TW201446140A - Tablet for preparing chlorine dioxide solution - Google Patents

Abstract

The present invention provides a tablet containing a metal chlorite, a chloride-releasing compound which would release chloride when contacting with water, a solid acid source, a metal stearate and a high molecular disintegrating agent, the total amount of the metal stearate and the high molecular disintegrating agent with respect to the whole tablet is in the range of 0.3 to 10% by weight. Regardless of the scale of the facility to be treated, the tablet can produce chlorine dioxide with a sufficient amount within a practicable time, and has a sufficient strength to prevent damages during moving and operation, and has good productivity.

Description

a tablet for preparing a chlorine dioxide solution

The present invention relates to a tablet for safe and simple preparation of an aqueous solution of chlorine dioxide, which is used for eliminating various uses such as bacteria, viruses, malodorous substances, molds, algae, water, odor, and divalent metal ions of water. use.

Chlorine dioxide is used as a strong oxidant in a wide range of applications such as bleaching, sterilization, virus inactivation, algae killing, iron removal, manganese removal, and elimination of water odor. However, although chlorine dioxide having such a useful use has various problems on the practical side.

Chlorine dioxide is explosive, toxic, and decomposable to light and heat in a gaseous state, and therefore cannot be directly transported in a gaseous state. Further, in the state of a chlorine dioxide solution having a higher stability than a gas, it is difficult to maintain the concentration of chlorine dioxide in the solution. Therefore, the US Environmental Protection Agency, the US Food and Drug Administration, the Ministry of Health, Labour and Welfare, etc., stipulate that chlorine dioxide should be produced in the actual place of use.

As a result, a device for generating a large amount of chlorine dioxide solution for large-scale water treatment has been developed and sold. However, the chlorine dioxide solution generating device is expensive. Moreover, the control of the reaction is difficult and requires complicated Drug management.

Specifically, in the conventional treatment with chlorine dioxide, a method of using a dangerous acid such as chlorine gas, hydrochloric acid or sulfuric acid which is dangerous in operation is generally used. Such a strong acid or chlorine gas can efficiently generate the reverse side of chlorine dioxide due to high reactivity, and the operation is extremely dangerous. Therefore, in order to maintain safety, a method in which a hypochlorite, an oxidizing agent, and a chlorite are prepared in individual tanks, and each solution is diluted with water, and then dispensed into a reaction tank to form a chlorine dioxide solution is used. Or a method of reacting chlorite with hydrochloric acid in a reaction tank to form a chlorine dioxide solution.

However, in this way, it is inevitable that there is a need to introduce various devices, which is economically burdensome, and there is a problem that the drug-derived adverse effects on the device. Furthermore, in order to generate chlorine dioxide in such a manner, it is necessary to have a large-scale apparatus capable of maintaining a water amount of several hundred tons or more.

On the other hand, for example, it is required to sterilize warm bath equipment, food manufacturing equipment, washing towers, and water of several tens of tons of scale, virus inactivation, elimination of odor, and deodorization. In terms of use, it is not cost-effective to use the above sterilization method. Further, if the above-described sterilizing apparatus is used, it is only possible to perform uniform treatment, and it is difficult to use it in such a small-scale and diverse use, and it is not practical.

On the other hand, in the chlorine dioxide generator which is used for such a small-scale and diverse use, there are solids and powders which are formed by gel and solid agent to ensure the sustained release of chlorine dioxide gas. Proposal.

However, this type of product is difficult to use due to its high cost and poor production efficiency of chlorine dioxide for handling a large amount of water. Difficult, at most it is used for deodorization in space. In particular, when the porous material contains chlorine dioxide to ensure storage stability and reactivity, the insoluble precipitate is formed due to introduction into water, and its properties are difficult to use in water treatment.

Specifically, in recent years, a technique in which a chlorite is mixed with a porous material and a function of dehumidifying and humidity-controlling the porous material is provided to impart a sustained release property to chlorine dioxide gas (Patent Document 1) is proposed. . However, this method is a method of slowly releasing chlorine dioxide gas in a limited space, and the mixture contains a large amount of insoluble porous material, so that it is difficult to dissolve in a water system.

