JP2000356841A - Concentrated fixing solution for silver halide photographic sensitive material, solid fixing agent and processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fixing concentrated solution for a silver halide photographic sensitive material excellent in preservability at high temperature, free from the deterioration of residual color property due to reduction in replenishment and not substantially containing a boron compound which adversely affects the environment by incorporating specified compounds. SOLUTION: The fixing concentrated solution contains a thiosulfate, a water-soluble aluminum salt, one or more of compounds of formulae I, II, etc., and a compound of formula III or the like. In formulae I and II, R11 is an aliphatic hydrocarbon group, an aryl or the like, Q11 is H, -L13-COOM14, L11-L15 are each alkylene, W11 is a carbon- containing divalent combining group, * indicates the fact that the absolute configuration is S body, M11-M14 are each H or a cation, R21-R25 are each H, an aliphatic group or the like, L21 and L22 are each a divalent aliphatic group, a divalent aromatic group or a divalent combining group comprising a combination of such groups and M21 and M22 are each H or a cation. In formula III, R41 and R42 are each an alkyl, amino or the like and M41 and M42 are each H or an alkali metal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixing concentrate for a silver halide photographic light-sensitive material, a solid fixing agent, and a method for processing a silver halide photographic light-sensitive material. No reduction in residual color even after reducing the concentration of a fixing compound for a silver halide photographic light-sensitive material substantially free of a boron compound having a large environmental load, a solid fixing agent, and
The present invention relates to a method for processing a silver halide photographic material using the concentrated solution or the fixing solution prepared with the fixing agent.

[0002]

2. Description of the Related Art In general, a hardening solution containing a water-soluble aluminum salt is used as a fixing solution for a silver halide black-and-white photographic light-sensitive material. A hardening fixer containing a water-soluble aluminum salt can prevent the formation of a sparingly soluble aluminum salt by lowering the pH.However, if the pH is lowered too much, it contains a thiosulfate as a fixing agent. Sulfidation becomes a problem when the storage conditions are high, for example, during storage. Also, when a solid fixing agent such as tablets, granules, and powders is used, if the pH is too low, sulfuration may occur due to the coexisting acid component during high-temperature storage. On the other hand, raising the pH improves fixing properties and is effective for elution and removal of dyes in the film during processing.
Poorly soluble aluminum salt is easily generated. It is generally known that a boron compound is added to a fixing agent as an effective technique for preventing the formation of a hardly soluble aluminum salt. The boron compound is brought into the washing step from the fixing step by the treatment of the film, and is discharged therefrom. In recent years, it has been desired to reduce the concentration of the boron compound in the wastewater from the viewpoint of global environmental protection.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a boron compound which is excellent in storage stability at high temperatures, does not deteriorate in residual color even if the replenishment amount is reduced, and has a large environmental load. A fixing method for a silver halide photographic light-sensitive material, a solid fixing agent, a solid fixing agent kit, and a method for processing a silver halide photographic light-sensitive material using a fixing solution prepared with the fixing concentrate or the solid fixing agent. To provide.

[0004]

The above object of the present invention has been attained by the following means.

[0005] 1. In a fixing concentrate for a silver halide photographic material containing at least a thiosulfate and a water-soluble aluminum salt, at least one of the compounds represented by the general formulas (1) to (3) and the general formula (A) or A fixing concentrate for a silver halide photographic material, characterized by containing the compound represented by (B).

[0006]

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(Wherein R ₁₁ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. Q ₁₁ represents a hydrogen atom or -L
₁₃ represents a -COOM _13. Q ₁₂ is a hydrogen atom or -L ₁₄ -
Represents COOM ₁₄ . L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ and L
₁₅ represents an alkylene group. m11 and n11
Represents 0 or 1, respectively. W ₁₁ represents a divalent linking group containing a carbon atom. * Indicates that the absolute configuration is S-configuration. M ₁₁ , M ₁₂ , M ₁₃ and M ₁₄ represent a hydrogen atom or a cation. )

[0008]

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Wherein R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅
Represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carboxyl group, a phosphono group, a hydroxyl group or a sulfo group, respectively. Provided that R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R
_At least one of ₂₅ represents an aliphatic group, an aryl group or a heterocyclic group substituted with a carboxyl group, a phosphono group or a sulfo group. L ₂₁ and L ₂₂ each represent a divalent aliphatic group, a divalent aromatic group or a divalent linking group composed of a combination thereof. M ₂₁ and M ₂₂ each represent a hydrogen atom or a cation. )

[0010]

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(Wherein, G ₃₁ and G ₃₂ each represent a carboxyl group, a phosphono group, a hydroxy group, a sulfo group, a mercapto group, an aryl group, a heterocyclic group, an alkylthio group, an amidino group, a guanidino group, or a carbamoyl group.
L ₃₁ , L ₃₂ and L ₃₃ each represent a divalent aliphatic group, a divalent aromatic group or a divalent linking group composed of a combination thereof. m31 and n31 each represent 0 or 1.
X ₃₁ represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group. M ₃₁ represents a hydrogen atom or a cation. )

[0012]

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(Wherein R ₄₁ and R ₄₂ each represent an alkyl group, an amino group, an alkoxy group, or an alkylthio group;
These may have a substituent and may combine with each other to form a ring. k41 represents 0 or 1, X ₄₁ when k41 = 1 represents -CO- or -CS-. M ₄₁ and M ₄₂ each represent a hydrogen atom or an alkali metal. ) General formula _{(B) R 51 - (A} 51) n51 -COOM 51 ( wherein, A ₅₁ represents an alkyl group or a carbonyl group having at least one hydroxyl group on a side chain, n51 is an integer of 0 or more R ₅₁ represents a hydrogen atom or an alkyl group having a hydroxyl group, and M ₅₁ represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group.) In a solid fixing agent for a silver halide photographic light-sensitive material containing at least thiosulfate and a water-soluble aluminum salt, at least one of the compounds represented by formulas (1) to (3) and the compound represented by formula (A) Or a solid fixing agent for a silver halide photographic light-sensitive material, which comprises the compound represented by (B).

3. A solid fixing agent for a silver halide photographic light-sensitive material, comprising a part containing a thiosulfate and a part containing a water-soluble aluminum salt, wherein the solid fixing agent has the general formula (1)
A solid fixing agent for a silver halide photographic light-sensitive material, comprising at least one compound represented by formulas (1) to (3) and a compound represented by formula (A) or (B).

4. The fixing concentrate for a silver halide photographic light-sensitive material according to claim 1, which is substantially free of a boron compound.

5. 4. The solid fixing agent for a silver halide photographic light-sensitive material as described in 2 or 3, wherein the solid fixing agent contains substantially no boron compound.

6. The concentrated solution for a silver halide photographic light-sensitive material according to the above 1 or 4, or the solid fixing agent for a silver halide photographic light-sensitive material according to the above 2, 3, or 5, having an oxygen permeability of 50.
A method for preserving a solid fixing agent for a silver halide photographic light-sensitive material, wherein the solid fixing agent is packaged in a packaging material of not more than ml / m ² · atom · day (temperature: 20 ° C, relative humidity: 65%).

[7] After developing the exposed silver halide photographic material, the fixing concentrate for silver halide photographic material described in 1 or 4 above or the solid fixing agent for silver halide photographic material described in 2, 3 or 5 above. Is processed with a fixing solution obtained by diluting or dissolving photographic light-sensitive material with water.

Hereinafter, the present invention will be described in detail.

The inventor of the present invention has conducted intensive studies on the above problems, and as a result, it has been found that even in a hardening solution excluding a boron compound, the formation of the above-mentioned insoluble aluminum compound is suppressed, and sulfurization due to the influence of an acid component is suppressed. At the same time, they have found a technique for preventing this and have reached the present invention.

That is, according to the present invention, the general formula (1)
By using a combination of at least one of the chelating agents represented by formulas (1) to (3) and the compound represented by formula (A) or (B), even if the boron compound conventionally used is removed, Insoluble in a fixer prepared using the same, due to the formation of a hardly soluble aluminum salt under the storage conditions of a hardening fixer concentrate containing a soluble aluminum salt or a solid fixer, or sulfurization caused by the action of an acid component. It is possible to provide a hardening fixing concentrated solution or a solid fixing agent which does not cause minuteness and deterioration of fixing property.

First, the compound represented by formula (1) will be described in detail below.

The aliphatic hydrocarbon group represented by R ₁₁ is a linear, branched or cyclic alkyl group (preferably having 1 to carbon atoms).
12, more preferably an alkyl group having 1 to 7 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, i
so-butyl, tert-butyl, n-heptyl, n-
Hexyl, cyclohexyl and the like can be mentioned. ), An alkenyl group (preferably an alkenyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, for example, vinyl, allyl and the like), and an alkynyl group ( It preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 2 carbon atoms.
And alkynyl groups such as propargyl. ).

