CN1659030A - 包括聚丙烯/烯烃弹性体混合物的取向膜 - Google Patents
包括聚丙烯/烯烃弹性体混合物的取向膜 Download PDFInfo
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Abstract
本发明涉及膜,包括纵向取向的聚合物膜,其由(A)熔体流动速率为约6到约30的至少一种丙烯均聚物或共聚物或它们的两种或两种以上的混合物及(B)熔体流动速率为0.5到10的烯烃弹性体制备得到。在一实施例中,膜还包括成核剂。在一实施例中,这些膜是清澈的。膜具有良好刚度和透明度,混浊度低。这些膜用于制备标签并可用作单层膜或多层膜。在一实施例中,膜是可印刷的。还公开了冲切标签,其包括由本发明挤出的纵向取向聚丙烯共聚物膜和为将所述标签贴到基体上而粘附到共聚物膜上的胶粘剂联合组成的复合物。还公开了包括标签面材材料的多层复合物,该标签面材材料具有本发明挤出的取向多层膜、与所述面材材料相结合的胶粘剂层、及防粘涂料涂覆的衬里或载体。还公开了与贴到基体如玻璃瓶的胶粘剂层相结合的本发明标签的组合。
Description
相关申请的交叉引用
本申请要求得自于2002年6月26日递交的序列号为60/391,983的美国专利临时申请、及2002年11月8日递交的序列号为60/424,883的美国专利临时申请的优先权。将这些临时申请全部列于此以作参考。
技术领域
本发明涉及制备纵向(machine-direction)取向的单层或多层膜的方法,及制造它们的方法。本发明还涉及采用这类纵向取向的聚合物膜来制造标签和其它复合物的方法。
背景技术
通过为标签或标牌提供表面或面材(facestock)材料层,标签的背面为覆盖有防粘衬里或载体的毫米级压敏胶粘剂层,而制造和分布用于标签的压敏胶粘剂用料,这很久以来就是公知的技术。衬里或载体在运输和储存期间保护胶粘剂,并使得在标签受到冲切和基材被从面材材料层剥离,直至各个标签按顺序被分配到标记线上之后,能有效地处理单个标签构成的阵列。从冲切到分配的时间中,衬里或载体保持未被切割,并可卷绕或展开,以便而储存、运输和使用载于其上的单个标签的阵列。
在许多标签应用中,希望构成面材的材料是某种聚合材料膜,该聚合材料膜能提供纸所缺乏的性质,如透明度、持久性、强度、耐水性、抗腐蚀性、光泽度以及其它性质。传统上采用了厚度大于约3密尔的面材材料,为的是确保自动贴签机的分配能力。然而,希望使面材材料减少厚度或“下调尺寸”,以便节省材料成本。而在标签厚度上的这种减少通常导致刚度下降,而且不能采用自动机械以可靠的商业上可接受的方式分配标签。
可靠分配失败的典型特点是载体跟着载体围绕剥离片,而不进行分配或者说不从载体上“离开”以便施用到基体上。据信这类失败与标签面材材料和衬里之间的分离(release)值过大有关。分离水平也跟面材的刚度有关。分配失败的特点还在于标签起皱现象,而标签起皱是在以分配速度使标签从载体转移到基体时缺乏标签刚度而造成的。由于增加线速度具有明显节约成本的优点,在许多贴签应用中,另一种特殊的需要就是要具有以高线速度来施用聚合物膜标签的能力。
近来,为实现由下调尺寸的膜而带来的成本节约,依现有技术,已建议在制备标签时采用聚合材料,包括厚度降低到约2.0密耳的聚合的双轴取向聚丙烯(“BOPP”),其相对较便宜且分配性良好。对分配来说,这类膜一般具有足够的刚度,但它们也通常具有不可接受的贴合性特性。将这种双轴取向膜施用到坚硬的基体如玻璃瓶时,由于刚度相对较大的标签往往在表面凹陷处或模制的缝隙处(这是玻璃成型过程导致的)架桥,其施用并不完全成功,这就导致出现类似于被留在内部的气泡的不希望有的外观。这种情况防碍了采用压敏胶粘剂标签来替代以前的玻璃瓶标记技术,如在玻璃瓶制造过程中直接与瓶表面结合的瓷墨。由于难闻的油墨成分和在回收过程中破碎的瓶子玻璃上的油墨造成的污染,这类瓷墨技术是不利于环境的。
其它的可用材料有未取向的聚乙烯膜和聚丙烯膜,它们也相对较便宜,还具有贴合性。然而,这两种膜都难以冲切,且在低厚度的情况下不易分配。
在某些情况下,还希望在玻璃瓶上采用清澈和基本透明的标签。目前可得到的用于标签的许多面材都十分缺乏适于这类应用的低度的不透明性和混浊性。已经建议在制备冲切标签时,采用树脂质的成膜材料,其中该树脂质的成膜材料是“软”极性添加剂(“SPA”)如乙烯-乙酸乙烯酯共聚物(EVA)与低价的油基材料的混合物,上述低价油基材料诸如为:聚丙烯、聚乙烯或者它们的组合,包括丙烯-乙烯共聚物;聚乙烯和聚丙烯相互的混合物;或者它们中的一种或两种与聚丙烯-聚乙烯共聚物的混合物。在专利号为5,186,782的美国专利中描述了挤出的热固性聚合物膜,这些挤出的热固性聚合物膜被冲切成标签,并在纵向和横向上进行了不同的处理,而在各个方向上具有不同的刚度之后,施用到可变形或可压缩的工件上。上述’782号专利中所描述的聚合物膜包括热固性单层膜,特别是聚乙烯膜,以及多层膜,而多层膜可以包括共挤出物,该共挤出物包含里层、位于共挤出物的表面侧上的表层、以及任选地位于共挤出物的内侧(与上述的表面侧相反)上的表层。一般在上述共挤出物的内侧上施加一个压敏胶粘剂层。所公开的用于表层和里层中的优选材料包括重量比范围为50/50到60/40的以下材料的物理混合物:(1)聚丙烯或丙烯和乙烯的共聚物,以及(2)乙烯-乙酸乙烯酯(EVA)。芯部材料也可以是比重范围在0.915到0.965之间的低、中、或高密度的聚乙烯。由烯烃-SPA混合物制成的膜具有过高的混浊度而不能用在玻璃瓶基体上。
本发明的纵向取向标签与由拉伸的未退火膜构成的皱缩膜形成对照。在专利号为4,581,262核4,585,679的美国专利可以找到这类皱缩膜标签的例子。皱缩的趋势导致了这类膜易于从边界收缩而留下暴露的胶粘剂。由于暴露的胶粘剂难看且易于沾上灰尘,因此暴露的胶粘剂是冲切标签应用中的一个值得注意的缺点。
发明内容
本发明涉及一种膜,其包括由以下材料制备而得的纵向取向的聚合物膜:(A)至少一种聚丙烯均聚物(propylene homopolymer)、聚丙烯共聚物(propylene copolymer),或它们的两种或两种以上的混合物,其中(A)具有的熔体流动速率为约5到约40;以及(B)一种烯烃弹性体(olefin elastomer),其中(A)与(B)是不相同的。在一个实施例中,上述膜是成核的(nucleated)。在另一实施例中,上述膜具有良好的刚度和透明性,而具有低混浊度。上述的膜用于制备标签,并可作为单层膜来使用,或用于多层膜中。在一个实施例中,上述膜是可印刷的。
本发明也描述了各种冲切标签,其包含复合物,该复合物由本发明的挤出的、纵向取向的聚丙烯共聚物膜,以及与所述共聚物膜结合以将所述标签粘结到基体上的胶粘剂层组成。
本发明也描述了多层复合物,其包括标签面材材料、胶粘剂层和防粘涂料涂覆的衬里或载体,其中所述的标签面材材料包括本发明的挤出成型的取向多层膜,而所述的粘胶层与所述面材材料相结合。本发明的标签可以与粘结到基体(如玻璃瓶)或可变形的基体(如可压缩的瓶)的粘结剂层相结合。
附图简述
图1是以本发明的单层膜制备而得的一个标签的横断面视图。
图2是本发明的一个多层膜的横断面视图。
图3是本发明的一个多层膜的横断面视图。
图4是以本发明的多层膜制备而得的一个标签的横断面视图。
图5是以本发明的多层膜制备而得的一个标签的横断面视图。
图6A是挤出膜的示意图。
图6B是热拉伸膜的示意图。
图6C是采取卷材形式的膜的示意图。
图7A是涂覆胶粘剂或防粘涂料的制造步骤示意图。
图7B是衬里或载体与面材相结合的制造步骤示意图。
图7C是冲切示意图。
图7D是将标签施用到工件上的示意图。
具体实施方式
本发明的膜是由:(A)至少一种聚丙烯均聚物、聚丙烯共聚物或它们的两种或两种以上的混合物,以及(B)至少一种烯烃弹性体获得的,条件是(A)和(B)不同。所述的膜可被用作单层膜,或是多层膜的一部分或多个部分。在一个实施例中,所述的膜是清澈的,甚至于是完全透明的。在一个实施例中,所述膜所具有的混浊度小于10%。混浊度是以BYK Gardner薄膜混浊度测量仪来测定的。本发明的取向聚丙烯膜所具有的不透明度约为10%或更低。
(A)丙烯聚合物
本发明涉及由丙烯聚合物制备而得的膜。该膜由(A)至少一种丙烯均聚物、丙烯共聚物,或它们的两种或两种以上的混合物制备得到,其中(A)所具有的熔体流动速率为从约5到约40,或从约6到约32,或从约6到约30,或从约8到约25。采用ASTM测试法D-1238测定熔体流动速率。在一个实施例中,聚合物(A)的熔体流动速率为从约8到约26,或从约10到约22。在此处或在说明书以及权利要求书中的其它地方,上述的范围和比率界限是可以合并的。
如上所述,纵向取向的膜包括(A)至少一种聚丙烯均聚物、共聚物、或它们的两种或两种以上的混合物。在一个实施例中,(A)通常占膜中聚合物重量的约40%到约98%,或约45%到约90%,或约50%到约85%,或约55%到约80%。在一个实施例中,(A)是具有上述熔体流动速率的两种或两种以上聚合物的混合物。该混合物可包括两种或两种以上丙烯均聚物的混合物、一种丙烯均聚物和一种丙烯共聚物的混合物、两种或两种以上丙烯均聚物和一种丙烯共聚物的混合物,或者两种或两种以上丙烯共聚物和一种丙烯均聚物的混合物。
在一个实施例中,丙烯膜(A)可以是成核的。这些膜可包含一种或多种成核剂。在一个特别有用的实施例中,成核剂是被混入到丙烯聚合物(A)中的。各种成核剂都可并入本发明的膜制剂中,且加入的成核剂的量应足以实现对晶体结构的所需改进,同时不对膜的所需光学性质带来负面影响。通常希望利用成核剂以改进晶体结构,和提供大量的相当小的晶体或球粒从而改进膜的透明性(清澈性)。加入膜制剂中的成核剂的量应不会对膜的清澈性造成有害作用。并入本发明的膜制剂中的成核剂的量通常相当少,其范围为约500,或约750或约850ppm。所添加的成核剂的量最多为约5000,或约3000,或约1000。
迄今为止,已被用于聚合物膜的成核剂包括矿物成核剂和有机成核剂。矿物成核剂的例子包括碳黑、硅石、高岭土和滑石。已经建议用于聚烯烃膜中的有机成核试剂包括脂肪族单-基或双-基酸或芳烷基酸的盐,如琥珀酸钠、戊二酸钠、己酸钠、4-甲基戊酸钠、苯乙酸铝,以及肉桂酸钠。芳香族和酯环族羧酸碱金属盐和铝盐如苯甲酸铝、苯甲酸钠或钾、β-萘酚钠、苯甲酸锂和叔丁基苯甲酸铝也都是有用的有机成核剂。Wijga在专利号为3,207,735、3,207,736和3,207,738的美国专利中,以及Wales在专利号为3,207,737和3,207,739的美国专利中揭示了脂肪族、酯环族以及芳香族羧酸、二羧酸或更高的多羧酸的相应酸酐和盐都是聚烯烃的有效成核剂(所有这些专利都在1966年9月21日获得专利授权)。他们还进一步指出苯甲酸型化合物,特别是苯甲酸钠,是成核剂的最佳实施例。
在一个实施例中,成核剂为山梨糖醇衍生物或有机磷酸酯。取代的山梨糖醇衍生物如其中烷基基团含有约2到约18个碳原子的二(烷基苯亚甲基)山梨糖醇是有用的成核剂。更具体地说,山梨糖醇衍生物如1,3,2,4-二-对-甲基苯亚甲基山梨糖醇和1,3,2,4-二-对-甲基苯亚甲基山梨糖醇是聚丙烯的有效成核剂。有用的成核剂可从多个来源、通过商业渠道获得。Millad 8C-41-10、Millad 3988和Millad 3905都是可从Milliken Chemical Co.购得的成核剂。
其它的山梨糖醇和木糖醇的缩醛是用于聚烯烃和其它热塑性塑料的典型成核剂。二苯亚甲基山梨糖醇(DBS)是在Hamada等获得的专利号为4,016,118的美国专利中首先公开的用于聚烯烃的有效成核剂和澄清剂。在此之后,已公开了大量的山梨糖醇和木糖醇的缩醛。代表性的美国专利包括:Kawai等的专利号为4,314,039的美国专利所公开的二(烷基苯亚甲基)山梨糖醇;Mahaffey,Jr.的专利号为4,371,645的美国专利中所公开的具有至少一个氯或溴取代基的山梨糖醇的二缩醛;Kobayashi等的专利号为4,532,280的美国专利中所公开的二(甲基或乙基取代的苯亚甲基)山梨糖醇;Rekers的专利号为5,049,605的美国专利中所公开的包括形成碳环的取代基的二(3,4-二烷基苯亚甲基)山梨糖醇。将所有这些专利列于此以作参考。
其它种类的成核剂在Nakahara等获得的专利号为4,463,113的美国专利中做了描述,在该专利中公开的是以环状二-苯酚磷酸酯作为聚烯烃树脂的成核剂和澄清剂。此后Kimura等在专利号为5,342,868的美国专利中描述了向基础的环状有机磷酸酯的多价金属盐中加入羧酸碱金属盐可进一步提高此类添加剂的澄清效果。基于这类技术的化合物以商品名NA-11和NA-21出售。将这些专利合并于此以作参考。
可从多个来源通过商业渠道获得有用的多种丙烯均聚物。下面表I中列出和描述了一些有用的均聚物。
表I
商业化的丙烯均聚物
商业化名称5390NSE66R36223576XMoplen HP400NP4G4K-038*9074*MED | 公司Dow ChemicalDow ChemicalAtofinaAtofinaBasellHuntsmanExxon Mobil | 熔体流动速率g/10min12.08.812.09.012.01224 | 密度(g/cm3)0.900.900.900.900.900.900.90 |
*含有成核剂
在另一实施例中,(A)可为丙烯共聚物。丙烯共聚物通常包括丙烯和以重量计最多为40wt%的至少一种α-烯烃的聚合物,所述的至少一种α-烯烃选自于乙烯和含有4到约12个,或4到约8个碳原子的α-烯烃。有用的α-烯烃的例子包括乙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯,以及1-辛烯。在一个实施例中,本发明所使用的丙烯聚合物包括无规共聚物和嵌段共聚物,但通常无规共聚物特别有用。在一个实施例中,膜中没有抗冲共聚物。可采用两种或两种以上的丙烯共聚物的混合物以及丙烯共聚物和丙烯均聚物的混合物。
在一个实施例中,上述丙烯共聚物为丙烯-乙烯共聚物,其中乙烯含量为约0.2wt%到约10wt%。在另一实施例中,乙烯含量为约3wt%到约10wt%,或为约3wt%到约6wt%。对于丙烯-1-丁烯共聚物,有用的1-丁烯含量最多达约15wt%。在一个实施例中,1-丁烯含量的范围通常为约3wt%到约15wt%,而在其它实施例中,这一范围可以为约5wt%到约15wt%。丙烯-1-己烯共聚物可最多含有约35wt%的1-己烯。在一个实施例中,1-己烯的重量最多达25wt%。本发明所采用的丙烯-1-辛烯共聚物可最多含有40wt%的1-辛烯。更常见的是,丙烯-1-辛烯共聚物可最多含有约20wt%的1-辛烯。
下面的表II中列出了一些有用的可通过商业渠道获得的丙烯共聚物。
表II
商业化的丙烯共聚物
商业化名称DS6D21KB4560KB4586KB49869433*13T25AP5M4K-046*P5M5K-047 | 公司Dow ChemicalBPAmocoBPAmocoBPAmocoBPAmocoHunstmanHunstmanHunstman | 熔体流动速率g/10min8.010103012251020 |
*含有成核剂
在一个实施例中,聚丙烯共聚物包括上述用于丙烯均聚物的成核剂。
用于制造本发明的膜面材的丙烯共聚物可用本领域技术人员公知的技术来制备,而且许多这样的共聚物是可通过商业渠道获得的。例如,用于本发明的共聚物可采用单点茂金属催化剂使丙烯与α-烯烃如乙烯或1-丁烯进行共聚合而获得。在一个实施例中,丙烯聚合物(A)中不含抗静电剂。
(B)烯烃弹性体
如本说明书所述,膜的组合物包括(B)至少一种烯烃弹性体。烯烃弹性体称为塑性体。在一个实施例中,烯烃弹性体的熔体流动速率为约0到约40,或为约3到约35,或为约5到约25g/10min。上述熔体流动速率是以在190℃下进行的ASTM测试法D-1238来测定的。在一个实施例中,(B)的熔体流动速率的范围为从约1到约25,或从约2到约10g/10min。所提供的烯烃弹性体的量典型地占膜中聚合物量的约2%到约55%,或约10%到约50%,或约15%到约45%。
在一种实施方式中,烯烃弹性体(B)典型具有的分子量分布指数(Mw/Mn)为约1.5到2.4,其中Mw是重均分子量,而Mn是数均分子量。在一个实施例中,烯烃弹性体所具有的密度为约0.82到约0.98,或为约0.84到0.97,或为约0.86到约0.91g/cc,或为约0.87g/cc到约0.91g/cc。在另一实施例中,烯烃弹性体的分子量为约5000到约50000,或为约20000到约30000。
烯烃弹性体包括既表现出热塑性又表现出弹性体特性的聚烯烃聚合物。这类聚合物包括乙烯或丙烯与α-烯烃的共聚物和三元共聚物。上述聚合物典型地包括约2wt%到约30wt%、或为约5wt%到约25wt%、或为约10wt%到约20wt%的α-烯烃。上文中已对α-烯烃进行了描述。α-烯烃包括1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯,以及1-十二碳烯。特别有用的α-烯烃包括1-丁烯和1-己烯。烯烃弹性体包括但不限于乙烯-丁烯共聚物、乙烯-辛烯共聚物、乙烯-己烯共聚物,以及乙烯-己烯-丁烯三元共聚物及其混合物。
在另一实施例中,可用于本发明的烯烃弹性体包括乙烯和至少一种C3-C20α-烯烃或C4-C8α-烯烃的共聚物,而且其中C3-C20α-烯烃或C4-C8α-烯烃的含量为约5到约32mol%,或为约7到约22mol%,或为约9到约18mol%。例如,所述共聚物可利用单点茂金属催化剂使乙烯或丙烯与α-烯烃如1-丁烯进行共聚合反应而获得。这样的共聚物可从Exxon Mobil Chemical Company、Basell和Dow Chemical Company获得。另一种有用的聚丙烯和1-丁烯共聚物可从Basel以商品名EP3C30HF购得。这一共聚物具有14%的丁烯,而熔体流动指数约为5.5g/10min。
烯烃弹性体的非限定性例子包括直链的乙烯-丁烯共聚物,例如:所具有的密度为约0.905gms/cc(ASTM D-1505),而熔融指数为4.5g/10min(ASTM D-1238)的EXACT 3024;所具有的密度为约0.900gms/cc(ASTM D-1505),而熔融指数为3.5g/10min(ASTM D-1238)的EXACT 3027;所具有的密度为约0.888gms/cc(ASTM D-1505),而熔融指数为2.2g/10min(ASTM D-1238)的EXACT 4011;所具有的密度为约0.873gms/cc(ASTM D-1505),而熔融指数为4.5g/10min(ASTMD-1238)的EXACT 4049;以及所具有的密度为约0.895gms/cc(ASTMD-1505),而熔融指数为3.5g/10min(ASTM D-1238)的EXACT 4150。有用的EXACT塑性体的其它非限定性例子有EXACT 3017和EXACT4053。也可采用诸如乙烯、丁烯和己烯这样的三元共聚物。所有上述的EXACT系列塑性体都可从EXXON Chemical Co.购得。
三元共聚物的例子有:EXXON Chemical Co.的Exact 3006(一种密度为0.910g/cm3(g/cc)而M.F.I为1.2g/10min(g/10’)的乙烯-丁烯-己烯三元共聚物)、Exact 3016(一种密度为0.910g/cm3(g/cc)而M.F.I为4.5g/10min(g/10’)的乙烯-丁烯-己烯三元共聚物)、Exact 3033(一种密度为0.900g/cm3(g/cc)而M.F.I为1.2g/10min(g/10’)的乙烯-丁烯-己烯三元共聚物)、Exact 3034(一种密度为0.900g/cm3(g/cc)而M.F.I为3.5g/10min(g/10’)的乙烯-丁烯-己烯三元共聚物);Dow Affinity PL 1840(一种乙烯-丙烯-丁烯三元共聚物);Dow Affinity PL 1845(一种乙烯-丙烯-丁烯三元共聚物);Dow Affinity PL 1850(一种乙烯-丙烯-丁烯三元共聚物);以及Exxon Mobil ZCE 2005(一种乙烯-丙烯-丁烯三元共聚物)。
在一个实施例中,EXACT塑性体所具有的分子量分布指数(Mw/Mn)独立地为约1.5到约2.4,其中Mw是重均分子量,而Mn为数均分子量;密度为约0.86到约0.91g/cc,或为约0.87g/cc到约0.91g/cc;分子量为约5,000到约50,000,或为约20,000到约30,000;熔点约为140-220F.;以及用ASTM D-1238在E条件下测定的熔体流动指数,其高于约0.50g/10mins,或为约1-10g/10mins。
本发明也可采用例如Dow Chemical Co.以商品名Affinity出售的那些塑性体。这些塑性体被认为是按照专利号为5,272,236的美国专利制备的,将该专利的指导内容全部引入于此以作参考。在一个实施例中,这些塑性体基本为直链聚合物,该直链聚合物所具有的密度按照ASTM D-792测定为约0.85gms/cc到约0.97gms/cc;熔融指数(“MI”)为约0.01gms/10min到约1000gms/min;熔体流动速率(I10/I2)为约7到约20,其中I10是按照ASTM D-1238(190/10)测定的,而I2则是按照ASTM D-1238(190/2.16)测定的;并且分子量分布指数Mw/Mn小于5,或小于约3.5,或为约1.5到约2.5之间。这些塑性体包括C2-C20烯烃如乙烯、丙烯、4-甲基-1-戊烯等等的均聚物,或者它们也可以是乙烯与至少一种C3-C20α-烯烃和/或C2-C20炔属不饱和单体和/或C4-C18α-烯烃的三元共聚物。这些塑性体通常具有聚合物骨架,该聚合物骨架为未取代的,或者是每1000个碳上最多被3个长链支链取代。此处所采用的长链支链是指链长至少为约6个碳,该链长以上的长度不能用13C核磁共振光谱鉴别出来。有用的Affinity塑性体的特征是饱和的乙烯-辛烯骨架,窄分子量分布指数Mw/Mn约为2,以及窄结晶度水平。这些塑性体也和颜料、增亮度剂、填料(如碳黑、碳酸钙和硅石),以及增塑剂(如石蜡工艺用油和脂环烃工艺用油)相容。本发明可采用其它能够通过商业渠道获得的塑性体,包括Mitsui制造的塑性体。
在一个实施例中,根据专利号为5,272,236的美国专利所制得的塑性体的分子量分布指数(Mw/Mn)约为2.0。这些塑性体的非限定性例子包括:所具有的密度约为0.897gms/cc,而熔体流动指数约为0.5g/10min的Affinity PF1140;所具有的密度约为0.90gms/cc,而熔融指数约为1g/10min的Affinity PF1146;所具有的密度约为0.902gms/cc,而熔融指数约为1.0g/10min的Affinity PF1880;所具有的密度约为0.87gms/cc,而熔融指数约为1g/10min的Affinity EG8100;所具有的密度约为0.868gms/cc,而熔融指数约为0.5g/10min的Affinity EG8150;所具有的密度约为0.87gms/cc,而熔融指数约为5g/10min的AffinityEG8200;以及所具有的密度约为0.87gms/cc,而熔融指数约为5g/10min的Affinity KC8552。
在一个实施例中,所述烯烃弹性体包括以单点茂金属催化剂形成的那些烯烃弹性体,其中上述单点茂金属催化剂例如为欧洲专利EP29368、美国专利第4,752,597号、美国专利第4,808,561号、及美国专利第4,937,299号中所公开的那些单点茂金属催化剂,在此将这些文献指导的内容引入以作参考。如本领域所公知的,可采用高压处理,以茂金属催化反应,通过使乙烯和其它单体如丁烯-1、己烯-1、辛烯-1、及4-甲基-1-戊烯在存在包括环戊二烯基-过渡金属化合物和铝氧烷的催化系统的条件下进行聚合而制备。
(C)成核剂
在一个实施例中,所述的膜包括成核剂。上文中已经对成核剂进行了描述。成核剂可加入到本发明的多层膜中的任一层或所有层中。如上所述,成核剂可加入到丙烯聚合物(A)中,或作为制剂的一种单独成分用于制造膜。成核剂也可与丙烯聚合物(A)或烯烃弹性体(B)预混合,以及作为膜制剂的一种单独成分来加入。通常,被加入到本发明膜制剂中的成核剂的总量一般相当小,其范围约为500或1000到3000或5000ppm。与(A)或(B)预混合的成核剂的用量可在两者之间均匀分配或不均匀分配,以及作为单独的组分(C)而存在。
本发明的单层或多层膜也可包含抗粘连剂。向膜制剂中加入抗粘连剂减少了膜在卷绕过程中发生粘连的可能,调节了膜的滑动性和抗静电性,并能从卷轴平滑地展开。本发明的膜制剂中可包括现有技术所公开的任何抗粘连剂,该抗粘连剂可用作改进聚合物膜特性、尤其是烯烃聚合物膜特性的有用添加剂。平均粒度为约2微米或更小的硅石可被用于这一目的,且仅需要少量(例如1000到5000ppm)的细硅石。若干基于合成硅石的抗粘连剂可从美国俄亥俄州Akon的A.Schulman,Inc.购得,其商品名为Polybatch。这些材料是防粘连的母料,且包括由丙烯均聚物或共聚物以及合成硅石组成的自由流动的颗粒。例如,Polybatch ABPP-05包括处于丙烯均聚物中的5%合成硅石;ABPP-10包括处于丙烯均聚物中的10%合成硅石;而ABPP-05SC包括5%合成硅石和无规丙烯共聚物。当在本发明的多层膜的制备中采用抗粘连剂时,通常只将抗粘连剂加入到表层的制剂中。有用的抗粘连剂是Ampacet的Seablock 1和Seablock 4。
在另一个实施例中,膜制剂包括至少一种加工助剂。加工助剂的作用是利于挤出成型。这些加工助剂包括六氟化碳聚合物。从商业渠道获得的可采用的加工助剂的一个例子是Ampacet 10919,它是Ampacet Corporation作为六氟化碳聚合物推出的一个产品。有用的加工助剂的另一个例子是Ampacet 401198。加工助剂的典型使用浓度最多为约1.5wt%,或从约0.5wt%到约1.2wt%。在另一实施例中,加工助剂的用量最多为约0.25wt%,在又一个实施例中则为约0.03wt%到约0.15wt%。
可采用本领域技术人员公知的方法制造膜。例如可采用挤出成型来制造膜。典型的是,在250到约500°F,或为约300到约500°F之间的温度下挤出膜。一种用于制造膜的有用方法是在450°F下进行挤出成型。
下列实例涉及可用于制造聚合物膜的聚合物组合物。在没有另外指出的情况下,用量都以重量份为单位,温度都以℃为单位,而压力是大气压。
表III
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | |
Huntsman丙烯均聚物P4G4K-038#(MFR12) | 50 | - | - | - | - | 60 | 65 | - | - | - | 15 | 65 |
Huntsman丙烯均聚物P5M4K-046#(MFR10) | - | 65 | - | - | 90 | - | - | - | - | - | - | - |
BP Amoco丙烯共聚物KB4986(MFR30) | - | - | 55 | - | - | - | - | 65 | - | 52 | - | - |
Dow丙烯共聚物D56D21(MFR8) | - | - | - | 80 | - | - | - | - | 65 | - | 50 | |
Exact 3025烯烃弹性体(MFI1.2) | - | - | 45 | - | - | - | 10 | - | - | - | - | 20 |
Exact 4049烯烃弹性体(MFI4.5) | - | 35 | - | - | 10 | 40 | - | 35 | 35 | - | 15 | |
Affinity 8500烯烃弹性体(MFI5.0) | 50 | - | - | 20 | - | - | 25 | - | - | - | 35 | - |
苯甲酸钠成核剂 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
硬脂酸钙 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
#:膜中不含抗静电剂
表III
13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | |
Huntsman丙烯均聚物P4G4K-038#(MFR12) | 25 | - | - | 88 | - | 60 | - | - | 15 | 35 |
Huntsman丙烯均聚物P5M4K-046#(MFR10) | - | 65 | - | - | 87.5 | - | - | 60 | - | 25 |
BP Amoco丙烯共聚物9433(MFR12) | 25 | - | 54.5 | - | - | - | 65 | - | 60 | |
Exact 3025烯烃弹性体(MFI1.2) | - | 15 | 45 | - | - | 37.5 | - | - | - | 20 |
Exact 4049烯烃弹性体(MFI4.5) | - | 20 | - | - | 10 | - | 42.5 | 37.5 | - | 17.5 |
Affinity 8500烯烃弹性体(MFI5.0) | 50 | - | - | 20 | - | - | - | - | 37.5 | - |
Miladd 3988(成核剂)& | 无 | 无 | 有 | 无 | 无 | 无 | 无 | 无 | 无 | 无 |
Polybatch ABPP 05SC | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
加工助剂 | 0.5 | 0.5 | 0.5 | 0 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
#:膜中不含抗静电剂
&:浓度为1900ppm的成核剂作为添加成分(未预混合于树脂中)
表III
23 | 24 | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | |
Huntsman丙烯均聚物P4G4K-038#(MFR12) | 25 | - | - | 88 | - | - | - | - | 15 | |
Huntsman丙烯均聚物P5M4K-046#(MFR10) | - | 65 | - | - | 87.5 | 65 | - | 65 | - | 35 |
Exact3025烯烃弹性体(MFI1.2) | - | 15 | 45 | - | - | - | - | - | - | 25 |
Exact4151烯烃弹性体(MFI2.2) | 50 | 20 | - | 20 | 10 | 35 | 42.5 | 35 | 37.5 | 17.5 |
Miladd3988(成核剂)& | 无 | 无 | 有 | 无 | 无 | 有 | 有 | 无 | 无 | 无 |
Polybatch ABPP 05SC | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
加工助剂 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
#:膜中不含抗静电剂
&:浓度为1900ppm的成核剂作为添加成分(未预混合于树脂中)
膜和结构
如本说明书所描述的,以上的膜可被单独地用作单层膜,或与其它的膜结合而制成多层膜结构。在多层膜结构中,整个结构都可由本发明的膜制备。在另一实施例中,本发明的膜构成多层膜结构中的至少一层。在另一个实施例中,本发明的膜构成多层膜结构中的至少一个表层。
在一个实施例中,构成纵向取向膜的聚合物仅是烃类聚合物。在另一实施例中,膜的组合物包括低于1%的极性组分,或者是不含极性组分。极性组分是由极性单体衍生得到的,并且包括丙烯酸酯、乙酸乙烯酯,等等。在一个实施例中,所述的膜不是从乙酸乙烯酯衍生得到的。在另一实施例中,所述的膜中不含由氯乙烯、丙烯酸或甲基丙烯酸或其酯类、丙烯腈、或丙烯酰胺衍生得到的聚合物。在又一个实施例中,芯部层包括低于5%、或低于1%的填料,或者是不含填料。在另一个实施例中,膜基本不含空隙。
根据膜的预期应用,膜的厚度范围为约0.5密尔(12.5微米)到约10密尔(250微米)。然而,本发明的膜的更常用厚度为小于7密尔(178微米)。对制造标签来说,特别有用的膜厚度为约1到约6密尔(25到150微米),更常用的为约1到约4密尔(25到100微米),而最常用的则为约1.5到约2.5密尔(37.5到62.5微米)。这些膜是纵向取向的膜。这些膜的取向方式是本领域的技术人员所公知的,并在本说明书中做了描述。典型的是,膜的拉伸比为9或更小,或介于2到8之间,或者是约为4到7。在一个实施例中,膜以大约7或更小的拉伸比进行纵向取向,通常所具有的总厚度(厚度)为约4密尔以下,而更常见的是厚度为约3密尔或更薄,例如厚度范围为约2.0到约3.0密尔。
如本说明书所描述的,可在标签结构中采用膜。对于可变形的基体如可压缩的和半可压缩的瓶,这些标签是特别有用的。标签会贴合基体的表面,在施用过程中几乎不形成气泡。标签具有良好的胶粘特性,并且通常不会发生剥离现象。图1举例说明了采用本发明的单层膜和胶粘剂的标签的横截面。标签10具有膜层11,膜层11粘附在胶粘剂层12上。可选择的是,胶粘剂层12可分离地附着在衬里或载体层13上。衬里或载体层13是可选择的。当标签是模内标签时,衬里层13将不存在。
胶粘剂层12可直接涂覆在膜层11的下表面上,或者可从与膜结合的衬里13转移胶粘剂。典型的是,胶粘剂层所具有的厚度范围为约0.1到约2密尔(2.5到50微米)。适用的胶粘剂是本领域通常采用的那些胶粘剂。一般来说,这些胶粘剂包括压敏胶粘剂、热活化胶粘剂、热熔胶粘剂,等等。压敏胶粘剂尤其有用。这些胶粘剂包括丙烯酸类胶粘剂以及其它的弹性体如天然橡胶或含有苯乙烯、丁二烯、丙烯腈、异戊二烯和异丁烯的聚合物或共聚物的合成橡胶。压敏胶粘剂包括丙烯酸基的、硅基的、和橡胶基的压敏胶粘剂。压敏胶粘剂在本领域中是公知的,且任何公知的胶粘剂都可与本发明的面材一起使用。在一个实施例中,压敏胶粘剂是基于丙烯酸酯类如丙烯酸2-乙基己基酯与极性单体如丙烯酸的共聚物。
在以根据本发明的单层和多层膜来制造标签用料的过程中,可以设置衬里或载体用料。衬里或载体用料可包括例如列于本说明书中以作参考的专利号为4,713,273的美国专利中所公开方法制成的多层衬里,或者可以是常规的衬里或载体,由卷材形式的单纸膜层组成。如果以前尚未设置防粘涂料,而衬里或载体本身并不包括固有的能在其胶粘剂接触面上产生防粘表面的组分,则可采用防粘涂料(如硅氧烷)涂覆衬里或载体。在施涂防粘涂料的情况下,采用任何合适的方法,在施涂之后使防粘涂料进行干燥和固化。
防粘衬里或载体的防粘表面可涂覆一层压敏胶粘剂,以便随后将该压敏胶粘剂转移到采用了该衬里或载体的标签用料上。当标签用料和衬里或载体结合时,胶粘剂便结合到膜上。之后,取掉衬里或载体而暴露出胶粘剂,胶粘剂便与膜保持永久性结合。
与压敏胶粘剂不同的是,在一些应用中,胶粘剂层可以是在模内标签中应用的热活化胶粘剂或热熔胶粘剂。如果胶粘剂是热活化胶粘剂或热熔胶粘剂,则无需像采用压敏胶粘剂时所要求的那样,提供具有固有防粘性的防粘衬里。
在另一个实施例中,本发明的膜为多层膜结构中的至少一层。该膜可为内部层,如芯部层、基层或里层,或者构成分界层,如用于分隔两个芯部层的层。膜还可以是通常被称为表层的外部层。当然应该理解,本发明的膜可既包括多层结构的内部层,又包括其外部层。
参见图2,图中举例说明了多层膜20。多层膜20具有包括上表面和下表面的基层或称芯部层21。表层22覆盖基层21的上表面。如本领域技术人员所公知的,可通过共挤出层21和22,或者通过将各层叠压在一起,而形成多层膜20。从合适的公知类型的共挤压模同时挤出,可形成图2的共挤出层,这些共挤出层以一致永久结合的状态相互粘附,从而提供了单一的共挤出物。
与一个或多个表层相比,基层或里层相对较厚。因此,里层的厚度可为每个表层厚度的约2到20倍。如图2中表示的两层膜的厚度比的例子包括90∶10、85∶15、80∶20、70∶30等等。在一个实施例中,当芯部层具有一个表层时,该表层的厚度占多层膜厚度的约0.5%到约20%,或约1%到约15%,或约2%到约12%。
图3举例说明了多层膜30,多层膜30具有包括上表面和下表面的基层或称芯部层31。表层32覆盖了基层31的上表面。这一多层膜可制备成如图2所示的两层膜。如图2所示的三层膜的厚度比包括:5∶90∶5,10∶80∶10,15∶70∶15,20∶60∶20,等等。两个表层的厚度不一定必须相等。当芯部层具有两个表层时,表层的厚度占多层膜厚度的约2%到约35%,或者约5%到约25%,或者约8%到约20%。
上述多层膜可用在标签结构中。参见图4,标签40具有包括上表面和下表面的基层或里层41。基层41的上表面被表层42所覆盖。基层41的下表面则粘附到胶粘剂层43上,任选地,该胶粘剂层43又可分离地附着于衬里44上。举例来说,如果标签是模内标签,则衬里44便不存在。
参见图5,标签50具有基层或称里层51,而基层或称里层51带有上表面和下表面。基层51的上表面被表层52所覆盖,而基层51的下表面则被表层53所覆盖。表层53粘附于胶粘剂层54上,而任选地,该胶粘剂层54又可分离地附着于衬里55上。举例来说,如果标签是模内标签,则衬里55便不存在。
如此处所述,标签层和膜层可由上述的膜组合物构成。在一个实施例中,基层或里层为成核的丙烯膜。
在另一实施例中,多层膜的表层为上述膜的那些表层。在这一实施例中,基层或里层包括密度在0.94g/cm3以上的聚乙烯、丙烯均聚物或共聚物,或者丙烯均聚物和至少一种丙烯共聚物的混合物。在一个实施例中,基层中的均聚物和共聚物的混合物可包括约5wt%到约95wt%的均聚物以及相应的约95wt%到约5wt%的共聚物。如此处所描述的既可单独使用又可与丙烯共聚物联合使用而作为基础材料的丙烯均聚物包括多种丙烯均聚物,如采用ASTM测试法D1238,在L条件下测定的熔体流动速率(MFR)为约1到约20的均聚物。上文中已经对丙烯均聚物进行了描述。在一个实施例中,MFRs至少约为4(或至少约为8)的丙烯均聚物是特别有用的,且其提供了具有改善的冲切性质的面材。有用的丙烯均聚物的特征可也在于其密度范围为约0.88到约0.92g/cm3。
在一个实施例中,芯部包括密度在0.94g/cm3以上的聚乙烯、丙烯均聚物或共聚物,或者丙烯均聚物和至少一种丙烯共聚物的混合物,以及约1wt%到约15wt%、或约3wt%到约10wt%、或约4wt%到约7wt%的一种或多种上述的烯烃弹性体。
可通过商业渠道从各个来源获得多种有用的丙烯均聚物。下面的表IV中列举并描述了一些有用的均聚物。
表IV
商业化的丙烯均聚物
商业化名称5A97Z9470Z9470HB3272 | 公司Dow ChemicalAtofinaAtofinaAtofina | 熔体流动指数g/10min3.95.05.01.8 | 密度(g/cm3)0.900.890.890.89 |
上文已经描述过用于芯部的丙烯共聚物。在一个实施例中,可用于基层或里层的丙烯共聚物通常包括丙烯共聚物,以及最多达40wt%的至少一种α-烯烃,该α-烯烃选自于乙烯和含有4到约12个碳原子、或约4到约8个碳原子的α-烯烃。有用的α-烯烃的例子包括乙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯,以及1-辛烯。更常见的是,用于本发明的丙烯共聚物包括无规和嵌段的共聚物,但通常来说无规共聚物特别有用。共聚物的混合物以及共聚物和丙烯均聚物的混合物可用作基层的组分。在一个实施例中,乙烯的含量为约0.2wt%到约10wt%。在一个实施例中,乙烯的含量为约3wt%到约10wt%,或从约3wt%到6wt%。对于丙烯-1-丁烯共聚物,有用的1-丁烯的含量最多为约15wt%。在一个实施例中,1-丁烯的含量一般可为约3wt%至最多为约15wt%,在另一实施例中,这一范围可为约5wt%到约15wt%。用于本发明的丙烯-1-辛烯共聚物可包含至多为约40wt%的1-辛烯。更常见的是,丙烯-1-辛烯共聚物将含有至多达约20wt%的1-辛烯。
用于制造本发明的膜面材的丙烯共聚物可借助本领域技术人员所公知的技术制备得到,且许多这类共聚物可以通过商业渠道获得。例如,用于本发明的共聚物可采用单点茂金属催化剂使丙烯与α-烯烃如乙烯或1-丁烯进行共聚合而获得。在下面的表V中列出了一些可从商业渠道获得的有用丙烯共聚物。用于本发明的丙烯共聚物所具有的MFR值为约1到约20,或为约1到约12。当采用MFRs至少约为4的丙烯共聚物时,可获得改善的冲切特性。
表V
商业化的丙烯共聚物
商业化名称DS4D05DS6D20DS6D81SR4-189 | 来源Dow ChemicalDow ChemicalDow ChemicalDow Chemical | %乙烯-3.25.5- | %1-丁烯14--8 | 熔体流动速率(g/10mins)6.51.95.05.7 | 密度(g/cm3)0.8900.8900.900.90 |
在本发明的另一实施例中,基层可包括最终沿纵向来取向的高密度聚乙烯。特别有用的是密度在约0.940g/cm3以上而至多达约0.980g/cm3,并已经沿纵向而拉伸取向的聚乙烯膜。拉伸比的范围可为约2∶1到约9∶1。在这一实施例中,任选地存在有介于基层和第一表层之间的粘结层,原因是这两层都包括聚乙烯。
基层可包含用以改进基层和面材性质的其它添加剂。在一个实施例中,芯部层包含至少一种颜料。例如,可包括在基层中的着色剂有TiO2,CaCO3等等。例如,少量TiO2的存在导致产生白色的面材。可采用的颜料包括金红石型和锐钛型晶体结构的二氧化钛。在一个实施例中,颜料以含有颜料和树脂载体的浓缩物的形式加入到芯部层材料中。该浓缩物举例来说包括约20wt%到约80wt%的颜料,约20wt%到约80wt%的树脂载体。该树脂载体可为所具有的熔点范围为约100℃到约265℃的任何热塑性聚合物。例子包括有聚乙烯、聚丙烯、聚丁烯、聚酯、尼龙,等等。在一个实施例中,所采用的二氧化钛浓缩物由约30wt%到70wt%的聚丙烯和约70wt%到约30wt%的二氧化钛的混合物组成。可由商业途径获得的能够使用的一种颜料浓缩物的例子,是可从A.Schulman Inc.按照商品名PolyBatch White P8555 SD购得的产品,其被鉴定为一种聚丙烯均聚物载体树脂中涂覆金红石型二氧化钛的浓度为50wt%的白色浓缩物。另一个例子是Ampacet 110233,它是Ampacet Corporation的产品,鉴定为含有50%金红石型TiO2和50%低密度聚乙烯的TiO2浓缩物。再一个例子是Ampacet 110069,它是直链低密度聚乙烯(熔融指数为1)中二氧化钛浓度为70%的白色浓缩物。可采用其它的颜色浓缩物以提供其它的颜色。在一个实施例中,对于2.5密尔的膜,膜所具有的透明度为约80到约90,或为约81到约88,或为约82到约85。
基层中还可包括抗粘连剂。上文中已经描述过抗粘连剂。芯部层可包括上述成核剂,用于处在类似处理层次上的膜组合物。
可借助图6A至图6C中所描述和示例的一般方法,通过挤出一批所需的丙烯共聚物,或通过共挤出用于多层膜的各层的几批成膜树脂,而形成共挤出物,进而制备得到纵向取向的挤出膜。
尽管图6A举例说明了经过流延膜挤制(即经过扁平模头)进行挤出,但可经过吹塑薄膜挤制(即通过圆型模头挤出)、然后经过辊子之间的吹塑台(blown stock)的公知方式,挤出或共挤出一层或多层的单批料或多批料。
对于这一实施例,可制备多批料,以便如图6A所示意性表明的,通过挤出模头70和平膜流延而挤出或共挤出。如上所述,用于表层的树脂料包括本说明书中所述的丙烯共聚物和烯烃弹性体。用于里层的树脂料包括如上所述的丙烯均聚物和丙烯共聚物。挤出的膜首先落在第一个冷却辊191上,然后继续环绕到第二个冷却辊192上,然后由脱离辊193拉向前方。
对于适当地分配标签来说,膜的刚度是重要的。图6B举例说明了热拉伸位置,在该位置处,扁平料的拉伸模量M在纵向上增加,典型的拉伸比为9或更小,或为3到7之间,或为约4到6。膜的MD拉伸模量的增加有利于尺寸稳定性和良好的印刷定位。在传送过经过预热的辊子201和202(它们使料软化)之后,被软化的料随后在一对取向辊205和206之间受到拉伸,后者以数倍于预热辊的旋转速度的速度而旋转,相应的拉伸比举例来说为5.5∶1或6.5∶1。上述的料然后被传送到退火辊209和210上,而在此处受到退火或热定形,最后被传送至冷却辊212上从而完成热拉伸操作。然后该料被制成图6C所示的卷材形式。在预热步骤中的时间比退火步骤中的时间长出1.5到4倍,或2到3倍。在一个实施例中,在230°F、或在高于240°F或高于245°F的温度下对膜进行取向。退火温度高于245°F,或高于250°F,或高于255°F。有益的退火温度为260°F。
通过上述一般步骤制得的纵向取向的单层和多层膜的刚度在纵向上应该至少为约10,并可高达100Gurley。在一个实施例中,上述的膜的特征是在纵向上具有的Gurley刚度为约10到约60,或为约10到约40。刚度是按照TAPPI Gurley刚度测试法T 543pm来测定的。在一个实施例中,横向的拉伸模量基本小于纵向的拉伸模量。在另一实施例中,横向的拉伸模量比纵向拉伸模量约小0.75倍。
在一个实施例中,横向(CD)伸长率基本大于综向(MD)伸长率。此外,本发明的膜的CD伸长率将大于30%,或50%,或大于100%,甚至是大于300%。
由上述的根据本发明的膜来制造标签用料的过程中,可采用衬里或载体料10(图7A-7D)。衬里或载体料10可包括多层衬里(该多层衬里例如按照列于此以作参考的专利号为4,713,273的美国专利中所公开的方法制备得到),或可为常规衬里或载体(其由单纸或可由以卷材形式提供的膜层组成)。如果以前尚未用过防粘涂料,而衬里或载体本身在其接触胶粘剂的表面上并不包括固有地形成防粘表面的成分,则可用防粘涂料(如硅氧烷)在R位置涂覆衬里或载体10,如图7A所示。在施用了防粘涂料的情况下,在施用之后,采用任何合适的手段(未示出)来使防粘涂料干燥和固化。
防粘衬里或载体的防粘表面可涂覆一层压敏胶粘剂,以便使胶粘剂随后转移到和衬里或载体一起使用的面材上。当衬里或载体与面材结合时,胶粘剂就结合到面材上。之后除去衬里或载体而暴露出胶粘剂,该胶粘剂与面材保持永久结合。
因此如图7A所示,在使先前在位置R处被施用的防粘涂料干燥和固化之后,再到位置S处施用胶粘剂。这可以是一前一后的涂覆操作,或胶粘剂的涂覆可以在单独的涂覆线上进行。另外,可在衬里或载体10与面材20结合之前的某个较晚时间施用胶粘剂。图7B举例说明了衬里或载体与面材20的结合过程。另外,可在面材与衬里或载体结合之前直接将胶粘剂涂覆到面材20上。
在一些应用中,胶粘剂可以是诸如在膜内标签应用中所采用的热活化胶粘剂或热熔胶粘剂,与压敏胶粘剂不同的是,在此情况下可能不需要像采用压敏胶粘剂时所要求的那样,提供防粘衬里或固有的防粘性。
在被冲切成单独的标签之前,可在一印刷位置(未示出)印刷标签面材。印刷步骤可以在衬里和面材结合之前或之后进行,但应在将面材冲切成各个单独的标签之前进行。膜在各印刷步骤之间(如不同颜色的连续压印步骤之间)必须保持精确的定位以使图像或纹理具有高质量,并在印刷和随后的冲切之间保持精确的定位以使图像或纹理被正确地安排到标签上。在印刷期间,膜处于拉力作用下,并且可能受到温度升高的影响(例如在UV油墨固化时),而在纵向上却不得有明显的拉伸。当采用聚合物膜的衬里时,或当要求不采用衬里时,面材膜的MD拉伸性质特别重要。
图7C举例说明了在位置T处将面材20冲切成为一系列间隔开的压敏标签34的过程,该标签带有防粘衬里或载体10。这一步骤可按照公知的方式借助于旋转冲切模进行,而且包括剥离在冲切时所形成的在标签周围的梯子形(梯子的“横档”代表连续的标签之间的间隔)的基体废弃物或者说切边(未示出)。在一个实施例中,可采用磁性模代替旋转模。这些标签然后就以彼此间隔开的关系而保持在衬里上,如图所示。这一操作中的一种失败方式涉及冲切不好的标签在基体被剥离时仍保留在基体上。在这种方式下,由于分离水平降低,不良的冲切更可能造成标签粘附在基体材料上,并在剥离基体期间与衬里分离。当被冲切的膜强度不足时,导致了另一种失败方式。由于基体材料的强度降低,当从衬里上取下被冲切的标签周围的基体时,基体易于撕裂。本发明的膜所具有的强度足以基体在被剥离时断裂。
图7D举例说明了借助于采用剥离刀38,通过从标签上逐渐揭掉衬里或载体而暴露出标签的胶粘剂面39,并使标签凸出而与经过的工件36相接触,来分配标签34,从而将标签34施用到经过的工件36之上。在本发明的内容中,工件36可构成坚硬的基体,如玻璃瓶或表面上容易带有不规则性的其它坚硬物件,并因此要求采用这样的标签:它是柔软的,且紧紧地粘附(贴合)基体表面,而不会于局部的表面凹陷处架桥。
应该理解图7A到图7D所示的操作可由不同的制造商、在不同的地方进行,或者图7A到图7D的操作可以合并起来进行。例如,图7A的步骤可由衬里和胶粘剂制造商来完成,图7B和图7C的步骤可由标签制造商在一次连续的传送中完成,而不被如图所示的卷绕或展开程序打断,并且图7D的步骤可通过包装制造好的产品来完成。
形成于标签中的面材通常是以卷材形式来卷绕或展开,并因此而具有被称为“卷材(roll stock)”或“卷形面材(roll facestock)”的其中一种形式,而相应的衬里或载体也被称为是“卷材衬里(roll liner)”。
由组合物,包括纵向取向膜和胶粘剂层,制备而得到的冲切标签为坚硬的基体如玻璃提供了可接受的贴标签方式,其中标签具有充分的柔软性和贴合性,来适应玻璃制造工艺所导致的不规则或起伏的玻璃表面性质。过于坚硬的标签膜如双轴取向膜易于导致在玻璃表面中的凹陷或模缝处架桥,而且这样的凹陷表现得就好像是标签和玻璃表面之间的内部气泡。
在一个实施例中,本发明的纵向取向的聚丙烯膜,以及由该聚丙烯膜制备的标签,其特征均在于是清澈的或完全透明的。因此,本发明的取向膜在纵向和横向上的不透明度约为10%或更低,而混浊度则为约10%或更低。在一个实施例中,不透明度和混浊度为8%或更低。在另一实施例中,混浊度为约5%或更低。膜的不透明度是采用TAPPI测试法T425os测定的,而混浊度是按照ASTM测试法D-1003测定的。
可对膜进行处理以改善其可打印性。处理膜的方法是公知的,包括电晕处理、等离子处理和其它处理。一种特别有用的处理方式是在6.5-8KW的功率下以每分钟400到450英尺的线速度对膜进行处理。功率密度约为2-3瓦特/ft2/分钟。
通过使实例1-32的膜组合物(作为表层)与芯部(由Huntsman丙烯均聚物P4G4K-038构成)共挤出,而制备得到有用的三层多层膜,其中芯部是在470°F温度下挤出的,且表层是在450°F温度下挤出的,从而形成了2.5密尔厚的多层膜,该多层膜具有两个表层和芯部,这两个表层中每一个的厚度占该多层膜的厚度的7.5%,而芯部则占该膜厚度的其余部分。膜为纵向取向的,在250°F下的拉伸比为6.5∶1,并在265°F下退火。
通过使实例1-32的膜组合物(作为表层)与芯部(由Huntsman丙烯均聚物P5M4K-046构成)共挤出,而制备得到有用的三层多层膜,其中芯部是在470°F温度下挤出的,且表层是在450°F温度下挤出的,从而形成了2.5密尔厚的多层膜,该多层膜具有两个表层和芯部,这两个表层中每一个的厚度占该多层膜的厚度的7.5%,而芯部占该膜厚度的其余部分。膜为纵向取向的,在245°F下的拉伸比为6.5∶1,并在270°F下退火。
通过共挤出实例1-32的膜组合物(作为表层)与芯部(由Huntsman丙烯均聚物P5M4K-046构成),而制备得到有用的两层多层膜,其中芯部是在470°F温度下挤出的,并且表层是在450°F温度下挤出的,从而形成2.5密尔厚的多层膜,该多层膜具有一个表层和芯部,表层的厚度占该多层膜的厚度的15%,而芯部占该膜的厚度的其余部分。膜为纵向取向的,在235°F下的拉伸比为6.5∶1,并在260°F下退火。
通过共挤出实例1-32的膜组合物(作为表层)与芯部(由Huntsman丙烯均聚物P4G4K-038构成),而制备得到有用的两层多层膜,其中芯部是在470°F温度下挤出的,而表层是在450°F温度下挤出的,从而形成具有一个表层和芯部的2.5密尔厚的多层膜,其中表层的厚度占该多层膜厚度的15%,而芯部占该膜厚度的其余部分。膜为纵向取向的,在240°F下的拉伸比为6.5∶1,并在275°F下退火。
通过共挤出实例1-32的膜组合物(作为表层)与芯部(由BPAmoco丙烯共聚物8439构成),而制备得到有用的三层多层膜,其中芯部是在470°F温度下挤出的,而表层是在450°F温度下挤出的,从而形成具有两个表层和芯部的2.5密尔厚的多层膜,这两个表层中每一个的厚度占多层膜的厚度的7.5%,芯部占该膜厚度的其余部分。膜为纵向取向的,在260°F下的拉伸比为6.5∶1,并在280°F下退火。
通过共挤出实例1-32的膜组合物(作为表层)与芯部(由BP Amoco丙烯共聚物8439构成),而制备得到有用的两层多层膜,其中芯部是在470°F温度下挤出的,而表层是在450°F温度下挤出的,从而形成具有一个表层和芯部的2.5密尔厚的多层膜,表层的厚度占该多层膜的厚度的15%,而芯部占该膜厚度的其余部分。膜为纵向取向的,在2550°F下的拉伸比为6.5∶1,并在270°F下退火。
通过共挤出实例1-32的膜组合物(作为表层)与芯部(由95wt%的Huntsman丙烯共聚物P5M4K-046与5wt%的Exact 4151相混合而形成),可制备得到有用的三层多层膜,其中芯部是在470°F温度下挤出的,而表层是在450°F温度下挤出的,从而形成具有两个表层和芯部的2.5密尔厚的多层膜,这两个表层中每一个的厚度占多层膜厚度的7.5%,芯部占该膜厚度的其余部分。膜为纵向取向的,在245°F下的拉伸比为6.5∶1,并在270°F下退火。
通过共挤出实例1-32的膜组合物(作为表层)与芯部(由95wt%的Huntsman丙烯共聚物P5M4K-046与5wt%的Exact 4151相混合而形成),可制备得到有用的两层多层膜,其中芯部是在470°F温度下挤出的,而表层是在450°F温度下挤出的,从而形成具有一个表层和芯部的2.5密尔厚的多层膜,表层的厚度占该多层膜的厚度的15%,芯部占该膜厚度的其余部分。膜为纵向取向的,在235°F下的拉伸比为6.5∶1,并在260°F下退火。
通过共挤出实例1-32的膜组合物(作为印刷表层)与芯部(由95%的Huntsman丙烯共聚物P5M4K-046和5%的Exact 4151构成)以及胶粘剂表层(由95%的Huntsman丙烯共聚物P5M4K-046、5%的Exact4151和1%的Ampacet 10919(加工助剂)构成),而制备得到有用的三层多层膜,其中芯部是在470°F温度下挤出的,而表层是在450°F温度下挤出的,从而形成具有两个表层和芯部的2.5密尔厚的多层膜,这两个表层中每一个的厚度占该多层膜厚度的7.5%,而芯部占该膜厚度的其余部分。膜为纵向取向的,在235°F下的拉伸比为6.5∶1,并在260°F下退火。
通过共挤出实例1-32的膜组合物(作为表层)与芯部(由95%的Huntsman丙烯共聚物P5M4K-046与5%的Huntsman L8148(具有熔融指数0.9和密度的LLDPE)相混合而形成),可制备得到有用的两层多层膜,其中芯部是在470°F温度下挤出的,而表层是在450°F温度下挤出的,从而形成具有一个表层和芯部的2.5密尔厚的多层膜,这两个表层中每一个的厚度占多层膜的厚度的7.5%,芯部占该膜厚度的其余部分。膜为纵向取向的,在235°F下的拉伸比为6.5∶1,并在260°F下退火。
通过使实例1-32的膜组合物(作为印刷表层)与芯部(由66%的Huntsman丙烯共聚物P5M4K-046、13%的Exact 4151和21%的Ampacet 110069(LLDPE(熔融指数1)中70%的二氧化钛)构成)以及胶粘剂表层(由95%的Huntsman丙烯共聚物P5M4K-046和5%的Huntsman L8148(具有熔融指数0.9和密度的LLDPE)构成)共挤出,而制备得到有用的三层多层膜,其中芯部是在470°F温度下挤出的,而表层是在450°F温度下挤出的,从而形成具有两个表层和芯部的2.5密尔厚的多层膜,这两个表层中每一个的厚度占该多层膜厚度的7.5%,而芯部占该膜厚度的其余部分。膜为纵向取向的,在245°F下的拉伸比为6.5∶1,并在270°F下退火。
通过共挤出实例1-32的膜组合物(作为印刷表层)与芯部(由95%的Huntsman丙烯共聚物P5M4K-046和5%的Exact 4151构成)以及胶粘剂表层(由95%的Huntsman丙烯共聚物P5M4K-046、5%的Exact4151和1%的Ampacet 10919(加工助剂)构成),而制备得到有用的两层多层白膜,其中芯部是在470°F温度下挤出的,而表层是在450°F温度下挤出的,从而形成具有两个表层和芯部的2.5密尔厚的多层膜,这两个表层中每一个的厚度占该多层膜厚度的15%,而芯部占该膜厚度的其余部分。膜为纵向取向的,在235°F下的拉伸比为6.5∶1,并在260°F下退火。
通过在450°F下挤出实例1-22的膜组合物而形成2.5密尔厚的膜,可制备得到单层膜。该膜是纵向取向的,在245°F下的拉伸比为6.5∶1,并在265°F下退火。
尽管已经参照优选实施例对本发明展开了阐述,应该理解的是,对于阅读了本说明书的本领域技术人员来讲,本发明的各种变化方案将是显而易见的。因此,应该理解在此所公开的本发明应当覆盖全部落入所附权利要求书范围内的那些变化方案。
Claims (47)
1.一种纵向取向的聚合物膜,包括:(A)至少一种丙烯均聚物、共聚物,或其两种或两种以上的混合物,其中(A)所具有的熔体流动速率为约5到约40;以及(B)至少一种烯烃弹性体。
2.如权利要求1所述的膜,其中(A)所具有的熔体流动速率为约6到约32。
3.如权利要求1所述的膜,其中(A)为丙烯均聚物。
4.如权利要求1所述的膜,其中(A)为由丙烯和具有2到约12个碳原子的烯烃制备而得的丙烯共聚物。
5.如权利要求1所述的膜,其中所述丙烯共聚物为丙烯与乙烯、丁烯、己烯、庚烯、辛烯、壬烯或癸烯中的一种或多种的共聚物。
6.如权利要求1所述的膜,其中(A)为丙烯-乙烯共聚物或丙烯-丁烯共聚物。
7.如权利要求1所述的膜,其中(B)为乙烯均聚物或共聚物、丙烯均聚物或共聚物,或其两种或两种以上的混合物。
8.如权利要求1所述的膜,其中(B)为乙烯-丁烯共聚物、乙烯-辛烯共聚物、乙烯-己烯共聚物,以及乙烯-己烯-丁烯三元共聚物,或其两种或两种以上的混合物。
9.如权利要求1所述的膜,其中(B)的熔体流动速率为约1到约40。
10.如权利要求1所述的膜,其中(A)或(B)是成核的。
11.如权利要求1所述的膜,其中所述膜是清澈的。
12.如权利要求1所述的膜,其中(A)是采用茂金属催化剂制备而得的。
