JP2010254669A - Concentrated chlorine dioxide gas supporting material supporting chlorine dioxide gas of high concentration, enabling visual recognition of residual amount of chlorine dioxide gas in use, with beautiful appearance and long-term storage stability and enabling concentration control in use, use thereof and method for storing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for developing, producing, using and storing a chlorine dioxide gas supporting material which can remove microorganisms, malodor and other chemical substances in a space and has excellent appearance, thereby provides a hitherto absent space-cleaning agent supporting chlorine dioxide gas having high concentration, stores the gas for a long time, releasing an arbitrary amount of the gas in use, and enables visual recognition of the residual amount of the chlorine dioxide gas in use. <P>SOLUTION: The supporting material is produced by impregnating a sodium chlorite solution in a transparent silica gel having a pH of ≤6.0, drying under reduced pressure at ≤35°C, to prepare a silica gel capable of supporting concentrated chlorine dioxide gas, adding ≥1% of silica gel based on the weight of the supporting silica gel, sealing with a chlorine dioxide gas permeable film having one or more fine pores having a diameter of ≥0.3 nm and ≤100,000 nm, putting the product in a bag or a vessel having a carbon dioxide gas permeability of ≤10 mL/(m<SP>2</SP>×day/MPa) and a water vapor permeability of ≤5 g/(m<SP>2</SP>×day), evacuating to ≤100 torr, to heat seal the bag, etc. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to sterilization and inactivation of microorganisms such as bacteria, molds and viruses possessed by chlorine dioxide, decomposition effects of malodorous substances, deodorizing effects of allergen proteins, deodorizing agents and in-space The present invention relates to a space purification agent that denatures proteins that cause pollen and various allergens by reducing the amount of microorganisms.

  Chlorine dioxide is a strong oxidizer, sterilization, virus inactivation, deodorization, removal of off-flavor taste of water, removal of iron and manganese, and a high purification effect for water including tap water for over 50 years. It has been used industrially. Since these water treatment agents can be used relatively safely by dissolving chlorine dioxide itself in water, they are still used for measures against Legionella in warm bath facilities.

  However, for the purpose of removing and inactivating microorganisms floating in the space instead of water, chlorine dioxide is a dangerous gas with explosive properties, and there is also an irritating odor of chlorine. There is only a method of making very low concentration chlorine dioxide like a gel like technical literature, or mixing it with a solid acid and releasing weak chlorine dioxide gas depending on the humidity in the space at the time of use. Bacteria and virus spiders that spread by microsprays such as new influenza and airborne infections did not have the ability to prevent or prevent.

  Therefore, it can be said that the application of the prior art documents so far has not fully utilized the effect of chlorine dioxide more than that used for limited freshness-keeping agents and deodorants.

  If the details of the prior art documents are categorized, three methods are broadly proposed as methods for releasing chlorine dioxide as a gas and maintaining the gas concentration in the space continuously.

  The first method is a method in which a chlorite solution is adsorbed on a water-absorbing resin to be gelled, and chlorine dioxide gas is released by adding an oxidizing agent or an activator at the time of use.

  The second method is a method proposed in Japanese Patent Application Laid-Open No. 11-27808 and Japanese Patent No. 4109165, which improves the disadvantages of the first method. Specifically, it is a method in which a chlorite solution is adsorbed on a water-absorbing resin and a clay or chlorine dioxide gas is blown when gelling. By doing so, it becomes possible to make a gel containing chlorine dioxide in advance, and there is no need to add an oxidizing agent or an activator when using it. Further, it is said that a stable gas concentration can be maintained over a long period of time from the viewpoint of the release of chlorine dioxide gas.

