WO2017033532A1 - Revêtement anti-buée, article à revêtement anti-buée, et procédé de production dudit article à revêtement anti-buée - Google Patents

Revêtement anti-buée, article à revêtement anti-buée, et procédé de production dudit article à revêtement anti-buée Download PDF

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WO2017033532A1
WO2017033532A1 PCT/JP2016/067490 JP2016067490W WO2017033532A1 WO 2017033532 A1 WO2017033532 A1 WO 2017033532A1 JP 2016067490 W JP2016067490 W JP 2016067490W WO 2017033532 A1 WO2017033532 A1 WO 2017033532A1
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Prior art keywords
film
fluorine
antifogging film
bond
antifogging
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PCT/JP2016/067490
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English (en)
Japanese (ja)
Inventor
井上　雅史
敏裕 平野
教和 藤浦
宏紀 深澤
濱口　滋生
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セントラル硝子株式会社
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Priority claimed from JP2016081900A external-priority patent/JP2017039906A/ja
Application filed by セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Publication of WO2017033532A1 publication Critical patent/WO2017033532A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to an antifogging film, an antifogging film forming article, and a method for producing an antifogging film forming article.
  • Cloudiness that occurs on the surface of a substrate such as a mirror or glass is caused by a dew condensation phenomenon in which countless minute water droplets are formed on the surface of the substrate.
  • hydrophilic coatings that have innumerable minute water droplets formed on the surface of the substrate as a uniform water film, water-absorbing coatings that incorporate water droplets into the coating, and the like have been formed on the substrate. .
  • Patent Document 1 as a method of forming a urethane resin-based antifogging film having excellent antifogging properties and abrasion resistance, a coating agent A containing an isocyanate component, polyethylene glycol, and copolymerization of oxyethylene / oxypropylene
  • An antifogging property obtained by coating a base material with a two-component curable antifogging film-forming coating agent comprising a polyol component having a polyol and a short-chain polyol, and a coating agent B containing a surfactant having an isocyanate-reactive group.
  • a method of forming a coating is disclosed.
  • the antifogging film of Patent Document 1 exhibits antifogging properties by two functions of water absorption by polyethylene glycol or oxyethylene / oxypropylene copolymer polyol and hydrophilicity by a surfactant.
  • the antifogging film described in Patent Document 1 needs to contain a large amount of a surfactant in the film in order to improve the hydrophilicity, and as a result, the scratch resistance may decrease, It was difficult to achieve both hydrophilicity and scratch resistance (see Comparative Examples 6 and 7 described later). Therefore, there has been a strong demand for an anti-fogging film that achieves both hydrophilicity and scratch resistance.
  • an object of the present invention is to provide an antifogging film and an antifogging film-formed article having both hydrophilicity and scratch resistance.
  • a fluorine-containing surfactant is added to the antifogging coating in the antifogging coating containing a urethane resin having an oxyethylene group, an oxypropylene group and an acyl group.
  • the fluorine-containing surfactant is localized on the surface of the anti-fogging coating, and all the atoms observed on the surface of the anti-fogging coating are analyzed by elemental analysis of the anti-fogging coating. It has been found that by setting the ratio of the number of fluorine atoms to the number to a specific value, an antifogging film having both hydrophilicity and scratch resistance can be formed, and the present invention has been achieved.
  • the present invention includes the following inventions.
  • An anti-fogging film comprising a urethane resin having an oxyethylene group, an oxypropylene group and an acyl group, The antifogging film contains a fluorine-containing surfactant, The surface layer thickness of the fluorine-containing surfactant in the antifogging film is 0.001 to 2% with respect to the film thickness of the film, An antifogging film, wherein the ratio of the number of fluorine atoms to the total number of atoms observed on the surface of the antifogging film is 5 to 30% by elemental analysis of the antifogging film.
  • Invention 2 2.
  • X represents a single bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or an arylene group which may have a substituent
  • Y represents a single bond.
  • a bond, an ester bond, an amide bond, a sulfonic acid ester bond, a sulfonic acid amide bond, or an ether bond is shown, but when X is a single bond, Y is combined with X to form a single bond.
  • N is a natural number from 2 to 22.
