CN1703327B - 由印刷电路板剥离银的方法 - Google Patents

由印刷电路板剥离银的方法 Download PDF

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CN1703327B
CN1703327B CN038066629A CN03806662A CN1703327B CN 1703327 B CN1703327 B CN 1703327B CN 038066629 A CN038066629 A CN 038066629A CN 03806662 A CN03806662 A CN 03806662A CN 1703327 B CN1703327 B CN 1703327B
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silver
printed circuit
circuit board
pcb
plating
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CN1703327A (zh
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丹娜·M·寇罗格
雷蒙德·A·里提兹
布莱恩·赖森
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MacDermid Inc
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    • CCHEMISTRY; METALLURGY
    • 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/32Alkaline compositions
    • C23F1/40Alkaline compositions for etching other metallic material
    • CCHEMISTRY; METALLURGY
    • 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/44Compositions for etching metallic material from a metallic material substrate of different composition
    • HELECTRICITY
    • 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
    • H05K3/02Apparatus 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
    • H05K3/06Apparatus 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 the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067Etchants
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03Metal processing
    • H05K2203/0361Stripping a part of an upper metal layer to expose a lower metal layer, e.g. by etching or using a laser
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H05K2203/0796Oxidant in aqueous solution, e.g. permanganate

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

发明涉及一种由印刷电路板剥离银的方法,其不会侵害下面的基底金属。该剥离溶液包含一种氧化剂、一种碱性pH值调节剂、及一种银加溶剂。当银自印刷电路板的表面被充分移除后,使该印刷电路板与一种中和溶液接触以移除保留在表面上的污物。该银剥离溶液不含氰化物或铬酸盐,而且不需要使用阳极电流。

Description

由印刷电路板剥离银的方法
技术领域
本发明涉及一种处理印刷电路板的方法,由该方法从印刷电路板上化学移除所镀敷的银而不须使用有害化学试剂或施加外部电流。
背景技术
在使用印刷电路制造电子设备时,电子组件至印刷电路的连接是通过焊接组件的引线至通孔、周围的焊盘、焊接区和其他连接点而完成。
为了利于此项焊接操作,需要印刷电路制造商安排通孔、焊盘、焊接区和其他连接点可接受随后的焊接过程。因此,这些表面必须是用焊料容易润湿的且允许与电子组件的引线或表面形成整体的导电连接。因为这些需要,印刷电路制造商发明了保持和加强表面的可焊性的各种方法。
直接焊接至铜表面曾经是困难且不相容的。这些问题主要是由于无法保持铜表面的清洁及不能使焊接操作全程无氧化。浸渍银沉积物被发现可提供优良可焊性的保持,其可特别适用于制造印刷电路板。银离子的可溶性源可得自多种银化合物。银浸渍镀敷方法的一个实例见于颁予Redline等人的美国第6,200,451号专利,其主题并入本文以供参考。该浸渍银溶液可用来镀敷一薄层的银于欲焊接的表面上。所产生的银涂层其厚度通常在1至100微英寸间,以有效地增强和保持表面的可焊性。
通常,浸渍镀敷方法由置换反应产生,由此被镀敷的表面溶入溶液中,同时被镀敷的金属自镀敷溶液沉积在该表面上。该浸渍镀敷可不需要表面的预先活化而引发。通常,欲镀敷的金属比表面金属贵重。因此,浸渍镀敷通常比化学镀敷显著地较易控制且更具成本效益,而化学镀敷需要复杂的自动催化镀敷溶液以及在镀敷前将表面活化的过程。
在制造印刷电路板的过程中,还可能需要随后从表面沉积有银的所有或局部的铜或其他金属上剥离银。例如,在必须直接镀敷另外一种金属例如镍或金至板上某些部份的铜上的情况下,或在需要涂敷阻焊掩模在某些裸铜表面上的情况下,形成了此种需要。还可能在处理不合格品以回收和再利用下面的铜材料的过程中,需要从铜层上剥离银。
在剥离银的技术领域中,公知使用化学试剂例如氰化物、铬酸盐及强酸溶液以利于从基板表面上移除银。另外,使用阳极电流以便利移除银,而不管使用或不使用这些化学试剂也是公知的。
有用的银剥离剂的实例是抑制酸或氰化物溶液。所述酸包括硫酸和磺酸及使用于剥离金属组合物中的其他无机酸。氰化物剥离剂组合物包括本领域技术人员所熟知的碱、碱土金属或铵的氰化物剥离组合物。抑制组合物典型的是由硝基化合物予以抑制的。有用的抑制化合物的实例包括硝基苯、硝基苯甲酸、硝基苯甲醛、硝基烷属烃及硝基烷烃。
虽然这些方法确实有利于移除所镀敷的银,但是由于与使用氰化物或铬酸盐相关的环境上的考虑,这些方法是不能接受的。现有技术中所使用的化学试剂还具有侵害下面的阻焊掩模或基板的趋势。另外,当使用阳极电流时,可能不能施加电流以越过整个印刷电路板。
授予Janikowski的美国法定发明登记H1,136(其主题并入本文以供参考)公开了一种电镀银的方法,其包括一种碱性氢氧化物和乙二胺的电镀溶液和/或剥离溶液。虽然该电镀和/或剥离溶液不含氰化物,但是该发明的方法需要阳极电流。
同样地,颁予Smith的美国第5,002,649号专利(其主题并入本文以供参考)公开了一种从一局部表面上电解或化学剥离镀敷材料(包括银镀敷物)的装置。该装置需要阳极电流,尽管可以电解或化学方式来进行剥离。另外,该化学剥离溶液可含有氰化物。
本发明的方法提供了一种用于移除银的新的剥离溶液,其不含任何现有技术剥离溶液的较多的有毒化学试剂或不需要使用阳极电流以利于移除所镀的银。另外,本发明的银剥离溶液不会侵害欲镀敷银的基底金属或阻焊掩模。该方法还提供一种有创造性的剥离溶液以从印刷电路板上以化学方式移除所镀敷的银,而没有现有技术中所发现的固有的各种问题。
发明概述
本发明涉及一种从印刷电路板上剥离银而不会侵害下面的基底金属的方法。本发明方法的另外优点是其具有选择性移除银而不会侵害阻焊掩模的能力。
本发明包括用于从印刷电路板上移除所镀敷的银的方法,该方法包括下列步骤:
(a)使印刷电路板与包含一种氧化剂、一种碱性pH值调节剂和一种银加溶剂的剥离溶液接触;及
(b)使用一种中和溶液将印刷电路板中和。
发明的详细描述
对印刷电路板涂布以一种基底金属,例如铜、镍或金,在该基底金属上镀敷银。调配本发明的银剥离组合物以剥离所镀敷的银,同时不会侵害镀敷银的基底金属。对于制造印刷电路板所需要的严格的公差和厚度规格,这点特别重要。剥离溶液的化学作用是使该溶液选择性地移除银而不会侵害阻焊掩模。另外,没有粘附性损失或基板的隆起、漂白或褪色的迹象,或完成加工后阻焊掩模的浸出的迹象。
本发明的剥离溶液包含一种强氧化剂、一种碱性pH值调节剂和一种银加溶剂。用于本发明的合适的强氧化剂包括高锰酸钾、高锰酸钠、亚氯酸钠或钾及氯酸钠或钾。高锰酸钠或钾是优选的。pH值调节剂通常是一种氢氧化物,例如氢氧化钠或氢氧化钾。用于本发明的合适的银加溶剂包括琥珀酰亚胺和氨水(氢氧化铵)或其他铵离子源。另外,存在于本发明剥离溶液中的其他非必要成份包括碳酸铵和碳酸氢铵。
氧化剂优选以1至30克/升的浓度存在于溶液中。碱性pH值调节剂优选以7至25克/升的浓度存在并具有充分的量以维持pH值在11至13.5之间,优选在12.5至13.5间。银加溶剂优选以1至5克/升的浓度存在于溶液中。如果使用非必要成份,其以2至15克/升的浓度存在于剥离溶液中。
通过使印刷电路板浸入剥离溶液中使印刷电路板与该溶液接触5分钟的时间。通常将剥离溶液加热至95°F至115°F范围内的温度。剥离的进展可通过周期性的目视检验或通过以周期性的间隔来测量基板的重量损失。
一旦银自表面上被充分移除,立即使印刷电路板经受标准中和步骤来移除自剥离银后残留在基板上的任何污物。使印刷电路板与中和溶液接触,该溶液优选含有硫酸羟胺和硫酸。

