JPH0578414B2 - - Google Patents
Info
- Publication number
- JPH0578414B2 JPH0578414B2 JP60015807A JP1580785A JPH0578414B2 JP H0578414 B2 JPH0578414 B2 JP H0578414B2 JP 60015807 A JP60015807 A JP 60015807A JP 1580785 A JP1580785 A JP 1580785A JP H0578414 B2 JPH0578414 B2 JP H0578414B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- laminate
- amino
- metal
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910001431 copper ion Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 8
- VURKRJGMSKJIQX-UHFFFAOYSA-N xanthopterin Chemical compound N1C(=O)C=NC2=C1C(=O)N=C(N)N2 VURKRJGMSKJIQX-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- -1 penzoguanamine Chemical compound 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims description 4
- NHIKDNWKXUBYHV-UHFFFAOYSA-N 2,3-dihydro-1h-isoindole-5-carbonitrile Chemical compound N#CC1=CC=C2CNCC2=C1 NHIKDNWKXUBYHV-UHFFFAOYSA-N 0.000 claims description 3
- LPXQRXLUHJKZIE-UHFFFAOYSA-N 8-azaguanine Chemical compound NC1=NC(O)=C2NN=NC2=N1 LPXQRXLUHJKZIE-UHFFFAOYSA-N 0.000 claims description 3
- 229960005508 8-azaguanine Drugs 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000002894 organic compounds Chemical group 0.000 claims description 3
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 claims description 3
- SILNNFMWIMZVEQ-UHFFFAOYSA-N 1,3-dihydrobenzimidazol-2-one Chemical compound C1=CC=C2NC(O)=NC2=C1 SILNNFMWIMZVEQ-UHFFFAOYSA-N 0.000 claims description 2
- QYNFYHMIUAYDRE-UHFFFAOYSA-N 1-(methylamino)-3-phenoxypropan-2-ol Chemical compound CNCC(O)COC1=CC=CC=C1 QYNFYHMIUAYDRE-UHFFFAOYSA-N 0.000 claims description 2
- PJUPKRYGDFTMTM-UHFFFAOYSA-N 1-hydroxybenzotriazole;hydrate Chemical compound O.C1=CC=C2N(O)N=NC2=C1 PJUPKRYGDFTMTM-UHFFFAOYSA-N 0.000 claims description 2
- XBTOSRUBOXQWBO-UHFFFAOYSA-N 1h-indazol-5-amine Chemical compound NC1=CC=C2NN=CC2=C1 XBTOSRUBOXQWBO-UHFFFAOYSA-N 0.000 claims description 2
- SWELIMKTDYHAOY-UHFFFAOYSA-N 2,4-diamino-6-hydroxypyrimidine Chemical compound NC1=CC(=O)N=C(N)N1 SWELIMKTDYHAOY-UHFFFAOYSA-N 0.000 claims description 2
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 claims description 2
- DUFGYCAXVIUXIP-UHFFFAOYSA-N 4,6-dihydroxypyrimidine Chemical compound OC1=CC(O)=NC=N1 DUFGYCAXVIUXIP-UHFFFAOYSA-N 0.000 claims description 2
- CLGFIVUFZRGQRP-UHFFFAOYSA-N 7,8-dihydro-8-oxoguanine Chemical compound O=C1NC(N)=NC2=C1NC(=O)N2 CLGFIVUFZRGQRP-UHFFFAOYSA-N 0.000 claims description 2
- QEUYATCJHJUQML-UHFFFAOYSA-N acridine-3,6-diamine;10-methylacridin-10-ium-3,6-diamine;chloride;hydrochloride Chemical compound Cl.[Cl-].C1=CC(N)=CC2=NC3=CC(N)=CC=C3C=C21.C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 QEUYATCJHJUQML-UHFFFAOYSA-N 0.000 claims description 2
- 229940002707 acriflavine hydrochloride Drugs 0.000 claims description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims 1
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical group OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 claims 1
- 238000011282 treatment Methods 0.000 description 40
- 238000000034 method Methods 0.000 description 22
