JPH04284690A - Copper foil for inner layer circuit of multilayer printed circuit board and manufacture thereof - Google Patents
Copper foil for inner layer circuit of multilayer printed circuit board and manufacture thereofInfo
- Publication number
- JPH04284690A JPH04284690A JP7208691A JP7208691A JPH04284690A JP H04284690 A JPH04284690 A JP H04284690A JP 7208691 A JP7208691 A JP 7208691A JP 7208691 A JP7208691 A JP 7208691A JP H04284690 A JPH04284690 A JP H04284690A
- Authority
- JP
- Japan
- Prior art keywords
- copper foil
- inner layer
- copper
- multilayer printed
- printed wiring
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000011889 copper foil Substances 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000011888 foil Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 238000007747 plating Methods 0.000 claims description 42
- 229910052802 copper Inorganic materials 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011135 tin Substances 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 238000007788 roughening Methods 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000007689 inspection Methods 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 28
- 239000000203 mixture Substances 0.000 description 18
- 229910000881 Cu alloy Inorganic materials 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910000990 Ni alloy Inorganic materials 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910000531 Co alloy Inorganic materials 0.000 description 3
- VRUVRQYVUDCDMT-UHFFFAOYSA-N [Sn].[Ni].[Cu] Chemical compound [Sn].[Ni].[Cu] VRUVRQYVUDCDMT-UHFFFAOYSA-N 0.000 description 3
- WDHWFGNRFMPTQS-UHFFFAOYSA-N cobalt tin Chemical compound [Co].[Sn] WDHWFGNRFMPTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 3
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 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
- 229910000597 tin-copper alloy Inorganic materials 0.000 description 2
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- 229940082569 selenite Drugs 0.000 description 1
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Production Of Multi-Layered Print Wiring Board (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、プリプレグとの密着性
が優れ、かつ、ハロ−イング現象が起こりにくく、さら
に、光学式検査が容易な多層プリント配線板内層回路用
銅箔及びその製造方法に関する。[Industrial Application Field] The present invention provides a copper foil for inner layer circuits of multilayer printed wiring boards that has excellent adhesion to prepreg, is less likely to cause the haloing phenomenon, and is easy to optically inspect, and a method for manufacturing the same. Regarding.
【0002】0002
【従来の技術】従来の多層プリント配線板の製造方法は
、銅箔を絶縁性基材に貼り合せて銅張積層板とし、その
表面の不要な銅箔部分をエッチング除去して内層回路を
形成し、さらにプリプレグとの密着性を向上させるため
に、その内層回路の銅表面を粗化や酸化処理した後に、
外層材をこれに積層し、この外層材に内層回路と外層回
路とを接続するためのスル−ホ−ルを開け、そのスル−
ホール部に無電解めっき等を用いて銅層を形成させて導
通を得た後、外層回路をエッチングして形成していた。[Prior Art] The conventional method for manufacturing multilayer printed wiring boards is to bond copper foil to an insulating base material to form a copper-clad laminate, and then remove unnecessary copper foil portions from the surface by etching to form inner layer circuits. Then, in order to further improve the adhesion with the prepreg, after roughening and oxidizing the copper surface of the inner layer circuit,
An outer layer material is laminated on this, a through hole is made in this outer layer material to connect the inner layer circuit and the outer layer circuit, and the through hole is formed.
After forming a copper layer in the hole using electroless plating or the like to obtain continuity, the outer layer circuit was formed by etching.
【0003】このような多層プリント配線板の製造工程
で、内層回路用銅箔は、種々の加工工程や回路基板形成
後の過酷な使用条件にさらされ、近年一段と加工条件や
使用条件が厳しくなってきているので、内層回路とプリ
プレグとの密着力を向上させるために、内層回路の銅表
面に、従来、下記■〜■の処理がなされていた。[0003] In the manufacturing process of such multilayer printed wiring boards, copper foil for inner layer circuits is exposed to various processing steps and harsh usage conditions after circuit board formation, and processing and usage conditions have become even more severe in recent years. In order to improve the adhesion between the inner layer circuit and the prepreg, the copper surface of the inner layer circuit has conventionally been subjected to the following treatments.
【0004】■ 通常の片面粗化銅箔で内層回路形成
後、酸化剤を含む化学処理液を用いて銅表面にブラウン
オキサイド又はブラックオキサイドと呼ばれる茶褐色又
は黒色の酸化銅を形成させる。■ 前記■のブラック
オキサイドをホルマリン等の還元剤で処理して還元銅を
形成させる(特開平1−310595号公報)。■
市販の両面粗化銅箔を使用する。[0004] After forming an inner layer circuit using a conventional single-sided roughened copper foil, a chemical treatment solution containing an oxidizing agent is used to form brown or black copper oxide called brown oxide or black oxide on the copper surface. (2) The black oxide in (1) above is treated with a reducing agent such as formalin to form reduced copper (Japanese Patent Application Laid-Open No. 1-310595). ■
Use commercially available double-sided roughened copper foil.
【0005】しかしながら、前記■のブラックオキサイ
ドを用いた内層回路用銅箔では、耐薬品性が乏しく、ハ
ロ−イングを生じやすいという欠点があり、ブラウンオ
キサイドを用いた内層回路用銅箔では、耐薬品性が不十
分で、しかもプリプレグとの密着力が劣るという欠点が
あった。[0005] However, the copper foil for inner layer circuits using black oxide described in (2) above has poor chemical resistance and is prone to haloing, while the copper foil for inner layer circuits using brown oxide has poor chemical resistance. It had the drawbacks of insufficient chemical properties and poor adhesion to the prepreg.
【0006】また、前記■の還元銅を用いた内層回路用
銅箔では、内層回路を形成した後、該回路を、例えば、
VISION 206 AOI(オプトロテック社
製)を使用して自動光学検査する際に、回路部分の銅色
と絶縁層部分の色差が小さいので、AOIでの誤報が多
く、その確認のために多大な時間を要するばかりでなく
、回路の欠陥を見過すという欠点があり、検査の効率及
び信頼性が不十分であった。[0006] In addition, in the above-mentioned copper foil for inner layer circuits using reduced copper, after forming the inner layer circuits, the circuits are processed by, for example,
When performing automatic optical inspection using the VISION 206 AOI (manufactured by Optrotech), the color difference between the copper color of the circuit part and the insulating layer part is small, so there are many false alarms with the AOI, and it takes a lot of time to confirm them. Not only does this require additional time, but it also has the disadvantage of overlooking circuit defects, resulting in insufficient inspection efficiency and reliability.
