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CN112239539A - 聚酰胺酸组成物、聚酰亚胺覆铜板及电路板 - Google Patents

聚酰胺酸组成物、聚酰亚胺覆铜板及电路板 Download PDF

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Publication number
CN112239539A
CN112239539A CN201910641390.3A CN201910641390A CN112239539A CN 112239539 A CN112239539 A CN 112239539A CN 201910641390 A CN201910641390 A CN 201910641390A CN 112239539 A CN112239539 A CN 112239539A
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structural formula
diamine monomer
monomer containing
dianhydride
bis
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CN201910641390.3A
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Inventor
苏赐祥
吴佩蓉
李冠纬
向首睿
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Zhen Ding Technology Co Ltd
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Zhen Ding Technology Co Ltd
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Priority to CN201910641390.3A priority Critical patent/CN112239539A/zh
Priority to US16/561,401 priority patent/US20210017336A1/en
Publication of CN112239539A publication Critical patent/CN112239539A/zh
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Abstract

一种聚酰胺酸组成物,由二酸酐单体与二胺单体聚合而成且所述二酸酐单体与所述二胺单体的摩尔比的范围为0.9~1.1;所述二胺单体包括含有液晶单元的二胺单体、含有柔软结构的二胺单体及含有氮杂环的二胺单体;在二胺单体中,含有氮杂环的二胺单体的摩尔百分比为3%~8%,所述含有液晶单元的二胺单体与所述含有柔软结构的二胺单体所占的摩尔百分比之和为92%~97%。本发明还提供一种由所述聚酰胺酸组成物环化制得的聚酰亚胺覆铜板及应用所述聚酰亚胺覆铜板制得的电路板。

Description

聚酰胺酸组成物、聚酰亚胺覆铜板及电路板
技术领域
本发明涉及一种聚酰胺酸组成物,由所述聚酰胺酸组成物环化制得的聚酰亚胺覆铜板及应用所述聚酰亚胺覆铜板制得的电路板。
背景技术
近年来,印刷电路板被广泛应用于各种电子产品上。目前,印刷电路板一般由覆铜板作为基材制得。其中,覆铜板包括铜箔、聚酰亚胺膜、及位于铜箔与聚酰亚胺膜之间用于将铜箔与聚酰亚胺膜结合在一起的胶粘层。
在电路板的制作过程中,会蚀刻掉结合在聚酰亚胺膜表面的部分铜箔,从而使得该区域的聚酰亚胺膜未结合铜箔而裸露,在电路板的安装等制程中会使用CCD照相机透视该未结合铜箔的聚酰亚胺膜,以对组件进行精准定位。如此就要求该未结合铜箔的聚酰亚胺膜具有优良的透光度。
为使去除铜箔后的聚酰亚胺膜具有较高的透光度,可以在表面粗糙度较低的铜箔的表面涂布形成聚酰亚胺膜,这样可以保证在去除铜箔后聚酰亚胺膜的表面粗糙度较低而具有较高的透光度。然而,现有的聚酰亚胺膜与表面粗糙度较低的铜箔的结合力较低,使用表面粗糙度较低的铜箔制作覆铜板时,铜箔与聚酰亚胺膜的结合力较低。
发明内容
有鉴于此,有必要提供一种新型的用于制作聚酰亚胺膜的聚酰胺酸组成物,以解决以上问题。
另,还有必要提供一种由所述聚酰胺酸组成物环化制得的聚酰亚胺覆铜板。
另,还有必要提供一种应用所述聚酰亚胺覆铜板制得的电路板。
一种聚酰胺酸组成物,由二酸酐单体与二胺单体聚合而成,且所述二酸酐单体与所述二胺单体的摩尔比的范围为0.9~1.1;所述二胺单体包括含有液晶单元的二胺单体、含有柔软结构的二胺单体及含有氮杂环的二胺单体;在所述二胺单体中,所述含有氮杂环的二胺单体的摩尔百分比为3%~8%,所述含有液晶单元的二胺单体与所述含有柔软结构的二胺单体所占的摩尔百分比之和为92%~97%。
