JPS58172246A - Surface treating agent for glass - Google Patents
Surface treating agent for glassInfo
- Publication number
- JPS58172246A JPS58172246A JP5372282A JP5372282A JPS58172246A JP S58172246 A JPS58172246 A JP S58172246A JP 5372282 A JP5372282 A JP 5372282A JP 5372282 A JP5372282 A JP 5372282A JP S58172246 A JPS58172246 A JP S58172246A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- group
- water
- water glass
- treatment agent
- 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
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)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、ガラス表面に撥水性、撥油性、耐汚染性、低
反射性などを付与する処理剤に関し、さらに詳しく言へ
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縮合物と水ガラスとからなる新規な
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 relates to a treatment agent that imparts water repellency, oil repellency, stain resistance, low reflectivity, etc. to a glass surface. The present invention relates to a novel glass surface treatment agent comprising a partially hydrolyzed condensate of a compound and water glass.
ガラス板、鏡、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
より水分が凝縮したり、水によって濡らされた場合、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
は周知である。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ー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
ばシリコン系ワックス、ポリシロキサンからなるシリコ
ン油や界面活性剤などを直接塗布する表面処理剤が提案
されでいる。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、且つ塗布時に発生する塗布ムラ、
あるいは処理剤自身のガラスへの接着力が低いことによ
る長期の耐久性、並びに撥油性、耐汚染性については満
足し得る結果は得られていない。Moisture condenses on the surfaces of glass products such as glass plates, mirrors, glass containers, glass utensils, and eyeglass lenses due to the influence of atmospheric humidity and temperature, and when wet with water, glass components may dissolve into the moisture. It is well known that the surface becomes alkaline and is easily eroded, 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, causing problems with the transparency or visibility of the glass. inhibit. For this reason, in order to make the glass surface water repellent, surface treatment agents have been proposed in which, for example, silicone wax, silicone oil made of polysiloxane, surfactant, etc. are directly applied. However, many of these require pre-treatment for application, and are prone to uneven coating that occurs during application.
Alternatively, satisfactory results have not been obtained regarding long-term durability, oil repellency, and stain resistance due to the low adhesion of the treatment agent itself to glass.
本発明者は、前記の如き問題点の認識に基ついて、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の表面処理剤を提供すべく
種々研究、検討を重ねた結果、本発明を完成したもので
ある。Based on the recognition of the above-mentioned problems, the present inventor has carried out various studies in order to provide an excellent glass surface treatment agent that can impart water repellency, oil repellency, stain resistance, etc. to the glass surface over a long period of time. As a result of repeated studies, the present invention was 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）含有化合物にお暦て、Ｒｆ基
の臨界表面張力は２０ ｄｙｎ／６ｎ以下と低く、水は
もとよシ油類のそれよりも低いため、ガラス表面をＲｆ
基含有化合物で覆うと撥水撥油性を付与できること、さ
らにＲｆ基含有化合物をガラス表面へ強固に接着して撥
水撥油性などを長期にわたシ付与するためにはガラス表
面の５ｉＯＨ基と反応する−８１−〇−Ｒ９−Ｓｉ −
Ｈａｌ （Ｈａｌはハロゲン）の存在が好ましく、−５
ｉ−０−Ｒは水の存在で加水分解し、架橋反応を起こし
７ガラス表面の５ｉＯＨと反応して化学的に接着するこ
とから、Ｒｆ基含有化合物とシラン化合物との反応によ
って得られるＲｆ基含有シラン化合物が優れていること
、又、該Ｒｆ基含有シラン化合物に水ガラスを混合する
ことにより、撥水撥油性が顕著に向上するという事実を
見出した。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、ガラス表面の反射率を低下させ
ることができ、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。That is, according to the research of the present inventors, in compounds containing polyfluoroalkyl groups (hereinafter abbreviated as Rf groups), the critical surface tension of Rf groups is as low as 20 dyn/6n or less, and it is difficult to absorb water as well as water. Since the Rf is lower than that of oils, the glass surface is
When coated with a group-containing compound, water and oil repellency can be imparted.Furthermore, in order to firmly adhere the Rf group-containing compound to the glass surface and impart water and oil repellency over a long period of time, it is necessary to react with the 5iOH group on the glass surface. -81-〇-R9-Si -
The presence of Hal (Hal is halogen) is preferred, -5
i-0-R hydrolyzes in the presence of water, causes a crosslinking reaction, and reacts with 5iOH on the glass surface to chemically bond, so the Rf group obtained by the reaction of an Rf group-containing compound and a silane compound. It has been discovered that the silane compound contained therein is excellent, and that water and oil repellency can be significantly improved by mixing water glass with the Rf group-containing silane compound. Furthermore, by forming a thin film of such a specific surface treatment agent on the glass surface, it is possible to reduce the reflectance of the glass surface, and as a result, it has the advantage that it is possible to eliminate factors that inhibit the transparency of the glass. Demonstrated.
