JP4118589B2

JP4118589B2 - Composite structure of resin and brittle material and manufacturing method thereof

Info

Publication number: JP4118589B2
Application number: JP2002108800A
Authority: JP
Inventors: 純明渡; 広典鳩野; 正勝清原; 達郎横山; 朋和伊藤; 勝彦森; 篤史吉田
Original assignee: Toto Ltd; National Institute of Advanced Industrial Science and Technology AIST
Current assignee: Toto Ltd; National Institute of Advanced Industrial Science and Technology AIST
Priority date: 2001-04-12
Filing date: 2002-04-11
Publication date: 2008-07-16
Anticipated expiration: 2022-04-11
Also published as: JP2003034003A

Description

【０００１】
【発明の属する技術分野】
本発明は、樹脂基材表面にセラミックスや半金属などの脆性材料からなる構造物を形成した複合構造物およびその作製方法に関する。
【０００２】
【従来の技術】
基材表面に金属やセラミックスなどの被膜を形成する方法として、ゾルゲル法、ＰＶＤやＣＶＤなどの蒸着法あるいは溶射法が知られている。
【０００３】
また、最近では新たな被膜形成方法として、ガスデポジション法（加集誠一郎：金属１９８９年１月号）や静電微粒子コーティング法（井川他：昭和５２年度精密機械学会秋季大会学術講演会前刷）が知られている。前者は金属やセラミックス等の超微粒子をガス攪拌にてエアロゾル化し、微小なノズルを通して加速せしめ、基材に衝突した際に運動エネルギーの一部が熱エネルギーに変換され、微粒子間あるいは微粒子と基材間を焼結することを基本原理としており、後者は微粒子を帯電させ電場勾配を用いて加速せしめ、この後はガスデポジション法と同様に衝突の際に発生する熱エネルギーを利用して焼結することを基本原理としている。
【０００４】
また、上記のガスデポジション法あるいは静電微粒子コーティング法を改良した先行技術として、特開平８−８１７７４号公報、特開平１０−２０２１７１号公報、特開平１１−２１６７７号公報、特開平１１−３３０５７７号公報或いは特開２０００−２１２７６６号公報に開示されるものが知られている。
【０００５】
【発明が解決しようとする課題】
上記した先行技術の多くは、被膜形成に樹脂が溶融あるいはガス化する程度の加熱を伴うため、樹脂基板の表面に脆性材料構造物を形成するには適さない。
また、上記した先行技術のうち、ガスデポジション法を改良したものの中には、加熱工程を伴わずに被膜を形成するものもあるが、脆性材料微粒子を樹脂基板に直接衝突させると、樹脂基板は一般的に無機材料に代表される脆性材料と比較して弾性に富み、また柔らかいために下記２つの不具合を生じる場合があった。
（１）不飽和ポリエステル、ナイロン、ゴム、フッ素樹脂等のように、弾性に富む場合には脆性材料微粒子が跳ね返されてうまく製膜できない。
（２）アクリル樹脂、エポキシ樹脂等のように、樹脂材料の中では比較的硬く塑性に乏しい場合には強く衝突させると樹脂基板が削られてしまう。
またポリカーボネートやポリプロピレンなどへの製膜も困難である。
【０００６】
そこで、本発明者らは樹脂基板の表面にも脆性材料構造物を形成できる方法を、国際出願（ＰＣＴＪＰ００／０７０７６）した。この発明は以下の知見に基づいてなされた。
即ち、延展性を持たない脆性材料（セラミックス）に機械的衝撃力を付加すると、結晶子同士の界面などの劈開面に沿って結晶格子のずれを生じたり、あるいは破砕される。そして、これらの現象が起こると、ずれ面や破面には、もともと内部に存在し別の原子と結合していた原子が剥き出しの状態となった新生面が形成される。この新生面の原子一層の部分は、もともと安定した原子結合状態から外力により強制的に不安定な表面状態に晒され、表面エネルギーが高い状態となる。この活性面が隣接した脆性材料表面や同じく隣接した脆性材料の新生面あるいは基板表面と接合して安定状態に移行する。外部からの連続した機械的衝撃力の付加は、この現象を継続的に発生させ、微粒子の変形、破砕などの繰り返しにより接合の進展、緻密化が行われ、脆性材料構造物が形成される。
そして、更に上記機械的衝撃を搬送ガスにて脆性材料を基材に衝突させるようにした本発明の一態様を以後、微粒子ビーム堆積法と称する。またこの方法はエアロゾルデポジション法とも呼ばれる。
【０００７】
上記の微粒子ビーム堆積法によって作製した脆性材料構造物の断面を観察したところ、噴射された微粒子または破砕した微細断片粒子が基材に突き刺さったアンカー部が存在し、その上に破砕・変形した脆性材料微粒子同士が、焼成することもなく緻密に接合して形成される構造となっていることがわかった。即ち、微粒子ビーム堆積法によってうまく脆性材料構造物が形成されるか否かは基材表面にアンカー部が存在しているか否かに大きく依存しており、一度薄いアンカー部が形成された後は、比較的容易にその上に脆性材料構造物が形成される。
【０００８】
そして、上記アンカー部は、一般的に弾性係数が高いか、また樹脂の中では比較的硬くかつ塑性に乏しい樹脂基材上に直接脆性材料構造物を形成しようとすると脆性材料微粒子が樹脂基材に弾かれたり、脆性材料微粒子により樹脂基材が削られたりしてうまく形成できないが、このような樹脂基材に対しては加熱等の手段で樹脂基材表面を塑性流動可能な状態まで柔らかくしておき、この状態で硬質粒子を打ち込む等すれば、下地層が形成されるという知見を得て本発明を成したものである。
【０００９】
即ち、本発明の第１の態様に属する樹脂と脆性材料との複合構造物は、樹脂基材表面にその一部が食い込む硬質材料からなる下地層が形成され、この下地層の上に多結晶で且つ実質的に結晶配向性がなく更に結晶同士の界面にガラス層からなる粒界層が実質的に存在しない脆性材料構造物が形成された構成である。
【００１０】
また、下地層と脆性材料構造物とは同一材料で構成してもよいし、異なる材料で構成してもよい。例えば、下地層を構成する硬質粒子の出発原料として内部歪の小さいものを選定することで、基材に衝突した際に破砕されにくく、大きな粒子のまま基材に食い込む。尚、下地層の厚さは１００ｎｍ以上が好ましい。
【００１１】
上記の複合構造物を作製するには、樹脂基材表面にこの樹脂基材よりも高硬度の粒子を食い込ませて下地層を形成し、次いでこの下地層に脆性材料微粒子を高速で衝突させ、この衝突の衝撃によって前記脆性材料微粒子を変形または破砕し、この変形または破砕にて生じた活性な新生面を介して微粒子同士を再結合せしめることで、下地層の上に多結晶の脆性材料構造物を形成する。
【００１２】
前記下地層を形成する手段としては、加圧または衝突による衝撃を高硬度粒子に加えることが考えられ、特に衝突による衝撃で下地層を形成する場合には、樹脂基材が削れてしまうのを防止するため硬質粒子の衝突速度を５０m/s以下とすることが好ましい。
【００１３】
また、樹脂基材が熱可塑性樹脂からなる場合には、この熱可塑性樹脂のガラス転移温度（Ｔg）以上に加熱して樹脂基材を軟化せしめ、この軟化した樹脂基材表面に硬質材料粒子を食い込ませて下地層を形成する。なお、脆性材料構造物の形成工程の温度は、前記熱可塑性樹脂のガラス転移温度（Ｔg）以下にするのが好ましい。
下地層を形成する際の温度の上限は樹脂基材があまり柔らかくなると硬質樹脂が完全に樹脂基材に埋没してしまうので、このような状態にならない温度範囲とする。
【００１４】
一方、樹脂基材が熱硬化性樹脂からなる場合には、この熱硬化性樹脂の前駆体を半硬化状態になるまで加熱し、この半硬化状態にある基材表面に硬質材料粒子を食い込ませて下地層を形成する。なお、脆性材料構造物の形成工程は、熱硬化性樹脂が硬化した後に、常温または加熱状態で形成する。
【００１５】
また、本発明の第２の態様に属する樹脂と脆性材料との複合構造物は、樹脂基材の表面に延性材料からなる下地層が形成され、この下地層の上に多結晶で且つ実質的に結晶配向性がなく更に結晶同士の界面にガラス層からなる粒界層が実質的に存在しない脆性材料構造物が形成された構成とした。
【００１６】
第２の態様に属する複合構造物を作製するには、樹脂基材表面にめっき、蒸着あるいは塗布にて延性材料からなる下地層を形成し、次いでこの下地層に脆性材料微粒子を高速で衝突させ、この衝突の衝撃によって前記脆性材料微粒子を変形または破砕し、この変形または破砕にて生じた活性な新生面を介して微粒子同士を再結合せしめることで、下地層の上に多結晶の脆性材料構造物を形成する。
【００１７】
