JPS62178262A - Processing method for color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the time for bleaching and fixing by executing a bleach fixing process in succession to a bleaching process after a color developing process. CONSTITUTION:A color negative film is subjected to specified exposure by a sensitometer, then to the color developing process. The bleaching bath contg. >=0.3mol metallic complex salt of an aminopolycarboxylic acid and >=1.9mol alkali halide is required to be used in this case. A mercaptotriazole compd. or mercaptothiadiazole compd. is preferably added to the bleach fixing bath. The time for bleaching and fixing is thereby reduced by half and the time for processing the entire part is reduced.

Description

[Detailed description of the invention] b) Industrial application field The present invention relates to the processing of color photographic materials.

More specifically, the present invention relates to a method for rapidly processing color photographic materials, particularly for rapidly bleaching and fixing silver images.

Conventional technology The basic processing of color photographic light-sensitive materials is after image exposure of the light-sensitive material, color development processing, bleaching processing, fixing processing, water washing processing, and drying processing, and each processing solution is used stably. There are also processing steps that are added to increase the physical strength and stability of the photosensitive material after processing.When processing color photographic materials in this way, it is necessary to process them stably and in large quantities. The method used is to replenish the necessary processing solution as a replenisher depending on the amount of photosensitive material to be processed, and in addition, automatic processors that can automatically perform this processing are used. Reducing the time required has become an important issue. Shortening the time required for processing has many advantages, such as the ability to produce photographs more quickly, the productivity of photographic processing increases, and the ability to downsize automatic processors.

The most common method for shortening processing time is to increase the processing temperature and processing at a high temperature, and shortening of processing time has so far been achieved by this method. However, processing temperatures are already quite high at present, and processing at higher temperatures may cause deterioration of the physical strength of the photosensitive material, deterioration of the processing solution due to high temperatures, and difficulty in controlling the processing temperature and processing time. It will happen. To shorten the processing time at current processing temperatures, there are two methods: reducing the number of processing steps and shortening the time of each processing step. As a method of reducing the number of processing steps, there is a method of performing a bleach-fixing process, which is already used in processing color paper, but it may not be possible to perform a sufficiently good process due to differences in the properties of light-sensitive materials.

On the other hand, in the method of shortening the processing time, there are only a limited number of steps in which the processing time can be shortened, and the steps with a high possibility of shortening the processing time are bleaching of the silver image generated in one-color development processing, fixing of undeveloped silver halide, These two processes, zero color development processing, are the most important processes that affect the performance of the photograph, so the processing time cannot be shortened, and the water washing process affects the stability of the finished photograph. Processing time cannot be shortened.The process of bleaching the silver image created by zero-color development and fixing the undeveloped silver halide takes up about half of the total process time, so this process can be shortened. This is effective in speeding up the processing, and there is a big difference compared to the same process of color paper processing mentioned earlier, so shortening these two steps is necessary to speed up the processing.

C) Problems that need to be solved Shorten the bleaching and fixing processes that are carried out to speed up the processing of color photographic materials.The bleaching process, which requires the longest processing time in one of these processes, needs to be shortened. There is. The bleaching solution used in the bleaching process is a metal complex salt of aminopolycarboxylic acid, which has a relatively weak effect. You have to make the most of it, and still make up for what you lack in power elsewhere.

2) Means for Solving the Problems Accordingly, an object of the present invention is to completely shorten the bleaching and fixing times in order to shorten the processing time of color photographic materials.

The present inventors have discovered that, as a method of shortening the bleaching and fixing times for shortening the processing time of color photographic materials, the objective can be achieved by performing a bleach-fixing process after the bleaching process.

System) Examples The present invention will be explained in detail with reference to Examples, but the embodiments of the present invention will not be limited thereby.The bleaching solution used here contains 0.3
It has been found that it is necessary to use a bleach solution containing 1.9 moles or more of an alkali halide, and that it is desirable to add a mercaptotriazole compound or a mercaptothiadiazole compound to the bleach-fix solution.

