JP6739282B2 - Chlorine dioxide generating composition - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention is a chlorine dioxide generator and a method for generating chlorine dioxide, particularly chlorine dioxide gas that is continuously generated for a long period of time, and is useful for living, work and other spaces, environmental sanitization, antibacterial, deodorant, and mildew-proofing agent The present invention relates to a chlorine generating composition.

As a conventional chlorine dioxide generating composition, Patent Publication No. 2009-256141 discloses that chlorine dioxide is obtained by contacting stabilized chlorine dioxide and granular citric acid by dropping granular citric acid onto the upper surface of gelled stabilized chlorine dioxide. A configuration for generating gas is disclosed.

However, in this prior art, since citric acid, which is highly water-soluble and hydrophilic, is used, it has a strong reaction with stabilized chlorine dioxide and cannot generate chlorine dioxide in a stable manner. It was necessary to drop an appropriate amount of citric acid into chlorine dioxide manually or automatically when desired.

In addition, as another conventional chlorine dioxide-generating composition, Patent Publication No. 2013-177282 discloses that chlorine dioxide generation comprising an aqueous chlorite solution and an acidifying agent that is granular or tablet-like to be added at the time of use. An agent is disclosed, and the acidifying agent can be made into a fine granular form, a granular form, a round granular form or a tablet form as a dosage form of an acidic substance dispersed and treated with a hydrophobic wax. A technique is disclosed in which the surface area per unit weight is reduced and the tablet-shaped dosage form having a large volume is selected if the elution of the acidic substance is to be delayed.

However, in this conventional technique, the acidifying agent is dispersed with a hydrophobic wax and processed into an activator having low hydrophilicity, so that the reaction with the initial aqueous solution in which the hydrophobic wax is particularly weak is weak. Since it becomes too much and cannot generate sufficient chlorine dioxide, it is necessary to use the acidic substance itself or a fine-grained or granular acidic substance together.

Patent Publication 2009-256141 Patent Publication No. 2013-177288

An object of the present invention is to obtain a chlorine dioxide-generating composition capable of stably generating an appropriate amount of chlorine dioxide for a long period of time.

The chlorine dioxide-generating composition of the present invention is a chlorite water gel filled in a container, and a tablet shape that is stored separately from the chlorite water gel (as long as it is a three-dimensional pressure shape, (The shape is not limited), and a chlorine dioxide configured to generate chlorine dioxide by placing the activator on the upper surface of the chlorite water gel when in use. In the composition , the activator contains 85% to 100% of a first acidic substance having a solubility in water of 0.4 g/100 ml or more and less than 2 g/100 ml at 25° C., and a solubility in water. At 25° C., 2 g/100 ml or more of the second acidic substance is blended in a proportion of 15% to 0% .

Further, the first acidic substance is composed of fumaric acid.

Furthermore, the second acidic material is characterized Rukoto a citric acid.

Further, the first acidic substance and/or the second acidic substance is a mixture of a plurality of acidic substances, and the first acidic substance is a mixture of a plurality of first acidic substances, 2 acidic substance, wherein the mixture der Rukoto of the plurality of second acidic substance.

Furthermore, it has a perfume that is stored separately from the chlorite water gel and the activator, and in use, the perfume is arranged so as not to come into direct contact with the chlorite water gel and the activator. It is characterized by

The chlorine dioxide generating composition of the present invention uses the first acidic substance having low water solubility as an activator, so that the first acidic substance having low water solubility gradually reacts with the chlorite water gel. By generating chlorine dioxide, it is possible to stably generate chlorine dioxide of about 10 ppm in the water tank so that it will be about 0.01 ppm in the actual space where the product is supposed to be used. By press molding, the reaction rate of each activator with the chlorite water gel is suppressed, the amount of initial chlorine dioxide generated is suppressed, and the period during which the required amount of chlorine dioxide can be generated is extended. It has the effect that

Further, in the chlorine dioxide generating composition of the present invention, by adding an appropriate amount of a highly water-soluble second acidic substance as an activator, in the initial stage, mainly the highly water-soluble second acidic substance is chlorite water. Chlorine dioxide is generated from the gel, and then the first acidic substance, which has low water solubility, gradually reacts with the chlorite water gel to generate chlorine dioxide, so that it can be stably used in the actual space where the product is supposed to be used. It is possible to generate chlorine dioxide of about 10 ppm in a water tank so that it will be about 0.01 ppm. Furthermore, by pressing the activator into a tablet shape, it becomes possible to form a chlorite water gel of each activator. The reaction rate can be suppressed, the amount of initial chlorine dioxide generated can be suppressed, and the period during which the required amount of chlorine dioxide can be generated can be extended.

A first embodiment of the present invention will be described below with reference to the drawings.

