JPH08202007A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To prevent the adhesion of fur, to improve transportability and to prevent acetic acid smell from remaining after drying by confining the acetic acid content in a fixer in specific range and incorporating antimicrobial calcium phosphate ceramics into tanks or transporting rollers. CONSTITUTION: The content of the acetic acid in the fixer used for automatic development processing is >=0.3 to <=1.5mol/liter and the tanks of a washing stage or stabilizing stage and the transporting rollers used in the stages contain the antimicrobial calcium phosphate ceramics. The pH when running equil. is attained increases and a hardening defect arises when the amt. of a buffer is decreased if the content of the acetic acid in the fixer is below 0.3mol/liter. The residual acetic acid smell of the silver halide photographic sensitive materials after processing and drying is strong and is undesirable at >=1.5mol/ liter. Then, the acetic acid smell does not remain in the silver halide photographic sensitive materials after processing and drying, the adhesion of fur at the washing tanks, washing rollers, etc., does not arise and the transferability improves if the content of the acetic acid in the fixer is above 0.3mol/liter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide photographic light-sensitive material which is free of scales, has good transportability, and has no acetic acid odor after drying. Regarding

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material for X-ray diagnosis is generally processed by an automatic processor after being exposed to X-rays.
That is, the film having been photographed is sequentially immersed in a developing tank, a fixing tank and a washing tank (stabilizing tank) for development, fixing and washing (stabilization), and then dried in a drying section. In each of the above steps, each processing solution is replenished in accordance with the processing of the light-sensitive material, and preferable processing conditions are always maintained.

In recent years, from the standpoint of environmental protection, low replenishment of processing solution has become an essential condition. However, when the replenishing amount of the fixer is reduced, the developer contained in the silver halide photographic light-sensitive material is brought into the fixer with respect to the amount of the fixer to be replenished. The pH is increased, causing a film hardening defect, which causes a conveyance defect due to a drying defect or a slip.

For this reason, it is necessary to increase the amount of acetic acid in order to maintain the pH of the fixing solution. However, the increase in acetic acid has a drawback that an acetic acid odor remains in the silver halide photographic light-sensitive material after processing and drying. A large amount of water is supplied, and the liquid in the tank overflows and is replaced with new water, improving the washing efficiency. In addition, a water-saving type is often used in which the washing water is supplied by the film detection mechanism only during the processing of the film, and when the processing is interrupted, the washing water is not replenished and purified by discharging.

In this case, when the treatment is completed, the replenishment of the washing water is stopped and the water is stored and stagnated in the washing tank.

[0006] Further, there is no replenishment of water during the treatment, and after a certain amount of treatment, the stored water system is the mainstream in small hospitals, clinics and the like. Flush water will be stored and stagnated for many days.

If the stored and stagnant washing water is left for a long time, water stains are generated on the washing tank, the washing roller, the washing roller rack and the like. In particular, the water stain generated and adhered to the roller immersed in water slips when the silver halide photographic light-sensitive material is transferred in the water washing step and causes a conveyance failure. There is also a problem that the treated film is contaminated mainly by water stains adhering to the roller.

In order to solve the above problems, the following water stain prevention techniques have been disclosed. It is possible to add chelating agents, bactericides, etc. to the wash water as anti-scaling agents, for example LEWes
t, "Water Quality Criteria" Phot. Sci. and Eng., Vo
l 9 No.6, page 398 (1965), MEBeach, "Microbiological G
routh in Motion-Picture Processing "SMPTE journal,
Vol.85, Mar. (1976) and RO Deegan, "Photoprocessing.
Wash Water Biocides "J.Imaging Tech., Vol.10, No.6,
Dec (1984) etc.

The addition of a bactericidal agent to washing water is disclosed in, for example, Japanese Patent Application Laid-Open
57-8542, 58-105145, and 57-157244, addition of various antibacterial agents such as thiazolylbenzimidazole compounds and isothiazolone compounds, and chelating agents of JP-A-62-115154 are used. Method, method using polyaminocarboxylic acids of No. 62-153952, halogen-containing phenol of No. 62-220951, phosphoniums, sulfanilamides,
A method of using antibacterial agents such as guanidines, triazines and benzotriazoles is disclosed.

However, these various antibacterial agents do not exhibit their bactericidal action below a certain concentration in water. Therefore, prevention of scales while supplying water requires addition of a large amount of antibacterial agent. If the amount of the antibacterial agent used is too large, there is a problem that the activated sludge such as the septic tank is affected. In addition, a control device for addition is also required, which has the disadvantage of high cost. Further, as a physical method, there are the ultraviolet irradiation method of JP-A-60-263939 and the method of using a magnetic field of JP-A-60-263940, but they are not effective means.

