CHLORINE DIOXIDE GAS GENERATING METHOD, LIQUID COMPOSITION, GEL COMPOSITION, AND CHLORINE DIOXIDE GAS GENERATING KIT
20200231436 ยท 2020-07-23
Inventors
Cpc classification
B65D81/3266
PERFORMING OPERATIONS; TRANSPORTING
A61L2209/21
HUMAN NECESSITIES
A01N59/00
HUMAN NECESSITIES
International classification
A01N59/00
HUMAN NECESSITIES
A61L9/04
HUMAN NECESSITIES
Abstract
Chlorine dioxide gas is immediately generated at a stable concentration from a liquid composition. The composition is obtained by mixing an aqueous chlorite solution, an activator that immediately adjusts the pH of the aqueous chlorite solution, an activation inhibitor that slowly mitigates an action of the activator, and a metal iodide such that the metal iodide is contained in a proportion of 0.4% by mass or less and the activation inhibitor is contained in a proportion of 1% by mass or less with respect to 1 L of 1% by mass aqueous chlorite solution.
Claims
1. A chlorine dioxide gas generating method for immediately generating chlorine dioxide gas at a stable concentration from a liquid composition, comprising obtaining the composition by mixing an aqueous chlorite solution, an activator that immediately adjusts a pH of the aqueous chlorite solution, thereby causing the aqueous chlorite solution to generate chlorine dioxide gas, an activation inhibitor that slowly mitigates an action of the activator, and a metal iodide such that the metal iodide is contained in a proportion of 0.4% by mass or less and the activation inhibitor is contained in a proportion of 1% by mass or less with respect to 1 L of 1% by mass aqueous chlorite solution.
2. A chlorine dioxide gas generating method for immediately generating chlorine dioxide gas at a stable concentration from a gel composition, comprising obtaining the composition by mixing an aqueous chlorite solution, an activator that immediately adjusts a pH of the aqueous chlorite solution, thereby causing the aqueous chlorite solution to generate chlorine dioxide gas, an activation inhibitor that slowly mitigates an action of the activator, a metal iodide, and an absorbent resin such that the metal iodide is contained in a proportion of 0.4% by mass or less and the activation inhibitor is contained in a proportion of 1% by mass or less with respect to 1 L of 1% by mass aqueous chlorite solution.
3. A liquid composition for immediately generating chlorine dioxide gas at a stable concentration, comprising an aqueous chlorite solution, an activator that immediately adjusts a pH of the aqueous chlorite solution, thereby causing the aqueous chlorite solution to generate chlorine dioxide gas, an activation inhibitor that slowly mitigates an action of the activator, and a metal iodide such that the metal iodide is contained in a proportion of 0.4% by mass or less and the activation inhibitor is contained in a proportion of 1% by mass or less with respect to 1 L of 1% by mass aqueous chlorite solution.
4. A gel composition for immediately generating chlorine dioxide gas at a stable concentration, comprising an aqueous chlorite solution, an activator that immediately adjusts a pH of the aqueous chlorite solution, thereby causing the aqueous chlorite solution to generate chlorine dioxide gas, an activation inhibitor that slowly mitigates an action of the activator, a metal iodide, and an absorbent resin such that the metal iodide is contained in a proportion of 0.4% by mass or less and the activation inhibitor is contained in a proportion of 1% by mass or less with respect to 1 L of 1% by mass aqueous chlorite solution.
5. A chlorine dioxide gas generating kit for immediately generating chlorine dioxide gas at a stable concentration from a liquid composition, comprising: a first agent containing an aqueous chlorite solution; and a second agent containing an activator that immediately adjusts a pH of the aqueous chlorite solution, thereby causing the aqueous chlorite solution to generate chlorine dioxide gas, wherein each of an activation inhibitor that slowly mitigates an action of the activator, and a metal iodide is contained in either the first agent or the second agent, 0.4% by mass or less of the metal iodide and 1% by mass or less of the activation inhibitor are contained with respect to 1 L of 1% by mass aqueous chlorite solution, and the composition is obtained by mixing the first agent and the second agent.
6. A chlorine dioxide gas generating kit for immediately generating chlorine dioxide gas at a stable concentration from a gel composition, comprising: a first agent containing an aqueous chlorite solution; and a second agent containing an activator that immediately adjusts a pH of the aqueous chlorite solution, thereby causing the aqueous chlorite solution to generate chlorine dioxide gas, and an absorbent resin, wherein each of an activation inhibitor that slowly mitigates an action of the activator, and a metal iodide is contained in either the first agent or the second agent, 0.4% by mass or less of the metal iodide and 1% by mass or less of the activation inhibitor are contained with respect to 1 L of 1% by mass aqueous chlorite solution, and the composition is obtained by mixing the first agent and the second agent.
7. The chlorine dioxide gas generating kit according to claim 5, wherein 0.03% by mass or more and 0.3% by mass or less of the activation inhibitor is contained with respect to 1 L of 1% by mass aqueous chlorite solution.
