JP2545642C - - Google Patents
Info
- Publication number
- JP2545642C JP2545642C JP2545642C JP 2545642 C JP2545642 C JP 2545642C JP 2545642 C JP2545642 C JP 2545642C
- Authority
- JP
- Japan
- Prior art keywords
- glass
- group
- film
- protective film
- fluorocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011521 glass Substances 0.000 claims description 59
- 230000001681 protective Effects 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- -1 methylsilyl Chemical group 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 125000004430 oxygen atoms Chemical group O* 0.000 claims description 3
- 125000004433 nitrogen atoms Chemical group N* 0.000 claims description 2
- 239000010408 film Substances 0.000 description 46
- NBVXSUQYWXRMNV-UHFFFAOYSA-N Fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 18
- 239000004094 surface-active agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000005871 repellent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N Chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 4
- 239000005046 Chlorosilane Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000003373 anti-fouling Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- DCAYPVUWAIABOU-UHFFFAOYSA-N Hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 210000002381 Plasma Anatomy 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001186 cumulative Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000005338 frosted glass Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、ガラスに関するものである。さらに詳しくは、家、または自動車、
電車、飛行機等の乗り物に用いられている窓ガラスや鏡、またはガラス容器や眼
鏡等のガラス表面が、直接、または保護膜を介して、フッ素を含む界面活性剤よ
りなる単分子膜状の被膜で覆われている、撥水撥油性に優れたガラスを提供する
ものである。
従来の技術
従来より、ガラス表面の撥水撥油性を改善する方法には、ガラス表面にＳｉ系
界面活性剤を塗布したり（たとえば特開昭５５−９６５２号公報）、フルオロカ
ーボン系ポリマーの懸濁液を塗布する方法が用いられてきた。
発明が解決しようとする課題
しかしながら、前記従来の塗布方法は、製造が容易である反面、シリコン系界
面活性剤では撥油性が乏しく、フルオロカーボン系ポリマー膜は表面エネルギー
が極めて小さく、ガラスに対して反応に乏しいため、ガラス表面と塗膜の密着性
を良くすることには限界があり、耐久性のよい塗膜は得られないという課題があ
った。特に、塗膜にピンホールが混在した場合、このピンホールが引金となり膜
剥がれが生じ易かった。
以上のような従来法の欠点に鑑み、本発明の目的は、表面に均一に且つピンホ
ール無くフルオロカーボン基を含む界面活性剤よりなる単分子膜状の耐剥離強度
の高い撥水撥油膜を備えた防汚性ガラスを提供することにある。
課題を解決するための手段
前記目的を達成するため、本発明のガラスは、下記一般式［１］
（式中、ｍ＝１〜１５、ｎ＝０〜１５、ただしｍ＋ｎ＝１０〜３０の各整数を表
わす）
または下記一般式［２］
（式中、ｍ＝１〜８、ｎ＝０〜２、ただしｍ＋ｎ＝１〜１０、ｐ＝５〜２５の各
整数を表し、Ａはジメチルシリル基（−Ｓｉ（ＣＨ3）2−）を表わす。）
で表わされる有機基がナノメーターレベルの膜厚の単分子膜で、親水性基を表面
に有するガラス基材の最表面または親水性基を有する保護膜で覆われたガラス基
材の最表面に酸素または窒素原子を介して化学結合してなることを特徴とする。
前記した本発明のガラスを得るには、下記一般式［３］
Ｆ（ＣＦ2）m（ＣＨ2）nＳｉＲqＸ3-q ［３］
（式中、ｍ＝１〜１５、ｎ＝０〜１５、ただしｍ＋ｎ＝１０〜３０の各整数を示
し、Ｒはアルキル基を表し、Ｘはハロゲン原子またはアルコキシ基を表わす）
または下記一般式［４］
