JP2008002007A - Nanoparticle support material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic material and its fiber assembly supporting nanoparticles having oxidation activities without light and exhibiting effects for inhibiting proliferation of bacteria or the like, and invalidation effects for carrying out deodorization and safening of a harmful gas or fine droplets, without using a binder. <P>SOLUTION: The organic material and the fiber assembly exposing the nanoparticles having the excellent functions on the surfaces are obtained by applying a suspension including functional nanoparticles which have an average primary particle diameter of >1 and <100 nm, of which the surfaces are covered with a hydrophilic inorganic compound, and in which at least 30 mass% of the functional nanoparticles is titanium oxide-based nanoparticles covered with the hydrophilic inorganic compound, to at least a part of the surface of an organic material so that the functional nanoparticles may be adsorbed, fixed and supported, and applying a peroxide to the titanium oxide-based nanoparticles. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention exhibits the effect of inhibiting the growth of microbes such as bacteria, sputum and viruses, the effect of suppressing the growth such as sterilization and sterilization, and the deodorizing and detoxifying effects of malodorous or harmful gases and fine droplets. The present invention relates to an organic material supporting a nanoparticle having a function and a fiber assembly.

  Conventionally, as a photocatalyst-supporting fiber product that requires light irradiation, for example, JP-A-9-78454 (Patent Document 1) discloses an outdoor sheet in which a photocatalyst is mixed with a resin that forms a surface film. . Japanese Patent No. 2939524 (Patent Document 2) discloses one in which photocatalyst particles are supported on a surface coating by thermocompression bonding. In particular, Patent Document 2 is presumed to assume a case where the photocatalyst particles are large. In recent years, many studies have been made to make photocatalyst particles fine, and fine photocatalysts have come to the market.

  The photocatalyst has a function to oxidize organic substances on the surface of the photocatalyst, and not only oxidative decomposition of organic dirt but also oxidative degradation of the resin holding or supporting the photocatalyst. Many photocatalyst processed products that cover the photocatalyst with difficult apatite or the like and protect the resin by avoiding direct contact with the resin that holds or carries the photocatalyst directly have been proposed.

  On the other hand, as a technique for supporting functional particles on a resin, fiber, or fiber product, for example, in Japanese Patent No. 2565371 (Patent Document 3), the film surface is roughened by a sputter etching process performed under a reduced pressure of 1 hPa or less. After performing this, a functional sheet on which functional powder is adsorbed is disclosed. Japanese Patent Application Laid-Open No. 10-61986 (Patent Document 4) discloses an air cleaner using a nonwoven fabric filter coated with an ultraviolet lamp and a photocatalyst. Japanese Patent Application Laid-Open No. 2003-250920 (Patent Document 5) and Japanese Patent Application Laid-Open No. 2003-334262 (Patent Document 6) have a sterilizing and deodorizing effect obtained by impregnating a woven fabric, a nonwoven fabric or the like with a titanium oxide aqueous solution that acts as a photocatalyst. A mask is disclosed.

  In JP 2003-250920 A (Patent Document 7) or JP 2003-334262 A (Patent Document 8), an aqueous solution of titanium oxide such as peroxotitanate anatase sol is attached to a fiber, and its oxidizing power is increased. The mask used is also disclosed.

Japanese Patent Laid-Open No. 9-78454 Japanese Patent No. 2939524 Japanese Patent No. 2565371 Japanese Patent Laid-Open No. 10-61986 JP 2003-250920 A JP 2003-334262 A Japanese Patent No. 2938376 Japanese Patent No. 2875993

  The function of sterilizing microscopic organisms such as bacteria, sputum and viruses, inhibiting growth such as sterilization and sterilization, deodorizing and detoxifying fine odors and harmful gases, and fine droplets is an organic function. In the material, all functions occur on the material surface, and it is most economical to make these functions possible on the material surface. In the current ordinary method, a drug having these functions is kneaded into a resin constituting the material or mixed with an adhesive and adhered to the material. However, in such a method, there are few functional agents exposed on the surface when kneaded into the material, and most of the kneaded functional agents do not contribute to the expression of the function at all, and they are stored deadly, which is uneconomical and problematic. It was. In addition, when mixed with an adhesive, the surface of the functional agent is covered with the adhesive, resulting in a problem that the ability is significantly lowered than the function that can be originally exhibited.

  For example, the non-woven fabric carrying the photocatalyst used in Patent Documents 4 to 6 is obtained by simply mixing the photocatalyst particles, which are functional particles, with an adhesive and simply applying it to the surface of the non-woven fabric. There is a problem that it is necessary to use it, it is not economical, the viscosity of the coating liquid becomes high, and uneven coating tends to occur. Since the method of fixing using the conventional binder is still taken, there existed a problem as mentioned above. Moreover, since photocatalyst particles are used, light irradiation and moisture have been indispensable factors in order to exert an oxidation function.

In addition, titanium peroxide (also known as peroxotitanium) having a chemical composition of Ti ₂ O ₅ (OH) _X proposed in Patent Documents 7 and 8 is stable only in a cationic state under strong acidity, and gradually becomes insoluble in yellow water. Of peroxotitanium hydrate Ti ₂ O ₅ (OH) ₂ . It is amorphous and does not have a photocatalytic function. That is, titanium oxide must be in a crystalline form in order to exert a photocatalytic function. In Patent Documents 7 and 8, this titanium peroxide is used as a precursor of a photocatalyst. However, since the titanium peroxide is unstable and causes hydrate precipitation, Patent Documents 7 and 8 attempt to stabilize the solution. Since this titanium peroxide has a chemical structure of Ti—O—O—Ti and Ti—OH and is non-crystalline, it is known that it has no function as an oxidizing agent, and exhibits antibacterial effects under no light, etc. It was unsuitable for use. This anatase dispersion (also known as peroxo-modified anatase sol) in which the peroxotitanium solution is stabilized is pure crystalline titanium oxide crystallized by a heat treatment exceeding 100 ° C., and has the same photocatalytic function as a conventional titanium oxide photocatalyst. have. However, like the conventional titanium oxide photocatalyst, it is considered that there is no function as an oxidant without light, and the study as an oxidant without light has not been studied at all. Furthermore, titanium oxide fine particles taking a crystal form as a photocatalyst are difficult to stably disperse in water for a long time without precipitation separation. For this reason, the anatase dispersion has been proposed, which means that the hydrophilicity of the titanium oxide fine particles themselves is insufficient, and the dispersion life is extremely short. Aggregation was a manufacturing problem.

  In order to solve the above-described conventional problems, the present invention can fully exhibit its function without burying titanium oxide fine particles in a binder or the like, and has an oxidizing action without light, and thus bacteria, sputum, virus It carries nanoparticles that have the function of inhibiting the growth of microscopic organisms such as sterilization, sterilization, sterilization, malodorous or harmful gas, and deodorizing and detoxifying fine droplets. An object is to provide organic materials and fiber assemblies.

  The present inventors have stated that there is a photocatalyst in which the photocatalyst is coated with an inorganic compound such as apatite in order to prevent the photocatalyst from oxidatively degrading organic matter and the surrounding organic matter is deteriorated. Presence of compound-coated photocatalyst, easy adsorption of inorganic compounds such as apatite, ease of physical adsorption of inorganic compound-coated photocatalyst, and the photocatalyst can be suspended in water and settled over a long period of time It was found that it can be made into an aqueous suspension that does not cause the separation phenomenon.

  Further, in the present invention, in particular, inorganic compounds having a high hydrophilicity such as silica, carbon black, apatite, etc. having gas adsorption ability, or coated particles whose particle surfaces are covered with these, the particle diameter of which is 100 nm. It was found that nano-sized nanoparticles with a size of less than 1 nano-particles adsorb and immobilize on these materials when they are suspended in water and applied to non-water-repellent, in other words, hydrophilic materials. .

  And, when titanium oxide used as a photocatalyst is irradiated with light in the presence of water, the Ti—O bond on the surface of the photocatalyst particle or in the vicinity of the surface changes to a Ti—O—OH bond, and when it comes into contact with the oxide,・ Estimated to generate OH radicals and oxidize, hypothesized, and measured the bactericidal properties of the organic material adsorbed and fixed nanoparticle photocatalyst fine particles and diluted hydrogen peroxide, no light was irradiated In both cases, it was found that the photocatalyst support material irradiated with light exhibits exactly the same bactericidal properties.

  That is, the nanoparticle-carrying material of the present invention is an organic material and a nanoparticle-carrying material comprising functional nanoparticles having an average primary particle diameter of more than 1 nm and less than 100 nm and having a particle surface coated with a hydrophilic inorganic compound. The functional nanoparticles are adsorbed and fixed and supported on at least a part of the surface of the organic material by at least the adsorption ability of the particles themselves, and at least 30% by mass of the functional nanoparticles are hydrophilic. Titanium oxide-based nanoparticles coated with an inorganic compound, characterized in that it includes nanoparticles in which at least a part of the titanium-oxygen bond of titanium oxide is hydroperoxidized having an oxidation function.

  The fiber assembly for a filter of the present invention includes functional nanoparticles in which one surface of the fiber assembly has an average primary particle diameter of more than 1 nm and less than 100 nm, and the particle surface is coated with a hydrophilic inorganic compound, The functional nanoparticles are adsorbed onto the fiber surface by at least the adsorbing ability of the particles themselves, and are surfaces including fibers that are fixed and supported, and at least 50% by mass of the functional nanoparticles are coated with a hydrophilic inorganic compound A titanium oxide-based nanoparticle having a nanoparticle-supporting surface including a hydroperoxide-ized nanoparticle in which at least a part of a titanium-oxygen bond of titanium oxide has an oxidation function. The surface is provided with the electret surface containing the electretized fiber.

