JP4113846B2 - Removal liquid and removal method of metal deposition catalyst adhering to resin surface, and method for producing printed wiring board using the same - Google Patents
Removal liquid and removal method of metal deposition catalyst adhering to resin surface, and method for producing printed wiring board using the same Download PDFInfo
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- JP4113846B2 JP4113846B2 JP2004019520A JP2004019520A JP4113846B2 JP 4113846 B2 JP4113846 B2 JP 4113846B2 JP 2004019520 A JP2004019520 A JP 2004019520A JP 2004019520 A JP2004019520 A JP 2004019520A JP 4113846 B2 JP4113846 B2 JP 4113846B2
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- catalyst
- resin surface
- metal deposition
- wiring board
- removal
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- 239000003054 catalyst Substances 0.000 title claims description 73
- 239000011347 resin Substances 0.000 title claims description 51
- 229920005989 resin Polymers 0.000 title claims description 51
- 239000007788 liquid Substances 0.000 title claims description 36
- 238000001465 metallisation Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 59
- 229910052802 copper Inorganic materials 0.000 claims description 57
- 239000010949 copper Substances 0.000 claims description 57
- 238000007747 plating Methods 0.000 claims description 45
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 230000002265 prevention Effects 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 10
- 229920006317 cationic polymer Polymers 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910001504 inorganic chloride Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- -1 chlorine ions Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 150000005215 alkyl ethers Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003567 thiocyanates Chemical class 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- YYYOQURZQWIILK-UHFFFAOYSA-N 2-[(2-aminophenyl)disulfanyl]aniline Chemical compound NC1=CC=CC=C1SSC1=CC=CC=C1N YYYOQURZQWIILK-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RLDQYSHDFVSAPL-UHFFFAOYSA-L calcium;dithiocyanate Chemical group [Ca+2].[S-]C#N.[S-]C#N RLDQYSHDFVSAPL-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000005440 nitrobenzoic acid derivatives Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 description 1
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical class S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本発明は多層プリント配線板製造時に、積層樹脂表面に残存・付着した金属析出触媒の除去液および除去方法ならびにこれを用いたプリント配線板の製造方法に関する。 The present invention relates to a removing solution and a removing method of a metal deposition catalyst remaining and adhered to the surface of a laminated resin during the production of a multilayer printed wiring board, and a method for producing a printed wiring board using the same.
多層プリント配線板の製造方法はいくつかあるが、多くのものは、外層に回路を形成した後に、その上に絶縁層として樹脂を積層し、さらにその樹脂上に銅回路を形成する、という工程を繰り返すことにより製造される。絶縁層である樹脂表面に銅回路を形成するには、まず前処理として樹脂表面全体にパラジウム等の金属析出触媒（以下、「触媒」という）を付着させる工程が必要である。そして前処理後の樹脂表面に無電解銅めっきを施すことにより、触媒を核として無電解銅めっき皮膜が形成される。次いで、その上に電気銅めっきで１０〜２０μｍの銅層を形成し、その後、レジストを利用して銅層の不要な部分をエッチングすることにより銅回路を形成する。 There are several methods for manufacturing a multilayer printed wiring board, but in many cases, after forming a circuit in the outer layer, a resin is laminated thereon as an insulating layer, and a copper circuit is formed on the resin. It is manufactured by repeating. In order to form a copper circuit on the resin surface that is an insulating layer, a step of attaching a metal deposition catalyst such as palladium (hereinafter referred to as “catalyst”) to the entire resin surface as a pretreatment is required. Then, by applying electroless copper plating to the resin surface after the pretreatment, an electroless copper plating film is formed using the catalyst as a nucleus. Next, a copper layer having a thickness of 10 to 20 μm is formed thereon by electrolytic copper plating, and then a copper circuit is formed by etching an unnecessary portion of the copper layer using a resist.
この銅回路形成時のエッチングによりレジストを施されていない銅層が除去され、外観的には樹脂表面が露出しているように見える。しかしながら銅層が除去された樹脂表面には無電解銅めっき皮膜を形成させるのに用いたパラジウム等の触媒が付着している場合が多く、その影響により配線間の絶縁性が低下するという問題があった。 Etching at the time of forming the copper circuit removes the copper layer that has not been subjected to the resist, and the appearance of the resin appears to be exposed. However, a catalyst such as palladium used to form an electroless copper plating film is often attached to the resin surface from which the copper layer has been removed. there were.
このような樹脂表面に付着したパラジウム等の触媒の除去液としては、シアン化物、ニトロ安息香酸誘導体を主成分とするものが知られている（特許文献１）。しかしながら、この除去液は銅に対する溶解性が高く、毒性も強いという問題があった。 As such a removal solution for a catalyst such as palladium adhering to the resin surface, a solution containing cyanide and a nitrobenzoic acid derivative as main components is known (Patent Document 1). However, this removal solution has a problem of high solubility in copper and strong toxicity.
