CN102165104A - 表面处理铜箔及镀铜层压板 - Google Patents

表面处理铜箔及镀铜层压板 Download PDF

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CN102165104A
CN102165104A CN2009801359023A CN200980135902A CN102165104A CN 102165104 A CN102165104 A CN 102165104A CN 2009801359023 A CN2009801359023 A CN 2009801359023A CN 200980135902 A CN200980135902 A CN 200980135902A CN 102165104 A CN102165104 A CN 102165104A
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copper foil
adhesion amount
surface treatment
untreated
alloy
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CN102165104B (zh
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藤泽哲
铃木裕二
宇野岳夫
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Furukawa Electric Co Ltd
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    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

为了提供同时满足铜箔与聚酰亚胺的粘接强度、耐酸性、蚀刻特性的表面处理铜箔和使用该表面处理铜箔的层叠电路基板，本发明采用在未处理铜箔的至少一面附着Ni-Zn合金而成的表面处理铜箔，Zn含有率(重量％)＝Zn附着量/(Ni附着量+Zn附着量)×100为6％以上15％以下，且Zn附着量在0.08mg/dm2以上；或者是将在未处理铜箔的至少一面附着Ni-Zn合金而成的表面处理铜箔与聚酰亚胺膜粘合而得的CCL，该CCL采用附着于所述铜箔表面的Ni-Zn合金中的Zn含有率(重量％)＝Zn附着量/(Ni附着量+Zn附着量)×100为6％以上15％以下且Zn附着量在0.08mg/dm2以上的表面处理铜箔。

Description

表面处理铜箔及镀铜层压板
技术领域
本发明涉及表面处理铜箔，特别是涉及适合作为与聚酰亚胺膜高温粘接来使用的镀铜层压板(以下也称CCL)(CCL，copper clad laminate)用的表面处理铜箔以及使用该铜箔的可形成正确的电路的CCL。
背景技术
对于CCL用铜箔，使该铜箔与树脂基板接合时必须提高其接合强度，且需要满足作为印刷布线板所需的电特性、蚀刻特性、耐热性、耐化学性。因此，采用了下述工艺等各种办法：对制箔后的铜箔(以下也称未处理铜箔)与树脂基板接合的接合表面实施粗糙化处理，再在实施了该粗糙化处理的表面上施以锌(Zn)镀层或镍(Ni)镀层等，进一步在施以该Zn镀层或Ni镀层等后的表面上实施铬酸盐处理等。
最近，驱动作为电脑、手机或PDA的显示部的液晶显示器的IC安装基板不断地高密度化，其制造过程中要求正确的电路结构和高温下的处理。
为了满足该要求，作为用于制造印刷布线板的CCL，为满足正确的电路结构和高温下的处理的要求，提供有将形成正确的导电电路的电解铜箔和作为可在高温下使用的树脂基板的聚酰亚胺膜粘接而得的CCL，该CCL中铜箔与聚酰亚胺膜在数百度的高温下热粘接。
