CN1248300A - 微多孔性铜覆膜及用于制备该铜覆膜的化学镀铜液 - Google Patents
微多孔性铜覆膜及用于制备该铜覆膜的化学镀铜液 Download PDFInfo
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- CN1248300A CN1248300A CN98802739A CN98802739A CN1248300A CN 1248300 A CN1248300 A CN 1248300A CN 98802739 A CN98802739 A CN 98802739A CN 98802739 A CN98802739 A CN 98802739A CN 1248300 A CN1248300 A CN 1248300A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010949 copper Substances 0.000 title claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 54
- 238000007747 plating Methods 0.000 title claims description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 229910000906 Bronze Inorganic materials 0.000 claims description 26
- 239000010974 bronze Substances 0.000 claims description 26
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 26
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 abstract description 3
- -1 hypophosphorous acid compound Chemical class 0.000 abstract description 3
- 239000008139 complexing agent Substances 0.000 abstract 1
- 238000007772 electroless plating Methods 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000011889 copper foil Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 208000003351 Melanosis Diseases 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
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- 239000004471 Glycine Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/1648—Porous product
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/125—Deflectable by temperature change [e.g., thermostat element]
- Y10T428/12514—One component Cu-based
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12903—Cu-base component
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Abstract
公开了一种在每1cm2面积上具有10万～10亿个微孔的金属铜覆膜和具有这种覆膜的镀覆制品。这种金属铜覆膜可以通过将被镀物置于一种含有铜离子、配合剂、次磷酸化合物、引发还原反应的金属催化剂和含炔键的化合物的化学镀铜液中浸渍而制得。
Description
技术领域
本发明涉及具有微多孔的金属铜覆膜，更详细地说，涉及一种具有许多微米级微孔的金属铜覆膜、用于形成该铜覆膜的化学镀铜液以及具有该金属铜覆膜的镀覆制品。
背景技术
迄今为止，多层印刷电路基板都是按照下述方法制备，即，首先通过制备敷铜层压板上的铜箔并形成印刷电路板上的线路来制备内层用敷铜层压板，然后通过对该铜箔进行表面前处理(通常是先脱脂，然后以过硫酸铵、过硫酸钠、氯化铜、硫酸-过氧化氢等为代表的体系进行软蚀刻处理和活化处理)来使其表面粗化，进而通过黑化处理或褐化处理等为代表的处理来形成氧化铜或氧化亚铜的针状覆膜，再在该内层用敷铜层压板上通过一层热固性树脂含浸基材(预浸料坯)层压粘接外层用敷铜层压板或铜箔，从而制成一种粘接性强的多层层压板。
