JPH09211819A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the amt. of a processing soln. and to prevent the stain and scuffing of a sensitive material even by processing with a slit processing machine by filling a processing soln. contg. an iron complex salt of a specified compd. and having bleaching ability into a specified tank and carrying out processing. SOLUTION: A sensitive material is processed with a processing soln. contg. an iron (III) complex salt of a compd. represented by formula I or II and having bleaching ability in a processing tank at a processing part. The thickness of a section of the tank perpendicular to the forward direction of the sensitive material at the vapor-liq. interface is 0.1-2cm. In the formula I, R1 is H, an aliphatic hydrocarbon, etc., each of L1 and L2 is an alkylene and each of M1 and M2 is H or a cation. In the formula II, each of R21 -R24 is H, an aliphatic hydrocarbon, etc., each of (t) and (u) is 0 or 1, W is a C-contg. divalent combining group and each of M21 -M24 is H or a cation.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material), and particularly to a processing solution having a bleaching ability for a light-sensitive material. The present invention relates to a method of processing in a slit-shaped processing path by using.

[0001]

2. Description of the Related Art Generally, a photosensitive material is developed by sequentially passing through a rectangular parallelepiped processing tank containing a processing solution. On this occasion,
The photosensitive material is processed by immersing it in a large amount of processing liquid in order to obtain a uniform and uniform finish performance.However, if a large amount of processing liquid is stored in the processing tank, the amount of photosensitive material to be processed will increase. Especially when the amount is small, the exchange rate of the liquid in the processing tank decreases,
This has been a cause of fluctuations in the performance of the processed light-sensitive material, such as deterioration of the processing liquid over time and fluctuations in composition due to concentration. In order to improve that, in the photosensitive material processing apparatus, the thickness of the processing tank is reduced, the capacity of the processing tank is significantly reduced, the exchange rate of the tank solution is increased, and the stability of the processing solution is improved, or the size of the processing solution is reduced. Proposals that enable the design of processors are U.S. Patents 5,311,325, 5,420,659,
No.5,386,261, Shokai 63-148944, Kaikaidai 2-69331,
JP-A 1-129253, 3-119846, 2-103043, 2-2301
46. However, at present, as a bleaching agent contained in a processing solution having a bleaching ability,
Ethylenediaminetetraacetic acid (EDTA) and 1,3-propanediamine
Iron (III) complex salts consisting of chelating agents such as -N, N, N ', N'-tetraacetic acid (1,3-PDTA) are widely used, but the treatment liquid containing them is treated near the gas-liquid interface. A development process with a slit-like processing path as described above, in which a tar-like product, which is considered to be caused by the deterioration of the developer components brought into the tank, tends to form crystalline precipitates on the inner wall or members of the tank. Since the machine has a narrow passage (processing path) through which the photosensitive material passes, it is easy for the photosensitive material and the wall surface of the processing path to come into contact with each other. If processing is continued for a long time, the processed photosensitive material, especially the edges, will become dirty and scratched. There was a problem that there is a risk of

[0002]

Therefore, according to the present invention, the amount of processing liquid can be reduced, and even if the processing is carried out by a slit developing machine which can be easily miniaturized, the photosensitive material is stained or scratched. It is an object of the present invention to provide a method of processing a silver halide color photographic light-sensitive material without fear.

[0003]

The present invention relates to a method of processing a silver halide color photographic light-sensitive material with a processing solution having a bleaching ability after color development, and the processing solution having the bleaching ability is represented by the following general formula (I ) Or (II) of the compound iron (II
I) In a tank of a processing section containing a processing solution containing at least one kind of complex salt and having the bleaching ability, the thickness at the gas-liquid interface of the tank cross section orthogonal to the traveling direction of the photosensitive material is W. And 0.1 ≤ W ≤ 2 cm
Was achieved by processing in a treatment tank which is Further, it was also confirmed that the effect of unexpectedly reducing the processing unevenness was further increased.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION Regarding a processing solution having a bleaching ability, which contains an iron (III) complex salt of a compound represented by the above general formula (I) or (II), European Patent Nos. 430,000 and 520,457 are cited.
No. 567,126, No. 588,289, No. 591,934, etc., but none of these specifications is able to find the recognition of the domain of the present invention. General formula (I)

[0005]

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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)

[0007]

[Chemical 6]

(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.)

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 bleaching ability in the present invention 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. Say. Specific examples of the desilvering process in the present invention are shown 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 Optionally, a water washing step may be provided between these treatments.

First, 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.

The substituent is, 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,
Examples include p-methylphenyl and the like. ), An alkoxy group (preferably having 1 to 8 carbon atoms, more preferably having 1 carbon atom)
To 6, particularly preferably 1 to 4 carbon atoms, for example, methoxy, ethoxy and the like. ), An aryloxy group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably having 6 to 8 carbon atoms, such as phenyloxy, etc.), and an acyl group (preferably carbon atom). Number 1 to 12, more preferably 2 to 1 carbon atoms
0, particularly preferably 2 to 8 carbon atoms, such as acetyl. ), An alkoxycarbonyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 1 carbon atoms)
0, particularly preferably 2 to 8 carbon atoms, such as methoxycarbonyl. ), An acyloxy group (preferably having 1 to 12 carbon atoms, more preferably having 2 carbon atoms)
10 to 10, particularly preferably 2 to 8 carbon atoms, such as acetoxy. ), An acylamino group (preferably having 1 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms,
Particularly preferably, it has 2 to 4 carbon atoms, such as acetylamino. ), A sulfonylamino group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms,
Particularly preferably, it has 1 to 4 carbon atoms, and examples thereof include methanesulfonylamino. ), A sulfamoyl group (preferably having 0 to 10 carbon atoms, more preferably having 0 carbon atoms).
To 6, particularly preferably 0 to 4 carbon atoms, such as sulfamoyl and methylsulfamoyl. ), A carbamoyl group (preferably having 1 to 10 carbon atoms,
More preferably 1 to 6 carbon atoms, particularly preferably 1 carbon atom
To 4, for example, carbamoyl, methylcarbamoyl and the like. ), An alkylthio group (preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, for example, methylthio, ethylthio, etc.), a sulfonyl group (preferably carbon 1 to 8, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, for example, methanesulfonyl and the like; a sulfinyl group (preferably 1 to 8 carbon atoms, more preferably carbon A number of 1 to 6, particularly preferably a carbon number of 1 to 4, such as methanesulfinyl, etc.), a hydroxy group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group Group, carboxy group, nitro group, heterocyclic group (for example, 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 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, and examples of the substituent include those listed 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, 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 carbon number). 2-6,
Particularly preferably, it has 2 to 4 carbon atoms, and examples thereof include 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, 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 and the like.

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, quinolyl and the like, 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 It preferably has 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, and examples thereof include vinyl and allyl), and alkynyl groups (preferably 2 to 4 carbon atoms).
8, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, such as propargyl. ) And the like.

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

The alkylene groups represented by L ₁ and L ₂ may be the same or different from each other, and may be linear, branched or cyclic. Further, it may have a substituent, and examples of the substituent include, in addition to those described as the substituent of the aliphatic hydrocarbon represented by R ₁ , an alkenyl group (preferably having 2 to 8 carbon atoms, more preferably Number 2
6, particularly preferably having 2 to 4 carbon atoms, such as 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, such as propargyl). L ₁ and L ₂
The substituent of the alkylene group represented is preferably an aryl group, an alkoxy group, a hydroxy group, a carboxy group,
A sulfo group, more preferably an aryl group, a carboxy group or a hydroxy group. The alkylene group represented by L ₁ and L ₂ preferably has an alkylene group moiety having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably substituted or unsubstituted methylene or ethylene. Is.

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

The cations represented by M ₁ and M ₂ 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.), etc. Is mentioned. M ₁ and M ₂ are preferably alkali metals and ammonium, and more preferably Na ⁺ and K.
⁺ , NH ₄ ⁺ . Among the compounds represented by the general formula (I), the compound represented by the general formula (Ia) is preferable. General formula (Ia)

[0023]

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(In the formula, L ₁ and M ₁ have the same meanings as those in formula (I), respectively, and the preferred ranges are also the same. M _a1 and M _a2 are M ₂ in formula (I). And more preferably in the general formula (Ia), L ₁ is a substituted or unsubstituted methylene or ethylene, and M ₁ ,
M _a1 and M _a2 are any of a hydrogen atom, an alkali metal and ammonium, more preferably L ₁ is a substituted or unsubstituted methylene, and M ₁ , M _a1 and M _a2 are a hydrogen atom and an alkali. It is either a metal or ammonium, and particularly preferably L ₁ is a substituted or unsubstituted methylene having a total carbon number of 1 to 10 including a substituent,
M ₁ , M _a1 , and M _a2 are hydrogen atoms, Na ⁺ , K ⁺ , NH ₄ ⁺
In either case.

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

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

In the formula, W ¹ and W ² may be the same or different, and may be a linear or branched alkylene group having 2 to 8 carbon atoms (eg ethylene, propylene, trimethylene), 5 to 10 carbon atoms. A 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.

[0029]

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[0030]

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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. 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.

[0033]

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[0034]

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[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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[0041]

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[0042]

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[0043]

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[0044]

[Chemical 21]

[0045]

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[0046]

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[0047]

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

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

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

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

The organic acid iron (III) complex salt contained in the bleaching treatment solution of the present invention may be used as an alkali metal salt or an ammonium salt. As the alkali metal salt, a lithium salt, a sodium salt, a potassium salt, and the like, and as the ammonium salt, an ammonium salt, a tetraethylammonium salt, and the like can be given.In the present invention, the ammonium ion concentration in the processing solution having the bleaching ability is 0-0.
It is preferably 4 mol / l, particularly preferably 0 to 0.2 mol / l.

In the present invention, as the bleaching agent, other than 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, glycol etherdiaminetetraacetic 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 compound represented by the general formula (I) or (II) is suitably 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.

The bleaching solution preferably contains a pH buffering agent, particularly glycolic acid, succinic acid, maleic acid,
Malonic acid, glutaric acid and the like, it is preferable to contain an organic acid having a low odor, in particular, glycolic acid, malonic acid,
Succinic acid is preferred. The concentration of these buffers is 0
The range is preferably from 3 to 3 mol / liter, particularly from 0.2 to
A range of 1.5 mol / l is preferred.

In the present invention, the replenisher for the processing solution having a bleaching ability is a solid (powder, granules, tablets) even if it is a liquid.
In the granules and tablets, 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, JP-A-4-85535,
As described in JP-A-4-85536, JP-A-4-88533, JP-A-4-85534, and JP-A-4-172341, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded. Then, any means such as forming a coating layer by molding or spraying a water-soluble binder on the surface of the photographic processing agent that has been temporarily molded can be adopted. A method for producing a tablet processing agent is described in, for example, Japanese Patent Laid-Open No.
No. 1-61837, No. 54-155038,
It can be produced by a general method described in JP-A No. 52-88025 and British Patent No. 1213808, and the granule treating agent is, for example, JP-A-2-109042, JP-A-2-109043, JP-A-3-109043. It can be produced by a general method described in JP-A-39735 and JP-A-3-39739. Further, the powder treating agent is described in, for example, JP-A-5
4-133332, British Patent 725892, 729862 and German Patent 373386.
It can be produced by a general method as described in Japanese Patent Publication No. 1 and the like.

When the replenishing agent for the processing solution having a bleaching ability is composed of a liquid, it may be one solution or a plurality of solutions containing different components. One or two liquids are 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.

Further, the pH of the processing solution having 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 order to achieve such a pH, it is preferable in the present invention 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 acids (inorganic acid, organic acid) 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 is carried out through a conditioning 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, nitric acid compounds such as ammonium nitrate and sodium nitrate are 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. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 12 minutes, more preferably 1 minute 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. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air,
Air is preferably released into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding the aeration, the matters described on pages BL-1 to BL-2 of Z-121, Eusing Process C-41 3rd edition (1982), published by Eastman Kodak Company can be used. In the treatment using the treatment liquid having the bleaching ability of the present invention, it is preferable that stirring is strengthened,
The contents described in JP-A-3-33847, page 8, upper right column, line 6 to lower left column, line 2 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, the polyamine compounds described in JP-B-45-8836, and the like 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.

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.
The sulfinic acid compound etc. described in the specification of No. 231051 can be contained. Furthermore, various fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained. Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having a fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediamine-N, N, N'. , N '
-Tetraacetic acid, diethylenetriaminepentaacetic acid, trans-1,2
-Cyclohexanediamine-N, N, N ', N'-tetraacetic acid, 1,2-propylenediaminetetraacetic acid can be mentioned.

It is also preferable to add a buffer to the bleach-fixing solution and the fixing solution in order to keep the pH of the solution constant. For example, phosphate, or imidazole, 1-methyl-
Examples thereof include imidazoles such as imidazole, 2-methyl-imidazole and 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, and N-benzoylpiperazine.

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.

