JP7617635B2 - Chlorine dioxide generator - Google Patents

Description

The present invention relates to a chlorine dioxide generator that generates chlorine dioxide gas by reacting a first component, which is a chlorite, with a second component that reacts with the chlorite to generate chlorine dioxide gas.

Conventionally, there are known tools and devices that generate chlorine dioxide gas by reacting a solution of chlorite with an acidic substance (for example, Patent Document 1).

JP 2007-145654 A

However, conventional chlorine dioxide generators were not developed with portability in mind, and most were either desk or floor mounted, or very large. Even if they were made small enough to be portable, there were problems such as the risk of liquid dripping from inside the device. Dripping can be prevented by ensuring the airtightness of the container, but this creates a new problem in that the release of chlorine dioxide gas is slowed down.

In addition, for example, when it is desired to disinfect a room or other similar space with chlorine dioxide gas in an environment where people are present, it is necessary to stably generate a relatively low concentration of chlorine dioxide gas for a long period of time. In order to continuously generate a low concentration of chlorine dioxide gas, for example, it is possible to reduce the concentration of the chlorite or acidic substance used.

When chlorine dioxide gas is generated in a container, the amount of chlorine dioxide gas generated depends on the area of the gas-liquid interface, etc., so the design of the container shape may be limited. In addition, from the perspective of mass production, the container may be made of synthetic resin. When chlorine dioxide gas is generated using a synthetic resin container, there is a risk that some of the generated chlorine dioxide gas will be adsorbed onto the container. When the generated chlorine dioxide gas is in low concentration, the effect of such adsorption onto the container cannot be ignored. Therefore, it has been desired to efficiently generate chlorine dioxide gas by effectively reacting chlorite and acidic substances, regardless of the shape or material of the container.

The present invention has been made in consideration of the above-mentioned circumstances, and its object is to provide a chlorine dioxide generator that is compact, allows the source of chlorine dioxide gas to be safely carried (portable), and can efficiently generate chlorine dioxide gas.

In order to achieve the above object, the chlorine dioxide generator of the present invention is a chlorine dioxide generator that generates chlorine dioxide gas by reacting a first component, which is a chlorite, with a second component that reacts with the chlorite to generate chlorine dioxide gas, and its first characteristic configuration is that it is configured so that its contents can be released by applying an external force, and includes an easily breakable first storage container in which an aqueous chlorite solution is sealed, a water-soluble second storage container in which a solid composition containing the second component is stored, and an outer container that stores the first storage container and the second storage container and has a ventilation part that is breathable , and the first storage container and the second storage container are arranged close to each other and stored in the outer container .

According to this configuration, the chlorine dioxide generating device can be constructed by enclosing it in an outer container that contains a first storage container and a second storage container, making the device compact and highly portable and suitable for mass production.

In addition, according to this configuration, in the outer container, the chlorite aqueous solution is sealed in the first storage container, and the second component is stored in the second storage container, so that the chlorite aqueous solution and the second component can be stored in a non-contact state. In this state, the outer container is deformed by applying an external force such as pressing, and the external force applied to the outer container is transmitted to the first storage container, so that the easily breakable first storage container stored inside can be easily broken. At this time, the chlorite aqueous solution can be released from the first storage container into the inside of the outer container. The released chlorite aqueous solution comes into contact with the second storage container, and at least a part of the water-soluble second storage container is dissolved or dispersed. As a result, the chlorite aqueous solution and the second component stored in the second storage container come into contact and react with each other, generating chlorine dioxide gas. The chlorine dioxide gas generated inside the outer container can be released to the outside of the outer container from the breathable ventilation part.

In this configuration, the second component is accommodated in the second container and is localized inside the outer container, and at least a part of the second container is dissolved or dispersed, so that the second component can be contacted with the chlorite aqueous solution. Therefore, compared with the case where the second component existing in a dispersed state is contacted with the chlorite aqueous solution, the chlorite aqueous solution and the second component can be easily reacted without excess or deficiency. Therefore, the chlorine dioxide generating device of the present invention can efficiently generate chlorine dioxide gas.
In this configuration, the first storage container and the second storage container are disposed adjacent to each other and stored in the outer container, so that water discharged from the first storage container can immediately contact the second storage container, and at least a portion of the second storage container can be dissolved or dispersed, allowing the chlorite to quickly come into contact with the second component.

A second characteristic configuration of the chlorine dioxide generator according to the present invention is a chlorine dioxide generator that generates chlorine dioxide gas by reacting a first component, which is a chlorite, with a second component that reacts with the chlorite to generate chlorine dioxide gas, and is configured so that the contents can be released by applying an external force, and includes an easily breakable first storage container in which an aqueous solution of the second component is sealed, a water-soluble second storage container in which a solid composition containing the chlorite is stored, and an outer container that stores the first storage container and the second storage container and has a ventilation part that is breathable , and the first storage container and the second storage container are arranged close to each other and stored in the outer container .

According to this configuration, the chlorine dioxide generating device can be constructed by enclosing it in an outer container that contains a first storage container and a second storage container, making the device compact and highly portable and suitable for mass production.

