CN113637165A - 一种双面导电聚酰亚胺柔性电路板的制备方法 - Google Patents
一种双面导电聚酰亚胺柔性电路板的制备方法 Download PDFInfo
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Abstract
本发明涉及一种双面导电聚酰亚胺柔性电路板的制备方法,属于层压板、芯片领域,所述双面导电聚酰亚胺层压板可作为通孔连接型双面柔性电路板。该双面导电聚酰亚胺柔性电路板的制备方法为分别制备具有低热膨胀系数和热塑性聚酰亚胺前驱体聚酰胺酸,然后将低热膨胀系数聚酰胺酸涂覆在铜箔上,烘干容积,再涂覆一层热塑性聚酰胺酸,得到热塑性聚酰胺酸/低热膨胀系数聚酰胺酸/铜箔,然后将两片热塑性聚酰胺酸/低热膨胀系数聚酰胺酸/铜箔的铜箔朝外,高温高压下热压成型得到双面导电聚酰亚胺柔性电路板。根据本发明,导电金属层压在聚酰亚胺树脂层的两个表面上,不需要使用粘合剂。本发明制得的聚酰亚胺的热膨胀系数小于3×10‑5℃‑1。
Description
技术领域
本发明涉及一种双面导电聚酰亚胺柔性电路板的制备方法,属于层压板、芯片领域,所述双面导电聚酰亚胺层压板可作为通孔连接型双面柔性电路板。
背景技术
近年来,在电子装置和使用该电子装置的电子装置中,对小型化和重量减轻的需求增加,并且据此,布线材料的简化和致密化的趋势已经发展,柔性印刷电路材料等也不例外。柔性印刷电路板是一种柔性印刷电路板,它极大地促进了电气设备和电子设备的小型化和重量减轻。对于该柔性印刷电路板,仅在其一侧具有导体层的单面结构和在绝缘层的两侧具有导体层且夹有绝缘层的双面通孔结构已投入实际使用。作为在绝缘层中提供内部通孔的方法,目前主要有两种方法,分别为激光法和光敏树脂法。其中,对于激光法,通孔钻孔速度低,生产率低,并且新需要专用设施,导致成本高。光敏树脂法使用光敏树脂,通常当紫外线照射在所需的掩模图案上,通孔形成速率较慢,效率低下。近年来,甚至需要在基板的两个表面上形成电路,并且近年来,双面均需要形成通孔结构。
在这种双面通孔结构的情况下,存在一个问题,即与单面结构的柔性印刷电路板相比,单面结构的柔性印刷电路板的柔性通常较低,通过将导体的铜箔或类似物粘合在作为绝缘层的基膜的两侧,并在基膜之间插入粘合剂而形成。还存在另外一个问题,即优异的耐热性、阻燃性等受损。此外,粘合层的另一个问题是电路可操作性恶化。具体而言,存在诸如在通孔加工时由于钻孔而产生的树脂涂抹、在电镀通孔电镀中的附着力降低以及在蚀刻加工时的大尺寸变化率等问题。另一方面,随着集成电路的密度增加,印刷线路小型化,密度增加,热量产生变大,并且有必要粘合良好的导热体。此外,还有一种集成外壳和接线的方法,使其更加紧凑。此外,可能需要不同电容量的布线或耐高温的布线材料。因此,本发明提出了一种双面导电聚酰亚胺柔性电路板的制备方法,其中绝缘材料层压在导体上而不使用粘合剂,而是直接使用聚酰亚胺绝缘层作为粘结剂。
发明内容
