CN103890119B - 脱模性能改进的自粘合保护膜和与该膜相粘合的产品 - Google Patents
脱模性能改进的自粘合保护膜和与该膜相粘合的产品 Download PDFInfo
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Abstract
本发明涉及一种脱模性能增强的自粘合保护膜以及与该膜相粘合的产品,本发明尤其涉及脱模性能显著增强的多层自粘合保护膜,上述性能通过在载体层中包含单分散小珠或者浮雕压花载体层来实现,还涉及与上述自粘合保护膜相粘合的产品。
Description
技术领域
本发明涉及脱模性能改进的自粘合保护膜和与该膜粘合的产品,特别地,涉及脱模性能显著增强的多层自粘合保护膜,这通过在载体层包含单分散小珠或者浮雕压花(embopattern)载体层来实现,还涉及与上述自粘合保护膜相粘合的产品。
背景技术
保护膜是指保护性膜、屏蔽膜、覆盖膜等,自粘合保护膜能够粘合于基底而不施加单独的粘合剂,这与通常的保护膜不同,因为膜本身具有粘合性能。
上述保护膜是用来保护IT产品和建筑材料的不同部件和材料的膜。上述膜施加到建筑材料和内饰材料以及IT产品,如移动电话、LCD和LED、家用电器和电子产品上,用于在长期运输或存储各种部件和材料时,防止外界的污染。
最近,随着IT产品所使用的部件和材料变得复杂化和小型化,公司研发高度有效的保护膜的需求增强,所述保护膜需具备零缺陷且不存在会导致缺陷的运输问题。
现有溶剂型保护膜的制备方法包含基底膜加载/释放过程,将预备涂料溶液涂覆于基底膜的涂覆过程,去除涂料溶液中残留液体的干燥过程,老化过程,切割过程以便应用各产品,等等。溶剂型粘合保护膜中使用的粘合剂为丙烯酸系,在涂覆过程中需要使用溶剂。目前所用的溶剂包括甲苯、二甲苯、乙酸丁酯等,上述溶剂因其毒性可能导致工作人员头晕或头痛等。此外,在干燥过程等过程中会产生对空气环境有害的挥发性有机化合物(VOC),因此,需要开发解决上述问题的根本问题的替代技术或方法。
最近,有人提出不使用溶剂的无溶剂型自粘合保护膜制备方法作为替代溶剂型保护膜制备方法的技术。所述无溶剂型自粘合保护膜还具有一优点在于,溶剂型保护膜因涂覆在表面上的粘合剂而可回收性低,而无溶剂型自粘合保护膜能够克服可回收性低这一缺点。
目前,由于自粘合保护膜的上述优势,开发其需求和兴趣极大提高,然而,考虑到国内产品的水平欠发达,小型和中型制造公司对技术研发的投入还不充分。
通常,为了在使用吹塑法或者流延法制备保护膜时具备自粘合性能,需要将保护膜加工成多层,其中将具有自粘合性能的乙烯乙酸乙烯酯、乙烯丙烯酸、VLDPE等共挤出形成粘合到基底的一层。
然而,与现有溶剂型粘合保护膜相比,施加乙酸乙烯酯基的粘合层的现有共挤出多层膜的不足在于其粘合力和耐热性等欠佳。此外,由于膜挤出过程中发生的缺陷导致残次品率高,这一缺点使得共挤出多层膜在要求高质量的光学薄片等中应用有限。
自粘合保护膜需要具备高粘合力,且其随时间的膜性能变化率极低以便增强耐热性。此外,当膜粘合到基底以后需易于切割,当膜剥离后在基底上无残留的物质,具备透明性,且多层膜的机械强度如抗拉强度和伸长率需可控。
鉴于以上内容,本发明人进行了研究,制备了自粘合保护膜,所述自粘合保护膜包含聚烯烃基树脂构成的载体层、聚烯烃基树脂构成的中间层和聚烯烃基树脂与弹性体树脂的混合物构成的粘合层,其中载体层包含单分散性小珠或者经浮雕压花,并研究了其脱模性能、粘合性能、切割性能和无残留特性,证实上述自粘合保护膜具有优异的脱模性能、粘合性能、切割性能和无残留性能,从而完成本发明。
发明内容
技术问题
本发明的目的在于提供脱模性能增强的多层自粘合保护膜,上述性能通过在载体层包含单分散小珠或者浮雕压花载体层实现。
本发明的另一个目的在于提供与上述脱模性能增强的多层自粘合保护膜相粘合的产品。
技术方案