进一步地,所述二酸酐单体包括含有液晶单元的二酸酐单体或含有柔软结构的二酸酐单体中的至少一种。
进一步地,在所述含有液晶单元的二胺单体与所述含有柔软结构的二胺单体中,所述含有液晶单元的二胺单体所占的百分比为30~70%,所述含有柔软结构的二胺单体所占的百分比为30~70%,两者相加为100%。
进一步地,所述柔软结构包括长链饱和脂肪烃基、长链不饱和脂肪烃基或醚基,所述长链是指四碳或四碳以上的碳氢直链结构。
进一步地,所述液晶单元为
Figure BDA0002131980900000021
Figure BDA0002131980900000022
Figure BDA0002131980900000023
中的至少一种;其中,R及R′为烃基,X及Y为-CH=CH-、-C≡C-、-CH=N-、-CH=N-及-COO-中的至少一种。
进一步地,所述含有液晶单元的二酸酐单体为3,3',4,4'-联苯四羧酸二酐、对苯基二(偏苯三酸酯)二酸酐及环己烷-1,4-二基双(亚甲基)双(1,3-二氧代-1,3-二氢异苯并呋喃-5-羧酸乙酯)中的至少一种,其中,所述3,3',4,4'-联苯四羧酸二酐的结构式为
Figure BDA0002131980900000031
所述对苯基二(偏苯三酸酯)二酸酐的结构式为
Figure BDA0002131980900000032
所述环己烷-1,4-二基双(亚甲基)双(1,3-二氧代-1,3-二氢异苯并呋喃-5-羧酸乙酯)的结构式为:
Figure BDA0002131980900000033
进一步地,所述含有液晶单元的二胺单体为对氨基苯甲酸对氨基苯酯、1,4-双(4-氨基苯氧基)苯及对苯二甲酸二对氨基苯酯中的至少一种;其中,所述对氨基苯甲酸对氨基苯酯的结构式为:
Figure BDA0002131980900000034
所述1,4-双(4-氨基苯氧基)苯的结构式为:
Figure BDA0002131980900000035
所述对苯二甲酸二对氨基苯酯的结构式为:
Figure BDA0002131980900000036
进一步地,所述含有柔软结构的二酸酐单体为4,4'-氧双邻苯二甲酸酐、2,3,3',4'-二苯醚四甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、3,3,4,4-二苯基砜四羧酸二酸酐、六氟二酐及双酚A型二醚二酐中的至少一种;其中,所述4,4'-氧双邻苯二甲酸酐的结构式为:
Figure BDA0002131980900000041
所述2,3,3',4'-二苯醚四甲酸二酐的结构式为:
Figure BDA0002131980900000042
所述3,3',4,4'-二苯甲酮四甲酸二酐的结构式:为
Figure BDA0002131980900000043
所述3,3,4,4-二苯基砜四羧酸二酸酐的结构式为:
Figure BDA0002131980900000044
所述六氟二酐的结构式为:
Figure BDA0002131980900000045
所述双酚A型二醚二酐的结构式为
Figure BDA0002131980900000046
进一步地,所述含有柔软结构的二胺单体为4,4'-二氨基二苯醚、4,4'-二(4-氨基苯氧基)联苯、2,2'-双[4-(4-氨基苯氧基苯基)]丙烷、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、1,3-双(4'-氨基苯氧基)苯及1,3-双(3-氨基苯氧基)苯、市售工业品号为D230和D400且结构为
Figure BDA0002131980900000051
的二胺、市售工业品号为DA-C6且结构为
Figure BDA0002131980900000052
的二胺、结构式为
Figure BDA0002131980900000053
的己二胺中的至少一种;其中,所述4,4'-二氨基二苯醚的结构式为:
Figure BDA0002131980900000054
所述4,4'-二(4-氨基苯氧基)联苯的结构式为:
Figure BDA0002131980900000055
所述2,2'-双[4-(4-氨基苯氧基苯基)]丙烷的结构式为:
Figure BDA0002131980900000056
所述2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷的结构式为:
Figure BDA0002131980900000061
所述1,3-双(4'-氨基苯氧基)苯的结构式为:
Figure BDA0002131980900000062
所述1,3-双(3-氨基苯氧基)苯的结构式为:
Figure BDA0002131980900000063
