JP2021172571A - Method for generating chlorine dioxide, chlorine dioxide generating kit and chlorine dioxide generating tool - Google Patents

Abstract

To provide a method for generating chlorine dioxide having good storage stability, capable of generating more chlorine dioxide than conventional products by a simple method, and generating less chlorine odor immediately after use, a chlorine dioxide generating kit and a chlorine dioxide generating tool.SOLUTION: There are provided a method for generating chlorine dioxide characterized in that chlorine dioxide is generated by allowing a solid (A) comprising a chlorite and a granulating agent and a solid (B) comprising a water-absorbing resin, a poorly water-soluble organic acid and a granulating agent to coexist in the same container and by pouring water into the container to gelatinize the whole; a chlorine dioxide generating kit comprising the solid (A), the solid (B), water and the container for storing them; and a gelated chlorine dioxide generating tool.SELECTED DRAWING: Figure 1

Description

The present invention relates to a chlorine dioxide generating method, a chlorine dioxide generating kit and a chlorine dioxide generating tool. More specifically, the present invention relates to a method for generating chlorine dioxide using two types of solids and water, a chlorine dioxide generation kit and a chlorine dioxide generator.

In recent years, chlorine dioxide has been attracting attention as an antibacterial agent to replace chlorine. Conventionally, many methods have been proposed as a method for generating chlorine dioxide. For example, a gel-like composition composed of stabilized chlorine dioxide and a water-absorbent resin (Patent Document 1) or a pure chlorine dioxide solution containing dissolved chlorine dioxide gas, chlorite and a pH adjuster contains a highly water-absorbent resin. There is a gelled composition (Patent Document 2).
Apart from this, the present inventors have previously proposed a one-component chlorine dioxide generating composition (Patent Document 3). This is a gel-like composition in a container, and chlorine dioxide is gradually generated just by opening the lid. When this lid is opened, there is almost no chlorine odor, and it is easy and easy for general users to use, and it is safe. I have you use it.

Japanese Unexamined Patent Publication No. 61-181532 Japanese Unexamined Patent Publication No. 11-278808 Patent No. 6385577

However, in the one-component chlorine dioxide generating composition as described above, since the reactivity of chlorine dioxide is large and the container is corroded when chlorine dioxide is generated even in a small amount, the reaction is completely suppressed in a closed state. There must be. However, it is very difficult to completely suppress the reaction, and there is a problem that the lid sometimes corrodes. On the contrary, if the reaction is suppressed too much, there is a problem that chlorine dioxide is generated too slowly when the lid is opened.
An object of the present invention is a chlorine dioxide generation method, a chlorine dioxide generation kit, which has good storage stability, can generate more chlorine dioxide than conventional products by a simple method, and generates less chlorine odor immediately after use. And to provide chlorine dioxide generators.

As a result of diligent studies, the inventor has found that the above object can be achieved by preserving each of the chlorite and the acidic substance as solids and bringing them into contact with water at the time of use, leading to the present invention.
That is, in the present invention, a solid substance (A) containing chlorite and a granulator, and a solid substance (B) containing a water-absorbent resin, a poorly water-soluble organic acid and a granulator coexist in the same container. It is a method for generating chlorine dioxide, which is characterized in that water is poured into the mixture to gel the whole body to generate chlorine dioxide.

Further, in the present invention, the disintegration rate of the solid substance (A) containing the chlorite and the granulator into water is the solid substance (B) containing the water-absorbent resin, the poorly water-soluble organic acid and the granulator. It is characterized by being faster than the rate of decay into water.

Further, the present invention is a chlorine dioxide generation kit used in the above-mentioned chlorine dioxide generation method, which is a solid substance (A) containing chlorite and a granulator, a water-absorbent resin, a poorly water-soluble organic acid and a granulator. It is a chlorine dioxide generation kit characterized by comprising a solid substance (B) containing, water, and a container for containing these.

The present invention is also characterized in that the poorly water-soluble organic acid is an organic carboxylic acid having a solubility in water of 5.8 g / 100 mL (20 ° C.) or less.

The present invention is also characterized in that the granulator is an inorganic mineral powder and / or an organic binder.

Further, the present invention is prepared by using the chlorine dioxide generation kit, and contains the solid substance (A) containing the chlorite and the granulator, the water-absorbent resin, the poorly water-soluble organic acid and the granulator. It is a chlorine dioxide generator characterized in that the solid substance (B) is gelled with water.