In addition, a method of preparing a tablet containing a raw material containing a chlorite, a solid acid, and a free chlorine source and dissolving it in water to prepare a low-concentration aqueous solution of stabilized chlorine dioxide has been proposed (Patent Document 2, Patent Document 3). However, the amount of chlorine dioxide produced by the conventionally proposed tablet has a very small amount and has no effective effect, or it is produced after the pellet is produced first, and the cost is high. Further, the hardness of the tablet is low, and it may be broken during transportation.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Special Opening 2002-370910

[Patent Document 2] Japanese Patent Laid-Open No. 52-123399

[Patent Document 3] Japanese Special Table 2003-521526

An object of the present invention is to provide a solution for preparing chlorine dioxide. The lozenge does not require the size of the facility to be treated, and can generate a sufficient concentration of chlorine dioxide in a practical period of time, and has sufficient strength, and is not damaged during handling such as handling and packaging. And the production is good.

In order to solve the above problems, the inventors of the present invention have carefully studied and found that a metal chlorite, a chlorine releasing compound which releases chlorine upon contact with water, a solid acid source, a metal stearate, and a polymer disintegrating agent are found. The total amount of the tablet, the stearic acid metal salt and the polymer-based disintegrating agent is 0.3 to 10% by weight based on the total amount of the tablet, and a sufficient amount of chlorine dioxide can be generated in a practically short time, which is not easily broken. In order to produce good ingots.

The present invention has been completed based on the above findings, and provides the following tablets and the like.

Item 1. A tablet which is characterized in that it contains a metal chlorite, a chlorine releasing compound which releases chlorine upon contact with water, a solid acid source, a metal stearate, and a polymer disintegrating agent, and is hard. The total amount of the fatty acid metal salt and the polymer-based disintegrating agent is from 0.3 to 10% by weight based on the entire tablet.

The lozenge according to Item 1, wherein the stearic acid metal salt is at least one selected from the group consisting of magnesium stearate, calcium stearate, lead stearate, and zinc stearate.

Item 3. The tablet according to Item 1 or 2, wherein the polymer-based disintegrating agent is at least one selected from the group consisting of polyvinylpyrrolidone and a carboxyvinyl polymer.

The lozenge according to any one of items 1 to 3, further comprising Sodium bicarbonate.

The lozenge according to any one of items 1 to 4, wherein the weight ratio of the stearic acid metal salt to the polymer disintegrating agent (metal stearate: disintegrating agent of the polymer) is 1 : 0.5 to 1:50 range.

The lozenge according to any one of items 1 to 5, wherein the chlorine releasing compound which releases chlorine upon contact with water is sodium dichlorotridosocyanate.

The tablet according to any one of items 1 to 6, wherein the solid acid source is at least one selected from the group consisting of sodium hydrogen sulfate, citric acid, succinic acid, and maleic acid. .

Item 8. A tablet comprising a metal chlorite, a chlorine releasing compound which releases chlorine upon contact with water, a solid acid source, a metal stearate, and a polymer disintegrating agent, and dissolving water The time is within 10 minutes.

The lozenge according to any one of claims 1 to 8, which is a chlorine dioxide generating agent.

Item 10. A use of the tablet according to any one of items 1 to 8 for producing a chlorine dioxide generating agent.

Item 11. The use of the tablet according to any one of items 1 to 8 as a chlorine dioxide generating agent.

Item 12. A method for producing chlorine dioxide, comprising the step of contacting the tablet according to any one of items 1 to 8 with water.

Item 13. A method for producing a chlorine dioxide solution, comprising the step of dissolving the tablet according to any one of items 1 to 8 in an aqueous solution.

Item 14. A chlorine dioxide solution obtained by dissolving the tablet according to any one of items 1 to 8 in an aqueous solution.

The tablet of the present invention is effective for the modulation of a chlorine dioxide solution. That is, chlorine dioxide is not generated during storage, and chlorine dioxide is generated when dissolved in water, and a stable aqueous solution of chlorine dioxide can be prepared.

Further, the tablet of the present invention has a moderate solubility to water, and a sufficient amount of chlorine dioxide can be produced in a practical time. The tablet of the present invention is a form which is easy to handle, and can generate chlorine dioxide in the same degree of reactivity as the method of producing chlorine dioxide by using a strong acid and/or chlorine. Further, unlike strong acid and chlorine, it is composed of a safety material that does not adversely affect the environment and people when the unreacted component remains in the water or when the tablet is discarded. Moreover, it is excellent in physical strength and is also suitable for long-term storage and transportation. Moreover, it is excellent in that it generates stable chlorine dioxide at the time of use without the risk of explosion. Further, the tablet of the present invention is easily peeled off from the mold during tableting, and the breakage during tableting is suppressed, and the productivity is good.

Hereinafter, embodiments of the present invention will be described.

The tablet of the present invention is a tablet containing a metal chlorite, a chlorine releasing compound which releases chlorine upon contact with water, a solid acid source, a metal stearate, and a polymer disintegrating agent, and a metal stearate and The total amount of the polymer-based disintegrating agent is 0.3 to 10% by weight based on the entire tablet.