8. The chlorine dioxide gas generating kit according to claim 5, wherein 0.01% by mass or more and 0.4% by mass or less of the metal iodide is contained with respect to 1 L of 1% by mass aqueous chlorite solution.
9. The chlorine dioxide gas generating kit according to claim 5, wherein a mass ratio between the activation inhibitor and the metal iodide is 3:1 to 1:3.
10. The chlorine dioxide gas generating kit according to claim 5, wherein the activation inhibitor is an alkali metal silicate or an alkaline-earth metal silicate.
11. The chlorine dioxide gas generating kit according to claim 10, wherein the activation inhibitor is a sodium silicate.
12. The chlorine dioxide gas generating kit according to claim 5, wherein the metal iodide is a potassium iodide.
13. The chlorine dioxide gas generating kit according to claim 5, wherein the activator is an inorganic acid or an organic acid, or a salt thereof.
14. The chlorine dioxide gas generating kit according to claim 5, wherein the first agent is sealed in a sealable first container, and the second agent is sealed in a sealable second container that is different from the first container.
15. The chlorine dioxide gas generating kit according to claim 5, wherein the first agent and the second agent are sealed in the same sealable container in a state of being separated from each other by a separating portion that can be manually deactivated.
16. The chlorine dioxide gas generating kit according to claim 15, wherein the separating portion is constituted by a labyrinth structure portion.
17. The chlorine dioxide gas generating kit according to claim 5, wherein the first agent is sealed in a sealable and easily breakable first container, and the second agent is sealed together with the first container in a sealable second container.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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BEST MODE FOR CARRYING OUT THE INVENTION
First Embodiment
[0057] Hereinafter, a chlorine dioxide gas generating method, a liquid composition, a gel composition, and a chlorine dioxide gas generating kit according to a first embodiment will be described. The chlorine dioxide gas generating method of this embodiment is a method for immediately generating chlorine dioxide gas at a stable concentration, by mixing an aqueous chlorite solution, a fast-acting activator, a metal iodide, a slow-acting activation inhibitor, and, optionally, an absorbent resin. In this embodiment, this method is performed using a chlorine dioxide gas generating kit K (see
[0058] In the description below, as an example, a case will be described in which chlorine dioxide gas is immediately generated at a stable concentration from the gel composition 3 by also mixing the absorbent resin that is an optional component.
[0059] The aqueous chlorite solution is an aqueous solution containing chlorite. There is no particular limitation on the chlorite contained in the aqueous chlorite solution, as long as it is substantially stable, and is activated by being mixed with the activator and produces chlorine dioxide gas. Examples of the chlorite include alkali metal chlorite and alkaline-earth metal chlorite. Examples of the alkali metal chlorite include sodium chlorite (NaClO.sub.2), potassium chlorite (KClO.sub.2), and lithium chlorite (LiClO.sub.2). Examples of the alkaline-earth metal chlorite include calcium chlorite (Ca (ClO.sub.2).sub.2), magnesium chlorite (Mg (ClO.sub.2).sub.2), and barium chlorite (Ba (ClO.sub.2).sub.2). Of these, it is preferable to use sodium chlorite.
[0060] There is no particular limitation on the pH of the aqueous chlorite solution before mixing, but it is preferably 9 or more and 13 or less. The pH of the aqueous chlorite solution is more preferably 10 or more and 12.5 or less, and even more preferably 11 or more and 12 or less. If the pH is within this range, the chlorite in the aqueous chlorite solution can be stabilized and stably stored for a long period of time. The pH of the aqueous chlorite solution can be adjusted using an alkali agent. Examples of the alkali agent include sodium hydroxide (NaOH) and potassium hydroxide (KOH).
[0061] The chlorite concentration of the aqueous chlorite solution is preferably 0.01% by mass or more and 25% by mass or less, and more preferably 0.1% by mass or more and 15% by mass or less.
[0062] The activator activates the chlorite in the aqueous chlorite solution, when mixed with the solution, thereby causing the chlorite to generate chlorine dioxide gas. Examples of the activator include an inorganic acid and an organic acid, and a salt thereof. Examples of the inorganic acid include hydrochloric acid (HCl), carbonic acid (H.sub.2CO.sub.3), sulfuric acid (H.sub.2SO.sub.4), phosphoric acid (H.sub.3PO.sub.4), and boric acid (H.sub.3BO.sub.3). Examples of a salt of the inorganic acid include sodium hydrogen carbonate (NaHCO.sub.3), sodium dihydrogen phosphate (NaH.sub.2PO.sub.4), and disodium hydrogen phosphate (Na.sub.2HPO.sub.4). As the inorganic acid and a salt thereof, it is also possible to use an anhydride (e.g., sulfuric anhydrite, pyrophosphoric acid, etc.), and, for example, it is preferable to use sodium dihydrogen pyrophosphate, or the like.
