JP2009029986A - Coating material and product with high water repellency and high sliding property - Google Patents
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本発明は、コーティング材及び高撥水・高しゅう動性製品に係り、特に、プラスチック、ゴム、金属、セラミックスやこれらの複合材、さらには耐熱性がなく、低強度の有機素材からなる有機基材を高撥水、高しゅう動性とするコーティング材及び高撥水・高しゅう動性製品に関する。 The present invention relates to a coating material and a highly water-repellent / sliding product, and in particular, an organic substrate made of a low-strength organic material having no heat resistance, in particular, plastic, rubber, metal, ceramics, and composite materials thereof. The present invention relates to a coating material that makes a material highly water-repellent and highly slidable, and a highly water-repellent and highly slidable product.
プラスチック、ゴム、金属、セラミックス等に代表される素材でできた建材などの有機基材の表面に、撥水性、耐摩耗性を付与することにより、製品を高耐久性化、長寿命化することができ、それによって、製品を高付加価値化することが可能となる。そのため、従来、さまざまな製品の研究開発が行われているが、基材表面に撥水性、高しゅう動性を共に付与することはなかなか困難であり、実用化されているのは少ないのが実情であった。 Improve product durability and longevity by imparting water repellency and wear resistance to the surface of organic base materials such as building materials made of materials such as plastic, rubber, metal, and ceramics. This makes it possible to increase the value of the product. For this reason, research and development of various products has been conducted in the past, but it is difficult to impart both water repellency and high slidability to the surface of the base material. Met.
その中で撥水性コーティングとしては現在よく用いられているのは、ＰＴＦＥ（Ｐｏｌｙ Ｔｅｔｒａ Ｆｌｕｏｒｏ Ｅｔｈｙｌｅｎｅ）コーティングであるが、焼き付けして製造されるため、例えば、耐熱性のない基材にコーティングすることが難しく、耐摩耗性も必ずしも十分とは言えず実用は限定されたものになっている。 Among them, the PTFE (Poly Tetra Fluoro Ethylene) coating is currently used as a water-repellent coating. However, since it is manufactured by baking, for example, it can be coated on a non-heat-resistant substrate. It is difficult and the wear resistance is not always sufficient, and its practical use is limited.
また、従来、ケイ酸塩やシリカをコーティングする方法が種々報告されており、例えば、亀裂を生じにくい安定塗膜を与える無機コーティング材、耐水性のガラス質コーティング膜の形成法、金属基体をコーティングするための組成物、その他、多数の技術が提案されている。このように、従来ケイ酸塩やシリカを安定性や耐水性コーティング材として使用することは公知技術である（例えば、特許文献１、２参照）。 In addition, various methods for coating silicate and silica have been reported in the past. For example, inorganic coating materials that provide stable coatings that do not easily crack, methods for forming water-resistant glassy coating films, and coating metal substrates A number of other techniques have been proposed. Thus, it is a publicly known technique to use conventional silicates and silica as stability and water-resistant coating materials (see, for example, Patent Documents 1 and 2).
しかしながら、従来、当該技術分野において、ケイ酸塩及びシリカコーティング膜を施して、基材に撥水性、高しゅう動性を共に付与することは実現されていなかった。 However, hitherto, it has not been realized in the technical field to provide both water repellency and high sliding property to a substrate by applying a silicate and silica coating film.
そこで、本発明の目的は、上記課題を解決し、基材に撥水性、耐摩耗性を共に付与することが可能なコーティング材及び高撥水・高しゅう動性製品を提供することにある。 Accordingly, an object of the present invention is to solve the above-mentioned problems and provide a coating material and a highly water-repellent / slidable product that can impart both water repellency and wear resistance to a substrate.
本発明は上記目的を達成するために創案されたものであり、請求項１の発明は、シリカコーティング膜を形成するためのコーティング材において、反応性官能基を有するシルセスキオキサンと改質ふっ素樹脂とからなり、前記シルセスキオキサン１００重量部に対し、前記改質ふっ素樹脂を１０〜１００重量部含有するコーティング材である。 The present invention was devised to achieve the above object, and the invention of claim 1 is directed to a coating material for forming a silica coating film, silsesquioxane having a reactive functional group, and modified fluorine. A coating material comprising 10 to 100 parts by weight of the modified fluororesin with respect to 100 parts by weight of the silsesquioxane.
請求項２の発明は、前記反応性官能基は、ビニル基、メタクリロ基、アクリロ基、エポキシ基のいずれかからなる請求項１に記載のコーティング材である。 The invention according to claim 2 is the coating material according to claim 1, wherein the reactive functional group is any one of a vinyl group, a methacrylo group, an acrylo group, and an epoxy group.
請求項３の発明は、前記改質ふっ素樹脂は、その原料となる原料ふっ素樹脂の融点以上の温度、大気圧下、かつ酸素濃度１．３ｋＰａ以下の条件の下、前記原料ふっ素樹脂に電離性放射線を照射して改質したものである請求項１または２に記載のコーティング材である。 According to a third aspect of the present invention, the modified fluororesin is ionizable to the raw fluororesin under conditions of a temperature equal to or higher than a melting point of the raw fluororesin used as a raw material, an atmospheric pressure, and an oxygen concentration of 1.3 kPa or lower. The coating material according to claim 1 or 2, which has been modified by irradiation with radiation.