また、触媒の除去液として硝酸、塩素イオンを主成分とし、含窒素複素環化合物、多価アルコール、非イオン界面活性剤、カチオン系界面活性剤のうち１種以上を添加したものも知られている（特許文献２）。しかしながら、この除去液を含む浴は何度も使用していくうちに樹脂上から除去されたパラジウムが液中に蓄積していくため、徐々にパラジウム濃度が高くなり、ある程度の濃度以上になると液中のパラジウムが銅表面に置換析出し銅表面が変色することがあった。そのため、この除去液を含む浴は長期間使用できないという問題がある。 In addition, a catalyst removal solution containing nitric acid and chlorine ions as main components and one or more of nitrogen-containing heterocyclic compounds, polyhydric alcohols, nonionic surfactants and cationic surfactants added is also known. (Patent Document 2). However, since the palladium removed from the resin accumulates in the bath over and over again, the concentration of palladium gradually increases. In some cases, palladium contained in the copper surface was deposited on the copper surface, and the copper surface was discolored. Therefore, there is a problem that the bath containing this removal liquid cannot be used for a long time.
本発明の目的は、触媒の除去能力は従来品と同等以上でありながら、銅に対する影響が少なく、長期間の使用に耐えうる、樹脂表面に付着した触媒の除去液を提供することにある。 An object of the present invention is to provide a catalyst removal solution attached to the surface of a resin, which has a catalyst removal capability equivalent to or higher than that of a conventional product, has little influence on copper, and can withstand long-term use.
本発明者らは上記課題を解決するために鋭意研究した結果、樹脂表面に付着した触媒を除去するには、硝酸および塩素イオンの他、カチオン性ポリマーを含む溶液を除去液として使用すればよいことを見出した。また、この組成の除去液は銅に対する溶解性が低いため、置換析出が起こりにくく長期間の使用に耐えうることを見出し、本発明を完成させた。また、この除去液をプリント配線板の製造方法に利用することにより、配線間の短絡等の防止された優れたプリント配線板を製造できることを見出した。 As a result of diligent research to solve the above problems, the present inventors can use a solution containing a cationic polymer in addition to nitric acid and chlorine ions as a removing solution in order to remove the catalyst attached to the resin surface. I found out. Moreover, since the removal liquid of this composition has low solubility with respect to copper, it has been found that substitutional precipitation hardly occurs and it can withstand long-term use, and the present invention has been completed. Further, it has been found that an excellent printed wiring board in which a short circuit between wirings is prevented can be produced by using this removing liquid in a method for producing a printed wiring board.
すなわち、本発明は硝酸、塩素イオンおよびカチオン性ポリマーを含有することを特徴とする樹脂表面に付着した触媒の除去液を提供するものである。 That is, the present invention provides a removing solution for a catalyst adhering to a resin surface, characterized by containing nitric acid, chlorine ions and a cationic polymer.
また、本発明は触媒が付着した樹脂表面に、上記触媒の除去液を作用させることを特徴とする樹脂表面に付着した触媒の除去方法を提供するものである。 The present invention also provides a method for removing a catalyst adhering to a resin surface, wherein the catalyst removing liquid is allowed to act on the resin surface adhering to the catalyst.
更に、本発明は配線基板の樹脂表面に金属析出触媒を付与後、無電解銅めっきを行い、その後電気銅めっきを行い、次いで不要な銅皮膜をエッチングすることにより回路パターンを形成し、その回路上に無電解金属めっきを行うプリント配線板の製造方法において、前記エッチングと無電解金属めっき工程の間に、配線基板の樹脂表面に上記の触媒除去液を作用させることを特徴とするプリント配線板の製造方法を提供するものである。 Furthermore, the present invention provides a circuit pattern by applying a metal deposition catalyst to the resin surface of the wiring board, followed by electroless copper plating, then performing electrolytic copper plating, and then etching an unnecessary copper film. In the printed wiring board manufacturing method for performing electroless metal plating on the printed wiring board, the catalyst removing liquid is allowed to act on the resin surface of the wiring board between the etching and the electroless metal plating step. The manufacturing method of this is provided.
また更に、本発明は配線基板の樹脂表面に金属析出触媒を付与後、無電解銅めっきを行い、その後電気銅めっきを行い、次いで不要な銅皮膜をエッチングすることにより回路パターンを形成し、その回路上に無電解金属めっきを行うプリント配線板の製造方法において、前記エッチングと無電解金属めっき工程の間に、配線基板の樹脂表面に上記の触媒除去液を作用させた後、更にブリッジ防止液を作用させることを特徴とするプリント配線板の製造方法を提供するものである。 Furthermore, the present invention provides a circuit pattern by applying a metal deposition catalyst to the resin surface of the wiring board, then performing electroless copper plating, then performing electrolytic copper plating, and then etching an unnecessary copper film, In the method of manufacturing a printed wiring board in which electroless metal plating is performed on a circuit, the above-described catalyst removal liquid is allowed to act on the resin surface of the wiring board between the etching and the electroless metal plating step, and then the bridge prevention liquid. The present invention provides a method for manufacturing a printed wiring board characterized in that
本発明の触媒の除去液は、銅に対する溶解性が抑制されたものでありながら、樹脂表面に付着した触媒を完全に除去することができるものである。 The catalyst removing solution of the present invention is capable of completely removing the catalyst adhering to the resin surface while suppressing its solubility in copper.
