JP2007238931A - Hydrophobic coating film-forming composition, the resultant hydrophobic coating film, method for forming the film, and functional material having the film - Google Patents
Hydrophobic coating film-forming composition, the resultant hydrophobic coating film, method for forming the film, and functional material having the film Download PDFInfo
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
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- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、疎水性コーティング膜形成組成物、疎水性コーティング膜、その形成方法及びそれを備えた機能性材料に関する。 The present invention relates to a composition for forming a hydrophobic coating film, a hydrophobic coating film, a method for forming the same, and a functional material including the same.
従来から、フッ素樹脂やシリコーン樹脂等を用いてコーティングするといった化学的処理により、金属、ガラス、紙、布、プラスティック等の基材表面に疎水性を付与することが行われている。 Conventionally, hydrophobicity is imparted to the surface of a substrate such as metal, glass, paper, cloth, and plastic by a chemical treatment such as coating with a fluororesin or a silicone resin.
例えば、特開平３−２１５５７０公報（特許文献１）には、表面張力が３２ｄｙｎｅ／ｃｍ以下の疎水性微粉末と吸水率０．５％以下の樹脂とからなる疎水性塗料が記載されており、疎水性の目安である水の接触角が１７０°以上の塗料が開示されている。また、特開平７−３２８５３２号公報（特許文献２）には、少なくとも表面が疎水性である平均粒子径が１ｎｍ〜１ｍｍの微粒子と樹脂塗膜とからなり、該微粒子が該樹脂塗膜表面積の２０％以上に露出されて固着されていることを特徴とする疎水性被膜が記載されており、水の接触角が１６０°以上の疎水性被膜が開示されている。さらに、特開２０００−２３０１４０号公報（特許文献３）には、基材の表面に疎水性の塗膜を付与する疎水性塗料であって、フッ素を含まない疎水性シランカップリング剤で表面処理された硬質微粒子と、該硬質微粒子を前記基材上に担持するためのバインダー樹脂と、該バインダー樹脂の溶剤とを少なくとも含むことを特徴とする疎水性塗料が記載されており、接触角が１５０°以上の疎水性塗料が開示されている。これらの技術は何れも、微粉末や微粒子をバインダー樹脂によって基材表面に固着させることにより、表面に凹凸を形成させ、疎水性を発現させるものである。 For example, JP-A-3-215570 (Patent Document 1) describes a hydrophobic paint comprising a hydrophobic fine powder having a surface tension of 32 dyne / cm or less and a resin having a water absorption of 0.5% or less. A paint having a water contact angle of 170 ° or more, which is a measure of hydrophobicity, is disclosed. Japanese Patent Laid-Open No. 7-328532 (Patent Document 2) includes at least a hydrophobic surface having an average particle diameter of 1 nm to 1 mm and a resin coating film, and the fine particle has a surface area of the resin coating film. A hydrophobic film characterized by being exposed and fixed to 20% or more is described, and a hydrophobic film having a water contact angle of 160 ° or more is disclosed. Furthermore, JP 2000-230140 A (Patent Document 3) discloses a hydrophobic coating that imparts a hydrophobic coating to the surface of a substrate, and is surface-treated with a hydrophobic silane coupling agent that does not contain fluorine. A hydrophobic paint comprising at least a hard resin fine particle, a binder resin for supporting the hard fine particle on the substrate, and a solvent for the binder resin. Hydrophobic paints at or above ° are disclosed. In any of these techniques, fine powders or fine particles are fixed to the surface of a substrate with a binder resin, thereby forming irregularities on the surface and developing hydrophobicity.
また、特開平１０−２５９０３７号公報（特許文献４）には、可視光透過率がガラス基板並み以上である透明シリカ膜を基板上に形成させることにより得られる、接触角が１４０°以上であることを特徴とする疎水性被膜が記載されている。さらに、特開平７−１９７０１７号公報（特許文献５）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も小さい周期の凹凸構造を含む多段凹凸構造を有し、その表面積倍増因子が５以上である疎水表面を有する固体が開示されており、１７４°以上の接触角が達成されている。また、特開平８−９２４９９号公報（特許文献６）には、使用環境温度以上の融点を有するワックス類、油脂類又はそれらの混合物を含有する疎水性塗料が開示されており、１４０〜１５０°の接触角が達成されている。さらに、特開平８−３２３２８０号公報（特許文献７）には、基材表面において、分子内に疎水基を有する反応性モノマー又はオリゴマーを重合させ、疎水基を有するポリマーからなる微細な凹凸構造を基材表面に形成させることを特徴とする基材表面への疎水性付与方法が開示されており、１５０〜１６０°程度の接触角が達成されている。 Japanese Patent Laid-Open No. 10-259037 (Patent Document 4) discloses that a contact angle obtained by forming a transparent silica film having a visible light transmittance equal to or higher than that of a glass substrate on a substrate is 140 ° or more. A hydrophobic coating characterized by this is described. Further, JP-A-7-97017 (Patent Document 5) discloses a multi-step concavo-convex structure in which a concavo-convex structure having a large period is formed on at least a part of the surface, and the concavo-convex structure includes a concavo-convex structure having a period smaller than the period. And a solid having a hydrophobic surface with a surface area doubling factor of 5 or greater is disclosed, and a contact angle of 174 ° or greater is achieved. JP-A-8-92499 (Patent Document 6) discloses a hydrophobic paint containing waxes, fats and oils or a mixture thereof having a melting point equal to or higher than the use environment temperature, 140 to 150 °. The contact angle is achieved. Further, JP-A-8-323280 (Patent Document 7) discloses a fine concavo-convex structure made of a polymer having a hydrophobic group by polymerizing a reactive monomer or oligomer having a hydrophobic group in the molecule on the substrate surface. A method for imparting hydrophobicity to a substrate surface characterized by forming the substrate surface is disclosed, and a contact angle of about 150 to 160 ° is achieved.
しかしながら、このようなフッ素樹脂、シリコーン樹脂等を用いた従来の疎水性を付与する組成物を用いる場合、樹脂によるコーティング膜を形成させるために、機械加工処理、電気メッキ処理、加熱／冷却処理といった特殊な処理を必要とするものであり、またその処理によっては高温での乾燥及びエージングに数日を要するという問題を有していた。また、形成された疎水性膜に凹凸をつけて疎水性を付与する場合、コーティング膜を形成する被処理材の材料によっては塗りムラができて疎水性にバラツキが発生したり、その耐久性が十分でないという問題を有していた。
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、疎水性が要求される様々な材質及び表面構造を有する被処理材に対して、疎水性、防汚性及びそれらの耐久性に優れた均一な疎水性コーティング膜をより簡単に且つ効率良く形成することを可能とする疎水性コーティング膜形成組成物及びその形成方法、並びにそれによって得られた疎水性コーティング膜及び機能性材料を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and has hydrophobicity, antifouling properties and durability for materials to be treated having various materials and surface structures that require hydrophobicity. Hydrophobic coating film forming composition and method for forming the same, and a hydrophobic coating film and a functional material obtained by the composition can be easily and efficiently formed with a uniform hydrophobic coating film having excellent properties The purpose is to provide.
本発明者は、上記目的を達成すべく鋭意研究を重ねた結果、ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物を樹脂化合物及び揮発性溶媒と組み合わせた疎水性コーティング膜形成組成物を用いることにより、様々な被処理材に対して疎水性及びそれらの耐久性に優れた均一な疎水性コーティング膜をより簡単に且つ効率良く形成することが可能となり、さらに特異的に防汚、超撥水、防水、防雪、防氷、防錆、防藻、防菌、防カビ等の機能が発揮されるようになることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor has obtained a hydrophobic coating film forming composition in which a hydrophobic fine silica compound modified with hexamethyldisilazane is combined with a resin compound and a volatile solvent. By using it, it becomes possible to more easily and efficiently form a uniform hydrophobic coating film excellent in hydrophobicity and durability for various materials to be treated. It has been found that functions such as water repellency, water proofing, snow proofing, ice proofing, rust proofing, algae proofing, antibacterial proofing and mold proofing will be exhibited, and the present invention has been completed.
