JP2010173274A - 金属と樹脂との複合体及びその製造方法 - Google Patents
金属と樹脂との複合体及びその製造方法 Download PDFInfo
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Abstract
【解決手段】金属よりなる金属部20と樹脂よりなる樹脂部30とが接着された金属と樹脂との複合体10であって、金属部20は表面にカルボキシル基及びアミノ基の少なくとも一方が付与されたものであり、樹脂30はエポキシ基を含む接着性改質剤が配合されたものであり、カルボキシル基及びアミノ基の少なくとも一方とエポキシ基との相互作用により、金属部20と樹脂部30とが接着されていることを特徴とする金属と樹脂との複合体。
【選択図】図1
Description
また、極性官能基と接着性官能基との相互作用は、極性官能基と接着性官能基との間に働く化学結合であり、具体的には、水素結合、共有結合、イオン結合、ファンデルワールス結合等である。
金属部の態様としては、特に限定はされないが、板状、箔状、塊状等が例示でき、複合体の用途にあわせて、加工機等により、予め所定形状に形成されていてもよいし、樹脂部との接着後に所定形状に形成されてもよい。
樹脂部の態様としては、特に限定はされないが、板状、フィルム状、塊状等が例示でき、複合体の用途にあわせて、金属部と接するように樹脂部を成形時に、所定形状にすることが、工程の削減になって好ましい。
また、樹脂は、機械的強度等を向上させるため、ガラス繊維、無機フィラー等が配合されていてもよいし、配合されていなくてもい。
接着性改質剤の含有量は、接着性改質剤の種類(接着性官能基の種類及び接着性改質剤中での接着性官能基の量等)によっても異なり、特に限定はされないが、樹脂と接着性改質剤との合計量100質量部に対し、5〜40質量部であることが好ましい。この値が5質量部未満では、金属部に対する樹脂部の接着性が低下し、40質量部を超えると、樹脂部を成形するときの離型性等が悪くなる。より好ましくは、10〜30質量部である。
樹脂と接着性改質剤との混合物(成形材料でもある)中における接着性官能基の含有量は、接着性官能基の種類によっても異なり、特に限定はされないが、樹脂と接着性改質剤との合計量の0.15〜1.2質量%であることが好ましい。この値が0.15質量%未満では、金属部に対する樹脂部の接着性が低下し、1.2質量%を超えると、樹脂部を成形するときの離型性等が悪くなる。より好ましくは、0.3〜0.9質量%である。
また、成形は、アニール工程を含んでいてもよいし、含んでいなくてもよい。
この相互作用は、金属部と樹脂部との界面で極性官能基及び接着性官能基の原子、電子等が互いに引き合う作用である。具体的には、極性官能基及び接着性官能基の原子間で、電子の移動・共有を伴う一次結合(イオン結合、共有結合等)と、極性官能基及び接着性官能基の中で、電子密度の偏在が生じ、両官能基同士がクローン力で引き合う二次結合(水素結合、ファンデルワールス結合等)とである。
金属と樹脂との複合体の態様としては、特に限定はされないが、板状、箔状、紐状、筒状、柱状、球状、塊状等が例示できる。
金属と樹脂との複合体の用途としては、特に限定はされないが、電子・電気部品、建築土木部材、自動車部品、農業資材、梱包資材、衣料、日用品等、又はこれらを製造するための材料等が例示できる。自動車部品としては、特に限定はされないが、エンジンオイル等をシールするシール部材、ハイブリット車等のバッテリーをシールするシール部材等が例示できる。
金属部は、長さ75mm、幅25mm、厚さ2mmのアルミニウム(A1050)の板であった。
樹脂は、ポリフェニレンサルファイド(PPS)、ポリアミド66(PA66)又はポリブチレンテレフタレート(PBT)であった。
接着性改質剤は、エチレンとスチレンとの共重合体がグリシジルメタクリレート(GMA)で変性された変性ポリエチレン−ポリスチレン共重合体(変性PE/PS)、又は、ポリエチレンがグリシジルメタクリレート(GMA)で変性された変性ポリエチレン(変性PE)であった。また、変性ポリエチレン−ポリスチレン共重合体及び変性ポリエチレンは共に、グリシジルメタクリレートの割合が10質量%であり、エポキシ基の含有量が3質量%であった。このうち、変性ポリエチレン−ポリスチレン共重合体は、ポリエチレンを主鎖とし、スチレン系モノマーを側鎖としたグラフト共重合体に、主鎖のポリエチレンがグリシジルメタクリレート(GMA)で変性され、接着性官能基として、エポキシ基(グリシジル基)を含む化合物であった。
金属表面にカルボキシル基を付与する化合物として、アクリル酸の単量体(分子量MW:72)、アクリル酸の重合体(分子量MW:5,000〜800,000)又はアクリル酸とマレイン酸の共重合体(アクリル酸/マレイン酸共重合体、分子量MW:10,000)を用いた。