进一步地,所述含有氮杂环的二胺单体为3,5-二氨基-1,2,4-三氮唑、2-(4-氨基苯基)-5-氨基苯并咪唑及2,5-双(4-氨基苯基)嘧啶中的至少一种;其中,所述3,5-二氨基-1,2,4-三氮唑的结构式为:
Figure BDA0002131980900000064
所述2-(4-氨基苯基)-5-氨基苯并咪唑的结构式为:
Figure BDA0002131980900000065
所述2,5-双(4-氨基苯基)嘧啶的结构式为:
Figure BDA0002131980900000066
一种聚酰亚胺覆铜板,其包括铜箔及结合于所述铜箔的表面的聚酰亚胺膜,所述聚酰亚胺膜由上述聚酰胺酸组成物涂布在所述铜箔的表面后经环化形成。
一种电路板,其包括电路基板及覆盖在所述电路基板至少一表面的覆盖膜,所述电路基板包括聚酰亚胺膜及结合在所述聚酰亚胺膜至少一表面的导电线路层,所述电路基板由覆铜板制成,所述覆铜板包括铜箔及结合于所述铜箔的表面的聚酰亚胺膜,所述导电线路层通过对铜箔进行图案化所形成,所述聚酰亚胺膜由上述聚酰胺酸组合物涂布在所述铜箔的表面后经环化形成。
本发明提供的聚酰胺酸组成物由二酐单体及二胺单体聚合而成,且所述二酸酐单体包括含有液晶单元的二酸酐单体或含有柔软结构的二酸酐单体中的至少一种,所述二胺单体中包括含有液晶单元的二胺单体、含有柔软结构的二胺单体及含有氮杂环的二胺单体;1)所述含有氮杂环的二胺单体中的氮杂环上的氮原子可与铜产生配位作用因而可提高聚酰亚胺与铜箔的接着强度,改善因高分子结构中的液晶单元紧密排列形成结晶所造成的刚硬性影响降低了聚酰亚胺与铜箔的接着强度;2)在高温条件下,所述含有液晶单元的二酸酐单体或二胺单体可使聚酰亚胺的高分子结构中的液晶单元紧密排列,形成结晶,降低了在高频电场下聚酰亚胺高分子结构的可动性,从而减少了介电损耗;3)所述含有柔软结构的二酸酐单体或二胺单体能够调节因高分子结构中的液晶单元紧密排列形成结晶所造成的刚硬性,并调节聚酰亚胺的热膨胀系数(CTE),使之能够与铜箔匹配,从而避免覆铜板翘曲。
附图说明
图1是本发明一较佳实施例的覆铜板的截面示意图。
图2是本发明一较佳实施例的电路板的截面示意图。
主要组件符号说明
聚酰亚胺覆铜板 100
铜箔 10
聚酰亚胺膜 20
电路板 200
电路基板 201
导电线路层 2011
覆盖膜 202
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
请结合参阅图1,本发明较佳实施方式提供一种聚酰胺酸组成物,其主要用于制作覆铜板100中结合于铜箔10表面的聚酰亚胺膜20。
所述聚酰胺酸组成物主要由二酸酐单体与二胺单体聚合而成。
其中,所述二酸酐单体包括含有液晶单元的二酸酐单体或含有柔软结构的二酸酐单体中的至少一种。其中,柔软结构是指柔软结构是指长链饱和脂肪烃基或长链不饱和脂肪烃基或醚基等。其中,长链的定义是指四碳或四碳以上的碳氢直链结构。
优选地,所述柔软结构中包含有-O-、-CH3CCH3-、-CF3CCF3-、-SO2-、-C=O-等基团中的至少一种。
其中,所述二胺单体包括含有液晶单元的二胺单体、含有柔软结构的二胺单体及含有氮杂环的二胺单体。其中,柔软结构是指柔软结构是指长链饱和脂肪烃基或长链不饱和脂肪烃基或醚基等。其中,长链的定义是指四碳或四碳以上之碳氢直链结构。优选地,所述柔软结构中包含有-O-、-CH3CCH3-、-CF3CCF3-、-SO2-、-C=O-等基团中的至少一种。
所述含有氮杂环的二胺单体中的氮杂环上的氮原子可与铜产生配位作用因而可提高聚酰亚胺与铜箔的接着强度,改善因高分子结构中的液晶单元紧密排列形成结晶所造成的刚硬性影响降低了聚酰亚胺与铜箔的接着强度。
在高温条件下,所述含有液晶单元的二酸酐单体或二胺单体可使聚酰亚胺的高分子结构中的液晶单元紧密排列,形成结晶,降低了在高频电场下聚酰亚胺高分子结构的可动性,从而减少了介电损耗。
所述含有柔软结构的二酸酐单体或二胺单体能够调节因高分子结构中的液晶单元紧密排列形成结晶所造成的刚硬性,并调节聚酰亚胺的热膨胀系数(CTE),使之能够与铜箔匹配,从而避免覆铜板翘曲。
其中,所述二酸酐单体与所述二胺单体的摩尔比的使用范围为0.9~1.1。聚酰亚胺是由1:1二酸酐单体与二胺单体的缩合聚合反应生成,当两者数量不相当的条件下进行缩合聚合反应时,所生成的聚合物平均分子量将过低,且分子量分布亦会过宽,若将此情况的聚合物进一步加工成工业运用的材料时,材料本身的物理化学特性或机械特性将无法符合工业规格标准。
其中,所述含有液晶单元的二胺单体与所述含有柔软结构的二胺单体的在所述二胺单体中所占的摩尔百分比之和为92%~97%。其中,在所述含有液晶单元的二胺单体与所述含有柔软结构的二胺单体中,所述含有液晶单元的二胺单体所占的百分比为30~70%,所述含有柔软结构的二胺单体所占的百分比为30~70%,两者相加为100%。其中,含量范围的差异会因为高分子的液晶单元或柔软单元的多寡间接或直接影响材料介电损耗高低与CTE值的变化。