[0011]

SUMMARY OF THE INVENTION Therefore, the present invention has been made to solve the above-mentioned problems, and the acetic acid content in the fixing solution is 0.3 mol / liter in the automatic developing machine processing step of the silver halide photographic light-sensitive material. Even after the above processing, the silver halide photographic light-sensitive material does not have an acetic acid odor after processing and drying, and a washing tank,
It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material, which has no stain on a water-washing roller and has good transportability.

[0012]

The above object was achieved by the present invention described below.

That is, in the automatic processor processing of a silver halide photographic light-sensitive material, the content of acetic acid in the fixing solution used in the automatic processor processing is 0.3 mol / liter or more and 1.5 mol / liter or less, and the washing step Alternatively, a method of processing a silver halide photographic light-sensitive material, characterized in that the tank of the stabilizing step or the conveying roller used in the step contains antibacterial calcium phosphate ceramics.

The present invention will be described in detail below.

The fixing agent used in the fixing solution of the present invention may be a commonly used fixing agent, for example, an aqueous solution containing thiosulfate.

Specifically, thiosulfates such as ammonium thiosulfate and sodium thiosulfate are preferable, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed.

The concentration of thiosulfate in the fixer is preferably
The range is preferably 0.1 to 5 mol / l, more preferably 0.7 to 3 mol / l.

The content of acetic acid in the fixing solution of the present invention is 0.3 mol / liter or more, preferably 0.3 mol / liter to 1 mol / liter.

When the acetic acid content in the fixing solution of the present invention is 0.3 mol or less, the pH at the time of reaching the running equilibrium increases when the amount of the buffer is reduced, and the hardening error occurs. The residual acetic acid odor of the silver halide photographic light-sensitive material is strong and not preferable. The preferred processing conditions for the fixing solution of the present invention are as follows: fixing time of 3.6 to 150 seconds, processing temperature of 15 to 45.
C., particularly preferably 25 to 38.degree.

A surfactant may be added to the fixing solution of the present invention. Preferred surfactants include, for example, anionic surfactants such as sulfate ester and sulfonate, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. To be

The fixer contains various acids in addition to the above compounds.
Additives such as salts, chelating agents and wetting agents can be included.

Examples of the acid include inorganic acids such as acetic acid, sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid and malic acid.

Examples of the salt include salts of these acids such as lithium, potassium, sodium and ammonium.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Among the above additives, acids and salts such as sulfuric acid, boric acid and aminopolycarboxylic acids are preferable. The preferable additive amount of the additive is 0.5 to 20 g / liter.

The replenisher according to the present invention comprises the same components as the above-mentioned fixer, and the replenisher replenishes the amount corresponding to processing fatigue. As a replenishment method, the width described in JP-A-55-126243,
Replenishment by feeding speed, area replenishment described in JP-A-60-104946, or controlled area replenishment by continuous processing number described in JP-A-1-149156 may be used, and the replenishment amount is 400 ml.
/ M ² or less is preferable.

The water washing tank and the stabilizing step tank containing the antibacterial calcium phosphate ceramics of the present invention have a general shape conventionally used in these tanks, and the material is preferably vinyl chloride, Molded by mixing antibacterial calcium phosphate with vinyl pellets.

The material of the conveying roller used in the washing and stabilizing process containing the antibacterial calcium phosphate ceramics of the present invention is a bakelite type (may include glass powder, metal powder, plastic powder) or rubber. A system (neoprene, isoprene, silicone rubber, etc.) can be used.

The shape of the carrying roller used in the washing and stabilizing process containing the antibacterial calcium phosphate ceramics of the present invention is a general shape which has been used as a conventional carrying roller.

Next, FIG. 1 shows an example of a method for adding the antibacterial calcium phosphate ceramics of the present invention to these roller materials.

When compounding the Bakelite-type or rubber-type conveying roller material 17, the antibacterial calcium phosphate ceramic powder 18 is dispersed and mixed, and then molded, and the molded conveying roller material is pressed into a stainless steel core material 19. After that, the surface is polished, or although not shown, the antibacterial calcium phosphate-based ceramic powder is microencapsulated using a microcapsulating agent or the like, which is core-celled with gelatin-arabic gum when masticating the roller material. After dispersion mixing, molded and processed,
For example, the roller material is molded and then coated with a layer containing antibacterial calcium phosphate-based ceramic powder, and the roller material is similarly molded and sprayed with antibacterial calcium phosphate-based ceramic fine powder on the roller surface.

