JPH09613A - Article with silica film containing powder of functional substance - Google Patents

Abstract

PURPOSE: To provide an article with silica film containing functional substance powder that excels in adhesion to a substrate and in lightfastness. CONSTITUTION: The article with a silica film is composed of a substrate, resin layer formed on the surface of the substrate, silica film fixed on the resin layer, and the powder of a functional substance fixed on the silica film; also, the article is such that the surface of a resin made on the substrate surface is coated with silica sol prepared by dispersing ester silicate, water and/or organic solvent so as to form a silica film, and that, after the silica film is coated with a coating material prepared by dispersing the powder of a functional substance in a silicic ester, water and/or an organic solvent, the article is heated at 400 deg.C or below.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article useful for decomposing, removing and sterilizing various malodorous gases and harmful gases generated in daily life, harmful compounds in water, etc. And a silica film containing a photocatalytically active substance such as titanium dioxide and zinc oxide, which exhibits an effect of decomposing inorganic substances, and a deodorant containing titanium dioxide, iron oxide, zinc oxide, and the like, fixed on the resin layer and the resin layer. The present invention relates to an article formed on a substrate via a silica film. The silica film on the surface of the obtained article is characterized by excellent workability and weather resistance.

[0002]

2. Description of the Related Art It is widely known that photocatalysts such as titanium dioxide, when irradiated with ultraviolet rays, transfer electrons from the valence band to the conduction band by photoexcitation to become n-type semiconductors, exhibiting decomposition and sterilizing effects of various compounds. Decomposition of organic matter in water (“Water and Wastewater”, vol. 30 No. 10 (198
8) p943-948), organic substance decomposition, deodorization, and sterilization ("Surface" vol. 25 No. 8 (1987) p47.
7-495, "Ceramics" 21 (1986) No.
4, p326-333) and the like. However, when actually using its photocatalytic activity for the purpose of decomposing and removing harmful gas in exhaust gas, bad smell gas such as cigarettes and toilets, harmful substances such as pesticides, environmental pollutants, sterilization, etc. It is necessary to carry and fix it on some kind of substrate. In addition, powders of various functional substances, such as deodorants, which have been recently developed, are rarely used in the form of powder.

As an example of the functional substance powder, a method of supporting titanium dioxide for photocatalyst on a substrate has been proposed, for example. (1) Titanium oxide fine powder is adhered to a film-like, bead-like, board-like, fiber-like substrate made of a light-transmitting substance material such as nitrocellulose, glass, polyvinyl chloride, nylon, methacrylic resin, and polypropylene. Method (JP-A-62-66861) (2) A porous glass support is impregnated with an alcohol solution of titanium (IV) tetrabutoxyoxide and heated to
Method of holding and fixing to a porous glass support by using anatase type titanium oxide (Japanese Patent Laid-Open No. 2-5015)
4) (3) Hold the semiconductor catalyst powder by a method such as press-fitting, impregnation, or adhesion in a porous polymer film (for example, polyfluoroethylene resin) having a photosensitizer such as a dye or a metal complex as a side chain. Method of fixing (JP-A-58-125602) (4) Method of supporting titanium oxide on a filtration filter made of polypropylene fiber or ceramics (JP-A-2-68190) (5) In the entanglement of quartz, glass and plastic fibers A method of holding and fixing titanium oxide powder on the both sides and holding both surfaces thereof with light-transmitting glass (US Pat. No. 4,888,810).
1) (6) Platinum is adhered to an alumina substrate by a sputtering method, a mixed dispersion liquid of anatase type titanium oxide powder and an organic solvent solution of methylmethacrylate is applied thereon by a spin coating method, and then bonded. While thermally decomposing methyl methacrylate as a binder,
Method for converting anatase-type titanium oxide into rutile-type titanium oxide (Robert E. Hetric, Appli
ed Physics Communications,
5, (3), 177-187 (1985)) (7) A method of thermally spraying titanium oxide on the surface of a polyester cloth by a low temperature thermal spraying method (Saji Sakurada, Surface Technology Vol. 41, 10
No., P60 (1990))

