JP4859232B2 - Electroless plating pretreatment agent and copper-clad laminate for flexible substrate - Google Patents

Electroless plating pretreatment agent and copper-clad laminate for flexible substrate Download PDF

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Publication number
JP4859232B2
JP4859232B2 JP2006535103A JP2006535103A JP4859232B2 JP 4859232 B2 JP4859232 B2 JP 4859232B2 JP 2006535103 A JP2006535103 A JP 2006535103A JP 2006535103 A JP2006535103 A JP 2006535103A JP 4859232 B2 JP4859232 B2 JP 4859232B2
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copper
electroless plating
pretreatment agent
clad laminate
plating
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JPWO2006027947A1 (en
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寿文 河村
徹 伊森
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
    • 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • H05K3/387—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component

Description

【技術分野】
【０００１】
本発明は、プリント配線用フレキシブル基板の素材等となる銅張り積層体の基材に用いる無電解めっき前処理剤、及びそれを用いて作製されたフレキシブル基板用銅張り積層体に関する。
【背景技術】
【０００２】
ポリイミド基板は、電子部品用の絶縁基板材料として多用されている。最近では電子機器の薄型化、小型化に伴い、ポリイミドフィルムに直接金属層を形成した、より自由度の高い２層銅ポリイミド基板が注目されているが、この基板は、ポリイミドフィルムと金属層の常態での初期密着力は実用レベルだが、耐熱・高温高湿環境での密着力などの特性が不安視されている。
【０００３】
また、ポリイミドフィルムのフレキシブル銅張り積層板について、金属層をスパッタリング法により製造する方法が例えば特許文献１に開示されている。しかしこの方法ではコスト高であり、耐熱・高温高湿環境での密着力は満足できるものではなかった。
【０００４】
ポリイミドフィルムと金属層の密着性を向上するための方法としてはプラズマ、ＵＶ等の乾式プロセス、アルカリ等での湿式プロセスがあるが、使用液の安全性・作業性や、過度に処理すると金属層表面に凹凸ができ、微細配線形成に悪影響を与える可能性がある。
【０００５】
また、特許文献２には、ポリイミドフィルムに樹脂組成物被膜を形成する工程、該被膜活性化工程、触媒付与工程、触媒活性化工程、無電解金属めっき工程の５工程からなる無電解銅めっきを行なった後電気銅めっきを行う方法が記載されている。この方法は密着付与層として樹脂組成物層を生成させることを主題としており、その結果樹脂組成物層の膜厚は１〜２０μｍを有し、工程が煩雑である。
【特許文献１】
特開平９−１３６３７８号公報
【特許文献２】
特開２００１−１６８４９６号公報
【発明の開示】
【発明が解決しようとする課題】
本発明は、基材と銅めっき層の常態での初期密着力、及び耐熱エージング試験（大気中、１５０℃、１６８時間）での密着力が０．４ｋｇｆ／ｃｍ以上となるフレキシブル基板用銅張り積層体に用いる無電解めっき前処理液、及び該無電解めっき前処理液を用いて作製されたフレキシブル基板用銅張り積層体を提供することを目的とする。
【課題を解決するための手段】
