WO2006062102A1 - 光触媒機能および熱線反射機能を有するガラス部材、ならびに、それを用いた複層ガラス - Google Patents
光触媒機能および熱線反射機能を有するガラス部材、ならびに、それを用いた複層ガラス Download PDFInfo
- Publication number
- WO2006062102A1 WO2006062102A1 PCT/JP2005/022378 JP2005022378W WO2006062102A1 WO 2006062102 A1 WO2006062102 A1 WO 2006062102A1 JP 2005022378 W JP2005022378 W JP 2005022378W WO 2006062102 A1 WO2006062102 A1 WO 2006062102A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- glass
- thickness
- glass member
- oxide
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 257
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 98
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 239000011941 photocatalyst Substances 0.000 claims description 111
- 230000002265 prevention Effects 0.000 claims description 24
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- 229910052718 tin Inorganic materials 0.000 claims description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 125000006850 spacer group Chemical group 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 150000003754 zirconium Chemical class 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 304
- 229910052581 Si3N4 Inorganic materials 0.000 description 54
- 238000000034 method Methods 0.000 description 37
- 206010040844 Skin exfoliation Diseases 0.000 description 32
- 239000002585 base Substances 0.000 description 31
- -1 chlorine ions Chemical class 0.000 description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 28
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 239000013078 crystal Substances 0.000 description 20
- 239000010408 film Substances 0.000 description 16
- 238000005259 measurement Methods 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 238000010894 electron beam technology Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000484 niobium oxide Inorganic materials 0.000 description 6
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910001923 silver oxide Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QIDSGAWIQBZWEZ-UHFFFAOYSA-N [O--].[O--].[O--].[Zn++].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[Zn++].[Zn++].[Zn++] QIDSGAWIQBZWEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005546 reactive sputtering Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- WSUTUEIGSOWBJO-UHFFFAOYSA-N dizinc oxygen(2-) Chemical compound [O-2].[O-2].[Zn+2].[Zn+2] WSUTUEIGSOWBJO-UHFFFAOYSA-N 0.000 description 3
- 238000004299 exfoliation Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000012788 optical film Substances 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- AKVPCIASSWRYTN-UHFFFAOYSA-N zinc oxygen(2-) silicon(4+) Chemical compound [Si+4].[O-2].[Zn+2].[O-2].[O-2] AKVPCIASSWRYTN-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- DUCFBDUJLLKKPR-UHFFFAOYSA-N [O--].[Zn++].[Ag+] Chemical group [O--].[Zn++].[Ag+] DUCFBDUJLLKKPR-UHFFFAOYSA-N 0.000 description 1
- FUWMBNHWYXZLJA-UHFFFAOYSA-N [Si+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] Chemical compound [Si+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] FUWMBNHWYXZLJA-UHFFFAOYSA-N 0.000 description 1
- YGZODFSAPJLMGJ-UHFFFAOYSA-N [Si+4].[O-2].[Zn+2].[O-2].[Ti+4] Chemical compound [Si+4].[O-2].[Zn+2].[O-2].[Ti+4] YGZODFSAPJLMGJ-UHFFFAOYSA-N 0.000 description 1
- FRIKWZARTBPWBN-UHFFFAOYSA-N [Si].O=[Si]=O Chemical compound [Si].O=[Si]=O FRIKWZARTBPWBN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- B01J35/39—
-
- 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
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/365—Coating different sides of a glass substrate
Definitions
- the present invention relates to a glass member in which a heat ray reflective layer is formed on one surface of a glass substrate, and a photocatalytic layer is formed on the other surface, and a multilayer glass using the same.
- a photocatalyst such as anatase type titanium dioxide has been known to exhibit anti-soiling effect that decomposes organic substances by ultraviolet irradiation, antibacterial activity and hydrophilicity, etc. Recently, visible light has a catalytic function.
- the photocatalytic ability to exert A photocatalytic layer for imparting such photocatalytic ability to a substrate such as glass is disposed on the surface of the substrate, and the method of forming the photocatalytic layer is generally a vacuum film formation method such as sputtering or vapor deposition, or a vacuum deposition method.
- the membrane method is widely adopted.
- Patent Document 1 discloses that when forming a medium comprising a photocatalyst composition on the surface of a glass substrate, the glass substrate, the medium, and the medium are prevented in order to prevent the medium function from being degraded by the alkali that dissolves by the glass force. And a method of forming an underlayer between them. For example, use of zirconium oxide, particularly amorphous zirconium oxide, has been proposed as the underlayer.
- Patent Document 2 discloses that zirconium oxide is used as an underlayer formed between a base material and a photocatalyst layer, and titanium oxide is used as the photocatalyst layer.
- Patent Document 3 a metal oxide layer containing zirconium oxide or the like is interposed between the base and the photocatalyst layer, and the acid from the photocatalyst layer to the base is formed by the metal oxide layer.
- Methods have been disclosed for suppressing the diffusion of elements.
- Patent Document 4 similarly discloses a method of providing a zirconium oxide layer between a substrate and a titanium oxide layer.
- Patent Document 5 discloses that zirconium oxide having a monoclinic crystal system is used as an underlayer, and titanium oxide having an anatase crystal system is used as a photocatalyst layer. There is.
- Patent Documents 6 and 7 disclose the relationship between the thickness of the underlayer and the photocatalyst layer and the optical properties.
- Patent Document 6 discloses tin oxide (SnO 2) and an acid as the underlayer.
- Patent Document 7 discloses a technique of providing a high temperature stable cubic or orthorhombic acid zirconium oxide layer between a base material and a titanium oxide layer, and further, it is used in automobiles and the like. In the case, the thickness of the titanium oxide layer should be such that the opposite side can be seen!
- a glass member having a heat ray reflective layer laminated on the surface of a glass substrate and a photocatalytic layer laminated on the other surface is used as a multilayer glass (Patent Document 8).
- the multi-layered glass is usually a glass having two glass plates on the outdoor side and the indoor side, both of which are disposed to allow a space between the two via a spacer.
- the glass member as described above is disposed, for example, as an outdoor side glass plate such that the photocatalyst layer is on the outermost layer of the multilayer glass and the inner side of the heat ray reflective multilayer glass.
- Patent Document 1 Japanese Patent Application Laid-Open No. 9-227167
- Patent Document 2 Japanese Patent Application Laid-Open No. 10-66878
- Patent Document 3 Japanese Patent Application Laid-Open No. 2000-312830
- Patent Document 4 Japanese Unexamined Patent Application Publication No. 2001-205094
- Patent Document 5 International Publication WO 03Z53577 Brochure
- Patent Document 6 Japanese Unexamined Patent Application Publication No. 2000-51369
- Patent Document 7 International Publication WO 02Z40417 Brochure
- Patent Document 8 International Publication WO 02Z62716 Pamphlet
- the photocatalytic function may not be sufficiently exhibited. Furthermore, the photocatalytic layer If not, there is a problem that the reflectance of the finally obtained glass member becomes large or interference color appears, as the function as a photocatalyst layer is not fully exhibited. For these reasons, it has been difficult to achieve both the photocatalytic function and the preferred reflectance and color tone for a glass member having a photocatalytic layer laminated thereon.