Claims (8)

1.一种从印刷电路板上移除所镀敷的银的方法,该印刷电路板包含基底金属的电路图形,该电路图形至少部分地被镀覆银沉积物所覆盖,所述方法包括下列步骤:
(a)使所述印刷电路板与包含一种氧化剂、一种碱性pH值调节剂和一种银加溶剂的剥离溶液接触;及
(b)使用一种中和溶液将所述印刷电路板中和,
其特征在于,所述剥离溶液中不含有氰化物,并且所述方法不包括使用阳极电流来移除所镀敷的银的步骤。
2.根据权利要求1所述的方法,其中重复进行步骤(a)和(b)。
3.根据权利要求1所述的方法,其中所述氧化剂是高锰酸钾。
4.根据权利要求1所述的方法,其中所述碱性pH值调节剂是氢氧化钠。
5.根据权利要求1所述的方法,其中所述银加溶剂选自琥珀酰亚胺和氨水。
6.根据权利要求1所述的方法,其中所述中和溶液包含硫酸羟胺和硫酸。
7.根据权利要求1所述的方法,其中所述基底金属选自铜、镍和金。
8.根据权利要求1所述的方法,其中所述剥离溶液还包含碳酸铵或碳酸氢铵。
CN038066629A 2002-03-25 2003-02-18 由印刷电路板剥离银的方法 Expired - Fee Related CN1703327B (zh)

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US10/106,522 2002-03-25
US10/106,522 US6783690B2 (en) 2002-03-25 2002-03-25 Method of stripping silver from a printed circuit board
PCT/US2003/004784 WO2003082605A1 (en) 2002-03-25 2003-02-18 Method of stripping silver from a printed circuit board

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ES (1) ES2410811T3 (zh)
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US4204013A (en) * 1978-10-20 1980-05-20 Oxy Metal Industries Corporation Method for treating polymeric substrates prior to plating employing accelerating composition containing an alkyl amine
US6126720A (en) * 1997-06-16 2000-10-03 Mitsubishi Materials Corporation Method for smelting noble metal

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JP3683896B2 (ja) 2005-08-17
JP2005520936A (ja) 2005-07-14
AU2003217557A1 (en) 2003-10-13
ES2410811T3 (es) 2013-07-03
EP1487646A4 (en) 2010-01-13
EP1487646A1 (en) 2004-12-22
US20030183598A1 (en) 2003-10-02
EP1487646B1 (en) 2013-05-22
US6783690B2 (en) 2004-08-31
TW200304507A (en) 2003-10-01
WO2003082605A1 (en) 2003-10-09
CN1703327A (zh) 2005-11-30
TWI256423B (en) 2006-06-11

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