本発明者らは、上記課題について鋭意検討した結果、フレキシブル基板用銅張り積層体の無電解めっき前処理剤として、金属捕捉能を有するシランカップリング剤と熱硬化性樹脂とを含む有機溶媒溶液からなる無電解めっき前処理剤を用いることにより、上記課題を解決することができることを見出した。即ち、本発明は以下の通りである。
【０００８】
（１）フレキシブル基板用銅張り積層体の基材に用いる無電解めっき前処理剤であって、アゾール系化合物またはアミン化合物とエポキシ系化合物との反応により得られる金属捕捉能を有するシランカップリング剤、またはγ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシランから選ばれる金属捕捉能を有するシランカップリング剤と、熱硬化性樹脂とを含むことを特徴とする無電解めっき前処理剤。
（２）前記熱硬化性樹脂がエポキシ樹脂であることを特徴とする前記（１）記載の無電解めっき前処理剤。
（３）基材を前記（１）又は（２）記載の無電解めっき前処理剤で処理した後、無電解めっきにより銅めっき層を形成し、その上に電気めっきにより銅めっき層を形成したことを特徴とするフレキシブル基板用銅張り積層体。
【発明の効果】
本発明の無電解めっき前処理剤を用いて基材を処理し、その後無電解銅めっき層、電気銅めっき層を積層したフレキシブル基板用銅張り積層体は、基材と銅めっき層の常態での初期密着力、及び耐熱エージング試験（大気中、１５０℃、１６８時間）での密着力が０．４ｋｇｆ／ｃｍ以上となる、密着性に優れた２層銅張りフレキシブル基板用銅張り積層体となる。基材表面へは乾式・湿式前処理を全く行なわずに密着力を付与できる。
【発明を実施するための最良の形態】
本発明の無電解めっき前処理剤は、金属捕捉能を有するシランカップリング剤と熱硬化性樹脂とを含む。
【００１３】
金属捕捉能を有するシランカップリング剤を添加することにより、被めっき面に対してシランカップリング剤を介して貴金属触媒をより均一に、より確実に固着することができる。
【００１４】
前記シランカップリング剤として、好ましいものはアゾール系化合物またはアミン化合物とエポキシ系化合物との反応により得られるものである。
アゾール系化合物としては、イミダゾール、オキサゾール、チアゾール、セレナゾール、ピラゾール、イソオキサゾール、イソチアゾール、トリアゾール、オキサジアゾール、チアジアゾール、テトラゾール、オキサトリアゾール、チアトリアゾール、ベンダゾール、インダゾール、ベンズイミダゾール、ベンゾトリアゾールなどが挙げられる。これらに制限されるものではないが、イミダゾールが特に好ましい。
【００１５】
また、アミン化合物としては、例えばプロピルアミン等の飽和炭化水素アミン、ビニルアミン等の不飽和炭化水素アミン、フェニルアミン等の芳香族アミン等を挙げることができる。
【００１６】
また前記シランカップリング剤とは、前記アゾール系化合物またはアミン化合物由来の貴金属捕捉基の他に、−ＳｉＸ１Ｘ２Ｘ３基を有する化合物であり、Ｘ１、Ｘ２、Ｘ３はアルキル基、ハロゲンやアルコキシ基などを意味し、被めっき物への固定が可能な官能基であれば良い。Ｘ１、Ｘ２、Ｘ３は同一でもまた異なっていても良い。
【００１７】
前記シランカップリング剤は、前記アゾール系化合物またはアミン化合物とエポキシシラン化合物を反応させることにより得ることができる。
【００１８】
このようなエポキシシラン化合物としては、
【化１】

Figure 0004859232
（式中、Ｒ1、Ｒ2は水素または炭素数が１〜３のアルキル基、ｎは０〜３）
で示されるエポキシカップリング剤が好ましい。
【００１９】
前記アゾール系化合物と前記エポキシ基含有シラン化合物との反応は、例えば特開平６−２５６３５８号公報に記載されている条件で行うことができる。
【００２０】
例えば、８０〜２００℃でアゾール系化合物１モルに対して０．１〜１０モルのエポキシ基含有シラン化合物を滴下して５分〜２時間反応させることにより得ることができる。その際、溶媒は特に不要であるが、クロロホルム、ジオキサン、メタノール、エタノール等の有機溶媒を用いてもよい。
【００２１】
特に好ましい例としてイミダゾール化合物とエポキシシラン系化合物の反応を下記に示す。
【化２】
Figure 0004859232
（式中、Ｒ1、Ｒ2は水素または炭素数が１〜３のアルキル基、Ｒ3は水素、または炭素数１〜２０のアルキル基、Ｒ4はビニル基、または炭素数１〜５のアルキル基、ｎは０〜３を示す。）
【００２２】
本発明に使用する金属捕捉能を持つ官能基を有するシランカップリング剤のその他の例として、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン等が挙げられる。