[0063] Examples of the organic acid include acetic acid (CH.sub.3COOH), citric acid (H.sub.3(C.sub.3H.sub.5O(COO).sub.3)), and malic acid (COOH(CHOH)CH.sub.2COOH). Examples of a salt of the organic acid include sodium acetate (CH.sub.3COONa), disodium citrate (Na.sub.2H(C.sub.3H.sub.5O(COO).sub.3)), trisodium citrate (Na.sub.3(C.sub.3H.sub.5O(COO).sub.3)), and disodium malate (COONa(CHOH)CH.sub.2COONa).
[0064] The activator immediately adjusts the pH of the aqueous chlorite solution, when mixed with the aqueous chlorite solution. More specifically, the activator immediately lowers the pH of the aqueous chlorite solution, and provides an acidic atmosphere. In this sense, the activator can be said to be a pH adjuster that immediately imparts acidity. The activator adjusts the pH of the aqueous chlorite solution preferably to 2.5 or more and 6.8 or less. The activator adjusts the pH of the aqueous chlorite solution more preferably to 3.5 or more and 6.5 or less, and even more preferably to 4.5 or more and 6.0 or less. Preferred examples of the activator include sodium metaphosphate whose 1% aqueous solution has a pH of 1.7 or more and 2.4 or less.
[0065] For example, if the chlorite contained in the aqueous chlorite solution is sodium chlorite, chlorous acid is produced following Formula (1) below, by adjusting the pH of the aqueous solution as described above to provide an acidic atmosphere.
NaClO.sub.2+H.sup.+.fwdarw.Na.sup.++HClO.sub.2(1)
[0066] Meanwhile, the equilibrium reaction in a case in which chlorine dioxide gas is dissolved in water is expressed by Formula (2) below.
2ClO.sub.2+H.sub.2OHClO.sub.2+HClO.sub.3(2)
[0067] At that time, Formula (3) below is obtained.
[HClO.sub.2][HClO.sub.3]/[ClO.sub.2]=1.210.sup.7(3)
[0068] When chlorous acid is produced following Formula (1) by mixing the aqueous chlorite solution and the activator to set the aqueous chlorite solution to an acidic atmosphere, the equilibrium reaction shifts leftward in Formula (2) according to the theorem of Formula (3), and thus chlorine dioxide gas can be generated in the aqueous solution at an overwhelming probability.
[0069] In the chlorine dioxide gas generating method of this embodiment, in addition to the activator that immediately adjusts the pH of the aqueous chlorite solution (which will be referred to as a first activator in this example), a second activator that slowly adjusts the pH of the aqueous chlorite solution may be mixed as well. In this sense, the second activator can be said to be a pH adjuster that slowly imparts acidity. The second activator may be an inorganic acid or organic acid with a level of acidity lower than that of the first activator, or a salt thereof. Preferred examples of the second activator include sodium pyrophosphate whose 1% aqueous solution has a pH of 3.8 or more and 4.5 or less.
[0070] The metal iodide produces iodide ions and acts as a catalyst in an aqueous chlorite solution, when mixed with the solution. The metal iodide facilitates the generation of chlorine dioxide gas in the early stage of mixing with the aqueous chlorite solution and the activator. Examples of the metal iodide include an alkali metal iodide and an alkaline-earth metal iodide. Specific examples thereof include a sodium iodide (NaI), a potassium iodide (KI), a magnesium iodide (MgI.sub.2), and a calcium iodide (CaI.sub.2). Of these, it is preferable to use a potassium iodide.
[0071] The amount of metal iodide added to the aqueous chlorite solution is 0.4% by mass or less, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). There is no particular limitation on the lower limit value of the amount of metal iodide added, but it is set to an amount (* not including zero) that enables an effect of facilitating the generation of chlorine dioxide gas in the early stage of mixing to be obtained. The amount of metal iodide added is preferably 0.01% by mass or more and 0.4% by mass or less, with respect to 1 L of 1% by mass aqueous chlorite solution. The amount of metal iodide added is more preferably 0.1% by mass or more and 0.25% by mass or less, with respect to 1 L of 1% by mass aqueous chlorite solution.
[0072] The activation inhibitor slowly mitigates the action of the activator, when mixed with the aqueous chlorite solution together with the activator. The activation inhibitor slowly mitigates the action of the activator of immediately lowering the pH of the aqueous chlorite solution. The activation inhibitor may substantially be a material that slowly increases the pH of the aqueous chlorite solution. In this sense, the activation inhibitor can be said to be a pH adjuster that slowly imparts alkalinity. Examples of the activation inhibitor include an alkali metal silicate and an alkaline-earth metal silicate. Examples of the alkali metal silicate include a lithium silicate (mLi.sub.2O.nSiO.sub.2), a sodium silicate (mNa.sub.2O.nSiO.sub.2), and a potassium silicate (mK.sub.2O.nSiO.sub.2). Examples of the alkaline-earth metal silicate include a magnesium silicate (mMgO.nSiO.sub.2), a calcium silicate (mCaO.nSiO.sub.2), and a strontium silicate (mSrO.nSiO.sub.2). Of these, it is preferable to use a sodium silicate (in particular, a sodium metasilicate). It is assumed that the alkali metal silicate and the alkaline-earth metal silicate include hydrates thereof.