金属表面にアミノ基を付与する化合物として、アリルアミンの単量体(分子量MW:57)又はアリルアミンの重合体(分子量MW:1,000〜25,000)を用いた。
金属表面にカルボキシル基とアミノ基との両方を付与する化合物として、ポリアミドを用いた。
・金属部の前処理
金属部は、表面を粒度#1,000のサンドペーパで擦って、油分を除去した。次いで、23℃の塩酸中に1分間浸漬して、表面のエッチングを行った。さらに、強アルカリ脱脂剤(日本パーカライジング社の「FC−E2001」)の70℃の水溶液中に1分間浸漬して脱脂を行った。
上記前処理を行った金属部の表面に、それぞれの表面処理に用いる化合物を塗布した後、150℃の恒温槽中にて、10分間の乾燥処理を行い、金属部の表面にそれぞれの化合物からなる膜(層)を形成した。なお、金属部の表面処理を行わないものは、本処理は行わなかった。
接着性改質剤を樹脂に配合するため、ラボプラストミル(東洋精機製作所社の「KF70V2」)を用い、表1、2の配合割合で樹脂と接着性改質剤とを、使用した樹脂が溶融する温度(PPS:320℃、PA66:300℃、PBT:260℃)で、5分間溶融混練を行い、成形材料とした。なお、樹脂に接着性改質剤を配合しないものは、本処理は行わなかった。
上記表面処理を行った金属部を金型内に配置した後、上記成形材料又は樹脂を金型内に入れ、成形材料に用いられている樹脂が溶融する上記温度で圧縮成形を行った。また、成形中に、次に示す条件でアニール工程を行った。
用いた樹脂がPPSのときは、金型の表面温度を150℃で3時間保持し、用いた樹脂がPA66又はPBTのときは、金型の表面温度を100℃で3時間保持した。
上記のようにして作成した複合体を、JIS K−6850(接着剤−剛性被着材の引張せん断接着強さ試験方法)に準拠して試験を行い、各複合体に破断を生じさせた。
金属部と樹脂部との界面で破断が生じ場合を×とし、樹脂部中で破断が生じ場合を○と評価した。
20 金属部
30 樹脂部
Claims (11)
- 金属よりなる金属部と樹脂よりなる樹脂部とが接着された金属と樹脂との複合体であって、
前記金属部は表面に極性官能基が付与されたものであり、
前記樹脂は前記極性官能基と相互に作用し合う接着性官能基を含む接着性改質剤が配合されたものであり、
前記極性官能基と前記接着性官能基との相互作用により、前記金属部と前記樹脂部とが接着されていることを特徴とする金属と樹脂との複合体。 - 前記極性官能基は、カルボキシル基及びアミノ基の少なくとも一方である請求項1記載の金属と樹脂との複合体。
- 前記接着性官能基は、エポキシ基である請求項1又は2記載の金属と樹脂との複合体。
- 前記接着性改質剤は、エチレンとスチレンとの共重合体がグリシジルメタクリレートで変性された変性エチレン−スチレン共重合体又はポリエチレンがグリシジルメタクリレートで変性された変性ポリエチレンである請求項3記載の金属と樹脂との複合体。
- 前記樹脂は、エンジニアリングプラスチックである請求項1〜4のいずれか一項に記載の金属と樹脂との複合体。
- 前記エンジニアリングプラスチックは、ポリフェニレンサルファイド、ポリアミド又はポリブチレンテレフタレートである請求項5記載の金属と樹脂との複合体。
- 前記金属は、アルミニウム又は銅である請求項1〜6のいずれか一項に記載の金属と樹脂との複合体。
- 金属よりなる金属部と樹脂よりなる樹脂部とが接着された金属と樹脂との複合体の製造方法であって、
前記金属部の表面に極性官能基を付与する表面処理と、
前記樹脂に前記極性官能基と相互に作用し合う接着性官能基を含む接着性改質剤を配合して成形材料とする配合処理とを行った後、
前記成形材料を用いて、前記金属部と接するように前記樹脂部を成形し、もって、前記極性官能基と前記接着性官能基との相互作用により、前記金属部と前記樹脂部とを接着させることを特徴とする金属と樹脂との複合体の製造方法。 - 前記表面処理は、アクリル酸の単量体、アクリル酸の重合体又はアクリル酸とマレイン酸との共重合体を用いて、前記金属部の表面に前記極性官能基としてのカルボキシル基を付与することである請求項8記載の金属と樹脂との複合体の製造方法。
- 前記表面処理は、アリルアミンの単量体又はアリルアミンの重合体を用いて、前記金属部の表面に前記極性官能基としてのアミノ基を付与することである請求項8記載の金属と樹脂との複合体の製造方法。
- 前記表面処理は、ポリアミドを用いて、前記金属部の表面に前記極性官能基としてのカルボキシル基及びアミノ基を付与することである請求項8記載の金属と樹脂との複合体の製造方法。
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US20100197882A1 (en) | 2010-08-05 |
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