JPH0829935A - Development processing method and processing apparatus therefor - Google Patents

Abstract

PURPOSE:To make a persulfuric acid salt-type bleaching liquid usable in a common miniaturized laboratory by using the persulfuric acid salt-type bleaching liquid in an automatic developing machine and using a specified stainless steel for parts of the machine which are possibly brought into contact with the bleaching liquid, said bleaching liquid has a high bleaching function even if its concentration is low, does not produce stains, and scarcely causes environmental pollution. CONSTITUTION:A persulfuric acid salt-type bleaching agent is used as a bleaching liquid for an automatic developing machine and portions of members which are possibly brought into contact with the bleaching liquid are made of a stainless steel containing 2-4wt.% of No, 10-15wt.% of Ni, 16-20wt.% of Cr, and <=0.08wt.% of C. The persulfuric acid salt-type bleaching liquid contains pyridine-2-boxylic acid having a formula I or pyridine-2,6-dicarboxylic acid having a formula II and also contains one of metal ions selected from ferric ion, cobaltic ion, and nickelic ion. In the formulas I, II, X1, X2, X3, and X4 independently stand for hydrogen atom, a hydroxyl group, -COOM, -SO3M, or -PO3M wherein M stands for hydrogen atom or an alkali metal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material processing method and a processing machine which are excellent in photographic characteristics and environmental protection.

2. Description of the Related Art Ethylenediaminetetraacetic acid ferric iron complex salt and ferric iron 1,3-diaminopropanetetraacetic acid are generally used as oxidizing agents in bleaching solutions conventionally used for color development and reducing solutions used in black and white photographic processing. Complex salts are used, but these are difficult to biodegrade. In recent years, from the viewpoint of environmental protection, detoxification of photographic processing waste liquid generated from these photographic processing steps has been desired, and substitution of the above-mentioned non-biodegradable bleaching agent has been studied.

As a bleaching agent having biodegradability, N-
The ferric complex salt of (2-carboxymethoxyphenyl) iminodiacetic acid is described in West German Patent Publication No. 3912551, and the ferric iron complex salt of β-alanine diacetic acid or glycine dipropionic acid is disclosed in European Patent Publication No. 430000A, ethylenediamine-N. Ferric acid complex salt of N, N'-disuccinic acid is disclosed in JP-A-5-72.
No. 695. However, a processing solution having a bleaching ability consisting of these bleaching agents cannot be said to have sufficient desilvering property, and continuous processing using these causes a problem that the desilvering property lowers compared to the initial stage of continuous processing and bleaching. It was found that there are problems such as deterioration of fog and insufficient prevention of stain over time. For these color processing, a small automatic developing machine called a minilab has recently been provided with a rapid processing service to customers, and in addition to quick bleaching, stability of these performances in continuous processing is an essential issue. . Further, also from the viewpoint of environmental protection, the concentration of the metal chelate compound used as a bleaching agent is reduced in order to reduce the concentration of the chemicals in the processing solution and reduce carry-out during carryover during processing of the light-sensitive material. It is desired However, the above-mentioned bleaching agent could not obtain sufficient desilvering property at a dilute concentration.

[0003]

Although a persulfuric acid bleaching solution has been conventionally known, it is not generally used because the persulfate salt itself is unstable and may cause an explosion. However, it may also be used as a bleaching solution in the development of motion picture films.
For example, British Journal of Photograpy p.196 (198
8). Further, during use, there are many processing steps such as color development, development stoppage, washing with water, bleaching, washing with water, fixing, washing with water, and it cannot be used for general amateur treatment. The persulfuric acid bleaching solution has a strong activity and cannot be used as it is, for example, in a minilab. For example, in a normal minilab, the tank is made of plastic, and the development rack always uses metal because the strength is insufficient unless the metal is used for the drive shaft and screws.

An object of the present invention is to provide a so-called eco-friendly persulfate type bleaching solution which has good bleaching performance even when the concentration of the drug is low, does not cause bleaching fog, that is, stains, and is biodegradable. It is an object of the present invention to provide a method for processing a silver halide light-sensitive material that can be used even in an ordinary minilab and an automatic developing machine for the same.

[0005]

[Means for Solving the Problems]

(1) In an automatic developing machine for a silver halide light-sensitive material having at least developing, development stopping, bleaching and fixing tanks,
A persulfate-type bleaching solution is used as the bleaching solution, and at least a part of the member that can come into contact with the bleaching solution contains 2 to 4% by weight of Mo, N
i 10 to 15% by weight, Cr 16 to 20% by weight, C ≦ 0.
An automatic processor for silver halide light-sensitive materials, characterized by being 08% by weight of stainless steel. (2) The persulfate-type bleaching solution contains at least 2-pyridinecarboxylic acid represented by the following formula (I) or 2,6-pyridinedicarboxylic acid represented by the following formula (II), And ferric ion, cobalt ion and second
The automatic developing machine for a silver halide light-sensitive material as described in (1) above, which contains at least one metal ion among nickel ions.

[0006]

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In the formulas (I) and (II), X ₁ , X ₂ and X ₃
Or X ₄ are each independently a hydrogen atom, a hydroxyl group, —C
Represents OOM, —SO ₃ M or —PO ₃ M, and M represents a hydrogen atom or an alkali metal. (3) The replenisher for the persulfate-type bleaching solution is divided into at least two parts, a persulfate portion and a metal ion portion, and the persulfate portion is removed by receiving a signal for setting a silver halide light-sensitive material to be processed. The light-sensitive material is replenished in a bleaching bath, and 1 to 15 minutes after the replenishment, the light-sensitive material is bleached, and the metal ion portion is replenished in the bleaching bath during the bleaching treatment or after or just before the bleaching treatment. The automatic developing machine for a silver halide light-sensitive material as described in (1) or (2) above, having a control mechanism as described above. (4) In an automatic processor for silver halide light-sensitive materials having at least each of development, development stop, bleaching, fixing or bleach-fixing tanks, the replenisher in one of the processing tanks is divided into two parts for halogenation. Receiving the signal that sets the silver photosensitive material, replenish the processing tank with any one of the above parts,
An automatic developing machine for silver halide light-sensitive materials having a control mechanism for replenishing another part to the processing tank after that. (5) The silver halide light-sensitive material described in (4) above, wherein the replenishment of the processing solution is performed by combining two or more switching cocks and a pump in two or more parts at different timings. Automatic developing machine. (6) In a method of processing a silver halide light-sensitive material, which comprises at least development, development stoppage, bleaching and fixing steps,
A persulfate type bleaching solution is used as the bleaching solution, and a member which can come into contact with the bleaching solution comprises 2 to 4% by weight of Mo, 10 to 15% by weight of Ni, 16 to 20% by weight of Cr, and C ≦ 0.08% by weight. A method of processing a silver halide light-sensitive material, which is made of steel and is replenished with a bleaching solution such that the solution exchange rate is 3% or more and 600% or less per day.

Furthermore, as one of preferred embodiments of the present invention, in the processing method of a silver halide light-sensitive material having at least each step of development, development stop, bleaching and fixing, the automatic developing machine described in (5) above is used. A persulfate-type bleaching solution is used as the bleaching solution, and a replenisher for the persulfate-type bleaching solution is divided into two parts, a persulfate part and a metal ion part, and processed. The persulfate portion is replenished to the bleaching solution tank in response to the signal set by, and the photosensitive material is bleached 1 to 15 minutes after the replenishment, during the bleaching treatment, after the bleaching treatment or after the bleaching treatment. It is a method of processing a silver halide light-sensitive material characterized by controlling so that the metal ion portion is replenished in a bleaching solution tank immediately before processing.

That is, by using a persulfate type bleaching solution in the method for processing a silver halide light-sensitive material of the present invention and in an automatic processor, the concentration of the chemical can be reduced and the persulfate is unstable and decomposes. It is easy to do and is decomposed into sodium sulphate etc. to be harmless, which is convenient for the environment, but bleaching fog (generation of stain) occurs. However, by combining a specific material of the automatic developing machine and a specific controlled replenishment method, these problems can be solved, stable bleaching performance can be obtained, and detoxification can be achieved.

Further, at least a pyridinecarboxylic acid represented by the above formula (I) or (II) is used as a metal chelating agent in the bleaching solution used in the present invention together with a persulfate, and a ferric ion is used as a metal ion. By using at least one of the second cobalt ion and the second nickel ion, the amount of the metal ion used can be less than the amount used in the conventional amateur, and the metal ion is taken out to the sensitive material and washed. The amount of metal ions in the processing waste liquid discharged to the outside of the system by soaking is also small. Furthermore, an aminopolycarboxylic acid type chelating agent has been conventionally used in order to allow the metal ions to stably exist in the aqueous solution, but this chelating agent is a compound which is hardly biodegradable. The pyridinecarboxylic acid used in the present invention is a bleaching solution that is easily biodegradable and has sufficient chelating ability, and as a result, is environmentally friendly. However, when it was used in a normal minilab, it had a problem of corrosion and could not be used in the past. In the present invention, this corrosion problem is solved by using the material of the bleaching bath described above. Further, by using the persulfate, metal ion, and a chelating agent in combination,
A persulfate that is less than conventional bleaching solutions and one that has less total metal ions than conventional aminopolycarboxylic acid iron type bleaching agents can be obtained, and a bleaching solution with less environmental load can be obtained. Further, it is preferable that the persulfate and the stainless steel used in the present invention are used so that the liquid exchange rate by replenishing the bleaching solution is 3% or more and 600% or less per day. As a result, the bleaching performance is stable, and bleaching fog (generation of stains) due to persulfate is suppressed. For example, if a processor with a small amount of tank liquid is used, stable processing can be performed even in the off-gas treatment.