- the double glazing using the glass member provided with the heat ray reflection layer as described above has a high reflectance on the outdoor side (photocatalyst layer side), so the reflected color tone on the outdoor side is colorless or slightly bluish Or, it was difficult to make a blue-green or greenish multi-layer glass.
- the photocatalytic layer has high photocatalytic activity, and low reflectance and colorless or thin blue color on the side of the photocatalytic layer.
- the purpose is to provide a glass member exhibiting a blue-green or green reflection tone, as well as a double glazing.
- the first glass member of the present invention is a glass member in which a heat ray reflective layer is laminated on one surface of a glass substrate and a photocatalytic layer is laminated on the other surface.
- the glass substrate and the heat ray reflective layer are in a state where the heat ray reflective layer is laminated on one surface of the glass substrate and the photocatalyst layer is not laminated on the other surface (hereinafter referred to as
- the reflection chromaticity (a *, b *) of the other surface of the glass substrate is in the range of ⁇ 4 ⁇ a * ⁇ 2 and 5 ⁇ b * ⁇ 0, And the visible light reflectance of the other surface of the glass substrate is 10% or less, and the other surface of the glass substrate includes a peeling prevention layer, a crystalline underlayer and a photocatalytic layer.
- the thickness of the crystalline underlayer is 2 ⁇ ⁇ !
- the thickness of the photocatalyst layer is 2 ⁇ ⁇ !
- the anti-stripping layer is at least one material selected from the group consisting of an oxide, an oxynitride and a nitride containing at least one of silicon and tin. I assume.
- the second glass member of the present invention is a glass member in which a heat ray reflective layer is laminated on one surface of a glass substrate and a photocatalytic layer is laminated on the other surface, and the above glass substrate
- the heat ray reflective layer has a reflection chromaticity (a *, b *) of the other surface of the single-plate glass substrate in the range of ⁇ 15 ⁇ a * ⁇ 2 and ⁇ 10 ⁇ b * ⁇ 10, And the above of the glass substrate It is a combination in which the visible light reflectance of the other surface is 13% or less, the thickness of the crystalline underlayer is in the range of 2 nm to 28 nm, and the thickness of the photocatalyst layer is 2 ⁇ !
- the anti-stripping layer is characterized by containing at least one substance selected from the group consisting of an oxide containing at least one of silicon and tin, an oxynitride and a nitride.
- the multilayer glass of the present invention has two glass plates, and the two glass plates have a spacer between them so that a space is formed between the opposing surfaces of the two glass plates.
- the glass member of the present invention when the heat ray reflective layer is laminated on the glass substrate, specifically, the reflection chromaticity (a *, b *) of the other surface of the single-plate characteristic black glass substrate Even if the visible light reflectance of the other surface of the glass substrate is within 10% in the range of -4 ⁇ a * ⁇ 2 and 5 ⁇ b * ⁇ 0, the reflection is low. Rate and a colorless or pale blue reflective color tone can be realized, and furthermore, excellent photocatalytic activity can be obtained.
- the characteristic of the single plate is “the reflection chromaticity (a *, b *) of the other surface of the glass substrate is in the range of ⁇ 15 ⁇ a * ⁇ 2 and ⁇ 10 ⁇ b * ⁇ 10, and Even when the visible light reflectance of the other surface of the glass substrate is 13% or less, low reflectance and blue-green or green reflection tone can be realized, and further, excellent photocatalytic activity can be obtained. You can get it. For this reason, according to the multilayer glass using the glass member of the present invention, it is possible to achieve both high photocatalytic activity and excellent reflectance and reflection color tone on the photocatalyst layer side. It is also suitable for large area double glazing for buildings, which is superior in appearance and in terms of appearance.
- FIG. 1 is a cross-sectional view showing an example of a glass member of the present invention.
- FIG. 2 is a cross-sectional view showing an example of the multilayer glass of the present invention.
- FIG. 3 shows the case where the thickness of the photocatalyst layer is changed in the embodiment of the present invention. It is a graph which shows the relationship between the said thickness and the reflectance of a multilayer glass.
- FIG. 4 is a graph showing the relationship between the thickness and the reflectance of the multilayer glass when the thickness of the crystalline underlayer is changed in another embodiment of the present invention.
- FIG. 5 is a graph showing the reflection chromaticity of the multilayer glass when the thickness of the photocatalyst layer is changed in still another embodiment of the present invention.
- FIG. 6 is a graph showing the reflection chromaticity of the multilayer glass when the thickness of the photocatalyst layer is changed in still another embodiment of the present invention.
- FIG. 7 is a graph showing the reflection chromaticity of the multilayer glass when the thickness of the crystalline underlayer is changed in still another embodiment of the present invention.
- FIG. 8 is a graph showing the reflection chromaticity of the multilayer glass when the thickness of the crystalline base layer is changed in still another embodiment of the present invention.
- FIG. 9 is a graph showing the relationship between the thickness and the reflectance of the multilayer glass when the thickness of the photocatalyst layer is changed in still another embodiment of the present invention.
- FIG. 10 is a graph showing the relationship between the thickness and the reflectance of the multilayer glass when the thickness of the crystalline underlayer is changed in yet another embodiment of the present invention.
- FIG. 11 is a graph showing the reflection chromaticity of the multilayer glass when the thickness of the photocatalyst layer is changed in still another embodiment of the present invention.
- FIG. 12 is a graph showing the reflection chromaticity of the multilayer glass when the thickness of the photocatalyst layer is changed in still another embodiment of the present invention.
- FIG. 13 is a graph showing the reflection chromaticity of the multilayer glass when the thickness of the crystalline underlayer is changed in yet another embodiment of the present invention.
- FIG. 14 is a graph showing the reflection chromaticity of the multilayer glass when the thickness of the crystalline underlayer is changed in still another embodiment of the present invention.
- the glass member of the present invention is not limited in any way by the shape, size, etc. of these.
- FIG. 1 is a cross-sectional view showing an example of the glass member of the present invention.
- Glass member 30 is a glass
- the heat ray reflective layer 14 is laminated on one surface of the substrate 10, and the peeling prevention layer 1, the crystalline base layer 2 and the photocatalyst layer 3 are laminated in this order on the other surface.
- “crystalline” in the present invention means, for example, that when a cross section of the laminated layer is observed with a transmission electron microscope or the like, a checkered pattern or an electron beam diffraction image is observed.
- the reflected chromaticity (a *, b *) of the other surface of the glass substrate 10 is The combination is in the range of 4 ⁇ a * ⁇ 2 and 5 ⁇ b * ⁇ 0, and the visible light reflectance of the other surface of the glass substrate 10 is within 10%.
- the thickness of the crystalline underlayer 2 is 2 ⁇ !
- the thickness of the photocatalyst layer 3 is in the range of 2 nm to 20 nm, and the anti-stripping layer 1 is selected from the group consisting of oxides, oxynitrides and nitrides containing at least one of silicon and tin. Including at least one.
