CN1931926B - 硅氧烷离型组合物和使用该组合物的硅氧烷离型塑料膜 - Google Patents

硅氧烷离型组合物和使用该组合物的硅氧烷离型塑料膜 Download PDF

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CN1931926B
CN1931926B CN2005101029309A CN200510102930A CN1931926B CN 1931926 B CN1931926 B CN 1931926B CN 2005101029309 A CN2005101029309 A CN 2005101029309A CN 200510102930 A CN200510102930 A CN 200510102930A CN 1931926 B CN1931926 B CN 1931926B
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李政祐
金相弼
李文馥
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Abstract

公开了硅氧烷离型组合物和使用该组合物的硅氧烷离型塑料膜。所述的硅氧烷离型组合物包含：含乙烯基聚硅氧烷、含氢聚硅氧烷、含环氧环己基硅烷、铂催化剂和聚醚或月桂基醚。当硅氧烷离型组合物在其制备过程中以在线涂覆方式涂覆在取向聚酯膜上时，可以获得具有优异的硅氧烷固化特性、硅氧烷层与塑料膜之间的界面粘附力和剥离特性的离型膜。

Description

硅氧烷离型组合物和使用该组合物的硅氧烷离型塑料膜 
相关申请的交叉引用 
本申请要求根据35 U.S.C§119享有2005年6月13日提交的韩国专利申请No.2005-50254的优先权，其整体内容通过引用并入本文。 
技术领域
本发明涉及新型硅氧烷离型组合物和使用该组合物的硅氧烷离型塑料膜。更具体而言，本发明涉及具有优异长期稳定性和老化后擦除(rub-off)性能的硅氧烷离型聚酯膜。 
背景技术
一般来说，硅氧烷离型剂包括硅氧烷骨架、硅氧烷固化剂和催化剂。硅氧烷骨架包含乙烯基聚硅氧烷或含有乙烯基的己烯基聚硅氧烷，固化剂包含含氢聚硅氧烷(hydrogen polysiloxane)。 
通常，通过将离型剂涂覆到诸如塑料膜或片层、纸或无纺布的基质上来获得离型层。根据美国专利No.3,076,726、3,169,884、3,427,270、3,900,617等，已知利用硅氧烷浴将硅氧烷层涂覆到诸如塑料膜、纤维素膜或纸的基质上。另外，美国专利No.4,667,160和5,672,428中公开了硅烷偶联剂用于改进硅氧烷层和基质之间粘附性的用途。但是，这种硅烷偶联剂的问题在于由于它们的耐化学性差和涂料溶液浸涂期限(涂料溶液稳定性)短而导致它们从硅氧烷层和聚酯基质中分离出来。此外，一旦形成，就难以通过使用涂料浴长期生产硅氧烷离型膜。简言之，由于涂料溶液的浸涂期限短，上述专利中公开的确保硅氧烷离型特性的材料或方法的问题在于难以长时间进行离型涂覆。 
发明内容
因此，提出本发明来解决现有技术中存在的上述问题。本发明的一个目的是提供用于提高对聚酯基质的粘附力、耐化学性和涂料溶液浸涂期限的离型组合物，其包含具有独特结构的硅烷偶联剂。 
本发明的另一个目的是提供涂覆有上述离型组合物的塑料膜。 
根据本发明的一个方面，提供了包含聚硅氧烷、具有至少一个环氧环己基的硅烷、表面活性剂和催化剂的硅氧烷离型组合物。 
根据本发明的另一个方面，提供了以在线涂覆方式涂覆有上述组合物的离型塑料膜，如聚酯膜。 
附图说明
通过参照附图描述本发明的特定实施方案将使本发明的上述方面和特征变得明显，其中： 
图1是说明如何测试硅氧烷的固化特征的示意图。 
具体实施方式
我们已经发现当具有至少一个环氧环己基的硅烷化合物(例如β-(3，4-环氧环己基)-烷基三烷氧基硅烷或β-(3，4-环氧环己基)-烷基三乙酰氧基硅烷)加入到硅氧烷离型组合物中并将所得的离型组合物涂覆到诸如聚酯膜的基质上时，可以获得聚酯膜和离型涂层之间的界面粘附力明显提高并且具有优异剥离强度的离型膜。表面活性剂优选是聚醚或月桂基醚，催化剂优选是铂、铑或锡。 
在根据本发明的一个优选实施方案中，硅氧烷离型组合物包含4-30重量％的己烯基聚硅氧烷或乙烯基聚硅氧烷作为离型剂，0.3-3重量％的含氢聚硅氧烷、0.002-0.005重量％的铂催化剂和0.003-0.5重量％的β-(3，4-环氧环己基)-烷基三烷氧基硅烷或β-(3，4-环氧环己基)-烷基三乙酰氧基硅烷。 
优选的是，具有环氧环己基的硅烷化合物在组合物中的用量为0.1-10重量份，基于100重量份的聚硅氧烷。 
作为离型剂的乙烯基聚硅氧烷具有0.01-1μm的平均粒径。根据本发明的硅氧烷 离型组合物可以直接涂覆到各种基质上，所述的基质包括聚酯膜、聚丙烯膜、聚乙烯膜、聚氯乙烯膜、尼龙膜、聚碳酸酯膜和包含这些种类塑料的层压膜；牛皮纸；和无纺布和纺织布。此外，所述组合物的总固含量优选为4-30重量％，更优选为6-20重量％。 
