JPH045754B2 - - Google Patents
Info
- Publication number
- JPH045754B2 JPH045754B2 JP2845786A JP2845786A JPH045754B2 JP H045754 B2 JPH045754 B2 JP H045754B2 JP 2845786 A JP2845786 A JP 2845786A JP 2845786 A JP2845786 A JP 2845786A JP H045754 B2 JPH045754 B2 JP H045754B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- oxide film
- potential
- copper oxide
- 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
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 23
- 239000005751 Copper oxide Substances 0.000 claims description 23
- 229910000431 copper oxide Inorganic materials 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 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
- 238000006722 reduction reaction Methods 0.000 description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 3
- 229960002218 sodium chlorite Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000005749 Copper compound 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
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 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
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- WROHAQZYIUQHNL-UHFFFAOYSA-N [Na].[Na].[Na].[P] Chemical compound [Na].[Na].[Na].[P] WROHAQZYIUQHNL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 aromatic aldehyde compounds Chemical class 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 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
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation 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
- 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
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide 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
- 239000012261 resinous substance Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 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
Classifications
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
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
ム水溶液、塩化第２銅と塩酸を含む水溶液等の薬
液で処理して銅箔表面を粗面化した後、更に亜塩
素酸ナトリウム系処理液で処理することによつて
酸化銅皮膜を形成した後、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
着し、スルーホールをあけ、スルーホール壁面に
無電解めつきを行う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）
この方法は次の問題点があつた。
この多層プリント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、またドリル穴明け時
に内層銅の切削断面に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銅皮膜形
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
発明は上記した酸化銅皮膜の耐薬品性が低いこと
によつておこる問題を解決できる金属と樹脂層と
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、銅表面を酸化剤を含む水溶液と接触
させて銅表面に酸化銅皮膜を形成させ、次に酸化
銅皮膜をpHが９以上であるホルムアルデヒド供
給源を含む水溶液と接触させ酸化銅皮膜の電位が
Ag−AgCl電極に対して−400mVよりも卑な電位
に少くとも一時的に保持するようにして酸化銅皮
膜を還元した後、樹脂層と接着することを特徴と
するものである。
酸化剤を含む水溶液（以下処理液Ａという）と
しては、亜塩素酸ナトリウムなどの酸化剤を含む
もので、更にOH-イオン源およびリン酸三ナト
リウムなどの緩衝剤を含むものが好ましい。この
処理液Ａの処理によつて銅酸化物からなる微細な
凹凸をもつ皮膜が形成される。次にホルムアルデ
ヒド供給源を含む水溶液（以下処理液Ｂという）
によつて、銅酸化物からなる微細な凹凸皮膜を還
元して金属銅からなる微細な凹凸表面に変化させ
る。処理液Ｂはアルカリ性でホルムアルデヒド供
給源、例えばホルムアルデヒド、パラホルムアル
デヒド、芳香族アルデヒド化合物を添加した水溶
液である。pHは９以上、望ましくは10.5以上で
ある。pHの高い方が還元力が大きくなる。pH調
整剤としては水溶液アルカリなどが用いられる。
ホルムアルデヒド供給源の添加量は0.01モル／
以上、好ましくは0.02モル／以上である。但
し、高濃度になると作業環境を悪化させるので好
ましくない。処理液Ｂの温度は水溶液が保たれる
温度であればどの温度でもかまわない。一般に低
温になると活性が低下するので成分濃度を上昇さ
せる必要がある。この処理液Ｂ中での酸化銅皮膜
の電位はAg−AgCl電極に対して約−150±
100mVである。しかし、この処理液Ｂ中で酸化
銅皮膜の電位をAg−AgCl電極に対して−400mV
よりも卑な電位に少なくとも一時的に保持する操
作を行うと、この操作を行わない場合と比べて著
しく速やかに還元反応を開始させられることを見
い出した。−400mVよりも卑な電位の保持時間
は、１秒間以下という短時間でも還元反応を開始
させることが可能である。保持する電位が大きく
卑である程、還元反応が速やかに終わる。したが
つてその電位は好ましくは−500mVよりも卑で
ある。卑な電位に保持する方法は処理液ＢでAg
−AgCl電極に対する電位が−500mVよりも卑で
ある銅、Pt、Pdなどの貴金属と酸化銅皮膜とを
処理液Ｂ中で接触させることによつて行うことが
できる。又は定電圧電源を用いて−400mVより
も卑の電位を与えることができる。この場合電位
を与えることが目的であり電流は小さくて良い。
処理液Ｂで処理する時間は卑な電位に保持するた
めの操作を除いた状態で、処理液Ｂ中での処理面
の電位がAg−AgCl電極に対して−500mVよりも
卑な電位になるまでの時間である。通常約120秒
であるがそれ以上でもかまわない。処理液Ｂ中で
の金属銅のAg−AgCl電極に対する電位は約−
800±200mVの範囲である。したがつて−500mV