According to this configuration, in the outer container, the aqueous solution of the second component is sealed in the first storage container, and the chlorite is stored in the second storage container, so that the chlorite and the aqueous solution of the second component can be stored in a non-contact state. In this state, the outer container is deformed by applying an external force such as pressing, and the external force applied to the outer container is transmitted to the first storage container, so that the easily breakable first storage container stored inside can be easily broken. At this time, the aqueous solution of the second component can be released from the first storage container into the inside of the outer container. The released aqueous solution of the second component comes into contact with the second storage container, and at least a part of the water-soluble second storage container is dissolved or dispersed. As a result, the aqueous solution of the second component (acidic substance) and the chlorite stored in the second storage container come into contact and react with each other, generating chlorine dioxide gas. The chlorine dioxide gas generated inside the outer container can be released to the outside of the outer container from the breathable ventilation part.

In this configuration, the chlorite is stored in the second storage container and is localized inside the outer container, and at least a part of the second storage container is dissolved or dispersed, so that the chlorite can be contacted with the aqueous solution of the second component. Therefore, compared with the case where the chlorite present in a dispersed state is contacted with the aqueous solution of the second component, the chlorite and the aqueous solution of the second component can be easily reacted without excess or deficiency. Therefore, the chlorine dioxide generator of the present invention can efficiently generate chlorine dioxide gas.
In this configuration, the first storage container and the second storage container are disposed adjacent to each other and stored in the outer container, so that water discharged from the first storage container can immediately contact the second storage container, and at least a portion of the second storage container can be dissolved or dispersed, allowing the chlorite to quickly come into contact with the second component.

A third characteristic configuration of the chlorine dioxide generator of the present invention is that the first storage container and the second storage container are stacked and contained in the outer container.

According to this configuration, the water (aqueous solution) released from the first storage container can be immediately brought into contact with the second storage container.

The fourth characteristic configuration of the chlorine dioxide generator according to the present invention is that the first storage container is made of a multilayer film having at least a peelable layer containing a polyester-based resin, an adhesive layer, and a barrier layer having a vapor deposition portion with a polyester-based resin as a base material laminated in this order.

According to this configuration, the multilayer film constituting the first storage container has an easily peelable layer, so that the first storage container can be easily destroyed by peeling it off. Furthermore, the multilayer film constituting the first storage container has a barrier layer, so that even if the first storage container is stored for a long period of time with water (aqueous solution) contained inside, the contained water can be prevented from evaporating as water vapor and dissipating to the outside, improving stability during long-term storage. Furthermore, the easily peelable layer and the barrier layer contain polyester-based resin and therefore have excellent chemical resistance, improving stability during long-term storage.

The fifth characteristic feature of the chlorine dioxide generating device of the present invention is that the easily peelable layer is an interlayer peelable film.

According to this configuration, by using a peelable film as the easily peelable layer, the first storage container (easily peelable layer) can be easily destroyed by peeling between layers. The easily peelable layer made of a peelable film is unlikely to peel between layers unless a predetermined force is applied, and the desired layer can be peeled off when a force equal to or greater than the predetermined force required for peeling the desired layer is applied when opening. Therefore, the first storage container reliably seals water (aqueous solution) during storage, and can be opened easily and cleanly when opening.

The sixth characteristic configuration of the chlorine dioxide generator of the present invention is that the ventilation section is formed by processing a synthetic resin material into a nonwoven fabric.

With this configuration, the ventilation section can be made gas permeable and liquid impermeable.

The seventh characteristic configuration of the chlorine dioxide generator of the present invention is that the solid composition is in the form of a powder.

According to this configuration, by making the solid composition into a powder, the reaction between the chlorite and the second component is carried out efficiently, and chlorine dioxide gas can be generated in the theoretical amount of the reaction.

The eighth characteristic configuration of the chlorine dioxide generator of the present invention is that the outer container is configured to be rectangular when viewed from above, and the ventilation portion is configured to be planar.

According to this configuration, the ventilation section can be formed on at least one side of the back surface of the outer container. This allows the chlorine dioxide gas generated inside the outer container to be released to the outside of the outer container from the entire surface of at least one side of the outer container.

The ninth characteristic configuration of the chlorine dioxide generator of the present invention is that the second component is an acidic substance.

According to this configuration, the second component that reacts with chlorite to generate chlorine dioxide gas is an acidic substance, so that chlorite and the acidic substance can be reacted to easily generate chlorine dioxide gas.

A tenth characteristic feature of the chlorine dioxide generator of the present invention is that the acidic substance is a phosphate and the chlorite is sodium chlorite or potassium chlorite.

According to this configuration, the phosphate salt as the acidic substance has excellent storage stability, does not generate corrosive gases, and is easy to handle. In addition, sodium chlorite or potassium chlorite as the chlorite salt is easily available, so the present invention can be easily implemented.

An eleventh characteristic configuration of the chlorine dioxide generator of the present invention is that the concentration of the chlorite is 0.1 to 30% by weight.

