JP2727138B2 - Processing solution for silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution for a silver halide photographic material, and more particularly to an acidic agent used in the processing solution.

[0002]

2. Description of the Related Art A silver halide photographic material is subjected to image exposure,
A photographic image is obtained by developing, fixing, washing and drying. Further, a stop process may be added between the developing process and the fixing process in order to prevent uneven development and improve the stability of the fixing solution. The developing solution used for developing silver halide photographic light-sensitive materials is alkaline, and the fixing solution following development is acidic, and the light-sensitive material moving during this period undergoes rapid changes, resulting in uneven development and resulting images. Cause a decrease in quality.

The developer used here comprises a developing agent, a preservative, an alkali, an inhibitor, various additives, a solvent and the like. The fixing solution comprises a fixing agent, a preservative, an acid agent, a hardener, a stabilizer and the like. The stop solution used between development and fixing consists of an acidic agent. Fixing solution is thiosulfate, the main fixing agent, as a preservative to prevent the decomposition of this thiosulfate, sulfite, acidic sulfite, metabisulfite, as an acid agent to keep the fixing solution acidic Acetic acid is used. Water-soluble aluminum and organic acids for preventing insolubilization of water-soluble aluminum are used as hardeners for increasing the physical strength of photographic light-sensitive materials. Acetic acid is most commonly used as an acidic agent for the stop solution.

The thiosulfates used in the fixing solution are generally ammonium thiosulfate and sodium thiosulfate, and the sulfites, acid sulfites and metabisulfites are sodium sulfite, ammonium sulfite, sodium bisulfite, and sulfite. Ammonium hydrogen, potassium metabisulfite,
Sodium metabisulfite is common. Acetic acid is generally used as the acidic agent. As the water-soluble aluminum, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum ammonium sulfate, aluminum potassium sulfate, and sodium aluminum sulfate are generally used. Further, as the organic acid used for preventing the insolubilization of water-soluble aluminum, citric acid, tartaric acid, succinic acid, malic acid and alkali salts thereof are generally used.

[0005]

In recent years, the processing of silver halide photographic light-sensitive materials has been accelerated with the use of automatic developing machines, and the processing temperature has been increased. The generated odor is strong and the use environment is bad. Particularly, acetic acid used as an acidic agent of the fixing solution causes odor. There is a method of using an acid agent other than acetic acid to remove this odor, and other organic acids may be used instead of acetic acid. Organic acids without odor are
Although organic acids are dicarboxylic acids and higher, these organic acids have the disadvantage that they react with water-soluble aluminum used as a hardener and lose their hardening properties.

When the fixer is viewed from the viewpoint of the hardening property, the fixer has a suitable acidity, and furthermore, the acidity of the fixer is reduced by the developer brought in, and it is necessary to prevent the hardening property from deteriorating. In addition, it must have a buffering property for suppressing a decrease in acidity. In particular, a large amount of an organic acid is required for buffering properties, but a large amount of the organic acid cannot be used because it causes a buffy coat. Similarly, acetic acid used in the stop solution also causes odor, and it is conceivable to use another organic acid without odor.However, it is necessary to reduce the acidity by reducing the acidity caused by the developer brought into the stop solution. Although a large amount of organic acid must be used, a large amount of organic acid must be used.

In a fixing solution used for processing a silver halide photographic light-sensitive material, acetic acid causing odor is not used, and the acidity suitable for the fixing solution and the acidity lowered by a developing solution brought in are suppressed. Fixing solution that has sufficient buffering properties and sufficient hardening properties, and does not use acetic acid that causes odor in the stop solution, and suppresses the acidity suitable for the stop solution and the acidity that is reduced by the developer brought in. It is desired to supply a stop solution that does not deteriorate the buffering property and the hardening property of the fixing solution.

An object of the present invention is to obtain a fixing solution not using acetic acid, and further to obtain a fixing solution having sufficient hardening properties. Another object is to obtain a stopping solution not using acetic acid. Another object of the present invention is to obtain a stop solution which does not impair the hardening property of the fixing solution. The present inventor has found a fixing composition which is sufficiently acidic, has a buffering property, and further has a sufficient hardening property by using nicotinic acid instead of acetic acid used in the fixing solution. Also, instead of acetic acid used in stop solution,
The use of nicotinic acid has sufficient acidity, has a buffering property, and has further found a stop solution composition that does not impair the hardening property of the fixing solution.As the fixing solution composition, at least thiosulfate, It is characterized by containing a sulfite, soluble aluminum and nicotinic acid, and is characterized by containing at least nicotinic acid as a stop solution composition .