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、Ｒｆ基含有シラン化合物又は該化合物の部分加
水分解縮合物と水ガラスとからなるガラスの表面処理剤
を新規に提供するものである。Thus, the present invention has been completed based on the above findings, and provides a new glass surface treatment agent comprising an Rf group-containing silane compound or a partially hydrolyzed condensate of the compound and water glass. .
而して、本発明の表面処理剤は優れた撥水撥油性、耐汚
染性、低反射性を発揮するとともに、その性能を長期間
維持させ得るものである。Thus, the surface treatment agent of the present invention exhibits excellent water and oil repellency, stain resistance, and low reflectance, and can maintain these properties for a long period of time.
重置萌における処理剤はＲｆ基含有シラン化合物又は該
化合−物の部分加水分解縮合物と水ガラスとからなるが
、好適な実施態様では、式（ＲｆＱ ）ａｓｉ （Ｚ）
ｂＹ４−ａ−ｂ のＲｆ基含有シラン化合物が選定
される。前記式において、Ｒｆは炭素数４〜１６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ｍは２〜１０の整数であることが好ましい。The treatment agent in superposition moe is composed of an Rf group-containing silane compound or a partially hydrolyzed condensate of the compound and water glass, and in a preferred embodiment, it has the formula (RfQ) asi (Z)
The Rf group-containing silane compound bY4-a-b is selected. In the above formula, it is preferable that Rf contains one or more perfluoroalkyl groups having 4 to 16 carbon atoms or one or more ether bonds, and particularly m is an integer of 2 to 10.
Ｑは二価の有機基であり、Ｚは炭素数１〜４のルキル基
であり、Ｙは好ましくは−Ｃ１，−０ＣＨ３゜−０Ｃ２
Ｈ５，ＣＨ３ＣＯＯ−、Ｃ２Ｈ５Ｃ０〇−が選定される
。Q is a divalent organic group, Z is an alkyl group having 1 to 4 carbon atoms, and Y is preferably -C1, -0CH3° -0C2
H5, CH3COO-, C2H5C00- are selected.
ａは１〜３の整数であシ、ｂは０又は１〜２の整数であ
る。a is an integer of 1-3, and b is 0 or an integer of 1-2.
而して、前記式のＲｆ基含有シラン化合物ｆｄ種々の方
法あるーは経路で入手され得るが、例えば、ＲｆＱ化合
物とＲ３１Ｙ３化合物との反応を含む工程によつヤ合成
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℃、反応時間は１
〜５０時間で行われる。Thus, although the Rf group-containing silane compound fd of the above formula can be obtained by various methods or routes, it is synthesized, for example, by a process involving the reaction of an RfQ compound and an R31Y3 compound. Such a synthetic reaction may use a solvent that does not have active hydrogen, the reaction temperature is 0 to 150°C, and the reaction time is 1.
Performed in ~50 hours.
本発明において、前記式のＲｆ基含有シラン化合物とし
ては、例えば、
Ｃ）（３
ＲｆＣＨ２ＣＨ２ＳｉＣ１３，ＲｆＣＨ２ＣＨ２ＳｉＣ
１２゜（ＲｆＣＨ２ＣＨ２）２ＳｉＣ１２，ＲｆＣＨｚ
ＣＨ２Ｓｉ（ＯＣＨａ）ｓ。In the present invention, as the Rf group-containing silane compound of the above formula, for example, C) (3 RfCH2CH2SiC13, RfCH2CH2SiC
12゜(RfCH2CH2)2SiC12, RfCHz
CH2Si(OCHa)s.
Ｒｆ Ｃ０ＮＨＣＨ２ＣＨ２ＣＨ２Ｓｉ （○Ｃ２Ｈ５
）３＋Ｒｆ Ｃ０ＮＨＣＨ２ＣＨ２ＣＨ２ＣＨＣＨ２Ｃ
Ｈ２ＣＨ２Ｓｉ （○ｃ２ Ｈ５）３ ＋Ｈ３
Ｒｆ ＳＯ２ＮＣＨ２ＣＨ２Ｃ０ＮＨＣＨ２ＣＨ２ＣＨ
２Ｓｉ （ＯＣ２Ｈ５）３ 。Rf C0NHCH2CH2CH2Si (○C2H5
)3+Rf C0NHCH2CH2CH2CHCH2C
H2CH2Si (○c2 H5)3 +H3 Rf SO2NCH2CH2C0NHCH2CH2CH
2Si(OC2H5)3.
