JP2002156732A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable method which does not cause environment pollution and in which toxic hydroquinone is not used as a processing method for a silver halide photographic sensitive material. SOLUTION: A developing solution of pH 9.8-10.5, not substantially containing a dihydroxybenzene developing agent or containing at least (a) 0.1-0.4 mol/l ascorbic acid or its derivative, (b) 0.001-0.25 mol/l 3-pyrazolidone auxiliary developing agent and/or p-aminophenol auxiliary developing agent, (c) 0.3-0.5 mol/l carbonate and (d) 0.1-0.4 mol/l sulfite is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a black-and-white silver halide photographic material using a developing solution which does not contain a hydroquinone-based developing agent having a large environmental load. The present invention relates to a processing method with improved stability.

[0002]

2. Description of the Related Art Generally, for plate making, microphotography, X
Black-and-white silver halide photographic materials for radiography and the like are developed with an alkaline developing solution containing hydroquinone as a developing agent and a 3-pyrazolidone compound or an aminophenol compound as an auxiliary developing agent, followed by fixing and washing with water. An image is formed by a development process through the steps. Particularly in rapid processing, a highly active developer containing a large amount of hydroquinone is used. However, with increasing awareness of environmental problems in recent years, the potential toxicity of hydroquinone-based developing agents has become a problem. As developing agents replacing hydroquinone, US Pat. No. 2,688,549
And ascorbic acid and derivatives thereof described in JP-A No. 3-249756 and JP-A-3-249756 are known.

However, a developer using ascorbic acid or a derivative thereof in place of hydroquinone has a problem that the pH tends to decrease over time. Since the developing activity of the developer is proportional to the pH,
If H decreases, the desired image density cannot be obtained. For this reason, a large amount of a buffer such as a carbonate is added to a developing solution containing an ascorbic acid-based compound as a developing agent in order to prevent a decrease in pH.

[0004]

However, a developer using an ascorbic acid-based compound as a developing agent has a higher stability than a conventional hydroquinone developer even when such a large amount of a buffer is added. There is a problem of inferiority. In particular, in rapid processing, in order to complete the development within a short development time, it is important to maintain the initial activity of the developer, and a decrease in the activity of the developer immediately leads to a decrease in image density. become. In addition, in recent years, due to increasing awareness of environmental problems, low replenishment processing which does not generate waste liquid of the processing liquid as much as possible has been demanded. However, it has been difficult to reduce the replenishment amount of a developing solution containing an ascorbic acid-based compound as a main agent because of its low stability.

Accordingly, an object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having excellent stability which enables rapid processing and low replenishment processing without using toxic hydroquinone. is there.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that when performing low replenishment processing using a developing solution containing an ascorbic acid-based compound as a developing agent, a buffer agent sufficient to maintain pH is used. In addition, it is found that the addition results in inferior stability, and the amount of the buffering agent is reduced to a predetermined amount while the auxiliary developing agent concentration and the sulfite concentration of the preservative are also set to the predetermined amounts. The remarkably low replenishment processing suitability has been improved, and it has been found that excellent rapid processing suitability can be maintained over a long period of time, leading to the present invention.The present invention is substantially free from dihydroxybenzene-based developing agents. Containing at least the following compound, and having a pH of 9.8 to 10.5.
The use of a developing solution is characterized in that: a. 0.1 to 0.4 mol / l ascorbic acid or a derivative thereof. b. 0.001-0.25 mol / l 3-pyrazolidone type auxiliary developing agent and / or p-aminophenol type auxiliary developing agent. c. 0.3-0.5 mol / l carbonate. d. 0.1-0.4 mol / l of sulfite.

With such a configuration, the development processing time is 2
Stable processing can be performed even in a rapid processing of 0 seconds or less. In addition, low replenishment processing, in particular, replenishing only water or processing liquid in an amount that does not substantially cause overflow drainage, or processing the specified amount of photosensitive material without replenishment at all and then replacing the whole processing liquid The present invention shows a remarkable effect in the non-replenishment processing, that is, the disposable processing.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, ascorbic acid or a derivative thereof used as a substitute for the hydroquinone-based developing agent can be represented by the following general formula (I). General formula (I)

Embedded image In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, a mercapto group, an acylamino group, an allylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group or an alkylthio group, and X represents a carbon atom, oxygen R ₁ , R ₂
Forms a 5- or 6-membered ring together with the two substituted vinyl carbons and the carbonyl carbon.

Specific examples of the ascorbic acid or its derivative represented by the general formula (I) include L-ascorbic acid, D-ascorbic acid, erythorbic acid, L-glycoscorbic acid, L-glucoascorbic acid, D-galactoscorbic acid, L-araboascorbic acid, sorbascorbic acid, 6-deoxy-L-ascorbic acid, L-rhamnoascorbic acid, D-glucoheptoascorbic acid, imino-L-erythorbic acid, imino- D
-Glucoascorbic acid, imino-6-deoxy-L-
Ascorbic acid, imino-D-glucoheptoascorbic acid and the like. These can be used in the form of an alkali metal salt such as a sodium salt, a potassium salt and a lithium salt.

The ascorbic acid or a derivative thereof used in the present invention is used in an amount of 0.1 to 0.4 mol per liter of a developing solution. If the amount is less than 0.1 mol / l, the necessary developing activity cannot be obtained, and if the amount is more than 0.4 mol / l, the amount of acid which is oxidized increases, so that the pH of the developing solution is increased. However, it becomes easier to fall, and it becomes difficult to maintain the necessary developer activity. From the viewpoint of photographic characteristics and stability of the developing solution, 0.1 to 0.1.
The use of 3 mol / l is preferable, and the use of 0.12 to 0.22 mol / l is particularly preferable in the case of using the non-replenishing method in view of the stability of the developing solution.

The developer used in the present invention contains 0.3 to
0.5 mol / l carbonate is added. By setting the amount of the carbonate added to this range, low replenishment treatment, especially in a non-replenishment method in which only the processing solution is not replenished at all or only the amount of water or the processing solution which does not substantially cause overflow drainage is replenished. In addition, stable processing in which development activity is maintained for a long period of time can be achieved. As the carbonate, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and the like can be preferably used.

The developer used in the present invention contains 0.00
1 to 0.25 mol / l of an auxiliary developing agent is added. The auxiliary developing agent as used herein refers to a 3-pyrazolidone developing agent and a p-aminophenol developing agent which are known to exhibit superadditivity in combination with hydroquinone in a hydroquinone developing solution. Specific compounds of the 3-pyrazolidone developing agents include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-p
-Aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. is there. Examples of p-aminophenol-based developing agents include p-aminophenol and N-
Examples include methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, and p-benzylaminophenol. In the developer used in the processing method of the present invention, 1-phenyl-3-pyrazolidone among these compounds can be particularly preferably used in view of photographic characteristics.

To the developer used in the present invention, 0.1 to 0.4 mol / l of a sulfite is added as a preservative. If the added sulfite is 0.1 mol / l or less, the preservative performance is inferior, and the developing agent is easily oxidized, so that the required developing activity cannot be maintained. Since the amount of silver sludge generated when processing the light-sensitive material increases in proportion to the amount of sulfite added, it is desirable to add as little as possible the amount of sulfite, so the optimal amount depends on the main agent amount and pH of the developer used. The amount is determined. In the developer used in the present invention, the addition of 0.25 to 0.35 mol / liter is optimal from the viewpoint of both the preservation performance and the amount of silver sludge generated. As the sulfite, sodium sulfite, potassium sulfite, sodium bisulfite, potassium metabisulfite and the like can be preferably used.

The developer used in the present invention has a pH of 9.8.
It is used in the range of ０．５10.5. When used at a lower pH, the developing activity is too low, and it is difficult to maintain the developing activity required for rapid processing. On the other hand, when used at a higher pH, ascorbic acid or its derivative, which is the main drug, is significantly deteriorated, and the stability of the developing solution is deteriorated. In particular, when used in the non-replenishment mode, the pH is 9.8 to 1
Use in the range of 0.3 is preferred from the viewpoint of stability. Sodium hydroxide, potassium hydroxide and the like can be used as an alkali agent for adjusting the pH of the developer to a desired pH.

The developer used in the present invention may further include an inorganic development inhibitor such as potassium bromide or potassium iodide, benzotriazole, 5-methylbenzotriazole,
Organic development inhibitors such as nitroindazole can be added.

Further, if necessary, it may contain a surfactant, a hardening agent, a color tone adjusting agent and the like. Examples of the water quality regulator include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid,
-Phosphonobutane-1,2,4-tricarboxylic acid, 1,
1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, 1 A chelating agent represented by aminopolycarboxylic acid such as -hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acid or a salt thereof can be added.

The developer used in the present invention can be supplied as a working solution or a 2-3 times concentrated solution.

As the fixing solution used in the present invention, an aqueous solution containing thiosulfate as a main fixing agent can be preferably used. Representative thiosulfates include ammonium thiosulfate and sodium thiosulfate. The pH of the fixing solution is preferably 3.8 or more, particularly 4.2 to 7.0.
It is. Further, the fixing solution may contain a water-soluble aluminum salt (aluminum sulfate, aluminum chloride, etc.) as a hardening agent, and at the same time, use an organic acid (tartaric acid, citric acid, gluconic acid, etc.) for the purpose of suppressing precipitation of the aluminum salt. May be included. In addition, preservatives such as sulfites, buffering agents (acetic acid, boric acid, etc.), p
A water quality adjusting agent such as an H adjusting agent and a chelating agent can be preferably contained.

[0019]

EXAMPLES Next, the present invention will be described specifically with reference to examples. Example 1 A commercially available microfilm (sensitive material name:
Kodak IMAGELINK HQ MICROF
ILM ("IMAGELINK" is a registered trademark of Eastman Kodak Company) was treated under the following conditions.