  The third method is a method proposed in Japanese Patent Application Publication No. 60-161307, Japanese Patent Application Publication No. 64-71804, Japanese Patent Application Publication No. Hei 9-202706, and Japanese Patent Application Publication No. 2002-370910. A sandy chlorine dioxide gas carrier is formed by impregnating a chlorite solution into a substance having a property as a porous inorganic solid acid or admixing chlorite. More specifically, silica alumina, crystalline silica zeolite or silica gel as a solid acid is impregnated with a chlorite solution, and potassium carbonate or an inorganic mineral is added as a reaction inhibitor to suppress the reaction. This method promotes the reaction between solid acid and chlorite and releases chlorine dioxide gas.

Patent application publication 60-161307 Patent Application Publication No. 64-71804 Patent Application Publication 9-202706 Patent Application Publication 2002-370910 Patent Application Publication 11-27808 Japanese Patent No. 4109165 Patent Application Publication No. Hei 6-233985

  First of all, the problem with the first method is that it takes time to add an oxidizing agent or an activator at the time of use, and it is disadvantageous in terms of cost because it is necessary to prepare a container for the oxidizing agent and the activator separately. Furthermore, since the concentration becomes too high for several days to several weeks immediately after the addition of the oxidizing agent, activator, etc., it is difficult to keep the concentration uniform over a long period of time. In addition, the gas is released over time, but the timing at which the release of chlorine dioxide gas stops is extremely difficult to understand, so it is left as it is even though the effect has already been lost. There is a drawback.

Next, the problem of the second method is that it is an excellent method that can eliminate the trouble of adding the activator of the first method in that a chlorine dioxide gel is formed in advance, but the reaction to chlorine dioxide gradually increases. Therefore, when stored in a closed container for a long period of time, the chlorine dioxide concentration inside the container will increase, causing damage or deterioration of the container, and if the concentration is lowered, the effective range and effective time will be reduced. Incurs reduction. In addition, various gums and polyacrylic acid used as a gelling agent are deteriorated by chlorine dioxide, resulting in water separation or gel formation. In addition, when prepared as a water-soluble gel, acceleration tests and severe tests are difficult, and long-term storage stability cannot be properly confirmed by tests. Further, when chlorine dioxide is already kept in a gel-like state in a container, it is released at a time when the container is opened for use, so that it becomes a high concentration immediately after use as in the first method.
Furthermore, when gelled with a water-absorbing resin, the gel turns white in the second half of the period of use, and it is not possible to see whether chlorine dioxide gas is still being released, so the timing of replacement is not known. It is.
As a result, the products on the market are not much different from the first method of adding the activator before use.

  By the way, when the state in which chlorine dioxide gas is released is referred to as the “on” state, and the state in which chlorine dioxide gas is not released is referred to as the “off” state, in the first method, “on” and “off” Means that the “switching method” is based on the physical method “addition of activator”, while the second method is always in the “on” state. In this second method, there is no need to switch "addition of activator", but that is because it is always in the "on" state and is not an essential solution. . Therefore, deterioration and breakage of the container occur secondary, and the initial concentration at the time of use becomes high, so that the resolvability cannot be obtained, and as a result, the activator is added at the time of use.

  Finally, the third problem is that in the case of mixing silica alumina or crystalline silica zeolite with chlorite, the appearance is similar to that of sand, so the end time of the effect cannot be visually recognized.

  Further, in the method of impregnating a chlorite solution with silica alumina described in “Patent Application Publication No. 60-161307”, there is no explanation about the acid strength of silica alumina, but as a solid acid that can sufficiently generate chlorine dioxide. Assuming that there is acid strength, when dried by a method of reduced pressure drying at a high temperature of 50 ° C., chlorine dioxide gas is excessively released from silica alumina at such a high temperature, which is accompanied with great danger in mass production. Therefore, practical application is difficult. Conversely, when silica alumina without sufficient acid strength is selected, chlorine dioxide gas is not sufficiently generated during use.

