JP2018080062A - Chlorine dioxide generator and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chlorine dioxide generator of a standing type including a hydrous gel that generates chlorine dioxide only by opening the lid, the chlorine odor is small when the lid is opened, and the hydrous gel is at least until the lid is opened. Provided is a chlorine dioxide generator having the form of SOLUTION: A chlorine dioxide generator in which a hydrous gel containing chlorite is contained in a container with a lid, the hydrous gel being gelled with a water-absorbing resin, the hydrous gel being organic or A chlorine dioxide generator characterized by containing a chlorine absorbent such as an inorganic ammonium salt and, if necessary, an inorganic thickener, and a water-containing gel filling the container, with a chlorine odor when the container lid is opened. Without chlorine, chlorine dioxide is gradually generated to exert its sterilizing and deodorizing effect. [Selection] Figure 1

Description

The present invention relates to a chlorine dioxide generator and a method for manufacturing the same. More specifically, the present invention relates to a chlorine dioxide generator comprising a container containing a hydrous gel containing chlorite and a method for producing the same.

In recent years, chlorine dioxide has attracted attention as a disinfectant to replace chlorine, and various chlorine dioxide generators such as a spray type, a neck type, and a stand type are used. In particular, a water-containing resin hydrous gel containing chlorite is used as a standing mold. However, when the hydrogel is stocked for a long time, the water-absorbing resin is decomposed and fluidized by chlorine dioxide, so that there is a problem that the product does not become a product. Therefore, it is a two-pack type product used as a hydrogel by mixing liquid and powder just before use (for example, Patent Documents 1 and 2).

JP 2012-11028 A JP 2011-201721 A

However, there is a problem that it is difficult for consumers to use it by mixing it before use, in that it is difficult to form a uniform gel. There is a demand for a stand-alone chlorine dioxide generator that can be used simply by opening the container lid.
An object of the present invention is a stand-alone chlorine dioxide generator including a hydrous gel that generates chlorine dioxide only by opening the lid, and has little chlorine odor when the lid is opened, and at least until the lid is opened It is to provide a chlorine dioxide generator in which the gel retains the gel form.

As a result of intensive studies, the inventor has found that the above object can be achieved by suppressing generation of chlorine dioxide as much as possible until the container lid is first opened.
That is, the present invention is a chlorine dioxide generator in which a hydrous gel containing chlorite is housed in a container with a lid, the hydrous gel being gelled with a water absorbent resin, A chlorine dioxide generator characterized by containing a chlorine absorbent and containing a hydrogel filling the container.

Furthermore, the present invention is characterized in that the hydrogel is composed of two upper and lower layers having different water-absorbing resin concentrations, and the upper layer contains a chlorine absorbent.
Furthermore, the present invention is characterized in that the chlorine absorbent is an organic or inorganic ammonium salt.
Furthermore, the present invention is characterized in that the hydrated gel further contains an inorganic thickener.
Further, the present invention is characterized in that after forming a hydrous gel containing chlorite in the container, water containing a chlorine absorbent is poured onto the hydrous gel to form a hydrous gel. It is a manufacturing method of a chlorine generator.

In the chlorine dioxide generator of the present invention, the hydrogel in the container keeps the gel form at least until the container lid is opened. Further, when the lid is opened, there is no chlorine odor, and chlorine dioxide is gradually generated to exert its sterilizing and deodorizing effect.

It is a schematic diagram of the chlorine dioxide generator of one embodiment in the present invention. (A) is a perspective view. (B) is sectional drawing when cut | disconnecting by the perpendicular | vertical surface containing the XY axis in (a).

Hereinafter, embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments. Various modifications can be made to the following embodiments within the same and equivalent scope as the present invention.