According to the present invention, a chlorine dioxide generation method and a chlorine dioxide generation kit, which have good storage stability, can generate more chlorine dioxide than conventional products by a simple method, and generate less chlorine odor immediately after use. And chlorine dioxide generators can be provided.

It is a conceptual diagram explaining the method of generating chlorine dioxide of this invention.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments. Within the same and equal scope as the present invention, various modifications can be made to the following embodiments.

The present invention is a chlorine dioxide generating method, a chlorine dioxide generating kit and a chlorine dioxide generating tool. A solid substance (A) containing chlorite and a granulator and a solid substance (B) containing a water-absorbent resin, a poorly water-soluble organic acid and a granulator are coexisted in the same container. When water is poured, the whole gels and chlorine dioxide can be gradually generated. In the present invention, the solid substance is a lump substance, and tablets molded into various shapes are preferable.

The solid substance in the present invention is used as a tablet, and its shape and size are not limited, and examples thereof include a ball shape, a rectangular shape, a conical shape, and a trapezoidal shape, and it is preferable that the solid substance is determined according to the intended use. Here, the tablet means a tablet or a briquette. Tablets or briquettes are powders or granules that are hardened, and tablets and briquettes are distinguished by how they are hardened. Tablets are preferred in the present invention.

(Solid substance containing chlorite and granulator (A))
The solid (A) essential contains a chlorite and a granulator.
The chlorite is not particularly limited as long as it reacts with an acid to produce chlorine dioxide, but for example, sodium chlorite, potassium chlorite, and lithium chlorite. Examples thereof include chlorite alkali metal salts such as, or chlorite alkaline earth metal salts such as calcium chlorite, magnesium chlorate, and barium chlorite. Of these, sodium chlorite is preferable because it is easily available and has no problem in use.

Chlorite dissolves in water and shows alkalinity, is chemically stable if the pH is 8.5 or higher, and can be stored for about 0.5 to 1 year by storing it in a sealed container. Is possible. However, when the chlorite aqueous solution becomes acidic, chlorine dioxide is generated. Therefore, even in solid matter, it must be alkaline with a pH of 8.5 or higher when made into an aqueous solution. Further, the stabilized chlorine dioxide aqueous solution, which is a stabilized aqueous solution in which chlorine dioxide is dissolved in an alkaline aqueous solution, has an equilibrium relationship with chlorite in the aqueous solution and contains the chlorite of the present invention. A stabilized aqueous chlorine dioxide solution can also be used as the chlorite in the present invention.

The amount of chlorite is preferably 2% by weight or more and 30% by weight or less with respect to the weight of the solid substance (A). More preferably, it is 4% by weight or more and 20% by weight or less. When it is 2% by weight or more, chlorine dioxide can be stably and sufficiently generated. When it is 30% by weight or less, the amount of chlorine dioxide generated can be controlled.

The granulator in the present invention has a role of granulating chlorite.
Examples of the granulating agent include powders of inorganic minerals and / or organic binders. The granulator can control the disintegration property of the solid into water and can maintain the stability of the solid when it is left in the air.

Examples of inorganic minerals include bentonite, kaolin minerals (kaolinite, dikite, nacrite, halosite, etc.), serpentine stones (chrysotile, lizardite, anticholite, amesite, etc.), and montmorillonite minerals (sodium montmorillonite, calcium montmorillonite, magnesium). Montmorillonite, etc.), smectite (saponite, hectrite, saconite, hyderite, etc.), pyrophyllite, talc, wax stone, mica (white mica, fengyite, sericite, illite, etc.), silica (Christobarite, quartz, etc.), compound Chain-type clay minerals (parigolskite, sepiolite, etc.), sulfate minerals such as plaster, dolomite, calcium silicate, calcium carbonate, gypsum, zeolite, boiling stone, tuffstone, vermiculite, laponite, pebble, diatomaceous soil, silas balloon, etc. Be done. Further, an inorganic material having hollow structure particles such as an alumina balloon, a glass balloon, a silica balloon, a shirasu balloon, a fly ash balloon (FA balloon), and a mullite balloon can also be preferably used.
Among these, sepiolite, zeolite, silica, bentonite, diatomaceous earth, hollow structure particles and the like are preferable from the viewpoint that the disintegration property of solid matter into water can be easily controlled and chlorine dioxide can be generated and retained in a large amount.