对于该高温下的粘接处理，对铜箔而言，高温下的与聚酰亚胺膜的粘接强度的提高成为课题。作为解决该课题的方法，例如专利文献1中揭示了用含Zn合金对未处理铜箔表面进行粗糙化处理的技术。
此外，作为将铜箔与聚酰亚胺膜高温粘接的方法，提出了对与聚酰亚胺膜粘接的未处理铜箔的表面用包含钼、铁、钴、镍、钨中的至少1种的电解液进行表面处理并进一步在该镀层上设置Ni镀层或Zn镀层或者Ni镀层+Zn镀层而得的表面处理铜箔(参照专利文献2)。
所述专利文献1和2中记载的含Zn层的粗糙化处理层在使铜箔与聚酰亚胺膜(树脂基板)之间的高温下的粘接强度提高方面具有效果。但是，如果在将铜箔粘接于聚酰亚胺膜(树脂基板)后通过采用酸溶液的蚀刻处理形成布线电路而构成电路基板，则由于锌易溶于酸，粘接铜箔和聚酰亚胺膜(树脂基板)的Zn层也发生溶出，电路形成后的铜箔与聚酰亚胺膜(树脂基板)的粘接强度极度下降，可能会发生使用电路基板时布线电路(铜箔)从聚酰亚胺膜(树脂基板)剥离的事故。为了防止这样的事故，必须缩短蚀刻时间来使Zn层的溶解流出保持在最低限度，蚀刻处理需要高级的技术和管理体系，存在使电路基板的生产性下降和导致成本升高的缺点。
如上所述，所述专利文献1、2中揭示的粗糙化处理无法同时满足与聚酰亚胺膜的粘接强度、耐化学性、蚀刻特性，目前没有满足这些特性的表面处理铜箔提供。
此外，没有同时满足粘接强度、耐化学性、蚀刻特性的CCL提供。
此外，专利文献3中，作为铜箔的表面处理，使用焦磷酸浴为镀浴实施Ni-Zn合金镀敷，提出了由该表面处理铜箔和聚酰亚胺膜形成的CCL，揭示了通过使用焦磷酸浴可获得膜厚均匀性良好的Ni-Zn合金层，对电路形成后的端子部进行镀锡时不易发生锡渗透至电路与聚酰亚胺树脂基材的界面的现象。
然而，使用焦磷酸浴的镀敷中，已知P共析至镀膜中，具有镀膜的溶解性因共析的P而提高的性质。对于该性质，如果蚀刻铜箔形成电路并对所形成的该电路的端子部进行镀锡，则无法充分防止锡镀液的渗透现象(耐化学性的劣化)，表面处理层因锡镀液而劣化，存在对布线电路的密合性产生影响的不利情况。
近年来，电路不断地密间距化，布线电路宽度变窄，电路和树脂基材的接合面积减少。如果在这样的密间距的电路中发生锡镀液的渗透现象，则电路的密合性下降，产生可靠性的问题，因此需要可抑制该锡镀液的渗透现象的铜箔。
专利文献1：日本专利特开2000-269637号公报
专利文献2：日本专利特开平11-256389号公报
专利文献3：日本专利特开2005-344174号公报
发明的概要
鉴于所述情况，本发明的目的在于提供同时满足与聚酰亚胺膜的粘接强度、耐化学性、蚀刻特性的表面处理铜箔和使用该表面处理铜箔的CCL。
本发明人对Ni-Zn合金镀层的溶解性进行了认真研究，结果获得了在密间距的电路中电路的密合性也不易下降、可靠性良好的铜箔。
本发明的表面处理铜箔是在未处理铜箔的至少一面附着Ni-Zn合金而成的表面处理铜箔，Zn含有率(重量％)＝Zn附着量/(Ni附着量+Zn附着量)×100为6％以上15％以下，且Zn附着量在0.08mg/dm2以上。
所述表面处理铜箔中，较好是附着于未处理铜箔的至少一面的Ni-Zn合金的Ni附着量为0.45～3mg/dm2。
本发明的镀铜层压板是将表面处理铜箔与聚酰亚胺膜粘合而得的镀铜层压板，所述表面处理铜箔是在未处理铜箔的至少一面附着Ni-Zn合金而成的表面处理铜箔，Zn含有率(重量％)＝Zn附着量/(Ni附着量+Zn附着量)×100为6％以上15％以下，且Zn附着量在0.08mg/dm2以上，该镀铜层压板的粘合面的初始剥离强度在0.6kN/m以上，在大气中于150℃加热168小时后的剥离强度为初始剥离强度的90％以上的强度。
本发明可以提供同时满足与聚酰亚胺膜的粘接强度、耐化学性、蚀刻特性的表面处理铜箔。
此外，本发明可以使用本发明的表面处理铜箔而提供同时满足粘接强度、耐化学性、蚀刻特性的层叠电路基板(CCL)。
实施发明的方式
