JPH06256756A - Water-repelling agent composition - Google Patents
Water-repelling agent compositionInfo
- Publication number
- JPH06256756A JPH06256756A JP5073031A JP7303193A JPH06256756A JP H06256756 A JPH06256756 A JP H06256756A JP 5073031 A JP5073031 A JP 5073031A JP 7303193 A JP7303193 A JP 7303193A JP H06256756 A JPH06256756 A JP H06256756A
- Authority
- JP
- Japan
- Prior art keywords
- group
- water
- formula
- compound
- fatty acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Paints Or Removers (AREA)
- Surface Treatment Of Glass (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ガラス、セラミック、
金属などの無機質表面処理に好適に用いられ、優れた撥
水性、防汚性を与えることができる有機溶剤可溶性の撥
水処理剤組成物に関する。The present invention relates to glass, ceramics,
The present invention relates to a water-repellent agent composition soluble in an organic solvent, which is suitably used for surface treatment of an inorganic material such as a metal and can impart excellent water repellency and antifouling property.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】ガラ
ス、セラミック、金属などの無機質材料は、その表面を
各種表面処理剤で処理することにより、表面の性質を改
良し、更に高性能化、応用範囲の拡大を図る研究が種々
行われている。2. Description of the Related Art Inorganic materials such as glass, ceramics and metals are improved in surface properties by treating the surface with various surface treatment agents to further improve performance and application. Various studies have been conducted to expand the scope.
【０００３】その１つとして、本来親水性の表面をシリ
コーン系組成物で処理することにより撥水性表面に改質
する方法も提案されており、特にパーフロロアルキル基
を含有するポリシロキサン又はポリシラザン（特開昭５
８−１４７４８４号公報、特開昭６０−２２１４７０号
公報、特開平４−９６９３５号公報）が撥水性に優れた
ものとして知られている。As one of the methods, there has been proposed a method of modifying a water-repellent surface by treating an originally hydrophilic surface with a silicone composition, and in particular, polysiloxane or polysilazane (containing a perfluoroalkyl group) ( JP-A-5
JP-A 8-147484, JP-A-60-212470 and JP-A-4-96935) are known to have excellent water repellency.
【０００４】しかしながら、これらは撥水効果には優れ
るものの、水滴の落下性に劣るため、例えば窓ガラス、
自動車のドアミラー、フロントガラスなどに適用した場
合、水滴が落下せずガラス表面に水玉状にとどまるの
で、空気中のチリ、油分などが付着して新たな汚れを生
じたり、視界を悪くしたりするという欠点があった。However, although these are excellent in water repellency, they are inferior in the drop property of water drops, and therefore, for example, window glass,
When applied to automobile door mirrors, windshields, etc., water droplets do not drop and stay in the shape of polka dots on the glass surface, so dust in the air, oil, etc. may attach and cause new stains and deteriorate visibility. There was a drawback.
【０００５】また、特開平３−２９０４３７号公報で提
案されている含フッ素シラザン化合物は、上記欠点は改
良されているものの、一般有機溶剤への溶解性が悪く、
フロン規制対象物質である１，１，３−トリクロロトリ
フロロエタンのようなフロン類や高価なフッ化炭化水素
類にしか安定に溶けず、そのため応用範囲が限定される
という問題があった。Further, the fluorine-containing silazane compound proposed in JP-A-3-290437 has improved the above-mentioned drawbacks, but has poor solubility in general organic solvents,
There is a problem that it can be stably dissolved only in freons such as 1,1,3-trichlorotrifluoroethane, which is a substance subject to freon regulation, and expensive fluorohydrocarbons, which limits the application range.
【０００６】本発明は、上記事情に鑑みなされたもの
で、優れた撥水性、防汚性を与えることができると共
に、一般の有機溶剤に溶解可能な撥水処理剤組成物を提
供することを目的とする。The present invention has been made in view of the above circumstances, and provides a water repellent composition capable of imparting excellent water repellency and antifouling property and soluble in general organic solvents. To aim.
