, more preferably 1 to 8 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. The processing solution having the bleaching ability of the present invention is particularly preferably subjected to aeration during processing, since photographic performance is extremely stably maintained. Means known in the art can be used for aeration, and blowing of air into the processing solution having a bleaching ability or absorption of air using an ejector can be performed. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak Company's Z-121, Eusing Process C-41 3rd Edition (1982), BL-1 to BL-
The items described on page 2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is intensified, and the practice thereof is JP-A-3-33847.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of the publication can be used as they are.

Further, in the present invention, various bleaching accelerators can be added to the prebath of the processing solution having a bleaching ability. Examples of such bleaching accelerators include, for example, US Pat. No. 3,893,858 and German Patents 1, 2
90,821, British Patent No. 1,138,842.
Specification, JP-A-53-95630, research
A compound having a mercapto group or a disulfide group described in Disclosure No. 17129 (July 1978 issue), a thiazolidine derivative described in JP-A No. 50-140129, described in US Pat. No. 3,706,561. Thiourea derivative of JP-A-58-16235
Iodide described in German Patent 2,748,43
The polyethylene oxides described in No. 0 specification and the polyamine compounds described in JP-B-45-8836 can be used. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material.

It is preferable to use ammonium as a cation in the solution having a bleaching ability and the solution having a fixing ability from the viewpoint of improving desilvering ability, but for the purpose of reducing environmental pollution, ammonium is reduced or reduced to zero. Is preferred. In the bleaching, bleach-fixing and fixing steps, JP-A-1-
It is particularly preferable to carry out jet agitation described in 309059.

In the bleach-fixing process and fixing process, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher. The bleach-fixing step and the fixing step can be composed of multiple processing tanks,
Preferably, each tank is cascaded to provide a multi-stage countercurrent system. In view of the balance with the size of the developing machine, the two-tank cascade configuration is generally efficient, and the processing time ratio between the front tank and the rear tank is 0.5: 1.
It is preferable to be in the range of from 1: 0.5 to 1: 0.5, and in particular, to 0.
The range of 8: 1 to 1: 0.8 is preferable.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. A specific method for strengthening the stirring is described in JP-A-62-183460 and JP-A-3-33847, page 8, on the emulsion side of the light-sensitive material described in line 6 of the upper right column to line 2 of the lower left column. A method of colliding a jet stream of a processing liquid,
A method of increasing the stirring effect using the rotating means of No. 62-183461, and further moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further stirring There are a method of improving the effect and a method of increasing the circulation flow rate of the whole treatment liquid. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

Automatic developing machines used for the light-sensitive material of the present invention are disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have the photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution. The bleaching solution of the present invention can be reused after recovering the overflow solution after use in the treatment and adding the components to correct the composition. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. For details of reproduction, see Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 processing (1990), published by Fuji Photo Film Co., Ltd.
(August 2013 revision) The matters described on pages 39-40 can be applied.

Regarding the regeneration of the liquid having a bleaching ability, in addition to the above-mentioned aeration, the method described in "Basics of photographic engineering-silver salt photograph edition-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., Ltd., 1979), etc. Can be used. Specifically, in addition to electrolytic regeneration,
Examples thereof include a method of regenerating a bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromic acid, ozone and the like. In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm to regenerate. And / or regenerating the fixing solution at the same time. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. In addition, it is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. The bleaching solution of the present invention has an oxygen permeation rate of 1 cc / m ² .d during storage.
It is preferable to keep it in a closed container of ay.atm or more.

The bleaching solution of the present invention preferably contains at least one of 1,2-benzisothiazolin-3-one and its derivatives. 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 bleaching solution basically contains the concentration of each component 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)

Next, the color developing solution will be described. The color developing solution is described in JP-A-4-121739, page 9, upper right column 1,
The compounds described in lines to page 11, lower left column, line 4 can be used. As a color developing agent for particularly rapid processing, 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline, 2-methyl-4-
[N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl-4- [N-ethyl-N-
(4-Hydroxybutyl) amino] aniline is preferred. The color developing solution contains 0.01 to 0.0 of a color developing agent.
It is preferable to contain 8 mol / liter, particularly 0.015 to 0.06 mol / liter, and further 0.0
It is preferably contained in an amount of 2 to 0.05 mol / liter. The replenisher for the color developing solution preferably contains 1.1 to 3 times this value.

