CN1894096A - 包含柔韧连接物的对抗剧烈撞击具有改进结构完整性的玻璃层合物 - Google Patents

包含柔韧连接物的对抗剧烈撞击具有改进结构完整性的玻璃层合物 Download PDF

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CN1894096A
CN1894096A CNA2004800376601A CN200480037660A CN1894096A CN 1894096 A CN1894096 A CN 1894096A CN A2004800376601 A CNA2004800376601 A CN A2004800376601A CN 200480037660 A CN200480037660 A CN 200480037660A CN 1894096 A CN1894096 A CN 1894096A
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interlayer
glass
laminated thing
laminated
ionomer resin
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C·A·史密斯
D·M·莱因哈特
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • B32B17/10018—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 only one glass sheet
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    • B32B17/10825—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts
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Abstract

本发明包括具有固定到结构支撑物上的透明层合物的窗用玻璃元件，以及其制备方法。所述层合物包括至少一层玻璃，所述玻璃具有直接自粘附到所述玻璃层的具有低雾度的热塑性聚合物层，其中热塑性聚合物层沿着层合物的边缘连接到结构支撑物。

Description

包含柔韧连接物的对抗剧烈撞击具有 改进结构完整性的玻璃层合物
                      发明背景
技术领域
本发明涉及层合玻璃结构。本发明尤其涉及可以承受剧烈撞击的层合玻璃结构。
现有技术描述
安全窗(threat-resistant windows)和玻璃结构是已知的。美国专利5960606(’606)和美国专利4799376(’376)各自都描述了被制造以承受很大力道的层合窗。例如，在国际公开WO 98/28515(IPN’515)中，玻璃层合物被放置在刚性槽中，其中邻近玻璃的弹性材料允许在弹性材料和刚性槽之间进行伸缩运动(flexing movement)。已有的固定玻璃窗板的其它方式例如胶带、垫圈、油灰等可以用于将玻璃板紧固到框架上。
然而，能够承受飓风和大力撞击的现有技术窗户和玻璃结构并不是完美无缺。例如，当经受严重的飓风时，在IPN’515窗户中的伸缩运动(其中玻璃在刚性槽内伸缩)逐渐将层合物拉出所述槽，导致丧失结构完整性。在’376中，固定在框架上的玻璃能够被打碎和压碎，引起窗户/框架结构丧失结构完整性。
在美国专利6737151B1(其通过引用引入本文)中，描述了在夹层的帮助下固定在窗框中的玻璃窗元件。所述夹层提供了连接到框架的方式。在一些情况下，理想地或甚至有利地是使用更加柔软的材料将窗用玻璃连接到框架中。但是，具有适合用作夹层的光学性能的柔韧热塑性材料可能不具有安全窗用玻璃的恶劣应用所需的模量或撕裂强度。
                       发明概述