  The method for producing a nanoparticle-supporting material according to the present invention includes functional nanoparticles having an average primary particle diameter of more than 1 nm and less than 100 nm, the particle surface being coated with a hydrophilic inorganic compound, and at least 30 functional nanoparticles. Mass% is a suspension containing titanium oxide nanoparticles coated with a hydrophilic inorganic compound applied to at least a part of the surface of the organic material, and the functional nanoparticles are adsorbed, fixed and supported. Thereafter, a peroxide is imparted to the titanium oxide nanoparticles.

  In the nanoparticle carrying material of the present invention, functional nanoparticles having a hydrophilic inorganic compound as the particle surface are adsorbed on the surface of the organic material by the adsorption ability of the particles themselves, and are exposed and fixed and carried on the organic material surface. Therefore, the fixed specific surface area is large, and harmful gases, droplets, bacteria and fungi can be adsorbed and removed. In addition, since the present invention uses titanium oxide nanoparticles coated with a hydrophilic inorganic compound, in addition to the function of adsorption / removal described above, titanium oxide nanoparticles encapsulating these adsorbents as photocatalysts. It can be rendered harmless by its oxidative decomposition ability.

  And, since the nanoparticle-supporting material of the present invention is a hydroperoxide having an oxidizing power, a part of the titanium oxide of the titanium oxide-based nanoparticle, even by the oxidative decomposition ability like the conventional photocatalyst, It can be detoxified. Hydroperoxide consumed using without light can be easily replenished, i.e. activated, for example by intermittent contact with hydrogen peroxide.

  The nanoparticle-supporting material of the present invention can carry nanoparticle support by simple application means such as application of water suspension, printing, etc., and activation treatment with peroxides such as hydrogen peroxide It can be carried out easily by applying a dilute hydrogen peroxide aqueous solution or the like.

  The nanoparticle-carrying material of the present invention is a nanoparticle-carrying material comprising an organic material, a functional nanoparticle having an average primary particle diameter of more than 1 nm and less than 100 nm and having a particle surface coated with a hydrophilic inorganic compound. The functional nanoparticles are adsorbed and fixed and supported on at least a part of the surface of the organic material by at least the adsorption ability of the particles themselves, and at least 30% by mass of the functional nanoparticles are hydrophilic inorganic compounds. The titanium oxide-based nanoparticles are coated with, and are characterized in that at least a part of the titanium-oxygen bond of titanium oxide is hydroperoxide-containing nanoparticles having an oxidation function. The organic material is composed of an organic substance and has, for example, a form such as a resin, a film, or a fiber. The present invention is an organic material in which a component that gets wet with water forms a surface by adsorbing and adhering to and adhering to the organic material with the adsorptive power of hydrophilic inorganic compound particles that are nanoparticles having a size of less than 100 nm. It is a nanoparticle-supporting material that is fixed and integrated without using a binder on its surface portion. Of the functional nanoparticles, titanium oxide nanoparticles also have a photocatalytic function, so they exhibit the effect of inhibiting the growth of microscopic organisms such as bacteria, sputum, and viruses such as bactericidal, antibacterial, and sterilization due to the oxidation effect of the photocatalytic particles. In addition, malodorous or harmful gases and fine droplets are adsorbed by the hydrophilic inorganic compound that coats the photocatalyst particles, and the deodorizing and detoxifying effects are exhibited by the oxidation effect of the contained photocatalyst. It has a function. As long as the light exposure is sufficient, the photocatalyst-supporting material can maintain these effects for at least one day and night, and for about one week depending on conditions.

  However, in order to exert this oxidation effect, there is a serious drawback that requires light and moisture, and there is also a problem that adaptation is limited to a thin planar shape capable of receiving light. Therefore, as a result of diligent investigation, when titanium oxide as photocatalyst particles is brought into contact with a peroxide such as hydrogen peroxide or ozone water to hydroperoxide, the same oxidation effect as that irradiated with light can be exhibited. It was discovered that the present invention was reached.

  First of all, hydrophilic inorganic compounds such as silica of silicic acid, phosphate apatite and charcoal were known to have good gas adsorption by the porous body having a large specific surface area. When these hydrophilic inorganic compounds become infinitely fine and become nanoparticles, when these are applied as a water suspension to a resin that can be wetted with water and dried, the surfaces of these resins are reversed. It was confirmed that it was adsorbed to and adhered and supported so that it could not be removed even by ultrasonic water treatment. With regard to the action of adsorbing, adhering, and supporting the nanoparticles, when the coating layer is coated with vinyl chloride resin, innumerable fine irregularities are generated on the surface of the coating layer, and the nanoparticles are trapped and held in the concaves. I was thinking, but when I observed the surface of the resin-coated sheet with an electron microscope, there were no fine irregularities, but gentle undulations, and there was a hole where the applied nanoparticles were completely settled and fixed. There was no smooth surface. In the case of not overcoating, it was clear that the sheet was adsorbed on the entire surface of the coated surface regardless of the surface shape of the undulating irregularities, although the sheet was not sputter-etched. In addition, even after washing with water for several days, even if it is overcoated, it will fall off, but its surface is covered with nanoparticles, and it does not peel off when rubbed with nails. When rubbed with a blade, it was confirmed that the substrate was covered with nanoparticles except where the substrate was shaved, and was firmly fixed, and it was confirmed that it was not fixed by a fine recess. When the water suspension was applied to cellophane and a thermoplastic resin film such as a soft vinyl chloride resin or a polyester (polyethylene terephthalate) resin, and its adhesion was observed, It was easy to apply thinly and uniformly, and when the suspension was dried, it became a film that looked like white natural pollen, but the adsorption effect was great, and the excess part of the overcoated photocatalyst was easily Although it was removed by rubbing, it was found that the photocatalyst on the film surface could not be removed easily and that it could not be removed easily even by ultrasonic cleaning. This was confirmed by hydrophilicity evaluation by exposing the washed product to sunlight and then dropping a water droplet. Directly, a finely coated photocatalyst was exposed to sunlight in the same manner, and was photographed with an electron microscope under non-gold vapor deposition. As an example, a sheet in which a fiber assembly surface was impregnated with a thermoplastic resin was shown in FIG. Show. As shown in FIG. 1, the charged state is different between the applied part (black part) and the unapplied part and can be observed. Also, the film and resin-impregnated fiber sheet were exposed outdoors to observe the function of the photocatalyst. However, the photocatalyst did not easily fall off, and the photocatalyst sustained sterilization, sterilization, sterilization, etc. I learned that the antifouling effect was demonstrated.

  Secondly, the inventors used a hydrophilic inorganic compound-coated photocatalyst in which photocatalyst particles are coated with an inorganic substance that does not undergo oxidative deterioration in order to suppress deterioration of the supported fibers and the like. It was found that by including a photocatalyst in the core of the nanoparticle, the hydrophilic inorganic compound on the surface of the particle is fixed and supported on the surface of an organic material such as a resin that can be wetted with water while having a photocatalytic function. . In other words, it is a photocatalyst-carrying material that adheres and supports without using a binder, using the phenomenon that nano-sized photocatalyst particles adhere to and adhere to fibers, etc., and irradiates the photocatalyst particles that are fixed with ultraviolet light or other light Then, the photocatalyst particles are coated with at least the effect of suppressing the growth of microscopic organisms such as bacteria, sputum, and viruses such as sterilization, sterilization, and sterilization, and odorous or harmful gases and fine droplets by the oxidation effect of the photocatalyst. If the hydrophilic inorganic compound is adsorbed and has a function of deodorizing or detoxifying by the oxidation effect of the encapsulated photocatalyst, if the light exposure is sufficient, at least one day and night, depending on the conditions For about a week, it is possible to obtain a photocatalyst-supporting material that maintains these effects. However, the photocatalyst-carrying material must be exposed to moisture and light in order to exert the photocatalytic oxidation effect. This is a major obstacle to the development of photocatalyst-carrying products. There has been a demand for a fiber aggregate exhibiting the oxidation effect of the above. In addition, when the functional agent used is a photocatalyst, there is a problem that it cannot be used in applications such as light does not strike, it is thick and does not reach the inside, and light cannot be applied.

  In the clean environment, the present inventors paid attention to the fact that these oxidation effects persist even after about one week after light irradiation, and examined the oxidation mechanism in detail. From the persistence of the oxidation effect, Not a simple OH radical, but as a precursor, at least a part of titanium oxide is hydroperoxide. This hydroperoxide, which has a longer lifetime than the OH radical, reacts with the oxide as needed. It was estimated that it generated and exhibited an oxidizing effect. Therefore, as a result of examining partial hydroperoxide conversion of titanium oxide, it was found that the same oxidation effect was exhibited by intermittent peroxide treatment without using light irradiation instead of light irradiation treatment. It came to. Specifically, titanium peroxide nanoparticles are generated from hydroperoxide by intermittently contacting peroxides such as hydrogen peroxide or ozone water with titanium hydroperoxide as part of the titanium oxide molecule. Even if there is no light irradiation, at least the effect of suppressing the growth of microscopic organisms such as bacteria, sputum, and viruses such as sterilization, sterilization, and sterilization, and the deodorization or harmful gas and fine droplets can be eliminated. In addition, it is possible to obtain an organic material and a fiber aggregate carrying nanoparticles having a function of exerting a defeating effect that makes them harmless. Further, the hydroperoxide formation does not limit the thickness of the fiber assembly required for light exposure.

