CN1329176C - 载体膜及其制造方法 - Google Patents

载体膜及其制造方法 Download PDF

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CN1329176C
CN1329176C CNB2004100033995A CN200410003399A CN1329176C CN 1329176 C CN1329176 C CN 1329176C CN B2004100033995 A CNB2004100033995 A CN B2004100033995A CN 200410003399 A CN200410003399 A CN 200410003399A CN 1329176 C CN1329176 C CN 1329176C
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贺屋政德
富宿勉
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AGC Inc
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Abstract

本发明涉及载体膜，该载体膜的特征是，它是在聚酯树脂的延伸膜的两面层叠了四氟乙烯-乙烯系共聚物膜的层压膜，按照JIS K7105的基准测定的该层压膜的浊度在5%以下。

Description

载体膜及其制造方法
技术领域
本发明涉及透明度、耐溶剂性及脱模性良好的载体膜。
背景技术
载体膜是由溶液形成流延膜时所用的承载膜，为了获得平滑的流延膜，要求载体膜的表面平滑性、耐溶剂性和脱模性(也称为剥离性)等特性良好。
以往，作为载体膜使用的是用于剥离模的含氟树脂膜(例如，参考专利文献1)、具有聚硅氧烷化合物的薄表面层的双轴延伸聚对苯二甲酸乙二醇酯膜(例如，参考专利文献2)等。
含氟树脂膜的耐溶剂性和脱模性等特性良好，但一般价格较高。如果减小含氟树脂膜的厚度，则虽然能够降低价格，但容易在含氟树脂薄膜上产生皱褶，出现处理性劣化的问题。此外，具有聚硅氧烷化合物的薄表面层的双轴延伸聚对苯二甲酸乙二醇酯膜存在聚硅氧烷化合物会转移至流延膜表面的问题。
由于对高品质的流延膜有不出现膜厚不均一、尘埃混入等缺陷的要求，所以在制造时要通过光学手段检测出这些缺陷，这就要求有透明度高的载体膜。专利文献2中揭示了用粘合剂对含氟树脂膜和双轴延伸聚对苯二甲酸乙二醇酯膜进行干式层压而制得的具有含氟树脂表面层的延伸PET膜形成的载体膜。但是，这种载体膜的透明度不够理想。
专利文献1：日本专利特开平6-226873号公报，专利文献2：日本专利特开2002-67241号公报。
本发明的目的是提供能够解决上述问题的透明度高、且具有良好耐溶剂性和脱模性的载体膜。
发明内容
本发明提供了载体膜，该膜的特征是，它是在聚酯树脂的延伸膜的两面层叠了四氟乙烯-乙烯系共聚物膜的层压膜，按照JIS K7105的基准测定的该层压膜的浊度在5％以下。
本发明还提供了前述载体膜的制造方法，该方法的特征是，通过挤压层叠在聚酯树脂的延伸膜的两面层叠四氟乙烯-乙烯系共聚物。
具体实施方式
本发明的四氟乙烯-乙烯系共聚物(以下称为ETFE)是四氟乙烯(以下称为TFE)、乙烯(以下称为E)及可与它们共聚的含氟乙烯基单体(四氟乙烯除外)的共聚物，基于TFE的聚合单元/基于E的聚合单元的摩尔比为50～60/50～40，基于含氟乙烯基单体的聚合单元的含量对应于全部聚合单元较好为2～7摩尔％。在此范围内，载体膜的透明度、耐溶剂性及脱模性良好。
基于TFE的聚合单元/基于E的聚合单元的摩尔比更好为53～60/47～40。基于含氟乙烯基单体的聚合单元的含量对应于全部聚合单元更好为2～5摩尔％。
前述含氟乙烯基单体较好为CH2＝CH-CnF2n+1(n为2～10的整数)表示的(全氟烷基)乙烯。如果含有基于含氟乙烯基单体的聚合单元，则载体膜的透明度、耐溶剂性和脱模性良好。n更好为2～6。其具体例子包括CH2＝CH-C2F5、CH2＝CH-C3F7、CH2＝CH-C4F9、CH2＝CH-C5F11、CH2＝CH-C6F13等。更好的是CH2＝CH-C4F9。
本发明的聚酯树脂的延伸膜是将聚对苯二甲酸乙二酯(以下称为PET)、聚萘二甲酸乙二酯、聚对苯二甲酸丁二酯、聚萘二甲酸丁二酯等聚酯树脂拉伸而形成的膜。其中，PET的延伸膜(以下称为延伸PET膜)的厚度精度、热特性和机械特性等良好，且价格低廉，所以最理想。
本发明的聚酯树脂的延伸膜(以下也称为延伸聚酯树脂膜)的厚度较好为10～100μm，更好为25～50μm。延伸聚酯树脂膜如果过薄，则处理性下降，如果过厚，则载体膜的厚度精度下降。在上述范围内的载体膜的处理性及厚度精度良好。聚酯树脂膜的延伸方法包括单轴或双轴延伸，更好的是双轴延伸。双轴延伸的聚酯树脂膜的拉伸断裂强度和透明度等良好，所以非常理想。
本发明的载体膜最好通过挤压层叠在延伸聚酯树脂膜的两面层叠ETFE而制得。挤压层叠是指用挤压机挤压成形ETFE膜，成形后的ETFE膜与延伸聚酯树脂膜重叠，然后插入滚筒间而层压。
