CN104755265A - 用于挡风玻璃的薄的叠层玻璃 - Google Patents
用于挡风玻璃的薄的叠层玻璃 Download PDFInfo
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Abstract
本发明描述了叠层玻璃制品,其包含至少一个外玻璃板、一个内玻璃板和位于两个玻璃板之间的聚合物***件,其中内板具有不大于1.5mm的厚度,外玻璃板为具有与内板不同的化学组成的玻璃板,温度Tp1和Tp2的差值小于80℃,温度Tp1定义为外玻璃板的退火温度上限和软化点之间的平均值,且温度Tp2定义为内玻璃板的退火温度上限和软化点之间的平均值。
Description
本发明涉及由至少两个薄的玻璃板组成的叠层玻璃制品(glazing)。本发明更特别地涉及用于机动车领域,尤其是用作挡风玻璃的叠层玻璃制品。
叠层玻璃制品通常用于机动车、航空或建筑领域,因为它们具有作为“安全”玻璃制品的优点。它们由通过由塑料(通常为聚乙烯醇缩丁醛(PVB))制造的***层连接在一起的至少两个玻璃板组成。通常,用于挡风玻璃的玻璃制品为非对称的并且由不同厚度的两个硅-钠-钙玻璃板组成,外板一般比内板厚。为了改善这种类型的玻璃制品的机械强度,通过使它们回火来增强构件玻璃板,并由此产生处于压缩的表面区域,和处于拉伸的中心区域是已知的实践。专利US 3 558 415描述了弯曲的叠层玻璃制品,其中已使外玻璃板和内玻璃板化学回火,从而具有处于压缩的表面区域。专利GB 1 339 980描述了挡风玻璃制品,其中仅使外玻璃板化学回火。
在机动车领域所遇到的常规问题涉及玻璃制品的重量。目前制造的挡风玻璃通常具有厚度为2.1至2.6mm的外板和厚度为1.6至2.1mm的内板。目前在试图降低玻璃制品的重量,然而同时不在机械强度性能方面妥协。专利申请WO2012/051 038和WO 2012/177 426描述了其中玻璃板具有小于2mm的厚度,并且使至少一个玻璃板化学回火的叠层玻璃。挡风玻璃的构件玻璃板的厚度的降低使其重量得以降低,但是可能导致机械问题,特别是当其暴露于砂砾投射时,其易碎性增加。由上文引用的文献所提出的用于改善机械强度的方案包括使外玻璃板化学回火。化学回火或离子交换的过程由以下所组成:利用更大离子半径的离子(通常为另—种碱金属,例如钾的离子)对玻璃板的离子(通常为碱金属,例如钠的离子)进行表面替换,并在所述板的表面至一定的深度产生残余压应力(residual compression stress)。这是相对昂贵和耗时的过程,并因此与连续的工业生产方法不良地兼容。
弯曲玻璃板的步骤对于所期望的应用来说是重要的。弯曲能够赋予玻璃板曲率,并因此有助于构成叠层玻璃制品的各种板的组装。可以使用多种弯曲工艺。例如将提到使用框架或通过抽吸来进行的通过重力弯曲,通过在传输辊之间穿过来弯曲,通过相对固体形式挤压来弯曲。在框架上通过重力和/或部分通过挤压来同时弯曲玻璃板(如在专利申请EP 0448447,WO 2004/087 590,WO02/064 519或WO 2006/072 721所描述的)是用于同时弯曲两个意在形成弯曲叠层玻璃制品(例如运输车辆挡风玻璃)的玻璃板的技术。通过具有期望轮廓的框架将一个放置在另一个上的两个玻璃板沿着它们的边缘末端基本上水平地支撑,即所述轮廓对应于两个弯曲玻璃板的最终轮廓。使由此支撑的两个玻璃板通过弯曲的烘箱(通常为具有不同的温度区域的烘箱)。当两个玻璃板具有不同的化学组成时,在这种弯曲步骤过程中它们的行为可能不同,并且出现缺陷或残余应力的风险因此而增加。在专利申请GB 2 078 169中描述了一种当玻璃板的物理化学特性和厚度不同的时候所提出的方案,该方案包括在弯曲工艺的过程中相对于在组装阶段中这些相同的板所具有的次序来逆转玻璃板的次序。