  In addition, when the nanoparticle-supporting material is a nanoparticle-supporting fiber or a nanoparticle-supporting fiber assembly, the nanoparticle adsorption phenomenon is used. Compared with silica, silica, phosphate apatite, and nanoparticles of hydrophilic inorganic compounds such as charcoal are supported on fiber materials with a large specific surface area, the specific surface area is extremely large. Therefore, it is an adsorbent fiber material that is most suitable for a filter that has an extremely high adsorption speed and that can adsorb and remove low-concentration ones. Furthermore, although nanoparticles are generally expensive, even if the amount used for coating is small, the effect of controlling bacteria can be exerted, so that, for example, the amount of expensive photocatalyst used can be made smaller than that using a conventional binder. It is economical.

  In the present invention, nanoparticles coated with a hydrophilic inorganic compound are adsorbed and fixed to a non-water-repellent material, more preferably a hydrophilic material, so that the hydrophilic inorganic compound is supported on the material. If the form of the material is a fiber, it is adsorbed / supported on a non-water-repellent material on the surface of the fiber. If the form of the material is a fiber assembly, the fiber constituting the fiber assembly The fiber surface is composed of a non-water-repellent material or all of the fibers exposed on the surface of the fiber assembly are adsorbed and supported on the fiber surface. When particles coated with a hydrophilic inorganic compound are photocatalyst particles, when the photocatalyst particles are activated by exposure to an ultraviolet lamp or direct sunlight, the oxidative effect of the photocatalyst particles causes bacteria such as sterilization, sterilization, and sterilization.・ Exhibits at least the effect of suppressing the growth of microscopic organisms such as spiders and viruses, and the effect of deodorizing or detoxifying odorous or harmful gases and fine droplets. However, if this is left in a general dark room for photographic development for about 10 days, there is a problem that these effects are reduced or lost, and light and humidity are indispensable for performing these functions. It became clear.

Therefore, when a titanium oxide photocatalyst among photocatalysts is irradiated with light in the presence of water, the Ti—O bond on the surface of the photocatalyst particle or in the vicinity of the surface changes to a Ti—O—OH bond, and comes into contact with the oxide. It was estimated that OH radicals were generated and oxidized. Spraying diluted hydrogen peroxide onto cellulose nonwoven fabric with adsorbed and fixed photocatalyst nanoparticles and measuring the bactericidal properties of the air-dried product shows exactly the same bactericidal properties as the irradiated nonwoven fabric without irradiating light. I found out. Furthermore, when 10% high-concentration hydrogen peroxide was applied (sprayed) to the nonwoven fabric overcoated with the photocatalyst nanoparticle suspension, the applied surface changed to the same yellow color as titanium peroxide (also known as peroxotitanium). It had bactericidal properties as well as hydrogen oxide application (spraying). With the application (spraying) of dilute aqueous hydrogen peroxide solution of several percent or less, the degree of yellowing decreased with decreasing concentration, and when it was 0.5% or less, yellowing was not observed but it had bactericidal properties. From this, it is presumed that a reaction other than the titanium peroxide formation reaction occurs, and the titanium peroxide finally becomes a stable yellow water-insoluble peroxotitanium hydrate Ti ₂ O ₅ (OH) ₂ . Since the bond between titanium and oxygen in the compound is known to be a peroxytitanium bond of Ti—O—O—Ti, it is estimated that the bond between titanium and oxygen is another type of bond. The In addition, since the nanoparticle-supporting material of the present invention retains bactericidal properties, there is no doubt that an oxidative bond exists, and the remaining form of the bond form is a Ti—O—OH hydroperoxide bond. It was only assumed that it took this form. This is exactly the same as the phenomenon assumed that the photocatalyst particles described above are generated by light irradiation in the presence of water, and is consistent with the evaluation of bactericidal properties. Thus, the photocatalyst-supported nonwoven fabric of the present invention can be determined to have a hydroperoxide bond.

  That is, in the present invention, the average primary particle diameter is more than 1 nm and less than 100 nm on the fiber surface covered with at least the non-water-repellent material. Yes, fine particles with a hydrophilic inorganic compound and at least a gas adsorption function are adsorbed to the fiber surface by at least the adsorption ability of the particles themselves, and as a result, the functionality of the nanoparticles being fixed and supported A nanoparticle-supporting fiber, which is a coated photocatalyst referred to as a titanium oxide-based apatite-coated photocatalyst in which at least 30% by mass of functional nanoparticles are coated with apatite, and at least 10% by mass of the titanium oxide is oxidized Nanoparticle support characterized in that at least part of the titanium-oxygen bond of titanium particles is hydroperoxided with an oxidation function It is preferable that the Wei. The water-repellent material referred to in the present invention is a concept that includes a resin that has been subjected to a hydrophilic treatment by adding a hydrophilic group or the like to a resin that is called a super water-repellent resin such as a fluororesin. is there.

  Furthermore, it is a fiber assembly such as paper, non-woven fabric, and woven or knitted fabric having this fiber as a constituent element, and is a functional nanoparticle-supporting fiber among the fibers forming at least one surface, and is at least 20% by weight of the constituent fiber. In order to ensure a bactericidal effect, the filter is a collection of nanoparticle-supported fibers, including paper, non-woven fabrics, woven and knitted fabrics, etc. that contain a majority of the fiber surface. It is preferable that the nanoparticle-carrying fiber assembly of the present invention is a nanoparticle-carrying fiber assembly in which the nanoparticle-carrying fibers of the present invention are unevenly distributed in a part of the surface of the fiber assembly.

  In the present invention, at least one surface of the nanoparticle-supporting fiber aggregate is a means for fixing fine nanoparticles having at least a gas adsorbing function by applying a nanoparticle suspension and printing. The nano-particles are adhered and immobilized on the fiber surface covered with the non-water-repellent material of the fiber where the majority of the fiber surface is occupied by the non-water-repellent material in all and / or a part of the orderly arrangement. Then, by applying a method such as spraying hydrogen peroxide and ozone water to the nanoparticle fixed fiber or the fiber aggregate containing the nanoparticle fixed fiber, at least a part of the titanium oxide particles is hydroperoxided. It is preferable that the aggregate is a nanoparticle-supported fiber assembly.

  As a specific application product of the nanoparticle-supporting fiber assembly, the fiber exposed on one surface of the fiber assembly supports functional nanoparticles containing at least 50% by mass of apatite-coated photocatalyst particles. One side is a nanoparticle-carrying fiber assembly for a filter composed of fibers that can be electretized, and can be an economical air filter material that significantly reduces the amount of photocatalyst used. The filter material can collect dust.

  As a liquid or gas filter material, the sheet-like nanoparticle-carrying fiber aggregate is pleated and folded into a pleat, and the sheet-like nanoparticle-carrying fiber aggregate is wound around a porous core material. Nanoparticles used as cylindrical wound cartridge filters, or cylindrical molded cartridge filters in which heat-adhesive fibers are mixed with sheet-like nanoparticle-supporting fiber aggregates and wound and heat-bonded with the heat-adhesive fibers When it is a supported fiber aggregate and used as a liquid filter, it can be used repeatedly by recovering and activating the oxidative function such as bactericidal property by intermittently flowing a diluted hydrogen peroxide solution at intervals of one day or several days. It becomes possible.

  Chemicals such as bactericides, fungicides and deodorants are exclusively used for fiber assemblies such as non-woven fabrics for applications requiring antibacterial, antifungal and deodorant properties. The fungicides and fungicides are in principle effective and ineffective, that is, there is a spectrum, there is no drug effective for all fungi and sputum, but the nanoparticles of the present invention activated by hydrogen peroxide The supported fibers and their fiber aggregates are oxidized and killed, and it is highly possible that these effects can be exerted over a wide range, but unlike bactericides that bleed out and exert their effectiveness over a wide range, the oxidation of the photocatalyst It is necessary to bring bacteria etc. at a distance that can be effective. When using titanium oxide particles having photocatalytic function activated by peroxides such as hydrogen peroxide of the present invention to exert these effects, the problem is that these bacteria are collected in the immediate vicinity of the hydrogen peroxide photocatalyst. Thus, in the present invention, the problem is solved by covering the photocatalyst with a hydrophilic inorganic compound having an adsorption function, or using it together with fine particles having an adsorption function.

  In general, fiber products such as sheets using a photocatalyst are used by kneading or mixing a photocatalyst with a thermoplastic resin, and since the photocatalyst is expensive, a resin kneaded in a part of the surface layer is arranged, Attempts have been made to reduce the amount of photocatalyst used. In these cases, measures are taken to prevent oxidative degradation of the resin kneaded with the photocatalyst alone or with the inorganic compound, but the resin is used as an adhesive to fix the photocatalyst to the sheet. The photocatalyst was not intended to be held on the sheet by adsorption. In the present invention, a photocatalyst covered with a porous hydrophilic inorganic compound such as apatite having fine adsorption ability is used, and the photocatalyst is basically held and fixed on the fiber surface by the adsorbing force of this apatite and the like. Since the fixing thickness is extremely thin, less than 200 nm, the amount of the photocatalyst attached is reduced to improve the transparency, and the whitishness due to the entire surface of the photocatalyst is avoided. However, in carrying out the present invention with a fiber assembly, the application by means of printing or the like is partially excluded because it may cause a part exceeding the photocatalyst fixing thickness. However, the portion exceeding the thickness is very small as viewed from the whole, and even if the excessively coated portion of this portion falls off, the fallout is extremely small and does not impair the commercial value. In the present invention, a peroxide such as hydrogen peroxide or ozone water is sprayed on an organic material such as a fiber and a fiber assembly in which nanophotocatalyst particles coated with a hydrophilic inorganic compound such as apatite are fixed by adsorption. For example, titanium oxide as photocatalyst particles can be hydroperoxided so that the same oxidation effect as that obtained by light irradiation can be exhibited even in the absence of light. Hereinafter, a fiber in which functional nanoparticles such as a photocatalyst coated with a hydrophilic inorganic compound (hereinafter simply referred to as inorganic compound-coated nanoparticles) are fixed by adsorption, and titanium oxide nanoparticles included in the functional nanoparticles are used. The description will be divided into hydroperoxide treatment.

