CN1064414C - 印刷电路板用电解铜箔及其制造方法 - Google Patents
印刷电路板用电解铜箔及其制造方法 Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000011889 copper foil Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims description 37
- 238000005498 polishing Methods 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims description 60
- 239000010949 copper Substances 0.000 claims description 60
- 238000012545 processing Methods 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 208000003351 Melanosis Diseases 0.000 claims description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims 2
- 238000010168 coupling process Methods 0.000 claims 2
- 238000005859 coupling reaction Methods 0.000 claims 2
- 229910000077 silane Inorganic materials 0.000 claims 2
- 230000008021 deposition Effects 0.000 claims 1
- 230000003746 surface roughness Effects 0.000 abstract description 16
- 238000009413 insulation Methods 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 13
- 238000001000 micrograph Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 239000011152 fibreglass Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 239000002659 electrodeposit Substances 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 7
- 238000009713 electroplating Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000002788 crimping Methods 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 210000000498 stratum granulosum Anatomy 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明为一种在形成电路图形时腐蚀特性及高频特性优越、绝缘可靠性优越、适合于超细电路图形用途的电解铜箔,其特征为:电解铜箔在进行瘤化处理之前的粗糙面表面粗糙度在1.5μm以下,在该粗糙面上进行瘤化处理后,表面粗糙度为1.5~2.0μm。本发明还提供了一种印刷电路板用的电解铜箔的制造方法,其特征为:电解铜箔的粗糙面利用抛光轮研磨、作瘤化处理之前,表面粗糙度在1.5以下,经过在该粗糙面上进行瘤化处理后,表面粗糙度为1.5~2.0μm。
Description
本发明涉及印刷电路板所用的电解铜箔及其制造方法,更详细地说,是涉及通过抛光研磨加工、使电解铜箔的粗糙面上具有微细颗粒状铜的电沉积物的高密度层,从而制成电路图形腐蚀特性优良、高频率特性及绝缘可靠性优良、适用于超细电路图形用途的电解铜箔。
