JP3744736B2 - Highly slidable base material and method for producing the same - Google Patents
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Description
【０００１】
【発明の属する分野】
本発明は、特に建築用窓ガラス、車両用窓ガラス、鏡、その他産業用窓ガラス等に用いることが可能な、極めて優れた滑水性（水滴滑落性）を示す高滑水性基材の製造方法に関する。
【０００２】
【従来の技術】
高い撥水耐久性（耐光性や耐摩耗性）を得るために、フルオロアルキル基含有シラン化合物を基材表面に処理した撥水性ガラスについて、非常に多くの発明がなされている。例えば、特開平６-１６４５５号公報には、ガラス表面に凹凸形状を有するシリカなどの下地膜を設けることが非常に有効であることが開示されている、一方、下地膜のないものとしては、特許第２５００１７８号公報には、ガラス表面に撥水撥油性の単分子膜を形成する方法が、特開平１０-５９７４５公報には、撥水処理するガラス表面をセリア研摩してさらに酸処理して基材の活性を高める方法や撥水処理液として重合度を増大または制御したフルオロアルキル基含有シラン化合物を用いる方法が開示されている。さらに、特開平８-３２５０３７号公報には、ガラス基材表面近傍にアルカリ金属を含まないか、またはアルカリ金属含有量が少ないアルカリバリアー層を形成後、フルオロアルキル基含有シラン化合物を処理することにより、耐久性の高い撥水処理ガラスを得る方法が開示されている。さらにまた、特開平９-４８６３９号公報には、ガラス基材表面を脱アルカリ層とすることによってナトリウム等のアルカリ成分量を減じた表面を形成させた後にフルオロアルキル基含有シラン化合物を処理することにより、耐熱性、耐水性および耐候性を高めることが開示されている。
【０００３】
一方、水滴滑落性をより改善することに重点を置いた検討もなされており、高水滴転落性または高滑水性ガラスが提案されている。例えば、シリコーン系ワックス、オルガノポリシロキサン、界面活性剤などを含む組成物が発明されており、特公昭５０-１５４７３号公報には、アルキルポリシロキサンおよび酸よりなる組成物、また、特開平５-３０１７４２号公報には、アミノ変性シリコーンオイルと界面活性剤とを含有する組成物が開示されている。
【０００４】
さらに、高い撥水耐久性（耐光性や耐摩耗性）と優れた水滴滑落性を兼ね備えた組成物の発明もなされており、特開平１１-１１６９４３号公報には、パーフルオロアルキル基含有シラン化合物のフルオロアルキル基の少なくとも末端のＦ原子をＨ原子で置換した組成物からなる表面処理剤が開示されている。また、特開平８-１２３７５公報には、パーフルオロアルキル基含有シラン化合物とポリジメチルシロキサンを混合後、加水分解して得た組成物をガラス基板などに塗布した撥水性物品が開示されている。
【０００５】
【発明が解決しようとする課題】
しかしながら、前記の特開平６-１６４５５号公報、特許第２５００１７８号公報、特開平１０-５９７４５公報、特開平８-３２５０３７号公報、特開平９-４８６３９号公報記載の、高い撥水耐久性（耐光性や耐摩耗性）を有するフルオロアルキル基含有シラン化合物を基材表面に処理した撥水性ガラスでは、水滴滑落性（滑水性）が悪く、例えば、自動車用ウィンドシールドの取り付け角度である３０°傾斜においては、静止時に少なくとも水滴の体積が約４０〜６０μl以上でないと水滴は滑落せずにガラス表面上に残存してしまう。
【０００６】
また、前記特公昭５０-１５４７３号公報、特開平５-３０１７４２号公報の方法で得られたものは、滑水性（水滴滑落性）は良好であり、中には３０°傾斜で約１５μl程度の水滴で滑落するものが得られているが、高い撥水耐久性（耐光性や耐摩耗性）を得るまでには至っていない。
【０００７】
さらに、特開平８-１２３７５公報記載の方法は、パーフルオロアルキル基含有シラン化合物とポリジメチルシロキサン化合物を混合して加水分解し、次いでこれを加水分解したアルコキシシラン化合物に混合して溶液を調製し、これを基材表面に塗布することが示されており、ハイブリッド膜の外側表面層に嵩高く剛直なパーフルオロアルキル基とサイズの小さいメチル基からなる疎水基を高い濃度で形成した撥水性物品が開示されている。しかし、これは積極的にパーフルオロアルキル基含有シラン化合物とポリジメチルシロキサンを共重合させた新たな組成物ではなく、３０°の傾斜で約１５μl以下の良好な滑水性（水滴滑落性）を示すものは得られていない。
【０００８】
【課題を解決するための手段】
本発明は、従来の前記課題に鑑みてなされたものであって、高い撥水耐久性（耐光性や耐摩耗性）と優れた滑水性（以下「水滴滑落性」という場合もある）を兼ね備えた高滑水性基材およびその製造方法を提供するものである。
【０００９】
すなわち、本発明の高滑水性基材は、基板表面に、一般式［１］で表されるパーフルオロアルキルトリクロロシランと一般式［２］で表されるジメチルシリコーンジオールを混合モル比がパーフルオロトリクロロシラン１に対して、ジメチルシリコーンジオールが０．１乃至２．０の条件で、非水溶媒中で２時間を越えて混合して反応させ共重合させた反応生成物を希釈溶媒で希釈してなる表面処理剤を塗布し、６０℃〜１９０℃で熱処理して被膜を形成したことを特徴とする。
【００１０】
【化３】
【００１１】
【化４】
【００１２】
また、本発明の高滑水性基材の製造方法は、基板表面に、一般式［１］で表されるパーフルオロアルキルトリクロロシランと一般式［２］で表されるジメチルシリコーンジオールを混合モル比がパーフルオロトリクロロシラン１に対して、ジメチルシリコーンジオールが０．１乃至２．０の条件で、非水溶媒中で２時間を越えて混合して反応させ共重合させた反応生成物を希釈溶媒で希釈してなる表面処理剤を塗布し、６０℃〜１９０℃で熱処理して被膜を形成することを特徴とする。
【００１３】
【発明の実施の形態】
本発明の高滑水性基材は、基板表面に、一般式［１］で表されるパーフルオロアルキルトリクロロシランと一般式［２］で表されるジメチルシリコーンジオールを非水溶媒中で混合して反応させ共重合させた反応生成物を希釈溶媒で希釈してなる表面処理剤を塗布した後、乾燥することにより製造することが出来る。
【００１４】
【化５】
【００１５】
【化６】
【００１６】
前記一般式［１］で表されるパーフルオロアルキルトリクロロシランとしては、例えばＣＦ3（ＣＦ2）11ＣＨ2ＣＨ2ＳｉＣｌ3、ＣＦ3（ＣＦ2）9ＣＨ2ＣＨ2ＳｉＣｌ3、ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2ＳｉＣｌ3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＳｉＣｌ3等を用いることができる。
【００１７】
一般式［２］で表されるジメチルシリコーンジオールとしては、例えば、ＨＯ-[Ｓｉ(ＣＨ3)2Ｏ-]10Ｈ、ＨＯ-[Ｓｉ(ＣＨ3)2Ｏ-]20Ｈ等を用いることができる。
【００１８】
非水溶媒としては、水の溶解度が小さく水分を実質的に含まない溶媒であり、例えば、酢酸エチル、酢酸ｎ-ブチル、酢酸ｎ-ヘキシルなどのエステル類、トルエン、キシレンなどの芳香族炭化水素類、ｎ−ブタン、ｎ−ヘキサンなどの脂肪族炭化水素類等を用いることができる。
【００１９】
希釈溶媒としては、イソプロピルアルコ−ル（以下、「ｉ−ＰＡ」と略す）の他に、メタノ−ル、エタノ−ルなど炭素数が５以下の低級アルコ−ル溶媒であってもよく、アルコ−ル以外にエ−テル類やケトン類を用いることができ、ことにｉ−ＰＡまたはエタノールを主成分としてなるアルコール類が好ましい。
【００２０】
なお、前記パーフルオロアルキルトリクロロシランとジメチルシリコーンジオールの混合モル比は、自在に選択可能であるが、パーフルオロアルキルトリクロロシラン：ジメチルシリコーンジオール＝１：０.１〜２の条件で共重合反応を行わせることが好ましく、パーフルオロアルキルトリクロロシラン１に対して、ジメチルシリコーンジオールが０．１以下の場合には、目的である滑水性の改善効果は得られなくなり、２以上の場合には、良好な滑水性は得られるものの耐光性などの耐久性能が大幅に低下して実用上好ましくない。
なお、前記パーフルオロアルキルトリクロロシランとジメチルシリコーンジオールを非水溶媒中で混合して共重合させる反応時間は２時間を越えて反応させる必要があり、それより短いと高滑水性が得られないので好ましくない。
【００２１】
表面処理剤を塗布した後の乾燥は、表面処理剤を塗布後に風乾により自然乾燥させてもよいし、乾燥後または乾燥と同時に室温を越え１９０℃以下の温度で熱処理を行うことも出来る。
なお、熱処理を行う場合には、室温を越え１９０℃の温度で熱処理を行う必要があり、その処理により未反応のフルオロアルキル基含有シランのＯＨ基を他のＯＨ基と結合させる。しかし、２００℃以上であると滑水性を改善するためのシリコーンオイルジオールが熱分解し易く、好ましくない。また、反応効率の点で６０℃以上がより好ましい。
【００２２】
本発明についての滑水性とは、後述の実施例の評価方法で述べるような方法、例えば、前記表面処理剤で処理された被膜を有するサンプルを３０°に傾斜させた状態で、該サンプル表面上にゆっくりとマイクロシリンジで純水を滴下する。このとき、水滴が動き始める時点の水滴量（体積）を滑水性（水滴転落性）とし、μlで示すものである。本発明の高滑水性とは前記方法により得られる滑水性が３０μl以下、より好ましくは２０μl以下、のものをいう。
【００２３】
本発明で得られる高滑水性被膜を有する基材は、フルオロアルキル基含有シランからなる撥水性被膜が基材表面に固定化されているため、前記滑水性とともに、優れた撥水性も兼ね備えている。
【００２４】
基材としては、ガラス、プラスチック等特に限定されるものではないが、例えば、ガラス基板の場合には、建築用窓ガラスや自動車用窓ガラス等に通常使用されているフロ−トガラスあるいはロ−ルアウト法で製造されたガラス等無機質の透明性がある板ガラスが好ましく、無色または着色、ならびにその種類あるいは色調、他の機能性膜との組み合わせ、ガラスの形状等に特に限定されるものではなく、さらに曲げ板ガラスとしてはもちろん各種強化ガラスや強度アップガラスであり、平板や単板で使用できるとともに、複層ガラスあるいは合わせガラスとしても使用できる。また、被膜はガラス基板の両面に成膜しても構わない。
表面処理剤が塗布される基材表面は、金属酸化物よりなる下地層を設けられていてもよい。
例えば、ガラス基板の場合には、下地層は、ケイ素酸化物等の金属酸化物を主成分とする酸化物薄膜が好ましく、その上に前記表面処理剤を塗布して高滑水性被膜を被覆することにより、高耐久性を有する高滑水性ガラスを得ることが出来る。
【００２５】
さらに、下地層表面を凹凸にすると耐久性がより向上するので特に好ましく、その方法としては、例えば金属アルコキシド系化合物或いは金属アセチルアセトネート系化合物の中から少なくとも２種以上選択し、しかも該選択した２つ以上の化合物における平均分子量が異なるものであって、該２つ以上の化合物を溶剤とともに混合して塗布溶液とし、該溶液を被覆後、加熱してマイクロピット状や凹凸状の表層をつくる方法等が採用できるが、下地層表面を凹凸にする方法はこれに限定されるものではない。
【００２６】
また、基材表面への表面処理剤の塗布方法としては、手塗り、ノズルフロ−コ−ト法、ディッピング法、スプレー法、リバ−スコ−ト法、フレキソ法、印刷法、フローコート法あるいはスピンコート法、ならびにそれらの併用等既知の塗布手段など各種塗布法が適宜採用し得る。また、簡易なタイプのスプレー式撥水処理剤などとしても使用することができる。
【００２７】
以下の実施例および比較例に共通な項目である、表面処理剤の調製、塗布用基板の作製および得られた滑水性基板の実用耐久性の評価方法については、以下の方法により行った。
【００２８】
［表面処理剤の調製］
図１に、表面処理剤の調製手順を示す。表面処理剤の調製には、撥水剤にヘプタデカフルオロデシルトリクロロシラン(ＣＦ3(ＣＦ2)7ＣＨ2ＣＨ2ＳｉＣｌ3：東芝シリコーン製ＴＳＬ８２３２、以下「ＦＡＳＣ」と記す)と平均重合度１０および２０のシリコーンオイルジオール(以下「Ｎ１０ＳＯＬ」および「Ｎ２０ＳＯＬ」と記す)を用いた。
【００２９】
例えば、ＦＡＳＣ-Ｎ１０ＳＯＬ(１:１)系の場合の手順としては、５.００ｇの酢酸エチルと３.９０ｇのＮ１０ＳＯＬを秤量して混合した。次に、この混合物に対して、攪拌しながら２.５０ｇのＦＡＳＣをゆっくりと滴下して加え、さらに室温で密栓した状態で０〜２４ｈ攪拌して母液を得た。次いで、１.０ｇの母液を９.０ｇのｉ-ＰＡで希釈して１０分程度攪拌して表面処理剤を得た。なお、ＦＡＳＣを秤量および添加する際には、ＦＡＳＣが大気中の水分を吸湿して加水分解することを可能な限り避けるために、実験室内の湿度を５５％ＲＨ以下に保つことが好ましかった。なお、表１に各系（( )内の比は混合モル比を示す）における各成分の秤量値（ｇ）を示す。
【００３０】
【表１】
【００３１】
［塗布用基板の作製］
基板としては、下記に示す３種類を用いた。
【００３２】
１)下地なしタイプ(以下、「基板Ａ」と記す)
２００ｍｍ×２００ｍｍ×２ｍｍｔサイズのフロートガラス、または、強化ガラスを通常のガラス洗浄機(当所製作品)で水洗および乾燥した。
【００３３】
２)下地なしタイプ(以下、「基板Ｂ」と記す)
２００ｍｍ×２００ｍｍ×２ｍｍｔサイズのフロートガラス、または、強化ガラスの表面を、研磨液とブラシポリッシャーを用いて研磨し、十分に研摩剤を除去した後、３５℃の０.１Ｎ硫酸水溶液中に１分間浸漬した。その後、通常のガラス洗浄機(当所製作品)にて水洗および乾燥した。なお、ここで用いた研磨液は、約１％のガラス用研摩剤ミレークＡ（三井金属工業製）を水に混合した懸濁液を用いた。
【００３４】
３)凹凸の表面形状を有するシリカ系下地層タイプ(以下、「基板Ｃ」と記す)
２００ｍｍ×２００ｍｍ×２ｍｍｔサイズのフロートガラス基板の表面を、約１％のガラス用研摩剤ミレークＡ（三井金属工業製）を水に混合した懸濁液とプラシポリッシャーを用いて表面を研磨したのち、充分に水洗・乾燥したものを塗布布用基板とした。なお、下地層用のコーティング液は、次のようにして調製した。
【００３５】
テトラエトキシシラン〔Ｓｉ(ＯＣ2Ｈ5)4：ＴＥＯＳ〕の重合ゾル(平均分子量Ｍｗ：約１０００〜３０００）とアセチルアセトンで安定化したテトラブトキシチタン〔Ｔｉ(Ｏ-Ｂｕ)4〕との混合ゾル（アセチルアセトンとで安定化したテトラブトキシチタンの合有量は酸化物換算でＳｉＯ2に対してモル比で約４mol％）を、イソプロピルアルコール(ｉＰＡ)溶媒を加え、固形分濃度として酸化物換算で５ｗｔ％になるまで希釈したものをゾル溶液Ａとした。また、メチルトリメトキシシラン〔ＣＨ3Ｓｉ(ＯＣＨ3)3：ＭＴＭＳ〕の重合ゾル(平均分子量Ｍｗ＝約１，０００)にイソプロピルアルコール(ｉＰＡ)を加え、固形分濃度として酸化物換算で約２０ｗｔ％になるまで希釈したものをゾル溶液Ｂとした。次に、ゾル溶液Ａ；２０ｇ、ゾル溶液Ｂ；２０ｇ、および、加水分解および脱水縮合反応の速度を調整するための溶媒としてのブタノール(ｎ-ＢｕＯＨ)；２５ｇとを混合し、約５０℃で約３時間密栓して撹拌した（ゾル溶液Ｃ）。さらに、ｉＰＡ(９０ｗｔ％)；３２４ｇとｎ-ＢｕＯＨ(１０ｗｔ％)；３６ｇの混合系溶媒約３６０ｇで先のゾル溶液Ｃを希釈してコーテイング液を得た。
【００３６】
塗布方法は、スピンコート法で行った。先ず、スピンコーター上に被覆用ガラス基板をセットし、先ず塗布被膜域（高速スピン回転）において、スピン回転を開始し、回転速度が１５０ｒｐｍで３秒後、上記塗布液の塗布量としては２０ｍｌ程度滴下し、１８秒回転速度を維持し被膜化した。続いてレベリング域(スピン回転停止)において、被膜化した塗布液が渇きはじめて流動性を失うようになる前に、スピン回転を一旦停止し６０秒間静止してレベリングせしめ、乾燥促進域(低速スピン回転)において、再度スピン回転を始め、５０ｒｐｍの低速回転で４０秒間維持し、塗膜の乾燥促進を行い、良好な成膜性のゲル膜を得た。
【００３７】
次に、該ゲル膜付きガラス基板を２５０℃で３０分間仮焼成を行い、さらにガラス温度で６３０℃〜６６０℃の本焼成を行い、表面に微細な凹凸形状を有するＳｉＯ2-ＴｉＯ2薄膜を得た。
【００３８】
［実用耐久性の評価方法］
得られた高滑水性ガラスの評価は、下記に示す４つの方法で行った。
【００３９】
１)初期接触角
水滴をサンプルに乗せたときの水滴と基盤表面とのなす角を接触角計で測定した。
【００４０】
接触角計：協和界面科学製ＣＡ−Ｘ型
測定環境：大気中(約２５℃)
水：純水(２μｌ)。
【００４１】
２)水滴転落性
サンプルを３０゜に傾斜させた状態で、サンプル表面上にゆっくりとマイクロシリンジで純水を滴下する。このとき、水滴が動き始める時点の水滴量（体積）をμlで示し、「滑水性」と表現した。
【００４２】
３)耐摩耗性
以下の試験機を用いて、摺動回数(３５００回)後、接触角θ(°)を測定した。
【００４３】
試験機：トラバース式摺動試験機（自社製作）
摺動面積：１００ｍｍ×２５ｍｍ
摩擦布：キャンバス布(ＪＩＳＬ３１０２-１９６1-1２０６)
荷重：０.１ｋｇ/ｃｍ2
ストローク：１００ｍｍの往復摺動(摺動回数は往復の回数)
摺動速度：３０往復／分。
【００４４】
４)耐光性
以下の試験機を用いて、メタルハライドランプの強力なＵＶ光をサンプルに２ｈ照射した後の接触角θ(°)を測定して評価した。
【００４５】
試験機 ：高速耐光性試験機（自社製作）
ランプ ：１.５ｋＷメタルハライドランプ（アイグラフィックス製Ｍ０１５-Ｌ３１２）
ランプ-サンプル間距離：１６０mm
なお、下記に示す実施例及び比較例で得られたサンプルの評価結果を表２に示す。
【００４６】
【実施例】
以下に、本発明の実施例について説明する。
【００４７】
実施例１
本例は、ＦＡＳＣとＮ１０ＳＯＬの混合比をモル比で１：１の場合である。
先ず、５.００ｇの酢酸エチルと３.９０ｇのＮ１０ＳＯＬを秤量して混合した。次に、この混合物に対して、攪拌しながら２.５０ｇのＦＡＳＣをゆっくりと滴下して加え、さらに室温（２０〜２５℃）で密栓した状態で６ｈ攪拌して母液を得た。次いで、１.０ｇの母液を９.０ｇのｉ-ＰＡで希釈して１０分程度攪拌して表面被膜形成用処理剤を得た。この表面処理剤を基板Ａに温度を２５℃、湿度を４５％ＲＨに保った環境下で、２ｍｌ/ｐｃの表面処理剤を滴下し、綿布（商品名；ベンコット）でガラス全面に十分引き伸ばした後、５分程度風乾した。その後、マッフル炉でガラス温度で１５０℃、５分程度の熱処理を行い、白濁して残った余剰な撥水剤をｉＰＡで拭き上げて透明なサンプルを得た。得られたサンプルの評価結果は表２に示すように、初期接触角は１００°、滑水性は１３μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９８°および９８°で試験前後の接触角の変化は殆どなかった。
なお、表２において、ＦＡＳ欄は使用したＦＡＳの種類を示し、-Cl3；トリクロロシランタイプ（ＦＡＳＣ）、 -OCH3；トリメトキシシランタイプである。また、添加量はすべて１molとした。
【００４８】
実施例２
表面処理剤の塗布を基板Ｂに行った以外は実施例１と同様にした。得られたサンプルの初期接触角は１０２°、滑水性は８μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、１００°および９６°で高い実用耐久性を示した。
【００４９】
実施例３
表面処理剤の塗布を基板Ｃに行った以外は実施例１と同様にした。得られたサンプルの初期接触角は１００°、滑水性は８μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９９°および９５°で高い実用耐久性を示した。
【００５０】
実施例４
表面処理剤を調製する際の反応時間を１２時間とした以外は実施例２と同様にした。得られたサンプルの初期接触角は１０１°、滑水性は８μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９８°および９８°で高い実用耐久性を示した。
【００５１】
実施例５
表面処理剤を調製する際の反応時間を１２時間とした以外は実施例３と同様にした。得られたサンプルの初期接触角は１０１°、滑水性は８μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９８°および９８°で高い実用耐久性を示した。
【００５２】
【表２】
【００５３】
実施例６
表面処理剤を調製する際の反応時間を２４時間とした以外は実施例２と同様にした。得られたサンプルの初期接触角は９９°、滑水性は８μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９８°および９８°で高い実用耐久性を示した。
【００５４】
実施例７
表面処理剤を調製する際の反応時間を２４時間とした以外は実施例３と同様にした。得られたサンプルの初期接触角は１００°、滑水性は８μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９８°および９８°で高い実用耐久性を示した。
【００５５】
実施例８
ＦＡＳＣとＮ１０ＳＯＬの混合比をモル比で１：２とした以外の条件は実施例２と同様とした。得られたサンプルの初期接触角は１０１°、滑水性は８μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９７°および９６°で高い実用耐久性を示した。
【００５６】
実施例９
表面処理剤の塗布を基板Ｃに行った以外は実施例８と同様にした。得られたサンプルの初期接触角は１００°、滑水性は１３μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９７°および９７°で高い実用耐久性を示した。
【００５７】
実施例１０
シリコーンオイルジオールに平均重合度が２０であるＮ２０ＳＯＬを用い、ＦＡＳＣとの混合比をモル比で１：２とした。その他の条件は実施例２と同様とした。得られたサンプルの初期接触角は１０１°、滑水性は１７μｌと良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９８°および９５°で高い実用耐久性を示した。
【００５８】
実施例１１
表面処理剤の塗布を基板Ｃに行った以外は実施例１０と同様にした。得られたサンプルの初期接触角は９８°、滑水性は１５μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９８°および９７°で高い実用耐久性を示した。
【００５９】
実施例１２
サンプル作製の際に、熱処理をしないこと以外は実施例２と同様にした。得られたサンプルの初期接触角は１００°、滑水性は１０μｌと極めて良好な水滴滑落性を示した。また、耐摩耗性および耐光性は、９８°および９８°で高い実用耐久性を示した。
【００６０】
比較例１
表面処理剤の調製の際に、シリコーンオイルジオールを混合しないで、ＦＡＳＣ１ｇに希釈溶媒であるｉＰＡ２５ｇと酸触媒である０.１Ｎ硝酸(ＨＮＯ3)を０.３ｇ加え、室温で約２時間攪拌して加水分解反応を終結させた。その他の条件は実施例２と同様とした。得られたサンプルの初期接触角は１０８°、滑水性は５０μｌと水滴の滑落性は悪かった。また、耐摩耗性および耐光性は、７０°および１００°で、耐摩耗性は実用に供するレベルでなかった。
【００６１】
比較例２
表面処理剤の塗布を基板Ｃに行った以外は比較例１と同様にした。得られたサンプルの初期接触角は１１２°、滑水性は５５μｌと悪いレベルであった。また、耐摩耗性および耐光性は、１１０°および１０６°であり、実用耐久性については実用に供することのできるレベルのものであったが、滑水性は満足できるものではなかった。
【００６２】
比較例３
表面処理剤の調製の際に、パーフルオロアルキルトリクロロシラン（ＦＡＳＣ）を混合しないで、Ｎ１０ＳＯＬ；１ｇをｉＰＡ；９ｇで希釈するのみとした。その他は実施例２と同様とした。得られたサンプルの初期接触角は９１°、滑水性は１５μｌと水滴の滑落性は良いレベルであったが、耐摩耗性は７６°、耐光性は８０°と実用に供するレベルでなかった。
【００６３】
比較例４
表面処理剤の調製の際に、パーフルオロアルキルトリクロロシラン（ＦＡＳＣ）を混合しないで、Ｎ２０ＳＯＬ；１ｇをｉＰＡ；９ｇで希釈するのみとした。その他は実施例２と同様とした。得られたサンプルの初期接触角は９４°、滑水性は１０μｌと水滴の滑落性は良いレベルであったが、耐摩耗性は８９°、耐光性は８９°と実用に供するレベルでなかった。
【００６４】
比較例５
サンプル作製の際に、熱処理温度を２００℃にした以外は実施例２と同様にした。得られたサンプルの初期接触角は１００°、滑水性は５０μｌと水滴の滑落性は悪かった。一方、耐摩耗性は１００°、耐光性は９８°と高い実用耐久性であった。
【００６５】
比較例６
サンプル作製の際に、熱処理温度を３５０℃にした以外は実施例２と同様にした。得られたサンプルの初期接触角は１０３°、滑水性は５５μｌと水滴の滑落性は悪かった。一方、耐摩耗性は１０１°、耐光性は９９°と高い実用耐久性であった。
【００６６】
比較例７
表面処理剤調製時の反応時間を１時間とした以外は実施例２と同様にした。得られたサンプルの初期接触角は１００°、滑水性は５５μlと水滴の滑落性は悪かった。一方、耐摩耗性は９５°、耐光性は９５°と実用耐久性は良好であった。
【００６７】
比較例８
表面処理剤調製時の反応時間を２時間とした以外は実施例２と同様にした。得られたサンプルの初期接触角は１０３°、滑水性は５０μlと水滴の滑落性は悪かった。一方、耐摩耗性は９５°、耐光性は９５°と実用耐久性は良好であった。
【００６８】
比較例９
表面処理剤の調製の際に、撥水剤をヘプタデカフルオロデシルトリメトキシシラン(ＣＦ3(ＣＦ2)7ＣＨ2ＣＨ2Ｓｉ(ＯＣＨ3)3：信越シリコーン製ＫＢＭ−７８０３、ＦＡＳＭと記す)を用いた以外は実施例２と同様にした。得られたサンプルの初期接触角は１０７°、滑水性は４０μlと水滴の滑落性は悪かった。一方、耐摩耗性は１０５°、耐光性は９６°と実用耐久性は良好であった。
【００６９】
比較例１０
表面処理剤を調製する際の反応時間を２４時間とした以外は比較例９と同様にした。得られたサンプルの初期接触角は１０７°、滑水性は４５μｌと水滴の滑落性は悪かった。一方、耐摩耗性は１０５°、耐光性は９５°と実用耐久性は良好であった。
【００７０】
比較例１１
表面処理剤を調製する際に、平均重合度が２０のシリコーンオイルジオールを用いた以外は、比較例９と同様にした。得られたサンプルの初期接触角は１１０°、滑水性は４０μlと水滴の滑落性は悪かった。一方、耐摩耗性は１０５°、耐光性は９５°と実用耐久性は良好であった。
【００７１】
比較例１２
表面処理剤を調製する際の反応時間を２４時間とした以外は比較例１１と同様にした。得られたサンプルの初期接触角は１１０°、滑水性は４０μｌと水滴の滑落性は悪かった。一方、耐摩耗性は１０５°、耐光性は９５°と実用耐久性は良好であった。
【００７２】
【発明の効果】
本発明は、極めて優れた水滴滑落性（滑水性）を示す新規な高滑水性基材およびその製造方法に関するものであり、滑水性（３０°傾斜）が１０μｌ以下を示し、かつ、良好な実用耐久性を兼ね備えた優れた撥水性と滑水性が得られる。これにより、従来から問題であったフッ素系撥水剤の水滴滑落性について、耐久性を大幅に損なうことなく、改善することが可能となった。
【図面の簡単な説明】
【図１】本発明の表面処理剤の調製工程を示すフロー図である[0001]
[Field of the Invention]
INDUSTRIAL APPLICABILITY The present invention is a method for producing a highly slidable base material exhibiting extremely excellent water slidability (water droplet slidability) that can be used particularly for architectural window glass, vehicle window glass, mirrors, and other industrial window glass. About.
[0002]
[Prior art]
In order to obtain high water repellency durability (light resistance and abrasion resistance), a great many inventions have been made on water-repellent glass obtained by treating a substrate surface with a fluoroalkyl group-containing silane compound. For example, JP-A-6-16455 discloses that it is very effective to provide a base film such as silica having an uneven shape on the glass surface. Japanese Patent No. 2500188 discloses a method for forming a water- and oil-repellent monomolecular film on a glass surface, and Japanese Patent Application Laid-Open No. 10-59745 discloses that a glass surface to be water-repellent treated is ceria polished and further acid-treated. A method of increasing the activity of the substrate and a method of using a fluoroalkyl group-containing silane compound having an increased or controlled degree of polymerization as a water repellent treatment liquid are disclosed. Further, JP-A-8-325037 discloses that a fluoroalkyl group-containing silane compound is treated after forming an alkali barrier layer containing no alkali metal or having a low alkali metal content in the vicinity of the glass substrate surface. A method for obtaining a highly durable water-repellent treated glass is disclosed. Furthermore, Japanese Patent Laid-Open No. 9-48639 discloses that a fluoroalkyl group-containing silane compound is treated after forming a surface with a reduced amount of alkali components such as sodium by making the glass substrate surface a dealkalized layer. Discloses improving heat resistance, water resistance and weather resistance.
[0003]
On the other hand, studies have been made with an emphasis on further improving the water drop slidability, and high water slidability or high water slidability glass has been proposed. For example, a composition containing a silicone wax, an organopolysiloxane, a surfactant and the like has been invented. Japanese Patent Publication No. 50-15473 discloses a composition comprising an alkylpolysiloxane and an acid, No. 301742 discloses a composition containing an amino-modified silicone oil and a surfactant.
[0004]
Further, a composition having both high water repellency durability (light resistance and abrasion resistance) and excellent water droplet sliding property has been invented. JP-A-11-116943 discloses a perfluoroalkyl group-containing silane compound. A surface treating agent comprising a composition in which at least the terminal F atom of the fluoroalkyl group is substituted with an H atom is disclosed. JP-A-8-12375 discloses a water-repellent article in which a composition obtained by hydrolyzing a perfluoroalkyl group-containing silane compound and polydimethylsiloxane is applied to a glass substrate or the like.
[0005]
[Problems to be solved by the invention]
However, high water repellency (light resistance) described in JP-A-6-16455, JP-A-2500188, JP-A-10-59745, JP-A-8-325037, and JP-A-9-48639. The water-repellent glass in which the substrate surface is treated with a fluoroalkyl group-containing silane compound having high resistance and wear resistance) has poor water drop slidability (water slidability), for example, an inclination angle of 30 ° which is an attachment angle of an automotive windshield In this case, at least when the volume of the water droplet is not more than about 40 to 60 μl at rest, the water droplet does not slide down and remains on the glass surface.
[0006]
Also, those obtained by the methods of Japanese Patent Publication No. 50-15473 and Japanese Patent Application Laid-Open No. 5-301742 have good sliding properties (water droplet sliding properties), in which about 30 μl is inclined at 30 °. Although a thing that slides down with water droplets has been obtained, it has not yet achieved high water repellency durability (light resistance and abrasion resistance).
[0007]
Further, in the method described in JP-A-8-12375, a perfluoroalkyl group-containing silane compound and a polydimethylsiloxane compound are mixed and hydrolyzed, and then mixed with the hydrolyzed alkoxysilane compound to prepare a solution. It is shown that this is applied to the surface of a substrate, and a water-repellent article in which a hydrophobic group comprising a bulky and rigid perfluoroalkyl group and a small-sized methyl group is formed on the outer surface layer of the hybrid film at a high concentration Is disclosed. However, this is not a new composition obtained by positively copolymerizing a perfluoroalkyl group-containing silane compound and polydimethylsiloxane, and exhibits a good water sliding property (water droplet sliding property) of about 15 μl or less at a 30 ° inclination. Nothing has been obtained.
[0008]
[Means for Solving the Problems]
The present invention has been made in view of the above-described conventional problems, and has high water repellency durability (light resistance and wear resistance) and excellent water slidability (hereinafter sometimes referred to as “water droplet slidability”). A highly water-slidable substrate and a method for producing the same are provided.
[0009]
That is, the highly lubricious base material of the present invention comprises perfluoroalkyltrichlorosilane represented by the general formula [1] and dimethyl silicone diol represented by the general formula [2] on the substrate surface.With the mixing molar ratio of perfluorotrichlorosilane 1 and dimethyl silicone diol being 0.1 to 2.0,In non-aqueous solventsOver 2 hoursA surface treatment agent is prepared by diluting the reaction product mixed and reacted and copolymerized with a diluent solvent.The film is formed by heat treatment at 60 ° C. to 190 ° C.
[0010]
[Chemical Formula 3]
[0011]
[Formula 4]
[0012]
In the method for producing a highly lubricious base material of the present invention, a perfluoroalkyltrichlorosilane represented by the general formula [1] and a dimethyl silicone diol represented by the general formula [2] are provided on the substrate surface.With the mixing molar ratio of perfluorotrichlorosilane 1 and dimethyl silicone diol being 0.1 to 2.0,In non-aqueous solventsOver 2 hoursA surface treatment agent is prepared by diluting the reaction product mixed and reacted and copolymerized with a diluent solvent.The film is formed by heat treatment at 60 ° C. to 190 ° C.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The highly water-slidable base material of the present invention is obtained by mixing perfluoroalkyltrichlorosilane represented by the general formula [1] and dimethyl silicone diol represented by the general formula [2] in a non-aqueous solvent on the substrate surface. It can be manufactured by applying a surface treatment agent obtained by diluting a reaction product obtained by reaction and copolymerization with a diluting solvent, followed by drying.
[0014]
[Chemical formula 5]
[0015]
[Chemical 6]
[0016]
Examples of the perfluoroalkyltrichlorosilane represented by the general formula [1] include CF.Three(CF2)11CH2CH2SiClThree, CFThree(CF2)9CH2CH2SiClThree, CFThree(CF2)7CH2CH2SiClThree, CFThree(CF2)FiveCH2CH2SiClThreeEtc. can be used.
[0017]
Examples of the dimethyl silicone diol represented by the general formula [2] include HO— [Si (CHThree)2O-]TenH, HO- [Si (CHThree)2O-]20H or the like can be used.
[0018]
Non-aqueous solvents are those having low water solubility and substantially no water content, such as esters such as ethyl acetate, n-butyl acetate and n-hexyl acetate, and aromatic hydrocarbons such as toluene and xylene. , Aliphatic hydrocarbons such as n-butane and n-hexane can be used.
[0019]
As a diluent solvent, in addition to isopropyl alcohol (hereinafter abbreviated as “i-PA”), a lower alcohol solvent having 5 or less carbon atoms such as methanol and ethanol may be used. Ethers and ketones can be used in addition to alcohol, and alcohols mainly composed of i-PA or ethanol are particularly preferable.
[0020]
The mixing molar ratio of the perfluoroalkyltrichlorosilane and dimethylsilicone diol can be freely selected. However, the copolymerization reaction is performed under the conditions of perfluoroalkyltrichlorosilane: dimethylsilicone diol = 1: 0.1-2. It is preferable to carry out the treatment. When the dimethyl silicone diol is 0.1 or less with respect to the perfluoroalkyltrichlorosilane 1, the intended effect of improving the water slidability cannot be obtained. Although good water slidability is obtained, durability performance such as light resistance is greatly lowered, which is not preferable in practice.
The reaction time for mixing the perfluoroalkyltrichlorosilane and dimethyl silicone diol in a non-aqueous solvent for copolymerization must exceed 2 hours, and if it is shorter than that, high lubricity cannot be obtained. It is not preferable.
[0021]
Drying after applying the surface treatment agent may be carried out by air drying after the application of the surface treatment agent, or heat treatment may be performed at a temperature of 190 ° C. or less exceeding room temperature after drying or simultaneously with drying.
When heat treatment is performed, it is necessary to perform the heat treatment at a temperature of 190 ° C. exceeding room temperature, and the OH group of the unreacted fluoroalkyl group-containing silane is bonded to other OH groups by the treatment. However, when the temperature is 200 ° C. or higher, the silicone oil diol for improving the water slidability is easily decomposed by heat, which is not preferable. Moreover, 60 degreeC or more is more preferable at the point of reaction efficiency.
[0022]
The slipperiness for the present invention is a method as described in the evaluation method of the examples described later, for example, on the surface of the sample in a state where the sample having the coating treated with the surface treatment agent is inclined at 30 °. Slowly add pure water dropwise with a microsyringe. At this time, the amount (volume) of water droplets at the time when the water droplets start to move is defined as the slidability (water droplet tumbling property) and expressed in μl. The high water slidability of the present invention refers to a water slidability obtained by the above method of 30 μl or less, more preferably 20 μl or less.
[0023]
The base material having a highly water-slidable film obtained in the present invention has an excellent water repellency along with the water slidability because the water-repellent film made of a fluoroalkyl group-containing silane is immobilized on the surface of the base material. .
[0024]
The base material is not particularly limited, such as glass and plastic. For example, in the case of a glass substrate, a float glass or a roll-out that is usually used for architectural window glass or automobile window glass is used. Inorganic transparent plate glass such as glass produced by the method is preferred, and it is not particularly limited to colorless or colored, as well as its type or color tone, combination with other functional films, glass shape, etc. Of course, various types of tempered glass and strength-enhancing glass can be used as the bent plate glass, and it can be used as a flat plate or a single plate, and can also be used as a double-layer glass or a laminated glass. The coating may be formed on both sides of the glass substrate.
The base material surface to which the surface treatment agent is applied may be provided with a base layer made of a metal oxide.
For example, in the case of a glass substrate, the underlayer is preferably an oxide thin film mainly composed of a metal oxide such as silicon oxide, and the surface treatment agent is applied thereon to cover the highly water-slidable film. As a result, a highly slippery glass having high durability can be obtained.
[0025]
Furthermore, it is particularly preferable to make the surface of the underlayer uneven, since durability is further improved. As the method, for example, at least two or more kinds selected from metal alkoxide compounds or metal acetylacetonate compounds are selected. Two or more compounds having different average molecular weights are mixed with a solvent to form a coating solution, and after coating the solution, it is heated to form a micropit-like or uneven surface layer. Although a method etc. can be employ | adopted, the method of making an underlayer surface uneven | corrugated is not limited to this.
[0026]
The surface treatment agent can be applied to the substrate surface by hand coating, nozzle flow coating method, dipping method, spray method, river coating method, flexo method, printing method, flow coating method or spin coating method. Various coating methods such as a coating method and known coating means such as a combination thereof can be appropriately employed. It can also be used as a simple type spray-type water repellent agent.
[0027]
The following methods were used for the preparation of the surface treatment agent, the production of the coating substrate, and the method for evaluating the practical durability of the resulting slidable substrate, which are items common to the following Examples and Comparative Examples.
[0028]
[Preparation of surface treatment agent]
In FIG. 1, the preparation procedure of a surface treating agent is shown. For the preparation of the surface treatment agent, heptadecafluorodecyltrichlorosilane (CFThree(CF2)7CH2CH2SiClThree: TSL 8232 manufactured by Toshiba Silicone, hereinafter referred to as “FASC”) and silicone oil diol having an average polymerization degree of 10 and 20 (hereinafter referred to as “N10SOL” and “N20SOL”) were used.
[0029]
For example, as a procedure for the FASC-N10SOL (1: 1) system, 5.00 g of ethyl acetate and 3.90 g of N10SOL were weighed and mixed. Next, 2.50 g of FASC was slowly added dropwise to the mixture with stirring, and the mixture was further stirred at room temperature for 0 to 24 hours to obtain a mother liquor. Next, 1.0 g of the mother liquor was diluted with 9.0 g of i-PA and stirred for about 10 minutes to obtain a surface treating agent. When weighing and adding FASC, it is preferable to keep the humidity in the laboratory below 55% RH in order to prevent FASC from absorbing and hydrolyzing moisture in the atmosphere as much as possible. It was. Table 1 shows the weighed value (g) of each component in each system (ratio in parentheses indicates mixing molar ratio).
[0030]
[Table 1]
[0031]
[Production of substrate for coating]
As the substrate, the following three types were used.
[0032]
1) Baseless type (hereinafter referred to as “Board A”)
A float glass or a tempered glass having a size of 200 mm × 200 mm × 2 mmt was washed with water and dried with an ordinary glass washer (produced by this company).
[0033]
2) Baseless type (hereinafter referred to as “Substrate B”)
The surface of float glass or tempered glass of 200 mm × 200 mm × 2 mmt size is polished with a polishing liquid and a brush polisher, and after sufficiently removing the abrasive, it is placed in a 0.1N sulfuric acid aqueous solution at 35 ° C. for 1 minute. Soaked. Thereafter, it was washed with water and dried with a normal glass washer (produced by our company). The polishing liquid used here was a suspension obtained by mixing approximately 1% of glass abrasive agent Mille A (Mitsui Metal Industry) with water.
[0034]
3) Silica-based underlayer type having an uneven surface shape (hereinafter referred to as “substrate C”)
After polishing the surface of a float glass substrate having a size of 200 mm × 200 mm × 2 mmt with a suspension obtained by mixing about 1% of glass abrasive Mille A (Mitsui Metal Industries) in water and a plus polisher, A sufficiently washed and dried substrate was used as a coated fabric substrate. The undercoat layer coating solution was prepared as follows.
[0035]
Tetraethoxysilane [Si (OC2HFive)Four: TEOS] polymerized sol (average molecular weight Mw: about 1000 to 3000) and tetrabutoxytitanium [Ti (O-Bu) stabilized with acetylacetoneFour] The mixed sol (the amount of tetrabutoxytitanium stabilized with acetylacetone is SiO in terms of oxide)2A sol solution A was prepared by adding an isopropyl alcohol (iPA) solvent to a molar ratio of about 4 mol% with respect to the total solid content and diluting to a solid content concentration of 5 wt% in terms of oxide. In addition, methyltrimethoxysilane [CHThreeSi (OCHThree)Three: MTMS], a sol solution B was prepared by adding isopropyl alcohol (iPA) to a polymerization sol (average molecular weight Mw = about 1,000) and diluting it to a solid content concentration of about 20 wt% in terms of oxide. Next, sol solution A; 20 g, sol solution B; 20 g, and butanol (n-BuOH) as a solvent for adjusting the rate of hydrolysis and dehydration condensation reaction; 25 g were mixed at about 50 ° C. Sealed and stirred for about 3 hours (sol solution C). Furthermore, the previous sol solution C was diluted with about 360 g of a mixed solvent of iPA (90 wt%); 324 g and n-BuOH (10 wt%); 36 g to obtain a coating solution.
[0036]
The coating method was a spin coating method. First, a coating glass substrate is set on a spin coater. First, in the coating film region (high-speed spin rotation), spin rotation is started, and after 3 seconds at a rotation speed of 150 rpm, the coating amount of the coating solution is about 20 ml. The solution was dropped to form a film while maintaining the rotation speed for 18 seconds. Subsequently, in the leveling area (spin rotation stop), before the coated coating solution begins to thirst and loses its fluidity, the spin rotation is temporarily stopped and allowed to stand still for 60 seconds, and the drying acceleration area (slow spin rotation) ), Spin rotation was started again and maintained at a low speed of 50 rpm for 40 seconds to accelerate the drying of the coating film, and a gel film with good film formability was obtained.
[0037]
Next, the glass substrate with the gel film is pre-baked at 250 ° C. for 30 minutes, further subjected to main baking at a glass temperature of 630 ° C. to 660 ° C., and SiO having a fine uneven shape on the surface.2-TiO2A thin film was obtained.
[0038]
[Method of evaluating practical durability]
The obtained highly slippery glass was evaluated by the following four methods.
[0039]
1) Initial contact angle
The angle formed between the water droplet and the substrate surface when the water droplet was placed on the sample was measured with a contact angle meter.
[0040]
Contact angle meter: Kyowa Interface Science CA-X type
Measurement environment: In the atmosphere (about 25 ℃)
Water: pure water (2 μl).
[0041]
2) Water drop fallability
While the sample is inclined at 30 °, pure water is slowly dropped onto the sample surface with a microsyringe. At this time, the amount (volume) of water droplets at the time when the water droplets started to move was expressed in μl and expressed as “sliding water”.
[0042]
3) Abrasion resistance
Using the following testing machine, the contact angle θ (°) was measured after the number of sliding times (3500 times).
[0043]
Testing machine: Traverse type sliding testing machine (manufactured in-house)
Sliding area: 100mm x 25mm
Friction cloth: canvas cloth (JISL3102-11961-1206)
Load: 0.1kg / cm2
Stroke: 100mm reciprocating sliding (sliding frequency is the number of reciprocating times)
Sliding speed: 30 reciprocations / minute.
[0044]
4) Light resistance
Using the following tester, the contact angle θ (°) after the sample was irradiated with powerful UV light from a metal halide lamp for 2 hours was evaluated.
[0045]
Testing machine: High-speed light resistance testing machine (manufactured in-house)
Lamp: 1.5kW metal halide lamp (M015-L312 made by Eye Graphics)
Lamp-sample distance: 160mm
Table 2 shows the evaluation results of the samples obtained in the following examples and comparative examples.
[0046]
【Example】
Examples of the present invention will be described below.
[0047]
Example 1
In this example, the mixing ratio of FASC and N10SOL is 1: 1 by molar ratio.
First, 5.00 g of ethyl acetate and 3.90 g of N10SOL were weighed and mixed. Next, 2.50 g of FASC was slowly added dropwise to the mixture with stirring, and the mixture was further stirred for 6 hours at room temperature (20 to 25 ° C.) to obtain a mother liquor. Next, 1.0 g of the mother liquor was diluted with 9.0 g of i-PA and stirred for about 10 minutes to obtain a surface film forming treatment agent. 2 ml / pc of the surface treatment agent was dropped on the substrate A in an environment where the temperature was kept at 25 ° C. and humidity was kept at 45% RH on the substrate A, and the surface was sufficiently stretched over the entire surface of the glass with a cotton cloth (trade name: Bencott). After that, it was air-dried for about 5 minutes. Thereafter, heat treatment was performed at 150 ° C. for about 5 minutes at a glass temperature in a muffle furnace, and the remaining water repellent remaining cloudy was wiped with iPA to obtain a transparent sample. As shown in Table 2, the evaluation results of the obtained sample showed an extremely good water drop sliding property with an initial contact angle of 100 ° and a sliding property of 13 μl. Further, the wear resistance and light resistance were 98 ° and 98 °, and there was almost no change in the contact angle before and after the test.
In Table 2, the FAS column indicates the type of FAS used, and is -Cl3; trichlorosilane type (FASC), -OCH3; trimethoxysilane type. The amount added was 1 mol.
[0048]
Example 2
The same procedure as in Example 1 was performed except that the surface treatment agent was applied to the substrate B. The obtained sample had an initial contact angle of 102 ° and a sliding property of 8 μl, which showed very good water droplet sliding properties. In addition, the wear resistance and light resistance were 100 ° and 96 °, indicating high practical durability.
[0049]
Example 3
The same procedure as in Example 1 was performed except that the surface treatment agent was applied to the substrate C. The obtained sample had an initial contact angle of 100 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 99 ° and 95 °.
[0050]
Example 4
Example 2 was repeated except that the reaction time for preparing the surface treatment agent was 12 hours. The obtained sample had an initial contact angle of 101 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0051]
Example 5
Example 3 was repeated except that the reaction time for preparing the surface treatment agent was 12 hours. The obtained sample had an initial contact angle of 101 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0052]
[Table 2]
[0053]
Example 6
Example 2 was repeated except that the reaction time for preparing the surface treatment agent was 24 hours. The sample obtained had an initial contact angle of 99 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0054]
Example 7
Example 3 was repeated except that the reaction time for preparing the surface treatment agent was 24 hours. The obtained sample had an initial contact angle of 100 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0055]
Example 8
The conditions were the same as in Example 2 except that the mixing ratio of FASC and N10SOL was 1: 2. The obtained sample had an initial contact angle of 101 ° and a sliding property of 8 μl, showing very good water droplet sliding properties. The abrasion resistance and light resistance were 97 ° and 96 °, indicating high practical durability.
[0056]
Example 9
The same procedure as in Example 8 was performed except that the surface treatment agent was applied to the substrate C. The obtained sample had an initial contact angle of 100 ° and a sliding property of 13 μl, which showed very good water drop sliding properties. Further, the wear resistance and light resistance were 97 ° and 97 °, and high practical durability was exhibited.
[0057]
Example 10
N20SOL having an average degree of polymerization of 20 was used for the silicone oil diol, and the mixing ratio with FASC was 1: 2. Other conditions were the same as in Example 2. The obtained sample had an initial contact angle of 101 ° and a sliding property of 17 μl, which showed good water drop sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 95 °.
[0058]
Example 11
The same procedure as in Example 10 was performed except that the surface treatment agent was applied to the substrate C. The obtained sample had an initial contact angle of 98 ° and a sliding property of 15 μl, which showed very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 97 °.
[0059]
Example 12
The sample was prepared in the same manner as Example 2 except that no heat treatment was performed. The obtained sample had an initial contact angle of 100 ° and a sliding property of 10 μl, showing very good water droplet sliding properties. In addition, the wear resistance and light resistance showed high practical durability at 98 ° and 98 °.
[0060]
Comparative Example 1
In the preparation of the surface treatment agent, without mixing silicone oil diol, 25 g of iPA as a diluting solvent and 0.1 N nitric acid (HNO as an acid catalyst) are added to 1 g of FASC.Three) Was added and stirred at room temperature for about 2 hours to complete the hydrolysis reaction. Other conditions were the same as in Example 2. The obtained sample had an initial contact angle of 108 °, a sliding property of 50 μl, and the sliding property of water droplets was poor. Further, the wear resistance and light resistance were 70 ° and 100 °, and the wear resistance was not at a practical level.
[0061]
Comparative Example 2
The same procedure as in Comparative Example 1 was performed except that the surface treatment agent was applied to the substrate C. The obtained sample had an initial contact angle of 112 ° and a sliding property of 55 μl, which was a bad level. Further, the wear resistance and light resistance were 110 ° and 106 °, and the practical durability was at a level that could be put to practical use, but the sliding property was not satisfactory.
[0062]
Comparative Example 3
In the preparation of the surface treatment agent, N10SOL; 1 g was diluted only with iPA; 9 g without mixing perfluoroalkyltrichlorosilane (FASC). Others were the same as in Example 2. The obtained sample had an initial contact angle of 91 ° and a sliding property of 15 μl, which was a good level of water drop sliding properties, but was wear resistance of 76 ° and light resistance of 80 °, which was not a practical level.
[0063]
Comparative Example 4
In the preparation of the surface treatment agent, N20SOL; 1 g was diluted with iPA; 9 g without mixing perfluoroalkyltrichlorosilane (FASC). Others were the same as in Example 2. The obtained sample had an initial contact angle of 94 ° and a sliding property of 10 μl, which was a good level of water drop sliding properties, but the wear resistance was 89 ° and the light resistance was 89 °, which was not a practical level.
[0064]
Comparative Example 5
The sample was prepared in the same manner as Example 2 except that the heat treatment temperature was set to 200 ° C. The obtained sample had an initial contact angle of 100 ° and a sliding property of 50 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 100 ° and the light resistance was 98 °, which was high practical durability.
[0065]
Comparative Example 6
The sample was prepared in the same manner as in Example 2 except that the heat treatment temperature was set to 350 ° C. The obtained sample had an initial contact angle of 103 ° and a sliding property of 55 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 101 ° and the light resistance was 99 °, which was high practical durability.
[0066]
Comparative Example 7
The same procedure as in Example 2 was conducted except that the reaction time at the time of preparation of the surface treatment agent was 1 hour. The obtained sample had an initial contact angle of 100 ° and a sliding property of 55 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 95 °, the light resistance was 95 °, and the practical durability was good.
[0067]
Comparative Example 8
The same procedure as in Example 2 was performed except that the reaction time during preparation of the surface treatment agent was 2 hours. The obtained sample had an initial contact angle of 103 ° and a sliding property of 50 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 95 °, the light resistance was 95 °, and the practical durability was good.
[0068]
Comparative Example 9
In the preparation of the surface treatment agent, the water repellent agent is heptadecafluorodecyltrimethoxysilane (CFThree(CF2)7CH2CH2Si (OCHThree)Three: KBS-7803 manufactured by Shin-Etsu Silicone, referred to as FASM). The obtained sample had an initial contact angle of 107 ° and a sliding property of 40 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 105 °, the light resistance was 96 °, and the practical durability was good.
[0069]
Comparative Example 10
Comparative Example 9 was carried out except that the reaction time for preparing the surface treating agent was 24 hours. The obtained sample had an initial contact angle of 107 ° and a sliding property of 45 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 105 °, the light resistance was 95 °, and the practical durability was good.
[0070]
Comparative Example 11
When preparing the surface treating agent, it was the same as Comparative Example 9 except that a silicone oil diol having an average degree of polymerization of 20 was used. The obtained sample had an initial contact angle of 110 ° and a sliding property of 40 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 105 °, the light resistance was 95 °, and the practical durability was good.
[0071]
Comparative Example 12
The same procedure as in Comparative Example 11 was conducted except that the reaction time for preparing the surface treatment agent was 24 hours. The obtained sample had an initial contact angle of 110 ° and a sliding property of 40 μl, and the sliding property of water droplets was poor. On the other hand, the wear resistance was 105 °, the light resistance was 95 °, and the practical durability was good.
[0072]
【The invention's effect】
The present invention relates to a novel highly slidable base material exhibiting extremely excellent water drop slidability (slidability) and a method for producing the same, and the slidability (30 ° inclination) is 10 μl or less, and is excellent in practical use. Excellent water repellency and water slidability with durability. As a result, it has become possible to improve the water drop sliding property of the fluorine-based water repellent, which has been a problem in the past, without significantly impairing the durability.
[Brief description of the drawings]
FIG. 1 is a flowchart showing a preparation process of a surface treatment agent of the present invention.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19995299A JP3744736B2 (en) | 1999-07-14 | 1999-07-14 | Highly slidable base material and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19995299A JP3744736B2 (en) | 1999-07-14 | 1999-07-14 | Highly slidable base material and method for producing the same |
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| JP2001025702A JP2001025702A (en) | 2001-01-30 |
| JP3744736B2 true JP3744736B2 (en) | 2006-02-15 |
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| JP4522357B2 (en) * | 2005-02-21 | 2010-08-11 | セントラル硝子株式会社 | Manufacturing method for water slidable glass articles |
| JP5314055B2 (en) * | 2008-03-12 | 2013-10-16 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Durable automotive windshield coating and its use |
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