JPH09255941A - Water-repellent treatment and preparation thereof - Google Patents
Water-repellent treatment and preparation thereofInfo
- Publication number
- JPH09255941A JPH09255941A JP6950796A JP6950796A JPH09255941A JP H09255941 A JPH09255941 A JP H09255941A JP 6950796 A JP6950796 A JP 6950796A JP 6950796 A JP6950796 A JP 6950796A JP H09255941 A JPH09255941 A JP H09255941A
- Authority
- JP
- Japan
- Prior art keywords
- water
- weight
- water repellent
- repellent treatment
- glass
- 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)
- 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、建築、自動車、車
両、航空機あるいは船舶などの風防ガラス、光学部品レ
ンズその他のガラス製品等の透明物品またはセラミック
スなどの不透明物品の親水性表面に優れた撥水性および
防汚性を与え、かつ、その処理作業性に優れた撥水処理
剤およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an excellent hydrophilic surface for a transparent article such as a windshield for an architectural, automobile, vehicle, aircraft or ship, an optical component lens or other glass products or an opaque article such as ceramics. The present invention relates to a water repellent treatment agent that imparts water resistance and antifouling properties and is excellent in treatment workability, and a method for producing the same.
【０００２】[0002]
【従来の技術】透明物品や不透明物品に表面処理を施し
て、撥水性、防汚性の機能を付加させることは、多くの
分野で重要な技術であり、ガラスやセラミックスなどの
無機質材料の表面を各種表面処理剤で処理して表面の性
質を改良し高性能化、応用範囲拡大等を図る研究が種々
行われている。その１つとして、本来親水性の表面をシ
リコーン系組成物など撥水剤で処理して撥水性表面に改
質するという方法が提案されており、特に特公昭５５−
２９０２４号公報にはパーフルオロアルキル基を含有す
るシラン、酸、および非極性有機溶媒からなるガラスの
撥水処理剤が開示され、特開平２−２３３５３５号公報
にはパーフルオロアルキル基を含有するシラン、オルガ
ノポリシロキサン、酸、および揮発性有機溶媒からなる
ガラスの表面処理が開示され、特開平４−１４４９４０
号公報には、オルガノポリシロキサン、パーフルオロア
ルキル基含有シランまたはシロキサン、および酸からな
る撥水撥油剤組成物が提案されている。2. Description of the Related Art It is an important technology in many fields to add a water-repellent and antifouling function to a transparent or opaque article by surface-treating it, and the surface of an inorganic material such as glass or ceramics. Various studies have been carried out to improve the properties of the surface by treating various kinds of surface treatment agents to improve the performance and expand the range of application. As one of them, there has been proposed a method in which an originally hydrophilic surface is treated with a water repellent agent such as a silicone-based composition so as to be modified into a water repellent surface.
No. 29024 discloses a water repellent treatment agent for glass comprising a silane having a perfluoroalkyl group, an acid, and a nonpolar organic solvent, and JP-A-2-233535 discloses a silane having a perfluoroalkyl group. , A surface treatment of a glass comprising an organopolysiloxane, an acid, and a volatile organic solvent is disclosed in Japanese Patent Application Laid-Open No. 4-144940.
The publication discloses a water / oil repellent composition comprising an organopolysiloxane, a perfluoroalkyl group-containing silane or siloxane, and an acid.
【０００３】更に特公平７−６３６７０号公報にはフル
オロアルキル基を含有するクロロシラン化合物をヘキサ
デカン、四塩化炭素、クロロホルムなどの非水系溶媒に
溶解して調製した吸着用液にガラスを浸漬する方法など
が示されている。Further, Japanese Patent Publication No. 7-63670 discloses a method of immersing glass in an adsorption liquid prepared by dissolving a chlorosilane compound containing a fluoroalkyl group in a non-aqueous solvent such as hexadecane, carbon tetrachloride or chloroform. It is shown.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、特公昭
５５−２９０２４号、特開平２−２３３５３５号および
特開平４−１４４９４０号公報では、塗布した後に過剰
の撥水剤を除去するのに手間がかかり、作業性に劣るな
どの欠点を有していた。However, in JP-B-55-29024, JP-A-2-233535 and JP-A-4-144940, it takes time and effort to remove an excess water repellent after coating. However, it had the drawback of being inferior in workability.
【０００５】特公平７−６３６７０号公報では溶媒中に
含まれる微量の水分によりクロロシラン化合物が自己縮
合してしまい、基材表面との反応性が低下するので、溶
媒に予め十分な脱水処理を行う必要があり、また反応工
程中は３５％以下の相対湿度を有する乾燥雰囲気環境を
必要とするため、建築用、自動車用ガラスなどの大きさ
を処理する場合には大がかりな設備が必要になり、更に
クロロシラン化合物の濃度を低く保つ化学吸着方式であ
るため浸漬処理時間を大きくする必要があり、生産性が
低いものであった。According to Japanese Patent Publication No. 7-63670, a chlorosilane compound self-condenses due to a small amount of water contained in the solvent, and the reactivity with the surface of the base material is lowered. In addition, since a dry atmosphere environment having a relative humidity of 35% or less is required during the reaction process, large-scale equipment is required when processing the size of glass for buildings and automobiles. Furthermore, since it is a chemical adsorption method that keeps the concentration of the chlorosilane compound low, it is necessary to lengthen the immersion treatment time, resulting in low productivity.
【０００６】本発明はこのような欠点を改良し、優れた
撥水性、防汚性を与えることができ、かつ処理時間も短
く撥水処理の作業性に優れた撥水処理剤およびその製造
方法を提供することを目的とする。The present invention has improved such drawbacks, provided excellent water repellency and antifouling property, and has a short treatment time and excellent workability in water repellent treatment, and a method for producing the same. The purpose is to provide.
【０００７】[0007]
【課題を解決するための手段】本発明は、アルコキシ基
またはアシロキシ基とフルオロアルキル基を有する有機
ケイ素化合物および／またはその加水分解物ならびに有
機溶媒を含有する撥水処理剤において、前記有機ケイ素
化合物および／またはその加水分解物が０．０１〜０．
１重量％の濃度で含有され、かつ前記有機溶媒が非極性
溶媒を５０〜９９．９５重量％含有することを特徴とす
る撥水処理剤である。The present invention provides a water repellent treatment agent containing an organic silicon compound having an alkoxy group or an acyloxy group and a fluoroalkyl group and / or a hydrolyzate thereof, and an organic solvent. And / or its hydrolyzate is from 0.01 to 0.
A water repellent agent, characterized in that it is contained at a concentration of 1% by weight, and the organic solvent contains a nonpolar solvent in an amount of 50 to 99.95% by weight.
【０００８】本発明の撥水処理剤において用いられるア
ルコキシ基またはアシロキシ基とフルオロアルキル基を
有する有機ケイ素化合物としては、アルコキシ基または
アシロキシ基を含有するフルオロアルキルシラン化合
物、アルコキシ基またはアシロキシ基とフルオロアルキ
ル基を有するシロキサン化合物が挙げられる。アルコキ
シ基またはアシロキシ基を有するフルオロアルキルシラ
ン化合物としては、１分子中にフルオロアルキル基とア
ルコキシ基またはアシロキシ基を有するシランであれば
特に限定されないが、下記式（１）で示されるフルオロ
アルキルシラン化合物が好ましい。 Ｒf（ＣＨ2）2Ｓi（ＣＨ3）p（Ｚ）3-p （１）The organosilicon compound having an alkoxy group or an acyloxy group and a fluoroalkyl group used in the water repellent agent of the present invention includes a fluoroalkylsilane compound having an alkoxy group or an acyloxy group, an alkoxy group or an acyloxy group and a fluoro group. Examples thereof include siloxane compounds having an alkyl group. The fluoroalkylsilane compound having an alkoxy group or an acyloxy group is not particularly limited as long as it is a silane having a fluoroalkyl group and an alkoxy group or an acyloxy group in one molecule, but a fluoroalkylsilane compound represented by the following formula (1) Is preferred. Rf (CH 2 ) 2 Si (CH 3 ) p (Z) 3-p (1)
【０００９】式（１）中のＲf は、炭素数が３〜２０、
好ましくは炭素数が６から１０のパーフルオロアルキル
基であり、アルコキシ基またはアシロキシ基Ｚは、−Ｏ
ＣＨ3、ＯＣ2Ｈ5、−ＯＣ3Ｈ6、−ＯＣ4Ｈ9、−ＯＣＯ
ＣＨ3、−ＯＣＯＣ2Ｈ5等が例示され、好ましくは−Ｏ
ＣＨ3，−ＯＣ2Ｈ5 で表されるアルコキシ基である。ｐ
は０、１または２であり、０、１が好ましい。このフル
オロアルキルシラン化合物としては、例えばヘプタデカ
フルオロデシルトリメトキシシラン ＣＦ3（ＣＦ2）
7（ＣＨ2）2Ｓi（ＯＣＨ3）3、 ヘプタデカフルオロデ
シルメチルジメトキシシラン ＣＦ3（ＣＦ2）7（Ｃ
Ｈ2）2ＳiＣＨ3（ＯＣＨ3）2 などが挙げられ、特にＣ
Ｆ3（ＣＦ2）7（ＣＨ2）2Ｓi（ＯＣＨ3）3が好ましい。Rf in the formula (1) has 3 to 20 carbon atoms,
Preferably, it is a perfluoroalkyl group having 6 to 10 carbon atoms, and the alkoxy group or acyloxy group Z is -O.
CH 3, OC 2 H 5, -OC 3 H 6, -OC 4 H 9, -OCO
CH 3, is exemplified -OCOC 2 H 5, etc., preferably -O
CH 3, an alkoxy group represented by -OC 2 H 5. p
Is 0, 1 or 2, with 0 and 1 being preferred. Examples of the fluoroalkylsilane compound include heptadecafluorodecyltrimethoxysilane CF 3 (CF 2 ).
