JP4331840B2 - Fine plating method - Google Patents

Description

【００１１】
上記のポリ乳酸は単独で使用してもよいし、ポリ乳酸を主成分とし、これに脂肪族ポリエステル（ポリヒドロキシカルボン酸、ヒドロキシカルボン酸又は脂肪族多価アルコールと脂肪族多価塩基酸とからなる脂肪族ポリエステル、ヒドロキシカルボン酸や脂肪族多価アルコールから選ばれる２種以上のモノマー成分と、脂肪族多価塩基酸から選ばれる２種以上のモノマー成分とからなるランダム共重合体やブロック共重合体等）の単独又は２種以上を、混合したものや、ランダム共重合又はブロック共重合させたものであってもよいし、また必要に応じてアルカリ分解促進剤、有機及び無機充填剤、可塑剤、湿潤剤、紫外線吸収剤、酸化防止剤、滑剤、着色剤等の汎用の合成樹脂に使用できる添加剤を混合したものであってもよい。
この脂肪族ポリエステルの混合量又は共重合量は、混合体又は共重合体の全量に対して１〜１０ｗｔ％程度、アルカリ分解促進剤の混合量は混合体全量に対して１〜１００ｗｔ％程度、好ましくは５〜８０ｗｔ％、より好ましくは１０〜６０ｗｔ％であり、その他の添加剤の混合量は混合体全量に対して１〜５％程度が適している。
【００１２】
なお、上記のポリ乳酸の重量平均分子量は、１万〜４０万程度が好ましく、脂肪族ポリエステルは、ポリ乳酸と混合させる場合の重量平均分子量は、１万〜５０万程度、好ましくは３万〜４０万程度、より好ましくは５万〜３０万程度が適しており、ポリ乳酸と共重合させる場合はその共重合体の重量平均分子量が、１万〜５０万程度、好ましくは３万〜４０万程度、より好ましくは５万〜３０万程度が適している。
上記のヒドロキシカルボン酸としては、グリコール酸、Ｌ−乳酸、Ｄ−乳酸、Ｄ／Ｌ−乳酸、３−ヒドロキシブチリックアシッド、４−ヒドロキシブチリックアシッド、３−ヒドロキシバレリックアシッド、５−ヒドロキシバレリックアシッド、６−ヒドロキシカプロン酸等が挙げられ、これらの１種以上が使用できる。
脂肪族多価アルコールとしては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、１，９−ノナンジオール、ネオペンチルグリコール、ポリテトラメチレングリコール、１，４−シクロヘキサンジメタノール、１，４−ベンゼンジメタノール等が挙げられ、これらの１種以上が使用できる。
脂肪族多価塩基酸としては、コハク酸、シュウ酸、マロン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、フェニルコハク酸、１，４−フェニレンジ酢酸等が挙げられ、これらの１種以上が使用できる。
アルカリ分解促進剤としては、デンプン、ポリビニルアルコール、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコール等のポリアルキレングリコール、ポリアミノ酸等の親水性高分子化合物、無水コハク酸、ポリコハク酸イミド等のアルカリ加水分解性化合物等が挙げられ、これらの１種以上が使用できる。中でも、ポリ乳酸や脂肪族ポリエステルへの分散性や相溶性、あるいはブリードアウトのし難さ等から、ポリアルキレングリコール、特にポリエチレングリコールが好ましい。
【００１３】
第１発明の微細メッキ工程：
第１発明は、図１（Ａ）〜（Ｈ）に示す工程で行われる。
先ず、図１（Ａ）に示す上記の基体１の表面に、図１（Ｂ）に示す第１工程でメッキ２を施すが、このメッキに先立ち、前処理工程として、基体１の表面を粗化し、次いでメッキ用触媒を付与する。
【００１４】
〔前処理工程〕
（基体表面の粗化）
基体の表面を粗化する方法としては、例えば、公知のエッチング方法が適用できる。
エッチング方法には、湿式と乾式とがあり、基体に使用されている材料の種類等により、適宜の方式のエッチング方法を採用すればよい。
乾式法は、例えば、プラズマを照射したり、気体を使用する等して行うことができる。
湿式法は、例えば、ＮａＯＨ、ＫＯＨ等のアルカリ金属水酸化物の水溶液、アルコール性ナトリウム、アルコール性カリウム等のアルカリ金属アルコラートの水溶液、あるいはジメチルホルムアミド等の有機溶剤を用い、これらのエッチング液を基体表面に塗布したり、これらの液中に基体を浸漬させる等して接触させて行うことができる。
このうち、ＮａＯＨ、ＫＯＨ等の水溶液を用いる方法は、濃度３５〜５０ｗｔ％程度、温度７０〜９５℃程度の条件とすることが好ましい。
なお、有機溶剤を使用する場合は、基体を膨潤するのみで、粗化まで至らないことがある。この場合は、有機溶剤での処理の後に、酸あるいはアルカリ処理を施せばよい。
【００１５】
なお、湿式法においては、上記のエッチング液と基体とを接触させた後に、塩酸やフッ酸等の酸溶液を用いて処理することが好ましい。この酸処理は、アルカリ性のエッチング液を単に中和するために行うのではなく、基体中に含まれるフィラーであって、かつ基体の表面近傍に存在しているフィラーの一部を除去し、基体表面の粗化効果をより一層高めるために行われる。
従って、この酸処理の条件（ｐＨ、温度、時間等）は、上記のフィラーが溶解する程度の条件とすることが好ましい。
【００１６】
（メッキ用触媒の付与）
メッキ用触媒（以下、単に触媒と記すこともある）としては、公知のものが使用でき、中でもＰｄやＰｔを含むものが好ましく、これらは、例えば、塩化物等の無機塩として使用される。
メッキ用触媒の付与は、上記の無機塩を基体に付着させた後、アクセレータ処理により上記の触媒金属を析出させることで行われる。
無機塩を基体に付着させるには、無機塩の溶液と基体とを接触させればよく、例えば、無機塩の溶液中に基体を浸漬したり、この水溶液を基体に塗布する等して行われる。
具体的な条件は、基体の材料、メッキの材料、メッキ用触媒の材料、無機塩の付着方法等により種々異なり一概には決められないが、メッキ用触媒の塩として塩化パラジウムを使用し、浸漬法を採用する場合を例にとれば、一例として次のようなものが挙げられる。
【００１７】
触媒塩溶液組成
ＰｄＣｌ_２・２Ｈ_２Ｏ：０．１〜０．３ｇ／ｄｍ^３
ＳｎＣｌ_２・２Ｈ_２Ｏ：１０〜２０ｇ／ｄｍ^３
ＨＣｌ ：１５０〜２５０ｃｍ^３／ｄｍ^３
浸漬条件
温度：２０〜４５℃
時間：１〜１０分
【００１８】
なお、メッキ用触媒塩溶液の溶媒としては、上記の塩酸以外に、メタノール、エタノール、イソプロピルアルコール等の有機溶剤を用いることもできる。
【００１９】
上記のようなメッキ用触媒塩の付着の後、水洗し、アクセレータ処理してメッキ用触媒（金属）を基体上に析出させる。
アクセレータ処理は、一般には、アクセレータ（促進液）と触媒塩付与後の基体とを、浸漬あるいは塗布等により接触させることにより行う。
この促進液としては、硫酸、塩酸、水酸化ナトリウム、アンモニア等の無機溶液が用いられる。
上記組成の触媒塩溶液を用い、上記条件での浸漬で触媒塩が付与されている場合は、水洗により、基体表面に付着しているＳｎ^２＋−Ｐｄ^２＋の錯体が加水分解され、Ｓｎ^２＋はＳｎ（ＯＨ）Ｃｌとなって沈殿し、続いて行うアクセレータ処理により、金属Ｐｄが基体上で生成する。この金属Ｐｄがメッキ用触媒として作用する。
【００２０】
〔第１工程《メッキ工程》〕
第１工程では、図１（Ｂ）に示すように、基体１の表面全面にメッキ２を施す。従って、上記の前処理も基体の表面全面に施す。
メッキ方法は、公知のメタライジング方法（無電解メッキ方法や電気メッキ方法）が採用できる。
メッキ金属としては、銅、ニッケル、金、その他各種の金属が挙げられる。
メッキ工程は、多数回に分けて行うこともできるし、１回で一度に行うこともできる。
なお、触媒付与工程の後に、予備メッキ工程を設けることもできる。予備メッキも、公知のメタライジング法で行うことができ、好ましくは無電解メッキ法であり、メッキ金属も、上記のいわゆる本メッキ工程での金属と同様のものが使用できる。この予備メッキ工程を設けることにより、本メッキ工程でのメッキ品質を一層良好なものとすることができる。
また、後メッキ工程を設けることもできる。後メッキ工程も、公知のメタライジング法で行うことができ、好ましくは無電解メッキ法であり、メッキ金属は、本メッキ工程での金属と同種であってもよいが、異種のものであってもよい。
【００２１】
〔第２工程《第１の被覆工程》〕
第２工程では、図１（Ｃ）に示すように、上記の被覆材を用いて、メッキ２面上に適宜パターン（図１（Ｃ）のパターンに限定されない）で部分的に第１の被覆３を施す。
この第１の被覆３は、射出成形方法により被覆形状を成形する手法であって、基体を型の一部とする射出成形法により被覆材の射出と同時に基体表面の所望箇所を被覆する手法である。
第１の被覆３の寸法は、パターンの形状によって異なるため、一概には言えないが、例えば、図１（Ｃ）に示すようなストライプ形状の場合は、幅０．２〜０．３ｍｍ程度、間隔０．０５〜０．１０ｍｍ程度が適している。
【００２２】
〔第３工程《１回目のメッキ除去工程》〕
第３工程で、図１（Ｄ）に示すように、上記の部分的な第１の被覆３が施されている以外の部分、すなわち露出している部分のメッキを除去する。
このメッキ材２の除去は、上記のようなメッキ金属は除去するが、第１の被覆３は除去しない手法であれば、どのような方法によってもよいが、一般には、塩化第二鉄、塩化第二銅、過硫酸アンモニウムなどの無機塩の溶液と、メッキ施工面とを、浸漬あるいは塗布等により接触させることにより行われる。
このメッキ除去工程は、第１発明において、微細メッキパターンを、細密に、かつ高精度で行う上で極めて重要な工程であり、例えば、以下のような条件で行われる。
【００２３】
上記の無機塩の溶液を用いる場合は、無機塩の濃度が０．５〜１００ｇ／リットル、好ましくは１．５〜４．０ｇ／リットルとする（以下、リットルをＬ、ミリリットルをｍＬと記す）。
０．５ｇ／Ｌ未満では、無機塩の量が少なすぎて溶液の単位重量当たりの処理力が充分でなくなり、１００ｇ／Ｌより多いと、被覆材や基体が損傷を受ける虞れがある。
接触時間は、短かすぎれば処理が充分でなく、長すぎれば被覆材や基体が損傷を受ける虞れがあるため、０．５〜１０分とする。
