JPH0545532B2 - - Google Patents
Info
- Publication number
- JPH0545532B2 JPH0545532B2 JP59087116A JP8711684A JPH0545532B2 JP H0545532 B2 JPH0545532 B2 JP H0545532B2 JP 59087116 A JP59087116 A JP 59087116A JP 8711684 A JP8711684 A JP 8711684A JP H0545532 B2 JPH0545532 B2 JP H0545532B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- water
- repellent
- compound
- polymer
- 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
Classifications
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、撥水性の膜を硝子の表面に形成して
撥水処理硝子を製造する方法に関する。本発明に
従い製造される撥水処理硝子は、建築物の窓硝
子、自動車、車輛、航空機あるいは船舶等の風防
硝子、眼鏡やカメラなどに使われる光学用硝子、
家庭用硝子器具（例えば、硝子製のコツプ、食
器、水槽、花瓶、哺乳瓶など）、およびその他撥
水性を必要とする硝子製品に大変有効に適用され
うる。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing water-repellent glass by forming a water-repellent film on the surface of the glass. The water-repellent glass manufactured according to the present invention includes window glass for buildings, windshield glass for automobiles, vehicles, aircraft, ships, etc., optical glass used for eyeglasses and cameras, etc.
It can be very effectively applied to household glassware (eg, glass cups, tableware, aquariums, vases, baby bottles, etc.) and other glass products that require water repellency.
（従来技術）
従来より、硝子の撥水処理剤としてシロキサン
結合を有する有機ケイ素化合物が多く使用されて
おり、そして硝子の表面にシロキサン重合物膜を
形成して撥水化させる方法としては、例えばア
ルキルハロシラン類の単量体ガスを硝子表面に作
用させしかる後加水分解する方法や、ポリジメ
チルシロキサン類の溶液を硝子表面に塗布ししか
る後加熱乾燥してシリコーン膜を硝子表面に形成
させる方法などが開発、利用されてきている。し
かしながら、このような従来の製法により得られ
た撥水処理硝子は、一般に撥水処理膜の硝子表面
との接着力が弱く、例えば撥水処理硝子表面に粘
着テープを貼り付けて引き剥すピーリングテスト
において撥水処理膜が容易に剥離するなど、撥水
処理の耐久性（耐ピーリング性等）に劣つてい
た。その上、前記の方法に従う製造過程におい
ては、有害なハロゲン化水素ガスが発生し、また
前記の方法では、加熱乾燥によつて硝子の強度
低下を招き、かつこれに従つて製造した硝子は撥
水処理膜より溶媒を除去するのに長時間必要とす
るなどの問題点を有していた。(Prior Art) Conventionally, organosilicon compounds having siloxane bonds have been widely used as water-repellent treatment agents for glass, and methods for forming a siloxane polymer film on the surface of glass to make it water-repellent include, for example. A method in which a monomer gas of alkylhalosilanes is applied to the glass surface and then hydrolyzed, or a method in which a solution of polydimethylsiloxane is applied to the glass surface and then heated and dried to form a silicone film on the glass surface. have been developed and used. However, water-repellent glass obtained by such conventional manufacturing methods generally has weak adhesion to the glass surface of the water-repellent film, and for example, a peeling test in which an adhesive tape is attached to the surface of the water-repellent glass and then peeled off. The durability of the water repellent treatment (peeling resistance, etc.) was poor, such as the water repellent treatment film peeling off easily. Moreover, in the manufacturing process according to the above method, harmful hydrogen halide gas is generated, and in the above method, the strength of the glass decreases due to heat drying, and the glass manufactured according to this method is repellent. This method has problems such as the need for a long time to remove the solvent from the water treatment membrane.
（発明の目的）
本発明の目的は、十分な撥水性を有するだけで
なく、耐久性が格段に優れ、しかも製法に基づく
前記の如き悪影響を生じない撥水処理硝子の製造
方法を提供することにある。(Objective of the Invention) An object of the present invention is to provide a method for producing water-repellent glass that not only has sufficient water repellency but also has outstanding durability and does not cause the above-mentioned adverse effects due to the manufacturing method. It is in.
