CN1997702B - 适于rf焊接应用的共混组合物 - Google Patents

适于rf焊接应用的共混组合物 Download PDF

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CN1997702B
CN1997702B CN2005800147490A CN200580014749A CN1997702B CN 1997702 B CN1997702 B CN 1997702B CN 2005800147490 A CN2005800147490 A CN 2005800147490A CN 200580014749 A CN200580014749 A CN 200580014749A CN 1997702 B CN1997702 B CN 1997702B
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copolymer
acid
component
ethylene
film
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CN1997702A (zh
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陈助
D·J·沃尔什
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EIDP Inc
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EI Du Pont de Nemours and Co
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Abstract

本发明公开了膜，其得自乙烯共聚物与有机酸盐改性的钾离聚共聚物的共混物。本发明的膜可用射频能量焊接。

Description

适于RF焊接应用的共混组合物
本申请要求2003年11月11日递交的美国专利申请第10/704,934号和2004年5月12日递交的美国临时申请第60/570,550号的权益。
发明领域
本发明涉及吸收射频能量的聚合物组合物。本发明更具体涉及得自聚合物组合物的膜，其可利用射频能量焊接。
背景技术
在包装应用中，人们往往可能期望在膜包装材料上不使用单独的粘合膜层就能密封该膜包装材料。可通过使用能自粘合的材料、或使用可使材料本身粘合到另一材料上的材料完成这种密封工艺。这类工艺中有一种是：在一种合适的材料上施加射频(RF)能量，在吸收了RF能量之后，该材料随即可自粘合或与不同的基材粘合而形成密封。这种工艺被称为RF焊接，而且适合这种工艺的材料已是周知的商品。例如聚氯乙烯(PVC)是一种对RF能量敏感的材料，非常适于RF焊接。然而，世界上某些地区不允许广泛使用PVC材料，因此在这些不欢迎PVC的地方，需要能实现PVC功能的代用材料。
为了用于利用RF焊接技术的包装应用而选择合适的代用材料并不是简单试验。在选择或开发合适的代用材料时，至少要满足三个标准。首先，该材料必须提供满足包装或其组件要求的良好物理和/或机械特性。第二，合适的聚合物膜应对RF能量敏感，即应当吸收RF能量。第三，该聚合物膜应能在恰当的压力和时间条件下受到RF能量时形成粘合、焊接或密封。
众所周知有多种聚合物适于在包装应用中使用。例如聚烯烃，如聚乙烯和聚丙烯是包装中有用的材料。已知某些聚合物材料对RF能量敏感。但是，其它材料可能由于成本过高或其它问题而不适合在这里所描述的应用中使用。例如，某些材料对RF能量敏感，但不能形成密封或焊接。某些材料需要更苛刻工艺条件，或要求增加某一成分而使其它物理/机械性能损害。例如EVA的敏感性很大程度上依赖于醋酸乙烯酯的含量。乙烯(甲基)丙烯酸性共聚物及其离聚物一般不具有RF敏感性。
离聚物和极性溶剂如甘油的混合物可制造吸收RF能量的组合物。然而，使用在挤出温度下具有相当高蒸气压的溶剂会导致其它问题，如在加工过程中薄膜会结雾。而且鉴于环保，不希望使用极性溶剂。
理想的是，能有一种组合物，其吸收RF能量，并能利用RF焊接而密封，同时还具有适于包装应用的物理和机械性能。
发明概述
一方面，本发明涉及可以吸收射频(RF)能量的一种膜，其中该膜含有：
(a)一种共混物，其包括(i)至少一种E/X/Y共聚物，其中E为乙烯、X为一种C3到C8的α，β烯属不饱合羧酸，且Y为一种软化性共聚单体，该单体选自丙烯酸烷基酯和甲基丙烯酸烷基酯，其中的烷基具有一至八个碳原子，其中X为该E/X/Y共聚物的约2-30重量％，且Y为该E/X/Y共聚物的约0-40重量％，其中该酸成分(X)的存在形式可为完全中和的羧酸盐或者部分中和的羧酸盐，和
(ii)一种或多种有机酸或其盐；其中该共混物的组合羧酸盐官能团至少部分地被钾中和；和
(iii)一种或多种选自多元醇和聚酯的极性化合物；和，
(b)非必要的至少一种其它聚合物组分，
其中该膜吸收射频(RF)能量。
发明详述
在一个实施方案中，本发明是得自一种共混物的聚合物膜，该共混物包括一种酸性共聚离聚物和一种脂肪酸盐。本发明的膜至少约0.001密耳厚。优选这种膜至少约1密耳厚至约25密耳厚。