The color developing solution contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It is common to include a development inhibitor or an antifoggant such as a bromide salt, an iodide salt, benzimidazoles, benzothiazoles or mercapto compounds. Further, if necessary, in addition to hydroxylamine and diethylhydroxylamine, N, N-bis (2-sulfonateethyl) hydroxylamine and other JP-A-3-14
Hydroxylamines represented by the general formula (I) of No. 4446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl
-3-Auxiliary developing agent such as pyrazolidone, viscosity imparting agent,
Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylimino Diacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxy) Representative examples thereof include phenylacetic acid) and salts thereof.

The processing temperature of the color developing solution in the present invention is 20 to 55 ° C, preferably 30 to 55 ° C. The processing time is 20 seconds to 10 minutes, preferably 30 seconds to 8 minutes for the photographic light-sensitive material. It is more preferably 1 minute to 6 minutes, and particularly preferably 1 minute 10 seconds to 3 minutes 30 seconds. For printing materials, it is 10 seconds to 1 minute 20 seconds, preferably 10 seconds to 60 seconds, and more preferably 10 seconds to 40 seconds.

When the reversal process is carried out, the black and white development is usually carried out before the color development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, or N. Known black-and-white developing agents such as aminophenols such as -methyl-p-aminophenol can be used alone or in combination. Further, the black-and-white developing solution is also used in the processing of the black-and-white light-sensitive material. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between processing solution and air (cm ² )] ÷ [volume of processing solution (cm ³ )] The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. It is. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. Further, a method of contacting a liquid covering the processing liquid surface, such as liquid paraffin, or a low-oxidizing and / or non-oxidizing gas with the processing liquid surface may also be used. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

When the replenishment amount is reduced or when the bromide ion concentration is set to a high value, 1-phenyl-3-pyrazolidone or 1-phenyl-
Pyrazolidones represented by 2-methyl-2-hydroxymethyl-3-pyrazolidone and 3,6-dithia-1,8
A thioether compound represented by octanediol,
It is also preferable to use sodium thiosulfate or potassium thiosulfate as a development accelerator. These development accelerators can also be preferably used in the color developing solution.

The shape and structure of the container for accommodating the color developing agent constituting the color developing solution can be arbitrarily designed according to the purpose. For example, JP-A-58-97046 and 63-50.
No. 839, JP-A No. 1-235950, Shokai 63-4.
Those having a flexible structure such as a bellows described in JP-A-5555, JP-A-58-52065 and JP-A-64-246061.
No. 62-2134646, which has a flexible partition wall to enable storage of waste liquid, JP-A-2-2
The structure described in No. 64950 in which a plurality of containers having variable inner volumes are connected is preferable. In order to supply the color developing agent from these containers to the processing solution tank of the developing machine, it may be placed in the replenishing solution tank once and then mixed with water automatically or manually to dilute it. The water and water may be separately sent directly to the treatment liquid tank. At the time of such work, it is preferable that the lid of the container has a structure that can be opened with one touch, and such an example is described in Japanese Utility Model Laid-Open No. 61-128646, JP-A-3-265849, and JP-A-4-240850. ing.

The color developing agent should be filled in a container made of a material having a carbon dioxide permeation rate of 25 ml / m ² 24 hrs · atm or less so that the porosity is 0.15 to 0.05. Is preferred. As a preferable material having such a carbon dioxide permeation rate, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, a laminated material of polyethylene or polypropylene and nylon, a laminated material of polyethylene or polypropylene and aluminum,
It is preferable to use glass or the like having a thickness of 300 to 2000 μm. Particularly, polyethylene terephthalate or a laminated material of polyethylene and nylon is preferably used.
Those having a thickness of 0 to 1000 μm are most preferable because they have a good balance of carbon dioxide permeability, mechanical strength and weight. The material of the container used in the present invention has an oxygen permeation rate of 20 ml / m ² · 24 hrs · atm.
The following is preferred.

Here, the porosity is a value obtained by subtracting the filling amount (ml) of the color developing agent from the volume (ml) of the container containing the color developing agent and dividing the value by the volume (ml) of the container. is there.
The liquid color developer of the present invention has a porosity of 0.
It is preferable that the filling amount be 15 to 0.05.

