JP2010069469A - Method of deodorizing/sterilizing with photocatalyst and transparent liquid photocatalyst used for this method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To increase the exposure level of a particle surface by uniformly dispersing an ultrafine particle fibrous titanium oxide alone in the fiber of clothes and make the fibrous titanium oxide adhere firmly to the fiber, and achieve the anchoring of the ultrafine particle of the fibrous titanium oxide strongly into the fibers of the clothes for a long time through drying at an extremely low temperature. <P>SOLUTION: This method employs a photocatalyst jet means to jet a liquid photocatalyst to a fibrous material e.g. clothes inside an airtight chamber, an ultraviolet irradiation means to irradiate ultraviolet rays to the photocatalyst adhering to the fibrous material, and a hot blast drying means to send a hot blast to and dry the liquid photocatalyst sticking to the fibrous material. The photocatalyst of the photocatalyst jet means is a fibrous titanium oxide ultrafine particle. Thus, a transparent liquid photocatalyst having an appropriate amount of the ultrafine particle dispersed is jetted. Besides, the temperature of the hot blast in the hot blast drying means is 30 to 120°C, and the ultrafine particle, with which the interior of the airtight chamber is filled, is uniformly fixed and dried in the interior of the fiber of the fibrous material by hot blast. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

Detailed Description of the Invention

  The present invention is a photocatalytic deodorizing and sterilizing method for deodorizing and sterilizing textile products such as clothes, lab coats, training clothes, etc., particularly in hospitals, nursing homes, laundry shops, food processing factories, livestock facilities, sports facilities, etc. The present invention relates to a transparent liquid photocatalyst used for this.

Background of the Invention

  Recently, various products having deodorizing and sterilizing functions utilizing the photocatalytic action of titanium oxide have been developed. These products are aimed at antibacterial and deodorizing effects due to decomposition of microorganisms and odorous substances adhering to the product surface by photocatalytic action such as titanium oxide. The photocatalytic action of titanium oxide is that when the titanium oxide particles are irradiated with ultraviolet rays, the holes generated on the surface of the photocatalyst react with the adsorbed water on the surface of the photocatalyst to generate radical OH (hydroxyl radical). It is considered that the radical OH breaks the molecular bond of the organic substance, which diffuses to the particle surface and acts as an oxidizing or reducing action on the surrounding organic substance.

  Titanium oxide has a wide range of uses that make use of its chemical properties. For example, it has a suitable binding force with oxygen and has acid resistance, so it has a redox catalyst or carrier, a cosmetic material or a plastic surface that uses ultraviolet blocking power. It is used as a coating agent, an anti-reflection coating agent that utilizes high refraction, an antistatic material that utilizes electrical conductivity, a combination of these effects, and a functional hard coating material. Used for fungicides, antifouling agents, super hydrophilic coatings, etc.

  The titanium oxide used as the photocatalyst is not limited to amorphous titanium oxide, but is preferably crystalline titanium oxide such as anatase-type titanium oxide, brookite-type titanium oxide, rutile-type titanium oxide, and mixed crystals and eutectics thereof. Type titanium oxide and brookite type titanium oxide are widely used because of their high band gap.

  The concentration of the water-dispersed sol of the titanium oxide particles and the titanium oxide-based composite oxide particles composed of oxides other than titanium oxide and titanium oxide is not particularly limited, but ranges from 5 to 40% by weight as oxides. In such a concentration range, it is known that the sol is stable and the titanium oxide particles can be produced efficiently without aggregation of the particles during the alkali treatment.

  In addition, since such a titanium oxide film having a photocatalytic action requires high-temperature treatment (150 ° C. to 400 ° C. or more) during film formation, it can be produced on glass, plastic, wood, fiber, cloth, etc. that are not heat resistant. The membrane is difficult. For this reason, it is possible to form a cured film at a relatively low temperature by adjusting the coating liquid for forming a film using titanium oxide particles treated at a high temperature, and forming the film by applying this coating liquid on a substrate. Has been tried. However, high-temperature treated titanium oxide particles generally have a large particle diameter and a high refractive index, so that light scattering by the titanium oxide particles in the coating is large, and a titanium oxide coating with excellent transparency cannot be obtained. is there.

  Furthermore, as a method for forming a titanium oxide film, a titanium oxide coating solution is applied to the surface of a substrate by a spinner method, a bar coater method, a spray method, a dip method, a flexo method, etc., and then dried and cured at high temperature. It has been known.