13.如权利要求1所述的膜,其中(B)是采用茂金属催化剂制备而得的。
14.如权利要求1所述的膜,其中所述膜的所有聚合物均为烃类聚合物。
15.如权利要求1所述的膜,进一步包括(C)至少一种成核剂。
16.如权利要求1所述的膜,其中通过以约2∶1到约9∶1的拉伸比在纵向上拉伸,而使所述膜被取向。
17.一种清澈的纵向取向膜,包括:(A)所具有的熔体流动速率为约5到约40的至少一种丙烯共聚物;以及(B)至少一种烯烃弹性体。
18.如权利要求17所述的膜,其所具有的厚度为约1到约7密尔。
19.如权利要求17所述的膜,其中(A)或(B)是成核的。
20.如权利要求17所述的膜,其中(A)或(B)是采用茂金属催化剂制备而得的。
21.如权利要求17所述的膜,进一步包括(C)至少一种成核剂。
22.如权利要求17所述的膜,其为单层膜。
23.如权利要求17所述的膜,其中(A)为丙烯-乙烯共聚物或丙烯-丁烯共聚物。
24.如权利要求17所述的膜,其中(B)为乙烯均聚物或共聚物、丙烯均聚物或共聚物,或其两种或两种以上的混合物。
25.如权利要求17所述的膜,其中(B)为乙烯-丁烯共聚物、乙烯-辛烯共聚物、乙烯-己烯共聚物,以及乙烯-己烯-丁烯三元共聚物,或其两种或两种以上的混合物。
26.一种清澈的纵向取向膜,包括:约50wt%到约90%的(A)至少一种丙烯-乙烯或至少一种丙烯-丁烯共聚物,其所具有的熔体流动速率为约6到约30;以及约10wt%到约50wt%的(B)至少一种乙烯-丁烯或至少一种乙烯-己烯共聚物。
27.一种多层膜,包括具有上表面和下表面的基层,以及位于上表面之上的至少一个表层,其中该表层是由权利要求1所述的膜制得的。
28.如权利要求27所述的膜,其中一表层位于所述基层的上表面和下表面之上。
29.一种多层膜,包括具有上表面和下表面的基层,以及至少一个表层,其中该表层位于所述上表面之上且是由权利要求17所述的膜制得的。
30.如权利要求29所述的膜,其中一表层位于所述基层的上表面和下表面之上。
31.一种多层膜,包括具有上表面和下表面的基层,以及至少一个表层,其中该表层位于所述上表面之上且是由权利要求26所述的膜制得的。
32.如权利要求31所述的膜,其中一表层位于所述芯部层的第一表面和第二表面之上。
33.一种可冲切的拉伸取向多层膜,包括:
(A)一基层,其具有上表面和下表面,且包括具有约0.840g/cm3或更低密度的聚乙烯、丙烯均聚物、丙烯共聚物,或其混合物;以及
(B)第一表层,其由(A)至少一种丙烯均聚物、共聚物,或其两种或两种以上的混合物,以及(B)至少一种烯烃弹性体制备而得,其中(A)具有约5到约40的熔融流动速率。
34.如权利要求33所述的多层膜,其中所述基层包括丙烯均聚物或共聚物。
35.如权利要求33所述的多层膜,其中所述基层包括具有约0.890到约0.925g/cm3密度的聚乙烯。
36.如权利要求33所述的多层膜,其中所述的基层或第一表层,或这两者,还含有成核剂。
37.如权利要求33所述的多层膜,包括第二表层,其覆盖在所述基层的下表面上。
38.如权利要求37所述的多层膜,其中所述第二表层的组成成分不同于所述第一表层的组成成分。
39.一种在粘胶标签中使用的含胶粘剂标签用料,包括:
(A)如权利要求1所述的膜;以及
(B)一胶粘剂层,其具有上表面和下表面,其中该胶粘剂层的上表面与基层的下表面结合。
40.如权利要求56所述的标签用料,其中所述胶粘剂层为压敏胶粘剂层。
41.一种在粘胶标签中使用的含胶粘剂标签用料,包括:
(A)如权利要求17所述的膜;以及
(B)一胶粘剂层,其具有上表面和下表面,其中该胶粘剂层的上表面与基层的下表面结合。
42.如权利要求41所述的标签用料,其中所述胶粘剂层为压敏胶粘剂层。
43.一种在粘胶标签中使用的含胶粘剂标签用料,包括:
(A)如权利要求33所述的膜;以及
(B)一胶粘剂层,其具有上表面和下表面,其中该胶粘剂层的上表面与基层的下表面结合。
44.如权利要求43所述的标签用料,其中所述胶粘剂层为压敏胶粘剂层。
45.一种压敏胶粘剂标签,其系由权利要求39所述的标签用料冲切而得。
46.一种压敏胶粘剂标签,其系由权利要求41所述的标签用料冲切而得。
47.一种压敏胶粘剂标签,其系由权利要求43所述的标签用料冲切而得。
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- 2003-06-26 DE DE60321090T patent/DE60321090D1/de not_active Expired - Lifetime
- 2003-06-26 KR KR1020117013144A patent/KR101186268B1/ko active IP Right Grant
- 2003-06-26 AT AT03014616T patent/ATE396472T1/de not_active IP Right Cessation
- 2003-06-26 US US10/606,461 patent/US7217463B2/en not_active Ceased
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- 2003-06-26 MX MXPA04012896A patent/MXPA04012896A/es unknown
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- 2003-06-26 EP EP20030014616 patent/EP1376516B1/en not_active Expired - Lifetime
- 2003-06-26 CN CNB038137518A patent/CN100560359C/zh not_active Expired - Lifetime
- 2003-06-26 AU AU2003247735A patent/AU2003247735B2/en not_active Ceased
- 2003-06-26 JP JP2004549833A patent/JP4268940B2/ja not_active Expired - Lifetime
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2015
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Also Published As
Publication number | Publication date |
---|---|
EP1376516A1 (en) | 2004-01-02 |
DE60321090D1 (de) | 2008-07-03 |
US7217463B2 (en) | 2007-05-15 |
JP4268940B2 (ja) | 2009-05-27 |
ES2305371T3 (es) | 2008-11-01 |
MXPA04012896A (es) | 2005-03-31 |
KR20110088562A (ko) | 2011-08-03 |
CN100560359C (zh) | 2009-11-18 |
JP2005531686A (ja) | 2005-10-20 |
AU2003247735A1 (en) | 2004-01-19 |
WO2004003874A3 (en) | 2004-03-18 |
KR101186268B1 (ko) | 2012-09-27 |
WO2004003874A2 (en) | 2004-01-08 |
ATE396472T1 (de) | 2008-06-15 |
AU2003247735B2 (en) | 2010-03-11 |
KR101186271B1 (ko) | 2012-09-27 |
EP1376516B1 (en) | 2008-05-21 |
CA2488551A1 (en) | 2004-01-08 |
KR20050016884A (ko) | 2005-02-21 |
USRE46911E1 (en) | 2018-06-26 |
US20040033349A1 (en) | 2004-02-19 |
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