- the thickness of the crystalline base layer 2 is in the range of 2 nm to 28 nm
- the thickness of the photocatalyst layer 3 is in the range of 2 nm to 14 nm
- the peeling prevention layer 1 is an oxide containing at least one of silicon and tin. And at least one selected from the group consisting of oxynitride and nitride.
- the present inventors have achieved the following findings as a result of earnest research, and reached the present invention.
- the inventors of the present invention observed the cross-sectional structure of the photocatalyst layer having the same thickness and showing the photocatalytic activity and the one not having the photocatalytic activity with an electron microscope.
- the crystal structure is an interfacial force with the substrate and the photocatalyst layer formed clearly and continuously to the surface of the photocatalyst layer has remarkable photocatalytic activity, it is near the interface with the substrate
- the photocatalyst layer in which an amorphous (amorphous) layer (hereinafter referred to as “dead layer”) is formed does not have sufficient photocatalytic activity. Therefore, we found that the formation of a dead layer can be suppressed by forming a crystalline base layer on the substrate to promote crystal growth of the photocatalyst layer and forming the photocatalyst layer on the surface of the substrate. .
- the do-layer is a layer in which the characteristics of amorphous (amorphous) strongly appear, and when the photocatalyst layer in which the dead layer exists is irradiated with the electron beam, the electron beam diffraction image is observed as a halo pattern, and the dead layer is dead.
- a photocatalyst layer substantially free of layers is irradiated with an electron beam, electron diffraction spots are observed.
- the photocatalyst layer reacts with anions such as chloride ion, for example, by reacting with alkali ions such as sodium present in the glass substrate to form a water-soluble salt. Since there is a risk of peeling with the underlayer and defects occur, there is a problem with durability.
- the "defect" refers to, for example, a spot-like or streak-like discolored portion or exfoliated portion produced by the generation of the water-soluble salt.
- the present inventors have conceived of the present invention from the following additional findings. That is, according to the present invention, by forming the photocatalyst layer through the underlayer that promotes the growth of the crystal particles of the photocatalyst, the appearance of the dead layer is suppressed, and further between the base and the underlayer, By providing the peeling prevention layer, it is possible to suppress the peeling of the glass substrate force and the occurrence of defects. In addition, by setting the thickness of the crystalline base layer and the thickness of the photocatalyst layer in the above-mentioned range, it is possible to realize low reflectance, colorless or pale blue, or blue-green or green reflected color tone (reflection unevenness and Uneven color tone).
- the exfoliation preventing layer, the crystalline base layer and the photocatalyst layer are provided on one surface of the glass substrate, for example, the glass member provided with only the heat ray reflective layer on one surface is used. It is possible to obtain a double glazing with improved solar heat gain compared to the double glazing used.
- the glass substrate and the heat ray reflective layer are the reflection chromaticity (a *, b *) of the other surface of the single-plate glass substrate.
- the combination is in the range of 4 ⁇ a * ⁇ 2 and 5 ⁇ b * ⁇ 0, and the visible light reflectance of the other surface of the glass substrate is within 10%.
- the thickness of the crystalline underlayer is 2 nm
- the thickness of the photocatalyst layer is in the range of 2 nm to 20 nm.
- the visible light reflectance on the photocatalyst layer side is within 20% and on the photocatalyst layer side.
- the reflection chromaticity (a *, b *) can be adjusted to ⁇ 5, a * ⁇ 0, ⁇ 12 ⁇ b ⁇ 0, and can provide excellent visible light reflectance and reflection chromaticity.
- the thickness of the crystalline underlayer is 3 ⁇ ⁇ ! In the range of ⁇ 20 nm, the thickness of the photocatalyst layer is 3 ⁇ ! It is preferable to set it in -12 nm. By setting the thicknesses of the both in such a range, the visible light reflectance of the photocatalyst layer side is within 17.5% and the photocatalyst layer side of the multilayer glass of the present invention described later. It is possible to adjust the reflection chromaticity (a *, b *) of 1 to 5 ⁇ a * ⁇ 0, 1 8 ⁇ b * ⁇ 0, and it is further excellent in both the visible light reflectance and the reflection chromaticity. Can provide
- the glass substrate and the heat ray reflective layer are formed of the reflection chromaticity (a *, b) of the other surface of the single plate glass substrate.
- *) Is a combination in the range of -15 ⁇ a * ⁇ -2 and -10 ⁇ b * ⁇ 10, and the visible light reflectance of the other surface of the glass substrate is within 13%.
- the thickness of the crystalline base layer is in the range of 2 nm to 28 nm, and the thickness of the photocatalyst layer is in the range of 2 nm to 14 nm.
- the double-layer glass described later using the glass member of the present invention has a visible light reflectance of 20% or less on the photocatalyst layer side, and a photocatalyst.
- the reflection chromaticity (a *, b *) on the layer side can be adjusted to -12, a *, -2,-, -10, b *, 5, and it is possible to have excellent visible light reflectance and reflection chromaticity. Can be provided.
- the thickness of the crystalline underlayer is 3 ⁇ ! It is preferable to set the thickness of the photocatalyst layer in the range of 3 nm to 8 nm. By setting the thicknesses of the both in such a range, the visible light reflectance on the photocatalyst layer side is further within 17.5% and on the photocatalyst layer side in the multilayer glass of the present invention described later. Adjustment of the reflection chromaticity (a *, b *) to -9 a *--3.7,-10-b * 4 and further excellent in both visible light reflectance and reflection chromaticity Can provide
- the thickness of the peeling prevention layer is not particularly limited, but is preferably 2 nm to 200 nm, more preferably 5 ⁇ ⁇ ⁇ ⁇ ⁇ ! ⁇ LOOnm. If the thickness of the peeling prevention layer is 2 nm or more, for example, the effect of suppressing layer peeling and the occurrence of defects is sufficiently obtained, and if 5 nm or more, generation of a water soluble salt by blocking of water is further enhanced. (Eg, completely) can be suppressed.
- the thickness of the peeling prevention layer is 200 nm or less, for example, the effect of suppressing delamination and the occurrence of defects and the economic viewpoint are further improved, and the delamination and defects even in the case of 100 nm or less.
- the effect of suppressing the occurrence is sufficiently obtained.
- the peeling prevention layer In the case where a layer whose refractive index is largely different from that of the glass substrate is selected as the peeling prevention layer, for example, it is preferable to make the thickness of the peeling prevention layer as small as possible in order to suppress a change in chromaticity.
- the glass substrate is not particularly limited, and a conventionally known glass substrate can be used, and the thickness thereof is not particularly limited, but usually 3 nm! It is ⁇ 12m m.
- the term "glass substrate” in the present invention refers to a substrate made of resin such as polycarbonate in place of a glass substrate as long as the single-plate properties satisfy the above range, in addition to general glass substrates. Can also be used.
- the anti-peeling layer in the present invention contains at least one of an oxide containing at least one of silicon and tin, an oxynitride, and a nitride, and specifically, silicon oxide, an acid, and the like.
- examples thereof include silicon nitride, silicon nitride, tin oxide, tin oxynitride, tin nitride and the like, and among them, it is preferable to contain silicon oxide.
