JP2000296169A - Toxic substance removing system using photoreactive semiconductor disk - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently deodorize and sterilize an odor material by combining a disk- shaped photoreactive semiconductor honeycomb disk applied with or internally added with a photoreacive semiconductor and being fabricated from a sheet such as metal, paper and nonwoven fabric with a luminaire having a circular fluorescent lamp. SOLUTION: A circular fluorescent lamp 2 for generating the radiation light for activating a photocatalyst function of a photoreactive semiconductor is arranged in a luminaire body 1, and a photoreactive semiconductor disk composed of a photoreactive semiconductor carrying sheet having a photoreactive semiconductor containing layer having a photocatalyst function is arranged in an upper position of the circular fluorescent lamp 2 on at least one surface of a support. This photoreactive semiconductor disk is desirably formed in a shape such as a circular shape, a triangular shape and a quadrangular shape so that the surface area of a honycomb shape, a lattice shape and a corrugate shape becomes large as much as possible. The photocatalyst function of the photoreactive semiconductor is activated by lighting of the fluorescent lamp 2 to deodorize and sterilize an odor material such as a formalin smell and a tobacco smell.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoreactive semiconductor disk and a harmful substance removing system using the same, and more particularly, to a round fluorescent lamp and a photoreactive semiconductor disk used as indoor lighting equipment. The present invention relates to a harmful substance removal system that performs indoor disinfection and deodorization by using in combination.

[0002]

2. Description of the Related Art With increasing interest in the living environment, there has been an increasing demand for the removal of harmful substances in daily life such as odors, and the development of air purifiers incorporating odor removal devices and the like has been actively carried out. I have. In these devices, a filter mainly containing activated carbon is used, and a method of adsorbing malodorous substances on activated carbon has been adopted. However,
Activated carbon has an adsorbing effect but has no decomposability, so it becomes saturated when a certain amount of malodorous substance is absorbed, and the filter must be replaced periodically.

In recent years, as a solution to such a problem, a composite material in which activated carbon and a catalyst for decomposing harmful substances are combined has been developed. For example, JP-A-1-234729 describes an air conditioner incorporating a photoreactive semiconductor composite in which titanium oxide is supported on honeycomb activated carbon. In this case, a part of the malodor component to be adsorbed is decomposed by OH radicals generated in the photoreactive semiconductor, so that the adsorption ability of the activated carbon can be maintained for a relatively long time.
However, this method requires activated carbon having a special honeycomb structure in order to support the photoreactive semiconductor and enhance the photoreaction efficiency, and requires a special process for retaining titanium oxide on the surface and inside the honeycomb. Was needed.

[0004] Japanese Patent Application Laid-Open No. 2-252241 describes a photocatalytic device in which a hollow cylindrical honeycomb structure made of a metal oxide catalyst is provided around an ultraviolet irradiation lamp.

Further, a method for removing harmful substances in a gas phase using photocatalytic titanium oxide is disclosed. For example, JP-A-2-253848 describes an ozone decomposition catalyst in which an anatase type titanium oxide is supported on an inorganic fibrous carrier. In Japanese Patent Application Laid-Open No. 3-233100, a mixture of titanium dioxide and activated carbon and a mixture having a wavelength of 300 n
It describes a ventilating facility consisting of a light source that emits light of m or more. JP-A-4-256755 discloses that titanium dioxide can be used as a deodorant and deodorant for home use by supporting it on granular pulp. In addition, Kusunaga et al. Carried out photodecomposition of organic halogen compounds by holding titanium dioxide on ceramic paper (Journal of the Electrochemical Society, vol. 60, p. 107, 1992).
Year).

The photocatalytic decomposition of a gas-phase harmful substance by a photoreactive semiconductor involves the approach and adsorption of a gas-phase harmful substance to a photoreactive semiconductor, photodecomposition by near-ultraviolet light, and by-products formed on the photoreactive semiconductor surface. It has been confirmed that the process proceeds through the process of withdrawal.

On the other hand, titanium oxide has long been known as one of the photoreactive semiconductors. However, the ability of titanium oxide to decompose harmful substances varies greatly depending on the type of titanium oxide. For example, conventionally, for the purpose of improving whiteness and opacity, titanium oxide has been widely used as an internal pigment for papermaking.The internal titanium oxide for papermaking has a large particle diameter of 0.1 to 0.2 microns. Therefore, the specific surface area was as low as about 10 m ² / g, and it was recognized that the photocatalytic decomposition ability of high-concentration gas-phase harmful substances was low.

Therefore, the present inventor has conducted a detailed investigation on the photocatalytic decomposition ability of internally added titanium oxide powder for papermaking, and
It has been found that, if it is a gas phase harmful substance of m order or less, the titanium oxide powder for papermaking has the ability to decompose gas phase harmful substance efficiently by near-ultraviolet light irradiation.

However, titanium oxide internally added for papermaking is used together with a binder such as polyvinyl alcohol and latex.
When a sheet is formed by coating a substrate such as paper, plastic, or non-woven fabric, the binder fixes the titanium oxide fine particles to the substrate, but also covers the surface of the titanium oxide fine particles at the same time. It was confirmed that the substance could not be adsorbed on the surface of the titanium oxide fine particles, and the photocatalytic decomposition ability was not sufficiently exhibited.

In order to improve the photocatalytic decomposition ability, the average particle diameter is 0.002 to 0.05 μm and the specific surface area is 100 to
Ultrafine titanium oxide of 350 m ² / g has been developed and is being put to practical use. However, ultrafine titanium oxide has a very high photocatalytic decomposition ability and decomposes organic compounds that come into contact with it, so it is coated on paper, plastic, nonwoven fabric, and other base materials together with binders such as polyvinyl alcohol and latex. When formed into a sheet, the binder and the base material are decomposed in a short time, so that it has been difficult to keep the ultrafine titanium oxide fixed on the base material.

Japanese Patent Application Laid-Open No. 9-31335 describes a resin composition in which a mixture of a titanium oxide photocatalyst coated with a porous inorganic substance and an inorganic deodorizing adsorbent is mixed with an organic resin. However, in this method, when coating the titanium oxide photocatalyst with the porous inorganic substance, 550
A calcination step of heat treatment at 1 ° C. for 1 hour was required, and the titanium oxide photocatalyst coated with a porous inorganic substance was taken out as a powder and then blended with an organic resin, which was complicated.