The antibacterial calcium phosphate-based ceramics contained, coated or sprayed in these roller materials are contained in the material constituting the roller or in any layer evenly or in a graded distribution in the material. From the standpoint of sustaining the effect of preventing water stains, it is preferable to carry out molding after dispersion-mixing at the time of masticating the carrier roller material.

After the stainless steel core material 19 is press-fitted into the molded transfer roller material, the surface is polished.

Further, the transport roller may be provided with irregularities, for example, irregularities having a depth of preferably 0.05 to 1.0 mm in order to improve the transportability.

The antibacterial calcium phosphate ceramics of the present invention means an antibacterial metal, particularly at least one metal or metal selected from the group consisting of silver, copper, zinc, nickel, platinum, tin, arsenic, cadmium and chrome. At least one calcium phosphate-based ceramic selected from the group consisting of salt-supported calcium triphosphate, calcium hydrogen phosphate, calcium pyrophosphate, calcium metaphosphate, hydroxyapatite, and halogenated apatite, and zirconia, alumina, silica, silicic acid, Iron oxide, titanium oxide, calcium oxide, magnesium oxide,
An antibacterial agent comprising at least one inorganic oxide selected from the group consisting of zinc oxide, copper oxide and zeolite, wherein the calcium phosphate ceramic antibacterial agent and the inorganic oxide are in a weight ratio of 99: 1 to 1:99. Calcium phosphate ceramics.

For the production method of these antibacterial calcium phosphate-based ceramics, see Japanese Patent Application Laid-Open Nos.
Although it can be produced by the method described in Nos. 1708 and 6-172113, it can be easily obtained under the trade name of Apacider A (manufactured by Sangi Co., Ltd.).

Instead of the antibacterial calcium phosphate ceramics, the antibacterial ceramics described in JP-A Nos. 5-124819 and 6-87714 may be used.

In the automatic processor according to the present invention, various conventionally known systems can be used for the developing section, the fixing section and the drying section, and the processing time can be selected by changing the processing speed. it can. The time from the end of development to the end of washing with water is preferably 30 to 40 ° C. and 20 to 150 seconds.

The amount of washing water is preferably 3 liters / minute or less, more preferably 0.1 liters / minute or more and 2 liters / minute or less.

The film to be treated is conveyed by the frictional resistance of a zigzag type or an opposed type conveying roller, developed, fixed and washed (stabilized), and then the squeeze roller removes adhering water and dries. To be done.

In addition, it is used in a washing process or a stabilizing process,
The tank containing the antibacterial calcium phosphate-based ceramics of the present invention or the conveying roller containing the antibacterial calcium phosphate-based ceramics may be used in combination with a known scale preventer.

Here, the known means for preventing scale formation means means such as addition of various antibacterial agents to the aforementioned washing tank.

The silver halide photographic light-sensitive material to which the rapid processing by the automatic processor of the present invention can be applied is applied to all silver halide photographic light-sensitive materials such as color light-sensitive material, black-and-white light-sensitive material, and color photographic paper. In particular, a film for direct X-rays, a ray film for indirect X-rays, a reversal film for duplication, a one-sided film for CT imager, an infrared film for laser imager, a line drawing film for printing plate making, a color separation film, and the like. Examples include a halftone film, a reversal film, and a gravure film.

[0045]

Embodiments of the present invention will be described below with reference to the drawings.

2 and 3 are sectional views of the automatic developing machine according to the present invention. In the examples, a washing tank molded by containing antibacterial calcium phosphate ceramics, and a carrying roller containing antibacterial calcium phosphate ceramics were used as the carrying rollers in the washing process.

As shown in FIG. 2, the automatic processor of the present invention is surrounded by a housing 16 for shielding external light. On the left side of the housing, a film insertion table 1 for supplying an unprocessed film of silver halide photographic material 2 is provided inside the housing between a film guide roller 3 and an exit roller 14 facing the film insertion table 1. A large number of transports for transporting at a constant speed and discharging from the film take-out port 15 are provided.

That is, the untreated silver halide photographic light-sensitive material 2 inserted from the insertion table 1 was conveyed at a constant speed between the film guide roller 3 and the exit roller 14 by a conveying roller driven at a constant speed.

