WO2006049008A1 - Composition de revêtement inorganique, film de revêtement hydrophile et procédé servant à former un film de revêtement hydrophile - Google Patents

Composition de revêtement inorganique, film de revêtement hydrophile et procédé servant à former un film de revêtement hydrophile Download PDF

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Publication number
WO2006049008A1
WO2006049008A1 PCT/JP2005/019064 JP2005019064W WO2006049008A1 WO 2006049008 A1 WO2006049008 A1 WO 2006049008A1 JP 2005019064 W JP2005019064 W JP 2005019064W WO 2006049008 A1 WO2006049008 A1 WO 2006049008A1
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Prior art keywords
coating composition
organic solvent
inorganic coating
water
coating film
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PCT/JP2005/019064
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English (en)
Japanese (ja)
Inventor
Youhei Kawai
Takashige Yoneda
Katsumasa Nakahara
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Asahi Glass Company, Limited
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Priority to JP2006542977A priority Critical patent/JPWO2006049008A1/ja
Publication of WO2006049008A1 publication Critical patent/WO2006049008A1/fr

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    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances

Definitions

  • the present invention relates to an inorganic coating composition, a hydrophilic coating film, and a method for forming a hydrophilic coating film capable of obtaining a hydrophilic coating film having excellent transparency.
  • organic base materials such as plastics are used for various purposes such as power bars of various lamps, spectacle lenses, goggles, covers of various instruments, agricultural films, etc. because of their excellent transparency. ing.
  • organic base materials such as plastics have a disadvantage that they tend to cause dew condensation because they are hydrophobic.
  • condensation may form on the inner surface of the cover, resulting in cloudy fogging, which may cause a problem that the display cannot be seen.
  • a method for imparting hydrophilicity to the surface of an organic substrate a method of forming an inorganic layer on the surface is known. Specifically, a method of forming a coating film by applying and drying an inorganic paint containing alumina sol or silica zonole (Patent Document 1) and the like can be mentioned. However, this method has a problem that the coating film to be formed is in a state in which the alumina particles and the silica particles are adhered to the organic base material by the surfactant, so that the adhesion to the base material is lacking.
  • Patent Document 1 Japanese Patent Laid-Open No. 60-69181
  • Patent Document 2 US Patent No. 4413088
  • the present invention has the following features.
  • An inorganic coating composition capable of forming a hydrophilic coating on an organic substrate, wherein (a) silica particles having an average particle size of 5 to 100 nm, (b) a surfactant, (c) organic Organic solvent A that can swell or dissolve the substrate and has a boiling point of 130 ° C or higher at an atmospheric pressure of 0. IMPa and is miscible with water. (D) The organic substrate is substantially swollen or dissolved. A water-miscible organic solvent B and (e) water having a boiling point of 50 to 120 ° C at a pressure of 0 ⁇ 1 MPa, and (e) water, and in the inorganic coating composition, The content of organic solvent A is:! ⁇ 10% by mass, the content of organic solvent B is 0 ⁇ 97.2% by mass, the solid content is 0.:! ⁇ 20% by mass, solid An inorganic coating composition containing 3.5 to 17 times the water content.
  • the organic solvent A is diglyme, N, N-dimethylformamide, N, N-dimethylacetamide, acetoacetate, N-methyl-1-pyrrolidinone, 2-pyrrolidinone, 1,3-dimethinole-2-imidazo
  • the inorganic coating composition according to the above (1) or (2) which is at least one selected from the group consisting of lysinone and dimethyl sulfoxide.
  • the solids content is 0.:! ⁇ 20% by mass, and the solids content is 3.5 ⁇ : 17 times the water content.
  • an inorganic film that has high transparency, high adhesion to an organic base material, high hydrophilicity, and excellent antifogging property, antifouling property, and flowability.
  • a coating composition, a hydrophilic coating film, and a method for forming a hydrophilic coating film can be obtained.
  • the inorganic coating composition of the present invention comprises (a) an average particle size of 5 to:! OOnm silica particles, (b) a surfactant, (c) an organic solvent A, (d) an organic solvent B and (e ) Contains water.
  • the silica particles serve as a main agent for forming a coating film.
  • the silica particles are preferably colloidal silica or gas phase synthetic silica.
  • the silica particles are required to have an average particle diameter of 5 to 100 nm. This is preferable because a coating film having excellent transparency can be obtained. If the average particle diameter of the silica particles is less than 5 nm, a dense film with a small pore volume is formed, and the hydrophilicity may be lowered. This is preferable because it may become cloudy and inferior in transparency.
  • the silica particles preferably have an average particle size of 10 to 20 nm, preferably an average particle size of 5 to 30 nm. Here, the average particle size is defined as that based on mass.
  • any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used.
  • Surfactants include: —CH 2 CH0—, —SO 1, —NR— (where R is a hydrogen atom or organic group), —NH, —SO
  • Y is hydrogen, sodium, potassium or ammonium
  • Nonionic surfactants having a structural unit of (on) are preferred.
  • the structure of -CH CH 0_ is used because there is no risk of impairing the storage stability and hydrophilicity of the inorganic coating composition.