当所述组合物的固含量低于4重量％时，不能获得均匀的覆盖和足够的离型/剥离特性。 
β-(3，4-环氧环己基)-烷基三烷氧基硅烷或β-(3，4-环氧环己基)-烷基三乙酰氧基硅烷是能够提高硅氧烷聚合物和诸如PET的基质之间界面粘附力的化合物。当上述硅烷化合物的用量为0.001-1重量％、优选0.003-0.5重量％时，可以确保稳定的物理特性。当上述硅烷化合物的用量低于0.003重量％时，基质(PET)和硅氧烷之间的界面粘附力下降，导致产生未反应的硅氧烷。另一方面，当上述硅烷化合物以高于0.7重量％的用量用在制造PET膜的工艺中时，在取向步骤期间和之后硅氧烷涂层膜破裂，导致剥离性能明显下降。此时，用于本发明的基质可以在进行离型涂覆之前加以电晕处理或等离子体处理，以形成基质和离型层之间的较强粘结。基质厚度为2mm或更小，优选为12-1500μm。此外，可以通过使用目前所用的底涂层如β-(3，4-环氧环己基)-烷基三烷氧基硅烷在待涂覆离型层的表面上预先对基质进行化学处理，以增强化学粘结。 
优选的是，在取向和干燥步骤之后，将离型组合物涂覆成厚度为0.1-2μm的涂层。此外，涂覆有硅氧烷离型组合物的聚酯膜的数均表面粗糙度适合为0.01-2μm，更优选为0.01-1.0m。当干燥后的涂层厚度大于2μm时，发生所谓的成块(blocking)现象，从而使涂覆硅氧烷的表面和未涂覆表面在一定压力下损坏(wound)。此外，在老化(24小时，50℃，95％RH)后发生所谓的擦除现象。硅氧烷层的这种擦除现象是由硅氧烷层和基质之间的粘附力不足引起的，这对于不含β-(3，4-环氧环己基)-烷基三烷氧基硅烷的离型组合物来说是个严重问题，下面的实施例和对比实施例说明了这一点。同时，使涂覆有离型层的基质热固化、干燥和取向的过程以下列方式进行：取向比为2.5-12，干燥/固化温度为60℃-250℃，干燥空气流速为8-40m/s，在干燥器中的停留时间为0.5秒-10分钟，优选1秒-1分钟。 
此外，当评价通过在线涂覆上述硅氧烷离型组合物而获得的聚酯离型膜的热稳定性时，优选聚酯离型膜在纵向上的热收缩为0.5％-1.5％，在横向上的热收缩为-0.03％-1.0％。更优选的是聚酯离型膜在纵向上的热收缩为0.3％-1％，在横向上的热收缩为-0.01％-0.4％。 
当在150℃/30分钟的条件下离型膜在横向上的热收缩大于0.5％时，不适合使用热熔胶粘剂的应用，因为在即时收缩或膨胀时，离型膜的硅氧烷层和聚酯层的每一个都在横向上具有不同的导热性，而热熔胶粘剂以垂直方向层压到离型膜上。 
用于本发明的β-(3，4-环氧环己基)-烷基三烷氧基硅烷具有下式所示的结构： 
Figure S051A2930920050920D000041
其中n为0或更大的整数，p为1或更大的整数。 
上述化合物的典型例子用下式表示： 
可以用于本发明的硅氧烷的典型例子包括下列化合物： 
Figure S051A2930920050920D000043
其中R1是CH＝CH2；R2是CH2-CH2-CH2-CH2-CH＝CH2或CH3；p和q分别表示0或 更大的整数。 
实施例 
在聚酯膜的制造工艺过程中，将包含上式所表示化合物的硅氧烷离型组合物以在线涂覆方式涂覆到聚酯膜上。这种在线涂覆可以通过凹板涂覆、绕线棒控涂覆(wirebar coating)、槽式涂覆(grooved coating)、刮刀式涂覆(comma coating)或MPG(Multi-Pressure-Gravure(多重压力凹板))5R/O或6R/O涂覆工艺。待涂覆硅氧烷离型组合物的塑料膜是通过对非取向薄片进行电晕处理或等离子体处理而获得的单轴取向膜；通过对非取向薄片进行电晕处理或等离子体处理并随后将其拉伸而获得的顺序双轴取向膜；或通过对非取向薄片进行电晕处理或等离子体处理并同时拉伸所获得的同时双轴取向膜。 
该实施例中用到的基质是发明人开发并可购自TORAY SAEHAN Co.的作为用于MLCC(多层陶瓷电容器)的离型载体的XD500-23、30、38或50μm基质。 
物理特性评价测试 
为了测定剥离强度，使用得自Chem.Instrument Co.的仪器Model AR1000。至于参比胶粘带，使用在2kgf的负载下，层压到硅氧烷离型膜表面上的TESA7475(商品名)。另外，使用得自Heraeus Co.的对流烘箱Model HC4033，以测定热老化之前和之后的剥离强度。使用4cm×15cm尺寸的样品，在100mm(长)×25.4mm(宽)的测定区中，在剥离速率为0.3m/分钟的180°剥离条件下测定剥离强度。测定的剥离强度以单位g/英寸表示，记录为5个测定值的平均值。 
胶粘带的剥离强度
将硅氧烷涂覆后固化的膜于2kgf的负载下在其涂覆硅氧烷的表面上和胶粘带(TESA7425)层压，以提供层压膜。将70g/cm2的铁棒置于离型膜上，将所得的结构于23℃/50％RH条件下存放24小时。然后，通过使用得自Chem.Instrument，Co.的仪器AR1000，以0.3m/分钟的剥离速率测定180°剥离强度。 