According to this configuration, if the concentration of chlorite is less than 0.1% by weight, there is a possibility that there will be a problem of insufficient chlorite in the generation of chlorine dioxide gas, and if it exceeds 30% by weight, there is a possibility that there will be a problem that the chlorite becomes saturated and crystals are easily precipitated. Therefore, in consideration of safety, stability, and the efficiency of generating chlorine dioxide gas, it is preferable to set the concentration at 0.1 to 30% by weight.

FIG. 1 is a diagram showing an outline of a chlorine dioxide generating device according to an embodiment. FIG. 1 is a cross-sectional view showing an outline of a chlorine dioxide generating device according to an embodiment. FIG. 1 is a diagram showing an outline of a chlorine dioxide generating device according to an embodiment. FIG. 2 is a diagram showing an outline (cross section) of a multilayer film constituting a first storage container. FIG. 13 is a photograph showing the results of an investigation into the stability of a chlorine dioxide generator (first storage vessel) during long-term storage. FIG. 11 is a photograph showing the results of investigating the stability of the first storage container of the comparative example during long-term storage.

Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
The chlorine dioxide generator of the present invention generates chlorine dioxide gas by reacting a first component, chlorite, with a second component that reacts with the chlorite to generate chlorine dioxide gas.

As shown in Figures 1 to 3, the chlorine dioxide generator X of the present invention is configured to be able to release its contents by application of an external force, and comprises a fragile first storage container 10 in which a chlorite aqueous solution 1 is sealed, a water-soluble second storage container 20 in which a solid composition containing a second component 2 is stored, and an outer container 30 which stores the first storage container 10 and the second storage container 20 and has a ventilation section 31 which is breathable.

The second component 2 may be any substance that reacts with chlorite to generate chlorine dioxide gas, such as an acidic substance, or a substance that does not contain an acidic substance and reacts with chlorite alone to generate chlorine dioxide. In this embodiment, a case in which the second component 2 is an acidic substance is described. The acidic substance is preferably an acidic substance that becomes acidic when dissolved in water.

(First storage container)
The first storage container 10 is a fragile container capable of sealing the chlorite aqueous solution 1. The first storage container 10 may contain contents other than the chlorite aqueous solution 1. In this specification, "fragile" refers to a property in which the container can be easily cracked, broken, or torn by applying a force from the outside to deform the container or by bending (or attempting to bend) it, but must not be damaged by shaking or light impact during transportation or storage. Examples of the fragile first storage container 10 include bags using a resin film, glass ampoules, and plastic containers with a relatively thin thickness. When a plastic container is used as the fragile first storage container 10, a fragile part may be artificially provided in advance on the container, and the fragile part may be cracked or broken (broken) by applying a force from the outside to bend (or attempt to bend).

The shape of the first storage container 10 may be, but is not limited to, a bag shape, a tube shape (test tube shape), a stick shape, a box shape, etc. In this embodiment, the first storage container 10 is bag-shaped, and the bag is made of a resin multilayer film 10A.

The multilayer film 10A is constructed by laminating, in this order, at least an easily peelable layer 11 containing a polyester-based resin, an adhesive layer 12, and a barrier layer 13 having a vapor deposition portion with a polyester-based resin base material (Figure 4).

The easily peelable layer 11 may be, for example, in a multi-layered film, such that one of the layers can be used as a peelable layer and can be easily peeled off from the other layers (the adhesive strength between layers is set to be weak). In this specification, the "easily peelable layer" refers to a property in which the desired layer can be easily peeled off by the application of a specific force applied from the outside, but it should not peel off due to shaking or light impact during transportation or storage.

A known interlayer peeling film containing a polyester resin can be used as such an easily peelable layer 11. Examples of the interlayer peeling film include, but are not limited to, Easy Open Film (manufactured by Mitsui Chemicals, Inc., thickness 30 μm), DIFAREN (manufactured by DIC Corporation, thickness 30 μm), and Easy Peel (manufactured by Okamoto Corporation, thickness 30 μm).

As in this configuration, the multilayer film constituting the first storage container 10 has an easily peelable layer 11, so that the first storage container 10 can be easily destroyed by peeling. In addition, by using a peelable film as the easily peelable layer 11, the first storage container 10 (easy peelable layer 11) can be easily destroyed by peeling. The easily peelable layer 11 made of a peelable film is unlikely to peel off unless a predetermined force is applied, and the desired layer can be peeled off when a force equal to or greater than a predetermined force for peeling the desired layer is applied when opening. Therefore, the first storage container 10 reliably seals the aqueous solution (chlorite aqueous solution 1) during storage, and can be easily and cleanly opened when opening. In addition, the easily peelable layer 11 contains a polyester resin, so it has excellent chemical resistance.

The adhesive layer (first adhesive layer) 12 may be a known thermocompression sheet or adhesive, etc., as long as it is capable of bonding the easily peelable layer 11 and the barrier layer 13. In this embodiment, a known low-density polyethylene (LDPE, thickness 20 μm) sheet is used as the first adhesive layer 12, and an embodiment is described in which the easily peelable layer 11 and the barrier layer 13 are bonded by thermocompression.