The persulfate type bleaching solution used in the present invention will be described. Here, the bleaching solution uses an oxidizing agent as a main agent, and specific examples of the main agent include persulfate, hydrogen peroxide, perborate, hypohalite, halogenate, permanganate, and permanganate. Examples thereof include halogenates and organic peroxides.
The persulfate type bleaching agent refers to a bleaching solution containing at least a persulfate as a main component. Persulfate bleach contains
There are (a) persulfate alone and (b) a combination of persulfate and metal. (A) Persulfate alone is dangerous because bleaching performance cannot be obtained unless the pH is 2 or less. Therefore, it is preferable to use (b) persulfate in combination with a metal. This will result in a relatively high pH (2-5) due to metal catalysis.
Can be processed by. Therefore, the persulfate-type bleaching agent as used herein includes (a) and (b), but preferably (b).

Of the persulfate type bleaching solutions, the bleaching solution containing unstable persulfate and metal salt is the most environmentally friendly. This is because the amount of persulfate which is an oxidant is small, and the amount of metal ions coexisting with persulfate is much smaller than that of a conventional EDTA iron salt bleaching solution, for example, a level of about 1/10 to 1/50. It can be used in. However, in this solution, metal ions accelerate the decomposition of persulfuric acid, so that they become more unstable if they coexist at the same time. Therefore, it is preferable to use the persulfate as a main component and the metal ion as a main component separately. In particular, it is preferable that the replenisher is separated and replenished. Moreover, it is preferable to mix and use immediately before the treatment. In this case, as the portion containing persulfate as the main agent, in addition to the persulfate, Cl, Br, I
Etc. may be included. In addition, an alkaline agent such as NaOH, KOH, Na ₂ CO ₃ , K ₂ CO as a pH adjusting agent
You can add ₃ etc. In the portion containing a metal ion as a main component, as a metal, for example, in addition to Fe, Co, Ni and the like, a chelating agent, preferably a chelating agent which is easily biodegradable, for example, pyridinecarboxylic acid is included. This allows the metal ions to exist stably in the liquid. In addition, an alkylcarboxylic acid such as acetic acid, citric acid, malic acid, succinic acid may be used as the pH adjusting agent.
The metal ions may be contained in the form of sulfate, nitrate or hydrochloride.

The bleaching solution used in the present invention contains at least a persulfate salt. Examples of persulfates include ammonium persulfate, potassium persulfate, and sodium persulfate. The concentration of persulfate in the bleaching solution is preferably 0.3 M or less, more preferably 0.01 M or more and 0.15 M or less. Instead of the above persulfate, hydrogen peroxide, perborates, hypohalites, halogenates,
Permanganates, perhalogenates, organic peroxides and the like can be used, but other than hydrogen peroxide, they are not preferable from the environmental viewpoint. The decomposition product of hydrogen peroxide is harmless because it is water,
It is difficult to handle from the viewpoint of stability and explosion hazard.

Metals preferably used in the bleaching solution in the present invention include iron (III), cobalt (III) and nickel.
Examples include polyvalent metals such as (III), from (VI), and copper (II). Among these, iron (III), cobalt (III),
Nickel (III) is preferred. By using these, these metals are preferable in that they are easy to handle in terms of pollution and have a small environmental load even if they are accidentally discharged.
More preferably, the second metal ion is inexpensive in terms of cost.
Iron salts are preferred. However, it is also possible to select cobalt from the photosensitive material to be processed and the material of the developing machine. The metal ion concentration in the bleaching solution is preferably set to a remarkably lower concentration than in the prior art in order to prevent stain over time and the like. Specifically, it is preferably 0.05 M or less, more preferably 0.0 M or less.
It is 01M or more and 0.03M or less.

Examples of the chelating agent preferably used in the bleaching solution in the present invention include pyridinecarboxylic acids and ethylenediaminetetraacetic acid. In terms of biodegradability,
It is preferable to use a heterocyclic compound having a carboxyl group in the molecule. Although details of these are not clear, they are more biodegradable than aminocarboxylic acids and can be used if they have an appropriate chelating ability. 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 heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, more preferably 5 to 6 containing a nitrogen atom.
A 5-membered aromatic heterocyclic group, more preferably a 5- to 6-membered aromatic heterocyclic group containing 1 to 2 nitrogen 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. These heterocycles may be substituted with 1 to 4 carboxyl groups so as to retain the ability to chelate with a metal. These compounds are Organic Syntheses Coll
The synthetic method is described in ective, Volume 3 , page 740.

Of the above chelating agents, pyridinecarboxylic acids are more preferred. Specifically, it is a pyridinecarboxylic acid represented by the above formula (I) or formula (II). This chelating agent has better biodegradability and is environmentally friendly than conventional aminopolycarboxylic acids. In formula (I) or (II), X ₁ to
X ₄ is independently a hydrogen atom, a hydroxyl group, —CO
OM, represents -SO ₃ M or -PO ₃ M, M represents a hydrogen atom, or an alkali metal. Here, examples of the alkali metal include sodium, potassium and lithium, and in some cases calcium and magnesium. Where X
_{1 to} X ₄ are preferably —COOM or —OH. More specific exemplary compounds of pyridinedicarboxylic acid preferably used in the present invention are as follows.

[0018]

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Of the above chelating agents, most preferably
It is 2,6-pyridinedicarboxylic acid from the viewpoint of low price and availability at present. The amount of the chelating agent added to the bleaching solution depends on the valence of the metal ion, but is preferably equimolar to 4 times the molar amount of the metal ion. The concentration of the chelating agent in the bleaching solution is preferably 0.001 to 0.5M,
It is more preferably 0.001 to 0.05M, and particularly preferably 0.001 to 0.03M. The replenishers are also used at the same concentration. In the bleaching solution used in the present invention, the persulfate, the metal ion, and the chelating agent are used in combination, so that the persulfate content is lower than that of the conventional bleaching solution, and the total metal content is higher than that of the conventional aminopolycarboxylic acid iron-type bleaching agent. A bleaching solution having a small amount of ions and having a good bleaching performance with a low environmental load can be obtained.

The pH of the bleaching solution is usually 1 to 7, preferably 3
~ 5 but lower pH for faster processing
It can also be processed with. If necessary, a bleaching accelerator can be used in the bleaching solution and the prebath thereof.
Specific examples of useful bleaching accelerators are described in the following specifications; U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-95630, Research. Disclosure No. 17129 (19
(July 1978) and the like, compounds having a mercapto group or a disulfide bond; thiazolidine derivatives described in JP-A No. 50-140129; US Pat.
The thiourea derivative described in Japanese Patent No. 561;
35, iodide salt; West German Patent 2,748,43
Polyoxyethylene compounds described in No. 0; JP-B-45
A polyamine compound described in -8836; bromide ion or the like can be used. Of these, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and is particularly described in U.S. Pat. Compounds are preferred. Further, U.S. Pat. No. 4,552,
The compounds described in No. 834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

In the present invention, the member which can be brought into contact with the bleaching solution is Mo2-4 wt%; Ni10-15.
wt%; Cr 16 to 20 wt%; C ≦ 0.08 wt%, at least stainless steel. here,
The member that can come into contact with the bleaching solution is each member that constitutes a bleaching solution tank or a bleaching solution rack, and more specifically, in the bleaching tank, the shaft of the drive gear, the screw that stops the gear, the drive gear,
These are the core of the roller, the side plate for holding the rack, and the guide plate. For example, in the case of plastic, it is most important to use the above-mentioned material for the shaft and screw of the drive gear for transporting the sensitive material which has insufficient mechanical strength.

The stainless steel parts as described above are
For example, SUS316 (Mo2-3 manufactured by Nippon Metal Industry Co., Ltd.)
% By weight; Ni 10-14% by weight; Cr 16-18% by weight; C ≦ 0.08% by weight), SUS317 (Mo 3-4)
% By weight; Ni 11-15% by weight; Cr 18-20% by weight; C ≦ 0.08% by weight); SUS317L (Mo3-
4 wt%; Ni 11-15 wt%; Cr 18-20 wt%; C ≦ 0.03 wt%), SUS316L (Mo2-
3% by weight; Ni 12 to 15% by weight; Cr 16 to 18% by weight; C ≦ 0.03% by weight). SUS303 that does not contain Mo (Ni 8-10 wt%; Cr 17-
19% by weight; C ≦ 0.15% by weight), SUS304 (N
i8 to 10.5% by weight; Cr 18 to 20% by weight; C ≦
0.08% by weight) is not preferable because corrosion easily occurs. Other than stainless steel, titanium steel or nickel steel can be used, but the above stainless steel is easy to use in terms of mechanical strength and price.

