JP4390181B2 - Negative ion generator - Google Patents

Description

  The present invention relates to a negative ion generator that efficiently generates negative ions, which are attracting attention to have a positive effect on the body, and a filter using the negative ion generator.

  In recent years, negative ions have attracted attention because they give a refreshing feeling to the body and also have a positive effect on the living body by activating physiological functions. It is known that many negative ions are generated in the natural world such as forests and waterfalls. It is also known that inhaling air containing a large amount of negative ions gives a human body a static action and can enjoy effects such as analgesia, pleasant sleep, antitussive, antiperspirant and fatigue prevention. Recently, paying attention to the physiological action of such negative ions, various methods for supplying negative ions to the living space, for example, air conditioners and air purifiers having a function of generating negative ions have been proposed. .

  Conventionally, as a method of artificially generating negative ions, those using the Leonard effect due to water splitting in the air seen around the waterfall, those using discharge by applying a high voltage between the electrodes, Examples thereof include a method using ionizing action by ionizing radiation such as α rays and γ rays emitted from natural radioactive rare element minerals that generate ion pairs and radicals.

In particular, the method utilizing the ionizing action of α-rays emitted from natural radioactive rare element minerals is applied by fixing fine powder of natural radioactive rare element minerals on a resin sheet or fiber surface together with a binder (for example, patent documents). 1), and can be used by filling the fiber (see, for example, Patent Document 2), so that it can be processed into various shapes such as a film shape, a mesh shape, and a filter shape, and at a lower cost. Can be applied in various fields. Recently, in consideration of safety, natural radioactive rare element minerals and fine particles having spontaneous polarization are mixed to provide a material that is excellent in safety and efficiently emits negative ions (see, for example, Patent Document 3). And materials filled with fibers (for example, see Patent Document 4) and fixed to the fiber surface with a binder (for example, see Patent Document 5) have also been proposed.
JP-A-11-200242 Japanese Patent Laid-Open No. 3-185109 Japanese Patent Laid-Open No. 2001-19420 JP 2001-20177 A JP 2001-17277 A

  However, the following problem exists in the method for generating negative ions. That is, the method using the Leonard effect has a problem that requires water, and the method using discharge has a problem that ozone, which is a carcinogenic substance, is generated along with generation of positive ions.

  In addition, natural radioactive rare element minerals can be obtained by fixing fine particles of natural radioactive rare element minerals on the fiber surface with a binder resin made of fiber or polymer material obtained by filling resin. Since the surface of the filled fiber or the binder resin made of a polymer material is easily charged by friction or the like, the generated negative ions are often adsorbed on the charged resin surface and are not substantially generated.

  In particular, when natural radioactive rare element minerals are used, the generation of negative ions is caused by the ionizing action of a small amount of α-rays emitted from the minerals. Then, it is important to fix the mineral fine particles to the outermost surface of the substrate.

  However, there has been proposed a method for fixing the mineral fine particles to the substrate surface, and as an alternative, a method of filling the mineral fine particles in a binder and fixing the mineral fine particles to the substrate surface (so-called adhesion method) has been proposed. However, with this method, the negative ion generation efficiency is low, and furthermore, depending on the type of binder resin and the type of base resin, the adhesion of the binder resin is hindered, or the texture of the base material is impaired. was there.

  Also, among various conventional products that generate negative ions, products manufactured using fine particles of natural radioactive rare element minerals are manufactured by the bonding method using the binder resin described above or the method of kneading into the resin. It has become. However, the conventional technique of fixing with a binder has a problem in that the fine particles of the mineral are easily peeled off because the binding force of the fine particles is not sufficiently strong, resulting in a product with poor durability in this respect. On the other hand, the conventional technique in which particles are kneaded and fixed in a resin has problems such as an inferior negative ion generation effect and a decrease in the mechanical strength of the resin.

  As a result of intensive research, the present inventors have made fine particles that generate negative ions by using a chemical bond of a silane compound so as not to impair the texture of the base material (that is, in the form of a thin film). It has been found that it is possible to bond firmly in an intermittent form (that is, in an island form), thereby obtaining the knowledge that the above-mentioned problems can be solved, and a negative ion generator having a novel configuration and Created a filter.