一方面，本发明是窗用玻璃元件(glazing element)，包括透明层合物和连接到该层合物(laminate)的支撑结构，所述层合物包括粘合到低雾度热塑性聚合物夹层的玻璃的至少一层，其中所述聚合物夹层以能够将所述层合物连接到所述支撑结构的方式外露，以及其中所述层合物通过所述聚合物夹层连接到所述支撑结构，所述聚合物夹层接着连接到包含(1)夹层相容性材料和(2)柔韧连接物(attachment)的复合材料。
                         发明详述
现在已经发现将夹层(玻璃层合物中的插入塑料层)连接到支撑结构提供具有改进完整性的窗用玻璃元件。本发明的窗用玻璃元件包括支撑窗用玻璃结构的支撑结构，其中所述窗用玻璃结构包括至少一层玻璃和直接自粘附到所述玻璃的至少一个表面上的至少一层热塑性聚合物层的层合物。在本发明的实践中，所述夹层片材具有高模量、优异的撕裂强度和直接面对玻璃时的优异粘附。优选地，所述热塑性聚合物层是特定的离聚物树脂。
在本发明的实践中，所述层合物夹层的周边通过连接部件(means)连接到支撑所述层合物窗用玻璃结构的结构(以下称为支撑结构)。所述支撑结构可以是框架、建筑物、螺栓、螺钉、线、绳索、钉子、卡钉、夹具、圈套、铆钉，上述的任意组合，以及用于支撑窗用玻璃元件的任何其它常规部件。可以从顶部、侧面、底部或通过夹层材料将夹层连接到支撑物。虽然优选所述支撑结构是围绕所述窗用玻璃结构的框架，但是不必排除其它支撑结构或部件。
本发明的层合物具有优异的耐久性、耐冲击性、韧性和耐玻璃切割性。本发明的层合物特别可用于易于经受飓风和风暴的建筑物中的建筑应用，并且也可以用作可能受到试图侵入车辆中的人员的反复攻击的汽车和卡车的侧窗。通过夹层连接到框架的本发明的层合物可以承受这样的应力或攻击而不会被从所述框架撕掉。本发明的层合物还具有低雾度和优异的透明度。这些性能使得其特别适合用作建筑玻璃，包括在其中例如减少太阳光线、声音控制、安全和可靠非常重要的应用中。
在一个实施方式中，本发明的层合物包括至少一层玻璃，所述玻璃具有直接自粘附到所述玻璃表面上的由具有低雾度的热塑性聚合物形成的夹层，其中所述夹层聚合物的外缘连接到环绕框架上。在本发明的方法中，所述层合物通过夹层被固定到框架上，所述夹层以能够将所述层合物连接到所述支撑结构的方式外露。
所述夹层被放置在玻璃板之间从而所述夹层以其可以被连接到环绕框架的方式外露。所述夹层可以沿着层合物的周边以连续方式连接到支撑结构。所述夹层可以在围绕层合物周边的多个点以不连续方式连接到结构支撑物。通过夹层将层合物连接到框架的任何方式都被认为是在本发明的范围之内。例如，环绕所述层合物的框架可以含有能够与层合物的玻璃表面粘合以及与框架粘合的夹层材料；所述夹层可以使用例如螺钉、钩子、钉子或夹具机械地固定到框架上。机械连接包括通过立刨、装配或模制支撑物以在结构支撑物内将夹层保持在位置上的对夹层的任何物理限制。所述夹层可以使用粘合剂材料化学粘合到框架，或通过使用机械和/或化学方法的任意组合将夹层固定到框架上。
可以将空气从层合物的层间除去，并且可以通过向所述结构施加热或压力将夹层粘合或粘附到玻璃板上。在优选实施方式中，不通过向所述结构施加增加的压力就可将所述夹层粘合。
本发明的一种优选层合物是两层玻璃与自粘附到至少一个玻璃表面上的中间热塑性聚合物夹层的透明层合物。
在一个优选的实施方案中，所述层合物的夹层是离聚物树脂的片材，其中所述离聚物树脂是乙烯和甲基丙烯酸或丙烯酸的聚合物的水不溶性盐，包含约14-24wt％的所述酸和约76-86wt％的乙烯。所述离聚物进一步的特征为用金属离子优选钠离子中和约10-80％的所述酸，和所述离聚物的熔融指数为约0.5-50。熔融指数根据ASTM D1238在190℃测定。离聚物树脂的制备公开于美国专利3404134中。可以使用已知的方法来得到具有合适的光学性质的离聚物树脂。例如，已知增加离聚物树脂的酸含量可以改进树脂的透明度。