  • [Invention 6] A method for producing an antifogging film-forming article comprising a base material and the antifogging film according to the invention 1 formed on the base material, An isocyanate compound having an isocyanate group, An oxyethylene / oxypropylene copolymer polyol having a molar ratio of oxyethylene / oxypropylene of 60:40 to 90:10 and a number average molecular weight of 2000 to 15000, An acrylic polyol having a number average molecular weight of 5000 to 25000, A fluorine-containing surfactant represented by the following general formula [1], Including The solid content of the isocyanate compound is 50 to 75 mass% with respect to 100 mass% of the total solid content of the urethane-forming component, The acrylic polyol has a solid content of 2 to 50% by mass with respect to 100% by mass of the total solid content of the polyol component, A coating agent for forming an antifogging film, wherein the fluorine-containing surfactant
  • X represents a single bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or an arylene group which may have a substituent
  • Y represents a single bond.
  • a bond, an ester bond, an amide bond, a sulfonic acid ester bond, a sulfonic acid amide bond, or an ether bond is shown, but when X is a single bond, Y is combined with X to form a single bond.
  • N is a natural number from 2 to 22.
  • An antifogging film having an oxyethylene group, an oxypropylene group, and an acyl group contains a fluorine-containing surfactant, and the fluorine-containing surfactant is localized on the surface layer of the antifogging film.
  • the antifogging film of the present invention is an antifogging film containing a urethane resin having an oxyethylene group, an oxypropylene group and an acyl group, and the antifogging film contains a fluorine-containing surfactant, and The surface layer thickness of the fluorine-containing surfactant in the cloudy film is 0.001 to 2% with respect to the film thickness, and is observed on the surface of the cloudy film by elemental analysis of the cloudy film.
  • the antifogging film is characterized in that the ratio of the number of fluorine atoms to the total number of atoms is 5 to 30%.
  • the urethane resin contained in the antifogging film of the present invention is a urethane resin having an oxyethylene group, an oxypropylene group and an acyl group.
  • the urethane resin can be formed, for example, by polycondensation of an isocyanate compound and a polyol component such as an oxyethylene / oxypropylene copolymer polyol or an acrylic polyol.
  • the above isocyanate compound is used as a raw material for urethane resin, and is a trifunctional polyisocyanate having diisocyanate, hexamethylene diisocyanate as a starting material and / or an isocyanate structure, diisophorone diisocyanate, diphenylmethane diisocyanate, bis (methyl (Cyclohexyl) diisocyanate, toluene diisocyanate and the like.
  • an isocyanate having a biuret structure using hexamethylene diisocyanate as a starting material is preferable from the viewpoint of weather resistance and chemical resistance.
  • the isocyanate compound is usually 50 to 75% by mass, more preferably 55 to 75% by mass with respect to 100% by mass of the total solid content of the urethane-forming component (referred to in the present invention as an isocyanate compound and a polyol component). More preferably, it is 55 to 65% by mass.
  • the isocyanate compound is more than 75% by mass, the polyol component is insufficient and the crosslinked structure is not sufficiently formed, so that the hardness of the film may be insufficient. Also, when the isocyanate compound is less than 50% by mass, the hardness of the film may be insufficient.
  • the total number of isocyanate groups present in the isocyanate compound is usually 1.0 to 15 times, more preferably 1.1 times the total number of hydroxyl groups present in the polyol constituting the urethane resin. It is preferable to adjust the amount to be 10 times or less, more preferably 1.1 times or more and 3 times or less. When the amount is less than 1.0 times, the curability of the coating agent may deteriorate.
  • ⁇ Polyol component> As raw materials for the urethane resin, polyol components such as oxyethylene / oxypropylene copolymer polyol and acrylic polyol can be used. ⁇ Oxyethylene / oxypropylene copolymer polyol>
  • the oxyethylene / oxypropylene copolymer polyol (hereinafter also referred to as EO / PO copolymer polyol) is available from the city, and uses a phosphazene compound, Lewis acid compound or alkali metal compound catalyst as an initiator. It is a polyether polyol obtained by ring-opening polymerization of ethylene oxide and propylene oxide and then block addition or random addition.
  • the oxyethylene / oxypropylene copolymer polyol is a component that mainly imparts a water-absorbing function to the coating and exhibits antifogging properties.
