CN1802404B - 包含双官能表面改性剂的聚乙烯醇缩丁醛片材 - Google Patents

包含双官能表面改性剂的聚乙烯醇缩丁醛片材 Download PDF

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CN1802404B
CN1802404B CN2004800157464A CN200480015746A CN1802404B CN 1802404 B CN1802404 B CN 1802404B CN 2004800157464 A CN2004800157464 A CN 2004800157464A CN 200480015746 A CN200480015746 A CN 200480015746A CN 1802404 B CN1802404 B CN 1802404B
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W·陈
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Abstract

一种具有高抗粘连性能的聚合物片材，该聚合物片材包含配置在经增塑的聚乙烯醇缩丁醛表面上的双官能表面改性剂。该双官能表面改性剂包含抗粘连链段和相容性链段，其中抗粘连链段包含聚乙烯嵌段或烃链嵌段，相容性链段包含聚(亚烷基二醇)嵌段。一种制造具有高抗粘连性能的聚合物片材的方法，该方法包括对聚合物进行熔融加工成片材以及将双官能表面改性剂配置在聚合物片材的表面上，该双官能表面改性剂包含聚乙烯嵌段或烃链嵌段和聚(亚烷基二醇)嵌段。一种提高聚合物片材抗粘连性的方法包括将双官能表面改性剂配置在聚合物片材表面上，该双官能表面改性剂包含抗粘连链段和相容性链段，其中抗粘连链段包含聚乙烯嵌段或烃链嵌段，相容性链段包含聚(亚烷基二醇)嵌段。

Description

包含双官能表面改性剂的聚乙烯醇缩丁醛片材
技术领域
本发明公开内容涉及聚合物片材，更具体地说，本发明涉及通过在聚乙烯醇缩丁醛片材的表面上配置一种双官能表面改性剂使其具有高抗粘连性的包含聚乙烯醇缩丁醛的聚合物片材。
背景技术
经增塑的聚乙烯醇缩丁醛(以下简称“PVB”)通常用于制造作为透光层压材料(如安全玻璃或聚合物层压材料)中的夹层的聚合物片材。安全玻璃通常是指两块玻璃之间夹有聚乙烯醇缩丁醛片材构成的透明层压材料。安全玻璃通常用于为建筑物和汽车的窗孔提供透明的阻隔层。该透明阻隔层的主要功能是吸收能量(如来自物体的冲击的能量)以避免冲击物体通过窗孔进入封闭区域，从而使对物体的损坏或对人身的伤害降至最低。加到片材配料中的添加剂通常包括粘合性调节剂(“ACA”)以改善片材与玻璃之间的粘合性从而保持适宜的粘合强度以防止玻璃破裂，并能充分地吸收冲击能量。该夹层片材还可经改性而使安全玻璃具有一些其它功能如衰减噪声、减少紫外光和/或红外光的透过，和/或提高窗户的美学感染力。
安全玻璃通常是通过下述方法制成的：将两层玻璃和一层塑料夹层(如PVB)组装放入预压机中，粘合成预压层压材料，然后加工成光学透明的层压材料。组装阶段包括铺置一块坡璃，其上叠合一片PVB片材，再铺上第二块玻璃，然后沿玻璃板的四边修剪多余的PVB。
塑料夹层通常是通过下述过程制成的：将PVB聚合物与一种或多种增塑剂以及任选地与一种或多种其它成分相混合，然后对混合物进行熔融加工形成薄片，片材通常经收集、卷绕以便贮存和运输。对于用作汽车挡风玻璃的层合方法来说，通常从PVB卷筒中切割出PVB片段，然后将这些切割出的片段成形和/或堆叠起来供组装。其后，可从堆叠的片段中取出切割片段与刚性基材(如具有特定光学质量的玻璃板)以夹层排列形式组合在一起，使刚性基材的一个面与切割片段的一个面紧密接触并形成预压层压材料组件。或者替代地，可将多层切割片段与多层刚性片材交替叠合形成该层压组件。