Metal chlorite

Metal chlorite which can be used in the tablet of the present invention, there is no particular limitation set. For example, an alkali metal chlorite such as sodium chlorite, potassium chlorite or lithium chlorite; an alkali metal chlorite such as magnesium chlorite or calcium chlorite can be exemplified. From the perspective of economy and practicality, alkali metal chlorite is preferred, and sodium chlorite is most desirable.

The metal chlorite may be used singly or in combination of two or more kinds.

The amount of the metal chlorite in the tablet is preferably 1% by weight or more based on the total amount of the tablet, more preferably 5% by weight or more, and most preferably 10% by weight or more. As in the above range, a sufficient concentration of chlorine dioxide can be produced in a practical time. Further, when it exceeds 25% by weight, it is a violent substance. Therefore, it is preferably 25% by weight or less, more preferably 20% by weight or less, and still more preferably 15% by weight or less. If it is within the above range, the combustion effect by heating, friction, or flushing can be reduced.

The amount of chlorite in the tablet may, for example, be 1 to 25% by weight, 1 to 20% by weight, 1 to 15% by weight, 5 to 25% by weight, 5 to 20% by weight, and 5 to 5 parts by weight of the entire tablet. 15% by weight, 10 to 25% by weight, 10 to 20% by weight, 10 to 15% by weight.

Moisture content

The degree of drying (water content) of the tablet of the present invention greatly affects the performance of the tablet for preparing a chlorine dioxide solution. That is, when the water content of the tablet is high, the decomposition reaction of the metal chlorite to the chlorate is promoted. Further, since the chlorine in the tablet is formed before the use of chlorine dioxide, the amount of chlorine dioxide generated during use is small as the water content in the tablet is high. For the above reasons, the water content in the tablet is preferably 10% by weight or less, and 5% by weight. The following is preferable, and 2% by weight or less is more preferable. It is ideal that the water is completely free, but the tablet contains water in the environment and contains an unavoidable amount of water. In particular, it may be contained in an amount of 0.5% by weight or more, or 1% by weight or more.

The water content in the tablet (weight ratio of water to the total weight of the tablet) may be, for example, 0.5 to 10% by weight, 0.5 to 5% by weight, 0.5 to 2% by weight, 1 to 10% by weight, 1 to 5% by weight, 1 to 2% by weight.

Chlorine releasing compound

A chlorine-releasing compound (hereinafter, also referred to as "chlorine-releasing compound") which releases chlorine when it is contacted with water which can be used in the tablet of the present invention. Usually, it can be used together with chlorite and solid acid to produce chlorine dioxide. , there are no special restrictions and can be used. For example, sodium dichlorotridosocyanate, potassium dichlorocyanate, sodium N-chloro-p-toluenesulfonate, sodium N-chlorobenzenesulfonamide, calcium hypochlorite or the like can be exemplified. From the perspective of economy and practicality, sodium dichlorosodium monochloride is preferred. Here, the above compound can be suitably selected from the chlorine release rate of the object and the corresponding chlorine dioxide production rate by those skilled in the art. The chlorine-releasing compound may be used alone or in combination of two or more.

In the tablet, the amount of the chlorine-releasing compound which releases chlorine when it comes into contact with water is preferably 1% by weight or more, more preferably 3% by weight or more, and most preferably 5% by weight or more. As in the above range, chlorine dioxide can be produced in a high yield. Further, it is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less. If it is in the above range, the amount of chlorine released can be suppressed.

The amount of the chlorine-releasing compound in the tablet can be exemplified with respect to the tablet. 1 to 30% by weight, 1 to 20% by weight, 1 to 10% by weight, 3 to 30% by weight, 3 to 20% by weight, 3 to 10% by weight, 5 to 30% by weight, 5 to 20% by weight, based on the whole, 5 to 10% by weight.

Solid acid source

The solid acid source which can be used in the tablet of the present invention is usually used without particular limitation as long as it can be used to produce chlorine dioxide together with the chlorinated compound as described above. For example, a mineral acid salt such as sodium hydrogen sulfate or potassium hydrogen sulfate; a salt of a strong acid-containing anion such as aluminum chloride, aluminum nitrate, cerium nitrate or iron sulfate and a weak base cation; citric acid and fubutene; Diacid, malonic acid, stearic acid, pyruvic acid, citric acid, malic acid, maleic acid, aconitic acid, oxalic acid, succinic acid, hydrocyanic acid, propionic acid, ascorbic acid, lactic acid, benzoic acid, tartaric acid, cinnamon An organic solid acid such as acid, itaconic acid, aminesulfonic acid, acetic anhydride, citric acid anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, benzoic anhydride or the like. From the viewpoints of safety, reactivity, and workability, inorganic acid salts and organic solid acids are preferred, and sodium hydrogen sulfate, citric acid, succinic acid, and maleic acid are particularly preferred. The solid acid source may be used alone or in combination of two or more.

