JPH01156479A - 銅の表面処理法 - Google Patents

銅の表面処理法

Info

Publication number
JPH01156479A
JPH01156479A JP62315750A JP31575087A JPH01156479A JP H01156479 A JPH01156479 A JP H01156479A JP 62315750 A JP62315750 A JP 62315750A JP 31575087 A JP31575087 A JP 31575087A JP H01156479 A JPH01156479 A JP H01156479A
Authority
JP
Japan
Prior art keywords
copper
soln
contact
copper surface
oxidized
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.)
Granted
Application number
JP62315750A
Other languages
English (en)
Other versions
JPH0713304B2 (ja
Inventor
Akishi Nakaso
昭士 中祖
Tomoko Watanabe
智子 渡辺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP62315750A priority Critical patent/JPH0713304B2/ja
Priority to DE8888306625T priority patent/DE3874867T2/de
Priority to EP88306625A priority patent/EP0321067B1/en
Priority to US07/224,911 priority patent/US4902551A/en
Priority to KR1019880009708A priority patent/KR910001549B1/ko
Publication of JPH01156479A publication Critical patent/JPH01156479A/ja
Priority to KR1019900018958A priority patent/KR910000573B1/ko
Priority to SG1309/92A priority patent/SG130992G/en
Publication of JPH0713304B2 publication Critical patent/JPH0713304B2/ja
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/12—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/60—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 using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0315—Oxidising metal
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1157—Using means for chemical reduction
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/427—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in metal-clad substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/901—Printed circuit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
    • Y10T156/1056—Perforating lamina
    • Y10T156/1057—Subsequent to assembly of laminae
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49117—Conductor or circuit manufacturing
    • Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
    • Y10T29/49155—Manufacturing circuit on or in base
    • Y10T29/49165—Manufacturing circuit on or in base by forming conductive walled aperture in base
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
    • Y10T428/24322—Composite web or sheet