ここで、本発明を理解する上で重要となる語句の解釈を以下に行う。
（下地層）
樹脂基材の最表面に無機材料や金属材料が接合された薄い層であり、基材との密着性を保つとともに、その上に脆性材料構造物を微粒子ビーム堆積法により形成した場合に、この構造物と強固に接合される層を指す。基材との接合はその一部が基材に食い込むようになっているのが望ましい。また、脆性材料構造物との接合は、脆性材料構造物粒子が衝突した際に、その一部が食い込んでアンカー部を形成するか、若しくは脆性材料構造物粒子の衝突によりその一部が破砕または変形されて新生面が形成される材料からなるのが望ましい。それら条件を満足する材料は、硬質材料であり、アンカー部を形成しやすいという観点では金属材料が、新生面を形成しやすいという観点では金属酸化物等の無機材料が好適に利用できる。この層は微粒子ビーム堆積法により形成させることができるが、めっき、ＰＶＤ、ＣＶＤその他の手法を用いてもよい。
（多結晶）
本件では結晶子が接合・集積してなる構造体を指す。結晶子は実質的にそれひとつで結晶を構成しその径は通常５ｎｍ以上である。ただし、微粒子が破砕されずに構造物中に取り込まれるなどの場合がまれに生じるが、実質的には多結晶である。
（結晶配向性）
本件では多結晶である構造物中での結晶軸の配向具合を指し、配向性があるかないかは、一般には実質的に配向性のないと考えられる粉末X線回折などによって標準データとされたJCPDS（ASTM）データを指標として判断する。
構造物層中の脆性材料結晶を構成する物質をあげたこの指標における主要な回折３ピークのピーク強度を１００％として、構造物層の同物質測定データ中、最も主要なピークのピーク強度をこれに揃えた場合に、他の２ピークのピーク強度が指標の値と比較して３０％以内にそのずれが収まっている状態を、本件では実質的に配向性がないと称する。
（界面）
本件では結晶子同士の境界を構成する領域を指す。
（粒界層）
界面あるいは焼結体でいう粒界に位置するある厚み（通常数ｎｍ〜数μｍ）を持つ層で、通常結晶粒内の結晶構造とは異なるアモルファス構造をとり、また場合によっては不純物の偏析を伴う。
（内部歪）
微粒子に含まれる格子歪のことで、Ｘ線回折測定におけるHall法を用いて算出される値であり、微粒子を十分にアニールした標準物質を基準として、そのずれを百分率表示する。
【００１８】
【発明の実施の態様】
以下に本発明の実施の形態を添付図面に基づいて説明する。ここで、図１〜図３は本発明に係る樹脂と脆性材料との複合構造物の第１の態様の拡大断面図、図４は第２の態様を示す拡大断面図である。
【００１９】
図１に示す複合構造物は、下地層と脆性材料構造物が同質で一体となっている。この場合は、軟化状態にある樹脂基材（熱可塑性樹脂の場合は、ガラス転移温度以上、熱硬化性樹脂の場合は前駆体が半硬化の状態にある温度）に、微粒子ビーム堆積法により硬質粒子（脆性材料微粒子）を用いて基材の一部に上記硬質粒子が食い込むように打ち込んで下地層を形成した後、樹脂を硬化させ、次いで、下地層の上に微粒子ビーム堆積法により脆性材料構造物を形成した場合などにあたる。
いずれも、粒子の破壊・変形などが起こっている。図中の粒状のイメージは、形成された脆性材料構造物の結晶粒を示し、これらはお互いに強固に結合している。
【００２０】
図２に示す複合構造物は、下地層と構造物が異質であることにより明確に下地層と脆性材料構造物とが分離して認識できる（境界部が認識できる）。この場合は、軟化状態にある樹脂基材に、微粒子ビーム堆積法により硬質粒子を用いて基材の一部に上記硬質粒子が食い込むように打ち込んだ下地層を形成した後、樹脂を硬化させ、次いで、下地層の上に微粒子ビーム堆積法により脆性材料構造物を形成した場合になどにあたる。下地層の材料は脆性材料や金属材料が考えられ、その粒径などはその上に形成する脆性材料構造物と同じでなくとも良い。
【００２１】
図３に示す複合構造物は、下地層と構造物が同質であるが、下地層を構成する粒子の大きさが構造物の粒子の大きさよりも大きい場合である。このように大きな粒子を基材に食い込ませることで、質量効果により基材に対してしっかり密着する。
【００２２】
図４に示す複合構造物は、基材の上に下地層として延性材料層が存在し、この上に脆性材料構造物が形成されている場合である。この場合は、あらかじめ樹脂基材にめっきやＰＶＤなどにより金属などの延性材料層を形成した後、微粒子ビーム堆積法によりある種の脆性材料微粒子を打ち込む。
【００２３】
次に、構造物の作製の方法に関する実施の態様を述べる。
熱可塑性樹脂基材上における脆性材料構造物の作製方法について説明する。熱可塑性樹脂材料に脆性材料を形成させる微粒子ビーム堆積装置図を図５に示す。装置の構成としては、熱可塑性樹脂材料をガラス転移温度（Ｔｇ）以上融点以下に温度制御できる加熱冷却プレート１、基材温度を測定する温度計２、基材温度を制御する温調器３、原料粉体である脆性材料微粒子を振動・攪拌する原料槽４、キャリアガスを貯留するキャリアガス貯留槽５、原料槽４とキャリアガス貯留槽５とを連結する連結管６、脆性材料微粒子をキャリアガス貯留槽５のキャリアガスによって樹脂基材７の表面に噴射させるための噴射管８、さらに、下地層を形成した樹脂基材を強制的に空冷によって冷却する噴射ノズル９により構成されている。
【００２４】
動作は、基材７を噴射管８の噴射口の先方にセットし、基材温度を制御する温調器３を用いて、基材７のガラス転移温度（Ｔｇ）以上融点以下の温度にセットする。基材表面の温度は基材に設置された温度計２によって測温され、温調器３によって制御される。基材７の温度が所定の温度に達した時点で、キャリアガス貯留槽５のバルブ１０を開き、キャリアガス貯留槽５内のキャリアガスを流し、原料槽４内にある脆性材料微粒子をキャリアガスと共に噴射管８を通って噴射口から噴出し、所定温度に制御された基材７の表面に衝突させる。
【００２５】
この際、基材表面の温度は樹脂基材のガラス転移温度以上かつ融点以下に制御されているので軟化した状態であり、噴射口から噴射された脆性材料微粒子は、基材表面に突き刺さり基材表面に下地層を形成する。このとき基材が軟らかいため脆性材料微粒子は変形されずに基板が変形するアンカーとなる。
【００２６】
下地層が形成された状態で、温調器３を用いて基材７の温度を水冷や空冷でガラス転移温度以下に下げ、基材の表面を硬化させると、樹脂基材表面には脆性材料微粒子が食い込んだ下地層が形成される。基材表面の硬化するスピードを促すために、別に設けた空冷用ノズル９からガスを吹き付ければさらに硬化スピードが増し効率的である。
【００２７】
この工程を経たのち、噴射口８から再び脆性材料微粒子を下地層に向けて高速で噴射させることにより、次には脆性材料微粒子が下地層に衝突して変形あるいは破砕を起こし、変形した活性な粒子や活性な表面を持つ破砕断片粒子が再接合することにより下地層から成長するようにして脆性材料の構造物が形成される。
【００２８】
上記した樹脂基材への脆性材料構造物の作製方法は、下地層形成工程から脆性材料構造物の形成工程までを連続的に行った例であるが、基本的に、下地層を形成した樹脂基材が十分に冷えてから、構造物形成工程を行うといった断続的製法にても樹脂基材上への脆性材料構造物は可能である。
【００２９】
この実施の態様に示した熱可塑性樹脂材料としては、ＡＢＳ、アセタール樹脂、メタクリル樹脂、酢酸セルロース、塩素化ポリエーテル、エチレン−酢酸ビニル共重合体、フッ素樹脂、アイオノマー、メチルペンテンポリマー、ナイロン、ポリカーボネート、ポリエチレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリイミド、ポリフェニレンオキサイド、ポリフェニレンスルフィド、ポリアクリレート、ポリプロピレン、ポリスチレン、ポリスルホン、酢酸ビニル樹脂、塩化ビニリデン樹脂、ＡＳ樹脂，塩化ビニル樹脂等が、脆性材料としては、Ａｌ₂Ｏ₃，ＮｉＯ，ＴｉＯ₂，ＣｕＯ，ＺｎＯ，ＺｒＯ₂，ＳｎＯ₂，ＭｇＯなどの酸化物，ＷＣ，ダイヤモンド，ＳｉＣ，Ｂ₄Ｃ等の炭化物，ＡｌＮ，Ｓｉ₃Ｎ₄等の窒化物，Ｃａ₂Ｆ，ＺｒＦ等のフッ化物などに代表される脆性材料を用い、搬送用キャリアガスとしては、乾燥空気、窒素、ヘリウム、アルゴン、酸素、水素、酸素分圧を制御した混合ガスなどを用いることができる。
【００３０】
ここで、下地層の形成工程についてであるが、上述の様に微粒子ビーム堆積法の応用により作成することは有用である。下地層の材質は脆性材料構造物の材質と必ずしも同じでなくとも良く、無機材料に限らず、金属材料でも良い。微粒子ビーム堆積法による脆性材料構造物形成は金属、無機材料上には非常に良好に適用できるからである。従って金属の場合は、これらの微粒子、たとえばＡｌ，Ｃｕ，Ｎｉ，Ｔｉ，Ｐｔ，Ａｕ，Ａｇ，Ｓｉ等を同じようにしてノズルより噴射させて、基材に食い込んで密着性を向上させた下地層となる。この後に脆性材料微粒子をノズルより噴射させて金属下地層に脆性材料微粒子が食い込むアンカー部を形成させ、さらにこの上に構造物を成長させていく。
【００３１】