- 239000011889 copper foil Substances 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000007788 roughening Methods 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 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 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 229960003280 cupric chloride Drugs 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- SZOJMCCLOONRGD-UHFFFAOYSA-N 1h-perimidin-2-amine;hydrochloride Chemical compound Cl.C1=CC(NC(N)=N2)=C3C2=CC=CC3=C1 SZOJMCCLOONRGD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 2
- 229960002218 sodium chlorite Drugs 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Description
（産業上の利用分野）
本発明は、導体金属による内層回路が形成され
た配線板をプリプレグを介して多層とする多層プ
リント配線板等のような金属と樹脂層との積層体
の製造法に関する。
（従来の技術）
多層プリント配線板は、次のようにして製造さ
れる。すなわち、
通常の銅張積層板の銅箔を加工してプリント
配線を形成することにより内層用銅張積層板を
つくり、この銅箔を過硫酸アンモニウム、塩化
第２銅、酢酸銅等の薬液で処理して銅箔表面を
粗面化したのち、この内層用銅張積層板に熱硬
化性樹脂含浸基材（プリプレグ）を介して外層
用銅張積層板を積層接着する。
銅箔の両面を粗化して接着性等を向上した銅
箔（両面粗化銅箔）を用いた銅張積層板をと
同様の方法で内層用銅張積層板をつくり、この
銅箔表面の粗面化はおこなわないで、この内層
用銅張積層板にプリプレグを介して外層用銅張
積層板を積層接着する。
と同様の方法で内層用銅張積層板をつく
り、と同様の薬液で処理して銅箔表面を粗面
化し、更に亜塩素酸ナトリウム系処理液で処理
したのち、この内層用銅張積層板にプリプレグ
を介して外層用銅張積層板を積層接着すること
によつて製造していた。
（発明が解決しようとする問題点）
これらの方法には次のような問題があつた。
の方法で製造した多層配線板は、内層銅箔と
プリプレグを硬化させた樹脂層との接着強度が
不十分である。また、完成した多層印刷回路板
に各種の電子部品を半田で固定する工程におい
て、回路銅箔と積層板との間で剥離が生じた
り、場合によつてはこの剥離が外部から肉眼で
確認される程の板のふくれとなつて現われるこ
とがあつた。
の方法では、両面粗化銅箔を使用するので、
内層用銅張積層板のプリント配線を形成するま
での工程で、粗化表面をきずつけることがあ
り、その場合、きずつけた部分では接着力が低
下する。また、プリント配線形成に使用する印
刷エツチングレジストやUV写真焼き付け方法
によるエツチングレジストのパターン精度が、
銅箔表面が粗面であるために劣つていた。
の方法で製造した多層配線板はスルーホール
めつきのためのスルーホール壁面へのめつき触
媒付与の工程での酸性溶液によつて、またスル
ーホールのドリル穴明け時に内層銅の切削断面
には付着する樹脂状物の除去工程で用いる酸性
溶液によつて、また無電解銅めつき液などによ
つて、これらの溶液が酸化皮膜形成層と絶縁樹
脂層の間にしみ込み、接着性や導体間の絶縁抵
抗が低下するという問題があつた。
本発明は、金属と樹脂層との接着力に優れる金
属と樹脂層との積層体の製造法を提供するもので
ある。
（問題点を解決するための手段）
本発明は、金属表面を、
銅イオン、銅イオンの錯化剤、銅イオンの還
元剤、PH調整剤、水、
および
分子内に−Ｎ＝と、−NH2および／または−
OHとをもつ有機化合物の少なくとも一種、
を含む無電解銅めつき液（以下処理液Ａという）
で銅めつきを行つた後、樹脂層と接着することを
特徴とするものである。
本発明において処理される金属の１例である内
層配線付積層板の配線パターンの導体は銅張積層
板をエツチングして得たもの、銅電気めつき、無
電解銅めつきおよびこれらを組み合せて得たもの
のいずれであつても良い。上記の銅の表面処理の
前工程として、内層配線付積層板の配線パターン
等の表面の“粗し”を目的として水、塩酸、硫
酸、リン酸、さく酸、塩化第２銅、硫酸銅などの
銅化合物、塩化第２鉄、硫酸第２鉄などの鉄化合
物、アルカリ金属塩化物、過硫酸アンモンなどか
ら選ばれる化合物の組み合せからなる水溶液で処
理しても良い。またこれらの化学的な方法の“粗
し”ではなく、液体ホーニング、研磨などの機械
的な方法でおこなつても良い。また処理される金
属表面としては、銅以外の金属たとえば、ステン
レスステイール、ニツケル、鉄等であつても良
い。これらの金属の場合は、本発明の処理の前工
程として、処理反応を均一にするために通常の無
電解めつき用触媒を付与しても良い。
本発明の処理液Ａにおいて、銅イオンは銅イオ
ン源として硫酸銅、硝酸銅、塩化第２銅など通常
の銅塩が用いられる。錯化剤としては上記の銅イ
オンと錯体を形成しアルカリ水溶液に可溶とする
ものでエチレンジアミン四酢酸、クアドロール
（アデカ製商品名）、酒石酸などが用いられる。還
元剤としては、ホルマリン、次亜リン酸塩などが
ある。また水酸イオンはこの処理液のPHを調整す
る目的で添加するもので水酸化ナトリウム、水酸
化カリウムなどが使用できる。水としてはイオン
交換水が望ましい。これらの成分から成る処理液
Ａの基本組成としては、例えば硫酸銅２ｇ／〜
20ｇ／、PH11.0〜13.5、錯化剤としてエチレン
ジアミン四酢酸の場合では硫酸銅濃度の1.0〜5.0
倍モル濃度、また還元剤としての37％ホルマリン
は２ml／〜20ml／が好ましい。
より一般的には銅イオンは0.004〜0.2モル／
、銅イオンの錯化剤は0.004〜0.1モル／、銅
イオンの還元剤は0.01〜0.25モル／、PH調整剤
はPHを11.0〜13.4にする量使用される。
分子内に−Ｎ＝と、−NH2および／または−
OHとをもつ有機化合物としては、８−アザグア
ニン、キサントプテリン、５−アミノインダゾー
ル、２−アミノペリジン塩酸塩、２−アミノペリ
ミジン臭化水素酸塩、ペンゾグアナミン、アクリ
フラビン塩酸塩、５−アミノ−IH−テトラゾル、
６−アミノ−２−フエニル−４−キノリル、２−
アミノ−６，８−ジヒドロキシプリン、２−アミ
ノピリミジン、６−ヒドロキシ−２，４，５−ト
リアミノピリミジン硫酸塩、２，４−ジアミノ−
６−ヒドロキシピリミジン、２−アミノ−４−ヒ
ドロキシ−６−メチルピリミジン、４，６−ジヒ
ドロキシピリミジン、ニトログアニジン、１−ヒ
ドロキシ−IH−ベンゾトリアゾール１水塩、２
−ヒドロキシベンズイミダゾール、３−アミノ−
３−ヒドロキシピリミジンなど及びこれらの混合
物がある。
添加量としては0.1mg／以上で良い。これら
の薬品は比較的高価なものが多いため、多量に添
加することはコストの点から好ましくはない。一
般的には１mg／から500mg／の範囲が好まし