すなわち、本発明の疎水性コーティング膜形成組成物は、（Ａ）ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物、（Ｂ）樹脂化合物、及び（Ｃ）揮発性溶媒を含有することを特徴とするものである。本発明の疎水性コーティング膜形成組成物においては、（Ａ）ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物、（Ｂ）樹脂化合物、及び（Ｃ）揮発性溶媒を、それらの均一分散物として含有していることが好ましい。 That is, the hydrophobic coating film-forming composition of the present invention contains (A) a hydrophobic fine silica compound modified with hexamethyldisilazane, (B) a resin compound, and (C) a volatile solvent. It is a feature. In the composition for forming a hydrophobic coating film of the present invention, (A) a hydrophobic fine silica compound modified with hexamethyldisilazane, (B) a resin compound, and (C) a volatile solvent are uniformly dispersed therein. It is preferable to contain as a product.
本発明の疎水性コーティング膜の形成方法は、前記本発明の疎水性コーティング膜形成組成物を被処理材の表面に塗布した後に乾燥させることを特徴とする方法である。 The method for forming a hydrophobic coating film of the present invention is a method characterized in that the hydrophobic coating film forming composition of the present invention is applied to the surface of a material to be treated and then dried.
また、本発明の疎水性コーティング膜は、（Ａ）ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物、及び（Ｂ）樹脂化合物を含有することを特徴とするものである。本発明の疎水性コーティング膜においては、（Ａ）ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物が、バインダーとしての（Ｂ）樹脂化合物中に分散していることが好ましい。 Moreover, the hydrophobic coating film of the present invention is characterized by containing (A) a hydrophobic fine silica compound modified with hexamethyldisilazane, and (B) a resin compound. In the hydrophobic coating film of the present invention, it is preferable that (A) a hydrophobic fine silica compound modified with hexamethyldisilazane is dispersed in (B) a resin compound as a binder.
さらに、本発明の機能性材料は、前記本発明の疎水性コーティング膜を備えることを特徴とするものである。 Furthermore, the functional material of the present invention is characterized by including the hydrophobic coating film of the present invention.
なお、本発明によって様々な被処理材に対して疎水性及びそれらの耐久性に優れた均一な疎水性コーティング膜をより簡単に且つ効率良く形成することが可能となり、さらに特異的に防汚、超撥水、防水、防雪、防氷、防錆、防藻、防菌、防カビ等の機能が発揮されるようになる理由は必ずしも定かではないが、本発明者は以下のように推察する。すなわち、ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物を樹脂化合物及び揮発性溶媒と組み合わせた本発明の疎水性コーティング膜形成組成物を被処理材の表面に塗布して乾燥させると、水分を寄せ付けない疎水性に優れた微細な凹凸であるいわゆる「フルクタル構造」を有する膜が効率良く且つ均一に形成される。そして、このように被処理材の表面に形成された疎水性コーティング膜は疎水性及びその耐久性に非常に優れているため、さらに特異的に防汚、超撥水、防水、防雪、防氷、防錆、防藻、防菌、防カビ等の機能が発揮されるようになると本発明者は推察する。 In addition, according to the present invention, it becomes possible to more easily and efficiently form a uniform hydrophobic coating film having excellent hydrophobicity and durability for various materials to be treated, and more specifically, antifouling, The reason why the functions such as super water repellency, water proof, snow proof, ice proof, rust proof, algae proof, fungus proof, and mold proof are not necessarily known, but the present inventors speculate as follows. . That is, when the hydrophobic coating film forming composition of the present invention in which a hydrophobic fine silica compound modified with hexamethyldisilazane is combined with a resin compound and a volatile solvent is applied to the surface of the material to be treated and dried, A film having a so-called “fractal structure” that is fine irregularities excellent in hydrophobicity that do not attract moisture is efficiently and uniformly formed. In addition, the hydrophobic coating film formed on the surface of the material to be treated in this way is very excellent in hydrophobicity and durability, so that it is more specifically antifouling, super water repellent, waterproof, snowproof, and iceproof. The present inventors infer that functions such as rust prevention, anti-algae, antibacterial, and antifungal will be exhibited.
本発明によれば、疎水性が要求される様々な材質及び表面構造を有する被処理材に対して、疎水性、防汚性及びそれらの耐久性に優れた均一な疎水性コーティング膜をより簡単に且つ効率良く形成することを可能とする疎水性コーティング膜形成組成物及びその形成方法、並びにそれによって得られた疎水性コーティング膜及び機能性材料を提供することが可能となる。 According to the present invention, a uniform hydrophobic coating film excellent in hydrophobicity, antifouling property and durability is more easily applied to materials to be processed having various materials and surface structures that require hydrophobicity. In addition, it is possible to provide a hydrophobic coating film forming composition and a method for forming the same, and a hydrophobic coating film and a functional material obtained thereby.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
先ず、本発明の疎水性コーティング膜形成組成物について説明する。本発明の疎水性コーティング膜形成組成物は、（Ａ）ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物、（Ｂ）樹脂化合物、及び（Ｃ）揮発性溶媒を含有することを特徴とするものである。 First, the hydrophobic coating film forming composition of the present invention will be described. The hydrophobic coating film-forming composition of the present invention comprises (A) a hydrophobic fine silica compound modified with hexamethyldisilazane, (B) a resin compound, and (C) a volatile solvent. To do.
本発明に用いる（Ａ）成分としての疎水性微細シリカ化合物は、微細シリカの表面のＯＨ基にヘキサメチルジシラザンを接触反応させて改質したものである。かかる疎水性微細シリカ化合物の一次粒子の平均粒子径は５〜５０ｎｍであることが好ましい。この平均粒子径が５ｎｍ未満であると、疎水性コーティング膜形成組成物をコーティングし、乾燥した後に生成する疎水性コーティング膜の形成性が劣る傾向になり、そのためコーティング膜から疎水性微細シリカ化合物が飛散し易くなって疎水性が減少する傾向にある。一方、この平均粒子径が５０ｎｍを超えると、均一な疎水性コーティング膜になり難くなって疎水性が減少する傾向にある。 The hydrophobic fine silica compound as the component (A) used in the present invention is modified by contact reaction of hexamethyldisilazane with OH groups on the surface of fine silica. The average particle diameter of the primary particles of the hydrophobic fine silica compound is preferably 5 to 50 nm. When the average particle size is less than 5 nm, the hydrophobic coating film forming composition tends to be inferior in formability after being coated with a hydrophobic coating film forming composition and dried. It tends to scatter and tends to reduce hydrophobicity. On the other hand, when the average particle diameter exceeds 50 nm, it becomes difficult to form a uniform hydrophobic coating film and the hydrophobicity tends to decrease.
また、かかる疎水性微細シリカ化合物中の炭素量は２〜５質量％であることが好ましく、２．２〜４質量％であることが特に好ましい。この炭素量が２質量未満であると微細シリカ表面の疎水性への改質が不十分になる傾向にあり、５質量％を超えると不均一な改質部位が発生し易くなり、良好な疎水性が妨げられる傾向にある。 Moreover, it is preferable that the carbon content in this hydrophobic fine silica compound is 2-5 mass%, and it is especially preferable that it is 2.2-4 mass%. If the amount of carbon is less than 2 mass, modification of the fine silica surface to hydrophobicity tends to be insufficient, and if it exceeds 5 mass%, non-uniform modification sites are likely to occur and good hydrophobicity is achieved. Sex tends to be disturbed.