The automatic processors used in 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 type of 1,2-benzisothiazolin-3-one or its derivative. Specific examples of these compounds are shown below, but the invention is not limited thereto.

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

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

The replenisher for the solution having a bleaching ability basically contains the concentrations of the respective components calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant. C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (processing tank liquid) C _P : Consumed during processing the concentration of component V _1: amount of replenisher having bleaching ability for the light-sensitive material of 1m _² (ml) V ^2: amount carried from previous bath by the photographic material of 1 m ² (m
l) Further, the processing tank having a bleaching ability of the present invention is preferably equipped with the bleaching / regenerating apparatus described in JP-A-2-67552.

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. For bleaching and fixing solutions,
From the viewpoint of improving the desilvering property, it is preferable to use ammonium as a cation, but from the purpose of reducing environmental pollution,
It is preferable to reduce or eliminate ammonium. In the bleaching, bleach-fixing and fixing steps, JP-A-1-309
It is particularly preferable to carry out jet stirring described in No. 059. The replenishing amount of the replenishing solution in the bleach-fixing or fixing step is 100 to 1000 ml, preferably 150 to 700 ml, and particularly preferably 200 to 6 per m ² of the light-sensitive material.
00 ml.

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 bleach-fixing solution and the fixing solution, it is preferable to allow a free chelating agent which is not a metal complex to be present from the viewpoint of improving the preservability.
As these chelating agents, it is preferable to use at least one compound represented by the general formula (I) or (II) or (A) of the present invention.

With respect 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 to prepare the replenisher or from the light-sensitive material is added to the processing solution.
Although various ionic components such as potassium ions are present, in the present invention, the sodium ion concentration in the final bath of the washing and stabilizing steps is particularly preferably in the range of 0 to 50 mg / liter, particularly 0 to 20 mg / liter. Is preferred.

The rinsing amount and the replenishing amount of the stabilizing solution are the same as those 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. In the processing method of the present invention, it is preferable that the processing solution having a bleaching ability and / or the processing solution having a fixing ability contain a compound represented by the following general formula (A) or (B). General formula (A)

[0078]

Embedded image

(In the formula, Q represents a group of non-metal atoms necessary for forming a heterocycle. P represents 0 or 1. M ₄ represents a hydrogen atom or a cation.) General formula (B)

[0080]

Embedded image

(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 NR _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. )

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 are, 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.) and the like.

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

[0091]

Embedded image

(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)

[0098]

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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)

[0101]

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(In the formula, Ma has the same meaning as that in formula (A). Q ³ represents a group of atoms necessary for forming a pyridine ring or an imidazole ring, and includes an alkyl group, an amino group, an alkoxy group and 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.

[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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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, the examples given as the substituent which the ring formed by Q _b may have are applicable. 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 substituents 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 represents 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)

[0121]

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(In the formula, X _b and M _b have the same meanings as those in formula (B), respectively, and the preferable 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.

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

[0126]

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(In the formula, X _b , M _b , and R _b1 have the same _{meanings as} those in formula (Ba), respectively, and their preferable ranges are also the same. R _b2 and R _b3 are represented by the formula (B). 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. )

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

[0129]

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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.

[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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If possible, the above compound may be a conjugated isomer thereof. 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.

Preferred among the above-exemplified compounds 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 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, but the range of 6.4 to 7.7 is particularly preferable. 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 10 per 1 m ² of the light-sensitive material.
0 to 1000 ml, preferably 150 to 700 ml,
Particularly, 200 to 600 ml is preferable.

The processing solution having a fixing ability contains a sulfite as a preservative (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 processor used in the method of the present invention will be described below. In the processing machine of the photosensitive material according to the present invention, when the thickness at the gas-liquid interface of the tank cross section orthogonal to the traveling direction of the photosensitive material in this processing tank is W, 0.1 ≦ W It is characterized in that the condition of ≦ 2 cm is satisfied, and more preferably 0.3 ≦ W ≦ 1.
cm. As described above, by reducing the thickness of the tank cross section at the gas-liquid interface, it is possible to reduce the area in which the processing liquid comes into contact with air and prevent the processing liquid from deteriorating. As described above, the known processing liquid forms a crystalline deposit on the inner wall or member of the processing tank near the gas-liquid interface, or a tar-like product that is considered to be caused by the deterioration of the carried-in developer component is attached. Easy to use, there is a possibility that stains and scratches may occur at the edge portion of the photosensitive material when a processing device having a narrow processing path is used, but the compound iron (III) having the specific structure is used.
These problems are solved by combining with a processing solution having a bleaching ability containing a complex salt. As a preferred mode of the processor that satisfies the above conditions, a processing tank (processing tank) in which a processing liquid for processing a photosensitive material is stored and formed in a V shape, and a part of an inner wall surface of the processing tank are formed. And a processing unit for processing a photosensitive material, which has a guide portion for guiding the photosensitive material and forming a transporting path of the photosensitive material, and a transporting unit which is disposed in the processing tank and transports the photosensitive material along the transporting path. For example, the photosensitive material processing device described in Japanese Patent Application Laid-Open No. 2-67552 can be used in which the tank forms a slit-shaped processing path. Further, by using such a thin tank cross section, V / L ≦ when the tank volume of the processing section is V milliliter and the path length of the photosensitive material from the inlet to the outlet of the processing section is L centimeter.
The processing tank may satisfy the condition of 25. The tank capacity (V) here means the capacity of the processing tank in the portion through which the photosensitive material passes, and excludes the capacity of the sub-tank for adjusting the liquid amount of the circulation system, temperature adjustment, aeration and the like. L means the path length of the processing section, and means the path length from the contact of the photosensitive material with the processing liquid in the processing tank to the discharge from the processing liquid. It is preferable that the relationship of V / L ≦ 25 be satisfied between the tank capacity (V) milliliter and the path length (L) centimeter,
More preferably, 1 ≦ V / L ≦ 20. The tank volume (V) is preferably in the range of 50 to 5000 ml, and more preferably 100 to 3000 ml from the viewpoint of the effect. The path length (L) varies depending on the type of processing liquid and the time required for processing, but is generally preferably 2 to 200 cm, and more preferably 4 to 120 cm.

A sectional view of an embodiment of a suitable photosensitive material processing apparatus that can be used in the method of the present invention is shown in FIG. As shown in FIG. 1, the photosensitive material processing apparatus 10 according to the present embodiment is provided with a slit-shaped processing path 12 in order to reduce the processing liquid amount and perform processing easily. The slit-shaped processing path 12 used here is a cross section obtained by cutting a path in a processing tank through which a photosensitive material passes at a right angle to the traveling direction of the photosensitive material, and a cross-sectional thickness (width direction of the photosensitive material) of the cross section. Means a so-called slit type. The slit shape may be rectangular or oval.
Further, in the processing tank, when the curvature formed by the processing path at the bottom of the processing tank is R, 10 ≦ R ≦ 70
mmφ is preferable, and 20 ≦ R ≦ 50.
It is preferably mmφ. When R is large, the processing apparatus becomes large, and when R is small, there is a possibility that conveyance failure of the photosensitive material occurs.

The path length of the processing path 12 is determined according to the type of the processing liquid and the time required for the processing (immersion time in the processing liquid). The slit-shaped processing path 12 may be provided in all the processing tanks of the photosensitive material processing apparatus, or in some processing tanks,
Other processing tanks may be the same processing tanks as in the past.
In this photosensitive material processing apparatus 10, all processing tanks are provided with slit-shaped processing paths 12, and a developing tank (color developing tank) 14 having a path length corresponding to the processing time and a bleaching tank 16 are adjacent to each other. The photosensitive material placed and developed in the developing tank 14 is sent to the bleaching tank 16 which is the next processing tank by a pair of conveying rollers 18. Further, the structure is such that four rinsing tanks 20 are arranged adjacent to the bleaching tank 16. The developing solution is stored in the developing tank 12, and the bleaching solution is stored in the bleaching tank 14.
A rinse liquid is stored in each of the rinse tanks 16. If desired, the bleaching tank 14 may be mixed with a processing solution having a fixing ability to form one bleaching / fixing tank. Therefore, the developing tank 14 of the photosensitive material processing apparatus 10
When the photographed negative film F is inserted from the open end side of the developing tank 14, the developing tank 14, the bleaching tanks 16 and 4 are processing tanks.
The negative film is soaked in the two rinse tanks 20 in sequence and the negative film is developed. Further, a drying zone 21 is arranged on the open end side of the last rinse tank (4) 20, and the negative film coming out of the rinse tank 20 is inserted into this drying fan to be dried.

Next, FIG. 2 shows a sectional view of a second embodiment of a suitable photosensitive material processing apparatus which can be used in the method of the present invention. As shown in FIG. 2, the photosensitive material processing apparatus 22 according to the present embodiment is provided with a slit-shaped processing path 12 for reducing the processing liquid amount and simply processing. The path length of the processing path 12 is determined according to the type of processing liquid and the time required for processing. The slit-shaped processing path 12 may be provided in all the processing tanks of the photosensitive material processing apparatus, or in some processing tanks,
Other processing tanks may be the same processing tanks as in the past.
In this photosensitive material processing device 22, all processing tanks are provided with slit-shaped processing paths 12, and a developing tank 24 and a bleaching tank 26 having a path length according to the processing time are arranged adjacent to each other. The photosensitive material developed in 24 is sent to a bleaching tank 26 which is the next processing tank by a pair of conveying rollers 18. Furthermore, adjacent to the bleaching tank 26,
It has a structure in which two stabilizers 28, a washing tank 30, and three stabilizing tanks 32 are respectively arranged. And the developing tank 2
4, the bleaching solution is stored in the bleaching tank 26, the fixing solution is stored in each of the two fixing tanks 28, and the rinsing water is stored in the washing tank 30. A stabilizing solution is stored in each stabilizing tank 32. If desired, the bleaching tank 26 and the fixing tank 28 may constitute one bleaching / fixing tank. Therefore, when the negative film having been photographed is inserted from the open end side of the developing tank 24 of the photosensitive material processing device 22, these developing tanks 2 which are processing tanks are inserted.
4, bleaching tank 26, two fixing tanks 28, washing tanks 30 and 2
The negative film is sequentially dipped in one of the stabilizing tanks 32 to develop the negative film. Also, the last stabilizing tank 32
A drying zone 34 is disposed on the open end side of the negative film, and the negative film coming out of the stabilizing tank 32 is inserted into the drying zone 34 and dried.

From the above, the bleaching tanks 16 and 26 are formed as slit-shaped tanks, and the portions of the developing tanks 16 and 26 that are the gas-liquid interface, for example, the position where the negative film starts to come into contact with the bleaching solution (processing tank) When the thickness of the tank cross section orthogonal to the traveling direction of the photosensitive material in the slit-shaped tank is W at the position where the negative film is discharged from the bleaching solution (inlet) or the position where the negative film is discharged from the inside of the bleaching solution, W is 0.1. ≤W≤2c
The contact area with the air of the bleaching solution is reduced to m. Further, slit-shaped spaces are similarly formed inside other processing tanks such as the developing tanks 14, 24, the fixing tank 28, and the rinse tank 20, and the processing tanks are arranged so as to be joined to each other.

Further, in the method of the present invention, the transport speed of the light-sensitive material is preferably 0.1 m to 5 m / min, more preferably 0.2 m to 3 m / min, and 0.
Particularly preferably, it is 3 m and 1.5 m. The method of conveying the photosensitive material applied to the processor used in the method of the present invention is not particularly limited, and a known conveying method, for example, a roller type conveying method for conveying the photosensitive material by the nip force of a pair of conveying rollers, a drum. It is possible to select a drum processing method, a so-called leader trailer transfer method, or the like, in which the photosensitive material is inserted, conveyed, and sent out in the processing liquid kept in a narrow space by the rotation of the above. By using such a processing apparatus, the negative film transport path is constituted by the bleaching tanks 16 and 26 having the slit-shaped processing paths and the processing path 12 having an extremely thin thickness. The area of the gas-liquid interface of the bleaching solution is reduced, and the bleaching solution in the bleaching tank can be reduced in quantity, and a large amount of replenishing solution is not required to maintain the characteristics of the bleaching solution. 10, 22
Running cost is reduced. Further, by reducing the amount of the bleaching solution in the above structure, the processing tank for storing the bleaching solution can be downsized, and accordingly, the photosensitive material processing apparatuses 10 and 22 can be downsized. Then, the developing tanks 14 and 2
Other processing tanks, such as 4 and the rinse tank 20, will operate in the same manner as above.

Next, the color developing solution used in the method of the present invention will be described. The color developing solution is described in JP-A-4-1217.
The compounds described in No. 39, page 9, upper right column, line 1 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. It is preferable that the color developing solution contains a color developing agent in an amount of 0.01 to 0.08 mol / liter, particularly 0.015 to 0.06 mol / liter, and further 0.02 to 0. It is preferably contained in an amount of 05 mol / liter. The replenisher for the color developing solution preferably contains 1.1 to 3 times this value.

The color developer contains a pH buffer 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 performed, color development is usually performed after black and white 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 level, 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 above 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.

