JP2821805B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide photographic light-sensitive material. More specifically, the present invention relates to a method for processing a silver halide photographic light-sensitive material. Not regarding the processing method.

[Background of the Invention]

In general, a silver halide color photographic light-sensitive material forms a dye image by a series of photographic processings including a color development step and a desilvering step as basic steps after image exposure.

In the above color developing step, the oxidized form of the color developing agent is
A dye image is formed by a coupling reaction with a coexisting color coupler, and at the same time, reduced silver is generated.
The silver thus formed is oxidized by the bleaching agent in the subsequent desilvering step, changes into a soluble silver complex under the action of the fixing agent, and is dissolved away by washing with water.

In the actual development processing step, in addition to the above-described basic steps for color development and desilvering, from the necessity for improving the photographic or physical properties of the image, a stop bath, a hardening bath,
An auxiliary treatment bath such as a stabilization bath and a backing removal treatment bath is provided.

On the other hand, in recent years, anhydrous washing processing for the purpose of reducing pollution has begun to be introduced to the market, and at present, almost all of the minilab market is an automatic developing machine of an anhydrous washing processing type. It is considered that the reason for this is that in the minilab market, there is a strong need for simplification of processing and reduction of installation area, and an anhydrous washing type automatic developing machine that does not require piping has met this need.

However, since the anhydrous lab type minilab was introduced to the market, there was a problem that an automatic developing machine for a color negative film often suffered a flaw, and in severe cases, the color film could not be conveyed, resulting in jamming. It turns out.

The present inventors have conducted investigation and analysis to solve the above problems, and as a result, have found the following.

That is, 1) a large amount of hard deposits are generated on the outer liquid rack and gears of the fixing bath and the stabilizing bath, and further on the rack from the fixing bath to the stabilizing bath, thereby causing scratches and jamming. 2) A large amount of hard deposits cannot be easily removed and is fixed at the above-mentioned location, and the main component is sulfur. 3) There is also a slight occurrence in the automatic developing machine for color paper. However, the deposits can be easily removed,
4) There are hanger (hanging) type and cine type automatic developing machines for color negative films in large laboratories. In the case of the hanger type, there is no claim at all. This is because the conveying method by hanging is adopted. Conceivable. Investigations have revealed that although the cine method has some adhered matter, it is considerably lighter than an automatic developing machine for minilabs.

These problems are completely unpredictable from conventional knowledge, and the above problems are not only lost when the color negative film is scratched, but appear as scratches on the print, and the worst case is lost. in the case of,
An urgent solution is also needed to waste user color film and seriously damage the reputation of minilab stores.

[Object of the invention]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a processing method and a processing apparatus which do not cause jamming or scratches by preventing fixation of a fixing solution component to a fixing bath or a transition portion to a bath following the bath. .

[Configuration of the invention]

The object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material comprising a step of carrying out color development in a processing tank and a step of processing with a processing solution having a fixing ability in a processing tank. The processing solution having a fixing ability contains a thiosulfate and a thiocyanate, and at least a part of the processing apparatus used in the processing method which is wet with the processing solution having the fixing ability and is in contact with air has the following general formula [I] This is achieved by a method for processing a silver halide photographic light-sensitive material, characterized by being formed from a polymer containing a repeating unit represented by formula (II) or (III).

General formula [I] In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a halogen atom, -CF ₃
Or -O-R represents _f, R _f represents a perfluoroalkyl group, at least one fluorine atom of R _1, R _2, R ₃ and R _4,
—CF ₃ or —O—R _f .

General formula (II) In the formula, R ₅ represents a hydrogen atom or a methyl group, and R ₆ represents a substituted or unsubstituted alkyl group.

General formula (III) In the formula, R ₇ represents a hydrogen atom, a chlorine atom or an alkyl group.

In the present invention, problems such as scratches and jamming, which are likely to occur particularly in a minilab, are mainly caused by fixation of a fixing solution component,
The present invention has been completed by elucidating from the market research and analysis that the sticking phenomenon is deeply related to the material of the rack and tank of the automatic developing machine.