さらに、本発明に用いる（Ａ）成分の疎水性微細シリカ化合物としては、ヘキサメチルジシラザンを接触反応させて改質する際に、まず微細シリカの表面のＯＨ基にメチルトリクロルシラン、ジメチルジクロルシラン等のアルキルハロゲノシランを接触反応させた後に、更にヘキサメチルジシラザンを接触反応させて改質した疎水性微細シリカ化合物であることが好ましい。このような本発明に用いる疎水性微細シリカ化合物の製造方法としては、例えば、特許２８８６０３７号公報、特許２８８６１０５号公報等に開示されている製造方法が挙げられる。また、本発明に用いる疎水性微細シリカ化合物は市販品としても入手することが可能であり、例えば、微細シリカの表面のＯＨ基にヘキサメチルジシラザンを接触反応させて改質したレオロシールＨＭ−２０Ｌ、ＨＭ−３０Ｓ（（株）トクヤマ製）や、微細シリカの表面のＯＨ基にアルキルハロゲノシランを接触反応させた後に、更にヘキサメチルジシラザンを接触反応させて改質したレオロシールＺＤ−３０ＳＴ（（株）トクヤマ製）等が挙げられる。 Furthermore, as the hydrophobic fine silica compound of the component (A) used in the present invention, when the hexamethyldisilazane is modified by contact reaction, first, methyltrichlorosilane, dimethyldichlorochloride is added to the OH group on the surface of the fine silica. It is preferably a hydrophobic fine silica compound modified by contact reaction of alkylhalogenosilane such as silane and further contact reaction of hexamethyldisilazane. Examples of the method for producing the hydrophobic fine silica compound used in the present invention include the methods disclosed in Japanese Patent No. 2886037 and Japanese Patent No. 2886105. The hydrophobic fine silica compound used in the present invention can also be obtained as a commercial product. For example, Leoroseal HM-20L modified by contact reaction of hexamethyldisilazane with OH groups on the surface of fine silica. HM-30S (manufactured by Tokuyama Co., Ltd.) or Rheolocyl ZD-30ST modified by contact reaction of hexamethyldisilazane with alkylhalogenosilane after contact reaction with OH groups on the surface of fine silica (( Etc.) manufactured by Tokuyama Corporation.
本発明に用いる（Ｂ）成分としての樹脂化合物は、被処理材の表面に対して（Ａ）成分の疎水性微細シリカ化合物を担持するためのバインダーとして機能するものである。このような樹脂化合物は特に限定されないが、例えば、アクリル樹脂、酢酸ビニル樹脂、ポリウレタン樹脂、エポキシ樹脂、脂環式飽和炭化水素樹脂、ロジンエステル系樹脂、アルキルフェノール樹脂（ノボラック型）、アルキルフェノール樹脂（レゾール型）、テルペンフェノール樹脂等を用いることができ、これらの中でも、アクリル樹脂、ポリウレタン樹脂、脂環式飽和炭化水素樹脂、ロジンエステル系樹脂が好ましく用いられる。このようなアクリル樹脂としては、固形分３０質量％での粘度が１００ｍＰａ・ｓ以下（Ｂ型粘度計にて測定）である、酸性アクリル共重合体を有するアクリル共重合体エマルジョンが特に好ましく用いられる。また、ポリウレタン樹脂としては、エステル系ポリウレタン樹脂エマルジョンが特に好ましく用いられる。さらに、脂環式飽和炭化水素樹脂としては軟化点が８０℃以上のものが特に好ましく、ロジンエステル系樹脂としては軟化点が９０℃以上のものが特に好ましく用いられる。このようにアクリル樹脂を用いることにより、得られるコーティング膜における疎水性を保持する耐久性や基材への密着性がより向上する傾向にある。また、ポリウレタン樹脂、脂環式飽和炭化水素樹脂又はロジンエステル系樹脂を用いることにより、疎水性微細シリカ化合物の担持力がより向上する傾向にある。さらに、脂環式飽和炭化水素樹脂やロジンエステル系樹脂を用いた場合には、疎水性（撥水性）が特に向上する傾向にある。このようなアクリル樹脂、ポリウレタン樹脂、脂環式飽和炭化水素樹脂及びロジンエステル系樹脂は市販品として入手することが可能であり、例えば、アクリル共重合体エマルジョンのリカボンドＦＫ−６１０（中央理化工業（株）製）、エステル系ポリウレタン樹脂エマルジョンのネオステッカー１２００（日華化学（株）製）、脂環式飽和炭化水素樹脂のアルコンＰ−９０（荒川化学工業（株）製）、ロジンエステル系樹脂のスーパーエステルＡ−１００（荒川化学工業（株）製）等を挙げることができる。 The resin compound as the component (B) used in the present invention functions as a binder for supporting the hydrophobic fine silica compound as the component (A) on the surface of the material to be treated. Such a resin compound is not particularly limited. For example, acrylic resin, vinyl acetate resin, polyurethane resin, epoxy resin, alicyclic saturated hydrocarbon resin, rosin ester resin, alkylphenol resin (novolak type), alkylphenol resin (resole) Type), terpene phenol resin, and the like, among which acrylic resin, polyurethane resin, alicyclic saturated hydrocarbon resin, and rosin ester resin are preferably used. As such an acrylic resin, an acrylic copolymer emulsion having an acidic acrylic copolymer having a viscosity at a solid content of 30% by mass of 100 mPa · s or less (measured with a B-type viscometer) is particularly preferably used. . As the polyurethane resin, an ester polyurethane resin emulsion is particularly preferably used. Further, as the alicyclic saturated hydrocarbon resin, those having a softening point of 80 ° C. or more are particularly preferable, and as the rosin ester-based resin, those having a softening point of 90 ° C. or more are particularly preferably used. Thus, by using an acrylic resin, it exists in the tendency which the durability which maintains the hydrophobicity in the coating film obtained, and the adhesiveness to a base material improve more. Further, the use of a polyurethane resin, an alicyclic saturated hydrocarbon resin, or a rosin ester resin tends to further improve the supporting ability of the hydrophobic fine silica compound. Furthermore, when an alicyclic saturated hydrocarbon resin or a rosin ester resin is used, the hydrophobicity (water repellency) tends to be particularly improved. Such acrylic resins, polyurethane resins, alicyclic saturated hydrocarbon resins, and rosin ester resins can be obtained as commercial products. For example, an acrylic copolymer emulsion Rikabond FK-610 (Chuo Rika Kogyo ( Co., Ltd.), Neo-sticker 1200 of ester polyurethane resin emulsion (manufactured by Nikka Chemical Co., Ltd.), Alcon P-90 of alicyclic saturated hydrocarbon resin (manufactured by Arakawa Chemical Industries, Ltd.), rosin ester resin Superester A-100 (manufactured by Arakawa Chemical Industries, Ltd.) and the like.
本発明に用いる（Ｃ）成分としての揮発性溶媒は、（Ａ）成分及び（Ｂ）成分を分散させるための分散媒として機能するものである。このような揮発性溶媒は特に限定されず、単一の有機溶剤であってもよいし、２種以上の有機溶剤の混合物であってもよく、またこれらの有機溶剤には水が含まれていてもよい。 The volatile solvent as the component (C) used in the present invention functions as a dispersion medium for dispersing the component (A) and the component (B). Such a volatile solvent is not particularly limited, and may be a single organic solvent or a mixture of two or more organic solvents, and these organic solvents contain water. May be.