【0007】前記■の両面粗化銅箔を用いた内層回路用
銅箔では、前記■と同様に回路部分の銅色と絶縁層部分
の色差が小さいので、検査の効率及び信頼性が不十分で
あり、また回路を形成した後、放置すると銅部分が錆び
るという欠点があった。[0007] In the copper foil for inner layer circuits using the double-sided roughened copper foil described in (2) above, the color difference between the copper color of the circuit part and the insulating layer part is small, as in the case (2) above, so the inspection efficiency and reliability are insufficient. Another drawback was that the copper parts would rust if left unattended after the circuit was formed.
【0008】さらに、このような従来の処理は、プレス
、エッチング後の基板を処理するかぎり、単板を処理槽
に浸漬するバッチ処理方式を採用しなければならないの
で、多大な設備投資と処理時間を要するという欠点があ
った。また、処理する内層回路部分は、スル−ホ−ル等
の回路が未完成であり、電気的に接続していない部分が
あるので、プリプレグとの密着力を高めるための粗化処
理やいわゆる黒化処理は、研磨等の機械的処理や電気を
通さずに薬品だけで処理せざるをえなかった。Furthermore, in such conventional processing, as long as the substrate after pressing and etching is processed, a batch processing method in which the veneer is immersed in a processing tank must be adopted, which requires a large amount of equipment investment and processing time. The disadvantage was that it required In addition, the inner layer circuit part to be treated has unfinished circuits such as through-holes, and there are parts that are not electrically connected, so roughening treatment and so-called blackening are required to increase the adhesion with the prepreg. Chemical treatment had to be carried out using only chemicals, without mechanical treatment such as polishing or electricity.
【0009】このため従来の処理では、電気を通して行
う電気化学的処理に比べて処理が不十分であり、また処
理時間が長いという欠点があった。また、銅箔を硫化銅
で黒化処理したものは、銅箔の下地との密着性が劣るの
で、熱膨張や熱収縮等により剥離し、プリント配線板用
としては、信頼性に欠けるという欠点があった。[0009] For this reason, conventional treatments have disadvantages in that the treatment is insufficient and the treatment time is long compared to electrochemical treatment in which electricity is passed. In addition, copper foil blackened with copper sulfide has poor adhesion to the base of the copper foil, so it peels off due to thermal expansion or contraction, making it unreliable for printed wiring boards. was there.
【0010】0010
【発明が解決しようとする課題】本発明の目的は、内層
回路とプリプレグとの密着性及び耐ハロ−イング性が優
れ、かつAOI検査の効率及び信頼性が高く、しかも、
バッチ方式の化学処理工程による粗化処理又は黒化処理
を経なくとも多層板を製造できる多層プリント配線板内
層回路用銅箔及びその製造方法を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to have excellent adhesion and haloing resistance between an inner layer circuit and a prepreg, and high efficiency and reliability of AOI inspection.
It is an object of the present invention to provide a copper foil for inner layer circuits of a multilayer printed wiring board and a method for manufacturing the same, which can manufacture a multilayer board without undergoing roughening treatment or blackening treatment by a batch-type chemical treatment process.
【0011】[0011]
【課題を解決するための手段】本発明者は、従来の内層
回路形成後に黒化処理する方法では、回路面全面への給
電ができないために、電気化学的処理法を採用できず、
そのため多大な設備と処理時間を費やし、しかも不十分
であった黒化処理工程を、銅箔製造の段階で特定の金属
を用いて電気化学的に行うことにより、内層回路とプリ
プレグとの密着性及び耐ハロ−イング性が優れ、かつA
OI検査の効率及び信頼性が高いプリント回路用銅箔が
得られることを見出して本発明に到達した。[Means for Solving the Problems] The present inventors discovered that the conventional method of blackening treatment after forming an inner layer circuit does not allow power to be supplied to the entire circuit surface, and therefore an electrochemical treatment method cannot be adopted.
Therefore, the blackening treatment process, which required a large amount of equipment and processing time and was insufficient, was carried out electrochemically using a specific metal at the copper foil manufacturing stage, which improved the adhesion between the inner layer circuit and the prepreg. and excellent haloing resistance, and A
The present invention was achieved by discovering that a copper foil for printed circuits with high OI inspection efficiency and reliability can be obtained.
【0012】本発明の第1は、あらかじめ両面が粗化さ
れた銅箔の少なくとも内層回路板の表面となる粗面上に
、さらに黒色の金属めっき層を設けたことを特徴とする
多層プリント配線板内層回路用銅箔である。[0012] The first aspect of the present invention is a multilayer printed wiring characterized in that a black metal plating layer is further provided on at least the rough surface of the copper foil, which is the surface of the inner layer circuit board, which has been roughened on both sides in advance. This is a copper foil for inner layer circuits.
【0013】本発明の第2は、銅箔の両面を粗化処理し
、該銅箔に黒色の金属めっき層を形成することを特徴と
する多層プリント配線板内層回路用銅箔の製造方法であ
る。The second aspect of the present invention is a method for producing a copper foil for inner layer circuits of a multilayer printed wiring board, which comprises roughening both sides of the copper foil and forming a black metal plating layer on the copper foil. be.
【0014】以下、本発明を詳細に説明する。本発明に
用いる両面が粗化された銅箔としては、公知の方法で得
られたものでよく、例えば硫酸酸性の硫酸銅浴中で陰極
処理して、銅箔表面に粗化粒子を付着したもの(特公昭
54−38053号公報、特公昭53−39327号公
報、特公昭53−38700号公報参照)、酸性浴中で
陽極処理して、銅箔表面をエッチングして粗化したもの
(特公昭61−54592号公報)を挙げることができ
る。また銅箔は、電解銅箔及び圧延銅箔を用いることが
できる。The present invention will be explained in detail below. The copper foil with roughened surfaces on both sides used in the present invention may be obtained by a known method, such as cathodic treatment in a sulfuric acid acidic copper sulfate bath to adhere roughening particles to the surface of the copper foil. (see Japanese Patent Publication No. 54-38053, Japanese Patent Publication No. 53-39327, Japanese Patent Publication No. 53-38700), copper foil surface roughened by etching by anodizing in an acid bath Publication No. 61-54592). Further, as the copper foil, an electrolytic copper foil or a rolled copper foil can be used.