The following can be used as the silver halide light-sensitive material and the processing agent which can be used in the present invention. First, the silver halide photosensitive material will be described. The silver halide light-sensitive material that can be used in the present invention is, for each application, for amateur, industrial material, medical, scientific, etc., and for each processing method, for black-and-white development, color development, ordinary negative type processing method, light -A positive method by reversal, a positive method by chemical reversal, a positive method with a reversal mechanism in emulsion, and a positive method by diffusion transfer can be used.

The support may be a transparent support, an opaque support or a semitransparent support, and the support has a thickness of 30 to 500 μm.
Level ones can be used. Emulsions include various halogen species and combinations of halogen species, that is, one-component, two-component, and three-component emulsions, those in which the distribution of halogen is changed in the grain formation process, and grains are laminated. Any of the above-mentioned grain structures, those having a different core / shell ratio, emulsions to which conversion has been added, and junction type emulsions can be used.

Further, the morphology of the particles includes hexahedron, octahedron,
A tetrahedral structure, a mixture thereof, a twin crystal, a flat plate, or a spherical one can be used. As the tabular one, those having various aspect ratios, a mixture thereof or a mixture with other particles can be used. Further, the particle size may be uniform or may have a distribution. For example, less than 0.1 μm, 0.1 to 0.4 μm, 0.4 to 1 μm
m, 1 μm or more and the like, or a single combination.

The emulsion may contain a binder other than gelatin. For example, it is preferable that a natural polymer, a synthetic polymer, or these are dispersed and mixed in various particle sizes.
Also, the allocation may be changed for each layer. These silver halide grains may adsorb various sensitizing dyes, desensitizing dyes, stabilizers, chemical sensitizers, and physical sensitizers, or may coexist during preparation. Further, the emulsion mixture may contain various dyes, surfactants, hardeners, oils and the like. An anti-fading agent, an anti-color mixing agent, a nucleating agent, a matting agent, a slip agent, a mordant, a toning agent, a development aid, and a developer may be contained directly or in oil.

Various metals may be added during the grain formation process, or may be added directly to the emulsion. Suitable metals are gold, platinum, rubidium, palladium, iron, cobalt, nickel, iridium, rhodium, silver and the like, but they may be mixed with various chelating agents and used. The color light-sensitive material may further contain various couplers.

Examples thereof include pivaloyl-based / benzoyl-based Y couplers, pyrazolone-based / pyrazoloazole-based M couplers, and phenol-naphthol-based C couplers. Further, various DIR couplers, colored couplers, polymer couplers, and couplers having various leaving groups can be used as the functional coupler. The light-sensitive material layer can be formed by combining the above-mentioned emulsion and various additives, or in the case of a color light-sensitive material, further combining various couplers. The function may be divided into two layers or three layers even with a black and white light-sensitive material, or in the case of a color light-sensitive material, it is divided into 3 colors, and in some cases 4 to 5, and the layers are assembled so as to be sensed by light. Good. Finally, in addition to the emulsion layer, an undercoat layer, an intermediate layer,
You may provide a protective layer, a peeling layer, a separation layer, a neutralization layer, a filter layer, a vapor deposition layer, a reflection layer, a light shielding layer, etc. Further, a light-sensitive material provided with a back layer for the purpose of curl correction, static prevention, magnetic recording and the like can be used for the back of the support. As a total value of these, the sensitivity is ISO 0.1 to ISO 2
000 and gradation of 0.1 to 10 can be used.

As another photosensitive material, a film having a magnetic recording portion on the back surface of a silver halide photosensitive material and a film obtained by photographing this film with a Switchable Format Camera described in Photographic Trade News June, 22 (1992) can be processed. . Details of such a light-sensitive material are disclosed in JP-A-59-
23505; ibid 4-096052; ibid 4-19572.
6; ibid 4-192116; ibid. 4-259911; ibid. 5-
081652.

The present invention can be applied to various processing liquids. The color developing solution is preferably an alkaline aqueous solution containing an aromatic primary amino type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 4- Amino-N-ethyl-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-δ-hydroxybutylaniline and their sulfates, hydrochlorides or p- Toluene sulfonate may be mentioned. Two or more kinds of these compounds may be used in combination depending on the purpose.

The color developer is a carbonate of alcal metal,
It generally contains a pH buffer such as borate or phosphate, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzthiazole or a mercapto compound, or an antifoggant. is there. In addition, if necessary, various preservatives such as hydroxylamine, N, N-di (sulfoethyl) hydroxylamine, diethylhydroxylamine, sulfite, hydrazines, phenylsemicarbazides, triethanolamine, and catecholdisphonic acid, ethylene. Glycol, organic solvent such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salt, fogging agent such as boron hydride, auxiliary developing agent such as 1-phenyl-3-pyrazolidone, tackifier, aminopolycarboxylic acid , Various chelating agents represented by aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid. , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -
N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid,
Ethylenediamine-di (o-hydroxyphenylacetic acid)
And their salts can be mentioned as typical examples.

The pH of these color developers is generally 9-12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 1 liter or less per 1 m 2 of the light-sensitive material, and is reduced to 300 ml or less by reducing the bromide ion concentration in the replenisher. You can also do it. Preferably 30 m
1 to 150 ml / m ² . When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached as described above. As the fixing agent in the present invention, thiosulfates, thiocyanates, thioether compounds,
Although thioureas and a large amount of iodide salts can be used, thiosulfates are generally used, and ammonium thiosulfate is most widely used.

Further, after the desilvering treatment, washing and / or stabilizing steps are generally performed. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as couplers), application, and further the rinsing water temperature, the number of rinsing tanks (the number of stages),
It can be set in a wide range depending on a replenishment method such as normal flow and various other conditions. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is shown in the Jouranl of the Society of Moti
on Picture and Television Engineers Volume 64, P248 ~
253 (May 1955 issue).

According to the multistage countercurrent system described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances produced to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Also, Japanese Patent Application Laid-Open No.
No. 8542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents," Sanitary Technology Society, "Microorganisms" Sterilization of
The sterilizing agents described in "Sterilization and Antifungal Technology" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of the washing water in the processing of the light-sensitive material in the present invention is 4-9, preferably 5-8. The washing water temperature and washing time may be variously set depending on the characteristics and intended use of the light-sensitive material, but generally 15 to 45 ° C. and 20 seconds to
A range of 10 minutes, preferably 30-40 seconds at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8
543, JP-A-58-14834, JP-A-60-2.
All the known methods described in No. 20345 can be used.

Various chelating agents and antifungal agents can also be added to this stabilizing bath. The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step.

As the method for processing the silver halide light-sensitive material in the present invention, any development processing system can be used. Further, the development processing in the present invention is usually carried out using an automatic developing machine (also referred to as an automatic processor). Specifically, a roller automatic developing machine (for details, see "Photo Industry" February 1975, p. 71, etc.), a cine automatic developing machine (for details, "Photo Industrial" March 1975, p. 70, April 40 issue, page 40, etc.), leader belt type automatic processing machine (detailed in "Photo Industry", May 1975 issue, page 36, etc.), roller-conveying automatic processing machine (detailed in "Photo" Kogyo, June 1975, p. 41, etc.) and the like can be used.
Among the functional items that make up the automatic processor, the important functions for automatically supplying the processing liquid to the photosensitive material are the agitation for physically diffusing the processing chemicals and the temperature control for accelerating the chemical reaction. is there. For more information on these, see Photography Industry 10
Monthly (1974) page 82 and July (1975) page 41. In addition, as the essential function of the automatic developing machine before entering the processing tank, a photosensitive material storage container (magazine, cassette, cartridge, packaging material, etc.), photosensitive material joining means, cutting means (splicer, cutter, etc.), exposure device, DX Examples thereof include a reading device for information held by a sensitive material such as a code, and other detectors (eg, detection of a blind spot). Drying is an essential function of the automatic processing machine after leaving the processing tank. The details of this drying are described in “Drying Device” (published by Nikkan Kogyo Shimbun) edited by Ryozo Kiriri and “Photo Industry” January issue (1975), page 41.