Ｆ（ＣＦ2）m（ＣＨ2）nＡ（ＣＨ2）pＳｉ（ＣＨ3）qＸ3-q ［４］
（式中ｍ＝１〜８、ｎ＝０〜２、ただしｍ＋ｎ＝１〜１０、ｐ＝５〜２５、ｑ＝
０〜２の各整数を示し、Ａはジメチルシリル基（−Ｓｉ（ＣＨ3）2−）を表わし
、Ｘはハロゲン原子またはアルコキシ基を表わす。）
で表わされるシラン系界面活性剤を用いて、ガラス表面と反応一体化させる。
作用
本発明のガラスでは、表面にはフッ化炭素基が露出し、ガラスや保護膜との界
面ではガラスや保護膜と共有結合した、すなわち基材と一体になった実用上剥離
しないナノメーターレベルの膜厚の撥水撥油性の被膜が形成されている。したが
って、ガラス本来の透明性や光沢が生かされ、且つ耐久性に優れた防汚効果を発
揮できる作用がある。
さらに、本発明のガラスでは、表面がフッ化炭素の有機基で覆われているため
、表面の摩擦係数が低くなりガラス自体の耐擦傷性が向上する作用もある。
実施例
以下、実施例を第１〜６図を用いて説明する。以下の実施例において％は重量
％を意味する。
例えば、第１図に示すように、あらかじめよく洗浄したガラス基材１（例えば
強化ガラス板）を用意しておく。一方、８０％ｎ−ヘキサデカン、１２％四塩化
炭素、８％クロロホルムよりなる有機溶媒の混合溶液にビニル基２（ＣＨ2＝Ｃ
Ｈ−）を含むシラン界面活性剤、たとえば、ＣＨ2＝ＣＨ−（ＣＨ2）n−ＳｉＣ
ｌ3（ｎ：整数。１０〜２０程度が最も扱いやすい）を３×１０-3〜５×１０-2
Ｍ程度の濃度で溶かした化学吸着液を調整しておき、前記ガラス基材１を室温で
１時間程度浸漬する（このとき、ガラス基材は必ずしも化学吸着液に浸漬する必
要はなく、液を塗布したりスプレーして、化学吸着液とガラス基材を接触させて
おけば良い）と、第１図に示したようにガラス基体１表面は水酸基を含んでいる
ため、クロロシラン系界面活性剤のクロロシリル基と水酸基とが反応して表面に
下記式［５］の結合が生成され、ビニル基２を含んだ単分子膜状の保護膜３ａ
が酸素原子を介して化学結合した形で、一層の保護膜として形成された。厚さは
２０〜３０オングストローム（２〜３ｎｍ）であった。 次に、酸素またはＮ2を含んだ雰囲気中で（空気中でもよい）、このガラス基
体をエネルギー線（電子線、Ｘ線、γ線、紫外線若しくはイオン線）で３Ｍｒａ
ｄ程度照射し、第２図に示したようにビニル基部２に水酸（−ＯＨ）基４（酸素
雰囲気の場合）、または第３図に示したようにアミノ（−ＮＨ2）基５（窒素雰
囲気の場合）を導入した。なお、雰囲気が空気の場合はこの両者が生成する。
なお、これらの官能基がビニル基に付加することは、ＦＴＩＲ分析により確認
された。
また、このとき表面に並んだビニル基は、Ｏ2及び／またはＮ2を含んだプラズ
マ中で処理する方法でも、第２図に示したような−ＯＨ基を付加させた単分子吸
着保護膜３ｂ、または第３図に示したような−ＮＨ2基を付加させた単分子吸着
保護膜３ｃを形成できる。
最後に、フッ化炭素基を含むシラン系の界面活性剤として下記一般式［６］
Ｆ（ＣＦ2）m（ＣＨ2）nＳｉＲqＸ3-q ［６］
（式中、ｍ＝１〜１５、ｎ＝０〜１５、ｍ＋ｎ＝１０〜３０、ｑ＝０〜２の各整
数を示し、Ｒはアルキル基を表わし、ＸはＦ，Ｃｌ，Ｂｒ，Ｉ等のハロゲン原子
またはアルコキシ基を表わす。なお前記において、ｍ＋ｎが１０未満であると分
子鎖がみじか過ぎて配向しにくくなり、また３０を越えると流動性が失われる。
またＲはメチル基のような低級アルキル基である。）
または下記一般式［７］
Ｆ（ＣＦ2）m（ＣＨ2）nＡ（ＣＨ2）pＳｉ（ＣＨ3）qＸ3-q ［７］
（式中、ｍ＝１〜８、ｎ＝０〜２、ｍ＋ｎ＝１〜１０、ｐ＝５〜２５、ｑ＝０〜
２の各整数を示し、Ａはジメチルシリル基（−Ｓｉ（ＣＨ3）2−）を表わし、Ｘ
はＦ，Ｃｌ，Ｂｒ，Ｉ等のハロゲン原子またはアルコキシ基を表わす。なお前記
において、ｍ＋ｎが１未満及びｐが５未満であると分子鎖がみじか過ぎて配向し
にくくなり、またｍ＋ｎが１０を越えかつｐが２５を越えると流動性が失われる
。）
で表わされる物質、例えばフッ化炭素基とクロロシリル基を含む下記式［８］
ＣＦ3ＣＨ2Ｏ（ＣＨ2）15ＳｉＣｌ3 ［８］
を用い、あらかじめ作製しておいた８０％ｎ−ヘキサデカン、１２％四塩化炭素
、８％クロロホルムよりなる有機溶媒の混合溶液に２×１０-3〜５×１０-2Ｍ程
度の濃度で溶かした化学吸着液を調製し、前記単分子吸着保護膜３ｂ、もしくは
３ｃが形成されたガラス基体１を１時間程度室温で浸漬すると（このときも、ガ
ラス基材は必ずしも化学吸着液に浸漬する必要はなく、液を塗布したりスプレー
して、化学吸着液とガラス基材を接触させておけば良い）、第２図に示したよう
に表面に−ＯＨ基や、第３図に示したように表面に−ＮＨ2基が露出しているた
め、フッ化炭素基を含むクロロシラン系界面活性剤のクロロシリル基と−ＯＨ基
または−ＮＨ2基とが脱離反応して表面に下記式［９］
の結合、または下記式［１０］
の結合が生成され、ガラス基体の表面にフッ化炭素基を含む単分子吸着膜６が、
第４図に示したような下層の単分子吸着保護膜３ｄと層間で化学結合した状態で
単分子累積膜７として形成でき、もしくは第５図に示したような下層の単分子吸
着保護膜３ｅと層間で化学結合した状態で単分子累積膜８として形成できた。
なお、表面の撥水撥油性膜とガラス基体の間に保護膜を必要としない場合には
、第１回目の化学吸着工程で、フルオロカーボン基を含むクロロシラン界面活性
剤を用いて、ガラス表面にフルオロカーボン基を含む単分子吸着膜のみ１層形成
することができた。
一方、複数層の単分子保護膜を必要とする場合には、吸着試薬としてＣＨ2＝
ＣＨ−（ＣＨ2）n−ＳｉＣｌ3を用い、化学吸着と放射線照射の工程を繰り返し
た後、最後に吸着試薬としてフルオロカーボン基を含むクロロシラン系界面活性
