JP6748431B2 - Antibacterial agents, antibacterial agents in bags and sheet type antibacterial agents - Google Patents

Description

The present invention relates to antibacterial agents. More specifically, the present invention relates to an antibacterial agent composed of particles of a water-absorbent resin that absorbs water containing or generating chlorine dioxide, and an antibacterial agent housed in a bag or formed into a sheet shape.

In recent years, chlorine dioxide has attracted attention as a sterilizing and disinfecting agent that replaces chlorine. Heretofore, as a method of generating chlorine dioxide, a mainstream has been to mix and react a chlorite with an acid (for example, Patent Document 1). However, this method has problems that it takes a lot of time and effort for mixing to cause a side reaction, and it is difficult to control the generation of chlorine dioxide gas, so that it cannot be easily used by general users. Here, chlorine dioxide is generated by the following reaction formula, for example. When sodium chlorite (NaClO ₂ ) is used as the chlorite and citric acid (C ₆ H ₈ O ₇ ) is used as the acid, when both react, the following reaction formula 15NaClO ₂ +4HO ₂ CC(OH) (CH ₂ CO ₂ H) ₂
→12ClO ₂ +4C ₆ H5Na ₃ O ₇ +3NaCl+2H ₂ O
Theoretically, 15 moles of sodium chlorite react with 4 moles of citric acid to generate 12 moles of chlorine dioxide.

As a technique for solving such a problem, a gel composition composed of stabilized chlorine dioxide and a water-absorbent resin (for example, Patent Document 2) and a pure composition containing a dissolved chlorine dioxide gas, a chlorite and a pH adjuster An antibacterial agent made of a gel composition (for example, Patent Document 3) containing a superabsorbent resin in a chlorine dioxide liquid agent is placed indoors, or chlorine dioxide is adsorbed and held on a porous inorganic carrier, and the inorganic solid is formed on the entire surface. A first bag having micropores having a diameter smaller than the particle size of the carrier and containing an antibacterial agent, and a release hole for containing the first bag and releasing chlorine dioxide into the atmosphere. A general user uses a bag-shaped antibacterial agent (for example, Patent Document 4) including a second bag body by hanging it from the neck.

JP-A-60-161307 JP, 61-181532, A JP, 11-278808, A Patent No. 5172002

However, the above-mentioned gel composition does not generate chlorine dioxide gas only from the surface of the gel even when put in a bag, and since the surface area of the gel is small, chlorine dioxide is less released and is not suitable as a bag-containing antibacterial agent. It is not suitable for hanging from the neck because it has a gel shape and is difficult to put in a bag. Further, the latter bag-containing antibacterial agent has a small absorption capacity or retention capacity of chlorine dioxide or its contained water in the porous inorganic carrier, and in order to absorb a large amount, a large amount of porous inorganic carrier must be used. It is not suitable for chlorine dioxide release during the period, and there is a problem that the end point of chlorine dioxide volatilization is unknown.

An object of the present invention is to provide an antibacterial agent having a large absorption capacity or retention capacity of water containing or generating chlorine dioxide, a long-term antibacterial effect even in a small amount, and an end point of chlorine dioxide volatilization to some extent, and a bag body for the same. The present invention is to provide a bag-type antibacterial agent or a sheet-type antibacterial agent housed inside.

As a result of intensive studies, the inventor has found that the above object can be achieved by forming a water-absorbent resin impregnated with water containing or generating chlorine dioxide into particles, and completed the present invention.

That is, the present invention is an antibacterial agent consisting of particles of a water-absorbent resin that absorbs water containing or generating chlorine dioxide, which releases chlorine dioxide and water.
The average particle diameter of the particles of the water absorbent resin before absorbing water containing chlorine dioxide or generated is 30 to 850 μm,
Ri average particle diameter 0.1~3mm der particles of water-absorbing resin has absorbed containing or generating water the chlorine dioxide,
An antibacterial agent in which the ratio of the water-absorbent resin before absorbing the water containing or generating chlorine dioxide and the water containing or generating chlorine dioxide is 1:3 to 1:10 in weight ratio,
A bag-containing antibacterial agent characterized by being enclosed in a bag body (1) made of an impermeable material provided with a release hole for releasing chlorine dioxide and water into the atmosphere.
Furthermore, the present invention is an antibacterial agent comprising chlorine-dioxide-containing or water-absorbing water-absorbent resin particles, which releases chlorine dioxide and water.
The average particle diameter of the particles of the water absorbent resin before absorbing water containing chlorine dioxide or generated is 30 to 850 μm,
The water-absorbent resin particles containing the chlorine dioxide or absorbing the generated water have an average particle diameter of 0.1 to 3 mm,
The ratio of the water absorbent resin before absorbing the water containing or generating chlorine dioxide and the water containing or generating chlorine dioxide is 1:3 to 1:10 by weight.
An antibacterial agent in which the particle surfaces of particles of the water absorbent resin before absorbing water containing or generating chlorine dioxide are treated with hydrophobic fine particles,
A bag-containing antibacterial agent characterized by being enclosed in a bag body (1) made of an impermeable material provided with a release hole for releasing chlorine dioxide and water into the atmosphere.

Further, the present invention is an antibacterial agent which comprises particles of a water-absorbent resin containing water containing chlorine dioxide or generating chlorine dioxide, which releases chlorine dioxide and water,
The average particle diameter of the particles of the water absorbent resin before absorbing water containing chlorine dioxide or generated is 30 to 850 μm,
The water-absorbent resin particles containing the chlorine dioxide or absorbing the generated water have an average particle diameter of 0.1 to 3 mm,
An antibacterial agent in which the ratio of the water-absorbent resin before absorbing the water containing or generating chlorine dioxide and the water containing or generating chlorine dioxide is 1:3 to 1:10 in weight ratio,
After being housed in a bag body (2) having fine pores having a diameter smaller than the particle diameter of the water-absorbent resin containing the chlorine dioxide or absorbing the generated water, chlorine dioxide and water are put into the atmosphere. An antibacterial agent in a bag, which is contained in a bag body (1) made of an impermeable material provided with a discharge hole for discharging .
Furthermore, the present invention is an antibacterial agent which comprises particles of a water-absorbent resin which absorbs water containing or generating chlorine dioxide, and which releases chlorine dioxide and water,
The average particle diameter of the particles of the water absorbent resin before absorbing water containing chlorine dioxide or generated is 30 to 850 μm,
The water-absorbent resin particles containing the chlorine dioxide or absorbing the generated water have an average particle diameter of 0.1 to 3 mm,
An antibacterial agent in which the ratio of the water-absorbent resin before absorbing the water containing or generating chlorine dioxide and the water containing or generating chlorine dioxide is 1:3 to 1:10 in weight ratio,
After being housed in a bag body (2) having fine pores having a diameter smaller than the particle diameter of the water-absorbent resin containing the chlorine dioxide or absorbing the generated water, chlorine dioxide and water are put into the atmosphere. An antibacterial agent in a bag, which is contained in a bag body (1) made of an impermeable material provided with a discharge hole for discharging.
Furthermore, the present invention is the bag-containing antibacterial agent according to any one of claims 1 to 4, wherein the release hole of the bag body (1) is covered with a peelable seal .
Furthermore, the present invention is the bag-containing antibacterial agent according to any one of claims 1 to 5, which contains cobalt chloride.