一般情况下,印刷电路板所用的电解铜箔是用铜电解液经过电解在电化学的阴极鼓面上形成的电沉积铜剥离后制成的,称作电解析离箔。采用这样的方法制成的电解析离箔的电解析出开始面(光泽面)比较平滑,而电解析出终了面(粗糙面)一般都有凹凸。用作印刷电路板用的覆铜层压板是在该电解析离箔的粗糙面侧上形成颗粒状的电沉积物(瘤化处理),然后将其处理面粘接在环氧树脂基的玻璃钢或聚酰亚胺等一类的树脂基材上制成的。印刷电路板就是将这种覆铜层压板经过腐蚀制成的。
可是,在近年来印刷电路板的超细电路图形的用途中,由于铜箔粗糙面侧的凹凸与电路图形相比相对地变大了,电路之间和层间的绝缘可靠性受到了不良的影响,这就是问题的所在。
为了对此加以改善,最近在使用电解析离的粗糙面的粗糙度低的超低粗糙度箔(VLP)。按照JIS B 0601的规定,18μm厚的普通电解析离箔粗糙面侧的粗糙度为5~8μm,如为VLP,则在3~5μm。不论是粗糙面还是光滑面(平滑面)要在转鼓面上进行转印,都不会受析离箔品种的限制,光泽面的表面粗糙度在1.5~2.0μm之间。
然而,由于就连VLP的表面粗糙度也存在比较低的、所谓的凹凸,在进行瘤化处理的时候,铜瘤会集中在波峰的顶端,待形成电路图形之后,残留的铜被埋入基材之中,要想将其除去,就必须将余下的部分再进行一次腐蚀,这就成了问题。另外,由于腐蚀会有过度,不得不使电路图形的宽度要比规定的细一些,这也成了问题。
另外,有人还发表过对电解析离箔的平滑表面进行瘤化处理,并使用将该表面粘接在基材上制成的覆铜层压板上形成细电路的方法(日本专利公报特开平6-270331)。
然而在该特开平6-270331所发表的方法中、在平滑面上进行瘤化处理的时候,平滑面的铜粒并不生成均匀的电沉积。经过瘤化处理之后的低粗糙度Rz在2.0~2.2之间。由于在局部部位会形成较大的颗粒,所以难以在更为超细的电路图形的用途中使用。
除此之外,还有人发表过将电解析离箔经过延压加工,使其粗糙面的形状达到完全消失的程度之后再进行瘤化处理的方法(特公昭62-42022),还发表过将该粗糙面进行研磨加工、切削加工、放电加工、甚至电解研磨加工等处理之后,再进行瘤化处理的方法(特开昭-59-145800)。
然而,在上述现有技术那样的瘤化处理方法中,由于不论在什么情况下铜箔的凹凸形状都会有部分残留,所以难以均匀进行微细瘤化处理,不能避免局部产生电沉积,由于难以将粗糙面侧表面所有的粗糙度减低到某种程度以下,所以制造不出具备形成电路图形的优良腐蚀特性和高频特性的、适用于高绝缘可靠性的超细电路图形用途的电解铜箔。
本发明就是要解决现有技术中的问题,提供在保持基材之间的结合力的同时制成具备形成电路图形的优良腐蚀特性和高频特性的、适用于高绝缘可靠性的超细电路图形用途的电解铜箔及其制造方法。
发明人经过着重对上述现有技术中的问题进行精心的研究的结果,通过对电解铜箔的粗糙面进行研磨加工,使原有粗糙面完全消失、形成新的微细凹凸面,其表面粗糙度在1.5μm以下,在该粗糙面上形成均一的上述的铜的沉积物(瘤化处理),其表面粗糙度为1.5~2.0μm的电解铜箔,从而解决了现有技术中的问题,制造出在保持基材之间的结合力的同时具备形成电路图形的优良腐蚀特性和高频特性的、适用于高绝缘可靠性的超细电路图形用途的电解铜箔,是完成本发明的产物。
这就是说,本发明的电解铜箔的其特征为:其原有粗糙面完全消失、形成新的微细凹凸研磨面,该电解铜箔在未做瘤化处理前的表面粗糙度在1.5μm以下,该粗糙面经过上述瘤化处理后的表面粗糙度为1.5~2.0μm。
图1为进行物理研磨前电解铜箔(18μm)的断面显微镜照片。
图2为电解铜箔(18μm)的粗糙面经过用1000#氧化铝抛光轮进行物理研磨后的断面显微镜照片。
图3是在实施例1中形成粒状铜层之后的电解铜箔的表面显微镜照片。
图4是电路图形部分的横向断面的倒立型显微镜照片。
图5是用于计算铜粒平均值及标准偏差的模式图。
图6是用于计算腐蚀系数Ef的模式图。
图7为在实施例1中制成的电解铜箔的处理面的电子显微镜照片。
图8为用于计算电路的直线性程度的模式图。