剤を吸着すれば、必要とする層数の保護膜を介して最表面にフルオロカーボン基
を含む単分子吸着膜が累積形成されたガラスを作製できた。
なお、上記実施例では、最表面に形成すべきフッ化炭素基を含むシラン系界面
活性剤としてＣＦ3ＣＨ2Ｏ（ＣＨ2）15ＳｉＣｌ3を用いたが、これ以外にも例え
ば
ＣＦ3（ＣＨ2）2Ｓｉ（ＣＨ3）2（ＣＨ2）15ＳｉＣｌ3
Ｆ（ＣＦ2）4（ＣＨ2）2Ｓｉ（ＣＨ3）2（ＣＨ2）9ＳｉＣｌ3
ＣＦ3ＣＯＯ（ＣＨ2）15ＳｉＣｌ3
ＣＦ3（ＣＦ2）7（ＣＨ2）2ＳｉＣｌ3
等が利用できた。また、上記物質においてクロロシリル基をアルコキシシリル基
に置換した物質をそれぞれ用いてもガラス基体表面に同様の被膜を形成できた。
次に、吸着形成した種々の単分子膜の臨界表面エネルギーを求めるために、い
ろいろな表面張力を持った各種液体を用い、液滴の濡れ角度による評価（自動接
触角計（協和界面科学（株）製））を行った。結果を第６図に示す。なお、第６
図では測定した接触角のｃｏｓθと液滴の表面張力との関係で示した。前記第６
図を用いると、各種被膜の臨界表面エネルギーを、それぞれのデータをｃｏｓθ
が１．０になるまで外挿することで求めることができる。
第６図より明らかなように、臨界表面エネルギーは被膜に含まれるフッ素の数
が多くなるほど小さくなり、フッ素の数が９以上では約１７ｄｙｎｅ／ｃｍ以下
となった。この値は、ポリ４フッ化エチレン（約１８ｄｙｎｅ／ｃｍ：機能性含
ふっ素高分子、日刊工業新聞社刊）のそれより小さく、これら被膜の表面では撥
水撥油性が極めて高いことが確認できた。
さらに、この表面の水に対する濡れ角度を測定すると、基材表面の粗さにも依
存するが１００〜１５０度となった。
従って、このガラス窓を用いれば乗り物の窓ガラスをワイパーレス化できたり
、眼鏡表面の曇を防止できる。
なお第６図中、
Ｆ１７は、Ｆ（ＣＦ2）8Ｓｉ（ＣＨ3）2（ＣＨ2）9ＳｉＣｌ3、
Ｆ９は、Ｆ（ＣＦ2）4（ＣＨ2）2Ｏ（ＣＨ2）15ＳｉＣｌ3、
Ｆ３は、ＣＦ3ＣＯＯ（ＣＨ2）15ＳｉＣｌ3、
ＮＴＳは、ＣＨ3（ＣＨ2）19ＳｉＣｌ3、
でそれぞれ作成された被膜を示す。
なお、上記実施例では、基材に強化ガラスを用いたが、本発明の方法は、家、
または自動車、電車、飛行機等の乗り物に用いられている窓ガラスや鏡、または
ガラス容器やレンズ等のガラス表面、その他撥水撥油性を必要としたガラス表面
の改質を目的とする全てのガラスに応用できる。また、無色透明なガラスに限定
されるものでもなく、例えば表面を粗面化したすりガラスや、さらに着色された
色ガラス、またはガラス繊維等でもよい。
要するに本発明は、親水性基を表面に有するガラスと、フルオロカーボン基を
含有するシラン界面活性剤とを化学吸着法を用いてガラス表面に化学結合させる
技術であれば、全て範疇にはいる。
なお保護膜は必ずしも単分子膜である必要はない。塗装された有機薄膜、その
他ゾルゲル法を用いたシリカコート膜や透明性の蒸着膜でもよい。ただし、表面
が親水性でない場合には、コロナ照射或はスパッタリング等の通常の手法により
表面を親水性にした後、本発明のフルオロカーボン基含有シラン界面活性剤を作
用させる必要がある。
発明の効果
本発明のガラスでは、ガラスまたは保護膜を有したガラスの表面にフルオロカ
ーボン基を含むクロロシラン系またはフルオロカーボン基を含むアルコキシシラ
ン系界面活性剤を吸着反応させて、表面にはフッ化炭素基が露出し、ガラスや保
護膜との界面ではガラスや保護膜と共有結合した、すなわち基材と一体になった
ナノメーターレベルの膜厚の撥水撥油性の被膜を形成できるので、ガラスの透明
性や光沢を損なうことなく、防汚性が高く且つ実用上剥離しない耐久性に優れた
ガラスを提供できる効果がある。
さらに、本発明のガラスでは、表面がフッ化炭素の有機基で覆われているため
、表面の摩擦係数が低くなりガラス自体の耐擦傷性が向上するので、基材ガラス
そのものよりもさらに強靭性を向上できる効果もある。Description: FIELD OF THE INVENTION The present invention relates to glass. For more information,
A monomolecular film-like coating made of a surfactant containing fluorine, either directly or via a protective film, on the glass surface of windows and mirrors used for vehicles such as trains and airplanes, or glass containers and glasses. The present invention is to provide a glass which is covered with, and has excellent water and oil repellency. 