In the chlorine dioxide generator of the present invention, a hydrous gel containing chlorite is stored in a lidded container. The hydrous gel containing chlorite is obtained by gelling water containing chlorite with a water absorbent resin.
Examples of water containing chlorite include, but are not limited to, an aqueous solution in which chlorite is dissolved, a stabilized aqueous solution of chlorine dioxide, and the like.
Examples of the chlorite include alkali metal chlorites such as sodium chlorite, potassium chlorite, and lithium chlorite, or calcium chlorite, magnesium chlorite, barium chlorite, and the like. Examples include alkaline earth metal chlorates. Among these, sodium chlorite is preferable because it is easily available and has no problem in use.

The concentration of chlorite in water containing chlorite is not particularly limited as long as it generates chlorine dioxide at a concentration effective for deodorization, sterilization, mold prevention, antiseptic, etc. If it does, 0.05 mass% or more and 25 mass% or less are preferable.

The water-absorbing resin that gels water containing chlorite is not particularly limited, whether natural or synthetic, but is inexpensive and has excellent water-absorbing properties such as safety, durability, water-absorbing capacity, and water-retaining capacity. In addition, those that do not have to worry about corruption are preferable.
Examples of such materials include synthetic water-absorbing resins, and are not particularly limited as long as they absorb and retain water. For example, crosslinked polyacrylic acid partially neutralized product, starch-acrylic acid graft Neutralized polymer, hydrolyzate of starch-acrylonitrile graft polymer, saponified vinyl acetate-acrylic ester copolymer, cross-linked isobutylene-maleic anhydride copolymer, 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-2-methylpropane sulfonate copolymer cross-linked product, (meth) acryloylalkane Cross-linked sulfonate copolymer, cross-linked carboxymethyl Cellulose salts, and the like crosslinked polymer of a cationic monomer. Among these, a polyacrylic acid partial neutralized product cross-linked product and a starch-acrylic acid graft polymer neutralized product are preferable because of their particularly good water absorption characteristics, safety and economic efficiency.

The above water-absorbing resins may be used alone or in combination of two or more. The water-absorbent resin is preferably in the form of particles, and there is no limitation on the shape such as an irregularly crushed shape, a spherical shape, a scale shape, a fiber shape, a rod shape, a lump shape, and a powder shape. From the viewpoint of generation of chlorine dioxide, it is more preferable that the powder form.

Although there is no limitation in particular about the average particle diameter of particle | grains, Preferably it is 30-850 micrometers, More preferably, it is 60-400 micrometers.
The water absorption ratio is preferably 20 to 1,000 g / g, more preferably 80 to 600 g / g. When the water absorption ratio is 20 g / g or more, the gel characteristics are good, and when it is 1,000 g / g or less, the gel form is easily maintained. The water absorption magnification is in accordance with the usual method for measuring water absorbent resin.

The amount of the water absorbent resin is 1% or more and 10% or less by mass with respect to water containing chlorite. If it is 1% or more, gelation is possible, and if it is 10% or less, the generated gel does not pass and is easy to handle. Preferably they are 2% or more and 5% or less.

Chlorine absorbents contained in hydrous gel containing chlorite include inorganic chlorine absorbents such as calcium carbonate, limestone, quicklime, slaked lime, zeolite, activated carbon, inorganic ammonium salts, and organic chlorines such as organic ammonium salts. An absorbent is mentioned. Preference is given to organic ammonium salts or inorganic ammonium salts which are water-soluble. If it is water-soluble, it can easily absorb chlorine dissolved in the hydrous gel.

The organic or inorganic ammonium salt is not particularly limited, but organic ammonium salts such as ammonium citrate, ammonium hydrogen citrate, ammonium maleate, ammonium hydrogen maleate; ammonium carbonate, ammonium hydrogen carbonate, phosphorus Examples thereof include inorganic ammonium salts such as acid ammonium salt, ammonium hydrogen phosphate salt, ammonium hydrogen sulfate salt, and ammonium hydrogen sulfite salt. Preferred are inorganic ammonium salts, and more preferred are inorganic hydrogen ammonium salts.

