JPH0232337A - Method and device for processing of processing liquid for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow sterilization and fungicidal action to a processing liquid without adversely affecting the processing liquid and photosensitive material by processing the processing liquid to be subjected to the sterilization and/or fungicidal action in fluctuating magnetic fields. CONSTITUTION:This device has a container 1 for containing the processing liquid, permanent magnets 2a, 2b, a ferromagnetic material 3 and a mechanism part 4 for rotating the ferromagnetic material 3. The insertion and extrication of the ferromagnetic material 3 into and out of the spacing part 2c of the permanent magnets 2a, 2b are repeated when the liquid to be processed is put into a container 1 consisting of a paramagnetic material and the ferromagnetic material 3 is rotated. The magnetic flux density of the magnetic field of the container 1 is thereby changed and the bacteria and fungi in the processing liquid in the container 1 are killed. The sterilization and fungicidal action of the processing liquid during the processing stage are executed in this way without adversely affecting the photosensitive material and the processing liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing a processing solution for silver halide photographic light-sensitive materials and an apparatus used therefor, and more particularly, to a method for processing a processing solution for silver halide photographic light-sensitive materials. The present invention relates to a novel sterilization and anti-mold method and a processing device to which the method is applied.

[Background of the invention]

When processing silver halide photographic materials using automatic processors, it is desirable to reduce or eliminate the amount of washing water used in the washing process due to environmental conservation and water resource issues. A technique has been proposed in which the material is treated with a stabilizing solution without washing with water.

However, when processing using a water washing alternative stabilizing solution is used for a long period of time, the amount of replenishment is extremely small compared to conventional water washing, so the solution is stored for a long period of time, and mold deposits are formed. There are problems that arise. In addition, bacteria and mold feed on the thiosulfate in the processing solution and multiply, and the sulfur produced by sulfurizing the thiosulfate adheres to the photosensitive material, causing spot failures.

Research on anti-fungal and fungicidal fungicides has been carried out since Yoshiki along with anti-bacterial sterilization. There has been considerable research into photographic materials, and anti-mold products are also commercially available. Furthermore, numerous documents have been disclosed regarding bactericidal and fungicidal agents that suppress the growth of bacteria and mold in the treatment solution. All of these agents are chemical agents and must have no interaction with photographic materials, so they have their own limitations.

Conventionally, the following properties have been desired for antifungal agents for aqueous compositions.

(1) It must be effective against all microorganisms that are involved in the deterioration of the target aqueous composition.

(2) Stability over a wide pI range from acidic to alkaline.

(3) Stability under temperature conditions.

(4) Chemical compatibility without reacting with the components of the composition.

(5) Safety including dermal and inhalation toxicity.

(6) Good workability.

(7) Biodegradability in drainage systems.

The anti-mildew agents for photographic light-sensitive materials are severely limited because they have no reactivity with both the light-sensitive material and the processing solution, and a decline in the performance of the processing solution cannot be tolerated.

Antifungal agents of alkylguanidine compounds known for photography are effective over a wide range of microorganisms, but the pH range in which they are used does not match the pH in which processing solutions for photographic light-sensitive materials are used.

Furthermore, antifungal agents made of triazine compounds are not sufficiently effective and have not yet been put to practical use.

Further, although some of these anti-mold agents are effective in processing solutions for photographic light-sensitive materials, it may be necessary to change the anti-mold agent depending on the composition or type of the processing solution for photographic light-sensitive materials.

Physical anti-mold methods meet the above seven conditions.
The seven items that satisfy condition (1) are mainly important, and the other six items have almost no relation. Regarding (4), such as changes in the performance of the processing solution for photographic light-sensitive materials, it is sufficient to kill the mold in a place where the processing reaction does not take place, and physical methods are extremely effective.

The present invention relates to a physical method, and provides a method for carrying out anti-mildew killing using physical effects at a location unrelated to the area of a photographic light-sensitive material where a chemical reaction takes place.

Recently, sterilization of various fungi by electrical methods has been researched and a comprehensive report (Bacterial and Antifungal Journal, Kore Matsunaga, Vol. 1.13. No. 5)
pp. 211-220). In these documents, reactions based on cell-electrode interactions,
The idea that conventional electrical sterilization methods mainly boil down to heat sterilization (see Hiroshi Horiguchi, The Chemistry of Antibacterial and Mildew Prevention, Sankyo Publishing, first edition on January IO, 1981), was developed into a new field. It is something. It is known that when voltage is applied to bacteria, coenzymes within the bacteria are oxidized, disrupting the function of substances in and out of cell membranes, and causing metabolic dysfunction.

This is because an electron transport element exists in the tricarboxylic acid cycle (TC 8he way) or the Krebs cycle discovered by Krebs, so it is an effective means as one of the effects that electricity has on cells.