  • This polyol has an oxyethylene group (—CH 2 CH 2 —O—) and an oxypropylene group (—CH 2 CH 2 CH 2 —O—, —CH (CH 3 ) CH 2 —O—). Since the oxyethylene group is excellent in the function of absorbing water as bound water, it is advantageous for forming an antifogging film exhibiting reversible absorption and dehydration with a high dehydration rate during dehydration, and the ambient temperature is 5 ° C. or lower. Even in such a low-temperature environment such as winter, a film formed using a copolymer polyol having an oxyethylene chain tends to exhibit antifogging properties.
  • the molar ratio of oxyethylene groups to oxypropylene groups (hereinafter also referred to as EO / PO ratio) of the oxyethylene / oxypropylene copolymer polyol is usually 60:40 to 90:10, and 70:30 to 90. : 10 is more preferable, and 75:25 to 85:15 is more preferable.
  • EO / PO ratio molar ratio of oxyethylene groups to oxypropylene copolymer polyol
  • the number average molecular weight of the oxyethylene / oxypropylene copolymer polyol is usually 500 to 20000, and when the number average molecular weight is less than 500, the ability to absorb water as bound water is low, and the number average molecular weight exceeds 20000 May cause problems such as poor curing of the coating agent and a decrease in film strength.
  • the water absorption, hydrophilicity, film strength, etc. of the coating it is preferably 2000 to 15000, more preferably 3000 to 12000, and more preferably 3000 to 6000.
  • the solid content of the oxyethylene / oxypropylene copolymer polyol is usually 25 to 75% by mass, preferably 30 to 70% by mass, more preferably 40 to 40% by mass with respect to 100% by mass of the total solid content of the polyol component. 60% by mass.
  • the acrylic polyol is used as a raw material for urethane resin, and is a copolymer of a hydroxyalkyl (meth) acrylate and a copolymerizable monomer such as alkyl (meth) acrylate, and has durability such as wear resistance of the film. It is a component used for improving the surface friction coefficient and reducing the surface friction coefficient, that is, for exhibiting slip properties on the film surface.
  • Acrylic polyols are commercially available and are hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, N-methylolacrylamide, and the like.
  • Styrene methyl methacrylate, ethyl methacrylate, methacrylate-n-butyl, isobutyl methacrylate, tertiary butyl methacrylate, acrylotolyl, methacrylonitrile, methyl acrylate, ethyl acrylate, acrylic acid-n- Those obtained by copolymerization with butyl, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, or the like can be used.
  • amino group-containing monomers such as 2-dimethylaminoethyl methacrylate and tert-butylaminoethyl methacrylate, glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, amino group-containing monomers such as acrylamide and methacrylamide, acrylic acid , Methacrylic acid, maleic anhydride, crotonic acid, fumaric acid, itaconic acid and other acid group-containing monomers, or fumaric acid esters, itaconic acid esters and the like may be copolymerized with the hydroxyl group-containing monomers.
  • the number average molecular weight of the acrylic polyol is usually 5000 to 25000, more preferably 10,000 to 25000, and further preferably 15000 to 20000.
  • the number average molecular weight of the acrylic polyol is smaller than 5000, the film becomes too dense and may become brittle.
  • it is larger than 25000 the volume of the acrylic polyol in the film increases, and the hydrophilicity tends to be lowered.
  • the solid content of the acrylic polyol is usually 2 to 50% by mass, more preferably 5 to 40% by mass, and further preferably 15 to 35% by mass with respect to 100% by mass of the total solid content of the polyol component.
  • the solid content of the acrylic polyol is larger than 50% by mass, the antifogging property and hydrophilicity are liable to be lowered, and when it is smaller than 2% by mass, it is difficult to obtain a sufficient hardness of the coating film.
  • the urethane resin preferably uses a short-chain polyol (in the present invention, a polyol having a number average molecular weight of 60 to 200 is called a short-chain polyol) as a raw material.
  • the short chain polyol is a component for improving the hardness of the antifogging coating.
  • the short chain polyol preferably has 2 or 3 hydroxyl groups. When the hydroxyl group is 1, the short-chain polyol does not act as a crosslinking component and does not serve as a skeleton component of the film, so that the film may not have sufficient hardness. In the case of 4 or more, the reactivity is too high and the coating agent may become unstable.
