JPH10312046A - Method of storing color developer for silver halide color photographic light-sensitive materials - Google Patents

Abstract

(57) [Problem] To provide a method for storing a color developing solution which contains all the components necessary for a color developing solution used for processing a silver halide color photographic light-sensitive material and is excellent in stability. The oxygen equivalent coefficient is 100 ml / (m ² · at).
(1) 0.08 mol / l or more of an aromatic primary amine color developing agent (2) 0.13 mol in a container made of a plastic material having a m.day (temperature of 20 ° C., relative humidity of 65%) or less. / L or more of the compound represented by the general formula (I) (3) A color developing solution comprising an alkali agent for adjusting the pH to 13 or more is stored. General formula (I) (R ₁ and R ₂ represent a substituted or unsubstituted alkyl group.)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preserving a color developing solution used for processing a silver halide color photographic light-sensitive material, and contains all compositions and is excellent in stability. The present invention relates to a method for storing a color developing solution for a photosensitive material.

[0002]

2. Description of the Related Art In recent years, rapid processing of silver halide color photographic light-sensitive materials has been made possible by improvement of the light-sensitive materials. Further, in processing, a large amount of processing can be easily performed by an automatic developing machine. In addition, the development of automatic developing machines has reduced the size and cost, and many machines have been used. In the processing of these photographs, an automatic processor is used to easily obtain a large number of photographs quickly, and in order to process this photosensitive material in a large amount, the processing is performed while replenishing a necessary amount of a processing solution as a replenisher. The processing is performed, and the photographic processing company requested by the photographer to perform the processing performs the processing to meet the request within a short time.

In order to process silver halide color photographic light-sensitive materials easily and quickly, the processing agents used in the processing are supplied in the form of a liquid, and can be prepared by simply diluting with water. Has become. Processing of silver halide color photographic light-sensitive materials includes color development processing, silver bleaching processing, silver halide fixing processing, bleach-fixing processing in which bleaching and fixing are performed simultaneously, water-washing, and water-washing after image exposure of the light-sensitive material. Alternative rinsing, stabilizing, and drying treatments are the basics, and some of the treatment solutions used in these treatments use solutions divided into multiple parts to make this treatment solution. , Many part liquids are supplied.

In the color developing process, a color developing agent oxidized by the exposed silver halide reacts with a coupler contained in a photosensitive material to form a dye image.
Therefore, this is the most important step in processing a silver halide color photographic light-sensitive material. For this reason, the color developing solution is supplied in three or more parts, and this is done so that a long time elapses from the production of the processing agent to its use, during which the processing agent does not deteriorate. Are supplied in a plurality of parts because they have a composition combination that does not cause a problem even if they are mixed.

[0005] However, in order to further facilitate the processing quickly, instead of supplying the composition required for the processing in a plurality of parts, it is preferable to use a processing agent containing all the compositions. In some cases, there is a need to provide a color developing solution having excellent stability and a method for storing the same. Regarding the method of storing the color developing solution, Japanese Patent Application No. 61-142819,
Although there are applications in Japanese Patent Application No. 63-243354, there are strict conditions for the material of the container to be used, and the use of an inexpensive and easily usable container is awaited.

[0006]

The color developing solution used for processing a silver halide color photographic light-sensitive material is the most important step in photographic processing, and therefore, stability is particularly important. It contains all the components, and the content of the color developing solution deteriorates due to oxidation during the period from production to use. In particular, due to weight loss and deterioration of the color developing agent,
The processed pictures can not be expressed well and can cause contamination. For this reason, it is desired to provide a method for storing a color developing solution which has a form of a color developing solution containing all the components and whose contents do not change during the period from production to use.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide:
A method for storing a color developer containing all the necessary components as a color developer, a storage method in which the color developer is stable for a long time, and a color developer which is easily and quickly used. It is another object of the present invention to provide a method for preserving a color developer. The present inventor has conducted intensive studies and the like in order to solve this problem, and as a result, the oxygen permeability coefficient was 1 unit.
In a container made of a plastic material of not more than 00 ml / (m ² · atm · day) (temperature 20 ° C., relative humidity 65%), at least (1) at least 0.08 mol / l of aromatic primary amine color development (2) a compound represented by the following general formula (I) in an amount of 0.13 mol / l or more;
It has been found that the object can be achieved by storing a color developing solution comprising the above alkaline agent. General formula (I)

Embedded image (R ₁ and R ₂ represent a substituted or unsubstituted alkyl group.)

