JPH05241280A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To forum images superior in image stability even in the case of processing a large amount of photosensitive materials and to prevent occurrence of silver sludge in a developing solution by processing the exposed photosensitive material with a specified developing solution, then, a fixing solution, and a stabilizing solution. CONSTITUTION:The imagewise exposed silver halide photographic sensitive material is processed with the developing solution containing at least one kind of compound selected from those represented by formulae I-III, then the fixing solution, and the stabilizing solution containing a compound represented by formula IV, and in formulae I-IV, R is SO3M, COOM, OH or H; each of B1 and D1 is, independently, an aliphatic, alicyclic, or aromatic aliphatic group; each of A2 and E2 is, independently, SO3M or COOM, and when each is COOM, each of B1 and D1 has no amino group; and M is H or a counter ion. The photographic printing paper for photocomposition on the market is imagewise exposed and processed by using a small-sized automatic developing machine.

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 a method for processing with a stabilizing processing solution instead of washing with water after processing with a processing solution containing thiosulfate. Is.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material is generally processed in the steps of developing, fixing and washing with water after imagewise exposure. Although various improvements have been made in developing and fixing, the washing method is a conventional method, and since the washing step is made efficient, the amount of water used is decreasing, but still A lot of water is used. Using a large amount of water for the water washing treatment is not preferable from the viewpoint of effective utilization of water resources, and is also not preferable in terms of wastewater treatment after use.

In recent years, the time required for processing photographic light-sensitive materials has been shortened, and the amount of processing liquid used for processing has been reduced. Reducing the processing time has the advantages of increasing the efficiency of processing a photograph and further reducing the size of the automatic processor. Further, the reduction in the amount of the treatment liquid used for the treatment results in the reduction of the waste liquid used. In addition, an automatic processor is generally used for photographic processing, and processing is performed by adding the necessary processing solution as a replenisher to the automatic developing machine in proportion to the amount of photosensitive material to be processed, and processing after processing. The liquid overflows from the automatic processor and becomes waste liquid.

In the photographic processing, an automatic developing machine is generally used today and it is easy to use. 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, in the washing process, the amount of water to be treated per unit area is large and it cannot be collected in a small container. In addition, the automatic developing machine must be connected to the tap water to supply the washing water, and must be connected to the water distribution pipe for drainage. .

In addition to removing the above-mentioned restrictions, it has become necessary to reduce the amount of washing water for environmental protection such as saving water resources and reducing the amount of treatment waste liquid. Since the fixing solution composition brought into the washing water is accumulated in the washing water when the amount of the washing water is reduced, the accumulated fixing solution composition remains in the light-sensitive material even after completion of the washing treatment. Therefore, there arises a problem that the image is discolored and the white background portion turns yellow due to long-term storage.

[0006] Stop using a large amount of water by washing treatment,
Instead of this, treatment with a small amount of treatment liquid has the effect of substituting with water, and as a method of not using a large amount of water, there is a treatment with a stabilizing liquid containing a mercapto compound.

According to this method, the replenishing amount of the stabilizing solution per unit area of the light-sensitive material can be significantly reduced as compared with the washing amount in the case of washing treatment. However, as the amount of the fixing composition remaining in the processed light-sensitive material increases, the developer composition also remains in the light-sensitive material. in this case,
In the developer, most of the compounds used as anti-silver agents react with the silver thiosulfate complex salt and color in the light-sensitive material with the passage of time. The sex is completely lost. Therefore, there is a demand for a processing method that does not deteriorate image stability and prevents silver stains in the developer.

Accordingly, it is an object of the present invention to provide a stabilization processing method which prevents silver stains in a developing solution without deteriorating long-term storage stability of an image.

[0008]

The above-mentioned object is to use an imagewise exposed silver halide photographic light-sensitive material as a separate sheet of general formula [I], [I].
I), after treatment with a developing solution containing at least one of the compounds represented by [III], followed by a fixing treatment and a stabilizing treatment solution containing a compound represented by the general formula [IV] Is achieved by.

In the attached formula, R is SO ₃ M, COOMOH or H, B ₁ and D ₁ are independently of each other an aliphatic group,
It is an alicyclic group or an araliphatic group, and A ₂ and E ₂ are each independently a group represented by SO ₃ M or COOM, provided that when the group represented by COOM is B ₁ and D ₂ have no α-amino group. M represents a hydrogen atom or a counter cation.

Examples of preferred compounds represented by the general formula [I] used in the present invention are shown below. 2-Mercaptobenzimidazole-5-sulfonate sodium, 2-
Mercaptobenzimidazole-5-carboxylic acid, 2-
Mercaptobenzimidazole-6-hydroxy-5-
Carboxylic acid, 2-mercaptobenzimidazole-5,
7-disulphonic acid.

Examples of preferred compounds represented by the general formula [II] are shown below. 2-mercaptobenzthiazole-5-sulfonic acid, 2-mercaptobenzthiazole-5-carboxylic acid, 2-mercaptobenzthiazole-
Sodium 5-sulfonate, 2-mercaptobenzthiazole-6-sulfonic acid, 2-mercaptobenzthiazole-5-carboxy-7-sulfonic acid, 2-mercaptobenzthiazole-5,7-disulphonic acid,
2-Mercaptobenzthiazole-5-hydroxy-6
-Sulfonic acid.

Examples of preferred compounds represented by the general formula [III] are shown below. 2,2'-dithiodibenzoic acid,
Dithiodiacetic acid, 2,2'-dithiodipropionic acid, 3,
3'-dithiodibutane-1,1'-sodium disulphonate, ditin disuccinate, dithio- (1,1 ')-dicyclohexane-4,4'-dicarboxylic acid, 4,4'-dithiophenyldicarboxylic acid, 3, 3'-dithiodipropionic acid, 4,4'-dithiodibutyric acid, 2,2'-dithiodiisobutyric acid, dithiodibivalic acid, 3,3'-dithiobis- (3,3'-dimethyl) -propionic acid, 3,3 ' −
Dithiobis- (3,3'diphenyl) -propionic acid,
4,4′-diamino-2,2′-dithiobis- (pyrimidyl-5,5′-dicarboxylic acid), dithiodiitamalic acid, 6,6-dithiodinicotinic acid, 3,3′-dithiobis- [3,3 ′ -Di (4 "-tolyl)]-propionic acid, dibenzyldisulfite-4,4'-dicarboxylic acid.

Examples of preferred compounds represented by the general formula [IV] are shown below. 1-phenyl-5-mercaptotetrazole, 1- (4-carboxyphenyl) -5-mercaptotetrazole, 1- (4-sulfophenyl)
-5-mercaptotetrazole, 1- (3-carboxy-4-hydroxyphenyl) -5-mercaptotetrazole, 1- (2-carboxyphenyl) -5-mercaptotetrazole, 1- (4-hydroxyphenyl) -5
-Mercaptotetrazole, 1- (3-carboxyphenyl) -5-mercaptotetrazole, 1- (2,4-
Disulfophenyl) -5-mercaptotetrazole.

[0014]

EXAMPLES The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereby. [Example 1] Using a small automatic processor (tank volume: 6 liters), a commercially available photographic printing paper was imagewise exposed and processed. The treatment liquid and treatment conditions used are as follows.

Developer sodium sulfite (anhydrous) 50.0 g 1-phenyl-3-pyrazolidinone 0.5 g hydroquinone 20.0 g benzotriazole 0.1 g potassium bromide 2.0 g ethylenediaminetetraacetic acid disodium 1.0 g potassium carbonate (anhydrous) ) 50.0 g Water was added to 1.0 l Processing conditions: development time 20 seconds, development temperature 34 ° C

Fixing solution Ammonium thiosulfate 150.0 g Sodium bisulfite 20.0 g Boric acid 15.0 g Tartaric acid 2.5 g Acetic acid (90%) 30.0 g Potassium aluminum sulfate 15.0 g Water was added and 1.0 l sodium hydroxide was added. Adjusted to pH = 4.75 Processing conditions: Fixing time 20 seconds, Fixing temperature 34 ° C

Stabilization treatment liquid 1- (4-hydroxyphenyl) -5-mercaptotetrazole 0.5 g Magnesium sulfate 15.0 g Sodium thiosulfate 2.0 g Sodium hydrogen sulfite 10.4 g (0.1 mol) Add water 1 PH was adjusted to 7.0 with sodium hydroxide. Treatment conditions: stabilization treatment time 20 seconds, stabilization treatment temperature 34 ° C.

The compound of the present invention was added to the developer as follows.

The above processing solution was put into each processing tank of the automatic processor, and in this state, 50 sheets of 23 cm × 27 cm typesetting printing paper were processed per day. The replenishment amount is 23 cm x 2
The developing solution was 10 ml, the fixing solution was 15 ml, and the stabilizing solution was 25 ml per 7 cm. The processed image is 60 ℃, 8
The following table shows the results of observing the change in the image by placing it in a 0% constant temperature and humidity chamber for 5 days.

[0020]

[0021]

[0022]

The yellow color change in the non-image area is represented by the densitometer X-Rit.
The blue reflection density was measured using e310. The change in the image area is visually measured, and ◯ is good and X is bad.

