WO2001021722A1 - Materiau de revetement hydrophile photocatalytique - Google Patents

Materiau de revetement hydrophile photocatalytique Download PDF

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Publication number
WO2001021722A1
WO2001021722A1 PCT/JP2000/006472 JP0006472W WO0121722A1 WO 2001021722 A1 WO2001021722 A1 WO 2001021722A1 JP 0006472 W JP0006472 W JP 0006472W WO 0121722 A1 WO0121722 A1 WO 0121722A1
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WO
WIPO (PCT)
Prior art keywords
hydrophilic coating
coating agent
photocatalytic hydrophilic
photocatalytic
weight
Prior art date
Application number
PCT/JP2000/006472
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English (en)
Japanese (ja)
Inventor
Masahiro Yamamoto
Minoru Takashio
Shigeru Kubozono
Junji Hiraoka
Kazuo Hirano
Mikio Horimoto
Original Assignee
Toto Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toto Ltd. filed Critical Toto Ltd.
Priority to AU73188/00A priority Critical patent/AU7318800A/en
Publication of WO2001021722A1 publication Critical patent/WO2001021722A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates

Definitions

  • the present invention relates to a photocatalytic hydrophilic coating agent that easily makes and maintains the surface of a member highly hydrophilic in the field. More specifically, the present invention provides a photocatalytic hydrophilic coating capable of preventing clouding and water droplet formation of members by making the surfaces of mirrors, lenses, glass, prisms and other transparent members highly hydrophilic while maintaining high transparency.
  • the present invention relates to a coating agent that forms The present invention also prevents the surface from being soiled or makes the surface self-cleaning (self-cleaning) by highly hydrophilizing the surface of a building, a window glass, a mechanical device, or an article with high transparency.
  • the present invention relates to a coating agent that forms a photocatalytic hydrophilic film that can be easily cleaned. Background art
  • the surface can be permanently maintained at a high degree of hydrophilicity, and the hydrophilicity can be improved even in light shielding. It has also been proposed that it can be maintained to some extent (Japanese Patent Application Laid-Open No. 9-1222710).
  • the present invention makes it possible to easily make the surface of a member highly hydrophilic while maintaining high transparency on site, The development of a photocatalytic hydrophilic coating agent to be maintained.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, have developed a photocatalytic hydrophilic coating agent that easily makes the surface of a member highly transparent while maintaining high transparency in the field. Disclosure of the invention
  • the total solid content is 1
  • the alkali metal silicate is 100 to 20% by weight of the 100% by weight.
  • the photocatalytic hydrophilic coating agent of the present invention may contain alcohols (D) for improving repelling properties and preventing freezing.
  • the photocatalytic hydrophilic coating agent of the present invention may contain a surfactant (E) for improving repelling properties and increasing viscosity.
  • the photocatalytic hydrophilic coating agent of the present invention may contain a polymer thickener (F) for increasing the viscosity.
  • the photocatalytic hydrophilic coating agent of the present invention may contain a preservative / antifungal agent (G) for preservative / antifungal purposes.
  • G preservative / antifungal agent
  • Fig. 1 shows the time of the contact angle with water on the surface of the photocatalytic hydrophilic film prepared by applying the photocatalytic hydrophilic coating agents # 1 to 4 and Comparative Examples 1 and 2 to the glass surface. It is the graph which investigated change. BEST MODE FOR CARRYING OUT THE INVENTION
  • the photocatalytic metal oxide (A) in the present invention includes anatase-type titanium oxide, brookite-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, bismuth trioxide, tungsten trioxide, ferric oxide, and titanium.
  • One or more selected from the group of strontium acid can be used.
  • the average crystallite diameter of the photocatalyst particles is preferably 100 nm or less.
  • the upper limit is preferably about 50 nm or less, and more preferably about 20 nm or less.
  • the lower limit is preferably about 1 nm or more.
  • titania is particularly preferable, and among them, neutral or alkaline titania sol is particularly preferable.
  • a titania sol to which an alkyl silicate is added is particularly preferable.
  • a titania sol whose surface is coated with silica is preferable for preventing aggregation and improving dispersion stability.
  • Acidic titania sol is not suitable for use because it causes coagulation and precipitation when mixed with alkali silicate.
  • alkyl silicate (B) tetraalkoxysilanes such as tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane and tetrabutoxysilane are preferable.
  • the alkali silicate (C) include alkali silicates represented by the general formula Me 2 ⁇ ⁇ nSi 0 2 (where Me represents an alkali metal) (for example, water glass, silicate Potassium, lithium silicate, and sodium silicate). Further, the alkali metal silicates may be used as a mixture or a composite. In the present invention, the alkali metal silicate-containing solution contains Fr, Cs, Rb, K, Na, and And at least one metal selected from the group consisting of Li. Also, instead of alkali metal salts, alkali silicates such as ammonium silicate may be used.
