JP3269314B2 - Water repellent agent - Google Patents
Water repellent agentInfo
- Publication number
- JP3269314B2 JP3269314B2 JP02729595A JP2729595A JP3269314B2 JP 3269314 B2 JP3269314 B2 JP 3269314B2 JP 02729595 A JP02729595 A JP 02729595A JP 2729595 A JP2729595 A JP 2729595A JP 3269314 B2 JP3269314 B2 JP 3269314B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- water
- carbon atoms
- repellent
- compound represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ガラス、セラミック
ス、金属等の無機質表面に優れた撥水性及び防汚性を与
えることができる有機溶剤に可溶性の撥水処理剤に関す
る。特には、雨水により無機質表面に自浄性を与えるこ
とのできる撥水処理剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-repellent treatment agent soluble in an organic solvent capable of imparting excellent water repellency and antifouling property to inorganic surfaces such as glass, ceramics and metal. In particular, the present invention relates to a water-repellent agent capable of imparting self-cleaning properties to an inorganic surface with rainwater.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
ガラス、セラミックス、金属等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、応用範囲の拡大化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、特に特開昭５８−１４７４８４号、同６
０−２２１４７０号及び特開平４−９６９３５号公報に
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
リシラザンが撥水性に優れていることが記載されてい
る。2. Description of the Related Art
Various studies have been made to improve the properties of the surface of inorganic materials such as glass, ceramics, and metals by treating them with various surface treatment agents, thereby improving the performance and expanding the range of application. As one of the methods, a method has been proposed in which a hydrophilic surface is treated with a silicone composition to modify the surface to a water-repellent surface, and in particular, JP-A-58-147484 and JP-A-58-147484.
No. 0-221470 and JP-A-4-96935 describe that polysiloxane or polysilazane containing a perfluoroalkyl group is excellent in water repellency.
【０００３】しかしながら、上記撥水処理剤は、撥水効
果には優れているものの水滴の落下性に劣るため、家
屋、ビルなどの建築物の窓ガラス等の防汚処理剤として
適用した場合、水滴が落下せずにガラス表面に水玉状に
留まり、これにより空気中のチリ、油分等が付着してか
えって汚れたりする場合があった。[0003] However, the above-mentioned water-repellent agent is excellent in water-repellent effect but is inferior in the dropping property of water droplets. Therefore, when the agent is applied as an antifouling agent for window glass of buildings such as houses and buildings, Water droplets did not fall and remained in a polka dot shape on the glass surface, which sometimes caused dust and oil in the air to adhere and contaminate them.
【０００４】また、特開平３−２９０４３７号公報には
含フッ素シラザン化合物が提案されているが、この化合
物は上記欠点は改良されている反面、一般有機溶剤への
溶解性が悪く、フロン規制対象物である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ないという問題があ
り、このため応用範囲が限定されるという欠点があっ
た。Japanese Unexamined Patent Publication (Kokai) No. 3-29037 proposes a fluorine-containing silazane compound. This compound has the above-mentioned disadvantages, but has a poor solubility in general organic solvents, and is subject to CFC regulations. However, there is a problem that it is stably soluble only in fluorocarbons such as 1,1,3-trichlorotrifluoroethane and expensive fluorohydrocarbons, which limits the range of application. .
【０００５】本発明は上記事情に鑑みなされたもので、
撥水性付与効果及び水滴の落下性改善効果に優れ、被処
理物表面に優れた撥水性、防汚性を与えることができ、
しかも有機溶剤に可溶性の撥水処理剤を提供することを
目的とする。[0005] The present invention has been made in view of the above circumstances,
Excellent effect of imparting water repellency and improving the dropping property of water droplets, and can impart excellent water repellency and stain resistance to the surface of the workpiece,
Moreover, an object of the present invention is to provide a water repellent agent soluble in an organic solvent.