本発明で（Ｃ）成分の揮発性溶媒として用いる有機溶剤としては、実質的に不活性なものが好ましく、好適な有機溶剤としては、例えば、メタノール、エタノール、イソプロピルアルコール、イソブチルアルコール等の炭素数１〜４の脂肪族アルコール；アセトン、エチルメチルケトン等のケトン類；酢酸エチル等のエステル類；ジエチルエーテル、ジイソプロピルエーテル、メチルｔ−ブチルエーテル等のエーテル類；脂肪族系炭化水素；脂環式系炭化水素；芳香族系炭化水素等を挙げることができる。 In the present invention, the organic solvent used as the volatile solvent of the component (C) is preferably substantially inactive, and examples of suitable organic solvents include carbon numbers such as methanol, ethanol, isopropyl alcohol, and isobutyl alcohol. 1 to 4 aliphatic alcohols; ketones such as acetone and ethyl methyl ketone; esters such as ethyl acetate; ethers such as diethyl ether, diisopropyl ether and methyl t-butyl ether; aliphatic hydrocarbons; Hydrocarbons; aromatic hydrocarbons and the like.
本発明の疎水性コーティング膜形成組成物は、前記（Ａ）成分、前記（Ｂ）成分及び前記（Ｃ）成分を含有するものであり、それらの均一分散物として含有していることが好ましい。 The hydrophobic coating film-forming composition of the present invention contains the component (A), the component (B) and the component (C), and preferably contains them as a uniform dispersion.
本発明の疎水性コーティング膜形成組成物においては、疎水性をより向上させる観点からは（Ａ）成分を増量し、耐久性（密着性）をより向上させる観点からは（Ｂ）成分を増量させることが好ましい傾向にあり、両者を両立させることによってより良好な疎水性と耐久性を備えたコーティング膜が得られる傾向にある。そしてそれら成分の相対的な量としては、（Ａ）：（Ｂ）の配合比率（質量基準）が５０：５０〜９９：１の範囲となるように配合することが好ましく、特に（Ｂ）成分としてアクリル樹脂やポリウレタン樹脂を用いる場合は（Ａ）：（Ｂ）の配合比率（質量基準）が８０：２０〜９９：１の範囲となるように配合することがより好ましく、また、（Ｂ）成分として脂環式飽和炭化水素樹脂やロジンエステル系樹脂を用いる場合は（Ａ）：（Ｂ）の配合比率（質量基準）が５０：５０〜９５：５の範囲となるように配合することがより好ましい。このような配合比率にすることによって、より良好な疎水性と耐久性（密着性）が達成される傾向にある。（Ａ）：（Ｂ）の配合比率（質量基準）が５０：５０未満、すなわち、（Ｂ）成分が５０質量％を超えた比率で配合すると疎水性が低下する傾向にあり、他方、（Ａ）：（Ｂ）の配合比率（質量基準）が９９：１を超えて、すなわち、（Ａ）成分を９９質量％を超えた比率で配合すると（Ａ）成分の疎水性微細シリカ化合物が疎水性コーティング膜から脱落しやすくなる傾向にある。 In the composition for forming a hydrophobic coating film of the present invention, the component (A) is increased from the viewpoint of further improving hydrophobicity, and the component (B) is increased from the viewpoint of further improving durability (adhesion). The coating film having better hydrophobicity and durability tends to be obtained by making both compatible. And as a relative quantity of these components, it is preferable to mix | blend so that the mixture ratio (mass basis) of (A) :( B) may be in the range of 50: 50-99: 1, (B) component especially When an acrylic resin or a polyurethane resin is used, it is more preferable that the blending ratio (mass basis) of (A) :( B) is in the range of 80:20 to 99: 1, and (B) When an alicyclic saturated hydrocarbon resin or rosin ester resin is used as a component, it may be blended so that the blending ratio (mass basis) of (A) :( B) is in the range of 50:50 to 95: 5. More preferred. By using such a blending ratio, better hydrophobicity and durability (adhesion) tend to be achieved. When the blending ratio (mass basis) of (A) :( B) is less than 50:50, that is, when the blending ratio of the component (B) exceeds 50% by mass, the hydrophobicity tends to decrease. ): The blending ratio (mass basis) of (B) exceeds 99: 1, that is, when the component (A) is blended in a ratio exceeding 99% by mass, the hydrophobic fine silica compound of the component (A) is hydrophobic. It tends to fall off the coating film.
また、本発明の疎水性コーティング膜形成組成物における（Ｃ）揮発性溶媒の配合量は特に制限されず、採用する塗布方法等に応じて適宜選択されるが、得られる疎水性コーティング膜形成組成物における不揮発分（固形分）の含有量が０．１〜６質量％程度となる量の（Ｃ）揮発性溶媒を配合することが一般的に好ましい。 Further, the blending amount of the volatile solvent (C) in the hydrophobic coating film forming composition of the present invention is not particularly limited and is appropriately selected depending on the coating method to be employed, but the obtained hydrophobic coating film forming composition It is generally preferable to add (C) a volatile solvent in such an amount that the content of the non-volatile content (solid content) in the product is about 0.1 to 6% by mass.
本発明においては、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分を使用時に混合して疎水性コーティング膜形成組成物として用いることもできるが、（Ａ）成分及び（Ｂ）成分の分散性が弱すぎる場合には、疎水性コーティング膜形成組成物の経時での分散安定性が悪くなることにより、疎水性コーティング膜中に分散不良による凝集粒子が混在するようになり、疎水性、耐久性（密着性）が低下する傾向にある。従って、本発明の疎水性コーティング膜形成組成物を調製する際には係る分散性について十分注意すべきであり、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の混合物を高速分散装置を用いて分散させることが好ましい。本発明において使用する（Ａ）成分の疎水性微細シリカ化合物は超微粒子であるので、良好な分散性を得るためには、ホモジナイザー、コロイドミル、ボールミル、ビーズミル、サンドミル、三本ロールミル、ニーダー及びエクストルーダー、超音波分散或いは高圧ジェットミル分散装置等の高速分散装置を用いて、安定性及び均一性に優れた疎水性コーティング膜形成組成物とすることが好ましい。 In the present invention, the component (A), the component (B) and the component (C) can be mixed at the time of use and used as a composition for forming a hydrophobic coating film, but the dispersion of the component (A) and the component (B) When the property is too weak, the dispersion stability of the hydrophobic coating film-forming composition deteriorates over time, and aggregated particles due to poor dispersion are mixed in the hydrophobic coating film, making it hydrophobic and durable. Tend to decrease the property (adhesiveness). Therefore, when preparing the hydrophobic coating film forming composition of the present invention, sufficient attention should be paid to the dispersibility, and the mixture of the component (A), the component (B) and the component (C) should be replaced with a high-speed dispersion device. It is preferable to use and disperse. Since the hydrophobic fine silica compound (A) used in the present invention is an ultrafine particle, in order to obtain good dispersibility, a homogenizer, a colloid mill, a ball mill, a bead mill, a sand mill, a three-roll mill, a kneader, and an extensible It is preferable to make a hydrophobic coating film forming composition excellent in stability and uniformity by using a high-speed dispersion device such as a ruder, ultrasonic dispersion or high-pressure jet mill dispersion device.
次に、本発明の疎水性コーティング膜の形成方法について説明する。 Next, a method for forming the hydrophobic coating film of the present invention will be described.
