CN103025678B - 具有防日光性能的玻璃板 - Google Patents
具有防日光性能的玻璃板 Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 83
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000010936 titanium Substances 0.000 claims abstract description 27
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 22
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 21
- 230000005855 radiation Effects 0.000 claims abstract description 21
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 15
- 239000010955 niobium Substances 0.000 claims description 38
- 238000003475 lamination Methods 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910017083 AlN Inorganic materials 0.000 claims description 10
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 claims description 5
- 229910020286 SiOxNy Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 230000002708 enhancing effect Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910001120 nichrome Inorganic materials 0.000 claims description 2
- 230000037072 sun protection Effects 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 69
- 230000005540 biological transmission Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- DUFGEJIQSSMEIU-UHFFFAOYSA-N [N].[Si]=O Chemical compound [N].[Si]=O DUFGEJIQSSMEIU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 230000005021 gait Effects 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/226—Glass filters
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- 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
- C03C17/3429—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 at least one of the coatings being a non-oxide coating
- C03C17/3435—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 at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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- 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
- C03C17/3602—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 the metal being present as a layer
- C03C17/3657—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 the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
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- 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
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- 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
-
- 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
- C03C17/3602—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 the metal being present as a layer
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- 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
- C03C17/3602—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 the metal being present as a layer
- C03C17/3657—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 the metal being present as a layer the multilayer coating having optical properties
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- 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
- C03C17/3602—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 the metal being present as a layer
- C03C17/3681—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 the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
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- 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
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
-
- G—PHYSICS
- G02—OPTICS
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- G02B5/20—Filters
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- G—PHYSICS
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
Abstract
本发明涉及防日光玻璃板,其包含玻璃基底和具有防日光功能的多层叠层,所述多层叠层包括选择性地吸收具有大于800纳米的波长的红外辐射的层,所述吸收层由用选自Nb或者Ta的元素X取代的二氧化钛组成,该原子百分率[X/Ti+X]为约4%至约9%和所述吸收层的厚度为20至200纳米。
Description
本发明涉及建筑或者汽车玻璃板类型的玻璃基底或者制品的领域,它们在其表面上包含为它们提供防日光性质的薄层类型涂层。术语“玻璃板”在本发明意义中理解为表示由一个或多个玻璃基底组成的任何玻璃产品,特别地单层玻璃板、双层玻璃板、三层玻璃板等等。措辞“防日光的”在本发明意义中理解为该玻璃板限制从住所或者客舱的外部向内部穿过它的能量通量,特别地红外辐射(IR)通量,同时保持足够的光透射,即典型地高于30%,甚至40%,甚至50%的能力。
这种配备有薄层叠层的玻璃板因此作用于入射日光辐射并且能够使客舱或者住所日光防护和/或隔热。此外,这些涂层必须在审美上是使人愉快的,即它们必须在透射中和在反射中具有足够中性的色度,使得不使用户不便,或者稍微蓝色或者绿色色调,特别地在建筑领域中如此。这些涂层最简单地是通常使用CVD类型沉积技术或目前更通常地使用真空溅射沉积技术(通常在本领域中被称为磁控管溅射)进行沉积,特别地当涂层由连续层的更复杂叠层组成时。
最通常,具有日光控制性质的薄层叠层包含一个甚至多个活性层。措辞“活性层”理解为表示对穿过所述玻璃板的日光辐射通量明显地作用的层。这种活性层,如已知那样,可以主要地以反射红外辐射的模式工作,或者主要地以吸收红外辐射的模式工作。
特别地,目前出售的最有效的叠层包括至少一个基本上以反射大部分入射IR(红外线)辐射的模式工作的银类型金属层。这些叠层最通常被定性为低辐射(英语为“低-e”)叠层。然而这些层对湿气很敏感并且因此仅仅用于双层玻璃板中(在其面2或者3上),以便防护湿气。根据本发明的叠层不包含这种银类型层。
在本领域中还描述了其它具有防日光功能的金属层,其包含Nb、Ta或者W类型或者这些金属的氮化物的功能层,如在例如申请WO01/21540中描述的那样。然而,在这种层内,日光辐射这次被吸收但是非选择性地被吸收,即IR辐射(即其波长在约780nm至2500nm)和可见辐射都非选择性地被吸收。这样的玻璃板因此具有选择性,如通过接近于1的TL/g比率(光透射因子/太阳因子g,如根据标准EN 410(或者NF EN410)中确定)举例说明。已知地并通常地,光透射因子或者光透射TL对应于按照光源D65,穿过玻璃板的入射光通量(即在380至780nm的波长范围中)的百分比。
已知地,该太阳因子g等于该穿过玻璃板(即进入房间)的能量与该入射太阳能的比率。更特别地,它对应于直接地透射穿过玻璃板的通量和由玻璃板(在其中包括任选地在它的表面之一上存在的多层叠层)所吸收然后任选地向内部(房间)再放出的通量。