（発明の構成）
本発明による撥水処理硝子の製造方法は、撥水
性処理膜を硝子の表面に形成して撥水処理硝子を
製造する方法において、
１ プラズマ重合法に従い接着成分の重合物およ
び撥水成分の重合物を硝子表面に被覆して、撥
水性処理膜を形成したこと、
２ (a) 接着成分の重合物のための原料化合物と
して、テトラメトキシシランおよびトリメト
キシメチルシランの群から選択されたシロキ
サン結合を有する有機ケイ素化合物を用い、
かつ、
(b) 撥水成分の重合物のための原料化合物と
して、
テトラエトキシシランおよびテトラプロ
ポキシシランの群から選択された(a)の有機
ケイ素化合物より炭素の組成割合が大きい
有機ケイ素化合物、
トリメチルメトキシシランおよびジメチ
ルジメトキシシランの群から選択された(a)
の有機ケイ素化合物より酸素の組成割合が
小さい有機ケイ素化合物、または
六フツ化プロピレンおよびテトラフルオ
ロエチレンの群から選択されたフツ素化合
物を用いたこと、並びに
３ 撥水性処理膜は、最初に前記化合物(a)を単独
で重合させるかまたは前記化合物(a)および前記
化合物(b)を化合物(a)が化合物(b)よりも多い組成
割合にて重合させ、そしてその後前記化合物(b)
を単独で重合させるかまたは前記化合物(a)およ
び前記化合物(b)を化合物(b)が化合物(a)よりも多
い組成割合にて重合させることにより、形成し
たことを特徴とするものである。(Structure of the Invention) A method for producing water-repellent glass according to the present invention is a method for producing water-repellent glass by forming a water-repellent film on the surface of the glass, which comprises: 1. A polymer of an adhesive component according to a plasma polymerization method; A water-repellent treated film was formed by coating the glass surface with a polymer of a water-repellent component; 2. (a) A raw material compound for the polymer of an adhesive component was selected from the group of tetramethoxysilane and trimethoxymethylsilane Using an organosilicon compound having a selected siloxane bond,
and (b) as a raw material compound for the polymerized water-repellent component, an organosilicon compound having a higher carbon composition ratio than the organosilicon compound of (a) selected from the group of tetraethoxysilane and tetrapropoxysilane, trimethyl. (a) selected from the group of methoxysilane and dimethyldimethoxysilane
or a fluorine compound selected from the group of propylene hexafluoride and tetrafluoroethylene; (a) is polymerized alone or said compound (a) and said compound (b) are polymerized in a composition ratio in which compound (a) is greater than compound (b), and then said compound (b) is polymerized;
It is characterized by being formed by polymerizing the compound (a) alone or the compound (b) at a composition ratio where the compound (b) is larger than the compound (a). .
すなわち、本発明は、撥水性処理膜（有機ケイ
素化合物の重合物をベースとする。）をプラズマ
重合法に従い硝子の表面に形成するとともに、そ
の重合プロセスにおいて、前記処理膜のうち硝子
に当接する面寄りの部分には、硝子との接着性が
良好な重合物（接着部分）が主に配され、かつ前
記処理膜のうち硝子に当接する面と反対側の面寄
りの部分には、撥水性に富む重合物（撥水成分）
が主に配されるようにすることにより、製造され
る撥水処理硝子について、良好な撥水性を確保し
た上で、硝子表面との接着力の向上を図つたもの
である。 That is, the present invention forms a water-repellent treated film (based on a polymer of an organosilicon compound) on the surface of glass according to a plasma polymerization method, and in the polymerization process, a water-repellent treated film (based on a polymer of an organic silicon compound) is formed on the surface of glass. A polymer material (adhesive part) that has good adhesion to glass is mainly arranged on the side of the film, and a repellent material is placed on the side of the treated film opposite to the side that comes into contact with the glass. Polymer rich in water (water repellent component)
By disposing mainly the water-repellent glass, it is possible to ensure good water repellency for the manufactured water-repellent glass and to improve the adhesive force with the glass surface.
本発明の製造方法のうちより好ましいものは、
次の２様態である。 More preferred among the manufacturing methods of the present invention are:
There are the following two modes.
１ 上記化合物(a)の単独重合により接着成分の重
合物のみから成る層が硝子に当接する面寄りの
部分に形成されるように、かつ、上記化合物(b)
の単独重合により撥水成分の重合物のみから成
る層が硝子に当接する面の反対側の面寄りの部
分に形成されるようにして、撥水性処理膜を硝
子表面に作る方法。1. By homopolymerizing the above compound (a), a layer consisting only of the polymer of the adhesive component is formed on the part near the surface that comes into contact with the glass, and the above compound (b)
A method of forming a water-repellent treated film on the glass surface by homopolymerizing the water-repellent component so that a layer consisting only of a polymer of the water-repellent component is formed on the surface opposite to the surface in contact with the glass.
