CN101167416B - 双面柔性印刷基板的制造方法及双面柔性印刷基板 - Google Patents
双面柔性印刷基板的制造方法及双面柔性印刷基板 Download PDFInfo
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0358—Resin coated copper [RCC]
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
- H05K2203/0759—Forming a polymer layer by liquid coating, e.g. a non-metallic protective coating or an organic bonding layer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
Abstract
Description
技术领域
本发明涉及具有足够的耐热性且制造工序简单的不需要复杂的设备的双面柔性印刷基板的制造方法。
背景技术
柔性印刷基板是在高分子绝缘膜的表面形成了导体电路的具有可挠性的电路板,近年来被大量用作实现电子设备的小型化、高密度化的装置。其中,使用芳族聚酰亚胺作为绝缘膜的基板占据主流。以往的柔性印刷基板通过以粘接剂贴合聚酰亚胺膜和铜箔的方法制造,因此耐热性、难燃性、电气特性、密合性等物性由所用粘接剂决定,聚酰亚胺的各种良好的特性无法充分发挥。作为解决该问题的方法,采用通过在金属箔上直接涂布聚酰胺酸(聚酰亚胺的前体)的清漆并除去溶剂、固化来制造的方法(专利文献1)。此外,最近随着基板的高密度化,在聚酰亚胺膜的两侧贴合铜箔的双面柔性基板的需求不断增加。对于该双面柔性印刷基板的情况,通常提出有在上述的单面柔性印刷基板上涂布热塑性聚酰亚胺等并以高热层合铜箔的方法。此外,专利文献2或3中记载了在不使用这些聚酰亚胺膜的情况下,可将粘接聚酰亚胺膜和金属箔的粘接剂层用作绝缘膜的可能性。
专利文献1:日本专利特开昭61-245868号公报
专利文献2:WO02/00791号公报
专利文献3:WO2004/048436号公报
发明的揭示
对于单面柔性印刷基板的情况,如果采用通过在金属箔上直接涂布聚酰胺酸(聚酰亚胺的前体)的清漆并除去溶剂、固化来制造的方法,则可以解决前述的粘接剂引发的各特性下降的问题。然而通常使聚酰胺酸热固化的工序需要在250~350℃的高热下加热2~5小时,在生产性方面存在问题。此外,聚酰胺酸的缩合工序中固化收缩大,因此存在制造后柔性印刷基板卷曲的问题。此外,制造双面柔性印刷基板的情况下,除了该单面柔性印刷基板的制造上的难点之外,还需要使用热塑性聚酰亚胺,它的熔点通常高达200℃以上,加热熔融需要大规模的设备。
本发明人鉴于这样的现状,以不需要在高温下长时间固化的工序且固化收缩小的双面柔性基板为目标进行了认真研究,从而完成了本发明。
即,本发明提供如下的发明。
(1)双面柔性印刷基板的制造方法,该方法由将含有以下述式(1)表示的芳族聚酰胺树脂、环氧树脂和有机溶剂的清漆直接涂布于金属箔的工序,除去溶剂、设置树脂层的工序以及将金属箔贴合于树脂层侧并使其固化的工序构成;
式中,m、n为平均值,m+n为2~200的正数,n为0.1以上的正数,Ar1、Ar3为二价的芳族基,Ar2为具有酚性羟基的二价芳族残基。
(2)通过上述(1)所述的制造方法得到的双面柔性印刷基板。
(3)双面柔性印刷基板,该基板由含酚性羟基的芳族聚酰胺树脂、环氧树脂形成的绝缘层及设置于其两面的金属箔这3层构成。
本发明的制造方法简便,不需要大规模的设备,成本较低。通过本发明得到的双面柔性基板具有接近于使用聚酰亚胺时的耐热性、难燃性的同时,可以在更一般的环氧树脂的固化条件下制造,因此在工业上是非常有利的。
实施发明的最佳方式
作为本发明中所使用的金属箔,可以例举铜、铝、铁、金、银、镍、钯、铬、钼等或它们的合金,为了提高与树脂层的粘接性,可以通过电晕放电、砂磨、镀覆、铝醇盐、铝螯合物、硅烷偶联剂等实施机械或化学的表面处理。其中,特别好是铜箔。铜箔的种类可以是电解铜箔,也可以是压延铜箔。金属箔的厚度通常为3~50μm,较好是4~40μm。