  Conventionally, for example, Cited Document 1 (Japanese Patent Laid-Open No. 2000-288405) discloses that “a photocatalyst characterized by granulating fibrous titanium oxide into porous particles, fibrous titanium oxide, and particulate titanium oxide. There is provided a photocatalyst body characterized by granulating a mixture into porous particles.

  And in the publication [0012], “as the shape of these fibrous titanium oxides, the average fiber diameter is 0.05 to 30 μm, preferably 0.1 to 5 μm, the average fiber length is 3 to 500 μm, preferably 5 to 200 μm, Examples having an average aspect ratio of 3 to 1000, preferably 6 to 200 can be exemplified.

  However, in the present invention, the granule is made into porous particles to increase the contact area with the object to be processed so as to obtain high photocatalytic activity. However, the fiber diameter is coarse and the fiber length is long. For this reason, when sprayed on the fiber of clothes, it is not a nanometer-sized particle, so it is not sufficiently dispersed in the fiber, and the adhesion to the fiber is weak. Further, since it is not a nanometer dispersion but a porous body, the specific surface area of titanium oxide is limited, and the exposed ratio of the particle surface is extremely small as a whole, and a high photocatalytic activity cannot be obtained.

Further, in cited document 2 (Japanese Patent Application Laid-Open No. 2001-205099), “in a photocatalyst using titanium dioxide (TiO ₂ ), the titanium dioxide is porous titanium having a porosity of 5 to 90% ( "Photocatalyst characterized in that it is anatase-type titanium dioxide formed by oxidation by sintering Ti) alloy".

  And, [0024] “It is a titanium alloy formed by sintering at 1200 to 1350 ° C. with the titanium dioxide catalyst 101 of the present invention, and the titanium fine powder is a fine particle of about 20 nm to 200 μm”, “This titanium alloy is then oxidized in an oxidizing atmosphere of 800 ° C. or lower to become an anatase-type porous titanium dioxide alloy having a porosity (or porosity) of 5 to 90%. Is explained.

  However, in the present invention, it is a porous titanium alloy having a porosity of 5 to 90% and is not fibrous, or is obtained by firing a woven fabric in which fibers are woven into a mesh shape, and when sprayed on clothes, Adhesive strength to the fabric is weak, and the baked product woven in a mesh shape does not sufficiently penetrate into the fibers of the clothes, resulting in poor adhesion.

  Further, cited document 3 (Japanese Patent Laid-Open No. 2005-329101) states that “a portable one-piece type comprising a plurality of ultraviolet lamps and a blower, and an area where air is irradiated with ultraviolet rays is long. And ozone is supplied into the room by an ozone generator provided with an ultraviolet lamp in the longitudinal direction of the space, and a suspension in which the photocatalyst powder is suspended in a liquid is sprayed into the room. And "deodorization and foul odor prevention method".

  [0025] “This photocatalyst is commercially available as a fine powder. The size is about several nm to several μm. This is added to water or alcohol to form a suspension.” [0027 When this photocatalyst suspension is sprayed on, for example, it adheres to a cloth or a wall surface and remains there. Therefore, it is natural to decompose the organic matter present in the vicinity by a photolysis reaction, but in the future, those attached in the vicinity will be decomposed. Therefore, it is demonstrated that it exhibits a preventive effect. "

  However, as described in [0026], the spraying of the photocatalyst suspension is explained to be “a normal spray or spraying”, and the photocatalyst suspension is described as described in [0030] to [0033]. The spraying of the liquid is performed separately from the ozone generator of the present invention. Therefore, the spraying of the photocatalyst suspension of the present invention is provided as a post-process of a preventive method that is separately performed after ozone supply by the ozone generator.

Moreover, in the cited document 3, the particle diameter of titanium oxide is only described as several nm to several μm, and there is no description that titanium oxide is fibrous, and the fiber width and thickness, fiber length, aspect ratio are not described. The ratio and specific surface area are unknown. Therefore, it cannot be understood whether or not sufficient adhesion to fibers can be obtained when sprayed on clothes.

  Further, cited document 4 (Japanese Patent Laid-Open No. 2005-034254) states that “deodorant comprising at least a photocatalyst and a structure having pores having an average diameter of gas molecules or more, and the photocatalyst carried on the structure. A deodorizing apparatus including an irradiating means and a blowing means for irradiating light containing at least ultraviolet rays to a deodorizing body is described.

