CN1196700A - 层压安全玻璃板的制造方法和用于制造的基片及其应用 - Google Patents

层压安全玻璃板的制造方法和用于制造的基片及其应用 Download PDF

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CN1196700A
CN1196700A CN96197008A CN96197008A CN1196700A CN 1196700 A CN1196700 A CN 1196700A CN 96197008 A CN96197008 A CN 96197008A CN 96197008 A CN96197008 A CN 96197008A CN 1196700 A CN1196700 A CN 1196700A
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彼得·科斯塔
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Abstract

本发明涉及一种制造在反射和传播光线时能避免发生由曲折引起的光学偏差的层压安全玻璃板。该玻璃板包含一第一玻璃板,一第二玻璃板和一由第一层压薄片和一由薄层系统组成的双轴向延伸的热塑基片和一第二层压薄片组成的多层中间层。由薄层系统形成的基片位于第一层压薄片上,其厚度为30至70μm。在120℃下热处理20秒后测得其两个延伸方向上的热皱缩为0.3至0.8%。第二层压薄片位于基片上,薄片块置于两玻璃板之间以免于折皱,加压和加热压制并与玻璃板成一体。本发明也包括用于制造层压玻璃板的合适的基片及其应用。

Description

层压安全玻璃板的制造方法和用于制造的基片及其应用
本发明涉及一种能避免光线在反射和传播时产生与折皱有关的光学偏差的层压安全玻璃板的制造方法，该层压安全玻璃板由一第一玻璃板，一第二玻璃板和一多层中间层组成，该中间层是由一第一层压薄片，一带一薄膜系统的双轴向延伸的热塑基片和一第二层压薄片组成的薄片层压件。本发明进一步涉及制造层压安全玻璃板的基片的应用和特别适用于该方法和该用途的基片。本发明还涉及平的、也可以是弯曲层压安全玻璃板的生产。平的层压安全玻璃板有许多用途，如用于建筑工业或作汽车上的侧窗。在本发明范围内，弯曲的层压安全玻璃板指简单地弯曲的和，尤其是双弯曲的(球状弯曲)的层压安全玻璃板即所谓的复合弯曲的层压安全玻璃板，它(们)至少在一些部分有大的弯曲，即小半径的弯曲。复合弯曲的层压安全玻璃板尤其用于汽车的挡风玻璃或后窗玻璃。
上述层压安全玻璃板中，薄膜系统形成所谓的功能层。用它制造的层压安全玻璃板能进行调整完成其他功能。这些功能中包括可加热性，光线和能量穿透率的改变与反射能力的改变和装设用于不同用途的天线。薄膜系统的结构及其生产方法是已知且有效的。尤其合适的薄膜系统以银层或半导体金属氧化物层为基础。这些薄膜系统在透明的热塑基片的帮助下与层压安全玻璃板成一体。目前已有技术可为如WO 90/08334，其描述了已有的基片、有效的薄膜系统和常用的层压薄片。
上面所述的层压安全玻璃板通常产生光学偏差。尤其在反射光线时。这些光学偏差由基片中的沟纹现象(Wellenbildung)引起。该光学偏差不仅在上述类型的平的层压安全玻璃板产生，而且在弯曲的，尤其是复合弯曲的层压安全玻璃板时会产生。
本发明的基础的已知方法(EP 0077672)涉及一在基片上的有选择地传播光或导电的膜片，其厚度在12和125μm之间，在120℃下热处理30分钟后产生以复杂方式取决于基片厚度的热皱缩。它在层压安全玻璃板中用于避免光学偏差，其中该基片与薄膜系统成一体。同样，这里的层压安全玻璃板可以是平的，或弯曲的。实验显示，根据这些教导所得的结果有缺陷。开头所述的在平的和带复合弯曲的层压安全玻璃板上，尤其在小半径弯曲的情况下的问题仍未解决。