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Laminated Bodies (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は、多層プリント配線板を製造する際に。
内層回路板とプリプレグとを積層一体化する工程におい
て内層回路板上の銅とプリプレグとの接着に適した銅表
面の処理方法に関する。
（従来の技術） 従来、多層プリント配線板は、ｖｉ４張積層積層板箔の
不要な部分をエツチング等によって除去して内層回路を
形成し、内層回路の銅表面を化学液で粗化し、粗化した
表面を酸化処理し、プリプレグ及び外層回路となる銅箔
をその上に重ねて積層−体化し、外層回路及び内層回路
の接続を必要とする箇所に穴をあけ、その穴内面に付着
した樹脂やガラスの片を化学液で除去した後に無電解め
っき等を用いて銅等の金属層を形成し、外層回路をエツ
チング等によって形成することによって、製造されてい
た。このとき、穴内面に露出した銅表面の酸化処理層が
、その後の酸性の化学処理液に侵され、穴の周囲の内層
銅箔とプリプレグの接着が維持されない部分（ハローイ
ングという）ができはんだ付は等の熱衝撃によって単離
するという問題があったので、酸化銅より酸性の化学処
理液に溶は難い表面を形成するために、特開昭５６−１
５３７９７に開示されているように、酸化銅を形成した
後に水素化ホウ素ナトリウム、ホルムアルデヒド等のア
ルカリ溶液に浸漬してその表面を一 還元することが行われている。
（発明が解決しようとする問題点） 水素化ホウ素ナトリウムを用いて酸化銅を還元した場合
は、処理後の外観がむらになりプリプレグとの接着が不
充分な場合がある。
また、ホルムアルデヒドの水溶液の場合は、処理速度が
小さいという問題が発生した。この原因として、鋭意研
究の結果、酸化処理した銅表面をホルムアルデヒドの水
溶液に接触させ銅のＡｇ−ＡｇＣｌ電極に対する電位が
一４００ｍＶより貴の電位である場合に還元処理速度が
小さくなることが分かった。
本発明は、このような問題を解決し、接着が充分に行え
処理速度の大きい酸化処理した銅表面の処理方法に関す
る。
（問題点を解決する手段） 本発明は２以下の工程を以下の順に含む処理工程によっ
て銅表面に形成した酸化銅を金属銅にｊ量元することを
特徴とする銅の表面処理法である。
ａ、銅表面を酸化剤を含む水溶液と接触させて。
銅表面に酸化銅を形成する工程。
ｂ、酸化処理した銅表面を水素化ホウ素アルカリを含む
水溶液と接触させることによって、酸化処理した銅表面
の電位をＡｇ−へｇｃｇ電極に対して−１，０００ｍＶ
以上で一４００ｍＶ以下の範囲内に変化させる工程。
ｃ．ホルムアルデヒドを含む水溶液と接触させることに
よって、酸化処理した銅表面の電位をＡｇ−Ａｇ（１！
電極に対して一１０００ｍＶよりも卑な電位に変化させ
る工程。
本発明において、工程ａの銅表面に酸化銅を形成する方
法は、一般に知られている亜塩素酸ナトリウム、過硫酸
アルカリ、塩素酸カリウム、過塩素酸カリウム等の酸化
剤を含む処理液に浸漬又はその処理液を吹き付けて行う
。この銅の酸化処理液組成の一例は。
ＮａＣｌ０ｚ　　；３０〜１５０ｇ／ＮＮａ３　ＰＯ４
−１２Ｈ２０ｉ　１０〜６０　ｇ／ｌＮａＯＨ；５〜３
０ｇ／ｆｆｉ である。また、その処理条件は、液温が５５〜９５℃で
ある。さらに、酸化銅を形成するための銅表面の前処理
として、脱脂を行い、過硫酸アンモニウム水？８　？＆
又は塩化第２銅と塩酸とを含む水溶液等に接触させて銅
表面を粗化することが好ましい。
工程すで使用する還元剤である水素化ホウ素アルカリと
は、水素化ホウ素ナトリウムや水素化ホウ素カルシウム
等である。この水素化ホウ素アルカリの濃度は、酸化処
理した銅表面の電位の変化する速度と、還元後の外観の
均一性とに影響する。その濃度は、０．１ｇ／ｊ！以上
、好ましくは０．２〜５ｇ／ｌで用いる。
また、水素化ホウ素アルカリは自然分解し易いので、抑
制するために、酢酸鉛、塩化鉛、硫酸鉛又はチオグリコ
ール酸を添加することが好ましく、また、ｐＨをｔｏ−
１３，５に維持することによっても可能である。
酸化処理した銅表面と水素化ホウ素アルカリの接触時間
は極めて重要である。酸化処理した銅表面を水素化ホウ
素アルカリに接触させると、酸化銅が還元され始め、酸
化処理した銅表面の電位が卑の方へ変化していく、この
とき、電位が一４００ｍＶ以上になるまで接触時間を長
くすると１次のＣの工程後に外観の不均一を発生し、接
着強度が大きくならないこともある。このような問題の
発生しない範囲が、−１０００ｍＶ以上で一４００ｍＶ
以下である。実際には、常に電位の監視をする必要はな
く、水素化ホウ素アルカリを含む水溶液の組成と温度に
よって、望ましい接触時間が決定できる。−例として、
水素化ホウ素ナトリウムの場合、濃度：１ｇ／ｊ！、ｐ
Ｈ；１２．５．温度；４０℃のときの望ましい接触時間
は３〜１８０秒である。
工程Ｃで用いるホルムアルデヒドの水溶液の濃度は、３
６％ホルマリンを使用した場合、０．５ｍ　ｅ　／　４
８以上で、２〜１５ｍｊ！／ｊ！が好ましい範囲である
。また、このホルムアルデヒドの水溶液のｐ　Ｈは９以
