JPH0854718A - Color developing composition - Google Patents

Abstract

PURPOSE:To prevent occurrence of sulfurous acid gas and to maintain high stability at the time of feeding a color developing agent as an aqueous solution. CONSTITUTION:The color developing composition contains a p-phenylenediamine- based color developing agent and a compound represented by the general formula in which each of R1 and R2 is, independently, H atom, or an alkyl or aryl group for which a hydroxyl, carboxyl, alkoxyl, amido, sulfonamido, or alkylsulfonamido group may be substituted; and R3 is a phenyl or naphthyl group for which a hydroxyl, carboxyl, alkoxyl, amido, sulfonamido, or alkylsulfonamido group, or an alkyl group for which any of these group may be substituted, may be substituted.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition used for processing a silver halide color photographic light-sensitive material, and more particularly to an aqueous solution composition of a paraphenylenediamine type color developing agent having excellent stability.

[0002]

2. Description of the Related Art Processing of a silver halide color photographic light-sensitive material is carried out by exposing the light-sensitive material to an image and then performing color development processing, silver bleaching processing
The silver halide fixing process, the bleach-fixing process in which the bleaching process and the fixing process are performed at the same time, the rinsing process, the rinsing process as an alternative to the rinsing process, the stabilizing process, and the drying process are basic processes.

Besides, in order to use each processing solution stably,
Alternatively, there are processing steps added to increase the physical strength and stability of the processed light-sensitive material.

Among the silver halide color photographic light-sensitive materials, the method most often used at present is to obtain a color print from a color negative film, and the user of this color print wants to see the print as soon as possible. However, we want to be able to print in a short time, and we need to speed up the process to accommodate this.

On the other hand, the processing of silver halide color photographic light-sensitive materials has become possible by the improvement of the light-sensitive materials. Further, in processing, a large amount of processing can be easily performed by an automatic developing machine, and at the same time, due to the development of the automatic developing machine, the size and cost are reduced, and many machines are used.

In these photographic processings, an automatic developing machine is used in order to easily obtain a large number of photographs quickly, and a necessary amount of processing solution is replenished as a replenishing solution for processing a large amount of a light-sensitive material. The processing is performed while the photographer requests the processing from the photographer, and the processing is performed to meet the request within a short time.

In order to process the silver halide color photographic light-sensitive material easily and quickly, the processing agent used for the processing is supplied in the form of a liquid, and the processing solution can be prepared by simply diluting with water. It has become.

It is desirable that the device be easy to use and that the operating environment be good. These feed solutions used for the treatment are in various states, and are not all usable under a sufficiently favorable environment.

In processing a silver halide color photographic light-sensitive material, a color developer is supplied in 3 to 4 parts. This is a combination of compositions in which there is no problem even if mixed, so that it takes a long time from the time the treatment agent is manufactured to the time it is used, and there is no deterioration of the treatment agent during that time. It is supplied by.

Of these, the color developing agent is oxidized by the exposed silver halide and reacts with the coupler contained in the light-sensitive material to form a dye image, and the color developing agent used is a paraphenylenediamine type color developing agent. It is a developing agent.

When the color developing agent is supplied in a liquid state, it should be a concentrated aqueous solution and stable under various storage conditions. This para-phenylenediamine color developing agent has a strong tendency to oxidize during storage, and in order to prevent this, it is common to add a sulfite compound as an antioxidant to make a concentrated aqueous solution, and the color development provided by this The developer has a very strong odor.

[0012]

Since the color developing agent used in the processing of silver halide color photographic light-sensitive materials is the most important composition in the photographic processing, the stability is particularly important, and therefore, To improve stability, a large amount of sulfite compound will be used. However, if the amount of sulfite compound used is large, the dye image may be abnormal.
No. 5-37957.

Further, there is a problem that the environment during use is deteriorated. As described in JP-B-45-37957, the concentrated aqueous solution has a pH of 4 or less, and more preferably has a pH of 1 or less, and since it is under acidity, the sulfite compound used as an antioxidant is gasified. , Accompanied by highly irritating gas.

Since this sulfurous acid gas strongly irritates the mucous membrane and may cause pain in the throat and chest and dyspnea, a sulfite compound that causes sulfurous acid gas is not used, and the color development is excellent in storage stability. It is desired to provide a developer composition.

[0015]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to
The color developing agent supplied as an aqueous solution does not generate sulfurous acid gas, and yet another purpose is to maintain good stability of the color developing agent aqueous solution.

The present inventors have conducted extensive studies in order to solve this problem, and as a result, a method for keeping good stability during storage in a color developing agent composition supplied as an aqueous solution without generation of sulfurous acid gas. Found.

