JPH0731390B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing an exposed silver halide color photographic light-sensitive material, and particularly to accelerate the bleaching action to shorten the processing time, and When continuously processing a silver halide color photographic light-sensitive material, it is possible to form a high-quality color photographic image without producing insoluble substances generated in a bleaching solution containing a bleaching accelerator. The present invention relates to a method of processing a silver color photographic light-sensitive material.

(B) Conventional Technology Generally, the basic steps of processing a silver halide color photographic light-sensitive material are a color developing step and a bleaching step. That is, by subjecting the exposed silver halide color photographic light-sensitive material to color development processing, the silver halide is reduced to produce a silver image, and the oxidized color developing agent reacts with the color developing agent to give a dye image. . Subsequently, in the bleaching step, the silver image formed in the previous step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and the halogen present in the bleaching solution becomes silver halide. Next, a silver complexing agent called a fixing agent forms a water-soluble silver complex, which is dissolved and removed. Therefore, the photographic material that has undergone these steps becomes only a dye image.

(C) Problems to be solved In general, red blood salts, dichromates, ferric ion complex salts, etc. are known as bleaching agents. Although red blood salts, dichromic acid, etc. are excellent in oxidizing power, there are problems in environmental pollution, and therefore various restrictions are imposed on their use. on the other hand,
Ferric ion complex salts (for example, ferric iron complex salts of aminopolycarboxylic acid) have relatively small oxidizing power and insufficient bleaching power, resulting in poor bleaching or a long bleaching time. .

In order to solve these problems by using a bleaching solution containing a ferric ion complex salt having insufficient bleaching power, various compounds such as a mercapto compound as described in US Pat. No. 3,893,858 have been used. Presented as a bleach accelerator.

However, although these compounds have a substantially sufficient bleaching promoting effect, they are insoluble in the bleaching solution when the silver halide color photographic light-sensitive material is continuously processed in the bleaching solution containing these compounds. The major drawback is that they produce material and stain the equipment, and in the worst case, the deposition of these insoluble materials reduces the quality of the color photographic image.

(D) Means for Solving the Problems The present invention is excellent in bleaching speed without using a chemical substance that causes environmental pollution, and even when a silver halide color photographic light-sensitive material is continuously processed, It is a processing method capable of forming a good quality color photographic image without producing an insoluble substance in a bleaching solution containing a bleaching accelerator.

In the processing method in which the silver halide color photographic light-sensitive material after exposure is subjected to color development processing and then bleaching processing, at least one of the bleaching accelerators represented by the general formula (I) is contained in the bleaching processing solution, It is characterized by containing at least one of the compounds represented by the general formulas (II-a) and (II-b).

In the formula, R ₁ and R ₂ represent a hydrogen atom, a methyl group or an ethyl group, and n represents an integer of 1 to 6.

In the formula, A represents an alkylene group having 1 to 3 carbon atoms or a phenylene group. B represents SO ₃ M or COOM, and M represents a hydrogen atom, an alkali metal atom or an ammonium ion.

(E) Examples Specific examples of the compounds represented by the general formulas (II-a) and (II-b) are shown below, but the present invention is not limited to these exemplified compounds.

(II-a)-(1) 1- (m-carboxyphenyl) -5
-Mercaptotetrazole (II-a)-(2) 1- (O-carboxyphenyl) -5
-Mercaptotetrazole (II-a)-(3) 1- (p-sulfophenyl) -5-
Mercaptotetrazole (II-a)-(4) 1-carboxymethyl-5-mercaptotetrazole (II-b)-(1) 4- (p-carboxyphenyl) -3.
5-dimercapto-1.2.4-triazole (II-b)-(2) 4- (m-carboxyphenyl) -3.
5-Dimercapto-1.2.4-triazole These compounds are described in British Patent No. 1,275,701, Japanese Patent Publication No. 59-52821, J. Indian Chem. Soc., 42 , 333 (196
5), J.Gen.Chem.USSR (English Transl) , 32, 927 (19
62) etc. can be referred to for synthesis.