The barrier layer 13 may have a vapor deposition portion with a polyester resin as a base material, and may have water vapor barrier properties. In this specification, "water vapor barrier properties" refers to the property of preventing the water (aqueous solution) contained in the first storage container 10 from dissipating to the outside by evaporating as water vapor under specified conditions for a long period of time. The specified conditions are, for example, conditions of room temperature to about 40°C and normal pressure, and it is sufficient if the water (chlorite aqueous solution 1) contained in the first storage container 10 can be prevented from dissipating to the outside under these conditions for, for example, six months or more.

As such a barrier layer 13, a known barrier film having a deposition portion with a polyester resin as a substrate can be used. The substrate can be, for example, a polyethylene terephthalate (PET) film, and the deposition portion can be, for example, silica deposition or alumina deposition, but is not limited to these. As the barrier film, for example, a silica deposition transparent PET film, Techbarrier (manufactured by Mitsubishi Chemical Corporation, thickness 12 μm), an alumina deposition transparent PET film, Barrierox (manufactured by Toray Film Processing Co., Ltd., thickness 12 μm), an alumina deposition transparent PET film, IB FILM (manufactured by Dai Nippon Printing Co., Ltd., thickness 12 μm), a ceramic deposition transparent PET film, Ecosiale (manufactured by Toyobo Co., Ltd., thickness 12 μm), an inorganic deposition transparent PET film, GL FILM (manufactured by Toppan Printing Co., Ltd., thickness 12 μm), a transparent deposition PET film, MOS (manufactured by Oike Pack Materials Co., Ltd., thickness 12 μm), etc. can be used, but are not limited to these.

In this configuration, the multilayer film constituting the first storage container has a barrier layer 13 having a vapor deposition portion with a polyester-based resin as a base material, so that even if the aqueous solution (chlorite aqueous solution 1) is stored inside the first storage container 10 for a long period of time, the stored water can be prevented from evaporating as water vapor and dissipating to the outside, thereby improving stability during long-term storage. In addition, the barrier layer 13 has excellent chemical resistance because it contains a polyester-based resin.

In this embodiment, the multilayer film 10A is described as a five-layer film in which, in addition to the easily peelable layer 11, first adhesive layer 12, and barrier layer 13, a second adhesive layer 14 and a base layer 15 are added to the barrier layer 13 side. The second adhesive layer 14 can be a known thermocompression sheet or adhesive. The base layer 15 can be a PET film (thickness 12 μm), etc.

As described above, the multilayer film 10A is required to have at least the easily peelable layer 11, the first adhesive layer 12, and the barrier layer 13, and therefore may have additional layers in addition to the adhesive layer 14 and the base layer 15. Furthermore, the thicknesses described for each layer are merely examples and may be changed as appropriate.

The first storage container 10 may be formed by processing the multilayer film 10A into a bag shape. In this embodiment, a rectangular multilayer film 10A is folded along its center line, and the edges are overlapped while the peripheral portion (three sides) is heat-sealed to form a bag shape. When folding the multilayer film 10A along its center line, the easily peelable layer 11 is placed on the inner surface side of the first storage container 10, and the easily peelable layers 11 are in close contact with each other, and the peripheral portions 10a of the three sides are heat-sealed with a predetermined width at the peripheral portions 10a. Any part of the seal portion 10b where the peripheral portion 10a is heat-sealed in this way becomes a part where the easily peelable layer 11 peels off when a predetermined force applied from the outside is applied to the first storage container 10. In other words, when opened, the easily peelable layer 11 peels off at any part of the sealed portion 10b, and the contents (chlorite aqueous solution 1) contained in the first storage container 10 can be released to the outside of the first storage container 10 from the peeled portion that penetrates the inside and outside of the first storage container 10.

The manner in which the multilayer film 10A is processed into a bag shape is not limited to the above manner, and for example, two rectangular multilayer films 10A of approximately the same shape may be stacked on top of each other and the peripheral portions (four sides) of the film may be heat sealed to form a bag shape.

In addition, the sealing of the peripheral portion 10a of the multilayer film 10A is not limited to heat sealing, but can be sealed by known methods such as ultrasonic sealing or adhesives.

(Second storage container)
The second storage container 20 is a water-soluble container capable of storing a solid composition containing the second component (acidic substance) 2. That is, the second storage container 20 is a container in a form in which at least a part of the second storage container 20 dissolves or disperses when it comes into contact with the water (chlorite aqueous solution) released from the first storage container 10. The material of the water-soluble container that can constitute the second storage container 20 is not particularly limited as long as it is at least a part of the second storage container 20 dissolves or disperses when it comes into contact with the water (chlorite aqueous solution), and for example, known water-soluble paper and films made of PVA (polyvinyl alcohol) can be used. For PVA, Kuraray Poval Film (manufactured by Kuraray Co., Ltd.), Hi-Selon (manufactured by Nippon Gosei Co., Ltd.), Solbron (manufactured by Aicello Co., Ltd.), etc., which are water-soluble PVA films having heat sealability, can be used.

