JPH09197629A - Method for processing halogenated silver photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple method for preventing the generation of sudden lowering of pH without lowering the developing performance even in the case of long time developing by processing the halogenated silver photosensitive material with the developing liquid, which includes a specified compound and which is mainly composed of the ascorbic acid or the derivative thereof. SOLUTION: The halogenated silver photosensitive material is processed with the developing liquid, which includes one kind of the compound expressed with a formula and which is mainly composed of ascorbic acid or the derivative thereof. In the formula, X, Y, Z mean hydrogen atom, hydroxyl group, carboxyl group or amino group. (l), (m), (n) mean the numeric 1 or more. As a compound expressed with the formula, diethanolamine, triethanolamine or the like is used. As the ascorbic acid or the derivative thereof to be used for the developing liquid, L-ascorbic acid, D-ascorbic acid or the like is used. Stabilized pH can be thereby maintained without lowering the developing activity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of developing and processing a silver halide light-sensitive material. More specifically, the present invention relates to a method for stably developing a silver halide photosensitive material over a long period of time using a developing solution containing ascorbic acid as a developing agent.

[0002]

2. Description of the Related Art A silver halide light-sensitive material requires a development step in order to obtain an image after forming an image by exposure. In this processing step, the processing method and the processing agent differ depending on the type of silver halide light-sensitive material. For example, typical processing steps for black-and-white photographic light-sensitive materials are development, fixing, washing with water, and drying. In addition, steps such as bleaching and stabilization may be required.

In the black-and-white developing solution used for processing the silver halide light-sensitive material, the developing agent usually used is generally dichtoxybenzene type such as hydroquinone. However, in recent years, the toxicity of hydroquinone and the pollution load of waste liquid (high COD, BOD) have become problems. When using hydroquinone, not only hydroquinone itself, but also solvents such as diethylene glycol and triethylene glycol used when making concentrated solutions of treating agent kits containing this, and sulfite salts that are indispensable as antioxidants of hydroquinone, Since COD and BOD are increased, as a result, the pollution load becomes very large.

Further, it is well known that sulfite acts as a solvent for silver halide in the developing solution, and silver ions dissolved in the developing solution are reduced to cause so-called silver stain. This is an unavoidable problem as long as hydroquinone is used. To this end, it is necessary to take measures such as adding a silver stain preventing agent at the expense of sensitivity and the like.

Therefore, in recent years, a developer using ascorbic acid as a developing agent has attracted attention. When ascorbic acid is used as a developing agent, its toxicity is low, its water solubility is higher than that of hydroquinone, and it is not necessary to use a solvent such as diethylene glycol. Furthermore, since the amount of sulfite can be greatly reduced, silver stain is reduced.

However, when ascorbic acid is used as a developing agent, a problem different from hydroquinone occurs. That is, when a large amount of silver halide light-sensitive material is processed, the pH is drastically lowered as compared with hydroquinone. For this reason,
This is a problem because the treatment activity becomes lower with a smaller amount of treatment than that of hydroquinone.

To solve this problem, for example, Japanese Patent Laid-Open No. 5-31
The 3318 monitors the pH value using a redox electrode,
The pH value is controlled using an alkaline solution. This method is problematic in that the sensitivity of the electrode to pH becomes a problem, or when the pH is lowered by air oxidation for a long period of suspension and the pH is changed with an alkali, the concentration of the developing agent is extremely decreased. In JP-A-6-19069, it is stated that carbonate ion is added in an amount of 0.5 mol / liter or more, which is larger than in a developer using hydroquinone as a developing agent. However, when a large amount of a carbonate is added, the progress of development of the silver halide light-sensitive material tends to decrease. Also, JP-A-7-92
In 627, the pH of the replenisher is set to be 0.15 or more higher than that of the starter to maintain the pH during running. However, in this method, the replenishment interval and the replenishment amount must be determined in detail, and there is a problem that the method of use becomes complicated.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a developing solution for a silver halide photosensitive material containing ascorbic acid or a derivative thereof as a developing agent without deteriorating the developing property even if the developing process is carried out for a long period of time. An object is to provide a simple method in which the pH does not drop rapidly.

[0009]

The above object of the present invention is to provide a silver halide photographic light-sensitive material containing ascorbic acid or a derivative thereof containing at least one compound represented by Chemical formula 3 or Chemical formula 4 as a developing agent. It was achieved by using a development processing method characterized by processing with a developing solution.

