JP4070082B2 - Substrate having polymer thin film and method for producing the same - Google Patents

Description

または、
一般式（II）
【化６】

で示される環状カルボン酸無水物単位を含む結合単位を各々１個以上有するポリマー（Ａ）を溶媒に溶解させ、その溶液に基材を接触させた後、基材を引き上げ、ポリマー（Ａ）が溶解する溶媒で洗浄し、次いで、乾燥させる方法が挙げられる。
【００４７】
この操作により、ポリマー（Ａ）は、静電相互作用、双極性の相互作用又は共有結合を介して、基材表面に結合したアミノ基またはカルボキシル基を有するカップリング剤に化学吸着させることができる。
【００４８】
本発明に使用するポリマー（Ａ）は、１分子中にアミノ基またはカルボキシル基を各々２つ以上有しているか、または、１分子中に一般式（I）又は一般式（II）で示される環状カルボン酸無水物単位などの結合単位を各々１つ以上有していれば、特に制限なく用いることができる。用いるポリマー（Ａ）は、ポリマーの側鎖に多数の上記官能基または結合単位を有するポリマーが好ましい。
【００４９】
効率よくポリマー薄膜を形成するためには、ポリマー１分子中に上記官能基の数が５〜５００あることが好ましく、中でも１０〜１００あることがより好ましく、また、ポリマー１分子中に上記結合単位の数が３〜２５０あることが好ましく、中でも５〜５０あることがより好ましい。また、ポリマー（Ａ）の分子量は特に制限されないが、５００〜１００万の範囲が好ましく、１０００〜１０万の範囲が特に好ましい。
【００５０】
ポリマー薄膜を作製する上で、ポリマー（Ａ）は柔軟性の高い分子構造を有することが好ましく、特に、重合性不飽和二重結合を有するモノマー、例えば、（メタ）アクリロイル基、ビニル基またはアリル基を有するモノマー、もしくは一般式（I）または一般式（II）で示される構造単位を有するモノマーから合成されるポリマーが好ましい。
【００５１】
これらのモノマーを例示すると、アリルアミン、Ｎ−メチルアリルアミン、Ｎ−アリルシクロペンチルアミン、Ｎ−アリルシクロヘキシルアミン、３−アミノ−１−プロピルビニルエーテル、Ｎ−アリルアニリン、４−ビニルアニリンなどのアミノ基を１つ含むモノマー、ジアリルアミン、トリアリルアミン等のアミノ基を複数含むモノマー、
【００５２】
（メタ）アクリル酸、クロトン酸、トランス−２−ペンテン酸、トランス−２−メチル−２−ペンテン酸、４−ビニル安息香酸などのカルボキシル基を１つ含むモノマー、イタコン酸、マレイン酸、フマル酸、シトラコン酸、メサコン酸、ジメチルマレイン酸などのカルボキシル基を２つ含むモノマー及びそれらのモノアルキルエステル、及び、イタコン酸無水物、マレイン酸無水物、シトラコン酸無水物およびジメチルマレイン酸無水物などのカルボン酸無水物モノマーなどが挙げられる。
【００５３】
これらのなかでも、アリルアミン、４−ビニルピリジン、マレイン酸、マレイン酸モノアルキルエステル、マレイン酸無水物、イタコン酸、イタコン酸モノアルキルエステルおよびイタコン酸無水物が好ましく用いられる。また、ポリエチレンイミンも好ましく用いることができる。
【００５４】
本発明に用いるポリマー（Ａ）は、上記モノマーから選ばれるモノマーのホモポリマー、又はそれらと共重合可能なモノマーとのコポリマーのいずれであってもよい。それらと共重合可能なモノマーは、生成するコポリマーが１分子中に上記の官能基を２つ以上、または上記の結合単位を１つ以上有していれば、特に制限されないが、柔軟性の高い分子構造を有するポリマーであることが好ましく、特に重合性不飽和二重結合を有するモノマー、例えば、（メタ）アクリロイル基、ビニル基またはアリル基を有するモノマーが好ましく用いられる。
【００５５】
これらの共重合可能な重合性不飽和二重結合を有するモノマーを例示すれば、メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、イソブチルビニルエーテル、ｔ−ブチルビニルエーテル、ｔ−ペンチルビニルエーテル、２−エチルヘキシルビニルエーテル、ドデシルビニルエーテル、エチレングリコールブチルビニルエーテル、トリ（エチレングリコール）メチルビニルエーテル、シクロヘキシルビニルエーテル、２−クロロエチルビニルエーテル、エチレングリコールビニルエーテル、１，４−ブタンジオールビニルエーテル、１，６−ヘキサンジオールビニルエーテル、ジエチレングリコールビニルエーテルなどのアルキルビニルエーテル類、
【００５６】
アリルエチルエーテル、アリルプロピルエーテル、アリルブチルエーテル、アリル−１，１，２，２−テトラフルオロエチルエーテル、アリル−１，１，２，２，３，３−ヘキサフルオロプロピルエーテルなどのアルキルアリルエーテル類、
【００５７】
スチレン、α−メチルスチレン、α，２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、４−ｔ−ブチルスチレン、２，４−ジメチルスチレン、３，５−ジメチルスチレン、２，４，６−トリメチルスチレン、１，１−ジフェニルエチレンなどのスチレンまたはスチレン誘導体、
【００５８】
４−ビニルビフェニル、２−ビニルナフタレン、９−ビニルアントラセン、１−ビニルピレンなどの縮合多環芳香族のビニル誘導体、
メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどの（メタ）アクリレート類が挙げられる。
【００５９】
中でもマレイン酸、マレイン酸モノアルキルエステル、マレイン酸無水物、イタコン酸、イタコン酸モノアルキルエステルまたはイタコン酸無水物などの電子受容性モノマーとの共重合性が高いことから、アルキルビニルエーテル類またはスチレンまたはスチレン誘導体などの電子供与性モノマーが特に好ましく用いられる。
【００６０】
上述のポリマー（Ａ）を溶媒に溶解させ、次いでカップリング剤を吸着させた基材に該ポリマー（Ａ）の溶液を接触させて、ポリマー（Ａ）を該基材に化学吸着させる。
【００６１】
ポリマー（Ａ）を溶解させる溶媒としては、該ポリマーを溶解でき、且つ、該ポリマー及び基材表面の官能基と反応しない有機溶媒であれば、特に制限なく用いることができる。ポリマーを溶解させる有機溶媒としては、例えば、アルコール類、ケトン類、エーテル類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホリックトリアミドなどの非プロトン性極性溶媒、脂肪族炭化水素類、芳香族炭化水素類、ハロゲン化炭化水素類など、またはこれらの混合物が挙げられる。
【００６２】
ポリマー（Ａ）の溶液を基材に接触させる際のポリマー溶液の温度は、０〜１５０℃であり、１５〜１００℃が好ましい。基材とポリマー（Ａ）溶液との接触処理時間は、１分間〜２４時間が好ましく、１０分間〜８時間がより好ましい。
【００６３】
基材をポリマー（Ａ）溶液から離した後の基材の洗浄操作は、未吸着のポリマー（Ａ）を基材表面から除去するために必要である。洗浄溶媒は、ポリマーを溶解することができる上記の溶媒が挙げられる。また、基材の乾燥方法も、前記と同様に行える。
【００６４】
次に、ポリマー（Ａ）を化学吸着させた基材に、アミノ基またはカルボキシル基を２個以上有する化合物（Ｂ）の溶液を接触させることにより、基材表面に吸着したポリマー（Ａ）中の未反応の上記の官能基または結合単位と化合物（Ｂ）中のカルボキシル基またはアミノ基との静電相互作用、双極性の相互作用又は共有結合を介して、化合物（Ｂ）を基材上のポリマー（Ａ）に化学吸着させる。
【００６５】
本発明に用いる化合物（Ｂ）は、１分子中にアミノ基またはカルボキシル基を各々２個以上有していれば、特に制限なく用いることができる。
そのような化合物を例示すると、エチレンジアミン、１，３−ジアミノプロパン、１，２−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノペンタン、２，２−ジメチル−１，３−プロパンジアミン、１，６−ジアミノヘキサン、１，８−ジアミノオクタン、１，１０−ジアミノデカン、１，１２−ジアミノドデカン、Ｎ−メチルエチレンジアミン、Ｎ−エチルエチレンジアミン、
【００６６】
Ｎ，Ｎ’−ジメチルエチレンジアミン、Ｎ，Ｎ’−ジエチルエチレンジアミン、Ｎ，Ｎ’−ジメチル−１，３−プロパンジアミン、Ｎ，Ｎ’−ジメチル−１，６−ヘキサンジアミン、２，２’−（エチレンジオキシ）−ビス（エチルアミン）、１，３−ジアミノ−２−ヒドロキシプロパン、シスタミンなどのアミノ基を２つ有する脂肪族化合物、
【００６７】
ジエチレントリアミン、Ｎ−（２−アミノエチル）−１，３−プロパンジアミン、Ｎ−（３−アミノプロピル）−１，３−プロパンジアミン、トリエチレンテトラミン、トリス（２−アミノエチル）アミン、テトラエチレンペンタミン、ペンタエチレンヘキサミンなどのアミノ基を３つ以上有する脂肪族化合物、
【００６８】
４，４’−メチレンビス（シクロヘキシルアミン）、４，４’−メチレンビス（２−メチルシクロヘキシルアミン）、トランス−１，４−ジアミノシクロヘキサン、１，３−シクロヘキサンビス（メチルアミン）などのアミノ基を２つ有する脂環式化合物、
【００６９】
４−（アミノメチル）ピペリジン、ピペラジン、２−メチルピペラジン、２，６−ジメチルピペラジン、トランス−２，５−ジメチルピペラジン、１−（２−アミノエチル）ピペラジン、１，４−ビス（３−アミノプロピル）ピペラジン、ホモピペラジン、１，４，７−トリアザシクロノナン、１，５，９−トリアザシクロドデカン、サイクレン、トリアザシクロテトラデカン、トリアザシクロペンタデカンなどのアミノ基を２つ以上有する複素環式化合物、
【００７０】
４，４’−エチレンジアニリン、４，４’−メチレンジアニリン、３，３’−メチレンジアニリン、４，４’−オキシジアニリン、４’’，４’’’−（ヘキサフルオロイソプロピリデン）−ビス（４−フェノキシアニリン）、４，４’−チオジアニリン、４−アミノフェニルジスルフィド、ｏ−トルイジン、４，４’−エチレンジ−ｍ−トルイジン、３，３’−ジアミノベンジジン、１，３−フェニレンジアミン、１，４−フェニレンジアミン、２，５−ジメチル−１，４−フェニレンジアミン、４，４’−（ヘキサフルオロイソプロピリデン）−ジアニリン、３，５−ジアミノ安息香酸、３，３’−ジメトキシベンジジン、１，５−ジアミノナフタレン、２，７−ジアミノフルオレン、２−アミノベンジルアミン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミンなどのアミノ基を２つ以上有する芳香族化合物
【００７１】
マロン酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、コハク酸、メチルコハク酸、２，２−ジメチルコハク酸、２，３−ジメチルコハク酸、グルタル酸、２−メチルグルタル酸、３−メチルグルタル酸、３，３−ジメチルグルタル酸、アジピン酸、３−メチルアジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、１，９−ノナンジカルボン酸、１，１０−デカンジカルボン酸、１，１１−ウンデカンジカルボン酸、１，１２−ドデカンジカルボン酸、１，１４−テトラデカンジカルボン酸、トリカルバリリック酸、１，２，３，４−ブタンテトラカルボン酸、マレイン酸、イタコン酸、フマル酸、シトラコン酸、メサコン酸、トランス−グルタコン酸、トランス−βヒドロムコン酸、トランス，トランス−ムコン酸、シス−アコンタン酸、
【００７２】
トランス−アコンタン酸、ヘキサフルオログルタル酸、ペルフルオロスベリン酸、ジグリコリン酸、３，６−ジオキサオクタンジオイン酸、チオジグリコリン酸、３，３’−チオジプロピオン酸、３，３’−ジチオジプロピオン酸、４，４’−ジチオジブタン酸、２，２’，２’’，２’’’−〔１，２−エタンジイリデン−テタラキス（チオ）〕−テトラキス酢酸などのカルボキシル基を２つ以上有する脂肪族化合物、
【００７３】
１，３−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸、１，３−アダマンタンジカルボン酸、１，３−アダマンタンジ酢酸、１，３，５−シクロヘキサントリカルボン酸、ケンプ酸、シクロブタンテトラカルボン酸、シクロヘキサンテトラカルボン酸などのカルボキシル基を２つ以上有する脂環式化合物、
【００７４】
１，３−フェニレンジ酢酸、１，４−フェニレンジ酢酸、４−カルボキシフェノキシ酢酸、１，４−フェニレンジプロピオン酸、１，４−フェニレンジアクリル酸、２，２’−イミノジ安息香酸、４，４’−（ヘキサフルオロイソプロピリデン）−ビス安息香酸、４，４’−オキシビス安息香酸、イソフタル酸、テレフタル酸、１，２，４−ベンゼントリカルボン酸、１，３，５−ベンゼントリカルボン酸、１，２，４，５−ベンゼンテトラカルボン酸、メリチン酸４，４’−ビフェニルジカルボン酸、１，４−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸などのカルボキシル基を２つ以上有する芳香族化合物が挙げられる。また、化合物（Ｂ）として、前記のアミノ基またはカルボキシル基を有するポリマー（Ａ）を用いることができる。
【００７５】
これらの中でも、基材表面への吸着効率が良いことから、エチレンジアミン、トランス−１，４−シクロヘキサンジアミン、コハク酸、トランス−１，４−シクロヘキサンジカルボン酸が特に好ましく用いられる。
【００７６】
溶媒に化合物（Ｂ）を溶解させた溶液を、ポリマー（Ａ）を吸着させた基材に接触させる。化合物（Ｂ）を溶解させる溶媒は、該化合物を溶解でき、且つ、該化合物、及び、基材表面の官能基と反応しない有機溶媒であれば、特に制限なく用いることができる。該化合物を溶解させる有機溶媒としては、例えば、アルコール類、ケトン類、エーテル類、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシドの如き非プロトン性極性溶媒、脂肪族炭化水素類、芳香族炭化水素類、ハロゲン化炭化水素類など、またはそれらの混合物が挙げられる。
【００７７】
化合物（Ｂ）と基材との接触処理温度は、０〜１５０℃が好ましく、より好ましくは１５〜１００℃である。処理時間は１分間〜２４時間、好ましくは１０分間〜８時間である。
【００７８】
該化合物（Ｂ）の溶液から基材を分離した後、該基材の洗浄に用いる溶媒は、化合物（Ｂ）を溶解することができる上記の溶媒が挙げられる。また、基材の乾燥方法も前記と同様である。
【００７９】
化合物（Ｂ）と基材との接触処理後に基材を加熱処理する。
この加熱処理により、基材に結合したカップリング剤とポリマー（Ａ）、ポリマー（Ａ）と化合物（Ｂ）との間の静電相互作用あるいは双極性の相互作用を介しての弱い吸着または化学吸着を、それらが有するアミノ基またはカルボキシル基との間でアミド結合またはイミド結合を形成させることにより強固な共有結合へと変換することができる。加熱処理温度は、１００〜５００℃が好ましく、１２０〜２５０℃がより好ましい。この加熱処理は、減圧下に行ってもよい。
【００８０】
加熱処理した基材に、更にポリマー（Ａ）の溶液を、カップリング剤を結合させた基材にポリマー（Ａ）の溶液を接触させたのと同様に接触させ、化合物（Ｂ）の未反応のアミノ基またはカルボキシル基との間での静電相互作用あるいは双極性の相互作用により、化合物（Ｂ）にポリマー（Ａ）を化学吸着させ、次いで該基材を上述の方法で、さらに化合物（Ｂ）の溶液に接触させて化合物（Ｂ）をポリマー（Ａ）に化学吸着させた後に加熱処理する工程を繰り返すことにより、基材上に形成されるポリマー（Ａ）と化合物（Ｂ）との繰り返しからなる、厚みを持った薄膜を基材上に形成させることができる。各工程の操作は、上記の方法で行うことができ、またこれらの繰り返し回数は、特に制限なく行うことができる。
【００８１】
また、この工程の繰り返し毎に、用いるポリマー（Ａ）と化合物（Ｂ）の種類を各々任意に変えることができる。すなわち、用いるポリマー（Ａ）と化合物（Ｂ）の種類は繰り返し工程毎に同一であっても異なる種類であっても良い。それらの複数のポリマー（Ａ）又は化合物（Ｂ）を用いるポリマー薄膜の作製は、異なる複数の機能を持つポリマー薄膜を有する基材の製造に有効である。
【００８２】
また、ポリマー（Ａ）と化合物（Ｂ）を吸着させるごとに加熱処理を行わずにポリマー（Ａ）と化合物（Ｂ）を吸着させる工程を繰り返し行った後に、加熱処理を行うことにより、吸着させたポリマー（Ａ）と化合物（Ｂ）とをまとめて一度にアミド結合またはイミド結合を形成させることにより、厚みを持つポリマー薄膜を同様に作製することができる。
【００８３】
また、同一のポリマー（Ａ）と化合物（Ｂ）の吸着後に、加熱処理を行い、更にポリマー（Ａ）と化合物（Ｂ）の種類を変えて吸着を行い、その後にまた加熱処理を行っても良く、これらは任意に選択できる。
【００８４】
本発明の製造方法によれば、１ｎｍ〜１００ｎｍの任意の膜厚のポリマー薄膜を有する基材を簡便に製造できる。本発明の製造方法により製造される基材のポリマー薄膜は、エリプソメトリーにより求めた膜厚値および走査型プローブ顕微鏡による表面プロファイルの測定から、標準偏差２．０ｎｍ以内の極めて良好な厚み精度とＲ_ｍｓ値（自乗平均面粗さ）２．０ｎｍ以内の高い表面平坦性を有し、且つ、優れた耐水性、耐溶剤性を備えている。
【００８５】
【実施例】
以下、実施例を用いて、本発明を更に詳細に説明する。しかしながら、本発明は、これらの実施例の範囲に限定されるものではない。