The amount of the inorganic mineral is preferably 5% by weight or more and 60% by weight or less, more preferably 10% by weight or more and 50% by weight or less, based on the total amount of the solid matter (A). The shape of the inorganic mineral is preferably powder. When it is a powder, it is easy to make a solid when mixed, it is possible to control the disintegration property into water when it is made into a solid, and the stability of the solid when the solid is left in the air can be improved. Can be maintained.

The average particle size (volume particle size) of the powder of the inorganic mineral is usually 1 to 100 μm, preferably 5 to 50 μm. Such an average particle size can be measured by a laser diffraction / scattering type particle size distribution measuring device (HORIBA LA-300, manufactured by HORIBA, Ltd.).

Organic binders include polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, dextran, purulan, xanthan gum, carboxymethyl cellulose (CMC), methyl cellulose (MC), sodium polyacrylate (SPA), hydroxypropyl methyl cellulose (HPMC), polyethylene oxide (PEO). And so on. Of these, polyvinyl alcohol is preferable.

The amount of the organic binder is preferably 0.2% by weight or more and 20% by weight or less, more preferably 0.5% by weight or more and 15% by weight or less, based on the total amount of the solid substance (A). The shape of the organic binder is preferably powder. When it is a powder, it is easy to make a solid when mixed, it is possible to control the disintegration property into water when it is made into a solid, and the stability of the solid when the solid is left in the air can be improved. Can be maintained.

Further, by combining several kinds of inorganic mineral powder and organic binder, it becomes easy to adjust the disintegration property of the solid substance into water. Even if the same pressure is applied during compression molding, the combination of the inorganic mineral powder and the organic binder changes the gaps and bulk density in the solid material, so that the rate at which water enters the solid material differs and the disintegration property differs. It is necessary to consider the optimum combination.

In addition, an alkaline substance may be added to improve the stability of the chlorite in the solid matter. Examples of the alkaline substance include sodium hydroxide, potassium hydroxide, calcium hydroxide, aluminum hydroxide, ammonium hydroxide, sodium sesquicarbonate, sodium hydrogencarbonate and the like.

The solid substance (A) is formed by mixing each component. The method of molding the solid material is not particularly limited, but for example, a method of molding one by one such as a mold method and a compression molding method, or a method of first producing a large solid material by this method is performed. It may be cut into a desired shape, preferably a compression molding method.

That is, preferably, the solid substance (A) is obtained by compression molding the dispersed granulated product by tableting molding or the like without mixing and heating the above materials or heating.

^{The pressure during compression molding is preferably 5 kgf / cm 2} or more in order to impart suitable mechanical strength to the obtained solid substance (A), and in order to improve the disintegration property into water. , 100 kgf / cm ² or less, preferably 80 kgf / cm ² or less. By adjusting such pressure, the disintegration property into water can be adjusted within a predetermined range.

In the above tablet method, a lock press basically composed of a compression device combined with a mortar and a pestle is used. When pressure is applied between the upper and lower pestle in the mortar via the compression device, a tablet having a shape formed by the mortar and the pestle is formed. As such a locking machine, a generally known single-shot locking machine that locks one tablet at a time can be used, or a rotary with high production efficiency provided along a disk that rotates a plurality of dies. A type lock machine can also be used.

In addition to the above materials, commonly used ingredients such as excipients, lubricants, binders, pigments and the like may be blended.

As described above, the shape of the tablet is not particularly limited, and examples thereof include a cylindrical shape, an elliptical pillar shape, a disk shape, a donut shape, a spherical shape, a trapezoidal shape, and a conical shape. In the case of cylindrical or trapezoidal tablets, the diameter is usually 10 to 100 mm, preferably 30 to 70 mm, and the height or thickness is usually 5 to 100 mm, preferably 10 to 50 mm.

When the solid substance (A) produced in this manner is immersed in water, it quickly disintegrates and scatters. As for the disintegration time in water, when 10 g of the solid substance (A) is immersed in water, the disintegration time of about 50% is 30 seconds or more and 60 seconds or less. It is easy to handle within this range.
As for the method of controlling the decay rate, the decay rate can be controlled by adjusting the pressure at the time of compression, changing the type and amount of the inorganic mineral and the organic binder, the ratio, and the like.