  An organic material such as a fiber and a fiber aggregate to which the inorganic compound-coated nanoparticles are fixed by adsorption (hereinafter also referred to as a photocatalyst-fixed fiber or the like) is obtained by thinly coating inorganic compound-coated nanoparticles, There is no need to be present on the entire surface of the fiber assembly, and the application form is partial printing as dot print dot printing, further reducing the absolute area and amount of inorganic compound-coated nanoparticles, resulting in an economic effect. Also included is an enhanced one. As in the case of the above-described sheet, the present invention can exhibit the effect of functional particles such as a photocatalyst of the same degree at a low cost by minimizing the amount of inorganic compound-coated nanoparticles used in the fiber assembly. In order to minimize the amount of inorganic compound-coated nanoparticles such as photocatalysts, no binder is used and the coating thickness is submicron order. In some cases, the coating is changed from full surface coating to partial coating, and the amount of photocatalyst used is further increased. Reduced. As a result, as described in the above-mentioned effect, it has succeeded in obtaining a good result corresponding to the case where the transparency is not applied.

  The present invention uses fine nanoparticles as small as several tens of nanometers coated with a hydrophilic inorganic compound such as apatite, and is more preferably non-hydrophobic for fibers due to the adsorption effect of apatite and the like that forms the surface of the nanoparticles. Is supported by being fixed to a hydrophilic surface. That is, when printing and applying a photocatalyst, the nanoparticle suspension is not repelled during printing, the fiber surface is hydrophilic to the extent that it fits, and at least the hydrophilic inorganic compound encapsulating the photocatalyst is adsorbed on the hydrophilic fiber surface To be fixed. That is, functional nanoparticles such as a photocatalyst adhere to the surface of the fiber or the like through the hydrophilic inorganic compound. This fixation is firmly fixed as described above, has a large adsorption effect, and can be made in a state where the coated inorganic compound-coated nanoparticles cannot be removed easily. Therefore, it is preferable that the coating thickness is smaller than the secondary aggregated particle size of the photocatalyst particles from the viewpoint of firmly fixing, and the average secondary particle size is less than several hundreds of nm, so that it is less than 200 nm. Therefore, in the present invention, since the photocatalyst nanoparticles and the like are coated with a hydrophilic inorganic compound, it is mainly used for application as a water suspension, so application to a material that does not repel this suspension is preferable, And it is necessary to apply very thinly. The means for thinly coating is applied by coating the entire surface of the photocatalyst suspension or fine spot-shaped partial coating using a coating device such as a transfer type roll coater, more preferably printing means such as flexographic printing, offset printing or dot printing. Can be easily achieved.

  Since the functional nanoparticles used in the present invention have an essential requirement for self-adsorption ability to the fiber material, the particle surface is preferably composed of at least a hydrophilic inorganic compound having a gas adsorption function. Furthermore, in order to exhibit self-adsorption ability, it is necessary to be nanoparticles, and the average primary particle diameter is less than 100 nm, and those having a particle diameter exceeding 1 nm are used for the convenience of application such as suspension production. . The fine nanoparticles composed of at least a hydrophilic inorganic compound having a gas adsorption function are adsorbed to the fiber surface by at least the adsorption ability of the particles themselves, and as a result, the particles are fixed and supported. In the fiber aggregate, it is preferable that at least the fibers exposed on the surface of the fiber aggregate are formed of the functional nanoparticle-supported fibers.

  Furthermore, as the photocatalyst particles that are one of the functional nanoparticles used in the present invention, known photocatalysts such as anatase-type titanium oxide are advantageously used, and these photocatalysts are hydrophilic for measures to reduce deterioration of surrounding resins. For example, it is preferable to use a photocatalyst covered with an absorptive inorganic compound, paying attention not only to measures for deterioration of the surrounding resin, but also to the adsorptivity. In addition, as the photocatalyst used in the present invention, a commercially available ultrafine powder is used, and those having an average primary particle diameter of less than 100 nm are also commercially available. In order to enhance the adsorption effect described later, 100 nm Is preferably less than 80 nm, more preferably 80 nm or less, and even more preferably 50 nm or less. In addition, it is preferable to avoid secondary aggregation of the fine powder, and the secondary aggregated particles when aggregated are small in number and preferably have a diameter of less than 1 μm. More preferably, it is less than 500 nm, and the smaller the surface area is, the more the surface area becomes larger, the adsorbing force is improved, and the adhering force becomes higher, which is further preferable.

  In the photocatalyst used in the present invention, the substance covering the photocatalyst is a hydrophilic inorganic compound. Examples of hydrophilic inorganic compounds include apatite and silica, and it is known that these fine powders are very easy to adsorb gas and the like. The present inventors have confirmed that the coated apatite-coated photocatalyst or silica-coated photocatalyst has a high adsorbing ability as in the case of a single compound, and conversely, the phenomenon of adsorbing and adhering to the hydrophilic polymer. In addition, it is known that the adsorption phenomenon is larger as the surface area is larger for the same adsorbent, and that the surface area per unit weight is larger as the particle diameter is smaller in the powder, that is, the smaller the adsorbent is, the smaller the adsorbent is. It will be easily adsorbed to objects. For this reason, the particle diameter of the photocatalyst used in the present invention is determined. The apatite-coated or silica-coated photocatalyst referred to in the present invention means a photocatalyst coated with an apatite-based or silica-based compound, and apatite-coated titanium oxide nanophotocatalyst particles are particularly preferable. Of course, the combined use with other coated nanophotocatalyst particles is not inconvenient, but the photocatalyst used has a specific activation reaction with a peroxide such as hydrogen peroxide, which will be described later, in combination with other nanoparticles. Even if it exists, it is necessary to contain at least 30% by mass of the hydrophilic inorganic compound-coated titanium oxide nanophotocatalyst particles. Furthermore, the coated inorganic compound is particularly preferably apatite from the record of adsorption. In the present invention, the coated inorganic compound preferably contains at least 30% by mass of apatite-coated titanium oxide nanophotocatalyst particles. In addition, when it becomes less than 30% by mass in combination with other nanoparticles, a phenomenon such as aggregation is likely to occur, and partial dispersion is likely to occur in coating, which is not preferable. In addition to the above-mentioned apatite and silica, the functional nanoparticles of the hydrophilic inorganic compound used in the present invention other than the above-described photocatalyst include carbon black, but are not limited thereto, and gas adsorption It is preferably used if it is a hydrophilic inorganic compound having a function and is a nanoparticle having the adsorption ability of the particle itself.

  Particles of inorganic compounds such as apatite, silica and activated carbon show good hydrophilicity, and particles of millimeter order to micrometer order are also good gas adsorbents. These can be easily dispersed in water to form a suspension, which precipitates after long-term storage. However, the fine particles of several tens of nm used in the present invention made of these materials have a thickening effect depending on the concentration, do not precipitate even after storage for one month, and when diluted with water, the viscosity depends on the pH of the diluted water. There is a phenomenon that is different from particles of millimeter order to micrometer order, such as uneven liquid (mamako), and these water suspensions are resin films that show hydrophilicity that does not repel this liquid (as a specific example When applied to a thin film on a vinyl chloride resin, polyethylene terephthalate resin, etc., and dried, it adheres cleanly to the film as if wet. Of course, the adhesion thickness is much smaller than the unevenness of the surface of the resin film, and even if the surface of the film is turned up with a sharp blade, only a part of the film surface is scraped off with the adhered particles. The adhered particles remained on the film surface, and even when washed in water, the surface from which the adhered particles were removed at the coated surface could not be found. Probably, the excessively applied particles are considered to have fallen off. However, even when washed with water, at least the portion where the photocatalyst was applied was covered with the particles.

  It should be noted that the functional nanoparticles used in the present invention are conveniently provided for application as a suspension of water so that the application is simple, in addition to water and photocatalyst particles, It is preferable to add or disperse a dispersant, a viscosity modifier, a pH adjuster, or the like as appropriate to prevent or delay secondary aggregation and precipitation separation of photocatalyst particles.

  Further, the photocatalyst particles used are not practically inconvenient even if the purity is not 100%, and only the apatite, silica or other hydrophilic inorganic compound covering the surface of the photocatalyst particles is equivalent to the photocatalyst particles of the present invention. It is not inconvenient if fine particles having a particle diameter are mixed. The ratio of the photocatalyst particles containing the photocatalyst to other particles is at least 30% by mass in the case of full-surface coating, and in the case of partial coating, the ratio of coated area (A area%) × photocatalyst particle mixing ratio (B A mass ratio of photocatalyst particles satisfying at least (mass%)> 30 is desirable. If the mixing ratio is less than the above range, the effect may be insufficient, which is not preferable.

  The functional nanoparticles and photocatalyst nanoparticles used in the present invention have a surface formed of a hydrophilic compound and are excellent in dispersibility in water. If it is necessary, it is not inconvenient to add an organic solvent compatible with water such as alcohol or acetone. Moreover, when a metal-containing compound such as a metal salt that is soluble in water is dissolved in the functional nanoparticle suspension used in the present invention, the sterilizing function having a deodorizing and halo phenomenon can be further enhanced. It is preferable. Examples of the metal-containing compound include copper compounds such as copper sulfate and copper acetate, and zinc compounds such as zinc sulfate, and these can be chemically collected using ammonia as a complex and hydrogen sulfide as a sulfide. There are many other known substances that react with harmful gases such as iron compounds.

  Hereinafter, in order to simplify the description of the present invention, an aqueous suspension of apatite-coated nanophotocatalyst particles will be described as an example.

