JP2003147340A - Super water repellent and super-water-repellent material made by using it - Google Patents

Super water repellent and super-water-repellent material made by using it

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JP2003147340A
JP2003147340A JP2001352319A JP2001352319A JP2003147340A JP 2003147340 A JP2003147340 A JP 2003147340A JP 2001352319 A JP2001352319 A JP 2001352319A JP 2001352319 A JP2001352319 A JP 2001352319A JP 2003147340 A JP2003147340 A JP 2003147340A
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water
repellent
super
coating
example
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Akira Nakajima
Koji Takeda
章 中島
宏二 武田
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Asti Ltd Advanced Systems Of Technology Incubation
Toto Ltd
東陶機器株式会社
株式会社先端技術インキュベーションシステムズ
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Abstract

PROBLEM TO BE SOLVED: To provide a low-temperature dryable super-water-repellent coating composition excellent in water repellency and transparency, and a super-water- repellent material made by coating a base material with the composition.
SOLUTION: This super water repellent is characterized in that it is obtained by dispersing (A) fine silica particles having hydrophobicity imparted thereto and (B) a hydrophobic resin at least containing one or more materials selected from the group consisting of fluororesins, hydrolyzable silanes, polyorganosiloxanes, acrylic silicone resins and acrylic resins in an organic solvent in such a manner that the weight fractions of the component A and component B respectively are 30-100% and 0-70% after evaporation and that the fine silica particles having hydrophobicity imparted thereto is subjected to ultrasonic waves having a frequency of 10-30 kHz and an amplitude of 10-50 μm before being dispersed in the organic solvent.
COPYRIGHT: (C)2003,JPO

Description

【発明の詳細な説明】 【0001】 【発明の属する技術分野】本発明は、超撥水剤およびそれを用いて作製される超撥水材に関する。 BACKGROUND OF THE INVENTION [0001] [Technical Field of the Invention The present invention relates to ultra-water repellent material prepared using a super water-repellent agent and it. 【0002】 【従来の技術】一般に、固体表面をフッ素やシリコーンなどを主成分とする低い表面エネルギーの物質で形成すれば優れた撥水性を持たせることができることが知られており、かつその表面に適切な粗さが付与されることによって撥水性がより強調されることが知られている。 [0002] In general, the solid surface is known to a fluorine or silicone can have a low surface energy repellent excellent be formed of a material of a main component, and the surface it is known that the water repellency is further emphasized by the proper roughness is imparted to. 【0003】例えば、特公平7−86146号公報には、400nm未満の凹凸が形成された基体の表面に、 [0003] For example, Japanese Patent Kokoku 7-86146, the surface of the substrate unevenness of less than 400nm are formed,
少なくともシロキサン結合を介してフッ素を含む化学吸着単分子膜が形成された撥水撥油防汚性被膜及びその製造方法が記載されている。 Chemisorption monomolecular film water- and oil-repellent formed antifouling coating film and a manufacturing method thereof comprising the fluorine through at least a siloxane bond is described. 凹凸の形成方法としては、サンドブラスト処理、フッ酸を用いた化学エッチング法、 As a method of forming the irregularities, sandblasting, chemical etching method using hydrofluoric acid,
サンドペーパーによるラビング法、電界エッチング等が例示されている。 Rubbing method by sandpaper, electric field etching and the like are exemplified. 【0004】また、特開平7−197017号公報には、表面の少なくとも一部に、大きい周期の凹凸構造が形成されその凹凸構造が前記周期より小さい周期の凹凸構造を有し、その表面積倍増因子が5以上である撥水表面を有する固体およびその生成方法が記載されている。 [0004] JP-A-7-197017, on at least a portion of the surface, the concavo-convex structure rough structure of a large period are formed has an uneven structure period smaller than the period, the surface area doubles factor There solids and generating method thereof repellent surface is 5 or more is described.
凹凸の周期が1mm以下10nm以上、凹凸の形成方法としては、機械加工、電気めっき等の化学反応処理、結晶析出、粒子を凝集させる等が開示されている。 Irregularities of cycle 1mm or less 10nm or more, as a method of forming the irregularities, machining, chemical reaction processes, such as electroplating, crystallization, or the like to aggregate particles is disclosed. 【0005】また、特開平9−202650号公報には、基体上に形成した花弁状透明アルミナ膜と、該花弁状透明アルミナ膜上に被覆した撥水膜とでなることを特徴とする撥水撥油防汚性膜及びその形成法が記載されている。 Further, JP-A-9-202650, water repellent, wherein the petal-like transparent alumina film formed on a substrate, to become in a water-repellent film coated on said curd valve like transparent alumina film oil repellent antifouling film and its formation method is described. 花弁状透明アルミナ膜の形成法としては、アルミニウムアルコキシドと安定剤から少なくともなる塗布液で被膜を、600℃以下で乾燥し熱処理して成膜したアモルファスアルミナ膜を、熱水処理し、乾燥、焼成させる方法が例示されている。 The method of forming the petal-like transparent alumina film, a film at least composed of a coating solution of aluminum alkoxide and a stabilizer, a dried amorphous alumina film formed by heat treatment at 600 ° C. or less, hot water treatment, drying, calcination method of is illustrated. 【0006】また特開平6−122838号公報には、 [0006] In addition to the Japanese Unexamined Patent Publication (Kokai) No. 6-122838,
分子量が500〜20000でかつ末端まで弗素化した低分子量四弗化エチレン粉末を、アクリルシリコン樹脂、ポリエステル樹脂、エポキシ樹脂、アクリル樹脂、 The low molecular weight tetrafluoride ethylene powder molecular weight was fluorinated to a and terminal 500 to 20,000, acrylic silicone resins, polyester resins, epoxy resins, acrylic resins,
ウレタン樹脂、弗素樹脂の中の少なくとも1種類以上の樹脂もしくは混合樹脂中に揮発成分揮発後の体積分率で1〜70体積%となるように混入分散させたことを特徴とする撥水性粉体塗料及びその塗装方法が記載されている。 Urethane resins, water-repellent powder to be at least one or more features that is mixed dispersed as a resin or a mixed resin at a volume fraction after volatile components volatilize a 1-70% by volume in the fluororesin paint and coating methods are described. 【0007】 【発明が解決しようとする課題】前述の特公平7−86 [0007] The object of the invention is to be Solved by the above-mentioned KOKOKU 7-86
146号公報、特開平7−197017号公報、特開平9−202650号公報のような方法では、撥水性は得られるものの、基材にまず化学的エッチング法、各種機械的加工、フォトリソグラフィー、プラズマ加工、熱水処理等の凹凸構造を形成させるための工程を施した後、 146 JP, Japanese Unexamined 7-197017 discloses a method such as Japanese Patent 9-202650 discloses, although the water repellency is obtained, first, chemical etching method, various mechanical processing to the substrate, photolithography, plasma processing, after performing the steps for forming the irregular structure of the hot water treatment or the like,
撥水処理を行っているため、工程が複雑で時間およびコストがかかる等の課題があり、また平滑な基材に対しての撥水処理では十分な撥水性が得られないという課題があった。 Since the performing water repellent treatment, process has problems such as complicated and time consuming and cost, also sufficient water repellency there is a problem that not available in water-repellent processing on the smooth substrate . 【0008】また前述の特開平6−122838号公報のような方法では、平滑な基材に対しても十分な撥水性は得られるものの、不透明になるという課題があった。 [0008] In the method as described above in JP-A 6-122838 and JP-although sufficient water repellency even for smooth substrates obtained, there is a problem that becomes opaque. 【0009】本発明は、従来技術における前記問題点に鑑みてなされたもので、その課題は、基材に対し、撥水性及び透明性に優れた低温乾燥型の超撥水塗料組成物および該塗膜を被覆した超撥水材を提供することにある。 [0009] The present invention has been made in view of the above problems in the prior art points, and an object thereof is to base, low temperature drying type super water-repellent coating composition excellent in water repellency and transparency and the and to provide a super water-repellent material coated with the coating film. 【0010】 【課題を解決するための手段】本発明は、前記課題を解決すべく、(A)疎水処理が施されたシリカ微粒子と、 [0010] According to an aspect of the present invention is to solve the above problems, and (A) fine silica particles hydrophobic treatment has been performed,
(B)フッ素含有樹脂、加水分解性シラン、ポリオルガノシロキサンから選ばれる1種または2種以上を少なくとも含有する疎水性樹脂が、揮発後の重量分率でそれぞれ(A)が30〜100%、(B)が0〜70%となるように含有され、周波数10〜30kHz、振幅10〜 (B) a fluorine-containing resin, hydrolyzable silane, one or a hydrophobic resin containing at least two or more selected from polyorganosiloxanes, respectively the weight fraction after volatilization (A) 30 to 100% (B) it is contained such that 0% to 70%, frequency 10~30KHz, amplitude 10
50μmの超音波を(A)疎水処理が施されたシリカ微粒子に照射し、有機溶媒中に分散させたことを特徴とする超撥水剤を提供する。 The ultrasound 50μm was irradiated in (A) fine silica particles hydrophobic treatment has been performed, providing a super water-repellent agent characterized by dispersed in an organic solvent. 上記超撥水剤では、周波数10 In the super-water repellent, frequency 10
〜30kHz、振幅10〜50μmの超音波を(A)疎水処理が施されたシリカ微粒子に照射されることで、超撥水剤中の疎水処理が施されたシリカ微粒子の分散性が著しく向上し、塗膜形成時に優れた撥水性及び透明性が発揮される。 ~30KHz, by ultrasonic amplitude 10 to 50 [mu] m (A) hydrophobic treatment is irradiated to the fine silica particles subjected, dispersibility of the silica fine particles to hydrophobic treatment in super water repellent has been applied is remarkably improved , excellent water repellency and transparency upon forming a coating film is exhibited. 【0011】また本発明は、前記課題を解決すべく、 [0011] The present invention is to solve the above problems,