That is, it has been found that the problem can be solved by a color developing composition containing a paraphenylenediamine type color developing agent and a compound represented by the following general formula (Formula 2) or a salt thereof. General formula

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R ₁ and R ₂ are each independently a hydroxyl group,
It represents an alkyl group, an aryl group or a hydrogen atom which may be substituted with a carboxyl group, an alkoxyl group, an amide group, a sulfonamide group or an alkylsulfonamide group. R ₃ represents a phenyl group or a naphthyl group, and these groups may be substituted with a hydroxyl group, a carboxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitroso group and these groups. It may be substituted with an alkyl group.

[0019] Para-phenylenediamine color developing agent used in the present invention, for example, Journal of American Chemical Society (J.Am.chem.Soc.,) 73, 310
It can be synthesized by 0, (1951). In addition, the compound represented by the general formula is a commercially available product, or Berichte (Ber.), 22 , 2092 (1
889), Journal of American Chemical Society (J. Am.chem.Soc.,) 73 , 3100, (1951).

Specific examples of the compound are shown below. Further, as salts of these compounds, sulfates, hydrochlorides of the following compounds,
Examples thereof include, but are not limited to, nitrates and paratoluene sulfonates.

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

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[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

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[Chemical 15]

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[Chemical 17]

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[Chemical 19]

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[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

Further, in the present invention, there is no drawback even if a sulfite compound used as a stabilizer for keeping the color developing agent stable is used in combination.

The sulfite compound which supplies sulfurous acid includes an alkali metal salt of sulfurous acid, an alkali metal salt of acidic sulfurous acid, and an alkali metal salt of metabisulfite. Commonly used compounds are lithium sulfite, sodium sulfite, and sulfite. Potassium, acidic sodium sulfite, acidic potassium sulfite, sodium metabisulfite, potassium metabisulfite and the like, and inorganic acids and organic acids can be used to make the composition acidic, for example, sulfuric acid, nitric acid, acetic acid and the like.

[0023]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 An aqueous solution of the color developing composition shown in Table 1 was prepared,
Put it in a 200 ml polyethylene container and stopper it.
In a constant temperature bath (Platinous Unicool PU-2G, manufactured by Tabai Seisakusho Co., Ltd.) for 200 hours. During this time, the caps were opened once a day for 30 minutes at room temperature to stabilize each color developing composition. Tested.

[Table 1] Color developing agent (A) is 4-amino-3-methyl-N-ethyl-N- (β-methylsulfonamidoethyl) aniline 3/2 sulfate monohydrate. (B) is 0.5 g of sodium bisulfite. (C) is a sulfate of the compound of the present invention, in which 12.8 g of 3-methyl-N-ethyl-N- (β-methylsulfonamidoethyl) aniline is dissolved in 50 ml of acetone, and 4.9 g of sulfuric acid is added. It is the obtained crystal.

The following color developing solution was prepared using the color developing composition after the stability test of the aqueous solution of the color developing composition shown in Table 1, and a constant exposure was carried out with a sensitometer using a commercially available color paper. The treatment was carried out according to the treatment steps shown in Table 2.

[Table 2]

Color developer Diethylenetriaminepentaacetic acid 2.0 g Sodium chloride 8.0 g Potassium carbonate (anhydrous) 25.0 g Diethylhydroxylamine 2.5 g Sodium sulfite (anhydrous) 0.2 g Fluorescent brightener (UVITEX MST manufactured by Ciba Geigy) 4 0.0 g Color-developing composition of Table 1 (amount to give 5 g of color-developing agent) Water was added to 1.0 l pH (using potassium hydroxide) 10.0

Bleach-fixing solution Ammonium thiosulfate 70.0 g Sodium sulfite (anhydrous) 17.0 g Ethylenediaminetetraacetic acid iron (III) ammonium 55.0 g Ethylenediaminetetraacetic acid disodium 5.0 g Water was added to 1.0 l pH (acetic acid was used) ) 6.0

Stabilizer 2-aminobenzothiazole 0.1 g 1-hydroxyalkylidene-1.1-diphosphonic acid 4.0 g Water was added to 1.0 l pH (using sodium hydroxide) 6.5

The processed light-sensitive material has a minimum density portion density.
(Dmin), low density area density (LD), high density area density (H
D) is measured, the difference between the high density portion density and the low density portion density is determined as contrast (HD-LD), and the results of using the color developing composition before the stability test and the color developing composition after the stability test are shown. The difference from the used result is the change in the minimum density (△ D
min), change in sensitivity (△ LD), change in contrast (△
HD-LD) was determined.

For the measurement, a reflection type densitometer (X-RITE
310) was used and the results are shown in Tables 3 and 4. In the table, indicates blue light density, indicates green light density, and indicates red light density.