Typical aminopolycarboxylic acids for making aminopolycarboxylic acid metal complex salts used in bleach and bleach-fix solutions are L, F, A, and MASON.

”PH0TOGRAPHIC PROCESS-ING
CHEMISTRY”, THE FO-CALPR
ESS, (p57 to p59), and the most commonly used metals are iron, copper, cobalt, nickel, etc. Common examples of these compounds are sodium acid and ammonium acid, and typical examples are sodium iron(III) ethylenediaminetetraacetate and ammonium iron(m) ethylenediaminetetraacetate. The alkali halides used in the bleaching solution include chlorine, bromine, and iodine as halogens, and sodium, potassium, and ammonium as alkalis, and the most commonly used ones are sodium bromide and ammonium bromide. Thiosulfates used in bleach-fix solutions are generally sodium thiosulfate and ammonium thiosulfate, and sulfites include sodium, potassium, and ammonium salts of sulfite, bisulfite, and metabisulfite. The ones used are
Typical mercaptotriazole compounds used in the eF white fixer, which are sodium sulfite and sodium bisulfite, are listed in the Chemical Substances Control Law, Existing Chemical Substances Handbook No. 2.
Edition” Kagaku Kogyo Nipposha (p.

318) Typical mercaptothiadiazole compounds are described in "Chemical Substances Control Law, Existing Chemical Substances Handbook 2nd Edition" Kagaku Kogyo Nipposha (p. 316). 10. Of/i, preferably 0.1 g/Jl to 1, Og/i.

Example 1 A commercially available color negative film is exposed to constant light using a photosensitive needle and processed using the following processing steps and processing solution.

Treatment (A) Color developer (A) Sodium hexametaphosphate 2. 'Og anhydrous sodium sulfite 4.0g anhydrous potassium carbonate 35.0g potassium bromide
l, 5g hydroxylamine sulfate
3.0g2-Methyl-4-N-ethyl-N-β-hydroxyethyl amino aniline sulfate
Add 5.0g water
1. O! Adjust the pH to 1 with L sodium hydroxide.
Set to 0.0.

Bleach solution (A) Disodium ethylenediaminetetraacetate 10.0g Ammonium iron (m) salt ethylenediaminetetraacetate 100.0g Ammonium bromide 150.0g Add water
Adjust the pH to 6.0 with aqueous ammonia.

Fixer (A) Ammonium thiosulfate 120.0g Anhydrous sodium sulfite 20.0g Add water
1. Adjust pH to 6.5 with Of acetic acid.

Stabilizer (A) Wetol (Chugai Photo Yakuhin Co., Ltd. product) lOlOm
l Formalin (37%) 5. Add ice water for 1.0 minutes (B) This is a process in which the total fixing time is 1/2, and the process liquid used in process (A) is used.

Processing (C) This is a process in which the total fixing time is halved.

The processing solutions used include a color developing solution (A), a stabilizing solution (A), and the following processing solutions.

Bleach solution (C) Disodium ethylenediaminetetraacetate 15.0g Ammonium iron (m) salt ethylenediaminetetraacetate 150.0g Ammonium bromide 225.0g Add water
1. On ammonia wood, set the pH to 6 and O.

Bleach-fix solution (C) Disodium ethylenediaminetetraacetate 8.0g Ammonium iron (m) salt of ethylenediaminetetraacetate 80. Og Anhydrous Sodium WLite 20.0g Ammonium Thiosulfate 120.0g Add water
1. Adjust the pH to 7.0 with ammonia water.

The blue light density of the films processed by each processing method was measured using a transmission type densitometer (Macbeth TD-504), and the results are as follows.

Treatment Treatment According to the presentation by the ex-husband, the treatment (C) of the present invention is the same as the treatment (A) (
The same results as those obtained using standard treatment were obtained. Treatment (B) is treatment (A), treatment (C) at blue light concentration.
Process (C) was found to be an excellent rapid processing method, as the higher density compared to Process (C) was due to the silver image remaining unbleached. The bleaching solution (C) of treatment (C) contains 0.38 mol of ethylenediaminetetraacetic acid ammonium iron (m) salt and 2.30 mol of ammonium bromide, whereas the bleaching solution (A) of treatment (B) contains Ethylenediaminetetraacetic acid ammonium iron (III) salt is 0.25 mol, and ammonium bromide is 1.53 mol. The time required for the treatment is 1 minute for treatment (C).