  An object of the present invention is to provide a negative ion generator excellent in durability in which fine particles that generate negative ions are firmly bonded to the surfaces of various substrates, and a filter using the negative ion generator. .

  Another object of the present invention is to provide a negative ion generator having an excellent antistatic effect on the surface and a filter using this negative ion generator.

  Furthermore, the object of the present invention is to impair the texture of these base materials by strongly bonding fine particles that generate negative ions in the form of islands or thin films to the surface of the base material composed of fibers, films, cloths, and the like. It is another object of the present invention to provide a negative ion generator that efficiently generates a very small amount of fine particles and a filter using the negative ion generator.

  The first configuration of the negative ion generator according to the present invention is characterized in that fine particles of a material that generates negative ions are bonded to the base by chemical bonding of the silane compound to the base surface.

Here, the material that generates negative ions is not particularly limited as long as it is a material in which generation of negative ions is recognized, but preferably, the fine particles of the material that generates negative ions are natural radioactive rare element minerals, spontaneous polarization. At least one or more materials selected from the materials having ferroelectricity and ferroelectrics can be selected . Further, the material of the substrate is not particularly limited as long as it can be chemically bonded by the silane compound, and preferably, at least the surface is made of a resin. The form (shape, size, etc.) of the substrate is not particularly limited, and various forms can be adopted depending on the purpose of use.

  The second configuration of the negative ion generator according to the present invention is characterized in that, in the first configuration, the chemical bond is graft polymerization.

  Furthermore, a third configuration of the negative ion generator according to the present invention is characterized in that, in the second configuration, the graft polymerization is radiation graft polymerization.

  The present invention also provides a filter comprising any one of these negative ion generators.

  According to the first configuration of the present invention, fine particles that generate negative ions are firmly bonded to the surface of the substrate by chemical bonding via the silane compound. For this reason, the microparticles | fine-particles with respect to a base | substrate hold | maintain sufficient durability.

  Therefore, according to the first configuration, it is possible to provide a negative ion generator excellent in durability in which fine particles that generate negative ions are firmly bonded to the surfaces of various base materials. In addition, according to the first configuration, it is possible to provide a negative ion generator that can be efficiently generated with a very small amount of fine particles without impairing the texture of a base material made of fiber, film, cloth or the like.

  In addition, according to the first configuration, the surface of the substrate is in a state in which fine particles that generate negative ions are firmly bonded by chemical bonding via a silane compound, and the surface has an excellent antistatic effect. In addition, it is possible to efficiently generate negative ions with a very small amount of fine particles while maintaining the texture of the base material.

  In addition, as the form of the substrate, for example, various forms suitable for the purpose of use such as a film form, a fiber form, a cloth form, a mesh form, and a honeycomb form can be taken. For example, a vacuum cleaner, a fan, an air conditioner, As a filter for various electric products such as air purifiers, ventilation fans, dryers, etc., or for bags, hot carpets, electric blankets, curtains, blinds, wall coverings, vehicle interior materials, carpets, cushions, handkerchiefs, tablecloths, umbrellas , Book covers, shoes, bedding (eg pillows, duvets, sheets, etc.), necklaces, bracelets, rings, brooches, earrings and other decorative accessories, belts, watch bands, clothing, raincoats, hats, glasses, etc. In addition, various kinds of practical accessories, multi-purpose sheets that can be cut, interior materials, insect nets, etc. It is possible to provide a product.

  According to the second configuration of the present invention, since the bond with the substrate is a graft polymerization based on a covalent bond, the fine particles that generate negative ions are firmly fixed to the substrate surface. Occurrence can be maintained.

  According to the third configuration of the present invention, since the graft polymerization uses radiation such as γ-rays, electron beams, and ultraviolet rays, fine particles that are extremely reactive and generate negative ions by graft polymerization in a short time are used. Since it can be fixed to the surface and does not require complicated processing, it is excellent in productivity, and a negative ion generator can be supplied at low cost.