  • Short chain polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, Alkyl polyols such as glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 1,2,6-hexanetriol, 2,2′-thiodiethanol, alkanolamines such as diethanolamine and triethanolamine They can be used alone or as a mixture or as a mixture A copolymer having a number average molecular weight of 60
  • ethylene glycol and triethylene glycol are preferable from the viewpoint of the hardness of the antifogging coating, and 1,2-propanediol, 1,2-butanediol, 1,3-butanediol,
  • a short-chain polyol having a secondary or tertiary hydroxyl group having a lower activity than the primary hydroxyl group such as 1,3-butanediol is preferred from the viewpoint of the stability of the coating solution (prolonging the pot life).
  • the anti-fogging property of the anti-fogging coating is lowered.
  • an antifogging film having excellent antifogging properties, abrasion resistance and the like can be obtained by containing an appropriate amount of a surfactant and an appropriate amount of a copolymer polyol.
  • the solid content of the short-chain polyol is usually 6 to 40% by mass, preferably 6 to 30% by mass, and more preferably 6 to 22% by mass with respect to 100% by mass of the total solid content of the polyol component. %.
  • polyethylene glycol may be used as the polyol component instead of the short-chain polyol.
  • the antifogging film of the present invention contains a fluorine-containing surfactant.
  • the fluorine-containing surfactant include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyltrimethylammonium salt, perfluoroalkylaminosulfonate, perfluoro Alkyl group-containing oligomer, perfluoroalkenyloxybenzene sulfonate, perfluoroalkenyloxybenzenesulfonyl sarcosine sodium, perfluoroalkenyl polyoxyethylene ether, perfluoroalkenyloxybenzenesulfone alkylammonium iodide, perfluoroalkenyloxybenzamide alkylammonium iodide Perfluoroalkenyloxyaralkylbetaine
  • an ionic interface that does not contain fluorine.
  • a surfactant when such a surfactant is used, localization of the surfactant on the surface layer of the coating is insufficient, resulting in hydrophilicity and scratch resistance. It was not excellent (refer to Comparative Examples 6 and 7 described later).
  • a fluorine-containing surfactant and localizing the fluorine-containing surfactant on the surface layer of the coating it was possible to achieve both hydrophilicity and scratch resistance (see Examples described later).
  • fluorine-containing surfactant it is preferable to use a fluorine-containing surfactant represented by the following general formulas [1] and [2]. These fluorine-containing surfactants do not have isocyanate-reactive groups such as hydroxyl groups, mercapto groups, and amino groups. Among the above-mentioned fluorine-containing surfactants, fluorine-containing surfactants represented by the following general formula [1] are preferable from the viewpoint of high hydrophilicity and film hardness.
  • X and Y are preferably single bonds, and n is preferably a natural number of 8 to 16.
  • the natural number is 9 to 13.
  • X represents a single bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or an arylene group which may have a substituent
  • Y represents a single bond.
  • a bond, an ester bond, an amide bond, a sulfonic acid ester bond, a sulfonic acid amide bond, or an ether bond is shown, but when X is a single bond, Y is combined with X to form a single bond.
  • N is a natural number from 2 to 20.
  • X represents a single bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or an arylene group which may have a substituent
  • Y represents a single bond.
  • a bond, an ester bond, an amide bond, a sulfonic acid ester bond, a sulfonic acid amide bond, or an ether bond is shown, but when X is a single bond, Y also becomes a single bond with X.
  • N is a natural number from 2 to 15.
  • the content of the fluorine-containing surfactant is preferably 0.1 to 5.0% by mass, and preferably 0.5 to 2.0% by mass, based on the total solid content of the urethane-forming component. Is more preferable.
  • the content of the fluorine-containing surfactant is increased, the quality of the obtained film is affected by the fluorine-containing surfactant, and the appearance and film strength may be hindered.
  • the content of the fluorine-containing surfactant is small, the hydrophilicity of the coating surface is not sufficiently obtained.
  • the fluorine atom in the fluorine-containing surfactant preferably accounts for 10 to 50% by mass, more preferably 20 to 40% by mass with respect to the total amount of the fluorine-containing surfactant.
  • the amount of fluorine atoms in the fluorine-containing surfactant is preferably 0.1 to 1.0% by mass, preferably 0.1 to 0.7% by mass, based on the total solid content of the urethane-forming component. % Is more preferable.
  • the surface layer thickness of the fluorine-containing surfactant in the antifogging coating of the present invention is 0.001 to 2% with respect to the thickness of the coating. If it exceeds 2%, it is inappropriate in that the appearance of the coating is clouded or the pencil hardness is lowered, and if it is less than 0.001%, it is inappropriate in that the hydrophilicity is lowered.