2. Description of the Related Art Conventionally, methods for improving the water / oil repellency of a glass surface include applying a Si-based surfactant to the glass surface (for example, Japanese Patent Application Laid-Open No. 55-9652) and suspending a fluorocarbon polymer. A method of applying a liquid has been used. Problems to be Solved by the Invention However, the conventional coating method is easy to manufacture, but has poor oil repellency with a silicon-based surfactant, has a very small surface energy of a fluorocarbon-based polymer film, and has a reaction with glass. Therefore, there is a limit in improving the adhesion between the glass surface and the coating film, and there is a problem that a coating film with good durability cannot be obtained. In particular, when pinholes were mixed in the coating film, the pinholes became triggers and the film was easily peeled. In view of the above-mentioned drawbacks of the conventional method, an object of the present invention is to provide a monomolecular film-like water- and oil-repellent film having a high peeling strength, which is made of a surfactant containing a fluorocarbon group uniformly and without pinholes on the surface. To provide antifouling glass. Means for Solving the Problems In order to achieve the above object, the glass of the present invention has the following general formula [1] (Wherein, m = 1 to 15, n = 0 to 15, where m + n = integers of 10 to 30) or the following general formula [2] (Wherein, m = 1~8, n = 0~2 proviso m + n = 1~10,, represent each an integer of p = 5 to 25, A is di methylsilyl (-Si (CH 3) 2 - a) The organic group represented by is a monomolecular film with a thickness of nanometer level, and the hydrophilic group is
Glass substrate covered with a protective film having a hydrophilic group or the outermost surface of a glass substrate having
It is characterized by being chemically bonded to the outermost surface of the material via oxygen or nitrogen atoms. In order to obtain the glass of the present invention, the following general formula [3] F (CF 2 ) m (CH 2 ) n SiR q X 3-q [3] (where m = 1 to 15, n = 0) To 15, where m + n = 10 to 30; R represents an alkyl group; X represents a halogen atom or an alkoxy group) or the following general formula [4]: F (CF 2 ) m (CH 2 ) n A (CH 2) p Si ( CH 3) q X 3-q [4] ( wherein m = 1~8, n = 0~2 proviso m + n = 1~10,, p = 5~25, q =
Indicates each integer of 0 to 2, A is di methylsilyl (-Si (CH 3) 2 - ) represents, X represents a halogen atom or an alkoxy group. The reaction is integrated with the glass surface using a silane-based surfactant represented by the formula (1). Action In the glass of the present invention, a fluorocarbon group is exposed on the surface, and is covalently bonded to the glass or the protective film at the interface