  Further, in the filter made of the negative ion generator of the present invention, the generated negative ions can be diffused in the room or the like by passing the gas through the filter.

  The present invention is described in further detail below.

The material for generating negative ions used in the present invention is not particularly limited as long as it is a material in which the generation of negative ions is recognized. Specific materials that can efficiently generate negative ions include davitite, senurite, blannelite, nymphite, lincaurite, carnotite, tchaumite, metachamunite, francesvilleite, tall stone, and coffin. Natural radioactive rare element minerals containing trace amounts of radioactive rare elements such as stones, Samarsky stones, thorium stones, tro rubber stones, samarsky stones, thorium stones, tro rubber stones, monazite, tantalum stones, bedelite, ilmenite, and one of these minerals Examples thereof include electrofused zirconia obtained by refining the part. Furthermore, in order to reduce the usage of natural radioactive rare element minerals in consideration of safety, materials with spontaneous polarization such as tourmaline, BaTiO ₃ , PbZrO ₃ , Pb (Zr, Ti) O ₃ , KnbO ₃ , One or more ferroelectric materials such as KtaO ₃ , K (Ta, Nb) O ₃ , and LiNbO ₃ are mixed and used. These materials are used as fine particles, and their particle diameters may be between 0.001 μm and 5.0 μm. When the particle diameter is larger than 5.0 μm, the fixing ability of these fine particles is lowered and it is easy to be detached from the surface of the base resin, and when the substrate is a fiber or cloth, the amount of silane compound required for fixing is large. Therefore, the texture of the fiber or cloth is impaired, which is not preferable. On the other hand, it is technically difficult to make the particle diameter smaller than 0.001 μm, and it is not preferable from the viewpoint of manufacturing cost.

  In the present invention, fine particles of metal oxides such as alumina, silica, titanium oxide, magnesium oxide, and zinc oxide, colloids thereof, aluminum hydroxide, hydroxide are used in order to further enhance the effect of suppressing frictional charging on the surface of the fiber or film. Fine particles such as metal hydroxides such as magnesium and zinc hydroxide, natural materials such as diatomaceous earth and mica may be used. The particle diameter may be between 0.001 μm and 5.0 μm.

  In addition to fine particles of a material that generates negative ions, fine particles of a material having a photocatalytic function, fine particles of a material having antibacterial properties, fine particles of a material that emits far infrared rays, and the like may be mixed.

  Here, examples of the fine particles exhibiting a photocatalytic function include known metal compound semiconductors such as titanium oxide, zinc oxide, tungsten oxide, iron oxide, strontium titanate, cadmium sulfide, and cadmium selenide, and these materials. Can be used singly or in combination of two or more.

  In addition, as the fine particles of the antibacterial material, for example, “Apatizer A” manufactured by Sangi Co., Ltd., “Dai Killer” manufactured by Dainichi Seika Kogyo Co., Ltd., Matsushita Electric Industrial Co., Ltd. “Ameni Top”, “Atomy Ball” manufactured by Catalyst Kasei Kogyo Co., Ltd., “Bacter Killer” manufactured by Kanebo Kasei Co., Ltd. and the like can be used, and these can be used singly or in combination of two or more.

Furthermore, as a material that emits far infrared rays, metal oxides such as Al ₂ O ₃ , TiO ₂ , ZrO ₂ , SiO ₂ , Fe ₂ O ₃ , CoO, CuO, MgO, and mixtures thereof, for example, cordierite, β-spodumene, ceramics such as aluminum titanate, and commercially available far-infrared ceramics, for example, OKTRADING SERAJIT, Mizusawa Chemical Industry Co., Ltd. Shiruton FI-85, and these are single or a combination of two or more Can be used.

