CN1090686C - 铜及铜合金的微蚀刻剂 - Google Patents

铜及铜合金的微蚀刻剂 Download PDF

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CN1090686C
CN1090686C CN96110803A CN96110803A CN1090686C CN 1090686 C CN1090686 C CN 1090686C CN 96110803 A CN96110803 A CN 96110803A CN 96110803 A CN96110803 A CN 96110803A CN 1090686 C CN1090686 C CN 1090686C
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牧善朗
中川登志子
山田康史
春田孝史
有村摩纪
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
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    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/383Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching
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    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
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    • H05K2203/125Inorganic compounds, e.g. silver salt
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H05K3/02Apparatus 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
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05K3/00Apparatus or processes for manufacturing printed circuits
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    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/46Manufacturing multilayer circuits
    • H05K3/4611Manufacturing multilayer circuits by laminating two or more circuit boards

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Abstract

一种由含有二价铜离子源、酸解离常数小于5的有机酸及卤离子源的水溶液组成的铜及铜合金表面的微蚀刻剂。所述微蚀刻剂可使铜及铜合金表面形成具有凹凸较深的粗化表面,使其具有与耐焊锡膜层等的优异的粘结性,且具有合适的锡焊性。

Description

铜及铜合金的微蚀刻剂
本发明涉及一种可用于铜表面及铜合金表面处理的微蚀刻剂。
已有技术
在印刷线路板的制作中,在对铜表面进行耐蚀刻剂和耐焊锡膜的表面覆层时,为了提高粘结性能,需对铜表面进行研磨。在该研磨方法中,有如抛光研磨、擦洗研磨等的机械研磨和微蚀刻(化学研磨)等,但对具有细线条图案的基片的表面处理来说,微蚀刻(研磨)更为合适。通常,在施以微蚀刻时,可在铜表面上蚀刻约1-5μm深度。
另外,在匀焊工序之前及电子元件封装之前,为了去除铜表面的氧化膜,提高锡焊性能,也常进行微蚀刻。在上述微蚀刻中,使用通常使用以硫酸和过氧化氢为主要成分的水溶液及以过硫酸盐为主要成分的水溶液。
发明课题
可是,随着形成于印刷电路板上的电路图案的高密度化发展,所用的耐焊锡膜也正在从已往的热固化型转而使用可形成优异的细线条图案的紫外线固化型的耐焊锡涂膜。不过,由于所述的紫外线固化型耐焊锡膜比起以往的耐焊锡涂膜来,其与铜表面的粘结性能较差,在以往的微蚀刻法所得的铜表面上的粘结性能不够,在其后的电镀工序、匀焊工序、电子元件的封装过程中,会产生耐蚀(耐焊锡)覆膜的剥离和气泡等不良现象。
另一方面,在匀焊工序中,在印刷线路板上表面安装元件用的垫片增加,在以以往的微蚀刻法所得的表面上的焊接性能不理想,会产生锡焊不良现象。
