JPH08188448A - Production of antifouling glass - Google Patents
Production of antifouling glassInfo
- Publication number
- JPH08188448A JPH08188448A JP21755295A JP21755295A JPH08188448A JP H08188448 A JPH08188448 A JP H08188448A JP 21755295 A JP21755295 A JP 21755295A JP 21755295 A JP21755295 A JP 21755295A JP H08188448 A JPH08188448 A JP H08188448A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- group
- film
- silane
- glass surface
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガラスの製造方法
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
優れたガラスの製造方法を提供するものである。[0001] The present invention relates to a method for producing glass. More specifically, the glass surface of a window glass or a mirror, or a glass container or glasses used for a vehicle such as a house, an automobile, a train, or an airplane, or a surface activity containing fluorine, directly or through a protective film. An object of the present invention is to provide a method for producing glass excellent in water and oil repellency, which is covered with a monomolecular film-like coating made of an agent.
【０００２】[0002]
【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（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。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 (Japanese Patent Application Laid-Open No. 55-9652) and a method of suspending a fluorocarbon polymer. A method of applying a suspension has been used.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記従
来の塗布方法で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、一方、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
に対して反応しにくいため、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
られないという問題があった。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。However, while the conventional coating method is easy to manufacture, the silicone surfactant has poor oil repellency, while the fluorocarbon polymer film has a very low surface energy, and is not suitable for glass. On the other hand, there is a limit in improving the adhesion between the glass surface and the coating film because the reaction is difficult, 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.
【０００４】本発明は、前記従来の問題を解決するた
め、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性の高
い撥水撥油性被膜を備えた防汚性ガラスの製造方法を提
供することを目的とする。[0004] In order to solve the above-mentioned conventional problems, the present invention comprises a monomolecular film-like water- and oil-repellent coating of a surfactant containing a fluorocarbon group uniformly and without pinholes on its surface. It is an object of the present invention to provide a method for producing an antifouling glass.
【０００５】[0005]
【課題を解決するための手段】前記目的を達成するた
め、本発明の防汚性ガラスの製造方法は、一端に−ＣＦ
3 基を有し他端にクロロシリル基またはアルコキシシリ
ル基を有するシラン系界面活性剤を含む有機溶液を用
い、ガラス表面または保護膜の形成されたガラス表面と
前記シラン系界面活性剤を反応させて、前記ガラス表面
または保護膜の形成されたガラス表面に化学結合した前
記界面活性剤の分子残基からできた被膜を形成するとい
う構成を備えたものである。[Means for Solving the Problems]
Therefore, the method for producing an antifouling glass according to the present invention comprises the steps of:
3 Chlorosilyl group or alkoxysilyl group at the other end.
Using an organic solution containing a silane-based surfactant with
The glass surface or the glass surface with the protective film
By reacting the silane-based surfactant, the glass surface
Or before chemically bonding to the glass surface with a protective film
To form a film made from the molecular residues of the surfactant
It is provided with the following configuration.
【０００６】前記方法においては、一端に−ＣＦ3 基を
有し他端にクロロシリル基またはアルコキシシリル基を
有するシラン系界面活性剤分子が前記一般式（化１）及
び（化２）から選ばれる少なくとも一つであることが好
ましい。In the above method, a silane surfactant molecule having a —CF 3 group at one end and a chlorosilyl group or an alkoxysilyl group at the other end is selected from the general formulas (1) and (2). Preferably, it is at least one.
【０００７】前記一般式（化１）及び（化２）で表わさ
れるシラン系界面活性剤を用ると、ガラス表面と反応一
体化させることで下記一般式（化３）または（化４）で
表わされる有機基がガラス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ガラスを製造する上で好都合
である。When the silane-based surfactants represented by the general formulas (1) and (2) are used, they are reacted and integrated with the glass surface to obtain the following general formula (3) or (4). This is convenient for producing a glass in which the organic group represented is chemically bonded to the outermost surface of the glass via an oxygen or nitrogen atom.
【０００８】[0008]
【化３】 Embedded image
【０００９】[0009]
【化４】 [Chemical 4]
【００１０】本発明のガラスの製造方法では、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
撥油性の被膜を作製できる。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。In the method for producing glass of the present invention, a fluorocarbon group is exposed on the surface, and at the interface with the glass or the protective film, it is covalently bonded to the glass or the protective film, that is, it is practically integrated with the substrate. A water-repellent and oil-repellent film having a nanometer-level film thickness that does not peel off can be produced. 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.
