CN1860083A - Functional glass article and process for producing the same - Google Patents
Functional glass article and process for producing the same Download PDFInfo
- Publication number
- CN1860083A CN1860083A CNA2004800280168A CN200480028016A CN1860083A CN 1860083 A CN1860083 A CN 1860083A CN A2004800280168 A CNA2004800280168 A CN A2004800280168A CN 200480028016 A CN200480028016 A CN 200480028016A CN 1860083 A CN1860083 A CN 1860083A
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- Prior art keywords
- glass article
- metal oxide
- oxide particle
- functional
- particle group
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- 239000011521 glass Substances 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 115
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 114
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000012808 vapor phase Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims description 37
- 230000002209 hydrophobic effect Effects 0.000 claims description 29
- 239000005357 flat glass Substances 0.000 claims description 19
- 238000005229 chemical vapour deposition Methods 0.000 claims description 18
- 238000009736 wetting Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229910000077 silane Inorganic materials 0.000 claims description 13
- -1 silane compound Chemical class 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- 238000005188 flotation Methods 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 230000003373 anti-fouling effect Effects 0.000 abstract 1
- 230000002940 repellent Effects 0.000 abstract 1
- 239000005871 repellent Substances 0.000 abstract 1
- 229910001887 tin oxide Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CZRDZAGTSCUWNG-UHFFFAOYSA-M chloro(dimethyl)tin Chemical compound C[Sn](C)Cl CZRDZAGTSCUWNG-UHFFFAOYSA-M 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSDVUOAFSGSYNN-UHFFFAOYSA-N C(CCCCCCCCC)[Si](Cl)(Cl)Cl.[F] Chemical compound C(CCCCCCCCC)[Si](Cl)(Cl)Cl.[F] CSDVUOAFSGSYNN-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- GZBAUYZREARCNR-UHFFFAOYSA-N C(CCCCCCCCC)[Si](OC)(OC)OC.[F] Chemical compound C(CCCCCCCCC)[Si](OC)(OC)OC.[F] GZBAUYZREARCNR-UHFFFAOYSA-N 0.000 description 1
- 101100165177 Caenorhabditis elegans bath-15 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- SBOSGIJGEHWBKV-UHFFFAOYSA-L dioctyltin(2+);dichloride Chemical compound CCCCCCCC[Sn](Cl)(Cl)CCCCCCCC SBOSGIJGEHWBKV-UHFFFAOYSA-L 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009156 water cure Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
Abstract
A glass article having a not-level structure of high durability and excelling in functions, such as water repellency and hydrophilicity. There is provided a functional glass article comprising a glass article; a metal oxide particle assemblage of 10 to 400 nm average height superimposed on a surface of the glass article so as to cover 50 to 90% of the surface; and at least one functional coating selected from among a water repellent coating, a hydrophilic coating and an antifouling coating, which functional coating is disposed so as to cover the metal oxide particle assemblage and to be in contact with the glass article surface. The metal oxide particle assemblage is, for example, a tin oxide particle assemblage formed by a chemical vapor phase growing method.
Description
Technical field
The present invention relates to a kind of glass article and manufacture method thereof with functions such as hydrophobicity, wetting abilities.
Background technology
If have hydrophobicity or hydrophilic article surface give concavo-convex, if if then its surface hydrophobicity then can be improved the hydrophobicity wetting ability and then can improve wetting ability.
Open in the flat 11-286784 communique the spy and to disclose a kind of method, promptly, to contain polycondensation product, metal oxide microparticle of metal alkoxide and contain fluoroalkyl or the treatment solution of the silane compound of alkyl, be coated on the surface of glass, by dry, heating, form porous matter metal oxide layer with micro concavo-convex structure that fluoroalkyl or alkyl expose.Open flat 11-286784 communique according to the spy, this method, cheap and simple and easy to do, can give glass surface with high hydrophobicity.But the durability not insufficient of the micro concavo-convex structure that obtains by this method is abundant.
Open in the 2001-17907 communique the spy, disclose a kind of method, that is, the solution coat that will contain aluminum compound, stablizer etc. forms tunicle on matrix, under the condition of not heat-treating, by being immersed in the hot water, form concavo-convex tissue at matrix surface.In this method,, can remove with the methyl aceto acetate and be the stablizer of representative or be the additive of representative with poly-glycol by hot-water cure.Therefore, according to this method, need not high temperature and just can form concavo-convex tissue.But concavo-convex the organizing that obtains by this method do not have sufficient weather resistance yet.