Further, as another point of view of the processing machine, the opening area [degree] (K = S / V) with respect to the interface area (S) between the processing liquid and air and the processing liquid volume (V) can be mentioned. From these viewpoints, there are applications such as JP-A Nos. 53-57835 and 61-153645. Further, it is preferable that an automatic machine having a small liquid volume (V) in the processing machine has a relatively high liquid exchange rate, a small opening ratio (K) and a small tank liquid volume (V) in the case of a sparing process. From these viewpoints, JP-A-63-131138
No. 63-216050, etc. can be used. A preferable function to be provided in these processors is a slit type processing tank having a small tank liquid volume (V) and a small opening ratio (K) (Japanese Patent Laid-Open No. 63-131138).
No. 63-216050). If the persulfate type bleaching solution is used at a low concentration and the bleaching performance divided into parts is left as it is, it is difficult to keep the bleaching activity stable. Therefore,
At the time of processing, it is preferable to use it by devising replenishment for each part or reducing the tank liquid amount (V) to increase the liquid exchange rate. As a result, stable bleaching can be performed even in the case of low-pressure treatment. In other words, such a low-concentration, low-pollution bleaching agent is effectively used only within a certain range where there is a liquid exchange rate derived from the treatment device material, the replenishment control divided into parts, and the treatment device structure. It is possible.

An example of an automatic processor suitable for the present invention will be described below. In the present invention, the shorter the in-air time when the photosensitive material moves between the processing solutions, that is, the crossover time, the shorter the better. The time is preferably 10 seconds or less, more preferably 7 seconds or less, and further preferably 5 seconds or less. . In order to achieve the above-mentioned short-time crossover, it is preferable to use a cine type automatic developing machine in the present invention, and a leader transporting method is particularly preferable. The linear velocity of conveyance is preferably high, but is generally 30 cm to 2 m per minute and preferably 50 cm to 1.5 m per minute in the above-mentioned reader method.
As a reader and a conveying means for the photosensitive material, Japanese Patent Laid-Open No. 60-
No. 191257, No. 60-191258, No. 60-1
The belt conveying method described in No. 91259 is preferable, and in particular, as the conveying mechanism, it is preferable to use each method described in JP-A-3-126944, JP-31277062, and JP3-127061. Further, in order to shorten the crossover time and prevent the processing liquid from being mixed, the structure of the crossover rack preferably has the mixing prevention plate described in JP-A-3-126943.

In the present invention, it is preferable that the stirring of each treatment liquid is strengthened as much as possible in order to more effectively exhibit the effects of the present invention. As a concrete method of strengthening stirring,
JP-A-62-183460, JP-A-62-18346
No. 1, that is, a color negative film processor FP-230 manufactured by Fuji Photo Film Co., Ltd.
A method in which a jet of a processing solution is made to collide with an emulsion surface of a light-sensitive material as used in B, a method of providing a stirring effect by using a rotating means of JP-A-62-183461, and further provided in the solution. Examples thereof include a method of moving the photosensitive material (film) while bringing the wiper blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Of these, the method of colliding the jet stream of the processing liquid is the most preferable, and it is preferable to adopt this method for all the processing tanks. In particular, in processing with a processing solution having fixing ability, the effect of the present invention is significantly improved by colliding the jet stream within 15 seconds after the photosensitive material comes into contact with the processing solution having fixing ability. More preferably 10
Within seconds, more preferably within 5 seconds. The reason why such an effect is obtained is not clear at present, but if stirring is weak immediately after the photosensitive material comes into contact with the liquid having fixing ability, a factor causing residual color may occur, causing a strong jet collision. Therefore, it is considered that this factor can be removed.

The method of jet impingement in each treatment liquid is described more specifically in JP-A-62-183460, page 3, lower right column to page 4, lower right column, Examples of the invention. A method in which the liquid pumped by a pump is discharged from a nozzle provided facing the emulsion surface is preferable. As a pump, Iwaki magnet pumps MD-10, MD-15, M
D-20 etc. can be used. The hole diameter of the nozzle is 0.5-2 mm, preferably 0.8-1.5 mm. Further, it is preferable that the nozzle is opened in a circular shape as perpendicular as possible to the chamber plate surface and the film surface, and the angle is 60 degrees to 1 from the transport direction side.
The shape may be rectangular or slit at 20 degrees. The number of nozzles is 1 to 50, preferably 10 to 30 per liter of tank capacity. Further, if the jet flow hits a part of the film in a biased manner, uneven development and residual color unevenness occur. Therefore, it is preferable to sequentially shift the positions of the nozzles so that they do not hit the same place. A preferable arrangement of the nozzles is a row of about 4 to 8 holes which are perpendicular to the transport direction and whose positions are gradually changed at appropriate intervals. If the distance from the nozzle to the film is too short, the above unevenness is likely to occur, and if it is too far, the stirring effect is weakened.
It is preferably 2 mm, and more preferably 3 to 9 mm.
Is.

The flow velocity of the liquid discharged from each nozzle similarly has an optimum range, and is preferably 0.5 to 5 m / sec, particularly preferably 1 to 3 m / sec. The circulation of the whole processing solution is
A circulation system may be provided only through the nozzle or separately. The total circulation flow rate is 0.2 to 5 liters per minute, preferably 0.5 to 5 liters per 1 liter of tank volume for each treatment tank.
Although it is 4 liters, it is preferable that the circulation flow rate is relatively high in each of the desilvering steps of bleaching, bleach-fixing and fixing, and the preferable range is 1.5 to 4 liters. The automatic processor used in the processing of the present invention preferably has a device for aerating the bleaching solution. Aeration can prevent a decrease in the bleaching rate due to the formation of a divalent iron complex during continuous processing and the formation of a cyan leuco dye called defective color restoration. Aeration is Japanese Patent Laid-Open No. 2-176
No. 746 and No. 2-176747, treatment tank 1 using a porous nozzle having a pore size of 300 μm or less.
It is preferable to supply a flow rate of 0.01 liter or more per liter. This aeration may be carried out before or during the replenishment of the persulfate portion with the bleaching solution in response to a signal for setting the photosensitive material, and after the processing of the photosensitive material, the aeration may be stopped or intermittent operation may be performed.

The process of continuously or intermittently processing the light-sensitive material while replenishing the replenisher is called a running process. The bleaching solution during the running process uses a surfactant eluted from the processed light-sensitive material. Very easy to foam. Therefore, when aeration is performed, a large amount of bubbles are generated and may overflow from the processing tank. In order to prevent this, it is preferable to provide a defoaming means, and specifically, JP-A-4-3057, JP-A-4-56853, and JP-A-4-56853.
The method described in Japanese Patent No. 56854 is effective. In the present invention, it is preferable to correct the evaporative concentration of the processing liquid during the running processing. The most preferable evaporation correction method is to add water corresponding to the amount of evaporation in anticipation, and as described in JP-A-4-1756, the information on the operating time, stop time, and temperature control time of the automatic processor is used. The amount of water added is calculated based on the coefficient determined in advance. In addition to this, JP-A-3-248155
No. 3,249,644, No. 3-249645, No. 3-249646, and No. 4-14042, the evaporation correction method using a liquid level sensor is also preferable. Also, it is necessary to devise to reduce the amount of evaporation,
This can be done by reducing the opening area or adjusting the air volume of the exhaust fan.

For example, the preferable opening ratio of the color developing solution is as described above, but it is preferable to reduce the opening area of other processing solutions as well. Exhaust fan is mounted in order to prevent dew condensation at the temperature control, the preferred engine displacement, per minute 0.1 m ³ to 1 m ^3, a particularly preferred displacement volume, 0.2 m ³ ~0 It is 0.4 m ³ . Further, the drying condition of the photosensitive material also affects the evaporation of the processing liquid. As drying method, it is preferable to use a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as the supply air volume, particularly 6 m ³ through 10m ³ preferred. The heating prevention thermostat of the ceramic warm air heater is preferably operated by heat transfer, and the mounting position is preferably attached to the leeward or upwind side through the heat radiation fins or the heat transfer portion. The drying temperature is preferably adjusted according to the water content of the light-sensitive material to be processed.
The optimum temperature is 5 to 55 ° C, and 55 to 65 ° C for the Brownie film.

A replenishing pump is used for replenishing the processing liquid, but a bellows type replenishing pump is preferable. As a method of improving replenishment accuracy, it is effective to reduce the diameter of the liquid supply tube to the replenishment nozzle in order to prevent backflow when the pump is stopped. 1-8m as a preferable inner diameter
m, and a particularly preferable inner diameter is 2 to 5 mm.

As a replenishing method of the bleaching solution in the present invention, a conventionally known replenishing method can be used. In the present invention, the bleaching solution is separated into at least two parts, a persulfate part and a metal ion part, and the persulfate part of the persulfate type bleaching solution is bleached in response to a signal for setting a silver halide light-sensitive material to be processed. The light-sensitive material is replenished in a liquid tank, and 1 to 15 minutes, preferably 3 to 15 minutes after the replenishment, the light-sensitive material is bleached, and a persulfuric acid bleaching is performed during the bleaching treatment or after the bleaching treatment or immediately before the bleaching treatment. It is preferable to control so that the metal ion portion of the liquor is replenished in the bleaching bath. This replenishment system requires less replenishment, maximizes bleaching capacity, and makes the bleaching process of the light-sensitive material almost complete.
Furthermore, the occurrence of corrosion of the metal part of the bleaching bath due to the persulfate is reduced. In addition, bleaching failure does not occur even during the light-sensitive processing of the light-sensitive material.