The amount of the chlorine absorbent contained in the water-containing gel is not limited as long as it does not cause a chlorine odor when the container lid is opened, and varies depending on the type of the chlorine absorbent. It is preferable that it is 0.1 mass% or more and 5 mass% or less with respect to the mass of a hydrous gel. 0.5 mass% or more and 3 mass% or less are more preferable. If it is 0.1 mass% or more, the effect of suppressing the chlorine odor when the lid is opened appears, and the stability of the gel is good until the lid is opened. If it is 5 mass% or less, the antibacterial and deodorizing effects of chlorine dioxide are good.

The method for gelling water containing chlorite with a water-absorbing resin is not particularly limited, but it can be easily obtained by adding the water-absorbing resin to water containing chlorite at room temperature and stirring. Moreover, it is preferable to mix a chlorine absorbent before gelling water containing chlorite.

A container with a lid for storing a hydrous gel containing chlorite can be made of plastic, glass, metal, etc., but plastic glass is preferred from the viewpoint of corrosion. The size of the container is not particularly limited, but is preferably 10 mL or more and 2 KL or less so that it can be easily used by consumers.

The container lid is preferably provided at the top. In the present invention, “the hydrated gel fills the container” means that there is no gap between the lid and the gel surface, but in reality, some gap is inevitably produced when the lid is covered. In the present invention, the gap between the lid and the gel surface is preferably 7 mL or less because the chlorine odor is not a concern. Therefore, in the present invention, “the hydrogel fills the container” means 7 mL or less.

The hydrated gel in the container may be placed in the container after the hydrated gel is prepared, but the hydrated gel is preferably produced in the container from the viewpoint of efficiency. In addition, chlorine is volatilized when the lid is opened, but chlorine in the space between the lid of the container and the gel is likely to volatilize, and then chlorine dissolved in the upper hydrous gel is volatilized. Even if it dissolves in the center or bottom of the hydrous gel, it is unlikely that it will evaporate immediately. Therefore, it is economical and preferable to control the upper hydrogel under the lid in the container. That is, the chlorine absorbent may be added to the entire hydrogel, but the container may be filled with the hydrogel, and the chlorine absorbent may be added only to the hydrogel portion under the lid and the upper portion of the hydrogel. The effects of the invention can be achieved.

When a chlorine absorbent is blended only in the upper layer part, after forming a hydrous gel containing chlorite in a container, water containing a chlorine absorbent is poured onto the hydrous gel to form a hydrous gel. preferable. A hydrogel may be formed separately and stacked in two layers, but after preparing a hydrogel containing chlorite and pouring water containing a chlorine absorbent from above, chlorite will be added. The water-absorbing resin in the water-containing gel contained further swells and absorbs water containing the above chlorine absorbent to swell and gel. In this case, it is necessary that the water-absorbent resin in the vicinity of the surface of the first hydrogel still has the capacity to absorb water. Since the water absorption capacity of the water absorbent resin in the container is proportional to the amount of the water absorbent resin and the water absorption magnification, it is preferable to prepare the first water-containing gel in consideration of this fact. In addition, since the amount of water increases when the gel is formed, it is preferable to add water containing a chlorine absorbent in consideration of the fact.
The ratio of the upper layer portion of the hydrogel to the lower layer portion below it is preferably 1/9 to 5/5 by volume.

That is, the hydrogel is composed of upper and lower two layers having different water absorbent resin concentrations, and the upper layer contains a chlorine absorbent. The upper layer has a low concentration of water-absorbing resin. In this case, the boundary between the upper and lower layers is not clear, and the concentration of the water-absorbent resin in the upper gel is smaller than that of the lower layer. The upper layer chlorine absorbent also moves to the lower layer, but its concentration is lower than that of the upper layer.

