JPH04330442A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To process an exposed silver halide photographic sensitive material with a stabilizing processing solution without water rinsing after fixing processing. CONSTITUTION:The imagewise exposed silver halide photographic sensitive material is developed and processed with an acidic fixing solution containing thiosulfate, and processed with the stabilizing processing solution containing 1-phenly1-5-mercapto-tetrazole or its derivative and a sulfite in the concentration of 0.01-0.2mol/l and having pH6.8-8.0 without rinsing it with water.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a method for processing silver halide photographic materials, and more particularly to a method for processing silver halide photographic materials using a stabilizing processing solution instead of washing with water after processing with at least an acidic fixing solution containing thiosulfate. be.

0002

[Prior Art and Problems] Silver halide photographic light-sensitive materials are processed through the steps of development, fixing, and water washing in an automatic processor after image exposure, and the fixing solution contains thiosulfate and has a stopping effect. Generally, an acidic fixer with a Although various improvements have been made regarding development and fixing, the washing process is still an old method, and as the washing process is made more efficient, the amount of water used is decreasing. Large amounts of water are still being used. Using a large amount of water for washing is not preferable from the standpoint of effective use of water resources, and is also not preferable from the standpoint of wastewater treatment after use.

[0003] In developing and fixing, since the amount of processing liquid required to process a unit area is small, the waste liquid after use can be collected in a small container. However, washing with water requires a large amount of water per unit area, and cannot be collected in a small container. In addition, the automatic developing machine must be connected to a water supply in order to supply this washing water, and must also be connected to a drain pipe for drainage. This restriction is a major restriction on the installation location of the automatic processor.

[0004] In order to eliminate this restriction, when the washing process is performed using a small amount of water, the fixing composition contained in the photosensitive material during the fixing process in the previous step is not sufficiently washed with water and remains in the photosensitive material. This results in a condition called insufficient washing, and the stability of the finished image during storage is extremely degraded.

[0005] Also, the use of a large amount of water in the washing process is stopped, and instead, the process is performed with a small amount of processing liquid, which has the effect of replacing washing with water. A stabilization processing method that does not limit the installation location of the developing machine is proposed in JP-A-2-132435, but this processing method also requires long-term processing, at least when using an acidic fixing agent containing thiosulfate. If this process is continued, there is a problem in that image storage properties equivalent to those obtained by washing with water cannot be obtained.

[0006] The object of the present invention is to provide automatic processor processing using at least an acidic fixing solution containing thiosulfate.
The object of the present invention is to provide a processing method with good storage stability for images instead of washing with water. Another objective is to avoid using large amounts of water in the washing process. Still another object is to eliminate the limitation on the installation location of an automatic developing machine by not performing a water washing process.

[0007]

[Means for Solving the Problems] The above object is to imagewise expose and develop a silver halide photosensitive material, and after processing it with at least an acidic fixing solution containing thiosulfate, instead of washing with water, at least the following pH including ingredients = 6.0-8
．． This is achieved by treatment with a stabilizing treatment solution of 0. (1) 1-phenyl-5-mercaptotetrazole or its derivative (2) 0.01-0.2 mol/l sulfite

0008
] The pH of at least the acidic fixing solution containing thiosulfate used in the present invention is preferably 3.5 to 5.5 because it has a stopping effect. If the pH is below 3.5, the fixer will decompose quickly, and if the pH is above 5.5, the stopping effect will be significantly reduced. In addition to thiosulfates, general compositions such as sulfites, polycarboxylic acids such as acetic acid and citric acid, boric acid, and water-soluble aluminum salts can be used.

[0009] The stabilizing treatment liquid used in the present invention is 1-
It contains phenyl-5-mercaptotetrazole or a derivative thereof and 0.01 to 0.2 mol/l of sulfite, and has a pH of 6.0 to 8.0. If the sulfite content is less than 0.01 mol/l, the pH value of the stabilizing solution will decrease significantly if at least the acidic fixer is brought into the stabilizing solution by the photosensitive material, and if the sulfite content is 0.2 mol/l or more, the photosensitive material The surface is rough and there are problems with the finish. Furthermore, if the pH is below 6.0, the stabilizing effect will deteriorate, and if the pH is above 8.0, the drying properties of the photosensitive material will be poor and the photosensitive material will easily get entangled with the drying roller of an automatic processor. In addition, lithium salts, magnesium salts, and molybdates can also be added.