The aliphatic hydrocarbon group represented by R ₁₁ may have a substituent. Examples of the substituent include an aryl group (preferably having 6 to 12 carbon atoms, more preferably having 6 to 12 carbon atoms). 10, particularly preferably an aryl group having 6 to 8 carbon atoms, for example, phenyl, p-methylphenyl, etc.), an amino group (preferably having 0 to 20 carbon atoms,
More preferably, it is an amino group having 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, and diethylamino. ), An alkoxy group (preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms).
And include, for example, methoxy, ethoxy and the like. ), An aryloxy group (preferably an aryloxy group having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably 6 to 8 carbon atoms, such as phenyloxy), and an acyl group (Preferably has 2 to 12 carbon atoms, more preferably 2 to 1 carbon atoms.
0, particularly preferably an acyl group having 2 to 8 carbon atoms, such as acetyl. ), An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as methoxycarbonyl). A carbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 1 carbon atoms)
5, particularly preferably an aryloxycarbonyl group having 7 to 10 carbon atoms, such as phenyloxycarbonyl. ), An acyloxy group (preferably an acyloxy group having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as acetoxy, etc.), an acylamino group (preferably Carbon number 2-10, more preferably carbon number 2-6,
Particularly preferred is an acylamino group having 2 to 4 carbon atoms,
For example, acetylamino and the like can be mentioned. ), An alkoxycarbonylamino group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and particularly preferably having 2 carbon atoms.
To 8 alkoxycarbonylamino groups, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 2 carbon atoms)
An aryloxycarbonylamino group having 0, more preferably 7 to 12 carbon atoms, and particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 carbon atom)
A sulfonylamino group having 10 to 10, more preferably 1 to 6, and particularly preferably 1 to 4 carbon atoms, such as methanesulfonylamino. ), A sulfamoyl group (preferably a sulfamoyl group having 0 to 10 carbon atoms, more preferably 0 to 6 carbon atoms, particularly preferably 0 to 4 carbon atoms, such as sulfamoyl and methylsulfamoyl). A carbamoyl group (preferably a carbamoyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as carbamoyl and methylcarbamoyl); and an alkylthio group (preferably Has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 1 carbon atoms.
And 4, for example, methylthio, ethylthio, carboxymethylthio and the like. ), An arylthio group (preferably an arylthio group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably 6 to 8 carbon atoms, such as phenylthio, etc.), and a sulfonyl group (preferably 1-8 carbon atoms, more preferably 1-6 carbon atoms, particularly preferably 1-carbon atoms
4, for example, methanesulfonyl and the like. ), A sulfinyl group (preferably a sulfinyl group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methanesulfinyl and the like), and a ureido group (preferably Is a ureido group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, such as ureide and methyl ureide.), A hydroxy group, a mercapto group, and 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, a hydroxamic acid group,
Heterocyclic groups (eg, imidazolyl, pyridyl) and the like. 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 amino group, an alkoxy group, a carboxyl group, a hydroxy group, a halogen atom, a cyano group, or a nitro group, more preferably an alkoxy group, a carboxyl group, a hydroxy group, or a halogen atom, and further more preferably , An alkoxy group, a carboxyl group,
A hydroxy group, particularly preferably a hydroxy group,
It is a carboxy group.

[0025] Preferably the aliphatic hydrocarbon group represented by R ₁₁ is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms Is an alkyl group. Specifically, methyl, ethyl, n-propyl, iso-propyl, n-butyl, benzyl, hydroxymethyl, carboxymethyl, and 5-imidazolylmethyl are preferred, and methyl,
Ethyl, n-propyl, iso-propyl, n-butyl are preferred.

The aryl group represented by R ₁₁ may be a single ring or a condensed ring with another ring, and preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms. And more preferably an aryl group having 6 to 12 carbon atoms.

The aryl group represented by R ₁₁ is preferably monocyclic or bicyclic, and includes, for example, phenyl and naphthyl, and more preferably phenyl. R ₁₁
The aryl group represented by may have a substituent. Examples of the substituent include those exemplified as the substituent of the aliphatic hydrocarbon represented by R ₁₁ , and an alkyl group, an alkenyl group, an alkynyl group, and the like. Is mentioned.

The heterocyclic group represented by R ₁₁ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, and these may be monocyclic. Alternatively, a condensed ring may be formed with another ring.

The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic ring, and more preferably a 5- or 6-membered aromatic heterocyclic ring.
And a 6-membered aromatic heterocycle, more preferably a 5- or 6-membered aromatic heterocycle containing 1 or 2 nitrogen atoms. Specific examples of these heterocycles include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline,
Pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole and the like can be mentioned. Preferably as a heterocycle, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline,
Phthalazine, quinoxaline, quinazoline, cinnoline,
Tetrazole, thiazole, oxazole, more preferably imidazole, pyrazole, pyridine, pyrazine, indole, indazole, thiadiazole,
Oxadiazole, quinoline, thiazole, oxazole, more preferably imidazole, pyridine,
Quinoline, particularly preferably imidazole and pyridine.

The heterocyclic group represented by R ₁₁ may have a substituent. Examples of the substituent include those exemplified as the substituent for the aliphatic hydrocarbon represented by R ₁₁ , and an alkyl group and an alkenyl group. And alkynyl groups. R ₁₁ is preferably an alkyl group having 1 to 7 carbon atoms or a phenyl group,
An alkyl group having 1 to 4 carbon atoms or a phenyl group is more preferred.

Q ₁₁ is a hydrogen atom or -L ₁₃ -COOM
It represents a _13, preferably a -L ₁₃ -COOM _13. Q
₁₂ represents a hydrogen atom or -L ₁₄ -COOM _14, preferably -L ₁₄ -COOM _14. Alkylene group represented by L ₁₁ ~L ₁₅ is a straight-chain may be branched or cyclic, preferably linear or branched alkylene group. The number of carbon atoms forming the alkylene group is preferably 1 to
10, more preferably 1 to 6, particularly preferably 1
~ 4.

L _{11 to} L ₁₅ are preferably methylene, and more preferably unsubstituted methylene. L ₁₂ ,
Preferred as L ₁₃ and L ₁₄ are methylene and ethylene. Further, the alkylene group represented by L _{11 to} L ₁₅ may have a substituent. Examples of the substituent include those described above as the substituent of the aliphatic hydrocarbon represented by R ₁₁ , an alkenyl group, And alkynyl groups. The L _12, L _14, substituted methylene are also preferred, as the substituent, R ₁₁
And alkenyl groups, alkynyl groups and the like, in addition to those mentioned as the substituents of the aliphatic hydrocarbon represented by

M11 and n11 represent 0 or 1, preferably (m11, n11) = (1, 0), (m
11, n11) = (0, 1), (m11, n11) =
(0, 0), and more preferably (m11, n11)
= (1,0), (m11, n11) = (0,0), and most preferably (m11, n11) = (0,0).

The divalent linking group represented by W ₁₁ can be preferably represented by the following general formula (W _11).

In the general formula (W ₁₁ )-(W ₁ -D) _s- (W ₂ ) _t-wherein W ₁ and W ₂ may be the same or different, and may have 2 to 8 carbon atoms. A linear or branched alkylene group (eg, ethylene, propylene), a cycloalkylene group having 5 to 10 carbon atoms (eg, 1,2-cyclohexyl), an arylene group having 6 to 10 carbon atoms (eg, o-phenylene),
Represents an aralkylene group having 7 to 10 carbon atoms (for example, o-xylenyl) or a carbonyl group. D is -O-, -S
-, -N (Rw)-, a divalent nitrogen-containing heterocyclic group.
Rw represents a hydrogen atom or -COOMa, -PO ₃ MbM
c, represents a -OH or -SO ₃ Md at 1-8 carbon atoms which may be substituted alkyl groups (e.g. methyl) or an aryl group having 6 to 10 carbon atoms (e.g., phenyl). M
a, Mb, Mc and Md each represent a hydrogen atom or a cation. The divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring in which the hetero atom is nitrogen, and those linked to W ₁ and W ₂ at adjacent carbon atoms such as an imidazolyl group are preferred. More preferred. As W ₁ and W ₂ , an alkylene group having 2 to 4 carbon atoms is preferable. s is 0
Represents an integer of ３3, and when s is 2 or 3, W ₁ -D may be the same or different. s is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.
t represents an integer of 1 to 3, and when t is 2 or 3, W ₂
May be the same or different. t is preferably 1 or 2.

The linking group represented by W ₁₁ may have a substituent. Examples of the substituent include an alkyl group (for example, R
What was mentioned as an alkyl group represented by ₁₁ can be applied. The same applies to the preferred range. ), An aryl group (a phenyl group and a naphthyl group are preferred, and a phenyl group is preferable. The aryl group may further have a substituent); a heterocyclic group (eg, an alkyl group represented by R ₁₁ ) What is mentioned as a heterocyclic group which may have is applicable.
The same applies to the preferred range. These heterocyclic groups may further have a substituent. ), An alkoxy group (an alkoxy group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4. For example, methoxy and ethoxy), and a hydroxy group Is mentioned.