い。
これらの薬品類は(株)同仁化学研究所や東京化成
工業(株)アルドリツチ社などから市販薬品として入
手できる。
処理液Ａの温度は処理液ＡのPHや還元剤の濃度
と主に関係しており、PHや還元剤濃度が高い場合
には低温でも処理可能になる。したがつて、処理
液の組成によつて室温から90℃までの範囲で選ぶ
ことができる。
処理時間は処理液Ａのめつき析出速度と関係す
る。又処理工程は短い方が好ましいので、一般的
には処理液への浸漬時間は１分間〜60分間であ
る。
導体金属による内層回路が形成された配線板
を、以上説明した処理液Ａで処理し、導体金属に
銅めつきを形成した後、その必要枚数を、紙、ガ
ラス布等の基材に熱硬化性樹脂を含浸、乾溶した
プリプレグを重ね合せて加熱加圧一体化して多層
プリント配線板を製造する。導体金属に形成され
る銅めつきの厚みは１〜5μｍが好ましい。
以上、金属と樹脂層との積層体として内層用配
線板とプリプレグを接着した多層プリント配線板
について説明したが、金属と樹脂層との積層体と
して、銅張積層板とその銅はく面に形成されるエ
ツチング、めつきレジストとの積層体導体回路が
形成された配線板とその表面に形成される半田レ
ジストとの積層体、銅はくとプリプレグとを積層
した銅張積層板、銅はくとフレキシブルフイルム
を積層したフレキシブル配線板用基板等がある。
内層回路をエツチング法やアデイテイブ法で形
成したのち、処理液Ａの処理を行い、スクリーン
印刷、カーテンコート法やホツトロールラミネー
ト法で絶縁性樹脂例えばレジストインクや接着材
を塗布または付着させることにより銅回路を上記
材料との間の密着力を確保することができる。こ
のようにして得られたものの外層に従来法で導体
を形成すれば多層板をプレス工程なしで製造する
ことができる。
樹脂層としては、プリプレグ、フイルム、カー
テンコート層等の形状で、材質としてはフエノー
ル、エポキシ、ポリエステル、ポリイミドなどの
熱硬化性樹脂およびテフロン、ポリサルフオン、
ポリエーテルカルフオン、ポリエーテルイミドな
どの熱可塑性樹脂も使用出来る。
処理液Ａで処理し金属表面に無光沢で暗色の銅
めつきを形成させる。太陽光の300〜800nｍに於
ける平均吸収率で0.5以上、好ましくは0.7以上で
ある。
金属を処理液Ａによる処理でも充分であるが、
処理表面と樹脂の接着力をより向上させたい場合
は、上記方法で処理した後、更に還元剤を含む水
溶液、酸溶液およびアンモニア水の少なくとも１
種以上の処理液Ｂで処理すれば良い。
還元剤を含む水溶液Ｂの還元剤は、ホルムアル
デヒド、パラホルムアルデヒド、次亜リン酸およ
び次亜リン酸塩などが用いられる。ホルムアルデ
ヒド、パラホルムアルデヒドの場合は還元性を付
与するために水溶液のPHを9.0〜13.5の範囲のア
ルカリ性にする。これらの還元剤の水溶液には銅
の錯化剤を添加しても良い。また、銅の塩類、水
酸イオン、銅の錯化剤、ホルマリンを含む無電解
銅めつき液で銅の塩類の濃度が低くて、無電解銅
めつき反応がほとんど進行しない溶液を用いても
処理することができる。これらの場合において
も、還元剤等の濃度、溶液の温度および処理時間
は処理液Ａの処理で得た無光沢で暗色の表面が残
る範囲でこの処理表面と樹脂の接着力が最大にな
る条件を選べば良い。
酸溶液としては塩酸溶液、硫酸溶液、過硫酸ア
ンモニウム溶液等を用いることができる。これら
の溶液Ｂの濃度、溶液の温度および処理時間は処
理液Ａの処理で得た無光沢で暗色の表面が残る範
囲で、この処理表面と樹脂の接着力が最大になる
条件を選べば良い。
アンモニア水の濃度、温度および処理時間は処
理液Ａの処理で得た無光沢で暗色の表面が残る範
囲でこの処理表面と樹脂の接着力が最大になる条
件を選べば良い。
これらの処理は処理液Ｂ中に内層配線付積層板
を浸漬することによつておこなつても良いし、又
処理液Ｂをスプレーすることなどによつておこな
つても良い。
実施例 １
エポキシ樹脂を使用した銅張積層板をあらかじ
め過硫酸アンモニウムで粗化処理した。次に基本
浴組成(A)に、それぞれペンゾグアナミン、８−ア
ザグアニン、キサントプテリン、２−アミノペリ
ミジン塩酸塩、２アミノピリミジン、６−ヒドロ
キシ−２、４、５−トリアミノピリミジン硫酸
塩、ニトログアニジンを10mg／を単独添加した
処理液（70±２℃）に５分間浸漬した。
基本浴組成(A)
CuSO4・5H2O＝10ｇ／
EDTA・2Na＝40ｇ／
PH＝12.5（室温、NaOHを用いて調整）
37％HCHO＝４ml／
純水＝総量で１になる量
処理して得た銅の表面の色、処理面の接着力テ
ストであるテープテストおよび処理後、接着力が
低下しないで積層接着できる可使時間の長さを示
す保存性の試験結果を表１に示す。テープテスト
は、10mm幅の粘着剤付きマイラーテープ（日東電
工製）を処理表面に貼り付け、貼り付けたテープ
が透明になるまでテープを処理面に密着させ、そ
の後ゆつくりとひきはがし、粘着剤の処理表面へ
の残り量を調べる方法である。残り量が多い処理
面ほど、多層プリント配線板を製造した時の接着
力が高い。判定基準は粘着剤の残らなかつたもの
を×、わずかに残つたものを△、半分ぐらい残つ
たものを○、全面にわたつて残つたものを◎とし
た。
保存性は、常温、常湿で７日間放置後、前記の
テープテストを行い、粘着剤の処理表明への残り
量をテープテストと同様の評価で調べることによ
り行つた。
比較例 １
エポキシ樹脂を使用した銅張積層板を過硫酸ア
ンモニウムで粗化処理した。この銅の表面の色、
テープテストおよび保存性を調べた結果を表１に
示す。
(Industrial Application Field) The present invention relates to a method for manufacturing a laminate of metal and resin layers, such as a multilayer printed wiring board, in which a wiring board on which an inner layer circuit made of conductive metal is formed is multilayered via prepreg. . (Prior Art) A multilayer printed wiring board is manufactured as follows. In other words, a copper-clad laminate for the inner layer is made by processing the copper foil of a normal copper-clad laminate to form printed wiring, and then this copper foil is treated with a chemical solution such as ammonium persulfate, cupric chloride, or copper acetate. After roughening the surface of the copper foil, a copper-clad laminate for the outer layer