在另一个优选的实施方式中，本发明包括增塑的聚乙烯醇缩丁醛，所述聚乙烯醇缩丁醛具有足够刚性的以用于本发明实践中的模量。合适的PVB夹层可以包括至少一种具有大于30℃的Tg的片材。
本发明的雾度和透明度根据ASTM D-1003-61使用HazegardXL211雾度计或Hazeguard Plus雾度计(BYK Gardner-USA)测量。雾度百分数是作为总光透射百分数的发散光透射。考虑适合用于建筑和运输应用。层合物的夹层通常需要具有至少90％的透明度和小于5％的雾度。
通过选择性地将层合物的玻璃表面定向于施加最大力的方向，可以实现进一步的改进。用于层合窗用玻璃结构的玻璃可以通过公知的并且常规的浮法玻璃法制造，其中熔融玻璃被浇注到液态锡浴表面上。以这种方式制造的玻璃表面通常认为具有锡侧和空气侧。对玻璃层进行定向使得锡侧被粘附到热塑性聚合物夹层可以减少剥落和在受到应力或冲击作用时玻璃的脱离。
在所述窗用玻璃元件的构建中，最有利的可能是使用具有相同表面尺寸的片材层合玻璃层和夹层。夹层的边缘可以延伸出层合物的周边。可以例如通过沿着层合物的周边放置夹层材料的条带(strip)将夹层连接到框架上。或者，夹层材料的条带可以被放置在框架内侧，所述条带和夹层材料的边缘相接触。在层合过程期间，材料相互接触并且当被加热时相互粘附。
对于本申请的目的，当提及所述热塑性聚合物层对玻璃是直接自粘附的时，这是指在热塑性聚合物层和玻璃之间不存在中间层。例如，在玻璃和热塑性聚合物层之间没有底漆或薄粘合剂层，玻璃或热塑性层的表面也没有被特别处理。
可以使用标准技术来形成树脂夹层片材。例如，可以使用压塑、注塑、挤出和/或压延。优选地，使用常规挤出技术。在典型方法中，适合用于本发明的离聚物树脂可以包括回收离聚物树脂以及新离聚物树脂。例如着色剂、抗氧化剂和UV稳定剂的添加剂可以被加入常规挤出机中并熔融共混并通过筒式熔体过滤器以除去污染物。所述熔体可以通过机头挤出并牵引通过压延辊以形成约0.38-4.6mm厚的片材。可以用于离聚物树脂中的典型着色剂是例如用于减少泛黄的上蓝剂或增白剂或可以被添加以着色玻璃或控制太阳光线的着色剂。
在挤出之后离聚物树脂片材可以具有光滑表面，但优选具有粗糙表面以在层合过程期间有效地从层合物中的表面间除去大部分空气。这可以例如通过在挤出后对所述片材进行轧花或通过在片材挤出期间的熔体破坏等来实现。
可以根据本领域已知的常规方法制备所述层合物。在典型方法中，将中间层放置在两片退火的浮法玻璃之间，所述玻璃的尺寸为12”×12”(305mm×305mm)以及标称厚度为2.5mm，已经在软化水中洗涤和漂洗。然后在设定为90-100℃的烘箱中加热所述玻璃/夹层/玻璃组合体30分钟。此后，所述组合体通过一组夹辊(辊压)从而可以将在玻璃夹层之间的空隙空间中的大部分空气挤出，并密封组合体的边缘。在这个阶段的组合体被称为预压体。然后将所述预压体放置于空气高压釜中，其中温度升至135℃，压力升至200psig(14.3bar)。保持这些条件20分钟，此后，将空气冷却但不再向高压釜中增加空气。在冷却20分钟之后当高压釜中的空气温度小于50℃时，释放过量的空气压力。
在优选的实施方式中，可以使用热、压力和真空将玻璃片、离聚物片和第二玻璃片层合到一起以除去空气。通过在框架中包括树脂片材的条带树脂片的边缘可以从玻璃的每个边缘延伸进框架中。离聚物树脂片可以在真空下(可以使用真空袋或真空环)被放置在两个玻璃板之间，并且可以被加热至约25-约135℃以得到组合体。将该组合体保持在该温度约15分钟-约2.0小时，然后冷却到环境温度，通常冷却到约25℃或更低。在该过程中所述树脂片的边缘可以与框架中的树脂片融合，产生整体结构。或者，可以根据相同的方法层合玻璃片和离聚物，除了使用环境大气压力以外。
对于建筑用途和对于在运输应用例如汽车、卡车和火车中的用途，层合物可以具有两层玻璃和自粘附到玻璃上的热塑性聚合物的夹层。本发明的层合物可以具有约3-30mm的总厚度。夹层可以具有约0.38-4.6mm的厚度，每个玻璃层可以是至少1mm厚。在优选实施方式中，所述夹层对玻璃是直接自粘附的，也就是说，在玻璃和夹层之间不使用中间粘合剂层或涂层。可以使用其它层合物构造，例如多层玻璃和热塑性夹层；或单层玻璃与热塑性聚合物夹层，在夹层上粘附有耐久透明塑料膜。任何上述层合物都可以涂覆有本领域已知的常规耐磨涂层。
