CN101889032B - 离聚物、含有该离聚物的树脂组合物、由该组合物形成的未拉伸膜、片材或成型体、以及具有该未拉伸膜层的层合体 - Google Patents

离聚物、含有该离聚物的树脂组合物、由该组合物形成的未拉伸膜、片材或成型体、以及具有该未拉伸膜层的层合体 Download PDF

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Publication number
CN101889032B
CN101889032B CN2008801195796A CN200880119579A CN101889032B CN 101889032 B CN101889032 B CN 101889032B CN 2008801195796 A CN2008801195796 A CN 2008801195796A CN 200880119579 A CN200880119579 A CN 200880119579A CN 101889032 B CN101889032 B CN 101889032B
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Prior art keywords
weight
potassium
ionomer
resin combination
film
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CN2008801195796A
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CN101889032A (zh
Inventor
松崎大介
铃木薰
秋山光纪
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Dow Mitsui Polychemicals Co Ltd
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Du Pont Mitsui Polychemicals Co Ltd
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Abstract

本发明提供一种非带电性及透明性优异的未拉伸膜和片材、制造该未拉伸膜或片材时使用的树脂组合物、以及该组合物中含有的钾离聚物。本发明提供一种钾离聚物，所述钾离聚物是含有30～60重量％(a)乙烯单元、30～60重量％(b)丙烯单元、2～10重量％(c)丁烯单元、0～10重量％(d)(甲基)丙烯酸酯单元及5～15重量％(e)(甲基)丙烯酸单元的聚合物或聚合物组合物(其中，成分单元(a)～(e)总计为100重量％)的钾离聚物，其中钾离子密度在0.5～1.5mmol/g的范围内。

Description

离聚物、含有该离聚物的树脂组合物、由该组合物形成的未拉伸膜、片材或成型体、以及具有该未拉伸膜层的层合体
技术领域
本发明涉及一种优选用作未拉伸膜或片材等的材料的离聚物(ionomer)、及含有该离聚物的树脂组合物。
背景技术
离子键树脂(ionomer resin)具有特殊的结构，即，将乙烯·甲基丙烯酸共聚物和乙烯·丙烯酸共聚物等的分子间用钠和锌等金属离子进行分子间键合，是抗静电性和透明性优异的树脂。
在离子键树脂中，钾离聚物(potassium ionomer)具有优异的抗静电性能，可以用作高分子抗静电剂。特别是已知含有钾离聚物及聚烯烃的树脂组合物具有优异的非带电性。
但是，对于由现有的在聚烯烃、特别是丙烯类共聚物中混合了钾离聚物的树脂组合物形成的未拉伸膜，其透明性根据此树脂组合物的种类和组成尚有改善的余地。
专利文献1：日本特开2005-343973号公报
发明内容
本发明的目的在于提供非带电性及透明性优异的未拉伸膜或片材，制造它们时使用的树脂组合物，以及该组合物中含有的钾离聚物。
