CN115216148A - 多孔聚酰亚胺薄膜 - Google Patents

多孔聚酰亚胺薄膜 Download PDF

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CN115216148A
CN115216148A CN202210409062.2A CN202210409062A CN115216148A CN 115216148 A CN115216148 A CN 115216148A CN 202210409062 A CN202210409062 A CN 202210409062A CN 115216148 A CN115216148 A CN 115216148A
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polyimide film
porous polyimide
less
diamine
film
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三岛慧
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Nitto Denko Corp
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Abstract

提供介电损耗角正切低的多孔聚酰亚胺薄膜。多孔聚酰亚胺薄膜为二胺成分与酸二酐成分的反应产物。二胺成分含有下述式(1)所示的芳香族二胺。(式中，Y表示选自由单键、‑COO‑、‑S‑、‑CH(CH3)‑、‑C(CH3)2‑、‑CO‑、‑NH‑及‑NHCO‑组成的组中的至少1者。)所述多孔聚酰亚胺薄膜的孔隙率为50％以上。
Figure DDA0003602984250000011

Description

多孔聚酰亚胺薄膜
技术领域
本发明涉及多孔聚酰亚胺薄膜。
背景技术
已知有作为二胺成分与酸二酐成分的反应产物的多孔聚酰亚胺薄膜(例如，参照下述专利文献1。)。专利文献1的实施例中，二胺成分包含苯二胺(PDA)及氧二苯胺(ODA)。
现有技术文献
专利文献
专利文献1：WO2018/186486号
发明内容
发明要解决的问题
对多孔聚酰亚胺薄膜要求低的介电损耗角正切。但是，对于降低专利文献1中记载的多孔聚酰亚胺薄膜的介电损耗角正切而言，存在极限。
本发明提供介电损耗角正切低的多孔聚酰亚胺薄膜。
用于解决问题的方案
本发明(1)包含一种多孔聚酰亚胺薄膜，其是二胺成分与酸二酐成分的反应产物，前述二胺成分含有下述式(1)所示的芳香族二胺，所述多孔聚酰亚胺薄膜的孔隙率为50％以上。
Figure BDA0003602984230000011
(式中，Y表示选自由单键、-COO-、-S-、-CH(CH3)-、-C(CH3)2-、-CO-、-NH-及-NHCO-组成的组中的至少1者。)
本发明(2)包含(1)所述的多孔聚酰亚胺薄膜，其10GHz下的介电损耗角正切为0.0028以下。
本发明(2)包含(1)或(2)所述的多孔聚酰亚胺薄膜，其中，前述孔隙率为95％以下。
发明的效果
本发明的多孔聚酰亚胺薄膜中，二胺成分含有式(1)所示的芳香族二胺，孔隙率为50％以上，因此多孔聚酰亚胺薄膜的介电损耗角正切低。
附图说明
图1为本发明的多孔聚酰亚胺薄膜的一实施方式的截面图。
附图标记说明
1多孔聚酰亚胺薄膜
具体实施方式
<多孔聚酰亚胺薄膜>
对本发明的多孔聚酰亚胺薄膜进行说明。多孔聚酰亚胺薄膜具有厚度。多孔聚酰亚胺薄膜沿面方向延伸。面方向与厚度方向正交。
多孔聚酰亚胺薄膜为多孔体(发泡体)。多孔聚酰亚胺薄膜例如具有闭孔结构和/或连续气泡结构。
<孔隙率>