这样制造的多层层压板有必要使各层之间通电，为此，必须在层压板上钻孔，然后进行通孔镀覆，但是，由于在为了进行通孔镀覆而赋予催化剂的工序中所用酸性溶液的渗入，或者在化学镀铜工序中镀液的渗入，会使氧化铜或氧化亚铜覆膜溶解，从而产生被称为粉红环(晕渗)现象，这是其缺点。
另一方面，由于利用以预先经过表面粗糙化的铜箔制得的敷铜层压板来形成印刷电路板的线路，因此省去上述铜箔表面粗糙化和氧化覆膜形成的工序也能形成多层印刷电路基，但是，按照该方法，由于铜箔表面已被粗糙化，因此存在引起印刷蚀刻保护膜或按紫外线照射方法的蚀刻保护膜的图形精度变差的问题。
为了解决上述的问题，本发明者们于最近开发了一种通过化学镀铜来形成粘接性优良并呈均匀针状的铜覆膜的方法，并对此提出了专利申请(特开平4-116176号和PCT/JP96/03829号)。按照这种技术，可以获得一种没有上述缺点的，具有粘接性强的铜覆膜的敷铜层压板。
发明内容
本发明者们为了进一步改进这种技术而进行了深入研究，结果发现，使用表面活性剂时所获的铜覆膜不是均匀针状的而是具有微多孔的，并且使用这种铜覆膜可以获得一种具有优良粘接性的铜覆膜的敷铜层压板。
进而发现，这种具有微多孔的铜覆膜是迄今为止尚未为人们所知的，它不仅可作为敷铜层压板使用，而且，将该覆膜取下时还可作为金属过滤器、催化剂或催化剂载体使用，至此便完成了本发明。
也就是说，本发明的第一个目的是提供一种在每1cm2面积上具有10万～10亿个微孔的金属铜覆膜。
另外，本发明的第二个目的是提供一种化学镀铜液，该化学镀铜液含有铜离子、配合剂、作为还原剂的次磷酸化合物和引发还原反应的金属催化剂，此外它还含有含炔键的化合物。
进而，本发明的第三个目的是提供一种具有微多孔铜覆膜的镀覆制品，该制品通过在上述化学镀铜液中浸渍而制得。
对附图的简单说明
图1是显示本发明化学镀铜覆膜外观的结晶结构的照片(×5,000)。
用于实施发明的最佳方案
作为配合在本发明化学镀铜液中的含炔键的化合物的例子，可以举出由下述通式(1)表示的化合物
(式中，R1和R2表示烷基，R3和R4表示氢原子或低级烷基)。
作为含有炔键的化合物的具体例，可以举出：2，4，7，9-四甲基-5-癸炔-4，7-二醇、3，6-二甲基-4-辛炔-3，6-二醇等炔二醇，它们以Surfinol 104(日信化学工业制)等商品名有市售。
作为本发明的化学镀铜液的成分，除了含有上述炔键的化合物之外，其余可以使用那些能用于公知的以次磷酸化合物作为还原剂的化学镀铜液中的化合物来配制。例如，化学镀铜液中的铜离子可以由硫酸铜、氯化铜、硝酸铜等通常的铜盐获得，另外，作为配合物，只要是能够配合上述铜离子的化合物即可，例如可以使用柠檬酸、酒石酸、苹果酸、EDTA、Quadrol(N，N，N′，N′-四(2-羟丙基)乙二胺)、甘氨酸等。
另外，作为还原剂的次磷酸化合物，可以举出次磷酸、次磷酸钠等。作为引发还原反应的金属催化剂，可以使用镍、钴、钯等，可以以它们的无机盐等形式使用。
在本发明的化学镀铜液中的各成分，在使用镍作为引发还原反应的金属催化剂的情况下，优选是铜离子为0.007～0.160mol/l、镍离子为0.001～0.023mol/l，希望铜离子与镍离子的摩尔比为13∶1左右。
另外，配合剂相对于铜离子的摩尔比优选为1～10倍，而作为还原剂的次磷酸化合物优选按0.1～1.0mol/l左右配合。
另外，在使用其他金属作为引发还原反应的金属催化剂的情况下也可以根据上述用量比通过实验来决定最适合的用量。
在本发明的化学镀液中，除了上述各成分之外，还可以根据需要添加其他各种成分。作为其他成分的例子，可以举出用于调节pH值的缓冲剂等。
另外，对于本发明的化学镀铜液来说，也可以采用首先将其配制成浓的化学镀铜液组合物，待使用时再用水将其稀释几倍至十几倍的方案。
对于本发明的化学镀铜工艺来说，可以使用按上述方法获得的本发明的化学镀铜液并按常规方法进行实施。在实施时，优选是预先除去化学镀铜液中的氧，为此，优选是预先用氮气、氩气等惰性气体向化学镀铜液中鼓泡。
另外，在本发明的化学镀铜工艺中，化学镀铜液的温度优选为40～100℃左右，镀覆时间优选在5分钟以上。另外，在本发明的化学镀铜工艺中，为了防止不必要的氧化，希望采用摇动搅拌的方法，但是，也可以使用惰性气体，将搅拌和脱氧操作同时进行。另外，本发明化学镀铜液的pH值优选在8～10的范围内。
由上述化学镀铜液析出的化学镀铜覆膜具有图1所示的外观，它在每1cm2面积上的微孔数在100,000～1,000,000,000的范围内，通常在3,000,000～300,000,000的范围内。另外，其微孔的孔径在0.01～100μm的范围内，通常在0.1～10μm的范围内。
这种具有许多微孔的铜覆膜是以往尚未为人们所知的新颖的铜覆膜，而且它可以按简单的化学方法制造，这一点具有很大意义。
而且，由于预浸料坯能进入所说铜覆膜上的许多微孔中，因此使得该铜覆膜具有优良的粘接性，不仅如此，由于它具有许多微孔，因此还可考虑它在其他方面的各种用途。
例如，可以使本发明的铜覆膜析出到平滑的玻璃板或塑料板上，然后将其剥离，这样就能获得一种具有许多微孔的铜箔，这种铜箔可以作为过滤器使用。另外，如果使适当的金属例如铑等贵金属或镍等金属析出在这种铜箔上，也可以将其作为催化剂使用。