(A)疎水処理が施されたシリカ微粒子と、(B)フッ素含有樹脂、加水分解性シラン、ポリオルガノシロキサンから選ばれる1種または2種以上を少なくとも含有する疎水性樹脂が、揮発後の重量分率でそれぞれ(A)が30〜99%、(B)が1〜70%となるように含有され、周波数10〜30kHz、振幅10〜50μmの超音波を(A)疎水処理が施されたシリカ微粒子に照射し、有機溶媒中に分散させたことを特徴とする超撥水剤を提供する。 And silica fine particles (A) hydrophobic treatment has been performed, (B) a fluorine-containing resin, hydrolyzable silane, one or a hydrophobic resin containing at least two or more selected from polyorganosiloxane, weight after volatilization in fraction respectively (a) is 30 to 99% (B) is contained such that 1 to 70%, frequency 10~30KHz, the ultrasonic amplitude 10 to 50 [mu] m (a) a hydrophobic process is performed irradiating the silica fine particles, to provide a super water-repellent agent characterized by dispersed in an organic solvent. 上記超撥水剤では、疎水性樹脂を必須成分をして含有することで優れた塗膜形成性が発揮される。 Above the super water repellent, excellent film forming properties by containing a hydrophobic resin to the essential components is exhibited. 【0012】本発明の好ましい態様においては、前記有機溶媒として、アルコール類、ケトン類、エステル類、 In a preferred embodiment of the present invention, as the organic solvent, alcohols, ketones, esters,
アルコールエステル類、ケトンエステル類、エーテル類、ケトンアルコール類、エーテルアルコール類、ケトンエーテル類、エステルエーテル類から選ばれる1種または2種以上を少なくとも含有するようにする。 Alcohol esters, ketones esters, ethers, ketones alcohols, ether alcohols, ketones ethers, so as to at least contain one or more selected from an ester ethers. 上記から選ばれる有機溶媒を含有することで、さらに分散性、 By containing the organic solvent selected from the above, further dispersibility,
均一性、保存安定性に優れた超撥水性剤を提供でき、撥水性が良好で、特にヘーズの低い良好な透明性を有する超撥水性塗膜が形成できる。 Uniformity, can provide excellent storage stability superhydrophobic agents, water repellency is good, can be superhydrophobic coating film formed having a particularly low good transparency haze. 【0013】本発明の好ましい態様においては、微粒子の平均1次粒子径が1〜20nmであるようにする。 In a preferred embodiment of the present invention has an average primary particle diameter of fine particles to be a 1 to 20 nm. 微粒子の平均1次粒子径を1〜20nmにすることで、さらに透明性、分散性、意匠性に優れた超撥水塗膜を提供できる。 By an average primary particle diameter of the fine particles in the 1 to 20 nm, further transparency, can provide a dispersion, ultra water-repellent coating film having excellent design property. 【0014】本発明では、上記超撥水剤を塗布後、硬化することにより超撥水被膜が形成されていることを特徴とする超撥水材を提供する。 [0014] In the present invention, provides a super water-repellent material, characterized in that the super-water-repellent film is formed by post-coating, curing the ultra-water repellent. 【0015】本発明の好ましい態様においては、前記硬化は、10〜150℃での乾燥により行う。 In a preferred embodiment of the present invention, the curing is performed by drying at 10 to 150 ° C.. それにより、部材の選択性が増加し、例えばPETフィルムやアクリルフィルムのようなガラス転移点の低い部材にも適用可能となる。 Thus, increased selectivity of members, it is applicable to a member having low glass transition point such as PET film or an acrylic film. さらに1回の工程で平滑面に適用できるため、基材に機械的、化学的な処理を施し、凹凸を付与する工程が不要となり、汎用性が増加する。 Since it more applicable to the smooth surface in one step, subjected to a mechanical, chemical treatment to the substrate, the step of imparting the unevenness becomes unnecessary, versatility is increased. 【0016】本発明の好ましい態様においては、前記超撥水被膜は、100nm以上2μm以下であるようにする。 In a preferred embodiment of the present invention, the super water-repellent coating, so that is 100nm or 2μm or less. 膜厚100nm以上2μm以下の塗膜にすることで、撥水性、透明性、耐久性に優れた超撥水性塗膜を提供できる。 By following the coating film thickness of 100nm or more 2 [mu] m, water repellency, transparency, can provide a superhydrophobic coating film having excellent durability. 【0017】 【発明の実施の形態】次に、本発明の実施の形態について具体的かつ詳細に説明する。 DETAILED DESCRIPTION OF THE INVENTION Next, a specific and described in detail the embodiments of the present invention. ここで超撥水という言葉には、学術的な定義はないが、一般的には、固体表面の水との接触角が150°以上の状態をいう。 Here the term superhydrophobic is not academic definition, in general, the contact angle with water of the solid surface refers to a state of more than 150 °. また、本発明における「水との接触角」は、接触角計(共和界面科学社製CX−150型)を用いて、内径0.1mmのP Furthermore, "contact angle with water" in the present invention, using a contact angle meter (Kyowa Interface Science Co., Ltd. CX-0.99 inch), an inner diameter of 0.1 mm P
TFE(ポリテトラフルオロエチレン)コートされたマイクロシリンジから約1μlの水滴を滴下直後の接触角である。 From TFE (polytetrafluoroethylene) coated microsyringe a contact angle immediately after dropping about 1μl of water droplets. 【0018】本発明の疎水処理が施されたシリカ微粒子は、微粒子粉末および市販の微粒子を分散させた分散体が使用できるが、溶媒の選択性および分散性および塗膜形成後の撥水性の点で微粒子粉末が好ましい。 The silica fine particles hydrophobic treatment has been performed of the present invention is a dispersion obtained by dispersing fine particles and commercially available particles can be used, in terms of water repellency of the solvent selectivity and dispersibility and film-forming in fine powder it is preferred. 【0019】微粒子の平均1次粒子径は、1nm〜20 [0019] The average primary particle diameter of the fine particles, 1nm~20
nmが好ましく、より好ましくは1nm〜16nm、さらに好ましくは1nm〜12nmである。 nm, more preferably 1Nm~16nm, more preferably from 1Nm~12nm. 粒子径が20 Particle size of 20
nmを超えると、表面の平均粗さ(Ra)を200nm Beyond nm, average surface roughness of (Ra) 200 nm
以下に抑えることが難しくなり、可視光の波長域での透明性が低下する。 It is difficult to keep below, transparency in the wavelength range of visible light is lowered. ここで、微粒子の平均1次粒子径は、 Here, the average primary particle diameter of the fine particles,
走査型電子顕微鏡もしくは透過型電子顕微鏡により測定する。 Measured by a scanning electron microscope or transmission electron microscope. 【0020】また凝集粒子の粒子径も1nm以上1μm [0020] particle size of the aggregated particles also 1nm or more 1μm
以下が好ましく、より好ましくは1nm以上200nm Or less, more preferably 1nm more than 200nm
以下である。 Less. 凝集粒子の粒子径が1μmを超えると、可視光の波長域での表面の散乱が大きくなり、膜が白濁する。 When the particle diameter of the agglomerated particles is more than 1 [mu] m, scattering of the surface in the wavelength range of visible light is increased, the film becomes clouded. 上記白濁を抑制するために、本発明では、周波数1 In order to suppress the clouding, the present invention, the frequency 1
0〜30kHz、振幅10〜50μmの超音波を疎水処理が施されたシリカ微粒子に照射して、シリカ微粒子の分散性を向上させる。 0~30KHz, by irradiating ultrasonic wave amplitude 10~50μm silica particles hydrophobic process is performed to improve the dispersibility of the silica fine particles. シリカ微粒子を溶液中に分散させる方法としては、高速回転分散機、媒体攪拌型分散機(ボールミル、サンドミルなど)、超音波分散機、コロイドミル分散機、ロールミル分散機、高圧分散機等従来公知の分散機を使用することができるが、均一かつ微細に分散できるという点で超音波分散機もしくは高圧分散機が好ましい。 As a method for dispersing the silica fine particles in the solution, high speed disperser, medium stirring type disperser (a ball mill, sand mill, etc.), ultrasonic dispersing machine, colloid mill dispersing machine, a roll mill disperser, a high-pressure dispersing machine known can be used a dispersing machine, ultrasonic dispersing machine or high-pressure dispersing machine are preferable in terms of uniformity and can finely dispersed. 超音波分散機は周波数20〜50kHz Ultrasonic dispersing machine frequency 20~50kHz
の超音波を照射することで固液界面にエネルギーを集中させることで分散させるものであり、非常に効率的かつ微細に分散させることが可能である。 Ultrasonic is intended to disperse by focusing the energy to the solid-liquid interface by irradiating, it is possible to very efficiently and finely dispersed in. 超音波による分散プロセスで重要となるのは、超音波キャビテーションであり、キャビテーション圧が高いほど分散能力が高い。 An important in a distributed process with ultrasound is the ultrasonic cavitation, is higher the higher dispersion ability cavitation pressure.
キャビテーションは一般に低い周波数の方が起こりやすいが、周波数15KHz以下では、可聴音域に入るため、また分散装置自体の大きくなるため都合が悪い。 Cavitation tends to occur toward the generally low frequencies, below the frequency 15KHz, since entering the audible range, also made for large dispersion device itself inconvenient. 印加する超音波の振幅としては10〜40μmであることが好ましい。 It is preferred as the ultrasonic amplitude to be applied is 10 to 40 [mu] m. 振幅が10μm以下であると分散性が低下し、40μm以上であると、装置の劣化が著しくなり都合が悪い。 Amplitude decreases dispersibility and is 10μm or less, if it is 40μm or more, the deterioration of the device is remarkably inconvenient. 【0021】本発明のシリカ微粒子に施す疎水化表面処理に使用される化合物や処理方法に特別の制限はないが、表面にフッ素やアルキル基が付与されることが好ましい。 [0021] Without particular restriction on the compound or treatment method that is used to hydrophobic surface treatment applied to the silica particles of the present invention, it is preferable that fluorine and alkyl groups are imparted to the surface. 例えばシリル化剤、チタネートカップリング剤、 For example a silylating agent, titanate coupling agent,
アルキルアルミニウム等の有機金属化合物が挙げられる。 Organometallic compound an alkyl aluminum and the like. シリル化剤は無機材料に対して親和性あるいは反応性を有する加水分解性シリル基に、アルキル基、アリール基、フッ素を含有したフルオロアルキル基等を結合させた化合物であり、ケイ素に結合した加水分解性基としては、アルコキシ基、ハロゲン、アセトキシ基、シラザン等が挙げられる。 Silylating agent to hydrolyzable silyl group having affinity or reactivity to the inorganic material, an alkyl group, an aryl group, the compound obtained by binding a fluorine fluoroalkyl group containing such, bonded to silicon hydrolytically the decomposable group, an alkoxy group, a halogen, an acetoxy group, a silazane, and the like. 【0022】本発明における疎水性樹脂としては、フッ素含有樹脂、加水分解性シラン、ポリオルガノシロキサン、アクリルシリコーン、アクリル樹脂が使用できる。 [0022] As the hydrophobic resin in the present invention, fluorine-containing resin, hydrolyzable silane, polyorganosiloxanes, acrylic silicone, acrylic resin.