[0010]Furthermore, various contaminations occur due to the composition of at least the acidic fixing solution which is the immediately preceding processing step, and a composition for removing this contamination may be included. An aminopolycarboxylic acid may be used at least to prevent insolubilization of the aluminum compound, which is a hardening agent component contained in the acidic fixer. Furthermore, an anti-bacterial agent can be used in combination to prevent the generation of microorganisms due to long-term use of the processing solution, and a fluorescent paint can also be added to improve the quality of the resulting image. In addition, as a dissolving agent,
It can also be used in combination with thiosulfate. Since this is the final stage of the development process for silver halide photographic light-sensitive materials, various surfactants can be added to eliminate uneven drying of the light-sensitive materials.

The processing method of the present invention can be applied to general photosensitive materials (negative and positive films for black-and-white photography, photographic paper for black-and-white photography) and photosensitive materials for plate making (lithographic film, phototypesetting film, photographic paper for phototypesetting). , photosensitive materials for copying (microfilm, graph film), photosensitive materials for X-rays, etc.

0012

[Examples] The present invention will be explained in detail with reference to Examples below, but the embodiments of the present invention are not limited thereto. [Example 1] Commercially available black and white photographic paper was subjected to image exposure and processing using a small automatic processor (tank capacity: 2 liters each). The processing liquid and processing conditions used are as follows. Developer Sodium sulfite (anhydrous)
25.0g
1-phenyl-3-pyrazolidinone
0.5g
hydroquinone
7.0g
sodium bromide

2.0g benzotriazole

0.1g ethylene glycol

30.0g Disodium ethylenediaminetetraacetate
1.0g potassium carbonate (anhydrous)

30.0g potassium hydroxide

Add 8.0g water

1.0l
Processing conditions: Developing time 50 seconds, developing temperature 30°C

001
3] Fixer ammonium thiosulfate
150.0g
Sodium sulfite (anhydrous)
20.0g
glacial acetic acid

Add 15.0g water

Adjust pH to 4.70 with 1.0l ammonia water (28%)
Processing conditions: Fixing time 50 seconds, fixing temperature 30°C

00
14] Stabilization treatment liquid (A) 1-phenyl-5-mercaptotetrazole 0.5g Magnesium chloride
10.0g
sodium thiosulfate
2.0g
add water
1.
pH by 0l sodium hydroxide
= 7.5 (B) 1-phenyl-5-mercaptotetrazole 0.5g
magnesium chloride
10.0g
sodium thiosulfate
2.
0g sodium bisulfite
Add 5.2g (0.05mol) water

Adjust the pH to 7.5 with 1.0l sodium hydroxide Treatment conditions: Stabilization time 50 seconds, stabilization temperature 30℃

The developing solution and fixing solution were placed in each processing solution tank of an automatic processor, and processing in the washing tank was carried out as follows. (1) Put the stabilization treatment liquid (A) into the washing tank. (Comparative Example) (2) Put the stabilizing treatment liquid (B) into the washing tank. (The present invention) In this state, 400 sheets of photographic paper each measuring 25.2 cm x 30.3 cm were processed at a rate of 20 sheets per day for 20 days. The replenishment amount is 25.2 for the developer, fixer, and stabilizing solution.
The volume was 20 ml per cm x 30.3 cm. The processed images were placed in a constant temperature and humidity chamber at 60° C. and 80% for 5 days, and changes in the images were observed. The results are shown in the table below.

[0016]

In the stabilization treatment method (1), a stabilization treatment liquid (A) is placed in a washing tank. (2): Put the stabilizing treatment liquid (B) into the washing tank. The yellow change in the non-image area was determined by measuring the blue reflection density using a densitometer X-Rite 310. In addition, the change in the image area was visually measured, and ◯ indicates good quality and × indicates poor quality. In addition, the pH value was measured using a pH meter Toa Denpa HM-30S at 25°C.
The pH value was measured. As is clear from the above table, in the processing method in which the stabilizing treatment liquid (B) of the present invention is placed in the washing tank, the pH value of the stabilizing treatment liquid decreases little over a long period of time, and the obtained images are stable. It is excellent and provides sufficient image stability.