The above-mentioned known methods for supporting photocatalytic titanium dioxide on a substrate have the following drawbacks.
Fixing with organic substances such as (1), (3), (4), and (5) as a binder causes most of the organic substances to be decomposed by the photocatalytic action of titanium dioxide, so fixing during long-term use is reliable. There is no. In the method (2), since the expensive organic titanium compound is used as the raw material and the glass is directly supported on the glass which is easily broken, the strength is not reliable. Further, the methods (6) and (7) are not preferable because the temperature becomes extremely high during fixing and the high photocatalytic activity of titanium dioxide is lost. In addition, as a method often used, an inorganic porous material, a method of impregnating and supporting a slurry of titanium dioxide on fibers, and a binder obtained by hydrolyzing or melting an alkali salt such as silica-based or alumina-based are used. There is a method to use, but in the former, the titanium dioxide particles are not fixed, so they easily fall off due to vibration and shock, and in the latter, the catalyst surface is coated with a binder for fixing the catalyst and activated. Was lost. Furthermore, since heat resistance and the like are required in these methods, the types of substrates that can be used are also limited, and it is difficult to fix and process them on a wide surface, resulting in high cost, but insufficient utilization of light energy. There was a problem. This problem is common to all photocatalysts other than titanium dioxide, and also to highly active substances such as adsorbents and germicides. When putting these highly active substances into practical use,
A fixing method that is excellent in strength, inexpensive, and easy to handle without decreasing activity has been desired.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above problems, and has a deodorizing effect of a deodorizing agent, an antibacterial effect of an antibacterial agent, and a malodorous gas such as acetaldehyde and mercaptan due to photocatalytic activity of titanium dioxide, harmful gas such as NO _X, harmful substances such as agricultural chemicals, excellent decomposition removal and sterilization effects of environmental pollutants, is to provide a superior article in processability and weather resistance.

[0006]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that a silicate ester, water and an arbitrary organic solvent are formed on a resin layer formed on the surface of a substrate. To form a silica film by applying a mixed solution of, a silicate ester on the silica film, water and any organic solvent was mixed to form a functional material powder was formed by applying a coating material, An article comprising a substrate, a resin layer formed on the surface of the substrate, a silica film fixed on the resin layer and a silica film containing a functional substance powder does not lose the characteristics of the functional substance,
Deodorizing effect of deodorant, bactericidal effect of the antimicrobial agents, aldehydes by irradiation with ultraviolet rays, malodorous gases mercaptan, harmful gases such as NO _X, harmful substances such as agricultural chemicals, the photocatalytic effects such as decomposition and removal and sterilization of environmental pollutants The present invention has been completed by finding out that it has excellent adhesiveness, workability and weather resistance even when applied to a substrate having no heat resistance such as an aluminum plate and a resin.

That is, the present invention provides an article having a substrate, a resin layer formed on the surface of the substrate, a silica film fixed to the resin layer, and a silica film containing a functional substance powder fixed on the silica film. Regarding The substrate may be any substrate as long as it can form a resin layer on its surface, but preferably contains at least one selected from the group consisting of aluminum, iron, nickel and copper as a main component. It is selected from metallic materials, glass, ceramics, resins, cloth, fibers, or combinations thereof. The type of the resin layer formed on the surface of the substrate is epoxy, as long as it has adhesion to the substrate and solubility in a mixture of silicate ester, water and any organic solvent or alcohol generated by hydrolysis of silicate ester, Any material such as ordinary paint resins such as acrylic, urethane, and silicone resin can be used. Of these, acrylic and epoxy resins are preferable, and epoxy resins are particularly preferable because they have strong adhesion to various substrates. As the epoxy resin, any of bisphenol A type, novolac type and aliphatic type resins can be used. The type of epoxy resin and the type of curing agent can be appropriately selected according to the type of substrate used and required performance.
It is also possible to add a pigment to the resin for coloring, or to add an ultraviolet absorber to improve the light resistance. It is sufficient that the thickness of the resin layer is 1 μm or more.