【0015】本発明の多層プリント配線板用銅箔は、こ
の両面が粗化された銅箔の少なくとも内層回路板の表面
となる側の面に黒色の金属めっき層を有する。本発明に
用いる黒色の金属めっき層(以下、黒色めっき層という
)としては、金属を黒色にめっきしたものであれば特に
制限はなく、金属を限界電流又はその近傍の電流密度で
処理した所謂ヤケめっき層であっても、限界電流密度よ
り低い電流密度で処理しためっき層であってもよい。The copper foil for a multilayer printed wiring board of the present invention has a black metal plating layer on at least the surface of the copper foil which is roughened on both sides and which becomes the surface of the inner layer circuit board. The black metal plating layer (hereinafter referred to as the black plating layer) used in the present invention is not particularly limited as long as it is a metal plated black, and the so-called discoloration layer that is obtained by treating the metal with a current density at or near the limiting current. It may be a plated layer or a plated layer treated at a current density lower than the limiting current density.
【0016】本発明に用いる黒色めっき層として好まし
いのは、ニッケル、コバルト、クロム、ロジウム、スズ
からなる群より選ばれた1種以上の金属を含有するめっ
き層であり、さらに好ましくは、ニッケル、ニッケル・
銅合金、ニッケル・スズ合金、ニッケル・スズ・銅合金
、スズ、スズ・コバルト合金、クロム、ロジウムを含有
するめっき層である。The black plating layer used in the present invention is preferably a plating layer containing one or more metals selected from the group consisting of nickel, cobalt, chromium, rhodium, and tin, and more preferably nickel, nickel·
It is a plating layer containing copper alloy, nickel-tin alloy, nickel-tin-copper alloy, tin, tin-cobalt alloy, chromium, and rhodium.
【0017】黒色めっき層は、可視光が反射しない程度
に微細な凹凸を有し、しかも下地の粗化面の凹凸形状を
維持できる厚さが好ましく、その厚さは、100〜10
,000オングストロ−ム、好ましくは100〜3,0
00オングストロ−ムである。また、黒色めっき層は、
銅箔の粗化面の凹凸部の全面を必ずしも完全に被覆しな
くともよく、例えば凹凸部の一部を被覆するものであっ
ても、外観が黒色に見えればよい。具体的には、JIS
Z 8701に規定されたYxy値が15%以下
、好ましくは14%以下、さらに好ましくは13%以下
の黒色めっき層である。Yxy値が15%を超えるとき
には、AOIでの誤報が多くなり、検査効率及び信頼性
が低下する場合がある。The black plating layer preferably has fine irregularities to the extent that visible light is not reflected, and has a thickness that maintains the irregular shape of the roughened surface of the base, and the thickness is 100 to 10
,000 angstroms, preferably 100-3.0 angstroms
00 angstroms. In addition, the black plating layer is
It is not necessary to completely cover the entire surface of the uneven portion of the roughened surface of the copper foil. For example, even if a portion of the uneven portion is covered, it is sufficient that the appearance appears black. Specifically, JIS
The black plating layer has a Yxy value defined in Z 8701 of 15% or less, preferably 14% or less, and more preferably 13% or less. When the Yxy value exceeds 15%, false alarms in the AOI increase, and inspection efficiency and reliability may decrease.
【0018】黒色めっき層における金属成分の含有量は
、例えば、ニッケル及びニッケル・銅合金の黒色めっき
層は、ニッケル量が2〜20mg/dm2であるのが好
ましい。スズ・ニッケル合金の黒色めっき層は、スズ量
が5〜30mg/dm2、ニッケル量が2〜12mg/
dm2であるのが好ましい。[0018] Regarding the content of the metal component in the black plating layer, for example, the black plating layer of nickel and nickel/copper alloy preferably has a nickel content of 2 to 20 mg/dm2. The black plating layer of tin-nickel alloy has a tin content of 5 to 30 mg/dm2 and a nickel content of 2 to 12 mg/dm2.
Preferably it is dm2.
【0019】ニッケル・スズ・銅合金の黒色めっき層は
、ニッケル量が1〜10mg/dm2、スズ量が5〜2
5mg/dm2、銅量が0.1〜2mg/dm2である
のが好ましい。スズ・コバルト合金の黒色めっき層は、
スズ量が5〜15mg/dm2、コバルト量が10〜3
0mg/dm2であるのが好ましい。The black plating layer of nickel-tin-copper alloy has a nickel content of 1 to 10 mg/dm2 and a tin content of 5 to 2.
It is preferable that the amount of copper is 5 mg/dm2 and the amount of copper is 0.1 to 2 mg/dm2. The black plating layer of tin-cobalt alloy is
The amount of tin is 5-15 mg/dm2, the amount of cobalt is 10-3
Preferably it is 0 mg/dm2.
【0020】上記黒色めっき層の各金属量が下限値未満
のときには、絶縁層との色差が得られない場合があり、
上限値を超えても、色差はあまり改善されず、経済的負
担が増大するので好ましくない場合がある。[0020] When the amount of each metal in the black plating layer is less than the lower limit, it may not be possible to obtain a color difference from the insulating layer.
Even if the upper limit is exceeded, the color difference will not be improved much and the economic burden will increase, which may not be preferable.
【0021】クロムの黒色めっき層は、クロム量が0.
2〜5mg/dm2であるのが好ましく、0.2mg/
dm2未満のときには、絶縁層との色差が得られない場
合があり、5mg/dm2を超えても、色差はあまり改
善されず、経済的負担が増大するので好ましくない。The black chromium plating layer has a chromium content of 0.
It is preferably 2 to 5 mg/dm2, and 0.2 mg/dm2.
If it is less than dm2, no color difference with the insulating layer may be obtained, and if it exceeds 5 mg/dm2, the color difference will not be improved much and the economic burden will increase, which is not preferable.
【0022】ロジウムの黒色めっき層は、ロジウム量が
5〜15mg/dm2であるのが好ましく、5mg/d
m2未満のときには、絶縁層との色差が得られない場合
があり、15mg/dm2を超えても、色差はあまり改
善されず、経済的負担が増大するので好ましくない。[0022] The rhodium black plating layer preferably has a rhodium content of 5 to 15 mg/dm2, preferably 5 mg/dm2.
If it is less than m2, no color difference with the insulating layer may be obtained, and if it exceeds 15 mg/dm2, the color difference will not be improved much and the economic burden will increase, which is not preferable.
【0023】ニッケル又はニッケル−銅合金のヤケめっ
き層を銅箔上に形成する方法としては、例えば、特開昭
55−58502号公報に示される方法を採用すること
ができ、具体的には、浴組成(硫酸ニッケル・・・ニッ
ケルとして1〜6g/l 、硫酸銅・・・銅として0.