为了解决上述问题,本发明提供了一种自粘合保护膜,所述自粘合保护膜包含聚烯烃基树脂构成的载体层;聚烯烃基树脂构成的中间层;和40-80重量%的聚烯烃基树脂和20-60重量%的具有环氧基、羟基或者胺基的弹性体树脂的混合物构成的粘合层,其中粘合层中所含具有环氧基、羟基或者胺基的弹性体树脂的熔融指数为1-12g/10分钟,密度为0.85-1.2g/cm3,且载体层包含单分散小珠或者经浮雕压花。
粘合层中所含具有环氧基、羟基或者胺基的弹性体树脂的熔融指数优选为1-4g/10分钟。此外,粘合层中所含具有环氧基、羟基或者胺基的弹性体树脂的密度优选为0.85-0.95g/cm3。
本发明中所使用的术语“自粘合性”是指这样的性能,膜能够粘合到所粘附表面而不使用任何其他粘合剂、不施加额外的压力或者加热、不使用如图钉、螺丝钉、订书钉、钉子或线等机械器件。
本发明中所使用的术语“保护膜”是指保护被粘物避免刮伤的膜或者通过粘合到被保护物表面且不易剥离下来从而保护被粘物表面的膜。
本发明中,载体层由聚烯烃基树脂构成。
本发明中,载体层的聚烯烃基树脂优选包含熔融指数为0.5-4g/10分钟且密度为0.90-1.10g/cm3的聚乙烯。
本发明中,载体层的聚烯烃基树脂可以利用齐格勒型催化剂、铬基催化剂、金属茂系催化剂等通过聚合方法制备,上述共聚物的形式可以为无规共聚物或者嵌段共聚物,分子结构可为无规立构、全同立构或者间同立构中的任一种,且聚合方法可以是低压方法、中压方法或者高压方法中任一种。可采用常用方法,将添加剂,如热稳定剂、紫外线吸收剂、抗静电剂或者荧光剂混合到上述聚烯烃基树脂中。
在本发明的自粘合保护膜中,载体层包含单分散小珠或者经浮雕压花,从而使得自粘合保护膜获得增强的脱模强度。
本发明中“单分散小珠”是指具有均一尺寸和形貌的小珠。
本发明中,单分散小珠的产品尺寸优选0.5-10um。如果单分散小珠的尺寸小于上述粒径范围的下限或者大于上述粒径范围的上限,则会有目标脱模强度达不到的缺点。
本发明中,单分散小珠优选包含丙烯酸基均聚物或者共聚物,但不限于上述物质。
本发明中,可用于聚合单分散小珠的丙烯酸基单体包括丙烯酸基均聚物或者共聚物、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、三羟甲基甲烷四丙烯酸酯(trimethylomethanetetraacrylate)、三羟甲基甲烷三丙烯酸酯、三羟甲基丁烷三丙烯酸酯、(甲基)丙烯酸缩水甘油酯、乙二醇二缩水甘油基甲基丙烯酸酯(ethyleneglycoldiglycidylmethacrylate)等可被单独或者以两种或者多种组合的形式使用。
本发明中,单分散小珠不难通过通用的分散聚合制备。
本发明中,通过将单分散小珠和树脂及载体层的添加剂混合得到浓缩母料后,载体层的树脂和母料混合搅拌并揉制,挤出,最后获得包含单分散小珠的膜状载体层。
本发明中术语“浮雕压花”是指在表面上作隆起的雕刻而形成图案。
本发明中,在膜加工的同时通过在载体层上用浮雕压花辊进行传动压花将浮雕图案引入载体层表面。
本发明中,浮雕压花的浮雕直径优选为1-1000um。如果浮雕压花的浮雕直径小于上述范围的下限或者大于上述范围的上限,则会有目标脱模强度达不到的缺点。
本发明的自粘合保护膜可以在载体层中包含上述单分散小珠或者载体层经浮雕压花,从而其脱模强度增强至4g/25mm或略小,优选为1-4g/25mm。特别是,在本发明的实施例中,制备的自粘合保护膜的脱模强度为1.5-3.5g/25mm。
本发明中,载体层的厚度优选为10-20um。
如果载体层的厚度小于上述下限,会有膜的机械强度变弱的缺点,如果载体层的厚度大于上述上限,会有膜的弹性降低的缺点。
本发明中,中间层由聚烯烃基树脂组成。
本发明中,中间层的聚烯烃基树脂优选包含熔融指数为4-8g/10分钟且密度为0.90-1.10g/cm3的聚乙烯。
本发明中,中间层的聚烯烃基树脂的制备方法、形式和添加剂与载体层的聚烯烃基树脂一样,但是,可调整熔融指数以具有差异。
本发明中,中间层的厚度优选为5-15um。