The processing solution of the present invention can be applied to photosensitive materials for general photography (negative film and positive film for black and white photography), photographic paper photosensitive materials for black and white, and photographic materials for plate making (lith film, typesetting film, typesetting). Photographic paper), photosensitive materials for copying (microfilms, graph films), photosensitive materials for X-rays, and the like.

[0010]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by these examples. Example 1 A commercially available X-ray film was processed according to the processing steps using a developing solution and a fixing solution having the following compositions.

[0011] developer (1) Sodium sulfite 50.0g 1-phenyl-3-Pirazoriji Roh emissions 1.0g Haidoroki non 20.0g benzotriazole 0.1g Potassium bromide 5.0 g Potassium carbonate 50.0g ethylenediaminetetraacetic acid Disodium (dihydrate) 2.0g Add water 1.0l

Fixer (1) Ammonium thiosulfate 130.0 g Sodium sulfite (anhydrous) 10.0 g Boric acid 10.0 g Acetic acid (90%) 21.0 g Citric acid (monohydrate) 3.0 g Sodium hydroxide 7.6 g Aluminum sulfate (crystal) 18.0 g Add water to make 1.0 l

Fixer (2) Ammonium thiosulfate 130.0 g Sodium sulfite (anhydrous) 10.0 g Boric acid 10.0 g Citric acid (monohydrate) 47.0 g Sodium hydroxide 19.0 g Aluminum sulfate (crystal) 18.0 g 1.0 liter with water

Fixing solution (3) Ammonium thiosulfate 130.0 g Sodium sulfite (anhydrous) 10.0 g Nicotinic acid 28.0 g Citric acid (monohydrate) 3.0 g Sodium hydroxide 3.0 g Aluminum sulfate (crystal) 18.0 g 1.0 liter with water

The dried state treated in the above-mentioned treatment steps is as shown in the following table.

When processing is carried out using the above-mentioned processing agents, the acidity of the fixing solution is reduced by the developing solution brought into the photosensitive material. The decrease (increase in pH) is as shown in the following table. The pH of each fixing solution with respect to the mixing ratio of the developing solution with the fixing solution
Changes (values are pH values).

According to the above results, by using nicotinic acid instead of acetic acid used for the fixing solution, the fixing solution (3) can eliminate the odor of acetic acid, and the hardening property of the fixing solution also uses acetic acid. The acidity and buffering property of the fixing solution are the same as those when acetic acid is used. On the other hand, although the fixing solution (2) using citric acid instead of acetic acid has no odor of acetic acid, it can be seen that the hardening property is inferior to the fixing solution using acetic acid.

Example 2 Commercially available typesetting photographic paper was processed according to the processing steps using a developing solution and a fixing solution having the following compositions. Developer (2) Sodium sulfite (anhydrous salt) 40.0 g 1-phenyl-3-Pirazoriji Roh emissions 0.5g hydroquinone 10.0g benzotriazole 0.1g Potassium bromide 1.0g Potassium carbonate 15.0g disodium ethylenediaminetetraacetate Sodium (dihydrate) 1.0 g Potassium hydroxide 3.0 g

Fixer (4) Ammonium thiosulfate 120.0 g Sodium sulfite (anhydrous) 15.0 g Acetic acid (90%) 20.0 g Ammonium tartrate 5.0 g Aluminum sulfate (35%) 36.0 g Sodium hydroxide 5.8 g Water Add 1.0l

Fixer (5) Ammonium thiosulfate 120.0 g Sodium sulfite (anhydrous) 15.0 g Nicotinic acid 38.0 g Ammonium tartrate 5.0 g Aluminum sulfate (35%) 36.0 g Sodium hydroxide 4.1 g Water was added. 1.0l

Fixer (6) Ammonium thiosulfate 120.0 g Sodium sulfite (anhydrous salt) 15.0 g Ammonium tartrate 100.0 g Aluminum sulfate (35%) 36.0 g Sodium hydroxide 37.0 g Add water 1.0 l

The dried state treated in the above-mentioned treatment steps is as shown in the following table.