従って、配線間の絶縁性低下の原因となるパラジウム等の触媒を有効に除去でき、かつ、形成された銅回路を溶解しにくいので、例えば、プリント配線板の製造において、配線間の絶縁性が高いプリント配線板を製造することができる。 Accordingly, it is possible to effectively remove a catalyst such as palladium that causes a decrease in insulation between the wirings, and it is difficult to dissolve the formed copper circuit. A high printed wiring board can be manufactured.
更に、上記プリント配線板の製造において、本発明の触媒の除去液に加えてブリッジ防止液を併用することにより、より高密度な配線間であってもブリッジの生じることのないプリント配線板を製造することができる。 Furthermore, in the production of the printed wiring board, by using a bridge preventing liquid in addition to the catalyst removing liquid of the present invention, a printed wiring board that does not cause bridging even between higher density wirings is produced. can do.
本発明の触媒の除去液（以下、「除去液」という）における硝酸の含有量は、６７.５％硝酸として５０〜５００ｍＬ／Ｌが好ましく、特に１００〜４００ｍＬ／Ｌが好ましい。硝酸の含有量が５０ｍＬ／Ｌより少ないと触媒の除去効果がほとんど得られない。また、５００ｍＬ／Ｌより多いと触媒の除去効果が向上しないだけではなく、回路を形成した銅に対する溶解性も大きくなってしまう。 The content of nitric acid in the catalyst removing solution of the present invention (hereinafter referred to as “removing solution”) is preferably 50 to 500 mL / L, particularly preferably 100 to 400 mL / L as 67.5% nitric acid. If the nitric acid content is less than 50 mL / L, the catalyst removal effect is hardly obtained. Moreover, when it exceeds 500 mL / L, not only the removal effect of a catalyst will not improve, but the solubility with respect to the copper which formed the circuit will also become large.
また、本発明除去液における塩素イオンの供給源は、硝酸溶液中で溶解して液中に塩素イオンを生成させるもので、かつ触媒の除去能力に影響を及ぼさないものならば特に制限無く使用することができる。しかしながら、本発明除去液は高濃度の硝酸を含むため、硝酸に対して安定な無機物の方が好ましい。このような無機物としては、塩酸または塩化ナトリウム、塩化カリウム、塩化アンモニウム、塩化銅、塩化鉄、塩化ニッケル、塩化コバルト、塩化スズ、塩化亜鉛、塩化リチウム等の無機塩化物が挙げられる。これらの無機物のうち、塩酸、塩化ナトリウムが好ましい。上記塩素イオンの含有量は、塩素イオンとして１〜６０ｇ／Ｌが好ましく、特に５〜５０ｇ／Ｌが好ましい。塩素イオンの含有量が１ｇ／Ｌより少ないと触媒の除去効果がほとんど得られない。また、６０ｇ／Ｌより多いと触媒の除去効果は向上しない。 Further, the supply source of chlorine ions in the removal liquid of the present invention is not particularly limited as long as it is dissolved in a nitric acid solution to generate chlorine ions in the liquid and does not affect the removal ability of the catalyst. be able to. However, since the removal liquid of the present invention contains a high concentration of nitric acid, an inorganic substance that is stable against nitric acid is preferred. Examples of such inorganic substances include inorganic chlorides such as hydrochloric acid or sodium chloride, potassium chloride, ammonium chloride, copper chloride, iron chloride, nickel chloride, cobalt chloride, tin chloride, zinc chloride, and lithium chloride. Of these inorganic substances, hydrochloric acid and sodium chloride are preferred. The chlorine ion content is preferably 1 to 60 g / L, particularly preferably 5 to 50 g / L, as chlorine ions. If the chloride ion content is less than 1 g / L, the catalyst removal effect is hardly obtained. On the other hand, if it exceeds 60 g / L, the catalyst removal effect is not improved.
