CN107107571A - 具有薄内板和薄外板的可加热的复合玻璃 - Google Patents
具有薄内板和薄外板的可加热的复合玻璃 Download PDFInfo
- Publication number
- CN107107571A CN107107571A CN201680003204.8A CN201680003204A CN107107571A CN 107107571 A CN107107571 A CN 107107571A CN 201680003204 A CN201680003204 A CN 201680003204A CN 107107571 A CN107107571 A CN 107107571A
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- China
- Prior art keywords
- glass
- inner panel
- outside plate
- vehicle
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000003475 lamination Methods 0.000 claims description 6
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- 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 claims description 2
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- B32—LAYERED PRODUCTS
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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
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- 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
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
- B32B17/1022—Metallic coatings
- B32B17/10229—Metallic layers sandwiched by dielectric layers
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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
- B32B17/10036—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
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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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- B32B17/10009—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
- B32B17/10119—Properties of the bulk of a glass sheet having a composition deviating from the basic composition of soda-lime glass, e.g. borosilicate
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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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- B32B17/10128—Treatment of at least one glass sheet
- B32B17/10137—Chemical strengthening
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- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
- B32B17/10201—Dielectric coatings
- B32B17/10211—Doped dielectric layer, electrically conductive, e.g. SnO2:F
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- 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
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
- B32B17/1022—Metallic coatings
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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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- B32B17/06—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
- B32B17/10761—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
用于分隔车辆内部空间与外部环境的车辆‑复合玻璃,其至少包括:‑由玻璃制成的内板(1),其包括内侧(III)和外侧(IV),‑由玻璃制成的外板(2),其包括内侧(II)和外侧(I),‑热塑性中间层(3),其将内板(1)的内侧(III)与外板(2)的内侧(II)接合,其中‑内板(1)的厚度为小于或等于1.4mm,‑外板(2)的厚度为小于或等于1.8 mm,并且‑在内板(1)的内侧(III)或外板(2)的内侧(II)上施加可电加热的涂层(4)。
Description
本发明涉及具有薄内板和薄外板的可加热的复合玻璃、其制造方法及其用途。
复合玻璃作为车辆领域中的装配玻璃是充分已知的。其通常由借助热塑性中间层相互接合的两个厚度为2 mm至3 mm的玻璃板构成。这类复合玻璃尤其用作挡风玻璃和顶玻璃,但也越来越多地用作侧玻璃和后玻璃。
目前,车辆工业力争降低车辆的重量,这伴随着降低的燃料消耗。降低装配玻璃的重量可以对此做出重要贡献,这尤其可通过降低的板厚度来实现。这类薄板的厚度尤其小于2 mm。尽管板厚度降低,但是,必须确保对玻璃板的稳定性和断裂强度的要求。
EP 2421704 B1公开了一种重量降低的复合玻璃板,其抗石击强度通过不对称的复合结构而有利提高。由此,该板满足了对车辆中的安全装配玻璃在机械刚性和强度以及抗石击强度方面的高要求(ECE-R 43:2004)。
在现代机动车中,经常使用可加热的挡风玻璃、侧玻璃或后玻璃,以保持车窗没有冰和冷凝水。出于美观原因以及安全性方面的考虑,存在于板中的加热元件对于观察者而言应是不可见或几乎不可见的。挡风玻璃的视野由于法律规定不允许有视线限制。挡风玻璃中的线形可加热元件虽然符合这些法律规定,但是这些线特别在昏暗和逆光的情况下造成干扰性反射。近年来,特别是在汽车领域中越来越多地使用具有红外反射导电涂层的板。这种涂层一方面具有好的导电性,这实现板的加热,并且此外具有红外反射性能,这避免不希望的内部空间被入射日光加热。这些层体系因此不仅在与安全性相关的方面,如不受限的视线,而且在生态角度上,如降低有害物质排放,以及改善车辆舒适度方面特别重要。这类功能涂层的各种实例是例如红外反射涂层或可加热涂层。热辐射反射涂层例如由EP 2141 135 A1、WO 2010115558 A1和WO 2011105991 A1已知,可加热涂层例如由WO 03/024155 A2、US 2007/0082219 A1和US 2007/0020465 A1已知。此外,对可加热涂层的领域进行了另外的改进,这降低了表面电阻并因此实现了板的更高的加热功率。WO 2013/104439和WO 2013/104438公开了包含具有至少两个导电层以及多个介电层的层堆叠体的导电涂层。这些涂层具有非常低的层电阻,例如0.7 Ω/□并且因此也非常适合用于加热大面积的板。通常,将这些涂层施加到复合板的玻璃板之一上,尤其通过阴极溅射(溅射)。