さらに，樹脂基材へ下地層を形成する方法としては，高温まで加熱を必要としないようなＣＶＤ法，ＰＶＤ法，ゾルゲル法さらにメッキ法も有効である。
【００３２】
次に、熱硬化性樹脂基材上における脆性材料構造物の作製方法について説明する。熱硬化性樹脂材料上に脆性材料構造物を形成する微粒子ビーム堆積装置図を図６に示す。
装置の構成としては、練り合わせた熱硬化性樹脂材料を硬化温度より１０℃低い温度以上硬化温度以下に制御できるような加熱プレート１１、基材温度を測定する温度計１２、基材温度を制御する温調器１３、原料粉体である脆性材料微粒子を振動・攪拌する原料槽１４、キャリアガスを貯留するキャリアガス貯留槽１５、原料槽１４とキャリアガス貯留槽１５とを連結する連結管１６、脆性材料微粒子をキャリアガス貯留槽１５のキャリアガスによって樹脂基材１７の表面に噴射させるための噴射管１８、さらに、下地層を形成した樹脂基材を強制的に空冷によって冷却する噴射ノズル１９により構成されている。
【００３３】
動作は、練り合わせた熱硬化性樹脂基材１７を噴射管１８の噴射口の先方にセットし、基材温度を制御する温調器１３を用いて、基材１７を基材硬化温度より１０℃低い温度以上硬化温度以下にセットする。基材表面の温度は基材に設置された温度計１２によって測温され、温調器１３によって制御される。基材１７の温度が所定の温度に達した時点で、キャリアガス貯留槽１５のバルブ２０を開き、キャリアガス貯留槽１５内のキャリアガスを流し、原料槽１４内にある脆性材料微粒子をキャリアガスと共に噴射管１８を通って噴射口から噴出し、所定温度に制御された基材１７の表面に衝突させる。
【００３４】
この際、基材表面の温度は樹脂材が硬化する温度以下に制御されているので硬化が完全には達成されていない軟らかい状態であるために、噴射口から噴射された脆性材料微粒子は、基材表面に突き刺さり基材表面に下地層が容易に形成される。下地層が形成された状態で、温調器１３を用いて基材１７の温度を基材の硬化温度以上に上げ硬化させると、樹脂基材表面には脆性材料微粒子が食い込んだ下地層の形成工程が完了する。
【００３５】
この工程を経た後、噴射口１８から再び脆性材料微粒子を下地層に向けて高速で噴射させることにより、次には脆性材料微粒子が下地層に衝突して変形あるいは破砕を起こし、変形した活性な粒子や活性な表面を持つ破砕断片粒子が再接合することにより下地層から成長するようにして脆性材料の構造物が形成される。上記に記した樹脂基材への脆性材料構造物の作製方法では、下地層形成工程から脆性材料構造物の形成工程までを連続的に行った例であるが、基本的に、下地層を形成した樹脂基材が十分に冷えてから、形成工程を行うといった断続的製法にても樹脂基材上への脆性材料構造物の形成は可能である。
【００３６】
この実施の態様に示した熱硬化性樹脂材料としては、アルキド樹脂、アリル樹脂、アミノ樹脂、メラミン樹脂、エポキシ樹脂，ユリア樹脂，フェノール樹脂、不飽和ポリエステル樹脂、シリコーン樹脂、ポリウレタン等が使用される。下地層の材質、脆性材料構造物の材質は前述した実施の態様と同じものが適用できる。
【００３７】
次にキャリアガス流速を制御して樹脂基材上における脆性材料構造物を作製する方法について説明する。キャリアガス流速を制御して樹脂材料に脆性材料構造物を形成する微粒子ビーム堆積装置図を図７に示す。
装置の構成としては、基材固定プレート２１、原料粉体である脆性材料微粒子を振動・攪拌する原料槽２４、キャリアガスを貯留するキャリアガス貯留槽２５、原料槽２４とキャリアガス貯留槽２５とを連結する連結管２６、原料槽２４の脆性材料微粒子をキャリアガス貯留槽２５のキャリアガスによって樹脂基材２７の表面に噴射させるための噴射管２８、さらに、下地層を形成するための脆性材料微粒子を振動・攪拌する原料槽２９、キャリアガスを貯留するキャリアガス貯留槽３０、原料槽２９とキャリアガス貯留槽３０とを連結する連結管３１、噴射口３２により構成されている。
【００３８】
動作は、基材２７を噴射口３２、噴射管２８の噴射口の前方にセットし、まず、キャリアガス貯留槽３０のバルブ３３、３４を開き、キャリアガス貯留槽３０内のキャリアガスを流し、原料槽２９内にある脆性材料微粒子をキャリアガスと共に噴射管を通って噴射口３２から噴出し、５０ｍ／ｓ以下のゆっくりした微粒子速度にて基材２７の表面に衝突させる。これにより、樹脂基材上を削ることなく、表層部には脆性材料微粒子が突き刺さった下地層を形成することができる。下地層形成が終了後、キャリアガス貯留槽３０のバルブ３３、３４を閉じ、キャリアガス貯留槽３０内のキャリアガスを止める。次に、キャリアガス貯留槽２５のバルブ３５、３６を開き、キャリアガス貯留槽２５内のキャリアガスを流し、原料槽２４内にある脆性材料微粒子をキャリアガスと共に噴射管２８を通って噴射口から噴出し、下地層が形成された樹脂基材２７の表面に衝突させ、破砕・変形が生じた脆性材料微粒子は、活性が高く、粒子が持っている運動エネルギーレベルで、瞬時に脆性材料同士の結合を起こし、下地層を形成した樹脂基材上に脆性材料構造物が形成される。
【００３９】
上記に記した樹脂基材への脆性材料構造物の作製方法では、下地層形成工程と脆性材料構造物の形成工程までを２つの噴射口を用いて行った例であるが、この方法を用いれば、下地層形成の材料とその上に形成する脆性材料構造物の組成や材質を変えることや、原料粉体である脆性材料微粒子の粒径を変えることによって、より効率的に複合構造物を形成することが可能になる。
【００４０】
樹脂上に形成する脆性材料構造物は、ガス流量を制御することによって、基本的には、１つの噴射口を用いて下地層形成工程、構造物形成工程を行うといった連続的製造も可能である。
樹脂材料としては、熱可塑性樹脂材料、熱硬化性樹脂材料のどちらでも適応できる。下地層、脆性材料構造物の材質も前述のものが同様に適用できる。
【００４１】
更に、本発明者らは同じ粒径の脆性材料を用いた場合でも、形成される構造物の形成速度、達成膜厚に相違があり、これは粒子の内部歪に起因するとの結論を得た。
そこで、内部歪と同一の形成時間で達成された構造物の膜厚の関係について実験した結果を図８に示す。実験は、純度９９.６％の酸化アルミニウム微粒子に遊星ミルを用いて粉砕処理を行い、微粒子のキャラクタリゼーションを変化させた後、超微粒子ビーム堆積法によりアルミニウム基板上に構造物を形成した。微粒子の内部歪はＸ線回折により測定し、歪量は同微粒子に熱エージングを施して内部歪を除去したものを０％として基準にした。
また、図８中のポイントＡ，Ｂ，Ｃにおける微粒子のＳＥＭ写真（日立製インレンズＳＥＭＳ−５０００）を図９、図１０及び図１１に示す。
【００４２】
図８から１μｍの膜厚を得るには０.０１〜２.５０％の内部歪があれば十分であることが分るが、安定した膜厚を得るには０.１〜２.０％の内部歪が好ましい。クラックと内部歪との関係は、内部歪がない場合には図９に示すようにクラックは発生しないが、内部歪が一定値以上、本件の場合には２．０％以上となると完全にクラックが形成されてしまい、さらには脱落した断片が表面に付着して図１１に示すような再凝集状態となってしまう。
【００４３】
このように微粒子に歪を与える粉砕処理は、微粒子にかかる粉砕のための衝撃を大きく与えることのできる粉砕手段を用いるのが好ましい。微粒子に比較的一様に大きな歪を付与することができるからである。このような粉砕手段としては、セラミックスの粉砕処理によく用いられるボールミルに比べて大きな重力加速度を与えることの出来る振動ミルやアトライタ、遊星ミルを用いるのが好ましく、とりわけボールミルに比べて格段に大きな重力加速度を与えることの出来る遊星ミルを用いることが最も好ましい。微粒子の状態に着目すれば、クラックは内部歪をキャンセルするものであるので、最も好ましいのは、クラックが生じる直前まで内部歪が高まっている微粒子ということになる。図１０に示す状態は若干のクラックが生じているが、十分に内部歪が残されている。
【００４４】
微粒子ビーム堆積法を用いてプラスチック材料上へ実際に構造物形成を試みた例について以下に説明する。
（参考例）
参考例では、プラスチック基板上に微粒子ビーム堆積法にて純度９９％以上のサブミクロン粒径の酸化アルミニウム微粒子を吹き付けて構造物形成を試みた例である。基材としてＡＢＳ、ポリプロピレン、アクリル樹脂、ポリエチレンテレフタレート、ポリカーボネート、ポリスチレン、ポリイミド、エポキシ樹脂ARALDITE XD911を用いた。構造物形成装置は図６に準じるようなもので基板の加熱は行わない。従って基板を空冷するための噴射ノズルは保有していない。噴射管である微粒子を噴射するノズルは１７ｍｍ×０．４ｍｍの開口を持ち、ここから酸化アルミニウム微粒子を窒素ガスに混合させたエアロゾルを７Ｌ／ｍｉｎの流量で吹き付けた。また構造物形成を行うチャンバーは真空ポンプにて１ｋＰａ以下に調整した。面積１７ｍｍ×５ｍｍで形成を行い、時間は１０分とした。表１に構造物の形成の有無と形成された場合の膜厚を示す。膜厚の測定は日本真空技術株式会社製触針式表面形状測定器Ｄｅｋｔａｋ３０３０を用いた。
【００４５】
【表１】