よりも卑であれば酸化銅の少なくとも一部分は還
元されている。
本発明において処理される銅の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、
硝酸、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
機械的な方法で行つてもよい。
内層回路が形成された配線板を処理液Ａ，Ｂで
処理した後、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、乾燥したプリプレグ
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。
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箔面に形成されるエツ
チング、めつきレジスタ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
スタとの積層体、銅箔とプリプレグとを積層した
銅張積層板、銅箔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。
内装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，Ｂ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
着剤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、ポルエーテルイミドな
どの熱可塑性樹脂も使用出来る。
実施例
あらかじめ内層回路を形成した内層用銅張積層
板を過硫酸アンモニウム水溶液で粗化処理した
後、次の処理液Ａの条件で処理し、酸化銅皮膜を
形成した。
水酸化ナトリウム＝0.5％
リン三ナトリウム＝1.5％
亜塩素酸ナトリウム＝３％
純 水＝95％
温 度＝75℃
処理時間＝２分
更に次の処理液Ｂに浸漬した。
pH＝12.5（NaOHを用いて調整）
37％CH2Ｏ＝0.06モル／
純 水＝１になる量
温 度＝60℃
処理液Ｂに浸漬した酸化銅皮膜の表面に金属銅
板を３秒間接触させた。この金属銅板は予め脱脂
および脱錆処理したものを用いた。この後120秒
間処理液Ｂ中に浸漬した。処理された面のAg−
AgCl電極に対する電位は−900mVであつた。次
にこの内層用銅張積層板の両面をエポキシ樹脂プ
リプレグではさみ、更にその両面を銅箔ではさみ
加圧、加熱（圧力60Kg／cm2、温度170℃、時間120
分）を行い多層化接着し、内層回路入銅張積層板
を作成した。
以上の如くして得た内層回路入銅張積層板の諸
特性を表１に示す。諸特性の評価方法は次の通り
である。
・ 内層銅箔引き剥し試験；JIS−C6481
・ 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。
・ 耐無電解銅めつき液性試験；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、次の条件のめつき液に浸漬させ
てめつき液が内層面に浸み込むまで時間を計測
する。
CuSO4・5H2Ｏ＝10g／
EDTA／2Na＝30g／
pH＝12.5（NaOHを用いて調整）
37％CH2Ｏ＝5m／
純 水＝全量が１になる量
比較例
実施例と同様にして酸化銅皮膜を形成した後、
実施例の処理液Ｂに60分間浸漬した。60分後の酸
化銅皮膜のAg−AgCl電極に対する電位は−
180mVであつた。
次にこの内層用銅張積層板を用いて実施例と同
じ方法で内層回路入銅張積層板を作成した。
諸特性を表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 made into multiple layers via prepreg. (Prior Art) A multilayer printed wiring board is manufactured as follows. That is, 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 this copper foil is treated with an aqueous solution of ammonium persulfate, cupric chloride, and hydrochloric acid, etc. After roughening the surface of the copper foil by treating it with a chemical solution, and forming a copper oxide film by further treating it with a sodium chlorite-based treatment solution, the inner layer copper-clad laminate is coated with prepreg. It was manufactured by laminating and bonding copper-clad laminates for the outer layer, drilling through holes, and performing electroless plating on the walls of the through holes. (Problems to be solved by the invention) This method had the following problems. This multilayer printed wiring board is manufactured by using an acidic solution during the process of applying a plating catalyst to the through-hole wall surface for through-hole plating, and during the process of removing resinous substances that adhere to the cut cross section of the inner copper layer during drilling. Due to the acidic solutions used in this process, as well as electroless copper plating solutions, these solutions seep into the gap between the copper oxide film forming layer and the insulating resin layer, reducing adhesiveness and insulation resistance between conductors. There was a problem. The present invention provides a method for producing a laminate of a metal and resin layer that has excellent adhesive strength between the metal and resin layer and can solve the problems caused by the low chemical resistance of the copper oxide film described above. . (Means for Solving the Problems) The present invention involves forming a copper oxide film on the copper surface by bringing the copper surface into contact with an aqueous solution containing an oxidizing agent, and then supplying the copper oxide film with formaldehyde having a pH of 9 or more. The potential of the copper oxide film increases when it comes into contact with an aqueous solution containing a source.