图9是在比较例1中形成粒状铜层后的电解铜箔的表面显微镜照片。
图10是在比较例1中制成的电解铜箔的处理面的电子显微镜照片。
图11是比较例2中形成粒状铜层后的电解铜箔的表面显微镜照片。
图12为比较例2中制成的电解铜箔的处理面的电子显微镜照片。
以下对本发明作详细说明。
本发明所用的铜箔可以是粗糙面的粗糙度大的普通铜箔;或者是粗糙度低的铜箔(VLP)等任何一种。以下就使用VLP铜箔的进行说明
本发明的印刷线路板所用的电解铜箔的粗糙面侧(电解析出终了面)的表面粗糙度如果在1.5μm以下,经过抛光研磨处理,该粗糙面经过瘤化处理后的表面粗糙度为1.5~2.0μm。
电解铜箔的粗糙面的表面粗糙度如果在1.5μm以上,在该粗糙面侧上形成粒子状铜的电沉积物(瘤化处理)的时候,铜的电沉积物容易在凹凸的波峰顶端集中,不很理想。
如果在该粗糙面上形成铜的电沉积物之后的表面粗糙度在1.5μm以下,形成印刷线路板的电路图形之后的剥离强度不太好。另外,如果表面粗糙度在2.0μm以上,有的部分生成大的处理粒子,会有损于腐蚀特性、高频特性及绝缘可靠性。
可是,在本发明的瘤化处理时,由于电解铜箔的基材粘接面之间产生固定效应,所以在电解液中该铜箔的粗糙面侧会形成均匀的粒子状的铜的电沉积物。
以下对本发明的印刷电路板用的电解铜箔的制造方法作详细说明。
本发明的电解铜箔的制造方法的特征是:电解铜箔的粗糙面经过研磨处理,原有粗糙面完全消失、形成新的微细凹凸研磨面,在未做瘤化处理前的表面粗糙度在1.5μm以下,该粗糙面经过上述瘤化处理后的表面粗糙度为1.5~2.0μm。
在本发明的电解铜箔制造方法中,首先对电解析离箔进行研磨处理,使其通过导向轮,粗糙面由于承受抛光轮的压力,使该粗糙面原来的形状完全消失,同时形成新的微细凹凸,表面粗糙度Rz在1.5μm以下。在此过程中,抛光轮的转速最好是在100~1000rpm之间。抛光轮的转速如果在100rpm以下,表面的粗糙的会变的不均匀,反之,如果在1000rpm以上,抛光轮的旋转不稳定,不论在什么情况下都难以制成表面粗糙度在1.5μm以下的电解铜箔。
还有,抛光轮的压力最好是在0.5~3.0kgf/cm2,更好是在1.0~2.0kgf/cm2。抛光轮的压力如果在0.5kgf/cm2以下,由于压力太小,达不到在预计的表面粗糙度以下的程度。反之,如果在3.0kgf/cm2以上,由于压力太强,对铜箔的物理影响太大,有时会使铜箔断裂。
另外,抛光轮研磨的线速度最好是在2~4m/分的条件下进行。如果超出这个范围以外,会使研磨不均匀,难以得到1.5μm以下的电解铜箔。
虽然不对该研磨所用的研磨剂的种类作具体规定,但是其颗粒范围最好在5~50μm。例如,采用氧化铝作研磨剂附着在1000号的抛光轮上的研磨效果就很优良。采用这种抛光轮研磨,研磨后的表面粗糙度在Rz1.5μm以下。采用这种抛光轮研磨,可以消除由于电解在铜箔的粗糙面上的凹凸(完全消除原来的形状),生成新的非常微细的告密度凹凸,使表面粗糙度达到规定以下。
再说,在对经过这样的1.5μm以下的研磨所得的粗糙面进行瘤化处理,一般在处理过程中,会在凹凸的顶端部位进行瘤状铜粒的电沉积。由于是在铜箔面上进行非常微细的凹凸处理,按单位面积计算,有利于在顶端部位产生均匀的电沉积,使铜粒的电沉积密度很高。在进行这样的瘤化处理时,要在待进行抛光轮研磨的粗糙面上配置不溶性的电极对铜电解液的电解。这样的瘤化处理要连续在黑化电镀、覆层电镀和后续电镀的一连串过程中进行。该一连串的电镀处理按下列的电解条件进行。
(1)黑化电镀
经过瘤化处理之后,在电解铜箔的粗糙面上配置不溶性电极,按以下电解条件进行。
铜浓度:5~30g/L
硫酸浓度:50~150g/L
液温:20~30℃
电流密度:20~40A/dm2
时间:5~15秒
采用这样的电解条件进行所谓的黑化电镀,在电解铜箔的粗糙面上形成粒子状的铜沉积层。
(2)覆层电镀
然后,在经过这样的黑化电镀处理的表面上,再按照以下的电解条件进行覆层电镀。
铜浓度:40~80g/L
硫酸浓度:50~150g/L
液温:45~55℃
电流密度:20~40A/dm2
时间:5~15秒
采用这样的电解条件进行所谓的覆层电镀,在上述粒子状的铜沉积层上形成铜的被覆层。
