US20160160052A1 - Anti-fogging, heat-insulating coating composition, method for preparing the same, and film formed from the same - Google Patents
Anti-fogging, heat-insulating coating composition, method for preparing the same, and film formed from the same Download PDFInfo
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- US20160160052A1 US20160160052A1 US14/582,588 US201414582588A US2016160052A1 US 20160160052 A1 US20160160052 A1 US 20160160052A1 US 201414582588 A US201414582588 A US 201414582588A US 2016160052 A1 US2016160052 A1 US 2016160052A1
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- United States
- Prior art keywords
- tungsten oxide
- doped tungsten
- mesoporous
- coating composition
- film
- Prior art date
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- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 20
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 60
- -1 polysiloxane Polymers 0.000 claims abstract description 52
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 42
- 239000013335 mesoporous material Substances 0.000 claims abstract description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011856 silicon-based particle Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims 2
- 239000000243 solution Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000000576 coating method Methods 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- DMKKMGYBLFUGTO-UHFFFAOYSA-N 2-methyloxirane;oxirane Chemical compound C1CO1.C1CO1.CC1CO1 DMKKMGYBLFUGTO-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J Tungsten(IV) chloride Inorganic materials Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- WOBGRZMVULAZPD-UHFFFAOYSA-N [C].[O].[W] Chemical compound [C].[O].[W] WOBGRZMVULAZPD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229960000800 cetrimonium bromide Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- BWKCCRPHMILRGD-UHFFFAOYSA-N chloro hypochlorite;tungsten Chemical compound [W].ClOCl BWKCCRPHMILRGD-UHFFFAOYSA-N 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BGRYSGVIVVUJHH-UHFFFAOYSA-N prop-2-ynyl propanoate Chemical compound CCC(=O)OCC#C BGRYSGVIVVUJHH-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YXPHMGGSLJFAPL-UHFFFAOYSA-J tetrabromotungsten Chemical compound Br[W](Br)(Br)Br YXPHMGGSLJFAPL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003657 tungsten Chemical group 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 1
- 229910021342 tungsten silicide Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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
- C09D183/04—Polysiloxanes
-
- C09D7/1216—
-
- C09D7/1225—
-
- C09D7/1266—
-
- C09D7/1275—
-
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/023—Silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Definitions
- the present disclosure relates to coating compositions, films formed from the same, and methods for preparing the same, and, more particularly, to a coating composition having anti-fogging and heat-insulating functions, a film formed from the same, and a method for preparing the same.
- the effect of the daily temperature difference causes the saturated water vapor inside an agricultural polyolefin shed film aggregate on the inner surface of the shed film to form water droplets, referred to as the “fogging phenomenon.”
- the fogging phenomenon affects daylight irradiation, and the high humidity inside in the shed is likely to induce pest damages to crops.
- heat-insulating and anti-fogging materials such as hydrophilicity and hydrophobicity
- most of the heat-insulating films or heat-insulating glass does not have the anti-fogging function.
- multiple steps are used in the modern technology for preparation. For example, coating a fogproof material on a heat-insulating film or attaching an anti-fogging film.
- the temperature and time for curing a fogproof coating or the process for forming a multi-layered film structure not only increases the production cost, but also limits the product use due to lowered light transmittance.
- one of the major objectives for developing the present disclosure is to develop a composite coating and a film-forming material having anti-fogging and heat-insulating functions, while maintaining high light transmittance.
- a coating composition having anti-fogging and heat-insulating functions which includes:
- M is an alkali metal element
- W is tungsten
- O is oxygen
- A is halogen, 0 ⁇ x ⁇ 1, and 0 ⁇ y ⁇ 0.5
- a film having anti-fogging and heat-insulating functions which includes: a matrix that is a continuous layer formed by organic polysiloxane; a plurality of mesoporous silicon particles dispersed in the matrix; and co-doped tungsten oxide, as shown in formula (I), embedded in the matrix and located between any two of the mesoporous silicon particles.
- a method for preparing a coating composition having anti-fogging and heat-insulating functions which includes the steps of: preparing a mesoporous material, co-doped tungsten oxide as shown in formula (I), and organic polysiloxane; and mixing the mesoporous material, the co-doped tungsten oxide as shown in formula (I), and the polysiloxane.
- FIG. 1 is a sectional view of a film having anti-fogging and heat-insulating functions according to the present disclosure.
- composition having anti-fogging and heat-insulating functions which includes:
- M is an alkali metal element
- W is tungsten
- O is oxygen
- A is halogen, 0 ⁇ x ⁇ 1, and 0 ⁇ y ⁇ 0.5
- the present disclosure provides, a method for preparing a coating composition, which includes the steps of: preparing a mesoporous material, co-doped tungsten oxide as shown in formula (I), and organic polysiloxane; and mixing the mesoporous material, the co-doped tungsten oxide as shown in formula (I), and the organic polysiloxane.
- the method includes preparing the mesoporous material by a sol-gel method; co-doping tungsten oxide with anions and cations; synthesizing the organic polysiloxane by hydrolysis; and blending the mesoporous material, the co-doped tungsten oxide and the organic polysiloxane, thereby forming the coating composition having anti-fogging and heat-insulating functions.
- the mesoporous material can include a precursor, a surfactant, and mesoporous particles.
- the mesoporous material is prepared by synthesizing the precursor; and self-assembling micelles and nanoparticles formed by using the surfactant in a solvent, so as to make the nanoparticles form mesoporous particles each having a mesoporous structure; and then blending the precursor and the mesoporous particles.