上、好ましくは１０．５以上である。
このｐ　Ｈを調整するには、水酸化アルカリ等を用いる
。
このホルムアルデヒドを含む水溶液に、酸化処理をし工
程すの処理をした銅表面を接触させると−１０００ｍ　
Ｖより卑に変化する。このホルムアルデヒドに接触させ
るのに、銅の電位が一１０００ｍＶより卑に変化するま
での時間が必要である。実際には、工程すと同様にホル
ムアルデヒドを含む水溶液の組成、濃度、温度を定めて
望ましい接触時間に替えることができる。−例として、
３６％ホルマリンを、濃度；　４ｍｌ／ｌ、ｐＨ；　１
２．５゜温度；５０℃のときの望ましい接触時間は、１
８０秒である。
工程すの処理を行った銅表面は、そのまま工程Ｃの処理
をすることもでき、水洗して工程Ｃの処理をしてもよい
。
また１本発明は、多層プリント配線板の内層回路表面の
処理のみでなく、プリント配線板の外層回路の表面処理
、銅箔と絶縁材との貼り合わせ等にも用いることができ
る。
実施例 あらかじめ、内層回路を形成した内層回路板を過硫酸ア
ンモニウム水溶液で粗化した後、以下の組成１条件で処
理して、内層回路の銅表面に酸化銅を形成した。
組成 水酸化ナトリウム１１５ｇ／Ａ リン酸３ナトリウム；　３０　ｇ／１ （Ｎａｓ　ＰＯ４・１２１１！　Ｏ） 亜塩素酸ナトリウム；　９０　ｇ　／　１水；以上の組
成物と合わせて１７！となる量条件 液温；８５℃ 処理時間；９０秒 次に、水洗した後以下の組成９条件で処理した。
組成 水素化ホウ素ナトリウム；　１　ｇ／ｌ水；組成物と合
わせて１１となる量 条件 ｐＨ，１２，，５ 液温：４０℃ 処理時間；４０秒 次に、以下の組成２条件で処理した。
組成 ３６％ホルマリン；４ｍＲ／１ 水；組成物と合わせて１１となる■ 条件 ｐＨ，１２，５ 液温；５０℃ 処理時間；５分 以」二のように処理した内層回路板を、水洗し、８０℃
で３０分乾燥した後、この両側にエポキシ変性ポリイミ
ド樹脂プリプレグであるＬ−６７（日立化成工業株式会
社、商品名）で挟みさらにその両外側を３５μｍの銅箔
で挟んで積み重ね、圧力５０ｋｇ／ａＪ、温度１７０℃
１時間９０分の条件で加熱加圧して積層一体化した試験
片を作成した。
比較例１ あらかじめ、内層回路を形成した内層回路板を過硫酸ア
ンモニウム水溶液で粗化した後、以下の組成１条件で処
理して、内層回路の銅表面に酸化銅を形成した。
組成 水酸化ナトリウム；１５ｇ／ｌ リン酸３ナトリウム：３０ｇ／１ （Ｎａ＝　ｐｏ、’１２Ｈｚ　Ｏ） 亜塩素酸ナトリウム；　９０　ｇ／ｊ！水；以上の組成
物と合わせて１１となる量条件 液温；８５℃ 処理時間；９０秒 次に、水洗した後以下の組成１条件で処理した。
組成 水素化ホウ素ナトリウム；Ｉｇ／ｊ！ 水；組成物と合わせてＩｚとなる量 条件 ｐＨ；１２．５ 液温；４０℃ 処理時間；１０分 以上のように処理した内層回路板を、水洗し、８０℃で
３０分乾燥した後、この両側にエポキシ変性ポリイミド
樹脂プリプレグであるＬ−６７（日立化成工業株式会社
、商品名）で挟みさらにその両外側を３５μｍの銅箔で
挟んで積み重ね、圧力５０ｋｇ／ｃｊ、温度１７０℃９
時間９０分の条件で加熱加圧して積層一体化した試験片
を作成した。
比較例２ あらかしめ、内層回路を形成した内層回路板を過硫酸ア
ンモニウム水溶液で粗化した後、以下の組成２条件で処
理して、内層回路の銅表面に酸化銅を形成した。
組成 水酸化ナトリウム；１５ｇ／ｌ リン酸３ナトリウム；　３０　ｇ　／　ｅ（Ｎ　ａ　！
Ｐ　Ｏｓ　　・１２８ｔ　Ｏ）亜塩素酸ナトリウム；　
９０　ｇ／ｌ 水：以上の組成物と合わせて１７！となる量条件 液温；８５℃ 処理時間；９０秒 次に、水洗した後以下の組成５条件で処理した。
組成 ３６％ホルマリン：４ｍＲ／１ 水；組成物と合わせて１１となる量 条件 ｐＨ；１２．５ 液温：５０℃ 処理時間；５分 以上のように処理した内層回路板を、水洗し、８０℃で
３０分乾燥した後、この両側にエポキシ変性ポリイミド
樹脂プリプレグである■、−６７（日立化成工業株式会
社、商品名）で挟みさらにその両外側を３５μｍの銅箔
で挟んで積み重ね、圧力５０ｋｇ／ａ！、温度１７０℃
１時間９０分の条件で加熱加圧して積層一体化した試験
片を作成した。
以上のようにして作成した各々の試験片に以下の試験を
行った。その結果を第１表に示す。
（１１内層銅箔引きＩ？ＪＩがし試験 試験法、ＪＩＳ−Ｃ６４８１ （２）耐塩酸試験 試験法； ■１３０ｍｍＸ　１３０ｍｍの大きさに切断加工０表面
銅箔を除去 ■直径１ｍｍの穴を３０箇所にあける ０１９％塩酸に浸漬 ■塩酸が内層に浸み込む時間の測定 （３）耐無電解めっき液試験 試験法； ■１３０ｍｍＸ　１３０ｍｍの大きさに切断加工０表面
銅箔を除去 ■直径１ｍｍの穴を３０箇所にあける ■以下の無電解めっき液に浸漬 組成 Ｃｕ５Ｏ，−５Ｈ，Ｑ：　１０ｇ／ｊ！ＥＤＴ八−２Ｎ
ａ：３０へ／１ ３６％ホルマリン：　５　ｍ　１　／　１純水：Ｍｉ成
物と合わせて１１となる量条件 温度ニア０℃ ｐＨ４１２，５ ■無電解めっき液が内層に浸み込む時間の測定（発明の
効果） 以上に説明したように１本発明によって外観が均一で処
理むらのない表面が得られ、接着強度が増し、また、工
程内での酸性の処理液等に耐性の手続補正書（自発） 昭和６３年　６月　９日 ｑ：

