CN113665209A - 一种聚酯液晶高分子薄膜及其制备方法 - Google Patents

一种聚酯液晶高分子薄膜及其制备方法 Download PDF

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CN113665209A
CN113665209A CN202010404611.8A CN202010404611A CN113665209A CN 113665209 A CN113665209 A CN 113665209A CN 202010404611 A CN202010404611 A CN 202010404611A CN 113665209 A CN113665209 A CN 113665209A
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polyester
lcp
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金亚东
周玉波
杨承翰
王雄伟
朱正平
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Ningbo Solartron Technology Co Ltd
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Abstract

本发明涉及一种聚酯液晶高分子(LCP)薄膜及其制备方法,该薄膜由AB层组成,厚度为100‑200μm;其中A层为液晶聚合物,属于功能层;B层为聚酯层,为支撑层;A层厚度占比为40‑70%,B层厚度占比为30‑60%。该薄膜拉伸强度为150‑250MPa,断裂伸长率40‑80%,CTE(热膨胀系数)为16‑22PPM/K,Dk(介电常数)为2.5‑2.8(20GHz),Df(介电损耗)为0.002‑0.003(20GHz),该薄膜通过双向拉伸制备而得,能够很好的替代聚酰亚胺薄膜。

Description

一种聚酯液晶高分子薄膜及其制备方法
技术领域
本发明涉及高分子薄膜加工技术领域,尤其涉及一种聚酯液晶高分子(LCP)薄膜及其制备方法。
背景技术
智能手机是当今世界上使用最广泛、最通用的电子设备。据IHS预计,自2017年起全球智能手机年出货量将超过15亿部。近年来随着通信网络网络从4G向5G过渡,网络频率不断提升。根据5G发展路线图,未来通信频率将分两个阶段进行提升。第一阶段的目标是在2020年前将通信频率提升到6GHz,第二阶段的目标是在2020年后进一步提升到30-60GHz。在市场应用方面,智能手机等终端天线的信号频率不断提升,高频应用越来越多,高速大容量的需求也越来越多。
传统终端天线主要采用基于PI(聚酰亚胺)基材的软板工艺(简称PI软板),通过对PI软板进一步加工得到天线模组(简称PI天线)。但是由于PI基材的介电常数和损耗因子较大、吸潮性较大、可靠性较差,因此PI软板的高频传输损耗严重。
液晶聚合物(LCP)是一种热塑性有机材料,可在保证较高可靠性的前提下实现高频高速软板。LCP具有优异的电学特征:(1)在高达110GHz的全部射频范围几乎能保持恒定的介电常数,一致性好;(2)正切损耗非常小,非常适合毫米波应用;(3)热膨胀特性非常小,可作为理想的高频封装材料。随着高频高速应用趋势的兴起,LCP将替代PI成为新的软板工艺。
传统制造液晶聚合物薄膜是先将其熔融后,再以例如射出模制、挤压模制、膨胀模制或吹气模制的方法来制造。但是,由于LCP的分子在排列上具有特定的方向性,因此,上述制造方法所形成的液晶聚合物薄膜内的分子排列是具有高度的同向性,薄膜容易因外应力而剥离或碎裂。因此本发明提供对LCP树脂进行改性,能够得到各项同性的薄膜,且具有很好的强度。
发明内容
本发明为得到一种聚酯液晶高分子(LCP)薄膜兼有良好的柔性能力和高频高速性能,并且能够满足5G天线和射频前端等高频电路的多层层压技术的模组化组装,已经成为通讯技术浪潮,所以在LCP薄膜组装成软板中,其机械强度和高频特性均非常重要。
本发明为提供一种聚酯液晶高分子(LCP)薄膜,其特征在于:该薄膜由AB层组成,厚度为100-200μm。
进一步的,所述的A层为改性液晶聚合物,属于功能层。
进一步的,所述的B层为聚酯层,为支撑层。
进一步的,所述的A层厚度占比为40-70%,B层厚度占比为30-60%。
进一步的,所述的薄膜拉伸强度为150-250MPa。
进一步的,所述的薄膜断裂伸长率60-120%。
进一步的,所述的薄膜热膨胀系数(CTE)为16-22PPM/K。
进一步的,所述的薄膜介电常数(Dk)为2.5-2.8(20GHz),介电损耗(Df)为0.002-0.003(20GHz)。
进一步的,所述的一种聚酯液晶高分子(LCP)薄膜的制备方法,其特征在于:
(1)将LCP树脂和聚酯树脂进入A双螺杆挤出机中,聚酯树脂和二氧化硅按照配比B双螺杆挤出机中,挤出机的温度控制在260-300℃,熔融塑化、流延铸片,模头温度为300-310℃,冷辊温度35℃;(2)将铸片进行同步拉伸,拉伸温度为180-280℃,收卷和分切,制备得聚酯液晶高分子(LCP)薄膜。
进一步的,所述的A层为改性液晶聚合物,由聚酯液晶高分子(LCP)和聚酯改性而得,其中聚酯液晶高分子(LCP)占80%(重量比),聚酯占20%(重量比)。
进一步的,所述的LCP为聚芳香酯类的热致型材料,其中含有-[-CO-Ar-O-]-[-OC-A-O-]-链节,其中Ar为苯基,A为萘基。
进一步的,所述的聚酯是聚对苯二甲酸1,4-环己烷二甲酯(PCT)、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PETG)和聚对苯二甲酸乙二醇酯(PET)的一种。
进一步的,所述的聚酯其中优选为聚对苯二甲酸1,4-环己烷二甲酯(PCT)。
进一步的,所述的B层为聚酯层,由聚酯和二氧化硅组成,其中聚酯占99.5%(重量比),二氧化硅占0.5%(重量比)。
进一步的,所述的聚酯是聚对苯二甲酸1,4-环己烷二甲酯(PCT)、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PETG)和聚对苯二甲酸乙二醇酯(PET)的一种。
进一步的,所述的聚酯其中优选为聚对苯二甲酸1,4-环己烷二甲酯(PCT)。
与现有技术相比,本发明制备的薄膜兼有良好的柔性能力和高频高速性能,并且能够满足5G天线和射频前端等高频电路的多层层压技术的模组化组装,
附图说明
图1为是本专利的结构示意图。
具体实施方式
本发明提供的一种聚酯液晶高分子(LCP)薄膜及其制备方法包括如下步骤:(1)将LCP树脂和聚酯树脂进入A双螺杆挤出机中,挤出机的温度分别为260、270、270、280、290、300、300、290、290℃,聚酯树脂和二氧化硅按照配比B双螺杆挤出机中,挤出机的温度分别为260、260、270、270、280、290、300、290、280℃,树脂在挤出机中熔融塑化、通过AB的熔体管道到模头,接着流延铸片,模头温度300-310℃,冷辊温度35℃;(2)将铸片进行同步拉伸,拉伸温度为180、200、240、260、280、260℃,收卷和分切,制备得LCP薄膜。
LCP薄膜的原料采购于以下公司:
(1)LCP树脂采购于日本宝理塑料公司,牌号为A950RX;
(2)PETG树脂采购于美国伊士曼化工有限公司,牌号为DN011;
(3)PCT树脂采购于美国杜邦,牌号为CG023;
(4)PET树脂采购于中国仪征化纤,牌号为FG720;
(5)二氧化硅采购于德国瓦克公司,牌号为HDK V15。
按照上述方法制备的LCP薄膜性能测试方法如下:
厚度:按照GB/T 6672-2001《塑料薄膜和薄片厚度测定机械测量法》。
拉伸强度和断裂伸长率:按照GB/T1040-2006标准,采用美国英斯特朗公司生产的INSTRON万能材料试验机。
热膨胀系数:按照ISO 11359-2-1999《塑料热力学分析(TMA)第2部分:线性热膨胀系数和玻璃化转变温度的测定》,使用PerkinElmer的TMA4000仪器进行测量。
介电常数和介电损耗:按照GB/T 1409-2006《测量电气绝缘材料在工频、音频、高频(包括米数波波长在内)下电容率和介质损耗因素的推荐方法》进行测试,设备使用北京智德创新仪器设备有限公司的QS37a橡胶塑料薄膜介电常数检测仪器,在20GHz条件进行测试。
实施例1
按照上述方法制备LCP薄膜,总厚度100μm,A层为40μm,B层为60μm。A层配比为80%A950RX,20%DN011;B层配方为99.5%DN011,0.5%V15。相关性能见表1。
实施例2
按照上述方法制备LCP薄膜,总厚度110μm,A层为45μm,B层为65μm。A层配比为80%A950RX,20%DN011;B层配方为99.5%DN011,0.5%V15。相关性能见表1。
实施例3
按照上述方法制备LCP薄膜,总厚度100μm,A层为50μm,B层为50μm。A层配比为80%A950RX,20%DN011;B层配方为99.5%DN011,0.5%V15。相关性能见表1。
实施例4
按照上述方法制备LCP薄膜,总厚度110μm,A层为50μm,B层为60μm。A层配比为80%A950RX,20%DN011;B层配方为99.5%CG023,0.5%V15。相关性能见表1。