本発明の疎水性コーティング膜の形成方法は、前記本発明の疎水性コーティング膜形成組成物を被処理材の表面に塗布した後に乾燥させることを特徴とする方法である。すなわち、本発明においては、前記（Ｃ）成分の揮発性溶媒に前記（Ａ）成分及び前記（Ｂ）成分を分散させた疎水性コーティング膜形成組成物を用いて被処理材の表面にコーティングを行い、溶剤を揮発、乾燥させることによって、疎水性のコーティング膜を形成させることができる。 The method for forming a hydrophobic coating film of the present invention is a method characterized in that the hydrophobic coating film forming composition of the present invention is applied to the surface of a material to be treated and then dried. That is, in the present invention, the surface of the material to be treated is coated with the hydrophobic coating film forming composition in which the component (A) and the component (B) are dispersed in the volatile solvent of the component (C). A hydrophobic coating film can be formed by performing evaporation and volatilization and drying of the solvent.
本発明の疎水性コーティング膜を形成させる方法において、被処理材（基材）の表面上にコーティングする前記組成物の量は、一般にコーティングで均一に塗布ができる量で充分な量であり、極端に薄い（例えば、１〜５０ｎｍ）膜厚でも疎水性の機能を発揮できるが、実際に使用されるコーティングではもっと厚くてもよい。 In the method for forming a hydrophobic coating film of the present invention, the amount of the composition to be coated on the surface of the material to be treated (substrate) is generally a sufficient amount that can be uniformly applied by coating. Even a very thin film thickness (for example, 1 to 50 nm) can exert a hydrophobic function, but a coating actually used may be thicker.
また、本発明の疎水性コーティング膜を形成させる方法においては、そのコーティング方法については特に限定されず、従来のコーティング方法を適用することができる。例えば、刷毛塗り、エアガン若しくはエアレスガン塗装機による直接コーティング；エアゾールスプレー若しくはトリガースプレー形態による直接スプレーコーティング；ローラー式刷毛を用いたコーティング；シート状基体によるコーティング等何れでも良い。 In the method for forming the hydrophobic coating film of the present invention, the coating method is not particularly limited, and a conventional coating method can be applied. For example, brush coating, direct coating using an air gun or an airless gun coating machine; direct spray coating using an aerosol spray or trigger spray; coating using a roller brush; coating using a sheet-like substrate may be used.
また、本発明の疎水性コーティング膜により優れた特性を発揮させるためには、疎水性コーティング膜を形成させる時に、被処理材のコーティング面に対して前処理を施しておくことが好ましい。また、本発明の疎水性コーティング膜により優れた耐久性を与えるためには、被処理材の表面を清浄化してから本発明の疎水性コーティング膜形成組成物をコーティングすることが好ましい。すなわち、コーティングに先立って、被処理材の表面から有機性の汚染物を実質的に除去しておくことが好ましく、そのような清浄化方法は被処理材の材質によっても異なるが、例えば、アセトンやエタノール等の有機溶媒を使用した溶媒による清浄化処理が効果的である。 Moreover, in order to exhibit excellent characteristics with the hydrophobic coating film of the present invention, it is preferable to pre-treat the coating surface of the material to be treated when forming the hydrophobic coating film. In order to give excellent durability to the hydrophobic coating film of the present invention, it is preferable to clean the surface of the material to be treated before coating with the hydrophobic coating film forming composition of the present invention. That is, prior to coating, it is preferable to substantially remove organic contaminants from the surface of the material to be treated. Such a cleaning method varies depending on the material of the material to be treated, for example, acetone. Cleaning with a solvent using an organic solvent such as ethanol is effective.
本発明の疎水性コーティング膜を形成させる方法において、被処理材の表面に塗布された前記疎水性コーティング膜形成組成物を乾燥させる（揮発性溶媒を揮発させる）方法は特に制限されず、本発明においては特に加熱せずに乾燥させることも可能である。すなわち、従来の疎水性コーティング膜を形成させる方法においては一般に加熱が必要であったが、本発明の疎水性コーティング膜形成組成物を用いた場合には、常温での乾燥で同様の機能を発揮させることができる。なお、本発明において加熱乾燥する方法を採用してもよく、その場合は疎水性コーティング膜を形成させる時間をより短縮させることが可能となる傾向にある。 In the method for forming the hydrophobic coating film of the present invention, the method for drying the hydrophobic coating film forming composition applied to the surface of the material to be treated (the volatile solvent is volatilized) is not particularly limited. In particular, it is possible to dry without heating. That is, in the conventional method for forming a hydrophobic coating film, heating was generally required, but when the hydrophobic coating film forming composition of the present invention was used, the same function was exhibited by drying at room temperature. Can be made. In addition, you may employ | adopt the method of heat-drying in this invention, In that case, it exists in the tendency for the time which forms a hydrophobic coating film | membrane to be shortened more.
次に、本発明の疎水性コーティング膜及び本発明の機能性材料について説明する。本発明の疎水性コーティング膜は、（Ａ）ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物、及び（Ｂ）樹脂化合物を含有することを特徴とするものである。また、本発明の機能性材料は、前記本発明の疎水性コーティング膜を備えることを特徴とするものである。 Next, the hydrophobic coating film of the present invention and the functional material of the present invention will be described. The hydrophobic coating film of the present invention comprises (A) a hydrophobic fine silica compound modified with hexamethyldisilazane, and (B) a resin compound. Moreover, the functional material of the present invention is characterized by including the hydrophobic coating film of the present invention.
本発明の疎水性コーティング膜は、前述の（Ａ）ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物及び（Ｂ）樹脂化合物により構成されており、（Ａ）ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物が、バインダーとしての（Ｂ）樹脂化合物中に均一に分散していることが好ましい。かかる疎水性コーティング膜における（Ａ）成分及び（Ｂ）成分の配合比率の好適範囲は前述のとおりである。また、被処理材の表面に担持される（Ａ）成分及び（Ｂ）成分の量は特に限定されないが、（Ａ）成分の担持量が０．１〜１００ｇ／ｍ２程度、（Ｂ）成分の担持量が０．０１〜１０ｇ／ｍ２程度であることが一般的に好ましい。さらに、本発明の疎水性コーティング膜の膜厚も特に限定されないが、１０〜３０ｎｍ程度であることが一般的に好ましい。 The hydrophobic coating film of the present invention is composed of the above-mentioned hydrophobic fine silica compound modified with (A) hexamethyldisilazane and (B) resin compound, and (A) modified with hexamethyldisilazane. It is preferable that the hydrophobic fine silica compound made to disperse | distribute uniformly in the (B) resin compound as a binder. The suitable range of the blending ratio of the component (A) and the component (B) in the hydrophobic coating film is as described above. Further, the amount of the component (A) and the component (B) supported on the surface of the material to be treated is not particularly limited, but the amount of the component (A) supported is about 0.1 to 100 g / m 2 , the component (B) It is generally preferred that the loading amount of is about 0.01 to 10 g / m 2 . Furthermore, the thickness of the hydrophobic coating film of the present invention is not particularly limited, but is generally preferably about 10 to 30 nm.
また、本発明を適用できる被処理材（基材）は特に制限されず、例えば、ガラス、金属、紙類、セラミックス、セメント材、合成樹脂、繊維、塗装面等の様々な材料からなる基材に対して本発明の疎水性コーティング膜を形成することができる。 In addition, the material to be treated (substrate) to which the present invention can be applied is not particularly limited, and for example, a substrate made of various materials such as glass, metal, paper, ceramics, cement material, synthetic resin, fiber, and painted surface. In contrast, the hydrophobic coating film of the present invention can be formed.