Taking this idea one step further, we focused on the fact that elementary reactions in the glycolytic pathway, TCA cycle, photosynthesis, etc. in the metabolism of microorganisms all involve the exchange of electrons, and by applying a fluctuating electric field or current, we We have reached the goal of killing microorganisms in photographic processing solutions.

[Purpose of the invention]

An object of the present invention is to provide a technique for improving the above-mentioned drawbacks caused by bacteria and mold in the processing solution used in the processing of silver halide photographic materials. Another object of the present invention is to provide a means for sterilizing and mold killing a photographic processing solution that does not adversely affect the processing solution and the light-sensitive material during the processing of silver halide photographic materials.

Still another object of the present invention is to provide a technique for sterilizing and killing fungi by physical means in a processing solution used in the processing of silver halide photographic materials.

[Structure of the invention]

The above object of the present invention is achieved by treating a processing solution for sterilization and/or anti-mold used in the processing of silver halide photographic materials with a fluctuating magnetic field.

Furthermore, JP-A No. 60-263940 discloses a technique for preventing an increase in stain when a photographic material after processing is stored under high temperature and high humidity by passing an anhydrous washing stabilizing solution through a magnetic field. . However, this technology is not related to sterilization and anti-mold, nor does it use a fluctuating magnetic field.

In addition, the magnetic water activator "Algalid" manufactured by Algalid of Australia is known to prevent algae and bacteria from forming in the flush tank by using a fixed magnetic field (permanent magnet), but this is extremely effective. It was weak, and after several years of use, its effects were almost unrecognizable, and it had major drawbacks for practical use.

Hereinafter, the present invention will be explained based on the drawings.

FIG. 1 is a schematic sectional view showing an example of an apparatus used in the treatment method of the present invention. In this figure, 1 is a container containing a processing liquid, 2a and 2b are permanent magnets (electromagnets may be used), 3 is a ferromagnetic material, and 4 is a mechanism for rotating the ferromagnetic material 3.

FIG. 2 is a drawing of the ferromagnetic body 3 of FIG. 1 viewed from a direction parallel to its rotation axis. The ferromagnetic body 3 rotates around a shaft 4a and repeatedly moves in and out of the gap 2c between the permanent magnets 2a and 2b intermittently. In the figure, the two-dot chain line indicates the state in which the ferromagnetic material 3 is inserted into the gap portion 2c.

3a and 3b instead of the ferromagnetic material 3 shown in FIG.
A divided ferromagnetic material as shown in the figure can be used.

FIG. 3b is a sectional view taken along line II in FIG. 3a. In FIG. 3b, 8 is a divided ferromagnetic material, and the divided ferromagnetic material 9 and the paramagnetic material 10 are alternately arranged in a disk shape as shown. When such a divided ferromagnetic body 8 is used, it is convenient that dΦ/dt can be made variable or large depending on the number of divided ferromagnetic bodies (8 in FIG. 3) multiplied by the number of rotations. Here, Φ is the magnetic flux density, and dΦ/dt represents the change in the magnetic flux density over time.

Next, the operation of such a device will be described.

When a liquid to be treated is placed in a container l made of a paramagnetic material and the ferromagnetic material 3 is rotated, the ferromagnetic material 3 is repeatedly inserted into and removed from the gap 2c of the permanent magnets 2a and 2b, thereby causing the container to The magnetic flux density of the magnetic field of l changes, which causes
Bacteria and mold in the treatment liquid in the container 1 are killed.

The amount of change in magnetic flux density is preferably 50% or more,
Moreover, the period of change in magnetic flux density is preferably in the range of 50 to 2000 c/s. The magnetic pole area depends on the processing amount, but it is usually 33-24 m per 100 m (2/win) of the processing amount.
Approximately 0a'' is appropriate.

As a method for providing a varying magnetic field in the present invention, a method of forming a varying magnetic field by excitation with an AC power source can be used.

An example of such a device is shown in FIG. In the figure, ■
12 is a paramagnetic material, and 13 is a coil. The paramagnetic material 12 is excited by passing an alternating current through the coil 13. In such an embodiment, the number of cycles of the AC power source is preferably about lkc/s - IMc/s.

In such an embodiment of the apparatus, a flow of electrons is generated in the processing liquid in the container 1 based on a principle similar to that of a betatron, thereby killing bacteria and mold. It is preferable to select conditions such as the number of cycles of the power supply so that current flows as much as possible around the periphery of the container l, and such a design can be easily made by a person skilled in the art.

The processing device using a fluctuating magnetic field may be provided so that the container 1 in FIG. The treatment may be carried out while sending the treatment liquid to.

An example of such a device is shown in FIG. In the figure, 15 is a processing tank, and 16 is a pipe connecting the processing tank 15 and a container l for applying a fluctuating magnetic field, and a pump (not shown) circulates the processing liquid in the processing tank 15 to the container l.

The photographic processing solution to which the method of the present invention is applied is a processing solution for color and black and white silver halide photographic light-sensitive materials.Particularly effective is a processing solution in which bacteria and mold easily grow. This is a processing liquid such as a stabilizing liquid (anhydrous washing stabilizing liquid) that is used as a substitute for a process in which there is no actual washing process.

〔Example〕

Example 1 The following three species were used as test bacteria.

(A) Chaetomium globosum A
TCC6205(B) Cadsoporium he
rbarum IAMF 517(C) Trichr
oderma viride ATCC9678 Each of these strains was separately diluted with sterile water (Tween 800.0
103-10'/m (2).

Plant culture test tube (flat bottom) 25mmIX 100m+nL
Three drops of the above suspension were added dropwise into 2+aQ sterile water using a 1 ml pipette.

A varying magnetic field of 900 G and 1200 c/s was applied to this test tube and sterilized for 2 minutes, 2 minutes, 3 minutes, and 4 minutes. After that, this test solution was incubated at 25°C ± 2° for 7 days on GDA medium.
The cells were cultured at a C1 relative humidity of 90 to 95% and the number of bacteria was determined. As a comparative example, an experiment similar to the above was conducted except that a varying magnetic field was not applied.

All equipment used in these tests was kept at 121°C.
The material was sterilized using high-pressure steam for 20 minutes.

The results are shown in Table 1.

Table 1 (Note) In Table 1, for example, "576" indicates that survival of the bacterial strain was observed in 5 out of 6 tests.

Example 2 Using the apparatus shown in FIG.
The container l for placing the 2mm (2) into the treatment tank 15 and treating it with a fluctuating magnetic field is made of polyvinyl chloride with a thickness of 2ff1m and has an inner diameter of 5cm (width) x 4cm (width) x loam (height). A container was used, the permanent magnets 2a and 2b had a magnetic flux density of 1200 G and a magnetic pole area of 5 cm, the gap 2C was 20 mm, and the ferromagnetic material was a divided ferromagnetic material 8 shown in FIG. MF is used for the ferromagnetic material 9.
A25(BH)max=0.23(AWb/m'x
10') was rotated at 60 rpm using hard polyvinyl chloride as the paramagnetic material IO. Then, the stabilizing liquid in the treatment tank 15 was circulated into the container 1 at a rate of 100 mQ/min.

Under the above conditions, the number of bacteria in the stabilized solution after being left at a temperature of 28° C. for 24 hours was measured by the culture method in the same manner as in Example 1. The treatment with the fluctuating magnetic field was carried out throughout the entire time of the above-mentioned standing time, and the state of bacterial production and sulfurization in the stabilization tank was observed.

Comparative Example 1 The same experiment as in Example 2 above was conducted except that the treatment with a varying magnetic field was not performed.

Comparative Example 2 Instead of the above-mentioned treatment using the fluctuating magnetic field, a Magne-Node water activator Algalid (manufactured by Algalid, Australia) was installed, and the same experiment as in Example 2 was conducted except for the above.

The above results are summarized in Table 2.

Table 2 (Note) In the table, the mark ○ means that there is no formation of bacteria or sulfurization, and the mark X means that the generation of bacteria and sulfurization are observed. This means that the degree is large.

Example 3 An experiment was carried out under the same conditions as in Example 2 above, except that the rotation speed of the divided ferromagnetic material was changed to 24 Orpm and the circulation rate of the stabilizing liquid was changed to 50 mQ/min. As a result, almost the same results as in Example 2 were obtained.

〔Effect of the invention〕

The present invention provides a new and physical means for sterilizing and preventing mold in processing solutions (developing solution, fixing solution, bleach-fixing solution, and anhydrous washing stabilizer) used in the processing steps of silver halide photographic materials. Ru.

According to the present invention, a higher level of sterilization and mold prevention than can be achieved by conventional chemical means is possible.

According to the present invention, the processing liquid can be sterilized and molded during the processing process without any adverse effect on the silver halide photographic light-sensitive material and the processing liquid.

[Brief explanation of the drawing]

FIGS. 1 and 2 are cross-sectional views and front views of essential parts of an example of a treatment liquid processing apparatus using a fluctuating magnetic field according to the present invention, and FIGS. 3a and 3b are ferromagnetic materials shown in FIG. 1. Fig. 4 is a plan view showing an example of a device that applies a fluctuating magnetic field using an AC power source, and Fig. 5 shows a device using a fluctuating magnetic field provided outside the processing tank. FIG.

Claims (2)

[Claims] (1) A method for processing a processing solution for a silver halide photographic light-sensitive material, which comprises processing at least one of the processing solutions for a photographic material in a fluctuating magnetic field. (2) A processing apparatus for silver halide photographic light-sensitive materials, characterized by having means for processing a processing liquid in a fluctuating magnetic field.