- silane or siloxane e.g., tetraethoxysilane (TEOS), tetramethoxysilane (TMOS)
- a non-ionic surfactant e.g., a surfactant with a ethylene oxide-propylene oxide-ethylene oxide triblock copolymer (e.g., P123 (HO(CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 70 (CH 2 CH 20 ) 20 H) and F127 (HO(CH 2 CH 2 O) 106 (CH 2 CH(CH 3 )O) 70 (CH 2 CH 2 O) 106 H)
- P123 HO(CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 70 (CH 2 CH 20 ) 20 H
- F127 HO(CH 2 CH 2 O) 106 (CH 2 CH(CH 3 )O) 70 (CH 2 CH 2 O) 106 H)
- P123 HO(CH 2 CH 2 O) 20 (CH 2 CH(CH 3
- the precursor is an inorganic porous macromolecule, such as inorganic polysiloxane or polysilane.
- the precursor is prepared by the following steps of: evenly mixing siloxane and a solvent (e.g., ethanol, water, and hydrochloric acid) to produce a siloxane solution; evenly mixing a surfactant with a triblock copolymer and a solvent (e.g., ethanol) to produce a surfactant solution; thoroughly mixing the siloxane solution and the surfactant solution; and then setting at room temperature to allow Si—OR of the siloxane molecules to stepwisely hydrolyze to generate Si—OH, and the siloxane molecules polymerize to form the precursor by dehydrating hydroxyl groups or undergoing dealcoholization.
- the inorganic polysiloxane molecule can retain hydroxyl groups as surface functional groups, by controlling the pH value, temperature, and time for the reaction.
- a cationic surfactant can be selected as a template for preparing mesoporous particles.
- the mesoporous particles are prepared by the following steps of: dissolving a cationic surfactant, cetrimonium bromide (CTABr), in polyoxyethylene-8-octyl-phenylether (Trinton-X-100) and concentrated hydrochloric acid to form a surfactant solution, wherein CTABr can form micelles in the solution; adding nanoparticles (e.g., nano silicon particles of silica) to the surfactant solution; setting after stirring to allow the nanoparticles to self-assemble on a template; washing with ionic water/ethanol several times; and then removing the template to obtain the mesoporous particles.
- CTABr cetrimonium bromide
- Trinton-X-100 polyoxyethylene-8-octyl-phenylether
- Trinton-X-100 polyoxyethylene-8-octyl-phenylether
- the mesoporous particles required by the present disclosure can be controlled by the selection of the surfactant used (i.e., the arrangement of the template) and the adjustment of the reaction conditions such as pH value, temperature, and time for the self-assembling reaction.
- the size of the particle diameter of the mesoporous particle can be greater than about 50 nm, such as greater than about 100 nm, such as between 200 nm to 1000 nm, and the specific surface area of a mesoporous particle can be greater than about 800 cm 2 /g.
- a tungsten oxide co-doped with anions and cations is prepared by the steps of: adding an alkali metal salt and a halogen salt at appropriate proportions during the process for synthesizing tungsten oxide; and heating the mixture from 300° C. to 800° C. in a hydrogen reduction environment, thereby obtaining the co-doped tungsten oxide powder having a chemical structure of M x WO 3-y A y , wherein M is an alkali metal element, W is tungsten, O is oxygen, A is halogen, 0 ⁇ x ⁇ 1, and 0 ⁇ y ⁇ 0.5.
- the precursor for synthesizing tungsten oxide can be selected from ammonium metatungstate, ammonium orthotungstate, ammonium paratungstate, alkali metal tungstate, tungstic acid, tungsten silicide, tungsten sulfide, tungsten oxychloride, tungsten alkoxide, tungsten hexachloride, tungsten tetrachloride, tungsten bromide, tungsten fluoride, tungsten carbide, carbon tungsten oxide, or other salts containing tungsten.
- the alkali metal salts can be selected from at least one of alkali metal carbonate, alkali metal bicarbonate, alkali metal nitrate, alkali metal nitrite, alkali metal hydroxide, alkali metal halogenated salt, alkali metal sulfate, alkali metal sulfite, and other alkali metal-containing salts.
- the halogenated salt can be selected from halogenated amine, organic ammonium salts, halogenated carbon, halogenated hydrogen, halogenated tungsten, halogenated benzene, halogenated aromatic group, halogenated alkane, or other halogen-containing salts.
- TW I402218 which is a patent owned by the Applicant, the entirely of which is incorporated by reference herein.
- the particle diameter of the co-doped tungsten oxide can be no more than 100 nm, such as between 50 to 100 nm, such as between 60 to 80 nm.
- inorganic metal oxide such as silica and/or titanium oxide and/or aluminum oxide and/or zirconium oxide is added, and the inorganic metal oxide is wrapped around the outer surface of the co-doped tungsten oxide, so as to avoid aggregation and the change in the surface characteristics of the particles of co-doped tungsten oxide.
- silane, tilane or organic metal groups can also be added to modify the surface properties of the co-doped tungsten oxide, so as to increase the dispersibility of the co-doped tungsten oxide in an organic solvent or a polymer and the compatibility of the co-doped tungsten oxide with an organic solvent or a polymer.
- the process of synthesizing an organic polysiloxane by hydrolysis includes the steps of providing a siloxane monomer (e.g., 3-(2,3-glycidoxy)propyltrimethoxysilane or vinyltrimethoxysilane), wherein siloxane monomer includes at least one functional group selected from a vinyl group, an acrylic acid group, and an ethoxy group; dissolving the siloxane monomer in an acidic solvent (e.g., hydrochloric acid aqueous solution), wherein the pH value of the reaction solution is from 1 to 5, the reaction temperature is from 10° C. to 40° C., and the reaction time is from 0.5 to 5 hours; and conducting hydrolysis-polymerization at room temperature while stirring. After completion of the reaction, distillation is conducted at a reduced pressure to extra additional solvent, and thereby obtaining the organic polysiloxane.