  In the present invention, fine particles of a material that generates negative ions are fixed on a resin substrate by a silane compound by crosslinking simultaneously with chemical bonding. Specific examples of the silane compound include a silane coupling agent represented by a general formula of X-Si (OR) 3. X is a functional group that reacts with organic matter, such as vinyl group, epoxy group, styryl group, methacrylo group, acryloxy group, isocyanate group, polysulfide group, amino group, mercapto group, chloro group, and R is hydrolyzable. A methoxy group, an ethoxy group, and the like. These alkoxy groups composed of methoxy groups and ethoxy groups are hydrolyzed to form silanol groups. It is known that functional groups having an unsaturated bond such as silanol group, vinyl group, epoxy group, styryl group, methacrylo group, acryloxy group and isocyanate group have high reactivity. In the present invention, by using a silane coupling agent having excellent reactivity, fine particles of a material that generates negative ions are bonded to the surface of a substrate by chemical bonding and crosslinking of a silane compound.

  Examples of silane coupling agents used in the present invention include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl. Trimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacrylo Cypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3- Aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-merca Examples thereof include puttopropyltrimethoxysilane.

  These silane coupling agents are used singly or in combination. As a form of use, a necessary amount of a silane coupling agent is dissolved in a solvent such as methanol or ethanol, and water necessary for hydrolysis is added and used. Solvents used include ethanol, methanol, lower alcohols such as propanol and butanol, lower alkyl carboxylic acids such as formic acid and propionic acid, aromatic compounds such as toluene and xylene, esters such as ethyl acetate and butyl acetate, methyl Cellosolves such as cellosolve and ethylcellosolve may be used alone or in combination. Furthermore, the silane coupling agent may be used in the form of an aqueous solution. If the solubility in water is poor, acetic acid is added to adjust the pH to a weak acidity and promote the hydrolyzability of alkoxysilane. Used with increased water solubility.

In the present invention, an alkoxysilane compound represented by Si (OR1) ₄ (wherein R1 represents an alkyl group having 1 to 4 carbon atoms), as an example, is added to the above-described solution of the silane coupling agent as necessary. , Tetramethoxysilane, tetraethoxysilane, and the like, R2 _n Si (OR3) _4-n (wherein R2 is a hydrocarbon group having 1 to 6 carbon atoms, R3 is an alkyl group having 1 to 4 carbon atoms, and n is 1) As an example, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, hexyltrimethoxysilane and the like are added. Used.

  The negative ion generator in the present invention is produced using a solution in which fine particles of a material that generates negative ions are dispersed in the above-described solution of the silane coupling agent. Dispersion of fine particles of materials that generate negative ions is performed by stirring and dispersing using a homomixer or a magnetic stirrer, dispersing using a ball mill, sand mill, high-speed rotating mill, jet mill, etc., or using ultrasonic waves. Is called.

  The material constituting the substrate used in the negative ion generator of the present invention may be any material that can be chemically bonded with a silane compound. Examples of such a material include various resins and natural fibers. Of these, resins are particularly suitable.

  In this respect, preferred examples of the substrate used in the negative ion generator of the present invention include those having at least the substrate surface made of a resin.

  Here, a synthetic resin or a natural resin is used as the resin constituting the substrate. Examples of the resin include a polyethylene resin, a polypropylene resin, a polystyrene resin, an ABS resin, an AS resin, an EVA resin, a polymethylpentene resin, and a polychlorinated resin. Vinyl resin, polyvinylidene chloride resin, polymethyl acrylate resin, polyvinyl acetate resin, polyamide resin, polyimide resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacetal resin, polyarylate resin, polysulfone resin, polyvinylidene fluoride Resin, PTFE and other thermoplastic resins, polylactic acid resin, polyhydroxybutyrate resin, modified starch resin, polycaprolacto resin, polybutylene succinate resin, polybutylene adipate terephthalate Resins, polybutylene succinate terephthalate resin, polyethylene succinate resin and other biodegradable resins, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin, silicon resin, acrylic resin Thermosetting resins such as urethane resins and urethane resins, elastomers such as silicone resins, polystyrene elastomers, polyethylene elastomers, polypropylene elastomers and polyurethane elastomers, natural resins such as lacquer, and the like can be mentioned.