A photocatalytic air purifier having a square or rectangular planar honeycomb formed from a sheet of paper or non-woven fabric containing photocatalyst titanium oxide and a corrugate already installed near a straight tube type ultraviolet lamp (black light). Machines and air conditioners are in practical use.

[0013]

On the other hand, as home lighting fixtures, lighting fixtures equipped with round fluorescent lamps have become widespread. However, by utilizing this round fluorescent lamp, indoor bacteria, viruses, formalin odor becomes a problem in the sick house syndrome, enters cigarette smell, from the main road to the room NO _x
There has never been a method for deodorizing odorous substances such as gas which poses a health problem.

In view of such circumstances, an object of the present invention is to provide a photoreactive semiconductor disk molded from a sheet of paper, nonwoven fabric, metal or the like coated with or internally coated with a photoreactive semiconductor. An object of the present invention is to provide a harmful substance removal system that efficiently removes and sterilizes indoors by using a combination of these.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a round fluorescent lamp for generating radiation that activates the photocatalytic function of a photoreactive semiconductor, and a light having a photocatalytic function on at least one surface of a support. A photoreactive semiconductor carrier sheet provided with a reactive semiconductor-containing layer, or a photoreactive semiconductor disc made from a photoreactive semiconductor carrier sheet having photoreactive semiconductor fine particles having a photocatalytic function added inside a support. The problem has been solved by providing a harmful substance removal system in which the round fluorescent lamp and the photoreactive semiconductor disk are provided in parallel contact or adjacent to each other.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The photoreactive semiconductor disk used in the present invention is desirably prepared so as to have as large a surface area as possible, such as a honeycomb shape, a lattice shape, and a corrugated shape. The shape of the photoreactive semiconductor disk includes various shapes such as a circle, a triangle, a square, a pentagon, a hexagon, and an octagon.When combined with a round fluorescent lamp, a circle and a square are preferable, and a circular shape is preferred. Disk-shaped photoreactive semiconductor disks are most desirable. The disk shape of the disk-shaped photoreactive semiconductor disk of the present invention means a complete disk shape and a substantially disk shape. Further, the present invention also encompasses a donut shape having a hole at the center of the disc-shaped photoreactive semiconductor disk.

While a straight fluorescent lamp emits light radially, a round fluorescent lamp has a donut shape, so that light crosses and there is a circular region where light intensity increases. Therefore, when a photoreactive semiconductor disk is installed in this circular area, the photocatalytic function is dramatically improved.

A photoreactive semiconductor honeycomb disk as an example of the photoreactive semiconductor disk of the present invention can be manufactured by the following method. First, a photoreactive semiconductor support sheet provided with a photoreactive semiconductor-containing layer by applying and drying a photoreactive semiconductor coating composition having a photocatalytic function on at least one surface of the support, or a photocatalytic function in the support. A photoreactive semiconductor supporting sheet internally containing the photoreactive semiconductor fine particles is prepared. Next, the photoreactive semiconductor supporting sheets are stacked while a fixed number of sheets are glued, and dried to obtain a honeycomb block. Further, this is cut and spread at a fixed width to produce a planar honeycomb. By bonding or cutting both ends of the planar honeycomb, photoreactive semiconductor honeycomb disks of various shapes can be obtained. If necessary, a fixing stopper can be attached to the center of the photoreactive semiconductor honeycomb disk.

Similarly, a photoreactive semiconductor lattice disk is obtained by forming the photoreactive semiconductor carrier sheet into a lattice having square or rectangular cells.
Also, the photoreactive semiconductor carrier sheet and the photoreactive semiconductor carrier sheet formed into a corrugated shape are laminated while alternately gluing them to obtain a laminated corrugated block, and a cylinder with a hole in the center by bonding both ends. A photoreactive semiconductor corrugated block is obtained. When this is cut to a desired thickness, a photoreactive semiconductor corrugated disk is obtained.

As another method, a honeycomb disk, a lattice disk, and a corrugated disk are prepared in advance, dipped in a coating solution containing a photoreactive semiconductor, and baked if necessary, thereby producing a photoreactive semiconductor. It can also be carried on a disk substrate.

The thickness of the photoreactive semiconductor disk is preferably from 1 to 50 mm, and most preferably from 5 to 20 mm.

In addition, round fluorescent lamps include 15, 20, 30, 32,
There are several sizes of 40 watts, but with a disc-shaped photoreactive semiconductor disk, by setting the diameter freely,
Compatible with any size round fluorescent lamp.

Further, the support is not particularly limited, such as metal such as aluminum, plastic, glass, ceramic, paper, non-woven fabric, coated paper, and synthetic paper. Particularly, metal, paper, non-woven fabric, coated paper, and synthetic paper are preferable. .

Regarding the positional relationship between the round fluorescent lamp and the photoreactive semiconductor disk, it is best that the round fluorescent lamp and the photoreactive semiconductor disk are in contact in a parallel arrangement.
This is because the photoreactive semiconductor disk is heated and dried by the heat generated from the fluorescent lamp due to direct contact with the fluorescent lamp, and the photocatalytic function of the photoreactive semiconductor is enhanced. However, a certain distance (50 mm or less) may be provided as long as the ultraviolet light receiving intensity does not decrease. In addition, the photoreactive semiconductor disk may be installed either above or below the round fluorescent lamp, but in order to prevent the illuminance of the luminaire from lowering, the photoreactive semiconductor disk should be installed above the round fluorescent lamp. Is preferable, and an effect as a light reflection plate can be expected. Further, when the photoreactive semiconductor disk is placed under a round fluorescent lamp, the illuminance is slightly reduced, but the effect of preventing light scattering from the fluorescent lamp can be expected.

In a household lighting fixture equipped with a commercially available round fluorescent lamp, the round fluorescent lamp is usually held on the lighting fixture body by three metal stoppers. Therefore, if slits are formed in three places on the outer periphery of the photoreactive semiconductor disk of the present invention, it can be easily fixed to the metal stopper of the round fluorescent lamp.