Ｒｆ ＣＨ２ＣＨ２０ＣＯＣＨ２ＣＨ２５ＣＨ２ＣＨ２
ＣＨ２Ｓｉ （ＯＣＨ３）３ 。Rf CH2CH20COCH2CH25CH2CH2
CH2Si(OCH3)3.
ＲｆＣＨ２ＣＨ２０ＣＯＮＨＣＨ２ＣＨ２Ｃ’Ｈ２Ｓｌ
（ＱＣ２Ｈ５）３゜ＲｆＣ○０ＣＨ２ＣＨＣＨ２０Ｃ
Ｈ２ＣＨ２ＣＨ２Ｓｉ （ＯＣ２Ｈ５）３ ＊Ｈ
Ｒｆ ＣＨ２ＣＨ２ＮＨＣＨ２ＣＨ２Ｓｉ （ＯＣＨ３
）３ ＋Ｒｆ ＣＨ２ＣＨ２ＮＨ２ＣＨ２Ｓｉ （ＯＣ
Ｈ２ＣＨ２０ＣＨａ ）３ 。RfCH2CH20CONHCH2CH2C'H2Sl
(QC2H5) 3゜RfC○0CH2CHCH20C
H2CH2CH2Si (OC2H5)3 *H Rf CH2CH2NHCH2CH2Si (OCH3
)3 +Rf CH2CH2NH2CH2Si (OC
H2CH20CHa)3.
ＣＦ３ ０Ｆ３
１ 、 １ ””’：１１：ＣＦａ ＣＦ
２０Ｆ２０ （ＣＦＣＦ２０ ）ｍ’ＣＦＣＯＮＨ（Ｃ
Ｈ２）３ Ｓｉ （０ＣＨ３）３が挙げられ得る。CF3 0F3 1, 1 ""':11:CFa CF
20F20 (CFCF20)m'CFCONH(C
Mention may be made of H2)3Si(0CH3)3.
水ガラスはＪＩＳ −Ｋ １４０８に規定されるごくあ
シふれたものでよく、５ｉ０２ ／Ｎａ２Ｏ＝ ０．５
〜４から選定され、例えば、メタけい酸ナトリウム（Ｎ
ａ２ Ｓｉ Ｏｓ ）及び種々の割合の水和物、オルト
けい酸ナトリウム（Ｎａ４５ｉＯ４） 、二けい酸ナト
リウム（Ｎａ２ Ｓｉｚ Ｏｓ ）、 四けい酸ナトリ
ウム（Ｎａ２５ｉ４０ｓ） が挙げられ、それぞれを
単独又は混合したものでもよい。The water glass may be a very coarse one specified in JIS-K 1408, 5i02 /Na2O = 0.5
For example, sodium metasilicate (N
a2SiOs) and hydrates in various proportions, sodium orthosilicate (Na45iO4), sodium disilicate (Na2SizOs), and sodium tetrasilicate (Na25i40s), each of which may be used alone or in combination. good.
本発明の処理剤は前記式のＲｆ基含有シラン化合物と水
ガラスとを有機溶剤、例えばテトラヒドロフランと共に
混合攪拌することにょシ、溶剤溶液型として得ることが
できる。Ｒｆ基含有シラン化合物と水ガラスの混合比率
はＲｆ基含有シラン化合物：水ガラス＝１：０．１〜５
０重量比であるのが望ましい。又、溶剤溶液型とする場
合、Ｒｆ基含有シラン化合物と水ガラスの混合物は溶剤
に対して１０〜３０重量係溶液として調製されるが、塗
布の作業性から１５〜２５重量％が好ましい。The treatment agent of the present invention can be obtained in the form of a solvent solution by mixing and stirring the Rf group-containing silane compound of the above formula and water glass with an organic solvent such as tetrahydrofuran. The mixing ratio of the Rf group-containing silane compound and water glass is Rf group-containing silane compound: water glass = 1:0.1 to 5.
Preferably, the weight ratio is 0. In addition, in the case of a solvent solution type, the mixture of the Rf group-containing silane compound and water glass is prepared as a solution with a weight ratio of 10 to 30% by weight to the solvent, but it is preferably 15 to 25% by weight from the viewpoint of workability of coating.