出于制品的光学质量、成本、重量和技术简化的目的,提供其机械强度与所期望的应用相适应,并且其由可同时弯曲的玻璃板组成,而无需在弯曲步骤和组装步骤之间改变玻璃板的次序的薄的叠层玻璃是有用的。同时弯曲和直接组装,无需逆转所述板,都是更有趣的,因为玻璃制品的构件板的厚度低。
本发明落入此范围内,其主题为叠层玻璃制品,该玻璃制品包含至少一个外玻璃板、一个内玻璃板和位于所述两个玻璃板之间的聚合物***件,其中内板具有不大于1.5mm的厚度,并且外玻璃板为具有与内板不同的化学组成的玻璃板,
温度Tp1和Tp2之间的差值ΔTp小于80℃,优选小于70℃,且甚至更优选小于60℃;
温度Tp1定义为外玻璃板的退火温度上限和软化点之间的平均值,和温度Tp2定义为内玻璃板的退火温度上限和软化点之间的平均值,定义温度Tp的通式为
Tp=(T软化+T退火)/2
退火温度上限对应于玻璃的粘度为1013泊时的温度,和软化点对应于玻璃的粘度为107.6泊时的温度。
根据本发明,对应于外板的如上定义的温度的平均值的温度Tp1高于对应于内板的如上定义的温度的平均值的温度Tp2。
温度Tp1高于温度Tp2,因此温度Tp1和Tp2之间的差值ΔTp为正数。
因此差值ΔTp在0℃和80℃之间。
在本发明中,术语“外”用于涉及接受玻璃制品的装置外部的任何事物。因此将外玻璃板设置为面向驾驶舱外部。相反地,术语“内”用于涉及接受玻璃制品的装置内部的那些。叠层玻璃制品的内板对应于面向驾驶舱内部设置的板。
本发明人已经证明能够制造总厚度小于4.5mm,或甚至4mm,具有不同的化学组成,并可以将其同时弯曲,然后直接组装,而无需逆转玻璃板的次序的两个玻璃板的叠层玻璃制品。因此,不需要分别弯曲两个板中的每一个即可获得制品,尽管它们具有不同的化学组成。其保有用作机动车挡风玻璃的令人满意的机械强度。最终制品的重要结果特别地在于其减轻的重量,这导致机动车重量的减轻和消耗减少。结合外玻璃板和非常薄的内玻璃板在厚度和化学组成方面的非对称组装,有利地使得其能够获得坚强的、轻质的挡风玻璃。
取决于其组成,各个玻璃板的特征在于其退火温度上限(或者简单地为“退火温度”)及其软化点(还被称为“利特尔顿温度”)。
退火温度对应于这样的温度,在该温度下,玻璃的粘度足够高以使得应力的消失能够完全在给定时间内发生(约15分钟的应力松弛时间)。其有时被称为“应力松弛温度”。该温度对应于液体的粘度η为1013泊的时刻。该温度的测定通常根据标准NF B30-105来进行。
软化点定义为这样的温度,在该温度下,直径约0.7mm且长度为23.5cm的玻璃纱在其自重下以1mm/min变长(标准ISO 7884-6)。相应的粘度为107.6泊。
温度Tp以如下方式来定义:
Tp=(T软化+T退火)/2
取决于其组成,各个玻璃板的特征在于温度Tp。根据本发明的叠层玻璃制品必须由温度Tp尽可能接近的两个玻璃板组成,以满足同时弯曲的所期望的需求。对于在机动车领域,特别是作为挡风玻璃的应用来说,重要的是确保制造叠层玻璃制品的工艺,特别是弯曲或成型步骤,没有在玻璃制品中产生缺陷。
根据本发明的叠层玻璃制品具有这样的优点,其能够弯曲,而不会增加产生残余应力或光学缺陷的风险。玻璃制品的两个构件玻璃板具有不同的化学组成,但它们是这样的,能够使其一起弯曲,不会由于两个玻璃板的化学组成不同而使得该工艺复杂化,并且特别是在弯曲步骤和组装步骤之间不需要逆转玻璃板的次序。
外玻璃板具有不大于2.1mm和优选不大于1.6mm的厚度。因此,这种相对低厚度的外板还有助于减轻叠层玻璃制品的重量。根据本发明的叠层玻璃制品具有良好的机械强度和在被砂砾投射损坏之后玻璃制品的良好的耐久性。由此降低了随后在脆化的玻璃制品上施加热梯度的过程中(例如,特别是在挡风玻璃的除冰过程中)破裂的风险。
