JPS58172245A - Surface treating agent for glass - Google Patents

Surface treating agent for glass

Info

Publication number
JPS58172245A
JPS58172245A JP5372182A JP5372182A JPS58172245A JP S58172245 A JPS58172245 A JP S58172245A JP 5372182 A JP5372182 A JP 5372182A JP 5372182 A JP5372182 A JP 5372182A JP S58172245 A JPS58172245 A JP S58172245A
Authority
JP
Japan
Prior art keywords
glass
group
compd
water
formula
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.)
Pending
Application number
JP5372182A
Other languages
Japanese (ja)
Inventor
Yoshio Oda
小田　吉男
Hitoshi Matsuo
仁 松尾
Nobuyuki Yamagishi
展幸 山岸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP5372182A priority Critical patent/JPS58172245A/en
Publication of JPS58172245A publication Critical patent/JPS58172245A/en
Pending legal-status Critical Current

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

Abstract

PURPOSE:To provide a surface treating agent which can provide water repellency, oil repellency, resistance to contamination, etc. to a glass surface over a long period of time by consisting the agent of a silane compd. contg. polyfluoroalkyl group (Rf groups) or partially hydrolyzed condensate thereof and a silane compd. CONSTITUTION:A silane compd. contg. Rf group expressed by the formula I [e.g.; C9F19CONH(CH2)3Si(OC2H5)3] and a silane compd. expressed by the formula II[e.g.; Si(OC2H5)4] are mixed in the presence of water and the mixture is allowed to react, whereby the intended surface treating agent for glass is obtained. The mixing ratio of the compd. of the formula II with respect to the compd. of the formula I is 10-90wt%, more preferably 30-70wt%. The atm. of the water to be added is 10-100mol%, more particularly 100-500mol% based on the amt. of the compd. of the formula I . This treating agent is prepd. in optional forms such as emulsion, solvent soln., aerosol or the like according to conventional methods.

Description

【発明の詳細な説明】 本発明は、ガラス大面に撥水性、゛撥油性、耐汚染性、
低反射性などを付与する処理剤に関し、更に詳しく言え
ば、ポリフルオロアルキル基含有シラン化合物又は、該
化合物の部分加水分解線金物とアルコキシあるいはハロ
ゲノ等シラン化合物とからなる新規なガラスの表面処理
剤に関するものである。Detailed Description of the Invention The present invention provides water repellency, oil repellency, stain resistance, and
Regarding the treatment agent that imparts low reflectivity, more specifically, a novel surface treatment agent for glass comprising a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed wire metal compound of the compound and an alkoxy or halogeno silane compound. It is related to.

ガラス板、境、ガラス容器、ガラス器具、メガネレンズ
などガラス製品の表面は大気中の湿度及び温度の影響に
よシ水分が凝縮したシ、水によって漏らされた場合、こ
れら水分中にガラス成分が溶出し、アルカリ性となるた
め表面が容易に浸蝕されて、いわゆる焼けを生ずること
は周知でちる。又、大気中に浮遊する微細な塵や油滴粒
子が付着してガラス表面を汚染したり、特に自動車、航
空機、鉄道車輛のウィンド−において雨水などの水滴が
付着してガラスの透明性あるいは透視性を阻害する。こ
のため、従来から、ガラス表面を撥水性にするため、例
えｔｆシリコン系ワックス、ポリシロキサンからガるシ
リコン油や界面活性剤などを面接塗布する表面処理剤が
提案されている。然るに、これらは塗布に伴う前処理を
必要とされるものが多く、特に塗布ムラ、長期の耐久性
、撥油性及び耐汚染性については満足し得る結果は得ら
れていない。The surfaces of glass products such as glass plates, borders, glass containers, glassware, and eyeglass lenses may condense moisture due to the influence of atmospheric humidity and temperature, and if water leaks, glass components may be contained in this moisture. It is well known that the surface is easily eroded because it dissolves and becomes alkaline, resulting in so-called burns. In addition, fine dust and oil droplets floating in the atmosphere may adhere to the glass surface, contaminating the glass surface, and water droplets such as rainwater may adhere to the windows of automobiles, airplanes, and railway vehicles, which may damage the transparency or visibility of the glass. inhibit sex. For this reason, in order to make the glass surface water repellent, surface treatment agents have been proposed in which, for example, TF silicone wax, silicone oil made from polysiloxane, surfactants, etc. are applied onto the glass surface. However, many of these require pretreatment for application, and satisfactory results have not been obtained particularly with respect to uneven application, long-term durability, oil repellency, and stain resistance.

本発明者は、前記の如き問題点の認識（基づいて、ガラ
ス表面に撥水性、撥油性、耐汚染性などを長期間にわた
って付与し得る優れたガラス表面の処理剤を提供すべく
種々研究、検￥１を重ねた結果、本発明を完成したもの
である。Recognizing the above-mentioned problems, the present inventor conducted various studies in order to provide an excellent glass surface treatment agent that can impart water repellency, oil repellency, stain resistance, etc. to glass surfaces over a long period of time. As a result of repeated testing, the present invention has been completed.