かくして得られる本発明の処理剤は溶剤溶液型の他にエ
アゾールなど任意の形態に調製されるが、エアゾール型
のものは前記溶剤型の溶液（てエアゾール噴射剤を添加
して適当な容器に充填すればよい。The treatment agent of the present invention obtained in this manner can be prepared in any form such as a solvent solution type or an aerosol type, but an aerosol type is prepared by adding an aerosol propellant to the above solvent type solution and filling it into a suitable container. do it.
本発明のガラスの表面処理剤は被処理ガラス製品の形状
や前記調製形態に応じて任意の方法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
法によりガラス表面に付着させる方法が採用され得る。The glass surface treatment agent of the present invention can be applied to a glass product to be treated by any method depending on the shape of the glass product and the preparation form. For example, in the case of a solvent solution type, a method of adhering to the glass surface by a known coating method such as dip coating or spraying may be employed.
ガラス表面に付着後は１００％相対湿度下６０〜１８０
℃の温度で１〜６０分間の処理を施すのが好ましく、処
理剤のガラス表面への接着を強固なものとなし得る。After adhering to the glass surface, 100% relative humidity 60-180
It is preferable to perform the treatment at a temperature of 1 to 60 minutes at a temperature of .degree. C., and this can strengthen the adhesion of the treatment agent to the glass surface.
本発明の表面処理剤はプロトン酸、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
よく、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 surface treatment agent of the present invention may be mixed with protonic acid, other Rf group-containing compounds, various polymers, other blenders, etc., and may also be used by adding appropriate additives such as antistatic agents and crosslinking agents. is also possible.
本発明の処理剤で処理され得るガラス製品は特に限定さ
れることなく種々の例が挙げられ、例えばガラス板、鏡
、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 treatment agent of the present invention are not particularly limited, and include various examples, such as glass plates, mirrors, glass containers, glass appliances, and eyeglass lenses.
本発明の処理剤の評価法は次の通りである。The evaluation method for the treatment agent of the present invention is as follows.
即ち、撥水性はガラス表面上に水を置き接触角を測定す
ることにより行い、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り１、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）を使用しで、入射角５° で測定した
。尚、塗膜の厚みは、“タリステップ” （Ｒａｎｋ’
Ｔａｙｌｏｒｌ−１ｏｂＳｏｎ社製）を使用し、針圧を
測定して求めた１、
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。That is, water repellency was determined by placing water on the glass surface and measuring the contact angle, oil repellency was similarly determined by measuring the contact angle of hexadecane1, and reflectance was determined by measuring the specular reflection light measurement. Measurements were made using a model 323 equipped with an automatic recording spectrophotometer (manufactured by Hitachi, Ltd.) at an incident angle of 5°. The thickness of the coating film is "Talystep"(Rank'
Taylor-1 (manufactured by obSon Inc.) and measured the stylus force.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. It is.
合成例１
ＣｎＦ２ｎＨＣＨ＝ ｃ）（、、（但し、ｎは６．８．
１０．’ １２の混合物であシ平均値は９．０ ） ９
９．２ Ｆ （０，２モル）、［■５ｉＣ１３３２，５
ｆ （０，２４モル）、Ｈ２ＰｔＣ１ａ・Ｈ２Ｏ０，０
５２Ｆを温度計、冷却管及び攪拌機を装着した内容積２
’ＯＯｍ／’の四ツロフラスコに入れ、乾燥窒素気流下
で攪拌しながら８０℃で２００時間反応せた。反応終了
後蒸留することにより反応生成物を得た。反応生成物は
ガスクロマトグラフィー、ＩＲ，ＮＭＲで確認するとＣ
ｎＦ２ｎＨＣＨ２ＣＨ２Ｓｉ Ｃ１３であり、それへの
転化率は９５チであった。Synthesis Example 1 CnF2nHCH=c)(,,(However, n is 6.8.
10. ' It is a mixture of 12 and the average value is 9.0) 9
9.2 F (0.2 mol), [■5iC1332,5
f (0.24 mol), H2PtC1a.H2O0.0
Internal volume 2 with 52F equipped with thermometer, cooling pipe and stirrer
The mixture was placed in an 'OOm/' four-way flask and reacted at 80° C. for 200 hours with stirring under a stream of dry nitrogen. After the reaction was completed, a reaction product was obtained by distillation. The reaction product was confirmed by gas chromatography, IR, and NMR.
The conversion rate to nF2nHCH2CH2Si C13 was 95%.