7 (CH 2 ) 2 Si (OCH 3 ) 3 , heptadecafluorodecylmethyldimethoxysilane CF 3 (CF 2 ) 7 (C
H 2 ) 2 SiCH 3 (OCH 3 ) 2 and the like, particularly C
F 3 (CF 2 ) 7 (CH 2 ) 2 Si (OCH 3 ) 3 is preferred.
【００１０】本発明の撥水処理剤においては、有機ケイ
素化合物および／またはその加水分解物が撥水処理剤中
に、０．０１〜０．１重量％、好ましくは０．０２〜
０．０９重量％の濃度で含有することが重要であり、
０．０１重量％より少なくても０．１重量％より多くて
も撥水性と作業性の両方を満足させることができない。In the water repellent agent of the present invention, the organosilicon compound and / or its hydrolyzate is contained in the water repellent agent in an amount of 0.01 to 0.1% by weight, preferably 0.02 to 0.1% by weight.
It is important to contain at a concentration of 0.09% by weight,
If it is less than 0.01% by weight or more than 0.1% by weight, both water repellency and workability cannot be satisfied.
【００１１】本発明の撥水処理剤は、有機ケイ素化合物
および／またはその加水分解物を有機溶媒と混合するだ
けでも良いが、アルコキシ基またはアシロキシ基を有す
る有機ケイ素化合物を水、触媒と共に、これらを溶解す
ることができる溶媒中で加水分解したものを用いること
が好ましい。The water repellent treatment agent of the present invention may be prepared by mixing the organic silicon compound and / or its hydrolyzate with an organic solvent. However, the organic silicon compound having an alkoxy group or an acyloxy group is used together with water and a catalyst. It is preferable to use a hydrolyzed product in a solvent capable of dissolving
【００１２】加水分解を行う際の溶媒は、極性溶媒が好
ましく、例えば、メタノール、エタノール、ｉ−プロパ
ノール、ｎ−プロパノール、ｎ−ブタノール、ｉ−ブタ
ノール、ｓ−ブタノール、ｔ−ブタノール等のアルコー
ル類、メチルセロソルブ、エチルセロソルブ、ブチルセ
ロソルブ、酢酸セロソルブ等のセロソルブ類、アセト
ン、メチルエチルケトン等のケトン類、ジオキサン、テ
トラヒドロフラン等のエーテル類などが挙げられる。使
用する極性性溶媒の量は有機ケイ素化合物１重量部に対
して通常１〜５０重量部であり、有機ケイ素化合物、
水、および触媒を溶解することができる必要最小限度に
できるだけ近い少量を使用することが好ましい。The solvent used for the hydrolysis is preferably a polar solvent, for example, alcohols such as methanol, ethanol, i-propanol, n-propanol, n-butanol, i-butanol, s-butanol and t-butanol. , Methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate and the like, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, and the like. The amount of the polar solvent used is usually 1 to 50 parts by weight with respect to 1 part by weight of the organosilicon compound.
It is preferred to use water, and a small amount as close as possible to the minimum needed to dissolve the catalyst.
【００１３】添加する水の量としては有機ケイ素化合物
中のアルコキシ基またはアシロキシ基のモル数に対して
０．１〜１０当量、好ましくは０．５〜２当量が適当で
ある。０．１当量未満の場合は加水分解の割合が不十分
であるため被処理面との反応性が弱くなる場合があり、
１０当量を越えても意味がない。The amount of water added is appropriately 0.1 to 10 equivalents, preferably 0.5 to 2 equivalents, relative to the number of moles of alkoxy groups or acyloxy groups in the organosilicon compound. If the amount is less than 0.1 equivalent, the reactivity with the surface to be treated may be weakened because of insufficient hydrolysis rate.
It does not make sense to exceed 10 equivalents.
【００１４】本発明での加水分解反応の触媒として酸ま
たは塩基性触媒が用いられるが、酸が使用されることが
多く、酸の例としては塩酸、硫酸、硝酸、ギ酸、酢酸、
シュウ酸、メタンスルホン酸、トリフロロメタンスルホ
ン酸，ｐ−トルエンスルホン酸、トリクロロ酢酸、リン
酸等が挙げられる。触媒の使用量は前記有機ケイ素化合
物に対して０．１〜２００重量％である。An acid or a basic catalyst is used as a catalyst for the hydrolysis reaction in the present invention, and an acid is often used. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid,
Examples thereof include oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, trichloroacetic acid and phosphoric acid. The amount of the catalyst used is 0.1 to 200% by weight based on the organosilicon compound.
【００１５】加水分解反応は、特に限定されないが、通
常室温〜１００℃程度の温度下で１分〜１０日間程度の
時間で行う。The hydrolysis reaction is not particularly limited, but is usually carried out at a temperature of room temperature to 100 ° C. for about 1 minute to 10 days.
【００１６】本発明においては、有機ケイ素化合物およ
び／またはその加水分解物以外にフルオロアルキル基を
有さないオルガノポリシロキサン化合物を添加してもよ
い。オルガノポリシロキサン化合物としては、直鎖また
は分鎖状で、ヒドロキシ基またはアルコキシ基、アミノ
基などの加水分解性基を含有するオルガノポリシロキサ
ン化合物が用いられる。以下にその例を示す。In the present invention, an organopolysiloxane compound having no fluoroalkyl group may be added in addition to the organosilicon compound and / or its hydrolyzate. As the organopolysiloxane compound, a linear or branched organopolysiloxane compound having a hydrolyzable group such as a hydroxy group, an alkoxy group, or an amino group is used. An example is shown below.
【００１７】[0017]
【化１】 Embedded image
【化２】 Embedded image
【化３】 Embedded image
【化４】 Embedded image
【００１８】ただし、上記化学式中で、ｒは１〜１００
の整数である。また、ｍは３〜１００の整数、ｎは０ま
たは１〜５０の整数で、かつ５≦ｍ＋ｎ≦１００であ
る。However, in the above chemical formula, r is 1 to 100.
Is an integer. Further, m is an integer of 3 to 100, n is 0 or an integer of 1 to 50, and 5 ≦ m + n ≦ 100.
【００１９】本発明において、オルガノポリシロキサン
化合物は、被撥水処理面との反応性があまり高くないの
で、上記の有機ケイ素化合物の加水分解の際に予め添加
して有機ケイ素化合物と共加水分解することが好まし
い。共加水分解することによってオルガノポリシロキサ
ン化合物の反応性が高めることができる。In the present invention, since the organopolysiloxane compound has not so high reactivity with the surface to be treated for water repellency, it is added in advance during the hydrolysis of the above organosilicon compound and cohydrolyzed with the organosilicon compound. Preferably. The co-hydrolysis can increase the reactivity of the organopolysiloxane compound.
【００２０】オルガノポリシロキサン化合物の添加量と
しては、重量比で有機ケイ素化合物１００重量部に対
し、０〜２００重量部の範囲が好ましい。この範囲を越
えると、有機ケイ素化合物の反応性が低下してしまい、
撥水処理すべき基材表面への吸着性能が不十分となる。The addition amount of the organopolysiloxane compound is preferably in the range of 0 to 200 parts by weight based on 100 parts by weight of the organosilicon compound. If this range is exceeded, the reactivity of the organosilicon compound will decrease,
Adsorption performance on the surface of the substrate to be water repellent is insufficient.
【００２１】次に前記の方法で極性溶媒中で加水分解さ
れた有機ケイ素化合物および／またはその加水分解物溶
液を非極性溶媒で希釈して撥水処理剤とする。この撥水
処理剤中の全有機溶媒中の非極性溶媒の比率が５０重量
％〜９９．９５重量％になるように配合することが重要
である。この非極性溶媒の比率は好ましくは９５重量％
〜９９．９５重量％、更に好ましくは９９．０重量％〜
９９．９５重量％である。非極性溶媒が５０重量％より
少ないと撥水性が不十分となることがあり、９９．９５
重量％より多いと被処理物への吸着性が悪くなる。非極
性溶媒の例としては、ｎ−ペンタン、ｉ−ペンタン、ｎ
−ヘキサン、シクロヘキサン、ｎ−オクタン、ｉ−オク
タン等の炭化水素；四塩化炭素、クロロホルム、Ｃ6Ｆ
14、Ｃ8Ｆ18等のハロゲン化炭化水素；トルエン、キシ
レン、ヘキサフルオロ−ｍ−キシレン等の芳香族炭化水
素などが挙げられる。Next, the solution of the organosilicon compound and / or its hydrolyzate hydrolyzed in the polar solvent by the above-mentioned method is diluted with a nonpolar solvent to obtain a water repellent treatment agent. It is important to mix the water repellent agent such that the proportion of the nonpolar solvent in all the organic solvents is 50% by weight to 99.95% by weight. The proportion of this non-polar solvent is preferably 95% by weight
~ 99.95% by weight, more preferably 99.0% by weight ~
It is 99.95% by weight. If the amount of the non-polar solvent is less than 50% by weight, the water repellency may be insufficient, resulting in 99.95.
If it exceeds 5% by weight, the adsorptivity to the object to be treated becomes poor. Examples of non-polar solvents include n-pentane, i-pentane, n
- hexane, cyclohexane, n- octane, hydrocarbons i- octane; carbon tetrachloride, chloroform, C 6 F
14, halogenated hydrocarbons such as C 8 F 18; toluene, xylene, and aromatic hydrocarbons such as hexafluoro -m- xylene.
