CN115214211A - 金属层层叠板用薄膜 - Google Patents
金属层层叠板用薄膜 Download PDFInfo
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- CN115214211A CN115214211A CN202210408694.7A CN202210408694A CN115214211A CN 115214211 A CN115214211 A CN 115214211A CN 202210408694 A CN202210408694 A CN 202210408694A CN 115214211 A CN115214211 A CN 115214211A
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Abstract
提供:虽然多孔树脂层的厚度方向整体的平均孔径小、但是第1区域的平均孔径相对于第5区域的平均孔径之比变得过小的情况被抑制的金属层层叠板用薄膜。金属层层叠板用薄膜(1)用于金属层(5)的层叠。金属层层叠板用薄膜(1)在厚度方向上依次具备:多孔树脂层(2)和表皮层(3)。多孔树脂层(2)的厚度方向整体中的平均孔径W为7.0μm以下。将多孔树脂层沿厚度方向5等分时,多孔树脂层(2)包含沿远离表皮层(3)的方向依次配置的第1区域(11)至第5区域(15)。第1区域(11)的平均孔径A1相对于第5区域(15)的平均孔径A5之比(A1/A5)为0.45以上且1以下。
Description
技术领域
本发明涉及金属层层叠板用薄膜,详细地涉及用于金属层的层叠的金属层层叠板用薄膜。
背景技术
已知有一种沿厚度方向依次具备多孔树脂层和表皮层的金属层层叠板用薄膜(例如参照下述专利文献1)。在金属层上层叠金属层层叠板用薄膜,得到金属层层叠板。
专利文献1的实施例2中记载的金属层层叠板用薄膜中,多孔树脂层的厚度方向整体的平均孔径大至约8μm(基于图4)。另外,将上述多孔树脂层沿厚度方向5等分时,包含沿远离表皮层的方向依次配置的第1区域至第5区域,第1区域的平均孔径相对于第5区域的平均孔径之比为约0.8,接近于1(基于图4)。亦即,第1区域的平均孔径与第5区域的平均孔径近似。
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
由金属层层叠板用薄膜制造金属层层叠板时,进而,对金属层层叠板进行加工时,有时对金属层层叠板用薄膜沿厚度方向进行加压(具体而言,为热压)。
然而,多孔树脂层的厚度方向整体的平均孔径大的情况下,上述加压后的厚度的减少率变得过大。如此,存在加压前后的介电常数大幅变动这样的不良情况。
另一方面,如果减小多孔树脂层的厚度方向整体的平均孔径,则第1区域的平均孔径相对于第5区域的平均孔径之比变得过小。具体而言,上述比接近于0。如此,第5区域的平均孔径相对于第1区域的平均孔径变得过大,其结果,存在加压前后的介电常数大幅变动这样的不良情况。
本发明提供:虽然多孔树脂层的厚度方向整体的平均孔径小、但是第1区域的平均孔径相对于第5区域的平均孔径之比变得过小的情况被抑制的金属层层叠板用薄膜。
用于解决问题的方案
本发明包含一种金属层层叠板用薄膜,其用于金属层的层叠,该金属层层叠板用薄膜在厚度方向上依次具备多孔树脂层和表皮层,前述多孔树脂层的厚度方向整体中的平均孔径为7.0μm以下,将前述多孔树脂层沿厚度方向5等分时,前述多孔树脂层包含沿远离前述表皮层的方向依次配置的第1区域至第5区域,前述第1区域的平均孔径相对于前述第5区域的平均孔径之比为0.45以上且1以下。
发明的效果