3〜0.6g/l 、硫酸アンモニウム・・・50〜1
00g/l 、ホウ酸・・・10〜40g/l ):p
H(2.5):浴温度(20〜50℃):電流密度(2
〜10A/dm2 )の条件で前記ニッケル量をヤケめ
っきする方法を挙げることができるが、これに限定され
るものではない。[0023] As a method for forming a discolored plating layer of nickel or nickel-copper alloy on copper foil, for example, the method disclosed in Japanese Patent Application Laid-Open No. 55-58502 can be adopted, and specifically, Bath composition (nickel sulfate...1 to 6 g/l as nickel, copper sulfate...0.
3-0.6g/l, ammonium sulfate...50-1
00g/l, boric acid...10-40g/l):p
H (2.5): Bath temperature (20-50°C): Current density (2
An example of this method is a method in which the amount of nickel is burnt-plated under conditions of 10 A/dm2), but the method is not limited thereto.
【0024】クロムの黒色めっき層を銅箔上に形成する
方法としては、例えば浴組成(無水クロム酸・・・22
5〜300g/l 、酢酸・・・210〜218g/l
、酢酸バリウム・・・5〜10g/l ):浴温度(
32〜46℃):電流密度(4〜10A/dm2 )の
条件で前記クロム量をめっきする方法を挙げることがで
きるが、これに限定されるものではない。As a method for forming a black chromium plating layer on copper foil, for example, the bath composition (chromic anhydride...22
5-300g/l, acetic acid...210-218g/l
, barium acetate...5 to 10 g/l): Bath temperature (
A method of plating the amount of chromium at a current density (4 to 10 A/dm2) (32 to 46 DEG C.) can be mentioned, but the present invention is not limited thereto.
【0025】スズ・コバルト合金の黒色めっき層を銅箔
上に形成する方法としては、例えば浴組成(ピロリン酸
第一スズ・・・8〜15g/l 、塩化コバルト・・・
25〜30g/l 、ピロリン酸カリウム・・・275
〜350g/l 、エバロイSNC#1[荏原ユ−ジラ
イト(株)製]・・・75〜125ml/l、エバロイ
SNC#3[荏原ユ−ジライト(株)製]・・・15〜
25ml/l:浴温度(45〜55℃):電流密度(0
.5〜2.0A/dm2 ):pH(8.5〜8.8)
の条件で前記スズ及びコバルト量をめっきする方法を挙
げることができるが、これに限定されるものではない。As a method for forming a black plating layer of tin-cobalt alloy on copper foil, for example, bath composition (stannous pyrophosphate...8 to 15 g/l, cobalt chloride...
25-30g/l, potassium pyrophosphate...275
~350g/l, Everoy SNC#1 [manufactured by Ebara Yugilite Co., Ltd.]...75-125ml/l, Evalloy SNC#3 [manufactured by Ebara Yugilite Co., Ltd.]...15~
25ml/l: Bath temperature (45-55°C): Current density (0
.. 5-2.0A/dm2): pH (8.5-8.8)
Examples include a method of plating the amounts of tin and cobalt under the following conditions, but the method is not limited thereto.
【0026】スズ・ニッケル合金の黒色めっき層を銅箔
上に形成する方法としては、例えば浴組成(ピロリン酸
第一スズ・・・8〜15g/l 、ピロリン酸カリウム
・・・150〜280g/l 、エバロイニッケル[荏
原ユ−ジライト(株)製]・・・160〜240ml/
l、エバロイSNC#3[荏原ユ−ジライト(株)製]
・・・10〜20ml/l:浴温度(45〜55℃):
電流密度(0.5〜2.0A/dm2 ):pH(8.
5〜8.8)の条件で前記スズ及びニッケル量をめっき
する方法を挙げることができるが、これに限定されるも
のではない。As a method for forming a black plating layer of a tin-nickel alloy on a copper foil, for example, the bath composition (stannous pyrophosphate...8 to 15 g/l, potassium pyrophosphate...150 to 280 g/l) is used. l, Everoy Nickel [manufactured by Ebara Yugilite Co., Ltd.]...160-240ml/
l, Everoy SNC #3 [manufactured by Ebara Yugilite Co., Ltd.]
...10-20ml/l: Bath temperature (45-55°C):
Current density (0.5-2.0A/dm2): pH (8.
Examples include a method of plating the amounts of tin and nickel under the conditions of 5 to 8.8), but are not limited thereto.
【0027】スズ・ニッケル・銅合金の黒色めっき層を
銅箔上に形成する方法としては、例えば浴組成(塩化ス
ズ・・・25〜30g/l 、塩化ニッケル・・・28
〜35g/l 、ピロリン酸カリウム・・・180〜2
50g/l 、硫酸銅・・・2〜3g/l 、グリシン
・・・18〜25g/l 、アンモニア水・・・3〜8
ml/l、:浴温度(45〜55℃):電流密度(0.
1〜1.0A/dm2 ):pH(8.0〜8.5)の
条件で前記スズ、ニッケル及び銅量をめっきする方法を
挙げることができるが、これに限定されるものではない
。As a method for forming a black plating layer of tin-nickel-copper alloy on copper foil, for example, the bath composition (tin chloride...25 to 30 g/l, nickel chloride...28
~35g/l, potassium pyrophosphate...180~2
50g/l, copper sulfate...2-3g/l, glycine...18-25g/l, ammonia water...3-8
ml/l: Bath temperature (45-55°C): Current density (0.
A method of plating the amounts of tin, nickel and copper under conditions of pH (8.0 to 8.5) (1 to 1.0 A/dm2) may be mentioned, but is not limited thereto.
【0028】ロジウムの黒色めっき層を銅箔上に形成す
る方法としては、例えば浴組成(硫酸ロジウム・・・7
〜15g/l 、硫酸・・・40〜160g/l :浴
温度(38〜50℃):電流密度(2.0〜10A/d
m2 )の条件で前記ロジウム量をめっきする方法を挙
げることができるが、これに限定されるものではない。As a method for forming a rhodium black plating layer on copper foil, for example, the bath composition (rhodium sulfate...7
~15g/l, sulfuric acid...40~160g/l: Bath temperature (38~50°C): Current density (2.0~10A/d
Examples include a method of plating the amount of rhodium under the conditions of (m2), but are not limited thereto.