另外，在本发明的化学镀铜方法中，也可以通过向化学镀铜液中加入象特开平4-116176号中公开的含炔键的表面活性剂例如Surfinol465(日信化学工业制)来获得一种在其全部表面上形成有细小针状晶体的微多孔铜覆膜。
下面举出实施例和试验例来更详细地描述本发明，但本发明不受这些实施例的限制。
实施例1
化学镀铜液的制备(1)：
按照下列组成并按常规方法制备化学镀铜液。(组成)硫酸铜 0.032mol/l柠檬酸钠 0.052mol/l次磷酸钠 0.270mol/l硼酸 0.500mol/l硫酸镍 0.0024mol/lSurfinol 104* 1.0g/lpH 9.0
*：日信化学工业制
使用该化学镀铜液，在60℃下对一块内层用敷铜层压板(FR-4；环氧树脂)进行化学镀覆30分钟。当使用扫描电子显微镜观察所获的铜覆膜时发现，该铜覆膜具有如图1所示那样的许多微孔。
实施例2
与树脂基材的粘接强度：
本发明的微多孔铜覆膜在各种树脂基材上的粘接强度可通过下述方法来评价，即，按实施例1的组成在树脂基材上施加电解镀铜后，通过预浸料坯压合，如此制成多层板，然后通过测定该多层板的剥离强度来评价。
其结果，在FR-4的情况下，所获强度为1.2kgf/cm，在BT-800树脂(双马来酰亚胺三嗪)的情况下为0.7kgf/cm，通过黑化处理可以获得高的粘接强度。另外，在PPE-S树脂(聚亚苯基醚)的情况下，通过黑化处理几乎不能获得粘接力，但是在形成本发明的微多孔铜覆膜的情况下，获得了0.2kgf/cm的粘接力。
如上所述，本发明的微多孔铜覆膜尤其是对于最近具有高耐热性、电学可靠性、耐药性的树脂基材来说，作为内层铜箔处理是有效的。
实施例3
化学镀铜液的配制(2)：
按照下列组成并按常规方法制备化学镀铜液。(组成)硫酸铜 0.032mol/l柠檬酸钠 0.052mol/l次磷酸钠 0.270mol/l硼酸 0.500mol/l硫酸镍 0.0024mol/lSurfinol 104* 1.0g/lSurfinol 465* 0.1g/lpH 9.0
*：日信化学工业制
与实施例1同样地在内层用敷铜层压板(FR-4)上进行化学镀铜，测得其粘接强度为1.3kgf/cm，当用扫描电子显微镜观察时发现，在包含微多孔的内侧在内的全部表面上形成有小的针状晶体。
工业实用性
通过使本发明的微多孔铜覆膜析出到基底铜箔与各种树脂基材之间，可以获得高的粘接强度，不仅如此，还可利用这种所谓微多孔的特性，期待许多方面的应用。
作为其例子，可以举出金属微过滤器、催化剂或其载体。
Claims (9)
1.一种具有微多孔的金属铜覆膜，它在每1cm2的面积上具有10万～10亿个微孔。
2.如权利要求1所述的具有微多孔的金属覆膜，它是通过将被镀物置于一种含有铜离子、配合剂、次磷酸化合物、引发还原反应的金属催化剂和含炔键的化合物的化学镀铜液中浸渍而制得的。
3.如权利要求2所述的具有微多孔的金属铜覆膜，其中所述的含炔键的化合物由通式(1)表示
(式中，R1和R2表示烷基，R3和R4表示氢原子或低级烷基)。
4.一种化学镀铜液，它含有铜离子、配合剂、作为还原剂的次磷酸化合物和引发还原反应的金属催化剂，其特征在于，其中还含有含炔键的化合物。
5.如权利要求4所述的化学镀铜液，其中所述的含炔键的化合物由通式(1)表示
(式中，R1和R2表示烷基，R3和R4表示氢原子或低级烷基)。
6.一种化学镀方法，其特征在于，将被镀物置于一种含有铜离子、配合剂、次磷酸化合物、引发还原反应的金属催化剂和含炔键的化合物的化学镀液中浸渍，使其析出微多孔性铜覆膜。
7.如权利要求6所述的化学镀方法，其中所述的含炔键的化合物由通式(1)表示
(式中，R1和R2表示烷基，R3和R4表示氢原子或低级烷基)。
8.一种具有微多孔铜覆膜的镀覆制品，它通过在一种含有铜离子、配合剂、次磷酸化合物、引发还原反应的金属催化剂和含炔键的化合物的化学镀铜液中浸渍而制得。
9.如权利要求8所述的具有微多孔铜覆膜的镀覆制品，其中所述的含炔键的化合物由通式(1)表示
(式中，R1和R2表示烷基，R3和R4表示氢原子或低级烷基)。
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| JP05250797A JP3198066B2 (ja) | 1997-02-21 | 1997-02-21 | 微多孔性銅皮膜およびこれを得るための無電解銅めっき液 |
| JP52507/1997 | 1997-02-21 | ||
| JP52507/97 | 1997-02-21 |
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| CN1248300A true CN1248300A (zh) | 2000-03-22 |
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| JP (1) | JP3198066B2 (zh) |
| KR (1) | KR100495531B1 (zh) |
| CN (1) | CN1204291C (zh) |
| AU (1) | AU6229798A (zh) |
| DE (1) | DE69807658T2 (zh) |
| HK (1) | HK1025365A1 (zh) |