  Furthermore, in order to suppress the generation amount of chlorine dioxide gas as a method of mixing with crystalline silica zeolite, a method of adjusting the pH to 6.5 to 9.0 has been proposed, but these solid acids are impregnated with chlorite. The method of generating chlorine dioxide gas is a method utilizing the fact that chlorine dioxide is generated according to the humidity in the surrounding environment at the time of use, and high concentration chlorine dioxide gas cannot be diffused. , The concentration cannot be controlled arbitrarily, it can only be left to the surrounding environment, that is, in the relationship of “on” and “off”, it gradually changes to the “on” state depending on the surrounding environment. The problem is that it cannot be switched independently.

  Further, according to this document, it is said that chlorine dioxide gas is generated too much when the pH is 6.0 or less. Thus, since the concentration cannot be arbitrarily controlled by this method, the pH has to be controlled so as to achieve a low concentration reaction.

  On the other hand, regarding the above-mentioned “on” and “off” control, in the case of this third method, the control is performed by drying, but due to the deliquescent nature of chlorite. As long as the drying process is not strict regardless of pH, chlorine dioxide gas is generated as the storage period becomes longer if the drying process is simply mixed by deliquescence. That is, even in this method, the problem of the second method cannot be solved in essence because the “off” state is vague due to the deliquescence of chlorite.

In the method of impregnating silica gel with a chlorite solution, sodium carbonate hydrogen peroxide adduct is added to suppress the reaction, but in this document, the choice of porous materials is ceramics, diatomaceous earth, silica gel, active A wide variety of materials, such as alumina, have different physical properties, and cannot be a single stable product. Further, since the physical properties of silica gel, including its pH, are different, it is not known from this document whether chlorine dioxide can be released stably.
If the pH is in the neutral to alkaline range, sufficient chlorine dioxide gas release cannot be expected by simply impregnating with chlorite. When silica gel having an acidic pH is used, a large amount of chlorine dioxide gas is generated only by impregnation, and it is extremely difficult to mass-produce.
Furthermore, in the proposal using these silica gels, in order to suppress the reaction and maintain the concentration over a long period of time, it is finally mixed with other substances such as sodium carbonate hydrogen peroxide adduct and gypsum and formed into tablets. Therefore, the timing of the end of use is still unknown.
The content using this silica gel is a content that was devised to suppress the reaction by simply using silica gel as a material for adsorbing a chlorite solution, so silica alumina or crystalline silica zeolite was used. It is essentially the same as the method and shares its problems.
In addition, these methods are basically mechanisms in which the reaction occurs at ambient humidity when chlorous acid is supported on the carrier and continues, so it is easy to stop the reaction once it has started. It is also a problem that cannot be made.

  Basically, this third method is a patented technique for making little reaction when mixing chlorite and some carrier, so that the release of chlorine dioxide during use is not effective in the environment during use. This is a fundamental difference from the present invention that will be described below.

  “Patent Application Publication No. Hei 6-233985” is a proposal to release chlorine dioxide gas at a stretch by adsorbing chlorine dioxide gas to a porous inorganic carrier such as silica gel and sending pressurized air to the adsorbed substance. However, this method is extremely difficult to put to practical use because high concentration chlorine dioxide gas must be handled during production, and production is unstable and dangerous.

  In other words, all the methods described in the conventional prior art documents do not solve or specify the following three problems.

The first problem is the product concept. All of the conventional technologies suppress the reaction when mixing chlorite and acidic substances, and only weak chlorine dioxide is generated because high concentration of chlorine dioxide is not supported during production. This is a product and technology that releases chlorine dioxide gas by using ambient humidity or adding an activator during use.
However, in such products, it takes time to add an activator, and in products in which chlorite and acidic carrier are mixed and molded, the chlorine dioxide concentration depends on the surrounding environment at the time of use. As the concentration at the time of use cannot be determined, the amount of chlorine dioxide generated significantly increases and decreases, and the chlorine dioxide concentration in the environment of use cannot be controlled, so it cannot be used as a sterilization or virus countermeasure, and as a deodorant Only the position of was practically possible.