２ 上記化合物(a)および上記化合物(b)の重合の
際、硝子に当接する面より硝子に当接する面の
反対側の面にかけて、化合物(a)の組成割合を減
らす一方で化合物(b)の組成割合を増やすことに
より、接着成分の重合物の組成割合が連続的に
減少しかつ撥水成分の重合物の組成割合が連続
的に増大するようにして、撥水性処理膜を硝子
表面に形成する方法。2. During polymerization of the above compound (a) and the above compound (b), the composition ratio of compound (a) is decreased from the surface that contacts the glass to the surface opposite to the surface that contacts the glass, while the composition ratio of compound (b) is reduced. By increasing the composition ratio of the water-repellent film on the glass surface, the composition ratio of the adhesive component polymer continuously decreases and the composition ratio of the water-repellent component polymer continuously increases. How to form.
さらに説明するに、本発明により製造される撥
水処理硝子は、例えば第１図に示すように、硝子
の表面１に接着成分としての重合物を接着させそ
の上に撥水成分としての重合物を被覆して、撥水
性処理膜２ａの硝子側部分に接着成分の層３を形
成し、かつその外部側部分に撥水成分の層４を形
成したものを挙げることができる。接着成分とし
てシロキサン結合を有する有機ケイ素化合物（テ
トラメトキシシラン（Si（OCH3）4）、トリメトキ
シメチルシラン（CH3Si（OCH3）3）の重合物を用
い、一方撥水成分として、該有機ケイ素化合物よ
り炭素の組成割合が大きい有機ケイ素化合物（接
着成分の化合物がテトラメトキシシランであると
き、テトラエトキシシラン（Si（OC2H5）4）、テト
ラプロポキシシラン（Si（OC3H7）4）の重合物、
若しくは上記有機ケイ素化合物より酸素の組成割
合が小さい有機ケイ素化合物（接着成分の化合物
がテトラメトキシシランであるとき、トリメチル
トキシシラン（（CH3）3SiOCH3）、ジメチルジメ
トキシシラン（（CH3）2Si（OCH3）2））の重合物、
若しくはフツ素化合物（六フツ化プロピレン
（CF2＝CF−CF3）、テトラフルオロエチレン
（CF2＝CF2）の重合物を適用する。上記の態様の
ように、接着部分の層３の硝子に当接する面およ
びその近傍部分に形成し、かつ、撥水成分の層４
を該当接面と反対側の面およびその近傍部分に形
成すると、撥水性処理膜２ａは、蒸留水との接触
角が90°を越え、良好な撥水性を有するとともに、
ピークリングテストにおいて剥離せず、硝子表面
との間に満足に高い接着力が得られる。 To further explain, the water-repellent glass manufactured according to the present invention is produced by adhering a polymer as an adhesive component to the surface 1 of the glass, and then applying a polymer as a water-repellent component thereon, as shown in FIG. 1, for example. For example, a layer 3 of an adhesive component is formed on the glass side portion of the water-repellent treated film 2a, and a layer 4 of a water-repellent component is formed on the outside portion thereof. Polymers of organosilicon compounds having siloxane bonds (tetramethoxysilane (Si(OCH 3 ) 4 ) and trimethoxymethylsilane (CH 3 Si(OCH 3 ) 3 ) are used as adhesive components, while as water-repellent components, Organosilicon compounds with a higher proportion of carbon than organosilicon compounds (when the adhesive component compound is tetramethoxysilane, tetraethoxysilane (Si(OC 2 H 5 ) 4 ), tetrapropoxysilane (Si(OC 3 H 7 ) ) 4 ) Polymer of
Or an organosilicon compound with a lower oxygen composition ratio than the above organosilicon compound (when the adhesive component compound is tetramethoxysilane, trimethyltoxysilane ((CH 3 ) 3 SiOCH 3 ), dimethyldimethoxysilane ((CH 3 ) 2 Polymer of Si( OCH3 ) 2 )),
Alternatively, a fluorine compound (polymer of propylene hexafluoride (CF 2 = CF-CF 3 ), tetrafluoroethylene (CF 2 = CF 2 ) is applied. As in the above embodiment, the glass of layer 3 of the adhesive part A layer 4 of a water-repellent component is formed on the surface that comes into contact with the surface and its vicinity.
is formed on the surface opposite to the contact surface and its vicinity, the water-repellent treated film 2a has a contact angle with distilled water of more than 90°, and has good water repellency.