【０００７】[0007]
【課題を解決するための手段及び作用】本発明者は、上
記目的を達成するため鋭意検討を重ねた結果、（Ａ）下
記一般式（１）で示されるパーフロロアルキル基含有有
機ケイ素化合物又は該化合物の部分加水分解縮合物、
（Ｂ）下記一般式（２）で示されるＳｉＨ基含有メチル
ポリシロキサン化合物、（Ｃ）脂肪酸金属塩又は金属ア
ルコキシドを含有する組成物が、撥水処理剤として有効
であることを知見した。Means and Actions for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has (A) a perfluoroalkyl group-containing organosilicon compound represented by the following general formula (1): A partially hydrolyzed condensate of the compound,
It has been found that a composition containing (B) a SiH group-containing methylpolysiloxane compound represented by the following general formula (2) and (C) a fatty acid metal salt or a metal alkoxide is effective as a water repellent treatment agent.
【０００８】[0008]
【化３】 （但し、式中Ｒ1、Ｒ2はそれぞれ炭素原子数１〜４の１
価の炭化水素基、Ｑは炭素原子数２〜１０の２価の有機
基、ｐは１〜１２の整数、ａは０又は１を表す。）[Chemical 3] (However, in the formula, R 1 and R 2 are each 1 to 4 carbon atoms.
A valent hydrocarbon group, Q represents a divalent organic group having 2 to 10 carbon atoms, p represents an integer of 1 to 12, and a represents 0 or 1. )
【０００９】[0009]
【化４】 （但し、式中Ａは水素原子又はメチル基、ｍは０〜１０
０の整数、ｎは０〜２００の整数、１０≦ｍ＋ｎ≦２０
０であるが、ｎ＝０のときＡは水素原子である。）[Chemical 4] (However, in the formula, A is a hydrogen atom or a methyl group, and m is 0 to 10.
An integer of 0, n is an integer of 0 to 200, 10 ≦ m + n ≦ 20
Although it is 0, when n = 0, A is a hydrogen atom. )
【００１０】すなわち、上記（Ａ）成分のパーフロロア
ルキル基含有有機ケイ素化合物が撥水性能を有すること
は公知であるが、上述したように（Ａ）成分のみでは水
滴の落下性が不十分である。ところが、これに（Ｂ）成
分のＳｉＨ基含有メチルポリシロキサン化合物、更に
（Ｃ）成分の脂肪酸金属塩又は金属アルコキシドを併用
することにより、優れた撥水性能を与えると共に、水滴
の落下性が向上し、しかも無機表面との化学結合も促進
されて、撥水耐久性、防汚耐久性が顕著に増大するこ
と、更にこれら（Ａ）、（Ｂ）、（Ｃ）成分それぞれが
一般の有機溶剤に可溶であるため、特殊なフッ素系溶剤
を使用しなくても良く、撥水処理剤として利用範囲が広
いことを見い出し、本発明をなすに至ったものである。That is, it is known that the perfluoroalkyl group-containing organosilicon compound as the component (A) has a water-repellent property, but as described above, the component (A) alone is not sufficient to drop water drops. is there. However, by using a SiH group-containing methylpolysiloxane compound as the component (B) and a fatty acid metal salt or metal alkoxide as the component (C) in combination with this, excellent water repellency is provided and the dropability of water droplets is improved. In addition, the chemical bond with the inorganic surface is promoted, and the water repellency durability and antifouling durability are remarkably increased. Furthermore, each of these components (A), (B) and (C) is a general organic solvent. Since it is soluble in water, it is not necessary to use a special fluorine-based solvent, and it has been found that it can be used as a water-repellent treatment agent in a wide range.
【００１１】従って、本発明は上記（Ａ）成分、（Ｂ）
成分及び（Ｃ）成分を含有することを特徴とする撥水処
理剤組成物を提供する。Therefore, the present invention is based on the above-mentioned components (A) and (B).