本发明的金属层层叠板用薄膜中,虽然多孔树脂层的厚度方向整体的平均孔径小至7.0μm以下,但是第1区域的平均孔径相对于第5区域的平均孔径之比为0.45以上,变得过小的情况被抑制。因此,可以抑制加压前后的介电常数的变动。
附图说明
图1为本发明的金属层层叠板用薄膜的一实施方式的截面图。
图2为金属层层叠板用薄膜的变形例的截面图。
附图标记说明
1 金属层层叠板用薄膜
2 多孔树脂层
3 表皮层
4 第2表皮层
5 第1金属层
6 第2金属层
10 金属层层叠板
11 第1区域
15 第5区域
具体实施方式
<金属层层叠板用薄膜的一实施方式>
参照图1,对本发明的金属层层叠板用薄膜的一实施方式进行说明。如图1所示,金属层层叠板用薄膜1具有厚度,沿与厚度方向正交的面方向延伸。金属层层叠板用薄膜1的厚度没有特别限定。金属层层叠板用薄膜1的频率10GHz下的介电常数例如为2.5以下、优选2.0以下,另外,例如超过1.0。金属层层叠板用薄膜1的介电常数由电介质共振器法来实测。金属层层叠板用薄膜1的厚度例如为2μm以上、优选5μm以上,另外,例如为1000μm以下、优选500μm以下。
金属层层叠板用薄膜1面向厚度方向一侧依次具备多孔树脂层2和表皮层3。
<多孔树脂层2>
多孔树脂层2形成金属层层叠板用薄膜1中的厚度方向另一面。多孔树脂层2沿面方向延伸。多孔树脂层2为多孔质。多孔树脂层2具有闭孔结构和/或连续泡孔结构。多孔树脂层2的孔隙率例如为50%以上、优选60%以上、更优选70%以上。
需要说明的是,多孔树脂层2的孔隙率例如低于100%,进而,为99%以下。多孔树脂层2由聚酰亚胺形成的情况下,孔隙率由下述式求出。
多孔树脂层2的介电常数=空气的介电常数×孔隙率+聚酰亚胺的介电常数×(1-孔隙率)
<厚度方向整体中的平均孔径W>
多孔树脂层2的厚度方向整体中的平均孔径W为7.0μm以下。多孔树脂层2的厚度方向整体中的平均孔径W超过7.0μm时,如果对金属层层叠板用薄膜1沿厚度方向进行加压(具体而言,热压),则加压的厚度的变动率是负的,而且其绝对值大。亦即,厚度的减少率过大。
如此,金属层层叠板用薄膜1的加压前后的介电常数的变动大。
多孔树脂层2的厚度方向整体中的平均孔径W优选6.0μm以下。另外,多孔树脂层2的厚度方向整体中的平均孔径W的下限无限定。多孔树脂层2的厚度方向整体中的平均孔径W的下限例如为0.1μm。多孔树脂层2的厚度方向整体中的平均孔径W的求算方法记载于后述的实施例。
<经5等分的5个区域>
将多孔树脂层2沿厚度方向5等分时,多孔树脂层2包含从厚度方向一面向另一面依次配置的第1区域11至第5区域15。具体而言,多孔树脂层2中,朝向厚度方向另一侧(朝向远离后述的表皮层3的方向)依次配置有:第1区域11、第2区域12、第3区域13、第4区域14和第5区域15。图1中,用一点划线表示厚度方向上相邻的区域的边界,但在实际的截面观察中,观察不到上述边界。
第1区域11形成多孔树脂层2的厚度方向一面。第5区域15形成多孔树脂层2的厚度方向另一面。第3区域13为厚度方向中央区域。第2区域12夹持于第1区域11与第3区域13。第4区域14夹持于第3区域13与第5区域15。第1区域11的厚度与第2区域12的厚度与第3区域13的厚度与第4区域14的厚度与第5区域15的厚度相同。
<平均孔径之比>
第1区域11的平均孔径A1相对于第5区域15的平均孔径A5之比(A1/A5)为0.45以上且1.0以下。
第1区域11的平均孔径A1相对于第5区域15的平均孔径A5之比(A1/A5)如果低于0.45,则第5区域15的平均孔径A5相对于第1区域11的平均孔径A1变得过大,其结果,加压前后的金属层层叠板用薄膜1的介电常数大幅变动。