【００２２】また本発明において、有機ケイ素化合物の
加水分解用の触媒とは別に、非極性溶媒で希釈する際に
酸などの触媒を添加してもよい。この時の触媒は被撥水
処理材表面のＯＨ基と有機ケイ素化合物および／または
その加水分解物の脱水縮合反応の触媒として作用する。
この場合の酸の例としては加水分解用の触媒と同様、塩
酸、硫酸、硝酸、ギ酸、酢酸、シュウ酸、メタンスルホ
ン酸、トリフロロメタンスルホン酸，ｐ−トルエンスル
ホン酸、トリクロロ酢酸、リン酸等が挙げられる。この
触媒の添加量は撥水処理剤に対して１０-5〜１重量％で
あるのが望ましい。In the present invention, in addition to the catalyst for hydrolysis of the organosilicon compound, a catalyst such as an acid may be added when it is diluted with a nonpolar solvent. At this time, the catalyst acts as a catalyst for the dehydration condensation reaction of the OH group on the surface of the water repellent material with the organic silicon compound and / or its hydrolyzate.
Examples of the acid in this case include hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, as in the case of the catalyst for hydrolysis. Etc. The amount of this catalyst added is preferably 10 −5 to 1% by weight with respect to the water repellent agent.
【００２３】本発明の撥水処理剤の配合およびその製造
方法の好ましい例は下記表１の通りである。ただし、
（Ａ）〜（Ｅ）を加水分解させた後、非極性溶媒を添加
する。The preferred examples of the blending of the water repellent agent of the present invention and the method for producing the same are as shown in Table 1 below. However,
After hydrolyzing (A) to (E), a nonpolar solvent is added.
【００２４】[0024]
【表１】 （Ａ）フルオロアルキルシラン化合物 ０．０１〜０．１重量部 （Ｂ）水 ０．００１〜０．１重量部 （Ｃ）酸または塩基性触媒 １０-5〜１重量部 （Ｄ）オルガノポリシロキサン化合物 ０〜０．１重量部 （Ｅ）極性溶媒 ０．１〜５０重量部 非極性溶媒 ５０〜９９．９重量部 （ただし合計１００重量部）Table 1 (A) Fluoroalkylsilane compound 0.01 to 0.1 part by weight (B) Water 0.001 to 0.1 part by weight (C) Acid or basic catalyst 10 -5 to 1 part by weight (D ) Organopolysiloxane compound 0 to 0.1 part by weight (E) polar solvent 0.1 to 50 parts by weight non-polar solvent 50 to 99.9 parts by weight (however, 100 parts by weight in total)
【００２５】本発明において、非極性溶媒を用いること
により、短時間の浸漬処理で優れた撥水性能が得られる
理由は、以下のように推定される。加水分解された有機
ケイ素化合物および／またはその加水分解物は親水性を
有する部分と疎水性を有するフルオロアルキル基からな
る。この有機ケイ素化合物および／またはその加水分解
物を含有する撥水処理剤とガラスなどの親水性表面を有
する被撥水処理基材を接触させる際、もし撥水処理剤の
溶媒に親水性溶媒を用いた場合、親水性溶媒は、有機ケ
イ素化合物および／またはその加水分解物に優先して、
親水性である被撥水処理面に吸着し易く、そのため有機
ケイ素化合物および／またはその加水分解物と被撥水処
理面の反応が阻害される傾向がある。または、有機ケイ
素化合物および／またはその加水分解物は親水性溶媒中
で安定に存在するので、親水性溶媒中を移動して被撥水
処理面の方に向かう誘引力が働かないのかも知れない。
それに対して、非極性溶媒は被撥水処理面に吸着し難
く、そして親水性溶媒中であれば安定に存在する有機ケ
イ素化合物の加水分解物は多量の非極性溶媒中では安定
な状態で存在せず、より安定な状態になる被撥水処理面
の親水性表面に近づいて親水性表面と反応しやすくなる
と考えられる。親水性溶媒よりも多量に存在する非極性
溶媒は、親水性溶媒が被撥水処理面に吸着するための移
動を妨げ、被撥水処理面には有機ケイ素化合物の加水分
解物が優先して吸着することになる。In the present invention, the reason why the excellent water repellent performance can be obtained by the immersion treatment for a short time by using the non-polar solvent is presumed as follows. The hydrolyzed organosilicon compound and / or its hydrolyzate is composed of a hydrophilic portion and a hydrophobic fluoroalkyl group. When a water repellent treatment agent containing this organosilicon compound and / or its hydrolyzate is brought into contact with a water repellent treated substrate having a hydrophilic surface such as glass, a hydrophilic solvent is added to the solvent of the water repellent treatment agent. When used, the hydrophilic solvent takes precedence over the organosilicon compound and / or its hydrolyzate,
It tends to be adsorbed on the hydrophilic surface to be treated, and therefore the reaction between the organosilicon compound and / or its hydrolyzate and the treated surface tends to be hindered. Alternatively, since the organosilicon compound and / or its hydrolyzate are stably present in the hydrophilic solvent, the attractive force of moving in the hydrophilic solvent toward the water-repellent treated surface may not work. .
On the other hand, non-polar solvents are difficult to adsorb on the surface to be treated, and hydrolyzates of organosilicon compounds that are stable in hydrophilic solvents are stable in large amounts of non-polar solvents. It is considered that the hydrophilic surface of the surface to be treated to be rendered more stable becomes closer to the hydrophilic surface and becomes more likely to react with the hydrophilic surface. The non-polar solvent that is present in a larger amount than the hydrophilic solvent prevents the hydrophilic solvent from moving to be adsorbed on the water-repellent treated surface, and the hydrolyzate of the organosilicon compound has priority on the water-repellent treated surface. It will be adsorbed.
【００２６】本発明の撥水処理剤を用いて撥水処理を行
う被撥水処理基板は、建築、自動車、車両、航空機ある
いは船舶などの風防ガラス、光学部品レンズその他のガ
ラス製品等の透明物品またはセラミックスなどの不透明
物品の親水性表面などである。撥水処理すべき基材を上
記の撥水処理剤と所定時間、通常は１秒〜３分間接触さ
せることにより、撥水処理剤中の有機ケイ素化合物の加
水分解物が基材表面に吸着する。この接触は例えば撥水
処理剤の中に撥水処理すべき基材を浸漬させることによ
りなされる。この場合、撥水処理剤の浴の必要な容積
は、撥水処理剤中の有機ケイ素化合物の加水分解物の濃
度にも依存するが、撥水処理すべき基材の表面積１ｍ2
あたり５００〜２００００ｃｍ3である。また撥水処理
剤の浴は、浴中の有機ケイ素化合物の加水分解物の濃度
がかなり低下するまで、複数回繰り返して使用すること
ができる。撥水処理剤の浴から基材を引き出し、乾燥
し、必要に応じて更に８０〜３００℃で１〜１０分間加
熱することにより撥水性物品が得られる。ガラス基材な
どに処理する場合、その表面にＳiＯ2膜、ＳiＯ2−Ｚr
Ｏ2膜などの金属酸化物薄膜をコーティングしたガラス
基板上に撥水処理することもできる。表面に微細な凹凸
形状を形成したものに処理してもよい。The water-repellent substrate to be subjected to the water-repellent treatment using the water-repellent treatment agent of the present invention is a transparent glass article such as a windshield for construction, automobiles, vehicles, aircraft or ships, optical parts lens and other glass products. Or the hydrophilic surface of an opaque article such as ceramics. The hydrolyzate of the organosilicon compound in the water repellent agent is adsorbed on the surface of the substrate by contacting the substrate to be water repellent with the above water repellent agent for a predetermined time, usually 1 second to 3 minutes. . This contact is made, for example, by immersing the substrate to be treated for water repellency in a water repellent agent. In this case, the required volume of the water-repellent agent bath depends on the concentration of the hydrolyzate of the organosilicon compound in the water-repellent agent, but the surface area of the substrate to be water-repellent is 1 m 2
It is 500 to 20000 cm 3 . Further, the bath of the water repellent agent can be repeatedly used a plurality of times until the concentration of the hydrolyzate of the organosilicon compound in the bath is considerably reduced. The water-repellent article is obtained by pulling out the substrate from the bath of the water repellent treatment agent, drying it, and further heating it at 80 to 300 ° C. for 1 to 10 minutes if necessary. When processing on a glass substrate, etc., a SiO 2 film or SiO 2 -Zr is formed on the surface.
Water repellent treatment can also be performed on a glass substrate coated with a metal oxide thin film such as an O 2 film. You may process it to what formed the fine uneven shape on the surface.
【００２７】上記の撥水処理剤浴の浸漬吸着の代わり
に、撥水処理すべき基材表面に撥水処理剤を少量滴下し
て、それを刷毛を用いて基材表面全面にのばし、乾燥し
て撥水処理ガラスを得ることもできる。また基材を水
平、斜め、または鉛直方向に保持して、その表面に撥水
処理剤を流し掛けることもできる。この場合、掛けられ
た撥水処理剤中で消費される有機ケイ素化合物および／
またはその加水分解物はわずかであるので、流れ出た余
剰の撥水処理剤は回収して繰り返し再使用することもで
きる。Instead of dipping and adsorption in the water repellent treatment bath described above, a small amount of the water repellent treatment agent is dropped on the surface of the base material to be treated for water repellent treatment, and this is spread on the entire surface of the base material using a brush and dried. It is also possible to obtain a water-repellent treated glass. It is also possible to hold the substrate horizontally, obliquely, or vertically and pour the water repellent treatment agent on the surface thereof. In this case, the organosilicon compound consumed in the applied water repellent and /
Alternatively, since the amount of the hydrolyzed product is small, the excess water repellent agent that has flowed out can be recovered and reused repeatedly.