【０００６】[0006]
【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、下記一般式
（Ｉ）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、下記一般式（ＩＩ）で示される加水分解性基
含有メチルポリシロキサン化合物との水及び親水性溶媒
中での共加水分解物が撥水処理剤として優れた特性を有
することを見出した。The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a perfluoroalkyl group-containing organosilicon compound represented by the following general formula (I): It has been found that a co-hydrolyzate of the hydrolyzable group-containing methylpolysiloxane compound represented by (II) in water and a hydrophilic solvent has excellent properties as a water-repellent agent.
【０００７】[0007]
【化３】 （但し、式中Ｒ1は炭素原子数１〜４の一価炭化水素
基、Ｒ2は炭素原子数１〜４のアルコキシ基又はアシロ
キシ基、Ｑは炭素原子数２〜１０の二価の有機基であ
り、ａは０又は１、ｐは４〜１２の整数である。）Embedded image (Wherein, R 1 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R 2 is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, and Q is a divalent organic group having 2 to 10 carbon atoms. A is 0 or 1, and p is an integer of 4 to 12.)
【０００８】[0008]
【化４】 （但し、式中Ｒ3は炭素原子数１〜４の一価炭化水素
基、Ｒ4は炭素原子数１〜４のアルコキシ基又はアシロ
キシ基、Ｚは酸素原子又は炭素原子数２〜１０の二価の
炭化水素基であり、ｂは０，１又は２、ｍは５〜１００
の整数である。）Embedded image (Where R 3 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R 4 is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, Z is an oxygen atom or a divalent hydrocarbon group having 2 to 10 carbon atoms. B is 0, 1 or 2, m is 5 to 100
Is an integer. )
【０００９】即ち、上記共加水分解物は、式（Ｉ）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付与
効果に、また、式（ＩＩ）の加水分解性基含有メチルポ
リシロキサン化合物が水滴の落下性改善効果に寄与する
と共に、これら両成分の共加水分解により無機質表面と
の反応性に富んだシラノール基を有するもので、それ
故、被処理物表面に優れた撥水性、防汚性を与えること
ができ、しかも親水性溶媒に可溶性で、特殊なフッ素系
溶剤を使用しなくてもよいため広範囲に利用でき、撥水
処理剤として有効であることを知見し、本発明をなすに
至ったものである。That is, in the above co-hydrolysate, the perfluoroalkyl group-containing organosilicon compound of the formula (I) has a water repellency-imparting effect, and the hydrolyzable group-containing methylpolysiloxane compound of the formula (II) has a water droplet. It has a silanol group rich in reactivity with the inorganic surface by co-hydrolysis of these two components, and therefore has excellent water repellency and antifouling property on the surface of the object to be treated. Can be used, and it is soluble in a hydrophilic solvent, and can be widely used because it does not require the use of a special fluorine-based solvent, and has been found to be effective as a water-repellent treatment agent. It has been reached.
【００１０】従って、本発明は、上記一般式（Ｉ）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、
上記一般式（ＩＩ）で示される加水分解性基含有メチル
ポリシロキサン化合物とから本質的になる成分の水及び
親水性溶媒中での共加水分解物を含有してなる撥水処理
剤を提供する。Accordingly, the present invention provides a perfluoroalkyl group-containing organosilicon compound represented by the above general formula (I),
Provided is a water-repellent treatment agent comprising a water-repellent agent and a co-hydrolyzate in a hydrophilic solvent, which are essentially composed of a hydrolyzable group-containing methylpolysiloxane compound represented by the general formula (II). .
【００１１】以下、本発明につき更に詳細に説明する
と、本発明の撥水処理剤の第一の原料は、下記一般式
（Ｉ）で示されるパーフロロアルキル基含有有機ケイ素
化合物である。Hereinafter, the present invention will be described in more detail. The first raw material of the water-repellent treating agent of the present invention is a perfluoroalkyl group-containing organosilicon compound represented by the following general formula (I).