本发明中所用的芳族聚酰胺树脂只要是具有酚性羟基的聚酰胺树脂即可,没有特别限制地使用,较好是以下述式(1)表示的芳族聚酰胺树脂。该芳族聚酰胺树脂可以根据例如日本专利特开平8-143661号公报等中所记载的方法获得。
式中,m、n为平均值,m+n为2~200的正数,n为0.1以上的正数,Ar1、Ar3为二价的芳族基,Ar2为具有酚性羟基的二价芳族残基。
以下,对本发明中所用的芳族聚酰胺树脂的制法进行说明。前述以式(1)表示的聚酰胺树脂可以通过在溶剂中加入相对于芳族二羧酸的摩尔数过量的芳族二胺进行缩聚而获得。
芳族二羧酸和芳族二胺的缩聚反应较好是在作为缩合剂的芳族亚磷酸酯和吡啶衍生物的存在下进行。
作为这时所用的芳族亚磷酸酯,可以例举亚磷酸三苯酯、亚磷酸二苯酯、亚磷酸三邻甲苯酯、亚磷酸二邻甲苯酯、亚磷酸三间甲苯酯、亚磷酸二间甲苯酯、亚磷酸三对甲苯酯、亚磷酸二对甲苯酯、亚磷酸三对氯苯酯等。芳族亚磷酸酯的使用量相对于1摩尔芳族二胺通常为0.5~3摩尔,较好是1~2.5摩尔。
作为吡啶衍生物,可以例举吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、2,4-二甲基吡啶、2,6-二甲基吡啶、3,5-二甲基吡啶等。吡啶衍生物的使用量相对于1摩尔芳族二胺通常为1~5摩尔,较好是2~4摩尔。
作为上述芳族聚酰胺树脂的制造中所用的芳族二胺的例子,可以例举二氨基苯、二氨基甲苯、二氨基苯酚、二氨基甲基苯、二氨基均三甲苯、二氨基氯苯、二氨基硝基苯、二氨基偶氮苯、二氨基萘、二氨基联苯、二氨基二甲氧基联苯、二氨基二苯基醚、二氨基二甲基二苯基醚、二苯氨基甲烷、双(甲氧基苯氨基)甲烷、双(二甲氧基苯氨基)甲烷、双(乙基苯氨基)甲烷、双(二乙氧基苯氨基)甲烷、双(乙氧基苯氨基)甲烷、双(二乙氧基苯氨基)甲烷、双(二溴苯氨基)甲烷、二苯氨基异丙烷、二苯氨基六氟异丙烷、二氨基二苯酮、二氨基二甲基二苯酮、二氨基蒽醌、二氨基二苯基硫醚、二氨基二苯基亚砜和二氨基芴等,其中较好是二氨基二苯基醚和双(二乙基苯氨基)甲烷。
作为上述芳族聚酰胺树脂的制造中所用的芳族二羧酸的例子,可以例举苯二甲酸、异苯二甲酸、对苯二甲酸、苯二乙酸、苯二丙酸、联苯二羧酸、氧联二苯甲酸、亚硫基二苯甲酸、亚二硫基二苯甲酸、亚二硫基双(硝基苯甲酸)、碳酰二苯甲酸、硫酰二苯甲酸、萘二羧酸、亚甲基二苯甲酸、异亚丙基二苯甲酸、六氟异亚丙基二苯甲酸、吡啶二羧酸等不具有酚性羟基的芳族二羧酸,羟基异苯二甲酸、羟基对苯二甲酸、二羟基异苯二甲酸、二羟基对苯二甲酸等具有酚性羟基的芳族二羧酸。本发明中,由于芳族聚酰胺树脂起到环氧树脂的固化剂的作用,因此芳族聚酰胺必须具有酚性羟基。为了获得这样的芳族聚酰胺树脂,以前述的芳族二羧酸成分中具有酚性羟基的芳族二羧酸占1摩尔%以上的比例使用。
反应时,如果使用无机盐作为催化剂,则反应容易进行,是理想的。作为无机盐的具体例子,可以例举氯化锂、氯化钙、硫酸钠和它们的混合物。这些无机盐的使用量相对于1.0摩尔所用的式(5)或式(1)的化合物通常为0.1~2.0摩尔,较好是0.2~1.0摩尔。
芳族聚酰胺树脂的制造中所用的溶剂只要是与芳族聚酰胺树脂发生溶剂化的溶剂即可,没有特别限定,具体例子可以例举N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、二甲亚砜等和它们的混合溶剂,特别好是N-甲基-2-吡咯烷酮。此外,溶液中的芳族聚酰胺树脂的浓度较好是2~50重量%,若考虑到生产效率和操作性好的溶液粘度,特别好是5~30重量%。
芳族聚酰胺树脂的制造中,缩合反应结束后向反应体系内滴加水。添加水时,通常在搅拌下于60~110℃、较好是70~100℃的范围内添加。水的添加量相对于反应液的总量通常为10~200重量%,较好是20~150重量%。
水的滴加时间通常为30分钟~15小时,较好是1~10小时。残存的缩合剂在该水的滴加工序中被水解为磷酸根离子和酚类。水的滴加在搅拌下持续至树脂层和水层开始分层。