在严重的环境污染和变得日益严格的环保法规的过程中,希望的是能降低车辆的有害物质排放。这一方面可以间接地通过降低车辆组件的重量和另一方面也可以直接地通过降低燃料消耗来实现。尤其是车辆中固定集成的负载如空调或可加热的板为车辆的燃料消耗作出贡献。因此,特别希望的是降低可加热的车辆板的能耗。
WO 2015/158464展示了一种具有厚度为0.1 mm至0.4 mm的内板的复合玻璃。WO2015058885展示了一种复合玻璃,其中功能涂层布置在载体层上。
本发明的目的在于,提供在始终不变的加热的情况下具有降低的能耗的可加热的复合玻璃,其具有足够的稳定性和断裂强度,以能用于车辆领域中,以及提供其制造方法及其用途。
根据本发明,本发明的目的通过根据权利要求1的复合玻璃、根据权利要求12的其制造方法以及根据权利要求15的其用途得以实现。优选的实施方案由从属权利要求获悉。
本发明的复合玻璃优选是用于车辆的复合玻璃(车辆-复合玻璃)。该复合玻璃被设置用于在开口中,特别是在车辆的窗口中将内部空间相对于外部环境分隔。
本发明的复合玻璃(或复合板)包括至少一个内板、一个外板和一个将内板与外板接合的热塑性中间层,以及在内板的内侧或外板的内侧上的可电加热的涂层。内板的内侧是内板的朝向热塑性中间层的表面,而内板的外侧在安装位置中朝向车辆内部空间。外板的内侧同样朝向热塑性中间层,而外板的外侧朝向车辆环境。所述内板和外板由玻璃构成。内板的厚度为小于或等于1.4 mm且外板的厚度为小于或等于1.8 mm。
可电加热涂层与具有这种薄内板和薄外板的复合玻璃的组合是特别有利的,因为通过降低材料厚度减少要加热的物料,由此可在相同的加热功率下实现降低的能耗。此外,本发明的复合玻璃具有足够的稳定性和断裂强度,以能用于车辆领域中。
在本发明范围内,内板表示复合板的面向内部空间(车辆内部空间)的板。外板表示面向外部环境的板。
已表明,具有用于外板和内板的本发明厚度的复合玻璃具有惊人高的稳定性和断裂强度,特别是耐刮强度和抗石击强度。该内板还可以具有比迄今通常认为的明显更小的厚度。该复合玻璃的稳定性和断裂强度通过根据本发明的外板厚度选择以及外和内板在厚度方面的显著不对称来实现。令人惊奇地,本发明的复合玻璃符合车辆领域中高的安全要求。这些要求通常通过标准化的断裂、击打和刮擦测试检验,例如通过根据ECE R43的落球测试。
本发明的复合玻璃特别优选是机动车的挡风玻璃。
在一个优选的实施方案中,所述内板是弯曲的板,即在层压成复合玻璃前经受了热弯曲工艺的板。虽然该内板原则上也可以是未预弯曲的板,由于其小的厚度,其在层压时与外板的形状相匹配。但是有利的是,特别是在空间的多个方向上的所谓的三维弯曲时,使用预弯曲的内板,因为所希望的形状可用小的光学失真来实现。因为该弯曲工艺在玻璃结构中留下特征性标记,本领域技术人员可以通过目视检测将预弯曲和未预弯曲的彼此区分开。
根据本发明,较厚的外板是预弯曲的。外板和内板优选完全一致地预弯曲,即它们具有相同的预弯曲。
所述内板的厚度可以是,例如,0.2 mm、0.3 mm、0.4 mm、0.5 mm、0.6 mm、0.7 mm、0.8 mm、0.9 mm、1.0 mm、1.1 mm、1.2 mm、1.3 mm或1.4 mm。
所述外板的厚度可以是,例如,0.7 mm、0.8 mm、0.9 mm、1.0 mm、1.1 mm、1.2 mm、1.3 mm、1.4 mm、1.5 mm、1.6 mm、1.7 mm或1.8 mm。
所述内板的厚度优选为0.2 mm至1.4 mm,特别优选0.5 mm至1.2 mm,特别是0.6mm至1.0 mm。所述外板的厚度优选为0.7 mm至1.4 mm、0.7 mm至1.8 mm,特别优选1.2 mm至1.7 mm。这些范围在高稳定性和断裂强度的情况下在复合玻璃的较小重量方面是有利的。在本发明的一个有利的实施方案中,外板是未施加预应力的,特别是未施加化学预应力,且该外板的厚度为0.7 mm至1.4 mm。
在复合玻璃的稳定性、板的重量减少和所需加热功率的降低方面,下列厚度组合被证明是特别有利的:
a) 外板1.8 mm且内板1.4 mm
b) 外板1.6 mm且内板0.7 mm
c) 外板1.6 mm且内板0.3 mm
d) 外板0.7 mm且内板0.7 mm。
在本发明的一个特别有利的实施方案中,外板和内板具有不同厚度,其中外板比内板厚。外板和内板之间的厚度不对称性导致高稳定性。
就这点而言,厚度小于或等于0.4mm的内板和厚度大于或等于1.5 mm的外板的强不对称组合在板的稳定性和抗石击强度方面被证明是特别有利的。因此,相比于传统的板厚度,可以实现极大的重量减轻,并且尽管如此,可以获得对于车辆领域中,特别是作为挡风玻璃的应用而言具有足够高强度的复合玻璃。由于降低的板厚度,此外得到显著降低的为了加热被加热的板要耗费的能量。在这一范围内,1.6 mm厚的外板和0.3 mm厚的内板的组合就所述效果而言被强调为是特别有利的。