(Solid substance (B) containing a water-absorbent resin, a poorly water-soluble organic acid, and a granulator)
The water-absorbent resin is not particularly limited to a natural type or a synthetic type, and may be any one as long as it absorbs water and swells to gel the whole. For example, cross-neutralized polyacrylic acid, neutralized starch-acrylic acid graft polymer, hydrolyzate of starch-acrylonitrile graft polymer, saponified product of vinyl acetate-acrylic acid ester copolymer, isobutylene- Maleic anhydride copolymer cross-linked product, acrylonitrile copolymer or acrylamide copolymer hydrolyzate or cross-linked product thereof, acrylate-acrylamide copolymer cross-linked product, polyvinyl alcohol cross-linked product, modified polyethylene oxide cross-linked product, acrylamide- Examples thereof include a 2-methylpropane sulfonate copolymer crosslinked product, a (meth) acryloyl alkane sulfonate copolymer crosslinked product, a crosslinked carboxymethyl cellulose salt, and a crosslinked polymer of a cationic monomer. Of these, the cross-linked product of the partially neutralized polyacrylic acid and the neutralized product of the starch-acrylic acid graft polymer are preferable because they have particularly good water absorption characteristics, safety and economy.

The above-mentioned water-absorbent resin may be used alone, or two or more kinds may be appropriately mixed and used. The water-absorbent resin is in the form of particles and may be granulated into a predetermined shape, and the shape is not limited to irregular crushed shape, spherical shape, scaly shape, fibrous shape, rod shape, lump shape, powder shape and the like. However, it is more preferable that the solid matter (B) is in the form of powder because it easily gels water when it disintegrates into water.

The average particle size of the particles is not particularly limited, but is preferably 30 to 850 μm, and more preferably 60 to 400 μm.
The water absorption ratio is preferably 20 to 1,000 g / g, more preferably 80 to 600 g / g.

The amount of the water-absorbent resin is 15% by weight or more and 50% by weight or less with respect to the weight of the solid substance (B). It is preferably 25% by weight or more and 40% by weight or less.

Examples of the poorly water-soluble organic acid used in the present invention include organic acids such as carboxylic acid, sulfonic acid, and isocyanuric acid. It is preferably an organic carboxylic acid.
In the present invention, poorly water-soluble means that the solubility in water is preferably lower than 2 g / 100 mL (20 ° C.).

Examples of the poorly water-soluble organic carboxylic acid include adipic acid (1.4 g (15 ° C.)), glutamic acid (0.84 g (25 ° C.)), phthalic acid (0.72 g (26 ° C.)), and fumaric acid (0). .63 g (25 ° C)), dibasic acids such as sebacic acid (0.1 g (20 ° C)); caprylic acid (0.068 g (25 ° C)), lauric acid (0.0005 g (25 ° C)), myristin Carbons such as acid (0.1 g or less (18 ° C.)), stearic acid (0.0003 g (20 ° C.)), palmitic acid (0.0005 g (25 ° C.)), behenic acid (0.015 g (25 ° C.)) Examples include intermediate to higher fatty acids having a number of 8 or more. The numbers in parentheses indicate the solubility in 100 mL of water.

Since the poorly water-soluble organic acid is difficult to dissolve in water, a small amount of dissolved organic acid gradually generates chlorine dioxide and stabilizes the amount of chlorine dioxide generated for a long period of time. Further, even if it is difficult to dissolve in water, it can adhere to an inorganic mineral or a water-absorbent resin to exert an effect as an acid.
It is easy to control the amount of chlorine dioxide generated by selecting these poorly water-soluble organic acids or combining several types. Most preferred are dibasic acids or intermediate to higher fatty acids and combinations thereof.

Among the poorly water-soluble organic acids, a powder or granular substance of an organic acid having a melting point of 30 ° C. or higher is particularly preferable. Among the above-mentioned poorly water-soluble organic carboxylic acids, organic carboxylic acids other than caprylic acid can be mentioned. When the powder or granular substance of an organic acid having a melting point of 30 ° C. or higher is used, the water-absorbent resin or granulating agent can be uniformly mixed with the powder or granular substance.