The amount of the solid acid source in the tablet is preferably 1% by weight or more based on the total amount of the tablet, more preferably 10% by weight or more, and still more preferably 20% by weight or more. As in the above range, chlorine dioxide can be produced in a high yield. Further, it is preferably 40% by weight or less, more preferably 35% by weight or less, and still more preferably 30% by weight or less. If it is in the above range, the decrease in pH due to excessive free hydrogen ions can be suppressed.

The amount of the solid acid source in the tablet can be exemplified with respect to the entire tablet. 1 to 40% by weight, 1 to 35% by weight, 1 to 30% by weight, 10 to 40% by weight, 10 to 35% by weight, 10 to 30% by weight, 20 to 40% by weight, 20 to 35% by weight, 20 Up to 30% by weight.

The weight ratio of metal chlorite, chlorine releasing compound, solid acid source contained in the tablet (metal chlorite: chlorine releasing compound: solid acid source), 1: (0.1 to 1): (1 to 3) Ideally, 1: (0.2 to 0.9): (1.2 to 2.5) is ideal, and 1: (0.3 to 0.7): (1.3 to 2) is more desirable.

Metal stearate

The metal stearate which can be used as the tablet of the present invention is usually used, for example, as a slip agent for a tablet, and can be used without particular limitation. For example, magnesium stearate, calcium stearate, lead stearate, or zinc stearate may be mentioned, and magnesium stearate is particularly preferable from the viewpoint of economy and practicality. The stearic acid metal salt may be used singly or in combination of two or more kinds.

The stearic acid metal salt is added in order to prevent the raw material powder from sticking to the mold column of the tablet machine and the mold cavity when the mixed powder is formed into a tablet by a compression type ingot machine. The stearic acid metal salt is useful for inhibiting the breakage of the tablet by the tableting die and suppressing the breakage of the tablet, and reducing the frequency of the maintenance operation of the tableting machine. As a result, the tablet can be produced with good productivity.

The amount of the stearic acid metal salt in the tablet is preferably 0.05% by weight or more based on the total amount of the tablet, more preferably 0.1% by weight or more, and most preferably 0.2% by weight or more. Further, it is preferably 5% by weight or less, more preferably 3% by weight or less, and still more preferably 1% by weight or less. When it is in the above range, the effect of adding a metal stearate can be sufficiently obtained, and the phenomenon of the top cracking (layering of the tablet, capping) and the reduction of the chlorine dioxide release rate can be prevented.

The amount of the stearic acid metal salt in the tablet may, for example, be 0.05 to 5% by weight, 0.05 to 3% by weight, 0.05 to 1% by weight, 0.1 to 5% by weight, or 0.1 to 3 by weight based on the total amount of the tablet. %, 0.1 to 1% by weight, 0.2 to 5% by weight, 0.2 to 3% by weight, 0.2 to 1% by weight.

Polymer disintegrating agent

The polymer-based disintegrating agent which can be used in the tablet of the present invention is usually used, for example, as a disintegrating agent for a tablet, and can be used without particular limitation. Examples of the polymer-based disintegrating agent usable in the tablet of the present invention include polyvinylpyrrolidone (povidone), cross-linked polyvinylpyrrolidone (crospovidone), carboxyvinyl polymer, and water-soluble acrylic polymer. Carboxymethyl cellulose, carboxymethyl cellulose salt (sodium salt, calcium salt, etc.), alginic acid, low-substituted hydroxypropyl cellulose, and the like. Since the polymer-based disintegrating agent is an organic substance, there is a possibility of burning, but these polymer disintegrating agents can exert an effect in a small amount. From the perspective of economy and practicality, polyvinylpyrrolidone or carboxyvinyl polymer is particularly preferred. The polymer-based disintegrating agent may be used singly or in combination of two or more kinds.

Here, the polymer-based disintegrating agent is a polymer compound which swells upon contact with water. In the state in which the polymer-based disintegrating agent is formed into a tablet, the physical strength is maintained at a very high state, and it is immersed in water to swell, and the tablet itself collapses to improve the solubility of the tablet, thereby shortening the tablet. Dissolution time. In this way, it is possible to obtain a tablet having sufficient strength, and it is not damaged during handling such as handling and packaging, and a tablet of chlorine dioxide having a desired concentration can be produced in a practical time.