【0029】[0029]
【実施例】実施例1
厚さ35μmの電解銅箔を陰極とし、その両側に鉛を陽
極として配置し、浴組成:硫酸銅・・・銅として30g
/l 、硫酸・・・60g/l 、亜砒酸・・・砒素と
して1g/l :浴温度24℃:電流密度17A/dm
2 :処理時間:12秒の条件で第1段処理して、銅箔
の粗面及び光沢面に銅粒子を付着させて凹凸をつけた後
、十分水洗し、次いで、浴組成:硫酸銅・・・銅として
70g/l 、硫酸・・・60g/l :浴温度49℃
:電流密度21.5A/dm2 :処理時間:12秒の
条件で第2段処理して、前記銅粒子を固定した。[Example] Example 1 Electrolytic copper foil with a thickness of 35 μm was used as a cathode, and lead was placed on both sides as an anode. Bath composition: Copper sulfate...30 g as copper.
/l, Sulfuric acid...60g/l, Arsenous acid...1g/l as arsenic: Bath temperature 24°C: Current density 17A/dm
2: First stage treatment under conditions of treatment time: 12 seconds to make unevenness by adhering copper particles to the rough and shiny surfaces of the copper foil, followed by thorough washing with water, and then bath composition: copper sulfate. ...70g/l as copper, 60g/l as sulfuric acid: Bath temperature 49℃
: Current density: 21.5 A/dm2 : Processing time: A second stage treatment was performed under the conditions of 12 seconds to fix the copper particles.
【0030】これを直ちに十分水洗した後、その銅箔の
光沢面側に、浴組成:硫酸ニッケル・・・ニッケルとし
て4g/l 、硫酸銅・・・銅として0.5g/l 、
硫酸アンモニウム・・・50g/l 、ホウ酸・・・1
0g/l :pH2.5:浴温度25℃:陰極電流密度
5.5A/dm2 の条件でニッケル5mg/dm2の
ニッケル・銅合金をヤケめっきし、水洗した。Immediately after washing thoroughly with water, bath composition: nickel sulfate...4 g/l as nickel, copper sulfate...0.5 g/l as copper,
Ammonium sulfate...50g/l, boric acid...1
A nickel-copper alloy containing 5 mg/dm2 of nickel was tan-plated under the following conditions: 0 g/l: pH 2.5: bath temperature 25° C.: cathode current density 5.5 A/dm2, and washed with water.
【0031】その後、箔の粗化面側に、浴組成:硫酸亜
鉛7水塩・・・亜鉛として5g/l 、水酸化ナトリウ
ム・・・70g/l :浴温度25℃:陰極電流密度0
.5A/dm2 :処理時間1秒の条件で亜鉛めっきし
た。次いで、これを直ちに水洗後、箔の両面に、浴組成
:重クロム酸ナトリウム・・・25g/l :pH6:
浴温度45℃:陰極電流密度2A/dm2 :処理時間
1秒の条件でクロメ−ト処理した後、水洗、乾燥して多
層プリント配線板内層回路用銅箔を作製した。Then, on the roughened side of the foil, bath composition: zinc sulfate heptahydrate...5 g/l as zinc, sodium hydroxide...70 g/l: bath temperature 25°C: cathode current density 0
.. 5A/dm2: Zinc plating was carried out under the condition that the processing time was 1 second. Next, after immediately washing it with water, bath composition: Sodium dichromate...25 g/l: pH 6:
After chromate treatment under the conditions of bath temperature: 45° C., cathode current density: 2 A/dm 2 and treatment time: 1 second, the copper foil was washed with water and dried to produce a copper foil for inner layer circuits of a multilayer printed wiring board.
【0032】得られた多層プリント配線板内層回路用銅
箔について、以下に示す評価を行った。結果を表1及び
表2に示す。
(1) 内層銅箔引剥し試験
JIS C 6481に準拠した。
(2) AOIによる内層回路検査の所要時間塩化第2
鉄溶液を用いてエッチングし、線幅80μm、線間16
0μmの内層回路を形成後、オプトロテック社製 VI
SION 206 AOI を使用して、500×50
0mmの回路板1枚当たりを検査するのに要した時間を
求めた。
(3) ハロ−イング性評価
前記(2) と同様にして作製した内層回路板の裏表に
エポキシ含浸プリプレグを重ね合せ、180℃、50k
g/cm2で、120分間加熱プレスし、4層板を作製
した。得られた4層板に径0.4mmφのドリル穴をあ
け、これを12%塩酸に5分間浸漬し、そのハロ−イン
グ長さを測定した。
(4) Yxy値測定
JIS Z 8701に準拠した。The obtained copper foil for inner layer circuits of a multilayer printed wiring board was evaluated as follows. The results are shown in Tables 1 and 2. (1) Inner layer copper foil peeling test Compliant with JIS C 6481. (2) Required time for inner layer circuit inspection using AOI
Etched using iron solution, line width 80 μm, line spacing 16
After forming the 0μm inner layer circuit, Optrotech VI
500×50 using SION 206 AOI
The time required to inspect one 0 mm circuit board was determined. (3) Evaluation of haloing property Epoxy-impregnated prepreg was superimposed on the front and back sides of the inner layer circuit board prepared in the same manner as in (2) above, and heated at 180℃ for 50k
A four-layer board was produced by hot pressing at a pressure of g/cm2 for 120 minutes. A drill hole with a diameter of 0.4 mm was made in the four-layer board obtained, and the hole was immersed in 12% hydrochloric acid for 5 minutes, and the harrowing length was measured. (4) Yxy value measurement: Compliant with JIS Z 8701.
【0033】実施例2
電解銅箔の両面に銅粒子を実施例1と同様にして、付着
、固定した後、ニッケル−銅合金のヤケめっきに代えて
、箔の光沢面側に、浴組成:無水クロム酸・・・250
g/l 、酢酸・・・215g/l 、酢酸バリウム・
・・7.5g/l :浴温度40℃:電流密度15A/
dm2 :処理時間60秒の条件で黒色のクロムのめっ
きを行ったほかは、実施例1と同様にして、多層プリン
ト配線板内層回路用銅箔を作製した。 得られた多層
プリント配線板内層回路用銅箔について、実施例1と同
様にして評価した。結果を表1及び表2に示す。Example 2 After depositing and fixing copper particles on both sides of an electrolytic copper foil in the same manner as in Example 1, instead of the tan plating of nickel-copper alloy, the shiny side of the foil was coated with a bath composition: Chromic anhydride...250
g/l, acetic acid...215g/l, barium acetate...