The content of the poorly water-soluble organic acid varies depending on the type, but is preferably 0.1% by weight or more and 15% by weight or less with respect to the weight of the solid substance (B). More preferably, it is 0.5% by weight or more and 10% by weight or less. When the content of the poorly water-soluble organic acid is 0.1% by weight or more, chlorine dioxide is sufficiently generated when gelled, and when it is 15% by weight or less, the odor of chlorine when gelled is small.

As the granulator, the powder of the inorganic mineral used in the solid substance (A) and the organic binder can be used, and the type, amount, and ratio thereof may be the same as those in the case of the solid substance (A), but the target water. It changes depending on the decay rate and gelation rate.

As the method for producing the solid substance (B), the same method as the method for producing the solid substance (A) can be applied. Since the decay rate to water is different from that of the solid substance (A), the decay rate is different from that of the solid substance (B) by adjusting the pressure at the time of compression, changing the type and amount of the inorganic mineral and the organic binder, and the ratio. The rate and gelation rate can be controlled. Gelation begins as soon as the solid (B) disintegrates into water.
All you have to do is add water and let it stand. You can shake it at first, but it will stop working after a while.

Regarding the disintegration time in water (gelling time), for example, when 10 g of the solid substance (B) is immersed in water, the gelling time of about 50% is 2 minutes or more and 10 minutes or less. Further, chlorine dioxide is generated from the moment water is added to the solid substance (A) and the solid substance (B), and the amount of chlorine dioxide generated in an amount that can be detected by the detector tube is obtained after about 30 minutes.

In the present invention, a solid substance (A) containing chlorite and a granulator, and a solid substance (B) containing a water-absorbent resin, a poorly water-soluble organic acid and a granulator are coexisted in the same container. It is a method of pouring water into the gel to gel the whole to generate chlorine dioxide.

The ratio of the solid matter (A) to the solid matter (B) is preferably 10:90 to 90:10 by weight, preferably 30:70 to 70:30.
The amount of water is preferably 200 parts by weight or more and 1200 parts by weight or less with respect to a total of 100 parts by weight of the solid matter (A) and the solid matter (B). When it is 200 parts by weight or more and 1200 parts by weight or less, it can gel and generate chlorine dioxide.

Chlorite generates chlorine dioxide at a pH of 6.5 or less, and the lower the pH, the greater the amount of chlorine dioxide generated. The poorly water-soluble organic acid in the solid (B) fulfills this role. In that case, chlorine dioxide is gradually generated so that the poorly water-soluble organic acid is less soluble in water. Further, since the whole is gelled by the water-absorbent resin in the solid substance (B), the collision of the materials becomes gentle and the generation of chlorine dioxide becomes gentle. Together, these can generate chlorine dioxide for a long period of time.

In this case, the rate of disintegration of the solid (A) containing chlorite and the granulator into water is such that the solid (B) containing the water-absorbent resin, the poorly water-soluble organic acid and the granulator is dissolved in water. It is preferably faster than the decay rate. If the rate of disintegration of the solid substance (A) into water is high, the chlorite of the solid substance (A) dissolves in water and diffuses before the water gels, so that chlorous acid is uniformly present throughout the water. become able to. After that, the poorly water-soluble organic acid in the solid substance (B) dissolves and disperses in water, so that chlorine dioxide can be generated. At that time, gelation progresses little by little, so that the poorly water-soluble organic acid can be evenly dissolved and dispersed in water.

Therefore, the set of the solid substance (A) containing chlorite and the granulator, the solid substance (B) containing the water-absorbent resin, the poorly water-soluble organic acid and the granulator, water and the container containing them is It is a chlorine dioxide generation kit.
Put the solid (A) containing chlorite and the granulator, and the solid (B) containing the water-absorbent resin, the poorly water-soluble organic acid and the granulator in a container, close the lid and leave it for a long time. Since the solids (A) and (B) are separate solids, they do not react and are stable for a long period of time. The lid can be opened and water can be poured to gel the whole. Only then can chlorine dioxide be generated. Further, the water does not have to be put in the container, and the required amount may be put in a pack and set with the container, or the required amount may be prepared at the time of use.