The amount of polymer-based disintegrating agent in the tablet, relative to the ingot The total amount of the agent is preferably 0.1% by weight or more, more preferably 1% by weight or more, and still more preferably 2% by weight or more. Further, it is preferably 10% by weight or less, more preferably 7% by weight or less, and most preferably 5% by weight or less. When it is in the above range, the effect of adding a polymer-based disintegrating agent can be sufficiently obtained, and deterioration of the tablet due to moisture absorption can be suppressed.

The amount of the polymer-based disintegrating agent in the tablet may, for example, be 0.1 to 10% by weight, 0.1 to 7% by weight, 0.1 to 5% by weight, 1 to 10% by weight, and 1 to 7 by weight based on the entire tablet. %, 1 to 5% by weight, 2 to 10% by weight, 2 to 7% by weight, 2 to 5% by weight.

The tablet of the present invention contains both a stearic acid metal salt and a polymer-based disintegrating agent, and is excellent in productivity during tableting, and has sufficient strength to be prevented from being damaged during handling and bagging, and is practical. A tablet of the desired concentration of chlorine dioxide can be produced over time.

When the tablet contains only the stearic acid metal salt among the stearic acid metal salt and the polymer-based disintegrating agent, the tableting at the time of tablet molding can be smoothly performed, but the physical properties of the tablet after molding cannot be expected. Sexual strength. Moreover, when immersed in water, the tablet itself does not easily collapse, and dissolution of the tablet takes a long time (solubility is deteriorated). On the other hand, in the tablet, when only the polymer-based disintegrating agent is contained in both the stearic acid metal salt and the polymer-based disintegrating agent, the molded tablet can maintain a state in which the physical strength is extremely high. Further, when immersed in water, it swells and the tablet itself collapses, the solubility of the tablet is high, and the dissolution time of the tablet is short. However, the tableting at the time of tablet molding cannot be smoothly performed, the frequency of maintenance of the tableting device becomes high, and proper tablet peelability and tablet completeness cannot be ensured.

The total amount of the stearic acid metal salt and the polymer-based disintegrating agent may be 0.3 to 10% by weight based on the total weight of the tablet, and preferably 1 to 8% by weight, and preferably 2 to 7% by weight. When it is in the above range, the effect of blending the stearic acid metal salt and the polymer-based disintegrating agent can be sufficiently obtained, and the solubility of the tablet can be not lost, or the tablet of the tablet can be floated in the water when the tablet is put into the tablet. The solubility of the tablet is not good, or the tablet of the tablet floats in the water when the tablet is put into the tablet, so that chlorine dioxide is not easily generated.

The weight ratio of the stearic acid metal salt to the polymer-based disintegrating agent in the tablet of the present invention (stearic acid metal salt: polymer-based disintegrating agent) is preferably in the range of about 1:0.5 to 1:50, and is about 1: A range of 2 to 1:30 is preferred, and a range of about 1:3 to 1:25 is more desirable.

Foaming agent

In the tablet of the present invention, one or two or more kinds of the above-mentioned respective components may be added to assist the tableting process, to improve the physical or appearance properties of the tablet to be produced, and/or A component that increases the solubility of the tablet and the yield of chlorine dioxide.

In particular, a foaming agent which promotes disintegration and solubility when the tablet is dissolved in water can be added. The foaming agent which can be used for the tablet of the present invention is usually not particularly limited as it is reacted with an acid to foam. For example, sodium carbonate, sodium hydrogencarbonate, potassium carbonate or the like can be exemplified, but sodium bicarbonate is preferred from the viewpoint of economy and practicality. The foaming agent may be used singly or in combination of two or more kinds.

The amount of the foaming agent in the tablet is preferably 1% by weight or more based on the total amount of the tablet, more preferably 3% by weight or more, and most preferably 5% by weight or more. If it is in the above range, the disintegration and dissolution of the tablet can be sufficiently promoted. Further, the amount of the foaming agent in the tablet is preferably 20% by weight or less based on the total weight of the tablet, and more preferably 15% by weight or less, more preferably 10% by weight or less. As in the above range, the solid acid is not consumed excessively.

The amount of the foaming agent in the tablet may, for example, be 1 to 20% by weight, 1 to 15% by weight, 1 to 10% by weight, 3 to 20% by weight, 3 to 15% by weight, or 3 with respect to the entire tablet. Up to 10% by weight, 5 to 20% by weight, 5 to 15% by weight, and 5 to 10% by weight.