测定硅氧烷固化特征
将3M 810胶粘带粘附于硅氧烷离型层，并再次分离。然后，将下列测试试剂滴加到胶粘带上，根据测试试剂形成的点的尺寸评价固化度。可以理解的是点尺寸的确定取决于未反应硅氧烷被胶粘带分离的程度。通常，当测试试剂滴到带上时，形成较大的点。相反，当测试试剂滴到污染有未反应硅氧烷的带上时，形成较小的点。
测试试剂＝IPA(异丙醇)+颜料(以预定比例混合)。IPA不能溶解涂覆硅氧烷的表面，但它能溶解3M810粘合带。利用点尺寸将硅氧烷离型层以“优异”、“良好”、“中等”和“差”分级(参见表1)。 
老化后的擦除特性
为了评价老化后的擦除特性，使用得自JEIOTECH，Co.的型号TH-I-180的仪器。涂覆硅氧烷的膜在50℃/95％RH条件下存放2个月后，用手指使劲摩擦硅氧烷离型层，以进行测定硅氧烷层从聚酯膜分离程度的擦除试验。由擦除试验可以测定固化硅氧烷层和PET膜之间的界面粘附力。 
耐化学性
为了测定耐化学性，将棉签用MEK(甲乙酮)、甲苯、IPA(异丙醇)或1，4-BD(1，4-丁二醇)润湿，然后用该棉签使劲擦硅氧烷涂层，以测定硅氧烷是否分离。 
[表1] 
Figure 2005101029309A00800061
由表1可以看出，当根据实施例1-3的包含β-(3，4-环氧环己基)-乙基三甲氧基硅烷的硅氧烷离型组合物涂覆到经电晕处理的聚酯膜表面上时提供优异的界面粘附力和离型特性。具体而言，在根据实施例1-3的硅氧烷离型组合物中，硅氧烷离型层由于化学键连而表现出更高的界面粘附力，因此在与参比胶粘带层压后易于剥离。此外，硅氧烷离型层随时间表现出优异的耐溶剂性和稳定性，这从上述试验可以看出，其中在50℃/95％RH条件下存放2个月后各硅氧烷离型层可用手指使劲擦下。 
相反，当根据对比实施例1-3的不含β-(3，4-环氧环己基)-乙基三甲氧基硅烷的硅氧烷离型组合物涂覆到基质上时，表现出所谓的条纹(ribbing)现象(条纹形式的缺陷)，并随时间提供不稳定的剥离强度和差的稳定性。对比实施例1-3提供的数据显示物理特性和稳定性随时间的变化取决于不使用β-(3，4-环氧环己基)-乙基三甲氧基硅烷的湿硅氧烷离型组合物的粘度和涂层厚度(干燥后)。根据这些数据，随着涂层厚度增加，所谓的擦除现象变得严重。 
从上述实施例可以看出，用在本发明中的β-(3，4-环氧环己基)-烷基三烷氧基硅烷或β-(3，4-环氧环己基)-烷基三乙酰氧基硅烷保证了离型涂层的平滑性和聚酯基质与硅氧烷离型层之间的均匀界面粘附力。此外，虽然通常难以预防静电的产生和确保与涂覆硅氧烷的表面相对的聚酯基质背侧的流动性，在聚酯膜的制造过程中，可以将根据本发明的硅氧烷离型组合物以在线方式涂覆，从而可以从用户工艺中省略至少两个步骤，因而降低总成本，并防止出现负面影响产品质量的问题。 
此时，在可通过商业来源获得的硅氧烷的情况下，不能完全(100％)固化硅氧烷离型层。因此，不可避免的是，未反应的含氢聚硅氧烷和乙烯基聚硅氧烷或己烯基聚硅氧烷仍作为残余物存在于根据本发明的组合物中。当这些未反应的残余物长时间暴露于空气时，它们是带负(“-”)电荷的，从而和空气中带正(“+”)电荷的灰尘或异物形成强键。这些电化学键可以充当离型膜或离型纸和胶粘剂之间的交联物。在这种情况下，实现了具有非常高可剥离性的离型层。此外，当使用离型涂料浴时，它们可表现出优异的固化特性和剥离强度的稳定性，即使暴露于环境不合需要的外界时也是如此。 
此时，硅氧烷(聚硅氧烷)具有独特的结构特征，在于硅原子和氧原子之间的转动能基本上为0kJ。由于上述结构特征，传统的硅氧烷离型组合物在涂覆到基质上 并随后干燥后表现出差的透气性。除了这种差的透气性，传统的硅氧烷离型组合物表现出延迟的擦除现象，这是由于在聚酯和作为固化剂的含氢聚硅氧烷之间反应后所产生的水的作用下发生水解。换言之，当干燥的硅氧烷离型膜经历水的作用较长时间并用手指擦离型膜时，该膜明显被擦除。但是，根据本发明，该问题可以通过使用在硅氧烷浴中具有独特分子结构的硅烷偶联剂得以解决。因此，当根据本发明的硅氧烷离型组合物涂覆在聚酯基质上并干燥时，可以获得硅氧烷涂层和聚酯之间的优异界面粘附力。 
如上所述，通过在聚酯膜制造过程中将硅氧烷离型组合物以在线涂覆方式均匀涂覆到聚酯膜上获得的离型膜可以用作在多种应用中具有高的、优选性能的离型膜。这些应用包括用于制造涂胶标签、偏光膜(polarized film)和多层陶瓷电容器的载体离型膜；可以和日光控制的胶粘膜层压的LCD保护离型膜；保护性层压膜(overlamination film)；医用贴片(medical patch)；FPC(柔性印刷电路)保护膜；心电图保护膜；等等。 
上述实施方案和优点仅是示例性的，不应认为是限制本发明。本教导易于应用到其他类型的离型膜中。另外，本发明实施方案的描述是用于说明，而不是用于限制权利要求的保护范围，许多替换、改动和改变对于本领域的技术人员来说是显而易见的。 