したがって、本発明によれば、上記のような様々な基材に対して、水分を寄せ付けない疎水性で微細な凹凸であるいわゆる「フルクタル構造」を有する疎水性コーティング膜を容易に形成させることができ、それによって特異的に防汚、超撥水、防水、防雪、防氷、防錆、防藻、防菌、防カビ等の機能を奏する各種の本発明の機能性材料を得ることができる。 Therefore, according to the present invention, it is possible to easily form a hydrophobic coating film having a so-called “fractal structure” that is a hydrophobic and fine unevenness that does not attract moisture on various substrates as described above. It is possible to obtain various functional materials of the present invention that have specific functions such as antifouling, super water repellency, waterproofing, snowproofing, iceproofing, rusting, algae, antibacterial, and antifungal. .
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例に用いた疎水性微細シリカ化合物、樹脂化合物、有機溶剤は以下の通りである。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the hydrophobic fine silica compound, the resin compound, and the organic solvent which were used for the Example are as follows.
＜ヘキサメチルジシラザンで改質させた疎水性微細シリカ化合物＞
レオロシールＨＭ−３０Ｓ（（株）トクヤマ製）
一次粒子の平均粒子径：７ｎｍ
炭素含有量：３．５質量％
レオロシールＺＤ−３０ＳＴ（（株）トクヤマ製）
一次粒子の平均粒子径：７ｎｍ
炭素含有量：２．８質量％。
<Hydromethyldisilazane modified hydrophobic fine silica compound>
Leolo Seal HM-30S (manufactured by Tokuyama Corporation)
Average particle diameter of primary particles: 7 nm
Carbon content: 3.5% by mass
Leoroseal ZD-30ST (manufactured by Tokuyama Corporation)
Average particle diameter of primary particles: 7 nm
Carbon content: 2.8% by mass.
＜樹脂化合物＞
ネオステッカー１２００（日華化学（株）製）
エステル系ポリウレタン樹脂エマルジョン
不揮発分：３７質量％
リカボンドＦＫ−６１０（中央理化工業（株）製）
アクリル共重合体エマルジョン
不揮発分：２８質量％
粘度：１８ｍＰａ・ｓ（Ｂ型、１号ロータ、６０ｒｐｍ、２５℃）
スーパーエステルＡ−１００（荒川化学工業（株）製）
ロジンエステル系樹脂
不揮発分：１００質量％
軟化点：約１００℃
アルコンＰ−９０（荒川化学工業（株）製）
脂環式飽和炭化水素樹脂
不揮発分：１００質量％
軟化点：約９０℃
＜有機溶剤＞
エクソールＤ−４０（エクソンモービル（有）製）
脂肪族炭化水素／脂環式炭化水素＝５０％／５０％。
<Resin compound>
Neo Sticker 1200 (manufactured by Nikka Chemical Co., Ltd.)
Ester polyurethane resin emulsion
Nonvolatile content: 37% by mass
Rikabond FK-610 (manufactured by Chuo Rika Kogyo Co., Ltd.)
Acrylic copolymer emulsion
Nonvolatile content: 28% by mass
Viscosity: 18 mPa · s (Type B, No. 1 rotor, 60 rpm, 25 ° C.)
Superester A-100 (Arakawa Chemical Industries, Ltd.)
Rosin ester resin
Nonvolatile content: 100% by mass
Softening point: about 100 ° C
Alcon P-90 (Arakawa Chemical Industries, Ltd.)
Alicyclic saturated hydrocarbon resin
Nonvolatile content: 100% by mass
Softening point: about 90 ° C
<Organic solvent>
Exor D-40 (manufactured by ExxonMobil Corporation)
Aliphatic hydrocarbon / alicyclic hydrocarbon = 50% / 50%.
（実施例１）
以下の諸成分：
レオロシールＨＭ−３０Ｓ（（株）トクヤマ製） ４．０質量％
ネオステッカー１２００（日華化学（株）製） １．０質量％
エチルアルコール ９５．０質量％
を予備混合した後、ホモジナイザー装置（ゴーリーン社製、商品名：ホモジナイザー、３０ＭＰａ）を用いて分散処理（５分間）を施し、安定な乳白色をした疎水性コーティング膜形成組成物を得た。
Example 1
The following ingredients:
Leolosil HM-30S (manufactured by Tokuyama Corporation) 4.0% by mass
Neo Sticker 1200 (Nikka Chemical Co., Ltd.) 1.0% by mass
Ethyl alcohol 95.0% by mass
Were pre-mixed and then subjected to dispersion treatment (5 minutes) using a homogenizer (trade name: Homogenizer, 30 MPa, manufactured by Gorin Co., Ltd.) to obtain a hydrophobic milky coating film-forming composition having a stable milky white color.
（実施例２）
以下の諸成分：
レオロシールＺＤ−３０ＳＴ（（株）トクヤマ製） ２．０質量％
リカボンドＦＫ−６１０（中央理化工業（株）製） ０．５質量％
イソプロピルアルコール ９７．５質量％
を予備混合した後、高圧ジェットミル分散装置（（株）スギノマシン製、商品名：アルチマイザー、１００Ｐａ）を用いて分散処理（５分間）を施し、安定な乳白色をした疎水性コーティング膜形成組成物を得た。
(Example 2)
The following ingredients:
Leolo Seal ZD-30ST (manufactured by Tokuyama Corporation) 2.0% by mass
Rikabond FK-610 (Chuo Rika Kogyo Co., Ltd.) 0.5% by mass
Isopropyl alcohol 97.5% by mass
Is pre-mixed and then subjected to dispersion treatment (5 minutes) using a high-pressure jet mill dispersion device (manufactured by Sugino Machine Co., Ltd., trade name: Ultimizer, 100 Pa) to form a hydrophobic milky coating film composition having a stable milky white color. I got a thing.
（実施例３）
以下の諸成分：
レオロシールＺＤ−３０ＳＴ（（株）トクヤマ製） １．０質量％
スーパーエステルＡ−１００（荒川化学工業（株）製） ０．５質量％
エクソールＤ−４０（エクソンモービル（有）製） ９８．５質量％
を予備混合した後、ホモジナイザー装置（ゴーリーン社製、商品名：ホモジナイザー、３０ＭＰａ）を用いて分散処理（５分間）を施し、安定な乳白色をした疎水性コーティング膜形成組成物を得た。
(Example 3)
The following ingredients:
Leolo Seal ZD-30ST (manufactured by Tokuyama Corporation) 1.0% by mass
Super Ester A-100 (Arakawa Chemical Industries, Ltd.) 0.5% by mass
Exol D-40 (manufactured by ExxonMobil) 98.5% by mass
Were pre-mixed and then subjected to dispersion treatment (5 minutes) using a homogenizer (trade name: Homogenizer, 30 MPa, manufactured by Gorin Co., Ltd.) to obtain a hydrophobic milky coating film-forming composition having a stable milky white color.
（実施例４）
以下の諸成分：
レオロシールＺＤ−３０ＳＴ（（株）トクヤマ製） １．０質量％
アルコンＰ−９０（荒川化学工業（株）製） ０．５質量％
エクソールＤ−４０（エクソンモービル（有）製） ９８．５質量％
を予備混合した後、ホモジナイザー装置（ゴーリーン社製、商品名：ホモジナイザー、３０ＭＰａ）を用いて分散処理（５分間）を施し、安定な乳白色をした疎水性コーティング膜形成組成物を得た。
Example 4
The following ingredients:
Leolo Seal ZD-30ST (manufactured by Tokuyama Corporation) 1.0% by mass
Alcon P-90 (Arakawa Chemical Industries, Ltd.) 0.5% by mass
Exol D-40 (manufactured by ExxonMobil) 98.5% by mass
Were pre-mixed and then subjected to dispersion treatment (5 minutes) using a homogenizer (trade name: Homogenizer, 30 MPa, manufactured by Gorin Co., Ltd.) to obtain a hydrophobic milky coating film-forming composition having a stable milky white color.