with the glass or the protective film, that is, the nanometer level which is not practically peeled off integrally with the substrate. A water-repellent and oil-repellent film having a film thickness of? Therefore, there is an effect that the original transparency and gloss of the glass can be utilized and an antifouling effect having excellent durability can be exhibited. Furthermore, since the surface of the glass of the present invention is covered with an organic group of fluorocarbon, the surface has a function of reducing the friction coefficient and improving the scratch resistance of the glass itself. Embodiment Hereinafter, an embodiment will be described with reference to FIGS. In the following examples,% means% by weight. For example, as shown in FIG. 1, a well-washed glass substrate 1 (for example, a tempered glass plate) is prepared in advance. On the other hand, a mixed solution of an organic solvent consisting of 80% n-hexadecane, 12% carbon tetrachloride, and 8% chloroform was added to a vinyl group 2 (CH 2 ＣC
Silane surfactant containing H-), for example, CH 2 = CH- (CH 2 ) n -SiC
l 3 (n: an integer; about 10 to 20 is easiest to handle) is 3 × 10 −3 to 5 × 10 −2
A chemically adsorbed liquid dissolved at a concentration of about M is prepared, and the glass substrate 1 is immersed at room temperature for about 1 hour (at this time, the glass substrate does not necessarily have to be immersed in the chemically adsorbed liquid. It is sufficient that the glass substrate is brought into contact with the chemically adsorbed liquid by applying or spraying), and since the surface of the glass substrate 1 contains a hydroxyl group as shown in FIG. The chlorosilyl group reacts with the hydroxyl group to form a bond of the following formula [5] on the surface, and the monolayer protective film 3a containing the vinyl group 2 is chemically bonded via an oxygen atom to form a single layer. It was formed as a protective film. The thickness was 20-30 Angstroms (2-3 nm). Next, in an atmosphere containing oxygen or N 2 (even in air), the glass substrate is irradiated with an energy beam (electron beam, X-ray, γ-ray, ultraviolet ray or ion beam) at 3 Mra.
