CN1151713A - 膜组合物 - Google Patents

膜组合物 Download PDF

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CN1151713A
CN1151713A CN95193541A CN95193541A CN1151713A CN 1151713 A CN1151713 A CN 1151713A CN 95193541 A CN95193541 A CN 95193541A CN 95193541 A CN95193541 A CN 95193541A CN 1151713 A CN1151713 A CN 1151713A
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film
pvoh
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polyvinyl alcohol
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R·巴龙尼
M·L·L·蔡
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ExxonMobil Oil Corp
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Abstract

从聚合体基质制备的一种金属化的多层膜，优先选择的基质为聚丙烯，它被马来酸酐改性的丙烯聚合体改性，它处于基质表面或掺入基质内，其上有一层能被金属化的聚乙烯醇。

Description

膜组合物
本发明涉及一种能金属化的膜组合物。更具体的说，本发明涉及一种具有能金属化的聚乙烯醇(PVOH)表层的聚合体膜基质。本发明亦涉及金属化的膜。
取向塑料膜，特别是双轴取向的聚丙烯膜被广泛用于包装产品，特别是包装食品。但是还没有一种未经改性的聚合体膜具有包装材料所要求的隔气防潮性质。
本发明涉及能够金属化的膜组合物，它含有一种聚合体基质，该基质表面被马来酸酐改性的丙烯均聚体或共聚体所改性，这种聚合体基质的改性表面有一聚乙烯醇表层。
本发明的膜组合物具有优良的金属粘附性。它能防止气味外溢及维持油墨不脱落。这种膜在不用底涂的情况下，能很好地与油墨粘合，并是油墨可印刷的。此膜还具有优良的不透气味/香味的性质，优良的层间结合强度和光学透明性。
本发明的多层膜结构含有一种聚烯烃基质，一般是聚丙烯。优选的聚丙烯基质材料有如下性质：密度0.91g.cc；熔点160℃或更高；熔体流动速率2到4。
聚烯烃基质被马来酸酐改性的聚丙烯改性。马来酸酐改性的聚丙烯表层能如任何一种方法，如美国专利3,433,777和4,198,327所公开的方法来制备。美国专利5,153,074描述了一种简单的制备方法。马来酸酐改性的聚丙烯也能通过与基质聚烯烃熔融共混或与基质聚合体共挤压而掺入到基质中。一种商售马来酸酐改性的聚丙烯或丙烯共聚物有如下物理性质：密度0.90(ASTM  D1505)，维卡(Vicat)软化点143℃(ASTM  D1525)；肖氏硬度67℃(ASTM  22-40)；熔点160℃(ASTM D2117)。马来酸酐改性的聚丙烯是粘结底物与PVOH的连结层。应用马来酸酐改性的聚丙烯的重要性在于，如果不用它底物就无法与PVOH配伍。商售的马来酸酐改性的聚丙烯有多种，例如，Mitsui公司的“ADMER”(商品名)，DuPont公司的“BYNEL”(商品名)及Quantum公司的“PLEXAR”(商品名)。通常如用挤压涂布，改性的基质在机器方向被拉伸4至7倍，然后用火焰处理。
一层聚乙烯醇(PVOH)被用于改性基质的表面。在基质与马来酸酐改性聚丙烯共挤压的场合，应用PVOH改性表面是重要的，不然PVOH将难于粘到基质上。PVOH能以任何一种用有效的方法制得的薄层来应用。薄层的厚度从0.01mil至0.20mil。需要指出的三种方法是1)用选择模塞(selector plug)或多模腔模头(multicavity die)将PVOH层与改性基质进行共挤压；2)在机器方向拉伸和横向拉伸之间将PVOH层挤压涂布到改性基质表面；3)在机器方向拉伸和横向拉伸之间将PVOH膜层压到改性聚丙烯层表面。一般来说，当PVOH层挤压涂布到基质上时，膜在横向被拉伸5至12倍，然后用火焰处理。
为了挤压涂布和共层压，优选方法是在施用PVOH之前，将基质的接合面进行电晕或火焰处理。
在PVOH的对面，基质上可加上一层可热合的膜。这可以通过挤压一层可热合的聚合体，共聚体或三元共聚物如乙烯-丙烯-丁烯三元共聚物于基质上而实现。
然后，PVOH层通过其上沉积金属而被金属化。任何一种本领域中已知的金属化的典型方法均可采用。通常考虑的典型的金属有铝、铜、铬、镁、镍、锌、锡、银、金、钛、硅、铋或任何含有上述金属的任何化合物或结合物。最典型被应用的是铝涂层，其厚度可产生1.5到3.5光密度。能满足此种光密度要求的铝涂层的厚度典型地为50到1000埃。PVOH表面足以粘合金属。
虽然我们发现用火焰或电晕处理表面是有益的，但在PVOH金属化之前做这样的处理是不需要的。
我们发现将挤压级PVOH进行熔体加工时，不出现粘合问题，如EPA461,722所描述的那样，在PVOH采用溶液涂布时会出现粘合问题。因为PVOH用熔体加工而没有粘合问题故得到的膜能容易地卷成卷。也因为挤压涂布方法的使用，可以形成0.01mil到0.20mil的膜，而EPA461,722或U.S.5,192,620中公开的溶液涂布方法通常只能形成0.02到0.06mil的膜。挤压PVOH的商售产品有Air Products and Chemicals公司的Vinex树脂。
这里所公开的在多层膜中应用100％PVOH的优越性是很多的。由于应用了100％的PVOH，这种膜比起早先应用PVOH共聚体或共混体的膜具有更好的阻氧透过性。我们还发现优异的金属粘合性，油墨可印刷性和层压性得益于PVOH的表面性能。PVOH的表面张力很高，未经火焰或电晕处理的PVOH的表面张力约为37dyne/cm，与之相比聚丙烯的表面张力为29dyne/cm，表面处理后，PVOH的表面张力可大于55dyne/cm。另外，由于PVOH具有高于170℃的极高的熔点和软化点，所以当在620°F下用101bs/rm LDPE挤压成层时膜不会出现金属开裂(metal fracture)。下表1列出具有EVOH、PVOH/EAA和100％PVOH表层的多层聚丙烯膜的熔点和金属开裂性，以资比较：
            表  1聚合体       熔点    金属开裂EVOH         158      小-无PVOH/EAA* ～100      有一些PVOH       ＞170      无
* 丙烯酸乙酯
任何级别的PVOH都能用做表层。一般来说，部分水解的(水解度约88％)PVOH可以应用，甚至羟基含量70％或更高的PVOH也可应用。
共挤压过程中形成的以及此处所用的热合层是乙烯丙烯(EP)共聚体或乙烯、丙烯、1-丁烯(EPB)三元共聚体，如上指出的那样，它们通常处于PVOH表层的相对面。乙烯、丙烯、1-丁烯的比例可为0至15％的乙烯、70至100％的丙烯和0至15％的1-丁烯；如2％乙烯，94％丙烯和4％1-丁烯。
被一种粘合剂如低密度聚乙烯粘附于金属化膜上的可印刷表面可以是任何一种聚合体，如烯烃均聚体、共聚体或三元共聚体，聚碳酸酯或聚酯。这种可印刷的表面的一个性质是表面自由能为34dynes/cm或更高。
下面的例子显示，PVOH与金属化结合以及PVOH上覆盖一种合适的层压膜，比之其它结构有更好的阻氧透过、隔离潮气及气味等功能。而在这些例子中，金属化通过常规真空沉积完成，也可由常规气相沉积完成。虽然前面的例子中以聚丙烯作为基质，但其它聚烯烃膜如聚乙烯、聚酯、聚丁烯、烯烃共聚体、聚酰胺、聚碳酸酯和聚丙烯腈也可应用。
下述实施例用以说明本发明。实施例1
本例子以比较为目的。
一种聚丙烯均聚体的膜被挤压成0.90mil厚，马来酸酐接枝的聚丙烯为连接层，另一面上以乙烯-丙烯-丁烯三元共聚体为热合层。膜的马来酸酐接枝的聚丙烯的面在真空中用铝进行金属化至2.5光密度。此膜用101bs/ream LDPE热熔融体与75gauge聚丙烯膜挤出复合。膜的性质列在表1中。实施例2
本例示出制备符合本发明膜的方法，此种膜具有优异的隔气防潮性能。
制备一种聚丙烯膜，其方法是将聚丙烯基质与乙烯-丙烯-丁烯三元共聚体密封材料共挤压在其一面，连接层马来酸酐接枝聚丙烯于另一面。此膜在机器方向拉伸5倍。膜的连结层面进行火焰处理。PVOH被挤压涂布在处理过的连结层面上，在PVOH面再一次火焰处理之前，沿横向，膜再拉伸八倍，并在滚筒上卷成卷。膜的PVOH面被用铝真空金属化至光密度2.5。铝涂层厚度为300-500埃。膜与75gauge聚丙烯膜用101bs/ream LDPE热熔融体挤出复合。膜的性质列于表1中。
每张膜的厚度为0.90mil。连接层(马来酸酐接枝的聚丙烯)在两个实施例中均为约0.05mil。
制得的金属化膜测量气障性。水汽透过率(g/100in2/24hr)在100°F，90％RH测定。氧透过率(cc/100in2/24hr)在73°F，0％RH测定。铝对基质的粘结水平从Scotch Brand 610胶带在铝表面上粘拉三次，从粘掉的铝的百分数来衡量。层间的结合牢度(g/in)在层压机中用101bs/ream熔融低密度聚乙烯于325℃熔点下在金属化的表面上层压一层0.75mil聚丙烯膜测定。然后在常规的剥离机上将得到的膜测定层间的结合强度。典型的层间结合强度测试机是Alfred Suter测定仪及Sintech Tensile测定仪。得到的膜的性质如下：
                            表  2实施    可金属化    处理水平    OTR1    WVTR2  金属     层间粘结例号      的层      dyne/cm                    脱落，％   强度g/in1      PP(对照)       40       10.0     0.15      80      802      PVOH(6ga)    ＞56       0.024    0.06      5       171
1氧气透过率
2水蒸汽透过率
如表1所示，这种膜的防止氧气和潮气透过的性质极好且金属与膜的粘接性能可满足大多数的使用目的。

Claims (9)

1.一种膜组合物，它包括聚合物基质，所述基质具有至少一个被马来酸酐改性的丙烯均聚体或共聚体改性的表面，聚合体基质的改性表面有一层可被金属化的基本由聚乙烯醇组成的表层。
2.根据权利要求1的一种膜组合物，其中的马来酸酐改性的丙烯均聚体或共聚体是一个独立的层。
3.根据权利要求1或2的一种膜组合物，其中基质包括一种取向的丙烯均聚体或共聚体。
4.根据前述任一项权利要求的膜组合物，其中膜的一面之上具有热合层。
5.根据前述任一项权利要求的膜组合物，其中聚乙烯醇表层基本上不含交联剂。
6.根据前述任一项权利要求的膜组合物，其中聚乙烯醇表层包括可挤塑的聚乙烯醇。
7.根据权利要求11的膜组合物，其中聚乙烯醇表层为部分水解级。
8.根据前述任一项权利要求的金属化膜组合物，其中基本上由聚乙烯醇组成的表层之上直接覆有一金属层。
9.根据权利要求8的金属化膜组合物，其中基质上与表层相对有一热合层。
CN95193541A 1994-06-10 1995-05-24 膜组合物 Pending CN1151713A (zh)

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US08/258,316 US5491023A (en) 1994-06-10 1994-06-10 Film composition
US08/258,316 1994-06-10

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CN (1) CN1151713A (zh)
AU (1) AU697585B2 (zh)
CA (1) CA2183771A1 (zh)
NZ (1) NZ287354A (zh)
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JPH10501196A (ja) 1998-02-03
CA2183771A1 (en) 1995-12-21
AU2604195A (en) 1996-01-05
US5491023A (en) 1996-02-13
EP0764083A1 (en) 1997-03-26
KR970703240A (ko) 1997-07-03
NZ287354A (en) 1998-05-27
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AU697585B2 (en) 1998-10-08
WO1995034424A1 (en) 1995-12-21

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