JP2704269B2 - Method for preventing mildew in anhydrous washing stabilization tank for silver halide photographic light-sensitive materials - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing mold from a stabilizing solution in an anhydrous washing stabilizing tank in a processing step of a silver halide photographic light-sensitive material, and an apparatus used therefor.

Here, “anhydrous washing stabilization tank” refers to a treatment tank for treating with a stabilizing solution instead of washing in a treatment step in which there is substantially no washing step in the treatment step.

[Conventional technology]

In processing of a silver halide photographic light-sensitive material by an automatic processor, it is desired to reduce or eliminate the washing water used in the washing step from the viewpoint of environmental conservation and water resources, so that the processing with a fixing solution or a bleach-fixing solution is required. Then, a technique of treating with a stabilizing solution without washing with water has been proposed.

However, when the solution is treated for a long time by the treatment method using a washing substitute stabilizer, the replenishing amount is extremely small as compared with the conventional washing, so that the solution is stored for a long period of time, and precipitates due to mold are reduced. There are problems that arise. In addition, molds grow by eating thiosulfate in the processing solution, and sulfur produced by sulfidizing thiosulfate adheres to the photosensitive material to cause spot defects.

[Object of the invention]

An object of the present invention is to provide a technique for improving the above-mentioned disadvantages caused by mold in a processing solution for a silver halide photographic light-sensitive material.

[Configuration of the invention]

The object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material, in which the anhydrous washing stabilizing solution is put into contact with the free surface of the stabilizing solution on the inner wall of the processing tank (hereinafter referred to as "liquid level portion"). This is achieved by adhering or adhering a tape-shaped fungicidal layer that can be adhered or adhered to the inner wall only within a range of 5 cm below the inner wall.

 Hereinafter, the present invention will be described in detail.

In the present invention, it is important that the antifungal layer is provided only on the inner wall within a range of 5 cm above and 5 cm below a portion of the inner wall of the anhydrous washing stabilization tank in contact with the free surface of the stabilizing solution (hereinafter, referred to as “liquid level portion”). is there. The reason is that the growth of mold in the anhydrous washing stabilization tank is remarkable in the treatment liquid portion in contact with air.

Examples of the tape-shaped antifungal layer include those obtained by applying or integrally molding an antifungal agent on a support such as plastic or the like and applying an adhesive via a subbing agent. As described above, by providing the tape-shaped antifungal layer by adhesion or adhesion, convenience in use is improved. That is, mold is not always generated in the processing by the automatic developing machine,
Rather, the level that does not occur is the level that can be said to be the majority, but once it occurs, it becomes a major problem. For this reason, it is preferable from an economic viewpoint that the tape-shaped antifungal layer is provided by bonding or sticking only to the automatic developing machine in which this problem occurs. Furthermore, molds and fungi often produce resistant bacteria with the passage of time against fungicides and the like,
In this case, a tape-type antifungal layer containing a different type of antifungal agent is simply laminated on the conventionally used tape-type antifungal layer, and is simply applied. It is economical to deal with. Some antifungal agents can also be produced without the undercoating agent.

In order to use this tape more conveniently, it is preferable that one or both of the surface of the adhesive and the surface of the fungicide be covered with a coating film so that the tape can be easily removed at the time of use.

Examples of the tape containing an antifungal agent include a suitable support such as paper, cloth, glass cloth, fiber, or foam impregnated with the antifungal agent, and a suitable support such as biaxial. Examples of the tape include a tape which is adhered on a stretched polypropylene and the other surface of the support is coated with an adhesive.

The surface of the inclusions such as paper, cloth, glass cloth, foam, etc. containing the antifungal agent exhibits the effect of the antifungal agent. In the case where is a substance having a property of eluting into the treatment liquid, it is desirable that the fungicide or the layer containing the fungicide is covered with a film imparting sustained release. As a film for imparting sustained release properties (sustained release film), a membrane having a transmittance corresponding to the permeability of the fungicide is effective.

The antifungal agent to be contained in such a tape is preferably one which does not adversely affect the stabilizing solution and the silver halide photographic material. Preferably used fungicides,
Hydroxybenzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine Compounds, sulfamide derivatives, amino acid compounds,
Triazole compounds, dehydroacetic acid and sodium dichloroisocyanurate.