The present invention can be applied to the processing of any photosensitive material. The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing this photosensitive material are Those described in the following patent publications, particularly European Patent EP0,355,660A2 (JP-A-2-139544) are preferably used. The places where the photographic components are described in the above publications are shown as a list.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5]

Next, the photosensitive material used in the method of the present invention will be described in detail. As the silver halide emulsion used in the present invention, emulsions having various halogen compositions such as silver iodobromide, silver iodochloride, silver iodochlorobromide, silver bromide and silver chloride can be used. In particular, it is preferable to have at least one emulsion layer containing silver halide grains of which silver chloride is 90 mol% or more. More preferably, it is an emulsion containing silver halide grains in which 95 to 99.9 mol% or more, and further preferably 98 to 99.9 mol% or more, are silver chloride, and all layers are 98 to 99.9 mol%. A silver chlorobromide emulsion consisting of the above silver chloride is particularly preferable. The amount of coated silver is not particularly limited and is preferably applied to a light-sensitive material of about 0.2 to 15 g / m ² .
It is preferably about 0.4 to 5.0 g / m ² .

Further, when the light-sensitive material used in the present invention is a color light-sensitive material, various couplers can be contained, and the details are as shown in Table 2. Further, as the cyan coupler, in addition to the diphenylimidazole-based cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine-based cyan coupler described in European Patent 333,185A2 (among others, listed as specific examples). 4-equivalent coupler of coupler (42) with a chlorine-eliminating group to make 2-equivalent, or coupler (6)
And (9) are particularly preferable) and the cyclic methylene cyan couplers described in JP-A-64-32260 (specifically, coupler examples 3, 8, and 34 listed as specific examples) are also preferably used.

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is used for the purpose of improving the sharpness of an image and the like, as disclosed in European Patent Publication EP 0,357,490A2, No. 27.
To page 76, a dye that can be decolorized by processing (among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more,
It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a divalent to tetravalent alcohol (eg, trimethylolethane). Further, in the light-sensitive material according to the present invention, a layer containing a coupler has a European published patent EP
It is preferred to use color image-storing compounds such as those described in 0,277,589 A2. In particular, combination use with a pyrazoloazole-based magenta coupler is preferable.

That is, the compound (F) which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or after the color development processing. It is possible to use the compound (G), which forms a chemically inactive and substantially colorless compound by being chemically bonded to the remaining oxidized product of the aromatic amine color developing agent, simultaneously or alone, for example, after the treatment. It is preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or the oxidation product thereof during storage. Further, in the light-sensitive material according to the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-271247 is used.
It is preferable to add an antifungal agent as described in No.

The effect of the present invention can be remarkably obtained when the dry film thickness of the silver halide color photographic light-sensitive material used in the present invention, excluding the support, is 25 μm or less. More preferable film thickness, particularly preferably 6 to 17 μm
m. These film thicknesses can be reduced by reducing the amount of gelatin, the amount of silver, the amount of oil, the amount of couplers, etc., but it is most preferable to reduce the amount of gelatin.
Here, the film thickness was measured after leaving the sample for 2 weeks at 25 ° C. and 65% RH.
It can be measured by a conventional method.

In the silver halide color photographic light-sensitive material used in the present invention, the film swelling degree of the photographic layer is 1.5 to.
A value of 4.0 is preferable from the viewpoint of improving stain and improving image storability. Particularly, in the range of 1.5 to 3.0, a further effect can be obtained. The swelling degree of the present invention means
A value obtained by dividing the film thickness of the photographic layer after dipping the color light-sensitive material in distilled water at 33 ° C. for 2 minutes by the film thickness of the dried photographic layer.

The photographic layer means a hydrophilic colloid group layer including at least one light-sensitive silver halide emulsion layer and having a water-permeable relationship with this layer. It does not include the back layer provided on the side opposite to the photographic photosensitive layer across the support. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and includes an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like in addition to the silver halide emulsion layer.

Any method may be used to adjust the degree of swelling described above. For example, the amount and type of gelatin used in the photographic film, the amount and type of hardener, or the drying after coating the photographic layer. It can be adjusted by changing the conditions or the aging conditions. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives;
Various synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. Can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. As the gelatin derivative, those obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, and maleimide compounds are used. .

The gelatin / graft polymer may be obtained by grafting onto acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, homopolymers or copolymers of vinyl monomers such as acrylonitrile and styrene. It can be used. In particular, a polymer having a certain degree of compatibility with gelatin, for example, a graft polymer with a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable. Examples of these are US Pat. Nos. 2,763,625 and 2,832.
No. 1,767, No. 2,956,884 and the like. Representative synthetic hydrophilic polymeric substances are, for example, West German Patent Application (OLS) 1,312,708, US Pat.
No. 620,751, No. 3,879,205, and Japanese Examined Patent Publication No. 43-7561.

Examples of the hardener include chromic acid (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), Dioxane derivatives (2,3-dihydrodioxane etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s
-Triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis [β- (vinylsulfonyl) propionamide] and the like), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), Isoxazoles, dialdehyde starch, 2
-Chlor-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Particularly preferred hardeners are aldehydes, active vinyl compounds and active halogen compounds.

As a support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used.
In order to further improve the sharpness, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.35 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set it in the range of 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726 upon exposure. As a result, light color mixing is removed, and color reproducibility is significantly improved.

The processing method of the present invention can be applied to various photosensitive materials. For example, a color negative film, a color negative paper, a color reversal paper, an auto positive paper, a color reversal film, a negative film for movies, a positive film for movies, a film for plate making such as an X-ray film, a lith film, a black and white negative film, and the like can be given. Especially, application to a color negative film or a color negative paper is preferable.

In the case of a color negative, it is particularly preferable to have a magnetic recording layer on the support. 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 a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder.The magnetic particles include ferromagnetic iron oxide such as γFe ₂ O ₃ and Co. Deposited γFe ₂ O ₃ , Co deposited 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.
Of these, Co-deposited ferromagnetic iron oxide such as Co-deposited γFe ₂ O ₃ is preferable. 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
And 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. Further, magnetic particles having a surface coated with an inorganic or organic material described in JP-A-4-259911 and 5-81652 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.

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EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 A color photographic paper was prepared by the method described below. (Preparation of Support) Titanium dioxide (30 wt%) was added to low density polyethylene (MRF = 3), and zinc stearate was added at a ratio of 3.0 wt% with respect to the amount of titanium dioxide. (1) (trade name, manufactured by Daiichi Kasei) and kneaded in a Banbury mixer, and then used for melt extrusion. Titanium dioxide has a particle size of 0.
15 to 0.35 μm, the coating amount of hydrated aluminum oxide in the form of Al ₂ O ₃ was 0.1.
75% by weight was used. After subjecting a paper substrate having a basis weight of 170 g / m ² to a corona discharge treatment of 10 kVA, a polyethylene composition containing 30% by weight of the above titanium dioxide and a polyethylene composition containing 18% by weight of titanium dioxide and 30% by weight of titanium dioxide prepared in the same manner. % Of polyethylene containing ultramarine blue using a multi-layer extrusion coating die
Melt extrusion was performed at 20 ° C., and the thickness of the upper layer was 2 μm (18% by weight of titanium dioxide), the intermediate layer was 21 μm (30% by weight), and the lower layer was 10 μm (0% by weight) (the lower layer means the paper substrate side). A polyethylene laminate layer was provided. The surface of this polyethylene layer was subjected to glow discharge treatment.

(Preparation of Color Printing Paper) Various photographic constituent layers were coated on the above reflective support to prepare a multilayer color printing paper having the following layer constitution. The coating solution was prepared as follows.

Preparation of coating liquid for third layer Magenta coupler (ExM) 40.0 g, ultraviolet absorber (UV-2) 40.0 g, color image stabilizer (Cpd-2)
7.5 g, 25.0 g of color image stabilizer (Cpd-5), 2.5 g of color image stabilizer (Cpd-6), color image stabilizer (Cpd-5)
7) 20.0 g, 2.5 g of color image stabilizer (Cpd-8),
5.0 g of the color image stabilizer (Cpd-10) was added to a solvent (Sol).
v-3) 32.5 g, solvent (Solv-4) 97.5
g, solvent (Solv-6) 65.0 g and ethyl acetate 1
This was dissolved in 10 ml, and this solution was emulsified and dispersed in 1500 g of a 7% gelatin aqueous solution containing 90 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion A-1. On the other hand, silver chlorobromide emulsion B-1 (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.55 μm and small size emulsion of 0.39 μm (silver molar ratio). Coefficient of variation of grain size distribution is 0.08 and 0.06, respectively.Each size emulsion contained 0.8 mol% of silver bromide locally on a part of the surface of the grain based on silver chloride. To 0.1 mg of potassium hexachloroiridium (IV) and 0.1 mg of potassium ferrocyanide were prepared. This emulsion is
The green-sensitive sensitizing dyes D, E, and F shown below are 3.0 × 10 ⁻⁴ mol, 4.0 × 10 ⁻⁵ mol, and 2.0 × 10 mol per mol of silver, respectively, for a large-sized emulsion. ^-4 moles, or 3.6 × each mole of silver for small size emulsions
After adding 10 ^-4 mol, 7.0 × 10 ^-5 mol, 2.8 × 10 ^-4 mol, a sulfur sensitizer and a gold sensitizer were added in the presence of a decomposed product of nucleic acid to optimize the chemistry. Sensitization was performed. The above emulsified dispersion A-1 and this silver chlorobromide emulsion B-1 were mixed and dissolved to prepare a third layer coating solution having the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

Other coating solutions for the first to seventh layers were prepared in the same manner as the coating solution for the third layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Moreover, Cpd-12 is added to each layer.
And Cpd-13 were added so that the total amounts were 25.0 mg / m ² and 50.0 mg / m ² , respectively. The size of the silver chlorobromide emulsion in each light-sensitive emulsion layer was adjusted in the same manner as in the silver chlorobromide emulsion B-1, and the spectral sensitizing dyes shown below were used. Blue-sensitive emulsion layer

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(1.4 × 10 ⁻⁴ mol each for a large-sized emulsion and 1.7 × 10 ⁻⁴ mol for a small-sized emulsion, per mol of silver halide). ) Green-sensitive emulsion layer

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(Sensitizing dye D per mol of silver halide, 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and Sensitizing dye E per mol of silver halide is 4.0 × 10 ⁻⁵ mol for large-sized emulsion, 7.0 × 10 ⁻⁵ mol for small-sized emulsion, and sensitized. Dye F is 2.0 × 1 per mol of silver halide for a large-sized emulsion.
0 ^-4 mol, or 2.8 x 10 ^-4 for small size emulsions
Mole was added. ) Red-sensitive emulsion layer

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(Sensitizing dye G per mol of silver halide was 4.0 × 10 ^-5 for a large-sized emulsion.
5.0 × each for moles and small emulsions
10 ^-5 mol, sensitizing dye H per mol of silver halide,
5.0 × 10 ⁻⁵ mol for large size emulsion and 6.0 × 1 mol for small size emulsion.
0 ^-5 mol was added. Further, the following compounds were added to the red-sensitive silver halide emulsion in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

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For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl) is used.
-5-Methylcaptotetrazole was added in an amount of 8.5 x 10 ^-4 mol, 3.0 x 10 ^-3 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mole and 2 × 10 ^-4 mole, respectively, per mole of silver halide. × 10 ^-4 mol was added.

Further, in order to prevent irradiation, the following dyes were added to the emulsion layer (the amount in parentheses represents the coating amount).

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(Layer Structure) The layer structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support (A) The resin layer on the first layer side contains a bluish dye (ultramarine).