[0073] There is no particular limitation on the molar ratio (the above-mentioned n/m) between an oxide of an alkali metal or an alkaline-earth metal silicate and a silicon dioxide, but it is preferably 0.9 or more and 1.2 or less.
[0074] For example, if the activation inhibitor is a sodium metasilicate, the sodium metasilicate dissociates (hydrolyzes) in the aqueous solution as in Formula (4) below.
Na.sub.2O.SiO.sub.2+2H.sub.2O.fwdarw.2NaOH+H.sub.2SiO.sub.3(4)
[0075] In this manner, sodium hydroxide (NaOH) produced after a short period of time has passed after mixing with the aqueous chlorite solution acts so as to partially neutralize the fast-acting activator (an acid in this example), thereby slowly mitigating the action of the activator. As a result, an abrupt increase in the chlorine dioxide gas concentration in the early stage after mixing is inhibited, and chlorine dioxide gas can be gradually released from the early stage.
[0076] Meanwhile, as in Formula (4), metasilicic acid (H.sub.2SiO.sub.3) is also produced in addition to sodium hydroxide. Metasilicic acid is produced after a short period of time has passed after mixing with the aqueous chlorite solution, and acts as an acid, and, in this sense, silicon dioxide (SiO.sub.2) from which metasilicic acid is produced is an example of the pH adjuster that slowly imparts acidity. Sodium hydroxide and metasilicic acid produced later further react with each other as in Formula (5) below.
2NaOH+H.sub.2SiO.sub.3.fwdarw.Na.sub.2O.SiO.sub.2+2H.sub.2O(5)
[0077] In this manner, sodium metasilicate serving as an activation inhibitor shifts between a state of being dissociated into sodium hydroxide and metasilicic acid and a state of being recombined, in the aqueous solution (see
[0078] Then, sodium metasilicate in the state of being dissociated into sodium hydroxide and metasilicic acid slowly adjusts the pH of the aqueous chlorite solution. That is to say, in the state in which sodium metasilicate has dissociated into sodium hydroxide and metasilicic acid, metasilicic acid acts as a supply source of hydrogen ions (H.sup.+), and sodium hydroxide acts as a supply source of hydroxide ions (OH.sup.), thereby slowly adjusting the pH of the aqueous chlorite solution. As a result, it is possible to slowly generate chlorine dioxide gas, and to generate chlorine dioxide gas at a stable concentration for a long period of time. Furthermore, when used together with the metal iodide, it is possible to immediately generate chlorine dioxide gas at a stable concentration.
[0079] In this example, generated at a stable concentration means that, in a closed system, the concentration of generated chlorine dioxide gas slowly increases without having a peak in the early stage after mixing and then keeps a constant level (see
[0080] Note that, in
[0081] Furthermore, according to the method of this embodiment, it is possible to freely control the concentration of generated chlorine dioxide gas. Conventionally, the concentration of generated chlorine dioxide gas depends on the concentration of chlorite, and control of the maximum concentration was not possible, whereas, in this method, the maximum concentration (preferably, final concentration) of chlorine dioxide gas can be freely controlled by adjusting the amount of activation inhibitor added. Thus, it is possible to easily generate chlorine dioxide gas at a concentration suitable for the purpose of use.
[0082] The amount of activation inhibitor added to the aqueous chlorite solution is 1% by mass or less, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). There is no particular limitation on the lower limit value of the amount of activation inhibitor added, but it is set to an amount (* not including zero) that enables an effect of realizing generation of chlorine dioxide gas at a stable concentration to be obtained. The amount of activation inhibitor added is preferably 0.03% by mass or more and 0.3% by mass or less, with respect to 1 L of 1% by mass aqueous chlorite solution. The amount of activation inhibitor added is more preferably 0.1% by mass or more and 0.25% by mass or less, with respect to 1 L of 1% by mass aqueous chlorite solution.
[0083] There is no particular limitation on the ratio between the amounts of metal iodide and activation inhibitor added, but it may be metal iodide:activation inhibitor=3:1 to 1:3. The ratio between the amounts of metal iodide and activation inhibitor added is preferably 2:1 to 1:2, more preferably 1.5:1 to 1:1.5, and even more preferably 1.25:1 to 1:1.25.
[0084] The absorbent resin absorbs moisture, and forms a gel composition. Examples of the absorbent resin include a starch-based absorbent resin, a cellulose-based absorbent resin, and a synthetic polymer-based absorbent resin. Examples of the starch-based absorbent resin include a starch-acrylonitrile graft copolymer and a starch-acrylic acid graft copolymer. Examples of the cellulose-based absorbent resin include a cellulose-acrylonitrile graft copolymer and a cross-linked carboxymethylcellulose. Examples of the synthetic polymer-based absorbent resin include a polyvinyl alcohol-based absorbent resin and an acrylic-based absorbent resin.
[0085] The activator, the metal iodide, the activation inhibitor, and the absorbent resin may be a solid (e.g., in a powdery form or a granular form) before mixed with the aqueous chlorite solution. Furthermore, the activator, the metal iodide, and the activation inhibitor may be dissolved when mixed with the aqueous chlorite solution.