Open in the 2003-236977 communique the spy, a kind of didirtresistance parts are disclosed, described didirtresistance parts have the concavo-convex tunicle that is made of the metal oxide that is formed on substrate surface, film with the hydrophobicity that forms on this concavo-convex tunicle surface, its outermost surface average roughness Ra is 0.004～10 μ m.The concavo-convex tunicle that obtains by this method is different from by above-mentioned 2 kinds of concaveconvex structures that method obtains, and metal oxide need not to get involved macromolecular compound and is formed directly on the substrate surface.Therefore, this concavo-convex tunicle has good weather resistance.But in the surface of this didirtresistance parts, the contact angle of water is 125 ° at most.This is because what form on successive tunicle surface is concavo-convex, does not have to substantially improve hydrophobic size.
Summary of the invention
The objective of the invention is, a kind of glass article is provided, described glass article has the good sag and swell of weather resistance, and the function of hydrophobicity, wetting ability etc. is good.
The invention provides a kind of functional glass article, described functional glass article contains, glass article; The metal oxide particle group of center line average that form, that cover the described surface below 90% more than 50% below the above 400nm of 10nm on the described glass article surface; With functional tunicle, described functional tunicle is, with cover described metal oxide particle group and also in succession the form in described glass article surface form, be selected from least a kind of film in hydrophobic film, hydrophilic film or the didirtresistance film.
The present invention also provides the manufacture method of above-mentioned functions glass article.This method is the manufacture method that comprises the functional glass article of following operation, and described operation is to contain chemical vapor-phase growing method (the chemical vapor depositionmethod of the unstripped gas of metallic compound and oxygenant by use; Hereinafter referred to as " CVD method ") on described glass article, form metal oxide particle group's operation and form the operation of the described functional tunicle that described metal oxide particle group is covered.
In the functional glass article of the present invention, because the metal oxide particle group directly forms on the surface of glass article, the sag and swell that is formed by the metal oxide particle group has good weather resistance.Functional tunicle, owing to be in the time of the surface of glass article, the metal oxide particle group to be covered in succession, the height of the protuberance that forms by the metal oxide particle group of activatable to greatest extent.Metal oxide particle group's center line average is in the scope of keeping that is suitable for taking into account by the improvement of the concavo-convex functions such as hydrophobicity that cause and weather resistance.The lip-deep metal oxide particle group's of glass article area ratio/occupancy ratio improves in the scope of function being suitable for.Like this, according to the present invention, can provide to have the functional glass article good sag and swell of weather resistance, that have good hydrophobicity etc.
In the manufacture method of the present invention, owing to be to form the metal oxide particle group by the CVD method, the metal oxide particle group can anchor at the surface of glass article.Therefore, the sag and swell that is formed by the metal oxide group has higher weather resistance.
The metal oxide microparticle subgroup that constitutes functional glass article of the present invention is formed in its surperficial glass article, if suitably select the material of metal oxide microparticle subgroup, only just can give play to good wetting ability whereby.Promptly, the present invention also provides a kind of wetting ability glass article, described wetting ability glass article comprise glass article and, on described glass article surface, form preferred be the metal oxide particle group of stannic oxide population, described metal oxide particle group covers the described surface below 90% more than 50%, its center line average is below the above 400nm of 10nm, and the contact angle of the water of measuring after dropping on the water droplet of 2mg on the described surface is below 20 °.This wetting ability glass article based on the sort of special surface shape, can be expressed the contact angle of low-down water, and utilizes its hydrophilicity to give play to good antifog property.
Description of drawings
Fig. 1 is illustrated in the manufacturing process of the sheet glass that utilizes flotation process by the synoptic diagram of CVD method in the configuration example of the film forming device of surperficial shape of glass ribbon.
Fig. 2 is the surface of the hydrophobic treatment glass that will make in embodiment 1 of expression, with scanning electron microscope (SEM), and the synoptic diagram of the state of multiplying power observation with * 100000.
Fig. 3 is the surface of the hydrophobic treatment glass that will make in embodiment 2 of expression, uses SEM, the synoptic diagram of the state of the multiplying power observation with * 100000.