在另一个优选的实施方案中,外板和内板具有相同厚度。这种组合可以在尽可能大的重量减轻方面,例如在板厚度为各自小于1 mm的情况下是有利的。
在本发明的一个有利的实施方案中,外板是未施加预应力的板。该外板可能经受负荷,如石击。如果石头,特别是小的尖石打到玻璃板上,则其可能贯穿其表面。在施加预应力的板的情况下,石块可以因此穿入到板内部的拉应力区中,这导致板的破裂。未施加预应力的外板在内部具有较宽的压应力区和较小的拉应力,因此对于尖锐物体的打入较不敏感。未施加预应力的外板因此总体上在车辆乘客的安全性方面非常有利。
在一个优选的实施方案中,外板含有钙钠玻璃或硼硅酸盐玻璃,特别是钙钠玻璃。钙钠玻璃是价廉可得的,并被证明对于用于车辆领域中是有利的。
在本发明的一个有利的实施方案中,内板是施加化学预应力的玻璃板。通过预应力,内板可以具备特别的断裂稳定性和耐刮强度。对于非常薄的玻璃板,如其根据本发明被设置作为内板,施加化学预应力在此比施加热预应力更适合。因为施加热预应力归因于表面区和核心区之间的温度差,施加热预应力以玻璃板的最小厚度为前提条件。足够的应力通常可以用商业上常见的热预应力施加装置在约2.5 mm 以上的玻璃厚度下实现。在较小的玻璃厚度下,通常不能达到预应力的通常要求的值(参见例如ECE-规定43)。在施加化学预应力时,通过离子交换改变玻璃的表面区域中的化学组成,其中通过扩散到表面区上的离子交换是有限的。因此,施加化学预应力特别适合于薄板。对于施加化学预应力,也常用化学回火、化学硬化或化学增强这些名称。
内板的稳定性可以通过应力的合适值和局部分布来改善,这通过在施加化学预应力时引入离子而产生。
施加化学预应力的内板的表面压应力优选为大于100 MPa,优选大于250 Mpa,特别优选大于350 Mpa。
板的压应力深度特别是其厚度的至少十分之一,优选其厚度的至少六分之一,例如内板的厚度的约五分之一。这一方面在板的断裂强度方面,另一方面在较不费时的施加预应力过程方面是有利的。在本发明范围内,压应力深度是指从板的表面测量的直至该板承受大于0 Mpa的值的压应力处的深度。如果内板的厚度例如为0.3 mm,则该内板的压应力深度优选为大于30 µm,特别优选大于50 µm,非常特别优选100 µm至150 µm。
所述内板原则上可以具有技术人员已知的每种化学组成。该内板可以含有例如钙钠玻璃或硼硅酸盐玻璃或由这些玻璃构成。优选地,该内板应适合于被施加化学预应力,并特别是具有对此合适的碱金属元素的含量,优选钠。该内板可以含有例如40重量%至90重量%的氧化硅(SiO2)、0.5重量%至10重量%的氧化铝(Al2O3)、1重量%至20重量%的氧化钠(Na2O)、0.1重量%至15重量%的氧化钾(K2O)、0重量%至10重量%的氧化镁(MgO)、0重量%至10重量%的氧化钙(CaO)和0重量%至15重量%的氧化硼(B2O3)。该内板可以还含有其它成分和杂质。
但是已经令人惊奇地表明,内板的特定化学组成特别适合于经受施加化学预应力。这表现为高速扩散过程和大的预应力深度(压应力深度),高速扩散过程产生有利的用于施加预应力过程的小的耗时,大的预应力深度产生稳定和抗断裂的玻璃。这些组成在本发明范围内是优选的。
在一个优选的实施方案中,该内板含有铝硅酸盐玻璃。该内板优选含有50重量%至85重量%的氧化硅(SiO2)、3重量%至10重量%的氧化铝(Al2O3)、8重量%至18重量%的氧化钠(Na2O)、5重量%至15重量%的氧化钾(K2O)、4重量%至14重量%的氧化镁(MgO)、0重量%至10重量%的氧化钙(CaO)和0重量%至15重量%的氧化硼(B2O3)。该内板还可以含有其它成分和杂质。该内板特别优选至少含有55重量%至72重量%(非常特别优选57重量%至65重量%)的氧化硅(SiO2)、5重量%至10重量%(非常特别优选7重量%至9重量%)的氧化铝(Al2O3)、10重量%至15重量%(非常特别优选12重量%至14重量%)的氧化钠(Na2O)、7重量%至12重量%(非常特别优选8.5重量%至10.5重量%)的氧化钾(K2O)和6重量%至11重量%(非常特别优选7.5重量%至9.5重量%)的氧化镁(MgO)。