  • Nonionic surfactants having 2 2 units are particularly preferred.
  • Nonionic surfactants include, for example, alkyl polyoxyethylene ethers, alkyl polyoxyethylene monopolypropylene ethers, fatty acid polyoxyethylene esters, fatty acid polyoxyethylene sorbitan esters, fatty acid polyoxyethylene sonolebitole esterol, Examples thereof include alkyl polyoxyethylene amine, alkyl polyoxyethylene amide, and polyether-modified silicone surfactants.
  • an organic solvent A is contained in the inorganic coating composition.
  • the adhesiveness of the obtained coating film can be improved.
  • the organic solvent A swells or dissolves the organic substrate, so that the surface of the organic substrate becomes microscopic. After the silica particles infiltrated into the micro-defect site and the organic solvent A volatilized, the resin contracted on the surface of the organic substrate, and the silica particle was embedded in the organic base material. It is thought that it is fixed in a state.
  • the organic solvent A can swell or dissolve the organic base material and has a boiling point of 130 ° C or higher at a pressure of 0. IMPa.
  • the organic solvent A is preferably mixed with water in the inorganic coating composition so that the inorganic coating composition causes phase separation.
  • the organic solvent A preferably has a water solubility of 2 or more.
  • the solubility in water means the amount (g) of the organic solvent A dissolved in 100 g of water at a temperature of 20 ° C.
  • the organic solvent A has a boiling point of 130 ° C or higher at a pressure of 0.1 IMPa, it can remain in the inorganic coating composition as compared with the organic solvent B and water. The effect can be shown.
  • organic solvent A has a boiling point of 160 to 300 ° C. at a pressure of 0. IMPa.
  • Organic solvents A are diglyme, N, N-dimethylformamide, N, N-dimethylase. Preference is given to at least one selected from the group consisting of toamide, acetyl acetoacetate, N-methyl 2 pyrrolidinone, 2 pyrrolidinone, 1,3 dimethyl 2-imidazolidinone and dimethyl sulfoxide.
  • the inorganic coating composition of the present invention contains an organic solvent B.
  • the organic solvent B Similarly to the organic solvent A, the organic solvent B must be mixed with water in the inorganic coating composition so that the inorganic coating composition does not cause phase separation when preparing the inorganic coating composition. For this reason, the organic solvent B preferably has a water solubility of 2 or more. Further, the organic solvent B must have a boiling point of 50 to 120 ° C. in a state of atmospheric pressure of 0.1 IMPa. As a result, the organic solvent A remains uniformly on the surface of the organic base material because it evaporates faster than the organic solvent A during drying after coating the inorganic coating composition, and the organic base material surface uniformly swells or dissolves. Is preferable.
  • the organic solvent B is preferably at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and t-butanol.
  • the inorganic coating composition of the present invention can contain a hydrophilic resin as necessary.
  • the inclusion of this hydrophilic resin is preferable because it has the effect of improving the strength of the resulting coating film.
  • the hydrophilic resin include polyacrylic acid, polyvinyl alcohol, polypropylene, polyurethane, and cellulose.
  • the content of the hydrophilic resin is preferably 100 parts by mass or less with respect to 100 parts by mass of the solid content of the inorganic coating composition. If the content of the hydrophilic resin is more than 100 parts by mass, it is not preferable because the durability of hydrophilicity may deteriorate the abrasion resistance.
  • the content of the hydrophilic resin is particularly preferably 50 parts by mass or less with respect to 100 parts by mass of the solid content of the inorganic coating composition.
  • the inorganic coating composition of the present invention can contain additives such as coloring dyes, pigments, ultraviolet absorbers and antioxidants as necessary.
  • the content of the organic solvent A needs to be 1 to 10% by mass of the inorganic coating composition.
  • the organic solvent A is considered to function to swell or dissolve the organic base material so that the silica particles are loaded in the base material. Therefore, the organic solvent A depends on the total concentration, not the solid content, in the inorganic coating composition which only needs to be present in an amount covering the surface of the organic substrate. If the content of organic solvent A is less than 1% by mass, the resulting coating This is not preferable because the adhesion of the film to the organic substrate may be reduced. If the content of the organic solvent A exceeds 10% by mass, the influence of erosion on the organic base material is increased, the surface smoothness may be impaired, and the transparency of the coating film may be lowered. This is preferable because the appearance of the film may be deteriorated.
  • the content of the organic solvent A is particularly preferably 3 to 7% by mass.
  • the content of the organic solvent B needs to be 0 to 97.2% by mass in the inorganic coating composition.
  • the content of 0% by mass means that no organic solvent B is contained. That is, the inorganic coating composition of the present invention may not contain any organic solvent B.
  • the organic solvent B plays a role in improving the coating property of the inorganic coating composition on the organic substrate.
  • the content of the organic solvent B is particularly preferably 0 to 50% by mass.