| MY (1) | MY128899A (zh) |
| TW (1) | TW402644B (zh) |
| WO (1) | WO1998037260A1 (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465336C (zh) * | 2000-10-03 | 2009-03-04 | 株式会社日立制作所 | 布线基底和其制造方法以及其中使用的化学镀铜溶液 |
| CN100497732C (zh) * | 2005-08-19 | 2009-06-10 | 广东光华化学厂有限公司 | 混合型非甲醛还原剂的化学镀铜液 |
| CN103531815A (zh) * | 2013-10-25 | 2014-01-22 | 深圳清华大学研究院 | 集流体用穿孔箔及其制作方法 |
| CN105696034A (zh) * | 2014-12-12 | 2016-06-22 | 英飞凌科技股份有限公司 | 电解质、形成铜层的方法以及形成芯片的方法 |
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| JP2003013247A (ja) * | 2001-04-24 | 2003-01-15 | Murata Mfg Co Ltd | 無電解銅めっき浴及び高周波用電子部品 |
| DE10221503A1 (de) * | 2002-05-14 | 2003-11-27 | Infineon Technologies Ag | Zur wenigstens teilweisen Beschichtung mit einer Substanz bestimmter Metallgegenstand |
| US20050112432A1 (en) * | 2002-08-27 | 2005-05-26 | Jonah Erlebacher | Method of plating metal leafs and metal membranes |
| US8115419B2 (en) * | 2008-01-23 | 2012-02-14 | Cree, Inc. | Lighting control device for controlling dimming, lighting device including a control device, and method of controlling lighting |
| JP5176618B2 (ja) * | 2008-03-17 | 2013-04-03 | 株式会社村田製作所 | インプリント用金型、およびそれを用いたインプリント方法 |
| JP4516991B2 (ja) * | 2008-06-26 | 2010-08-04 | シャープ株式会社 | 電子写真用キャリア及びその用途 |
| WO2012029405A1 (ja) * | 2010-08-31 | 2012-03-08 | 株式会社村田製作所 | 多孔質金属膜、電極、集電体、それを用いた電気化学センサ、蓄電デバイス及び摺動部材並びに多孔質金属膜の製造方法 |
| WO2013113068A1 (en) * | 2012-02-02 | 2013-08-08 | Nano-Nouvelle Pty Ltd | Thin coatings on materials |
| CN103422079B (zh) * | 2012-05-22 | 2016-04-13 | 比亚迪股份有限公司 | 一种化学镀铜液及其制备方法 |
| JP2015001016A (ja) * | 2013-06-17 | 2015-01-05 | 古河電気工業株式会社 | 銅箔、銅張積層板及びプリント配線板 |
| CN103481583B (zh) * | 2013-10-09 | 2017-01-04 | 北京科技大学 | 一种表面具有多孔结构的处理铜箔的制备方法 |
| KR101809985B1 (ko) | 2017-03-30 | 2017-12-18 | 와이엠티 주식회사 | 다공성 구리박의 제조방법 및 이를 이용한 다공성 구리박 |
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| US4563217A (en) * | 1983-07-25 | 1986-01-07 | Hitachi, Ltd. | Electroless copper plating solution |
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| JPH02118097A (ja) | 1988-10-27 | 1990-05-02 | Eagle Ind Co Ltd | 軸受摺動面の表面処理方法 |
| JP2892428B2 (ja) * | 1989-09-05 | 1999-05-17 | 新光電気工業株式会社 | 無電解金めっき液 |