  • the alkali silicate (C) preferably contains 10 to 40% by weight of the total solids of 100% by weight.
  • Alkali metal silicates are cured immediately after coating at room temperature, so they are suitable for in-situ coating, which cannot be heated, and can compensate for the disadvantages of alkyl silicate (B), which has a slow curing rate.
  • 100% by weight of alkali silicate (C) was added to 100% by weight of the total solid content. It is preferable to include the above.
  • alkali silicate (C) has a large amount of non-crosslinking oxygen and has a function of maintaining hydrophilicity in the absence of light.
  • the non-woven fabric is impregnated with the photocatalytic hydrophilic coating agent of the present invention and then applied to the substrate, if the alkali silicate (C) is too much, the liquid will gather in a streak shape during drying, resulting in poor appearance.
  • the content is preferably less than 40% by weight based on the total solid content.
  • the alkali metal silicate (C) contains 10 to 20% by weight of the total solid content of 100% by weight. .
  • Alcohols (D) include methanol, ethanol, 1-propanol, 2-propanol, t-butanol, 2-butanol, and 1-butanol. These can be used alone or in combination of two or more. Of these, highly polar ethanol, methanol and 2-propanol, which are difficult to separate from water due to the salting-out effect of the alkali silicate during drying, are particularly preferred. To prevent freezing, it is preferable to add 5% by weight or more. . Further, in order not to cause gelation of the alkali silicate, the amount of alcohol added is preferably 20% by weight or less.
  • surfactant (E) examples include polyhydric alcohol-type nonionic surfactants (eg, fatty acid monoester of glycerol, sorbitan ester, and fatty acid ester of sugar), and polyethylene glycol-type nonionic surfactant (such as higher alcohol).
  • polyhydric alcohol-type nonionic surfactants eg, fatty acid monoester of glycerol, sorbitan ester, and fatty acid ester of sugar
  • polyethylene glycol-type nonionic surfactant such as higher alcohol
  • Polyoxyalkylene oxide adducts alkylphenol polyoxyalkylene oxide adducts, fatty acid polyoxyalkylene oxide adducts, higher aliphatic amines Polyoxyalkylene oxide adducts, pull nick type nonionic surfactants, polyoxyalkylene oxide additives of polyhydric alcohol type nonionic surfactants, polyether-modified organosiloxanes, etc.), fatty acids
  • Nonionic surfactants such as alcohol amides, perfluoroalkyl sulfonates, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adducts, perfluoroalkyltrimethylammonium salts, Perfluoroalkylaminosulfonate, oligomer containing perfluoroalkyl group (eg, “MegaFac” manufactured by Dainippon Ink and Chemicals, Inc.), perfluoroalkenyloxybenzenesulfon
  • the addition amount of the surfactant (E) is preferably from 0.001 to 0.3% by weight. If the content is less than 0.001% by weight, there is no effect of improving the leveling property and the viscosity, and if the content is more than 0.3% by weight, the coating film is whitened and the appearance is poor.
  • polymeric thickener (F) examples include water-soluble polymers, carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, xanthan gum, guar gum, agar, dextrin, starch, pectin, sodium alginate , Arabic gum, Gelatin, Lignin sulfonate, Polyethylene glycol, Polypropylene glycol, Polyoxyvinyl polymer, Acrylic ester polymer, Polyacrylate, Polyacrylamide, Polyvinyl alcohol, Polyvinylpyrrolidone, Polyvinyl acetate, Polyvinyl acetate Compound, acrylic acid ester polymer, isobutyl maleic acid copolymer, acrylic acid Z-methacrylic acid copolymer, acrylic acid Z Use may be made of, for example, a lactic acid copolymer, a methyl vinyl ether maleic anhydride copolymer, a urethane resin, an acrylic resin, and the like
  • the amount of the polymer thickener (F) to be added is preferably 0.05 to 0.3% by weight.
  • Addition of less than 0.005% by weight does not have the effect of improving the viscosity, while addition of more than 0.3% by weight is not preferable because the coating film is whitened and poor appearance is caused.
  • Any preservative or fungicide (G) can be used as long as it is water-soluble.
  • salts containing copper ions such as copper sulfate and ionic ones such as sodium azide can be particularly preferably used. Copper ions are easily precipitated by alkalization and can be suitably used at less than 200 ppm, and sodium azide is preferably 0.1% by weight or less from the viewpoint of toxicity.
  • a fragrance, an antioxidant, a chelating agent, an antifoaming agent and the like may be mixed or used in combination, if necessary.
  • the method of applying the composition according to the present invention to the surface of the substrate may be appropriately selected.
  • examples thereof include a spray coating method, an aerosol coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, and a brush.
  • Methods such as coating, sponge coating, and non-woven fabric coating can be suitably used.
  • the product form of the photocatalytic hydrophilic coating agent of the present invention includes aerosol spray, A hand spray, a container form in which the nonwoven fabric or sponge for application is integrated with the bottle, and the liquid is leached from the bottle through the nonwoven fabric or the like described above. Further, a product obtained by impregnating a nonwoven fabric, sponge, cloth, paper, or the like with the present composition can be sealed in a pack formed of resin-laminate film to obtain a product.