  • the solid content of the inorganic coating composition of the present invention is required to be 0.:! To 20% by mass. If the solid content is less than 0.1% by weight, unevenness tends to occur when the inorganic coating composition is applied. Therefore, when the solid content is more than 20% by weight, it is difficult to apply. This is not preferable because the workability of the is deteriorated. It is particularly preferable that the solid content of the inorganic coating composition is 0.:! To 10% by mass.
  • the water content needs to be 3.5 to 17 times the solid content (mass basis) of the inorganic coating composition.
  • Water plays a role in stabilizing the dispersibility of the silica particles in the inorganic coating composition. It is preferable that the water content is less than 3.5 times the solid content of the inorganic coating composition, because in the inorganic coating composition, the stability of the silica particles is reduced and aggregation may occur and sediment. Nare ,. If the water content is more than 17 times the solid content of the inorganic coating composition, the wettability of the inorganic coating composition is reduced, and the workability during application may be deteriorated. .
  • the water content is preferably 5 to 11 times the solid content of the inorganic coating composition.
  • the content of the surfactant is preferably:! If the surfactant content is less than 1 ppm, the wettability of the inorganic coating composition will decrease, and the workability during application may deteriorate, so the surfactant content is more than 500 ppm. If there is, there is a possibility that the quality of the appearance of the coating film to be obtained may be deteriorated, which is preferable.
  • Surfactant content should be 10-400ppm Particularly preferred.
  • the inorganic coating composition of the present invention can be applied to an organic substrate to form a hydrophilic coating film.
  • the organic base material various materials can be used as necessary, but it is preferable to use a substrate made of polycarbonate or acrylic resin. Further, the shape of the substrate is not limited to a flat plate, and may have a curvature on the entire surface or a part thereof.
  • the hydrophilicity of the resulting coating film can be evaluated by the contact angle with water.
  • the contact angle of the resulting coating film is preferably 20 ° or less. If the contact angle is more than 20 °, the hydrophilicity of the resulting coating film becomes insufficient, which is preferable.
  • the contact angle is particularly preferably 10 ° or less, and most preferably 5 ° or less.
  • the obtained coating film is excellent in transparency, it is suitable for use particularly when the organic substrate is transparent.
  • the haze value of the obtained coating film is preferably 1% or less. If the haze value is more than 1%, the transparency of the coating film is deteriorated and the transmittance is lowered, which is not preferable.
  • the haze value of the obtained coating film is particularly preferably 0.5% or less.
  • the pore volume of the obtained coating film is preferably 0.3 to 1.5 ml / g.
  • the pore volume is less than 0.3 ml / g, the pores become smaller, the amount of hydrophilic groups decreases, and the antifogging property of the resulting coating film decreases, which is not preferable.
  • the pore volume is more than 1.5 ml / g, the transparency of the coating film is impaired, and the mechanical strength of the coating film may be lowered.
  • the pore volume is particularly preferably from 0.5 to: 1.2 ml / g.
  • the pore volume of the coating is preferably measured by the nitrogen adsorption / desorption method.
  • silica particles having an average particle diameter of 5 to 100 nm, (b) a surfactant, (c) an organic solvent A, (d) an organic solvent B and (e) water are mixed to form an organic
  • the content of solvent A is:! ⁇ 10 mass%
  • the content of organic solvent B is 0 ⁇ 97.2 mass%
  • the solid content is 0.:! ⁇ 20 mass%
  • the solid content is 3.5-:
  • a hydrophilic coating film can be formed.
  • the application method of the inorganic coating composition can be performed by a conventionally known method.
  • examples include brush coating, roller coating, hand coating, spin coating, dip coating, coating by various printing methods, curtain flow, die coating, flow coating, spray coating, and the like.
  • heating or irradiation with electromagnetic waves may be performed as necessary. Heating is determined based on the heat resistance of the organic substrate, but 60 to 100 ° C is preferable.
  • the inorganic coating composition of the present invention no pretreatment is required for the organic substrate, but plasma treatment, corona treatment, UV treatment, ozone treatment is performed for the purpose of further improving the adhesion of the coating film.
  • plasma treatment, corona treatment, UV treatment, ozone treatment is performed for the purpose of further improving the adhesion of the coating film.
  • Etc. chemical treatment such as water, acid or alkali, or physical treatment using an abrasive.
  • the film thickness of the obtained coating film is preferably 30 to 3000 nm. If the coating film thickness is less than 30 nm, the hydrophilicity and sustainability of the effect may be reduced. If the coating film thickness is more than 3000 nm, cracks are likely to occur or interference occurs. If stripes are generated or scratched, it is not preferable because the scratches become conspicuous.
  • the film thickness is particularly preferably from 50 to:! OOOnm.
  • Example 3 As a comparative example, Example 3,
  • silica sol (Catalyst Kasei Kogyo Co., Ltd., trade name: Catalloy KS, model: SI_ 30, average particle size: 12 nm, solid content 30%) 30 g, water 55 g, N 1, N —Dimethylacetamide (pressure 0. boiling point 166 ° C at IMPa, solubility in water: dissolves in any proportion)