通常,在本说明书中存在的所有光特征根据在欧洲(和法国)标准EN 410中关于测定用在建筑物用玻璃中的玻璃板的光和日光特征所描述的原理和方法获得。
本发明的一个目的因此是提供玻璃板,该玻璃板包含为它们提供防日光性质并且具有高选择性(在如上所述的意义上来说,即非常高于1的TL/g比率)的多层叠层,所述叠层是经时持久的而不需要特别的预防措施。本发明的另一目的是提供防日光玻璃板,其中所述叠层可以,特别地热处理(如淬火)之后,特别地在透射中或者在反射中,保持基本上中性的颜色或较不强烈的蓝绿色调,如特别地在建筑物领域中寻求的那样。措辞“中性颜色”或者“蓝绿色调”在本发明意义上理解为表示,在(L*,a*,b*)比色体系中,低于或者接近于10并且为负的a*和b*值。
根据本发明的玻璃板因此有利地允许通过促进光波(即具有约380至780nm波长的光波)的透射和选择性地吸收大部分红外辐射(即具有大于780nm的波长的辐射),特别地近红外辐射(即具有约780nm至约1400nm波长的辐射)选择穿过它的辐射。
根据本发明,因此使得维持用玻璃板保护的房间或者客舱明亮,同时使进入其中的热量被减到最少成为可能。
根据本发明的另一个优点,根据本发明的配备有叠层的玻璃板制备简单以及还允许显著地降低生产成本(与其它已知的具有防日光性质的玻璃板,特别地包含银基叠层的那些相比较)。
更确切地说,本发明涉及防日光玻璃板,其包含玻璃基底和具有防日光功能的多层叠层,所述多层叠层包括选择性地吸收具有大于800纳米的波长的红外辐射的层,所述吸收层由用选自Nb或者Ta的元素X取代的二氧化钛组成,该原子百分率[X/Ti+X]为约4%至约9%和所述吸收层的厚度为20至200纳米。
根据本发明的优选实施方案:
- 该原子百分率[X/Ti+X]为约4%至约7%,更优选地为约5至约7%;
- 所述吸收层的厚度为30至100纳米;和
- X是铌。
优选地,根据本发明,该防日光玻璃板包含由以下层序列组成的叠层,从该玻璃基底的表面开始:
- 一个或多个用于保护吸收层以防来自玻璃基底的碱金属离子迁移的下层,其具有总计5至150nm的几何厚度;
- 所述由用选自Nb或者Ta,优选Nb的掺杂元素X取代的二氧化钛组成的吸收层;和
- 一个或多个上层,其用于保护吸收层以防在空气中的氧,特别地在热处理(如淬火或者退火)期间,所述一个或多个层具有总计5至150nm的几何厚度。
优选地所述一个或多个下保护层或/和上保护层选自:氮化硅Si3N4,其任选地用Al、Zr或B掺杂;氮化铝AlN;氧化锡;混合氧化锌锡SnyZnzOx;二氧化硅SiO2;非掺杂的二氧化钛TiO2和氮氧化硅SiOxNy。
根据本发明一个可能并且优选的实施方案,特别地如果该玻璃板必须经受热处理(如淬火),该叠层此外,在所述保护层和吸收层之间,包括金属层,其任选地部分地或者完全地被氧化和/或氮化,具有小于5纳米的厚度,优选地具有小于3纳米,甚至小于2纳米的厚度。
这种薄层将部分地或者完全地氧化或者氮化并且由此将保护该吸收层,当所述上层例如在氮存在时通过反应溅射进行沉积(如同沉积Si3N4上保护层的情况一样)时,甚至在淬火类型热处理期间将氧化。所述薄层优选地基于金属,如铌Nb、钽Ta、钛Ti、铬Cr、镍Ni或者这些金属中至少两种的合金,如Ni-Cr合金。如果其仅仅用于充当“牺牲”层时,它可以是极其薄的,特别地约0.2至1.5nm,优选地0.5至1.5nm厚,以便尽可能少地在光透射方面对叠层不利。如果它还用于将光透射量调节至希望的水平,特别地如果更希望制备具有减小TL的防日光玻璃板,还可以为它提供可高达5nm的厚度。
优选地,金属选自Ti或者NiCr合金。
根据一个具有更好性能的实施实施方案,该叠层包含由以下层的序列,从该玻璃基底的表面开始:
- 具有5至150nm的厚度的下层,其选自:氮化硅Si3N4,其任选地用Al、Zr或者B掺杂,氮化铝AlN、氧化锡、混合氧化锌锡SnyZnzOx;二氧化硅SiO2;非掺杂的二氧化钛TiO2和氮氧化硅SiOxNy;
- 所述由用Nb取代的二氧化钛组成的吸收层,在所述吸收层中的原子百分率[Nb/Ti+Nb]为约4%至约7%和它的厚度为30至100nm;
- 具有5至150nm的厚度的上层,其选自:氮化硅Si3N4,其任选地用Al、Zr或者B掺杂,氮化铝AlN、氧化锡、混合氧化锌锡SnyZnzOx、二氧化硅SiO2、非掺杂的二氧化钛TiO2和氮氧化硅SiOxNy;和
- 优选地,在所述保护层和所述吸收层之间,任选地部分地或者完全地被氧化和/或氮化的金属钛层,其具有厚度小于3纳米。
举例来说,根据本发明的该防日光玻璃板包含由以下层的序列组成的叠层,从该玻璃基底的表面开始:
- 具有5至100nm,特别地5至70nm的厚度的Si3N4层;
- 部分地或者完全地氧化和/或氮化的金属钛层,其具有小于2nm的几何厚度;
- 所述吸收红外辐射的层,其由用Nb取代的二氧化钛组成,在所述吸收层中的原子百分率[Nb/Ti+Nb]为约4%至约7%和它的厚度为30至100nm;
- 部分地或者完全地氧化和/或氮化的金属钛层,其具有小于2nm的几何厚度;
- 具有5至100nm,特别地5至70nm的厚度的Si3N4层。
本发明还涉及用于制备防日光玻璃板的方法,包括以下步骤:
- 制备玻璃基底;
- 在玻璃基底上使用磁控管增强的真空阴极溅射技术沉积多层叠层,
其中由用选自Nb或者Ta的掺杂元素X取代的二氧化钛组成的吸收层通过在氩或者氩和氧的混合物的残余气氛中使由用选自Nb或者Ta的元素X取代的二氧化钛组成的靶溅射获得,其中原子百分率[X/Ti+X]为约4%至约9%。
用于制备根据本发明的防日光玻璃板的可替代方法包括以下步骤:
- 制备玻璃基底;
- 在玻璃基底上使用磁控管增强的真空阴极溅射技术沉积多层叠层,