【００４６】
（実施例１）
つぎに熱可塑性樹脂としてポリエチレンテレフタレート基板に、参考例で用いた酸化アルミニウム微粒子を用いて下地層を形成し、この上に構造物の形成を行った例について説明する。まず酸化アルミニウム微粒子をエタノールに分散させたスラリーをポリエチレンテレフタレート基板上に滴下して、乾燥させて基板上に微粒子の付着層を形成させた後、表面を押圧状態にして基材が軟らかくなる温度として１００℃１時間保持して微粒子を基板に食い込ませて、付着層を下地層として基板上に固定した。こののち基板に超音波洗浄を施して、固定化されなかった微粒子を除去した。次に参考例と同様の方法で微粒子ビーム堆積法にて構造物形成を行った。この結果下地層の上に５１．５μmの構造物の膜が形成された。参考例の場合と比較して構造物形成がなされたことがわかる。
【００４７】
（実施例２）
次に熱硬化性樹脂としてエポキシ樹脂ARALDITE XD911基板に、参考例で用いた酸化アルミニウム微粒子を用いて層を形成し、この上に構造物の形成を行った例について説明する。まずＳＵＳ３０４基材上に未硬化のエポキシ樹脂を流し込み表面をフラットにした上に、酸化アルミニウム微粒子をエタノールに分散させたスラリーを滴下して、室温にて乾燥させて基板上に微粒子の付着層を形成させた後、樹脂の硬化温度である１２０℃１時間の硬化処理を行い、付着層を下地層として基板上に固定した。こののち基板に超音波洗浄を施して、固定化されなかった微粒子を除去した。次に参考例と同様の方法で微粒子ビーム堆積法にて構造物形成を行った。この結果、膜厚が１μm程度の薄膜であったが、参考例で見られたような基板の削れは見られず、構造物が形成されることがわかった。
【００４８】
（実施例３）
次に樹脂基板表面に金属下地層を形成した後に構造物を形成した例について述べる。基材として構造物形成が達成されなかったポリカーボネート基板に銅、ニッケル、クロムの多層めっきを施し、これに参考例と同様の方法で微粒子ビーム堆積法にて構造物形成を行った。この結果下地層表面に膜厚４μmの構造物の形成が確認された。
【００４９】
【発明の効果】
以上に説明したように本発明によれば、従来では困難であった柔らかい樹脂基材表面への脆性材料構造物を下地層を介在させることで形成することができる。
【図面の簡単な説明】
【図１】本発明の第１の態様に係る樹脂と脆性材料との複合構造物の拡大断面図
【図２】別実施の態様を示す図１と同様の図
【図３】別実施の態様を示す図１と同様の図
【図４】本発明の第２の態様に属する複合構造物を示す図１と同様の図
【図５】本発明に係る樹脂と脆性材料との複合構造物の作製装置の概略図
【図６】作製装置の別実施の態様を示す概略図
【図７】作製装置の別実施の態様を示す概略図
【図８】脆性材料微粒子の内部歪と膜厚との関係を示すグラフ
【図９】図８のポイントＡにおける微粒子のＳＥＭ写真
【図１０】図８のポイントＢにおける微粒子のＳＥＭ写真
【図１１】図８のポイントＣにおける微粒子のＳＥＭ写真[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composite structure in which a structure made of a brittle material such as ceramics or a semimetal is formed on the surface of a resin substrate, and a method for manufacturing the same.
[0002]
[Prior art]
As a method for forming a film of metal or ceramic on the surface of the substrate, a sol-gel method, a vapor deposition method such as PVD or CVD, or a thermal spraying method is known.
[0003]
Recently, as new film formation methods, the gas deposition method (Seiichiro Kashu: Metals, January 1989 issue) and electrostatic fine particle coating method (Igawa et al .: Preprint of the academic conference of the Japan Society for Precision Machinery Fall 1977 )It has been known. In the former, ultrafine particles such as metals and ceramics are aerosolized by gas agitation and accelerated through a minute nozzle. When they collide with a substrate, part of the kinetic energy is converted into thermal energy, and between particles or between the particles and the substrate. The latter is based on the basic principle. The latter is charged with fine particles and accelerated using an electric field gradient. After that, similar to the gas deposition method, the latter is sintered using thermal energy generated at the time of collision. The basic principle is to do.
[0004]
Further, as prior arts improved from the above-described gas deposition method or electrostatic fine particle coating method, JP-A-8-81774, JP-A-10-202171, JP-A-11-21777, JP-A-11-330577 are disclosed. And those disclosed in Japanese Patent Application Laid-Open No. 2000-212766.
[0005]
[Problems to be solved by the invention]
Many of the above-described prior arts are not suitable for forming a brittle material structure on the surface of a resin substrate because the film formation involves heating to such an extent that the resin is melted or gasified.
Among the above-described prior arts, some of the improved gas deposition methods form a film without a heating step. However, when the brittle material fine particles directly collide with the resin substrate, the resin substrate In general, it is rich in elasticity compared to brittle materials typified by inorganic materials, and since it is soft, the following two problems may occur.
(1) When it is rich in elasticity, such as unsaturated polyester, nylon, rubber, fluororesin, etc., brittle material fine particles are rebounded and film formation cannot be performed well.
(2) If the resin material is relatively hard and poor in plasticity, such as an acrylic resin or an epoxy resin, the resin substrate will be scraped if it is strongly collided.
Also, it is difficult to form a film on polycarbonate or polypropylene.
[0006]
Therefore, the present inventors made an international application (PCT JP00 / 07076) for a method capable of forming a brittle material structure on the surface of a resin substrate. This invention was made based on the following findings.
That is, when a mechanical impact force is applied to a brittle material (ceramics) that does not have spreadability, the crystal lattice shifts along the cleaved surface such as the interface between crystallites or is crushed. When these phenomena occur, a new surface is formed on the slipping surface or fracture surface, in which atoms originally present inside and bonded to other atoms are exposed. The part of the atomic layer on the new surface is exposed to an unstable surface state by an external force from a stable atomic bond state, and the surface energy is high. The active surface joins the adjacent brittle material surface, the newly formed brittle material surface, or the substrate surface, and shifts to a stable state. The addition of a continuous mechanical impact force from the outside continuously generates this phenomenon, and the joining is progressed and densified by repeated deformation and crushing of fine particles, thereby forming a brittle material structure.
Further, an embodiment of the present invention in which the above-described mechanical impact is caused to cause the brittle material to collide with the substrate with the carrier gas is hereinafter referred to as a fine particle beam deposition method. This method is also called an aerosol deposition method.
[0007]
When the cross section of the brittle material structure prepared by the fine particle beam deposition method was observed, there was an anchor part where the injected fine particles or crushed fine fragment particles pierced the base material, and the brittleness that was crushed and deformed on it It was found that the material fine particles had a structure formed by closely bonding without firing. That is, whether or not a brittle material structure is successfully formed by the fine particle beam deposition method depends largely on whether or not the anchor portion exists on the surface of the substrate. Once the thin anchor portion is formed, A brittle material structure is formed on it relatively easily.
[0008]
The anchor portion generally has a high elastic modulus, and when an attempt is made to directly form a brittle material structure on a resin base material that is relatively hard and poor in plasticity, the brittle material fine particles are formed on the resin base material. The resin base material is scraped by the brittle material fine particles and cannot be formed well. However, such a resin base material is softened to a state where the resin base material can be plastically flowed by means such as heating. In addition, the present invention has been achieved by obtaining the knowledge that, if hard particles are implanted in this state, an underlayer is formed.
[0009]
That is, in the composite structure of the resin and the brittle material belonging to the first aspect of the present invention, a base layer made of a hard material partially digging into the resin base material surface is formed, and the polycrystalline layer is formed on the base layer. In addition, a brittle material structure having substantially no crystal orientation and having substantially no grain boundary layer composed of a glass layer at the interface between crystals is formed.
[0010]
Further, the underlayer and the brittle material structure may be made of the same material or different materials. For example, by selecting a material having a small internal strain as a starting material for the hard particles constituting the base layer, it is difficult to be crushed when it collides with the base material, and bites into the base material as a large particle. Note that the thickness of the underlayer is preferably 100 nm or more.
[0011]
In order to produce the above composite structure, particles having a hardness higher than that of the resin substrate are formed on the resin substrate surface to form a foundation layer, and then the brittle material fine particles collide with the foundation layer at a high speed. The brittle material fine particles are deformed or crushed by the impact of the collision, and the fine particles are recombined with each other through the active new surface generated by the deformation or crushing, so that the polycrystalline brittle material structure is formed on the underlying layer. Form.
[0012]
As a means for forming the underlayer, it is conceivable to apply impact due to pressurization or collision to the high-hardness particles. In particular, when the underlayer is formed by impact due to collision, the resin base material may be scraped. In order to prevent this, the collision speed of the hard particles is preferably 50 m / s or less.
[0013]
When the resin base material is made of a thermoplastic resin, the resin base material is softened by heating to a temperature higher than the glass transition temperature (Tg) of the thermoplastic resin, and hard material particles are applied to the surface of the softened resin base material. A base layer is formed by biting. In addition, it is preferable that the temperature of the formation process of a brittle material structure shall be below the glass transition temperature (Tg) of the said thermoplastic resin.
The upper limit of the temperature when forming the base layer is set to a temperature range in which such a state is not caused because the hard resin is completely buried in the resin substrate when the resin substrate becomes too soft.
[0014]