Claims (7)

1.硅氧烷离型组合物，包含4-30重量％的己烯基聚硅氧烷或乙烯基聚硅氧烷作为离型剂，0.3-3重量％的含氢聚硅氧烷，0.002-0.005重量％的铂催化剂，和0.003-0.5重量％的β-(3，4-环氧环己基)-烷基三烷氧基硅烷或β-(3，4-环氧环己基)-烷基三乙酰氧基硅烷。
2.权利要求1所述的硅氧烷离型组合物，其中三烷氧基部分是甲氧基、乙氧基或其组合。
3.权利要求1或2所述的硅氧烷离型组合物，其中所述组合物还包含作为表面活性剂的聚醚或月桂基醚。
4.塑料离型膜，通过在塑料膜制造过程中经在线涂覆步骤将权利要求1所述的硅氧烷离型组合物涂覆到塑料膜的一个或两个表面上至预定涂覆厚度以形成硅氧烷离型层而获得。
5.权利要求4所述的塑料离型膜，其中待涂覆硅氧烷离型组合物的塑料膜是通过对非取向薄片进行电晕处理或等离子体处理而获得的单轴取向膜；通过对非取向薄片进行电晕处理或等离子体处理并随后将其拉伸而获得的顺序双轴取向膜；或通过对非取向薄片进行电晕处理或等离子体处理并同时拉伸所获得的同时双轴取向膜。
6.权利要求4所述的塑料离型膜，其中所述的塑料膜是聚酯膜、聚乙烯膜、聚丙烯膜、尼龙膜、聚碳酸酯膜、聚氯乙烯膜或聚乙烯醇膜。
7.权利要求6所述的塑料离型膜，其干燥后的涂层厚度为0.06μm-2μm。
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