其中,在所述二胺单体中,所述含有氮杂环的二胺单体的摩尔百分比为3%~8%。所述含量范围可以由所述聚酰胺酸组成物制得的聚酰亚胺膜具有较强的剥离强度的同时具有较好的透光度。实验表明,当所述含有氮杂环的二胺单体的摩尔量大于3%~8%的范围时,对所制得的聚酰亚胺膜的剥离强度的提升不大,却因含有氮杂环的二胺单体在吸光时有较大的电荷转移效应而导致透光度明显降低。
其中,所述液晶单元为
Figure BDA0002131980900000091
Figure BDA0002131980900000092
Figure BDA0002131980900000093
中的至少一种;其中,R及R′为烃基,X及Y为-CH=CH-、-C≡C-、-CH=N-、-CH=N-及-COO-中的至少一种。
具体地,所述含有液晶单元的二酸酐单体优选为芳香族四羧酸二酐。其中,所述含有液晶单元的二酸酐单体可以为但不局限于3,3',4,4'-联苯四羧酸二酐(3,3′,4,4′-Biphenyltetracarboxylic dianhydride,BPDA;CAS:2420-87-3)、对苯基二(偏苯三酸酯)二酸酐(p-Phenylene bis(trimellitate)dianhydride,TAHQ;CAS:2770-49-2)及环己烷-1,4-二基双(亚甲基)双(1,3-二氧代-1,3-二氢异苯并呋喃-5-羧酸乙酯)(cyclohexane-1,4-diylbis(methylene)bis(1,3-dioxo-1,3-dihy-droiso benzofuran-5-carboxylate),TA-CHDM)中的至少一种。
其中,所述3,3',4,4'-联苯四羧酸二酐的结构式为
Figure BDA0002131980900000101
所述对苯基二(偏苯三酸酯)二酸酐的结构式为
Figure BDA0002131980900000102
所述环己烷-1,4-二基双(亚甲基)双(1,3-二氧代-1,3-二氢异苯并呋喃-5-羧酸乙酯)的结构式为:
Figure BDA0002131980900000103
具体地,所述含有液晶单元的二胺单体可以为但不局限于对氨基苯甲酸对氨基苯酯(4-Aminobenzoic acid 4-aminophenyl ester,APAB;CAS:20610-77-9)、1,4-双(4-氨基苯氧基)苯(1,4-Bis(4-aminobenzo-yloxy)benzene,ABHQ;CAS:22095-98-3)及对苯二甲酸二对氨基苯酯(1,4-Benzenedicarboxylic acid bis(4-aMinophenyl)ester,BPTP;CAS:16926-73-1)中的至少一种。
其中,所述对氨基苯甲酸对氨基苯酯的结构式为:
Figure BDA0002131980900000111
所述1,4-双(4-氨基苯氧基)苯的结构式为:
Figure BDA0002131980900000112
所述对苯二甲酸二对氨基苯酯的结构式为:
Figure BDA0002131980900000113
其中,所述含有柔软结构的二酸酐单体优选为芳香族四羧酸二酐。具体地,所述含有柔软结构的二酸酐单体可以为但不局限于4,4'-氧双邻苯二甲酸酐(4,4′-Oxydiphthalic anhydride,ODPA;CAS:1823-59-2)、2,3,3',4'-二苯醚四甲酸二酐(3,4'-Oxydiphthalic Anhydride,A-ODPA;CAS:50662-95-8)、3,3',4,4'-二苯甲酮四甲酸二酐(Benzophenone-3,3′,4,4′-tetracarboxylic dianhydride,BTDA;CAS:2421-28-5)、3,3,4,4-二苯基砜四羧酸二酸酐(3,3',4,4'-DiphenylsulfonetetracarboxylicDianhydride,DSDA;CAS:2540-99-0)、六氟二酐(4,4′-(Hexafluoroisopropylidene)diphthalic anhydride,6FDA;CAS:1107-00-2)及双酚A型二醚二酐(4,4'-(4,4'-isopropylidenediphenoxy)bis-(phthalic anhydride),BPADA;CAS:38103-06-9)中的至少一种。
其中,所述4,4'-氧双邻苯二甲酸酐的结构式为:
Figure BDA0002131980900000114
所述2,3,3',4'-二苯醚四甲酸二酐的结构式为:
Figure BDA0002131980900000121
所述3,3',4,4'-二苯甲酮四甲酸二酐的结构式:为
Figure BDA0002131980900000122
所述3,3,4,4-二苯基砜四羧酸二酸酐的结构式为:
Figure BDA0002131980900000123
所述六氟二酐的结构式为:
Figure BDA0002131980900000124
所述双酚A型二醚二酐的结构式为
Figure BDA0002131980900000125
其中,所述含有柔软结构的二胺单体为芳香族二胺或脂肪族二胺等。具体地,所述含有柔软结构的二胺单体可以为但不局限于4,4'-二氨基二苯醚(4,4'-Oxydianiline,ODA;CAS:101-80-4)、4,4'-二(4-氨基苯氧基)联苯(4,4'-Bis(4-aminophenoxy)biphenyl,BAPB;CAS:13080-85-8)、2,2'-双[4-(4-氨基苯氧基苯基)]丙烷(4,4'-(4,4'-Isopropylidenediphenyl-1,1'-diyldioxy)dianiline,m-BAPP;CAS:13080-86-9)、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷(2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane,HFBAPP;CAS:69563-88-8)、1,3-双(4'-氨基苯氧基)苯(4,4'-(1,3-Phenylenedioxy)dianiline,TPE-R;CAS:2479-46-1)及1,3-双(3-氨基苯氧基)苯(1,3-Bis(3-aminophenoxy)benzene,TPE-M;CAS:10526-07-5)、市售工业品号为D230和D400且结构为
Figure BDA0002131980900000131
的二胺、市售工业品号为DA-C6且结构为
Figure BDA0002131980900000132
的二胺、结构式为
Figure BDA0002131980900000133
的己二胺中的至少一种。
其中,所述4,4'-二氨基二苯醚的结构式为:
Figure BDA0002131980900000134
所述4,4'-二(4-氨基苯氧基)联苯的结构式为:
Figure BDA0002131980900000135
所述2,2'-双[4-(4-氨基苯氧基苯基)]丙烷的结构式为:
Figure BDA0002131980900000136
所述2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷的结构式为:
Figure BDA0002131980900000141
所述1,3-双(4'-氨基苯氧基)苯的结构式为:
Figure BDA0002131980900000142
所述1,3-双(3-氨基苯氧基)苯的结构式为:
Figure BDA0002131980900000143
其中,所述含有氮杂环的二胺单体可以为但不局限于3,5-二氨基-1,2,4-三氮唑(1,2,4-Triazole-3,5-diamine,DTZ;CAS:1455-77-2)、2-(4-氨基苯基)-5-氨基苯并咪唑(2-(4-Aminophenyl)-1H-benzimidazol-5-amine,APBIA;CAS:7621-86-5)及2,5-双(4-氨基苯基)嘧啶(4,4'-pyrimidine-2,5-diyldianiline,PRM;CAS:102570-64-9)中的至少一种。
其中,所述3,5-二氨基-1,2,4-三氮唑的结构式为:
Figure BDA0002131980900000144
所述2-(4-氨基苯基)-5-氨基苯并咪唑的结构式为:
Figure BDA0002131980900000145
所述2,5-双(4-氨基苯基)嘧啶的结构式为:
Figure BDA0002131980900000146
所述聚酰胺酸组成物的制备方法可以为:将含有液晶单元的二胺单体、含有柔软结构的二胺单体及含有氮杂环的二胺单体加入具有溶剂的反应瓶中;高速搅拌使含有液晶单元的二胺单体、含有柔软结构的二胺单体及含有氮杂环的二胺单体完全溶解在溶剂中;接着,将含有液晶单元的二酸酐单体或含有柔软结构的二酸酐单体中的至少一种加入所述反应瓶中,搅拌反应一段时间,即制得聚酰胺酸组成物。其中,所述溶剂优选为双极性的质子惰性溶剂。所述双极性的质子惰性溶剂可以为二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAC)、N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)等。所述溶剂的添加量可根据需要进行变更,只要使所述含有液晶单元的二胺单体、含有柔软结构的二胺单体及含有氮杂环的二胺单体及含有液晶单元的二酸酐单体及/或含有柔软结构的二酸酐单体能完全溶解即可。所述高速搅拌的转速可以为1400rpm(转每分钟)左右。