The second problem is a concentration problem during use. Chlorine dioxide is harmful to the human body at high concentrations, and its levels are guided by the American Industrial Hygienists Association (ACGIH). According to it, the short-term exposure concentration is 0.3 ppm and the long-term exposure concentration is 0.1 ppm. As pointed out in the first problem, all the products of the prior art cannot control the concentration. There are many cases that should not be sold as defective products, and those that should not be sold as defective products are not yet established in the small indoors. At a level where chlorine dioxide can be perceived as a chlorine odor, the concentration is already high, and a concentration that is effective for the decomposition of microorganisms such as bacteria and viruses, malodorous substances, and allergens is possible at a lower concentration. In other words, unless it is a product that maintains the chlorine dioxide concentration at a very low concentration that humans cannot perceive, and knows when the chlorine dioxide concentration has disappeared, it is necessary to ask for the sterilization and inactivation of bacteria and viruses floating in the space There is a problem that can lead to error.
In this way, products based on the conventional technology stably carry high concentration of chlorine dioxide on some kind of carrier, cannot be stably released during use, and the user does not know when to end the effect. Only products that are very ambiguous with respect to the concentration of can be achieved with the prior art.

The third problem is storage stability. In order to supply products stably in the general consumer market, the storage stability must be guaranteed for at least one year, usually three years. The conventional technique has not established a method for stably storing high-concentration chlorine dioxide, which leads to the product concept pointed out in the first problem.
In addition, in the prior art, products that react weakly when chlorite and a carrier are mixed or products in which chlorine dioxide is gelled with a water-absorbing resin cannot obtain storage stability at high temperatures and high humidity. In the case of a product in which the reaction is excessively suppressed and made into one agent such as gelling, the chlorine dioxide is hardly released at the time of use and the effect of the original chlorine dioxide gas cannot be obtained. As a result, products other than those of the type that add the activator have virtually disappeared from the market.

  As a means for solving the above three problems, the present inventor has intensively studied and as a result, has taken the approach completely opposite to that of the prior art, and has reached the present invention. First, as a solution to the first problem, a method for inventing a method for stably producing a large amount of chlorine dioxide gas at a high concentration was invented. In the prior art, a stable production method has not been established for a gas composition containing high concentration of chlorine dioxide, but the present inventors impregnated a transparent silica gel having a pH of 6.0 or less with a chlorite aqueous solution. The first feature is that a high concentration of chlorine dioxide gas can be generated and adsorbed by controlling the heat of reaction at the time of heating and maintaining the temperature at 35 ° C. or lower and drying under reduced pressure.

  The solution to the second problem is that a high concentration of chlorine dioxide gas is supported on transparent silica gel so that the gas loading and release status can be visually recognized with the light and dark shades of chlorine dioxide. In order to release chlorine dioxide gas at a constant concentration for an arbitrary period of time, the silica gel supporting high concentration chlorine dioxide has one or more fine pores of 0.3 nm or more and 100,000 nm or less so that the chlorine dioxide gas supported on time is not released. The second feature is that it is used in a sealed bag.

The solution to the third problem is that the carbon dioxide permeability is 10 ml / m ² · day / MPa or less and the moisture permeability is 5 g / m in order to preserve the silica gel carrying a high concentration of chlorine dioxide gas over a long period of time. ^The gas adsorption rate is 8 at a relative humidity of 20% or less with respect to the weight of the silica gel carrying the high-concentration chlorine dioxide gas. The above-mentioned silica gel is mixed in an amount of 1% or more, preferably 20% to 25%, and further reduced in pressure to 100 torr or less, and then sealed, so that the chlorine dioxide gas is equilibrated in a sealed bag or container. I found that I could maintain the state. As a result, the problem of storage stability, which was a problem in the prior art, was solved, and long-term storage stability was ensured.