【００２３】
本発明の無電解めっき前処理剤に用いる熱硬化性樹脂としては、エポキシ樹脂、尿素樹脂、フェノール樹脂、メラミン樹脂、ウレタン樹脂等が挙げられる。熱硬化性樹脂を添加することにより、密着力が向上する。熱硬化性樹脂としては、エポキシ樹脂を用いると特に密着力向上の効果が大きく、好ましい。
【００２４】
本発明において、無電解めっき前処理剤に貴金属化合物が含有されることは必須ではない。本めっき前処理剤に浸漬後、塩化パラジウム水溶液に浸漬することでめっき活性を得ることができる。しかし、めっき前処理剤が貴金属化合物等の触媒を含有することがより好ましい。触媒としては、パラジウム、銀、白金、金等の貴金属化合物、例えば、それらのハロゲン化物、水酸化物、硫酸塩、炭酸塩、貴金属石鹸等を挙げることができ、特にパラジウム化合物が好ましい。また、従来の塩化スズなどの触媒も本発明の目的の範囲内において含有させることができる。
【００２５】
貴金属石鹸は、脂肪酸、樹脂酸、またはナフテン酸と、貴金属化合物との反応により得ることができ、本発明において好ましく用いることができる。
【００２６】
脂肪酸としては、炭素原子数が５〜２５のものが好ましく、より好ましくは８〜１６である。脂肪酸の炭素数が４以下であると、有機溶媒に溶解しにくくなり、不安定となる。また炭素原子数が２６以上であると有機溶媒への可溶分が限定されること、貴金属含有量が低下することで添加量が多くなり実用的でない。
【００２７】
前記脂肪酸としては、オクチル酸、ネオデカン酸、ドデカン酸、ペンタデカン酸、オクタデカン酸等の飽和脂肪酸、オレイン酸、リノール酸等の不飽和脂肪酸、ヒドロキシテトラデカン酸、カルボキシデカン酸等の含酸素脂肪酸、あるいはこれらの混合物を挙げることができる。
【００２８】
また、前記脂肪酸、樹脂酸、ナフテン酸のうち、好ましいものを例示すると、ナフテン酸、オクチル酸、ネオデカン酸、ペンタデカン酸等を挙げることができる。
【００２９】
また、前記貴金属化合物としては無電解めっき液から被めっき物表面に銅やニッケルなどを析出させる際の触媒効果を示すパラジウム、銀、白金、金等のハロゲン化物、水酸化物、硫酸塩、炭酸塩等の化合物であって、脂肪酸等と石鹸を形成し得る化合物を挙げることができるが、特にパラジウム化合物が好ましい。
【００３０】
本発明に使用する貴金属石鹸は、前記脂肪酸等と前記貴金属化合物とを複分解法、直接法等の金属石鹸製造法の常法により得ることができる。
【００３１】
本発明に使用する貴金属石鹸として好ましいナフテン酸パラジウムを下記に示す。
【化３】
Figure 0004859232
【００３２】
本発明に使用する前記貴金属石鹸は、有機溶剤に可溶性であり、また溶液として安定である。このような有機溶剤としては、例えば、ブタノール、２−エチルへキサノール、オクチルアルコール等のアルコール、キシレン等の芳香族炭化水素、ヘキサン等の脂肪族炭化水素、クロロホルム、ジオキサン等を挙げることができる。
【００３３】
本発明の無電解めっき前処理剤は、上記金属捕捉能を有するシランカップリング剤、熱硬化性樹脂、貴金属石鹸等を、例えば、ブタノール、２−エチルへキサノール、オクチルアルコール等のアルコール、キシレン等の芳香族炭化水素、ヘキサン等の脂肪族炭化水素、クロロホルム、ジオキサン等の有機溶剤に溶解させて用いる。
【００３４】
無電解めっき前処理剤中の金属捕捉能を有するシランカップリング剤の濃度はこれに限ったものではないが、０．００１〜１０重量％が好ましく、０．０５〜３重量％がより好ましい。０．００１重量％未満の場合、基材の表面に付着する化合物量が低くなりやすく、効果が得にくい。また、１０重量％を超えると付着量が多すぎて乾燥しにくかったり、粉末の凝集を起こしやすくなる。
【００３５】
無電解めっき前処理剤中の熱硬化性樹脂の濃度は０．００１〜３０重量％が好ましく、０．０５〜１０重量％がより好ましい。０．００１重量％より少ないと効果がなく、３０重量％を超えると液粘度が高くなりすぎるため、めっき付きにむらが出る。
【００３６】
また、貴金属石鹸は、無電解めっき前処理剤の溶液中において、１〜３００００ｍｇ／Ｌ、好ましくは５０〜１００００ｍｇ／Ｌの濃度（貴金属換算）で使用することができる。
【００３７】
本発明のフレキシブル基板用銅張り積層体の基材としては、各種ポリイミドフィルム、ＰＥＴ等が好ましく用いられる。ポリイミドフィルムとしては、例えば、カプトン（東レデュポン製）、ユーピレックス（宇部興産製）等が、ＰＥＴとしては、ルミラー（東レ製）が挙げられる。
【００３８】