In other words, this problem has become apparent with the introduction and spread of minilabs, and has never been seen before. Therefore, there is little knowledge about the prior art to solve this problem, and it has been revealed by careful market research and analysis.

The present inventors previously provided a solution to the above technical problem in Japanese Patent Application No. 2-36618, but the present invention further enhances the effect by using a combination of thiosulfate and thiocyanate as a fixing agent. It was something that could be done.

 Hereinafter, the present invention will be described in detail.

The polymer having a repeating unit represented by the general formula [I], [II] or [III] in the present invention (hereinafter referred to as “the polymer of the present invention”) includes a copolymer. Among the polymers of the present invention, a polymer having a repeating unit represented by the general formula [I] is preferable, and it is particularly preferable that R _{1 to} R ₄ in the general formula [I] contain no hydrogen atom.

In the general formula [II], the alkyl group represented by R ₆ may be linear, branched or cyclic, and preferably has 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. As the substituent of the alkyl group represented by R _6, for example, one having 1 carbon atom which may be substituted by a fluorine atom
And groups such as 3 to 3 alkoxy groups. In the general formula [II], R ₅ is preferably a methyl group, and particularly preferably, both R ₅ and R ₆ are methyl groups.

In the general formula [III], the alkyl group represented by R ₇ may be linear or branched, and preferably has 1 to 3 carbon atoms, and examples include a methyl group, an ethyl group, and a propyl group. R ₇ is particularly preferably a methyl group or a hydrogen atom.

The polymer of the present invention may contain a copolymer component other than the general formulas [I], [II] and [III] as long as the effects of the present invention are not impaired.

 Next, specific examples of the polymer of the present invention will be described.

2-1 Polymethyl acrylate resin 2-2 Polymethyl methacrylate resin 2-3 Polyethyl acrylate resin 2-4 Vinyl chloride-methyl acrylate copolymer resin 2-5 Vinyl chloride-methyl methacrylate copolymer resin 3 -1 Polyethylene 3-2 Polypropylene 3-3 Polyvinyl chloride The polymer of the present invention may be used alone or in a form to which a filler such as an antioxidant, an ultraviolet absorber, a pigment, and the like which are usually used is added. Is also good.

Resins consisting of the exemplified polymers 1-1 to 1-9 are commercially available under the following trade names.

In the method of the present invention, the processing solution having a fixing ability is preferably a fixing solution or a bleach-fixing solution, and the processing before the processing with the fixing solution is preferably a processing with a bleaching solution.

When a bleaching solution or a bleach-fixing solution is used in the processing method of the present invention, a bleaching agent which is generally used such as a ferric aminopolycarboxylic acid complex salt can be used as the bleaching agent.

In the present invention, a processing solution having a bleaching ability may contain a bleaching accelerator which is generally used. Typical specific examples of the bleaching accelerator are described in Japanese Patent Application No. 63-32501, 17-39.
(I-1) to (I-10), (II-1) to (II-)
27), (III-1) to (III-15), (IV-1) to (IV-
3), (V-1) to (V-23), (VI-1) to (VI-1)
7), (VII-1) to (VII-15), (VIII-1) to (VII
I-7), (IX-1) to (IX-5), (A-1) to (A
-8).

These bleaching accelerators may be used alone or two or more of them may be used in combination.
Good results are obtained in the range of 0.01 to 100 g.

However, in general, when the addition amount is too small, the bleaching accelerating effect is small, and when the addition amount is too large, precipitation occurs, which may contaminate the silver halide color photographic light-sensitive material to be processed. 0.05 to 50 g per liquid having the ability is preferable, and more preferably 0.05 to 50 g.
~ 15g.

When a bleaching accelerator is added, it may be added and dissolved as it is. However, it is general that the bleaching accelerator is dissolved in water, an alkali, an organic acid, or the like in advance, and then added, and if necessary, methanol, ethanol, acetone, etc. Can be added by dissolving using the above organic solvent.