外板的化学组成不同于内玻璃板的化学组成。有利地,根据本发明的叠层玻璃具有由“特种玻璃”制成的外玻璃板,其组成选自下文所给出的组成。
下文玻璃组成仅提及了实质组分。它们并没有给出组成的次要成分,例如常规使用的精炼剂,例如砷、锑、锡和铈氧化物,金属卤化物或硫化物或着色剂,特别是例如铁氧化物,钴、铬、铜、钒、镍和硒氧化物,其为在机动车玻璃制品的玻璃应用中最为常用的必需品。
根据一个实施方案,外玻璃板具有硼硅酸盐类型的化学组成。外玻璃板可以是这样的,其化学组成包含在下文所定义的重量含量范围内的以下氧化物:
根据另一个实施方案,外玻璃板还可以是铝硅酸钠类型的,由此其化学组成包含在下文所定义的重量含量范围内的以下氧化物:
这种类型的玻璃描述在例如专利EP-B-0914298中。
叠层玻璃制品优选在厚度上不对称:外玻璃板的厚度大于内玻璃板的厚度。
根据一个实施方案,外玻璃板为非增强的玻璃板。
出于本发明的目的,术语“非增强的”是指在弯曲之前所述板既未经化学增强,也未经热增强。因为它们未经化学增强,所以所述板在表面通常不包含相对于芯部来说过度集中的碱金属(例如Na或K)的氧化物。然而,,在玻璃中可能出现一定的应力(有利地处于压缩下),并且该应力由与聚合物***件的组装导致。
然而,如果用户希望如此并且如果玻璃允许如此,可以通过回火来化学增强玻璃板。
叠层玻璃制品的内板具有不大于1.5mm的厚度。优选地,该板具有不大于1.1mm,或甚至是小于1mm的厚度。有利地,内玻璃板具有小于或等于0.7mm的厚度。该玻璃板的厚度为至少50μm。
优选地,内玻璃板具有硅-钠-钙类型的化学组成。
常规地,内玻璃板为硅-钠-钙组成的玻璃,由此其包含在下文所定义的重量范围内的以下氧化物:
出于成本的原因,制造仅具有一个特种玻璃板的叠层玻璃制品实际上更有利。有利地,叠层玻璃制品的着色和/或功能通过内玻璃板来提供。为了实现此目的,可以选择具有光学和/或能量功能(energy function)的内玻璃板,例如通过使用有色的内玻璃板。根据一个优选的实施方案,根据本发明的叠层玻璃制品包含硅-钠-钙类型(普通玻璃)的内板和由特种玻璃制造的非硅-钠-钙类型的外板。
聚合物***件可以由一层或多层热塑性材料组成。其可以特别地由聚氨酯、聚碳酸酯、聚乙烯醇缩丁醛(PVB)、聚甲基丙烯酸甲酯(PMMA)、乙烯-醋酸乙烯酯(EVA)或离聚物树脂制成。聚合物***件可以呈具有特定功能的多层膜的形式,例如更好的声学性能、抗UV性能等。
聚合物***件的厚度为50μm至4mm。一般地,***件的厚度小于1mm。在机动车玻璃制品中,聚合物***件的厚度通常为0.76mm。
当玻璃板非常薄并且具有小于1mm的厚度时,使用厚度大于1mm,或甚至大于2或3mm的聚合物板可以有利于赋予玻璃制品刚性,而不会导致结构重量的过度增加。
通常地,所述***件包含至少一个聚乙烯醇缩丁醛(或PVB)的层。
根据本发明的叠层玻璃制品有利地构成机动车玻璃制品,特别是挡风玻璃。在与聚合物***件组装以形成最终制品之前,使叠层玻璃制品的构件板一起弯曲。
下文的实施例说明了本发明,但不限制其范围。
下表描述了五种不同玻璃的化学组成。
-组成C1:硅-钠-钙类型的标准透明玻璃
-组成C2:硼硅酸盐类型的玻璃
-组成C3:铝硅酸钠类型的玻璃
-组成C4:根据现有技术的化学增强的铝硅酸盐类型的玻璃(如在专利申请WO 2012/177426中描述的)
-组成C5:不含碱金属的硼硅酸盐类型的玻璃
重量% | C1 | C2 | C3 | C4 | C5 |
SiO2 | 71.1 | 80.6 | 60.7 | 61.9 | 63.6 |