On the other hand, when the resin substrate is made of a thermosetting resin, the precursor of the thermosetting resin is heated until it is in a semi-cured state, and the hard material particles are digged into the surface of the substrate in the semi-cured state. To form an underlayer. In addition, the formation process of a brittle material structure is formed at room temperature or in a heated state after the thermosetting resin is cured.
[0015]
In the composite structure of the resin and the brittle material belonging to the second aspect of the present invention, a base layer made of a ductile material is formed on the surface of the resin base material, and is polycrystalline and substantially on the base layer. In this structure, a brittle material structure having no crystal orientation and having substantially no grain boundary layer composed of a glass layer at the interface between crystals is formed.
[0016]
In order to produce the composite structure belonging to the second aspect, a base layer made of a ductile material is formed on the surface of the resin base material by plating, vapor deposition or coating, and then brittle material fine particles collide with the base layer at a high speed. The brittle material fine particles are deformed or crushed by the impact of the collision, and the fine brittle material structure is formed on the underlayer by recombining the fine particles with each other through the active new surface generated by the deformation or crushing. Form things.
[0017]
Here, the interpretation of the words that are important for understanding the present invention will be described below.
(Underlayer)
This is a thin layer in which an inorganic material or a metal material is bonded to the outermost surface of the resin base material. This maintains the adhesion to the base material, and when a brittle material structure is formed on it by a fine particle beam deposition method. A layer that is firmly bonded to a structure. It is desirable that a part of the bonding with the base material bites into the base material. Further, in the joining with the brittle material structure, when the brittle material structure particles collide, a part thereof bites in to form an anchor portion, or a part of the brittle material structure particles is crushed or collided by the collision of the brittle material structure particles. It is desirable to be made of a material that is deformed to form a new surface. A material that satisfies these conditions is a hard material, and a metal material can be suitably used from the viewpoint of easily forming an anchor portion, and an inorganic material such as a metal oxide can be suitably used from the viewpoint of easily forming a new surface. This layer can be formed by a fine particle beam deposition method, but plating, PVD, CVD, or other methods may be used.
(Polycrystalline)
In this case, it refers to a structure in which crystallites are joined and integrated. The crystallite is essentially one crystal, and its diameter is usually 5 nm or more. However, the case where the fine particles are taken into the structure without being crushed rarely occurs, but is substantially polycrystalline.
(Crystal orientation)
In this case, it refers to the degree of orientation of crystal axes in a polycrystal structure, and whether or not there is orientation is standard data by powder X-ray diffraction, which is generally considered to have substantially no orientation. JCPDS (ASTM) data is used as an index.
The peak intensity of the three major diffraction peaks in this index, which is the material constituting the brittle material crystal in the structure layer, is defined as 100%. In the present case, the state in which the deviation of the peak intensity of the other two peaks is within 30% of the index value is referred to as having substantially no orientation.
(interface)
In this case, it refers to the region that forms the boundary between crystallites.
(Grain boundary layer)
It is a layer with a certain thickness (usually several nm to several μm) located at the grain boundary in the interface or sintered body. It usually has an amorphous structure different from the crystal structure in the crystal grain, and in some cases, segregates impurities. Accompany.
(Internal distortion)
The lattice strain contained in the fine particles is a value calculated by using the Hall method in the X-ray diffraction measurement, and the deviation is expressed as a percentage with reference to a standard material in which the fine particles are sufficiently annealed.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
Embodiments of the present invention will be described below with reference to the accompanying drawings. Here, FIG. 1 to FIG. 3 are enlarged sectional views of the first aspect of the composite structure of resin and brittle material according to the present invention, and FIG. 4 is an enlarged sectional view showing the second aspect.
[0019]
In the composite structure shown in FIG. 1, the base layer and the brittle material structure are the same and integrated. In this case, the resin substrate in a softened state (in the case of a thermoplastic resin, the glass transition temperature or higher, in the case of a thermosetting resin, the temperature at which the precursor is in a semi-cured state) is hardened by a fine particle beam deposition method. The base layer is formed by using particles (brittle material fine particles) so that the hard particles penetrate into a part of the base material, and then the resin is cured, and then the brittle material is formed on the base layer by a fine particle beam deposition method. This is the case when a structure is formed.
In both cases, destruction and deformation of particles are occurring. The granular image in the figure shows the crystal grains of the brittle material structure formed, which are firmly bonded to each other.
[0020]
In the composite structure shown in FIG. 2, since the underlayer and the structure are different, the underlayer and the brittle material structure can be clearly separated and recognized (a boundary portion can be recognized). In this case, on the resin base material in the softened state, after forming a base layer in which the hard particles bite into a part of the base material using hard particles by a fine particle beam deposition method, the resin is cured, Next, it corresponds to a case where a brittle material structure is formed on the underlayer by a fine particle beam deposition method. The material for the underlayer may be a brittle material or a metal material, and the particle size thereof may not be the same as that of the brittle material structure formed thereon.
[0021]
In the composite structure shown in FIG. 3, the base layer and the structure are the same, but the size of the particles constituting the base layer is larger than the size of the particles of the structure. By letting such large particles bite into the base material, it adheres firmly to the base material due to the mass effect.
[0022]
The composite structure shown in FIG. 4 is a case where a ductile material layer exists as a base layer on a base material and a brittle material structure is formed thereon. In this case, after a ductile material layer such as metal is formed on a resin base material in advance by plating or PVD, certain brittle material fine particles are implanted by a fine particle beam deposition method.
[0023]
Next, an embodiment relating to a method of manufacturing a structure will be described.
A method for producing a brittle material structure on a thermoplastic resin substrate will be described. FIG. 5 shows a diagram of a fine particle beam deposition apparatus for forming a brittle material on a thermoplastic resin material. The configuration of the apparatus includes a heating / cooling plate 1 that can control the temperature of the thermoplastic resin material to a glass transition temperature (Tg) or higher and a melting point or lower, a thermometer 2 that measures the substrate temperature, a temperature controller 3 that controls the substrate temperature, A raw material tank 4 that vibrates and stirs brittle material fine particles as raw material powder, a carrier gas storage tank 5 that stores carrier gas, a connecting pipe 6 that connects the raw material tank 4 and the carrier gas storage tank 5, and brittle material fine particles as a carrier An injection pipe 8 for injecting the surface of the resin base material 7 with the carrier gas in the gas storage tank 5 and an injection nozzle 9 for forcibly cooling the resin base material on which the base layer is formed by air cooling are configured.
[0024]
The operation is performed by setting the base material 7 at the tip of the injection port of the injection pipe 8 and using the temperature controller 3 for controlling the base material temperature to a temperature not lower than the melting point of the glass transition temperature (Tg) of the base material 7. To do. The temperature of the substrate surface is measured by a thermometer 2 installed on the substrate and controlled by a temperature controller 3. When the temperature of the base material 7 reaches a predetermined temperature, the valve 10 of the carrier gas storage tank 5 is opened, the carrier gas in the carrier gas storage tank 5 is flowed, and the brittle material fine particles in the raw material tank 4 are transferred to the carrier gas. At the same time, it is ejected from the ejection port through the ejection tube 8 and collides with the surface of the substrate 7 controlled to a predetermined temperature.
[0025]
At this time, the temperature of the base material surface is controlled to be higher than the glass transition temperature and lower than the melting point of the resin base material, so that it is in a softened state, and the brittle material fine particles injected from the injection port pierce the base material surface. An underlayer is formed on the surface. At this time, since the base material is soft, the brittle material fine particles are not deformed and become anchors for deforming the substrate.