如果中间层的厚度小于上述范围的下限,会有膜的机械强度变弱的缺点,如果其厚度大于上述范围的上限,会有膜的弹性降低的缺点。
本发明中,粘合层由40-80重量%的聚烯烃基树脂和20-60重量%的具有环氧基、羟基或者胺基的弹性体树脂的混合物组成。如果弹性体树脂的混合比例高于上述范围,成膜将很难,如果其混合比例低于上述范围,可靠性下降。
本发明中术语“弹性体树脂”是指具有与橡胶相似性能的合成聚合物材料,包括:当变形时可以恢复到其原始形状,即有弹性,耐用,不会轻易磨损,耐化学试剂。尽管弹性体树脂具有高的粘合能力,但是其在保护膜中的应用有限,这是因为弹性体树脂在粘合后难以分离导致其自粘合困难,此外,由于其粘着性导致使用弹性体树脂成膜很困难,这进一步限制了其应用。
本发明中,为了同时利用弹性体树脂的高粘合性且保证易于分离和易于成膜,提供聚烯烃基树脂按适当的比例与弹性体树脂混合得到的混合物作为粘合层。
本发明中,就成膜的便利性和可靠性而言,粘合层更优选为40-60重量%的聚烯烃基树脂和40-60重量%的弹性体树脂的混合物构成的粘合层。
本发明中,弹性体树脂选自下组:乙烯基、苯乙烯基、丙烯基、丙烯腈基、丁二烯基、丙烯酸基、异戊二烯基、聚氨酯基和硅氧烷基弹性体树脂,但并不限于上组。
本发明中,优选地,弹性体树脂的重均分子量为500-2000000。如果弹性体树脂的重均分子量在上述范围之外,会有膜很难加工的缺点。
本发明实施例中,SG-P3TEA(长濑产业株式会社(Nagase)生产,日本制造)作为弹性体树脂被用作弹性体树脂,其包含15重量%的环氧基。
本发明中,粘合层中所用的聚烯烃基树脂与中间层中描述的相同。
本发明中,粘合层的厚度优选为10-20um。
如果粘合层的厚度小于上述范围的下限,会有可靠性下降的缺点,如果厚度大于上述范围的上限,会有制备成本升高的缺点。
本发明中,载体层:中间层:粘合层的厚度之比优选为:10-20:5-15:10-20。这是为了控制保护膜更好的耐用性和机械强度。
本发明中,多层自粘合保护膜可以被粘合到塑料、金属或者玻璃的表面,但并不限于上述材料。
本发明的自粘合保护膜可通过常规的吹塑法和/或流延法制得。
发明人制备了上述多层自粘合保护膜,其中载体层包含单分散小珠或者被浮雕压花,并研究了其脱模性能、粘合性能、切割性能和无残留性能,并证实所述自粘合保护膜具有优异的脱模性能,粘合性能,切割性能和无残留性能。
此外,本发明提供了与上述多层自粘合保护膜粘合的产品,其中载体层包含单分散小珠或者经浮雕压花。
本发明中,所述产品包括但并不限于:光学薄片、移动电话、计算机屏、电视机、干膜光致抗蚀剂(DFR),制作平板显示设备的塑料板、触屏膜、载体膜或者柔性印刷电路板的输入板、建筑材料、精密玻璃、汽车内饰材料、儿童玩具、厨房容器或者加热和冷却装置。
有益效果
本发明提供自粘合保护膜,所述自粘合保护膜包含聚烯烃基树脂构成的载体层;聚烯烃基树脂构成的中间层;聚烯烃基树脂和弹性体树脂的混合物构成的粘合层,其中所述载体层包含单分散小珠或者经浮雕压花,从而自粘合保护膜具有优异的粘合性能,切割性能和无残留性能,且具有显著增强的脱模性能。将上述膜应用于家用电器、电子产品、建筑材料等上可以极大促进各种部件和材料工业生产的发展。
本发明的实施方式
在下文,参照以下实施例详细描述本发明。然而,这些实施例仅为了说明目的,本发明的保护范围并不限于此。
实施例1-6和对比例1-2:制备自粘合保护膜
利用以下树脂制备自粘合保护膜,其中各层的混合比例和厚度之比如表1所示。
具体地说,通过将小球状的树脂干混或者熔融混合获得小球状的各层树脂,称量这些树脂并添加到各料斗,然后使用两种常用的单螺杆挤出机或者双螺杆挤出机(震创塑料机械工程有限公司(JennChongPlasticsMachineryWorksCo.Ltd.),JC-LH系列)在250℃挤出环境下熔融挤出形成载体层和中间层,在150℃下熔融挤出形成粘合层。为了对模具上铺展的层叠膜的载体层引入脱模性能,可以通过混合的方式在载体层中添加单分散小珠或者对模具上铺展的膜使用浮雕压花辊进行传动压花,再冷却层叠膜,最终使用空气冷却方法或者水冷法冷却整个层叠膜从而获得厚度为30-50um的多层自粘合表面保护膜。此时,在1000到10000级的干净房间中制备自粘合保护膜。
