JP3697561B2 - Component gradient composite of organic polymer and metal oxide and method for producing the same - Google Patents

Description

（式中、Ｍは珪素原子、ＲはＣ_ｍＨ_２ｍ＋１、ｍは１〜４の整数、ｎは１〜１０の整数を表わす。）
【００２３】
本発明は、有機高分子と金属アルコキシドとそれらの共通溶媒及び／又は金属アルコキシドの重合触媒からなる均質溶液を、有機高分子または無機の基材上に塗布したものを、水及び／又は金属アルコキシドの重合触媒及び／又は有機溶媒を空気中に含ませた雰囲気下に保持した後、乾燥、熱処理を行うことを特徴とする有機高分子と金属酸化物との成分傾斜複合体の製造方法を含むものである。
【００２４】
本発明の有機高分子と金属酸化物との成分傾斜複合体の製造方法は、その金属酸化物成分が、有機高分子成分の存在下で金属アルコキシドまたはその低縮合物の加水分解・重縮合により、有機高分子成分中に均質に分散して得られたものであり、特に金属アルコキシドが一般式１で示されるシリコンアルコキシドまたはその低縮合物であることを特徴とする有機高分子と金属酸化物との成分成分傾斜複合体の製造法である。
【００２５】
（一般式１）
【化４】

（式中、Ｍは珪素原子、ＲはＣ_ｍＨ_２ｍ＋１、ｍは１〜４の整数、ｎは１〜１０の整数を表わす。）
【００２６】
また本発明の有機高分子と金属酸化物との成分傾斜複合体の製造方法は、特に雰囲気中及び／又は均質溶液中に含まれる金属アルコキシドの重合触媒として、同種または異種の塩基性物質を用いることを特徴とする有機高分子と金属酸化物との成分傾斜複合体の製造方法を含むものである。
【００２７】
即ち、本発明は、少なくとも１種ずつの有機高分子と金属酸化物を含有する有機高分子と金属酸化物との複合体において、含有される金属酸化物成分が複合体の内部において異なる濃度で存在し、複合体の表面から深さ方向に、金属酸化物成分濃度が連続的に変化する成分傾斜構造を形成していること、
【００２８】
且つ複合体中の金属酸化物成分濃度が最も高い所で５〜１００重量％、最も低いところで０〜５０重量％であること、且つ高い所と低い所との含有率の比が１．５以上であることを特徴とする有機高分子と金属酸化物との成分傾斜複合体に関するものであり、特に有機高分子存在下で金属アルコキシドまたはその低縮合物を重縮合して得られる金属酸化物と有機高分子からなる、有機高分子と金属酸化物との成分傾斜複合体を中心としたものである。
【００２９】
当該有機高分子と金属酸化物との成分傾斜複合体では、複合体の少なくとも１つの表面において、金属酸化物成分が複合体の平均金属酸化物濃度を越えて存在しているもの、または少なくとも１つの表面において金属酸化物成分が複合体の平均金属酸化物濃度以下であるものを含む。また当該有機高分子と金属酸化物との成分傾斜複合体は、深さ方向において金属酸化物の最高含有率を有する厚みより金属酸化物濃度傾斜を有する厚みが大きいものを含むものである。
【００３０】
また当該有機高分子と金属酸化物との成分傾斜複合体は、複合体中に含有される金属酸化物の大きさが平均径０．０１μｍ〜５μｍであるものを含む。また当該有機高分子と金属酸化物との成分傾斜複合体は、その形態が塗膜や糸、フィルム、球状のものであるほかブロック等の各種形状の成形体であるものを含む。
【００３１】
本発明においては、金属酸化物が有機高分子中において深さ方向以外では均質性を保ちながら、深さ方向に連続的に変化している領域を有することを基本とする。従って、単に不規則な凝集や相分離により、不連続的に金属酸化物濃度の異なる領域を有するものや、塗装により形成される一定金属酸化物含有率を有する均一塗膜を基材の表面上に有するものなどとは異なる。
【００３２】
本発明に使用できる有機高分子としては、有機高分子存在下での金属アルコキシドの重縮合により、均質な有機高分子と金属酸化物との複合体をつくることが可能なものであればよく、特に限定されないが、具体的には、例えばフェノ−ル樹脂、エポキシ樹脂、アクリル樹脂、アルキド樹脂、メラミン樹脂、尿素樹脂等の熱硬化性樹脂やナイロン、ポリエステル、アクリル樹脂等の熱可塑性樹脂、またポリブタジエンやＳＢＳのようなゴム系樹脂等を用いることが可能であり、特に熱硬化性樹脂、中でもエポキシ樹脂、アクリル樹脂、アルキド樹脂、メラミン樹脂が好ましい。
【００３３】
製造上の容易さからの観点では、金属アルコキシドやその縮合物またはそれらと溶媒等からなる均質溶液に溶解するか、または膨潤する有機高分子またはその前駆体樹脂であるものが望ましい。
【００３４】
本発明における金属アルコキシドとしては、一般式１に示されるシリコンアルコキシド及び／またはその縮合物が用いられる。その他の金属アルコキシド類としては、Ｔｉ、Ａｌ、Ｚｒ等の金属アルコキシドも可能であるが、Ｓｉのアルコキシド類、またはＳｉを主成分とする他金属アルコキシド類との混合物を用いると、加水分解・重縮合の反応速度が緩やかで濃度傾斜を制御する上で特に好ましい。
【００３５】
本発明における有機高分子と金属酸化物との成分傾斜複合体は、金属酸化物成分（Ａ）の複合体中での含有率（以下、単に金属酸化物含有率と言うことがある。）の最も高い部分が５〜１００重量％であり、最も低い部分では０〜５０重量％であるものが好ましい。
【００３６】
最も高い部分での金属酸化物含有率が５重量％未満では、複合化の効果が不十分であり、また最も低い部分での金属酸化物含有率が５０重量％を越えるものは複合体が脆くなったり、クラック等の発生が生じ易くなったり、また複合体全体の厚みが非常に薄くなくてはならない等の制限が大きくなり、好ましくない。
【００３７】
また金属酸化物含有率の最も高い所と低い所との比は１．５以上、好ましくは２以上であることが必要である。当該比が１．５未満では成分傾斜複合体としての効果が不十分である。また金属酸化物濃度が深さ方向に傾斜的に変化している厚み（ｄ1）が、最も高い金属酸化物含有率を示す領域の厚み（ｄ2）より大きい場合に傾斜複合材としての効果がより明確である。
【００３８】
本発明における金属酸化物の大きさとしては、直径０．０１μｍ〜５μｍである。特に金属酸化物の大きさが０．０１μｍ〜０．５μｍで、用いる有機高分子が透明なものである場合は、本発明の複合体は透明〜半透明の外観を有する。
また金属酸化物の大きさが０．５μｍ〜５μｍの場合は、半透明〜不透明の外観を有する。
【００３９】
いずれにしても、金属アルコキシドまたはその縮合物を有機高分子存在下で重縮合させて得られる金属酸化物と有機高分子からなる成分傾斜複合体では、予め製造された金属酸化物粒子と有機高分子を混合分散させるのに比べて、金属酸化物粒子の粒径制御が極微小粒径まで容易である。
【００４０】
従来のシリカ等の補強添加用粒子としては、直径１〜２μｍ程度のものまでが均質分散の可能性またコスト的にみて、その限界となっている。さらに小さい微粒子を用いる場合は、有機高分子との密度差や微粒子の凝集により、均質な分散またはその制御が困難である場合が多い。
【００４１】
本発明においては、金属酸化物の平均粒径がナノメ−タ−サイズのものまで均質に含まれ、且つ分散構造制御された成分傾斜複合体を得ることができる。
本発明における金属酸化物の大きさは、走差型電子顕微鏡等による測定では０．０１μｍ以下の粒径をとらえるのが難しいことから０．０１μｍの数値を付しているが、０．０１μｍより小さくてもなんら差し支えない。しかし平均粒径が５μｍ以上では均質な成分傾斜複合体が得られ難くなる。
【００４２】
本発明の有機高分子と金属酸化物との成分傾斜複合体を得る方法としては、最終的に得られる成分傾斜複合体がミクロ的に均質な分散を保ちながら、且つ複合体の深さ方向に連続的に金属酸化物濃度が変化する領域を有するものであれば良く、特に製造方法によって限定されないものである。
【００４３】
しかしながら、その具体的製造方法の一例を挙げれば、例えば、有機高分子成分及び金属アルコキシドまたはその縮合物、及び／又は水、及び／または触媒、及び／または有機溶媒を原料として用いて、金属アルコキシドの加水分解・重縮合、樹脂の硬化反応、及び／または溶媒キャストを行わせる際に、最終的に得られる複合体の深さ方向において不均一な金属アルコキシド類の加水分解・重縮合を生じるような操作を行うものである。
【００４４】
更に具体的には、上記原料の内、特定の原料成分（例えば、金属アルコキシドや塩基性触媒や水）の濃度分布を深さ方向にもたせたり、一方向からの外部刺激（例えば加熱）を行うことにより、傾斜的な金属酸化物濃度分布を発現させることが可能である。
【００４５】
例えば、有機高分子と金属アルコキシドまたはその縮合物とそれらの共通溶媒及び／又は金属アルコキシドの重合触媒からなる均質溶液を基材上に塗布したものを、水及び／又は金属アルコキシドの重合触媒及び／又は有機溶媒を空気中に含ませてなる雰囲気下に保持した後、乾燥、熱処理を行うことで、塗膜中での金属酸化物濃度の傾斜を発現させることができる。
【００４６】
本発明において、雰囲気中または均質溶液中に含まれる金属アルコキシドの重合触媒としては同一または異種の酸または塩基性物質が用いられるが、特に各種アミン化合物やアンモニアのような塩基性物質を用いるのは傾斜複合体中の金属酸化物の微粒子化や成分傾斜制御において好ましい。
【００４７】
また本発明において雰囲気中に含まれる有機溶媒としては、有機高分子等からなる溶液と均質に混和するものが好ましく、また溶液中に既に含まれている有機溶媒とは異なる種類のものであるのが特に好ましい。
【００４８】
本発明の有機高分子と金属酸化物との成分傾斜複合体は、塗膜や糸、フィルム、微粒子等の各種成形体や成形原料に用いることが可能である。また他の金属やガラス等の無機繊維及び／またはセルロ−スやアラミド等有機繊維及び／またはそれらの粉末を含んだ系にて調製することも可能である。
【００４９】
本発明の有機高分子と金属酸化物との成分傾斜複合体では、例えば複合体全体の金属酸化物の平均濃度が非常に低いにもかかわらず、少なくとも１つの表面部に５〜１００重量％と高い金属酸化物濃度を有しており、且つその表面部から内部にかけて傾斜的にその濃度が漸減している分散状態の構造を有するものが可能である。
【００５０】
従って、この場合は表面部のみは金属酸化物濃度がより高いことによる特性、例えば、高硬度や優れた耐溶剤性、耐熱性を有するが、その層は表面からの一定厚みに限定されるため、例えばクラック等による劣化因子が見られず、且つ内部にかけて成分傾斜的になっているために、加熱や経時変化により表層面だけの剥離が生じるようなことが無く、安定した複合材特性を発現することができる。
逆に、内部の金属酸化物濃度が表面部より高いものや、より複雑に多層濃度分布を示すものも可能である。
【００５１】
【実施例】
次いで本発明を実施例によって更に説明する。尚、例中の％は特に断りの無い限り重量基準である。
【００５２】
（実施例１）
アクリル樹脂（大日本インキ化学工業株式会社製：アクリディック Ａ−４０５）３０ｇ（樹脂分５７％；キシレン、ブタノール溶液）、メラミン樹脂（大日本インキ化学工業株式会社製：スーパーベッカミン Ｇ−８２１）６.５ｇ（樹脂分６０％；イソブチル溶液）、エポキシ樹脂（大日本インキ化学工業株式会社製：エピクロン １０５０）２.５ｇ、テトラメトキシシラン（以下、ＴＭＯＳと呼ぶ。：東京化成工業社製 特級試薬）１０ｇ、及び脱水テトラヒドロフラン（ＴＨＦ；関東化学株式会社製 特級試薬）２０ｇからなる均質溶液を
【００５３】
基材（ナイロン−６６板）上に滴下し、０.０９モル／ｌのアンモニア濃度の飽和水蒸気雰囲気下で約５時間放置した後、更に、２８℃、５０％に約１日間放置した。８０℃で２時間、更に１５０℃で１時間熱処理を行いアクリル樹脂／シリカ系からなる塗膜（約４０ミクロン厚）を得た。
【００５４】
電子線マイクロアナライザー（ＥＰＭＡ）を用いて、塗膜の断面のＳｉの分布を表面からスキャンした結果を図１に示す。図１の結果より、表面側に強いＳｉの分布が見られ、且つ約４０ミクロンの深さ方向に渡って連続的にＳｉ濃度が変化していることが認められる。
【００５５】
また、かかる深さ方向のＳｉ濃度分布は、同じ塗膜の異なる数カ所の位置で測定しても同じ分布を示すことより、深さ方向と直角の方向には均質なＳｉ濃度を保持していることがわかった。以上の結果より、得られた塗膜は、塗膜全体の平均金属酸化物濃度より高い濃度のシリカ含有層を表面部に持ち、深さ方向と直角方向には均質で、且つ深さ方向には連続的な濃度変化を有する複合体（塗膜）であることが確認された。ここで、
【００５６】
濃度傾斜領域の厚み＝約２３μｍ、濃度傾斜領域厚み／全体厚み＝０．５４
濃度傾斜領域厚み／最大濃度領域厚み＝約９
最大金属酸化物濃度／最低金属酸化物濃度＝２８重量％／３.５重量％＝７.３
であった。
【００５７】
この成分傾斜複合体は薄い白濁を呈しており、走査型電子顕微鏡（ＳＥＭ）を用いて塗膜断面の観測を行ったところ、直径０．２〜０．４μｍの大きさのシリカ微粒子が観測された。シリカ粒子の分布の状態は均質であるが、塗膜表面付近で高く分布し、塗膜内部に行くにつれて低下していた。
【００５８】
尚、ＥＰＭＡは島津製作所株式会社製のＥＰＭ−８１０型を用いて、出力１５ｋＶ−５０ｎＡ、分解能１〜１.５ミクロン、１０ミクロン／分のスキャン速度、検出はＳｉのＫα線（７.１２６オングストロ−ム）で行った。また、ＳＥＭは、日立製作所株式会社製のＳ−８００型のオームストロングＳＥＭを用い、約３ｎｍのプラチナをスパッタリングした試料で観測を行った。
【００５９】
（実施例２）
実施例１の製造条件において、ＴＨＦ２０ｇのかわりにメタノ−ル２０ｇを用い、更に均質溶液のキャストをアンモニア水の飽和水蒸気中で行う代わりに、２５℃、５０％の雰囲気下で行った場合について検討した。透明性に優れた塗膜が得られた。ＥＰＭＡ測定の結果を図２に示す。基盤側に高い金属酸化物濃度を有する成分傾斜複合体となっているのがわかる。
【００６０】
濃度傾斜領域の厚み＝４０μｍ、濃度傾斜領域厚み／全体厚み＝０.７
濃度傾斜領域厚み／最大濃度領域厚み＝１０
最大金属酸化物濃度／最低金属酸化物濃度＝１１.５重量％／４.５重量％＝２.５であった。
【００６１】
成分傾斜複合体は透明で、ＳＥＭ観測では直径約０.０４〜０.１μｍの微粒子がミクロな範囲で均質に分散しているのが観測された。
【００６２】
（比較例１）
実施例１の均質溶液に５ｇの蒸留水を添加して得られる均質溶液を用いて、実施例１と同様な手法でサンプルを作成し検討を行った。ＥＰＭＡ測定の結果を図３に示す。シリカ濃度に傾斜は見られなく、均質に分布しているのが判る。
【００６３】
濃度傾斜領域の厚み＝０μｍ、
最大金属酸化物濃度／最低金属酸化物濃度＝１２重量％／１１重量％＝１.１
複合体は透明で、ＳＥＭ観測では直径０.０６〜０.１５μｍの微粒子が均質に分散しているのが確認された。
【００６４】
（比較例２）
実施例１におけるアンモニア水のアンモニア濃度を０.５モル／ｌとした場合について、実施例１と同様な方法でサンプルを調製し検討を行った。ＥＰＭＡ測定の結果を図４に示す。シリカ濃度に傾斜は見られなく、均質に分布しているのが判る。
【００６５】
濃度傾斜領域の厚み＝０μｍ、
最大金属酸化物濃度／最低金属酸化物濃度＝１３.５重量％／１２.５重量％＝１.１で複合体は透明体であった。
【００６６】
（実施例３）
実施例１と同じ均質溶液をナイロン−６６板上に滴下し、０.０６モル／ｌのアンモニア水とメタノールの１０：３（重量比）混合溶液の飽和水蒸気雰囲気下で２２℃で約１０時間放置した後、実施例１と同様な処理を行いアクリル樹脂／シリカ系からなる塗膜（約７５ミクロン厚）を得た。ＥＰＭＡ測定の結果を図５に示す。塗膜表面側に極めて高いシリカ濃度を有する傾斜複合体が得られているのが判る。
【００６７】
濃度傾斜領域厚み＝４０μｍ、濃度傾斜領域厚み／全体厚み＝０.５３
濃度傾斜領域厚み／最大濃度領域厚み＝１３．３
最大金属酸化物濃度／最低金属酸化物濃度＝３０重量％／３重量％＝１０
傾斜複合体は白濁を呈しており、ＳＥＭ観測では直径約０.３〜２μｍの粒子がミクロな範囲で均質に分散しているのが観測された。
【００６８】
（実施例４）
実施例１と同じ均質溶液に更に０.０６ｇのトリエチルアミン（東京化成工業株式会社製、特級試薬）を添加して得られる均質溶液を用いて、実施例３と同様な条件で溶媒キャストと熱処理を行いアクリル樹脂／シリカ系からなる塗膜（約１２０ミクロン厚）を得た。ＥＰＭＡ測定の結果を図６に示す。塗膜表面側に高いシリカ濃度を有する傾斜複合体となっているのが判る。
【００６９】
濃度傾斜領域厚み＝７０μｍ、濃度傾斜領域厚み／全体厚み＝０.５８
濃度傾斜領域厚み／最大濃度領域厚み＝１７．５
最大金属酸化物濃度／最低金属酸化物濃度＝４０重量％／７.５重量％＝５.３
【００７０】
実施例３の複合体に比べて、金属酸化物の濃度傾斜がなだらかになっている。
傾斜複合体は薄い白濁を呈しており、ＳＥＭ観測では直径約６０〜２００ｎｍの微粒子がミクロな範囲で均質に分散しているのが観測された。実施例３の複合体に比べて、粒径の小さな分散粒子が得られた。
【００７１】
（実施例５）
ビスフェノール型エポキシ樹脂（大日本インキ化学工業株式会社製：エピクロン ８５０）１０ｇと脂肪族ポリアミン系エポキシ硬化剤（大日本インキ化学工業株式会社製：エピクロン Ｂ−０５３）２ｇとＴＨＦ ５ｇの混合溶液を室温で２６時間混合攪拌させた後、５ｇのＴＭＯＳを均質に混合した。得られた均質ゾル溶液を基板に塗布し、室温（１８℃、４０％）で溶媒キャストし、８０℃で５時間、１５０℃で３時間熱処理を行いエポキシ樹脂とシリカとの複合体を得た。ＥＰＭＡ測定の結果を図７に示す。塗膜表面の約５０μｍ内部にシリカ濃度が最大となる形態の傾斜複合体となっているのが判る。
【００７２】
濃度傾斜領域厚み＝１７０μｍ、濃度傾斜領域厚み／全体厚み＝０.７、濃度傾斜領域厚み／最大濃度領域厚み＝８.５、最大金属酸化物濃度／最低金属酸化物濃度＝２６.５重量％／１０.０重量％＝２.６５であった。傾斜複合体は均質透明であり、ＳＥＭ観測では直径約３０〜２００ｎｍの微粒子がミクロな範囲で均質に分散しているのが観測された。
【００７３】
（実施例６）
アルキド樹脂（大日本インキ化学工業株式会社製：ベッコゾール １３４３）１５ｇとブチル化メラミン樹脂（大日本インキ化学工業株式会社製：スーパーベッカミン Ｇ−８２１−６０）５ｇとエタノール １０ｇとＴＭＯＳ ５ｇの混合溶液を攪拌し、均質ゾル溶液を得た。得られた均質ゾル溶液を基板に塗布し、０.４モル／ｌのアンモニア水の雰囲気下（３０℃）で溶媒キャストをした後、８０℃で５時間、１５０℃で１時間熱処理を行いアルキド樹脂とシリカとの複合体を得た。ＥＰＭＡ測定の結果を図８に示す。塗膜表面部にシリカ濃度が最大となる形態の傾斜複合体となっているのが判る。傾斜は膜厚（約１２０μｍ）全体に渡って形成されており、乳白濁化していた。
【００７４】
濃度傾斜領域厚み＝１２０μｍ、濃度傾斜領域厚み／全体厚み＝１、濃度傾斜領域厚み／最大濃度領域厚み＝１２０以上、最大金属酸化物濃度／最低金属酸化物濃度＝６２重量％／１４重量％＝４.４であった。
【００７５】
【発明の効果】
本発明により得られる有機高分子と金属酸化物との成分傾斜複合体は、有機高分子中に種々の大きさ（μｍオ−ダ−から約１０ｎｍまで）の金属酸化物を極めて均質に分散させ、且つ当該複合体の厚み方向に金属酸化物の含有濃度が分布を持つように分散されているため、例えば、表面部もしくは内部に、複合体全体での金属酸化物の平均濃度よりも高い（低い）金属酸化物濃度を有する部分を有する複合体の製造が可能で、高（もしくは低）金属酸化物濃度を含有する有機高分子複合体特有の物性を有し、且つ金属酸化物濃度が傾斜的に変化していることにより、一般の塗膜のように加熱や経時変化により表層面と内部の剥離が生じるようなことがない、安定な複合材を提供できる。
【図面の簡単な説明】
【図１】実施例１で得られた有機高分子と金属酸化物との成分傾斜複合体（塗膜）の厚み方向の電子線マイクロアナライザ−（ＥＰＭＡ）によるＳｉ分布測定結果を示す図である。
【図２】実施例２で得られた有機高分子と金属酸化物との成分傾斜複合体（塗膜）の厚み方向のＥＰＭＡによるＳｉ分布測定結果を示す図である。
【図３】比較例１で得られた有機高分子と金属酸化物との複合体（塗膜）の厚み方向のＥＰＭＡによるＳｉ分布測定結果を示す図である。
【図４】比較例２で得られた有機高分子と金属酸化物との複合体（塗膜）の厚み方向のＥＰＭＡによるＳｉ分布測定結果を示す図である。
【図５】実施例３で得られた有機高分子と金属酸化物との成分傾斜複合体（塗膜）の厚み方向のＥＰＭＡによるＳｉ分布測定結果を示す図である。
【図６】実施例４で得られた有機高分子と金属酸化物との成分傾斜複合体（塗膜）の厚み方向のＥＰＭＡによるＳｉ分布測定結果を示す図である。
【図７】実施例５で得られた有機高分子と金属酸化物との成分傾斜複合体（塗膜）の厚み方向のＥＰＭＡによるＳｉ分布測定結果を示す図である。
【図８】実施例６で得られた有機高分子と金属酸化物との成分傾斜複合体（塗膜）の厚み方向のＥＰＭＡによるＳｉ分布測定結果を示す図である。[0001]
BACKGROUND OF THE INVENTION
In the composite of a metal oxide obtained by hydrolysis / polycondensation reaction of a metal alkoxide and an organic polymer, the present invention has a region in which the content of the metal oxide is inclined differently in the thickness direction of the composite. The present invention relates to a component gradient composite of an organic polymer and a metal oxide characterized by the following:
[0002]
[Prior art]
In order to improve the performance of organic polymers, various methods have been studied so far. A resin with novel properties can be prepared by blending multiple organic polymers or combined with different types of reinforcing materials. For example, it has been widely practiced to prepare a molded article having desired characteristics.
[0003]
For example, when blending organic polymers together, search for compatible organic polymers and make them into homogeneous composites by methods such as melt mixing, or incompatible organic polymers with a microphase separation structure. Organic polymers have been modified in accordance with the purpose of use, for example, by devising blending conditions so as to have a specific dispersion structure including
[0004]
On the other hand, physical property modification by mixing and dispersing a reinforcing material in an organic polymer has been extensively studied. Specifically, organic or inorganic fibrous materials such as aramid fiber, pulp, glass fiber, and carbon fiber, and powdered inorganic materials such as calcium carbonate, silica, and alumina are widely mixed with organic polymers. Yes.
[0005]
In particular, compounding by mixing with an inorganic material has been widely studied as an easy high-performance reforming means because it makes use of the excellent heat resistance and mechanical properties of the inorganic material.
However, in the case of inorganic materials, it is difficult to control the dispersion state microscopically due to the difference in properties from organic polymer materials in terms of heat infusibility, chemical insolubility, high specific gravity, surface characteristics, etc. In general, it is not simple, but is generally compounded for the purpose of obtaining a bulk composite material that is as homogeneous as possible.
[0006]
That is, in order to improve the modification effect, it is possible to select a reinforcing inorganic material having a smaller shape and good wettability with the matrix polymer, and disperse them as uniformly as possible in a predetermined amount. It is an important factor in compounding.
However, even in this case, there is a problem that as the inorganic material becomes finer, homogeneous dispersion becomes more difficult and the energy and cost are higher.
[0007]
Therefore, in order to obtain a high-performance organic material / inorganic material composite material composed of an organic material and a particulate inorganic material, which is microscopically homogeneous and whose dispersion structure is controlled, It is quite difficult to mix fine inorganic materials with organic polymers, and new technology needs to be developed.
[0008]
The present inventors have conducted research and development of a novel composite material of an organic material and an inorganic material effective for such purposes. One example is a micro-hybrid composite material of a metal oxide obtained from a metal alkoxide and an organic polymer.
[0009]
The composite is subjected to in-situ hydrolysis and polycondensation of metal alkoxides in an organic polymer matrix so that nano-order to micro-order metal oxide particles are wetted in the organic polymer. It is a composite material composed of an organic material and an inorganic material, which is well dispersed and uniformly dispersed and has excellent properties including mechanical properties.
[0010]
However, if the proportion of the metal oxide component in the composite is excessively increased, a good composite material cannot be obtained due to the difference in essential characteristics between the organic polymer to be combined and the metal oxide. . That is, when the metal oxide content is high, cracks are likely to be generated, the mold becomes brittle, the moldability is deteriorated, and warping and deformation such as strain are generated. On the other hand, if the metal oxide content is very small, desired composite properties cannot be obtained.
[0011]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to obtain a good composite that can effectively express the characteristics up to a high content region of the metal oxide, more specifically, cracks hardly occur, It is another object of the present invention to provide a component-graded composite of an organic polymer and a metal oxide having a good moldability in which only the surface layer is not peeled off due to heating or changes over time, and a method for producing the same.
[0012]
[Means for Solving the Problems]
The present inventors have intensively studied to obtain a composite having excellent characteristics in a wide range of composition in a composite composed of an organic polymer and a metal oxide, and have completed this research.
[0013]
That is, the present invention is a complex of an organic polymer and a metal oxide containing at least two components of an organic polymer component and a metal oxide component (A), and the depth from the surface of the complex. The content of the metal oxide component (A) in the composite continuously changes, the composition has a gradient structure, and the content is 5 to 100% by weight at the highest place, and 0 at the lowest place. It is a component gradient composite of an organic polymer and a metal oxide, characterized in that it is ˜50% by weight and the ratio of the content ratio between the high part and the low part is 1.5 or more.
[0014]
Specifically, the component-graded composite of the organic polymer and metal oxide of the present invention is such that the metal oxide component (A) is hydrolyzed / decomposed of a metal alkoxide or a low condensate thereof in the presence of the organic polymer component. It is a component gradient composite of an organic polymer and a metal oxide, which is obtained by polycondensation.
[0015]
In addition, in the component gradient composite of the organic polymer and metal oxide of the present invention, in detail, the metal oxide component (A) exceeds the average content of the entire composite on at least one surface of the composite. It is a feature that exists.
[0016]
Furthermore, in the component gradient composite of the organic polymer and metal oxide of the present invention, the metal oxide component (A) is present at a ratio of not more than the average content of the entire composite on at least one surface of the composite. It is a component gradient composite of an organic polymer and a metal oxide.
[0017]
The component gradient composite of the organic polymer and metal oxide of the present invention has a thickness (d1) in which the content of the metal oxide component (A) continuously changes in the depth direction of the composite. A component-graded composite of an organic polymer and a metal oxide, characterized in that it is larger than the thickness (d2) showing the highest content of the metal oxide component (A).
[0018]
Furthermore, the component gradient composite of the organic polymer and metal oxide of the present invention is characterized in that the size of the metal oxide in the composite is an average diameter of 0.01 to 5 μm, Component gradient composite of metal oxide, and component gradient of organic polymer and metal oxide characterized in that the average size of the metal oxide in the composite is 0.01 to 0.5 μm It contains a complex.
[0019]
In addition, the component gradient composite of the organic polymer and the metal oxide of the present invention is obtained by hydrolysis / polycondensation of the metal oxide component or metal alkoxide or a low condensate thereof in the presence of the organic polymer component. In particular, it is a component gradient composite of an organic polymer and a metal oxide, characterized in that the metal alkoxide or the condensate thereof is represented by the general formula 1.
[0020]
(General formula 1)
[Chemical 3]

(Wherein M is a silicon atom, R is C _m H _{2m + 1} , M represents an integer of 1 to 4, and n represents an integer of 1 to 10. )
[0023]
The present invention relates to water and / or metal alkoxide obtained by applying a homogeneous solution comprising an organic polymer, metal alkoxide, a common solvent thereof and / or a metal alkoxide polymerization catalyst on an organic polymer or an inorganic substrate. Including a method for producing a component gradient composite of an organic polymer and a metal oxide, wherein the polymerization catalyst and / or an organic solvent is maintained in an atmosphere containing air, followed by drying and heat treatment. It is a waste.
[0024]
The method for producing a component gradient composite of an organic polymer and a metal oxide according to the present invention is such that the metal oxide component is obtained by hydrolysis / polycondensation of a metal alkoxide or a low condensate thereof in the presence of the organic polymer component. An organic polymer and a metal oxide obtained by homogeneously dispersing in an organic polymer component, in particular, wherein the metal alkoxide is a silicon alkoxide represented by the general formula 1 or a low condensate thereof And a method for producing a component-gradient composite.
[0025]
(General formula 1)
[Formula 4]

(Wherein M is a silicon atom, R is C _m H _{2m + 1} , M represents an integer of 1 to 4, and n represents an integer of 1 to 10. )
[0026]
The method for producing a component gradient composite of an organic polymer and a metal oxide according to the present invention uses the same or different basic substance as a polymerization catalyst for a metal alkoxide contained in an atmosphere and / or homogeneous solution. The manufacturing method of the component inclination composite_body | complex of the organic polymer and metal oxide characterized by the above is included.
[0027]
That is, the present invention relates to a composite of an organic polymer and a metal oxide containing at least one organic polymer and a metal oxide, and the contained metal oxide component has a different concentration inside the composite. A component gradient structure in which the metal oxide component concentration continuously changes in the depth direction from the surface of the composite,
[0028]
And the metal oxide component concentration in the composite is 5 to 100% by weight at the highest point, 0 to 50% by weight at the lowest point, and the ratio of the content ratio between the high and low parts is 1.5 or more. And a metal oxide obtained by polycondensing a metal alkoxide or a low condensate thereof in the presence of the organic polymer. The main component is a component gradient composite of an organic polymer and a metal oxide.
[0029]
In the component gradient composite of the organic polymer and the metal oxide, the metal oxide component is present beyond the average metal oxide concentration of the composite on at least one surface of the composite, or at least 1 In one surface, the metal oxide component is less than or equal to the average metal oxide concentration of the composite. In addition, the component gradient composite of the organic polymer and the metal oxide includes one having a thickness having a metal oxide concentration gradient larger than the thickness having the highest content of metal oxide in the depth direction.
[0030]
In addition, the component gradient composite of the organic polymer and the metal oxide includes those in which the size of the metal oxide contained in the composite is an average diameter of 0.01 μm to 5 μm. In addition, the component gradient composite of the organic polymer and the metal oxide includes those in which the form is a coating film, a thread, a film, a spherical shape, or a molded body having various shapes such as a block.
[0031]
In the present invention, the metal oxide basically has a region that continuously changes in the depth direction while maintaining homogeneity in the organic polymer except in the depth direction. Therefore, a uniform coating film having a different metal oxide concentration discontinuously due to irregular agglomeration or phase separation or a uniform coating film having a constant metal oxide content formed by coating is applied on the surface of the substrate. It is different from what you have.
[0032]
As the organic polymer that can be used in the present invention, any organic polymer that can form a complex of a homogeneous organic polymer and a metal oxide by polycondensation of a metal alkoxide in the presence of the organic polymer may be used. Specific examples include, but are not limited to, thermosetting resins such as phenol resin, epoxy resin, acrylic resin, alkyd resin, melamine resin, and urea resin, and thermoplastic resins such as nylon, polyester, and acrylic resin. Rubber-based resins such as polybutadiene and SBS can be used, and thermosetting resins, particularly epoxy resins, acrylic resins, alkyd resins, and melamine resins are particularly preferable.
[0033]
From the viewpoint of ease of production, an organic polymer or precursor resin thereof that dissolves or swells in a homogeneous solution comprising a metal alkoxide, a condensate thereof or a solvent thereof and the like is desirable.
[0034]
As the metal alkoxide in the present invention, a silicon alkoxide represented by the general formula 1 and / or a condensate thereof is used. As other metal alkoxides, metal alkoxides such as Ti, Al, and Zr can be used. However, when a mixture of Si alkoxides or other metal alkoxides mainly containing Si is used, hydrolysis / The condensation reaction rate is slow, which is particularly preferable for controlling the concentration gradient.
[0035]
The component gradient composite of the organic polymer and the metal oxide in the present invention has a content of the metal oxide component (A) in the composite (hereinafter sometimes simply referred to as a metal oxide content). The highest part is 5 to 100% by weight, and the lowest part is preferably 0 to 50% by weight.
[0036]
If the metal oxide content in the highest part is less than 5% by weight, the effect of the composite is insufficient, and if the metal oxide content in the lowest part exceeds 50% by weight, the composite is brittle. Such as cracking, cracking, and the like, and the total thickness of the composite must be very thin.
[0037]
Further, the ratio between the place with the highest metal oxide content and the place with the lowest metal oxide content needs to be 1.5 or more, preferably 2 or more. If the ratio is less than 1.5, the effect as a component gradient composite is insufficient. Further, when the thickness (d1) in which the metal oxide concentration changes in the depth direction is larger than the thickness (d2) of the region showing the highest metal oxide content, the effect as the graded composite material is more effective. It is clear.
[0038]
The size of the metal oxide in the present invention is 0.01 μm to 5 μm in diameter. In particular, when the size of the metal oxide is 0.01 μm to 0.5 μm and the organic polymer used is transparent, the composite of the present invention has a transparent to translucent appearance.
Moreover, when the size of the metal oxide is 0.5 μm to 5 μm, it has a translucent to opaque appearance.
[0039]
In any case, in the component gradient composite composed of a metal oxide and an organic polymer obtained by polycondensation of a metal alkoxide or a condensate thereof in the presence of an organic polymer, the metal oxide particles prepared in advance and the organic polymer Compared to mixing and dispersing molecules, it is easier to control the particle size of the metal oxide particles up to a very small particle size.
[0040]
Conventional particles for reinforcing additives such as silica have a limit of about 1 to 2 μm in diameter in view of the possibility of homogeneous dispersion and cost. When smaller fine particles are used, it is often difficult to uniformly disperse or control the fine particles due to the density difference from the organic polymer and the aggregation of the fine particles.
[0041]
In the present invention, it is possible to obtain a component gradient composite in which the average particle diameter of the metal oxide is homogeneously contained up to that of nanometer size and the dispersion structure is controlled.
The size of the metal oxide in the present invention is given a numerical value of 0.01 μm because it is difficult to capture a particle size of 0.01 μm or less by measurement with a scanning electron microscope or the like. There is no problem even if it is small. However, when the average particle size is 5 μm or more, it is difficult to obtain a homogeneous component gradient composite.
[0042]
As a method for obtaining the component gradient composite of the organic polymer and the metal oxide of the present invention, the final component gradient composite is maintained in a microscopically uniform dispersion while maintaining a microscopically homogeneous dispersion. What is necessary is just to have the area | region where a metal oxide density | concentration changes continuously, and it is not specifically limited by a manufacturing method.
[0043]
However, an example of a specific production method thereof includes, for example, an organic polymer component and a metal alkoxide or a condensate thereof, and / or water, and / or a catalyst, and / or an organic solvent as raw materials. Hydrolysis and polycondensation of heterogeneous metal alkoxides in the depth direction of the final composite will occur during hydrolysis / polycondensation of resin, resin curing reaction, and / or solvent casting This is a simple operation.
[0044]
More specifically, the concentration distribution of a specific raw material component (for example, metal alkoxide, basic catalyst, or water) among the above raw materials is given in the depth direction, or external stimulation (for example, heating) from one direction is performed. Thus, it is possible to develop a gradient metal oxide concentration distribution.
[0045]
For example, water and / or metal alkoxide polymerization catalyst and / or a solution in which a homogeneous solution comprising an organic polymer and a metal alkoxide or a condensate thereof and a common solvent thereof and / or a metal alkoxide polymerization catalyst is coated on a substrate is used. Or after hold | maintaining in the atmosphere which contains the organic solvent in the air, the gradient of the metal oxide density | concentration in a coating film can be expressed by performing drying and heat processing.
[0046]
In the present invention, the same or different acid or basic substance is used as the polymerization catalyst for the metal alkoxide contained in the atmosphere or in the homogeneous solution. In particular, various amine compounds and basic substances such as ammonia are used. This is preferable in the formation of fine particles of metal oxide in the gradient composite and the component gradient control.
[0047]
In the present invention, the organic solvent contained in the atmosphere is preferably one that is homogeneously mixed with a solution comprising an organic polymer or the like, and is of a different type from the organic solvent already contained in the solution. Is particularly preferred.
[0048]
The component gradient composite of the organic polymer and metal oxide of the present invention can be used for various molded products such as coating films, yarns, films, and fine particles, and molding raw materials. It is also possible to prepare in a system containing other inorganic fibers such as metal and glass and / or organic fibers such as cellulose and aramid and / or powders thereof.
[0049]
In the component gradient composite of the organic polymer and the metal oxide of the present invention, for example, the average concentration of the metal oxide of the entire composite is very low, but at least one surface portion is 5 to 100% by weight. What has a high metal oxide density | concentration and has the structure of the dispersion state which the density | concentration decreases gradually from the surface part to the inside is possible.
[0050]
Therefore, in this case, only the surface portion has characteristics due to higher metal oxide concentration, for example, high hardness, excellent solvent resistance, and heat resistance, but the layer is limited to a certain thickness from the surface. For example, no deterioration factors due to cracks, etc. are seen, and since the components are inclined toward the inside, peeling of only the surface layer does not occur due to heating or change over time, and stable composite material characteristics are expressed can do.
Conversely, a metal oxide having an internal metal oxide concentration higher than that of the surface portion or a more complicated multi-layer concentration distribution is also possible.
[0051]
【Example】
The invention is then further illustrated by the examples. In the examples, “%” is based on weight unless otherwise specified.
[0052]
(Example 1)
30 g of acrylic resin (Dainippon Ink Chemical Co., Ltd .: Acrydic A-405) (57% resin content; xylene, butanol solution), melamine resin (Dainippon Ink Chemical Co., Ltd .: Super Becamine G-821) 6.5 g (resin content 60%; isobutyl solution), epoxy resin (Dainippon Ink & Chemicals, Inc .: Epicron 1050) 2.5 g, tetramethoxysilane (hereinafter referred to as TMOS): Tokyo Kasei Kogyo Co., Ltd. A homogeneous solution consisting of 10 g and 20 g of dehydrated tetrahydrofuran (THF; special grade reagent manufactured by Kanto Chemical Co., Ltd.)
[0053]
The solution was dropped on a base material (nylon-66 plate), allowed to stand for about 5 hours in a saturated water vapor atmosphere having an ammonia concentration of 0.09 mol / l, and further allowed to stand at 28 ° C. and 50% for about 1 day. Heat treatment was performed at 80 ° C. for 2 hours and further at 150 ° C. for 1 hour to obtain a coating film (about 40 microns thick) made of an acrylic resin / silica system.
[0054]
The result of scanning the distribution of Si in the cross section of the coating from the surface using an electron beam microanalyzer (EPMA) is shown in FIG. From the results of FIG. 1, it can be seen that a strong Si distribution is seen on the surface side, and that the Si concentration continuously changes over a depth direction of about 40 microns.
[0055]
Moreover, the Si concentration distribution in the depth direction shows the same distribution even when measured at several different positions of the same coating film, so that a uniform Si concentration is maintained in the direction perpendicular to the depth direction. I understand. From the above results, the obtained coating film has a silica-containing layer having a concentration higher than the average metal oxide concentration of the entire coating film on the surface portion, and is homogeneous in the direction perpendicular to the depth direction and in the depth direction. Was confirmed to be a composite (coating film) having a continuous concentration change. here,
[0056]
Concentration gradient region thickness = about 23 μm, concentration gradient region thickness / overall thickness = 0.54
Concentration gradient region thickness / maximum concentration region thickness = approximately 9
Maximum metal oxide concentration / minimum metal oxide concentration = 28 wt% / 3.5 wt% = 7.3
Met.
[0057]
This component gradient composite is thinly clouded. When the cross section of the coating film is observed using a scanning electron microscope (SEM), silica fine particles having a diameter of 0.2 to 0.4 μm are observed. It was. The distribution of the silica particles was homogeneous, but it was highly distributed in the vicinity of the coating film surface and decreased as it went into the coating film.
[0058]
The EPMA is an EPM-810 model manufactured by Shimadzu Corporation. The output is 15 kV-50 nA, the resolution is 1 to 1.5 microns, the scanning speed is 10 microns / minute, and the detection is Si Kα ray (7.126 Å). -). In addition, SEM was observed with a sample obtained by sputtering about 3 nm of platinum using an S-800 ohm strong SEM manufactured by Hitachi, Ltd.
[0059]
(Example 2)
In the production conditions of Example 1, 20 g of methanol was used instead of 20 g of THF, and a case where the homogeneous solution was cast in a saturated water vapor of ammonia water instead of 25 ° C. in a 50% atmosphere was examined. did. A coating film excellent in transparency was obtained. The results of EPMA measurement are shown in FIG. It can be seen that the component gradient composite has a high metal oxide concentration on the substrate side.
[0060]
Thickness of concentration gradient region = 40 μm, concentration gradient region thickness / total thickness = 0.7
Concentration gradient region thickness / maximum concentration region thickness = 10
The maximum metal oxide concentration / minimum metal oxide concentration = 11.5 wt% / 4.5 wt% = 2.5.
[0061]
The component gradient composite was transparent, and it was observed by SEM that fine particles having a diameter of about 0.04 to 0.1 μm were uniformly dispersed in a micro range.
[0062]
(Comparative Example 1)
Using a homogeneous solution obtained by adding 5 g of distilled water to the homogeneous solution of Example 1, a sample was prepared and examined in the same manner as in Example 1. The results of EPMA measurement are shown in FIG. It can be seen that there is no gradient in the silica concentration, and the silica concentration is homogeneously distributed.
[0063]
Thickness of concentration gradient region = 0 μm,
Maximum metal oxide concentration / minimum metal oxide concentration = 12 wt% / 11 wt% = 1.1
The composite was transparent, and SEM observation confirmed that fine particles having a diameter of 0.06 to 0.15 μm were uniformly dispersed.
[0064]
(Comparative Example 2)
In the case where the ammonia concentration in Example 1 was 0.5 mol / l, a sample was prepared and examined in the same manner as in Example 1. The results of EPMA measurement are shown in FIG. It can be seen that there is no gradient in the silica concentration, and the silica concentration is homogeneously distributed.
[0065]
Thickness of concentration gradient region = 0 μm,
The maximum metal oxide concentration / minimum metal oxide concentration = 13.5 wt% / 12.5 wt% = 1.1, and the composite was transparent.
[0066]
(Example 3)
The same homogeneous solution as in Example 1 was dropped on a nylon-66 plate, and the mixture was stirred at 22 ° C. for about 10 hours in a saturated steam atmosphere of a 0.06 mol / l ammonia water / methanol 10: 3 (weight ratio) mixed solution. After being allowed to stand, the same treatment as in Example 1 was performed to obtain a coating film (about 75 microns thick) made of an acrylic resin / silica system. The results of EPMA measurement are shown in FIG. It can be seen that a gradient composite having an extremely high silica concentration is obtained on the coating surface side.
[0067]
Concentration gradient region thickness = 40 μm, concentration gradient region thickness / total thickness = 0.53
Density gradient area thickness / maximum density area thickness = 13.3
Maximum metal oxide concentration / minimum metal oxide concentration = 30 wt% / 3 wt% = 10
The tilted composite was cloudy, and SEM observation showed that particles having a diameter of about 0.3 to 2 μm were uniformly dispersed in a microscopic range.
[0068]
(Example 4)
Using a homogeneous solution obtained by adding 0.06 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., special grade reagent) to the same homogeneous solution as in Example 1, solvent casting and heat treatment were performed under the same conditions as in Example 3. A coating film (about 120 microns thick) made of an acrylic resin / silica system was obtained. The results of EPMA measurement are shown in FIG. It can be seen that the gradient composite has a high silica concentration on the coating surface side.
[0069]
Concentration gradient region thickness = 70 μm, concentration gradient region thickness / total thickness = 0.58
Density gradient area thickness / maximum density area thickness = 17.5
Maximum metal oxide concentration / minimum metal oxide concentration = 40 wt% / 7.5 wt% = 5.3
[0070]
Compared to the composite of Example 3, the concentration gradient of the metal oxide is gentle.
The tilted composite was thinly clouded, and SEM observation showed that fine particles having a diameter of about 60 to 200 nm were uniformly dispersed in a micro range. Compared with the composite of Example 3, dispersed particles having a small particle size were obtained.
[0071]
(Example 5)
A mixed solution of 10 g of a bisphenol type epoxy resin (Dainippon Ink Chemical Co., Ltd .: Epicron 850), 2 g of an aliphatic polyamine epoxy curing agent (Dainippon Ink Chemical Co., Ltd .: Epicron B-053) and 5 g of THF is used at room temperature. Then, the mixture was stirred for 26 hours, and 5 g of TMOS was mixed homogeneously. The obtained homogeneous sol solution was applied to a substrate, solvent casted at room temperature (18 ° C., 40%), and heat-treated at 80 ° C. for 5 hours and at 150 ° C. for 3 hours to obtain a composite of epoxy resin and silica. . The results of EPMA measurement are shown in FIG. It can be seen that the gradient composite has a form in which the silica concentration is maximum within about 50 μm of the coating surface.
[0072]
Concentration gradient region thickness = 170 μm, Concentration gradient region thickness / overall thickness = 0.7, Concentration gradient region thickness / Maximum concentration region thickness = 8.5, Maximum metal oxide concentration / Minimum metal oxide concentration = 26.5 wt% /10.0% by weight = 2.65. The tilted composite was homogeneous and transparent, and SEM observation showed that fine particles with a diameter of about 30 to 200 nm were uniformly dispersed in a micro range.
[0073]
(Example 6)
A mixed solution of 15 g of alkyd resin (Dainippon Ink Chemical Co., Ltd .: Beckosol 1343), 5 g of butylated melamine resin (Dainippon Ink Chemical Co., Ltd .: Super Becamine G-821-60), 10 g of ethanol and 5 g of TMOS Were stirred to obtain a homogeneous sol solution. The obtained homogeneous sol solution was applied to a substrate and casted with a solvent in an atmosphere of 0.4 mol / l ammonia water (30 ° C.), followed by heat treatment at 80 ° C. for 5 hours and 150 ° C. for 1 hour to obtain alkyd A composite of resin and silica was obtained. The results of EPMA measurement are shown in FIG. It can be seen that the gradient composite has a form in which the silica concentration is maximized on the surface of the coating film. The slope was formed over the entire film thickness (about 120 μm) and was milky white.
[0074]
Concentration gradient region thickness = 120 μm, concentration gradient region thickness / overall thickness = 1, concentration gradient region thickness / maximum concentration region thickness = 120 or more, maximum metal oxide concentration / minimum metal oxide concentration = 62 wt% / 14 wt% = 4.4.
[0075]
【The invention's effect】
The component-graded composite of organic polymer and metal oxide obtained by the present invention has extremely uniform dispersion of metal oxides of various sizes (from μm order to about 10 nm) in the organic polymer. In addition, since the concentration of the metal oxide is dispersed in the thickness direction of the composite, the concentration is higher than the average concentration of the metal oxide in the entire composite, for example, on the surface or inside ( It is possible to produce a composite having a portion having a low (low) metal oxide concentration, a physical property unique to an organic polymer composite containing a high (or low) metal oxide concentration, and a gradient of the metal oxide concentration. As a result, it is possible to provide a stable composite material in which peeling between the surface layer surface and the inside is not caused by heating or a change over time unlike a general coating film.
[Brief description of the drawings]
FIG. 1 is a diagram showing the results of Si distribution measurement by an electron microanalyzer (EPMA) in the thickness direction of a component gradient composite (coating film) of an organic polymer and a metal oxide obtained in Example 1. FIG. .
2 is a graph showing the Si distribution measurement result by EPMA in the thickness direction of the component gradient composite (coating film) of organic polymer and metal oxide obtained in Example 2. FIG.
FIG. 3 is a diagram showing the results of Si distribution measurement by EPMA in the thickness direction of a composite (coating film) of an organic polymer and a metal oxide obtained in Comparative Example 1.
4 is a graph showing Si distribution measurement results by EPMA in the thickness direction of a composite (coating film) of an organic polymer and a metal oxide obtained in Comparative Example 2. FIG.
5 is a diagram showing the results of Si distribution measurement by EPMA in the thickness direction of a component gradient composite (coating film) of an organic polymer and a metal oxide obtained in Example 3. FIG.
6 is a graph showing the results of Si distribution measurement by EPMA in the thickness direction of the component gradient composite (coating film) of organic polymer and metal oxide obtained in Example 4. FIG.
7 is a graph showing the results of Si distribution measurement by EPMA in the thickness direction of the component gradient composite (coating film) of organic polymer and metal oxide obtained in Example 5. FIG.
8 is a graph showing the Si distribution measurement result by EPMA in the thickness direction of the component gradient composite (coating film) of organic polymer and metal oxide obtained in Example 6. FIG.

Claims (12)

  A composite of an organic polymer and a metal oxide containing at least two components of an organic polymer component and a metal oxide component (A), wherein the metal oxide component (A) has an average diameter of 0.01 to 0.5 μm particles, having a component gradient structure in which the content of the metal oxide component (A) in the composite continuously changes in the depth direction from the surface of the composite, and the content 5 to 100% by weight in the highest place, 0 to 50% by weight in the lowest place, and the ratio of the content ratio between the high place and the low place is 1.5 or more Inclined composite of metal and metal oxide.   The organic polymer and metal oxide according to claim 1, wherein the metal oxide component (A) is obtained by hydrolysis and polycondensation of a metal alkoxide or a low condensate thereof in the presence of the organic polymer component. Ingredient gradient complex.   The component of the organic polymer and the metal oxide according to claim 1 or 2, wherein the metal oxide component (A) is present on at least one surface of the composite in excess of the average content of the entire composite. Tilted complex.   3. The organic polymer and the metal oxide according to claim 1 or 2, wherein the metal oxide component (A) is present on at least one surface of the composite at a ratio equal to or less than the average content of the entire composite. Component graded complex.   The thickness (d2) in which the thickness (d1) in which the content of the metal oxide component (A) continuously changes in the depth direction of the composite shows the highest content of the metal oxide component (A) The component inclination composite_body | complex of the organic polymer and metal oxide as described in any one of Claims 1-4 larger than. The component gradient composite of an organic polymer and a metal oxide according to any one of claims 2 to 5, wherein the metal alkoxide or a low condensate thereof is represented by the general formula 1.
(General formula 1)

(In the formula, M represents a silicon atom, R represents C _m H _{2m + 1} , m represents an integer of 1 to 4, and n represents an integer of 1 to 10.)   In an atmosphere in which a homogeneous solution composed of an organic polymer, a metal alkoxide and a common solvent thereof is applied on an organic polymer or an inorganic substrate, and a water and / or metal alkoxide polymerization catalyst is contained in the air. A method for producing a component-graded composite of an organic polymer and a metal oxide, which is dried and heat-treated after being held in the container.   The method for producing a component gradient composite of an organic polymer and a metal oxide according to claim 7, wherein an organic solvent is further contained in an air atmosphere containing a polymerization catalyst of water and / or metal alkoxide.   The method for producing a component gradient composite of an organic polymer and a metal oxide according to claim 8, wherein the organic solvent contained in the atmosphere is different from the organic solvent used for preparing the homogeneous solution.   The component of the organic polymer and the metal oxide according to any one of claims 7 to 9, further comprising a metal alkoxide polymerization catalyst in a homogeneous solution comprising the organic polymer, the metal alkoxide and a common solvent thereof. A method of manufacturing a tilted composite.   11. The organic catalyst according to claim 7, wherein the metal alkoxide polymerization catalyst contained in the air atmosphere and the metal alkoxide polymerization catalyst contained in the homogeneous solution are the same or different basic substances. A method for producing a component gradient composite of a polymer and a metal oxide. The method for producing a component gradient composite of an organic polymer and a metal oxide according to any one of claims 7 to 11, wherein the metal alkoxide is a silicon alkoxide represented by the general formula 1 or a low condensate thereof.
(General formula 1)

(In the formula, M represents a silicon atom, R represents C _m H _{2m + 1} , m represents an integer of 1 to 4, and n represents an integer of 1 to 10.)

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