[0026]
When the temperature of the substrate 7 is lowered to the glass transition temperature or lower by water cooling or air cooling using the temperature controller 3 with the base layer formed, and the surface of the substrate is cured, a brittle material is formed on the resin substrate surface. A base layer in which the fine particles have eroded is formed. In order to accelerate the curing speed of the substrate surface, if a gas is blown from a separately provided air cooling nozzle 9, the curing speed is further increased and efficient.
[0027]
After this step, the brittle material fine particles are again sprayed from the injection port 8 toward the underlayer at a high speed, and then the brittle material fine particles collide with the underlayer to cause deformation or crushing. A brittle material structure is formed such that the particles and crushed fragment particles having an active surface re-join and grow from the underlayer.
[0028]
The above-described method for producing a brittle material structure on a resin base material is an example in which the process from the base layer formation process to the brittle material structure formation process is continuously performed. A brittle material structure on the resin substrate can be obtained even by an intermittent manufacturing method in which the structure forming step is performed after the substrate is sufficiently cooled.
[0029]
The thermoplastic resin material shown in this embodiment includes ABS, acetal resin, methacrylic resin, cellulose acetate, chlorinated polyether, ethylene-vinyl acetate copolymer, fluororesin, ionomer, methylpentene polymer, nylon, polycarbonate. , Polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyimide, polyphenylene oxide, polyphenylene sulfide, polyacrylate, polypropylene, polystyrene, polysulfone, vinyl acetate resin, vinylidene chloride resin, AS resin, vinyl chloride resin, etc. ₂ O _Three , NiO, TiO ₂ , CuO, ZnO, ZrO ₂ , SnO ₂ , MgO and other oxides, WC, diamond, SiC, B _Four Carbide such as C, AlN, Si _Three N _Four Nitride such as Ca ₂ A brittle material typified by fluoride such as F and ZrF is used, and as a carrier gas for conveyance, dry air, nitrogen, helium, argon, oxygen, hydrogen, a mixed gas with controlled oxygen partial pressure, or the like is used. it can.
[0030]
Here, regarding the formation process of the underlayer, it is useful to create it by applying the fine particle beam deposition method as described above. The material of the underlayer is not necessarily the same as the material of the brittle material structure, and is not limited to an inorganic material but may be a metal material. This is because the formation of a brittle material structure by the fine particle beam deposition method can be applied to metals and inorganic materials very well. Therefore, in the case of a metal, these fine particles, for example, Al, Cu, Ni, Ti, Pt, Au, Ag, Si, etc. are sprayed from the nozzle in the same manner, and are eroded into the base material to improve adhesion. It becomes a stratum. Thereafter, brittle material fine particles are sprayed from a nozzle to form an anchor portion into which the brittle material fine particles bite into the metal underlayer, and a structure is further grown thereon.
[0031]
Further, as a method for forming the base layer on the resin base material, a CVD method, a PVD method, a sol-gel method and a plating method which do not require heating to a high temperature are also effective.
[0032]
Next, a method for producing a brittle material structure on a thermosetting resin substrate will be described. FIG. 6 shows a fine particle beam deposition apparatus for forming a brittle material structure on a thermosetting resin material.
As a configuration of the apparatus, a heating plate 11 capable of controlling the kneaded thermosetting resin material at a temperature 10 ° C. lower than the curing temperature to a curing temperature or less, a thermometer 12 for measuring the substrate temperature, and the substrate temperature are controlled. A temperature controller 13, a raw material tank 14 for vibrating and stirring the brittle material fine particles as raw material powder, a carrier gas storage tank 15 for storing carrier gas, a connecting pipe 16 for connecting the raw material tank 14 and the carrier gas storage tank 15, By an injection pipe 18 for injecting fine particles of brittle material onto the surface of the resin base material 17 by the carrier gas in the carrier gas storage tank 15, and by an injection nozzle 19 for forcibly cooling the resin base material on which the base layer is formed by air cooling. It is configured.
[0033]
The operation is performed by setting the kneaded thermosetting resin base material 17 at the tip of the injection port of the injection pipe 18 and using the temperature controller 13 for controlling the base material temperature, the base material 17 is 10 ° C. from the base material curing temperature. Set at a low temperature or higher and below a curing temperature. The temperature of the substrate surface is measured by a thermometer 12 installed on the substrate and controlled by a temperature controller 13. When the temperature of the base material 17 reaches a predetermined temperature, the valve 20 of the carrier gas storage tank 15 is opened, the carrier gas in the carrier gas storage tank 15 is flowed, and the brittle material fine particles in the raw material tank 14 are transferred to the carrier gas. At the same time, it is ejected from the ejection port through the ejection pipe 18 and collides with the surface of the base material 17 controlled to a predetermined temperature.
[0034]
At this time, since the temperature of the substrate surface is controlled to be equal to or lower than the temperature at which the resin material is cured, the brittle material fine particles ejected from the ejection port are based on a soft state in which curing is not completely achieved. The base layer is easily formed on the surface of the substrate by sticking into the surface of the material. When the temperature of the base material 17 is raised to a temperature higher than the curing temperature of the base material using the temperature controller 13 in a state where the base layer is formed, formation of the base layer in which brittle material fine particles have digged into the surface of the resin base material. The process is complete.
[0035]
After passing through this step, the brittle material fine particles are again sprayed from the injection port 18 toward the underlayer at a high speed, and then the brittle material fine particles collide with the underlayer to cause deformation or crushing. A brittle material structure is formed such that the particles and crushed fragment particles having an active surface re-join and grow from the underlayer. In the above-described method for producing a brittle material structure on a resin base material, the process from the base layer formation process to the brittle material structure formation process is performed continuously. The brittle material structure can be formed on the resin base material even by an intermittent manufacturing method in which the forming step is performed after the resin base material is sufficiently cooled.
[0036]
As the thermosetting resin material shown in this embodiment, alkyd resin, allyl resin, amino resin, melamine resin, epoxy resin, urea resin, phenol resin, unsaturated polyester resin, silicone resin, polyurethane, etc. are used. . The same material as that of the above-described embodiment can be applied to the material of the underlayer and the material of the brittle material structure.
[0037]
Next, a method for producing a brittle material structure on a resin substrate by controlling the carrier gas flow rate will be described. FIG. 7 shows a fine particle beam deposition apparatus for controlling the carrier gas flow rate to form a brittle material structure in the resin material.
The configuration of the apparatus includes a base material fixing plate 21, a raw material tank 24 that vibrates and stirs brittle material fine particles as raw material powder, a carrier gas storage tank 25 that stores a carrier gas, a raw material tank 24 and a carrier gas storage tank 25, A connecting pipe 26 for connecting the particles, brittle material fine particles in the raw material tank 24 to the surface of the resin base material 27 by the carrier gas in the carrier gas storage tank 25, and a brittle material for forming a base layer A raw material tank 29 that vibrates and stirs fine particles, a carrier gas storage tank 30 that stores carrier gas, a connecting pipe 31 that connects the raw material tank 29 and the carrier gas storage tank 30, and an injection port 32 are included.
[0038]
In operation, the base material 27 is set in front of the injection port 32 and the injection port of the injection pipe 28, first, the valves 33 and 34 of the carrier gas storage tank 30 are opened, and the carrier gas in the carrier gas storage tank 30 flows. The brittle material fine particles in the raw material tank 29 are ejected from the ejection port 32 through the ejection pipe together with the carrier gas, and collide with the surface of the base material 27 at a slow particulate velocity of 50 m / s or less. Thereby, it is possible to form an underlayer in which brittle material fine particles are pierced on the surface layer portion without cutting the resin base material. After the formation of the underlayer is completed, the valves 33 and 34 of the carrier gas storage tank 30 are closed, and the carrier gas in the carrier gas storage tank 30 is stopped. Next, the