  The photocatalyst-carrying fiber assembly of the present invention can be obtained by thinly applying the photocatalyst particle suspension by a roll transfer method. However, as described above, a known partial application (dot printing) is possible without applying to the entire surface. However, it can be a fiber assembly having antibacterial and deodorizing functions. Needless to say, it is possible to squeeze into a thin suspension, nip and squeeze it, and hold it on all layers of fibers. Examples of the means for partial application include flexographic printing, gravure printing, screen printing, and dot printing, which can be used conveniently. It should be noted that in intaglio printing gravure printing or the like, excessive application is required unless the concentration of the photocatalyst particle suspension is made thinner than flexographic printing. In the present invention, as described above, it is also preferable from the economical viewpoint to reduce the amount of photocatalyst used to print and apply the photocatalyst with dot-like dots on the surface of the fiber assembly. The dot-like dot shape may be a circle, an ellipse, a polygon, or an indeterminate shape, but in order to reduce the printing area of the photocatalyst, each printing point needs to be arranged orderly and regularly. Polygons such as quadrilaterals are particularly preferred, and their areas are also preferred in order to achieve the effect of inhibiting the growth of bacteria and the like, as well as deodorizing and detoxifying effects, by printing with a small area.

  The use amount of the photocatalyst of the present invention is 50% compared to the method of applying to the entire surface even if the surface coating ratio is 50%, and 5% or less compared with the conventional resin impregnation method generally used. Therefore, even if the cost for printing increases somewhat, the economic effect is great for achieving the same effect.

  Roll transfer to apply a uniform and thin photocatalyst particle suspension is, for example, flexographic printing. First, apply a thin coater to the surface of the first roll with a roll coater, transfer it to the printing roll, and use it for printing. It is convenient to replace the roll with a rubber-coated roll having a smooth surface or a printing roll having a mirror finish. However, flexographic printing with a large printing area is convenient for a thinner coating surface. This is because, even if the photocatalyst particle suspension is partially applied to the printing roll, it can be applied thinly as a whole because there is an escape space for the liquid. In this case, the excess suspension is extruded into the recesses of the flexographic printing plate, and the portion is overcoated, but the area occupied by the whole is small, and it is difficult to cause obvious defects such as white turbidity. It is particularly preferable because it can be expected to fall out. In the description of the present invention, the discussion will proceed with an aqueous suspension. Needless to say, a combination of an organic solvent soluble in water such as alcohol or acetone is also preferable for the demand for quick drying in production. .

  In the present invention, since the photocatalyst coated with a hydrophilic compound is mainly applied as a water suspension, the material forming the fiber surface on which the nanoparticles are supported may be wet or dry rayon fibers, defatted cotton, Cellulose, which is a natural fiber such as hemp, is particularly preferable in terms of fixing. Polyester resins such as polyethylene and terephthalate resins, polyamide resins, polyvinyl alcohol resins, acrylic resins, soft vinyl chloride resins including plasticizers, and ethylene and vinyl acetate. It is a material derived from a natural raw material such as a resin, a wool or the like based on one or more kinds of non-water-repellent materials selected from polymers, chloroprene rubber, chlorosulfonated ethylene rubber, or urethane elastomer resin It is preferable to apply the photocatalyst particle suspension by applying a hydrophilic treatment as described later. Rather a any inconvenience water-repellent resin such as polyolefin resin is possible, of course, further hydrophilization of the hydrophilic resin is more preferred.

  Specifically, the fiber aggregate of the present invention is generally used as a material, cellulose fibers such as cotton and rayon, polyethylene terephthalate fibers, polyamide fibers, polyaramid fibers, polyvinyl alcohol fibers, acrylic fibers and It is convenient to use a woven fabric or non-woven fabric made of one or more types of fibers selected from glass fibers. For non-woven fabrics, rayon spunbonded non-woven fabric (trade name: Benlyse (manufactured by Asahi Kasei Fibers Co., Ltd.)) or thermal bonding fiber A hydroentangled nonwoven fabric and a heat-bonded nonwoven fabric that are mixed with cotton are particularly convenient.

  In the present invention, it is economical to use fiber assemblies such as woven fabrics and nonwoven fabrics that are currently widely used, and in order to improve liquid wettability when water wettability is insufficient, It is highly preferable to perform hydrophilic treatment used for adhesion improvement treatment using adhesives such as surface modification such as corona discharge treatment and flame plasma treatment, sulfonation treatment, ozone oxidation treatment and fluorine treatment. . However, it is also important to consider the selling price, and most of these surface treatments are unnecessary if attention is paid to the non-addition or mixing of water-repellent substances.

  In the woven or knitted fabric, the fibers constituting the fiber assembly are preferably yarns such as spun yarns, multifilament fibers, and core yarns, which are easy to weave. In addition, when the fiber is a split type fiber, a fabric including ultrafine fibers obtained by splitting these yarn fabrics by high-pressure hydroentanglement processing is preferable because it can improve drape.

  The fiber assembly of the present invention is a woven or knitted fabric, a non-woven fabric, or paper. More specifically, one of them is a hydroentangled non-woven fabric or a heat-bonded non-woven fabric, at least 10% by mass of which is a heat-adhesive conjugate fiber. The low-melting-point thermal bonding component of the composite fiber is melted and contributes to the bonding and integration of the nonwoven fabric. If the thermal bonding fiber is less than 10% by mass, the nonwoven fabric is likely to have a strong problem, and preferably Absent.

  The second is that the fiber carrying the functional nanoparticles is exposed on one surface of the fiber assembly, and the fiber layer composed of the electret-treated fiber is arranged on the other side. In addition, the functional nanoparticles include at least 50% by mass of apatite-coated photocatalyst particles and 0 to 50% by mass of carbon fine particles. The fiber aggregate is composed of defatted cotton, wet or dry rayon fiber or acetate fiber, cellulose fiber such as pulp or coconut fiber, synthetic fiber such as defatted wool or silk, or vinylon or polyester fiber. A non-water-repellent material mainly composed of fibers 100 to 30% by mass, a base material layer composed of 70 to 0% by mass of heat-bonding fibers, a spunbond nonwoven fabric layer composed of one or more kinds of polyolefin resins such as polypropylene, The spunbond nonwoven fabric consists of an electretable fiber layer that is at least fused and bonded to the spunbond nonwoven fabric, and the base layer fibers are tangled and integrated with the spunbond nonwoven fabric. A fiber assembly in which a material layer and an electretable fiber layer each form a nonwoven fabric surface There have, which functional nanoparticles on the surface of the fibers of at least the nonwoven fabric surface exposed base layer forming the surface is supported, they are very useful as a filter material, such as air filters.

  The third is a fiber assembly in which the functional nanoparticle-supporting fiber assembly is a composite nonwoven fabric, and specifically, the composite nonwoven fabric has a function of adsorbing gas and the like. The nonwoven fabric layer composed of electret or electretable fibers on one side of the conductive nanoparticle-supporting fiber aggregate is fused and integrated with at least the constituent fiber components of the nonwoven fabric, or hot melt resin It is a composite nonwoven fabric that is bonded and integrated with an adhesive such as a functional nanoparticle having at least one apatite-coated titanium oxide nanophotocatalyst component as a constituent element, and a fiber carrying a photocatalyst. It is a fiber assembly that constitutes one side, or further covers the one side with a translucent fiber layer to improve the textile product characteristics such as tactile sensation. It is useful in such temper partition curtain.

  The fourth is that the fiber assembly is a woven or knitted fabric, one side of which is coated and printed with functional nanoparticles, the functional nanoparticles are fixed, and the other side is a dyed or processed curtain. Designed fiber aggregates such as drape, or one side of which is coated with a non-water-repellent resin, and a composite surgical bed in which the functional nanoparticles of the present invention are also carried on the coated resin surface It is a functional nanoparticle-supporting fiber assembly that is optimal for water-proof sheets such as covers and incontinence mats, and has a water-blocking and breathable structure in which a porous film is bonded and integrated instead of a resin coating. It is a composite of functional nanoparticle-supported fibers that are composited, and further, the composite functional nanoparticle is supported with the functional nanoparticle of the present invention supported on the surface of the porous film that forms one surface thereof. Fiber assembly , It is processed activating spraying hydrogen peroxide to be described later at the time of washing.

  Fifth, non-woven fabrics and nimen meshes for air filters that are not expected to emit light at all, and filters for liquid filtration, particularly water filtration, where the nanoparticle-supporting fiber aggregate is pleated. It is molded into a cartridge filter shape that is folded into a cylindrical shape or wound in a cylindrical shape or heat-bonded in a cylindrical shape. Further, in the liquid filter, the oxidizing function of the nanoparticle-supporting fiber and the fiber aggregate of the present invention can be easily activated by passing the diluted hydrogen peroxide aqueous solution intermittently.

  In addition, since the fiber aggregate of the present invention is almost colorless and transparent even when a photocatalyst is applied, it is difficult to distinguish it from those that are not applied, and it is applied by adding an organic dye with poor light resistance to the photocatalyst solution and coloring it. The status can be visualized to facilitate production quality control. In addition, it is also preferable to print precautions for use with this liquid, and these sheets are discolored and become uncolored after several weeks of use due to the action of the photocatalyst.

  Furthermore, the fiber aggregate of the present invention is sterilized and deodorized from the beginning because the photocatalyst is not coated with resin or binder at all and is exposed on the fiber surface as compared with a conventional resin in which a photocatalyst is dispersed. In order to prevent the excess photocatalyst from dropping off and adhesion of the photocatalyst to other objects, the surface on which the photocatalyst has been printed is washed with water after drying, and further diluted aqueous hydrogen peroxide solution By applying or spraying water, it is possible to easily exhibit the antifouling effect without dropping off the photocatalyst immediately after use.