上記樹脂のうち、加水分解性シラン、ポリオルガノシロキサンから選ばれる1種または2種以上を含有してなる疎水性樹脂が特に好ましい。 Among the above resins, hydrolyzable silane, one or a hydrophobic resin comprising two or more selected from a polyorganosiloxane is particularly preferred. ここでフッ素含有樹脂としては、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体樹脂、ポリクロロトリフルオロエチレン樹脂、テトラフルオロエチレン−エチレン共重合体樹脂、クロロトリフルオロエチレン−エチレン共重合体樹脂、ポリフッ化ビニリデン樹脂、ポリフッ化ビニル樹脂、ポリテトラフルオロエチレン樹脂、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体樹脂などの結晶性フッ素樹脂、フルオロオレフィンおよび他の単量体を共重合して得られる非結晶性フッ素樹脂等が挙げられるが、透明性、溶剤分散性から非結晶性フッ素樹脂であることが好ましい。 Here, as the fluorine-containing resin, tetrafluoroethylene - perfluoroalkyl vinyl ether copolymer resins, polychlorotrifluoroethylene resins, tetrafluoroethylene - ethylene copolymer resin, chlorotrifluoroethylene - ethylene copolymer resin, polyvinylidene fluoride resins, polyvinyl fluoride resins, polytetrafluoroethylene resins, tetrafluoroethylene - crystalline fluorocarbon resins such as hexafluoropropylene copolymer resin, fluoroolefin and non-crystal obtained by copolymerizing another monomer Although sexual fluorocarbon resins, transparency, it is preferable from a solvent dispersion noncrystalline fluororesin. 前記非結晶性フッ素樹脂は、硬化剤と反応する官能基を有することが好ましく、 The amorphous fluororesin preferably has a functional group which reacts with a curing agent,
反応性官能基としては、ヒドロキシ基、カルボキシル基、加水分解可能な基を有する有機珪素基、エポキシ基等が挙げられる。 The reactive functional group, hydroxy group, carboxyl group, an organic silicon group having a hydrolyzable group and an epoxy group. また、硬化剤としては、モノマー型、 Further, as the curing agent, monomeric,
プレポリマー型または樹脂であってもよく、例えば官能基がヒドロキシ基、カルボキシル基またはエポキシ基である場合には、メラミン系硬化剤、尿素樹脂硬化剤、多塩基酸硬化剤、イソシアネート硬化剤、エポキシ硬化剤等を官能基量に応じて適当量使用できる。 May be a prepolymer type or resin, for example, when the functional group is a hydroxy group, a carboxyl group or an epoxy group, a melamine curing agent, urea resin curing agent, polybasic acid curing agent, an isocyanate curing agent, epoxy the curing agent or the like can be used an appropriate amount depending on the amount of functional groups. ここで加水分解性シランとしては、メチルトリメトキシシラン、エチルトリメトキシシラン、エチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、 Examples of the hydrolyzable silane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane,
メチルトリプロポキシシラン、エチルトリプロポキシシラン、n−プロピルトリメトキシシラン、n−プロピルトリエトキシシラン、n−プロピルトリプロポキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、イソプロピルトリプロポキシシラン、メチルトリブトキシシラん、エチルトリブトキシシラン、n−プロピルトリブトキシシラン、イソプロピルトリブトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリプロポキシシラン、フェニルトリブトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリプロポキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタ Methyl tripropoxysilane, ethyl tripropoxysilane, n- propyltrimethoxysilane, n- propyl triethoxysilane, n- propyl tripropoxysilane, isopropyl trimethoxy silane, isopropyl triethoxysilane, isopropyl tripropoxysilane, methyl tributoxysilane Sila N, ethyl tributoxy silane, n- propyl tributoxy silane, isopropyl tributoxy silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyl tripropoxysilane, phenyl tributoxy silane, .gamma.-glycidoxypropyltrimethoxysilane, gamma - glycidoxypropyl triethoxysilane, .gamma.-glycidoxypropyl tripropoxysilane, .gamma.-methacryloxypropyl trimethoxysilane, .gamma. meta クリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリプロポキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、トリフルオロプロピルトリメトキシシラン、トリフルオロプロピルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、フェニルメチルジメトキシシラン、フェニルメチルジエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジエトキリシ Methacryloxypropyl triethoxysilane, .gamma.-methacryloxypropyl tripropoxysilane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, beta-(3,4-epoxycyclohexyl) ethyl triethoxy silane, .gamma.-aminopropyl trimethoxysilane, .gamma.-aminopropyltriethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, .gamma.-mercaptopropyl triethoxysilane, trifluoropropyl trimethoxysilane, trifluoropropyl triethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane silane, vinyl tripropoxysilane, phenylmethyl dimethoxysilane, phenylmethyl diethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, diethyl diethyl Toki Rishi ン、 Down,
ジフェニルジメトキシシラン、ジフェニルジエトキシシラン等の加水分解性オルガノシラン、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトラn−プロポキシシラン、テトラブトキシシラン、ジメトキシジエトキシシラン等のテトラアルコキシシラン等が使用できる。 Diphenyldimethoxysilane, hydrolyzable organosilane such as diphenyl diethoxy silane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n- propoxysilane, tetrabutoxysilane, tetraalkoxysilane such as dimethoxy diethoxy silane It can be used. ここでポリオルガノシロキサンとしては、上記加水分解性シラン、アルキルシリケート、それらの(部分)加水分解物、加水分解縮合物等が使用できる。 Examples of the polyorganosiloxane, the hydrolyzable silane, alkyl silicates, their (partial) hydrolysates, hydrolysis condensates may be used. また、加水分解性シラン、ポリオルガノシロキサンと併用して塩酸、硝酸、硫酸、酢酸、マレイン酸等の加水分解を促進する触媒や、トリブチルアミン、 Further, a hydrolyzable silane, hydrochloride in combination with polyorganosiloxane, the catalyst and to accelerate nitric acid, sulfuric acid, acetic acid, the hydrolysis of maleic acid, tributylamine,
ヘキシルアミンなどの塩基性化合物類、アルミニウムトリイソプロポキシド、テトライソプロピルチタネートの酸性有機金属化合物類等の加水分解性シラン、ポリオルガノシロキサンの硬化を促進させる触媒を使用できる。 Basic compounds such as hexylamine, aluminum triisopropoxide, hydrolyzable silane, such as acidic organometallic compounds such as tetraisopropyl titanate, a catalyst to accelerate the cure of polyorganosiloxane can be used. 【0023】本発明の塗料組成物は、シリカ微粒子、疎水性樹脂が揮発後の重量分率でそれぞれ30〜100 The coating composition of the present invention, each silica fine particles, a hydrophobic resin in a weight fraction after volatilization 30-100
%、0〜70%であり、好ましくはそれぞれ40〜10 %, And 0 to 70%, each preferably 40 to 10
0%、0〜60%である。 0%, 0 to 60%. 揮発後の微粒子の重量分率が30%以下であると、所望の粗さが得られず、撥水性が低下する。 If the weight fraction of the fine particles after volatilization is less than 30%, desired roughness can not be obtained, the water repellency is lowered. 【0024】本発明の塗料組成物の溶剤としては、アルコール類、ケトン類、エステル類、アルコールエステル類、ケトンエステル類、エーテル類、ケトンアルコール類、エーテルアルコール類、ケトンエーテル類、エステルエーテル類から選ばれる1種または2種以上を少なくとも含有する有機溶剤が挙がられる。 [0024] As the solvent of the coating composition of the present invention include alcohols, ketones, esters, alcohol esters, ketone esters, ethers, ketones alcohols, ether alcohols, ketones ethers, ester ethers one or organic solvent containing at least two or more selected is go up. 芳香族炭化水素類の有機溶媒は疎水処理が施されたシリカ微粒子の分散安定性を著しく低下させるため、その含有量は極力少ないことが好ましい。 Since organic solvents aromatic hydrocarbons significantly reduce the dispersion stability of the silica fine particles hydrophobic treatment has been performed, its content is preferably as small as possible. 【0025】本発明の塗料組成物には、レベリング剤、 [0025] The coating composition of the present invention, a leveling agent,
カップリング剤、増粘剤、紫外線吸収剤、光安定剤、凍結防止剤等も本発明の効果に悪影響を与えない範囲内で添加してもよい。 Coupling agents, thickeners, UV absorbers, light stabilizers, may be added within a range that does not adversely affect the effects of the present invention antifreezing agent. 【0026】密着性をより向上させるためには、基体に本発明の超撥水剤を塗布したり、吹き付けたりしてコーティングする前に、中間層を少なくとも一層コーティングすることが望ましい。 [0026] In order to improve the adhesion, or coating a super water-repellent agent of the present invention to a substrate, prior to coating or spraying, it is desirable to at least one layer coating the intermediate layer. 【0027】基体に本発明の超撥水剤を塗布したり、吹き付けたりしてコーティングするには特に限定がなく、 [0027] or coated with a super water-repellent agent of the present invention to a substrate is not particularly limited to coating or spraying,
例えばスピンコーティング法、ディップコーティング法、フローコーティング法、スプレーコーティング法、 For example, spin coating, dip coating, flow coating, spray coating,
ディップコーティング法、ロールコーティング法、スクリーン印刷法、バーコーター法、刷毛塗り、スポンジ塗り等の従来公知の塗布方法が使用できる。 Dip coating, roll coating, screen printing method, a bar coater method, brush coating, conventionally known coating methods sponge coating, etc. can be used. 【0028】本発明の超撥水剤をコーティングし、形成された塗膜の膜厚は、100nm以上2μm以下であり、好ましくは200nm以上1.5μm以下、さらに好ましくは200nm以上1μmである。 The coated super water-repellent agent of the present invention, the thickness of the formed coating film is at 100nm than 2μm or less, preferably 200nm or 1.5μm or less, more preferably 200nm or more 1 [mu] m. 膜厚が100 The film thickness is 100
nmより薄いとフラクタル構造が発現せず、所望の撥水性を実現させることができない。 Thin and fractal structure does not express more nm, it is impossible to achieve the desired water repellency. 膜厚が2μmを超えると、光線のヘーズ値が著しく上昇し、さらに塗膜の強度も低下する。 If the film thickness exceeds 2 [mu] m, increased haze value of the optical significantly, also decreases the strength of the further coating. 【0029】光線のヘーズ値はJIS K 7105で規格される試験方法に基づき、積分球式光線透過率測定装置を用いて測定されるものである。 The haze value of the light beam on the basis of the test method stipulated in JIS K 7105, is measured using an integrating sphere type light transmittance measuring apparatus. 拡散透過率および全光線透過率を測定し、その比を表したものである。 The diffuse transmittance and total light transmittance were measured, it illustrates a ratio thereof. 【0030】本発明の塗料組成物を被覆使用できる基材としては、その材質としては、金属、セラミックス、ガラス、プラスチック、木、石、セメント、コンクリート、繊維、布帛、紙、それらの組合わせ、それらの積層体、それらの塗装体等である。 [0030] As the base material of the coating composition coating can be used in the present invention, examples of the material, metals, ceramics, glass, plastics, wood, stone, cement, concrete, fiber, cloth, paper, combinations thereof, laminates thereof, their coating and the like. 本発明の適用可能な部材は、表面の防滴性、防錆性、水切れ性、水系汚れ付着防止性、流水洗浄性、着氷雪防止性等が要求されるあらゆる部材に適用できる。 Applicable member of the present invention, drip of the surface, rust resistance, drainage, water-based stains antiadhesive can be applied to any member of flowing water detergency, Chakuhyosetsu preventing property and the like are required. 【0031】具体的には、外壁や屋根のような建築外装;窓枠;自動車、鉄道車両、航空機、船舶、自転車、 [0031] More specifically, building exterior, such as the outer wall and roof; window frame; automobile, railway vehicle, aircraft, ship, bicycle,