The hydrogel preferably further contains an inorganic thickener. When used together with an inorganic thickener, the inorganic thickener thickens water without being decomposed by chlorine dioxide, so it is effective in slowing the fluidization of the gel, and the shape of the gel after opening the lid is good Can be held in.
As the inorganic thickener, commonly used inorganic thickeners can be used, silicon dioxide, sodium silicate, wollastonite, magnesium silicate, tricalcium silicate, aluminum silicate, magnesium chloride, and bentonite Sepiolite, montmorillonite, diatomaceous earth, talc, alumina gel, alumina / silica gel, calcium silicate, calcined aggregate such as shellfish / coral, and calcined clay. Of these, bentonite, sepiolite, and montmorillonite are preferable.

The same range as the above water-absorbent resin can be used for the shape and particle diameter of the inorganic thickener. The usage-amount of an inorganic thickener is 3 to 30 mass% with respect to the mass of a hydrogel. If the inorganic thickener is 3% by mass or more, the gel form can be maintained for a long time, and if it is 30% by mass or less, chlorine dioxide can be released for a long time. Preferably they are 5 mass% or more and 20 mass% or less.

You may mix | blend the following compounds with a hydrous gel with a chlorite, and separately normally using a chlorine dioxide generator.
When water is absorbed by the water-absorbent resin, the pH of the water in the inside is lowered, but an acid (acidic substance) can be further used in combination to promote generation of chlorine dioxide. Examples of such acids include inorganic acids such as phosphoric acid, organic acids such as citric acid, malic acid, succinic acid, and tartaric acid, bleached powder, and isocyanuric acids.

Hydrogen salts (excluding ammonium salts) can be used in combination to further promote the generation of chlorine dioxide. The hydrogen salt is a salt in which H ⁺ of a polyvalent acid is substituted with a cation, and still has H ⁺ remaining, for example, sodium hydrogen sulfate, potassium hydrogen sulfate, sodium dihydrogen phosphate, phosphorus Examples thereof include disodium oxyhydrogen, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

In addition, if too much gel is put in the lid, the gel adheres to the lid and the gel adheres to the body when used. As a precaution, a breathable sheet can be placed on the gel surface. The breathable sheet is not limited as long as chlorine dioxide does not pass through and the gel does not pass through, and examples thereof include paper, cloth sheets, and plastic porous sheets. Further, chlorine may be further adsorbed by using an activated carbon adhering sheet or the like as the breathable sheet, and the passing amount of chlorine dioxide or chlorine may be adjusted by adjusting the thickness of the semipermeable membrane film or sheet. .

The semipermeable membrane film can suppress gas volatilization as described above. At the same time, the release of chlorine dioxide from the system can be suppressed, and the release rate can be made more uniform overall. The semipermeable membrane film is not particularly limited, and the semipermeable membrane film may be selected so as to obtain a more uniform release rate of target chlorine dioxide.
Examples of such semipermeable membrane films include polyvinyl alcohol films (vinylon films), cellophane, low-stretch nylon films, ethylene vinyl acetate copolymer films, ethylene-vinyl alcohol copolymer films, and porous films. (Film with micropores) and the like are exemplified, but not limited thereto.

FIG. 1 is a schematic diagram of a chlorine dioxide generator 1 according to an embodiment of the present invention. (A) is a perspective view. (B) is sectional drawing when cut | disconnecting by the perpendicular | vertical surface containing the XY axis in (a). (A), (b) is the state sealed with the lid | cover 3 of the container 2. FIG. The container 2 is almost filled with the hydrogel 3. The hydrogel 4 is composed of upper and lower two layers 4a and 4b. A breathable sheet 5 is placed on top of the hydrogel 4 just below the lid 2. Since the container 2 having such a configuration is filled with the hydrogel 4, the gel state can be maintained until the lid 2 is opened.

The chlorine dioxide generator produced as described above does not have a chlorine odor when the lid is opened, and chlorine dioxide is gradually generated to exhibit the sterilization and deodorizing effect. Further, at least until the container lid is opened, the hydrated gel in the container maintains the gel form.

