JPH0728218A - Method for processing silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To stably process the photosensitive material and to improve the stability of a processed picture at the time of using the photosensitive material for a long time by independently using several washing tanks, allowing a processing soln. to flow in the opposite direction to the flow of the photosensitive material and processing the material with a small supply of processing soln. CONSTITUTION:A processing soln. contg. 1-(2-(2,4-dichlorophenyl)-2-(2- propenyloxy)ethyl)-1H imidazole is used instead of washing in succession to a fixer consisting of a thiosulfate and instead of washing in succession to a processing soln. to be used and a bleach-fixing bath consisting of the iron salt of an aminopolycarboxylic acid and a thiosulfate. Consequently, the space is reduced in an automatic developing machine having a small number of processing tanks, a small amt. of the soln. is used and hence the soln. is recovered from the vessel since a small amt. of soln. is used, the water supply and discharge device need not be set for washing, and an area is not limited for installation.

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, and in order to carry out efficient rinsing with a small amount of rinsing water as much as possible, it is sufficient to increase the number of rinsing tanks. By doing so, rinsing water is used, The time it takes to stay in the washing tank until it becomes discharged water causes the generation of microorganisms, which causes defects that adhere to images. At the same time, increasing the washing tank to increase the efficiency of washing is a space for automatic processor facilities. The drawback of increasing the value of the surface comes to the surface.

[0011]

There is a demand for a new method for eliminating such drawbacks, and as a method therefor, two to four washing baths are independently used to perform processing in reverse to the flow of the photosensitive material. One of the purposes is achieved by flowing the liquid and treating with a treatment liquid with a small amount of replenishment.

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 machine in a small processing tank and using a small amount of processing liquid, it is possible to collect it in a container because the amount of discharged liquid decreases, and it is not necessary to install water supply and 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 processing liquid and the processing 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. Instead of the washing treatment following the solution, the treating solution to be used and the washing treatment following the bleach-fixing solution consisting of the iron salt of aminopolycarboxylic acid and thiosulfate are replaced with at least 1- (2- (2 A treatment solution containing .4-dichlorophenyl) -2- (2-propenyloxy) ethyl) -1Himidazole 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 shown in Tables 1 and 2.

[Table 1]

[Table 2]

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 Water was added (pH adjusted to 10.1 with sodium hydroxide) 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 sulphate 5.5g Water was added (pH adjusted to 10.1 with sodium hydroxide) 1.0l

Bleaching solution Ammonium bromide 140.0 g Ethylenediaminetetraacetic acid ammonium ammonium 90.0 g Ethylenediaminetetraacetic acid 5.0 g Water was added (pH adjusted to 6.0 with ammonium hydroxide) 1.0 l

Bleaching 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 (pH adjusted to 5.7 with ammonium hydroxide) 1.0 l

Fixing solution Ammonium thiosulfate 140.0 g Sodium bisulfite 14.0 g Ammonia water 5.0 g Water was added (pH was adjusted to 6.7 with acetic acid) 1.0 l

Fixing replenisher Ammonium thiosulfate 170.0 g Sodium bisulfite 17.0 g Ammonia water 10.0 g Water was added (pH was adjusted to 6.7 with acetic acid) 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) 600 ml per 35 mm 24 film film
Washing with water (tap water). (Methods used so far) (2) 35 ml of 24 mm 35-film film was washed with water (tap water). (Comparison method) (3) 35 mm of processing liquid was used per 35 mm 24-shot film. (Invention)

The composition of this treatment liquid is as follows. Treatment liquid 1- (2- (2.4-dichlorophenyl) -2- (2-propenyloxy) ethyl) -1Himidazole 0.1 g Water was added to 1.0 l The pH was adjusted to 6.0 with sodium hydroxide. To do.

Using the above treatment method and treatment liquid, 2
As a result of the processing of 00 lines, the states of the treatment liquid and the washing water after the fixing treatment are as shown in Table 3.

[Table 3]

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 4 and Table 5 show the results of comparing the durability of images by placing them in the constant temperature and humidity chamber. The densitometer used for the concentration measurement is X-RITE310RT.