多孔聚酰亚胺薄膜的孔隙率为50％以上。
多孔聚酰亚胺薄膜的孔隙率不足50％时，无法充分降低多孔聚酰亚胺薄膜的介电损耗角正切。具体而言，多孔聚酰亚胺薄膜的孔隙率不足50％时，即使作为原料的二胺成分含有后述特定的芳香族二胺，也无法充分降低多孔聚酰亚胺薄膜的介电损耗角正切。
多孔聚酰亚胺薄膜的孔隙率优选为60％以上、更优选为70％以上、进一步优选为75％以上。
多孔聚酰亚胺薄膜的孔隙率例如为95％以下，优选为90％以下、更优选为85％以下、进一步优选为75％以下、特别优选为70％以下。多孔聚酰亚胺薄膜的孔隙率为上述的上限以下时，可确保多孔聚酰亚胺薄膜的机械强度，从而处理性优异。
多孔聚酰亚胺薄膜的孔隙率通过介电常数向下式中的代入来求出。
多孔聚酰亚胺薄膜的介电常数＝空气的介电常数×孔隙率+聚酰亚胺树脂的介电常数×(1-孔隙率)
代入至上式的多孔聚酰亚胺薄膜的介电常数利用谐振器在频率10GHz下进行测定。另外，介电常数在温度22℃、相对湿度50％下进行测定。
<孔隙率以外的物性>
多孔聚酰亚胺薄膜的平均孔径例如为10μm以下，优选为5μm以下、更优选为4μm以下，另外，例如为0.1μm以上，优选为1μm以上、更优选为2μm以上。平均孔径通过截面SEM照片的图像解析来测定。
10GHz下的多孔聚酰亚胺薄膜的介电常数没有限定。10GHz下的多孔聚酰亚胺薄膜的介电常数例如为2.50以下，优选为2.00以下，更优选为1.80以下、进一步优选为1.75以下、特别优选为1.70以下、最优选为1.60以下。另外，10GHz下的多孔聚酰亚胺薄膜的介电常数超过1.00。多孔聚酰亚胺薄膜的介电常数使用谐振器来测定。
10GHz下的多孔聚酰亚胺薄膜的介电损耗角正切例如为0.0028以下，优选为0.0025以下、更优选为0.0020以下、进一步优选为0.0018以下、特别优选为0.0017以下、最优选为0.0016以下。多孔聚酰亚胺薄膜的介电损耗角正切为上述的上限以下时，作为具有低介电损耗角正切的多孔聚酰亚胺薄膜，例如，适合用于第五代(5G)的标准的无线通信和/或高速柔性印刷电路板(FPC)。
另外，10GHz下的多孔聚酰亚胺薄膜的介电损耗角正切超过0.0000。多孔聚酰亚胺薄膜的介电损耗角正切使用谐振器来测定。
多孔聚酰亚胺薄膜的厚度没有限定。多孔聚酰亚胺薄膜的厚度例如为2μm以上，优选为5μm以上，另外，例如为1,000μm以下，优选为500μm以下。
<多孔聚酰亚胺薄膜的原料>
本发明的多孔聚酰亚胺薄膜为二胺成分与酸二酐成分的反应产物。换言之，多孔聚酰亚胺薄膜的原料含有二胺成分和酸二酐成分。
<二胺成分>
二胺成分含有芳香族二胺。芳香族二胺由下述式(1)表示。
Figure BDA0003602984230000041
(式中，Y表示选自由单键、-COO-、-S-、-CH(CH3)-、-C(CH3)2-、-CO-、-NH-及-NHCO-组成的组中的至少1者。)
<芳香族二胺的种类>
具体而言，作为二胺成分，可举出Y为单键的4,4’-二氨基联苯、Y为-COO-的4-氨基苯甲酸(4-氨基苯基)酯、Y为-S-的双(4-氨基苯基)硫醚、Y为-CH(CH3)-的4,4’-二氨基二苯基乙烷、Y为-C(CH3)2-的4,4’-二氨基二苯基丙烷、Y为-CO-的4,4’-二氨基二苯甲酮、Y为-NH-的4,4’-二氨基亚苯基胺、及Y为-NHCO-的4,4’-二氨基苯酰替苯胺。从进一步降低多孔聚酰亚胺薄膜的介电损耗角正切的观点出发，优选可举出4-氨基苯甲酸(4-氨基苯基)酯。需要说明的是，4-氨基苯甲酸(4-氨基苯基)酯有时也简称为APAB。上述的芳香族二胺可以单独使用或组合使用。优选可举出APAB的单独使用。
另一方面，二胺成分不含上述的芳香族二胺的情况下，无法充分降低多孔聚酰亚胺薄膜的介电损耗角正切。具体而言，二胺成分不含上述的芳香族二胺的情况下，即使使孔隙率高为50％以上，也无法充分降低多孔聚酰亚胺薄膜的介电损耗角正切。