其中吸收层由用选自Nb或者Ta的掺杂元素X取代的二氧化钛组成,并且通过在氧和氩的残余气氛中使由金属钛和选自Nb或者Ta的金属X混合物组成的靶溅射获得,在该靶中的原子百分率[X/Ti+X]为约4%至约9%。
仅仅地作为举例说明给出以下实施例而在它们描述的方面中不限制本发明的范围。出于比较的目的,在安装为双层玻璃板的玻璃基底上合成所有以下实施例的叠层。该叠层的所有层使用传统的磁控管溅射真空沉积技术进行沉积。出于直接比较它们的性能的目的,所有的在下面实施例中最后获得的玻璃板是由两个6毫米厚的Planilux®玻璃基底(其用16毫米厚充氩气腔分隔)组成的双层玻璃板(6/16Ar/6)。
实施例1
在该根据本发明的实施例中,使用传统的磁控管技术将由以下层的序列组成的叠层沉积在Planilux®类型玻璃基底上:
。
通过磁控管溅射技术使用包括6at%铌的TiO2靶([Nbat/(Tiat+Nbat)=0.06])获得TiO2层。通过最终获得的层的电子探针微量分析(也被称为EPMA)和SIMS(次级离子质谱法)来验证在其中的掺杂率显著地与在该靶组成相同。
带有其叠层的基底然后经受由加热至650℃持续几分钟然后淬火组成的热处理。这种处理代表如果玻璃板必须进行淬火或弯曲时它所经受的条件。
将基底安装在具有另一个Planilux®基底双层玻璃板内(6/16Ar/6),使得多层叠层位于该叠层的面2上。
为了确定这种双层玻璃板的选择性,测量它的TL和g因子。
对比实施例1:
在该实施例中,以与实施例1相同的方式实施并获得基本上相同的叠层,除了用于沉积TiO2层的靶这次不包含铌。
为了确定这种双层玻璃板的选择性,在与先前相同的条件下测量它的TL和g因子。
对比实施例2:
在该实施例中,使用由Saint-Gobain Glass France以商标Cool Lite KN 164销售的双层玻璃板(6/16Ar/6),其活性层,即作用于该穿过所述玻璃板的日光辐射的层是约10纳米厚的银层,所述银层被设置在叠层中,该叠层被沉积在该双层玻璃板的面2上。
为了确定这种可商业获得的双层玻璃板的选择性,在与先前相同的条件下测量它的TL和g因子。
对比实施例3:
在该实施例中,使用由Saint-Gobain Glass France以商标Cool Lite ST 167销售的双层玻璃板(6/16Ar/6),其活性层,即作用于该穿过所述玻璃板的日光辐射的层,是约15纳米厚的铌氮化物层,所述铌氮化物层被设置在叠层中,该叠层被沉积在该双层玻璃板的面2上。
为了确定这种可商业获得的双层玻璃板的选择性,在与先前相同的条件下测量它的TL和g因子。
对比实施例4:
在该实施例中,与实施例1相同的方式实施,但是进行以下改变:
- 通过磁控管溅射技术使用包含约1.7at%铌的TiO2靶获得TiO2层;
- 调节玻璃基底在该磁控管腔室中的行进速度使得沉积的TiO2:Nb层具有等于300纳米的厚度。
为了确定这种双层玻璃板的选择性,在与先前相同的条件下测量它的TL和g因子。
获得的不同玻璃板的特性,其根据标准EN 410测量,在以下表1中给出:
表1
在表1中给出的数据的比较显示50nm厚的非掺杂的TiO2层(对比实施例1)不是选择性的并且对可见光和对热量(特别地对热红外线)呈现相对透明的。然而,根据本发明以约6%的高浓度将掺杂剂Nb引入到该层中(实施例1)使得可以,通过保持完全同样小的薄层厚度,显著地提高玻璃板的选择性。如此获得的选择性水平因此更接近于对于基于银层的低辐射叠层(对比实施例2)观察到的选择性水平,其然而不以吸收近红外线模式而是以反射近红外线模式工作。在这方面,这种结果是非常令人惊奇的。
根据本发明的实施例1和对比实施例3的比较表明,根据本发明的带有主要通过吸收日光辐射进行工作的活性层的玻璃板是比其它根据这种相同原理工作的已知的具有防日光功能性的层(特别地铌基层或者铌氮化物基层)更加选择性的。
最后,根据本发明的实施例1和对比实施例4的比较表明:接近于6%的铌掺杂水平和小的层厚度(50纳米)的组合最终使得可以获得这样的叠层,其选择性高于包含活性层(该活性层的掺杂水平是较低的但是其厚度为六倍大)的叠层的选择性。这种结果是意料之外的,这是由于众所周知透明氧化物层(如TiO2)的红外线反射性质随着它的厚度强烈地提高。
在(L*,a*,b*)体系中,玻璃板的比色特性还在透射中、在内部反射(客舱侧)中和在外部反射(外侧)中进行了测量并且在以下表2中给出。
表2
在表2中示出的数据显示根据本发明的带有叠层的玻璃板的理想的比色性质:根据实施例1的a*和b*参数总是负的并且相对低的,无论观察者的位置和视角怎样,在透射中还是在反射中。
这种比色性质产生玻璃板的较不强烈的蓝绿色或者中性颜色,如目前在建筑领域中所希望的。
根据另一个优点,根据本发明的防日光叠层,其活性层基于具有相对小的厚度(即数十纳米)的掺杂二氧化钛,是制备极其简单的和便宜的,特别地使用所谓“磁控管”的阴极溅射真空沉积技术:该二氧化钛层的小的厚度事实上允许获得不可忽视的生产率增长,因为基底在该沉积腔室中的行进速度与所述层的希望厚度直接相关的。
此外,附加的耐用性测试显示这种层可以容易地在单个玻璃板的面2上沉积,而没有使后者由于化学作用(湿气)或者由于机械作用(叠层的磨损)而退化的风险。
Claims (12)
1.汽车或建筑的防日光玻璃板,其包含玻璃基底和具有防日光功能的多层叠层,作用于日光辐射以能够使客舱或者住所日光防护和/或隔热,所述多层叠层包括选择性地吸收具有大于800纳米的波长的红外辐射的层,所述吸收层由用选自Nb或者Ta的掺杂元素X取代的二氧化钛组成,原子百分率[X/Ti+X]为4%至9%和所述吸收层的厚度为20纳米至200纳米,其中该多层叠层不包含银类型层。