【００２８】[0028]
【発明の実施の形態】以下、本発明を実施例によって更
に詳細に説明するが、本発明はこれら実施例に限定され
るものではない。 ＜評価および試験方法＞ １）接触角 ：接触角計（協和界面科学（株）製ＣＡ−
Ｄ）を用い、静滴法により水の接触角を測定した。１サ
ンプルにつき５箇所測定し、平均値を接触角の値とし
た。 ２）耐煮沸性：沸騰水中にサンプルを４時間浸漬した
後、水の接触角を測定した。 ３）耐摩耗性：新東科学製ＨＥＩＤＯＮ−１８を用い
て、ネル布を３００ｇ／ｃｍ2 の荷重で押しつけ、７２
００ｍｍ／分の速度で５０００往復摩耗した後、水の接
触角を測定した。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. <Evaluation and test method> 1) Contact angle: Contact angle meter (CA- manufactured by Kyowa Interface Science Co., Ltd.)
Using D), the contact angle of water was measured by the sessile drop method. Five points were measured for each sample, and the average value was used as the contact angle value. 2) Boiling resistance: After immersing the sample in boiling water for 4 hours, the contact angle of water was measured. 3) Abrasion resistance: HEIDON-18 manufactured by Shinto Kagaku Co., Ltd. was used to press a flannel cloth with a load of 300 g / cm 2 and then 72
The contact angle of water was measured after 5,000 reciprocating abrasions at a speed of 00 mm / min.
【００２９】実施例１ 厚み３ｍｍ、１５０ｍｍ×１５０ｍｍのソーダ石灰珪酸
塩系ガラス（フロート板ガラス）基板表面を酸化セリウ
ム系微粒子を含む研磨剤（ＨＳ−３、新日金化学（株）
製）で研磨洗浄し、純水ですすいで風乾し洗浄済みガラ
ス基板を得た。以下の実施例、比較例ではこの洗浄済み
ガラスを用いる。Example 1 A soda lime silicate glass (float plate glass) having a thickness of 3 mm and a size of 150 mm × 150 mm, an abrasive containing cerium oxide fine particles on the surface of the substrate (HS-3, manufactured by Nippon Steel Chemical Co., Ltd.)
Polishing), rinsed with pure water and air-dried to obtain a washed glass substrate. This cleaned glass is used in the following examples and comparative examples.
【００３０】ヘプタデカフルオロデシルトリメトキシシ
ラン（化学式ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓi（ＯＣ
Ｈ3）3）２重量部をｔ−ブタノール３２重量部に溶解し
た。これに０．１Ｎ塩酸０．４６ｇを添加し、２０℃で
２４時間攪拌し加水分解し、さらにｎ−ヘキサン６４重
量部を添加し撥水処理剤原液を得た。この撥水処理剤原
液をシクロヘキサンで重量比で１００倍に希釈して撥水
処理剤を調合した。非極性溶媒（ｎ−ヘキサンおよびシ
クロヘキサン）はこれと極性溶媒（ｔ−ブタノール）と
の合計に対して９９．６８重量％含有されている。そし
て撥水処理剤中のヘプタデカフルオロデシルトリメトキ
シシランの加水分解物の濃度は約０．０２重量％であっ
た。Heptadecafluorodecyltrimethoxysilane (chemical formula CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OC
H 3) 3) 2 parts by weight was dissolved in t- butanol 32 parts by weight. 0.46 g of 0.1N hydrochloric acid was added thereto, and the mixture was stirred at 20 ° C. for 24 hours for hydrolysis, and 64 parts by weight of n-hexane was further added to obtain a water repellent treatment stock solution. This stock solution of water-repellent agent was diluted with cyclohexane 100 times by weight to prepare a water-repellent agent. The non-polar solvent (n-hexane and cyclohexane) is contained in 99.68% by weight based on the total amount of the non-polar solvent and the polar solvent (t-butanol). The concentration of the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent treatment was about 0.02% by weight.
【００３１】この撥水処理剤約８００ｃｍ3 の浴中に、
洗浄済みガラスを浸漬し、約３秒後に引き上げて乾燥
後、さらに１００℃，２０分の加熱を行い撥水処理ガラ
スを得た。この撥水ガラスは透明性も良く、余分な撥水
剤の付着はほとんど認められなかった。このようにして
得られた撥水処理ガラスの水に対する接触角は１０４度
であった。またこれらの撥水処理ガラスの耐摩耗性試験
後の接触角は９３度を示し、耐久性能にも優れているこ
とが示された。In a bath of about 800 cm 3 of this water repellent treatment agent,
The washed glass was dipped, and after about 3 seconds, pulled up and dried, and further heated at 100 ° C. for 20 minutes to obtain a water-repellent treated glass. The water-repellent glass also had good transparency, and almost no extra water-repellent was attached. The contact angle of water of the water-repellent treated glass thus obtained was 104 degrees. In addition, the contact angle of these water-repellent treated glasses after the abrasion resistance test was 93 degrees, showing that they were also excellent in durability performance.
【００３２】実施例２ 実施例１で調合した撥水処理剤原液をシクロヘキサンで
それぞれ重量比で３０倍、８０倍、１１０倍に希釈し３
種類の撥水処理剤を調合した。非極性溶媒（ｎ−ヘキサ
ンおよびシクロヘキサン）はこれと極性溶媒（ｔ−ブタ
ノール）との合計に対して上記希釈度に対応してそれぞ
れ９８．９５重量％、９９．４７重量％および９９．７
１重量％含有されている。そして撥水処理剤中のヘプタ
デカフルオロデシルトリメトキシシランの加水分解物の
濃度は上記希釈度に対応してそれぞれ約０．０７重量
％、０．０３重量％および０．０２重量％であった。Example 2 The stock solution of the water repellent agent prepared in Example 1 was diluted with cyclohexane to a weight ratio of 30 times, 80 times, and 110 times, respectively.
Various types of water repellent treatments were prepared. The non-polar solvent (n-hexane and cyclohexane) corresponds to the above dilution degree with respect to the sum of this and the polar solvent (t-butanol), respectively. 98.95% by weight, 99.47% by weight and 99.7% by weight, respectively.
It is contained by 1% by weight. The concentrations of the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent treatment were about 0.07% by weight, 0.03% by weight and 0.02% by weight, respectively, corresponding to the above dilution degree. .
【００３３】この３種類の撥水処理剤各約８００ｃｍ3
の浴中に、それぞれ洗浄済みガラスを浸漬し、約３秒後
に引き上げて撥水処理ガラスを得た。この撥水ガラスは
透明性も良く、余分な撥水剤の付着はほとんど認められ
なかった。Each of these three types of water repellent treatment agents is approximately 800 cm 3
The washed glass was immersed in each of the baths, and after about 3 seconds, it was pulled up to obtain a water-repellent treated glass. The water-repellent glass also had good transparency, and almost no extra water-repellent was attached.
【００３４】このようにして得られた、シクロヘキサン
で３０倍、８０倍、および１１０倍に希釈した３種類の
撥水処理剤で処理した撥水ガラスの水に対する接触角は
それぞれ１０５度、１０５度、および１０４度であっ
た。またこれらの撥水処理ガラスの耐摩耗性試験後の接
触角はそれぞれ、９５、９３、および９３度を示し、耐
久性能にも優れていることが示された。The contact angles of water of the water-repellent glass thus treated with three kinds of water-repellent treatment agents diluted with cyclohexane to 30 times, 80 times and 110 times are 105 ° and 105 °, respectively. , And 104 degrees. Further, the contact angles of these water-repellent treated glasses after the abrasion resistance test were 95, 93, and 93 degrees, respectively, showing that they were also excellent in durability performance.
【００３５】実施例３ ヘプタデカフルオロデシルトリメトキシシラン（化学式
ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓi（ＯＣＨ3）3）２重量部
をｔ−ブタノール３２重量部に溶解した。これに０．１
Ｎ塩酸０．４６ｇを添加し、２０℃で２４時間攪拌し加
水分解し、さらにｎ−ヘキサン６４重量部を添加し撥水
処理剤原液を得た。この撥水処理剤原液を四塩化炭素、
トルエン、およびｍ−キシレンを用いて重量比１００倍
に希釈し３種類の撥水処理剤を調合した。非極性溶媒
（ｎ−ヘキサン、四塩化炭素、トルエン、およびｍ−キ
シレン）はこれと極性溶媒（ｔ−ブタノール）との合計
に対して９９．６８重量％含有されている。そして撥水
処理剤中のヘプタデカフルオロデシルトリメトキシシラ
ンの加水分解物の濃度は約０．０２重量％であった。Example 3 2 parts by weight of heptadecafluorodecyltrimethoxysilane (chemical formula CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 ) was dissolved in 32 parts by weight of t-butanol. 0.1
0.46 g of N hydrochloric acid was added, and the mixture was stirred at 20 ° C. for 24 hours for hydrolysis, and 64 parts by weight of n-hexane was further added to obtain a water repellent treatment stock solution. This water repellent treatment stock solution is carbon tetrachloride,
Three types of water repellent treatment agents were prepared by diluting with toluene and m-xylene to a weight ratio of 100 times. The nonpolar solvent (n-hexane, carbon tetrachloride, toluene, and m-xylene) is contained in 99.68% by weight based on the total amount of the nonpolar solvent and the polar solvent (t-butanol). The concentration of the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent treatment was about 0.02% by weight.