  • nonionic surfactant with 0.1% content (Nippon Tunica Co., Ltd., trade name: L-77) 10 g of ethanol solution was added and stirred at 20 ° C. for 1 hour to obtain an inorganic coating composition having a solid content of 9%.
  • the N, N-dimethylacetamide content was 5%
  • the ethanol content was 10%
  • the water content relative to the solid content of the inorganic coating composition was 8.44 times.
  • 3 g of the obtained inorganic coating composition was applied onto a polycarbonate plate (100 mm x 100 mm, thickness 3.5 mm) wiped with ethanol, spin-coated at 150 rpm for 70 seconds, and then at 100 ° C for 10 minutes
  • the film was dried to form a 300 nm thick coating film.
  • the thickness of the coating film was measured with a stylus type film thickness meter (manufactured by Sloan, model: Dektak3030).
  • Tables 1 and 2 show the evaluation results.
  • the obtained inorganic coating composition was used, and the same operation as in Example 1 was performed to form a coating film and evaluated.
  • the evaluation results are also shown in Tables 1 and 2.
  • the contact angle of the coating film with water was evaluated.
  • the contact angle of water on the surface of the coating film was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model: CA-XI 50). Measurements were taken at five different points, and the average value was calculated.
  • the sample was allowed to stand for 1 month in an environment of a temperature of 25 ° C and a humidity of 50%, and the hydrophilicity of the coating film after being allowed to stand was evaluated.
  • the anti-fogging durability evaluation was performed after the coating film product was left for 1 month in an environment of a temperature of 25 ° C and a humidity of 50%.
  • the coated product was inclined 45 degrees and exposed outdoors for 1 month. After that, the sample is collected, and distilled water is applied to the surface of the Sampnore coating to maintain hydrophilicity. The product was visually observed. Yes, when hydrophilicity is maintained in an area of 90% or more, ⁇ , when hydrophilicity is maintained in an area of 50% or more, and hydrophilicity is maintained only in an area of 50% or less. The case was evaluated as X.
  • the surface of the coating film of the sample was worn back and forth 100 times with a cotton cloth, and the peeling state of the coating film was observed with the naked eye.
  • the case where the coating film was not peeled at all was marked as ⁇
  • the case where more than half was peeled off was marked as X.
  • the refractive index of the sample was measured with a spectroscopic ellipsometer (manufactured by Otsuka Electronics, model: FTM7700W).
  • the pore volume was measured with a gas adsorption measuring device (manufactured by Cantachrome, model: Autosorb 3B type).
  • Example 1 silica sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: Cataloid S, model: SI- 45 P, average particle size: 45 nm, solid content 40%) 22.5 g was used and 62.5 g of water was used. Except for the above, the same operation as in Example 1 was carried out to obtain an inorganic coating composition.
  • the N, N-dimethylacetamide content was 5%
  • the ethanol content was 10%
  • the water content was 8.44 times the solid content of the inorganic coating composition.
  • Example 2 An inorganic coating composition was obtained in the same manner as in Example 1 except that 40 g of water and 20 g of N-dimethylacetamide were used in Example 1.
  • the N, N-dimethylacetamide content was 20%
  • the ethanol content was 10%
  • the water content relative to the solid content of the inorganic coating composition was 6.78 times. .
  • Example 2 An inorganic coating composition was obtained in the same manner as in Example 1 except that 65 g of water and N-dimethylacetamide were not added in Example 1.
  • the ethanol content is 10%.
  • the content of water with respect to the solid content of the inorganic coating composition was 9.56 times.
  • Example 1 In Example 1, except that 58g is used, and 2-pyrrolidinone (pressure 0. boiling point 245 ° C at IMPa, solubility in water: dissolves at an arbitrary ratio) is 2g instead of N-dimethylacetamide.
  • the operation was conducted in the same manner as in Example 1 to obtain an inorganic coating composition.
  • the content of 2_pyrrolidinone was 2%, the content of ethanol was 10%, and the content of water with respect to the solid content of the inorganic coating composition was 8.78 times.
  • Example 1 an operation was carried out in the same manner as in Example 1 except that the surfactant was not added, to obtain an inorganic coating composition.
  • Example 1 instead of the nonionic surfactant “L_77”, a fluorine-containing nonionic surfactant (CF CH CH CH (CH) 0 (CH CH O) (CH CH (CH) O) H, x: y
  • Polyvinyl alcohol (manufactured by KURARENE, trade name: POVAL 124) was mixed with water to obtain a polybulal alcohol aqueous solution having a content of 3%.
  • Acrylic ester copolymer dispersion (manufactured by Nippon Pure Chemical Co., Ltd., trade name: Diyurimer APO-601N, solid content 17%) is mixed with water to disperse 3% acrylic ester copolymer. A liquid was obtained.
  • Example 8 instead of 3% polybulal alcohol aqueous solution, 3% content An inorganic coating composition having a solid content of 9% was obtained in the same manner as in Example 1 except that the acrylic ester copolymer dispersion was used.
  • the N, N-dimethylacetamide content was 5%
  • the ethanol content was 10%
  • the water content was 8.44 times the solid content of the inorganic coating composition.
  • a coating film was formed in the same manner as in Example 1 except that the base material was changed to polymethyl methacrylate in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