- These substances are preferably amorphous. In addition, any of these substances may be used alone, or two or more of them may be used in combination.
- the tin alteration layer or the amorphous tin oxide layer formed on the contact surface between the glass substrate and the tin bath at the time of production of the substrate is peeled off.
- It can also be a protective layer.
- the anti-peeling layer has a function of blocking ions and water molecules having a small ion diameter such as chlorine ions and preventing them from reaching the external force glass substrate. Therefore, by providing the anti-peeling layer on a glass substrate, the generation of water-soluble salts by the ions and water molecules is prevented, and crystals are dissolved by dissolution of the water-soluble salts. It is possible to suppress the peeling off of the glass substrate force.
- the crystalline underlayer in the present invention preferably contains, for example, at least one of a crystalline metal oxide and a metal oxide nitride.
- the metal oxide include zirconium oxide
- examples of the metal oxynitride include zirconium oxynitride.
- the crystalline underlayer includes zirconium oxide and zirconium oxynitride. It is preferable to include at least one.
- the crystal system of these metal substances is preferably monoclinic, and these substances may be used alone or in combination of two or more.
- the crystalline underlayer may further contain a slight amount of nitrogen, tin, carbon or the like.
- the photocatalyst layer in the present invention preferably contains, for example, at least one of a metal oxide and a metal oxynitride.
- the metal oxide include titanium oxide and titanium oxycarbide (TiO 2 C), and examples of the metal oxynitride include titanium oxynitride and any one of them may be used. And two or more may be used in combination.
- the photocatalyst layer preferably contains at least one of titanium oxide and titanium oxynitride.
- the crystal system of these metal substances is not particularly limited, but is preferably anatase type (tetragonal system).
- the photocatalytic layer may further contain trace amounts of nitrogen, tin and carbon.
- the photocatalytic layer can also promote the generation of carriers by doping the metal inside, thereby improving the photocatalytic effect.
- the metal Zn, Mo, and Fe are preferable because they have a high photocatalytic activity improvement effect.
- the content of the metal in the photocatalyst layer is preferably 0.1% to 1% by mass, and more preferably 0.2% to 0.5% by mass.
- the content of Fe in the photocatalyst layer is preferably 0.5% by mass. If the addition amount of the metal is equal to or more than the lower limit, the effect of the doping can be sufficiently exhibited.
- the addition amount is equal to or less than the upper limit, for example, the crystal structure of the photocatalyst is disturbed or recombined by It is possible to sufficiently avoid the possibility that the formation of the photocatalytic activity of the photocatalytic layer is reduced.
- the crystalline underlayer and the photocatalytic layer are In particular, at least one of a crystalline metal oxide and a metal oxynitride is preferable, and in particular, at least one of the oxygen interatomic distances in the crystal forming the underlayer is the photocatalyst. It is preferable to approximate to one of the oxygen interatomic distance in the crystal constituting the layer.
- the preferred underlayer ie, the monoclinic acid-zirconium layer
- the interplanar spacing of the (111) oriented plane is, for example, 0.20-0. 30 nm, and the interplanar spacing of the (-111) oriented plane is, for example, 0.30-0. 34 nm.
- the anatase type titanium oxide layer as a preferable photocatalyst layer has a (101) plane as an electron beam diffraction image obtained by electron beam irradiation from a direction (normal direction) perpendicular to the layer cross section. There is a diffraction image from.
- the surface separation of the (101) oriented surface is, for example, 0.33 to 0.37 mm.
- strain is generated in the crystal and the oxygen position of the crystal plane is shifted, and the position of the oxide that forms the crystalline underlayer with oxygen. The influence on the rapid crystal growth of the photocatalyst layer due to the decrease in the integrity of the catalyst can be sufficiently avoided.
- examples of the heat ray reflective layer include low radiative films.
- the low radiation film is not particularly limited, but a multi-layer laminate in which dielectrics, silver, dielectrics, silver and dielectrics are laminated in this order by a known film forming method such as sputtering method (substrate Z first Dielectric layer Z first silver layer Z second dielectric layer Z second silver layer Z third dielectric layer) and the like are preferable.
- the dielectric for example, titanium oxide, zinc oxide, tin oxide, niobium oxide, tantalum oxide, silicon nitride, silicon oxynitride and the like can be used.
- the thickness of the heat ray reflective layer is not particularly limited, but preferably ⁇ ⁇ ⁇ ⁇ ⁇ !
- the reflection chromaticity and the visible light reflectance of the single plate can be appropriately set by those skilled in the art depending on, for example, the thickness, the material, the layer structure, and the like of the heat ray reflective layer.
- the method for producing the glass member of the present invention is not particularly limited !, for example, the following methods may be mentioned. First, a peeling prevention layer is formed on one surface of a glass substrate, subsequently, a crystalline base layer is formed on the surface of the peeling prevention layer, and then a photocatalytic layer is formed on the surface of the crystalline base layer. On the other hand, a heat ray reflective layer is formed on the other surface of the glass substrate.
- a conventionally known method can be used, and examples thereof include a sputtering method, a vacuum evaporation method and the like.
- Examples of the method for forming the crystalline base layer include conventionally known methods such as liquid phase method (sol gel method, liquid phase deposition method, etc.), vapor phase method (sputtering method, vacuum evaporation method, CVD method, etc.) Can be used.
- liquid phase method sol gel method, liquid phase deposition method, etc.
- vapor phase method sputtering method, vacuum evaporation method, CVD method, etc.
- the method of forming the photocatalyst layer is also not particularly limited, and the same method as the crystalline underlayer can be used, and in particular, the gas phase method is preferably used.
- the method of forming the heat ray reflective layer is not particularly limited, and a conventionally known method may be mentioned.
- a conventionally known method can be used, and examples thereof include a sputtering method and the like.
- the thickness of the glass substrate, the peeling prevention layer, the crystalline base layer, the photocatalyst layer and the heat ray reflective layer of the present invention can be adjusted by a conventionally known method.
- an example of the multilayer glass of the present invention will be described with reference to FIG.
- the multi-layer glass of the present invention is not limited in any configuration except for the use of the glass member of the present invention.
- FIG. 2 is a cross-sectional view showing an example of the multilayer glass of the present invention, and the same reference numerals as in FIG. 1 denote the same parts in FIG.
- the glass plate 20 and the glass member 30 are disposed via the spacer 40 so that a gap is formed between the opposing surfaces of the two, and the glass member 30 has the photocatalyst layer 3 thereof.
- the outermost layer of the multilayer glass 50 is disposed.
- the heat ray reflective layer 24 is a low radiation film made of dielectric 5aZ silver 6aZ dielectric 5bZ silver 6bZ dielectric 5c, but is not limited thereto.
- Such a multilayer glass 50 is usually disposed so that the surface on which the glass member 30 is disposed (specifically, the surface of the photocatalyst layer 3) is on the outdoor side and the other glass plate 20 is on the indoor side. Used.
- door side glass plate there is no particular limitation on the other glass plate (hereinafter referred to as “indoor side glass plate”) different from the glass member of the present invention in addition to the multi-layer glass of the present invention, as described above.