First Layer (Blue Sensitive Emulsion Layer) Silver Chlorobromide Emulsion A-1 0.27 (cubic, 5: 5 mixture of large size emulsion with average grain size 0.88 μm and small size emulsion with 0.70 μm) (Molar ratio of silver) Coefficients of variation of grain size distribution are 0.08 and 0.10 respectively, 0.3 mol% of silver bromide and a part of grain surface based on silver chloride for each size emulsion. 0.1 mg of potassium hexachloroiridium (IV) and 0.1 mg of potassium ferrocyanide were added to the inside of the grain and the silver bromide localized layer.) Gelatin 1.22 Yellow Coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-) 5) 0.01 solvent (Solv-1 0.13 solvent (Solv-5) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 0.90 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.25 solvent (Solv-8) 0.03

Third Layer (Green Sensitive Emulsion Layer) The Silver Chlorobromide Emulsion B-1 0.13 Gelatin 1.45 Magenta Coupler (ExM) 0.16 UV Absorber (UV-2) 0.16 Color Image Stability Agent (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.10 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.08 Color image stabilizer ( Cpd-8) 0.01 Color image stabilizer (Cpd-10) 0.02 Solvent (Solv-4) 0.39 Solvent (Solv-5) 0.26

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.68 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.18 Solvent (Solv-8) 0.02

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C-1 0.18 (cubic, large size emulsion C having average grain size 0.50 μm and small size emulsion C having 0.41 μm 1: 4 mixture (silver molar ratio) .The coefficient of variation of the grain size distribution is 0.09 and 0.11, respectively.Each size emulsion contains 0.8 mol% of silver bromide on the surface of grains based on silver chloride. It was partially contained locally, and further, 0.1 mg of potassium hexachloroiridium (IV) was added to the inside of the grain and the silver bromide localized layer, and 0.1 mg of potassium ferrocyanide was added. 0.80 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer Cpd-8) 0.01 Color Image Stabilizer (Cpd-9) 0.02 Color Image Stabilizer (Cpd-10) 0.01 solvent (Solv-1) 0.01 solvent (Solv-7) 0.22

Sixth Layer (Ultraviolet Absorbing Layer) Gelatin 0.48 Ultraviolet Absorber (UV-1) 0.38 Color Image Stabilizer (Cpd-5) 0.01 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-9) 0.05

Seventh Layer (Protective Layer) Gelatin 1.01 Acrylic Modified Copolymer of Polyvinyl Alcohol (Degree of Modification 17%) 0.04 Liquid Paraffin 0.02 Surfactant (Cpd-11) 0.01

[0207]

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The color photographic paper produced by the above method was processed by two types of roller transport type automatic processors. Automatic developing machine (photosensitive material processing device) used at this time 1
The structure of 0 is as shown in FIG. The photosensitive material was conveyed at a speed of 1.2 m / min and processed at a rate of 1 m ² per day for 3 weeks (5 days per week). The tank capacity and V / L value of each tank are shown in the table below. Here, the thickness W value of the processing tank of the processing machine (1) is 0.8 cm, and the width is 13.0 cm.
The thickness W value of the processing tank portion of the processing machine (2) was 1.6 cm and the width was 13.0 cm.

The processing steps and processing liquid compositions are shown below. (Processing process) Processing machine (1) Processing machine (2) Processing process time Temperature Replenishment amount * Tank capacity (V / L) Tank capacity (V / L) Color development 45 seconds 38.5 ℃ 45 ml 2.0 liters (23.4) 1.0 liters (11.7) Bleach and fix 45 seconds 38.0 ℃ 35 ml 2.0 liters (23.4) 1.0 liter (11.7) Rinse (1) 22 seconds 38.0 ℃ ―― 1.0 liter (25.0) 0.5 liters (12.5) Rinse (2) 22 seconds 38.0 ℃ ― ― 1.0 liter (25.0) 0.5 liter (12.5) Rinse (3) 22 seconds 38.0 ℃ ―― 1.0 liter (25.0) 0.5 liter (12.5) Rinse (4) 22 seconds 38.0 ℃ 175 ml 1.0 liter (25.0) 0.5 liter (12.5 ) Drying 40 seconds 80 ° C * Replenishing amount per 1 m ^{2 of} light-sensitive material Rinsing is a countercurrent method from (4) to (1). Also,
The amount brought into the next bath was 40 ml per 1 m ² of the light-sensitive material. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

(Color developer) Tank solution Replenisher Cation-exchanged water 800 ml 800 ml Dimethylpolysiloxane-based surfactant (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g 0.1 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g 4 1,5-Dihydroxybenzene-1,3-disulfonic acid sodium 0.5g 0.5g triethanolamine 12.0g 12.0g potassium chloride 12.0g-potassium bromide 45mg-triazinyl-4,4-diaminostilbene-based fluorescence enhancement Whitening agent (Hakkor OW-10EX / Showa Chemical Industry) 1.0g 3.0g Sodium phosphite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.0g 15.0g Triisopropyl Naphthalene (β) sodium sulfonate 0.1g 0.1g N-ethyl-N (β-methanesulfonamido ethyl) -3-methyl -4-Aminoaniline ・ 3/2 sulfuric acid ・ monohydrate 5.0 g 18.0 g Potassium carbonate 27.0 g 27.0 g Water was added to 1000 ml 1000 ml pH (at 25 ° C./KOH or sulfuric acid) 10.15 12. 6

(Bleach-fixing solution) Tank solution Replenishing solution Water 700 ml 700 ml Ammonium thiosulfate (750 g / liter) 100 ml 100 ml Ammonium sulfite 35.0 g 100 g Chelating agent described in Table 1 0.11 mol 0.33 mol Table 1 Additive 0.05 mol 0.15 mol Iron (III) nitrate / decahydrate 0.1 mol 0.3 mol m-carboxybenzenesulfinic acid 0.2 mol 0.5 mol Imidazole 8.0 g 18.0 g Water In addition 1000 ml 1000 ml pH (25 ℃ / sulfuric acid or ammonia water) 7.00 6.00

(Rinse) Tank liquid and replenisher are common Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Table 6 below shows the results of observing the light-sensitive material processed by the above method and evaluating stains and scratches on the light-sensitive material and color unevenness in the image area.

[0219]

[Table 6]

As shown in Table 6, by using the treatment liquid containing the compound of the present invention, the thickness W of the treatment tank was about 0.
Doesn't stain or scratch the light-sensitive material even when processed with 8 cm and 1.6 cm processors, or
It was extremely small, and it was revealed that the obtained image was an excellent processing method with no color unevenness. On the other hand, in the method of the comparative example in which a conventional chelate compound was added using these processing devices, stains and scratches were generated on the photosensitive material, color unevenness was likely to occur, and the level was not practically usable.

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

(2) Coating of Undercoat Layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides, and then gelatin 0.1 g / m ² and sodium α-on each side. Sulfodi-2-ethylhexyl succinate 0.01g / m ² , salicylic acid 0.04g / 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 After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as a back layer on one surface of the support.

(3-1) Coating of Antistatic Layer A dispersion of fine particles of tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm and a specific resistance of 5 Ω · cm (secondary agglomerated particle diameter of about 0.08 μm). 0.2 g / m ² , gelatin 0.05 g / 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 (polymerization degree 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 aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06g / m ² of 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. .

Onto the above-mentioned support having an undercoat layer formed thereon, each layer having the following composition was multi-layer coated 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

11th 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

Twelfth 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

13th 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

Fourteenth 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.

[0242]

[Table 7]

In Table 7, (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. The structures of the compounds used are shown below.

[0246]

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[0247]

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[0260]

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[0261]

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The sample 101 prepared as described above is set to 24 mm
The sheet is cut into a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. 32 sets of these two sets
U.S. Pat. No. 5,296,887
It was housed in a plastic film cartridge described in Figs.

This sample 101 was replaced with a head gap of 5 μm.
m, the number of turns was 50, and it was mounted in a camera having a magnetic recording device made of a permalloy material, and digital saturation recording was performed at a recording wavelength of 50 μm.

[0264] The above sample 101 was treated with 0.5 m ² per day.
Processing was performed for one month (5 days per week) using the automatic processor 22 shown in FIG. At this time, the conveying speed of the photosensitive material was 50 cm / min, the tank thickness W value was 0.8 cm, and the width was 4.1 cm.

A developing tank 24, a bleaching tank 26, two fixing tanks 28, a washing tank 30 and two stabilizing tanks 32, each having a slit-like processing which can be preferably used in the processing method of the present invention shown in FIG. Processing was performed in the following steps using the automatic developing machine (photosensitive material processing device) 22.

The processing steps and processing liquid compositions are shown below. (Processing process) Processing time Time Temperature Replenishment amount * Tank capacity (V / L) Color development 3 minutes 50 seconds 38.0 ℃ 260 ml 0.5 liter (3.3) Bleach 50 seconds 38.0 ℃ 130 ml 0.2 liter (4.8) Fixing (1) 50 seconds 38.0 ℃ -0.2 liters (4.8) Fixing (2) 50 seconds 38.0 ℃ 200 ml 0.2 liters (4.8) Washing with water 30 seconds 38.0 ℃ 450 ml 0.15 liters (6.0) Stable (1) 20 seconds 38.0 ℃ -0.15 liters ( 9.0) Stable (2) 20 seconds 38.0 ° C 390 ml 0.15 liter (9.0) Dry 1 minute 30 seconds 60 ° C * Replenishment amount per 1 m ^{2 of} light-sensitive material Stabilizer and fixer are from (2) to (1) Is a flow system,
All the overflow of the washing water was introduced into the fixing bath (2). The fixer is also connected from (2) to (1) by a countercurrent pipe. The amount of the color developing solution brought into the bleaching step, the amount of the bleaching solution brought into the fixing step, and the amount of the fixing solution brought into the water washing step were 65 ml, 52 ml and 52 ml per 1 m ² of the light-sensitive material, respectively. .
The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. A film processor FP360B manufactured by Fuji Photo Film Co., Ltd. was used as a comparative processor. The structure of the tank bath of this comparative processor, the tank capacity and the V / L value are shown in the table below. The thickness W value of the treatment tank was 2.5 cm. The conveying speed of the light-sensitive material was 47 cm / min.

(Treatment process) Treatment process time Temperature Replenishment amount * Tank capacity (V / L) Color development 3 minutes 50 seconds 38.0 ° C 260 ml 11.5 liters (82) Bleach 50 seconds 38.0 ° C 130 ml 4.0 liters (102) Fixing (1) 50 seconds 38.0 ℃ -4.0 liters (102) Fixing (2) 50 seconds 38.0 ℃ 200 ml 4.0 liters (102) Washing with water 30 seconds 38.0 ℃ 450 ml 3.0 liters (128) Stable (1) 20 seconds 38.0 ℃- 3.0 liters (191) Stable (2) 20 seconds 38.0 ℃ 390 ml 3.0 liters (191) Dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 1 m ^{2 of} light-sensitive material

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonic acid dinatrium 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Hydroxylamine sulfate 5.0 6.5 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 sulfate 4.5 6.5 Water was added to 1.0 liter 1.0 liter pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.21

(Bleaching Solution) Tank Solution Replenisher Compound of the present invention (I-1) 0.24 mol 0.4 mol Compound of the present invention (I-15) 0.12 mol 0.2 mol Iron nitrate (III) 9 Hydrate 0.24 mol 0.4 mol Ammonium bromide 0.4 mol 0.6 mol Inventive compound (A-7) 0.05 mol 0.12 mol Glycolic acid 0.7 mol 1.2 mol Succinic acid 0.3 mol 0.5 mol Add water 1000 ml 1000 ml pH (at 25 ° C nitric acid or ammonia water) 4.0 3.5

(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 Ethylenediaminetetraacetic acid 13.0 39.0 Imidazole 7.0 21.0 Add water 1000 ml 1000 ml pH (adjust with ammonia water and acetic acid) 7.4 7.5

(Washing Water) Common to Tank Liquid and Replenisher Tap water is H type strong acid 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.

(Stabilizing Solution) Tank Solution and Replenishing Solution 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 added 1 liter pH (adjusted with ammonia water and nitric acid) 8.5

Table 8 shows the results of observing the light-sensitive material processed by the above method and evaluating stains and scratches on the light-sensitive material and color unevenness in the image area.

[0274]

[Table 8]

As shown in Table 8, by using the treatment liquid containing the compound of the present invention, the thickness W of the treatment tank was reduced to 0.
Even if the treatment is performed using a small treatment machine with a reduced treatment liquid of 8 cm, the treatment tank has a thickness W of 2.5 cm compared with a treatment machine that requires a normal treatment liquid amount. It was clarified that the processing method was excellent, and the obtained image was free from stains and scratches on the light-sensitive material, and the obtained image had no color unevenness.

[0276]

According to the method of processing a silver halide color photographic light-sensitive material of the present invention, the amount of processing liquid can be reduced, and even if it is processed by a slit developing machine which can be easily downsized, It has an excellent effect that the photosensitive material is not likely to be stained or scratched.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a photosensitive material processor having a developing layer, a bleaching layer, and four rinse tanks, each having a slit-shaped processing path that can be used in the processing method of the present invention.

FIG. 2 is a schematic cross-sectional view showing a photosensitive material processor having a developing layer, a bleaching layer, two fixing tanks, a water washing tank and two stabilizing tanks, each having a slit-shaped processing path that can be used in the processing method of the present invention. Is. 10 Automatic Developing Machine (Photosensitive Material Processing Device) 12 Slit-shaped Processing Path 14 Developing Tank 16 Bleaching Tank 20 Rinsing Tank 22 Automatic Developing Machine (Photosensitive Material Processing Equipment) 24 Developing Tank 26 Bleaching Tank 28 Fixing Tank 30 Washing Tank 32 Stabilizing Tank

[Procedure amendment]

[Submission date] March 13, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

Title: Processing method of silver halide color photographic light-sensitive material

[Claims]

Embedded image (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)

Embedded image (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.

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

Embedded image (In the formula, Q _b represents a nonmetallic atom group 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, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. ). M _b represents a hydrogen atom or a cation. )

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material), and particularly to a processing solution having a bleaching ability for a light-sensitive material. The present invention relates to a method of processing in a slit-shaped processing path by using.