なお、この無機塩溶液の溶媒は、水や低級アルコール（メチルアルコール、エチルアルコールなど）などを使用する。
【００２４】
〔第４工程《第１の被覆材除去工程》〕
第４工程では、図１（Ｅ）に示すように、第１の被覆材３を除去する。
被覆材３の除去は、水溶性高分子材料の場合は水を用いて行い、加水分解性高分子材料の場合はアルカリ水溶液や酸液（各種の無機酸の液）を用いて行う。
この被覆材３の除去工程も、第１発明において、微細メッキパターンを、細密に、かつ高精度で行う上で極めて重要な工程であり、例えば、以下のような条件で行われる。
被覆材３が水溶性高分子材料の場合、高分子材料の種類にもよるが、一般には、２５〜９５℃程度の温水中に２〜３５時間浸漬して除去するのが好ましい。
被覆材３が加水分解性高分子材料、特にポリ乳酸の場合は、濃度２〜１５ｗｔ％程度で温度２５〜７０℃程度のカ性アルカリ（ＮａＯＨ、ＫＯＨ等）水溶液中に１〜１２０分程度浸漬して除去するのが好ましい。
【００２５】
〔第５工程《第２の被覆工程》〕
第５工程では、図１（Ｆ）に示すように、第３工程でメッキ２が除去された部分（メッキ除去部）と、メッキ２が除去されなかった部分（メッキ残存部）とに渡って適宜パターンで部分的に、上記の被覆材を用いて、第２の被覆４を施す。
このときのパターンは、図１（Ｆ）に示すものに限らず、メッキ除去部とメッキ残存部とに渡れば、どのようなパターンであってもよい。
第２の被覆材４は、上記の第１の被覆材３と同材であってもよいし、異材であってもよい。
また、第２の被覆４も、上記の第１の被覆３の場合と同様に、射出成形方法により被覆形状を成形する手法であって、基体を型の一部とする射出成形法により被覆材の射出と同時に基体表面の所望箇所を被覆する手法である。
第２の被覆４の寸法も、前記第１の被覆３の場合と同様に、一概には言えないが、例えば、図１（Ｃ）に示すようなストライプ形状の場合は、前記第１の被覆３の場合と同様の幅、間隔が適している。
【００２６】
〔第６工程《２回目のメッキ除去工程》〕
第６工程においては、図１（Ｇ）に示すように、第２の被覆４以外の部分のメッキを除去するが、このメッキ除去は、上記した第３工程でのメッキ除去と同様の手法により行われる。
【００２７】
〔第７工程《第２の被覆材除去工程》〕
この第７工程は、図１（Ｈ）に示すように、第２の被覆材４を除去する。この被覆材４の除去は、上記した第４工程での第１の被覆材３の除去と同様の手法により行われる。
以上の第１〜第７工程を経ることにより、例えば、幅０．１ｍｍ程度の微細なメッキ２を得ることができる。
【００２８】
第２発明の微細メッキ工程：
第２発明は、図２（Ａ）〜（Ｈ）に示す工程で行われる。
先ず、図２（Ａ）に示すように、上記の基体１の表面に、第１工程で第１の被覆３を施すが、この被覆に先立ち、前処理工程として、基体１の表面を粗化する。
【００２９】
〔前処理工程《基体表面の粗化》〕
基体１の表面粗化方法は、前述した第１発明の場合と同様の公知のエッチング方法が適用できる。
この表面粗化は、第１発明の場合と同様に、基体１の全面に施される。
【００３０】
〔第１工程《第１の被覆工程》〕
第１工程は、図２（Ａ）に示すように、粗化された基体１に、前記の被覆材を用いて、適宜パターン（図２（Ａ）に示すパターンに限定されない）で部分的に第１の被覆３を施す。
この第１の被覆３は、第１発明の場合の第１、第２の被覆３、４と同様に、射出成形方法により被覆形状を成形する手法であって、基体を型の一部とする射出成形法により被覆材の射出と同時に基体表面の所望箇所を被覆する手法である。
第１の被覆３の寸法も、前記第１発明の第１、第２の被覆３、４と同様に一概には言えないが、該第１発明の第１、第２の被覆３、４と同様の幅、間隔が適している。
【００３１】
〔第２工程《第１のメッキ用触媒付与工程》〕
第２工程では、図２（Ｂ）に示すように、第１の被覆材３で被覆されていない部分の基体１表面に、第１のメッキ用触媒１１を付与する。
このメッキ用触媒１１の種類や、メッキ用触媒１１の付与方法は、前述の第１発明における前処理工程での触媒付与の場合と同様である。
なお、メッキ用触媒塩溶液の溶媒として、メタノール、エタノール、イソプロピルアルコール等の有機溶剤を用いる場合は、上記した水溶性又は加水分解性高分子材料からなる被覆材が一部溶出されることがあるが、一部溶出しても差し支えない。
【００３２】
〔第３工程《第１の被覆材除去工程》〕
第３工程は、図２（Ｃ）に示すように、第１の被覆材３を除去する。
被覆材３の除去は、前述の第１発明の場合と同様であるが、被覆材３が加水分解性高分子材料、特にポリ乳酸の場合、カ性アルカリ水溶液が高温、高濃度程、被覆材３ばかりか、メッキ用触媒をも脱落することがあるため、濃度２〜１５ｗｔ％程度で温度２５〜７０℃程度のカ性アルカリ（ＮａＯＨ、ＫＯＨ等）水溶液中に１〜１２０分程度浸漬して除去するのが好適である。
【００３３】
〔第４工程《第１のメッキ工程》〕
第４工程では第１のメッキを施すが、このメッキ２は、図２（Ｄ）に示すように、第１のメッキ用触媒１１が付与されている部分のみに施される。
メッキ方法、メッキ金属は、前述の第１発明の場合と同様である。
【００３４】
〔第５工程《第２の被覆工程》〕
第５工程は、図２（Ｅ）に示すように、第４工程でメッキが施されなかった部分（非メッキ部）と、メッキ２が施された部分（メッキ部）とに渡って、適宜パターンで部分的に、上記の被覆材を用いて、第２の被覆４を施す。
このときのパターンは、図２（Ｅ）のαに示すように、非メッキ部とメッキ部とに渡ってメッキ部の全てを被覆するように、あるいは同図のβに示すように、非メッキ部とメッキ部とに渡ってメッキ部の一方の面は被覆するが他方の面は被覆しない（露出する）ようにしてもよいし、また図２（Ｅ）に示すものに限らず、非メッキ部とメッキ部とに渡れば、どのようなパターンであってもよい。
この第２の被覆材４は、前述の第１発明の場合と同様に、上記の第１の被覆材３と同材であってもよいし、異材であってもよい。
また、第２の被覆４も、上記の第１の被覆３の場合と同様に、射出成形方法により被覆形状を成形する手法であって、基体を型の一部とする射出成形法により被覆材の射出と同時に基体表面の所望箇所を被覆する手法である。
第２の被覆４の寸法も、前記第１の被覆３の場合と同様に一概には言えないが、該第１の被覆３の場合と同様の幅、間隔が適している。
【００３５】
〔第６工程《第２の触媒付与工程》〕
第６工程では、図２（Ｆ）に示すように、第２の被覆材４で被覆されていない部分の基体１表面に、第２のメッキ用触媒１２を付与する。
このメッキ用触媒１２の種類や、メッキ用触媒１２の付与方法は、上記の第３工程での第１のメッキ用触媒１１の付与の場合と同様である。
【００３６】
〔第７工程《第２の被覆材除去工程》〕
第７工程においては、図２（Ｇ）に示すように、第２の被覆材４を除去する。 被覆材４の除去は、上記の第１の被覆材３の除去と同様である。
この第７工程により、図２（Ｇ）に示すように、第２のメッキ用触媒１２は、第１のメッキ部２に接触して付与されることとなる。
【００３７】
〔第８工程《第２のメッキ工程》〕
第８工程で第２のメッキが施されるが、この第２のメッキ５は、図２（Ｈ）に示すように、第２のメッキ用触媒１２と、第１のメッキ２とに渡って施される。
すなわち、第４工程で既に施されている第１のメッキ２が核となって、該メッキ２上に第２のメッキ５が施されると共に、この第１のメッキ２に接触して付与されている第２のメッキ用触媒１２上に第２のメッキ５が施されることとなり、図２（Ｈ）に示すようなメッキ態様となる。
【００３８】
以上の第１〜第８工程を経ることにより、例えば、幅０．２ｍｍ程度の微細なメッキ部２あるいは５が得られ、幅０．１ｍｍ程度の非メッキ部が得られる。
図２（Ｈ）に示すメッキ部２とメッキ部５の厚さは、メッキ部５がメッキ部２に比してやや厚めとなる。
なお、上記の第５〜第８工程は、１回に限らず、更に複数回付加することもできる。すなわち、第１〜第８工程後に、更に第５工程の第２（実際は第３）の被覆工程、第６工程の第３のメッキ用触媒付与工程、第７工程の第３の被覆材除去工程、第８工程の第３のメッキ工程を付加することもでき、この第５〜第８工程を複数回繰り返すこともできる。
【００３９】
【実施例】
実施例１
第１、第２の被覆材として水溶性高分子材を用い、図１（Ａ）〜（Ｈ）の工程に沿って実施した。
【００４０】
〔前処理工程〕
（基体の成形工程）
図１（Ａ）において、芳香族系ポリエステル（液晶ポリマー《米国セラニース社製商品名“ベクトラＣ８１０”を使用》）により、１次金型を用いて、平板形状の基体１を成形した。
この基体１を、６０℃に加熱した脱脂液（奥野製薬社製商品名“エースクリーンＡ２２０”５０ｇ／リットル《以下、リットルをＬ、ミリリットルをｍＬと記す》水溶液）に１０分間浸漬した後、水洗して脱脂した。
【００４１】
（基体表面の粗化工程）
メチルアルコール１Ｌに金属Ｎａ３５０〜５００ｇ（本例では４３０ｇ）を溶解したアルカリ溶液を９０℃に加熱し、この加熱溶液中に、上記脱脂後の基体１を浸漬し、３０〜８０分間（本例では４０分間）保持して、基体１の表面を粗化した。
なお、メチルアルコールに変えてエチルアルコール（金属Ｎａ４３０ｇ）を使用した場合も、同様の条件で粗化することができた。
また、メチルアルコールに変えてイソプロピルアルコール（金属Ｎａ４３０ｇ）を使用した場合は、このアルカリ溶液を６０℃に加熱し、上記脱脂後の基体１を浸漬し、１０分間保持の後、クロム酸混液（ＣｒＯ_３２２ｗｔ％と濃硫酸５４ｗｔ％の混合溶液）を６０℃に加熱した中に入れることにより、粗化することができた。
更に、水１ＬにＮａＯＨ３５０〜５００ｇ（本例では４３０ｇ）を溶解したアルカリ溶液を使用した場合は、上記のメチルアルコールを使用した場合と同様の条件で粗化することができた。
【００４２】
（メッキ用触媒の付与工程）
メチルアルコールに、メッキ用触媒塩としての塩化第一スズと塩化パラジウムとの混合塩酸液（荏原ユージライト社製商品名“エニレックスＣＴ−８”）を２０ｍＬ／Ｌの割合で添加し、これを３０℃に保持し、この溶液中に、上記の表面粗化基体１を３〜５分間（本例では４分間）浸漬した後、水洗し、６０℃に加温した塩酸（５０ｍＬ／Ｌ）中に６０分間浸漬（アクセレータ処理）し、基体１の表面全面にメッキ用触媒を付与した。