The color developing agent can be used as it is as a color developing solution or a replenishing solution, but it is preferably mixed and diluted with water and used as a color developing solution or a replenishing solution. When used as a color developing solution, it is preferable to add a pH adjuster and a starter containing a bromide in addition to water. When using it as a replenisher, mix and dilute it with water beforehand and stock it in a replenisher tank.
The treatment liquid tank may be used to quantitatively replenish it from here, or the treatment liquid tank may be directly quantitatively replenished separately from water and mixed and diluted in the treatment liquid tank.
Further, as an intermediate method, a method may be used in which the solution is continuously mixed with water and diluted while being fed to the treatment liquid tank. In this case, a known method such as providing a mixing tank in the middle can be applied.

With regard to the washing and stabilizing steps, the contents described in JP-A-4125558, page 12, lower right column, line 6 to page 13, lower right column, line 16 can be preferably applied. In particular, azolylmethylamines described in European Patent Publication Nos. 504609 and 519190 or JP-A-4-3629 instead of formaldehyde in the stabilizing solution.
Use of N-methylolazoles described in No. 43 or dimerization of the magenta coupler to form a surfactant-free liquid containing no image stabilizer such as formaldehyde is preferred from the viewpoint of preserving the working environment. preferable. In the present invention, it is particularly preferable not to include an image stabilizer in the bath of the final step in order to improve the reading performance of magnetic recording information.

Calcium ion, magnesium on, sodium ion, or the like as an elution component from the preparation water used for preparing the replenisher or from the light-sensitive material, was added to the processing solution.
Although there are various ionic components such as potassium ions, in the present invention, the sodium ion concentration in the final bath of the washing or stabilizing step is particularly preferably in the range of 0 to 50 mg / liter, particularly 0 to 20 mg / liter. Is preferred.

The amount of washing and replenishment of the stabilizing solution depends on the amount of the light-sensitive material 1.
80-1000 ml per m ² is preferred, especially 100-
500 ml, more preferably 150 to 300 ml, is a preferable range from the viewpoint of ensuring the washing or stabilizing function and reducing the waste liquid for environmental protection. In the treatment performed with such a supplement amount, thiabendazole, 1,2-benzisothiazolin-3one,
Known antifungal agents such as 5-chloro-2-methylisothiazolin-3-one and antibiotics such as gentamicin,
It is preferable to use water deionized with an ion exchange resin or the like. It is more effective to use deionized water in combination with antibacterial agents and antibiotics. Further, the liquids washed or washed in the stabilizing liquid tank are described in JP-A-3-46652 and JP-A-3-5652.
No. 3246, No. 3-121448, No. 3-12603
It is also preferable to perform the reverse osmosis membrane treatment described in No. 0 to reduce the replenishment amount, and in this case, the reverse osmosis membrane is preferably a low pressure reverse osmosis membrane.

In the processing of the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid as disclosed in JIII Journal of Technical Disclosure No. 94-4992. Especially the second
A method of making a correction using the temperature and humidity information of the developing machine installation environment based on (Equation-1) on page is preferable. The water used for evaporation correction is preferably collected from a replenishing tank for washing, and in that case, deionized water is preferably used as the washing replenishing water.

With respect to the automatic processor used in the present invention, the film processor described in lines 22 to 28 in the right column of page 3 of the above-mentioned Kokai Giho is preferable. Specific examples of preferred processing agents, automatic processors, and evaporation correction methods for carrying out the present invention are described on page 5, right column, line 11 to page 7, right column, last line. .

Next, the 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 preferable to be 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.

Examples of the binder used for the magnetic particles include thermoplastic resins, thermosetting resins, radiation-curable resins, reactive resins, acids, alkalis or biodegradable polymers, and natural products described in JP-A-4-219569. 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 for 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 lubricity improvement, curl control, antistatic, adhesion prevention and head polishing, or may be provided with another functional layer 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 to be processed in the present invention is preferably a light-sensitive material for photographing, and its support is preferably polyester. For details thereof, refer to Kokai Giho, Koho Giho No. 94-6023. 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, and 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 transporting the support 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 raising the ends only slightly to prevent cut-out of the core. 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.
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.

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 coloring dye has an appropriate diffusibility include US Pat. No. 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 (patrone) for storing a light-sensitive material 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 that rotates the spool 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 part 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.