所述框架可以由各种材料制造，例如：木材；铝；钢铁；和各种强塑料材料包括聚氯乙稀和尼龙。取决于所使用的材料和安装类型，可能需要或也可能不需要所述框架与所述层合物重叠以在所述框架和所述层合物夹层之间得到相当刚性的粘结。
所述框架可以选自窗用玻璃领域很多可使用的框架设计，条件是所述夹层可以被固定到所述框架上。夹层可以使用或不使用粘合剂材料而被连接到或固定到框架上。已经发现由离聚物树脂制备的夹层牢固地自粘附到大多数框架材料上，例如木材、钢铁、铝和塑料。在一些应用中，可能希望沿着框架的边缘使用额外的紧固件例如螺钉、螺栓和夹具。将夹层固定到框架上的任何方法都适合用于本发明中。
本发明的夹层具有约50-约1000MPa(兆帕)的储能杨氏模量，并优选具有约100-约500MPa的储能杨氏模量，根据ASTM D 5026-95a测量。夹层应该在高达40℃的温度保持其储能杨氏模量为50-1000MPa。
在本发明窗用元件的制备中，可以省略高压釜处理。本领域公知的步骤例如辊压(1)、真空环或袋预压(2)或真空环或袋作用(bagging)(3)可以被用于制备本发明的层合物。将这些层紧密接触并加工成最终的层合物，所述最终层合物没有气泡并具有良好的光学和充分的性能以在应用的使用期限内确保层合物性能。在这些过程中目标是挤出或压出在玻璃和塑料层之间的大部分空气。在一个实施方案中所述框架可用作真空环。外压的使用，除了驱除出空气外，还使玻璃和塑料层发生直接接触并产生粘附。
在特别优选的实施方案中，层合物的夹层可以粘合到复合材料，所述复合材料包括包含与夹层相容的至少一种聚合物或其它材料的织物或网(以后称为网)。相容，是指夹层和相容材料可以相互粘附粘合以形成强粘附连接的物质。所述相容材料可以是任何材料，其中所述材料能够与夹层材料粘合并且能够给出承受来自层合物重量的压力和用作玻璃层合物窗用结构部件的应力所需的粘合强度类型。适合用于本发明的所述网是柔韧材料，其具有足够的结构完整性从而在对抗由层合物的重量施加的力或由用作玻璃层合物窗用结构部件产生的其它力时保持完整。所述网可以由选自下组的材料制造：金属或金属复合材料例如铝、铜、锡和钢铁；天然织物例如棉、羊毛和麻；合成聚合物例如聚乙烯、聚丙烯、聚酰胺、聚酯、芳族聚酰胺；或玻璃纤维、碳纤维等。优选的是芳族聚酰胺，例如以商品名Kevlar从E.I.Dupont deNemours and Company得到的芳族聚酰胺。柔韧网材料可以用所述相容聚合物进行浸渍以形成本发明的柔韧复合材料。该复合材料可以在一点连接到夹层并在所述复合材料上的另一点可以使用所述框架或支撑结构或其它连接工具来固定所述柔韧复合材料，从而将层合物固定到期望的位置中。
可以以任何常规方式通过将所述柔韧连接物连接到夹层，或任何有效将所述柔韧连接物粘合到层合物的方式，实现连接。例如，所述柔韧连接物可以通过机械方式例如螺栓、夹具、销钉、卡钉或系材连接。或者，所述连接物可以使用物理和/或化学方式而与夹层连接，例如通过使用粘合剂或改变表面以在所述连接物和夹层之间产生化学粘附。或者，可以通过加热夹层从而夹层软化或优选流进和/或包围所述连接物形成物理/机械结合而连接夹层和网。
可以独立地使用或结合使用各种方法以连接所述柔韧连接物和所述夹层，但是，优选地是将连接物连接到夹层的步骤可以在不多于将玻璃片层合到夹层所花费的时间内完成。优选地，连接步骤花费的时间少于1小时，更优选地连接步骤花费的时间少于30分钟，最优选地连接步骤花费的时间少于20分钟。
在优选的实施方案中，在热过程中实施连接步骤，在夹层与柔软材料接触的同时使夹层与加热的元件接触。
实施例只是用于说明目的，并不限制本发明的范围。
实施例
一般层合步骤