  In order to express the oxidation function of the nanoparticle-supporting fiber and the fiber assembly of the present invention, at least part of the titanium-oxygen bond of the titanium oxide particle of the apatite-coated nanophotocatalyst particle is hydroperoxide having an oxidation function. The apatite-coated nanophotocatalyst particle-fixed fiber of the present invention and its fiber assembly are applied with a diluted hydrogen peroxide aqueous solution by means of spraying or dipping, and the nanophotocatalyst particle and hydrogen peroxide are brought into contact with each other. Can easily be achieved. The application of hydrogen peroxide depends on the concentration and amount of hydrogen peroxide. Generally, it is convenient to use a liquid having a hydrogen peroxide concentration of 10 to 0.01% by mass, and 5 to 0 by spraying. .1% by mass, and 2 to 0.01% by mass for immersion is good. When the concentration is high, it is yellow, and it is not preferable because it looks bad. Coloring is lowered as the concentration is lower, and it is preferable that coloring is not possible at 2% by mass or less, but the concentration is too low. And the amount of hydroperoxide generated is reduced, that is, the oxidizing effect such as sterilization is reduced, so that the purpose is not met. Further, when low concentration hydrogen peroxide is used, it also has a photocatalytic function, which is more convenient. Note that activation such as sterilization can be achieved by spraying hydrogen peroxide in the same manner as described above. In the hydroperoxide formation, the titanium oxide in which at least part of the titanium-oxygen bond in the titanium oxide particles is preferably at least 10% by mass of the total amount of titanium oxide added. The change becomes severe, and when it is less than 10%, coating spots are likely to occur, which is not preferable. Moreover, it is preferable to heat and dry after application of hydrogen peroxide to prevent a feeling of water wetting. In some cases, it may not be necessary to dry the sprayed hydrogen peroxide immediately after drying after application of the nanoparticles or the apatite-coated nanophotocatalyst particle-fixed fibers and their fiber aggregates.

The amount of the titanium oxide-based nanoparticles fixed to the organic material is most preferably applied seamlessly when viewed from one side of the fiber assembly, and this state can be easily realized by at least one side of the fiber assembly. There is to print on. In this printing on at least one side, the effect can be exhibited as long as the fixed amount of the titanium oxide nanoparticles exceeds 0.5 g / m ² . In consideration of coating unevenness, 1 to 3 g / m ² is sufficient, but if it is desired to apply to the surface of the non-water-repellent fiber material of the fiber assembly, it depends on the basis weight of the fiber assembly, but is 100 g / m ^2. May be necessary. In addition, when the titanium oxide nanoparticles used in the present invention are printed or coated with a water suspension, fine dot-like printing, that is, dot printing, spreads and adsorbs and adheres to the periphery, which is sufficiently effective. It can be demonstrated. In addition, since it may fall even if it apply | coats excessively thickly, it is preferable to apply | coat the quantity corresponding to the target fiber surface area.

  In the nanoparticle-supporting material of the present invention, fine nanoparticles having a hydrophilic inorganic compound having a gas adsorbing function as the particle surface are not encapsulated in an adhesive or resin, that is, a binder, and at least the particles themselves. Adsorbed on the fiber surface by adsorption capacity, and as a result, the functional nanoparticle-carrying fiber to which the particles are fixed and supported and the fiber aggregate containing the fiber have a large specific surface area that is fixed. Like zeolite, it has the effect of adsorbing and removing harmful gases, droplets, bacteria and fungi. Since the present invention uses an apatite-coated nanophotocatalyst, in addition to the above-described adsorption / removal function, it has the effect of detoxifying by the oxidative decomposition ability of the apatite-coated nanophotocatalyst encapsulating these adsorbates. Detoxification is the same as the oxidation effect possessed by photocatalysts, and it exhibits at least the effect of inhibiting the growth of microscopic organisms such as bacteria, sputum, and viruses such as bactericidal, antibacterial, and sterilization. Alternatively, it refers to an invalidating effect in which harmful inorganic gases or fine droplets are adsorbed by the hydrophilic inorganic compound covering the photocatalyst particles and deodorized or rendered harmless by the oxidation effect of the encapsulated photocatalyst.

  Furthermore, since a part of the photocatalyst of the present invention is converted into hydroperoxide having oxidizing power, it has an effect of detoxifying even in the absence of light by oxidative decomposition ability as in the case of a conventional photocatalyst. Replenishment, i.e. activation, of the hydroperoxide consumed in the absence of light can be facilitated by laundering or contact with hydrogen peroxide intermittently within approximately one week. Note that the intermittent contact with hydrogen peroxide was within one week because the coated photocatalyst fine particles had an oxidation effect of at least 1 even if they were not exposed to light once they were exposed to light. Based on the fact that it lasts more than one week depending on the conditions day and night, similar results were obtained with the non-woven fabric of the present invention subjected to the hydrogen peroxide activation treatment.

  Although the titanium oxide nanoparticles used in the present invention depend on the concentration and amount of hydrogen peroxide to be activated, some of them are hydroperoxides and lose their original functions as photocatalysts. Therefore, when sufficiently exposed to light, at least in the air, the excitation energy is maintained for 1 day to 1 week or more, and even when not exposed to light, it exhibits an oxidizing effect such as sterilization. The hydroperoxidized nanoparticle-supporting material of the present invention is particularly useful when used for a long period of time when light irradiation cannot be expected, and the conventional photocatalyst-supported fiber assembly requires light irradiation. Easy-to-use cloth and non-woven window lace curtains, sunbathing chairs such as nursing homes and rehabilitation centers, and masks used when attending school children Although the present invention is limited to textiles that are exposed to sunlight, the fiber assembly of the present invention requires intermittent exposure to hydrogen peroxide, but these restrictions can be eliminated, so masks, sheets, and towels can be removed. Deodorizing, disinfecting, and preventing easily, without exposing care or medical textiles such as cases, bandages, surgical drapes, lab coats, surgical gowns and covers, hospital room or clinic room divider curtains, etc. It can be a dwarf textile product.

  The greatest feature of the present invention is that it is not developed as a new product, but it requires intermittent exposure to hydrogen peroxide, but the already popular textile product is a functional product with sterilization and deodorizing functions. Since it is easy to divert, market development can be simplified. In particular, textile products that are regularly washed, such as sheets, have already been sterilized with hydrogen peroxide in sheets for business use, and are more useful because they can be used as they are. Moreover, the hydroperoxide-ized nanoparticle-supporting fiber of the present invention and the fiber assembly thereof can carry nanoparticle support by a simple means such as printing of a water suspension and activate hydrogen peroxide. The treatment can be easily carried out by spraying a dilute aqueous hydrogen peroxide solution. Also, washing can be accomplished by washing with Marcel soap or the like and then spraying in the same manner. Especially for curtains, the fiber aggregate of the present invention has an adsorption capacity, and therefore adsorbs bacteria floating in the air and dust adhering to the bacteria by the adsorption action, and oxidizes with nanoparticles. This is useful because it can be rendered harmless.

  Since the nanoparticle-supporting material of the present invention is at least a part of the fiber surface covered with an extremely thin layer of a photocatalyst or the like coated with a hydrophilic inorganic compound having a thickness of less than 200 nm, more preferably less than 100 nm, Even if a photocatalyst or the like is carried, light scattering on the surface occurs slightly, but it is colorless and transparent, and the same applies to the activation treatment with hydrogen peroxide. However, it can be used as a photocatalyst carrier with functions such as growth suppression effect and invalidation effect with excellent color vividness that do not impair the color and texture, etc., and the amount of photocatalyst used can be extremely small, so these are inexpensive. It is advantageous for market penetration.

  The antibacterial effect includes the use of conventional photocatalysts, such as the seating material for seats installed in places exposed to light, such as vehicle seats and hospital waiting room seats. In addition to curtains such as hospital room partition curtains and home window curtains and covers such as bed sheets and bedding covers, the product of the present invention does not expect light irradiation. It is extremely useful as a liquid cartridge filter for sterilization of air cleaners, air conditioners, and food manufacturing washing water, which could not be applied in the past. The photocatalyst whose surface is coated with a hydrophilic inorganic compound that easily adsorbs bacteria, etc., is adsorbed by bacteria that are floating in the air due to its adsorption action. That dust adsorbs, photocatalyst, or cause such as bacteria adhered in the vicinity by sterilizing or inactivate the oxidation action of a photocatalyst. In addition, a combined effect such as antibacterial effect and deodorization is caused by adsorbing and oxidizing organic harmful dust, gas, and droplets in the same manner as described above.

  In addition, when antibacterial effect is expected, it is preferable to print the photocatalyst particle suspension on the entire surface, but dot printing is not inconvenient, and the photocatalyst is printed when using a flexographic printing machine, gravure printing machine or dot printer. Arbitrary pigments can be printed on the parts that are not, so it is easy to draw letters and design pictures at the same time as photocatalyst application. Since these are mostly used for viewing from a certain distance rather than close-up, the purpose of display can be sufficiently exhibited. In addition, in order to confirm the printing state of the photocatalyst, a dye such as methylene blue having no weather resistance is added to the photocatalyst printing liquid, and printing makes it easy to grasp the state of the printing state, and when this is exposed to sunlight or sprayed with hydrogen peroxide, In direct sunlight, the dye is oxidatively decomposed and colorless in a few hours, generally in a few weeks, and returns to the same state as an unadded product. By using this principle, it is possible to print dimensional display and shape of fiber aggregates such as woven and knitted fabrics, non-woven fabrics and papers, making it easy to sew, and printing precautions for end users. .