[0086] The chlorine dioxide gas generating method of this embodiment may be performed using the chlorine dioxide gas generating kit K shown in
[0087] Furthermore, the second agent 2 formed as a solid (the activator and the absorbent resin) is contained in a second container 20 obtained by sticking plastic films to each other. The second container 20 may be obtained by stacking two plastic films and causing their entire peripheral edge portions to adhere to each other, or by folding one plastic film in half and causing the peripheral edge portions other than the folded portion to adhere to each other. In this manner, the second agent 2 is sealed in the sealable second container 20 that is different from the first container 10.
[0088] There is no limitation on the material and the shape of the first container 10 and the second container 20, as long as they are sealable containers. The material for forming the first container 10 and the second container 20 is not limited to plastic, and may be, for example, metal. Furthermore, the shape of the first container 10 is not limited to a fixed shape, and may be a deformable shape. The shape of the second container 20 is not limited to a deformable shape, and may be a fixed shape. Moreover, a configuration may also be employed in which the first agent 1 and the second agent 2 are contained in an integrated container having two container sections, and can be mixed with each other by bringing the two container sections into communication with each other at the time of use.
[0089] In the chlorine dioxide gas generating kit K of this embodiment, the first agent 1 is distributed in the form of an aqueous chlorite solution, and the storage safety is excellent. For example, the storage safety is higher than that in a case of distributing an aqueous chlorite solution in which chlorine dioxide gas is dissolved while keeping the pH acidic.
[0090] Chlorine dioxide gas can be actually generated using the chlorine dioxide gas generating kit K of this embodiment as follows. That is to say, as shown in
[0091] Then, the content is converted into a gel form in the first container 10 (the container main body 11), and chlorine dioxide gas is immediately generated at a stable concentration from the obtained gel composition 3 (see
[0092] In the description above, a configuration may also be employed in which the second agent 2 does not contain the absorbent resin, and only the aqueous chlorite solution, the fast-acting activator, the metal iodide, and the slow-acting activation inhibitor are mixed with each other. In this case, chlorine dioxide gas can be immediately generated at a stable concentration from the obtained liquid composition. Also, in this case, an antibacterial effect, a deodorant effect, and the like can be provided immediately at the time of use and stably for a long period of time due to the strong oxidizability of chlorine dioxide gas gradually released immediately and at a stable concentration.
Second Embodiment
[0093] Hereinafter, a chlorine dioxide gas generating method, a liquid composition, a gel composition, and a chlorine dioxide gas generating kit according to a second embodiment will be described. In this embodiment, the aqueous chlorite solution, the fast-acting activator, the metal iodide, the slow-acting activation inhibitor, and the absorbent resin are allocated to the first agent 1 and the second agent 2 of the chlorine dioxide gas generating kit K in a manner different from that of the first embodiment. Furthermore, the specific configuration of the container of the chlorine dioxide gas generating kit K is different from that of the first embodiment.
[0094] Hereinafter, the chlorine dioxide gas generating kit K of this embodiment will be described mainly focusing on differences from the first embodiment. Note that constituent elements not specifically described are as in the first embodiment, and thus they are denoted by the same reference numerals, and a description thereof has been omitted.
[0095] The chlorine dioxide gas generating kit K of this embodiment includes a first agent 1 containing an aqueous chlorite solution, and a second agent 2 containing a fast-acting activator, a metal iodide, a slow-acting activation inhibitor, and an absorbent resin. As shown in
[0096] The internal portion of the container 30 is separated into two spaces consisting of a first container section 32 and a second container section 33 by a separating portion 31 that can be manually deactivated. As shown in
[0097] Chlorine dioxide gas can be actually generated using the chlorine dioxide gas generating kit K of this embodiment as follows. That is to say, as shown in
[0098] In the description above, a configuration may also be employed in which the second agent 2 does not contain the absorbent resin, and only the aqueous chlorite solution, the fast-acting activator, the metal iodide, and the slow-acting activation inhibitor are mixed with each other. In this case, chlorine dioxide gas can be immediately generated at a stable concentration from the obtained liquid composition. Also, in this case, an antibacterial effect, a deodorant effect, and the like can be provided immediately at the time of use and stably for a long period of time due to the strong oxidizability of chlorine dioxide gas gradually released immediately and at a stable concentration.
Third Embodiment
[0099] Hereinafter, a chlorine dioxide gas generating method, a liquid composition, a gel composition, and a chlorine dioxide gas generating kit according to a third embodiment will be described. In this embodiment, the aqueous chlorite solution, the fast-acting activator, the metal iodide, slow-acting activation inhibitor, and the absorbent resin are allocated to the first agent 1 and the second agent 2 of the chlorine dioxide gas generating kit K in a manner different from that of the first and second embodiments. Furthermore, the specific configuration of the container of the chlorine dioxide gas generating kit K is different from that of the first and second embodiments. Hereinafter, the chlorine dioxide gas generating kit K of this embodiment will be described mainly focusing on differences from the first embodiment. Note that constituent elements not specifically described are as in the first embodiment, and thus they are denoted by the same reference numerals, and a description thereof has been omitted.