需要说明的是,在后述的制造方法中,第5区域15的平均孔径A5不可能低于第1区域11的平均孔径A1。因此,第1区域11的平均孔径A1相对于第5区域15的平均孔径A5之比(A1/A5)不超过1.0。
第1区域11的平均孔径A1相对于第5区域15的平均孔径A5之比(A1/A5)优选0.50以上。
为了将第1区域11的平均孔径A1相对于第5区域15的平均孔径A5之比(A1/A5)设定为上述范围,调整如下说明的树脂的配方(组成)、多孔前体溶液的粘度、涂布机间隙、多孔树脂层2的厚度等。
第1区域11的平均孔径A1例如为1.0μm以上、优选2.0μm以上,另外,例如低于4.0μm、优选3.5μm以下。第5区域15的平均孔径A5例如为9.0μm以下、优选8.0μm以下,另外,例如为2.0μm以上、优选4.0μm以上。
第1区域11的平均孔径A1与第5区域15的平均孔径A5由SEM截面观察求出。求算方法的详情记载于后述的实施例。
作为金属层层叠板用薄膜1的材料,例如可以举出热固性树脂。作为热固性树脂,例如可以举出聚碳酸酯树脂、聚酰亚胺树脂、氟化聚酰亚胺树脂、环氧树脂、酚醛树脂、脲树脂、三聚氰胺树脂、苯二甲酸二烯丙酯树脂、有机硅树脂、热固性聚氨酯树脂、氟树脂(含氟烯烃的聚合物(具体而言,为聚四氟乙烯(PTFE)))、和液晶聚合物(LCP)。它们可以单独使用或并用2种以上。上述树脂中,从机械强度的观点出发,优选可以举出聚酰亚胺树脂。需要说明的是,包含聚酰亚胺树脂的物性和制造方法的详情例如记载于WO2018/186486号中。
多孔树脂层2的厚度例如为60μm以下、优选50μm以下、更优选40μm以下,另外,为10μm以上、优选25μm以上。多孔树脂层2的厚度如果为上述上限以下,则可以容易将上述平均孔径之比(A1/A5)设定为上述范围。
<表皮层3>
表皮层3配置于多孔树脂层2的厚度方向一面。因此,多孔树脂层2中,第1区域11至第5区域15沿远离表皮层3的方向(相当于厚度方向另一侧)依次配置。另外,表皮层3与多孔树脂层2的第1区域11的厚度方向一面整面接触。表皮层3沿面方向延伸。表皮层3形成金属层层叠板用薄膜1的厚度方向一面。表皮层3实质上为无孔质。表皮层3的孔隙率例如为1%以下。表皮层3的材料没有特别限定。优选表皮层3的材料与多孔树脂层2的材料相同。该情况下,表皮层3相对于多孔树脂层2的厚度方向一面一体地形成。表皮层3的厚度例如为1μm以上,另外,例如为5μm以下。表皮层3的厚度相对于金属层层叠板用薄膜1的厚度之比例如为0.01以上,另外,例如为0.2以下。
接着,对金属层层叠板用薄膜1的制造方法进行说明。
具体而言,首先,准备由金属形成的基材薄膜7(括号和虚拟线)。基材薄膜7沿面方向延伸。作为金属,例如可以举出铜、铁、银、金、铝、镍、和它们的合金(不锈钢、青铜)。作为金属,优选可以举出铜。基材薄膜7的厚度例如为0.1μm以上、优选1μm以上,另外,例如为100μm以下、优选50μm以下。
然后,制备包含上述树脂的前体、多孔化剂、成核剂和溶剂的清漆,然后,将清漆涂布于基材薄膜7的厚度方向一面,形成涂膜。清漆中的多孔化剂、成核剂和溶剂的、种类和配混比例等例如记载于WO2018/186486号中。
对树脂为聚酰亚胺树脂的情况进行说明。聚酰亚胺树脂的前体例如为二胺成分与酸二酐成分的反应产物。作为二胺成分,例如可以举出芳香族二胺、脂肪族二胺、和脂环族二胺。作为二胺成分,优选可以举出芳香族二胺。
作为芳香族二胺,可以举出第1二胺、第2二胺、和第3二胺。
第1二胺含有一个芳香环。作为第1二胺,例如可以举出苯二胺、二甲基苯二胺、和乙基甲基苯二胺。从机械强度的观点出发,优选可以举出苯二胺。作为苯二胺,例如可以举出邻苯二胺、间苯二胺、和对苯二胺。作为苯二胺,优选可以举出对苯二胺。