L'invention concerne une composition de revêtement inorganique laquelle permet de former un film de revêtement ayant une excellente transparence, une excellente adhérence à un substrat, une excellente hydrophilie et similaire. L'invention concerne précisément une composition de revêtement inorganique laquelle permet de former un film de revêtement hydrophile sur un substrat organique. Une telle composition de revêtement inorganique contient (a) des particules de silice ayant un diamètre moyen des particules de 5-100 nm ; (b) un tensioactif ; (c) un solvant organique miscible avec l'eau A qui est capable de faire gonfler ou de dissoudre le substrat organique et a un point d'ébullition qui n'est pas inférieur à 130°C sous une pression d'air de 0,1 MPa ; (d) un solvant organique miscible avec l'eau B qui ne fait pas gonfler ou ne dissout pas de façon importante le substrat organique et a un point d'ébullition de 50-120°C sous une pression d'air de 0,1 MPa ; et (e) de l'eau. Dans la composition de revêtement inorganique, la teneur du solvant organique A est de 1-10 % en poids, la teneur du solvant organique B est de 0-97,2 % en poids, la teneur des matières solides est de 0,1-20 % en poids et la teneur en eau est de 3,5-17 fois celle des matières solides.
PCT/JP2005/019064 2004-11-08 2005-10-17 Composition de revêtement inorganique, film de revêtement hydrophile et procédé servant à former un film de revêtement hydrophile WO2006049008A1 (fr)