There is provided a water repellent treatment agent composition comprising a component and a component (C).
【００１２】以下、本発明について更に詳しく説明する
と、本発明の撥水処理剤組成物を構成する（Ａ）成分
は、上述したように下記一般式（１）で示されるパーフ
ロロアルキル基含有有機ケイ素化合物又は該化合物の部
分加水分解縮合物である。The present invention will be described in more detail below. The component (A) which constitutes the water repellent composition of the present invention is, as described above, a perfluoroalkyl group-containing organic compound represented by the following general formula (1). It is a silicon compound or a partially hydrolyzed condensate of the compound.
【００１３】[0013]
【化５】 [Chemical 5]
【００１４】この式中、Ｒ1、Ｒ2は、それぞれ炭素原子
数１〜４の１価炭化水素基であり、具体的にはメチル
基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−
ブチル基、イソブチル基、ｓ−ブチル基などが例示され
る。Ｑはパーフロロアルキル基とケイ素原子とを結合す
る炭素原子数２〜１０の２価の有機基であり、具体的に
は下記式のものが例示される。−ＣＨ2ＣＨ2−，−ＣＨ
2ＯＣＨ2ＣＨ2ＣＨ2−，−ＣＯＮＨＣＨ2ＣＨ2ＣＨ
2−，−ＣＯＮＨＣＨ2ＣＨ2ＮＨＣＨ2ＣＨ2ＣＨ2−，−
ＳＯ2ＮＨＣＨ2ＣＨ2ＣＨ2−，−ＣＨ2ＣＨ2ＯＣＯＮＨ
ＣＨ2ＣＨ2ＣＨ2−また、ｐはパーフロロアルキル基の
炭素数を表すもので、１〜１２であり、ｐが１２を超え
ると有機溶剤への溶解性がなくなってしまう。更に、ａ
は０又は１である。In this formula, R 1 and R 2 are each a monovalent hydrocarbon group having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-
A butyl group, an isobutyl group, an s-butyl group and the like are exemplified. Q is a divalent organic group having 2 to 10 carbon atoms which bonds a perfluoroalkyl group and a silicon atom, and specific examples thereof include those having the following formulas. -CH 2 CH 2 -, - CH
2 OCH 2 CH 2 CH 2 —, —CONHCH 2 CH 2 CH
2 -, - CONHCH 2 CH 2 NHCH 2 CH 2 CH 2 -, -
SO 2 NHCH 2 CH 2 CH 2 -, - CH 2 CH 2 OCONH
CH 2 CH 2 CH 2 — In addition, p represents the number of carbon atoms of the perfluoroalkyl group and is 1 to 12, and when p exceeds 12, solubility in an organic solvent is lost. Furthermore, a
Is 0 or 1.
【００１５】このような式（１）で示されるパーフロロ
アルキル基含有有機ケイ素化合物としては、次のような
化合物を例示することができる。As the perfluoroalkyl group-containing organosilicon compound represented by the formula (1), the following compounds can be exemplified.
【００１６】[0016]
【化６】 [Chemical 6]
【００１７】この（Ａ）成分は上記一般式（１）で示さ
れる化合物そのまま用いても良く、また式（１）で示さ
れる化合物の部分加水分解物を使用しても良く、更にこ
れらの１種を単独で又は２種以上併用して用いることが
できる。As the component (A), the compound represented by the general formula (1) may be used as it is, or a partial hydrolyzate of the compound represented by the formula (1) may be used. The seeds may be used alone or in combination of two or more.
【００１８】次に、本発明の撥水処理剤組成物を構成す
る（Ｂ）成分のＳｉＨ基含有メチルポリシロキサン化合
物は、下記一般式（２）で示される化合物である。Next, the SiH group-containing methylpolysiloxane compound as the component (B) which constitutes the water repellent composition of the present invention is a compound represented by the following general formula (2).