In the present invention, the water-absorbent resin which absorbs water containing or generating chlorine dioxide (hereinafter sometimes referred to as antibacterial water) is in a particle state rather than a conventional gel state, and therefore, the following effects are obtained. In the present invention, the particle state means a state in which particles are separated from each other, individual particles can be clearly confirmed, and the whole has fluidity.
(1) Since the water-absorbent resin has a remarkably large water-absorption capacity as compared with the conventional inorganic water-absorbent material, a small amount of the water-absorbent resin can hold a large amount of antibacterial water and maintain the antibacterial effect for a long time. You can
(2) The surface area of the particles is large and the amount of antibacterial water absorbed does not vary, and water and chlorine dioxide are easily volatilized from the surface of the particles.
(3) Since the antibacterial water is absorbed by the particles of the water-absorbent resin, the antibacterial water is less likely to come into direct contact with the surface of a container such as a bag as compared with a normal gel-like material. Therefore, the influence of the components in the antibacterial water on the container containing the antibacterial water is reduced. Therefore, chlorine dioxide in the antibacterial water is less likely to corrode the container.
(4) Since the water-absorbent resin is in the form of particles rather than gel, the workability of storing the water-absorbent resin in a container such as a bag is improved.

(5) When water and chlorine dioxide are volatilized from the water-absorbent resin, the water-absorbent resin shrinks more and more, and finally, most of the water is released. When the water absorbent resin is placed in the bag, the volume or amount of the water absorbent resin can be confirmed by touching the surface of the bag with hands. Of course, when the water absorbent resin loses its water content, chlorine dioxide also disappears. Then, the amount of remaining water can be known, and the end point of volatilization can be grasped to some extent.

Furthermore, since the average particle diameter of the particles of the water absorbent resin that has absorbed antibacterial water in the present invention is 0.1 to 3 mm, it does not become dust and is easy to handle. In addition, the whole is easy to flow, and the particles collide due to vibration during use, and the release of water and chlorine dioxide from the particles is further sustained.

Furthermore, the present invention, since the water-absorbent resin is treated with hydrophobic fine particles, the surface of the water-absorbent resin is dry, particles of the water-absorbent resin that have absorbed antibacterial water are less likely to stick to each other, and thus become in a particle state. Cheap. Also, since the particles are dry, it is easy to handle and easy to put in a container, which is advantageous in production.

Further, according to the present invention, the above antibacterial agent (a) is enclosed in a bag body (1) formed of an impermeable material provided with a release hole for releasing chlorine dioxide and water into the atmosphere. Therefore, it is easy to handle as an antibacterial agent, and since water and chlorine dioxide are emitted only from the discharge holes, an antibacterial effect is exerted for a long time.

Furthermore, according to the present invention, the antibacterial agent (a) is stored in a bag body (2) having fine pores having a diameter smaller than the particle diameter of the water-absorbent resin that has absorbed the antibacterial water, and then stored in a bag (2). Since it is housed in the bag body (1) made of an impermeable material provided with a release hole for releasing chlorine and moisture into the atmosphere, the water absorbent resin which has absorbed the antibacterial water is stored in the bag body (2). ), the bag body (2) containing the antibacterial agent (a) may be put into the bag body (1) without leaking, and the work is simplified. Further, since chlorine dioxide released outside the bag body (2) is released into the atmosphere from the release hole of the bag body (1), chlorine dioxide is released into the atmosphere at once even when strong vibration or shock is applied. Can be suppressed.

Furthermore, in the present invention, since the release hole is covered with a peelable seal, nothing comes out of the bag when not in use, but when the seal is peeled off during use, chlorine dioxide and water vaporize from the inside. The antibacterial effect of the present invention is exhibited.

Further, the present invention is a sheet type antibacterial agent (d), wherein the antibacterial agent (a) is housed in a flat container having at least one surface formed of a semipermeable membrane, and the sheet type antibacterial agent (d). Is a sheet type antibacterial agent (e) enclosed in a container made of a further sealed impermeable material, so that the release of water is suppressed and the release of chlorine dioxide is made more uniform during use. It is released stably over a long period of time.

Further, since the bag-containing antibacterial agent or sheet-type antibacterial agent of the present invention contains cobalt chloride, when the water content in the water-absorbent resin is lost, the pink color of cobalt chloride gradually fades and becomes blue. Due to the change in coloring, the amount of water in the water-absorbent resin can be visually ascertained, and the amount of water and chlorine dioxide can be understood to some extent.

Objects, features, and advantages of the present invention will become more apparent from the following detailed description and drawings.

1 is an embodiment of the present invention, and is a front view of a bag-containing antibacterial agent (c) including a bag body (1) containing a bag body (2). FIG. 1B is a cross-sectional view taken along a plane including the X-Y axes of FIG. 1A and perpendicular to the plane of the drawing. It is a perspective view of sheet type antibacterial agent (d) which is one embodiment in the present invention. FIG. 2B is an enlarged cross-sectional view of the sheet-type antibacterial agent (d) taken along a plane that includes the XY axes illustrated in FIG. 2A and is perpendicular to the paper surface. It is sectional drawing of the sheet|seat type|mold antibacterial agent (e) enclosed with the airtight container formed of the impermeable material to the sheet|seat type antibacterial agent (d) of FIG. 2B.

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

In the present invention, the antibacterial agent (a) absorbs water containing or generating chlorine dioxide (antibacterial water), and the water-absorbent resin absorbing water containing chlorine dioxide or generating chlorine (antibacterial water) is in a particulate state. Is. In the present invention, the water-absorbent resin is not used as a gel containing a large amount of water as in the conventional case, but is used as a particle state by reducing the amount of water absorption and slightly swelling. Naturally the particles are wet.

The water-absorbent resin before absorbing antibacterial water is not particularly limited, whether natural or synthetic, but is inexpensive, has excellent water-absorbing properties such as safety, durability, water absorption capacity and water retention, and is not susceptible to decay. Those that are not worried are preferred.

Specific examples thereof include synthetic water-absorbing resins, and as long as they absorb and retain water, they are not particularly limited. For example, polyacrylic acid partially neutralized crosslinked products, starch-acrylic acid grafts, etc. Neutralized product of polymer, hydrolyzate of starch-acrylonitrile graft polymer, saponified product of vinyl acetate-acrylic acid ester copolymer, isobutylene-maleic anhydride copolymer crosslinked product, acrylonitrile copolymer or acrylamide copolymer Hydrolyzate or cross-linked product of these, acrylic acid-acrylamide copolymer cross-linked product, polyvinyl alcohol cross-linked product, modified polyethylene oxide cross-linked product, acrylamido-2-methylpropane sulfonate copolymerized cross-linked product, (meth)acryloyl alkane Examples thereof include sulfonate copolymer cross-linked products, cross-linked carboxymethyl cellulose salts, and cross-linked polymers of cationic monomers. Among these, a partially crosslinked polyacrylic acid neutralized product and a neutralized product of a starch-acrylic acid graft polymer are preferable because they have particularly good water absorption properties, safety, and economical efficiency.

The water-absorbent resin in the present invention can be obtained by drying and pulverizing a hydrogel polymer of the water-absorbent resin obtained by polymerization/crosslinking, but an absorbent obtained by further adjusting the particle size if necessary. It is more preferable to use a surface-crosslinked water-absorbent resin in which the surface vicinity of the particles is surface-crosslinked with a crosslinking agent having at least two functional groups capable of reacting with an acid group such as a carboxyl group and/or its base.