- a siloxane monomer e.g., 3-(2,3-glycidoxy)propyltrime
- the mesoporous material and co-doped tungsten oxide with appropriate particle diameters are screened for and selected, wherein the ratio of the particle diameter of a mesoporous particle (e.g., a mesoporous silicon particle) to that of the co-doped tungsten oxide can be from 20:1 to 1:1, such as from 20:1 to 2:1, such as from 16:1 to 2:1.
- a mesoporous particle e.g., a mesoporous silicon particle
- the mesoporous material, the co-doped tungsten oxide and the organic polysiloxane are blended in an appropriate weight ratio ranging, for example, from 42.5:57:0.5 to 8.5:76.5:15, so as to make the mesoporous material and the co-doped tungsten oxide to evenly disperse in the organic polysiloxane.
- an appropriate weight ratio ranging, for example, from 42.5:57:0.5 to 8.5:76.5:15, so as to make the mesoporous material and the co-doped tungsten oxide to evenly disperse in the organic polysiloxane.
- FIG. 1 is a schematic sectional view of a film according to the present disclosure.
- a film 1 having anti-fogging and anti-insulating functions includes a transparent layer 11 having anti-fogging and insulating functions formed on a substrate 12 .
- the substrate 12 can be glass or plastic.
- the plastic can be selected from, but not limited to, polyethylene (PE), polyethylene terephthalate (PET), polyimide, etc.
- the transparent layer 11 can be constituted by a matrix 113 , a plurality of mesoporous silicon particles 111 , and co-doped tungsten oxide 112 as shown in formula (1).
- the matrix 113 is a continuous layer formed by organic polysiloxane
- the mesoporous silicon particles 111 are dispersed in the matrix 113
- any two of the mesoporous silicon particles 111 are spaced apart
- the co-doped tungsten oxide 112 is embedded in the matrix 113 , and located between any two of the mesoporous silicon particles 111 .
- the matrix 113 can further includes a precursor, a surfactant, and the like.
- the precursor is an inorganic polysilane or polysiloxane molecule having a hydrophilic group, which can increase the hydrophilicity of the transparent layer 11 .
- Organic polysiloxane provides adhesion and support, such that it can effectively improve the film formation and thickness of the transparent layer 11 .
- the thickness of the transparent layer 11 can be about 0.1 ⁇ m or higher, such as about 1 ⁇ m or higher, such as from 1 to 50 ⁇ m.
- the surfaces of the mesoporous silicon particles 111 also have hydrophilic groups.
- the affinity between the matrix 113 and each of the mesoporous silicon particles 111 allow any two of the mesoporous silicon particles 111 to be dispersed in the matrix 113 in a way that they are spaced part.
- the width W of the spacing parallel to a surface of the matrix 113 can be greater than about 50 nm. In another embodiment, the spacing on a surface parallel to a surface of the matrix can be no more than 50 nm.
- the co-doped tungsten oxide 112 has a structure of M x WO 3-y A y , wherein M is a metal alkali element, W is tungsten oxide, O is oxygen, A is halogen, 0 ⁇ x ⁇ 1, and 0 ⁇ y ⁇ 0.5.
- the particle diameter of a mesoporous silicon particle 111 can be from 50 to 1000 nm.
- the specific surface area of a mesoporous silicon particle can be greater than 800 cm 2 /g.
- the particle diameter of the co-doped tungsten oxide 112 can be from 50 to 100 nm.
- the ratio of the particle diameter of the mesoporous silicon particle 111 to that of the co-doped tungsten oxide 112 can be from 20:1 to 1:1, such as from 20:1 to 2:1, such as from 16:1 to 2:1.
- the apexes of a portion of the mesoporous silicon particles 111 protrude from a surface of the matrix 113 .
- the hydrophilic groups on the surfaces of the mesoporous silicon particles 111 and the matrix 113 can cause the contact angle of a water molecule on a surface of the transparent layer 111 to rapidly decrease to 0° from 10°, so that the film 1 imparts an anti-fogging effect.
- the alkali metal and the halogenated co-doped tungsten oxide 112 have high conductivity, such that 74% or more of the infrared ray with a wavelength of 800 nm or higher can be effectively blocked.
- the film 1 has a heat-insulating function for blocking infrared ray, while maintaining the transmittance of visible light to 60%, or even 80% or higher.
- the present disclosure further provided is a method for preparing a film having anti-fogging and heat-insulating functions.
- the method includes the steps of coating the coating composition described above in the present disclosure on a substrate; and drying the coating composition to form a transparent film on a surface of the substrate.
- the mesoporous material, the co-doped tungsten oxide and the organic polysiloxane in the coating composition are in a weight ratio ranging from 42.5:57:0.5 to 8.5:76.5:15.
- the thickness of the coating can be from 0.1 to 50 ⁇ m.
- the coating composition according to the present disclosure can be dried at a lower temperature (such as no higher than 100° C., such as can be no higher than 60° C.) to remove the solvent and/or surfactant, and thereby forming a transparent layer having anti-fogging and heat-insulating functions on the substrate.