使用下面的步骤制备玻璃和离聚物层合物：用去离子水洗涤2”宽10”长的玻璃片(3mm厚-经退火)并干燥。将具有表面构造的离聚物树脂片(2.3mm)厚放置在两片(two lites)玻璃之间。在这些实施例中，一些层合物使用1层90mil(2.3mm)厚离聚物树脂夹层以及一些层合物使用2层90mil(2.3mm)厚离聚物树脂夹层和2层厚度各为10mm的玻璃制成，其中所述离聚物树脂由81％乙烯和19％甲基丙烯酸组成，用钠离子中和37％，熔融指数是2。所述离聚物树脂从E.I.Dupont de Nemoursand Company作为Surlyn离聚物树脂得到。
实施例1
不添加柔韧边缘连接物。将所述层合物放置在各自具有1英寸宽度并与层合物两个表面的周边边缘的接触面积为0.5英寸的两个氯丁橡胶垫圈(80肖氏硬度A)之间，以模拟常规垫圈-玻璃安装或‘干-釉(dry-glazed)’安装。
实施例2
通过首先将离聚物树脂片材条带放置在层合物边缘和角架(angle)内表面之间将铝金属角架0.5”×0.5”×0.125”连接到层合物的边缘。
实施例3
沿着分开约2英寸的两个平行区域(宽度为约1英寸，长度为所述材料长度)放置arial密度为xxx厚度约为0.015”的Kevlar芳族聚酰胺网络或网与离聚物树脂(厚度也为0.015”)接触。加热该组合体以将树脂和网结合在一起。检测所得复合材料结构的拉伸强度。
通过放置上述离聚物/网复合材料与玻璃/离聚物层合物的离聚物树脂‘夹层’的一部分接触制备实施例4。一片(one lite)玻璃样品短0.8英寸，从而露出相当一部分该样品的离聚物树脂‘夹层’，从而产生0.8平方英寸接触面积并且向该样品施加拉力以模拟‘搭接-剪切(lap-shear)’测试。样品中的玻璃发生自破碎并且所产生的破碎玻璃层合物发生伸长。
通过使用与实施例3中相同的复合材料并且通过加热且施加一些压力到层合物边缘粘合到离聚物树脂夹层部分，其中所述离聚物树脂夹层本身通常是存在于标准层合物构型中的。在本情况下所述层合物的夹层厚度为0.180英寸。
实施例6-实施例9是按和实施例5相同的方式制备的，除了所有的层合物夹层的厚度都是0.09英寸之外。
实施例10是按照与实施例6-9类似的方式制备，与所有其它实施例不同的是网的取向是45度偏向，而所述所有其它实施例的取向是一个织向(weave direction)‘垂直’与层合物的边缘且另一个织向平行于层合物的边缘(分别为90&0度)。实施例10放置于(45度，45度)偏向织向。
将层合物放置于真空袋中或者施加真空以从所述层合物空间除去空气，然后将层合物放入在135℃为220PSIG(1.6MPa)的空气高压釜中90分钟。
实施拉伸测试以测量连接物的强度和完整性。在尺寸为1或2英寸×10英寸的样品上进行测试。每个样品的一端被夹具牢固地夹持到固定机构，另一端被连接到载荷传感器。使用几种不同的构型来评估复合材料网络的力学性质以及它们与层合样品的完整性。这对于每个样品还将进一步进行描述。拉伸测试速度是3英寸/分钟并且通过经校准的载荷传感器和位移电位技收集数据。然后通过数据采集系统收集所述数据用于作图和数据处理。
使用C-形金属夹具对实施例2进行拉伸测试，所述C-形金属夹具能够和铝角架互锁从而可以测量力-位移性质。
在实施例3中，在两端都进行夹持从而不会发生滑动并且破坏将由材料的撕裂表现出来。
在实施例4-6中在两端都进行夹持以避免任何可能的滑动。
通过围绕钢棒形成网络材料环从而机械地不是通过夹持作用实现固定，对实施例7进行拉伸测试。
通过穿过网络材料沿着线放置代表铆钉、钉子、螺钉或类似物以及标准固定方法的四个0.25英寸钢针，来对实施例8的样品进行测试。
通过在外侧边缘(平行于窗用玻璃)粘合额外的离聚物树脂条带对实施例9的样品进行测试。用0.05英寸宽2英寸长的狭缝产生钢C-夹持装置。在所述网络材料的较厚部分被强迫的情况下，该网络材料滑进该狭缝中。
通过以与实施例9样品相同的方式固定对实施例10的样品进行测试。