  • the nonwoven fabric is impregnated with a fixed amount of the solution and applied to the user in order to keep the amount of the coating solution constant.
  • regenerated cellulose fibers having good water retention such as picose rayon, Cubraammonium rayon, and lyocell, are particularly preferable.
  • a non-woven fabric can be impregnated with a fixed amount of a photocatalytic hydrophilic coating agent, and the product can be enclosed in a resin or laminate film pack to form a product. At this time, it is desirable that the film contains an aluminum foil layer to impart strength.
  • a layer of polyacrylonitrile or polyolefin is particularly desirable on the liquid contact surface to prevent loss of adsorption of the photocatalytic metal oxide (A).
  • the hydrophilicity-restoring agent of the present invention can be used for a photocatalytic hydrophilic film whose hydrophilicity has been impaired by the attachment of a contaminant.
  • Substrates to be used in anti-fog applications include glass, transparent plastics, lenses, and prisms. It is a transparent substrate such as a mirror.
  • mirrors such as bathroom or toilet mirrors, vehicle rearview mirrors, dental tooth mirrors, road mirrors; spectacle lenses, optical lenses, camera lenses, endoscope lenses, illumination lenses, Lenses such as semiconductor manufacturing lenses; prisms; windows of buildings and watchtowers; vehicles such as cars, railcars, aircraft, ships, submersibles, snowmobiles, ropeway gondolaes, amusement park gondolas, and spacecraft Windshields for vehicles such as cars, railway vehicles, aircraft, ships, submersibles, snowmobiles, snowmobiles, motorcycles, ropeway gondolaes, amusement park gondolas; protective or sport goggles Or shields for masks (including diving masks); helmet shields; glass for frozen food display cases; cover glass for measuring instruments; and Adhered possible film to these products goods, is the emblem and the like.
  • building exteriors such as exterior walls and roofs; window frames; exteriors and coatings of vehicles such as cars, railcars, airplanes, ships, bicycles, and motorcycles; windowpanes; signboards, traffic signs, soundproofing.
  • Substrates targeted for applications where cleaning by water washing can be expected include, for example, metals, ceramics, glass, plastic, wood
  • Substrates that can be expected to promote drying include, for example, window sashes, radiating fins for heat exchangers, pavements, bathroom toilet mirrors, greenhouse ceilings, vanities, automobile bodies and their products. Possible films, patches, etc.
  • the optical excitation of the optical semiconductor is performed by irradiating the optical semiconductor with light having energy larger than the energy gap (ie, shorter wavelength) between the conduction electron band and the valence band of the optical semiconductor crystal.
  • the wavelength is 387 ⁇ m or less when the optical semiconductor is an analog-type titanium oxide, the wavelength is 413 nm or less when the rutile titanium oxide is used, and the wavelength is when the tin oxide is tin oxide. Irradiate a light beam containing light with a wavelength of 344 nm or less, or in the case of zinc oxide, a wavelength of 378 nm or less.
  • the illuminance of light necessary for photoexcitation of the optical semiconductor required for hydrophilizing the composite material surface is 0.000 lmWZcms or more, preferably 0.001 mW / cm2 or more, more preferably 0.01 mW / c or more. m2 or more.
  • the photocatalytic coating composition is a group of silver, copper, palladium, platinum, rhodium, platinum, ruthenium, gold, zinc, cobalt, iron, nickel, sodium, lithium, strontium, potassium, calcium, magnesium, or a compound of these metals. One or more selected from the following may be added.
  • Antibacterial properties can be imparted by adding at least one selected from the group consisting of silver, copper, zinc and compounds of these metals.
  • the photocatalytic coating composition can include a substance having a refractive index of 2 or less.
  • the addition of a substance having a refractive index of 2 or less has the advantage that visible light can be effectively prevented from being reflected on the applied surface.
  • Substances with a refractive index of 2 or less that can be added to the photocatalyst coating composition include silicic acid (refractive index: 1.5), tin oxide (1.9), calcium carbonate (1.6), and hydroxylic acid. (1.6), Magnesium carbonate (1.5), Strontium carbonate (1.5), Dolomite (1.7), Calcium fluoride (1.4), Magnesium fluoride (1) 4), Alumina (same as 1.6), Kee sand (same as 1.6), Zeolite (same as above)
  • the member surface becomes hydrophilic in response to photoexcitation of the photocatalyst.
  • the illuminance of the excitation light may be 0.001 mW / cm2 or more, but 0.01 mW / cm2. More preferably, it is more than 0.1 mWZ cm2.
  • the photocatalytic oxide is anatase-type titanium oxide, rutile-type titanium oxide, zinc oxide, or strontium titanate
  • the light source used for photoexcitation of the photocatalyst is a solar light, indoor lighting, a fluorescent lamp, a mercury lamp, an incandescent lamp, Xenon lamps, high-pressure sodium lamps, metal halide lamps, BLB lamps, etc.
  • the photocatalytic oxide is tin oxide, a germicidal lamp, a BLB lamp, or the like can be suitably used.
  • the thickness of the surface layer formed by a coating film on the member surface is preferably set to 0.4 m or less. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent.