经增塑的PVB片材无论是呈卷筒形态还是呈堆叠形态，在室温下，在进行层压过程前和层压过程中都有发生自身粘连的倾向。为了提高PVB的抗粘连性，已进行了多种试验，其中包括增加片材表面的机械粗糙度(例如压纹)，在片材表面施加粉料(如碳酸氢钠)以及对PVB片材表面进行化学或物理处理。不幸的是，这些表面处理过程常会增加不希望有的搬运操作或会产生玻璃粘合问题。避免发生这类粘连现象的其它常用方法包括：使PVB片材与其它片材(如聚乙烯)交替叠合，或在低温(如在约5°-15℃)下贮存和运输。然而，对于标准PVB片材的变体(如添加高含量增塑剂以提高降低噪声功能的PVB片材)，即使在低温条件下也会发生粘连现象。
此外，已经提出了在PVB中添加各种抗粘连材料的方法。然而，向PVB添加这类抗粘连材料会对制成的层压材料的光学性能产生负面影响，或者会对PVB片材与玻璃的粘合性能产生不利的影响。
因此，需要一种改进方法能提高PVB片材的抗粘连性，但不会对层压材料的光学透明度产生负面影响，也不会对制成的PVB片材与玻璃的粘合性能产生不利影响。
发明内容
业已出人意料地发现，根据本发明，在所述聚合物片材表面上配置有双官能表面改性剂会使该聚合物片材具有高的抗粘连性而不会对光学性能和粘合性能产生负面影响。同时，还发现包括将双官能表面改性剂配置在所述聚合物片材表面上的制造方法可赋予聚合物片材表面抗粘连特性。此外，本发明还包括由两块玻璃板与其间配置的聚合物片材夹层构成的层压安全玻璃，其中聚合物片材包含配置在聚合物片材表面上的双官能表面改性剂。
本文公开的内容是包含聚乙烯醇缩丁醛、加入聚乙烯醇缩丁醛中的增塑剂以及配置的经增塑的聚乙烯醇缩丁醛表面上的双官能表面改性剂的聚合物片材的例证性实施方案，该双官能表面改性剂包含聚(亚烷基二醇)与聚乙烯链或烃链的嵌段共聚物，当该嵌段共聚物施加PVB片材上时，其中的嵌段可分别使改性剂具有抗粘连性和相容性的双重功能。
一种制造聚合物片材的方法包括对聚合物进行熔融加工成为片材以及将包含聚乙烯嵌段或烃链嵌段与聚(亚烷基二醇)嵌段的双官能表面改性剂配置在聚合物片材的表面上。
层压安全玻璃包括两块玻璃板与配置在其间的聚合物片材夹层，其中聚合物片材包含配置在该聚合物片材表面上的双官能表面改性剂，所述双官能表面改性剂包含抗粘连链段和相容性链段。
具体实施方式
根据本发明，呈片材形态的经增塑的聚合物包含配置在聚合物片材表面上的双官能表面改性剂。虽然下述实施方案所指聚合物是PVB，但应当知道，该聚合物可以是任何一种具有适宜玻璃化转变温度的聚合物。一般来说，这类聚合物包括聚乙烯醇缩丁醛、聚氨酯、聚氯乙烯、乙烯-醛酸乙烯酯共聚物、以及上述聚合物的混合物等。该表面改性剂具有抗粘连功能和相容性功能的双功能特性。因此，该双官能表面改性剂为包含抗粘连链段和相容性链段的两亲结构聚合物。抗粘连部分能提高聚合物片材的抗粘连性，而相容性部分能赋予聚合物片材适宜的相容性，以保持聚合物片材的光学透明度和聚合物片材与玻璃间的最佳粘合性。
PVB通常是通过已知的缩醛化方法制得的，该方法包括在酸催化剂存在下，使PVOH与丁醛相反应，随后中和该催化剂，将树脂分离、稳定化并干燥。该聚合物通常包含约13-约30重量％，优选15-约22重量％(按PVOH计算)的羟基。该聚合物还包含至多约10重量％，优选至多约3重量％(按聚醋酸乙烯酯计算)的残酯基团，其余为缩醛，优选缩丁醛，但也任选地包含其它缩醛基团如2-乙基己醛基团。一般来说，产物PVB的分子量高于约70000克/摩尔。本文所用术语“分子量”应看作是平均分子量。制备PVB的适宜方法的细节对技术熟练人员来说是众所周知的。PVB可从Solutia Inc.，st.Louis，Missouri以ButvarTM树脂商购。