Irradiation of about d, a hydroxyl (—OH) group 4 (in an oxygen atmosphere) on the vinyl group 2 as shown in FIG. 2, or an amino (—NH 2 ) group 5 (as shown in FIG. 3) (In a nitrogen atmosphere). When the atmosphere is air, both are generated. The addition of these functional groups to the vinyl group was confirmed by FTIR analysis. In addition, the vinyl groups arranged on the surface at this time can be treated in a plasma containing O 2 and / or N 2 by a single-molecule adsorption protective film to which an —OH group is added as shown in FIG. 3b or a monomolecular adsorption protective film 3c to which an -NH 2 group is added as shown in FIG. 3 can be formed. Finally, the following general formula as a silane-based surfactant containing a fluorocarbon group [6] F (CF 2) m (CH 2) n SiR q X 3-q [6] ( wherein, m =. 1 to 15, n = 0 to 15, m + n = 10 to 30, and q = 0 to 2; R represents an alkyl group; X represents a halogen atom such as F, Cl, Br, I or an alkoxy group. In the above, if m + n is less than 10, the molecular chains are too short to be easily oriented, and if it exceeds 30, the fluidity is lost.
R is a lower alkyl group such as a methyl group. Or the following general formula [7] F (CF 2 ) m (CH 2 ) n A (CH 2 ) p Si (CH 3 ) q X3 -q [7] (where m = 1 to 8, n = 0-2, m + n = 1-10, p = 5-25, q = 0
Indicates each integer of 2, A is di methylsilyl (-Si (CH 3) 2 - ) represents, X
Represents a halogen atom such as F, Cl, Br, I or an alkoxy group. In the above, if m + n is less than 1 and p is less than 5, the molecular chains are too short to be easily oriented, and if m + n exceeds 10 and p exceeds 25, the fluidity is lost. Substances represented by), for example, using the following equation containing a fluorocarbon group and a chlorosilyl group [8] CF 3 CH 2 O (CH 2) 15 SiCl 3 [8], 80% n- hexadecane had been previously prepared , 12% carbon tetrachloride, 8% chloroform in a mixed solution of an organic solvent at a concentration of about 2 × 10 −3 to 5 × 10 −2 M to prepare a chemical adsorption solution, Alternatively, when the glass substrate 1 on which 3c is formed is immersed at room temperature for about 1 hour (in this case, the glass substrate does not necessarily need to be immersed in the chemical adsorption solution, and the solution is applied or sprayed to form the chemical adsorption solution. And a glass substrate). As shown in FIG. 2, the surface has --OH groups, and as shown in FIG. 3, --NH 2 groups are exposed on the surface. Chlorosilane Surfactants Containing Fluorinated Carbon Groups Formula on the surface and chlorosilyl groups and -OH group or -NH 2 groups by elimination reaction [9] Or the following formula [10] Is formed, and the monomolecular adsorption film 6 containing a fluorocarbon group is formed on the surface of the glass substrate.
