JP2005031513A - Sulfurous-acid-containing aqueous solution and method for storing the aqueous solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developing solution for a silver halide photographic sensitive material and a method for storing the same by which when an alkaline aqueous solution containing sulfurous acid is stored in a plastic container, deposition due to leached matter from the container can be suppressed, and particularly even in the case of storing a processing agent of a high pH containing sulfurous acid, such as a developing solution for a silver halide photosensitive material, no occurrence of an insoluble deposit by leached matter from a storage container is ensured and long-term stable storage is enabled. <P>SOLUTION: The sulfurous-acid-containing aqueous solution is an aqueous solution of ≥pH 9.0 containing a sulfite, wherein an Na to K molar ratio is ≤0.1. In a method for storing an aqueous solution of ≥pH 9.0 containing a sulfate in a plastic container, an Na to K molar ratio in the sulfurous-acid-containing aqueous solution stored in the container is adjusted to ≤0.1. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an alkaline aqueous solution containing sulfurous acid and a method for storing the aqueous solution, and particularly when a developer for a silver halide photosensitive material is stored, the aqueous solution containing sulfurous acid that can be stably stored for a long period of time and the aqueous solution. It relates to the storage method.

  Is the developer for the silver halide photosensitive material, which is an alkaline solution containing sulfurous acid, supplied as a concentrated solution or part solution and mixed with water at a predetermined ratio at the time of use and used as a use solution and a replenisher solution? Or, it is generally supplied as a use liquid and taken out from the packaging material at the time of use and used as it is.

  Most of these developers are stored in containers such as bottle type, cubic type, film type, standing pouch type, bag-in-box, etc., and supplied to users.

  However, when a processing agent containing a sulfite of 0.1 mol / liter or more at a high pH such as a developer for a silver halide photosensitive material is stored in the above packaging container for a long time, from the liquid contact surface of the container material A part of the material component is eluted, and precipitates are generated in the developer. This insoluble precipitate is thought to be derived from additives such as plasticizers, antistatic agents, anti-aging agents, UV absorbers, stabilizers, and lubricants added to the polymer material. The product does not re-dissolve in the developing solution, significantly lowers the commercial value, and also causes various troubles such as adhering to the photosensitive material during photographic processing and clogging the circulation system of the automatic processor. The technique for suppressing the exudation of the eluate from the container material is, for example, a technique related to a polyolefin having a specific structure or composition (for example, see Patent Documents 1 to 3), or a technique related to a polyamide having a specific physical property (for example, Patent Documents). 4). In addition, according to the ordinance of milk and the like, containers used for storage of yogurt and the like have established a certain standard regarding the amount of elution on the wetted surface in consideration of the adverse effects of the elution. When the aqueous alkali sulfite solution is stored in these containers, although a reduction in the amount of elution is confirmed, it is not a satisfactory level.

JP 7-178150 A JP-A-9-85913 JP-A-9-308682 JP 2001-328681 A

  Accordingly, an object of the present invention is to provide a sulfite-containing aqueous solution that suppresses precipitation due to an eluate from a container when an alkaline aqueous solution containing sulfurous acid is stored in a plastic container, and a method for storing the aqueous solution. Halogens that can be stored stably for a long period of time, even when storing processing agents containing sulfurous acid at high pH, such as developer solutions for materials, without the generation of insoluble precipitates due to eluate from the storage container It is an object to provide a developer for a silver halide photographic light-sensitive material and a storage method thereof.

The object of the present invention is solved by the following means.
(1) A sulfite-containing aqueous solution, which is an aqueous solution containing sulfite and having a pH of 9.0 or more, wherein the molar ratio of Na / K is 0.1 or less.
(2) The aqueous sulfuric acid solution according to (1), wherein the aqueous sulfuric acid solution contains 0.1 mol or more of sulfite per liter.
(3) The aqueous sulfurous acid solution according to (1) or (2), wherein the aqueous sulfuric acid solution is a processing solution for a silver halide photographic light-sensitive material.
(4) The aqueous sulfuric acid solution according to (1) or (2), wherein the aqueous sulfuric acid solution is a developer for a silver halide photographic material.
(5) In a method of storing an aqueous solution containing sulfite and having a pH of 9.0 or more in a plastic container, the molar ratio of Na / K of the aqueous sulfite solution stored in the container is 0.1 or less. A method for storing a sulfite-containing aqueous solution.
(6) The method for preserving a sulfite-containing aqueous solution according to (5), wherein the sulfite-containing aqueous solution contains 0.1 mol or more of sulfite per liter.
(7) The method for preserving a sulfite-containing aqueous solution as described in (5) or (6) above, wherein the sulfite-containing aqueous solution is a processing solution for a silver halide photographic light-sensitive material.
(8) The method for preserving a sulfite-containing aqueous solution as described in (5) or (6) above, wherein the sulfite-containing aqueous solution is a developer for a silver halide photographic light-sensitive material.

