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CN1978499B - 在宽度上具有改善的长度变化均一性的含聚乙烯醇缩醛的薄膜 - Google Patents

在宽度上具有改善的长度变化均一性的含聚乙烯醇缩醛的薄膜 Download PDF

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CN1978499B
CN1978499B CN2006101531959A CN200610153195A CN1978499B CN 1978499 B CN1978499 B CN 1978499B CN 2006101531959 A CN2006101531959 A CN 2006101531959A CN 200610153195 A CN200610153195 A CN 200610153195A CN 1978499 B CN1978499 B CN 1978499B
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CN1978499A (zh
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A·卡平斯基
F·威德曼恩
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Kuraray Co Ltd
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Abstract

本发明涉及基于含增塑剂的聚乙烯醇缩醛的在宽度上具有改善的长度变化的均一性的用于制备复合玻璃化物的薄膜及其在复合玻璃化物或者太阳能电池组件中的用途。

Description

在宽度上具有改善的长度变化均一性的含聚乙烯醇缩醛的薄膜
技术领域
本发明涉及基于含增塑剂的聚乙烯醇缩醛的在薄膜宽度上具有改善的长度变化均一性的薄膜以及由该薄膜制备的复合玻璃制品。
背景技术
基于含有增塑剂的聚乙烯醇缩醛(通常为聚乙烯醇缩丁醛)的薄膜长久以来用于制备复合玻璃制品。其中将该薄膜铺设到第一玻璃板上，用第二玻璃板覆盖，然后通过辊或者类似物轧制成预复合物。在复合物制备时，薄膜以几毫米的过量覆盖在下层覆盖玻璃上。在铺设薄膜后铺设上层覆盖玻璃，随后切除过量薄膜。这种修剪可以手工或者机械进行。取决于工艺，该薄膜齐玻璃边缘切除或者留下几毫米的限定过量。为了保持均一的层压边缘，需要在整个预复合工艺期间使薄膜边缘平行于玻璃边缘移动。
对于这些复合玻璃制品的中间层膜实际上仅通过连续挤出含增塑剂的聚乙烯醇缩醛物料制备。其中涉及所谓挤出薄膜的“向内弯曲”，即在边沿范围中横向的物料汇流，这导致在薄膜边缘的收缩变大。这种收缩造成薄膜的后端和前端横截边缘在预复合工艺期间在宽度上经受不同强度的长度变化，这导致横截边缘不再平行于玻璃边缘移动。
如果这种薄膜在切边后立即齐玻璃边缘封闭，那么这将导致在复合工艺期间在复合玻璃制品的边沿区域中没有薄膜的空心位置。这通常导致不能利用整个层压区域，而必须首先修剪横截边缘。在最差的情况下，这可在预复合炉中导致在空心位置处玻璃破裂。
如果这种薄膜在切边后立即沿玻璃边缘伸出，那么在层压工艺期间薄膜将在边沿区域收缩到玻璃边缘，但是在中部区域继续外伸。在这种情况下不会出现空心位置，但是必须修剪横截边缘，以没有损失地利用该层压件。在最差的情况下，这可导致辊在预复合炉中被伸出的薄膜污染或者在高压釜中与层压件粘合到一起，这可导致玻璃破裂。
横截边缘平行性不足的原因尤其是由于薄膜在其宽度上的不同纵向应力状态，这在具有高应力的区域导致在铺设和切除后的弛豫期间薄膜变短。尤其是然后当在边缘区域出现这种缩短时，导致镰刀状的横截边缘。
强边沿应力的作用主要是在较大的板尺寸下(例如从2×2m起)才是可见的。目前在玻璃工业中的约3×6m的最大尺寸的复合玻璃制品中观察到横截边缘的平行程度的特别明显的损害。
已知的是，具有均一厚度特性(即薄膜的外边缘具有和中部区域相同的厚度)的薄膜倾向于在外边缘产生较高应力。对于该问题领域，WO 2005/070651A1记载了在薄膜边沿区域具有较大厚度的PVB薄膜的制备。其中推荐薄膜的标准厚度为0.38mm和薄膜的边沿区域为0.4mm。该公开文献没有进一步详细说明增大厚度的边沿范围。此外，与0.38mm的标准厚度相比，薄膜在边沿处推荐的增大厚度较大，这可在层压工艺期间导致滞留空气增多。
发明内容
因此，本发明的任务在于提供在其宽度上具有均一长度变化的薄膜。
令人惊奇地发现，相对于均一厚度的薄膜，在限定的边沿区域中具有轻微边缘凸缘的膜在宽度上具有改善的长度变化均一性。
因此，本发明的主题在于在其宽度上具有改善的长度变化均一性的基于含增塑剂的聚乙烯醇缩醛的薄膜，其特征在于，该薄膜在最小宽度为100cm情况下在从膜边沿不超过20cm的边沿区域相对于其余膜区域的厚度平均值(或者膜中心)具有增加了0.15％-4.5％的厚度。
相对于WO 2005/070651，令人惊奇地发现，长度变化没有随变大的边沿厚度而改善。这表明根据本发明的0.1％-4.5％的低边沿增厚对于实现所需效果和同时避免在层压工艺中的负面效应(例如滞留空气)而言是足够的。