オートバイのような乗物の外装及び塗装;防音壁、ビニールハウス、碍子、乗物用カバー、テント材、反射板、 Vehicle exteriors and paints such as motorcycle; soundproof walls, vinyl houses, insulators, vehicle covers, tent materials, reflectors
雨戸、網戸、太陽電池用カバー、太陽熱温水器等の集熱器用カバー、街灯、舗道、屋外照明、人工滝、人工噴水用石材、タイル、橋、温室、外壁材、壁間や碍子間のシーラー、ガードレール、ベランダ、自動販売機、エアコン室外機、屋外ベンチ、各種表示装置、シャッター、料金所、料金ボックス、防塵カバー及び塗装、機械装置や物品の塗装、広告塔の外装及び塗装、構造部材及びそれら物品に粘着可能なフィルム、ワッペン等である。 Shutters, screen doors, solar cell covers, covers for heat collectors of solar water heaters, street lamps, pavements, outdoor lighting, artificial waterfalls, artificial fountains stone, tiles, bridges, greenhouses, outer wall materials, between walls and insulator sealer , guardrails, verandas, vending machines, air conditioning outdoor unit, outdoor benches, various display devices, shutter, toll booth, fee box, dust-proof cover and painting, painting of machinery and goods, advertising towers of the exterior and painting, structural members and adhesive can be a film to them article, a patch and the like. 【0032】また看板、標識、方向指示板、銅像、彫刻等、各種の意匠材や透明なプラスチックフィルム、建築物や乗物もしくは各種計器類の窓材、眼鏡、サングラス、車両用バックミラー、浴室用または洗面所用鏡、歯科用鏡、道路鏡、光学レンズ、内視鏡レンズ、ゴーグル、シールド等透明な塗膜が要求される部材に対しても適用可能である。 Further signboards, signs, direction indicator plate, statue, engraving, etc., various designs material or a transparent plastic film, buildings and vehicles or a window material for various instruments, glasses, sunglasses, a rearview mirror for vehicles, bathroom or washroom mirror, a dental mirror, road mirrors, is also applicable to members optical lens, endoscopic lens, goggles, shields such as transparent coating film is required. 【0033】 【実施例】以下に、実施例を掲げてこの発明をさらに具体的に説明するが、この発明の技術範囲はこれらの例示に限定されるものではない。 [0033] EXAMPLES The following is a more detailed description of the present invention by way of examples, the technical scope of the present invention is not limited to these examples. (調合例1)フッ素樹脂塗料(三菱レイヨン社製フロロナールFL6002)1.3重量部とキシレン30.0 (Formulation Example 1) Fluorine resin paint (manufactured by Mitsubishi Rayon Co. Furoronaru FL6002) 1.3 parts by weight of xylene 30.0
重量部、酢酸ブチル7.5重量部の混合溶剤とを混合し、常温で5分マグネチックスターラーにて攪拌した後、疎水性コロイダルシリカ(日本アエロジル社製RX Parts, was mixed with a mixed solvent of 7.5 parts by weight of butyl acetate, followed by stirring at 5 minutes magnetic stirrer at room temperature, hydrophobic colloidal silica (manufactured by Nippon Aerosil Co. RX
200)を0.8重量部を添加し、温度が上昇し過ぎないよう注意しけながら、超音波分散機(エスエムテー社製UH−150)を用い、発振周波数20KHz、振幅約30μmで断続的に20分間超音波を照射した。 200) was added 0.8 part by weight, while the barge careful temperature does not increase excessively, ultrasonic dispersing machine (manufactured by SMT Co., Ltd. UH-0.99) using the oscillation frequency 20 KHz, intermittently with amplitude of about 30μm It was irradiated for 20 minutes ultrasound. さらにポリイソシアネート型硬化剤(大日本インキ化学工業社製バーノックDN990S)を0.4重量部添加し、常温で60分マグネチックスターラーにて攪拌し、塗料組成物A1を得た。 Polyisocyanate type curing agent (manufactured by Dainippon Ink and Chemicals, Inc. Burnock DN990S) was added 0.4 part by weight, the mixture was stirred at 60 min magnetic stirrer at room temperature to obtain a coating composition A1. 【0034】(調合例2)調合例1でフッ素樹脂塗料、 The fluororesin paint (Formulation Example 2) Formulation Example 1,
キシレン、酢酸ブチル、疎水性コロイダルシリカの配合量を表1に示した以外調合例1と同様にして、塗料組成物A2,A3を得た。 Xylene, butyl acetate, the amount of hydrophobic colloidal silica in the same manner as in Formulation Example 1 except as shown in Table 1, to obtain a coating composition A2, A3. 【0035】(調合例3)フッ素樹脂塗料(セントラル硝子社製セフラルコートFG730B)4.6重量部と酢酸ブチル35.2重量部を混合し、常温で5分マグネチックスターラーにて攪拌した後、ポリイソシアネート型硬化剤(日本ポリウレタン社製コロネートHX)を0.2重量部添加し、常温で10分間マグネチックスターラーにて攪拌し、疎水性樹脂分散液iを得た。 [0035] (Formulation Example 3) Fluorine resin paint mixing (Central Glass Co., Ltd. CEFRAL COAT FG730B) 4.6 parts by weight of butyl acetate 35.2 parts by weight, was stirred at 5 minutes magnetic stirrer at room temperature, poly isocyanate curing agent were added 0.2 parts by weight (manufactured by Nippon polyurethane Co., Ltd. Coronate HX), and stirred for 10 minutes at a magnetic stirrer at room temperature, to obtain a hydrophobic resin dispersion i. 酢酸ブチル28.5重量部に疎水性コロイダルシリカ(日本アエロジル社製RX200)を1.5重量部を添加し、温度が上昇し過ぎないよう注意しながら、超音波分散機(エスエムテー社製UH−150)を用い、発振周波数2 Hydrophobic colloidal silica 28.5 parts by weight of butyl acetate (Nippon Aerosil Co., Ltd. RX200) was added 1.5 parts by weight, being careful that the temperature does not increase excessively, ultrasonic dispersing machine (manufactured by SMT Co. UH- using the 150), the oscillation frequency 2
0KHz、振幅約30μmで断続的に20分間超音波を照射し、コロイダルシリカ分散液i'を得た。 0 kHz, intermittently irradiated with ultrasonic waves for 20 minutes at an amplitude of about 30 [mu] m, to obtain a colloidal silica dispersion i '. 疎水性樹脂分散液i4.2重量部とコロイダルシリカ分散液i' Hydrophobic resin dispersion i4.2 parts by weight of colloidal silica dispersion i '
2.8重量部を混合し、常温で50分間マグネチックスターラーにて攪拌し、塗料組成物B3を得た。 2.8 parts by weight were mixed and stirred at 50 min magnetic stirrer at room temperature to obtain a coating composition B3. 【0036】(調合例4)調合例3で疎水性樹脂分散液 [0036] (Formulation Example 4) hydrophobic resin dispersion in Formulation Example 3
iとコロイダルシリカ分散液i'の配合量を表2(a)に示す値に変えた以外は調合例3と同様にして、塗料組成物B1,B2,B4,B5,B6,B7を得た。 The amount of i colloidal silica dispersion i 'in the same manner as in Formulation Example 3 except for changing the values ​​shown in Table 2 (a), to obtain a coating composition B1, B2, B4, B5, B6, B7 . 【0037】(調合例5)調合例3で、超音波分散機を超音波洗浄機(井内盛栄堂社製US−3)に変え、配合比を表2(a)に示す配合比にした以外調合例3と同様にして、塗料組成物B8を得た。 [0037] In (Formulation Example 5) Formulation Example 3, except that changing the ultrasonic dispersion machine ultrasonic cleaner (Iuchi Co. US-3), the mixing ratio was compounding ratio shown in Table 2 (a) in the same manner as formulation example 3, to obtain a coating composition B8. 【0038】(調合例6)フッ素樹脂塗料(セントラル硝子社製セフラルコートFG730B)6.5重量部と酢酸ブチル33.3重量部を混合し、常温で5分マグネチックスターラーにて攪拌した後、ポリイソシアネート型硬化剤(日本ポリウレタン社製コロネートHX)を0.2重量部添加し、常温で10分間マグネチックスターラーにて攪拌し、疎水性樹脂分散液iiを得た。 [0038] (Formulation Example 6) Fluororesin coating a mixture of (Central Glass Co., Ltd. CEFRAL COAT FG730B) 6.5 parts by weight of butyl acetate 33.3 parts by weight, was stirred at 5 minutes magnetic stirrer at room temperature, poly isocyanate curing agent were added 0.2 parts by weight (manufactured by Nippon polyurethane Co., Ltd. Coronate HX), and stirred for 10 minutes at a magnetic stirrer at room temperature, to obtain a hydrophobic resin dispersion ii. 酢酸ブチル27.9重量部に疎水性コロイダルシリカ(日本アエロジル社製RX200)を2.1重量部を添加し、温度が上昇し過ぎないよう注意しながら、超音波分散機(エスエムテー社製UH−150)を用い、発振周波数2 It was added 2.1 parts by weight of hydrophobic colloidal silica (Nippon Aerosil Co., Ltd. RX200) to 27.9 parts by weight of butyl acetate, taking care that the temperature does not increase excessively, ultrasonic dispersing machine (manufactured by SMT Co. UH- using the 150), the oscillation frequency 2
0KHz、振幅約30μmで断続的に20分間超音波を照射し、コロイダルシリカ分散液ii'を得た。 0 kHz, intermittently irradiated with ultrasonic waves for 20 minutes at an amplitude of about 30 [mu] m, to obtain a colloidal silica dispersion ii '. 疎水性樹脂分散液ii4.2重量部とコロイダルシリカ分散液ii' Hydrophobic resin dispersion ii4.2 parts by weight of colloidal silica dispersion ii '
2.8重量部を混合し、常温で50分間マグネチックスターラーにて攪拌し、塗料組成物C3を得た。 2.8 parts by weight were mixed and stirred at 50 min magnetic stirrer at room temperature to obtain a coating composition C3. 【0039】(調合例7)調合例6で疎水性樹脂分散液 [0039] (Formulation Example 7) Hydrophobic Resin Dispersion in Formulation Example 6
iiとコロイダルシリカ分散液ii'の配合量を表3に示す値に変えた以外は調合例6と同様にして、塗料組成物C Except that the amount of ii colloidal silica dispersion ii 'was changed to the values ​​shown in Table 3 in the same manner as Formulation Example 6, the coating composition C
1,C2,C4,C5,C6,C7を得た。 1, C2, to obtain a C4, C5, C6, C7. 【0040】(調合例8)シリコーンコーティング剤(信越化学工業社製KR−400)1.5重量部とn− [0040] (Formulation Example 8) silicone coating agent (manufactured by Shin KR-400) and 1.5 parts by weight of n-
ブタノール28.5重量部を混合し、常温で5分マグネチックスターラーにて攪拌し、疎水性樹脂分散液iiiを得た。 It was mixed butanol 28.5 parts by weight, and stirred at 5 minute magnetic stirrer at room temperature, to obtain a hydrophobic resin dispersion iii. n−ブタノール28.5重量部に疎水性コロイダルシリカ(日本アエロジル社製RX200)を1.5重量部添加し、温度が上昇し過ぎないよう注意しながら、 Hydrophobic colloidal silica (Nippon Aerosil Co., Ltd. RX200) was added 1.5 parts by weight 28.5 parts by weight n- butanol, being careful that the temperature does not increase excessively,
超音波分散機(エスエムテー社製UH−150)を用い、 Using an ultrasonic disperser (manufactured by SMT Co., Ltd. UH-150),
発振周波数20KHz、振幅約30μmで断続的に20 Oscillation frequency 20 KHz, intermittently 20 with an amplitude of about 30μm
分間超音波を照射し、コロイダルシリカ分散液iii'を得た。 Ultrasonic wave irradiation, to obtain a colloidal silica dispersion iii 'minutes. 疎水性樹脂分散液iii3.5重量部とコロイダルシリカ分散液iii'3.5重量部を混合し、常温で15 Mixing a hydrophobic resin dispersion iii3.5 parts by weight of colloidal silica dispersion iii'3.5 parts, 15 at room temperature
分間マグネチックスターラーにて攪拌し、塗料組成物D It was stirred at minute magnetic stirrer, the coating composition D
4を得た。 4 was obtained. 【0041】(調合例9)調合例8で疎水性樹脂分散液 [0041] (Formulation Example 9) hydrophobic resin dispersion in Formulation Example 8
iiiとコロイダルシリカ分散液iii'の配合量を表4に示す値に変えた以外は調合例8と同様にして、塗料組成物D1,D2,D3,D5,D6,D7を得た。 Except that the amount of iii colloidal silica dispersion iii 'was changed to the values ​​shown in Table 4 in the same manner as Formulation Example 8 to obtain a coating composition D1, D2, D3, D5, D6, D7. 【0042】(調合例10)アクリルシリコーンコーティング液(信越化学工業社製X−22−8004)3. [0042] (Formulation Example 10) Acrylic silicone coating solution (Shin-Etsu Chemical Co., Ltd. X-22-8004) 3.