【００８６】
用いた測定、評価方法を以下に示す。
（１）エリプソメトリー：
Ｈｅ−Ｎｅレーザーを光源とした自動エリプソメーター（フォトデバイス製ＭＡＲＹ−１０２）を用い、入射角７０°にてポリマー薄膜の膜厚を測定した。
【００８７】
（２）フーリエ変換赤外分光分析（ＦＴ−IＲ）：
フーリエ変換赤外分光光度計（バイオ−ラッド製ＦＴＳ−６０Ａ）を用いて、反射吸収モード（入射角８５°）にてポリマー薄膜のＦＴ−IＲスペクトルを測定した。
【００８８】
（３）Ｘ線光電子分光分析（ＸＰＳ）：
Ｘ線光電子分光分析装置（島津製作所ＥＳＣＡ−８５０）を用い、Ｘ線源をＭｇＫαとして、ポリマー薄膜のＸＰＳスペクトルを測定した。
【００８９】
（４）原子間力顕微鏡（ＡＦＭ）：
走査型プローブ顕微鏡（セイコー電子製ＳＰI３７００）を用い、コンタクトモードにてポリマー薄膜の表面プロファイルを測定した。
【００９０】
＜実施例１＞
表面に厚さ１５０ｎｍの金層を製膜したガラス製の基材を、シスタミンの５ミリモル／リットルのエタノール溶液中に５０℃で３時間浸漬した後、取り出し、エタノール中で超音波洗浄し、窒素ガスによりブロー乾燥した。これの工程を工程（II）と称する。
【００９１】
このようにして得た基材をマレイン酸モノメチルエステルとスチレンとの交互コポリマー（重量平均分子量５０，０００）の繰り返し単位当たり０．１ミリモル／リットルの２−ブタノン溶液に、室温にて１時間浸漬した後、該溶液中から取り出し、２−ブタノン中に浸漬することにより洗浄し、更に窒素ガスによりブロー乾燥させた。これらの工程を、工程（II）と称する。
【００９２】
次に、該基材を、エチレンジアミンの２５ミリモル／リットルのトルエン溶液に室温で１時間浸漬した後、該溶液中から取り出し、トルエン中に浸漬することにより洗浄し、更に、窒素ガスによりブロー乾燥させた。これらの工程を、工程（III）と称する。
【００９３】
更に、該基材を１８０℃の恒温槽で０．０１Ｐａ以下の減圧下で６時間加熱処理した。この工程を、工程（IV）と称する。
【００９４】
このようにして得た基材に、更に工程（II）〜工程（IV）を繰り返して行うことにより、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【００９５】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（IV）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。繰り返し回数に伴なう膜厚の変化を図１に示した。ポリマー薄膜の膜厚は、工程（II）〜工程（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１０．９ｎｍであった。
【００９６】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸モノメチルエステルとスチレンとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４０ｃｍ^-1；ν_C=O，１７０１ｃｍ^-1；Ｎ_1s結合エネルギー，４０１ｅＶ。
【００９７】
また、ＡＦＭ（原子間力顕微鏡）像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより、いずれも膜厚値に変化がないことから、高い膜安定性が証明された。
【００９８】
以上の方法で、金層上にマレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【００９９】
＜実施例２＞
工程（IV）を行わない以外は、実施例１と同様にして得た基材を１８０℃の恒温槽で０．０１Ｐａ以下の減圧下で６時間加熱処理して、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１００】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（III）を１〜９回繰り返し行った際、並びに該基材を加熱処理した後で、薄膜の膜厚をエリプソメトリーにより測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（III）の繰り返し回数に比例して増加することが確認され、９回繰り返して得られた薄膜の膜厚は８．８ｎｍであり、また、加熱処理後の薄膜の膜厚は８．８ｎｍであった。
【０１０１】
９回の繰り返し操作後に加熱処理して得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸モノメチルエステルとスチレンとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４５ｃｍ^-1；ν_C=O，１７０２ｃｍ^-1；Ｎ_1s結合エネルギー，４０１．２ｅＶ。
【０１０２】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１０３】
以上の方法で、金層上にマレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１０４】
＜実施例３＞
工程（III）において、基材をエチレンジアミンの２５ミリモル／リットルのトルエン溶液に室温で１時間浸漬した後、該溶液中から取り出し、トルエン中に浸漬することにより洗浄する代わりに、基材をポリアリルアミン（重量平均分子量１５，０００）の繰り返し単位当たり０．１ミリモル／リットルのメタノール溶液に室温で１時間浸漬した後、該溶液中から取り出し、メタノール中に浸漬することにより洗浄した以外は、実施例１と同様にして、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１０５】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（IV）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１３．１ｎｍであった。
【０１０６】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸モノメチルエステルとスチレンとの交互コポリマーとポリアリルアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４１ｃｍ^-1；ν_C=O，１７０２ｃｍ^-1；Ｎ_1s結合エネルギー，４０１ｅＶ。
【０１０７】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１０８】
以上の方法で、金層上にマレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１０９】
＜実施例４＞
表面に金層を製膜したガラス製の基材に代えて、表面に厚さ１５０ｎｍの金層を製膜したポリエチレンテレフタレート（ＰＥＴ）樹脂製基材を用いた以外は、実施例１と同様にして、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１１０】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（IV）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１１．５ｎｍであった。
【０１１１】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸モノメチルエステルとスチレンとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４０ｃｍ^-1；ν_C=O，１７０３ｃｍ^-1；Ｎ_1s結合エネルギー，４０１．２ｅＶ。
【０１１２】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１１３】
以上の方法で、金層上にマレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するＰＥＴ樹脂製基材を作製した。
【０１１４】
＜実施例５＞
表面に金層を製膜したガラス製の基材に代えて、石英基材を用い、また、工程（I）で、基材をシスタミンの５ミリモル／リットルのエタノール溶液中に５０℃で３時間浸漬した後、エタノール中で超音波洗浄する代わりに、３−アミノプロピルトリメトキシシランの５ミリモル／リットルのメタノール溶液中に５０℃で３時間浸漬した後、メタノール中で超音波洗浄した以外は、実施例１と同様にして、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１１５】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（IV）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１１．３ｎｍであった。
【０１１６】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸モノメチルエステルとスチレンとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４２ｃｍ^-1；ν_C=O，１７０１ｃｍ^-1；Ｎ_1s結合エネルギー，４０１．１ｅＶ。
【０１１７】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１１８】
以上の方法で、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有する石英基材を作製した。
【０１１９】
＜実施例６＞
工程（IV）を行わない以外は、実施例５と同様にして得た基材を、１８０℃の恒温槽で０．０１Ｐａ以下の減圧下で６時間加熱処理して、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１２０】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（III）を１〜９回繰り返し行った際、並びに該基材を加熱処理した後で、薄膜の膜厚をエリプソメトリーにより測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（III）の繰り返し回数に比例して増加することが確認され、９回繰り返して得られた薄膜の膜厚は８．９ｎｍであり、また、加熱処理後の薄膜の膜厚は８．９ｎｍであった。
【０１２１】
９回の繰り返し操作後に加熱処理して得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸モノメチルエステルとスチレンとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４１ｃｍ^-1；ν_C=O，１７０１ｃｍ^-1 ；Ｎ_1s結合エネルギー，４０１．２ｅＶ。
【０１２２】
また、ＡＦＭ像から平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１２３】
以上の方法で、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有する石英基材を作製した。
【０１２４】
＜実施例７＞
エチレンジアミンの代わりに、トランス−１，４−シクロヘキサンジアミンを用いた以外は、実施例５と同様にして、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１２５】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（IV）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１１．７ｎｍであった。
【０１２６】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸モノメチルエステルとスチレンとの交互コポリマーとトランス−１，４−シクロヘキサンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４３ｃｍ^-1；ν_C=O，１７００ｃｍ^-1；Ｎ_1s結合エネルギー，４０１ｅＶ。
【０１２７】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１２８】
以上の方法で、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有する石英基材を作製した。
【０１２９】
＜実施例８＞
工程（II）において、マレイン酸モノメチルエステルとスチレンとの交互コポリマー（重量平均分子量５０，０００）の代わりに、マレイン酸とメチルビニルエーテルとの交互コポリマー（重量平均分子量７０，０００）を用いた以外は、実施例１と同様にして、マレイン酸とメチルビニルエーテルとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１３０】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（IV）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１１．３ｎｍであった。
【０１３１】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸とメチルビニルエーテルとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４２ｃｍ^-1；ν_C=O，１７０３ｃｍ^-1；Ｎ_1s結合エネルギー，４０１．１ｅＶ。
【０１３２】
またＡＦＭ像から平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１３３】
以上の方法で、金層上にマレイン酸とメチルビニルエーテルとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１３４】
＜実施例９＞
工程（II）において、マレイン酸モノメチルエステルとスチレンとの交互コポリマー（重量平均分子量５０，０００）の代わりに、マレイン酸とスチレンとの交互コポリマー（重量平均分子量７０，０００）を用いた以外は、実施例５と同様にして、マレイン酸とスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１３５】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（IV）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１１．５ｎｍであった。
【０１３６】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸とスチレンとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された。
：ν_C=O，１６４５ｃｍ^-1；ν_C=O，１７０１ｃｍ^-1；Ｎ_1s結合エネルギー，４０１ｅＶ。
【０１３７】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１３８】
以上の方法で、マレイン酸とスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有する石英基材を作製した。
【０１３９】
＜実施例１０＞
工程（II）において、マレイン酸モノメチルエステルとスチレンとの交互コポリマー（重量平均分子量５０，０００）に代えて、マレイン酸無水物とスチレンとの交互コポリマー（重量平均分子量５０，０００）を用いた以外は、実施例１と同様にして、マレイン酸無水物とスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１４０】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（IV）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１１．２ｎｍであった。
【０１４１】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸無水物とスチレンとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４５ｃｍ^-1；ν_C=O，１７０２ｃｍ^-1；Ｎ_1s結合エネルギー，４０１ｅＶ。
【０１４２】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１４３】
以上の方法で、金層上にマレイン酸無水物とスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１４４】
＜実施例１１＞