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Cited By (10)

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JP2006265462A (ja) * 2005-03-25 2006-10-05 Ishihara Chem Co Ltd 親水防汚コーティング組成物、それを用いた被膜の形成方法及び用途
DE102007032886A1 (de) 2007-07-14 2009-01-15 Bayer Materialscience Ag Hydrophile Hardcoatbeschichtungen
DE102008004622A1 (de) 2008-01-16 2009-07-23 Bayer Materialscience Ag Silikahaltige UV-vernetzbare Hardcoatbeschichtungen mit Urethanacrylaten
CN101798781A (zh) * 2010-03-25 2010-08-11 西安三业精细化工有限责任公司 一种造纸制浆用的有机硅消泡剂及其制备方法
WO2010091802A1 (fr) 2009-02-12 2010-08-19 Bayer Materialscience Ag Revêtements antireflets / antibuée
JP2012166195A (ja) * 2012-03-27 2012-09-06 Asahi Kasei Chemicals Corp 防汚層の形成方法
WO2013127054A1 (fr) * 2012-02-27 2013-09-06 3M Innovative Properties Company Compositions basiques incluant des nanoparticules d'oxyde inorganique et une base organique, substrats enduits, articles, et procédés
JP2013203774A (ja) * 2012-03-27 2013-10-07 Central Automotive Products Ltd 有機基材用防曇防汚剤及び当該防曇防汚剤で有機基材を被覆する方法
CN107400387A (zh) * 2017-06-06 2017-11-28 东莞唯智美新材料科技有限公司 用于水下眼镜镜片的防雾化亲水涂层、防雾化水下眼镜镜片及使用方法
CN116041993A (zh) * 2018-12-07 2023-05-02 佳能株式会社 透明构件和图像拾取装置、以及透明构件的制造方法

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TWI483848B (zh) * 2012-09-24 2015-05-11 3M Innovative Properties Co 親水性膜、其製備方法和應用

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JP2002282785A (ja) * 2001-03-26 2002-10-02 Matsushita Electric Works Ltd 塗膜の形成方法
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JP2005298570A (ja) * 2004-04-07 2005-10-27 Asahi Glass Co Ltd 無機塗料組成物及び親水性塗膜

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JPS56862A (en) * 1979-04-27 1981-01-07 Gen Electric Silicone coated composition and use
JPS6430681A (en) * 1987-07-24 1989-02-01 Matsushita Electric Works Ltd Formation of porous inorganic coated film
JP2002282785A (ja) * 2001-03-26 2002-10-02 Matsushita Electric Works Ltd 塗膜の形成方法
JP2004099647A (ja) * 2002-09-05 2004-04-02 Toto Ltd 光触媒性親水性被膜を形成するためのコーティング組成物および光触媒性親水性部材とその製造方法
JP2005298570A (ja) * 2004-04-07 2005-10-27 Asahi Glass Co Ltd 無機塗料組成物及び親水性塗膜

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006265462A (ja) * 2005-03-25 2006-10-05 Ishihara Chem Co Ltd 親水防汚コーティング組成物、それを用いた被膜の形成方法及び用途
DE102007032886A1 (de) 2007-07-14 2009-01-15 Bayer Materialscience Ag Hydrophile Hardcoatbeschichtungen
DE102008004622A1 (de) 2008-01-16 2009-07-23 Bayer Materialscience Ag Silikahaltige UV-vernetzbare Hardcoatbeschichtungen mit Urethanacrylaten
US8101673B2 (en) 2008-01-16 2012-01-24 Bayer Materialscience Ag Silica-containing UV-crosslinkable hardcoat coatings comprising urethane acrylates
WO2010091802A1 (fr) 2009-02-12 2010-08-19 Bayer Materialscience Ag Revêtements antireflets / antibuée
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WO2013127054A1 (fr) * 2012-02-27 2013-09-06 3M Innovative Properties Company Compositions basiques incluant des nanoparticules d'oxyde inorganique et une base organique, substrats enduits, articles, et procédés
JP2012166195A (ja) * 2012-03-27 2012-09-06 Asahi Kasei Chemicals Corp 防汚層の形成方法
JP2013203774A (ja) * 2012-03-27 2013-10-07 Central Automotive Products Ltd 有機基材用防曇防汚剤及び当該防曇防汚剤で有機基材を被覆する方法
CN107400387A (zh) * 2017-06-06 2017-11-28 东莞唯智美新材料科技有限公司 用于水下眼镜镜片的防雾化亲水涂层、防雾化水下眼镜镜片及使用方法
CN116041993A (zh) * 2018-12-07 2023-05-02 佳能株式会社 透明构件和图像拾取装置、以及透明构件的制造方法

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