  • the surface layer thickness of the surfactant refers to the fluorine contained in the surfactant by performing elemental analysis while etching in the depth direction from the coating surface by elemental analysis using X-ray photoelectron spectroscopy (XPS). It means the depth from the coating surface where the sulfur concentration is below the detection limit.
  • the surface layer thickness of the fluorine-containing surfactant is more preferably 0.01 to 1% with respect to the film thickness, and further preferably 0.01 to 0.5% with respect to the film thickness. .
  • the ratio of the number of fluorine atoms to the total number of atoms observed on the surface of the coating by elemental analysis is 5 to 30%.
  • the ratio of the number of fluorine atoms is determined by performing an elemental analysis on the surface of the film using X-ray photoelectron spectroscopy (XPS), and determining the area of peaks derived from existing fluorine, sulfur, carbon, oxygen, and nitrogen. This area was multiplied by a coefficient depending on the detection sensitivity of each element, and converted into the number of atoms to calculate the atomic composition percentage.
  • XPS X-ray photoelectron spectroscopy
  • the ratio of the number of fluorine atoms is less than 5%, the fluorine-containing surfactant is not sufficiently present on the surface of the coating, and the hydrophilicity becomes insufficient. Is not preferred because it becomes cloudy.
  • the ratio of the number of fluorine atoms is more preferably 10 to 30%, still more preferably 17 to 30%.
  • a method for producing the antifogging film-formed article of the present invention will be described.
  • a method for producing an antifogging film-formed article of the present invention is a method for producing an antifogging film-forming article having a base material and the above-described antifogging film formed on the base material.
  • An isocyanate compound having an isocyanate group An oxyethylene / oxypropylene copolymer polyol having a molar ratio of oxyethylene / oxypropylene of 60:40 to 90:10 and a number average molecular weight of 2000 to 15000, An acrylic polyol having a number average molecular weight of 5000 to 25000, A fluorine-containing surfactant represented by the following general formula [1], Including The solid content of the isocyanate compound is 50 to 75 mass% with respect to 100 mass% of the total solid content of the urethane-forming component, The acrylic polyol has a solid content of 2 to 50% by mass with respect to 100% by mass of the total solid content of the polyol component, A coating agent for forming an antifogging film, wherein the fluorine-containing surfactant is 0.1 to 5.0% by mass with respect to the total solid content of the urethane-forming component, and a substrate.
  • X represents a single bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or an arylene group which may have a substituent
  • Y represents a single bond.
  • a bond, an ester bond, an amide bond, a sulfonic acid ester bond, a sulfonic acid amide bond, or an ether bond is shown, but when X is a single bond, Y is combined with X to form a single bond.
  • N is a natural number from 2 to 22.
  • a base material and a coating agent for forming an antifogging film are prepared.
  • a base material glass is typically used.
  • the glass is a plate glass usually used for automobiles, architectural and industrial glasses, and is a plate glass by a float method, a duplex method, a roll-out method, etc., and the manufacturing method is not particularly limited.
  • glass types it can be used for various colored glasses such as clear, green and bronze, various functional glasses such as UV, IR cut glass and electromagnetic shielding glass, netted glass, low expansion glass, zero expansion glass and fireproof glass.
  • various glass products such as glass, tempered glass or similar glass, laminated glass, multilayer glass, mirrors produced by the silvering method or vacuum film forming method, flat plates, bent plates and the like can be used.
  • the plate thickness is not particularly limited, but is preferably 1.0 mm or more and 10 mm or less, and particularly preferably 1.0 mm or more and 5.0 mm or less.
  • the antifogging film may be formed on the substrate surface only on one side of the substrate or on both sides depending on the application. Further, the antifogging film may be formed on the entire surface or a part of the substrate surface.
  • a liquid having a silane coupling agent is applied before application of the antifogging film forming coating agent. Furthermore, it is preferable to apply to the surface of the glass substrate.
  • Suitable silane coupling agents include amino silanes, mercapto silanes and epoxy silanes. Preferred are ⁇ -glycidoxypropyltrimethoxy, ⁇ -aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, and the like.
  • a resin film such as polyethylene terephthalate, a resin such as polycarbonate, or the like can be used as a base material.