  Then, in [0039], a deodorizing body (nano-deodorizing body) containing titanium oxide prepared by the method described in [0038] was measured as shown in FIG. In addition, the honeycomb body shown in FIG. 5 is a “200-cell honeycomb body in which this deodorized body (including titanium oxide) is made into a slurry containing 30 wt% silica sol, dipped in a ceramic honeycomb, and dried and fired” in [0041]. It is explained that there is.

  Therefore, the deodorizing body in this invention is a porous structure having an average diameter of gas molecules or more, or a deodorizing body (including titanium oxide) honeycomb body, and contains transparent ultrafine particles that can be sprayed on the clothes fibers. It is not a liquid catalyst.

  Further, cited document 5 (Japanese Patent Laid-Open No. 9-104852) discloses “a paste characterized by containing one of an antibacterial member and an antistatic agent” [Claim 1], wherein “air pressure or vaporization”. A spray type in which paste is sprayed by gas ”[Claim 6],“ This paste contains a photocatalyst such as titanium dioxide, and the external dimensions of the photocatalyst are 0.03 to 100 μm in powder form, and are dried after application. The article to be coated is clothing or paper, and the paste is dried and fixed by ironing after spray application ”[Claim 20] to [Claim 25].

  And [0022] to [0023], “In the present invention, as part of gluing and ironing operations for home use or business use, at least one of the antibacterial member and antistatic agent is applied to clothing, towels, sheets, etc. As a result, it is possible to wear sterilized clothing even at home, and to enable a healthy and comfortable life.

  Furthermore, [0050] states that “a fine powder particle of photocatalyst made of titanium dioxide or a mixture of titanium dioxide and activated carbon included in the paste has an outer shape of 0.03 to 100 μm, a film of several μm to 100 μm It may be sprayed or printed to a thickness ".

However, in this invention, the fine powder particles of photocatalyst such as titanium oxide are extremely rough with an outer shape of 0.03 to 100 μm, and there is no description that titanium oxide is fibrous, and the fiber width and thickness, and fiber length. Since the aspect ratio and specific surface area are unknown, it is unclear whether or not it has sufficient adhesion to fibers when sprayed on clothes. In addition, although the article to be coated is described as clothing, it is pasty, so it cannot sufficiently enter into the fibers of the clothing, and since it is pasty, it takes a lot of moisture and takes a long time to dry. Since the paste is coated, the surface exposure of the particles is extremely poor.

  Further, in cited document 6 (Japanese Patent Laid-Open No. 10-314543), “the malodorous gas component in the air to be treated 11 is adsorbed to the titanium dioxide particles 5 in the deodorizing tower 3, and the titanium dioxide particles 5 are passed through the pipe 37. It is guided to the regeneration tower 7 and irradiated with black light from the black light illuminator 31 to oxidatively decompose and regenerate the adsorbed malodorous gas component ”.

  "Titanium dioxide particles have a light specific gravity and a diameter of 1.4 to 2.0 mm, so that they can be easily fluidized by air flow" [0026] "and" ... float. The titanium dioxide particles 5 are irradiated with black light such as ultraviolet rays from a black light illuminator 31 provided on the side of the reproduction shelf 27. By this irradiation, malodorous gas components adsorbed on the titanium dioxide particles 5 are emitted. It is oxidized and decomposed by the light energy of black light and is not brominated.Titanium dioxide particles 5 promote oxidative decomposition as a photocatalyst.Thus, titanium dioxide particles 5 regenerate the adsorption performance again ”[0027] Yes.

  However, in the present invention, the titanium oxide particles are as coarse as 1.4 to 2.0 mm [Claim 2], and when sprayed onto the fibers of clothes, they are not nanometer-sized particles and are sufficiently dispersed in the fibers. The adhesion to fibers is weak. In addition, the specific surface area is not limited to a nanometer dispersion, the exposure rate of the particle surface is small, and a high photocatalytic activity cannot be obtained.

  Further, cited document 7 (utility model registration No. 312458) discloses a “multifunctional sterilization deodorizing apparatus composed of a fuselage, an ozone generator, a sterilizer, a fan and an installation table, and sterilized / disinfected inside. The airframe is composed of a sealed box with a space for storing articles to be used, and has an air vent at the top, an ozone generator that is installed at the upper end of the airframe and sterilizes by blowing out ozone, It is composed of a sterilizer that is installed and performs sterilization / slow odor action, a fan that is installed above the machine and exhausts air inside the machine from the ventilation holes, and a table on which articles to be sterilized and disinfected are placed. A multi-functional sterilization deodorizing apparatus characterized in that "Claim 1" is described.