2.根据权利要求1的防日光玻璃板,其中原子百分率[X/Ti+X]为4%至7%。
3.根据权利要求1或2的防日光玻璃板,其中所述吸收层的厚度为30至100纳米。
4.根据权利要求1-2之一的防日光玻璃板,其中X是铌。
5.根据权利要求1-2之一的防日光玻璃板,其中叠层由以下层的序列组成,从该玻璃基底的表面开始:
- 一个或多个用于保护吸收层以防来自玻璃基底的碱金属离子迁移的下层,其具有总计5至150nm的几何厚度;
- 所述由用选自Nb或者Ta的掺杂元素X取代的二氧化钛组成的吸收层;和
- 一个或多个用于保护吸收层以防空气中的氧的上层,所述一个或多个上层具有总计5至150nm的几何厚度。
6.根据权利要求5的防日光玻璃板,其中所述一个或多个用于保护吸收层的下层和用于保护吸收层的上层选自:氮化硅Si3N4,其任选地用Al、Zr或B掺杂、氮化铝AlN、氧化锡、混合氧化锌锡SnyZnzOx、二氧化硅SiO2、非掺杂的二氧化钛TiO2、氮氧化硅SiOxNy。
7.根据权利要求5的防日光玻璃板,其中该叠层此外在所述用于保护吸收层的下层和用于保护吸收层的上层与吸收层之间包括金属层,该金属层任选地部分地或者完全地被氧化和/或氮化,具有小于5纳米的厚度。
8.根据权利要求7的防日光玻璃板,其中金属选自Ti或者NiCr合金。
9.根据权利要求5的防日光玻璃板,其中该叠层包含由以下层的序列,从该玻璃基底的表面开始:
- 具有5至150nm的厚度的下层,其选自:氮化硅Si3N4,其任选地用Al、Zr或B掺杂,氮化铝AlN、氧化锡、混合氧化锌锡SnyZnzOx;二氧化硅SiO2;非掺杂的二氧化钛TiO2和氮氧化硅SiOxNy;
- 所述由用Nb取代的二氧化钛组成的吸收层,在所述吸收层中的原子百分率[Nb/Ti+Nb]为4%至7%和它的厚度为30至100nm;
- 具有5至150nm的厚度的上层,其选自:氮化硅Si3N4,其任选地用Al、Zr或B掺杂,氮化铝AlN、氧化锡、混合氧化锌锡SnyZnzOx、二氧化硅SiO2、非掺杂的二氧化钛TiO2和氮氧化硅SiOxNy;和
- 在所述用于保护吸收层的下层、用于保护吸收层的上层和所述吸收层之间,任选地部分地或者完全地被氧化和/或氮化的金属钛层,其厚度小于2纳米。
10.根据权利要求1-2之一的防日光玻璃板,其中该叠层由以下层的序列组成,从该玻璃基底的表面开始:
- 具有5至100nm的厚度的Si3N4层;
- 部分地或者完全地氧化和/或氮化的金属钛层,其具有小于2nm的几何厚度;
- 所述由用Nb取代的二氧化钛组成的吸收红外辐射的层,在所述吸收层中的原子百分率[Nb/Ti+Nb]为4%至7%和它的厚度为30至100nm;
- 部分地或者完全地氧化和/或氮化的金属钛层,其具有小于2nm的几何厚度;和
- 具有5至100nm的厚度的Si3N4层。
11.用于制备根据权利要求1-10之一的防日光玻璃板的方法,其包括以下步骤:
- 制备玻璃基底;
- 在玻璃基底上使用磁控管增强的真空阴极溅射技术沉积多层叠层,
其中由用选自Nb或者Ta的掺杂元素X取代的二氧化钛组成的吸收层通过在氩或者氩和氧的混合物的残余气氛中使由用选自Nb或者Ta的掺杂元素X取代的二氧化钛组成的靶溅射获得,其中原子百分率[X/Ti+X]为4%至9%。
12.用于制备根据权利要求1-10之一的防日光玻璃板的方法,包括以下步骤:
- 制备玻璃基底,
- 在玻璃基底上使用磁控管增强的真空阴极溅射技术沉积多层叠层,
其中吸收层由用选自Nb或者Ta的掺杂元素X取代的二氧化钛组成,并且通过在氧和氩的残余气氛中使由金属钛和选自Nb或者Ta的金属X混合物组成的靶溅射获得,在该靶中的原子百分率[X/Ti+X]为4%至9%。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1056531A FR2963788B1 (fr) | 2010-08-10 | 2010-08-10 | Vitrage a proprietes antisolaires |
FR1056531 | 2010-08-10 | ||
PCT/FR2011/051776 WO2012020189A1 (fr) | 2010-08-10 | 2011-07-22 | Vitrage a proprietes antisolaires |
Publications (2)
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CN103025678A CN103025678A (zh) | 2013-04-03 |
CN103025678B true CN103025678B (zh) | 2016-10-26 |
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CN201180038189.8A Expired - Fee Related CN103025678B (zh) | 2010-08-10 | 2011-07-22 | 具有防日光性能的玻璃板 |
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US (1) | US9354368B2 (zh) |
EP (1) | EP2603469B1 (zh) |
JP (1) | JP5824046B2 (zh) |
CN (1) | CN103025678B (zh) |
BR (1) | BR112013001564B1 (zh) |
CA (1) | CA2806251C (zh) |
EA (1) | EA023332B1 (zh) |