7.5g/l: Bath temperature 40℃: Current density 15A/
dm2: A copper foil for an inner layer circuit of a multilayer printed wiring board was produced in the same manner as in Example 1, except that black chromium plating was performed under the conditions of a processing time of 60 seconds. The obtained copper foil for inner layer circuits of a multilayer printed wiring board was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【0034】実施例3
厚さ35μmの電解銅箔を陰極とし、その両側に鉛を陽
極として配置し、浴組成:硫酸銅5水塩・・・銅として
30g/l 、硫酸・・・80g/l :浴温度30℃
:電流密度15A/dm2 :処理時間:10秒の条件
で処理し、銅箔の粗面及び光沢面に銅粒子を付着させて
凹凸をつけた後、十分水洗し、ニッケル量3mg/dm
2のニッケル・銅合金をヤケめっきしたほかは、実施例
1と同様にして、多層プリント配線板内層回路用銅箔を
作製した。得られた多層プリント配線板内層回路用銅箔
について、実施例1と同様にして評価した。結果を表1
及び表2に示す。Example 3 Electrolytic copper foil with a thickness of 35 μm was used as a cathode, and lead was placed on both sides as an anode. Bath composition: copper sulfate pentahydrate...30 g/l as copper, sulfuric acid...80 g/l. l: Bath temperature 30℃
:Current density: 15A/dm2 :Processing time: Processed under the conditions of 10 seconds to create unevenness by adhering copper particles to the rough and glossy surfaces of the copper foil, and then washing thoroughly with water to reduce the amount of nickel to 3mg/dm.
A copper foil for an inner layer circuit of a multilayer printed wiring board was produced in the same manner as in Example 1, except that the nickel/copper alloy of No. 2 was plated with discoloration. The obtained copper foil for inner layer circuits of a multilayer printed wiring board was evaluated in the same manner as in Example 1. Table 1 shows the results.
and shown in Table 2.
【0035】実施例4
電解銅箔に代えて、厚さ35μmの圧延銅箔を用いたほ
かは、実施例1と同様にして、多層プリント配線板内層
回路用銅箔を作製した。得られた多層プリント配線板内
層回路用銅箔について、実施例1と同様にして評価した
。結果を表1及び表2に示す。Example 4 A copper foil for an inner layer circuit of a multilayer printed wiring board was produced in the same manner as in Example 1, except that a rolled copper foil having a thickness of 35 μm was used in place of the electrolytic copper foil. The obtained copper foil for inner layer circuits of a multilayer printed wiring board was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【0036】実施例5
ニッケル・銅合金ヤケめっきを光沢面側及び粗面側の両
方に形成したほかは、実施例1と同様にして、多層プリ
ント配線板内層回路用銅箔を作製した。得られた多層プ
リント配線板内層回路用銅箔について、実施例1と同様
にして評価した。結果を表1及び表2に示す。Example 5 A copper foil for an inner layer circuit of a multilayer printed wiring board was produced in the same manner as in Example 1, except that nickel/copper alloy discoloration plating was formed on both the glossy side and the rough side. The obtained copper foil for inner layer circuits of a multilayer printed wiring board was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【0037】比較例1
電解銅箔の粗面のみに、実施例1と同様にして、銅粒子
を付着、固定し、次いで、ニッケル・銅合金のヤケめっ
きをせずに、この粗面側のみに実施例1と同様にして亜
鉛めっき及びクロメ−ト処理して内層回路板用銅張板を
作製した。Comparative Example 1 Copper particles were attached and fixed only to the rough surface of an electrolytic copper foil in the same manner as in Example 1, and then only this rough surface was coated without tanning plating with nickel-copper alloy. A copper clad board for an inner layer circuit board was prepared by galvanizing and chromate treatment in the same manner as in Example 1.
【0038】次に、これを塩化第2鉄溶液を用いてエッ
チングし、線幅80μm、線間160μmの内層回路を
形成後、光沢面側のみに、浴組成:水酸化ナトリウム・
・・15g/l 、第三リン酸ナトリウム12水塩・・
・30g/l 、亜塩素酸ナトリウム・・・90g/l
:浴温度85℃:処理時間90秒の条件で黒色酸化処
理後、水洗して内層回路板を作製した。得られた内層回
路板について、実施例1と同様にして評価した。結果を
表1及び表2に示す。Next, this was etched using a ferric chloride solution to form an inner layer circuit with a line width of 80 μm and a line spacing of 160 μm, and then only the glossy side was etched with a bath composition of sodium hydroxide.
...15g/l, trisodium phosphate dodecahydrate...
・30g/l, sodium chlorite...90g/l
After black oxidation treatment under the following conditions: bath temperature: 85° C.: treatment time: 90 seconds, the inner layer circuit board was prepared by washing with water. The obtained inner layer circuit board was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【0039】比較例2
電解銅箔の粗面のみに、実施例1と同様にして、銅粒子
を付着、固定し、次いで、ニッケル・銅合金のヤケめっ
きに代えて、光沢面側のみに、浴組成:水酸化ナトリウ
ム・・・15g/l 、第三リン酸ナトリウム12水塩
・・・30g/l 、亜塩素酸ナトリウム・・・90g
/l :浴温度85℃:処理時間90秒の条件で黒色酸
化処理したほかは、実施例1と同様にして、多層プリン
ト配線板内層回路用銅箔を作製した。得られた多層プリ
ント配線板内層回路用銅箔について、実施例1と同様に
して評価した。結果を表1及び表2に示す。Comparative Example 2 Copper particles were adhered and fixed only to the rough surface of the electrolytic copper foil in the same manner as in Example 1, and then, instead of the faded plating of nickel-copper alloy, only the shiny surface was coated. Bath composition: Sodium hydroxide...15g/l, trisodium phosphate dodecahydrate...30g/l, sodium chlorite...90g
/l: A copper foil for an inner layer circuit of a multilayer printed wiring board was produced in the same manner as in Example 1, except that the black oxidation treatment was carried out under the conditions of bath temperature 85° C. and treatment time 90 seconds. The obtained copper foil for inner layer circuits of a multilayer printed wiring board was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【0040】比較例3
比較例2と同様にして作製した多層プリント配線板内層
回路用銅箔の光沢面側を、浴組成:水素化ホウ素ナトリ
ウム・・・1g/l :pH12.5:浴温度40℃:
処理時間40秒の条件で処理して水洗後、さらに、浴組
成:36%ホルマリン・・・4g/l 、硫酸ナトリウ
ム・・・71g/l :pH12.5:浴温度40℃:
処理時間・・・銅の表面の電位が−1200mV(銀−
塩化銀参照電極)になるまでの時間の条件で処理した後
、水洗して還元銅形成処理箔を作製した。得られた還元
銅形成処理箔について、実施例1と同様にして評価した
。結果を表1及び表2に示す。Comparative Example 3 The glossy side of the copper foil for the inner layer circuit of a multilayer printed wiring board produced in the same manner as in Comparative Example 2 was coated with a bath composition: Sodium borohydride...1 g/l: pH 12.5: Bath temperature 40℃:
After processing for 40 seconds and washing with water, bath composition: 36% formalin...4 g/l, sodium sulfate...71 g/l: pH 12.5: Bath temperature: 40°C:
Processing time: The potential of the copper surface is -1200 mV (silver -
The foil was treated with water to produce a reduced copper-forming treated foil. The obtained reduced copper-forming treated foil was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【0041】比較例4
電解銅箔の光沢面側に銅粒子を付着、固定しなかったほ
かは、実施例1と同様にして、多層プリント配線板内層
回路用銅箔を作製した。得られた多層プリント配線板内
層回路用銅箔について、実施例1と同様にして評価した
。結果を表1及び表2に示す。Comparative Example 4 A copper foil for an inner layer circuit of a multilayer printed wiring board was produced in the same manner as in Example 1, except that copper particles were not attached or fixed to the glossy side of the electrolytic copper foil. The obtained copper foil for inner layer circuits of a multilayer printed wiring board was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【0042】比較例5
電解銅箔の両面に、浴組成:硫酸銅5水塩・・・銅とし
て30g/l 、硫酸・・・80g/l 、塩酸酸性三
酸化アンチモン・・・アンチモンとして0.1g/l
、亜セレン酸・・・セレンとして0.1g/l :浴温
度30℃:電流密度15A/dm2 :処理時間:10
秒の条件で処理し、銅箔の粗面及び光沢面に銅粒子を付
着させて凹凸をつけた後、十分水洗し、ニッケル・銅合
金のヤケめっきをしなかったほかは、実施例1と同様に
して、多層プリント配線板内層回路用銅箔を作製した。
得られた多層プリント配線板内層回路用銅箔について、
実施例1と同様にして評価した。結果を表1及び表2に
示す。なお、本比較例の内層銅箔引剥し試験では、銅の
残りが多く認められた。Comparative Example 5 Both sides of the electrolytic copper foil were coated with bath composition: copper sulfate pentahydrate...30 g/l as copper, sulfuric acid...80 g/l, hydrochloric acid acidic antimony trioxide...0.0 g/l as antimony. 1g/l
, selenite...0.1 g/l as selenium: Bath temperature 30°C: Current density 15 A/dm2: Processing time: 10
The procedure was the same as that of Example 1, except that copper particles were applied to the rough and shiny surfaces of the copper foil to create irregularities, and then the copper foil was thoroughly washed with water and the nickel-copper alloy was not plated. In the same manner, a copper foil for an inner layer circuit of a multilayer printed wiring board was produced. Regarding the obtained copper foil for inner layer circuits of multilayer printed wiring boards,
Evaluation was made in the same manner as in Example 1. The results are shown in Tables 1 and 2. In addition, in the inner layer copper foil peeling test of this comparative example, a large amount of copper residue was observed.
【0043】比較例6
ニッケル・銅合金のヤケめっきをしなかったほかは、実
施例1と同様にして、多層プリント配線板内層回路用銅
箔を作製した。得られた多層プリント配線板内層回路用
銅箔について、実施例1と同様にして評価した。結果を
表1及び表2に示す。Comparative Example 6 A copper foil for an inner layer circuit of a multilayer printed wiring board was produced in the same manner as in Example 1, except that the nickel-copper alloy was not plated with discoloration. The obtained copper foil for inner layer circuits of a multilayer printed wiring board was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【0044】比較例7
ニッケル・銅合金のヤケめっき処理に代えて、比較例2
と同様に黒色酸化銅処理したほかは、実施例1と同様に
して、多層プリント配線板内層回路用銅箔を作製した。
得られた多層プリント配線板内層回路用銅箔につい
て、実施例1と同様にして評価した。結果を表1及び表
2に示す。Comparative Example 7 In place of the tan plating treatment of nickel/copper alloy, Comparative Example 2
A copper foil for an inner layer circuit of a multilayer printed wiring board was produced in the same manner as in Example 1, except that the copper foil was treated with black copper oxide in the same manner as in Example 1. The obtained copper foil for inner layer circuits of a multilayer printed wiring board was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【0045】[0045]
【表1】[Table 1]
【0046】[0046]
【表2】[Table 2]
【0047】[0047]
【発明の効果】本発明の多層プリント配線板内層回路用
銅箔によると、銅箔の両面に粗化処理がされているので
、内層回路とプリプレグとの密着性が向上し、さらに、
その粗化処理面上に黒色の金属めっき層を有しているの
で、ハロ−イング現象を起こさず、かつ短時間でしかも
正確にAOI検査できる。[Effects of the Invention] According to the copper foil for the inner layer circuit of a multilayer printed wiring board of the present invention, since both sides of the copper foil are roughened, the adhesion between the inner layer circuit and the prepreg is improved, and further,
Since a black metal plating layer is provided on the roughened surface, the haloing phenomenon does not occur, and the AOI test can be performed accurately in a short time.
【0048】また、本発明の製造方法によると、銅箔を
製造するときに、箔の両面粗化処理と金属の黒色めっき
処理を行うので、生産効率が優れ、さらに、多層プリン
ト配線板を製造する工程で、バッチ方式の化学処理工程
が省略できるので、多層プリント配線板の品質向上と生
産性の向上を同時に達成することができる。Furthermore, according to the manufacturing method of the present invention, since both sides of the foil are roughened and the metal is black-plated when manufacturing copper foil, production efficiency is excellent, and furthermore, multilayer printed wiring boards can be manufactured easily. Since the batch-type chemical treatment process can be omitted in the process, it is possible to simultaneously improve the quality and productivity of multilayer printed wiring boards.
Claims (4)
なくとも内層回路板の表面となる粗面上に、さらに黒色
の金属めっき層を設けたことを特徴とする多層プリント
配線板内層回路用銅箔。1. Copper for inner layer circuit of a multilayer printed wiring board, characterized in that a black metal plating layer is further provided on at least the rough surface of the copper foil which has been roughened on both sides, which will become the surface of the inner layer circuit board. foil.
バルト、クロム、ロジウム及びスズからなる群より選ば
れた1種以上の金属を含有する請求項1記載の多層プリ
ント配線板内層回路用銅箔。2. The copper foil for inner layer circuits of multilayer printed wiring boards according to claim 1, wherein the black metal plating layer contains one or more metals selected from the group consisting of nickel, cobalt, chromium, rhodium, and tin. .