(3)胡须电镀
然后,在经过这样的黑化电镀处理的表面上按照以下的电解条件进行胡须电镀。
铜浓度:5~30g/L
硫酸浓度:30~60g/L
液温:20~30℃
电流密度:10~40A/dm2
时间:5~15秒
采用这样的电解条件进行所谓的胡须电镀,在上述铜的被覆层上形成胡须状的铜。
经过这样瘤化处理的铜箔粗糙表面上的粗糙度为Rz1.5~2.0μm。如果表面粗糙度在1.5以下,就不能预期当形成在基板上沾接的电路时会有足够的剥离强度。另外,如果表面粗糙度在2.0μm以上,就会在部分表面上形成大的处理瘤,从而会有损于腐蚀特性、高频特性以及绝缘可靠性。
要在经过以上的粗糙面上的瘤化处理的电解铜箔上继续进行防锈处理。在相应的技术领域中一般使用的处理方法对于该防锈处理的条件都可以适用。
该防锈处理按以下所示,在进行过瘤化处理的铜箔表面上进行镀锌处理之后,进行铬酸处理,然后再进行硅烷耦合剂处理。
首先进行锌处理,锌浓度:5g/L、硫酸浓度:50g/L、液温:25℃、电流密度:5A/dm2、时间:8秒,进行镀锌。
然后再在经过锌处理的表面上使用铬酸酐2g/L、硫酸浓度:50g/L、液温:25℃、pH4的电解溶液,以电流密度:5A/dm2、时间:8秒、电解铬酸盐处理。
最后,在经过这样的铬酸盐处理的表面上利用γ-缩水甘油丙基三甲氧基硅烷的硅烷耦合剂进行涂布。
将经过这样的处理制成的电解铜箔的研磨面进行加热,采用众所周知的方法,热压在环氧树脂基的玻璃钢或聚酰亚胺一类的树脂基板的一个面上,制成覆铜层压板。
然后,将经过这样制成的覆铜层压板采用众多周知的方法进行干膜层压,利用规定的线路宽度及电路间隔的图形膜,经过紫外线曝光,形成电路图形。经过这样形成的电路图形的腐蚀是用市售的氯化铜腐蚀液、采用众所周知的方法进行腐蚀,制成所希望的有电路图形的印刷电路板。
本发明的电解铜箔的粗糙面经过抛光研磨,使其原有粗糙面完全消失,将形成的新的微细凹凸的表面粗糙度控制在1.5μm以下,再对电解铜箔的粗糙面上的微细均匀颗粒状的铜的电沉积物进行高密度瘤化处理,从而能够在保持基材之间的粘合力不变的同时,能以制造出绝缘可靠性高的超细电路图形用途的电解铜箔。此外,在本发明中,由于电解铜箔的两面的粗糙度都低,所以能以制造在形成超细图形的印刷电路板的时候使其层间绝缘可靠性高、而且高频特性优良的超细电路图形的用途中使用的电解铜箔。
以下根据实施例及比较例对本发明再做具体说明。实施例1
将光泽面粗糙度(Rz)为1.60μm、粗糙面粗糙度(Rz)为2.50,厚度为18μm的电解铜箔用1000号的氧化铝抛光轮(角田电刷厂制)以转速200rpm、压力1.0kgf/cm2、线速度3m/分的条件进行研磨。研磨后粗糙面的粗糙度(Rz)为1.5μm。研磨前的电解铜箔(18μm)的显微镜断面照片(1000倍)以及研磨后该粗糙面的显微镜断面照片(1000倍)分别如图1及图2所示。由显微镜照片所示可见,研磨后的粗糙面的原来的形状完全消失,形成新的高密度的微细凹凸。
然后,采用铜浓度为12g/L、硫酸浓度为100g/L、液温为25℃的电解溶液,在电流密度为30A/dm2的条件下、采用在经过抛光轮研磨的一面配置不溶性电极的方式进行10秒的黑化电镀处理。然后,采用铜浓度为60g/L、硫酸浓度为100g/L、液温为50℃的电解溶液,在电流密度为30A/dm2的条件下、进行10秒的覆层电镀处理。
然后,采用铜浓度为12g/L、硫酸浓度为45g/L、液温为25℃的电解溶液,在电流密度为10A/dm2的条件下、进行胡须电镀处理,形成颗粒状的铜层。经过瘤化处理后,粗糙面的粗糙度(Rz)为1.89μm。经过这样的瘤化处理后,电解铜箔的表面显微照片如图3所示。由图3的显微照片可见,沿着粗糙处理面的微细凹凸的粒状铜瘤是电沉积物。
然后,在经过瘤化处理的电解铜箔的粗糙面上进行以下所示的防锈处理。
首先,采用锌浓度为5g/L、硫酸浓度为50g/L、液温为25℃的电解溶液,在电流密度为5A/dm2的条件下、进行8秒的镀锌处理。再采用铬酸酐浓度为2g/L、pH4的电解溶液,在电流密度为1A/dm2的条件下、进行5秒的电解铬酸盐处理,用流水洗净,温风干燥。