[0002]

2. Description of the Related Art Generally, a photosensitive material is developed by sequentially passing through a rectangular parallelepiped processing tank containing a processing solution. On this occasion,
The photosensitive material is processed by immersing it in a large amount of processing liquid in order to obtain a uniform and uniform finish performance.However, if a large amount of processing liquid is stored in the processing tank, the amount of photosensitive material to be processed will increase. Especially when the amount is small, the exchange rate of the liquid in the processing tank decreases,
This has been a cause of fluctuations in the performance of the processed light-sensitive material, such as deterioration of the processing liquid over time and fluctuations in composition due to concentration. In order to improve that, in the photosensitive material processing apparatus, the thickness of the processing tank is reduced, the capacity of the processing tank is significantly reduced, the exchange rate of the tank solution is increased, and the stability of the processing solution is improved, or the size of the processing solution is reduced. Proposals that enable the design of processors are U.S. Patents 5,311,325, 5,420,659,
No.5,386,261, Shokai 63-148944, Kaikaidai 2-69331,
JP-A 1-129253, 3-119846, 2-103043, 2-2301
46. However, at present, as a bleaching agent contained in a processing solution having a bleaching ability,
Ethylenediaminetetraacetic acid (EDTA) and 1,3-propanediamine
Iron (III) complex salts consisting of chelating agents such as -N, N, N ', N'-tetraacetic acid (1,3-PDTA) are widely used, but the treatment liquid containing them is treated near the gas-liquid interface. A development process with a slit-like processing path as described above, in which a tar-like product, which is considered to be caused by the deterioration of the developer components brought into the tank, tends to form crystalline precipitates on the inner wall or members of the tank. Since the machine has a narrow passage (processing path) through which the photosensitive material passes, it is easy for the photosensitive material and the wall surface of the processing path to come into contact with each other. If processing is continued for a long time, the processed photosensitive material, especially the edges, will become dirty and scratched. There was a problem that there is a risk of

[0003]

Therefore, according to the present invention, the amount of processing liquid can be reduced, and even if the processing is carried out by a slit developing machine which can be easily miniaturized, the photosensitive material is stained or scratched. It is an object of the present invention to provide a method of processing a silver halide color photographic light-sensitive material without fear.

[0004]

The present invention relates to a method of processing a silver halide color photographic light-sensitive material with a processing solution having a bleaching ability after color development, and the processing solution having the bleaching ability is represented by the following general formula (I ) Or (II) of the compound iron (II
I) In a tank of a processing section containing a processing solution containing at least one kind of complex salt and having the bleaching ability, the thickness at the gas-liquid interface of the tank cross section orthogonal to the traveling direction of the photosensitive material is W. And 0.1 ≤ W ≤ 2 cm
Was achieved by processing in a treatment tank which is Further, it was also confirmed that the effect of unexpectedly reducing the processing unevenness was further increased.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Regarding a processing solution having a bleaching ability, which contains an iron (III) complex salt of a compound represented by the above general formula (I) or (II), European Patent Nos. 430,000 and 520,457 are cited.
No. 567,126, No. 588,289, No. 591,934, etc., but none of these specifications is able to find the recognition of the domain of the present invention. General formula (I)

[0006]

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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)

[0008]

[Chemical 6]

(In the formulae, 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. 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.)

In the present invention, the light-sensitive material is processed with a color developing solution, desilvered, and then washed with water and / or processed with a stabilizing solution. 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 bleaching ability in the present invention 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. Say. Specific examples of the desilvering process in the present invention are shown 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 Optionally, a water washing step may be provided between these treatments.

First, 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,
Examples include p-methylphenyl and the like. ), An alkoxy group (preferably having 1 to 8 carbon atoms, more preferably having 1 carbon atom)
To 6, particularly preferably 1 to 4 carbon atoms, for example, methoxy, ethoxy and the like. ), An aryloxy group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably having 6 to 8 carbon atoms, such as phenyloxy, etc.), and an acyl group (preferably carbon atom). Number 1 to 12, more preferably 2 to 1 carbon atoms
0, particularly preferably 2 to 8 carbon atoms, such as acetyl. ), An alkoxycarbonyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 1 carbon atoms)
0, particularly preferably 2 to 8 carbon atoms, such as methoxycarbonyl. ), An acyloxy group (preferably having 1 to 12 carbon atoms, more preferably having 2 carbon atoms)
10 to 10, particularly preferably 2 to 8 carbon atoms, such as acetoxy. ), An acylamino group (preferably having 1 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms,
Particularly preferably, it has 2 to 4 carbon atoms, such as acetylamino. ), A sulfonylamino group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms,
Particularly preferably, it has 1 to 4 carbon atoms, and examples thereof include methanesulfonylamino. ), A sulfamoyl group (preferably having 0 to 10 carbon atoms, more preferably having 0 carbon atoms).
To 6, particularly preferably 0 to 4 carbon atoms, such as sulfamoyl and methylsulfamoyl. ), A carbamoyl group (preferably having 1 to 10 carbon atoms,
More preferably 1 to 6 carbon atoms, particularly preferably 1 carbon atom
To 4, for example, carbamoyl, methylcarbamoyl and the like. ), An alkylthio group (preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, for example, methylthio, ethylthio, etc.), a sulfonyl group (preferably carbon 1 to 8, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, for example, methanesulfonyl and the like; a sulfinyl group (preferably 1 to 8 carbon atoms, more preferably carbon A number of 1 to 6, particularly preferably a carbon number of 1 to 4, such as methanesulfinyl, etc.), a hydroxy group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group Group, carboxy group, nitro group, heterocyclic group (for example, 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 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.), 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, and examples of the substituent include those listed 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, 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 carbon number). 2-6,
Particularly preferably, it has 2 to 4 carbon atoms, and examples thereof include 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, such as propargyl).

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

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, quinolyl and the like, 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 It preferably has 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, and examples thereof include vinyl and allyl), and alkynyl groups (preferably 2 to 4 carbon atoms).
8, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, such as propargyl. ) And the like.

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, such as 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, such as propargyl). L ₁ and L ₂
The substituent of the alkylene group represented is preferably an aryl group, an alkoxy group, a hydroxy group, a carboxy group,
A sulfo group, more preferably an aryl group, a carboxy group or a hydroxy group. The alkylene group represented by L ₁ and L ₂ preferably has an alkylene group moiety having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably substituted or unsubstituted methylene or ethylene. Is.

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

The cations represented by M ₁ and M ₂ 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.), etc. Is mentioned. M ₁ and M ₂ are preferably alkali metals and ammonium, and more preferably Na ⁺ and K.
⁺ , NH ₄ ⁺ . Among the compounds represented by the general formula (I), the compound represented by the general formula (Ia) is preferable. General formula (Ia)

[0024]

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(In the formula, L ₁ and M ₁ have the same meanings as those in formula (I), respectively, and the preferred ranges are also the same. M _a1 and M _a2 are M ₂ in formula (I). And more preferably in the general formula (Ia), L ₁ is a substituted or unsubstituted methylene or ethylene, and M ₁ ,
M _a1 and M _a2 are any of a hydrogen atom, an alkali metal and ammonium, more preferably L ₁ is a substituted or unsubstituted methylene, and M ₁ , M _a1 and M _a2 are a hydrogen atom and an alkali. It is either a metal or ammonium, and particularly preferably L ₁ is a substituted or unsubstituted methylene having a total carbon number of 1 to 10 including a substituent,
M ₁ , M _a1 , and M _a2 are hydrogen atoms, Na ⁺ , K ⁺ , NH ₄ ⁺
In either case.

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

The divalent linking group represented by W 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 may be a linear or branched alkylene group having 2 to 8 carbon atoms (eg ethylene, propylene, trimethylene), 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.

[0030]

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[0031]

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More preferably, W is ethylene or propylene.
Pyrene, trimethylene, 2,2-dimethyltrimethylene
And ethylene and trimethylene are particularly preferred.
M_{twenty one}, M_{twenty two}, M_{twenty three}, M_{twenty four}Is a hydrogen atom or
Thione, these are M in the general formula (I).₁, M
_TwoIs synonymous with A compound represented by the general formula (II)
Chi, R_{twenty two}, R_{twenty four}Is a hydrogen atom, and t and u are 1
Preferably, more preferably R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}But water
It is an elementary atom and t and u are 1. General formula (II)
More preferably, among the compounds represented by_{twenty one}, R_{twenty two},
R_{twenty three}, R _{twenty four}Is a hydrogen atom, t, u is 1, W is ethylene, M
_{twenty one}, M_{twenty two}, M_{twenty three}, M_{twenty four}Is a hydrogen atom, Na⁺, K⁺, NH
_Four ⁺Selected from and R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}But
Hydrogen atom, t and u are 1, W is trimethylene, M_{twenty one},
M_{twenty two}, M_{twenty three}, M_{twenty four}Is a hydrogen atom, Na⁺, K⁺, NH_Four ⁺
It was chosen from.

When the compound represented by 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. 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.

[0034]

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[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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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

[Chemical 21]

[0046]

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[0047]

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[0048]

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

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

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

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

The organic acid iron (III) complex salt contained in the bleaching treatment solution of the present invention may be used as an alkali metal salt or an ammonium salt. As the alkali metal salt, a lithium salt, a sodium salt, a potassium salt, and the like, and as the ammonium salt, an ammonium salt, a tetraethylammonium salt, and the like can be given.In the present invention, the ammonium ion concentration in the processing solution having the bleaching ability is 0-0.
It is preferably 4 mol / l, particularly preferably 0 to 0.2 mol / l.

In the present invention, as the bleaching agent, other than 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 compound represented by the general formula (I) or (II) is suitably 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.

The bleaching solution preferably contains a pH buffering agent, particularly glycolic acid, succinic acid, maleic acid,
Malonic acid, glutaric acid and the like, it is preferable to contain an organic acid having a low odor, in particular, glycolic acid, malonic acid,
Succinic acid is preferred. The concentration of these buffers is 0
The range is preferably from 3 to 3 mol / liter, particularly from 0.2 to
A range of 1.5 mol / l is preferred.

In the present invention, the replenisher for the processing solution having a bleaching ability is a solid (powder, granules, tablets) even if it is a liquid.
In the granules and tablets, 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, JP-A-4-85535,
As described in JP-A-4-85536, JP-A-4-88533, JP-A-4-85534, and JP-A-4-172341, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded. Then, any means such as forming a coating layer by molding or spraying a water-soluble binder on the surface of the photographic processing agent that has been temporarily molded can be adopted. A method for producing a tablet processing agent is described in, for example, Japanese Patent Laid-Open No.
No. 1-61837, No. 54-155038,
It can be produced by a general method described in JP-A No. 52-88025 and British Patent No. 1213808, and the granule treating agent is, for example, JP-A-2-109042, JP-A-2-109043, JP-A-3-109043. It can be produced by a general method described in JP-A-39735 and JP-A-3-39739. Further, the powder treating agent is described in, for example, JP-A-5
4-133332, British Patent 725892, 729862 and German Patent 373386.
It can be produced by a general method as described in Japanese Patent Publication No. 1 and the like.

When the replenisher for the processing solution having the bleaching ability is composed of a liquid, it may be one solution or a plurality of solutions containing different components, but from the viewpoint of storage space of the replenisher and operability during preparation of the solution. One or two liquids are 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.

Further, 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 order to achieve such a pH, it is preferable in the present invention 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 acids (inorganic acid, organic acid) can be used.

The treatment with the bleaching solution 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 acid 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, nitric acid compounds such as ammonium nitrate and sodium nitrate are 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. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 12 minutes, more preferably 1 minute 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. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air,
Air is preferably released into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding the aeration, the matters described on pages BL-1 to BL-2 of Z-121, Eusing Process C-41 3rd edition (1982), published by Eastman Kodak Company can be used. In the treatment using the treatment liquid having the bleaching ability of the present invention, it is preferable that stirring is strengthened,
The contents described in JP-A-3-33847, page 8, upper right column, line 6 to lower left column, line 2 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 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, the polyamine compounds described in JP-B-45-8836, and the like 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.

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.
The sulfinic acid compound etc. described in the specification of No. 231051 can be contained. Furthermore, various fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained. Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having a fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediamine-N, N, N'. , N '
-Tetraacetic acid, diethylenetriaminepentaacetic acid, trans-1,2
-Cyclohexanediamine-N, N, N ', N'-tetraacetic acid, 1,2-propylenediaminetetraacetic acid can be mentioned.

It is also preferable to add a buffer to the bleach-fixing solution and the fixing solution in order to keep the pH of the solution constant. For example, phosphate, or imidazole, 1-methyl-
Examples thereof include imidazoles such as imidazole, 2-methyl-imidazole and 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, and N-benzoylpiperazine.

In the desilvering process, 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.

The automatic developing machine used in the light-sensitive material of the present invention is 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 the bleaching ability, in addition to the above-mentioned aeration, the methods described in "Basics of Photographic Engineering-Silver Salt Photographs-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 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 concentrations of the respective components calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant. C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (processing tank liquid) C _P : Consumed during processing the concentration of component V _1: amount of replenisher having bleaching ability for the light-sensitive material of 1m _² (ml) V ^2: amount carried from previous bath by the photographic material of 1 m ² (m
l) Further, the processing tank having a bleaching ability of the present invention is preferably equipped with the bleaching / regenerating apparatus described in JP-A-2-67552.