The monomolecular accumulation protective film 3e shown in FIG. 5 can be formed as a monomolecular accumulation film 7 in a state of being chemically bonded to the lower monomolecular adsorption protective film 3d, or as shown in FIG. Thus, a monomolecular cumulative film 8 was formed in a state of being chemically bonded between the layers. When a protective film is not required between the water-repellent and oil-repellent film on the surface and the glass substrate, a fluorocarbon group-containing chlorosilane surfactant is used on the glass surface in the first chemical adsorption step. Only one monomolecular adsorption film containing groups could be formed. On the other hand, when a plurality of monolayer protective films are required, CH 2 =
Using CH— (CH 2 ) n —SiCl 3 and repeating the steps of chemisorption and irradiation, and finally adsorbing a chlorosilane-based surfactant containing a fluorocarbon group as an adsorption reagent, the number of required layers can be reduced. A glass having a monomolecular adsorption film containing fluorocarbon groups accumulated on the outermost surface via the protective film was produced. In the above embodiment, CF 3 CH 2 O (CH 2 ) 15 SiCl 3 was used as a silane-based surfactant containing a fluorocarbon group to be formed on the outermost surface. However, other than this, for example, CF 3 ( CH 2) 2 Si (CH 3 ) 2 (CH 2) 15 SiCl 3 F (CF 2) 4 (CH 2) 2 Si (CH 3) 2 (CH 2) 9 SiCl 3 CF 3 COO (CH 2) 15 SiCl 3 CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 could be used. In addition, a similar coating could be formed on the surface of the glass substrate by using each of the above substances in which a chlorosilyl group was substituted with an alkoxysilyl group. Next, in order to determine the critical surface energy of various monolayers formed by adsorption, various liquids with various surface tensions were evaluated by the wetting angle of the droplets (automatic contact angle meter (Kyowa Interface Science Co., Ltd. ))). The results are shown in FIG. The sixth
The figure shows the relationship between the measured contact angle cos θ and the surface tension of the droplet. The sixth
Using the figure, the critical surface energies of the various coatings are expressed as cos θ
Can be obtained by extrapolating until is 1.0. As is clear from FIG. 6, the critical surface energy became smaller as the number of fluorine contained in the coating increased, and became about 17 dyne / cm or less when the number of fluorine was 9 or more. This value was smaller than that of polytetrafluoroethylene (about 18 dyne / cm: functional fluorine-containing polymer, published by Nikkan Kogyo Shimbun), and it was confirmed that the water- and oil-repellency of the surface of these films was extremely high. . Further, when the wetting angle of the surface with water was measured, it was 100 to 150 degrees depending on the roughness of the substrate surface. Therefore, by using this glass window, the window glass of the vehicle can be made wiper-less, and fogging of the eyeglass surface can be prevented. In FIG. 6, F17 is F (CF 2 ) 8 Si (CH 3 ) 2 (CH 2 ) 9 SiCl 3 , and F9 is F (CF 2 ) 4 (CH 2 ) 2 O (CH 2 ) 15 SiCl 3 , F3 indicates a film formed of CF 3 COO (CH 2 ) 15 SiCl 3 , and NTS indicates a film formed of CH 3 (CH 2 ) 19 SiCl 3 . In addition, in the said Example, although the tempered glass was used for the base material, the method of this invention