本发明的膜含有酸共聚离聚物(“离聚物”)，其为聚合物领域众所周知的一些共聚物。离聚物是通过一种α-烯烃，例如乙烯、丙烯、1-丁烯和其它1-不饱和烃，与一种不饱和羧酸，例如举例来说，丙烯酸、甲基丙烯酸或马来酸及非必要的软化性共聚单体的共聚反应形成的离子共聚物。随后经如本发明所使用的那样获得离聚物，在本申请中用到时，术语“共聚物”可描述为通过至少两种不同种类单体的共聚获得的聚合物。术语“三元共聚物”可用于专门描述自三种不同单体共聚获得的共聚物。至少一种碱金属、过渡金属或碱土金属的阳离子，如锂、钠、钾、镁、钙或锌，或者这些阳离子的组合可作为中和盐的羧酸根阴离子的平衡离子。特别优选至少部分被钾阳离子中和的离聚物。三元共聚物也可用烯烃如乙烯、不饱合羧酸和软化性共聚单体如(甲基)丙烯酸烷基酯制造，提供可被中和形成柔软离聚物的“柔软”树脂。
在本发明实施中有用的共混物包括：至少一种E/X/Y酸性共聚物成分，其中E为乙烯、X为一种C3到C8的α，β烯属不饱合羧酸，且Y为一种软化性共聚单体，该单体选自其中的烷基具有一至八个碳原子的丙烯酸烷基酯和甲基丙烯酸烷基酯，其中X为该E/X/Y共聚物的约2-30重量％，且Y为该E/X/Y共聚物的约0至约40重量％。这种酸性共聚物可完全和部分用已知且常规的手段中和，以便提供酸性共聚离聚物(离聚物)。本发明实施中适用的离聚物是公知的，而且可以从E.I.DuPont de Nemours and Company获得商品名Surlyn的商品。
另外，本发明的膜包括有机酸或其盐(有机盐)。在本发明的实践中，提到有机酸也可指该酸的盐或者该酸和该盐的混合物。在本发明实践中有用的共混物包括至少约5wt％的有机酸。优选该共混物中包括约5wt％至50wt％的有机酸。更优选该共混物中包括至少约10wt％的有机酸，甚至更优选包括至少约20wt％的，并最优选至少约30wt％的有机酸和/或其盐。这些有机盐的平衡离子优选至少部分是钾离子。优选共混物中大于70％的所有酸成分被中和，更优选大于90％被中和，最优选共混物中100％的所有酸成分被中和。
本发明的有机酸具体为那些非挥发和非迁移性的，例如含有约6-约38个碳原子的酸。有机酸的非限定的说明性例子是：硬脂酸及其异构体，油酸及其异构体，芥酸及其异构体，和山萮酸及其异构体。优选硬脂酸和油酸及其异构体。甚至更优选合适有机酸的支化异构体，例如硬脂酸和油酸的支化异构体，例如异硬脂酸和异油酸。在2003年11月11日递交的标题为“可透湿透气的无孔(Non-Porous)离聚物膜”的美国专利申请中，可以找到用于本发明的合适酸和共混物的更完整描述，经引用将其全部并入本申请。优选这些有机酸被中和，并且带有选自钾(K)、钠(Na)、锂(Li)、铷(Rb)和镁(Mg)的离子的平衡离子。更优选平衡离子为钾(K)。
在一个优选实施方案中，本发明包括作为有机酸的C6至C38有机酸的异构体。特别优选的是油酸的异构体，如2-甲基油酸(异油酸)，和硬脂酸的异构体，如2-甲基硬脂酸(异硬脂酸)。还在本发明的实践中优选使用官能化的脂肪酸，例如举例来说，氨基-和羟基-官能化的脂肪酸。羟基硬脂酸例如举例来说12-羟基硬脂酸，可作为一种优选的官能化脂肪酸。
用于本发明实践中的合适共混物可包括非必要的聚合物成分。这样的非必要成分可包括一种第二离聚共聚物，包括二元共聚物离聚物和三元共聚物离聚物；和/或热塑性树脂。这些热塑性树脂可非限定地说明示例性地包括：热塑性弹性体，例如聚氨酯、聚-醚-酯、聚-酰胺-醚、聚醚-脲、PEBAX(基于聚醚-嵌段-酰胺的嵌段共聚物一族，可由Atochem供应商品)；苯乙烯-丁二烯-苯乙烯(SBS)嵌段共聚物；苯乙烯(乙烯-丁烯)-苯乙烯嵌段共聚物；(低聚和聚合的)聚酰胺；聚酯；聚乙烯醇；聚烯烃，包括聚乙烯、聚丙烯、乙烯/丙烯共聚物；具有各种共聚单体的乙烯共聚物，例如乙烯/醋酸乙烯酯、乙烯/(甲基)丙烯酸酯、乙烯/(甲基)丙烯酸、乙烯/环氧官能化单体、乙烯/CO、乙烯/乙烯醇(多元醇)；具有接枝的马来酸酐官能团的官能化聚合物类和环氧化聚合物；弹性体，例如EPDM、茂金属催化的聚乙烯和共聚物、热固性弹性体的磨碎的粉末。非必要的第二种聚合物成分可为一种共混物，该共混物含任何这些材料中至少一种，包括对RF辐射不敏感的那些材料。
优选该第二成分是乙烯的共聚物，例如举例来说，各种共聚单体的乙烯共聚物，例如乙烯/醋酸乙烯酯，乙烯/(甲基)丙烯酸酯，乙烯/(甲基)丙烯酸及其离聚物，乙烯/环氧官能化单体，乙烯/CO，乙烯/乙烯醇，或者含这些当中至少一种的共混物。更优选第二聚合物成分选自乙烯醋酸乙烯酯树脂(EVA)；乙烯/丙烯酸烷基酯；乙烯/(甲基)丙烯酸和它们的离聚物；或含这些材料中至少一种的共混物。
如果包含这种非必要的聚合物成分，其包含量优选为整个钾离聚物成分量的99wt％至约1wt％。优选这种非必要的聚合物成分的含量为约95wt％至约50wt％，更优选含量为约93wt％至约70wt％。
本发明的膜可用于单层或多层结构。本发明的膜可非限定地用于，例如膜包装材料，容器和罩盖的包装应用中。
不饱和羧酸的例子包括丙烯酸、甲基丙烯酸、富马酸、马来酸酐、马来酸单甲酯、马来酸单乙酯。特别优选丙烯酸和/或甲基丙烯酸。可以起到共聚成分作用的极性单体的例子包括：乙烯酯类，如醋酸乙烯酯和丙酸乙烯酯；不饱和羧酸酯类，如丙烯酸甲酯、丙烯酸乙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸正己基酯、丙烯酸异辛基酯、甲基丙烯酸甲酯、马来酸二甲酯和马来酸二乙酯；一氧化碳。具体地，不饱和羧酸酯类是适合的共聚成分。
实施例
所用材料
Elvaloy AC1224是乙烯醋酸乙烯酯与乙烯甲基丙烯酸共聚物的一种共聚物共混物，皆可从E.I.DuPont de Nemours and Company(DuPont)获得商品。
单硬脂酸甘油酯(GMS)(或聚甘油的潜酯)或单硬脂酸山梨(糖)醇酯可用于本发明的实践中。
通用程序
制备共混物膜：将Elvaloy
Figure 10003_1
AC1224(从DuPont获得的商品)共聚物与不同水平的RF增强剂共混，所述不同水平介于5％和15％之间，然后在棱柱挤出机(prism extruder)上挤出这些共混物，制备6-12密耳厚度的膜，测试这些膜的可焊接性。将两层膜衬在Kapton
Figure 10003_2
片材上，放在RF源的电极中间，在轻微的正压下，通常暴露2秒。
可采用介电测量方法测定RF吸附。或者较简单的相应方法是，测量将材料引入交变信号的电容区域的影响，并测定对该信号宽度或“Q值”(频率除以宽度)的影响。Q值变低表示吸附，而且由于这是相对给定电路的，所以Q降低的百分数是一个有用的值。
可如下进行焊接试验，在某一压力下，使一对膜样品接受交变场的一段定时处理。
表1
Q值降低的％
PVC(9次测定的平均值)9密耳                     12.4±3
填充的PVC，重增塑的(3次的平均值)9密耳         18.8±2
Elvaloy*AC1224(5次的平均值)6密耳              19.7±3
Elvax*3170 18密耳                             18.8
Surlyn*8140                                   8
Surlyn*8150+20％甘油6密耳                     60(湿度达50％)
95(75％的湿度)
Surlyn*8150+20％GMS                           13(湿度达50％)
Surlyn*8140+30％12-羟基硬脂酸钾               78(湿度达50％)
96(75％的湿度)
Surlyn*8140+20％异-硬脂酸钾                   89(25％的湿度)
95(75％的湿度)
按照主观标度(arbitrary scale)对焊接性能进行了评级。等级值4是常规可焊接组合物的标准等级值。可影响结果的因素例如是膜厚度、时间和电压。
0-膜之间的粘着可忽略
1-粘着可察觉
2-剥离时粘着足以使膜变形
3-沿着焊接位的一些部分不是剥离而是膜撕裂
4-沿着整个焊接位没有剥离而是膜撕裂
获得的结果等级(selection)为：
PVC                                       4
高增塑，填充的PVC                         4
Elvaloy*AC1224                            0
AC1224+10％(Surlyn
Figure 10003_3
+甘油)    25％湿度    4
75％湿度    4
AC1224+10％(Surlyn
Figure 10003_4
+GMS)
25％湿度    1
75％湿度    2
AC1224+10％(Surlyn
Figure 10003_5
+羟基硬脂酸钾)
25％湿度    3
75％湿度    3
Elvax*3170                                 20％湿度    1(在3-4kV/3s)
3(在4.5kV/3s)
Elvax*3170+10％(Surlyn
Figure 10003_6
+异硬脂酸钾*)
50％湿度    3(在3.2kV/2.5s)
Elvax*3170+20％(Surlyn
Figure 10003_7
+异硬脂酸钾*)      50％湿度    4(在2.8kV1s)
Elvax*3170+30％(Surlyn
Figure 200580014749010000210003_8
+异硬脂酸钾*)      50％湿度    4(在2kV/1s)
Q值下降的％
SiSt1                                (25％RH)               89％
(50％RH)               95％
(75％RH)               96％
实施例A1：Elvax3170/10％SiSt         (25％RH)               15％
(50％RH)               59％
(75％RH)               43％
实施例A2：Elvax3170/20％SiSt         (25％RH)               53％
(50％RH)               80％
(75％RH)               49％
实施例A3：Elvax3170/30％SiSt         (25％RH)               86％
(50％RH)               89％
(75％RH)               90％
焊接实验：
焊接等级
实施例A1                             3(在3.2kV/2.5s)
实施例A2：                           4(在2.8kV/1s)
实施例A3：                           4(在2.0kV/1s)
Elvax3170                            1-2(在～3.5kV/3s)
*异硬脂酸钾
1Surlyn8140/20％异硬脂酸钾

Claims (2)

1.一种吸收射频能量的膜，该膜含有：
(a)包含以下(i)和(ii)的混合物的第一组分，
(i)至少一种E/X/Y共聚物，其中E为乙烯、X为一种C3到C8的α，β烯属不饱合羧酸，且Y为一种软化性共聚单体，该单体选自丙烯酸烷基酯和甲基丙烯酸烷基酯，其中的烷基具有一至八个碳原子，其中基于E/X/Y共聚物重量，该E/X/Y共聚物包含2-30重量％共聚单元的X，和0-40重量％共聚单元的Y，其中该酸成分X的存在形式为完全中和的羧酸盐或者部分中和的羧酸盐，和
(ii)选自含有6-38个碳原子的有机酸、所述有机酸的盐和它们的混合物的一种物质；
其中存在于所述共聚物和所述组分(ii)的物质中的组合羧酸基团的至少一部分被钾离子中和；和
(b)50wt％-95wt％的第二组分，其中所述第二组分不同于所述第一组分的至少一种聚合物，并且选自聚乙烯、聚丙烯、乙烯丙烯共聚物、乙烯醋酸乙烯酯共聚物、乙烯丙烯酸酯共聚物、乙烯甲基丙烯酸酯共聚物、乙烯环氧官能化单体共聚物、乙烯一氧化碳共聚物、乙烯乙烯醇共聚物和它们的混合物。
2.权利要求1的膜，其中组分(b)的含量为70重量％-93重量％。
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JP4778509B2 (ja) 2011-09-21
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US7875680B2 (en) 2011-01-25
AU2005245891A1 (en) 2005-12-01
JP2007537349A (ja) 2007-12-20
KR101217929B1 (ko) 2013-01-02
US20050255328A1 (en) 2005-11-17
CN1997702A (zh) 2007-07-11
US8071223B2 (en) 2011-12-06
US20080171165A1 (en) 2008-07-17
US8043664B2 (en) 2011-10-25
AU2005245891B2 (en) 2011-02-03
KR20070007922A (ko) 2007-01-16
WO2005113670A1 (en) 2005-12-01
EP1745098A1 (en) 2007-01-24
US20110079534A1 (en) 2011-04-07

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