This method is characterized in that the copper oxide film is reduced by at least temporarily maintaining a potential lower than -400 mV with respect to the Ag-AgCl electrode, and then adhered to the resin layer. The aqueous solution containing an oxidizing agent (hereinafter referred to as treatment solution A) preferably contains an oxidizing agent such as sodium chlorite, and further contains an OH - ion source and a buffering agent such as trisodium phosphate. By this treatment with treatment liquid A, a film made of copper oxide and having fine irregularities is formed. Next, an aqueous solution containing a formaldehyde source (hereinafter referred to as treatment solution B)
The finely uneven film made of copper oxide is reduced to a finely uneven surface made of metallic copper. Treatment liquid B is an alkaline aqueous solution containing a formaldehyde source, such as formaldehyde, paraformaldehyde, and aromatic aldehyde compounds. The pH is 9 or higher, preferably 10.5 or higher. The higher the pH, the greater the reducing power. As the pH adjuster, an aqueous alkali or the like is used.
The amount of formaldehyde source added is 0.01 mol/
The amount is preferably 0.02 mol/or more. However, high concentrations are not preferable because they worsen the working environment. The temperature of the treatment liquid B may be any temperature as long as it maintains an aqueous solution. Generally, the activity decreases at low temperatures, so it is necessary to increase the component concentration. The potential of the copper oxide film in this treatment solution B is approximately -150± with respect to the Ag-AgCl electrode.
It is 100mV. However, in this treatment solution B, the potential of the copper oxide film was set to -400 mV with respect to the Ag-AgCl electrode.
It has been found that by performing an operation of at least temporarily holding the potential at a more base potential than that, the reduction reaction can be started significantly more quickly than when this operation is not performed. The reduction reaction can be started even if the holding time of a potential more base than -400 mV is as short as 1 second or less. The greater and more base the potential held, the more quickly the reduction reaction ends. The potential is therefore preferably less than -500 mV. The method to maintain a base potential is to use processing solution B to
This can be carried out by bringing the copper oxide film into contact with a noble metal such as copper, Pt, or Pd whose potential relative to the -AgCl electrode is less than -500 mV in treatment solution B. Alternatively, a potential more base than -400mV can be applied using a constant voltage power supply. In this case, the purpose is to apply a potential, and the current may be small.
During the treatment time with treatment solution B, the potential of the treated surface in treatment solution B becomes more base than -500 mV with respect to the Ag-AgCl electrode, excluding the operation to maintain the base potential. This is the time until. Usually it is about 120 seconds, but it can be longer. The potential of metallic copper in treatment solution B with respect to the Ag-AgCl electrode is approximately -
The range is 800±200mV. Therefore −500mV
If the copper oxide is baser than the copper oxide, at least a portion of the copper oxide has been reduced. The conductor of the wiring pattern of the laminate with inner layer wiring, which is an example of the copper 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 above-mentioned copper surface treatment, water, hydrochloric acid, sulfuric acid,
From a combination of compounds selected from nitric acid, phosphoric acid, citric acid, copper compounds such as cupric chloride and copper sulfate, iron compounds such as ferric chloride and ferric sulfate, alkali metal chlorides, ammonium persulfate, etc. It may be treated with an aqueous solution. Moreover, instead of these chemical methods of "roughening", mechanical methods such as liquid honing and polishing may be used. After treating the wiring boards on which inner layer circuits have been formed with treatment liquids A and B, the required number of boards are stacked with prepregs that have been impregnated with thermosetting resin and dried into a base material such as paper or glass cloth, and then heated and pressed. It is integrated to produce a multilayer printed wiring board. Above, we have described a multilayer printed wiring board in which an inner layer wiring board and a prepreg are bonded together as a laminate of metal and resin layers. A laminate of a wiring board with a conductor circuit formed thereon and a solder resistor formed on its surface, a copper-clad laminate made of a laminate of copper foil and prepreg, a laminate of copper foil and a flexible material. There are substrates for flexible wiring boards, etc., which are laminated with films. After forming the internal circuit by an etching method or an additive method, processing with processing liquids A and B is performed, and an insulating resin such as resist ink or adhesive is applied or adhered by screen printing, curtain coating, or hot roll lamination. This makes it possible to ensure adhesion between the copper circuit and the above-mentioned material. 