（比較例１）
市販されているフッ素系撥水剤であるＮＫガードＮＤＮ−７ＥＧ（日華化学（株）社製）を疎水性コーティング膜形成組成物としてそのまま用いた。
(Comparative Example 1)
NK guard NDN-7EG (manufactured by Nikka Chemical Co., Ltd.), which is a commercially available fluorine-based water repellent, was used as it was as a hydrophobic coating film forming composition.
（比較例２）
市販されているシリコーン系撥水剤であるドライポン３００（日華化学（株）社製）を疎水性コーティング膜形成組成物としてそのまま用いた。
(Comparative Example 2)
Drypon 300 (manufactured by Nikka Chemical Co., Ltd.), which is a commercially available silicone water repellent, was used as it was as a hydrophobic coating film forming composition.
［評価用試料の作製］
コーティング基材（被処理材）として市販のガラス板（１２ｃｍ×１２ｃｍ）を用い、先ず、表面の残留物を除去するためにアセトンを用いて前処理清浄を施した。次に、実施例及び比較例で得られた疎水性コーティング膜形成組成物を基材の表面にコーティング（塗布量：５ｍｌ）した後に室温で乾燥し、疎水性コーティング膜を有する評価用の試料を得た。
[Preparation of sample for evaluation]
A commercially available glass plate (12 cm × 12 cm) was used as a coating substrate (material to be treated), and first, pretreatment was performed using acetone in order to remove surface residues. Next, the hydrophobic coating film forming compositions obtained in the examples and comparative examples were coated on the surface of the substrate (coating amount: 5 ml) and then dried at room temperature to prepare a sample for evaluation having a hydrophobic coating film. Obtained.
[接触角の測定試験]
協和界面科学（株）製のＤＣＡ−ＷＺ型接触角計測器を用いて、動的接触性測定システムにより試料表面の接触角を計測した。なお、蒸留水滴下量を１３．６μＬとして計測を行った。
[Contact angle measurement test]
Using a DCA-WZ type contact angle measuring instrument manufactured by Kyowa Interface Science Co., Ltd., the contact angle of the sample surface was measured by a dynamic contact measuring system. In addition, it measured by making distilled water dripping amount 13.6 microliters.
[疎水性の評価試験]
以下の水滴試験、水滴易動度試験、及びスプレー試験を実施し、試料表面の疎水性を評価した。
[Hydrophobic evaluation test]
The following water drop test, water drop mobility test, and spray test were performed to evaluate the hydrophobicity of the sample surface.
ａ．水滴試験：
水平に置いた評価用試料の疎水性コーティング膜の表面を横切る線上に数滴の水を落とし、これらの水滴の接触角を観察して、疎水性を下記の基準に基づいて評価した。
優：まとまった、真円に近い、きらきら輝きのある水滴が主として存在し、９５度以上の優れた接触角を有する。
良：僅かに広がった、真円から少しくずれた、輝きのある水滴が主として存在し、８５〜９５度の良好な接触角を有する。
可：少し広がった、僅かに平らになった水滴が主として存在し、７０〜８５度の普通の接触角を有する。
劣る：広がっていて、平らな小さい水滴が主として存在し、７０度以下の接触角を有する。
a. Water drop test:
A few drops of water were dropped on a line across the surface of the hydrophobic coating film of the evaluation sample placed horizontally, and the contact angle of these water drops was observed, and the hydrophobicity was evaluated based on the following criteria.
Excellent: There are mainly water droplets that are gathered, close to a perfect circle, and brilliantly shining, and have an excellent contact angle of 95 degrees or more.
Good: There are mainly brilliant water droplets that are slightly spread, slightly deviated from the perfect circle, and have a good contact angle of 85 to 95 degrees.
Acceptable: There are mainly slightly flattened, slightly flattened water droplets with a normal contact angle of 70-85 degrees.
Inferior: Wide, flat, small water droplets are mainly present and have a contact angle of 70 degrees or less.
ｂ．水滴易動度試験：
次に、疎水性コーティング膜の表面に置かれた複数の水滴の線と平行な位置にある評価用試料のへり部をゆっくりと持ち上げた。水滴が傾いた表面を流れ始める時の角度、又は持ち上げられたへりの水平な支持面からの高さを観察した。角度又はへりの高さが小さいほど疎水性と接触角が良好であり、下記の基準に基づいて評価した。
優：０〜１０度の傾き（０〜２ｃｍのへり部高さ）。
良：１０〜２０度の傾き（２〜３．５ｃｍのへり部高さ）。
可：２０〜３０度の傾き（３．５〜５ｃｍのへり部高さ）。
劣る：３０度より大きい傾き（５ｃｍより高いへり部高さ）。
b. Water drop mobility test:
Next, the edge portion of the sample for evaluation at a position parallel to the plurality of water droplet lines placed on the surface of the hydrophobic coating film was slowly lifted. The angle at which the water drop began to flow on the tilted surface, or the height of the lifted edge from the horizontal support surface was observed. The smaller the angle or the edge height, the better the hydrophobicity and the contact angle, and the evaluation was made based on the following criteria.
Excellent: Inclination of 0 to 10 degrees (edge height of 0 to 2 cm).
Good: Inclination of 10 to 20 degrees (edge height of 2 to 3.5 cm).
Good: 20-30 degree inclination (3.5-5 cm edge height).
Inferior: slope greater than 30 degrees (edge height higher than 5 cm).
ｃ．スプレー試験：
水を霧状か細い流れ状で吹付けられるように調節することができる吹付け部を備えた霧吹きびんを使用した。そして、再び水平に置いた評価用試料の疎水性コーティング膜の表面に、４〜５回霧吹きびんのポンプを押して霧状／流れ状の水を水平位置から少し上がった位置の水流で吹付けた。霧吹きの小滴は吹付けた領域全体について観察された。これらの小滴は大きさが異なっており、上述の水落下試験と同様に順位付けされるが、より小さい水滴の多さについての観察を加えた。このような試験を５回繰り返して同様の観察を行い、下記の基準に基づいて評価した。
優：水滴は、まとまった、真円に近い、きらきら輝きのある水滴であり、優れた接触角を示し、多数の微細な水滴が吹付けパターン中に存在する。
良：水滴は、僅かに広がった、真円から少しくずれた、輝きのある水滴であり、良好な接触角を示し、かなりの数の微細な水滴が吹付けパターン中に存在する。
可：水滴は、少し広がった、僅かに平らになった水滴であり、普通の接触角を示し、少数の微細な水滴が吹付けパターン中に存在する。
劣る：水滴は、広がっていて平らな水滴であり、小さい接触角を示す。
c. Spray test:
A mist bottle with a spraying part that can be adjusted to spray water in a mist or thin stream was used. Then, the spray bottle was pressed 4-5 times on the surface of the hydrophobic coating film of the evaluation sample placed again horizontally to spray the water in a mist / flow state with a water flow slightly raised from the horizontal position. . Spray droplets were observed throughout the sprayed area. These droplets differed in size and were ranked in the same manner as the water drop test described above, but with the observation of a smaller number of water droplets. Such a test was repeated 5 times, the same observation was performed, and evaluation was performed based on the following criteria.
Excellent: Water droplets are collected, close to a perfect circle, sparkling water droplets, exhibit an excellent contact angle, and many fine water droplets are present in the spray pattern.
Good: Water droplets are slick water droplets that are slightly spread, slightly out of perfect circle, exhibit a good contact angle, and there are quite a few fine water droplets present in the spray pattern.