分层开始后,通过停止搅拌并静置,分为上层(水层)和下层(树脂层),除去上层的水层。该情况下,通常树脂层的粘度高而形成浆料,所以水层可以通过倾析等容易地除去。此外,也可以通过泵等输送至体系外。水层中包括磷酸、亚磷酸、催化剂、酚类、吡啶等杂质和溶剂的一部分。
除去水层而残留的树脂层也被去除部分溶剂,粘度大幅上升而不易处理,因此再次加入有机溶剂稀释。该情况下可使用的有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、二甲亚砜等。使用的溶剂的量只要是在粘度充分下降的范围内,没有特别限定,通常相对于清洗前的反应液的重量为5~100重量%,较好是10~80重量%。
通常通过重复上述的清洗工序1~10次,较好是2~8次,得到离子性杂质和低分子量有机杂质被减少了的芳族聚酰胺树脂的处理液。
将经清洗·稀释的处理液加入到弱溶剂中,使聚酰胺树脂析出。弱溶剂只要是不易与聚酰胺树脂发生溶剂化的液体,没有特别限定,具体例子可以例举水、甲醇、乙醇等和它们的混合溶剂。其使用量理想的是在析出的聚酰胺树脂可以在操作上没有问题地过滤分离的范围内尽可能少的量,相对于1重量份反应所用的溶剂较好是0.5~50重量份,特别好是1~10重量份。
经清洗的处理液和弱溶剂的混合可以是在搅拌下向处理液中缓缓添加弱溶剂,也可以是在搅拌下向弱溶剂中添加反应液。使用送液泵、压缩机和2流体喷嘴或者送液泵和1流体喷嘴将反应液喷雾到弱溶剂中的方法可以容易地析出适度粒径的芳族聚酰胺树脂,因此是理想的。进行反应液和弱溶剂的混合的温度通常为0~100℃,较好是20~80℃。
通过与弱溶剂的混合而析出的芳族聚酰胺树脂通过过滤被分离,通过用水进行滤饼清洗而除去离子性杂质。通过干燥该滤饼而获得聚酰胺树脂,通过再用水溶性有机溶剂进行清洗,可以进一步减少离子性杂质。
作为水溶性有机溶剂,可以例举甲醇、乙醇、正丙醇、异丙醇等醇类和丙酮等,它们可以单独或混合使用,特别好是甲醇。
采用水溶性有机溶剂的清洗即使是将上述通过过滤分离的芳族聚酰胺树脂滤饼在过滤器上清洗也具有效果,但通过将分离的含溶剂和弱溶剂的聚酰胺树脂滤饼或该滤饼暂时经干燥除去了溶剂和弱溶剂的聚酰胺树脂与上述水溶性有机溶剂重新加入到容器中,搅拌悬浮后,再次过滤分离,从而可发挥更好的纯化效果。该情况下的水溶性有机溶剂的使用量相对于1重量份纯净的聚酰胺树脂为1~100重量份,较好是2~50重量份,搅拌的温度较好是常温~悬浮液的沸点,特别好是在沸点下搅拌。此外,搅拌时间为0.1~24小时,较好是1~5小时。另外,通常该操作在常压下进行,但也可以在加压条件下进行。
进行上述悬浮处理后,将芳族聚酰胺树脂过滤分离,通常再用上述水溶性有机溶剂进行滤饼清洗,接着根据情况进一步用水进行滤饼清洗后,进行干燥,从而可以获得作为目标的离子性杂质少的芳族聚酰胺树脂。
本发明中使用的芳族聚酰胺树脂的固有粘度值(在30℃的0.5g/dl的N,N-二甲基乙酰胺溶液中测定)较好是在0.1~4.0dl/g的范围内。一般是否具有优选的平均聚合度通过参照固有粘度进行判断。如果固有粘度小于0.1dl/g,则成膜性和作为芳族聚酰胺树脂的性质表现不充分,因此是不理想的。相反地,如果固有粘度大于4.0dl/g,则聚合度过高,产生溶剂溶解性变差而且成形加工性变差的问题。
这样得到的式(1)的聚酰胺树脂的m和n的值由不具有酚性羟基的芳族二羧酸与具有酚性羟基的芳族二羧酸的添加比决定,通常以平均值计为2~200,较好是5~150。
本发明的制造方法中,树脂层是从含有芳族聚酰胺树脂和环氧树脂以及有机溶剂的清漆中除去有机溶剂而获得。可在该清漆中使用的环氧树脂的具体例子只要是在1分子中具有2个以上环氧基的环氧树脂即可,没有特别限定,例如可以例举双酚A型环氧树脂、双酚F型环氧树脂、苯酚酚醛清漆型树脂、甲酚酚醛清漆型环氧树脂、联苯酚型环氧树脂、三苯基甲烷型环氧树脂、联苯酚醛清漆型环氧树脂、脂环式环氧树脂等。它们可以单独使用,也可以2种以上并用。