工程（II）において、マレイン酸モノメチルエステルとスチレンとの交互コポリマー（重量平均分子量５０，０００）に代えて、マレイン酸無水物とスチレンとの交互コポリマー（重量平均分子量５０，０００）を用いた以外は、実施例２と同様にして、マレイン酸無水物とスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１４５】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（III）を１〜９回繰り返し行った際、並びに該基材を加熱処理した後で、薄膜の膜厚をエリプソメトリーにより測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（III）の繰り返し回数に比例して増加することが確認され、９回繰り返して得られた薄膜の膜厚は９．３ｎｍであり、また、加熱処理後の薄膜の膜厚は９．３ｎｍであった。
【０１４６】
９回の繰り返し操作後に加熱処理して得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸無水物とスチレンとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４０ｃｍ^-1；ν_C=O，１７０２ｃｍ^-1；Ｎ_1s結合エネルギー，４０１．２ｅＶ。
【０１４７】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１４８】
以上の方法で、金層上にマレイン酸無水物とスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１４９】
＜実施例１２＞
工程（II）において、マレイン酸モノメチルエステルとスチレンとの交互コポリマー（重量平均分子量５０，０００）に代えて、イタコン酸無水物とスチレンとの交互コポリマー（重量平均分子量４２，０００）を用いた以外は、実施例１と同様にして、イタコン酸無水物とスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１５０】
得られたポリマー薄膜を有する基材について、工程（II）〜工程（IV）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（II）〜工程（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１１．８ｎｍであった。
【０１５１】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、イタコン酸無水物とスチレンとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４５ｃｍ^-1；ν_C=O，１７０２ｃｍ^-1；Ｎ_1s結合エネルギー，４０１ｅＶ。
【０１５２】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１５３】
以上の方法で、金層上にイタコン酸無水物とスチレンとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１５４】
＜実施例１３＞
表面に厚さ１５０ｎｍの金層を製膜したガラス製の基材を、３−メルカプトプロピオン酸の５ミリモル／リットルのエタノール溶液中に５０℃で３時間浸漬した後、取り出しエタノール中で超音波洗浄し、窒素ガスによりブロー乾燥した。これらの工程を、工程（V）と称する。
【０１５５】
得られた基材を、ポリアリルアミン（重量平均分子量１５，０００）の繰り返し単位当たり０．１ミリモル／リットルのメタノール溶液に、室温にて１時間浸漬した後、該溶液中から取り出し、メタノール中に浸漬することにより洗浄し、更に窒素ガスによりブロー乾燥させた。これらの工程を、工程（VI）と称する。
【０１５６】
次に、該基材を、コハク酸の２５ミリモル／リットルのメタノール溶液に室温で１時間浸漬した後、該溶液中から取り出し、メタノール中に浸漬することにより洗浄し、更に、窒素ガスによりブロー乾燥させた。これらの工程を、工程（VII）と称する。
【０１５７】
更に該基材を１８０℃の恒温槽で０．０１Ｐａ以下の減圧下で６時間加熱処理した。これらの工程を、工程（VIII）と称する。
【０１５８】
このようにして得た基材に、更に、工程（VI）〜工程（VIII）を繰り返して行うことにより、ポリアリルアミンを構成要素としたポリマー薄膜を有する基材を得た。
【０１５９】
得られたポリマー薄膜を有する基材について、工程（VI）〜工程（VIII）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（VI）〜工程（VIII）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１０．１ｎｍであった。
【０１６０】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、ポリアリルアミンとコハク酸との間のアミド結合の生成が確認された：ν_C=O，１６４５ｃｍ^-1；Ｎ_1s結合エネルギー，４０１ｅＶ。
【０１６１】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１６２】
以上の方法で、金層上にポリアリルアミンを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１６３】
＜実施例１４＞
工程（VIII）を行わない以外は、実施例１３と同様にして得た基材を、１８０℃の恒温槽で０．０１Ｐａ以下の減圧下で６時間加熱処理して、ポリアリルアミンを構成要素としたポリマー薄膜を有する基材を得た。
【０１６４】
得られたポリマー薄膜を有する基材について、工程（VI）〜工程（VII）を１〜９回繰り返し行った際、並びに該基材を加熱処理した後で、薄膜の膜厚をエリプソメトリーにより測定した。ポリマー薄膜の膜厚は、工程（VI）〜工程（VII）の繰り返し回数に比例して増加することが確認され、９回繰り返して得られた薄膜の膜厚は８．８ｎｍであり、また、加熱処理後の薄膜の膜厚は８．９ｎｍであった。
【０１６５】
９回の繰り返し操作後に加熱処理して得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、ポリアリルアミンとコハク酸との間のアミド結合の生成が確認された：ν_C=O，１６４８ｃｍ^-1；Ｎ_1s結合エネルギー，４０１．２ｅＶ。
【０１６６】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１６７】
以上の方法で、金層上にポリアリルアミンを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１６８】
＜実施例１５＞
工程（VI）において、ポリアリルアミン（重量平均分子量１５，０００）に代えて、ポリエチレンイミン（重量平均分子量１０，０００）を用いた以外は、実施例１３と同様にして、ポリエチレンイミンを構成要素としたポリマー薄膜を有する基材を得た。
【０１６９】
得られたポリマー薄膜を有する基材について、工程（VI）〜工程（VIII）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（VI）〜工程（VIII）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１０．８ｎｍであった。
【０１７０】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、ポリエチレンイミンとコハク酸との間のアミド結合の生成が確認された：ν_C=O，１６４４ｃｍ^-1；ν_C=O；Ｎ_1s結合エネルギー，４０１．２ｅＶ。
【０１７１】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１７２】
以上の方法で、金層上にポリエチレンイミンを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１７３】
＜実施例１６＞
工程（VI）において、ポリアリルアミン（重量平均分子量１５，０００）に代えて、４−ビニルアニリンとスチレンとのコポリマー（重量平均分子量３０，０００、４−ビニルアニリン含有率３５モル％）を、また、工程（VII）において、コハク酸の２５ミリモル／リットルのメタノール溶液に代えて、トランス−１，４−シクロヘキサンジカルボン酸の５ミリモル／リットルのメタノール溶液を用いた以外は、実施例１３と同様にして、４−ビニルアニリンとスチレンとのコポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１７４】
得られたポリマー薄膜を有する基材について、工程（VI）〜工程（VIII）を１〜１０回繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。ポリマー薄膜の膜厚は、工程（VI）〜工程（VIII）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は１１．３ｎｍであった。
【０１７５】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、ポリエチレンイミンとコハク酸との間のアミド結合の生成が確認された：ν_C=O，１６４５ｃｍ^-1；ν_C=O；Ｎ_1s結合エネルギー，４０１ｅＶ。
【０１７６】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１７７】
以上の方法で、金層上に４−ビニルアニリンとスチレンとのコポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１７８】
＜実施例１７＞
実施例１と同様にして、工程（I）〜工程（IV）を行った。次に、該基材を、マレイン酸とメチルビニルエーテルとの交互コポリマー（重量平均分子量７０，０００）の繰り返し単位当たり０．１ミリモル／リットルの２−ブタノン溶液に、室温にて１時間浸漬した後、該溶液中から取り出し、２−ブタノン中に浸漬することにより洗浄し、更に窒素ガスによりブロー乾燥させた。これらの工程を工程（IX）と称する。続いて、該基材に、工程（III）及び工程（IV）を施した。
【０１７９】
このようにして得た基材に、更に、各工程（II）、（III）、（IV）、（IX）、（III）および（IV）をこの順序で繰り返して行うことにより、マレイン酸モノメチルエステルとスチレンとの交互コポリマー、及びマレイン酸とメチルビニルエーテルとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１８０】
得られたポリマー薄膜を有する基材について、各工程（II）、（III）、（IV）、（IX）、（III）、（IV）をこの順序で繰り返し、各回毎にエリプソメトリーにより膜厚を測定した。繰り返し回数に伴なう膜厚値の変化を図２に示した。ポリマー薄膜の膜厚は、各工程（II）、（III）、（IV）、（IX）、（III）および（IV）の繰り返し回数に比例して増加することが確認され、１０回繰り返して得られた薄膜の膜厚は２３．１ｎｍであった。
【０１８１】
１０回の繰り返し操作から得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸モノメチルエステルとスチレンとの交互コポリマー、及びマレイン酸とメチルビニルエーテルとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４５ｃｍ^-1；ν_C=O，１７０１ｃｍ^-1；Ｎ_1s結合エネルギー，４０１ｅＶ。
【０１８２】
また、ＡＦＭ像から平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより、いずれも膜厚値に変化がないことから、高い膜安定性が証明された。
【０１８３】
以上の方法で、金層上にマレイン酸モノメチルエステルとスチレンとの交互コポリマー、及びマレイン酸とメチルビニルエーテルとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１８４】
＜実施例１８＞
工程（IV）を行わない以外は、実施例１７と同様にして得た基材を、１８０℃の恒温槽で０．０１Ｐａ以下の減圧下で６時間加熱処理して、マレイン酸モノメチルエステルとスチレンとの交互コポリマー、及びマレイン酸とメチルビニルエーテルとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。
【０１８５】
得られたポリマー薄膜を有する基材について、各工程（II）、（III）、（IX）および（III）を１〜９回繰り返し行った際、並びに該基材を加熱処理した後で、薄膜の膜厚をエリプソメトリーにより測定した。ポリマー薄膜の膜厚は、各工程（II）、（III）、（IX）および（III）の繰り返し回数に比例して増加することが確認され、９回繰り返して得られた薄膜の膜厚は１８．２ｎｍであり、また、加熱処理後の薄膜の膜厚は１８．１ｎｍであった。
【０１８６】
９回の繰り返し操作後に加熱処理して得られたポリマー薄膜を有する基材について、ＦＴ−IＲ測定、及びＸＰＳ分析から、マレイン酸モノメチルエステルとスチレンとの交互コポリマー、及びマレイン酸とメチルビニルエーテルとの交互コポリマーとエチレンジアミンとの間のアミド結合及びイミド結合の生成が確認された：ν_C=O，１６４２ｃｍ^-1；ν_C=O，１７０２ｃｍ^-1；Ｎ_1s結合エネルギー，４０１ｅＶ。
【０１８７】
また、ＡＦＭ像から、平坦性に優れた表面プロファイルが観察され、一方、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストにより膜厚値に変化がないことから、高い膜安定性が証明された。
【０１８８】
以上の方法で、金層上にマレイン酸モノメチルエステルとスチレンとの交互コポリマー、及びマレイン酸とメチルビニルエーテルとの交互コポリマーを構成要素とした、膜安定性が高く、厚み精度に優れ、且つ表面平坦性の良好なポリマー薄膜を有するガラス製基材を作製した。
【０１８９】
＜比較例１＞
工程（IV）を行わない以外は、実施例１と同様にして、マレイン酸モノメチルエステルとスチレンとの交互コポリマーを構成要素としたポリマー薄膜を有する基材を得た。９回繰り返し操作後のポリマー薄膜を有する基材について、エリプソメトリーから８．８ｎｍの膜厚を有することが確認されたが、水、エタノール、クロロホルム、トルエンに５０℃にて４８時間浸積する耐溶剤テストの結果、それぞれ、８．７、４．５、６．２、７．５ｎｍへと膜厚値が減少し、耐溶剤性が高くないことが判った。
【０１９０】
＜比較例２＞
表面に厚さ１５０ｎｍの金層を製膜したガラス製の基材を、シスタミン二塩酸塩の５ミリモル／リットルのエタノール溶液中に５０℃で３時間浸漬した後、取り出し、エタノール中で超音波洗浄し、窒素ガスによりブロー乾燥した。
【０１９１】
得られた基材を、ポリ（４−スチレンスルホン酸ナトリウム）（重量平均分子量７０，０００）の繰り返し単位当たり０．１ミリモル／リットルの水溶液に、室温にて１時間浸漬した後、該溶液中から取り出し、水中に浸漬することにより洗浄し、更に窒素ガスによりブロー乾燥させた。次に、該基材をポリアリルアミン塩酸塩の繰り返し単位当たり０．１ミリモル／リットルの水溶液に室温で１時間浸漬した後、該溶液中から取り出し、水中に浸漬することにより洗浄し、更に窒素ガスによりブロー乾燥させた。
【０１９２】
以上の操作を繰り返し、１０回繰り返し操作後のポリマー薄膜を有する基材について、エリプソメトリーの分析から１５．５ｎｍの膜厚を有することが確認されたが、水、エタノールに４０℃にて４８時間浸積する耐溶剤テストの結果、それぞれ、８．５、７．５ｎｍへと膜厚値が減少し、耐溶剤性が高くないことが確認された。
【０１９３】
＜比較例３＞
石英基材を、メタクリル酸３−トリメトキシシリルプロピルの５ミリモル／リットルのメタノール溶液中に５０℃で３時間浸漬した後、取り出し、メタノール中で超音波洗浄し、更に、１００℃の恒温槽で０．０１Ｐａ以下の減圧下で１時間加熱処理した。得られた基材を、メタクリル酸メチルの２５ミリモル／リットルのトルエン溶液に浸積させ、アゾビスイソブチロニトリル（メタクリル酸メチルに対して、１モルパーセント）の存在下、６０℃にて、３０分間、２時間、１２時間、又は４８時間重合反応を行った。
【０１９４】
得られたポリマー薄膜を有する基材のエリプソメトリーによる膜厚測定の結果、重合反応時間が３０分間、２時間、１２時間、４８時間の薄膜が、それぞれ、２５．２、２７．３、２７．８、３０．１ｎｍの膜厚値を示した。以上の結果より、この方法では、制御された膜厚のポリマー薄膜を有する基材を製造することは容易でないことが判った。
【０１９５】
【発明の効果】
本発明は、高い結合安定性と優れた平坦性を持つポリマー薄膜を有する基材とナノメートル単位で膜厚を制御できる該ポリマー薄膜を有する基材の簡便な製造方法を提供する。また本発明のポリマー薄膜を有する基材のポリマー薄膜は、優れた厚み精度と耐溶剤性を有する。
【図面の簡単な説明】
【図１】 実施例１で作製した、マレイン酸モノメチルエステルとスチレンとの交互コポリマーからなるポリマー薄膜の膜厚変化を示す図である。
【図２】 実施例１７で作成した、マレイン酸モノメチルエステルとスチレンとの交互コポリマー及びマレイン酸とメチルビニルエーテルとの交互コポリマーからなるポリマー薄膜の膜厚変化を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a substrate having a polymer thin film and a method for producing the same.