The photoreactive semiconductor in the present invention includes:
Metal oxide particles such as zinc oxide, tungsten trioxide, titanium dioxide, cerium oxide, and titanium peroxide are good, and titanium dioxide is particularly preferable.

Hereinafter, titanium oxide as a photoreactive semiconductor,
A photoreactive semiconductor supporting sheet using a support mainly composed of an organic composition as a support, that is, a titanium oxide supporting sheet will be described.

The titanium oxide-carrying sheet of the present invention is a sheet provided with a titanium oxide-containing layer on a support or a sheet in which titanium oxide is internally added to the support. When the titanium oxide-containing layer is provided on the support, the titanium oxide-containing layer may be provided on both sides of the support, and the photocatalytic efficiency can be maximized by the double-side coating. The amount of the titanium oxide-containing layer applied to the support is preferably 0.1 to 20 g / m ^{2 on} one side, and most preferably 1 to 10 g / m ² , in consideration of the transmission efficiency of ultraviolet rays. Further, an under layer may be provided between the support and the titanium oxide-containing layer, if desired, for improving the adhesion.

The titanium oxide used in the present invention may be a conventional titanium dioxide, a titanium oxide compound called hydrous titanium oxide, hydrated titanium oxide, metatitanic acid, orthotitanic acid, or titanium hydroxide, or water. Includes all oxides. These titanium oxides are hydrolyzed by a titanium oxide source such as titanyl sulfate, titanium chloride, or an organic titanium compound in the presence of seeds for nucleation if necessary (hydrolysis method), and nucleation if necessary. A method of neutralizing by adding an alkali agent to a titanium oxide source while coexisting seeds for use (neutralization method), a method of vapor-phase oxidation of titanium chloride or an organic titanium compound (gas-phase oxidation method), and further hydrolysis And a method of firing the titanium oxide obtained by the neutralization method (a firing method). In addition, pure titanium oxide particles obtained by chemically modifying the surface of pure titanium oxide may be used as long as the photocatalytic function is activated by appropriate radiation. It is particularly preferable that the titanium oxide according to the present invention has many hydroxyl groups on its surface.

In the case of a titanium oxide supporting sheet having a titanium oxide-containing layer provided on a support, in a coating composition comprising titanium oxide and a binder, an inorganic binder wherein the binder is selected from silica sol and alumina sol It is preferable to apply a water-based titanium oxide coating composition comprising an organic polymer binder and an organic binder.

In the case of a titanium oxide supporting sheet having a titanium oxide-containing layer provided on a support, one of the important factors for determining the decomposability of harmful substances is that the titanium oxide fine powder is used during the drying process of the titanium oxide-containing paint. Powder and titanium oxide composite particles formed from an inorganic binder selected from silica or alumina sol and a delicate bond balance between the titanium oxide composite particles and the organic polymer binder. Improve by contacting more with decomposed substances,
Therefore, the larger the specific surface area of titanium oxide, the better. The specific surface area of the titanium oxide according to the present invention can be easily measured with a BET surface area measuring device. However, in consideration of practical resolution, the preferable specific surface area of the fine titanium oxide powder according to the present invention is 10 to 350 m ² / g. It is. Also, most titanium oxides do not have porosity and can be simply filled with a small particle size. The preferred particle size of the primary X-ray particles of the titanium oxide fine powder according to the present invention is 2 to 150 nm, and the particle size of the secondary particles generated by agglomeration of the primary particles is preferably 0.1 to 5 microns.

In the present invention, the mixing ratio of the titanium oxide fine powder and the inorganic binder selected from silica sol and alumina sol is one of the important factors which determines the effect of the present invention. That is, the mixing ratio determines the structure and function of the titanium oxide composite particles formed in the drying step. The mixing ratio of the titanium oxide fine powder and the silica sol or alumina sol is 5: 1 to 1: 5 by weight, and more preferably 2: 1 to 1: 2.

The organic polymer binder to be added when the titanium oxide-containing layer is provided on the support includes a water-soluble organic polymer compound or a thermoplastic polymer emulsion. The water-soluble organic high molecular compound means an organic high molecular compound which becomes a highly permeable colloid solution when dissolved in water, and has a film formed by drying and has high ultraviolet transmittance. Specific examples include starch, modified starch, polyvinyl alcohol, modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, polyacrylamide, cluster dextrin, chitosan, alginates, and cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose. In order to increase the transmittance, it is preferable that the reflection, scattering and absorption be as small as possible. In that respect, polyvinyl alcohol and polyacrylamide which are completely dissolved in water are preferable.

Further, the thermoplastic polymer emulsion is
It refers to a thermoplastic polymer emulsion that is a thermoplastic polymer dispersed in water. Specifically, an acrylic resin, a styrene-acryl copolymer, a styrene-butadiene copolymer, an ethylene-vinyl acetate copolymer, polypropylene, or the like can be used.

An appropriate addition ratio of the organic polymer binder to the titanium oxide fine powder is 3 to 25% by weight based on the whole solid content of the coating material. If it is less than 3%, the immobilization of the titanium oxide fine particles on the support is insufficient. When the content exceeds 25% by weight, the binding power increases, but the transmitting power of the active radiation decreases and the photodecomposition ability decreases.

The aqueous titanium oxide coating composition can be applied to a support by a conventional size press, a gate roll size press, a film transfer type size press device, or the like, a roll coater, a rod (bar) coater. , A blade coater, a spray coater, an air doctor (knife) coater, a curtain coater, and the like, and a method in which a small amount of other appropriate binder is applied together with a small amount of other appropriate binder in the same manner as in a general coating process. . Especially in the impregnation method,
The support may be wetted in advance.

In the case of a titanium oxide-carrying sheet in which titanium oxide is internally added to a support, the sheet contains titanium oxide fine powder and silica sol or alumina sol in a mixing ratio of 5: 1 to 1: 5 with respect to the titanium oxide fine powder. It is preferable to use titanium oxide composite particles produced by drying the aqueous dispersion. The average particle diameter of the titanium oxide composite particles is
3-15 microns are preferred.