二胺成分中的芳香族二胺的摩尔分数例如为5摩尔％以上，优选为10摩尔％以上、更优选为15％以上，另外，例如为75摩尔％以下，优选为60摩尔％以下、更优选为40摩尔％以下。
<其他二胺成分>
对于其他二胺成分，例如，除了上述的芳香族二胺以外，还可以含有第2二胺及第3二胺。
<第2二胺>
第2二胺含有一个芳香环。作为第2二胺，例如，可举出苯二胺、二甲基苯二胺、及乙基甲基苯二胺。从机械强度的观点出发，优选可举出苯二胺。作为苯二胺，例如，可举出邻苯二胺、间苯二胺、及对苯二胺。作为苯二胺，优选可举出对苯二胺。对苯二胺有时也简称为PDA。
二胺成分中的第2二胺的摩尔分数例如为10摩尔％以上，优选为20摩尔％以上、更优选为30％以上，另外，例如为80摩尔％以下，优选为70摩尔％以下、更优选为65摩尔％以下。
<第3二胺>
第3二胺含有多个芳香环和配置于它们之间的醚键。作为第3二胺，例如，可举出氧二苯胺。作为氧二苯胺，例如，可举出3,4’-氧二苯胺、及4,4’-氧二苯胺。从机械强度的观点出发，优选可举出4,4’-氧二苯胺(别名：4,4’-二氨基二苯基醚)。4,4’-氧二苯胺有时也简称为ODA。
二胺成分中的第3二胺的摩尔分数例如为5摩尔％以上，优选为10摩尔％以上，另外，例如为40摩尔％以下，优选为30摩尔％以下。
另外，相对于第2二胺和第3二胺的合计100摩尔份，上述的芳香族二胺的摩尔份例如为5摩尔份以上，优选为10摩尔份以上、更优选为20摩尔份以上，另外，例如为100摩尔份以下，优选为50摩尔份以下、更优选为30摩尔份以下。
<酸二酐成分>
酸二酐成分例如含有包含芳香环的酸二酐。作为包含芳香环的酸二酐，例如，可举出芳香族四羧酸二酐。作为芳香族四羧酸二酐，例如，可举出苯四羧酸二酐、二苯甲酮四羧酸二酐、联苯四羧酸二酐、联苯砜四羧酸二酐、及萘四羧酸二酐。
作为苯四羧酸二酐，例如，可举出苯-1,2,4,5-四羧酸二酐(别称：均苯四甲酸二酐)。作为二苯甲酮四羧酸二酐，例如，可举出3,3’,4,4’-二苯甲酮四羧酸二酐。作为联苯四羧酸二酐，例如，可举出3,3’,4,4’-联苯四羧酸二酐、2,2’,3,3’-联苯四羧酸二酐、2,3,3’,4’-联苯四羧酸二酐、及3,3’,4,4’-二苯基醚四羧酸二酐。作为联苯砜四羧酸二酐，例如，可举出3,3’,4,4’-联苯砜四羧酸二酐。作为萘四羧酸二酐，例如，可举出2,3,6,7-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、1,2,4,5-萘四羧酸二酐、及1,4,5,8-萘四羧酸二酐。这些可以单独使用或组合使用。作为酸二酐成分，从机械强度的观点出发，优选可举出联苯四羧酸二酐，更优选可举出3,3’,4,4’-联苯四羧酸二酐。需要说明的是，3,3’,4,4’-联苯四羧酸二酐有时也简称为BPDA。
二胺成分的氨基(-NH2)的摩尔量与酸二酐成分的酸酐基(-CO-O-CO-)的摩尔量例如为等量。
接着，参照图1对多孔聚酰亚胺薄膜1的制造方法进行说明。
该方法中，例如，首先，准备由金属形成的基材薄膜2(括号内及虚拟线)。基材薄膜2沿面方向延伸。作为金属，例如，可举出铜、铁、银、金、铝、镍、及它们的合金(不锈钢、青铜)。作为金属，优选可举出铜。基材薄膜2的厚度例如为0.1μm以上，优选为1μm以上，另外，例如为100μm以下，优选为50μm以下。
接着，制备包含聚酰亚胺树脂的前体、多孔化剂、成核剂和溶剂的清漆，接着，将清漆涂布于基材薄膜2的厚度方向的一个面而形成涂膜。清漆中的多孔化剂、成核剂及溶剂的、种类及配混比例等例如记载于WO2018/186486号。
