JP3111368B2 - Color developing replenisher and processing method for silver halide color photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing replenisher and a processing method for a silver halide color photographic light-sensitive material, and more particularly to an automatic developing machine for preventing the precipitation of a color developing agent in a high-concentration color developing replenisher. The present invention relates to a replenisher for color development of a silver halide color photographic light-sensitive material whose photographic performance is stabilized and a processing method thereof.

[0002]

2. Description of the Related Art A color photographic light-sensitive material is processed by exposing the light-sensitive material to an image and then performing color development, silver bleaching, silver halide fixing, bleach-fixing in which bleaching and fixing are performed simultaneously, washing, and washing. Rinsing and drying instead of the processing are the basic processings. In addition, in order to use each processing solution stably, to increase the physical strength of the photosensitive material after processing, and to increase the stability There are additional processing steps.

In recent years, there has been a tendency to reduce the time required for processing color photographic light-sensitive materials, and to reduce the amount of processing solution used for processing. Reducing the time required for processing increases the efficiency of processing a photograph, and has the advantage that the size of an automatic processor can be reduced.
Further, the reduction in the amount of the processing liquid used in the processing corresponds to a reduction in the amount of the waste liquid used.

In general, an automatic developing machine is used for photographic processing, and a necessary processing solution is used as a replenisher and added to the automatic developing machine in proportion to the amount of the photosensitive material to be processed. The processing liquid overflows from the automatic developing machine and becomes a waste liquid. This waste liquid is collected for collective disposal.

The reason for the recovery is that the automatic developing machine has been reduced in size and can be installed anywhere, and that there is no free piping for discarding the overflowing liquid. Further, the overflow liquid cannot be discharged to the natural world as it is from the viewpoint of environmental pollution, and is processed so as to be able to flow to the natural world after being collected. It can be seen from the viewpoint of the recovery cost and the number of times that the overflow liquid is discarded that the smaller the overflow liquid is, the better the recovery is.

Therefore, in recent years, in order to reduce the overflow solution, a method of regenerating a color developer using an ion exchange resin method or an electrodialysis method, a method of regenerating a color developer simply using a regenerant, or a method of replenishing color development. A low replenishment treatment method for increasing the concentration of a liquid component has been proposed and put to practical use.

[0007]

The regeneration of the color developing solution is as follows.
It consists of removing insoluble accumulations and replenishing missing components, or simply replenishing missing components. The color developing solution is regenerated by these methods. However, in order to adopt these methods, special equipment, space, and management of the analysis of the developing solution components to stabilize the photographic performance are required. Therefore, there are many problems such as time spent on them and complicated operations.

On the other hand, the method of using a high-concentration replenisher at a low replenishment rate is a very suitable method because it does not require a special device, management and the like. However, when a color developing replenisher is prepared at a high concentration, a new problem arises in that a color developing agent having low solubility at a high pH is precipitated as crystals at a low temperature.

Since the crystals thus precipitated are not easily dissolved, they cause serious problems such as abnormal color developer composition, clogging of the circulation system, and damage to the photosensitive material.

[0010] To solve such a problem, Japanese Patent Laid-Open No. 4-147 is disclosed.
No. 138 and Japanese Patent Application No. 3-130383 (name of the invention, "color developing solution for color photographic light-sensitive materials"), and the like. I have.

According to this method, the concentration of the color developing agent can be increased to some extent.
This method is insufficient to achieve an ultra-low replenishment process of 80 ml or less per m ^2, and a more excellent method for preventing the precipitation of a color developing agent has been desired.

[0012]

Means for Solving the Problems The present inventors have conducted intensive studies on this problem, and as a result, a high-concentration color developing and replenishing solution is represented by sodium alkyldiphenyletherdisulfonate and the following formula (I). It has been found that this object is achieved by the addition of the compound to be added, and an ultra-low replenishment treatment becomes possible.

Embedded image R ₁ and R ₂ each independently represent a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, or an alkyl group which may be substituted with an alkylsulfonamide group. R ₃
Represents a phenyl group or a naphthyl group, and these groups are substituted with a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitrory group, and an alkyl group which may be substituted with these groups. May be.

That is, the replenisher for color development of the silver halide color photographic light-sensitive material according to the present invention can be used in an ultra-low replenishment process such that the replenishment rate per m ^{2 of} the photographic material is 80 ml or less during continuous processing. The color developing solution is characterized by containing sodium alkyldiphenyl ether disulfonate and a compound represented by the following formula (I).

Embedded image R ₁ and R ₂ each independently represent a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, or an alkyl group which may be substituted with an alkylsulfonamide group. R ₃
Represents a phenyl group or a naphthyl group, and these groups are substituted with a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitrory group, and an alkyl group which may be substituted with these groups. May be.

[0014]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by these examples. Specific examples of the compound of sodium alkyldiphenyl ether disulfonate used in the present invention are shown below. (A) Sodium nonyl diphenyl ether disulfonate (B) Sodium decyl diphenyl ether disulfonate (C) Sodium dodecyl diphenyl ether disulfonate These compounds are added in an amount of 0.05 to 1 liter of color developing replenisher.
Preferably, it is used at 0.5 g. These compounds are available as commercial products.