为防止在制造层压安全玻璃板的过程中带薄膜系统，尤其是与开头所述的那类层压玻璃板成一体的由聚对苯二甲酸乙二醇酯制成的薄膜系统的基片改变其性能并因而导致光学偏差，已知的方法(EP 0 457 209A2)是在温度高于所谓的玻璃化温度时双轴向延伸基片，然后热固化，热固化之后再在温度低于玻璃化温度时进一步延伸。该已知的方法很复杂，且结果也不令人满意，开头提到的问题仍未解决。
本发明的目的在于，提出适用于工业规模生产层压安全玻璃板的简单方法，用它可以制造在反射和/或传播光线时不发生光学偏差的如开头所述的那种平的和弯曲的层压安全玻璃板。
为解决这个技术问题，本发明的主题是根据权利要求1的方法。为了避免由空气夹杂物(Lufteinschlue.sse)引起的层压安全玻璃板用于偏差，通常使用和要求进行属于本发明教导的排气。就层压安全玻璃板作为一个整体而言和就由层压薄片和基片构成的薄片层压件而言，需有效地和充分地进行排气。特征1.2)应理解为在层压安全玻璃制造中常用的层压方法。根据特征1.1)的方法步骤包括生产由第一层压薄片和基片及必要时第二层压薄片组成的，预层压件的可能性。在这种情况下，在以这种方式生产出的预层压件切成一定尺寸并放置在两玻璃板之间之前，将待预层压的薄片抽出，尤其是从原料辊上抽出，并在压力和热作用下连接在一起，同时或在加热前排气。
具体说来，在本发明范围内，存在实现根据本发明方法的几种可能性。根据本发明的一个优选实施例，由第一层压薄片和基片形成的预层压件置于第一玻璃板上，然后，第二层压薄片放在它的上面。当使用不能作为卷绕件的第二层压薄片时可用这种操作方法，正如使用根据挡风玻璃形状延伸的带防眩带的层压薄片时已知的那样。当必须制造弯曲层压安全玻璃板时，将预层压件置于第一玻璃板的凹侧面。放置预层压件之后，可加压和加热进行预压制，然后放置并压制第二层压薄片。本发明范围之内，需进行一预层压，由此形成一预层压片，它带一第一层压薄片、带薄膜系统的基片和第二层压薄片。可是，也可以采用这种方式，即第一层压薄片，基片和第二层压薄片都放在第一玻璃板上，然后进行整个层压件的压制。当生产弯曲层压安全玻璃板时，第一层压薄片置于第一玻璃板的凹侧面上。虽然，在根据本发明方法的范围内，推荐如上述方式工作，但制造弯曲层压安全玻璃板时，也可相反，将层压薄片或预层压件置于第一玻璃板的凸面侧上。在这个过程中需时时小心，不要在层压薄片或基片中形成折皱。
根据本发明的方法，可避免或抑制基片中的偏差变形和薄膜系统的破坏。本发明基于如下认识；即上述在反射光线中的光学偏差是由于微米级范围内的折皱而引起的。这些折皱是不正确加工的结果，及由于在通常的层压方法中使用不合适的基片而产生，也尤其在要求的排气过程中产生和当加压和加热把层压安全玻璃的组成部分连接在一起时产生。当制造弯曲的，尤其是复合弯曲玻璃板时，形成这种折皱的危险特别大。在制造层压安全玻璃板的过程中，如基片有折皱，当考察其反射时这就会很明显。
令人惊奇的是，根据本发明方法可避免在传播的，尤其是反射的光线时的光学偏差。现有技术难以使人们想到本发明能达到这一点。不仅在于制造平的层压安全玻璃板，而且在于制造弯曲的和复合弯曲的层压安全玻璃板时都能达到此效果。这还适用于当复合弯曲很大以致于在带薄膜系统的基片适应这些弯曲的过程中，会产生显著的折皱之时。原则上，该方法用于所有通常用于制造层压安全玻璃板的层压薄片和所有常见的带薄膜系统的基片。作为层压薄片，尤其是适合用以聚乙烯醇缩丁醛，乙烯乙酸乙烯酯，聚氨基甲酸酯和聚氯乙烯为基体的薄片，其中，尤其合适的是由聚酯及其衍生物，尤其是聚对苯二甲酸乙二醇酯构成的基片。用于基片的其他材料可以是纤维素酯或丙烯酸聚合物(acrylpolymers)和聚碳酸酯和聚氟乙烯。对此，材料需这样选择，它应能成为用于薄膜系统的尺寸稳定的基质，且能与层压薄片兼容并充分附着在其上。此外，它们还必须能经受层压过程而不被破坏，与薄膜系统相一致、透明且对UV稳定。