[Table 4]

[Table 5]

In Tables 4 and 5, 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, there is no contamination of the image, and there is no water stain inside the treatment tank. However, in the treatment method (2), the condition of the treatment liquid is bad, and the water stains inside the treatment tank are generated, and further, the image is contaminated and the image is deteriorated. It can be seen that it can be used instead of the method.

Example 2 Using a small automatic processor,
Commercial color papers were processed as in Table 6.

[Table 6]

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 5.5g Water was added (pH adjusted to 10.1 with sodium hydroxide) 1.0l

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 was added (pH adjusted to 10.4 with sodium hydroxide) 1.0 l

Bleach-fixing solution Ammonium thiosulfate 70.0 g Ammonium ethylenediaminetetraacetate 50.0 g Ethylenediaminetetraacetic acid 4.0 g Anhydrous sodium sulfite 15.0 g Acetic acid 10.0 g Water is added (pH is adjusted to 5.5 with ammonium hydroxide). ) 1.0l

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 was added (pH was adjusted to 5.5 with ammonium hydroxide). Yes) 1.0l

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} light-sensitive material (tap water).
(Methods so far) (2) Washing with 300 ml of water per 1 m ^{2 of} light-sensitive material (tap water). (Comparison method) (3) 300 ml of processing solution is used per 1 m ^{2 of} light-sensitive material.
(Invention)

The composition of this treatment liquid is as follows. Treatment liquid 1- (2- (2.4-dichlorophenyl) -2- (2-propenyloxy) ethyl) -1H imidazole 0.15 g Water was added to 1.0 l The pH was adjusted to 6.0 with sodium hydroxide. To do.

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 7.

[Table 7]

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 8 and Table 9 show the results of comparing the changes in the images by putting them in the constant temperature and humidity chamber. The densitometer used for the concentration measurement is X-RITE310RT.

[Table 8] Density before and after the test of the part without image

Table 9: Density of processed images before and after testing

In Tables 8 and 9, 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) were in good condition for both the washing water and the treatment liquid, and there was no image contamination and no water stain inside the treatment tank. Although there is no image deterioration, the processing method (2) has a bad condition of the processing liquid, the generation of water stains inside the processing tank, image contamination and image deterioration, and (3) of the present invention is the conventional washing method. It can be seen that it can be used instead of.

[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) 1- (2- (2.4-Dichlorophenyl) -2- (2-propenyloxy) ethyl) -1H imidazole 0.1 g Diethylenetriamine sodium pentaacetate 1.0 g Water was added to 1.0 l sulfuric acid Adjust the pH to 6.0.

The processing liquid after the bleach-fixing treatment is in good condition, and the treated paper is free from contamination. Also, there is no generation of scale inside the treatment tank.

Further, the color papers subjected to constant exposure were treated, and the amount thereof was placed in a constant temperature and humidity chamber having a temperature of 60 ° C. and a humidity of 70%, and the results of comparison of image changes are shown in Tables 10 and 11. . The densitometer used for the concentration measurement is the same as in Example 2.

[Table 10] Density before and after the test of the part without image

Table 11: Density of processed images before and after testing

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 the condition of the treatment liquid of the present invention is good, and neither the image is contaminated nor deteriorated.

As described above, according to the present invention, in the processing of the silver halide color light-sensitive material, at least 1- (2) is used instead of the washing processing after the processing with the fixing solution and the bleach-fixing solution.
By treating with the treatment liquid containing-(2.4-dichlorophenyl) -2- (2-propenyloxy) ethyl) -1Himidazole, the washing water can be washed without using a large amount of washing water. Since it is not used, there is no need to install a water supply / drainage device, there is no restriction on the location of the facility, it can be processed anywhere, and the device can be simplified.

Claims (2)

[Claims] 1. Regarding the processing of a silver halide color light-sensitive material, after color development processing, processing is carried out with a fixing solution containing a thiosulfate, and at least 1- (2-
A method of processing a silver halide color light-sensitive material, which comprises using a processing liquid containing (2.4-dichlorophenyl) -2- (2-propenyloxy) ethyl) -1Himidazole. 2. A method of 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 with subsequent washing with at least 1- (2- (2.4-Dichlorophenyl) -2- (2-propenyloxy) ethyl) -1H
A method for processing a silver halide color light-sensitive material, which comprises using a processing solution containing imidazole.