  And it is described that “the sterilizer is an ultraviolet ray tube [Claim 6], a photocatalyst sterilizer [Claim 7], a black light ultraviolet ray tube [Claim 9]”.

As described in [0010], each of these sterilizers is an independent sterilizer and is not an ultraviolet tube or a black light ultraviolet tube provided to promote activation of a photocatalyst made of titanium oxide.

  Further, in cited document 8 (Japanese Patent Laid-Open No. 11-028144), “a clothing holding inner mold provided with a hook suspended on a bag or the like and a hinge can be opened and closed like a shell, and the clothing holding inner mold and the gap A deodorizing box having a deodorizer and a fan, and an exhaust port and the deodorizing box in communication with each other. A clothing deodorizing apparatus comprising an exhaust pipe through which exhaust flows, an intake pipe through which the air blowing hole communicates with the deodorizing box and through which the air flows ”[Claim 1] Are listed.

  Further, it is stated that “the deodorizer includes at least one deodorizer among an ultraviolet deodorizer, a photocatalyst deodorizer, an ozone deodorizer, and an ozone catalyst deodorizer” [Claim 5].

  As described in [0020] to [0022], this sterilization apparatus "... blows air strongly to the clothing surface from a short distance and constantly replaces the clothing surface with fresh air to volatilize malodors. Furthermore, it is designed to deodorize bad odors in the exhaust gas .... Moreover, since no deodorant is used, there is no danger of stains or alteration of clothes.

  That is, in this invention, the photocatalyst deodorizer 13 is not described as being fibrous titanium oxide. Therefore, it cannot be understood whether or not there is sufficient adhesion to the fibers when sprayed on the fibers of the clothes. In addition, since titanium oxide is not a dispersion but a porous body, the specific surface area is limited, and the exposure rate of the particle surface is small and a high photocatalytic activity cannot be obtained.

  Further, in cited reference 9 (Japanese Patent Laid-Open No. 10-323239), “a storage container for storing a garment configured to be hermetically sealed, and an insect repellent attached to the garment provided in the storage container and / or A deodorizing apparatus for clothing comprising a deodorizing unit that decomposes and / or adsorbs gas generated from fine particles of a dry cleaning solvent is described.

  Further, “the deodorizing unit includes an ultraviolet lamp and a photocatalyst that receives ultraviolet rays from the ultraviolet lamp” [Claim 4], and “... Stores the air sealed in the storage container. A blower forcibly circulating through the deodorizing part in the container is disposed ”[Claim 5].

  “The deodorizing section includes an ultraviolet lamp and a photocatalyst that receives the ultraviolet light from the ultraviolet lamp. The photocatalyst reacts to decompose a toxic gas on the surface and change it into harmless and odorless. By this, it is possible to remove harmful gases ”[0012] [0013].

  However, in the present invention, the photocatalytic deodorizer 13 is not described as being titanium oxide, and is not intended to spray a solvent containing titanium oxide fibrous fine powder onto clothing fibers.

Problems to be solved by the invention

  In the present invention, fibrous titanium oxide is dispersed in the fiber of clothes and firmly adhered to the fiber, and the exposure degree of the particle surface is extremely increased to 90% or more, and the temperature of the hot air in the hot air drying means is changed to the fiber. Photocatalytic deodorizing and sterilizing method, which can be dried at an extremely low temperature of 30 to 120 ° C. without causing any troubles, and the fibrous titanium oxide can be firmly and firmly fixed to the entire fiber of clothes by hot air to obtain a high photocatalytic activity. And it is providing the transparent liquid photocatalyst used for this.