The high-concentration chlorine dioxide gas-supported silica gel according to the present invention is produced in the form of hard beads having a yellowish brown color. Since storage and adsorption / desorption of chlorine dioxide gas is maintained in the bag or container for a long period of time, there is little deterioration until immediately before use, and after use, the bag or container is not affected by ambient humidity. The amount of gas released is controlled with a positive correlation with the gas permeability.
As a result, at the end of the effect, it changes into a transparent bead shape, the replacement timing becomes obvious at a glance, and the carried chlorine dioxide gas is controlled by controlling the permeability of the contained bag or container. Depending on the application, it can be released at any concentration, and it has become possible to sterilize spaces, inactivate viruses, deodorize malodorous substances, decompose allergens, and maintain freshness very easily.

  The chlorite used in the present invention includes alkali metal chlorites such as sodium chlorite, potassium chlorite and lithium chlorite, and alkaline earth metals chlorite such as calcium chlorite. Salts can be mentioned, but sodium chlorite is the most readily available and can be used without problems in terms of use and cost. As the chlorite solution, a commercially available sodium chlorite solid dissolved in purified water and adjusted to 25% can be used, or a solution adjusted to 30% can also be used. Further, there is no problem even if the sodium chlorite solution already adjusted as 32% or 25% which is already marketed as a solution is used as it is, but by using a higher concentration chlorite solution, it is inevitably higher. Silica dioxide gas-supported silica gel having a concentration can be produced. At this time, if the concentration of chlorite is less than 20%, the concentration is low and the efficiency becomes poor. Therefore, it is desirable to adjust it to 25% to 35%.

  As silica gel for adsorption reaction of chlorite, any substance can be used as long as the pH is adjusted to 6.0 or less and the adsorption rate at relative humidity 20% or less is 8 or more. From the viewpoint of preventing cracks in appearance, it is desirable to use silica gel with high water resistance.

In the vacuum drying, a commercially available general vacuum dryer or freeze vacuum dryer can be used. As is well known, the boiling point drops under reduced pressure depending on the degree. Further, in normal hot air drying, in drying a porous body such as silica gel, water must ooze out from the surface and evaporate, and chlorine dioxide leaks out as a solution, which is not efficient. In this respect, if it is a vacuum drying method, unnecessary moisture can be sublimated in a shorter time.
In addition, the heat of reaction caused by impregnating silica gel with a sodium chlorite solution can be used to prevent temperature drop due to moisture sublimation. At this time, if the temperature exceeds 35 ° C., desorption of chlorine dioxide gas becomes severe and the working efficiency is lowered. Therefore, the temperature is preferably 35 ° C. or less.

  In the present invention, the drying under reduced pressure is not for suppressing the reaction but for promoting the reaction and generating a higher concentration of chlorine dioxide, and controlling the temperature to increase the concentration of chlorine dioxide generated at a high concentration. It can be supported on silica gel. At this time, the pressure may be reduced as long as the drying can be sufficiently performed, and the pressure may be reduced according to the boiling point drop in the range of -5 ° C to 25 ° C. The chlorite solution to be added can be arbitrarily selected from 10% to 60% with respect to the weight of the silica gel, but in the range of 25% to 35% in terms of production efficiency and chlorine dioxide production and loading efficiency. It is desirable to add a solution having a concentration of chlorite of 35% or more and 50% or less based on the weight of the silica gel.

  If there is no cost functional restriction in the apparatus, the most efficient method is a method using a freeze vacuum dryer. According to this method, it is possible to carry out the most efficient production with minimal desorption while producing a high concentration chlorine dioxide gas-supporting silica gel.

  In storage, the silica gel immediately after supporting the high concentration chlorine dioxide gas prepared by the above-described method tends to release and release chlorine dioxide gas rapidly. Add additional. The amount added should be such that the released amount and the adsorbed amount are kept in equilibrium, and the desired added amount depends on the adsorption capacity of the silica gel, but at least 1% is required, preferably 10% or more, more preferably Add 18% to 23%. At this time, since the drying process is performed, the relative humidity is sufficiently reduced. In such an environment where the relative humidity is low, the change in performance due to the type of silica gel is slight, so that any additional silica gel can be added at this time.