将经过这样处理过的电解铜箔置于环氧树脂基的玻璃钢树脂基板(FR-4)的一个面上,在研磨面的一边加热压紧,做成覆铜层压板。
以后,将这样制成的覆铜层压板加干膜(日合α公司制)层叠,利用规定的线路宽度及电路间隔的图形膜,经过紫外线曝光,形成电路图形。经过这样形成的电路图形的腐蚀,是用市售的氯化铜腐蚀液,于液温50℃进行30秒的腐蚀,制成所希望的有电路图形的印刷电路板。
接着,对于该印刷电路板进行以下的评价试验。
(1)在环氧树脂基玻璃钢基板中埋入的铜粒粒度试验
用一块印刷电路板作为埋入用的冷态埋入树脂,放置一昼夜,使其完全硬化,然后沿电路的横向形成端面,用倒立显微镜拍摄1500倍的照片(图4)。
以后按图5所示划一直线,按等间距取15个测定点,测定从直线到铜粒的距离,算出平均值及标准偏差。由于该标准偏差是表示铜粒粒度的标准离差的评价指针,如果该标准偏差小,则表示标准偏差小。
求出的平均值为0.48;标准偏差为0.43。
(2)腐蚀系数
腐蚀系数取(1)中的同断面的树脂块,拍摄600倍的光学显微照片,从该照片按以下所述进行计算。即,按图6所示,以W1、W2分别表示印刷电路板的上底和下底,以T表示铜箔厚度,用下式求出腐蚀系数Ef。
Ef=2T/(W2-W1)
图中的电路断面接近于四边形的样子,也就是说是锐角的样子。说明腐蚀系数大。由式中算出的腐蚀系数是在六个取树脂块上的六个点的平均值,为3.69。
(3)电路图形的直线性
采用实施例1中制成的电解铜箔,将其粗糙面压接粘合在环氧树脂基的玻璃钢基材上,制成50-100μm的电路。将该电路放在电子显微镜的式样台上,用电解放射型电子显微镜(日立制造所制,S-4100)拍成600倍的显微镜照片(图7)。由于本发明制成的电解铜箔两面的粗糙度都低,电路的直线性良好。虽然与这样的腐蚀系数有所不同,电路下部(底部)的凹凸情况值得注意。现根据以下的凹凸程度对腐蚀系数进行评价。
在电路下部(底部)的宽度上沿着电路的纵向绘出平行线,按等距离取15个点,测取测定点处的宽度,算出彼此之间的平均值和标准偏差。该标准偏差是表示电路下部直线性程度的指针,数值小,宽度的偏差也小,也就是说,腐蚀后的残留物是接近于直线的形状。采用本发明制成的电路宽度的标准偏差为0.67μm,直线性良好。因此,经过腐蚀后,在电路的底部残留的铜极少,从而使电路的层间绝缘性良好。
(4)抗剥强度
然后测定电路图形中的10mm的电路宽度的抗剥强度。测得的抗剥强度为1.02kgf/cm。
现将测得的结果汇总列表如表1所示。比较例1
将光泽面粗糙度(Rz)为1.60μm、粗糙面粗糙度(Rz)为4.60μm的、厚度为18μm的电解铜箔的粗糙面不经研磨处理,在实施例同样的条件下形成粒状铜层。采用这样的办法制成的粗糙面的粗糙度为5.75μm。将形成的这样的粒状层的电解铜箔的表面显微镜照片(5000倍)示于图9。由图9所示可见,在粗糙面上有不规则的电沉积粒状铜瘤。
然后,将形成这样的粒状铜瘤的电解铜箔按照与实施例相同的条件进行防锈处理。
将经过这样的表面处理的电解铜箔放在与实施例相同的环氧树脂基玻璃钢基板上,在研磨面上加热压接,制成覆铜层压板。
然后再将这样制成的覆铜层压板按照实施例同样的条件用线路宽度为50μm、电路间隔为100μm的电路图形薄膜经过紫外线曝光形成电路图形,再经腐蚀,制成印刷电路板。
针对该印刷电路板按照实施例1相同的方式进行评价试验。
在基板内埋没的铜粒粒度的平均值为2.01,标准偏差为1.67。
腐蚀系数在电路板块上六个点上的平均值为1.86。
按照实施例同样的方式,将电解铜箔粘接在环氧树脂基玻璃钢基材上,制成50-100μm的电路,拍摄成600倍的显微镜照片(图10)。由该显微照片可见,由于铜箔的粗糙面的粗糙度高,说明电路的直线性不好。
然后在按与实施例相同的方式,在电路下部(底部)的宽度上沿着电路的纵向绘出平行线,按等距离取15个点,测取测定点处的宽度,算出彼此之间的平均值。
还有,10mm的电路宽度的抗剥强度为1.51kgf/cm。
将这样测得的粗糙面的粗糙度、腐蚀系数及电路的直线性的评价试验的结果分别汇集列于表1。比较例2