【００１９】[0019]
【化７】 [Chemical 7]
【００２０】この式（２）中、Ａは水素原子又はメチル
基であり、ｍは０〜１００の整数、ｎは０〜２００の整
数である。また、ｍ＋ｎが１０未満では水滴の落下性が
不足して防汚性が悪くなり、２００を超えると組成物の
安定性が悪くなるので、ｍ＋ｎは１０〜２００を満足す
る必要がある。なお、ｎが０のときＡは水素原子であ
る。In the formula (2), A is a hydrogen atom or a methyl group, m is an integer of 0 to 100, and n is an integer of 0 to 200. Further, when m + n is less than 10, the drop property of water drops is insufficient and the antifouling property is deteriorated, and when it exceeds 200, the stability of the composition is deteriorated, and therefore m + n needs to satisfy 10 to 200. When n is 0, A is a hydrogen atom.
【００２１】これらの（Ａ）成分と（Ｂ）成分との配合
比率は、重量比で（Ａ）／（Ｂ）＝５／９５〜９５／
５、特に２０／８０〜８０／２０の範囲とすることが好
ましい。（Ａ）成分の比率が５重量部未満では十分な撥
水性が得られない場合があり、９５重量部を超えると水
滴の落下性が不足し、十分な防汚性が得られなくなる場
合がある。The mixing ratio of these components (A) and (B) is (A) / (B) = 5/95 to 95 / by weight.
The range of 5, especially 20/80 to 80/20 is preferable. If the ratio of the component (A) is less than 5 parts by weight, sufficient water repellency may not be obtained, and if it exceeds 95 parts by weight, drop properties of water droplets may be insufficient and sufficient antifouling property may not be obtained. .
【００２２】本発明の撥水処理剤組成物を構成する
（Ｃ）成分の脂肪酸金属塩及び金属アルコキシドは、
（Ａ）、（Ｂ）両成分と無機質表面との反応に触媒とし
て作用するもので、具体的にはジブチル錫ジラウレー
ト、ジブチル錫ジアセテート、ジブチル錫ジオクトエー
ト、鉄オクトエート、テトライソプロピルチタネート、
テトラブチルチタネート、テトラブチルチタネートの加
水分解縮合物などが例示される。この（Ｃ）成分の配合
量は、（Ａ）、（Ｂ）成分の合計１００部（重量部、以
下同様）に対して０．１〜１０部、特に０．５〜５部の
範囲とすることが好ましい。The fatty acid metal salt and metal alkoxide of the component (C) constituting the water repellent composition of the present invention are
It acts as a catalyst in the reaction between both components (A) and (B) and the inorganic surface, and specifically includes dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, iron octoate, tetraisopropyl titanate,
Examples thereof include tetrabutyl titanate and hydrolyzed condensates of tetrabutyl titanate. The blending amount of the component (C) is in the range of 0.1 to 10 parts, particularly 0.5 to 5 parts, relative to 100 parts (parts by weight, the same applies hereinafter) of the components (A) and (B). It is preferable.
【００２３】本発明の組成物は、上述した（Ａ）、
（Ｂ）及び（Ｃ）成分を必須成分とするものであるが、
これらのほかガラスビーズ、石英粉、カーボン、グラフ
ァイト、タルク、マイカ、更には銀、銅、ニッケル、ア
ルミニウム、亜鉛などの金属粉末、アルミナ、亜鉛華、
酸化チタンなどの金属酸化物、ガラス繊維、カーボン繊
維、有機繊維などの繊維物質、窒化ほう素、炭化けい素
を本発明の目的を損わない範囲で配合しても差し支えな
い。The composition of the present invention comprises the above-mentioned (A),
Although the components (B) and (C) are essential components,
In addition to these, glass beads, quartz powder, carbon, graphite, talc, mica, metal powder such as silver, copper, nickel, aluminum and zinc, alumina, zinc white,
Metal oxides such as titanium oxide, fiber materials such as glass fibers, carbon fibers and organic fibers, boron nitride and silicon carbide may be blended within a range that does not impair the object of the present invention.