is laminated and bonded to the copper-clad laminate for the inner layer via a thermosetting resin-impregnated base material (prepreg). A copper-clad laminate for the inner layer was made using a copper-clad laminate using copper foil whose adhesion properties were improved by roughening both sides of the copper foil (double-sided roughened copper foil). Without roughening, the copper-clad laminate for the outer layer is laminated and bonded to the copper-clad laminate for the inner layer via the prepreg. A copper-clad laminate for the inner layer was made in the same manner as above, the surface of the copper foil was roughened by treatment with the same chemical solution, and then treated with a sodium chlorite-based treatment solution. It was manufactured by laminating and bonding a copper-clad laminate for the outer layer to the outer layer through prepreg. (Problems to be solved by the invention) These methods had the following problems. The multilayer wiring board manufactured by the above method has insufficient adhesive strength between the inner layer copper foil and the resin layer made of hardened prepreg. In addition, during the process of fixing various electronic components to the completed multilayer printed circuit board with solder, peeling may occur between the circuit copper foil and the laminate, and in some cases, this peeling may be visible from the outside with the naked eye. In some cases, it appeared as a bulge in the board. The method uses double-sided roughened copper foil, so
The roughened surface may be damaged during the process of forming the printed wiring of the copper-clad laminate for the inner layer, and in this case, the adhesive strength will be reduced in the damaged area. In addition, the pattern accuracy of the printed etching resist used for forming printed wiring and the etching resist produced by the UV photo printing method is
It was inferior because the surface of the copper foil was rough. The multilayer wiring board manufactured by the above method is coated with an acidic solution during the process of applying a plating catalyst to the wall surface of the through-hole for through-hole plating, and also adheres to the cut cross section of the inner layer copper when drilling the through-hole. Due to the acidic solution used in the resin-like material removal process, or electroless copper plating solution, these solutions seep into the space between the oxide film forming layer and the insulating resin layer, resulting in poor adhesion and problems between conductors. There was a problem that the insulation resistance of the The present invention provides a method for manufacturing a laminate of metal and resin layers that has excellent adhesive strength between the metal and resin layers. (Means for Solving the Problems) The present invention provides a method for treating a metal surface with copper ions, a complexing agent for copper ions, a reducing agent for copper ions, a PH regulator, water, and -N= in the molecule, - NH2 and/or −
An electroless copper plating solution (hereinafter referred to as treatment solution A) containing at least one kind of organic compound having OH.