[0010]

Embedded image

[0011]

Embedded image

In the formula, X, Y, Z, V and W represent a hydrogen atom, a hydroxyl group, a carboxyl group or an amino group.
l, m, n, p and q represent integers of 1 or more.

Specific examples of the compounds represented by Chemical formulas 3 and 4 are shown below, but the invention is not limited thereto. , Diethanolamine, triethanolamine, diisopropanolamine, N-methylethanolamine, N-aminoethylethanolamine, N, N-
Dibutylbutanolamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, 3-aminopropanol, 1-amino-propane-
2-ol, 4-aminobutanol, 5-amino-pentan-1-ol, 3,3′-iminodipropanol,
N-ethyl-2,2'-iminodiethanol, 2-amino-2- (hydroxymethyl) propane-1,3-diol, 2-amino-2-methylpropane-1,3-diol, 3-diethylaminopropanoic acid , Hydroxyiminodiacetic acid, trimethylamine, triethylamine, and the like.

The amount of the compound used in the present invention is preferably 0.05 to 1.5 mol, and more preferably 0.3 to 0.9 mol, per liter of the developer used.

The silver halide light-sensitive material used in the present invention is a black-and-white photographic material (for example, a medical or industrial X-ray photographic material, a photolithographic light-sensitive material such as a lith type photographic material, a micro-photographic material, an X-ray micro material. Inverse photographic material, computer typesetting paper, negative photographic material for general photography, photographic paper, etc.).

Further, in the field of graphic arts, an image forming system capable of obtaining super-high contrast photographic characteristics is required in order to improve reproduction of continuous gradation by a halftone dot image, and a hydrazine compound is used in an emulsion or a developing solution. It is known to add. JP-A-7-258782 describes a method in which hydrazine or a substance that promotes nucleation thereof is contained in a photosensitive material and is processed with a developing solution containing ascorbic acid. These photosensitive materials can be used for the developer of the present invention.

Further, JP-A-61-267759 discloses a method of adding a human hydrazine compound and an amino compound which promotes contrast enhancement to a developing solution, JP-A-60-179734 and US Pat. No. 5,104,769. No. 4,798,780, a method using various hydrazine compounds having a high contrast-increasing effect,
JP-A-1-179939 and JP-A-1-179940 disclose a method in which a nucleation accelerator and a hydrazine compound are used in combination, and further, US Pat. Nos. 4,998,604 and 4,994,3.
No. 65 describes a similar method for increasing the contrast, but the processing method of the present invention can be used for processing a light-sensitive material containing a hydrazine compound described therein.
In this case, the effects of the compounds of Chemical formulas 3 and 4 of the present invention are not impaired even if the developer contains an amino compound that promotes contrast enhancement.

The silver halide used in the photosensitive silver halide emulsion layer of the above light-sensitive material is not particularly limited, and silver chlorobromide,
Although silver chloroiodobromide, silver iodobromide, silver bromide, etc. can be used, when silver chloroiodobromide or silver iodobromide is used, the content of silver iodide is 5 mol%. The following is preferable. The morphology, habit crystals, and size distribution of the silver halide grains are not particularly limited, but those having an average grain size of 0.7 micron or less, particularly 0.5 micron or less are preferable, and the total number of grains is 90. % Or more preferably has a particle size within the range of ± 10% of the average particle size. The method for preparing the silver halide emulsion may be any of known methods such as forward mixing, reverse mixing, and simultaneous mixing.

Ascorbic acid or its derivative used in the developing solution of the present invention, for example, L-ascorbic acid, D-ascorbic acid, L-erythroascorbic acid, D-glucoascorbic acid, 6-deoxy-L-ascorbic acid, L-rhamnoascorbic acid, D-glucoheptoascorbic acid, imino-L
-Erythroascorbic acid, imino-D-glucoascorbic acid, imino-6-deoxy-L-ascorbic acid, imino-D
-Glucoheptoascorbic acid, glycoascorbic acid, D-galactoascorbic acid, L-araboascorbic acid, sorboascorbic acid, sodium isoascorbate, sodium ascorbate and the like can be mentioned. These compounds may be salts of alkali metals and the like.