【００２４】本発明の組成物を構成する（Ａ）、（Ｂ）
及び（Ｃ）成分は、いずれも一般の有機溶剤に可溶であ
り、使用に当っては有機溶剤に溶解して希釈することが
好ましい。この溶剤としては、例えばベンゼン、トルエ
ン、キシレンなどの芳香族炭化水素類、アセトン、メチ
ルエチルケトン、メチルイソブチルケトンなどのケトン
類、酢酸エチル、酢酸イソブチルなどのエステル類、塩
化メチレン、トリクロロエチレン、パークロロエチレン
などの塩素化炭化水素類のような一般的な有機溶剤が使
用できる。なお、アルコール類は保存中に（Ｂ）成分が
脱水素反応を起こすため、好ましくない。このような溶
液にする場合、固形分の濃度は、０．１〜５重量％程度
とすることが良い。(A), (B) constituting the composition of the present invention
Both the component (C) and the component (C) are soluble in general organic solvents, and it is preferable that the components (C) are dissolved in an organic solvent and diluted before use. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and isobutyl acetate, methylene chloride, trichloroethylene and perchloroethylene. Common organic solvents such as chlorinated hydrocarbons can be used. In addition, alcohols are not preferable because the component (B) causes a dehydrogenation reaction during storage. In the case of using such a solution, the solid content concentration is preferably about 0.1 to 5% by weight.
【００２５】本発明の撥水処理剤組成物は、ガラス、金
属、セラミックなどの特に無機質材料の表面を浸漬、ス
プレー、刷毛塗り、スピンナー等の手段で塗布した後、
乾燥することにより、これらの表面を耐久性のある撥水
性、防汚性に優れた表面にすることができる。この場
合、乾燥は室温で十分であるが、４０〜２００℃で５〜
６０分加熱することが好ましく、これにより耐久性を向
上させることができる。また、対象となる被処理物とし
ては、家屋、自動車、鉄道、航空機などの窓ガラス、
鏡、ガラス、レンズなどの光学製品、各種ガラス器具、
陶器、タイル、あるいは反射防止やシリコーンハードコ
ーティングなどの処理をしたプラスチック材料などが例
示される。The water repellent composition of the present invention is applied to the surface of an inorganic material such as glass, metal or ceramic by dipping, spraying, brush coating, spinner, etc.
By drying, these surfaces can be made durable and have excellent water repellency and antifouling properties. In this case, drying at room temperature is sufficient, but at 40 to 200 ° C for 5 to 5
It is preferable to heat for 60 minutes, which can improve durability. In addition, as the target object to be processed, window glass of a house, an automobile, a railroad, an aircraft,
Optical products such as mirrors, glass and lenses, various glass appliances,
Examples include ceramics, tiles, and plastic materials that have been subjected to antireflection treatment, silicone hard coating, and the like.
【００２６】[0026]
【実施例】以下、実施例と比較例を示し、本発明を具体
的に示すが、本発明は下記の実施例に制限されるもので
はない。EXAMPLES Hereinafter, the present invention will be specifically shown by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００２７】［実施例１〜５、比較例１、２］表１に示
すパーフロロアルキル基含有有機ケイ素化合物、ＳｉＨ
基含有メチルポリシロキサン、ジブチル錫ジラウレー
ト、テトラブチルチタネート、有機溶剤を同表に示す量
で配合して撥水処理剤組成物を調製した。なお、表中の
数字は重量部を示す。[Examples 1 to 5, Comparative Examples 1 and 2] Perfluoroalkyl group-containing organosilicon compounds shown in Table 1 and SiH
A water-repellent agent composition was prepared by mixing group-containing methylpolysiloxane, dibutyltin dilaurate, tetrabutyl titanate, and an organic solvent in the amounts shown in the table. The numbers in the table indicate parts by weight.