本发明的目的是针对单面结构的柔性印刷电路板的柔性通常较低,将导体的铜箔或类似物粘合在作为绝缘层的基膜的两侧得到的双面导电电路板存在优异的耐热性、阻燃性等受损,粘合层可能导致电路可操作性恶化等问题,提出一种双面导电聚酰亚胺柔性电路板的制备方法,制备在耐热性、机械特性和电气特性方面优异的双面导体聚酰亚胺层压板。具体为分别制备具有低热膨胀系数和热塑性聚酰亚胺前驱体聚酰胺酸,然后将低热膨胀系数聚酰胺酸涂覆在铜箔上,烘干容积,再涂覆一层热塑性聚酰胺酸,得到热塑性聚酰胺酸/低热膨胀系数聚酰胺酸/铜箔,然后将两片热塑性聚酰胺酸/低热膨胀系数聚酰胺酸/铜箔的铜箔朝外,高温高压下热压成型得到双面导电聚酰亚胺柔性电路板。
所述的一种双面导电聚酰亚胺柔性电路板的制备方法,其特征在于:其制备方法步骤以下:
(1)在氮气气氛保护下,向反应瓶中加入二元胺单体和N,N-二甲基乙酰胺,配成浓度为1~10wt%的二元胺溶液,然后在0.5~2h内加入四羧酸二酸酐,室温下搅拌反应8~16h,得到低热膨胀系数聚酰胺酸溶液,其中二元胺中含有5~20mol%的具有附图1所示结构的二元胺,其他二元胺为2’-甲氧基-4,4’-二氨基苯甲酰苯胺、4,4’-二氨基二苯醚、对苯二胺中的一种以上,四羧酸二酸酐为均苯四甲酸酐、3,3’,4,4’-联苯四酸酐中的一种,二元胺与四羧酸二酸酐的摩尔比为1:1;
(2)在氮气气氛保护下,向反应瓶中加入二元胺单体和N,N-二甲基乙酰胺,配成浓度为1~10wt%的二元胺溶液,然后在0.5~2h内加入3,3’,4,4’-二苯砜四羧酸酐,室温下搅拌反应8~16h,得到热塑性聚酰胺酸溶液,其中二元胺为3,3’-二氨基二苯砜、1,3-[双(3-氨基苯氧基)]苯、2,2-双[4-(氨基苯氧基)苯基)丙烷中的一种以上,二元胺与3,3’,4,4’-二苯砜四羧酸酐的摩尔比为1:1;
(3)将步骤(1)得到的低热膨胀系数聚酰胺酸溶液涂覆在20~40μm铜箔上,在120~180℃烘干溶剂,重复涂覆控制其厚度在3~10μm,然后将步骤(2)得到的热塑性聚酰胺酸溶液涂覆在低热膨胀系数聚酰胺酸表面,在120~180℃烘干溶剂,重复涂覆控制其厚度在20~50μm;
(4)将两片步骤(3)得到的产品铜箔在外,聚酰胺酸层在内叠加在一起,然后在压力为5~20MPa,温度为180~220℃条件下处理时间为2~4h,然后卸去压力,自然冷却至室温,去除模具得到层压板;
(5)将步骤(4)得到产品置于马弗炉中,于330~360℃下保温1~3h,自然冷却至室温,得到双面导电聚酰亚胺柔性电路板。
本发明的有益效果体现在:由于本发明制备的低热膨胀系数聚酰亚胺中含有邻苯二甲腈基团,其可以与铜箔形成酞菁铜提高层间剥离强度,在高温亚胺化时,两片热塑性聚酰胺酸/低热膨胀系数聚酰胺酸/铜箔中的热塑性聚酰胺酸相互反应,形成均已材料。根据本发明,导电金属层压在聚酰亚胺树脂层的两个表面上,不需要使用粘合剂。将制备得到的双面导电聚酰亚胺柔性电路的铜箔刻蚀掉后,所剩下的聚酰亚胺的热膨胀系数小于3×10-5℃-1。本发明制备方法采用一次热压加工成型,方法简单、节约成本。
附图说明
图1是含有邻苯二甲腈基团的二元胺的结构式
图2是热塑性聚酰胺酸/低热膨胀系数聚酰胺酸/铜箔的刨面图
图3是两片热塑性聚酰胺酸/低热膨胀系数聚酰胺酸/铜箔热压后的刨面图
图4是双面导电聚酰亚胺柔性电路板的刨面图
具体实施方式
以下通过具体实施方式的描述对本发明做进一步说明,但这并非对本发明的限制,本领域技术人员根据本发明的基本思想,可以做出各种变型或改性,只要不脱离本发明的基本思想,均在本发明的范围之内。
实施案例1