なお、メチルアルコールに変えてエチルアルコールを使用した場合も、同様の条件でメッキ用触媒を付与することができた。
【００４３】
〔第１工程《メッキ工程》〕
基体１に、表１に示す組成の銅メッキ浴を使用し、表２に示すメッキ条件で、あるいは表３に示すロッシェル型またはＥＤＴＡ型のいずれかの銅メッキ浴を使用して予備メッキを行った後に表４に示す組成の銅メッキ浴を使用して本メッキを行って（この２段階メッキの場合の条件は予備、本メッキ共に表２の通りとした）、厚さ０．３〜２０．０μｍ（本例では１０μｍ）となるように、無電解銅メッキを施し、図１（Ｂ）に示す態様（基体１表面全面へ）のメッキ２を得た。また、無電解銅メッキを０．５μｍ厚さとなるように施した後、電気銅メッキを０．５μｍ厚さとなるように施した場合も、図１（Ｂ）に示す態様のメッキ２を得た。
【００４４】
【表１】
銅メッキ浴組成
ＣｕＳＯ_４・５Ｈ_２Ｏ ：０．０４モル／Ｌ
ＨＣＨＯ（３７％溶液）：０．１モル／Ｌ
ＮａＯＨ ：０．２モル／Ｌ
ＥＤＴＡ・４Ｎａ ：０．０８モル／Ｌ
α，α′−ジピリジル ：５〜１０ｐｐｍ
ＰＥＧ−１０００^＊１ ：５０〜１００ｐｐｍ
＊１ＰＥＧ−１０００；安定剤
【００４５】
【表２】
メッキ条件
浴温度 ：６０〜７０℃
エア攪拌：０．１Ｌ／Ｌ・分
浴 ：０〜１ｄｍ^２／Ｌ
【００４６】
【表３】

【００４７】
【表４】
本銅メッキ浴組成
ＣｕＳＯ_４・５Ｈ_２Ｏ ：０．０４モル／Ｌ
ＨＣＨＯ（３７％溶液）：０．０６モル／Ｌ
ＮａＯＨ ：ｐＨ１２
ＥＤＴＡ・４Ｎａ ：０．１モル／Ｌ
安定剤^＊２ ：若干
【００４８】
〔第２工程《第１の被覆工程》〕
メッキ２施工後の基体１をセットし５〜３０℃（本例では１０℃）に保持した２次金型内に、１５０〜２６０℃（本例では１９０℃）に加熱した第１の被覆材３としての水溶性高分子材（ポリビニルアルコール《以下、ＰＶＡ》《クラレ社製商品名“ポバール”を使用》）を、射出圧２００〜１２００ｋｇ／ｃｍ^２（本例では３５０ｋｇ／ｃｍ^２）で射出し、図１（Ｃ）に示す態様の厚さ１ｍｍ、幅０．３ｍｍ、間隔０．１ｍｍの部分被覆３を得た。
【００４９】
〔第３工程《１回目のメッキ除去工程》〕
濃度３ｇ／Ｌの塩化第二鉄水溶液中に１〜１０分間浸漬して、部分被覆３以外の部分のメッキ除去を行い、図１（Ｄ）に態様のものを得た。
【００５０】
〔第４工程《第１の被覆材除去工程》〕
第３工程終了後の基体１を、濃度７重量％で３０℃のＮａＯＨ水溶液中に４０分間浸漬して、第１の被覆材３を除去し、図１（Ｅ）に示す態様のものを得た。
【００５１】
〔第５工程《第２の被覆工程》〕
第２工程と同様にして、図１（Ｆ）に示す態様の厚さ１ｍｍ、幅０．３ｍｍ、間隔０．１ｍｍの部分被覆４を得た。
【００５２】
〔第６工程《２回目のメッキ除去工程》〕
第３工程と同様にしてメッキ２を除去し、図１（Ｇ）に示す態様のものとした。
【００５３】
〔第７工程《第２の被覆材除去工程》〕
第４工程と同様にして第２の被覆材４を除去した。
以上により、図１（Ｈ）に示すような態様で、メッキ（回路）幅及び回路間隔幅共に約０．１ｍｍのメッキ製品を得ることができた。
【００５４】
実施例２
第１、第２の被覆材として加水分解性高分子材を用い、実施例１と同様に、図１（Ａ）〜（Ｈ）の工程に沿って実施した。
〔前処理工程〕
実施例１と同様にして実施例１と同様の基体１を成形し、粗化し、メッキ用触媒を付与した。
【００５５】
〔第１工程《メッキ工程》〕
実施例１と同様にして無電解銅メッキを施した。
また、実施例１と同様にして、無電解銅メッキを施した後、電気銅メッキを施した。
いずれの場合も、実施例１と同様に、図１（Ｂ）に示す態様の厚さ１０μｍのメッキ２を得ることができた。
【００５６】
〔第２工程《第１の被覆工程》〕
メッキ２施工後の基体１をセットし５〜３０℃（本例では１０℃）に保持した２次金型内に、１５０〜２６０℃（本例では１９０℃）に加熱した被覆材３としての加水分解性高分子材（ポリ乳酸樹脂《三井化学社製商品名“ＬＡＣＥＡ”を使用》）を、射出圧２００〜１２００ｋｇ／ｃｍ^２（本例では３５０ｋｇ／ｃｍ^２）で射出し、図１（Ｃ）に示す態様の厚さ０．５ｍｍ、幅０．３ｍｍ、間隔０．１ｍｍの部分被覆３を得た。
【００５７】
〔第３工程《１回目のメッキ除去工程》〕
実施例１の第３工程と同様にして部分被覆３以外の部分のメッキ除去を行い、図１（Ｄ）に態様のものを得た。
【００５８】
〔第４工程《第１の被覆材除去工程》〕
第３工程終了後の基体１を、実施例１の第４工程と同様にして第１の被覆材３を除去し、図１（Ｅ）に示す態様のものとした。
【００５９】
〔第５工程《第２の被覆工程》〕
第２工程と同様にして、図１（Ｆ）に示す態様の厚さ０．５ｍｍ、幅０．３ｍｍ、間隔０．１ｍｍの部分被覆４を得た。
【００６０】
〔第６工程《２回目のメッキ除去工程》〕
第３工程と同様にしてメッキ２を除去し、図１（Ｇ）に示す態様のものとした。
【００６１】
〔第７工程《第２の被覆材除去工程》〕
第４工程と同様にして第２の被覆材４を除去した。
以上により、図１（Ｈ）に示すような態様で、メッキ（回路）幅及び回路間隔幅共に約０．１ｍｍのメッキ製品を得ることができた。
【００６２】
実施例３
第１、第２の被覆材として水溶性高分子材を用い、図２（Ａ）〜（Ｈ）の工程に沿って実施した。
【００６３】
〔前処理工程〕
実施例１と同様にして実施例１と同様の基体１を成形し、粗化した。
【００６４】
〔第１工程《第１の被覆工程》〕
表面粗化後の基体１をセットし５〜３０℃（本例では１０℃）に保持した２次金型内に、１５０〜２６０℃（本例では１９０℃）に加熱した被覆材３としての水溶性高分子材（ＰＶＡ《クラレ社製商品名“ポバール”》）を、射出圧２００〜１２００ｋｇ／ｃｍ^２（本例では３５０ｋｇ／ｃｍ^２）で射出し、図２（Ａ）に示す態様の厚さ０．５ｍｍ、幅０．２ｍｍ、間隔０．２ｍｍの部分被覆３を得た。
【００６５】
〔第２工程《第１のメッキ用触媒付与工程》〕
メチルアルコールに、メッキ用触媒塩としての塩化第一スズと塩化パラジウムとの混合塩酸液（荏原ユージライト社製商品名“エニレックスＣＴ−８”）を２０ｍＬ／Ｌの割合で添加し、これを３０℃に保持し、この溶液中に、上記の第１の部分被覆３を施した基体１を３〜５分間（本例では４分間）浸漬した後、水洗し、６０℃に加温した塩酸（５０ｍＬ／Ｌ）中に６０分間浸漬（アクセレータ処理）し、図２（Ｂ）に示すように、基体１の非被覆面（露出面）に第１のメッキ用触媒１１を付与した。
【００６６】
〔第３工程《第１の被覆材除去工程》〕
メッキ用触媒１１付与の後、実施例１の第４工程と同様にして第１の被覆材３を除去し、図２（Ｃ）に示す態様のものを得た。
【００６７】
〔第４工程《第１のメッキ工程》〕
被覆材除去後の基体１に、実施例１と同様にして無電解銅メッキを施した。
また、実施例１と同様にして、無電解銅メッキを施した後、電気銅メッキを施した。
いずれの場合も、図２（Ｄ）に示すように、メッキ用触媒１１付与面のみに、銅メッキ２が施されていた。
【００６８】
〔第５工程《第２の被覆工程》〕
第１工程と同じ樹脂を用い、第１工程と同様にして、図２（Ｅ）に示すように、メッキ２が施されている部分（メッキ部）と、施されていない部分（非メッキ部）とに渡って、厚さ０．５ｍｍ、幅０．２〜０．４ｍｍ、間隔０．１ｍｍの第２の被覆４を得た。
【００６９】
〔第６工程《第２のメッキ用触媒付与工程》〕
第２工程の第１のメッキ用触媒と同じ触媒を、第２工程と同様にして、図２（Ｆ）に示すように、基体１の非被覆面（露出面）に、第２のメッキ用触媒１２を付与した。
【００７０】
〔第７工程《第２の被覆材除去工程》〕
第３工程と同様にして、第２の被覆材４を除去し、図２（Ｇ）の態様のものを得た。
【００７１】
〔第８工程《第２のメッキ工程》〕
第４工程と同じメッキ材を、第４工程と同様にして第２のメッキを施した。
この第２のメッキ５は、第１のメッキ２上と、該第１のメッキ２に接触して付与されている第２のメッキ用触媒１２上とに渡って施され、図２（Ｈ）に示す態様の製品を得た。
なお、メッキ５は、幅０．２〜０．３ｍｍ、間隔０．１〜０．０５ｍｍ、厚さ０．５〜５．０μｍであった。
【００７２】
実施例４
第１、第２の被覆材として加水分解性高分子材を用い、実施例３と同様に、図２（Ａ）〜（Ｈ）の工程に沿って実施した。
〔前処理工程〕
実施例３と同様にして実施例１と同様の基体１を成形し、粗化した。
【００７３】
〔第１工程《第１の被覆工程》〕
粗化後の基体１をセットし５〜３０℃（本例では１０℃）に保持した２次金型内に、１５０〜２６０℃（本例では１９０℃）に加熱した被覆材３としての加水分解性高分子材（ポリ乳酸樹脂《三井化学社製商品名“ＬＡＣＥＡ”を使用》）を、射出圧２００〜１２００ｋｇ／ｃｍ^２（本例では３５０ｋｇ／ｃｍ^２）で射出し、図２（Ａ）に示す態様の厚さ０．５ｍｍ、幅０．２ｍｍ、間隔０．２ｍｍの部分被覆３を得た。
【００７４】
〔第２工程《第１のメッキ用触媒付与工程》〕
実施例３の第２工程と同様にして、実施例３と同様の第１のメッキ用触媒１１を、図２（Ｂ）に示すように、基体１の非被覆面（露出面）に付与した。
【００７５】
〔第３工程《第１の被覆材除去工程》〕
実施例３の第３工程と同様にして、第１の被覆材３を除去した。
【００７６】
〔第４工程《第１のメッキ工程》〕
実施例３の第４工程と同様にして、無電解銅メッキを施した。
また、実施例３の第４工程と同様にして、無電解銅メッキを施した後、電気銅メッキを施した。
いずれの場合も、図２（Ｄ）に示すように、メッキ用触媒１１付与面のみに、銅メッキ２が施されていた。
【００７７】
〔第５工程《第２の被覆工程》〕
第１工程と同じ樹脂を用い、第１工程と同様にして、図２（Ｅ）に示すように、メッキ２が施されている部分（メッキ部）と、施されていない部分（非メッキ部）とに渡って、厚さ０．５ｍｍ、幅０．２〜０．３ｍｍ、間隔０．１ｍｍの第２の被覆４を得た。
【００７８】
〔第６工程《第２のメッキ用触媒付与工程》〕
第２工程の第１のメッキ用触媒と同じ触媒を、第２工程と同様にして、図２（Ｆ）に示すように、基体１の非被覆面（露出面）に、第２のメッキ用触媒１２を付与した。
