JPH0836249A - Processing method of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease environmental loading of a waste liquid, to suppress fog due to bleaching and to improve the stability of a color image and desilverizing property. CONSTITUTION:This photosensitive material contains a radical scavenger. The processing liquid having bleaching ability contains (a) a heteroring compd. having a carboxyl group or its salt in the molecule, (b) at least one kind of persulfuric acid or its salt, hydrogen peroxide or its salt, perboric acid or its salt, permanganic acid or its salt, hypohalogenated acid or its salt, halogenated acid or its salt, perhalogenated acid or its salt, org. peracid, org. peroxide, iodosyl compd., N-halocarboxylic acid amide, N-halosulfonic acid amide, and quinone, and (c) ferric ion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art Generally, the processing of a silver halide color photographic light-sensitive material basically consists of a color development step and a desilvering step. The desilvering step is carried out in two steps of bleaching and fixing.
It may be performed in one step such as bleach-fixing, or may be a combination of both. Further, as other treatment steps, there are steps such as washing with water, stabilization, and rinsing treatment. In the bleaching step, the silver halide in the light-sensitive material is reduced with a developing agent in a developing bath to develop silver which can be fixed by oxidizing it with an oxidizing agent called a bleaching agent. At this time, the bleaching agent is reduced by the equivalent amount of oxidized silver.

Examples of bleaching agents that have been widely used conventionally include ferric complex salts of ethylenediaminetetraacetic acid and ferric complex salts of 1,3-diaminopropanetetraacetic acid. These compounds are difficult to biodegrade. From the viewpoint of environmental protection in recent years,
There is a demand for detoxifying waste liquid generated from photographic processing, and alternatives to the above-mentioned non-biodegradable bleaching agents are being researched. EP 602600 A2 discloses a bleaching solution containing a persulfate salt and the biodegradable compound picolinic acid or 2,6-pyridinedicarboxylic acid and ferric ion. However, it has been found that when the treatment liquid described in the patent is used, there is a problem that bleaching fog is large and the color image produced is easily discolored.

[0004]

SUMMARY OF THE INVENTION According to the present invention, even when a processing liquid having a small environmental load of waste liquid is used, fogging due to bleaching is suppressed, a color image is stable, and an image is formed with excellent desilvering property. To provide a method.

[0005]

The present invention has achieved the above object by the following method. That is, (1) in a method in which an imagewise exposed silver halide color photographic light-sensitive material is subjected to color development and then treated with a processing solution having a bleaching ability, the light-sensitive material is used in at least one photographic constituent layer in at least one kind. (A) at least one heterocyclic compound having a carboxyl group or its salt in the molecule, and (b) persulfuric acid or its salt, hydrogen peroxide or its Salt, perboric acid or its salt, permanganic acid or its salt, hypohalous acid or its salt, halogenic acid or its salt, perhalogenic acid or its salt, organic peracid, organic peroxide, iodosyl compound, N −
A method of processing a silver halide color photographic light-sensitive material, which comprises at least one kind of halocarboxylic acid amide, N-halosulfonic acid amide, or quinones, and (c) contains ferric ion. (2) The silver halide color photographic light-sensitive material as described in (1) above, wherein the heterocyclic compound having a carboxyl group or a salt thereof in the molecule is a compound represented by the following general formula (I). Processing method.

[0006]

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In the formula, Q represents a group of non-metal atoms necessary for forming a heterocycle. p represents 0 or 1, and is preferably 0. Ma represents a hydrogen atom or an organic or inorganic cation. (3) The method for processing a silver halide color photographic light-sensitive material as described in (1) or (2) above, wherein the radical scavenger is a compound represented by the following general formula (A).

[0008]

[Chemical 4]

In the general formula (A), R _a1 is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group,
Sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group,, R _a2 represents a group represented hydrogen atom or a R _a1, also form a 5- to 7-membered ring R _a1 and R _a2 each other good. However, when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. (4) The processing method for a silver halide color photographic light-sensitive material as described in (1), (2) or (3) above, wherein the processing solution having the bleaching ability further contains a hydrocarbon dicarboxylic acid.

The present invention will be described in detail below. First, the radical scavenger contained in the light-sensitive material of the present invention will be described. The light-sensitive material of the present invention is characterized by containing at least one radical scavenger in at least one of the photographic constituent layers. The radical scavenger in the present invention means galvinoxyl 0.05 mmoldm ⁻³ ethanol solution at 25 ° C. and 2. a test compound.
5 mmoldm ⁻³ ethanol solution is mixed by the stopped-flow method, the time change of the absorbance at 430 nm is measured, and it means a compound that substantially decolors galvinoxyl (decreases the absorbance at 430 nm). The decolorization rate constant of galvinoxyl determined by the above method is preferably 0.01 mmol ⁻¹ s ⁻¹ dm ³ or more, more preferably 0.1 mmol ⁻¹ s ⁻¹ dm ³ or more. The method of determining radical scavenging rate using galvinoxyl is described in Microche
mical Journal 31 , 18-21 (1985), regarding the stopped-flow method, for example, Spectroscopic Research Vol. 19 No. 6 (1970).
It is described on page 321.

In the present invention, it is more preferable to use a compound represented by the following general formula (A) as the radical scavenger. The compound represented by formula (A) is described in detail below.

[0012]

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In the general formula (A), R _a1 is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group,
Sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, R _a2 represents a group represented hydrogen atom or a R _a1, bonded R _a1 and R _a2 each other,
A 5- to 7-membered ring may be formed. However, when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group.

The compound represented by formula (A) will be described in more detail. In the general formula (A), R _a1 is an alkyl group (eg, methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl), an alkenyl group (eg, allyl). , 2-butenyl,
Isopropenyl, oleyl, vinyl), aryl groups (eg phenyl, naphthyl), heterocyclic groups (5- to 7-membered heterocyclic rings having at least one of nitrogen atom, sulfur atom, oxygen atom or phosphorus atom as a ring-constituting atom) A group that forms, for example, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, pyridin-2
-Yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuranyl, morpholinyl), an acyl group (for example, Acetyl, benzoyl, pivaloyl, α- (2,4-di-tert-amylphenoxy) butyryl, myristoyl, stearoyl, naphthoyl, m-pentadecylbenzoyl, isonicotinoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, Toluenesulfonyl), sulfinyl group (eg methanesulfinyl, benzenesulfinyl), carbamoyl group (eg N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbyl) Moil, N- butyl -N-
Phenylcarbamoyl), sulfamoyl group (eg N
-Methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), alkoxycarbonyl group (for example, Methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or an aryloxycarbonyl group (eg phenoxycarbonyl, naphthoxycarbonyl). R _a2 represents a hydrogen atom or the group represented by R _a1 . R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring, and examples thereof include a succinimide ring, a phthalimide ring, a triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring.

R _a1 and R _a2 represented by the general formula (A)
The group may be further substituted with a substituent. Examples of these substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an alkylamino group, Arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples thereof include an acyloxy group and a hydroxyamino group.

Among the compounds represented by the general formula (A),
Preferred is when R _a1 is a heterocyclic group. More preferably, R _a1 is a heteroaromatic ring group (including a heterocyclic group that can formally form a heteroaromatic ring in the equilibrium structure; hereinafter used in this sense). More preferable ones are represented by the following general formula (AI).

[0017]

[Chemical 6]

In the general formula (AI), _R'a2 represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. Z represents a heteroaromatic ring group.

Of the compounds represented by formula (AI), those in which _R'a2 is a hydrogen atom or an alkyl group are preferable. Further, Z is preferably such that the ring-constituting atom is a carbon atom or a nitrogen atom. Most preferably, the general formula (A-I
It is a compound represented by I).

[0020]

[Chemical 7]

In the general formula (A-II), _R'a2 represents the same group as _R'a2 in the general formula (AI). R _a3 and R _{a4, which} may be the same or different, each represents a hydrogen atom or a substituent. R _a3 and R _a4 among the compounds represented by formula (A-II) are hydroxyamino groups,
A hydroxyl group, amino group, alkylamino group, arylamino group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyl group or aryl group is preferred. Among such R _a3 and R _a4 , more preferably R _a3 is a hydroxyamino group or a dialkylamino group, and most preferably R _a3 is a hydroxyamino group or an alkyl group having 7 or more carbon atoms.
It has a dialkylamino group. Specific examples of the compound represented by formula (A) of the present invention are shown below, but the present invention is not limited thereto.

[0022]

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[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

These compounds of the present invention are described in J. Org. Chem., 2
7, 4054 ('62), J. Amer. Chem. Soc., 73, 2981 ('51), JP-B-49-10692, and the like, or a method analogous thereto.

The radical scavenger of the present invention can be added to any of the constituent layers of the photographic light-sensitive material. Especially, having a high water solubility effects can be obtained by adding at any layer to diffuse the light-sensitive material. Further, those having low water solubility are preferably added to each photosensitive layer. As a specific layer, a protective layer, an intermediate layer, a photosensitive layer, a yellow filter layer and the like are preferable. As a method of addition, a water-soluble substance is preferably dissolved in water, an organic solvent such as methanol or ethanol, or a mixed solvent thereof and added. Further, those having low water solubility are preferably added after being dissolved or emulsified and dispersed in an organic solvent. The preferred addition amount of the radical scavenger of the present invention is 0.1 mg to 1 per 1 m ² of the light-sensitive material.
g, particularly preferably 0.5 mg to 0.5 g, and most preferably 1 mg to 100 mg.