More specifically, the present invention is a substrate having a highly stable polymer thin film that is useful in a wide range of fields such as an optical functional film, an optical / electronic element, and a separation film, and the film thickness can be controlled in nanometer units. The present invention relates to a method for producing a substrate having a polymer thin film.
[0002]
[Prior art]
In recent years, extensive research has been conducted on the development of a base material modified with a polymer thin film having a thickness of nanometer order. The field of application covers a wide range, including catalysts, material separation, sensor technology, electrooptic technology, and photonic technology.
[0003]
Conventionally, a Langmuir-Blodget (LB) method using a polymer or a monomer imparted with amphiphilic properties is frequently used as a method for producing a substrate having a polymer thin film whose film thickness and composition are controlled at the nanometer level. (For example, JP-A-6-32913 and JP-A-2000-143831).
[0004]
For example, by forming a hydrophilic polymer monomolecular film having a hydrophobic site such as a long-chain alkyl group on the water surface and repeatedly transferring it onto the substrate, a substrate having a polymer thin film can be formed relatively easily. Obtainable. Alternatively, a substrate having a polymer thin film can be obtained relatively easily by forming a monomolecular film of an amphiphilic monomer on the water surface, repeatedly transferring it onto the substrate and further polymerizing it.
[0005]
However, in order to obtain a thin film with good thickness accuracy, an expensive and relatively large LB film manufacturing apparatus is required. Moreover, since each layer of the obtained polymer multilayer thin film is laminated | stacked only based on physical adsorption, the stability of a polymer thin film is not necessarily high.
[0006]
On the other hand, a method of forming a stable polymer thin film on a substrate by immobilizing a monomer having a functional group capable of being chemically adsorbed on a solid surface or a polymerization initiator on the substrate and performing a polymerization reaction using them. Have been studied in the field of “polymer brush” (Japanese Patent Laid-Open Nos. 5-17595 and 2000-143705).
[0007]
For example, a monomer or a polymerization initiator having a functional group such as an alkoxysilyl group or a mercapto group is dissolved in a suitable solvent, and the substrate is immersed in the monomer or polymerization initiator to fix the monomer or polymerization initiator to the surface of the substrate. A substrate having a polymer thin film can be obtained by immersing the substrate in a solution containing a monomer or a monomer and a polymerization initiator and polymerizing the substrate. Although these can provide high film stability, they are polymer thin film formation based on a sequential polymerization reaction on a substrate, and thus are not necessarily advantageous methods for controlling the film thickness and composition at the molecular level.
[0008]
In recent years, a method for producing a substrate having a polymer thin film by laminating a charged polymer (hereinafter referred to as “polymer electrolyte”) on a substrate alternately with a polymer electrolyte having an opposite charge has been proposed (for example, JP-A-10-167707, “Prog. ColloId Polym. ScI. 89, 160, 1992”.
[0009]
For example, a base material subjected to a cationic treatment is immersed in a solution containing an anionic polymer electrolyte such as poly (sodium 4-styrenesulfonate), and then the base material is cationic polymer such as polyallylamine hydrochloride. By immersing in an electrolyte and repeating these steps, a thin film in which an anionic polymer electrolyte and a cationic polymer electrolyte are alternately laminated can be produced on a substrate.
[0010]
This method can produce a polymer multilayer thin film easily and in a short time, but the stability is not necessarily high because the connection between layers depends on ionic interaction. Recently, a method for producing a base material having a polymer thin film by alternately laminating polymers each having an electron-donating group and an electron-accepting group using charge transfer interaction has been proposed (Japanese Patent Laid-Open No. 10-101). 244616). However, since this method also forms a polymer thin film by non-covalent bonding, it has a defect of low stability like the other methods described above.
[0011]
On the other hand, the present inventors have found that an alternating copolymer of maleic acid monoalkyl ester and alkyl vinyl ether can form a stable polymer thin film via an imide bond on the surface of a substrate to which a coupling agent having an amino group is bonded. (Japanese Patent Laid-Open No. 10-120790). However, the film thickness of the polymer thin film is as thin as about 3 nm, and no means for forming a polymer thin film obtained by laminating a polymer having a large film thickness and no means for controlling the film thickness of the polymer thin film have been found.
[0012]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a substrate having a polymer thin film having high bond stability and excellent flatness and a simple method for producing the substrate having the polymer thin film capable of controlling the film thickness in nanometer units. It is to provide.
[0013]
[Means for Solving the Problems]
In order to easily produce a substrate having a polymer thin film that has high bonding stability and whose film thickness and composition can be controlled at the nanometer level, the present inventors have used a molecular adsorption method such as chemical adsorption. It was considered that the polymer was laminated on the substrate and then the interaction between the polymers was converted into a strong bond such as a covalent bond.
[0014]
The inventors contact a coupling agent having a functional group capable of forming an amide bond or an imide bond such as an amino group or a carboxyl group on the surface of the substrate, and then the substrate is brought into contact with the functional group and the amino group or carboxyl group. A polymer (A) having two or more functional groups capable of forming an amide bond or an imide bond, such as a group, and contacting the polymer (A) with the substrate; The substrate is heated by contact with a solution of the compound (B) having two or more functional groups each capable of forming an amide bond or an imide bond such as a carboxyl group, and then immediately or after repeating these one more times. In this way, the polymers that have been in contact with and adsorbed to the base material are bonded to each other with an amide or imide bond to form a strong covalent bond on the base material It found that to form a substrate having a polymer film, thereby completing the present invention.
[0015]
That is, the present invention includes (1) a step of bringing a coupling agent having one kind of functional group capable of forming an imide bond or an amide bond into contact with the substrate surface to bond the coupling agent to the substrate surface;
(2) One or more functional groups possessed by the coupling agent bonded to the substrate have one or more functional groups capable of forming an imide bond or an amide bond, or an imide bond or an amide bond. A step of bringing the base material into contact with a solution of the polymer (A) having one or more structural units of the following, and chemically adsorbing the polymer (A) to a coupling agent bonded to the base material:
[0016]
(3) The base material on which the polymer (A) has been chemically adsorbed has two or more of one type of functional group or structural unit of the polymer (A) and one type of functional group capable of forming an imide bond or an amide bond. Contacting the solution of the compound (B) to cause the polymer (A) to chemisorb the compound (B);
(4) A polymer thin film characterized by heating the base material to form an imide bond or an amide bond, and (5) repeating the steps (2) to (4) at least once on the base material. Provided is a method for producing a substrate having the same.
[0017]
The present invention also provides a metal selected from the group consisting of Au, Ag, Cu, and Pt, or SIO. ₂ , Al ₂ O _Three , InO ₂ , SnO ₂ , ZrO ₂ , TIO ₂ And HfO ₂ A coupling agent having an amino group or a carboxyl group is bonded onto a substrate made of glass, quartz or resin, the surface of which is coated with a metal oxide selected from the group consisting of:
A polymer (A) bonded with a functional group of the coupling agent by forming an imide bond or an amide bond;
A compound selected from the group consisting of unreacted functional groups or structural units of the polymer (A) and ethylenediamine, trans-1,4-cyclohexanediamine, polyallylamine, succinic acid, or trans-1,4-cyclohexanedicarboxylic acid ( B) is bonded to form an imide bond or an amide bond,
Further, the unreacted functional group of the compound (B) is bonded to the polymer (A) of the same or different type by forming an imide bond or an amide bond with the polymer (A). One or more types of polymers (A) and one or more types of compounds (B) in which the group or structural unit is bonded to the compound (B) that is the same or different from the compound (B) by forming an imide bond or an amide bond Provided is a substrate having a polymer thin film composed of a plurality of repeating bonds formed by forming an imide bond or an amide bond.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described in detail below.
The base material used for the base material having the polymer thin film of the present invention is obtained by bringing the base material into contact with a coupling agent having a functional group capable of forming an imide bond or an amide bond, and using these coupling agents as the base material. Any material that can be bonded to the surface can be used without particular limitation. More specifically, a substrate made of glass, metal or resin can be used.
[0019]
Among them, at least the surface to be contacted with a coupling agent described later is a metal selected from the group consisting of Au, Ag, Cu and Pt, or SIO ₂ , Al ₂ O _Three , InO ₂ , SnO ₂ , ZrO ₂ , TIO ₂ And HfO ₂ A base material coated with a metal oxide selected from the group consisting of is preferable because the coupling agent easily binds to the surface.
[0020]
Next, a coupling agent having a functional group capable of forming an imide bond or an amide bond will be described.
The coupling agent having a functional group capable of forming an imide bond or an amide bond used in the present invention is a functional group that can be covalently bonded to the substrate surface used in one molecule and an imide bond such as an amino group or a carboxyl group. Alternatively, any compound having a functional group capable of forming an amide bond can be used without particular limitation.
[0021]
Specifically, as a coupling agent that can be used for a substrate having a metal whose surface is selected from the group consisting of Au, Ag, Cu, and Pt, for example, a sulfur compound having an amino group or a carboxyl group can be mentioned.
[0022]
In general, when a substrate having a metal selected from the group consisting of Au, Ag, Cu, and Pt is immersed in a solution of an active sulfur compound on the surface of the substrate, the sulfur-containing group is chemically bonded to the substrate surface. It is known to bond and form a stable monolayer on the surface of the substrate [A. Ulman, "Introduction to ultra-thin organic films from Langmuir-Blodgett method to self-assembly." (An Introduction to Ultrathin OrganIc FIlms from LangmuIr-Blodgett to Self-Assembly) "(AcademIc Press Inc. Boston, 1991).
[0023]
Examples of the sulfur compound having an amino group or a carboxyl group include 2-aminoethyl mercaptan, 3-aminopropyl mercaptan, 4-aminobutyl mercaptan, 6-aminohexyl mercaptan, 12-aminododecyl mercaptan, 4-aminothiophenol and the like. A mercaptan having an amino group, a sulfide compound having an amino group such as 2,2′-diaminoethyl sulfide, a disulfide compound having an amino group such as cystamine,
[0024]
Carboxyl such as 3-mercaptopropionic acid, 4-mercaptobutanoic acid, 6-mercaptohexanoic acid, 8-mercaptooctanoic acid, 10-mercaptodecanoic acid, 12-mercaptododecanoic acid, 16-mercaptohexadecanoic acid, 18-mercaptooctadecanoic acid A mercaptan having a group,
[0025]
Examples include 2,2′-dicarboxyethyl disulfide, 5,5′-dicarboxypentyl disulfide, 11,11′-dicarboxyundecyl disulfide, disulfide compounds having a carboxyl group such as lipoic acid, and the like. Is not to be done.
[0026]
In order to treat a substrate with a sulfur compound having an amino group or a carboxyl group, for example, any one of the compounds is dissolved in a solvent, the substrate is brought into contact with the solution, and then the substrate is pulled up. A method of washing with a solvent in which the compound is dissolved may be mentioned.
[0027]
Examples of the solvent for dissolving a sulfur compound having an amino group or a carboxyl group include alcohol compounds such as methanol and 2-propanol; ketone compounds such as acetone and 2-butanone; aliphatic hydrocarbons such as hexane and hexadecane; Aromatic hydrocarbons such as toluene and xylene;
[0028]
Examples include halogenated hydrocarbons such as methylene chloride and 1,1,2-trichloroethane; ether compounds such as tetrahydrofuran and 1,4-dioxane, and mixtures thereof, but are not limited to these solvents. Any solvent that does not react with sulfur-containing groups, amino groups or carboxyl groups can be used.