【００７９】
〔第７工程《第２の被覆材除去工程》〕
第３工程と同様にして、第２の被覆材４を除去し、図２（Ｇ）の態様のものを得た。
【００８０】
〔第８工程《第２のメッキ工程》〕
第４工程と同じメッキ材を、第４工程と同様にして第２のメッキを施した。
この第２のメッキ５は、第１のメッキ２上と、該第１のメッキ２に接触して付与されている第２のメッキ用触媒１２上とに渡って施され、図２（Ｈ）に示す態様の製品を得た。
なお、メッキ５は、幅０．２〜０．３ｍｍ、間隔０．１〜０．０５ｍｍ、厚さ０．５〜５．０μｍであった。
【００８１】
【発明の効果】
本発明（第１、第２発明）の方法によれば、ファインパターンでのメッキを極めて高精度で施すことができる。
【００８２】
このときの被覆材として、水溶性高分子材料又は加水分解性高分子材料を使用すれば、該被覆材の除去を、有機溶剤を使用することなく、水溶性高分子材料では水を使用することで、また加水分解性高分子材料ではアルカリ水溶液や酸液を使用することで行うことができる。
これらの高分子材料として生分解性のものを使用すれば、土中や水中の微生物により水と二酸化炭素に容易に分解されるため、環境問題の懸念がなく、基体から除去後の廃棄処理が極めて簡単である。
【００８３】
また、水溶性高分子材料又は加水分解性高分子材料は、従来この種の被覆材として使用されていたプラスチックやゴム等に比して、射出成形した場合の転写性（型の形状通りに成形される性質）に優れる上、固化速度が緩慢であるため、基体（一般に被覆材とは異なる材料を使用）との界面密着性が高まり、寸法精度の高いファインメッキが可能となり、高品質のファインメッキ品を得ることができる。
【００８４】
しかも、この水溶性高分子材料又は加水分解性高分子材料は、最終的にはメッキ製品から除去されるため、これらの高分子材料による被覆形状は、最終製品の形状や寸法に左右されず、専らメッキ操作に好都合な設計とすることができ、最終製品の軽薄短小化に寄与する。すなわち、メッキ工程時の被覆材の形状や寸法によって最終製品の形状や寸法が制約されないため、基体を自由に被覆することができ、これにより基体上への立体的なパターンでの回路電極の形成が可能となって、回路電極、延いては該回路電極を装備する各種電子・電気部品の設計の自由度が増し、これら電子・電気部品の小型化・軽量化を一層進めることができる。
【００８５】
更に、本発明では、メッキが施されていない部分には、メッキ用触媒が残らないため、メッキ後の言い換えれば回路成形後の電気的な表面抵抗値が高くなり、製品の電気的特性を向上させることができる。
【００８６】
本発明によれば、従来のレジストの塗布・硬化・除去工程を省略することができ、従って有機溶剤による環境問題の懸念もないし、工程を短縮することもできる。
また、寸法精度が高く、かつ電気的表面抵抗値の高い、高品質の電子・電気部品を提供することができる。
【図面の簡単な説明】
【図１】第１発明の方法の一実施態様例を工程順に説明するための図である。
【図２】第２発明の方法の一実施態様例を工程順に説明するための図である。
【符号の説明】
１ 基体
２ メッキ
３ 第１の被覆材
４ 第２の被覆材[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for plating a substrate made of a synthetic resin or other material with a partial and fine pattern, and in particular, for manufacturing electronic / electric parts such as printed circuit boards and lead frame insert molded circuit parts. The present invention relates to a plating method with a partial and fine pattern on the substrate.
[0002]
[Technical background]
Conventionally, as a method of partially plating a synthetic resin substrate (molded product),
(1) The surface of the molded product is roughened (for example, etched), and a plating catalyst based on Pd, Pt, etc. is applied, and then a resist is applied by a silk printing method, a dispenser coating method, etc. leaving the portion to be plated. And then plating and removing the resist,
(2) Insert the molded article after applying the catalyst into a mold, and inject (inject) plastic, rubber or the like (electrical insulating material) into the mold, A method of coating, then plating, and removing the coating material if necessary,
Etc. are known (CMC Co., Ltd., “Composite Technology for Plastic Molding” P260-275, Japanese Patent Laid-Open No. 7-316825, Japanese Patent Laid-Open No. 63-4092, Japanese Patent No. 2592243, etc.).
[0003]
However, in the method (1), a resist curing step by heat drying or the like is necessary after resist application. In addition, when removing the resist after plating, it is necessary to use an organic solvent such as methylene chloride. This organic solvent such as methylene chloride is considered to be a cause of ozone layer destruction like chlorofluorocarbon (CFC), and is discarded. If this increases, there is a concern that skin cancer and cataracts will increase, or that ecosystems such as plants and plankton will be destroyed.
In the method (2), since the adhesion of the coating material is low, the plating solution enters the boundary surface of the coating material, and the dimensional accuracy is low. Moreover, when removing a coating | covering material as needed, there exists a concern similar to said resist.
[0004]
On the other hand, in recent years, partial plating technology (fine plating technology) with extremely fine patterns has been accompanied by increasing demands for electronic and electrical components that are lighter, thinner, and smaller, and for electronic and electrical components that can be used in higher frequency bands. The development and practical use of is considered an urgent task.
However, a plating method with a fine pattern (fine pattern) satisfying such a requirement has not been known until now, in addition to the methods (1) and (2).
One reason for this is the fluidity of the conventional coating material made of thermoplastic resin or the coating material made of polylactic acid in the previous proposal by the present inventor (Japanese Patent Application No. 11-175460). When using a simple coating material, the limit was to reduce the circuit interval (non-plated portion) width to about 0.3 to 0.25 mm.