挤压层叠时为了粘合延伸聚酯树脂膜和ETFE膜最好使用粘合剂。使用粘合剂能够获得ETFE膜和延伸聚酯树脂膜的层间粘合力高的载体膜。所用粘合剂包括聚酯系粘合剂、聚氨酯系粘合剂、丙烯酸系粘合剂等。其中，特别好的是聚酯系粘合剂。聚酯粘合剂的具体例子为旭硝子株式会社制AG-9014A、东亚合成株式会社制PES111SK-20、PES140、PES120等。
制造工序的具体例子如下所述。利用凹印滚筒在双轴延伸PET膜上涂布聚酯系粘合剂并使其干燥，制得单面具有粘合剂层的双轴延伸PET膜(以下称为单面粘合性PET膜)后，将该膜卷成滚筒状。然后，将该滚筒固定在卷绕机中。用挤压机挤压成形的ETFE膜与成形后从卷绕机中送出的单面粘合性PET膜在单面粘合性PET膜的粘合剂涂布面层叠，然后插入加热后的金属滚筒和水冷后的聚硅氧烷橡胶制后滚筒之间完成层压，再将所得双层层压膜卷成滚筒状。接着，对双轴延伸PET膜的另一面进行同样的操作，制得作为本发明的载体膜的ETFE膜/延伸聚酯树脂膜/ETFE膜的三层层压膜。
粘合剂层的厚度较好为0.1～5μm，更好为0.3～2μm。金属滚筒的加热温度较好为100～170℃，更好为120～150℃。层压膜的卷绕速度较好为5～30m/分钟，更好为15～20m/分钟。
本发明的载体膜中的ETFE膜的厚度较好为1～10μm，更好为1～7μm，最好为1～5μm。在上述范围内，载体膜的耐擦伤性良好，挤压层叠时不会产生小孔，并能维持良好的ETFE脱模性和非粘合性等特性。
本发明的载体膜的厚度较好为10～200μm，更好为12～150μm，最好为15～100μm。在此范围内处理性良好。
按照JIS K7105的基准测定的本发明的载体膜的浊度在5％以下，较好的是在4％以下，更好的是在3％以下。在此范围内透明度高，对流延膜的缺陷进行光学检查时，光学检测机的S/N比有向上的倾向。按照JIS K7105的基准测定的浊度是指用积分球式光线透过率测定装置测定扩散透过率及全部的光线透过率，由其比值表示的值。
本发明的载体膜中的聚酯树脂膜和ETFE膜的层间粘合力较好为3～80g/cm，更好为6～60g/cm，最好为10～40g/cm。在此范围内使用时，层间难剥离，使用耐久性良好。
本发明的载体膜的用途包括耐溶剂性剥离膜、易剥离性膜、耐热性剥离膜、耐酸性剥离膜、耐碱性剥离膜等。特别好的是易于剥离含有无机粒子和粘合剂的组合物溶液通过辊冷成膜形成的膜的易剥离性载体膜，以及通过辊冷成膜由溶液形成高分子膜时所用的耐溶剂性载体膜等。
以下例举实施例对本发明进行具体说明，但本发明并不仅限于此。此外，采用下述方法对载体膜的脱模性、浊度、断裂强度和拉伸度进行测定。
[脱模性]使加成反应型的固化型液状聚硅氧烷橡胶(信越化学工业株式会社制KE1988(A/B))溶于甲基乙基甲酮/甲基异丁基甲酮/甲苯(质量比25/25/50)的混合溶剂中，获得固形成分浓度为5质量％的溶液。在层压膜上涂布该溶液，使在150℃干燥1分钟的聚硅氧烷固化。然后，用手从层压膜剥离该聚硅氧烷，对层压膜的脱模性进行评价。容易剥离的情况记为“○”，难剥离的情况记为“×”。
[浊度(％)]采用スガ试验机株式会社制SM全色计算机SM-5，按照JISK7105的基准测定层压膜的浊度。
[断裂强度及拉伸度]按照ASTM D-638的基准，测定载体膜的断裂强度及拉伸度。MD表示膜的挤压方向，TD表示膜的宽度方向。
[实施例1]
在厚38μm、宽1200mm的双轴延伸PET膜(帝人株式会社制，GEC38)的一面上涂布聚酯系粘合剂(旭硝子株式会社制，AG-9014A)，使干燥涂膜的厚度达到0.4μm。将所得的涂布了粘合剂的PET膜设置于挤压层叠装置。
在320℃熔融挤压聚合物组成为基于TFE的聚合单元/基于E的聚合单元/基于(全氟丁基)乙烯(以下称为PFBF)的聚合单元＝56.3/40.7/3.0(摩尔比)的ETFE。然后，调整模唇使挤压后的ETFE膜的膜厚达到4μm。于130℃用后滚筒将挤压的ETFE膜层叠于PET膜的粘合剂涂布面。
对双轴延伸PET的相反侧的一面进行同样的操作，制得ETFE膜/双轴延伸PET膜/ETFE膜的三层层压膜形成的载体膜。ETFE层的厚度为4μm，双轴延伸PET层的厚度为38μm，载体膜的厚度为46.8μm。厚度差及脱模性的测定结果如表1所示。在脱模试验后的载体膜的表面未观察到皱褶和膨胀等，说明耐溶剂性良好。所得聚硅氧烷橡胶的流延膜具有无皱褶、波纹等缺陷的平滑的表面。
[比较例1]
除了使用组成为基于TFE的聚合单元/基于E的聚合单元/基于PFBE的聚合单元＝52.3/46.4/1.3(摩尔比)的ETFE之外，其他都与实施例1相同，获得在双轴延伸PET膜的两面层叠了ETFE膜的层压膜。厚度差及脱模性的测定结果如表1所示。
表1
  ETFE组成(摩尔比)TFE/E/PFBE 浊度(％) 脱模性 断裂强度MD/TD(MPa) 拉伸度MD/TD(％)
实施例1  56.3/40.7/3.0  3.1 ○  163/183 140/120
比较例1  52.3/46.4/1.3  5.7 ○  186/180 152/120
本发明的载体膜具有良好的透明度、耐溶剂性和脱模性。制造时容易通过光学手段检测出流延膜的缺陷。

Claims (7)

1.载体膜，其特征在于，它是在聚酯树脂的延伸膜的两面层叠了四氟乙烯-乙烯系共聚物膜的层压膜，按照JIS K7105的基准测定的该层压膜的浊度在5％以下，前述四氟乙烯-乙烯系共聚物是四氟乙烯、乙烯及可与它们共聚的除四氟乙烯以外的含氟乙烯基单体的共聚物，基于四氟乙烯的聚合单元/基于乙烯的聚合单元的含有摩尔比为50～60/50～40，基于含氟乙烯基单体的聚合单元的含量对应于全部聚合单元为2～7摩尔％。
2.如权利要求1所述的载体膜，其特征还在于，前述含氟乙烯基单体为CH2＝CH-CnF2n+1表示的(全氟烷基)乙烯，其中的n为2～10的整数。
3.如权利要求1或2所述的载体膜，其特征还在于，聚酯树脂的延伸膜的厚度为10～100μm。
4.如权利要求1～3中任一项所述的载体膜，其特征还在于，聚酯树脂为聚对苯二甲酸乙二醇酯。
5.如权利要求1～4中任一项所述的载体膜，其特征还在于，四氟乙烯-乙烯系共聚物膜的厚度为1～10μm。
6.如权利要求1～5中任一项所述的载体膜，其特征还在于，载体膜的厚度为10～200μm。
7.权利要求1～6中任一项所述的载体膜的制造方法，其特征在于，通过挤压层叠在聚酯树脂的延伸膜的两面层叠四氟乙烯-乙烯系共聚物。
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AT502234B1 (de) 2005-07-21 2008-06-15 Isovolta Verfahren zur herstellung witterungsbeständiger laminate für die einkapselung von solarzellensystemen
KR101306537B1 (ko) 2008-06-04 2013-09-09 콜게이트-파아므올리브캄파니 캐비테이션 시스템을 가진 구강 관리기구
US8858850B2 (en) * 2009-07-02 2014-10-14 E I Du Pont De Nemours And Company Process for preparing decorative surface appearance in acrylic material employing anisotropic particles
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KR101734425B1 (ko) 2013-09-24 2017-05-11 주식회사 엘지화학 드라이 필름 솔더 레지스트의 제조 방법과, 이에 사용되는 필름 적층체

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