可向PVB聚合物添加各种添加剂以提高最终产品的性能。这类添加剂包括(但不受此限制)染料、颜料、稳定剂(例如紫外光稳定剂)、抗氧化剂以及上述添加剂的混合物等。
PVB片材通常在每百份树脂(“phr”)中包含约20-80份，更常见约25-60份增塑剂。增塑剂的含量会影响PVB片材的Tg。一般来说，增加增塑剂用量会降低Tg。通常，PVB片材的Tg为约30℃或以下。Tg低于约20℃的PVB片材常用作隔声PVB片材。通常采用的增塑剂为多元酸或多元醇的酯。适用的增塑剂包括例如三甘醇二-(2-乙基丁酸酯)，三甘醇二-(2-乙基己酸酯)，三甘醇二庚酸酯，四甘醇二庚酸酯，己二酸二己酯，己二酸二辛酯、环己基己二酸己酯，己二酸庚酯与己二酸壬酯的混合物，己二酸二异壬酯，己二酸庚基壬酯，癸二酸二丁酯，聚合物增塑剂如油改性的癸二酸醇酸以及如公开在美国专利3841890中的磷酸酯与己二酸酯的混合物和公开在美国专利4144217中的己二酸酯。常用的增塑剂还有如公开在美国专利5013779中的由C4-C9烷基醇与环C4-C10醇制得的混合己二酸酯。C6-C8己二酸酯如己二酸二己酯是优选的增塑剂。
PVB聚合物与增塑剂添加剂可经热加工而成形为片材形态。成形PVB片材的一种例证性方法包括强制地使熔融的PVB树脂+增塑剂+添加剂(下文称为“熔体”)通过挤片模头(例如模口的一个方面尺寸远大于垂直方向尺寸的模头)进行挤塑。成形PVB片材的另一种例证性方法包括将来自模头的熔融树脂或半熔融树脂流延在辊子上，使树脂固化，随后移出呈片状的固化树脂。在另一个实施方案中，片材的一侧或两侧的表面纹理结构可通过调整模口的表面网纹结构或在辊表面刻花进行控制。控制片材表面纹理结构的其它技术包括改变反应物材料的参数(例如树脂的含水量和/或增塑剂、熔体温度或上述参数的组合)。此外，该片材还可成形为具有彼此隔开的凸起部分的结构，这些凸起部分表明形成了暂时性的表面不规则性，有利于片材在层压过程中脱气，其后的高温、高压层压过程会使凸出部分熔入片材中，从而得到光滑外观的表面。在任何一个实施方案中，挤出片材的厚度通常为约0.3-约2.5毫米。
双官能表面改性剂优选或以涂层的方式直接配置在PVB片材的表面上，或先将双官能表面改性剂加入到片材材料的本体中，然后再迁移至形成的PVB片材的表面上的方法进行配置。双官能表面改性剂包含抗粘连链段和相容性链段。抗粘连链段优选包含聚乙烯嵌段或烃链嵌段，相容性链段优选包含聚(亚烷基二醇)嵌段。双官能表面改性剂的通式优选以下式表示：
R2-(OR1)nOH
式中R1为亚烷基，R2为聚乙烯或烃链，n为亚烷基二醇重复单元数。优选的双官能表面改性剂包含两亲的聚乙烯-聚(亚烷基二醇)嵌段共聚物(下文称“PEPEG”)，其通式为：
CH3CH2(CH2CH2)m-(OCH2CH2)nOH
式中m为约5-约24，n为约3-约30。在这样的一个实施方案中，聚乙烯嵌段优选通过聚(乙二醇)嵌段锚接在PVB片材表面上。更优选的是，聚乙烯嵌段在聚合物微区内结晶而在聚(乙二醇)嵌段上形成纳米结构层。在聚(乙二醇)嵌段上形成纳米结构层有助于降低PVB片材的粘连性，尤其是片材卷绕时。