Such a surface cross-linking type water absorbent resin is excellent in water absorption and water retention under normal pressure as well as under pressure, and also has high gel strength, so that the water retention is further good and suitable for the present invention. ..

As the cross-linking agent used for the above surface cross-linking, known cross-linking agents that have been conventionally used can be applied. As specific examples, polyglycidyl ether compounds having 2 to 10 epoxy groups in one molecule [ethylene glycol diglycidyl ether, glycerin-1,3-diglycidyl ether, glycerin triglycidyl ether, etc.]; divalent to 20-valent polyol compound [glycerin, ethylene glycol, polyethylene glycol (degree of polymerization 2-100), etc.; divalent-20-valent polyamine compound (ethylenediamine, diethylenetriamine, etc.); polyamine resin having a molecular weight of 200-500,000 (polyamide) Polyamine epichlorohydrin resin, polyamine epichlorohydrin resin, etc.), alkylene carbonate [ethylene carbonate, etc.], aziridine compound, oxazoline compound, polyimine compound and the like.

Of these, preferred are polyglycidyl ether compounds, polyamine resins, and aziridine compounds in that they can be surface-crosslinked at a relatively low temperature.

The above water-absorbent resins may be used alone, or may be used by appropriately mixing two or more kinds. The water-absorbent resin is in the form of particles, and may be granulated into a predetermined shape, and the shape is not limited, such as crushed irregular shape, spherical shape, scale shape, fibrous shape, rod shape, lump shape, and powder shape. However, in order to improve the water absorption property, it is more preferable that it is in powder form.

The average particle size of the particles is not particularly limited, but is preferably 30 to 850 μm, more preferably 60 to 400 μm. When the average particle size of the particles is 30 μm or more, the water absorption property is good and the production is easy. If the average particle size of the particles is 850 μm or less, blocking is difficult even when placed in a bag. The particle size distribution of the particles is not particularly limited, but the particle size distribution is preferably such that particles in the range of 30 to 850 μm account for 95% by mass or more. Here, the average particle size means the mass average particle size, the mass average particle size, each particle size distribution of the cross-linked polymer is plotted on the logarithmic probability paper of the particle size on the horizontal axis, the vertical axis is the mass-based content, It is measured by the method of determining the particle size where 50% of the whole is occupied. For example, a normal sieving method can be applied.

The water absorption capacity of the water absorbent resin is preferably 20 to 1,000 g/g, more preferably 80 to 600 g/g. When the water absorption capacity of the water absorbent resin is 20 g/g or more, the water absorption and water retention are good, and when it is 1,000 g/g or less, the antibacterial water is likely to be absorbed into a dry powder. The water absorption amount can be controlled by various production conditions of the above water-absorbent resin.

The water retention/water absorption ratio of the water absorbent resin is preferably 0.55 to 1.00, more preferably 0.65 to 1.00. If the water retention/water absorption ratio of the water absorbent resin is 0.55 or more, it is easy to retain the chlorine dioxide water for a long period of time. The ratio of water retention capacity/water absorption capacity can be controlled by the type of monomer and the crosslinking conditions.

The water absorption capacity and water retention capacity of the water absorbent resin can be measured as follows.
[Water absorption ratio]
A tea bag made of 250 mesh nylon net, size 10×20 cm, heat seal width of 5 mm or less, and pure water are prepared. The water-absorbent resin is sieved through a JIS standard sieve, and particles having a particle size of 30 to 100 mesh are sampled to obtain a measurement sample.

0.20 g of the sample is put into a tea bag, and it is soaked in pure water about 15 cm from the bottom of the tea bag. After left for 1 hour, the tea bag is pulled up, hung vertically and drained for 15 minutes. The weight (Ag) is measured. The weight (Bg) is measured by performing the same operation using an empty tea bag containing no sample. The measurement is performed 3 times and averaged. Calculated from the water absorption capacity (g/g)=(AB)/0.2.

[Water retention amount]
A centrifugal separator capable of exerting a centrifugal force of 150 G (1100 rpm, r=10 cm) is prepared. A tea bag containing the sample after measuring the water absorption amount is set in a centrifuge, an empty tea bag is set diagonally with the tea bag, and centrifugation is performed at 150 G×90 seconds. The weight of each tea bag is measured, and the water retention capacity (g/g)=(AB)/0.2 is calculated.
The water retention amount/water absorption ratio can be calculated by using the above numerical values.

The water-absorbent resin is in a particle state even if it absorbs water (antibacterial water) containing or generating chlorine dioxide, and in the present invention, it must maintain the shape of particles. If the water content in the water-absorbent resin is low, the shape of the particles can be easily maintained, and if the water content is high, the particles will collapse and become in a gel state. As such a water-absorbent resin, a surface-crosslinked resin is preferable because it easily retains its shape. Further, it is more preferable that the surface of the particles is treated with hydrophobic fine particles to make the surface of the particles hydrophobic so that the surface becomes more dry and the particle state is more easily maintained. By doing so, the water absorbent resin that has absorbed the antibacterial water can be easily made into a particle state.

The hydrophobic fine particles used when the particle surface is subjected to the hydrophobic treatment are not particularly limited as long as they are hydrophobic and are smaller than the particle diameter of the water absorbent resin. The hydrophobic inorganic fine particles are suitable. The average primary particle diameter of the inorganic fine particles is preferably 7 nm or more and 300 nm or less. If the inorganic fine particles are within this range, they can be attached to the surface of the particles of the water absorbent resin to improve the hydrophobicity of the water absorbent resin. The average primary particle diameter of the inorganic fine particles is more preferably 10 nm or more and 100 nm or less.

Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica ash. Stone, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like can be mentioned, but in the present invention silica Is preferable because it has versatility.

Examples of the hydrophobizing agent for hydrophobizing the inorganic fine particles include, for example, trimethylchlorosilane, methyltrichlorosilane, bromomethyldimethylchlorosilane, 3-chloropropyltrimethoxysilane, vinylmethoxysilane, and γ-methacryloxypropyltrisilane. Methoxysilane, dimethylvinylchlorosilane, octyltrichlorosilane, dipentyldichlorosilane, trihexylchlorosilane, tridecylchlorosilane, dioctylmethylchlorosilane, isobutyltrimethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, hexamethyldichlorosilane Organic silane compounds such as silazane and diethyltetratyldisilazane, dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methylhydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, Alcohol modified silicone oil, amino modified silicone oil, epoxy modified silicone oil, epoxy/polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic, methacryl modified silicone oil, α-methylstyrene modified Examples thereof include silicone oils such as silicone oil, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, and aluminum coupling agents. Of these, organic silane compounds are preferable.

Hydrophobic inorganic fine particles are obtained by treating the inorganic fine particles with the above-mentioned hydrophobic treatment agent, and among these, hydrophobic silica fine particles are preferable. Examples of commercially available hydrophobized silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21 (all manufactured by Hoechst) and R972, R974, RX200, RY200, R202, R805, R812 (all Nippon Aerosil). Manufactured by Cabot Corporation), TS530, TS720 (manufactured by Cabot Corporation) and the like, and these can be used.

As a method for treating the water-absorbent resin with the hydrophobic fine particles, the hydrophobic fine particles are mixed with the water-absorbent resin and mixed at preferably 0 to 50° C., more preferably 10 to 30° C. Preferably, 1 to 20 parts by weight, more preferably 2 to 7 parts by weight, of the hydrophobic fine particles are mixed and mixed with 100 parts by weight of the water absorbent resin. The mixing method can be obtained by putting both in a container, stirring and mixing, or shaking. Moreover, when putting in the bag body (1) or the bag body (2) explained below, you may mix in this.