The compound represented by the general formula (II-a) or (II-b) used in the present invention is known as an example of a bleaching accelerator in JP-A-53-28426 and JP-A-60-61749, The bleaching acceleration effect is not sufficient and the purpose of accelerating the bleaching process cannot be achieved. However, when the compound represented by the general formula (II-a) or (II-b) is used in combination with the bleaching accelerators represented by the general formula (I) having a sufficient bleaching effect, the compound contains the bleaching accelerator. It has been found that the bleaching solution has an excellent effect of preventing the generation of an insoluble substance caused by continuous processing of a silver halide color photographic light-sensitive material.

The addition amount when the compound represented by the general formula (II-a) or (II-b) is contained in the bleaching solution varies depending on the type of processing solution, the type of photographic material to be processed, processing conditions, etc. It is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol per treatment liquid.

The compound used as the bleaching accelerator in the present invention is represented by the above general formula (I), and the preferred specific compound examples are shown below.

(I)-(1) 2-Aminoethanethiol (I)-(2) 3-Aminopropanethiol (I)-(3) Dimethylaminoethanethiol (I)-(4) Dimethylaminopropanethiol (I)- (5) Dimethylaminobutanethiol (I)-(6) Dimethylaminohexanethiol (I)-(7) N-methyl-N-ethylaminoethanethiol (I)-(8) Diethylaminoethanethiol (I)-( 9) Diethylaminobutanethiol The synthesis of the above compounds is described in US Pat. No. 4,285,984, Helv. Chim. Acta., 38 , 1147 (1955), J. Am. Chem. So.
c., 70 , 950 (1948).

The bleaching accelerator used in the present invention, that is, the addition amount when the compound represented by the general formula (I) is contained in the bleaching solution is
Depending on the type of processing liquid, the type of photographic material to be processed, processing conditions, etc., 1 × 10 ^{-4 to} 5 × 10 per processing liquid
^-2 mol is preferred.

In the bleaching solution constituting the present invention, the bleaching agent used is a ferric ion complex, and examples thereof include ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or salts thereof. Is a complex of. Representative examples of aminopolycarboxylic acids and aminopolyphosphonic acids include ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid 1,2-propylenediaminetetraacetic acid 1,3-propylenediaminetetraacetic acid nitrilotriacetic acid cyclohexanediaminetetraacetic acid glycol etherdiaminetetraacetic acid 1,3-Propylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1-hydroxyethylidene-1,1-diphosphonic acid and the like can be mentioned, but of course, the compounds are not limited to these exemplified compounds.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1. A commercial color negative film was exposed to daylight and then continuously developed according to the following processing steps. The compounds of the general formulas (II-a) and (II-b) of the present invention shown in Table 1 and the bleaching accelerator represented by the general formula (I) were added to the bleaching solution and used.

Treatment process Temperature Time Coloring phenomenon 38 ℃ 3 minutes 15 seconds Bleach 38 ℃ 3 minutes Fixing 38 ℃ 3 minutes 15 seconds Washing 35 ℃ 2 minutes 10 seconds Stability 35 ℃ 1 minute Dry 40 ℃ The above treatment is Starting with one mother liquor of each processing solution having the following composition, continuously treating while supplementing the replenishing solution of each processing solution having the following composition, until the formation of an insoluble substance in the bleaching solution with the naked eye. The number of color negative films to be processed was calculated.

Before continuously processing the color negative film, commercially available color negative control strips were each treated with the mother liquor of the various bleaching solutions shown in Table 1 according to the above-mentioned treatment steps, and then each with a transmission densitometer X-RITE310. The Dmax of the film was measured, and the bleached state was measured from the difference from the Dmax value Dmax 'when the bleaching was completed. The results are shown in Table 1.