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the aromatic primary amine color developing agent used in the present invention include: (1) 4-amino-3-methyl-N-diethylaniline hydrochloride (2) 4-amino- N-ethyl-N- (β-hydroxyethyl) aniline sulfate (3) 4-amino-3-methyl-N-ethyl-N- (β
-Methylsulfonamidoethyl) aniline 3/2 sulfate monohydrate (4) 4-amino-3-methyl-N-ethyl-N- (β
-Hydroxyethyl) aniline sulfate monohydrate (5) 4-amino-3- (β-methylsulfonamidoethyl) -N-diethylaniline hydrochloride (6) 4-amino-N-ethyl-N- (β -Methoxyethyl) aniline / 2-paratoluenesulfonate (7) 4-amino-N-butyl-N- (β-butylsulfonate) aniline sulfate and the like.

Further, specific examples of the general formula (I) used in the present invention include (I-1)

Embedded image (I-2)

Embedded image (I-3)

Embedded image (I-4)

Embedded image (I-5)

Embedded image (I-6)

Embedded image (I-7)

Embedded image (I-8)

Embedded image (I-9)

Embedded image (I-10)

Embedded image (I-11)

Embedded image (I-12)

Embedded image (I-13)

Embedded image (I-14)

Embedded image (I-15)

Embedded image (I-16)

Embedded image (I-17)

Embedded image (I-18)

Embedded image Etc.

Further, specific examples of the alkaline agent used to adjust the pH to 13 or more used in the present invention include potassium hydroxide, sodium hydroxide, trisodium phosphate, and tripotassium phosphate.

[0011]

The present invention will be described below in detail with reference to examples, but the present invention is not limited by these examples. Example 1 A bag-like container made of a plastic material having a different oxygen permeability coefficient was prepared, the following color developing solution was sealed in this container, and stored in a thermostat at 60 ° C. for 450 hours. Stability was tested. Color developing solution (1) Triethanolamine 16.0 g Diethylhydroxylamine 5.0 g Sodium chloride 1.0 g Potassium carbonate 30.0 g Diethyltriaminepentaacetic acid 2.0 g Sodium sulfite 0.05 g Fluorescent brightener ( UVITEX MST Ciba Geigy) 10.0 g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 3/2 sulfate monohydrate 15.5 g Add water 1.0 l pH (using potassium hydroxide) 12.0 Color developing solution (2) Water is added to the composition of the color developing solution (1) to make 0.7 l. The pH at this time is 12.8. Color developing solution (3) Water is added to the composition of the color developing solution (1) to make 0.4 liter. The pH at this time is 13.2.

The materials used for the containers are as follows. Container A Oxygen permeability coefficient is 200 ml / (m ² · atm · day)
(Temperature 20 ° C., relative humidity 65%) Plastic material container Container B Oxygen permeability coefficient is 90 ml / (m ² · atm · day)
(Temperature 20 ° C., relative humidity 65%) Plastic material container Container C Oxygen permeability coefficient is 50 ml / (m ² · atm · day)
(Temperature: 20 ° C., relative humidity: 65%) Plastic material container Color developing solutions (1), (2), and (3) stored in a thermostat at 60 ° C. for 450 hours using liquid chromatography to develop each color. The results of measuring the amount of 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 3/2 sulfate monohydrate in the developer are shown in Table 1.

[Table 1] Residual rate of color developing agent in each container Residual rate = amount after storage test / amount before storage test × 100

In the color developing solutions (1), (2) and (3),
Table 2 shows the amount of the aromatic primary amine color developing agent, the amount of the compound represented by the formula (I), and the pH.