Bleach-fixing time is 4 minutes 30 seconds, 5 minutes 30 seconds, treatment (A) is 11 minutes, bleaching time is 6 minutes 30 seconds, fixing time is 4 minutes 30 seconds, processing time is 172 seconds of treatment (A). It is.

Example 2 A color negative film was exposed to constant light using a sensitometer and processed using the following processing steps and processing solution.

Treatment (A) Color developer (A) Sodium hexametaphosphate 2.0g Anhydrous sodium sulfite 4.0g Anhydrous potassium carbonate 35.0g Potassium bromide
1.0g hydroxylamine sulfate
3.0g2-Methyl-4-N-ethyl-N-β-hydroxyethyl amino aniline sulfate
Add 5.0g water
1. Adjust the pH to 10 with O-tachiki sodium oxide.
．． Let it be O.

Bleach solution (A) Disodium ethylenediaminetetraacetate 10,0g Ammonium iron (III) salt ethylenediaminetetraacetate 100.0g Ammonium bromide 150.0g Add water
1. O! Adjust the pH to 6 with L ammonia water.
Set to 0.

Fixer (A) Ammonium thiosulfate 120.0g Anhydrous sodium sulfite 20.0g Add water
Adjust the pH to 6.5 with acetic acid.

Stabilizer (A) Wetol (Chugai Photo Yakuhin Co., Ltd. Keihin) 1O2OmJ
l Formalin (37%) 5, On sample added l, 0 viewing process (B) This is a process where the total fixing time is l/2.44,
As the treatment liquid, the treatment liquid of treatment (A) is used.

Processing (C) is a process in which the total fixing time is l/2,44,
The processing solutions used include a color developing solution (A), a stabilizing solution (A), and the following processing solutions.

Bleach solution (C) Disodium ethylenediaminetetraacetate 13,0g Ammonium iron (m) salt of ethylenediaminetetraacetate 130.0g Ammonium bromide 195.0g Add water.
l, 0 sentences Adjust the pH to 6.0 with ammonia water.

Bleach-fix solution (C) Disodium ethylenediaminetetraacetate 8, Og Ammonium iron (m) salt of ethylenediaminetetraacetate go, 0g Anhydrous sodium sulfite 20.0g Ammonium thiosulfate 120.0g Add water
Adjust the pH to 7.0 with 1.0-aqueous ammonia water.

The blue light density of the film treated with each treatment method was measured using a transmission type meter (Macbeth TD-504), and the results are as follows.

Treatment Treatment According to the presentation of the treatment diagram, the treatment (C) of the present invention gave the same results as the treatment (A) (standard treatment). In terms of blue light density, processing (B) has a higher density than processing (A) and processing (C) because the silver image remains unbleached, and processing (C) is an excellent rapid processing method. It turned out to be.

The bleaching solution (C) of treatment (C) contains 0.33 mol of ethylenediaminetetraacetic acid ammonium iron (m) salt.

Ammonium bromide if l is 99 mol, whereas bleach solution (A) of treatment (B) contains 0.25 mol of ethylenediaminetetraacetic acid ammonium iron (m) salt and 1.53 mol of ammonium bromide. In addition, the time required for processing is
C) is 4 minutes 3 with a bleaching time of 1 minute and a bleach-fixing time of 3 minutes and 30 seconds.
0 seconds, treatment (A) was 11 minutes with bleaching time of 6 minutes 30 seconds and fixing time of 4 minutes 30 seconds, and treatment time of treatment (C) was treatment (
It is 1/2.44 of A).

Example 3 A commercially available color negative film is subjected to constant exposure using a photosensitive needle and processed in the following processing steps.