  • the antifogging film may be formed on the surface of the resin transparent substrate to form an antifogging film-formed article, and the article may be attached to a glass substrate.
  • the coating agent for forming an antifogging film is obtained by mixing a chemical solution containing an isocyanate compound having an isocyanate group and a chemical solution containing a polyol component and a fluorine-containing surfactant.
  • the isocyanate group reacts with the hydroxyl group of the polyol component, a urethane bond is formed, and a urethane resin starts to be formed.
  • the kind and ratio of the urethane forming component (polyol component and isocyanate compound) and the fluorine-containing surfactant in the coating agent for forming the antifogging film are as described above for the urethane resin contained in the antifogging film. It is the same as the kind and ratio of the raw material and the fluorine-containing surfactant contained in the antifogging film.
  • an application step of applying an antifogging film-forming coating agent to the substrate is performed.
  • the coating means known means such as dip coating, flow coating, spin coating, roll coating, spray coating, screen printing, flexographic printing and the like can be employed.
  • a curing process for curing the coating agent for forming an antifogging film is usually performed by standing at room temperature or by heat treatment at 170 ° C. or lower to form an antifogging film on the substrate. If the temperature of the heat treatment exceeds 170 ° C., the urethane resin may be carbonized to cause problems such as a decrease in film strength. In order to accelerate the curing reaction of the coating agent, it is preferable to perform a heat treatment at 80 ° C. to 170 ° C.
  • the film thickness of the antifogging film is desirably about 5 to 40 ⁇ m after the curing reaction of the coating agent for forming the antifogging film, more preferably 5 to 20 ⁇ m, and further preferably 5 to 15 ⁇ m. If it is less than 5 ⁇ m, the durability tends to be inferior. If it exceeds 40 ⁇ m, defects such as optical distortion may occur in appearance quality.
  • the use of the antifogging film-formed article of the present invention is as follows: mirrors for bathrooms, bathroom vanities, etc. for buildings, window glasses, etc., windows, mirrors, etc. for vehicles, ships, aircrafts, etc.
  • room mirrors, door mirrors, etc. other lenses such as glasses and cameras, goggles, helmet shields, refrigerated showcases, frozen showcases, testing machines, precision instrument cases, etc. openings and viewing windows, road reflections Display of mobile communication bodies such as mirrors and mobile phones.
  • a coating agent for forming an antifogging film for forming an antifogging film was prepared, applied on a substrate and dried to produce an antifogging film-formed article.
  • the method for preparing the coating agent and the method for producing the antifogging film-formed article are as described below.
  • quality evaluation was performed by the method shown below about the obtained antifogging film formation article.
  • Film thickness The film thickness was measured by cutting the surface of the film with a cutter, etc., and measuring the level difference between the film surface and the substrate surface with a surface roughness meter (Surfcoder ET-4000A manufactured by Kosaka Laboratory). The five-point average value was taken as the film thickness.
  • the measurement was performed by irradiating the surface of the antifogging film-formed article with a monochromatic AIK ⁇ ray 50W 15KV to a photoelectron take-off angle of 45 ° and etching with an argon-gas cluster ion beam.
  • the etching rate was about 4 nm / min for the anti-fogging coating.
  • the measurement was performed by irradiating the surface of the antifogging film-formed article with a monochrome AIK ⁇ ray 50 W 15 KV at a 200 ⁇ m square, and a photoelectron take-off angle of 45 °.
  • Anti-fogging evaluation In a room at room temperature (temperature 24 ° C., humidity 45%), exhale with an interval of 20 mm between the coating and the examiner's mouth against the coating surface of the anti-fogging coating-formed article. . Observing the cloudiness while illuminating the reflected light with a fluorescent lamp, the mark that could be recognized as a map was marked as ⁇ , and the mark that was cloudy and could not be recognized as a mark.
  • SW Resistance As an evaluation of SW resistance, the number of scratches after 10 reciprocating slides on the substrate surface at a strength of about 325 g / cm 2 with SW (count: # 0000). was measured. After the test, those with less than 10 scratches were marked with ⁇ (fine scratches), those with 10 to less than 30 scratches were marked with ⁇ (light scratches), and those with 30 or more scratches were marked with x (heavy scratches).