The shape of the second storage container 20 may be, but is not limited to, a bag shape, a tube shape (test tube shape), a stick shape, a box shape, etc. In this embodiment, the second storage container 20 is described as having a bag shape.

In this embodiment, a rectangular water-soluble PVA film is folded along its center line, and the edges are overlapped and then heat-sealed to form a bag. At this time, the three edges 20a are heat-sealed to provide a predetermined width.

In addition, the sealing of the peripheral portion 20a of the second storage container 20 is not limited to heat sealing, but can be sealed by known methods such as ultrasonic sealing or adhesives.

In this embodiment, a case will be described in which a water-absorbing polymer (not shown) is contained in the second storage container 20 together with the second component (acidic substance) 2. By containing the water-absorbing polymer, the water-absorbing polymer can absorb a certain amount of the water (chlorite aqueous solution) released from the first storage container 10, preventing a sudden reaction between the chlorite and the second component (acidic substance). Therefore, the amount of chlorine dioxide gas generated can be controlled by adjusting the amount of water-absorbing polymer.

In this embodiment, a configuration will be described in which the first storage container 10 and the second storage container 20 are stacked and stored in the outer container 30. This allows the water (chlorite aqueous solution) released from the first storage container 10 to immediately contact the second storage container 20, dissolving or dispersing at least a portion of the second storage container 20, allowing the chlorite and the second component (acidic substance) to come into contact quickly. In addition, the first storage container 10 and the second storage container 20 may be stacked and adhered to each other with double-sided tape or the like so as not to be misaligned inside the outer container 30.

The manner in which the first storage container 10 and the second storage container 20 are accommodated in the outer container 30 is not limited to this manner, and any manner may be used as long as the first storage container 10 and the second storage container 20 are accommodated so as to be adjacent to each other inside the outer container 30.

In addition, in this embodiment, the sizes of the first storage container 10 and the second storage container 20 are described as being larger than the first storage container 10 that seals water (chlorite aqueous solution), but the present invention is not limited to this embodiment. A specific size ratio between the first storage container 10 and the second storage container 20 is preferably, for example, about 2 to 10 times the volume ratio.

(Outer container)
The outer container 30 is a container that is configured to be able to accommodate the first storage container 10 and the second storage container 20, and is provided with a ventilation part 31 that has ventilation. The shape of the outer container 30 may be, for example, a bag-like, tubular (test tube-like), stick-like, or box-like, but is not limited thereto. In this embodiment, the outer container 30 is a bag-like container configured to be rectangular in top view, and the ventilation part 31 is configured to be planar, but is not limited thereto. In this configuration, the ventilation part 31 can be formed on at least one side of the back surface of the outer container 30. This allows chlorine dioxide gas generated inside the outer container 30 to be released to the outside of the outer container 30 from the entire surface of at least one side of the outer container 30.

At least one of the front and back surfaces of the outer container 30 is gas permeable and liquid impermeable. That is, the front surface of the outer container 30 may be gas permeable and liquid impermeable and the back surface may be gas-liquid impermeable, or the front surface may be gas-liquid impermeable and the back surface may be gas-permeable and liquid impermeable, or both the front and back surfaces may be gas permeable and liquid impermeable.

In order to make the front or back surface of the outer container 30 gas permeable and liquid impermeable, the ventilation section 31 provided on the front or back surface may be made by processing a synthetic resin material into a nonwoven fabric. The nonwoven fabric may be, for example, a sheet of high-density polyethylene nonwoven fabric, but is not limited to this. The nonwoven fabric may be, for example, Exepol (registered trademark, manufactured by Mitsubishi Chemical Corporation), Tyvek (registered trademark, manufactured by DuPont), Elves (registered trademark, manufactured by Unitika Co., Ltd.), Gore-Tex (registered trademark, manufactured by WL Gore & Associates Co., Ltd.), Melfit (registered trademark, manufactured by Unicel Co., Ltd.), etc., but is not limited to these. In addition, the front or back surface of the outer container 30 may be treated to be water repellent.

To make the front or back surface of the outer container 30 impermeable to gas and liquid, a sheet made of a synthetic resin material such as acrylonitrile styrene (AS) resin, acrylonitrile butadiene styrene (ABS) resin, ethylene vinyl alcohol (EVOH) resin, polyvinyl chloride resin, vinylidene chloride resin, polyethylene resin, polypropylene resin, or polyolefin resin can be used, but is not limited to these.

In this embodiment, the outer container 30 is made of the above-mentioned material, and the edges of the front sheet and the back sheet are overlapped and heat-sealed to form a bag. At this time, the four edges 30a are heat-sealed with a predetermined width.

In addition, the sealing of the peripheral portion 30a of the outer container 30 is not limited to heat sealing, but can be done by known methods such as ultrasonic sealing or adhesives.

(Chlorite)
The chlorite used in the present invention can be, for example, alkali metal chlorite or alkaline earth metal chlorite.The alkali metal chlorite can be, for example, sodium chlorite, potassium chlorite, and lithium chlorite, and the alkaline earth metal chlorite can be, for example, calcium chlorite, magnesium chlorite, and barium chlorite.Among them, sodium chlorite and potassium chlorite are preferred from the viewpoint of easy availability, and sodium chlorite is most preferred.These chlorites can be used alone or in combination of two or more.