[0029]
The concentration of the sulfur compound having an amino group or a carboxyl group in the solution is usually 0.001 mmol / liter to 5 mol / liter, and preferably 0.1 to 100 mmol / liter. When the concentration is less than 0.001 mmol / liter, the reaction tends to take a long time.
[0030]
10-120 degreeC is preferable and the processing temperature by the solution of the sulfur compound which has an amino group or a carboxyl group has an especially preferable 15-80 degreeC. The treatment time with the solution is usually 1 minute to 24 hours, but generally a long treatment time is required when the treatment temperature is low. Therefore, it is preferable to adjust the treatment temperature so that the treatment time is 30 minutes to 6 hours. .
[0031]
The washing operation after separating the base material from the solution of the sulfur compound having an amino group or a carboxyl group is important for removing the unreacted sulfur compound. As the solvent for this washing, the above-mentioned solvent capable of dissolving the sulfur compound can be used. There is no restriction | limiting in particular in the drying method, You may carry out by 10-100 degreeC on pressure reduction conditions, and you may carry out by gas blows, such as air, nitrogen, and argon.
[0032]
Next, the surface is SIO ₂ , Al ₂ O _Three , InO ₂ , SnO ₂ , ZrO ₂ , TIO ₂ And HfO ₂ Examples of the coupling agent that can be used for a substrate having a metal oxide selected from the group consisting of an alkoxysilane or halogenated silane having an amino group or a carboxyl group (hereinafter, a silane having an amino group or a carboxyl group at the terminal) Abbreviated as a compound).
[0033]
In general, when a substrate having a metal oxide on the surface is immersed in a silane compound solution as described above, the silyl group in the silane compound is chemically bonded to the substrate surface, and a stable monomolecular film layer is formed on the substrate surface. It is known to form.
[0034]
Examples of the silane compound having an amino group or a carboxyl group used in the present invention include 3-aminopropyltrichlorosilane, 3-aminopropylmethyldichlorosilane, 3-aminopropyldimethylchlorosilane, 3-aminopropyltrimethoxysilane, and 3-amino. Propylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane,
[0035]
3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 6-aminohexyltrichlorosilane, 6-aminohexyltrimethoxysilane, 6-aminohexyltriethoxysilane , 11-aminoundecyltrichlorosilane, 11-aminoundecyltrimethoxysilane, 11-aminoundecyltriethoxysilane-containing alkoxysilane or halogenated silane having an amino group,
[0036]
3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 4-trimethoxysilylbutanoic acid, 4-triethoxysilylbutanoic acid, 6-trimethoxysilylhexanoic acid, 6-triethoxysilylhexanoic acid, 12- Examples include alkoxysilanes having a carboxyl group such as trimethoxysilyldodecanoic acid and 12-triethoxysilyldodecanoic acid.
[0037]
As a method of treating a substrate using a silane compound having these amino groups or carboxyl groups, for example, after dissolving any one of these compounds in a solvent and contacting the substrate with the solution, A method of pulling up the substrate and washing with a solvent in which the compound is dissolved may be mentioned.
[0038]
Examples of the solvent for dissolving these silane compounds include aliphatic hydrocarbons such as hexane and hexadecane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated carbonization such as methylene chloride and 1,1,2-trichloroethane. Hydrogen; ether compounds such as tetrahydrofuran and 1,4-dioxane are included.
[0039]
However, the solvent is not limited to these solvents, and any solvent that does not have a hydroxyl group or a carbonyl group and that does not react with an amino group or a carboxyl group can be used. However, when a compound having a silicon atom bonded to an alkoxy group is used, an alcohol compound such as methanol or propanol; a ketone compound such as acetone or 2-butanone, or a mixed solvent thereof can be used.
[0040]
The concentration of the silane compound having an amino group or a carboxyl group in the solution is 0.001 mmol / liter to 5 mol / liter, preferably 0.1 to 100 mmol / liter. When the concentration of the silane compound having an amino group or a carboxyl group in the solution is less than 0.001 mmol / liter, the reaction tends to take a long time.
[0041]
The processing temperature using the solution of the silane compound which has an amino group or a carboxyl group is 10-120 degreeC normally, and 15-80 degreeC is preferable. The treatment time is not particularly limited, but the treatment time is preferably in the range of 1 minute to 24 hours, and more preferably in the range of 30 minutes to 6 hours.
[0042]
The cleaning operation after separating the substrate from the solution of the silane compound having an amino group or carboxyl group is important for removing the unreacted silane compound. As the cleaning solvent, the silane compound having an amino group or carboxyl group is used. The above-mentioned solvent which can dissolve can be used. Moreover, heat-treating the treated substrate is effective for complete treatment with the silane compound. The heat treatment temperature is preferably in the range of 50 to 200 ° C, more preferably in the range of 50 to 120 ° C.
[0043]
In this way, a coupling agent having one type of functional group capable of forming an imide bond or an amide bond is brought into contact with the substrate surface, and the coupling agent is bonded to the substrate surface.
[0044]
Next, the functional group of the coupling agent bonded to the substrate has two or more functional groups that can form an imide bond or an amide bond, or one kind that can form an imide bond or an amide bond. A method of bringing the base material into contact with a solution of the polymer (A) having one or more structural units and chemically adsorbing the polymer (A) to the base material will be described.
[0045]
As a method of chemically adsorbing a polymer (A) having two or more types of functional groups that can form an imide bond or an amide bond with a functional group possessed by a coupling agent bonded to a base material on the base surface, an amino group Alternatively, after bringing the substrate into contact with a solution of the polymer (A) having two or more carboxyl groups, the substrate is pulled up, washed with a solvent in which the polymer (A) is dissolved, and then dried. It is done.
[0046]
As a method of chemically adsorbing a polymer (A) having at least one kind of bonding unit capable of forming an imide bond or an amide bond with a functional group of a coupling agent bonded to a substrate on the substrate surface,
Formula (I)
[Chemical formula 5]

Or
Formula (II)
[Chemical 6]

The polymer (A) having one or more bond units each containing a cyclic carboxylic acid anhydride unit represented by the formula (1) is dissolved in a solvent, and the substrate is brought into contact with the solution. A method of washing with a dissolving solvent and then drying is mentioned.
[0047]
By this operation, the polymer (A) can be chemisorbed to the coupling agent having an amino group or a carboxyl group bonded to the surface of the substrate through electrostatic interaction, bipolar interaction or covalent bond. .
[0048]
The polymer (A) used in the present invention has two or more amino groups or carboxyl groups in one molecule, or is represented by general formula (I) or general formula (II) in one molecule. If it has one or more bond units, such as a cyclic carboxylic acid anhydride unit, it can be used without particular limitation. The polymer (A) to be used is preferably a polymer having a large number of the above functional groups or bonding units in the side chain of the polymer.
[0049]
In order to efficiently form a polymer thin film, the number of functional groups in the polymer molecule is preferably 5 to 500, more preferably 10 to 100, and the bonding unit in the polymer molecule. Is preferably 3 to 250, and more preferably 5 to 50. The molecular weight of the polymer (A) is not particularly limited, but is preferably in the range of 500 to 1,000,000, particularly preferably in the range of 1,000 to 100,000.
[0050]
In preparing the polymer thin film, the polymer (A) preferably has a highly flexible molecular structure, and in particular, a monomer having a polymerizable unsaturated double bond, such as a (meth) acryloyl group, a vinyl group or an allyl group. A polymer synthesized from a monomer having a group or a monomer having a structural unit represented by general formula (I) or general formula (II) is preferred.
[0051]
Examples of these monomers include amino groups such as allylamine, N-methylallylamine, N-allylcyclopentylamine, N-allylcyclohexylamine, 3-amino-1-propyl vinyl ether, N-allylaniline, 4-vinylaniline, and the like. Monomers containing two or more amino groups such as diallylamine and triallylamine,
[0052]
Monomers containing one carboxyl group such as (meth) acrylic acid, crotonic acid, trans-2-pentenoic acid, trans-2-methyl-2-pentenoic acid, 4-vinylbenzoic acid, itaconic acid, maleic acid, fumaric acid , Monomers containing two carboxyl groups such as citraconic acid, mesaconic acid, dimethylmaleic acid and their monoalkyl esters, and itaconic acid anhydride, maleic acid anhydride, citraconic acid anhydride, dimethylmaleic acid anhydride, etc. Examples thereof include carboxylic acid anhydride monomers.
[0053]
Among these, allylamine, 4-vinylpyridine, maleic acid, maleic acid monoalkyl ester, maleic anhydride, itaconic acid, itaconic acid monoalkyl ester and itaconic anhydride are preferably used. Polyethyleneimine can also be preferably used.
[0054]
The polymer (A) used in the present invention may be either a homopolymer of a monomer selected from the above monomers or a copolymer with a monomer copolymerizable therewith. The monomer copolymerizable with them is not particularly limited as long as the copolymer to be produced has two or more of the above functional groups or one or more of the above bonding units in one molecule, but is highly flexible. A polymer having a molecular structure is preferable, and a monomer having a polymerizable unsaturated double bond, for example, a monomer having a (meth) acryloyl group, a vinyl group or an allyl group is preferably used.
[0055]
Examples of these monomers having a polymerizable unsaturated double bond capable of copolymerization include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, t-pentyl vinyl ether, 2-ethylhexyl vinyl ether. , Dodecyl vinyl ether, ethylene glycol butyl vinyl ether, tri (ethylene glycol) methyl vinyl ether, cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol vinyl ether, 1,4-butanediol vinyl ether, 1,6-hexanediol vinyl ether, diethylene glycol vinyl ether, etc. Alkyl vinyl ethers,
[0056]
Alkyl allyl ethers such as allyl ethyl ether, allyl propyl ether, allyl butyl ether, allyl-1,1,2,2-tetrafluoroethyl ether, allyl-1,1,2,2,3,3-hexafluoropropyl ether ,
[0057]
Styrene, α-methylstyrene, α, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6 -Styrene or styrene derivatives such as trimethylstyrene, 1,1-diphenylethylene,
[0058]
Condensed vinyl polycyclic aromatic vinyl derivatives such as 4-vinylbiphenyl, 2-vinylnaphthalene, 9-vinylanthracene, 1-vinylpyrene,
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) Examples include (meth) acrylates such as acrylate, octadecyl (meth) acrylate, and isobornyl (meth) acrylate.
[0059]
Among them, since it has high copolymerizability with an electron accepting monomer such as maleic acid, maleic acid monoalkyl ester, maleic anhydride, itaconic acid, itaconic acid monoalkyl ester or itaconic anhydride, alkyl vinyl ethers or styrene or Electron donating monomers such as styrene derivatives are particularly preferably used.
[0060]
The polymer (A) is dissolved in a solvent, and then the solution of the polymer (A) is brought into contact with the base material on which the coupling agent is adsorbed, so that the polymer (A) is chemisorbed on the base material.
[0061]
The solvent for dissolving the polymer (A) can be used without particular limitation as long as it is an organic solvent that can dissolve the polymer and does not react with the functional group of the polymer and the substrate surface. Examples of the organic solvent for dissolving the polymer include aprotic polar solvents such as alcohols, ketones, ethers, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoric triamide. , Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like, or a mixture thereof.
[0062]
The temperature of the polymer solution when the polymer (A) solution is brought into contact with the substrate is 0 to 150 ° C, and preferably 15 to 100 ° C. The contact treatment time between the substrate and the polymer (A) solution is preferably 1 minute to 24 hours, and more preferably 10 minutes to 8 hours.
[0063]
The washing operation of the substrate after separating the substrate from the polymer (A) solution is necessary to remove the unadsorbed polymer (A) from the substrate surface. Examples of the washing solvent include the above solvents that can dissolve the polymer. Moreover, the drying method of a base material can also be performed similarly to the above.
[0064]
Next, the polymer (A) in the polymer (A) adsorbed on the substrate surface is brought into contact with the substrate on which the polymer (A) is chemically adsorbed by bringing a solution of the compound (B) having two or more amino groups or carboxyl groups into contact therewith. Through electrostatic interaction, bipolar interaction or covalent bond between the above-mentioned unreacted functional group or bonding unit and the carboxyl group or amino group in compound (B), compound (B) is bonded onto the substrate. Chemisorbed on the polymer (A).
[0065]
The compound (B) used in the present invention can be used without particular limitation as long as it has two or more amino groups or carboxyl groups in one molecule.