Fig. 4 is the surface of the hydrophobic treatment glass that will make in embodiment 3 of expression, uses SEM, the synoptic diagram of the state of the multiplying power observation with * 100000.
Embodiment
In the functional glass article of the present invention, be that metal oxide particle group below the above 400nm of 10nm has formed sag and swell by center line average.If the not enough 10nm of metal oxide particle group's center line average, then can not form enough big concavo-convex.On the other hand, if metal oxide particle group's center line average surpasses 400nm, then might cause the weather resistance variation of sag and swell, the problem of the glass surface of growing greatlyyer metal oxide particle and occupy.The center line average of metal oxide particle is more preferably more than the 50nm.
The metal oxide particle group's on glass article surface area ratio/occupancy ratio is more than 50% below 90%.If will improve the function of hydrophobicity etc., preferably exist a plurality of by metal oxide particle constitute concavo-convex, if the form with the successive film exists but metal oxide particle is in contact with one another, then the concavo-convex meeting that is made of the metal oxide particle group diminishes.Consider this point, preferably making the metal oxide particle group is not to cover fully to the surface of glass article, and it is over half but cover.Make to keep its flat more than 10% in the surface of glass article, and cover at least a portion in this flat by functional tunicle.
Metal oxide particle also can exist with the form that its part is piled up.Consider this point, on the surface of glass article, preferably with 50/μ m
2More than 150/μ m
2Following density (individual number density) forms metal oxide particle.When counting the number of metal oxide particle, its part fuses even be bonded with each other, but as long as grow respectively as particle as can be seen, just estimates with the number before engaging.
Metal oxide particle group's center line average can be judged based on the photo of the scanning electron microscope (SEM) that photographs with * 100000 multiplying power, 5 ° the angle of depression.Metal oxide particle group's area ratio/occupancy ratio and density (individual number density) can be judged based on the SEM photo that photographs with * 45000 multiplying power, 30 ° the angle of depression.
Metal oxide particle is preferably the crystallinity particle.To the profile of metal oxide particle without limits, its profile can be subjected to the influence of crystalline growth process etc., also can be dome (dome) shape, for example roughly hemispherical or polygonal column, for example quadrangular prism shape.Dome-shaped being meant, the multiplying power * 100000,5 ° inclination angle are taken pictures in the SEM photo that obtains, and there is not acute angle portion in its profile.
To the material that constitutes metal oxide particle without limits, metal oxide particle preferably contains at least a kind that is selected from for example titanium oxide, zirconium white, Indium sesquioxide, zinc oxide and the stannic oxide.With stannic oxide or titanium oxide is the metal oxide particle of principal constituent, and resistance to chemical reagents is good, can use cheap raw material to form.From this viewpoint, especially preferred is the metal oxide particle of principal constituent with stannic oxide.
In this manual, " principal constituent " be meant, according to custom, the ratio that contains this composition more than 50 weight %, be preferably contain this composition multiplying power more than 70 weight %, more preferably more than 90 weight %.
The frequency distribution of relevant metal oxide particle height can be 1 peak (1 a mountain shape), if but good wetting ability, hydrophobicity can be brought into play in 2 peaks or 3 peaks.That is, be preferably high protuberance and be mixed in form among low metal oxide particle (protuberance) group.If the situation at 2 peaks or 3 peaks belongs to metal oxide particle (protuberance) group's at climax center line average, preferably belong to the protuberance group's of ebb more than 2 times of center line average, especially preferably more than 3 times.
Be formed with the glass article of the metal oxide particle group with above-mentioned center line average and area ratio/occupancy ratio, can provide and to bring into play good hydrophobic shape,, then only just can become surface whereby with high-hydrophilic if suitably select metal oxide.As the metal oxide particle group, be preferably the stannic oxide population.With regard to hydrophilic degree, the contact angle of the water of measuring during the water droplet of the 2mg that drips on its surface is below 20 °, more preferably below 15 °.Hydrophilic surface with this degree, good with the affinity of the material of formation alkali screened film described later or functional tunicle, also be suitable for making functional glass article.In the surface of this wetting ability glass article, the density of metal oxide particle is 50/μ m preferably also
2More than 150/μ m
2Below.In the zone that does not form the metal oxide particle group, also can expose the surface of glass article.