请结合参阅图1~2,一种聚酰亚胺覆铜板100,其用于制作电路板200。所述聚酰亚胺覆铜板100包括铜箔10及结合于所述铜箔10一表面的聚酰亚胺膜20。所述铜箔10的表面具有较低的粗糙度。其中,所述铜箔10的表面粗糙度在0.12um~2.1um之间。所述聚酰亚胺膜20通过将上述聚酰胺酸组成物涂布在所述铜箔10的表面后经高温环化形成。
其中,所述聚酰胺酸组成物经高温环化形成所述聚酰亚胺膜20的原理为:
Figure BDA0002131980900000151
因所述聚酰胺酸组成物包括含有氮杂环的二胺单体,所述含有氮杂环的二胺单体中的氮杂环上的氮原子可与所述铜箔10产生配位作用,从而使得所述聚酰亚胺膜20与所述铜箔10之间具有较强的结合力。如此,可以使用表面粗糙度较低的铜箔10来制作聚酰亚胺覆铜板100,这样可以使在铜箔10表面所形成的聚酰亚胺膜20的表面较为平整,从而使得该聚酰亚胺膜20具有较高的透光度。
其中,所述聚酰亚胺覆铜板100的所述铜箔10与所述聚酰亚胺膜20直接结合在一起,所述铜箔10与所述聚酰亚胺膜20之间未设置胶粘层,如此可以进一步提高所述聚酰亚胺膜20的透光度,并且可以节约成本。
一种上述聚酰亚胺覆铜板100的制作方法:
提供铜箔10,所述铜箔10的表面粗糙度在0.12um~2.1um之间。
提供聚酰胺酸组成物,将所述聚酰胺酸组成物涂布在所述铜箔10的表面。
高温环化,使所述铜箔10表面的聚酰胺酸组成物高温下脱水而进行闭环,得到结合在铜箔10表面的聚酰亚胺膜20,即制得覆铜板100。其中,所述高温环化的温度范围大致为300~400℃。
本发明还提供一种聚酰亚胺膜20,所述聚酰亚胺膜20通过将所述聚酰胺酸组成物涂覆在基材的表面后经高温环化形成。其中,所述基材可以为离型膜、金属箔、树脂等常规应用于制备聚酰亚胺膜的基材。在高温环化过程中,所述聚酰胺酸组成物会在高温下脱水而进行闭环,从而得到结合在基材表面的聚酰亚胺膜20。
请参阅图2,一种电路板200,其应用于电脑、电子阅读器、平板电脑、智能手表等电子装置(图未示)上。该电路板200包括电路基板201及覆盖在该电路基板201至少一表面的覆盖膜202。该电路基板201包括所述聚酰亚胺膜20及结合在所述聚酰亚胺膜20至少一表面的导电线路层2011。所述导电线路层2011通过对聚酰亚胺覆铜板100的铜箔10图案化所形成。所述覆盖膜202结合于所述导电线路层2011的远离所述聚酰亚胺膜20的表面。
下面通过具体实施例进一步对本发明的聚酰胺酸组成物进行说明。
实施例1
于500mL反应瓶中分别加入NMP(203.37g)、APAB(0.068mol,15.52g)、ODA(0.027mol,5.41g)、DTZ(0.005mol,0.50g),待高速搅拌至溶解后,再加入BPDA(0.1mol,29.42g)于无水氮气环境下,以低于室温条件搅拌反应48小时,即配置完成聚酰胺酸组成物。
实施例2
于500mL反应瓶中分别加入NMP(205.77g)、APAB(0.078mol,17.80g)、ODA(0.017mol,3.40g)、DTZ(0.005mol,0.50g),待高速搅拌至溶解后,再加入ODPA(0.02mol,6.20g)、BPDA(0.08mol,23.54g)于无水氮气环境下,以低于室温条件搅拌反应48小时,即配置完成聚酰胺酸组成物。
实施例3
于500mL反应瓶中分别加入NMP(250.75g)、APAB(0.045mol,10.27g)、ODA(0.060mol,12.01g)、DTZ(0.005mol,0.50g),待高速搅拌至溶解后,再加入ODPA(0.04mol,12.41g)、TAHQ(0.06mol,27.50g)于无水氮气环境下,以低于室温条件搅拌反应48小时,即配置完成聚酰胺酸组成物。
实施例4
于500mL反应瓶中分别加入NMP(211.68g)、APAB(0.085mol,19.40g)、ODA(0.010mol,2.00g)、DTZ(0.005mol,0.50g),待高速搅拌至溶解后,再加入ODPA(0.1mol,31.02g)于无水氮气环境下,以低于室温条件搅拌反应48小时,即配置完成聚酰胺酸组成物。
比较例1
于500mL反应瓶中分别加入NMP(170.66g)、PDA(0.068mol,7.34g)、ODA(0.027mol,5.41g)、DTZ(0.005mol,0.50g),待高速搅拌至溶解后,再加入BPDA(0.1mol,29.42g)于无水氮气环境下,以低于室温条件搅拌反应48小时,即配置完成聚酰胺酸组成物。
比较例2
于500mL反应瓶中分别加入NMP(205.61g)、APAB(0.070mol,15.98g)、ODA(0.030mol,6.01g),待高速搅拌至溶解后,再加入BPDA(0.1mol,29.42g)于无水氮气环境下,以低于室温条件搅拌反应48小时,即配置完成聚酰胺酸组成物。
比较例3
于500mL反应瓶中分别加入NMP(263.41g)、ODA(0.1mol,20.02g),待高速搅拌至溶解后,再加入TAHQ(0.1mol,45.83g)于无水氮气环境下,以低于室温条件搅拌反应48小时,即配置完成聚酰胺酸组成物。
比较例4
于500mL反应瓶中分别加入NMP(208.98g)、APAB(0.1mol,22.83g),待高速搅拌至溶解后,再加入BPDA(0.1mol,29.42g)于无水氮气环境下,以低于室温条件搅拌反应48小时,即配置完成聚酰胺酸组成物。
将上述实施例1~4及比较例1~4中所制得的聚酰胺酸组成物分别涂布在铜箔10的表面,将涂布有聚酰胺酸组成物的铜箔10分别置于高温环境下,使聚酰胺酸组成物高温环化聚合形成结合在铜箔10表面的聚酰亚胺膜20,制得覆铜板100。
对所述覆铜板100分别进行剥离强度测试、漂锡测试、热膨胀系数(CTE)测试、热重测试(Tg)、介电常数(Dk)及介质损耗(Df)。测试结果参见表一。其中,所述漂锡测试中,若漂锡测试在温度为288℃下持续10sec,锡不脱落,则漂锡测试结果为“通过”,表明覆铜板100达到了漂锡测试的需求。
表一:由实施例1~4及比较例1~4的聚酰胺酸组成物所制得的覆铜板的剥离强度、漂锡性、热膨胀系数、热重及聚酰亚胺膜的介电常数及介质损耗的测试结果
Figure BDA0002131980900000181
Figure BDA0002131980900000191
由上表可知,实施例1~4为本发明导入含有液晶单元的单体与含氮杂环的二胺单体,其仍保有与铜箔良好的剥离强度并可降低介电损失Df值为0.004~0.006,而比较例1因为不含液晶单元单体的聚酰胺酸组成物,其介电损失Df值为0.014。比较例2~4虽含有液晶单元的单体但因缺少含氮杂环的二胺单体,所以与铜箔的剥离强度则会下降至非常低。比较例3含液晶单元的单体只搭配柔软单体,则CTE值则偏大会造成覆铜板翘曲。比较例4含液晶单元的单体无搭配柔软单体,则CTE值偏低,也会造成覆铜板翘曲。
本发明提供的聚酰胺酸组成物由二酐单体及二胺单体聚合而成,且所述二酸酐单体包括含有液晶单元的二酸酐单体或含有柔软结构的二酸酐单体中的至少一种,所述二胺单体中包括含有液晶单元的二胺单体、含有柔软结构的二胺单体及含有氮杂环的二胺单体;1)所述含有氮杂环的二胺单体中的氮杂环上的氮原子可与铜产生配位作用因而可提高聚酰亚胺与铜箔的接着强度,改善因高分子结构中的液晶单元紧密排列形成结晶所造成的刚硬性影响降低了聚酰亚胺与铜箔的接着强度;2)在高温条件下,所述含有液晶单元的二酸酐单体或二胺单体可使聚酰亚胺的高分子结构中的液晶单元紧密排列,形成结晶,降低了在高频电场下聚酰亚胺高分子结构的可动性,从而减少了介电损耗;3)所述含有柔软结构的二酸酐单体或二胺单体能够调节因高分子结构中的液晶单元紧密排列形成结晶所造成的刚硬性,并调节聚酰亚胺的热膨胀系数(CTE),使之能够与铜箔匹配,从而避免覆铜板翘曲。
另外,对于本领域的普通技术人员来说,可以根据本发明的技术构思做出其它各种相应的改变与变形,而所有这些改变与变形都应属于本发明权利要求的保护范围。

Claims (12)

1.一种聚酰胺酸组成物,由二酸酐单体与二胺单体聚合而成,且所述二酸酐单体与所述二胺单体的摩尔比的范围为0.9~1.1;其特征在于,其中,所述二胺单体包括含有液晶单元的二胺单体、含有柔软结构的二胺单体及含有氮杂环的二胺单体;在所述二胺单体中,所述含有氮杂环的二胺单体的摩尔百分比为3%~8%,所述含有液晶单元的二胺单体与所述含有柔软结构的二胺单体所占的摩尔百分比之和为92%~97%。
2.如权利要求1所述的聚酰胺酸组成物,其特征在于,所述二酸酐单体包括含有液晶单元的二酸酐单体或含有柔软结构的二酸酐单体中的至少一种。
3.如权利要求1所述的聚酰胺酸组成物,其特征在于,在所述含有液晶单元的二胺单体与所述含有柔软结构的二胺单体中,所述含有液晶单元的二胺单体所占的百分比为30~70%,所述含有柔软结构的二胺单体所占的百分比为30~70%,两者相加为100%。
4.如权利要求1或2所述的聚酰胺酸组成物,其特征在于,所述柔软结构包括长链饱和脂肪烃基、长链不饱和脂肪烃基或醚基,所述长链是指四碳或四碳以上的碳氢直链结构。
5.如权利要求1-3任一项所述的聚酰胺酸组成物,其特征在于,所述液晶单元为
Figure FDA0002131980890000011
Figure FDA0002131980890000012
中的至少一种;其中,R及R′为烃基,X及Y为-CH=CH-、-C≡C-、-CH=N-、-CH=N-及-COO-中的至少一种。
6.如权利要求5所述的聚酰胺酸组成物,其特征在于,所述含有液晶单元的二酸酐单体为3,3',4,4'-联苯四羧酸二酐、对苯基二(偏苯三酸酯)二酸酐及环己烷-1,4-二基双(亚甲基)双(1,3-二氧代-1,3-二氢异苯并呋喃-5-羧酸乙酯)中的至少一种,其中,所述3,3',4,4'-联苯四羧酸二酐的结构式为
Figure FDA0002131980890000021
所述对苯基二(偏苯三酸酯)二酸酐的结构式为
Figure FDA0002131980890000022