valves

35 and 36 of the carrier gas storage tank 25 are opened, the carrier gas in the carrier gas storage tank 25 is allowed to flow, and the brittle material fine particles in the raw material tank 24 pass through the injection pipe 28 together with the carrier gas from the injection port. The brittle material fine particles that are ejected and collided with the surface of the resin base material 27 on which the base layer is formed, and are crushed and deformed, have high activity, and the kinetic energy level possessed by the particles instantaneously increases A brittle material structure is formed on the resin base material on which bonding has occurred and the underlayer is formed.
[0039]
The above-described method for producing a brittle material structure on a resin base material is an example in which the base layer forming step and the brittle material structure forming step are performed using two injection ports, but this method is used. For example, the composite structure can be made more efficient by changing the composition and material of the material for forming the underlying layer and the brittle material structure formed thereon, or by changing the particle size of the brittle material fine particles that are the raw material powder. It becomes possible to form.
[0040]
The brittle material structure formed on the resin can basically be manufactured continuously by controlling the gas flow rate to perform the underlayer forming process and the structure forming process using one injection port. .
As the resin material, either a thermoplastic resin material or a thermosetting resin material can be applied. The above-mentioned materials can be similarly applied to the material of the underlayer and the brittle material structure.
[0041]
Furthermore, the present inventors have concluded that even when brittle materials having the same particle size are used, there is a difference in the formation speed and the achieved film thickness of the structure to be formed, which is caused by the internal strain of the particles. .
FIG. 8 shows the result of an experiment on the relationship between the film thickness of the structure and the internal strain achieved in the same formation time. In the experiment, aluminum oxide fine particles having a purity of 99.6% were pulverized using a planetary mill to change the characterization of the fine particles, and then a structure was formed on the aluminum substrate by an ultrafine particle beam deposition method. The internal strain of the fine particles was measured by X-ray diffraction, and the amount of strain was determined based on 0% obtained by subjecting the fine particles to thermal aging to remove the internal strain.
Moreover, the SEM photograph (Hitachi in-lens SEM S-5000) of the microparticles | fine-particles in point A, B, C in FIG. 8 is shown in FIG.9, FIG10 and FIG.11.
[0042]
It can be seen from FIG. 8 that 0.01 to 2.50% of internal strain is sufficient to obtain a film thickness of 1 μm, but 0.1 to 2.0% to obtain a stable film thickness. Is preferable. As shown in FIG. 9, when there is no internal strain, the crack does not occur when there is no internal strain. However, when the internal strain exceeds a certain value, in this case, 2.0% or more, the crack is completely cracked. 11 is formed, and the dropped pieces adhere to the surface, resulting in a re-aggregation state as shown in FIG.
[0043]
Thus, it is preferable to use a pulverizing means capable of giving a large impact for the pulverization applied to the fine particles in the pulverization treatment for distorting the fine particles. This is because a large strain can be imparted to the fine particles relatively uniformly. As such a pulverizing means, it is preferable to use a vibration mill, an attritor, or a planetary mill that can give a large acceleration of gravity compared to a ball mill often used for pulverizing ceramics. Most preferably, a planetary mill that can provide acceleration is used. Focusing on the state of the fine particles, since the crack cancels the internal strain, the most preferable is the fine particle whose internal strain is increased until just before the crack is generated. In the state shown in FIG. 10, some cracks are generated, but sufficient internal strain remains.
[0044]
An example of actually trying to form a structure on a plastic material using the fine particle beam deposition method will be described below.
(Reference example)
In the reference example, an aluminum oxide fine particle having a submicron particle diameter of 99% or more is sprayed on a plastic substrate by a fine particle beam deposition method to try to form a structure. ABS, polypropylene, acrylic resin, polyethylene terephthalate, polycarbonate, polystyrene, polyimide, and epoxy resin ARALDITE XD911 were used as the base material. The structure forming apparatus conforms to FIG. 6 and does not heat the substrate. Therefore, it does not have an injection nozzle for air-cooling the substrate. A nozzle for injecting fine particles, which is an injection tube, has an opening of 17 mm × 0.4 mm, and an aerosol in which aluminum oxide fine particles were mixed with nitrogen gas was sprayed at a flow rate of 7 L / min. The chamber for forming the structure was adjusted to 1 kPa or less with a vacuum pump. Formation was performed with an area of 17 mm × 5 mm, and the time was 10 minutes. Table 1 shows the presence or absence of the structure and the film thickness when it is formed. The film thickness was measured using a stylus type surface shape measuring device Dektak 3030 manufactured by Nippon Vacuum Technology Co., Ltd.
[0045]
[Table 1]