Further, a solid substance (A) prepared by using the above chlorine dioxide generation kit and containing a chlorite and a granulator, and a solid substance (B) containing a water-absorbent resin, a poorly water-soluble organic acid and a granulator. What is gelled with water becomes a chlorine dioxide generator.
As described above, chlorine dioxide is generated because the chlorite in the solid substance (A) and the poorly water-soluble organic acid in the solid substance (B) are present in the gel.

FIG. 1 is a conceptual diagram illustrating a method of generating chlorine dioxide of the present invention. In FIG. 1A, the solid matter (A) 2 and the solid matter (B) 3 are stacked and stored in the container 1. The lid has been removed, and water 4 is about to be poured into the container 1 from above. The set of the container 1, the solid substance (A) 2, the solid substance (B) 3, and water is the chlorine dioxide generation kit 5 of the present invention. When water is added in FIG. 1A and 5 minutes or more have passed, the solid matter (A) 2 and the solid matter (B) 3 disintegrate into water and gel as shown in FIG. 1B, and the container 1 Inside is gelled product 6. This is the chlorine dioxide generator 7 of the present invention. In this state, chlorine dioxide is gradually generated.

The method of producing a chlorine dioxide generator using the chlorine dioxide generation kit of the present invention to generate chlorine dioxide can generate chlorine dioxide by a simple method even if it is not a one-component type, and immediately after use. There is little chlorine odor. Chlorine dioxide can be stably generated for a long period of time. Further, long-term storage stability is good even if the solid substance (A) and the solid substance (B) coexist in the container until water is added.

This will be described in the following examples, but the present invention is not limited to this.
(Manufacturing Example 1) (Manufacturing of solid substance (A))
39.2 parts by weight of "Silbrite 25" (manufactured by Nippon Carlit, stabilized chlorine dioxide, 250,000 ppm), 9.8 parts by weight of a 5% by weight aqueous solution of "CMC-1390" (manufactured by Daicel, carboxymethyl cellulose), 19.6 parts by weight of "Super Clay" (Hojun, Bentnite), 29.4 parts by weight of "Marlite M-60H" (Shirasu Balloon, manufactured by Marunaka Shirotsuchi), 2 parts by weight of 5% sodium hydroxide aqueous solution After putting it in a stainless beaker and stirring and mixing with a spiral blade (pH at this time is 11.5 to 12), transfer about 10 parts by weight to a cylindrical mold and ^{compress with a press pressure of 50 kgf / cm 2} for 30 seconds. About 8 parts by weight (the shape is cylindrical) of the solid substance (A) was obtained.

(Manufacturing Example 2) (Manufacturing of solid substance (B))
"Sunwet ST-500D" (manufactured by Sanyo Kasei Kogyo Co., Ltd., crosslinked polyacrylate type water-absorbent resin) 25 parts by weight, "PEG4000S" (manufactured by Sanyo Kasei Kogyo Co., Ltd., polyethylene glycol number average molecular weight 4000) 16.7 parts by weight , "Super Clay" (Hojun, Bentnite) 16.7 parts by weight, "Marlite M-60H" (Marunaka Shirotsuchi, Silas Balloon) 16.7 parts by weight, Stearic acid (reagent) 8.2 by weight 16.7 parts by weight of water was put into a stainless steel beaker, and after stirring and mixing with spiral blades (pH at this time was 6 to 7), about 12 parts by weight was transferred to a cylindrical mold and a press pressure of 50 kgf / cm ² 11.8 parts by weight (shape is cylindrical) of solid matter (B) was obtained by compression for 30 seconds.

(Example 1)
8 parts by weight of the solid substance (A) and 11.8 parts by weight of the solid substance (B) were placed in a 140 mL wide-mouthed bottle, the lid was closed, and the mixture was left for 3 months. The lid was opened 3 months later, but no change was seen. 120 parts by weight of water was put into this. The solid matter (A) began to disintegrate first, and after a while, the solid matter (B) began to disintegrate. When the solid substance (B) collapsed, gelation began to occur gradually, and gelation gradually progressed, and after 5 minutes, it completely gelled. The condition remained muddy. In this way, the chlorine dioxide generator of the present invention was obtained.
Chlorine dioxide seemed to be gradually generated from this, but no chlorine odor was detected. The amount of chlorine dioxide generated changed as shown in Table 1.