基材を無電解めっき前処理剤で処理する方法としては、浸漬、刷毛塗り、スピンコート等の方法が一般的であるが、これらに限定されるものではなく、表面に前処理剤を付着させる方法であれば良い。
【００３９】
表面処理後に使用した溶剤を揮発させるにはこの溶媒の揮発温度以上に加熱して表面を乾燥すれば十分であるが、さらに６０〜１２０℃で３〜６０分間加熱することが好ましい。
また、本発明の無電解めっき前処理剤層の膜厚は１〜２００ｎｍが好ましい。
【００４０】
本発明のフレキシブル基板用銅張り積層体は、これまで述べてきた前処理を施した基材上に、常法の無電解めっき法により銅めっき層を形成し、更に常法の電気めっきにより銅めっき層を形成したものである。こうして、本発明により、均一で密着性に優れたフレキシブル基板用銅張り積層体を得ることができる。
【実施例】
【００４１】
以下、実施例によって本発明を更に詳細に説明する。
【００４２】
実施例１
市販のポリイミドフィルムカプトン（２００Ｈ、東レデュポン製）の表面に、イミダゾールシラン（イミダゾールと３−グリシドキシプロピルトリメトキシシランの等モル反応生成物）１ｇ／Ｌと、Ｐｄ石鹸（ナフテン酸Ｐｄ、日鉱マテリアルズ製）０．５ｇ／Ｌ（Ｐｄ換算１００ｍｇ／Ｌ）と、エポキシ樹脂（エピコートＥＰ８２８、ジャパンエポキシレジン製）１ｇ／Ｌを含んだ有機溶媒（ブタノール）系無電解めっき前処理剤を塗布した。１５０℃で溶媒除去し、膜厚７０ｎｍの前処理剤層を形成した後、無電解銅めっき（めっき液：ＮＫＭ５５４、日鉱メタルプレーティング製）により膜厚０．５μｍの銅めっき層を形成し、次に、電流密度２Ａ／ｄｍ２で電気銅めっき（めっき液：硫酸銅系、日鉱メタルプレーティング製）を行ない、膜厚３５μｍの銅めっき層を形成した。その常態でのピール強度、その後空気中１５０℃、１６８時間エージングした後のピール強度をそれぞれ測定した。ピール強度はＪＩＳ Ｃ−６４８１に基づく９０度引き剥がし試験による。以下の実施例、比較例においても同様である。結果は表１の通り、エージング後での強度も０．７ｋｇｆ／ｃｍと高い数値を示した。
【００４３】
実施例２
市販のポリイミドフィルムカプトン（２００Ｈ、東レデュポン製）の表面に、イミダゾールシラン（イミダゾールと３−グリシドキシプロピルトリメトキシシランの等モル反応生成物）１ｇ／ＬとＰｄ石鹸（ナフテン酸Ｐｄ、日鉱マテリアルズ製）０．５ｇ／Ｌ（Ｐｄ換算１００ｍｇ／Ｌ）と、フェノール樹脂（ＸＬＣ−４Ｌ、三井化学製）２ｇ／Ｌを含んだ有機溶媒（ブタノール）系無電解めっき前処理剤を塗布した。１５０℃で溶媒除去し、膜厚７０ｎｍの前処理剤層を形成した後、無電解銅めっき（めっき液：ＮＫＭ５５４、日鉱メタルプレーティング製）により膜厚０．５μｍの銅めっき層を形成し、次に、電気銅めっき（めっき液：硫酸銅系、日鉱メタルプレーティング製）を行ない、膜厚３５μｍの銅めっき層を形成した。その常態でのピール強度、その後空気中１５０℃、１６８時間エージングした後のピール強度をそれぞれ測定した。
【００４４】
実施例３
実施例１のイミダゾールシランの変わりにアミノシラン（γ−アミノプロピルトリエトキシシラン、信越化学製）を用いた以外は実施例１と同様に処理・試験を行なった。結果は表１の通り、エージング後での強度も０．４ｋｇｆ／ｃｍと高い数値を示した。
【００４５】
比較例１
エポキシ樹脂を含まない以外は実施例１と同様に処理・試験を行なった。結果は表１の通り、初期ピール強度は０．９ｋｇｆ／ｃｍと高かったが、エージング後のピール強度は０．１ｋｇｆ／ｃｍと低いものとなった。
【００４６】
比較例２
スパッタリング法により銅シード層を０．５μｍ形成した後、実施例１と同様に電気銅めっきで３５μｍの銅めっき層を形成し、実施例１と同様に試験を行なった。結果は表１の通り、初期ピール強度は０．９ｋｇｆ／ｃｍと高かったが、エージング後は低いものとなった。
【００４７】
【表１】
Figure 0004859232
【Technical field】
[0001]
The present invention relates to an electroless plating pretreatment agent used for a base material of a copper-clad laminate that is a material for a flexible substrate for printed wiring, and a copper-clad laminate for a flexible substrate produced using the same.