When glass article contains alkaline components,, be preferably formed the alkali screened film in order to suppress the diffusion of alkaline components to functional tunicle.That is, can further contain the alkali screened film in the functional glass article, described alkali screened film be formed on be selected between glass article and the metal oxide particle group, among at least one side between metal oxide particle group and the functional tunicle.If form the alkali screened film on the surface of glass article, then functional tunicle is when covering the metal oxide particle group, not with glass article but contact with the surface of alkali screened film.If form and cover metal oxide particle group's alkali screened film, then functional tunicle covers the metal oxide particle group across the alkali screened film, and is formed on the surface of glass article across the alkali screened film.With the alkali screened film that the metal oxide particle group covers, role is the weather resistance that improves sag and swell.
The alkali screened film can be to contain at least a kind the film that is selected from silicon oxide, aluminum oxide, silicon oxide carbide and the silicon oxynitride, preferably is the film of principal constituent with the silicon oxide.
In order to suppress the diffusion of alkaline components, mitigation within reason simultaneously by the metal oxide particle group form concavo-convex, the thickness of alkali screened film is preferably below the above 100nm of 5nm, especially is preferably below the above 50nm of 10nm.By above-mentioned illustrative material alkali screened film that constitute, that have above-mentioned scope thickness, can follow the metal oxide particle group well, reflect its shape, number etc. well.In this case, also can grasp metal oxide particle group's shape, number from the surface shape of alkali screened film.
Functional tunicle is at least a kind that is selected from hydrophobic film, hydrophilic film and the didirtresistance film.Functional tunicle also can have other functions of antifog property and so on, also can have hydrophobicity and didirtresistance, wetting ability and didirtresistance, wetting ability and the functions more than 2 kinds such as antifog property, didirtresistance and antifog property simultaneously.
Hydrophobic film is preferably and contains at least a kind the film that is selected from fluoroalkyl and the alkyl.As alkyl, can be illustrated as octyl group, decyl, dodecyl.Hydrophobic film can form by containing a kind the silane compound that is selected from fluoroalkyl and the alkyl at least.Silane compound as such can exemplify out CF
3(CF
2)
7(CH
2)
2Si (OCH
3)
3, CF
3(CF
2)
5(CH
2)
2Si (OCH
3)
3, CF
3(CF
2)
7(CH
2)
2SiCl
3, CF
3(CF
2)
5(CH
2)
2SiCl
3Deng, the preferably reactive and high 3-17 fluorine decyl Trimethoxy silane (CF of hydrophobicity
3(CF
2)
7(CH
2)
2Si (OCH
3)
3), 3-17 fluorine decyltrichlorosilane (CF
3(CF
2)
7(CH
2)
2SiCl
3).These can use separately, also can multiplely be used in combination.
Hydrophobic film, the contact angle of the water of measuring when preferably having the water droplet of the 2mg that drips on its surface be more than 130 °, the hydrophobicity of degree more than 135 ° more preferably.
Hydrophilic film can also be the film that for example contains tensio-active agent.
The didirtresistance film preferably contains the film that gathers alkylene oxide group.This film can be formed by the silane compound that contains poly-alkylene oxide group.As such silane compound, can exemplify out [alkoxyl group (poly-alkylene oxide group) alkyl] trialkoxy silane, N-(triethoxysilylpropyltetrasulfide)-O-polyoxyethylene allylic carbamate, [alkoxyl group (poly-alkylene oxide group) alkyl] trichlorosilane, N-(Trichloromonosilane base propyl group)-O-polyoxyethylene allylic carbamate etc., preferably [methoxyl group (poly-inferior ethoxyl) propyl group] Trimethoxy silane.These can use separately, also can a plurality ofly be used in combination.
Comprise in the manufacture method of the present invention, with the CVD method form the metal oxide particle group operation and, form the operation of functional tunicle.The metal oxide particle group is contained the CVD method of the unstripped gas of metallic compound and oxygenant, is more specifically said so and form by the hot CVD method by use.When on the glass article surface, forming the metal oxide particle group time, the metal oxide particle group can be anchored on this surface by the CVD method.