  • Example 1 Preparation of antifogging film-forming coating agent
  • an isocyanate prepolymer 18.11 g of a biuret type polyisocyanate (trade name “N3200”, manufactured by Sumitomo Bayer Urethane) of hexamethylene diisocyanate was prepared. This is drug A.
  • An oxyethylene / oxypropylene copolymer having a number average molecular weight of 4000 (trade name “Toho Polyol PB-4000”; manufactured by Toho Chemical Co., Ltd.) is added to 65.53 g of a mixed solvent of isobutyl acetate and diacetone alcohol as a diluting solvent.
  • 92 g and 2.37 g of a short-chain polyol (ethylene glycol; manufactured by Kishida Chemical Co., Ltd.) having a number average molecular weight of 62 are mixed, and a mixed solution (trade name “Acridick” having 45.0% by mass of an acrylic polyol having a number average molecular weight of 18000 is mixed therewith.
  • DBTDL dibutyltin dilaurate
  • the total solid content of the urethane-forming component in 100% by mass of the coating agent for forming an antifogging film prepared here is 30%.
  • the content of the fluorine-containing surfactant is 0.5% by mass with respect to the total solid content of the urethane-forming component
  • the number of isocyanate groups relative to the isocyanate prepolymer component of the drug A is the oxyethylene /
  • the amount is 1.2 times the number of hydroxyl groups present in the oxypropylene copolymer, ethylene glycol, and acrylic polyol component (described as “NCO / OH ratio” in Table 1).
  • the solid content of the drug A was 60.5 with respect to 100 mass% of the total solid content of the urethane-forming component (in Example 1, the isocyanate compound, copolymer polyol, acrylic polyol, and short chain polyol). Mass% is included.
  • the coating agent for forming the antifogging film obtained above is applied to the substrate by spin coating, and the glass plate of the coating agent is heat-treated at about 150 ° C. for about 10 minutes, thereby preventing the film thickness of 10 ⁇ m. A cloudy film-formed article was obtained.
  • Examples 2 to 9 As shown in Table 1, the types, ratios and addition amounts of oxyethylene / oxypropylene copolymer, acrylic polyol, short chain polyol, polyethylene glycol, isocyanate compound and surfactant were changed. Carried out.
  • Table 1 shows each component of the coating agent for forming an antifogging film and its ratio for each example and each comparative example. Further, regarding the antifogging film-formed article obtained in each Example and each Comparative Example, the surface layer thickness of the surfactant / the film thickness, the film thickness, the fluorine / sulfur atomic ratio on the coating surface, the appearance The measurement results of the observation results, antifogging properties, initial water contact angle, pencil hardness, scratch resistance, and SW resistance are shown in Table 2 below.
  • the antifogging film contains a urethane resin having an oxyethylene group, an oxypropylene group and an acyl group, and a fluorine-containing surfactant.
  • the surface layer thickness of the fluorine-containing surfactant is 0.001 to 2% of the film thickness, and the ratio of the number of fluorine atoms to the total number of atoms observed on the surface of the film by elemental analysis is It was 5% to 30%, and both hydrophilicity and scratch resistance were compatible. The appearance, antifogging properties and pencil hardness were also good.
  • Comparative Example 1 did not contain a fluorine-containing surfactant and was inferior to Examples in terms of antifogging property, hydrophilicity, and the like.
  • Comparative Example 2 the fluorine atom ratio on the coating surface was small, and the antifogging property, hydrophilicity, etc. were inferior to those of the Examples.
  • the surface thickness of the fluorine-containing surfactant is as thick as 2.5% of the film thickness, and the fluorine atom ratio on the film surface is too large at 45%, so that the appearance of the film surface is cloudy. And it was bad. Moreover, the pencil hardness was also inferior to the Example.
  • Example 4 when the oxyethylene / oxypropylene copolymer used in Example 1 was replaced with polyethylene glycol (PEG), the fluorine atom ratio on the coating surface was as low as 2%, and antifogging property, hydrophilicity, etc. It was inferior to the Example.
  • PEG polyethylene glycol
  • Comparative Example 5 did not contain an acrylic polyol, and the appearance, antifogging properties, hydrophilicity, etc. were inferior to those of the examples.
  • Comparative Example 6 a conventionally used surfactant having a hydroxyl group which is an isocyanate-reactive group was used, but the antifogging property and hydrophilicity were inferior to those of the Examples.