【００３６】１５０ｍｍ×１５０ｍｍで厚み３ｍｍの洗
浄済みガラスに、上記の３種類の撥水処理剤を５ｃｃず
つ滴下し、刷毛を用いてガラス全面にのばしながら乾燥
させてそれぞれ撥水処理ガラスを得た。これらの撥水処
理ガラスはいずれも透明性も良く、余分な撥水剤の付着
は認められなかった。四塩化炭素、トルエン、およびｍ
−キシレンを用いて希釈した３種類の撥水処理剤で処理
した撥水ガラスの接触角はそれぞれ１０３、１０４、お
よび１０４度を示した。5 cc of each of the above three kinds of water repellent treatment agents was dropped onto a washed glass having a size of 150 mm × 150 mm and a thickness of 3 mm, and dried while being spread on the entire surface of the glass with a brush to obtain each water repellent treatment glass. . All of these water-repellent treated glasses had good transparency, and no extra water-repellent was attached. Carbon tetrachloride, toluene, and m
-The contact angles of the water repellent glass treated with the three types of water repellent treatment diluted with xylene were 103, 104, and 104 degrees, respectively.
【００３７】実施例４ ヘプタデカフルオロデシルトリメトキシシラン（化学式
ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓi（ＯＣＨ3）3）２重量部
と末端シラノール変性ジメチルシロキサン（平均分子量
１７００）２重量部をｔ−ブタノール３２重量部に溶解
した。０．１Ｎ塩酸０．４６ｇを添加し、２０℃で２４
時間攪拌し加水分解し、さらにｎ−ヘキサン６４重量部
を添加し撥水処理剤原液を得た。この撥水処理剤原液を
シクロヘキサンで重量比で１００倍に希釈し撥水処理剤
を得た。非極性溶媒（ｎ−ヘキサンおよびシクロヘキサ
ン）はこれと極性溶媒（ｔ−ブタノール）との合計に対
して９９．６８重量％含有されている。そして撥水処理
剤中のヘプタデカフルオロデシルトリメトキシシランの
加水分解物および末端シラノール変性ジメチルシロキサ
ンの濃度はそれぞれ約０．０２重量％であった。Example 4 2 parts by weight of heptadecafluorodecyltrimethoxysilane (chemical formula CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 ) and 2 parts by weight of terminal silanol-modified dimethylsiloxane (average molecular weight 1700). Was dissolved in 32 parts by weight of t-butanol. Add 0.46 g of 0.1N hydrochloric acid and add 24 at 20 ° C.
The mixture was stirred for hydrolysis for a period of time, and 64 parts by weight of n-hexane was added to obtain a water repellent treatment stock solution. This stock solution of water repellent treatment was diluted with cyclohexane 100 times by weight to obtain a water repellent treatment. The non-polar solvent (n-hexane and cyclohexane) is contained in 99.68% by weight based on the total amount of the non-polar solvent and the polar solvent (t-butanol). The concentrations of the hydrolyzate of heptadecafluorodecyltrimethoxysilane and the terminal silanol-modified dimethylsiloxane in the water repellent agent were each about 0.02% by weight.
【００３８】１５０ｍｍ×１５０ｍｍで厚み３ｍｍの洗
浄済みガラスに、この撥水処理剤を５ｃｃ滴下し、刷毛
を用いてガラス全面にのばしながら乾燥させて撥水処理
ガラスを得た。この撥水処理ガラスは透明性も良く、余
分な撥水剤の付着は認められなかった。この撥水処理ガ
ラスの接触角は１０４度を示した。5 cc of this water repellent treatment agent was dropped on a washed glass having a size of 150 mm × 150 mm and a thickness of 3 mm, and the water repellent treatment glass was obtained by drying while spreading the entire surface of the glass with a brush. This water-repellent treated glass had good transparency, and no excessive water-repellent agent was attached. The contact angle of this water-repellent treated glass was 104 degrees.
【００３９】実施例５ ヘプタデカフルオロデシルトリメトキシシラン（化学式
ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓi（ＯＣＨ3）3）２．７３
重量部をｔ−ブタノール４．６６重量部に溶解した。
０．１Ｎ塩酸０．６８ｇを添加し、２０℃で４日間攪拌
し加水分解し、さらにｎ−ヘキサン６４重量部を添加し
撥水処理剤原液を得た。この撥水処理剤原液を、それぞ
れ重量比１／９９、５／９５、３０／７０、および５０
／５０で混合したｔ−ブタノール／シクロヘキサン溶液
で重量比で１００倍に希釈し４種の撥水処理剤を得た。
非極性溶媒（ｎ−ヘキサンおよびシクロヘキサン）はこ
れと極性溶媒（ｔ−ブタノール）との合計に対してそれ
ぞれ９８．９４重量％、９４．９８重量％、７０．２２
重量％および５０．４重量％含有されている。そして撥
水処理剤中のヘプタデカフルオロデシルトリメトキシシ
ランの加水分解物の濃度は０．０４重量％であった。こ
れら各撥水処理剤に洗浄済みガラス基板をそれぞれ３秒
間浸漬して得られた撥水処理ガラス接触角はそれぞれ、
１０５、９８、９７、および９５度であった。Example 5 Heptadecafluorodecyltrimethoxysilane (chemical formula CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 ) 2.73
Part by weight was dissolved in 4.66 parts by weight of t-butanol.
0.68 g of 0.1N hydrochloric acid was added, the mixture was stirred at 20 ° C. for 4 days for hydrolysis, and 64 parts by weight of n-hexane was further added to obtain a water repellent treatment stock solution. The stock solutions of the water repellent treatment were respectively applied in a weight ratio of 1/99, 5/95, 30/70, and 50.
A water-repellent treatment agent of four types was obtained by diluting 100 times by weight with a t-butanol / cyclohexane solution mixed at a ratio of / 50.
The non-polar solvent (n-hexane and cyclohexane) is 98.94% by weight, 94.98% by weight, and 70.22% with respect to the total of this and the polar solvent (t-butanol), respectively.
% And 50.4% by weight. The concentration of heptadecafluorodecyltrimethoxysilane hydrolyzate in the water repellent agent was 0.04% by weight. The water-repellent treated glass contact angles obtained by immersing the washed glass substrate in each of these water-repellent treating agents for 3 seconds are:
105, 98, 97, and 95 degrees.
【００４０】実施例６ ヘプタデカフルオロデシルトリメトキシシラン（化学式
ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓi（ＯＣＨ3）3）２重量部
と末端シラノール変性ジメチルシロキサン（平均分子量
１７００）２重量部をｔ−ブタノール３２重量部に溶解
した。０．１Ｎ塩酸０．４６ｇを添加し、２０℃で２４
時間攪拌し加水分解し、さらにｎ−ヘキサン６４重量部
を添加し撥水処理剤原液を得た。この撥水処理剤原液１
ｇをシクロヘキサン１００ｇで希釈した。さらに９重量
％のｐ−トルエンスルホン酸のｔ−ブタノール溶液を
４．７ｇ添加し撥水処理剤を得た。非極性溶媒（ｎ−ヘ
キサンおよびシクロヘキサン）はこれと極性溶媒（ｔ−
ブタノール）との合計に対して９５．６３重量％含有さ
れている。そして撥水処理剤中のヘプタデカフルオロデ
シルトリメトキシシランの加水分解物および末端シラノ
ール変性ジメチルシロキサンの濃度はそれぞれ約０．０
２重量％であった。Example 6 2 parts by weight of heptadecafluorodecyltrimethoxysilane (chemical formula CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 ) and 2 parts by weight of terminal silanol-modified dimethylsiloxane (average molecular weight 1700). Was dissolved in 32 parts by weight of t-butanol. Add 0.46 g of 0.1N hydrochloric acid and add 24 at 20 ° C.
The mixture was stirred for hydrolysis for a period of time, and 64 parts by weight of n-hexane was added to obtain a water repellent treatment stock solution. This water repellent treatment stock solution 1
g was diluted with 100 g of cyclohexane. Furthermore, 4.7 g of a 9 wt% p-toluenesulfonic acid t-butanol solution was added to obtain a water repellent treatment agent. Non-polar solvents (n-hexane and cyclohexane) and polar solvents (t-hexane
Butanol) and the total content thereof is 95.63% by weight. The concentration of the hydrolyzate of heptadecafluorodecyltrimethoxysilane and the terminal silanol-modified dimethylsiloxane in the water repellent treatment agent is about 0.0, respectively.
It was 2% by weight.
【００４１】１５０ｍｍ×１５０ｍｍで厚み３ｍｍの洗
浄済みガラスに、この撥水処理剤を５ｃｃ滴下し、綿布
を用いてガラス全面にのばしながら乾燥させて撥水処理
ガラスを得た。この撥水処理ガラスは余分な撥水剤の付
着はわずかに認められたが、エタノールをしみこませた
綿布を用いて容易に取り除くことができた。5 cc of this water repellent treatment agent was dropped onto a washed glass having a size of 150 mm × 150 mm and a thickness of 3 mm, and the glass was dried while being spread on the entire surface of the glass to obtain a water repellent treatment glass. Although the surplus water repellent was slightly adhering to the water-repellent treated glass, it could be easily removed by using a cotton cloth soaked with ethanol.
【００４２】この撥水処理ガラスの接触角は１０５度を
示した。また耐煮沸性試験後、および耐摩耗性試験後の
接触角はそれぞれ９０度、および９５度を示し、高耐久
性を有することが示された。The contact angle of this water-repellent treated glass was 105 degrees. Further, the contact angles after the boiling resistance test and after the abrasion resistance test were 90 degrees and 95 degrees, respectively, showing that they have high durability.