1重量部とテトラヒドロフラン21.9重量部を混合し、常温で5分間マグネチックスターラーにて攪拌し、 1 part by weight of tetrahydrofuran 21.9 parts by weight, and stirred for 5 minutes at a magnetic stirrer at room temperature,
疎水性樹脂分散液ivを得た。 To obtain a hydrophobic resin dispersions iv. テトラヒドロフラン33. Tetrahydrofuran 33.
3重量部に疎水性コロイダルシリカ(日本アエロジル社製RX200)を1.8重量部添加し、温度が上昇し過ぎないよう注意しながら、超音波分散機(エスエムテー社製UH−150)を用い、発振周波数20KHz、振幅約30μmで断続的に20分間超音波を照射し、コロイダルシリカ分散液iv'を得た。 3 parts by weight of hydrophobic colloidal silica (Nippon Aerosil Co., Ltd. RX200) was added 1.8 parts by weight, being careful that the temperature does not increase excessively, ultrasonic dispersing machine (manufactured by SMT Co., Ltd. UH-0.99) using, oscillation frequency 20 KHz, intermittently irradiated with ultrasonic waves for 20 minutes at an amplitude of about 30 [mu] m, to obtain a colloidal silica dispersion iv '. 疎水性樹脂分散液ivとコロイダルシリカ分散液iv'を表5に示す値で混合し、常温で15分間マグネチックスターラーにて攪拌し、塗料組成物E1,E2,E3,E4を得た。 A hydrophobic resin dispersion iv colloidal silica dispersion iv 'were mixed at the values ​​shown in Table 5, and stirred for 15 minutes at a magnetic stirrer at room temperature to obtain a coating composition E1, E2, E3, E4. 【0043】(調合例11)調合例10の疎水性樹脂分散液ivを、アクリル樹脂塗料(大日本インキ化学工業社製アクリディックA−166)2.8重量部とテトラヒドロフラン22.2重量部を混合し、常温で5分間マグネチックスターラーにて攪拌し、得た疎水性樹脂分散液 [0043] The (Formulation Example 11) Hydrophobic Resin Dispersion iv of Formulation Example 10, the acrylic resin paint (manufactured by Dainippon Ink and Chemicals, Inc. ACRYDIC A-166) 2.8 parts by weight of tetrahydrofuran 22.2 parts by weight mixed and stirred for 5 minutes at a magnetic stirrer at room temperature, resulting hydrophobic resin dispersion
vに変えた以外は調合例10と同様にし、塗料組成物F v except for using the the same manner as Formulation Example 10, coating compositions F
1,F2,F3,F4を得た。 To obtain a 1, F2, F3, F4. 【0044】(調合例12)調合例10の疎水性樹脂分散液ivを、アルキド樹脂塗料(大日本インキ化学工業社製ベッコゾールES−4505−60X)2.1重量部とテトラヒドロフラン22.9重量部を混合し、常温で5分間マグネチックスターラーにて攪拌し、得た疎水性樹脂分散液viに変えた以外は調合例10と同様にし、塗料組成物G1,G2,G3,G4を得た。 [0044] (Formulation Example 12) a hydrophobic resin dispersion iv of Formulation Example 10, alkyd resin paint (manufactured by Dainippon Ink and Chemicals, Incorporated Beckosol ES-4505-60X) 2.1 parts by weight of tetrahydrofuran 22.9 parts by weight It was mixed and stirred for 5 minutes at a magnetic stirrer at room temperature, except for changing the obtained hydrophobic resin dispersion vi in ​​the same manner as formulation example 10 to obtain a coating composition G1, G2, G3, G4. 【0045】(調合例13)調合例10の疎水性樹脂分散液ivを、ポリエステル樹脂塗料(日本合成化学社製ポリエスターTP−220)3.1重量部とテトラヒドロフラン21.9重量部を混合し、常温で5分間マグネチックスターラーにて攪拌し、得た疎水性樹脂分散液vii [0045] (Formulation Example 13) a hydrophobic resin dispersion iv of Formulation Example 10, a polyester resin paint (Nippon Synthetic Chemical Industry Co., Ltd. Polyester TP-220) 3.1 was mixed with parts of tetrahydrofuran 21.9 parts by weight , stirred for 5 minutes at a magnetic stirrer at room temperature, resulting hydrophobic resin dispersion vii
に変えた以外は調合例10と同様にし、塗料組成物H Except for using the the same manner as Formulation Example 10, the coating composition H
1,H2,H3,H4を得た。 To obtain a 1, H2, H3, H4. 【0046】(調合例14)調合例10の疎水性樹脂分散液ivを、不飽和ポリエステル樹脂塗料(日本合成化学社製ゴーセラック540)1.8重量部とテトラヒドロフラン23.2重量部を混合し、常温で5分間マグネチックスターラーにて攪拌し、得た疎水性樹脂分散液viii [0046] (Formulation Example 14) a hydrophobic resin dispersion iv of Formulation Example 10, the unsaturated polyester resin paint (Nippon Synthetic Chemical Industry Co., Ltd. Goserakku 540) were mixed 1.8 parts by weight of tetrahydrofuran 23.2 parts by weight, It was stirred for 5 minutes at a magnetic stirrer at room temperature, resulting hydrophobic resin dispersion viii
に変えた以外は調合例10と同様にし、塗料組成物I In the same manner as Formulation Example 10 except for changing the coating composition I
1,I2,I3,I4を得た。 1, was obtained I2, I3, I4. 【0047】(調合例15)シリコーンコーティング剤(信越化学工業社製KR−400)1.5重量部とn− [0047] (Formulation Example 15) Silicone coating agent (manufactured by Shin KR-400) and 1.5 parts by weight of n-
ブタノール28.5重量部を混合し、常温で5分マグネチックスターラーにて攪拌し、シリコーン分散液iiiを得た。 It was mixed butanol 28.5 parts by weight, and stirred at 5 minute magnetic stirrer at room temperature, yielding a silicone dispersion iii. n−ブタノール28.5重量部に疎水性コロイダルシリカ(日本アエロジル社製RX300)を1.5重量部添加し、温度が上昇し過ぎないよう注意しながら、 Hydrophobic colloidal silica (Nippon Aerosil Co., Ltd. RX300) was added 1.5 parts by weight 28.5 parts by weight n- butanol, being careful that the temperature does not increase excessively,
超音波分散機(エスエムテー社製UH−150)を用い、 Using an ultrasonic disperser (manufactured by SMT Co., Ltd. UH-150),
発振周波数20KHz、振幅約30μmで断続的に20 Oscillation frequency 20 KHz, intermittently 20 with an amplitude of about 30μm
分間超音波を照射し、コロイダルシリカ分散液iii'− Min ultrasound was irradiated, colloidal silica dispersion iii'-
aを得た。 It was obtained a. シリコーン分散液iiiとコロイダルシリカ分散iii'−aを表5に示す値で混合し、常温で15分間マグネチックスターラーにて攪拌し、塗料組成物J1, Silicone dispersion iii colloidal silica dispersion III'-a were mixed in values ​​shown in Table 5, and stirred for 15 minutes at a magnetic stirrer at room temperature, paint compositions J1,
J2,J3,J4を得た。 It was obtained J2, J3, J4. 【0048】(調合例16)調合例15で疎水性コロイダルシリカを日本アエロジル社製NX90に変え、コロイダルシリカ分散液iii'−bを調製した以外は、調合例15と同様にし、塗料組成物K1,K2,K3,K4 [0048] changing the hydrophobic colloidal silica (Formulation Example 16) Formulation Example 15 to Nippon Aerosil NX90, except the preparation of the colloidal silica dispersion III'-b is in the same manner as Formulation Example 15, the coating composition K1 , K2, K3, K4
を得た。 It was obtained. 【0049】(調合例17)調合例15で疎水性コロイダルシリカを日本アエロジル社製NAX50に変え、コロイダルシリカ分散液iii'−cを調製した以外は、調合例15と同様にし、塗料組成物L1,L2,L3,L [0049] changing the hydrophobic colloidal silica (Formulation Example 17) Formulation Example 15 to Nippon Aerosil NAX50, except the preparation of the colloidal silica dispersion III'-c is the same manner as Formulation Example 15 A coating composition L1 , L2, L3, L
4を得た。 4 was obtained. 【0050】(調合例18)疎水性コロイダルシリカ(日本アエロジル社製RX200)と酢酸ブチルとを表6に示す配合量で混合した後、温度が上昇し過ぎないよう注意しながら、超音波分散機(エスエムテー社製UH [0050] (Formulation Example 18) After a hydrophobic colloidal silica (Nippon Aerosil Co., Ltd. RX200) and butyl acetate were mixed in the amounts shown in Table 6, being careful that the temperature does not increase excessively, an ultrasonic dispersing machine (SMT Co., Ltd. UH
−50)を用い、発振周波数20KHz、振幅約30μ With -50), the oscillation frequency 20 KHz, an amplitude of about 30μ
mで断続的に20分間超音波を照射し、コロイダルシリカ分散液M'−a,M'−bを得た。 Intermittently irradiated with ultrasonic waves for 20 minutes at m, to obtain a colloidal silica dispersion M'-a, the M'-b. 【0051】(調合例19)調合例18で酢酸ブチルを表6に示した配合に変えた以外は調合例18と同様にして、コロイダルシリカ分散液N'−a,O'−a,O' [0051] (Formulation Example 19) except that the butyl acetate in Formulation Example 18 was changed to the formulation shown in Table 6 in the same manner as Formulation Example 18, the colloidal silica dispersion N'-a, O'-a, O '
−b,P'−a,P'−b,Q'−a,Q'−b,R' -b, P'-a, P'-b, Q'-a, Q'-b, R '
−a,R'−bを得た。 -a, to obtain a R'-b. 【0052】(調合例20)疎水性コロイダルシリカ(日本アエロジル社製RX200)0.16重量部とキシレン7.84重量部を混合した後、温度が上昇し過ぎないよう注意しながら、超音波分散機(エスエムテー社製UH−50)を用い、発振周波数20KHz、振幅約30μmで表7に示す時間で超音波を照射し、コロイダルシリカ分散液S'−0,S'−0.25,S'−0. [0052] (Formulation Example 20) Hydrophobic colloidal silica (Nippon Aerosil Co., Ltd. RX200) were mixed 0.16 parts by weight of xylene 7.84 parts by weight, being careful that the temperature does not increase excessively, ultrasonic dispersion machine (manufactured by SMT Co., Ltd. UH-50) using the oscillation frequency 20 KHz, the ultrasound irradiated by the time shown in Table 7 at an amplitude of about 30 [mu] m, colloidal silica dispersion S'-0, S'-0.25, S ' -0.
5,S'−1.0,S'−3.0,S'−5.0,S' 5, S'-1.0, S'-3.0, S'-5.0, S '
−10,S'−20,を得た。 -10, was obtained S'-20, a. 【0053】(調合例21)疎水性コロイダルシリカ(日本アエロジル社製RX200)0.24重量部とn [0053] (Formulation Example 21) Hydrophobic colloidal silica (Nippon Aerosil Co., Ltd. RX200) 0.24 parts by weight of n
−ブタノール7.76重量部を混合した後、温度が上昇し過ぎないよう注意しながら、超音波分散機(エスエムテー社製UH−50)を用い、発振周波数20KHz、 - After mixing butanol 7.76 parts by weight, being careful that the temperature does not increase excessively, ultrasonic dispersing machine (manufactured by SMT Co., Ltd. UH-50) using the oscillation frequency 20 KHz,
振幅約30μmで表7に示す時間で超音波を照射し、コロイダルシリカ分散液N'−0,N'−0.25,N' Irradiated with ultrasonic waves at an amplitude of about 30μm time shown in Table 7, colloidal silica dispersion N'-0, N'-0.25, N '
−0.5,N'−1.0,N'−3.0,N'−10, -0.5, N'-1.0, N'-3.0, N'-10,
N'−b,N'−30を得た。 N'-b, to give the N'-30. 【0054】(調合例22)フッ素樹脂塗料(セントラル硝子社製セフラルコートFG730B)2.8重量部と酢酸ブチル36.3重量部を混合し、常温で5分マグネチックスターラーにて攪拌した後、疎水性コロイダルシリカ(日本アエロジル社製RX200)を0.8重量部を添加し、温度が上昇し過ぎないよう注意しながら、 [0054] (Formulation Example 22) Fluorine resin paint mixing (Central Glass Co., Ltd. CEFRAL COAT FG730B) 2.8 parts by weight of butyl acetate 36.3 parts by weight, was stirred at 5 minutes magnetic stirrer at room temperature, hydrophobic sex colloidal silica (Nippon Aerosil Co., Ltd. RX200) was added 0.8 part by weight, being careful that the temperature does not increase excessively,
超音波分散機(エスエムテー社製UH−150)を用い、 Using an ultrasonic disperser (manufactured by SMT Co., Ltd. UH-150),
発振周波数20KHz、振幅を表8に示す値で、断続的に20分間超音波を照射した。 Oscillation frequency 20 KHz, with the values ​​shown in Table 8 amplitude was intermittently irradiated with ultrasonic waves for 20 minutes. さらにポリイソシアネート型硬化剤(日本ポリウレタン社製コロネートHX)を0.1重量部添加し、常温で60分間マグネチックスターラーにて攪拌し、塗料組成物B−a,B−b,B− Polyisocyanate type curing agent (Nippon Polyurethane Industry Co. Coronate HX) were added 0.1 part by weight, and stirred for 60 minutes a magnetic stirrer at room temperature, the coating composition B-a, B-b, B-
c,B−dを得た。 c, to obtain a B-d. 【0055】(調合例23)フッ素樹脂塗料(三菱レイヨン社製フロロナールFL6002)1.3重量部とキシレン28.5重量部、酢酸ブチル7.1重量部の混合溶剤とを混合し、常温で5分間マグネチックスターラーにて攪拌した後、コロイダルシリカゾル(日産化学工業社製スノーテックスXBA−ST)2.6重量部、ポリイソシアネート型硬化剤(大日本インキ化学工業社製バーノックDN990S)を0.4重量部添加し、常温で60分間マグネチックスターラーにて攪拌し、塗料組成物Tを得た。 [0055] (Formulation Example 23) Fluorine resin paint (manufactured by Mitsubishi Rayon Co., Ltd. Furoronaru FL6002) 1.3 parts by weight of xylene 28.5 parts by weight, was mixed with a mixed solvent of butyl acetate 7.1 parts by weight, at room temperature 5 after stirring at minute magnetic stirrer, a colloidal silica sol (manufactured by Nissan Chemical Industries, Ltd. Snowtex XBA-ST) 2.6 parts by weight of polyisocyanate type curing agent (manufactured by Dainippon Ink and Chemicals, Inc. Burnock DN990S) 0.4 It was added parts, stirred for 60 minutes a magnetic stirrer at room temperature to obtain a coating composition T. 【0056】(実施例1)90×90mmに切断したポリエチレンテレフタレートフィルム(東レ・デュポン社製ルミラー100−U94、以下PETフィルム)に調合例1で作製した塗料組成物A1を2cc滴下し、スピンコーター(エイブル社製ASS301)にて1500 [0056] (Example 1) polyethylene terephthalate was cut into 90 × 90 mm phthalate film (manufactured by Du Pont-Toray Co., Ltd. Lumirror 100-U94, PET film hereinafter) a coating composition A1 prepared in Formulation Example 1 To 2cc dropwise, spin coater at (Able Co., Ltd. ASS301) 1500
rpmで20秒スピンコートし、塗料組成物A1の被覆物試験板a1を得た。 20 seconds spin-coated at rpm, to obtain a coating test plate a1 of the coating composition A1. 【0057】(比較例1)実施例1と同様にして、調合例2で作製した塗料組成物A2,A3をPETフィルムにスピンコートし、塗料組成物A2,A3の被覆物試験板a2,a3を得た。 [0057] (Comparative Example 1) In the same manner as in Example 1, a coating composition A2, A3 prepared in Formulation Example 2 was spin-coated on a PET film, the coating test plate a2 of the coating composition A2, A3, a3 It was obtained. 【0058】(実施例2)実施例1と同様にして、調合例3、調合例4で作製した塗料組成物B3,B4,B [0058] In the same manner as Example 2 Example 1, Formulation Example 3, the coating composition prepared in Formulation Example 4 B3, B4, B
5,B6,B7をPETにスピンコートし、塗料組成物B3,B4,B5,B6,B7の被覆試験板b3,b 5, B6, B7 was spin-coated on the PET, the coating composition B3, B4, B5, B6, B7 coated test plate b3 of, b
4,b5,b6,b7を得た。 4, b5, b6, were obtained b7. 【0059】(比較例2)実施例1と同様にして、調合例4で作製した塗料組成物B1,B2をPETフィルムにスピンコートし、塗料組成物B1,B2の被覆物試験板b1,b2を得た。 [0059] (Comparative Example 2) In the same manner as in Example 1, the coating composition B1, B2 prepared in Formulation Example 4 was spin-coated PET film, the coating test plate b1 of the coating composition B1, B2, b2 It was obtained. 【0060】(比較例3)実施例1と同様にして、調合例5で作製した塗料組成物B8をPETフィルムにスピンコートし、塗料組成物B8の被覆物試験板b8を得た。 [0060] (Comparative Example 3) In the same manner as in Example 1, a coating composition B8 was prepared in Formulation Example 5 was spin-coated on a PET film to give a coating test panel b8 of the coating composition B8. 【0061】(実施例3)実施例1と同様にして、調合例6、調合例7で作製した塗料組成物C3,C7をPE [0061] In the same manner as Example 3 Example 1, Formulation Example 6, a coating composition C3, C7 prepared in Formulation Example 7 PE
Tにスピンコートし、塗料組成物C3,C7の被覆試験板c3,c7を得た。 Was spin-coated on the T, to obtain a coated test plate c3, c7 of the coating composition C3, C7. 【0062】(比較例4)実施例1と同様にして、調合例7で作製した塗料組成物C1,C2,C4,C5,C [0062] (Comparative Example 4) In the same manner as in Example 1, the coating composition C1 was prepared in Formulation Example 7, C2, C4, C5, C
6をPETにスピンコートし、塗料組成物C1,C2, Was spin-coated 6 to PET, the coating composition C1, C2,
C4,C5,C6の被覆試験板c1,c2,c4,c C4, C5, C6 covered test plate of c1, c2, c4, c
5,c6を得た。 5, was obtained c6. 【0063】(実施例4)実施例1と同様にして、調合例8、調合例9で作製した塗料組成物D4,D5,D [0063] In the same manner as Example 4 Example 1, Formulation Example 8 A coating composition prepared in Formulation Example 9 D4, D5, D
6,D7をPETにスピンコートし、塗料組成物D4, 6, D7 was spin-coated on the PET, the coating composition D4,
D5,D6,D7の被覆試験板d4,d5,d6,d7 D5, D6, D7 coated test panels d4, d5, d6, d7
を得た。 It was obtained. 【0064】(比較例5)実施例1と同様にして、調合例9で作製した塗料組成物D1,D2,D3をPETにスピンコートし、塗料組成物D1,D2,D3の被覆試験板d1,d2,d3を得た。 [0064] (Comparative Example 5) In the same manner as in Example 1, a coating composition D1, D2, D3 prepared in Formulation Example 9 was spin-coated on PET, the coating composition D1, D2, D3 coated test panels d1 to give the d2, d3. 【0065】(実施例5)実施例1と同様にして、調合例10で作製した塗料組成物E3,E4をPETにスピンコートし、塗料組成物E3,E4の被覆試験板e3, [0065] In the same manner as Example 5 Example 1, a coating composition E3, E4 prepared in Formulation Example 10 was spin-coated on PET, the coating composition E3, E4 coated test plate e3 of
e4を得た。 It was obtained e4. 【0066】(比較例6)実施例1と同様にして、調合例10で作製した塗料組成物E1,E2をPETにスピンコートし、塗料組成物E1,E2の被覆試験板e1, [0066] (Comparative Example 6) In the same manner as in Example 1, a coating composition E1, E2 produced in Formulation Example 10 was spin-coated on PET, the coating composition E1, E2 coated test plate e1 of
e2を得た。 It was obtained e2. 【0067】(実施例6)実施例1と同様にして、調合例11で作製した塗料組成物F3,F4をPETにスピンコートし、塗料組成物F3,F4の被覆試験板f3, [0067] In the same manner as Example 6 Example 1, a coating composition F3, F4 prepared in Formulation Example 11 was spin-coated on PET, the coating composition F3, F4 coated test plate f3 of
f4を得た。 It was obtained f4. 【0068】(比較例7)実施例6と同様にして、調合例11で作製した塗料組成物F1,F2をPETにスピンコートし、塗料組成物F1,F2の被覆試験板f1, [0068] (Comparative Example 7) In the same manner as in Example 6, the coating compositions F1, F2 prepared in Formulation Example 11 was spin-coated on PET, coated test plate f1 of the coating composition F1, F2,
f2を得た。 It was obtained f2. 【0069】(比較例8)実施例5と同様にして、調合例12で作製した塗料組成物G1,G2,G3,G4をPETにスピンコートし、塗料組成物G1,G2,G [0069] In the same manner as Comparative Example 8 Example 5 A coating composition was prepared in Formulation Example 12 G1, G2, G3, G4 was spin-coated on the PET, the coating composition G1, G2, G
3,G4の被覆試験板g1,g2,g3,g4を得た。 3, G4 of the coating test plate g1, g2, g3, to obtain a g4. 【0070】(比較例9)実施例5と同様にして、調合例13で作製した塗料組成物H1,H2,H3,H4をPETにスピンコートし、塗料組成物H1,H2,H [0070] In the same manner as Comparative Example 9 Example 5, the coating composition H1, H2, H3, H4 prepared in Formulation Example 13 was spin-coated on PET, the coating composition H1, H2, H
3,H4の被覆試験板h1,h2,h3,h4を得た。 3, H4 coated test plate h1 of, h2, h3, was obtained h4. 【0071】(比較例10)実施例5と同様にして、調合例14で作製した塗料組成物I1,I2,I3,I4 [0071] (Comparative Example 10) In the same manner as in Example 5, coating compositions prepared in Formulation Example 14 I1, I2, I3, I4
をPETにスピンコートし、塗料組成物I1,I2,I Was spin-coated on the PET, the coating composition I1, I2, I
3,I4の被覆試験板i1,i2,i3,i4を得た。 3, I4 coated test panels i1, i2, i3, was obtained i4. 【0072】(実施例7)実施例1と同様にして、調合例15で作製した塗料組成物J4をPETフィルムにスピンコートし、塗料組成物J4の被覆物試験板j4を得た。 [0072] In the same manner as Example 7 Example 1, a coating composition J4 prepared in Formulation Example 15 was spin coated on a PET film to give a coating test panel j4 of the coating composition J4. 【0073】(比較例11)実施例7と同様にして、調合例15で作製した塗料組成物J1,J2,J3をPE [0073] In the same manner as Comparative Example 11 Example 7, coating compositions J1, J2, J3 prepared in Formulation Example 15 PE
Tフィルムにスピンコートし、塗料組成物J1,J2, Was spin-coated on the T film, the coating composition J1, J2,
J3の被覆物試験板j1,j2,j3を得た。 J3 coating test panels j1, j2, to obtain a j3. 【0074】(比較例12)実施例7と同様にして、調合例16で作製した塗料組成物K1,K2,K3,K4 [0074] (Comparative Example 12) In the same manner as in Example 7, coating compositions prepared in Formulation Example 16 K1, K2, K3, K4
をPETフィルムにスピンコートし、塗料組成物K1, It was spin-coated on a PET film, the coating composition K1,
K2,K3,K4の被覆物試験板k1,k2,k3,k K2, K3, K4 coating test panels k1, k2, k3, k
4を得た。 4 was obtained. 【0075】(比較例13)実施例7と同様にして、調合例17で作製した塗料組成物L1,L2,L3,L4 [0075] In the same manner as Comparative Example 13 Example 7, coating compositions prepared in Formulation Example 17 L1, L2, L3, L4
をPETフィルムにスピンコートし、塗料組成物L1, Was spin-coated on a PET film, the coating composition L1,
L2,L3,L4の被覆物試験板l1,l2,l3,l L2, L3, L4 coating test panels l1, l2, l3, l
4を得た。 4 was obtained. 【0076】(実施例8)実施例1と同様にして、調合例18で作製したコロイダルシリカ分散液M'−bをP [0076] In the same manner as Example 8 Example 1, a colloidal silica dispersion M'-b prepared in Formulation Example 18 P
ETフィルムにスピンコートし、塗料組成物M'−bの被覆物試験板m'−bを得た。 Was spin-coated on ET film, to obtain a coating test panel m'-b of the coating composition M'-b. 【0077】(比較例14)実施例8と同様にして、調合例18で作製したコロイダルシリカ分散液M'−aをPETフィルムにスピンコートし、塗料組成物M'−a [0077] In the same manner as Comparative Example 14 Example 8, colloidal silica dispersion M'-a prepared in Formulation Example 18 was spin-coated on a PET film, the coating composition M'-a
の被覆物試験板m'−aを得た。 Was obtained coatings test plate m'-a. 【0078】(実施例9)実施例1と同様にして、調合例19で作製したコロイダルシリカ分散液O'−b, [0078] In the same manner as Example 9 Example 1, colloidal silica dispersion O'-b prepared in Formulation Example 19,
P'−b,Q'−b,R'−bをPETフィルムにスピンコートし、塗料組成物O'−b,P'−b,Q'− P'-b, Q'-b, it was spin-coated R'-b PET film, the coating composition O'-b, P'-b, Q'-
b,R'−bの被覆物試験板o'−b,p'−b,q' b, the coating test plate o'-b of R'-b, p'-b, q '
−b,r'−bを得た。 -b, were obtained r'-b. 【0079】(比較例15)実施例9と同様にして、調合例19で作製したコロイダルシリカ分散液N'−a, [0079] (Comparative Example 15) In the same manner as in Example 9, colloidal silica dispersion N'-a prepared in Formulation Example 19,
O'−a,P'−a,Q'−a,R'−aをPETフィルムにスピンコートし、塗料組成物N'−a,O'− O'-a, P'-a, Q'-a, was spin-coated R'-a PET film, the coating composition N'-a, O'
a,P'−a,Q'−a,R'−aの被覆物試験板n' a, P'-a, Q'-a, the coating test plate n of R'-a '
−a,o'−a,p'−a,q'−a,r'−aを得た。 -a, o'-a, p'-a, q'-a, to give a r'-a. 【0080】(実施例10)実施例1と同様にして、調合例20で作製したコロイダルシリカ分散液S'−0. [0080] (Example 10) In the same manner as in Example 1, a colloidal silica dispersion S'-0 prepared in Formulation Example 20.
5,S'−1.0をPETフィルムにスピンコートし、 5, was spin-coated on a PET film S'-1.0,
塗料組成物S'−0.5,S'−1.0の被覆物試験板s'−0.5,s'−1.0を得た。 The coating composition S'-0.5, the coating test plate s'-0.5 of S'-1.0, was obtained s'-1.0. 【0081】(比較例16)実施例10と同様にして、 [0081] In the same manner (Comparative Example 16) Example 10,
調合例20で作製したコロイダルシリカ分散液S'− Colloidal silica dispersion prepared in Formulation Example 20 S'
0,S'−0.25,S'−3.0,S'−5.0, 0, S'-0.25, S'-3.0, S'-5.0,
S'−10,S'−20をPETフィルムにスピンコートし、塗料組成物S'−0,S'−0.25,S'− S'-10, was spin-coated S'-20 PET film, the coating composition S'-0, S'-0.25, S'-
3.0,S'−5.0,S'−10,S'−20の被覆物試験板s'−0,s'−0.25,s'−3.0, 3.0, S'-5.0, S'-10, the coating test plate s'-0 of S'-20, s'-0.25, s'-3.0,
s'−5.0,s'−10,s'−20を得た。 s'-5.0, s'-10, was obtained s'-20. 【0082】(実施例11)実施例1と同様にして、調合例21で作製したコロイダルシリカ分散液N'−0. [0082] (Example 11) In the same manner as in Example 1, the colloidal silica prepared in Formulation Example 21 Dispersion N'-0.
25,N'−0.5,N'−1.0,N'−3.0, 25, N'-0.5, N'-1.0, N'-3.0,
N'−10,N'−bをPETフィルムにスピンコートし、塗料組成物N'−0.25,N'−0.5,N'− N'-10, was spin-coated N'-b PET film, the coating composition N'-0.25, N'-0.5, N'-
1.0,N'−3.0,N'−10,N'−20の被覆物試験板n'−0.25,n'−0.5,n'−1. 1.0, N'-3.0, N'-10, the coating test plate n'-0.25 of N'-20, n'-0.5, n'-1.