The functional substance powder used in the production of the silica film of the present invention means a powder having a function of photocatalyst, deodorizing and antibacterial, and titanium dioxide, iron oxide and deodorizing are those having a photocatalytic function. Compounds having a function include titanium dioxide, iron oxide and zinc oxide, and compounds having an antibacterial function include compounds such as silver, copper and zinc. Further, it also includes a porous body supporting these and a microcapsule containing a drug. Although these have high activity, when immobilized, the surface is covered,
There are many problems such that the activity is easily lost by heating or the like, and when the resin is made into a paint and fixed, the resin is deteriorated due to the activity. The fixing by the silica film of the present invention is carried out by fixing these highly active substances uniformly in the silica film at a relatively low temperature, and further by fixing them on the resin layer formed on the substrate surface through the silica film. The resin layer can be fixed to the substrate by using the resin layer as a strong binder without fear of degrading the layer. The particle size of the functional substance powder is preferably 5 μm or less, more preferably 0.5 μm or less, and most preferably 0.1 μm or less for the strength of the coating film. As an example of the functional substance powder, titanium dioxide for photocatalyst is preferably anatase type and has a specific surface area of 20 m ² /
It is preferably at least g, more preferably at least 50 m ² / g. Also, for titanium dioxide, W, Sn, Mo, V, M
It is also preferable to contain a metal oxide such as n, Pt, Ni, Ag, Cu and Zn that improves the catalytic activity. In addition to the functional substance powder, a pigment or the like can be added to the silica film.

In the article of the present invention, since the silica film containing the functional substance powder is fixed to the substrate via the silica film fixed on the resin layer, the functional substance powder does not deteriorate the resin. Particularly in the case of titanium dioxide for photocatalyst and a deodorant containing titanium dioxide, the resin tends to be decomposed by irradiation of ultraviolet rays, but the silica film of the present invention is characterized in that the resin layer is not easily deteriorated even by long-time ultraviolet rays. There is. Further, both silica films fixed on the resin layer are integrated with each other on their adhesive surfaces, and the silica sol is dehydrated by the hydrolysis of the silicate ester, and the volume is contracted due to the evaporation of the solvent. Since it is divided into blocks, even if it is deformed such as bending and processing a metal plate with both silica films fixed, or folding the cloth with both silica films fixed, the deformation can be absorbed, so peeling is unlikely to occur It also has the advantage of. Since the strength tends to decrease as the thickness of both silica films increases, the film thickness is 100
It is preferably μm or less. The ratio of the functional substance powder in the silica film containing the functional substance powder, which is fixed on the silica film fixed on the resin layer, is 10 to 90% by weight.
Is more preferable, 20 to 85% by weight is more preferable, and 40 to 80% by weight is most preferable. Known methods can be used as a method for providing a resin layer on the surface of the substrate, a method for providing a silica film on the resin layer, and a method for providing a silica film containing a functional substance powder on the silica film, but Depending on the shape, an appropriate coating method such as coating, spraying or dipping can be selected.

The present invention further provides a method for producing the above article, which comprises forming a mixed solution of a silicate ester, water and an arbitrary organic solvent on a resin layer formed on the surface of a substrate, and further forming a film on the resin layer. Provided is a manufacturing method in which a coating material in which a functional substance powder is dispersed in an acid ester, water and an arbitrary organic solvent is formed into a film and then heat-treated at 400 ° C. or lower. Any known silicate ester can be used, but methyl silicate, ethyl silicate, and butyl silicate are preferred, and ethyl silicate is most preferred. In the mixed liquid which is a raw material of the silica film to be formed on the resin layer, the organic solvent is mixed with the silicate ester and its decomposition product, alcohol, in order to adhere the silica film to the substrate well. It is necessary to be able to dissolve the resin layer. Further, in the coating material in which the functional substance powder is dispersed, the organic solvent has an affinity for the silica sol generated by the hydrolysis of the silicate ester to enhance the dispersibility of the functional substance powder particles and facilitate the application. is necessary.
If the alcohol produced by the hydrolysis of the silicate has the property of dissolving the resin layer and the amount thereof is sufficient, it is not necessary to add a solvent.