Specific examples of the compound represented by the general formula (I) used in the present invention are represented by the following formulas (I-1) to (I-23).
It is shown in Chemical formula 27. Formula (I-1)

Embedded image Formula (I-2)

Embedded image Formula (I-3)

Embedded image Formula (I-4)

Embedded image Formula (I-5)

Embedded image Formula (I-6)

Embedded image Formula (I-7)

Embedded image Formula (I-8)

Embedded image Formula (I-9)

Embedded image Formula (I-10)

Embedded image Formula (I-11)

Embedded image Formula (I-12)

Embedded image Formula (I-13)

Embedded image Formula (I-14)

Embedded image Formula (I-15)

Embedded image Formula (I-16)

Embedded image Formula (I-17)

Embedded image Formula (I-18)

Embedded image Formula (I-19)

Embedded image Formula (I-20)

Embedded image Formula (I-21)

Embedded image Formula (I-22)

Embedded image Formula (I-23)

Embedded image

These compounds are used in an amount of 1 l of a color developing replenisher.
It is preferable to use 0.05 to 1.0 g.
These compounds are also available from Journal of American Chemical
Luss Society (J. Am. Chem. Soc.),7
3, 3116 (1951).
Can be synthesized.

Example The following composition was dissolved to prepare a color developing replenisher. Diethylenetriaminepentaacetic acid 2.0 g Sodium chloride 1.5 g Potassium carbonate (anhydrous) 25.0 g Diethylhydroxylamine 5.0 g Sodium sulfite (anhydrous) 0.3 g Fluorescent brightener (4.4′-diaminostilbene) 7.5 g Developing agent precipitation inhibitor described in Table 1 N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate described in Table 1 Described in Table 1 Added water 1.0 l pH (using potassium hydroxide) listed in Table 1

The prepared replenisher was stored in a thermostat at 5 ° C. Tables 1 and 2 show the results.

[Table 1]

[Table 2] (P-Ts: p-toluenesulfonic acid) 〇: No precipitation occurs for 5 days or more. Δ: Precipitation occurs in less than 5 days. X: Precipitation occurs in less than 24 hours.

[0019] As can be seen from the above results, when the amount of the color developing agent is about 1.8 × 10- ² mol per 1l, p
-By adding toluenesulfonic acid, it is possible to suppress the precipitation of the active ingredient, but 2.2 × 1
0 ² becomes a high concentration of about moles be increased the amount of p- toluenesulfonic acid would cause the precipitation of color developing agent (Experiment 2-7).

Meanwhile, by adding an alkyl diphenyl ether sodium disulfonate, it is said with 1l per color developing agent to allow higher concentrations of up to about 2.2 × 10- ² mol, 2.4 × 10- ² mol or more per 1l It can be seen that when the concentration becomes too high, precipitation of the main drug still occurs even when the amount of alkyldiphenyletherdisulfonic acid is increased (Experiments 8 to 11).

[0021] Also, although the effect by the addition of general formula (I) compound represented by alone seen, the still color developing agent is 2.4 × 10- ² moles or more ultra-high density, results in precipitation of agent (Experiments 18 to 20).

However, when sodium alkyldiphenyl ether disulfonate and the compound represented by the general formula (I) are used together as in the present invention, the replenisher 1
in ultra-high concentrations color developing agent referred to 2.8 × 10- ² mol with the addition of about 0.05~0.2g per l, at a low temperature,
It can be seen that an excellent effect of not causing precipitation of the main drug is exhibited (Experiments 12 to 17).

[0023]

As described above, according to the present invention, when a silver halide color photographic light-sensitive material is subjected to image development and then color development processing is carried out under ultra-low replenishment, the color development replenisher contains sodium alkyldiphenyl ether disulfonate and a compound represented by the general formula ( By adding the compound represented by I), a high-concentration color developing replenisher which does not cause precipitation of the color developing agent can be obtained, and it is understood that the industrial use effect is large.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 7/44 G03C 7/407

Claims (5)

(57) [Claims] 1. A color developing replenisher for a silver halide color photographic light-sensitive material, comprising sodium alkyldiphenyl ether disulfonate and a compound represented by the following formula (I). Embedded image R ₁ and R ₂ each independently represent a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, or an alkyl group which may be substituted with an alkylsulfonamide group. R ₃
Represents a phenyl group or a naphthyl group, and these groups are substituted with a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitrory group, and an alkyl group which may be substituted with these groups. May be. 2. A 2.3 color developing agent × 10- ² mol /
2. The replenisher for color development according to claim 1, which contains 1 or more. 3. The method according to claim 1, wherein the color developing agent is N-ethyl-N- (β-
The color developing replenisher according to claim 2, which is (methanesulfonamidoethyl) -3-methyl-4-aminoaniline. 4. After imagewise exposing a silver halide color photographic light-sensitive material, a color developing replenisher containing sodium alkyldiphenyletherdisulfonate and a compound represented by the following formula (I) is subjected to a color developing process. A method for processing a silver halide color photographic light-sensitive material, wherein the processing is performed while replenishing. Embedded image R ₁ and R ₂ each independently represent a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, or an alkyl group which may be substituted with an alkylsulfonamide group. R ₃
Represents a phenyl group or a naphthyl group. May be. 5. The silver halide color photographic light-sensitive material according to claim 4, wherein in the color development processing, the color development replenisher according to claim 4 is replenished in an amount of 80 ml or less per 1 m ^{2 of the} light-sensitive material. Processing method.