将双官能表面改性剂配置在PVB片材表面上的例证性技术包括(但不受此限制)以物理涂布技术将该改性剂涂布在片材表面上的技术。表面改性剂的物理涂布技术包括(但不受此限制)喷涂技术、浸涂技术、凹槽辊涂布技术、熔体挤出技术等。在喷涂技术的一个例证实施方案中，改性剂配制在载液中，经雾化后喷涂在PVB片材表面上。在浸涂技术的一个例证性实施方案中，将PVB片材浸入载持有改性剂的液体中，当取出片材时，载体随之挥发，片材表面即涂上了表面改性剂涂层。在凹槽辊涂布技术的一个例证性技术方案中，在水性或溶剂基溶液中的改性剂通过压型镀铬辊(凹槽涂布辊)上料，过量改性剂被刮除，液体从凹槽涂布辊的料槽转移到PVB卷筒膜片上。对任何一种技术来说，载体可以是水性或溶剂基的(例如乙醇、甲醇、丙酮、甲乙酮以及这些溶剂的混合物等)。当改性剂一旦沉积在PVB片材上，载体经挥发而脱除，从而使改性在载体中的浓度应足以达到PVB片材表面上所要求的改性剂浓度。在通常的喷涂技术中，双官能表面改性剂在载体中的浓度为约0.1-约40重量％(以液体总重量计)。在上述任何一种涂布技术中，沉积在聚合物片材表面上的双官能表面改性剂的数量为每百万份约50-30000份(ppm)，优选约150-约10000ppm，更优选为约300-约5000ppm。
在熔体挤出技术的一个例证性实施方案中，通过将双官能表面改性剂与经增塑的PVB树脂熔融混合，然后对混合物进行熔体挤出或熔融加工成片材，从而将双官能表面改性剂加到PVB片材中。当经挤出或压制而成的片材冷却到约15℃时，双官能表面改性剂就会迁移至片材表面上。熔体中改性剂的浓度足以达到所要求的抗粘连性，并能保持光学透明性和粘合性能。在熔融共混技术中另一个例证实施方案中，通过改性剂与PVB树脂共挤出可获得包含任何PVB片材与添加了改性剂的PVB片材相复合的层合结构。
制得的包含双官能表面改性剂的PVB片材的粘连值与包含PVB树脂，但不含双官能表面改性剂的聚合物片材的粘连值相比，至少低约50％，优选至少低约70％，更优选至少低约90％。其上含或不含双官能表面改性剂的PVB片材的透明度可通过测定雾度值来加以确定，雾度值是指透过的散射光的百分比，散射光的方向偏离入射光束方向应大于一规定的角度，雾度值可根据ASTM D1003方法进行测定。优选的是，雾度值低于约3％，更优选低于约2％，最优选低于约1％。
含有双官能表面改性剂的PVB片材的粘合性基本上不受双官能表面改性剂的存在的影响。优选的粘合性值(PVB片材与玻璃的粘合趋向的定量化)为不具有双官能表面改性剂的PVB片材的粘合性值的约20％以内，更优选为约10％以内，最优选为约5％以内。粘合性可通过例如打击粘合性试验(但不受此限制)来测定，该试验用来测定PVB片材与玻璃间的粘合强度。
实施例
用于实施例中的试验项目
1：打击粘合性
在标准热压罐层压条件下制备两层玻璃层压材料试样。将该层压材料冷却至-17.8℃，用锤子以人工击碎玻璃。然后除去没有粘附在PVB片材上的碎玻璃，以目测法对仍粘附在PVB片材上的玻璃数量与一组标准相比较。该标准相应表示仍粘附在PVB片材上的玻璃数量的一个标尺。具体地说，在打击标准为零时，表示PVB片材上没有玻璃粘附。在打击标准为10时，表示100％玻璃仍粘附在PVB片材上。
2.粘连性
该试验用来测定PVB片材本身发生粘连的倾向性。在该试验中，切割出两片长方形膜条并完全成对叠合在一起。将每对的上层片材粘合在一片相应尺寸的胶带上。然后，将该膜条对居中放置在两块钢板之间，并在7℃和69千帕的压力下处理24小时。然后将该膜条置于剥离试验装置上以每分钟84英寸的剥离速度进行90°剥离试验予以剥离。粘连力以每线英寸磅(PLI)表示。
3.％雾度(透明度)
本试验用来测定以PVB片材制造的层压材料的透明度，测定是按照ASTM D1003-61(1977重新核定)-步骤A-采用光源C进行的，观察角为2°，测定雾度数值的仪器是D25型雾度计，购自Hunterlab。
实施例1：PVB片材的制备