The substituent is preferably an alkyl group or a hydroxy group, and more preferably an alkyl group.

The linking group represented by W ₁₁ is preferably unsubstituted. Specific examples of W _11, for example, the following.

[0039]

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[0040]

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The cations represented by M ₁₁ , M ₁₂ , M ₁₃ and M ₁₄ may be organic cations or inorganic cations. When there are two or more cations in the same molecule, they may be different cations. Examples of the cation include alkali metals (eg, Li ⁺ , Na ⁺ ,
K ⁺ , Cs ⁺ etc.), alkaline earth metals (eg Ca ²⁺ ,
Mg ²⁺ ), ammonium (eg, ammonium, tetraethylammonium, etc.), pyridinium, phosphonium (eg, tetrabutylphosphonium, tetraphenylphosphonium, etc.). Preferably, it is an inorganic cation, and more preferably, it is an alkali metal ion.

Among the compounds represented by the general formula (1), a compound represented by the following general formula (1-a) is preferable. More preferred are compounds represented by the following general formula (1-b), and most preferred are compounds represented by the following general formula (1-b)
It is a compound represented by c).

[0043]

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In the formula, R _11a represents an aliphatic hydrocarbon group or an aryl group. The aliphatic hydrocarbon group and the aryl group represented by R _{11a have the same} meaning as the aliphatic hydrocarbon group and the aryl group represented by R ₁₁ in the general formula (1),
The same applies to the preferred range. L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ ,
L ₁₅ , m 11, n ₁₁ , *, W ₁₁ , M ₁₁ , M ₁₂ , M ₁₃ and M ₁₄ have the same meanings as those in formula (1), respectively, and their preferred ranges are also the same.

[0045]

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In the formula, R _11a represents an aliphatic hydrocarbon group or an aryl group. The aliphatic hydrocarbon group and the aryl group represented by R _11a have the same meanings as the aliphatic hydrocarbon group and the aryl group represented by R ₁₁ in Formula (1), and the preferred ranges are also the same. W _{11 a} is an alkylene group having 2 to 8 carbon atoms in W ₁₁ in the general formula (1), and preferred ranges are also the same. _{L 13, L 14, m11,} *,
M ₁₁ , M ₁₂ , M ₁₃ and M ₁₄ are each represented by the general formula (1)
And the preferred range is also the same.

[0047]

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In the formula, R _11a represents an aliphatic hydrocarbon group or an aryl group. The aliphatic hydrocarbon group and the aryl group represented by R _{11a have the same} meaning as the aliphatic hydrocarbon group and the aryl group represented by R ₁₁ in the general formula (1),
The same applies to the preferred range. W _11a is an alkylene group having 2 to 8 carbon atoms at W ₁₁ in formula (1), and the preferred range is also the same. L ₁₃ , L ₁₄ , *, M ₁₁ ,
M ₁₂ , M ₁₃ and M ₁₄ have the same meanings as those in formula (1), respectively, and their preferred ranges are also the same. ) These compounds have structural features such as aliphatic hydrocarbon groups,
It is substituted with an aryl group or a heterocyclic group, and the asymmetric carbon at the substitution position has at least one carboxyalkyl in the S configuration. When there is one asymmetric carbon, a racemic mixture (the absolute configuration is 1: 1 of S-form and R-form)
mixture. The relationship between the R-form and the S-form is called an optical isomer. ) And a diastereomeric mixture (a mixture of SS, RR, RS, and SR isomers) when there are two asymmetric carbons. An SS isomer and an RR isomer are an optical isomer, an SS isomer and an RS isomer, or an RR isomer is The relationship between the RS isomers is referred to as diastereomer.). Normally, when there is one asymmetric carbon, the R-form and the S-form are produced at a ratio of 1: 1. Without any optical resolution, the S-form does not exceed 50%. Even when there are two asymmetric carbons, RR-forms: SS-forms: RS-forms are produced in a ratio of 1: 1: 2 unless intentionally trying to obtain a substance having a high optical purity. When used in the present invention, these optical isomers are in S-form, and diastereomers are compounds having at least one S such as SS-form and SR-form (SS-form, SR-form)
The effect of the present invention is high when the ratio of the (body) is 50% or more of the whole, preferably 75% or more, more preferably 90% or more. Above all, the higher the abundance ratio of the SS body is, the larger the effect is, and the abundance ratio of the SS body is usually 25%, but in order to expect a sufficient effect, the abundance ratio of the SS body must be 50% or more of the whole Preferably, it is at least 80%, particularly preferably at least 90%. It is said that the S-form and the SS-form are better in biodegradability, and are likely to be degraded, so that the effect is low. However, it is probably because the chelating property is good.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto. The asterisk in the specific examples indicates that it is an asymmetric carbon.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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The compounds represented by the general formula (1) of the present invention are described, for example, in Inorganic Chemistry, Vol. 8, No. 6, p. 1374 (1969) (Inorganic).
ic Chemistry, 8 (6), 1374 (19
69)) According to the method described in JP-A-10-2218.
The compound can be synthesized by the method described in No. 28.

Next, the compound represented by formula (2) will be described in detail below. R ₂₁ , R ₂₂ , R ₂₃ , R
Examples of the aliphatic group represented by ₂₄ and R ₂₅ include a linear, branched or cyclic alkyl group (preferably having 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 6 carbon atoms), and an alkynyl group (preferably C2-6), preferably an alkyl group. Examples of the aliphatic group include a methyl group, an ethyl group, a cyclohexyl group, a benzyl group, and an allyl group. The aliphatic group may have a substituent. Examples of the substituent include an alkyl group (for example, methyl and ethyl), an aralkyl group (for example, phenylmethyl), an alkenyl group (for example, allyl), an alkynyl group, and an alkoxy group (for example, Methoxy, ethoxy), aryl group (eg, phenyl, p-methylphenyl), acylamino group (eg, acetylamino), sulfonylamino group (eg, methanesulfonylamino), ureido group, alkoxycarbonylamino group (eg, methoxycarbonylamino), aryl Oxycarbonylamino group (eg, phenoxycarbonylamino), aryloxy group (eg, phenyloxy), sulfamoyl group (eg, methylsulfamoyl), carbamoyl group (eg, carbamoyl, methylcarbamoyl), alkylthio group (eg, For example, methylthio,
Carboxylmethylthio), an arylthio group (eg, phenylthio), a sulfonyl group (eg, methanesulfonyl), a sulfinyl group (eg, methanesulfinyl),
Hydroxy group, halogen atom (eg, chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxyl group, phosphono group, aryloxycarbonyl group (eg, phenyloxycarbonyl), acyl group (eg, acetyl, benzoyl), alkoxy Examples include a carbonyl group (eg, methoxycarbonyl), an acyloxy group (eg, acetoxy), a nitro group, a hydroxamic acid group, a heterocyclic group (eg, imidazolyl, pyridyl).

The aryl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ may be monocyclic or bicyclic, preferably
It has 6 to 20 carbon atoms and includes, for example, a phenyl group and a naphthyl group. The aryl group may have a substituent. As the substituent, for example, those exemplified as the substituents that the aliphatic group represented by R _{21 to} R ₂₅ may have can be applied.

The heterocyclic group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ is a 3- to 10-membered heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Yes, they may be saturated or unsaturated, and they may be monocyclic or may form a condensed ring with another aromatic or heterocyclic ring. The heterocyclic ring is preferably a 5- to 6-membered unsaturated heterocyclic ring, more preferably a 5- to 6-membered aromatic heterocyclic group in which a hetero atom is a nitrogen atom. The heterocycle is preferably pyridine, pyrazine, pyrimidine, pyridazine, thiophene, pyrrole, imidazole, pyrazole, thiazole, oxazole, indole, more preferably pyridine, imidazole, indole. R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are preferably a hydrogen atom, a carboxyl group, a hydroxy group, a carboxymethyl group or a hydroxymethyl group.
R ₂₄ is more preferably a carboxyl group.

As the divalent aliphatic group for L ₂₁ and L _22, a linear, branched or cyclic alkylene group (preferably having 1 carbon atom)
To 6), an alkenylene group (preferably having 2 to 6 carbon atoms),
An alkynylene group (preferably having 2 to 6 carbon atoms) is exemplified. Further, the divalent aliphatic group of L ₂₁ and L ₂₂ may have a substituent, and examples of the substituent include a substituent which the aliphatic group represented by R _{21 to} R ₂₅ may have. The ones listed are applicable. Specific examples of the divalent aliphatic group for L ₂₁ and L ₂₂ include a methylene group, an ethylene group, a 1-carboxymethylene group, a 1-carboxyethylene group, a 2-hydroxyethylene group, a 2-hydroxypropylene group, Examples include a phosphonomethylene group, a 1-phenylmethylene group, and a 1-carboxybutylene group.