[Table 3]

[Table 4]

As can be seen from the above results, the color developing composition containing the compound of the present invention, like the color developing composition (2) containing the sulfite compound, does not contain a stabilizer. Minimum density area density compared to (1)
The increase in (Dmin) is small, the decrease in low-density portion (LD) is small, the contrast (HD-LD) is small, and the compound of the present invention is an excellent stabilizer and has no odor. Also proves to be an excellent stabilizer.

Example 2 An aqueous solution of the color developing composition shown in Table 5 was prepared, placed in a 200 ml volume polyethylene container and capped, and a constant temperature bath (Platinous Unicool PU-
The sample was left to stand in 2G (Tabai Seisakusho Co., Ltd.) for 200 hours, and during this time, it was opened once a day for 30 minutes at room temperature, and the stability of each color developing composition was tested.

[Table 5] Color developing agent (D) is 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaminoaniline sulfate monohydrate. (E) is 0.3 g of sodium hydrogen sulfite. (C) is the same compound as the compound of Example 1.

The following color developing solution was prepared using the color developing composition after the stability test of the aqueous solution of the color developing composition shown in Table 5, and a constant exposure was carried out by a sensitometer using a commercially available color negative film. It was given and treated in the treatment steps of Table 6.

[Table 6]

Color developing solution Potassium carbonate (anhydrous) 30.0 g Sodium sulfite (anhydrous) 0.5 g Sodium bromide 1.3 g Hydroxylamine sulfate 2.0 g Diethylenetriaminepentaacetic acid 2.0 g Color developing composition of Table 5 (color developing The amount of the developing agent is 4.5 g) Water is added to 1.0 l pH (using potassium hydroxide) 10.0

Bleaching solution Iron (III) ammonium diamine tetraacetate 100.0 g Disodium ethylenediamine tetraacetate 5.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to 1.0 l pH (using ammonia water) 6.0

Fixing solution Ammonium thiosulfate 120.0 g Disodium ethylenediaminetetraacetate 1.0 g Sodium bisulfite 15.0 g Sodium hydroxide 2.5 g Water was added to 1.0 l pH (using acetic acid) 6.5

Stabilizer Wetitol (product of Chugai Photo Chemicals Co., Ltd.) 5.0 ml Formalin (37%) 1.0 ml Water is added to 1.0 l

The processed light-sensitive material has a minimum density portion density.
(Dmin), low density area density (LD), high density area density (H
D) is measured, the difference between the high density portion density and the low density portion density is determined as contrast (HD-LD), and the results of using the color developing composition before the stability test and the color developing composition after the stability test are shown. The difference from the used result is the change in the minimum density (△ D
min), change in sensitivity (△ LD), change in contrast (△
HD-LD) was determined.

For the measurement, a transmission densitometer (X-RITE3
10) was used, and the results are shown in Tables 7 and 8. In the table, indicates blue light density, indicates green light density, and indicates red light density.

[Table 7]

[Table 8]

As can be seen from the above results, the color developing composition containing the compound of the present invention, like the color developing composition (10) containing the sulfite compound, does not contain a stabilizer. Minimum density area density compared to (9)
The increase in (Dmin) is small, the decrease in low-density portion (LD) is small, the contrast (HD-LD) is small, and the compound of the present invention is an excellent stabilizer and has no odor. Also proves to be an excellent stabilizer.

[0040]

As described above, according to the present invention, a color developing composition containing a paraphenylenediamine type color developing agent and a compound represented by the following general formula (Formula 30) or a salt thereof has excellent stability. It can be seen that a color developing composition having no odor and excellent stability in photographic processing performance can be obtained. General formula

Embedded image R ₁ and R ₂ are each independently a hydroxyl group, a carboxyl group, an alkoxyl group, an amide group, a sulfonamide group,
An alkyl group, an aryl group or a hydrogen atom which may be substituted with an alkylsulfonamide group is shown. R ₃ represents a phenyl group or a naphthyl group, and these groups may be substituted with a hydroxyl group, a carboxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitroso group and these groups. It may be substituted with an alkyl group.

Claims (3)

[Claims] 1. A color developing composition comprising a paraphenylenediamine color developing agent and a compound represented by the following general formula (Formula 1) or a salt thereof. General formula: R ₁ and R ₂ are each independently a hydroxyl group, a carboxyl group, an alkoxyl group, an amide group, a sulfonamide group,
An alkyl group, an aryl group or a hydrogen atom which may be substituted with an alkylsulfonamide group is shown. R ₃ represents a phenyl group or a naphthyl group, and these groups may be substituted with a hydroxyl group, a carboxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitroso group and these groups. It may be substituted with an alkyl group. 2. A para-phenylenediamine color developing agent is 4-amino-3-methyl-N-ethyl-N- (β-methylsulfonamidoethyl) aniline 3/2 sulfate monohydrate. The color developing composition according to claim 1. 3. A para-phenylenediamine color developing agent is 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate monohydrate. The color developing composition according to item 1.