The tank of the bleaching solution of the automatic processor which can be preferably used in the present invention is preferably high in the rate of replacement of the tank solution because the stability of the persulfuric acid type bleaching solution is poor. For this reason, it is preferable that the bleaching solution tank has a small tank volume because it can be dealt with during the off-gas treatment. The liquid exchange rate here means a percentage obtained by dividing the replenishing liquid amount R (liter) newly replenished in one day by the tank liquid amount V (liter). That is, the exchange rate P = (R /
V) × 100% The exchange rate P per day is 1
The daily amount is 3% or more and 600% or less, and more preferably 5% or more and 400% or less. With the above exchange rate, desilvering failure hardly occurs, and a more preferable color image print can be obtained. Furthermore, the corrosion of the metal parts of the processor can be further reduced. Further, considering the ultra-quiet processing, it is better to use a slit type processing tank in which the amount of the tank liquid is smaller than the photosensitive material processing area or a processing tank in which a portion other than a portion through which the photosensitive material passes in a normal processing tank is filled with a filling material. For example, when the tank liquid volume is Vcm ³ and the area of the photosensitive material to be immersed in the processing tank is Mcm ² , the ratio H = V
/ M (cm) is 100 or less, or when the area of the tank in contact with air is Scm ² and the opening degree is K, log
It is preferable to use a treatment tank satisfying K ≦ −1.8 × 10 ⁻⁵ V-1.5. For example, JP-A-63-131138;
63-216050; 63-148944; 63.
-148945; 63-235940; 61-77.
851; 64-64938; 64-26855; JP-A-1-140148; 1-114847; 1-1.
29253; 1-154155; 1-16374.
3; It is preferable to use the treatment tank of the application of each of the same No. 1-166040.

In the automatic processor of the present invention, various plastic component materials are used in addition to the stainless steel portion of the bleaching tank described above, and preferable materials are described below.
A modified PPO (modified polyphenylene oxide) resin and a modified PPE (modified polyphenylene ether) resin are preferable as a tank material such as a processing tank and a temperature control tank, and as a material for guides of the processing rack and the liquid contact part. Examples of the modified PPO include "Noryl" manufactured by GE Plastics Co., Ltd., and modified PPE include "Zylon" manufactured by Asahi Kasei Kogyo Co., Ltd. and "Yupiace" manufactured by Mitsubishi Gas Chemical Company. These materials have excellent chemical resistance to a developing solution, a fixing solution, a bleach-fixing solution and the like. These materials are suitable for injection molding and have an advantage that various hollow molding such as low foam molding, sympress molding, and gas counter pressure molding can be performed. By using these molding methods, it has become possible to integrally mold the processing tank and temperature control tank, as well as the guides and racks having a complicated structure.
Furthermore, it became possible to make thick members such as thick molded bodies and blocks. It can also be used for large housing members such as covers for automatic processors by engineering blow molding. Since these materials have a higher heat resistance temperature than general ABS (acrylonitrile-butadiene-styrene resin), they can be used as a material for drying members of an automatic processor. When heat resistance and rigidity are required, glass fiber reinforced or filler-added grade can be used.

Since ABS has chemical resistance to processing solutions (for example, color developing solution, bleaching solution, fixing solution, bleach-fixing solution), it can be used for a part of tanks and racks. it can. ABS resin from each company such as "Denka" manufactured by Denki Kagaku, "Psycholac" manufactured by Ube Industries, Mitsubishi Monsanto Kasei, and Japan Synthetic Rubber can be used. ABS is 8
It is preferably used in an environment of 0 ° C or lower. Also, AB
S is a material suitable for a housing of an automatic processor because it has good moldability by injection molding, has few sink marks during molding, and can be molded with good flatness. This material is also suitable for the processor supply section and cassettes. Also, PE of olefin resin
(Polyethylene) and PP (polypropylene) have high chemical resistance to general processing solutions (for example, color developing solution, bleaching solution, fixing solution, stabilizing solution). PE has many products such as Showa Denko and Ube Industries. There are many PP products such as Ube Industries, Chisso, Mitsui Toatsu Chemicals, and Asahi Kasei. It is used as a material for replenishment tanks and waste liquid tanks in automatic processors. Since the material is inexpensive and the large-sized tank can be easily manufactured by hollow molding, it can be preferably used in a portion that does not require high dimensional accuracy.

PVC (polyvinyl chloride resin) is
It has excellent chemical resistance, is inexpensive and can be easily welded, and has excellent workability. Many types of PVC are produced by many companies, such as various chemical manufacturers such as the electrochemical industry and Riken Vinyl Industry. Sheet materials extruded from Takiron Industrial "Taquilon Plate" and Mitsubishi Plastics "Hishi Plate" are commercially available, and various modified PVCs are also commercially available and can be easily used.
Acrylic-modified PVC is commercially available from in-cylinder plastic “Kyduck” and Sunarrow Chemical. Acrylic-modified PVC is a suitable material that has a smooth surface and good water repellency, and when used in a tank, does not easily cause precipitation of a processing solution (for example, precipitation of a main agent from a color developing solution). As a device for extruding PVC or smoothing the surface of an injection-molded article, it is highly effective to add soybean oil or the like in addition to modified PVC to improve the fluidity during molding. Addition of soybean oil (preferably modified soybean oil) not only smoothes the resin surface and does not impair the quality of the photosensitive material due to scratches, but also has the effect of improving the fluidity during molding.

As a material for the guide of the processing tank or the processing section in order to prevent the deposition of the color developing agent or the like and to improve the transportability of the light-sensitive material,
Crystalline polymers can be used. PBT (polybutylene terephthalate), HDPE (ultra high density polyethylene resin), PTFE (polytetrafluoroethylene resin),
PFA (ethylene tetrafluoride / perfluoroalkoxy ethylene resin), PVDF (polyvinylidene fluoride resin)
And the like are suitable for a guide in contact with a photosensitive material and a liquid interface portion where a processing liquid (for example, a color developing solution) is likely to be deposited. The above-mentioned fluoride is effective even if it is coated on another material such as PPE.

As the roller material of the processing section, PVC is used.
(Polyvinyl chloride resin), PP (Polypropylene), P
Thermoplastic resins such as E (polyethylene), UHMPE (ultra high molecular weight polyethylene), PMP (polymethylpentene), PPS (polyphenylene sulfide), modified PPO (modified polyphenylene oxide), modified PPE (modified polyphenylene ether) are suitable. . PP, P
Olefin resins such as E and PMP can be injection-molded smoothly on the surface of the roller, and since the specific gravity is small, the rotational load can be reduced. Therefore, the emulsion surface of the conveyed photosensitive material is not easily scratched and is suitable. These are often used for drum rollers in the turn section. UHMPE or PTFE (PFA or P
Materials such as (including VDF) are suitable for the parts where the sensitive material is squeezed or where the processing solution needs to be watered. It has the effect of preventing the sensitive material from being scratched by the solidified substance of the deposit of the treatment liquid on the roller. A roller provided with these materials on the roller surface (including coating) is suitable for the roller located at the interface of the treatment liquid and the roller for the squeeze portion. PVC is suitable for being easily processed into rollers by extrusion. Further, it is preferable that the roller having a soft resin portion having a low hardness on the surface of the roller can be easily manufactured by the double extrusion molding, and the roller can be brought into soft contact with the photosensitive material. In addition to PVC, modified PPO, modified PPE,
Modified PPS or the like is suitable because it has high rigidity and can withstand high rotational torque. It is preferable to use glass fiber-reinforced or mineral-added strengthening agents such as mica, talc and potassium titanate in order to further enhance rigidity. By adding the reinforcing material, the bending elastic modulus of the roller can be improved and the cleave deformation due to aging can be prevented, and the long-term use can ensure stable transportability without bending the roller. Further, by adding an inorganic substance to the resin and molding, the surface can be roughened by the inorganic particles appearing on the roller surface to prevent it from slipping. The surface roughness of the roller can be controlled by adjusting the particle size and amount of the added inorganic material.

The thermosetting resin is suitable for a carrier roller having a small diameter and a photosensitive material having a wide width and a long roller length. PF (phenolic resin), thermosetting urethane resin, and unsaturated polyester resin are preferable. Epoxy resins are also suitable for some processing solutions other than alkaline processing solutions. The PF is preferably a resol type, and Mitsui Toatsu Chemicals “OR-85” is particularly suitable. Graphite may be added for reinforcement. Since this roller can be made thin (for example, the outer diameter is 8 mm), the processing rack can be downsized.
As the thermosetting urethane resin, Nippon Unipolymer "Unilon", Dainippon Ink and Chemicals "Pandex", Takeda Chemical Industries "Takenate" and the like are suitable. A roller coated with a fluorine-based resin is also preferable in order to prevent contamination with a developing solution, specifically, JP-A-4-16195.
The resin disclosed in No. 5 can be used. An elastomer can be used for a soft roller such as a nip roller. For example, olefin elastomer,
Styrene-based elastomers, urethane-based elastomers, vinyl chloride-based elastomers and the like are preferable.