Examples of the divalent aromatic group represented by L ₂₁ and L ₂₂ include a divalent aromatic hydrocarbon group (arylene group) and a divalent aromatic heterocyclic group. The divalent aromatic hydrocarbon group (arylene group) may be monocyclic or bicyclic, preferably
It has 6 to 20 carbon atoms and includes, for example, a phenylene group and a naphthylene group. As the divalent aromatic heterocyclic group, a 3- to 10-membered group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom, and even if it is a single ring, it is further substituted with another aromatic ring or a heterocyclic ring. A condensed ring may be formed. Preferably, the hetero atom is a 5- to 6-membered aromatic heterocyclic group having a nitrogen atom. Examples of the divalent aromatic heterocyclic group include the following.

[0067]

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The divalent aromatic group is preferably an arylene group (preferably having 6 to 20 carbon atoms), more preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group. The divalent aromatic group of L ₂₁ and L ₂₂ may have a substituent.
Has aliphatic group represented by ₂₁ to R ₂₅ may are the same as those mentioned may also be a substituent. L ₂₁ and L ₂₂ may be a combination of a divalent aliphatic group and a divalent aromatic group, for example,

[0069]

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And the like. L ₂₁ and L ₂₂ are preferably an alkylene group or an o-phenylene group having 1 to 3 carbon atoms which may be substituted, more preferably a methylene group or an ethylene group which may be substituted, and particularly preferably a substituted methylene group or an ethylene group. A methylene group which may be

The cations represented by M ₂₁ and M ₂₂ are organic and inorganic cations such as ammonium (eg, ammonium and tetraethylammonium), pyridinium and alkali metals (eg, lithium, sodium,
Potassium) and the like.

Among the compounds represented by the general formula (2), a compound represented by the following general formula (2-a) is preferable.

[0073]

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In the formula, M ₂₁ and M ₂₂ have the same meanings as in the general formula (2). R ₂₁ , R ₂₂ , R ₂₃ and R
₂₅ represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carboxyl group, a phosphono group, a hydroxy group or a sulfo group, respectively. Provided that R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R
_At least one of ₂₅ represents an aliphatic group, an aryl group or a heterocyclic group substituted with a carboxyl group, a phosphono group or a sulfo group. M ₂₃ is M ₂₁ in the general formula (2).
Is synonymous with

Specific examples of the compound represented by formula (2) are shown below, but the present invention is not limited to these.

[0076]

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[0077]

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[0078]

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[0079]

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The above compounds may be used in the form of an ammonium salt, an alkali metal salt or the like. The compounds represented by the general formula (2) are described in JP-A-63-267750 and JP-A-63-267750.
267751, JP-A-2-115172 and 2-2
It can be synthesized according to the method described in US Pat.

Next, the compound represented by formula (3) will be described in detail. Aryl group represented by G ₃₁ and G ₃₂ (aromatic hydrocarbon group) may be monocyclic or bicyclic, preferably 6 to 20 carbon atoms, such as phenyl group, naphthyl group. The aryl group may have a substituent, and examples of the substituent include those described as the substituents that the aliphatic group represented by R _{21 to} R ₂₅ in formula (2) may have. Applicable.

The heterocyclic group represented by G _{31 or} G ₃₂ is a 3- to 10-membered heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. And these may be a single ring, or may form a condensed ring with another aromatic or heterocyclic ring. The heterocyclic ring is preferably a 5- to 6-membered unsaturated heterocyclic ring, more preferably a 5- to 6-membered heterocyclic ring having a nitrogen atom.
Membered aromatic heterocyclic group. The heterocycle is preferably pyridine, pyrazine, pyrimidine, pyridazine, thiophene, pyrrole, imidazole, pyrazole, thiazole, oxazole, triazole, indole, and more preferably pyridine, imidazole, indole.

The alkylthio groups represented by G ₃₁ and G ₃₂ are represented by —SRs (Rs represents an alkyl group). The alkyl group represented by Rs is a linear, branched, or cyclic alkyl group, and preferably has 1 to 6 carbon atoms.
Particularly, a straight chain having 1 to 4 carbon atoms is preferable. The alkyl group represented by Rs may have a substituent, and the substituent includes:
For example, those exemplified as the substituents which the aliphatic group represented by R _{21 to} R ₂₅ in the general formula (2) may have can be applied. Specific examples of the alkylthio group represented by G ₃₁ and G _32, for example, methylthio group, ethylthio group, hydroxyethyl thio group, and carboxyl methyl thio group. Preferred are a methylthio group and an ethylthio group.

The carbamoyl groups represented by G ₃₁ and G ₃₂ may be substituted and can be represented by —CONR _a1 (R _a2 ). Here, R _a1 and R _a2 each represent a hydrogen atom, an alkyl group or an aryl group. The alkyl group represented by R _a1 and R _a2 is a linear, branched or cyclic alkyl group, which may be substituted, and preferably has 1 to 10 carbon atoms. The aryl group represented by R _a1 or R _a2 may be substituted, preferably has 6 to 10 carbon atoms, and more preferably has a phenyl group. Further, R _a1 and R _a2 may be linked to form a ring. Particularly preferred as R _a1 and R _a2 are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted, and a phenyl group which may be substituted. _Ra1 , _Ra2
As the substituents of the alkyl group and the aryl group, those exemplified as the substituents which the aliphatic group represented by R _{21 to} R ₂₅ in formula (2) may have can be applied. G ₃₁
And specific examples of the carbamoyl group represented by G ₃₂ may
For example, carbamoyl group, N-methylcarbamoyl group, N
-Phenylcarbamoyl group, morpholinocarbamoyl group and the like.

G ₃₁ is preferably a carboxyl group, a hydroxy group, an aryl group or a heterocyclic group, and most preferably a carboxyl group. The G _32, carboxyl group, hydroxy group, sulfo group, a phosphono group, an aryl group, a heterocyclic group are preferred, a carboxyl group, an aryl group, more preferably a heterocyclic group, a carboxyl group is most preferred.

[0086] L _31, L ₃₂ and divalent aliphatic group represented by L _33, divalent aromatic group or a divalent linking group composed of a combination thereof, L ₂₁ in the general formula (2), L ₂₂ as synonymous. m31 and n31 are 0 or 1. m31 is preferably 1. n31 is preferably 0. The aliphatic group represented by X _31, linear, branched or cyclic alkyl group (preferably having 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 6 carbon atoms), an alkynyl group (preferably the number of carbon atoms 2 to 6), preferably an alkyl group. Examples of the aliphatic group include a methyl group, an ethyl group, a cyclohexyl group, a benzyl group, and an allyl group.

The aryl group represented by X ₃₁ may be monocyclic or bicyclic, and preferably has 6 to 20 carbon atoms, such as phenyl and naphthyl. The heterocyclic group represented by X ₃₁ is a 3- to 10-membered heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom, and may be saturated or unsaturated; These may be monocyclic or may form a condensed ring with another aromatic or heterocyclic ring. The heterocyclic ring is preferably a 5- to 6-membered unsaturated heterocyclic ring, more preferably a 5- to 6-membered aromatic heterocyclic group in which a hetero atom is a nitrogen atom. The heterocycle is preferably pyridine, pyrazine, pyrimidine, pyridazine, thiophene, pyrrole, imidazole, pyrazole, thiazole, indole, and more preferably pyridine, imidazole.

The aliphatic group, aryl group and heterocyclic group represented by X ₃₁ may have a substituent. Examples of the substituent include aliphatic groups represented by R _{21 to} R ₂₅ in formula (2). What was mentioned as the substituent which the group may have may be applied.
X ₃₁ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. M ₃₁ has the same meaning as M ₂₁ and M ₂₂ in formula (2). Among the compounds represented by the general formula (3), a compound represented by the following general formula (3-a) is preferable.

[0089]

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In the formula, G ₃₂ , L ₃₃ and M ₃₁ have the same meanings as those in formula (3), respectively. M ₃₂ represents a hydrogen atom and a cation.

Specific examples of the compound represented by formula (3) are shown below, but the present invention is not limited thereto.

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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The above compounds may also be used in the form of ammonium salts, alkali metal salts and the like. The above compound represented by the general formula (3) can be synthesized by a method according to the method described in JP-A-7-159961.

Next, the compound represented by formula (A) will be described.

The compound represented by the general formula (A) is ascorbic acid or a derivative thereof. In particular, in the general formula (A), R ₄₁ and R ₄₂ are bonded to each other to form a ring (A- It is preferred to use the compounds represented by a).