  According to the present invention, when an alkaline aqueous solution containing sulfurous acid is stored in a plastic container, it is possible to suppress precipitation due to the effluent from the container. Even when storing a processing agent containing sulfurous acid at a high pH, such as a developer for a silver halide photosensitive material, insoluble precipitates are not generated due to eluate from the storage container, and stable for a long period of time. Saving is now possible. The product value of the alkaline aqueous solution containing sulfurous acid stored in the plastic container is maintained, and insoluble precipitates due to eluate from the storage container adhere to the photosensitive material during photographic processing, and the circulation system of the automatic processor is used. Various troubles such as clogging can be prevented.

  The sulfite-containing aqueous solution of the present invention and the sulfite-containing aqueous solution used for the storage method of the aqueous solution contain sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, an amine sulfite adduct and the like. The concentration of sulfite is not particularly limited, but in the case of a sulfite-containing aqueous solution of less than 0.1 mol / liter, the generation of insoluble matter from the container is not observed or is minimal, and in the case of 0.1 mol / liter or more, The effectiveness of the present invention remarkably appears.

  In the alkaline sulfite-containing aqueous solution used in the storage method of the present invention, a normal water-soluble inorganic alkali metal salt (for example, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, etc.) can be used as an alkaline agent. When the pH of the aqueous sulfite solution is less than 9.0, the generation of insoluble matter from the container is not observed or is negligible. When the pH is 9.0 or more, particularly when the pH is 9.5 or more, the effectiveness of the present invention is remarkable. Appear in

  When the alkaline aqueous sulfite solution used in the storage method of the present invention is Na / K of the aqueous solution, that is, when the molar ratio of sodium to potassium is 0.1 or less, generation of insoluble matter from the storage container is effectively suppressed, and 0 0.08 or less is more preferable, and 0.05 or less is most preferable.

  Examples of the processing solution for the silver halide photosensitive material of the present invention include a developing solution for a silver halide photosensitive material, a color developing solution for a silver halide color photosensitive material, and the like. Part liquid etc. are mentioned when it is supplied by. Among them, a monochrome developer, particularly an X-ray developer, contains a large amount of sulfite and easily generates precipitates. Therefore, depending on the sulfite-containing aqueous solution of the present invention and the storage method of the aqueous solution, The occurrence of precipitation can be prevented even in the storage state.

The processing solution for silver halide photographic light-sensitive material used in the present invention will be described below.
The developer for a silver halide photographic light-sensitive material of the present invention contains a developing agent. As a developing agent, dihydroxybenzene-based developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, Examples include, but are not limited to, potassium hydroquinone monosulfonate. As an ascorbic acid developing agent, L-ascorbic acid, D-ascorbic acid, L-erythroascorbic acid, D-glucoascorbic acid, 6-deoxy-L-ascorbic acid, L-rhamnoascorbic acid, D-glucoheptaascorbine Acid, imino-L-erythroascorbic acid, imino-D-glucoascorbic acid, imino-6-deoxy-L-ascorbic acid, imino-D-glucoheptascorbic acid, sodium isoascorbate, L-glycoscorbic acid, D -Galactose ascorbic acid, L-araboascorbic acid (erythorbic acid), sorboascorbic acid, ascorbic acid and their salts. Examples of the salt include, but are not limited to, alkali metal salts such as sodium salt and potassium salt. The amount used is 0.10 to 1.0 mol / L, more preferably 0.2 to 0.7 mol / L in the case of a dihydroxybenzene developing agent. Ascorbic acid developing agents are preferably used in an amount of 0.01 to 0.8 mol / L, more preferably 0.1 to 0.4 mol / L.

  The developer for silver halide photographic light-sensitive material of the present invention contains sulfite as a preservative. Examples of sulfites include, but are not limited to, sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite. The amount of sulfite used is preferably 0.06 to 1.5 mol / L, more preferably 0.3 to 1.0 mol / L.

  The developer for a silver halide photographic light-sensitive material of the present invention preferably uses a 3-pyrazolidone-based or p-aminophenol-based auxiliary developing agent in combination. Examples of 3-pyrazolidones include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 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. Of these, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone is preferred.

  Examples of p-aminophenols include N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) -glycine, 2-methyl-p-amino. There are phenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable.

  When 1-phenyl-3-pyrazolidones or p-aminophenols are used in combination with an auxiliary developing agent together with a developing agent, the former is 0.01 mol / L to 0.5 mol / L and the latter is 0.001 mol / L. It is preferably used in an amount of L to 0.1 mol / L.