本发明人等为了解决上述课题，对具有优异的非带电性、在与热塑性树脂、特别是丙烯类共聚物混合时能够赋予优异的非带电性和透明性的钾离聚物进行了潜心研究，从而完成了本发明。
即，本发明包括以下内容。
[1]一种钾离聚物，是含有30～60重量％(a)乙烯单元、30～60重量％(b)丙烯单元、2～10重量％(c)丁烯单元、0～10重量％(d)(甲基)丙烯酸酯单元及5～15重量％(e)(甲基)丙烯酸单元的聚合物(x)或聚合物组合物(y)(其中，成分单元(a)～(e)的总计为100重量％)的钾离聚物，该钾离聚物的钾离子密度在0.5～1.5mmol/g的范围内。
[2]一种树脂组合物，含有低于100重量份～2重量份的[1]所述的钾离聚物(A)、和高于0重量份～98重量份的除钾离聚物(A)之外的热塑性树脂或弹性体(B)(其中，钾离聚物与热塑性树脂或弹性体的总计为100重量份)。
[3]如[2]所述的树脂组合物，其中，上述热塑性树脂为聚烯烃。
[4]如[2]或[3]所述的树脂组合物，其中，上述热塑性树脂为丙烯均聚物或丙烯共聚物。
[5]如[2]～[4]中任一项所述的树脂组合物，其特征在于，上述树脂组合物中的(甲基)丙烯酸残基的含量为0.1～15重量％，另外，其钾离子密度在0.01～1.5mmol/g的范围内。
[6]如[1]～[5]中任一项所述的钾离聚物或树脂组合物，其中，在23℃、相对湿度(RH)50％下的表面电阻率为1.0E+11Ω/sq以下。
[7]未拉伸膜、片材或成型体，是由[1]～[6]中任一项所述的钾离聚物或树脂组合物形成的。
[8]如[7]所述的未拉伸膜，其中，雾度(haze)为20以下。
[9]一种层合体，具有至少1层由未拉伸膜形成的层，所述未拉伸膜由[1]～[6]中任一项所述的钾离聚物或树脂组合物形成。
[10]一种层合体，是在未拉伸膜的单面或两面上层合聚烯烃膜而形成的，所述未拉伸膜由[1]～[6]中任一项所述的钾离聚物或树脂组合物形成。
使用本发明的离聚物或含有该离聚物的树脂组合物形成的未拉伸膜、片材或其他成型品、以及含有本发明的未拉伸膜的层合体，具有优异的非带电性及透明性，另外，高频熔接性也优异。
具体实施方式
<钾离聚物>
本发明的钾离聚物是以下述含量含有单体单元(a)～(e)的聚合物或聚合物组合物中所含的单体单元(e)的羧基的一部分或全部被钾(离子)中和而得到的，其钾离子密度在0.5～1.5mmol/g的范围内。
聚合物或聚合物组合物
本发明中的聚合物或聚合物组合物是以下述含量含有下述单体单元(a)～(e)的聚合物或聚合物组合物。
(a)乙烯单元：30～60重量％(优选为30～50重量％)
(b)丙烯单元：30～60重量％(优选为40～60重量％)
(c)丁烯单元：2～10重量(优选为3～8重量％)
(d)(甲基)丙烯酸酯单元：0～10重量％(优选为0～5重量％)
(e)(甲基)丙烯酸单元(b5)：5～15重量％(优选为7～14重量％)
〔其中，单体单元(a)～(e)的总计为100重量％〕
在本发明中，聚合物(x)是指单独的共聚物(single copolymer)，聚合物组合物(y)是指2种以上的聚合物或共聚物的组合物(混合物)。即，在本发明中，聚合物(x)是指以上述含量含有单体单元(a)～(e)的共聚物，聚合物组合物(y)是指作为组合物的整体以上述含量含有(a)～(e)的组合物，该组合物含有2种以上均聚物或共聚物，所述均聚物具有1种选自单体单元(a)～(e)中的单体单元，所述共聚物具有2种以上选自单体单元(a)～(e)中的单体单元。
另外，本发明中(甲基)丙烯酸是指丙烯酸或甲基丙烯酸，(甲基)丙烯酸酯是指丙烯酸酯或甲基丙烯酸酯。
作为导入丁烯单元(c)的单体，可以举出1-丁烯及2-丁烯。
作为导入(甲基)丙烯酸酯单元(d)的单体，可以举出烷基的碳原子数为1～10的(甲基)丙烯酸烷基酯，具体而言，可以举出丙烯酸甲酯、丙烯酸乙酯、丙烯酸异丙酯、丙烯酸异丁酯、丙烯酸正丁酯、丙烯酸异辛酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异丙酯、甲基丙烯酸异丁酯、甲基丙烯酸正丁酯及甲基丙烯酸异辛酯等。
作为构成上述聚合物组合物的均聚物或共聚物，即，作为具有1种选自单体单元(a)～(e)中的单体单元的均聚物或具有2种以上选自单体单元(a)～(e)中的单体单元的共聚物，具体而言，例如可以举出聚乙烯、聚丙烯、聚丁烯、乙烯·甲基丙烯酸共聚物、乙烯·丙烯酸共聚物、乙烯·丙烯酸甲酯共聚物、丙烯·1-丁烯无规共聚物、丙烯·乙烯·1-丁烯无规共聚物、聚丙烯、聚乙烯、聚丁烯、乙烯·丁烯共聚物、丙烯·乙烯共聚物等。其中，优选乙烯·甲基丙烯酸共聚物、丙烯·1-丁烯无规共聚物、丙烯·乙烯·1-丁烯无规共聚物及丙烯·乙烯共聚物。
作为上述均聚物或共聚物、即在本发明中作为原料聚合物使用的聚合物的制造方法，通常可以使用例如高温·高压下的自由基聚合法。
本发明的钾离聚物可以采用例如以下方法得到。
(i)方法：将导入单体单元(a)～(e)(其中(d)为任意成分)的各单体通过高压聚合而共聚得到聚合物，将所得聚合物的羧基的一部分或全部用钾离子中和。
(ii)方法：将导入单体单元(a)～(d)(其中(d)为任意成分)的各单体1种以上与导入单体单元(e)的单体共聚形成共聚物，将所得共聚物的羧基的一部分或全部用钾离子中和得到钾离聚物，将所得的钾离聚物与将导入单体单元(a)～(d)的各单体1种以上共聚得到的聚合物混合。
(iii)方法：将导入单体单元(a)～(d)(其中(d)为任意成分)的各单体1种以上与导入单体单元(e)的单体形成共聚物，由该共聚物和下述聚合物形成组合物，所述聚合物包含1种以上导入单体单元(a)～(d)(其中(d)为任意成分)的各单体，然后，将所得组合物中的羧基的一部分或全部用钾离子中和。
本发明的钾离聚物是通过将上述具有烯烃单元等的聚合物的羧基用钾的氧化物、碳酸盐、碳酸氢盐及氢氧化物等中和而得到的。
如果考虑加工性及与热塑性树脂的混合性等，则本发明的钾离聚物的熔体流动速率(MFR)(在230℃、2160g负荷，按照JIS K7210-1999)通常为0.1～100g/10分钟、优选为0.5～10g/10分钟。
本发明的钾离聚物中的钾(离子)密度通常在0.5～1.5mmol/g(每1g钾离聚物为0.5～1.5毫摩尔)的范围内。如果钾(离子)密度在上述范围内，则能够使本发明的未拉伸膜呈现出优异的抗静电效果。
本发明中，可以适当地选择原料聚合物，即，以上述特定含量含有单体单元(a)～(e)的共聚物或作为组合物的整体以上述特定含量含有(a)～(e)的组合物，并且所述组合物包含2种以上聚合物，所述聚合物具有选自单体单元(a)～(e)中的1种或2种以上单体单元，然后将上述聚合物或聚合物组合物中的羧基(单体单元(e)的羧基)用钾离子中和，适当调节其中和度，由此可以制备钾离子含量为期望值的钾离聚物。利用钾离子进行的中和，例如可以通过使上述聚合物或聚合物组合物与钾的氢氧化物或钾盐(碳酸盐等)等反应来进行。
<热塑性树脂或弹性体>
作为本发明的热塑性树脂或弹性体，是除钾离聚物之外的热塑性树脂或弹性体，具体而言可以举出高压法聚乙烯、线型低密度聚乙烯(例如使用茂金属催化剂制造得到的聚乙烯等)、中密度聚乙烯、高密度聚乙烯、聚丙烯、聚-1-丁烯及聚-4-甲基-1-戊烯之类的烯烃均聚物或共聚物；乙烯与乙酸乙烯酯及丙酸乙烯酯等乙烯酯以及丙烯酸甲酯、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2-乙基己基酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯及马来酸二甲酯等不饱和羧酸酯等不饱和酯形成的共聚物；将2种以上碳原子数2～12的α-烯烃共聚形成的结晶度(X射线衍射法)为40％以下的非结晶性或低结晶性的α-烯烃类共聚物、例如乙烯与碳原子数3～12的α-烯烃形成的非结晶性或低结晶性的无规共聚物；聚苯乙烯；AS树脂、ABS树脂、苯乙烯·丁二烯嵌段共聚物及苯乙烯·丁二烯·苯乙烯嵌段共聚物以及它们的氢化物；苯乙烯·异戊二烯嵌段共聚物及苯乙烯·异戊二烯·苯乙烯嵌段共聚物以及它们的氢化物；尼龙6、尼龙66、尼龙610、尼龙11、尼龙12、尼龙6·66、尼龙6·12及尼龙6TI等聚酰胺；聚对苯二甲酸乙二醇酯、聚对苯二甲酸丙二醇酯及聚对苯二甲酸四亚甲酯等聚酯；聚碳酸酯；聚缩醛；聚苯醚；丙烯酸树脂；以及聚氯乙烯等。
在上述热塑性树脂或弹性体中，从可以得到能与钾离聚物均匀混合、透明性高、且加工性等优异的树脂组合物的观点考虑，优选聚烯烃，从与钾离聚物的相容性及透明性的观点考虑，特别优选丙烯类聚合物。上述丙烯类共聚物可以为丙烯均聚物及丙烯共聚物中的任一种。
作为上述丙烯类聚合物，从与钾离聚物的相容性及低粘着性等方面考虑，优选丙烯的均聚物(丙烯均聚物)或者丙烯含量小于100重量％且为90重量％以上、烯烃(不包括丙烯)的含量高于0重量％且为10重量％以下(高于0重量％、10重量％以下)的丙烯·烯烃聚合物。作为上述烯烃，可以举出乙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯等碳原子数4～12的α-烯烃。
从与本发明的钾离聚物的相容性等方面考虑，热塑性树脂或弹性体的熔体流动速率(MFR)(190℃(为丙烯类聚合物时为230℃)、2160g负荷、按照JIS K7210-1999)、特别是聚烯烃的MFR通常为0.1～100g/10分钟、优选为0.5～50g/10分钟。
<树脂组合物>
本发明的树脂组合物通过将钾离聚物(A)、热塑性树脂或弹性体(B)和根据需要的其他添加剂等同时或依次进行干混或熔融混合得到。进行干混的情况下，可以使用亨舍尔混合机及滚动混合机等各种混合机。进行熔融混合的情况下，可以使用单螺杆或双螺杆挤出机、班伯里混合机、辊及捏合机等混炼装置，在140～230℃温度下通过混炼得到。
本发明的树脂组合物可以通过混合钾离聚物与热塑性树脂或弹性体而得到，所述钾离聚物通常为低于100重量份～2重量份、优选为10～50重量份，所述热塑性树脂或弹性体通常为高于0重量份～98重量份(高于0重量份、98重量份以下)，优选为50～90重量份。其中，钾离聚物(A)与热塑性树或弹性体(B)的总计为100重量份。如果钾离聚物小于2重量份，则本发明的树脂组合物存在非带电性变得不充分的倾向。
本发明的树脂组合物中含有的(甲基)丙烯酸残基的含量通常为0.1～15重量％，另外，树脂组合物中的钾离子密度通常为0.01～1.5mmol/g，具有良好的非带电性。需要说明的是，本发明中“(甲基)丙烯酸残基”是指被钾离子离子化之前的聚合物中的(甲基)丙烯酸单元。
如上所述得到的本发明的钾离聚物或树脂组合物，在23℃、相对湿度(RH)50％下的表面电阻率通常为1.0E+11Ω/sq以下，优选为1.0E+10Ω/sq以下，较优选为1.0E+9Ω/sq以下，在23℃、相对湿度(RH)50％下的10％静电衰减时间(Electrostatic charge decay time)通常为20秒以下、优选为10秒以下、较优选为2秒以下。表面电阻率及静电衰减时间在上述范围内时，本发明的钾离聚物或树脂组合物具有优异的非带电性。
本发明的钾离聚物或树脂组合物的未拉伸膜的雾度(haze)通常为20以下，具有优异的透明性。
本发明的钾离聚物或树脂组合物的熔体流动速率(MFR)(在230℃、2160g负荷下)通常为0.1～100g/10分钟，优选为0.5～50g/10分钟。
可以根据需要，在本发明的钾离聚物或树脂组合物中配合少量(例如10重量％以下左右)抗氧化剂、紫外线吸收剂、光稳定剂、颜料表面活性剂(阴离子、阳离子及非离子型表面活性剂)及抗静电剂等添加剂。
<未拉伸膜、片材或成型体>
本发明的钾离聚物或树脂组合物可以成型为膜(未拉伸膜)、片材、管、纤维及其他成型品等各种形状。例如未拉伸膜可以通过铸塑成型及吹胀成型等进行制造，片材及其他成型品可以通过注塑成型及吹塑成型等公知的方法进行制造。需要说明的是，未拉伸膜的厚度通常为1～500μm左右。
另外，除未拉伸膜之外，本发明的钾离聚物或树脂组合物还可以加工成片材、带、纤维、织物、无纺布、软管(tube)、导管(pipe)、棒、袋、容器、各种注塑成型品及各种中空成型品等。
<层合体>
本发明的钾离聚物或树脂组合物，除用作单层的未拉伸膜或片材之外，例如还可以将本发明的树脂组合物彼此层合，或将该树脂组合物与其他材料层合，制成具有至少一层由本发明的树脂组合物形成的未拉伸膜层的多层层合体。此时，作为上述其他材料，可以使用各种聚合物，例如聚乙烯、聚丙烯、聚酯及聚酰胺等热塑性树脂、以及热塑性弹性体、热固性树脂、粘合剂、纸、金属、织物、无纺布、木材及陶瓷等。使用热塑性树脂作为其他材料时，由热塑性树脂形成的层(膜)可以未拉伸，也可以为单轴或双轴拉伸。其中，优选在上述未拉伸膜层的单面或两面上层合聚烯烃膜层形成的多层层合体。
在上述多层层合体中，由本发明的钾离聚物或树脂组合物形成的未拉伸膜层的厚度优选为1～500μm，由其他材料形成的层的厚度优选为1μm～5mm，较优选为10～500μm。
本发明的层合体可以具有一层由其他材料形成的层，也可以具有两层以上。本发明的钾离聚物或树脂组合物，如上所述作为单层的未拉伸膜、或者作为该未拉伸膜与其他材料形成的层合体可以加工成膜、片材、带、纤维、织物、无纺布、软管、导管、棒、袋、容器、各种注塑成型品及各种中空成型品等。作为更具体的用途，可以举出切割胶带(dicing tape)基材及背面研磨膜等半导体用胶带或膜；掩膜、IC载带及电子部件镶边带(taping tape)之类电气·电子材料、食品包装材料、卫生材料、保护膜、钢丝被覆材料、清洁室窗帘、壁纸、垫、地板材料、挠性容器内袋、容器、鞋、电池隔层、透湿膜、防污膜、防尘膜、PVC代替膜以及各种化妆品、洗涤剂、洗发剂及冲洗剂等的软管或瓶子等。
例如将本发明的钾离聚物或树脂组合物用作切割胶带基材时，在由上述钾离聚物或树脂组合物形成的胶带基材上涂布橡胶类、丙烯酸类及有机硅类等粘合剂，再在其上贴合剥离膜制成产品。由于本发明的离聚物或树脂组合物具有优异的非带电性(抗静电性)，所以作为高分子型的抗静电剂有用。另外，本发明的离聚物或树脂组合物不仅非带电性优异，而且高频焊接性也优异，所以可以用作高频熔接用材料，例如用作可以用于高频密封材料的单层膜或与其他材料形成的层合膜。在上述层合膜中，为了同时具有非带电性及高频密封性，也可以将本发明的离聚物或树脂组合物用作热封层(heat seal layer)，或者与热封层相邻的层。此时，作为上述其他材料，除上述热塑性树脂之外，还可以举出铝箔、铝蒸镀膜、二氧化硅蒸镀膜及乙烯·乙烯醇共聚物等。需要说明的是，上述层合膜不仅可以具有一层而且也可以具有两层以上由上述其他材料形成的层。
〔实施例〕
以下根据实施例更详细地说明本发明。需要说明的是，含有钾离聚物的树脂组合物的物性评价方法(测定方法)如下所述。
<表面电阻率>
将试样在规定温度及湿度下保存24小时后用三菱化学社制HIGH RESTER UP(探针：URS)进行测定。
<静电衰减时间>
将在23℃、50％RH下保存24小时的试样使用美国ETS公司制Static Decay Meter Model 4060，将外加电压从+5000V衰减到+500V(10％)的时间作为静电衰减时间进行测定。
<雾度(haze)>
使用Haze Meter，按照JIS K 7105测定1片试验片的光线透射率。
[实施例1]
在乙烯·甲基丙烯酸共聚物中配合丙烯·α-烯烃共聚物，制备具有下述成分组成的聚合物组合物，将该聚合物组合物中的羧基的一部分用钾离子中和，由此得到钾离聚物(以下称作“KIO-A”)(钾离子浓度：0.86mmol/g、MFR(230℃、2160g负荷)：5.9g/10分钟、密度：932kg/m3)。
(a)乙烯单元          38.1重量％
(b)丙烯单元          48.7重量％
(c)1-丁烯单元        4.1重量％
(d)丙烯酸酯单元      0.6重量％
(e)甲基丙烯酸单元    8.5重量％
[实施例2]
作为热塑性树脂，将80重量份均聚丙烯树脂(mp 161℃、MFR(按照JIS K-7210；230℃、2160g负荷)3g/10分钟)(以下称作“PP-1”)及20重量份KIO-A进行干混，利用铸塑成型装置
Figure GPA00001151307400101
在230℃下将上述混合物挤出，得到厚度为50μm的未拉伸膜。测定上述膜的雾度(haze)、表面电阻率及静电衰减时间。
结果示于表1。
[实施例3]
在实施例2中，将PP-1变更为70重量份及将KIO-A变更为30重量份，除此之外，与实施例2同样地得到未拉伸膜。测定上述膜的雾度(haze)、表面电阻率及静电衰减时间。
结果示于表1。
[实施例4]
作为热塑性树脂，将70重量份无规共聚丙烯树脂(mp139℃、MFR(230℃，2160g负荷)7g/10分钟)(以下称作“PP-2”)及30重量份KIO-A进行干混，利用铸塑成型装置
Figure GPA00001151307400111
在230℃下将上述混合物挤出，得到厚度为50μm的未拉伸膜。测定上述膜的雾度(haze)、表面电阻率及静电衰减时间。
结果示于表1。
[实施例5]
使用加压成型机，在210℃下对KIO-A进行加压，得到厚度为1mm的加压片材。
片材的表面电阻率(Ω/sq)的测定结果示于表1。
Figure GPA00001151307400121
[实施例6]
将乙烯·甲基丙烯酸共聚物(甲基丙烯酸单元含量20重量％)、丙烯·乙烯·1-丁烯无规共聚物(丙烯单元含量95.6重量％、乙烯单元含量2.4重量％、1-丁烯单元含量2.0重量％)与丙烯·1-丁烯无规共聚物(丙烯含量72重量％、1-丁烯含量28重量％)熔融混合，制备具有下述成分组成的聚合物组合物，将该聚合物组合物中的羧基的一部分用钾离子中和，由此得到钾离聚物(以下称作“KIO-B”)(钾离子浓度：0.86mmol/g、MFR(230℃、2160g负荷)：5.9g/10分钟、密度：932kg/m3)。
(a)乙烯单元        38.3重量％
(b)丙烯单元        49.0重量％
(c)1-丁烯单元      4.1重量％
(e)甲基丙烯酸单元  8.6重量％
[实施例7]
作为热塑性树脂，将80重量份均聚丙烯树脂(mp161℃、MFR(按照JIS K-7210；230℃、2160g负荷)3g/10分钟)(以下称作“PP-1”)及20重量份KIO-B进行干混，利用铸塑成型装置
Figure GPA00001151307400131
在230℃下将上述混合物挤出，得到厚度为50μm的未拉伸膜。测定上述膜的雾度(haze)、表面电阻率及静电衰减时间。
结果示于表2。
[实施例8]
在实施例7中，将PP-1变更为70重量份及将KIO-B变更为30重量份，除此之外，与实施例7同样地得到未拉伸膜。测定上述膜的雾度(haze)、表面电阻率及静电衰减时间。
结果示于表2。
[实施例9]
作为热塑性树脂，将70重量份无规共聚丙烯树脂(mp139℃、MFR(230℃，2160g负荷)7g/10分钟)(以下称作“PP-2”)及30重量份KIO-B进行干混，利用铸塑成型装置
Figure GPA00001151307400132
在230℃下将上述混合物挤出，得到厚度为50μm的未拉伸膜。测定上述膜的雾度(haze)、表面电阻率及静电衰减时间。
结果示于表2。
[实施例10]
使用加压成型机在210℃下对KIO-B进行加压，得到厚度为1mm的加压片材。
片材的表面电阻率(Ω/sq)的测定结果示于表2。
Figure GPA00001151307400151
[实施例11]