The pH of the bleaching solution can be used from 1.0 to 7.0, preferably pH 2.0
When the ferric complex of 1,3 diaminopropanetetraacetic acid is used as a bleaching agent, it is preferably used at pH 2 to 5.5 in view of bleaching fog and stability. The pH of the bleach-fixing solution is preferably from 3.0 to 9.0, and more preferably from 4.0 to 8.0. The temperature of processing is used at 20-45 ° C,
Desirably, it is 25 ° C to 42 ° C.

The bleaching solution or the bleach-fixing solution may be usually used by adding a halide such as ammonium bromide.The bromide may be used in a small amount when the bleaching agent is used in the bleaching solution because the bleaching agent has a strong oxidizing power. 2.5 mol /
Hereinafter, it is preferably 0.5 to 2.0 mol /.

In addition, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
A pH buffer comprising various salts such as sodium acetate and anamonium hydroxide can be used alone or in combination of two or more.

In the present invention, it is preferable to use acetic acid which reduces bleach fog and is inexpensive as a pH buffer.
The preferred amount of acetic acid is 0.1 to 3 mol /, particularly preferably 0.4 to 2 mol /. When the amount of acetic acid is low, the bleaching fog increases, while when the amount of acetic acid is high, the desilvering property decreases.

In the present invention, the use of nitrates is preferred as an embodiment. When used in combination with the bleaching agent, the effect is particularly great, preventing the formation of ferrous complex salts and improving poor color reproduction. Furthermore, there is a rust-preventive effect, and the merit in cost is great.

The nitrate is 0.1 to 3 mol /, preferably 0.3 to 2 mol /
Used in the range.

Furthermore, various fluorescent whitening agents, antifoaming agents, surfactants and deterrents can be contained.

When the method of the present invention is applied to color processing, from the viewpoint of rapid processing, processing is preferably carried out with a bleaching solution and subsequently with a fixing solution or a bleach-fixing solution.

Preferred specific processing steps of the processing method according to the present invention are shown below.

(1) Color development-bleaching-fixing-processing with alternative washing solution (2) Color development-bleaching-fixing-rinsing-processing with alternative washing solution (3) Color development-bleaching-bleaching-fixing solution Processing (4) Color development-bleaching-bleach-fixing-rinsing-processing with alternative washing solution (5) Color development-bleaching-fixing-processing with alternative washing solution (6) Color development-bleach-fixing-rinse-washing alternative solution Among these steps, (1), (2),
(3) and (4) are preferred, and especially (1),
(2) is preferred.

The processing solution having a fixing ability in the method of the present invention, for example, a fixing solution and a bleach-fixing solution, and the thiosulfate which causes the formation of the fixed matter is, for example, potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate and the like. The amount of addition is 3 mol or less, more preferably 0.3 to 2 mol, and most preferably 0.5 to 2 mol per processing solution exhibiting fixing ability. Preferably, when the processing solution having a fixing ability is a fixing solution and contains the thiosulfate, the effect of the present invention becomes more remarkable.

As the thiocyanate contained in the processing solution having a fixing ability in the present invention, for example, ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate,
Thiocyanocatechol and the like. The amount of addition is 5 mol or less, more preferably 0.5 mol or more and 5 mol or less, most preferably 1 mol or more and 3 mol or less per processing solution exhibiting fixing ability.

In addition to these fixing agents, fixing solutions and bleach-fixing solutions also include
Sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, and carbonic acid Consists of various salts such as sodium, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide
A pH buffer may be used alone or in combination of two or more.

Further, those known to be added to ordinary fixing solutions and bleach-fixing solutions such as pH buffers, alkylamines and polyethylene oxides can be added as appropriate.

In the method of the present invention, air or oxygen may be blown in the processing bath and in the processing replenisher storage tank if desired in order to increase the activity of the bleaching solution or bleach-fixing solution, or a suitable oxidizing agent, For example, hydrogen peroxide, bromate, persulfate and the like may be appropriately added.