本发明的目的是,提供一种微蚀刻剂,所述微蚀刻剂可使铜合金表面及铜表面形成具有较深的凹凸形状的粗糙面,使其具有与耐焊锡膜层等的优异的粘结性能,也可使该表面状态更适于焊锡性。
为达到上述目的,本发明者们经多次刻意研究,结果找到了一种由含有二价铜离子源、酸解离常数pKa为5以下的有机酸及卤离子源的水溶液组成的微蚀刻剂,从而完成了本发明。
发明的实施形态
本发明中所用的二价铜离子源是用作用于氧化金属铜等的氧化剂的铜离子源。在本发明中,由于将二价铜离子源用作氧化剂,在用于微蚀刻剂时,可使其具有合适的蚀刻速度,且可在铜表面稳定地形成具有较深的凹凸形状。作为上述二价铜离子源,可举出如有机酸的铜盐和氯化铜(二价)、溴化铜(二价)、氢氧化铜(二价)等。形成所述铜盐的有机酸并无什么特别限制,但最好是如下所述的、pKa在5以下的有机酸。也可合并使用二种以上的上述二价铜离子源。
上述二价铜离子源的含量,换算为金属铜较理想的是0.01-20%(重量,以下同),更好地是0.1-10%。如所述含量过少,则蚀刻速度变慢;另一方面,如所述含量过多,则溶解困难,会产生粉状物。
本发明中所用的pKa在5以下的有机酸,可掺用于因其二价铜离子源而氧化的铜的溶解,或掺用于pH的调节。但是,如上述有机酸的pKa超过5,则不能充分溶解氧化铜。作为pKa小于5的有机酸,可具体举例出,如甲酸、乙酸、丙酸、丁酸、戊酸、己酸等的饱和脂肪酸;如丙烯酸、巴豆酸、异巴豆酸等的不饱和脂肪酸;如草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸等的脂肪族饱和二羧酸;如马来酸等的脂肪族不饱和二羧酸;如苯甲酸、邻苯二甲酸、肉佳酸等的芳香族羧酸;如乙醇酸、乳酸、苹果酸、柠檬酸等的羟基羧酸;如氨基磺酸、β-氯丙酸、烟酸、抗坏血酸、羟基三甲基乙酸、乙酰丙酸等的带有取代基的羧酸;及其衍生物等。上述有机酸也可二种以上合并使用。
上述有机酸的含量以0.1-30%左右为理想。如该含量过少,则不能充分溶解氧化铜,残留有粉状物,不能得到稳定的蚀刻速度;而另一方面,如该含量过多,则铜的溶解稳定性降低,或在铜表面上发生再次氧化。
本发明中所用的卤离子源的掺用,是为了辅助铜的溶解,以形成具优异的粘结性能和钎焊性能的铜表面。作为所述的卤离子源,可举出氯离子、溴离子等的离子源,例如,盐酸、氢溴酸、氯化钠、氯化钾、氯化钙、氯化铵、溴化钾、氯化铜、溴化铜、氯化锌、氯化铁、溴化锡等,及其它可在溶液中解离卤离子的化合物。上述卤离子源可合并使用二种以上。另外,如氯化铜(二价)可作为即具有卤离子源,又具有二价离子源的离子源使用。
上述卤离子源最好含有0.01-20%左右的卤离子。上述含量过少及过多时,就不能得到具有优异的与树脂的粘结性及优异焊接性能的铜表面。
再者,在本发明的微蚀刻剂中,另减少在作微蚀刻处理时的pH值的变动,可添加有机酸的钠盐、钾盐及铵盐等;为了提高铜的溶解稳定性,也可添加如乙二胺、吡啶、苯胺、氨、一乙醇胺、二乙醇胺、三乙醇胺、N-甲基二乙醇胺等的配位剂;也可按需要,添加其它各种添加剂。
本发明的微蚀刻剂的使用方法并无特别限制,例如,对欲处理的铜或铜合金表面作喷雾处理、喷涂的方法,及将铜或铜合金浸渍于表面处理剂中的方法等。浸渍时,为由对铜和铜合金的蚀刻,将处理剂中生成的一价铜离子氧化为二价铜离子,可由鼓泡法鼓入空气。又,本发明的微蚀刻剂使用后,其废液处理也方便,例如,可用通常的,使用中和、高分子凝聚剂等的、简便方法进行处理。
在用本发明的微蚀刻处理剂处理后,为了进一步提高其与树脂的密着性能,也可用如偶氮类的水溶液和醇溶液进行处理,如同美国专利说明书3645772号所揭示的。另外,在用本发明的微蚀刻剂处理之后,还可作被称为棕色氧化和黑色氧化的氧化处理。
本发明的微蚀刻剂可广泛使用于铜及铜合金的化学研磨等研磨中。特别是,由该处理,可在处理的铜等的表面上形成较深的凹凸状,使其与预浸渍膜、耐焊锡膜层、耐干膜膜层、耐电镀涂层等的树脂层具有良好的密着性能,而且,该表面具优异的钎焊性,特别有用于如包括脉冲信号引线阵列(PGA)和压块引线阵列(BGA)等用的各种印刷线路板的制作。此外,本发明的蚀刻剂也可用于对引线框架的表面处理。
例如,在印刷电路板用的镀铜层合板的制作中,用本发明的微蚀刻剂对铜膜进行处理,使之表面粗化,则该表面与预浸渍片的粘结强度增大,且在形成图案时具有优异的蚀刻性。又,在制造多层印刷线路板时,将本发明的微蚀刻剂用于其内层基片的铜表面的粗化处理时,则可制得与预浸渍片的粘结强度优异、且具优异的耐引线冷却性能的表面。再有,用本发明的微蚀刻剂处理的表面,与以往用硫酸、过氧化氢系的蚀刻剂等处理的表面比较,其光泽度较低,因此,在涂敷或层合感光性树脂时,不但可得到提高其与树脂的密着性的效果,而且,曝光时的光散射也减少,还可得到提高感光性树脂分辨率的效果。实施例实施例1-4