[Background]
[0002]
Polyimide substrates are frequently used as insulating substrate materials for electronic components. Recently, with the thinning and miniaturization of electronic devices, a two-layer copper polyimide substrate with a higher degree of freedom, in which a metal layer is directly formed on a polyimide film, has attracted attention. The initial adhesion in the normal state is at a practical level, but there are concerns about characteristics such as adhesion in a heat-resistant, high-temperature, high-humidity environment.
[0003]
Further, for example, Patent Document 1 discloses a method of manufacturing a metal layer by a sputtering method for a flexible copper-clad laminate of polyimide film. However, this method is expensive, and the adhesion in a heat-resistant, high-temperature and high-humidity environment is not satisfactory.
[0004]
Methods for improving the adhesion between the polyimide film and the metal layer include dry processes such as plasma, UV, etc., and wet processes using alkali, etc. The surface may be uneven, which may adversely affect the formation of fine wiring.
[0005]
Patent Document 2 discloses electroless copper plating comprising five steps: a step of forming a resin composition coating on a polyimide film, the coating activation step, a catalyst application step, a catalyst activation step, and an electroless metal plating step. A method of performing electrolytic copper plating after performing is described. This method is intended to produce a resin composition layer as an adhesion-imparting layer. As a result, the film thickness of the resin composition layer is 1 to 20 μm, and the process is complicated.
[Patent Document 1]
JP-A-9-136378 [Patent Document 2]
[Patent Document 1] Japanese Patent Application Laid-Open No. 2001-168896
[Problems to be solved by the invention]
The present invention provides a copper-clad for a flexible substrate in which the initial adhesion strength of the base material and the copper plating layer in a normal state and the adhesion strength in a heat aging test (in the atmosphere, 150 ° C., 168 hours) are 0.4 kgf / cm or more It aims at providing the electroless-plating pretreatment liquid used for a laminated body, and the copper clad laminated body for flexible substrates produced using this electroless-plating pretreatment liquid.
[Means for Solving the Problems]
As a result of intensive studies on the above problems, the present inventors have found that an organic solvent solution containing a silane coupling agent having a metal capturing ability and a thermosetting resin as a pretreatment agent for electroless plating of a copper-clad laminate for a flexible substrate It has been found that the above-described problems can be solved by using an electroless plating pretreatment agent comprising: That is, the present invention is as follows.
[0008]
(1) A pretreatment agent for electroless plating used as a base material for a copper-clad laminate for a flexible substrate, and having a metal scavenging ability obtained by a reaction between an azole compound or an amine compound and an epoxy compound , Or γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ- An electroless plating pretreatment agent comprising a silane coupling agent having a metal capturing ability selected from mercaptopropyltrimethoxysilane and a thermosetting resin.
(2) The electroless plating pretreatment agent according to (1), wherein the thermosetting resin is an epoxy resin.
(3) After the substrate was treated with the electroless plating pretreatment agent described in (1) or (2) above, a copper plating layer was formed by electroless plating, and a copper plating layer was formed thereon by electroplating. A copper-clad laminate for a flexible substrate.
【Effect of the invention】
The copper-clad laminate for a flexible substrate, in which the base material is treated using the electroless plating pretreatment agent of the present invention, and then the electroless copper plating layer and the electrolytic copper plating layer are laminated, is a normal state of the base material and the copper plating layer. A copper-clad laminate for a two-layer copper-clad flexible substrate with excellent adhesion, wherein the initial adhesion and the adhesion in a heat-resistant aging test (in the atmosphere, 150 ° C., 168 hours) are 0.4 kgf / cm or more, Become. Adhesion can be applied to the substrate surface without any dry or wet pretreatment.