【００１２】[0012]
【化５】 （但し、式中Ｒ1は炭素原子数１〜４の一価炭化水素
基、Ｒ2は炭素原子数１〜４のアルコキシ基又はアシロ
キシ基、Ｑは炭素原子数２〜１０の二価の有機基であ
り、ａは０又は１、ｐは４〜１２の整数である。）Embedded image (Wherein, R 1 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R 2 is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, and Q is a divalent organic group having 2 to 10 carbon atoms. A is 0 or 1, and p is an integer of 4 to 12.)
【００１３】上記式（Ｉ）において、Ｒ1としては例え
ばメチル基、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−ブチル基等が挙
げられ、Ｒ2としては例えばメトキシ基、エトキシ基、
ｎ−プロポキシ基、イソプロポキシ基、イソプロペノキ
シ基、ｎ−ブトキシ基、アセトキシ基等が挙げられる。
また、Ｑはパーフロロアルキル基とケイ素原子を結合す
る基であり、二価炭化水素基又は分子中に酸素原子、窒
素原子又は硫黄原子を含む二価炭化水素基が挙げられ、
具体的に−ＣＨ2ＣＨ2−，−ＣＨ2ＯＣＨ2ＣＨ2ＣＨ
2−，−ＣＯＮＨＣＨ2ＣＨ2ＣＨ2−，−ＣＯＮＨＣＨ2
ＣＨ2ＮＨＣＨ2ＣＨ2ＣＨ2−，−ＳＯ2ＮＨＣＨ2ＣＨ2
ＣＨ2−，−ＣＨ2ＣＨ2ＯＣＯＮＨＣＨ2ＣＨ2ＣＨ2−等
の基が例示される。更に、ｐはパーフロロアルキル基の
炭素数を示すもので４〜１２であり、ｐが１２を越える
と有機溶剤への溶解性が悪くなる。ａは０又は１であ
る。[0013] In the above formula (I), for example a methyl group as R 1, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, s- butyl group and the like, as R 2 is For example, a methoxy group, an ethoxy group,
Examples thereof include an n-propoxy group, an isopropoxy group, an isopropenoxy group, an n-butoxy group, and an acetoxy group.
Q is a group connecting a perfluoroalkyl group and a silicon atom, and examples thereof include a divalent hydrocarbon group or a divalent hydrocarbon group containing an oxygen atom, a nitrogen atom or a sulfur atom in a molecule,
Specifically -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
Examples include groups such as CH 2 —, —CH 2 CH 2 OCONHCH 2 CH 2 CH 2 —. Further, p represents the number of carbon atoms of the perfluoroalkyl group and is 4 to 12, and if p exceeds 12, the solubility in an organic solvent becomes poor. a is 0 or 1.
【００１４】上記式（Ｉ）のパ−フロロアルキル基含有
有機ケイ素化合物として具体的には、下記化合物を例示
することができ、これら化合物の１種類を単独で又は２
種類以上を混合して使用することができる。Specific examples of the perfluoroalkyl group-containing organosilicon compound of the above formula (I) include the following compounds. One of these compounds may be used alone or
More than one kind can be mixed and used.
【００１５】[0015]
【化６】 Embedded image
【００１６】次に、第二原料の加水分解性基含有メチル
ポリシロキサン化合物は、下記一般式（ＩＩ）で示され
る化合物である。Next, the hydrolyzable group-containing methylpolysiloxane compound as the second raw material is a compound represented by the following general formula (II).
【００１７】[0017]
【化７】 （但し、式中Ｒ3は炭素原子数１〜４の一価炭化水素
基、Ｒ4は炭素原子数１〜４のアルコキシ基又はアシロ
キシ基、Ｚは酸素原子又は炭素原子数２〜１０の二価の
炭化水素基であり、ｂは０，１又は２、ｍは５〜１００
の整数である。）Embedded image (Where R 3 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R 4 is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, Z is an oxygen atom or a divalent hydrocarbon group having 2 to 10 carbon atoms. B is 0, 1 or 2, m is 5 to 100
Is an integer. )
【００１８】ここで、Ｒ3としては、前記Ｒ1と同様の基
が挙げられ、Ｒ4としては、前記Ｒ2と同様の基が挙げら
れる。また、Ｚとしては、酸素原子のほか、二価の炭化
水素基として下記の基（アルキレン基）が例示される。Here, R 3 is the same group as R 1, and R 4 is the same group as R 2 . Examples of Z include the following groups (alkylene groups) as divalent hydrocarbon groups in addition to oxygen atoms.