本发明的薄膜优选通过以90cm、100cm、200cm、250cm或者300cm的最小宽度挤出进行制备。特别优选地，本发明的薄膜以目前对于玻璃加工工业而言321cm(即310cm至330cm)的最大宽度进行制备。
薄膜的最小长度为200cm，但是也可以在挤出方向为10m、50m、100m、200m、500m、1000m或者2000m。
优选地，本发明的薄膜仅在位于膜的长度方向或者挤出方向的两个边沿方向具有增加的厚度。在边沿区域该膜的增大厚度也可以较低，例如相对于其余膜区域厚度的平均值为0.9％-2.8％。
在其中本发明的薄膜具有增加厚度的边沿区域可以为最多20cm(从薄膜边沿测量)宽。可能的是，在边沿范围内的厚度变化降低到不超过15cm(从薄膜边沿测量)或者不超过10cm(从薄膜边沿测量)。优选地，在此区域内薄膜的厚度从边沿到薄膜中部呈线性变化。
除了具有增加的薄膜厚度的边沿范围外，边沿区域之外的薄膜厚度波动降低另外改善了本发明薄膜在宽度上的长度变化的均一性。因此，在所谓的增厚边沿范围之外，本发明的薄膜优选具有最大±10％的厚度差，基于薄膜在该截面中的厚度平均值计。这种厚度波动下降得越低，通常在薄膜宽度上的长度变化的均一性就越好。因此，本发明的薄膜优选在边沿区域外具有最大±5％、最大±3％、最大±2％和特别优选最大±1.5％的厚度差。
在边沿区域外的范围内，本发明的薄膜具有对于复合玻璃制品的0.38、0.76、1.14、1.52或2.28mm的中间层薄膜国际惯用厚度作为平均厚度。
聚乙烯醇缩醛薄膜通常为了运输而卷绕在圆柱形芯体上。无根据本发明的边沿凸缘的薄膜在开卷时在边沿处收缩特别强烈，使得所得的薄膜滚筒不是圆柱形的，而是在边沿处比在中间处具有较低厚度。与之相反，由本发明的薄膜制成的滚筒几乎是圆柱形的或者甚至在滚筒侧部具有一定程度增大的厚度。
本发明的薄膜优选含有与一种或者多种增塑剂(例如己二酸二己酯(DHA)和/或乙二醇低聚物如3G7(三甘醇己酸酯)或者3G8(三甘醇辛酸酯)混合的聚乙烯醇缩醛(例如聚乙烯醇缩丁醛)。所用的聚乙烯醇缩丁醛可以未经交联的形式使用，或者如DE 10143109A1或者WO 02/40578A1所述以交联形式使用。特别优选的未经交联的组合物例如在EP 0185863、WO 03/097347或者WO 01/43963A1中公开。
本发明的薄膜可以以常规方式以真空工艺、轧制工艺、层压工艺、微波工艺或者高压釜工艺加工成复合玻璃层压体(EP 1235683B1或者EP 1181258B1)。因此，本发明的另一主题是由至少两块玻璃板和至少一层本发明的薄膜构成的复合玻璃层压体。该复合玻璃制品优选由两块玻璃板和设置在之间的本发明的薄膜构成。
本发明的薄膜可以在建筑领域或者汽车领域中用于制备复合玻璃化物。通过根据本发明的低的薄膜的长度变化尤其使得面积超过2m2的大面积复合玻璃化物的制备变得容易。
此外，本发明的薄膜可以用于制备太阳能电池组件。这种太阳能电池组件由透明覆层和背面及至少两层根据本发明的薄膜组成，在该两层薄膜间设置有太阳能电池。作为覆层可以使用玻璃或者透明的耐候性薄膜(例如PTFE、聚偏1，1-二氟乙烯或者聚氟乙烯(Tedlar，Dupont)。作为背面可以应用玻璃、PTFE、聚偏1，1-二氟乙烯、金属或者透明或者不透明的聚合物。
附图说明
图1示出了薄膜的均一厚度特性。
图2a示出了具有空心位置的层压件，图2b示出了具有伸出薄膜残余物的层压件。
图3示出了根据WO 2005/070651的薄膜的厚度特性。
图4a示出了具有空心位置的层压件，图4b阐述了具有伸出薄膜残余物的层压件。
图5示出了根据WO 2005/070651的薄膜制备的预复合件的侧视图。
图6示出了根据本发明的薄膜的厚度特征。
图7示出了根据本发明的薄膜制备的复合玻璃层压件。
具体实施方式
实施例：
制备了具有下面组成的含增塑剂的PVB混合物并将其加工成宽度为321cm和平均厚度为0.76mm的薄膜(对比例2∶0.38mm)。组成：75.5重量％的Mowital B68(残余乙酸酯含量小于1％，PVOH含量约29％)、24.5重量％的含稳定剂Tinuvin P和BHT的己二酸二己酯。使用乙酸钾作为阻粘剂。
对比实施例1：
制备了具有根据图1的均一厚度特性的薄膜。在用相应大小的玻璃板制备预复合件之后，观察到根据图2a的层压件中的空心位置或者观察到根据图2b的伸出薄膜残余物。
对比实施例2
根据WO 2005/070651制备了厚度为0.38mm和边沿凸缘大于5％的薄膜。图3示出了这种薄膜的厚度特性。在用相应大小的玻璃板制备预复合件之后，观察到根据图4a的层压件中的空心位置或者根据图4b的伸出薄膜残余物。另外，由此制备的预复合件显示出可能由于在薄膜内的不均一纵向应力分布而导致的薄膜外边沿区域振实(Stauchung)。这可能导致起泡或者不均一性(例如光学干扰)。图5示出了一个这种预复合件的侧视图，其中A表示在铺设前的上层覆盖玻璃，B表示下层玻璃，C(连续线)表示由于薄膜在外边沿处振实形成的波形或者褶皱的薄膜边沿，而D(虚线)表示在薄膜中部位于薄膜边沿后面的非波形部分。
本发明的实施例
制备了具有根据图6的厚度特征的薄膜。该薄膜在边沿区域(距离边沿最大12cm)具有增加约1.8％的厚度。用该薄膜制备的复合玻璃层压件具有根据图7的平行于玻璃边沿移动的薄膜边沿。薄膜和玻璃是叠合的，并可以无需进一步修正或者修剪而进行进一步加工。此外，在预复合件中仅观察到低的薄膜轴位(wellenlage)，即薄膜几乎平面地铺设在玻璃上。