[Table 2]

As can be seen from the above results, the amount of the aromatic primary amine color developing agent of the present invention is 0.08 mol / l.
As described above, in the color developing solution in which the amount of the compound represented by the general formula (I) is 0.13 mol / l or more and the pH is 13 or more, the oxygen permeability coefficient is 90 ml / 50 ml / (m ² · atm ·
day) (temperature 20 ° C., relative humidity 65%) in a plastic material container, 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 3/2 sulfate monohydrate Is high, the amount of the aromatic primary amine color developing agent is 0.08 mol / l or less, the amount of the compound represented by the general formula (I) is 0.13 mol / l or less, pH And a plastic material container having an oxygen transmission coefficient of 100 ml / (m ² · atm · day) (temperature 20 ° C., relative humidity 65%) or more are 4-amino-3-methyl-N-. Ethyl-N- (β
It can be seen that the residual ratio of-(methanesulfonamidoethyl) aniline 3/2 sulfate monohydrate is low.

Example 2 The color developing solution (3) used in Example 1 had an oxygen transmission coefficient of 90 ml / (m ² · atm ·
day) (temperature 20 ° C., relative humidity 65%), and 200
ml / (m ² · atm · day) (temperature 20 ° C., relative humidity 65%) placed in a plastic material container, allowed to stand for 6 months, and given a commercially available color paper with a constant exposure using a sensitometer, And according to Table 3. Color developing solution (A) Oxygen permeability coefficient is 90 ml / (m ² · atm · day)
The following additives were added to 600 ml of a processing solution that was placed in a plastic material container (temperature: 20 ° C., relative humidity: 65%) and left standing for 6 months to make a 2.5-fold volume of a color developing solution using water. Processing liquid. Color developing solution (B) Oxygen permeability coefficient is 200 ml / (m ² · atm · day)
The following additives were added to 600 ml of a processing solution that was placed in a plastic material container (temperature: 20 ° C., relative humidity: 65%) and left standing for 6 months to make a 2.5-fold volume of a color developing solution using water. Processing liquid. Color developer (C) A processing solution obtained by adding the following additives to 600 ml of the color developer (1) used in Example 1. Additives Potassium chloride 10.0 g Potassium hydrogen carbonate 10.0 g Potassium carbonate 7.0 g Add water 400.0 ml

Bleaching / fixing solution (A) 90.0 g ammonium thiosulfate 35.0 g ammonium ferrous ethylenediaminetetraacetate 60.0 g 6.0 g ethylenediaminetetraacetic acid 5.8

Rinse solution (A) 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

[Table 3]

The photosensitive material processed with the color developing solutions (A), (B) and (C) is subjected to a minimum density density (Dmin) and a low density density (Dmin) using a reflection type densitometer, X-RITE310. LD),
The high density part density (HD) is measured, and the difference between the density of the color developer (A) and the density of the color developer (C) is defined as the value of the color developer (A). Table 4 shows the difference between the density and the density of the color developer (C) as the value of the color developer (B).

[Table 4]

As can be seen from the above results, when a plastic material container having an oxygen permeability coefficient of the present invention of 90 ml / (m ² · atm · day) (temperature 20 ° C., relative humidity 65%) is used, It can be seen that there is no difference in the photographic processing performance between a new color developing solution (C) and a new color developing solution (C) even when the color developing solution is used for a long time. (B), when the time from manufacture to use is long, there is a deterioration in the performance of photographic processing between it and a new color developing solution (C),
It cannot be used as a color developer.

[0020]

As described above, according to the present invention, even in a color developing solution containing all the compositions, the properties thereof can be kept stable for a long period of time. An excellent method for preserving a color developer can be provided.

Claims (1)

[Claims] An oxygen permeability coefficient of 100 ml / (m ² · at)
m.day) (temperature: 20 ° C., relative humidity: 65%). A color developing solution comprising at least the following (1), (2), and (3) is stored in a container made of a plastic material. A method for storing a color developing solution for a silver halide color photographic light-sensitive material. (1) Aromatic primary amine color developing agent of 0.08 mol / l or more (2) Compound of the following general formula (I) of 0.13 mol / l or more (3) pH of 13 or more Alkali agent General formula (I) (R ₁ and R ₂ represent a substituted or unsubstituted alkyl group.)