When silica gel loaded with high-concentration chlorine dioxide gas is left as it is in an open system, all chlorine dioxide gas is released within a few days. Therefore, in the present invention, the produced high-concentration chlorine dioxide gas-supported silica gel has fine pores larger than chlorine dioxide molecules and smaller than the size of water droplets such as drizzle, that is, fine pores of 0.3 nm or more and 100,000 nm or less. Seal in a bag of waterproof and breathable material.
At this time, by controlling the amount of chlorine dioxide gas released from the silica gel carrying high-concentration chlorine dioxide gas by increasing or decreasing the size and number of micropores within the above range, the target can be controlled with low-concentration chlorine dioxide gas for any period of time. The hygiene management of the space can be performed. As a bag having such properties, waterproof and moisture-permeable materials used for bags for keeping food fresh and diapers can be widely used.

  When one having an aeration flow rate of 5000 cc / min or more is used, a chlorine dioxide gas release property of about 3 days to 1 week can be obtained. When it is desired to obtain longer-term release properties, it can be realized by using a bag of 20 to 200 cc / min.

The silica gel carrying chlorine dioxide gas and the additional silica gel are simply mixed, put in a bag or container with a moisture permeability of 5 g / m ² · day or less, and sealed by vacuum sealing to 100 torr or less. The amount of water vapor entering the inside of the bag depends on the moisture permeability of the package. As a result, the internal relative humidity hardly increases, and the chlorine dioxide gas desorbed from the silica gel carrying the chlorine dioxide gas is adsorbed by the additional silica gel to keep the chlorine dioxide concentration in the entire silica gel uniform and preserved. Sometimes adsorption and desorption of chlorine dioxide gas from silica gel can be kept in equilibrium. In addition, if the carbon dioxide permeability is 10 ml / m ² · day / MPa or less, desorption of chlorine dioxide gas from the inside of the bag to the outside can be almost suppressed, so that long-term storage stability can be achieved by adsorption / desorption inside the bag. It is possible to have it. For moisture permeability and carbon dioxide permeability, the smaller the value, the longer the storage stability can be obtained, so the above values are the values that guarantee the minimum long-term storage stability, It goes without saying that it is desirable to use the best gas barrier film available rather than being bound.

  As a bag or container as described above, it is a film material used for a fresh food vacuum pack, etc. as the simplest one, and a gas barrier property provided by various companies as long as it is a film provided with a gas barrier property by EVOH or silica deposition. Can be used without problems with film. In the example shown below, Tech Barrier HX made by Mitsubishi Plastics was used.

  The silica gel carrying high-concentration chlorine dioxide gas prepared by the method as described above is prepared by dissolving 25 g of sodium chlorite (manufactured by Nippon Carlit) in 75 g of purified water, and 100 g of the resulting 25% sodium chlorite solution is 300 g of RD type. Add to silica gel. After confirming that the temperature of the silica gel is about 30 ° C., it is dried under reduced pressure by a vacuum dryer. 100 g of RD-type silica gel is added to and mixed with the high-concentration chlorine dioxide gas-supported silica gel, and then heat sealed after reducing the pressure to 100 torr again in a bag made of SivmPET12 / ON15 / LLDPE50 used in a vacuum pack. Can be obtained.

  Next, the effects of the present invention will be described with reference to examples and comparative examples.

  Table 1 compares the amount of chlorine dioxide retained by the chlorine dioxide gas-carrying silica gel produced by each method of Example 1, Comparative Example 1, and Comparative Example 2. 100 g of the gas carrier produced by each method was pulverized and dispersed in 1 L of water, and after 1 hour, the chlorine dioxide concentration was measured by the DPD glycine method.

  Table 2 compares the appearance change with time and the amount of gas retained for the gas carriers produced by the methods of Example 2, Comparative Example 3, and Comparative Example 4.