The support mainly comprising an organic composition according to the present invention is not particularly limited as long as it can internally add titanium oxide or impregnate and apply an aqueous titanium oxide coating composition. The paper, the coated paper, the nonwoven fabric, the plastic film and the like mainly composed of synthetic resin (fiber) are used. Further, as the support, a support produced by mixing inorganic fibers such as glass fibers and carbon fibers or an inorganic composition with organic fibers can also be used.

The plant fibers used in the support material according to the present invention include chemical pulp such as kraft pulp, sulfite pulp and alkali pulp from softwood and hardwood, semi-chemical pulp, semi-mechanical pulp and mechanical pulp. In addition to wood fibers such as mulberry, mitsumata, straw, kenaf, bamboo, linter, bagasse, and vegetable non-wood fibers such as espart, regenerated fibers such as rayon and processed natural fibers such as cellulose derivative fibers are used. May be.

Further, olefin resins such as polyethylene and polypropylene, polyester resins such as declon, polyvinyl acetate, ethylene vinyl copolymer resin, polyamide resins such as nylon, polyacrylonitrile, acrylan, auron, Dynel, and Thermoplastic synthetic resin fibers made of acrylic resin such as Berel, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl ether, polyvinyl ketone, polyether, polyvinyl alcohol resin, diene resin, polyurethane resin, etc., phenol resin In addition to thermosetting synthetic resin fibers such as furan resin, urea resin, melamine resin, aniline resin, unsaturated polyester resin, alkyd resin, and epoxy resin, silicone-based fibers, fluorine-based fibers, and gold such as stainless steel wool. Fibers, various glass fibers and the like can be also used. The fibers used in the present invention may be of a single type or a combination of two or more types.

Further, flame retardancy can be imparted by adding a flame retardant to the support. Examples of the flame retardant include guanidine sulfamate, guanidine phosphate, guanidine tetraborate, ammonium sulfamate, ammonium phosphate, melamine phosphate, tetrabromobisphenol A, antimony trioxide, aluminum hydroxide, and magnesium hydroxide. Can be As a method of impregnating the flame retardant, the impregnation may be carried out by a size press in a paper making process, or may be added in advance in a stock preparation step to make a paper.

In processing the above-mentioned plant fiber raw material into a support according to the present invention, rosin and its modified product, if desired,
Emulsions of vegetable wax or maleic anhydride, α-olefin, and styrene / acrylate synthetic resins, sizing agents such as alkyl ketene dimer, alkenyl succinic anhydride and stearic anhydride, starch and modified products thereof, guar gum And denatured products thereof, dextrin, carboxymethylcellulose, polyvinyl alcohol, polyethylene oxide, polyethyleneimine, polyacrylamide, polyamide epichlorohydrin, various emulsions (including latex), urea formalin resin, melamine formalin resin, and other paper strength enhancers and binders. Besides, various additives such as a retention aid, a surfactant, an antifoaming agent, a dye, a fluorescent brightener, an antioxidant, and a slime control agent may be added or paper-made. For the paper making of the support, a combination paper machine such as a round net paper machine, a fourdrinier paper machine, a Yankee paper machine, a twin wire paper machine, a hybrid former and a top former can be used.

Further, as the plant fiber used for the support according to the present invention, a water-soluble inorganic substance is allowed to act on the plant fiber before forming into a sheet, and the inorganic substance-supporting fiber obtained by insolubilizing the inorganic substance with water is supported. May be used. As a method for insolubilizing and supporting a water-soluble inorganic substance on plant fiber (pulp), JP-A-3-146766, JP-A-3-152295, JP-A-4-18193, JP-A-4-24299 , And JP
There is a method described in JP-A-4-57964. That is, the hydrophilic fiber material is impregnated with an aqueous solution containing a water-soluble inorganic compound that reacts with a specific gas or aqueous solution to generate a water-insoluble inorganic substance, and then is contacted with a gas or an aqueous solution that makes these inorganic substances water-insoluble. By doing so, a water-insoluble inorganic substance can be carried inside the fiber material.

As the support according to the present invention, a coated paper obtained by coating a paper base material with an inorganic pigment or an organic pigment together with a binder and performing a smoothing treatment can be used.

The nonwoven fabric used for the support according to the present invention may be a wet method in which the above synthetic resin fibers are suspended in water and formed into a sheet by a papermaking method, a resin bond by resin bonding, a needle punch using crossing with a needle, or the like. The so-called dry method such as stitch bond knitted by yarn or thermal bond bonding by heat, water entanglement method in which high-pressure water is sprayed from a nozzle to entangle the fibers, spun bond to form a sheet while spinning directly, direct spinning In this case, it can be manufactured by a melt blow method or the like in which a sheet is formed while producing fine fibers by applying the principle of spraying. The thickness of the nonwoven fabric,
The porosity, the shape of the void, the degree of porosity, the flexibility, the elasticity, the fluff, the texture, and the like can be adjusted by selecting the above-described production method. Further, in the present invention, since the aqueous treatment is performed, the nonwoven fabric needs to have a certain degree of water wettability, and a web made of hydrophilic fibers is preferable. Further, it is preferable to process the nonwoven fabric by a spun bond or spun lace method from the viewpoint of sheet strength.

[0046]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. The parts by weight described below indicate parts by weight of dry solids.

[Example 1] <Preparation of titanium oxide coating composition> Ultrafine titanium oxide fine powder (trade name: FINNTI S-150, X-ray particle size 2)
nm, 100 parts by weight of KEMIRA) and 2 parts by weight of sodium polycarboxylate (trade name: ARON T-40, manufactured by Toa Gosei) were mixed with water, and stirred at high speed with a laboratory mixer for 1 hour to disperse fine titanium oxide powder. . Next, 160 parts by weight of silica sol (trade name: Snowtex ST-40, manufactured by Nissan Chemical Co., Ltd.) was added to this dispersion, and the mixture was stirred at a high speed for 1 hour and the solid content was 20% by weight.
Was prepared. further,
To this titanium oxide / silica sol dispersion, 7.7 parts by weight of starch as a water-soluble organic polymer compound and 38.3 parts by weight of a styrene-acryl copolymer as a thermoplastic polymer emulsion were added, and slowly added for 30 minutes so as not to form bubbles. The mixture was stirred to prepare a titanium oxide coating composition. At this time, the blending ratio of the organic polymer binder to the total solid content of the coating composition was 15% by weight.
Met.