【００１１】さらに、本発明のガラスの製造方法で作製
したガラスは、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。Further, since the surface of the glass produced by the method for producing glass of the present invention is covered with an organic group of fluorocarbon, the coefficient of friction of the surface is reduced and the abrasion resistance of the glass itself is improved. There is also.
【００１２】[0012]
【実施例】以下、実施例を用いて本発明をさらに具体的
に説明する。なお下記の実施例中、％は重量％である。EXAMPLES The present invention will be described in more detail below with reference to examples. In the following examples,% means% by weight.
【００１３】（実施例）例えば、図１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非水系有
機溶媒の混合溶液に、ビニル基２（ＣＨ 2＝ＣＨ−）を
含むシラン界面活性剤、たとえば、ＣＨ2＝ＣＨ−（Ｃ
Ｈ2）n−ＳｉＣｌ3 （ｎ：整数。１０〜２０程度が最も
扱いやすい。本実施例ではｎ＝１２：テトラデセニルト
リクロロシラン、ｎ＝１６：オクタデセニルトリクロロ
シラン、ｎ＝１７：ノナデセニルトリクロロシランをそ
れぞれ用いた。）を３×１０ -3〜５×１０- 2Ｍ（モル）
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）。この処理により、図１
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
酸基とが脱塩化水素反応して表面に下記式（化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保護膜と
して形成された。この保護膜３ａは２０〜３０オングス
トローム（２〜３ｎｍ）の厚さであった。(Embodiment) For example, as shown in FIG.
A glass substrate 1 (for example, tempered glass)
Board). On the other hand, 80% n-hexadecane,
Non-aqueous with 12% carbon tetrachloride and 8% chloroform
Vinyl group 2 (CH 2= CH-)
A silane surfactant containing, for example, CH2= CH- (C
H2)n-SiCl3 (N: integer. 10 to 20 is the most
easy to handle. In this embodiment, n = 12: tetradecenyl
Lichlorosilane, n = 16: octadecenyltrichloro
Silane, n = 17: Nonadecenyl trichlorosilane
I used each one. ) Is 3 × 10 -3~ 5 × 10- 2M (mol)
Adjust the chemical adsorption solution dissolved at a concentration of about
The glass substrate 1 is immersed at room temperature for about one hour (at this time,
The glass substrate does not necessarily have to be immersed in the chemisorbent.
Chemical spray and glass
What is necessary is just to contact a base material). By this processing, FIG.
As shown in, the surface of the glass substrate 1 contains hydroxyl groups.
Therefore, the chlorosilyl group of the chlorosilane-based surfactant and water
The acid group reacts with dehydrochlorination to form a bond of the following formula (Formula 5) on the surface.
Protective film in the form of a monolayer containing vinyl groups 2
3a is chemically bonded through an oxygen atom to form a single protective film.
Was formed. This protective film 3a has a thickness of 20 to 30 Å.
It was thick (2-3 nm).
【００１４】[0014]
【化５】 Embedded image
【００１５】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３
Ｍｒａｄ程度照射し、図２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）、または図
３に示したようにアミノ（−ＮＨ2）基５（窒素雰囲気
の場合）を付加させる（なお、雰囲気が空気の場合はこ
の両者が生成する）。Next, the glass substrate is irradiated with an energy beam (an electron beam, an X-ray, a γ-ray, an ultraviolet ray or an ion beam) in an atmosphere containing oxygen or N 2 (may be in the air).
Irradiate about Mrad, and as shown in FIG.
Hydroxyl (-OH) group 4 (in an oxygen atmosphere) or amino (-NH 2 ) group 5 (in a nitrogen atmosphere) as shown in FIG. 3 is added (when the atmosphere is air, Both are generated).
【００１６】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やＮ2を含んだプラズ
マ中で処理する方法でも、図２に示したような−ＯＨ基
を付加させた単分子吸着保護膜３ｂ、または図３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。The addition of these functional groups to the vinyl group was confirmed by FTIR analysis. Further, the vinyl groups arranged on the surface at this time can be treated in a plasma containing O 2 or N 2 by a monomolecular adsorption protective film 3 b to which an —OH group is added as shown in FIG. The monomolecular adsorption protective film 3c to which the -NH 2 group is added as shown in FIG.
Can be formed.