Processing (A) use

Bleach solution (A) Disodium ethylenediaminetetraacetate 10,0g Sodium ethylenediaminetetraacetic acid iron (m) salt 100.0g Sodium bromide 150.0g Add water
1. pH 6.0 with OfL ammonia water
shall be.

Fixer (A) Add sodium thiosulfate iso, 0g ammonium bisulfite 20.0g water
i, o Adjust pH to 6 with aqueous ammonia
．． 5.

Processing (B) is a process in which the total fixing time is 172.44,
As the treatment liquid, the treatment liquid of treatment (A) is used.

Processing (C) This processing (C) is a process in which the total time of the bleaching time and fixing time of Processing (A) is 172.44, and the processing solution is a color developer (A), a stabilizer solution (A), and the following. Use a treatment solution of

Bleach solution (C) Disodium ethylenediaminetetraacetate 13,0g Sodium ethylenediaminetetraacetic acid iron (III) salt 130.0g Ammonium bromide 200.0g Add water
l, 0 sentence pH 6, O with ammonia water
shall be.

Bleach-fix solution (C) Disodium ethylenediaminetetraacetate 8,0g Sodium iron(m) salt ethylenediaminetetraacetate 80.0g Anhydrous sodium sulfite 20.0g Ammonium thiosulfate
Add 120.0g water
1. Set the pH to 7.0 with On ammonia wood.

0.4 of 3-mercapto-1,2,4 triazole was added to the Miyama fixer (C) as a mercaptotriazole compound.
Add g/l. Separately, 0.5 g/cross of 2-amino-5-mercapto-1,3,4-thiadiazole is added as a mercaptotriazole compound.

The blue light density of the films processed by each processing method was measured using a transmission type densitometer (Macbeth TD-504), and the results are as follows.

Treatment Treatment Treatment The results when 4-triazole was added, and the lower row shows the results when 2-amino-5-mercapto-1,3,4-thiadiazole was added.

According to my ex-husband's presentation, treatment (C) of the present invention yielded the same results as treatment (A) (standard treatment). The reason that processing (B) has higher blue light density than processing (A) and processing (C) is because the silver image remains unbleached, and processing (C) is an excellent processing method. It turned out to be. The bleaching solution (C) of treatment (C) contains 0.31 mol of sodium iron (m) of ethylenediaminetetraacetate and 2.0 mol of ammonium bromide.
On the other hand, in the bleaching solution (A) of treatment (B), sodium iron (m) of ethylenediaminetetraacetate is 0.24 mol and sodium bromide is 1.46 mol. The time required for the treatment is 4 minutes and 30 seconds with a bleaching time of 1 minute for treatment (C) and a bleaching time of 3 minutes and 30 seconds for e:4, and a bleaching time of 6 minutes for treatment (A).
The processing time was 11 minutes (minute 30 seconds, fixing time 4 minutes 30 seconds).
C) (7) Processing time is 1/2.44 of processing (A).

f) Effects of the Invention As described above, according to the present invention, when processing a color photographic light-sensitive material after image exposure, the bleaching and fixing time can be halved by processing with the bleach-fix solution included after the color development process. The processing time is significantly reduced and the practical effect of shrinkage is great.

Claims (4)

[Claims] (1) A method for processing a color photographic material, which comprises performing a color development process on the color photographic material after image exposure, followed by a bleaching process, followed by a bleach-fixing process. (2) The bleaching solution used in the bleaching treatment is a bleaching solution containing at least 0.3 mol or more of an aminopolycarboxylic acid metal complex salt or more than 1.9 mol or more of an alkali halide. A method of processing color photographic materials. (3) The color photographic light-sensitive material according to claim 1, characterized in that the bleach-fix solution used in the bleach-fixing process is a bleach-fix solution containing at least an aminopolycarboxylic acid metal complex salt, thiosulfate, and sulfite. processing method. (4) The method for processing a color photographic light-sensitive material according to claim 1, characterized in that the bleach-fix solution used in the bleach-fix treatment is a bleach-fix solution containing a mercaptotriazole compound and/or a mercaptothiadiazole compound.