請求項４の発明は、前記コーティング材は、さらに、前記シルセスキオキサン１００重量部に対し過酸化物重合開始剤またはカチオン重合開始剤を０．５〜５重量部の範囲内で含有する請求項１〜３いずれかに記載のコーティング材である。 In the invention of claim 4, the coating material further contains a peroxide polymerization initiator or a cationic polymerization initiator in a range of 0.5 to 5 parts by weight with respect to 100 parts by weight of the silsesquioxane. The coating material according to any one of Items 1 to 3.
請求項５の発明は、前記コーティング材は、さらに、前記シルセスキオキサン１００重量部に対しラジカル重合開始剤を０．５〜５重量部の範囲内で含有する請求項１〜３いずれかに記載のコーティング材である。 According to a fifth aspect of the present invention, the coating material further comprises a radical polymerization initiator in the range of 0.5 to 5 parts by weight with respect to 100 parts by weight of the silsesquioxane. It is a coating material of description.
請求項６の発明は、プラスチック、ゴム、金属、セラミックス等に代表される素材からなる基材に、請求項１〜５いずれかに記載のコーティング材を塗布し、これを硬化させて前記基材にシリカコーティング膜を形成した高撥水・高しゅう動性製品である。 The invention of claim 6 applies the coating material according to any one of claims 1 to 5 to a base material made of a material typified by plastic, rubber, metal, ceramics, etc., and cures it to form the base material. It is a highly water-repellent and highly slidable product with a silica coating film formed on it.
本発明によれば、基材の表面に高撥水・高しゅう動性に優れたシリカコーティング膜を形成できるコーティング材及び高撥水・高しゅう動性製品を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the coating material which can form the silica coating film | membrane excellent in high water repellency and high sliding property on the surface of a base material, and high water repellency and high sliding property product can be provided.
以下、本発明の好適な実施形態を説明する。 Hereinafter, preferred embodiments of the present invention will be described.
本発明者らは、上記従来技術に鑑みて、上記従来技術の諸問題を抜本的に解決すると共に、基材に撥水性、耐摩耗性を共に付与できる高撥水・高しゅう動性製品を開発することを目標として鋭意研究を重ねた結果、基材の表面に、反応性官能基を有するシルセスキオキサンと改質ふっ素樹脂からなるシリカコーティング膜を施すことにより高撥水・高しゅう動性に優れた製品が得られることを見出した。 In view of the above prior art, the present inventors have drastically solved the problems of the above prior art, and have developed a highly water repellent / slidable product that can impart both water repellency and wear resistance to a substrate. As a result of intensive research with the goal of developing, the surface of the substrate is coated with a silica coating film made of silsesquioxane having a reactive functional group and a modified fluororesin. It was found that a product with excellent properties can be obtained.
本発明の好適な実施形態を示すコーティング材は、反応性官能基を有するシルセスキオキサンと改質ふっ素樹脂とからなり、シルセスキオキサン１００重量部に対し、改質ふっ素樹脂を１０〜１００重量部含有するものである。 A coating material showing a preferred embodiment of the present invention comprises a silsesquioxane having a reactive functional group and a modified fluororesin, and the modified fluororesin is 10 to 100 per 100 parts by weight of the silsesquioxane. Contains part by weight.
本実施形態では基材として、好適には、例えばプラスチック、ゴム、金属、セラミックス、木材、紙、竹、有機繊維、それらの組み合わせ、およびそれらの積層体を用いる。しかし、これらに限定されるものではなく、これらと同等ないし類似のものであれば同様に用いることができる。 In the present embodiment, for example, plastic, rubber, metal, ceramics, wood, paper, bamboo, organic fiber, a combination thereof, and a laminate thereof are preferably used as the base material. However, the present invention is not limited to these, and any equivalent or similar ones can be used.
また、上記シルセスキオキサンは、３官能性シランを加水分解することで得られる（ＲＳｉＯ１．５）ｎの構造を持つネットワーク型ポリマー、または多面体クラスターである。ここで、Ｒは炭化水素基、ｎは１以上の自然数である。 The silsesquioxane is a network polymer or polyhedral cluster having a structure of (RSiO 1.5 ) n obtained by hydrolyzing a trifunctional silane. Here, R is a hydrocarbon group, and n is a natural number of 1 or more.
シルセスキオキサンの反応性官能基は、ビニル基、メタクリロ基、アクリロ基、またはエポキシ基のいずれかからなるとよい。 The reactive functional group of silsesquioxane is preferably composed of any one of a vinyl group, a methacrylo group, an acrylo group, and an epoxy group.