[0046]
(Example 1)
Next, an example in which a base layer is formed on a polyethylene terephthalate substrate as a thermoplastic resin using the aluminum oxide fine particles used in the reference example, and a structure is formed thereon will be described. First, a slurry in which aluminum oxide fine particles are dispersed in ethanol is dropped on a polyethylene terephthalate substrate and dried to form a fine particle adhesion layer on the substrate, and then the surface is pressed to make the substrate soft The fine particles were bitten into the substrate by maintaining at 100 ° C. for 1 hour, and the adhesion layer was fixed on the substrate as a base layer. Thereafter, the substrate was subjected to ultrasonic cleaning to remove fine particles that were not immobilized. Next, a structure was formed by a fine particle beam deposition method in the same manner as in the reference example. As a result, a film having a structure of 51.5 μm was formed on the underlayer. It can be seen that the structure was formed as compared with the reference example.
[0047]
(Example 2)
Next, an example will be described in which a layer is formed on the epoxy resin ARALDITE XD911 substrate as a thermosetting resin using the aluminum oxide fine particles used in the reference example, and a structure is formed thereon. First, an uncured epoxy resin is poured onto a SUS304 base material to flatten the surface, and a slurry in which aluminum oxide fine particles are dispersed in ethanol is dropped and dried at room temperature to form a fine particle adhesion layer on the substrate. After the formation, a curing treatment at 120 ° C. for 1 hour, which is the curing temperature of the resin, was performed, and the adhesion layer was fixed on the substrate as a base layer. Thereafter, the substrate was subjected to ultrasonic cleaning to remove fine particles that were not immobilized. Next, a structure was formed by a fine particle beam deposition method in the same manner as in the reference example. As a result, although it was a thin film with a film thickness of about 1 μm, it was found that the substrate was not scraped as in the reference example, and a structure was formed.
[0048]
(Example 3)
Next, an example in which a structure is formed after forming a metal underlayer on the surface of the resin substrate will be described. A polycarbonate substrate on which a structure was not formed as a base material was subjected to multilayer plating of copper, nickel, and chromium, and a structure was formed by a fine particle beam deposition method in the same manner as in the reference example. As a result, it was confirmed that a structure having a film thickness of 4 μm was formed on the surface of the underlayer.
[0049]
【The invention's effect】
As described above, according to the present invention, it is possible to form a brittle material structure on the surface of a soft resin substrate, which has been difficult in the past, by interposing an underlayer.
[Brief description of the drawings]
FIG. 1 is an enlarged sectional view of a composite structure of a resin and a brittle material according to a first embodiment of the present invention.
FIG. 2 is a view similar to FIG. 1 showing another embodiment.
FIG. 3 is a view similar to FIG. 1 showing another embodiment.
FIG. 4 is a view similar to FIG. 1 showing a composite structure belonging to the second aspect of the present invention.
FIG. 5 is a schematic view of an apparatus for producing a composite structure of a resin and a brittle material according to the present invention.
FIG. 6 is a schematic view showing another embodiment of the manufacturing apparatus.
FIG. 7 is a schematic view showing another embodiment of a manufacturing apparatus.
FIG. 8 is a graph showing the relationship between internal strain and film thickness of brittle material fine particles.
9 is an SEM photograph of fine particles at point A in FIG.
10 is an SEM photograph of fine particles at point B in FIG.
11 is an SEM photograph of fine particles at point C in FIG.

Claims

A brittle material in which a base layer made of a hard material that partially penetrates on the surface of the resin base material is formed, and there is substantially no grain boundary layer made of a glass layer at the interface between crystals on the base layer. A structure is formed by an aerosol deposition method, and the average particle size of the hard particles constituting the underlayer is larger than the average particle size of the particles constituting the brittle material structure. Composite structure.

The composite structure of a resin and a brittle material according to claim 1, wherein the underlayer has a thickness of 100 nm or more.

The composite structure of the resin according to claim 1 and a brittle material, wherein a part of the material constituting the foundation layer is crushed or deformed by collision of particles constituting the brittle material structure, thereby generating a new surface. A composite structure of a resin and a brittle material, wherein the brittle material structure and the base layer are joined.

The composite structure of the resin and the brittle material according to claim 1, wherein a part of the brittle material structure bites into the underlayer to form an anchor portion, and the resin and the brittle material Composite structure.

A base layer is formed by causing particles with a hardness higher than that of the resin base to penetrate the surface of the resin base material, and then the brittle material fine particles collide with the base layer at a high speed, and the brittle material fine particles are deformed by the impact of the collision. Or a composite structure of a resin and a brittle material that forms a polycrystalline brittle material structure on an underlayer by crushing and recombining fine particles with each other through an active new surface generated by this deformation or crushing In the manufacturing method of the product, the resin base material is made of a thermoplastic resin, and the resin base material is softened by heating above the glass transition temperature (Tg) of the thermoplastic resin. A method for producing a composite structure of a resin and a brittle material, characterized in that a base layer is formed by biting hard material particles.

6. The method for producing a composite structure of a resin and a brittle material according to claim 5, wherein a temperature of the brittle material structure forming step is set to be equal to or lower than a glass transition temperature (Tg) of the thermoplastic resin. A method for manufacturing a composite structure of a resin and a brittle material.

A base layer is formed by causing particles with a hardness higher than that of the resin base to penetrate the surface of the resin base material, and then the brittle material fine particles collide with the base layer at a high speed, and the brittle material fine particles are deformed by the impact of the collision. Or a composite structure of a resin and a brittle material that forms a polycrystalline brittle material structure on an underlayer by crushing and recombining fine particles with each other through an active new surface generated by this deformation or crushing In the manufacturing method of the product, the resin base material is made of a thermosetting resin, the precursor of the thermosetting resin is heated to a semi-cured state, and a hard material is applied to the surface of the base material in the semi-cured state. A method for producing a composite structure of a resin and a brittle material, characterized by forming a base layer by entraining particles.

8. The method of manufacturing a composite structure of a resin and a brittle material according to claim 7, wherein the brittle material structure forming step is performed after the thermosetting resin is cured. A method for producing a composite structure.

A metal underlayer is formed on the surface of the resin base material by plating or vapor deposition , and a glass layer is formed on the metal underlayer by an aerosol deposition method so as to be polycrystalline and substantially free of crystal orientation. A composite structure of a resin and a brittle material, in which a brittle material structure substantially free of a grain boundary layer is formed.

A composite structure of a resin and a brittle material according to claim 9, wherein a part of the brittle material structure bites into the metal underlayer to form an anchor portion, and a brittle material, Composite structure.

Forming a metal backing layer on the plating or vapor deposition on the resin substrate surface Te made of a metallic material is bonded to the metal material and the resin base material, then fast brittle material fine particles by aerosol deposition on the metal base layer And causing the brittle material fine particles to bite into the surface of the metal underlayer to form anchor portions to join the brittle material fine particles and the metal material, and the brittle material fine particles are deformed or crushed by the impact of the collision. A resin and a brittle material, characterized in that a polycrystalline brittle material structure is formed on the metal underlayer by recombining fine particles with each other through an active new surface generated by the deformation or crushing. And a method for producing a composite structure.