Further, as a comparative example, a gel-like chlorine dioxide generator composed of two layers prepared by the method of Japanese Patent No. 6385577 was prepared as Reference Example 1. The composition is 85.0 parts by weight of sodium chlorite aqueous solution (12500 ppm), 5 parts by weight of Sunwet ST-500D, 5 parts by weight of Bangel AV (Sepiolite, manufactured by Kusumoto Kasei Co., Ltd.), 2 parts by weight of Bengel HV (Bentonite, manufactured by Hojun). By weight, 43.0 parts by weight of aqueous ammonium dihydrogen phosphate solution (0.5%), totaling 137.9 parts by weight.
The chlorine dioxide generator of the present invention and the comparative chlorine dioxide generator were evaluated for the amount of chlorine dioxide generated, the deodorization of tobacco, the amount of chlorine generated when the container lid was opened, and the chlorine odor. The results are shown in Table 1.

(Evaluation method)
1. 1. How to measure the amount of chlorine dioxide generated Place the chlorine dioxide generator in a 10L gas repair bag, and after 30 minutes, shake the bag up and down to make the gas inside uniform, and then use a detector tube to make the chlorine dioxide in the bag uniform. The emission concentration (ppm) was measured. As the detector tube, the chlorine dioxide measurement detector tube No. 116 (manufactured by Komei Chemical Industry Co., Ltd.) was used. The same applies hereinafter.

2. One day after preparing the deodorant chlorine dioxide generator for cigarettes, the chlorine dioxide generator was placed in a 15 L plastic container filled with cigarette smoke for 15 seconds, sealed, and the time until the cigarette odor disappeared was measured. ..

3. 3. Chlorine odor and amount of chlorine generated 5 minutes after the chlorine dioxide generator was prepared, it was placed in a 4 L plastic container and the plastic container was covered. After standing for 10 minutes, the chlorine odor in the container was sniffed with the nose, and the degree of the chlorine odor was judged by 5 people. The amount of chlorine generated was measured with a Kitagawa type detector tube.
Chlorine odor: No or no small chlorine odor, but not noticeable
There is a slight chlorine odor, and the chlorine odor is annoying.
Large chlorine odor

From Table 1, Example 1 had almost no chlorine odor, and the deodorant property of tobacco, which is the effect of chlorine dioxide, was good. In addition, it was confirmed that the amount of chlorine dioxide generated was large and the deodorant property was improved as compared with Comparative Example 1. That is, the chlorine dioxide generator of the present invention generates chlorine dioxide even though the storage stability is improved as compared with the gel-like chlorine dioxide generator having two layers produced by the method of Patent No. 6385557. It was confirmed that the amount is large and it can be used as a deodorant.

1 container 1
2 Solid (A)
3 Solid (B)
4 Water 5 Chlorine dioxide generator kit 6 Gelled product 7 Chlorine dioxide generator

Claims (6)

Water (A) containing chlorite and a granulator, and solid (B) containing a water-absorbent resin, a poorly water-soluble organic acid and a granulator coexisted in the same container. A method for generating chlorine dioxide, which comprises pouring and gelling the whole to generate chlorine dioxide. The rate of disintegration of the solid matter (A) containing the chlorite and the granulator into water is such that the solid matter (B) containing the water-absorbent resin, the poorly water-soluble organic acid and the granulator disintegrates into water. The method for generating chlorine dioxide according to claim 1, wherein the speed is faster than the speed. A chlorine dioxide generation kit used in the method for generating chlorine dioxide according to claim 1 or 2, which is a solid substance (A) containing chlorite and a granulator, a water-absorbent resin, a poorly water-soluble organic acid, and granulation. A chlorine dioxide generation kit comprising a solid substance (B) containing an agent, water, and a container containing these. The chlorine dioxide generation kit according to claim 3, wherein the poorly water-soluble organic acid is an organic carboxylic acid having a solubility in water of 5.8 g / 100 mL (20 ° C.) or less. The chlorine dioxide generation kit according to claim 3 or 4, wherein the granulating agent is a powder of an inorganic mineral and / or an organic binder. The solid (A) containing the chlorite and the granulator, the water-absorbent resin, the poorly water-soluble organic acid, and the granulator, which are prepared by using the chlorine dioxide generation kit according to claim 4 or 5. A chlorine dioxide generator, characterized in that the solid matter (B) contained is gelled with water.

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