It is characterized by being bonded to the resin layer after copper plating is performed. The conductor of the wiring pattern of the laminate with inner layer wiring, which is an example of the metal treated in the present invention, is obtained by etching a copper-clad laminate, copper electroplating, electroless copper plating, or a combination thereof. It can be anything you get. As a pre-process for the copper surface treatment mentioned above, water, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, cupric chloride, copper sulfate, etc. are used to roughen the surface of the wiring pattern of the laminate with inner layer wiring. The treatment may be carried out with an aqueous solution consisting of a combination of compounds selected from copper compounds, iron compounds such as ferric chloride and ferric sulfate, alkali metal chlorides, and ammonium persulfate. Moreover, instead of these chemical methods of "roughening", mechanical methods such as liquid honing and polishing may be used. Further, the metal surface to be treated may be a metal other than copper, such as stainless steel, nickel, or iron. In the case of these metals, a usual catalyst for electroless plating may be applied as a pre-step to the treatment of the present invention in order to make the treatment reaction uniform. In the treatment solution A of the present invention, common copper salts such as copper sulfate, copper nitrate, and cupric chloride are used as copper ion sources. The complexing agent is one that forms a complex with the above-mentioned copper ion and becomes soluble in an alkaline aqueous solution, such as ethylenediaminetetraacetic acid, Quadrol (trade name, manufactured by Adeka), tartaric acid, and the like. Examples of reducing agents include formalin and hypophosphite. Further, hydroxide ions are added for the purpose of adjusting the pH of this treatment solution, and sodium hydroxide, potassium hydroxide, etc. can be used. Ion-exchanged water is preferable as water. The basic composition of treatment liquid A consisting of these components is, for example, copper sulfate 2 g/~
20g/, pH 11.0-13.5, copper sulfate concentration 1.0-5.0 in the case of ethylenediaminetetraacetic acid as a complexing agent
Double molar concentration, and 37% formalin as a reducing agent is preferably 2 ml/~20 ml/. More generally copper ions are 0.004 to 0.2 mol/
The copper ion complexing agent is used in an amount of 0.004 to 0.1 mol/, the copper ion reducing agent is used in an amount of 0.01 to 0.25 mol/, and the pH adjuster is used in an amount to adjust the pH to 11.0 to 13.4. -N= in the molecule, -NH 2 and/or -
Organic compounds with OH include 8-azaguanine, xanthopterin, 5-aminoindazole, 2-aminoperidine hydrochloride, 2-aminoperimidine hydrobromide, penzoguanamine, acriflavine hydrochloride, 5-aminoperidine hydrochloride, Amino-IH-tetrasol,
6-amino-2-phenyl-4-quinolyl, 2-
Amino-6,8-dihydroxypurine, 2-aminopyrimidine, 6-hydroxy-2,4,5-triaminopyrimidine sulfate, 2,4-diamino-
6-hydroxypyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine, 4,6-dihydroxypyrimidine, nitroguanidine, 1-hydroxy-IH-benzotriazole monohydrate, 2
-Hydroxybenzimidazole, 3-amino-
3-hydroxypyrimidine, etc. and mixtures thereof. The amount added may be 0.1 mg/or more. Since many of these chemicals are relatively expensive, it is not preferable to add them in large amounts from the viewpoint of cost. Generally, a range of 1 mg/ to 500 mg/ is preferred. These chemicals are available as commercial chemicals from Dojindo Kagaku Kenkyusho Co., Ltd., Tokyo Kasei Kogyo Co., Ltd., Aldrich Co., Ltd., and others. The temperature of the treatment liquid A is mainly related to the pH of the treatment liquid A and the concentration of the reducing agent, and when the pH and the concentration of the reducing agent are high, the treatment can be performed even at a low temperature. Therefore, the temperature can be selected from room temperature to 90°C depending on the composition of the processing solution. The treatment time is related to the plating deposition rate of treatment solution A. Further, since it is preferable that the treatment step be short, the immersion time in the treatment liquid is generally 1 minute to 60 minutes. A wiring board on which an inner layer circuit made of conductive metal is formed is treated with processing liquid A described above to form copper plating on the conductive metal, and then the required number of sheets are heat-cured onto a base material such as paper or glass cloth. A multilayer printed wiring board is manufactured by stacking prepregs impregnated and dry-dissolved with a synthetic resin and integrating them under heat and pressure. The thickness of the copper plating formed on the conductive metal is preferably 1 to 5 μm. Above, a multilayer printed wiring board in which an inner layer wiring board and a prepreg are bonded together as a laminate of metal and a resin layer has been described. A laminate of a wiring board with a conductor circuit formed thereon and a solder resist formed on its surface, a copper-clad laminate made of a laminate of a copper foil and a prepreg, There are substrates for flexible wiring boards, etc., which are laminated with flexible films. After forming the inner layer circuit by an etching method or an additive method, it is treated with processing solution A, and an insulating resin such as a resist ink or an adhesive is applied or adhered by screen printing, curtain coating, or hot roll laminating to form copper. Adhesion between the circuit and the above material can be ensured. If a conductor is formed on the outer layer of the product thus obtained by a conventional method, a multilayer board can be manufactured without a pressing process. The resin layer is in the form of prepreg, film, curtain coat layer, etc., and the material is thermosetting resins such as phenol, epoxy, polyester, polyimide, Teflon, polysulfon, etc.