The alkali screened film also can form by the CVD method.Promptly, glass article contains alkaline components and functional glass article and also further comprises and be formed between glass article and the metal oxide particle group and during the alkali screened film of at least one side between metal oxide particle group and the functional tunicle, manufacture method of the present invention also can further comprise the operation that forms above-mentioned alkali screened film by the CVD method.The alkali screened film can form by the hot CVD method that use contains the unstripped gas of metallic compound and oxygenant.
At glass article is under the situation of sheet glass, making in the operation of this sheet glass by flotation (Off ロ one ト) method, on become the glass ribbon of sheet glass, forms the metal oxide particle group by the CVD method and gets final product.The metal oxide particle group preferably forms on the surface of the glass article below 750 ℃ more than 600 ℃.In this case, the alkali screened film also can form on glass ribbon by the CVD method.CVD method on the glass ribbon (online CVD method) can be carried out in flotation is bathed, and also can carry out in the downstream that flotation is bathed.In the online CVD method,, under the high temperature of above-mentioned degree, unstripped gas is carried out thermooxidizing owing to can matrix not heated with thermal utilization that glass ribbon had in thermal oxidative reaction.
When functional glass article contains alkali screened film and this alkali screened film at least between metal oxide particle group and functional tunicle is when being principal constituent with the silicon oxide, if with above-mentioned illustrative silane compound as raw material to form functional tunicle, then can improve the affinity of alkali screened film and functional tunicle.
As operable metallic compound in the unstripped gas that forms the metal oxide particle group, the metallic compound that preferably contains halogen, especially chlorine, for example tin protochloride, tin chloride, titanium chloride, zinc chloride, indium chloride, aluminum chloride, zirconium chloride, monobutyl-tin-trichloride, dimethyltin chloride, dibutyl tin dichloride, dioctyl tindichloride.As operable metallic compound in the unstripped gas that forms the alkali screened film, can be with the hydride of metal, muriate, their alkyl-modified thing etc., for example, can be illustrated as the hydride of single silane etc.As oxygenant, can be illustrated as oxygen, water, water vapour, ozone, dry air.
In Fig. 1, illustration be used to implement the example of formation of the device of online CVD method.
The frit of fusing flows into flotation from melting furnace 11 and bathes in 12, forms glass ribbon 10 and moves on the molten tin bath 15, become semi-solid shape after, the traction by running roller 17 is admitted to Xu Lenglu 13.In Xu Lenglu 15 solidified glass ribbon is used in the cutting unit that has omitted in the diagram, is cut into the sheet glass of defined size.
Flotation is bathed in 12, from surperficial a distance of glass ribbon 10, is provided with the spreader 16 (being 3 spreader 16a, 16b, 16c) of regulation number in shown position.From these spreaders 16, unstripped gas is supplied on the glass ribbon 10 continuously, on the surface of glass ribbon 10, form metal oxide particle group, alkali screened film.
Unstripped gas can carry out metallic compound, oxygenant, thinner etc. to supply with behind the thorough mixing.If do not carry out thorough mixing, the composition of metal oxide particle for example takes place easily also or size is uneven or the uneven phenomenon of the thickness of alkali screened film.
In unstripped gas, can also further add reaction suppressor.As reaction suppressor, the hydrogenchloride in the time of can exemplifying out from tin chloride generation stannic oxide.If the mixture ratio of hydrogenchloride is too high, then can not generate stannic oxide, so be suitable with respect to the mol ratio less than 1 of the hydrogenchloride of tin chloride.By having used the CVD method of the different unstripped gas more than 2 kinds of hydrogen cloride concentration, may form the different metal oxide particle group more than 2 kinds of center line average.For example, can use the higher unstripped gas of hydrogen cloride concentration, form the lower stannic oxide particle of a small amount of center line average, supply with the lower unstripped gas of hydrogen cloride concentration then.By supply with the lower unstripped gas of hydrogen cloride concentration, can form the stannic oxide particle that will at first form as stannic oxide population nuclear, that center line average is higher of crystalline growth and, the lower stannic oxide population of center line average that directly forms at glass surface.Thus, can obtain the stannic oxide population that frequency distribution is 2 peaks.Single silane also is reactive higher raw material.As reaction suppressor, can exemplify out unsaturated hydrocarbon compounds such as ethene, acetylene, toluene at single silane.