Or any glass used for vehicles such as automobiles, trains, airplanes, etc., for the purpose of modifying glass surfaces such as window glass and mirrors, glass containers and lenses, and other glass surfaces that require water and oil repellency Applicable to Further, the glass is not limited to colorless and transparent glass, and may be, for example, frosted glass having a roughened surface, colored glass that is further colored, or glass fiber. In short, the present invention is included in any category as long as it is a technique in which glass having a hydrophilic group on the surface and a silane surfactant containing a fluorocarbon group are chemically bonded to the glass surface using a chemisorption method. Note that the protective film does not necessarily need to be a monomolecular film. It may be a coated organic thin film, a silica coat film using a sol-gel method, or a transparent vapor-deposited film. However, when the surface is not hydrophilic, it is necessary to make the surface hydrophilic by a usual method such as corona irradiation or sputtering, and then act on the fluorocarbon group-containing silane surfactant of the present invention. Effects of the Invention In the glass of the present invention, a chlorosilane-based surfactant containing a fluorocarbon group or an alkoxysilane-based surfactant containing a fluorocarbon group is caused to adsorb to the surface of glass or glass having a protective film, and a fluorocarbon group is formed on the surface. Is exposed and covalently bonded to the glass and the protective film at the interface with the glass and the protective film, that is, a water- and oil-repellent film with a thickness of nanometer level integrated with the substrate can be formed. This has the effect of providing a glass having high antifouling properties and practically excellent durability which does not peel off without impairing the properties and gloss. Furthermore, in the glass of the present invention, since the surface is covered with an organic group of fluorocarbon, the friction coefficient of the surface is reduced and the scratch resistance of the glass itself is improved, so that the glass is more tough than the base glass itself. There is also an effect that can be improved.
【図面の簡単な説明】
第１図〜第５図は、本発明の一実施例の化学吸着膜作成時のガラス表面の状態
を分子レベルまで拡大した工程断面概念図、第６図は各種化学吸着膜の表面エネ
ルギーを求めるためにそれぞれの被膜上で測定した、各種表面張力を有する液滴
に対する接触角のｃｏｓθをプロットした図である。
１ ガラス基体
２ ビニル基
３ａ，３ｂ，３ｃ 単分子吸着保護膜
３ｄ，３ｅ 下層の単分子吸着保護膜
４ 水酸基
５ アミノ基
６ フルオロカーボン基を含む単分子吸着膜
７，８ 単分子累積膜BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 to FIG. 5 are conceptual diagrams of process cross-sections in which the state of a glass surface at the time of forming a chemisorption film according to one embodiment of the present invention is enlarged to the molecular level, and FIG. FIG. 9 is a diagram plotting cos θ of a contact angle with respect to a droplet having various surface tensions, which is measured on each of the films to determine the surface energy of the adsorption film. DESCRIPTION OF SYMBOLS 1 Glass base 2 Vinyl group 3a, 3b, 3c Monomolecular adsorption protective film 3d, 3e Lower monomolecular adsorption protective film 4 Hydroxyl group 5 Amino group 6 Monomolecular adsorption film containing fluorocarbon group 7,8 Monomolecular accumulation film
Claims (1)
わす） または下記一般式［２］（式中、ｍ＝１〜８、ｎ＝０〜２、ただしｍ＋ｎ＝１〜１０、ｐ＝５〜２５の各
整数を表し、Ａはジメチルシリル基（−Ｓｉ（ＣＨ3）2−）を表わす。） で表わされる有機基がナノメーターレベルの膜厚の単分子膜で、親水性基を表面
に有するガラス基材の最表面または親水性基を有する保護膜で覆われたガラス基
材の最表面に酸素または窒素原子を介して化学結合してなることを特徴としたガ
ラス。[Claims] (1) The following general formula [1] (Wherein, m = 1 to 15, n = 0 to 15, where m + n = integers of 10 to 30) or the following general formula [2] (Wherein, m = 1~8, n = 0~2 proviso m + n = 1~10,, represent each an integer of p = 5 to 25, A is di methylsilyl (-Si (CH 3) 2 - a) The organic group represented by is a monomolecular film with a thickness of nanometer level, and the hydrophilic group is
Glass substrate covered with a protective film having a hydrophilic group or the outermost surface of a glass substrate having
Glass characterized by being chemically bonded to the outermost surface of a material via oxygen or nitrogen atoms.
Family
ID=
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