The reason for the above effects is not clear, but can be estimated as follows.
Chlorite generates chlorine dioxide with acid, but the reaction is in equilibrium. Chlorine dioxide becomes a gas at 11 ° C. and accumulates in the space in the container to maintain a vapor-liquid equilibrium relationship. Gas tends to gather in a space without liquid, and the smaller the space, the less chlorine dioxide. Therefore, the generation amount of chlorine dioxide is also suppressed. Chlorine is also generated with the generation of chlorine dioxide, and the amount of generated chlorine is similarly reduced as the container space is reduced. Chlorine is slightly dissolved in water together with chlorine dioxide, but chlorine is absorbed and retained by the chlorine absorbent dissolved in the gel. Then, the chlorine odor is further suppressed when the lid is first opened. Although chlorine dioxide and chlorine are gradually generated after opening the lid of the container, it has been confirmed that the sterilization and deodorizing effect is exhibited even if chlorine dioxide is generated within a range where the chlorine odor is not a concern. If the generation amount of chlorine dioxide is controlled within that range, it can be used practically.

Further, since the gel of the water absorbent resin is an organic gel, it is gradually decomposed by chlorine dioxide and gradually fluidized. However, as described above, the water-containing gel can suppress the generation of chlorine dioxide as well as the generation of chlorine by reducing the space without the gel together with the chlorine absorbent. When the amount of chlorine dioxide is small, decomposition of the water-absorbent resin is delayed, and the gel is difficult to fluidize for a long period of time. At least the form of the gel can be maintained until the container lid is opened.

Examples will be described below, but the present invention is not limited thereto.
Example 1
"Sunwet ST-500D" (manufactured by Sanyo Kasei Kogyo Co., Ltd.) in water obtained by dissolving 1.25 g of sodium chlorite in a polypropylene container having a diameter of 5.8 cm and a depth of 5,5 cm having the shape shown in FIG. Polyacrylic acid type water-absorbing resin) 3.5 g, “Pangel AD” (manufactured by Enomoto Kasei Co., Ltd., inorganic thickener, sepiolite) was added and mixed. Gelation occurred after a few minutes. Approximately 60% of the container was filled. Further, a 1.0% ammonium hydrogen carbonate aqueous solution was added from above and allowed to stand for a while to cause the above water to gel. The gel went up to the top of the lid. After completely gelling, a non-woven sheet (polyester / acrylic blend) was placed on the surface of the hydrogel to match the shape, and the lid was closed and sealed from above to produce the chlorine dioxide generator A of the present invention. Although the container was filled with the hydrogel, the space between the lid and the hydrogel surface was 6 mL.

(Example 2)
In Example 1, instead of 1.25 g of sodium chlorite, 3.5 g of “Sunwet ST-500D”, 7 g of “Pangel AD”, 1.0% ammonium hydrogen carbonate aqueous solution, 2.5 g of sodium chlorite , “Sunwet ST-500D” 4.0 g, “Pangel AD” 9 g, and 2.0% ammonium hydrogen carbonate aqueous solution, except that a chlorine dioxide generator B of the present invention is produced in the same manner as in Example 1. did. The space between the lid and the hydrogel surface was 5 mL.

(Example 3)
In Example 1, “Pangel AD” 7 g and 1.0% ammonium hydrogen carbonate aqueous solution in place of “Pangel AD” 9 g and 1.0% ammonium hydrogenphosphate aqueous solution in the same manner as in Example 1 Thus, the chlorine dioxide generator C of the present invention was produced. The space between the lid and the hydrogel surface was 7 mL.

Example 4
In Example 2, a chlorine dioxide generator D of the present invention was produced in the same manner as in Example 2 except that a 1.0% ammonium carbonate aqueous solution was used instead of the 2.0% ammonium bicarbonate aqueous solution. The space between the lid and the hydrogel surface was 2 mL.