材料信息
树脂A:熔融指数为1.2g/10分钟且密度为0.93g/cm3的低密度聚乙烯
树脂B:熔融指数为0.9g/10分钟且密度为0.96g/cm3的高密度聚乙烯
树脂C:熔融指数为5.2g/10分钟且密度为0.94g/cm3的中密度聚乙烯
树脂D:SG-P3TEA,包含15重量%环氧基的弹性体树脂(长濑产业株式会社制造,日本制造)
小珠(2):产品直径2um,PMMA(聚甲基丙烯酸甲酯)树脂组成
小珠(4):产品直径4um,PMMA(聚甲基丙烯酸甲酯)树脂组成
小珠(6):产品直径6um,PMMA(聚甲基丙烯酸甲酯)树脂组成
小珠(8):产品直径10um,PMMA(聚甲基丙烯酸甲酯)树脂组成
浮雕(50μm):浮雕直径为50um的浮雕压花
浮雕(200μm):浮雕直径为200μm的浮雕压花
【表1】
实施例1:研究本发明自粘合保护膜的物理性能
如下所示检测本发明的自粘合保护膜的物理性能。
对脱模性能和粘合性能而言,在室温下使用3Kg的辊将粘合层和用作基底层的聚碳酸酯粘合在一起。30分钟以后,使用万能试验机,以300mm/分钟的速度拉伸来测量脱模性能和粘合性能(g/25mm)作为在膜和基底之间剥离强度。
对粘合性能随时间的变化率,将膜置于50℃且无人看管的烘箱中2天后,通过180°剥离测试来观察变化率,其中宽度为25mm,剥离速率为300mm/分钟。
对切割性能,当膜样本被粘合到基底上并切割成特定尺寸时,通过全面地判断切割的便利性,边缘是否被拉伸,是否产生粉末等等(○优,△中,×差)来评估保护膜的切割性能。
对残留性能而言,将膜剥离下来,然后通过鉴定是否有残留物存在,使用肉眼两步评估残留在基底上的物质(○存在,×不存在)。
测量结果如下表2所示。
【表2】
如表2所示,可证明与对比例中的保护膜相比,实施例中的自粘合保护膜具有显著增强的脱模性能,此外,也证明实施例中的自粘合保护膜具有优异的性能,包括:粘合性能、随时间变化率、切割性能和无残留性能。因此,从如上结果可证明本发明的上述自粘合保护膜具有特别优异的脱模性能,和粘合性能,切割性能以及无残留性能。
Claims (15)
1.一种自粘合保护层叠膜,其包含:
聚烯烃基树脂构成的载体层;
聚烯烃基树脂构成的中间层;和
40-80重量%的聚烯烃基树脂和20-60重量%的具有环氧基、羟基或者胺基的弹性体树脂的混合物构成的自粘合膜,
其中所述自粘合膜中所包含的具有环氧基、羟基或者胺基的弹性体树脂的熔融指数为1-12g/10分钟,其密度为0.85-1.2g/cm3;和
所述载体层包含单分散小珠或者经浮雕压花,从而使得所述自粘合保护层叠膜具有优异的粘合性能和脱模性能。
2.如权利要求1所述的自粘合保护层叠膜,其特征在于,所述载体层的聚烯烃基树脂包含熔融指数为0.5-4g/10分钟且密度为0.90-1.10g/cm3的聚乙烯。
3.如权利要求1所述的自粘合保护层叠膜,其特征在于,所述单分散小珠为丙烯酸基均聚物或共聚物。
4.如权利要求1所述的自粘合保护层叠膜,其特征在于,所述浮雕压花的浮雕直径为1-1000um。
5.如权利要求1所述的自粘合保护层叠膜,其特征在于,所述自粘合保护层叠膜的脱模强度为1-4g/25mm。
6.如权利要求1所述的自粘合保护层叠膜,其特征在于,所述中间层的聚烯烃基树脂包含熔融指数为4-8g/10分钟且密度为0.90-1.10g/cm3的聚乙烯。
7.如权利要求1所述的自粘合保护层叠膜,其特征在于,所述自粘合膜由40-60重量%的聚烯烃基树脂和40-60重量%的具有环氧基、羟基或者胺基的弹性体树脂的混合物构成。