  The developer for a silver halide photographic light-sensitive material of the present invention may contain carbonate or phosphate as a buffer. As the carbonate, those having high water solubility are preferable, and examples thereof include potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like, and examples of the phosphate include tribasic sodium phosphate and tribasic potassium phosphate. . The amount used is preferably 0.05 to 1.0 mol / L, more preferably 0.10 to 0.6 mol / L.

  The developer for a silver halide photographic light-sensitive material of the present invention is set to pH 9.0 or higher, preferably pH 9.5 or higher. As the alkali agent, usual water-soluble inorganic alkali metal salts (for example, sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, etc.) can be used.

  The developer for a silver halide photographic light-sensitive material of the present invention includes a development inhibitor such as potassium bromide and sodium bromide, an organic solvent such as ethylene glycol and diethylene glycol, a water quality adjusting agent, and a surfactant if necessary. , A foam-extinguishing agent, a hardening agent, and the like may be included.

  The Na / K molar ratio of the developer for silver halide photographic light-sensitive materials of the present invention is 0.1 or less. When the ratio is higher than this, there is a case where precipitates are generated due to elution of insoluble substances from the liquid contact surface of the packaging container due to long-term storage, thereby impairing the commercial value. The molar ratio of Na / K is more preferably 0.08 or less, and most preferably 0.05 or less.

  Next, the color developing solution for silver halide color light-sensitive material of the present invention will be described. Examples of the color developing solution for a silver halide color light-sensitive material of the present invention include a working solution, a concentrated solution, or a plurality of concentrated part solutions.

  In the color developer of the present invention, a color developing agent, an antioxidant, a chelating agent and other additives as shown below can be used in addition to the sulfite compound and the alkali agent.

  The color developing agent is preferably a paraphenylenediamine type, and examples thereof include the following. 4-amino-3-methyl-N, N-diethylaniline, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N -(Β-methanesulfonamidoethyl) aniline, 4-amino-N-butyl-N- (β-butyl sulfonate) aniline and the like. The amount of the color developing agent used is preferably 0.005 to 0.03 mol, more preferably 0.007 to 0.02 mol per liter of the color developer.

  Sulphite is used as the antioxidant. The amount used is preferably from 0.01 to 0.2 mol per liter of color developer. As other antioxidants, hydroxylamine, N-alkylhydroxylamine, N, N-dialkylhydroxylamine and the like and derivatives thereof can be used. The amount used in this case is preferably 0.01 to 0.1 mol per liter of color developer.

  As the chelating agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid or phosphonocarboxylic acid can be used, and the amount used is preferably 0.2 to 5 g per liter of color developer. As the alkali agent, sodium hydroxide, potassium hydroxide, or the like can be used.

  As the pH buffering agent, alkali metal borates, carbonates, bicarbonates, phosphates, and the like can be used. In addition, alkali metal chloride salts, bromide salts, iodide salts, benzimidazoles, and benzothiazoles can also be used as development inhibitors. An organic solvent such as ethylene glycol, diethylene glycol, polyethylene glycol, N-methyl-2-pyrrolidone may be added. Furthermore, surfactants such as polyoxyethylene alkylphenyl ether and triazinyl stilbene-based fluorescent whitening agents can be added. The pH of the color developer of the present invention is 9.0 or more, particularly preferably 9.0 to 11.5, and more preferably 9.5 to 10.5.

  The color developer is generally assembled in a product form as a concentrated solution from the viewpoint of storage cost and transportation cost. In this case, in order to improve the stability of each composition, it is divided into, for example, an alkali agent part, a color developing agent part, and an antioxidant part. In this case, sulfurous acid is preferably added to the alkaline agent part in order to prevent decomposition into sulfur dioxide.

  The molar ratio of Na / K in the color developing solution for silver halide color photographic light-sensitive material of the present invention or the alkaline agent part containing sulfurous acid is 0.1 or less. If the ratio of potassium ions is lower than this, there is a case where precipitates are generated due to elution of insoluble substances from the liquid contact surface of the packaging container due to long-term storage, thereby impairing the commercial value. The molar ratio of Na / K is more preferably 0.08 or less, and most preferably 0.05 or less.