合成例２
合成例１の生成物ＣｎＦ２ｎ＋ＩＣＨ２ＣＨｚＳＩＣ１
３６，３２ｆ（０，１モル）、メタノール２０２を混合
し、乾燥窒素をバブリングして生成するＨＣＩを除去し
ながら反応させた。反応の終点は生成したＨＣＩを定量
して確認した。反応終了後、過剰のメタノールを留去し
て反応生成物を得た。反応生成物はガスクロマトグラフ
ィー、ＩＲ，ＮＭＲで確認するとＣｎＦ２ｎ＋ｌＣＨ２
ＣＨ２ｓｉ （ＯＣＨｓ ）ｓであシ、それへの転化率
は１００％であった。Synthesis Example 2 Product of Synthesis Example 1 CnF2n+ICH2CHzSIC1
36,32f (0.1 mol) and methanol 202 were mixed and reacted while bubbling dry nitrogen to remove generated HCI. The end point of the reaction was confirmed by quantifying the amount of HCI produced. After the reaction was completed, excess methanol was distilled off to obtain a reaction product. The reaction product was confirmed by gas chromatography, IR, and NMR as CnF2n+lCH2
The conversion rate to CH2si(OCHs)s was 100%.
合成例３
ＣｎＦ２ｎ＋Ｉ Ｃ００ＣＨ（１，’Ｈ３）２ （但し
、ｎは６．８．１０゜１２の混合物であり平均値は９．
０ ） １１１．２９（０，２モル）、Ｈ２Ｎ（ＣＨ２
）３５ｉ（ＯＣ２Ｈ５）３４４．２５’（０，２モル）
、乾燥テトラヒドロフラン１５０りを温度計、冷却管及
び攪拌機を装着した内容積３００−の四ツロフラスコに
入れ、乾燥窒素気流中で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留去し
反宅生成物を得た。反応生成物はガスクロマトグラフィ
ー、ＩＲ，ＮＭＲで確認するとＣｎＦ２ｎ＋ＩＣ０ＮＨ
（ＣＨ２）３ ｓｉ （○Ｃ２Ｈ５）３ であシ、そ
れへの転化率は１００％であった。Synthesis Example 3 CnF2n+I C00CH(1,'H3)2 (However, n is a mixture of 6.8.10°12 and the average value is 9.
0) 111.29 (0.2 mol), H2N (CH2
)35i(OC2H5)344.25'(0.2 mol)
, 150 liters of dry tetrahydrofuran was placed in a 300-liter four-tube flask equipped with a thermometer, condenser, and stirrer, and heated to reflux temperature (approximately 60 liters) while stirring in a stream of dry nitrogen.
℃) for 5 hours. Tetrahydrofuran was distilled off to obtain a crude product. The reaction product was confirmed by gas chromatography, IR, and NMR as CnF2n+IC0NH.
The conversion rate to (CH2)3si(○C2H5)3 was 100%.
合成例４
（０，１モル）、Ｅ（２Ｎ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ
５）３ ２２．１９（０，１モル）、乾燥テトラヒドロ
フラン１５０２を合成例３と同様の方法で反応させて、
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、ＩＲ，ＮＭＲで確認すると
であり、それへの転化率は１００％であった。Synthesis Example 4 (0.1 mol), E(2N(CH2)3Si(OC2H
5) 3 22.19 (0.1 mol) and dry tetrahydrofuran 1502 were reacted in the same manner as in Synthesis Example 3,
A reaction product was obtained. The reaction product was confirmed by gas chromatography, IR, and NMR, and the conversion rate thereto was 100%.
実施例１
合成例１の反応生成物ＣｎＦ２ｎ＋４ ＣＨ２ＣＨ２Ｓ
ｉ Ｃ１５２Ｏｆ、１モル／ｌの水ガラス１号（側溝化
学して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（ソーダ
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、１６０
℃で２０分間キユアリングした。この表面に水を滴下し
て水の接触角を、ヘキサデカンを滴下してヘキサデカン
の接触角をそれぞれ測定した。測定結果を第１表に示す
。Example 1 Reaction product of Synthesis Example 1 CnF2n+4 CH2CH2S
i C152Of, 1 mol/l water glass No. 1 (a solvent solution was prepared by gutter chemistry. Separately, a glass plate (soda lime glass) was prepared which was washed with detergent and acetone, immersed in a 1% hydrochloric acid solution, and then dried. Apply the prepared solvent solution to the surface using an applicator, and apply the prepared solvent solution to the surface at 160° C.
Cure for 20 minutes. The contact angle of water was measured by dropping water on this surface, and the contact angle of hexadecane was measured by dropping hexadecane. The measurement results are shown in Table 1.