Functional tunicle can form by being coated with the above-mentioned illustrative solution that contains silane compound.Solvent as in this case has no particular limits, and is hydrophilic solvent, paraffinic hydrocarbon, freonll-11 (flon) class of representative, the non-water kind solvent of silicone oil but can be illustrated as with the alcohols.Method about coating solution has no particular limits, and is coated with method, dipping absorption method etc. but can be illustrated as flow coat method, dip coating, curtain formula curtain coating, spin-coating method, spraying method, rod.Preferred coating process is flow coat method, spraying method.
Functional glass article of the present invention can contain the parts of film beyond the above-mentioned illustration etc.For example, adhere to securely in order to make functional tunicle, also can be before forming functional tunicle, primer coating is to form tunicle.
Below, by embodiment the present invention is carried out specific description, but the present invention is not limited to following embodiment.
Embodiment
At first, the measuring method that uses in estimating is described.
(center line average of metal oxide particle)
From using SEM, try to achieve the center line average of particle at * 100000 multiplying power, 5 ° the captured photo in the angle of depression.
(area ratio/occupancy ratio of particle and density)
From using SEM, try to achieve the ratio and the Particle Density (individual number density) of the occupied area of particle at * 45000 multiplying power, 30 ° the captured photo in the angle of depression.
(contact angle)
(republicanism interface science corporate system CA-DT), to the drip water droplet of distilled water of 2mg of the surface of maintenance level, is measured static contact angle with the contact angle meter.
Embodiment 1
With device with structure shown in Figure 1, on glass ribbon, form metal oxide particle group and alkali screened film, this glass ribbon cutting is obtained sheet glass.In bathing, flotation supplies with the nitrogen of 98 volume % and the hydrogen of 2 volume %, in bathing, keep non-oxidizable atmosphere, from being arranged in the spreader at upper reaches, supply contains the unstripped gas with the helium dilution of 0.38mol% dimethyltin chloride (steam), 17.35mol% water vapour, 6.97mol% oxygen, be that forming with stannic oxide is the metal oxide particle group of principal constituent on 720 ℃ the glass ribbon in temperature.Next, from the spreader of downstream side, supply with the unstripped gas of single silane with nitrogen dilution, ethene, oxygen, what form thickness and be 40nm is the alkali screened film of principal constituent with the silicon oxide.The metal oxide particle group's who obtains center line average, area ratio/occupancy ratio, individual number density are all within above-mentioned preferable range.
Secondly, when the decamethylcyclopentasiloxane to 98g stirs, with the 17 fluorine decyltrichlorosilane (CF of 2g
3(CF
2)
7(CH
2)
2SiCl
3) add and obtain the hydrophobic treatment agent, with resulting hydrophobic treatment agent, on the sag and swell that forms by the metal oxide particle group, be 30%, under the condition of room temperature, be coated with flow coat method in relative humidity.After leaving standstill 1 minute, clean its surface with ethanol, seasoning forms hydrophobic film.The surface of the hydrophobic treatment glass that obtains like this, with the contact angle of water be 140.5 °.
Embodiment 2
With the method identical, obtained forming metal oxide particle group's sheet glass with embodiment 1.But, the metal oxide particle group, be with contain 0.27mol% dimethyltin chloride (steam), 19.88mol% water vapour, 7.99mol% oxygen, form with the unstripped gas of helium dilution.Do not form the alkali screened film.The metal oxide particle group's who obtains center line average, area ratio/occupancy ratio, individual number density are all within above-mentioned preferable range.Secondly, use method similarly to Example 1 to form hydrophobic film.The surface of the hydrophobic treatment glass that obtains like this, with the contact angle of water be 138.5 °.
Embodiment 3
With the method identical, obtained forming metal oxide particle group's sheet glass with embodiment 1.But the metal oxide particle group is to form with containing unstripped gas O.11mol% tin chloride (steam), 19.29mol% water vapour, that dilute with helium.With the method identical, form the alkali screened film with embodiment 1.The metal oxide particle group's who obtains center line average, area ratio/occupancy ratio, individual number density are all within above-mentioned preferable range.Secondly, use method similarly to Example 1 to form hydrophobic film.The surface of the hydrophobic treatment glass that obtains like this, with the contact angle of water be 132.7 °.