<Preparation of Titanium Oxide-Supporting Sheet> The above-mentioned titanium oxide coating composition coating solution was dried on a 70-μm-thick transparent PET film using a Mayer bar, and the coated amount after drying was 4 g / m ^{2 on the} F side. , W-side coating 4g / m ²
After drying, a titanium oxide supporting sheet was prepared.

<Preparation of Disc-shaped Titanium Oxide Honeycomb Disc> 400 sheets of titanium oxide supporting sheet A4 size prepared by the above-mentioned method were laminated and dried while gluing 400 sheets.
The sheet was cut at a width of 7 mm to obtain a honeycomb block having a length of 12 cm, a width of 5 cm and a thickness of 0.7 cm. Further, two ends in the longitudinal direction of the honeycomb block were glued and expanded so as to form a disc, thereby obtaining a disc-shaped titanium oxide honeycomb disc having a diameter of 24 cm.

<Confirmation test of photocatalytic effect> The above diameter 24c
As shown in FIG. 1, a m-shaped disc-shaped titanium oxide honeycomb disc was set on a round fluorescent lamp of an indoor lighting lamp equipped with a 20 W round fluorescent lamp. This was placed in a closed chamber having a volume of 200 L. Initial concentration inside chamber is 20
Acetaldehyde gas was injected into the chamber so as to be ppm. Then, the illumination lamp was turned on, and the concentration of acetaldehyde in the chamber was measured by a gas chromatograph with FID. As a result, the decomposition rate after 10 hours was 100%, and it was confirmed that acetaldehyde was completely photolyzed.

Example 2 <Preparation of Disc-shaped Titanium Oxide Lattice Disk> The titanium oxide-carrying sheet prepared in Example 1 was cut into a piece having a length of 1 cm and a width of 25 cm.
100 cm strips were produced. Next, add 0.5cm to this strip
Cut 0.5cm deep at intervals of
A 0.5 cm × 0.5 cm square titanium oxide grid disk measuring 25 cm long × 25 cm wide was obtained. Furthermore, this is diameter 24c
m, cut into a disk shape, diameter 24cm, thickness 1c
m, a disk-shaped titanium oxide lattice disk having a cell size of 0.5 cm × 0.5 cm was obtained.

<Confirmation test of photocatalytic effect> The above diameter 24c
In the same manner as in Example 1, a disc-shaped titanium oxide lattice disk of m was set on a round fluorescent lamp of an indoor lighting lamp equipped with a round fluorescent lamp of 20 W. This was placed in a closed chamber having a volume of 200 L. Initial concentration inside chamber is 20p
Acetaldehyde gas was injected into the chamber so that the pressure became pm. Then, the illumination lamp was turned on, and the concentration of acetaldehyde in the chamber was measured by a gas chromatograph with FID. As a result, the decomposition rate after 10 hours was 100%, and it was confirmed that acetaldehyde was completely photolyzed.

Example 3 <Production of Disc-shaped Titanium Oxide Corrugated Disk> The titanium oxide-carrying sheet produced in Example 1 (length 30 cm × width 75 c)
m) Titanium oxide supporting sheet formed into 20 sheets and corrugated (length 30
20 cm x 75 cm), alternately laminated, glued, dried, and laminated 40 sheets to make a titanium oxide corrugate, and then glued at both ends to form a cylindrical titanium oxide corrugated block with an inner diameter of 5 cm and an outer diameter of 24 cm I got In addition, this thickness
Cut to 0.7cm, inner diameter 5cm, outer diameter 24cm, thickness 0.7c
m was obtained.

<Confirmation test of photocatalytic effect> The above outer diameter 24c
The m-shaped disc-shaped titanium oxide corrugated disk was set on a round fluorescent lamp of an indoor lighting lamp equipped with a 20 W round fluorescent lamp in the same manner as in Example 1. This was placed in a closed chamber having a volume of 200 L. The initial concentration inside the chamber
Acetaldehyde gas was injected into the chamber to 20 ppm. Then, the illumination lamp was turned on, and the concentration of acetaldehyde in the chamber was measured by a gas chromatograph with FID. As a result, the decomposition rate after 10 hours was 100%, and it was confirmed that acetaldehyde was completely photolyzed.

Example 4 <Preparation of Titanium Oxide Paint Composition> Ultrafine titanium oxide fine powder (trade name: FINNTI S-150, X-ray particle size 2)
nm, 100 parts by weight of KEMIRA) and 2 parts by weight of sodium polycarboxylate (trade name: Alon T-40, manufactured by Toagosei Co., Ltd.) were mixed with water, and the mixture was stirred at high speed with a laboratory mixer for 1 hour to disperse fine titanium oxide powder. . Next, 160 parts by weight of silica sol (trade name: Snowtex ST-40, manufactured by Nissan Chemical Co., Ltd.) was added to this dispersion, and the mixture was stirred at a high speed for 1 hour and the solid content was 20% by weight.
Was prepared. further,
To this titanium oxide / silica sol dispersion, 15.4 parts by weight of polyvinyl alcohol as a water-soluble organic polymer compound and 30.6 parts by weight of a styrene-butadiene copolymer as a thermoplastic polymer emulsion were added, and slowly added to prevent foaming. After stirring for a minute, a titanium oxide coating composition was prepared. At this time, the blending ratio of the organic polymer binder to the total solid content of the coating composition was 15% by weight.

<Preparation of Titanium Oxide-Supported Sheet> The titanium oxide coating composition coating solution was dried on a 70-μm-thick aluminum plate using a Mayer bar to obtain a coating amount of F.
Both surfaces were coated and dried so that the surface became 4 g / m ² and the W surface became 4 g / m ² , thereby producing a titanium oxide supporting sheet.