即ち、本発明者の研究によれば、ポリフルオロアルキル
基（以下、Ｒｆ基と略す）含有の表面処理剤においてＲ
ｆ　基の臨界表面張力は２０ｄｙｎ　／　ｃｍ以下と低
く、水けもとよシ油類のそれよ沙も低いため、Ｒｆ基が
ガラス表面を覆うと撥水撥油性が付与できること、さら
に、Ｒｆ　基をガラス表面に効率よく配向させるにはア
ミド基が有用であり、撥水撥油性を高める機能を付与し
得るという事実を見出した。又、Ｒｆ基含有化合物をガ
ラス表面へ強固に接着して、撥水撥油性を長期にわたシ
付与するためにはガラス表面の８１０Ｈ基と反応する一
３ｉ−０−Ｒ、−３ｉ−Ｈａｌ（Ｈａｌはハロゲン）の
存在が好まし、く、か＼る一３ｉ−〇−Ｒなどは水の存
在で加水分解し、架橋反応を起すこと及びガラス表面の
５ｉＯＨと反応してガラス表面に化学的に接着し得るこ
とが可能となる。That is, according to the research of the present inventor, in a surface treatment agent containing a polyfluoroalkyl group (hereinafter abbreviated as Rf group), R
The critical surface tension of the f group is low at 20 dyn/cm or less, and the water resistance and that of oils are also low, so when the Rf group covers the glass surface, water and oil repellency can be imparted, and furthermore, the Rf group It has been discovered that amide groups are useful for efficiently aligning glass on the surface of glass, and that they can provide a function of increasing water and oil repellency. In addition, in order to firmly adhere the Rf group-containing compound to the glass surface and provide water and oil repellency for a long period of time, -3i-0-R, -3i-Hal( (Hal is a halogen) is preferable; It becomes possible to adhere to the

而して、本発明者の研究によれＶｉＲｆ基含有化合物と
シラン化合物の反応によシ合成されるＲｆ基含有シラン
化合物に、アルコキシあるいはハロゲノ等シラン化合物
を混合使用するとガラスとの接着面における架橋度が増
大し、接着性及び撥水撥油性が向上し、高性能の表面処
理剤が得られるという事実を見出したものである。According to the research of the present inventor, when a silane compound such as an alkoxy or halogeno compound is mixed with an Rf group-containing silane compound synthesized by the reaction of a ViRf group-containing compound and a silane compound, crosslinking occurs at the adhesive surface with glass. The inventors have discovered the fact that a high-performance surface treatment agent can be obtained with increased adhesiveness and water/oil repellency.

また、か＼る特定の表面処理剤の薄膜をガラス表面に形
成させると、反射率が小さくなり、その結果ガラスの透
視性などの阻害要因を解消可能であるという利点も発揮
される。Furthermore, when a thin film of such a specific surface treatment agent is formed on the glass surface, the reflectance is reduced, and as a result, there is an advantage in that it is possible to eliminate factors that inhibit the transparency of the glass.

かくして、本発明は前記知見に基づいて完成されたもの
であり、 １ 〔但し、Ｒｆは炭素数１〜２０個のポリフルオロアルキ
ル基であってエーテル結合を１僻以上含んでいてもよい
、Ｒ１は水素原子又は低級アルキル基、又は−〇０Ｎ（
Ｒ２）−Ｑ−又は−５０２Ｎ（Ｒ”）−ｑ、−（但し、
Ｒ２は水素原子又は低級アルキル基、Ｑは二価の有機基
を示す）、Ａはアルキレン基、Ｚは低級アルキル基、Ｙ
ｌ及びではそれぞれノーロゲン、アルコキシ基又はＲ３
ｃｏｏ−（世し　Ｒ３は水層チとは低級アルキル基）、
ｎは０又は１の整数、ａは１〜３の整数、ｂは０又は１
〜２の整数を示す。〕で表わされるＲｆ　基含有シラン
化合物又は該化合物の部分加水分解線金物と、−ラン化
合物からなる新規がガラスの表面処理剤を提供するもの
である。Thus, the present invention was completed based on the above knowledge, is a hydrogen atom or a lower alkyl group, or -〇ON(
R2) -Q- or -502N(R") -q, - (however,
R2 is a hydrogen atom or a lower alkyl group, Q is a divalent organic group), A is an alkylene group, Z is a lower alkyl group, Y
l and are respectively norogen, alkoxy group or R3
coo- (R3 is a lower alkyl group),
n is an integer of 0 or 1, a is an integer of 1 to 3, b is 0 or 1
Indicates an integer between ~2. The present invention provides a novel glass surface treatment agent comprising an Rf group-containing silane compound represented by the above formula or a partially hydrolyzed metal wire of the compound, and a -ran compound.

