JPH07239541A - Replenished solution for color development of silver halide color photogrpahic sensitive material and processing method therefor - Google Patents

Abstract

PURPOSE:To inhibit the deposition of a color developing agent of a silver halide color photographic sensitive material. CONSTITUTION:A compd. represented by the formula and arom. sulfonic acid or its salt are incorporated into a replenished soln. for color development of a silver halide color photographic sensitive material. In the formula, each of R1 and R2 is optionally substd. alkyl, the substituent is hydroxyl, alkoxyl, amido, sulfonamido or alkylsulfonamido, R3 is optionally substd. phenyl or naphthyl and the substituent is hydroxyl, alkoxyl, amido, sulfonamido, alkylsulfonamido, nitroso or alkyl which may have such a group as a substituent.

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 silver halide color photographic light-sensitive materials, and more specifically, to prevent precipitation of a color developing agent in a high-concentration color developing replenisher, and an automatic developing machine. The present invention relates to a color development replenisher and a processing method for a silver halide color photographic light-sensitive material in which continuous processing and photographic performance are stabilized.

[0002]

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

In recent years, the time required for processing color photographic light-sensitive materials has been shortened, and the amount of processing liquid used for processing has been reduced. Reducing the processing time has the advantages of increasing the efficiency of processing a photograph and further reducing the size of the automatic processor.
Further, the decrease in the amount of the processing liquid used for the processing means the decrease in the amount of the waste liquid used.

For the photographic processing, an automatic developing machine is generally used, and the necessary processing solution is added to the automatic developing machine in proportion to the amount of the photosensitive material to be processed as a replenishing solution and the processing is carried out. The processing solution overflows from the automatic processor and is discarded. This waste liquid is collected for collective disposal.

The reason for the collection is that the automatic processor is downsized and can be installed anywhere, and the piping for discarding the overflowing liquid is not free. Furthermore, the overflow liquid cannot be discharged to the natural world as it is from the viewpoint of environmental pollution, and it is treated so that it can be discharged to the natural world after being collected. It can be seen from the viewpoint of recovery cost and the number of times of recovery that the less overflow liquid is discarded, it is better for recovery.

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

[0007]

Regeneration of the color developing solution is
It consists of removing insoluble debris and replenishing deficient components, or simply replenishing deficient components. The color developing solution is regenerated by these methods. In order to incorporate these methods, special equipment, space, and management of analysis of developing solution components for stabilizing photographic performance are required. Therefore, there are many problems such as time spent on them, complicated operations, and the like.

On the other hand, the method of using the high-concentration replenisher at a low replenishment does not require special equipment, management, etc., and is therefore a very suitable method. However, when the color developing replenisher is prepared at a high concentration, the low-developing color developing agent is generated as crystals on the replenishing tank wall surface, floating balls, etc. at high pH, and especially at low temperature, the entire tank bottom is covered. It causes new problems such as the formation of crystals.

The crystals thus deposited do not dissolve easily and cause serious problems such as abnormal composition of the color developing solution, clogging of the replenishing system and circulation system, and damage to the light-sensitive material.

To solve this problem, Japanese Patent Publication No. 46-41
No. 676 and Japanese Patent Publication No. 50-21250, a method of adding celluloses, Japanese Patent Publication No. 47-20743, of adding polyvinyl alcohol and polyvinylpyrrolidone, and Japanese Patent Publication No. 58-16179 of adding a specific polymer. Method,

British Patent No. 669,505 discloses a method of using an alkylbenzene sulfonate, International Patent Publication WO
-87/04534 and JP-A-2-77743, a method using a styrene polymer having a sulfonic acid group introduced therein, JP-A-4-67038 and JP-A-4-81751.
JP-A-4-204733 describes a method of adding a surfactant, and JP-A-4-350855 describes a method of using a surfactant and an aromatic sulfonate together.

By using these methods, precipitation can be prevented up to a certain concentration of the main drug. However,
When the replenishing amount of the color developing solution per 1 m ^{2 of the} light-sensitive material which is commonly used today is about 80 ml or less, the concentration of the color developing agent is further increased,
It turns out that the known methods cannot handle it.

Further, in the method of adding a surfactant,
New problems such as an increase in the foamability of the treatment liquid have also occurred.

[0014]

OBJECTS OF THE INVENTION The first object of the present invention is to provide a high-concentration color development replenisher that does not produce crystal deposits, and secondly uses a high-concentration color development replenisher that does not produce crystal deposits. Thirdly, the third method is to provide a high-concentration color development replenisher that does not cause clogging in the replenishment system of an automatic processor, and fourthly, color development that does not cause damage to the light-sensitive material. To provide a high-concentration color developing replenisher.