Al2O3 | 0.65 | 2.3 | 7.7 | 16.6 | 16 |
B2O3 | 13 | 13.5 | 10.7 | ||
Na2O | 13.8 | 3.4 | 13.1 | 2.9 | |
K2O | 0.25 | 0.6 | 9.55 | ||
Li2O | |||||
CaO | 8.75 | 7.8 | |||
MgO | 4 | 8.4 | 3.4 | 0.1 | |
ZnO | 0.7 |
表1:所使用的玻璃的组成
组成C1至C5的玻璃的温度Tp在表2中给出。
Tp=(T退火+T软化)/2(℃) | |
C1 | (545+725)/2=635 |
C2 | (560+821)/2=690 |
C3 | (540+740)/2=640 |
C4 | (609+843)/2=726 |
C5 | (722+971)/2=846 |
表2:在表1中描述的各个组成的温度Tp
根据本发明的叠层玻璃制品使用组成C3、1.6mm厚的外玻璃板、0.76mm厚的PVB***件和组成C1、0.55mm厚的内玻璃板来制造。这两个玻璃板的温度Tp的差值为5℃:使这两个板同时弯曲。
组成C3的玻璃板尤其能够通过回火来化学增强。化学组成C3的化学增强的玻璃板与硅-钠-钙玻璃的薄的内玻璃板的组装可以获得低厚度且具有良好的机械强度的叠层玻璃制品,并且对于该玻璃制品,可以同时弯曲所述两个玻璃板。
出于对照的目的,通过将组成C4、1mm厚的外玻璃板与0.76mm的PVB***件和组成C1的内玻璃板组装来制备叠层玻璃制品。从机械的视角来看,强度测试是可接受的,外玻璃得以化学增强。另一方面,这两个玻璃板之间的温度Tp的差值为91℃:无法同时弯曲所述两个玻璃板。
为了对比不同的叠层玻璃制品对砂砾投射的抵抗力,进行压痕试验(称为“Sarbacane”试验)。该试验包括在固定在柔性胶框(rubber frame)内,尺寸为200×200mm的叠层玻璃制品板的外面之上从不同高度处(100至2000mm)释放称重的(重3.2g)维氏金刚石(Vickers diamond)压头。该柔性框允许叠层玻璃制品在压头的冲击过程中变形。由此可以测得在对外玻璃板冲击之后(冲击深度为100至150μm),直到利用显微镜检查能够观察到星形裂纹,或其最大尺寸超过10mm时的跌落高度(drop height)。注意到在压头每次落下和观察到裂纹的第一高度之间,高度增加了100mm。使每个叠层玻璃制品在九个不同的冲击点进行测试。在下文的实施例中给出的跌落高度值对应于九个破裂高度(fracture height)值的平均值。在使维氏压头跌落之后立刻进行裂纹的检测。
组装包含组成C2、1.1mm厚的外玻璃板,0.76mm的PVB***件和组成C1、0.55mm厚的内玻璃板的叠层玻璃制品。在该叠层玻璃制品上进行压痕试验(“Sarbacane”试验):所测得的平均跌落高度为1918mm。出于对照的目的,在由组成为C1的两个玻璃板构成的叠层玻璃制品(其中分别的厚度为:外板1.1mm和内板0.55mm)上进行相同的试验,得到所测得的平均跌落高度为989mm。根据本发明的叠层玻璃制品的机械强度对于目标应用来说是令人满意的。此外,两个玻璃板的温度Tp的差值为55℃:使所述两个玻璃板同时弯曲。
组装包含组成C5、0.7mm厚的外玻璃板,0.76mm的PVB***件和组成C1、0.7mm厚的内玻璃板的叠层玻璃制品。在该叠层玻璃制品上进行压痕试验(“Sarbacane”试验):所测得的平均跌落高度为1960mm。出于对照的目的,在由组成C1的两个玻璃板构成的叠层玻璃制品(其中分别的厚度为:外板0.7mm和内板0.7mm)上进行相同的试验,,得到所测得的平均跌落高度为633mm。叠层玻璃制品的机械强度对于目标应用来说是令人满意的。然而,两个玻璃板的温度Tp的差值为211℃:无法同时弯曲所述两个玻璃板。该组装件的机械强度满足所期望的标准,但是因为两个玻璃板的化学组成不同,且粘性行为也极其不同,所以无法一起弯曲这两个板。