本発明の処理剤は、Ｒｆ　基が高密度化されているので
高い撥水撥油性を発揮し得るものである。しかも、アミ
ド基を含み、Ｒｆ基をガラス表面に配向させやすくし、
さらに、シランは水の存在で加水分解することにより、
架橋反応及びガラスの５ｉＯＨ基との反応が促進されて
、ガラス表面に化学的に接着する。又、シラン化合物は
架橋密度を増大させるのにＭ用であり、さらに、接着性
及び撥水撥油性などを向上させ得るものである。The processing agent of the present invention can exhibit high water and oil repellency because the Rf groups are highly densified. Moreover, it contains an amide group, making it easier to orient the Rf group on the glass surface,
Additionally, silanes can be hydrolyzed in the presence of water.
Cross-linking reactions and reactions with the 5iOH groups of the glass are promoted to chemically adhere to the glass surface. Further, the silane compound is used for M to increase the crosslinking density, and can also improve adhesiveness, water and oil repellency, and the like.

本発明における処理剤は前記の如き一般式０）のＲｆ基
含有シラン化合物又は、該化合物の部９加水分解縮合物
と、一般式（ＩＩ）のシラン化合物とからなるが、Ｒｆ
　　基含有シラン化合物のＲｆハ炭素数１〜２０個のパ
ーフルオロアルキル基あるいはエーテル結合を１個以上
含む 特に炭素ｆｉ　４〜１２個のパーフルオロアルキル基、
ｍは２〜１０の整数であることが好適である。Ｒ１は水
素原子又は炭素数１〜４の低級アルキル基のいずれでも
良い。Ｘは−ＣＯＮ（Ｒ２）−Ｑ−又は−３Ｏ２１ＪＩ
Ｒ２）−Ｑ、−が選定されるが、Ｒ２は水素原子又は炭
素数１〜４の低級アルキル基であシ、Ｑは二価の有機基
で、好ましくは−（ＣＨｚ）２−　。The treatment agent in the present invention is composed of the Rf group-containing silane compound of the general formula 0) or the Part 9 hydrolyzed condensate of the compound, and the silane compound of the general formula (II).
Rf of the group-containing silane compound is a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroalkyl group having 4 to 12 carbon atoms, especially containing one or more ether bonds;
It is suitable that m is an integer of 2 to 10. R1 may be a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. X is -CON(R2)-Q- or -3O21JI
R2) -Q, - are selected, where R2 is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and Q is a divalent organic group, preferably -(CHz)2-.

〜４の低級アルキル基が選定される。Ｙｌ及びＹ２Ｙ２
は好ましくはＣ１、−ｏｃＨ３，−０Ｏ２Ｈ５，ＣＨ３
ｃｏｏ−０２Ｈ５ｃＯＯ−が選定される。ｎはＯ又は１
の整数であり、ａは１〜３の整数であシ、ｂは０又は１
〜２の整数である。~4 lower alkyl groups are selected. Yl and Y2Y2
is preferably C1, -ocH3, -0O2H5, CH3
coo-02H5cOO- is selected. n is O or 1
is an integer of 1 to 3, b is 0 or 1
It is an integer between ~2.

而して、一般式（１）のＲｆ　基含有シラン化合物は種
々の方法あるいは軽路で入手され得るが、通常はＲｆ（
Ｘ）ｎ−ＣＯＯＲＩ化合物とＨ２ＮＡＳｉＹｓ化合物と
の反応を含む工程によって合成される。かかる合成反応
は活性水素をもたない溶媒を使用してもよく、反応温度
は０〜１５０℃、好ましくは４０〜８０℃、反応時間は
１〜５０時間、好ましくは２〜１０時間で行われる。Therefore, the Rf group-containing silane compound of general formula (1) can be obtained by various methods or by easy route, but usually Rf (
X) Synthesized by a process involving reaction of n-COORI compound and H2NASiYs compound. Such a synthetic reaction may use a solvent without active hydrogen, the reaction temperature is 0 to 150°C, preferably 40 to 80°C, and the reaction time is 1 to 50 hours, preferably 2 to 10 hours. .

本発明において、一般式（１）のＲｆ基含有シラン化合
物としては、例えば ＯｇＦｌｇＣＯＮＨ（ＣＨ２）３ｓｔ（ＱＣ２Ｈ，）３
１ＣｇＦ！Ｉｇ０ＯＮＨ（ＯＨ２）３８１０１ｇ　。In the present invention, as the Rf group-containing silane compound of general formula (1), for example, OgFlgCONH(CH2)3st(QC2H,)3
1CgF! Ig0ONH(OH2) 38101g.

ＣＨ３ ０９Ｆ１９ＣＯＮＨ（ＣｎＨ２）３ＳｉＯ１２。CH3 09F19CONH(CnH2)3SiO12.