  The form of these resins is not particularly limited in the present invention as long as it has a shape and size suitable for the purpose of use, such as plate, film, fiber, cloth, mesh, and honeycomb. In addition, it is laminated in the form of a film on the surface of metal materials such as aluminum, magnesium, and iron, and the surface of inorganic materials such as glass and ceramics, and coating methods such as spray painting, immersion painting, electrostatic painting, and screen printing. Alternatively, it may be formed as a thin film by a printing method such as offset printing. Furthermore, these resins may be colored with pigments, dyes, or the like, or may be filled with inorganic materials such as silica, alumina, diatomaceous earth, and mica.

  On the other hand, examples of natural fibers constituting the substrate include cotton, hemp, silk, and the like.

  Examples of the radiation used in the graft polymerization according to the present invention include α rays, β rays, γ rays, electron beams, ultraviolet rays, etc., but for use in the present invention, γ rays, electron beams, ultraviolet rays are used. Is suitable.

  The negative ion generator using the graft polymerization according to the present invention applies a silane coupling agent solution in which fine particles of the material generating negative ions described above are dispersed to the surface of the substrate to be bonded, and if necessary, a solvent Is removed by a method such as heat drying, and then irradiated with radiation such as γ rays, electron beams, and ultraviolet rays onto the surface of the substrate coated with a mixture of fine particles of a material that generates negative ions and a silane coupling agent, Graft polymerization of the silane coupling agent on the surface of the substrate, and at the same time, so-called simultaneous irradiation graft polymerization performed by bonding fine particles of a material that generates negative ions, and a substrate to bond the fine particles of materials that generate negative ions Negative ions are generated after irradiating the surface with radiation such as γ rays, electron beams, and ultraviolet rays. Two methods of so-called pre-irradiation graft polymerization in which a silane coupling agent solution is dispersed by applying a silane coupling agent solution in which fine particles of the material to be dispersed are reacted, and at the same time, the fine particles of the material that generates negative ions are fixed. More manufactured.

  In addition, in order to carry out graft polymerization of the silane coupling agent efficiently and uniformly, the surface of the resin substrate is previously subjected to corona discharge treatment, plasma discharge treatment, flame treatment, oxidizing properties such as chromic acid and perchloric acid. It is particularly preferable if the surface is hydrophilized by chemical treatment with an acid aqueous solution.

  Thus, the negative ion generator of the present embodiment chemically binds the fine particles of the material that generates negative ions to the surface of the resin substrate by radiation graft polymerization of the silane compound. Silanol groups generated by hydrolysis are strongly chemically bonded to the surface of fine particles of materials that generate negative ions by a dehydration condensation reaction. In addition, vinyl groups, epoxy groups, styryl groups, methacrylo groups, acryloxy groups of silane compounds A group, an isocyanate group, a polysulfide group, and the like are chemically bonded to the surface of a resin substrate by graft polymerization using radicals generated by irradiation with radiation.

  Therefore, the negative ion generator of the present embodiment has various kinds of fine particles of the material that generates negative ions, because the fine particles of the material that generate negative ions are in a strong bonding state based on chemical bonding by the silane compound to the resin substrate surface. Even when used in a rough environment, desorption of fine particles of a material that generates negative ions hardly occurs, and the durability is excellent.

  In addition, the silanol group formed by hydrolysis of the alkoxy group is condensed to form a dense silicon oxide thin film, and this dense silicon oxide thin film has a function of preventing charging of the resin surface. The surface is not charged by friction. Therefore, the negative ion generator of the present embodiment does not adsorb the generated negative ions and can efficiently generate negative ions.