実施例２
合成ｑ’に反応生成物ＣｎＦ２ｎ４４ ＣＨ２ＣＨ２Ｓ
ｌ（○Ｃ）Ｉｓ）ｓ２０ｆ、１モル／ｌの水ガラス１号
（側溝化学社製）２０−、テトラヒドロフラン１００Ｐ
’ｉ実施例１と同様の方法で混合して溶剤溶液を調製し
た。調製液を実施例１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。測定
結果を第１表に示す。Example 2 Synthesis q' with reaction product CnF2n44 CH2CH2S
l(○C)Is)s20f, 1 mol/l water glass No. 1 (manufactured by Samizo Kagaku Co., Ltd.) 20-, tetrahydrofuran 100P
'i A solvent solution was prepared by mixing in the same manner as in Example 1. Apply the prepared solution to a glass plate in the same manner as in Example 1,
After treatment, the contact angles of water and hexadecane were measured. The measurement results are shown in Table 1.
実施例３〜４
合成例３の反応生成物ＣｎＦ２ｎ４４ Ｃ０ＮＨ（ＣＨ
２）ａ Ｓ １（ＯＣ’ｚＨｓ）ｓ ２０ ｆ 、又
は、合成例４の反応生成物
２０２．１モル／ｚの水ガラス（ＪＩＳ −Ｋ １４０
８）２０ｍ／、テトラヒドロフラン１００ｆを実施例１
と同様の方式で混合して溶剤溶液を調製した。調製液を
実施例１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。測定結果を第１表
に示す。Examples 3-4 Reaction product CnF2n44C0NH(CH
2) a S 1 (OC'zHs) s 20 f or water glass (JIS-K 140
8) 20m/, 100f of tetrahydrofuran in Example 1
A solvent solution was prepared by mixing in the same manner as above. The prepared solution was applied to a glass plate in the same manner as in Example 1, and after treatment, the contact angles of water and hexadecane were measured. The measurement results are shown in Table 1.
実施例５〜６
１モル／ｌの水ガラス３号（側溝化学社製）、又はメタ
ケイ酸ナトリウムＮａ２５ｌ○３・９Ｈ２Ｏを使用［７
た他は実施例２と同様の方法で溶剤溶液を調製した後、
実施例１と同様の方法で接触角を測定した。測定結果を
第１表に示す。Examples 5 to 6 Using 1 mol/l water glass No. 3 (manufactured by Samizo Kagaku Co., Ltd.) or sodium metasilicate Na25l○3.9H2O [7
After preparing a solvent solution in the same manner as in Example 2,
The contact angle was measured in the same manner as in Example 1. The measurement results are shown in Table 1.
比較例１〜２
合成例１の反応生成物ＣｎＦ２ｎ＋Ｉ ＣＨ２ＣＨ２Ｓ
ｉ Ｃ１３２０１又は合成例２の反応生成物ＣｎＦ２
ｎＨＣＨ２ＣＨ２５ｉ（○ＣＨ３）３２０ ｆ及びテト
ラヒドロフラン１２０２を混合して溶剤溶液を調製した
後、実施例１と同様の方法で接触角を測定した。測定結
果を第１表に示す。Comparative Examples 1-2 Reaction product of Synthesis Example 1 CnF2n+I CH2CH2S
i C13201 or the reaction product CnF2 of Synthesis Example 2
After preparing a solvent solution by mixing nHCH2CH25i(○CH3)320f and tetrahydrofuran 1202, the contact angle was measured in the same manner as in Example 1. The measurement results are shown in Table 1.
実施例７
実施例１における第１表記載の組成物５２を、トリクロ
ロトリフルオロエタン／アセトンの混合溶媒（３／１
）で稀釈して５００ｆ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係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。このガ
ラス板を前記溶剤溶液中に浸漬し、引上速度５０儒／分
で引き上げ、１６０℃で１時間乾燥した。Example 7 Composition 52 described in Table 1 in Example 1 was mixed with a mixed solvent of trichlorotrifluoroethane/acetone (3/1
) 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 1st hydrochloric acid solution, and then dried. This glass plate was immersed in the solvent solution, pulled up at a pulling rate of 50 F/min, and dried at 160°C for 1 hour.
膜厚は０．１μであり、反射率は１．１％であった（光
の波長５４０ｍμ）。尚、未処理ガラス板の反射率は４
．２％であった。The film thickness was 0.1μ, and the reflectance was 1.1% (light wavelength 540mμ). The reflectance of the untreated glass plate is 4.
．． It was 2%.
実施例８
実施例７において、実施例１の組成物の代りに実施例４
の組成物を使用した他は、同様に処理シフ、膜厚０．１
μの薄膜をガラス板表面に形成した。反射率は１．０％
であらた。Example 8 In Example 7, Example 4 was substituted for the composition of Example 1.
