CN101213246B - 包含酸酐接枝聚烯烃的组合物 - Google Patents

包含酸酐接枝聚烯烃的组合物 Download PDF

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CN101213246B
CN101213246B CN2006800240687A CN200680024068A CN101213246B CN 101213246 B CN101213246 B CN 101213246B CN 2006800240687 A CN2006800240687 A CN 2006800240687A CN 200680024068 A CN200680024068 A CN 200680024068A CN 101213246 B CN101213246 B CN 101213246B
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C·勒伯夫
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Dow Chemical Co
Dow Global Technologies LLC
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Abstract

组合物由马来酸酐接枝的金属茂线性低密度聚乙烯(mLLDPE)或马来酸酐接枝的金属茂甚低密度聚乙烯(mVLDPE)与烯烃聚合物组合物共混产生的。所得的马来酸酐接枝的聚合物组合物对金属膜如铝膜的粘附很好。该组合物同样具有流变性以使组合物有效地用于共挤塑法。同样也提供了一种制备马来酸酐接枝的丙烯聚合物组合物的方法。

Description

包含酸酐接枝聚烯烃的组合物
本发明涉及包含接枝聚烯烃的组合物,涉及包含接枝聚烯烃的镀金属组合物或膜,涉及包含接枝聚烯烃和乙烯共聚物的组合物,涉及生产镀金属膜的方法,并且涉及与此有关的产品,如食品包装。
背景技术
镀金属膜是在其上沉积(例如真空法)一层如铝的热塑性薄膜。它们用于食品包装工业作为湿气和气体的阻挡层。镀金属膜可包括诸如聚对苯二甲酸乙二醇酯(PET)或聚丙烯(PP)的聚酯作为热塑性膜组分。聚乙烯(PE)有时也镀金属。镀金属膜经常与其它材料如聚乙烯(PE)、取向聚丙烯(OPP)、取向PET(OPET)、纸和纸板结合成多层结构。这些其它材料可作为例如妄用(abuse)层或密封层。它们同样也可提供劲度和印刷表面。因此,包含粘附于热塑性组合物和其它衬底的镀金属膜的多层结构可用作为包装膜。应用包括诸如粉状饮料混合袋的许多干燥食品包装以及非包装应用。妄用和/或印刷层的实例包括取向聚对苯二甲酸乙二醇酯、取向或流延聚丙烯、高密度聚乙烯(HDPE)、纸、纸板和双轴取向尼龙。密封膜的实例包括低密度聚乙烯(LDPE)、乙烯/醋酸乙烯酯(EVA)共聚物、离聚物(即部分中和的乙烯/酸共聚物)、线性低密度聚乙烯(LLDPE)PE和甚低密度聚乙烯PE(VLDPE)。
粘合剂能将膜的镀金属表面粘附到相邻层上。例如,低密度聚乙烯(LDPE)可作为粘合层。其它粘合层包括乙烯酸共聚物。参看例如美国专利USP6,165,610。
使用LDPE将衬底粘附于镀金属膜可通过在高涂布温度(300至330℃)加工完成,使得部分聚乙烯氧化。LDPE的氧化生成对镀金属表面提供适度粘附的极性物质。
使用LDPE将聚乙烯膜挤塑层压到镀金属膜上所伴随的问题是镀金属层对其基膜的粘附随时间“老化”。例如,LDPE对镀金属膜的粘附在开始时仅仅是勉强够格的,但是历经一个至几个星期后,键强度经常降低到不再有使用功能的水平。一种解释可能是老化与LDPE的次级结晶度有关。LDPE在层压过程期间淬火非常快,初级结晶几乎不能发生。经一段时间,小的“次级”结晶可能形成。随着PE结晶,其收缩。收缩能对键施加应力并降低剥离强度。在真空沉积镀金属层和其基膜之间的键是结构中最弱的键。
极性较强的聚合物相比极性较弱的聚合物更易于粘附到镀金属膜上。很好粘附到镀金属膜的极性聚合物可能对非极性聚合物粘附不好。因此,提供允许既粘附到镀金属膜上又粘附到非极性聚合物上的性能均衡的粘结层(tie layer)是所期望的。
用于促进粘附热塑性膜衬底的化学底漆增加了成本并且采用基于溶剂的体系可能引起环境关注。期望开发不使用底漆将镀金属膜粘附到膜或聚合物的组合物或方法。
发明概述
本发明包括可镀金属的烯烃聚合物组合物。该组合物包含聚烯烃和酸酐接枝的第二聚烯烃、酸酐单酯接枝的乙烯聚合物或二者,或由其制成。酸酐可包括马来酸酐、富马酸酐、琥珀酸酐或其两种或多种的组合。酸酐单酯可包括马来酸酐单酯、富马酸酐单酯、琥珀酸酐单酯或其两种或多种的组合。酸酐接枝的乙烯聚合物在组合物中能够以约0.001至约5%,或约0.01至约4%,或约0.1至约4%存在和酸酐单酯接枝的乙烯聚合物在组合物中能够以约0.1至约20%,约0.5至约15%,或约1至约10%存在。
本发明同样包括包含组合物和镀金属膜如铝膜的膜,或由其制成的膜。
本发明同样包括包含第一层和第二层的包装膜,所述第一层包含金属膜,第二层包含如上公开的组合物。
本发明还提供能防止湿气和氧气透过的食品包装。该包装可包含或基本上由下述组成:包装膜或镀金属聚烯烃(如聚丙烯)层和一层或多层含有聚烯烃的层,其中镀金属聚烯烃层包含或由下述制成:聚烯烃和马来酸酐(或其单酯)接枝的mLLDPE(金属茂催化的线性低密度聚乙烯)、马来酸酐(或其单酯)接枝的mVLDPE(金属茂催化的甚低密度聚乙烯)、马来酸酐(或其单酯)接枝的LLDPE、VLDPE、ULDPE、乙烯共聚物或其两种或多种的组合。包装优选具有附加的聚丙烯阻挡层和热密封层。
本发明同样包括能够用于生产马来酸酐接枝的聚烯烃组合物或其膜的方法。该方法包括或基本上由下述组成:在有机过氧化物存在时在使酸酐有效接枝到聚烯烃上的条件下混合聚烯烃与酸酐。
发明详述
“可镀金属的”表示能够有效与金属结合。酸酐可包括任何酸酐、它的单酯或其组合。酸酐的实例包括马来酸酐、马来酸酐单酯、琥珀酸酐、琥珀酸酐单酯、富马酸酐、富马酸酐单酯或其两种或更多种的组合。
聚烯烃可包括含有由烯烃得到的重复单元的任何聚合物并包括聚乙烯、聚丙烯、聚丁烯、聚异丁烯以及任何这些聚烯烃的共聚物。这种共聚物可以包括共聚单体,包括丁烯、己烯、辛烯、癸烯、十二碳烯或其两种或更多种的组合。
例如,聚丙烯(PP)聚合物包括均聚物、无规共聚物、嵌段共聚物和丙烯三元共聚物。丙烯共聚物包括丙烯与其它烯烃如乙烯、1-丁烯、2-丁烯及各种戊烯异构体等的共聚物,并优选丙烯与乙烯的共聚物。丙烯三元共聚物包括丙烯与乙烯和一种其它烯烃的共聚物。无规共聚物,也称为统计共聚物,是其中丙烯与共聚单体在整个聚合物链中无规则分布,其比例对应于丙烯与共聚单体进料比。嵌段共聚物由丙烯均聚物组成的链段和例如由丙烯和乙烯的无规共聚物组成的链段构成。“聚丙烯”是指包含上述丙烯的聚合物的任何一个或全部。通过众所周知的方法如Ziegle-Natta催化剂体系能够生产PP。由于该方法众所周知,为简便起见这里省去其描述。
实例同样包括具有约1wt%至6wt%的低含量乙烯单体的乙烯和丙烯的共聚物。在表3中示出了产生改善聚丙烯对铝粘附性的预期效果的改性聚丙烯组合物的另外实例。
乙烯聚合物可以是HDPE、LLDPE、VLDPE、超低密度聚乙烯(ULDPE)、LDPE、mLLDPE、mVLDPE、乙烯共聚物或其两种或多种的组合。可通过各种方法制备PE,包括众所周知的Ziegle-Natta催化剂聚合法(参看例如USP4,076,698和3,645,992)、金属茂催化剂聚合法(参看例如USP5,198,401和5,405,922)和自由基聚合法。聚乙烯聚合物可以包括HDPE、LLDPE、甚低或超低密度聚乙烯(VLDPE或ULDPE)。聚乙烯的密度范围为0.865g/cc至0.970g/cc。“聚乙烯”是指包含上述乙烯的聚合物的任何一个或全部。
酸酐或酸酐单酯接枝的乙烯聚合物可以通过本领域技术人员已知的任何方法进行生产。例如,在自由基引发剂和酸酐或其单酯二者都存在下在双螺杆挤出机中通过熔融挤塑聚烯烃可生产接枝物。酸酐(例如马来酸酐)官能团所接枝的聚合物主链可以是以上公开的任何聚烯烃如LLDPE、VLDPE、mLLDPE、mVLDPE或是它们两种或多种的组合。
以酸酐或酸酐单酯的浓度计,在组合物中能够存在的酸酐或酸酐单酯≥约3.0wt%、≥约4wt%、≥约5wt%、≥约6wt%或甚至约≥7wt%。
粘合到金属薄膜的可镀金属组合物可以从乙烯共聚物制成或包含乙烯共聚物。金属膜优选是真空沉积铝层。
乙烯共聚物可以包含衍生自乙烯和不饱和羧酸、羧酸盐、羧酸酯、羧酸盐酯,如(甲基)丙烯酸酯或(甲基)丙烯酸C1至C8烷基酯或是其两种或多种的组合的聚合物单元(重复单元)。“(甲基)丙烯酸烷基酯”可包括丙烯酸烷基酯、甲基丙烯酸烷基酯或二者。“(甲基)丙烯酸”可包括丙烯酸、甲基丙烯酸或二者。例如,(甲基)丙烯酸甲酯可指甲基丙烯酸甲酯或丙烯酸甲酯。
丙烯酸烷基酯的实例包括丙烯酸甲酯、丙烯酸乙酯和丙烯酸丁酯。例如,“乙烯/丙烯酸甲酯(EMA)”意指乙烯和丙烯酸甲酯(MA)的共聚物;“乙烯/丙烯酸乙酯(EEA)”意指乙烯和丙烯酸乙酯(EA)的共聚物;“乙烯/丙烯酸丁酯(EBA)”意指乙烯和丙烯酸丁酯(BA)的共聚物;并既包括丙烯酸正丁酯又包括丙烯酸异丁酯或是其两种或多种的组合。
乙烯和丙烯酸酯的共聚物是众所周知的。“乙烯丙烯酸酯共聚物”也可称为乙烯-丙烯酸酯共聚物。它们可以由两个高压自由基方法制造:管式法或高压釜法。由该两种方法制造的乙烯丙烯酸酯共聚物的差别叙述在例如“由高压管式法制造高柔韧性EMA”Annual TechnicalConference-Society of Plastic Engineers(2002),60th(Vol.2),1832-1836。在本发明中优选由管式法生产的乙烯丙烯酸共聚物。
乙烯共聚物也可以包括另一种共聚单体如一氧化碳、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯和缩水甘油基乙烯基醚或其两种或多种的组合。
乙烯共聚物可以含有约15wt%至约40wt%,或约18wt%至约35wt%丙烯酸酯共聚单体。增加丙烯酸酯共聚单体可改善弹性性能并提高共聚物的粘合性。乙烯共聚物可以具有约0.1至约100,或约0.5至约20g/10min的熔融指数(MI),用ASTM D-1238,条件E(190℃,2160克重)测量。
乙烯共聚物也包括含有衍生自乙烯和不饱和羧酸的重复单元的酸共聚物,如(甲基)丙烯酸、马来酸、富马酸、马来酸酐、富马酸酐、马来酸单酯、富马酸单酯或是其两种或多种的组合。“(甲基)丙烯酸系”是指丙烯酸、甲基丙烯酸或其组合。例如,“乙烯/甲基丙烯酸(EMAA)”意指乙烯(E)和甲基丙烯酸(MAA)的共聚物;“乙烯/丙烯酸(EAA)”意指乙烯和丙烯酸(EAA)的共聚物。也包括多于一个共聚单体的实例。例如“乙烯/丙烯酸异丁酯/甲基丙烯酸(E/iBA/MAA)”意指乙烯(E)、丙烯酸异丁酯(iBA)和甲基丙烯酸(MAA)三元共聚物。酸共聚物可以包含约1至约25mol%的衍生自二酸的酸或酸酐或单酯的重复单元。
引入到乙烯酸共聚物中的(甲基)丙烯酸共聚单体可从全部共聚物的0.01wt%或5wt%改变至高达40wt%或甚至更高,例如从5wt%至30wt%,或从10wt%至25wt%。酸共聚物也可能含有高达具有烷基的丙烯酸烷基酯10wt%的C1-C8烷基基团。
可选择地,引入到乙烯共聚物中的(甲基)丙烯酸烷基酯或(甲基)丙烯酸共聚单体可从约0.01wt%改变至约30wt%,或从1wt%至25wt%,或从1wt%至10wt%。可选择地,诸如丙烯酸正丁酯的(甲基)丙烯酸烷基酯或(甲基)丙烯酸可以引入到聚合物中,以≤约6wt%或≤约5wt%或≤约4wt%或≤约3wt%或甚至≤约1wt%存在。
乙烯酸共聚物和它们的制备方法是本领域中众所周知的,如公开于USP3,264,272,3,404,134,3,355,319和4,321,337中。适用于在此的本发明的商业酸共聚物可从各种来源得到,包括E.I.du Pont de Nemoursand Company,Wilmington,DE(DuPont)的商标Nucrel
Figure 2006800240687_0
乙烯酸共聚物可以是直接共聚物或接枝共聚物。“直接共聚物”是由单体一起同时聚合而制成的共聚物,与单体在已存在的聚合物链上聚合的接枝共聚物不同。当直接或接枝酸共聚物具有约0.0001%至约90%用金属离子中和而离子化的羧酸基团时,它们被称为离子共聚物,或“离聚物”,其具有交联聚合物的固态性能和非交联热塑性聚合物的熔融加工特性。商业离聚物包括来自DuPont的Surlyn
Figure 2006800240687_1
离聚物。
酸共聚物或离聚物优选存在量范围为约5wt%至约50wt%,更优选约10wt%至约30wt%,最优选约8wt%至约15wt%。酸共聚物优选含有约4wt%至25wt%的酸,并更优选约8wt%至约15wt%的酸。酸共聚物可具有0.1至500,优选1至100,最优选1至30g/10min的熔融指数。
离聚物可具有约0.1至100,或约0.5至20g/10min的熔融指数,并衍生自具有约4wt%至约25wt%,或约8wt%至约15wt%酸,又具有约20wt%至70wt%中和度的酸聚合物。
基于酸酐或酸酐单酯的浓度,酸酐或酸酐单酯接枝乙烯聚合物可以约0.5wt%至约5wt%,约1wt%至约4wt%,或约1wt%至约2wt%存在于组合物中。
诸如食品包装的多层阻挡膜可以包括一个层,该层含有以上公开的聚合物组合物作为可镀金属层。例如,层1可以是薄金属膜,其可以通过真空沉积金属如铝、铜、银、铬、金、其两种或多种的合金或其两种或多种组合而制备。该层可作为氧气和湿气的阻挡层。层2可以是可镀金属的聚合物层。该层可以含有以上公开的可镀金属聚合物组合物,如包含聚烯烃和酸酐接枝第二聚烯烃者。层2可以具有约10至约25μ的厚度。第三层可以粘附到层2上并包含如聚丙烯的聚烯烃。它可以作为阻挡层并可以具有约10至约25μ的厚度。层4可以粘附到层3上。第四层16可以是可热封聚烯烃层。聚烯烃可是聚丙烯、聚丙烯/聚乙烯共聚物、弹性体、聚丙烯/丁烯-1共聚物、聚丙烯/聚乙烯/丁烯-1三元共聚物、聚酮或其两种或多种的组合。
一层或多层也可含有一种或多种添加剂。添加剂的实例包括防粘剂、抗静电剂、摩擦系数改进剂、加工助剂和着色剂、澄清剂。这些是在本领域中众所周知的添加剂。
多层膜的暴露层或最外层可以经表面处理使膜可接受印刷油墨、粘合剂和涂料。这些表面处理的层随后可以被层压在其它膜或表面上。通过本领域已知的如电晕放电处理或火焰处理的任何方法可以实现表面处理。
任选地,涂料可施用于膜的最外层的暴露表面的一面或两面以便于层压。在施用涂料之前,膜可经表面处理或涂底漆层。实例涂料包括丙烯酸系涂料和PVDC(聚偏氯乙烯)涂料。乙烯醇聚合物也可用作涂料组合物。适用的底漆材料是聚乙烯亚胺、环氧底漆等。
膜的外表面可经如以上指出的处理以提高它的表面能并因此保证涂层可强力地粘附到其上,由此降低了涂层剥落或从膜上剥离的可能性。使用已知的技术可以完成该处理,例如膜氯化,即将膜表面暴露于氯水,用诸如铬酸的氧化剂处理,热空气或蒸汽处理,电晕处理等。电晕处理包括在使膜通过一对有间隔的电极之间时,将膜表面暴露于高压电晕放电。在膜表面电晕处理后,而后将涂料组合物施用到其上。
已处理的或未处理的表面可与适用的粘合剂一起层压,例如诸如低密度聚乙烯、乙烯-甲基丙烯酸酯共聚物的热熔粘合剂,诸如聚偏氯乙烯胶乳的水基粘合剂等。
实施例
通过将选择的改性剂粒料(表2)共混入选择的基础树脂粒料(表1)中,并直接把粒料共混物送进装备有至少三台挤出机的膜流延管线的挤出机中,由此能够使用装备有合适模块以破裂不同进料的挤出模头挤出3种不同的树脂而获得可镀金属聚丙烯组合物。于是两(2)种不同的聚丙烯(PP)树脂用表2中列出的二十三(23)种不同的PP改性剂进行改性。在某些情况中PP基础树脂以两种或多种不同水平被改姓,显示出对提高改性剂水平的粘附响应。
表1
Figure 2006800240687A00800011
(1)Chisso’s FW4BM,丙烯、乙烯和丁烯的三元共聚物。
(2)Dow’s 6D81,丙烯和乙烯的共聚物。
表2
Figure 2006800240687A00800012
(1)聚丙烯均聚物
(2)丙烯和乙烯的共聚物
(3)ENGAGE8180乙烯和辛烯的共聚物
(4)ENGAGE
Figure 2006800240687_13
8180来自DuPont Dow Elastomers的乙烯和辛烯的共聚物
(5)ENGAGE
Figure 2006800240687_14
8411来自DuPont Dow Elastomers的乙烯和辛烯的共聚物
(6)Dow’s 6D20:丙烯和乙烯共聚物
(7)Surlyn
Figure 2006800240687_15
RX1014是包含衍生自10.5wt%丙烯酸和15.5wt%丙烯酸正丁酯的单元的离聚物
(8)Surlyn
Figure 2006800240687_16
RX1018是包含衍生自6.2wt%丙烯酸和28.0wt%丙烯酸正丁酯的单元的离聚物
(9)Elvaloy
Figure 2006800240687_17
4924是来自DuPont的乙烯/乙酸乙烯酯/一氧化碳的三元共聚物
(10)Elvaloy
Figure 2006800240687_18
HF441是来自DuPont的乙烯/丙烯酸正丁酯/一氧化碳的三元共聚物
(11)Bynet
Figure 2006800240687_19
2002是乙烯/丙烯酸乙酯/丙烯酸的三元共聚物
(12)Lotader2210是来自AtoFina的乙烯/丙烯酸丁酯(6%)/马来酸酐(2.6%)的三元共聚物
(13)Lotader3410是来自AtoFina的乙烯/丙烯酸丁酯(18%)/马来酸酐(3%)的三元共聚物
(14)LODATER TX8030是来自AtoFina的乙烯/丙烯酸丁酯(12.5%)/马来酸酐(2.5%)的三元共聚物
(15)LotaderAX8840是来自AtoFina的乙烯/甲基丙烯酸缩水甘油酯(8%)共聚物
(16)Orevac9314是来自AtoFina的乙烯/乙酸乙烯酯/马来酸酐的三元共聚物
(17)FUSABOND
Figure 2006800240687_20
EP 1021是乙烯和MAME(马来酸酐单酯,9.5%)的共聚物
(18)FUSABOND
Figure 2006800240687_21
A EB 560D是EP 1021和ElvaloyAC 3427的共混物
(19)Lotader4210是来自AtoFina的乙烯/丙烯酸丁酯(6%)/马来酸酐(3.8%)的三元共聚物
(20)马来酸酐接枝量%
在表3“顶层”栏中列出用作三层结构中可镀金属PP层的改性PP的组合物。
表3cPP三层膜结构
Figure 2006800240687A00800021
(a)此栏标示膜结构;
(b)顶层聚合物含量(括号中为wt%)是:膜F1(100);F2-F3
(80);F4-F13(84);F14和F17-F24(92.5);F13(90);F15(90);F25-F34和F39(90);F35(84);F38(78);F37(95.6);F38(92.9);F40(96.8);F41(94.9);F42(92.8);F43(98.3);F44(97.3);F45(96.2);F46(94.9);F47(91.6);F48(86.6);F49(81.1);F50(97.9);F51(96.6);F52(95.3);F53(94.9);和F54(84).
改性剂构成余量(至100%)。此栏标示基础树脂。
(c)此栏标示改性剂组成。
(d)VM-cPP膜(基于三层PP的膜,顶层由改性PP制成,芯层由5D98 homo-PP制成,底层由6D20 co-PP制成)。
使用8英寸(约20厘米)共挤塑流延管线共挤出每一种改性PP组合物,在三层膜中,使用Dow的5D98 homo-PP作为芯层,并使用Dow的7C06冲击改性PP或Dow的6D20 co-PP作为衬里层。每一膜结构首先经电晕处理至约41-45达因/厘米,而后用铝镀金属(约200纳米厚层)。可镀金属层对沉积铝的粘附力在用双棒热密封器将铝顶层热密封到来自DuPont的乙烯酸共聚物Nucrel
Figure 2006800240687_23
膜上之后再评定。从热密封衬底上剪下一英寸(2.54厘米)宽试条,用手开始剥离并用Instron测量在铝/改性PP界面处的剥离强度。在所有镀金属的3层PP膜结构中的粘附性能示于表3。每一镀金属的3层PP膜结构的性能描述在表3剥离强度(克/英寸剥离力)下。基于现存在的商用膜,对于全功能性剥离强度最小“可接受”值是130克/英寸。
膜F1、F2和F3例示顶PP层使用马来酸酐接枝PP的改性效果。不足以满足目标粘附力。很早也确认了电晕处理能提高粘附力并且对于表3示出的全部实施例,3层PP膜在镀金属之前经电晕处理。
在表3中示出的粘附力数据包括几种满足或超过130克/英寸的最小粘附力指标的膜结构,也包括几种不满足的。总之,依据产生改性PP对铝的良好粘附力和不产生的改性剂类型,这些实施例公开如下。
有效的改性剂:
MAH-g-mVLDPE(M3至M6,M19,M20),MF4至MF11,MF36至MF44;
E/MAME共聚物(M21),MF45至MF48;
E/MAME共聚物+ELVALOY
Figure 2006800240687_24
AC(M22),MF49至MF51;和
E/nBA/MAH三元共聚物(M23),MF52至MF55;
无效的改性剂:
coPP/mVLDPE与MAH(M7),MF12,MF13,MF16,MF17共聚接枝;
E/nBA/AA三元共聚物(M8,M9),MF18,MF19,MF27,MF28;
E/VA/CO三元共聚物(M10),MF20,MF29;
E/nBA/CO三元共聚物(M11),MF21,MF30;
E/MA/AA三元共聚物(M12,M13),M22,M23;
E/nBA/MAH三元共聚物(M14,M15),MF24,MF25,MF31,MF32,MAH≤3.0%;nBA>6%;
E/EA/MAH三元共聚物(M16),MF26,MF33;
E/GMA共聚物(M17),MF34;和
E/VA/MAH三元共聚物(M18),MF35。
镀金属聚合物组合物的制备
测量为4英寸×英寸(约11厘米×11厘米)的四方膜试样在真空镀金属室中处理。真空系统泵低至2×10-5乇并且铝被加热以便以每秒5埃的速率沉积在膜表面上到200埃厚度。沉积铝层的厚度使用预先确立的校正关系通过表面电阻率或透光率测定,这两种方法对本领域技术人员均是公知的。
多层镀金属聚合物膜的制备
在中试规模共挤塑管线上流延用于粘附性能评价的膜,所述管线装备有三个挤出机、一个Killion 8”宽流延辊单元和一个构造用于与三种树脂进料运转的Cloeren 8”(5-叶片)流延膜模头。
模头构造:AABBC选择器塞。
A:13/4”直径NRM单螺杆挤出机,进料选择用于内层的材料。
B:1.0”直径Davis标准单螺杆,进料选择作为芯层的材料。
C:1 1/4”直径Wayne单螺杆挤出机,进料改性-PP组合物。
总线速度:20fpm(9.1米/分)。
总膜厚度:3密耳(约0.008厘米)。
表4
Figure 2006800240687A00800031
Figure 2006800240687A00800032
随后对3层流延膜进行电晕处理。电晕处理参数被设定以获得最终表面能为41达因/厘米2,线速度为100英尺/分(45.5米/分)。
所用的粘附试验
聚合物可镀金属层对真空沉积铝膜的粘附力用如下方法测量。使用具有2×1英寸(5.1×2.54厘米)宽分开热密封的棒的Sencorp Systems热密封器,首先在铝层上用Nucrel903膜热密封真空镀金属试样。在40psi/135℃(1psi=0.275MPa)下以0.5秒保压时间密封Nucrel
Figure 2006800240687_26
膜。在改性PP/铝界面开始剥离,而后使用Instron机械试验仪在环境条件下以12英寸/分(305厘米/分)夹头速度测定剥离力。以Ib ft/in报告结果。

Claims (7)

1.一种膜,由组合物和镀金属膜制成,其中所述组合物包含聚烯烃和改性剂,其中
该改性剂是马来酸酐接枝的乙烯聚合物;
该乙烯聚合物是金属茂催化的线性低密度聚乙烯、金属茂催化的甚低密度聚乙烯、乙烯共聚物或其两种或多种的组合;
该马来酸酐接枝的乙烯聚合物在组合物中以0.1至20%存在。
2.权利要求1的膜,其中所述聚烯烃是聚丙烯。
3.权利要求1的膜,其中所述聚烯烃是聚丙烯,并且所述乙烯共聚物包含衍生自乙烯和马来酸或马来酸酐的重复单元。
4.权利要求1或2的膜,其中所述聚烯烃是聚丙烯,并且所述乙烯共聚物包含衍生自乙烯和(甲基)丙烯酸烷基酯、(甲基)丙烯酸或马来酸酐甲酯的重复单元。
5.权利要求4的膜,其中乙烯共聚物是乙烯和丙烯酸乙酯的共聚物;乙烯、丙烯酸正丁酯和马来酸酐的共聚物;或其组合。
6.权利要求1的膜,其中所述膜是多层膜;所述镀金属膜是第一层;包含所述组合物或由其制成的膜是第二层;所述膜是食品包装;并且所述食品包装任选包含另外的聚丙烯阻挡层、可热密封层或二者。
7.组合物作为改进第一膜与镀金属膜的粘附力的改性剂的用途,其中第一膜包含在权利要求1、2、3、4或5中表征的组合物或由其制成。
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