[0199]

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) Each layer having the following composition was multilayer coated on a cellulose triacetate film support provided with an undercoat layer to prepare a color negative film.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units 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

Ninth 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-sensitive 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 × 10 ^-2 HBS-4 5.0 × 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, each layer may be provided with W-1 to W-3, B-4 to B-. 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.

[0216]

[Table 1]

In Table 1, (1) Emulsions J to L were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. ing. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high voltage 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
ml and 5 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) and 0.5 g were put in a 700 ml pot mill and the dye ExF- was added. 5.0 g of 2 and 500 ml of zirconium oxide beads (diameter: 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used.
After dispersion, take out the contents and use 8 g of 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 fine dye particles was 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 was dispersed by the microprecipitation dispersion method described in Example 1 of EP549,489A. The average particle size was 0.06 μm.

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The above sample 101 was cut into a 135 type film size (corresponding international standard ISO 1007),
After the wedge exposure, a light-sensitive material of 6 m ² per day was processed for 2 months under the following conditions. An automatic processor FNCP-300II manufactured by Fuji Photo Film Co., Ltd. was used as a processor, and the temperature of the processing liquid was continuously set to the processing temperature during the test period.

Treatment Process Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38.0 ° C 550ml / m ² 82 liters Bleach 3 minutes 00 seconds 38.0 ° C 150ml / m ² 118 liters Washing water (1) 15 seconds 24.0 ℃ From (2) to (1) 20 liters countercurrent piping system Washing (2) 15 seconds 24.0 ℃ 200ml / m ² 20 liters fixed 3 minutes 00 seconds 38.0 ℃ 400ml / m ² 77 liters Washing (3) 30 Second 24.0 ℃ From (4) to (3) 40 liters countercurrent piping system Washing (4) 30 seconds 24.0 ℃ 1000ml / m ² 40 liters Stability 30 seconds 38.0 ℃ 300ml / m ² 40 liters Drying 4 minutes 20 seconds 55 ° C

The composition of the treatment liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.2 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.2 Sodium sulfite 4.0 4.0 4.8 Potassium carbonate 30.0 39.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 3.3 Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 2 0.02.8 4 (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 6.0 Water was added 1000 ml 1000 ml pH 10.05 10.15

(Bleaching solution) Tank solution Replenishing solution 1,3-diaminopropane-N, N, N ', N'-tetraacetic acid 0.17 mol 0.25 mol Iron nitrate (III) nonahydrate 65. 0 g 100.0 g Ammonium bromide 80.0 g 120.0 g Acetic acid (90%) 50.0 g 75.0 g Water was added 1000 ml 1000 ml pH (adjusted with ammonia water and nitric acid) 4.3 3.8

(Fixer) Tank solution (g) Replenisher (g) Ammonium thiosulfate 0.7 mol 1.0 mol Ammonium sulfite 0.2 mol 0.3 mol Inventive compound (described in Table 2) 0.02 mol 0.03 mol acetic acid (90%) 3.0 4.0 Add water 1000 ml 1000 ml pH (shown in Table 2) (adjust with ammonia water and acetic acid)

(Stabilizing Solution) Tank Solution / Replenishing Solution Common (g) p-Nonylphenoxypolyglycidol (Glycidol Average Polymerization Degree 10) 0.2 Ethylenediamine-N, N, N ′, N′-tetraacetic Acid 0.05 1 , 2,4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 glycolic acid 0.02 gentamicin 0.01 hydroxyethyl cellulose 0.1 (Daicel Chemistry HEC SP -2000) 1,2-Benzisothiazolin-3-one 0.05 Water was added to 1 liter pH (adjusted with aqueous ammonia and nitric acid) 8.5

The processed photosensitive material was evaluated for stain and image storability by the following methods. Stain: The sample after the treatment was subjected to concentration measurement, and Dmin measured with red light (R light) was read from the characteristic curve. Image aging: Measure the density of the processed sample,
The Dmax measured with green light (G light) was read from the characteristic curve. Then, the light-sensitive material after the measurement was stored under the following conditions, and the Dmax after the lapse of time was similarly measured. Then, the change with time of Dmax of the magenta dye was determined as follows. Storage condition: 70 ° C, relative humidity 70%, 4 weeks Dmax change with time (ΔDmax (G)) = (Dmax after storage)-
(Dmax before storage) Further, with respect to the processing solution having the same composition as the tank solution of the above fixing solution, 2000 ppm of iron (III) ion, 400 ppm of calcium ion, and 150 ppm of magnesium ion.
Each added solution was separately prepared and allowed to stand at 40 ° C. for 4 weeks, and the occurrence of precipitation was observed. Table 2 shows the results.