前述清漆中,环氧树脂的使用量相对于1当量芳族聚酰胺树脂的活性氢当量较好是0.5~1.5当量。芳族聚酰胺树脂的活性氢当量可以由分子末端的氨基和分子中的酚性羟基量算出。相对于1当量活性氢不到0.5当量或超过1.5当量时,固化都不完全,可能会无法获得良好的固化物。
此外,前述清漆中也可以使用固化促进剂。作为可以使用的固化促进剂的例子,可以例举2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-苯基咪唑、2-苯基-4,5-二羟基甲基咪唑、2-苯基-4-甲基-5-二羟基甲基咪唑等咪唑类,2-(二甲基氨基甲基)苯酚、1,8-二氮杂-双环〔5,4,0〕十一烯-7等叔胺类,三苯膦等膦类,辛酸锡等金属化合物。固化促进剂根据需要相对于100重量份芳族聚酰胺树脂使用0.01~5.0重量份。
本发明的环氧树脂组合物可以根据需要包含无机填充剂。可使用的无机填充剂的具体例子可以例举二氧化硅、氧化铝、滑石等。无机填充剂的用量在本发明的环氧树脂组合物中占0~90重量%。另外,本发明的环氧树脂组合物中可以添加各种掺合剂,如硅烷偶联剂,硬脂酸、棕榈酸、硬脂酸锌、硬脂酸钙等脱模剂,颜料等。
本发明中所用的清漆可以将上述所述的环氧树脂、芳族聚酰胺树脂溶解于有机溶剂而获得。作为可用的溶剂,例如可以例举γ-丁内酯类,N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺、N,N-二甲基咪唑啉酮等酰胺类溶剂,环丁砜等砜类,二乙二醇二甲醚、二乙二醇二乙醚、丙二醇、丙二醇单甲醚、丙二醇单甲醚乙酸酯、丙二醇单丁醚等醚类溶剂,甲基乙基酮、甲基异丁基酮、环戊酮、环己酮等酮类溶剂,甲苯、二甲苯等芳族类溶剂。得到的清漆中的固体成分浓度(除溶剂以外的成分的浓度)通常为10~80重量%,较好是20~70重量%。
本发明中,为了使树脂层工业化地形成于金属箔上,使上述的清漆从制膜用狭缝吐出于金属箔的表面。作为该涂布方法,可以例举采用辊涂机、逗号式涂布机(comma coater)、刮板涂布机、刮刀涂布机、密闭涂布机等的方法。在实验室简易地进行涂布的情况下,可以使用涂布器。
接着,从涂布于金属箔上的清漆中将有机溶剂在60~180℃加热除去。该工序可以在减压下进行,也可以在红外线的照射下进行。溶剂除去后,在树脂面贴合金属箔,加压下于150~250℃使树脂层加热固化0.1~10小时,从而可以获得作为目标的双面柔性印刷基板。树脂层的厚度由涂布的清漆的固体成分浓度决定,通常为2~200μm,较好是3~150μm。
实施例
以下,通过实施例对本发明进一步进行具体的说明,下述中只要没有特别说明,份为重量份。
合成例1
对安装了温度计、冷凝管、分馏管、搅拌机的烧瓶实施氮气净化的同时,加入2.7份5-羟基异苯二甲酸、119.6份异苯二甲酸、150份3,4′-二氨基二苯基醚、7.8份氯化锂、811.5份N-甲基吡咯烷酮、173.6份吡啶,搅拌溶解后,加入376.2份亚磷酸三苯酯,在95℃进行缩合反应4小时,得到聚酰胺树脂的反应液(A)。在该反应液(A)中用2小时在90℃滴加490份水,静置。由于分层为上层的水层、下层的油层(树脂层),将上层通过倾析除去。废水的量为1100份。在油层(树脂层)中加入610份N,N-二甲基甲酰胺进行稀释。接着,在90℃用1小时滴加245份水。将上层通过倾析除去。废水的量为1100份。再将该清洗工序重复3次,得到1600份芳族聚酰胺树脂的处理液。将该聚酰胺溶液用滴液漏斗滴加到被搅拌的3200份水中,使微粒状的芳族聚酰胺树脂析出,过滤分离。使得到的湿滤饼分散于2400份甲醇中,在搅拌下回流2小时。接着,过滤分离甲醇,以1600份水清洗,干燥,从而得到240份以下述式(2)
表示的芳族聚酰胺树脂。将该芳族聚酰胺树脂中所含的所有磷量通过硫酸·硝酸湿式氧化分解后,通过钼蓝-抗坏血酸吸光光度法定量,结果为550ppm。得到的芳族聚酰胺树脂的固有粘度为0.52dl/g(二甲基乙酰胺溶液,30℃),式中,m的值为约39.2,n的值为约0.8。此外,由加入比例计算的含酚性羟基的芳族聚酰胺树脂的相对于环氧基的活性氢当量为约5000g/eq。
