JP3195993B2 - Color developing replenisher and processing method for silver halide color photographic light-sensitive 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, in which P-toluenesulfonic acid salt is used as a dissolving agent for a color developing agent. 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 made intensive studies on this problem, and as a result, have found that a compound represented by the following general formula (I) is added to a high-concentration color developing replenisher. It has been found that this object has been achieved and ultra-low replenishment processing is possible.

Embedded image R ₁ , R ₂ and R _{3 each} represent a hydrogen atom or a C ₁ to C 3
Represents an alkyl group, which may be the same or different.
X represents a hydrogen atom, NO group, methyl group or ethyl group
Indicates the difference .

[0013] That is, the color developing replenisher for a silver halide color photographic material according to the present invention, during the continuous processing, the photosensitive material 1 m ² per supplementary charges in the ultra-low replenishment processing such that the following 80 ml, emitting color The following general formula (I) is used for the developer.
Characterized by containing a compound represented by the formula:

Embedded image R ₁ , R ₂ and R _{3 each} represent a hydrogen atom or a C ₁ to C 3
Represents an alkyl group, which may be the same or different.
X represents a hydrogen atom, NO group, methyl group or ethyl group
Indicates the difference .

[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 represented by the general formula (I) used in the present invention are shown in the following formulas (I-1) to (I-8) . 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

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 1 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 repeatedly stored at 25 ° C. to -5 ° C. once a day and stored for one week. Tables 1 and 2 show the results.

[Table 1]

[Table 2]

[0018] 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
-It is possible to suppress the precipitation of the main drug by adding toluenesulfonic acid, but it is 2.3 × 1 per liter.
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).

However, it can be seen that precipitation of the color developing agent can be easily suppressed by adding only about 0.5 g of the compound represented by the general formula (I) of the present invention per liter of replenisher. (Experiments 8-10).

Example 2 Using a commercially available color paper, after image exposure, processing was performed using the processing steps and processing solutions shown in Table 3.

[Table 3]

Color developing solution Mother liquor Replenisher (I) Replenisher (II) Diethylenetriaminepentaacetic acid 2.0 g 2.0 g 2.0 g Sodium chloride 8.0 g 1.5 g 0.5 g Potassium carbonate (anhydrous) 25.0 g 25 5.0 g 25.0 g diethylhydroxylamine 2.7 g 4.0 g 5.4 g sodium sulfite (anhydrous) 0.2 g 0.3 g 0.3 g Optical brightener (4.4′-diaminostilbene) 4.0 g 6. 0 g 7.5 g table 4 N-ethyl-N-(beta-methanesulfonamidoethyl) according to developer precipitation inhibitor table 4 according to 3-methyl-4-amino aniline sulfate 1.2 × 10- ² 2.0 × 10- ² 2.5 × 10- ² Mol mol mol water 1.0 l 1.0 l 1.0 l pH (using potassium hydroxide) 10.05 10.60 11.00

Bleach-fix solution (mother liquor and replenisher are the same) Ammonium thiosulfate 70.0 g Sodium sulfite (anhydrous) 17.0 g Ammonium iron (IV) ethylenediaminetetraacetate 55.0 g Disodium ethylenediaminetetraacetate 5.0 g Water was added. 1.0 l pH (with acetic acid) 6.0

Stabilizer (mother liquor and replenisher are the same) 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) T) 7.0 Table 4 shows the results.

[Table 4]

During continuous processing, in the color developing step, the concentration of the color developing agent in the running solution is reduced by the amount used for the development. However, the conditions such as accumulation of eluted materials are not always improved.

[0025] Also, the crystal nucleus such that many adverse conditions compared to replenisher such that tends to occur in the drive portion or the like of the automatic developing machine, at a low temperature running solution as Experiment 12 to induce the precipitation of color developing agent It turns out that precipitation occurs.

However, as is clear from the experimental results, by using a color developing replenisher to which the compound represented by the general formula (I) is added, it is possible to perform ultra-low replenishment of a high-concentration replenisher during continuous processing. It can also be seen that the precipitation of the color developing agent in the running solution can be prevented. (Experiment 16)

[0027]

As described above, the present invention relates to a method for preparing a silver halide color photographic light-sensitive material, comprising the steps of: It can be seen that a high-concentration color-developing replenisher that does not cause precipitation of the color-developing agent can be obtained by the addition, and has a large industrial use effect.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 7/407 G03C 7/44

Claims (5)

(57) [Claims] 1. A replenisher for color development of a silver halide color photographic light-sensitive material, comprising a compound represented by the following general formula (I): Embedded image R ₁ , R ₂ and R _{3 each} represent a hydrogen atom or a C ₁ to C 3
Represents an alkyl group, which may be the same or different.
X represents a hydrogen atom, NO group, methyl group or ethyl group
Indicates the difference . Wherein the color developing agent 2.0 × 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 image-wise exposure of the silver halide color photographic light-sensitive material, it Oite be performed while replenishing the color developer replenisher contains a compound represented by the following general formula (I) of 2 to color development A method for processing a silver halide color photographic light-sensitive material, comprising: Embedded image R ₁ , R ₂ and R _{3 each} represent a hydrogen atom or a C ₁ to C 3
Represents an alkyl group, which may be the same or different.
X represents a hydrogen atom, NO group, methyl group or ethyl group
Indicates the difference . 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.