BEST MODE FOR CARRYING OUT THE INVENTION
The electroless plating pretreatment agent of the present invention includes a silane coupling agent having a metal capturing ability and a thermosetting resin.
[0013]
By adding a silane coupling agent having a metal scavenging ability, the noble metal catalyst can be more uniformly and more reliably fixed to the surface to be plated via the silane coupling agent.
[0014]
Preferred as the silane coupling agent is one obtained by reaction of an azole compound or an amine compound with an epoxy compound.
Examples of azole compounds include imidazole, oxazole, thiazole, selenazole, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, thiatriazole, benzazole, indazole, benzimidazole, and benzotriazole. It is done. Although not limited thereto, imidazole is particularly preferable.
[0015]
Examples of the amine compound include saturated hydrocarbon amines such as propylamine, unsaturated hydrocarbon amines such as vinylamine, and aromatic amines such as phenylamine.
[0016]
Also, the a silane coupling agent, in addition to the noble metal capture group derived from the azole compound or amine compound is a compound having a -SiX 1 X 2 X 3 group, X 1, X 2, X 3 is an alkyl group It means a halogen, an alkoxy group or the like, and any functional group that can be fixed to an object to be plated. X 1 , X 2 and X 3 may be the same or different.
[0017]
The silane coupling agent can be obtained by reacting the azole compound or amine compound with an epoxy silane compound.
[0018]
As such an epoxy silane compound,
[Chemical 1]
Figure 0004859232
(Wherein R 1 and R 2 are hydrogen or an alkyl group having 1 to 3 carbon atoms, n is 0 to 3)
The epoxy coupling agent shown by these is preferable.
[0019]
The reaction between the azole compound and the epoxy group-containing silane compound can be performed under the conditions described in, for example, JP-A-6-256358.
[0020]
For example, it can be obtained by dropping 0.1 to 10 moles of an epoxy group-containing silane compound at 80 to 200 ° C. with respect to 1 mole of an azole compound and reacting them for 5 minutes to 2 hours. At that time, a solvent is not particularly required, but an organic solvent such as chloroform, dioxane, methanol, ethanol or the like may be used.
[0021]
As a particularly preferred example, the reaction between an imidazole compound and an epoxysilane compound is shown below.
[Chemical formula 2]
Figure 0004859232
(Wherein R 1 and R 2 are hydrogen or an alkyl group having 1 to 3 carbon atoms, R 3 is hydrogen or an alkyl group having 1 to 20 carbon atoms, R 4 is a vinyl group, or 1 to 5 carbon atoms) An alkyl group, n represents 0-3.)
[0022]
Other examples of the silane coupling agent having a functional group having a metal scavenging ability used in the present invention include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-β (aminoethyl) γ-amino. Examples include propyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, and γ-mercaptopropyltrimethoxysilane.
[0023]
Examples of the thermosetting resin used for the electroless plating pretreatment agent of the present invention include an epoxy resin, a urea resin, a phenol resin, a melamine resin, and a urethane resin. By adding a thermosetting resin, the adhesion is improved. As the thermosetting resin, use of an epoxy resin is preferable because the effect of improving the adhesion is particularly large.
[0024]
In the present invention, it is not essential that the pretreatment agent for electroless plating contains a noble metal compound. Plating activity can be obtained by dipping in an aqueous palladium chloride solution after dipping in the pretreatment agent for plating. However, it is more preferable that the pretreatment agent for plating contains a catalyst such as a noble metal compound. Examples of the catalyst include noble metal compounds such as palladium, silver, platinum, and gold, such as halides, hydroxides, sulfates, carbonates, noble metal soaps, and the like, and palladium compounds are particularly preferable. Conventional catalysts such as tin chloride can also be included within the scope of the object of the present invention.
[0025]
The noble metal soap can be obtained by a reaction between a fatty acid, a resin acid, or naphthenic acid and a noble metal compound, and can be preferably used in the present invention.
[0026]
As a fatty acid, a C5-C25 thing is preferable, More preferably, it is 8-16. When the number of carbon atoms of the fatty acid is 4 or less, it becomes difficult to dissolve in an organic solvent and becomes unstable. On the other hand, if the number of carbon atoms is 26 or more, the soluble amount in an organic solvent is limited, and the amount of addition is increased due to a decrease in the noble metal content.