Cited Document 1 JP 2000-288405 JP Cited Document 2 JP 2001-205099 JP Cited Document 3 JP 2005-329101 JP Cited Document 4 JP 2005-034254 JP Cited Document 5 JP 09-104852 A Cited Reference 6 Japanese Patent Laid-Open No. 10-314543 Cited Reference 7 Utility Model Registration No. 31244458 Cited Reference 8 Japanese Patent Laid-Open No. 11-028144 Cited Reference 9 Japanese Patent Laid-Open No. 10-323239

Means to solve the problem

  The invention according to claim 1 is a photocatalyst ejecting means for ejecting a liquid photocatalyst to a fiber material such as clothes in a sealed chamber, an ultraviolet irradiation means for irradiating the photocatalyst adhering to the fiber material with ultraviolet light, and a liquid adhering to the fiber material. And hot air drying means for blowing hot air to the photocatalyst and drying the photocatalyst. The photocatalyst ejecting means ejects a transparent liquid photocatalyst in which an appropriate amount of the fibrous titanium oxide ultrafine particles is dispersed. Thus, the temperature of the hot air in the hot air drying means is 30 to 120 ° C., and the fibrous titanium oxide ultrafine particles filling the sealed chamber are uniformly fixed to the whole fiber of the fibrous material by hot air and dried. A method is provided.

  In the present invention, the fibrous titanium oxide ultrafine particles are dispersed in the fibers of the clothes alone and firmly adhered to the fibers, and the degree of exposure of the particle surface can be extremely increased to 90% or more, and the hot air drying is performed. The temperature of the hot air in the means can be dried and fixed at an extremely low temperature of 30 to 120 ° C., which does not interfere with the fiber, and the fibrous titanium oxide is firmly dried and fixed to the entire fiber of the clothes by the hot air, even in a dark sealed room. A photocatalytic activity can be obtained. Moreover, since the said liquid photocatalyst is transparent, a fiber thing after a process does not discolor. And the photocatalyst deodorizing sterilization method which can maintain a deodorizing, disinfection, and antifungal effect over a long period of time can be provided. In addition, the fiber of the garment is composed of a starting yarn as a raw material, an intermediate raw material thread obtained by stitching this yarn, and a final woven fiber obtained by stitching this intermediate raw material yarn. The fibrous titanium oxide of the present invention Since the ultrafine particles can penetrate into the starting yarn fibers that are the raw material and can be fixed, they can be firmly fixed to maintain the above effect over a long period of time.

  The invention of claim 2 is that the inorganic element in the liquid photocatalyst in the photocatalyst ejecting means is a semi-quantitative value, at least Ti is 90 to 97 wt%, Si is 2.3 to 3.0 wt%, Ag is 1.4 to 2 A transparent liquid photocatalyst containing 0.2 wt% and 0.2 to 0.3 wt% Zn is provided.

  In the present invention, it is possible to adjust the ultraviolet absorption region, dielectric constant, photocatalytic activity, proton conductivity, solid acid characteristics, etc. of titanium oxide obtained by the above oxide remaining, and further, thermal stability and Chemical stability and the like can also be adjusted. Further, by adding Ag, a high photocatalytic activity can be obtained even in a dark sealed room. Furthermore, by containing Si, the viscosity can be lowered and the fluidity can be increased, and the fibrous titanium oxide ultrafine particles can easily enter the fibers of the clothes and can be quickly dried. If it is out of the above range, it is considered that these effects cannot be obtained.

  According to a third aspect of the present invention, the organic element in the liquid photocatalyst in the photocatalyst ejecting means has a quantitative value, at least C is 55 to 65 wt%, H is 8 to 12 wt%, and N is 0.2 to 0.4 wt%. A liquid photocatalyst is provided.

  In the present invention, when the organic element of CHN is in the above range, the temperature of the hot air in the hot air drying means is 30 to 120 ° C., which does not hinder the fibers, and the fibrous titanium oxide is firmly attached to the clothes fibers. And the drying speed can be extremely fast. If it is out of the above range, it is considered that these effects cannot be obtained.

In the invention of claim 4, the fibrous titanium oxide in the liquid photocatalyst is ultrafine particles, the average fiber width and thickness are 1 to 50 nm, the average fiber length is 10 to 1000 nm, the average aspect ratio is 2 to 100, A transparent liquid photocatalyst having a specific surface area of 30 m ² / g or more is provided.

In this invention, very fine fibrous titanium oxide can be dispersed throughout the fiber of the garment and firmly adhered to the fiber of the garment, and the degree of exposure of the particle surface can be greatly increased by 90% or more, resulting in high photocatalytic activity. The effect can be obtained. Further, extremely fine fibrous titanium oxide can be dispersed throughout the fiber of the clothes, and the hot air in the hot air drying means can be dried at an extremely low temperature of 30 to 120 ° C. which does not affect the fiber. If it is outside the above range, the reaction diffusion of the fibrous titanium oxide is not sufficiently performed, and a high photocatalytic activity cannot be obtained. Preferably, the average fiber width and thickness are 10 to 30 nm, the average fiber length is 20 to 100 nm, the average aspect ratio is 3 to 50, and the specific surface area is 50 m ² / g or more.