It does not peel off in the peak ring test, and satisfactorily high adhesive strength is obtained between it and the glass surface.
これに対し、撥水成分の層４のみを硝子表面に
形成した場合、並びに接着成分と撥水成分との混
合物よりなるほぼ均質な層を硝子表面に形成した
場合、形成された処理膜は、ピーリングテストに
おいて剥離し、従来と同様硝子表面との接着力が
弱く、顕著な改良がみられない。さらに、接着成
分の層３のみを硝子表面に形成した場合、形成さ
れた処理膜は、蒸留水との接触角が90°未満であ
り、撥水性処理硝子として必要な機能を果たし得
るものでない。 On the other hand, when only the layer 4 of the water-repellent component is formed on the glass surface, or when a substantially homogeneous layer consisting of a mixture of the adhesive component and the water-repellent component is formed on the glass surface, the formed treated film is It peeled off in the peeling test, and like the conventional product, the adhesion to the glass surface was weak, and no significant improvement was seen. Furthermore, when only the layer 3 of the adhesive component is formed on the glass surface, the formed treated film has a contact angle with distilled water of less than 90°, and cannot fulfill the necessary function as water-repellent treated glass.
また、第１図に示した上記態様とは異なる二三
の態様として、本発明により製造される撥水処理
硝子は、第２図に示すように、撥水性処理膜２ｂ
を、硝子に当接する面より硝子に当接する面の反
対側の面にかけて、接着成分の重合物の組成割合
が連続的に減少しかつ撥水成分の重合物の組成割
合が連続的に増大するように形成したものでもよ
く、さらに第３図に示すように、撥水性処理膜２
ｃの硝子に当接する面およびその近傍部分には接
着成分の層３をかつ硝子に当接する面と反対側の
面およびその近傍部分には撥水成分の層４を夫々
形成し、さらにその中央部分の層５では、接着成
分および撥水成分の重合物が第２図の場合と同様
に化学組成を変化させて存在してなるものでもよ
い。また、本発明の撥水処理硝子を製造するに当
つては、プラズマ重合法により、減圧雰囲気下で
接着成分および撥水成分の原料化合物を、順次ま
たは混合割合を連続的に変化させて、硝子表面に
接着被覆させかつ重合反応を起こさせて、接着成
分および撥水成分の重合物を層状にまたは両者の
組成割合を連続的に変化させて成る撥水性処理膜
を形成してもよい。プラズマ重合法によれば、製
造過程において有害ガスの発生が無くかつ溶媒除
去に関する問題も生じず、さらに硝子の強度低下
等の不具合な現象を惹起しない。 In addition, as a few aspects different from the above-mentioned aspect shown in FIG. 1, the water-repellent treated glass manufactured by the present invention has a water-repellent treated film 2b
The composition ratio of the adhesive component polymer continuously decreases and the composition ratio of the water-repellent component polymer continuously increases from the surface that contacts the glass to the surface opposite to the surface that contacts the glass. Furthermore, as shown in FIG.
A layer 3 of an adhesive component is formed on the surface of c that contacts the glass and its vicinity, and a layer 4 of a water-repellent component is formed on the surface opposite to the surface that contacts the glass and its vicinity, and furthermore, a layer 4 of a water-repellent component is formed on the surface opposite to the surface that contacts the glass and its vicinity. In the layer 5 of the portion, a polymer of an adhesive component and a water-repellent component may be present with different chemical compositions as in the case of FIG. 2. In addition, in producing the water-repellent treated glass of the present invention, the raw material compounds of the adhesive component and the water-repellent component are sequentially or continuously changed in the mixing ratio under a reduced pressure atmosphere using a plasma polymerization method. A water-repellent treated film may be formed by coating the surface with an adhesive and causing a polymerization reaction to form a layer of a polymer of an adhesive component and a water-repellent component, or by continuously changing the composition ratio of both components. According to the plasma polymerization method, no harmful gases are generated during the manufacturing process, there are no problems related to solvent removal, and there is no problem such as a decrease in the strength of glass.
（実施例） 以下、本発明の実施例を説明する。(Example) Examples of the present invention will be described below.
実施例 １
スライド硝子をベルジヤー型反応器内に収め、
最初にテトラメトキシシランをしかる後テトラエ
トキシシランを供給しながら、プラズマ重合（圧
力0.1Torr，入力100W，周波数13.56MHz）を行
なつて、硝子表面にテトラメトキシシランの重合
物（接着成分）を接着させその上にテトラエトキ
シシランの重合物（撥水成分）を被覆してなる実
施例１の撥水処理硝子（第１図）を製造した。該
硝子の撥水特性、例えば硝子表面のぬれ性を知る
べく、その目安となる蒸留水との接触角を表面接
触角測定装置を用いて調べたところ、接触角が
90°を越えぬれない硝子であることが認められた。
未処理のスライド硝子の場合には接触角が10°で
あつた。また、当該撥水処理硝子は、透明で、水
中に浸漬ししかる後水上に引上げて目視してみた
ところ、ただちに硝子の向こう側の視界が明瞭に
現われた。未処理硝子の場合には、視界が暫の間
滲みぼやけていた。さらに、実施例１の硝子の場
合には、硝子表面の水を容易に紙で拭取り除去す
ることができた。Example 1 A glass slide was placed in a Bergier type reactor,
First, tetramethoxysilane is applied, and then plasma polymerization (pressure 0.1 Torr, input 100 W, frequency 13.56 MHz) is performed while tetraethoxysilane is supplied to bond the tetramethoxysilane polymer (adhesive component) to the glass surface. The water-repellent glass of Example 1 (FIG. 1) was prepared by coating the glass with a polymer of tetraethoxysilane (water-repellent component). In order to know the water-repellent properties of the glass, such as the wettability of the glass surface, we investigated the contact angle with distilled water, which is a guideline, using a surface contact angle measuring device, and found that the contact angle was
It was confirmed that the glass cannot be wetted at angles exceeding 90°.
In the case of untreated glass slides, the contact angle was 10°. Furthermore, the water-repellent glass was transparent, and when it was immersed in water and then lifted out of the water for visual inspection, the view on the other side of the glass immediately became clear. In the case of untreated glass, the vision was blurred for a while. Furthermore, in the case of the glass of Example 1, water on the surface of the glass could be easily wiped off with paper.
また、撥水処理の耐久性を知るべく、その目安
となるピーリングテスト（粘着テープを硝子表面
に貼付けしかる後テープを引剥す。）を行なつて
みたところ、実施例１の場合、硝子表面の撥水性
処理膜は剥離しなかつた。 In addition, in order to find out the durability of the water repellent treatment, we conducted a peeling test (applying adhesive tape to the glass surface and then peeling off the tape), and found that in the case of Example 1, the glass surface The water-repellent treated film did not peel off.
実施例 ２
テトラメトキシシラン及びトリメチルメトキシ
シランを、両者の組成を第４図に示すように重合
時間と共に連続的に変化させて供給しながら、実
施例１と同様な条件でプラズマ重合を行なつて、
撥水性処理膜を、硝子に当接する面より硝子に当
接する面の反対側の面にかけて、テトラメトキシ
シランの重合物の組成割合が連続的に減少しかつ
トリメチルメトキシシランの重合物の組成割合が
連続的に増大するように形成した実施例２の撥水
処理硝子（第２図）を製造した。該硝子の撥水性
を実施例１と同様に調べたところ、表面の接触角
は90°を越えていた。また、ピーリングテストを
実施例１と同様に行なつたところ、表面の膜は剥
離しなかつた。Example 2 Plasma polymerization was carried out under the same conditions as in Example 1, while supplying tetramethoxysilane and trimethylmethoxysilane while changing the composition of both continuously with the polymerization time as shown in Figure 4. ,
The composition ratio of the polymer of tetramethoxysilane decreases continuously from the surface that contacts the glass to the surface opposite to the surface that contacts the glass, and the composition ratio of the polymer of trimethylmethoxysilane decreases. The water-repellent glass of Example 2 (FIG. 2), which was formed so as to increase continuously, was manufactured. When the water repellency of the glass was examined in the same manner as in Example 1, the contact angle on the surface was over 90°. Further, when a peeling test was conducted in the same manner as in Example 1, the surface film did not peel off.
実施例 ３
トリメトキシメチルシラン及び六フツ化プロピ
レンを、両者の組成を第５図に示すように連続的
に変化させて供給しながら、プラズマ重合（他の
条件は実施例１と同一）を行なつて、撥水性処理
膜を、硝子に当接する面より硝子に当接する面の
反対側の面にかけて、トリメトキシメチルシラン
の重合物の組成割合が連続的に減少しかつ六フツ
化プロピレンの重合物の組成割合が連続的に増大
するように形成した実施例３の撥水処理硝子を製
造した。実施例１と同様に測定したところ、この
処理硝子の表面の接触角は95°であつて、ぬれな
い硝子であることが確かめられた。また、実施例
１と同様のピーリングテストにおいて、硝子表面
の撥水性処理膜は剥離しなかつた。Example 3 Plasma polymerization was carried out (other conditions were the same as in Example 1) while supplying trimethoxymethylsilane and propylene hexafluoride while changing the composition of both continuously as shown in Figure 5. As a result, the composition ratio of the trimethoxymethylsilane polymer continuously decreases from the surface that contacts the glass to the surface opposite to the surface that contacts the glass, and the polymerization of propylene hexafluoride decreases. The water-repellent glass of Example 3 was manufactured in such a manner that the composition ratio of the glass was continuously increased. When measured in the same manner as in Example 1, the contact angle on the surface of this treated glass was 95°, and it was confirmed that the glass did not get wet. Furthermore, in the same peeling test as in Example 1, the water-repellent treated film on the glass surface did not peel off.
実施例 ４
トリメトキシメチルシラン及びテトラフルオロ
エチレンを原料として、、両者の組成を第６図に
示すように変化させてプラズマ重合（他の条件は
実施例１と同様）を行なつて、撥水性処理膜の硝
子に当接する面およびその近傍部分にトリメトキ
シメチルシランの重合物の層をかつ硝子に当接す
る面と反対側の面およびその近傍部分にテトラフ
ルオロエチレンの重合物の層を夫々形成し、さら
にその中央部分ではトリメトキシシラン重合物及
びテトラフルオロエチレン重合物の組成割合が実
施例２と同様に連続的に変化してなる実施例４の
撥水処理硝子（第３図）を製造した。この硝子の
表面の接触角は100°であつた。ピーリングテスト
において撥水性処理膜は剥離しなかつた。なお、
測定条件は実施例１と同様である。Example 4 Using trimethoxymethylsilane and tetrafluoroethylene as raw materials, plasma polymerization was performed with the compositions of both changed as shown in Figure 6 (other conditions were the same as in Example 1) to obtain water repellency. A layer of trimethoxymethylsilane polymer is formed on the surface of the treated membrane that comes into contact with the glass and the vicinity thereof, and a layer of tetrafluoroethylene polymer is formed on the surface opposite to the surface that comes into contact with the glass and the vicinity thereof. Furthermore, in the central part, the water-repellent glass of Example 4 (Fig. 3) was produced, in which the composition ratio of the trimethoxysilane polymer and the tetrafluoroethylene polymer was continuously changed as in Example 2. did. The contact angle on the surface of this glass was 100°. In the peeling test, the water-repellent treated film did not peel off. In addition,
The measurement conditions are the same as in Example 1.
比較のため、テトラフルオロエチレンの重合物
の層を硝子の表面に単独被覆してなる撥水処理硝
子Ａ、トリメトキシメチルシランの重合物の層を
硝子の表面に単独被覆してなる撥水処理硝子Ｂ、
およびこれら両重合物の混合物をほぼ均質に硝子
の表面に被覆してなる撥水処理硝子Ｃをそれぞれ
製造した。 For comparison, water-repellent glass A is obtained by coating the surface of the glass with a layer of a polymer of tetrafluoroethylene, and water-repellent treatment is obtained by coating the surface of the glass with a layer of a polymer of trimethoxymethylsilane. Glass B,
A water-repellent glass C was prepared by coating the surface of the glass almost homogeneously with a mixture of these two polymers.
撥水処理硝子ＡおよびＣについては、ピーリン
グテストにおいて、処理膜が剥離してしまつた。
また、撥水処理硝子Ｂについては、蒸留水との接
触角が90未満であり、撥水処理硝子としての効果
が認められなかつた。 Regarding the water-repellent treated glasses A and C, the treated film peeled off in the peeling test.
Further, regarding water-repellent glass B, the contact angle with distilled water was less than 90, and no effect as a water-repellent glass was recognized.