[0005]
OBJECT OF THE INVENTION
The present invention is required for partial plating with extremely fine patterns, particularly for photoelectric conversion packages and high-frequency packages that are used in high-frequency bands, in order to meet the demands for further miniaturization and higher performance of electronic and electrical components. The main purpose is to provide a fine plating method (fine plating method) that can obtain a high circuit interval of about 0.10 mm with high accuracy. At this time, there is no resist coating / curing / removing step, so organic It is a secondary object to provide a fine plating method that does not cause environmental problems due to the solvent, can shorten the process, and can provide high-quality electronic / electric parts with high conductivity.
[0006]
SUMMARY OF THE INVENTION
In the present invention, [1] plating the entire surface of the substrate in advance and repeating the coating and the removal of the plating from the uncoated portion (hereinafter referred to as the first invention), or [2] the substrate. It is intended to achieve high-precision fine plating by repeatedly applying a plating catalyst to the non-coated portion, removing the coating material, and plating (hereinafter referred to as the second invention). is there.
Further, according to the methods of the first and second inventions, the circuit interval (non-plated portion) can be obtained even if the water-soluble polymer material or hydrolyzable polymer material used in the previous proposal of the present inventor is used as a coating material. ) By obtaining the knowledge that the width can be reduced to 0.25 mm or less and using these materials, the above-mentioned secondary purpose is also achieved.
[0007]
  That is, the fine plating method of the present invention is
[1] The first invention is
  (1) a step of plating the surface of the substrate;
  (2) By an injection molding method in which the base is a part of the mold partly in an appropriate pattern on the plated part,Water-soluble polymer material or hydrolyzable polymer materialApplying a first coating;
  (3) a step of removing plating in a portion other than the first covering portion;
  (4) a step of removing the first covering material;
  (5) By an injection molding method in which the base is part of the mold, partially in an appropriate pattern over the plating removal portion and the plating remaining portion,Water-soluble polymer material or hydrolyzable polymer materialApplying a second coating;
  (6) a step of removing plating on portions other than the second covering portion;
  (7) removing the second covering material;
It is characterized by going in this order,
[2] The second invention is
  (1) By an injection molding method in which the surface of the substrate is partly in an appropriate pattern and the substrate is a part of the mold,Water-soluble polymer material or hydrolyzable polymer materialApplying a first coating;
  (2) a step of applying a first plating catalyst to a portion other than the first covering portion;
  (3) removing the first covering material;
  (4) applying the first plating;
  (5) By an injection molding method in which the base is a part of the mold partly in an appropriate pattern over the non-plated part and the plated part,Water-soluble polymer material or hydrolyzable polymer materialApplying a second coating;
  (6) A step of applying a second plating catalyst to a portion other than the second covering portion,
  (7) removing the second covering material;
  (8) applying a second plating;
It is characterized by going through in this order.
  In the second invention, the steps (5) to (8) may be added more than once.Good.
[0008]
[Substrate]
In the present invention, the substrate may be composed of an inorganic material such as ceramic or glass in addition to a synthetic resin such as a thermoplastic resin or a thermosetting resin.
Preferably, aromatic liquid crystal polymer, polysulfone, polyether polysulfone, polyarylsulfone, polyetherimide, polyester, acrylonitrile-butadiene-styrene copolymer resin, polyamide, modified polyphenylene oxide resin, norbornene resin, phenol resin, epoxy resin, etc. It is comprised from.
More preferably, it is a polyester-based liquid crystal polymer that is close to a metal under temperature conditions with a wide range of heat resistance and thermal expansion coefficient, and has the same stretchability as that of a metal film, and has excellent characteristics equivalent to that of a metal film in a thermal cycle test. It is comprised from.
These substrates may be those added with glass fibers, calcium pyrophosphate, wollastonite, calcium carbonate, barium titanate, carbon fibers, quartz fibers, barium sulfate, and the like as fillers.
The substrate may be a flat plate or may be molded into various shapes (molded product).
[0009]
  (Coating material)
  Coating material is a water-soluble or hydrolyzable polymer materialBecauseA material that can be molded into a fixed shape on the substrate can be used, and a biodegradable material is particularly preferable in order to avoid environmental problems.
  Specifically, in addition to the polyvinyl alcohol represented by Formula 1 of Chemical Formula 1, the modified polyvinyl alcohol represented by Formula 2, the polylactic acid represented by Formula 3, starch, microbial fermented aliphatic polyester, aliphatic polyester-dicarboxylic acid And diglycol condensates, aliphatic caprolactone resins, cellulose acetate resins, and the like, particularly preferably hydrolyzable polylactic acid or a mixture or copolymer of aliphatic polyester mainly composed of polylactic acid It is a combination (random copolymer, block copolymer).
[0010]
[Chemical 1]

[0011]
The above polylactic acid may be used alone or as a main component of polylactic acid, and an aliphatic polyester (from polyhydroxycarboxylic acid, hydroxycarboxylic acid or aliphatic polyhydric alcohol and aliphatic polybasic acid). A random copolymer or block copolymer comprising two or more monomer components selected from aliphatic polyesters, hydroxycarboxylic acids and aliphatic polyhydric alcohols, and two or more monomer components selected from aliphatic polybasic acids. A polymer or the like) or a mixture of two or more thereof, a random copolymer or a block copolymer, and an alkali decomposition accelerator, an organic or inorganic filler, if necessary, What mixed the additive which can be used for general purpose synthetic resins, such as a plasticizer, a wetting agent, a ultraviolet absorber, antioxidant, a lubricant, and a coloring agent, may be used.
The mixing amount or copolymerization amount of the aliphatic polyester is about 1 to 10 wt% with respect to the total amount of the mixture or copolymer, the mixing amount of the alkali decomposition accelerator is about 1 to 100 wt% with respect to the total amount of the mixture, Preferably it is 5-80 wt%, More preferably, it is 10-60 wt%, and about 1-5% is suitable for the mixing amount of another additive with respect to the mixture whole quantity.
[0012]
In addition, the weight average molecular weight of the polylactic acid is preferably about 10,000 to 400,000, and the aliphatic polyester has a weight average molecular weight of about 10,000 to 500,000 when mixed with polylactic acid, preferably 30,000 to About 400,000, more preferably about 50,000 to 300,000 is suitable. When copolymerizing with polylactic acid, the weight average molecular weight of the copolymer is about 10,000 to 500,000, preferably 30,000 to 400,000. About 50,000 to 300,000 is more suitable.
Examples of the hydroxycarboxylic acid include glycolic acid, L-lactic acid, D-lactic acid, D / L-lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, and 5-hydroxyvaleric acid. Rick acid, 6-hydroxycaproic acid and the like can be mentioned, and one or more of these can be used.
Examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 3-methyl-1,5-pentane. Diol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, and the like, one or more of these Can be used.
Aliphatic polybasic acids include succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, phenylsuccinic acid, 1, 4-phenylenediacetic acid and the like can be mentioned, and one or more of these can be used.
Examples of the alkali decomposition accelerator include starch, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyalkylene glycols such as polyoxytetramethylene glycol, hydrophilic polymer compounds such as polyamino acids, and alkaline hydrolysis such as succinic anhydride and polysuccinimide. Examples include decomposable compounds, and one or more of these can be used. Among these, polyalkylene glycol, particularly polyethylene glycol is preferable from the viewpoint of dispersibility and compatibility with polylactic acid and aliphatic polyester, difficulty in bleeding, and the like.
[0013]
The fine plating process of the first invention:
1st invention is performed at the process shown to FIG. 1 (A)-(H).
First, plating 2 is applied to the surface of the substrate 1 shown in FIG. 1A in the first step shown in FIG. 1B. Prior to this plating, the surface of the substrate 1 is roughened as a pretreatment step. And then a plating catalyst is applied.
[0014]
[Pretreatment process]
(Roughening of substrate surface)
As a method for roughening the surface of the substrate, for example, a known etching method can be applied.
There are wet and dry etching methods, and an appropriate etching method may be employed depending on the type of material used for the substrate.
The dry method can be performed, for example, by irradiating plasma or using gas.
The wet method uses, for example, an aqueous solution of an alkali metal hydroxide such as NaOH or KOH, an aqueous solution of an alkali metal alcoholate such as alcoholic sodium or alcoholic potassium, or an organic solvent such as dimethylformamide. It can be carried out by applying to the surface or by contacting the substrate by immersing the substrate in these liquids.
Among these, the method using an aqueous solution of NaOH, KOH or the like is preferably performed under conditions of a concentration of about 35 to 50 wt% and a temperature of about 70 to 95 ° C.
In addition, when using an organic solvent, only a base | substrate is swollen and it may not lead to roughening. In this case, an acid or alkali treatment may be performed after the treatment with the organic solvent.
[0015]
In the wet method, it is preferable to perform treatment using an acid solution such as hydrochloric acid or hydrofluoric acid after bringing the etching solution into contact with the substrate. This acid treatment is not performed simply to neutralize the alkaline etching solution, but a part of the filler that is contained in the substrate and is present in the vicinity of the surface of the substrate is removed. This is performed to further enhance the surface roughening effect.
Therefore, it is preferable that the conditions for the acid treatment (pH, temperature, time, etc.) are such that the filler is dissolved.
[0016]
(Addition of catalyst for plating)
As the catalyst for plating (hereinafter, sometimes simply referred to as catalyst), known ones can be used, and among them, those containing Pd and Pt are preferable, and these are used as inorganic salts such as chlorides, for example.
The application of the catalyst for plating is performed by depositing the above catalyst metal by an accelerator treatment after adhering the above inorganic salt to the substrate.
In order to allow the inorganic salt to adhere to the substrate, the inorganic salt solution and the substrate may be brought into contact with each other, for example, by immersing the substrate in an inorganic salt solution or applying this aqueous solution to the substrate. .
The specific conditions differ depending on the substrate material, plating material, plating catalyst material, inorganic salt deposition method, etc., and cannot be determined unconditionally, but use palladium chloride as the plating catalyst salt and immerse it. Taking the case of adopting the law as an example, the following can be cited as an example.
[0017]
Catalyst salt solution composition
PdCl₂・ 2H₂O: 0.1 to 0.3 g / dm³
SnCl₂・ 2H₂O: 10 to 20 g / dm³
HCl: 150-250 cm³/ Dm³
Immersion conditions
Temperature: 20-45 ° C
Time: 1-10 minutes
[0018]
As the solvent for the catalyst salt solution for plating, an organic solvent such as methanol, ethanol, isopropyl alcohol or the like can be used in addition to the above hydrochloric acid.
[0019]
After adhesion of the plating catalyst salt as described above, it is washed with water and subjected to an accelerator treatment to deposit the plating catalyst (metal) on the substrate.
In general, the accelerator treatment is performed by bringing an accelerator (accelerating liquid) and the base after application of the catalyst salt into contact with each other by dipping or coating.
As this accelerating liquid, an inorganic solution such as sulfuric acid, hydrochloric acid, sodium hydroxide, ammonia or the like is used.
When a catalyst salt solution having the above composition is used and the catalyst salt is applied by immersion under the above conditions, Sn adhered to the substrate surface by washing with water²⁺-Pd²⁺The complex of²⁺Precipitates as Sn (OH) Cl, and subsequent accelerator treatment produces metal Pd on the substrate. This metal Pd acts as a plating catalyst.
[0020]
[First step << Plating step >>]
In the first step, plating 2 is applied to the entire surface of the base 1 as shown in FIG. Therefore, the above pretreatment is also applied to the entire surface of the substrate.
As a plating method, a known metalizing method (electroless plating method or electroplating method) can be adopted.
Examples of the plating metal include copper, nickel, gold, and other various metals.
The plating process can be performed in multiple times or can be performed once at a time.
In addition, a preliminary plating process can also be provided after a catalyst provision process. Pre-plating can also be performed by a known metalizing method, preferably an electroless plating method, and a plating metal similar to the metal in the so-called main plating process can be used. By providing this preliminary plating step, the plating quality in the main plating step can be further improved.
Further, a post plating step can be provided. The post-plating step can also be performed by a known metalizing method, preferably an electroless plating method, and the plating metal may be the same type as the metal in the main plating step, but is different. Also good.
[0021]
  [Second Step << First Coating Step >>]
  In the second step, as shown in FIG. 1 (C), using the above-mentioned coating material, the first coating is partially applied in an appropriate pattern (not limited to the pattern of FIG. 1 (C)) on the plating 2 surface. 3 is applied.
  This first coating 3 isBirthMethod of forming the covering shape by the forming methodAnd the groupIn this method, a desired portion of the surface of the substrate is coated simultaneously with the injection of the coating material by an injection molding method using the body as a part of the mold.
  Since the dimension of the first coating 3 varies depending on the shape of the pattern, it cannot be generally stated. For example, in the case of a stripe shape as shown in FIG. 1C, the width is about 0.2 to 0.3 mm. A distance of about 0.05 to 0.10 mm is suitable.
[0022]
[Third step << first plating removal step]
In the third step, as shown in FIG. 1 (D), the plating of the portion other than the portion where the partial first coating 3 is applied, that is, the exposed portion is removed.
The plating material 2 can be removed by any method as long as it removes the plating metal as described above but does not remove the first coating 3. In general, ferric chloride, chloride, etc. It is carried out by bringing a solution of an inorganic salt such as cupric or ammonium persulfate into contact with the plating surface by dipping or coating.
This plating removal process is an extremely important process in the first invention for performing a fine plating pattern precisely and with high accuracy, and is performed under the following conditions, for example.
[0023]
When the inorganic salt solution is used, the concentration of the inorganic salt is 0.5 to 100 g / liter, preferably 1.5 to 4.0 g / liter (hereinafter, the liter is referred to as L and the milliliter is referred to as mL). .
If the amount is less than 0.5 g / L, the amount of the inorganic salt is too small and the processing power per unit weight of the solution is not sufficient. If the amount is more than 100 g / L, the coating material or the substrate may be damaged.
If the contact time is too short, the treatment is not sufficient. If the contact time is too long, the coating material or the substrate may be damaged.
In addition, water, lower alcohol (methyl alcohol, ethyl alcohol, etc.) etc. are used for the solvent of this inorganic salt solution.
[0024]
[Fourth Step << First Covering Material Removal Step]
In the fourth step, the first covering material 3 is removed as shown in FIG.
Removal of the covering material 3 is performed using water in the case of a water-soluble polymer material, and using an aqueous alkali solution or an acid solution (various inorganic acid solutions) in the case of a hydrolyzable polymer material.
This step of removing the covering material 3 is also an extremely important step in carrying out the fine plating pattern precisely and with high accuracy in the first invention, and is performed under the following conditions, for example.
When the covering material 3 is a water-soluble polymer material, depending on the type of the polymer material, it is generally preferable to remove it by immersing it in warm water at about 25 to 95 ° C. for 2 to 35 hours.
When the covering material 3 is a hydrolyzable polymer material, particularly polylactic acid, it is immersed for about 1 to 120 minutes in a caustic (NaOH, KOH, etc.) aqueous solution having a concentration of about 2 to 15 wt% and a temperature of about 25 to 70 ° C It is preferable to remove it.
[0025]
[Fifth step << second covering step >>]
  In the fifth step, as shown in FIG. 1 (F), the portion from which the plating 2 has been removed in the third step (plating removal portion) and the portion from which the plating 2 has not been removed (plating remaining portion) are covered. The second coating 4 is applied partially in an appropriate pattern using the above-described coating material.
  The pattern at this time is not limited to that shown in FIG. 1 (F), and any pattern may be used as long as it extends to the plating removal portion and the plating remaining portion.
  The second covering material 4 may be the same material as the first covering material 3 or may be a different material.
  Further, the second coating 4 is also irradiated in the same manner as the first coating 3 described above.BirthMethod of forming the covering shape by the forming methodAnd the groupIn this method, a desired portion of the surface of the substrate is coated simultaneously with the injection of the coating material by an injection molding method using the body as a part of the mold.
  Similarly to the case of the first coating 3, the dimensions of the second coating 4 cannot be generally specified. For example, in the case of a stripe shape as shown in FIG. The same width and interval as in the case of 3 are suitable.
[0026]
[Sixth step << second plating removal step]
In the sixth step, as shown in FIG. 1 (G), the plating of portions other than the second coating 4 is removed. This plating removal is performed by the same method as the plating removal in the third step described above. Done.
[0027]
[Seventh Step << Second Coating Material Removal Step]
In the seventh step, the second covering material 4 is removed as shown in FIG. The removal of the covering material 4 is performed by the same method as the removal of the first covering material 3 in the fourth step described above.
By passing through the above first to seventh steps, for example, a fine plating 2 having a width of about 0.1 mm can be obtained.
[0028]
The fine plating process of the second invention:
The second invention is performed in the steps shown in FIGS.
First, as shown in FIG. 2 (A), the first coating 3 is applied to the surface of the substrate 1 in the first step. Prior to this coating, the surface of the substrate 1 is roughened as a pretreatment step. To do.
[0029]
[Pretreatment step << Roughening of substrate surface >>
As the surface roughening method of the substrate 1, a known etching method similar to the case of the first invention described above can be applied.
This surface roughening is applied to the entire surface of the substrate 1 as in the case of the first invention.
[0030]
[First step << first covering step >>]
  In the first step, as shown in FIG. 2 (A), the above-described coating material is used on the roughened substrate 1, and the pattern is appropriately limited (not limited to the pattern shown in FIG. 2 (A)). A first coating 3 is applied.
  This first coating 3 is the same as the first and second coatings 3 and 4 in the first invention.BirthMethod of forming the covering shape by the forming methodAnd the groupIn this method, a desired portion of the surface of the substrate is coated simultaneously with the injection of the coating material by an injection molding method using the body as a part of the mold.
  The dimensions of the first coating 3 cannot be generally described in the same way as the first and second coatings 3 and 4 of the first invention, but the first and second coatings 3 and 4 of the first invention Similar widths and spacings are suitable.
[0031]
[Second step << first plating catalyst application step}
In the second step, as shown in FIG. 2 (B), the first plating catalyst 11 is applied to the surface of the base 1 in a portion not covered with the first coating material 3.
The type of the plating catalyst 11 and the method of applying the plating catalyst 11 are the same as in the case of applying the catalyst in the pretreatment step in the first invention described above.
When an organic solvent such as methanol, ethanol, isopropyl alcohol or the like is used as a solvent for the plating catalyst salt solution, a part of the coating material made of the above water-soluble or hydrolyzable polymer material may be eluted. However, it may be partially eluted.
[0032]
[Third step << first covering material removing step]
In the third step, the first covering material 3 is removed as shown in FIG.
The removal of the covering material 3 is the same as in the case of the first invention described above. However, when the covering material 3 is a hydrolyzable polymer material, particularly polylactic acid, the caustic alkaline aqueous solution has a higher temperature and concentration. 3 as well as the catalyst for plating may fall off, soak it in caustic (NaOH, KOH, etc.) aqueous solution at a concentration of about 2 to 15 wt% and a temperature of about 25 to 70 ° C. for about 1 to 120 minutes. It is preferable to remove.
[0033]
[Fourth Step << First Plating Step >>]
In the fourth step, the first plating is applied, but this plating 2 is applied only to the portion to which the first plating catalyst 11 is applied, as shown in FIG.
The plating method and the plating metal are the same as in the case of the first invention described above.
[0034]
[Fifth step << second covering step >>]
  As shown in FIG. 2 (E), the fifth step is appropriately performed over the portion that has not been plated in the fourth step (non-plated portion) and the portion that has been plated 2 (plated portion). A second coating 4 is applied partially in the pattern using the above-described coating material.
  As shown by α in FIG. 2 (E), the pattern at this time is such that all of the plated portion is covered over the non-plated portion and the plated portion, or as shown by β in FIG. One surface of the plated portion may be covered over the portion and the plated portion, but the other surface may not be covered (exposed), and is not limited to that shown in FIG. Any pattern may be used as long as it extends over the part and the plating part.
  The second covering material 4 may be the same material as the first covering material 3 or may be a different material as in the case of the first invention.
  Further, the second coating 4 is also irradiated in the same manner as the first coating 3 described above.BirthMethod of forming the covering shape by the forming methodAnd the groupIn this method, a desired portion of the surface of the substrate is coated simultaneously with the injection of the coating material by an injection molding method using the body as a part of the mold.
  The dimensions of the second coating 4 cannot be generally specified as in the case of the first coating 3, but the same width and interval as in the case of the first coating 3 are suitable.
[0035]
[Sixth Step << Second Catalyst Application Step}
In the sixth step, as shown in FIG. 2 (F), a second plating catalyst 12 is applied to the surface of the base 1 in a portion not covered with the second coating material 4.
The type of the plating catalyst 12 and the method for applying the plating catalyst 12 are the same as in the case of applying the first plating catalyst 11 in the third step.
[0036]
[Seventh Step << Second Coating Material Removal Step]
  In the seventh step, the second covering material 4 is removed as shown in FIG. The removal of the covering material 4 is the same as the removal of the first covering material 3 described above.
  By this seventh step, as shown in FIG. 2 (G), the second plating catalyst 12 becomes the first plating portion.2It will be given in contact with.
[0037]
[Eighth process << second plating process >>
In the eighth step, the second plating is performed. The second plating 5 is divided into the second plating catalyst 12 and the first plating 2 as shown in FIG. Applied.
That is, the first plating 2 already applied in the fourth step serves as a nucleus, and the second plating 5 is applied on the plating 2 and is applied in contact with the first plating 2. The second plating 5 is applied on the second plating catalyst 12, and a plating mode as shown in FIG. 2 (H) is obtained.
[0038]
By passing through the above first to eighth steps, for example, a fine plated portion 2 or 5 having a width of about 0.2 mm is obtained, and a non-plated portion having a width of about 0.1 mm is obtained.
The thickness of the plated portion 2 and the plated portion 5 shown in FIG. 2 (H) is slightly thicker than that of the plated portion 2 in the plated portion 5.
In addition, said 5th-8th process is not restricted to once, and can also be added in multiple times. That is, after the first to eighth steps, a second (actually third) coating step in the fifth step, a third plating catalyst application step in the sixth step, and a third coating material removal step in the seventh step The third plating step of the eighth step can be added, and the fifth to eighth steps can be repeated a plurality of times.
[0039]
【Example】
Example 1
A water-soluble polymer material was used as the first and second coating materials, and the steps were carried out along the steps of FIGS.
[0040]
[Pretreatment process]
(Substrate molding process)
In FIG. 1A, a plate-shaped substrate 1 was molded from an aromatic polyester (liquid crystal polymer “trade name“ Vectra C810 ”manufactured by Celanese, USA)” using a primary mold.
The substrate 1 was immersed for 10 minutes in a degreasing solution heated to 60 ° C. (trade name “A Screen A220” manufactured by Okuno Pharmaceutical Co., Ltd., 50 g / liter (hereinafter referred to as L, milliliter as mL) aqueous solution), and then washed with water. And degreased.
[0041]
(Roughening process of substrate surface)
An alkaline solution in which 350 to 500 g of metal Na (430 g in this example) is dissolved in 1 L of methyl alcohol is heated to 90 ° C., and the degreased substrate 1 is immersed in this heated solution for 30 to 80 minutes (in this example). 40 minutes), the surface of the substrate 1 was roughened.
In addition, when using ethyl alcohol (metal Na430g) instead of methyl alcohol, roughening was possible under the same conditions.
When isopropyl alcohol (metal Na 430 g) is used instead of methyl alcohol, this alkaline solution is heated to 60 ° C., the degreased substrate 1 is immersed, held for 10 minutes, and then mixed with chromic acid (CrO₃It was possible to roughen by adding 22 wt% and concentrated sulfuric acid 54 wt% mixed solution) to 60 ° C.
Further, when an alkaline solution in which 350 to 500 g of NaOH (430 g in this example) was dissolved in 1 L of water was used, roughening could be performed under the same conditions as in the case of using the above methyl alcohol.
[0042]
(Plating catalyst application process)
To methyl alcohol, a mixed hydrochloric acid solution of stannous chloride and palladium chloride as a catalyst salt for plating (trade name “Enylex CT-8” manufactured by Sugawara Eugleite Co., Ltd.) was added at a rate of 20 mL / L. The surface roughened substrate 1 was immersed in this solution for 3 to 5 minutes (4 minutes in this example), washed with water, and heated in hydrochloric acid (50 mL / L) heated to 60 ° C. The substrate was immersed for 60 minutes (accelerator treatment), and a plating catalyst was applied to the entire surface of the substrate 1.
In addition, also when using ethyl alcohol instead of methyl alcohol, the catalyst for plating was able to be provided on the same conditions.
[0043]
[First step << Plating step >>]
The substrate 1 is pre-plated using a copper plating bath having the composition shown in Table 1 and plating conditions shown in Table 2 or using either a Rochelle type or EDTA type copper plating bath shown in Table 3. Thereafter, the main plating is performed using a copper plating bath having the composition shown in Table 4 (the conditions for the two-step plating are as shown in Table 2 for both preliminary and main plating), and the thickness is 0.3 to 20 Electroless copper plating was performed so as to have a thickness of 0.0 μm (in this example, 10 μm), thereby obtaining a plating 2 having the form shown in FIG. In addition, when electroless copper plating was applied to a thickness of 0.5 μm and then electrolytic copper plating was applied to a thickness of 0.5 μm, plating 2 having the form shown in FIG. 1B was obtained. .
[0044]
[Table 1]
Copper plating bath composition
CuSO₄・ 5H₂O: 0.04 mol / L
HCHO (37% solution): 0.1 mol / L
NaOH: 0.2 mol / L
EDTA · 4Na: 0.08 mol / L
α, α'-dipyridyl: 5 to 10 ppm
PEG-1000^{* 1}  : 50-100ppm
* 1 PEG-1000; Stabilizer
[0045]
[Table 2]
Plating conditions
Bath temperature: 60-70 ° C
Air agitation: 0.1 L / L · min
Bath: 0-1dm²/ L
[0046]
[Table 3]

[0047]
[Table 4]
Copper plating bath composition
CuSO₄・ 5H₂O: 0.04 mol / L
HCHO (37% solution): 0.06 mol / L
NaOH: pH 12
EDTA · 4Na: 0.1 mol / L
Stabilizer^{* 2}            :Slightly
[0048]
[Second Step << First Coating Step >>]
First covering material heated to 150 to 260 ° C. (190 ° C. in this example) in a secondary mold in which the base body 1 after plating 2 is set and held at 5 to 30 ° C. (10 ° C. in this example) 3 water-soluble polymer material (polyvinyl alcohol (hereinafter referred to as “PVA”) “Kuraray brand name“ Poval ”is used)), injection pressure 200 to 1200 kg / cm²(In this example, 350 kg / cm²) To obtain a partial coating 3 having a thickness of 1 mm, a width of 0.3 mm, and an interval of 0.1 mm as shown in FIG.
[0049]
[Third step << first plating removal step]
It was immersed in a ferric chloride aqueous solution having a concentration of 3 g / L for 1 to 10 minutes, and the portions other than the partial coating 3 were removed by plating to obtain the embodiment shown in FIG.
[0050]
[Fourth Step << First Covering Material Removal Step]
After completion of the third step, the substrate 1 is immersed in a 30 ° C. NaOH aqueous solution at a concentration of 7% by weight for 40 minutes to remove the first coating material 3 to obtain the embodiment shown in FIG. It was.
[0051]
[Fifth step << second covering step >>]
In the same manner as in the second step, partial coating 4 having a thickness of 1 mm, a width of 0.3 mm, and an interval of 0.1 mm as shown in FIG.
[0052]
[Sixth step << second plating removal step]
In the same manner as in the third step, the plating 2 was removed to obtain the embodiment shown in FIG.
[0053]
[Seventh Step << Second Coating Material Removal Step]
The second covering material 4 was removed in the same manner as in the fourth step.
As described above, a plated product having a plating (circuit) width and a circuit interval width of about 0.1 mm could be obtained in the manner shown in FIG.
[0054]
Example 2
A hydrolyzable polymer material was used as the first and second coating materials, and the same procedures as in Example 1 were performed in accordance with the steps of FIGS.
[Pretreatment process]
In the same manner as in Example 1, the same substrate 1 as in Example 1 was molded, roughened, and a plating catalyst was applied.
[0055]
[First step << Plating step >>]
In the same manner as in Example 1, electroless copper plating was performed.
Further, in the same manner as in Example 1, after electroless copper plating, electrolytic copper plating was performed.
In any case, similarly to Example 1, a plating 2 having a thickness of 10 μm in the form shown in FIG. 1B could be obtained.
[0056]
[Second Step << First Coating Step >>]
As a coating material 3 heated to 150 to 260 ° C. (190 ° C. in this example) in a secondary mold in which the base body 1 after plating 2 is set and held at 5 to 30 ° C. (10 ° C. in this example) Hydrolyzable polymer material (polylactic acid resin (using trade name “LACEA” manufactured by Mitsui Chemicals, Inc.)), injection pressure 200 to 1200 kg / cm²(In this example, 350 kg / cm²) To obtain a partial coating 3 having a thickness of 0.5 mm, a width of 0.3 mm, and an interval of 0.1 mm as shown in FIG.
[0057]
[Third step << first plating removal step]
In the same manner as in the third step of Example 1, parts other than the partial coating 3 were removed by plating to obtain the embodiment shown in FIG.
[0058]
[Fourth Step << First Covering Material Removal Step]
After completion of the third step, the base 1 was removed from the first covering material 3 in the same manner as in the fourth step of Example 1 to obtain an embodiment shown in FIG.
[0059]
[Fifth step << second covering step >>]
In the same manner as in the second step, partial coating 4 having a thickness of 0.5 mm, a width of 0.3 mm, and a spacing of 0.1 mm as shown in FIG.
[0060]
[Sixth step << second plating removal step]
In the same manner as in the third step, the plating 2 was removed to obtain the embodiment shown in FIG.
[0061]
[Seventh Step << Second Coating Material Removal Step]
The second covering material 4 was removed in the same manner as in the fourth step.
As described above, a plated product having a plating (circuit) width and a circuit interval width of about 0.1 mm could be obtained in the manner shown in FIG.
[0062]
Example 3
A water-soluble polymer material was used as the first and second coating materials, and the steps were carried out along the steps of FIGS.
[0063]
[Pretreatment process]
In the same manner as in Example 1, the same substrate 1 as in Example 1 was molded and roughened.
[0064]
[First step << first covering step >>]
As a covering material 3 heated to 150 to 260 ° C. (190 ° C. in this example) in a secondary mold in which the substrate 1 after surface roughening is set and held at 5 to 30 ° C. (10 ° C. in this example) Water-soluble polymer material (PVA << trade name "Poval" manufactured by Kuraray Co., Ltd.)], injection pressure 200-1200kg / cm²(In this example, 350 kg / cm²) To obtain a partial coating 3 having a thickness of 0.5 mm, a width of 0.2 mm, and an interval of 0.2 mm as shown in FIG.
[0065]
[Second step << first plating catalyst application step}
To methyl alcohol, a mixed hydrochloric acid solution of stannous chloride and palladium chloride as a catalyst salt for plating (trade name “Enylex CT-8” manufactured by Sugawara Eugleite Co., Ltd.) was added at a rate of 20 mL / L. The substrate 1 coated with the first partial coating 3 was immersed in this solution for 3 to 5 minutes (4 minutes in this example), washed with water, and heated to 60 ° C. with hydrochloric acid ( 50 ml / L) for 60 minutes (accelerator treatment), and as shown in FIG. 2B, the first plating catalyst 11 was applied to the uncoated surface (exposed surface) of the substrate 1.
[0066]
[Third step << first covering material removing step]
After the plating catalyst 11 was applied, the first covering material 3 was removed in the same manner as in the fourth step of Example 1 to obtain the embodiment shown in FIG.
[0067]
[Fourth Step << First Plating Step >>]
Electroless copper plating was applied to the substrate 1 after removing the covering material in the same manner as in Example 1.
Further, in the same manner as in Example 1, after electroless copper plating, electrolytic copper plating was performed.
In either case, as shown in FIG. 2D, the copper plating 2 was applied only to the surface to which the plating catalyst 11 was applied.
[0068]
[Fifth step << second covering step >>]
As shown in FIG. 2 (E), using the same resin as in the first step, as shown in FIG. 2 (E), a portion where plating 2 is applied (plating portion) and a portion where plating is not performed (non-plating portion) ), A second coating 4 having a thickness of 0.5 mm, a width of 0.2 to 0.4 mm, and an interval of 0.1 mm was obtained.
[0069]
[Sixth step << second plating catalyst application step}
As shown in FIG. 2 (F), the same catalyst as the first plating catalyst in the second step is applied to the non-coated surface (exposed surface) of the substrate 1 as shown in FIG. Catalyst 12 was applied.
[0070]
[Seventh Step << Second Coating Material Removal Step]
In the same manner as in the third step, the second covering material 4 was removed to obtain the embodiment of FIG.
[0071]
[Eighth process << second plating process >>
The same plating material as in the fourth step was subjected to the second plating in the same manner as in the fourth step.
The second plating 5 is applied over the first plating 2 and over the second plating catalyst 12 applied in contact with the first plating 2, as shown in FIG. The product of the aspect shown to this was obtained.
The plating 5 had a width of 0.2 to 0.3 mm, an interval of 0.1 to 0.05 mm, and a thickness of 0.5 to 5.0 μm.
[0072]
Example 4
A hydrolyzable polymer material was used as the first and second coating materials, and the same procedures as in Example 3 were performed along the steps of FIGS.
[Pretreatment process]
In the same manner as in Example 3, the same substrate 1 as in Example 1 was molded and roughened.
[0073]
[First step << first covering step >>]
The substrate 1 after the roughening is set, and the water as the coating material 3 heated to 150 to 260 ° C. (190 ° C. in this example) is placed in a secondary mold held at 5 to 30 ° C. (10 ° C. in this example). Decomposable polymer material (polylactic acid resin (using the trade name “LACEA” manufactured by Mitsui Chemicals, Inc.)), injection pressure 200 to 1200 kg / cm²(In this example, 350 kg / cm²) To obtain a partial coating 3 having a thickness of 0.5 mm, a width of 0.2 mm, and an interval of 0.2 mm as shown in FIG.
[0074]
[Second step << first plating catalyst application step}
In the same manner as in the second step of Example 3, the first plating catalyst 11 similar to that of Example 3 was applied to the uncoated surface (exposed surface) of the substrate 1 as shown in FIG. .
[0075]
[Third step << first covering material removing step]
In the same manner as in the third step of Example 3, the first covering material 3 was removed.
[0076]
[Fourth Step << First Plating Step >>]
In the same manner as in the fourth step of Example 3, electroless copper plating was performed.
Further, in the same manner as in the fourth step of Example 3, after electroless copper plating, electrolytic copper plating was performed.
In either case, as shown in FIG. 2D, the copper plating 2 was applied only to the surface to which the plating catalyst 11 was applied.
[0077]
[Fifth step << second covering step >>]
As shown in FIG. 2 (E), using the same resin as in the first step, as shown in FIG. 2 (E), a portion where plating 2 is applied (plating portion) and a portion where plating is not performed (non-plating portion) ), A second coating 4 having a thickness of 0.5 mm, a width of 0.2 to 0.3 mm, and an interval of 0.1 mm was obtained.
[0078]
[Sixth step << second plating catalyst application step}
As shown in FIG. 2 (F), the same catalyst as the first plating catalyst in the second step is applied to the non-coated surface (exposed surface) of the substrate 1 as shown in FIG. Catalyst 12 was applied.
[0079]
[Seventh Step << Second Coating Material Removal Step]
In the same manner as in the third step, the second covering material 4 was removed to obtain the embodiment of FIG.
[0080]
[Eighth process << second plating process >>
The same plating material as in the fourth step was subjected to the second plating in the same manner as in the fourth step.
The second plating 5 is applied over the first plating 2 and over the second plating catalyst 12 applied in contact with the first plating 2, as shown in FIG. The product of the aspect shown to this was obtained.
The plating 5 had a width of 0.2 to 0.3 mm, an interval of 0.1 to 0.05 mm, and a thickness of 0.5 to 5.0 μm.
[0081]
【The invention's effect】
According to the method of the present invention (first and second inventions), the plating with a fine pattern can be performed with extremely high accuracy.
[0082]
If a water-soluble polymer material or a hydrolyzable polymer material is used as the coating material at this time, the coating material is removed without using an organic solvent, and water is used in the water-soluble polymer material. In the case of a hydrolyzable polymer material, an alkaline aqueous solution or an acid solution can be used.
If biodegradable materials are used as these polymer materials, they are easily decomposed into water and carbon dioxide by microorganisms in the soil and water, so there is no concern about environmental problems, and disposal after removal from the substrate is possible. It is extremely simple.
[0083]
In addition, water-soluble polymer materials or hydrolyzable polymer materials are more transferable when molded by injection (molded according to the shape of the mold) than plastics and rubber that have been used as this type of coating material. In addition, the solidification rate is slow and the interfacial adhesion to the substrate (generally using a material different from the coating material) increases, enabling fine plating with high dimensional accuracy and high-quality fines. A plated product can be obtained.
[0084]
Moreover, since this water-soluble polymer material or hydrolyzable polymer material is finally removed from the plated product, the coating shape by these polymer materials is not affected by the shape or dimensions of the final product, It can be designed exclusively for the plating operation and contributes to the reduction of the thickness and thickness of the final product. That is, since the shape and dimensions of the final product are not restricted by the shape and dimensions of the coating material during the plating process, the substrate can be freely coated, thereby forming circuit electrodes in a three-dimensional pattern on the substrate. Therefore, the degree of freedom in designing circuit electrodes and, in turn, various electronic / electrical parts equipped with the circuit electrodes is increased, and the electronic parts / electrical parts can be further reduced in size and weight.
[0085]
Furthermore, in the present invention, since the catalyst for plating does not remain in the unplated portion, the electrical surface resistance value after circuit forming after the plating is increased, and the electrical characteristics of the product are improved. Can be made.
[0086]
According to the present invention, the conventional resist coating / curing / removing step can be omitted, and therefore there is no concern about environmental problems due to the organic solvent, and the step can be shortened.
In addition, it is possible to provide high-quality electronic / electrical parts with high dimensional accuracy and high electrical surface resistance.
[Brief description of the drawings]
FIG. 1 is a diagram for explaining an embodiment of the method of the first invention in the order of steps.
FIG. 2 is a diagram for explaining an embodiment of the method of the second invention in the order of steps.
[Explanation of symbols]
1 Base
2 plating
3 First covering material
4 Second covering material

Claims (3)

(1) a step of plating the surface of the substrate;
(2) A step of applying a first coating that is a water-soluble polymer material or a hydrolyzable polymer material by an injection molding method in which the substrate is a part of the mold partially in an appropriate pattern on the plated portion;
(3) a step of removing plating in a portion other than the first covering portion;
(4) a step of removing the first covering material;
(5) A second water-soluble polymer material or a hydrolyzable polymer material is formed by an injection molding method in which the base is part of the mold, partially in an appropriate pattern over the plating removal portion and the plating remaining portion. Applying a coating;
(6) a step of removing plating on portions other than the second covering portion;
(7) removing the second covering material;
A fine plating method characterized by passing through in this order. (1) A step of applying a first coating that is a water-soluble polymer material or a hydrolyzable polymer material by an injection molding method in which the surface of the substrate is partly in an appropriate pattern and the substrate is a part of a mold,
(2) a step of applying a first plating catalyst to a portion other than the first covering portion;
(3) removing the first covering material;
(4) applying the first plating;
(5) The second coating which is a water-soluble polymer material or a hydrolyzable polymer material by an injection molding method in which the base is part of the mold partly in an appropriate pattern over the non-plated part and the plated part. The process of applying,
(6) A step of applying a second plating catalyst to a portion other than the second covering portion,
(7) removing the second covering material;
(8) applying a second plating;
A fine plating method characterized by passing through in this order. The fine plating method according to claim 2, wherein the steps (5) to (8) are further added a plurality of times.

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