The type of solvent can be appropriately selected according to the type of resin layer used, and typical ones are cellosolves, carbitols,
Examples include alcohols. Among the cellosolves, those having an alkyl group are preferable, and butyl cellosolve having a butyl group is particularly preferable. Among carbitols, carbitol and carbitol acetate are preferred. Among alcohols, ethanol and butanol are preferable.

The water added to the paint is used for the hydrolysis of the silicate ester, but the paint pH is preferably acidic in order to improve the dispersibility of the functional substance powder in the paint and the coating strength. , PH 4 or lower is more preferable, and pH 2 or lower is particularly preferable. As a method of lowering the paint pH,
It is preferable to adjust the coating pH by adding a small amount of acid to water. In addition, the pH is preferably acidic even in the mixed liquid which does not contain the functional substance powder and serves as the silica film raw material. As the acid to be added to water, any of hydrochloric acid, sulfuric acid, nitric acid and the like can be used.

First, the mixing ratio of the mixed liquid as the raw material of the silica film to be fixed on the resin layer is 25 to 100 parts by weight of water, preferably 50 to 1 part by weight with respect to 100 parts by weight of silicate ester.
The amount of the organic solvent is 0 to 2000 parts by weight, preferably 0 to 500 parts by weight. Next, the mixing ratio of the coating material for producing the silica film containing the functional substance powder to be fixed on the silica film is such that ethyl silicate is used as the silicate ester based on 100 parts by weight of the functional substance powder. , Ethyl silicate is 30 to 3200 parts by weight, preferably 60 to 1400 parts by weight, more preferably 80 to 5 parts by weight.
20 parts by weight, and when methyl silicate and butyl silicate are used as the silicate ester, the preferable amount is a coefficient corresponding to the ratio of the respective molecular weights, and 0.73 and 1.54 are converted into numerical values in ethyl silicate. Multiplied value. Solvent 0-1
000 parts by weight, preferably 0 to 500 parts by weight, and water 10 to 1100 parts by weight, preferably 20 to 500 parts by weight, more preferably 30 to 200 parts by weight. When the amount of the functional substance powder is less than the above-mentioned mixing ratio in the above mixing ratio, the photocatalytic activity as a film becomes low, and when it exceeds the mixing ratio, the adhesion and strength of the silica film are deteriorated, which is not preferable.

The silica film obtained by coating the resin layer after a long time has passed after preparing a mixed solution of silicate ester, water and any organic solvent is easily peeled off. Particularly, the acid concentration and the liquid temperature of the mixed solution are high. Since the tendency is strong when the value is high, the mixed solution is preferably applied at 90 ° C. or lower, preferably within one week. When the coating material for forming the silica film containing the functional substance powder is applied immediately after the mixed liquid of silicate ester, water and any organic solvent is applied, both are completely mixed and the functional substance is mixed. This is the same as applying a silica film containing a small amount of powder, and it is not preferable because the functional substance powder comes into contact with the resin. In order to integrate the silica film fixed on the resin layer and the silica film containing the functional substance powder fixed on the silica film on the adhesive surface,
After coating a mixture of a silicate ester, water and any organic solvent on a resin layer formed on a substrate, the temperature is 90 ° C. or lower, preferably 60 ° C. or lower within 1 week, preferably within 3 days, particularly preferably. It is preferable to apply the coating material containing the functional substance powder within one day. The heat treatment after applying the latter is preferably carried out within a temperature range where oxidation, alteration and deformation of the resin layer and the substrate do not occur. Generally, the temperature is preferably 400 ° C. or lower, but if the temperature is 100 ° C. or lower, it takes a long time to gel the silica sol, and it is difficult to obtain the film strength. The silica film containing the functional substance powder of the present invention becomes porous by evaporation of alcohol generated by hydrolysis of silicate ester, dehydration of silica sol, evaporation of solvent, and contact between the functional substance powder and the atmosphere. However, in order to make the silica film more porous, a soluble substance such as boric acid has been added to the coating material in which the functional substance powder is dispersed, and the silica film is solidified, and then the coating film is heated with warm water. It is also possible to remove soluble substances by washing with. Even if no soluble substance is added to the paint, washing the coating film removes free silica, deposits, etc., so that the activity of the functional substance powder in the film is improved. Further, when the functional substance powder has a photocatalytic activity, the activity is further enhanced by irradiating with ultraviolet rays to decompose the organic substance on the surface of the functional substance powder particles.