The hydroxybenzoic acid-based compound includes hydroxybenzoic acid and an ester compound of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester, and butyl ester, and is preferably hydroxybenzoic acid butyl ester, isobutyl ester, and propyl ester. And more preferably a mixture of the above three hydroxybenzoic acid esters.

Phenol compounds, unsubstituted or alkyl machine C1 ~
And a compound having 6 alkyl groups as substituents, preferably phenol, orthophenylphenol, and orthocyclohexylphenol.

The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, preferably 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4. -Isothiazoline-3-
On, 5-chloro-2-methyl-4-isothiazoline-
3-one and 2- (4-thiazolylbenzimidazole. Specific examples of pyridine-based compounds include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, and sodium-2-.
There are pyridinethiol-1-oxide and the like, and preferably sodium-pyridinethiol-1-oxide.

Guanidine compounds are specifically cyclohexidine,
Polyhexamethylene biquanidine hydrochloride and dodecyl guanidine hydrochloride, preferably dodecyl guanidine and its salts.

Specific examples of the carbamate-based compound include methyl-1- (butylcarbamoyl) -2-benzimidazole carbamate and methylimidazocarbamate.

Specific examples of the morpholine-based compound include 4- (2-nitrobutyl) morpholine and 4- (3-nitrobutyl) morpholine.

Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc.
Preferred are tetraalkylphosphonium salts, and more particularly preferred compounds are tributyl-tetradecylphosphonium chloride and tri-phenylnitrophenylphosphonium chloride.

Specific examples of the quaternary ammonium compound include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, and alkylpyridinium salts, and specific examples include dodecyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, laurylpyridinium chloride, and the like. .

The urea compounds are specifically N- (3,4-dichlorophenyl) -N '-(4-chlorophenyl) urea, N- (3
-Trifluoromethyl-4-chlorophenyl) -N'-
(4-chlorophenyl) urea and the like.

Specific examples of the isoxazole-based compound include 3-hydroxy-5-methyl-isoxazole.

The propanolamine-based compounds include propanols and isopropanols. Specifically, DL-2-benzylamino-1-propanol, 3-diethylamino-1-
Propanol, 2-dimethylamino-2-methyl-1-
Propanol, 3-amino-1-propanol, isopropanolamine, diisopropanolamine, N, N-
And dimethyl-isopropanolamine.

Sulfamide derivatives are specifically fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, sulfanilamide, acetosulfamine, sulfapyridine, sulfaguanidine, sulfathiazole, sulfadiazine, sulfamerazine, sulfamethazine, sulfamide Physoxazole, homosulfamine, sulfisomidine, sulfaguanidine, sulfamethizole, sulfavirazine, phthalisosulfathiazole, succinylsulfathiazole and the like.

Amino acid compounds include N-lauryl-β-alanine.

Examples of the triazole-based compound include benzotriazole, triazole, and chlorotriazole.

Among the above fungicides, the compound preferably used in the present invention is 2-methyl-4-isothiazoline-3-.
On, 2-octyl-4-isothiazolin-3-one,
5-chloro-2-methyl-4-isothiazolin-3-one, benzotriazole, phenol, o-phenylphenol, dehydroacetic acid, sodium dichloroisocyanurate.

These antifungal agents may be contained in the stabilizing solution in combination with the method of the present invention. In this case, the amount of the antifungal agent added to the stabilizing solution is preferably in the range of 0.002 to 50 g per stabilizing solution. ,
More preferably, it is in the range of 0.005 to 10 g.

 Next, the present invention will be described with reference to the drawings.

FIG. 1 is a schematic sectional view showing an example of an anhydrous washing stabilization tank having an antifungal layer according to the method of the present invention. In this figure, 1 is an anhydrous washing stabilization tank, 2 is a stabilizing solution, 3 is its free surface, and 4 is a fungicide tank. The antifungal tank 4 is provided at the height and width shown in the figure over the entire circumference of the inner wall of the anhydrous washing stabilization tank.