更に、本発明除去液に添加されるカチオン性ポリマーは、回路を形成する銅の溶解性を抑制するための成分である。このようなカチオン性ポリマーとしては、硝酸、塩素イオンを含有する液に対して十分な溶解性があるものが好ましく、具体的には、ポリエチレンイミン（ＰＥＩ）、ポリアミンスルホン（ＰＡＳ）、ポリビニルイミダゾール（ＰＶＩ）が挙げられる。より具体的なカチオン性ポリマーとしては、ポリエチレンイミンであれば、エポミン（日本触媒（株）製）が、ポリアミンスルホンであれば、ＰＡＳ（日東紡績（株）製）が、ポリビニルイミダゾールであれば、ＢＡＳＴＲＯＮＩＣ ＰＶＩ（ＢＡＳＦ製）がそれぞれ挙げられる。上記カチオン性ポリマーの含有量は０.０１〜５０ｇ／Ｌが好ましく、特に０.０５〜２０ｇ／Ｌが好ましい。カチオン性ポリマーの含有量が０.０１ｇ／Ｌより少ないと銅に対する溶解性を低下させる効果がほとんどなく、５０ｇ／Ｌより多いと銅に対する溶解性を低下させる効果がないばかりでなく触媒の除去効果も低下する。 Furthermore, the cationic polymer added to the removal liquid of the present invention is a component for suppressing the solubility of copper forming a circuit. As such a cationic polymer, those having sufficient solubility in a liquid containing nitric acid and chlorine ions are preferable. Specifically, polyethyleneimine (PEI), polyaminesulfone (PAS), polyvinylimidazole ( PVI). As a more specific cationic polymer, if polyethyleneimine, Epomin (manufactured by Nippon Shokubai Co., Ltd.) is polyamine sulfone, PAS (manufactured by Nitto Boseki Co., Ltd.) is polyvinyl imidazole, Examples include BATRONIC PVI (manufactured by BASF). The content of the cationic polymer is preferably from 0.01 to 50 g / L, particularly preferably from 0.05 to 20 g / L. When the content of the cationic polymer is less than 0.01 g / L, there is almost no effect of lowering the solubility in copper, and when it is more than 50 g / L, there is not only an effect of lowering the solubility in copper but also the catalyst removal effect. Also decreases.
更にまた、本発明除去液には上記各成分の他、触媒の除去に影響を与えない量で樹脂や銅への浸透性や濡れ性の向上のために通常用いられる界面活性剤やＮＯＸ抑制剤を添加することもできる。界面活性剤としては、ノニオン系のものが好ましく、具体的にはポリオキシエチレン・ポリオキシプロピレン共重合体、ポリオキシエチレンアルキルエーテルの構造のものが挙げられ、その添加量は１〜１０ｇ／Ｌが好ましい。また、ＮＯｘ抑制剤としては、尿素、スルファミン酸が挙げられ、その添加量は１〜１０ｇ／Ｌが好ましい。 Furthermore, in addition to the above components in the present invention removing solution, usually surfactants and NO X suppression used to improve the permeability and wettability of an amount that does not affect the removal of the catalyst to the resin and copper An agent can also be added. As the surfactant, nonionic surfactants are preferred, and specific examples include polyoxyethylene / polyoxypropylene copolymers and polyoxyethylene alkyl ether structures, and the addition amount is 1 to 10 g / L. Is preferred. Further, examples of the NO x inhibitor include urea and sulfamic acid, and the addition amount is preferably 1 to 10 g / L.
斯くして得られる本発明の除去液は、触媒が付着した樹脂表面に作用させることにより、触媒を除去することができる。具体的に、触媒が付着した樹脂表面から触媒を除去するには、触媒が付着している樹脂表面を含む樹脂そのものを本発明除去液に浸漬するか、触媒が付着している樹脂表面に本発明除去液をスプレー等により噴射して作用させればよい。また本発明除去剤の使用条件は、浸漬、スプレーとも、１０〜５０℃の液温で、３０秒〜３分間作用させることが好ましい。 Thus, the removal liquid of this invention obtained can remove a catalyst by making it act on the resin surface to which the catalyst adhered. Specifically, in order to remove the catalyst from the resin surface to which the catalyst is adhered, the resin itself including the resin surface to which the catalyst is adhered is immersed in the removal solution of the present invention, or the resin is adhered to the resin surface to which the catalyst is adhered. The invention removing liquid may be sprayed to act. Moreover, as for the use conditions of this invention removal agent, it is preferable to make it act for 30 second-3 minutes at the liquid temperature of 10-50 degreeC also for immersion and spray.
このような触媒が付着した樹脂表面の具体例としては、例えば、プリント配線板の製造工程において、配線基板の樹脂上にパラジウム等の触媒付与後、無電解銅めっきを行い、次いでエッチングにより不要な無電解銅めっき皮膜を取除き、回路パターンを形成した後の樹脂表面等が挙げられる。 As a specific example of the resin surface to which such a catalyst adheres, for example, in the manufacturing process of a printed wiring board, after applying a catalyst such as palladium on the resin of the wiring board, electroless copper plating is performed, and then unnecessary by etching. The resin surface etc. after removing an electroless copper plating film and forming a circuit pattern are mentioned.