（発明の効果）
したがつて、本発明の製造方法によれば、以下
のような特性を有する撥水処理硝子が得られる。
即ち、該硝子は、十分な撥水性を有し、表面が汚
れ難く、洗浄しても乾燥し易く、また乾燥後も清
潔である。また、水をかけても、ただちに硝子の
向こう側の視界が明瞭に現われる。それだけでな
く、本発明の製法に従う硝子の撥水性処理膜は硝
子表面との接着力が強く、撥水処理の耐久性が著
しく向上している。その上、本発明による製法
は、撥水処理硝子をプラズマ重合法に従い製造す
るものであるので、この製造過程において従来例
における各種の悪影響（有害ガスの発生等）を生
じない。(Effects of the Invention) Therefore, according to the manufacturing method of the present invention, water-repellent glass having the following characteristics can be obtained.
That is, the glass has sufficient water repellency, the surface is hard to stain, is easy to dry even after washing, and remains clean even after drying. Also, even if you sprinkle water on it, the view on the other side of the glass will immediately appear clearly. In addition, the water-repellent treatment film for glass according to the manufacturing method of the present invention has strong adhesion to the glass surface, and the durability of the water-repellent treatment is significantly improved. Moreover, since the manufacturing method according to the present invention produces water-repellent glass according to the plasma polymerization method, various adverse effects (such as the generation of harmful gases) that occur in the prior art do not occur during this manufacturing process.
第１図ないし第３図は本発明の方法に従う製造
される各種の撥水処理硝子の主要部を示す断面
図、第４図ないし第６図は本発明の実施例２ない
し実施例４の方法に従い撥水処理硝子を製造する
ときのプラズマ重合条件を示すグラフである。
図中、１……硝子表面、２ａ，２ｂ，２ｃ……
撥水性処理膜、３……接着成分の層、４……撥水
成分の層。
1 to 3 are cross-sectional views showing the main parts of various types of water-repellent glass manufactured according to the method of the present invention, and FIGS. 4 to 6 are methods according to embodiments 2 to 4 of the present invention. 3 is a graph showing plasma polymerization conditions when producing water-repellent glass according to the method. In the figure, 1...Glass surface, 2a, 2b, 2c...
Water-repellent treated film, 3...Adhesive component layer, 4...Water-repellent component layer.
Claims (1)
理硝子を製造する方法において、 １ プラズマ重合法に従い接着成分の重合物およ
び撥水成分の重合物を硝子表面に被覆して、撥
水性処理膜を形成したこと、 ２ (a) 接着成分の重合物のための原料化合物と
して、テトラメトキシシランおよびトリメト
キシメチルシランの群から選択されたシロキ
サン結合を有する有機ケイ素化合物を用い、
かつ、 (b) 撥水成分の重合物のための原料化合物とし
て、 テトラエトキシシランおよびテトラプロ
ポキシシランの群から選択された(a)の有機
ケイ素化合物より炭素の組成割合が大きい
有機ケイ素化合物、 トリメチルメトキシシランおよびジメチ
ルジメトキシシランの群から選択された(a)
の有機ケイ素化合物より酸素の組成割合が
小さい有機ケイ素化合物、または 六フツ化プロピレンおよびテトラフルオ
ロエチレンの群から選択されたフツ素化合
物を用いたこと、並びに ３ 撥水性処理膜は、最初に前記化合物(a)を単独
で重合させるかまたは前記化合物(a)および前記
化合物(b)を化合物(a)が化合物(b)よりも多い組成
割合にて重合させ、そしてその後前記化合物(b)
を単独で重合させるかまたは前記化合物(a)およ
び前記化合物(b)を化合物(b)が化合物(a)よりも多
い組成割合にて重合させることにより、形成し
たことを特徴とする撥水処理硝子の製造方法。 ２ 撥水性処理膜は、接着成分の重合物のみから
成る層を硝子に当接する面寄りの部分に形成し、
かつ、撥水成分の重合物のみから成る層を硝子に
当接する面の反対側の面寄りの部分に形成してな
ることを特徴とする特許請求の範囲第１項記載の
撥水処理硝子の製造方法。 ３ 撥水性処理膜は、硝子に当接する面より硝子
に当接する面の反対側の面にかけて、接着成分の
重合物の組成割合が連続的に減少しかつ撥水成分
の重合物の組成割合が連続的に増大するように形
成してなることを特徴とする特許請求の範囲第１
項記載の撥水処理硝子の製造方法。[Scope of Claims] 1. A method for producing water-repellent glass by forming a water-repellent film on the surface of glass, comprising: 1 applying a polymer of an adhesive component and a polymer of a water-repellent component to the surface of glass according to a plasma polymerization method. 2. (a) An organosilicon compound having a siloxane bond selected from the group of tetramethoxysilane and trimethoxymethylsilane as a raw material compound for the polymerized adhesive component. using
and (b) as a raw material compound for the polymerized water-repellent component, an organosilicon compound having a higher carbon composition ratio than the organosilicon compound of (a) selected from the group of tetraethoxysilane and tetrapropoxysilane, trimethyl. (a) selected from the group of methoxysilane and dimethyldimethoxysilane
or a fluorine compound selected from the group of propylene hexafluoride and tetrafluoroethylene; (a) is polymerized alone or said compound (a) and said compound (b) are polymerized in a composition ratio in which compound (a) is greater than compound (b), and then said compound (b) is polymerized;
or by polymerizing the compound (a) and the compound (b) at a composition ratio in which the compound (b) is larger than the compound (a). Glass manufacturing method. 2. The water-repellent treatment film is made by forming a layer consisting only of a polymeric adhesive component on the surface that comes into contact with the glass.