[0020]

[Table 1] After dissolving the compositions shown in Table 1, each of the test solutions was tested. (1) to (3) are KOH and pH = 10.00
To the test developer No. (4) is KOH, pH = 1
After adjusting to 0.10, each was added with water to make 1.0 liter to prepare each test developer. Incidentally, Liprodol F manufactured by Chugai Photochemical Co., Ltd. was used as the fixing solution.

The test processing conditions are as shown in Table 2.

[Table 2] In addition, each processing liquid was performed without replenishment, and water washing was also carried out and water washing was performed.

Under the above conditions, each of the test developers was subjected to a running test in which the exposed microfilm having a width of 16 mm was processed every 3 m every day except for Saturday and Sunday, and a total of 30 m was processed in two weeks. Evaluation of each processing method,
Control at the start and end of the running test
The strips were processed and evaluated by comparing the performance of the following items.

Photographic Density Value The photographic density of a solid exposure patch (approximately density 1.0) exposed on a control strip was measured using a densitometer X-Rite
361T was used to measure the photographic density from the start to the end of the running, and the developer stability of each processing method was measured. This decrease in density was represented by what percentage of the photographic density at the end of running, when the density value at the start was 100%.

Resolution Using a JIS resolution test chart (JIS Z6008-1982) exposed on a control strip, the stability of the developer in each processing method was evaluated by comparing the resolution at the start and the end of the running. did.

Evaluation of resolving power 〇: There is no difference in resolving power between the start and the end. Δ: The resolving power at the end is slightly inferior to that at the start. X: The resolving power at the end is significantly inferior to that at the start.

Contamination of Film and Automatic Developing Machine For film contamination, the degree of contamination by silver sludge on the film processed daily was compared. In addition, the contamination of the automatic developing machine was evaluated by checking the silver sludge stain in the developing tank at the end of the running.

Table 3 shows the evaluation results.

[Table 3]

From the results of the processing method using the test developer (3), in the non-replenishment system, when the carbonate as a buffer is added in an amount exceeding the range of the present invention, the decrease in pH is suppressed. As a result, it turns out that the stability of the developer is inferior. Further, when erythorbic acid, which is an ascorbic acid-based developing agent, as in the test developer (2) is added in an amount exceeding the range of the present invention, the pH of the developer significantly decreases, and the required developing activity cannot be maintained. I understand.

In comparison, the processing method of the present invention using the test developer (1) shows the same development stability as that of the test developer (4) using the hydroquinone developing agent. Furthermore, the processing method of the present invention using the test developer (1) has less generation of silver sludge than the case where the test developer (4) using a hydroquinone developing agent is used. It can be seen that there is little pollution.

Example 2 A running test was carried out under the same conditions as in Example 1 using the following test developers. Test developer No. (5): Test developer No. used in Example 1. Using the same composition as in (1), use KOH to adjust pH
= 10.50. Test developer No. (6): No. of test developer used in Example 1. Using the same composition as in (1), use KOH to adjust pH
= 10.60. Test developer No. (7): Test developer No. used in Example 1. Using the same composition as in (1), use KOH to adjust pH
= 9.78. Test developer No. (8): Test developer No. used in Example 1. Using the same composition as in (3), use KOH to adjust pH
= 10.50.

Table 4 shows the results of the same evaluation as in Example 1.
Shown in

[Table 4]

Test developer No. The processing method of the present invention using (5) and a test developer N containing a large amount of carbonate
o. Comparing the processing methods using (8), the developer pH
It can be seen that the effect of the present invention is particularly remarkable when is high. The test developer No. (6) or the test developer No. Comparing the results using (7), it can be seen that stable processing can be achieved if the developer pH is within the range of the present invention from the time of running to the time of completion. In particular, at both the start and end, the test developer No. having a pH outside the range of the present invention was used. It can be seen that the method using (7) is extremely inferior in stability.

[0033]

As described above, according to the method of the present invention, ascorbic acid or a derivative thereof can be used without using a toxic dihydroxybenzene-based developing agent represented by hydroquinone, and the stability can still be obtained. Even when performing rapid processing with a replenishment amount significantly reduced by a method excellent in the above, stable development processing in which development activity is maintained for a long period of time is possible.

Claims (3)

[Claims] Claims: 1. A composition containing at least the following compound without substantially containing a dihydroxybenzene-based developing agent,
9.8 to 10.5, using a developing solution. a. 0.1 to 0.4 mol / l ascorbic acid or a derivative thereof. b. 0.001-0.25 mol / l 3-pyrazolidone type auxiliary developing agent and / or p-aminophenol type auxiliary developing agent. c. 0.3-0.5 mol / l carbonate d. 0.1-0.4 mol / l sulfite 2. The processing method for a silver halide photographic material according to claim 1, wherein the development processing time is 20 seconds or less. 3. The processing of a silver halide photographic light-sensitive material according to claim 1, wherein water or a processing solution is replenished without replenishment or in an amount that does not substantially cause overflow drainage. Method.