In carrying out the method of the present invention, silver or halogen may be recovered from the fixing solution or the bleach-fixing solution by a known method. For example, electrolysis (described in French Patent No. 2,299,667), precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, German patent
2,331,220), ion exchange method (JP-A-51-1
No. 7,114, described in German Patent 2,548,237, and a metal substitution method (described in British Patent 1,353,805) can be effectively used.

If these silver recovery or halogen recovery is performed in-line from the tank, silver recovery or halogen recovery will improve the suitability for rapid processing and the liquid storage stability of the washing-substitute stable liquid, and
Although particularly preferred, silver may be recovered from the overflow waste liquid and recycled.

In the method of the present invention, after treatment with a processing solution having a fixing ability containing a thiosulfate, it can be subsequently treated with a washing alternative stabilizing treatment solution (hereinafter referred to as “rinsing alternative stabilizing solution”) which is the final processing step. .

The treatment with the washing substitute stabilizing solution is a stabilizing treatment in which the stabilizing treatment is performed immediately after the treatment with the treating solution having a fixing ability, and substantially no washing treatment is performed.

In the present invention, when the number of stabilizing tanks is 1 to 5, the effect of the present invention is great, and particularly preferably 1 to 3 tanks.

It is preferable to add a surfactant and an antifungal agent to the washing substitute stabilizer.

The pH of the washing substitute stabilizer is preferably in the range of 2.0 to 10.0, and more preferably in the range of 3.0 to 9.5.

The pH adjuster that can be contained in the washing substitute stabilizer is
Any of the commonly known alkali or acid agents can be used.

When the processing solution in the pre-bath is a bleach-fixing solution in the washing alternative stabilizer, it is preferable to add a chelating agent having a chelate stability constant for iron ions of 8 or more.

Here, the chelate stability constant is LGSillen ・ AEMa
“Stability Constants of Metali on Complexe” by rtell
s ", The Chemical Society, London (1964), S. Chaberek
-"Organic Sequestering Agents" by AE Martell, Will
y (1959) means a constant generally known.

Examples of the chelating agent having a chelate stability constant for iron ions of 8 or more preferably used in the washing substitute stabilizing solution include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Can be In addition, the said iron ion is ferric ion (Fe
³⁺ ).

Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include the following compounds, but are not limited thereto.

That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid,
Glycol ether diamine tetraacetic acid, ethylenediamine trirakismethylene phosphonic acid, nitrilotrimethylene phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2
-Phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrilapolyphosphate, Examples include sodium hexametaphosphate, and particularly preferred are an organic phosphonic acid chelating agent and an inorganic condensed phosphoric acid chelating agent, and among them, 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the above chelating agent used is per stabilizing solution instead of washing.
The content is preferably 0.01 to 100 g, more preferably 0.05 to 50 g, which has the effect of significantly improving the white background performance of the unexposed portion and improving the image storability after processing.

The replenishment amount of the washing-substitute stabilizing solution is 2 to 30 times, preferably 3 to 20 times the amount of the prebath brought in by the silver halide color photographic light-sensitive material.

If the replenishment amount is outside the above range, for example, if it is less than 2 times, the backside stain of the photosensitive material becomes severe, and if it exceeds 30 times, the effect of the present invention, particularly the effect on image storability, is reduced. Occurs.

The processing temperature of the stabilization treatment with the washing substitute stabilizer is 15 to
The temperature is preferably in the range of 60 ° C, preferably 20 to 45 ° C.

The processing time is also preferably as short as possible from the viewpoint of rapid processing, but is usually from 20 seconds to 10 minutes, most preferably from 1 to 3 minutes. It is preferable that the processing time is longer in the later tank.

In the case of using a multi-tank countercurrent method, it is preferable to supply a post-bath bath and overflow the pre-bath in a stabilizing treatment step by supplying a washing-substituting stable liquid. Of course, it can also be processed in a single tank.

In the method of the present invention, the developing solution used for the developing treatment is not limited, and a commonly used developing solution can be used.

In the present invention, the part of the processing apparatus to which the polymer of the present invention is applied is a part that is at least wetted by the processing liquid having a fixing ability and is in contact with air. Causes of wetting with the processing solution,
There is no limitation on the process and the like, and the cause of wetting includes, for example, the case where the processing solution is wetted by the photosensitive material to which the processing solution adheres, or the case where the processing solution rises on the wall surface of the tank or the upper part of the rack due to capillary development, and becomes wet. Such a portion is typically provided, for example, with a squeezing roller, a roller for conveyance and guidance, a drive sprocket, and a guide for conveyance in a transfer section from, for example, a processing bath having a fixing ability to a next processing bath. It is at least a surface portion of a plate, an outboard rack or the like. At least the surface portion of such a member is composed of the polymer of the present invention (including coating the surface of the member with the polymer of the present invention), and a thiol is used as a fixing agent in a processing solution having a fixing ability. By using thiocyanate in combination with sulfate,
It is possible to more completely prevent the formation of the adhered matter due to the contact of the wetting with the processing solution containing thiosulfate as air.

FIG. 1 is a schematic sectional view showing an example of a processing apparatus according to the present invention. In the same figure, CD is the developing section, BL is the bleaching section, Fix
Is a fixing section, Stab is a stabilizing section for performing stabilization processing, 51 is a developing tank, 61 is a bleaching tank, 71a and 71b are fixing tanks, 81a, 81b and 81c are stabilizing tanks, 63, 73a, 73b, 83a and 83b. Is a squeeze roller,
Numerals 65, 75a, 75b, 85a, 85b, 85c, 86a, and 86b denote drive sprockets of the cross transport section, 77a and 77b denote guide rollers, and F denotes a transport path of the photosensitive material.

In the apparatus shown in FIG. 1, the members which are effective by applying the polymer of the present invention include squeeze rollers 73a and 73b, drive sprockets 75a, 75b and 75c of the transfer section, and guide rollers 77.
a, 77b and a rack outside the liquid, at least the surface of which is formed of the polymer of the present invention.

With this configuration, the components of the processing solution are prevented from sticking to the surface of the member that is wet with a processing solution containing a thiosulfate and has a fixing ability and that comes into contact with air, and therefore, the surface of the component when transported is conveyed. This eliminates the problem that the surface of the photosensitive material that comes into contact with the surface is rubbed with the adhered substance, causing scratches, and the occurrence of jamming that can be carried normally by the adhered substance.

An object to which the polymer of the present invention is effective is a part where the above-mentioned solid matter is generated in a processing apparatus. Particularly effective objects are a part where the above-mentioned solid matter is easily formed, specifically, thiosulfate. At a relatively high concentration (specifically 0.4 mol /
The above-mentioned processing liquid is used as a transfer part for transferring from a processing bath using a processing solution (for example, a fixing solution for rapid processing of a color negative film) to a stable bath with anhydrous washing. It is a part that is exposed to air for a long time in a wet state.

As a photosensitive material to which the present invention is particularly advantageously applied, a color negative film, for example, Konica Color DD manufactured by Konica Corporation
100, Konica Color GX200, Konica Color DD400, Konica Color GX3200, Super HG10 manufactured by Fuji Photo Film Co., Ltd.
0, Super HG200, Super HG400, Super HG1600,
KODAKARA GOLD 100, KODAKARA GOLD 200, KODAKARA GOLD 400, KODAKARA GOLD 1600, Ekta 25, etc., manufactured by Eastman Kodak Company.

〔Example〕

 Hereinafter, the method of the present invention will be described more specifically with reference to examples.

Example 1 Exemplary compound of the polymer of the present invention and the following comparative compound R
After washing the surface of the -1 to R-3 plate-shaped resin with distilled water, 0.1 ml of a fixing solution having the following composition is dropped on the dried sample.
After these were stored for 20 days at 80 ° C. and 60% humidity, 0.1 ml of a fixer having the same composition was dropped again, and the temperature was adjusted to 80 ° C. and 60% humidity.
After preservation for 20 days under the conditions described above, the surface was wiped off with a paper towel moistened with water, and the state of the surface was visually observed. The results are shown in Table 1. However, the condition of the surface was based on the following evaluation criteria (the same applies to Example 2 and thereafter).

◎: There is no adhesion to the surface and no deterioration of the surface.

：: Slightly adheres to the surface but can be removed with strong rubbing.

Δ: adhered to the surface and removed with strong rubbing.

×: sticks to the surface and the surface is slightly deteriorated.

XX: Strongly adheres to the surface, and the surface is remarkably deteriorated.

<Fixing solution composition> Ammonium thiosulfate 1.5 mol Ammonium thiocyanate 2.0 mol Sodium sulfite 20 g Bleaching solution (to be described below) 100 ml Finished to 1 and adjusted to pH 6.0 with acetic acid or aqueous ammonia.

<Bleaching solution> Ethylenediaminetetraacetic acid ferric ammonium 0.25 mol Ethylenediaminetetraacetic acid disodium 2.0 g Ammonium bromide 140 g Glacial acetic acid 15 ml Ammonium nitrate 30 g 3-mercapto-1,2,4-triazole 0.5 g Or with glacial acetic acid
Adjust to pH 6.0.

<Comparative compound> R-1 polystyrene resin R-2 acrylonitrile-styrene copolymer resin R-3 poly-4,4-dioxydiphenyl-2,2-propane carbonate resin As is clear from the results in Table 1, there is a difference in the state of fixation depending on the type of resin, and the fixation is severe when the comparative resin is used, and the fixability is clearly improved by using the resin of the present invention. It can be seen that the sticking property is greatly affected by the type of the resin.

Also, Polyflon TFE, Fluon, Algotlon, HalonTFE, Hos
taflonTF, neoflon PFA, neoflon FEP, Aflon COP,
NEOFLON ETFE, Tetzel, NEOFLON CTFE, KF Polymer Hal
Although ar, neoflon VDF and Tedlar were also examined, almost the same effect was obtained.

Example 2 The same experiment as in Example 1 was performed, except that the amounts of ammonium thiosulfate and ammonium thiocyanate in the fixing solution in Example 1 were changed to the amounts shown in Table 2. Table-Results
It is shown in FIG.

As is clear from the results in Table 2, there is a difference in the state of fixation depending on the concentration of ammonium thiosulfate and ammonium thiocyanate. When the concentration of ammonium thiosulfate is 0.5 mol / mol or more, the fixation is significantly large in the sample using the polymer of the present invention. It is improved, and the effect is greater when ammonium thiocyanate is used.

Further, ammonium thiosulfate and ammonium thiocyanate in the fixing solution were changed to potassium thiosulfate and potassium thiocyanate, respectively, and similar results were obtained.

The same results were obtained when ammonium thiosulfate and ammonium thiocyanate were replaced with sodium thiosulfate and sodium thiocyanate, respectively.

Example 3 Rollers made of the materials shown in Table 3 were used as drive sprockets 75a, 75b, 85a, 85b and guide rollers 77a, 77b, 86 in FIG.
a, 86b, Konica DD100 (manufactured by Konica Corporation) using an automatic developing machine installed on squeezing rollers 73a, 73b, 83a, 83b.
Kodacolor Gold 100 (manufactured by Eastman Kodak)
And a color negative film of Super HG100 (manufactured by Fuji Film Co., Ltd.).

Each of the above photosensitive materials was exposed at a ratio of 2: 1: 2,
0 (24 shots) were processed for 4 months.

The processing conditions and the composition of the processing solution are as shown below.

<Processing conditions> (Note) 1. The fixing step and the processing step using the washing substitute stabilizing solution are 2 tank and 3 tank counter currents, respectively.

2.Bring amount of bleach solution during fixing by photosensitive material is 80ml / m
²

 The color developing solution and the color developing replenisher have the following compositions.