这些优选的玻璃组成除了施加化学预应力的可能性之外还具有其它令人惊奇的优点。这类板适用于与由传统的钙钠玻璃(也称为普通玻璃)制成的板一起完全一致地弯曲。对此负责的是类似的热性能,由此这两种玻璃类型在相同的温度范围中可弯曲,即大约450℃至700℃。如本领域技术人员足够已知的那样,完全一致弯曲的板由于其最佳相互匹配的形状特别地适合于接合成复合玻璃。具有优选的化学组成的内板因此特别适合于用于具有另一组成的,特别是由钙钠玻璃制成的外板的复合玻璃中。
或者,所述内板也可以是未施加预应力的板。特别是在非常薄的玻璃板的情况下,通过施加化学预应力可达到的应力值和因此稳定的作用减少越来越多。如果内板是未施加预应力的,则其在一个优选的实施方案中含有硼硅酸盐玻璃。已表明,由此可以实现特别突出的稳定性和断裂强度。
所述热塑性中间层含有至少一层热塑性薄膜,并且在一个有利的实施方案中通过一层热塑性薄膜形成。这在复合玻璃的简单结构和小的总厚度方面是特别有利的。该热塑性中间层或热塑性薄膜优选至少含有聚乙烯醇缩丁醛(PVB)、乙烯-乙酸乙烯酯(EVA)、聚氨酯(PU)或它们的混合物或共聚物或衍生物,其被证明对于复合玻璃有利。
所述热塑性中间层的厚度优选为0.2 mm至1.0 mm。例如可以使用0.76 mm标准厚度的热塑性薄膜。
该外板、内板和热塑性中间层可以是无色透明的,但也可以是有色或着色的。透过该复合玻璃的总透射率在一个优选的实施方案中为大于70%,特别是当该复合玻璃是挡风玻璃时。术语总透射率基于通过ECE-R 43,附件3,§ 9.1规定的用于检测机动车窗玻璃的透光性的方法。
所述复合玻璃优选在空间的一个或多个方向上弯曲,如对于机动车窗玻璃常见的那样,其中典型的曲率半径为约10 cm至约40 m。但该复合玻璃也可以是平坦的,例如当其被设置作为公交车、火车或拖拉机的板时。
本发明的复合玻璃具有在内板的内侧或外板的内侧上的可电加热的涂层。该可电加热的涂层优选设置在外板上。在一个优选的实施方案中较厚的此外优选由普通玻璃构成的外板可以在技术上比通常较薄的内板更简单和更价廉地涂覆,例如通过物理气相沉积(如溅射)。特别地,涂覆和施加化学预应力在技术上仅可以非常困难地组合。在施加预应力之前施加的涂层在施加化学预应力时干扰离子扩散过程。在施加化学预应力之后的涂覆由于通常高的温度改变板中的应力分布。功能涂层优选设置在外板的朝向热塑性中间层的内侧上,在此处其被保护免受腐蚀和损伤。
该可电加热的涂层也可以沉积在内板的内侧上,特别是如果该内板是未施加化学预应力的。
该可电加热的涂层可以在内板或外板的整个内侧上延伸。但是,该可电加热的涂层或者也可以仅在所述表面的一部分上延伸。该可电加热的涂层优选在透明基底的表面的至少50%,特别优选至少70%,非常特别优选至少90%上延伸。
所述可电加热的涂层的合适的材料组成例如可从WO 2013/104439和WO 2013/104438获知。
优选地,所述可电加热的涂层包含至少两个功能层,它们覆盖整面(flächendeckend)地叠置布置。每个功能层在此至少包含
- 导电涂层(2),其具有至少两个叠置布置的功能层(3),并且每个功能层(3)至少包含
○ 抗反射层(4),
○ 在抗反射层(4)上的第一匹配层(6),和
○ 在第一匹配层(6)上的导电层(7),和
- 至少一个设置在两个导电层(7)之间的抗反射层(4),其至少包含
○ 折射指数小于2.1的介电材料层(9),和
折射指数大于或等于2.1的高光学折射材料层(10)。
这些层以给出的次序以与板(其上施加有所述涂层)增大的距离设置。在最上面的功能层的上方设置覆盖层。
通过所述可电加热的涂层的相应安排,实现有利降低的表面电阻和因此随之而来的对于红外区域的改进的反射性能和改进的比加热功率。具有可电加热的涂层的根据本发明的透明板的光学性能在此符合车辆制造中对装配玻璃的法律要求。
优选地,该可电加热的涂层的表面电阻为0.4Ω/□至0.9Ω/□,例如0.9 Ω/□、0.7Ω/□或0.5Ω/□。
优选地,所有导电层的总层厚度为50 nm至60 nm。
优选地,在最上面的功能层的上方设置另一抗反射层。
优选地,最上面和最下面的抗反射层配置为折射指数大于或等于2.1的高光学折射材料层并且优选至少含有硅-金属-混合氮化物,特别优选硅-锆-混合氮化物,如掺铝的硅-锆-混合氮化物。
优选地,该高光学折射材料层的厚度为包含该高光学折射材料层的抗反射层厚度的10 %至99 %,优选25 %至75 %。
优选地,每个设置在两个导电层之间的抗反射层包含至少一个折射指数小于2.1的介电材料层和折射指数大于或等于2.1的高光学折射材料层。
优选地,设置在两个导电层之间的抗反射层的厚度为35 nm至70 nm,优选45 nm至60 nm。
优选地,该高光学折射材料层含有至少一种硅-金属-混合氮化物,特别优选硅-锆-混合氮化物,如掺铝的硅-锆-混合氮化物。