It is also possible to add antibacterial water to the water-absorbent resin and then add hydrophobic fine particles to the mixture to further mix them to make the mixture even more dry.

Examples of water containing or generating chlorine dioxide (antibacterial water) include chlorite aqueous solution, stabilized chlorine dioxide aqueous solution, aqueous solution of chlorine dioxide dissolved in water (for example, pure chlorine dioxide aqueous solution or pure neutral chlorine dioxide aqueous solution). Etc.), but are not limited thereto. Preferred are chlorite aqueous solution and stabilized chlorine dioxide aqueous solution. Hypochlorite may be contained in these.

The chlorite aqueous solution means an aqueous solution containing chlorite. The chlorite is not particularly limited as long as it reacts with an acid to generate chlorine dioxide, and examples thereof include alkali metal chlorite such as sodium chlorite, potassium chlorite, and lithium chlorite. Examples thereof include salts, alkaline earth metal chlorite salts such as calcium chlorite, magnesium chlorite, barium chlorite, and the like. Among these, sodium chlorite is preferred because it is easily available and has no problem in use.

The aqueous chlorite solution is chemically stable if it has a pH of 8.5 or more, and can be stored for about 0.5 to 1 year by storing it in a sealed container. Here, as the aqueous solution of sodium chlorite, a commercially available product such as a 32 mass% product or a 25 mass% product can be used.

The stabilized chlorine dioxide aqueous solution is an aqueous solution in which chlorine dioxide is dissolved and stabilized in an alkaline aqueous solution, and existing chemical substances 1-143, CAS No. 10049-04-4, which is a chemical substance identified by the same number as chlorine dioxide. On the other hand, the sodium chlorite and the sodium chlorite solution are both existing chemical substances 1-238, CAS No. It is a chemical substance specified in 7758-19-2.

The carboxyl group of the water absorbent resin reacts with chlorite to generate chlorine dioxide. The carboxyl groups in the water absorbent resin are not completely neutralized, and normally 20 to 30 mol% of the carboxyl groups are unneutralized. Since the water-absorbent resin in the particles is a resin and cannot move around in the water in the water-absorbent resin, the chlorite existing in the water in the particles moves and contacts the carboxyl groups of the water-absorbent resin. And react. When the antibacterial agent (a) is used, the chlorite reacts with the carboxyl group due to volatilization of water, vibration of particles, and collision, so that chlorine dioxide can be continuously generated. Further, by volatilizing the water, there is a surplus in the absorption capacity of the water absorbent resin, and the generated chlorine dioxide can be retained and contribute to the sustainability.

The stabilized chlorine dioxide aqueous solution is not particularly limited in its production method as long as it is a solution in which dissolved chlorine dioxide is stabilized. For example, sodium percarbonate is added while blowing chlorine dioxide gas into the sodium carbonate aqueous solution. It is obtained by Moreover, a stabilizer for stabilizing chlorine dioxide dissolved in the solution may be added in some cases.

Chlorine dioxide content contained in the stabilized chlorine dioxide aqueous solution used in the present invention is not particularly limited, from the viewpoint of maintaining a stable concentration of chlorine dioxide in deodorization, sterilization, fungicides, preservatives, etc., It is preferably from 0.05% by mass to 25% by mass.

As a commercial product of the stabilized chlorine dioxide aqueous solution, Anthium Dioxcide manufactured by International Dioxide INC is 5 mass% (50000 ppm) chlorine dioxide, 3.65 mass% sodium carbonate, and 91.35 mass% water, including. EZ Flow 25% made by Rio Linda Chemical Co contains 25% by weight chlorine dioxide, 5% by weight sodium chloride, 2% by weight sodium carbonate and 68% by weight water. Bio-Cide Chemical Co. Purogen from Inc contains 2 wt% (20000 ppm) chlorine dioxide.

The ratio of the water absorbent resin before absorbing the antibacterial water (hereinafter, also referred to as water absorbent resin before containing water) and the antibacterial water is preferably 1:1 to 1:40 by weight. When the ratio of the antibacterial water is 1 or more, the antibacterial agent (a) can volatilize chlorine dioxide and water, and when the ratio is 40 or less, the water-absorbent resin after hydration tends to be particulate. More preferably, it is 1:3 to 1:10.

When the water-absorbent resin before water absorption absorbs the antibacterial water, the amount of the antibacterial water is preferably 1/10 or less, more preferably 1/30 or less, and particularly preferably 1/80 or less of the water absorption capacity of the water absorbent resin. .. When it is 1/10 or less, the water absorbent resin absorbs the antibacterial water and is likely to be in the form of particles.

The method of absorbing the antibacterial water in the water absorbent resin can be carried out, for example, by spraying the water absorbent resin powder with the antibacterial water at room temperature, or by mixing the water absorbent resin and the antibacterial water in a container such as a bag and then closing and stirring or shaking.

The shape of the particles after the water-absorbent resin has absorbed the antibacterial water is not particularly limited, but a powder is preferable because it is easy to handle and the volatilization of chlorine dioxide water is good.

The average particle diameter of the particles of the water absorbent resin (hereinafter, also referred to as antibacterial agent (a)) that has absorbed antibacterial water is preferably 0.1 to 3 mm. Naturally, the water-absorbent resin that has absorbed the antibacterial water swells, but if the amount of the antibacterial water is suppressed to a certain level or less as described above, the shape of the particles can be maintained without gelation. When the particle size after water absorption is in the above range, the surface area is much larger than in the case of gelling, and chlorine dioxide and water are more likely to be volatilized. Further, since the whole has fluidity, when impact or vibration is applied to the antibacterial agent (a), the air around the antibacterial agent (a) vibrates, the antibacterial agent (a) moves, and the particles collide. Chlorine dioxide is released from the particles along with water. When the average particle diameter of the particles of the antibacterial agent (a) is 0.1 mm or more, it is easy to maintain the particle shape and easy to handle. When the average particle diameter of the particles of the antibacterial agent (a) is 3 mm or less, blocking is difficult even when put in a bag. The average particle diameter of the particles of the antibacterial agent (a) is preferably 0.3 mm or more and 2 mm or less. Within this range, it can be more preferably used as a particle state. The particle size distribution of the particles of the antibacterial agent (a) is not particularly limited, but is preferably such that the particles in the range of 0.1 to 3 mm are 80% by mass or more. Here, the average particle size and the particle size distribution are the same as in the case of the water absorbent resin before containing water.

Further, since the antibacterial agent (a) is in the form of particles, it can be formed into a sheet like the particles of ordinary water absorbent resin. A known method can be applied to form a sheet. For example, particles of a water-absorbent resin or antibacterial agent (a) (hereinafter sometimes simply referred to as powder) are fixed to a base material, the particles are dispersed on the base material, and sandwiched between the other base materials in a sandwich form. Examples include those in which particles are integrated by a method such as an embossing method, a needle punch method, a stitch bond method, and a fusion method. The position of the particles on the base material is preferably continuously sprayed whether it is the entire surface of the base material or a linear shape having a width.

As the base material, for example, a cotton-like material such as wood pulp or various fibers such as water-absorbent fibers are formed into a sheet by an appropriate method such as papermaking, mechanical adhesion, binder adhesion, spunbond method, spunlace method, etc. A laminated body formed by laminating these is exemplified. Preferred are those in which particles are immobilized on one or both sides of a substrate such as cloth (particularly preferably non-woven fabric) or paper using an adhesive or a binder resin, and particularly preferred are cotton pulp of wood pulp. Objects, laminates, tissues, etc. with powder fixed on them, sandwiched between substrates, then embossed, needle punched to integrate the powders, adhesive on one or both sides of the plastic film The particles are fixed using an agent or a binder resin, and examples thereof include those in which the particles are dispersed on the adhesive surface using cellophane or vinyl adhesive tape and fixed by a pressure roll.

The antibacterial agent (a) may be formed into a sheet shape as described above, or after the particles of the water-absorbent resin are formed into a sheet shape, an amount of the antibacterial water after absorbing the antibacterial water is converted into particles in the sheet. You may drop on the particle|grains of water-absorbent resin, and may be made to absorb. The former is preferable.

A fixed amount of the particles is preferably 1 to 100 g / m ^2, more preferably from 10 to 60 g / m ^2, particularly preferably 20 to 50 g / m ^2.

The thickness of the sheet is preferably 0.001 to 5 mm, more preferably 0.01 to 3 mm.

The antibacterial agent (a) of the present invention can be used in the form of particles or in the form of a sheet, and can be used as it is in a place for antibacterial purposes, sprinkled on a target substance, or mixed. Preferably, it can be used as (1) a bag-shaped antibacterial agent (b) housed in a bag and (2) a sheet-shaped antibacterial agent (d) formed in a sheet shape. The bag-shaped antibacterial agent (b) of (1) is preferably flat in use, and since the antibacterial agent (a) is in the form of particles, it is suitable for being housed in a bag. In the case of the sheet type antibacterial agent (d) of (2), for example, the antibacterial agent (a) is held on one or more base materials as described above, and then the other materials are combined and compressed. It can be formed into a sheet by adhesion or the like. In this case, it is necessary to devise another material to release chlorine dioxide, and it is necessary to put a seal on it so that it cannot be released before use and peel off the seal at the time of use, but it is limited to this. Not done.

A preferred structure of the bag-containing antibacterial agent (b) is, for example, a bag body (the antibacterial agent (a) formed of an impermeable material provided with a release hole for releasing chlorine dioxide and moisture into the atmosphere ( It is an antibacterial agent in a bag that is enclosed in 1). In particular, after the antibacterial agent (a) is accommodated in a bag body (2) having fine pores having a diameter smaller than the particle size of the water absorbent resin that has absorbed antibacterial water, the bag body (2) Is preferably a bag-containing antibacterial agent (c) housed in the bag body (1). When the bag body (2) is used, chlorine dioxide released to the outside of the bag body (2) is released from the release holes of the bag body (1) into the atmosphere, so that even if strong vibration or shock is applied, In addition, the release of chlorine dioxide into the atmosphere can be suppressed.

The shape of the bag body (1) is not particularly limited, and examples thereof include a rectangular shape, a circular shape, and an elliptical shape, but a flat polygonal shape is preferable when it is lowered from the neck or put in a pocket. The size of the bag body (1) is also not particularly limited, but for example, a rectangular shape of 40 to 60 mm×60 to 90 mm is preferable.

The material forming the bag body (1) is not limited as long as it is an impermeable material that does not allow chlorine dioxide gas to pass through, but is preferably a light-shielding material from the viewpoint of maintaining the stability of chlorine dioxide. Examples of such a material include, but are not limited to, a laminated film of an aluminum layer and a plastic layer, an aluminum vapor deposition film, and the like.

The discharge holes may be provided anywhere in the bag body (1), but by providing the discharge holes at the edges of a plurality of polygonal sides, it is possible to ensure a flow path of air even when stationary and to efficiently. It can release chlorine dioxide. The size and number of the release holes can control the release of chlorine dioxide existing in the bag body (1) to the outside.

It is more preferable that the discharge holes provided in the bag body (1) are provided in a plurality of discharge holes on one or both sides of the edge portion with a space between the discharge holes. The size of the discharge hole is preferably such that particles of the water-absorbent resin do not come out from the discharge hole. However, the bag body (2) containing the particles of the water-absorbent resin is packed in the bag body (1). If accommodated, the size of the discharge hole is arbitrary. Further, since the fine holes described in the bag body (2) below can also function as the discharge holes, it is not necessary to specifically provide the holes. Micropores are also emission holes. Before use, these discharge holes are closed with a peelable seal, and when used, the seal is peeled off to open the discharge holes. With such a configuration, it is possible to prevent the emission of chlorine dioxide from the emission holes when not in use, and it is suitable for storage. The same seal material as the conventional one can be used.

The size of the bag body (2) is preferably slightly smaller than that of the bag body (1) because it is used in the bag body (1). The shape of the bag body (2) is preferably matched with the shape of the bag body (1), for example, a flat polygonal shape. On the entire surface of the bag body (2), fine pores having a diameter smaller than the diameter of the water absorbent resin that has absorbed antibacterial water are formed. The fine pores do not allow particles of the water-absorbent resin to pass through, but chlorine dioxide molecules do. As a material for such a bag (2), a plastic film having fine pores formed therein (for example, a semipermeable membrane film that allows water vapor to pass therethrough but does not allow water to pass therethrough), or a cloth such as a plate, a knitted fabric, or a nonwoven fabric is used. Can be used. Of these, semipermeable membranes and non-woven fabrics are preferable from the viewpoint of ease of use, since there is no leakage of water-absorbent resin particles. Further, when a semipermeable membrane is used, the vaporization rate of water is slowed down, the release of chlorine dioxide is suppressed due to the effect, and the release of chlorine dioxide is stabilized as a whole, which is preferable for long-term use. The bag (2) can be manufactured by a conventionally known method, for example, one manufactured by folding one nonwoven fabric in two and pasting the periphery thereof.

Chlorine dioxide supported on the water-absorbent resin that constitutes the antibacterial agent (a) is the surface of the particles due to the flow of air generated by the vibration of the antibacterial agent contained in the bag and the collision of the particles that constitute the antibacterial agent (a). And is released to the outside of the bag body (2) through the fine pores formed on the entire surface of the bag body (2) made of a non-woven fabric. After that, it is discharged from the discharge hole of the bag body (1).

Regarding the shape and configuration of the bag body (1) and the bag body (2), those described in Japanese Patent No. 5172002 can be used.

Another aspect of the present invention is a sheet type antibacterial agent (d) in which the above antibacterial agent (a) is contained in a flat container having at least one surface formed of a semipermeable membrane. Further, the sheet type antibacterial agent (d) is a sheet type antibacterial agent (e) which is enclosed in a container formed of a sealed impermeable material.

The antibacterial agent (a) of the present invention is an antibacterial agent composed of particles of a water absorbent resin that absorbs water containing chlorine dioxide or generated (antibacterial water), and since the water absorbent resin is in a particle state, Due to its high volatilization rate, chlorine dioxide is also released along with it. However, as the evaporation rate of water becomes slower, the release rate of chlorine dioxide becomes slower, and if the release rate of water is controlled, the release rate of chlorine dioxide can be stably controlled as a whole. The rate of evaporation of water can be controlled by the size and number of the release holes in the bag (1), that is, the area of the opening in the bag (1). By optimizing the ratio of the opening area to the surface area of the bag body (1), the release rate of chlorine dioxide can be controlled according to the purpose.

Furthermore, by controlling the micropores of the bag body (2) in addition to the control of the release holes of the bag body (1), it becomes possible to deal with antimicrobial agents of all forms. If the pore diameter of the micropores having a diameter smaller than the particle diameter of the water-absorbent resin is further reduced, and the bag body (2) is formed of a semipermeable membrane film that allows water vapor to pass through at least one surface but does not allow liquid water to pass therethrough. The rate of evaporation of water can be reduced considerably. However, if the diameter of the micropores is too small, the release rate of chlorine dioxide may be slow, and it is preferable to determine the vaporization rate of water according to the application. That is, since a thin material such as a sheet or a material such as a patch having a small area does not have a large amount of antibacterial water therein, it is necessary to reduce the evaporation rate of water. In that case, since it is difficult to control with the above-mentioned release hole, it is preferable to package the antibacterial agent (a) with a semi-permeable film that allows water vapor to pass but does not allow liquid water to pass. That is, another embodiment of the present invention is a sheet type antibacterial agent (d) in which the above antibacterial agent (a) is contained in a flat container having at least one surface formed of a semipermeable membrane. Further, the sheet type antibacterial agent (d) is a sheet type antibacterial agent (e) which is enclosed in a container formed of a sealed impermeable material.

The semipermeable membrane has a small gas permeability, and can suppress volatilization of water gas (referred to as water or water vapor in the present invention). At the same time, the release of chlorine dioxide from the system can be suppressed, and the release rate can be made more uniform as a whole. The semipermeable membrane is not particularly limited, and the semipermeable membrane may be selected so that the desired more uniform release rate of chlorine dioxide can be obtained.

Examples of such a semipermeable film include a polyvinyl alcohol film (vinylon film), cellophane, a low-stretching nylon film, an ethylene vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, a porous film. (A film having fine pores) and the like, but not limited thereto. The porous film is, for example, of a type in which 10 to 1,000 fine holes having a diameter of 0.01 to 100 μm are opened per 1 m ² , and numerous scratches are made on the entire film (partially penetrating therethrough). However, there is a type in which the amount of water vapor permeation is controlled by the depth and number of scratches.

In the present invention, a semipermeable membrane film that is permeable to liquid water but permeable to water vapor is practical and preferable. If a semipermeable membrane that does not allow liquid water to pass through but allows water vapor to pass through is used, the semipermeable membrane does not allow liquid water to pass through even if the product container is exposed to an acidic aqueous solution such as soy sauce or vinegar. Therefore, the generation of chlorine dioxide is not promoted and the harmful effect is reduced.

The method for producing the sheet-type antibacterial agent (d) is not particularly limited, for example, a shape in which at least one surface is a semipermeable membrane film, the other surface is made of an impermeable base material, and a part is left to be closed. After heat-sealing, the above particles and sheet are inserted and heat-sealed to hermetically seal. In this state, water evaporates, so that the sheet type antibacterial agent (e) can be obtained by enclosing the container in a container made of an impermeable material and sealing it. At this time, an adhesive or an adhesive tape may be attached to the thick impermeable base material and attached to the garment at the time of use.

As the impermeable base material, the same material as that used for the material forming the bag body (1) can be applied.

The size of the sheet type antibacterial agent (d) is arbitrary, but it may be large when it is attached to a wall, but it is small when it is attached to clothes such as patches or attached to a box of Japanese sweets. used. The shape is also arbitrary, and examples thereof include a rectangular shape and a circular shape. The thickness is preferably about 0.5 mm to 10 mm.

The amount of the antibacterial agent (a) in the sheet type antibacterial agent (d) is arbitrary and may be used depending on the use and size.

In the bag-containing antibacterial agent or sheet-type antibacterial agent of the present invention, the volume of the particles of the water-absorbent resin contracts because the antibacterial water in the water-absorbent resin is volatilized, and the user can press the water-absorbent resin from the outside of the container. It is possible to know the volume or amount, and thus the approximate amount of chlorine dioxide remaining.

Further, it is preferable to add cobalt chloride to the bag-containing antibacterial agent or the sheet-type antibacterial agent. Cobalt chloride (CoCl ₂ ) is pink when absorbing water, and gradually turns blue when the water evaporates. The amount of water can be visually grasped by the change in color. If it turns blue, it means that the water has evaporated. When the inside of the bag-containing antibacterial agent (b) or the sheet-type antibacterial agent (d) is made visible to the naked eye, the coloring of cobalt chloride in the bag can be seen. The amount can be grasped. Such cobalt chloride is preferably in the form of particles, and the smaller the average particle size, the more preferable. This is because the area is increased and the water adsorption performance is improved. The average particle size of cobalt chloride is preferably 100 μm or less. Cobalt chloride is added together with the antibacterial agent (a), but it is preferable not to contact it. This is to prevent cobalt chloride from contacting the antibacterial agent (a) and affecting the generation of chlorine dioxide.

Further, when water is absorbed by the water-absorbent resin, the pH of the contained water is lowered, but an acid (acidic substance) can be further used in combination to promote generation of chlorine dioxide. Examples of such an acid include inorganic acids such as phosphoric acid, organic acids such as citric acid, malic acid, succinic acid and tartaric acid, bleaching powder, isocyanuric acids and the like.

It is also possible to use hydrogen salt in combination to further promote the generation of chlorine dioxide. The hydrogen salt is a salt in which H ⁺ of a polyvalent acid is replaced with a cation and still retains H ⁺ , and examples thereof include sodium hydrogen sulfate, potassium hydrogen sulfate, sodium dihydrogen phosphate and phosphorus. Examples thereof include disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium hydrogen carbonate and potassium hydrogen carbonate.

Further, a gas generation regulator may be used together. The gas generation regulator is a regulator for continuously generating the generated chlorine dioxide gas, and when the amount of chlorine dioxide gas produced is large, at least a part of the chlorine dioxide gas is generated on the surface and/or inside. Retains the chlorine dioxide gas that is retained and releases the retained chlorine dioxide gas when the amount of chlorine dioxide gas produced decreases or disappears, thereby having a function of continuously generating chlorine dioxide gas from the antibacterial agent (a). ..

The gas generation regulator is not particularly limited in material and shape as long as it can efficiently disperse chlorine dioxide gas generation, but for example, sepialite, montmorillonite, diatomaceous earth, talc, alumina gel, alumina silica gel, silica. Examples thereof include calcium acid, calcined aggregates such as shellfish and coral, calcined clay, and zeolite. Among them, sepiolite, montmorillonite, diatomaceous earth, talc, zeolite and the like having a relatively large surface area are preferable from the viewpoint of retaining a large amount of chlorine dioxide gas. Further, from the viewpoint of increasing the surface area, it is preferably powdery, granular and/or porous.

Here, sepiolite is a natural mineral of magnesium silicate and has a chemical structural formula represented by (OH ₂ ) ₄ (OH ₂ ) ₄ (OH ₂ ) ₄ Mg ₈ Si ₁₂ O ₃₀ ·6 to 8H ₂ O. Its crystal structure is fibrous and has a large number of grooves on the surface, and has a large number of clearances of a tubular tunnel structure inside, and is a material with a very large surface area.
These are preferably used together with the antibacterial agent (a).

FIG. 1A and FIG. 1B show an example of an antibacterial agent (c) in a bag, which is an embodiment of the present invention and is composed of a bag body (1) containing a bag body (2), but is not limited thereto. .. 1A is a front view thereof, and FIG. 1B is a sectional view taken along a plane including the XY axes of FIG. 1A and perpendicular to the plane of the drawing.