(1)在氮气气氛保护下,向反应瓶中加入2.22g二元胺单体和N,N-二甲基乙酰胺100g,配成浓度为2wt%的二元胺溶液,然后在1h内加入2.2g的均苯四甲酸酐,室温下搅拌反应12h,得到低热膨胀系数聚酰胺酸溶液,其中二元胺中含有0.42g(10mol%)的具有附图1所示结构的二元胺,其他二元胺为1.8g(90mol%)4,4’-二氨基二苯醚;
(2)在氮气气氛保护下,向反应瓶中加入3,3’-二氨基二苯砜2.48g和N,N-二甲基乙酰胺100g,配成浓度为2wt%的二元胺溶液,然后在1h内加入3,3’,4,4’-二苯砜四羧酸酐3.58g,室温下搅拌反应16h,得到热塑性聚酰胺酸溶液;
(3)将步骤(1)得到的低热膨胀系数聚酰胺酸溶液涂覆在25μm铜箔上,在160℃烘干溶剂,重复涂覆控制其厚度在5μm,然后将步骤(2)得到的热塑性聚酰胺酸溶液涂覆在低热膨胀系数聚酰胺酸表面,在160℃烘干溶剂,重复涂覆控制其厚度在50μm,所得到的产品的刨面图如附图2所示;
(4)将两片步骤(3)得到的产品铜箔在外,聚酰胺酸层在内叠加在一起,然后在压力为10MPa,温度为180℃条件下处理时间为2h,然后卸去压力,自然冷却至室温,去除模具得到层压板,所得到的产品的刨面图如附图3所示;
(5)将步骤(4)得到产品置于马弗炉中,于350℃下保温2h,自然冷却至室温,得到双面导电聚酰亚胺柔性电路板,所得到的产品的刨面图如附图4所示,制得的聚酰亚胺的热膨胀系数为2.5×10-5℃-1。
实施案例2
(1)在氮气气氛保护下,向反应瓶中加入1.85g二元胺单体和N,N-二甲基乙酰胺100g,配成浓度为2wt%的二元胺溶液,然后在1h内加入2.2g的均苯四甲酸酐,室温下搅拌反应12h,得到低热膨胀系数聚酰胺酸溶液,其中二元胺中含有0.42g(10mol%)的具有附图1所示结构的二元胺,其他二元胺为1.0g(50mol%)4,4’-二氨基二苯醚和0.43g(40mol%)对苯二胺;
(2)与实施例(1)步骤(2)一致;
(3)与实施例(1)步骤(3)一致;
(4)与实施例(1)步骤(4)一致;
(5)与实施例(1)步骤(5)一致,聚酰亚胺的热膨胀系数为2.4×10-5℃-1。
实施案例3
(1)在氮气气氛保护下,向反应瓶中加入2.22g二元胺单体和N,N-二甲基乙酰胺100g,配成浓度为2wt%的二元胺溶液,然后在1h内加入2.94g的3,3’,4,4’-联苯四酸酐,室温下搅拌反应12h,得到低热膨胀系数聚酰胺酸溶液,其中二元胺中含有0.42g(10mol%)的具有附图1所示结构的二元胺,其他二元胺为1.8g(90mol%)4,4’-二氨基二苯醚;
(2)与实施例(1)步骤(2)一致;
(3)与实施例(1)步骤(3)一致;
(4)与实施例(1)步骤(4)一致;
(5)与实施例(1)步骤(5)一致,聚酰亚胺的热膨胀系数为2.6×10-5℃-1。
实施案例4
(1)与实施例(1)步骤(1)一致;
(2)在氮气气氛保护下,向反应瓶中加入1,3-[双(3-氨基苯氧基)]苯2.92g和N,N-二甲基乙酰胺100g,配成浓度为3wt%的二元胺溶液,然后在1h内加入3,3’,4,4’-二苯砜四羧酸酐3.58g,室温下搅拌反应16h,得到热塑性聚酰胺酸溶液;
(3)与实施例(1)步骤(3)一致;
(4)与实施例(1)步骤(4)一致;
(5)与实施例(1)步骤(5)一致,聚酰亚胺的热膨胀系数为2.2×10-5℃-1。