Examples of such compounds are ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine. 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, N-methylethylenediamine, N-ethylethylenediamine,
[0066]
N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-dimethyl-1,3-propanediamine, N, N′-dimethyl-1,6-hexanediamine, 2,2 ′-( Aliphatic compounds having two amino groups such as ethylenedioxy) -bis (ethylamine), 1,3-diamino-2-hydroxypropane, cystamine,
[0067]
Diethylenetriamine, N- (2-aminoethyl) -1,3-propanediamine, N- (3-aminopropyl) -1,3-propanediamine, triethylenetetramine, tris (2-aminoethyl) amine, tetraethylenepenta An aliphatic compound having three or more amino groups, such as min and pentaethylenehexamine;
[0068]
An amino group such as 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), trans-1,4-diaminocyclohexane, 1,3-cyclohexanebis (methylamine), etc. Having an alicyclic compound,
[0069]
4- (aminomethyl) piperidine, piperazine, 2-methylpiperazine, 2,6-dimethylpiperazine, trans-2,5-dimethylpiperazine, 1- (2-aminoethyl) piperazine, 1,4-bis (3-amino Propyl) piperazine, homopiperazine, 1,4,7-triazacyclononane, 1,5,9-triazacyclododecane, cyclen, triazacyclotetradecane, complex having two or more amino groups such as triazacyclopentadecane Cyclic compounds,
[0070]
4,4′-ethylenedianiline, 4,4′-methylenedianiline, 3,3′-methylenedianiline, 4,4′-oxydianiline, 4 ″, 4 ′ ″-(hexafluoroisopropylidene ) -Bis (4-phenoxyaniline), 4,4′-thiodianiline, 4-aminophenyl disulfide, o-toluidine, 4,4′-ethylenedi-m-toluidine, 3,3′-diaminobenzidine, 1,3- Phenylenediamine, 1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 4,4 ′-(hexafluoroisopropylidene) -dianiline, 3,5-diaminobenzoic acid, 3,3′- Dimethoxybenzidine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 2-aminobenzylamine, m-xylylenediamine, p-xylylene Aromatic compounds having an amino group such as an amine of two or more
[0071]
Malonic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric Acid, 3,3-dimethylglutaric acid, adipic acid, 3-methyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11 -Undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, tricarbacrylic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid , Mesaconic acid, trans-glutaconic acid, trans-β hydromuconic acid, trans, trans-mucon Cis - Akontan acid,
[0072]
Trans-Acontanic acid, hexafluoroglutaric acid, perfluorosuberic acid, diglycolinic acid, 3,6-dioxaoctanedioic acid, thiodiglycolinic acid, 3,3'-thiodipropionic acid, 3,3'-dithiodipropionic acid , 4,4′-dithiodibutanoic acid, 2,2 ′, 2 ″, 2 ′ ″-[1,2-ethanediylidene-tetarakis (thio)]-tetrakisacetic acid and other aliphatic compounds having two or more carboxyl groups ,
[0073]
1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,3-adamantanediacetic acid, 1,3,5-cyclohexanetricarboxylic acid, kempic acid, cyclobutanetetracarboxylic acid, An alicyclic compound having two or more carboxyl groups such as cyclohexanetetracarboxylic acid,
[0074]
1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, 4-carboxyphenoxyacetic acid, 1,4-phenylenedipropionic acid, 1,4-phenylenediacrylic acid, 2,2′-iminodibenzoic acid, 4 , 4 ′-(hexafluoroisopropylidene) -bisbenzoic acid, 4,4′-oxybisbenzoic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, Aromatics having two or more carboxyl groups such as 1,2,4,5-benzenetetracarboxylic acid, melittic acid 4,4′-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid Compounds. Moreover, the polymer (A) which has the said amino group or carboxyl group can be used as a compound (B).
[0075]
Among these, ethylenediamine, trans-1,4-cyclohexanediamine, succinic acid, and trans-1,4-cyclohexanedicarboxylic acid are particularly preferably used because of their high adsorption efficiency to the substrate surface.
[0076]
A solution in which the compound (B) is dissolved in a solvent is brought into contact with the substrate on which the polymer (A) is adsorbed. The solvent for dissolving the compound (B) can be used without any particular limitation as long as it can dissolve the compound and does not react with the compound and the functional group on the surface of the base material. Examples of the organic solvent for dissolving the compound include alcohols, ketones, ethers, aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide, aliphatic hydrocarbons, aromatic hydrocarbons, Halogenated hydrocarbons and the like, or a mixture thereof.
[0077]
0-150 degreeC is preferable and, as for the contact processing temperature of a compound (B) and a base material, More preferably, it is 15-100 degreeC. The treatment time is 1 minute to 24 hours, preferably 10 minutes to 8 hours.
[0078]
Examples of the solvent that can be used for washing the base material after separating the base material from the solution of the compound (B) include the above-mentioned solvents that can dissolve the compound (B). The substrate drying method is the same as described above.
[0079]
The substrate is heated after the contact treatment between the compound (B) and the substrate.
This heat treatment causes weak adsorption or chemistry through electrostatic or bipolar interactions between the coupling agent bound to the substrate and polymer (A), polymer (A) and compound (B). The adsorption can be converted into a strong covalent bond by forming an amide bond or an imide bond with the amino group or carboxyl group which they have. The heat treatment temperature is preferably from 100 to 500 ° C, more preferably from 120 to 250 ° C. This heat treatment may be performed under reduced pressure.
[0080]
The polymer (A) solution is further brought into contact with the heat-treated base material in the same manner as in the case where the polymer (A) solution is brought into contact with the base material to which the coupling agent is bonded, and the unreacted compound (B). The polymer (A) is chemisorbed on the compound (B) by electrostatic interaction or bipolar interaction with the amino group or carboxyl group of the compound, and then the substrate is further treated with the compound ( The polymer (A) and the compound (B) formed on the substrate are repeated by repeating the heat treatment step after contacting the solution of B) with the compound (B) and chemically adsorbing the compound (B) to the polymer (A). A thin film having a thickness can be formed on the substrate. The operation of each step can be performed by the above method, and the number of repetitions can be performed without any particular limitation.
[0081]
In addition, each time this step is repeated, the types of the polymer (A) and the compound (B) to be used can be arbitrarily changed. That is, the types of the polymer (A) and the compound (B) to be used may be the same or different for each repeating step. Production of a polymer thin film using the plurality of polymers (A) or compound (B) is effective for the production of a substrate having polymer thin films having a plurality of different functions.
[0082]
In addition, each time the polymer (A) and the compound (B) are adsorbed, the process of adsorbing the polymer (A) and the compound (B) is repeatedly performed without performing the heat treatment, and then the heat treatment is performed to cause the adsorption. The polymer (A) and the compound (B) are combined to form an amide bond or an imide bond at a time, whereby a polymer thin film having a thickness can be similarly produced.
[0083]
Moreover, after adsorption | suction of the same polymer (A) and a compound (B), it heat-processes, Furthermore, it changes by the kind of a polymer (A) and a compound (B), and also adsorb | sucks, and also heat-processes after that. Well, these can be chosen arbitrarily.
[0084]
According to the production method of the present invention, a substrate having a polymer thin film having an arbitrary film thickness of 1 nm to 100 nm can be easily produced. The polymer thin film of the base material produced by the production method of the present invention has an extremely good thickness accuracy within a standard deviation of 2.0 nm and R based on the film thickness value obtained by ellipsometry and the measurement of the surface profile by a scanning probe microscope. _ms It has a high surface flatness within a value (root mean square surface roughness) of 2.0 nm, and has excellent water resistance and solvent resistance.
[0085]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the scope of these examples.
[0086]
The measurement and evaluation methods used are shown below.
(1) Ellipsometry:
The film thickness of the polymer thin film was measured at an incident angle of 70 ° using an automatic ellipsometer (MARY-102 manufactured by Photodevice) using a He—Ne laser as a light source.
[0087]
(2) Fourier transform infrared spectroscopy (FT-IR):
The FT-IR spectrum of the polymer thin film was measured in a reflection absorption mode (incident angle of 85 °) using a Fourier transform infrared spectrophotometer (Bio-Rad FTS-60A).
[0088]
(3) X-ray photoelectron spectroscopy (XPS):
Using an X-ray photoelectron spectrometer (Shimadzu ESCA-850), the XPS spectrum of the polymer thin film was measured using MgKα as the X-ray source.
[0089]
(4) Atomic force microscope (AFM):
The surface profile of the polymer thin film was measured in contact mode using a scanning probe microscope (SPI3700 manufactured by Seiko Denshi).
[0090]
<Example 1>
A glass substrate having a gold layer with a thickness of 150 nm formed on the surface was immersed in a 5 mmol / l ethanol solution of cystamine at 50 ° C. for 3 hours, then taken out, ultrasonically washed in ethanol, and nitrogen. Blow dry with gas. This process is referred to as process (II).
[0091]
The base material thus obtained was immersed in a 2-butanone solution of 0.1 mmol / l of a repeating unit of an alternating copolymer of maleic acid monomethyl ester and styrene (weight average molecular weight 50,000) at room temperature for 1 hour. Then, it was taken out from the solution, washed by being immersed in 2-butanone, and further blow-dried with nitrogen gas. These steps are referred to as step (II).
[0092]
Next, the substrate was immersed in a 25 mmol / liter toluene solution of ethylenediamine at room temperature for 1 hour, then taken out of the solution, washed by immersion in toluene, and further blow-dried with nitrogen gas. It was. These steps are referred to as step (III).
[0093]
Further, the substrate was heat-treated in a constant temperature bath at 180 ° C. under a reduced pressure of 0.01 Pa or less for 6 hours. This step is referred to as step (IV).
[0094]
By further repeating the steps (II) to (IV) on the substrate thus obtained, a substrate having a polymer thin film composed of an alternating copolymer of maleic acid monomethyl ester and styrene is obtained. It was.
[0095]
About the base material which has the obtained polymer thin film, process (II)-process (IV) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The change in film thickness with the number of repetitions is shown in FIG. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (IV), and the film thickness of the thin film obtained by repeating 10 times was 10.9 nm.
[0096]
Formation of amide bond and imide bond between alternating copolymer of maleic acid monomethyl ester and styrene and ethylenediamine from FT-IR measurement and XPS analysis on substrate having polymer thin film obtained from 10 repeated operations Was confirmed: ν _{C = O} , 1640cm ^-1 Ν _{C = O} , 1701cm ^-1 N _1s Binding energy, 401 eV.
[0097]
In addition, from the AFM (Atomic Force Microscope) image, a surface profile with excellent flatness was observed. On the other hand, all of the films were tested by a solvent resistance test immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. Since there was no change in the thickness value, high film stability was proved.
[0098]
By the above method, a glass substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic acid monomethyl ester and styrene as a constituent element on a gold layer. A material was prepared.
[0099]
<Example 2>
Except not performing step (IV), the base material obtained by carrying out similarly to Example 1 was heat-processed for 6 hours under the reduced pressure of 0.01 Pa or less with a 180 degreeC thermostat, and maleic acid monomethyl ester, styrene, A base material having a polymer thin film having an alternating copolymer as a constituent element was obtained.
[0100]
About the base material which has the obtained polymer thin film, when the process (II)-process (III) were repeated 1-9 times, and after heat-processing this base material, the film thickness of a thin film was measured by ellipsometry did. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of the steps (II) to (III), the film thickness of the thin film obtained by repeating 9 times was 8.8 nm, The thickness of the thin film after the heat treatment was 8.8 nm.
[0101]
About the base material which has the polymer thin film obtained by heat-processing after 9 times of repeating operations, from FT-IR measurement and XPS analysis, the amide bond between the alternating copolymer of maleic acid monomethyl ester and styrene, and ethylenediamine, and Formation of imide bond was confirmed: ν _{C = O} , 1645cm ^-1 Ν _{C = O} , 1702cm ^-1 N _1s Binding energy, 401.2 eV.
[0102]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0103]
By the above method, a glass substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic acid monomethyl ester and styrene as a constituent element on a gold layer. A material was prepared.
[0104]
<Example 3>
In step (III), instead of immersing the substrate in a 25 mmol / liter toluene solution of ethylenediamine at room temperature for 1 hour and then removing it from the solution and washing it by immersing in toluene, the substrate is polyallylamine. Except that it was immersed in a methanol solution of 0.1 mmol / L per repeating unit (weight average molecular weight 15,000) at room temperature for 1 hour, then taken out from the solution and washed by immersion in methanol. In the same manner as in Example 1, a substrate having a polymer thin film composed of an alternating copolymer of maleic acid monomethyl ester and styrene as a constituent element was obtained.
[0105]
About the base material which has the obtained polymer thin film, process (II)-process (IV) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (IV), and the film thickness of the thin film obtained by repeating 10 times was 13.1 nm.
[0106]
From the FT-IR measurement and the XPS analysis, the amide bond and the imide bond between the alternating copolymer of maleic acid monomethyl ester and styrene and the polyallylamine were obtained from the substrate having the polymer thin film obtained from 10 repeated operations. Generation confirmed: ν _{C = O} , 1641cm ^-1 Ν _{C = O} , 1702cm ^-1 N _1s Binding energy, 401 eV.
[0107]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0108]
By the above method, a glass substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic acid monomethyl ester and styrene as a constituent element on a gold layer. A material was prepared.
[0109]
<Example 4>
The same procedure as in Example 1 was used except that a polyethylene terephthalate (PET) resin substrate having a 150 nm thick gold layer formed on the surface was used instead of the glass substrate having a gold layer formed on the surface. Thus, a base material having a polymer thin film composed of an alternating copolymer of maleic acid monomethyl ester and styrene was obtained.
[0110]
About the base material which has the obtained polymer thin film, process (II)-process (IV) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (IV), and the film thickness of the thin film obtained by repeating 10 times was 11.5 nm.
[0111]
Formation of amide bond and imide bond between alternating copolymer of maleic acid monomethyl ester and styrene and ethylenediamine from FT-IR measurement and XPS analysis on substrate having polymer thin film obtained from 10 repeated operations Was confirmed: ν _{C = O} , 1640cm ^-1 Ν _{C = O} , 1703cm ^-1 N _1s Binding energy, 401.2 eV.
[0112]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0113]
By the above method, it is made of PET resin having a polymer thin film with high film stability, excellent thickness accuracy, and good surface flatness, which is composed of an alternating copolymer of maleic acid monomethyl ester and styrene on the gold layer. A substrate was prepared.