[0015]

DISCLOSURE OF THE INVENTION As a result of intensive studies, the inventors of the present invention have found that a compound of the following general formula (I) and an aromatic sulfone can be added to a high-concentration color developing replenisher. It has been found that the addition of an acid or a salt thereof solves this problem and enables ultra-low replenishment treatment.

[Chemical 3] R ₁ and R ₂ each independently represent an alkyl group which may be substituted with a hydroxyl 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 are substituted with a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitroso group and an alkyl group which may be substituted with these groups. May be.

That is, the color developing replenisher for the silver halide color photographic light-sensitive material according to the present invention is an ultra-low replenishment processing such that the replenishment amount per 1 m ^{2 of} the light-sensitive material is about 80 ml or less during continuous processing. In the color developer, the following general formula
(I) A compound represented by Chemical formula 4 and an aromatic sulfonic acid or a salt thereof are contained.

[Chemical 4] R ₁ and R ₂ each independently represent an alkyl group which may be substituted with a hydroxyl 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 are substituted with a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitroso group and an alkyl group which may be substituted with these groups. May be.

[0017]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. 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-23) to 27. Formula (I-1)

[Chemical 5] Formula (I-2)

[Chemical 6] Formula (I-3)

[Chemical 7] Formula (I-4)

[Chemical 8] Formula (I-5)

[Chemical 9] Formula (I-6)

[Chemical 10] Formula (I-7)

[Chemical 11] Formula (I-8)

[Chemical 12] Formula (I-9)

[Chemical 13] Formula (I-10)

[Chemical 14] Formula (I-11)

[Chemical 15] Formula (I-12)

[Chemical 16] Formula (I-13)

[Chemical 17] Formula (I-14)

[Chemical 18] Formula (I-15)

[Chemical 19] Formula (I-16)

[Chemical 20] Formula (I-17)

[Chemical 21] Formula (I-18)

[Chemical formula 22] Formula (I-19)

[Chemical formula 23] Formula (I-20)

[Chemical formula 24] Formula (I-21)

[Chemical 25] Formula (I-22)

[Chemical formula 26] Formula (I-23)

[Chemical 27]

These compounds are preferably used in an amount of 0.05 to 1.0 g per liter of color developing replenisher.
Further, these compounds are commercially available from Journal of the American Chemical Society (J. Am. Chem. Soc.),
73 , 3116 (1951), and can be easily synthesized.

Specific examples of the aromatic sulfonic acid or its salt used in the present invention include the following formulas (S-1) -28 to (S-27) -54. Formula (S-1)

[Chemical 28] Formula (S-2)

[Chemical 29] Formula (S-3)

[Chemical 30] Formula (S-4)

[Chemical 31] Formula (S-5)

[Chemical 32] Formula (S-6)

[Chemical 33] Formula (S-7)

[Chemical 34] Formula (S-8)

[Chemical 35] Formula (S-9)

[Chemical 36] Formula (S-10)

[Chemical 37] Formula (S-11)

[Chemical 38] Formula (S-12)

[Chemical Formula 39] Formula (S-13)

[Chemical 40] Formula (S-14)

[Chemical 41] Formula (S-15)

[Chemical 42] Formula (S-16)

[Chemical 43] Formula (S-17)

[Chemical 44] Formula (S-18)

[Chemical formula 45] Formula (S-19)

[Chemical formula 46] Formula (S-20)

[Chemical 47] Formula (S-21)

[Chemical 48] Formula (S-22)

[Chemical 49] Formula (S-23)

[Chemical 50] Formula (S-24)

[Chemical 51] Formula (S-25)

[Chemical 52] Formula (S-26)

[Chemical 53] Formula (S-27)

[Chemical 54]

These compounds are preferably used in an amount of about 0.5 to 50 g per liter of color developing replenisher.
Further, these compounds are available as commercial products.

Example 1 The following composition was dissolved to prepare a color developing replenisher. Diethylenetriamine pentaacetic acid 3.0 g Triethanolamine 12.0 g N, N-diethylhydroxylamine 5.0 g Sodium chloride 1.5 g Tyrone 0.3 g Sodium sulfite 0.2 g Potassium carbonate 25.0 g Optical brightener (UVITEX MST: Ciba Geigy) Manufactured) 4.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate (CD-3) As described in Table 1, deposition of the developing agent represented by the general formula (I). Inhibitor Listed in Table 1 Aromatic sulfonic acid or sulfonate Listed in Table 1 Add water 1.0 l pH (using potassium hydroxide) pH 11.0

The prepared replenisher was stored in a constant temperature bath at 5 ° C. for one week. The results are shown in Table 1, Table 2 and Table 3.
The addition amount of the developing agent precipitation inhibitor represented by the general formula (I) is represented by% by weight based on the amount of the color developing agent. The evaluation of each experiment was performed according to the following criteria. 〇 No precipitation of crystals and no precipitation of oily substances. × Crystalline color developing agent is precipitated. Δ Crystalline color developing agent does not precipitate, but oily substance precipitates.

[Table 1]

[Table 2]

[Table 3]

From Table 1, Table 2 and Table 3, it can be seen that the effect of preventing the precipitation of the crystalline color developing agent and the effect of preventing the precipitation of the oily substance can be recognized only by the combination of the present invention.

[Example 1] Using a commercially available color paper, after imagewise exposure, the processing steps and processing solutions shown in Table 4 were applied.

[Table 4]

Color developer Mother liquor Replenisher Diethylenetriaminepentaacetic acid 2.0 g 3.0 g Triethanolamine 8.0 g 12.0 g N, N-diethylhydroxylamine 2.5 g 5.0 g Sodium chloride 8.0 g 1.5 g Tyrone 0.2g 0.3g Sodium sulfite 0.15g 0.2g Potassium carbonate 25.0g 25.0g Optical brightener (UVITEX MST manufactured by Ciba Geigy) 2.0g 4.0g N-ethyl-N- (β-methanesulfonamide amidoethyl) ) -3-Methyl-4-amino aniline sulfate (CD-3) 5.3 g 10.6 g developing agent precipitation inhibitor represented by the general formula (I): described in Table 5: aromatic sulfonic acid or Sulfonate ━━━━━ Shown in Table 5 Add water 1.0 liter 1.0 liter pH (using potassium hydroxide) 10.05 11.00

Bleach-fixing solution (mother liquor and replenisher are the same) 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. 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) ) 7.0 The above results are shown in Table 5.

[Table 5]

It can be said that the concentration of the color developing agent in the running solution is reduced by the amount used for the development in the color developing step during the continuous processing. The conditions such as the accumulation of the eluate of are not necessarily improved.

For example, there are many disadvantageous conditions as compared with the replenisher such as crystal nuclei which induce the precipitation of the color developing agent in the driving portion at the interface with air, and the driving as in Experiments 1 and 2. The deposits accumulated on the parts stain or scratch the photosensitive material. In addition, the strainer, valve, etc. of the replenishing device system are clogged, which causes many problems such as a decrease in the replenishing amount.

However, as is clear from Experiment 4, by using the color developing replenisher containing the compound represented by the general formula (I) and the aromatic sulfonic acid or a salt thereof, it is possible to obtain a high concentration during continuous processing. It can be seen that even if ultra-low replenishment of the replenisher is performed, various problems such as precipitation of crystals on the drive unit and clogging of the replenisher are not caused.

[0031]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, when a silver halide color photographic light-sensitive material is imagewise exposed and then color development processing is carried out at an extremely low replenishment rate, a compound represented by the general formula (I) and a fragrance are added to a color developing solution. By adding the group sulfonic acid or its salt, a high-concentration color developing replenisher which does not cause precipitation of the color developing agent can be obtained, and low replenishing processing is possible, and it is understood that the industrial application effect is great.

Claims (2)

[Claims] 1. A color developing replenisher for a silver halide color photographic light-sensitive material, which comprises a compound represented by the following general formula (I) 1, and an aromatic sulfonic acid or a salt thereof. [Chemical 1] R ₁ and R ₂ each independently represent an alkyl group which may be substituted with a hydroxyl 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 are substituted with a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitroso group and an alkyl group which may be substituted with these groups. May be. 2. A silver halide color photographic light-sensitive material, after imagewise exposure, is subjected to color development processing by color development replenishment containing a compound represented by the general formula (I) below and an aromatic sulfonic acid or a salt thereof. A method of processing a silver halide color photographic light-sensitive material, which comprises processing while supplementing a liquid. [Chemical 2] R ₁ and R ₂ each independently represent an alkyl group which may be substituted with a hydroxyl 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 are substituted with a hydroxyl group, an alkoxyl group, an amide group, a sulfonamide group, an alkylsulfonamide group, a nitroso group and an alkyl group which may be substituted with these groups. May be.