第2二胺含有:多个芳香环、和配置于它们之间的醚键。作为第2二胺,例如可以举出氧二苯胺。作为氧二苯胺,例如可以举出3,4’-氧二苯胺、和4,4’-氧二苯胺。从机械强度的观点出发,优选可以举出4,4’-氧二苯胺。
第3二胺含有:多个芳香环、和配置于它们之间的酯键。第3二胺是用于提高多孔树脂层2中的上述比(A1/A5)的成分。作为第3二胺,例如可以举出氨基苯甲酸氨基苯酯,优选可以举出4-氨基苯甲酸(4-氨基苯基)酯。
需要说明的是,作为芳香族二胺,除第1二胺至第3二胺之外,例如还可以举出4,4’-亚甲基二苯胺、4,4’-二亚甲基二苯胺、4,4’-三亚甲基二苯胺、和双(4-氨基苯基)砜。
上述二胺成分可以单独使用,另外,可以并用它们。作为二胺成分,优选可以举出第1二胺、第2二胺、和第3二胺的组合。更优选可以举出对苯二胺、4,4’-氧二苯胺、和4-氨基苯甲酸(4-氨基苯基)酯的组合。
需要说明的是,对苯二胺有时简称为PDA。4,4’-氧二苯胺(别称:4,4’-二氨基二苯醚)有时简称为ODA。4-氨基苯甲酸(4-氨基苯基)酯有时简称为APAB。
二胺成分中的第1二胺的摩尔分数优选10摩尔%以上、更优选20摩尔%以上,另外,例如为70摩尔%以下、优选65摩尔%以下。二胺成分中的第2二胺的摩尔分数优选5摩尔%以上、更优选10摩尔%以上,另外,例如为40摩尔%以下、优选30摩尔%以下。二胺成分中的第3二胺的摩尔分数优选5摩尔%以上、更优选10摩尔%以上,另外,例如为40摩尔%以下、优选30摩尔%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,例如可以举出芳香族四羧酸二酐。作为芳香族四羧酸二酐,例如可以举出苯四羧酸二酐、二苯甲酮四羧酸二酐、联苯四羧酸二酐、联苯砜四羧酸二酐、和萘四羧酸二酐。
作为苯四羧酸二酐,例如可以举出苯-1,2,4,5-四羧酸二酐(别称:均苯四酸二酐)。作为二苯甲酮四羧酸二酐,例如可以举出3,3’,4,4’-二苯甲酮四羧酸二酐。作为联苯四羧酸二酐,例如可以举出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、和3,3’,4,4’-二苯基醚四羧酸二酐。作为联苯砜四羧酸二酐,例如可以举出3,3’,4,4’-联苯砜四羧酸二酐。作为萘四羧酸二酐,例如可以举出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、和1,4,5,8-萘四羧酸二酐。它们可以单独使用或并用。作为酸二酐成分,从机械强度的观点出发,优选可以举出联苯四羧酸二酐,更优选可以举出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简称为BPDA。
二胺成分与酸二酐成分的比例以二胺成分的氨基(-NH2)的摩尔量与酸二酐成分的酸酐基(-CO-O-CO-)的摩尔量例如成为等量的方式进行调整。
为了制备聚酰亚胺树脂的前体,将上述二胺成分、上述酸二酐成分和溶剂配混,制备清漆,将上述清漆加热,制备前体溶液。然后,在前体溶液中配混成核剂和多孔化剂,制备多孔前体溶液。
多孔前体溶液的25℃下的粘度可以根据如下说明的涂布机的条件和前体薄膜的厚度而适宜设定。具体而言,多孔前体溶液的25℃下的粘度例如为5Pa·s以上、优选10Pa·s以上,另外,例如为100Pa·s以下、优选50Pa·s以下。多孔前体溶液的25℃下的粘度由E型粘度测量定。
之后,将多孔前体溶液涂布于基材薄膜7的厚度方向一面,形成涂膜。涂膜的形成中,使用涂布机。涂布机没有特别限定。作为涂布机,例如可以举出凹版辊涂布机、逆转辊涂布机、辊舐涂布机、浸渍辊涂布机、棒涂机、刮刀涂布机、喷涂机、逗点涂布机(commacoater)、直接涂布机、和模涂机。优选可以举出逗点涂布机和模涂机。另一方面,使用模的方法中,有时涂膜变得过厚,变得不适合。