[0114]
<Example 5>
Instead of a glass substrate having a gold layer formed on the surface, a quartz substrate is used, and in step (I), the substrate is placed in a 5 mmol / liter ethanol solution of cystamine at 50 ° C. for 3 hours. After immersing, instead of ultrasonically cleaning in ethanol, the sample was immersed in a 5 mmol / liter methanol solution of 3-aminopropyltrimethoxysilane at 50 ° C. for 3 hours, and then ultrasonically cleaned in methanol. In the same manner as in Example 1, a base material having a polymer thin film containing an alternating copolymer of maleic acid monomethyl ester and styrene as a constituent element was obtained.
[0115]
About the base material which has the obtained polymer thin film, process (II)-process (IV) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (IV), and the film thickness of the thin film obtained by repeating 10 times was 11.3 nm.
[0116]
Formation of amide bond and imide bond between alternating copolymer of maleic acid monomethyl ester and styrene and ethylenediamine from FT-IR measurement and XPS analysis on substrate having polymer thin film obtained from 10 repeated operations Was confirmed: ν _{C = O} , 1642cm ^-1 Ν _{C = O} , 1701cm ^-1 N _1s Binding energy, 401.1 eV.
[0117]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0118]
By the above method, a quartz substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic acid monomethyl ester and styrene as a constituent element was produced.
[0119]
<Example 6>
A base material obtained in the same manner as in Example 5 except that step (IV) was not carried out was heat-treated in a thermostatic bath at 180 ° C. under a reduced pressure of 0.01 Pa or less for 6 hours to obtain monomethyl maleate and styrene. A base material having a polymer thin film having an alternating copolymer as a constituent element was obtained.
[0120]
About the base material which has the obtained polymer thin film, when the process (II)-process (III) were repeated 1-9 times, and after heat-processing this base material, the film thickness of a thin film was measured by ellipsometry did. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (III), and the film thickness of the thin film obtained by repeating 9 times was 8.9 nm, The thickness of the thin film after the heat treatment was 8.9 nm.
[0121]
About the base material which has the polymer thin film obtained by heat-processing after 9 times of repeating operations, from FT-IR measurement and XPS analysis, the amide bond between the alternating copolymer of maleic acid monomethyl ester and styrene, and ethylenediamine, and Formation of imide bond was confirmed: ν _{C = O} , 1641cm ^-1 Ν _{C = O} , 1701cm ^-1 N _1s Binding energy, 401.2 eV.
[0122]
In addition, a surface profile with excellent flatness is observed from the AFM image, and on the other hand, there is no change in film thickness value due to a solvent resistance test that is immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. Membrane stability was demonstrated.
[0123]
By the above method, a quartz substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic acid monomethyl ester and styrene as a constituent element was produced.
[0124]
<Example 7>
A base material having a polymer thin film having an alternating copolymer of maleic acid monomethyl ester and styrene as constituents was obtained in the same manner as in Example 5 except that trans-1,4-cyclohexanediamine was used instead of ethylenediamine. It was.
[0125]
About the base material which has the obtained polymer thin film, process (II)-process (IV) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (IV), and the film thickness of the thin film obtained by repeating 10 times was 11.7 nm.
[0126]
For a substrate having a polymer thin film obtained from 10 repetitive operations, an FT-IR measurement and XPS analysis showed that between an alternating copolymer of maleic acid monomethyl ester and styrene and trans-1,4-cyclohexanediamine. Formation of amide bond and imide bond was confirmed: ν _{C = O} , 1643cm ^-1 Ν _{C = O} , 1700cm ^-1 N _1s Binding energy, 401 eV.
[0127]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0128]
By the above method, a quartz substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic acid monomethyl ester and styrene as a constituent element was produced.
[0129]
<Example 8>
In step (II), instead of the alternating copolymer of maleic acid monomethyl ester and styrene (weight average molecular weight 50,000), an alternating copolymer of maleic acid and methyl vinyl ether (weight average molecular weight 70,000) was used. In the same manner as in Example 1, a base material having a polymer thin film containing an alternating copolymer of maleic acid and methyl vinyl ether as a constituent element was obtained.
[0130]
About the base material which has the obtained polymer thin film, process (II)-process (IV) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (IV), and the film thickness of the thin film obtained by repeating 10 times was 11.3 nm.
[0131]
From the FT-IR measurement and XPS analysis, the formation of the amide bond and the imide bond between the alternating copolymer of maleic acid and methyl vinyl ether and ethylenediamine was carried out on the substrate having the polymer thin film obtained from 10 repeated operations. Confirmed: ν _{C = O} , 1642cm ^-1 Ν _{C = O} , 1703cm ^-1 N _1s Binding energy, 401.1 eV.
[0132]
In addition, a surface profile with excellent flatness was observed from the AFM image. On the other hand, the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. Stability proved.
[0133]
By the above method, a glass substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic acid and methyl vinyl ether as a constituent element on a gold layer. Was made.
[0134]
<Example 9>
In the step (II), an alternating copolymer of maleic acid and styrene (weight average molecular weight 70,000) was used instead of the alternating copolymer of maleic acid monomethyl ester and styrene (weight average molecular weight 50,000). In the same manner as in Example 5, a substrate having a polymer thin film composed of an alternating copolymer of maleic acid and styrene as a constituent element was obtained.
[0135]
About the base material which has the obtained polymer thin film, process (II)-process (IV) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (IV), and the film thickness of the thin film obtained by repeating 10 times was 11.5 nm.
[0136]
About the base material which has the polymer thin film obtained from 10 repetition operations, the formation of the amide bond and the imide bond between the alternating copolymer of maleic acid and styrene and ethylenediamine was confirmed from FT-IR measurement and XPS analysis. It was done.
: Ν _{C = O} , 1645cm ^-1 Ν _{C = O} , 1701cm ^-1 N _1s Binding energy, 401 eV.
[0137]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0138]
By the above method, a quartz substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic acid and styrene as a constituent element was produced.
[0139]
<Example 10>
In step (II), instead of the alternating copolymer of maleic acid monomethyl ester and styrene (weight average molecular weight 50,000), the alternating copolymer of maleic anhydride and styrene (weight average molecular weight 50,000) was used. In the same manner as in Example 1, a base material having a polymer thin film composed of an alternating copolymer of maleic anhydride and styrene as a constituent element was obtained.
[0140]
About the base material which has the obtained polymer thin film, process (II)-process (IV) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (IV), and the film thickness of the thin film obtained by repeating 10 times was 11.2 nm.
[0141]
Formation of amide bond and imide bond between alternating copolymer of maleic anhydride and styrene and ethylenediamine from FT-IR measurement and XPS analysis on substrate having polymer thin film obtained from 10 repeated operations Was confirmed: ν _{C = O} , 1645cm ^-1 Ν _{C = O} , 1702cm ^-1 N _1s Binding energy, 401 eV.
[0142]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0143]
By the above method, a glass substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic anhydride and styrene as a constituent element on a gold layer. A material was prepared.
[0144]
<Example 11>
In step (II), instead of the alternating copolymer of maleic acid monomethyl ester and styrene (weight average molecular weight 50,000), the alternating copolymer of maleic anhydride and styrene (weight average molecular weight 50,000) was used. In the same manner as in Example 2, a substrate having a polymer thin film composed of an alternating copolymer of maleic anhydride and styrene was obtained.
[0145]
About the base material which has the obtained polymer thin film, when the process (II)-process (III) were repeated 1-9 times, and after heat-processing this base material, the film thickness of a thin film was measured by ellipsometry did. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (III), and the film thickness of the thin film obtained by repeating 9 times was 9.3 nm, The thickness of the thin film after the heat treatment was 9.3 nm.
[0146]
About the base material which has the polymer thin film obtained by heat-processing after 9 times of repeating operations, from FT-IR measurement and XPS analysis, the amide bond between the alternating copolymer of maleic anhydride and styrene, and ethylenediamine, and Formation of imide bond was confirmed: ν _{C = O} , 1640cm ^-1 Ν _{C = O} , 1702cm ^-1 N _1s Binding energy, 401.2 eV.
[0147]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0148]
By the above method, a glass substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of maleic anhydride and styrene as a constituent element on a gold layer. A material was prepared.
[0149]
<Example 12>
In step (II), an alternating copolymer of itaconic anhydride and styrene (weight average molecular weight 42,000) was used instead of the alternating copolymer of maleic acid monomethyl ester and styrene (weight average molecular weight 50,000). In the same manner as in Example 1, a substrate having a polymer thin film composed of an alternating copolymer of itaconic anhydride and styrene was obtained.
[0150]
About the base material which has the obtained polymer thin film, process (II)-process (IV) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (II) to (IV), and the film thickness of the thin film obtained by repeating 10 times was 11.8 nm.
[0151]
Formation of amide bonds and imide bonds between an alternating copolymer of itaconic anhydride and styrene and ethylenediamine from a FT-IR measurement and XPS analysis on a substrate having a polymer thin film obtained from 10 repeated operations Was confirmed: ν _{C = O} , 1645cm ^-1 Ν _{C = O} , 1702cm ^-1 N _1s Binding energy, 401 eV.
[0152]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0153]
By the above method, a glass substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising an alternating copolymer of itaconic anhydride and styrene as a constituent element on a gold layer. A material was prepared.
[0154]
<Example 13>
A glass substrate having a gold layer with a thickness of 150 nm formed on the surface was immersed in a 5 mmol / l ethanol solution of 3-mercaptopropionic acid at 50 ° C. for 3 hours, and then removed and ultrasonically cleaned in ethanol. And blow-dried with nitrogen gas. These steps are referred to as step (V).
[0155]
The obtained base material was immersed in a 0.1 mmol / liter methanol solution of polyallylamine (weight average molecular weight 15,000) per unit at room temperature for 1 hour, then taken out from the solution and put into methanol. It was washed by dipping and further blow-dried with nitrogen gas. These steps are referred to as step (VI).
[0156]
Next, the substrate was immersed in a 25 mmol / liter methanol solution of succinic acid at room temperature for 1 hour, then taken out from the solution, washed by immersing in methanol, and blow-dried with nitrogen gas. I let you. These steps are referred to as step (VII).
[0157]
Further, the base material was heat-treated in a constant temperature bath at 180 ° C. under a reduced pressure of 0.01 Pa or less for 6 hours. These steps are referred to as step (VIII).
[0158]
A base material having a polymer thin film containing polyallylamine as a constituent element was obtained by repeating the steps (VI) to (VIII) on the base material thus obtained.
[0159]
About the base material which has the obtained polymer thin film, process (VI)-process (VIII) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (VI) to (VIII), and the film thickness of the thin film obtained by repeating 10 times was 10.1 nm.
[0160]
About the base material which has the polymer thin film obtained from 10 repetition operation, the production | generation of the amide bond between polyallylamine and succinic acid was confirmed from the FT-IR measurement and XPS analysis: (nu) _{C = O} , 1645cm ^-1 N _1s Binding energy, 401 eV.
[0161]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0162]
By the above method, a glass substrate having a polymer thin film having polyallylamine as a constituent element on the gold layer and having high film stability, excellent thickness accuracy, and good surface flatness was produced.
[0163]
<Example 14>
Except not performing step (VIII), the base material obtained by carrying out similarly to Example 13 was heat-processed in the thermostat of 180 degreeC under pressure reduction of 0.01 Pa or less for 6 hours, and polyallylamine was made into the component. A substrate having a polymer thin film was obtained.
[0164]
About the base material which has the obtained polymer thin film, when the process (VI)-process (VII) were repeated 1-9 times, and after heat-processing this base material, the film thickness of a thin film was measured by ellipsometry did. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (VI) to (VII), and the film thickness of the thin film obtained by repeating 9 times was 8.8 nm, The thickness of the thin film after the heat treatment was 8.9 nm.
[0165]
About the base material which has the polymer thin film obtained by heat-processing after 9 repetition operation, the production | generation of the amide bond between polyallylamine and succinic acid was confirmed from the FT-IR measurement and XPS analysis: (nu) _{C = O} , 1648cm ^-1 N _1s Binding energy, 401.2 eV.
[0166]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0167]
By the above method, a glass substrate having a polymer thin film having polyallylamine as a constituent element on the gold layer and having high film stability, excellent thickness accuracy, and good surface flatness was produced.
[0168]
<Example 15>
In the step (VI), polyethyleneimine was used as a constituent in the same manner as in Example 13 except that polyethyleneimine (weight average molecular weight 10,000) was used instead of polyallylamine (weight average molecular weight 15,000). A substrate having a polymer thin film was obtained.
[0169]
About the base material which has the obtained polymer thin film, process (VI)-process (VIII) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (VI) to (VIII), and the film thickness of the thin film obtained by repeating 10 times was 10.8 nm.
[0170]
About the base material which has the polymer thin film obtained from 10 repetition operation, the production | generation of the amide bond between a polyethyleneimine and a succinic acid was confirmed from the FT-IR measurement and the XPS analysis: (nu) _{C = O} , 1644cm ^-1 Ν _{C = O} N _1s Binding energy, 401.2 eV.
[0171]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0172]
By the above method, a glass substrate having a polymer thin film having polyethylene imine as a constituent element on the gold layer, high film stability, excellent thickness accuracy, and good surface flatness was produced.
[0173]
<Example 16>
In step (VI), instead of polyallylamine (weight average molecular weight 15,000), a copolymer of 4-vinylaniline and styrene (weight average molecular weight 30,000, 4-vinylaniline content 35 mol%), In Step (VII), the same procedure as in Example 13 was used, except that a methanol solution of 5 mmol / l of trans-1,4-cyclohexanedicarboxylic acid was used in place of the 25 mmol / liter methanol solution of succinic acid. Thus, a base material having a polymer thin film having a copolymer of 4-vinylaniline and styrene as a constituent element was obtained.
[0174]
About the base material which has the obtained polymer thin film, process (VI)-process (VIII) were repeated 1 to 10 times, and the film thickness was measured by ellipsometry every time. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of steps (VI) to (VIII), and the film thickness of the thin film obtained by repeating 10 times was 11.3 nm.
[0175]
About the base material which has the polymer thin film obtained from 10 repetition operation, the production | generation of the amide bond between a polyethyleneimine and a succinic acid was confirmed from the FT-IR measurement and the XPS analysis: (nu) _{C = O} , 1645cm ^-1 Ν _{C = O} N _1s Binding energy, 401 eV.
[0176]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0177]
By the above method, a glass substrate having a polymer thin film having a high film stability, excellent thickness accuracy, and good surface flatness, comprising a copolymer of 4-vinylaniline and styrene as a constituent element on a gold layer. Was made.
[0178]
<Example 17>
In the same manner as in Example 1, the steps (I) to (IV) were performed. Next, the substrate was immersed in a solution of 0.1 mmol / l 2-butanone per repeating unit of an alternating copolymer of maleic acid and methyl vinyl ether (weight average molecular weight 70,000) at room temperature for 1 hour. The solution was taken out of the solution, washed by dipping in 2-butanone, and further blow-dried with nitrogen gas. These steps are referred to as step (IX). Subsequently, Step (III) and Step (IV) were performed on the substrate.
[0179]
By further repeating each step (II), (III), (IV), (IX), (III) and (IV) in this order on the substrate thus obtained, monomethyl maleate was obtained. A substrate having a polymer thin film composed of alternating copolymers of ester and styrene and alternating copolymers of maleic acid and methyl vinyl ether was obtained.
[0180]
For the substrate having the polymer thin film obtained, the steps (II), (III), (IV), (IX), (III), (IV) were repeated in this order, and the film thickness was measured by ellipsometry each time. Was measured. The change of the film thickness value with the number of repetitions is shown in FIG. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of each step (II), (III), (IV), (IX), (III) and (IV). The film thickness of the obtained thin film was 23.1 nm.
[0181]
For substrates having polymer thin films obtained from 10 repeated operations, from FT-IR measurement and XPS analysis, alternating copolymer of maleic acid monomethyl ester and styrene and alternating copolymer of maleic acid and methyl vinyl ether and ethylenediamine Formation of an amide bond and an imide bond between and _{C = O} , 1645cm ^-1 Ν _{C = O} , 1701cm ^-1 N _1s Binding energy, 401 eV.
[0182]
In addition, a surface profile with excellent flatness is observed from the AFM image. On the other hand, the film thickness value does not change in any of the solvent resistance tests that are immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. From this, high membrane stability was proved.
[0183]
By the above method, the film has high film stability, excellent thickness accuracy, and surface flatness, which are composed of alternating copolymer of maleic acid monomethyl ester and styrene and alternating copolymer of maleic acid and methyl vinyl ether on the gold layer. A glass substrate having a polymer thin film with good properties was produced.
[0184]
<Example 18>
Except for not performing step (IV), the base material obtained in the same manner as in Example 17 was heat-treated in a thermostatic bath at 180 ° C. under a reduced pressure of 0.01 Pa or less for 6 hours to obtain monomethyl maleate and styrene. And a substrate having a polymer thin film composed of an alternating copolymer of maleic acid and methyl vinyl ether.
[0185]
About the base material which has the obtained polymer thin film, after repeating each process (II), (III), (IX) and (III) 1 to 9 times, and after heat-processing this base material, a thin film The film thickness was measured by ellipsometry. The film thickness of the polymer thin film was confirmed to increase in proportion to the number of repetitions of each step (II), (III), (IX) and (III). The film thickness was 18.2 nm, and the thickness of the thin film after the heat treatment was 18.1 nm.
[0186]
About the base material which has the polymer thin film obtained by heat-processing after 9 times of repeating operation, from FT-IR measurement and XPS analysis, the alternating copolymer of maleic acid monomethyl ester and styrene, and maleic acid and methyl vinyl ether Formation of amide and imide bonds between the alternating copolymer and ethylenediamine was confirmed: v _{C = O} , 1642cm ^-1 Ν _{C = O} , 1702cm ^-1 N _1s Binding energy, 401 eV.
[0187]
Also, from the AFM image, a surface profile with excellent flatness was observed, while the film thickness value was not changed by a solvent resistance test that was immersed in water, ethanol, chloroform, and toluene at 50 ° C. for 48 hours. High membrane stability was demonstrated.
[0188]
By the above method, the film has high film stability, excellent thickness accuracy, and surface flatness, which are composed of alternating copolymer of maleic acid monomethyl ester and styrene and alternating copolymer of maleic acid and methyl vinyl ether on the gold layer. A glass substrate having a polymer thin film with good properties was produced.
[0189]
<Comparative Example 1>
Except not performing process (IV), it carried out similarly to Example 1, and obtained the base material which has the polymer thin film which used the alternating copolymer of maleic acid monomethylester and styrene as a component. The base material having the polymer thin film after repeated operation 9 times was confirmed to have a film thickness of 8.8 nm by ellipsometry, but it was resistant to immersion in water, ethanol, chloroform and toluene at 50 ° C. for 48 hours. As a result of the solvent test, it was found that the film thickness values decreased to 8.7, 4.5, 6.2, and 7.5 nm, respectively, and the solvent resistance was not high.
[0190]
<Comparative example 2>
A glass substrate having a gold layer with a thickness of 150 nm formed on the surface was immersed in a 5 mmol / liter ethanol solution of cystamine dihydrochloride at 50 ° C. for 3 hours, then taken out and ultrasonically cleaned in ethanol. And blow-dried with nitrogen gas.
[0191]
The obtained base material was immersed in an aqueous solution of 0.1 mmol / L per repeating unit of poly (sodium 4-styrenesulfonate) (weight average molecular weight 70,000) at room temperature for 1 hour. It was taken out from the water, washed by dipping in water, and blow-dried with nitrogen gas. Next, the substrate is immersed in an aqueous solution of 0.1 mmol / liter of polyallylamine hydrochloride per unit at room temperature for 1 hour, then taken out of the solution, washed by immersing in water, and further nitrogen gas. Was blow dried.
[0192]
The above operation was repeated, and the substrate having the polymer thin film after the 10th repeated operation was confirmed to have a film thickness of 15.5 nm by ellipsometry analysis, but in water and ethanol at 40 ° C. for 48 hours. As a result of the solvent resistance test to be immersed, the film thickness values decreased to 8.5 and 7.5 nm, respectively, and it was confirmed that the solvent resistance was not high.
[0193]
<Comparative Example 3>
The quartz substrate was immersed in a methanol / trimethyl methacrylate solution of 3-trimethoxysilylpropyl at a concentration of 3 mmol / liter at 50 ° C. for 3 hours, then taken out, ultrasonically washed in methanol, and further kept in a constant temperature bath at 100 ° C. Heat treatment was performed for 1 hour under a reduced pressure of 0.01 Pa or less. The resulting substrate was immersed in a 25 mmol / l toluene solution of methyl methacrylate and at 60 ° C. in the presence of azobisisobutyronitrile (1 mole percent relative to methyl methacrylate) The polymerization reaction was carried out for 30 minutes, 2 hours, 12 hours, or 48 hours.
[0194]
As a result of measuring the thickness of the substrate having the polymer thin film by ellipsometry, the thin films having a polymerization reaction time of 30 minutes, 2 hours, 12 hours, and 48 hours were 25.2, 27.3, and 27. respectively. The film thickness value was 8, 30.1 nm. From the above results, it was found that it was not easy to produce a substrate having a polymer thin film with a controlled film thickness by this method.
[0195]
【The invention's effect】
The present invention provides a substrate having a polymer thin film having high bond stability and excellent flatness and a simple method for producing a substrate having the polymer thin film capable of controlling the film thickness in nanometer units. The polymer thin film of the substrate having the polymer thin film of the present invention has excellent thickness accuracy and solvent resistance.
[Brief description of the drawings]
FIG. 1 is a graph showing changes in film thickness of a polymer thin film made of an alternating copolymer of maleic acid monomethyl ester and styrene prepared in Example 1. FIG.
2 is a graph showing changes in the film thickness of a polymer thin film made of an alternating copolymer of maleic acid monomethyl ester and styrene and an alternating copolymer of maleic acid and methyl vinyl ether prepared in Example 17. FIG.

Claims (13)

(1) A step of bringing a coupling agent having one type of functional group capable of forming an imide bond or an amide bond into contact with the substrate surface to bond the coupling agent to the substrate surface;
(2) One or more functional groups possessed by the coupling agent bonded to the substrate have one or more functional groups capable of forming an imide bond or an amide bond, or an imide bond or an amide bond. A step of bringing the base material into contact with a solution of the polymer (A) having one or more structural units of the following, and chemically adsorbing the polymer (A) to a coupling agent bonded to the base material:
(3) The base material on which the polymer (A) has been chemically adsorbed has two or more of one type of functional group or structural unit of the polymer (A) and one type of functional group capable of forming an imide bond or an amide bond. Contacting the solution of the compound (B) to cause the polymer (A) to chemisorb the compound (B);
(4) A polymer thin film characterized by heating the base material to form an imide bond or an amide bond, and (5) repeating the steps (2) to (4) at least once on the base material. The manufacturing method of the base material which has. The functional group capable of forming an imide bond or an amide bond is an amino group or a carboxyl group, and the structural unit capable of forming an imide bond or an amide bond is represented by the general formula (I)

Or general formula (II)

The manufacturing method of the base material which has a polymer thin film of Claim 1 which is a cyclic carboxylic anhydride unit shown by these. Polymer (A) having a carboxyl group having one or more selected from the group consisting of maleic acid, maleic acid monoalkyl ester, itaconic acid and itaconic acid monoalkyl ester as a polymerization component, or copolymerized with the polymerization component The method for producing a substrate having a polymer thin film according to claim 1, which is a copolymer having a carboxyl group with a possible monomer. Polymer (A) is
Formula (I)

Or general formula (II)

The method for producing a substrate having a polymer thin film according to claim 1, which is a polymer having a cyclic carboxylic anhydride unit represented by the formula (1) or a copolymer with a monomer copolymerizable therewith. The polymer (A) is a polymer having an amino group having at least one of allylamine and 4-vinylaniline as a polymerization component, a copolymer having an amino group with a monomer copolymerizable with the polymerization component, or polyethyleneimine. A method for producing a substrate having the polymer thin film according to 1. The polymer thin film according to claim 1, wherein the compound (B) is one selected from the group consisting of ethylenediamine, trans-1,4-cyclohexanediamine, polyallylamine, succinic acid and trans-1,4-cyclohexanedicarboxylic acid. The manufacturing method of the base material which has this. Substrate, the surface is contacted with at least a coupling agent, Au, Ag, metal selected from the group consisting of Cu and Pt _{or,, SIO 2, Al 2 O} 3, InO 2, SnO 2, ZrO 2, TIO 2 The method for producing a substrate having a polymer thin film according to claim 1, wherein the substrate is coated with a metal oxide selected from the group consisting of HfO ₂ and HfO ₂ . The method for producing a substrate having a polymer thin film according to claim 1, wherein in the step (2) after the second time, the substrate is brought into contact with the same or different solution of the polymer (A) for each repetition. Claims (2) and (3) are repeated one or more times without performing the step (4) to form an imide bond or an amide bond by heating the substrate, and then the substrate is heat-treated. A method for producing a substrate having the polymer thin film according to 1. Au, Ag, Cu, metal selected from the group consisting of Pt, or _{SIO 2, Al 2 O 3,} InO 2, SnO 2, ZrO 2, TIO 2 and the surface of a metal oxide selected from the group consisting of HfO ₂ is A coupling agent having an amino group or a carboxyl group is bonded to a coated glass, quartz or resin base material,
A polymer (A) bonded with a functional group of the coupling agent by forming an imide bond or an amide bond;
A compound selected from the group consisting of unreacted functional groups or structural units of the polymer (A) and ethylenediamine, trans-1,4-cyclohexanediamine, polyallylamine, succinic acid, or trans-1,4-cyclohexanedicarboxylic acid ( B) is bonded to form an imide bond or an amide bond,
Further, the unreacted functional group of the compound (B) is bonded to the polymer (A) of the same or different type by forming an imide bond or an amide bond with the polymer (A). One or more types of polymers (A) and one or more types of compounds (B) in which the group or structural unit is bonded to the compound (B) that is the same or different from the compound (B) by forming an imide bond or an amide bond A substrate having a polymer thin film composed of a plurality of repetitions in which and form an imide bond or an amide bond. Polymer (A) is an alternating copolymer of maleic acid monomethyl ester and styrene, an alternating copolymer of maleic acid and methyl vinyl ether, an alternating copolymer of maleic acid and styrene, an alternating copolymer of maleic anhydride and styrene, itaconic anhydride 11. A substrate having a polymer thin film according to claim 10, which is selected from the group consisting of an alternating copolymer of styrene and styrene, polyallylamine, a copolymer of ethyleneimine 4-vinylaniline and styrene. The substrate having a polymer thin film according to claim 10, wherein the coupling agent is 3-aminopropyltrimethoxysilane, cystamine or 3-mercaptopropionic acid. The base material which has a polymer thin film couple | bonded by the covalent bond obtained by the manufacturing method as described in any one of Claims 1-9.

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