实施例11和13是通过上述相同一般方法制备的更大样品(5’×5’)，除了玻璃是6mm热强化的以及使用一层2.3mm(90mil)离聚物树脂片作为层合物夹层以外。玻璃尺寸是61英寸×120英寸，并且通过常规高压釜方法(135℃/60分钟保温时间)来制备层合物。制造Kevlar/离聚物树脂网络作为约3”宽50”长的条带。所述网络材料背衬有薄铝箔(0.002”厚度)。放置接触加热工具(在10英寸长的平坦金属表面上温度为170℃)与网络的铝箔侧接触，以提供足够的热量从而在承载在Kevlar网络材料上的离聚物树脂和窗用玻璃元件的离聚物树脂材料之间产生熔体融合结合。在这种情况下结合时间是约3英寸/分钟横动速度。由于起始耐热玻璃破裂机会的增加，所以没有研究更高的温度。所述网络边缘的放置与层合物的外侧表面的表面是齐平的，然后延伸超出玻璃的内侧表面约2.5英寸作为片状悬垂物。然后所述网络的柔韧性允许将未连接的‘片状悬垂物’末端置于挤出的铝‘压力板’之下，所述挤出的铝‘压力板’通常用于窗用玻璃工业以组装窗用玻璃单元以及提供机械强度和天气密封性。所述压力板用位于8英寸中心的自攻丝(self-tapping)#8机用螺钉连接到窗户竖框之下。
附在这里的是使用离聚物材料浸渍的Kevlar网的产品试验的实施例，其被常规框架体系固定并施加力进行测试。本发明的柔韧连接物使得层合物在一些情况下实际上可以伸长而不是崩断或断裂。
表1
  实施例   描述   边缘接触面积(平方英寸)   拉力(磅-英寸)   伸长(英寸)
  1   标准垫圈窗用玻璃   0   14   0
  2   金属角架   0.52   89   0.23
  3   柔韧网   N/a   611   1.53
  4   柔韧网/层合物   0.8   420   6.9*
  5   柔韧网/层合物   0.18   330   0.49
  6   柔韧网/层合物   0.090   197   0.31
  7   柔韧网/层合物   0.090   188   0.30
  8   柔韧网/层合物   0.090   201   0.33
  9   柔韧网/层合物   0.090   212   0.35
  10   柔韧网/层合物   0.090   181   0.82
注释*：所施加的应力导致层合的窗用玻璃元件自发开始玻璃破碎并发生样品的伸长。没有观察到柔韧连接物和窗用玻璃之间的破坏。
实施例2
  实施例   描述   边缘紧锁   循环压力   测试结果
  11   标准窗用玻璃安装   14mm   50psf   失败-边缘拉出
  12   柔韧连接物   14mm   150psf   通过-9000次循环
  12a-在应力下   由上述继续进行测试   175psf   由于边缘拉出-柔韧连接物和层合物边缘之间结合而失败
a实施例12的层合物经过US 6737151 B1中描述的飓风循环步骤地处理。

Claims (4)

1.一种窗用玻璃元件，包括透明层合物和连接到该层合物的支撑结构，所述层合物包括粘合到低雾度热塑性聚合物夹层的玻璃的至少一层，其中所述聚合物夹层以能够将所述层合物连接到所述支撑结构的方式外露，以及其中所述层合物通过所述聚合物夹层连接到所述支撑结构，所述聚合物夹层接着被连接到包含(1)夹层相容性材料和(2)柔韧连接物的复合材料。
2.权利要求1的窗用玻璃元件，其中使用的所述夹层相容材料的组成与所述夹层相同。
3.权利要求2的窗用玻璃元件，其中所述夹层是离聚物树脂。
4.权利要求3的元件，其中所述离聚物树脂基本上由乙烯和甲基丙烯酸或丙烯酸的聚合物的水不溶性钠盐组成，其包含14-24wt％的所述酸并用钠离子中和约30-50wt％的所述酸，和所述离聚物树脂的熔融指数为约0.5-50。
CNA2004800376601A 2003-12-16 2004-12-16 包含柔韧连接物的对抗剧烈撞击具有改进结构完整性的玻璃层合物 Pending CN1894096A (zh)

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