[0101]

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[0102] In the formula, R ₄₃ is a hydrogen atom, each substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group, or a sulfo group, a carboxyl group, an amide group, a sulfonamide group, Y ₄₁ is O Or S, Y ₄₂ is O,
It represents S or NR _44. R ₄₄ represents a substituted or unsubstituted alkyl group or aryl group.

The following formula (A) or (Aa)
Specific examples of preferred compounds represented by are shown below, but are not limited thereto.

[0104]

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[0105]

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[0106]

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[0107]

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Next, the compound represented by the following formula (B) will be described.

[0109] Formula _{(B) R 51 - (A} 51) in _n51 -COOM ₅₁ formula, A ₅₁ represents an alkylene group or a carbonyl group having at least one hydroxyl group on a side chain. n51 represents an integer of 0 or more, when R ₅₁ is a hydrogen atom n51 is 1
Represents the above integer. R ₅₁ represents a hydrogen atom or an alkyl group having a hydroxyl group. Moreover, the general formula (B) contains one carboxyl group in the form of the free acid or salt but, R ₅₁ and A
_No carboxyl group is substituted in the portion ₅₁ , and two or more are not contained in one molecule in total. The number of carbon atoms in the general formula (B) is preferably 2 to 10. M ₅₁ represents a hydrogen atom, an alkali metal atom (for example, potassium or sodium) or a quaternary ammonium group, and a metal atom is preferably used from the viewpoint of the solubility of the material and the safety of work.

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

[0111]

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[0112]

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[0113]

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In the present invention, substantially not containing a boron compound means that the concentration in the fixing working solution is 0.04 mol / liter or less.

Next, the fixing concentrate, the solid fixing agent, and the fixing solution (hereinafter collectively referred to as a fixing agent) used in the present invention will be described.

The fixing agent contains a thiosulfate.
Thiosulfates are usually lithium, potassium, sodium,
Although it is used as an ammonium salt, sodium thiosulfate and ammonium thiosulfate are preferably used. A fixing solution having a high fixing speed can be obtained by using it as an ammonium salt, but a sodium salt is preferred from the viewpoint of storage stability and the like.

The concentration of the thiosulfate is preferably from 0.1 to 5 mol / l, more preferably from 0.5 to 2 mol / l, even more preferably from 0.7 to 5 mol / l as the concentration of the dissolved or diluted fixing solution.モ ル 1.8 mol / liter. In addition, iodide salts, thiocyanates and the like can also be used as fixing agents.

The fixing agent may optionally contain a sulfite, a bisulfite or a metabisulfite. Sulfites,
As bisulfite or metabisulfite, lithium,
Potassium, sodium, ammonium salts and the like are preferably used.

The fixing agent used in the present invention contains a water-soluble aluminum salt. Examples of the water-soluble aluminum salt include aluminum sulfate, potassium aluminum chloride, and aluminum chloride. Further, a water-soluble chromium salt may be contained. Examples of the water-soluble chromium salt include chromium alum. The amount of the chromium salt or aluminum salt added is 0.2 to 30 g / l, preferably 1.2 to 20 g / l, as the concentration of the dissolved or diluted fixing solution.

Further, the fixing agent may contain acetic acid, citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof. These salts include, for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate,
Potassium hydrogen tartrate, potassium tartrate, sodium bitartrate, sodium tartrate, ammonium bitartrate,
Lithium, potassium, sodium, ammonium salts represented by ammonium potassium tartrate, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate and the like are preferred.

Among the above compounds, more preferred are acetic acid, citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof. The amount of compound added is 0.2 to
0.6 mol / l is preferred. Other acids include, for example, sulfuric acid, hydrochloric acid, inorganic acids and salts such as nitric acid,
Organic acids such as formic acid, propionic acid, oxalic acid, and malic acid are included. The preferred concentration of the acid is 0.5 to 40 g / liter as the concentration of the dissolved or diluted fixer.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. Is mentioned. As a fixing accelerator, for example,
5-35754, JP-B-58-122535, 5
Thiourea derivative, alcohol having a triple bond in the molecule, U.S. Pat. No. 4,126,45
Thioether described in JP-A No. 9 and a meso-ion compound described in JP-A-4-229860. The pH during use of the fixing solution is usually 3.8 or higher, preferably 4.2 to 5.5.
Having.

The solid fixing agent referred to in the present invention refers to a powder, granule, granule, lump or tablet form.

In the solid fixing agent of the present invention comprising a part containing a thiosulfate and a part containing a water-soluble aluminum salt, the compound represented by the general formula (1) to (3) and the compound represented by the general formula (A) or (A) The compound represented by (B) may be contained in either part. The general formula (1)
And a compound represented by formula (A) or (B)
May be added to the same part or to another part.

The solid fixing agent of the present invention preferably contains a compound represented by the following formula (L).

[0127] Formula (L) R '- (O ) x S y O z M containing 3.0% 0.01% of the total weight of the solid processing agent as weight or less, preferably 0.1% or more, 2.5% or less, more preferably 0.5% or more and 2.0% or less.

In the general formula (L), examples of the aliphatic group represented by R ′ include an alkyl group, an alkenyl group and an alkynyl group. Examples of the alkyl group include methyl,
Examples include groups such as ethyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and dodecyl. These alkyl groups further include a halogen atom (for example, an atom such as chlorine, bromine, and fluorine), an alkoxy group (for example, each group such as methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy), and an aryloxy group (Eg, phenoxy, naphthyloxy, etc.), aryl group (eg, phenyl, naphthyl, etc.), alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl, etc.), aryl An oxycarbonyl group (for example, each group such as phenoxycarbonyl and naphthyloxycarbonyl), an alkenyl group (for example, each group such as vinyl and allyl), and a heterocyclic group (for example, 2-pyridyl, 3-pyridyl,
4-pyridyl, morpholyl, piperidine, piperazil,
Pyrimidine, pyrazoline, furyl, etc.), alkynyl group (eg, propargyl group), amino group (eg, amino, N, N-dimethylamino, anilino, etc.), cyano group, sulfamide group (eg, methylsulfonylamino, Ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.).

Examples of the alkenyl group include a vinyl group,
Examples include an allyl group and the like, and examples of the alkynyl group include a propargyl group.

Examples of the aromatic group represented by R ′ include a phenyl group and a naphthyl group.

Examples of the heterocyclic group represented by R ′ include a pyridyl group (each group such as 2-pyridyl, 3-pyridyl, 4-pyridyl, etc.), a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group and a phenyl group. , A pyrrolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulfolanyl group, a pipedilinyl group, a pyrazolyl group, a tetrazolyl group, and the like.

The above-mentioned alkenyl group, alkynyl group, aromatic group and heterocyclic group can be substituted by the same groups as the alkyl group represented by R 'and the groups shown as the substituent of the alkyl group. .

X is 0 or 1, y is 1 or 2, and z is 2
Represents an integer of ８8.

The group represented by M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (ammonium, tetramethylammonium,
Ion such as tetrabutylammonium), phosphonium ion (tetraphenylphosphonium ion), and guanidyl ion.

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

L-1 C ₂ H ₅ SO ₃ Na L-2 CH ₃ (CH ₂ ) ₆ SO ₃ Na L-3 CH ₃ (CH ₂ ) ₇ SO ₃ Na L-4 CH ₃ (CH ₂ ) ₅ OSO the _{3 Na L-5 CH 3 (} CH 2) 6 OSO 3 Na L-6 CH 3 (CH 2) 7 OSO 3 Na L-7 CH 3 O (CH 2) 2 SO 3 Na fixing agent of the present invention, A surfactant may be contained,
Examples thereof include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants. Further, a wetting agent may be contained. For example, alkanolamine, alkylene glycol and the like can be mentioned. Further, a fixing accelerator may be further contained. For example, thiourea derivatives, alcohols having a triple bond in the molecule, thioethers and the like can be mentioned.

Next, the developer used in the present invention will be described.

The developer used in the present invention preferably contains reductones, particularly ascorbic acid and / or erythorbic acid (stereoisomer), as a developing agent.

Further, the following developing agents may be contained. Dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, etc., 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, -Phenyl-4-methyl-3-pyrazolidone, 1
-Phenyl-4,4-dimethyl-3-pyrazolidone, 1
-Phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1
-Phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazole) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc., aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), 1-allyl-
3-aminopyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p
-Amino-m-methylphenyl) -3-aminopyrazoline, pyrazolones (eg, 4-aminopyrazolone), and the like, or a mixture thereof.

The amount of carbonate in the developing solution of the present invention is 0.1.
It is preferably at least 3 mol / l and less than 0.8 mol / l.

The developer used in the present invention preferably contains a sulfite and / or metabisulfite. Further, when the tablet is dissolved to form a developer, the amount of sulfite in the solution is preferably 0.05 mol / L or more and less than 0.3 mol / L, more preferably 0.1 mol / L or more and less than 0.3 mol / L. .