Claims (1)

    【特許請求の範囲】
  1. １．以下の工程を以下の順に含む処理工程によって銅表
    面に形成した酸化銅を金属銅に還元することを特徴とす
    る銅の表面処理法。 ａ．銅表面を酸化剤を含む水溶液と接触させて，銅表面
    に酸化銅を形成する工程。 ｂ．酸化処理した銅表面を水素化ホウ素アルカリを含む
    水溶液と接触させることによって，酸化処理した銅表面
    の電位をＡｇ−ＡｇＣｌ電極に対して−１０００ｍＶ以
    上で−４００ｍＶ以下の範囲内に変化させる工程。 ｃ．ホルムアルデヒドを含む水溶液と接触させることに
    よって，酸化処理した銅表面の電位をＡｇ−ＡｇＣｌ電
    極に対して−１０００ｍＶよりも卑な電位に変化させる
    工程。
JP62315750A 1987-12-14 1987-12-14 銅の表面処理法 Expired - Lifetime JPH0713304B2 (ja)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP62315750A JPH0713304B2 (ja) 1987-12-14 1987-12-14 銅の表面処理法
DE8888306625T DE3874867T2 (de) 1987-12-14 1988-07-20 Verfahren zur behandlung einer kupferoberflaeche.
EP88306625A EP0321067B1 (en) 1987-12-14 1988-07-20 Process for treating copper surface
US07/224,911 US4902551A (en) 1987-12-14 1988-07-27 Process for treating copper surface
KR1019880009708A KR910001549B1 (ko) 1987-12-14 1988-07-30 구리표면의 처리방법과 이를 이용한 구리-피착 라미네이트 및 필름
KR1019900018958A KR910000573B1 (ko) 1987-12-14 1990-11-22 다층 배선판
SG1309/92A SG130992G (en) 1987-12-14 1992-12-21 Process for treating copper surface

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62315750A JPH0713304B2 (ja) 1987-12-14 1987-12-14 銅の表面処理法

Publications (2)

Publication Number Publication Date
JPH01156479A true JPH01156479A (ja) 1989-06-20
JPH0713304B2 JPH0713304B2 (ja) 1995-02-15

Family

ID=18069094

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62315750A Expired - Lifetime JPH0713304B2 (ja) 1987-12-14 1987-12-14 銅の表面処理法

Country Status (6)

Country Link
US (1) US4902551A (ja)
EP (1) EP0321067B1 (ja)
JP (1) JPH0713304B2 (ja)
KR (1) KR910001549B1 (ja)
DE (1) DE3874867T2 (ja)
SG (1) SG130992G (ja)

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US4902551A (en) 1990-02-20
KR890010277A (ko) 1989-08-07
DE3874867D1 (de) 1992-10-29
EP0321067A1 (en) 1989-06-21
DE3874867T2 (de) 1993-03-04
SG130992G (en) 1993-03-12
KR910001549B1 (ko) 1991-03-15
JPH0713304B2 (ja) 1995-02-15
EP0321067B1 (en) 1992-09-23

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