  • Comparative Example 7 when the addition amount of the surfactant having a hydroxyl group that is an isocyanate-reactive group was increased as compared with Comparative Example 6, the antifogging property and hydrophilicity were slightly improved, but the hydrophilicity was higher than that in Examples. In addition, scratch resistance and pencil hardness were insufficient.
  • the antifogging film-formed article of the present invention has both scratch resistance and hydrophilicity, it can be used for a long time even in an environment where wiping is frequently performed. For example, it can be used in mirrors for bathrooms and vanities, glass for automobiles, camera lenses, and the like.

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  • Paints Or Removers (AREA)
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Abstract

Le problème abordé par la présente invention est de pourvoir à un revêtement anti-buée et à un article à revêtement anti-buée doué à la fois d'hydrophilicité et de résistance à la rayure. La solution selon l'invention porte sur un revêtement anti-buée contenant une résine uréthane ayant un groupe oxyéthylène, un groupe oxypropylène, et un groupe acyle, et caractérisé en ce que le revêtement anti-buée contient un tensioactif fluoré, l'épaisseur de la couche superficielle de tensioactif fluoré dans le revêtement anti-buée représentant de 0,001 à 2 % de l'épaisseur du revêtement, et le rapport du nombre d'atomes de fluor au nombre d'atomes totaux qui sont observés à la surface du revêtement anti-buée par analyse élémentaire du revêtement anti-buée étant de 5 à 30 %.
PCT/JP2016/067490 2015-08-21 2016-06-13 Revêtement anti-buée, article à revêtement anti-buée, et procédé de production dudit article à revêtement anti-buée WO2017033532A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021171745A1 (fr) 2020-02-27 2021-09-02 ユニマテック株式会社 Composite d'alcool contenant du fluor

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JP2004244612A (ja) * 2002-12-25 2004-09-02 Central Glass Co Ltd 防曇性膜及びその形成方法並びに防曇性膜形成用塗布剤
JP2004244471A (ja) * 2003-02-12 2004-09-02 Toto Ltd 自動車用ガラス親水化剤
JP2006169440A (ja) * 2004-12-17 2006-06-29 Central Glass Co Ltd 防曇性物品及びその製造法、並びに防曇性被膜形成用塗布剤
JP2006241447A (ja) * 2005-02-03 2006-09-14 Asahi Lite Optical Co Ltd プライマー組成物及びこれを用いたプラスチックレンズ
JP2013103990A (ja) * 2011-11-14 2013-05-30 Nippon Synthetic Chem Ind Co Ltd:The 樹脂組成物および、それを用いてなるフィルム、防曇用フィルム、抗菌用フィルム、並びにコーティング剤
JP2013158990A (ja) * 2012-02-03 2013-08-19 Central Glass Co Ltd 防曇性物品
JP2014148042A (ja) * 2011-05-26 2014-08-21 Asahi Glass Co Ltd 防曇性物品およびその製造方法

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Publication number Priority date Publication date Assignee Title
JP2004244612A (ja) * 2002-12-25 2004-09-02 Central Glass Co Ltd 防曇性膜及びその形成方法並びに防曇性膜形成用塗布剤
JP2004244471A (ja) * 2003-02-12 2004-09-02 Toto Ltd 自動車用ガラス親水化剤
JP2006169440A (ja) * 2004-12-17 2006-06-29 Central Glass Co Ltd 防曇性物品及びその製造法、並びに防曇性被膜形成用塗布剤
JP2006241447A (ja) * 2005-02-03 2006-09-14 Asahi Lite Optical Co Ltd プライマー組成物及びこれを用いたプラスチックレンズ
JP2014148042A (ja) * 2011-05-26 2014-08-21 Asahi Glass Co Ltd 防曇性物品およびその製造方法
JP2013103990A (ja) * 2011-11-14 2013-05-30 Nippon Synthetic Chem Ind Co Ltd:The 樹脂組成物および、それを用いてなるフィルム、防曇用フィルム、抗菌用フィルム、並びにコーティング剤
JP2013158990A (ja) * 2012-02-03 2013-08-19 Central Glass Co Ltd 防曇性物品

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021171745A1 (fr) 2020-02-27 2021-09-02 ユニマテック株式会社 Composite d'alcool contenant du fluor
KR20220141860A (ko) 2020-02-27 2022-10-20 유니마테크 가부시키가이샤 함불소 알코올 컴포지트

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