In addition, as a buffering agent (for example, boric acid, borate, alkanolamine, etc. in addition to carbonate), an alkali agent such as alkali hydroxide, a solubilizing agent (such as polyethylene glycols and esters thereof), and a pH adjusting agent ( For example, organic acids such as citric acid), sensitizers (for example, quaternary ammonium salts), development accelerators, hardeners (for example, dialdehydes such as glutaraldehyde), surfactants, and azoles as antifoggants Organic antifoggants (eg, indazole, imidazole, benzimidazole, triazole, benzotriazole, tetrazole, thiadiazole), concealing agents for concealing calcium ions mixed in tap water used in treatment liquids As sodium hexametaphosphate, calcium hexametaphosphate , Polyphosphates, may contain a diethylenetriamine pentaacetic acid and the like.

Further, a silver stain inhibitor such as JP-A-56-2
The compound described in No. 4347 can also be used.

Further, the pH of the developer used in the present invention is 1
It is preferably in the range of 0.5 or less, more preferably 9
To 10.4, and particularly preferably 9.9 to 1.
0.3.

Further, amino compounds such as alkanolamines described in JP-A-56-106244 can be used in the developer used in the present invention.

In addition to the above, the developer used in the present invention includes L.P. F. A. Mason, "Photographic Processing Chemistry" Published by Focal Press (1
966), pp. 22-229, U.S. Pat.
No. 015, No. 2,592,364, JP-A-48-6
No. 4933 may be used.

Next, tableting of the processing agent for a photosensitive material will be described.

In order to make the photographic processing agent into a tablet, the photographic processing agent in the form of a concentrated liquid, a fine powder or a granular material and a water-soluble binder (binder) are kneaded and molded, or For example, a coating layer is formed by spraying a water-soluble binder on the surface, and JP-A-4-29136 and JP-A-4-85535.
Nos. 4-85536, 4-85533, 4-
Any means described in JP-A-85534 and JP-A-4-172341 can be employed.

As a preferable tablet production method, a solid processing agent component may be simply mixed and formed by a compression tableting step. However, a powdered solid processing agent is granulated in a granulation step and then obtained. A method of molding granules in a compression tableting step is more preferred.

As the granulation method, known methods such as rolling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. The average particle size of the granules obtained in the granulation step is preferably from 100 to 800 μm in that the components are not made uniform, that is, so-called segregation does not easily occur during pressure compression (compression tableting). , More preferably 200 to 750 μm. Further, the particle size distribution is such that 60% or more of the granulated particles are ± 100 to 1
Those with a deviation of 50 μm are preferred. When the obtained granules are subjected to compression molding (compression tableting), a known compressor is used.
For example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, a pre-cutting machine, or the like can be used.

The tablet production method of the present invention is described in, for example, JP-A-51-61837, JP-A-54-155038, and
Reference can be made to the methods described in the specifications such as 2-88025 and British Patent No. 1,213,808.

That is, the cylindrical tablet of the present invention can be easily formed into a tablet by the above-mentioned compressor equipped with a punch and a die or a tableting machine having a punch and a die.

In the tablet of the present invention, each component may be formed as a separate tablet. Also, when solidifying the developer,
When all components such as a developing agent, an alkaline agent, a reducing agent, etc. are converted into a solid processing agent and compressed into tablets, at least 3
One agent can be used within the agent. Alternatively, tablets may be divided into two or more agents.

In the tablet used in the present invention, each component may be formed as a separate tablet and packaged in the same manner.

The preferable bulk density of the solid processing agent of the present invention is as follows:
Preferably ^{0.4g / cm 3 ~2.5g / cm 3} , 1.0
ones g / cm ³ ~2.0g / cm ³ is more preferred.

As the light-sensitive material used in the present invention, a light-sensitive material containing a silver halide emulsion produced by a known method can be used. For example, Research Disclosure (RD) 17643 (December, 1978) 22- 23
Page 1 “Emulsion Preparative Method (Emulsion Prepar)
nation and types) and (RD) 18
716 (November 1979) page 648.

Also, T.I. H. James "The th
eory of the photographic
process "4th edition, published by Macmillan (1
977), pages 88 to 104; F. Da
"Photographic Emulsion Chemistry" by Uffin
ice emulation Chemistry ", Fo
cal press (1966); Glaf
"The Physics and Chemistry of Photography" by Kimides
t physique photographiqu
e "Paul Montel, Inc. (1967);
L. "Manufacture and coating of photographic emulsions" by Zelikman et al.
“Making and CoatingPhotog
raphic Emulsion "Focal pre
A silver halide emulsion prepared by a method described in ss Co., Ltd. (1964) or the like may be used.

Examples of preferably used silver halide emulsions include, for example, JP-A-59-177535 and JP-A-61-8.
No. 02237, No. 61-132943, No. 63-49
No. 751 and JP-A-2-85846. Silver chlorobromide or silver chloride having a silver chloride content of 50 mol% or more is also preferable.

The crystal structure of silver halide is preferably a core / shell type monodisperse emulsion having a two-layer structure comprising a low iodine shell layer in a high iodine core portion. The silver iodide content of the high iodine part is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

A silver halide emulsion preferably used is
Tabular grains having an average aspect ratio of greater than 1. The advantages of such tabular grains are known to provide improved spectral sensitization efficiency, improved image graininess and sharpness, and the like.

These emulsions can be prepared by using a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. Good. The emulsion may be subjected to a water washing method such as a noodle washing method or a flocculation sedimentation method to remove soluble salts.

As a preferred washing method, for example,
A method using a sulfo group-containing aromatic hydrocarbon aldehyde resin described in JP-A-5-16086, or JP-A-63-15 / 1988.
A method using an aggregating polymer agent (exemplified G3, G8) described in No. 8644 and the like are mentioned as a particularly preferred desalting method.

As a method for chemically ripening a silver halide emulsion, gold sensitization, sulfur sensitization, reduction sensitization, sensitization with a chalcogen compound, and a combination thereof are preferably used. Various photographic additives can be used in the emulsion before and after physical ripening or chemical ripening. In the emulsion, a hydrazine compound or a tetrazolium compound can be used as a high contrast agent. Further, a nucleation promoter can be used.

Other known additives to the emulsion include:
For example, the aforementioned RD17643 (December 1978) 23
Pp. 29, 18716 (November 1979) 648-
Pages 651 and 308119 (December 1989) 99
The compounds described on pages 6 to 1009 can be added.

Examples of the support that can be used for the light-sensitive material include RD17643, page 28 and RD3081.
19, page 1009.
A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, or the like in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided. Further, an emulsion layer may be present on both sides of the support, or only one side thereof. In the case of both sides, both sides may have the same performance or different performances.

[0166]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of photosensitive material) <Preparation of emulsion EM-1> Solution A Inert gelatin 30 g 4,5,6-Triaminopyrimidine 100 g Sodium chloride 1054 g Sodium bromide 68.7 g Distilled water 6000 ml Solution B 1135 g of silver nitrate 2000 ml with distilled water At 40 ° C., the pH of solution A was adjusted to 5.6 in a reaction vessel having a mixing stirrer described in JP-B-58-58288.
, And 6 ml of solution B was added over 1 minute. The addition rate was linearly accelerated (9.8 times from the start to the end) over a further 55 minutes, during which the entire amount of solution B was added. 5
After minutes and 18 minutes, 400 g of a 4 molar sodium chloride solution and 100 g of a 20 mmol 4,5,6-triaminopyrimidine solution were added. During the addition of the above materials, the inflow of silver
Stopped for minutes and the additives were mixed homogeneously.

During this period, the pH was controlled to be constant by adding sodium hydroxide or nitric acid. After the addition,
Excess salts were precipitated and desalted by a conventional method.

Observation of about 3000 particles of the obtained EM-1 with an electron microscope revealed an aspect ratio of 15 (average equivalent circle diameter 1.80 μm, average thickness 0.12 μm), and
Tabular silver chlorobromide grains containing 90 mol% of silver chloride.

<Preparation of photosensitive material> Emulsion EM-1 obtained
The following spectral sensitizing dyes (SD-1) and (SD
-2) was added at a weight ratio of 20: 1 to 400 mg per mol of silver halide. SD-1: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt SD-2: Anhydro-5,5'-di- ( (Butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-
Sulfobutyl) benzimidazolocarbocyanine sodium salt After 10 minutes, an appropriate amount of ammonium thiocyanate, chloroauric acid and sodium thiosulfate, and a dispersion of triphenylphosphine selenide were added, followed by chemical ripening. Forty minutes before the completion of ripening, a silver iodide fine grain emulsion of 0.06 μm was added in an amount of 6 × 10 ⁻⁴ mol per mol of silver, and then 4-hydroxy-6-methyl-1,3,3a, 7- as a stabilizer was added. Tetrazaindene (ST-1) was added in an amount of 3 × 10
^-2 mol was added and dispersed in an aqueous solution containing 70 g of gelatin.