  Next, the effects of the present invention will be specifically described with reference to examples. In the following explanation, explanation will be made using an apatite-coated titanium oxide photocatalyst, and a combination with a photocatalyst coated with another hydrophilic inorganic compound or simple functional nanoparticles will not be explained. It will be easy to use. Also, it is mainly explained with copper ammonia rayon spunbonded nonwoven fabric (trade name: Benlyse, manufactured by Asahi Kasei Fibers Co., Ltd.), a heat-adhesive composite fiber (hereinafter also referred to as PH) having a polypropylene resin as a core component and a sheath component as a polyethylene resin. ) 30 mass% and water entangled non-woven fabric blended with rayon (hereinafter also referred to as R) 70 mass%, hydroentangled fabric blended with 30 mass% of fibers made of polyethylene terephthalate resin (hereinafter also referred to as PET) and 70 mass% rayon. A nonwoven fabric, a rayon hydroentangled nonwoven fabric, a nylon mesh (hereinafter also referred to as Ny), and these plain fabrics and hydroentangled nonwoven fabrics will be described, but other materials can be similarly implemented.

(Photocatalyst used)
The titanium oxide photocatalyst covered with the apatite-based compound used in the examples can be easily obtained from Showa Denko Co., Ltd. as an example, and the average primary particle size is about 30 nm, and the aggregated secondary The particle diameter is 200 to 500 nm. Printing is performed using a photocatalyst uniformly dispersed in a solvent. The solvent is obtained by adding a small amount of drug to water.

  Since the photocatalyst is sufficiently fine, it is very easy to be adsorbed on objects. For example, in order to uniformly disperse the photocatalyst in water, a very small amount of a dispersion thickener or penetrating agent is added, and in some cases, a printing liquid is added with alcohols to prevent sedimentation of particles and Conveniently, it is possible to improve the stability of the turbid liquid and improve the printing suitability.

  The photocatalyst was fine, and when it was dot-printed and placed on the coating film, it was tightly adsorbed on the film surface as shown in FIG. The photograph in FIG. 1 was taken with a scanning electron microscope without gold deposition, and the portion where the apatite photocatalyst is adsorbed is shown in black. This is presumably because the apatite-based photocatalyst has some conductivity, and the charged state of the surface is small compared to the non-adsorbed portion. Even if further expanded in this situation, the photocatalyst was so fine that it could not be confirmed as particles. The photocatalyst used in the present invention can be used in the same manner by covering not only anatase-type titanium oxide but also a generally known photocatalyst with an apatite-based or silica-based compound. The size of the photocatalyst nanoparticles covered with the apatite-based or silica-based compound used in the present invention is preferably less than 100 nm because the photocatalyst is mainly adsorbed and fixed, and the photocatalyst solution is designed to prevent secondary aggregation as much as possible. Is preferred. Further, the average primary particle diameter of the coated photocatalyst is more preferably as fine as 50 nm or less, more preferably 30 nm or less.

For the above reasons, the photocatalyst will be described in the following examples. The silica-based photocatalyst coated with silica, which is hydrophilic as the apatite, was the same as the apatite-based photocatalyst. The average primary particle size was measured by the following method.
[Average primary particle size]
Observed with a transmission electron microscope, 100 particles were arbitrarily extracted, the particle diameter of each particle was measured, and the average particle diameter was calculated.

  The printing liquid stock solution used in the examples of the present invention was composed of 20% by mass of apatite-based photocatalyst fine particles coated with an apatite compound manufactured by Showa Denko K.K. with a particle size of 0.5% by weight of a penetrating agent for particle dispersion. Water dispersion with a viscosity of several hundreds (about 300) centipoise, added with 0.4% by weight of a dispersion thickener to make it difficult to settle and separate dispersed photocatalyst fine particles during storage. It is a liquid. Viscosity can be arbitrarily set by changing the amount of dispersion thickener added, and according to the flexographic printing machine, the above-mentioned printing liquid stock solution is diluted with ion-exchanged water adjusted to pH by adding penetrant and dispersion thickener. A 5% by mass suspension of photocatalyst particles was prepared and used as a printing liquid for rubber roll printing. This was appropriately diluted with ion-exchanged water and used for other coating and impregnation.

(Carbon black to be used)
Specifically, the carbon black used in the present invention can be easily obtained from Mitsubishi Chemical Corporation with an average primary particle size of about 24 nm and an aggregated secondary particle size of about 100 nm. is there. Rubber roll printing is carried out using a material that is uniformly dispersed while being ground in water. The solvent is obtained by adding a small amount of drug to water.

(Copper ammonia rayon spunbond nonwoven fabric used)
Benlyse NN500 manufactured by Asahi Kasei Fibers Co., Ltd. having a basis weight of 52 g / m ² was used (hereinafter referred to as A nonwoven fabric).

(Rayon hydroentangled nonwoven fabric used)
(1) R nonwoven fabric A 1.7 dtex R fiber was opened to form a web, which was hydroentangled to obtain a hydroentangled nonwoven fabric having a basis weight of about 35 g / m ² (hereinafter referred to as R nonwoven fabric).
(2) RH1 nonwoven fabric 30% by mass of 2.2 dtex PH fiber and 1.7 dtex R fiber were formed into a web and hydroentangled into a hydroentangled nonwoven fabric having a basis weight of about 35 g / m ² ( Hereinafter referred to as RH1 non-woven fabric).
(3) RH2 non-woven fabric 30% by mass of 6.7 dtex PH fiber and 6.7 dtex R fiber were opened to form a web, and hydroentangled with a hydroentangled non-woven fabric having a basis weight of about 35 g / m ² ( Hereinafter referred to as RH2 non-woven fabric).
(4) RH3 non-woven fabric 30% by mass of 2.2 dtex PET fiber and 1.7 dtex R fiber were opened to form a web, and hydroentangled into a hydroentangled non-woven fabric having a basis weight of about 35 g / m ² ( Hereinafter referred to as RH3 non-woven fabric).

(Used synthetic fiber hydroentangled nonwoven fabric)
(1) PET nonwoven fabric A 1.7 dtex PET staple fiber was opened to form a web, which was hydroentangled to obtain a hydroentangled nonwoven fabric having a basis weight of about 40 g / m ² (hereinafter referred to as PET nonwoven fabric).
(2) PE non-woven fabric Blended with 85% by mass of 2.2 dtex PET staple fiber and 15% by mass of 2.2 dtex PH fiber with a composite ratio of 1/1, hydroentangled, dried and further heated to 145 ° C. to be polyethylene Was melted and heat-bonded to give a guessed entangled nonwoven fabric with a basis weight of about 40 g / m ² that prevented fluffing (hereinafter referred to as PE nonwoven fabric).
(3) AR nonwoven fabric Acrylic staple fibers of about ² dtex were opened to form a web, which was hydroentangled to obtain a hydroentangled nonwoven fabric with a basis weight of about 45 g / m ² (hereinafter referred to as AR nonwoven fabric).

(Ny mesh used)
About 30-mesh 6 nylon mesh was used which was hydroentangled to remove oligomers and the like.

(Plain fabric used)
A plain woven 30th TC blended yarn of 30% by weight of 1.1 dtex PET staple fiber and 70% by weight of cotton is used as a cut shirt fabric with a basis weight of 160 g / m ² , refined, degreased and dried. used.

[Examples 1 to 5, Comparative Example 1]
In a dark room, a 5% by mass suspension of Showa Denko Co., Ltd. apatite-coated nanophotocatalyst particles was hung on a smooth glass plate, and thinly and evenly spread on the glass plate using a rubber roll used for printing a photocopier. This suspension was transferred to the same rubber roll and applied to A nonwoven fabric. The rotation of the rubber roll was marked on the nonwoven fabric, and this was dried for 1 hour with a dryer at 140 ° C. to obtain an apatite-coated nanophotocatalyst particle-fixed nonwoven fabric. The amount of increase in mass at each rotation was measured, and the weight per unit area of the photocatalyst applied was H (g / m ² ).

The apatite-coated nano photocatalyst particle-fixed non-woven fabric is a non-woven fabric in which the photocatalyst at the second rotation of the rubber roll is fixed at 2 g / m ^2. It dried and produced the non-woven fabric which carried out hydroperoxidation of Examples 1-5. The obtained nonwoven fabric was evaluated for bactericidal / antibacterial activity. This was further washed, and the washing durability test was similarly evaluated. In addition, as a reference value, a sample subjected to direct sunlight exposure for 3 days was also evaluated in the same manner. The spraying conditions and results are shown in Table 1.

  The nonwoven fabric of Comparative Example 1 is an original fabric of the photocatalyst-fixed nonwoven fabric used in these Examples, and is left in a dark room without light for about 1 month. The evaluation methods in Table 1 are as follows.

[Degree of yellowing]
The degree of yellowing was indicated as good when visually uncolored, fine when slightly but slightly observed, slightly recognized as slightly, and colored as yellow.

[Bactericidal and antibacterial activity values]
The bactericidal and antibacterial activity values were obtained by measuring the viable cell count of Staphylococcus aureus by dilution plate culture method using the microbial liquid absorption method of JIS-L-1902. As the blank unprocessed cloth, a standard cotton cloth was used, and the bactericidal activity value was determined to be effective when the value was 0 or more, and the antibacterial activity value was determined to be effective when the value was 2 or more. A pass (judgment with effect) was marked with a circle, and a test with no effect was marked with a failure, and an x was marked. The value ▲ indicates a minus value. From this result, it was found that if the spray of hydrogen peroxide is too much, yellowing occurs, but there is a sufficient bactericidal and antibacterial effect. In addition, it was found that a sterilizing / antibacterial effect is sufficient even when washed with Marcel soap or water. Of course, the same results were obtained even when exposed to sunlight, and the photocatalytic function was maintained.