对于7.50份得到的芳族聚酰胺树脂,使用0.42份作为环氧树脂的NC-3000(日本化药株式会社制,环氧当量275g/eq,软化点55℃)、0.01份作为固化促进剂的2PHZ-PW(四国化成制)、17份作为溶剂的N-甲基吡咯烷酮,搅拌溶解,调制成清漆。
试验例1
将合成例1中得到的清漆用涂布器在厚18μm的电解铜箔的粗糙面涂布100μm,通过在130℃干燥30分钟除去溶剂。接着,通过在180℃固化1小时,得到单面柔性基板。固化后,未发现室温下的卷曲。
将得到的单面柔性基板煮沸30分钟后,使聚酰亚胺面在260℃的焊锡浴上接触30秒,观察铜箔表面的外观,结果未观察到异常。
将得到的单面柔性基板的铜箔通过蚀刻除去,测定树脂层的玻璃化温度,结果为235℃。此外,基于UL94标准观察难燃性,结果为V-0级。
实施例1
将合成例1中得到的清漆用涂布器在厚18μm的电解铜箔的粗糙面涂布100μm,通过在130℃干燥30分钟除去溶剂。接着,在树脂面贴合厚18μm的电解铜箔,用热板压机在30Kg/cm2的压力下在180℃固化1小时,得到双面柔性基板。
对于得到的双面柔性基板的粘接性,基于JIS-C6471标准进行铜箔拉剥试验,测定结果为2.1Kg/cm。
Claims (3)
2.双面柔性印刷基板,其特征在于,通过权利要求1所述的制造方法得到。
3.双面柔性印刷基板,其特征在于,包括由权利要求1的式(1)表示的含酚性羟基的芳族聚酰胺树脂、环氧树脂形成的绝缘层及设置于其两面的金属箔的3层。
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KR101312369B1 (ko) | 2005-10-31 | 2013-09-27 | 니폰 가야꾸 가부시끼가이샤 | 고무 변성 폴리아미드 수지, 에폭시 수지 조성물 및 그경화물 |
JP5459842B2 (ja) * | 2006-09-09 | 2014-04-02 | テイジン・アラミド・ビー.ブイ. | 架橋可能なアラミドコポリマー |
JP4884298B2 (ja) * | 2007-05-17 | 2012-02-29 | 日本化薬株式会社 | 樹脂層付き銅箔 |
CN101722694A (zh) * | 2009-11-17 | 2010-06-09 | 丹阳市永和电器科技有限公司 | 一种高Tg高导热型铝基覆铜箔层压板 |
CN106661222A (zh) * | 2014-07-02 | 2017-05-10 | 东洋油墨Sc控股株式会社 | 热硬化性树脂组合物、聚酰胺、接着性片、硬化物及印刷配线板 |
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US7608336B2 (en) * | 2002-11-28 | 2009-10-27 | Nippon Kayaku Kabushiki Kaisha | Flame-retardant epoxy resin composition and cured product obtained therefrom |
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JP3949676B2 (ja) * | 2003-07-22 | 2007-07-25 | 三井金属鉱業株式会社 | 極薄接着剤層付銅箔及びその極薄接着剤層付銅箔の製造方法 |
JP3977790B2 (ja) * | 2003-09-01 | 2007-09-19 | 古河サーキットフォイル株式会社 | キャリア付き極薄銅箔の製造方法、及び該製造方法で製造された極薄銅箔、該極薄銅箔を使用したプリント配線板、多層プリント配線板、チップオンフィルム用配線基板 |
JP2005089616A (ja) * | 2003-09-18 | 2005-04-07 | Nippon Kayaku Co Ltd | 熱硬化性樹脂組成物及びその硬化物 |