A developing roller 5 is provided in the developing tank 4, a fixing roller 7 is provided in the fixing tank 6, and a washing roller R and the like are provided in the water washing tank 8 in the form of racks. The transport roller R of this water washing process rack is the roller RA or RB containing the antibacterial calcium phosphate ceramics of the present invention.
Is used. Blower 13 is a hot air blowing nozzle 12
More out.

Transfer roller 9 to each processing tank, drying section 10
The transport roller 11 of is built-in. The conveyance rollers are arranged in a staggered type and a counter type, and are conveyed. A film is inserted from the film insertion table 1 and sequentially conveyed by a conveying roller through a developing tank, a fixing tank, a washing tank and a drying section at a constant speed.

(Preparation of Washing Tank 8 Containing Antibacterial Calcium Phosphate Ceramics) The washing tank containing the antibacterial calcium phosphate ceramics of the present invention is a general molding die conventionally used for molding these tanks. Apatizer A powder (manufactured by Sangi Co., Ltd.) was added to vinyl chloride pellets, and the mixture was molded.

A washing tank I containing 5% by weight of apatizer A powder and a washing tank II containing 0.5% by weight thereof were prepared.

As a comparative washing tank, an automatic processor SRX-501 is used.
A commercially available water washing tank (manufactured by Konica Corporation) was used as the water washing tank III.

(Preparation of Conveyor Roller RA) 5% by weight of Apatizer A powder (manufactured by Sangi Co., Ltd.) was added to a commercially available silicone rubber compound (mixture of raw rubber and filler), and the mixture was masticated to form a core material in a tube. As a diameter of 8 mm and a length of 50
0mm stainless steel core material is press-fitted to a diameter of 24mm, 3
RAs of 2 mm and 50.7 mm conveying rollers R were prepared for 9, 2 and 1 RA, respectively, and after polishing finish, they were incorporated in a washing rack of a washing process section.

(Preparation of Conveyor Roller RB) 0.5 wt% of the powder of Apatizer A was added to a commercially available compound of ethylene propylene rubber, and the mixture was masticated in the same manner as in the above RA, and the core material was pressed into a molded tube to obtain a diameter of 24 mm, 32 mm After forming 9, 2 and 1 RBs of 50.7 mm conveying rollers R, polishing and finishing the RBs, the RBs were mounted on a treatment rack of the washing process section.

For the comparative washing tank (III) and the comparative washing step roller RC, a washing tank for the Konica automatic developing machine SRX-503 and a washing roller rack (manufactured by Konica Corporation) were used. (Preparation of treatment liquid) The composition of each treatment liquid used in the present invention is as follows.

Developer formulation (for 10.8 liter finish) Part-A Potassium hydroxide 340 g Potassium sulfite (50%) 2150 g Diethylenetriamine pentaacetic acid 32.3 g Sodium hydrogencarbonate 108 g 1-Phenyl-5-mercaptotetrazole 15 mg 5-Methylbenzotriazole 150 mg 1,4-Dihydroxybenzene 280g Add water to make 3600ml Part-B Glacial acetic acid (90%) 150g Triethylene glycol 144g 1-Phenyl-3-pyrazolidone 19.5g N-acetyl-D, L-penicillamine 1.0g 5- Nitroindazole 0.32g Starter solution formulation (for 1.0 liter finish) Glacial acetic acid (90%) 138g Potassium bromide 325g _5- Methylbenzotriazole 1.5g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 20mg Add water to finish to 1.0 liter Mix Part A and Part B and finish with water to obtain a pH of 10.60
Adjusted to. 20 ml of a starter was added to 1 liter of this developing solution to adjust the pH to 10.40, which was used as a developing solution.

Fixer formulation (for finishing 16.4 liters) Sodium thiosulfate (70 wt / vol%) 4100 g Sodium sulfite 410 g Ethylenediamine tetraacetic acid disodium 0.5 g Ammonium thiosulfate 150 g Sodium acetate Table 1 Glacial acetic acid (90%) Table 1 Indicated amount 52.5 g tartaric acid 82 g boric acid 56 g aluminum sulphate Add water to finish to 5000 ml The pH after finishing is shown in Table 1.

Next, the operation of the embodiment of the present invention will be described.

The film 2 is inserted from the insertion table 1, detected by a detection sensor (not shown) provided in the vicinity of the insertion opening, and sequentially immersed in the developing solution in the developing tank 4 by the guide roller 3 and the developing roller 5 to be developed. . After the development processing, it is sent to the fixing tank 6 through the transition roller rack 9 and is transferred to the fixing roller 7.
Is fixed while being transported by a transfer rack 9 and is transferred to a washing tank 8 molded from vinyl chloride containing the antibacterial calcium phosphate ceramics of the present invention through a transfer rack 9 and conveyed containing the antibacterial calcium phosphate ceramics of the present invention. While being conveyed by the washing roller constituted by the roller R, the washing process is performed, and the sheet is discharged from the film take-out port 15 via the cross roller and the drying roller 11 of the drying unit 10 and the exit roller 14.