[Examples 6 to 11]
In the same manner as in Example 1, coating was performed with a printing liquid having a photocatalyst concentration of 20, 10, 2, and 1% by mass using a rubber roll used for printing of a copying plate. This was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Examples 12 to 20, Reference Examples 1 to 3]
Using the nonwoven fabric, mesh, and woven fabric shown in Table 3 instead of the nonwoven fabric of Example 9, a fiber assembly according to the present invention was prepared by performing hydrogen peroxide activation treatment under exactly the same conditions as in Example 1. Produced. Tables 3 and 4 show the results of evaluating the bactericidal and antibacterial effects of the obtained nonwoven fabric. In addition, the photocatalyst adhesion amount was in the range of 3 to 6% by mass, and the bactericidal and antibacterial effects were also the same. In Reference Examples 1 to 3, the exposure to sunlight was carried out for 3 days in the same manner as in Comparative Example 1 without performing the hydrogen peroxide activation treatment.

[Example 21]
^On the polypropylene spunbond nonwoven fabric having a basis weight of 15 g / m ² , a spread web of the same rayon staple fiber as in Example 12 is laminated, and hydroentangled from the web side in the same manner as in Example 1, and fiber entangled. An integrated hydroentangled nonwoven fabric was prepared. Next, a photocatalyst was applied to the surface of the rayon fiber layer in the same manner as in Example 1, dried, and then an aqueous hydrogen peroxide solution was sprayed at the outlet of the dryer to prepare a nanoparticle-supporting base fabric. On the spunbond nonwoven fabric side of the base fabric, a melt blown nonwoven fabric of about 2 dtex composite fiber having polybutene-1 as a sheath component and polypropylene as a core component is fused and bonded to form a composite nonwoven fabric, which is then heated to 120 ° C. The electret filter was subjected to electret processing in an electric field of 10 to 20 KV during drying and cooling. When the composite nonwoven fabric was evaluated in the same manner as in Example 1 for the bactericidal and antibacterial effect on the photocatalyst-coated surface, the same results as in Example 12 were obtained. In addition, according to the JIS-Z-2911 fiber product test / wet method, the composite nonwoven fabric was pasted on an agar medium, and the mold resistance test of the fiber product sprayed with the spore suspension was performed. In addition, it was possible to obtain a result that no cocoon growth was observed for at least 10 days, and to confirm the antifungal property.

[Examples 22 to 23, Comparative Example 2]
The non-woven fabric coated with hydrogen peroxide-treated photocatalyst used in Examples 13 and 14 was heated with a hot air dryer at 145 ° C. and wound around an iron core at the outlet, and the inner diameter was 28 mmφ and the outer diameter was 68 mmφ, respectively. A cylindrical mold type cartridge filter having a length of 250 mm was produced. Mount the cartridge filter on an existing cartridge filter housing, dilute the pond water for agricultural use with industrial water that has not been sterilized to 1/50, feed it from the plastic container to the housing using a pump, and filter Use a Daimler fermentation tube called the LB-BGLB method, in which the liquid in excess of 20L is collected, the liquid itself is not diluted, and the sensitivity of JIS-K-0101 63.5 is sensitive. As a result, no E. coli was detected. As a comparative example, a prefabricated mold type cartridge filter produced by winding a heat-adhesive conjugate fiber of about 2 dtex with polyethylene as the sheath component and polypropylene as the core component under the same conditions was prepared and implemented. Evaluation similar to Example 21 was performed. The cartridge filter of Comparative Example 2 was detected even after dilution, and it was in the order of several thousand pieces / ml when measured by the agar medium measurement method of JIS-K-0102-72.3, which has low sensitivity.

[Examples 24 to 25, Comparative Examples 3 to 4]
A 10 cm × 10 cm sample of Sample A of Example 1 was placed in a 5 L Tedlar bag and exposed to 50 ppm of diluted acetic acid air for 24 hours to give 4 ppm (Example 24). It became 19 ppm in the rayon spunbond nonwoven fabric to which no photocatalyst was adhered (Comparative Example 3). The difference was 15 ppm, and an increase in adsorption effect was recognized. Here, the adsorption effect is because the oxidation effect of the photocatalyst has not been confirmed. Further, when ethylene gas, which is a plant maturation hormone, was evaluated in the same manner in place of acetic acid, it was 1 ppm when 10 ppm of diluted gas was exposed for 24 hours (Example 25). Similarly, the blank rayon spunbond nonwoven was 8 ppm (Comparative Example 4). It was confirmed that there was at least an adsorption effect.

[Examples 26 to 28]
In Example 6, the printing means is a flexographic printing machine, the urethane resin-coated printing roll has an area per dotted dot of 0.1 mm ² , and the printed area is 40%, 25% of the total target area, And 15% sculptured rolls, and dot printing using each roll, with a printing ratio of 40 area% and 25 area%, and a fixed amount of photocatalyst of 7, 3.5 g / m ² Fabricated with nonwoven fabric. Subsequently, when the fixed nonwoven fabric was activated in the same manner as in Example 6 to evaluate the bactericidal / antibacterial effect, almost the same results were obtained (Examples 26 and 27). Also, a fixed nonwoven fabric having a printing ratio of 15 area% and a photocatalyst fixing amount of 0.5 g / m ² was produced. Next, activation treatment was performed in the same manner as in Example 6 to evaluate the bactericidal / antibacterial effect (Example 28). The non-woven fabric of Example 28 had a result that the bactericidal activity value was significantly reduced to 1 and the antibacterial activity value was significantly decreased to 3, but it passed the standard.

[Examples 29 and 30]
Using the 5% by mass photocatalyst printing liquid used in Example 1, 1.7 dtex rayon of non-fat cotton was drawn on a glass plate, and the photocatalyst was applied to the fiber in the same manner as in Example 1. This was put in a polyethylene bag, mixed well in the manner of scouring and coated with a photocatalyst on the whole, dried with a dryer at 100 ° C., and made slightly wet cotton. Next, the coated fiber is mixed with uncoated rayon fiber so that the mixed fiber ratio is 30% by mass (Example 29) and 15% by mass (Example 30), to produce a card web, and fiber entanglement with a needle punch machine It was made into the entangled nonwoven fabric of 70 g / m < ² >. The nonwoven fabric of Example 29 showed the same bactericidal and bactericidal effect as Example 1. The nonwoven fabric of Example 30 resulted in a significant decrease in bactericidal activity value of 1 and antibacterial activity value of 3, but passed the standard.

[Example 31]
After the nonwoven fabric of Example 17 was subjected to corona discharge machining, a photocatalyst was applied in the same manner as in Example 17, and hydrogen peroxide activation treatment was performed to obtain a fixed nonwoven fabric. When this was evaluated in the same manner as in Example 17 for the bactericidal / antibacterial effect, the same result as in Example 1 was obtained.

It is the fiber aggregate surface non-gold vapor deposition scanning electron micrograph which dot-printed the suspension containing a titanium oxide type nanoparticle.

Claims (9)

A nanoparticle-supporting material comprising an organic material and functional nanoparticles having an average primary particle diameter of more than 1 nm and less than 100 nm, and the particle surface coated with a hydrophilic inorganic compound,
The functional nanoparticles are adsorbed and fixed and supported on at least a part of the surface of the organic material by at least the adsorption ability of the particles themselves,
At least 30% by mass of the functional nanoparticles are titanium oxide-based nanoparticles coated with a hydrophilic inorganic compound, and at least a part of the titanium-oxygen bond of titanium oxide is hydroperoxided with an oxidizing function. A nanoparticle-supporting material comprising nanoparticles.   The nanoparticle-supporting material according to claim 1, wherein the titanium oxide-based nanoparticles have a photocatalytic function.   The organic material is a fiber in which a majority of the fiber surface is occupied by a non-water-repellent material, and the functional nanoparticles are adsorbed to the fiber surface by at least the adsorption ability of the particles themselves, and are fixed and supported. Item 3. The nanoparticle carrying material according to Item 1 or 2.   The organic material is a non-water-repellent material and a fiber aggregate including fibers in which a majority of the fiber surface is occupied, and the functional nanoparticles are adsorbed on the fiber surface by at least the adsorption ability of the particles themselves, and are fixed and supported. The nanoparticle-supporting material according to claim 1 or 2.   The nanoparticle carrying material according to any one of claims 1 to 4, wherein the fiber is a cellulosic fiber.   The nanoparticle-carrying material according to claim 4 or 5, wherein the fiber aggregate is molded into one shape selected from a folded pleated shape, a wound shape, or a tubular shape that is heat-bonded after winding. One surface of the fiber aggregate includes a functional nanoparticle having an average primary particle diameter of more than 1 nm and less than 100 nm, and the particle surface is coated with a hydrophilic inorganic compound, and the functional nanoparticle is at least of the particle itself It is a surface containing fibers that are adsorbed to the fiber surface by adsorbing ability and fixed and supported, and at least 50% by mass of the functional nanoparticles are titanium oxide-based nanoparticles coated with a hydrophilic inorganic compound, Comprising a nanoparticle-supporting surface including nanoparticles in which at least a part of a titanium-oxygen bond of titanium oxide is hydroperoxide having an oxidation function;
A fiber assembly for a filter, wherein the other surface has an electret surface containing electretized fibers. The average primary particle diameter is greater than 1 nm and less than 100 nm, and the surface of the particles includes functional nanoparticles coated with a hydrophilic inorganic compound, and at least 30% by mass of the functional nanoparticles are coated with a hydrophilic inorganic compound. A suspension containing titanium-based nanoparticles,
After being applied to at least a part of the surface of the organic material, the functional nanoparticles are adsorbed, fixed and supported,
The manufacturing method of the nanoparticle support material which provides a peroxide to the said titanium oxide type nanoparticle.   The method for producing a nanoparticle-supporting material according to claim 8, wherein the peroxide is hydrogen peroxide or ozone water.