之后,通过加热将涂膜干燥,从而形成前体薄膜。通过上述加热,进行溶剂的去除的同时,制备将成核剂作为核的、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。另外,上述基于加热的干燥的温度低,另外,干燥的时间短。具体而言,干燥温度例如为160℃以下。干燥时间例如为1000秒以下。通过上述基于加热的干燥,在前体薄膜的厚度方向一面形成表皮层3。
之后,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(抽出或者去除)。
之后,通过加热使前体薄膜固化,形成由聚酰亚胺树脂形成的金属层层叠板用薄膜1。该金属层层叠板用薄膜1朝向厚度方向另一侧依次具备表皮层3和多孔树脂层2。表皮层3的厚度方向一面与基材薄膜7接触。
之后,根据需要,如图1的实线所示,将基材薄膜7去除。例如,用剥离液使基材薄膜7溶解。作为剥离液,例如可以举出FeCl3。由此,得到金属层层叠板用薄膜1。需要说明的是,制造后述的金属层层叠板10时,作为第1金属层5残留而不将上述基材薄膜7去除。
<用途>
接着,如图1的虚拟线所示,对具备金属层层叠板用薄膜1的金属层层叠板10进行说明。该金属层层叠板10具备:金属层层叠板用薄膜1、和用虚拟线表示的2个金属层5、6。
金属层层叠板10中具备金属层层叠板用薄膜1。亦即,金属层层叠板用薄膜1用于如下说明的2个金属层5、6的层叠。
2个金属层5、6包含第1金属层5和第2金属层6。第1金属层5配置于金属层层叠板用薄膜1的厚度方向一面。具体而言,第1金属层5与表皮层3的厚度方向一面整面接触。作为第1金属层5的材料,可以举出基材薄膜7中示例的金属。优选可以举出铜。第1金属层5的厚度例如为0.1μm以上、优选1μm以上,另外,例如为100μm以下、优选50μm以下。
第2金属层6配置于金属层层叠板用薄膜1的厚度方向另一面。具体而言,第2金属层6与多孔树脂层2(第5区域15)的厚度方向另一面整面接触。需要说明的是,第2金属层6可以借助未图示的粘接剂层配置于多孔树脂层2的厚度方向另一面。作为第2金属层6的材料,可以举出基材薄膜7中示例的金属。第2金属层6的厚度与第1金属层5的厚度同样。
对金属层层叠板10的制造方法进行说明。首先,在制造中途,在具备基材薄膜7和金属层层叠板用薄膜1的层叠体的厚度方向另一面配置第2金属层6。另一方面,基材薄膜7由金属形成,因此,作为第1金属层5直接残留(转用为第1金属层5)。由此,得到具备金属层层叠板用薄膜1、以及配置于其厚度方向一面和另一面的第1金属层5和第2金属层6的金属层层叠板10。
之后,例如通过蚀刻等,将第1金属层5和第2金属层6形成为图案。
根据用途和目的,在上述图案的形成前、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进行热压。
该金属层层叠板10用于例如第五代(5G)的标准的无线通信、高速柔性印刷电路板(FPC)。
(一实施方式的作用效果)
该金属层层叠板用薄膜1中,虽然多孔树脂层2的厚度方向整体的平均孔径W小至7.0μm以下,但是第1区域11的平均孔径A1相对于第5区域15的平均孔径A5之比(A1/A5)为0.45以上,变得过小的情况被抑制。因此,可以抑制金属层层叠板用薄膜1加压前后的介电常数的变动。
(变形例)
以下的变形例中,对与上述一实施方式同样的构件和工序标注相同的附图标记,省略其详细说明。另外,变形例除特别说明之外,可以发挥与一实施方式同样的作用效果。进一步,可以将一实施方式和其变形例适宜组合。