[0243]

[Table 2]

From Table 2, it was found that in the present invention, the stability of the fixing solution and the temporal stability of the cyan stain and magenta dyes are excellent.

Example 2 The same procedure as in Example 1 was carried out except that the bleaching solution / fixing solution / stabilizing solution was changed to the following in Example 1 of the present application, and the change with time of cyan stain and magenta dye was determined. . Table 3 shows the results.

(Bleaching solution) Tank solution Replenishing solution Chelating agent for bleaching solution (shown in Table 3) 0.17 mol 0.25 mol Iron (III) nitrate 9-hydrate 65.0 g 100.0 g Sodium bromide 80 0.0g 120.0g Glycolic acid 40.0g 65.0g Succinic acid 20.0g 30.0g Add water 1000ml 1000ml pH (adjusted with NaOH and nitric acid: listed in Table 3)

(Fixer) Tank solution (g) Replenisher (g) Sodium thiosulfate 0.7 mol 1.0 mol Sodium sulfite 0.2 mol 0.3 mol Compounds of the present invention (described in Table 3) 0.05 Mol 0.08 mol acetic acid (90%) 3.0 4.0 add water 1000 ml 1000 ml pH (adjusted with NaOH and acetic acid) 6.4 6.6

(Stabilizing Solution) Tank Solution / Replenishing Solution Common (g) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 1,2,4-triazole 1.3 1-hydroxymethyl- 1,2-4-Triazole 0.75 Gentamicin 0.01 1,2-Benzisothiazolin-3-one 0.05 Water was added to 1 liter pH (adjusted with ammonia water and nitric acid) 8.5

[0249]

[Table 3]

From Table 3, when the compound represented by the general formula (I) or (II) is used as the bleaching agent in the present invention, and particularly in the bleaching solution, the general formula (A) or (B) is used. It is understood that the effect appears when the compound represented by () is used.

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 surfaces thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione were formed on each surface. -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 size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size 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 produced 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.

The sample 102 was subjected to wedge exposure, and then mounted in a camera having a head gap of 5 μm, a number of turns of 50, and a magnetic recording device made of a permalloy material.
Digital saturation recording was performed at a recording wavelength of 50 μm. The sample 102 in which the magnetic information was written in this way was prepared as in Example 1.
4m ² per day by mixing with the sample 101 described in 1.
The light-sensitive material was processed under the following conditions for 3 months. At this time, the ratio of the throughputs of the samples 101 and 102 is 5:
And 2. As the processor, an automatic processor FP-560B manufactured by Fuji Photo Film Co., Ltd. was used. The overflow solution of the bleaching bath was modified so that it was entirely discharged into the waste liquid tank without flowing into the post bath. Further, this FP-560B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992. The treatment process and the treatment liquid composition are shown below.

(Treatment process) Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 05 seconds 37.8 ° C 400 ml / m ² 17 liters Bleach 50 seconds 38.0 ° C 100 ml / m ² 5 liters Fixing (1) 50 seconds 38.0 ° C-5 liters Fixing (2) 50 seconds 38.0 ° C 300 ml / m ² 5 liters Water washing 30 seconds 38.0 ° C 500 ml / m ² 3.5 liters Stable (1) 20 seconds 38.0 ° C-3 liters stable (2) 20 seconds 38.0 ℃ 500 ml / m ² 3 liter Dry 1 minute 30 seconds 60 ℃ Stabilizer and fixer are countercurrent from (2) to (1).
All the overflow of the washing water was introduced into the fixing bath (2). Incidentally, amount carried to the bleaching step of the color developing solution, the amount of carryover of the fixing step of the bleaching solution, bring volume to the washing step of the fixer photosensitive material 35mm wide 1 m ² per each 65 ml 50 ml 50 ml, Fifty
It was milliliters. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 with the color developer.
cm ^2, the bleaching solution in 120cm ^2, other processing solutions about 100
It was cm ² .