混合表1所述的各成分,配制本发明的微蚀刻剂。其次,以所述的微蚀刻剂,在40℃、60秒的条件下,对印刷线路板用镀铜层合板(FR-4)作喷雾处理。然后,涂敷耐锡焊涂膜(PSR-4000,太阳印墨制造株式会社制),使其曝光,显象、固化(后固化),形成各种图案。接着,涂敷以无洗净型的后焊剂(AP-4626美克株式会社制),用喷流式的自动钎焊装置进行钎焊,观察其后的耐焊锡膜的状态。另外,缩短耐锡焊涂膜的后固化时间至少于标准时间内,使耐锡焊涂膜易于剥离,提高后焊剂的浓度达3倍。其结果示于表2。
又,用表1所示的微蚀刻剂,在40℃、60秒的条件下,对带有多个直径1mm的圆形垫片、其余部分覆有耐焊锡膜的印刷线路板用的镀铜膜叠层板(FR-4)作喷雾处理后,涂敷以匀焊用焊剂(W-2556,美克株式会社制),以水平型匀焊机作钎焊,调查钎焊合格率(焊上焊锡的垫片比率)。其结果示于表2。比较例1-4
与实施例1同样,调节表1所示的微蚀刻剂,并作评价。其结果示于表2。
表1
实施例编号            组成(%)
1 氯化铜(二价)·二水合物 4醋酸)(kPa=4.56)       5离子交换水             余
2 甲酸铜(二价)           5甲酸(kPa=3.55)        2氯化铵                 8离子交换水             余
3 醋酸铜(二价)           5丙烯酸(kPa=4.26)      20氯化钠                 4乙二胺                 1离子交换水             余
4 溴化铜(二价)           2乙醇酸(kPa=3.63)      10离子交换水             余
比较例1 硫酸                   1035%过氧化氢水溶液     5离子交换水             余
比较例2 过硫酸钠          10硫酸              1离子交换水        余
比较例3 氯化铜(二价)      4盐酸              5离子交换水        余
比较例4 氯化铜(二价)      4尿酸(kPa=5.61)   0.5离子交换水        余
表2
实施例编号   锡焊合格率(%)   耐锡焊膜的剥离、起泡
    1     100       完全无
    2     97.4       完全无
    3     96.6       完全无
    4     95.3       完全无
比较例1     60.2         有
比较例2     54.3         有
比较例3     80.8        稍有
比较例4     50.0         有
(注)比较例3的微蚀刻剂在重复多次对镀铜叠层板进行处理后,其蚀刻
    性能(蚀刻速度)不稳定,很难作均匀的处理。
比较例4的微蚀刻剂处理的铜表面上产生了结晶态粉状物。另外,锡焊后的焊锡表面光泽度变差。
发明效果
用本发明的微蚀刻剂处理铜或铜合金,由此可使铜表面与预浸渍涂膜及耐蚀膜层等的树脂的粘结性良好,也可形成具优异的软钎焊性能的表面。而且,如此所得的表面与以往的微蚀刻方法所得的表面比较,由于其光泽度小,因此当将该铜表面用作感光性树脂的衬底材料时可以得到提高分辨率的效果,在以自动光学检测仪(AOI)对印刷线路板的电路作检测时,也可减少误动作。因而,本发明的微蚀刻剂是一种完全可适用于今后图案日益线条细化和高强度化的印刷线路板的制造。

Claims (1)

1.一种铜及铜合金的微蚀刻剂,由含以下物质的水溶液组成:
(a)二价铜离子源,换算为金属铜,含量为0.01~20重量%;
(b)氨基磺酸或选自饱和脂肪酸、不饱和脂肪酸、脂肪族饱和二元酸、脂肪族不饱和二元酸、芳香族羧酸、羟基羧酸和带有取代基的羧酸的酸解离常数pKa小于5且碳原子数为1-6的有机酸,含量为0.1~30重量%;及
(c)卤原子源,以卤原子计为0.01~20重量%。
CN96110803A 1995-08-01 1996-07-10 铜及铜合金的微蚀刻剂 Expired - Lifetime CN1090686C (zh)

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US5807493A (en) 1998-09-15
CN1147025A (zh) 1997-04-09
KR970011017A (ko) 1997-03-27
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