- the thickness of the glass plate is not particularly limited, and is the same as described above.
- the spacers are also not particularly limited, and conventionally known ones can be used.
- the gap between the glass member and the indoor side glass plate via the spacer may be hollow or may be sealed with any material.
- the distance of the space between the glass member and the indoor-side glass plate is not particularly limited, but is preferably 6 mn! It is ⁇ 18 mm.
- the method for producing the multilayer glass having the glass member of the present invention is not particularly limited, and a conventionally known method can be used.
- the glass member shown in FIG. 1 was produced by the following method, and the double-layered glass shown in FIG. 2 was produced using this.
- the heat ray reflective layer 24 was formed on one surface of a glass substrate 10 (10 cm in length, 10 cm in width, 3 mm in thickness).
- the optical characteristics of a single plate composed of the glass substrate 10 and the heat ray reflective layer 24 are the reflection chromaticity (a *, b *)-4 ⁇ a * ⁇ 2 and -5 ⁇ of the glass substrate side.
- the dielectric 5a is set so that the range of b * ⁇ 0 and the visible light reflectance on the side of the glass substrate is within 10%.
- a low radiation film (Low-E film; thickness: 16 nm) which is a configuration of Z silver 6aZ dielectric 5bZ silver 6bZ dielectric 5c was formed.
- the specific configuration of the heat ray reflective layer 24 is as follows.
- Each layer of the heat ray reflective layer 24 was formed by the following method.
- the titanium oxide layer and the zinc oxide layer were formed by reactive sputtering using a metal target of titanium and zinc and using a mixed gas of argon gas and oxygen gas as a discharge gas.
- the silicon nitride layer was formed by reactive sputtering using a Si target and using a mixed gas of argon gas and nitrogen gas as a discharge gas.
- the silver layer was formed by sputtering using a silver target and argon gas as a discharge gas.
- a direct current pulse power source was used as the discharge power source.
- optical characteristics of a single plate composed of the glass substrate 10 and the heat ray reflective layer 24 were as follows as a result of measurement.
- An amorphous silicon oxide (SiO 2) layer is formed on the other surface of the glass substrate 10 as a peeling prevention layer 1 by reactive sputtering, and then a crystalline base is formed on the surface of the peeling prevention layer 1.
- a monoclinic acid zirconium (ZrO 2) layer is formed by reactive sputtering.
- a glass member 30 was manufactured by forming an anatase-type titanium oxide (TiO 2) layer as a photocatalyst layer 3 on the surface of the crystalline base layer 2 by a sputtering method.
- TiO 2 anatase-type titanium oxide
- the obtained glass member 30 and the indoor-side glass plate 20 (3 mm in thickness) are disposed via a spacer (12 mm in thickness) so as to create a space between the opposing surfaces of both, A laminated glass 50 was produced. (Change in thickness of photocatalyst layer)
- the thickness of the photocatalyst layer is changed at 2 nm pitch, and the thickness of the peeling prevention layer 1 (SiO layer) is 10 nm.
- the thickness of the crystalline underlayer 2 (ZrO layer) was set to 5 nm by the method described above.
- a multilayer glass was produced.
- the thickness of the crystalline underlayer is changed at 2 nm pitch, and the thickness of the peeling prevention layer 1 (SiO layer) is 1
- the thickness of Onm and photocatalyst layer 3 (TiO layer) is set to 5 nm
- a multilayer glass was produced.
- the visible light reflectance (R%) on the photocatalyst layer 3 side of each double glazing 50 obtained as described above was measured according to JIS R3106. These results are shown in FIGS. 3 and 4.
- FIG. 3 is a graph showing the relationship between the thickness of the photocatalyst layer 3 and the visible light reflectance
- FIG. 4 is a graph showing the relationship between the thickness of the crystalline underlayer 2 and the visible light reflectance.
- the visible light reflectance (R%) is preferably 20% or less, more preferably 17.5% or less.
- the change in the reflection chromaticity (a *, b *) of the photocatalyst layer 3 was measured for the multilayer glass obtained as described above.
- the measurement of the reflection chromaticity was calculated based on JIS Z8729 using the spectrum from which the spectrophotometer power was also obtained.
- FIGS. 5 and 6 are graphs showing the reflection chromaticities (a *, b *) of the multilayer glass in which the thickness of the photocatalyst layer is changed
- FIG. 5 is a graph showing the visible chromaticity based on the results of FIG.
- the range in which the light reflectance is 20% or less is surrounded by a square
- FIG. 6 is a square in which the range in which the visible light reflectance is 17.5% or less is squared based on the results of FIG.
- FIGS. 5 and 6 are graphs showing the reflection chromaticities (a *, b *) of the multilayer glass in which the thickness of the photocatalyst layer is changed
- FIG. 5 is a graph showing the visible chromaticity based on the results of FIG.
- the range in which the light reflectance is 20% or less is surrounded by a square
- FIG. 6 is a square in which the range in which the visible light reflectance is 17.5% or less is squared based on the results of FIG.
- FIG. 7 and 8 are graphs showing the reflection chromaticities (a *, b *) of the multilayer glass in which the thickness of the crystalline base layer is changed, and FIG. 7 is based on the results of FIG. The range in which the visible light reflectance is 20% or less is surrounded by a square, and FIG. 8 is a diagram in which the range in which the visible light reflectance is 17.5% or less is surrounded by a square based on the result of FIG. There is. (Measurement of photocatalytic activity)
- the photocatalytic activity of the double glazing obtained as described above was evaluated by the following method. First, using a black lamp (center wavelength: 365 nm) as a light source, the contact angle ( ⁇ ) of water after UV irradiation was performed for 60 minutes under the conditions of illuminance lmWZ cm 2 was measured. Specifically, after UV irradiation is performed on the photocatalyst layer side of the multilayer glass under the conditions described above, the multilayer glass is placed on a horizontal base so that the surface of the photocatalyst layer becomes horizontal, and the light is emitted. Water 0.4: z L was dropped onto the surface of the catalyst layer.
- the contact angle of the water droplet on the surface is measured using a contact angle measuring device (CA-150 manufactured by Kyowa Interface Science Co., Ltd.), and the contact angle ( ⁇ ) shows a result of 15 degrees or less and 20 degrees or less.
- the thickness of the crystalline underlayer 2 and the thickness of the photocatalyst layer 3 were determined for each of the multilayer glasses.
- reflection chromaticity 5 ⁇ a * ⁇ 0, and 1 12 ⁇ b * ⁇ 0 is a range where the reflection color is light blue
- reflection chromaticity 5 ⁇ a * ⁇ 0, 1 8 ⁇ b * ⁇ 0 is a range in which the color becomes blue lighter than the reflection color.