Since it is preferable that the functional substance powder is spread and fixed as fine particles in order to improve efficiency, it is preferably applied as a paint on a substrate and fixed as a coating film. In the production method according to the present invention, by adding an organic solvent to the mixed solution of silicic acid ester and water, not only the stability as a mixed solution, viscosity, dispersibility, drying rate is improved, but also on the substrate surface. The resin is dissolved by applying it to the surface of the prepared resin layer to form a layer in which silica and resin are mixed, and then a coating material containing functional substance powder is applied on top of it, and both silica layers are bonded to each other. We succeeded in fixing it firmly on the resin layer at the same time as it was integrated with. Moreover, since the functional substance powder itself is fixed in the silica film and passes through the silica film fixed on the resin layer, the effect of not directly contacting the resin and deteriorating the resin can be obtained. Further, even if the resin is weak to ultraviolet rays, the silica film and the functional substance fixed on the resin layer block ultraviolet rays, so that it also has an advantage of preventing deterioration of the resin. Incidentally, in forming the first silica film, it is possible to apply a solution prepared by dissolving a resin in the mixed solution in advance onto a substrate on which a resin layer is not prepared, and fix the resin by the resin. According to this method, the functional substance comes into contact with the resin and the resin is deteriorated, which is not preferable.

The silica film in the article of the present invention becomes porous by dehydration from the silica sol formed by hydrolysis of silicate ester, evaporation of alcohol, and evaporation of organic solvent, and the functional substance powder particles contained therein become the atmosphere. Since it is easy to come into contact with the gas, water, surface adsorbing substances such as bacteria, it can react efficiently with these. The article according to the present invention is preferably used as a deodorant. That is, the present invention, as one aspect thereof, a substrate, a resin layer formed on the substrate surface,
Provided is a deodorant having a silica film fixed on a resin layer and a silica film fixed on the silica film and containing a powder of a functional substance such as deodorant or titanium dioxide having photocatalytic activity. Among the functional substances, for such as titanium dioxide having photocatalytic activity, aldehyde, in addition to deodorization effects such as mercaptans, NO _X, ammonia, harmful substances inorganic gases and pesticides such as hydrogen sulfide, environmental pollutants It is obvious that the decomposition and removal of lactic acid and the sterilization and removal of fungi and algae are known as photocatalytic effects, and when the deodorizing effect is obtained, other effects known as the photocatalytic effect can be obtained at the same time. Hereinafter, the contents of the present invention will be described in more detail with reference to Examples, but these Examples are merely examples, and the scope of the present invention is not limited thereto.