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. For bleaching and fixing solutions,
From the viewpoint of improving the desilvering property, it is preferable to use ammonium as a cation, but from the purpose of reducing environmental pollution,
It is preferable to reduce or eliminate ammonium. In the bleaching, bleach-fixing and fixing steps, JP-A-1-309
It is particularly preferable to carry out jet stirring described in No. 059. The replenishing amount of the replenishing solution in the bleach-fixing or fixing step is 100 to 1000 ml, preferably 150 to 700 ml, and particularly preferably 200 to 6 per m ² of the light-sensitive material.
00 ml.

In the bleach-fixing and fixing steps, 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 bleach-fixing solution and the fixing solution, it is preferable to allow a free chelating agent which is not a metal complex to be present from the viewpoint of improving the preservability.
As these chelating agents, it is preferable to use at least one compound represented by the general formula (I) or (II) or (A) of the present invention.

With respect 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 to prepare the replenisher or from the light-sensitive material,
Although various ionic components such as potassium ions are present, in the present invention, the sodium ion concentration in the final bath of the washing and stabilizing steps is particularly preferably in the range of 0 to 50 mg / liter, particularly 0 to 20 mg / liter. Is preferred.

The washing amount and the replenishment amount of the stabilizing solution are the same as those 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. In the processing method of the present invention, it is preferable that the processing solution having a bleaching ability and / or the processing solution having a fixing ability contain a compound represented by the following general formula (A) or (B). General formula (A)

[0079]

Embedded image

(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)

[0081]

Embedded image

(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. )

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.) and the like.

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

[0092]

Embedded image

(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)

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(In the formula, 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)

[0102]

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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 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.

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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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, the examples given as 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 those exemplified as 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)

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(In the formula, X _b and M _b have the same meanings as those in formula (B), respectively, and the preferable 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.

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

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(In the formula, X _b , M _b , and R _b1 have the same _{meanings as} those in 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. )

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

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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.

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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If possible, the above compound may be a conjugated isomer thereof. 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 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, but the range of 6.4 to 7.7 is particularly preferable. 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 10 per 1 m ² of the light-sensitive material.
0 to 1000 ml, preferably 150 to 700 ml,
Particularly, 200 to 600 ml is preferable.

The processing solution having a fixing ability contains a sulfite as a preservative (for example, 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 processor used in the method of the present invention will be described below. In the processing machine of the photosensitive material according to the present invention, when the thickness at the gas-liquid interface of the tank cross section orthogonal to the traveling direction of the photosensitive material in this processing tank is W, 0.1 ≦ W It is characterized in that the condition of ≦ 2 cm is satisfied, and more preferably 0.3 ≦ W ≦ 1.
cm. As described above, by reducing the thickness of the tank cross section at the gas-liquid interface, it is possible to reduce the area in which the processing liquid comes into contact with air and prevent the processing liquid from deteriorating. As described above, the known processing liquid forms a crystalline deposit on the inner wall or member of the processing tank near the gas-liquid interface, or a tar-like product that is considered to be caused by the deterioration of the carried-in developer component is attached. Easy to use, there is a possibility that stains and scratches may occur at the edge portion of the photosensitive material when a processing device having a narrow processing path is used, but the compound iron (III) having the specific structure is used.
These problems are solved by combining with a processing solution having a bleaching ability containing a complex salt. As a preferred mode of the processor that satisfies the above conditions, a processing tank (processing tank) in which a processing liquid for processing a photosensitive material is stored and formed in a V shape, and a part of an inner wall surface of the processing tank are formed. And a processing unit for processing a photosensitive material, which has a guide portion for guiding the photosensitive material and forming a transporting path of the photosensitive material, and a transporting unit which is disposed in the processing tank and transports the photosensitive material along the transporting path. For example, the photosensitive material processing device described in Japanese Patent Application Laid-Open No. 2-67552 can be used in which the tank forms a slit-shaped processing path. Further, by using such a thin tank cross section, V / L ≦ when the tank volume of the processing section is V milliliter and the path length of the photosensitive material from the inlet to the outlet of the processing section is L centimeter.
The processing tank may satisfy the condition of 25. The tank capacity (V) here means the capacity of the processing tank in the portion through which the photosensitive material passes, and excludes the capacity of the sub-tank for adjusting the liquid amount of the circulation system, temperature adjustment, aeration and the like. L means the path length of the processing section, and means the path length from the contact of the photosensitive material with the processing liquid in the processing tank to the discharge from the processing liquid. It is preferable that the relationship of V / L ≦ 25 be satisfied between the tank capacity (V) milliliter and the path length (L) centimeter,
More preferably, 1 ≦ V / L ≦ 20. The tank volume (V) is preferably in the range of 50 to 5000 ml, and more preferably 100 to 3000 ml from the viewpoint of the effect. The path length (L) varies depending on the type of processing liquid and the time required for processing, but is generally preferably 2 to 200 cm, and more preferably 4 to 120 cm.

A sectional view of an embodiment of a suitable photosensitive material processing apparatus that can be used in the method of the present invention is shown in FIG. As shown in FIG. 1, the photosensitive material processing apparatus 10 according to the present embodiment is provided with a slit-shaped processing path 12 in order to reduce the processing liquid amount and perform processing easily. The slit-shaped processing path 12 used here is a cross section obtained by cutting a path in a processing tank through which a photosensitive material passes at a right angle to the traveling direction of the photosensitive material, and a cross-sectional thickness (width direction of the photosensitive material) of the cross section. Means a so-called slit type. The slit shape may be rectangular or oval.
Further, in the processing tank, when the curvature formed by the processing path at the bottom of the processing tank is R, 10 ≦ R ≦ 70
mmφ is preferable, and 20 ≦ R ≦ 50.
It is preferably mmφ. When R is large, the processing apparatus becomes large, and when R is small, there is a possibility that conveyance failure of the photosensitive material occurs.

The path length of the processing path 12 is determined according to the type of the processing liquid and the time required for the processing (immersion time in the processing liquid). The slit-shaped processing path 12 may be provided in all the processing tanks of the photosensitive material processing apparatus, or in some processing tanks,
Other processing tanks may be the same processing tanks as in the past.
In this photosensitive material processing apparatus 10, all processing tanks are provided with slit-shaped processing paths 12, and a developing tank (color developing tank) 14 having a path length corresponding to the processing time and a bleaching tank 16 are adjacent to each other. The photosensitive material placed and developed in the developing tank 14 is sent to the bleaching tank 16 which is the next processing tank by a pair of conveying rollers 18. Further, the structure is such that four rinsing tanks 20 are arranged adjacent to the bleaching tank 16. The developing solution is stored in the developing tank 12, and the bleaching solution is stored in the bleaching tank 14.
A rinse liquid is stored in each of the rinse tanks 16. If desired, the bleaching tank 14 may be mixed with a processing solution having a fixing ability to form one bleaching / fixing tank. Therefore, the developing tank 14 of the photosensitive material processing apparatus 10
When the photographed negative film F is inserted from the open end side of the developing tank 14, the developing tank 14, the bleaching tanks 16 and 4 are processing tanks.
The negative film is soaked in the two rinse tanks 20 in sequence and the negative film is developed. Further, a drying zone 21 is arranged on the open end side of the last rinse tank (4) 20, and the negative film coming out of the rinse tank 20 is inserted into this drying fan to be dried.

Next, FIG. 2 shows a sectional view of a second embodiment of a suitable photosensitive material processing apparatus which can be used in the method of the present invention. As shown in FIG. 2, the photosensitive material processing apparatus 22 according to the present embodiment is provided with a slit-shaped processing path 12 for reducing the processing liquid amount and simply processing. The path length of the processing path 12 is determined according to the type of processing liquid and the time required for processing. The slit-shaped processing path 12 may be provided in all the processing tanks of the photosensitive material processing apparatus, or in some processing tanks,
Other processing tanks may be the same processing tanks as in the past.
In this photosensitive material processing device 22, all processing tanks are provided with slit-shaped processing paths 12, and a developing tank 24 and a bleaching tank 26 having a path length according to the processing time are arranged adjacent to each other. The photosensitive material developed in 24 is sent to a bleaching tank 26 which is the next processing tank by a pair of conveying rollers 18. Furthermore, adjacent to the bleaching tank 26,
It has a structure in which two stabilizers 28, a washing tank 30, and three stabilizing tanks 32 are respectively arranged. And the developing tank 2
4, the bleaching solution is stored in the bleaching tank 26, the fixing solution is stored in each of the two fixing tanks 28, and the rinsing water is stored in the washing tank 30. A stabilizing solution is stored in each stabilizing tank 32. If desired, the bleaching tank 26 and the fixing tank 28 may constitute one bleaching / fixing tank. Therefore, when the negative film having been photographed is inserted from the open end side of the developing tank 24 of the photosensitive material processing device 22, these developing tanks 2 which are processing tanks are inserted.
4, bleaching tank 26, two fixing tanks 28, washing tanks 30 and 2
The negative film is sequentially dipped in one of the stabilizing tanks 32 to develop the negative film. Also, the last stabilizing tank 32
A drying zone 34 is disposed on the open end side of the negative film, and the negative film coming out of the stabilizing tank 32 is inserted into the drying zone 34 and dried.

From the above, the bleaching tanks 16 and 26 are formed as slit-like tanks, and the portions of the developing tanks 16 and 26 which are the gas-liquid interface, for example, the position where the negative film starts to come into contact with the bleaching solution (processing tank) When the thickness of the tank cross section orthogonal to the traveling direction of the photosensitive material in the slit-shaped tank is W at the position where the negative film is discharged from the bleaching solution (inlet) or the position where the negative film is discharged from the inside of the bleaching solution (W), ≤W≤2c
The contact area with the air of the bleaching solution is reduced to m. Further, slit-shaped spaces are similarly formed inside other processing tanks such as the developing tanks 14, 24, the fixing tank 28, and the rinse tank 20, and the processing tanks are arranged so as to be joined to each other.

In the method of the present invention, the conveying speed of the light-sensitive material is preferably 0.1 m to 5 m per minute, more preferably 0.2 m to 3 m per minute, and is preferably 0.
Particularly preferably, it is 3 m and 1.5 m. The method of conveying the photosensitive material applied to the processor used in the method of the present invention is not particularly limited, and a known conveying method, for example, a roller type conveying method for conveying the photosensitive material by the nip force of a pair of conveying rollers, a drum. It is possible to select a drum processing method, a so-called leader trailer transfer method, or the like, in which the photosensitive material is inserted, conveyed, and sent out in the processing liquid kept in a narrow space by the rotation of the above. By using such a processing apparatus, the negative film transport path is constituted by the bleaching tanks 16 and 26 having the slit-shaped processing paths and the processing path 12 having an extremely thin thickness. The area of the gas-liquid interface of the bleaching solution is reduced, and the bleaching solution in the bleaching tank can be reduced in quantity, and a large amount of replenishing solution is not required to maintain the characteristics of the bleaching solution. 10, 22
Running cost is reduced. Further, by reducing the amount of the bleaching solution in the above structure, the processing tank for storing the bleaching solution can be downsized, and accordingly, the photosensitive material processing apparatuses 10 and 22 can be downsized. Then, the developing tanks 14 and 2
Other processing tanks, such as 4 and the rinse tank 20, will operate in the same manner as above.

Next, the color developing solution used in the method of the present invention will be described. The color developing solution is described in JP-A-4-1217.
The compounds described in No. 39, page 9, upper right column, line 1 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. It is preferable that the color developing solution contains a color developing agent in an amount of 0.01 to 0.08 mol / liter, particularly 0.015 to 0.06 mol / liter, and further 0.02 to 0. It is preferably contained in an amount of 05 mol / liter. The replenisher for the color developing solution preferably contains 1.1 to 3 times this value.

The color developing solution may be a pH buffer 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, black and white development is usually carried out and then color development is carried out. 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 represented 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.

Further, when the replenishment amount is reduced or when the bromide ion concentration is set to a high level, 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 above 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 above 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.

The present invention can be applied to the processing of any photosensitive material. The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing this photosensitive material are Those described in the following patent publications, particularly European Patent EP0,355,660A2 (JP-A-2-139544) are preferably used. The places where the photographic components are described in the above publications are shown as a list.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5]

Next, the photosensitive material used in the method of the present invention will be described in detail. As the silver halide emulsion used in the present invention, emulsions having various halogen compositions such as silver iodobromide, silver iodochloride, silver iodochlorobromide, silver bromide and silver chloride can be used. In particular, it is preferable to have at least one emulsion layer containing silver halide grains of which silver chloride is 90 mol% or more. More preferably, it is an emulsion containing silver halide grains in which 95 to 99.9 mol% or more, and further preferably 98 to 99.9 mol% or more, are silver chloride, and all layers are 98 to 99.9 mol%. A silver chlorobromide emulsion consisting of the above silver chloride is particularly preferable. The amount of coated silver is not particularly limited and is preferably applied to a light-sensitive material of about 0.2 to 15 g / m ² .
It is preferably about 0.4 to 5.0 g / m ² .