Claims (13)
1.叠层玻璃制品,其包含至少一个外玻璃板、一个内玻璃板和位于所述两个玻璃板之间的聚合物***件,其中
内板具有不大于1.5mm的厚度,
外玻璃板为具有与内板不同的化学组成的玻璃板,
温度Tp1和Tp2之间的差值小于80℃,
温度Tp1定义为外玻璃板的退火温度上限和软化点之间的平均值,且温度Tp2定义为内玻璃板的退火温度上限和软化点之间的平均值,定义温度Tp的通式为
Tp=(T软化+T退火)/2
退火温度上限对应于玻璃的粘度为1013泊时的温度,并且软化点对应于玻璃的粘度为107.6泊时的温度。
2.如前述权利要求的玻璃制品,其特征在于温度Tp1和Tp2之间的差值小于70℃,且优选小于60℃。
3.如前述权利要求中任一项的玻璃制品,其特征在于温度Tp1和Tp2之间的差值为正数。
4.如前述权利要求中任一项的玻璃制品,其特征在于外玻璃板具有不大于2.1mm,且优选不大于1.6mm的厚度。
5.如权利要求1至4中任一项的玻璃制品,其特征在于聚合物***件包含一层或多层热塑性材料,其选自聚氨酯、聚碳酸酯、聚乙烯醇缩丁醛(PVB)、聚甲基丙烯酸甲酯(PMMA)和乙烯-醋酸乙烯酯(EVA)或离聚物树脂。
6.如前述权利要求的玻璃制品,其特征在于其包含至少一个由聚乙烯醇缩丁醛制造的层。
7.如前述权利要求中任一项的玻璃制品,其特征在于外玻璃板具有硼硅酸盐类型的化学组成。
8.如权利要求7的玻璃制品,其特征在于外玻璃板包含
9.如权利要求1至6中任一项的玻璃制品,其特征在于外玻璃板具有铝硅酸钠类型的化学组成。
10.如权利要求9的玻璃制品,其特征在于外玻璃板包含
11.如权利要求1至10中任一项的玻璃制品,其特征在于内玻璃板具有不大于1.1mm且优选小于1mm的厚度。
12.如权利要求1至11中任一项的玻璃制品,其特征在于内板具有硅-钠-钙类型的组成。
13.如前述权利要求中任一项的玻璃制品,其特征在于其构成机动车玻璃制品,特别是挡风玻璃。
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- 2014-10-22 PL PL14805976T patent/PL3060397T3/pl unknown
- 2014-10-22 EA EA201690771A patent/EA033246B1/ru not_active IP Right Cessation
- 2014-10-22 JP JP2016525579A patent/JP6646574B2/ja active Active
- 2014-10-22 ES ES14805976T patent/ES2824251T3/es active Active
- 2014-10-22 EP EP14805976.9A patent/EP3060397B1/fr active Active
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CN107108332A (zh) * | 2015-12-17 | 2017-08-29 | 法国圣戈班玻璃厂 | 化学增强的有色薄玻璃 |
CN107108332B (zh) * | 2015-12-17 | 2020-08-28 | 法国圣戈班玻璃厂 | 化学增强的有色薄玻璃 |