The same treatment shift and film thickness of 0.1 were used except that the composition of
A thin film of μ was formed on the surface of a glass plate. Reflectance is 1.0%
So it's new.
実施例９
実施例７において、実施例１の組成物の代シに実施例５
の組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１．１俤であった。Example 9 In Example 7, Example 5 was substituted for the composition of Example 1.
The reflectance of a glass plate treated in the same manner except that the composition was used was 1.1.
実施例１０〜１６
Ｒｒ”基含有シラン化合物を異にする他は実施例１と同
様の方法で溶剤溶液を調製した後、実施例１と同様の方
式で接触角を測定した。測定結果を第２表に示す。Examples 10 to 16 Solvent solutions were prepared in the same manner as in Example 1, except that the Rr'' group-containing silane compound was different, and then contact angles were measured in the same manner as in Example 1. It is shown in Table 2.
Claims (1)
化合物の部分加水分解組合物と水ガラスとからなるガラ
スの表面処理剤。 ２、 ポリフルオロアルキル基含有７ラン化合物が、式 ％式％ 〔但し、上記式において、Ｒｆは炭素数４〜１６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、Ｑは二価の有機基、Ｚは低級アルキ
ル基、ｙはハロゲン、アルコキシ基又はＲＣＯＯ−（Ｒ
は水素原子又は低級アルキル基）、ａは１〜３の整数、
ｂは０又は１〜２の整数を示す。〕 で表わされる特許請求の範囲第１項記載の表面処理剤。 ３、 ボ１）フルオロアルキル基が炭素数４〜１６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項又
は第２項記載の表面処理剤。 ４、 ポリフルオロアルキル基が 上の整数）である特許請求の範囲第１項又は第２項記載
の表面処理剤。 ５、 ポリフルオロアルキル基含有シラン化合物と水ガ
ラスがｉ：０．１〜１の重量比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 glass surface treatment agent comprising a 17-fluoroalkyl group-containing silane compound or a partially hydrolyzed combination of the compound and water glass. 2. The polyfluoroalkyl group-containing 7-ran compound has the formula % formula % [However, in the above formula, Rf is a polyfluoroalkyl group having 4 to 16 carbon atoms and may contain one or more ether bonds. , Q is a divalent organic group, Z is a lower alkyl group, y is a halogen, an alkoxy group, or RCOO-(R
is a hydrogen atom or a lower alkyl group), a is an integer of 1 to 3,
b represents 0 or an integer of 1-2. ] The surface treatment agent according to claim 1, which is represented by: 3. B1) The surface treatment agent according to claim 1 or 2, wherein the fluoroalkyl group is a perfluoroalkyl group having 4 to 16 carbon atoms. 4. The surface treatment agent according to claim 1 or 2, wherein the polyfluoroalkyl group is the above integer. 5. The surface treatment agent according to claim 1, wherein the weight ratio of the polyfluoroalkyl group-containing silane compound and water glass is i:0.1 to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5372282A JPS58172246A (en) | 1982-04-02 | 1982-04-02 | Surface treating agent for glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5372282A JPS58172246A (en) | 1982-04-02 | 1982-04-02 | Surface treating agent for glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58172246A true JPS58172246A (en) | 1983-10-11 |
Family
ID=12950716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5372282A Pending JPS58172246A (en) | 1982-04-02 | 1982-04-02 | Surface treating agent for glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58172246A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02138286A (en) * | 1988-02-09 | 1990-05-28 | Matsushita Electric Ind Co Ltd | Perfluoroalkyl terminus silane compound, production thereof and coating agent using the same |
| JPH02311485A (en) * | 1989-05-26 | 1990-12-27 | Shin Etsu Chem Co Ltd | Fluorine-containing organosilicon compound and its production |
| JPH0377892A (en) * | 1989-08-21 | 1991-04-03 | Shin Etsu Chem Co Ltd | Fluorine-containing organic silicon compound and its preparation |
| JPH0377893A (en) * | 1989-08-21 | 1991-04-03 | Shin Etsu Chem Co Ltd | Fluorine-containing cyclic organic silicon compound and its preparation |
| JPH04132637A (en) * | 1990-09-26 | 1992-05-06 | Matsushita Electric Ind Co Ltd | Glass and production thereof |
| EP0513690A2 (en) * | 1991-05-17 | 1992-11-19 | Asahi Glass Company Ltd. | Surface-treated substrate |