０９Ｆ＋ｏ０ＯＮＨ（ＯＨ２）ＮＲ，、（ＣＨ２）ａｓ
ｉ（Ｏｃ２Ｈ，）３゜Ｃ，Ｆ、９０ＯＮＨ（ＣＨ２）５
ＣＯＮＨ（ＣＨ２）３　Ｓｉ　（００２Ｈ５）ａ　。09F+o0ONH(OH2)NR,,(CH2)as
i(Oc2H,)3°C,F,90ONH(CH2)5
CONH(CH2)3Si(002H5)a.

ＯｓＦ＋ｔＳＯｚＮＨ（（！Ｈ２）５ＣＯＮＨ（ＯＨ２
）３Ｓｉ（ＱＣ！２Ｈ５）３　。OsF+tSOzNH((!H2)5CONH(OH2
)3Si(QC!2H5)3.

が挙げられる。can be mentioned.

一般式（ＩＩ）　　Ｓ　１Ｒ２ｏＹ２４−ｏのシラン化
合物において、Ｒ２は水素原子又は炭素数１〜４の低級
アルキル基、ではハロゲン又は炭素数１〜４個のアルコ
キシ基あるいはＲ４ＣＯＯ−から選定され、好ましくは
ａｌ、　”Ｏ（１！Ｈ３＋　−ｏｃ２Ｈ５，ｃＨ３ｃｏ
ｏ−。In the silane compound of general formula (II) S1R2oY24-o, R2 is selected from a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, or R4COO-, preferably al, ”O(1!H3+ -oc2H5,cH3co
o-.

Ｃ２Ｈ３Ｃｏｏ−である。C2H3Coo-.

本発明の処理剤は一般式（１）のＲｆ基含有シラン化合
物と一般弐〇〕のシラン化合物とを混合することによシ
提供されるが、両化合物を水の存在下に混合して反応す
ることによシ得ることができる。両化合物の混合割合は
Ｒｆ基含有シラン化合物に対してシラン化合物１０〜９
０重量％、好ましくは６０〜７０重量％である。水の添
加量はＲｆ基含有シラン化合物に対して１０〜１０００
モル係、好ましくは１００〜５００モルチである。The treatment agent of the present invention is provided by mixing the Rf group-containing silane compound of the general formula (1) and the silane compound of the general formula (20). You can get it by doing this. The mixing ratio of both compounds is 10 to 9 silane compounds to the Rf group-containing silane compound.
0% by weight, preferably 60-70% by weight. The amount of water added is 10 to 1000 to the Rf group-containing silane compound.
The molar ratio is preferably 100 to 500 molar.

かくして得られる本発明の処理剤は、常法に従って乳濁
液、溶剤溶液、エアゾールなど任意の形態に調製される
。例えば、溶剤溶液型のものは、混合生成物を塩素系あ
るいは弗素系など適当な有機溶剤の１種又は２種以上の
混合溶媒し、さらにエアゾール噴射剤を添加して適当な
れるが、塗布の作業性から１５〜２５重量％が好ましい
。The processing agent of the present invention thus obtained can be prepared in any form such as an emulsion, a solvent solution, or an aerosol according to a conventional method. For example, in the case of a solvent solution type, the mixed product can be mixed with one or more suitable organic solvents such as chlorine-based or fluorine-based, and an aerosol propellant can be added. From the viewpoint of properties, it is preferably 15 to 25% by weight.

で被処理ガラス製品に適用され得る。例えば、溶剤溶液
型のものである場合には、浸漬塗布、吹付けなどの如き
被覆加工の既知の方法によりガラス製品の表面に付着さ
せる方法が採用され得る。ガラス表面に付着後は１００
％相対湿度下、１００℃以上の温良で２０分間以上の処
理を施こすのが好ましく、処理剤のガラス表面への接着
を強固なものとなし得る。can be applied to treated glass products. For example, in the case of a solvent solution type, a method of adhering to the surface of the glass product by a known coating method such as dip coating or spraying may be employed. 100 after adhering to the glass surface
It is preferable to perform the treatment at a temperature of 100° C. or higher for 20 minutes or more under % relative humidity, which can strengthen the adhesion of the treatment agent to the glass surface.

本発明の処理剤は他のＲｆ基含有化合物、各種重合体、
その他のブレンダーなどを混合しても良く、さらに帯電
防止剤、架橋剤など適宜添加剤を添加して使用すること
も可能である。The processing agent of the present invention includes other Rf group-containing compounds, various polymers,
Other blenders and the like may be mixed, and further additives such as antistatic agents and crosslinking agents may be added as appropriate.

本発明の表面処理剤で処理され得るガラス製品は特に限
定されること々く種々の例が挙けられ、例えば、ガオス
板、鐘、ガラス容器、ガラス器具、メガネレンズなどに
適用され得る。Glass products that can be treated with the surface treatment agent of the present invention are not particularly limited, but include various examples, such as glass plates, bells, glass containers, glass appliances, and eyeglass lenses.