<Color developing solution> Potassium carbonate 30 g Sodium hydrogen carbonate 2.7 g Potassium iodide 1.2 mg Potassium sulfite 2.8 g Sodium bromide 1.3 g Hydroxylamine sulfate 3.2 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N -(Β-hydroxylethyl) aniline sulfate 4.6 g diethylenetriaminepentaacetic acid 3.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g potassium hydroxide 1.3 g Add water to make 1 and add potassium hydroxide or 20% sulfuric acid. Adjust to pH10.01 using

<Color developing replenisher> Potassium carbonate 40 g Sodium bicarbonate 3 g Potassium sulfite 7 g Sodium bromide 0.9 g Hydroxylamine sulfate 3.2 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.0 g Diethylenetriaminepentaacetic acid 3.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Potassium hydroxide 2 g Add water to 1 and adjust to pH 10.12 using potassium hydroxide or 20% sulfuric acid. I do.

<Bleaching solution> Ferric complex ammonium salt of Exemplified compound A-1 0.3 mol 1,3-propylenediaminetetraacetic acid 5 g Ammonium bromide 95 g Glacial acetic acid 50 g Ammonium nitrate 40 g Add water to make 1 and use ammonium water or glacial acetic acid. Adjust to pH 4.5.

<Bleaching replenisher> Ferric complex ammonium salt of Exemplified Compound A-1 0.42 mol 1,3-propylenediaminetetraacetic acid 7 g Ammonium bromide 136 g Glacial acetic acid 70 g Ammonium sulfate 57 g Add water to make 1 to make ammonium water or glacial acetic acid Adjust to pH 3.5 using

<Fixing solution, Fixing replenisher> Ammonium thiosulfate 1.0 mol Ammonium thiocyanate 2.0 mol Ammonium sulfite 10 g Disodium ethylenediaminetetraacetate 1 g Water was added to 1 to adjust the pH to 1 using acetic acid and ammonia water.
Adjust to 6.5.

<Washing substitute stabilizer and replenisher> The results are shown in Table-3.

As is evident from the results in Table 3, the effects of the present invention in running experiments are also significantly improved by using the roller material of the present invention.

〔The invention's effect〕

According to the present invention, a portion of a processing apparatus used for a processing method in which a silver halide photographic light-sensitive material is conveyed and immersed in a processing solution in a processing tank is wetted with a processing solution containing thiosulfate and in contact with air. The formation of the resulting sticking is prevented. This prevents the occurrence of jamming and flaws during transportation of the silver halide photographic light-sensitive material caused by the adhered matter. Further, the burden of maintenance of the apparatus caused by the generation of the adhered matter is eliminated.

The formation of the adhered matter is as follows.
As described above, the content is particularly large when the content is contained at a concentration of 0.8 mol / or more, and the effect of the present invention is particularly large under these conditions.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a processing apparatus according to the present invention. 51 Development tank 61 Bleaching tank 71a, 71b Fixing tank 81a, 81b, 81c Stabilization tank

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 7/24 G03D 3/00 G03D 3/08

Claims (3)

(57) [Claims] 1. A method for processing a silver halide color photographic light-sensitive material, comprising the steps of: carrying a silver halide color photographic light-sensitive material; and, in a processing tank, performing color development and processing with a processing solution having a fixing ability. The processing solution having the fixing ability contains a thiosulfate and a thiocyanate, and at least a part of the processing apparatus used in the processing method which is wet with the processing solution having the fixing ability and which comes into contact with air has the following general formula [I ],
A method for processing a silver halide color photographic light-sensitive material characterized by being formed from a polymer containing a repeating unit represented by the formula (II) or (III): General formula (I) Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a halogen atom, -CF ₃
Or -O-R represents _f, R _f represents a perfluoroalkyl group, at least one fluorine atom of R _1, R _2, R ₃ and R _4,
—CF ₃ or —O—R _f . General formula [II] [Wherein, R ₅ represents a hydrogen atom or a methyl group, and R ₆ represents a substituted or unsubstituted alkyl group. General formula [III] [In the formula, R ₇ represents a hydrogen atom, a chlorine atom or an alkyl group. ] 2. The processing method according to claim 1, wherein said processing solution having a fixing ability is a fixing solution or a bleach-fixing solution. 3. The processing method according to claim 1, wherein the processing solution having the fixing ability contains a thiosulfate, and the thiosulfate contains at least 0.4 mol / content. .