The production of fibrous titanium oxide ultrafine particles is achieved by hydrothermally treating an aqueous dispersion sol in which a titanium oxide composite oxide is dispersed in water in the presence of at least an alkali metal hydroxide of SiO ₂ , AgO, and ZnO. can get. These fibrous titanium oxides preferably have a fiber width and thickness of 1 to 50 nm, a fiber length of 10 to 1000 nm, and an aspect ratio of 2 to 100 or more, and water dispersion of titanium oxide composite oxide particles. Use sol. With the above particle size, a stable water-dispersed sol can be obtained, and fibrous titanium oxide ultrafine particles having excellent particle dispersibility at a very high level can be obtained.

  The concentration of the water-dispersed sol of the titanium oxide particles and the titanium oxide-based composite oxide particles composed of oxides other than titanium oxide and titanium oxide is preferably in the range of 2 to 50% by weight as oxides. In such a concentration range, the sol is stable and the fibrous titanium oxide ultrafine particles can be efficiently generated without aggregation of the particles during the alkali treatment.

As described above, particularly when an alkali metal hydroxide of SiO ₂ , AgO, or ZnO is contained, fibrous titanium oxide ultrafine particles are easily generated, and the ultraviolet absorption region and photocatalytic activity of the fibrous titanium oxide ultrafine particles are adjusted. Furthermore, thermal stability and chemical stability can be obtained. Content of oxides other than the said titanium oxide is 1-25 weight%, Preferably it is 3-8 weight%. In such a range, fibrous titanium oxide ultrafine particles are generated at a high level.

  In this embodiment, a binder made of titanium peroxide or composite titanium peroxide and an organic polymer compound is used for the composite titanium oxide ultrafine particles. Such titanium peroxide or composite titanium peroxide is usually in a solution state (transparent liquid photocatalyst). Such a titanium peroxide or composite titanium peroxide has a refractive index comparable to that of the composite titanium oxide fine particles, so that it does not scatter light due to coating components and has excellent transparency. It can be.

A titanium chloride aqueous solution was diluted with pure water to prepare a titanium chloride aqueous solution having a concentration of 5% by weight as TiO ₂ . This aqueous solution was neutralized and hydrolyzed by adding it to 15% aqueous ammonia adjusted to a temperature of 5 ° C. Subsequently, the produced gel was washed by filtration to obtain an orthotitanic acid gel having a concentration of 9% by weight as TiO ₂ .

After 100 g of this orthotitanic acid gel was dispersed in 2900 g of pure water, 800 g of hydrogen peroxide having a concentration of 35% by weight was added and heated at 85 ° C. for 3 hours with stirring to prepare a peroxotitanic acid aqueous solution. The concentration of the obtained peroxotitanic acid aqueous solution as TiO ₂ was 0.5% by weight. Then heated for 10 hours at 95 ° C. and a titanium oxide particle dispersion liquid, the molar ratio of TiO ₂ dispersion in the titanium oxide particle dispersion liquid was added tetramethylammonium hydroxide oxa de so that 0.016. Next, a slight amount of SiO ₂ , AgO and ZnO was added and hydrothermally treated at 230 ° C. for 5 hours to prepare a composite titanium oxide particle dispersion, that is, a transparent liquid photocatalyst used in the present invention. The titanium oxide at this time was fibrous titanium oxide ultrafine particles having an average fiber width and thickness of 1 to 50 nm, an average fiber length of 10 to 1000 nm, and an average aspect ratio of 2 to 100.

  The measurement result of the composition ratio of the inorganic element and the organic element of the transparent liquid photocatalyst is shown below. In order to grasp the composition of the transparent liquid photocatalyst, water was evaporated from the transparent liquid photocatalyst, and only the dissolved components were concentrated and collected, and the amounts of inorganic elements and organic elements contained therein were examined. The sample solution was put into a beaker, water was evaporated using a 120 ° C. hot plate, and the catalyst component was concentrated and collected. CHN analysis was also added because of the expected presence of organics.