<Preparation of Disc-shaped Titanium Oxide Honeycomb Disk> 400 sheets of titanium oxide-carrying sheet A4 size prepared by the above-mentioned method were laminated and dried while gluing 400 sheets.
The sheet was cut at a width of 7 mm to obtain a honeycomb block having a length of 12 cm, a width of 5 cm, and a thickness of 0.7 cm. Further, two ends in the longitudinal direction of the honeycomb block were glued and expanded so as to form a disc, thereby obtaining a disc-shaped titanium oxide honeycomb disc having a diameter of 24 cm.

<Confirmation test of photocatalytic effect> The above diameter 24c
The m-shaped disc-shaped titanium oxide honeycomb disc was set on a round fluorescent lamp of an indoor lighting equipped with a 20 W round fluorescent lamp. This was placed in a closed chamber having a volume of 200 L. Acetaldehyde gas was injected into the chamber such that the initial concentration inside the chamber became 20 ppm.
Then, the illumination lamp was turned on, and the concentration of acetaldehyde in the chamber was measured by a gas chromatograph with FID. As a result, the decomposition rate after 10 hours was 100%, and it was confirmed that acetaldehyde was completely photolyzed.

Example 5 <Preparation of Titanium Oxide Paint Composition> Ultrafine titanium oxide fine powder (trade name: FINNTI S-150, X-ray particle size 2)
nm, 100 parts by weight of KEMIRA) and 2 parts by weight of sodium polycarboxylate (trade name: Alon T-40, manufactured by Toagosei Co., Ltd.) were mixed with water, and the mixture was stirred at high speed with a laboratory mixer for 1 hour to disperse fine titanium oxide powder. . Next, alumina sol (trade name:
160 parts by weight of alumina sol (manufactured by Nissan Chemical Co., Ltd.) was added to this dispersion and stirred at high speed for 1 hour to prepare a titanium oxide / alumina sol dispersion having a solid content of 20% by weight. Further, 46 parts by weight of polyvinyl alcohol as a water-soluble organic polymer compound was added to the titanium oxide / alumina sol dispersion liquid, and the mixture was slowly stirred for 30 minutes without foaming to prepare a titanium oxide coating composition. At this time, the blending ratio of the organic polymer binder to the total solid content of the coating composition was 15% by weight.

<Preparation of titanium oxide supporting sheet>
Guanidine sulfanilate as a flame retardant
Basis weight 60g / m ^TwoTitanium oxide paint composition on high quality paper
Using a Meyer bar to dry the coating liquid
Surface 4g / m^Two, W surface 4g / m^TwoApply and dry on both sides to become
Then, a titanium oxide supporting sheet was prepared.

<Preparation of Disc-shaped Titanium Oxide Honeycomb Disk> 400 sheets of titanium oxide-carrying sheet A4 prepared by the above method were laminated and dried while gluing 400 sheets.
The sheet was cut at a width of 7 mm to obtain a honeycomb block having a length of 12 cm, a width of 5 cm, and a thickness of 0.7 cm. Further, two ends in the longitudinal direction of the honeycomb block were glued and expanded so as to form a disc, thereby obtaining a disc-shaped titanium oxide honeycomb disc having a diameter of 24 cm.

<Confirmation test of photocatalytic effect> The above diameter 24c
The m-shaped disc-shaped titanium oxide honeycomb disc was set on a round fluorescent lamp of an indoor lighting equipped with a 20 W round fluorescent lamp. This was placed in a closed chamber having a volume of 200 L. Acetaldehyde gas was injected into the chamber such that the initial concentration inside the chamber became 20 ppm.
Then, the illumination lamp was turned on, and the concentration of acetaldehyde in the chamber was measured by a gas chromatograph with FID. As a result, the decomposition rate after 10 hours was 100%, and it was confirmed that acetaldehyde was completely photolyzed.

Example 6 <Production of Titanium Oxide Composite Particles> Fine titanium oxide powder (trade name: FINNTI S-150, X-ray particle size 2 nm, KE
100 parts by weight of MIRA (manufactured by MIRA) and 2 parts by weight of sodium polycarboxylate (trade name: ARON T-40, manufactured by Toagosei Co., Ltd.) were mixed with water, and the mixture was stirred at a high speed for 1 hour with a laboratory mixer to disperse fine titanium oxide powder. Next, silica sol (trade name: ST-40,
160 parts by weight (manufactured by Nissan Chemical Industries, Ltd.) was added to this dispersion, and the mixture was stirred at high speed for 1 hour to prepare a titanium oxide / silica sol dispersion having a solid content of 20% by weight. Further, this dispersion was dried with a dryer at 100 ° C. for 1 hour to obtain titanium oxide / silica sol composite particles.

<Preparation of Titanium Oxide-Supported Sheet> 100 parts by weight of the titanium oxide / silica sol composite particles prepared by the above method and sodium polycarboxylate (trade name: Alon T-40,
2 parts by weight of Toa Gosei Co., Ltd.) are mixed with water and wet-pulverized for 2 hours using a horizontal wet-type pulverizer to obtain a titanium oxide / silica sol composite particle dispersion having an average particle diameter of 10 μm and a solid content of 20% by weight. Obtained. Softwood bleached kraft pulp (hereinafter abbreviated as NBKP) in 500 parts by weight of this dispersion and 4000 parts by weight of water
9 parts by weight and a dispersion liquid, and further 1% by weight
An anion-modified polyacrylamide was added, and a sheet to which titanium oxide / silica sol composite particles having a basis weight of 60 g / m ² was internally added was formed on a circular mesh type paper machine and dried at 120 ° C. to obtain a titanium oxide supporting sheet.

<Preparation of Disc-shaped Titanium Oxide Honeycomb Disk> 400 sheets of titanium oxide-carrying sheet A4 size prepared by the above-described method were laminated and dried while gluing 400 sheets.
The sheet was cut at a width of 7 mm to obtain a honeycomb block having a length of 12 cm, a width of 5 cm, and a thickness of 0.7 cm. Further, two ends in the longitudinal direction of the honeycomb block were glued and expanded so as to form a disc, thereby obtaining a disc-shaped titanium oxide honeycomb disc having a diameter of 24 cm.