本发明中，未处理铜箔可以是电解铜箔和压延铜箔中的任一种，不需要特别对它们进行区分时，也简单地表述为铜箔或未处理铜箔。未处理铜箔的厚度较好是5μm～35μm。这是因为如果铜箔的厚度小于5μm，则制造时产生例如皱纹等，薄铜箔的制造成本高，不实用。
还因为箔厚大于35μm时，超出驱动作为电脑、手机或PDA的显示部的液晶显示器的IC安装基板等薄型·小型化的规格。
本发明中的未处理铜箔表面的表面粗糙度较好是Rz为0.1μm～1.0μm，Ra为0.15μm以下。
此外，为了提高剥离强度、耐化学性，进行粗糙化处理是有效的。但是，若考虑到弯曲性等，较好是Rz在1.5μm以下的粗糙化。
本发明中，对上述未处理铜箔表面或未处理铜箔表面实施粗糙化而得的粗糙化处理铜箔的表面实施以Ni-Zn的二元合金层为主体的表面处理。
对铜箔表面实施以Ni-Zn的二元合金层为主体的表面处理的理由如下。使Ni-Zn表面处理层含有Ni的原因是为了防止铜从铜箔扩散至表面处理层，其Ni的附着量较好是0.45mg/dm2～3mg/dm2。Ni的附着量在3mg/dm2以上时，如果进行蚀刻加工而完全除去残渣，则处理时间延长，因而可能会产生电路梯形化的问题，因此不理想。另一方面，Ni附着量在0.45mg/dm2以下时，铜容易从铜箔扩散，大气加热后的剥离强度无法维持在初始剥离强度的90％以上，所以不理想。若考虑到蚀刻、剥离强度等，Ni附着量更好是0.5mg/dm2～2.0mg/dm2，进一步更好是0.5mg/dm2～1.5mg/dm2。
使实施于铜箔表面的表面处理层含有Zn的原因是为了提高与树脂基板(特别是聚酰亚胺膜)的粘接强度并防止粘接时的热量导致的粘接强度劣化。
Zn的附着量在0.08mg/dm2以上，且Zn的附着比例(Zn的含有率)相对于(Ni附着量+Zn附着量)为6％以上且低于15％(重量％，下同)，较好是7％以上且低于12％，更好是8％以上且低于10％。
使Zn的附着量在0.08mg/dm2以上且附着比例为6％以上且低于15％的原因是因为附着比例在6％以上时耐热性显著得到改善，但如果附着比例达到15％以上，则耐化学性变差。
进行上述表面处理后，在其表面施以Cr金属、Cr水合物或氧化物或者有机被膜。对于Cr的附着量，较好是0.01mg/dm2以上0.3mg/dm2以下。如果Cr附着量多，则蚀刻变得困难，因此不理想。此外，如果Cr附着量少，则在防锈方面产生问题，因此0.01mg/dm2以下时不理想。此外，作为有机被膜，施以市售的硅烷偶联剂等而形成被膜。
〔实施方式1〕(实施例1～9、比较例1～5)
将厚度为12μm、表面粗糙度为Rz：1.0的古河电路铜箔株式会社(FURUKAWA CIRCUIT FOLL CO.)制的WZ铜箔作为未处理铜箔。
对于该未处理铜箔按照下述步骤进行表面处理，获得达到表1所示的金属含有率和金属附着量的表面处理铜箔。
1.Ni-Zn合金镀敷
以下述的镀浴和镀敷条件对所述未处理铜箔表面实施Ni-Zn合金镀敷。
(镀浴和镀敷条件)
硫酸镍：镍浓度为0.1g/L～200g/L，较好是20g/L～60g/L
硫酸锌：锌浓度为0.01g/L～100g/L，较好是0.05g/L～5.0g/L
硫酸铵：0.1～100g/L，较好是0.5～40g/L
液温20～60℃
pH2～7
电流密度0.3～10A/dm2
2.表面处理
Ni-Zn合金镀敷处理后，在该合金层表面施以Cr处理层、硅烷偶联处理层而制成试验片。
作为Cr处理，使用铬酸酐，将该铬酸酐制成0.1g/L～100g/L的铬酸浴，以液温20～50℃、电流密度0.1～20A/dm2的条件进行处理。
作为硅烷偶联处理，使用γ-氨基丙基三甲氧基硅烷制成0.1g/L～10g/L的浴，以20～50℃的液温通过浸渍或喷涂等方法进行处理。
对于制成的表面处理铜箔，进行了下述的测定。测定结果示于表1。
表1
Figure BPA00001330099300051
初始剥离强度(单位：kN/m)