优选地,该介电材料层至少含有氮化硅。
优选地,在导电层上方的每个功能层包含第二匹配层。
所述导电涂层优选地包含至少一个平滑层,其设置在第一匹配层之一的下方,并且其中优选每个功能层包含一个在第一匹配层下方的平滑层。
优选地,所述平滑层含有至少一种非结晶氧化物,优选非结晶混合氧化物,特别优选锡-锌-混合氧化物,如掺锑的锡-锌-混合氧化物并优选具有3 nm至20 nm,特别优选4 nm至12 nm的层厚度。
优选地,所述导电层至少含有银或含银合金,并优选具有8 nm至25 nm的层厚度。
优选地,所述第一匹配层和/或第二匹配层含有氧化锌ZnO1-δ,其中0 < δ < 0.01,例如掺铝的氧化锌,并优选具有3 nm至20 nm,特别优选4 nm至12 nm的厚度。
优选地,至少一个功能层,特别优选每个功能层含有至少一个阻隔层,其设置在导电层的直接上方和/或直接下方并优选至少含有铌、钛、镍、铬或它们的合金,特别优选镍-铬-合金,并且其优选具有0.1 nm至2 nm的层厚度。
在本发明的一个有利的实施方案中,可电加热的涂层通过集流体与电压源连接并且施加到导电涂层上的电压优选具有12 V至15 V的值。该集流体,所谓的母线用于电功率的传输。合适的集流体的实例由DE 103 33 618 B3和EP 0 025 755 B1已知。
所述集流体有利地通过印刷导电膏来制造。如果该板在施加导电涂层之后弯曲,则优选在将该板弯曲之前和/或在弯曲过程中烧制导电膏。该导电膏优选含有银颗粒和玻璃料。烧制的导电膏的层厚度优选为5 µm至20 µm。
在一个替代实施方案中,将薄且窄的金属箔条或金属线用作集流体,其优选含有铜和/或铝,特别使用厚度优选为10 µm至200 µm,例如约50 µm的铜箔条。该铜箔条的宽度优选为1 mm至10 mm。可电加热的涂层和集流体之间的电接触可以例如通过焊接或用导电胶粘剂胶粘来制造。此外,该金属箔条或金属线可以在合并复合层时铺设到可电加热的涂层上。在随后的高压釜过程中,通过热和压力的作用实现集流体和涂层之间的可靠电接触。
作为用于接触在复合玻璃板内部的集流体的引线,使用车辆领域中常见的薄膜导体。薄膜导体的实例描述在DE 42 35 063 A1、DE 20 2004 019 286 U1和DE 93 13 394 U1中。
柔性的薄膜导体,有时也称为扁平导体或扁平带导体,优选由厚度为0.03 mm至0.1 mm且宽度为2 mm至16 mm的镀锡的铜带构成。铜被证明对于这种导体带(Leiterbahn)有利,因为其具有好的导电性和制成薄膜的好的可加工性。同时,材料成本低。还可以使用可加工成薄膜的其它导电材料。对此的实例是铝、金、银或锡和它们的合金。
所述复合玻璃还可以通过使热塑性中间层具有功能嵌入物,例如具有红外吸收、紫外吸收、赋色或声学性能的嵌入物而具备附加功能。这些嵌入物例如是有机或无机离子、化合物、聚集体、分子、晶体、颜料或染料。
本发明进一步通过制造本发明的复合玻璃的方法得以实现,其中
(a) 将内板、热塑性中间层和外板以这一次序平面地叠置布置,并且
(b) 将内板和外板通过层压相互接合。
如果该复合玻璃应是弯曲的,则至少使外板在层压之前经受弯曲过程。
在一个优选的实施方案中,内板同样经受弯曲过程。这特别是在空间的多个方向上强烈弯曲(所谓的三维弯曲)时是有利的。
替代地,没有预弯曲内板。这特别是在具有非常小厚度的内板时是有利的,因为其具有薄膜性质的柔性并因此可以与预弯曲的外板匹配而不必本身被预弯曲。
外板和内板可以单独地弯曲。优选地,外板和内板一起(即同时并通过同一工具)完全一致地弯曲,因为由此板的形状对于稍后进行的层压而言最佳地相互匹配。用于玻璃弯曲过程的典型的温度为例如500℃至700℃。
在一个优选的实施方案中,内板经受施加化学预应力。任选地,内板在弯曲之后缓慢冷却。过快的冷却在板中产生热应力,其在稍后的化学回火中可能导致形状改变。冷却速度优选为0.05℃/秒至0.5℃/秒,特别优选0.1℃/秒至0.3℃/秒,直至冷却到400℃的温度。通过这种缓慢冷却,可以避免玻璃中的热应力,其特别导致光学缺陷并且导致对后续施加化学预应力的负面影响。此后可以进一步冷却,甚至以更高的冷却速度,因为低于400℃产生热应力的风险小。
所述施加化学预应力优选在300℃至600℃,特别优选400℃至500℃的温度下进行。在此,用盐熔体处理内板,例如浸入盐熔体中。在该处理过程中,特别是玻璃的钠离子被更大的离子,特别是更大的碱金属离子交换,由此生成所希望的表面压应力。该盐熔体优选是钾盐,特别优选硝酸钾(KNO3)或硫酸钾(KSO4),非常特别优选硝酸钾(KNO3)的熔体。