Next, the following additives were added to this emulsion.
The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-butylcatechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonium Chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 4.0 g Sodium 2-mercaptobenzimidazole-5-sulfonate 15 mg 1-Phenyl-5-mercaptotetrazole 10 mg Trimethylolpropane 10 g C ₄ H ₉ OCH ₂ CH ( CH ₃ ) CH ₂ N (CH ₂ COOH) ₂ 1 g Compound a 60 mg Compound b 35 mg

[0173]

Embedded image

Further, 1.0 g of the following emulsified dye dispersion was used.
Was added to obtain an emulsion coating solution.

(Preparation of Dye Emulsion Dispersion) The following dye (F-
1) 10 kg was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresyl phosphate and 85 liters of ethyl acetate. This is called an oil-based solvent. On the other hand, 9.3 containing 1.35 kg of sodium tri-i-propylnaphthalenesulfonate (SU-1) which is an anionic surfactant is contained.
% Gelatin solution is referred to as an aqueous solvent.

Next, the oil-based solvent and the aqueous-based solvent were placed in a dispersion vessel, and dispersed while maintaining the liquid temperature at 40 ° C. An appropriate amount of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane was added to the obtained dispersion, and the mixture was made up to 240 kg with water to obtain a finished dye emulsion dispersion.

[0177]

Embedded image

The additives used for the protective layer are as follows. The amount of addition is indicated by the amount per liter of the coating solution.

(Coating solution for protective layer) Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Polymethyl methacrylate (matting agent having an average particle size of 5.0 μm) 1.1 g Silicon dioxide particles (matting agent having an average particle size of 3.0 μm) 0.5 g Ludox AM (Colloidal silica manufactured by DuPont) 30 g Glyoxal 40% aqueous solution (hardener) 1.5 ml (CH ₂ ＣＨCHSO ₂ CH ₂ ) ₂ O (hardener) 500 mg C ₁₂ H ₂₅ CONH (CH _{2) CH 2 O) 5 H 2.0g SU} -2 ( surfactant) 20mg SU-3 (surfactant) 7mg SU-4 _{(surfactant) 7mg C 12 H 25 CONH (} CH 2 CH 2 O) 6 H 62 mg DI-1 (antifungal agent) 0.9 mg

[0180]

Embedded image

175 μm thick colored blue at a concentration of 0.15
On both surfaces of the polyethylene terephthalate support of m, a coating solution prepared such that the coating amount per one surface was the following composition was applied to form an undercoat layer. The amount of addition is shown in the amount of application per 1 m ² .

(Coating solution for undercoat layer) Dye (F-2) 30 mg Gelatin 0.5 g p-nonylphenoxypolyethylene oxide (degree of polymerization = 10) 6 mg 1-morpholinylcarbonyl-3- (pyridinio) methanesulfonate 80 mg polymethyl Methacrylate (mat agent with an average particle size of 2.5 μm) 2 mg

[0183]

Embedded image

[0184] 0 The emulsion coating solution on a support which has been subjected to the undercoating 1.8 g / m ² on one surface per terms of silver value, 1.6 g / m ² as a weight with a gelatin protective layer as weight with gelatin.
The emulsion layer and the protective layer were simultaneously coated on both sides at a speed of 90 m / min with two slide hopper coaters so as to obtain 9 g / m ^2, and dried for 2 minutes and 30 seconds to obtain a coated sample.

(Preparation of Fixing Concentrate) Formulation of Fixing Concentrate (1 liter finishing amount) Pure water 300 g Sodium sulfite 20 g Boric acid The amount described in Tables 2 and 3 Acetic acid (90%) 23 g Sodium acetate trihydrate 32 g Tartaric acid 2. 3 g Aluminum sulfate octahydrate 15 g Compounds represented by general formulas (1) to (3) Tables 2 and 3 described amounts Compounds represented by general formula (A) or (B) Tables 2 and 3 described amounts 1 -(N, N-dimethylamino) -ethyl-5-mercaptotetrazole 18 g Ammonium thiosulfate (70 wt / vol%) 260 g (Evaluation of high-temperature storage property) Fixing concentrate 1 prepared by the above-mentioned formulation
Fill the finished amount of 00cc in the packaging material shown in Table 1
Was stored for 40 days under the conditions described in (1) to prepare a high temperature storage sample. 10 samples of the high-temperature storage sample and the fixing concentrate stored at room temperature
After finishing to 0 cc, the photosensitive material was put in a beaker at 25 ° C. and immersed in the fixing solution at 25 ° C., and the time until the silver halide in the photosensitive material was dissolved was measured. Table 2 shows the results
And Table 3. In addition, the formation of sulfide in the high-temperature sample was observed.

[0186]

[Table 1]

[0187]

[Table 2]

[0188]

[Table 3]

As can be seen from Tables 2 and 3, the fixing concentrate of the present invention has improved high-temperature storage performance.

Example 2 A tablet containing a water-soluble aluminum salt was prepared as follows.

[0191] <Preparation of solid fixing agent> The [granules (1)] aluminum sulfate octahydrate as the water-soluble aluminum salts _{(Al 2 (SO 4) 3} · 8H 2 O) 15
50 g, boric acid as described in Table 3, 1100 g of succinic acid, 300 g of tartaric acid, average 10 μm in a commercially available bantam mill
Crush until it becomes D-Mannit 2 is added to these fine powders.
50 g and 50 g of D-Sorbit were added, and the amount of water added was 3
The mixture was dried at 50 ° C. with a fluidized bed drier to remove water to 10.0% (weight ratio) or less, and further sized with a 1.0 mm mesh. The granulated product was obtained by granulating with a machine.

Further, the granules are represented by the general formula (1)
A compound represented by the general formula (L) of the present invention comprising the compound represented by the formula (3) and the compound represented by the general formula (A) or (B) in the amounts described in Tables 4, 5 and 6, sodium acetate 750 g. (L-3) was added to make up 1.0% of the total weight;
The mixture was uniformly mixed for 7 minutes using a rotary mixer in a room conditioned at 5 ° C. and 40% RH or less.

The thus obtained mixture of the granulated product (1), sodium acetate and the compound (L-3) was treated with a mixture having a diameter of 30.
1 per tablet using a modified tableting machine equipped with a tough press collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Compression tableting was performed so that the amount became 0 g, to thereby prepare a fixing tablet A.

Next, a fixing tablet containing a fixing agent thiosulfate was prepared as follows.

[Preparation of granulated product (2)] Ammonium thiosulfate / sodium thiosulfate (90/10 weight ratio) 145
80 g are ground in a commercial bantam mill to an average of 10 μm. 550 g of sodium sulfite, 750 g of sodium metabisulfite, pine flow 1220
g was added, the amount of water added was 50 ml, and the mixture was stirred and granulated. The granulated product was dried at 50 ° C. using a fluidized bed drier to remove water to 1.0% (weight ratio) or less. The granulated product (2) was obtained by sizing with a sizing machine equipped with a 0.0 mm mesh.

[Preparation of Fixing Tablet] The granules (2) thus obtained are combined with the compounds represented by the general formulas (1) to (3) and the compound represented by the general formula (1) or (2). The compounds described in Tables 4, 5 and 6 were added, 4330 g of sodium acetate, and the compound (L-3) represented by the general formula (L) was added to 1.5% of the total weight. 5 by machine
The mixture thus obtained was mixed with a punch having a diameter of 30 mm and manufactured by Kikusui Seisakusho Co., Ltd., Tough Press Collect 1527H.
U was subjected to compression tableting using a modified tableting machine so that each tablet weighed 10 g, thereby producing a fixed tablet B having a diameter of 30 mm.

(Evaluation of High-Temperature Storage Property) The fixing tablets A and B thus obtained were placed in the packaging materials shown in Table 1 of Example 1 and stored at 60 ° C. for 40 days to prepare high-temperature storage samples. 4 samples of high temperature storage sample and fixing tablet A stored at room temperature
And 17 fixing tablets B were dissolved in water to obtain a final fixing solution of 1 liter. Put the obtained fixer in a beaker and add
The photographic material prepared in Example 1 was immersed in the above-mentioned fixing solution under the condition of ° C., and the time until the silver halide in the photographic material dissolved was measured. The results are shown in Tables 4, 5 and 6. or,
The formation of sulfide in the hot sample was observed.

[0198]

[0199]

[Table 4]

[0200]

[Table 5]

[0201]

[Table 6]

As can be seen from Tables 4, 5 and 6, the solid fixing agent of the present invention has improved high-temperature storage performance.