In each of the examples of the present invention, the chlorine dioxide generating composition of the present invention is a chlorite water gel filled in a container and isolated from the outside air by a sealing material or the like, and a moisture proof isolated from the chlorite water gel. It consists of an activator stored in a bag etc., and is configured to generate chlorine dioxide by putting a tablet-shaped activator pressure-molded on the upper surface of the chlorite water gel when in use. ..

The activator of the present invention comprises a first acidic substance having a solubility in water of 0.4 g/100 ml or more and less than 2 g/100 ml at 25° C., and the chlorite water gel in Examples has a chlorite concentration. Is 1.25%, but the chlorous acid concentration of the chlorite water gel of the present invention is not limited to the chlorous acid concentration of the present example, and is 0.1 to 10 depending on the use environment and application. %, but particularly when the chlorous acid concentration is in the range of 0.1% to 3%, good effects can be obtained.

In Example 1, the activator was powdered fumaric acid (manufactured by Fuso Kagaku Co., Ltd.) having a solubility in water of 0.63 g/100 ml (0.779 g) as a first acidic substance, a diameter of 17.2 mm, and a thickness of 2 A pressure-molded tablet having a size of 0.7 mm is used.

Table 1 shows the test results of the chlorine dioxide-generating composition according to the present invention. Example 1 of the present invention and Comparative Example 1 and Example in which the activator of Example 1 was changed to granular citric acid only. Comparative Example 2 in which the activator of 1 was changed to powdered fumaric acid only, was placed on the upper surface of the chlorite water gel having a chlorous acid concentration of 1.25%, which was filled in each container, and was placed in a room at 25°C. It was volatilized and stored in an 18 L water tank for 1 day, and then the concentration of chlorine dioxide was measured.

In Example 1, by using fumaric acid, which is a low-water-soluble first acidic substance, as the activator, the low-water-soluble first acidic substance gradually reacts with the chlorite water gel. By generating chlorine dioxide, it is possible to generate chlorine dioxide of about 10 ppm in the water tank so that it will be about 0.01 ppm stably in the actual space where the product is supposed to be used. By pressure molding, the reaction rate of each activator with the chlorite water gel can be suppressed, the amount of initial chlorine dioxide generated can be suppressed, and the period during which the required amount of chlorine dioxide can be generated can be extended. it can.

In Comparative Example 1, since only the highly water-soluble second acidic substance, citric acid, is used as the activator, chlorine dioxide is rapidly generated from the chlorite water gel in the initial stage, and therefore in the initial stage. Since chlorine dioxide is excessively generated, it may have an adverse effect on the human body, and after that, the amount of chlorine dioxide generated continues to decrease. The period during which chlorine dioxide can be generated becomes shorter.

In Comparative Example 2, since only fumaric acid, which is the first acidic substance having low water solubility, is used as the activator, Comparative Example 1 in which only citric acid, which is the second acidic substance having high water solubility, is used Although the generation of chlorine dioxide in the initial stage is suppressed, the generation area of chlorine dioxide in the initial stage is increased because the contact area with the water gel is higher than in Example 1.

In Example 2 of the present invention, as the activator, phthalic acid (water was used as the first acidic substance having a solubility in water of 0.4 g/100 ml or more and less than 2 g/100 ml instead of fumaric acid of Example 1). It has a solubility of 0.72 g/100 ml at 26° C. and is pressure-molded into a tablet having a diameter of 17.2 mm and a thickness of 2.7 mm.

In Example 2, by using phthalic acid, which is a first acidic substance having low water solubility, as the activator, the first acidic substance having low water solubility gradually reacts with the chlorite water gel and is oxidized. By generating chlorine, it is possible to stably generate about 10 ppm chlorine dioxide in the water tank, which is about 0.01 ppm, in the actual space where the product is supposed to be used. By pressure molding, the reaction rate of each activator with chlorite water gel can be suppressed, the amount of initial chlorine dioxide generated can be suppressed, and the period during which the required amount of chlorine dioxide can be generated can be extended. ..

In Comparative Example 3, the components of the activator were the same as in Example 2, but the activator was not pressure-molded into a tablet shape. A large amount of chlorine is generated, and thereafter, similarly to Comparative Example 1 and Comparative Example 2, the generation of chlorine dioxide continues to decrease, and the period during which the required amount of chlorine dioxide can be generated becomes shorter.

As the first acidic substance of the present invention, instead of phthalic acid or fumaric acid, for example, cyanuric acid (solubility in water is 0.27 g/100 ml at 25° C.), adipic acid (solubility in water is 1.4 g/100 ml at 15° C.) or the like can be used, and a plurality of the first acidic substances may be mixed and used.