2 and 3 are cross-sectional views of examples of a tape containing an antifungal agent used as an antifungal tank according to the method of the present invention, where 10 is an adhesive layer, 11 is an undercoat layer, and 12 is a supporter. 13 is a fungicide-containing layer, 14 is a film for imparting sustained release, and 15 is a coating film.

〔Example〕

Example 1 A tape having a structure shown in FIG. 2 was prepared as an antifungal layer as follows.

Preparation of tape Trichlorocarbanilite (white powder) is sandwiched between a polypropylene film (100 μm thickness) and a perforated polyester film (0.1 μm hole, 20 μm thickness), and is molded into a 0.1 g / m ² drug. The density of the film.

This tape was dried and stabilized as shown in Fig. 1 (capacity 5).
Affixed over the entire circumference of the lower part, including the liquid surface part of the inner wall, of 4 cm in width, stabilizing solution 4 having the following composition, 120 ml of bleach-fixing solution of the following element and Aspergillus niger, Penicillium fun
iculosum, Chaetomium globosom, Trichoderma SP, Pullul
10 ml of the mixed spore suspension of aria pullulaus was added thereto, stirred and mixed, and allowed to stand at 35 ° C. Then, the growth state and sulfidation state of the mold were observed (Experiment 1-1).

Stabilizer Sodium dichloroisocyanurate 0.1 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g Benzotriazole 0.1 g Ethylene glycol 1.0 g 2-octyl -4-isothiazolin-3-one 0.01 g 1-hydroxyethylidene-1,1-diphosphonic acid (60%
Aqueous solution) and 1 3.0 g BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} 0.2g of ammonia water (ammonium 25% aqueous hydroxide) 2.5 g nitrilotriacetic acid, trisodium salt 1.5g water, ammonia water and sulfuric acid To pH 7.0.

Bleaching-fixing solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust pH to 5.5 with potassium carbonate or glacial acetic acid and water. In addition, the total amount is set to 1.

Separately, the same experiment as in Experiment 1-1 was performed except that the tape was not attached to the inner wall of the anhydrous washing stabilization tank (Experiment 1-).
2).

 The above results are shown in Table 1 below.

From the above experiments, it can be seen that the present invention can achieve a remarkable fungicidal and sulfidation-preventing effect by a very simple method.

〔The invention's effect〕

ADVANTAGE OF THE INVENTION According to the present invention, the growth of mold in the anhydrous washing stabilization tank in the processing step of the silver halide photographic light-sensitive material is suppressed, the generation of the precipitate by the mold and the sulfidation of the thiosulfate are prevented, and the sensitization caused by these is prevented. Material failure occurrence is improved.

Further, according to the present invention, convenience in use is improved by providing a tape-shaped fungicide tank by bonding or sticking.
That is, molds are not always generated in the processing by the automatic developing machine, and the molds that do not are generated do not often occur. For this reason, the tape-shaped antifungal layer can be stuck and provided only on the automatic developing machine in which mold is generated, which is economically preferable. Furthermore, molds and fungi often produce resistant bacteria with the passage of time against fungicides and the like. In this case, a tape-shaped fungicide layer containing another kind of fungicide has been conventionally used. By laminating and applying the tape-shaped antifungal layer on top, it is possible to easily cope with only an automatic developing machine having a problem, and it is economical.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of an apparatus according to the present invention, and FIGS. 2 and 3 are sectional views showing examples of a tape containing an antifungal agent. 1 stabilizing tank for anhydrous washing, 2 stabilizing solution 3 free surface of stabilizing solution, 4 antifungal layer 5 passage for photosensitive material, 10 adhesive layer 11 subbing layer, 12 subbing layer Support 13: layer containing deodorant, 14: film for imparting sustained-release property 15: coating film

Claims (2)

(57) [Claims] 1. A method for processing a silver halide photographic light-sensitive material, comprising: A method for controlling fungi in an anhydrous washing stabilization tank, comprising bonding or sticking a tape-shaped fungicide layer which can be adhered or adhered. 2. A tape-shaped antifungal tank that can be adhered or adhered to the inner wall only in a range of 5 cm above and 5 cm below a portion of the inner wall of the anhydrous washing stabilization tank that contacts the free surface of the stabilizing liquid. An anhydrous washing stabilization bath for silver halide photographic light-sensitive materials, characterized in that: