CN116239774A - 一种聚酰亚胺、聚酰亚胺薄膜及其制备方法和应用 - Google Patents
一种聚酰亚胺、聚酰亚胺薄膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种聚酰亚胺、聚酰亚胺薄膜及其制备方法和应用,兼具低热膨胀系数、高热粘性、高耐热性和高拉伸强度,可应用于层压法制作无胶双面柔性覆铜板。该聚酰亚胺高分子结构单元中含有可提供配位点和空间位置的N,O原子,如吡啶,恶唑,吡唑等强配位结构,可在热加工过程与覆铜板表面裸露的铜元素形成键能较强的配位键,使聚酰亚胺薄膜与覆铜板之间具有超强的粘结力,同时薄膜本体具有出色的力学性能、热学性能和力学性能。该热粘型聚酰亚胺薄膜无需外加环氧树脂或丙烯酸等粘结剂,就可在热加工过程中强有力附着在铜箔,因此适合热压法快速制备双面柔性覆铜板,其剥离强度达到0.6N/mm以上,最高达到1.4N/mm,在无胶柔性覆铜板领域有巨大应用前景。
Description
技术领域
本发明涉及电子材料的技术领域,尤其是涉及一种聚酰亚胺、聚酰亚胺薄膜及其制备方法和应用。
背景技术
覆铜箔层压板是将电子玻纤布或其它增强材料浸以树脂,一面或双面覆以铜箔并经热压而制成的一种板状材料,简称为覆铜板。聚酰亚胺(PI Polyimide)薄膜作为一类优质的绝缘高分子材料,具有优异的热稳定性、化学稳定性、机械性能以及低介电常数,自上个世纪五十年代开始投入市场商用以来,目前已在航天航空,电子,工程等高新技术领域取得了广泛的应用。在电子器件领域,传统的刚性电路板正在被具有轻薄,柔韧特性的柔性印刷电路板(FPC Flexible Printed Circuit board)所取代,用于生产FPC的聚酰亚胺柔性覆铜板(FCCL Flexible Copper Clad Lamination),是当前PI薄膜应用研究的一大重点方向。
FCCL按其结构可分为三层柔性覆铜板(3L-FCCL)与二层柔性覆铜板(2L-FCCL),两者间的主要差异在于聚酰亚胺薄膜与铜箔基板之间是否存在胶粘剂;前者作为传统型FPC材料技术手段已较为成熟:采用热层压工艺粘结铜箔与聚酰亚胺膜层,得到铜箔/胶粘剂/聚酰亚胺的三层结构,胶粘剂多为环氧树脂或丙烯酸酯类,目前投入商业应用最为广泛;然而,3L-FCCL的性能受胶粘剂本身性质的显著影响,具体表现在其耐热性能受胶粘剂的限制,精密加工时由于胶粘剂的存在引起尺寸的偏差,高温时出现剥离分层以及厚度较大等问题,因此,对于更优性能的FCCL的需求强烈。近年来研发的新型FPC二层柔性覆铜板2L-FCCL,直接复合铜箔与聚酰亚胺薄膜,取消了中间胶粘剂层,也即无胶覆铜板,很好地克服了以上3L-FCCL中由胶粘剂带来的性能不足,由于目前国内尚处研发与生产的初级阶段,具有广阔的应用前景。用于2L-FCCL是PI薄膜难点在于,热性能和粘结性能之间的矛盾:结构柔性越出色热粘性越强,到同时导致热膨胀系数和热稳定性较差。
发明内容
本发明要解决的技术问题是针对上述现有技术的不足,而提供一种聚酰亚胺、聚酰亚胺薄膜及其制备方法和应用,该聚酰亚胺薄膜兼具低热膨胀系数、高热粘性、高耐热性和高拉伸强度,可应用于层压法制作无胶双面柔性覆铜板(2L-FCCL)。
为实现上述目的,本发明的聚酰亚胺、聚酰亚胺薄膜及其制备方法和应用的具体技术方案如下:
一种聚酰亚胺,包含下式所示的重复单元:
上式中,Ar1属于至少含有一个芳环的二胺的一部分,Ar2属于至少含有一个芳环的二酸酐的一部分。
进一步,所述Ar1的结构中含有不少于一个芳环或者芳杂环,芳环上、芳杂环上或相连的结构上含有N原子和O原子中的至少一种。
进一步,所述Ar1与芳环或芳杂环相连的结构中含有N原子和O原子、可以直接相连的环内原子或者是环上的取代基含有的原子。
进一步,二胺的结构式中的Ar1为以下结构中的一种:
进一步,所述Ar2的结构中含有至少一个芳环。
本发明还提供了一种聚酰亚胺薄膜,所述聚酰亚胺薄膜部分或全部包含以上所述的聚酰亚胺。
本发明还提供了一种聚酰亚胺薄膜的制备方法,其包括以下步骤:
S1、制备溶液:在5-10℃下,将二胺和二酐在溶剂中缩聚成聚酰亚胺酸溶液;
S2、制成胶膜:使用聚酰亚胺酸溶液在玻璃或者钢板上利用流涎法成膜,得到湿膜,湿膜经真空烘箱烘干制得胶膜;
S3、得到薄膜:将胶膜揭下,四边用夹棍夹住,送入高温烘箱中亚胺化得到薄膜,将薄膜泡入水中,从玻璃或钢板上揭下,并烘干。
进一步,
步骤S1中,
聚酰亚胺酸溶液的固含量为10-30%,粘度为5000-30000mPa·s;
溶剂采用强极性溶剂,为丙酮、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、γ-丁内酯中的一种或多种;
二酐单体与二胺单体的总摩尔数之比为(0.95-1.05):1;
步骤S2中,
利用流涎法得到的湿膜的厚度为800-2000um;湿膜烘干制得胶膜的真空烘箱的烘干温度为60-80℃;
步骤S3中,
亚胺化采用阶梯式升温后自然冷却的方式,阶梯式升温的过程为:第一阶段:在150℃下加热2h;第二阶段:升温至200℃,保温1h;第三阶段:升温至250℃,保温1h;第四阶段:升温至300℃,保温0.5h;第五阶段:升温至350℃,保温0.5h;
薄膜揭下后烘干的烘干温度为80℃,烘干时间为2h。
本发明还提供了一种聚酰亚胺薄膜的应用,将所述聚酰亚胺薄膜应用在二层柔性覆铜板中,采用热压法直接将铜箔与聚酰亚胺薄膜压制成二层柔性覆铜板;热压法的热压温度为330-360℃,压力为0.5Mpa,热压时间为30-60s。
与现有技术相比,本发明的有益效果是:
一、本发明在聚酰亚胺中引入联吡啶,恶唑,咪唑等含N,O原子的结构的单体,采用该方法所制备得到的含N,O原子配位基元的热粘型聚酰亚胺薄膜兼具出色的热膨胀系数和高热粘性,解决了热粘性和热膨胀之间的不可兼得的矛盾。
二、本发明的制备含N,O原子配位基元的热粘型聚酰亚胺,同时具备出色的力学性能和玻璃化温度,能够满足2F-FCCL领域的应用,值得广泛推广进行应用。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为三层(3L-FCCL)和双层(2L-FCCL)覆铜板工艺差异的示意图;
图2为聚酰亚胺所包含的重复单元;
图3为说明书实验例1中的表2中的实施例6的DSC图;
图4为说明书实验例1中的表2中的实施例7的DSC图。
具体实施方式
为了更好地了解本发明的目的、结构及功能,下面结合附图和具体较佳实施方式,对本发明一种聚酰亚胺、聚酰亚胺薄膜及其制备方法和应用做进一步详细的描述。
实施例1:
请参阅图1-4,本发明提供一种技术方案:
一种聚酰亚胺,包含下式所示的重复单元:
其中酸酐为原料形成的酰亚胺键,Ar1属于至少含有一个芳环的二胺,Ar2属于至少含有一个芳环的二酸酐。
进一步,所述Ar1的结构中含有不少于一个芳环或者芳杂环,芳环上、芳杂环上或相连的结构上含有N原子和O原子中的至少一种。
进一步,所述Ar1与芳环或芳杂环相连的结构中含有N原子和O原子、可以直接相连的环内原子或者是环上的取代基含有的原子。
进一步,二胺的结构式中的Ar1为以下结构中的一种:
进一步,所述Ar2的结构中含有至少一个芳环。