| JPH0517489A (en) * | 1991-07-04 | 1993-01-26 | Shin Etsu Chem Co Ltd | Siloxane compound |
| US5360869A (en) * | 1992-10-30 | 1994-11-01 | University Of North Carolina At Chapel Hill | Method of making fluorinated copolymers |
| JPH08169729A (en) * | 1995-08-25 | 1996-07-02 | Matsushita Electric Ind Co Ltd | Water repellent/oil repellent glass |
| JPH08188448A (en) * | 1995-08-25 | 1996-07-23 | Matsushita Electric Ind Co Ltd | Production of antifouling glass |
| US5709741A (en) * | 1995-02-28 | 1998-01-20 | Dow Corning Toray Silicone Co., Ltd. | Water repellent for application to glass and water-repellent glass |
| US6403225B1 (en) | 1998-11-10 | 2002-06-11 | Nissan Motor Co., Ltd. | Article superior in slipping waterdrops down surface thereof |
| US6939613B2 (en) | 2002-03-18 | 2005-09-06 | Hoya Corporation | Optical member, process of producing optical member, and process of producing thin film |
| US7150917B2 (en) | 2002-08-02 | 2006-12-19 | Hoya Corporation | Optical member |
| JP2017014452A (en) * | 2015-07-06 | 2017-01-19 | Dic株式会社 | Surface modification agent, coating composition and article |
| JP2017031347A (en) * | 2015-08-04 | 2017-02-09 | Dic株式会社 | Coating composition and article |
-
1982
- 1982-04-02 JP JP5372282A patent/JPS58172246A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02138286A (en) * | 1988-02-09 | 1990-05-28 | Matsushita Electric Ind Co Ltd | Perfluoroalkyl terminus silane compound, production thereof and coating agent using the same |
| JPH02311485A (en) * | 1989-05-26 | 1990-12-27 | Shin Etsu Chem Co Ltd | Fluorine-containing organosilicon compound and its production |
| JPH0377892A (en) * | 1989-08-21 | 1991-04-03 | Shin Etsu Chem Co Ltd | Fluorine-containing organic silicon compound and its preparation |
| JPH0377893A (en) * | 1989-08-21 | 1991-04-03 | Shin Etsu Chem Co Ltd | Fluorine-containing cyclic organic silicon compound and its preparation |
| JPH04132637A (en) * | 1990-09-26 | 1992-05-06 | Matsushita Electric Ind Co Ltd | Glass and production thereof |
| EP0759413A1 (en) * | 1991-05-17 | 1997-02-26 | Asahi Glass Company Ltd. | Surface-treated substrate |
| EP0513690A2 (en) * | 1991-05-17 | 1992-11-19 | Asahi Glass Company Ltd. | Surface-treated substrate |
| JPH0517489A (en) * | 1991-07-04 | 1993-01-26 | Shin Etsu Chem Co Ltd | Siloxane compound |
| US5360869A (en) * | 1992-10-30 | 1994-11-01 | University Of North Carolina At Chapel Hill | Method of making fluorinated copolymers |
| US6458420B1 (en) | 1995-02-28 | 2002-10-01 | Dow Corning Toray Silicone Co., Ltd. | Water repellent for application to glass and water-repellent glass |
| US5709741A (en) * | 1995-02-28 | 1998-01-20 | Dow Corning Toray Silicone Co., Ltd. | Water repellent for application to glass and water-repellent glass |
| JP2577203B2 (en) * | 1995-08-25 | 1997-01-29 | 松下電器産業株式会社 | Method for producing antifouling glass |
| JP2577204B2 (en) * | 1995-08-25 | 1997-01-29 | 松下電器産業株式会社 | Water and oil repellent glass |
| JPH08188448A (en) * | 1995-08-25 | 1996-07-23 | Matsushita Electric Ind Co Ltd | Production of antifouling glass |
| JPH08169729A (en) * | 1995-08-25 | 1996-07-02 | Matsushita Electric Ind Co Ltd | Water repellent/oil repellent glass |
| US6403225B1 (en) | 1998-11-10 | 2002-06-11 | Nissan Motor Co., Ltd. | Article superior in slipping waterdrops down surface thereof |
| US6939613B2 (en) | 2002-03-18 | 2005-09-06 | Hoya Corporation | Optical member, process of producing optical member, and process of producing thin film |
| US7150917B2 (en) | 2002-08-02 | 2006-12-19 | Hoya Corporation | Optical member |
| JP2017014452A (en) * | 2015-07-06 | 2017-01-19 | Dic株式会社 | Surface modification agent, coating composition and article |
| JP2017031347A (en) * | 2015-08-04 | 2017-02-09 | Dic株式会社 | Coating composition and article |
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