8.如权利要求7所述的自粘合保护层叠膜,其特征在于,所述自粘合膜的聚烯烃基树脂包含熔融指数为4-8g/10分钟且密度为0.90-1.10g/cm3的聚乙烯。
9.如权利要求1所述的自粘合保护层叠膜,其特征在于,所述弹性体树脂选自下组:乙烯基、苯乙烯基、丙烯基、丙烯腈基、丁二烯基、丙烯酸基、异戊二烯基、聚氨酯基和硅氧烷基弹性体树脂。
10.如权利要求9所述的自粘合保护层叠膜,其特征在于,所述弹性体树脂的重均分子量为500-2000000。
11.如权利要求1所述的自粘合保护层叠膜,其特征在于,所述载体层:中间层:自粘合膜的厚度比为10-20:5-15:10-20。
12.如权利要求1所述的自粘合保护层叠膜,其特征在于,所述自粘合保护膜粘合到塑料、金属或者玻璃的表面。
13.如权利要求1所述的自粘合保护层叠膜,其特征在于,自粘合膜的厚度为10-20um。
14.一种与如权利要求1-13任一所述的自粘合保护层叠膜相粘合的产品。
15.如权利要求14所述产品,其特征在于,所述产品包括:光学薄片、移动电话、计算机屏、电视机、干膜光致抗蚀剂,制作平板显示设备的塑料板、触屏膜、载体膜或者柔性印刷电路板的输入板、建筑材料、精密玻璃、汽车内饰材料、儿童玩具、厨房容器或者加热和冷却装置。
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KR1020110106596A KR101329641B1 (ko) | 2011-10-18 | 2011-10-18 | 이형성이 개선된 자기점착성 보호필름 및 이를 부착한 물품 |
KR10-2011-0106596 | 2011-10-18 | ||
PCT/KR2012/008457 WO2013058526A2 (ko) | 2011-10-18 | 2012-10-17 | 이형성이 개선된 자기점착성 보호필름 및 이를 부착한 물품 |
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US (1) | US20140255675A1 (zh) |
KR (1) | KR101329641B1 (zh) |
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KR101329641B1 (ko) * | 2011-10-18 | 2013-11-14 | 한국생산기술연구원 | 이형성이 개선된 자기점착성 보호필름 및 이를 부착한 물품 |
DE102016223550A1 (de) * | 2016-03-10 | 2017-09-14 | Tesa Se | Verbundsystem mit schwach klebendem Abdeckmaterial |
KR102495564B1 (ko) * | 2019-10-18 | 2023-02-07 | 쇼와 덴코 가부시키가이샤 | 투명 도전 필름 적층체 및 그 가공 방법 |
CN111806023B (zh) * | 2020-06-23 | 2021-05-14 | 江门市华龙膜材股份有限公司 | 一种用于感光干膜的聚乙烯保护膜及其制备方法 |
KR102298328B1 (ko) * | 2020-09-17 | 2021-09-07 | 주식회사 알앤에프케미칼 | 박리력과 자기점착 특성이 우수한 열접착성 필름 및 이의 제조방법 |
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CN102066512A (zh) * | 2008-06-27 | 2011-05-18 | 屈德加薄膜产品股份有限公司 | 具有释放表面的保护膜 |
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US5026597A (en) * | 1983-04-01 | 1991-06-25 | Ppg Industries, Inc. | Soluble polymer interleaving material |