As the gear and sprocket of the processing section, P
A (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS
Thermoplastic crystalline resins such as (polyphenylene sulfide), LCP (wholly aromatic polyester resin, liquid crystal polymer), PEEK (polyether ether ketone) are suitable. As PA, 66 nylon, 6 nylon, 12
In addition to polyamide resins such as nylon, aromatic polyamides having an aromatic ring in the molecular chain and modified polyamides are included. Toray and DuPont “Zytel” are suitable as 66 nylon and 6 nylon, and Toray “Rilsan” and Daicel Hüls “Daiamide” are suitable as 12 nylon. Suitable aromatic polyamides include Mitsubishi Gas Chemical's "Renny" polyamide MXD6, and modified polyamides such as Mitsui Petrochemical's "Alen" modified polyamide 6T. PA is preferably a glass fiber reinforced or carbon fiber reinforced grade because it has a high water absorption rate and easily swells in the treatment liquid. Aromatic polyamides have a relatively low water absorption rate and thus are less likely to swell, and high dimensional accuracy can be obtained. In addition, high molecular weight products such as MC nylon obtained by compression molding can obtain sufficient performance without fiber reinforcement. In addition, oil-impregnated nylon resin such as "Polyslider" is also used. Contrary to PA, PBT has a very low water absorption rate, and thus has high chemical resistance to the treatment liquid. Toray and PBT of Dainippon Ink and Chemicals
And Nippon GE Plastics "Barox" are used. PBT is used depending on the site, whether it is a glass fiber reinforced product or an unreinforced product. In order to improve the meshing of gears, it is preferable to use a glass reinforced product and an unreinforced product in combination. As UHMPE, unreinforced products are suitable, and Mitsui Petrochemical's "Lubemer", "Hi-Zex Million", Sakushin Kogyo "New Light", Asahi Kasei "Sunfine", Dai Nippon Printing "Ultra High Molecular Weight Polyethylene UHM"
W "is suitable. As the PPS, those reinforced with glass fiber or carbon fiber are preferable. As LCP, ICI Japan "Pictrex", Sumitomo Chemical "Econor",
Nippon Oil "Zyder", polyplastics "Vectra", etc. can be used. PEEK is a suitable material that has extremely good chemical resistance and durability against any processing liquid of the developing machine and is an unreinforced product and exhibits sufficient performance.

As the material of the bearing and the like, ultra high molecular weight polyethylene and the like are preferable. As the springs and springs used in the processing liquid of the automatic developing machine other than the bleaching tank, usually stainless steel (SUS304, 316), titanium or the like is used. Plastic springs can be used if the spring or spring cannot be made properly with titanium. For applications where the amount of deformation when a load is applied is small (critical strain according to Hooke's law is 1.6% or less), PBT (for example, Nippon GE Plastics "Barox 310")
Etc.), PP (for example, Asahi Kasei “M-1500” and the like), modified PPO (for example, Japan GE Plastics “Noryl 731J” and the like), and modified PPE (for example, Asahi Kasei “Zylon 220V” and the like).
When the spring force is weak, it is also effective to use a glass fiber reinforced material. In order for the spring to obtain a stable nip force for a long period of time, PSF (polysulfone), PAR (polyarylate), PES (polyethersulfone), PEI (polyetherimide), PAI
(Polyamideimide) is suitable. In particular, super-embra's non-crystalline resin is excellent and PSP, PES, PE
I is particularly preferred. PSF is Amoco "Udel P1"
700 ", PES is ICI" VICTREX 4800
For G "and PEI, Japan GE Plastics" Ultem "can be used. Crystals such as PEEK, PPS, and LCP are used for springs that are used for a long time under a heavy load. Amorphous resins have less cleaving and have very good dimensional accuracy during molding. Is suitable. Crystalline resin is suitable for the parts that require high fatigue limit stress, and PEEK is ICI "VI
CTREX 450G ", PPS" Ryton ", LCP
Type I Sumitomo Chemical "Econor E2000", LCPII
Typical grade is type polyplastic "Vectra A950".

As a soft material such as a squeeze roller,
Foam, vinyl chloride resin, silicon foam resin, and urethane foam resin are suitable. Examples of the urethane foam resin include "Rubicel" manufactured by Toyo Polymer Co., Ltd. EPD for rubber and elastomers such as pipes, pipe joints, agitation jet pipe joints, and sealing materials
M rubber, silicone rubber, viton rubber, olefin elastomer, styrene elastomer, urethane elastomer, vinyl chloride elastomer and the like are preferable. For example, as specific examples, "Sumiflex" manufactured by Sumitomo Bakelite Co., Ltd., "Milastomer" manufactured by Mitsui Petrochemical Co., Ltd.
(Olefin Elastomer), Mitsubishi Yuka Co., Ltd. “Thermoran” (Rubber-containing olefin elastomer), the same “Lavalon”, Nippon Monsanto Kasei Co., Ltd. or AES Japan Co., Ltd. “Santplane”, Mitsubishi "Sunplane" (high-elasticity vinyl chloride type elastomer) manufactured by Kasei Vinyl Co., Ltd., and silicone rubber and viton rubber described in JP-A-3-198052 can be used.

As a core material of a belt such as a conveyor belt,
Ultra high strength polyethylene resin fiber (for example, Japanese Patent Laid-Open No. 4-6
No. 554), polyvinylidene fluoride resin fibers (for example, described in JP-A-4-16941), aramid fibers (for example, “Kepra” manufactured by Toray DuPont Co., Ltd.) and the like can be used. Regarding the materials such as plastics used in each part such as the processing tank of the processing apparatus described above, "Plastic Molding Material Commerce Handbook-Characteristics Data Base 1991 Edition" issued by Synthetic Resin Industry Newspaper Co., Ltd. Can be easily selected and obtained. The material of the refill cartridge used in the present invention is
Any material such as paper, plastic and metal can be used, but the oxygen permeability coefficient is 50 ml / m.
A plastic material of ² · atm · day or less is preferable. The oxygen permeability coefficient is "O ₂ permeation of plastic c
ontainer, Modern Packing; NJ Calyan, 1968) 1
It can be measured by the method described in the February issue, pages 143-145.

Specific examples of preferable plastic materials include vinylidene chloride (PVDC) and nylon (N
Y), polyethylene (PE), polypropylene (P
P), polyester (PES), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVAL), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), etc. Can be mentioned. For the purpose of reducing oxygen permeability, PVDC, NY, PE, EVA,
The use of EVAL and PET is preferred. These materials may be used alone and may be molded and used, or a method of forming a film shape and laminating a plurality of kinds (so-called composite film) may be used. Also, as the shape of the container,
Although various shapes such as a bottle type, a cubic type, and a pillow type can be used, the present invention is particularly preferably a cubic type and a structure similar to this which are flexible and easy to handle and can be reduced in volume after use.

When used as a composite film, the structures shown below are particularly preferable, but not limited thereto.・ PE / EVAL / PE ・ PE / aluminum foil / PE ・ NY / PE / NY ・ NY / PE / EVAL ・ PE / NY / PE / EVAL / PE ・ PE / NY / PE / PE / PE / NY / PE ・PE / SiO ₂ film / PE ・ PE / PVDC / PE ・ PE / NY / aluminum foil / PE ・ PE / PP / aluminum foil / PE ・ NY / PE / PVDC / NY ・ NY / EVAL / PE / EVAL / NY ・NY / PE / EVAL / NY-NY / PE / PVDC / NY / EVAL / PE-PP / EVAL / PE-PP / EVAL / PP-NY / EVAL / PE-NY / Aluminum foil / PE-Paper / Aluminum foil / PE ・ Paper / PE / Aluminum foil / PE ・ PE / PVDC / NY / PE ・ NY / PE / Aluminum foil / PE ・ PET / EVAL / E · PET / aluminum foil / PE · PET / aluminum foil / PET / PE

The composite film has a thickness of about 5 to 1500 microns, preferably about 10 to 1000 microns. The content of the finished container is 100 ml to 20 liter, preferably 500 ml to
It is about 10 liters. The above container (cartridge)
May have a cardboard or plastic outer box,
It may be formed integrally with the outer box. Various processing liquids can be filled in the cartridge of the present invention. For example, a color developing solution, a black and white developing solution, a bleaching solution, an adjusting solution, an inversion solution, a fixing solution, a bleach-fixing solution, a stabilizing solution and the like can be mentioned. It is preferred to use developers, fixers and bleach-fixers. The automatic processor of the present invention may also be capable of processing a film which has already been recorded and which has magnetic recording information. In this case, it is preferable to use an automatic processor equipped with the magnetic recording / reading device described in JP-A-6-110120 at the entrance of the automatic processor.

