CN113728149A - 制备具有高gsm波透过率的绝缘玻璃制品的方法 - Google Patents

制备具有高gsm波透过率的绝缘玻璃制品的方法 Download PDF

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CN113728149A
CN113728149A CN202180001940.0A CN202180001940A CN113728149A CN 113728149 A CN113728149 A CN 113728149A CN 202180001940 A CN202180001940 A CN 202180001940A CN 113728149 A CN113728149 A CN 113728149A
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glass article
glass
thickness
insulating
air gap
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T·翁加雷洛
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/663—Elements for spacing panes
    • E06B3/66309—Section members positioned at the edges of the glazing unit
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
    • E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
    • E06B3/6612—Evacuated glazing units
    • 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
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    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B32B17/10045—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets with at least one intermediate layer consisting of a glass sheet
    • B32B17/10055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets with at least one intermediate layer consisting of a glass sheet with at least one intermediate air space
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    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
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    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
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    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B7/04—Interconnection of layers
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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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
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Abstract

本发明的目的是：‑具有高GSM波传输率的绝缘玻璃制品，该玻璃制品由彼此平行且各自厚度最大等于10mm的第一玻璃制品和第二玻璃制品组成，所述第一玻璃制品和第二玻璃制品通过气隙彼此隔开，其特征在于：气隙的厚度最大为10mm；‑绝缘玻璃制品的应用，例如用于陆地、水上或空中的交通工具的玻璃制品，或作为用于建筑物的玻璃制品。

Description

制备具有高GSM波透过率的绝缘玻璃制品的方法
本发明涉及具有隔热功能的双层玻璃制品的领域。
目前，标准绝缘玻璃制品由双层玻璃制品单元（DGU）组成，该单元通常由两块可变厚度的玻璃板组成，两块玻璃板彼此平行安装，并带有通常为16 mm的间隙，并充满空气或气体如氩气。该配置使得可以最小化内部与外部之间的热传递，从而减少了热损失并且改善了热舒适性和节能。
在例如火车的运输工具中，双层玻璃制品用作侧窗，在双层玻璃制品中通常装有一个或多个涂层以改善热能性能，以控制太阳光并降低辐射率。日光控制是对太阳辐射的反射和过滤，以减少封闭空间内部感应的热量，低辐射率是对壳体的热辐射的反射，以保留其热量。然而，使用这种对日光控制和低发射率具有高选择性的涂层的缺点之一是在GHz频带内GSM频率的衰减。这是由于在涂层中存在多个金属层，这些金属层凭借其导电性表现为GHz范围内电磁波的完美反射物质。
在用于运输车辆的玻璃制品领域中，特别地，需要通过设置有一个或多个导电涂层的双层玻璃制品来提高GSM频率的传输率水平。为此，可以想到对该（这些）涂层进行部分激光烧蚀。
根据不同的方法，本发明已经实现了该目的，因此本发明的主题是一种具有高GSM波传输率的绝缘玻璃制品，该绝缘玻璃制品由彼此平行的第一玻璃制品和第二玻璃制品组成。且其厚度最大等于10mm，由气隙彼此隔开，其特征在于，所述气隙的厚度最大等于10mm。与标准气隙为16毫米厚的双层玻璃制品相比，通过减小构成双层玻璃制品的两个玻璃制品之间的气隙厚度，可以改变系统的共振频率，从而提高GSM波的传输率，特别是在3.4和3.8GHz的关键频带内。
气隙可以由空气或气体（例如氩气，氙气，氪气）或真空组成。关于通过本发明的方法制造的绝缘玻璃制品的隔热性能，应当强调的是，气隙的厚度从16mm减小到10mm引起了绝缘玻璃制品的Ug系数的非常有限的变化，仅0.2 W/m2K。
优选地，第一和第二玻璃制品包括聚合物材料和矿物玻璃的片材，其Fe含量最大等于0.1重量％。第一玻璃和第二玻璃制品彼此独立地是整体式的，也就是说它们由单个刚性透明片材组成，或者更具体地讲，它们是层压件，因此它们由两个刚性透明片材组成，所述两个刚性透明片材通过粘合中间层彼此粘合。刚性透明片材由聚合物材料制成，例如聚甲基丙烯酸甲酯（PMMA），聚碳酸酯（PC），聚氨酯（PU），或由矿物质玻璃制成，例如钠钙玻璃，铝硅酸盐，硼硅酸盐等。粘合中间层例如由聚乙烯醇缩丁醛（PVB），热塑性聚氨酯（TPU）或乙烯-乙酸乙烯基酯（EVA）制成。通过使用Fe含量最多限制为0.1重量％的矿物玻璃来形成绝缘玻璃制品的第一和/或第二玻璃制品，与更高含量相比，这保证了更好的在3.4至3.8 GHz之间以及最大达28 GHz的频率下的GSM传输率。因此，例如硼硅酸盐或铝硅酸盐玻璃是非常合适的。矿物玻璃特别优选具有0.01至0.099重量％的Fe含量。
在本发明的绝缘玻璃制品的有利实施方式中，第一玻璃制品和第二玻璃制品中的一个或两者具有最大等于5mm的厚度。双层玻璃制品的这种相对厚度足以在许多应用中保证所需的机械强度，同时限制了玻璃制品的重量。进一步有利于GSM波的传输率。
优选地，气隙在真空下并且厚度最大等于0.3mm。像这样薄的真空下的气隙可提供与大气压下厚很多的气隙相当的绝热性能，并且其GSM波的传输率接近于厚度等于双层玻璃制品的两个玻璃制品总厚度的实心（整体式）玻璃制品的GSM波的传输率。
在根据本发明的绝缘玻璃制品的优选实施方式中，第一玻璃制品和第二玻璃制品中的至少一个是层压玻璃制品，该层压玻璃由两个通过粘合中间层彼此粘合的矿物玻璃片材组成。对于具有合理的每单位面积的厚度和重量，层压玻璃制品可抵抗渗透/破裂和进入。
因此，粘合中间层优选选自聚乙烯醇缩丁醛（PVB），热塑性聚氨酯（TPU），乙烯-乙酸乙烯基酯（EVA）。
优选地，所述绝缘玻璃制品包括至少一个薄的日光控制层和/或薄的低辐射层，所述薄的日光控制层和/或薄的低辐射层已经经历了部分激光烧蚀以允许GSM波通过。术语“薄层”是指单层，或更普遍地是指（总）厚度最多为约几十纳米的几层的叠层。叠层通常包括交替的导电层，包括金属层和介电层。如上所述，这些薄层的功能是反射红外范围内的不同热辐射（太阳辐射，来自封闭空间的内部热量）。由于这些薄层不传输诸如GSM的电磁波，因此可以设想，根据本发明方法的这种变型，通过激光烧蚀从其中去除优选规则地分布在薄层整个表面上的部分，这允许GSM波通过。
本发明的另一个目的在于应用上述的绝缘玻璃制品，作为用于陆地、水上或空中的交通工具的玻璃制品，或作为用于建筑物的玻璃制品，特别是作为火车侧部玻璃制品。
通过以下示例性实施例说明本发明。
在第一个测试系列中，测量了GSM波通过双层玻璃制品的传输率，每个双层玻璃制品由被气隙分隔的两个层压玻璃制品组成。
每个双层玻璃制品的组成在下表中给出。第一层压玻璃制品由两个玻璃片材（分别表示为I（玻璃I）和II（玻璃II））通过PVB彼此粘合，第二层压玻璃制品由两个玻璃片材组成，分别表示为III（玻璃III）和IV（玻璃IV），也通过PVB彼此粘合。除非另有说明，玻璃是钠钙玻璃或硼硅酸盐浮法玻璃。每个双层玻璃制品的所有构成件的厚度以毫米表示。
所有双层玻璃制品的总厚度为26.25毫米。
[表1]
Figure 927266DEST_PATH_IMAGE001
。
下表列出了六个双层玻璃制品的各自频率范围值或离散频率（以GHz为单位），给出了GSM波的最小传输率（以dB为单位）。
[表2]
Figure 197842DEST_PATH_IMAGE002
。
与标准双层玻璃制品（气隙为14毫米）相比，双层玻璃制品“厚PVB”和“厚玻璃”（其气隙约为10 mm）在3.4-3.8 GHz的临界频率范围内具有更好的GSM传输率。通过用硼硅酸盐浮法玻璃（厚PVB硼硅酸盐和厚玻璃硼硅酸盐）代替钠钙玻璃，在这方面的情况甚至更好。
硼硅酸盐玻璃还可以在高达28 GHz的频率上实现良好的GSM传输率，这对于将来的5G应用至关重要。
通过减小气隙的厚度，即使仅使用钠钙玻璃也可以显著提高GSM的传输率。从16减小到10 mm的气隙，Ug系数（双层玻璃制品的隔热性能）的损失仅为0.2 W/m2K。
在第二系列测试中，通过双层玻璃制品测量GSM波的传输率，各双层玻璃制品由两个玻璃制品组成，一方面由真空气隙隔开，另一方面在大气压力下并通过整体式矿物玻璃制品隔开。
各玻璃制品的组成在下表中给出。对于双层玻璃制品，第一玻璃制品标记为I（玻璃I），和第二玻璃制品标记为II（玻璃II）。该玻璃是钠钙玻璃（法国圣戈班玻璃公司Saint-Gobain Glass France出售的PLC，Planiclear®）或硼硅酸盐浮法玻璃。每个双层玻璃制品的所有成分的厚度以毫米表示。对于整体式玻璃制品，按照惯例，气隙的厚度和第二玻璃制品II的厚度等于0。
[表3]
玻璃制品No. I 气隙 II 玻璃
1 6.1 0 0 硼硅酸盐
2 6.1 0 0 PLC
3 3 0.1 3 硼硅酸盐
4 3 0.1 3 PLC
5 2.1/0.76/1.6 0.1 2.1/0.76/1.6 硼硅酸盐
6 2.1/0.76/1.6 0.1 2.1/0.76/1.6 PLC
双层玻璃制品5和6包括两个层压玻璃制品，其由一个2.1mm厚的玻璃片材组成，并通过一个0.76mm厚的PVB层粘结到一个1.6mm厚的玻璃片材上。
在所有这些玻璃制品中都测量了0.7至28 GHz之间的GSM波的最小传输率（以dB为单位）。
对于两个玻璃制品，GSM波的传输率是相同的，不同之处仅在于，一个玻璃制品的0.1毫米厚的气隙是在大气压力下，另一个玻璃制品的0.1毫米厚的气隙是在真空下。
通过基于铁含量较低的玻璃的玻璃制品（玻璃制品No.1、分别地3、分别地5）的GSM波的传输率比通过仅玻璃成分不同（较高的铁含量）的相应玻璃制品（玻璃制品2、分别地4、分别地6）的GSM波的传输率更好。
下表列出了通过上述玻璃制品1、3和5在2.6 GHz，3.8 GHz，6 GHz和28 GHz下GSM波的最小传输率（以dB为单位）。
[表4]
T<sub>min</sub>(dB) 玻璃制品No.1 玻璃制品No.3 玻璃制品No.5
2.6 GHz -1.1 -1.1 -1.6
3.8 GHz -1.8 -1.8 -2.1
6 GHz -2.3 -2.3 -1.1
28 GHz -2.3 -2.0 -3.2
玻璃制品1和3的比较显示，在真空下具有薄气隙的双层玻璃制品（玻璃制品3）传输的GSM波实际上与该双层玻璃制品相同的玻璃且厚度相同的整体玻璃制品（玻璃制品1 ）相同。
玻璃制品No. 5表明，用铁含量相对较低的玻璃可以设计出具有两个层压玻璃制品的双层玻璃制品，在本发明的背景下，其高频传输率大于-5 dB。
使用0.1mm的真空气隙，可以获得具有与标准双层玻璃制品（两个玻璃片材为6mm和4mm，由16毫米的气隙分隔）相同的隔热性（Ug系数）的双层玻璃制品。此外，该玻璃制品的GSM波衰减低。

Claims (10)

1.具有高GSM波传输率的绝缘玻璃制品，其由彼此平行且各自厚度最大等于10mm的第一玻璃制品和第二玻璃制品组成，所述第一玻璃制品和第二玻璃制品通过气隙彼此隔开，其特征在于气隙的厚度最大等于10mm。
2.根据权利要求1所述的绝缘玻璃制品，其特征在于，所述第一玻璃制品和第二玻璃制品包括聚合物材料的片材和矿物玻璃的片材，其Fe含量至多等于0.1重量％。
3.根据权利要求2所述的绝缘玻璃制品，其特征在于，所述矿物玻璃具有0.01重量％至0.099重量％的Fe含量。
4.根据前述权利要求中任一项所述的绝缘玻璃制品，其特征在于，所述第一玻璃制品和第二玻璃制品中之一具有最大等于5mm的厚度。
5.根据前述权利要求中任一项所述的绝缘玻璃制品，其特征在于，所述第一玻璃制品和第二玻璃制品的厚度最大等于5mm。
6.根据前述权利要求中任一项所述的绝缘玻璃制品，其特征在于，所述气隙在真空下并且具有最大等于0.3mm的厚度。
7.根据前述权利要求中任一项所述的绝缘玻璃制品，其特征在于，所述第一玻璃制品和第二玻璃制品中的至少一个是层压玻璃制品，所述层压玻璃制品由两个通过粘合中间层彼此粘合的矿物玻璃的片材组成。
8.根据权利要求7所述的绝缘玻璃制品，其特征在于，所述粘合中间层选自聚乙烯醇缩丁醛（PVB），热塑性聚氨酯（TPU），乙烯-乙酸乙烯基酯（EVA）。
9.根据前述权利要求中任一项所述的绝缘玻璃制品，其特征在于，所述绝缘窗玻璃制品包括至少一个薄的阳光控制层和/或薄的低辐射层，所述薄的阳光控制层和/或薄的低辐射层已经历部分激光烧蚀以允许GSM波通过。
10.根据前述权利要求中任一项所述的绝缘玻璃制品的用途，其作为用于陆地、水上或空中的交通工具的玻璃制品，或作为用于建筑物的玻璃制品。
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