Comparative example
On the sheet glass that does not form the metal oxide particle group, use the method identical with embodiment 1, form hydrophobic film.The contact angle of the water of the hydrophobic treatment glass that obtains like this is 110.0 °.
The SEM photo on the surface of the hydrophobic treatment glass that obtains by embodiment (multiplying power is * 100000) is illustrated respectively among Fig. 2 (embodiment 1), Fig. 3 (embodiment 2), Fig. 4 (embodiment 3).As shown in Fig. 2～Fig. 4, in the surface of each hydrophobic treatment glass, metal oxide particle does not cover whole glass surface, but roughly is evenly distributed on all zones of glass surface.As shown in Fig. 2, Fig. 4, the alkali screened film is got involved between the metal oxide particle that constitutes the metal oxide particle group, joins with the surface of sheet glass.
Embodiment 4
With the method identical, obtained forming metal oxide particle group's sheet glass with embodiment 1.With this sheet glass under the condition that does not form alkali screened film and hydrophobic film directly as trial target, estimate its wetting ability and antifog property.
Wetting ability is to measure the contact angle of water by method same as described above and estimate.The contact angle of water on surface that has formed metal oxide particle group's sheet glass is 14 °, and littler than the contact angle (26 °) on the surface of the sheet glass that does not form the metal oxide particle group, both differences are more than 10 °.
Antifog property is to estimate as follows.In 60 ℃, relative humidity are 100% environment, trial target is remained its surface (mensuration face) become plumbness, on the mensuration face, use water spray, it is all soaked the formation moisture film.Then, trial target was kept 15 minutes in above-mentioned environment, observe the area ratio (moisture film storage rate) that keeps moisture film in the mensuration face.Its result has formed in metal oxide particle group's the surface of sheet glass, and the storage rate of moisture film is 100%, and does not form in metal oxide particle group's the surface of sheet glass, and moisture film does not have residual basically.
Utilize possibility on the industry
Glass article provided by the invention has good durability and good function concurrently, as hydrophobic Property glass, hydrophily glass, soil resistance glass etc., the glass pane of the glass pane of building, automobile, In the purposes of the glass of showcase, mirror etc., bigger value is arranged.
Claims (16)
1. functional glass article wherein comprises:
Glass article;
Form on the described glass article surface, cover 90% the following stated surface more than 50%, the metal oxide particle group of center line average below the above 400nm of 10nm; With
Cover described metal oxide particle group and to be selected from least a kind of functional tunicle in hydrophobic film, hydrophilic film and the didirtresistance film in what the form on described glass article surface formed in succession.
2. functional glass article according to claim 1, wherein, described metal oxide particle group is to form by the chemical vapor-phase growing method on the surface of described glass article.
3. functional glass article according to claim 1, wherein, described glass article contains alkaline components, also contains the alkali screened film that forms at least one place that is selected between described glass article and the described metal oxide particle group and between described metal oxide particle group and the described functional tunicle.
4. functional glass article according to claim 3, wherein, described alkali screened film contains at least a kind that is selected from silicon oxide, aluminum oxide, silicon oxide carbide and the silicon oxynitride.
5. functional glass article according to claim 1, wherein, described functional tunicle is a hydrophobic film.
6. functional glass article according to claim 5, wherein, described hydrophobic film contains at least a kind that is selected from fluoroalkyl and the alkyl.
7. functional glass article according to claim 5, wherein, the contact angle of the water of measuring after the water droplet of 2mg is dripped on the surface of described hydrophobic film is more than 130 °.
8. functional glass article according to claim 1, wherein, on the surface of described glass article, described metal oxide particle is with 50/μ m
2More than 150/μ m
2Following density forms.
9. the manufacture method of a functional glass article, described functional glass article comprises glass article, the metal oxide particle group who covers the described surface below 90% more than 50% who on described glass article surface, forms, with the functional tunicle that covers described metal oxide particle group, described metal oxide particle group's center line average is below the above 400nm of 10nm, described functional tunicle is to form in the form on described glass article surface in succession, for being selected from hydrophobic film, in hydrophilic film and the didirtresistance film at least a kind, the manufacture method of described functional glass article comprises:
The chemical vapor-phase growing method that contains the unstripped gas of metallic compound and oxygenant by use, formation metal oxide particle group's operation on described glass article; With
Form the operation of functional tunicle in the mode that covers described metal oxide particle group.