The present invention will be specifically described below with reference to the drawings. FIG. 1 shows a conceptual diagram of the automatic developing machine of the minilab of the present invention. When the photographed film 9 is joined to a reader (not shown) and is inserted into the film insertion portion 1, the sensor 8 senses it, and the counter roller is driven to feed the film 9 in order to insert the film 9. As will be described later, it is preferable to replenish the persulfate portion 17 of the bleaching solution with the information obtained by the sensor 8 detecting the film 9. Next, the film 9 is conveyed, and when the film 9 reaches the end of the cartridge, tension is applied to the film conveyance.
Works and the film 9 and the cartridge are cut. The cut patrone drops into the empty patrone receiver 3 at the bottom,
Films are sequentially colored development (N1) tank, stopped (CS)
Bath, bleaching (N2) bath 7, rinse (R) bath, fixing (N3)
The film is conveyed to the tank, rinse (R) tank, stable (N4) tank, and drying section 4, and finally a leader (not shown) is accumulated in the film leader accumulating section 5, and the film hangs down below the leader to form a film storage box. Fits within 6

Next, a preferable replenishing mechanism of the bleaching solution in the bleaching solution tank in the present invention will be described with reference to the drawings. FIG. 2 is an enlarged view of the bleaching (N2) tank 7 of FIG. 1 and shows a replenishing mechanism thereof. Bleaching solution 7 in bleaching tank 7
And the photographed film 9 is conveyed and processed therein. The bleach replenishment tank 11 is filled with the metal ion portion 16 of the bleach replenisher, and the bleach replenishment tank 12 is filled with the persulfate portion 17 of the bleach replenisher. Figure 2
The two-way cock valve 14 is moved by the control panel 13 of the automatic developing machine, and the pump P15 is driven to feed the replenisher into the bleaching solution tank 7.

Since the bleaching replenisher is divided into the metal ion portion 16 and the persulfuric acid portion 17, decomposition and deterioration of the replenishing tank over time can be significantly suppressed. Moreover, piping 1
Since the metal ion portion 16 and the persulfuric acid portion 17 do not exist in each of 8, 19, 20, and 21, there is no decomposition deterioration in the pipe. At the same time as receiving the signal from the sensor 8 at the time of inserting the film 9 shown in FIGS. 1 and 2 to move the counter roller, the control panel 13 which receives the signal opens the two-way cock valve 14 and the persulfuric acid portion 17. After connecting, the pump P15 is driven for a certain period of time. In this way, the replenisher persulfate portion 17 is introduced into the bleaching tank 7 and is thoroughly mixed with the bleaching solution 10. Although not shown in the figure, a liquor circulation system is incorporated in the bleaching tank 7 to make the composition of the bleaching solution 10 uniform and the temperature uniform. By this uniform mixing, the activity of the bleaching solution is gradually improved, and the bleaching ability is sufficiently recovered after 1 minute to 15 minutes. After that, the film 9 is bleached.
During the bleaching treatment of the film 9, after the bleaching treatment or immediately before the bleaching treatment, the metal ion portion 1 is treated in the same manner as in the conventional method.
Replenishing 6 maximizes bleaching ability. Here, the replenishment of the metal ion portion 16 immediately before the bleaching treatment is performed by the persulfate portion 17
Not before the addition of. After the bleaching process of the film is completed, the bleaching solution 10 loses its activity, and the persulfate is further decomposed until the next film is processed, which further prevents the corrosion of the metal part of the bleaching machine parts. can do. It is expected that this is because the persulfate in the bleaching solution is less than that in the conventional case (preferably 0.3 M or less) and the amount of metal ions is less (preferably 0.05 M or less).

The metal ion portion 16 is replenished by receiving the conventional replenishment signal, connecting the two-way cock valve 14 to open the metal ion portion 16, and then driving the pump P15 for a certain period of time. In this state, the pipes 20 and 21 are filled only with the metal ion portion 16, and there is no deterioration of the replenisher in the pipes. Two-way cock valve 14 and pump P1
The shorter the pipe 20 between 5 and 5, the better the stability of the replenisher. In the present invention, the bleaching solution can be replenished by any conventionally known method, but two types of parts are replenished at different timings by a combination of two switching cocks and a pump as shown in FIG. The method is preferred. This can facilitate pump savings and refill control.

In the case of the present invention, in addition to the above bleaching solution, a developing solution,
The replenishing system of the present invention can be used for replenishing the bleach-fixing solution. That is, in the case of replenishment of the developing solution, the developing activity comes out only after the developing solution is made alkaline. If the developing solution replenishing tank is made alkaline in advance, the developing replenishing solution may be deteriorated during storage of the replenishing solution, especially in the case of a dispersal process. Therefore, if the developer replenisher is divided into the developing agent component and the alkaline component and placed in separate tanks and replenished separately as described above, the deterioration of the developer replenisher as described above can be prevented. In the case of a developing replenisher, it is preferable to replenish the developing agent component first.

On the other hand, in the case of the bleach-fixing solution, when the bleaching component which is an oxidizing agent component and the fixing component which is a weak reducing component are premixed and stored in a replenishing tank as a bleach-fixing replenishing solution, especially in the case of a quiet process In some cases, the action of both components may be reduced in the tank and the replenisher may deteriorate. Therefore, as described above, when the bleach-fix replenisher is divided into the oxidizing agent component and the weak reducing component and placed in separate tanks and separately replenished, the above-described deterioration of the bleach-fix replenisher can be prevented. In the case of a bleach-fixing replenisher, it is preferable to replenish the above-mentioned bleaching components first.

[0068]

EXAMPLES The present invention will be specifically described below with reference to examples, but the contents of the present invention are not limited thereto. Example 1 FP560B, a color negative minilab automatic developing machine manufactured by Fuji Photo Film Co., Ltd., was modified so that it could be processed in the following steps. Treatment process Temperature Time Composition Tank Replenishment capacity (135mm width 1m) Color development 37.6 ± 0.15 ℃ 3 minutes 15 seconds 1 tank 2 racks 17.2 liters 22ml Stop solution 35-41 ℃ 1 minute 30 seconds 1 tank 1 rack 8.6 Liter 11ml Bleach 35-41 ℃ 1 min 30 sec 1 tank 1 rack 8.6 liter 25ml Rinse 1 ^{* 1} 〃 1 min 30 sec 1 tank 1 rack 8.6 liter 50ml Fixed 〃 1 min 30 sec 1 tank 1 rack 8.6 liter 15ml Rinse 2 ^{* 2} 〃 1 minute 30 seconds 1 tank 1 rack 8.6 liters 50ml Stability ^{* 3} 〃 45 seconds 1 tank 1 rack 4.3 liters 31 ml Dry 35-70 ℃ 1 minute 30 seconds 1 rack −

The overflow solution of the stabilizing solution (* 3) was introduced into the rinse 2 (* 2), and the rinse 2 was 135 mm wide x 1
It is replenished with 50 ml per m, so a total of 135 mm x 1
81 ml will be replenished per m. Rinse 2 again
The overflow of (* 2) is introduced into rinse 1 (* 1). Therefore, the total replenishing amount per 135 mm × 1 m of the rinse 2 is 131 ml (assuming the carry-in / over are the same). The color developing solution, fixing solution, and stabilizing solution used here are respectively Fuji Photo Film Co., Ltd. Color negative treatment agent CN-16X NIX and NIXR, N3X
And N3XR, N4 and N4R were used. (R is a replenisher) As a stop solution, a 2% sulfuric acid solution was used for both mother liquor and replenisher. Rinse solution is deionized water maker FR manufactured by Fuji Photo Film Co., Ltd.
The tap liquor treated with SS was used as both the mother liquor and the replenisher.

As the bleaching solution, a solution having the following formulation was used for both the mother liquor and the replenisher. Bleach (P Formulation) 2,6-pyridinedicarboxylic acid 5g glacial acetic acid _{6ml Fe (NO 3) 3 ·} 9H 2 O 6g Na 2 S 2 O 8 was added to 63 g NaCl 9 g NaOH about 3g water to adjust 1 liter NaOH To pH 4.2

(A) As a photosensitive material, color negative film super HG100 and HG400 manufactured by Fuji Photo Film Co., Ltd. were subjected to a running treatment for 200 times a day at a ratio of 1: 1 for one month. Here, the replenishment of the bleaching solution is performed by FP560.
The replenishing system attached to B (blending liquor replenishing system) was used as it was. In addition, the gear shaft of the bleaching solution rack is set to SUS
316 to stainless steel SUS304, SUS3
16, SUS316L or SUS317, respectively. When the photographic properties at the time of running equilibrium were examined, it was found that the minimum density (Dmin) of the blue layer (BL) was remarkably increased and that it was not. The results are shown below. Increase in Dmin of material BL SUS304 0.37 SUS316 0.03 SUS316L 0.02 SUS317 0.02 From the above results, it is clear that SUS304 markedly increased stain and could not obtain a good print. (B) Stopping the stop solution in the processing process and skipping the processing solution for the rack using the SUS316, SUS316L, and SUS317 shafts, the gradation of the green layer was remarkably reduced during one-month running equilibrium, and good prints were obtained. I couldn't do it. Therefore, it was found that the stop solution was essential during the treatment process.