たYxy値が15%以下の黒色めっき層を有する請求項
1記載の多層プリント配線板内層回路用銅箔。3. The copper foil for internal layer circuits of a multilayer printed wiring board according to claim 1, which has a black plating layer having a Yxy value of 15% or less as defined in JIS Z 8701.
色の金属めっき層を形成することを特徴とする多層プリ
ント配線板内層回路用銅箔の製造方法。4. A method for manufacturing a copper foil for inner layer circuits of a multilayer printed wiring board, which comprises roughening both sides of the copper foil and forming a black metal plating layer on the copper foil.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7208691A JPH04284690A (en) | 1991-03-13 | 1991-03-13 | Copper foil for inner layer circuit of multilayer printed circuit board and manufacture thereof |
TW080103802A TW208110B (en) | 1990-06-08 | 1991-05-16 | |
US07/706,053 US5320919A (en) | 1990-06-08 | 1991-05-28 | Copper foil for inner layer circuit of multi-layered printed circuit board, method of producing the same and multi-layered printed circuit board having the same |
EP91304818A EP0460856B1 (en) | 1990-06-08 | 1991-05-29 | Copper foil for inner layer circuit of multi-layered printed circuit board, method of producing the same and multi-layered printed circuit board having the same |
DE69121143T DE69121143T2 (en) | 1990-06-08 | 1991-05-29 | Copper foil for the inner layer circuit of a multilayer printed circuit board, process for its production and multilayer printed circuit board containing it |
KR1019910008954A KR100272992B1 (en) | 1990-06-08 | 1991-05-30 | Copper foil for inner layer circuit of multi-layered printed circuit board, method of procucing the same and multi-l.... |
MYPI91001004A MY106538A (en) | 1990-06-08 | 1991-06-07 | Copper foil for inner layer circuit of multi-layered printed circuit board, method of producing the same and multi-layered printed circuit board having the same. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7208691A JPH04284690A (en) | 1991-03-13 | 1991-03-13 | Copper foil for inner layer circuit of multilayer printed circuit board and manufacture thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04284690A true JPH04284690A (en) | 1992-10-09 |
Family
ID=13479242
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7208691A Pending JPH04284690A (en) | 1990-06-08 | 1991-03-13 | Copper foil for inner layer circuit of multilayer printed circuit board and manufacture thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04284690A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996017503A1 (en) * | 1994-12-01 | 1996-06-06 | Ibiden Co., Ltd. | Multilayer printed wiring board and process for producing the same |
US5800930A (en) * | 1994-01-21 | 1998-09-01 | Olin Corporation | Nodular copper/nickel alloy treatment for copper foil |
JP2001168481A (en) * | 1999-12-08 | 2001-06-22 | Ibiden Co Ltd | Copper-clad laminate, and circuit substrate for printed wiring board and manufacturing method therefor |
JP2002176242A (en) * | 2000-12-05 | 2002-06-21 | Nikko Materials Co Ltd | Copper foil for electronic circuit and method for forming electronic circuit |
US6544664B1 (en) | 1999-05-25 | 2003-04-08 | Mitsui Mining & Smelting Co., Ltd. | Copper foil for printed wiring board |
JP2004349693A (en) * | 2003-04-30 | 2004-12-09 | Mec Kk | Resin adhesive layer on surface of copper |
JP2007115993A (en) * | 2005-10-21 | 2007-05-10 | Sumitomo Bakelite Co Ltd | Printed wiring board, its production method and multilayered printed wiring board |
JP2007207812A (en) * | 2006-01-31 | 2007-08-16 | Nikko Kinzoku Kk | Copper foil for printed wiring board and printed wiring board using the same |
JP2012094918A (en) * | 2003-04-30 | 2012-05-17 | Mec Kk | To-resin adhesive layer on surface of copper, wiring board, and method for forming adhesive layer |
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-
1991
- 1991-03-13 JP JP7208691A patent/JPH04284690A/en active Pending
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5800930A (en) * | 1994-01-21 | 1998-09-01 | Olin Corporation | Nodular copper/nickel alloy treatment for copper foil |
CN1117512C (en) * | 1994-12-01 | 2003-08-06 | 揖斐电株式会社 | Multilayer printed wiring board and process for producing the same |
EP0743812A4 (en) * | 1994-12-01 | 1999-05-06 | Ibiden Co Ltd | Multilayer printed wiring board and process for producing the same |
KR100269580B1 (en) * | 1994-12-01 | 2000-10-16 | 엔도 마사루 | Multilayer printed wiring board and process for producing the same |
US5827604A (en) * | 1994-12-01 | 1998-10-27 | Ibiden Co., Ltd. | Multilayer printed circuit board and method of producing the same |
WO1996017503A1 (en) * | 1994-12-01 | 1996-06-06 | Ibiden Co., Ltd. | Multilayer printed wiring board and process for producing the same |
US6544664B1 (en) | 1999-05-25 | 2003-04-08 | Mitsui Mining & Smelting Co., Ltd. | Copper foil for printed wiring board |
JP4486196B2 (en) * | 1999-12-08 | 2010-06-23 | イビデン株式会社 | Single-sided circuit board for multilayer printed wiring board and manufacturing method thereof |
JP2001168481A (en) * | 1999-12-08 | 2001-06-22 | Ibiden Co Ltd | Copper-clad laminate, and circuit substrate for printed wiring board and manufacturing method therefor |
JP2002176242A (en) * | 2000-12-05 | 2002-06-21 | Nikko Materials Co Ltd | Copper foil for electronic circuit and method for forming electronic circuit |
JP2004349693A (en) * | 2003-04-30 | 2004-12-09 | Mec Kk | Resin adhesive layer on surface of copper |
JP2012094918A (en) * | 2003-04-30 | 2012-05-17 | Mec Kk | To-resin adhesive layer on surface of copper, wiring board, and method for forming adhesive layer |
JP2007115993A (en) * | 2005-10-21 | 2007-05-10 | Sumitomo Bakelite Co Ltd | Printed wiring board, its production method and multilayered printed wiring board |
JP2007207812A (en) * | 2006-01-31 | 2007-08-16 | Nikko Kinzoku Kk | Copper foil for printed wiring board and printed wiring board using the same |
JP4683640B2 (en) * | 2006-01-31 | 2011-05-18 | Jx日鉱日石金属株式会社 | Copper foil for printed wiring board and printed wiring board using the same |
JPWO2016093109A1 (en) * | 2014-12-08 | 2017-09-14 | 三井金属鉱業株式会社 | Method for manufacturing printed wiring board |
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