JPH06242577A - Processing method of silver halide color light-sensitive material - Google Patents

Abstract

PURPOSE:To unnecessitate the installation of a water supplying and discharging system because a large amt. of washing water is not used and to simplify a device by carrying out processing with a processing soln. contg. 2- aminobenzothiazole and diethylenetriaminepentaacetic acid or a salt thereof in place of washing after processing with a fixing soln. and a bleach fixing soln. CONSTITUTION:Processing is carried out with a processing soln. contg. at least 2-aminobenzothiazole and diethylenetriaminepentaacetic acid or a salt thereof in place of washing after processing with a fixing soln. contg. a thiosulfate and a bleach fixing soln. contg. iron aminopolycarboxylate and a thiosulfate. At the time of using the processing soln. over a long period of time, processing excellent in stability can be carried out and the stability of a processed photographic image can be improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a silver halide color light-sensitive material, and more specifically, a processing method using a processing solution instead of a washing treatment after fixing treatment, and a washing treatment after bleach-fixing treatment. The present invention relates to a treatment method using a treatment liquid instead of treatment.

[0002]

2. Description of the Related Art The processing of silver halide color light-sensitive materials is
After color development processing, it is processed with a bleaching solution containing an iron salt and a halogen salt of aminopolycarboxylic acid, then with a fixing solution containing thiosulfate, and washed with running water.
Further, after color development processing, processing is performed with a bleach-fixing solution containing an iron salt of aminopolycarboxylic acid and thiosulfate, and washing processing with running water is performed.

When a silver halide color light-sensitive material is processed in this manner, a method for stably processing a large amount is as follows.
It is carried out by a method in which a necessary amount of a processing solution is replenished as a replenisher according to the amount of a light-sensitive material to be processed. In recent years, this replenishment amount has become small and the amount of processing liquid discharged after use has been small, so that it can be collected in a container.

On the other hand, the rinsing treatment is carried out using a large amount of water, and since a large amount of rinsing water is used, it is impossible to collect the waste water after use in a container. An automatic processor for processing photosensitive materials requires facilities for supplying water and draining water after use for this washing,
This facility will limit the location of automatic processors.

Further, since a large amount of rinsing water is used at a water temperature suitable for rinsing, a large amount of fuel is required to obtain the optimum temperature water, which is one of the causes of cost increase.

Therefore, various methods have been tried,
As one of them, in order to efficiently perform washing with a small amount of washing water, a cascade method in which many washing tanks are independently used to flow the washing water in the opposite direction of the flow of the photosensitive material has been known for a long time.

It is certain that this method can be efficiently washed with water, and if the small amount of photograph is processed as in the hand development processing, the purpose is sufficiently fulfilled. Even when a large amount of photosensitive materials are continuously processed by using an automatic processor as in today's day, it can be used as a washing method for an automatic processor and has a large number of washing tanks.

[0008] In this washing tank, washing water is added from the last tank of washing, and the overflowing portion is sequentially sent to the previous tank, and the light-sensitive material is sent in the reverse order of this flow, and the light-sensitive material is sequentially washed with fresh water. This step will be completed.

When such an automatic processor is used, the fixing solution or the bleach-fixing solution, which is a step before washing with water, is carried by the light-sensitive material to be processed and has a constant concentration in each washing tank. Even in a fixing solution or a bleach-fixing solution that does not decompose, the composition is out of balance in some of the washing tanks and decomposition occurs.

This causes deterioration of image quality,
In order to perform efficient rinsing with the smallest possible amount of rinsing water as much as possible, it is sufficient to increase the number of rinsing tanks connected in a cascade.By doing this, rinsing water is used, and rinsing is performed until it becomes discharged water. The time to stay in the tank becomes longer, microorganisms are generated, and defects that adhere to the image occur.At the same time, increasing the number of washing tanks to increase the efficiency of rinsing exposes the drawback of increasing the space of the automatic processor facility. Come on.

[0011]

A new method for eliminating such drawbacks is demanded, and as a method therefor, two or three water washing tanks are connected in a cascade and treated with a small amount of replenishing treatment liquid. And, it achieves one of its goals.

Further, a processing liquid is used so as to obtain a high quality image and an image with sufficient stability of this image,
In addition, by reducing the space with an automatic developing solution in a small processing tank and using a small amount of processing solution, it is possible to collect with a container because the amount of discharged liquid decreases, and it is not necessary to install water supply / drainage for washing. There are no restrictions on places.

In treating with such a small number of washing tanks,
It is necessary to obtain a high-quality image, and the stability of this image is sufficiently good, and the stability of the treated water and the treatment efficiency should be improved. In order to efficiently and stably continue processing a large amount of silver halide light-sensitive materials using an automatic processor, the processing solution to be used must be stable, and a highly stable processing method is desired. ing.

[0014]

The present invention relates to a method of using a processing solution instead of a fixing solution containing a thiosulfate and a bleaching solution containing an iron salt of aminopolycarboxylic acid and a thiosulfate. The present invention relates to a method of using a treatment liquid instead of the washing treatment subsequent to the fixing liquid.

The purpose thereof is to make it possible to perform processing with excellent stability upon long-term use, and further to improve the stability of the processed photographic image. In place of the washing treatment following the solution, the treating solution to be used and the bleach-fixing solution consisting of the iron salt and thiosulfate of aminopolycarboxylic acid are replaced with at least 2-aminobenzothiazole and diethylenetriamine. A treatment liquid containing pentaacetic acid or a salt thereof is used.

[0016]

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,
Commercially available color films were processed as in Table 1.

[Table 1]

The composition of each processing solution used for this processing is as follows. Color developer Anhydrous sodium sulfite 3.5 g Anhydrous potassium carbonate 35.0 g Potassium bromide 1.2 g Hydroxylamine sulfate 2.5 g Diethylenetriaminepentaacetic acid 1.0 g 3-Methyl-4-amino-N-ethyl-N- (β- Hydroxyethyl) -aniline sulfate 5.0 g Sodium hydroxide 1.0 g Water was added to 1.0 l

Color development replenisher: anhydrous sodium sulfite 4.0 g anhydrous potassium carbonate 40.0 g potassium bromide 1.0 g hydroxylamine sulfate 3.0 g diethylenetriaminepentaacetic acid 1.5 g 3-methyl-4-amino-N-ethyl-N -(Β-Hydroxyethyl) -aniline sulfate 5.5 g Sodium hydroxide 1.0 g Water was added to 1.0 l

Bleaching solution Ammonium bromide 140.0 g Ethylenediaminetetraacetic acid ammonium ammonium 90.0 g Ethylenediaminetetraacetic acid 5.0 g Water was added to 1.0 l

Bleach Replenisher Ammonium Bromide 170.0 g Ethylenediaminetetraacetic acid ammonium ammonium 110.0 g Ethylenediaminetetraacetic acid 8.0 g Hydroacetic acid 5.0 g Water was added to 1.0 l

Fixing solution Ammonium thiosulfate 140.0 g Sodium bisulfite 14.0 g Ammonia water 5.0 g Water was added to 1.0 l

Fixing replenisher Ammonium thiosulfate 170.0 g Sodium bisulfite 17.0 g Ammonia water 10.0 g Water was added to 1.0 l

Stabilizer Wetitol (product of Chugai Photo Chemicals Co., Ltd.) 5.0 ml Formalin 5.0 ml Water is added to 1.0 l

Stable replenisher The above stabilizer is used.

Upon processing, the replenishment amount for color development is 35
38 ml per 24 mm film, the bleach replenishment amount is 22 ml, and the fixing and stable replenishment amount is 35 ml.
performed in ml.

The process following fixing was carried out as follows. (1) 620ml of 35mm 24 piece film
Wash with water. (Methods used so far) (2) Washing with 31 ml of water per 25 mm 35-film film. (Comparison method) (3) 31 ml of processing liquid was used per 35 mm 24-shot film. (Invention)

The composition of this treatment liquid is as follows. Treatment liquid 2-aminobenzothiazole 0.2 g Diethylenetriaminepentaacetic acid 0.1 g Water is added and the pH is adjusted to 7.0 with 1.0 l sodium hydroxide.

Using the above treatment method and treatment liquid, 2
As a result of the treatment of 00 lines, the state of the treatment liquid and the washing water after the fixing treatment is as shown in Table 2.

[Table 2]

Further, the sample treated with the color film subjected to constant exposure is irradiated with sunlight, and the temperature is 60 ° C. and the humidity is 70%.
Table 3 and Table 4 show the results of comparing the durability of the images by placing them in a constant temperature and humidity chamber. The densitometer used for the concentration measurement is X-RITE310RT.

[Table 3]

[Table 4]

In Tables 3 and 4, BD is blue light density, G
D is the green light density, and RD is the red light density.

From these results, the treatment methods (1) and (3) are in good condition with both the washing water and the treatment liquid, and there is no image contamination or deterioration of the image processed together. In 2), the state of the treatment liquid is bad, and further, image contamination and image deterioration occur, and it is understood that the present invention (3) can be used in place of the conventional washing method.

Example 2 Using a small automatic processor,
Commercially available color papers were processed as shown in Table 5.

[Table 5]

The composition of each processing solution used for this processing is as follows. Color developer Anhydrous sodium sulfite 0.1 g Anhydrous potassium carbonate 20.0 g N, N-diethylenehydroxylamine 3.0 g Diethylenetriaminepentaacetic acid 2.0 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfone Amidoethyl) aniline sulfate 5.5 g Water is added and the pH is adjusted to 10.1 with 1.0 l sodium hydroxide.

Color development replenisher: anhydrous sodium sulfite 0.15 g anhydrous potassium carbonate 30.0 g N, N-diethylenehydroxylamine 4.0 g diethylenetriaminepentaacetic acid 2.0 g 3-methyl-4-amino-N-ethyl-N- ( β-Methanesulfonamidoethyl) aniline sulfate 7.5 g Water is added and the pH is adjusted to 10.4 with 1.0 l sodium hydroxide.

Bleach-fixing solution Ammonium thiosulfate 70.0 g Ethylenediaminetetraacetic acid ammonium ammonium 50.0 g Ethylenediaminetetraacetic acid 4.0 g Anhydrous sodium sulfite 15.0 g Acetic acid 10.0 g Water was added and pH was adjusted to 5 with ammonium hydroxide. Adjust to .5.

Bleach-fixing replenisher Ammonium thiosulfate 70.0 g Ethylenediaminetetraacetic acid ammonium ammonium 50.0 g Ethylenediaminetetraacetic acid 4.0 g Anhydrous sodium sulfite 20.0 g Acetic acid 15.0 g Water is added and pH is adjusted with 1.0 l ammonium hydroxide. Adjust to 5.5.

Upon processing, the replenishment amount for color development is 1
The replenishing amount for bleach-fixing was 160 ml per m ² , and the replenishing amount for bleach-fixing was 220 ml per m ² .

The processing subsequent to the bleach-fixing processing was performed as follows. (1) Washing with 12 l of water per 1 m ^{2 of the} light-sensitive material. (Previous Method) (2) Washing with 0.3 l of water per 1 m ^{2 of the} light-sensitive material. (Comparison method) (3) 0.3 l of the processing solution is used per 1 m ^{2 of the} light-sensitive material.
(Invention)

The composition of this treatment liquid is as follows. Treatment liquid 2-aminobenzothiazole 0.1 g Diethylenetriaminepentaacetic acid 0.5 g Water is added and the pH is adjusted to 7.0 with 1.0 l sodium hydroxide.

Using the above treatment method and treatment liquid, 1
As a result of 50 m ² treatment, the condition of the treatment liquid and the washing water after the bleach-fixing treatment is shown in Table 6.

[Table 6]

Further, the sample treated with the color paper which has been subjected to constant exposure is irradiated with sunlight, and the temperature is 60 ° C. and the humidity is 70%.
Table 7 and Table 8 show the results of comparing the changes in the images by placing them in a constant temperature and constant humidity tank. The densitometer used for the concentration measurement is X-RITE310RT.

[Table 7]

[Table 8]

In Tables 7 and 8, BD is blue light density, G
D is the green light density, and RD is the red light density.

From these results, the treatment methods (1) and (3) are in good condition for both the washing water and the treatment liquid, and there is no image contamination and no deterioration of the image processed together, but the treatment method (2 In (), the condition of the treatment liquid is poor, and further, image contamination and image deterioration occur, and it can be seen that (3) of the present invention can be used in place of the conventional washing method.

[Embodiment 3] Using a small automatic processor,
A commercial color paper was processed. The standard processing steps, color developing solution, color developing replenishing solution, bleach-fixing solution, bleach-fixing replenishing solution and their replenishing amounts are the same as in Example 2.

The processing subsequent to the bleach-fix processing was carried out as follows. The processing solution used here has the following composition, and the replenishing amount is 300 ml per 1 m ² of the light-sensitive material. Treatment Liquid (Invention) 2-Aminobenzothiazole 0.3 g Diethylenetriamine sodium pentaacetate 1.0 g Water is added and the pH is adjusted to 7.0 with 1.0 l sulfuric acid.

Treatment liquid (comparison) 2-aminobenzothiazole 0.3 g Ethylenediaminetetraacetic acid 1.0 g Water is added to adjust the pH to 7.0 with 1.0 l sodium hydroxide.

As a result of processing the light-sensitive material by 150 m ² using the above-mentioned processing method and processing solution, the conditions of the processing solution and washing water after the bleach-fixing process are as shown in Table 9.

[Table 9]

Further, the samples obtained by treating the color papers to which constant exposure was applied were placed in a thermo-hygrostat at a temperature of 60 ° C. and a humidity of 70%, and the results of comparing the changes in the images are shown in Tables 10 and 11. The densitometer used for the concentration measurement is the same as in Example 2.

[Table 10]

[Table 11] Density before and after testing of the images processed by exposure to blue, green and red light, respectively.

In Tables 10 and 11, BD is blue light density, GD is green light density, and RD is red light density.

From these results, it can be seen that both the treatment liquid of the present invention and the treatment liquid of the comparative example were in good condition, but the image did not change when treated with the treatment liquid of the present invention. On the other hand, when treated with the comparative treatment liquid, a large change was observed in the blue light density in the change in the part without the image,
Contamination occurs.

The aminopolycarboxylic acid ethylenediaminetetraacetic acid used in the comparative treatment liquid is the most common, and the diethylenetriaminepentaacetic acid or its salt used in the treatment liquid of the present invention is Has a special effect.

[0053]

As described above, according to the present invention, in the processing of a silver halide color light-sensitive material, at least 2-aminobenzothiazole is used instead of the washing treatment after the processing with the fixing solution and the bleach-fixing solution. Also, by treating with a treatment liquid containing diethylenetriaminepentaacetic acid or its salt, a large amount of washing water is not used and no washing water is used, so there is no need to install a water supply / drainage facility. There is no place restriction, you can process anywhere,
Practical effects are great such that the device can be simplified.

Claims (2)

[Claims] 1. Processing of a silver halide color light-sensitive material, after color development processing, processing is carried out with a fixing solution containing thiosulfate and at least 2-aminobenzothiazole and diethylenetriaminepentaacetic acid or its substitute for the subsequent washing with water. A method of processing a silver halide color light-sensitive material, which comprises using a processing solution containing a salt. 2. A method for processing a silver halide color light-sensitive material, which comprises, after color development processing, processing with a bleach-fixing solution containing an iron salt of aminopolycarboxylic acid and a thiosulfate, and replacing the subsequent washing with at least 2- A method for processing a silver halide color light-sensitive material, which comprises using a processing solution containing aminobenzothiazole and diethylenetriaminepentaacetic acid or a salt thereof.