- the thickness of the crystalline underlayer 2 is 2 ⁇ ! ⁇ 28 m m
- the thickness of the photocatalyst layer 3 2 ⁇ ⁇ ! By setting the thickness to -20 nm, it has been found that a double glazing that achieves both excellent photocatalytic activity and visible light reflectance and reflection chromaticity is achieved. Further, by setting the thickness of the crystalline base layer 2 to 3 nm to 20 nm and the thickness of the photocatalyst layer 3 to 3 nm to 12 nm, the photocatalytic activity and visible light reflectance more excellent, and colorless or light blue reflection chromaticity The It was a force that could be achieved.
- a glass member 30 having the same configuration as that of FIG. 1 is manufactured by the same method as that of Example 1 except that the specific film configuration of the heat ray reflective layer 24 is changed, and using this, the same as FIG. A double layer glass 50 was produced.
- the heat ray reflective layer 24 was formed on one surface of the glass substrate 10 in the same manner as in Example 1.
- the optical characteristics of a single plate consisting of the glass substrate 10 and the heat ray reflection layer 24 are as follows: the reflection chromaticity (a *, b *) of the glass substrate side is -15 ⁇ a * ⁇ -2 and -10 ⁇ b * ⁇ 10
- the visible light reflectance on the side of the glass substrate is set to 13% or less, and the film thickness of the low emissivity film is 148 nm.
- the specific configuration of the heat ray reflective layer 24 is as follows.
- the optical characteristics of a single plate composed of the glass substrate 10 and the heat ray reflective layer 24 were as follows.
- Example 1 the thickness of the photocatalyst layer and the crystalline underlayer is changed to produce a multilayer glass, and the visible light reflectance and reflection of the photocatalyst layer 3 in the same manner as in Example 1. The chromaticity was measured. Further, the photocatalytic activity was measured by the same method as in Example 1.
- FIG. 9 is a graph showing the relationship between the thickness of the photocatalyst layer 3 and the visible light reflectance
- FIG. 10 is a graph showing the relationship between the thickness of the crystalline underlayer 2 and the visible light reflectance.
- FIG. 11 and FIG. 12 are graphs showing the reflection chromaticity (a *, b *) of the multilayer glass in which the thickness of the photocatalyst layer is changed, and FIG. 11 is a visible light based on the result of FIG.
- the range in which the reflectance shows 20% or less is surrounded by a square
- FIG. 12 the range in which the visible light reflectance shows 17.5% or less is surrounded by a square based on the result of FIG.
- FIG. 13 and 14 are graphs showing the reflection chromaticities (a *, b *) of the multilayer glass in which the thickness of the crystalline base layer is changed, and FIG. 13 is based on the results of FIG.
- the visible light reflectance of 20% or less is surrounded by a square, and FIG. 14 is the square of the visible light reflectance of 17.5% or less based on the result of FIG. .
- the reflection color tone of the multi-layer glass in this embodiment is particularly preferably in the range of bluish green to green, and is preferably 12 to 20 * b * 5.
- the preferred range of the reflection chromaticity is -9 a * 3.17 10 b * 4.
- the thickness of the crystalline underlayer 2 is 2 ⁇ ! ⁇ 28 m m
- a double-glazed glass having both the rate and the reflection chromaticity can be obtained.
- the photocatalytic activity, the visible light reflectance and the blue-green or green reflection color tone can be further improved. It turned out that it could be realized.
- a double-glazed glass 50 was produced in the same manner as in Example 1 except that the thicknesses of the peeling prevention layer 1, the crystalline base layer 2 and the photocatalyst layer 3 were 10 nm, 5 nm and 5 nm, respectively. Then, the chromaticity (transmission chromaticity) of the transmitted light, the reflection chromaticity (the photocatalytic layer 3 side and the indoor side glass plate 20 side), the visible light transmittance, the visible light reflectance, the solar radiation transmission in this double-layered glass. The rate and solar heat gain rate were measured. The visible light reflectance, the transmission chromaticity, and the reflection chromaticity were measured by the same method as in Example 1. The visible light transmittance and the solar radiation transmittance were measured based on JIS R3106, and the solar heat gain rate was calculated based on JIS R3106 using a spectrum measured by a spectrophotometer.
- a double-glazed glass was manufactured and measured in the same manner as in Example 3 except that the thickness of each of the peeling prevention layer 1, the crystalline base layer 2 and the photocatalyst layer 3 was 10 nm.
- a multilayer glass was manufactured in the same manner as in Example 1 except that only the heat ray reflective layer was laminated on the glass substrate without forming the peeling prevention layer, the crystalline base layer and the photocatalyst layer, the above Example The same measurement as in 5 was performed.
- Example 3 -2.80 3.25 -1.07-3.78 -0.21 71.1
- Each heat ray reflective layer shown in Table 4 below was laminated on a glass substrate. Then, in the same manner as in Example 3, except that the thicknesses of the peeling prevention layer 1, the crystalline base layer 2 and the photocatalyst layer 3 were 10 nm, 10 nm and 5 nm, respectively, It measured.
- Each heat ray reflective layer is formed by forming a first dielectric layer, a first silver layer, a second dielectric layer, a second silver layer, and a third dielectric layer on the surface of a glass substrate. is there.
- Table 4 below shows the material of the layer constituting the heat ray reflective layer
- Table 5 below shows the film thickness of the layer constituting the heat ray reflective layer
- Table 6 below shows the optical film thickness of the dielectric layer and the silver layer at a wavelength of 530 nm.
- the film thickness shown in Table 5 below is a physical film thickness obtained by measuring the cross section of the layer using a transmission electron microscope (manufactured by Topcon Corporation: transmission electron microscope EM002B), and the optical film shown in Table 6 below
- the film thickness is a value obtained by multiplying the physical film thickness by the refractive index at 530 nm.
- Refractive index is a spectroscopic ellipsometer (US First dielectric layer First silver layer Second dielectric layer Second silver layer Third dielectric layer
- Sample 9 Zinc oxide, silver oxide, niobium oxide, silicon nitride, silicon nitride, silicon nitride, silicon nitride, silicon nitride
- Zinc oxide Oxidation sub IS Zinc oxide Silver oxidation
- Sample 1 Silver oxide, niobium oxide, silicon nitride, silicon nitride, zinc oxide, silver oxide, niobium oxide, silicon nitride
- Test sample 1 Zinc oxide Silver Titanium oxide Zinc oxide Silicon nitride Oxide iS Silicon nitride Zinc oxide Silver Titanium oxide Zinc oxide Silicon nitride
- the second abductor layer The second silver layer The second dielectric layer The second silver sheet The second attractive layer
- Table 7 The measurement results of the reflection chromaticity on the glass surface side of the single plate, the transmission chromaticity of the multilayer glass, and the reflection chromaticity on the indoor side and the outdoor side of the multilayer glass are shown in Table 7 below.
- Table 8 below shows the results of measurement of the visible light reflectance on the glass surface side of the single plate, the visible light transmittance of the multilayer glass, and the visible light reflectance on the indoor side and the outdoor side of the multilayer glass.