【００１７】最後に、フッ化炭素基を含むシラン系の界
面活性剤として一般式 Ｆ（ＣＦ2）m（ＣＨ2）nＳｉＲqＸ3 -q （式中ｍ＝１〜１５、ｎ＝０〜１５、（なお、被膜を形
成する上で分子配向性の最適値はｍ＋ｎ＝１０〜３０で
あった）、ｑ＝０〜２の各整数を示し、Ｒはアルキル基
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）または Ｆ（ＣＦ2）m（ＣＨ2）nＡ（ＣＨ2）pＳｉ（ＣＨ3）qＸ
3-q （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は酸素原子
（−Ｏ−）、オキシカルボニル基（−ＣＯＯ−）、また
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
わされる物質、例えばフッ化炭素基とクロロシリル基を
含む ＣＦ3ＣＨ2Ｏ（ＣＨ2）15ＳｉＣｌ3 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）、図２に示したように表面に−ＯＨ基や、
図３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 基とが脱塩化水
素反応して表面に下記式（化６）の結合、または（化
７）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、図４に示したような下層の
単分子内層膜３ｄ、もしくは図５に示したような下層の
単分子内層膜３ｅと層間で酸素分子または窒素分子を介
して化学結合した状態で単分子累積膜７として形成でき
た。Finally, as a silane-based surfactant containing a fluorocarbon group, a general formula F (CF 2 ) m (CH 2 ) n SiR q X 3 -q (where m = 1 to 15, n = 0) To 15, (the optimum value of molecular orientation for forming a film was m + n = 10 to 30), q = 0 to 2, R represents an alkyl group, X represents halogen. An atom or an alkoxy group) or F (CF 2 ) m (CH 2 ) n A (CH 2 ) p Si (CH 3 ) q X
3-q (where m = 1 to 8, n = 0 to 2, m + n = 1 to 10, p
= 5 to 25, shows each integer q = 0 to 2, A is an oxygen atom (-O-), an oxycarbonyl group (-COO-), or dimethylsilyl groups (-Si (CH 3) 2 - ) a Represent
X represents a halogen atom or an alkoxy group. ), For example, CF 3 CH 2 O (CH 2 ) 15 SiCl 3 containing a fluorocarbon group and a chlorosilyl group, is used to prepare 80% n-hexadecane, 12% carbon tetrachloride, 8% Prepared by dissolving in a mixed solution of an organic solvent consisting of 1% chloroform at a concentration of about 2 × 10 −3 to 5 × 10 −2 M, and forming the monomolecular adsorption protective film 3b or 3c on the glass. When the substrate 1 is immersed for about 1 hour at room temperature (also at this time, the glass base material does not necessarily have to be immersed in the chemical adsorption liquid, but the liquid may be applied or sprayed to bring the chemical adsorption liquid into contact with the glass base material. As shown in Figure 2, -OH groups on the surface,
Because the -NH 2 group on the surface as shown in FIG. 3 is exposed, the chlorosilane-based surface chlorosilyl group of an active agent and a -OH group or -NH 2 group is dehydrochlorination containing fluorocarbon group A bond of the following formula (Formula 6) or a bond of the formula (Formula 7) is generated on the surface, and a monomolecular adsorption film 6 containing a fluorocarbon group is formed on the surface of the glass substrate as shown in FIG. The monomolecular cumulative film 7 can be formed in a state where the monomolecular inner film 3d or the lower monomolecular inner film 3e as shown in FIG. 5 is chemically bonded via oxygen molecules or nitrogen molecules between the layers.
【００１８】[0018]
【化６】 [Chemical 6]
【００１９】[0019]
【化７】 [Chemical 7]
【００２０】なお、表面の撥水撥油性膜とガラス基体の
間に内層の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。In the case where an inner protective film is not required between the water- and oil-repellent film on the surface and the glass substrate, a chlorosilane surfactant containing a fluorocarbon group is used in the first chemical adsorption step. As a result, only one monomolecular adsorption film containing a fluorocarbon group was formed on the glass surface.
【００２１】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。On the other hand, when a multi-layered monomolecular protective film is required, CH 2 ═CH— (CH 2 ) n − as an adsorption reagent.
After repeating the steps of chemisorption and radiation irradiation using SiCl 3 , if a chlorosilane-based surfactant containing a fluorocarbon group is finally adsorbed as an adsorption reagent, it will reach the outermost surface through the protective film with the required number of layers. A glass on which a monomolecular adsorption film containing a fluorocarbon group was cumulatively formed could be produced.