以上説明した本発明除去液は、上記回路パターン形成後の樹脂表面に残存・付着したパラジウム金属等の触媒金属を、銅に対する溶解性を押さえつつ有効に除去できる。従って、例えば、配線基板の樹脂表面に金属析出触媒を付与後、無電解銅めっきを行い、その後電気銅めっきを行い、次いで不要な銅皮膜をエッチングすることにより回路パターンを形成し、その回路上に無電解金属めっきを行うプリント配線板の製造方法において、前記エッチングと無電解金属めっき工程の間に、配線基板の樹脂表面に本発明除去液を作用させておけば、プリント配線板の配線間の絶縁性を保つことが可能となる。 The removal liquid of the present invention described above can effectively remove catalyst metals such as palladium metal remaining and adhered to the resin surface after the circuit pattern is formed while suppressing solubility in copper. Therefore, for example, after applying a metal deposition catalyst to the resin surface of the wiring board, electroless copper plating is performed, then electrolytic copper plating is performed, and then an unnecessary copper film is etched to form a circuit pattern. In the method of manufacturing a printed wiring board in which electroless metal plating is performed, if the removal solution of the present invention is allowed to act on the resin surface of the wiring board between the etching and the electroless metal plating step, the wiring between the printed wiring boards It becomes possible to maintain the insulation.
また、上記プリント配線板の製造方法において、特にプリント配線板の最外層に端子部分を形成するために無電解金属めっきとして無電解ニッケルめっきや無電解金めっき等を行う場合には、本発明除去液を作用させた後に、更にブリッジ防止液を作用させることが好ましい。このブリッジ防止液を作用させることにより、本発明除去液を単独で作用させた場合よりも、より配線間が狭いものについても絶縁性を保ったまま無電解金属めっきをすることができる。 Further, in the method for manufacturing a printed wiring board, the present invention is removed particularly when electroless nickel plating or electroless gold plating is performed as electroless metal plating in order to form a terminal portion on the outermost layer of the printed wiring board. It is preferable that a bridging preventing liquid is further acted after the liquid is acted. By applying this anti-bridging solution, electroless metal plating can be performed while maintaining insulation even for a wire having a narrower distance than the case where the removal solution of the present invention is operated alone.
ここで、ブリッジ防止液とは、配線間（絶縁部）への不必要なめっきの析出を防止することができるものである。このようなブリッジ防止液は、公知のものを特に制限なく利用することができる。ブリッジ防止液として公知のものとしては、例えば、特許第３３８７５０７号に記載されているチオ硫酸ナトリウムを含有するもの等が挙げられる。これらのブリッジ防止液は、公知の方法により樹脂に作用させればよい。 Here, the bridging prevention liquid can prevent unnecessary deposition of plating between wirings (insulating part). As such an anti-bridging solution, a known one can be used without particular limitation. Examples of the known anti-bridging solution include those containing sodium thiosulfate described in Japanese Patent No. 3387507. These anti-bridging solutions may be applied to the resin by a known method.
また、ブリッジ防止液としては本発明者らが見出した、含イオウ有機物を含有するものも使用することができる。この含イオウ有機物としては、有機化合物中に硫黄原子と炭素原子を含むものであれば、特に制限されないが、チオ硫酸ナトリウム等の硫黄を含んでいても炭素原子を含まないものは含まれない。このような含イオウ有機物としてはチオ尿素誘導体、チオール類、スルフィド、チオシアン酸塩類、スルファミン酸またはその塩類が挙げられる。具体的なチオ尿素誘導体としては、チオ尿素、ジエチルチオ尿素、テトラメチルチオ尿素、１−フェニル−２−チオ尿素、チオアセトアミドが挙げられる。また、チオール類としては２−メルカプトイミダゾール、２−メルカプトチアゾリン、３−メルカプト−１，２，４−トリアゾール、メルカプトベンゾイミダゾール、メルカプトベンゾキサゾール、メルカプトベンゾチアゾール、メルカプトピリジンが挙げられる。更に、スルフィドとしては、２−アミノフェニルジスルフィド、テトラメチルチウラムジスルフィド、チオジグリコール酸が挙げられる。チオシアン酸塩類としては、チオシアン酸ナトリウム、チオシアン酸カリウム、チオシアン酸アンモニウムが挙げられる。また更に、スルファミン酸またはその塩類としては、スルファミン酸、スルファミン酸アンモニウム、スルファミン酸ナトリウム、スルファミン酸カリウムが挙げられる。これらの含イオウ有機物のうち、メルカプト基を有するチオール類またはチオシアン基を有するチオシアン酸塩が好ましい。本発明防止液における含イオウ有機物の濃度は、０.１〜１００ｇ／Ｌが好ましく、特に０.２〜５０ｇ／Ｌが好ましい。 Moreover, what contains the sulfur-containing organic substance which the present inventors discovered as bridge | bridging prevention liquid can also be used. The sulfur-containing organic substance is not particularly limited as long as it contains a sulfur atom and a carbon atom in the organic compound, but does not include an organic compound that does not contain a carbon atom even if it contains sulfur such as sodium thiosulfate. Examples of such sulfur-containing organic substances include thiourea derivatives, thiols, sulfides, thiocyanates, sulfamic acids or salts thereof. Specific examples of thiourea derivatives include thiourea, diethylthiourea, tetramethylthiourea, 1-phenyl-2-thiourea, and thioacetamide. Examples of thiols include 2-mercaptoimidazole, 2-mercaptothiazoline, 3-mercapto-1,2,4-triazole, mercaptobenzimidazole, mercaptobenzoxazole, mercaptobenzothiazole, and mercaptopyridine. Further, examples of the sulfide include 2-aminophenyl disulfide, tetramethylthiuram disulfide, and thiodiglycolic acid. Examples of thiocyanates include sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate. Still further, examples of sulfamic acid or salts thereof include sulfamic acid, ammonium sulfamate, sodium sulfamate, and potassium sulfamate. Of these sulfur-containing organic substances, thiols having a mercapto group or thiocyanate having a thiocyan group are preferable. The concentration of the sulfur-containing organic substance in the present prevention liquid is preferably 0.1 to 100 g / L, particularly preferably 0.2 to 50 g / L.