Example 3 (Preparation of developer) <Preparation of granulated product (3)> Potassium carbonate 51 as a carbonate
70 g is pulverized with a commercially available bantam mill until the average is about 50 μm. To this powder were added 100 g of diethylenetriaminepentaacetic acid, 5 g of 1-phenyl-5-mercaptotetrazole, 5 g of sodium 5-mercapto- (1H) -tetrazole, 1000 g of D-mannitol, and 300 g of D-sorbit, and the mixture was added to a commercially available stirring granulator. At room temperature with water 22
After granulating by adding 0 ml, the obtained granulated product was dried at 40 ° C. for 2 hours in a fluidized drier, and further dried for 1.0 hour.
The granulated product (3) was obtained by sizing with a sizing machine equipped with a mesh of mm.

<Preparation of Developed Tablet A> To the granulated product (3) thus obtained was added 1.5% of the total weight of methyl-β-cyclodextrin, and the compound (L-3) was further added. 25%, 40% R
7 using a rotary mixer in a room conditioned below H
After homogenous mixing for 30 minutes, the resulting mixture was
10g per tablet by a modified tableting machine of Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd.
Compressed tableting was performed with the filling amount of, to prepare a developed tablet A.

Next, a developing tablet containing sodium erythorbate as a developing agent was prepared as follows.

[Preparation of Granulated Material (4)] 1-Phenyl-3
-360 g of pyrazolidone, 10 g of N-acetyl D, L-penicillamine, 500 g of sodium glutaraldehyde bisulfite, 1200 g of sodium metabisulfite, 4000 g of sodium erysorbate, and 500 g of D-sorbit are added, and the mixture is stirred at room temperature in a commercially available stirring granulator. After granulating by adding water at 40 ° C, the granulated material is
For 2 hours to remove the water content of the granulated product to 1.0% or less, and then sized using a sizing machine equipped with a 1.0 mm mesh to obtain a granulated product (4).

[Preparation of Developed Tablet B] The granules (4) thus obtained were uniformly mixed for 7 minutes using a rotary mixer in a room conditioned at 25 ° C. and 40% RH or less. Thereafter, compression tableting was performed using a modified tableting machine equipped with a 30 mm diameter punch equipped with Kikusui Seisakusho's Tough Press Collect 152HU while changing the filling rate per tablet to produce a developed tablet B.

(Preparation of Developing Working Solution) Developing Working Solution was obtained by dissolving 12 developing tablets A and B in water per 1 liter of the finished amount.

(Preparation of Fixing Solution) (Preparation by Dilution of Fixing Concentrate) The concentrate of Example 1 (stored at room temperature) was finished with water to prepare a fixer.

(Preparation by Dissolving Fixing Tablets) Four fixing tablets A and 17 fixing tablets B of Example 2 were dissolved in water (stored at room temperature) per 1 liter of the finished amount to obtain a fixing solution.

(Running Evaluation) A running was performed using the film sample, the developing solution and the fixing solution obtained above.

The developing solution and the fixing solution were transferred to an automatic developing machine TCX-70.
1 and a running test was performed in the 30-second mode under the following conditions.

The developing temperature and the fixing temperature were both 35 ° C.
After the photosensitive material prepared in Example 1 was exposed to an optical density of 1.0, the photosensitive material was subjected to a running treatment every day for 3 weeks at 5 m ² . Both the replenishment amounts of the developing solution and the fixing solution are 1 m ^{2 of the} photosensitive material.
The amount was as shown in Table 7 per hit. At the start of the running, acetic acid was added to the developing tank of the automatic developing machine as a starter in such an amount that the pH of the developing solution became 10.00, and potassium bromide was added in an amount of 1 to 10.
An amount giving a concentration of 2.2 g / l was added to obtain a new solution.

(Evaluation of Remaining Color) After reaching an equilibrium state by running, the unexposed photosensitive material was processed under the above conditions, and evaluated in five steps according to the following criteria. The results are shown in Table 7.

5: No pigment residue at all 4: Pigment residue at a close look 3: Pigment residue 2: Pigment residue partially conspicuous 1: Pigment residue conspicuous on entire surface

[0216]

[Table 7]

As can be seen from Table 7, the present invention does not deteriorate the residual color even if the replenishment amount is reduced.

[0218]

The environmental load is reduced by removing the boron compound having a large environmental load from the fixing concentrate, solid fixing agent, and solid fixing agent kit for the silver halide photographic light-sensitive material.
Fixing solution which has excellent storage stability at high temperature of the concentrated solution, solid fixing agent and solid fixing agent kit, and which does not deteriorate in residual color even if the replenishing amount is reduced, and a method for processing a silver halide photographic material using the same Can be provided.

Claims (7)

[Claims] 1. A fixing concentrate for silver halide photographic materials containing at least a thiosulfate and a water-soluble aluminum salt, wherein at least one of the compounds represented by formulas (1) to (3) is used. A fixing concentrate for a silver halide photographic material, comprising a compound represented by formula (A) or (B). Embedded image (In the formula, R ₁₁ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. Q ₁₁ represents a hydrogen atom or —L ₁₃ —COOM.
Represents ₁₃ . Q ₁₂ represents a hydrogen atom or -L ₁₄ -COOM _14. L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ and L ₁₅ each represent an alkylene group. m11 and n11 represent 0 or 1, respectively. W ₁₁ represents a divalent linking group containing a carbon atom. * Indicates that the absolute configuration is S-configuration. M _11, M
_12, M ₁₃ and M ₁₄ represent a hydrogen atom or a cation. ) (Wherein, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ each represent a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, a carboxyl group, a phosphono group, a hydroxyl group or a sulfo group. R _21, at least one of R _22, R _23, R ₂₄ and R _25, a carboxyl group, substituted with a phosphono group or a sulfo group aliphatic group, an aryl group or a heterocyclic group .L ₂₁ and L ₂₂ represents a divalent aliphatic group, a divalent aromatic group, or a divalent linking group comprising a combination thereof, and M ₂₁ and M ₂₂ each represent a hydrogen atom or a cation. (Wherein, G ₃₁ and G ₃₂ are each a carboxyl group, a phosphono group, a hydroxy group, a sulfo group, a mercapto group, an aryl group, a heterocyclic group, an alkylthio group, an amidino group, .L ₃₁ representing a guanidino group or a carbamoyl group, L ₃₂ and L
₃₃ represents a divalent aliphatic group, a divalent aromatic group or a divalent linking group composed of a combination thereof. m31 and n31 each represent 0 or 1. X ₃₁ is a hydrogen atom,
Represents an aliphatic group, an aryl group or a heterocyclic group. M ₃₁ represents a hydrogen atom or a cation. ) (In the formula, R ₄₁ and R ₄₂ each represent an alkyl group, an amino group, an alkoxy group, or an alkylthio group, which may have a substituent and may combine with each other to form a ring. represents 0 or 1, X ₄₁ when k41 = 1 -
Represents CO- or -CS-. M ₄₁ and M ₄₂ each represent a hydrogen atom or an alkali metal. ) General formula _{(B) R 51 - (A} 51) n51 -COOM 51 ( wherein, A ₅₁ represents an alkylene group or a carbonyl group having at least one hydroxyl group on a side chain, is n51 0
Represents the above integer. R ₅₁ represents a hydrogen atom or an alkyl group having a hydroxyl group, and M ₅₁ represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group. ) 2. A solid fixing agent for a silver halide photographic light-sensitive material containing at least a thiosulfate and a water-soluble aluminum salt, wherein at least one of the compounds represented by formulas (1) to (3) is used. The general formula (A) or (B)
A solid fixing agent for a silver halide photographic light-sensitive material, characterized by containing a compound represented by the formula: 3. A solid fixing agent for a silver halide photographic light-sensitive material, comprising a part containing a thiosulfate and a part containing a water-soluble aluminum salt, wherein
A solid fixing agent for a silver halide photographic light-sensitive material, comprising at least one compound represented by formula (3) and a compound represented by formula (A) or (B). 4. The fixing concentrate for a silver halide photographic light-sensitive material according to claim 1, wherein the fixing concentrate does not substantially contain a boron compound. 5. The solid fixing agent for a silver halide photographic light-sensitive material according to claim 2, wherein the solid fixing agent contains substantially no boron compound. 6. The concentrated solution for a silver halide photographic light-sensitive material according to claim 1 or 4, or the solid fixing agent for a silver halide photographic light-sensitive material according to claim 2, 3 or 5, having an oxygen permeability of 5%.
A method for preserving a solid fixing agent for a silver halide photographic light-sensitive material, wherein the solid fixing agent is packaged in a packaging material of 0 ml / m ² · atom-day (temperature: 20 ° C, relative humidity: 65%) or less. 7. A fixing concentrate for a silver halide photographic material according to claim 1 or 4, or a silver halide according to claim 2, 3 or 5 after developing the exposed silver halide photographic material. A method for processing a silver halide photographic light-sensitive material, characterized by processing with a fixing solution obtained by diluting or dissolving a solid fixing agent for a photographic light-sensitive material with water.