【００２８】[0028]
【表１】 [Table 1]
【００２９】上記のように調製した撥水処理剤組成物
を、予めアセトンで脱脂洗浄し、乾燥したガラス板上
に、浸漬によりコーティングを行った後、１００℃で１
０分間熱処理を施した。この表面を下記に示すような方
法で水の接触角、水滴落下角度、防汚性を測定した。結
果を表２に示す。 （水の接触角）水平に保ったガラス板上に５μｌの水を
垂らし、Ｃｏｎｔａｃｔ ＡｎｇｌｅｍｅｔｅｒＣＡ−
Ａ（協和科学（株）製）にて接触角を測定した。 （水滴落下角度）静摩擦係数測定器（新東科学（株）製
ＨＥＩＤＯＮ−１０型）にガラス板を水平にセットし、
１００μｌの水を垂らす。次いで、徐々に傾きをかけ、
水が落下し始めたときの角度を測定した。 （防汚性）サンシャインウエザーメーター（スガ試験機
製）中にガラス板を４５°の角度でセットし、１００時
間暴露した後、外観を観察した。The water repellent composition prepared as described above was degreased and washed with acetone in advance, and a dried glass plate was coated by dipping and then at 100 ° C. for 1 hour.
Heat treatment was performed for 0 minutes. The surface was measured for contact angle of water, water drop angle, and antifouling property by the following methods. The results are shown in Table 2. (Contact angle of water) 5 μl of water was dropped on a glass plate kept horizontal, and the Contact Anglemeter CA-
The contact angle was measured with A (manufactured by Kyowa Kagaku Co., Ltd.). (Water drop drop angle) A glass plate was set horizontally on a static friction coefficient measuring device (HEIDON-10 type manufactured by Shinto Scientific Co., Ltd.),
Drop 100 μl of water. Then gradually incline,
The angle at which the water started to fall was measured. (Anti-fouling property) A glass plate was set in a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) at an angle of 45 °, exposed for 100 hours, and then the appearance was observed.
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【発明の効果】本発明の撥水処理剤組成物は、一般の有
機溶剤に可溶で使い易いと共に、無機質表面を処理する
ことにより簡単に耐久性のある撥水性、防汚性表面を与
えることができる。EFFECT OF THE INVENTION The water repellent composition of the present invention is soluble in general organic solvents and is easy to use, and by treating the inorganic surface, it easily gives a durable water repellent and antifouling surface. be able to.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 83/05 8319−4Ｊ Ｃ０９Ｄ 5/00 ＰＰＧ 6904−4Ｊ 183/04 ＰＭＴ 8319−4Ｊ 183/05 ＰＭＵ 8319−4Ｊ (72)発明者 一戸 省二 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 (51) Int.Cl. 5 Identification number Internal reference number FI Technical display location C08L 83/05 8319-4J C09D 5/00 PPG 6904-4J 183/04 PMT 8319-4J 183/05 PMU 8319-4J (72) Inventor Shoji Ichinohe No. 1 Hitomi, Osamu Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory
Claims (1)
フロロアルキル基含有有機ケイ素化合物又は該化合物の
部分加水分解縮合物、 【化１】 （但し、式中Ｒ1、Ｒ2はそれぞれ炭素原子数１〜４の１
価の炭化水素基、Ｑは炭素原子数２〜１０の２価の有機
基、ｐは１〜１２の整数、ａは０又は１を表す。） （Ｂ）下記一般式（２）で示されるＳｉＨ基含有メチル
ポリシロキサン化合物、 【化２】 （但し、式中Ａは水素原子又はメチル基、ｍは０〜１０
０の整数、ｎは０〜２００の整数、１０≦ｍ＋ｎ≦２０
０であるが、ｎ＝０のときＡは水素原子である。） （Ｃ）脂肪酸金属塩又は金属アルコキシドを含有してな
ることを特徴とする撥水処理剤組成物。1. (A) A perfluoroalkyl group-containing organosilicon compound represented by the following general formula (1) or a partial hydrolysis-condensation product of the compound: (However, in the formula, R 1 and R 2 are each 1 to 4 carbon atoms.