The water-repellent glass according to claim 1, wherein a layer consisting only of a polymer of a water-repellent component is formed on a portion of the glass that is opposite to the surface that comes into contact with the glass. Production method. 3. In the water-repellent treated film, the composition ratio of the adhesive component polymer continuously decreases from the surface that contacts the glass to the surface opposite to the surface that contacts the glass, and the composition ratio of the water-repellent component polymer continuously decreases. Claim 1 characterized in that it is formed so as to increase continuously.
A method for producing water-repellent glass as described in .
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8711684A JPS60231442A (en) | 1984-04-28 | 1984-04-28 | Manufacturing method for water-repellent glass |
| US06/728,698 US4649071A (en) | 1984-04-28 | 1985-04-29 | Composite material and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8711684A JPS60231442A (en) | 1984-04-28 | 1984-04-28 | Manufacturing method for water-repellent glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60231442A JPS60231442A (en) | 1985-11-18 |
| JPH0545532B2 true JPH0545532B2 (en) | 1993-07-09 |
Family
ID=13905980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8711684A Granted JPS60231442A (en) | 1984-04-28 | 1984-04-28 | Manufacturing method for water-repellent glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60231442A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3210045B2 (en) * | 1991-11-20 | 2001-09-17 | 旭硝子株式会社 | Surface treated substrate |
| US5413865A (en) * | 1992-01-31 | 1995-05-09 | Central Glass Company, Limited | Water-repellent metal oxide film and method of forming same on glass substrate |
| JP3498881B2 (en) * | 1996-05-27 | 2004-02-23 | セントラル硝子株式会社 | Manufacturing method of water-repellent glass |
| US6051321A (en) * | 1997-10-24 | 2000-04-18 | Quester Technology, Inc. | Low dielectric constant materials and method |
| US6140456A (en) * | 1997-10-24 | 2000-10-31 | Quester Techology, Inc. | Chemicals and processes for making fluorinated poly(para-xylylenes) |
| US6086679A (en) * | 1997-10-24 | 2000-07-11 | Quester Technology, Inc. | Deposition systems and processes for transport polymerization and chemical vapor deposition |
| US6020458A (en) | 1997-10-24 | 2000-02-01 | Quester Technology, Inc. | Precursors for making low dielectric constant materials with improved thermal stability |
| KR20010071175A (en) | 1998-05-01 | 2001-07-28 | 세슈 비. 데스 | Oxide/organic polymer multilayer thin films deposited by chemical vapor deposition |
| US6495208B1 (en) | 1999-09-09 | 2002-12-17 | Virginia Tech Intellectual Properties, Inc. | Near-room temperature CVD synthesis of organic polymer/oxide dielectric nanocomposites |
| JP4517761B2 (en) * | 2004-07-30 | 2010-08-04 | パナソニック株式会社 | Heat-resistant and antifouling substrate and cooking device using the same |
| JP5597193B2 (en) * | 2009-03-31 | 2014-10-01 | シチズンファインテックミヨタ株式会社 | Sensor with cover and method for manufacturing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5529944B2 (en) * | 1973-05-19 | 1980-08-07 | ||
| JPS5529026B2 (en) * | 1973-05-19 | 1980-07-31 | ||
| JPS5356177A (en) * | 1976-11-02 | 1978-05-22 | Asahi Glass Co Ltd | Forming method for anti-foggig film on transparent body |
-
1984
- 1984-04-28 JP JP8711684A patent/JPS60231442A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60231442A (en) | 1985-11-18 |
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