Good: Water droplets are slightly flattened, slightly flattened water droplets, exhibiting a normal contact angle, and a few fine water droplets are present in the spray pattern.
Inferior: Water droplets are spread and flat water droplets and exhibit a small contact angle.
実施例及び比較例の疎水性コーティング膜形成組成物を用いて得られた疎水性コーティング膜について実施したそれぞれの評価試験の結果をまとめて表１に示す。また、比較のため、未処理の基材について同様に評価した結果も併せて表１に示す。 Table 1 summarizes the results of the respective evaluation tests performed on the hydrophobic coating films obtained using the hydrophobic coating film-forming compositions of Examples and Comparative Examples. For comparison, Table 1 also shows the results of a similar evaluation for an untreated substrate.
表１に示した結果から明らかなように、実施例１〜４で得た本発明の疎水性コーティング膜形成組成物を用いて得られた疎水性コーティング膜については、水滴滴下試験における接触角が良好な結果を示していることが確認された。また、疎水性の評価試験の結果では、実施例１〜４で得た本発明の疎水性コーティング膜形成組成物を用いて得られた疎水性コーティング膜においては全ての試験項目について「優」の結果が得られたが、比較例１〜２の疎水性コーティング膜形成組成物を用いて得られた疎水性コーティング膜においては実施例で得られたものに比べてかなり劣ることが確認された。 As is clear from the results shown in Table 1, the hydrophobic coating film obtained using the hydrophobic coating film-forming composition of the present invention obtained in Examples 1 to 4 has a contact angle in a water drop test. It was confirmed that good results were shown. In addition, as a result of the hydrophobicity evaluation test, in the hydrophobic coating film obtained using the hydrophobic coating film forming composition of the present invention obtained in Examples 1 to 4, “excellent” was obtained for all the test items. Although the result was obtained, it was confirmed that the hydrophobic coating films obtained by using the hydrophobic coating film forming compositions of Comparative Examples 1 and 2 were considerably inferior to those obtained in the examples.
次に、実施例及び比較例の疎水性コーティング膜形成組成物を用いて得られた疎水性コーティング膜について、以下の試験方法で防汚性、疎水性の持続性、及び膜密着性について評価した。 Next, for the hydrophobic coating films obtained using the hydrophobic coating film forming compositions of Examples and Comparative Examples, antifouling property, hydrophobic durability, and film adhesion were evaluated by the following test methods. .
[防汚性の試験]
前記の評価用試料を、４５°の角度を有する屋外暴露試験台に装着して２週間（雨天日３日）の暴露の後、下記の基準に基づいて３人のパネラーにより判定した。判定結果を平均し、平均点が１以上１．５未満の場合を◎、１．５以上２未満の場合を○、２以上３未満の場合を△、３以上の場合を×とした。
１：汚れの付着が見られない
２：やや汚れの付着が見られるが満足できるレベルである
３：汚れの付着が見られる
４：かなり汚れの付着が見られる。
[Anti-fouling test]
The sample for evaluation was mounted on an outdoor exposure test stand having an angle of 45 ° and exposed for 2 weeks (3 days on a rainy day), and then judged by three panelists based on the following criteria. Judgment results were averaged, and the case where the average score was 1 or more and less than 1.5 was evaluated as “◎”, the case where it was 1.5 or more and less than 2, “◯”, the case where it was 2 or more and less than 3, and the case where it was 3 or more.
1: No adhesion of dirt is observed 2: Slight adhesion of dirt is seen but at a satisfactory level 3: Adherence of dirt is seen 4: Adhesion of dirt is seen considerably.
[疎水性の持続性の試験]
前記の評価用試料を６ヶ月放置し、６ヶ月経過後に表面に散水して下記の基準に基づいて疎水性を目視にて判定し、疎水性の持続性を評価した。
◎：試料の全面で水滴が真球状になり転がり落ちる
○：水滴が真球状になり転がり落ちるが、試料の一部に水滴が付着して塗面に残る
△：水滴が付着したまま塗面に残る
×：濡れて水が浸透する。
[Hydrophobic durability test]
The sample for evaluation was allowed to stand for 6 months. After 6 months, water was sprayed on the surface, and the hydrophobicity was visually determined based on the following criteria to evaluate the persistence of hydrophobicity.
◎: Water droplets become spherical and roll over the entire surface of the sample ○: Water droplets become spherical and roll down, but water droplets adhere to part of the sample and remain on the coating surface △: Water droplets remain on the coating surface Remaining x: Wet and water penetrates.
[膜密着性の試験]
前記の評価用試料に形成させた疎水性コーティング膜の表面状態を目視で評価し、下記の基準に基づいて判定した。
○：異常なし
△：部分的に斑、剥がれがある。
[Film adhesion test]
The surface state of the hydrophobic coating film formed on the evaluation sample was visually evaluated and judged based on the following criteria.
○: No abnormality Δ: Partial spots and peeling
実施例及び比較例の疎水性コーティング膜形成組成物を用いて得られた疎水性コーティング膜について実施したそれぞれの評価試験の結果をまとめて表２に示す。また、比較のため、未処理の基材について同様に防汚性を評価した結果も併せて表２に示す。 Table 2 summarizes the results of the evaluation tests performed on the hydrophobic coating films obtained using the hydrophobic coating film-forming compositions of Examples and Comparative Examples. For comparison, Table 2 also shows the results of evaluation of antifouling properties for untreated substrates.
表２に示した結果から明らかなように、実施例１〜４、特に実施例３及び実施例４で得た本発明の疎水性コーティング膜形成組成物を用いて得られた疎水性コーティング膜については、防汚性、疎水性の持続性、膜密着性の全ての評価において良好な結果が得られたが、比較例１〜２の疎水性コーティング膜形成組成物を用いて得られた疎水性コーティング膜においては実施例で得られたものに比べてかなり劣ることが確認された。 As is clear from the results shown in Table 2, the hydrophobic coating film obtained using the hydrophobic coating film forming composition of the present invention obtained in Examples 1 to 4, especially Example 3 and Example 4. Obtained favorable results in all evaluations of antifouling property, hydrophobic durability, and film adhesion, but the hydrophobicity obtained using the hydrophobic coating film forming compositions of Comparative Examples 1 and 2 It was confirmed that the coating film was considerably inferior to that obtained in the example.
以上説明したように、本発明によれば、疎水性が要求される様々な材質及び表面構造を有する被処理材に対して、疎水性、防汚性及びそれらの耐久性に優れた均一な疎水性コーティング膜をより簡単に且つ効率良く形成することを可能とする疎水性コーティング膜形成組成物及びその形成方法、並びにそれによって得られた疎水性コーティング膜及び機能性材料を提供することが可能となる。 As described above, according to the present invention, a uniform hydrophobicity excellent in hydrophobicity, antifouling property and durability of materials to be processed having various materials and surface structures that require hydrophobicity. It is possible to provide a hydrophobic coating film forming composition and a method for forming the same, and a hydrophobic coating film and a functional material obtained thereby, which can form a functional coating film more easily and efficiently Become.
したがって、本発明は、例えば、防水コンクリート、防水テント、防錆鋼材加工部品、医療施設での抗菌カーテンといった分野で幅広く利用することができる、防汚、超撥水、防水、防雪、防氷、防錆、防藻、防菌、防カビ等の機能を発揮できる機能性材料を提供する技術として有用である。
Therefore, the present invention can be widely used in fields such as waterproof concrete, waterproof tents, rust-proof steel parts, antibacterial curtains in medical facilities, antifouling, super water-repellent, waterproof, snowproof, iceproof, This is useful as a technique for providing a functional material capable of exhibiting functions such as rust prevention, algae prevention, bacteria prevention and mold prevention.
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