US7740936B2 (en) * | 2004-11-10 | 2010-06-22 | Hitachi Chemical Co., Ltd. | Adhesion assisting agent fitted metal foil, and printed wiring board using thereof |
CN101208373B (zh) * | 2005-07-21 | 2010-12-01 | 日本化药株式会社 | 聚酰胺树脂,环氧树脂组合物及其固化物 |
KR101312369B1 (ko) * | 2005-10-31 | 2013-09-27 | 니폰 가야꾸 가부시끼가이샤 | 고무 변성 폴리아미드 수지, 에폭시 수지 조성물 및 그경화물 |
JP4884298B2 (ja) * | 2007-05-17 | 2012-02-29 | 日本化薬株式会社 | 樹脂層付き銅箔 |
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2005
- 2005-04-28 JP JP2005131794A patent/JP2006310574A/ja active Pending
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2006
- 2006-04-28 CN CN2006800146524A patent/CN101167416B/zh not_active Expired - Fee Related
- 2006-04-28 WO PCT/JP2006/308958 patent/WO2006118239A1/ja active Application Filing
- 2006-04-28 ES ES06732461T patent/ES2366800T3/es active Active
- 2006-04-28 EP EP06732461A patent/EP1876873B1/en not_active Not-in-force
- 2006-04-28 CA CA002605613A patent/CA2605613A1/en not_active Abandoned
- 2006-04-28 KR KR1020077025068A patent/KR101258891B1/ko not_active IP Right Cessation
- 2006-04-28 TW TW095115451A patent/TWI392587B/zh active
- 2006-04-28 US US11/918,975 patent/US20090056982A1/en not_active Abandoned
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TW200709923A (en) | 2007-03-16 |
EP1876873A4 (en) | 2009-07-22 |
CA2605613A1 (en) | 2006-11-09 |
ES2366800T3 (es) | 2011-10-25 |
WO2006118239A1 (ja) | 2006-11-09 |
CN101167416A (zh) | 2008-04-23 |
KR101258891B1 (ko) | 2013-04-29 |
TWI392587B (zh) | 2013-04-11 |
KR20080003846A (ko) | 2008-01-08 |
EP1876873B1 (en) | 2011-07-27 |
US20090056982A1 (en) | 2009-03-05 |
JP2006310574A (ja) | 2006-11-09 |
EP1876873A1 (en) | 2008-01-09 |
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