When the light-sensitive material used in the present invention is a color light-sensitive material, various couplers can be contained, and details are as shown in Table 2. Further, as the cyan coupler, in addition to the diphenylimidazole-based cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine-based cyan coupler described in European Patent 333,185A2 (among others, listed as specific examples). 4-equivalent coupler of coupler (42) with a chlorine-eliminating group to make 2-equivalent, or coupler (6)
And (9) are particularly preferable) and the cyclic methylene cyan couplers described in JP-A-64-32260 (specifically, coupler examples 3, 8, and 34 listed as specific examples) are also preferably used.

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is used for the purpose of improving the sharpness of an image and the like, as disclosed in European Patent Publication EP 0,357,490A2, No. 27.
To page 76, a dye that can be decolorized by processing (among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more,
It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a divalent to tetravalent alcohol (eg, trimethylolethane). Further, in the light-sensitive material according to the present invention, a layer containing a coupler has a European published patent EP
It is preferred to use color image-storing compounds such as those described in 0,277,589 A2. In particular, combination use with a pyrazoloazole-based magenta coupler is preferable.

That is, the compound (F) which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or after the color development processing. It is possible to use the compound (G), which forms a chemically inactive and substantially colorless compound by being chemically bonded to the remaining oxidized product of the aromatic amine color developing agent, simultaneously or alone, for example, after the treatment. It is preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or the oxidation product thereof during storage. Further, in the light-sensitive material according to the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-271247 is used.
It is preferable to add an antifungal agent as described in No.

The effect of the present invention can be particularly remarkably obtained when the dry film thickness of the silver halide color photographic light-sensitive material used in the present invention, excluding the support, is 25 μm or less. More preferable film thickness, particularly preferably 6 to 17 μm
m. These film thicknesses can be reduced by reducing the amount of gelatin, the amount of silver, the amount of oil, the amount of couplers, etc., but it is most preferable to reduce the amount of gelatin.
Here, the film thickness was measured after leaving the sample for 2 weeks at 25 ° C. and 65% RH.
It can be measured by a conventional method.

In the silver halide color photographic light-sensitive material used in the present invention, the film swelling degree of the photographic layer is 1.5 to.
A value of 4.0 is preferable from the viewpoint of improving stain and improving image storability. Particularly, in the range of 1.5 to 3.0, a further effect can be obtained. The swelling degree of the present invention means
A value obtained by dividing the film thickness of the photographic layer after dipping the color light-sensitive material in distilled water at 33 ° C. for 2 minutes by the film thickness of the dried photographic layer.

The term "photographic layer" as used herein refers to a hydrophilic colloid group layer which comprises at least one photosensitive silver halide emulsion layer and has a water-permeable relationship with this layer. It does not include the back layer provided on the side opposite to the photographic photosensitive layer across the support. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and includes an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like in addition to the silver halide emulsion layer.

Any method may be used to adjust the degree of swelling. For example, the amount and type of gelatin used in the photographic film, the amount and type of hardener, or the drying after coating the photographic layer. It can be adjusted by changing the conditions or the aging conditions. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives;
Various synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers. Can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. As the gelatin derivative, those obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, and maleimide compounds are used. .

The gelatin / graft polymer may be obtained by grafting onto acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, homopolymers or copolymers of vinyl monomers such as acrylonitrile and styrene. It can be used. In particular, a polymer having a certain degree of compatibility with gelatin, for example, a graft polymer with a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyalkyl methacrylate is preferable. Examples of these are US Pat. Nos. 2,763,625 and 2,832.
No. 1,767, No. 2,956,884 and the like. Representative synthetic hydrophilic polymeric substances are, for example, West German Patent Application (OLS) 1,312,708, US Pat.
No. 620,751, No. 3,879,205, and Japanese Examined Patent Publication No. 43-7561.

Examples of the hardening agent include chromic acid (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), Dioxane derivatives (2,3-dihydrodioxane etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s
-Triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis [β- (vinylsulfonyl) propionamide] and the like), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), Isoxazoles, dialdehyde starch, 2
-Chlor-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Particularly preferred hardeners are aldehydes, active vinyl compounds and active halogen compounds.

As the support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used.
In order to further improve the sharpness, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.35 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set it in the range of 0.8.

The light-sensitive material of the present invention may be exposed to visible light or infrared light. The exposure method may be low illuminance exposure or high illuminance short time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726 upon exposure. As a result, light color mixing is removed, and color reproducibility is significantly improved.

The processing method of the present invention can be applied to various photosensitive materials. For example, a color negative film, a color negative paper, a color reversal paper, an auto positive paper, a color reversal film, a negative film for movies, a positive film for movies, a film for plate making such as an X-ray film, a lith film, a black and white negative film, and the like can be given. Especially, application to a color negative film or a color negative paper is preferable.

In the case of a color negative, it is particularly preferable to have a magnetic recording layer on the support. 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 a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder.The magnetic particles include ferromagnetic iron oxide such as γFe ₂ O ₃ and Co. Deposited γFe ₂ O ₃ , Co deposited 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.
Of these, Co-deposited ferromagnetic iron oxide such as Co-deposited γFe ₂ O ₃ is preferable. 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
And 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. Further, magnetic particles having a surface coated with an inorganic or organic material described in JP-A-4-259911 and 5-81652 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 above 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 also have functions such as lubricity improvement, curl control, antistatic, adhesion prevention, and head polishing, or another functional layer may be provided to impart these functions. Alternatively, at least one kind of particles is preferably a non-spherical inorganic particle abrasive having a Mohs hardness of 5 or more. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
4, 5,229,259, 5,215,874 and EP 466,130.

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EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 A color photographic paper was prepared by the method described below. (Preparation of Support) Titanium dioxide (30 wt%) was added to low density polyethylene (MRF = 3), and zinc stearate was added at a ratio of 3.0 wt% with respect to the amount of titanium dioxide. (1) (trade name, manufactured by Daiichi Kasei) and kneaded in a Banbury mixer, and then used for melt extrusion. Titanium dioxide has a particle size of 0.
15 to 0.35 μm, the coating amount of hydrated aluminum oxide in the form of Al ₂ O ₃ was 0.1.
75% by weight was used. After subjecting a paper substrate having a basis weight of 170 g / m ² to a corona discharge treatment of 10 kVA, a polyethylene composition containing 30% by weight of the above titanium dioxide and a polyethylene composition containing 18% by weight of titanium dioxide and 30% by weight of titanium dioxide prepared in the same manner. % Of polyethylene containing ultramarine blue using a multi-layer extrusion coating die
Melt extrusion was performed at 20 ° C., and the thickness of the upper layer was 2 μm (18% by weight of titanium dioxide), the intermediate layer was 21 μm (30% by weight), and the lower layer was 10 μm (0% by weight) (the lower layer means the paper substrate side). A polyethylene laminate layer was provided. The surface of this polyethylene layer was subjected to glow discharge treatment.

(Preparation of Color Photographic Paper) Various photographic constituent layers were coated on the above reflective support to prepare a multilayer color photographic paper having the following layer constitution. The coating solution was prepared as follows.

Preparation of Third Layer Coating Solution Magenta coupler (ExM) 40.0 g, ultraviolet absorber (UV-2) 40.0 g, color image stabilizer (Cpd-2)
7.5 g, 25.0 g of color image stabilizer (Cpd-5), 2.5 g of color image stabilizer (Cpd-6), color image stabilizer (Cpd-5)
7) 20.0 g, 2.5 g of color image stabilizer (Cpd-8),
5.0 g of the color image stabilizer (Cpd-10) was added to a solvent (Sol).
v-3) 32.5 g, solvent (Solv-4) 97.5
g, solvent (Solv-6) 65.0 g and ethyl acetate 1
This was dissolved in 10 ml, and this solution was emulsified and dispersed in 1500 g of a 7% gelatin aqueous solution containing 90 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion A-1. On the other hand, silver chlorobromide emulsion B-1 (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.55 μm and small size emulsion of 0.39 μm (silver molar ratio). Coefficient of variation of grain size distribution is 0.08 and 0.06, respectively.Each size emulsion contained 0.8 mol% of silver bromide locally on a part of the surface of the grain based on silver chloride. To 0.1 mg of potassium hexachloroiridium (IV) and 0.1 mg of potassium ferrocyanide were prepared. This emulsion is
The green-sensitive sensitizing dyes D, E, and F shown below are 3.0 × 10 ⁻⁴ mol, 4.0 × 10 ⁻⁵ mol, and 2.0 × 10 mol per mol of silver, respectively, for a large-sized emulsion. ^-4 moles, or 3.6 × each mole of silver for small size emulsions
After adding 10 ^-4 mol, 7.0 × 10 ^-5 mol, 2.8 × 10 ^-4 mol, a sulfur sensitizer and a gold sensitizer were added in the presence of a decomposed product of nucleic acid to optimize the chemistry. Sensitization was performed. The above emulsified dispersion A-1 and this silver chlorobromide emulsion B-1 were mixed and dissolved to prepare a third layer coating solution having the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

Other coating solutions for the first to seventh layers were prepared in the same manner as the third layer coating solution. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Moreover, Cpd-12 is added to each layer.
And Cpd-13 were added so that the total amounts were 25.0 mg / m ² and 50.0 mg / m ² , respectively. The size of the silver chlorobromide emulsion in each light-sensitive emulsion layer was adjusted in the same manner as in the silver chlorobromide emulsion B-1, and the spectral sensitizing dyes shown below were used. Blue-sensitive emulsion layer

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(1.4 × 10 ⁻⁴ mol each for a large-sized emulsion and 1.7 × 10 ⁻⁴ mol for a small-sized emulsion, per mol of silver halide). ) Green-sensitive emulsion layer

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(Sensitizing dye D per mol of silver halide, 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and Sensitizing dye E per mol of silver halide is 4.0 × 10 ⁻⁵ mol for large-sized emulsion, 7.0 × 10 ⁻⁵ mol for small-sized emulsion, and sensitized. Dye F is 2.0 × 1 per mol of silver halide for a large-sized emulsion.
0 ^-4 mol, or 2.8 x 10 ^-4 for small size emulsions
Mole was added. ) Red-sensitive emulsion layer

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(Sensitizing dye G per mol of silver halide was 4.0 × 10 ^-5 for a large emulsion.
5.0 × each for moles and small emulsions
10 ^-5 mol, sensitizing dye H per mol of silver halide,
5.0 × 10 ⁻⁵ mol for large size emulsion and 6.0 × 1 mol for small size emulsion.
0 ^-5 mol was added. Further, the following compounds were added to the red-sensitive silver halide emulsion in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

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For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)
-5-Methylcaptotetrazole was added in an amount of 8.5 x 10 ^-4 mol, 3.0 x 10 ^-3 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mole and 2 × 10 ^-4 mole, respectively, per mole of silver halide. × 10 ^-4 mol was added.

For the purpose of preventing irradiation, the following dyes were added to the emulsion layer (the coating amount is shown in parentheses).

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(Layer Structure) The layer structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support (A) The resin layer on the first layer side contains a bluish dye (ultramarine).

First Layer (Blue Sensitive Emulsion Layer) Silver Chlorobromide Emulsion A-1 0.27 (cubic, 5: 5 mixture of large size emulsion having average grain size 0.88 μm and small size emulsion 0.70 μm) (Molar ratio of silver) Coefficients of variation of grain size distribution are 0.08 and 0.10 respectively, 0.3 mol% of silver bromide and a part of grain surface based on silver chloride for each size emulsion. 0.1 mg of potassium hexachloroiridium (IV) in total and 0.1 mg of potassium ferrocyanide in total inside the grain and in the silver bromide localized layer were contained.) Gelatin 1.22 Yellow Coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-) 5) 0.01 solvent (Solv-1 0.13 solvent (Solv-5) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 0.90 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.25 solvent (Solv-8) 0.03

Third Layer (Green Sensitive Emulsion Layer) The Silver Chlorobromide Emulsion B-1 0.13 Gelatin 1.45 Magenta Coupler (ExM) 0.16 UV Absorber (UV-2) 0.16 Color Image Stability Agent (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.10 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.08 Color image stabilizer ( Cpd-8) 0.01 Color image stabilizer (Cpd-10) 0.02 Solvent (Solv-4) 0.39 Solvent (Solv-5) 0.26

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.68 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.18 Solvent (Solv-8) 0.02

Fifth Layer (Red Sensitive Emulsion Layer) Silver Chlorobromide Emulsion C-1 0.18 (Cube, Large Size Emulsion C with Average Grain Size 0.50 μm and Small Size Emulsion C with 0.41 μm 1: 4 mixture (silver molar ratio) .The coefficient of variation of the grain size distribution is 0.09 and 0.11, respectively.Each size emulsion contains 0.8 mol% of silver bromide on the surface of grains based on silver chloride. In addition, 0.1 mg of potassium hexachloroiridium (IV) and 0.1 mg of potassium ferrocyanide were contained in the grains and in the silver bromide localized layer. 0.80 Cyan coupler (ExC) 0.33 UV absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer Cpd-8) 0.01 Color Image Stabilizer (Cpd-9) 0.02 Color Image Stabilizer (Cpd-10) 0.01 solvent (Solv-1) 0.01 solvent (Solv-7) 0.22

Sixth Layer (UV Absorbing Layer) Gelatin 0.48 UV Absorber (UV-1) 0.38 Color Image Stabilizer (Cpd-5) 0.01 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-9) 0.05

Seventh layer (protective layer) Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-11) 0.01

[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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The color photographic paper produced by the above method was processed by two types of roller transport type automatic processors. Automatic developing machine (photosensitive material processing device) used at this time 1
The structure of 0 is as shown in FIG. The photosensitive material was conveyed at a speed of 1.2 m / min and processed at a rate of 1 m ² per day for 3 weeks (5 days per week). The tank capacity and V / L value of each tank are shown in the table below. Here, the thickness W value of the processing tank of the processing machine (1) is 0.8 cm, and the width is 13.0 cm.
The thickness W value of the processing tank portion of the processing machine (2) was 1.6 cm and the width was 13.0 cm.