本発明の処理剤の評価法は、撥水性はガラス表面上に水
を置き接触角を測定することによシ行い、撥油性は同様
にヘキサデカンの接触角を測定することにより行った。In the evaluation method of the treatment agent of the present invention, water repellency was determined by placing water on the glass surface and measuring the contact angle, and oil repellency was similarly determined by measuring the contact angle of hexadecane.

また、反射率は、正反射光測定付属装置付３２３形（日
立製作所社製の自動記録分光光度計）を使用して、入射
角５°で測定した。尚、塗膜の厚みは、　′°タリステ
ップ”　（、Ｒａｎｋ　Ｔａｙｌｏｒ）’Ｈｏ”ｂＢｏ
ｎ社製）を使用し、針圧を測定して求めた。Further, the reflectance was measured at an incident angle of 5° using a model 323 (automatic recording spectrophotometer manufactured by Hitachi, Ltd.) equipped with a specular reflection light measurement accessory. The thickness of the coating film is as follows: '°Talystep' (Rank Taylor) 'Ho'bBo
(manufactured by n company) and measured the stylus pressure.

次に本発明の実施例について、さらに具体的に説明する
が、この説明が本発明を限定するものでないことは勿論
である。Next, examples of the present invention will be described in more detail, but it goes without saying that this description does not limit the present invention.

１２の混合物であシ平均値は９．’０）１１１．２Ｓ（
０２モル）、Ｈ２Ｎ（ＯＨ２）３Ｓｉ（００２Ｈ５）３
　４４．２　ｔ（０，２％ル）、乾燥テトラヒドロフラ
ン１５０１を、温度計、冷却管及び攪拌機を装着した内
容積３００−のガラス製四ツ目フラスコに入れ、乾燥窒
素気流下でゆつぐシ攪拌しながら還流温度（約６０℃）
で５時間反応させた。テトラヒドロフランを溜去し反応
生成物を得た。反応生成物はガスクロマトグラフィーで
分析するとＯｎＦ　２ｎ＋　Ｉ　Ｃ０ＮＨ（Ｃ４Ｈ６）
３Ｓ　ｉ　（００２Ｈ５）３　　であシ、転化率は１０
０％であった。The average value is 9. '0)111.2S(
02 mol), H2N(OH2)3Si(002H5)3
44.2 t (0.2%) of dry tetrahydrofuran 1501 was placed in a 300-meter glass four-eye flask equipped with a thermometer, cooling tube, and stirrer, and stirred under a stream of dry nitrogen. while refluxing temperature (approximately 60℃)
The reaction was carried out for 5 hours. Tetrahydrofuran was distilled off to obtain a reaction product. When the reaction product is analyzed by gas chromatography, it is OnF 2n+ I C0NH (C4H6)
3S i (002H5)3, conversion rate is 10
It was 0%.

合成例２ （０，１−［１−ル）、Ｈ２Ｎ（ＣＨ２）３Ｓｉ（ＱＣ
！２Ｈ５）３２２．１９（ｏ、　１　モル）、乾燥テト
ラヒドロフラン１５゜２を合成例１と同様の方法で反応
させた。Synthesis Example 2 (0,1-[1-l), H2N(CH2)3Si(QC
! 2H5) 322.19 (o, 1 mol) and 15°2 of dry tetrahydrofuran were reacted in the same manner as in Synthesis Example 1.

反応生成物はガスクロマトグラフィーで分析ＣＦａ　　
　　　ＣＦ３ １ するとＣＦ３０Ｆ２０Ｆ２Ｑ（ＯＦＯＦ２０）２０ＦＣ
ＯＮＨ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３であシ、転化
率は・１００％であった。The reaction product was analyzed by gas chromatography as CFa.
CF3 1 Then CF30F20F2Q(OFOF20)20FC
ONH(CH2)3Si(OC2H5)3 was used, and the conversion rate was 100%.

実施例１ 合成例１で合成した０ｎＦ２ｎＨＣＯＮＨ（ＯＨ２）３
ｓｉ（ＱＣ！２Ｈ５）３　（ｎは６．８，１０．１２の
混合物であり平均値は９．０　）　７１．７　ｔ　（ｏ
、　１モル）、５ｉ（００２Ｈ６）４！＋　５．８．５
’　（０，２モル）、水６．６０２（０，３７モル）を
温度計及び攪拌機を装着した内容積２５　Ｃ１ｔｌ！の
三つロフラスコに仕込み、２５℃で攪拌しながら１０分
間反応後、Ｈ２Ｓ　ｏ４０．２２を添加してさらに２５
℃で攪拌しながら２０分間反応を行い、ＯｎＦ　２ｎ＋
１０ＯＮＨ（ＣＨ２）３８１（ＯＣ２比）３／　５ｉ（
ＱＣ！２１（５）４　　の反応生成物を得た。Example 1 0nF2nHCONH(OH2)3 synthesized in Synthesis Example 1
si(QC!2H5)3 (n is a mixture of 6.8 and 10.12, and the average value is 9.0) 71.7 t (o
, 1 mol), 5i(002H6)4! +5.8.5
' (0.2 mol), water 6.602 (0.37 mol) in an internal volume of 25 C1tl equipped with a thermometer and a stirrer! After reacting for 10 minutes with stirring at 25°C, add H2SO40.22 and further react for 25 min.
The reaction was carried out for 20 minutes with stirring at °C, and OnF 2n+
10ONH (CH2) 381 (OC2 ratio) 3/5i (
QC! A reaction product of 21(5)4 was obtained.