The proportion of chlorite in the chlorite aqueous solution is preferably 0.1% to 30% by weight. If it is less than 0.1% by weight, there is a possibility that there will be a problem of insufficient chlorite in the generation of chlorine dioxide gas, and if it exceeds 30% by weight, there is a possibility that there will be a problem of saturation of chlorite and easy precipitation of crystals. In consideration of safety, stability, and the efficiency of generation of chlorine dioxide gas, a proportion of 3% to 25% by weight is preferable, and more preferably a range of 3% to 15% by weight for stable generation and 15% to 25% by weight for rapid generation.

(acidic substances)
The acidic substances that can be used in the present invention include inorganic acids, organic acids, and their salts, such as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, metaphosphoric acid, pyrophosphoric acid, and sulfamic acid, and organic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, pyruvic acid, citric acid, malic acid, tartaric acid, gluconic acid, glycolic acid, fumaric acid, malonic acid, maleic acid, oxalic acid, succinic acid, acrylic acid, crotonic acid, oxalic acid, and glutaric acid, and their salts. In addition, examples of salts of inorganic acids include phosphates such as dihydrogen phosphate (sodium salt or potassium salt, the same applies below), and mixtures of dihydrogen phosphate and monohydrogen phosphate. Among them, it is preferable to use phosphates because they have excellent storage stability, do not generate corrosive gases, and do not change in concentration during storage. In the state in which the phosphate is contained in the solid composition, the final concentration of the phosphate should be 30% by weight or less. The acidic substances may be used alone or in combination of two or more kinds.

(Solid Composition)
The solid composition may be in any form as long as it contains the second component (acidic substance), and may be, for example, in the form of crystals or powder of an acidic substance, or a porous substance containing an acidic substance. In this embodiment, a case where the solid composition is a powder will be described. That is, the above-mentioned "solid composition containing the second component 2" refers to a substance containing an acidic substance that exhibits acidity when dissolved in water.

By making the solid composition into a powder, the reaction between the aqueous chlorite solution and the acidic substance can be carried out efficiently, and chlorine dioxide gas can be generated in the amount theoretically expected for the reaction. The solid composition may be in the form of granules.

The above-mentioned porous material may be, for example, a porous material or a calcined aggregate, but is not limited thereto. Examples of the porous material include porous silica, sepiolite, montmorillonite, diatomaceous earth, talc, zeolite, activated clay, molecular sieve, activated alumina, etc. Among them, it is preferable to use porous silica, which is easily available, has excellent porosity (wide pore space), and is easy to contain acidic substances or chlorite. There is no particular limitation on the specific surface area of these porous silicas, etc.
As the fired aggregate, for example, bones of animals (including mammals, fish and birds), shells and coral which have been fired into crushed pieces, particles or powder can be used.

In the above-mentioned chlorine dioxide generating device X, the chlorite aqueous solution 1 is sealed in the first storage container 10 and the second component 2 of the acidic substance is stored in the second storage container 20 in the outer container 30, so that the chlorite aqueous solution 1 and the second component 2 of the acidic substance can be stored in a non-contact state. In this state, the outer container 30 is deformed by applying an external force such as pressing, and the external force applied to the outer container 30 is transmitted to the first storage container 10, so that the easily destructible first storage container 10 stored inside can be easily destroyed. At this time, the chlorite aqueous solution 1 can be released from the first storage container 10 into the outer container 30. The released chlorite aqueous solution 1 comes into contact with the second storage container 20, and at least a part of the water-soluble second storage container 20 is dissolved or dispersed. As a result, the chlorite aqueous solution 1 and the second component (acidic substance) 2 stored in the second storage container 20 come into contact and react with each other, generating chlorine dioxide gas. The chlorine dioxide gas generated inside the outer container 30 can be released to the outside of the outer container 30 through the ventilation part 31 having air permeability.

In the chlorine dioxide generator X of the present invention, the second component (acidic substance) 2 is stored in the second storage container 20 and is in a localized state (not dispersed state) inside the outer container 30, and the second component (acidic substance) 2 can be brought into contact with the chlorite aqueous solution 1 by dissolving or dispersing at least a part of the second storage container 20. Therefore, it is possible to easily cause the chlorite aqueous solution 1 and the second component (acidic substance) 2 to react without excess or deficiency, compared to the case where the second component (acidic substance) 2 present in a dispersed state is brought into contact with the chlorite aqueous solution. Therefore, the chlorine dioxide generator X of the present invention can efficiently generate chlorine dioxide gas.

There is no particular limit to the places where the chlorine dioxide generator X of the present invention can be used, and it can be used in a variety of situations, such as in ordinary homes (living rooms, entrances, bathrooms, kitchens, etc.), industrial (factory) use, medical facilities such as hospitals, clinics, and nursing homes, and public facilities such as schools, train stations, and public toilets. It can also be used not only in relatively large spaces such as indoor spaces where people can live, but also in small spaces such as refrigerators, shoe cabinets, and the inside of vehicles (cars, buses, and trains). In this way, there is no particular limit to the size of the space to which the generator of the present invention can be applied.