The processing steps and processing liquid compositions are shown below. (Processing process) Processing machine (1) Processing machine (2) Processing process time Temperature Replenishment amount * Tank capacity (V / L) Tank capacity (V / L) Color development 45 seconds 38.5 ℃ 45 ml 2.0 liters (23.4) 1.0 liters (11.7) Bleach and fix 45 seconds 38.0 ℃ 35 ml 2.0 liters (23.4) 1.0 liter (11.7) Rinse (1) 22 seconds 38.0 ℃ ―― 1.0 liter (25.0) 0.5 liters (12.5) Rinse (2) 22 seconds 38.0 ℃ ― ― 1.0 liter (25.0) 0.5 liter (12.5) Rinse (3) 22 seconds 38.0 ℃ ―― 1.0 liter (25.0) 0.5 liter (12.5) Rinse (4) 22 seconds 38.0 ℃ 175 ml 1.0 liter (25.0) 0.5 liter (12.5 ) Drying 40 seconds 80 ° C * Replenishing amount per 1 m ^{2 of} light-sensitive material Rinsing is a countercurrent method from (4) to (1). Also,
The amount brought into the next bath was 40 ml per 1 m ² of the light-sensitive material. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

(Color developer) Tank solution Replenisher Cation-exchanged water 800 ml 800 ml Dimethylpolysiloxane-based surfactant (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g 0.1 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g 4 1,5-Dihydroxybenzene-1,3-disulfonic acid sodium 0.5g 0.5g triethanolamine 12.0g 12.0g potassium chloride 12.0g-potassium bromide 45mg-triazinyl-4,4-diaminostilbene fluorescence increase Whitening agent (Hakkor OW-10EX / Showa Chemical Industry) 1.0g 3.0g Sodium phosphite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.0g 15.0g Triisopropyl Naphthalene (β) sodium sulfonate 0.1g 0.1g N-ethyl-N (β-methanesulfonamido ethyl) -3-methyl -4-Aminoaniline ・ 3/2 sulfuric acid ・ monohydrate 5.0 g 18.0 g Potassium carbonate 27.0 g 27.0 g Water was added to 1000 ml 1000 ml pH (at 25 ° C./KOH or sulfuric acid) 10.15 12. 6

(Bleach-fixing solution) Tank solution Replenishing solution Water 700 ml 700 ml Ammonium thiosulfate (750 g / liter) 100 ml 100 ml Ammonium sulfite 35.0 g 100 g Chelating agent described in Table 1 0.11 mol 0.33 mol Table 1 Additive 0.05 mol 0.15 mol Iron (III) nitrate / decahydrate 0.1 mol 0.3 mol m-carboxybenzenesulfinic acid 0.2 mol 0.5 mol Imidazole 8.0 g 18.0 g Water In addition 1000 ml 1000 ml pH (25 ℃ / sulfuric acid or ammonia water) 7.00 6.00

(Rinse) Tank liquid and replenisher are common Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

The following Table 6 shows the results of observing the light-sensitive material processed by the above method and evaluating stains and scratches on the light-sensitive material and color unevenness in the image area.

[0220]

[Table 6]

As shown in Table 6, by using the treatment liquid containing the compound of the present invention, the thickness W of the treatment tank was reduced to 0.
Doesn't stain or scratch the light-sensitive material even when processed with 8 cm and 1.6 cm processors, or
It was extremely small, and it was revealed that the obtained image was an excellent processing method with no color unevenness. On the other hand, in the method of the comparative example in which a conventional chelate compound was added using these processing devices, stains and scratches were generated on the photosensitive material, color unevenness was likely to occur, and the level was not practically usable.

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

(2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-on each side. Sulfodi-2-ethylhexyl succinate 0.01g / m ² , salicylic acid 0.04g / 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 After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as a back layer on one surface of the support.

(3-1) Coating of antistatic layer A dispersion of fine particle powder having a specific resistance of 5 Ω · cm of a tin oxide-antimony oxide composite having an average particle size of 0.005 μm (secondary agglomerated particle size of about 0.08 μm) 0.2 g / m ² , gelatin 0.05 g / 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 (polymerization degree 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 aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06g / m ² of 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. .

Layers each having the following composition were coated in layers on the above-mentioned support having 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: Ultraviolet 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 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

13th 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 the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 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.

[0243]

[Table 7]

In Table 7, (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.

In the same manner, 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. The structures of the compounds used are shown below.

[0247]

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[0248]

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[0249]

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[0250]

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[0251]

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[0253]

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[0254]

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[0255]

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[0256]

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[0258]

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[0259]

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[0260]

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[0261]

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[0262]

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The sample 101 prepared as described above is set to 24 mm
The sheet is cut into a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. 32 sets of these two sets
U.S. Pat. No. 5,296,887
It was housed in a plastic film cartridge described in Figs.

This sample 101 was replaced with a head gap of 5 μm.
m, the number of turns was 50, and it was mounted in a camera having a magnetic recording device made of a permalloy material, and digital saturation recording was performed at a recording wavelength of 50 μm.

[0265] The above sample 101 was treated with 0.5 m ² per day.
Processing was performed for one month (5 days per week) using the automatic processor 22 shown in FIG. At this time, the conveying speed of the photosensitive material was 50 cm / min, the tank thickness W value was 0.8 cm, and the width was 4.1 cm.

The developing tank 24, the bleaching tank 26, the two fixing tanks 28, the washing tank 30 and the two stabilizing tanks 32, each having a slit-like processing which can be preferably used in the processing method of the present invention shown in FIG. 2, are provided. Processing was performed in the following steps using the automatic developing machine (photosensitive material processing device) 22.

The processing steps and processing liquid compositions are shown below. (Processing process) Processing time Time Temperature Replenishment amount * Tank capacity (V / L) Color development 3 minutes 50 seconds 38.0 ℃ 260 ml 0.5 liter (3.3) Bleach 50 seconds 38.0 ℃ 130 ml 0.2 liter (4.8) Fixing (1) 50 seconds 38.0 ℃ -0.2 liters (4.8) Fixing (2) 50 seconds 38.0 ℃ 200 ml 0.2 liters (4.8) Washing with water 30 seconds 38.0 ℃ 450 ml 0.15 liters (6.0) Stable (1) 20 seconds 38.0 ℃ -0.15 liters ( 9.0) Stable (2) 20 seconds 38.0 ° C 390 ml 0.15 liter (9.0) Dry 1 minute 30 seconds 60 ° C * Replenishment amount per 1 m ^{2 of} light-sensitive material Stabilizer and fixer are from (2) to (1) Is a flow system,
All the overflow of the washing water was introduced into the fixing bath (2). The fixer is also connected from (2) to (1) by a countercurrent pipe. The amount of the color developing solution brought into the bleaching step, the amount of the bleaching solution brought into the fixing step, and the amount of the fixing solution brought into the water washing step were 65 ml, 52 ml and 52 ml per 1 m ² of the light-sensitive material, respectively. .
The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. A film processor FP360B manufactured by Fuji Photo Film Co., Ltd. was used as a comparative processor. The structure of the tank bath of this comparative processor, the tank capacity and the V / L value are shown in the table below. The thickness W value of the treatment tank was 2.5 cm. The conveying speed of the light-sensitive material was 47 cm / min.

(Treatment process) Treatment process time Temperature Replenishment amount * Tank capacity (V / L) Color development 3 minutes 50 seconds 38.0 ℃ 260 ml 11.5 liters (82) Bleach 50 seconds 38.0 ℃ 130 ml 4.0 liters (102) Fixing (1) 50 seconds 38.0 ℃ -4.0 liters (102) Fixing (2) 50 seconds 38.0 ℃ 200 ml 4.0 liters (102) Washing with water 30 seconds 38.0 ℃ 450 ml 3.0 liters (128) Stable (1) 20 seconds 38.0 ℃- 3.0 liters (191) Stable (2) 20 seconds 38.0 ℃ 390 ml 3.0 liters (191) Dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 1 m ^{2 of} light-sensitive material

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonic acid dinatrium 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Hydroxylamine sulfate 5.0 6.5 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 sulfate 4.5 6.5 Water was added to 1.0 liter 1.0 liter pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.21

(Bleaching solution) Tank solution Replenishing solution Compound (I-1) of the present invention 0.24 mol 0.4 mol Compound (I-15) of the present invention 0.12 mol 0.2 mol Iron nitrate (III) 9 Hydrate 0.24 mol 0.4 mol Ammonium bromide 0.4 mol 0.6 mol Inventive compound (A-7) 0.05 mol 0.12 mol Glycolic acid 0.7 mol 1.2 mol Succinic acid 0.3 mol 0.5 mol Add water 1000 ml 1000 ml pH (at 25 ° C nitric acid or ammonia water) 4.0 3.5

(Fixer) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution (750 g / l) 240.0 ml 720.0 ml Ammonium methanethiosulfonate 5.0 15.0 Ammonium methanesulfinate 10.0 30 0.0 Ethylenediaminetetraacetic acid 13.0 39.0 Imidazole 7.0 21.0 Add water 1000 ml 1000 ml pH (adjust with ammonia water and acetic acid) 7.4 7.5

(Washing water) Common to tank liquid and replenishing liquid Tap water is H type strong acid 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 added 1 liter pH (adjusted with ammonia water and nitric acid) 8.5

Table 8 shows the results of observing the light-sensitive material processed by the above method and evaluating stains and scratches on the light-sensitive material and color unevenness in the image area.

[0275]

[Table 8]

As shown in Table 8, by using the treatment liquid containing the compound of the present invention, the thickness W of the treatment tank was about 0.
Even if the treatment is performed using a small treatment machine with a reduced treatment liquid of 8 cm, the treatment tank has a thickness W of 2.5 cm compared with a treatment machine that requires a normal treatment liquid amount. It was clarified that the processing method was excellent, and the obtained image was free from stains and scratches on the light-sensitive material, and the obtained image had no color unevenness.

[0277]

According to the method of processing a silver halide color photographic light-sensitive material of the present invention, the amount of processing liquid can be reduced, and even if it is processed by a slit developing machine which can be easily downsized, It has an excellent effect that the photosensitive material is not likely to be stained or scratched.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a photosensitive material processor having a developing layer, a bleaching layer, and four rinse tanks, each having a slit-shaped processing path that can be used in the processing method of the present invention.

FIG. 2 is a schematic cross-sectional view showing a photosensitive material processor having a developing layer, a bleaching layer, two fixing tanks, a water washing tank and two stabilizing tanks, each having a slit-shaped processing path that can be used in the processing method of the present invention. Is. 10 Automatic Developing Machine (Photosensitive Material Processing Device) 12 Slit-shaped Processing Path 14 Developing Tank 16 Bleaching Tank 20 Rinsing Tank 22 Automatic Developing Machine (Photosensitive Material Processing Equipment) 24 Developing Tank 26 Bleaching Tank 28 Fixing Tank 30 Washing Tank 32 Stabilizing Tank

Claims (2)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material after color development with a processing solution having bleaching ability, wherein the processing solution having bleaching ability is represented by the following general formula (I) or (II).
In the tank of the processing section, which contains at least one iron (III) complex salt of the compound represented by, and which stores the processing solution having the bleaching ability, a tank cross section orthogonal to the traveling direction of the light-sensitive material When the thickness at the gas-liquid interface of the above is W, 0.1 ≤ W ≤ 2 cm is processed in a processing tank satisfying the relation represented by the above formula. . 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. 2. The processing method according to claim 1, wherein the processing solution having the bleaching ability contains at least one compound represented by the following general formula (A) or (B). General formula (A) General formula (B): [0001]