During this processing, the developing solution and the fixing solution are constantly replenished by receiving the signal from the detection sensor, and the washing water is also supplied and drained by the overflow method to maintain the preferable processing conditions. At this time, the replenishment amount is 15 ml of development / 4 pieces 1
Sheets, fixing 20 ml / 4 pieces, 1 sheet.

The temperature of the treatment liquid is controlled to a constant temperature via a temperature sensor. After the treatment is finished, the supply of the treatment liquid and the washing water is stopped and the treatment tank is stagnated.

(Evaluation of transportability and scale) The effect was measured as follows. The automatic processor of the present invention (developing layer 16 liters,
Orthofilm type SRG for direct X-ray photography (Konica Corporation) using a fixing tank of 10 liters and a water washing tank of 10 liters
300 sheets were manufactured and exposed to give a density of 1.0 on the assumption of treatment at a clinical site, and the average number of processed sheets per day was 300, and running treatment was performed for 30 days.

On the first day and the 30th day, 10 SRG films as sample films were cut into a cabinet plate (118 x 163 mm), which is a size in which transport slip is likely to occur, and development processing was carried out. Time required is n = 10
And the conveyance delay due to slip was compared. That is, the slipped material is delayed in conveyance.

At this time, the transportation roller was touched to test the generation state of scale, and the evaluation was made according to the following three-level evaluation criteria.

Evaluation Criteria a) There is no slime on the conveying roller and the washing tank in the washing process section, and no generation of scale is observed b) The slimming due to scale is felt on the conveying roller and the washing tank in the washing process section c) The washing step Clearly slimy on the transport rollers and the washing tank in some parts, and water stains are generated.

(Evaluation of Residual Odor of Film) Running Treatment 100 sheets on 30th day A quarter cut film was treated on 101 sheets of running and immediately after being discharged from the discharge port of the automatic developing machine, sensory evaluation was carried out according to the following evaluation criteria. did.

Evaluation Criteria 1: Does not smell at the normal diagnostic film reading distance 2: Slightly smells when the nose is approached 3: Smells when the nose approaches 4: Smells at the normal diagnostic film reading distance 5: Discharge port The results are summarized in Table 1.

[0069]

[Table 1]

As is clear from Table 1, in the treatment using the washing tank or the washing roller containing the antibacterial calcium phosphate ceramics (Apacider A) of the present invention,
Compared with the comparative treatment method, the treatment using a fixer with an acetic acid content of 0.3 mol / liter or more in the fixer does not cause any scales even if the number of days of stagnation is longer, and the film slips during transport. There is no odor on the film after 30 days running and after processing and drying.

[0071]

The washing layer used in the washing step according to the present invention,
Thus, a method of processing a silver halide photographic light-sensitive material was obtained in which the generation of scales on the transfer roller was eliminated, the amount of slip in the transfer of the automatic developing machine was small, rapid processing was possible, and no odor remained on the film after processing and drying.

[Brief description of drawings]

FIG. 1 is an explanatory view of a carrying roller of the present invention.

FIG. 2 is a sectional view showing an example of an automatic developing machine used in Examples.

FIG. 3 is a cross-sectional view showing another example of the automatic developing machine used in the examples.

[Explanation of symbols]

 1 Film Inserting Table 2 Film 3 Guide Roller 4 Developing Tank 5 Developing Roller 6 Fixing Tank 7 Fixing Roller 8 Water Washing Tank 9 Crossing Roller 10 Drying Section 11 Drying Roller 12 Hot Air Blow Nozzle 13 Blower 14 Exit Roller 15 Film Exit 16 Housing 17 Conveyor roller material 18 Antibacterial calcium phosphate ceramics 19 Stainless steel core material R Washing roller

Claims (1)

[Claims] 1. In an automatic processor treatment of a silver halide photographic light-sensitive material, the content of acetic acid in a fixing solution used for the automatic processor treatment is 0.3 mol / liter or more and 1.5 mol / liter or less, and a water washing step. Alternatively, a method of processing a silver halide photographic light-sensitive material, characterized in that the tank of the stabilizing step or the conveying roller used in the step contains antibacterial calcium phosphate ceramics.