×：低于0.6，△：0.6以上且低于0.7，○：0.7以上且低于0.8，◎：0.8以上。
耐热性试验后的剥离强度(单位：kN/m)
×：低于0.54，△：0.54以上且低于0.63，○：0.63以上且低于0.72，◎：0.72以上。
耐化学性试验后的剥离强度(单位：kN/m)
×：低于0.6，△：0.6以上且低于0.7，○：0.7以上且低于0.8，◎：0.8以上。
蚀刻特性(单位：μm)
◎：低于4.0，○：4.0以上且低于5.0，△：5.0以上且低于6.0，×：6.0以上。
金属附着量
通过荧光X射线(株式会社理学(Rigaku Co.)制ZSX Primus，分析直径：35Φ)分析。
(2)初始剥离强度
将经表面处理的试验片(铜箔)与聚酰亚胺树脂(宇部兴产株式会社(Ube industries，ltd.)制UPILEX 25VT)以330℃、20kg/cm2、15分钟的条件粘接。粘接后，测定了剥离强度。对于初始剥离强度，0.6kN/m以上视为合格，其判定标准示于表1。
(3)耐热性(热处理后的剥离强度)
将与聚酰亚胺粘接后的试验片在150℃进行168小时的加热处理后，测定其剥离强度。热处理后的剥离强度的判定标准为将初始剥离强度的90％以上视为合格。还有，判定标准(计算方法)示于表1。
(4)耐化学性(酸处理后的剥离强度)
将与聚酰亚胺粘接后的试验片在常温下于水∶盐酸＝1∶1的盐酸溶液浸渍1小时，测定这之后的剥离强度。
(5)蚀刻特性
将与聚酰亚胺粘接后的试验片通过氯化铜溶液制成1mm宽的电路，通过SEM测定底宽和顶宽，求出它们的差。判定标准示于表1。
表1所示的判定标准在各评价中分别为◎：更优选、○：优选、△：基准值范围内、×：基准值范围外。
如表1所示，实施例1～2中，Ni附着量为0.90～1.30mg/dm2(在更优选的0.5～1.5mg/dm2的范围内)，Zn含有率为9％(在更优选的8～10％的范围内)，各评价项目均在更优选的范围内(综合评价◎)。
实施例3中，Zn附着比例为9％，Ni附着量为1.7mg/dm2，Ni的附着量在比作为更优选的范围的1.5mg/dm2更多的优选范围内。因此，蚀刻特性在优选的范围内，作为整体在优选的范围内(综合评价○)。
实施例4中，Zn附着比例为9％，Ni附着量为2.1mg/dm2，Ni的附着量比作为优选范围的2mg/dm2更多。因此，蚀刻特性为△，但作为整体在基准值范围内(综合评价△)。
实施例5中，Zn附着比例为6％(范围内)，耐热性为△，但作为整体在基准值范围内(综合评价△)。
实施例6中，Zn附着比例为7％，耐热性在优选的范围内，作为整体在优选的范围内(综合评价○)。
实施例7中，Zn附着比例为优选范围内的11％，耐化学性在优选的范围内，作为整体在优选的范围内(综合评价○)。
实施例8中，Zn附着比例为13％，耐化学性为△，但作为整体在基准值范围内(综合评价△)。
实施例9中，Zn附着量为0.08mg/dm2，附着比例为14％，Ni为0.48mg/dm2，所以虽然耐热性、耐化学性都为△，但作为整体在基准值范围内(综合评价△)。
比较例1中，虽然Zn附着比例为9％，但Ni附着量为3.1mg/dm2，Ni的附着量多(范围外)，因此蚀刻特性差，难以制成精细电路(综合评价×)。
比较例2中，虽然Zn附着比例在0.08mg/dm2以上，但附着比例低于6％，因此耐热性在基准值范围外(综合评价×)。
比较例3中，虽然Zn附着比例为9％，但附着比例为0.07mg/dm2，低于0.08mg/dm2，因此耐热性在基准值范围外(综合评价×)。
比较例4中，虽然Zn附着比例为0.13mg/dm2，在0.08mg/dm2以上，但附着比例高至16％，因此耐化学性在基准值范围外(综合评价×)。
比较例5中，Z附着量为0.08mg/dm2，附着比例高达17％，因此蚀刻特性在基准值范围外，且Ni为0.40mg/dm2，耐热性也在基准值范围外(综合评价×)。