  Table 3 shows each chlorine dioxide gas after the chlorine dioxide gas-supported silica gel produced by each method of Example 3, Comparative Example 5, Comparative Example 6, and Comparative Example 7 was stored at 40 ° C. and relative humidity of 85% or more for one month. The reduction rate of the amount of chlorine dioxide gas retained by the supported silica gel was compared.

In Table 4, each sample of Example 4, Comparative Example 8, and Comparative Example 9 was put in a 1 m ³ experimental facility, and the internal chlorine dioxide gas concentration was measured over time. For the measurement, chlorine dioxide gas detection tubes 23M and 23L manufactured by Gastec Corporation were used.

  Table 5 shows the bacteria when Example 5 and the non-woven mask were sent to the Japan Food Analysis Center, and the non-woven mask was sterilized, and then the bacterial solution of spore bacteria, Escherichia coli, and Salmonella was added and installed in the same container as Example 5. The change in number was measured.

25 g of sodium chlorite (manufactured by Nippon Carlit) was dissolved in 75 g of purified water, impregnated in 300 g of RD type silica gel (manufactured by Fuji Silysia Chemical) having a specific surface area of 720 m ³ / g and a pore diameter of 2.2 nm, and reached 35 ° C. What was dried under reduced pressure to 100 torr at the time.

Comparative Example 1

  What was impregnated in the same manner as in Example 1 and dried with hot air at 50 ° C.

Comparative Example 2

  What was impregnated in the same manner as in Example 1 and was not vacuum-dried.

  100 g of chlorine dioxide gas-supported silica gel produced by the method of Example 1 was placed in a glass container and closed with a silicon vent plug.

Comparative Example 3

  100 g of silica alumina added with 25 g of sodium chlorite and mixed uniformly, 100 g in a glass container similar to that of Example 2, and closed with a silicon vent plug.

Comparative Example 4

  25 g of sodium chlorite was put in 75 g of purified water, dissolved in chlorine dioxide gas, and then swollen and gelled in a water-absorbent resin, 100 g was put in the same glass container as in Example 2, and the silicone vent plug was used. Closed one.

  25 g of RD type silica gel was added to and mixed with 75 g of silica gel carrying high-concentration chlorine dioxide gas produced by the method of Example 1, and then placed in a film laminated with three layers of SivmPET12 / ON15 / LLDPE50, and the pressure was reduced to 100 torr and sealed by heat sealing. What you did.

Comparative Example 5

  What was sealed in an OPP bag after production in the same manner as in Example 3.

Comparative Example 6

  A gel produced in the same manner as in Comparative Example 4 and sealed in a PE container.

Comparative Example 7

  What was sealed without adding RD type silica gel after manufacturing by the same method as Example 3.

  A mixture of 75 g of high-concentration chlorine dioxide gas-supported silica gel produced by the method of Example 1 and mixed with 25 g of RD-type silica gel and sealed in a waterproof and moisture-permeable bag having fine pores and an air flow rate of 50 cc / min.

Comparative Example 8

  Gelatinized by adding 10 g of water-absorbing resin and 5 g of citric acid as a gelling agent to 50 g of 25% sodium chlorite solution.

Comparative Example 9

※１：ガス検知管による検出上限値以上
※２：ガス検知管による検出下限値未満Use 100 g of commercially available stabilized chlorine dioxide gel.

* 1: More than upper limit of detection by gas detector tube * 2: Less than lower limit of detection by gas detector tube

※１：検出限界未満After adding 25 g of RD type silica gel to 75 g of high concentration chlorine dioxide gas-supporting silica gel produced by the method of Example 1, 20 g was weighed and sealed in a waterproof and moisture-permeable bag having fine pores and a ventilation rate of 20 cc / min. thing.

* 1: Below detection limit

  As is clear from Table 1, the chlorine dioxide gas-carrying silica gel of Example 1 produced according to the present invention carries several times more gas than other Comparative Examples 1 and 2 and 3. Further, the product manufactured by the method of Comparative Example 1 was difficult to manufacture because a very high concentration of chlorine dioxide gas was desorbed from the silica gel at the time of manufacture.