【００１９】[0019]
【化８】 Embedded image
【００２０】また、ｍは５〜１００、好ましくは５〜５
０の整数、ｍが５未満では前記した水滴の落下性が不足
して防汚性が悪くなり、１００を越えると共加水分解物
の安定性が悪くなる。M is 5 to 100, preferably 5 to 5
If the integer of 0 and m is less than 5, the dropping property of the water droplets described above is insufficient, and the antifouling property is deteriorated. If it exceeds 100, the stability of the co-hydrolyzate is deteriorated.
【００２１】上記式（Ｉ）のパーフロロアルキル基含有
有機ケイ素化合物と式（ＩＩ）の加水分解性基含有メチ
ルポリシロキサン化合物との配合比は、重量比で（Ｉ）
／（ＩＩ）が１０／９０〜９０／１０、特に２０／８０
〜８０／２０であることが好ましい。式（Ｉ）の化合物
の配合比率が１０重量％未満では十分な撥水性が得られ
ない場合があり、９０重量％を越えると水滴の落下性が
不足して十分な防汚性が得られなくなる。The compounding ratio of the perfluoroalkyl group-containing organosilicon compound of the above formula (I) and the hydrolyzable group-containing methylpolysiloxane compound of the formula (II) is (I)
/ (II) is from 10/90 to 90/10, especially 20/80
It is preferably 80 to 20. If the compounding ratio of the compound of the formula (I) is less than 10% by weight, sufficient water repellency may not be obtained, and if it exceeds 90% by weight, dropping property of water drops is insufficient and sufficient antifouling property cannot be obtained. .
【００２２】更に、上記両化合物の共加水分解に使用す
る親水性溶媒としては、上記式（Ｉ）、（ＩＩ）の化合
物及び水を溶解するものであれば特に制限はなく、例え
ばメタノール、エタノール、イソプロパノール、ｎ−プ
ロパ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。親水性溶媒の使用量は特に制限はな
いが、式（Ｉ）及び（ＩＩ）の化合物の濃度が１〜３０
重量％、特に３〜１５重量％となる範囲が好ましい。The hydrophilic solvent used for the co-hydrolysis of the two compounds is not particularly limited as long as it can dissolve the compounds of the above formulas (I) and (II) and water. Alcohols such as isopropanol and n-propanol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and cellosolve acetate; ketones such as acetone and methyl ethyl ketone; and ethers such as dioxane and tetrahydrofuran. The amount of the hydrophilic solvent used is not particularly limited, but the concentration of the compound of the formulas (I) and (II) is 1 to 30.
%, Particularly preferably in the range of 3 to 15% by weight.
【００２３】また、共加水分解は水を使用するが、水の
添加量は式（Ｉ）及び（ＩＩ）の化合物中に含まれるア
ルコキシ基及びアシロキシ基の合計量に対して０．５当
量以上、特に０．５〜２当量が適当であり、０．５当量
に満たないと加水分解率が不十分であるため無機質表面
との反応性が弱くなる場合があり、２当量を越えても意
味がない場合がある。The co-hydrolysis uses water, and the amount of water added is 0.5 equivalent or more based on the total amount of alkoxy groups and acyloxy groups contained in the compounds of the formulas (I) and (II). In particular, 0.5 to 2 equivalents is appropriate. If the amount is less than 0.5 equivalent, the hydrolysis rate is insufficient, so that the reactivity with the inorganic surface may be weak. There may not be.
【００２４】本発明では、共加水分解時に反応を促進す
る目的で系のｐＨを７未満、好ましくはｐＨ５以下とす
るように酸を微量添加してもよい。酸としては、塩酸、
硫酸、硝酸、酢酸、メタンスルホン酸、トリフロロメタ
ンスルホン酸、パラトルエンスルホン酸、トリフロロ酢
酸、リン酸等が挙げられる。In the present invention, for the purpose of accelerating the reaction during co-hydrolysis, a small amount of acid may be added so that the pH of the system is less than 7, preferably 5 or less. As the acid, hydrochloric acid,
Sulfuric acid, nitric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, trifluoroacetic acid, phosphoric acid, and the like.
【００２５】上記共加水分解反応は、別に限定されない
が、５０〜１００℃で２〜１０時間行うことが望まし
い。The above-mentioned cohydrolysis reaction is not particularly limited, but is preferably carried out at 50 to 100 ° C. for 2 to 10 hours.
【００２６】本発明の撥水処理剤は、上記共加水分解物
をそのまま使用してもよいが、必要に応じて上述した親
水性溶媒、あるいはベンゼン、トルエン、キシレン等の
芳香族炭化水素類、酢酸エチル、酢酸イソブチル等のエ
ステル類などの有機溶剤で０．１〜５％程度の濃度に希
釈して使用してもよい。被処理物への使用方法として
は、被処理物表面に浸漬、スプレー、刷毛塗り、スピン
ナー等の手段で塗布、乾燥すれば耐久性のある撥水・防
汚表面を得ることができる。なお、乾燥は室温で十分で
あるが、４０〜２００℃で５〜６０分加熱することが耐
久性の点でより好ましい。As the water-repellent treatment agent of the present invention, the above-mentioned co-hydrolysate may be used as it is, but if necessary, the above-mentioned hydrophilic solvent or aromatic hydrocarbons such as benzene, toluene and xylene; It may be used after being diluted with an organic solvent such as esters such as ethyl acetate and isobutyl acetate to a concentration of about 0.1 to 5%. As a method of using the material to be treated, a durable water-repellent and stain-resistant surface can be obtained by immersing, spraying, brushing, applying or drying on the surface of the material to be treated and drying. Drying at room temperature is sufficient, but heating at 40 to 200 ° C. for 5 to 60 minutes is more preferable in terms of durability.
【００２７】[0027]
【発明の効果】本発明の撥水処理剤は、撥水性付与効果
及び水滴の落下性改善効果に優れ、被処理物表面に優れ
た撥水性、防汚性を与えることができ、しかも有機溶剤
に可溶性であるもので、各種の無機質の表面を有する材
料の表面処理に利用することができ、具体的には建築
物、鉄道、車両、航空機等の窓ガラス、鏡、ガラスレン
ズ等の光学部品、各種ガラス器具、陶器、タイル、無機
系の反射防止コートやシリコーンハードコート等の処理
をしたプラスチック材料などの表面処理に広範囲に使用
することができる。The water-repellent treating agent of the present invention is excellent in the effect of imparting water repellency and the effect of improving the dropping property of water droplets, and can impart excellent water repellency and antifouling property to the surface of the object to be treated. It is soluble in water and can be used for surface treatment of materials having various inorganic surfaces. Specifically, optical components such as windows, mirrors, glass lenses, etc. of buildings, railways, vehicles, aircrafts, etc. It can be widely used for surface treatment of various kinds of glass utensils, pottery, tiles, and plastic materials treated with inorganic anti-reflection coats and silicone hard coats.
【００２８】[0028]
【実施例】以下、実施例及び比較例を示して本発明を具
体的に説明するが、本発明は下記実施例に制限されるも
のではない。EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
【００２９】〔実施例１〕 温度計、攪拌機、冷却器を備えた１リットルガラス反応
器に式Ｃ8Ｆ17ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3で示される
パーフロロ基含有有機ケイ素化合物１０．０ｇ、下記式
（２）で示される加水分解性基含有メチルポリシロキサ
ン化合物１０．０ｇ、親水性溶媒としてイソプロパノー
ル４８０．０ｇ及び０．１Ｎ硫酸水１．１７ｇを仕込
み、８０℃で２時間共加水分解反応を行い、撥水処理剤
溶液を得た。なお、系のｐＨは２．５であった。Example 1 A perfluoro group-containing organosilicon compound represented by the formula C 8 F 17 CH 2 CH 2 Si (OCH 3 ) 3 was placed in a 1 liter glass reactor equipped with a thermometer, a stirrer, and a cooler. 0 g, 10.0 g of a hydrolyzable group-containing methylpolysiloxane compound represented by the following formula (2), 480.0 g of isopropanol as a hydrophilic solvent, and 1.17 g of 0.1 N sulfuric acid aqueous solution were charged and co-hydrolyzed at 80 ° C. for 2 hours. A decomposition reaction was performed to obtain a water-repellent treating agent solution. The pH of the system was 2.5.
【００３０】[0030]
【化９】 Embedded image
【００３１】〔比較例１〜２〕 パーフロロ基含有有機ケイ素化合物、加水分解性基含有
メチルポリシロキサン化合物、水、親水性溶媒の種類と
添加量、共加水分解条件を表１に示すように変えた以外
は実施例１と同様にして撥水処理剤溶液を得た。Comparative Examples 1-2 The types and amounts of perfluoro group-containing organosilicon compound, hydrolyzable group-containing methylpolysiloxane compound, water and hydrophilic solvent, and cohydrolysis conditions were changed as shown in Table 1. A water-repellent treating agent solution was obtained in the same manner as in Example 1 except for the above.
【００３２】[0032]
【００３３】次に、上記実施例及び比較例で得られた撥
水処理剤溶液をそれぞれ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４μｍ厚さにコーティン
グを行った後、１００℃で１０分間熱処理を施した。こ
れらの表面について、下記方法で水の接触角、水滴落下
角度、防汚性を測定した。結果を表１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、接触角
測定装置〔Ｃｏｎｔａｃｔ Ａｎｇｌｅ Ｍｅｔｅｒ
ＣＡ−Ａ（協和科学株式会社製）〕にて接触角を測定し
た。水滴落下角度 静摩擦係数測定機（新東科学株式会社製、ＨＥＩＤＯＮ
−１０型）にガラス板を水平にセットし、１００μｌの
水を垂らした後、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 サンシャインウェザーメーター（スガ試験機社製）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。Next, each of the water repellent treatment solutions obtained in the above Examples and Comparative Examples was previously degreased and washed with acetone, coated on a dried glass plate by dipping to a thickness of 4 μm, and then dried at 100 ° C. For 10 minutes. For these surfaces, the contact angle of water, the drop angle of water droplets, and the antifouling property were measured by the following methods. Table 1 shows the results. Contact angle of water 5 μl of water is dropped on a glass plate kept horizontal, and a contact angle measuring device [Contact Angle Meter] is used.
CA-A (manufactured by Kyowa Science Co., Ltd.)]. Water Drop Fall Angle Static Friction Coefficient Measuring Machine (Shinto Kagaku Co., Ltd., HEIDON
(−10 type), the glass plate was set horizontally, and 100 μl of water was dropped on the glass plate. Then, the glass plate was gradually tilted, and the angle at which the water started to fall was measured. The glass plate was set at an angle of 45 ° in an antifouling sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), and after exposure for 100 hours, the external appearance was observed.
【００３４】表１の結果より、本発明の撥水処理剤（実
施例）は、撥水効果及び水滴の落下性に優れ、被処理物
表面に優れた撥水性、防汚性を与えることができること
が確認された。From the results shown in Table 1, it can be seen that the water-repellent treating agent of the present invention (Example) is excellent in water-repellent effect and dropping property of water droplets, and can impart excellent water-repellent property and antifouling property to the surface of the object to be treated. It was confirmed that it was possible.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【化１０】 Embedded image
───────────────────────────────────────────────────── フロントページの続き (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 (56)参考文献 特開 平３−275726（ＪＰ，Ａ) 特開 平２−233535（ＪＰ，Ａ) 特開 昭50−126033（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09K 3/18 104 C03C 17/30 C08G 77/24 C09D 183/08 C09K 3/00 112 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shoji Ichinohe 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronics Materials Research Laboratory (56) References JP-A-3-275726 (JP, A) JP-A-2-233535 (JP, A) JP-A-50-126033 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C09K 3/18 104 C03C 17 / 30 C08G 77/24 C09D 183/08 C09K 3/00 112
Claims (1)
アルキル基含有有機ケイ素化合物と、下記一般式（Ｉ
Ｉ）で示される加水分解性基含有メチルポリシロキサン
化合物とから本質的になる成分の水及び親水性溶媒中で
の共加水分解物を含有してなることを特徴とする撥水処
理剤。 【化１】 （但し、式中Ｒ1は炭素原子数１〜４の一価炭化水素
基、Ｒ2は炭素原子数１〜４のアルコキシ基又はアシロ
キシ基、Ｑは炭素原子数２〜１０の二価の有機基であ
り、ａは０又は１、ｐは４〜１２の整数である。） 【化２】 （但し、式中Ｒ3は炭素原子数１〜４の一価炭化水素
基、Ｒ4は炭素原子数１〜４のアルコキシ基又はアシロ
キシ基、Ｚは酸素原子又は炭素原子数２〜１０の二価の
炭化水素基であり、ｂは０，１又は２、ｍは５〜１００
の整数である。）1. A perfluoroalkyl group-containing organosilicon compound represented by the following general formula (I):
A water-repellent treating agent comprising a co-hydrolyzate in water and a hydrophilic solvent, which is a component consisting essentially of the hydrolyzable group-containing methylpolysiloxane compound represented by I). Embedded image (Wherein, R 1 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R 2 is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, and Q is a divalent organic group having 2 to 10 carbon atoms. A is 0 or 1, and p is an integer of 4 to 12.) (Where R 3 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, R 4 is an alkoxy group or an acyloxy group having 1 to 4 carbon atoms, Z is an oxygen atom or a divalent hydrocarbon group having 2 to 10 carbon atoms. B is 0, 1 or 2, m is 5 to 100
Is an integer. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02729595A JP3269314B2 (en) | 1994-01-31 | 1995-01-23 | Water repellent agent |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2734194 | 1994-01-31 | ||
| JP6-27341 | 1994-01-31 | ||
| JP02729595A JP3269314B2 (en) | 1994-01-31 | 1995-01-23 | Water repellent agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07252472A JPH07252472A (en) | 1995-10-03 |
| JP3269314B2 true JP3269314B2 (en) | 2002-03-25 |
Family
ID=26365199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02729595A Expired - Fee Related JP3269314B2 (en) | 1994-01-31 | 1995-01-23 | Water repellent agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3269314B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19649954A1 (en) * | 1996-12-03 | 1998-06-04 | Huels Chemische Werke Ag | Fluoroalkyl-functional organosiloxane-containing compositions based on alcohol, process for their preparation and their use |
| DE60005910T2 (en) | 1999-11-16 | 2004-08-19 | Asahi Glass Co., Ltd. | Substrate with treated surface layers and process for its production |
| DE60031220T2 (en) | 1999-11-16 | 2007-08-23 | Asahi Glass Co., Ltd. | Substrate with treated surfaces and process for its preparation |
| JP5553297B2 (en) * | 2009-04-21 | 2014-07-16 | 独立行政法人産業技術総合研究所 | Coating composition |
-
1995
- 1995-01-23 JP JP02729595A patent/JP3269314B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07252472A (en) | 1995-10-03 |
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