  • the thickness of the surface layer is set to 0.2 or less. By doing so, it is possible to prevent coloration of the surface layer due to light interference.
  • the thinner the surface layer the better its transparency. Further, if the film thickness is reduced, the wear resistance of the surface layer is improved.
  • Table 1 shows the compositions of the photocatalytic hydrophilic coating agents # 1 to # 4 of the present invention and Comparative Examples 1 to 3.
  • # 1 to # 4 and Comparative Examples 1 and 2 were prepared by diluting S1 with water (deionized water or distilled water) in order to avoid a sharp pH change in And mixed slowly.
  • T1 was constantly stirred with a magnetic stirrer.
  • Comparative Example 3 11-propanol was gradually added to T2 and mixed.
  • T 2 was constantly stirred with a magnetic stirrer.
  • T2 “ST- ⁇ 03” manufactured by Ishihara Sangyo Co., Ltd. (analyte type titanium dioxide and ethyl silicate 10% by weight in total, 2-propanol, water, methanol and nitric acid in total 9
  • the compositions # 1 to 4 and Comparative Examples 1 to 3 shown in Table 1 were prepared using Asahi Kasei Corporation's cupra nonwoven fabric “Benrize TS_100” ( (Size: 20 OmmX 265 mm) was impregnated with 14 g, and slid in one direction at a speed of 30 cmZs and smeared. After the coated glass was dried at room temperature (251 :) for 30 minutes, the contact angle of the coating with water was measured, and the contact angle with water immediately after coating was determined.
  • Table 2 shows the contact angle of the coating film surface with water immediately after application.
  • the photocatalytic hydrophilic coating agents # 1 to # 4 containing 10 to 40% by weight of alkali silicate had a contact angle of 10 degrees or less.
  • the temperature was higher than 10 degrees
  • Comparative Examples 2 to 3 containing no alkali silicate the temperature was higher than 20 degrees.
  • compositions # 1 to 4 and Comparative Examples 1 to 2 shown in Table 1 were applied to the surface of soda lime glass (size: 10 O mm X 10 O mm X 2 mm) under the same conditions as in Evaluation 1, and Dried for 30 minutes at warm (at 25).
  • Figure 1 shows the change over time of the contact angle of the coating film surface with water in a dark place after coating.
  • the photocatalytic hydrophilic coating agents # 1 to # 4 containing 10 to 40% by weight of alkali silicate maintained a contact angle of 30 ° or less for 16 hours after application.
  • Comparative Example 1 containing 8.7% by weight of the alkali silicate gave almost the same results.
  • Comparative Example 2 containing no alkali silicate had a temperature of 40 ° C. or higher.
  • compositions # 1 to # 4 and Comparative Examples 1 and 2 shown in Table 1 were applied to the surface of soda lime glass (size: 10 O mm x 10 O mm X 2 mm) under the same conditions as in Evaluation 1. After the coating was dried at room temperature (at 25) for 24 hours, the surface of the coating was rubbed with a finger and the appearance of the coating was visually observed. Table 3 shows the results. Of the total solids of 100% by weight, the higher the concentration of alkali silicate, the higher the physical height of the membrane.
  • Photocatalytic hydrophilic coating agent containing 10 to 40% by weight of alkali silicate # 1 to # 4 hardly rubs with fingers Although the whitening did not occur or the whitening was slight, in Comparative Examples 1 and 2, the physical strength of the film was weak and the whitening was clearly observed.
  • compositions # 1 to # 4 and Comparative Examples 1 and 2 shown in Table 1 were applied to the surface of soda lime glass (size: 10 OmmX 10 OmmX 2 mm) under the same conditions as in Evaluation 1. After coating, the coating was dried at room temperature (25) for 30 minutes, and then tap water was showered at 6 LZ for 20 minutes, and the peeling state of the film was observed. Table 4 shows the results. Since the photocatalytic hydrophilic coating agents # 1 to # 4 did not change their visual appearance and their contact angles remained low, it was judged that the films did not peel. In Comparative Examples 1 and 2, whitening and film flow were observed immediately after showering, and it was determined that the film was peeled.
  • compositions # 1 to # 4 and Comparative Examples 1 to 2 shown in Table 1 were applied to the surface of soda lime glass (size: 10 OmmX 10 OmmX 2 mm) under the same conditions as in Evaluation 1. After the coating was dried at room temperature (25) for 30 minutes, the coating film surface was visually observed. The results are shown in Table 5. The visual appearance of the photocatalytic hydrophilic coating agents # 1 to # 2 is almost the same as before coating. Very good, almost unchanged. The photocatalytic hydrophilic coating agents # 3 to # 4 were slightly conspicuous. For substrates that require extremely high transparency, photocatalytic hydrophilic coating agents # 1 to # 2 containing 100 to 20% by weight of alkali silicate out of 100% by weight of the total solids are used.
  • photocatalytic hydrophilic coating agents # 3 to # 4 containing 20 to 40% by weight of aluminum silicate are suitable.
  • the appearance of the coating films of Comparative Examples 1 and 2 was good.
  • Table 6 shows the compositions of the photocatalytic hydrophilic coating agents # 5 to # 9 of the present invention and Comparative Examples 4 to 5.
  • T 1 “STS_200” manufactured by Ishihara Sangyo Co., Ltd. (anatase type titanium dioxide and methyl silicate in total 4.8% by weight, water, methanol and 2-propanol in total 95.2% by weight, titanium dioxide Z silica weight ratio 5) 5, pH 6.1 1)