将比较例1中的光泽面粗糙度(Rz)为1.60μm、粗糙面粗糙度(Rz)为2.50μm的、厚度为18μm的电解铜箔的粗糙面不经研磨处理,在实施例同样的条件下形成粒状铜层。光泽面的粗糙度为2.09μm。将形成的这样的粒状层的电解铜箔的表面显微镜照片(5000倍)示于图11。由图11所示可见,在粗糙面上有不规则的电沉积粒状铜瘤。
然后,将形成这样的粒状铜瘤的电解铜箔按照与实施例相同的条件进行防锈处理。
将经过这样的表面处理在光泽面上形成粒状铜层的电解铜箔按照与实施例相同的方式进行处理,用线路宽度为50μm、电路间隔为100μm的电路图形薄膜经过紫外线曝光形成电路图形,再经腐蚀,制成印刷电路板。
将该印刷电路板按照实施例1相同的方式进行评价试验。
在基板内埋没的铜粒粒度的平均值为0.98,标准偏差为0.81。
腐蚀系数在电路板块上六个点上的平均值为2.22。
按照实施例1样的方式,将电解铜箔粘接在环氧树脂基玻璃钢基材上,制成50-100μm的电路,拍摄成600倍的显微镜照片(图12)。由该显微照片可见,作为超细图形的用途时直线性不太好。
然后在按与实施例相同的方式,在电路下部(底部)的宽度上沿着电路的纵向绘出平行线,按等距离取15个点,测取测定点处的宽度,算出彼此之间的平均值。
还有,10mm的电路宽度的抗剥强度为1.13kgf/cm。
将这样测得的粗糙面的粗糙度、腐蚀系数及电路的直线性的评价试验的结果分别汇集列于表1。表1
注)
处理前表面粗糙度Rz(μm)的平均a) | 实施例12.50 | 比较例14.60 | 比较例2e)1.60(光泽面) | ||
研磨后表面粗糙度Rz(μm)的平均a) | 1.50 | 未研磨 | 未研磨 | ||
粒状铜层形成后表面粗糙度Rz(μm)的平均a) | 1.89 | 5.75 | 2.09 | ||
铜粒直径 | 平均(μm)b) | 0.97 | 1.62 | 1.34 | |
标准偏差(μm)b) | 0.113 | 0.49 | 0.276 | ||
铜粒埋入基材深度 | 平均(μm)c) | 0.48 | 2.01 | 0.98 | |
标准偏差(μm)c) | 0.430 | 1.67 | 0.781 | ||
电路宽度(底部) | 平均(μm)d) | 50.08 | 63.5 | 68.3 | |
标准偏差(μm)d) | 0.67 | 2.89 | 1.02 | ||
腐蚀系数 | 3.69 | 1.86 | 2.22 | ||
剥离强度 | 1.02 | 1.51 | 1.13 | ||
绝缘可靠性 | 层间绝缘性 | 非常良好 | 不好 | 不好 | |
电路间绝缘性 | 非常良好 | 不好 | 不好 |
a)所示为在计算表面粗糙度时取3个点的测定值的平均值。
b)所示为在铜箔粗糙面的显微镜照片(×5000)中随机测取10个点的铜粒直径测定值的平均值及其标准偏差。
c)所示为将环氧树脂基玻璃钢基材与铜箔的粗糙面经压床压接,在15个点处测定的铜瘤埋入深度值的平均值及其标准偏差。
d)所示为将铜箔的瘤化处理面与环氧树脂基玻璃钢基材经压床压接,制成50-100μm的电路,在电路上的15个点处的测定值的平均值。
e)比较例2中所示的数值全部为光泽面的数值。
Claims (9)
1、具有粗糙面和光滑面的电解铜箔,其中,所述粗糙面的原有形状通过抛光完全除去,重新在其上形成了具有线形条纹的微细凹凸,所述抛光后表面的表面粗糙度Rz在1.5微米以下,
此后所述抛光后表面经过瘤化处理后的表面粗糙度为1.5-2.0微米。
2、权利要求1的电解铜箔,其特征是在瘤化处理后,防锈层被淀积在所述粗糙面上。
3、权利要求2的电解铜箔,其特征是所述防锈层由镀锌层和所述镀锌层上形成的铬酸盐处理层构成。
4、权利要求3的电解铜箔,其特征是在所述铬酸盐处理层上淀积有硅烷耦合层。
5、具有粗糙面和光滑面的印刷电路板用电解铜箔的制造方法,包括以下步骤:
抛光电解铜箔的粗糙面完全除去粗糙面的原有形状,
进一步抛光粗糙面形成具有线形条纹的微细凹凸并将粗糙面的表面粗糙度Rz控制在1.5微米以下,以及
对所述抛光后粗糙面实施瘤化处理,在所述瘤化处理后将表面粗糙度Rz控制在1.5-2.0微米。