  From Table 2, the silica gel carrying the chlorine dioxide gas produced according to the present invention changed the color of the silica gel from dark tan to transparent according to the desorption of the chlorine dioxide gas, while the other Comparative Example 3 had no change in appearance. In Comparative Example 4, the gel turned white in about one week, and the timing of the end of use was not known.

  From Table 3, what was preserved by the method of Example 3 according to the present invention maintained high stability even in a harsh environment, while Comparative Example 5 had a chlorine dioxide concentration decreased by about 40%. In this method, the container deteriorated and it was damaged only by applying light force.

As shown in Table 4, the concentration change of the sample used in the method of Example 4 according to the present invention gradually changed over a long period of time. Although the target space was set to 1 m ³ based on the measurement range of the detector tube used for the measurement, when the concentration was diluted to about 10 tatami mat (1.62 m ² × 10) ceiling height 2.6 m, the comparative example 8 of the prior art In the initial stage, the values exceeded both the long-term exposure concentration and the short-term exposure concentration stipulated in ACGIH. On the other hand, in Example 4, the concentration gradually changed without always exceeding the ACGIH standard, and high practicality was confirmed. Comparative Example 9 is a commercially available product that exhibits a deodorizing effect by gelling stabilized chlorine dioxide to improve the storage stability problem. However, as shown in Table 4, the chlorine dioxide gas concentration is quite high. It could not be detected, suggesting the possibility that a practical effect cannot be obtained.

  By using the sample of Example 5 according to the present invention from Table 5, a sterilizing effect of 99.998% or more was obtained even after 6 hours even with the most resistant spore fungus. For other Escherichia coli, Salmonella, etc., the bactericidal effect of Salmonella is 99.99% or more up to the detection limit in E. coli after 1 hour, and an expensive mask such as N95 mask can be used without being disposable. Was suggested.

The silica gel loaded with high-concentration chlorine dioxide obtained by the present invention is fundamentally different from the conventional products that admit the release of chlorine dioxide, the concentration control for the target space is perfect, and the expiration date is also visually confirmed and grasped. Therefore, the present invention is not limited to applications that can perceive the effect, such as deodorization, and can be widely used for hygiene management of spaces. Specifically, it can be used for the prevention of influenza in spaces such as stations, underground malls, various commercial facilities, libraries, social welfare facilities, and schools where unspecified number of users gather and are closed. Since masks that were previously assumed to be disposable can be easily sterilized at a very low cost and can be reused.
While being able to obtain such an excellent effect, the yellow transparent hard beads can be widely used in facilities that are excellent in aesthetics and in which it is difficult to install an antiseptic deodorant.

Claims (3)

  A high-concentration chlorine dioxide gas-supported silica gel characterized by impregnating a porous silicate adjusted to pH 6 or lower with a chlorite aqueous solution and reacting under reduced pressure drying with the temperature controlled at 35 ° C. or lower A silica gel of 20% (weight ratio conversion) or more is added to the weight of the silica gel carrying the high-concentration chlorine dioxide gas according to claim 1, carbon dioxide gas permeability is 10 ml / (m ² · day / MPa) or less, and water vapor permeability It is put in a container or bag of 5 g / (m ² · day) or less and sealed under reduced pressure to 100 torr or less to keep the desorption amount and adsorption amount of chlorine dioxide gas from the silica gel inside the bag in an equilibrium state. Saving method   2. A chlorine dioxide gas-permeable film having 1% (by weight ratio) or more of silica gel added to the weight of the high-concentration chlorine dioxide gas-supporting silica gel according to claim 1 and having one or more micropores of 0.3 nm or more and 100,000 nm or less. Of using silica gel carrying high-concentration chlorine dioxide gas for sanitary management of space and water, which is sealed in a container and releases chlorine dioxide gas