The light-sensitive material applicable to the present invention can be applied to any color light-sensitive material and is preferably used as a color negative film or a color reversal film. Other photosensitive materials used in the present invention are disclosed in JP-A-4-125558.
The contents of page 14, lower left column, line 14 to page 18, lower right column, line 11 can be preferably applied. Particularly, as a silver halide emulsion, the average silver iodide content is 3 to 20 mol%.
Of silver iodobromide are preferable, and tabular grains having an aspect ratio of 5 or more and double structure grains having different halogen compositions inside and outside are preferable. Aspect ratio is especially 5-20
Is preferable, and 6-12 is more preferable. Further, tabular grains having a tabularity of 50 or more described in U.S. Pat. No. 5,183,727, page 12, line 47 to page 15, line 56 are also preferable. Regarding the coupler, a pyrazoloazole type magenta coupler and a 5-amidonaphthol type cyan coupler are particularly preferable.

Next, the processing solution having a bleaching ability of the present invention will be described. First, the heterocyclic compound having a carboxyl group or a salt thereof in the molecule which is the component (a) of the present invention will be described. The heterocycle is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O or S atoms, which may be a single ring or may be a condensed ring with another ring. You may form.

The hetero ring 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 1 to 1 nitrogen atom. It is a 5- to 6-membered aromatic heterocyclic group containing 2 atoms.

Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline,
Examples thereof include pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole and oxazole. The hetero ring is preferably pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline,
Phthalazine, quinoxaline, quinazoline, cinnoline,
Tetrazole, thiazole, oxazole, more preferably imidazole, pyrazole, pyridine, pyrazine, indole, indazole, thiadiazole,
Oxadiazole, quinoline, thiazole, oxazole, more preferably imidazole, pyridine,
Quinoline is preferable, and imidazole and pyridine are particularly preferable.

The heterocycle may have a substituent, and examples of the substituent include an alkyl group (preferably having a carbon number of 1 to 1).
12, more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms, and examples thereof include methyl and ethyl. ), An aralkyl group (preferably an aralkyl group having 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, particularly preferably 7 to 11 carbon atoms, and examples thereof include phenylmethyl and phenylethyl).
An alkenyl group (preferably an alkenyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, and examples thereof include allyl).
Alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, such as propargyl and the like), aryl group (preferably having carbon number). 6 to 20, more preferably 6 to 15 carbons, and particularly preferably 6 to 1 carbon atoms.
It is an aryl group of 0, and examples thereof include phenyl and p-methylphenyl. ), An amino group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 10, and particularly preferably a carbon number of 0 to 6), and examples thereof include amino, methylamino, dimethylamino, diethylamino and the like. .), An alkoxy group (preferably having a carbon number of 1 to 8, more preferably a carbon number of 1 to 6, and particularly preferably a carbon number of 1 to 4), such as methoxy,
Examples include ethoxy and the like. ), An aryloxy group (preferably having 6 to 12 carbon atoms, and more preferably having 6 to 1 carbon atoms).
0, particularly preferably an aryloxy group having 6 to 8 carbon atoms, and examples thereof include phenyloxy and the like. ), An acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include acetyl), and an alkoxycarbonyl group (preferably Has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
Is an alkoxycarbonyl group, and examples thereof include methoxycarbonyl. ), An acyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms,
Particularly preferred is an acyloxy group having 2 to 8 carbon atoms,
For example, acetoxy and the like can be mentioned. ), An acylamino group (preferably having 2 to 10 carbon atoms, and more preferably having 2 carbon atoms).
To 6, particularly preferably an acylamino group having 2 to 4 carbon atoms, and examples thereof include acetylamino and the like. ), A sulfonylamino group (preferably a C1-C10, more preferably a C1-C6, particularly preferably a C1-C4 sulfonylamino group such as methanesulfonylamino), and a sulfamoyl group. (Preferably a sulfamoyl group having 0 to 10 carbon atoms, 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 1 to 1 carbon atoms
0, more preferably a carbamoyl group having 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, for example, carbamoyl group,
Methylcarbamoyl and the like can be mentioned. ), An alkylthio group (preferably an alkylthio group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably an alkylthio group having 1 to 4 carbon atoms, and examples thereof include methylthio and ethylthio). Preferably 6 to 20 carbon atoms,
More preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms.
~ 8 arylthio groups, such as phenylthio. ), A sulfonyl group (preferably having 1 to 8 carbon atoms,
More preferably, it has 1 to 6 carbon atoms, and particularly preferably 1 carbon atom.
~ 4 sulfonyl group, for example, methanesulfonyl and the like. ), A sulfinyl group (preferably a C1-8, more preferably a C1-6, particularly preferably a C1-4 sulfinyl group such as methanesulfinyl), a ureido group, a hydroxy group. Group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, mercapto group, heterocyclic group (eg imidazolyl, pyridyl), etc. To be 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 or a mercapto group, 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.

The heterocyclic compound having a carboxyl group or a salt thereof in the molecule is preferably the following general formula (I)
Is a compound represented by. General formula (I)

[0035]

[Chemical 13]

(In the formula, Q represents a group of nonmetallic atoms necessary for forming a heterocycle. P represents 0 or 1. Ma
Represents a hydrogen atom or an organic or inorganic cation. ) The heterocycle formed by Q has the same meaning as the heterocycle described above. As the substituent of the heterocyclic ring formed by Q, an alkyl group having a total carbon number of 1 to 12, an amino group having a total carbon number of 0 to 20, an alkoxy group having a total carbon number of 1 to 8, a carboxyl group, a hydroxy group, It is a halogen atom, a cyano group, a nitro group or a mercapto group, more preferably an amino group having a total carbon number of 0 to 10, a carboxyl group, a hydroxy group or a mercapto 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.), an alkaline earth metal ion (eg, Ca ²⁺ , Mg ^2+). Etc.), ammonium (eg ammonium, tetraethylammonium),
Examples thereof include pyridinium and phosphonium (eg, tetrabutylphosphonium, tetraphenylphosphonium, etc.).

Of the compounds represented by the general formula (I), the compounds represented by the following general formula (Ia) are preferable. General formula (Ia)

[0038]

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

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

The nitrogen-containing heterocycle is preferably a 5- to 6-membered nitrogen-containing aromatic heterocyclic group, more preferably a 5- to 6-membered nitrogen-containing aromatic heterocyclic group containing 1 to 2 nitrogen atoms. is there.

Specific examples of the nitrogen-containing heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine,
Pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, Examples thereof include thiazole and oxazole. Preferably as a nitrogen-containing heterocycle, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole,
Thiadiazole, oxadiazole, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, oxazole, more preferably imidazole, pyrazole, pyridine, pyrazine, indole, indazole, thiadiazole, oxadiazole, quinoline, thiazole, Oxazole, more preferably imidazole, pyridine and quinoline, particularly preferably imidazole and pyridine.

The nitrogen-containing heterocycle may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 carbon atom). To 3 alkyl groups, such as methyl and ethyl, and aralkyl groups (preferably having 7 to 20 carbon atoms, more preferably having 7 to 1 carbon atoms).
5, particularly preferably an aralkyl group having 7 to 11 carbon atoms, and examples thereof include phenylmethyl and phenylethyl. ), An alkenyl group (preferably having a carbon number of 2 to 1)
2, more preferably an alkenyl group having 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, and examples thereof include allyl and the like. ), An alkynyl group (preferably having 2 to 1 carbon atoms)
2, more preferably an alkynyl group having 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, and examples thereof include propargyl and the like. ), An aryl group (preferably having 6 carbon atoms)
To 20, more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 10 carbon atoms, such as phenyl,
Examples include p-methylphenyl and the like. ), An amino group (preferably having 0 to 20 carbon atoms, and more preferably having 0 carbon atoms).
-10, particularly preferably an amino group having 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino and diethylamino. ), An alkoxy group (preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms,
Particularly preferably, it is an alkoxy group having 1 to 4 carbon atoms, and examples thereof include methoxy and ethoxy. ), An aryloxy group (preferably an aryloxy group having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms, and examples thereof include phenyloxy). (Preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 carbon atoms.
~ 8 acyl groups, such as acetyl. ), An alkoxycarbonyl group (preferably having 2 carbon atoms)
To 12, more preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include methoxycarbonyl. ), An acyloxy group (preferably having a carbon number of 2 to 12, more preferably a carbon number of 2 to 10, particularly preferably a carbon number of 2 to 8 and examples thereof include acetoxy), and an acylamino group (preferably). Carbon number 2-10,
More preferably 2 to 6 carbon atoms, and particularly preferably 2 to 2 carbon atoms.
4 is an acylamino group, and examples thereof include acetylamino. ), A sulfonylamino group (preferably a C1-C10, more preferably a C1-C6, particularly preferably a C1-C4 sulfonylamino group such as methanesulfonylamino), and a sulfamoyl group. (Preferably a sulfamoyl group having 0 to 10 carbon atoms, 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 carbamoyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, and examples thereof include carbamoyl and methylcarbamoyl.), An alkylthio group (preferably 1 to 8 carbon atoms). , More preferably 1 to 6 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
4 is an alkylthio group, and examples thereof include methylthio and ethylthio. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably an arylthio group having 6 to 8 carbon atoms, for example, phenylthio etc.), a sulfonyl group (preferably 1 carbon atom). To 8, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, and examples thereof include methanesulfonyl and the like.), Sulfinyl group (preferably 1 to 8 carbon atoms, more preferably carbon atoms). Carbon number 1
To 6, particularly preferably a sulfinyl group having 1 to 4 carbon atoms, and examples thereof include methanesulfinyl. ), Ureido group, hydroxy group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom),
Examples thereof include 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 or a mercapto group, 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 and Ma have the same meanings as those in formula (I), and the preferred ranges are also the same. General formula (I-
Among the compounds represented by a), the compounds represented by the following general formula (Ib) are preferable. General formula (Ib)

[0045]

[Chemical 15]

(In the formula, Ma has the same meaning as in formula (I). Q ² is a nitrogen-containing heterocyclic group, an alkyl group,
It may be substituted with an amino group, an alkoxy group, a carboxyl group, a hydroxy group, a halogen atom, a cyano group, a nitro group, or a mercapto group. ) Of the compounds represented by the general formula (Ib), more preferably the following general formula (I-
It is a compound represented by c). General formula (I-c)

[0047]

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(In the formula, Ma has the same meaning as that in formula (I). 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. , A hydroxy group, a halogen atom, a cyano group, a nitro group, or a mercapto group may be substituted.)

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

[0050]

[Chemical 17]

[0051]

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[0052]

[Chemical 19]

[0053]

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[0054]

[Chemical 21]

[0055]

[Chemical formula 22]

The above compounds may be used in the form of ammonium salts, alkali metal salts and the like. The compound represented by the general formula (I) 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 compounds represented by the general formula (I), particularly preferable are 2-carboxypyridine, 2,6-pyridinedicarboxylic acid, 2-carboxyimidazole, and 4
-Carboxyimidazole and its derivatives, more preferably 2-carboxypyridine and 2,6-pyridinedicarboxylic acid. The compound represented by the general formula (I) of the present invention is preferably contained in an amount of 0.0001 to 1.0 mol, more preferably 0.001 to 0.3 mol, per liter of the processing liquid having a bleaching ability. , 0.01
˜0.2 mol is more preferred. Excellent performance can be exhibited in such a range.

Next, the component (b) will be described. The salts of persulfuric acid, hydrogen peroxide, perboric acid, permanganic acid, hypohalous acid, halogenic acid and perhalogenic acid used in the present invention include lithium salt, sodium salt, potassium salt,
Ammonium salts, quaternary ammonium salts and the like can be used.
The sodium salt is preferred.

Examples of persulfuric acid or salts thereof used in the present invention include ammonium persulfate, sodium persulfate, potassium persulfate and the like. Examples of hydrogen peroxide or a salt thereof used in the present invention include hydrogen peroxide, sodium peroxide, barium peroxide and the like, and hydrogen peroxide is preferable. Examples of the perboric acid or a salt thereof used in the present invention include perboric acid, sodium perborate,
Examples thereof include potassium perborate, and sodium perborate is preferable. Examples of permanganic acid or salts thereof used in the present invention include potassium permanganate. The hypohalous acid or a salt thereof used in the present invention, for example, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, hypobromite, sodium hypobromite,
Examples thereof include potassium hypobromite, hypoiodic acid, sodium hypoiodite, potassium hypoiodite, and the like, with hypochlorous acid, sodium hypochlorite and potassium hypochlorite being preferred.

The halogen acid or its salt used in the present invention includes chloric acid, sodium chlorate, potassium chlorate,
Silver chlorate, barium chlorate, rubidium chlorate, bromic acid, sodium bromate, potassium bromate, iodic acid, sodium iodate, potassium iodate, potassium hydrogen iodate, silver iodate and the like, preferably chlorine Acid, sodium chlorate and potassium chlorate. The perhalogen acid or salt thereof used in the present invention, perchloric acid, lithium perchlorate, sodium perchlorate, potassium perchlorate, magnesium perchlorate, barium perchlorate,
Silver perchlorate, iron perchlorate, ammonium perchlorate, tetraethylammonium perchlorate, tetrapropylammonium perchlorate, tetrabutylammonium perchlorate,
Perbromic acid, sodium perbromate, potassium perbromate, periodate, sodium periodate, potassium periodate and the like, preferably perchloric acid, sodium perchlorate, potassium perchlorate, perchlorate. Ammonium acid, perbromic acid, sodium perbromate, potassium perbromate, periodate, sodium periodate and potassium periodate.

The organic peracid used in the present invention is, for example, "New Experimental Chemistry Course, Vol. 15," pages 697-747 (Maruzen).
Examples thereof include the organic peracids described above, preferably perbenzoic acid, metachloroperbenzoic acid, monoperoxyphthalic acid, performic acid, peracetic acid, trifluoroperacetic acid or salts thereof.
Examples of the organic peroxide used in the present invention include the organic peroxides described in "New Experimental Chemistry Course Vol. ), Peresters (such as tert-butyl peracetic acid), diacyl peroxides (such as benzoyl peroxide), and the like.

The iodosyl compound used in the present invention is, for example, "New Experimental Chemistry Course, Vol. 15," 697-747.
The iodosyl compound described in page (Maruzen) is mentioned, and iodosylbenzene and iodosylbenzene acetate are preferable. Examples of the N-halocarboxylic acid amide used in the present invention include "New Experimental Chemistry Course Vol. 15" 410-420.
Examples of the N-halocarboxylic acid amides described in page (Maruzen) are N-bromoacetamide, N-bromosuccinimide, N-bromophthalimide, isocyanuric chloride, N-bromocaprolactam, and 1-chlorobenzotriazole. Examples of the N-halosulfonic acid amide used in the present invention include, for example, "New Experimental Chemistry Course Vol. 15".
Examples thereof include N-halosulfonic acid amides described on pages 420 to 422 (Maruzen), preferably sodium N-chloro.
p-toluenesulfonamide and sodium N-chlorobenzenesulfonamide. Examples of the quinones used in the present invention include “New Experimental Chemistry Course Vol. 15” 844.
To 870 (Maruzen), preferably benzoquinone, naphthoquinone, sulfobezoquinone,
Carboxybenzoquinone, 2,3-dichloro-5,6-
Dicyano-1,4-benzoquinone, tetrachloro-1,
2-benzoquinone and tetrachloro-1,4-benzoquinone.

Of the above compounds, hydrogen peroxide or a salt thereof, persulfuric acid or a salt thereof, perboric acid or a salt thereof are preferable, and hydrogen peroxide or a persulfate salt is more preferable.
Perborate, more preferably hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate,
Sodium perborate and potassium perborate are preferred, and hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate are particularly preferred. The above compound is preferably contained in an amount of 0.001 to 1.0 mol, more preferably 0.01 to 0.3 mol, and further preferably 0.01 to 0.2 mol, per liter of the processing solution having a bleaching ability. Preferably, excellent performance can be exhibited in such a range.

Further, in the processing method of the present invention, the processing solution having a bleaching ability contains ferric ion. As an addition method, an inorganic salt (for example, ferric nitrate, ferric sulfate, ferric chloride, etc.) or an iron (III) complex can be added. As an example of the iron (III) complex, an iron complex of the heterocyclic compound of the present invention or an aminopolycarboxylic acid iron (III) complex may be added. Examples of preferable compounds are shown below, but the invention is not limited thereto. 2-carboxypyridine, 2,6-dicarboxypyridine, 1,3-diaminopropanetetraacetic acid, ethylenediaminetetraacetic acid, N, N'-ethylenediaminedisuccinic acid, N, N'-propanediaminedisuccinic acid, glycol etherdiamine Iron (III) such as tetraacetic acid, cyclohexanediaminetetraacetic acid, 1,4-diaminobutanetetraacetic acid, 1,2-propylenediaminetetraacetic acid, thioglycoletherdiaminetetraacetic acid, 1,3-butylenediaminetetraacetic acid, and methyliminodiacetic acid. Complex salts and the like are preferable. The amount of ferric ion added is preferably 0.0001 mol to 0.3 mol / liter, more preferably 0.003 to 0.05 mol / liter, and further preferably 0.01 to 0.05 mol / liter. . Is. In addition to the iron (III) complex, an aminopolycarboxylic acid salt can be added.

The bleaching solution of the present invention preferably contains a hydrocarbon dicarboxylic acid. Hydrocarbon dicarboxylic acids include saturated hydrocarbon dicarboxylic acids having two carboxyl groups in one molecule, unsaturated hydrocarbon dicarboxylic acids, aromatic hydrocarbon dicarboxylic acids, and alkali metal salts and ammonium salts thereof. In the present invention, dicarboxylic acids represented by the following general formula (B) and salts thereof are preferred. General formula (B) HOOC-L-COOH (In formula, L represents a single bond or a C1-C4 saturated or unsaturated aliphatic coupling group, and an arylene group.) Moreover, the aliphatic represented by L. The linking group (for example, methylene, ethylene, propylene, butylene) and the arylene group (for example, 1,2-phenylene) may have a substituent, and examples of the substituent include a saturated or unsaturated aliphatic group. , Amino group, hydroxylamino group, hydroxyl group, sulfo group and the like are preferable.

Examples of preferable hydrocarbon dicarboxylic acids are shown below, but the invention is not limited thereto. Examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, aspartic acid, glutamic acid, phthalic acid and sulfophthalic acid. Among these, particularly preferable are malonic acid, succinic acid, glutaric acid, maleic acid, and sulfophthalic acid, and it is also preferable to use two or more (preferably two or three) of them in combination, and particularly succinic acid and Most preferably, maleic acid or succinic acid and glutaric acid are used in combination. The preferable addition amount is 0.01 mol to 2.0 mol, and more preferably 0.05 mol to 1.5 mol in 1 liter of the bleaching solution.

The liquid having a bleaching ability constituting the present invention includes
In addition, rehalogenating agents such as bromides such as potassium bromide, sodium bromide, ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included. Multiple rehalogenating agents may be used in combination. Chloride is preferably used as the rehalogenating agent. The concentration of the rehalogenating agent is 0.02 to 2 mol, preferably 0.1 to 1.
It is 5 mol. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate,
Salts of phosphorous acid, phosphoric acid, sodium phosphate, etc., imidazoles, etc. may be added.

The liquid having a bleaching ability preferably contains gelatin or a nitrogen-containing heterocyclic compound in order to prevent generation of harmful gas. An imidazole compound is mentioned as a particularly preferable compound. Among them, imidazole and lower alkyl-substituted imidazole having a carbon number of 1 to 3 (2-
Methyl imidazole, 2,4-dimethyl imidazole,
2-ethylimidazole, 2-propylimidazole and the like) are preferred. The preferable addition amount of these compounds is 0.001 to 1 liter of a liquid having a bleaching ability.
0.3 mol, more preferably 0.003 to 0.1 mol,
More preferably, it is 0.005-0.05 mol.

Further, a bleaching accelerator may be used in the bleaching solution of the present invention. Examples of bleaching accelerators include US Pat. No. 3,893,858, British Patent No. 1,138,
No. 842, JP-A Nos. 53-141623 and 53-95.
631 and 54-52534, various mercapto compounds, disulfide compounds described in JP-A-53-95630, JP-B-45-8506, and JP-A-49-42.
Thiourea derivative described in JP-A-53-949.
No. 27, an isothiourea derivative, JP-B-53-98
Thiazolidine derivatives described in JP-A No. 54-54, JP-A-49-42
Thioamide compounds described in JP-A No. 349, JP-A-55-26
The dithiocarbamate salts described in No. 506 can be used. As the pH adjuster, organic and inorganic acids and alkalis can be used, but it is preferable to adjust the amounts of acetic acid, nitric acid, sodium hydroxide, potassium hydroxide, ammonia and the above-mentioned dicarboxylic acid.

The replenishing amount of the bleaching solution in the present invention is usually 100 ml to 2000 ml per 1 m ^{2 of the} light-sensitive material,
Preferably 150 ml to 1500 ml, more preferably 30
It is 0 ml to 1000 ml. The pH of the bleaching solution of the present invention is used in the range of 2.0 to 7.0, preferably 2.5 or more and 5.5 or less, and particularly preferably 3.0 to
It is in the range of 5.0. The treatment time with a solution having a bleaching ability is 1 minute to 6 minutes 30 seconds, preferably 1 minute 30 seconds or more and 4 minutes 20 seconds or less. The treatment temperature is 30 ° C. to 50 ° C., preferably 33 ° C. to 45 ° C., more preferably 35 ° C. to 40 ° C.

In the present invention, the ammonium salt can be replaced with an alkali metal salt. Specifically, it is preferable to use sodium salt, potassium salt, potassium bromide, sodium bromide, potassium nitrate, sodium nitrate or the like instead of each ammonium salt. Also, the pH
The ammonia water used for adjustment is preferably changed to potassium hydroxide or sodium hydroxide. The bleaching solution of the present invention can be used again as a replenishing solution by adding the consumed amount of the component in the overflow caused by the replenishment. In that case, it is preferable to adjust pH and specific gravity.

The conventional bleaching solution uses a high concentration of iron ions and a chelating agent, and the waste solution thereof has a large load on the environment. If the concentration is lowered to reduce the environmental load, the bleaching ability will be insufficient. Like the present invention,
By using a peracid such as persulfuric acid as a liquid having a bleaching ability, the amount of iron or a chelating agent having a large environmental load can be significantly reduced.

The bleaching solution of the present invention specifically means a bleaching solution or a bleach-fixing solution. Next, other processes used in the present invention will be sequentially described. The preferred treatment steps in the present invention are listed below, but the present invention is not limited thereto. Color development-stop-washing-bleaching-fixing-washing-stable-
Dry color development-stop-wash-bleach-bleach-fix-fix-wash-stable-dry color-develop-stop-wash-bleach-bleach-fix-wash-stable-dry color develop-stop-wash-bleach-fix- Wash-
Stable-drying Color development-stopping-washing-bleach-fixing-washing-stable-drying In the above processing step, washing in the step before stabilization can be omitted. It is also possible to omit the final stabilizing bath. Further, the stop bath and the washing bath after the color development may be omitted. When the color reversal light-sensitive material is processed, black-and-white development, reversal exposure or treatment with a reversal bath and, if necessary, a water washing step are performed prior to the above steps.

Regarding the processing solution used for processing a color negative film or a color reversal film, see Japanese Patent Application Laid-Open No.
The description from column 81, line 8 to column 93, line 17 of Japanese Patent No. 34887 can be cited. Particularly, as a color developing solution, JP-A-3-158849 and 3-174152.
A liquid containing a hydroxylamine having a substituent as described in JP-A No. 2004-108242 is preferable, and a liquid containing a hydroxylamine having a sulfoalkyl group as a substituent is particularly preferable. Further, those containing diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and 4,5-dihydrosibenzene-1,3-disulfonic acid as the chelating agent are preferable. The replenisher for the color developing solution has a bromide ion concentration of 0.0 to reduce the replenishment amount.
It is preferably reduced to 04 mol / liter or less, and particularly preferably a bromide ion concentration of 0.002 mol / liter or less. Preferred examples of these color developing solutions include:
Fuji Photo Film Co., Ltd. process CN-16X,
Examples thereof include a color developing solution and a color developing replenishing solution of CN-16Q and CN-16FA, and a color developing solution and a color developing replenishing solution of Process CR-56P.

In the processing of the present invention, the color developing solution is preferably replenished with a color developing replenishing solution. The color developing replenisher contains a compound contained in the color developing solution. The role of the color developing replenisher is to control the concentration of the compound eluted from the light-sensitive material by the processing, and replenishment of the compound to the color developing solution, which is decreased by the processing of the light-sensitive material and deterioration in the automatic processor over time. This keeps the developing performance constant. Therefore, the former compound has a higher concentration than the color developing tank solution, and the latter compound has a lower concentration. The former compound is a color developing agent or preservative, and the replenisher contains 1.1 to 2 of the tank solution.
Double amount is included. The latter compound is a development inhibitor represented by a halide (for example, potassium bromide), and the replenisher contains 0 to 0.6 times the tank liquid. The halide concentration in the replenisher is usually 0.006 mol / liter or less, but it is necessary to reduce the concentration as the replenisher becomes lower, and in some cases it may not be contained at all. In addition, a compound that is unlikely to change its concentration due to processing or aging is usually contained in approximately the same concentration as the color developing tank solution. Examples of this are chelating agents and buffers. Further, the pH of the color developing replenisher is to prevent the pH of the tank solution from decreasing due to processing.
It is about 0.05 to 0.5 higher than the tank liquid. This p
It is necessary to increase the difference in H as the replenishment amount decreases. The replenishing amount of color developer is 3000 ml per 1 m ^{2 of} light-sensitive material.
It is carried out below, but it is preferably 100 ml to 1500 ml, and most preferably 100 ml to 600 ml.

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

In the present invention, it is preferable to use a stop bath. The stop bath is used for the purpose of stopping development with an alkaline developer. Known organic or inorganic acids are usually used in the stop bath. Specifically, acetic acid or the like is preferably used. Concentration is 1 to 15% by weight
Is preferred.

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

The processing solution having fixing ability contains a fixing agent. As the fixing agent, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate, thiocyanates (rhodan salts) such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, thiourea, Thioether etc. can be mentioned. Of these, ammonium thiosulfate is preferably used. The amount of the fixing agent is 0.3 to 3 mol, preferably 0.5 to 2 mol, per liter of the processing liquid having fixing ability. Further, from the viewpoint of accelerating the fixing, thiosulfate is added to the above-mentioned ammonium thiocyanate (rhodanammonium), thiourea, thioether (for example, 3,6-dithia-1,8-octanediol), thiosulfonic acid (for example, ammonium methanethiosulfonate). )
It is also preferable to use in combination. Of these, it is most preferable to use thiosulfate and thiocyanate or thiosulfate and thiosulfonate together. In particular, the combined use of ammonium thiosulfate and ammonium methanethiosulfonate is preferable. The amount of these compounds used in combination is 0.01 to 1 mol, preferably 0.1 to 0.5 mol, per liter of the processing liquid having fixing ability, but in the case of thiocyanic acid, The fixing promoting effect can be greatly enhanced by using 1 to 3 mol. When thiosulfonic acid is used, it is preferable to use sulfinic acid described later in combination.

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. No. 231051 may be contained. Further, various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like 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 fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediamine. Examples thereof include tetraacetic acid, 1,2-propylenediaminetetraacetic acid, and 1,3-diaminopropanetetraacetic acid. Among these, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,3-diaminopropanetetraacetic acid and ethylenediaminetetraacetic acid are particularly preferable. The amount of the chelating agent added is 0.01 to 0.3 mol, preferably 0.03 to 1 mol, per liter of the treatment liquid.
It is 0.2 mol. The pH of the fixing solution is preferably 5-9, more preferably 6-8. Further, in the bleach-fixing solution, it is preferably 4.0 to 7.0, more preferably 5.0 to 6.5. To adjust the processing solution having fixing ability to such a pH range, and as a buffer,
It is preferable to contain a compound having a pKa in the range of 6.0 to 9.0. These compounds include imidazole,
Imidazoles such as 2-methyl-imidazole are preferred. These compounds are preferably 0.1 to 10 mol, preferably 0.2 mol to 3 mol, per liter of the treatment liquid.

The bleach-fixing solution may further contain a compound which can be contained in the bleaching solution described above. In the present invention, a bleach-fixing solution at the start of processing (start solution)
Is prepared by dissolving the above-mentioned compound used in the bleach-fixing solution in water, but it may be prepared by mixing an appropriately prepared bleaching solution and a separately-prepared fixing solution. When the replenishing system is adopted, the replenishing amount of the fixing solution or the bleach-fixing solution is 1 m of the light-sensitive material.
^It is preferably 100 to 3000 ml per ^2, but more preferably 300 to 1800 ml. The bleach-fixing solution may be replenished as a bleach-fixing replenishing solution.
Alternatively, an overflow solution of a bleaching solution and a fixing solution may be used as described in JP-A-143755 and JP-A-3-213853. Further, in the present invention, the total processing time of the processing having fixing ability is 0.5 to 5 minutes, preferably 1.5 to 4
Min, particularly preferably 2 to 3.5 min. In the processing liquid having fixing ability of the present invention, the processing temperature is 25 to 50 ° C.,
It is preferably 35 to 45 ° C.

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

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

Further, various kinds of antibacterial agents and antifungal agents may be contained in the washing water in order to prevent water stains and molds generated on the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents are JP-A-57 / 1982.
-157244 and 58-105145, thiazolylbenzimidazole compounds, isothiazolone compounds as shown in JP-A-57-8542, and chlorophenol compounds represented by trichlorophenol. Compounds, bromophenol compounds,
Quaternary compounds represented by organotin and organozinc compounds, thiocyanic acid and isothiocyanic acid compounds, acid amide compounds, diazine and triazine compounds, thiourea compounds, benzotriazole alkylguanidine compounds and benzalkonium chloride. Ammonium salts, antibiotics such as penicillin, etc., Journal Antibacterial & Antifung. Agents Vol 1. N
o.5, p. One or more general-purpose antifungal agents described in 207 to 223 (1983) may be used in combination. In addition, JP-A-48-
Various fungicides described in No. 83820 can also be used. Further, it is preferable to contain various chelating agents.
Preferred compounds of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid and diethylenetriamine-N, N, N ', N'-. Organic phosphonic acid such as tetramethylenephosphonic acid, or European Patent 3451
The hydrolyzate of the maleic anhydride polymer described in 72A1 and the like can be mentioned. Further, it is preferable that the wash water contains a preservative that can be contained in the fixing solution or the bleach-fixing solution.

The stabilizing solution used in the stabilizing step is a processing solution for stabilizing the dye image. For example, pH 3-6
Although a liquid having a buffering capacity, a liquid containing formaldehyde (for example, formalin), and the like can be used, the stabilizing liquid preferably used in the present invention will be described below. In the present invention, it is preferable that the stabilizing solution contains substantially no formaldehyde. Substantially free of formaldehyde means that the total amount of free formaldehyde and its hydrate is 0.0 per liter of stabilizing solution.
It represents not more than 03 mol. By using such a stabilizing solution, it is possible to suppress the scattering of formaldehyde vapor during processing. In this case, for the purpose of stabilizing the magenta dye, it is preferable that an image stabilizer other than formaldehyde (hereinafter referred to as formaldehyde substitute) is present in the stabilizing solution or the bleaching solution or its pre-bath (for example, preparation bath).

The preferred compound as a formaldehyde substitute is hexamethylenetetramine, and its derivatives,
Formaldehyde bisulfite adducts, benzaldehydes, azolylmethylamines and N-methylol compounds. In addition to stabilizing the magenta dye, these preferable compounds suppress the generation of yellow stain over time. Hexamethylenetetramine and its derivatives are known as "Beilsteins Handbuch der Organ".
Ishen Chemie) Volume II Supplement 26, P.200-P.212
Although the compounds described in 1) can be used, hexamethylene tetramine is particularly preferable. Further, as the formaldehyde bisulfite addition product, sodium formaldehyde bisulfite is preferable. As benzaldehydes, o
-Hydroxybenzaldehyde is preferred.

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

Of the above formaldehyde substitutes, particularly preferred are hexamethylenetetramine, formaldehyde sodium bisulfite, and the above-mentioned preferred azolylmethylamine and N-methylol compounds. Among them, N, N'-bis (1,2,4-triazol-1-ylmethyl) piperazine and N, N'-bis (pyrazol-1-ylmethyl) piperazine are most preferable. When the above-mentioned azolylmethylamine or N-methylol compound is used, it is preferable to coexist an amine compound such as triazole or pyrazole in the treatment liquid.
Coexistence of 0 times the molar concentration is preferable. The preferable addition amount of the above formaldehyde substitute is 0.0 per liter of the processing liquid.
The amount is 03 to 0.2 mol, preferably 0.005 to 0.05 mol. Two or more of these formaldehyde substitutes may be used in combination in the bath.

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

Next, the light-sensitive material used in the present invention will be further described. The silver halide photographic light-sensitive material of the present invention is preferably provided with a magnetic recording layer on the side opposite to the side provided with the silver halide emulsion layer with the support interposed therebetween.

The ferromagnetic fine powder used in the magnetic recording layer of the present invention includes ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metal powder, and ferromagnetic powder. Alloy powder, barium ferrite, etc. can be used. As an example of the ferromagnetic alloy powder, the metal content is 75
wt% or more, and 80 wt% or more of the metal content is at least one kind of ferromagnetic metal or alloy (Fe, Co, N
i, Fe-Co, Fe-Ni, Co-Ni, Co-Fe
-Ni, etc.) and other components (Al, Si, S, Sc, Ti, V, Cr, Mn, 20 wt% or less of the metal content).
Cu, Zn, Y, Mo, Rh, Pd, Ag, Sn, S
b, B, Ba, Ta, W, Re, Au, Hg, Pb,
P, La, Ce, Pr, Nb, Te, Bi, etc.) can be mentioned. Further, the ferromagnetic metal component may contain a small amount of water, hydroxide or oxide. The method for producing these ferromagnetic powders is known, and the ferromagnetic powder used in the present invention can also be produced according to known methods.

The shape and size of the ferromagnetic powder are not particularly limited and can be widely used. As the shape, needle shape, rice grain,
It may have a spherical shape, a cubic shape, a plate shape, or the like, but a needle shape or a plate shape is preferable in terms of electromagnetic conversion characteristics. The crystallite size and non-surface area are not particularly limited, but the crystallite size is 400 Å or less, S
It is preferably 1m ² / g~80m ² / g in _BET, 1m ² / _g~6
0 m ² / g is particularly preferred. The pH and surface treatment of the ferromagnetic powder can be used without particular limitation (titanium, silicon,
It may be surface-treated with a substance containing an element such as aluminum, or an organic compound such as a carboxylic acid, a sulfonic acid, a sulfuric acid ester, a phosphonic acid, a phosphoric acid ester or an adsorptive compound having a nitrogen-containing heterocyclic ring such as benzotriazole. Optionally treated with a compound). The preferred pH range is 5-10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular limitation on the ratio of divalent iron / trivalent iron. Regarding these magnetic recording layers, JP-A-47-32812
No. 53-109604. Content of ferromagnetic fine powder per 1 m ^{2 of} transparent support is 4 × 10 ⁻⁴
G～3g, preferably 10 ^-3 g~1g, more preferably ^{4 × 10 -3 g~4 × 10 -1} g.

The binder of the magnetic recording layer used in the present invention is a known thermoplastic resin, thermosetting resin, radiation curable resin, or the like which has been conventionally used as a binder for magnetic recording media.
Reactive resins and mixtures thereof can be used. The Tg of the resin is −40 ° C. to 150 ° C., and the weight average molecular weight is 10,000 to 300,000, preferably 10,000 to 100,000.
Examples of the thermoplastic resin include vinyl chloride / vinyl acetate copolymer, vinyl chloride, vinyl acetate and vinyl alcohol,
Copolymers with maleic acid and / or acrylic acid, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / acrylonitrile copolymers, vinyl copolymers such as ethylene / vinyl acetate copolymers, nitrocellulose, cellulose acetate Cellulose derivatives such as propionate and cellulose acetate butyrate resin, acrylic resin,
Polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin,
Amino resin, styrene butadiene resin, rubber resin such as butadiene acrylonitrile resin, silicone resin,
Fluorine-based resins may be mentioned. Of these, vinyl chloride resins are preferred because of their high dispersibility in ferromagnetic fine powder. As the radiation curable resin, the above-mentioned thermoplastic resin to which a group having a carbon-carbon unsaturated bond is bonded as a radiation curable functional group is used. Preferred functional groups include an acryloyl group and a methacryloyl group. In the binder molecules listed above, polar groups (epoxy group, -CO _{2
M, -OH, -NR 2, -NR} 3 X, -SO 3 M, -OS
_{O 3 M, -PO 3 M 2} , -OPO 3 M 2, wherein M is hydrogen,
It is an alkali metal or ammonium, and when there are a plurality of M's in one group, they may be different from each other. R
Is hydrogen or an alkyl group, and X is an anion)
May be introduced. The polymer binders listed above are used alone or in a mixture of several kinds, and can be cured by adding a known isocyanate-based crosslinking agent and / or a radiation-curable vinyl-based monomer.

Further, a hydrophilic binder may be used in the magnetic recording layer of the present invention. The hydrophilic binder used is Research Disclosure (RD) N
17643, page 26, and ibid. No. 18716, 6
It is described on page 51, and water-soluble polymers, cellulose esters, latex polymers, water-soluble polymer esters, etc. are exemplified. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and cellulose esters such as carboxymethyl cellulose and hydroxyethyl cellulose. Is. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable. Gelatin is a so-called alkali-processed (lime-processed) gelatin that is immersed in an alkali bath before extraction of gelatin, an acid-processed gelatin that is immersed in an acid bath, and a double-immersed gelatin that has been subjected to both of these processes in the manufacturing process. Any of gelatin may be used. If necessary, a part thereof may be colloidal albumin, casein, carboxymethyl cellulose, cellulose derivative such as hydroxyethyl cellulose, agar, sodium alginate, starch derivative, sugar derivative such as dextran, synthetic hydrophilic colloid such as polyvinyl alcohol, poly N- Vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof, partial hydrolysates, gelatin derivatives and the like may be used in combination with gelatin.

It is preferable to harden the magnetic recording layer containing gelatin, and as a hardening agent usable for the magnetic recording layer,
For example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,3.
5-triazine and others U.S. Pat. No. 3,288,77
5, 2,732,303, British Patent 974,7
23, 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others. US Patent No. 3,
Compounds having a reactive olefin described in 635,718, 3,232,763, British Patent 994,869, etc., N-hydroxymethylphthalimide, and other U.S. Pat. No. 2,732,316. Issue 2
N-methylol compounds described in US Pat. No. 586,168, isocyanates described in US Pat. No. 3,103,437, and US Pat. No. 3,017,28.
0, 2,983,611 and the like, aziridine compounds, US Pat. Nos. 2,725,294 and 2,725,295 and the like, acid derivatives,
Examples thereof include epoxy compounds described in US Pat. No. 3,091,537 and halogen carboxaldehydes such as mucochloric acid. Alternatively, as an inorganic compound hardening agent, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-32699.
No., Belgian Patent No. 825,726, JP-A-60-22
5148, JP-A-51-126125, JP-B-58
Examples include carboxyl group-activating type hardeners described in JP-A-50699, JP-A-52-54427, US Pat. No. 3,321,313 and the like.

The amount of the hardener used is usually 0.01 to 30% by weight, preferably 0.05 to 20% by weight based on dry gelatin.
% By weight. The thickness of the magnetic recording layer is 0.1 μm to 10 μm
m, preferably 0.2 μm to 5 μm, more preferably 0.5 μm to 3 μm.

It is preferable that the magnetic recording layer of the present invention is substantially transparent and is provided on the back surface of the photosensitive material almost all over. The magnetic recording layer can be provided by coating, printing or adhering on the back surface of the transparent support. It is also preferable to co-cast a solution of a polymer in which magnetized particles are dispersed and a solution of a polymer for preparing a transparent support to prepare a transparent support having a magnetic recording layer. In this case, it is preferable that the compositions of the two types of polymers are substantially the same. The magnetic recording layer may have functions such as lubricity improvement, curl control, antistatic and adhesion prevention, or may be provided with another functional layer to impart these functions. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve the scratch resistance. The back surface of the transparent support having a magnetic recording layer is subjected to calendering to improve smoothness, and S
The / N ratio can be improved. In this case, it is preferable to apply the photosensitive layer on the transparent support after the calendering treatment.

The material for the support of the light-sensitive material used in the present invention is not particularly limited, but various plastic films can be used, and preferred are cellulose derivatives (eg diacetyl, triacetyl, propionyl, butanoyl, acetyl). Propionyl-acetate, etc.), polyamide, polycarbonate described in U.S. Pat. No. 3,023,101, polyester described in Japanese Patent Publication No. 4040414 (eg polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene na). Phthalate, etc.), polystyrene, polypropylene, polyethylene, polysulfone, polyarylate, polyetherimide, etc.,
Particularly preferred are triacetyl cellulose, polyethylene terephthalate and polyethylene naphthalate.
Some of these films have polar groups (epoxy, -COO
_{2 M, -OH, -NR 2,} -NR 3 X, -SO 3 M, -OS
_{O 3 M, -PO 3 M 2} , -OP 3 M 2, however, M is hydrogen,
Alkali metal or ammonia, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, and X is an anion). Particularly preferred supports include polyethylene terephthalate, polyethylene naphthalate,
Polyarylate and copolymers and polymer blends using these as raw materials. These supports are preferably used after being heat-set after biaxial stretching, and may be heat-relaxed if necessary. Furthermore, it is preferable that these supports are preliminarily heat-treated at a temperature of Tg or lower in order to reduce the curling tendency. For example, in the case of polyethylene naphthalate, the Tg is about 120 ° C and therefore 119 ° C.
The heat treatment is preferably carried out at the following temperature for 0.2 to 48 hours, more preferably at 115 ° C. for 24 hours. In particular, in order to perform the heat treatment in a short time, it is preferable to raise the temperature once to Tg or more and gradually cool it in the vicinity of Tg because the efficiency is greatly improved. In the case of polyethylene naphthalate, once maintain a temperature between 130 ° C and 200 ° C, cool it to 125 ° C, and then to 100 ° C 4
By gradually cooling in 0 minutes, the heat treatment time can be significantly shortened. When the support subjected to such heat treatment is measured by a differential thermal analyzer, an endothermic peak appears in the vicinity of Tg.
It is preferable that the heat treatment is performed so as to be at least al / g and at most 1000 mcal / g, and more preferably at least 200 mcal / g and at most 500 mcal / g.

These supports of the present invention have a thickness of 6
0 μm or more and 300 μm or less, more preferably 70
μm to 200 μm. When the thickness is less than 60 μm, the toy-like curl generated by the shrinkage stress of the emulsion layer during drying becomes remarkable and the flatness is easily deteriorated.
A plasticizer may be added to these supports for the purpose of imparting flexibility and the like. Particularly in the case of cellulose ester, a plasticizer-containing material such as triphenyl phosphate, biphenyl diphenyl phosphate, dimethyl ethyl phosphate, etc. is preferable. Chemical treatment for firmly adhering a photographic layer (for example, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer or a layer having conductivity) on these supports,
Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment,
After surface activation treatment such as high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a photographic emulsion may be directly applied to obtain the adhesive strength. A method of forming an undercoat layer after surface treatment or without surface treatment and coating a photographic emulsion layer thereon may be used. Of these, particularly preferable are corona discharge treatment, flame treatment, ultraviolet treatment, and glow discharge treatment, and the treatment at a high temperature during treatment (for example,
100 ° C or higher, preferably 200 ° C or higher for several seconds
It is preferably several minutes). For the cellulose derivative, a single layer of gelatin solution dispersed in a methylene chloride / ketone / alcohol mixed organic solvent is applied to form an undercoat layer. Gelatin hardeners include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), epichlorohydrido. Don resins, vinyl sulfoalkyl-based curing agents and the like can be mentioned. Various additives may be contained in these undercoat liquids, if necessary. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments,
Examples include coating aids and antifoggants. When the undercoating liquid is used, an etching agent such as resorcin, chloral hydrate, chlorophenol and the like can be contained in the undercoating liquid.

The light-sensitive material of the present invention preferably has a layer having conductivity, and the conductivity has an electric resistance of 10 ³ Ω / cm to 10 ¹² Ω / cm (25 ° C., before and after development processing).
It is preferably 10% RH). In the light-sensitive material of the present invention, the electric resistance is about 10 ¹⁵ to 10 ¹⁶ Ω / cm (25 ° C., 10% RH) when the layer having conductivity is not provided. The conductive material used preferably is a crystalline metal oxide particle, and those containing oxygen vacancies and those containing a small amount of a foreign atom forming a donor with respect to the metal oxide used are generally conductive. In particular, the latter is particularly preferable because it does not give fog to the silver halide emulsion. Examples of metal oxides are ZnO and Ti
O ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
O, BaO, MoO ₃ , V ₂ O _{5 and the} like, or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing different kinds of atoms include, for example, addition of Al, In, etc. to ZnO, Sb to SnO ₂ ,
It is effective to add Nb, a halogen element and the like, and to TiO ₂ , add Nb, Ta and the like. The addition amount of these heteroatoms is preferably in the range of 0.01 mol% to 30 mol%, and particularly preferably 0.1 mol% to 10 mol%. Furthermore, in order to improve fine particle dispersibility and transparency,
A silicon compound may be added when the fine particles are formed. These metal oxide fine particles have conductivity, and their volume resistivity is 10 ⁷ Ω / cm or less, particularly 10 ⁵ Ω / cm or less. The lower limit of the volume resistivity is preferably 10 ⁻⁴ Ω /
It is about cm. Regarding these oxides, JP-A-56
-143431, 56-120519, 58-
No. 62647 and the like.

Further, as described in JP-B-59-6235, a conductive material in which the above-mentioned metal oxide is attached to other crystalline metal oxide particles or fibrous material (for example, titanium oxide) is used. May be. The particle size that can be used is preferably 1 μm or less, but when it is 0.5 μm or less, stability after dispersion is good and it is easy to use. Further, in order to make the light scattering property as small as possible, it is very preferable to use conductive particles of 0.3 μm or less because a transparent photosensitive material can be formed. When the conductive material is needle-like or fibrous, the length is preferably 30 μm or less and the diameter is 1 μm or less,
Particularly preferred is a length of 10 μm or less and a diameter of 0.3 μm
And the length / diameter ratio is 3 or more.

These conductive metal oxides may be coated from the coating liquid without a binder, and in that case, it is preferable to further coat the binder thereon.
It is further preferred that the metal oxide is coated with a binder. The binder is not particularly limited, but the binder used in the magnetic layer described above may be used. For example, a water-soluble binder such as gelatin, dextran, polyacrylamide, starch, or polyvinyl alcohol may be used, or a poly (meta) may be used. ) Acrylic ester, polyvinyl acetate, polyurethane, polyvinyl chloride, polyvinylidene chloride, styrene / butadiene copolymer, polystyrene, polyester, polyethylene,
Synthetic polymer binders such as polyethylene oxide, polypropylene and polycarbonate may be used in the organic solvent, and further these polymer binders may be used in the form of an aqueous dispersion. Further, these metal oxides may be used as a mixture of spherical and fibrous ones. In the present invention, the content of metal oxide is 0.0005 to 1 g
/ M ² is preferable, more preferably 0.0009 to 0.5
g / m ^2, particularly preferably 0.0012~0.3g / m ^2.