所述环己烷-1,4-二基双(亚甲基)双(1,3-二氧代-1,3-二氢异苯并呋喃-5-羧酸乙酯)的结构式为:
Figure FDA0002131980890000023
7.如权利要求5所述的聚酰胺酸组成物,其特征在于,所述含有液晶单元的二胺单体为对氨基苯甲酸对氨基苯酯、1,4-双(4-氨基苯氧基)苯及对苯二甲酸二对氨基苯酯中的至少一种;其中,所述对氨基苯甲酸对氨基苯酯的结构式为:
Figure FDA0002131980890000024
所述1,4-双(4-氨基苯氧基)苯的结构式为:
Figure FDA0002131980890000025
所述对苯二甲酸二对氨基苯酯的结构式为:
Figure FDA0002131980890000031
8.如权利要求1或2所述的聚酰胺酸组成物,其特征在于,所述含有柔软结构的二酸酐单体为4,4'-氧双邻苯二甲酸酐、2,3,3',4'-二苯醚四甲酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、3,3,4,4-二苯基砜四羧酸二酸酐、六氟二酐及双酚A型二醚二酐、市售工业品号为D230和D400且结构为
Figure FDA0002131980890000032
的二胺、市售工业品号为DA-C6且结构为
Figure FDA0002131980890000033
的二胺、结构式为
Figure FDA0002131980890000034
的己二胺中的至少一种;其中,所述4,4'-氧双邻苯二甲酸酐的结构式为:
Figure FDA0002131980890000035
所述2,3,3',4'-二苯醚四甲酸二酐的结构式为:
Figure FDA0002131980890000036
所述3,3',4,4'-二苯甲酮四甲酸二酐的结构式:为
Figure FDA0002131980890000037
所述3,3,4,4-二苯基砜四羧酸二酸酐的结构式为:
Figure FDA0002131980890000041
所述六氟二酐的结构式为:
Figure FDA0002131980890000042
所述双酚A型二醚二酐的结构式为
Figure FDA0002131980890000043
9.如权利要求1或3所述的聚酰胺酸组成物,其特征在于,所述含有柔软结构的二胺单体为4,4'-二氨基二苯醚、4,4'-二(4-氨基苯氧基)联苯、2,2'-双[4-(4-氨基苯氧基苯基)]丙烷、2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷、1,3-双(4'-氨基苯氧基)苯及1,3-双(3-氨基苯氧基)苯中的至少一种;其中,所述4,4'-二氨基二苯醚的结构式为:
Figure FDA0002131980890000044
所述4,4'-二(4-氨基苯氧基)联苯的结构式为:
Figure FDA0002131980890000045
所述2,2'-双[4-(4-氨基苯氧基苯基)]丙烷的结构式为:
Figure FDA0002131980890000046
所述2,2-双[4-(4-氨基苯氧基)苯基]-1,1,1,3,3,3-六氟丙烷的结构式为:
Figure FDA0002131980890000051
所述1,3-双(4'-氨基苯氧基)苯的结构式为:
Figure FDA0002131980890000052
所述1,3-双(3-氨基苯氧基)苯的结构式为:
Figure FDA0002131980890000053
10.如权利要求1所述的聚酰胺酸组成物,其特征在于,所述含有氮杂环的二胺单体为3,5-二氨基-1,2,4-三氮唑、2-(4-氨基苯基)-5-氨基苯并咪唑及2,5-双(4-氨基苯基)嘧啶中的至少一种;其中,所述3,5-二氨基-1,2,4-三氮唑的结构式为:
Figure FDA0002131980890000054
所述2-(4-氨基苯基)-5-氨基苯并咪唑的结构式为:
Figure FDA0002131980890000055
所述2,5-双(4-氨基苯基)嘧啶的结构式为:
Figure FDA0002131980890000056
11.一种聚酰亚胺覆铜板,包括铜箔及结合于所述铜箔的表面的聚酰亚胺膜,其特征在于,所述聚酰亚胺膜由如权利要求1-3及10任一项所述的聚酰胺酸组成物涂布在所述铜箔的表面后环化形成。
12.一种电路板,其包括电路基板及覆盖在所述电路基板至少一表面的覆盖膜,所述电路基板包括聚酰亚胺膜及结合在所述聚酰亚胺膜至少一表面的导电线路层,所述电路基板由聚酰亚胺覆铜板制成,所述聚酰亚胺覆铜板包括铜箔及结合于所述铜箔的表面的聚酰亚胺膜,所述导电线路层通过对铜箔进行图案化形成,其特征在于,所述聚酰亚胺膜由如权利要求1-3及10任一项所述的聚酰胺酸组合物涂布在所述铜箔的表面后经环化形成。
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