Example 1 According to the method described in Japanese Examined Patent Publication No. 3-33022, a deodorant consisting of a tightly bound body of titanium dioxide and zinc oxide was produced by the following procedure. 1 liter of pure water was dispensed into a 5 liter beaker and heated and maintained at a temperature of 60 ° C. with stirring. Next, 144 g of TiO ₂ separately prepared and Zn
2 liters of a titanium sulfate-zinc sulfate mixed aqueous solution containing 16 g as O and an aqueous ammonia solution were mixed with p of the combined solution.
While being careful to maintain H at 7.5, the solution was simultaneously dropped into the pure water over 30 minutes. After filtering and washing the product 2
After drying at 00 ° C. for 3 hours, a deodorizing agent (specific surface area 410 m ² / g, composed of particles of a tightly bound body of titanium dioxide and zinc oxide,
An average particle size of 0.4 μm) was produced. 6 g of the above deodorant,
9 g of ethyl silicate, 3 g of water added with 0.5 mol of hydrochloric acid,
Boric acid 0.12g and butyl cellosolve 6g 3mm
90 g of glass beads of No. 1 was charged into a 120 ml mayonnaise bottle, and the mixture was dispersed and mixed for 10 minutes with a paint conditioner manufactured by Red Devil Co. to obtain a deodorant-containing paint. Further, 6 g of ethyl silicate and 2 g of water to which 0.05 mol of hydrochloric acid was added were charged into a 120 ml mayonnaise bottle and dispersed for 1 minute with a paint conditioner manufactured by Red Devil Co. to prepare a mixed solution. Sky Aluminum Co., Ltd. Skycoat epoxy resin coated surface (60
(mm × 150 mm × 0.5 mm), the above silica sol was applied with a 2 mil doctor blade, and after 30 minutes, the above coating material was applied with a 2 mil doctor blade. After air-drying for 24 hours, baking at 150 ° C. for 1 hour to produce a silica film, washing with warm water at 60 ° C. to remove boric acid,
The organic substances attached to the surface of the deodorant particles were decomposed and removed by irradiation with ultraviolet rays. From scanning electron microscope observation, it was confirmed that a silica film containing deodorant particles was formed on the surface of the substrate on a silica film not containing deodorant, and these films were fixed on the substrate by a resin. It was The thickness of the silica film is about 20 μm, and the weight of the silica film is about 1.5 m.
It was g / cm ² . When the adhesiveness and hardness of the coating film of this film were examined by the method of JIS-K5400, the adhesiveness was 10 at the evaluation point and the pencil hardness was 3H or more. Cut the coating surface 5 cm x 1 cm into a 120 ml glass bottle and add acetaldehyde at a gas concentration of 1000 pp in the bottle.
After injecting to an amount of m, and leaving it at room temperature for 1 hour, the air in the bottle is filled with gas chromatograph G3800 manufactured by Yanagimoto Seisakusho.
When measured by (detector FID), the acetaldehyde concentration was 0 ppm. Acetate 10
In each case of 0 ppm, trimethylamine 1000 ppm, ethyl mercaptan 1000 ppm, and dimethyl sulfide 50 ppm, after 1 hour,
ppm. In addition, 10 mg of the deodorant powder used
When a deodorizing test of acetaldehyde was carried out in the same manner (about the same amount as contained in the coating surface of 5 cm x 1 cm), the rate of decrease in concentration was almost the same, and the activity due to the coating film did not decrease. It seems that there are not many. Table 6 shows the deodorizing data of this time for acetaldehyde and ethyl mercaptan. Further, this coating film was irradiated with ultraviolet rays of 3.0 mW / cm ² × 500 hours using a Sue Tester Co., Ltd. Dew Panel Light Control Weather Meter, but no discoloration or strength deterioration of the coating film occurred. It was