聚酰亚胺树脂的前体为上述的二胺成分与酸二酐成分的反应产物。为了制备聚酰亚胺树脂的前体，将上述的二胺成分、上述的酸二酐成分和溶剂配混，制备清漆，对所述清漆进行加热，制备前体溶液。接着，在前体溶液中配混成核剂及多孔化剂，制备多孔前体溶液。
其后，将多孔前体溶液涂布于基材薄膜2的厚度方向的一个面，形成涂膜。
其后，通过加热对涂膜进行干燥，由此形成前体薄膜。通过上述的加热，在进行溶剂的去除的同时，制备将成核剂制成核的、具有聚酰亚胺树脂前体与多孔化剂的相分离结构的前体薄膜。
其后，例如，通过使用超临界二氧化碳作为溶剂的超临界萃取法，从前体薄膜提取多孔化剂(抽出或去除)。
其后，通过加热使前体薄膜固化，形成由聚酰亚胺树脂形成的多孔聚酰亚胺薄膜1。多孔聚酰亚胺薄膜1形成于基材薄膜2的厚度方向的一个面。
其后，根据需要，如图1的实线那样将基材薄膜2去除。例如，使用剥离液将基材薄膜2溶解。作为剥离液，例如，可举出FeCl3。由此，得到多孔聚酰亚胺薄膜1。需要说明的是，制造后述的金属层层叠板10时，不去除上述的基材薄膜2，作为第1金属层3而残留。
<用途>
接着，如图1的虚拟线和实线所示，对具备多孔聚酰亚胺薄膜1的金属层层叠板10进行说明。该金属层层叠板10具备多孔聚酰亚胺薄膜1和由虚拟线所示的2个金属层3、4。
金属层层叠板10中具备多孔聚酰亚胺薄膜1。即，多孔聚酰亚胺薄膜1用于接下来说明的2个金属层3、4的层叠。
2个金属层3、4包含第1金属层3和第2金属层4。第1金属层3配置于多孔聚酰亚胺薄膜1的厚度方向的另一面。作为第1金属层3的材料，可举出基材薄膜2中例示出的金属。优选可举出铜。第1金属层3的厚度例如为0.1μm以上，优选为1μm以上，另外，例如为100μm以下，优选为50μm以下。
第2金属层4配置于多孔聚酰亚胺薄膜1的厚度方向的一个面。需要说明的是，第2金属层4可以借助未图示的粘接剂层配置于多孔聚酰亚胺薄膜1的厚度方向的一个面。作为第2金属层4的材料，可举出基材薄膜2中例示出的金属。第2金属层4的厚度与第1金属层3的厚度同样。
对金属层层叠板10的制造方法进行说明。首先，在制造途中，将第2金属层4配置于具备基材薄膜2和多孔聚酰亚胺薄膜1的层叠体20的厚度方向的一个面。另一方面，由于基材薄膜2由金属形成，因此作为第1金属层3而直接残留(转用为第1金属层3)。由此，得到具备多孔聚酰亚胺薄膜1和分别配置于其厚度方向的一个面及另一面的第2金属层4及第1金属层3的金属层层叠板10。
其后，例如，通过蚀刻等，使第1金属层3和第2金属层4形成为图案。
根据用途及目的，在上述的图案的形成前、形成中和/或形成后，对金属层层叠板10进行加压。具体而言，对金属层层叠板10进行热加压。
该金属层层叠板10例如用于第五代(5G)的标准的无线通信和/或高速柔性印刷电路板(FPC)。
<一实施方式的作用效果>
上述的多孔聚酰亚胺薄膜1中，二胺成分含有式(1)所示的芳香族二胺，孔隙率为50％以上，因此多孔聚酰亚胺薄膜的介电损耗角正切低。
多孔聚酰亚胺薄膜1的介电损耗角正切为0.0028以下时，作为具有低介电损耗角正切的多孔聚酰亚胺薄膜1，适合用于例如第五代(5G)的标准的无线通信和/或高速柔性印刷电路板(FPC)。
另外，多孔聚酰亚胺薄膜1的孔隙率为95％以下时，多孔聚酰亚胺薄膜的机械强度优异。
[实施例]
以下，示出实施例及比较例，更具体地对本发明进行说明。需要说明的是，本发明不受实施例及比较例的任何限定。另外，以下的记载中使用的配混比例(含有比例)、物性值、参数等的具体的数值可以替换为上述的“具体实施方式”中记载的、对应于它们的配混比例(含有比例)、物性值、参数等该记载的上限(定义为“以下”、“不足”的数值)或下限(定义为“以上”、“超过”的数值)。
<实施例1>