ES (1) | ES2701439T3 (zh) |
FR (1) | FR2963788B1 (zh) |
MX (1) | MX347558B (zh) |
PL (1) | PL2603469T3 (zh) |
PT (1) | PT2603469T (zh) |
WO (1) | WO2012020189A1 (zh) |
Families Citing this family (11)
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FR2988387B1 (fr) * | 2012-03-21 | 2017-06-16 | Saint Gobain | Vitrage de controle solaire |
US10871600B2 (en) | 2012-12-17 | 2020-12-22 | Guardian Glass, LLC | Window for reducing bird collisions |
FR2999563B1 (fr) | 2012-12-19 | 2015-02-27 | Eurokera | Feuille de vitroceramique munie d'un revetement de couches minces |
FR3013043B1 (fr) | 2013-11-08 | 2015-11-20 | Saint Gobain | Substrat revetu d'un empilement a couches fonctionnelles presentant des proprietes mecaniques ameliorees |
FR3019173B1 (fr) * | 2014-03-28 | 2016-03-25 | Saint Gobain | Vitrage muni d'un empilement de couches minces pour la protection solaire |
EP3194477A4 (en) * | 2014-09-15 | 2018-05-30 | Saint-Gobain Performance Plastics Corporation | Optical film including an infrared absorption layer |
US10571610B2 (en) | 2014-11-21 | 2020-02-25 | Saint-Gobain Performance Plastics Corporation | Infra-red control optical films having metal nitride between encapsulating layers containing oxide |
FR3045033B1 (fr) * | 2015-12-09 | 2020-12-11 | Saint Gobain | Procede et installation pour l'obtention d'un vitrage colore |
FR3107703B1 (fr) * | 2020-02-28 | 2023-06-23 | Saint Gobain | Vitrage de controle solaire comprenant une couche de nitrure de titane |
FR3132096B1 (fr) | 2022-01-27 | 2024-05-24 | Saint Gobain Glass France | Substrat transparent muni d’un empilement fonctionnel de couches minces |
WO2023144222A1 (fr) | 2022-01-27 | 2023-08-03 | Saint-Gobain Glass France | Substrat transparent muni d'un empilement fonctionnel de couches minces |
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JP2007329109A (ja) * | 2006-06-09 | 2007-12-20 | Nippon Sheet Glass Co Ltd | 透明電極基材及びそれを用いた光電変換装置 |
FR2927897A1 (fr) * | 2008-02-27 | 2009-08-28 | Saint Gobain | Vitrage antisolaire presentant un coefficient de transmission lumineuse ameliore. |
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JPH0764599B2 (ja) * | 1988-12-20 | 1995-07-12 | 旭硝子株式会社 | 耐久性の優れた熱線反射性を有する光学体 |
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EP1980539A1 (fr) | 2007-03-19 | 2008-10-15 | AGC Flat Glass Europe SA | Vitrage à faible emissivite |