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- 1997-02-21 JP JP05250797A patent/JP3198066B2/ja not_active Expired - Lifetime
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- 1998-02-19 WO PCT/JP1998/000689 patent/WO1998037260A1/ja active IP Right Grant
- 1998-02-19 DE DE69807658T patent/DE69807658T2/de not_active Expired - Lifetime
- 1998-02-19 AU AU62297/98A patent/AU6229798A/en not_active Abandoned
- 1998-02-19 EP EP98904387A patent/EP0964076B1/en not_active Expired - Lifetime
- 1998-02-19 CN CNB988027399A patent/CN1204291C/zh not_active Expired - Fee Related
- 1998-02-19 KR KR10-1999-7007206A patent/KR100495531B1/ko not_active IP Right Cessation
- 1998-02-19 US US09/355,983 patent/US6329072B1/en not_active Expired - Fee Related
- 1998-02-20 TW TW087102387A patent/TW402644B/zh active
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2000
- 2000-07-19 HK HK00104452A patent/HK1025365A1/xx not_active IP Right Cessation
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465336C (zh) * | 2000-10-03 | 2009-03-04 | 株式会社日立制作所 | 布线基底和其制造方法以及其中使用的化学镀铜溶液 |
| CN100497732C (zh) * | 2005-08-19 | 2009-06-10 | 广东光华化学厂有限公司 | 混合型非甲醛还原剂的化学镀铜液 |
| CN103531815A (zh) * | 2013-10-25 | 2014-01-22 | 深圳清华大学研究院 | 集流体用穿孔箔及其制作方法 |
| CN103531815B (zh) * | 2013-10-25 | 2015-12-09 | 深圳清华大学研究院 | 集流体用穿孔箔及其制作方法 |
| CN105696034A (zh) * | 2014-12-12 | 2016-06-22 | 英飞凌科技股份有限公司 | 电解质、形成铜层的方法以及形成芯片的方法 |
| US10648096B2 (en) | 2014-12-12 | 2020-05-12 | Infineon Technologies Ag | Electrolyte, method of forming a copper layer and method of forming a chip |
Also Published As
| Publication number | Publication date |
|---|---|
| MY128899A (en) | 2007-02-28 |
| EP0964076A4 (en) | 2000-01-26 |
| EP0964076B1 (en) | 2002-09-04 |
| KR100495531B1 (ko) | 2005-06-14 |
| US20020046679A1 (en) | 2002-04-25 |
| AU6229798A (en) | 1998-09-09 |
| CN1204291C (zh) | 2005-06-01 |
| HK1025365A1 (en) | 2000-11-10 |
| DE69807658D1 (de) | 2002-10-10 |
| KR20000070941A (ko) | 2000-11-25 |
| WO1998037260A1 (fr) | 1998-08-27 |
| EP0964076A1 (en) | 1999-12-15 |
| JPH10237664A (ja) | 1998-09-08 |
| JP3198066B2 (ja) | 2001-08-13 |
| US6329072B1 (en) | 2001-12-11 |
| DE69807658T2 (de) | 2003-05-08 |
| TW402644B (en) | 2000-08-21 |
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