Qualitative and semi-quantitative determination of inorganic elements (fluorescence X-ray method);
Measured with the following equipment and conditions, qualitative and semi-quantitative analysis of the contained elements.
Apparatus: Rigaku Electric Co., Ltd. fully automatic X-ray fluorescence analyzer, RIX-3000
Tube; Rh tube Measurement diameter: 25mmφ

Judgment amount result of inorganic element (element heavier than Na)

Determination of CHN (combustion thermal conductivity method);
Equipment: MT-700CN made by Yanaco

CHN measurement results

Analysis of measurement results From the measurement results, the amount of elements contained in the liquid photocatalyst is calculated as follows.

Content of the said inorganic element was computed from the measured value by the following formula.
Inorganic element content = measured value of inorganic element x (100-CHN content) / 100
That is, the content (about 70%) of CHN considered to be derived from organic substances was excluded from the total amount, and the remaining (about 30%) was allocated by the inorganic element content. However, in this measurement, since the content of 0 (oxygen) that is necessarily contained cannot be grasped, “<” is added to the content of inorganic elements. Assuming that the form of Ti is TiO ₂ , the weight ratio of Ti and O contained is 100: 67, and the estimated values in the above table are converted as shown in the following table.

Content estimate (considering oxygen O content)

CN is judged to be an element derived from an organic binder, and occupies about 70% or more of the content (in addition, there is a high possibility that oxygen O is present). Ti (TiO ₂ ) is the main component of the photocatalyst.

Ag is a component added mainly as an antibacterial substance, but its content is judged to be far less than that of TiO ₂ . Moreover, high photocatalytic activity can be obtained even in a dark sealed room by adding Ag.

Zn is added for improving the adsorptivity of the photocatalyst. In some cases, basic ZnO is added to acidic TiO ₂ .

  Si is a binder component (silica sol), which can lower the viscosity and increase the fluidity. K and Cl are not essential components.

Sterilization test Test method; light irradiation film adhesion method reference; polyester film irradiation condition; about 1000 to 2000 Lx
Room temperature: 20-25 ° C

  A high sterilization effect can be confirmed from the above test results. In addition, even in the case of light shielding, there is a high sterilization effect, which seems to be exerting the effect of silver ions of added silver (AgO).

Sterilization evaluation 1 kg of cotton towel was put into an apparatus using the photocatalyst deodorizing and sterilizing method of the present invention for 30 minutes, and hot air was blown at 100 ° C. to dry to obtain a sample towel. In addition, a part of the treated sample towel was washed for 10 minutes using a detergent (High Top manufactured by Kao Soap Co., Ltd.) and then washed with tap water for 5 minutes 50 times, and finally at 100 ° C. And dried to obtain another sample towel.
2. Instead of the cotton towel, 1 kg of polyester fiber cloth was used. Otherwise, the same operation as above was performed.
3. Antibacterial test E. coli and Staphylococcus aureus were suspended in phosphate buffer, 75 ml of this solution and 0.75 g of the transparent liquid photocatalyst used in the present invention were placed in a 200 ml Erlenmeyer flask, and kept at 25 ° C. ± 5 ° C. And vibration treatment at 330 rpm for 1 hour. The number of viable bacteria in this treatment solution was measured, and the following sterilization rate was calculated.

＊すべて無臭であった。

* All were odorless.

  From the above results, it is understood that the photocatalyst deodorizing and sterilizing method of the present invention shows excellent sterilization not only for cotton cloth but also for polyester fiber, and the sterility is hardly lowered even after washing. Is done. This is presumably because the adhesion of the titanium oxide ultrafine particles to the fibers is extremely strong according to the photocatalyst deodorizing and sterilizing method of the present invention and the transparent liquid photocatalyst.

  The ultraviolet irradiation means used in the present invention is black light and has the following wavelength range of 300 to 400 nm. Moreover, a high photocatalytic activity can be obtained even in a dark sealed room.

  As an apparatus used for the sterilization evaluation using the method of the present invention, for example, a transparent liquid photocatalyst is ejected from one or a plurality of nozzles toward the peripheral direction of clothes in a sealed chamber, and a mist is filled in the sealed chamber. The transparent liquid photocatalyst in the form of hot air is blown out from one or a plurality of air outlets, the titanium oxide ultrafine particles of the transparent liquid photocatalyst enter the clothing fibers, and the titanium oxide ultrafine particles are adhered to the clothing fibers and fixed. Allow to dry. The sealed chamber may be a square or a circular box. In addition, one or more black lights are provided on the sealed indoor wall at locations where the titanium oxide ultrafine particles adhering to the clothes fibers are uniformly irradiated. Further, the hot air can be jetted first, and the cool air after the treatment can be jetted to accelerate the curing of the transparent liquid photocatalyst.