JP5057485B2 (ja) * | 2007-06-11 | 2012-10-24 | 独立行政法人産業技術総合研究所 | 可視光透過日射熱反射膜 |
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FR2939788A1 (fr) * | 2008-12-12 | 2010-06-18 | Saint Gobain | Substrat a fonction verriere pour module photovoltaique |
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2010
- 2010-08-10 FR FR1056531A patent/FR2963788B1/fr not_active Expired - Fee Related
-
2011
- 2011-07-22 CN CN201180038189.8A patent/CN103025678B/zh not_active Expired - Fee Related
- 2011-07-22 ES ES11752277T patent/ES2701439T3/es active Active
- 2011-07-22 WO PCT/FR2011/051776 patent/WO2012020189A1/fr active Application Filing
- 2011-07-22 PL PL11752277T patent/PL2603469T3/pl unknown
- 2011-07-22 MX MX2013001505A patent/MX347558B/es active IP Right Grant
- 2011-07-22 EA EA201390212A patent/EA023332B1/ru not_active IP Right Cessation
- 2011-07-22 EP EP11752277.1A patent/EP2603469B1/fr active Active
- 2011-07-22 CA CA2806251A patent/CA2806251C/fr not_active Expired - Fee Related
- 2011-07-22 JP JP2013523651A patent/JP5824046B2/ja not_active Expired - Fee Related
- 2011-07-22 US US13/814,754 patent/US9354368B2/en active Active
- 2011-07-22 PT PT11752277T patent/PT2603469T/pt unknown
- 2011-07-22 BR BR112013001564A patent/BR112013001564B1/pt not_active IP Right Cessation
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JP2007329109A (ja) * | 2006-06-09 | 2007-12-20 | Nippon Sheet Glass Co Ltd | 透明電極基材及びそれを用いた光電変換装置 |
FR2927897A1 (fr) * | 2008-02-27 | 2009-08-28 | Saint Gobain | Vitrage antisolaire presentant un coefficient de transmission lumineuse ameliore. |
Also Published As
Publication number | Publication date |
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ES2701439T3 (es) | 2019-02-22 |
BR112013001564B1 (pt) | 2019-11-26 |
JP5824046B2 (ja) | 2015-11-25 |
JP2013535403A (ja) | 2013-09-12 |
CA2806251C (fr) | 2019-05-14 |
EP2603469A1 (fr) | 2013-06-19 |
EA201390212A1 (ru) | 2013-05-30 |
FR2963788B1 (fr) | 2016-01-22 |
EP2603469B1 (fr) | 2018-09-12 |
FR2963788A1 (fr) | 2012-02-17 |
CN103025678A (zh) | 2013-04-03 |
BR112013001564A2 (pt) | 2016-05-10 |
PL2603469T3 (pl) | 2019-03-29 |
US20130155496A1 (en) | 2013-06-20 |
US9354368B2 (en) | 2016-05-31 |
CA2806251A1 (fr) | 2012-02-16 |
WO2012020189A1 (fr) | 2012-02-16 |
PT2603469T (pt) | 2018-12-17 |
MX347558B (es) | 2017-05-03 |
MX2013001505A (es) | 2013-02-27 |
EA023332B1 (ru) | 2016-05-31 |
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