CN102083928B - 聚烯烃剥离膜及其用途 - Google Patents
聚烯烃剥离膜及其用途 Download PDFInfo
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- CN102083928B CN102083928B CN200980124588.9A CN200980124588A CN102083928B CN 102083928 B CN102083928 B CN 102083928B CN 200980124588 A CN200980124588 A CN 200980124588A CN 102083928 B CN102083928 B CN 102083928B
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- stripping film
- ethene polymers
- membrane
- film
- ranvier
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Abstract
本发明披露了包含至少一层膜元件的分离膜,其具有基础膜,在基础膜上任选设置其它层。将剥离层施用至所述膜元件的至少一个面。所述分离膜的特征在于:所述基础膜含有密度为0.86-0.89g/cm3且最低晶体熔点为105℃的乙烯聚合物A和最低密度为0.90g/cm3的乙烯聚合物B。
Description
本发明涉及由至少单层膜结构制成的剥离膜,该剥离膜的至少一面施用了剥离层。
当胶带已经在一面或两面上涂覆有粘合剂时,在制造过程的结尾通常将它们以阿基米德螺线的形式卷绕成卷。将覆盖材料层压至暴露的粘合剂,然后与胶带一起卷绕;这样做的目的是,在两面上均有粘合剂的胶带的情况中,防止粘合剂彼此接触,或者在一面上有粘合剂的胶带的情况中,防止暴露的粘合剂面与载体背面粘合。对于这些覆盖材料,本领域技术人员使用术语“衬垫(liner)”。衬垫不仅用于覆盖在一面或两面上有粘合剂的胶带,而且用于覆盖标签。
衬垫(剥离纸,剥离膜)不是胶带或标签的构成部分,仅是其生产或贮存的辅助物,或者充当胶带/标签的进一步加工的辅助物,例如在冲压工艺(punching processes)中。而且与胶带基底相反,衬垫不与粘合剂层牢固粘合。
衬垫一般为剥离纸(在一面或两面上具有有机硅涂层的纸)。
少量使用的其它材料是膜,其由聚酯、聚丙烯或聚乙烯制成且具有有机硅涂层。本领域技术人员对基于膜的衬垫(当这些衬垫用于自粘合产品时)使用的术语为剥离膜-其中具体地,聚烯烃膜经由挤出吹胀或平膜挤出制造。
衬垫用于胶带制造工艺(将压敏粘合剂涂覆到衬垫上,干燥,将干燥粘合剂转移至基底,并除去衬垫)。衬垫也可用于贮存(例如在双面胶带的情况中)。衬垫提供压敏粘合剂层的保护性覆盖,并在应用中在粘合剂粘合之前除去。
对于许多在进一步加工领域中的应用(称为转化应用(convertingapplications)),不能使用剥离纸,实例是冲切部分的制造,这是因为剥离纸在暴露于湿度水平变化时尺寸上不稳定,而且厚度公差经常过度。此外,在冲压工艺后,来自于剥离纸的纸纤维粘附于胶带的切割边缘,当所述冲切部分用于卫生应用和电子设备应用时,例如在平板屏幕(flat screens)或移动电话的组合体中使用的冲切部分,这是不可接受的。
这种类型的应用目前使用50μm或75μm厚的硅化聚酯膜。尽管它们不具有剥离纸的上述缺点,但是从实用目的来看,它们相对昂贵并且仅可以无色形式获得。
当将在两面上有粘合性并且配有衬垫的胶带从卷中移除,并且使它的暴露的(即,无衬垫)粘合剂面与不平基底(例如弯曲或浮凸的表面、管或具有凸缘(beading)或铆钉的片材)粘结时,通常不可能获得胶带的无褶皱施用。
为获得无褶皱施用能力,胶带和衬垫必须是可伸展的,因此,用于不平基底粘结的材料尤其是由柔软且可伸展的聚乙烯(LDPE)制成的衬垫。然而,这些材料具有两个实质性缺点。
首先,当将有机硅施用至所述衬垫时,它不彻底硬化,这是因为需要的温度必须低(由于基础膜的软化点低),因此,低分子量有机硅余留在所述衬垫的表面并降低位于其上的压敏粘合剂的粘合性,这是低分子量有机硅随后转移至压敏粘合剂上的结果。而且,不能用粘合剂直接涂覆剥离膜,因此,必须将一个或多个粘合剂层施用至辅助衬垫(例如硅化聚酯膜),然后通过层压工艺转移至LDPE衬垫。该步骤不仅具有高操作成本,而且产生辅助衬垫形式的废物。
溶剂基的压敏粘合剂不能直接涂覆到PE膜上,这是因为它不耐溶剂或热。当使用热熔压敏粘合剂涂覆时,如果机器意外停止,则剥离膜熔融,这导致不希望的破坏。
可提高聚乙烯的耐热性以克服这些缺点,具体地,通过使用较高密度聚合物,例如MDPE或HDPE,但是这不利地将所需伸展性降低至前述值的一部分。
本发明的目的是提供具有良好伸展性的剥离膜,所述剥离膜不仅对于剥离涂覆(release coating),而且对于用压敏粘合剂直接涂覆具有足够的耐热性,并且不具有所述的现有技术的缺点。
所述目的以令本领域技术人员惊讶的和预料不到的方式,通过具体特征如独立权利要求所述的剥离膜实现。从属权利要求描述本发明的有利实施方式。本发明的主旨也涵盖本发明剥离膜的用途。
因此,本发明提供了由至少单层膜结构(其中存在基础膜,在基础膜上视需要存在其它的层)制成的剥离膜,其中已将剥离层施用至所述膜结构的至少一面。
所述基础膜包含密度为0.86-0.89g/cm3且晶体熔点为至少105℃的乙烯聚合物A,和密度为至少0.90g/cm3的乙烯聚合物B。
在本发明中,表述乙烯聚合物是指均聚物或基于重量的主要组分由乙烯组成的共聚物。
所述一个或多个剥离层覆盖所述膜结构的一个或多个外侧。
在本发明的一种优选实施方式中,基于聚乙烯聚合物的总量,在基础膜中乙烯聚合物A的比例为20-80重量%。
优选所述基础膜仅由乙烯聚合物A和B组成,并且进一步优选所述基础膜包含所述两种聚乙烯聚合物A和B的比率为1∶4-4∶1的混合物。
基于乙烯的离聚物的使用便于用手撕基础膜。在显著降低的Elmendorf撕裂强度值(ASTM D1922)中也看出这一点。因此在本发明的另一优选实施方式中,所述基础膜包含含有乙烯的离聚物。当使用这种方法时,在胶带的应用期间,可将覆盖有本发明剥离膜的胶带用手截成一定长度,由此使得可不使用任何刀或剪。
本发明剥离膜在MD(机器方向)上的机械性质优选在以下范围内:
●在10%拉伸应变时的力为3-30N/cm,优选为7-18N/cm,
●断裂拉伸应变为50-800%,优选为200-400%,和/或
●断裂力为10-50N/cm,优选为15-35N/cm。
在本发明的另一优选实施方式中,膜结构的厚度为45-200μm,优选为75-125μm。
所述膜结构在一面上,优选在两面上具有剥离层。可将已知脱模剂用于该目的(如果适合,以与其它聚合物共混的形式)。实例是硬脂基化合物(例如聚硬脂基氨基甲酸乙烯基酯(polyvinyl stearylcarbamate)、过渡金属如Cr或Zr的硬脂基化合物和由聚乙烯亚胺和异氰酸硬脂基酯制成的脲)、聚硅氧烷(例如以与聚氨酯的共聚物或与聚脲的共聚物的形式,或者以与聚烯烃的接枝共聚物的形式)和热塑性含氟聚合物。优选具有由辐射方法、缩合方法或加成反应产生的交联的聚硅氧烷。特别优选与甲基含氢硅氧烷在含铂催化剂的存在下交联的乙烯基聚二甲基硅氧烷。
所述剥离层可通过涂覆方法施用,但是在本发明中也可以共挤出具有所述膜结构的剥离层。
当使用含溶剂的剥离溶液(release solution)时,所述剥离层的施用量优选为0.2-0.8g/m2。如果通过无溶剂方法施用脱模剂,则施用量优选为1.0-3g/m2。
为了改善与表面的粘合,优选将所述膜结构的待配有剥离层的那些面预处理。这可通过化学涂覆或衍生自气相(例如含氟气体)的处理,或者通过物理处理(例如火焰处理或等离子处理,具体地,电晕处理)实现。
更优选的是,在所述基础层上,明确地存在一个共挤出外层或者优选在两侧上存在两个共挤出外层,所述外层由结晶度比基础层(优选地,内层)高的聚合物制成,其抑制在卷起剥离膜时剥离膜的粘连。此处该布置的外层在一个或多个剥离层下,即,在基础膜和剥离层之间。
所述一个或多个外层优选使用密度为至少0.90g/cm3,优选至少0.92g/cm3的聚乙烯,以及任选使用填料(抗粘连剂)。所述外层的另一种组分可为PE离聚物,以改善手撕灵敏性。所述一个或多个外层的厚度通常为芯层,即所述膜结构厚度的约5-20%。
在本发明中,优选的是,乙烯聚合物A的挠曲模量低于90MPa,同时乙烯聚合物B的挠曲模量为至少90MPa。
乙烯聚合物A和B的优选的熔体指数各自低于10g/10min。
已经证实,有利的是,乙烯聚合物A的密度为0.86-0.88g/cm3,和/或晶体熔点为至少115℃。特别有利的是,乙烯聚合物A的密度为0.86-0.87g/cm3。更优选的是,所述乙烯聚合物A包含C3-C10烯烃,特别是1-辛烯,作为共聚单体。特别优选的是,乙烯聚合物A的熔体指数为2-10g/10min。
在本发明的另一优选实施方式中,乙烯聚合物B的密度为至少0.92g/cm3,优选为0.94g/cm3。
乙烯聚合物B的实例为LLDPE、HDPE、MDPE、金属茂PE、EVA、EBA和EMA,特别优选为MDPE和HDPE。还特别优选具有宽峰或双峰分子量分布的乙烯聚合物。该聚合物的熔体稳定性由此实现稳定的吹制过程。
乙烯聚合物A和B的制备可使用其它聚烯烃,或常用添加剂,例如填料、颜料、抗氧化剂、成核剂、抗冲改性剂或润滑剂。
所述膜结构或者所述基础膜(如果这是单层结构),在这两者充当剥离膜制造工艺的基础的情况下,可通过流延或优选通过挤出,并且特别是通过吹塑薄膜挤出制造。
将所述膜结构离开生产机器的方向称为机器方向。即使剥离膜随后被冲压或切割以得到部分,所述机器方向仍继续得以明确限定且是可确定的。
本发明的剥离膜可用于制造标签或胶带。
可将本发明剥离膜层压至在两面上提供粘合性的压敏粘合剂,或者涂覆有在两面上提供粘合性的压敏粘合剂(以得到″无基底″胶带)。用本发明剥离膜覆盖的胶带也可包含基底,例如薄的纸(薄纸(tissue))、箔、织物、聚烯烃泡沫体或非织造布。
优选的是,所述胶带在两面上具有粘合剂,并且特别优选包含由薄纸、非织造布或泡沫体制成的基底。
适合的压敏粘合剂描述于D.Satas,Handbook of Pressure SensitiveAdhesive Technology(第三版,1999,Van Nostrand Reinhold)。特别适合的压敏粘合剂是基于丙烯酸酯类(acrylate)、基于天然橡胶或基于热塑性苯乙烯嵌段共聚物或聚异丁烯或有机硅的压敏粘合剂。优选压敏丙烯酸酯类粘合剂,以及可以分散体形式或热熔体形式施用,或者由溶液施用的这些压敏丙烯酸酯类粘合剂。使用的自粘性粘合剂可与一种或多种添加剂共混,以使性质最佳化,例如增粘剂(树脂)、增塑剂、填料、颜料、UV吸收剂、光稳定剂、抗氧化剂、交联剂、交联促进剂或弹性体。粘合剂层可通过热或通过高能辐射交联。
粘合剂在胶带基底上的涂层厚度优选为每面18-200g/m2,特别为40-120g/m2。如果胶带没有基底,则粘合剂在剥离膜上的涂层厚度优选为36-400g/m2,特别为80-240g/m2。
对于本发明,一般表达″胶带″包括所有片状结构,例如二维伸展的膜或膜部分、具有伸展长度和受限宽度的带、带部分、冲切部分和标签等。
当使双面胶带(其粘合剂已被所述剥离膜覆盖)退卷并在不平基底上用暴露的粘合剂面与所述剥离膜一起粘结时,本发明的剥离膜是特别有利的。其机械性质允许胶带的无褶皱施用。
测试方法
测量在以下温度和湿度条件下进行:23±1℃和50±5%相对湿度。
聚合物密度根据ISO 1183测定并用g/cm3表示。
熔体指数根据ISO 1133使用190℃和2.16kg测定并用g/10min表示。
晶体熔点(Tcr)通过薄层色谱法(TLC),使用10℃/min的加热速率,根据ISO 3146测定。
挠曲模量根据ASTM D790(2%拉伸应变的割线模量)测定。
剥离膜的拉伸应变行为在2型试样(150mm长和(在可能的情况下)15mm宽的矩形试条)上,根据DIN EN ISO 527-3/2/300,使用300mm/min的测试速率,100mm的夹持长度和0.3N/cm的预拉伸力测定;使用锐刀片修剪用于测定此处数据的样品。
拉伸应变行为在机器方向(MD,运行方向)上测试。力用N/试条宽度(以cm计)表示,以及断裂拉伸应变用%表示。
手撕灵敏性难以用数字表示,不过断裂力、断裂拉伸应变和耐拉伸冲击性(在纵向上测量)具有明显的影响。对所述剥离膜进行两种类型的撕扯:在两对拇指/食指之间横向撕扯,然后在施用后,以纵向动力(impulse)撕扯。
评价:
●++=良好
●+=可使用
●-=可费劲地使用
●--=撕扯需要施加大的力,末端不规则
在23℃贮存4周后评价所述膜结构的粘连。所述测试检查膜的剥离是否为:
●容易的(+)
●困难的(0)或者
●不可能的(-)。
所述剥离膜的膜结构的厚度根据DIN 53370测定。
下面将使用实施例说明本发明,本发明不受这些实施例的限制。
实施例
内容:
本发明实施例的描述
本发明实施例的结果的表格式整理
对比例的描述
对比例的结果的表格式整理
本发明的实施例1
在吹塑薄膜设备上制造具有下列结构的膜(膜中的层结构为1,2,3):
层1,18μm:
25重量%的 LD 251(ExxonMobil的LDPE,熔体指数8g/10
min,密度0.9155g/cm3,挠曲模量180MPa,晶
体熔点104℃)
75重量%的 Novex M21E760(Ineos的具有Zn离子的PE离聚
物,熔体指数0.5g/10min,密度0.933g/cm3,
晶体熔点107℃,挠曲模量200MPa)
层2,34μm:
78重量%的 INFUSE D9507(Dow的由乙烯和辛烯制成的聚
乙烯,密度0.866g/cm3,熔体指数5g/10min,
挠曲模量14MPa,晶体熔点120℃)
17重量%的 Hostalen GD9555(Basell的HDPE,密度
0.953g/cm3,晶体熔点132℃,挠曲模量
1050MPa,熔体指数0.9g/10min)
5重量%的 Plasblack PE 1851(Cabot的炭黑母料)
层3,18μm:
如层1
层2具有本发明的构造。
将所得膜结构在两面上电晕处理,然后在23℃贮存4周。在退卷时测试粘连。
然后使所述膜结构分别涂有由下列物质制成的混合物的溶液:
●96.5重量份Dehesive 914(Wacker Silicones的乙烯基聚二甲基硅氧烷),
●2.5重量份Crosslinker V24(Wacker Silicones的甲基含氢聚硅氧烷),和
●1重量份Catalyst OL(Wacker Silicones的在聚二甲基硅氧烷中的催化剂),
然后,所述涂层经通过烘箱硬化。
然后,使完成的剥离膜涂覆有丙烯酸酯类热熔粘合剂,具体地,以100g/m2施用粘合剂,其中丙烯酸酯类热熔粘合剂的组分如下:
8kg丙烯酸
48kg NTBAM(N-叔丁基丙烯酰胺)
8kg马来酸酐
368kg丙烯酸2-乙基己酯
368kg丙烯酸正丁酯
600kg丙酮/异丙醇(97∶3)
400g+400g的Vazo 67(DuPont的2,2′-偶氮二(2-乙基丙腈))
制造这种粘合剂的精确方法可参见DE 101 45 229A1的实施例。
然后,将15g/m2薄纸(Toyota Tsuho Corporation的TS Tape Paper)层压至粘合剂层并将整个材料卷起来以得到卷。
在第二操作中,使该前体材料退卷并再次类似地用压敏粘合剂涂覆,但是这次是在所述薄纸的无粘合剂的面上涂覆,然后将所述材料卷起来以得到母卷(parent roll)并切割。
可将退卷胶带与剥离膜覆盖物一起在不平表面上用暴露的粘合剂面施用,而无褶皱。
本发明的实施例2
在吹塑薄膜设备上,制造由33重量%INFUSE D9507和67重量%LD251制成的150μm厚的膜。将所得基础膜在两面上进行电晕处理,然后在23℃贮存四周。在退卷时测试粘连。
然后使所述膜分别涂有由下列物质制成的混合物的溶液:
●96.8重量份SL 6670(具有铂催化剂的乙烯基聚二甲基硅氧烷,GESilicones),和
●3.2重量份SS 4300C(甲基含氢聚硅氧烷,GE Silicones),
然后,所述涂层通过烘箱硬化。
施用至完成的剥离膜的粘合剂包含丙烯酸酯类-溶剂粘合剂,例如Rikidyne BDF 505(Sankyo Chemical),并添加有Desmodur Z 4470MPA/X(Bayer MaterialScience的脂族聚异氰酸酯),具体地,1重量份/100重量份粘合剂,按干含量计算,使用50g/m2。
将LDPE膜(Huhtamaki制造的LDPE Film 16000red 100,每单位面积重量15g/m2)层压至所述粘合剂。
在第二操作中,使该前体材料退卷并再次用压敏粘合剂涂覆,但是这次是在LDPE膜的无粘合剂的面上涂覆,然后,将所述材料卷起来以得到母卷并切割。
可将退卷胶带与剥离膜覆盖物一起在不平表面上用暴露的粘合剂面施用,而无褶皱。
实施例的性质
本发明的 本发明的
实施例1 实施例2
膜厚[mm] 0.07 0.15
在10%拉伸应变时的力[N/cm] 11 11
手撕灵敏性 ++ +
膜粘连 + 0
对比例1
制造过程如本发明的实施例1中所述,但是用Hostalen GD9555代替INFUSE D9507。
所得胶带不能无褶皱地在不平基底上施用。
对比例2
所述基础膜如本发明的实施例2中所述制造,但是用INFUSE D9507代替LD 251。
即使在膜新鲜时,也难以退卷。
对比例3
所述基础膜如本发明的实施例2中所述制造,但是用Exact0203(DexPlastomers的由乙烯和辛烯制成的软LLDPE,密度0.902g/cm3,熔体指数3g/10min,挠曲模量70MPa,晶体熔点95℃)代替LD 251和INFUSED9507。
即使在膜新鲜时,也难以退卷。
对比例4
使用的剥离膜包含Huhtamaki的LDPE膜(LDPE Film 16000 red 100)。类似于本发明的实施例1进行涂覆过程。
当所述膜停止时,它由于熔融而撕裂。在如本发明的实施例2的涂覆过程中,所述剥离膜严重收缩,并且在第一粘合剂涂覆过程后,产品具有严重皱纹。当干燥温度降低时,粘合剂涂层未充分干燥。
对比例的性质:
对比例1 对比例2 对比例3 对比例4
膜厚[mm] 0.07 0.15 0.15 0.09
在10%拉伸应变 33 1.3 5.0 11
时的力[N/cm]
手撕灵敏性 + -- -- -
膜粘连 + - - 未知
本发明剥离膜没有在剥离纸中,在取向剥离膜中或者在聚乙烯剥离膜中发现的所述缺点。
Claims (20)
1.由至少单层膜结构制成的剥离膜,其中存在基础膜,在所述基础膜上任选存在其它层,其中已经将剥离层施用至所述膜结构的至少一面,
其特征在于
所述基础膜包含密度为0.86-0.89g/cm3且晶体熔点为至少105℃的乙烯聚合物A,和密度为至少0.90g/cm3的乙烯聚合物B;
其中乙烯聚合物A包括1-辛烯作为共聚单体,基于所述聚乙烯聚合物的总量,在所述基础膜中,乙烯聚合物A的比例为20-80重量%。
2.权利要求1的剥离膜,
其特征在于
所述基础膜仅由乙烯聚合物A和B组成。
3.权利要求1的剥离膜,
其特征在于
所述基础膜包含含有乙烯的离聚物。
4.权利要求2的剥离膜,
其特征在于
所述基础膜包含含有乙烯的离聚物。
5.权利要求1-4中任一项的剥离膜,
其特征在于
所述剥离膜在机器方向上的机械性质在下列范围内:
·在10%拉伸应变时的力为3-30N/cm,
·断裂拉伸应变为50-800%,和/或
·断裂力为10-50N/cm。
6.权利要求1-4中任一项的剥离膜,
其特征在于
所述膜结构的厚度为45-200μm。
7.权利要求1-4中任一项的剥离膜,
其特征在于
在所述基础膜上,明确地存在一个共挤出外层,该共挤出外层抑制所述剥离膜的粘连。
8.权利要求1-4中任一项的剥离膜,
其特征在于
所述乙烯聚合物A的挠曲模量低于90MPa,同时所述乙烯聚合物B的挠曲模量为至少90MPa,和/或所述乙烯聚合物A和B的熔体指数分别低于10g/10min,其中熔体指数根据ISO 1133使用190℃和2.16kg测定。
9.权利要求1-4中任一项的剥离膜,