Thermoplastic resins such as polyether calfon and polyetherimide can also be used. Treat with treatment solution A to form a matte, dark copper plating on the metal surface. The average absorption rate of sunlight in the wavelength range of 300 to 800 nm is 0.5 or more, preferably 0.7 or more. Although it is sufficient to treat the metal with treatment solution A,
If it is desired to further improve the adhesion between the treated surface and the resin, after the above treatment, at least one of an aqueous solution containing a reducing agent, an acid solution and aqueous ammonia is added.
The treatment may be performed using more than one type of treatment liquid B. As the reducing agent of the aqueous solution B containing a reducing agent, formaldehyde, paraformaldehyde, hypophosphorous acid, hypophosphite, etc. are used. In the case of formaldehyde and paraformaldehyde, the pH of the aqueous solution is made alkaline in the range of 9.0 to 13.5 in order to impart reducing properties. A copper complexing agent may be added to the aqueous solution of these reducing agents. In addition, even if an electroless copper plating solution containing copper salts, hydroxide ions, a copper complexing agent, and formalin is used, the concentration of copper salts is low and the electroless copper plating reaction hardly progresses. can be processed. In these cases, the concentration of the reducing agent, temperature of the solution, and treatment time are such that the adhesive strength between the treated surface and the resin is maximized while the matte, dark-colored surface obtained by treatment with treatment solution A remains. All you have to do is choose. As the acid solution, a hydrochloric acid solution, a sulfuric acid solution, an ammonium persulfate solution, etc. can be used. The concentration of Solution B, the temperature of the solution, and the treatment time should be selected so that the matte, dark-colored surface obtained by treatment with Treatment Solution A remains, and the conditions that maximize the adhesion between the treated surface and the resin can be selected. . The concentration, temperature, and treatment time of the ammonia water may be selected from conditions that maximize the adhesion between the treated surface and the resin within a range in which the matte, dark-colored surface obtained by treatment with treatment liquid A remains. These treatments may be performed by immersing the laminate with inner layer wiring in the treatment liquid B, or by spraying the treatment liquid B. Example 1 A copper-clad laminate using an epoxy resin was roughened in advance with ammonium persulfate. Next, the basic bath composition (A) was added to penzoguanamine, 8-azaguanine, xanthopterin, 2-aminoperimidine hydrochloride, 2-aminopyrimidine, 6-hydroxy-2,4,5-triaminopyrimidine sulfate, respectively. , and immersed for 5 minutes in a treatment solution (70±2°C) to which 10 mg of nitroguanidine was added alone. Basic bath composition (A) CuSO 4・5H 2 O = 10g / EDTA・2Na = 40g / PH = 12.5 (room temperature, adjusted using NaOH) 37% HCHO = 4ml / Pure water = amount that makes the total amount 1 Treated Table 1 shows the color of the surface of the copper obtained, the tape test that tests the adhesive strength of the treated surface, and the shelf life test that shows the length of pot life during which lamination can be bonded without decreasing adhesive strength after treatment. . In the tape test, a 10 mm wide adhesive-coated mylar tape (manufactured by Nitto Denko) was applied to the treated surface, and the tape was kept in close contact with the treated surface until the pasted tape became transparent, then gently peeled off and the adhesive was removed. This is a method to check the amount remaining on the treated surface. The treated surface with a larger residual amount has a higher adhesive strength when a multilayer printed wiring board is manufactured. The evaluation criteria were: × if no adhesive remained, △ if a little adhesive remained, ○ if about half of the adhesive remained, and ◎ if it remained all over the surface. The storage stability was determined by performing the tape test described above after leaving the product at room temperature and humidity for 7 days, and examining the amount of adhesive remaining after processing using the same evaluation method as the tape test. Comparative Example 1 A copper-clad laminate using an epoxy resin was roughened with ammonium persulfate. The color of this copper surface,
Table 1 shows the results of the tape test and storage stability.