实施案例5
(1)与实施例(1)步骤(1)一致;
(2)与实施例(1)步骤(2)一致;
(3)将步骤(1)得到的低热膨胀系数聚酰胺酸溶液涂覆在25μm铜箔上,在160℃烘干溶剂,重复涂覆控制其厚度在10μm,然后将步骤(2)得到的热塑性聚酰胺酸溶液涂覆在低热膨胀系数聚酰胺酸表面,在160℃烘干溶剂,重复涂覆控制其厚度在20μm;
(4)与实施例(1)步骤(4)一致;
(5)与实施例(1)步骤(5)一致,聚酰亚胺的热膨胀系数为2.5×10-5℃-1。
实施案例6
(1)与实施例(1)步骤(1)一致;
(2)与实施例(1)步骤(2)一致;
(3)与实施例(1)步骤(3)一致;
(4)将两片步骤(3)得到的产品铜箔在外,聚酰胺酸层在内叠加在一起,然后在压力为20MPa,温度为200℃条件下处理时间为2h,然后卸去压力,自然冷却至室温,去除模具得到层压板;
(5)与实施例(1)步骤(5)一致,聚酰亚胺的热膨胀系数为2.6×10-5℃-1。
实施案例7
(1)与实施例(1)步骤(1)一致;
(2)与实施例(1)步骤(2)一致;
(3)与实施例(1)步骤(3)一致;
(4)与实施例(1)步骤(4)一致;
(5)将步骤(4)得到产品置于马弗炉中,于360℃下保温3h,自然冷却至室温,得到双面导电聚酰亚胺柔性电路板,聚酰亚胺的热膨胀系数为2.1×10-5℃-1。
Claims (1)
1.一种双面导电聚酰亚胺柔性电路板的制备方法,其特征在于:其制备步骤以下:
(1)在氮气气氛保护下,向反应瓶中加入二元胺单体和N,N-二甲基乙酰胺,配成浓度为1~10wt%的二元胺溶液,然后在0.5~2h内加入四羧酸二酸酐,室温下搅拌反应8~16h,得到低热膨胀系数聚酰胺酸溶液,其中二元胺中含有5~20mol%的具有式I所示结构的二元胺,其他二元胺为2’-甲氧基-4,4’-二氨基苯甲酰苯胺、4,4’-二氨基二苯醚、对苯二胺中的一种以上,四羧酸二酸酐为均苯四甲酸酐、3,3’,4,4’-联苯四酸酐中的一种,二元胺与四羧酸二酸酐的摩尔比为1:1;
(2)在氮气气氛保护下,向反应瓶中加入二元胺单体和N,N-二甲基乙酰胺,配成浓度为1~10wt%的二元胺溶液,然后在0.5~2h内加入3,3’,4,4’-二苯砜四羧酸酐,室温下搅拌反应8~16h,得到热塑性聚酰胺酸溶液,其中二元胺为3,3’-二氨基二苯砜、1,3-[双(3-氨基苯氧基)]苯、2,2-双[4-(氨基苯氧基)苯基)丙烷中的一种以上,二元胺与3,3’,4,4’-二苯砜四羧酸酐的摩尔比为1:1;
(3)将步骤(1)得到的低热膨胀系数聚酰胺酸溶液涂覆在20~40μm铜箔上,在120~180℃烘干溶剂,重复涂覆控制其厚度在3~10μm,然后将步骤(2)得到的热塑性聚酰胺酸溶液涂覆在低热膨胀系数聚酰胺酸表面,在120~180℃烘干溶剂,重复涂覆控制其厚度在20~50μm;
(4)将两片步骤(3)得到的产品铜箔在外,聚酰胺酸层在内叠加在一起,然后在压力为5~20MPa,温度为180~220℃条件下处理时间为2~4h,然后卸去压力,自然冷却至室温,去除模具得到层压板;
(5)将步骤(4)得到产品置于马弗炉中,于330~360℃下保温1~3h,自然冷却至室温,得到双面导电聚酰亚胺柔性电路板。
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