Further, a heat-resistant agent, a weather-resistant agent, inorganic particles, a water-soluble resin, an emulsion, etc. may be added to the layer made of a metal oxide for matting and improving the film quality within a range not impairing the effects of the present invention. good. For example, inorganic fine particles may be added to the layer made of a metal oxide. Examples of the inorganic fine particles to be added include silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like. The fine particles have an average particle size of 0.01 to
10 μm is preferable, and more preferably 0.01 to 5 μm.
m, 0.05 to 10 by weight ratio with respect to the solid content in the coating agent
Parts are preferred, and particularly preferred is 0.1 to 5 parts.

The additive layer of the conductive metal oxide used in the present invention is not particularly limited. Can be mentioned. Of these, preferred are a protective layer, an intermediate layer, an antihalation layer, an undercoat layer, a back layer, and a back protective layer,
More preferred are an undercoat layer, a back layer, an intermediate layer and an antihalation layer. More specifically, it is particularly preferable to add a conductive material to the back layer (in particular, the back first layer closest to the support).

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with the formaldehyde described in No. 7 and No. 4,435,503. The light-sensitive material of the present invention is disclosed in
No. 0-107029, JP-A No. 60-252340, JP-A No. 1-44940, and JP-A No. 1-445687, and a fog agent, a development accelerator, and a halogen by a redox reaction with an oxidized form of the developer. A compound that releases a silver halide solvent or the like can be contained. U.S. Pat. No. 4,740,454 and JP-A-62-018539 are used for the light-sensitive material of the present invention.
U.S. Pat. No. 4,788,132, JP-A-1-283.
It is preferable to include the mercapto compound described in No. 551 or the like.

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

In the light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272 are used.
248, and 1, described in JP-A No. 1-80941.
2-benzisothiazolin-3-one, n-butyl, p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various antiseptics or antifungal agents such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

In addition, as the light-sensitive material used in the present invention, the contents described in JP-A-4-62543, page 6, upper right column, line 17 to page 10, upper right column, line 17 and the Institute of Invention and Innovation Public Technical Report 94. Those described on pages 2 to 90 of -6023 can be preferably applied.

The package (patrone) for accommodating the light-sensitive material of the present invention may be any existing or publicly known one, and in particular, US Pat. No. 4,834,306, F.
IG. 1-FIG. 3 and the shape of FIG. 3 of US Pat. No. 4,846,418. 1-FIG. 3 or the U.S. Pat. No. 5,296,887 FIG. 1-FIG. Those described in 7 are preferable. The film format used in the present invention is defined in Japanese Industrial Standards "JIS. K-7519 (1982)" 13
5 type, Japanese Patent Laid-Open Nos. 4-123047 and 4-12
No. 3059, No. 4-123051, No. 4-12556
In addition to the formats described in No. 0, No. 4-126450 and No. 4-287040, any known format can be used.

The processed film can be stored by any method. Normally, in the case of a negative film, it is returned from the laboratory as a negative sheet or the like. You may. In particular, it is preferable that the photosensitive material having a magnetic recording layer be stored in a cartridge after being processed.

Specific examples of the light-sensitive material which is preferable to contain the radical scavenger of the present invention are listed below. Fuji Photo Film Co., Ltd. Fujicolor SUPER G100 〃 Fujicolor SUPER G200 〃 Fujicolor SUPER G400 〃 Fujicolor SUPER HG1600 〃 Fujicolor REALA 〃 Fujicolor FUJICOLA FUJICOLA Professional Fujicolor Super FUJICOLA FUJICOLA Super FUJICOLA Professional FUJICOLA Professional FUJICOLA Professional Fujicolor Super FUJICOLA Professional Fujicolor Super FUJICOLA Professional FUJICOLA Professional FUJICOLA Professional FUJICOLA Professional FUJICOLA Professional FUJICOLA Professional FUJICOLA FUJICOLA Professional FUJICOLA Professional FUJICOLA FUJICOLA Professional FUJICOLA Professional FUJICOLA FUJICOLA Professional FUJICOLA Professional Super Color Kodak Super Gold 200 〃 Kodak Gold 400 〃 Kodak Gold 1600 〃 Kodak Ector 25 〃 Kodak Ector 100 〃 Kodak Ector 1000 〃 Vericolor III Professional Film Type S 〃 Vericolor II Professional Film Type L Konica Color D Super K1 Photosensitive materials capable of C-41 processing by Eastman Kodak Company or CN-16 processing by Fuji Photo Film, such as 00 Konica Color Super DD200, Konica Color XG400, and Konica Color GX3200 are preferably used.

[0111]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 Sample 101, which is a multilayer color light-sensitive material, is processed as follows.
Was produced. 1) Support The support used in this example was prepared by the following method. 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
P. 2 parts by weight of 326 (manufactured by Geigy) are dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.0 times at 140 ° C., and subsequently at 130 ° C. for 3. The film was transversely stretched 0 times and further heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. further,
A part thereof was wound around a stainless steel core having a diameter of 20 cm and subjected to a heat history of 110 ° C. for 48 hours.

2) Coating of Undercoat Layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, glow discharge treatment, and flame treatment on both sides,
An undercoat liquid having the following composition was applied to each surface to form an undercoat layer on the high temperature surface side during stretching. For the corona discharge treatment, use a solid state corona treatment machine 6KVA model manufactured by Pillar Co.
A 0 cm wide support is treated at 20 m / min. At this time, the object to be treated is 0.375 KV.
A · minute / m ² was processed. The discharge frequency during processing is
The gap clearance between the electrode and the dielectric roll was 9.6 KHz and 1.6 mm. The UV discharge treatment is 75
Discharge treatment was performed while heating at ℃. Further, the glow discharge treatment was performed by irradiating with a cylindrical electrode at 3000 W for 30 seconds. Gelatin 3 g Distilled water 25 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Salicylic acid 0.1 g Diacetyl cellulose 0.5 g p-Chlorophenol 0.5 g Resorcin 0.5 g Cresol 0.5 g (CH ₂ =) CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.2 g trimethylolpropane triazine 0.2 g trimethylolpropane tristoluene diisocyanate 0.2 g methanol 15 cc acetone 85 cc formaldehyde 0.01 g acetic acid 0.01 g concentrated hydrochloric acid 0.01 g

3) Coating of Back Layer After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were provided as a back layer on one surface of the support. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution became 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. Colloidal precipitate from which excess ions have been removed 2
100 parts by weight of water was redispersed in 1500 parts by weight of water, and sprayed in a baking furnace heated to 650 ° C. to obtain a bluish average particle diameter of 0.0
A fine powder of 05 μm tin oxide-antimony oxide composite was obtained. The specific resistance of this fine particle powder was 5 Ω · cm. A mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, and roughly dispersed by a stirrer, and then a horizontal sand mill (trade name Dynomill; WILLYA.BACHO).
It was prepared by dispersing with FENAG) until the residence time reached 30 minutes. The average particle size of the secondary aggregate at this time is about 0.04.
μm.

3-1-2) Coating of conductive layer The following formulation was applied to give a dry film thickness of 0.2 μm,
It was dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight p-Chlorophenol 0.5 parts by weight Resorcin 2 parts by weight Polyoxyethylene nonylphenyl ether 0. 01 parts by weight The resistance of the obtained conductive film was 10 ^8.0 (100 V), and it had an excellent antistatic property.

3-1) Coating of magnetic recording layer Magnetic substance Co-adhered γ-Fe ₂ O ₃ (needle-like with major axis 0.14 μm, minor axis 0.03 μm, specific surface area 41 m ² / g, saturation magnetization 89 emu / g, the surface was surface-treated with 2% by weight of Fe ₂ O ₃ with aluminum oxide and silicon oxide, respectively.
0 Oe, Fe ^{+ 2} / Fe ⁺³ ratio is 6/94) 1100 g of water and 220 g of water and poly (degree of polymerization 16) oxysilanepropyl trimethoxysilane silane coupling agent 15
0 g was added and kneaded well in an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for one day to remove water, and then heated at 110 ° C. for 1 hour for treatment to prepare surface-treated magnetic particles. Further, the following formulation was used, and the mixture was kneaded again in an open kneader.

The above-mentioned surface-treated magnetic particles 1000 g Diacetyl cellulose 17 g Methyl ethyl ketone 100 g Cyclohexanone 100 g Furthermore, 200 with a sand mill (1/4 G) with the following formulation.
Finely dispersed at rpm for 4 hours. The above kneaded product 100 g Diacetyl cellulose 60 g Methyl ethyl ketone 300 g Cyclohexanone 300 g Further diacetyl cellulose and C ₂ H ₅ C (CH ₂ O) as a curing agent
20% by weight of CONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ with respect to the binder
Was added. The obtained liquid was diluted with equal amounts of methyl ethyl ketone and cyclohexanone so that the viscosity was about 80 cp. The coating was carried out on the above conductive layer with a bar coater, and the film thickness was 1.2 μm. The amount of magnetic material is 0.6
It was applied so as to be g / m ² . Also, silica particles (0.3 μm) as a matting agent and aluminum oxide (0.5 μm) as a polishing agent.
m) was added so as to be 10 mg / m ² . Drying was performed at 115 ° C. for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C.). When the blue filter was used in the status M of X-light, the increase in the color density of D ^B of the magnetic recording layer was about 0.1. The saturation magnetization moment of the magnetic recording layer is 4.2 emu /
The m ² , the coercive force was 923 Oe, and the squareness ratio was 65%.