As is apparent from the above table, when 2,5-dimercapto-1,3,4-thiadiazole other than the compound of the present invention is used, an abnormal image occurs in a state where the amount of treatment is small, and at the same time, stabilization is performed. Insoluble matter is generated in the processing solution, and when the silver stain preventing agent is not added to the developing solution, silver stain is generated in the developing solution and the resulting image is contaminated, whereas the method of the present invention is used. In the case of carrying out, even if a large amount of processing is carried out, there is no discoloration of the image, there is no silver stain in the developing solution, and there is no generation of insoluble matter in the stabilizing processing solution.

[Example 2] A small automatic processor (tank volume: 6 liters) was used to image-expose a commercial plate-making film.
Processed. The treatment liquid and treatment conditions used are as follows.

Developer sodium sulfite (anhydrous) 60.0 g 1-phenyl-3-pyrazolidinone 0.5 g hydroquinone 25.0 g benzotriazole 0.5 g potassium bromide 3.0 g ethylenediaminetetraacetic acid disodium 3.0 g potassium carbonate (anhydrous) ) 15.0 g Potassium hydroxide 15.0 g Water was added to 1.0 l Processing conditions: development time 20 seconds, development temperature 38 ° C

Fixing solution Ammonium thiosulfate 170.0 g Sodium hydrogen sulfite (anhydrous) 15.0 g Boric acid 8.0 g Acetic acid (90%) 17.0 g Citric acid (monohydrate) 1.5 g Aluminum sulfate 10.0 g Water was added. PH = 4.20 with 1.0 liter sodium hydroxide Treatment conditions: Fixing time 20 seconds, Fixing temperature 38 ° C

Stabilization Treatment Solution 1-Phenyl-5-mercaptotetrazole 0.5 g Magnesium chloride 10.0 g Sodium thiosulfate 2.0 g Sodium bisulfite 10.4 g (0.1 mol) Add water 1.0 liter Sodium hydroxide Adjusted to pH = 7.5 Treatment conditions: Stabilization treatment time 20 seconds, stabilization treatment temperature 38 ° C.

The compound of the present invention was added to the developer as follows.

The above-mentioned processing solution was put into each processing tank of the automatic processor, and in this state, 25 pieces of 25.3 cm × 30.3 cm plate-making film were processed per day. The replenishment amount was 25 ml of the developing solution, 30 ml of the fixing solution and 30 ml of the stabilizing solution per 25.3 cm × 30.3 cm. The processed image is put in a constant temperature and humidity chamber of 60 ° C. and 80% for 5 days, and the result of observing the change of the image is as shown in the table below.

[0031]

[0032]

[0033]

The yellow change in the non-image area is represented by the densitometer X-Rit.
The blue reflection density was measured using e310. The change in the image area is visually measured, and ◯ is good and X is bad.

As is clear from the above table, when 2,5-dimercapto-1,3,4-thiadiazole other than the compound of the present invention is used, an abnormal image occurs in a state where the amount of processing is small, and at the same time, stabilization occurs. Whereas insoluble matter was generated in the processing solution, when the method of the present invention was carried out, there was no discoloration of the image even if a large amount of processing was carried out, there was no silver mud in the developing solution, and
No insoluble matter is generated in the stabilizing solution.

As described above, according to the present invention, the silver halide photographic light-sensitive material is treated with a developing solution containing at least one of the compounds represented by the general formulas [I], [II] and [III] in the attached sheet. After that, through a fixing process, since it was treated with a stabilizing treatment liquid containing a compound represented by the general formula [IV] attached sheet,
An image having excellent image stability can be obtained even if a large amount of processing is performed, and further, silver mud is not generated in the developing solution, and the effect on use is great. R in the attached sheet is SO ₃ M, COOMOH
Or H, B ₁ and D ₁ are each independently an aliphatic group, an alicyclic group or an araliphatic group, and A ₂ and E ₂ are each independently a group represented by SO ₃ M or COOM. However, when the group is represented by COOM, the corresponding B ₁ and D ₂ do not have an α-amino group. M represents a hydrogen atom or a counter cation.

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4]

Claims (1)

[Claims] 1. An imagewise exposed silver halide photographic light-sensitive material is treated with a developing solution containing at least one of the compounds represented by the general formulas [I], [II] and [III] on a separate sheet,
A method of processing a silver halide photographic light-sensitive material, which comprises performing a fixing treatment and then performing treatment with a stabilizing treatment liquid containing a compound represented by the general formula [IV]. R in the attached sheet is SO ₃
M, COOMOH or H, B ₁ and D ₁ are independently of each other an aliphatic group, an alicyclic group or an araliphatic group, and A ₂ and E ₂ are independently of each other SO ₃ M or CO.
A group represented by OM, provided that the corresponding B ₁ and D ₂ are α-
It shall not have an amino group. M represents a hydrogen atom or a counter cation.