将乙烯·甲基丙烯酸共聚物(甲基丙烯酸单元含量20重量％)、丙烯·乙烯·1-丁烯无规共聚物(丙烯单元含量95.6重量％、乙烯单元含量2.4重量％、1-丁烯单元含量2.0重量％)与丙烯·1-丁烯无规共聚物(丙烯含量72重量％、1-丁烯含量28重量％)熔融混合，制备具有下述成分组成的聚合物组合物，将该聚合物组合物中的羧基的一部分用钾离子中和，由此得到钾离聚物(以下称作“KIO-C”)(钾离子浓度：0.87mmol/g、MFR(230℃、2160g负荷)：5.5g/10分钟、密度：937kg/m3)。
(a)乙烯单元        41.9重量％
(b)丙烯单元        45.1重量％
(c)1-丁烯单元      3.7重量％
(e)甲基丙烯酸单元  9.3重量％
使用加压成型机，在210℃下对KIO-C进行加压，得到厚度为1mm的加压片材。片材的表面电阻率(Ω/sq)的测定结果示于表2。
接下来，使用上述钾离聚物，与实施例7-9同样地制作未拉伸膜。可以期待该未拉伸膜的抗静电性能及雾度均良好。
[实施例12]
将乙烯·甲基丙烯酸共聚物(甲基丙烯酸单元含量20重量％)、丙烯·乙烯·1-丁烯无规共聚物(丙烯单元含量95.6重量％、乙烯单元含量2.4重量％、1-丁烯单元含量2.0重量％)和丙烯·1-丁烯无规共聚物(丙烯含量72重量％、1-丁烯含量28重量％)熔融混合，制备具有下述成分组成的聚合物组合物，将该聚合物组合物中的羧基的一部分用钾离子中和，由此得到钾离聚物(以下称作“KIO-D”)(钾离子浓度：0.90mmol/g、MFR(230℃、2160g负荷)：5.0g/10分钟、密度：936kg/m3)。
(a)乙烯单元    41.9重量％
(b)丙烯单元    45.1重量％
(c)1-丁烯单元        3.7重量％
(e)甲基丙烯酸单元    9.3重量％
使用加压成型机，在210℃下对KIO-D进行加压，得到厚度为1mm的加压片材。片材的表面电阻率(Ω/sq)的测定结果示于表2。
接下来，使用钾离聚物，与实施例7-9同样地制作未拉伸膜。可以期待该未拉伸膜的抗静电性能及雾度均良好。

Claims (8)

1.一种树脂组合物，含有2重量份以上至低于100重量份的钾离聚物(A)和高于0重量份至98重量份以下的除钾离聚物(A)之外的聚烯烃(B)，
所述钾离聚物(A)是将含有30～60重量％(a)乙烯单元、30～60重量％(b)丙烯单元、2～10重量％(c)丁烯单元、0～10重量％(d)(甲基)丙烯酸酯单元及5～15重量％(e)(甲基)丙烯酸单元的聚合物或聚合物组合物的羧基用钾离子中和得到的钾离聚物，其中，成分单元(a)～(e)的总计为100重量％，所述钾离聚物的钾离子密度在0.5～1.5mmol/g的范围内，
其中，钾离聚物(A)与聚烯烃(B)的总计为100重量份。
2.如权利要求1所述的树脂组合物，其中，所述聚烯烃(B)为丙烯均聚物或丙烯共聚物。
3.如权利要求1所述的树脂组合物，其特征在于，所述树脂组合物中的被钾离子中和之前的聚合物中所含有的(甲基)丙烯酸单元的含量为0.1～15重量％，另外，其钾离子密度在0.01～1.5mmol/g的范围内。
4.未拉伸膜、片材或成型体，是由权利要求1～3中任一项所述的树脂组合物形成的。
5.如权利要求4所述的未拉伸膜，雾度为20以下。
6.一种层合体，具有至少1层由未拉伸膜形成的层，所述未拉伸膜由权利要求1～3中任一项所述的树脂组合物形成。
7.一种层合体，是在未拉伸膜的单面或两面上层合聚烯烃膜而形成的，所述未拉伸膜由权利要求1～3中任一项所述的树脂组合物形成。
8.一种含有钾离聚物的高分子型抗静电剂，所述钾离聚物是含有30～60重量％(a)乙烯单元、30～60重量％(b)丙烯单元、2～10重量％(c)丁烯单元、0～10重量％(d)(甲基)丙烯酸酯单元及5～15重量％(e)(甲基)丙烯酸单元的聚合物或聚合物组合物的羧基用钾离子中和得到的钾离聚物，其中，成分单元(a)～(e)的总计为100重量％，所述钾离聚物的钾离子密度在0.5～1.5mmol/g的范围内。
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