【００４３】実施例７ ヘプタデカフルオロデシルトリメトキシシラン（化学式
ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓi（ＯＣＨ3）3）２重量部
と末端シラノール変性ジメチルシロキサン（平均分子量
１７００）２重量部をｔ−ブタノール３２重量部に溶解
した。０．１Ｎ塩酸０．４６重量部を添加し、２０℃で
２４時間攪拌し加水分解し、さらにｎ−ヘキサン６４重
量部を添加し撥水処理剤原液を得た。この撥水処理剤原
液１ｇをシクロヘキサン６６ｇで希釈した。さらに０．
６重量％のｐ−トルエンスルホン酸のｔ−ブタノール溶
液を３３ｇ添加混合し、撥水処理剤を得た。非極性溶媒
（ｎ−ヘキサンおよびシクロヘキサン）はこれと極性溶
媒（ｔ−ブタノール）との合計に対して６６．８０重量
％含有されている。そして撥水処理剤中のヘプタデカフ
ルオロデシルトリメトキシシランの加水分解物および末
端シラノール変性ジメチルシロキサンの濃度はそれぞれ
約０．０２重量％であった。１５０ｍｍ×１５０ｍｍで
厚み３ｍｍの洗浄済みガラスに、この撥水処理剤を５ｃ
ｃ垂らし、綿布を用いてガラス全面にのばしながら溶媒
を乾燥させ、撥水処理ガラスを得た。この撥水処理ガラ
スは余分な撥水剤の付着はなく、透明であった。この撥
水処理ガラスの接触角は１０５度を示した。また耐煮沸
性試験後、および耐摩耗性試験後の接触角はそれぞれ９
２度、９７度を示し、高耐久性を有することが示され
た。Example 7 2 parts by weight of heptadecafluorodecyltrimethoxysilane (chemical formula CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 ) and 2 parts by weight of terminal silanol-modified dimethylsiloxane (average molecular weight 1700). Was dissolved in 32 parts by weight of t-butanol. 0.46 part by weight of 0.1N hydrochloric acid was added, and the mixture was stirred at 20 ° C. for 24 hours for hydrolysis, and 64 parts by weight of n-hexane was further added to obtain a water repellent treatment stock solution. 1 g of this water repellent treatment stock solution was diluted with 66 g of cyclohexane. Furthermore, 0.
33 g of a 6 wt% p-toluenesulfonic acid t-butanol solution was added and mixed to obtain a water repellent treatment agent. The non-polar solvent (n-hexane and cyclohexane) is contained in an amount of 66.80% by weight based on the total amount of the non-polar solvent and the polar solvent (t-butanol). The concentrations of the hydrolyzate of heptadecafluorodecyltrimethoxysilane and the terminal silanol-modified dimethylsiloxane in the water repellent agent were each about 0.02% by weight. 5c of this water repellent treatment is applied to washed glass with a thickness of 150 mm x 150 mm and a thickness of 3 mm.
The solvent was dried while c was dropped and spread on the entire surface of the glass with a cotton cloth to obtain a water-repellent treated glass. This water-repellent treated glass was transparent without any additional water-repellent agent attached. The contact angle of this water-repellent treated glass was 105 degrees. The contact angles after the boiling resistance test and after the abrasion resistance test were 9
It showed 2 degrees and 97 degrees, showing that it has high durability.
【００４４】実施例８ 実施例６で調合した撥水剤原液１ｇをシクロヘキサン１
００ｇで希釈した。さらに２０重量％の酢酸のｔ−ブタ
ノール溶液を２．０ｇ添加し撥水処理剤を得た。非極性
溶媒（ｎ−ヘキサンおよびシクロヘキサン）はこれと極
性溶媒（ｔ−ブタノール）との合計に対して９９．２９
重量％含有されている。そして撥水処理剤中のヘプタデ
カフルオロデシルトリメトキシシランの加水分解物およ
び末端シラノール変性ジメチルシロキサンの濃度はそれ
ぞれ約０．０２重量％であった。Example 8 1 g of the water repellent stock solution prepared in Example 6 was added to cyclohexane 1
Diluted with 00g. Further, 2.0 g of a 20% by weight acetic acid solution in t-butanol was added to obtain a water repellent treatment agent. The non-polar solvent (n-hexane and cyclohexane) is 99.29 with respect to the total of this and the polar solvent (t-butanol).
It is contained by weight%. The concentrations of the hydrolyzate of heptadecafluorodecyltrimethoxysilane and the terminal silanol-modified dimethylsiloxane in the water repellent agent were each about 0.02% by weight.
【００４５】１５０ｍｍ×１５０ｍｍで厚み３ｍｍの洗
浄済みガラスに、この撥水処理剤を５ｃｃ滴下し、綿布
を用いてガラス全面にのばしながら乾燥させて撥水処理
ガラスを得た。5 cc of this water repellent treatment agent was dropped on a washed glass having a size of 150 mm × 150 mm and a thickness of 3 mm, and the glass was dried while being spread on the entire surface of the glass to obtain a water repellent treatment glass.
【００４６】この撥水処理ガラスは余分な撥水剤の付着
はわずかに認められたが、エタノールをしみこませた綿
布を用いて容易に取り除くことができた。この撥水処理
ガラスは透明性も良く、余分な撥水剤の付着は認められ
なかった。In this water-repellent treated glass, an extra water-repellent agent was slightly adhering, but it could be easily removed by using a cotton cloth soaked with ethanol. This water-repellent treated glass had good transparency, and no excessive water-repellent agent was attached.
【００４７】この撥水処理ガラスの接触角は１０３度を
示した。また耐煮沸性試験後、および耐摩耗性試験後の
接触角はそれぞれ８６度、および９３度を示し、高耐久
性を有することが示された。The contact angle of this water-repellent treated glass was 103 degrees. Further, the contact angles after the boiling resistance test and after the abrasion resistance test were 86 degrees and 93 degrees, respectively, showing that they have high durability.
【００４８】実施例９ テトラエトキシシラン５２．１０ｇとイソプロパノール
３８３．００ｇを混合し２０分間攪拌し、さらに水１
０．５８ｇ、１Ｎ塩酸を２．７０ｇを加えて２時間攪拌
した。この溶液を密封容器にいれ、５０℃で３時間攪拌
したのち、さらに２０℃で１５時間攪拌した後、コロイ
ダルシリカ（日産化学工業製「スノーテックスＯＬ」、
粒子直径５０ｎｍ、固形分２０重量％）７３．７０ｇ、
イソプロパノール４４９．８０ｇを加え、さらに２０℃
で５時間攪拌し、凹凸被膜作製用組成物を得た。Example 9 52.10 g of tetraethoxysilane and 383.00 g of isopropanol were mixed and stirred for 20 minutes, and water 1 was added.
0.58 g and 1.70 g of 1N hydrochloric acid were added and stirred for 2 hours. This solution was placed in a sealed container and stirred at 50 ° C. for 3 hours, then at 20 ° C. for 15 hours, and then colloidal silica (“Snowtex OL” manufactured by Nissan Chemical Industries, Ltd.,
Particle diameter 50 nm, solid content 20% by weight) 73.70 g,
Add 44.80 g of isopropanol and add 20 ° C.
The mixture was stirred for 5 hours to obtain a composition for producing an uneven coating.
【００４９】上記で得られた撥水被膜用組成物中に洗浄
済みの１５０×１５０×３mmのフロートガラス板（ソー
ダ石灰珪酸塩ガラス）を浸漬し、引き上げ速度１００ｍ
ｍ／分のディップ法により塗膜し、室温下で１時間乾燥
させた。さらに電気炉中で１００℃／時間の割合で５０
０℃まで昇温し、５００℃で１時間保持した後、１００
℃／時間の割合で室温まで降温して、厚みが約８０ｎｍ
の凹凸被膜をガラス基板上に作製した。A washed 150 × 150 × 3 mm float glass plate (soda lime silicate glass) was immersed in the water-repellent coating composition obtained above, and the pulling speed was 100 m.
A coating film was applied by a dipping method of m / min and dried at room temperature for 1 hour. Furthermore, 50 at a rate of 100 ° C / hour in an electric furnace.
After raising the temperature to 0 ° C and holding at 500 ° C for 1 hour, 100
The temperature is lowered to room temperature at a rate of ℃ / hour and the thickness is about 80 nm.
The concavo-convex coating film was prepared on a glass substrate.
【００５０】この凹凸被膜付きガラス基板を純水中で超
音波を５分間あて乾燥した後、ＵＶ／オゾン処理装置
（ＵＶ−３００型、（株）サムコインターナショナル研
究所製）を用い主波長２５３．７ｎｍ、この波長での照
度１５ｍＷ／ｃｍ2 において３分間照射し、凹凸被膜の
表面を洗浄した後、ただちに実施例１で使用したと同じ
撥水処理剤に浸漬し約１０秒後に引き上げ凹凸形状を有
する撥水処理ガラスを作製した。This glass substrate with a concavo-convex film was exposed to ultrasonic waves in pure water for 5 minutes to dry it, and then a UV / ozone treatment device (UV-300 type, manufactured by Samco International Laboratories, Inc.) was used to obtain a main wavelength of 253. Irradiation at 7 nm and an illuminance of 15 mW / cm 2 at this wavelength for 3 minutes was performed to wash the surface of the concavo-convex coating film, and then immediately immersed in the same water repellent agent as used in Example 1 to raise the concavo-convex shape after about 10 seconds. A water-repellent treated glass was prepared.
【００５１】この撥水被膜の水の接触角と摩耗耐久性試
験後の変化を評価した。摩耗耐久性試験は、長さ５ｃｍ
に切断した自動車用ワイパーブレードに１００ｇの荷重
をかけ、１分間に２０ｃｃの割合で水滴を滴下しなが
ら、撥水被膜表面を５００００回往復摩耗した。摩耗試
験前の水の接触角は１１５．６度、摩耗試験後の水の接
触角は１０５．３度を示し、ワイパーゴムでの摩耗に対
しても耐久性に優れていることがわかる。The water contact angle of this water repellent coating and the change after the abrasion durability test were evaluated. Abrasion durability test is 5 cm long
A load of 100 g was applied to the automobile wiper blade cut into pieces, and the surface of the water-repellent coating was reciprocally abraded 50,000 times while dropping water drops at a rate of 20 cc per minute. The contact angle of water before the abrasion test was 115.6 degrees, and the contact angle of water after the abrasion test was 105.3 degrees, which shows that the durability against abrasion by the wiper rubber is excellent.