如上所述，本发明的表面处理铜箔是满足与聚酰亚胺的粘接强度、耐酸性、蚀刻特性的在工业上优良的表面处理铜箔。
此外，如果采用本发明的铜箔的表面处理方法，则可以提供在工业上满足与聚酰亚胺的粘接强度、耐酸性、蚀刻特性的铜箔的表面处理方法。
另外，如果采用本发明的层叠电路基板，则可以提供树脂基板、特别是聚酰亚胺与铜箔的粘接强度强且形成电路时具有耐酸性并且满足蚀刻特性的层叠电路基板，具有良好的效果。

Claims (3)

1.一种表面处理铜箔，它是在未处理铜箔的至少一面附着Ni-Zn合金而成的表面处理铜箔，其特征在于，Zn含有率(重量％)＝Zn附着量/(Ni附着量+Zn附着量)×100为6％以上15％以下，且Zn附着量在0.08mg/dm2以上。
2.如权利要求1所述的表面处理铜箔，其特征在于，附着于所述未处理铜箔的至少一面的Ni-Zn合金的Ni附着量为0.45～3mg/dm2。
3.一种镀铜层压板，它是将表面处理铜箔与聚酰亚胺膜粘合而得的镀铜层压板，其特征在于，所述表面处理铜箔是在未处理铜箔的至少一面附着Ni-Zn合金而成的表面处理铜箔，Zn含有率(重量％)＝Zn附着量/(Ni附着量+Zn附着量)×100为6％以上15％以下，且Zn附着量在0.08mg/dm2以上，粘合面的初始剥离强度在0.6kN/m以上，在大气中于150℃加热168小时后的剥离强度为初始剥离强度的90％以上的强度。
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TWI262041B (en) * 2003-11-14 2006-09-11 Hitachi Chemical Co Ltd Formation method of metal layer on resin layer, printed wiring board, and production method thereof
JP4570070B2 (ja) * 2004-03-16 2010-10-27 三井金属鉱業株式会社 絶縁層形成用の樹脂層を備えたキャリア箔付電解銅箔、銅張積層板、プリント配線板、多層銅張積層板の製造方法及びプリント配線板の製造方法
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CN104822525B (zh) * 2012-11-30 2017-08-11 Jx日矿日石金属株式会社 附载体铜箔
CN103501580A (zh) * 2013-10-09 2014-01-08 北京科技大学 一种表面处理铜箔及其制备方法
CN105323958A (zh) * 2014-05-28 2016-02-10 Jx日矿日石金属株式会社 表面处理铜箔、附载体铜箔、积层体、印刷配线板、电子机器、表面处理铜箔的制造方法及印刷配线板的制造方法
CN105323958B (zh) * 2014-05-28 2018-04-20 Jx日矿日石金属株式会社 表面处理铜箔、附载体铜箔、积层体、印刷配线板、电子机器、表面处理铜箔的制造方法及印刷配线板的制造方法
TWI806296B (zh) * 2020-12-23 2023-06-21 日商Ｊｘ金屬股份有限公司 表面處理銅箔、覆銅積層板及印刷配線板

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EP2312022A1 (en) 2011-04-20
WO2010010893A1 (ja) 2010-01-28
TWI468559B (zh) 2015-01-11
US8512873B2 (en) 2013-08-20
JPWO2010010893A1 (ja) 2012-01-05
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