10. the manufacture method of functional glass article according to claim 9, wherein, described glass article contains alkaline components, described functional glass article also contains the alkali screened film that forms at least one place that is selected between described glass article and the described metal oxide particle group and between described metal oxide particle group and the described functional tunicle, and described manufacture method also further comprises the operation that forms described alkali screened film by the chemical vapor deposition method.
11. the manufacture method of functional glass article according to claim 9, wherein, described glass article is a sheet glass, is making by flotation process in the operation of described sheet glass, is becoming the described metal oxide particle of formation on the glass ribbon of described sheet glass.
12. the manufacture method of functional glass article according to claim 9 wherein, forms described metal oxide particle group on the surface of the glass article below 750 ℃ more than 600 ℃.
13. the manufacture method of functional glass article according to claim 9, wherein, described functional glass article contains described alkali screened film at least between described metal oxide particle group and described functional tunicle,
Described alkali screened film is principal constituent with the silicon oxide,
And be that raw material forms described functional tunicle with the silane compound.
14. a wetting ability glass article wherein comprises glass article; With
Form on the described glass article surface, cover 90% the following stated surface more than 50%, the metal oxide particle group of center line average below the above 400nm of 10nm;
The contact angle of the water of measuring after the water droplet of 2mg is dripped on described surface is below 20 °.
15. wetting ability glass article according to claim 14, wherein, described metal oxide particle group is the stannic oxide population.
16. wetting ability glass article according to claim 14, wherein, on the surface of described glass article, described metal oxide particle is with 50/μ m
2More than 150/μ m
2Following density forms.
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| JP4670057B2 (en) * | 2006-06-28 | 2011-04-13 | 国立大学法人 香川大学 | Method for producing water and oil repellent antifouling glass plate |
| JP4654443B2 (en) * | 2006-06-28 | 2011-03-23 | 国立大学法人 香川大学 | Manufacturing method of solar energy utilization device |
| JP4876123B2 (en) * | 2006-12-11 | 2012-02-15 | 国立大学法人三重大学 | Method for producing response glass membrane for ion electrode, response glass membrane for ion electrode, and ion electrode |
| JP4929459B2 (en) * | 2006-12-22 | 2012-05-09 | 国立大学法人 香川大学 | Method for producing water and oil repellent antifouling glass plate |
| JP5347123B2 (en) * | 2006-12-22 | 2013-11-20 | 国立大学法人 香川大学 | Water and oil repellent antifouling glass plate, method for producing the same, vehicle and building using the same |
| JP5314055B2 (en) * | 2008-03-12 | 2013-10-16 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Durable automotive windshield coating and its use |
| JP5716663B2 (en) * | 2009-04-30 | 2015-05-13 | コニカミノルタ株式会社 | Antifouling laminate |
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| JPH11171594A (en) * | 1997-12-15 | 1999-06-29 | Nippon Sheet Glass Co Ltd | Water repellent glass article and its production |
| JP3926946B2 (en) * | 1998-06-05 | 2007-06-06 | 富士フイルム株式会社 | Antireflection film and image display device |
| JP2000239045A (en) * | 1999-02-17 | 2000-09-05 | Asahi Glass Co Ltd | Antifogging vehicular glass and its production |
| JP2001033608A (en) * | 1999-07-26 | 2001-02-09 | Nippon Sheet Glass Co Ltd | Hydrophilic cloudiness-proof mirror |
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| KR20040052516A (en) * | 2001-11-08 | 2004-06-23 | 니혼 이타가라스 가부시키가이샤 | Article coated with coating film, and functional article coated with coating film using the same |
| JP3896453B2 (en) * | 2002-03-18 | 2007-03-22 | 独立行政法人産業技術総合研究所 | Glass substrate having both photocatalytic function and low emissivity characteristics and method for producing the same |
| WO2004052639A1 (en) * | 2002-12-10 | 2004-06-24 | Nippon Sheet Glass Co., Ltd. | Article having coating film thereon, method for manufacture thereof, and applying material for forming coating film |
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| CN103228447B (en) * | 2010-12-07 | 2016-01-20 | 旭硝子株式会社 | Anti-fog properties article and manufacture method thereof |
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