采用高强度混合器对用于制造PVB片材的经增塑的PVB配料进行预混合。该配料包含100重量份其中含16.3重量％羟基(按PVOH计算)的PVB树脂，52份三甘醇二-(2-乙基己酸酯)以及包括粘合性调节剂、紫外光吸收剂、抗氧化剂和其它成分的其它添加剂。然后使经增塑的配料在挤塑机中熔融，并强制熔体通过由一对相对的模唇为界的前向端具有一矩形模口的挤片模头。熔体温度为约180℃。挤出片材的厚度为约30密耳(0.76毫米)。片材的每一面都为粗糙表面，以利于在层压过程中从片材与玻璃界面上排除空气。
实施例2：PVB片材的喷涂
在通常的喷涂方法中，采用空气雾化器和供给压力为约70-约700千帕(约10-约100磅/平方英寸(psi))的外压缩空气源使含双官能表面改性剂的液体雾化。含双官能表面改性剂的液体是通过将改性剂溶解或分散成不同浓度的水性溶液而制得的。然后，采用喷涂设备使液体雾化并将其喷涂在PVB片材的至少一侧表面上，随后通过干燥过程脱除载体，以使改性剂沉积在PVB片材的表面上。
表1列出了经通式为CH3CH2(CH2CH2)m-(OCH2CH2)nOH的具有不同分子结构的PEPEG喷涂的PVB片材试样的打击试验、粘连性试验和雾度试验的结果。
表2列出了经不同浓度的CH3CH2(CH2CH2)9-19-(OCH2CH2)10OH溶液喷涂的PVB片材试样的打击试验、粘连性试验和雾度试验的结果。
表3列出了经各种浓度的CH3CH2(CH2CH2)8-(OCH2CH2)20OH溶液喷涂的PVB片材试样的打击试验、粘连性试验和雾度试验的结果。
表1
Figure G2004800157464D00081
表2
表3
Figure G2004800157464D00091
实施例3：凹槽辊涂布PVB片材
采用每一单元具有多种可替换的方形料筒头(QCH)的凹槽辊涂布设备，用10重量％的PEPEG CH3CH2(CH2CH2)8-(OCH2CH2)20OH水溶液，以不同的涂布厚度涂布PVB片材。表4列出了用这种方法涂布的PVB片材的打击试验、粘连性试验和雾度试验的结果。
表4
aQCH(方形涂布料筒头)，一单元测定凹槽辊每单位面积的槽容积。
b承压辊对凹槽辊的转速比。承压辊的速度为每分钟20英尺。
实施例4：通过熔融混合制备的含PEPEG的PVB片材
使100重量份其中含有16.3重量％羟基(按PVOH计算)的PVB树脂、52重量份三甘醇二-(2-乙基己酸酯)、约0.1-约0.2重量份PEPEG以及包括粘合性调节剂、紫外光吸收剂、抗氧化剂等的其它添加剂的混合物在Brabender混炼机中于180℃下进行熔融混合7分钟，并在约150℃下进行熔体压制制成厚度为约0.76毫米(0.03英寸)的PVB片材。表5列出了含PEPEG的PVB片材试样的打击试验、粘连性试验和雾度试验的结果。
表5
Figure G2004800157464D00101
上述表面上配置有双官能表面改性剂的PVB片材的实施方案适用作层压安全玻璃的典型PVB夹层。此外，由于片材表面进行了改性而具有高的抗粘连性，因此上述实施方案还特别适用于制造非交替的隔声PVB夹层产品。
上述PVB片材与表面上未沉积双官能表面改性剂的PVB片材相比，具有几个优点。第一，表面上配置有双官能表面改性剂的PVB片材呈明显低的粘连倾向而同时能保持足够高的光学质量，并且该片材夹入层压安全玻璃中时对玻璃具有最佳的粘合性。由于PVB片材具有低的粘连倾向，因此不需冷却或夹入衬层就可进行贮存或运输。第二，由于上述公开的双官能表面改性剂是至少部分与PVB相容的，因此不必进行额外的加工步骤如洗净片材以除去粉料的步骤。该片材的其它优点对技术熟练人员来说是不言而喻的。
虽然已根据例证性实施方案对本发明进行了说明，但技术人员应知道，在不偏离本发明范围的前提下可对本发明内容作各种变换和等同替代。此外，为使具体的条件或材料适应本发明教导的要求，在不偏离本发明基本范围的前提下可制定多种变体。因此，本发明不限于所述的作为实施本发明最佳模式的具体实施方案，而是包括所有属于所附权利要求书规定范围内的实施方案。