上記ブリッジ防止液は、本発明除去液を作用させるのと同様に浸漬、スプレー等でめっき前の樹脂表面に作用させればよい。浸漬、スプレーとも１０〜５０℃の液温で、１０秒〜５分作用させることが好ましい。 The bridge prevention liquid may be applied to the resin surface before plating by dipping, spraying, or the like in the same manner as the removal liquid of the present invention. Both immersion and spraying are preferably performed at a liquid temperature of 10 to 50 ° C. for 10 seconds to 5 minutes.
更に、上記ブリッジ防止液には、上記含イオウ有機物の溶解性を向上させるために、あるいは浸透性の向上等よるブリッジ防止効果の向上のために、硫酸、塩酸、リン酸等の無機酸、水酸化ナトリウム、水酸化カリウム等のアルカリ塩類、アルコール、エーテル、ケトン等の有機溶媒、アルキル硫酸化ナトリウム、ポリオキシエチレンアルキルエーテル等の界面活性剤を添加しても良い。 Furthermore, the anti-bridging solution includes an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, water, etc., in order to improve the solubility of the sulfur-containing organic substance or to improve the bridging prevention effect by improving the permeability. An alkali salt such as sodium oxide or potassium hydroxide, an organic solvent such as alcohol, ether or ketone, or a surfactant such as sodium alkyl sulfate or polyoxyethylene alkyl ether may be added.
以下、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例になんら制約されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not restrict | limited at all by these Examples.
実 施 例 １
触媒除去液の調製（１）：
表１に示す各成分を混合し、更に所定濃度となるまでの量の水を加えて各触媒除去液を調製した。
Example 1
Preparation of catalyst removal solution (1):
Each component shown in Table 1 was mixed, and an amount of water until a predetermined concentration was further added to prepare each catalyst removal solution.
比 較 例 １
比較触媒除去液の調製：
表２に示す成分を混合し、更に所定濃度となるまでの量の水を加えて各比較触媒除去液を調製した。
Comparative Example 1
Preparation of comparative catalyst removal solution:
The components shown in Table 2 were mixed, and each comparative catalyst removal solution was prepared by adding water in an amount up to a predetermined concentration.
実 施 例 ２
触媒除去試験（１）：
１０ｃｍ×５ｃｍに切断した銅張積層板（コア材：ＭＣＬ−Ｅ６７、日立化成工業（株）製）を使用し、以下のように触媒除去試験を行った。まず、上記銅張積層板上の銅箔を硫酸２００ｍＬ／Ｌ、過酸化水素１５０ｍＬ／Ｌの水溶液により剥離し、この樹脂基材に、下記の無電解銅めっき工程により、無電解銅めっきを施した。
Example 2
Catalyst removal test (1):
A copper-clad laminate (core material: MCL-E67, manufactured by Hitachi Chemical Co., Ltd.) cut to 10 cm × 5 cm was used, and a catalyst removal test was performed as follows. First, the copper foil on the copper-clad laminate is peeled off with an aqueous solution of sulfuric acid 200 mL / L and hydrogen peroxide 150 mL / L, and electroless copper plating is applied to the resin substrate by the following electroless copper plating process. did.