(C) Next, in the formulation P of the bleaching solution, the formulation was divided into two as follows. The conditions other than this are the same as those in Example 1 (b). (Part A) 2,6-pyridinedicarboxylic acid 5g glacial acetic acid 6 ml Fe (NO ₃₎ mechanism of the addition of ₃ · 9H ₂ O 6 g water 500ml refill unit see FIG. 2 (Part _{B) Na 2 S 2 O 8} 63g NaCl 9g NaOH 3g Water was added 500ml As in the case of Fig. 2 above, when the film was inserted into the film insertion part during the processing of the sensitive material, a film insertion signal was taken. The above solution was replenished with 8 ml of each film, and Part A was replenished with 7.3 ml per 135 mm width × 1 m as a conventional replenishing method when the film entered the bleaching tank. In this way, the replenishment amount of the bleaching solution could be reduced by 40%, at the same time, stain was not generated, the soft tone of the green layer was not, and stable performance was obtained.
On the other hand, in order to investigate the desilvering performance, the amount of residual silver in the film after 6 months of processing was measured by fluorescent X-ray with Super HG400. As a result, as shown below, the desilvering performance was good. Method (a) 5.3 μg / cm ² Method (c) 4.7 μg / cm ² That is, by only running the persulfate part separately, bleaching performance is sufficient and stable performance without stain is obtained. Was given. Incidentally, when the axis used in (a) above was observed with an electron microscope, SUS316, SUS316L,
It was found that even SUS317 had a slight pinhole. However, the SUS31 used in (c) above
6, SUS316L and SUS317 had no pinholes. That is, it was found that metal corrosion can be surprisingly prevented by supplementing each part.

Example 2 A running process was performed in the same manner as in (c) of Example 1 except that the bleaching solution formulation in Example 1 (c) was changed to the following bleaching solution formulations Q, R and S. However, (c) of Example 1
Similar to the above, the amount of replenishment can be reduced, the bleaching performance is not deteriorated, and the treatment can be performed without any fear of corrosion. Adjust with 1 liter aqueous ammonia added Q prescription 2,8-pyridinedicarboxylic acid _{5g Fe (NO 3) 3 ·} 9H 2 O 6g glacial acetic acid _{57ml Na 2 S 2 O 8 30g} NaCl 8g concentrated aqueous ammonia to about 40ml water Adjust to pH 4.3

[0074] R Formulation 1,2,4-benzenetricarboxylic acid 21g 2,6-pyridinedicarboxylic acid _{2g Fe (NO 3) 3 ·} 9H 2 O 2.5g Na 2 S 2 O 8 30g NaCl 15g Na 2 CO 3 to about 5 g of water is added to adjust the pH to 3.7 by finely adjusting 1 liter of Na ₂ CO _3. S formulation Q formulation in which 5 g / liter of picolinic acid is added instead of 2,8-pyridinedicarboxylic acid.

Example 3 Five running lines per day were carried out in Example 1, and the running performances of Example 1 (b) and (c) were compared.
In order to examine the desilvering performance, the amount of residual silver in the film after 3 months processing was used as a color negative film, Super HG400.
Was measured by X-ray fluorescence. The results were as shown below. Results of silver analysis by fluorescent X-ray (residual silver amount due to poor bleaching) 1 month 3 months later Method (b) 17.3 μg / cm ² 20.8 μg / cm ² Method (c) 4.5 μg / cm ² 4.3 μg / Cm ^{2 In} the method (b) of Example 1, the bleaching failure occurred as described above even in the first month, but in the method (c) of Example 1 it did not occur even in the third month. Moreover, it was stable without the generation of stains. That is, it was found that the method (c) of Example 1 was a method in which the amount of replenishment was small, stain was not generated, the contrast was not softened, there was no fear of corrosion, and the bleaching failure was not generated even in the case of the off-gas treatment. .

Example 4 Similar results could be obtained by using the following photographic materials instead of Super HG 100 and 400 used in Example 1. Fuji Color SUPER HG100 Fuji Color SUPER HG200 Fuji Color SUPER HG400 Fuji Color SUPER HG800 Fuji Color SUPER HG1600 Fujicolor REALA Kodak SUPER Gold100 Kodak SUPER Gold200 Kodak SUPER Gold400 Kodak SUPER Gold1600 Konica color SUPERDD 100 Konica color SUPERDD 200 Konica Color XG400 Konica color GX3200 PLOFESSIONAL

Example 5 In Example 1 (b), the amount of photographic film processed per day was changed, and the tank solution exchange rate of the bleaching solution was changed variously as shown in Table 1 below. . The desilvering failure at that time was examined by fluorescent X-rays as in the above. Table 1 shows the results.

[0078]

[Table 1]

Clearly exchange rate 3% or more [15% / 1w
(5 days or more), it can be seen that the desilvering failure is less likely to occur. Example 6 In Example 1 (b), the amount of the tank liquid was reduced to 4.3 liters by putting a filling in a place other than the portion related to the transportation of the bleaching liquid tank. In this way, desilvering failure did not occur even with the treatment of 7 films per day (7 films / day). At this time, if the method of Example 1 (c) is used, 5 films /
Desilvering failure did not occur even in the day processing. Therefore, if you fill the processing tank with filling material or use a slit type processing tank to reduce the tank liquid volume, the liquid exchange rate will increase,
With the persulfuric acid type bleaching solution, the bleaching performance can be stably obtained even in the quiet treatment (the number of treatments per day is 5 to 10).

[0080]

EFFECTS OF THE INVENTION According to the present invention, a so-called environmentally friendly persulfate type bleaching solution which has good bleaching performance even if the concentration of the drug is low, does not cause bleaching fog, that is, stain, and is biodegradable. The object of the present invention is to provide a processing method of a silver halide light-sensitive material which can be used in a normal minilab, and an automatic developing machine thereof.

[Brief description of drawings]

FIG. 1 is a conceptual diagram showing an aspect of an automatic processor of the present invention.

FIG. 2 is a diagram showing a bleaching solution replenishing mechanism in the present invention.

[Explanation of symbols] 1 film insertion part 2 cutter 3 empty cartridge holder 4 drying part 5 film leader stacking part 6 film storage box 7 bleaching tank 8 sensor 9 film 10 bleaching solution 11 bleaching replenishing tank 12 bleaching replenishing tank 13 control panel 14 2 One-way cock valve 15 Pump 16 Metal ion part 17 Persulfate part 18, 19, 20, 21 Piping

Claims (6)

[Claims] 1. A member capable of contacting with a bleaching solution, wherein a persulfate type bleaching solution is used as a bleaching solution in an automatic developing machine for a silver halide light-sensitive material having at least developing, development stopping, bleaching and fixing tanks. At least a part of Mo is 2 to 4% by weight, Ni is 10 to 15% by weight, Cr is 16 to 20% by weight, C
An automatic processor for silver halide light-sensitive materials, which is stainless steel consisting of ≤0.08% by weight. 2. The persulfate type bleaching solution contains at least 2-pyridinecarboxylic acid represented by the following formula (I) or 2,6-pyridinedicarboxylic acid represented by the following formula (II). 2. The automatic developing machine for silver halide light-sensitive materials according to claim 1, further comprising at least one metal ion selected from ferric ions, secondary cobalt ions and secondary nickel ions. Embedded image In formulas (I) and (II), X ₁ , X ₂ , X _{3 and} X ₄ are each independently a hydrogen atom, a hydroxyl group, —COOM, —S.
Represents O ₃ M or —PO ₃ M, and M represents a hydrogen atom or an alkali metal. 3. A persulfate salt bleach replenisher is divided into at least two parts of a persulfate salt portion and a metal ion portion, and the persulfate salt is received in response to a signal for setting a silver halide light-sensitive material to be processed. Part is replenished in a bleaching solution tank, and 1 to 15 minutes after the replenishment, the light-sensitive material is bleached, and the metal ion part is bleached during the bleaching step, immediately after the bleaching step or immediately before the bleaching step. An automatic developing machine for silver halide light-sensitive materials according to claim 1 or 2, which has a control mechanism for replenishing the same. 4. An automatic processor for silver halide light-sensitive materials having at least each of development, development stop, bleaching, fixing or bleach-fixing tanks, and the replenisher in either processing tank is divided into two parts for processing. Halogen characterized by having a control mechanism for receiving a signal for setting a silver halide light-sensitive material and replenishing any one of the parts to the processing tank, and then replenishing another part to the processing tank later. Automatic processor for silver halide photosensitive materials. 5. The silver halide photographic material according to claim 4, wherein the replenishment of the processing solution is carried out by combining two or more switching cocks and pumps for two or more parts at different timings. Automatic developing machine. 6. A method of processing a silver halide light-sensitive material comprising at least development, cessation of development, bleaching and fixing steps, wherein a persulfate type bleaching solution is used as a bleaching solution, and a member which can come into contact with the bleaching solution is used. , Mo2-4% by weight, Ni10-1
5% by weight, Cr 16 to 20% by weight, C ≦ 0.08% by weight
And a bleaching solution is replenished at a solution exchange rate of 3% or more and 600% or less per day.