[Another embodiment]
In the above-described embodiment, a case has been described in which a chlorite aqueous solution 1 is sealed in the first storage container 10, and a second component 2, which is an acidic substance, is stored in the second storage container 20. In contrast, in the present embodiment, a case will be described in which an aqueous solution of the second component, which is an acidic substance, is sealed in the first storage container 10, and a solid composition containing chlorite is stored in the second storage container 20.

That is, the chlorine dioxide generator X of another embodiment is configured to be able to release the contents by applying an external force, and includes an easily breakable first storage container 10 in which an aqueous solution of the second component (acidic substance) is sealed, a water-soluble second storage container 20 in which a solid composition containing chlorite is stored, and an outer container 30 that stores the first storage container 10 and the second storage container 20 and has a ventilation part 31 that is breathable. The first storage container 10 may store contents other than the aqueous solution of the second component.

In the chlorine dioxide generator X having such a configuration, the aqueous solution of the second component, which is an acidic substance, is sealed in the first storage container 10 in the outer container 30, and the chlorite is stored in the second storage container 20, so that the chlorite and the aqueous solution of the second component, which is an acidic substance, can be stored in a non-contact state. In this state, the outer container 30 is deformed by applying an external force such as pressing, and the external force applied to the outer container 30 is transmitted to the first storage container 10, so that the easily destructible first storage container 10 stored inside can be easily destroyed. At this time, the aqueous solution of the second component (acidic substance) can be released from the first storage container 10 into the outer container 30. The released aqueous solution of the second component (acidic substance) comes into contact with the second storage container 20, and at least a part of the water-soluble second storage container 20 is dissolved or dispersed. As a result, the aqueous solution of the second component (acidic substance) and the chlorite stored in the second storage container 20 come into contact with each other and react, generating chlorine dioxide gas. The chlorine dioxide gas generated inside the outer container 30 can be released to the outside of the outer container 30 through the ventilation part 31 having air permeability.

In the chlorine dioxide generator X of the present invention, the chlorite can be stored in the second storage container 20 and brought into contact with the aqueous solution of the second component (acidic substance) in a state where it is localized inside the outer container 30 (not in a dispersed state). Therefore, compared to the case where the chlorite present in a dispersed state is brought into contact with the aqueous solution of the second component (acidic substance), it is possible to make it easier to react the chlorite and the aqueous solution of the second component (acidic substance) without excess or deficiency. Therefore, the chlorine dioxide generator X of the present invention can efficiently generate chlorine dioxide gas.

The acidic substance that can be used in this embodiment can be any of the above-mentioned acidic substances. When sulfuric acid is used as the acidic substance, the concentration of the aqueous solution is preferably 30% by weight or less.
In addition, in this embodiment, the final concentration of the chlorite contained in the solid composition is preferably 30% by weight or less, and more preferably 3 to 15% by weight, from the viewpoints of safety, stability, and efficiency of generating chlorine dioxide gas.

Example 1
As the chlorine dioxide generator X of the present invention, a sodium chlorite aqueous solution 1 was contained in a first storage container 10, a second storage container 20 was contained with potassium dihydrogen phosphate (powder) as a second component 2, and these were contained in an outer container 30 in a stacked state.

Three types of multilayer films 10A having the configurations shown in Table 1 were produced by conventional methods (Examples 1-1 to 1-3). The multilayer films 10A were folded along the center line so that the easily peelable layer 11 was on the inner surface, and the ends were overlapped and heat sealed at the peripheral portions (three sides) 10a to a seal width of 10 mm. The resulting bag was processed into a rectangular bag (100 mm x 150 mm) when viewed from above, which was used as the first storage container 10.

The second storage container 20 was made of a water-soluble PVA film, Solvron (manufactured by Aicello), processed into a bag shape. That is, the film was folded along the center line, the ends were overlapped, and the peripheral portion (three sides) 20a was heat sealed so that the seal width was 10 mm, and the bag was processed into a rectangular shape (80 mm x 100 mm) when viewed from above. This was used as the second storage container 20.

The outer container 30 is made of a sheet with a Melfit (registered trademark, manufactured by Unicel) surface and a linear low-density polyethylene (LLDPE, manufactured by Tosoh) back surface, which are heat-sealed together so that the seal width around the periphery (four sides) 30a is 10 mm, and processed into a bag (120 mm x 200 mm) that is rectangular when viewed from above.

In three types of chlorine dioxide generators X manufactured by separately housing the first storage container 10 made from the multilayer film 10A of Examples 1-1 to 1-3, an external force was applied to the outer container 30 by pressing it with a finger from the outside, causing it to deform. At this time, the external force applied to the outer container 30 was transmitted to the easily destructible first storage container 10, causing the first storage container 10 to deform, and the internal pressure increased, causing the easily peelable layer 11 to peel off from the interlayer, allowing the first storage container 10 to be easily destroyed.