所述离子交换通过碱金属离子的扩散来确定。表面压应力和压应力深度的所需值因此尤其可以通过施加预应力过程的温度和持续时间来调节。常见的持续时间为2小时至48 小时。
在用盐熔体处理之后,将板冷却到室温。随后清洁该板,优选用硫酸(H2SO4)。
所述热塑性中间层优选作为薄膜来提供。所述通过层压制造复合玻璃使用本领域技术人员本身已知的常见方法,例如高压釜法、真空袋法、真空环法、压延机法、真空层压机或它们的组合来进行。外板和内板的接合在此通常在热、真空和/或压力的作用下进行。
本发明进一步包括本发明的复合板在车辆,优选机动车,特别优选轿车中,特别是作为挡风玻璃、侧玻璃、后玻璃或顶玻璃的用途。
下面借助附图和实施例更详细阐述本发明。该附图是示意图而不是按比例的。该附图决不限制本发明。
其中:
图1a和1b显示了 根据本发明的复合玻璃的一个实施方案的俯视图和截面,并且
图2显示了本发明方法的一个实施方案的流程图。
图1a和1b显示了根据本发明的复合玻璃,其包括内板1和外板2。内板1具有内侧III和外侧IV。外板2具有内侧II和外侧I。板1和2的内侧II和III通过热塑性中间层3相互接合。在内板的内侧III上存在可电加热的涂层4。可电加热的涂层4包括三个导电银层与设置在它们之间的介电层并具有R = 0.9 Ω/□的层电阻。导电涂层4借助磁控管溅射沉积在内板1 上。中间层3由厚度为0.76 mm的单个PVB薄膜形成。在可电加热的涂层4上,两个集流体5导电接触,其中一个集流体 5基本上平行于顶边缘 A且一个集流体 5基本上平行于发动机边缘 B延伸。在这些集流体5之间施加14 V的电压,其相应于常见的机动车车载电压。借助所产生的经过可电加热的涂层4的电流,加热该复合玻璃。在将该装配玻璃装配在车辆车身中之后,与车身的A柱相邻延伸的复合板的边缘称为侧边缘 C。图1b显示了沿着切割线D-D‘的图1a装置的截面。在侧边缘 C之间,在复合玻璃的中心延伸有中线M,其与侧边缘C的距离在每个位置处相应于与对面的侧边缘C的距离并因此将该复合玻璃划分成两个相同大小的区域。该复合玻璃被设置为机动车的挡风玻璃。该复合玻璃,如对于机动车-挡风玻璃常见的那样,是三维弯曲的。这表示,该板在空间的多个方向上具有曲度,特别是在水平和垂直方向上。但是为了简化,该图中的复合玻璃示意性地示为平面的。
对图1a和1b的根据本发明的复合玻璃和具有其它板厚度的另外的根据本发明的复合玻璃(实施例1、2和3,见表1)言和对具有传统厚度的复合玻璃(对比例,见表1),比较为了加热板所需的直至达到最高温度的加热时间。所有复合玻璃的结构和几何形状在此是相同的并符合图1a和1b中的描述,仅仅如表1中所示那样改变外板和内板的厚度。在23℃的环境温度下进行测量。对于最高温度的测量,首先确定板的具有最高温度的点。这可以以简单的方式借助热像仪进行。板的具有最高温度的位置对于所有实施例和对比例是相同的,因为板设计是相同的。接着测量在该点处在多少时间后达到约70℃的最高温度。
表1
表1显示了,通过根据本发明地降低板厚度,可以减少直至 70℃温度的所需加热时间。实施例1和对比例的比较已经得到9.7 %的降低。随加热时间的减少,板是的能耗也随之相应降低。在根据实施例2和3的进一步减小板厚度的情况下,可以看出加热时间的和因此能耗的进一步降低。这对于本领域技术人员而言是令人惊奇和未预料到的。此外,根据实施例1、2和3的复合玻璃具有高的稳定性和断裂强度并因此特别好地适用于车辆领域中的应用。此外,通过降低板厚度可以观察到复合玻璃的重量降低,这同样导致减少的燃料消耗。
在第二实验中,对实施例1(实施例1,见表2)和对比例(对比例,见表2)研究4分钟加热时间后沿着图1b的切割线 D-D‘的温度分布。切割线 D-D‘在此在所谓的B视野的中心处切割中线 M,由此位于D-D‘和顶边缘 A之间的B视野部分与位于D‘和发动机边缘之间的B视野部分刚好一样大。B视野的定义及其在预先确定的板上的确定对于本领域技术人员而言是充分已知的。为此可参阅欧洲联合国经济委员会的规定43(ECE R 43),包括直至2011年12月12日的所有修订(规定43,包括修改1-7的第2版),其A自己(die das A-Sich)。
表2
沿着DD‘的最低温度Tmin | 沿着DD‘的最高温度Tmax | 沿着DD‘的温度偏差ΔT | 沿着DD‘的平均温度Tav | |
对比例 | 29.2℃ | 29.6℃ | 0.4℃ | 29.4℃ |
实施例1 | 30.7℃ | 31.2℃ | 0.5℃ | 30.9℃ |