在具备搅拌机及温度计的反应装置中，放入PDA(第2二胺)64.88g(0.60摩尔)、ODA(第3二胺)40.05g(0.20摩尔)、及APAB(由式(1)表示、且Y为-COO-的芳香族二胺)45.65g(0.20摩尔)，加入作为溶剂的N-甲基-2-吡咯烷酮(NMP)2300g，在40℃下进行20分钟搅拌，制备PDA、ODA及APAB的NMP溶液。
需要说明的是，NMP溶液含有二胺成分1.00摩尔。
接着，在上述的NMP溶液中加入3,3’,4,4’-联苯四羧酸二酐(BPDA)294.2g(1.00摩尔)，进而加入N-甲基-2-吡咯烷酮(NMP)18g，升温至80℃后，进行10小时搅拌，得到聚酰亚胺前体溶液。
相对于聚酰亚胺前体溶液的固体成分100质量份，加入作为成核剂的中值粒径1μm以下的PTFE粉末3质量份、作为多孔化剂的重均分子量为400的聚氧乙烯二甲基醚(日油株式会社制等级：MM400)150质量份、及2-甲基咪唑(四国化成工业株式会社制2Mz-H)4质量份，得到多孔前体溶液。将得到的多孔前体溶液涂布于由铜形成的基材薄膜2，形成涂膜。其后，使涂膜在135℃下进行15分钟干燥，制作前体薄膜。
将该前体薄膜浸渍于在60℃下被加压成30MPa的二氧化碳，进行4小时流通，由此促进多孔化剂的提取去除及残存NMP的相分离、多孔的形成。其后，对二氧化碳进行减压。
其后，将前体薄膜在真空下、以390℃的温度进行约185分钟的加热，促进残存成分的去除及酰亚胺化，由此得到配置于基材薄膜2的厚度方向的一个面的多孔聚酰亚胺薄膜1。其后，使基材薄膜2及多孔聚酰亚胺薄膜1(层叠体20)浸渍于FeCl3溶液，将基材薄膜2去除。
表1中记载各成分的g数及质量份数。表2中记载二胺成分及酸二酐成分的摩尔分数。
<实施例2～实施例6及比较例1～比较例3>
与实施例1同样地操作，制造多孔聚酰亚胺薄膜1。其中，按照表1及表2变更配方。
<评价>
对于实施例2～实施例6及比较例1～比较例3的各个多孔聚酰亚胺薄膜1，测定下述的事项。将它们的结果(其中不包括平均孔径。)记载于表2。
<介电常数及介电损耗角正切>
使用谐振器在频率10GHz分别测定多孔聚酰亚胺薄膜1的介电常数及介电损耗角正切。在温度22℃、相对湿度50％下测定介电常数及介电损耗角正切。
<孔隙率>
将上述中求出的介电常数代入下式，求出多孔聚酰亚胺薄膜1的孔隙率。
多孔聚酰亚胺薄膜的介电常数＝空气的介电常数×孔隙率+聚酰亚胺树脂的介电常数×(1-孔隙率)
<平均孔径>
通过截面SEM照片的图像解析测定实施例1及比较例1的各多孔聚酰亚胺薄膜1的平均孔径。
其结果，实施例1的多孔聚酰亚胺薄膜1的平均孔径为3.6μm。另一方面，比较例1的多孔聚酰亚胺薄膜1的平均孔径为5.3μm。
[表1]
Figure BDA0003602984230000121
[表2]
Figure BDA0003602984230000131
需要说明的是，上述发明作为本发明的例示的实施方式而提供，但这不过是单纯的例示，并不限定性地解释。对于本领域技术人员而言显而易见的本发明的变形例包含在前述权利要求书中。

Claims (3)

1.一种多孔聚酰亚胺薄膜，其是二胺成分与酸二酐成分的反应产物，
所述二胺成分含有下述式(1)所示的芳香族二胺，
所述多孔聚酰亚胺薄膜的孔隙率为50％以上，
Figure FDA0003602984220000011
式中，Y表示选自由单键、-COO-、-S-、-CH(CH3)-、-C(CH3)2-、-CO-、-NH-及-NHCO-组成的组中的至少1者。
2.根据权利要求1所述的多孔聚酰亚胺薄膜，其10GHz下的介电损耗角正切为0.0028以下。
3.根据权利要求1或2所述的多孔聚酰亚胺薄膜，其中，所述孔隙率为95％以下。
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