- Visible light reflectance (%) Visible light selectivity (%) Visible light reflectance (%) Visible light reflectance (%) Visible light reflectance (%)
- the glass member of the present invention low reflectance and colorless or pale blue, blue-green or green reflected color tone can be realized, and furthermore, excellent photocatalytic activity can be obtained. Can. For this reason, according to the multilayer glass using the glass member of the present invention, it is possible to achieve both high photocatalytic activity and excellent reflectance and reflection color tone on the photocatalyst layer side. Therefore, it is suitable for a large-area double glazing for buildings which is excellent in the photocatalytic function and which emphasizes exhilaration etc. in terms of appearance.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2005800418844A CN101072735B (zh) | 2004-12-06 | 2005-12-06 | 具有光催化剂功能和红外线反射功能的玻璃构件以及使用该玻璃构件的多层玻璃 |
JP2006546708A JP5121002B2 (ja) | 2004-12-06 | 2005-12-06 | 光触媒機能および熱線反射機能を有するガラス部材、ならびに、それを用いた複層ガラス |
EP05814220A EP1852402A1 (en) | 2004-12-06 | 2005-12-06 | Glass member having photocatalytic function and heat ray reflective function, and double layer glass employing it |
US11/758,360 US20070237968A1 (en) | 2004-12-06 | 2007-06-05 | Glass Member Having Photocatalytic Function and Heat Reflecting Function and Double Paned Glass Including The Same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004-353436 | 2004-12-06 | ||
JP2004353436 | 2004-12-06 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/758,360 Continuation US20070237968A1 (en) | 2004-12-06 | 2007-06-05 | Glass Member Having Photocatalytic Function and Heat Reflecting Function and Double Paned Glass Including The Same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006062102A1 true WO2006062102A1 (ja) | 2006-06-15 |
Family
ID=36577929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/022378 WO2006062102A1 (ja) | 2004-12-06 | 2005-12-06 | 光触媒機能および熱線反射機能を有するガラス部材、ならびに、それを用いた複層ガラス |
Country Status (5)
Country | Link |
---|---|
US (1) | US20070237968A1 (ja) |
EP (1) | EP1852402A1 (ja) |
JP (1) | JP5121002B2 (ja) |
CN (1) | CN101072735B (ja) |
WO (1) | WO2006062102A1 (ja) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1466665B1 (en) * | 2001-12-21 | 2012-10-10 | Nippon Sheet Glass Co., Ltd. | Member having photocatalytic function and method for manufacture thereof |
US20060264525A1 (en) * | 2003-03-11 | 2006-11-23 | Jsr Corporation | Composition for photocatalyst coating and coating film |
DE602005003228T2 (de) | 2004-07-12 | 2008-08-28 | Cardinal Cg Co., Eden Prairie | Wartungsarme beschichtungen |
WO2006067102A2 (fr) * | 2004-12-21 | 2006-06-29 | Glaverbel | Feuille de verre portant un empilage multi-couches |
CA2648686C (en) | 2006-04-11 | 2016-08-09 | Cardinal Cg Company | Photocatalytic coatings having improved low-maintenance properties |
US20080011599A1 (en) | 2006-07-12 | 2008-01-17 | Brabender Dennis M | Sputtering apparatus including novel target mounting and/or control |
US7820309B2 (en) | 2007-09-14 | 2010-10-26 | Cardinal Cg Company | Low-maintenance coatings, and methods for producing low-maintenance coatings |
JP5217023B2 (ja) * | 2009-08-24 | 2013-06-19 | 独立行政法人国立高等専門学校機構 | 光触媒多層金属化合物薄膜及びその作成方法 |
CN102442778B (zh) * | 2010-09-30 | 2014-06-04 | 惠州晶宝光电科技有限公司 | 一种荧光玻璃及其制备方法与应用 |
KR102041003B1 (ko) * | 2012-06-21 | 2019-11-05 | 닛토덴코 가부시키가이샤 | 적외선 반사 기능이 있는 투광성 기판 |
JP6282142B2 (ja) * | 2014-03-03 | 2018-02-21 | 日東電工株式会社 | 赤外線反射基板およびその製造方法 |
CN104044314A (zh) * | 2014-07-04 | 2014-09-17 | 苏州普京真空技术有限公司 | 红外反射调光玻璃 |
EP3541762B1 (en) | 2016-11-17 | 2022-03-02 | Cardinal CG Company | Static-dissipative coating technology |
GB201910988D0 (en) * | 2019-08-01 | 2019-09-18 | Pilkington Group Ltd | Touchenable coated substrate |
EP4041691A1 (en) * | 2019-10-08 | 2022-08-17 | Guardian Glass, LLC | Low-e matchable coated articles having absorber film and corresponding methods |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08104547A (ja) * | 1994-08-01 | 1996-04-23 | Nippon Sheet Glass Co Ltd | 断熱ガラス |
WO2003053577A1 (fr) * | 2001-12-21 | 2003-07-03 | Nippon Sheet Glass Co., Ltd. | Element avec fonction photocatalytique et procede de fabrication de celui-ci |
JP2004518603A (ja) * | 2001-02-08 | 2004-06-24 | カーディナル・シージー・カンパニー | 被覆基材の縁部処理方法 |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3934961A (en) * | 1970-10-29 | 1976-01-27 | Canon Kabushiki Kaisha | Three layer anti-reflection film |
CH563945A5 (ja) * | 1971-10-20 | 1975-07-15 | Balzers Patent Beteilig Ag | |
CH557546A (de) * | 1972-10-19 | 1974-12-31 | Balzers Patent Beteilig Ag | Aus einer mehrzahl von einfachen oder zusammengesetzen (lambda)/4-schichten bestehender reflexionsvermindernder belag. |
US4440822A (en) * | 1977-04-04 | 1984-04-03 | Gordon Roy G | Non-iridescent glass structures |
US4322276A (en) * | 1979-06-20 | 1982-03-30 | Deposition Technology, Inc. | Method for producing an inhomogeneous film for selective reflection/transmission of solar radiation |
US4465575A (en) * | 1981-09-21 | 1984-08-14 | Atlantic Richfield Company | Method for forming photovoltaic cells employing multinary semiconductor films |
US4814056A (en) * | 1987-06-23 | 1989-03-21 | Vac-Tec Systems, Inc. | Apparatus for producing graded-composition coatings |
CN2080065U (zh) * | 1990-11-01 | 1991-07-03 | 伟光镀膜玻璃有限公司 | 四层膜结构的镀膜玻璃 |
US5254392A (en) * | 1991-06-24 | 1993-10-19 | Ford Motor Company | Anti-iridescence coatings |
US5194990A (en) * | 1991-10-07 | 1993-03-16 | Ford Motor Company | Low color purity, anti-reflection coatings for transparent glazings oriented at high angles of incidence |
FR2684095B1 (fr) * | 1991-11-26 | 1994-10-21 | Saint Gobain Vitrage Int | Produit a substrat en verre muni d'une couche a basse emissivite. |