[0027]
Examples of the fatty acid include saturated fatty acids such as octylic acid, neodecanoic acid, dodecanoic acid, pentadecanoic acid and octadecanoic acid, unsaturated fatty acids such as oleic acid and linoleic acid, oxygen-containing fatty acids such as hydroxytetradecanoic acid and carboxydecanoic acid, or these Can be mentioned.
[0028]
Examples of the fatty acid, resin acid, and naphthenic acid include naphthenic acid, octylic acid, neodecanoic acid, and pentadecanoic acid.
[0029]
The noble metal compounds include palladium, silver, platinum, gold and other halides, hydroxides, sulfates, carbonates that exhibit a catalytic effect when copper or nickel is deposited on the surface of the object to be plated from an electroless plating solution. A compound such as a salt, which can form a soap with a fatty acid or the like, can be mentioned, and a palladium compound is particularly preferable.
[0030]
The noble metal soap used in the present invention can be obtained by a conventional method of producing a metal soap such as a metathesis method and a direct method using the fatty acid or the like and the noble metal compound.
[0031]
Palladium naphthenate preferable as a noble metal soap used in the present invention is shown below.
[Chemical 3]
Figure 0004859232
[0032]
The noble metal soap used in the present invention is soluble in an organic solvent and is stable as a solution. Examples of such an organic solvent include alcohols such as butanol, 2-ethylhexanol and octyl alcohol, aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as hexane, chloroform and dioxane.
[0033]
The electroless plating pretreatment agent of the present invention is a silane coupling agent having a metal scavenging ability, a thermosetting resin, a noble metal soap, etc., for example, alcohol such as butanol, 2-ethylhexanol, octyl alcohol, xylene, etc. Aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, and organic solvents such as chloroform and dioxane are used.
[0034]
Although the density | concentration of the silane coupling agent which has the metal capture | capture ability in an electroless-plating pretreatment agent is not restricted to this, 0.001-10 weight% is preferable and 0.05-3 weight% is more preferable. If it is less than 0.001% by weight, the amount of the compound adhering to the surface of the substrate tends to be low, and the effect is difficult to obtain. On the other hand, if it exceeds 10% by weight, it is difficult to dry because the amount of adhesion is too much, or the powder tends to agglomerate.
[0035]
The concentration of the thermosetting resin in the electroless plating pretreatment agent is preferably 0.001 to 30% by weight, and more preferably 0.05 to 10% by weight. If it is less than 0.001% by weight, there is no effect, and if it exceeds 30% by weight, the liquid viscosity becomes too high, resulting in uneven plating.
[0036]
Further, the noble metal soap can be used in a concentration of 1 to 30000 mg / L, preferably 50 to 10000 mg / L (precious metal conversion) in the solution of the electroless plating pretreatment agent.
[0037]
As a base material of the copper-clad laminate for a flexible substrate of the present invention, various polyimide films, PET and the like are preferably used. Examples of the polyimide film include Kapton (manufactured by Toray DuPont) and Upilex (manufactured by Ube Industries), and examples of PET include Lumirror (manufactured by Toray Industries, Inc.).
[0038]
As a method of treating the substrate with the electroless plating pretreatment agent, methods such as dipping, brush coating, and spin coating are common, but are not limited thereto, and the pretreatment agent is attached to the surface. Any method is acceptable.
[0039]
In order to volatilize the solvent used after the surface treatment, it is sufficient to heat the solvent to a temperature higher than the volatilization temperature and dry the surface, but it is preferable to heat at 60 to 120 ° C. for 3 to 60 minutes.
Moreover, the film thickness of the electroless plating pretreatment agent layer of the present invention is preferably 1 to 200 nm.
[0040]
The copper-clad laminate for a flexible substrate of the present invention is obtained by forming a copper plating layer by a conventional electroless plating method on a base material subjected to the pretreatment described so far, and further performing copper plating by a conventional electroplating method. A plating layer is formed. Thus, according to the present invention, a copper-clad laminate for a flexible substrate that is uniform and excellent in adhesion can be obtained.
【Example】
[0041]
Hereinafter, the present invention will be described in more detail with reference to examples.