In the ascorbic acid developer used in the present invention, it is preferable to use an auxiliary super-additive developing agent. Examples of this include 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl
-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl -
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, etc.), aminophenols (eg, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) , 1-aryl-3-aminopyrazolidones (eg, 1- (p-hydroxyphenyl) -3-aminopyrazolidone, 1- (p-methylaminophenyl) -3-aminopyrazolidone, 1- ( p-amino-m-methylphenyl) -3-aminopyrazolidone or the like, or a mixture thereof. The combination of ascorbic acids and 1-phenyl-3-pyrazolidones is most preferred for the developing agent used in the black-and-white developer used in the present invention because good performance is easily obtained. In addition, a p-aminophenol-based developing agent may be contained.

In addition to this, LF Mason Photographic Process
ing Chemistry (Focal Press, 1966) 226-229
And those described in JP-A-48-64933 may be used.

These developing agents are usually used in an amount of 0.1 to 80 g / l, preferably 0.2 to 50 g / l. Of these, the auxiliary developing agent exhibiting superadditivity is preferably contained in an amount of 1 to 10% by weight.

In the developer of the present invention, it is not necessary to add a large amount of sulfite ion. However, if it is not added at all, the storability deteriorates, so it is preferable to add a small amount. As the sulfite, for example, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like can be used. The amount of sulfite ion added is preferably 0.01 to 0.3 mol / liter.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, it is in the range of pH 9.0 to 12. In addition to the compounds shown in Chemical formulas 3 and 4, sodium hydroxide,
Inorganic compounds such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate may be included.

As additives used in addition to the above components, development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol. Such an organic solvent may be contained, and if necessary, a toning agent, a defoaming agent, a water softening agent and the like may be contained.

[0026]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example developer water 600 ml sodium sulfite 10 g pH buffer X mol ascorbic acid 30 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 0.7 g benzotriazole 0.2 g NaBr 1.5 g ethylenediamine tetra Acetic acid disodium salt 1 g After adding water to make 1 L, pH was adjusted to 10.50 with KOH.
(25 ° C.).

Comparative Examples 1 and 2 are prepared by adding 0.5 mol and 1.0 mol of potassium carbonate per liter as a pH buffering agent to the above developing solution. Moreover, what added 1 mol of diethanolamine, triethanolamine, hydroxyiminodiacetic acid, and triethylamine as a pH buffer agent per liter is set as this invention 1, 2, 3, 4.

Comparative Examples 1 and 2 and Inventions 1 to 4 were used in a developing tank of LD221 (automatic developing machine manufactured by Dainippon Screen Co., Ltd.).
The developer is added and the fixer is used as a fixer in Mitsubishi Paper Mills Ltd.
CF901 manufactured by K.K. Light sensitive film for light room (DCL
-EHF trade name (manufactured by Mitsubishi Paper Mills, Ltd.) was exposed through a step wedge with a reversing printer for light room P617 (manufactured by Dainippon Screen Co., Ltd.) and processed at 38 ° C for 20 seconds. Similarly, a light-sensitive film light-sensitive material was exposed to a document such that the image was 50% of the whole, and after processing 10 m ² per liter, DCL-EHF similarly exposed to a step wedge was processed.

The maximum density (Dmax), the minimum density (Dmin) and the sensitivity of the wedge sample prepared by the above method were measured using a Macbeth densitometer TR927. The measurement results are shown in Tables 1 and 2. In Tables 1 and 2, the sensitivities are shown as relative values with the reciprocal of the exposure amount required to obtain a transmission density of 3.0 in Comparative Example 1 being 100.

[0031]

[Table 1]

[0032]

[Table 2]

As can be seen from Tables 1 and 2, Comparative Example 1
The developing solution of No. ² had a drastic drop in pH after treatment of 10 m ² per liter, and the photographic characteristics changed significantly. Further, the developing solution of Comparative Example 2 had no change in pH, but the sensitivity and the maximum density were low from the beginning. On the other hand, the developer of the present invention is 10 m ² even in the initial processing.
Even after the processing, the photographic characteristics did not change, and the processing could be performed stably. Further, the developer of the present invention was so small that the change from the initial pH was not a problem.

[0034]

According to the present invention, it is possible to maintain a stable pH in a developing solution for a silver halide light-sensitive material without degrading the developing activity.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material is treated with a developing solution containing ascorbic acid or a derivative thereof containing at least one compound represented by Chemical formula 1 or Chemical formula 2 as a developing agent. Development processing method. Embedded image Embedded image In the formula, X, Y, Z, V and W are hydrogen atom, hydroxyl group,
Represents a carboxyl group or an amino group. l, m, n,
p and q represent an integer of 1 or more.