The invention's effect

  In the present invention, the fibrous titanium oxide ultrafine particles are dispersed in the fibers of the clothes alone and firmly adhered to the fibers, and the degree of exposure of the particle surface can be extremely increased to 90% or more, and the hot air drying is performed. The temperature of the hot air in the means can be dried and fixed at an extremely low temperature of 30 to 120 ° C., which does not interfere with the fiber, and the fibrous titanium oxide is firmly dried and fixed to the entire fiber of the clothes by the hot air, even in a dark sealed room. A photocatalytic activity can be obtained. Further, since the liquid photocatalyst is transparent, the treated fiber is not discolored. And the photocatalyst deodorizing sterilization method which can maintain a deodorizing, disinfection, and antifungal effect over a long period of time can be provided. In addition, the fiber of the garment is composed of a starting yarn as a raw material, an intermediate raw material thread obtained by stitching this yarn, and a final woven fiber obtained by stitching this intermediate raw material yarn. The fibrous titanium oxide of the present invention Since the ultrafine particles can enter and fix the fibers of the starting yarn as a raw material, it is possible to provide a photocatalyst deodorizing and sterilizing method that can be firmly fixed and maintain the above effect for a long time.

  In addition, the ultraviolet absorption region, dielectric constant, photocatalytic activity, proton conductivity, solid acid characteristics, etc. of titanium oxide obtained by the above oxide remaining can be adjusted, and further, thermal stability and chemical stability can be adjusted. Sex etc. can also be adjusted. Further, by adding Ag, a high photocatalytic activity can be obtained even in a dark sealed room. Furthermore, by containing Si, the viscosity can be lowered and the fluidity can be increased.

  Further, when the organic element of CHN is in the above range, the temperature of the hot air in the hot air drying means is firmly fixed to the clothes fibers at a temperature as low as 30 to 120 ° C. which does not affect the fibers. And the drying rate can be very fast.

  Furthermore, ultra-fine fibrous titanium oxide particles can be uniformly dispersed in the fibers of the garment and firmly adhered to the entire garment fibers, and the degree of exposure of the particle surface can be greatly increased by 90% or more, resulting in high photocatalytic activity. Obtainable. Also, the ultrafine fibrous titanium oxide particles can be dispersed throughout the fiber of the clothes, and the hot air in the hot air drying means can be dried at an extremely low temperature of 30 to 120 ° C., which does not interfere with the fiber. In addition, since the photocatalyst is transparent, there is no fear that the clothes will be colored even when it is white.

Claims (4)

A photocatalyst ejecting means for ejecting a liquid photocatalyst to a fiber material such as clothes in a sealed room, an ultraviolet irradiation means for irradiating the photocatalyst attached to the fiber material with ultraviolet light, and hot air is blown to the liquid photocatalyst attached to the fiber material. A hot air drying means for drying, wherein the photocatalyst in the photocatalyst ejecting means is a fibrous titanium oxide ultrafine particle, and a transparent liquid photocatalyst in which an appropriate amount of the fibrous titanium oxide ultrafine particle is dispersed is ejected, and the hot air drying means The photocatalyst deodorizing and sterilizing method in which the temperature of the hot air in is set to 30 to 120 ° C., and the fibrous titanium oxide ultrafine particles filled in the sealed chamber are uniformly fixed to the whole fiber of the fiber material by hot air and dried. When the inorganic element in the liquid photocatalyst in the photocatalyst ejecting means is a semi-quantitative value, at least Ti is 90 to 97 wt%, Si is 2.3 to 3.0 wt%, Ag is 1.4 to 2.2 wt%, and Zn is 0. A transparent liquid photocatalyst containing 2 to 0.3 wt%. A transparent liquid photocatalyst containing at least C in an amount of 55 to 65 wt%, H in an amount of 8 to 12 wt%, and N in an amount of 0.2 to 0.4 wt% in a quantitative value of an organic element in the liquid photocatalyst in the photocatalyst ejecting means. The titanium oxide in the liquid photocatalyst is a fibrous ultrafine particle having an average fiber width and thickness of 1 to 50 nm, an average fiber length of 10 to 1000 nm, an average aspect ratio of 2 to 100, and a specific surface area of 30 m ² / The transparent liquid photocatalyst which is more than g.