表2证实了表1中在这方面所示出的结果,即在4分钟的相同加热时间下,相比于对比例1,根据本发明的实施例1的复合玻璃板的最低温度、最高温度和平均温度可以提高。在此通过沿着 DD‘的温度偏差得出的温度均匀度在此保持大致恒定。
图2显示了制造根据本发明的复合玻璃的本发明方法的一个实施例的流程图,其包括下列步骤:
I 将内板1和外板2共同弯曲
II 对内板1 在460℃下在KNO3的熔体中施加化学预应力
III 用H2SO4洗涤内板1
IV 将内板1、热塑性中间层3 和外板2叠置布置
V 使内板1与外板2通过层压接合。
步骤II和III在此是任选的。但是如果进行步骤II,就也应进行步骤III。如果不希望施加步骤II的化学预应力,可以在步骤I后继续进行步骤IV。
内板1和外板2以平面的起始状态来提供。内板1和外板2一起经受弯曲过程并完全一致地弯曲成其最终的三维形状。
任选地,内板1在弯曲之后经受化学预应力。此外,内板1在弯曲之后缓慢冷却,以避免热应力。合适的冷却速度为例如0.1℃/秒。随后,将内板1在460℃的温度下用硝酸钾熔体处理数小时,例如4小时的时间段,并在此期间施加化学预应力。该处理造成钠离子被更大的钾离子通过扩散驱使交换通过玻璃表面。由此产生表面压应力。随后,将内板1冷却,然后用硫酸洗涤,以去除硝酸钾的残留物。
随后,将热塑性中间层3设置在内板1和外板2之间。将由内板1、中间层3和外板2制成的堆叠体以传统方式通过层压,例如通过真空袋方法接合。
附图标记列表:
(1) 内板
(2) 外板
(3) 热塑性中间层
(4) 可电加热的涂层
(5) 集流体
(A) 顶边缘
(B) 发动机边缘
(C) 侧边缘
(M) 中线
D-D‘ 切割线
(I) 外板的外侧
(II) 外板的内侧
(III) 内板的内侧
(IV) 内板的外侧。
Claims (15)
1.用于分隔车辆内部空间与外部环境的车辆-复合玻璃,其至少包括:
- 由玻璃制成的内板(1),其包括内侧(III)和外侧(IV),
- 由玻璃制成的外板(2),其包括内侧(II)和外侧(I),
- 热塑性中间层(3),其使内板(1)的内侧(III)与外板(2)的内侧(II)接合,其中
- 内板(1)的厚度为0.5 mm至1.2 mm,
- 外板(2)的厚度为小于或等于1.8 mm,并且
- 在内板(1)的内侧(III)或外板(2)的内侧(II)上施加可电加热的涂层(4)。
2.根据权利要求1的车辆-复合玻璃,其是挡风玻璃。
3.根据权利要求1或2的车辆-复合玻璃,其中内板(1)的厚度为0.6 mm至1.0 mm。
4.根据权利要求1至3任一项的车辆-复合玻璃,其中外板(2)的厚度为0.7 mm至1.8mm,优选1.2 mm至1.7 mm。
5.根据权利要求1至4任一项的车辆-复合玻璃,其中热塑性中间层(3)通过单个的热塑性薄膜形成,其优选至少含有聚乙烯醇缩丁醛(PVB)、乙烯-乙酸乙烯酯(EVA)、聚氨酯(PU)或它们的混合物或共聚物或衍生物。
6.根据权利要求1至5任一项的车辆-复合玻璃,其中热塑性中间层(3)的厚度优选为0.2 mm至1 mm。
7.根据权利要求1至6任一项的车辆-复合玻璃,其中可电加热的涂层(2)包含至少一个导电层,该导电层至少含有银或导电氧化物且厚度优选为10 nm至200 nm。
8.根据权利要求1至7的车辆-复合玻璃,其中内板(1)是施加化学预应力的板并且可电加热的涂层(2)施加在外板(2)的内侧(II)上。
9.根据权利要求8的车辆-复合玻璃,其中内板(1)含有铝硅酸盐玻璃并优选含有55重量%至72重量%的氧化硅(SiO2)、5重量%至10重量%的氧化铝(Al2O3)、10重量%至15重量%的氧化钠(Na2O)、7重量%至12重量%的氧化钾(K2O)和6重量%至11重量%的氧化镁(MgO)。
10.根据权利要求1至7的车辆-复合玻璃,其中内板(1)是未施加预应力的板并含有硼硅酸盐玻璃。
11.根据权利要求1至10任一项的车辆-复合玻璃,其中外板(2)是未施加预应力的板并优选含有钙钠玻璃。
12.制造根据权利要求1至11任一项的车辆-复合玻璃的方法,其中
(a) 将内板(1)、热塑性中间层(3)和外板(2)以此次序平面地叠置布置,并且
(b) 将内板(1)和外板(2)通过层压相互接合。
13.根据权利要求12的方法,其中使内板(1)和外板(2)一起弯曲。
14.根据权利要求12或13的方法,其中内板(1)在弯曲状态下被施加化学预应力。
15.根据权利要求1至11任一项的车辆-复合玻璃在机动车,优选轿车,特别是作为挡风玻璃、侧玻璃、后玻璃或顶玻璃的用途。
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