基材薄膜7的材料可以为树脂。该情况下,制造金属层层叠板用薄膜1后,将基材薄膜7去除后,根据需要用粘接剂层将第1金属层5贴附于表皮层3的厚度方向一面。此时,利用加压(具体而言,为热压)。
如图2所示,变形例的金属层层叠板用薄膜1具备2个表皮层3、4。2个表皮层3、4包含上述表皮层3和第2表皮层4。第2表皮层4配置于多孔树脂层2的厚度方向另一面。具体而言,第2表皮层4与多孔树脂层2(第5区域15)的厚度方向另一面整面接触。第2表皮层4的材料和厚度与上述表皮层3的材料和厚度同样。
实施例
以下示出实施例和比较例,对本发明进一步具体地进行说明。需要说明的是,本发明不受实施例和比较例的任何限定。另外,以下的记载中使用的配混比例(含有比例)、物性值、参数等具体数值可以替换为上述“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”、“低于”的数值)或下限(定义为“以上”、“超过”的数值)。
(实施例1)
在具备搅拌机和温度计的反应装置中,放入PDA 71.37g(0.66摩尔)、ODA 44.05g(0.22摩尔)、和APAB 50.22g(0.22摩尔),加入作为溶剂的N-甲基-2-吡咯烷酮(NMP)2300g并搅拌,制备PDA、ODA和APAB的NMP溶液。需要说明的是,NMP溶液含有二胺成分1.10摩尔。
然后,在PDA、ODA和APAB的NMP溶液中,缓慢地添加3,3’,4,4’-联苯四羧酸二酐(3,3’,4,4’-BPDA)323.64g(1.10摩尔),进一步加入N-甲基-2-吡咯烷酮(NMP)331g,升温至80℃后,搅拌10小时,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)200质量份、和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。多孔前体溶液的25℃下的粘度为50Pa·s。用逗点涂布机将该多孔前体溶液涂布于由铜形成的基材薄膜7(第2金属层6),形成涂膜。逗点涂布机具有隔着间隙对向配置的2根辊。使基材薄膜7与一根辊接触,将基材薄膜7与另一根辊的最接近距离(间隙)设定为225μm。
之后,使涂膜以120~160℃干燥540秒,制作厚度为约50μm的前体薄膜。
使该前体薄膜浸渍于在60℃下加压至30MPa的二氧化碳,流通8小时,从而促进多孔化剂的提取去除、残留NMP的相分离和多孔的形成。之后,将二氧化碳减压。
之后,将前体薄膜在真空下、以300℃~400℃的温度热处理约5小时,促进残留成分的去除和酰亚胺化,从而得到配置于基材薄膜7的厚度方向一面的金属层层叠板用薄膜1。之后,使基材薄膜7和金属层层叠板用薄膜1浸渍于FeCl3溶液,使基材薄膜7溶解并去除。由此,制造具备多孔树脂层2和表皮层3的金属层层叠板用薄膜1。
实施例1的多孔树脂层2、表皮层3和金属层层叠板用薄膜1的厚度分别为40.7μm、3.0μm、和43.7μm。金属层层叠板用薄膜1的厚度用薄膜厚度测定器(HKT-1200、Fujiwork公司制)测定。表皮层3的厚度由后述的SEM观察求出。对于多孔树脂层2,从金属层层叠板用薄膜1的厚度中减去表皮层3的厚度而求出。之后的例子的厚度也与上述同样地求出。
金属层层叠板用薄膜1的频率10GHz下的介电常数为1.62。介电常数用PNA网络分析仪(Agilent Technologies公司制)、由Split Post电介质共振器(SPDR)法求出。之后的例子的介电常数也与上述同样地求出。
(实施例2)
与实施例1同样地,制造金属层层叠板用薄膜1。其中,将间隙变更为250μm,将干燥时间变更为900秒。实施例2的多孔树脂层2、表皮层3和金属层层叠板用薄膜1的厚度分别为44.9μm、3.9μm、和48.8μm。实施例2的金属层层叠板用薄膜1的频率10GHz下的介电常数为1.61。