【表】
実施例 ２
エポキシ樹脂を使用した銅張積層体（両面板）
に内層回路を形成し印刷回路としたものを次の方
法によつて処理した。
脱脂→過硫酸アンモニウム粗化→水洗→基本浴
組成(A)にキサントプテリンあるいは２−アミノペ
リミジン塩酸塩あるいはニトログアニジンを15
mg／それぞれ単独添加した70℃の浴に５分間浸
漬→水洗→乾燥（100℃30分間）した。この印刷
回路板を第１図に示す構成によつて加熱加圧（圧
力60Kg／cm2、温度170℃、時間120分）をおこない
多層化接着し、多層プリント配線板を作成した。
得られた多層プリント配線板の特性を表２に示
す。特性の評価方法は次の通りである。
Γ内層銅箔引剥し試験；JIS−C6481
Γ耐塩酸性試験；130×30mmに切断し、表面銅箔
を除去した試験片に直径１mmの穴を36穴あけ、
19％塩酸に浸漬させて塩酸が内層面に浸み込む
までの時間を計測する。
比較例 ２
エポキシ樹脂を使用した銅張積層板（両面板）
に内層回路を形成し印刷回路としたものを次の方
法によつて処理した。
脱脂→過硫酸アンモニウム粗化→水洗→乾燥
（100℃30分）。この印刷回路板を用いて実施例２
と同様に多層化接着して多層プリント配線板を作
成した。このものの特性を表２に示す。
実施例 ３
実施例２と同様に処理液Ａで処理した後、次の
処理液Ｂで処理して実施例２と同様にして多層プ
リント配線板を作成した。得られた多層プリント
配線板の特性を表２に示す。
処理液Ｂ
組成：１％塩酸水溶液
処理液の温度：20−25℃
処理時間：30秒
比較例 ３
エポキシ樹脂を使用した銅張積層板（両面板）
に内層回路を形成し印刷回路としたものを次の方
法によつて処理した。脱脂→粗化→水洗→（水酸
化ナトリウム0.5％＋リン酸三ナトリウム１％＋
亜塩素酸ナトリウム３％）水溶液70℃、１分間浸
漬→水洗→乾燥（100℃で30分間）この印刷回路
板を用いて実施例２と同様に多層化接着して多層
プリント配線板を作成した。このものの特性を表
２に示す。
比較例 ４
両面粗化銅箔を使用したエポキシ樹脂銅張積層
板（両面板）に内層回路を形成し、印刷回路とし
たものを実施例２と同様に多層化接着して多層プ
リント配線板を作成した。このものの特性を表２
に示す。[Table] Example 2 Copper-clad laminate using epoxy resin (double-sided board)
A printed circuit with an inner layer circuit formed thereon was processed by the following method. Degreasing → Roughening with ammonium persulfate → Washing with water → Add 15% of xanthopterin, 2-aminoperimidine hydrochloride, or nitroguanidine to basic bath composition (A)
mg/individually added to a bath at 70°C for 5 minutes, washing with water, and drying (100°C for 30 minutes). This printed circuit board was heat-pressed (pressure: 60 kg/cm 2 , temperature: 170° C., time: 120 minutes) to bond the printed circuit board into multiple layers using the configuration shown in FIG. 1, thereby producing a multilayer printed wiring board.
Table 2 shows the properties of the obtained multilayer printed wiring board. The characteristics were evaluated as follows. Γ Inner layer copper foil peeling test; JIS-C6481 Γ Hydrochloric acid resistance test; Cut 130 x 30 mm, remove the surface copper foil, and drill 36 holes with a diameter of 1 mm.
Immerse it in 19% hydrochloric acid and measure the time it takes for the hydrochloric acid to penetrate into the inner surface. Comparative example 2 Copper-clad laminate using epoxy resin (double-sided board)
A printed circuit with an inner layer circuit formed thereon was processed by the following method. Degreasing → roughening with ammonium persulfate → washing with water → drying (100℃ 30 minutes). Example 2 using this printed circuit board
A multilayer printed wiring board was created by bonding multiple layers in the same manner as above. The properties of this product are shown in Table 2. Example 3 A multilayer printed wiring board was prepared in the same manner as in Example 2 by treating with treatment liquid A and then with treatment liquid B. Table 2 shows the properties of the obtained multilayer printed wiring board. Treatment liquid B Composition: 1% aqueous hydrochloric acid solution Temperature of treatment liquid: 20-25℃ Treatment time: 30 seconds Comparative example 3 Copper-clad laminate using epoxy resin (double-sided board)
A printed circuit with an inner layer circuit formed thereon was processed by the following method. Degreasing → roughening → washing with water → (sodium hydroxide 0.5% + trisodium phosphate 1% +
Sodium chlorite 3%) aqueous solution 70°C, 1 minute immersion → water washing → drying (100°C for 30 minutes) Using this printed circuit board, a multilayer printed wiring board was created by multilayer bonding in the same manner as in Example 2. . The properties of this product are shown in Table 2. Comparative Example 4 An inner layer circuit was formed on an epoxy resin copper-clad laminate (double-sided board) using double-sided roughened copper foil, and a printed circuit was bonded in a multilayer manner in the same manner as in Example 2 to form a multilayer printed wiring board. Created. Table 2 shows the characteristics of this product.
Shown below.
【表】
※ 内層回路のライン精度；優：ライン端部の直線性
の良いもの、劣：ライン端部が蛇行するもの。
（発明の効果）
以上説明したように、本発明に於てはプリプレ
グ等の樹脂材料と導体回路等の金属との密着性が
向上し、多層プリント板に於ては、内層回路のラ
イン精度が優れ、耐塩酸性に優れた多層印刷配線
板を得ることができる。[Table] * Line accuracy of inner layer circuit; Excellent: Line with good linearity at the end, Poor: Line with meandering end.
(Effects of the Invention) As explained above, the present invention improves the adhesion between resin materials such as prepreg and metals such as conductor circuits, and improves the line precision of inner layer circuits in multilayer printed boards. A multilayer printed wiring board with excellent hydrochloric acid resistance can be obtained.
第１図は多層板の製造法を示す断面図である。
符号の説明、１……内層用銅張積層板、２……
内層回路基板上の回路銅箔、３……プリプレグ、
４……銅箔。
FIG. 1 is a sectional view showing a method for manufacturing a multilayer board. Explanation of symbols, 1... Copper-clad laminate for inner layer, 2...