【００２２】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ＣＦ3
ＣＨ2Ｏ（ＣＨ2）15ＳｉＣｌ3を用いたが、これ以外に
も例えば等が利用できた。 （１）ＣＦ3（ＣＨ2）2Ｓｉ（ＣＨ3）2（ＣＨ2）15Ｓｉ
Ｃｌ3 （２）Ｆ（ＣＦ2）4（ＣＨ2）2Ｓｉ（ＣＨ3）2（Ｃ
Ｈ2）9ＳｉＣｌ3 （３）ＣＦ3ＣＯＯ（ＣＨ2）15ＳｉＣｌ3 （４）ＣＦ3（ＣＦ2）7（ＣＨ2）2ＳｉＣｌ3 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材表
面に同様の被膜を形成できた。In the above embodiment, CF 3 is used as the silane-based surfactant containing a fluorocarbon group to be formed on the outermost surface.
Although CH 2 O (CH 2 ) 15 SiCl 3 was used, other materials such as, for example, could be used. (1) CF 3 (CH 2 ) 2 Si (CH 3 ) 2 (CH 2 ) 15 Si
Cl 3 (2) F (CF 2 ) 4 (CH 2 ) 2 Si (CH 3 ) 2 (C
H 2 ) 9 SiCl 3 (3) CF 3 COO (CH 2 ) 15 SiCl 3 (4) CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 In the above substance, the chlorosilyl group was replaced with an alkoxysilyl group. A similar coating could be formed on the surface of the glass substrate using each of the substances.
【００２３】（実施例２）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。結果を図６に示す。なお、図６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。こ
の図６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。Example 2 Next, in order to determine critical surface energies of various monolayers formed by adsorption, various liquids having various surface tensions were used, and evaluation was made based on the wetting angle of the droplets (automatic contact). An angle meter (manufactured by Kyowa Interface Science Co., Ltd.) was performed. FIG. 6 shows the results. FIG. 6 shows the relationship between the measured contact angle cos θ and the surface tension of the droplet. Using FIG. 6, the critical surface energies of various coatings are
It can be obtained by extrapolating each data until cos θ becomes 1.0.
【００２４】図６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１８
ｄｙｎｅ／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。As is clear from FIG. 6, the critical surface energy becomes smaller as the number of fluorine contained in the film increases, and becomes about 17 dyne / cm or less when the number of fluorine is 9 or more. This value is equivalent to polytetrafluoroethylene (about 18
dyne / cm: smaller than that of a 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.
【００２５】さらに、この表面の水に対する濡れ角度を
測定すると、基材表面の荒さにも依存するが１００〜１
５０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。Further, when the wetting angle of this surface to water is measured, it depends on the roughness of the surface of the base material, but it is 100 to 1
It was 50 degrees. 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.
【００２６】なお図６中の記号は次の化合物で形成され
た単分子膜を示している。 （１）Ｆ１７：Ｆ（ＣＦ2）8Ｓｉ（ＣＨ3）2（ＣＨ2）9
ＳｉＣｌ3 （２）Ｆ９：Ｆ（ＣＦ2）4（ＣＨ2）2Ｏ（ＣＨ2）15Ｓ
ｉＣｌ3 （３）Ｆ３：ＣＦ3ＣＯＯ（ＣＨ2）15ＳｉＣｌ3 （４）ＮＴＳ：ＣＨ3（ＣＨ2）19ＳｉＣｌ3 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。The symbols in FIG. 6 indicate monomolecular films formed of the following compounds. (1) F17: F (CF 2 ) 8 Si (CH 3 ) 2 (CH 2 ) 9
SiCl 3 (2) F9: F (CF 2 ) 4 (CH 2 ) 2 O (CH 2 ) 15 S
iCl 3 (3) F3: CF 3 COO (CH 2 ) 15 SiCl 3 (4) NTS: CH 3 (CH 2 ) 19 SiCl 3 In the above embodiment, a tempered glass was used for the base material.
The method of the present invention is applied to the modification of a glass surface such as a window glass or a mirror used in a house or a vehicle such as an automobile, a train, or an airplane, or a glass container or a lens, or other glass surface requiring water / oil repellency. Applicable to all glasses for quality. Further, the glass is not limited to colorless and transparent glass, and may be, for example, frosted glass whose surface is roughened, colored glass which is further colored, or glass fiber.
【００２７】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。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. .
【００２８】なお保護膜は必ずしも単分子膜である必要
はない。塗布された有機膜、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接触さ
せる必要がある。The protective film does not necessarily need to be a monomolecular film. A coated organic film, a silica coat film using a sol-gel method, or a transparent vapor deposition film may be used. However, when the surface is not hydrophilic, it is necessary to contact the fluorocarbon group-containing silane surfactant of the present invention after making the surface hydrophilic by a usual method such as corona irradiation or sputtering.
【００２９】[0029]
【発明の効果】本発明のガラスの製造方法を用いれば、
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。According to the method for producing 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 undergo an adsorption reaction on the surface of the glass or the glass having the protective film, and the fluorocarbon group is exposed on the surface, and the glass or the protective film and At the interface of the glass, a water- and oil-repellent film with a thickness of nanometer level can be formed covalently bonded to the glass or protective film, that is, integrated with the substrate, so that the glass can be protected without impairing its transparency and gloss. This has the effect of providing glass with high fouling and excellent durability that does not peel off practically.
【００３０】さらに、本発明のガラスの製造方法を用い
れば、表面をフッ化炭素の有機基で被うので、ガラス表
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。したがって、基材ガラスそのものよりもさらに強靭
性に優れたガラスを提供できる効果もある。Further, according to the method for producing glass of the present invention, since the surface is covered with the organic group of fluorocarbon, the coefficient of friction of the glass surface is lowered and the scratch resistance of the glass itself is improved. Therefore, there is an effect that a glass having higher toughness than the base glass itself can be provided.
【図１】 本発明の実施例１の末端にビニル基を有する
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。FIG. 1 is a conceptual cross-sectional view of a process in which the state of a glass surface at the time of preparing a chemisorption film having a vinyl group at a terminal in Example 1 of the present invention is enlarged to a molecular level.
【図２】 同、図１の状態から末端ビニル基を水酸基に
置換した工程断面概念図。FIG. 2 is a conceptual cross-sectional view of a process in which a terminal vinyl group is replaced with a hydroxyl group from the state of FIG.
【図３】 同、図１の状態から末端ビニル基をアミノ基
に置換した工程断面概念図。FIG. 3 is a conceptual cross-sectional view of a process in which a terminal vinyl group is replaced with an amino group from the state of FIG. 1;
【図４】 同、図２の分子膜の表面にフロロカーボン基
を有する分子膜を形成した工程断面概念図。FIG. 4 is a conceptual cross-sectional view of a process in which a molecular film having a fluorocarbon group is formed on the surface of the molecular film in FIG. 2;
【図５】 同、図３の分子膜の表面にフロロカーボン基
を有する分子膜を形成した工程断面概念図。FIG. 5 is a conceptual cross-sectional view of a process in which a molecular film having a fluorocarbon group is formed on the surface of the molecular film in FIG. 3;
【図６】 本発明の実施例２の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。FIG. 6 was measured on each coating to determine the surface energy of the various chemisorption films of Example 2 of the present invention;
The figure which plotted cos (theta) of the contact angle with respect to the droplet which has various surface tensions.
１ ガラス基体 ２ ビニル基 ３ａ，３ｂ、３ｃ 単分子吸着保護膜 ３ｄ，３ｅ 単分子内層膜 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 DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Vinyl group 3a, 3b, 3c Monomolecular adsorption protective film 3d, 3e Monomolecular inner layer film 4 Hydroxy group 5 Amino group 6 Monomolecular adsorption film containing fluorocarbon group 7,8 Monomolecular accumulation film
Claims (2)
リル基またはアルコキシシリル基を有するシラン系界面
活性剤を含む有機溶液を用い、ガラス表面または保護膜
の形成されたガラス表面と前記シラン系界面活性剤を反
応させて、前記ガラス表面または保護膜の形成されたガ
ラス表面に化学結合した前記界面活性剤の分子残基から
できた被膜を形成する防汚性ガラスの製造方法。1. An organic solution containing a silane-based surfactant having a —CF 3 group at one end and a chlorosilyl group or an alkoxysilyl group at the other end, and a glass surface or a glass surface on which a protective film is formed. A method for producing an antifouling glass, comprising reacting a silane-based surfactant to form a coating made of molecular residues of the surfactant chemically bonded to the glass surface or the glass surface on which the protective film is formed.