The bag-containing antibacterial agent (b) 1 shown in FIG. 1A is composed of a rectangular bag body (1) 2. Two laterally long discharge holes 3 are formed at the edges of both upper ends of the bag body (1) 2, and the discharge holes 3 are covered with a seal 4. In FIG. 1B, the bag body (2) 5 is housed in the bag body (1) 2, and the bag body (2) 5 is an antibacterial agent that is particles of a water-absorbent resin that has absorbed antibacterial water. (A) It is shown that 6 is included.

2A and 2B show the sheet type antibacterial agent (d), and FIG. 2C shows the sheet type antibacterial agent (e). FIG. 2A is a perspective view of the sheet type antibacterial agent (d). FIG. 2B is an enlarged cross-sectional view of the sheet-type antibacterial agent (d) taken along a plane that includes the XY axes shown in FIG. 2A and is perpendicular to the paper surface. FIG. 2C shows a sheet type antibacterial agent (e) obtained by enclosing the sheet type antibacterial agent (d) of FIG. 2B in a closed container formed of an impermeable material. The sheet-type antibacterial agent (d) 7 has a rectangular shape, both sides are formed of a semipermeable membrane film 8, and heat seals 9 are provided on four sides. The double-sided adhesive tape 10 is attached to one surface. A sheet 11 containing the particulate antibacterial agent (a) 6 is enclosed therein. Since the antibacterial agent (a) 6 is particles, there are many gaps, and chlorine dioxide is released to the outside through these gaps. Further, in the sheet type antibacterial agent (e) 13 shown in FIG. 2C, since the sheet type antibacterial agent (d) 7 is enclosed in a closed container formed of the impermeable material 14, water and chlorine dioxide are not released. .. At the time of use, the sheet type antibacterial agent (d) 7 can be taken out from the closed container and the release paper 12 can be removed from the double-sided adhesive tape 10 and attached to clothes. Chlorine dioxide is released together with water through the semipermeable membrane 8 and the surroundings can be made into an antibacterial atmosphere.

Examples will be described below, but the invention is not limited thereto.
(Example) Preparation of antibacterial agent (a)-1 "Sunfresh ST-500D" (polyacrylic acid cross-linking type water absorbent resin, powder, water absorption capacity 400 times, particle size) in a double polypropylene bag 106-850 μm, average particle size 370 μm; Sanyo Chemical Industry Co., Ltd.) 6 g and “R-972” (hydrophobic silica, Nippon Aerosil Co., Ltd.; average particle size 16 nm) 0.18 g are put, shaken at room temperature for 10 minutes, and absorbed water. The hydrophobic resin was subjected to a hydrophobic treatment.

Into this, 31 g of an aqueous solution of a commercially available stabilized chlorine dioxide solution (60,000 ppm as chlorine dioxide) diluted with purified water (3,000 ppm as chlorine dioxide, pH 10.3, hereinafter may be simply referred to as chlorine dioxide solution) was added. Then, the mixture was shaken at room temperature for 20 minutes to prepare an antibacterial agent (a)-1 of the present invention which absorbed an aqueous chlorine dioxide solution. Although it swelled slightly, it remained in the form of particles and had a free-flowing fluidity. This product had 6 g of chlorine dioxide water absorbed in 1 g of a water-absorbent resin that had been subjected to a hydrophobic treatment, and the absorption amount was 6 times, which was 1/67 of the water absorption capacity (400 times).

(Example 2) Preparation of antibacterial agent (a)-2 Using 6 g of "Sunfresh ST-500D" and 1.0 g of "R-972" used in Example 1, water absorption was performed in the same manner as in Example 1. The hydrophobic resin was subjected to a hydrophobic treatment.

Furthermore, 36 g of an aqueous solution (pH 10.1) obtained by diluting the above-mentioned stabilized chlorine dioxide aqueous solution to 1000 ppm was added thereto, and the mixture was shaken at room temperature for 20 minutes to absorb the chlorine dioxide aqueous solution of the present invention (a)-2. Was manufactured. Although it swelled considerably, it remained in the form of particles and had a free-flowing fluidity. This product absorbed 40 g of chlorine dioxide water in 1 g of the water-absorbent resin subjected to the hydrophobic treatment, the absorption amount was 40 times, which was 1/10 of the water absorption capacity (400 times).

(Comparative Example 1) Comparative antibacterial agent (a)-3
When 600 g of an aqueous solution (pH 10.1) obtained by diluting the stabilized chlorine dioxide aqueous solution described above to 1000 ppm was added to 6 g of the hydrophobized "Sunfresh ST-500D" produced in the same manner as in Example 2, and shaken. The whole was in a gel form, and comparative antibacterial agent (a)-3 was produced. The chlorine dioxide water absorption of the water absorbent resin was 100 times, which was about 1/4 of the water absorption capacity.

(Comparative Example 2) Comparative antibacterial agent (a)-4
100 g of an aqueous solution (pH 10.1) obtained by diluting the above-mentioned stabilized chlorine dioxide aqueous solution to 1000 ppm was added to 10 g of zeolite powder, allowed to stand for 30 minutes and then filtered through a filter paper to prepare a comparative antibacterial agent (a)-4. 1 g of zeolite absorbed 0.25 g of chlorine dioxide water.

(Examples 3 and 4, Comparative Examples 3 and 4)
A 90 mm×130 mm non-woven fabric (weight per unit area: 50 g/m ² ) was vertically folded in two, and one side was left and the surrounding three sides were pasted with a width of 5 mm. Put 10 g of each of the above-mentioned antibacterial agents (a)-1 to 4 from the opening on the remaining side, immediately seal and attach with a width of 5 mm, store in a polypropylene bag impermeable to chlorine dioxide water. did. Thus, the antibacterial agent contained in the rectangular bag body (2) of 45 mm×65 mm was manufactured.

On the other hand, a card-shaped case having a size of 65 mm×95 mm in length was prepared from an aluminum vapor-deposited polyester film. In this case, one side is left and three sides are bonded with a width of 5 mm, and two 5 mm × 10 mm horizontally long emission holes are provided at both ends of the upper part (1 cm from the top) on the front side. , The entire front side is sealed with a polyester film. The above-mentioned bag bodies (2) were inserted from the remaining one opening of the case, and then closed and adhered and sealed with a width of 5 mm. In this manner, the bagged antibacterial agents A and B of the present invention and the comparative bagged antibacterial agents C and D were produced.

The amount of chlorine dioxide solution contained in each bag of antibacterial agent is as follows.
Example 3: Antibacterial agent A in a bag Amount of antibacterial water=8.33 g
Example 4: Antibacterial agent B in a bag Amount of antibacterial water=8.37 g
Comparative Example 3: Antibacterial agent C in a bag Amount of antibacterial water=9.90 g
Comparative Example 4: Antibacterial agent D in a bag Amount of antibacterial water = 2.00 g

In the same 10 g as the antibacterial agent (a), the bagged antibacterial agents A to C absorbed a large amount of chlorine dioxide water, but the amount of chlorine dioxide water in the bagged antibacterial agent D whose carrier was zeolite was small. ..