[Example 2] Using a small automatic processor (tank capacity: 6 liters each), commercially available phototypesetting paper was subjected to image exposure and processing. The processing liquid and processing conditions used are as follows. Developer Sodium sulfite (anhydrous)
50.0g
1-phenyl-3-pyrazolidinone
0.5g
hydroquinone
20.0g
benzotriazole
0.
1g potassium bromide

2.0g Disodium ethylenediaminetetraacetate 1
．． 0g potassium carbonate (anhydrous)
5
Add 0.0g water

1.0l Processing conditions: Developing time 20 seconds, developing temperature 34°C

Fixer ammonium thiosulfate
150.0g
sodium bisulfite
20.0
g Boric acid

15.0g tartaric acid

2.5g acetic acid (90%)
30.0g
Potassium aluminum sulfate
15.0g
add water
1
．． pH = 4 with 0l sodium hydroxide.
Adjusted to 75 Processing conditions: Fixing time 20 seconds, fixing temperature 34°C

Stabilization treatment liquid (A) 1-(4-hydroxyphenyl)
-5-mercaptotetrazole 0.5g
magnesium sulfate
15.0g
sodium thiosulfate
2.0
g Add water

Adjust pH to 7.0 with 1.0l sodium hydroxide (B) 1-(4-
hydroxyphenyl)
-5-mercaptotetrazole
0.5g magnesium sulfate
15.0g Sodium thiosulfate
2.0g Sodium bisulfite
10.4g (0.1mol) Add water
1.0l
Adjust pH to 7.0 with sodium hydroxide
Processing conditions: stabilization processing time 20 seconds,
Stabilization treatment temperature 34℃

The developing solution and fixing solution were placed in each processing solution tank of an automatic developing machine, and processing in the washing tank was carried out as follows. (1) Put the stabilization treatment liquid (A) into the washing tank. (Comparative Example) (2) Put the stabilizing treatment liquid (B) into the washing tank. (This invention) In this state, 10 phototypesetting papers each measuring 23 cm x 27 cm
00 sheets were processed for 20 days at a rate of 50 sheets per day. The amount of replenishment was 10 ml of the developer, 15 ml of the fixer, and 25 ml of the stabilizing solution per 23 cm x 27 cm. The processed images were placed in a constant temperature and humidity chamber at 60° C. and 80% for 5 days, and changes in the images were observed. The results are shown in the table below.

[0022]

[0023] In the stabilization treatment method (1), a stabilization treatment liquid (A) is placed in a washing tank. (2): Put the stabilizing treatment liquid (B) into the washing tank. As is clear from the table above, in the processing method in which the stabilizing solution (B) of the present invention is placed in the washing tank, the pH value of the stabilizing solution decreases little over a long period of time, and the resulting images are stable. It is excellent and provides sufficient image stability.

[Example 3] Using a small automatic developing machine (tank capacity: 6 liters each), a commercially available plate-making film was image-exposed.
processed. The processing liquid and processing conditions used are as follows. Developer Sodium sulfite (anhydrous)
60.0g
1-phenyl-3-pyrazolidinone
0.5g
hydroquinone
25.0g
benzotriazole
0.
5g potassium bromide

3.0g Disodium ethylenediaminetetraacetate 3
．． 0g potassium carbonate (anhydrous)
1
5.0g potassium hydroxide

Add 15.0g water

1.0l Processing conditions: Developing time 20 seconds, developing temperature 38°C

Fixer ammonium thiosulfate
170.0g
Sodium sulfite (anhydrous)
15.0g
Boric acid

8.0g Acetic acid (90%)

17.0g citric acid (monohydrate)
1.5g aluminum sulfate
Add 10.0g water
1.0l
Adjust pH to 4.20 with sodium hydroxide Processing conditions: Fixing time 20 seconds, fixing temperature 38°C

Stabilization treatment liquid (A) 1-phenyl-5-mercaptotetrazole 0.5g Magnesium chloride
10.0g
sodium thiosulfate
2.0g
add water
1.
pH by 0l sodium hydroxide
= 7.5 (B) 1-phenyl-5-mercaptotetrazole 0.5g
magnesium chloride
10.0g
sodium thiosulfate
2.
0g sodium bisulfite
10.4g (0.1 mol)
add water

Adjust the pH to 7.5 with 1.0l sodium hydroxide Treatment conditions: Stabilization time 20 seconds, stabilization temperature 38℃

0
The developing solution and fixing solution were placed in each processing solution tank of an automatic processor, and processing in the washing tank was carried out as follows. (1) Put the stabilization treatment liquid (A) into the washing tank. (Comparative Example) (2) Put the stabilizing treatment liquid (B) into the washing tank. (Present Invention) In this state, 800 sheets of plate-making film each measuring 25.2 cm x 30.3 cm were processed at a rate of 20 sheets per day for 20 days. The amount of replenishment was 25 ml of the developing solution, 30 ml each of the fixing solution and the stabilizing solution per 25.2 cm x 30.3 cm. The processed images were placed in a constant temperature and humidity chamber at 60° C. and 80% for 5 days, and changes in the images were observed. The results are shown in the table below.