基片可简单地以这种方式延伸，即使所产生的热皱缩性能在制造层压安全玻璃板之前就得到保证。相应的方法是已知的。为制造适合于本发明方法的基片，原始薄片在高于所谓的玻璃化温度下双轴向延伸1％或更多，然后使延伸部分热固定。重要点在于，以这种方式来实施置上薄膜系统的方法，即使基片至多只发生轻微皱缩，这样，相应于特征1.12)的皱缩行为在涂覆之后和在本发明方法范围内使用之前仍存在。如果需要，需保证在涂覆过程中基片的充分冷却，或把薄片机械张紧在里面。令人惊奇的是，为确保根据特征1.12)的热皱缩基片在两个方向要求的延伸在完成后的层压安全玻璃板中不产生干扰的双折射效果。根据本发明的一个优选的实施例，根据特征1.12)其热皱缩率在0.3至0.6％范围内的带薄膜系统的基片置于层压薄片上。根据本发明层压安全玻璃板的各个玻璃板为通常厚度。它们可以是通常冷却的或化学或热预应力玻璃。也可使用部分预应力玻璃板。
上述的本发明的重要结果。可在通常厚度的层压薄片上获得。该厚度为0.38mm或其几倍的尺寸。厚度在40至60μm之间，最好大约50μm的基片放在第一层压薄片上。根据所用材料和压制时的温度或加压时间，不必用特殊方法来保证层压薄片和基片之间的连接。可是，当由两面至少有40MJ/m2表面能的薄膜系统形成的基片放置在第一层压薄片上时，在这个薄片层压件中获得了一个特别密切的连接。这样，在基片未涂覆一侧可进行如电晕(corona)或等离子处理。
当使用聚乙烯醇缩丁醛(PVB)或乙烯乙酸乙烯酯一共聚物(EVA)的层压薄片和聚对苯二甲酸乙二醇酯(PET)的基片时，所形成的参数值特别有利和优化。根据特征1.2)的压制通常在温度为120℃至130℃之间且压力低于13巴下进行。需再次注意到通常在生产层压件或预层压件之前需要的排气。可用常用方式如联接辊(gliederwalzen)、真空袋或真空唇(Vakuumlippen)进行排气。
根据本发明，特别准备的带薄膜系统的基片用于特殊目的，即用于制造能避免与折皱有关的光学偏差的层压安全玻璃板，尤其是弯曲的和复合弯曲的层压安全玻璃板。由于对本发明很重要的措施1.11)和1.12)使上述目的成为可能。这也适用于所述的预层压件(双板/三板)。也就是说，本发明也涉及上述的根据权利要求10至14的应用，以解决出现的技术问题。所述和所要求的应用也可以由由层压薄片和基片及必要时的第二层压薄片构成的预层压件实现。制造弯曲的，尤其是复合弯曲的层压安全玻璃板时，薄膜系统除了压力与温度的影响外，还要经受外力作用，以保证原始的薄片系统平的薄片与所造的层压安全玻璃的单或双弯曲相适应。当制造双弯曲的层压安全玻璃板时，这些力似乎产生压缩现象。这尤其适用于制造复合弯曲的层压安全玻璃板。另外，还有可以说是薄膜系统中的薄片带来的内力引起的变形。当制造单弯曲的弯曲层压安全玻璃板时，这些力可能产生剪切现象并且还产生内力的其他影响。制造平的层压安全玻璃板时情形相似。令人惊奇的是，本发明的教导在所有情况下解决了形成本发明基础的技术问题。当在排气过程中发生另外的机械的影响(空气流沟道的形成)时这也适用。
本发明也覆盖特别适用于上述方法和上述用途的基片。这些基片形成权利要求15至19的主题。
下面将参考一个具体的实施例来详细解释本发明。该具体的实施例涉及复合弯曲的层压安全玻璃板的制造，但不仅限于此。
-Monsanto公司的两面经过粒面处理(narben)的0.38mm厚的PVB层压薄片，-Southwall公司的带双银层的高透光性太阳保护膜(产品牌号XIR 75)的PET基片，和一第二个Monsanto公司的两面经粒面处理的0.38mm厚的PVB层压薄片，从辊筒上抽下，并在60至70℃温度下，在辊对之间连在一起，形成排过气的且部分粘合的预层压件，然后切成所需尺寸。