Claims (10)

1.基于含增塑剂的聚乙烯醇缩醛的在宽度上具有改善的长度变化均一性的薄膜，其特征在于，相对于其余薄膜区域的厚度平均值，最小宽度为90cm的薄膜在不超过20cm的边沿区域厚度增加0.1-4.5％。
2.权利要求1的薄膜，其特征在于，所述薄膜边沿厚度增加0.9-2.8％。
3.权利要求1或2的薄膜，其特征在于，在所述薄膜的纵向上边沿区域具有增加的厚度。
4.权利要求1或2的薄膜，其特征在于，薄膜在边沿区域外的厚度差最大为该片段中厚度平均值的±10％。
5.权利要求1或2的薄膜，其特征在于，薄膜在边沿区域外具有0.38、0.76、1.14、1.52或2.28mm的平均厚度。
6.权利要求1或2的薄膜，其特征在于，薄膜具有200cm的最小宽度。
7.权利要求1或2的薄膜，其特征在于，薄膜具有200cm的最小长度。
8.复合玻璃制品，由至少两块玻璃板和至少一层根据权利要求1-7中任一项的薄膜构成。
9.太阳能电池组件，由透明覆层和背面和至少两层根据权利要求1-7中任一项的薄膜构成，在该两层薄膜之间设置有太阳能电池。
10.权利要求9的太阳能电池组件，其特征在于，所述覆层由玻璃或者透明的耐候性薄膜组成，而背面由玻璃、透明或者不透明的聚合物或者金属组成。
CN2006101531959A 2005-12-09 2006-12-11 在宽度上具有改善的长度变化均一性的含聚乙烯醇缩醛的薄膜 Active CN1978499B (zh)

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