The composition of the treatment liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate dinatrium salt 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 4.5 6.0 Potassium bromide 1.3-Potassium iodide 1.3 mg-4-Hydroxy-6-methyl-1 , 3,3a, 7-Tetrazaindene 0.05-2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulphate 4.5 6.5 Add water 1. 0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.21

(Bleaching solution) Tank solution (g) Replenishing solution (g) Chelating agent for bleaching solution (described in Table 4) 0.30 mol 0.40 mol Iron nitrate (III) 9-hydrate 0.30 mol 0.40 mol Sodium bromide 70.0 105.0 1,2-benzisothiazolin-3-one-Na 0.03 0.05 Inventive exemplified compound (A-7) 0.08 mol 0.13 mol succinic acid 20.0 30.0 Glycolic acid 60.0 90.0 Add water 1000 ml 1000 ml pH (adjusted with NaOH and nitric acid) 4.6 4.0

(Fixer) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution (750 g / liter) 240.0 ml 720.0 ml Ammonium methanethiosulfonate 5.0 15.0 Ammonium methanesulfinate 10.0 30 0.0 compound of the present invention (described in Table 4) 0.07 mol 0.2 mol imidazole 7.0 20.0 Water was added to 1000 ml 1000 ml pH (adjusted with aqueous ammonia and acetic acid) 7.4 7.5

(Washing water) Common to tank liquid and replenisher Tap water is used as H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA). -4
00) to reduce the concentration of calcium and magnesium ions to 3 mg / l or less, followed by 20 mg / l of sodium diisocyanurate dichloride.
Liters and 150 mg / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Tank solution and replenisher common 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.4 g 1,2,4-triazole 0.5 g polyoxyethylene-p -Monononyl phenyl ether 0.2 g (average degree of polymerization 10) 1,2-benzisothiazolin-3-one. Sodium 0.10 g Water was added to 1 liter pH (adjusted with ammonia water and nitric acid) 8.5 The sodium ion concentration in the stabilized solution (2) after the treatment was measured and found to be 18 mg / liter.

After the processing was completed under each condition, the output signal level of the isolated frequency was measured using a magnetic reproducing head made of Sendust material with a head gap of 2.5 μm, a turn number of 2000, and a sample 102 of 150 m back from the processing completion. did. Table 4 shows the results. In the magnetic output, the average output from the start of measurement to 1 m was set to 100, and the average output for the final 1 m was expressed as%.

[0265]

[Table 4]

As shown in Table 4, in the present invention, the effectiveness was obtained for the magnetic output.

[0267]

According to the present invention, it is possible to provide a processing method using a processing solution having a fixing ability excellent in liquid stability, and to obtain a stain such as cyan stain using the processing solution having a fixing ability according to the present invention. It can be remarkably suppressed, and is further improved by using the solution having the bleaching ability according to the present invention. Furthermore, the magnetic output for a photosensitive material having a magnetic recording layer can be improved by the method of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G11B 5/627 G11B 5/627

Claims (4)

[Claims] 1. Color development processing, desilvering processing, water washing and / or
Alternatively, in the processing method of a silver halide color photographic light-sensitive material comprising processing with a stabilizing solution, the processing solution having fixing ability used in the desilvering processing is represented by the following general formula (A) or (B).
A method for processing a silver halide color photographic light-sensitive material, comprising a compound represented by the formula (1) and having a pH of 6.1 to 8.0. General formula (A) (In the formula, Q represents a non-metal atom group necessary for forming a heterocycle. P represents 0 or 1. M _a represents _a hydrogen atom or a cation.) General formula (B) (In the formula, Q _b represents a group of non-metal atoms necessary to form a ring structure. X _b represents an oxygen atom, a sulfur atom or N—R _b.
(R _b represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group). M _b represents a hydrogen atom or a cation. ) 2. A processing solution having a bleaching ability used in the desilvering process contains at least one iron (III) complex salt of a compound represented by the following general formula (I) or (II), and has a pH value of Is 3 to 7, and the method of processing a silver halide color photographic light-sensitive material according to claim 1. General formula (I) (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 represent an alkylene group. M ₁ and M ₂ each represent a hydrogen atom or a cation. General formula (II): (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 each 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. 3. The halogenation according to claim 2, wherein the processing solution having a bleaching ability contains the compound represented by the general formula (A) or (B) according to claim 1. Processing method of silver color photographic light-sensitive material. 4. The silver halide color photographic light-sensitive material has a magnetic recording layer containing magnetic particles on the side opposite to the light-sensitive layer with respect to the support. 5. A method for processing a silver halide color photographic light-sensitive material described in.