实施例5
按照上述方法制备LCP薄膜,总厚度120μm,A层为50μm,B层为70μm。A层配比为80%A950RX,20%DN011;B层配方为99.5%CG023,0.5%V15。相关性能见表1。
实施例6
按照上述方法制备LCP薄膜,总厚度125μm,A层为50μm,B层为75μm。A层配比为80%A950RX,20%DN011;B层配方为99.5%FG720,0.5%V15。相关性能见表1。
实施例7
按照上述方法制备LCP薄膜,总厚度110μm,A层为60μm,B层为50μm。A层配比为80%A950RX,20%DN011;B层配方为99.5%FG720,0.5%V15。相关性能见表1。
表1实施例1-7薄膜性能测试表
Figure BDA0002489679210000031
实施例8
按照上述方法制备LCP薄膜,总厚度120μm,A层为60μm,B层为60μm。A层配比为80%A950RX,20%CG023;B层配方为99.5%DN011,0.5%V15。相关性能见表2。
实施例9
按照上述方法制备LCP薄膜,总厚度130μm,A层为60μm,B层为70μm。A层配比为80%A950RX,20%CG023;B层配方为99.5%DN011,0.5%V15。相关性能见表2。
实施例10
按照上述方法制备LCP薄膜,总厚度140μm,A层为60μm,B层为80μm。A层配比为80%A950RX,20%CG023;B层配方为99.5%DN011,0.5%V15。相关性能见表2。
实施例11
按照上述方法制备LCP薄膜,总厚度150μm,A层为60μm,B层为90μm。A层配比为80%A950RX,20%CG023;B层配方为99.5%CG023,0.5%V15。相关性能见表2。
实施例12
按照上述方法制备LCP薄膜,总厚度100μm,A层为70μm,B层为30μm。A层配比为80%A950RX,20%CG023;B层配方为99.5%CG023,0.5%V15。相关性能见表2。
实施例13
按照上述方法制备LCP薄膜,总厚度110μm,A层为70μm,B层为40μm。A层配比为80%A950RX,20%CG023;B层配方为99.5%FG720,0.5%V15。相关性能见表2。
实施例14
按照上述方法制备LCP薄膜,总厚度120μm,A层为70μm,B层为50μm。A层配比为80%A950RX,20%CG023;B层配方为99.5%FG720,0.5%V15。相关性能见表2。
表2实施例8-14薄膜性能测试表
Figure BDA0002489679210000041
实施例15
按照上述方法制备LCP薄膜,总厚度125μm,A层为80μm,B层为35μm。A层配比为80%A950RX,20%FG720;B层配方为99.5%DN011,0.5%V15。相关性能见表3。
实施例16
按照上述方法制备LCP薄膜,总厚度130μm,A层为80μm,B层为50μm。A层配比为80%A950RX,20%FG720;B层配方为99.5%DN011,0.5%V15。相关性能见表3。
实施例17
按照上述方法制备LCP薄膜,总厚度160μm,A层为80μm,B层为80μm。A层配比为80%A950RX,20%FG720;B层配方为99.5%DN011,0.5%V15。相关性能见表3。
实施例18
按照上述方法制备LCP薄膜,总厚度120μm,A层为90μm,B层为30μm。A层配比为80%A950RX,20%FG720;B层配方为99.5%CG023,0.5%V15。相关性能见表3。
实施例19
按照上述方法制备LCP薄膜,总厚度150μm,A层为90μm,B层为60μm。A层配比为80%A950RX,20%FG720;B层配方为99.5%CG023,0.5%V15。相关性能见表3。
实施例20
按照上述方法制备LCP薄膜,总厚度160μm,A层为100μm,B层为60μm。A层配比为80%A950RX,20%FG720;B层配方为99.5%FG720,0.5%V15。相关性能见表3。
实施例21
按照上述方法制备LCP薄膜,总厚度200μm,A层为100μm,B层为100μm。A层配比为80%A950RX,20%FG720;B层配方为99.5%FG720,0.5%V15。相关性能见表3。
表3实施例15-21薄膜性能测试表
Figure BDA0002489679210000051
以上所述,仅为本发明的较佳实施例而已,并非用于限定本发明的保护范围。凡是根据本发明内容所做的均等变化与修饰,均涵盖在本发明的专利范围内。

Claims (10)

1.一种聚酯液晶高分子(LCP)薄膜,其特征在于:该薄膜由AB层组成,厚度为100-200μm,该薄膜拉伸强度为150-250MPa,断裂伸长率60-120%。
2.根据权利要求1所述的聚酯液晶高分子(LCP)薄膜,其特征在于:所述的薄膜热膨胀系数(CTE)为16-22PPM/K。
3.根据权利要求1所述的聚酯液晶高分子(LCP)薄膜,其特征在于:所述的薄膜介电常数(Dk)为2.5-2.8(20GHz),介电损耗(Df)为0.002-0.003(20GHz)。
4.根据权利要求1所述的聚酯液晶高分子(LCP)薄膜,其特征在于:所述的A层为改性液晶聚合物,属于功能层;B层为聚酯层,为支撑层;A层厚度占比为40-70%,B层厚度占比为30-60%。
5.根据权利要求1所述的聚酯液晶高分子(LCP)薄膜,其特征在于:所述的A层为改性液晶聚合物,由聚酯液晶高分子(LCP)和聚酯改性而得,其中聚酯液晶高分子(LCP)占80%(重量比),聚酯占20%(重量比)。
6.根据权利要求5所述的聚酯液晶高分子(LCP)薄膜,其特征在于:所述的LCP为聚芳香酯类的热致型材料,其中含有-[-CO-Ar-O-]-[-OC-A-O-]-链节,其中Ar为苯基,A为萘基。
7.根据权利要求5的聚酯液晶高分子(LCP)薄膜,其特征在于:所述的聚酯是聚对苯二甲酸1,4-环己烷二甲酯(PCT)、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PETG)和聚对苯二甲酸乙二醇酯(PET)的一种,其中优选为聚对苯二甲酸1,4-环己烷二甲酯(PCT)。
8.根据权利要求1所述的聚酯液晶高分子(LCP)薄膜,其特征在于:所述的B层为聚酯层,由聚酯和二氧化硅组成,其中聚酯占99.5%(重量比),二氧化硅占0.5%(重量比)。
9.根据权利要求8所述的聚酯液晶高分子(LCP)薄膜,其特征在于:所述的聚酯是聚对苯二甲酸1,4-环己烷二甲酯(PCT)、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PETG)和聚对苯二甲酸乙二醇酯(PET)的一种,其中优选为聚对苯二甲酸1,4-环己烷二甲酯(PCT)。
10.一种聚酯液晶高分子(LCP)薄膜的制备方法,其特征在于:包括如下步骤:(1)将LCP树脂和聚酯树脂进入A双螺杆挤出机中,聚酯树脂和二氧化硅按照配比B双螺杆挤出机中,挤出机的温度控制在260-300℃,熔融塑化、流延铸片,模头温度300-310℃,冷辊温度35℃;(2)将铸片进行同步拉伸,拉伸温度为180-280℃,收卷和分切,制备得聚酯液晶高分子(LCP)薄膜。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114133603A (zh) * 2021-12-14 2022-03-04 宁波长阳科技股份有限公司 一种液晶高分子薄膜力学性能的改善方法及液晶高分子薄膜

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114133603A (zh) * 2021-12-14 2022-03-04 宁波长阳科技股份有限公司 一种液晶高分子薄膜力学性能的改善方法及液晶高分子薄膜
CN114133603B (zh) * 2021-12-14 2023-08-29 宁波长阳科技股份有限公司 一种液晶高分子薄膜力学性能的改善方法及液晶高分子薄膜

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