[0042]
Example 1
On the surface of a commercially available polyimide film Kapton (200H, manufactured by Toray DuPont), 1 g / L of imidazole silane (equimolar reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane) and Pd soap (naphthoic acid Pd, Nikko) Materials) 0.5 g / L (100 mg / L in terms of Pd) and an organic solvent (butanol) electroless plating pretreatment agent containing 1 g / L of epoxy resin (Epicoat EP828, manufactured by Japan Epoxy Resin) were applied. . After removing the solvent at 150 ° C. and forming a pretreatment agent layer having a thickness of 70 nm, a copper plating layer having a thickness of 0.5 μm is formed by electroless copper plating (plating solution: NKM554, manufactured by Nikko Metal Plating), Next, electrolytic copper plating (plating solution: copper sulfate, manufactured by Nikko Metal Plating) was performed at a current density of 2 A / dm 2 to form a copper plating layer having a thickness of 35 μm. The peel strength in the normal state and then the peel strength after aging in air at 150 ° C. for 168 hours were measured. The peel strength is based on a 90-degree peeling test based on JIS C-6481. The same applies to the following examples and comparative examples. As a result, as shown in Table 1, the strength after aging was as high as 0.7 kgf / cm.
[0043]
Example 2
On the surface of a commercially available polyimide film Kapton (200H, manufactured by Toray DuPont), 1 g / L of imidazole silane (equimolar reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane) and Pd soap (naphthene acid Pd, Nikko Materials) An organic solvent (butanol) electroless plating pretreatment agent containing 0.5 g / L (100 mg / L in terms of Pd) and 2 g / L of a phenol resin (XLC-4L, manufactured by Mitsui Chemicals) was applied. After removing the solvent at 150 ° C. and forming a pretreatment agent layer having a thickness of 70 nm, a copper plating layer having a thickness of 0.5 μm is formed by electroless copper plating (plating solution: NKM554, manufactured by Nikko Metal Plating), Next, electrolytic copper plating (plating solution: copper sulfate, manufactured by Nikko Metal Plating) was performed to form a copper plating layer having a thickness of 35 μm. The peel strength in the normal state and then the peel strength after aging in air at 150 ° C. for 168 hours were measured.
[0044]
Example 3
The treatment and test were conducted in the same manner as in Example 1 except that aminosilane (γ-aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of imidazolesilane in Example 1. As a result, as shown in Table 1, the strength after aging was as high as 0.4 kgf / cm.
[0045]
Comparative Example 1
The treatment and test were conducted in the same manner as in Example 1 except that no epoxy resin was contained. As a result, as shown in Table 1, the initial peel strength was as high as 0.9 kgf / cm, but the peel strength after aging was as low as 0.1 kgf / cm.
[0046]
Comparative Example 2
After forming a copper seed layer by a sputtering method to a thickness of 0.5 μm, a copper plating layer of 35 μm was formed by electrolytic copper plating in the same manner as in Example 1, and the test was performed in the same manner as in Example 1. As a result, as shown in Table 1, the initial peel strength was as high as 0.9 kgf / cm, but was low after aging.
[0047]
[Table 1]
Figure 0004859232

Claims (3)

フレキシブル基板用銅張り積層体の基材に用いる無電解めっき前処理剤であって、アゾール系化合物またはアミン化合物とエポキシ系化合物との反応により得られる金属捕捉能を有するシランカップリング剤、またはγ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシランから選ばれる金属捕捉能を有するシランカップリング剤と、熱硬化性樹脂とを含むことを特徴とする無電解めっき前処理剤。Electroless plating pretreatment agent used for base material of copper-clad laminate for flexible substrate, silane coupling agent having metal capture ability obtained by reaction of azole compound or amine compound and epoxy compound, or γ -Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-mercaptopropyltri An electroless plating pretreatment agent comprising a silane coupling agent having a metal scavenging ability selected from methoxysilane and a thermosetting resin. 前記熱硬化性樹脂がエポキシ樹脂であることを特徴とする請求の範囲１記載の無電解めっき前処理剤。The electroless plating pretreatment agent according to claim 1, wherein the thermosetting resin is an epoxy resin. 基材を請求の範囲１又は２記載の無電解めっき前処理剤で処理した後、無電解めっきにより銅めっき層を形成し、その上に電気めっきにより銅めっき層を形成したことを特徴とするフレキシブル基板用銅張り積層体。After the base material is treated with the electroless plating pretreatment agent according to claim 1 or 2, a copper plating layer is formed by electroless plating, and a copper plating layer is formed thereon by electroplating. Copper-clad laminate for flexible substrates.
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