JPH07225463A - Method for preventing fur of washing section of automatic developing machine - Google Patents

Abstract

PURPOSE:To provide the method for preventing fur of a washing section which lessens adhesion of slime and generation of black stains in a photosensitive material to be processed in spite of decreasing of the replenishing amt. of a developer and/or fixer to be replenished, is excellent in finishing and preservable property of a silver image and is capable of decreasing maintenance operations of an automatic developing machine. CONSTITUTION:This method for preventing the fur of the washing section of the automatic developing machine for black and white silver halide photographic sensitive materials having a developing section, fixing section and washing section comprises adding a glutaraldehyde and chelate agent to the washing water of the washing section. The glutaraldehyde is further added to the fixer in the fixing section as well. The amt. of the fixer to be replenished at the time of processing is adjusted to <=480cc per 1m<2> photosensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing scale stains on the washing part of an automatic developing machine for black and white silver halide photographic light-sensitive materials. The present invention relates to a method for preventing water stains on a washing part of an automatic developing machine for a black and white silver halide photographic light-sensitive material, which can effectively purify and regenerate and guarantee the finishing performance of a silver halide photographic light-sensitive material to be processed.

[0002]

2. Description of the Related Art In recent years, in the field of printing plate making, in order to reduce the amount of waste liquid in the processing step of a silver halide photographic light-sensitive material used as an intermediate recording medium and to improve the handleability of a processing solution in a kit, It is desired to reduce the replenishment amount of the fixer.

An automatic processor for processing an exposed silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material) is provided with a plurality of processing tanks containing processing liquids for development, fixing, washing and the like. Processing is carried out by sequentially transporting the photosensitive material and immersing it in each processing solution for a predetermined time. Therefore the developer,
When the replenishing amount of the fixing solution is reduced, the concentration of substances eluted from the photosensitive material in the developing solution and the fixing solution increases.

On the other hand, in the water washing tank, organic substances such as gelatin are used as nutrients to generate scales (slime, etc.) due to bacteria, mold, etc., and the slime is transferred to the light-sensitive material to be processed, resulting in deterioration of image quality. It has been known in the past that even the conveyance failure of the automatic developing machine is caused, but due to the decrease in the replenishment amount, the occurrence of scale becomes more likely to occur.

A technique of adding a bactericidal agent or an antifungal agent has been conventionally known as a method for preventing scale in the washing tank, but in the case of processing a black and white silver halide photographic light-sensitive material, it is used in an automatic processor. Since the washing water used is continuously supplied and is used in a state of running off, it must be used in a large amount in order to maintain an effective concentration, and when it is used in a large amount, the running cost increases and the silver image There is a problem such as yellowing with time.

[0006] In addition, Japanese Patent Laid-Open No. 3-43734 describes a method using ozone, but there are problems such as local generation of scale and safety.

Further, the applicant of the present invention has disclosed Japanese Unexamined Patent Publication Nos. 2-244139 and 2-24.
The method of preventing scale using the oxidizing agent proposed in No. 4141 and No. 4-276745 is a process in which the fixing agent brought into the washing water and the oxidizing agent react with each other, and silver oxide and silver sulfide are by-products. When silver compounds such as the above are generated, and these silver compounds have high water-saving efficiency in washing water, they may accumulate in the washing tank and adhere to the light-sensitive material to be processed, resulting in black stains.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a finished product which is free from slime and black stains on the light-sensitive material to be processed even if the replenishment amount of the developing solution and / or the fixing solution is reduced. It is an object of the present invention to provide a method for preventing water stains on a washing part, which has excellent storability of silver images and can reduce maintenance work of an automatic processor.

[0009]

The above object of the present invention is to provide glutaraldehyde and a chelating agent in the washing water of the washing section of an automatic developing machine for black and white silver halide photographic light-sensitive materials having a developing section, a fixing section and a washing section. A method for preventing scale stains on the washing section of an automatic processor, adding glutaraldehyde to the fixing solution in the fixing section, and replenishing the fixing solution at a processing amount of 480 cc or less per 1 m ^{2 of the} light-sensitive material, Achieved by

The present invention will be described in detail below.

The amount of washing water used in the present invention is preferably ^{2 to} 40 liters per 1 m ² of the light-sensitive material.

A commercially available product can be used as glutaraldehyde. When added to the washing water, it is preferable to dilute a commercial product of glutaraldehyde with an appropriate solvent so that the pH is 5 or less, and the addition amount is 1.0 × 10 5 / l of washing water.
^{-4 to} 1.0 x 10 ^-2 mol is preferable.

Glutaraldehyde is further added to the fixing solution in an amount of 0.01 to
It is preferable to add 10 mol / l because it is effective in preventing water stain.

This is considered to be due to the effect of suppressing the elution from the light-sensitive material due to the hardening effect of glutaraldehyde and the effect of bringing glutaraldehyde into the washing water. The pH of the fixing solution is preferably 4.0 to 5.5.

In the present invention, the amount of the chelating agent added is preferably 10 mg to 10 g, and more preferably 50 mg to 1 g per liter of washing water during the washing treatment.

Specific examples of preferably used chelating agents include ethylenediaminetetra4acetic acid (EDTA), propylenediaminetetraacetic acid (PDTA), diethylenetriamine5acetic acid, citric acid, ethylenediamine4 (methylenesulfonic acid), dipicolinic acid, Examples thereof include, but are not limited to, tetrasodium pyrophosphate, nitrilotriacetic acid, uramil triacetic acid, dimethylglyoxime, dithizone, oxine, acetylacetone, glycine, pyridinecarboxylic acid, and salts thereof.

In the present invention, glutaraldehyde and the chelating agent may be separately added to the washing water.
Further, it may be manually added to the washing tank, but it is preferably added automatically by using a pump or the like.

The automatic developing machine used in the present invention preferably has at least a developing section, a fixing section and a water washing section, and preferably has a means capable of draining a part of the washing water. Hereinafter, it will be described in more detail with reference to the drawings.

FIG. 1 is a schematic view showing an example of a mechanism adopting the method for preventing water stains on the washing section of the automatic processor of the present invention.
According to this, the means 2 for supplying the additive containing the glutaraldehyde and the chelating agent and the means for supplying the washing water 3 are connected to the washing tank 1 of the automatic developing machine on the basis of the processed area information of the photosensitive material, and the means 4 for draining the washing water 4 Is configured to prevent contamination of washing water due to accumulation of eluate from the light-sensitive material. The glutaraldehyde and the chelating agent can be added individually by different supplying means, but it is preferable to configure as shown in the figure in terms of downsizing of the device. Further, the additive supply means 2 is preferably housed in an automatic processor.

A well-known stirring means such as a circulation pump and an impeller can be adopted in the water washing tank 1 to effectively prevent water stains.

Further, in order to keep the contaminated concentration of the washing water within the water quality standard, it is preferable to perform drainage of ^{2 to} 40 l per 1 m ^{2 of the} processed area of the light-sensitive material while controlling the pH of the washing water so as not to fall below 5.7. .

Various conventionally known means can be adopted in the water washing section of the automatic processor to which the present invention is applied.

The black and white silver halide photographic light-sensitive material to which the present invention is applied include, in addition to the above-mentioned printing film (for example, gravure film), a facsimile film, a mask film for the electronic industry, a black-and-white paper, and a computer typesetting. Paper, etc., and particularly, a high contrast type containing a hydrazine compound or a tetrazolium compound in a light-sensitive material can be favorably processed.

For the developing section, fixing section and drying section of the automatic developing machine to which the present invention is applied, all of various conventionally known systems can be used.

The black and white developer is preferably a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones as developing agents, but other p-aminophenol or ascorbic acid developing agents may be used. Good.

Examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethyl. There are hydroquinone and the like, but hydroquinone is particularly preferable.

As 1-phenyl-3-pyrazolidone or its derivative developing agent, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
There is pyrazolidone.

N-as a p-aminophenol-based developing agent
Methyl-p-aminophenol, p-aminophenol, N-
There are (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc., but N-methyl-p-aminophenol is preferable.

The developing agent is preferably used in the range of usually 0.01 mol to 1.2 mol per 1 liter of the developing solution.

The pH of the developer is preferably 9 to 13. More preferably, it is 10-12.

For adjusting the pH, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium triphosphate, sodium triphosphate or the like may be used.

Sucrose, acetoxime, 6-sulfosalicylic acid and the like described in JP-A-60-93439 are disclosed in JP-A-60-93439.
Buffers such as borate described in 61-28708, and phosphate and carbonate may be used.

Other additives such as sulfites, development inhibitors, organic solvents, antifoggants, toning agents, surfactants, defoamers, water softeners, amino compounds described in JP-A-56-106244 , A silver stain inhibitor, compounds described on pages 226-229 of "Photographic Processin Chemistry" by LFA Meson (1966, published by Focal Press), described in US Pat. Nos. 2,193,015 and 2,592,364. Compounds such as those described in JP-A-48-64933 may be used.

The fixing solution is an aqueous solution containing a thiosulfate such as sodium thiosulfate and ammonium thiosulfate as a fixing agent, and contains thiosulfate ion and ammonium ion as essential components. From the viewpoint of the fixing speed, it is preferable to contain ammonium thiosulfate. The fixing agent is generally 0.1 to 6 mol /
Used in the range of 1.

The fixing solution may contain a water-soluble aluminum salt such as aluminum chloride, aluminum sulfate, or potassium alum that acts as a hardening agent.

The fixer contains tartaric acid, potassium tartarate, sodium tartarate, potassium sodium tartarate, citric acid,
Sodium citrate, potassium citrate, lithium citrate, ammonium citrate and the like can be used alone or in combination. These compounds per liter of fixer
It is effective to contain 0.005 mol or more, especially 0.01 mol / l
.About.0.03 mol / l is particularly effective. Furthermore, preservatives such as sulfites and bisulfites, pH buffering agents such as acetic acid and nitric acid,
A pH adjusting agent such as sulfuric acid, a chelating agent capable of softening water, and the like can be included.

The replenishing amount of the fixing solution when processing the photosensitive material is 1 m ²
The effect of the present invention is remarkable in a processing system in which the amount of replenishment is reduced, such as 480 cc or less.

[0038]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 Using the automatic processor shown in FIG. 1, the additives shown in Table 1 and 3.5 liters of water for each processing area corresponding to the overall size of the printing plate making film of 508 mm × 610 mm were developed by the automatic processor. Information was added from the liquid replenishment operation signal to the water washing section at any time, and the washing water in the water washing tank was drained by the amount of the replenishment and treated. Consecutive 135 sheets of all size films at the fixing replenishment amount shown in Table 2
The following criteria were used for visual evaluation of slime stains in the washing tank, slime stains of the film, and silver sludge stains when the treatment was continued for a month. The results are shown in Table 2.

<Washing tank slime stain> ○ No occurrence △ Slightly adhered to the bottom × Adhered to the entire surface << Film adhered slime stain >> ○ Not generated △ Only adhered to the first sheet at the start of processing × Adhered every several sheets 《Black (silver sludge) stain》 ○ No occurrence △ Only adhered to the first sheet at the start of processing × Adhered to every several sheets Also, the processed film was stored at 50 ° C, 80% RH for 3 days, and then silver image Was observed.

<Silver image storability> ○ No change × Change to brown color The film used was Konica Corporation's bright room return film RC, a plate-making printer P- made by Dainippon Screen Co., Ltd. A blackening rate of about 20% exposed with 607 (light source: ultra-high pressure mercury lamp URT-CHM-1000), the developer is made by Konica Corporation
CDM-671 was used.

[Formulation of fixer] Ammonium thiosulfate (72.5 wt% aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g Sulfuric acid (50 wt / vol% aqueous solution) 4.7 g Glutaraldehyde Amount shown in Table 1 These are sequentially dissolved in 500 ml of water, and the volume is adjusted to 1 liter with p-acetic acid.
The H was adjusted to 4.8.

[0043]

[Table 1]

[0044]

[Table 2]

Example 2 The developer used in Example 1 was RA manufactured by Eastman Kodak Company.
-2000, the photographic light-sensitive material was S manufactured by Eastman Kodak Company.
Evaluation was carried out by running treatment for 3 months in the same manner as in Example 1 except that AI was used and exposed with an argon laser at a blackening rate of 50%. The results are shown in Table 3.

[0046]

[Table 3]

[0047]

As demonstrated in the examples, according to the method for preventing scale formation of the present invention, it is understood that slime is not generated and silver sludge is not contaminated even when the replenishing amount of the fixing solution is reduced.

[Brief description of drawings]

FIG. 1 is an example of an automatic developing machine that employs the scale prevention method of the present invention.

[Explanation of symbols]

 1 Washing Tank 2 Additive Supplying Means 3 Washing Water Supplying Means 4 Draining Means 5 Developing Unit 6 Fixing Unit

Claims (3)

[Claims] 1. An automatic developing machine for a black and white silver halide photographic light-sensitive material having a developing section, a fixing section and a water washing section, wherein glutaraldehyde and a chelating agent are added to the washing water in the water washing section. How to prevent water stains on the washing part. 2. The method for preventing scale stains in a washing section of an automatic processor according to claim 1, wherein glutaraldehyde is added to the fixing solution in the fixing section. 3. The replenishing amount of the fixing solution when processing the photosensitive material is 1 m ²
3. The method for preventing water stains in the washing section of the automatic processor according to claim 1, wherein the amount is 480 cc or less.