Example 2 Titanium dioxide (anatase type, specific surface area 60 m ² / g,
6 g of average particle diameter 0.1 μm), 9 g of ethyl silicate, 3 g of water added with 0.5 mol of hydrochloric acid, 0.12 g of boric acid and 6 g of butyl cellosolve were put in a 120 ml mayonnaise bottle together with 90 g of 3 mm glass beads, and red devil was added. A paint conditioner manufactured by the company was used to disperse and mix for 10 minutes to obtain a paint containing titanium dioxide. Further, 6 g of ethyl silicate, 2 g of water to which 0.05 mol of hydrochloric acid was added, and 4 g of butyl cellosolve were placed in a 120 ml mayonnaise bottle and dispersed for 1 minute with a paint conditioner manufactured by Red Devil to prepare a mixed solution. The above mixture was applied to the epoxy resin coated surface (60 mm × 150 mm × 0.5 mm) of Sky Aluminum Co., Ltd. (60 mm × 150 mm × 0.5 mm) with a doctor blade of 2 mil, and after 30 minutes, the coating composition of 2 mil was coated. It was applied with a doctor blade. After air-drying for a whole day and night, it was baked at 150 ° C. for 1 hour to form a silica film, washed with warm water at 90 ° C. to remove boric acid, and then irradiated with ultraviolet rays to decompose and remove organic substances attached to the catalyst. . It was confirmed by scanning electron microscope observation that a silica film containing titanium dioxide was formed on the surface of the substrate on a silica film not containing titanium dioxide, and these films were fixed on the substrate by a resin. The thickness of the silica film is about 20 μm, and the weight of the silica film is about 1.5 m.
It was g / cm ² . When the adhesiveness and hardness of the coating film of this film were examined by the method of JIS-K5400, the adhesiveness was 10 at the evaluation point and the pencil hardness was 3H or more. 5 cm x
The coating film cut out to 1 cm is put in a 120 ml glass bottle, and acetaldehyde is added to the bottle at a gas concentration of 1000 pp.
After injecting an amount of m to reach 350 m, and irradiating ultraviolet rays having a wavelength of 350 nm at 4.0 to 4.4 mW / cm ² for 1 hour from outside the bottle, the air in the bottle is gas chromatograph G3800 manufactured by Yanagimoto Seisakusho
When measured by (detector FID), the acetaldehyde concentration was 0 ppm. Similarly, acetic acid 50pp
m, trimethylamine 1000ppm, and dimethyl sulfide 50ppm, 0p after 1 hour of UV irradiation.
pm. Also, ethyl mercaptan 1000pp
In m, it became 60 ppm after 1 hour of ultraviolet irradiation. In addition, 10 mg of the titanium dioxide powder for catalyst used above was used.
When a decomposition test of acetaldehyde was carried out in the same manner (about the same amount as contained in the coated surface of 5 cm x 1 cm), the rate of decrease in concentration was almost the same, and the catalytic activity decreased due to the coating film this time. Is thought to be scarce. Table 7
Shows the removal data of acetaldehyde and ethyl mercaptan by ultraviolet irradiation this time. 5cm x 1cm coating film and water 2 in a glass test tube
When 0 ml was added and the mixture was allowed to stand outdoors for one week, algae were found to be generated in the film without coating, but there was no change in the film with coating. Furthermore, this coating film was irradiated with ultraviolet rays of 300 mW / cm ² × 500 hours using a Dewpanel light control weather meter manufactured by Suga Test Instruments Co., Ltd. However, discoloration and strength deterioration of the coating film did not occur.

Example 3 In Example 1, the coating material was iron oxide (plate-like hematite,
Specific surface area 40 m ² / g, major axis / minor axis ratio 5) 6 g, ethyl silicate 9 g, water 3 g added with 0.5 mol of nitric acid, boric acid 0.12 g and butyl cellosolve 6 g 120 ml together with 3 mm glass beads 90 g In the same manner, except that the silica film containing iron oxide and the silica film containing no iron oxide were prepared in the same manner except that they were prepared by dispersing and mixing for 10 minutes with a paint conditioner manufactured by Red Devil Co., Ltd. Was prepared on a substrate.

Example 4 In Example 1, the coating material was zinc oxide (specific surface area 10 m
² / g) 6 g, ethyl silicate 9 g, water 3 g to which 0.5 mol of nitric acid was added, and butyl cellosolve 6 g were charged together with 90 mm of 3 mm glass beads in a 120 ml mayonnaise bottle, and a red Devil paint conditioner for 10 minutes. A silica film containing zinc oxide and a silica film not containing zinc oxide were prepared on a substrate in the same manner except that they were prepared by dispersion and mixing.