【００５２】比較例１ 実施例１と同じ方法により作製した撥水処理剤原液を、
実施例１でのシクロヘキサンの代わりにｉ−プロパノー
ルを用いて１００倍に希釈し撥水処理剤を得た。非極性
溶媒（ｎ−ヘキサン）はこれと極性溶媒（ｔ−ブタノー
ルおよびｉ−プロパノール）との合計に対して０．６５
重量％含有されている。そして撥水処理剤中のヘプタデ
カフルオロデシルトリメトキシシランの加水分解物の濃
度は約０．０２重量％であった。この撥水処理剤に洗浄
済みガラス基板を３秒間浸漬して得られた撥水処理ガラ
ス接触角は５０度であった。また上記浸漬時間を長くし
て１０分にしたが撥水処理ガラス接触角は７０度であっ
た。これより極性溶媒を用いた場合は撥水処理性能は著
しく低下することがわかる。Comparative Example 1 A stock solution of a water repellent agent prepared by the same method as in Example 1 was used.
A water repellent treatment agent was obtained by diluting 100 times with i-propanol instead of cyclohexane in Example 1. The non-polar solvent (n-hexane) is 0.65 relative to the sum of this and the polar solvents (t-butanol and i-propanol).
It is contained by weight%. The concentration of the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent treatment was about 0.02% by weight. The water-repellent glass contact angle obtained by immersing the washed glass substrate in this water-repellent agent for 3 seconds was 50 degrees. Although the immersion time was lengthened to 10 minutes, the contact angle of the water-repellent glass was 70 degrees. From this, it can be seen that the water repellent treatment performance is remarkably reduced when a polar solvent is used.
【００５３】比較例２ 実施例１と同じ方法により作製した撥水処理剤原液を、
実施例１でのシクロヘキサンの代わりにそれぞれｔ−ブ
タノール、酢酸エチルおよびアセトンを用いて１００倍
に希釈し、３種類の撥水処理剤を得た。非極性溶媒（ｎ
−ヘキサン）はこれと極性溶媒（ｔ−ブタノール、酢酸
エチルおよびアセトン）との合計に対してそれぞれ０．
６５重量％含有されている。そして撥水処理剤中のヘプ
タデカフルオロデシルトリメトキシシランの加水分解物
の濃度は約０．０２重量％であった。これらの撥水処理
剤に洗浄済みガラス基板を３秒間浸漬して得られた撥水
処理ガラス接触角はそれぞれ、５３、４３、５８度であ
った。また上記浸漬時間を長くして１０分にしたが撥水
処理ガラス接触角はそれぞれ７５度，６６度および８１
度であった。これらの極性溶媒を用いた場合でも撥水処
理性能は著しく低下することがわかる。Comparative Example 2 A stock solution of a water repellent agent prepared by the same method as in Example 1 was used.
Instead of cyclohexane used in Example 1, t-butanol, ethyl acetate and acetone were used to dilute 100 times to obtain three types of water repellent treatment agents. Non-polar solvent (n
-Hexane) was added to the polar solvent (t-butanol, ethyl acetate and acetone), and the total amount of the solvent was 0.
The content is 65% by weight. The concentration of the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent treatment was about 0.02% by weight. The contact angles of the water-repellent glass obtained by immersing the washed glass substrate in these water-repellent agents for 3 seconds were 53, 43 and 58 degrees, respectively. Further, the immersion time was increased to 10 minutes, but the contact angles of the water-repellent glass were 75 °, 66 ° and 81 °, respectively.
Degree. It can be seen that the water-repellent treatment performance is significantly reduced even when these polar solvents are used.
【００５４】比較例３ 実施例４と同様の方法で得られた撥水処理剤原液を重量
比で６０／４０で混合したｔ−ブタノール／シクロヘキ
サン溶液で重量比で１００倍に希釈し撥水処理剤を得
た。非極性溶媒（ｎ−ヘキサンおよびシクロヘキサン）
はこれと極性溶媒（ｔ−ブタノール）との合計に対して
４０．２５重量％含有されている。そして撥水処理剤中
のヘプタデカフルオロデシルトリメトキシシランの加水
分解物および末端シラノール変性ジメチルシロキサンの
濃度はそれぞれ約０．０２重量％であった。Comparative Example 3 Water repellent treatment was carried out by diluting the stock solution of the water repellent agent obtained in the same manner as in Example 4 with a t-butanol / cyclohexane solution mixed at a weight ratio of 60/40 to a weight ratio of 100 times. I got an agent. Non-polar solvent (n-hexane and cyclohexane)
Is contained in an amount of 40.25% by weight based on the total of this and the polar solvent (t-butanol). The concentrations of the hydrolyzate of heptadecafluorodecyltrimethoxysilane and the terminal silanol-modified dimethylsiloxane in the water repellent agent were each about 0.02% by weight.
【００５５】この撥水処理剤に洗浄済みガラス基板を３
秒間浸漬して得られた撥水処理ガラス接触角は８５度で
あり、実施例５と比較し撥水処理性能が低下したことが
わかる。3 glass substrates washed with this water repellent treatment are added.
The contact angle of the water-repellent treated glass obtained by immersing for a second was 85 degrees, which shows that the water-repellent treatment performance was lower than that of Example 5.
【００５６】比較例４ 実施例１と同じ方法により作製した撥水処理剤原液をシ
クロヘキサンで重量比で３００倍に希釈し撥水処理剤を
得た。非極性溶媒（ｎ−ヘキサンおよびシクロヘキサ
ン）はこれと極性溶媒（ｔ−ブタノール）との合計に対
して９８．８９重量％含有されている。そして撥水処理
剤中のヘプタデカフルオロデシルトリメトキシシランの
加水分解物の濃度は約０．００７重量％であった。Comparative Example 4 A water repellent treatment agent was obtained by diluting a stock solution of a water repellent treatment agent prepared by the same method as in Example 1 with cyclohexane at a weight ratio of 300 times. The non-polar solvent (n-hexane and cyclohexane) is contained in an amount of 98.89% by weight based on the total amount of the non-polar solvent and the polar solvent (t-butanol). The concentration of the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent agent was about 0.007% by weight.
【００５７】この撥水処理剤に洗浄済みガラス基板を３
秒間浸漬して得られた撥水処理ガラス接触角は６１度で
あった。また上記浸漬時間を長くして１０分にしたが撥
水処理ガラス接触角は６５度であった。これより撥水処
理剤中のヘプタデカフルオロデシルトリメトキシシラン
の加水分解物の濃度低い場合、撥水処理性能は著しく低
下することがわかる。Three glass substrates that have been washed with this water repellent treatment are used.
The contact angle of the water-repellent treated glass obtained by soaking for seconds was 61 degrees. Although the immersion time was lengthened to 10 minutes, the contact angle of the water repellent glass was 65 degrees. From this, it can be seen that when the concentration of the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent treatment agent is low, the water repellent treatment performance is significantly reduced.
【００５８】比較例５ ヘプタデカフルオロデシルトリメトキシシラン（化学式
ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓi（ＯＣＨ3）3）０．２重
量部をｔ−ブタノール４０重量部に溶解した。これに１
Ｎ塩酸０．４６ｇを添加し、２０℃で２４時間攪拌し加
水分解し、さらにｎ−ヘキサン６０重量部を添加し撥水
処理剤を得た。非極性溶媒（ｎ−ヘキサン）はこれと極
性溶媒（ｔ−ブタノール）との合計に対して６０重量％
含有されている。そして撥水処理剤中のヘプタデカフル
オロデシルトリメトキシシランの加水分解物の濃度は約
０．２重量％であった。Comparative Example 5 0.2 parts by weight of heptadecafluorodecyltrimethoxysilane (chemical formula CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 ) was dissolved in 40 parts by weight of t-butanol. This one
0.46 g of N hydrochloric acid was added, and the mixture was stirred at 20 ° C. for 24 hours for hydrolysis, and 60 parts by weight of n-hexane was further added to obtain a water repellent treatment agent. The non-polar solvent (n-hexane) is 60% by weight with respect to the total of this and the polar solvent (t-butanol).
It is contained. The concentration of the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent agent was about 0.2% by weight.
【００５９】１５０ｍｍ×１５０ｍｍで厚み３ｍｍの洗
浄済みガラスに、この撥水処理剤を５ｃｃ滴下し、綿布
を用いてガラス全面にのばしながら乾燥させて撥水処理
ガラスを得た。5 cc of this water repellent treatment agent was dropped on a washed glass having a size of 150 mm × 150 mm and a thickness of 3 mm, and the glass was dried while being spread on the entire surface of the glass to obtain a water repellent treatment glass.
【００６０】この撥水処理ガラスは余分な撥水剤が付着
し透明性が非常に悪くなりエタノールをしみこませた綿
布を用いても完全に取り除くことは困難であった。The water-repellent treated glass had an extra water-repellent agent attached and had very poor transparency, and it was difficult to completely remove it even with a cotton cloth soaked with ethanol.