＜無電解銅めっき工程＞
脱脂（ＰＢ−１１９Ｓ）５０℃、５分
↓
水洗
↓
ソフトエッチ（ＰＢ−２２８）３０℃、２分
↓
水洗
↓
プリディップ（塩酸）３０℃、１分
↓
触媒付与（ＰＢ−３１８）３０℃、５分
↓
水洗
↓
アクセラレーター（ＰＢ−４４５）３０℃、５分
↓
水洗
↓
無電解銅めっき（ＰＢ−５０３）３０℃、１５分
（塩酸以外の薬品は何れも荏原ユージライト（株）製）
<Electroless copper plating process>
Degreasing (PB-119S) 50 ° C, 5 minutes ↓
Washing with water ↓
Soft etch (PB-228) 30 ° C, 2 minutes ↓
Washing with water ↓
Pre-dip (hydrochloric acid) 30 ° C, 1 minute ↓
Catalyst application (PB-318) 30 ° C, 5 minutes ↓
Washing with water ↓
Accelerator (PB-445) 30 ° C, 5 minutes ↓
Washing with water ↓
Electroless copper plating (PB-503) 30 ° C, 15 minutes
(All chemicals other than hydrochloric acid are manufactured by Ebara Eugleite Co., Ltd.)
上記で得られた無電解銅めっき皮膜を硫酸２００ｍＬ／Ｌ、過酸化水素１５０ｍＬ／Ｌの水溶液に浸漬して剥離し、樹脂基材表面にパラジウム触媒が残存する試験片１を得た。また、銅張積層板（コア材）を試験片２とした。 The electroless copper plating film obtained above was immersed in an aqueous solution of 200 mL / L sulfuric acid and 150 mL / L of hydrogen peroxide and peeled to obtain a test piece 1 in which the palladium catalyst remained on the resin substrate surface. A copper clad laminate (core material) was used as test piece 2.
表１および表２に示す各除去液を３０℃に加温し、これに各試験片を１分間浸漬し、各除去液のパラジウム除去能力、および銅に対する溶解性を調べた。パラジウムの除去能力は、試験片１を除去液に浸漬した後に再度無電解銅めっき液に浸漬したときの表面への銅の再析出状況を観察することにより調べた。また、銅に対する溶解性は、試験片２の除去液の処理前後の重量変化から求めた。更に、試験片１に付着しているパラジウム量を求め、１０ｄｍ２／Ｌ処理時に相当する量を順次加えながら試験片２を処理し、パラジウム析出による銅の変色が認められた時点のパラジウム濃度から処理量を調べた。その結果を表３に示した。 Each removal liquid shown in Table 1 and Table 2 was heated to 30 ° C., and each test piece was immersed in this for 1 minute, and the palladium removal ability of each removal liquid and the solubility in copper were examined. The ability to remove palladium was examined by observing the state of reprecipitation of copper on the surface when the test piece 1 was immersed in the electroless copper plating solution after being immersed in the removal solution. Moreover, the solubility with respect to copper was calculated | required from the weight change before and behind the process of the removal liquid of the test piece 2. FIG. Further, the amount of palladium adhering to the test piece 1 is obtained, the test piece 2 is treated while sequentially adding the corresponding amount at the time of 10 dm 2 / L treatment, and from the palladium concentration at the time when discoloration of copper due to palladium deposition is observed. The throughput was examined. The results are shown in Table 3.
以上の結果より、本発明除去液は比較除去液と比べて、触媒の除去能力が高いだけでなく、銅に対する溶解性も低く、置換析出も起こりにくいことから、長期間繰り返し使用することができる優れたものであることがわかった。 From the above results, the removal solution of the present invention not only has a high catalyst removal ability but also has a low solubility in copper and is less likely to cause precipitation of substitution compared to the comparative removal solution, so that it can be used repeatedly for a long time. It turned out to be excellent.
実 施 例 ３
触媒除去液の調製（２）：
表４に示す各成分を混合し、更に所定濃度となるまでの量の水を加えて各触媒除去液を調製した。
Example 3
Preparation of catalyst removal solution (2):
Each component shown in Table 4 was mixed, and each catalyst removal solution was prepared by adding an amount of water up to a predetermined concentration.
実 施 例 ４
触媒除去試験（２）：
銅張積層板（コア材：日立化成製、ＭＣＬ−Ｅ６７）上の銅箔を２００ｍＬ／Ｌ、過酸化水素１５０ｍＬ／Ｌの水溶液により剥離した樹脂基材を用い、これをセミアディティブ法により処理し、ライン／スペース（Ｌ／Ｓ）＝５０／５０、７５／７５、１００／１００（μｍ）の３種類の銅配線パターンを有する試験片３を作成した。
Example 4
Catalyst removal test (2):
Using a resin base material in which the copper foil on the copper clad laminate (core material: MCL-E67 manufactured by Hitachi Chemical Co., Ltd.) is peeled off with an aqueous solution of 200 mL / L and hydrogen peroxide 150 mL / L, this is treated by the semi-additive method. A test piece 3 having three types of copper wiring patterns of line / space (L / S) = 50/50, 75/75, and 100/100 (μm) was prepared.