Example 5-7 The same procedure as in Example 2 was carried out except that the substrate was Skycoat Co., Ltd. Skycoat polyester, acrylic and fluorine resin coated surface (60 mm × 150 mm × 0.5 mm). , A silica film containing titanium dioxide and a silica film not containing titanium dioxide were prepared on a substrate. These are shown in Table 1 and Table 2.

Example 8-21 Formulation of a coating composition prepared by dispersing silica sol containing no titanium dioxide particles and titanium dioxide particles in Example 2,
A film was prepared by changing the type of resin applied to the substrate and the coating method. These are shown in Table 1 and Table 2. Further, in the same manner as in Example 2 with respect to Example 8-21, acetaldehyde and ethyl mercaptan removal data by ultraviolet irradiation were used.
Table 7 shows the data.

Examples 22 and 23 Example 2 was repeated except that the substrate was polypropylene cloth or fiber.
A film was prepared in the same manner as in 1. Even if they were bent 100 times or more and washed in a washing machine, no weight reduction due to peeling of the silica film was observed.

COMPARATIVE EXAMPLE 1 In Example 1, the coating containing titanium dioxide was directly applied to an aluminum plate and baked at 150 ° C. for 1 hour. Comparative Example 2 A paint prepared by dispersing titanium dioxide in an acrylic resin with the paint composition shown in Table 5 was applied to an aluminum plate. The acrylic resin film was peeled off by irradiation with ultraviolet rays for 500 hours using a Suga Test Instruments Co., Ltd. Dew Panel Light Control Weather Meter. Comparative Example 3 A paint prepared by dispersing titanium dioxide in a urethane resin with the paint composition shown in Table 5 was applied to an aluminum plate. The urethane resin film was peeled off by UV irradiation for 200 hours using a Suga Tester Co., Ltd. Dew Panel Light Control Weather Meter. Comparative Example 4 An aluminum plate coated with a coating in which titanium dioxide was dispersed in melamine and an alkyd resin had no aldehyde decomposition effect.

[0025]

[Table 1]

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

[0029]

[Table 5]

[0030]

[Table 6]

[0031]

[Table 7]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 5/14 PQM C09D 5/14 PQM 7/12 PSK 7/12 PSK 201/00 PDC 201/00 PDC (72) Inventor Tatsuo Saito 25 Titan Industry Co., Ltd., 1978, Kogushi, Ube, Ube City, Yamaguchi Prefecture

Claims (7)

[Claims] 1. An article having a substrate, a resin layer formed on the surface of the substrate, a silica film fixed on the resin layer, and a silica film containing the functional substance powder fixed on the silica film. 2. A metal material whose main component is at least one selected from the group consisting of aluminum, iron, nickel and copper, glass, ceramics, resin, cloth, fiber,
Or the article of claim 1 selected from a combination thereof. 3. The article of claim 1, wherein the functional material powder is selected from titanium dioxide, zinc oxide and iron oxide, or combinations thereof. 4. A silica film is produced by coating the surface of a resin layer formed on the surface of a substrate with a mixed solution of a silicate ester, water and / or an organic solvent, and further adding a silicate ester, water and / or an organic solvent. The method for producing an article according to claim 1, wherein after coating the silica film with a coating material in which the functional substance powder is dispersed, heat treatment is performed at 400 ° C or lower. 5. The mixed solution comprises 25 to 100 parts by weight of water and 0 to 200 parts of an organic solvent based on 100 parts by weight of silicate ester.
The manufacturing method according to claim 4, wherein the amount is 0 part by weight. 6. The coating composition comprises 20 to 5000 parts by weight of silicate ester and 1 part of water based on 100 parts by weight of the functional substance powder.
The manufacturing method according to claim 4, wherein the coating material is a coating material prepared by mixing and dispersing at a ratio of 0 to 1100 parts by weight and an organic solvent of 0 to 1000 parts by weight. 7. A deodorant having a substrate, a resin layer formed on the substrate surface, a silica film fixed on the resin layer, and a silica film fixed on the silica film and containing a functional substance powder.