【００６１】比較例６ ヘプタデカフルオロデシルトリメトキシシラン（化学式
ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓi（ＯＣＨ3）3）０．０２
重量部、ｎ−ヘキサン１００重量部および０．１Ｎ塩酸
０．０５ｇを攪拌しながら２０℃で６時間加水分解し外
観が白濁した撥水処理剤を得た。全溶媒に対して非極性
溶媒（ｎ−ヘキサン）は１００重量％含有されている。
そして撥水処理剤中のヘプタデカフルオロデシルトリメ
トキシシランの加水分解物の濃度は約０．０２重量％で
あった。Comparative Example 6 Heptadecafluorodecyltrimethoxysilane (Chemical Formula CF 3 (CF 2 ) 7 CH 2 CH 2 Si (OCH 3 ) 3 ) 0.02
By weight, 100 parts by weight of n-hexane and 0.05 g of 0.1N hydrochloric acid were hydrolyzed at 20 ° C. for 6 hours with stirring to obtain a water repellent treatment having a cloudy appearance. The non-polar solvent (n-hexane) is contained in 100% by weight with respect to all the solvents.
The concentration of the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent treatment was about 0.02% by weight.
【００６２】この撥水処理剤に洗浄済みガラス基板を３
秒間浸漬して得られた撥水処理ガラス接触角は４６度で
あった。また上記浸漬時間を長くして１０分にしたが撥
水処理ガラス接触角は５４度であった。これより非極性
溶媒中で加水分解を行った場合、撥水処理剤中のヘプタ
デカフルオロデシルトリメトキシシランの加水分解物が
析出し撥水処理性能は著しく低下することがわかる。A glass substrate that has been washed with 3 parts of this water repellent treatment is added.
The contact angle of the water-repellent treated glass obtained by soaking for seconds was 46 degrees. Although the immersion time was lengthened to 10 minutes, the contact angle of the water-repellent glass was 54 degrees. From this, it is understood that when the hydrolysis is carried out in a non-polar solvent, the hydrolyzate of heptadecafluorodecyltrimethoxysilane in the water repellent agent is deposited and the water repellent performance is remarkably lowered.
【００６３】[0063]
【発明の効果】従来の撥水処理剤は１日以上の接触時間
であっても９０度未満の接触角しか示さないが、本発明
の撥水処理剤は、液相吸着、すなわち洗浄済みのガラス
基板のような親水性表面を有する被撥水処理基材を撥水
処理剤とわずか数秒接触させて化学吸着させた後の基材
表面は９５〜１０５度の接触角を示し、作業性、撥水性
共に優れたものとなる。Although the conventional water repellent treatments show a contact angle of less than 90 degrees even for a contact time of 1 day or more, the water repellent treatments of the present invention are liquid phase adsorbed, that is, washed. The water-repellent treated base material having a hydrophilic surface such as a glass substrate is brought into contact with the water-repellent treatment agent for only a few seconds to be chemically adsorbed, and thus the base material surface exhibits a contact angle of 95 to 105 degrees. It has excellent water repellency.
【００６４】本発明により、優れた撥水性、防汚性を与
えることができ、かつ処理時間も短くて済み、撥水処理
の作業性に優れた撥水処理剤を得ることができる。According to the present invention, it is possible to provide a water repellent treatment agent which can provide excellent water repellency and antifouling property, can be treated in a short time, and has excellent workability in water repellent treatment.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 弘一 大阪市中央区道修町３丁目５番11号 日本 板硝子株式会社内 (72)発明者 寺西 豊幸 大阪市中央区道修町３丁目５番11号 日本 板硝子株式会社内 (72)発明者 工藤 宗夫 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社シリコーン電子材料 技術研究所内 (72)発明者 浅井 光雄 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社シリコーン電子材料 技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koichi Suzuki, 3-5-11 Doshumachi, Chuo-ku, Osaka City, Japan Sheet Glass Co., Ltd. (72) Inventor, Toyoyuki Teranishi 3-5-11, Doshomachi, Chuo-ku, Osaka Japan Sheet Glass Co., Ltd. (72) Inventor Muneo Kudo 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor, Mitsuo Asai Oita, Matsuida-cho, Usui-gun, Gunma Prefecture Mi No. 1 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory
Claims (5)
オロアルキル基を有する有機ケイ素化合物および／また
はその加水分解物ならびに有機溶媒を含有する撥水処理
剤において、前記有機ケイ素化合物および／またはその
加水分解物が０．０１〜０．１重量％の濃度で含有さ
れ、かつ前記有機溶媒が非極性溶媒を５０〜９９．９５
重量％含有することを特徴とする撥水処理剤。1. An organosilicon compound having an alkoxy group or an acyloxy group and a fluoroalkyl group and / or a hydrolyzate thereof and a water repellent agent containing an organic solvent, wherein the organosilicon compound and / or a hydrolyzate thereof is The organic solvent is contained in a concentration of 0.01 to 0.1% by weight, and the organic solvent is a nonpolar solvent in the range of 50 to 99.95.
A water repellent treatment agent, characterized in that the water repellent is contained in an amount of wt%.
の加水分解物がアルコキシ基またはアシロキシ基を有す
るフルオロアルキルシランの加水分解物である請求項１
記載の撥水処理剤。2. The organosilicon compound and / or its hydrolyzate is a hydrolyzate of a fluoroalkylsilane having an alkoxy group or an acyloxy group.
The water repellent treatment described.
９９．９０重量％含有する請求項１または２記載の撥水
処理剤。3. The organic solvent comprises the non-polar solvent in an amount of 95-
The water repellent treatment agent according to claim 1 or 2, containing 99.90% by weight.
の加水分解物が０．０２〜０．０９重量％の濃度で含有
される請求項１〜３のいずれかに記載の撥水処理剤。4. The water repellent treatment agent according to claim 1, wherein the organosilicon compound and / or its hydrolyzate is contained in a concentration of 0.02 to 0.09% by weight.
オロアルキル基を有する有機ケイ素化合物、触媒および
水を、これらを溶解することができる溶媒中で加水分解
した後に、非極性溶媒を添加することを特徴とする請求
項１〜４のいずれかに記載の撥水処理剤の製造方法。5. An organosilicon compound having an alkoxy group or an acyloxy group and a fluoroalkyl group, a catalyst and water are hydrolyzed in a solvent capable of dissolving them, and then a nonpolar solvent is added. The method for producing the water repellent treatment agent according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6950796A JPH09255941A (en) | 1996-03-26 | 1996-03-26 | Water-repellent treatment and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6950796A JPH09255941A (en) | 1996-03-26 | 1996-03-26 | Water-repellent treatment and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09255941A true JPH09255941A (en) | 1997-09-30 |
Family
ID=13404734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6950796A Pending JPH09255941A (en) | 1996-03-26 | 1996-03-26 | Water-repellent treatment and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09255941A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036820A (en) * | 1996-07-26 | 1998-02-10 | Cci Corp | Water repellent and method for water repellent finishing |
| WO2002098983A1 (en) * | 2001-05-30 | 2002-12-12 | Dow Corning Toray Silicone Co., Ltd. | Silicone composition for water-repellent coating |
| WO2006022118A1 (en) * | 2004-08-27 | 2006-03-02 | Central Glass Company, Limited | Treatment for forming waterdrop slidable films and process for forming waterdrop slidable films |
| JP2009519362A (en) * | 2005-12-15 | 2009-05-14 | エボニック デグサ ゲーエムベーハー | Storage-stable coating composition for wear- and weather-resistant application of easy-clean properties to smooth inorganic surfaces |
| JP2009519363A (en) * | 2005-12-15 | 2009-05-14 | エボニック デグサ ゲーエムベーハー | Storage-stable coating composition for wear- and weather-resistant application of easy-clean properties to smooth inorganic surfaces |
| JP2020158692A (en) * | 2019-03-27 | 2020-10-01 | 日本山村硝子株式会社 | Fluorine-containing condensed type organopolysiloxane prepolymer and cured product thereof |
-
1996
- 1996-03-26 JP JP6950796A patent/JPH09255941A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036820A (en) * | 1996-07-26 | 1998-02-10 | Cci Corp | Water repellent and method for water repellent finishing |
| WO2002098983A1 (en) * | 2001-05-30 | 2002-12-12 | Dow Corning Toray Silicone Co., Ltd. | Silicone composition for water-repellent coating |
| WO2006022118A1 (en) * | 2004-08-27 | 2006-03-02 | Central Glass Company, Limited | Treatment for forming waterdrop slidable films and process for forming waterdrop slidable films |
| KR100894079B1 (en) * | 2004-08-27 | 2009-04-21 | 샌트랄 글래스 컴퍼니 리미티드 | Treatment for forming waterdrop slidable films and process for forming waterdrop slidable films |
| JP2009519362A (en) * | 2005-12-15 | 2009-05-14 | エボニック デグサ ゲーエムベーハー | Storage-stable coating composition for wear- and weather-resistant application of easy-clean properties to smooth inorganic surfaces |
| JP2009519363A (en) * | 2005-12-15 | 2009-05-14 | エボニック デグサ ゲーエムベーハー | Storage-stable coating composition for wear- and weather-resistant application of easy-clean properties to smooth inorganic surfaces |
| KR101354818B1 (en) * | 2005-12-15 | 2014-01-22 | 에보니크 데구사 게엠베하 | Storage-stable coating composition for abrasion-resistantly and weathering-stably providing smooth inorganic surfaces with easy-to-clean properties |
| KR101354874B1 (en) * | 2005-12-15 | 2014-02-18 | 에보니크 데구사 게엠베하 | Storage-stable coating composition for abrasion-resistantly and weathering-stably providing smooth inorganic surfaces with easy-to-clean properties |
| EP1960482B1 (en) * | 2005-12-15 | 2019-01-02 | Evonik Degussa GmbH | Storage-stable coating composition for abrasion-resistantly and weathering-stably providing smooth inorganic surfaces with easy-to-clean properties |
| JP2020158692A (en) * | 2019-03-27 | 2020-10-01 | 日本山村硝子株式会社 | Fluorine-containing condensed type organopolysiloxane prepolymer and cured product thereof |
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