(Test example)
Each bag-containing antibacterial agent was removed from the seal and hung on the wall, and after 1 to 4 weeks, the weight of the bag-containing antibacterial agent was measured to confirm how much chlorine dioxide was volatilized with water. The results are shown in Table 1. Also, after 1 to 4 weeks, put the bag-containing antibacterial agent into a 10 L gas repair bag, shake the bag up and down 1 hour to homogenize the gas inside, and then use a detector tube to put it inside the bag. The chlorine dioxide emission concentration (ppm) was measured. The results are also shown in Table 1.

From Table 1, the weight reduction amount of the bag-containing antibacterial agents C and D of the comparative example was small, but the weight reduction amount of the bag-containing antibacterial agents A and B of the example was large. It is considered that this is because the bag-containing antibacterial agent C was in the form of a gel and thus the amount of volatilization from the surface was small, and the bag-containing antibacterial agent D was originally small in the content of chlorine dioxide water, and thus the release amount was small. It is considered that the bag-containing antibacterial agents A and B of the examples had a larger surface area than the bag-containing antibacterial agent C and the release amount of the chlorine dioxide aqueous solution was larger than that of the bag-containing antibacterial agent C.

When the bag-containing antibacterial agent was touched from the outside with the hands, the bag-containing antibacterial agents C and D were not much different from the initial contents, but the bag-containing antibacterial agent A had a considerably small content. By confirming that the content volume has decreased, the amount of residual chlorine dioxide aqueous solution can be confirmed.

The amount of chlorine dioxide released after 4 weeks from the bag-containing antibacterial agents A and B was larger than that from the bag-containing antibacterial agents C and D. The bag-containing antibacterial agents A and B of the present invention, which are made of a particulate water-absorbing resin that absorbs an aqueous chlorine dioxide solution, are more effective than the bag-like antibacterial agents C and D that are absorbed by a gel-like water-absorbing resin or an inorganic material. It can be seen that it has a long-term antibacterial effect.

(Example 5)
In Example 1, a commercially available stabilized chlorine dioxide aqueous solution (60,000 ppm as chlorine dioxide) was replaced with an aqueous solution diluted with purified water (3,000 ppm as chlorine dioxide) to obtain commercially available stabilized chlorine dioxide (60,000 ppm). Was diluted with purified water (5,000 ppm as chlorine dioxide) to replace the non-woven fabric (Basis weight 50 g/m ² ) in Example 3 with a semi-permeable membrane film 40 μm and a PET non-woven fabric laminated with a ventilation membrane (air 100 cc A bag-containing antibacterial agent E was prepared in the same manner as in Example 1 and Example 3, except that it took 4500 to 7000 seconds to pass through. The bag-containing antibacterial agent E was removed from the seal and left on the wall, and the weight of the bag-containing antibacterial agent after 1 to 4 weeks was measured to confirm how much chlorine dioxide was volatilized with water. The results are shown in Table 2.

If a microporous plastic film (semi-permeable film) is used for the bag containing the antibacterial agent to reduce air permeability and slow the volatilization rate of water, the release rate of chlorine dioxide will be uniformized and released for a long time. The result is that

The present invention can be embodied in various other forms without departing from the spirit or the main characteristics thereof. Therefore, the above-described embodiments are merely examples in all respects, and the scope of the present invention is shown in the claims and not limited to the text of the specification. Furthermore, all modifications and changes belonging to the scope of claims are within the scope of the present invention.

1 bag of antibacterial agent (b)
2 bags (1)
3 Discharge hole 4 Seal 5 Bag body (2)
6 Antibacterial agent (a)
7 Sheet type antibacterial agent (d)
8 Semi-permeable film 9 Heat seal part 10 Double-sided adhesive tape 11 Sheet-shaped antibacterial agent 12 Release paper 13 Sheet-type antibacterial agent (e)
14 impermeable material

Claims (6)

An antibacterial agent comprising chlorine-dioxide-containing or water-absorbing water-absorbent resin particles, which releases chlorine dioxide and water,
The average particle diameter of the particles of the water absorbent resin before absorbing water containing chlorine dioxide or generated is 30 to 850 μm,
Ri average particle diameter 0.1~3mm der particles of water-absorbing resin has absorbed containing or generating water the chlorine dioxide,
An antibacterial agent in which the ratio of the water-absorbent resin before absorbing the water containing or generating chlorine dioxide and the water containing or generating chlorine dioxide is 1:3 to 1:10 in weight ratio,
An antibacterial agent in a bag, which is enclosed in a bag body (1) made of an impermeable material provided with a release hole for releasing chlorine dioxide and water into the atmosphere . An antibacterial agent which is composed of particles of a water-absorbent resin containing chlorine dioxide or which has generated water and which releases chlorine dioxide and water,
The average particle diameter of the particles of the water absorbent resin before absorbing water containing chlorine dioxide or generated is 30 to 850 μm,
The water-absorbent resin particles containing the chlorine dioxide or absorbing the generated water have an average particle diameter of 0.1 to 3 mm,
The ratio of the water absorbent resin before absorbing the water containing or generating chlorine dioxide and the water containing or generating chlorine dioxide is 1:3 to 1:10 by weight.
An antibacterial agent in which the particle surfaces of particles of the water absorbent resin before absorbing water containing or generating chlorine dioxide are treated with hydrophobic fine particles,
An antibacterial agent in a bag, which is enclosed in a bag body (1) made of an impermeable material provided with a release hole for releasing chlorine dioxide and water into the atmosphere . An antibacterial agent which is composed of particles of a water-absorbent resin containing chlorine dioxide or which has generated water and which releases chlorine dioxide and water,
The average particle diameter of the particles of the water absorbent resin before absorbing water containing chlorine dioxide or generated is 30 to 850 μm,
The water-absorbent resin particles containing the chlorine dioxide or absorbing the generated water have an average particle diameter of 0.1 to 3 mm,
An antibacterial agent in which the ratio of the water-absorbent resin before absorbing the water containing or generating chlorine dioxide and the water containing or generating chlorine dioxide is 1:3 to 1:10 in weight ratio,
After being housed in a bag body (2) having fine pores having a diameter smaller than the particle diameter of the water-absorbent resin containing the chlorine dioxide or absorbing the generated water, chlorine dioxide and water are put into the atmosphere. An antibacterial agent in a bag, which is contained in a bag body (1) made of an impermeable material provided with a release hole for release . An antibacterial agent which is composed of particles of a water-absorbent resin containing chlorine dioxide or which has generated water and which releases chlorine dioxide and water,
The average particle diameter of the particles of the water absorbent resin before absorbing water containing chlorine dioxide or generated is 30 to 850 μm,
The water-absorbent resin particles containing the chlorine dioxide or absorbing the generated water have an average particle diameter of 0.1 to 3 mm,
The ratio of the water absorbent resin before absorbing the water containing or generating chlorine dioxide and the water containing or generating chlorine dioxide is 1:3 to 1:10 by weight.
An antibacterial agent in which the particle surfaces of particles of the water absorbent resin before absorbing water containing or generating chlorine dioxide are treated with hydrophobic fine particles,
After being housed in a bag body (2) having fine pores having a diameter smaller than the particle diameter of the water-absorbent resin containing the chlorine dioxide or absorbing the generated water, chlorine dioxide and water are put into the atmosphere. An antibacterial agent in a bag, which is contained in a bag body (1) made of an impermeable material provided with a release hole for release . The bag-like antibacterial agent according to any one of claims 1 to 4, wherein the release hole of the bag body (1) is covered with a peelable seal. The bag-containing antibacterial agent according to any one of claims 1 to 5 , further comprising cobalt chloride.

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