前記反応生、成物２０ｔをフロン（Ｒ−１１３：旭硝子
社製品）で稀釈して１００ｔとし、溶剤溶液を調製した
。別に、洗剤及びアセトンで洗浄し、１％塩酸溶液に浸
漬後乾隊したガラス板（ンーダ石灰ガラス）を用意して
、表面に調製済みの溶剤溶液をアプリケーターで塗布し
、１００チ相対湿度中、１２０℃、２０分間キユアリン
グを行った後、水及びヘキサデカンの接触角を測定した
。測定結果を第１表に示す。A solvent solution was prepared by diluting 20 t of the reaction product and product to 100 t with Freon (R-113: manufactured by Asahi Glass Co., Ltd.). Separately, prepare a glass plate (Nuda lime glass) that has been cleaned with detergent and acetone, immersed in 1% hydrochloric acid solution, and then dried.The prepared solvent solution is applied to the surface with an applicator, and the temperature is set at 100 degrees of relative humidity. After curing at 120° C. for 20 minutes, the contact angles of water and hexadecane were measured. The measurement results are shown in Table 1.

実施例２ 実施例１におけるＣｎＦ２ｎ＋Ｉ　ＣＩＩ（（ＯＨ２）
３Ｓｉ　（ＯＣ２Ｈ５）３／　Ｓｉ　（ＱＣ！２１（５
）４の反応生成物５２を、Ｒ−１１！＋／アセトン混合
溶媒（３／１）で稀釈して５００２とし、溶剤溶液を調
製した。別に洗剤及びアセトンで洗浄し、１チ塩酸溶液
に浸漬後乾燥したガラス板（ンーダ石灰ガラス）を用意
した。Example 2 CnF2n+I CII((OH2) in Example 1
3Si (OC2H5)3/ Si (QC!21(5
) 4 reaction product 52, R-11! +/acetone mixed solvent (3/1) to give 5002 to prepare a solvent solution. Separately, a glass plate (Nuda lime glass) was prepared which was washed with a detergent and acetone, immersed in a 1T hydrochloric acid solution, and then dried.

このガラス板を前記溶剤溶液中に浸漬し、引上速度５０
ｃｒｎ／分で引き上げ、１６０℃で１時間転線した。膜
厚は０，１μであり、反射率は１．１チであった（光の
波長５４０ｍμ）。尚、未処理ガラス板の反射率は４．
２チであった。This glass plate was immersed in the solvent solution, and the pulling rate was 50.
It was pulled up at crn/min and turned over at 160°C for 1 hour. The film thickness was 0.1μ, and the reflectance was 1.1ch (light wavelength 540mμ). The reflectance of the untreated glass plate is 4.
It was 2 chi.

実施例３ Ｃｕｔ’３ 合成例２で合成したＣＦ３０Ｆ２０Ｆ２Ｑ（ＯＦＯＦ２
０）２ＣＨ３ １ ＯＦｏＯＮＨ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３　と５
ｉ（０（４Ｈｓ）ｔ　　を実施例１と同様の方法で反応
させて０Ｆ３Ｃ！Ｆ２ａＦ２Ｏの反応生成物を得た。こ
の反応生成物を実施例１と同様の方法でガラス板の塗布
、処理後、水及びヘキサデカンの接触角を測定した。測
定結果を第１表に示す。Example 3 Cut'3 CF30F20F2Q (OFOF2
0)2CH3 1 OFoONH(CH2)3Si(OC2H5)3 and 5
i(0(4Hs)t) was reacted in the same manner as in Example 1 to obtain a reaction product of 0F3C!F2aF2O.This reaction product was coated on a glass plate in the same manner as in Example 1, and then treated. The contact angles of , water and hexadecane were measured.The measurement results are shown in Table 1.

実施例４ 実施例２において、実施例１の反応生成物の代りに実施
例３の反応生成物を使用した他は、同様に処理し、膜厚
０．１μの薄膜をガラス板表面に形成した。反射率は１
．０チであった。Example 4 In Example 2, the reaction product of Example 3 was used instead of the reaction product of Example 1, and the same treatment was carried out to form a thin film with a thickness of 0.1μ on the surface of the glass plate. . Reflectance is 1
．． It was 0chi.