  Furthermore, since the negative ion generator of this embodiment can be in various forms (shape, size, etc.) suitable for the purpose of use, such as film, fiber, cloth, mesh, and honeycomb, For example, as a filter for various electrical products such as electric vacuum cleaners, electric fans, air conditioners, air purifiers, ventilation fans, dryers, etc., or firewood, hot carpets, electric blankets, curtains, blinds, wall coverings, vehicle interior materials, Carpets, cushions, handkerchiefs, tablecloths, umbrellas, book covers, shoe covers, bedding (eg pillows, duvets, sheets, etc.), necklaces and bracelets, rings, brooches, earrings and other decorative accessories, belts and watch bands, Various practical accessories such as clothing, raincoats, hats, glasses, etc., multi-purpose sheets that can be cut, interior materials, insect nets, Etc., it is possible to provide the material products and application products in various fields.

  In particular, when the negative ion generator of the present invention is applied to the above-described filter, it is possible to diffuse the generated negative ions into the room by passing a gas through the filter. It becomes possible to provide products with extremely high practical value.

  Further, if the negative ion generator of the present invention is arranged at a location where gas passes, it becomes possible to move or diffuse negative ions to various locations, so that, for example, gas passes through the negative ion generator of the present invention. It is possible to increase the added value and practical value of these products by applying to various types of pipes and tubes, or the part of the spray outlet of a spray can (or sprayer), as well as a screen door. Furthermore, by applying the negative ion generator of the present invention to a part or product that is a source of gas, such as a fan blade member or a fan, for example, an added value of these parts or products. In addition, the practical value can be increased.

  As described above, the present invention can be provided as material products and applied products in various fields, and is extremely useful with excellent practicality.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

<Preparation of negative ion generator>
The production of the negative ion generator in the present invention was carried out using an electro curtain type, CB250 / 15 / 180L manufactured by Iwasaki Electric Co., Ltd. as an electron beam irradiation apparatus.
Example 1:
After 15 g of γ-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) is dissolved in 950 g of methanol, 4 g of water (3 mol equivalent or more of water relative to the silane compound) is added. A part of the silane coupling agent was hydrolyzed. 35 g of a mixture of fine particles of tourmaline and fine particles of ilmenite which is a natural radioactive rare element mineral (manufactured by Nakazatoya Co., Ltd.) is added to the silane coupling agent solution as fine particles of a material that generates negative ions. The fine particles of the material that generates negative ions were pulverized and dispersed using a machine (Dynomill, manufactured by Willy et Bacofen), and the silane coupling agent was adsorbed on the surface of the pulverized fine particles.

  Further, a silane coupling agent solution in which fine particles of a material generating negative ions are dispersed after corona discharge treatment in the air on the surface of a 125 μm polyester film (Lumirror, manufactured by Panac Co., Ltd.) as a substrate (substrate). Was applied by spraying and dried at 110 ° C. for 3 minutes. Next, a polyester film coated with a silane coupling agent solution is irradiated with an electron beam at an acceleration voltage of 200 kV for 5 Mrad, so that a mixture of tourmaline fine particles and natural radioactive rare element mineral ilmenite fine particles is a silane coupling agent. A negative ion generator bonded on a polypropylene film was obtained.

Example 2:
In addition to the silane coupling agent used in Example 1, 20 g of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903) was added, and negative ions were generated under the same conditions as in Example 1. Got the body.

Example 3:
A negative ion generator was obtained under the same conditions as in Example 2, except that a 200-mesh mesh cloth made of 55 μm polyester filament was used instead of the polyester film used in the substrate in Example 2.

Example 4:
Instead of the polyester film used for the substrate in Example 2, a negative ion generator was obtained under the same conditions as in Example 2 except that a 50 μm polypropylene film (Torphan NO manufactured by Toray Synthetic Film Co., Ltd.) was used. .

Example 5:
After dissolving 50 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) in 900 g of methanol, 12 g of water (3 mol equivalent or more of water relative to the silane compound) was added. A part of the silane coupling agent was hydrolyzed. After adding 50 g of fused zirconia (FZR- # 325 manufactured by JFE Materials Co., Ltd.) containing a trace amount of radioactive rare elements as fine particles of a material that generates negative ions to this silane coupling agent solution, a circulating wet pulverizer (Willy) -The fine particles of the material that generates negative ions were pulverized and dispersed using an e-Baccofen Co., Ltd. dyno mill), and the silane coupling agent was adsorbed on the surface of the pulverized fine particles.

  Further, after the corona discharge treatment was performed on the surface of the polyester nonwoven fabric (manufactured by Asahi Kasei Co., Ltd., Ertas E01040) as the substrate in the air, the silane coupling agent solution in which the fused zirconia was dispersed was applied by a spray, Dry for 3 minutes. Next, a negative ion generator formed by irradiating a polyester nonwoven fabric coated with a silane coupling agent solution with an electron beam at 10 krad at an acceleration voltage of 200 kV to bond fused zirconia fine particles onto the polyester nonwoven fabric with a silane coupling agent. Got.

Example 6:
Add 800 g of methanol and 6 g of water to 100 g of a 40 wt% methanol solution of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (KBM-575, manufactured by Shin-Etsu Chemical Co., Ltd.) A part of the silane coupling agent was hydrolyzed. After adding 100 g of vaterite fine particles (ZB480 manufactured by Mino Pigment Chemical Co., Ltd.), a natural radioactive rare element mineral, as a fine particle of a material that generates negative ions in this silane coupling agent solution, a circulation type wet pulverizer (Willy ・The fine particles of the material that generates negative ions were pulverized and dispersed using a dyno mill manufactured by D. Baccofen, and the silane coupling agent was adsorbed on the surface of the pulverized fine particles.

  Further, after the surface of a 100 μm-thick polyethylene film (manufactured by Lintec Corporation) as a substrate was subjected to corona discharge treatment in the air, the silane coupling agent solution in which the vaterite fine particles were dispersed was applied by spraying, Dry for 5 minutes. Next, by irradiating the polyethylene film coated with the silane coupling agent solution with an electron beam at 10 Mrad at an acceleration voltage of 200 kV, a negative ion generator in which the fine particles of the vaterite are bonded on the polyethylene film with the silane coupling agent. Obtained.

Example 7:
50 g of 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-9007) is dissolved in 850 g of isopropyl alcohol, and 11 g of water (3 mol equivalent water or more with respect to the silane compound) is added to the silane cup. A part of the ring agent was hydrolyzed. To this silane coupling agent solution, 100 g of a mixture of diatomite fine particles and ilmenite fine particles (Nakazaya Co., Ltd.), a natural radioactive rare element mineral, was added, and then a circulation type wet pulverizer (manufactured by Willy et Bacofen) The fine particles of the material that generates negative ions were pulverized and dispersed using a dyno mill, and the silane coupling agent was adsorbed on the surface of the pulverized fine particles.

  In addition, as a base made of resin, a thermosetting acrylic paint (MG1000, manufactured by Kansai Paint Co., Ltd.) is applied on an aluminum plate having a thickness of 1.0 mm by spraying, and then dried at 180 ° C. for 30 minutes. Thus, a coating-coated aluminum plate on which a coating film having a thickness of 30 μm was formed was obtained. Next, a silane coupling agent solution in which fine particles of the material that generates the negative ions are dispersed is applied by spraying, dried at 130 ° C. for 3 minutes, and then applied to the coated aluminum plate coated with the silane coupling agent solution. A negative ion formed by irradiating an electron beam with an acceleration voltage of 240 kV at 10 Mrad to couple a mixture of diatomaceous earth fine particles and ilmenite fine particles, a natural radioactive rare element mineral, onto a coated aluminum plate with a silane coupling agent. A generator was obtained.

Comparative Example 1:
A polyester resin (manufactured by Nippon Unipet Co., Ltd.) was filled with 5.0% by weight of fine particles of the material that generates negative ions used in Example 1 by a biaxial kneader to produce pellets. Next, a negative ion generator composed of a film having a thickness of 100 μm filled with fine particles of a material that generates negative ions was obtained by a stretched film forming apparatus using the obtained pellets.

Comparative Example 2:
Filled with fine particles of a material that generates negative ions under the same conditions as in Comparative Example 1, except that the amount of fine particles of the material that generates negative ions into the polyester resin in Comparative Example 1 is changed to 10.0% by weight. Thus, a negative ion generator made of a 100 μm thick film was obtained.