<Confirmation test of photocatalytic effect> The above diameter 24c
The m-shaped disc-shaped titanium oxide honeycomb disc was set on a round fluorescent lamp of an indoor lighting equipped with a 20 W round fluorescent lamp. This was placed in a closed chamber having a volume of 200 L. Acetaldehyde gas was injected into the chamber such that the initial concentration inside the chamber became 20 ppm.
Then, the illumination lamp was turned on, and the concentration of acetaldehyde in the chamber was measured by a gas chromatograph with FID. As a result, the decomposition rate after 10 hours was 100%, and it was confirmed that acetaldehyde was completely photolyzed.

Example 7 <Preparation of Titanium Oxide Paint Composition> Ultrafine titanium oxide fine powder (trade name: FINNTI S-150, X-ray particle size 2)
nm, 100 parts by weight of KEMIRA) and 2 parts by weight of sodium polycarboxylate (trade name: Alon T-40, manufactured by Toagosei Co., Ltd.) were mixed with water, and the mixture was stirred at high speed with a laboratory mixer for 1 hour to disperse fine titanium oxide powder. . Next, alumina sol (trade name:
160 parts by weight of alumina sol (manufactured by Nissan Chemical Co., Ltd.) (160 parts by weight) was added to the dispersion, and the mixture was stirred at high speed for 1 hour to prepare a titanium oxide / alumina sol dispersion having a solid content of 20% by weight. further,
To this titanium oxide / alumina sol dispersion, 46 parts by weight of polyvinyl alcohol as a water-soluble organic polymer compound was added, and the mixture was stirred slowly for 30 minutes without foaming to prepare a titanium oxide coating composition. At this time, the blending ratio of the organic polymer binder to the total solid content of the coating composition was 15% by weight.

<Preparation of Titanium Oxide-Supporting Sheet> A nonwoven fabric was prepared in advance by the following method. 40 parts by weight of polyethylene terephthalate fiber with a fineness of 0.15 denier (fiber diameter 4 microns) and a fiber length of 7.5 mm and a fineness of 1.5 denier (fiber diameter 1
2.4 microns) and 60 parts by weight of a polyester-based flame-retardant fiber having a fiber length of 15 mm were put into water together with a surfactant, and the mixture was vigorously stirred with a pulper until the fiber bundle disappeared. After dilution with water, an aqueous solution of high molecular polyacrylamide was added while gently stirring with an agitator to increase the viscosity, and stirring was continued to obtain a uniformly dispersed fiber slurry. Using this slurry, a non-woven fabric was obtained by papermaking with a circular paper machine so that the basis weight was 80 g / m ² . Using a Mayer bar, apply the above-mentioned titanium oxide coating composition coating solution on both sides of this non-woven fabric so that the application amount after drying becomes 4 g / m ² on the F side and 4 g / m ^{2 on} the W side, and then dry and oxidize. A titanium-carrying sheet was produced.

<Preparation of Disc-shaped Titanium Oxide Honeycomb Disc> 400 sheets of titanium oxide-carrying sheet A4 prepared by the above method were laminated and dried while gluing 400 sheets.
The sheet was cut at a width of 7 mm to obtain a honeycomb block having a length of 12 cm, a width of 5 cm, and a thickness of 0.7 cm. Further, two ends in the longitudinal direction of the honeycomb block were glued and expanded so as to form a disc, thereby obtaining a disc-shaped titanium oxide honeycomb disc having a diameter of 24 cm.

<Confirmation test of photocatalytic effect> The above diameter 24c
The m-shaped disc-shaped titanium oxide honeycomb disc was set on a round fluorescent lamp of an indoor lighting equipped with a 20 W round fluorescent lamp. This was placed in a closed chamber having a volume of 200 L. Acetaldehyde gas was injected into the chamber such that the initial concentration inside the chamber became 20 ppm.
Then, the illumination lamp was turned on, and the concentration of acetaldehyde in the chamber was measured by a gas chromatograph with FID. As a result, the decomposition rate after 10 hours was 100%, and it was confirmed that acetaldehyde was completely photolyzed.

Comparative Example 1 <Preparation of Titanium Oxide Paint Composition> Ultrafine titanium oxide fine powder (trade name: FINNTI S-150, X-ray particle size 2)
nm, 100 parts by weight of KEMIRA) and 2 parts by weight of sodium polycarboxylate (trade name: Alon T-40, manufactured by Toagosei Co., Ltd.) were mixed with water, and the mixture was stirred at high speed with a laboratory mixer for 1 hour to disperse fine titanium oxide powder. . Next, 160 parts by weight of silica sol (trade name: Snowtex ST-40, manufactured by Nissan Chemical Industries, Ltd.) was added to the dispersion, and the mixture was stirred at a high speed for 1 hour, and the solid content was 20% by weight.
Was prepared. further,
To this titanium oxide / silica sol dispersion, 7.7 parts by weight of starch as a water-soluble organic polymer compound and 38.3 parts by weight of a styrene-acryl copolymer as a thermoplastic polymer emulsion were added, and slowly added for 30 minutes so as not to form bubbles. The mixture was stirred to prepare a titanium oxide coating composition. At this time, the blending ratio of the organic polymer binder to the total solid content of the coating composition was 15% by weight.
Met.

<Preparation of titanium oxide supporting sheet>
/ M ² of high-quality paper, the coating amount of the titanium oxide coating composition was dried using a Meyer bar using a Meyer bar, and the coated amount was 4 g / F side.
Both surfaces were coated and dried so as to obtain m ² and W surface of 4 g / m ² , thereby producing a titanium oxide supporting sheet.

<Preparation of Titanium Oxide Honeycomb> The titanium oxide supporting sheet A4 size 400 prepared by the above method was
After laminating and drying 400 sheets while gluing, the sheet was cut into 7 mm width to obtain a honeycomb block having a length of 7 cm, a width of 5 cm and a thickness of 0.7 cm. Furthermore, this honeycomb block is extended and
A rectangular titanium oxide honeycomb having a size of 7 cm, a width of 58 cm and a thickness of 0.7 cm was obtained.