US5853866A (en) * | 1993-12-10 | 1998-12-29 | Toto Ltd. | Multi-functional material with photocalytic functions and method of manufacturing same |
US6352755B1 (en) * | 1994-10-04 | 2002-03-05 | Ppg Industries Ohio, Inc. | Alkali metal diffusion barrier layer |
US5811191A (en) * | 1994-12-27 | 1998-09-22 | Ppg Industries, Inc. | Multilayer antireflective coating with a graded base layer |
FR2730990B1 (fr) * | 1995-02-23 | 1997-04-04 | Saint Gobain Vitrage | Substrat transparent a revetement anti-reflets |
FR2734811B1 (fr) * | 1995-06-01 | 1997-07-04 | Saint Gobain Vitrage | Substrats transparents revetus d'un empilement de couches minces a proprietes de reflexion dans l'infrarouge et/ou dans le domaine du rayonnement solaire |
FR2736632B1 (fr) * | 1995-07-12 | 1997-10-24 | Saint Gobain Vitrage | Vitrage muni d'une couche conductrice et/ou bas-emissive |
US6037289A (en) * | 1995-09-15 | 2000-03-14 | Rhodia Chimie | Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions |
FR2738813B1 (fr) * | 1995-09-15 | 1997-10-17 | Saint Gobain Vitrage | Substrat a revetement photo-catalytique |
FR2748743B1 (fr) * | 1996-05-14 | 1998-06-19 | Saint Gobain Vitrage | Vitrage a revetement antireflet |
US5780149A (en) * | 1996-09-13 | 1998-07-14 | Libbey-Ownes-Ford Co. | Glass article having a solar control coating |
FR2759362B1 (fr) * | 1997-02-10 | 1999-03-12 | Saint Gobain Vitrage | Substrat transparent muni d'au moins une couche mince a base de nitrure ou d'oxynitrure de silicium et son procede d'obtention |
US6027766A (en) * | 1997-03-14 | 2000-02-22 | Ppg Industries Ohio, Inc. | Photocatalytically-activated self-cleaning article and method of making same |
US5935716A (en) * | 1997-07-07 | 1999-08-10 | Libbey-Owens-Ford Co. | Anti-reflective films |
JP4174862B2 (ja) * | 1998-08-04 | 2008-11-05 | ソニー株式会社 | 薄膜トランジスタの製造方法および半導体装置の製造方法 |
US6165598A (en) * | 1998-08-14 | 2000-12-26 | Libbey-Owens-Ford Co. | Color suppressed anti-reflective glass |
US6294441B1 (en) * | 1998-08-18 | 2001-09-25 | Semiconductor Energy Laboratory Co., Ltd. | Method of manufacturing a semiconductor device |
US6193378B1 (en) * | 1999-06-25 | 2001-02-27 | Gentex Corporation | Electrochromic device having a self-cleaning hydrophilic coating |
JP3622585B2 (ja) * | 1999-08-05 | 2005-02-23 | 日本板硝子株式会社 | 光触媒活性を有する物品 |
JP3477148B2 (ja) * | 1999-12-02 | 2003-12-10 | カーディナル・シージー・カンパニー | 耐曇り性透明フィルム積層体 |
JP2001240960A (ja) * | 1999-12-21 | 2001-09-04 | Nippon Sheet Glass Co Ltd | 光触媒膜が被覆された物品、その物品の製造方法及びその膜を被覆するために用いるスパッタリングターゲット |
US6677063B2 (en) * | 2000-08-31 | 2004-01-13 | Ppg Industries Ohio, Inc. | Methods of obtaining photoactive coatings and/or anatase crystalline phase of titanium oxides and articles made thereby |
EP1637225A4 (en) * | 2003-06-09 | 2007-12-19 | Nippon Sheet Glass Co Ltd | PHOTOCATALYST ELEMENT |
EP1640149A4 (en) * | 2003-06-20 | 2009-09-16 | Nippon Sheet Glass Co Ltd | LINK WITH PHOTOCATALYTIC ACTIVITY AND MULTILAYER GLASS |
-
2005
- 2005-12-06 JP JP2006546708A patent/JP5121002B2/ja not_active Expired - Fee Related
- 2005-12-06 EP EP05814220A patent/EP1852402A1/en not_active Withdrawn
- 2005-12-06 WO PCT/JP2005/022378 patent/WO2006062102A1/ja active Application Filing
- 2005-12-06 CN CN2005800418844A patent/CN101072735B/zh not_active Expired - Fee Related
-
2007
- 2007-06-05 US US11/758,360 patent/US20070237968A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08104547A (ja) * | 1994-08-01 | 1996-04-23 | Nippon Sheet Glass Co Ltd | 断熱ガラス |
JP2004518603A (ja) * | 2001-02-08 | 2004-06-24 | カーディナル・シージー・カンパニー | 被覆基材の縁部処理方法 |
WO2003053577A1 (fr) * | 2001-12-21 | 2003-07-03 | Nippon Sheet Glass Co., Ltd. | Element avec fonction photocatalytique et procede de fabrication de celui-ci |
Also Published As
Publication number | Publication date |
---|---|
JP5121002B2 (ja) | 2013-01-16 |
CN101072735A (zh) | 2007-11-14 |
CN101072735B (zh) | 2011-08-10 |
EP1852402A1 (en) | 2007-11-07 |
US20070237968A1 (en) | 2007-10-11 |
JPWO2006062102A1 (ja) | 2008-06-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2006062102A1 (ja) | 光触媒機能および熱線反射機能を有するガラス部材、ならびに、それを用いた複層ガラス | |
CA2630363C (en) | Solar control low-emissivity coatings | |
EP3319916B1 (fr) | Materiau muni d'un empilement a proprietes thermiques | |
JP4362476B2 (ja) | 光触媒機能を有する部材および複層ガラス | |
JP4763569B2 (ja) | 高赤外反射コーティング、薄膜コーティング堆積方法および関連技術 | |
JP3849008B2 (ja) | 高性能自動調光窓コーティング材料 | |
EP2714608B1 (fr) | Substrat verrier transparent portant un revetement de couches successives | |
US7632572B2 (en) | Double silver low-emissivity and solar control coatings | |
US9482799B2 (en) | Solar-control glazing unit | |
EP2611750B1 (en) | Temperable three layer antireflective coating, coated article including temperable three layer antireflective coating, and/or method of making the same | |
JP4031760B2 (ja) | 低放射率コーティングを備えた基材 | |
JP4370396B2 (ja) | 多機能自動調光断熱ガラス及び空調方法 | |
US11709297B2 (en) | Articles coated with coatings containing light absorption materials | |
RU2759408C2 (ru) | Изделие с низкоэмиссионным покрытием, имеющим отражающий ик-излучение слой или слои и диэлектрический слой или слои из легированного оксида титана | |
US20130070340A1 (en) | Antireflective coating and substrates coated therewith | |
WO2014160357A1 (en) | Color shift improvement after heat treatment | |
US9212090B2 (en) | Photocatalytic material | |
KR20200118069A (ko) | 4중 금속층을 갖는 태양광 제어 코팅 | |
KR20190124763A (ko) | Ir 반사 층(들) 및 니오븀-도핑된 산화티타늄 유전체 층(들)을 구비한 저-e 코팅을 갖는 코팅된 물품 및 그의 제조 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KN KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2006546708 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11758360 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200580041884.4 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005814220 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 11758360 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 2005814220 Country of ref document: EP |