リル基またはアルコキシシリル基を有するシラン系界面
活性剤分子が下記一般式（化１）及び（化２）から選ば
れる少なくとも一つである請求項１に記載の防汚性ガラ
スの製造方法。 【化１】 【化２】 2. A silane-based surfactant molecule having a —CF 3 group at one end and a chlorosilyl or alkoxysilyl group at the other end, at least one selected from the following general formulas (1) and (2): The method for producing an antifouling glass according to claim 1, wherein Embedded image Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7217552A JP2577203B2 (en) | 1995-08-25 | 1995-08-25 | Method for producing antifouling glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7217552A JP2577203B2 (en) | 1995-08-25 | 1995-08-25 | Method for producing antifouling glass |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2258032A Division JP2545642B2 (en) | 1990-09-26 | 1990-09-26 | Glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08188448A true JPH08188448A (en) | 1996-07-23 |
| JP2577203B2 JP2577203B2 (en) | 1997-01-29 |
Family
ID=16706054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7217552A Expired - Lifetime JP2577203B2 (en) | 1995-08-25 | 1995-08-25 | Method for producing antifouling glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2577203B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0842908A1 (en) * | 1996-11-18 | 1998-05-20 | Nippon Sheet Glass Co., Ltd. | Water repellant glass plate and method for manufacturing the same |
| JPH10194784A (en) * | 1996-11-18 | 1998-07-28 | Nippon Sheet Glass Co Ltd | Water-repellent glass |
| US7148369B2 (en) * | 2000-01-20 | 2006-12-12 | Centre National De La Recherche Scientifique (Cnrs) | Organosilicon compounds, preparation method and uses thereof |
| JP2011026402A (en) * | 2009-07-23 | 2011-02-10 | Shin-Etsu Chemical Co Ltd | Water-repellent composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5097616A (en) * | 1973-12-28 | 1975-08-02 | ||
| JPS5294884A (en) * | 1976-02-06 | 1977-08-09 | Teijin Ltd | Water and oil repellent laminated product |
| JPS58167448A (en) * | 1982-03-30 | 1983-10-03 | Asahi Glass Co Ltd | Glass having low reflectance |
| JPS58172246A (en) * | 1982-04-02 | 1983-10-11 | Asahi Glass Co Ltd | Surface treating agent for glass |
| JPS5926944A (en) * | 1982-08-04 | 1984-02-13 | Asahi Glass Co Ltd | Glass of low reflectance |
| JPH01195181A (en) * | 1988-01-28 | 1989-08-07 | Hino Motors Ltd | Rear wheel steering device |
-
1995
- 1995-08-25 JP JP7217552A patent/JP2577203B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5097616A (en) * | 1973-12-28 | 1975-08-02 | ||
| JPS5294884A (en) * | 1976-02-06 | 1977-08-09 | Teijin Ltd | Water and oil repellent laminated product |
| JPS58167448A (en) * | 1982-03-30 | 1983-10-03 | Asahi Glass Co Ltd | Glass having low reflectance |
| JPS58172246A (en) * | 1982-04-02 | 1983-10-11 | Asahi Glass Co Ltd | Surface treating agent for glass |
| JPS5926944A (en) * | 1982-08-04 | 1984-02-13 | Asahi Glass Co Ltd | Glass of low reflectance |
| JPH01195181A (en) * | 1988-01-28 | 1989-08-07 | Hino Motors Ltd | Rear wheel steering device |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0842908A1 (en) * | 1996-11-18 | 1998-05-20 | Nippon Sheet Glass Co., Ltd. | Water repellant glass plate and method for manufacturing the same |
| JPH10194784A (en) * | 1996-11-18 | 1998-07-28 | Nippon Sheet Glass Co Ltd | Water-repellent glass |
| US6001485A (en) * | 1996-11-18 | 1999-12-14 | Nippon Sheet Glass Co., Ltd. | Water repellant glass plate and method for manufacturing the same |
| US7148369B2 (en) * | 2000-01-20 | 2006-12-12 | Centre National De La Recherche Scientifique (Cnrs) | Organosilicon compounds, preparation method and uses thereof |
| JP2011026402A (en) * | 2009-07-23 | 2011-02-10 | Shin-Etsu Chemical Co Ltd | Water-repellent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2577203B2 (en) | 1997-01-29 |
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