[0100] The chlorine dioxide gas generating kit K of this embodiment includes a first agent 1 containing an aqueous chlorite solution and a metal iodide, and a second agent 2 containing a fast-acting activator, a slow-acting activation inhibitor, and an absorbent resin. As shown in
[0101] The first container 10 is obtained, for example, by sticking plastic films to each other. The first container 10 may be obtained by stacking two plastic films and causing their entire peripheral edge portions to undergo easy peel sealing, or by folding one plastic film in half and causing the peripheral edge portions other than the folded portion to undergo easy peel sealing. In this manner, the first agent 1 is sealed in the sealable and easily breakable first container 10.
[0102] The second container 20 is made of a gas-permeable film. The second container 20 may be obtained by stacking two gas-permeable films and causing their entire peripheral edge portions to adhere to each other, or by folding one gas-permeable film in half and causing the peripheral edge portions other than the folded portion to adhere to each other. In this manner, the second agent 2 is sealed together with the first container 10 in the sealable and gas-permeable second container 20.
[0103] Chlorine dioxide gas can be actually generated using the chlorine dioxide gas generating kit K of this embodiment as follows. That is to say, the first container 10 is broken inside the second container 20, by applying a force from the outside of the second container 20 to a region in which the first container 10 is located. For example, an easily peelable portion of the first container 10 is peeled away by applying a force from the outside, and the first agent 1 formed as a liquid (an aqueous chlorite solution in which the metal iodide is dissolved) is released from the first container 10. Then, chlorine dioxide gas is immediately generated at a stable concentration from a gel composition obtained by mixing the first agent 1 and the second agent 2. The second container 20 is made of a gas-permeable film, and thus generated chlorine dioxide gas permeates the second container 20 and is released into a room. Thus, an antibacterial effect, a deodorant effect, and the like can be provided immediately at the time of use and stably for a long period of time due to the strong oxidizability of chlorine dioxide gas gradually released immediately and at a stable concentration.
[0104] In the description above, a configuration may also be employed in which the second agent 2 does not contain the absorbent resin, and only the aqueous chlorite solution, the fast-acting activator, the metal iodide, and the slow-acting activation inhibitor are mixed with each other. In this case, chlorine dioxide gas can be immediately generated at a stable concentration from the obtained liquid composition. Also, in this case, an antibacterial effect, a deodorant effect, and the like can be provided immediately at the time of use and stably for a long period of time due to the strong oxidizability of chlorine dioxide gas gradually released immediately and at a stable concentration.
[0105] Hereinafter, the present invention will be described in more detail by way of examples.
Example 1
[0106] First, 100 g of 4000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 1.71 g of 7.3% hydrochloric acid serving as an activator, 0.15 g of potassium iodide, and 0.11 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The potassium iodide and the sodium silicate pentahydrate were contained in the mixed liquid respectively in proportions in % by mass of 0.37% and 0.27%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Example 2
[0107] First, 100 g of 4000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 1.71 g of 7.3% hydrochloric acid serving as an activator, 0.08 g of potassium iodide, and 0.2 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The potassium iodide and the sodium silicate pentahydrate were contained in the mixed liquid respectively in proportions in % by mass of 0.2% and 0.5%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Example 3
[0108] First, 100 g of 4000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 2 g of phosphoric acid serving as an activator, 0.1 g of potassium iodide, and 0.11 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The potassium iodide and the sodium silicate pentahydrate were contained in the mixed liquid respectively in proportions in % by mass of 0.25% and 0.27%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Example 4
[0109] First, 100 g of 11250 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 1.16 g of phosphoric acid serving as an activator, 0.1 g of potassium iodide, and 0.05 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The potassium iodide and the sodium silicate pentahydrate were contained in the mixed liquid respectively in proportions in % by mass of 0.09% and 0.04%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Example 5
[0110] First, 100 g of 120000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 6.3 g of phosphoric acid serving as an activator, 0.1 g of potassium iodide, and 1.19 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The potassium iodide and the sodium silicate pentahydrate were contained in the mixed liquid respectively in proportions in % by mass of 0.01% and 0.1%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a non-sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in an open system.
Example 6
[0111] First, 100 g of 120000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 6.3 g of phosphoric acid serving as an activator, 0.25 g of potassium iodide, and 1.19 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The potassium iodide and the sodium silicate pentahydrate were contained in the mixed liquid respectively in proportions in % by mass of 0.02% and 0.1%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a non-sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in an open system.
Example 7
[0112] First, 100 g of 120000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 6.3 g of phosphoric acid serving as an activator, 0.5 g of potassium iodide, and 1.19 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The potassium iodide and the sodium silicate pentahydrate were contained in the mixed liquid respectively in proportions in % by mass of 0.04% and 0.1%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a non-sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in an open system.
Example 8
[0113] First, 100 g of 120000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 6.3 g of phosphoric acid serving as an activator, 1 g of potassium iodide, and 1.19 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The potassium iodide and the sodium silicate pentahydrate were contained in the mixed liquid respectively in proportions in % by mass of 0.08% and 0.1%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a non-sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in an open system.