Other components which can be added include a desiccant such as anhydrous calcium chloride and anhydrous magnesium chloride, a stabilizer such as sodium sulfate, a dye, and a curing inhibitor. Here, anhydrous calcium chloride and anhydrous magnesium chloride also function as a binder, and sodium sulfate also functions as an excipient.

The present invention also includes a chlorine-releasing compound containing a metal chlorite, releasing chlorine upon contact with water, a solid acid source, a metal stearate, and a polymer-based disintegrating agent, and the dissolution time for water is within 10 minutes. Lozenges. The weight per ingot is set to be about 0.1 to 20 g, and the type and amount of each component are adjusted within the above-described range, and a tablet having a dissolution time for water of 10 minutes or less can be obtained. Moreover, the foaming agent and water can also be adjusted in the range described above.

The dissolution time was determined by measuring the time required to completely dissolve one spindle in 1000 ml of distilled water at 30 ° C.

The tablet of the present invention can be produced in accordance with a commonly used tablet manufacturing method. For example, a metal chlorite, a chlorine-releasing compound that releases chlorine when it comes into contact with water, and a solid acid source are separately dried to remove water in each component, and then the components are mixed, and then a metal stearate and a polymer are added. In the range of 0.3 to 10% by weight based on the total amount of the tablet, the total amount of the components is reduced to 0.3 to 10% by weight based on the total amount of the tablet, and the tablet is processed by pressurization to obtain a tablet. Further, the obtained tablet may be subjected to a drying step if necessary. Here, the drying method at this time is not particularly limited, and examples thereof include a vacuum dryer, a flow dryer, a shelf dryer, a rotary dryer, and the like.

The tablet of the present invention is contacted with water to produce chlorine dioxide. Therefore, it can be used as a chlorine dioxide generating agent. For example, the tablet of the present invention is subjected to, for example, introduction and/or immersion in an aqueous solution (treatment target water or the like) to be treated, and is dissolved to form a chlorine dioxide solution. The aqueous solution may contain water, and examples thereof include tap water. In this way, a stable chlorine dioxide solution can be obtained. By using the tablet of the present invention, a chlorine dioxide solution can be safely and rapidly produced under a controlled method. When the chlorine dioxide concentration of the obtained chlorine dioxide solution is the usual chlorine dioxide concentration (0.5 to 200 ppm by weight) of tap water, the chlorine dioxide solution is substantially free of free chlorine, free chlorite anion, and/or Free hypochlorous acid anion with a moderate neutral pH (ie pH 7 to 9). Here, rapid generation means, for example, within 20 minutes, preferably within 15 minutes, and more preferably within 6 minutes to complete the generation of chlorine dioxide.

The tablet of the present invention does not generate chlorine dioxide during storage, and generates chlorine dioxide when water is dissolved, thereby modulating a stable aqueous solution of chlorine dioxide. That is, it is preferable to suppress the contact of the tablet with water before use, and it is preferable to block the chlorine dioxide before use.

More specifically, when not in use, it is placed in a material that is not easily permeable to water. The container or the packaging material that is not easily permeable to water is used to inhibit the generation of chlorine dioxide. When it is used, it is taken out from the container, or the packaging material is taken apart to make it contact with water for the first time, so that the chlorine dioxide gas is slowly slowed down. Produced, a stable aqueous solution of chlorine dioxide can be prepared.

In the tablet of the present invention, in order to suppress contact with water when not in use, the tablet may be contained in a container or packaged in a package, and the water vapor transmission rate of the container or the package is desirably 5 × 10 ^-9 cc ( STP)/cm ² ‧sec‧cmHg or less is preferably 1000×10 ^-10 cc (STP) mm/cm ² ‧sec‧cmHg or less. In particular, when the container or the enamel material is formed of a film having a thickness of 50 μm, the container or the enamel material is preferably 1000 × 10 ^-10 cc (STP) mm/cm ² ‧ sec ‧ cmHg or less. For materials that are not easily permeable to water vapor, metal or glass may be considered. However, for packaging materials and container materials, plastic films are easy to use. Examples of the plastic include aluminum vapor-deposited polyethylene (especially aluminum vapor-deposited polyethylene film), vinyl chloride, polychlorotrifluoroethylene, and the like.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples.

Example 1 (tablet forming)

The components of the composition shown below were dried at 70 ° C for 1 hour in advance, and then the components were mixed. 7 g of the mixed component was placed in a metal mold having a diameter of 20 mm, and a tablet having a tablet hardness of 30 kg was prepared by a continuous tableting machine manufactured by Kikusui.