从结构上分析,含芳环共轭结构具有较高的热稳定性,使聚酰亚胺薄膜具有较高的玻璃化温度,同时多芳环共轭结构之间的堆积作用使得聚酰亚胺薄膜具有较低的热膨胀系数。通过二胺单体引入含有N,O原子基元,增强聚酰亚胺分子间给受电子作用,强化堆积作用和链与链之间的缠绕,提供了出色的热稳定性和力学性能;含N,O原子的单体与铜箔表面的铜原子在高温下形成配位键强度远大于铜与共轭键的配位作用,因此以配位键形式的铜箔粘结效用更强。
实施例2:
本发明还提供了一种聚酰亚胺薄膜,所述聚酰亚胺薄膜部分或全部包含以上所述的聚酰亚胺。
实施例3:
本发明还提供了一种聚酰亚胺薄膜的制备方法,其包括以下步骤:
S1、制备溶液:在5-10℃下,将二胺和二酐在溶剂中缩聚成聚酰亚胺酸溶液(PAA);
S2、制成胶膜:使用聚酰亚胺酸溶液在玻璃或者钢板上利用流涎法成膜,得到湿膜,湿膜经真空烘箱烘干制得胶膜;
S3、得到薄膜:将胶膜揭下,四边用夹棍夹住,送入高温烘箱中经历高温完全亚胺化得到薄膜,将薄膜泡入水中,从玻璃或钢板上揭下,并烘干。
该薄膜为结构单元中含有可以提供配位点和空间位置的N,O原子的结构,引入该类强配位结构,可以在热加工过程与覆铜板表面裸露的铜元素形成键能较强的配位键,使聚酰亚胺薄膜与覆铜板之间具有超强的粘结力。采用该方法所制备得到的热粘型聚酰亚胺薄膜具有出色的力学性能、热学性能以及与铜箔的出色粘结性能,可以制备无胶型2L-FCCL,值得广泛推广进行应用。
进一步,
步骤S1中,
为能获得更高的力学性能和热学性能的薄膜,二胺和二酐单体采用多种单体共聚得到PAA溶液,其中至少有一种单体符合实施例1中的规定。
聚酰亚胺酸溶液的固含量为10-30%,粘度为5000-30000mPa·s;
溶剂采用强极性溶剂,为丙酮、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、γ-丁内酯中的一种或多种;
二酐单体与二胺单体的总摩尔数之比为(0.95-1.05):1;
缩聚反应式如下:
步骤S2中,
利用流涎法得到的湿膜的厚度为800-2000um;湿膜烘干制得胶膜的真空烘箱的烘干温度为60-80℃;
步骤S3中,
亚胺化采用阶梯式升温后自然冷却的方式,阶梯式升温的过程为:第一阶段:在150℃下加热2h;第二阶段:升温至200℃,保温1h;第三阶段:升温至250℃,保温1h;第四阶段:升温至300℃,保温0.5h;第五阶段:升温至350℃,保温0.5h;
薄膜揭下后烘干的烘干温度为80℃,烘干时间为2h。
实施例4:
本发明还提供了一种聚酰亚胺薄膜的应用,将所述聚酰亚胺薄膜应用在二层柔性覆铜板中,采用热压法直接将铜箔与聚酰亚胺薄膜压制成二层柔性覆铜板;热压法的热压温度为330-360℃,压力为0.5Mpa,热压时间为30-60s。
进一步,根据国家标准GB/T 13555-2017测试无胶覆铜板的剥离强度,当剥离强度≥0.6N/mm为合格。
实验例1:
以实施例1作为组别1为基础,其他组别二胺和二酐的制备PAA溶液和亚胺化成膜的工艺一致,只是将选择不同的Ar1、Ar2,然后将二胺单体和二酐制备成聚酰亚胺膜在室温25℃进行检测,厚度均为30μm。将聚酰亚胺膜与25um厚铜箔进行三层热压合,测试剥离强度。
表1、Ar1、Ar2对二胺单体结构式的影响:
表2、Ar1、Ar2对聚酰亚胺膜性能的影响:
通过分析实施例1-10以及对比例1-2所制成的PI薄膜的拉伸强度,玻璃化温度,热膨胀系数和用PI和覆铜板热压合之后的剥离强度。可以发现,除8和9以外,大部分对比例使用单体中含有N,O原子配位基元的二胺和二酐,可以制备具有高拉伸强度,高玻璃化温度和低热膨胀系数的PI薄膜,且PI薄膜与覆铜板热压合可获得高剥离强度的PI覆铜板。
工作原理:
本发明公开了一种聚酰亚胺、聚酰亚胺薄膜及其制备方法和应用,具体为一种新型含N,O原子配位基元的热粘型聚酰亚胺薄膜,兼具低热膨胀系数、高热粘性、高耐热性和高拉伸强度,可应用于层压法制作无胶双面柔性覆铜板(2L-FCCL)。在该聚酰亚胺高分子结构单元中含有可以提供配位点和空间位置的N,O原子,例如吡啶,恶唑,吡唑等强配位结构,可以在热加工过程与覆铜板表面裸露的铜元素形成键能较强的配位键,使聚酰亚胺薄膜与覆铜板之间具有超强的粘结力,同时薄膜本体具有出色的力学性能、热学性能和力学性能。本发明中的热粘型聚酰亚胺薄膜无需外加环氧树脂或丙烯酸等粘结剂,就可以在热加工过程中强有力附着在铜箔,因此适合热压法快速制备双面柔性覆铜板(2L-FCCL),其剥离强度达到0.6N/mm以上,最高达到1.4N/mm,在无胶柔性覆铜板领域有巨大应用前景。
可以理解,本发明是通过一些实施例进行描述的,本领域技术人员知悉的,在不脱离本发明的精神和范围的情况下,可以对这些特征和实施例进行各种改变或等效替换。另外,在本发明的教导下,可以对这些特征和实施例进行修改以适应具体的情况及材料而不会脱离本发明的精神和范围。因此,本发明不受此处所公开的具体实施例的限制,所有落入本申请的权利要求范围内的实施例都属于本发明所保护的范围内。
Claims (10)
2.根据权利要求1所述的聚酰亚胺,其特征在于,所述Ar1的结构中含有不少于一个芳环或者芳杂环,芳环上、芳杂环上或相连的结构上含有N原子和O原子中的至少一种。
3.根据权利要求2所述的聚酰亚胺,其特征在于,所述Ar1与芳环或芳杂环相连的结构中含有N原子和O原子、可以直接相连的环内原子或者是环上的取代基含有的原子。
5.根据权利要求1所述的聚酰亚胺,其特征在于,所述Ar2的结构中含有至少一个芳环。
6.一种聚酰亚胺薄膜,其特征在于,其包含权利要求1-5任一项所述的聚酰亚胺。
7.一种如权利要求6所述的聚酰亚胺薄膜的制备方法,其特征在于,包括以下步骤:
S1、制备溶液:将二胺和二酐在溶剂中缩聚成聚酰亚胺酸溶液;
S2、制成胶膜:使用聚酰亚胺酸溶液在玻璃或者钢板上利用流涎法成膜,得到湿膜,湿膜经真空烘箱烘干制得胶膜;
S3、得到薄膜:将胶膜揭下,四边用夹棍夹住,送入高温烘箱中亚胺化得到薄膜,将薄膜泡入水中,从玻璃或钢板上揭下,并烘干。
8.根据权利要求7所述的聚酰亚胺薄膜的制备方法,其特征在于:
步骤S1中,
二胺和二酐进行缩聚反应的温度为5-10℃;
聚酰亚胺酸溶液的固含量为10-30%,粘度为5000-30000mPa·s;
溶剂采用强极性溶剂,为丙酮、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、γ-丁内酯中的一种或多种;
二酐单体与二胺单体的总摩尔数之比为(0.95-1.05):1。
9.根据权利要求7所述的聚酰亚胺薄膜的制备方法,其特征在于:
步骤S2中,
利用流涎法得到的湿膜的厚度为800-2000um;湿膜烘干制得胶膜的真空烘箱的烘干温度为60-80℃;
步骤S3中,
亚胺化采用阶梯式升温后自然冷却的方式,阶梯式升温的过程为:第一阶段:在150℃下加热2h;第二阶段:升温至200℃,保温1h;第三阶段:升温至250℃,保温1h;第四阶段:升温至300℃,保温0.5h;第五阶段:升温至350℃,保温0.5h;
薄膜揭下后烘干的烘干温度为80℃,烘干时间为2h。
10.一种如权利要求6所述的聚酰亚胺薄膜的应用,其特征在于,将所述聚酰亚胺薄膜应用在二层柔性覆铜板中,采用热压法直接将铜箔与聚酰亚胺薄膜压制成二层柔性覆铜板;热压法的热压温度为330-360℃,压力为0.5Mpa,热压时间为30-60s。
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