<Confirmation test of photocatalytic effect> The above vertical 7c
A rectangular titanium oxide honeycomb having a length of 58 cm, a width of 58 cm and a thickness of 0.7 cm was set on a straight fluorescent lamp of an indoor lighting equipped with a 20 W straight fluorescent lamp having a length of 58 cm. This is 20
It was installed in a closed chamber having a volume of 0 L. Acetaldehyde gas was injected into the chamber such that the initial concentration inside the chamber became 20 ppm. Then, the lighting is turned on and the acetaldehyde concentration in the chamber is measured by FI.
It was measured by a gas chromatograph with D. As a result, the decomposition rate after 10 hours was 50%, and the decomposition rate of acetaldehyde was low.

Comparative Example 2 <Production of Titanium Oxide Composite Particles> Titanium oxide fine powder (trade name: FINNTI S-150, X-ray particle size 2 nm, KE
100 parts by weight of MIRA (manufactured by MIRA) and 2 parts by weight of sodium polycarboxylate (trade name: ARON T-40, manufactured by Toagosei Co., Ltd.) were mixed with water, and the mixture was stirred at high speed with a laboratory mixer for 1 hour to disperse fine titanium oxide powder. Next, silica sol (trade name: ST-4)
160 parts by weight (Nissan Chemical Co., Ltd.) was added to this dispersion and stirred at a high speed for 1 hour to prepare a titanium oxide / silica sol dispersion having a solid content of 20% by weight. Further, this dispersion was dried with a dryer at 100 ° C. for 1 hour to obtain titanium oxide / silica sol composite particles.

<Preparation of Titanium Oxide-Supporting Sheet> 100 parts by weight of the titanium oxide / silica sol composite particles prepared by the above method and sodium polycarboxylate (trade name: Alon T-40,
Toa Gosei) 2 parts by weight are mixed with water and wet milled for 2 hours using a horizontal wet mill to obtain 20
A weight% titanium oxide / silica sol composite particle dispersion was obtained.
A mixture of 500 parts by weight of this dispersion and a dispersion obtained by mixing 9 parts by weight of NBKP in 4000 parts by weight of water and further adding 1% by weight of anion-modified polyacrylamide was used. / M ² , a sheet to which titanium oxide / silica sol composite particles were internally added was formed and dried at 120 ° C. to obtain a titanium oxide supporting sheet.

<Production of Titanium Oxide Honeycomb> The titanium oxide supporting sheet A4 size 400 produced by the above method was
After laminating and drying 400 sheets while gluing, the sheet was cut into 7 mm width to obtain a honeycomb block having a length of 7 cm, a width of 5 cm and a thickness of 0.7 cm. Furthermore, this honeycomb block is extended and
A rectangular titanium oxide honeycomb having a size of 7 cm, a width of 58 cm and a thickness of 0.7 cm was obtained.

<Confirmation test of photocatalytic effect> The above vertical 7c
A rectangular titanium oxide honeycomb having a length of 58 cm, a width of 58 cm and a thickness of 0.7 cm was set on a straight fluorescent lamp of an indoor lighting equipped with a 20 W straight fluorescent lamp having a length of 58 cm. This is 20
It was installed in a closed chamber having a volume of 0 L. Acetaldehyde gas was injected into the chamber such that the initial concentration inside the chamber became 20 ppm. Then, the lighting is turned on and the acetaldehyde concentration in the chamber is measured by FI.
It was measured by a gas chromatograph with D. As a result, the decomposition rate after 10 hours was 40%, and the decomposition rate of acetaldehyde was low.

[0079]

The effects of the present invention will be described below. 1) A luminaire equipped with a round fluorescent lamp, which is widely used as a household luminaire, and a disk molded from a sheet of metal, paper, non-woven fabric, etc. coated or internally coated with a photoreactive semiconductor. The use of a combination of a photoreactive semiconductor honeycomb disk and a combination of a rectangular titanium oxide honeycomb and a straight tube fluorescent lamp, which has been conventionally known, makes it possible to detect indoor bacteria, viruses, and sickhouses. Efficient odor substances such as formalin odor, tobacco odor, and NOx gas entering the room from the main road can be efficiently deodorized and sterilized. 2) Since the titanium oxide coating composition is composed of titanium oxide fine particles, an inorganic binder selected from silica sol or alumina sol, and an appropriate ratio of an organic polymer binder, the film strength is strong and the film is irradiated by ultraviolet rays. There is no deterioration.

[0080]

[Brief description of the drawings]

FIG. 1 is a perspective view showing a lighting fixture equipped with a round fluorescent lamp used in the present invention.

FIG. 2 is a perspective view showing a disc-shaped photoreactive semiconductor honeycomb disk of the present invention.

FIG. 3 is a perspective view of a disc-shaped photoreactive semiconductor honeycomb disk of the present invention, in which a fixing stopper is attached to a central portion.

FIG. 4 is a perspective view of the disk-shaped photoreactive semiconductor honeycomb disk of the present invention installed on a round fluorescent lamp.

FIG. 5 is a perspective view in which a rectangular photoreactive semiconductor honeycomb used in a comparative example is set on a straight tube fluorescent lamp.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Lighting fixture main body 2 Round fluorescent lamp 3 Disc-shaped photoreactive semiconductor honeycomb disk 4 Fixing stopper 5 Rectangular photoreactive semiconductor honeycomb 6 Straight tube fluorescent lamp

Claims (2)

[Claims] 1. A photoreactive semiconductor comprising: a round fluorescent lamp for generating radiation for activating a photocatalytic function of a photoreactive semiconductor; and a photoreactive semiconductor-containing layer having a photocatalytic function provided on at least one surface of a support. A harmful substance removal system comprising a photoreactive semiconductor disk comprising a semiconductor supporting sheet, wherein the round fluorescent lamp and the photoreactive semiconductor disk are provided in parallel contact or adjacent to each other. 2. A photoreactive semiconductor comprising a round fluorescent lamp for generating radiation for activating the photocatalytic function of a photoreactive semiconductor and a photoreactive semiconductor support sheet having photoreactive semiconductor fine particles having a photocatalytic function internally added in a support. A harmful substance removing system comprising a photoreactive semiconductor disk, wherein the round fluorescent lamp and the photoreactive semiconductor disk are provided in parallel contact or adjacent to each other.