[0028]

In the stabilization treatment method (1), a stabilization treatment liquid (A) is placed in a washing tank. (2): Put the stabilizing treatment liquid (B) into the washing tank. The yellow change in the non-image area was determined by measuring the blue transmission density using a densitometer X-Rite 310. Further, the visual judgment of the image area and the method of measuring the pH value are the same as in Example 1. As is clear from the table above, the stabilization treatment liquid (B) of the present invention was placed in the washing tank.
The treatment method that includes
The decrease in H value is small, the obtained image is excellent in stability, and sufficient image stability can be obtained.

[Example 4] Commercially available X-ray films were processed using a small automatic processor (tank capacity: 3 liters each). The processing liquid and processing conditions used are as follows. Developer potassium metabisulfite
50.0
g 1-phenyl-3-pyrazolidinone
1.2g
hydroquinone
25.0
g triethylene glycol
20.0
g boric acid

10.0g potassium bromide

5.0g Disodium ethylenediaminetetraacetate
3.0g 5-methylbenzotriazole
0.05g glutaraldehyde
5.0g potassium carbonate (anhydrous)
50.0g potassium hydroxide
Add 50.0g water
1.0l
Processing conditions: development time 30 seconds, development temperature 34°C

[
Fixer ammonium thiosulfate
200.0g
Sodium sulfite (anhydrous)
20.0g
Boric acid

8.0g Acetic acid (90%)

17.0g citric acid (monohydrate)
1.5g aluminum sulfate
Add 10.0g water
1.0l
Adjust pH to 4.30 with sodium hydroxide. Processing conditions: Fixing time 30 seconds, fixing temperature 34
℃

Stabilization treatment liquid (A) 1-(4-acetylphenyl)
-5-mercaptotetrazole 1.0g
lithium hydroxide
10.0g
sodium thiosulfate
2.0
g Add water

pH with 1.0l hydrochloric acid
= Adjusted to 7.5. (B) 1-(4-acetylphenyl)
-5-mercaptotetrazole 1.0g
lithium hydroxide
10.0g
sodium thiosulfate
2.0
g Sodium bisulfite
15.6g (015mol) Add water

Adjust pH to 7.5 with 1.0l sodium hydroxide. Processing conditions: Stabilization processing time 30 seconds, stabilization processing temperature 34℃

The developing solution and fixing solution were placed in each processing solution tank of an automatic developing machine, and processing in the washing tank was carried out as follows. (1) Put the stable treatment liquid (A) into the washing tank. (Comparative example)
(2) Put the stable treatment liquid (B) into the washing tank. (Present invention)
In this state, 600 X-ray films each measuring 25.2 cm x 30.3 cm were processed at a rate of 30 sheets per day for 20 days. The amount of replenishment was 35 ml per 25.2 cm x 30.3 cm for each of the developer, fixer, and stabilizing solution. The processed images were placed in a constant temperature and humidity chamber at 60° C. and 80% for 4 weeks, and changes in the images were observed. The results are shown in the table below.

[0034]

In the stabilization treatment method (1), a stabilization treatment liquid (A) is placed in a washing tank. (2): Put the stabilizing treatment liquid (B) into the washing tank. The method for measuring concentration, visual measurement of the image area, and measuring method for pH value are the same as in Example 3. As is clear from the previous table,
The processing method in which the stabilizing treatment liquid (B) of the present invention is placed in a water washing tank has a small decrease in the pH value of the stabilizing treatment liquid over a long period of time, and the resulting images have excellent stability, resulting in sufficient image stability. You can get sex.

[0036]

As described above, according to the present invention, after a silver halide photographic material is developed and treated with at least an acidic fixing solution containing thiosulfate, 1-phenyl-5-mercaptotetrazole is or its derivative and 0
．． pH 6.0 with 01-0.2 mol/l sulfite
By processing with a stabilizing processing liquid of ~8.0, it is possible to obtain an image with excellent image stability even if the processing is continued for a long period of time, and the effect in use is great.

Claims (1)

[Claims] [Claim 1] A silver halide photosensitive material is imagewise exposed and developed, and after being processed with at least an acidic fixing solution containing thiosulfate, the material contains at least the following components instead of washing with water, pH = 6.0 to 8. 1. A method for processing a silver halide photographic material, comprising processing with a stabilizing processing solution of .0. (1) 1-phenyl-5-mercaptotetrazole or its derivative (2) 0.01-0.2 mol/l sulfite