Claims (16)

1.一种聚合物片材，该片材包含：
配置在所述聚合物片材的表面上的双官能表面改性剂，所述双官能表面改性剂包含抗粘连链段和相容性链段，其中所述聚合物片材包含聚乙烯醇缩丁醛，所述双官能表面改性剂包含具有下列通式的两亲聚乙烯-聚乙二醇嵌段聚合物：
CH3CH2(CH2CH2)m-(OCH2CH2)nOH
式中m为5-24，n为3-30。
2.权利要求1的聚合物片材，其中所述双官能表面改性剂喷涂在所述聚合物片材表面上。
3.权利要求1的聚合物片材，其中所述双官能表面改性剂是通过将所述聚合片材浸入包含所述双官能表面改性剂的溶液中而配置在所述聚合物片材表面上的。
4.权利要求1的聚合物片材，其中所述双官能表面改性剂是熔融共混在所述聚合物中的。
5.权利要求1的聚合物片材，其中配置在所述聚合物片材上的双官能表面改性剂数量为50-30000ppm。
6.权利要求1的聚合物片材，其中配置在所述聚合物片材上的双官能表面改性剂数量为150-10000ppm。
7.权利要求1的聚合物片材，其中配置在所述聚合物片材上的双官能表面改性剂数量为300-5000ppm。
8.权利要求1的聚合物片材，其中聚合物是包含按聚乙烯醇计算为13-30重量％烃基基团的聚乙烯醇缩丁醛树脂。
9.权利要求1的聚合物片材，其中聚合物是增塑的聚乙烯醇缩丁醛，其中增塑剂含量为每100份树脂20-80份增塑剂。
10.权利要求9的聚合物片材，其中聚合物是增塑的聚乙烯醇缩丁醛，其中增塑剂含量为每100份树脂25-60份增塑剂。
11.权利要求10的聚合物片材，其中聚合物是增塑的聚乙烯醇缩丁醛，其中增塑剂选自三甘醇二-(2-乙基丁酸酯)、三甘醇二-(2-乙基己酸酯)、三甘醇二庚酸酯、四甘醇二庚酸酯、己二酸二己酯、己二酸二辛酯、环己基己二酸己酯、己二酸庚酯和壬酯的混合物、己二酸二异壬酯、己二酸庚基壬酯、癸二酸二丁酯以及它们的混合物。
12.一种制造聚合物片材的方法，所述方法包括：
将聚合物熔融加工成片材，以及
将双官能表面改性剂配置在所述聚合物片材的表面上，其中所述聚合物片材包含聚乙烯醇缩丁醛，所述双官能表面改性剂包含抗粘连链段和相容性链段，所述双官能表面改性剂包含具有下列通式的两亲聚乙烯-聚乙二醇嵌段聚合物：
CH3CH2(CH2CH2)m-(OCH2CH2)nOH
式中m为5-24，n为3-30。
13.权利要求12的方法，其中所述双官能表面改性剂是喷涂在所述聚合物片材表面上。
14.权利要求12的方法，其中所述双官能表面改性剂是通过将所述聚合物片材浸入含所述双官能表面改性剂的溶液中而配置在所述聚合物片材表面上。
15.权利要求12的方法，其中所述双官能表面改性剂是熔融共混在所述聚合物片材中的。
16.一种层压的安全玻璃，包括其间配置有聚合物片材夹层的两块玻璃板，其中聚合物片材包含配置在所述聚合物片材的表面上的双官能表面改性剂，其中所述聚合物片材包含聚乙烯醇缩丁醛，所述双官能表面改性剂包含抗粘连链段和相容性链段，所述双官能表面改性剂包含具有下列通式的两亲聚乙烯-聚乙二醇嵌段聚合物：
CH3CH2(CH2CH2)m-(OCH2CH2)nOH
式中m为5-24，n为3-30。
CN2004800157464A 2003-06-09 2004-06-07 包含双官能表面改性剂的聚乙烯醇缩丁醛片材 Expired - Fee Related CN1802404B (zh)

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