0,n'−3.0,n'−10,n'−bを得た。 0, n'-3.0, n'-10, was obtained n'-b. 【0083】(比較例17)実施例11と同様にして、 [0083] In the same manner (Comparative Example 17) Example 11
調合例21で作製したコロイダルシリカ分散液N'− Colloidal silica dispersion prepared in Formulation Example 21 N'
0,N'−30をPETフィルムにスピンコートし、塗料組成物N'−0,N'−30の被覆物試験板n'− 0, was spin-coated N'-30 the PET film, the coating composition N'-0, of N'-30 coating the test plate n'-
0,n'−30を得た。 0 to give the n'-30. 【0084】(実施例12)実施例1と同様にして、調合例22で作製した塗料組成物B−c,B−dをPET [0084] In the same manner as Example 12 Example 1, the coating composition B-c prepared in Formulation Example 22, the B-d PET
フィルムにスピンコートし、塗料組成物B−c,B−d It was spin-coated film, the coating composition B-c, B-d
の被覆物試験板b−c,b−dを得た。 The coating test panel b-c of, to give the b-d. 【0085】(比較例18)実施例12と同様にして調合例22で作製した塗料組成物B−a,B−bをPET [0085] (Comparative Example 18) Example 12 a coating composition B-a prepared in Formulation Example 22 in a similar manner, the B-b PET
フィルムにスピンコートし、塗料組成物B−a,B−b It was spin-coated film, the coating composition B-a, B-b
の被覆物試験板b−a,b−bを得た。 The coating test panel b-a of the to give the b-b. 【0086】(比較例19)実施例1と同様にして調合例23で作製した塗料組成物TをPETフィルムにスピンコートし、塗料組成物Tの被覆物試験板tを得た。 [0086] (Comparative Example 19) The coating composition T was prepared in Formulation Example 23 in the same manner as in Example 1 was spin-coated on a PET film to give a coating test plate t of the coating composition T. 【0087】(評価) (1)撥水性の評価作製した試験片a〜fを試験片作製後室温にて3日間放置した後、接触角計(共和界面科学製CX−150型) [0087] (Evaluation) (1) was allowed to stand 3 days specimen a~f assessed Preparation of water repellent in the test specimen was room temperature, the contact angle meter (manufactured by Kyowa Interface Science CX-0.99-inch)
を用い、内径0.1mmのPTFE(ポリテトラフルオロエチレン)コートされた針の先端に約1μlの水滴を形成させた後、弾き落とすことで約1μlの水滴を試験片上にのせ、接触角を測定した。 The used, after forming about 1μl of water droplets at the tip of the inner diameter 0.1mm of PTFE (polytetrafluoroethylene) coated needles, placed on the specimen for about 1μl of water droplets dropping play, measuring the contact angle did. (2)透明性の評価JIS−K7105に準じて、被覆物試験板の全光線透過率およびヘーズを測定した。 (2) in accordance with evaluation JIS-K7105 transparency was measured for total light transmittance and haze of the coating test plate. 【0088】(結果)表1〜10に評価結果を示す。 [0088] (Results) The evaluation results are shown in Table 1 to 10. 表より、本発明の実施例では、光線のヘーズ値10%以下かつ水との接触角150°以上となり、優れた透明性と撥水性を同時に発揮することがわかる。 From Table, in the embodiment of the present invention, it is the contact angle 150 ° or more and a haze value of 10% or less and water of the light beam, it can be seen that excellent transparency and water-repellent at the same time. また、保存安定性も良好であった。 Further, it had high preservation stability. それに対して、比較例は光線のヘーズ値10%以下と水との接触角150°以上とのいずれかを満足せず、それに近い値である被覆物試験板o'− In contrast, Comparative Examples did not satisfy either the contact angle 150 ° or more and a haze value of 10% or less and the water of the ray, it is a value close coating test plate o'-
a,s'−0.25,s'−3.0,s'−5.0, a, s'-0.25, s'-3.0, s'-5.0,
s'−10,s'−20,n'−30においてはコロイダルシリカ分散液板O'−a,S'−0.25,S'− s'-10, s'-20, colloidal silica dispersion plate O'-a in n'-30, S'-0.25, S'-
3.0,S'−5.0,S'−10,S'−20,N' 3.0, S'-5.0, S'-10, S'-20, N '
−30の保存安定性がなかった。 There was no storage stability of -30. 【0089】 【表1】 [0089] [Table 1] 【0090】 【表2】 [0090] [Table 2] 【0091】 【表3】 [0091] [Table 3] 【0092】 【表4】 [0092] [Table 4] 【0093】 【表5】 [0093] [Table 5] 【0094】 【表6】 [0094] [Table 6] 【0095】 【表7】 [0095] [Table 7] 【0096】 【表8】 [0096] [Table 8] 【0097】 【表9】 [0097] [Table 9] 【0098】 【表10】 [0098] [Table 10] 【0099】 【発明の効果】本発明によれば、基材に対し、撥水性及び透明性に優れた低温乾燥型の超撥水塗料組成物および該塗膜を被覆した超撥水材を提供することが可能となる。 [0099] According to the present invention, with respect to the substrate, provides a low-temperature drying type super water-repellent coating compositions and super water-repellent material and the coating film by coating with excellent water repellency and transparency it is possible to become.

フロントページの続き (51)Int.Cl. 7識別記号 FI テーマコート゛(参考) C08J 7/04 CFD C08J 7/04 CFDZ C09D 5/00 C09D 5/00 Z // C08L 27:12 C08L 27:12 67:02 67:02 (72)発明者 中島 章 神奈川県茅ヶ崎市本村2丁目8番1号 株 式会社先端技術インキュベーションシステ ムズ内Fターム(参考) 4F006 AA35 AB19 AB24 AB39 AB76 BA11 4F070 AA23 AC23 CA16 CB05 CB12 4H020 BA02 BA03 BA12 BA32 4J038 CD091 CG001 CL001 DL031 HA446 KA20 NA07 Of the front page Continued (51) Int.Cl. 7 identification mark FI theme Court Bu (Reference) C08J 7/04 CFD C08J 7/04 CFDZ C09D 5/00 C09D 5/00 Z // C08L 27:12 C08L 27:12 67 : 02 67:02 (72) inventor Akira Nakajima Chigasaki, Kanagawa Prefecture Motomura 2-chome No. 8 No. 1 Co., Ltd. advanced technology incubation system Chelmsford in the F-term (reference) 4F006 AA35 AB19 AB24 AB39 AB76 BA11 4F070 AA23 AC23 CA16 CB05 CB12 4H020 BA02 BA03 BA12 BA32 4J038 CD091 CG001 CL001 DL031 HA446 KA20 NA07

Claims (1)

  1. 【特許請求の範囲】 【請求項1】 (A)疎水処理が施されたシリカ微粒子と(B)フッ素含有樹脂、加水分解性シラン、ポリオルガノシロキサン、アクリルシリコーン樹脂、アクリル樹脂から選ばれる1種または2種以上を少なくとも含有する疎水性樹脂が、揮発後の重量分率でそれぞれ(A)が30〜100%、(B)が0〜70%となるように含有され、周波数10〜30kHz、振幅10〜50μmの超音波を(A)疎水処理が施されたシリカ微粒子に照射し、有機溶媒中に分散させたことを特徴とする超撥水剤。 Claims 1. A (A) and fine silica particles hydrophobic processing is performed (B) a fluorine-containing resin, hydrolyzable silane, polyorganosiloxanes, acrylic silicone resin, one selected from an acrylic resin or hydrophobic resin containing at least two or more kinds, respectively the weight fraction after volatilization (a) is 30% to 100%, is contained as (B) is 0% to 70%, frequency 10~30KHz, super water repellent, characterized in that irradiating the amplitude 10~50μm of ultrasonic waves (a) fine silica particles hydrophobic treatment has been performed, are dispersed in an organic solvent. 【請求項2】 (A)疎水処理が施されたシリカ微粒子と(B)フッ素含有樹脂、加水分解性シラン、ポリオルガノシロキサン、アクリルシリコーン樹脂、アクリル樹脂から選ばれる1種または2種以上を少なくとも含有する疎水性樹脂が、揮発後の重量分率でそれぞれ(A)が30〜99%、(B)が1〜70%となるように含有され、周波数10〜30kHz、振幅10〜50μmの超音波を(A)疎水処理が施されたシリカ微粒子に照射し、有機溶媒中に分散させたことを特徴とする超撥水剤。 Wherein (A) and fine silica particles hydrophobic processing is performed (B) a fluorine-containing resin, hydrolyzable silane, polyorganosiloxanes, acrylic silicone resin, at least one or more selected from acrylic resin hydrophobic resin containing, respectively the weight fraction after volatilization (a) is 30 to 99%, is contained so as to have 1 to 70% (B), the frequency 10~30KHz, amplitude 10~50μm super irradiating sound waves to the (a) fine silica particles hydrophobic processing is performed, an ultra water-repellent agent characterized by dispersed in an organic solvent. 【請求項3】 前記有機溶媒として、アルコール類、ケトン類、エステル類、アルコールエステル類、ケトンエステル類、エーテル類、ケトンアルコール類、エーテルアルコール類、ケトンエーテル類、エステルエーテル類から選ばれる1種または2種以上を少なくとも含有することを特徴とする請求項1又は2記載の超撥水剤。 As claimed in claim 3, wherein the organic solvent, alcohols, ketones, esters, alcohol esters, ketone esters, ethers, ketones alcohols, ether alcohols, ketones ethers, one selected from an ester ethers or super water-repellent agent according to claim 1 or 2, wherein the at least containing two or more. 【請求項4】 前記微粒子の平均1次粒子径が1〜20 Wherein an average primary particle size of the fine particles is 1 to 20
    nmである請求項1乃至3記載の超撥水剤。 nm ultra water repellent of claims 1 to 3, wherein a. 【請求項5】 基材表面に、請求項1乃至4に記載の超撥水剤を塗布後、硬化することにより超撥水被膜が形成されていることを特徴とする超撥水材。 5. A substrate surface, after coating a super water-repellent agent according to claims 1 to 4, ultra-water repellent material, characterized in that the super-water-repellent film is formed by curing. 【請求項6】 前記硬化は、10〜150℃での乾燥により行うことを特徴とする請求項5記載の超撥水材。 Wherein said curing is super water-repellent material of claim 5, wherein the performing by drying at 10 to 150 ° C.. 【請求項7】 前記超撥水被膜は、100nm以上2μ Wherein said super water-repellent coating, 100 nm or more 2μ
    m以下であることを特徴とする請求項5又は6記載の超撥水材。 Claim 5 or 6 super water-repellent material, wherein the m or less. 【請求項8】 光線のヘーズ値10%以下、水との接触角が150°以上であることを特徴とする請求項7記載の超撥水材。 8. 10% haze value of the optical hereinafter super water-repellent material of claim 7, wherein the contact angle with water is characterized in that at 150 ° or more.
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JP2005113110A (en) * 2003-09-17 2005-04-28 Keio Gijuku Surface treatment agent, treated material, and method for treating surface
JP4635217B2 (en) * 2003-09-17 2011-02-23 学校法人慶應義塾 Surface treatment agent, and materials and surface treatment methods
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CN100489049C (en) 2006-07-06 2009-05-20 北京中化科城技术研究所 Elastic water-proof material
JP2008038096A (en) * 2006-08-09 2008-02-21 Soft99 Corporation Agent for water-repelling treatment and method for water-repelling treatment
JP2008050380A (en) * 2006-08-22 2008-03-06 Snt Co Water repellent and use thereof
JP2009136710A (en) * 2007-12-03 2009-06-25 Inoue Mfg Inc Roll mill and dispersion or pulverization method using it
US8314037B2 (en) 2007-12-07 2012-11-20 E. I. Du Pont De Nemours And Company Fluoropolymer emulsions
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US8507601B2 (en) 2009-11-09 2013-08-13 E. I. Du Pont De Nemours And Company Method using fluoropolymer emulsions
US8329822B2 (en) 2009-11-09 2012-12-11 E.I. Du Pont De Nemours And Company Fluoropolymer emulsions
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KR101468817B1 (en) * 2013-09-09 2014-12-11 광운대학교 산학협력단 a method of fabricating superhydrophobic surface coatings
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JP2015155512A (en) * 2014-02-21 2015-08-27 三菱電機株式会社 Coating composition and method for producing the same, water repellant member, and exhaust fan

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