3-1) Preparation of Sliding Layer The following formulation liquid was applied so that the solid coating amount of the compound was as follows, and dried at 110 ° C. for 5 minutes to apply a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC 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 Compound a / Compound b (6: 9) was xylene and propylene glycol monomethyl ether (volume ratio 1:
1) is heated to 105 ° C in the same amount of the solution and dissolved, and this solution is added to 1
0 times the amount of propylene glycol monomethyl ether (2
5 ° C.) to give a fine dispersion. Further dilute in 5 times the amount of acetone and use a high pressure homogenizer (200 atm).
Redispersion was carried out to prepare a dispersion (average particle size 0.01 μm), and then added and used. The performance of the obtained sliding layer was as follows: dynamic friction coefficient 0.06 (5 mmφ stainless hard ball, load 10
0 g, speed 6 cm / min), static friction coefficient 0.07 (clip method), and excellent properties. The sliding property with respect to the emulsion surface, which will be described later, also had a dynamic friction coefficient of 0.12.

4) Coating of Light-Sensitive Material Layer Next, each layer having the following composition was multilayer coated on the side opposite to the back layer obtained above to prepare a color negative photographic 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 number corresponding to each component indicates the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per 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 Silver 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 ExM-6 0.020 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 ExM-6 0.030 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

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

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve storage stability, 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-15 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0137]

[Table 1]

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

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

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

[0141]

[Chemical formula 23]

[0142]

[Chemical formula 24]

[0143]

[Chemical 25]

[0144]

[Chemical formula 26]

[0145]

[Chemical 27]

[0146]

[Chemical 28]

[0147]

[Chemical 29]

[0148]

Embedded image

[0149]

[Chemical 31]

[0150]

Embedded image

[0151]

[Chemical 33]

[0152]

Embedded image

[0153]

Embedded image

[0154]

Embedded image

[0155]

Embedded image

[0156]

[Chemical 38]

[0157]

[Chemical Formula 39]

Samples 102 to 107 were prepared by adding the radical scavenger to the 13th layer of this sample 101 in a different manner as shown in Table 2.

[0159]

[Table 2]

As shown in Table 3, the heterocyclic compound was changed to carry out continuous treatment with the treatment liquid formulation shown below until the replenishing amount of the bleaching solution became 3 times the tank volume. Processing is sample 101-
107 was cut and subjected to imagewise exposure, and each sample was continuously processed at the same area ratio.

Treatment Process Treatment Time Treatment Temperature Replenishment Amount * Tank Capacity (° C) (ml) (liter) Color development 3 minutes 15 seconds 38 22 40 Stop 1 minute 38 10 20 Wash with water (1) 1 minute 24 200 20 Bleach 3 minutes 38 10 40 Washing with water (2) 1 minute 24 200 20 Settling 3 minutes 38 15 40 Washing with water (3) 1 minute 24 --- 20 Washing with water (4) 1 minute 24 200 20 Stability 1 minute 38 15 20 20 Dry 4 Min 55 * Replenishment amount is per 35 mm width of photosensitive material and 1 m length. Supplied with countercurrent piping from flush (4) to flush (3). The bleaching tank liquid was equipped with an aeration device and was aerated at a flow rate of 1 liter per minute. The crossover time is 3 seconds in each case, and this time is included in the processing time of the previous step. The composition of the treatment liquid is shown below.

(Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 1.2 1.2 1-Hydroxyethylidene-1,1-2.7 3.3 Diphosphonic acid Caustic potassium 1.72 1. 9 Sodium sulfite 3.84 4.8 Sodium bicarbonate 1.8-Potassium carbonate 31.7 39.0 Potassium bromide 1.4 0.37 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.5 3.1 Compound of the following chemical formula 40 0.044 −

[0163]

[Chemical 40]

2-Methyl-4- [N-ethyl-N-4.7 5.9 (β-hydroxyethyl) amino] aniline sulphate Water was added to 1.0 liter 1.0 liter pH 10.05 10 .15

(Stop solution) Tank solution (g) Replenisher solution (g) Acetic acid (90%) 40.0 g 60.0 g Water was added to 1.0 liter 1.0 liter pH 4.00 3.00

(Bleach) As shown in Table 3

[0167]

[Table 3]

In Table 3, "○" in the prescriptions A to M
Compounds marked with are the components included in each formulation. Compound group (X): (1) sodium persulfate (2) hydrogen peroxide (3) sodium perborate (4) potassium chlorate (5) potassium permanganate (6) 1-chlorobenzotriazole compound Z: 2 -Aminopyridine In addition, the pH of each replenisher was adjusted to 3.70 by doubling the concentration of each component. The pH was adjusted with sodium hydroxide and sulfuric acid.

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 21 23 Ammonium thiosulfate aqueous solution 288 320 ml (750 g / liter) Ethylenediaminetetraacetic acid 0.6 0.68 Water was added to 1.0 liter 1. 0 liter pH [adjusted with aqueous ammonia and acetic acid] 6.8 6.8

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH-type strongly basic anion exchange resin (Amberlite IRA-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3
Treatment to less than mg / liter, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 15
0 mg / l was added. The pH of this solution is 6.5
It was in the range of 7.5.

(Stabilizing Solution and Stable Replenishing Solution) (Unit g) Triazole 1.5 N, N′-bis (1,2,4-triazo 0.5 ru-1-ylmethyl) piperazine p-toluenesulfinic acid 05 sodium polyoxyethylene-p-monononyl 0.2 phenyl ether (average degree of polymerization 10) ethylenediaminetetraacetic acid disodium salt 0.05 water was added to 1.0 liter pH 8.0

Samples 101 to 107 were added to the liquid after the continuous treatment.
The sample exposed to 20 CMS and the sample unexposed were processed, and the magenta transmission density of the exposed area and the yellow transmission density of the unexposed area were measured. Table 4 shows the difference in transmission density of magenta from that of the standard processing of CN-16X manufactured by Fuji Photo Film Co., Ltd. Each color density is Fuji Photo Film Co., Ltd.
It was measured using a photographic densitometer FSD103. The amount of residual silver in the exposed area was quantified with a fluorescent X-ray analyzer. The results are shown in Table 4.

[0173]

[Table 4]

As shown in Table 4, a processing method showing good desilvering property, little fog, and no color image fading even when the processing is carried out using a bleaching agent having a small environmental load in the practice of the present invention. It can be seen that it is. Further, it can be seen that Samples 104 to 107 using the preferred radical scavenger of the present invention have less fog and less fading of the color image than Samples 102 and 103.

Example 2 Preparation of Sample 201 Sample 2 of Example 2 of JIII Journal of Technical Disclosure No. 94-6023
01, ExS-205 and ExS-206 are as follows, and F-210 and F-211 are A-3 in the text.
A sample 201 was prepared in place of 9, A-3.

[0176]

Embedded image

Processing was carried out in the same manner as in Example 1 except that the bleaching solution and the bleaching replenishing solution were changed as shown below and in Table 5. (Bleaching solution) Tank solution Replenishing solution Heterocyclic compound (shown in Table 5) 14 mmol 21 mmol Organic acids (shown in Table 5) 100 mmol 150 mmol Iron nitrate 9-hydrate 2.55 g 3.83 g Acetic acid (90%) 67.0 g 100.0 g Sodium hydroxide 38 ml 50 ml Sodium persulfate 30.0 g 45.0 g Imidazole 0.5 g 0.75 g Sodium chloride 15.0 g 22.5 g Gelatin 0.5 g 0.75 g Water added 1.0 liter 1.0 liter pH 3.5 3.3

Sample 201 exposed to 5 CMS and unexposed sample 201 were processed, and the magenta transmission density of the exposed area and the yellow transmission density of the unexposed area were measured in the same manner as in Example 1. The amount of residual silver in the exposed area was quantified with a fluorescent X-ray analyzer, and the results are shown in Table 5.

[0179]

[Table 5]

As is clear from the results in Table 5, by adding a dicarboxylic acid to the bleaching solution of the present invention, it is possible to further suppress fogging and ensure excellent desilvering property.

[0181]

EFFECTS OF THE INVENTION According to the present invention as shown in the above text and examples, a bleaching solution having good biodegradability is used,
It is possible to provide a processing method that ensures excellent desilvering property, suppresses bleaching fog, and suppresses fading of a color image. Further, by using a preferable radical scavenger in the light-sensitive material, the effect of the present invention can be made more remarkable.

Claims (4)

[Claims] 1. A method of subjecting an imagewise exposed silver halide color photographic light-sensitive material to color development and then processing with a processing solution having a bleaching ability, wherein the light-sensitive material is contained in at least one photographic constituent layer of at least one kind. (A) at least one heterocyclic compound having a carboxyl group or its salt in the molecule, and (b) persulfuric acid or its salt, hydrogen peroxide or its Salt, perboric acid or its salt, permanganic acid or its salt, hypohalous acid or its salt,
Halogen acid or its salt, perhalogen acid or its salt, organic peracid, organic peroxide, iodosyl compound, N-
A method of processing a silver halide color photographic light-sensitive material, which comprises at least one kind of halocarboxylic acid amide, N-halosulfonic acid amide, or quinones, and (c) contains ferric ion. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the heterocyclic compound having a carboxyl group or a salt thereof in the molecule is a compound represented by the following general formula (I). Material processing method. Embedded image In the formula, Q represents a nonmetallic atom group necessary for forming a heterocycle. p represents 0 or 1. Ma represents a hydrogen atom or an organic or inorganic cation. 3. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the radical scavenger is a compound represented by the following general formula (A). Embedded image In formula (A), R _a1 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, R _a2 represents a group represented hydrogen atom or R _a1, R _a1 and R _a2 may form a 5- to 7-membered ring together. Provided that when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is a heterocyclic group, an acyl group,
A sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. 4. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution having a bleaching ability further contains a hydrocarbon dicarboxylic acid.