Comparative Example 1
[0114] First, 100 g of 4000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 1.71 g of 7.3% hydrochloric acid serving as an activator and 0.11 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The sodium silicate pentahydrate was contained in the mixed liquid in a proportion in % by mass of 0.27%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Comparative Example 2
[0115] First, 100 g of 4000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 1.71 g of 7.3% hydrochloric acid serving as an activator and 0.15 g of potassium iodide were mixed with the aqueous sodium chlorite solution. The potassium iodide was contained in the mixed liquid in a proportion in % by mass of 0.37%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Comparative Example 3
[0116] First, 100 g of 4000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 2 g of phosphoric acid serving as an activator and 0.11 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The sodium silicate pentahydrate was contained in the mixed liquid in a proportion in % by mass of 0.27%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Comparative Example 4
[0117] First, 100 g of 4000 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 2 g of phosphoric acid serving as an activator and 0.1 g of potassium iodide were mixed with the aqueous sodium chlorite solution. The potassium iodide was contained in the mixed liquid in a proportion in % by mass of 0.25%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Comparative Example 5
[0118] First, 100 g of 11250 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 1.16 g of phosphoric acid serving as an activator and 0.05 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The sodium silicate pentahydrate was contained in the mixed liquid in a proportion in % by mass of 0.04%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Comparative Example 6
[0119] First, 100 g of 11250 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 1.16 g of phosphoric acid serving as an activator and 0.1 g of potassium iodide were mixed with the aqueous sodium chlorite solution. The potassium iodide was contained in the mixed liquid in a proportion in % by mass of 0.09%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
Comparative Example 7
[0120] First, 100 g of 11250 ppm aqueous sodium chlorite solution was prepared by dissolving sodium chlorite in pure water. Then, 3.01 g of 7.3% hydrochloric acid serving as an activator, 0.5 g of potassium iodide, and 2 g of sodium silicate pentahydrate serving as an activation inhibitor were mixed with the aqueous sodium chlorite solution. The potassium iodide and the sodium silicate pentahydrate were contained in the mixed liquid respectively in proportions in % by mass of 0.44% and 1.78%, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite). Subsequently, the mixed liquid was stored in a sealed state at room temperature, and the pH of the mixed liquid and the concentration of generated chlorine dioxide gas were measured in a closed system.
TABLE-US-00001 TABLE 1 Hydrochloric Phosphoric Na-silicate NaClO.sub.2 acid acid KI Na KI content content (ppm) (g) (g) (g) (g) (1/10000 ppm) (1/10000 ppm) Ex. 1 4000 1.71 0.15 0.11 0.37% 0.27% Ex. 2 4000 1.71 0.08 0.20 0.20% 0.50% Ex. 3 4000 2.00 0.10 0.11 0.25% 0.27% Ex. 4 11250 1.16 0.10 0.05 0.09% 0.04% Ex. 5 120000 6.30 0.10 1.19 0.01% 0.10% Ex. 6 120000 6.30 0.25 1.19 0.02% 0.10% Ex. 7 120000 6.30 0.50 1.19 0.04% 0.10% Ex. 8 120000 6.30 1.00 1.19 0.08% 0.10% Com. Ex. 1 4000 1.71 0.11 0.27% Com. Ex. 2 4000 1.71 0.15 0.37% Com. Ex. 3 4000 2.00 0.11 0.27% Com. Ex. 4 4000 2.00 0.10 0.25% Com. Ex. 5 11250 1.16 0.05 0.04% Com. Ex. 6 11250 1.16 0.10 0.09% Com. Ex. 7 11250 3.01 0.50 2.00 0.44% 1.78%
[0121] Measurement results were as follows.
TABLE-US-00002 TABLE 2 Elapsed time 1 min 10 min 30 min 24 hr 7 d Ex. 1 pH 2.8 2.8 2.8 2.9 2.9 ClO.sub.2 (ppm) 1028 1032 1045 998 1119 Ex. 1 pH 3.0 3.0 3.0 3.5 3.6 ClO.sub.2 (ppm) 581 554 534 696 517 Com. pH 2.5 2.5 2.5 2.8 2.8 Ex. 1 ClO.sub.2 (ppm) 67 111 178 897 894 Com. pH 2.4 2.4 2.4 2.4 2.3 Ex. 1 ClO.sub.2 (ppm) 1354 1418 1482 1468 732
[0122] In Comparative Example 1 in which a potassium iodide was not mixed, the generation of chlorine dioxide gas in the early stage (especially within 30 minutes) after mixing was slow, and, in Comparative Example 2 in which sodium silicate pentahydrate was not mixed, the concentration of chlorine dioxide gas after a long period of time had elapsed (specifically, after 7 days) was unstable. On the other hand, in Examples 1 and 2 in which both a potassium iodide and sodium silicate pentahydrate were mixed, it was seen that chlorine dioxide gas was released at a stable concentration over a long period of time from the early stage after mixing.