When the processing is carried out using the above-mentioned processing agent, the acidity of the fixing solution is reduced by the developing solution brought into the photosensitive material. The decrease (increase in pH) is as shown in the following table. PH change of each fixing solution depending on the mixing ratio of the developing solution to the fixing solution (the value is a pH value).

According to the above results, by using nicotinic acid instead of acetic acid used in the fixing solution, the fixing solution (5) can remove the odor of acetic acid, and the hardening property of the fixing solution also uses acetic acid. The acidity and buffering property of the fixing solution are the same as those when acetic acid is used. On the other hand, although the fixing solution (6) using ammonium tartrate has no odor of acetic acid, it can be seen that the hardening property is poor as compared with the fixing solution using acetic acid.

Example 3 A commercially available X-ray film was processed according to the processing steps using a developing solution, a stopping solution and a fixing solution having the following compositions. Developer (3) sodium sulfite (anhydrous salt) 50.0 g 1-phenyl-3-Pirazoriji Roh emissions 1.0g hydroquinone 20.0g benzotriazole 0.5g of sodium bromide 5.0g Potassium carbonate (anhydrous salt) 50.0 g Disodium ethylenediaminetetraacetate (dihydrate) 2.0 g

Stop solution (1) Acetic acid (99%) 15.0 g Water added to 1.0 L Stop solution (2) Citric acid (monohydrate) 18.0 g Water added 1.0 L Stop solution (3) Nicotinic acid 25.0g Add water and add 1.0l

Fixer (7) Ammonium thiosulfate 150.0 g Sodium sulfite (anhydrous salt) 10.0 g Boric acid 5.0 g Acetic acid (90%) 16.0 g Citric acid (monohydrate) 3.0 g Sodium hydroxide 8g Ammonium sulfate (crystal) 17.0g Water added to 1.0l

[0028]

The dried state treated in the above-mentioned treatment steps is as shown in the following table.

When the processing is carried out using the above-mentioned processing agent, the stop solution is not brought into the fixing solution by the photosensitive material at the start of the process, so that the fixing solution has a sufficient hardening property, and Good. When the amount to be processed is increased, a large amount of the stop solution is brought into the fixer, and the effect of the stop solution appears in the fixer. The film property is reduced, and the dried state is poor. On the other hand, acetic acid having the composition of the stop solution (1) and nicotinic acid having the composition of the stop solution (3) do not deteriorate the hardening property of the fixing solution, and thus have a good dry state. Further, a stop solution (1)
Since acetic acid is used, it has a strong odor, whereas the stop solution (2) and the stop solution (3) have no odor.

The stop solution needs to have an acidity to neutralize the alkalinity of the developer, and the acidity of the stop solution is reduced by the developer brought into the photosensitive material by the processing.
The decrease (increase in pH) is as shown in the following table. PH change of each stop solution depending on the mixing ratio of the developer to the stop solution (the value is a pH value).

[0032] Instead of the acetic acid used for stop solution, stop solution to use the acid (3) neutralize Similarly developer and stop liquid using acetic acid (1). The stop solution (2) using citric acid can neutralize the developer,
As described above, the hardening property of the fixer is reduced.

According to the above results, the odor of acetic acid can be eliminated by using nicotinic acid in place of acetic acid used for the stopping solution, and the hardening property of the fixing solution is not reduced. The acidity and buffering properties of the liquid are the same as those when acetic acid is used. On the other hand, when citric acid is used, the odor of acetic acid can be removed, but the hardening property of the fixing solution is reduced.

[0034]

As described above, according to the present invention, in a processing solution for a silver halide photographic light-sensitive material, nicotinic acid is used in place of acetic acid in a fixing solution and acetic acid in a composition of a stop solution. By using nicotinic acid, the effect is remarkable, for example, it is possible to remove the environmental deterioration due to the odor of acetic acid while having the same treatment liquid action as when using acetic acid.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-24434 (JP, A) JP-A-61-50140 (JP, A) JP-A-49-127623 (JP, A) JP-A 55-124 153939 (JP, A) JP-A-63-142349 (JP, A) JP-A-55-62450 (JP, A) JP-A-55-153940 (JP, A)

Claims (2)

(57) [Claims] 1. A processing solution for a silver halide photographic material, which comprises at least a thiosulfate, a sulfite, a soluble aluminum, and a nicotinic acid as a fixing solution composition. 2. A processing solution for a silver halide photographic light-sensitive material, which comprises at least nicotinic acid as a composition of a stop solution.