表４に示す各除去液を３０℃に加温し、これの何れか一方に試験片３を１分間浸漬した。次いで、試験片３をブリッジ防止液（チオ硫酸ナトリウム（５０ｇ／Ｌ）またはチオシアン酸カリウム（１ｇ／Ｌ））を３０℃に加温したものに１分間浸漬した。更に、試験片３を乾燥させた後、下記の無電解ニッケルめっき工程により、無電解ニッケルめっきを施した。 Each removal liquid shown in Table 4 was heated to 30 ° C., and the test piece 3 was immersed in one of these for 1 minute. Next, the test piece 3 was immersed in a bridging prevention solution (sodium thiosulfate (50 g / L) or potassium thiocyanate (1 g / L)) heated to 30 ° C. for 1 minute. Furthermore, after drying the test piece 3, electroless nickel plating was performed by the following electroless nickel plating process.
＜無電解ニッケルめっき工程＞
酸性脱脂（ＰＢ−２４２Ｄ）、４５℃、５分
↓
水洗
↓
ソフトエッチ（ＰＢ−２２８）、３０℃、１分
↓
水洗
↓
スマット除去（硫酸）、３０℃、１分
↓
水洗
↓
触媒付与（ＰＢ−３００）、３０℃、３分
↓
水洗
↓
無電解ニッケルめっき（エニパックＡＣ−ＤＸ）、８５℃、２０分
（硫酸以外の薬品は何れも荏原ユージライト（株）製）
<Electroless nickel plating process>
Acid degreasing (PB-242D), 45 ° C, 5 minutes ↓
Washing with water ↓
Soft etch (PB-228), 30 ° C, 1 minute ↓
Washing with water ↓
Smut removal (sulfuric acid), 30 ° C, 1 minute ↓
Washing with water ↓
Catalyst application (PB-300), 30 ° C, 3 minutes ↓
Washing with water ↓
Electroless nickel plating (Enipack AC-DX), 85 ° C, 20 minutes
(All chemicals other than sulfuric acid are manufactured by Ebara Eugleite Co., Ltd.)
無電解ニッケルめっきを施した試験片３の各パターン間のめっき析出状態を調べ、下記評価基準により評価した。また、比較として触媒除去液およびブリッジ防止液に浸漬しなかったもの（未処理）とブリッジ防止液のみに浸漬したものについても同様に調べ、評価した。その結果を表５に示した。 The plating deposition state between each pattern of the test piece 3 subjected to electroless nickel plating was examined and evaluated according to the following evaluation criteria. Further, as a comparison, those not immersed in the catalyst removal liquid and the bridge prevention liquid (untreated) and those immersed only in the bridge prevention liquid were also examined and evaluated in the same manner. The results are shown in Table 5.
＜めっき析出状態の評価基準＞
（評 価） （状 態）
◎ ： ほとんど析出がない
○ ： 部分的に析出がある（短絡はなし）
× ： 析出が多い（短絡がある）
×× ： 全面的に析出がある
<Evaluation criteria for plating deposition state>
(Evaluation) (State)
◎: Almost no precipitation ○: Partial precipitation (no short circuit)
×: A lot of precipitation (there is a short circuit)
XX: Precipitation is entirely present
以上の結果より、本発明除去液のみで触媒を除去した樹脂に無電解ニッケルめっきを施した場合は、配線間が狭いと短絡が生じていたが、本発明除去液により触媒を除去した後に、更にブリッジ防止液を作用させた樹脂に無電解ニッケルめっきを施した場合は、配線間が狭い場合であってもほとんど析出もなく短絡も生じないことがわかった。 From the above results, when electroless nickel plating was applied to the resin from which the catalyst was removed only with the present removal solution, a short circuit occurred when the wiring was narrow, but after removing the catalyst with the present removal solution, Furthermore, it was found that when electroless nickel plating was applied to a resin to which an anti-bridging solution was applied, even when the distance between wirings was narrow, there was almost no precipitation and no short circuit occurred.
本発明除去液は、樹脂表面に付着した触媒を完全に除去することができるため、配線間の高い絶縁性が要求される多層プリント配線板の製造に利用することができる。
以 上
Since the removal liquid of the present invention can completely remove the catalyst adhering to the resin surface, it can be used for manufacturing a multilayer printed wiring board that requires high insulation between wirings.
more than
Claims (7)
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| JPWO2011099597A1 (en) * | 2010-02-15 | 2013-06-17 | 株式会社Ｊｃｕ | Method for manufacturing printed wiring board |
| JP5911145B2 (en) * | 2010-12-03 | 2016-04-27 | 株式会社Ｊｃｕ | Etching solution maintenance method |
| KR20130048103A (en) * | 2011-11-01 | 2013-05-09 | 삼성전기주식회사 | Method for preparing the printed circuit board |
| ES2727075T5 (en) * | 2015-02-23 | 2022-05-27 | Macdermid Enthone Inc | Inhibiting composition for frames when chrome-free mordants are used in a galvanizing process on plastic materials |
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