涂覆前，双轴向延伸和热加固该PET基片。在下面的条件下进行延伸和涂覆，即使该PET基片在涂覆后和制成预层压件之前呈现下列热皱缩行为：即在浸入加热至120℃的聚乙二醇(分子量大约为400)液浴中20秒时，涂覆后的PET基片在薄片平面中平行和垂直于纵向延伸方向皱缩约0.4％。将长150mm，宽15mm的薄片带两端夹紧在长度测量装置的爪之间来进行测量皱缩。在相同的起始温度下测量薄片带在浸入温度浴之前和热处理完成时的长度，由此，在一给定皱缩温度和停留时间时，长度变化的百分数可算作皱缩值。
为保证与层压薄片的充分粘合，涂覆后的PET基片的两面的表面能要大于40mJ/m2。
如上所述生产的预层压件无折皱地放在厚度为2.1mm的复合弯曲玻璃板的凹侧面。该玻璃板纵向和横向弯曲且有强的弯曲侧面部分。沿其边缘有压印上的和烧渗的不透明防眩带。然后，将一厚度为1.5mm的第二复合弯曲玻璃板(其弯曲与第一玻璃板相应)放在预层压件上。
将伸出玻璃板的边之外的预层压件的边部分切掉。如通常由制造弯曲层压安全玻璃所知的，沿板的周边形成一与真空系统连接的唇形部以便排气。
在随后的排气过程中，一真空施于唇形部约20分钟，这样，玻璃薄片束得以排气。然后，在保持真空的同时，在高压釜中辅以最高约为100℃的热处理约半小时进行预层压，间歇冷却后，再在高压釜中在125℃左右加热预层压玻璃薄片和在低于13巴的压力下进行压力处理，从而进行实际层压过程。
从高压釜中取出之后，可检测完成了的层压安全玻璃的光学反射与传播性能。同样，在玻璃板较强烈弯曲的侧面部分，涂覆后的PET基片基本上无折皱，并且玻璃板可达到汽车挡风玻璃或后部窗玻璃对于安全性能和光学反射/传播性能的严格要求。
用这种涂覆基体薄片进行对比实验，即其热皱缩性显然在本发明的要求范围之外，且其在120℃下热处理20分钟时皱缩小于0.3％，则不能形成不带所述光学偏差的层压安全玻璃，尤其在于在玻璃板的光学反射中，它会产生显著搓板现象(Waschbretteffekt)。当使用皱缩超过0.8％的基片时就会观察到所谓的桔皮现象(Orangenhauteffekt)，它是由于基片中形成的不规则的凹凸部分而引起的。另外，所要求厚度范围以外的基片的实验总的来说也不能得到满意的结果。

Claims (19)

1.一个制造在反射和/或传播光线时能避免与皱折有关的光学偏差的层压安全玻璃的方法，所述层压安全玻璃包括第一玻璃板，一相应的第二玻璃板和一多层中间层，该中间层是包含一第一层压薄片，一双轴向延伸的带薄膜系统的热塑基片和一第二层压薄片的薄片层压件，其特征在于：
1.1)在第一层压薄片上设置一带薄膜系统的基片，该基片
1.11)厚度为30至70μm，和
1.12)在120℃下热处理20秒后测得在两个延伸方向上的热皱缩率为0.3至0.8％，并且第二层压薄片位于基片上，
1.2)根据特征1.1)的薄片无折皱地设在两玻璃板之间并通过加压和加热进行压制，并与玻璃板连接。
其中在根据1.1)和/或1.2)的方法的范围内至少进行一次排气。
2.根据权利要求1的方法，其特征在于包含第一层压薄片和基片的预层压件放置于第一玻璃板上，第二层压薄片放置于预层压件上。
3.根据权利要求2的方法，其特征在于在放置上预层压件后用加压和加热进行预压制，然后放上第二层压薄片并压制。
4.根据权利要求1的方法，其特征在于在第一玻璃板上放上第一层压薄片，基片和第二层压薄片，或者包括这些薄片的预层压件，然后进行压制。
5.根据权利要求1至4的任一项的方法，其特征在于带薄膜系统的基片放置在第一层压薄片上，根据特征1.12)或2.12)其热皱缩率在0.3至0.6％范围内。
6.根据权利要求1至5的任一项的方法，其特征在于基片放在第一层压薄片上，其厚度为40至60μm，最好大约为50μm。
7.根据权利要求1至6的任一项的方法，其特征在于带薄膜系统的基片放在第一层压薄片上，其两个表面的表面能至少为40mJ/m2。