In the present invention, in addition to the first acidic substance having a water solubility of 0.4 g/100 ml or more and less than 2 g/100 ml at 25° C., the activator has a water solubility of 2 g/100 ml or more at 25° C. The second acidic substance may be blended in a proportion of 15% or less. In Example 3 of the present invention, 0.76 g of the first acidic substance made of fumaric acid of Example 1 as an activator was further added. As the acidic substance of No. 2, 0.076 g of granular citric acid having a solubility in water of 73 g/100 ml (manufactured by Komatsuya Co., Ltd.) was mixed, and the mixture was pressed into tablets.

In Example 3, as an activator, fumaric acid, which is a low-water-soluble first acidic substance, is used as a main component, and citric acid, which is a high-water-soluble second acidic substance, is added in an appropriate amount. Then, the second acidic substance having high water solubility mainly generates chlorine dioxide from the chlorite water gel, and then the first acidic substance having low water solubility gradually reacts with the chlorite water gel to generate chlorine dioxide. By generating it, it is possible to stably generate about 10 ppm of chlorine dioxide in the water tank so that it will be about 0.01 ppm in the actual space where the product is supposed to be used. Furthermore, the activator is pressure-molded into a tablet shape. By doing so, the reaction rate of each activator with the chlorite water gel can be suppressed, the amount of initial chlorine dioxide generated can be suppressed, and the period during which the required amount of chlorine dioxide can be generated can be extended.

In Comparative Example 4, the components of the activator were the same as those in Example 3, but the activator was not pressure-molded into a tablet shape. A large amount of chlorine is generated, and thereafter, similarly to Comparative Examples 1 to 3, the generation of chlorine dioxide continues to decrease, and the period during which the required amount of chlorine dioxide can be generated becomes shorter. In Comparative Example 5, the tablet-like pressure molding was carried out in the same manner as in Example 3, but 0.76 g of the first acidic substance made of fumaric acid as the activator, and further as the second acidic substance, Since 0.152 g of 20% granular citric acid (manufactured by Komatsuya) is mixed, much chlorine dioxide is generated in the initial stage, as in Comparative Examples 1 to 4, and then Comparative Examples 1 to Comparative As in Example 4, the generation of chlorine dioxide continues to decrease, and the period during which the required amount of chlorine dioxide can be generated becomes shorter.

In the present invention, as the second acidic substance, instead of the citric acid, a second acidic substance having a solubility in water of 2 g/100 ml or more, such as oxalic acid (solubility in water at 20° C. is 10 0.2 g/100 ml), malic acid (solubility in water is 55.8 g/100 ml at 20° C.), maleic acid (solubility in water is 79 g/100 ml at 25° C.), etc. relative to the total amount of the activator. It can be blended in a proportion of 15% or less, and in the present invention, a plurality of the second acidic substances may be mixed and used.

Furthermore, the chlorine dioxide generating composition of the present invention stores a fragrance in a moisture-proof bag or the like separated from the chlorite water gel, and does not directly contact the fragrance taken out from the moisture proof bag with the chlorite water gel when in use. The scent can be emitted without hindering the generation of chlorine dioxide by arranging it at the position. Although the fragrance may be liquid, existing fragrance absorbing techniques such as a calcium silicate molded body impregnated with the fragrance and a felt-like absorber absorbing the fragrance can be used.

As described above, the chlorine dioxide-generating composition of the present invention can stably generate an appropriate amount of chlorine dioxide for a long period of time, and is used at home, in factories, in vehicles, other spaces, environmental sterilization, and antibacterial. It is useful as a deodorant and mildew proofing agent.

Claims (5)

Chlorite water gel filled in a container,
An activator pressure-molded into a tablet shape that is stored separately from the chlorite water gel,
Becomes
At the time of use, on the upper surface of the chlorite water gel, by placing the activator, in a chlorine dioxide generating composition configured to generate chlorine dioxide,
The activator is
The first acidic substance having a solubility in water of 0.4 g/100 ml or more and less than 2 g/100 ml at 25° C. is blended in a proportion of 85% to 100%,
A chlorine dioxide-generating composition, characterized in that the second acidic substance having a solubility in water at 25° C. of 2 g/100 ml or more is mixed in a proportion of 15% to 0% . The chlorine dioxide generating composition according to claim 1, wherein the first acidic substance is fumaric acid . The chlorine dioxide generating composition according to claim 1, wherein the second acidic substance comprises citric acid . The first acidic substance and/or the second acidic substance is a mixture of a plurality of acidic substances , the first acidic substance is a mixture of a plurality of first acidic substances, and the second acidic substance is chlorine dioxide generating composition according to claim 1, wherein the acidic substance, wherein mixture der Rukoto of the plurality of second acidic substance. It has a perfume stored separately from the chlorite water gel and the activator, and in use, the perfume is arranged so as not to come into direct contact with the chlorite water gel and the activator. The chlorine dioxide-generating composition according to any one of claims 1 to 4, which is characterized in that .