Comparative Example 3:
By using pellets filled with 5.0% by weight of fine particles of a material that generates negative ions produced in Comparative Example 1, a polyester filament is spun by a melt spinning apparatus, and further drawn, so that the negative ions have a diameter of 60 μm. Polyester filaments filled with fine particles of a material that generates water were obtained. Next, using the obtained polyester filament, a negative ion generator composed of mesh cloth filled with fine particles of a material that generates 200 mesh negative ions was obtained.

Comparative Example 4:
An acrylic one-component paint having a solvent composition of 15.0% by weight of toluene, 15.0% by weight of butanol, 7.0% by weight of isopropyl alcohol, 8.0% by weight of butyl acetate, and 15.0% by weight of ethyl acetate Spray coating of 5.0% by weight of fused zirconia fine particles containing a trace amount of radioactive rare element used in No. 5 on the surface of a polyester nonwoven fabric (Arutas E01040, manufactured by Asahi Kasei Co., Ltd.). After that, by drying at 80 ° C. for 30 minutes, a negative ion generator made of a polyester nonwoven fabric coated with a 15.0 μm thick coating film containing fine particles of a material that generates negative ions was obtained.

Comparative Example 5:
A mixture of the diatomaceous earth fine particles used in Example 7 and the fine particles of ilmenite, a natural radioactive rare element mineral (manufactured by Nakazatoya Co., Ltd.), the solid content of a thermosetting acrylic paint (manufactured by Kansai Paint Co., Ltd., MG1000). 40.0% by weight was dispersed. Next, after spray-coating the paint on an aluminum plate having a thickness of 1.0 mm, the coating film having a thickness of 30 μm containing fine particles of a material that generates negative ions is dried at 180 ° C. for 30 minutes. A negative ion generator composed of a coated aluminum plate was obtained.

<Evaluation of negative ion generator>
As a characteristic of the obtained negative ion generator, the amount of negative ions generated was measured using an ion counter SC-50 manufactured by Sigma Tech Co., Ltd., using a sample having a size of 20 cm × 20 cm. As for the antistatic effect, the surface sheet resistance value was measured as a substitute characteristic value by using a resistance measuring instrument manufactured by Yokogawa-Hewlett-Packard Co., Ltd., High Resistance Meter 4329A. These measurement results are shown in Table 1.

  As shown in the results of Table 1, the surface of the negative ion generator obtained by the radiation graft polymerization of the present invention is shown to be a surface having an excellent antistatic effect, and the negative ions are stable and It was confirmed that it was generated efficiently. In contrast to these results, in the negative ion generator obtained in the comparative example, generation of negative ions was observed when the resin or coating film was filled with fine particles of a material that generates negative ions at a high concentration (comparison). Example 2) However, as shown in Table 1, the generation amount was extremely low as compared with the Example. The sheet resistance value was relatively low only in the case of Comparative Example 2 in which fine particles of a material that generates negative ions were filled at a high concentration, whereas the sheet resistance value was high at low concentration filling, It was confirmed that there was no prevention effect.

  As described above, according to the present invention, negative ions, which are attracting attention to have a positive effect on the body, can be easily, safely and efficiently without damaging the texture of the substrate made of fiber, film, cloth or the like. A negative ion generator that generates well and a filter using the negative ion generator can be provided, which is extremely useful in industry.

Claims (5)

  A negative ion generator in which fine particles of a material that generates negative ions are bonded to a substrate by chemical bonding of a silane compound to the substrate surface.   The negative ion generator according to claim 1, wherein the chemical bond is graft polymerization.   The negative ion generator according to claim 2, wherein the graft polymerization is radiation graft polymerization. The fine particles of the material that generates negative ions are selected from at least one kind selected from natural radioactive rare element minerals, materials having spontaneous polarization, and ferroelectrics. The negative ion generator according to any one of the above. A filter comprising the negative ion generator according to any one of claims 1 to 4 .