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Catalysts (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Surface Treatment Of Glass (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un matériau de revêtement hydrophile photocatalytique pouvant être facilement appliqué in situ sur la surface d'un élément de manière à lui conférer un degré élevé d'hydrophilie ainsi qu'une grande transparence, ce qui préserve sa capacité hydrophile. Ce matériau de revêtement contient de l'eau, un oxyde métallique photocatalytique (A), un silicate d'alkyle (B), et un silicate alcalin (C). Les proportions du composant (A) par rapport au composant (B) sur une base solide s'expriment par le rapport de TiO2 qui est compris entre 2/8 et 8/2. La teneur en silicate d'alkyle est comprise entre 10 et 40 % en poids sur la base de tous les composants solides.
PCT/JP2000/006472 1999-09-21 2000-09-21 Materiau de revetement hydrophile photocatalytique WO2001021722A1 (fr)

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Application Number Priority Date Filing Date Title
AU73188/00A AU7318800A (en) 1999-09-21 2000-09-21 Photocatalytic hydrophilic coating material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP26665299A JP2001089706A (ja) 1999-09-21 1999-09-21 光触媒性親水性コート剤
JP11/266652 1999-09-21

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WO2001021722A1 true WO2001021722A1 (fr) 2001-03-29

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CN105542523A (zh) * 2016-02-23 2016-05-04 西北永新涂料有限公司 一种室内高效除甲醛光触媒清漆
CN109762377A (zh) * 2018-12-28 2019-05-17 山西艾珂灵环境科技有限公司 纳米自清洁薄膜及制备方法和灯具

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BRPI0719476A2 (pt) 2006-12-22 2014-02-11 3M Innovative Propereties Company "artigo revestido, grânulo revestido para telhado, composição de revestimento e método para fabricação de um artigo revestido e de um grânulo revestido para telhado"
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KR101594025B1 (ko) * 2008-12-27 2016-02-15 니끼 쇼꾸바이 카세이 가부시키가이샤 고 굴절률 금속 산화 미립자를 포함하는 도료 조성물 및 그 도료 조성물을 기재 위에 도포하여 수득된 경화성 도막
JP5452249B2 (ja) * 2010-01-26 2014-03-26 パナソニック株式会社 塗料組成物と塗装品並びに塗装方法
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