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. Example A copper-clad laminate for an inner layer on which an inner layer circuit had been formed in advance was roughened with an aqueous ammonium persulfate solution, and then treated under the following conditions of treatment solution A to form a copper oxide film. Sodium hydroxide = 0.5% Trisodium phosphorus = 1.5% Sodium chlorite = 3% Pure water = 95% Temperature = 75°C Treatment time = 2 minutes It was further immersed in the following treatment solution B. pH = 12.5 (adjusted using NaOH) 37% CH 2 O = 0.06 mol / Amount to make pure water = 1 Temperature = 60°C A metal copper plate was brought into contact with the surface of the copper oxide film immersed in treatment solution B for 3 seconds. Ta. This metal copper plate was previously subjected to degreasing and derusting treatment. After that, it was immersed in treatment liquid B for 120 seconds. Ag− of treated surface
The potential to the AgCl electrode was -900 mV. Next, both sides of this copper-clad laminate for the inner layer were sandwiched between epoxy resin prepregs, and then both sides were sandwiched between copper foils, and then pressurized and heated (pressure 60 kg/cm 2 , temperature 170°C, time 120
), and multi-layer bonding was performed to create a copper-clad laminate with inner layer circuitry. Table 1 shows various properties of the copper-clad laminate with inner layer circuitry obtained as described above. The evaluation method of various characteristics is as follows.・ Inner layer copper foil peeling test; JIS-C6481 ・ Hydrochloric acid resistance test Cut 130 x 30 mm, remove 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.・Electroless copper plating liquid resistance test: Cut 130 x 30 mm, remove the surface copper foil, make 36 holes with a diameter of 1 mm, and immerse it in the plating solution under the following conditions. Measure the time until it soaks into the inner surface. CuSO 4・5H 2 O = 10 g / EDTA / 2Na = 30 g / pH = 12.5 (adjusted using NaOH) 37% CH 2 O = 5 m / Pure water = amount that makes the total amount 1 Comparative example Same as the example After forming the copper oxide film,
It was immersed in the treatment solution B of Example for 60 minutes. The potential of the copper oxide film after 60 minutes with respect to the Ag−AgCl electrode is −
It was 180mV. Next, using this inner layer copper clad laminate, a copper clad laminate with an inner layer circuit was created in the same manner as in the example. Various properties are shown in Table 1.
【表】
（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、耐塩酸性、耐
無電解銅めつき液性に優れた多層印刷配線板を得
ることができる。[Table] (Effects of the invention) As explained above, in the present invention, the adhesion between resin materials such as prepreg and metals such as conductor circuits is improved, and in multilayer printed boards, hydrochloric acid resistance, A multilayer printed wiring board with excellent resistance to electroless copper plating liquid can be obtained.
Claims (1)
表面に酸化銅皮膜を形成させ、次に酸化銅皮膜を
pHが９以上であるホルムアルデヒド供給源を含
む水溶液と接触させ酸化銅皮膜の電位がAg−
AgCl電極に対して−400mVよりも卑な電位に少
くとも一時的に保持するようにして酸化銅皮膜を
還元した後、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。1 A copper oxide film is formed on the copper surface by contacting the copper surface with an aqueous solution containing an oxidizing agent, and then a copper oxide film is formed on the copper surface.
When brought into contact with an aqueous solution containing a formaldehyde source with a pH of 9 or higher, the potential of the copper oxide film changes to Ag-
A laminate of a metal and a resin layer, characterized in that the copper oxide film is reduced by holding at least temporarily at a potential lower than -400 mV with respect to an AgCl electrode, and then bonded to the resin layer. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2845786A JPS62185884A (en) | 1986-02-12 | 1986-02-12 | Production of laminate of metal and resin layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2845786A JPS62185884A (en) | 1986-02-12 | 1986-02-12 | Production of laminate of metal and resin layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62185884A JPS62185884A (en) | 1987-08-14 |
| JPH045754B2 true JPH045754B2 (en) | 1992-02-03 |
Family
ID=12249193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2845786A Granted JPS62185884A (en) | 1986-02-12 | 1986-02-12 | Production of laminate of metal and resin layer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62185884A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4618466B2 (en) * | 2000-10-11 | 2011-01-26 | 日立化成工業株式会社 | Copper surface treatment |
| JP2006249519A (en) * | 2005-03-11 | 2006-09-21 | Hitachi Chem Co Ltd | Surface treatment method for copper and copper |
-
1986
- 1986-02-12 JP JP2845786A patent/JPS62185884A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62185884A (en) | 1987-08-14 |
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