- the coating compositions in the examples and the weight proportion (%) of each of the ingredients in the comparative examples in the present disclosure wherein the precursor solution was prepared by dissolving inorganic polysiloxane prepared from tetraethoxysilane in a solution of ethanol and water, and the solid ingredient of the inorganic polysiloxane can be about 10%; the mesoporous silicon particles were solids; the co-doped tungsten oxide solution was prepared by dissolving the co-doped tungsten oxide in a toluene solution, and the solid ingredient of the co-doped tungsten oxide was about 20%; the polysiloxane solution was prepared by dissolving organic polysiloxane prepared from 3-(2,3-glycidoxy)propyltrimethoxysilane in a solution of ethanol and water, and the solid ingredient of the organic polysiloxane is about 75%.
- Precursor solution 38.02% Mesoporous silicon particles 0.18% Co-doped tungsten oxide solution 57.03% Organic polysiloxane solution 4.77%
- Precursor solution 18.99% Mesoporous silicon particles 0.32% Co-doped tungsten oxide solution 75.94% Organic polysiloxane solution 4.75%
- Precursor solution 18.96% Mesoporous silicon particles 0.45% Co-doped tungsten oxide solution 75.85% Organic polysiloxane solution 4.74%
- compositions in coating composition examples 1-3 and comparative examples 3 and 4 were coated on a transparent glass, and dried to form film examples 1-3, an anti-fogging film of comparative example 3, and heat-insulating film of comparative film 4 .
- a Fourier transform infrared spectroscopy (FTIR) was used to measure the weight ratios of the ingredients of film examples 1-3, and the results of the measurements are shown in Table 1.
- the contact angles of water on film examples 1-3, the anti-fogging film of comparative example 3, and the heat-insulating film of comparative example 4 were measured.
- the transmittance of visible light and blockage of infrared ray were measured with a visible ray spectrometer (UV-VIS) and FTIR, respectively. The results of the measurements are shown in Table 2.
- the coating composition according to the present disclosure includes a mesoporous material, co-doped tungsten oxide and organic polysiloxane, wherein the mesoporous material has an anti-fogging effect, and the co-doped tungsten oxide has an heat insulating effect from blocking infrared ray.
- the coating composition according to the present disclosure has a composite effect of anti-fogging and heat insulation.
- the mesoporous silicon particles and the co-doped tungsten oxide are successfully combined at uniquely designed compositional ratio, so as to make the formed film impart excellent hydrophilicity, transmittance of visible light transmittance, and blockage of infrared ray.
- the coating composition is suitable for use in the automobile, architectural and agricultural industries, for achieving the effects of energy conservation, heat insulation and anti-fogging.
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Abstract
MxWO3-yAy
Description
- This application claims foreign priority under 35 U.S.C. §119(a) to Patent Application No. 103142118, filed on Dec. 4, 2014, in the Intellectual Property Office of Ministry of Economic Affairs, Republic of China (Taiwan, R.O.C.), the entire content of which Patent Application is incorporated herein by reference.
- The present disclosure relates to coating compositions, films formed from the same, and methods for preparing the same, and, more particularly, to a coating composition having anti-fogging and heat-insulating functions, a film formed from the same, and a method for preparing the same.
- Most of the current heat-insulating films and heat-insulating glass for automobiles do not have an anti-fogging function. As a result, during a cold winter or a rainy season, the water vapors in the hot air inside an automobile forms fog droplets on the surface of the relatively colder glass. As such, the field of vision of a driver is affected, and a traffic accident might even occur. Electroautomobiles do not have the hot air from motors for defogging. In the case of fogging on the glass of an electroautomobile, air-conditioning is switched on for defogging. The extra electrical energy consumed by the air-conditioning would decrease the mileage. Moreover, the effect of the daily temperature difference causes the saturated water vapor inside an agricultural polyolefin shed film aggregate on the inner surface of the shed film to form water droplets, referred to as the “fogging phenomenon.” The fogging phenomenon affects daylight irradiation, and the high humidity inside in the shed is likely to induce pest damages to crops.
- Because of the chemical properties of heat-insulating and anti-fogging materials, such as hydrophilicity and hydrophobicity, it is difficult to evenly mix the two materials in a coating or a film-forming material. As a result, most of the heat-insulating films or heat-insulating glass does not have the anti-fogging function. In order to add the anti-fogging function to a heat-insulating film, multiple steps are used in the modern technology for preparation. For example, coating a fogproof material on a heat-insulating film or attaching an anti-fogging film. However, the temperature and time for curing a fogproof coating or the process for forming a multi-layered film structure not only increases the production cost, but also limits the product use due to lowered light transmittance.
- Therefore, in order to resolve the above issues, one of the major objectives for developing the present disclosure is to develop a composite coating and a film-forming material having anti-fogging and heat-insulating functions, while maintaining high light transmittance.
- Provided is a coating composition having anti-fogging and heat-insulating functions, which includes:
- a mesoporous material;
- co-doped tungsten oxide as shown in formula (I)
-
MxWO3-yAy - wherein M is an alkali metal element, W is tungsten, O is oxygen, A is halogen, 0<x≦1, and 0<y≦0.5; and
- organic polysiloxane.
- Provided is a film having anti-fogging and heat-insulating functions, which includes: a matrix that is a continuous layer formed by organic polysiloxane; a plurality of mesoporous silicon particles dispersed in the matrix; and co-doped tungsten oxide, as shown in formula (I), embedded in the matrix and located between any two of the mesoporous silicon particles.
- Provided is a method for preparing a coating composition having anti-fogging and heat-insulating functions, which includes the steps of: preparing a mesoporous material, co-doped tungsten oxide as shown in formula (I), and organic polysiloxane; and mixing the mesoporous material, the co-doped tungsten oxide as shown in formula (I), and the polysiloxane.
-
FIG. 1 is a sectional view of a film having anti-fogging and heat-insulating functions according to the present disclosure. - In order to make the above and other objectives, features and advantages of the present disclosure more readily conceivable, the following preferred embodiments are provided, along with the appended figure, for more detailed descriptions. From the disclosure of the present specification, a person skilled in the art can conceive the other advantages and effects of the present disclosure. The present disclosure can also be implemented or applied by other different embodiments. Based on different aspects and applications, each of the details of the present disclosure can also be modified and altered in various ways, without departing from the spirit of the present disclosure. It should be understood that the following specific elements and arrangements are merely used for describing the present disclosure. Of course, these contents are merely used for exemplification, and not intended to limit the present disclosure.
- Unless otherwise specified herein, the following terms used in the specification and the appended claims having the following meanings. Specifically, the singular forms “a,” “an” and “the” include the plural forms. The terms “about” and “approximately” usually indicate a given value, or within 20%, preferably within 10%, and more preferably within 5% of a range; if a given amount is an approximate amount, it may imply the term “about” or “approximately” in a non-specified way. The term “mesoporous” indicates that the pore diameter of a pore is between 2 to 50 nm.
- The present disclosure provides a composition having anti-fogging and heat-insulating functions, which includes:
- a mesoporous material;
- co-doped tungsten oxide as shown in formula (I)
-
MxWO3-yAy - wherein M is an alkali metal element, W is tungsten, O is oxygen, A is halogen, 0<x≦1, and 0<y≦0.5; and
- organic polysiloxane.
- The present disclosure provides, a method for preparing a coating composition, which includes the steps of: preparing a mesoporous material, co-doped tungsten oxide as shown in formula (I), and organic polysiloxane; and mixing the mesoporous material, the co-doped tungsten oxide as shown in formula (I), and the organic polysiloxane. Specifically, the method includes preparing the mesoporous material by a sol-gel method; co-doping tungsten oxide with anions and cations; synthesizing the organic polysiloxane by hydrolysis; and blending the mesoporous material, the co-doped tungsten oxide and the organic polysiloxane, thereby forming the coating composition having anti-fogging and heat-insulating functions.
- In the present disclosure, the mesoporous material can include a precursor, a surfactant, and mesoporous particles. The mesoporous material is prepared by synthesizing the precursor; and self-assembling micelles and nanoparticles formed by using the surfactant in a solvent, so as to make the nanoparticles form mesoporous particles each having a mesoporous structure; and then blending the precursor and the mesoporous particles.
- Specifically, silane or siloxane (e.g., tetraethoxysilane (TEOS), tetramethoxysilane (TMOS)), and a non-ionic surfactant (e.g., a surfactant with a ethylene oxide-propylene oxide-ethylene oxide triblock copolymer (e.g., P123 (HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH20)20H) and F127 (HO(CH2CH2O)106(CH2CH(CH3)O)70(CH2CH2O)106H)) can be selected to synthesize a precursor. The precursor is an inorganic porous macromolecule, such as inorganic polysiloxane or polysilane. In an embodiment, the precursor is prepared by the following steps of: evenly mixing siloxane and a solvent (e.g., ethanol, water, and hydrochloric acid) to produce a siloxane solution; evenly mixing a surfactant with a triblock copolymer and a solvent (e.g., ethanol) to produce a surfactant solution; thoroughly mixing the siloxane solution and the surfactant solution; and then setting at room temperature to allow Si—OR of the siloxane molecules to stepwisely hydrolyze to generate Si—OH, and the siloxane molecules polymerize to form the precursor by dehydrating hydroxyl groups or undergoing dealcoholization. In an embodiment, the inorganic polysiloxane molecule can retain hydroxyl groups as surface functional groups, by controlling the pH value, temperature, and time for the reaction.
- A cationic surfactant can be selected as a template for preparing mesoporous particles. In an embodiment, the mesoporous particles are prepared by the following steps of: dissolving a cationic surfactant, cetrimonium bromide (CTABr), in polyoxyethylene-8-octyl-phenylether (Trinton-X-100) and concentrated hydrochloric acid to form a surfactant solution, wherein CTABr can form micelles in the solution; adding nanoparticles (e.g., nano silicon particles of silica) to the surfactant solution; setting after stirring to allow the nanoparticles to self-assemble on a template; washing with ionic water/ethanol several times; and then removing the template to obtain the mesoporous particles. In an embodiment, the mesoporous particles required by the present disclosure can be controlled by the selection of the surfactant used (i.e., the arrangement of the template) and the adjustment of the reaction conditions such as pH value, temperature, and time for the self-assembling reaction. For example, the size of the particle diameter of the mesoporous particle can be greater than about 50 nm, such as greater than about 100 nm, such as between 200 nm to 1000 nm, and the specific surface area of a mesoporous particle can be greater than about 800 cm2/g.
- Moreover, a tungsten oxide co-doped with anions and cations is prepared by the steps of: adding an alkali metal salt and a halogen salt at appropriate proportions during the process for synthesizing tungsten oxide; and heating the mixture from 300° C. to 800° C. in a hydrogen reduction environment, thereby obtaining the co-doped tungsten oxide powder having a chemical structure of MxWO3-yAy, wherein M is an alkali metal element, W is tungsten, O is oxygen, A is halogen, 0<x≦1, and 0<y≦0.5.
- More specifically, the precursor for synthesizing tungsten oxide can be selected from ammonium metatungstate, ammonium orthotungstate, ammonium paratungstate, alkali metal tungstate, tungstic acid, tungsten silicide, tungsten sulfide, tungsten oxychloride, tungsten alkoxide, tungsten hexachloride, tungsten tetrachloride, tungsten bromide, tungsten fluoride, tungsten carbide, carbon tungsten oxide, or other salts containing tungsten. The alkali metal salts can be selected from at least one of alkali metal carbonate, alkali metal bicarbonate, alkali metal nitrate, alkali metal nitrite, alkali metal hydroxide, alkali metal halogenated salt, alkali metal sulfate, alkali metal sulfite, and other alkali metal-containing salts. The halogenated salt can be selected from halogenated amine, organic ammonium salts, halogenated carbon, halogenated hydrogen, halogenated tungsten, halogenated benzene, halogenated aromatic group, halogenated alkane, or other halogen-containing salts. The preparation and characteristics of the above tungsten oxide co-doped with anions and cations can be referred to TW I402218, which is a patent owned by the Applicant, the entirely of which is incorporated by reference herein.
- After the co-doped tungsten oxide is obtained, it can be subjected to a grinding process, in order to control the size of the particle diameter of the co-doped tungsten oxide required by the present disclosure. The particle diameter of the co-doped tungsten oxide can be no more than 100 nm, such as between 50 to 100 nm, such as between 60 to 80 nm. During the above grinding process, a small amount of inorganic metal oxide, such as silica and/or titanium oxide and/or aluminum oxide and/or zirconium oxide is added, and the inorganic metal oxide is wrapped around the outer surface of the co-doped tungsten oxide, so as to avoid aggregation and the change in the surface characteristics of the particles of co-doped tungsten oxide. Further, a small amount of silane, tilane or organic metal groups can also be added to modify the surface properties of the co-doped tungsten oxide, so as to increase the dispersibility of the co-doped tungsten oxide in an organic solvent or a polymer and the compatibility of the co-doped tungsten oxide with an organic solvent or a polymer.
- Moreover, the process of synthesizing an organic polysiloxane by hydrolysis includes the steps of providing a siloxane monomer (e.g., 3-(2,3-glycidoxy)propyltrimethoxysilane or vinyltrimethoxysilane), wherein siloxane monomer includes at least one functional group selected from a vinyl group, an acrylic acid group, and an ethoxy group; dissolving the siloxane monomer in an acidic solvent (e.g., hydrochloric acid aqueous solution), wherein the pH value of the reaction solution is from 1 to 5, the reaction temperature is from 10° C. to 40° C., and the reaction time is from 0.5 to 5 hours; and conducting hydrolysis-polymerization at room temperature while stirring. After completion of the reaction, distillation is conducted at a reduced pressure to extra additional solvent, and thereby obtaining the organic polysiloxane.
- After the mesoporous material, co-doped tungsten oxide and organic polysiloxane are prepared, the mesoporous material and co-doped tungsten oxide with appropriate particle diameters are screened for and selected, wherein the ratio of the particle diameter of a mesoporous particle (e.g., a mesoporous silicon particle) to that of the co-doped tungsten oxide can be from 20:1 to 1:1, such as from 20:1 to 2:1, such as from 16:1 to 2:1. The mesoporous material, the co-doped tungsten oxide and the organic polysiloxane are blended in an appropriate weight ratio ranging, for example, from 42.5:57:0.5 to 8.5:76.5:15, so as to make the mesoporous material and the co-doped tungsten oxide to evenly disperse in the organic polysiloxane. As a result, a coating composition having anti-fogging and heat-insulating functions is obtained.
- The present disclosure further provides a film having anti-fogging and heat-insulating functions.
FIG. 1 is a schematic sectional view of a film according to the present disclosure. As shown inFIG. 1 , afilm 1 having anti-fogging and anti-insulating functions includes atransparent layer 11 having anti-fogging and insulating functions formed on asubstrate 12. Thesubstrate 12 can be glass or plastic. The plastic can be selected from, but not limited to, polyethylene (PE), polyethylene terephthalate (PET), polyimide, etc. - As shown in
FIG. 1 , thetransparent layer 11 can be constituted by amatrix 113, a plurality ofmesoporous silicon particles 111, andco-doped tungsten oxide 112 as shown in formula (1). In an embodiment, thematrix 113 is a continuous layer formed by organic polysiloxane, themesoporous silicon particles 111 are dispersed in thematrix 113, any two of themesoporous silicon particles 111 are spaced apart, and theco-doped tungsten oxide 112 is embedded in thematrix 113, and located between any two of themesoporous silicon particles 111. - In an embodiment, the
matrix 113 can further includes a precursor, a surfactant, and the like. The precursor is an inorganic polysilane or polysiloxane molecule having a hydrophilic group, which can increase the hydrophilicity of thetransparent layer 11. Organic polysiloxane provides adhesion and support, such that it can effectively improve the film formation and thickness of thetransparent layer 11. The thickness of thetransparent layer 11 can be about 0.1 μm or higher, such as about 1 μm or higher, such as from 1 to 50 μm. Moreover, the surfaces of themesoporous silicon particles 111 also have hydrophilic groups. The affinity between thematrix 113 and each of themesoporous silicon particles 111 allow any two of themesoporous silicon particles 111 to be dispersed in thematrix 113 in a way that they are spaced part. The width W of the spacing parallel to a surface of thematrix 113 can be greater than about 50 nm. In another embodiment, the spacing on a surface parallel to a surface of the matrix can be no more than 50 nm. Theco-doped tungsten oxide 112 has a structure of MxWO3-yAy, wherein M is a metal alkali element, W is tungsten oxide, O is oxygen, A is halogen, 0<x≦1, and 0<y≦0.5. The particle diameter of amesoporous silicon particle 111 can be from 50 to 1000 nm. The specific surface area of a mesoporous silicon particle can be greater than 800 cm2/g. The particle diameter of theco-doped tungsten oxide 112 can be from 50 to 100 nm. In order to fill theco-doped tungsten oxide 112 in the space among the plurality ofmesoporous particles 111, the ratio of the particle diameter of themesoporous silicon particle 111 to that of theco-doped tungsten oxide 112 can be from 20:1 to 1:1, such as from 20:1 to 2:1, such as from 16:1 to 2:1. - In an embodiment, as the
mesoporous silicon particles 111 and theco-doped tungsten oxide 112 in an appropriate ratio of particle diameter is selected in the present disclosure, the apexes of a portion of themesoporous silicon particles 111 protrude from a surface of thematrix 113. The hydrophilic groups on the surfaces of themesoporous silicon particles 111 and thematrix 113 can cause the contact angle of a water molecule on a surface of thetransparent layer 111 to rapidly decrease to 0° from 10°, so that thefilm 1 imparts an anti-fogging effect. Further, the alkali metal and the halogenatedco-doped tungsten oxide 112 have high conductivity, such that 74% or more of the infrared ray with a wavelength of 800 nm or higher can be effectively blocked. Hence, thefilm 1 has a heat-insulating function for blocking infrared ray, while maintaining the transmittance of visible light to 60%, or even 80% or higher. - In the present disclosure further provided is a method for preparing a film having anti-fogging and heat-insulating functions. The method includes the steps of coating the coating composition described above in the present disclosure on a substrate; and drying the coating composition to form a transparent film on a surface of the substrate.
- In an embodiment of the present disclosure, the mesoporous material, the co-doped tungsten oxide and the organic polysiloxane in the coating composition are in a weight ratio ranging from 42.5:57:0.5 to 8.5:76.5:15. The thickness of the coating can be from 0.1 to 50 μm. In an embodiment, the coating composition according to the present disclosure can be dried at a lower temperature (such as no higher than 100° C., such as can be no higher than 60° C.) to remove the solvent and/or surfactant, and thereby forming a transparent layer having anti-fogging and heat-insulating functions on the substrate.
- The followings specifically exemplify the coating compositions in the examples and the weight proportion (%) of each of the ingredients in the comparative examples in the present disclosure, wherein the precursor solution was prepared by dissolving inorganic polysiloxane prepared from tetraethoxysilane in a solution of ethanol and water, and the solid ingredient of the inorganic polysiloxane can be about 10%; the mesoporous silicon particles were solids; the co-doped tungsten oxide solution was prepared by dissolving the co-doped tungsten oxide in a toluene solution, and the solid ingredient of the co-doped tungsten oxide was about 20%; the polysiloxane solution was prepared by dissolving organic polysiloxane prepared from 3-(2,3-glycidoxy)propyltrimethoxysilane in a solution of ethanol and water, and the solid ingredient of the organic polysiloxane is about 75%.
-
-
Precursor solution 38.02% Mesoporous silicon particles 0.18% Co-doped tungsten oxide solution 57.03% Organic polysiloxane solution 4.77% -
-
Precursor solution 18.99% Mesoporous silicon particles 0.32% Co-doped tungsten oxide solution 75.94% Organic polysiloxane solution 4.75% -
-
Precursor solution 18.96% Mesoporous silicon particles 0.45% Co-doped tungsten oxide solution 75.85% Organic polysiloxane solution 4.74% -
-
Precursor solution 90.78% Mesoporous silicon particles 0.57% Organic polysiloxane solution 9.13% -
-
Precursor solution 57.14% Mesoporous silicon particles 38.10% Organic polysiloxane solution 4.76% -
-
Precursor solution 89.47% Mesoporous silicon particles 0.10% Organic polysiloxane solution 1.88% -
-
Co-doped tungsten oxide solution 100% - The phenomenon of the particle aggregation and precipitation (i.e., gelling) occurred shortly in comparative examples 1 and 2 after blending, such that the products have a storage problem and cannot form continuous coatings. Although a portion of particles aggregated in examples 1 and 3 after a longer period of time, the effect of use was not affected. It is clear that the unique design of the compositional ratio of each of the ingredients can allow a mixture to be stable.
- Each of the compositions in coating composition examples 1-3 and comparative examples 3 and 4 was coated on a transparent glass, and dried to form film examples 1-3, an anti-fogging film of comparative example 3, and heat-insulating film of comparative film 4. A Fourier transform infrared spectroscopy (FTIR) was used to measure the weight ratios of the ingredients of film examples 1-3, and the results of the measurements are shown in Table 1. The contact angles of water on film examples 1-3, the anti-fogging film of comparative example 3, and the heat-insulating film of comparative example 4 were measured. The transmittance of visible light and blockage of infrared ray were measured with a visible ray spectrometer (UV-VIS) and FTIR, respectively. The results of the measurements are shown in Table 2.
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TABLE 1 Weight ratio of ingredient Film Film Film example 1 example 2 example 3 Precursor 20.06% 9.06% 9.0% Mesoporous silicon particle 0.94% 1.55% 2.12% Co-doped tungsten oxide 60.17% 72.41% 72.01% Organic polysiloxane 18.83% 16.98% 16.87% -
TABLE 2 Film Film Film Compar- Compar- exam- exam- exam- ative ative ple 1 ple 2 ple 3 example 3 example 4 Contact angle of 8.7 to 0 9.6 to 0 7.0 to 0 7.4 89.6 water Visible light 80 74 60 91 69 transmittance (%) Blockage of 74 84 97 11 94 infrared ray (%) - From the above, the coating composition according to the present disclosure includes a mesoporous material, co-doped tungsten oxide and organic polysiloxane, wherein the mesoporous material has an anti-fogging effect, and the co-doped tungsten oxide has an heat insulating effect from blocking infrared ray. As such, the coating composition according to the present disclosure has a composite effect of anti-fogging and heat insulation. In an embodiment of the present disclosure, the mesoporous silicon particles and the co-doped tungsten oxide are successfully combined at uniquely designed compositional ratio, so as to make the formed film impart excellent hydrophilicity, transmittance of visible light transmittance, and blockage of infrared ray. Hence, the coating composition is suitable for use in the automobile, architectural and agricultural industries, for achieving the effects of energy conservation, heat insulation and anti-fogging.
- The above examples are provided only to illustrate the principle and effect of the present disclosure, and they do not limit the scope of the present disclosure. One skilled in the art should understand that, modifications and alterations can be made to the above examples, without departing from the spirit and scope of the present disclosure. Therefore, the scopes of the present disclosure should be accorded to the disclosure of the appended claims.
Claims (18)
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| TW103142118A TWI523919B (en) | 2014-12-04 | 2014-12-04 | Anti-fogging and heat insulating coating composition, method for preparing therefof and film formed from the composition |
| TW103142118 | 2014-12-04 |
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| US9359506B1 US9359506B1 (en) | 2016-06-07 |
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| US (1) | US9359506B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11655160B2 (en) | 2017-05-05 | 2023-05-23 | William Blythe Limited | Tungsten oxide-based material |
| US12084356B2 (en) | 2017-05-05 | 2024-09-10 | William Blythe Limited | Tungsten oxide-based material |
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| CN109987855B (en) * | 2017-12-29 | 2022-08-12 | 法国圣戈班玻璃公司 | Thermal insulation glass, preparation method and thermal insulation glass product |
| CN109991813B (en) | 2017-12-29 | 2022-06-21 | 财团法人工业技术研究院 | Photosensitive composite material and method for forming composite film using the same |
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| EP0989166A4 (en) | 1998-04-10 | 2001-11-28 | Matsushita Electric Works Ltd | Inorganic coating composition and hydrophilic inorganic coating film |
| PL202047B1 (en) | 2002-04-25 | 2009-05-29 | Alpla Werke | Plastic bottle |
| CN100346992C (en) | 2004-01-02 | 2007-11-07 | 清华大学 | Autombobile windshield glass possessing infrared reflection performance and its preparation method |
| SI22672A (en) | 2007-12-04 | 2009-06-30 | Univerza v Novi Gorici Laboratorij za raziskave v okolju | PREPARATION OF TiO2/SiO2 SOLS AND THEIR USE FOR APPLICATION OF SELF-CLEANING AND ANTI-FOGGING COATINGS |
| JP5597532B2 (en) | 2008-03-04 | 2014-10-01 | 株式会社東芝 | Hydrophilic member and hydrophilic product using the same |
| CN102311234B (en) | 2010-07-09 | 2013-05-01 | 中国科学院理化技术研究所 | Transparent self-cleaning SiO2Antifogging coating and preparation method thereof |
| JP5087184B2 (en) | 2010-08-06 | 2012-11-28 | Dic株式会社 | One-pack type coating composition, photocatalyst used therefor, coating film thereof, and production method thereof |
| WO2012020981A2 (en) | 2010-08-10 | 2012-02-16 | 연세대학교 산학협력단 | Glass substrate manufacturing method and glass thereof |
| CN102560480B (en) * | 2010-12-07 | 2014-10-15 | 财团法人工业技术研究院 | Heat insulating material and method for producing same |
| TWI408183B (en) | 2010-12-07 | 2013-09-11 | Ind Tech Res Inst | Heat shielding material and method of manufacturing the same |
| JP6214539B2 (en) * | 2011-10-28 | 2017-10-18 | アファンタマ アクチェンゲゼルシャフト | Tungsten oxide buffer layer that can be manufactured by solution process and organic electronic device including the same |
| JP6123680B2 (en) * | 2011-12-15 | 2017-05-10 | 旭硝子株式会社 | Anti-fogging article and method for producing the same, water-absorbing layer forming composition, and article for transport equipment |
| TWI480345B (en) * | 2012-11-23 | 2015-04-11 | Ind Tech Res Inst | Paint, preparing method thereof, and film formed from the paint |
| TWI531602B (en) * | 2012-12-28 | 2016-05-01 | 財團法人工業技術研究院 | Transparent heat shielding composition |
| CN103304878A (en) | 2013-06-24 | 2013-09-18 | 苏州新区佳合塑胶有限公司 | Heat isolation and heat preservation plastic thin film |
| CN103664003A (en) | 2013-10-28 | 2014-03-26 | 滁州旭中化工有限公司 | Preparation method of heat-insulating anti-fogging film |
| CN103818082A (en) | 2013-12-31 | 2014-05-28 | 保定宝理塑研包装有限公司 | Coating type multifunctional long-lasting mirror surface sunlight greenhouse membrane and production method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11655160B2 (en) | 2017-05-05 | 2023-05-23 | William Blythe Limited | Tungsten oxide-based material |
| US12084356B2 (en) | 2017-05-05 | 2024-09-10 | William Blythe Limited | Tungsten oxide-based material |
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| Publication number | Publication date |
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| TW201621008A (en) | 2016-06-16 |
| CN105778754B (en) | 2018-12-18 |
| CN105778754A (en) | 2016-07-20 |
| TWI523919B (en) | 2016-03-01 |
| US9359506B1 (en) | 2016-06-07 |
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