CA2083057A1 (en) * | 1990-05-18 | 1991-11-19 | Georgia M. Huff | Polyolefin laminate cling films |
JPH0625620A (ja) * | 1991-08-16 | 1994-02-01 | Okura Ind Co Ltd | 自己粘着性フィルム |
JP3064090B2 (ja) * | 1992-02-17 | 2000-07-12 | 住友ゴム工業株式会社 | ゴルフボール |
US20040023019A1 (en) * | 2002-08-02 | 2004-02-05 | 3M Innovative Properties Company | Particulate transfer film with improved bead carrier |
TWI370057B (en) * | 2005-01-11 | 2012-08-11 | Mitsubishi Plastics Inc | Heat shrinkable laminated film |
WO2007130277A1 (en) * | 2006-05-05 | 2007-11-15 | Exxonmobil Chemical Patents Inc. | Linear low density polymer blends and articles made therefrom |
JP2008208173A (ja) * | 2007-02-23 | 2008-09-11 | Nitto Denko Corp | 表面保護シート |
KR20090103434A (ko) * | 2008-03-28 | 2009-10-01 | 제일모직주식회사 | 반도체 조립용 접착 필름용 조성물, 이에 의한 접착 필름및 이를 포함하는 다이싱 다이 본드 필름 |
JP2011102400A (ja) * | 2011-01-27 | 2011-05-26 | Nitto Denko Corp | 表面保護シートおよびその製造方法 |
KR101329641B1 (ko) * | 2011-10-18 | 2013-11-14 | 한국생산기술연구원 | 이형성이 개선된 자기점착성 보호필름 및 이를 부착한 물품 |
JP6126457B2 (ja) * | 2013-05-22 | 2017-05-10 | 株式会社細川洋行 | チャック成型品 |
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CN1656190A (zh) * | 2002-05-28 | 2005-08-17 | 3M创新有限公司 | 分段的可固化转移带 |
CN102066512A (zh) * | 2008-06-27 | 2011-05-18 | 屈德加薄膜产品股份有限公司 | 具有释放表面的保护膜 |
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WO2013058526A3 (ko) | 2013-06-20 |
US20140255675A1 (en) | 2014-09-11 |
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WO2013058526A2 (ko) | 2013-04-25 |
KR20130042345A (ko) | 2013-04-26 |
KR101329641B1 (ko) | 2013-11-14 |
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