比較例１〜２ 合成例１で合成したＣｎＦ２ｎ＋１０ＯＮＨ（ＣＨｚ　
）ｓ　５ｉ（Ｏｆ：！ｚＨｓ）ａ及び合成例２で合成し
た０Ｆ３Ｃ！Ｆ２０１１’２０１と同様の方法でガラス
板に塗布、処理後、水及びヘキサデカンの接触角を測定
した。それぞれの測定結果を第１表に示す。Comparative Examples 1-2 CnF2n+10ONH (CHz
)s 5i(Of:!zHs)a and 0F3C! synthesized in Synthesis Example 2! After coating and treating a glass plate in the same manner as F2011'201, the contact angles of water and hexadecane were measured. The results of each measurement are shown in Table 1.

第　　１　　表 実施例５〜１０ Ｒｆ　　基含有シラン化合物を異にする他は合成例１と
同様の方法で反応生成物を得た後、実施例１と同様の方
法でシラン化合物と反応させ、反応生成物をガラス板表
面に塗布、処理し、水及びヘキサデカンの接触角を測定
した。Table 1 Examples 5 to 10 A reaction product was obtained in the same manner as in Synthesis Example 1 except that the Rf group-containing silane compound was different, and then reacted with a silane compound in the same manner as in Example 1. The product was applied and treated on the surface of a glass plate, and the contact angles of water and hexadecane were measured.

測定結果を第２表に示す。The measurement results are shown in Table 2.

第　　２　　表 実施例１１ 実施例２において、実施例１の反応生成物の代りに実施
例１０の生成物を使用した他は同様に処理したガラス板
の反射率は１゜２チであった。Table 2 Example 11 A glass plate treated in the same manner as in Example 2 except that the product of Example 10 was used in place of the reaction product of Example 1 had a reflectance of 1°2.

実施例１２〜１４ 合成例１で得たＣｎＦ２ｎ＋１０ＯＮＨ（ＣＨ２）３Ｓ
１（ＯＣ２Ｈ５）３を使用して、シラン化合物を異にす
る他は実施例１と同様の反応方法で得だ反応生成物をガ
ラス表面に塗布、処理し、水及びヘキサデカンの接触角
を測定した。測定結果をｗ、　３表に示す。Examples 12-14 CnF2n+10ONH(CH2)3S obtained in Synthesis Example 1
The obtained reaction product was applied and treated on a glass surface using the same reaction method as in Example 1 except that the silane compound was different using 1(OC2H5)3, and the contact angles of water and hexadecane were measured. . The measurement results are shown in Table 3.

第一３表Table 13

Claims (1)

【特許請求の範囲】 １ 表わされるポリフルオロアルキル基含有シラン化合物又
は該化合物の部分加水分解線金物と、一般式５ｉＲ２ｏ
Ｙ２４−ｏで表わされるシラン化合物とからカるガラス
の表面処理剤。 〔但し、上記一般式において、Ｒｆ　は炭素数１〜２０
個のポリフルオロアルキル基であってエーテル結合を１
個以上含んでいてもよい、Ｒ１及びＲ２は水素原子又は
低級アルキル基、Ａはアルキレン基、２は低級アルキレ
基、ｙｌ及びψはそれぞれ）・ロゲン、アルコキシ基又
はＲ’ＣＯＯ−（但し、Ｒ３は水素原子又は低級アルキ
ル基を示す）、ｎはＯ又は１の整数、ａは１が３の整数
、ｂは０又は１〜２の整数、Ｃは０又は１〜２の整数を
示す、〕 （２１Ｒｆ　が炭素数１〜２０個のパーフルオロアルキ
ル基である特許請求の範囲第１項記載の表面処理剤。 ”ｓ　　　ＯＦ３ １ （３）Ｒｆが０Ｆ３ｃＦ２ｃ？２０（ｃＦＣＦ２０）ｍ
ＯＦ−（但し、ｍは１以上の整数）である特許請求の範
囲第１項記載の表面処理剤。[Scope of Claims] 1 A polyfluoroalkyl group-containing silane compound represented by the above formula or a partially hydrolyzed metal wire of the compound, and a compound having the general formula 5iR2o.
A surface treatment agent for glass that dissolves in a silane compound represented by Y24-o. [However, in the above general formula, Rf has 1 to 20 carbon atoms
Polyfluoroalkyl groups with 1 ether bond
R1 and R2 are hydrogen atoms or lower alkyl groups, A is an alkylene group, 2 is a lower alkylene group, yl and ψ are respectively), rogene, alkoxy group or R'COO- (however, R3 represents a hydrogen atom or a lower alkyl group), n is an integer of O or 1, a is an integer of 1 to 3, b is 0 or an integer of 1 to 2, C is 0 or an integer of 1 to 2,] (Surface treatment agent according to claim 1, wherein 21Rf is a perfluoroalkyl group having 1 to 20 carbon atoms."s OF3 1 (3) Rf is 0F3cF2c?20(cFCF20)m
The surface treatment agent according to claim 1, which is OF- (where m is an integer of 1 or more).
JP5372182A 1982-04-02 1982-04-02 Surface treating agent for glass Pending JPS58172245A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5372182A JPS58172245A (en) 1982-04-02 1982-04-02 Surface treating agent for glass