CN109843826A (zh) * | 2016-11-07 | 2019-06-04 | 日本电气硝子株式会社 | 夹层玻璃 |
US11104209B2 (en) | 2016-11-07 | 2021-08-31 | Nippon Electric Glass Co., Ltd. | Laminated glass |
CN112638832A (zh) * | 2018-08-30 | 2021-04-09 | 康宁股份有限公司 | 用于共成形的层压件的玻璃组合物 |
CN112638832B (zh) * | 2018-08-30 | 2023-10-13 | 康宁股份有限公司 | 用于共成形的层压件的玻璃组合物 |
CN109265023A (zh) * | 2018-09-26 | 2019-01-25 | 福耀玻璃工业集团股份有限公司 | 一种非对称厚度的夹层玻璃及其制造方法 |
CN109265023B (zh) * | 2018-09-26 | 2020-02-21 | 福耀玻璃工业集团股份有限公司 | 一种非对称厚度的夹层玻璃及其制造方法 |
CN113771433A (zh) * | 2021-09-30 | 2021-12-10 | 福耀玻璃工业集团股份有限公司 | 车用夹层玻璃 |
CN113771433B (zh) * | 2021-09-30 | 2022-08-19 | 福耀玻璃工业集团股份有限公司 | 车用夹层玻璃 |
WO2023051151A1 (zh) * | 2021-09-30 | 2023-04-06 | 福耀玻璃工业集团股份有限公司 | 车用夹层玻璃 |
Also Published As
Publication number | Publication date |
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HUE052365T2 (hu) | 2021-04-28 |
EP3060397B1 (fr) | 2020-07-22 |
KR20160077060A (ko) | 2016-07-01 |
JP2017500261A (ja) | 2017-01-05 |
FR3012072A1 (fr) | 2015-04-24 |
BR112016006751B1 (pt) | 2021-11-30 |
MX2016005143A (es) | 2016-07-18 |
CA2926172C (fr) | 2022-03-08 |
CN104755265B (zh) | 2017-09-01 |
US20160257094A1 (en) | 2016-09-08 |
EA033246B1 (ru) | 2019-09-30 |
KR102283764B1 (ko) | 2021-08-02 |
PL3060397T3 (pl) | 2021-07-12 |
US10343378B2 (en) | 2019-07-09 |
WO2015059407A1 (fr) | 2015-04-30 |
FR3012072B1 (fr) | 2021-01-01 |
CA2926172A1 (fr) | 2015-04-30 |
EA201690771A1 (ru) | 2016-08-31 |
JP6646574B2 (ja) | 2020-02-14 |
ES2824251T3 (es) | 2021-05-11 |
BR112016006751A2 (pt) | 2017-08-01 |
EP3060397A1 (fr) | 2016-08-31 |
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