其特征在于
所述乙烯聚合物A包含C3-C10烯烃作为共聚单体,所述乙烯聚合物A的密度为0.86-0.88g/cm3,所述乙烯聚合物A的熔体指数为2-10g/10min和/或晶体熔点为至少115℃,其中熔体指数根据ISO 1133使用190℃和2.16kg测定。
10.权利要求1-4中任一项的剥离膜,
其特征在于
所述乙烯聚合物B的密度为至少0.92g/cm3。
11.权利要求1-4中任一项的剥离膜,
其特征在于
所述任选存在的两个剥离层中的至少一个包含有机硅。
12.权利要求2的剥离膜,
其特征在于
所述两种聚乙烯聚合物A和B的比率为1∶4-4∶1。
13.权利要求5的剥离膜,
其特征在于
所述剥离膜在机器方向上的机械性质在下列范围内:
·在10%拉伸应变时的力为7-18N/cm,
·断裂拉伸应变为200-400%,和/或
·断裂力为15-35N/cm。
14.权利要求6的剥离膜,
其特征在于
所述膜结构的厚度为75-125μm。
15.权利要求1-4中任一项的剥离膜,
其特征在于
在所述基础膜上,明确地在两侧上存在两个共挤出外层,该共挤出外层抑制所述剥离膜的粘连。
16.权利要求9的剥离膜,
其特征在于
所述C3-C10烯烃为1-辛烯,所述乙烯聚合物A的密度为0.86-0.87g/cm3。
17.权利要求10的剥离膜,
其特征在于
所述乙烯聚合物B的密度为至少0.94g/cm3。
18.权利要求11的剥离膜,
其特征在于
所述有机硅为乙烯基聚二甲基硅氧烷。
19.前述权利要求中的任一项的剥离膜用于覆盖在一面或两面上具有粘合性的标签、冲切胶带部分或胶带的粘合剂层的用途。
20.权利要求19的剥离膜的用途,
其特征在于
所述粘合剂层基于丙烯酸酯类。
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DE200810021842 DE102008021842A1 (de) | 2008-04-30 | 2008-04-30 | Polyolefinfolie und Verwendung derselben |
PCT/EP2009/055288 WO2009133182A1 (de) | 2008-04-30 | 2009-04-30 | Trennfolie aus polyolefin und verwendung derselben |
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CA (1) | CA2722330A1 (zh) |
DE (2) | DE102008021842A1 (zh) |
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DE102016213661A1 (de) * | 2016-07-26 | 2018-02-01 | Tesa Se | Releaseliner mit unterschiedlicher Oberflächenbeschichtung |
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- 2009-04-30 WO PCT/EP2009/055288 patent/WO2009133182A1/de active Application Filing
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DE102008021842A1 (de) | 2009-11-05 |
CN102083928A (zh) | 2011-06-01 |
PL2274391T3 (pl) | 2014-12-31 |
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JP5547177B2 (ja) | 2014-07-09 |
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