Lozenge composition

Sodium chlorite 1.050g

Sodium dichlorosodium isocyanate 0.525g

Succinic acid 1.820g

Anhydrous magnesium chloride 2.100g

Sodium bicarbonate 0.560g

Sodium sulfate 0.749g

Magnesium stearate (slip agent) 0.021g

Polyvinylpyrrolidone (disintegrating agent) 0.175g

(Total amount of slip agent and disintegrating agent is 2.8% by weight)

1000 tablets of the above composition were prepared, and the tableting property, the chipping resistance and the solubility of the tablet were measured, and an average value or an average evaluation was performed. The results are shown in Table 1.

(evaluation method) Spinning

The tableting property is evaluated by the degree of adhesion, and is ○ when there is no adhesion at all, △ when there is a little adhesion, and × when it is immediately adhered.

Adhesion refers to the phenomenon that the mixed powder adheres to the surface of the mold post when the tablet is ingot. When the degree of adhesion is large, the ingot cannot be continuously ingot, and the surface of the tablet is rough due to the adhesion of the powder to the ingot mold column, resulting in a decrease in quality. Further, the tablet hardness (destruction resistance of the tablet) is too large, and the quality of the tablet is also different.

Destructive resistance

When the tablet is naturally dropped from a height of 1.5 m to the concrete surface, it is ○ when there is almost no damage, and is × when a large gap is generated.

Solubility

The solubility (dissolution time) of the tablet was evaluated by adding one tablet (7 g) to 1000 ml of distilled water and measuring the time required for complete dissolution at 30 °C.

Chlorine dioxide concentration, chlorite ion concentration, residual chloride ion concentration (iodine titration)

The chlorine dioxide concentration, the chlorous acid ion concentration, and the residual chloride ion concentration were measured according to the measurement methods described below.

1. Take a specified amount of distilled water in a container and put in a tablet.

2. After the dissolution of the tablet is finished, stir the plastic bottle to a uniform solution.

3. 10 mL of the chlorine dioxide solution obtained in 2 was weighed by a graduated cylinder, and diluted with distilled water to obtain a chlorine dioxide solution of 100 ppm.

Test 1

About 200 mL of distilled water was placed in a 300 mL Erlenmeyer flask, and about 0.5 mL of potassium iodide and a buffer of pH=7 were added in an amount of about 1 mL. The above-prepared 10 mL amount of chlorine dioxide solution was added to the correct amount with a pipette. The adjusted solution was immediately titrated with "0.01 N sodium thiosulfate solution". This titration was set to A (mL).

A(mL)=Cl ₂ +1/5ClO ₂

To the solution after the above titration, 2 to 3 mL of 2.3 M hydrochloric acid was added, and the reaction was carried out for about 5 minutes in the dark. Then, it was titrated with "0.01 N sodium thiosulfate solution". This titration was set to B (mL).

B(mL)=4/5ClO ₂ +ClO ₂ ^-

Test 2

In the gas washing bottle, about 200 mL of distilled water of about 1 mL of a buffer solution of pH=7 was prepared. In the same manner as in Test 1 above, a 10 mL amount of chlorine dioxide solution was accurately added as a pipette. Next, nitrogen gas was aerated (0.4 L/min) for about 10 minutes to remove chlorine dioxide. Then, the sample was transferred to a 300 mL Erlenmeyer flask, and about 0.5 g of potassium iodide was added. Immediately, the adjusted solution was titrated with "0.01 N sodium thiosulfate solution".

This titration was set to C (mL).

C(mL)=Cl ₂

To the titrated solution, 2 to 3 mL of 2.3 M hydrochloric acid was added, and the reaction was carried out in the dark for about 5 minutes. Then, it was titrated again with "0.01 N sodium thiosulfate solution". This titration was set to D (mL).

D(mL)=ClO ₂ ^-

Trial 3

Approximately 1 mL of a 5% potassium bromide solution and approximately 10 mL of 12N hydrochloric acid were placed in a 50 mL glass stoppered flask. The above-prepared chlorine dioxide solution was carefully pipetted with 10 mL of the chlorine dioxide solution and added to the above flask. Immediately stopper, stir, and react in the dark for 20 to 30 minutes. Add about 1 g of potassium iodide and stir. This was transferred to a 300 mL Erlenmeyer flask, and 25 mL of a saturated sodium phosphate solution was added thereto, and diluted to 200 mL with distilled water. Titrate with "0.01 N sodium thiosulfate solution". The sampling was repeated 3 times. Further, the usual supply water (that is, the sample of the chlorine dioxide solution was not added) was used, and the sample was prepared in the same manner and measured to obtain a blank value.