Stabilizer Mother liquor Replenisher Weettol (product of Chugai Photo Chemicals Co., Ltd.) 10.0 ml 15.0 ml Formalin (37%) 5.0 ml 7.0 ml Water added 1.0l 1.0l As shown in Table 1, the general formula ( When the bleaching accelerator represented by I) is used alone, although the bleaching property is good, continuous treatment of about 5 color negative films produces insoluble substances in the bleaching solution. However, when the compound represented by the general formula (II-a) or (II-b) of the present invention is used in combination, an insoluble substance may not be produced even after 30 continuous treatments without impairing the desilvering property. Recognize. As is clear from the results of Samples 2 and 3, the general formula (I
It can be seen that the compound represented by Ia) or (II-b) alone has almost no bleaching promoting ability.

Thus, by using the bleaching accelerator represented by the general formula (I) and the compounds represented by the general formulas (II-a) and (II-b) in combination, a color photograph can be obtained without impairing the bleaching promoting ability. It can be seen that even if a large amount of the light-sensitive material is continuously processed, it has an excellent performance of not producing an insoluble substance in the bleaching solution.

Example 2 A commercial color reversal film was imagewise exposed and then continuously developed according to the following steps. The compounds of the general formulas (II-a) and (II-b) of the present invention shown in Table 2 and the bleaching accelerator represented by the general formula (I) were added to the bleaching solution and used.

Treatment process Temperature Time First development 38 ° C 6 minutes First water washing 38 ° C 2 minutes Reversal 38 ° C 2 minutes Color development 38 ° C 6 minutes Bleach 38 ° C 4 minutes Fixed 38 ° C 4 minutes Second water washing 38 ° C 4 minutes Cheap Constant room temperature 1 minute Dry 40 ° C Note that the above treatment is started using one mother liquor of each treatment liquid of the following composition, and continuously treated while supplementing the replenisher of each treatment liquid of the following composition. The number of processed color reversal films required until the formation of an insoluble substance in the bleaching solution was visually determined.

Before continuously processing the color reversal film, a commercially available control strip for color reversal is shown in Table 2.
Using the mother liquor of the various bleaching solutions described in 1, after each processing according to the above processing steps, measure the Dmax of each film with a transmission densitometer (X-RITE310), Dm when bleaching is completed
The bleached state was measured from the difference from the ax value Dmax ′. The results are shown in Table 2.

Stabilizer Mother liquor Replenisher Weettol (product of Chugai Photo Chemicals Co., Ltd.) 10.0 ml 15.0 ml Formalin (37%) 5.0 ml 7.0 ml Water added 1.0l 1.0l As is clear from the results in Table 2, the present invention General formula (II-
It can be seen that when the compound represented by a) or (II-b) is used in combination with the bleaching accelerator represented by the general formula (I), an insoluble substance is not produced in the bleaching solution even in the reversal processing system.

Thus, by using the bleaching accelerator represented by the general formula (I) and the compounds represented by the general formulas (II-a) and (II-b) in combination, the bleaching promoting ability is impaired even in the reversal processing system. It can be seen that even if a large amount of color light-sensitive material is continuously processed, it does not produce an insoluble substance in the bleaching solution.

(E) Effect of the Invention As described above, according to the present invention, the bleaching accelerator is excellent in the bleaching speed without using a chemical substance that causes environmental pollution, and even when the silver halide color light-sensitive material is continuously processed. It is possible to form a good quality color photographic image without producing an insoluble substance in the bleaching solution containing, and the effect on use is great.

Claims (1)

[Claims] 1. A processing method in which a silver halide color photographic light-sensitive material after exposure is subjected to color development processing and then bleaching processing,
The bleaching solution contains at least one bleaching accelerator represented by the general formula (I), and further contains the general formulas (II-a) and (II
-b) A method for processing a silver halide color photographic light-sensitive material, which comprises at least one of the compounds shown below. In the formula, R ₁ and R ₂ represent a hydrogen atom, a methyl group or an ethyl group, and n represents an integer of 1 to 6. In the formula, A represents an alkylene group having 1 to 3 carbon atoms or a phenylene group. B represents SO ₃ M or COOM, and M represents a hydrogen atom, an alkali metal atom or an ammonium ion.