8.根据权利要求1至6的任一项的方法，其特征在于使用聚乙烯醇缩丁醛或乙烯乙酸乙烯酯为基础的层压薄片和聚对苯二甲酸乙二醇酯的基片。
9.根据权利要求1至8的任一项的方法，其特征在于根据特征1.1)的压制在温度在115至135℃范围下，最大压力为13巴下进行。
10.带薄膜系统的拉伸过的热塑塑料基片的应用，该基片厚度为30至70μm，并可双轴向延伸，用来制造层压安全玻璃，尤其是制造在反射和/或传播光线时不产生与折皱有关的光学偏差的层压安全玻璃，它包括第一玻璃板，一相应的第二玻璃板和一多层中间层，该多层中间层为包含第一层压薄片、双轴向延伸的基片和一第二层压薄片的薄片层压件的形式，
其条件为在120℃下热处理20秒后测量时，该基体薄片在两个延伸方向上的热皱缩率为0.3至0.8％。
11.根据权利要求10的应用，其条件为基片的热皱缩率在0.3至0.6％范围内。
12.根据权利要求10或11的任一项的应用，其条件为基片的厚度在40至60μm，最好大约为50μm。
13.根据权利要求10至12的任一项的应用，其条件为基片两个表面的表面能至少为40mJ/m2。
14.根据权利要求10至13的任一项的应用，其条件为基片由聚对苯二甲酸乙二醇酯构成。
15.用于实现根据权利要求1至9的任一项的方法的带薄膜系统的延伸过的热塑塑料基片的厚度为30至70μm，在120℃下热处理20秒后测得在两个延伸方向上的热皱缩率为0.3至0.8％。
16.用于根据权利要求10至14的任一项的应用的带薄膜系统的延伸过的  热塑塑料基片，其厚度为30至70μm，在120℃下热处理20秒后测得其在两个延伸方向上的热皱缩率为0.3至0.8％。
17.根据权利要求15或16的任一项的延伸过的基片，其厚度为40至60μm，最好为50μm。
18.根据权利要求15至17之一的延伸过的基片的两个表面的表面能至少为40mJ/m2。
19.根据权利要求15至18之一的延伸过的基体薄片由聚对苯二甲酸乙二醇酯制成。
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KR19990044644A (ko) 1999-06-25
US6242088B1 (en) 2001-06-05
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ZA967802B (en) 1997-04-07
ES2134003T5 (es) 2009-11-11
WO1997010099A1 (de) 1997-03-20
KR100433721B1 (ko) 2004-09-16
DE19534420A1 (de) 1997-03-20
PL183922B1 (pl) 2002-08-30
JP3669709B2 (ja) 2005-07-13
PL325559A1 (en) 1998-08-03
EP0877664A1 (de) 1998-11-18
EP0877664B2 (de) 2009-06-24
EP0877664B1 (de) 1999-06-23
CA2226969A1 (en) 1997-03-20
US20010028940A1 (en) 2001-10-11
JPH11512351A (ja) 1999-10-26
DE19534420C2 (de) 1999-05-12
AU696327B2 (en) 1998-09-10
CN1090559C (zh) 2002-09-11
DE59602305D1 (de) 1999-07-29
ATE181527T1 (de) 1999-07-15
CA2226969C (en) 2002-04-30
MX9801881A (es) 1998-05-31

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