Next, the packaging material used in the present invention will be described.
The material of the wetted surface of the plastic container used for storage of the aqueous sulfuric acid solution of the present invention is not particularly limited, but materials selected from the following group A are mainly used.
Group A Polyolefin Ethylene-vinyl acetate copolymer Ethylene-vinyl alcohol copolymer Polyester Polyamide

  In addition to the materials shown in Group A, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, acrylonitrile resins, polyvinyl alcohol resins, polyvinylidene halide resins, and the like are preferably used. These materials include plasticizers such as camphor, phthalate ester, phosphate ester, metal particles such as copper and aluminum, antistatic agents such as graphite and carbon black, anti-aging agents, and ultraviolet absorption such as trivalent iron powder. Additives such as agents, stabilizers such as lime carbonate, asbestos, glass fiber, and lubricants such as talc, kaolin, and molybdenum disulfide may be appropriately selected and added.

  The form of the container using Group A is not particularly limited, and examples include a bottle type, a cubic type, a film type, and a standing pouch type. In particular, it is a flexible type obtained by processing film materials such as film type, standing pouch type, bag-in-carton type, pillow (three-side seal) type, stick type, etc. Especially, the material of the wetted surface is low density polyethylene (LDPE) In addition, in the case of a container which is a linear low density polyethylene (LLDPE) having excellent performance in strength and stress cracking property among them, in the case of storing an aqueous solution containing sulfite, pH 9.0, more particularly pH 9.5 or more, Since there is much dissolution from the container and it is easy to be noticed even when it is deposited, the effect of setting the Na / K molar ratio to 0.1 or less can be clearly obtained. The container may further have a multilayer structure made of a plurality of materials for the purpose of improving strength, gas barrier properties and the like. In this case, in addition to the materials shown in Group A, polyamide resins, polyethylene terephthalate resins, polyethylene naphthalate resins, acrylonitrile resins, polyvinyl alcohol resins, poly (vinylidene halide) resins, ceramics, aluminum, and the like are preferably used. It is done.

The present invention will be described below with reference to examples.
As shown in Table 1 below, as test developers, Comparative Examples 1 to 8 and Developers 1 to 8 of the present invention, which are Examples of the present invention, were prepared. It was put in the container of the material. This was left in a 50 ° C. constant temperature bath for 200 hours, and then the state of the developer was visually confirmed.

Further, as shown in Table 2 below, alkaline part solutions of color developing solutions for silver halide color light-sensitive materials of Comparative Examples 9 to 11 and Inventions 9 to 12 which are examples of the present invention were prepared. Similarly, after standing in a thermostatic bath at 50 ° C. for 200 hours, the state of the developer was visually confirmed.

(result)
The developing solutions for silver halide photosensitive materials of Comparative Examples 1 to 8 have a high molar concentration of sodium ions with respect to potassium ions (exceeding 0.1), and generation of eluate from the container is observed after the heat storage test ( However, in Comparative Example 6, since the concentration of sulfurous acid is low, generation of eluate is not observed.) On the other hand, in the developing solutions for silver halide photosensitive materials of 1 to 8 of the present invention in which the molar concentration of sodium ions with respect to potassium ions is low (0.1 or less), generation of eluate from the container is not observed.

  In the alkaline part of the color developing solution for silver halide color light-sensitive materials, when the molar concentration of sodium ions relative to potassium ions is high (exceeding 0.1), elution is observed after the heat storage test (Comparative Examples 9 to 11). ), The alkali concentration of 9 to 12 of the present invention in which the molar concentration of sodium ion relative to potassium ion was lowered (0.1 or less), generation of eluate from the container was not observed.

Claims (8)

  A sulfite-containing aqueous solution containing a sulfite and having a pH of 9.0 or more and a Na / K molar ratio of 0.1 or less.   The aqueous sulfite solution according to claim 1, wherein the aqueous sulfite solution contains 0.1 mol or more of sulfite per liter.   The aqueous sulfuric acid solution according to claim 1 or 2, wherein the aqueous sulfuric acid solution is a processing solution for a silver halide photographic light-sensitive material.   The aqueous sulfuric acid solution according to claim 1 or 2, wherein the aqueous sulfuric acid solution is a developer for a silver halide photographic light-sensitive material.   A method for preserving an aqueous solution containing sulfite and having a pH of 9.0 or higher in a plastic container, wherein the molar ratio of Na / K of the aqueous sulfurous acid solution stored in the container is 0.1 or less. Storage method of aqueous solution.   6. The method for preserving a sulfite-containing aqueous solution according to claim 5, wherein the sulfite-containing aqueous solution contains 0.1 mol or more of sulfite per liter.   The method for preserving a sulfite-containing aqueous solution according to claim 5 or 6, wherein the sulfite-containing aqueous solution is a processing solution for a silver halide photographic light-sensitive material.   The method for preserving a sulfite-containing aqueous solution according to claim 5 or 6, wherein the sulfite-containing aqueous solution is a developer for a silver halide photographic light-sensitive material.