A valent hydrocarbon group, Q represents a divalent organic group having 2 to 10 carbon atoms, p represents an integer of 1 to 12, and a represents 0 or 1. (B) SiH group-containing methylpolysiloxane compound represented by the following general formula (2): (However, in the formula, A is a hydrogen atom or a methyl group, and m is 0 to 10.
An integer of 0, n is an integer of 0 to 200, 10 ≦ m + n ≦ 20
Although it is 0, when n = 0, A is a hydrogen atom. (C) A water repellent composition comprising a fatty acid metal salt or a metal alkoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7303193A JP2776190B2 (en) | 1993-03-08 | 1993-03-08 | Water repellent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7303193A JP2776190B2 (en) | 1993-03-08 | 1993-03-08 | Water repellent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06256756A true JPH06256756A (en) | 1994-09-13 |
| JP2776190B2 JP2776190B2 (en) | 1998-07-16 |
Family
ID=13506577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7303193A Expired - Fee Related JP2776190B2 (en) | 1993-03-08 | 1993-03-08 | Water repellent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2776190B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996009993A1 (en) * | 1994-09-27 | 1996-04-04 | Metallgesellschaft Aktiengesellschaft | Mixture for treating silicon-containing substrates |
| WO2002077116A1 (en) * | 2001-03-21 | 2002-10-03 | Daikin Industries, Ltd. | Surface-treating agent comprising inorganic/organic composite material |
| JP2007520740A (en) * | 2003-12-23 | 2007-07-26 | スリーエム イノベイティブ プロパティズ カンパニー | Composition of oligomeric fluorosilane and surface treatment of retroreflective sheet |
| US7847015B2 (en) | 2006-11-15 | 2010-12-07 | Shin-Etsu Chemical Co., Ltd. | Coating composition |
| WO2012157507A1 (en) * | 2011-05-17 | 2012-11-22 | 東亞合成株式会社 | Surface-treating agent and surface treatment method |
-
1993
- 1993-03-08 JP JP7303193A patent/JP2776190B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996009993A1 (en) * | 1994-09-27 | 1996-04-04 | Metallgesellschaft Aktiengesellschaft | Mixture for treating silicon-containing substrates |
| BE1008724A3 (en) * | 1994-09-27 | 1996-07-02 | Couttenier Andre | COMPOSITION FOR PROTECTING WATER REPELLENT AND MAKING A siliceous substrate. |
| JPH10506144A (en) * | 1994-09-27 | 1998-06-16 | メタルゲゼルシャフト・アクチエンゲゼルシャフト | Mixture for treating silicon-containing substrates |
| US6030444A (en) * | 1994-09-27 | 2000-02-29 | Metallgesellschaft Aktiengesellschaft | Mixture for treating silicon-containing substrates |
| WO2002077116A1 (en) * | 2001-03-21 | 2002-10-03 | Daikin Industries, Ltd. | Surface-treating agent comprising inorganic/organic composite material |
| US7125926B2 (en) | 2001-03-21 | 2006-10-24 | Daikin Industries, Ltd. | Surface treatment agent comprising inorganic-organic hybrid material |
| JP2007520740A (en) * | 2003-12-23 | 2007-07-26 | スリーエム イノベイティブ プロパティズ カンパニー | Composition of oligomeric fluorosilane and surface treatment of retroreflective sheet |
| US7847015B2 (en) | 2006-11-15 | 2010-12-07 | Shin-Etsu Chemical Co., Ltd. | Coating composition |
| WO2012157507A1 (en) * | 2011-05-17 | 2012-11-22 | 東亞合成株式会社 | Surface-treating agent and surface treatment method |
| JPWO2012157507A1 (en) * | 2011-05-17 | 2014-07-31 | 東亞合成株式会社 | Surface treatment agent and surface treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2776190B2 (en) | 1998-07-16 |
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