Circuit copper foil on inner layer circuit board, 3...prepreg,
4...Copper foil.
Claims (1)
元剤、PH調整剤、水、および 分子中に−Ｎ＝と、−NH2および／または−
OHとをもつ有機化合物の少なくとも一種、 を含む無電解剤銅めつき液で銅めつきを行つた
後、樹脂層と接着することを特徴とする金属と樹
脂層との積層体の製造法。 ２ 分子内に−Ｎ＝と、−NH2および／または−
OHとをもつ有機化合物が、８−アザグアニン、
キサントプテリン、５−アミノインダゾール、２
−アミノペリジン塩酸塩、２−アミノペリミジン
臭化水素酸塩、ペンゾグアナミン、アクリフラビ
ン塩酸塩、５−アミノ−IH−テトラゾル、６−
アミノ−２−フエニル−４−キノリル、２−アミ
ノ−６，８−ジヒドロキシプリン、２−アミノピ
リミジン、６−ヒドロキシ−２，４，５−トリア
ミノピリミジン硫酸塩、２，４−ジアミノ−６−
ヒドロキシピリミジン、２−アミノ−４−ヒドロ
キシ−６−メチルピリミジン、４，６−ジヒドロ
キシピリミジン、ニトログアニジン、１−ヒドロ
キシ−IH−ベンゾトリアゾール１水塩、２−ヒ
ドロキシベンズイミダゾール、３−アミノ−３−
ヒドロキシピリミジンであることを特徴とする特
許請求の範囲第１項記載の金属と樹脂層との積層
体の製造法。 ３ 金属表面を銅めつきした後、還元剤を含む水
溶液、酸溶液およびアンモニア水の少なくとも１
種以上の液で処理した後樹脂層と接着することを
特徴とする特許請求の範囲第１項又は第２項記載
の金属と樹脂層との積層体の製造法。[Claims] 1. The metal surface is treated with copper ions, a complexing agent for copper ions, a reducing agent for copper ions, a PH adjuster, water, and -N= in the molecule, -NH 2 and/or -
A method for producing a laminate of a metal and a resin layer, which comprises plating copper with an electroless copper plating solution containing at least one organic compound having OH and then adhering it to a resin layer. 2 -N= in the molecule, -NH 2 and/or -
The organic compound with OH is 8-azaguanine,
Xanthopterin, 5-aminoindazole, 2
-Aminoperidine hydrochloride, 2-aminoperimidine hydrobromide, penzoguanamine, acriflavine hydrochloride, 5-amino-IH-tetrazole, 6-
Amino-2-phenyl-4-quinolyl, 2-amino-6,8-dihydroxypurine, 2-aminopyrimidine, 6-hydroxy-2,4,5-triaminopyrimidine sulfate, 2,4-diamino-6-
Hydroxypyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine, 4,6-dihydroxypyrimidine, nitroguanidine, 1-hydroxy-IH-benzotriazole monohydrate, 2-hydroxybenzimidazole, 3-amino-3-
The method for producing a laminate of a metal and resin layer according to claim 1, wherein the layer is hydroxypyrimidine. 3 After copper plating the metal surface, at least one of an aqueous solution containing a reducing agent, an acid solution, and ammonia water is applied.
3. The method for producing a laminate of a metal and a resin layer according to claim 1 or 2, wherein the laminate is bonded to a resin layer after being treated with at least one liquid.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60015807A JPS61173932A (en) | 1985-01-30 | 1985-01-30 | Manufacture of laminate of metal and resin layer |
| KR1019850004563A KR890004583B1 (en) | 1984-06-29 | 1985-06-26 | Process for treating metal surface |
| DE8585304636T DE3582531D1 (en) | 1984-06-29 | 1985-06-28 | METHOD FOR TREATING METAL SURFACES. |
| EP85304636A EP0170414B1 (en) | 1984-06-29 | 1985-06-28 | Process for treating metal surface |
| US06/750,780 US4643793A (en) | 1984-06-29 | 1985-07-01 | Process for treating metal surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60015807A JPS61173932A (en) | 1985-01-30 | 1985-01-30 | Manufacture of laminate of metal and resin layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61173932A JPS61173932A (en) | 1986-08-05 |
| JPH0578414B2 true JPH0578414B2 (en) | 1993-10-28 |
Family
ID=11899115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60015807A Granted JPS61173932A (en) | 1984-06-29 | 1985-01-30 | Manufacture of laminate of metal and resin layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61173932A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2758634B2 (en) * | 1988-03-14 | 1998-05-28 | シャープ株式会社 | Data transmission equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59219459A (en) * | 1983-05-27 | 1984-12-10 | Nec Corp | Solution for holding activity of electroless plated copper film |
| JPS6017080A (en) * | 1983-07-08 | 1985-01-28 | Nec Corp | Electroless copper plating solution |
-
1985
- 1985-01-30 JP JP60015807A patent/JPS61173932A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59219459A (en) * | 1983-05-27 | 1984-12-10 | Nec Corp | Solution for holding activity of electroless plated copper film |
| JPS6017080A (en) * | 1983-07-08 | 1985-01-28 | Nec Corp | Electroless copper plating solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61173932A (en) | 1986-08-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |