JP3572989B2 - Polyhedral organosilicon compounds having perfluoroalkyl groups - Google Patents

Description

【００１９】
このような多面体構造を持つ有機ケイ素化合物については、Ｒがアルキル基、モノフルオロ置換アルキル基、またはペルフルオロフェニル置換アルキル基である化合物が、Ｅｃｋｈａｒｄ Ｒｉｋｏｗｓｋｉら、Ｐｏｌｙｈｅｄｒｏｎ， Ｖｏｌ． １６， Ｎｏ． １９， ｐｐ． ３３５７−３３６１ （１９９７） 等に報告されているが、ペルフルオロアルキル基で置換されたアルキル基を持つこの種の化合物はこれまで知られていなかった。
【００２０】
これは、前述したように、ペルフルオロアルキル基を有するシラン化合物は、加水分解と縮合が進んで重合度が増加するにつれて有機溶媒への溶解度が極端に低下するため、アルキル基が非置換であるか、または水素であるシラン化合物に比べて、加水分解と縮合反応を進行させにくく、多面体構造になるまで縮合を十分に進行させることが困難であったことが理由ではないかと考えられる。
【００２１】
本発明では、Ｏ、Ｎ、Ｆ、およびＣｌから選ばれた少なくとも１種の元素を含有する有機溶媒中で、水および塩基性化合物の存在下に加水分解と縮合反応を行うことにより、従来法では困難であったペルフルオロアルキル基を有する多面体構造を持つポリシロキサン化合物の合成が可能となる。その結果、次の反応式に示すように、一般式（３） で示されるペルフルオロアルキル基を有する３官能型シランモノマーから、一般式（１） で示される多面体ポリシロキサン構造を持つ有機ケイ素化合物を得ることができる。
【００２２】
【化２】

上記式中、Ｒｆ、Ｘ、ａ、Ｙ、およびｍは上記と同じ意味である。
【００２３】
上記一般式において、Ｘは好ましくは−ＣＨ_２− 、−Ｏ− 、−Ｎ（Ｒ）−、−Ｓ− 、−Ｃ（Ｏ）Ｏ− 、 −ＣＯＮ（Ｒ）− および−ＳＯ_２Ｎ（Ｒ）− よりなる群から選ばれ、ここでＲは水素または炭素数１〜１０のアルキル基もしくはアルケニル基である。Ｒは好ましくは水素または炭素数１〜４のアルキル基である。Ｒｆは好ましくは炭素数１〜１０、より好ましくは炭素数２〜８のペルフルオロアルキル基である。Ｒｆの炭素数が大きい方が、疎水性のより高い膜を形成することができる。一般式（１） で示される有機ケイ素化合物のうち特に好ましいのは、式： （Ｒｆ−ＣＨ_２−ＣＨ_２−ＳｉＯ_１．５）_ｍ で示される、Ｘ＝−ＣＨ_２−、ａ＝１の化合物であるが、Ｘ＝−ＣＯＮＨ−または−ＳＯ_２Ｎ（Ｃ_３Ｈ_７）−、ａ＝３である化合物も好ましい。
【００２４】
一般式（３） におけるＹは、好ましくは炭素数１〜５のアルコキシ基または塩素であり、より好ましくはメトキシ基、エトキシ基または塩素である。なお、三つのＹ基は同一でも異なるものでもよい。一般式（１） におけるｍの値は、好ましくは８〜１６である。
【００２５】
上記反応に触媒として用いる塩基性化合物としては、金属水酸化物、アミン化合物、および第四級アンモニウム塩水酸化物よりなる群から選んだ１種もしくは２種以上を使用することが好ましいが、アンモニア （水酸化アンモニウムまたはアンモニアガス） も使用できる。アミン化合物は第三級アミンが好ましい。塩基性化合物の好ましい例としては、ＫＯＨ 、ＮａＯＨ、ＬｉＯＨなどのアルカリ金属水酸化物、Ｃａ（ＯＨ）_２ 、Ｂａ（ＯＨ）_２ などのアルカリ土類金属水酸化物、トリメチルアミン、トリエチルアミン、ピリジン、ルチジン等のアミン、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム等の第四級アンモニウム塩水酸化物が挙げられる。
【００２６】
シラン化合物の加水分解触媒として、従来は一般に酸 （例、塩酸、硝酸などの鉱酸） が使用されてきたが、酸触媒を使用した場合には、反応が部分的にしか進行せず、上記のかご型の多面体シロキサン生成物を得ることはできない。
【００２７】
上記反応に使用する塩基性化合物と水の量は、一般式（３） で示される原料モノマー１モルに対して、塩基性化合物が１×１０^−５〜２モル、好ましくは１×１０^−３〜１モルであり、水が１〜２０モル、好ましくは １．５〜６モルである。触媒の塩基性化合物の量が多すぎると反応が急激に進行し、ゲル化を生ずることがある。また、少なすぎると反応が十分に進行せず、未反応物の割合が多くなる。水は原料モノマーの加水分解に必要である。水の量が１モルより少なくなると、加水分解と縮合が十分に進行しない。水が多すぎると、原料モノマーと溶媒が相分離を起こし、目的とする多面体化合物を形成しない。
【００２８】
また、本発明の別の態様によれば、一般式（４） 、（５） でそれぞれ示される、いずれもペルフルオロアルキル基を有する、複数種類の （即ち、互いに異なる） ３官能型シランモノマーを出発物質として使用して、上述した一般式（３） で示される１種類のシランモノマーを使用する場合と同様に加水分解および縮合反応を行うことにより、次の反応式に示すように、一般式（２） で示される、１分子中にペルフルオロアルキル基を含有する異なる有機を持った単量体ポリシロキサン構造を持つ有機ケイ素化合物を製造することができる。本発明は、このような有機ケイ素化合物とその製造方法も提供するものである。
【００２９】
【化３】

式中、Ｒｆ’ とＲｆ” はそれぞれ炭素数１〜２０のペルフルオロアルキル基、Ｘ’ とＸ” はそれぞれ２価結合基、ａとｂはそれぞれ０〜１０の整数、ｍとｎはそれぞれ１〜１９の整数、かつｍ＋ｎは４〜２０であり、Ｙ’ とＹ” はそれぞれ炭素数１〜８のアルコキシ基またはＣｌであり、Ｒｆ’ とＲｆ” 、Ｘ’ とＸ” 、およびａとｂの少なくとも１つの組合わせは互いに同一ではない。
【００３０】
Ｒｆ’ とＲｆ” 、およびＸ’ とＸ” の具体例や好ましい例は、それぞれＲｆおよびＸについて上述した通りである。一般式（２） で示される有機ケイ素化合物のうち特に好ましいのは、式：（Ｒｆ’−ＣＨ_２−ＣＨ_２−ＳｉＯ_１．５）_ｍ （Ｒｆ”−ＣＨ_２−ＣＨ_２−ＳｉＯ_１．５）_ｎ で示される、Ｘ’ ＝Ｘ” ＝−ＣＨ_２−で、ａ＝ｂ＝１である化合物であるが、Ｘ’ とＸ” が−ＣＯＮＨ−または−ＳＯ_２Ｎ（Ｃ_３Ｈ_７）−であり、ａ＝ｂ＝３である化合物も好ましい。
【００３１】
化合物（４） および（５） から化合物（２） の合成は、上述した化合物（３） から化合物（１） への合成と同様にして実施することができ、塩基性化合物の種類やその使用量、水の使用量も上記と同様でよい。なお、使用するシランモノマーは、２種類に制限されるものではなく、３種類以上の異なる有機シランモノマーを使用してもよい。
【００３２】
一般式（１） と（２） のいずれの有機ケイ素化合物を製造する場合についても、反応溶媒は、Ｏ、Ｎ、Ｆ、およびＣｌから選ばれた少なくとも１種の元素を含有する有機溶媒である。溶媒は、原料モノマーと生成ポリマーのどちらも良好に溶解するものを使用する。このような溶媒の例は、アルコール類、ケトン類、エーテル類、フッ素化および／もしくは塩素化炭化水素類、アミン類、アミド類等である。なお、アミン系溶媒は触媒と溶媒の両方として機能しうる。溶媒は２種以上の混合溶媒としてもよい。
【００３３】
好ましい溶媒の具体例としては、メタノール、エタノール、プロパノール、イソプロパノール、アセトン、メチルエチルケトン、シクロヘキサノン、イソホロン、ジエチルエーテル、ジオキサン、テトラヒドロフラン、トリクロロトリフルオロエタン、トリクロロエタン、トリエチルアミン、ピリジン、ルチジン、ジメチルホルムアミド、ジメチルアセトアミド等、およびこれらの混合溶媒が挙げられる。
【００３４】
加水分解および縮合反応は、例えば、原料モノマーのシラン化合物を上記の有機溶媒に溶解させ、得られた溶液に、触媒の塩基性化合物の水溶液を滴下するか、塩基性化合物と水を一緒または別々に滴下または添加することにより実施できる。但し、反応方法はこれに限られるものではない。反応は１０〜１５０ ℃の温度で行うことができるが、高収率を得るには反応温度を５０〜１２０ ℃とすることが好ましい。反応時間は、加水分解と縮合反応が可及的に完結するように設定し、反応温度によっても異なるが、通常は１〜７２時間程度である。
【００３５】
上記のようにして、一般式（３） で示される３官能型シランモノマーの加水分解および縮合反応を行うと一般式（１） で示されるシロキサン化合物が生成し、一般式（４） および（５） で示される３官能型シランモノマーの加水分解および縮合反応を行うと一般式（２） で示されるシロキサン化合物が生成する。生成物は有機溶媒と水からなる媒質に溶解した状態で得られる。反応液から生成物を単離するには、例えば、有機溶媒と水を留去し、残渣を適当な手法で精製 （例、抽出、再結晶、蒸留、クロマトグラフィー） すればよい。或いは、純度が問題にならなければ、反応液をそのまま （例、単に不溶物を濾去しただけで） で成膜材料として使用することができる。また、反応液から水と触媒の塩基性化合物を適当な手法 （例、留去、抽出、水洗等） で除去して生成物が有機溶媒に溶解した溶液にしてもよい。この溶液状態で長期間保存し、成膜材料として使用することができる。
【００３６】
生成した多面体シロキサン化合物は、重合体であるが、ＧＰＣ（ゲル浸透クロマトグラフィー） による分子量分布の測定で極めて幅の狭いピークを示す、均一重合度 （一定のｍ値 ［一般式（１）］またはｍ＋ｎ値［ 一般式（２）］を持つ化合物である。生成物を^２９Ｓｉ−ＮＭＲおよびＧＰＣ で分析すると、^２９Ｓｉ−ＮＭＲ測定では１つのケイ素原子に対してＳｉ−Ｏ−Ｓｉ 結合を３つ持つ ［即ち、 Ｒ−Ｓｉ（Ｏ−Ｓｉ−）_３骨格に帰属する］ 単一のピークのみが得られ、ＧＰＣ による分子量分布の測定では、ほとんどの場合１本のピークが得られる。これらの結果から、生成した化合物が上記のかご型の多面体構造を持つことがわかる。
【００３７】
このシロキサン化合物は、上の
【化１】に示したようなかご型の多面体構造を持ち、加水分解後も残留するペルフルオロアルキル基を有する有機基 ［例、一般式（１） ではＲｆ−Ｘ−（ＣＨ_２）_ａ−基］ が「かご」の周囲の◎の位置に存在する。
【００３８】
この多面体シロキサン化合物は、鎖状のポリシロキサンとは異なり、構造中に反応点 （例、分子末端の水酸基またはアルコキシ基） を全くもたないため、極めて安定である。従って、これを溶液状態で保存しても、変性や析出物を生ずることがないので、保存安定性に優れており、また溶解性も良好に維持される。
【００３９】
本発明のペルフルオロアルキル基を有する多面体有機ケイ素化合物は各種目的での成膜材料として有用である。この化合物は、反応に使用することができる前述したような有機溶媒への溶解性に優れているので、溶液の状態でスピンコート、浸漬、スプレー等の各種の湿式成膜法に容易に利用することができる。また、好ましくは固体状態、または溶液状態で、真空蒸着による乾式成膜法を採用することもできる。形成された膜の厚みは特に制限されないが、 ０．１〜２μｍ程度が適当である。湿式成膜後の乾燥は６０〜２００ ℃で行うことが好ましい。
【００４０】
本発明の多面体有機ケイ素化合物から成膜された膜は、多面体構造の表面に現れるペルフルオロアルキル基の存在により、優れた撥水・撥油性を示す。しかし、ポリテトラフルオロエチレンのような撥水・撥油性フッ素樹脂とは異なり、分子の骨組みがシロキサン結合 （−Ｓｉ−Ｏ−Ｓｉ−） から構成されるため、この膜は各種基材との密着性にも優れている。さらに、シロキサン結合の膜に固有の優れた耐熱性および耐火性も示す。従って、従来にない優れた密着性と耐熱性を備えた撥水・撥油膜となる。この撥水・撥油膜は、例えば、ガラス板への撥水・撥油性の付与といった用途に有用である。
【００４１】
この膜は、撥水・撥油性に加えて、屈折率と誘電率が低いという特徴を持つので、低反射膜および低誘電率膜としても有用である。低反射膜は、例えば、ＴＶのブラウン管や各種ディスプレイ装置 （ＣＲＴ、液晶、ＥＬ、プラズマ等） の表面に画質向上のために形成することができる。低誘電率膜は、例えば、半導体素子の層間絶縁膜等として有用である。
【００４２】
本発明の多面体有機ケイ素化合物から成る膜はまた、一定温度で気化するので、膜中に色素を分散させれば、レーザ等の熱によるパターニングにも適しており、精密に （高い解像度で） パターニングすることができる。色素は、使用するレーザの波長近傍に吸収極大を有するものが好ましい。成膜は多面体有機ケイ素化合物の溶液を用いて行い、この溶液に適量の色素を添加して溶解させることにより、色素が分散した膜を形成することができる。膜は有機溶媒に溶解可能であるので、パターニングした後、必要に応じてエッチングにより除去することもできる。従って、例えば、半導体素子の微細加工等にレジストとして使用することができる。
【００４３】
【実施例】
以下、本発明を実施例により具体的に説明する。
【００４４】
【実施例１】
（ＣＦ _３ ＣＨ _２ ＣＨ _２ ＳｉＯ _１．５ ） _８ の合成
磁気攪拌装置、温度計、滴下ロートを備えた容量１００ ｃｍ^３ 三つ口フラスコに、［ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ２１．８ｇ（０．１ ｍｏｌ） およびアセトン２１．８ｇを入れ、生成した溶液を５０℃に保持しながら、１Ｎ−ＮａＯＨ 水溶液６．０ ｇ（ＮａＯＨ ６ ｍｍｏｌ、水０．３ ｍｏｌ）を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で１５時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去すると、白色粉が得られた （収量８５％） 。この白色粉を水洗して精製した （精製後の収量８０％） 。
【００４５】
精製した生成物を、Ｓｈｏｄｅｘ^ＴＭＫＦ８０１＋８０２ カラムを使用し、０．７５ ｃｍ^３／ｍｉｎでテトラヒドロフランを溶離液としてＧＰＣ による分子量分布を測定したところ、１７．２２ ｍｉｎ に１本のピークが得られた。このピークの溶出時間から、ポリスチレン換算により分子量を算出したところ、ｍ＝８の分子量に相当した。
【００４６】
この生成物の元素分析結果、ＩＲスペクトル （特徴的ピークのみ、以下同じ） および^２９Ｓｉ−ＮＭＲスペクトル （標準物質：ＴＭＳ 、溶媒：アセトン、以下同じ） は下記のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００４７】
以上より、生成物をかご型多面体構造の (CF₃CH₂CH₂SiO_1.5)₈ と同定した。

IR：2920、2960、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−70.5。
【００４８】
精製した生成物の熱特性を、ＴＧ−８１１０ （ＲＩＧＡＫＵ 製） を用いたＴＧ−ＤＴＡ測定により調べた。試料を空気中で室温から１０℃／ｍｉｎで昇温すると、２６０ ℃までの重量減少は５％以下と安定な熱特性を示した。さらに昇温を続けると、２６０ ℃付近で吸熱とともに急激な重量減少を示した。３５０ ℃まで加熱した後の残留物は５％以下と、ほとんとが揮発していた。さらに、測定後のアルミパンは、試料を入れる前と外観上の変化は見られず、残留物および着色等は認められなかった。
【００４９】
【実施例２】
（ＣＦ _３ ＣＨ _２ ＣＨ _２ ＳｉＯ _１．５ ） _１２ の合成
実施例１と同様の反応装置に、［ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ２１．８ｇ（０．１ ｍｏｌ） およびテトラヒドロフラン６５．４ｇを入れ、得られた溶液を６０℃に保持しながら、１Ｎ−ＫＯＨ水溶液 ３．０ｇ（ＫＯＨ ３ ｍｍｏｌ 、水０．１６７ ｍｏｌ）を約３０分間かけて滴下した後、反応混合物を同じ温度で２４時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去すると、白色粉が得られた （収量８４％） 。この白色粉を水洗により精製した （精製後の収量７５％） 。
【００５０】
精製した生成物の分子量分布を、実施例１と同様にしてＧＰＣ により測定したところ、１６．７５ ｍｉｎ に１本のピークが得られた。このピークの溶出時間から、ポリスチレン換算により分子量を算出したところ、ｍ＝１２の分子量に相当した。
この生成物の元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは下記のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００５１】
以上より、生成物をかご型多面体構造の (CF₃CH₂CH₂SiO_1.5)₁₂と同定した。

IR：2920、2960、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−71.0
【００５２】
【実施例３】
（ＣＦ _３ ＣＦ _２ ＣＨ _２ ＣＨ _２ ＳｉＯ _１．５ ） _１０ の合成
実施例１と同様の反応装置に ［ＣＦ_３ＣＦ_２ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ２６．８ｇ（０．１ ｍｏｌ） およびアセトン４０ｇを入れ、得られた溶液を５０℃に保持しながら、１．２５Ｎ−ＮａＯＨ水溶液 ７．３ｇ（ＮａＯＨ ９．１ ｍｍｏｌ、水３．７ ｍｏｌ）を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で２４時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去すると、白色粉が得られた （収量８５％） 。この白色粉を水から再沈殿させて精製した （精製後の収量７８％） 。
【００５３】
精製した生成物の分子量分布を、実施例１と同様にしてＧＰＣ により測定したところ、１６．９３ ｍｉｎ に１本のピークが得られた。このピークの溶出時間から、ポリスチレン換算により分子量を算出したところ、ｍ＝１０の分子量に相当した。
この生成物の元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは下記のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００５４】
以上より、生成物をかご型多面体構造の(CF₃CF₂CH₂CH₂SiO_1.5)₁₀と同定した。

IR：2960、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−70.5
精製した生成物の熱特性を実施例１と同様にして測定した。試料を空気中で室温から10℃/minで昇温すると、275 ℃までの重量減少は５％以下と安定な熱特性を示した。さらに昇温を続けると、275 ℃以下で吸熱とともに急激な重量減少を示した。350 ℃まで加熱した後の残留物は５％以下と、ほとんとが揮発していた。さらに、測定後のアルミパンは、試料を入れる前と外観上の変化は見られず、残留物および着色等は認められなかった。
【００５５】
【実施例４】
（Ｃ _４ Ｆ _９ ＣＨ _２ ＣＨ _２ ＳｉＯ _１．５ ） _１０ の合成
容量５００ ｃｍ^３ の三つ口フラスコを用いた以外は実施例１と同様の反応装置に、 ［Ｃ_４Ｆ_９ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ３６．８ｇ（０．１ ｍｏｌ） およびアセトン／メタノール（１／１ ｗｔ／ｗｔ） 混合溶媒 ２２０ｇを入れ、得られた溶液を５０℃に保持しながら、１Ｎ−ＮａＯＨ 水溶液１２ｇ（ＮａＯＨ １２ ｍｍｏｌ 、水０．６ ｍｏｌ）を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で２４時間攪拌して、加水分解と縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去すると、白色粉が得られた （収量８０％） 。この白色粉を水洗により精製した （精製後の収量７３％） 。
【００５６】
精製した生成物の分子量分布を、実施例１と同様にしてＧＰＣ により測定したところ、１６．３７ ｍｉｎ に１本のピークが得られた。このピークの溶出時間から、ポリスチレン換算により分子量を算出したところ、ｍ＝１０の分子量に相当した。
この生成物の元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは下記のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００５７】
以上より、生成物をかご型多面体構造の (C₄F₉CH₂CH₂SiO_1.5)₁₀ と同定した。

IR：2920、2960、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−71.2
【００５８】
【実施例５】
（Ｃ _８ Ｆ _１７ ＣＨ _２ ＣＨ _２ ＳｉＯ _１．５ ） _８ の合成
容量１０００ ｃｍ^３の三つ口フラスコを用いた以外は実施例１と同様の反応装置に、［Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ５６．８ｇ（０．１ ｍｏｌ） および１，１，２−トリクロロ−２，２，１−トリフルオロエタン ５００ｇを入れ、得られた溶液を４０℃に保持しながら、水酸化テトラメチルアンモニウムの１０％メタノール溶液３４ｇ （塩基３７ ｍｍｏｌ）と水１２ｇ（６６７ ｍｍｏｌ）を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で３時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去し、得られた粘稠液体を水洗して精製した （精製後の収量７６％） 。
【００５９】
精製した生成物の分子量分布を、実施例１と同様にしてＧＰＣ により測定したところ、１６．０３ ｍｉｎ に１本のピークが得られた。このピークの溶出時間から、ポリスチレン換算により分子量を算出したところ、ｍ＝８の分子量に相当した。
この生成物の元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは下記のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００６０】
以上より、生成物をかご型多面体構造の(C₈F₁₇CH₂CH₂SiO_1.5)₈と同定した。

IR：2920、2960、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−71.5
【００６１】
【実施例６】
（Ｃ _７ Ｆ _１５ ＣＯＮＨ（ＣＨ _２ ） _３ ＳｉＯ _１．５ ） _１２ の合成
実施例４と同様の反応装置に ［Ｃ_７Ｆ_１５ＣＯＮＨ（ＣＨ_２）_３Ｓｉ（Ｃｌ）_３］ ５９．０ｇ（０．１ ｍｏｌ） および１，４−ジオキサン １８１．５ｇを入れ、次にトリエチルアミン１．０ ｇ（９．９ ｍｍｏｌ）と水２０．０ｇ （１．１ ｍｏｌ）を加えて、１００ ℃で１２時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去し、残渣を水洗し、その後ヘキサンに投入して不溶分を分離除去して精製した （精製後の収量７４％） 。
【００６２】
精製した生成物の分子量分布を実施例１と同様にＧＰＣ により測定し、ポリスチレン換算により分子量を概算したところ、上記化合物の分子量に相当した。
この生成物の元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは次のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは主に強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００６３】
以上より、生成物をかご型多面体構造の(C₇F₁₅CONH(CH₂)₃SiO_1.5)₁₂ と同定した。

IR：2920、2960、1720、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−71.4
【００６４】
【実施例７】
（Ｃ _８ Ｆ _１７ ＳＯ _２ Ｎ（Ｃ _３ Ｈ _７ ）（ＣＨ _２ ） _３ ＳｉＯ _１．５ ） _１０ の合成
実施例５と同様の反応装置に、［Ｃ_８Ｆ_１７ＳＯ_２Ｎ（Ｃ_３Ｈ_７）（ＣＨ_２）_３Ｓｉ（ＯＥｔ）_３］ ７４．５ｇ（０．１ ｍｏｌ） およびアセトン ６７０ｇを入れ、得られた溶液を５０℃に保持しながら、水酸化テトラメチルアンモニウムの１０％メタノール溶液 ５．５ｇ （塩基６．０ ｍｍｏｌ） と水 ３．０ｇ（１６７ ｍｍｏｌ）を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で２４時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去し、残渣を水洗して精製した （精製後の収量６７％） 。
【００６５】
精製した生成物の分子量分布を実施例１と同様にＧＰＣ により測定し、ポリスチレン換算により分子量を概算したところ、上記化合物の分子量に相当した。
この生成物の元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは次のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００６６】
以上より、生成物をかご型多面体構造の(C₈F₁₇SO₂N(C₃H₇)(CH₂)₃SiO_1.5)₁₀ と同定した。

IR：2920、2960、1400、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−70.9
【００６７】
【実施例８】
（ＣＦ _３ ＣＨ _２ ＣＨ _２ ＳｉＯ _１．５ ） _７ （Ｃ _８ Ｆ _１７ ＣＨ _２ ＣＨ _２ ＳｉＯ _１．５ ） _１ の合成
実施例１と同様の反応装置に［ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ １８．７ｇ（０．０８６ ｍｏｌ） 、 ［Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ８．１ｇ（０．０１４ ｍｏｌ） および溶媒のテトラヒドロフラン２７ｇを入れ、得られた溶液を５０℃に保持しながら、１Ｎ−ＮａＯＨ 水溶液 ８．０ｇ（ＮａＯＨ ８．３ ｍｍｏｌ、水０．４ ｍｏｌ）を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で１５時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去すると、白色粉が得られた （収量８５％） 。この白色粉を水から再沈殿させて精製した。
【００６８】
精製した生成物の分子量分布を実施例１と同様にしてＧＰＣ により測定したところ、１７．０９ ｍｉｎ に１本のピークが得られた。このピークの溶出時間からポリスチレン換算により分子量を算出したところ、上記化合物の分子量に相当した。
この生成物の元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは下記のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００６９】
以上より生成物をかご型多面体構造の(CF₃CH₂CH₂SiO_1.5)₇(C₈F₁₇CH₂CH₂SiO_1.5)₁と同定した。

IR：2920、2960、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−69.7
精製した生成物の熱特性を実施例１と同様にして測定した。試料を空気中で室温から10℃/minで昇温すると、270 ℃までの重量減少は５％以下と安定な熱特性を示した。さらに昇温を続けると、270 ℃以下で吸熱とともに急激な重量減少を示した。400 ℃まで加熱した後の残留物は５％以下と、ほとんとが揮発していた。さらに、測定後のアルミパンは、試料を入れる前と外観上の変化は見られず、残留物および着色等は認められなかった。
【００７０】
【実施例９】
（ＣＦ _３ ＣＨ _２ ＣＨ _２ ＳｉＯ _１．５ ） _８ （Ｃ _４ Ｆ _９ ＳＯ _２ Ｎ（Ｃ _３ Ｈ _７ ）（ＣＨ _２ ） _３ ＳｉＯ _１．５ ） _２ の合成
実施例４と同様の反応装置に、［ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ２１．８ｇ（０．１ ｍｏｌ） 、 ［Ｃ_４Ｆ_９ＳＯ_２Ｎ（Ｃ_３Ｈ_７）（ＣＨ_２）_３Ｓｉ（ＯＭｅ）_３］ １２．６ｇ（０．０２５ ｍｏｌ） および溶媒のトリクロロトリフルオロエタン １０３ｇを入れ、得られた溶液を３０℃に保持しながら、水酸化テトラメチルアンモニウムの１０％メタノール溶液 ６．０ｇ （塩基６．６ ｍｍｏｌ） 、および水７ｇ （０．３９ ｍｏｌ） を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で２４時間攪拌して、加水分解および縮合反応を完結させた。次に、反応液から減圧下で溶媒と水を含む低沸点物を留去すると、白色粉が得られた （収量７７％） 。この白色粉を水から再沈殿させて精製した。
【００７１】
精製した生成物の分子量分布を実施例１と同様にＧＰＣ により測定し、ポリスチレン換算により分子量を概算したところ、上記化合物の分子量に相当した。
この生成物の元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは下記のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００７２】
以上より生成物をかご型多面体構造の(CF₃CH₂CH₂SiO_1.5)₈(C₄F₉SO₂N(C₃H₇)(CH₂)₃SiO_1.5)₂ と同定した。

IR：2920、2960、1400、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−69.5
【００７３】
【実施例１０】
（Ｃ _４ Ｆ _９ ＳＯ _２ Ｎ（Ｃ _３ Ｈ _７ ）（ＣＨ _２ ） _３ ＳｉＯ _１．５ ） _７ （Ｃ _８ Ｆ _１７ ＣＨ _２ ＣＨ _２ ＳｉＯ _１．５ ） _１ の合成
実施例４と同様の反応装置に、 ［Ｃ_４Ｆ_９ＳＯ_２Ｎ（Ｃ_３Ｈ_７）（ＣＨ_２）_３Ｓｉ（ＯＭｅ）_３］ ５０．３ｇ（０．１ ｍｏｌ） 、［Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ １０ｇ（１８ ｍｍｏｌ） 、および溶媒のアセトン １２０ｇを入れ、得られた溶液を５０℃に保持しながら、約０．５Ｎ−ＫＯＨ水溶液８ｇ（ＫＯＨ ４ ｍｍｏｌ 、水０．４ ｍｏｌ）を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で２４時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去すると、白色粉が得られた （収量７２％） 。この白色粉を水から再沈殿させて精製した。
【００７４】
精製した生成物の分子量分布を実施例１と同様にＧＰＣ により測定し、ポリスチレン換算により分子量を概算したところ、上記化合物の分子量に相当した。
この生成物の元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは下記のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い１本のピークが得られた。そのピーク位置は３官能性シロキサンのピークと一致した。
【００７５】
以上より生成物をかご型多面体構造の(C₄F₉SO₂N(C₃H₇)(CH₂)₃SiO_1.5)₇(C₈F₁₇CH₂CH₂SiO_1.5)₁ と同定した。

IR：2920、2960、1400、1130、1070cm^-1
29Si-NMR：δ(ppm) ＝−69.7
【００７６】
【比較例１】
実施例１と同様の反応装置に、［ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ２１．８ｇ（０．１ ｍｏｌ） とアセトン２１．８ｇを入れ、生成した溶液を５０℃に保持しながら、０．２Ｎ−ＨＣｌ水溶液１．０ ｇ （ＨＣｌ ０．２ ｍｍｏｌ、水０．０５６ ｍｏｌ）を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で１５時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去すると、淡黄色の高粘性油状物が得られた （収量８１％） 。
【００７７】
この生成物の分子量分布を、実施例１と同様にしてＧＰＣ により測定したところ、モノマーピークを含む複数のピークが得られた。その元素分析結果、ＩＲスペクトルおよび^２９Ｓｉ−ＮＭＲスペクトルは次のとおりであった。^２９Ｓｉ−ＮＭＲスペクトルでは強い３本のピークが得られ、そのピーク位置はモノマーならびに１および２官能性シロキサンのピークと一致した。
【００７８】

【００７９】
この生成物の熱特性を実施例１と同様にしてＴＧ−ＤＴＡ測定により調べた。試料を空気中で室温から１０℃／ｍｉｎで昇温すると、２２０ ℃と３５０ ℃で段階的に重量減少が見られ、残留分は３５０ ℃で６５％であった。さらに４００ ℃まで昇温しても、４０％以上が残留していた。この残留物はアルミパン上で黒化していた。
【００８０】
以上より、酸触媒を使用した場合には、本発明で目的とするかご型多面体構造の有機ケイ素化合物が得られないことがわかる。
【００８１】
【比較例２】
実施例１と同様の反応装置に［ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ２１．８ｇ（０．１ ｍｏｌ） とアセトン２１．８ｇを入れ、生成した溶液を５０℃に保持しながら、０．０１Ｎ−ＮａＯＨ水溶液 １．０ｇ（ＮａＯＨ ０．０１ ｍｍｏｌ 、水０．０５６ ｍｏｌ）を滴下した。滴下終了後、反応混合物を同じ温度で２４時間攪拌して、加水分解および縮合反応を完結させた。次いで、反応液から減圧下で溶媒と水を含む低沸点物を留去すると、無色透明の高粘性油状物が得られた （収量８２％） 。
【００８２】
この生成物の試料を用いて、実施例１と同様にＧＰＣ による分子量分布の測定を行ったところ、モノマーピークを含む複数のピークが得られた。本例では、水の使用量が少なすぎたため、目的とする多面体構造の有機ケイ素化合物を得ることができなかった。
【００８３】
【比較例３】
実施例１と同様の反応装置に［ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ２１．８ｇ（０．１ ｍｏｌ） とアセトン２１．８ｇを入れ、生成した溶液を５０℃に保持しながら、１Ｎ−ＮａＯＨ 水溶液 ６．０ｇ（ＮａＯＨ ６ ｍｍｏｌ） を滴下し、次に水３４ｇ （水は合計２．２ ｍｏｌ）を滴下した。水の滴下中に白色沈殿を生じた。本例では、水の使用量が多すぎたため、目的とする多面体構造の有機ケイ素化合物を得ることができなかった。
【００８４】
【実施例１１】
実施例１で得られた反応液を０．４５μｍのメンブレンフィルターでろ過して、不溶物を除去した。この溶液を、溶媒の揮発を防ぐようにしたスピンコータを用いて、回転速度４５００ ｒｐｍでシリコン基板上に塗布し、次いで １５０℃に３０分間加熱して塗膜を乾燥させることにより成膜して、ペルフルオロアルキル基を持つポリシロキサン膜を形成した。
【００８５】
乾燥後の膜厚を走査型電子顕微鏡を用いて測定したところ ０．３μｍであった。得られた膜は、無色透明であり、穴や突起のない平滑な面であった。この膜上に直径２ｍｍの円形電極を金蒸着によって作製し、ＬＣＲ メータ （日本ピューレット・パッカード製：４２８４Ａ）を用いて金電極とシリコン基板に挟まれた部分の静電容量を測定し、誘電率を算出したところ、誘電率２．９５であった。
【００８６】
【実施例１２】
実施例１で得られた生成した白色粉を使用し、小型真空蒸着装置 ＬＵＭＩＮＯ（日本真空製） を用いて ０．５×１０^−３ Ｐａ の条件下でシリコン基板に真空蒸着することにより ０．２μｍ厚の膜を得た。この膜の誘電率を実施例１１と同様に求めたところ、２．７５であった。
【００８７】
【比較例４】
シリコン基板を電気炉中で約 ９００℃に熱し、その中に飽和水蒸気を５ｌ／ｍｉｎ で導入することによってシリコン基板表面にＳｉＯ_２酸化膜を形成した。この酸化膜の膜厚は ０．３μｍであった。この膜の誘電率を実施例１１と同様に求めたところ ３．７であった。
【００８８】
【比較例５】
実施例１と同様の装置にプロピルトリメトキシシラン５０ｇとアセトン５０ｇを入れ、５０℃に保持しながら約３０分間かけて１Ｎ−ＮａＯＨ 水溶液 ６．０ｇを滴下した。滴下終了後、反応混合物を１５時間攪拌して、加水分解および縮合反応を完結させた。得られた反応液を用いて、実施例１１と同様にして、スピンコート法による成膜と膜の誘電率の測定を行ったところ、誘電率は ３．５であった。
実施例１１で成膜したペルフルオロメチル基を有する膜の誘電率は２．９５であるので、ペルフルオロメチル基の導入により膜の誘電率が低下することがわかる。
【００８９】
【実施例１３】
実施例４で得られた反応液を０．４５μｍのメンブレンフィルターでろ過して、不溶物を除去した。この溶液を、溶媒の揮発を防ぐようにしたスピンコータを用いて、回転速度４５００ ｒｐｍでガラス基板上に塗布し、次いで ２００℃に３０分間加熱して塗膜を乾燥させることにより成膜して、ペルフルオロアルキル基を持つポリシロキサン膜を形成した。
【００９０】
得られた膜の水との接触角を測定するため、室温で約２μｌ の水滴をマイクロシリンダの針先に作り、これを塗布面に滴下させ、接触角測定器で塗布面と水との接触角を測定したところ １０１°であった。
【００９１】
また、ガラス基板の背面 （塗布面と反対側の面） に黒色テープを貼付して背面からの反射を防止してから、塗布面の反射率を反射率測定装置を用いて波長 ２４０ｍｍ〜８００ｍｍ の範囲で測定したところ、反射率は１．３ ％であった。
【００９２】
【比較例６】
テトラエトキシシランの加水分解物を含有する１０％メタノール溶液を０．４５μｍのメンブレンフィルターでろ過して不溶物を除去した。この溶液を用いて、実施例１０と同様にガラス基板上への塗布を乾燥を行ってＳｉＯ_２膜を成膜した。
【００９３】
この膜の水との接触角および反射率を実施例１０と同様に測定したところ、水との接触角は２５°、反射率は４％であった。
【００９４】
【実施例１４】
実施例１で得られた反応液に黒インクを滴下し、十分に攪拌して液を着色した。この着色液を０．４５μｍのメンブレンフィルターでろ過して不溶物を除去した。この着色液にガラス基板を浸漬し、２ｍｍ／ｍｉｎの一定速度で基板を引き上げることにより塗布を行った。塗布した基板を１５０ ℃に３０分間加熱して膜を乾燥させた。乾燥後の膜の外観は、目視では穴や突起のない平滑な黒色膜であった。
【００９５】
この黒色膜に、波長５３２ ｎｍ、出力１８０ ｍＪのＹＡＧ レーザを１秒、５秒、１０秒、および２０秒間照射し、照射後の表面状態を観察した。ビーム径はいずれも約１ｃｍであった。膜は１秒のレーザ照射によって、ビーム照射部分のみが完全に焼失し、ガラス面が出た。照射時間が２０秒でも結果は同じであった。レーザ光によって膜が焼失した部分には膜の焦げや、変性物などはなかった。
【００９６】
【比較例７】
ポリアクリル酸１０ｇを３０ｇのメタノールに溶解し、得られた溶液に黒インクを滴下し、溶液を十分攪拌して着色した。この着色液を０．４５μｍのメンブレンフィルターでろ過して不溶物を除去した。この着色液にガラス基板を浸漬し、２ｍｍ／ｍｉｎの一定速度で基板を引き上げることにより塗布を行った。塗布した基板を１５０ ℃に３０分間加熱して膜を乾燥させた。乾燥後の膜の外観は、目視では穴や突起のない平滑な黒色膜であった。
【００９７】
このポリアクリル酸の膜に、実施例１１と同様にして波長５３２ ｎｍ、出力１８０ ｍＪのＹＡＧ レーザを照射し、表面状態を観察した。膜はレーザ照射によってビームが当たった部分が変質し、ガラス基板上で黒く焼き焦げていた。
【００９８】
【比較例８】
実施例１と同様の反応装置に、［ＣＦ_３ＣＨ_２ＣＨ_２Ｓｉ（ＯＭｅ）_３］ ５０ｇ（０．２３ ｍｏｌ）とテトラヒドロフラン５０ｇを入れ、生成した溶液を５０℃に保持しながら、０．２Ｎ−ＨＣｌ水溶液６．０ ｇ（ＨＣｌ １．２ ｍｍｏｌ）を約３０分間かけて滴下した。滴下終了後、反応混合物を同じ温度で１５時間攪拌して、加水分解および縮合反応を完結させた。
【００９９】
得られた反応液に黒インクを滴下し、溶液を十分に攪拌して、液を黒く着色した。この液を０．４５μｍのメンブレンフィルターでろ過して不溶物を除去した。この着色液にガラス基板を浸漬し、１０ ｍｍ／ｍｉｎ の一定速度で基板を引き上げることにより塗布を行った。塗布した基板を１５０ ℃に３０分間加熱して膜を乾燥させた。乾燥後の膜の外観は、目視では穴や突起のない平滑な黒色膜であった。
【０１００】
このペルフルオロアルキル基を有するポリシロキサンの膜に、実施例１１と同様にして波長５３２ ｎｍ、出力１８０ ｍＪのＹＡＧ レーザを照射し、表面状態を観察した。膜はレーザ照射によってビームが当たった部分が変質し、ガラス基板上でやや黒く焼き焦げていた。
【０１０１】
【発明の効果】
本発明により、特定の有機溶媒に溶解し、溶解状態で安定に保存できる、ペルフルオロアルキル基を有するかご型多面体構造の単一分子量の有機ケイ素化合物が提供される。この有機ケイ素化合物は、湿式法および乾式法により成膜材料として使用するのに適している。この成膜により、ポリテトラフルオロエチレンのようなフッ素樹脂とは異なり、密着性のよいペルフルオロアルキル基含有膜を各種基材の表面に形成することが可能となる。
【０１０２】
こうして本発明の有機ケイ素化合物から形成された膜は、ポリシロキサン質であるため、耐熱性や耐火性に優れ、またペルフルオロアルキル基の存在に起因する撥水・撥油性を示す上、低誘電率、低屈折率、高硬度、色素添加によりレーザ等によるパターニングが可能、といった特徴を持ち、また溶媒への溶解性を利用してエッチングが可能であるので、撥水・撥油膜、低誘電率膜、低反射膜、色素添加したパターニング用膜などとして有望である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel cage-shaped polyhedral organosilicon compound containing a perfluoro group, a method for producing the same, and a use thereof. The organosilicon compound of the present invention is useful as a film-forming material to which both a dry film-forming method and a wet film-forming method can be applied, has a low dielectric constant and a low refractive index, exhibits water / oil repellency, and contains a dye. By doing so, patterning is possible, and a high-quality film having heat resistance and fire resistance can be formed.
[0002]
[Prior art]
Tetraalkoxysilanes (also called alkyl silicates) such as tetraethoxysilane, tetramethoxysilane, and tetrapropoxysilane are tetrafunctional silane monomers. The product of hydrolysis and condensation of these compounds (substantially completely hydrolyzed is called silica sol) forms a high-hardness film with excellent heat resistance, corrosion resistance, and transparency. As a system hard coat agent, it has been widely used for film formation applications such as paints and surface modifiers. However, since the formed film is an inorganic silica, the film characteristics are almost determined.
[0003]
On the other hand, monoalkyl trialkoxysilanes (eg, monomethyltrimethoxysilane, monoethyltriethoxysilane, monomethyltripropoxysilane, etc.) in which one of the four alkoxy groups is substituted with an alkyl group in the above compound are trifunctional silane monomers. is there. The product obtained by hydrolyzing and condensing the trifunctional silane monomer becomes a polysiloxane-type polymer containing an alkyl group since the alkyl group remains. This product is noted as an organic-inorganic composite material because the remaining alkyl group exhibits properties as an organic compound.
[0004]
[Problems to be solved by the invention]
When a product synthesized from such a trifunctional silane monomer is used as a film forming material, the film is formed by changing the chain length of the remaining alkyl group or introducing various substituents into the alkyl group. Is likely to change, so that the application range is expected to be wider than that of a tetrafunctional silane monomer. For example, when a fluorine group is introduced into an alkyl group, a film having water and oil repellency inherent to an organic fluorine group may be formed.
[0005]
However, in practice, a film-forming material synthesized from a trifunctional silane monomer having an organic fluorine group through hydrolysis and condensation according to a conventional method cannot obtain a polymer, and thus has a low film hardness. There is a problem that it is difficult to form a film that can withstand practical use, or conversely, it becomes gel-like, loses solubility in a solvent, and is not suitable for coating. The products obtained by hydrolyzing and condensing these compounds have low stability to moisture, and also have the disadvantage that during storage they are denatured or precipitated, making it difficult to use them as stable film-forming materials.
[0006]
Conventionally, a fluorine-based polymer such as polytetrafluoroethylene has been used as a material for imparting water / oil repellency to a substrate surface, but this type of polymer has poor adhesion to a substrate, Since the solubility in a solvent is low, there is a problem that it is difficult to use as a film forming material.
[0007]
An object of the present invention is to provide an organosilicon compound which is excellent in adhesion to a substrate, exhibits water and oil repellency, can form a high-quality film, can be stably stored in a solution state, and is suitable as a film-forming material. In particular, it is an object of the present invention to provide an organosilicon compound having a perfluoroalkyl group. Another object of the present invention is to provide a method for producing this organosilicon compound and its use.
[0008]
[Means for Solving the Problems]
It is possible to obtain a trialkoxysilane-type organosilicon compound containing a perfluoroalkyl group by substituting the alkyl group of the monoalkyl trialkoxysilane-type compound with a perfluoroalkyl group. Even if a material obtained by hydrolyzing and condensing the compound in the presence of an acid catalyst according to a conventional method is used for film formation, a high-quality film cannot be obtained, so that the above-mentioned problem cannot be solved. The hydrolyzate of this compound also has low stability.
[0009]
The trifunctional silane compound having a perfluoroalkyl group has another problem. In other words, this type of silane compound having a perfluoroalkyl group, when hydrolysis and condensation proceed to increase the degree of polymerization, the solubility in an organic solvent is extremely reduced. It is more difficult to promote the hydrolysis than the hydrogen silane compound substituted with.
[0010]
The present inventors hydrolyze and condense a trialkoxysilane compound having a perfluoroalkyl group in a specific solvent in the presence of a basic catalyst, and these reactions smoothly proceed to form a cage-shaped polyhedral structure. It was found by accident that an organosilicon compound having the formula: Since this organosilicon compound is dissolved in a specific solvent, it can be used as a film-forming material by either a wet method such as spin coating or a dry method such as vapor deposition, and forms a high-quality film by film formation. Since the formed film has a structure mainly composed of siloxane bonds, it has excellent heat resistance and fire resistance as compared with a hydrocarbon-based resin film. This film exhibits a low refractive index and a low dielectric constant as well as water and oil repellency due to the perfluoroalkyl group, and is therefore useful as a low reflection film and a low dielectric constant film. Further, since it is dissolved in a specific solvent, it can be etched. If a dye is contained, it can be used as a film for patterning using heat of a laser or the like.
[0011]
The present invention has been completed based on the above findings, and provides an organosilicon compound having a polyhedral structure containing a perfluoroalkyl group and represented by the following general formula (1), a method for producing the same, and a use thereof.
[0012]
[Rf-X- (CH₂)_a-SiO_1.5]_m          (1)
In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, X is a divalent bonding group, a is an integer of 0 to 10, and m is an integer of 4 to 20.
[0013]
The organosilicon compound represented by the general formula (1) is obtained by converting a compound represented by the following general formula (3) into an organic solvent containing at least one element selected from O, N, F, and Cl in water. And a hydrolysis and condensation reaction in the presence of a basic compound.
[0014]
Rf-X- (CH₂)_a-Si (Y)₃              (3)
In the formula, Y is an alkoxy group having 1 to 8 carbon atoms or Cl, and Rf, X and a have the same meanings as described above. In the present specification, the alkyl group and the alkoxy group may be linear or branched.
[0015]
The organosilicon compound represented by the general formula (1) according to the present invention is useful as a film-forming material and can be used in a state of being dissolved in a specific organic solvent. Since the film formed from this organosilicon compound has water / oil repellency, a low refractive index and a low dielectric constant, it is useful as a low dielectric constant film, a low reflection film, and a water / oil repellent film. Can be used as a film for patterning by dispersing and containing.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
In general, a compound composed of a siloxane bond (Si—O—Si) (that is, polysiloxane) is classified into a chain polysiloxane, a cyclic polysiloxane, a ladder-type polysiloxane, and a polyhedral (cage-type) depending on the configuration of the siloxane bond. ) Broadly classified into four types of polysiloxane.
[0017]
Polysiloxane with cage-shaped polyhedral structure is,General formula (RSiO_1.5) m is an organosilicon compound represented by the formula, and is generically referred to as silsesquioxane (where R is an organic group and m is an integer). This compound is obtained by hydrolysis and condensation of a trifunctional silane compound. The structure of the polyhedral silane compound when m (for the compound of the general formula (1)) or m + n (for the compound of the general formula (2)) is 8 or 12, is shown below.
[0018]
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[0019]
As for the organosilicon compound having such a polyhedral structure, a compound in which R is an alkyl group, a monofluoro-substituted alkyl group, or a perfluorophenyl-substituted alkyl group is described in Eckhard Rikowski et al., Polyhedron, Vol. 16, No. 19 pp. 3357-3361 (1997), etc., but this type of compound having an alkyl group substituted with a perfluoroalkyl group has not been known so far.
[0020]
This is because, as described above, the solubility of the silane compound having a perfluoroalkyl group in an organic solvent is extremely reduced as the degree of polymerization increases due to hydrolysis and condensation, and therefore the alkyl group is unsubstituted. It is considered that the reason is that the hydrolysis and the condensation reaction are less likely to proceed as compared with the silane compound which is hydrogen or hydrogen, and it is difficult to proceed the condensation sufficiently until the polyhedral structure is obtained.
[0021]
In the present invention, the hydrolysis and condensation reaction are carried out in an organic solvent containing at least one element selected from O, N, F, and Cl in the presence of water and a basic compound, thereby obtaining a conventional method. This makes it possible to synthesize a polysiloxane compound having a polyhedral structure having a perfluoroalkyl group, which has been difficult. As a result, as shown in the following reaction formula, an organosilicon compound having a polyhedral polysiloxane structure represented by the general formula (1) is converted from a trifunctional silane monomer having a perfluoroalkyl group represented by the general formula (3). Obtainable.
[0022]
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In the above formula, Rf, X, a, Y, and m have the same meaning as described above.
[0023]
In the above general formula, X is preferably -CH₂-, -O-, -N (R)-, -S-, -C (O) O-, -CON (R)-and -SO₂Selected from the group consisting of N (R)-, wherein R is hydrogen or an alkyl or alkenyl group having 1 to 10 carbon atoms. R is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms. Rf is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. The larger the carbon number of Rf, the more hydrophobic the film can be formed. Particularly preferred among the organosilicon compounds represented by the general formula (1) are those represented by the formula: (Rf-CH₂-CH₂-SiO_1.5)_mX = —CH represented by₂-, A = 1, but X = —CONH— or —SO₂N (C₃H₇)-, A = 3 is also preferable.
[0024]
Y in the general formula (3) is preferably an alkoxy group having 1 to 5 carbon atoms or chlorine, and more preferably a methoxy group, an ethoxy group or chlorine. The three Y groups may be the same or different. The value of m in the general formula (1) is preferably from 8 to 16.
[0025]
As the basic compound used as a catalyst in the above reaction, it is preferable to use one or more selected from the group consisting of metal hydroxides, amine compounds, and quaternary ammonium salt hydroxides. Ammonium hydroxide or ammonia gas) can also be used. The amine compound is preferably a tertiary amine. Preferred examples of the basic compound include alkali metal hydroxides such as KOH, NaOH, and LiOH, and Ca (OH)₂, Ba (OH)₂Alkaline earth metal hydroxides, such as trimethylamine, triethylamine, pyridine, lutidine, and the like; and quaternary ammonium salt hydroxides, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.
[0026]
Conventionally, an acid (eg, a mineral acid such as hydrochloric acid or nitric acid) has been generally used as a catalyst for hydrolyzing a silane compound. However, when an acid catalyst is used, the reaction only partially proceeds. No caged polyhedral siloxane product can be obtained.
[0027]
The amount of the basic compound and water used in the above reaction is 1 × 10 4 mol of the basic compound per 1 mol of the raw material monomer represented by the general formula (3).^-5２2 mol, preferably 1 × 10^-3１1 mol, and water is 1-20 mol, preferably 1.5-6 mol. If the amount of the basic compound of the catalyst is too large, the reaction may proceed rapidly and gelation may occur. On the other hand, if the amount is too small, the reaction does not proceed sufficiently, and the proportion of unreacted substances increases. Water is necessary for the hydrolysis of the starting monomers. When the amount of water is less than 1 mol, hydrolysis and condensation do not proceed sufficiently. If the amount of water is too large, the raw material monomer and the solvent undergo phase separation, and the desired polyhedral compound is not formed.
[0028]
According to another aspect of the present invention, a plurality of (that is, different from each other) trifunctional silane monomers each having a perfluoroalkyl group and represented by the general formulas (4) and (5) are used as starting materials. By performing hydrolysis and condensation in the same manner as in the case of using one type of silane monomer represented by the above general formula (3) as a substance, as shown in the following reaction formula, 2) An organosilicon compound having a monomeric polysiloxane structure having a different organic compound and having a perfluoroalkyl group in one molecule, represented by the following formula, can be produced. The present invention also provides such an organosilicon compound and a method for producing the same.
[0029]
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In the formula, Rf ′ and Rf ″ are each a perfluoroalkyl group having 1 to 20 carbon atoms, X ′ and X ″ are each a divalent bonding group, a and b are each an integer of 0 to 10, m and n are each 1 to An integer of 19, m + n is 4 to 20, Y 'and Y "are each an alkoxy group having 1 to 8 carbon atoms or Cl, and Rf' and Rf", X 'and X ", and a and b At least one combination is not identical to one another.
[0030]
Specific examples and preferred examples of Rf ′ and Rf ″ and X ′ and X ″ are as described above for Rf and X, respectively. Particularly preferred among the organosilicon compounds represented by the general formula (2) are those represented by the formula: (Rf'-CH₂-CH₂-SiO_1.5)_m(Rf "-CH₂-CH₂-SiO_1.5)_nX ′ = X ″ = − CH₂-, Where a = b = 1, wherein X ′ and X ″ are —CONH— or —SO₂N (C₃H₇)-, And a = b = 3 is also preferable.
[0031]
The synthesis of compound (2) from compounds (4) and (5) can be carried out in the same manner as the synthesis of compound (1) from compound (3) described above. And the amount of water used may be the same as above. The silane monomer used is not limited to two types, and three or more different organic silane monomers may be used.
[0032]
In the case of producing any of the organosilicon compounds of the general formulas (1) and (2), the reaction solvent is an organic solvent containing at least one element selected from O, N, F and Cl. . The solvent used is one in which both the raw material monomer and the produced polymer are well dissolved. Examples of such solvents are alcohols, ketones, ethers, fluorinated and / or chlorinated hydrocarbons, amines, amides and the like. Note that the amine solvent can function as both a catalyst and a solvent. The solvent may be a mixture of two or more solvents.
[0033]
Specific examples of preferred solvents include methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, cyclohexanone, isophorone, diethyl ether, dioxane, tetrahydrofuran, trichlorotrifluoroethane, trichloroethane, triethylamine, pyridine, lutidine, dimethylformamide, dimethylacetamide and the like. And a mixed solvent thereof.
[0034]
In the hydrolysis and condensation reaction, for example, a silane compound as a raw material monomer is dissolved in the above-mentioned organic solvent, and an aqueous solution of a basic compound as a catalyst is dropped into the obtained solution, or the basic compound and water are combined or separately. Can be carried out by dropping or adding to the mixture. However, the reaction method is not limited to this. The reaction can be carried out at a temperature of 10 to 150 ° C, but the reaction temperature is preferably 50 to 120 ° C to obtain a high yield. The reaction time is set so that the hydrolysis and condensation reactions are completed as much as possible, and varies depending on the reaction temperature, but is usually about 1 to 72 hours.
[0035]
As described above, when the hydrolysis and condensation reaction of the trifunctional silane monomer represented by the general formula (3) is performed, a siloxane compound represented by the general formula (1) is generated, and the general formulas (4) and (5) When the trifunctional silane monomer represented by the formula (1) is subjected to hydrolysis and condensation reaction, a siloxane compound represented by the general formula (2) is produced. The product is obtained in a state of being dissolved in a medium consisting of an organic solvent and water. In order to isolate the product from the reaction solution, for example, the organic solvent and water may be distilled off, and the residue may be purified by an appropriate method (eg, extraction, recrystallization, distillation, chromatography). Alternatively, if purity is not an issue, the reaction solution can be used as it is (eg, by simply filtering off insolubles) as a film-forming material. Alternatively, a solution in which the product is dissolved in an organic solvent may be obtained by removing water and a basic compound of the catalyst from the reaction solution by an appropriate method (eg, distillation, extraction, washing with water, etc.). This solution can be stored for a long time and used as a film forming material.
[0036]
The resulting polyhedral siloxane compound is a polymer, and has a uniform degree of polymerization (constant m value [general formula (1)] or a constant m value showing a very narrow peak in the molecular weight distribution measured by GPC (gel permeation chromatography). A compound having an m + n value [general formula (2)].²⁹When analyzed by Si-NMR and GPC,²⁹In Si-NMR measurement, one silicon atom has three Si—O—Si bonds [that is, R—Si (O—Si—)₃A single peak is obtained, and in most cases, one peak is obtained by measuring the molecular weight distribution by GPC. From these results, it can be seen that the produced compound has the above cage-shaped polyhedral structure.
[0037]
This siloxane compound is
An organic group having a cage-shaped polyhedral structure as shown in the following and having a perfluoroalkyl group remaining after hydrolysis [eg, in the general formula (1), Rf-X- (CH₂)_a-Group] exists at the position of ◎ around the “basket”.
[0038]
This polyhedral siloxane compound, unlike a chain polysiloxane, is extremely stable because it has no reaction points (eg, a hydroxyl group or an alkoxy group at the molecular end) in the structure. Therefore, even if it is stored in a solution state, it does not cause denaturation or precipitation, so that it has excellent storage stability and good solubility.
[0039]
The polyhedral organosilicon compound having a perfluoroalkyl group of the present invention is useful as a film-forming material for various purposes. Since this compound has excellent solubility in the above-mentioned organic solvents that can be used for the reaction, it is easily used in various wet film forming methods such as spin coating, dipping, and spraying in a solution state. be able to. Further, a dry film formation method by vacuum evaporation, preferably in a solid state or a solution state, can also be adopted. The thickness of the formed film is not particularly limited, but is preferably about 0.1 to 2 μm. Drying after the wet film formation is preferably performed at 60 to 200 ° C.
[0040]
The film formed from the polyhedral organosilicon compound of the present invention exhibits excellent water and oil repellency due to the presence of a perfluoroalkyl group appearing on the surface of the polyhedral structure. However, unlike water- and oil-repellent fluororesins such as polytetrafluoroethylene, the molecular framework is composed of siloxane bonds (-Si-O-Si-), so this film adheres to various substrates. Also excellent in nature. In addition, they exhibit excellent heat resistance and fire resistance inherent in siloxane-bonded films. Therefore, a water-repellent / oil-repellent film having unprecedented excellent adhesion and heat resistance is obtained. This water-repellent / oil-repellent film is useful for applications such as imparting water / oil repellency to a glass plate.
[0041]
This film has characteristics of low refractive index and low dielectric constant in addition to water repellency and oil repellency, and thus is useful as a low reflection film and a low dielectric constant film. The low reflection film can be formed, for example, on the surface of a cathode ray tube of a TV or various display devices (CRT, liquid crystal, EL, plasma, etc.) for improving image quality. The low dielectric constant film is useful, for example, as an interlayer insulating film of a semiconductor device.
[0042]
Since the film made of the polyhedral organosilicon compound of the present invention is also vaporized at a constant temperature, if a dye is dispersed in the film, it is suitable for patterning by heat such as laser, and is precisely (with high resolution) patterning. can do. The dye preferably has an absorption maximum near the wavelength of the laser used. Film formation is performed using a solution of a polyhedral organosilicon compound, and an appropriate amount of a dye is added to the solution and dissolved to form a film in which the dye is dispersed. Since the film can be dissolved in an organic solvent, it can be removed by etching after patterning, if necessary. Therefore, for example, it can be used as a resist for fine processing of a semiconductor element.
[0043]
【Example】
Hereinafter, the present invention will be described specifically with reference to examples.
[0044]
Embodiment 1
(CF ₃ CH ₂ CH ₂ SiO _1.5 ) ₈ Synthesis of
100 cm capacity with magnetic stirrer, thermometer, dropping funnel³  [CF]₃CH₂CH₂Si (OMe)₃21.8 g (0.1 mol) and 21.8 g of acetone were added, and while maintaining the resulting solution at 50 ° C., 6.0 g of a 1N aqueous NaOH solution (6 mmol of NaOH, 0.3 mol of water) was added. It was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 15 hours to complete the hydrolysis and condensation reactions. Then, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure to obtain a white powder (yield: 85%). The white powder was washed and purified (80% yield after purification).
[0045]
The purified product can be purchased from Shodex^TM0.75 cm using a KF801 + 802 column³When the molecular weight distribution was measured by GPC using tetrahydrofuran as an eluent at / min, one peak was obtained at 17.22 min. When the molecular weight was calculated in terms of polystyrene from the elution time of this peak, it corresponded to the molecular weight of m = 8.
[0046]
The result of elemental analysis of this product, IR spectrum (only characteristic peak, the same applies hereinafter) and²⁹The Si-NMR spectrum (standard substance: TMS, solvent: acetone, the same applies hereinafter) was as follows.²⁹One strong peak was obtained in the Si-NMR spectrum. The peak position coincided with the peak of the trifunctional siloxane.
[0047]
From the above, the productCage-shaped polyhedral structure (CF_ThreeCH_TwoCH_TwoSiO_1.5)₈Was identified.

IR: 2920, 2960, 1130, 1070cm^-1
29Si-NMR: δ (ppm) = -70.5.
[0048]
The thermal properties of the purified product were examined by TG-DTA measurement using TG-8110 (manufactured by RIGAKU). When the sample was heated from room temperature to 10 ° C./min in air, the weight loss up to 260 ° C. was 5% or less, showing stable thermal characteristics. When the temperature was further increased, an endotherm was observed at around 260 ° C., and a sharp decrease in weight was observed. The residue after heating to 350 ° C. was less than 5%, and most of them were volatilized. Further, the aluminum pan after the measurement did not show any change in appearance from before the sample was put, and no residue or coloring was observed.
[0049]
Embodiment 2
(CF ₃ CH ₂ CH ₂ SiO _1.5 ) ₁₂ Synthesis of
In the same reactor as in Example 1, [CF₃CH₂CH₂Si (OMe)₃21.8 g (0.1 mol) and 65.4 g of tetrahydrofuran were added, and while maintaining the obtained solution at 60 ° C., 3.0 g of a 1N aqueous KOH solution (3 mmol of KOH, 0.167 mol of water) was added to the solution. After the dropwise addition over 30 minutes, the reaction mixture was stirred at the same temperature for 24 hours to complete the hydrolysis and condensation reaction. Then, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure to obtain a white powder (yield 84%). The white powder was purified by washing with water (yield after purification: 75%).
[0050]
The molecular weight distribution of the purified product was measured by GPC in the same manner as in Example 1. As a result, one peak was obtained at 16.75 min. When the molecular weight was calculated in terms of polystyrene from the elution time of this peak, it corresponded to the molecular weight of m = 12.
The result of elemental analysis, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹One strong peak was obtained in the Si-NMR spectrum. The peak position coincided with the peak of the trifunctional siloxane.
[0051]
From the above, the productCage-shaped polyhedral structure (CF_ThreeCH_TwoCH_TwoSiO_1.5)₁₂Was identified.

IR: 2920, 2960, 1130, 1070cm^-1
29Si-NMR: δ (ppm) =-71.0
[0052]
Embodiment 3
(CF ₃ CF ₂ CH ₂ CH ₂ SiO _1.5 ) ₁₀ Synthesis of
In the same reactor as in Example 1, [CF₃CF₂CH₂CH₂Si (OMe)₃26.8 g (0.1 mol) and 40 g of acetone are added, and while the obtained solution is kept at 50 ° C., 7.3 g of a 1.25 N NaOH aqueous solution (9.1 mmol of NaOH, 3.7 mol of water). Was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 24 hours to complete the hydrolysis and condensation reactions. Then, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure to obtain a white powder (yield: 85%). The white powder was purified by reprecipitation from water (yield after purification: 78%).
[0053]
The molecular weight distribution of the purified product was measured by GPC in the same manner as in Example 1. As a result, one peak was obtained at 16.93 min. When the molecular weight was calculated from the elution time of this peak in terms of polystyrene, it corresponded to the molecular weight of m = 10.
The result of elemental analysis, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹One strong peak was obtained in the Si-NMR spectrum. The peak position coincided with the peak of the trifunctional siloxane.
[0054]
From the above, the productCage-shaped polyhedral structure(CF_ThreeCF_TwoCH_TwoCH_TwoSiO_1.5)_TenWas identified.

IR: 2960, 1130, 1070cm^-1
29Si-NMR: δ (ppm) = -70.5
The thermal properties of the purified product were measured as in Example 1. When the sample was heated from room temperature at room temperature at a rate of 10 ° C./min, the weight loss up to 275 ° C. was less than 5%, showing stable thermal characteristics. When the temperature was further increased, endothermic absorption and a sharp decrease in weight were observed below 275 ° C. The residue after heating to 350 ° C. was less than 5%, indicating that most of the residue was volatile. Further, the aluminum pan after the measurement did not show any change in appearance from before the sample was put, and no residue or coloring was observed.
[0055]
Embodiment 4
(C ₄ F ₉ CH ₂ CH ₂ SiO _1.5 ) ₁₀ Synthesis of
500 cm capacity³[C] in the same reactor as in Example 1 except that a three-necked flask was used.₄F₉CH₂CH₂Si (OMe)₃36.8 g (0.1 mol) and 220 g of an acetone / methanol (1/1 wt / wt) mixed solvent are added, and while maintaining the obtained solution at 50 ° C., 12 g of a 1N-NaOH aqueous solution (NaOH 12 mmol, (0.6 mol of water) was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 24 hours to complete the hydrolysis and condensation reactions. Then, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure to obtain a white powder (yield: 80%). This white powder was purified by washing with water (yield after purification: 73%).
[0056]
When the molecular weight distribution of the purified product was measured by GPC in the same manner as in Example 1, one peak was obtained at 16.37 min. When the molecular weight was calculated from the elution time of this peak in terms of polystyrene, it corresponded to the molecular weight of m = 10.
The result of elemental analysis, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹One strong peak was obtained in the Si-NMR spectrum. The peak position coincided with the peak of the trifunctional siloxane.
[0057]
From the above, the productCage-shaped polyhedral structure (C_FourF₉CH_TwoCH_TwoSiO_1.5)_TenWas identified.

IR: 2920, 2960, 1130, 1070cm^-1
29Si-NMR: δ (ppm) =-71.2
[0058]
Embodiment 5
(C ₈ F ₁₇ CH ₂ CH ₂ SiO _1.5 ) ₈ Synthesis of
1000 cm capacity³[C] in the same reactor as in Example 1 except that the three-necked flask was used.₈F₁₇CH₂CH₂Si (OMe)₃56.8 g (0.1 mol) and 500 g of 1,1,2-trichloro-2,2,1-trifluoroethane were added, and while maintaining the obtained solution at 40 ° C., tetramethylammonium hydroxide 34 g (base 37 mmol) of a 10% methanol solution and 12 g (667 mmol) of water were added dropwise over about 30 minutes. After the completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 3 hours to complete the hydrolysis and condensation reactions. Subsequently, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure, and the resulting viscous liquid was washed with water and purified (yield after purification: 76%).
[0059]
The molecular weight distribution of the purified product was measured by GPC in the same manner as in Example 1. As a result, one peak was obtained at 16.03 min. When the molecular weight was calculated in terms of polystyrene from the elution time of this peak, it corresponded to the molecular weight of m = 8.
The result of elemental analysis, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹One strong peak was obtained in the Si-NMR spectrum. The peak position coincided with the peak of the trifunctional siloxane.
[0060]
From the above, the productCage-shaped polyhedral structure(C₈F₁₇CH_TwoCH_TwoSiO_1.5)₈Was identified.

IR: 2920, 2960, 1130, 1070cm^-1
29Si-NMR: δ (ppm) = -71.5
[0061]
Embodiment 6
(C ₇ F _Fifteen CONH (CH ₂ ) ₃ SiO _1.5 ) ₁₂ Synthesis of
In the same reactor as in Example 4, [C₇F_FifteenCONH (CH₂)₃Si (Cl)₃59.0 g (0.1 mol) and 181.5 g of 1,4-dioxane were added, and then 1.0 g (9.9 mmol) of triethylamine and 20.0 g (1.1 mol) of water were added. The mixture was stirred at 100 ° C. for 12 hours to complete the hydrolysis and condensation reaction. Next, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure, the residue was washed with water, and then poured into hexane to separate and remove insolubles, thereby purifying the product (yield after purification: 74%).
[0062]
The molecular weight distribution of the purified product was measured by GPC in the same manner as in Example 1, and the molecular weight was roughly calculated in terms of polystyrene, which was equivalent to the molecular weight of the above compound.
The result of elemental analysis, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹In the Si-NMR spectrum, one strong peak was mainly obtained. The peak position coincided with the peak of the trifunctional siloxane.
[0063]
From the above, the productCage-shaped polyhedral structure(C₇F₁₅CONH (CH_Two)_ThreeSiO_1.5)₁₂Was identified.

IR: 2920, 2960, 1720, 1130, 1070cm^-1
29Si-NMR: δ (ppm) =-71.4
[0064]
Embodiment 7
(C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₃ SiO _1.5 ) ₁₀ Synthesis of
In the same reactor as in Example 5, [C₈F₁₇SO₂N (C₃H₇) (CH₂)₃Si (OEt)₃74.5 g (0.1 mol) and 670 g of acetone were added, and while maintaining the resulting solution at 50 ° C., 5.5 g (6.0 mmol of base) of a 10% methanol solution of tetramethylammonium hydroxide and water were added. 3.0 g (167 mmol) was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 24 hours to complete the hydrolysis and condensation reactions. Subsequently, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure, and the residue was washed with water and purified (yield after purification: 67%).
[0065]
The molecular weight distribution of the purified product was measured by GPC in the same manner as in Example 1, and the molecular weight was roughly calculated in terms of polystyrene, which was equivalent to the molecular weight of the above compound.
The result of elemental analysis, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹One strong peak was obtained in the Si-NMR spectrum. The peak position coincided with the peak of the trifunctional siloxane.
[0066]
From the above, the productCage-shaped polyhedral structure(C₈F₁₇SO_TwoN (C_ThreeH₇) (CH_Two)_ThreeSiO_1.5)_TenWas identified.

IR: 2920, 2960, 1400, 1130, 1070cm^-1
29Si-NMR: δ (ppm) =-70.9
[0067]
Embodiment 8
(CF ₃ CH ₂ CH ₂ SiO _1.5 ) ₇ (C ₈ F ₁₇ CH ₂ CH ₂ SiO _1.5 ) ₁ Synthesis of
In the same reactor as in Example 1, [CF₃CH₂CH₂Si (OMe)₃18.7 g (0.086 mol), [C₈F₁₇CH₂CH₂Si (OMe)₃8.1 g (0.014 mol) and 27 g of tetrahydrofuran as a solvent are added, and while maintaining the obtained solution at 50 ° C., 8.0 g of a 1N aqueous solution of NaOH (8.3 mmol of NaOH, 0.4 mol of water). Was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 15 hours to complete the hydrolysis and condensation reactions. Then, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure to obtain a white powder (yield: 85%). This white powder was purified by reprecipitation from water.
[0068]
When the molecular weight distribution of the purified product was measured by GPC in the same manner as in Example 1, one peak was obtained at 17.09 min. When the molecular weight was calculated from the elution time of this peak in terms of polystyrene, it corresponded to the molecular weight of the above compound.
The result of elemental analysis, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹One strong peak was obtained in the Si-NMR spectrum. The peak position coincided with the peak of the trifunctional siloxane.
[0069]
From the above, the productCage-shaped polyhedral structure(CF_ThreeCH_TwoCH_TwoSiO_1.5)₇(C₈F₁₇CH_TwoCH_TwoSiO_1.5)₁Was identified.

IR: 2920, 2960, 1130, 1070cm^-1
29Si-NMR: δ (ppm) = -69.7
The thermal properties of the purified product were measured as in Example 1. When the temperature of the sample was raised from room temperature to 10 ° C./min in air, the weight loss up to 270 ° C. was 5% or less, showing stable thermal characteristics. When the temperature was further increased, endothermic absorption and rapid weight loss were observed below 270 ° C. The residue after heating to 400 ° C. was less than 5%, indicating that most of the residue was volatile. Further, the aluminum pan after the measurement did not show any change in appearance from before the sample was put, and no residue or coloring was observed.
[0070]
Embodiment 9
(CF ₃ CH ₂ CH ₂ SiO _1.5 ) ₈ (C ₄ F ₉ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₃ SiO _1.5 ) ₂ Synthesis of
In the same reactor as in Example 4, [CF₃CH₂CH₂Si (OMe)₃21.8 g (0.1 mol), [C₄F₉SO₂N (C₃H₇) (CH₂)₃Si (OMe)₃12.6 g (0.025 mol) and 103 g of a solvent, trichlorotrifluoroethane, were added, and the resulting solution was maintained at 30 ° C., and 6.0 g of a 10% methanol solution of tetramethylammonium hydroxide (base 6. 6 mmol) and 7 g (0.39 mol) of water were added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 24 hours to complete the hydrolysis and condensation reactions. Next, a low-boiling substance containing a solvent and water was distilled off from the reaction solution under reduced pressure to obtain a white powder (yield: 77%). This white powder was purified by reprecipitation from water.
[0071]
The molecular weight distribution of the purified product was measured by GPC in the same manner as in Example 1, and the molecular weight was roughly calculated in terms of polystyrene, which was equivalent to the molecular weight of the above compound.
The result of elemental analysis, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹One strong peak was obtained in the Si-NMR spectrum. The peak position coincided with the peak of the trifunctional siloxane.
[0072]
From the above, the productCage-shaped polyhedral structure(CF_ThreeCH_TwoCH_TwoSiO_1.5)₈(C_FourF₉SO_TwoN (C_ThreeH₇) (CH_Two)_ThreeSiO_1.5)_TwoWas identified.

IR: 2920, 2960, 1400, 1130, 1070cm^-1
29Si-NMR: δ (ppm) = -69.5
[0073]
Embodiment 10
(C ₄ F ₉ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₃ SiO _1.5 ) ₇ (C ₈ F ₁₇ CH ₂ CH ₂ SiO _1.5 ) ₁ Synthesis of
In the same reactor as in Example 4, [C₄F₉SO₂N (C₃H₇) (CH₂)₃Si (OMe)₃50.3 g (0.1 mol), [C₈F₁₇CH₂CH₂Si (OMe)₃10 g (18 mmol) and 120 g of acetone as a solvent are added, and while keeping the obtained solution at 50 ° C., about 0.5 N-KOH aqueous solution 8 g (KOH 4 mmol, water 0.4 mol) is added for about 30 minutes. The solution was dropped. After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 24 hours to complete the hydrolysis and condensation reactions. Then, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure to obtain a white powder (yield: 72%). This white powder was purified by reprecipitation from water.
[0074]
The molecular weight distribution of the purified product was measured by GPC in the same manner as in Example 1, and the molecular weight was roughly calculated in terms of polystyrene, which was equivalent to the molecular weight of the above compound.
The result of elemental analysis, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹One strong peak was obtained in the Si-NMR spectrum. The peak position coincided with the peak of the trifunctional siloxane.
[0075]
From the above, the productCage-shaped polyhedral structure(C_FourF₉SO_TwoN (C_ThreeH₇) (CH_Two)_ThreeSiO_1.5)₇(C₈F₁₇CH_TwoCH_TwoSiO_1.5)₁Was identified.

IR: 2920, 2960, 1400, 1130, 1070cm^-1
29Si-NMR: δ (ppm) = -69.7
[0076]
[Comparative Example 1]
In the same reactor as in Example 1, [CF₃CH₂CH₂Si (OMe)₃21.8 g (0.1 mol) and acetone (21.8 g) were added, and while maintaining the resulting solution at 50 ° C., 1.0 g of a 0.2 N HCl aqueous solution (0.2 mmol of HCl, 0.056 of water) was added. mol) was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 15 hours to complete the hydrolysis and condensation reactions. Then, low-boiling substances containing a solvent and water were distilled off from the reaction solution under reduced pressure to obtain a pale yellow highly viscous oil (yield 81%).
[0077]
When the molecular weight distribution of this product was measured by GPC in the same manner as in Example 1, a plurality of peaks including a monomer peak were obtained. Its elemental analysis results, IR spectrum and²⁹The Si-NMR spectrum was as follows.²⁹In the Si-NMR spectrum, three strong peaks were obtained, and the peak positions coincided with the peaks of the monomer and the mono- and bifunctional siloxane.
[0078]

[0079]
The thermal properties of this product were examined by TG-DTA measurement in the same manner as in Example 1. When the sample was heated in air at a rate of 10 ° C./min from room temperature, weight loss was observed stepwise at 220 ° C. and 350 ° C., and the residue was 65% at 350 ° C. Even when the temperature was further raised to 400 ° C., 40% or more remained. This residue had turned black on an aluminum pan.
[0080]
From the above, it can be seen that when an acid catalyst was used, an organosilicon compound having a cage polyhedral structure intended in the present invention could not be obtained.
[0081]
[Comparative Example 2]
In the same reactor as in Example 1, [CF₃CH₂CH₂Si (OMe)₃21.8 g (0.1 mol) and acetone (21.8 g) were added, and while maintaining the resulting solution at 50 ° C., 1.0 g of a 0.01 N aqueous NaOH solution (0.01 mmol of NaOH, 0.056 mol of water) ) Was added dropwise. After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 24 hours to complete the hydrolysis and condensation reactions. Next, a low-boiling substance containing a solvent and water was distilled off from the reaction solution under reduced pressure to obtain a colorless, transparent and highly viscous oil (yield: 82%).
[0082]
Using a sample of this product, the molecular weight distribution was measured by GPC in the same manner as in Example 1. As a result, a plurality of peaks including a monomer peak were obtained. In this example, the amount of water used was too small, so that an intended organosilicon compound having a polyhedral structure could not be obtained.
[0083]
[Comparative Example 3]
In the same reactor as in Example 1, [CF₃CH₂CH₂Si (OMe)₃21.8 g (0.1 mol) and acetone (21.8 g) were added, and while maintaining the resulting solution at 50 ° C., 6.0 g (NaOH 6 mmol) of a 1N aqueous NaOH solution was added dropwise, and then 34 g of water ( Water (2.2 mol in total) was added dropwise. A white precipitate formed during the addition of the water. In this example, since the amount of water used was too large, the intended organosilicon compound having a polyhedral structure could not be obtained.
[0084]
Embodiment 11
The reaction solution obtained in Example 1 was filtered with a 0.45 μm membrane filter to remove insolubles. This solution was applied on a silicon substrate at a rotation speed of 4500 rpm using a spin coater that prevented the solvent from volatilizing, and then heated at 150 ° C. for 30 minutes to dry the coating, thereby forming a film. A polysiloxane film having a perfluoroalkyl group was formed.
[0085]
The film thickness after drying was measured using a scanning electron microscope and found to be 0.3 μm. The obtained film was colorless and transparent, and had a smooth surface without holes or protrusions. A circular electrode having a diameter of 2 mm was formed on this film by gold deposition, and the capacitance between the gold electrode and the silicon substrate was measured using an LCR meter (Puret Packard Japan: 4284A). When the ratio was calculated, the dielectric constant was 2.95.
[0086]
Embodiment 12
Using the white powder produced in Example 1 and a small vacuum evaporation apparatus LUMINO (manufactured by Nippon Vacuum), 0.5 × 10^-3  Vacuum evaporation was performed on the silicon substrate under the condition of Pa 2 to obtain a film having a thickness of 0.2 μm. When the dielectric constant of this film was determined in the same manner as in Example 11, it was 2.75.
[0087]
[Comparative Example 4]
The silicon substrate is heated to about 900 ° C. in an electric furnace, and saturated water vapor is introduced therein at a rate of 5 l / min.₂An oxide film was formed. The thickness of this oxide film was 0.3 μm. The dielectric constant of this film was determined in the same manner as in Example 11, and was found to be 3.7.
[0088]
[Comparative Example 5]
50 g of propyltrimethoxysilane and 50 g of acetone were placed in the same apparatus as in Example 1, and 6.0 g of a 1N aqueous solution of NaOH was added dropwise over about 30 minutes while maintaining the temperature at 50 ° C. After completion of the dropwise addition, the reaction mixture was stirred for 15 hours to complete the hydrolysis and condensation reactions. Using the obtained reaction solution, film formation by a spin coating method and measurement of the dielectric constant of the film were performed in the same manner as in Example 11, and the dielectric constant was 3.5.
Since the dielectric constant of the film having a perfluoromethyl group formed in Example 11 is 2.95, it can be seen that the dielectric constant of the film is reduced by the introduction of the perfluoromethyl group.
[0089]
Embodiment 13
The reaction solution obtained in Example 4 was filtered with a 0.45 μm membrane filter to remove insolubles. This solution was applied on a glass substrate at a rotation speed of 4500 rpm using a spin coater that prevented the solvent from volatilizing, and then heated to 200 ° C. for 30 minutes to dry the coating, thereby forming a film. A polysiloxane film having a perfluoroalkyl group was formed.
[0090]
In order to measure the contact angle of the obtained film with water, a water drop of about 2 μl was made at room temperature on the tip of the microcylinder at the room temperature, and this was dropped on the coating surface. The angle was measured to be 101 °.
[0091]
Also, after applying a black tape to the back surface (the surface opposite to the application surface) of the glass substrate to prevent reflection from the back surface, the reflectance of the application surface is measured using a reflectance measuring device at a wavelength of 240 mm to 800 mm. When measured in the range, the reflectance was 1.3%.
[0092]
[Comparative Example 6]
A 10% methanol solution containing a hydrolyzate of tetraethoxysilane was filtered through a 0.45 μm membrane filter to remove insolubles. Using this solution, the coating on the glass substrate was dried in the same manner as in Example 10 to obtain SiO 2.₂A film was formed.
[0093]
When the contact angle with water and the reflectance of this film were measured in the same manner as in Example 10, the contact angle with water was 25 ° and the reflectance was 4%.
[0094]
Embodiment 14
Black ink was dropped into the reaction liquid obtained in Example 1, and the liquid was colored by sufficiently stirring. The coloring solution was filtered through a 0.45 μm membrane filter to remove insolubles. The glass substrate was immersed in the coloring liquid, and the substrate was pulled up at a constant speed of 2 mm / min to perform coating. The coated substrate was heated to 150 ° C. for 30 minutes to dry the film. The appearance of the dried film was a smooth black film having no holes or protrusions visually.
[0095]
The black film was irradiated with a YAG laser having a wavelength of 532 nm and an output of 180 mJ for 1, 5, 10 and 20 seconds, and the surface state after irradiation was observed. Each beam diameter was about 1 cm. The film was completely burned off by the laser irradiation for one second, and only the beam irradiation part was completely burned out, and the glass surface was exposed. The result was the same even when the irradiation time was 20 seconds. There was no burnt or denatured film in the portion where the film was burned off by the laser light.
[0096]
[Comparative Example 7]
10 g of polyacrylic acid was dissolved in 30 g of methanol, black ink was dropped into the obtained solution, and the solution was sufficiently stirred to be colored. The coloring solution was filtered through a 0.45 μm membrane filter to remove insolubles. A glass substrate was immersed in the coloring liquid, and the substrate was pulled up at a constant speed of 2 mm / min to perform coating. The coated substrate was heated to 150 ° C. for 30 minutes to dry the film. The appearance of the dried film was a smooth black film having no holes or protrusions visually.
[0097]
This polyacrylic acid film was irradiated with a YAG laser having a wavelength of 532 nm and an output of 180 mJ in the same manner as in Example 11, and the surface state was observed. The portion of the film irradiated with the laser beam was altered by laser irradiation, and was burnt black on the glass substrate.
[0098]
[Comparative Example 8]
In the same reactor as in Example 1, [CF₃CH₂CH₂Si (OMe)₃50 g (0.23 mol) and 50 g of tetrahydrofuran were added, and 6.0 g (1.2 mmol of HCl) of a 0.2 N HCl aqueous solution was added dropwise over about 30 minutes while maintaining the resulting solution at 50 ° C. . After completion of the dropwise addition, the reaction mixture was stirred at the same temperature for 15 hours to complete the hydrolysis and condensation reactions.
[0099]
Black ink was added dropwise to the obtained reaction solution, and the solution was sufficiently stirred to color the solution black. This solution was filtered through a 0.45 μm membrane filter to remove insolubles. The glass substrate was immersed in the coloring liquid, and the substrate was pulled up at a constant speed of 10 mm / min to perform coating. The coated substrate was heated to 150 ° C. for 30 minutes to dry the film. The appearance of the dried film was a smooth black film having no holes or protrusions visually.
[0100]
This polysiloxane film having a perfluoroalkyl group was irradiated with a YAG laser having a wavelength of 532 nm and an output of 180 mJ in the same manner as in Example 11, and the surface state was observed. The portion of the film irradiated with the laser beam was altered by laser irradiation, and was slightly burnt black on the glass substrate.
[0101]
【The invention's effect】
According to the present invention, there is provided a cage-type polyhedral single-molecule organosilicon compound having a perfluoroalkyl group, which can be stably stored in a dissolved state in a specific organic solvent. This organosilicon compound is suitable for use as a film-forming material by a wet method and a dry method. By this film formation, unlike a fluororesin such as polytetrafluoroethylene, it is possible to form a perfluoroalkyl group-containing film having good adhesion on the surface of various substrates.
[0102]
Since the film formed from the organosilicon compound of the present invention is polysiloxane, it has excellent heat resistance and fire resistance, exhibits water and oil repellency due to the presence of the perfluoroalkyl group, and has a low dielectric constant. It has features such as low refractive index, high hardness, patterning by laser etc. by adding dye, and it is possible to etch by using solubility in solvent, so water-repellent / oil-repellent film, low dielectric constant film , A low reflection film, a patterning film added with a dye, and the like.

Claims (18)

An organosilicon compound having a cage polyhedral structure containing a perfluoroalkyl group and represented by the following general formula (1).
[Rf-X- (CH ₂ ) _a -SiO _1.5 ] _m (1)
In the formula, Rf is a C 1-20 perfluoroalkyl group , and X is -CH _2- , -O-, -N (R)-, -S-, -C (O) O-, -CON ( R) - and -SO ₂ N (R) - is a divalent linking group selected from the group consisting of, wherein R is an alkyl or alkenyl group of hydrogen or carbon number. 1 to 10, a is 0 An integer of 10 and m is an integer of 4 to 20. An organosilicon compound having a cage polyhedral structure containing a perfluoroalkyl group and represented by the following general formula (2). .
[Rf'-X '- (CH 2) a -SiO 1.5] m [Rf "-X" - (CH 2) b -SiO 1.5] n (2)
Wherein, Rf 'and Rf "are each a perfluoroalkyl group having 1 to 20 carbon atoms, X' and X" -CH ₂ is respectively -, -O-, -N (R) -, -S-, - C (O) O-, -CON ( R) - and -SO ₂ N (R) - is a divalent linking group selected from the group consisting of, wherein R is hydrogen or an alkyl group having a carbon number of 1-10 Or a and b are each an integer of 0 to 10, m and n are each an integer of 1 to 19, and m + n is 4 to 20, Rf 'and Rf ", X' and X" , And at least one combination of a and b are not identical to one another. _{Formula: (Rf-CH 2 -CH 2} -SiO 1.5) represented by _m, claim 1 organic silicon compound according. _{Formula: (Rf'-CH 2 -CH 2} -SiO 1.5) m (Rf "-CH 2 -CH 2 -SiO 1.5) is indicated by _n, Rf 'and Rf" are different, the organosilicon of claim 2, wherein Compound. X, or X 'and X "are, -CONH- or _{-SO 2 N (C 3 H 7} ) - a and, a, or a and b is 3, in any one of claims 1 to 4, The organosilicon compound according to the above. The organosilicon compound according to any one of claims 1 to 5 , wherein Rf, Rf 'and Rf "are perfluoroalkyl groups having 1 to 10 carbon atoms. The organosilicon compound according to claim 6 , wherein Rf, Rf 'and Rf "are perfluoroalkyl groups having 2 to 8 carbon atoms. A compound represented by the following general formula (3) is subjected to a hydrolysis and condensation reaction in an organic solvent containing at least one element selected from O, N, F, and Cl in the presence of water and a basic compound. A method for producing an organosilicon compound having a cage-shaped polyhedral structure containing a perfluoroalkyl group and represented by the following general formula (1) :
[Rf-X- (CH ₂ ) _a -SiO _1.5 ] _m (1)
Rf-X- (CH ₂ ) _a -Si (Y) ₃ (3)
In the formula, Rf is a C 1-20 perfluoroalkyl group , and X is -CH _2- , -O-, -N (R)-, -S-, -C (O) O-, -CON ( R) - and -SO ₂ N (R) - is a divalent linking group selected from the group consisting of, wherein R is an alkyl or alkenyl group of hydrogen or carbon atoms. 1 to 10, Y is carbon number A is an integer of 0 to 10; m is an integer of 4 to 20; The presence of water and a basic compound in an organic solvent containing at least one element selected from the group consisting of O, N, F, and Cl by mixing a plurality of types of compounds represented by the following general formulas (4) and (5) A method for producing an organosilicon compound having a cage-shaped polyhedral structure containing a perfluoroalkyl group and represented by the following general formula (2) , wherein the organosilicon compound is subjected to hydrolysis and condensation reaction below .
[Rf '- X' - ( CH 2) a - SiO 1.5] m [Rf "- X" - (CH 2) b - SiO 1.5] n (2)
Rf '- X' - (CH 2) a - Si (Y ') 3 (4)
Rf "- X" - (CH 2) b - Si (Y ") 3 (5)
Wherein, Rf 'and Rf "are each a perfluoroalkyl group of from 1 to 20 carbon, X' and X" -CH ₂ is respectively -, -O-, -N (R) -, -S-, - C (O) O-, -CON ( R) - and -SO ₂ N (R) - is a divalent linking group selected from the group consisting of, wherein R is hydrogen or an alkyl group having a carbon number of 1-10 Or an alkenyl group, Y ′ and Y ″ are each an alkoxy group having 1 to 8 carbon atoms or Cl , a and b are each an integer of 0 to 10 , m and n are each an integer of 1 to 19 , And m + n is 4 to 20 , and at least one combination of Rf ′ and Rf ″ , X ′ and X ″ , and a and b is not the same as each other. The method according to claim 8 or 9, wherein the basic compound is selected from the group consisting of a metal hydroxide, an amine compound and a quaternary ammonium salt hydroxide. 1 × 10 ⁻⁵ to 2 mol of the basic compound is added to 1 mol of the compound represented by the general formula (3) or 1 mol of the total of two kinds of the compounds represented by the general formulas (4) and (5). The method according to any one of claims 8 to 10 , wherein 1 to 20 mol of water is used. The method according to any one of claims 8 to 11, wherein the hydrolysis and the condensation reaction are performed at a temperature of 10 to 150 ° C. Film forming material comprising an organic silicon compound according to any one of claims 1-7. 14. The film forming material according to claim 13, wherein the organosilicon compound is dissolved in an organic solvent. Low dielectric constant film comprising an organic silicon compound according to any one of claims 1-7. Low-reflection film made of an organic silicon compound according to any one of claims 1-7. Any water--repellent film composed of an organic silicon compound according to one of claims 1 to 7. A patterning film comprising the organosilicon compound according to any one of claims 1 to 7 , which contains a dispersed dye.