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5372182A JPS58172245A (en) 1982-04-02 1982-04-02 Surface treating agent for glass

Publications (1)

Publication Number Publication Date
JPS58172245A true JPS58172245A (en) 1983-10-11

Family

ID=12950688

Family Applications (1)

Application Number Title Priority Date Filing Date
JP5372182A Pending JPS58172245A (en) 1982-04-02 1982-04-02 Surface treating agent for glass

Country Status (1)

Country Link
JP (1) JPS58172245A (en)

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US5328768A (en) * 1990-04-03 1994-07-12 Ppg Industries, Inc. Durable water repellant glass surface
US5424130A (en) * 1991-05-13 1995-06-13 Toyota Jidosha Kabushiki Kaisha Water repellent glass and process for producing the same
US5446115A (en) * 1993-08-26 1995-08-29 Dow Corning Toray Silicon Co., Ltd. Surface-treatment composition
US5622784A (en) * 1986-01-21 1997-04-22 Seiko Epson Corporation Synthetic resin ophthalmic lens having an inorganic coating
US5674967A (en) * 1990-04-03 1997-10-07 Ppg Industries, Inc. Water repellent surface treatment with integrated primer
US5681914A (en) * 1995-05-25 1997-10-28 Dow Corning Toray Silicone Co., Ltd. Curable silicone composition
US5707740A (en) * 1990-04-03 1998-01-13 Ppg Industries, Inc. Water repellent surface treatment with acid activation
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US5783299A (en) * 1986-01-21 1998-07-21 Seiko Epson Corporation Polarizer plate with anti-stain layer
US6025025A (en) * 1990-04-03 2000-02-15 Ppg Industries Ohio, Inc. Water-repellent surface treatment
US6403225B1 (en) 1998-11-10 2002-06-11 Nissan Motor Co., Ltd. Article superior in slipping waterdrops down surface thereof
US6942924B2 (en) 2001-10-31 2005-09-13 Chemat Technology, Inc. Radiation-curable anti-reflective coating system
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US20150299469A1 (en) * 2014-04-18 2015-10-22 Canon Finetech Inc. Water-repellent and oil-repellent composition, and water-repellent film formed by using the composition

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JPS6468477A (en) * 1987-09-09 1989-03-14 Nisshin Steel Co Ltd Manufacture of surface-treated steel sheet excellent in water-repelling property and durability
JPH02311485A (en) * 1989-05-26 1990-12-27 Shin Etsu Chem Co Ltd Fluorine-containing organosilicon compound and its production
JPH0377893A (en) * 1989-08-21 1991-04-03 Shin Etsu Chem Co Ltd Fluorine-containing cyclic organic silicon compound and its preparation
JPH0377892A (en) * 1989-08-21 1991-04-03 Shin Etsu Chem Co Ltd Fluorine-containing organic silicon compound and its preparation
US5707740A (en) * 1990-04-03 1998-01-13 Ppg Industries, Inc. Water repellent surface treatment with acid activation
US5980990A (en) * 1990-04-03 1999-11-09 Ppg Industries Ohio, Inc. Water repellent surface treatment with acid activation
US5328768A (en) * 1990-04-03 1994-07-12 Ppg Industries, Inc. Durable water repellant glass surface
US5674967A (en) * 1990-04-03 1997-10-07 Ppg Industries, Inc. Water repellent surface treatment with integrated primer
US6025025A (en) * 1990-04-03 2000-02-15 Ppg Industries Ohio, Inc. Water-repellent surface treatment
US5424130A (en) * 1991-05-13 1995-06-13 Toyota Jidosha Kabushiki Kaisha Water repellent glass and process for producing the same
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US5446115A (en) * 1993-08-26 1995-08-29 Dow Corning Toray Silicon Co., Ltd. Surface-treatment composition
US5681914A (en) * 1995-05-25 1997-10-28 Dow Corning Toray Silicone Co., Ltd. Curable silicone composition
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US6403225B1 (en) 1998-11-10 2002-06-11 Nissan Motor Co., Ltd. Article superior in slipping waterdrops down surface thereof
US6942924B2 (en) 2001-10-31 2005-09-13 Chemat Technology, Inc. Radiation-curable anti-reflective coating system
US20150299469A1 (en) * 2014-04-18 2015-10-22 Canon Finetech Inc. Water-repellent and oil-repellent composition, and water-repellent film formed by using the composition
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