Results E (mL) = sample titration - blank titration

E(mL)=Cl ₂ +ClO ₂ +ClO ₂ ^- +ClO ₃ ^-

Calculation method

The content of each oxidizing agent was calculated by the following calculation formula.

Chlorite ion ppm=D×F×0.01×16,863/10

Chlorine dioxide ppm=(B-D)×F×0.01×16,863/10

Free chlorine ppm=[A-(B-D)/4]×F×0.01×35,450/10

Chlorate ion ppm=[E-(A+B)]×F×0.01×13,908/10

F: correction factor of 0.01M sodium thiosulfate solution

10: sample amount 10mL

The evaluation results of the tablet of Example 1 are shown in the following Table 1.

Further, the chlorine dioxide concentration, the chlorous acid ion concentration, and the residual chloride ion concentration of the chlorine dioxide aqueous solution obtained by dissolving the tablet of Example 1 were measured by an iodine titration method. The results are shown in Table 2.

As shown in Table 2, it is possible to modulate a stable dioxane with a practical concentration. A solution having a chlorine concentration can also provide a highly safe solution containing almost no chlorite ion and residual chloride ion. Here, the chlorous acid ion concentration of 44 ppm is an amount far below the quantitative lower limit.

Examples 2 to 5 and Comparative Examples 1 to 3

The tablets of Examples 2 to 5 and Comparative Examples 1 to 3 were produced in the same manner as in Example 1 using the composition shown in Table 3.

The obtained tablet was evaluated for tableting resistance and tableting resistance in the same manner as in Example 1. Destructive, soluble. The results are shown in Table 4. The results of Example 1 are also described in the fourth table.

As is clear from the results of the fourth table, the tablet containing both the magnesium stearate and the polymer-based disintegrating agent has excellent tableting properties, has appropriate hardness as a tablet, and has a short dissolution time, so that handling is easy and it is possible to prepare Good chlorine dioxide solution of any concentration.

Examples 6 to 10

The tablets of Examples 6 to 9 were produced in the same manner as in Example 1 using the composition shown in Table 5.

The obtained tablet was evaluated for tableting properties, tableting resistance, and solubility in the same manner as in Example 1. Further, the chlorine dioxide concentration, the chlorous acid ion concentration, and the residual chloride ion concentration of the obtained chlorine dioxide aqueous solution were measured by an iodine titration method. The results are shown in Table 6.

As shown in the sixth table, the tablets of Examples 6 to 9 produced a solution having the same chlorine dioxide concentration as that of the tablet of Example 1. Further, residual chlorite ions and chloride ions were hardly detected in all the tablets. As a result, the tablet for preparing a chlorine dioxide solution of the present invention is easy to manufacture, and a good chlorine dioxide solution of any concentration can be prepared in a short time as long as the tablet is immersed in water.

[Industry use possibility]

The tablet of the present invention can be suitably used for safe and simple preparation of an aqueous solution of chlorine dioxide which can eliminate the odor of bacteria, viruses, malodorous substances, molds, algae, water, and divalent metal ions of water. Used for various purposes.

Claims (8)

A tablet containing a metal chlorite, a chlorine releasing compound which releases chlorine when contacted with water, a solid acid source, a metal stearate, a polymer disintegrating agent, a metal stearate and The total amount of the polymer-based disintegrating agent is from 0.3 to 10% by weight based on the entire tablet. The tablet according to claim 1, wherein the stearic acid metal salt is at least 1 selected from the group consisting of magnesium stearate, calcium stearate, lead stearate, and zinc stearate. Kind. The tablet according to the first or second aspect of the invention, wherein the polymer-based disintegrating agent is at least one selected from the group consisting of polyvinylpyrrolidone and a carboxyvinyl polymer. The tablet according to any one of claims 1 to 3, which further contains sodium hydrogencarbonate. The tablet according to any one of claims 1 to 4, wherein the weight ratio of the stearic acid metal salt to the polymer-based disintegrating agent (metal stearate: polymer disintegrating agent) In the range of 1:0.5 to 1:50. The tablet according to any one of claims 1 to 5, wherein the chlorine releasing compound which releases chlorine upon contact with water is sodium dichlorotridosocyanate. The tablet according to any one of the preceding claims, wherein the solid acid source is selected from the group consisting of sodium hydrogen sulfate, citric acid, succinic acid, and maleic acid. At least one. a lozenge characterized by containing a metal chlorite and contacting with water When it releases chlorine, it releases a chlorine-releasing compound, a solid acid source, a stearic acid metal salt, and a polymer-based disintegrating agent, and the dissolution time for water is within 10 minutes.