The sodium chlorite aqueous solution released into the outer container 30 by destroying the first container 10 immediately came into contact with the second container 20, and part of the water-soluble second container 20 dissolved. Furthermore, by shaking the outer container 30 side to side several times, most of the water-soluble second container 20 dissolved. As a result, the sodium chlorite aqueous solution and the potassium dihydrogen phosphate contained in the second container 20 came into contact with each other and reacted, generating chlorine dioxide gas.

The potassium dihydrogen phosphate is stored in the second storage container 20 and localized inside the outer container 30, and at least a portion of the second storage container 20 dissolves or disperses, bringing the potassium dihydrogen phosphate into contact with the sodium chlorite aqueous solution, allowing the sodium chlorite aqueous solution and potassium dihydrogen phosphate to react without excess or deficiency.

Example 2
In the chlorine dioxide generator X of Example 1, the stability of the first storage vessel 10 containing an aqueous solution during long-term storage was examined.

When the first storage container 10 was left at 40°C and normal pressure, the amount of the aqueous sodium chlorite solution remained almost unchanged even after 10 months. Furthermore, no deterioration (discoloration to white) or other changes were observed in the heat-sealed seal portion 10b of the periphery 10a of the first storage container 10 (Figure 5).

Therefore, in the chlorine dioxide generator X of the present invention, it is possible to prevent the stored water (aqueous solution) from evaporating as water vapor and dissipating to the outside even during long-term storage (10 months or more), and since it has excellent chemical resistance, it has been recognized that the stability during long-term storage is improved.

As a comparative example, the stability during long-term storage was examined for a case in which the constituent material of the multilayer film of the first storage container was an IMX film (manufactured by J Film, thickness 30 μm), which is a cohesive peeling type PE/PP sheet, and no barrier layer. That is, the multilayer film of the comparative example was a three-layer film consisting of a cohesive peeling type PE/PP sheet, a low-density polyethylene sheet (LDPE, thickness 20 μm) as an adhesive layer, and a PET film (thickness 16 μm) as a base layer. The container of the comparative example was produced by heat-sealing the peripheral portion (four sides) of the multilayer film so that the seal width of the peripheral portion was 10 mm.

When the container of this comparative example was left for one month under conditions of 40° C. and normal pressure, the heat-sealed portion around the periphery of the container deteriorated (discolored white), and a weight loss of about 18% was observed (FIG. 6).
Therefore, the container of this comparative example was deemed unsuitable for long-term storage.

The present invention can be used in a chlorine dioxide generator that generates chlorine dioxide gas by reacting a first component, which is a chlorite salt, with a second component that reacts with the chlorite salt to generate chlorine dioxide gas.

X Chlorine dioxide generator 10 First storage container 20 Second storage container 30 Outer container 31 Ventilating section

Claims (11)

A chlorine dioxide generator that generates chlorine dioxide gas by reacting a first component, a chlorite, with a second component that reacts with the chlorite to generate chlorine dioxide gas,
A first easily breakable storage container configured to be capable of releasing contents by application of an external force and sealing a chlorite aqueous solution therein;
a water-soluble second container containing a solid composition containing the second component;
an outer container that accommodates the first storage container and the second storage container and has a ventilation part that has ventilation ,
The chlorine dioxide generating apparatus comprises the first storage container and the second storage container disposed adjacent to each other and housed in the outer container . A chlorine dioxide generator that generates chlorine dioxide gas by reacting a first component, a chlorite, with a second component that reacts with the chlorite to generate chlorine dioxide gas,
a first easily breakable container configured to release the contents by application of an external force and sealingly holding an aqueous solution of the second component;
a water-soluble second container containing a solid composition containing the chlorite;
an outer container that accommodates the first storage container and the second storage container and has a ventilation part that has ventilation ,
The chlorine dioxide generating apparatus comprises the first storage container and the second storage container disposed adjacent to each other and housed in the outer container . The chlorine dioxide generator according to claim 1 or 2, in which the first storage container and the second storage container are stacked and stored in the outer container. The chlorine dioxide generator according to any one of claims 1 to 3, wherein the first storage container is made of a multilayer film in which at least an easily peelable layer containing a polyester resin, an adhesive layer, and a barrier layer having a vapor deposition portion with a polyester resin base material are laminated in this order. The chlorine dioxide generator according to claim 4, wherein the easily peelable layer is a peelable film. The chlorine dioxide generator according to any one of claims 1 to 5, wherein the ventilation section is made of synthetic resin material processed into nonwoven fabric. The chlorine dioxide generator according to any one of claims 1 to 6, wherein the solid composition is a powder. The chlorine dioxide generator according to any one of claims 1 to 7, in which the outer container is rectangular in top view and the ventilation section is planar. The chlorine dioxide generator according to any one of claims 1 to 8, wherein the second component is an acidic substance. The chlorine dioxide generator according to claim 9, wherein the acidic substance is a phosphate and the chlorite is sodium chlorite or potassium chlorite. The chlorine dioxide generator according to claim 9 or 10, wherein the concentration of the chlorite is 0.1 to 30% by weight.

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