(实施例3)
与实施例2同样地,制造金属层层叠板用薄膜1。其中,使得将配方升温至聚酰亚胺前体溶液制备时的80℃后的搅拌时间由10小时变更为15小时,从而将多孔前体溶液的25℃下的粘度变更为10Pa·s。实施例3的多孔树脂层2、表皮层3和金属层层叠板用薄膜1的厚度分别为42.0μm、3.0μm、和45.0μm。实施例3的金属层层叠板用薄膜1的频率10GHz下的介电常数为1.63。
(实施例4)
与实施例1同样地,制造金属层层叠板用薄膜1。其中,将间隙变更为260μm,将干燥时间变更为900秒。实施例4的多孔树脂层2、表皮层3和金属层层叠板用薄膜1的厚度分别为49.1μm、3.7μm、和52.8μm。实施例4的金属层层叠板用薄膜1的频率10GHz下的介电常数为1.65。
(比较例1)
与实施例1同样地,制造金属层层叠板用薄膜1。其中,将间隙变更为275μm,将干燥时间变更为900秒。比较例1的金属层层叠板用薄膜1的厚度为58.3μm,频率10GHz下的介电常数为1.54。
(比较例2)
按照专利文献1的实施例2的配方制造金属层层叠板用薄膜1。实施例2的多孔树脂层2、表皮层3和金属层层叠板用薄膜1的厚度分别为94μm、6μm、和100μm,频率10GHz下的介电常数为1.48。
<评价>
对于各实施例和比较例的金属层层叠板用薄膜1,评价如下事项。将它们的结果记载于表1中。
<平均孔径>
用SEM(SU8020、Hitachi,Ltd.制),在加速电压2.0kV的条件下,观察金属层层叠板用薄膜1的截面的二次电子图像,获得SEM图像。由该SEM图像,确定第1区域11至第5区域15,分别测定第1区域11的平均孔径A1、第5区域15的孔径A5、和厚度方向整体的平均孔径W两次。各孔径由以SEM图像的比例尺为基准的孔的最大孔径的测量求出。然后,得到两次测定值的平均值分别作为第1区域11的平均孔径A1、第5区域15的孔径A5、和厚度方向整体的平均孔径W。另外,也一并算出上述中得到的第1区域11的平均孔径A1相对于第5区域15的平均孔径A5之比(A1/A5)。
<热压性>
由金属层层叠板用薄膜1制作大小40mm×40mm的样品。将该样品安装于瞬间真空层叠装置VS008-1515(Mikado Technos公司制),在160℃下、以5MPa压力加压300秒。求出加压后的厚度和介电常数。然后,分别基于下述式求出加压前后的厚度的变动率和介电常数的变动率。
加压前后的厚度的变动率(%)=(加压后的厚度-加压前的厚度)/加压前的厚度×100
加压前后的介电常数的变动率(%)=(加压后的介电常数-加压前的介电常数)/加压前的介电常数×100
[表1]
*1:相当于WO2018/186486号的实施例2 *2:120℃
需要说明的是,上述发明作为本发明的示例的实施方式提供,但这些只过是单纯的示例,不作限定性解释。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于前述的权利要求书中。
Claims (1)
1.一种金属层层叠板用薄膜,其用于金属层的层叠,
所述金属层层叠板用薄膜在厚度方向上依次具备多孔树脂层和表皮层,
所述多孔树脂层的厚度方向整体中的平均孔径为7.0μm以下,
将所述多孔树脂层沿厚度方向5等分时,所述多孔树脂层包含沿远离所述表皮层的方向依次配置的第1区域至第5区域,
所述第1区域的平均孔径相对于所述第5区域的平均孔径之比为0.45以上且1以下。
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