6、权利要求5的方法,其特征是所述瘤化处理由三步构成:进行黑化电镀形成瘤沉积物、接着进行覆层电镀形成被覆层、以及最后进行胡须电镀形成胡须状的铜。
7、权利要求5的方法,还包括在所述瘤化处理后淀积防锈层的步骤。
8、权利要求7的方法,其特征是所述防锈层由镀锌层和在所述镀锌层上形成的铬酸盐处理层构成。
9、权利要求8的方法,其特征是在所述铬酸盐处理层上沉积硅烷耦合层。
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JP21618/1996 | 1996-01-16 | ||
JP02161896A JP3155920B2 (ja) | 1996-01-16 | 1996-01-16 | プリント配線板用電解銅箔及びその製造方法 |
JP21618/96 | 1996-01-16 |
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US (2) | US5858517A (zh) |
EP (1) | EP0785295B1 (zh) |
JP (1) | JP3155920B2 (zh) |
KR (1) | KR100291856B1 (zh) |
CN (1) | CN1064414C (zh) |
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MY (1) | MY117454A (zh) |
TW (1) | TW410533B (zh) |
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JPH03236955A (ja) * | 1990-02-14 | 1991-10-22 | Shin Kobe Electric Mach Co Ltd | サーマルヘッド用金属箔張り積層板ならびにサーマルヘッド |
JPH04202796A (ja) * | 1990-11-30 | 1992-07-23 | K D K Kk | プリント基板用銅箔及びその製造方法 |
US5482784A (en) * | 1993-12-24 | 1996-01-09 | Mitsui Mining And Smelting Co., Ltd. | Printed circuit inner-layer copper foil and process for producing the same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104884245A (zh) * | 2012-12-21 | 2015-09-02 | Sk新技术株式会社 | 多层柔性金属包层层合板及其制造方法 |
Also Published As
Publication number | Publication date |
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EP0785295B1 (en) | 2003-07-09 |
KR970061019A (ko) | 1997-08-12 |
US5858517A (en) | 1999-01-12 |
DE69723327D1 (de) | 2003-08-14 |
JPH09195096A (ja) | 1997-07-29 |
DE69723327T2 (de) | 2004-07-22 |
CN1163318A (zh) | 1997-10-29 |
TW410533B (en) | 2000-11-01 |
US5897761A (en) | 1999-04-27 |
JP3155920B2 (ja) | 2001-04-16 |
MY117454A (en) | 2004-06-30 |
EP0785295A1 (en) | 1997-07-23 |
KR100291856B1 (ko) | 2001-06-01 |
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