TABLE-US-00003 TABLE 3 Elapsed time 1 min 10 min 30 min 24 hr 7 d Ex. 3 pH 5.9 5.9 6.0 6.0 6.0 ClO.sub.2 (ppm) 118 128 134 148 134 Com. Ex. 3 pH 5.9 5.9 5.9 5.9 5.9 ClO.sub.2 (ppm) 0 3 5 10 17 Com. Ex. 4 pH 5.4 5.4 5.4 5.5 5.4 ClO.sub.2 (ppm) 242 242 239 186 128
[0123] In Comparative Example 3 in which a potassium iodide was not mixed, generation of chlorine dioxide gas was slow, and, in Comparative Example 4 in which sodium silicate pentahydrate was not mixed, the concentration of chlorine dioxide gas after a long period of time had elapsed (specifically, after 7 days) was unstable. On the other hand, in Example 3 in which both a potassium iodide and sodium silicate pentahydrate were mixed, it is seen that, even when a weak acid was used as an activator, chlorine dioxide gas was promptly released from the early stage (substantially within 10 minutes) after mixing. Furthermore, it was seen that chlorine dioxide gas was released at a stable concentration over a long period of time after that early stage.
TABLE-US-00004 TABLE 4 Elapsed time 1 min 10 min 30 min 24 hr 7 d Ex. 4 pH 6.0 6.0 6.0 6.0 6.0 ClO.sub.2 (ppm) 144 138 148 128 158 Com. Ex. 5 pH 5.9 5.9 5.9 5.9 6.0 ClO.sub.2 (ppm) 14 23 35 24 67 Com. Ex. 6 pH 5.6 5.6 5.6 5.7 5.7 ClO.sub.2 (ppm) 208 201 192 141 138 Com. Ex. 7 pH 12.7 12.7 12.7 12.8 12.8 ClO.sub.2 (ppm) 0 0 0 0 0
[0124] In Comparative Example 5 in which a potassium iodide was not mixed, generation of chlorine dioxide gas was slow, and, in Comparative Example 6 in which sodium silicate pentahydrate was not mixed, the concentration of chlorine dioxide gas after a predetermined period of time had elapsed (after 24 hours) was unstable. On the other hand, in Example 4 in which both a potassium iodide and sodium silicate pentahydrate were mixed, it was seen that, even when a weak acid was used as an activator, chlorine dioxide gas was promptly released from the very early stage (within 1 minute) after mixing. Furthermore, it was seen that chlorine dioxide gas was released at a stable concentration over a long period of time after that very early stage.
[0125] Furthermore, in Comparative Example 7 in which both a potassium iodide and sodium silicate pentahydrate were mixed but the amounts thereof added were excessive, generation of chlorine dioxide gas itself was not seen. On the other hand, referring to Examples 1 to 4, it was seen that, when the potassium iodide and the sodium silicate pentahydrate were contained respectively in proportions in % by mass of 0.4% or less and 1% or less, with respect to 1 L of 1% by mass aqueous chlorite solution (i.e., with respect to 10000 ppm of chlorite), chlorine dioxide gas was promptly released at a stable concentration.
TABLE-US-00005 TABLE 5 Elapsed time 1 min 10 min 30 min 24 hr 7 d Ex. 5 pH 6.0 6.0 6.0 6.1 6.2 ClO.sub.2 (ppm) 521 511 507 837 1045 Ex. 6 pH 6.0 6.0 6.0 6.1 6.2 ClO.sub.2 (ppm) 709 712 689 954 1038 Ex. 7 pH 6.1 6.1 6.1 6.2 6.2 ClO.sub.2 (ppm) 907 900 860 914 857 Ex. 8 pH 6.1 6.1 6.1 6.1 6.1 ClO.sub.2 (ppm) 1193 1169 1068 1048 827
[0126] In Examples 5 to 8, it was seen that, substantially, chlorine dioxide gas was promptly released at a stable concentration also in an open system.
[0127] In the description above, embodiments (including examples) of the chlorine dioxide gas generating method, the liquid composition, the gel composition, and the chlorine dioxide gas generating kit K were described in detail by way of specific examples, but the scope of the present invention is not limited to the foregoing specific examples and embodiments. The examples and embodiments disclosed in this specification are, in all respects, illustrative and not limiting. Various modifications may be made without departing from the gist of the invention.
[0128] For example, a configuration may also be employed in which the first agent 1 contains the aqueous chlorite solution and the slow-acting activation inhibitor, and the second agent 2 contains the fast-acting activator, the metal iodide, and the absorbent resin.
DESCRIPTION OF REFERENCE SIGNS
[0129] 1 First agent [0130] 2 Second agent [0131] 3 Gel composition [0132] 10 First container [0133] 11 Container main body [0134] 12 Sealing cap [0135] 14 Opening cap [0136] 15 Opening [0137] 20 Second container [0138] 30 Container [0139] 31 Separating portion [0140] 32 First container section [0141] 33 Second container section [0142] 35 Holding member [0143] K Chlorine dioxide gas generating kit