(Comparative Example 1)
A single layer of gel was prepared in the container used in Example 1. 4.0 g of “Sunwet ST-500D” and 9 g of “Pangel AD” were added to water in which 2.5 g of sodium chlorite had been dissolved, and mixed. Gelation occurred after a few minutes. A comparative chlorine dioxide generator E filling about 60% of the container was produced. The space between the lid and the hydrogel surface was 30 mL.

(Comparative Example 2)
A single layer of gel was prepared in the container used in Example 1. 3.5 g of “Sunwet ST-500D” and 7 g of “Pangel AD” were placed in water in which 1.25 g of sodium chlorite had been dissolved, and mixed to fill about 60% of the container and gelled. Distilled water was added from above and gelled to prepare a comparative chlorine dioxide generator F. The space between the lid and the hydrogel surface was 7 mL.

(Comparative Example 3)
A single layer of gel was prepared in the container used in Example 1. Put "Sunwet ST-500D" 3.5g and "Pangel AD" 7g in water in which 1.25g of sodium chlorite is dissolved, mix and fill to about 95% in the container to gel. A chlorine dioxide generator G was produced. The space between the lid and the hydrogel surface was 6 mL

(Comparative Example 4)
In Comparative Example 1, a comparative chlorine dioxide generator H was prepared in the same manner except that 1.3 g of ammonium bicarbonate was added. The space between the lid and the hydrogel surface was 30 mL.

With respect to the chlorine dioxide generator of the present invention and the comparative chlorine dioxide generator, the chlorine odor and chlorine generation amount, gel stability, and tobacco deodorization properties when the container lid was opened were evaluated by the following test methods. The results are shown in Table 1.

(Test method)
1. When the container lid was opened, the chlorine odor and chlorine generation amount container was sealed and allowed to stand at 25 ° C. for 28 days, and then the lid was opened and placed in a 4 L plastic container to cover the plastic container. After standing for 10 minutes, the smell of chlorine in the container was sniffed with a nose, and the degree of chlorine smell was judged by five people. The amount of generated chlorine was measured with a Kitagawa type detector tube.
Chlorine odor: Small There is no chlorine odor, but there is no concern
Medium There is a slight odor of chlorine.
Large Chlorine smell

2. The stability of the gel container was covered and allowed to stand in a thermostatic chamber at 37 ° C. for 30 days, then the lid was opened and the container was tilted to observe the fluidity of the gel.
○: Retains gel form
Δ: Somewhat fluidized
×: Completely fluidized

3. The container was opened for 7 days in a tobacco deodorant room. This container was put into a 15 L plastic container in which tobacco smoke was sealed for 15 seconds, and the time until the tobacco odor disappeared after sealing was measured.

From Table 1, Examples 1-4 have almost no chlorine smell and the deodorizing property of the tobacco which is the effect of chlorine dioxide is also favorable. The stability of the gel is also good at 30 ° C. for 30 days. It was confirmed that the effect of the present invention was achieved if the space without gel in the container was reduced and a chlorine absorbent was added to the upper layer portion.

1 Chlorine dioxide generator 2 Container 3 Lid 4, 4a, 4b Water-containing gel 5 Breathable sheet

Claims (5)

A chlorine dioxide generator in which a hydrous gel containing chlorite is housed in a container with a lid,
A chlorine dioxide generator characterized in that the water-containing gel is gelled with a water-absorbing resin, the water-containing gel contains a chlorine absorbent, and the water-containing gel fills the inside of the container.   2. The chlorine dioxide generator according to claim 1, wherein the hydrous gel is composed of two upper and lower layers having different water absorbent resin concentrations, and the upper layer contains a chlorine absorbent. The chlorine dioxide generator according to claim 1 or 2, wherein the chlorine absorbent is an organic or inorganic ammonium salt. The chlorine dioxide generator according to any one of claims 1 to 3, wherein the hydrogel further contains an inorganic thickener. The hydrous gel containing chlorite is formed in the container, and then the hydrous gel is formed by pouring water containing a chlorine adsorbent onto the hydrogel. The manufacturing method of the chlorine dioxide generator of any one of Claims.

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