すなわち、反応性官能基を有するシルセスキオキサンとしては、ポリシロキサンの誘導体であるエポキシ基含有シルセスキオキサン、ビニル基含有シルセスキオキサン、アクリロイル基含有シルセスキオキサン、メタクリロイル基含有のシルセスキオキサンを用いるとよい。 That is, as silsesquioxanes having reactive functional groups, epoxy group-containing silsesquioxanes, vinyl group-containing silsesquioxanes, acryloyl group-containing silsesquioxanes, and methacryloyl group-containing silices, which are polysiloxane derivatives, are used. Sesquioxane may be used.
改質ふっ素樹脂は、その原料となる原料ふっ素樹脂の融点以上の温度、大気圧下、かつ酸素濃度１．３ｋＰａ（１０ｔｏｒｒ）以下の条件の下、原料ふっ素樹脂に電離性放射線を照射して改質したものである。 The modified fluororesin is modified by irradiating the raw fluororesin with ionizing radiation under a temperature not lower than the melting point of the raw fluororesin used as a raw material, an atmospheric pressure, and an oxygen concentration of 1.3 kPa (10 torr) or lower. It is quality.
原料ふっ素樹脂としては通常のＰＴＦＥを用い、このＰＴＦＥを上述の条件で改質して改質ふっ素樹脂とした後、ジェットミルにより微粉砕した。 Ordinary PTFE was used as the raw material fluororesin, and the PTFE was modified under the above conditions to obtain a modified fluororesin, and then finely pulverized by a jet mill.
この微粉砕した改質ふっ素樹脂を上記シルセスキオキサンに加えるが、このとき、シルセスキオキサン１００重量部に対し、改質ふっ素樹脂を１０〜１００重量部含有するようにする。 The finely pulverized modified fluororesin is added to the silsesquioxane. At this time, 10 to 100 parts by weight of the modified fluororesin is contained with respect to 100 parts by weight of the silsesquioxane.
これは、改質ふっ素樹脂が１０重量部未満であると、撥水性、耐摩耗性ともに低くなり、改質ふっ素樹脂が１００重量部を超えると、撥水性は高いが、耐摩耗性が低くなるためである。 This is because when the modified fluororesin is less than 10 parts by weight, both the water repellency and wear resistance are low, and when the modified fluororesin exceeds 100 parts by weight, the water repellency is high but the wear resistance is low. Because.
また、本実施形態では、反応性官能基を有するシルセスキオキサンを熱や光により硬化させ、目的とする物性を付与させる。 Moreover, in this embodiment, the silsesquioxane which has a reactive functional group is hardened | cured with a heat | fever or light, and the target physical property is provided.
熱硬化の場合、シルセスキオキサンに過酸化物重合開始剤やカチオン重合開始剤を添加するとよい。 In the case of thermosetting, a peroxide polymerization initiator or a cationic polymerization initiator may be added to silsesquioxane.
過酸化重合開始剤としては、ジクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ベンゾイルパーオキサイド等を、カチオン重合開始剤としては、第４級アンモニウム塩、スルホニウム塩、ホスニウム塩等を用いるとよい。 As the peroxide polymerization initiator, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide or the like may be used, and as the cationic polymerization initiator, quaternary ammonium salt, sulfonium salt, phosnium salt or the like may be used. .
熱硬化の場合、本実施形態に係るコーティング材は、シルセスキオキサン１００重量部に対し、過酸化重合開始剤またはカチオン重合開始剤を０．５〜５重量部の範囲内で含有するとよい。 In the case of thermosetting, the coating material according to this embodiment may contain a peroxide polymerization initiator or a cationic polymerization initiator within a range of 0.5 to 5 parts by weight with respect to 100 parts by weight of silsesquioxane.
これは、過酸化重合開始剤またはカチオン重合開始剤が０．５重量部未満であると、硬化が不十分でコーティング材の硬度が低く耐摩耗性等の強靱性が得られず、５重量部を超えると、硬化後のシリカコーティング膜中にボイドを生じやすくなるためである。 This is because when the peroxide polymerization initiator or the cationic polymerization initiator is less than 0.5 parts by weight, the curing is insufficient, the hardness of the coating material is low, and the toughness such as wear resistance cannot be obtained. This is because voids tend to occur in the cured silica coating film.
一方、光硬化の場合には、ラジカル重合開始剤を添加し、可視光、紫外線、電子線等の照射によりラジカルを発生させ、このラジカルによりシルセスキオキサンを硬化させるとよい。 On the other hand, in the case of photocuring, it is preferable to add a radical polymerization initiator, generate radicals by irradiation with visible light, ultraviolet rays, electron beams, etc., and cure the silsesquioxane with these radicals.
ラジカル重合開始剤としては、アセトフェノン、ベンゾフェノン、トリアジン等を用いるとよい。 As the radical polymerization initiator, acetophenone, benzophenone, triazine or the like may be used.
光硬化の場合、本実施形態に係るコーティング材は、シルセスキオキサン１００重量部に対し、ラジカル重合開始剤を０．５〜５重量部の範囲内で含有するとよい。 In the case of photocuring, the coating material according to this embodiment may contain a radical polymerization initiator in the range of 0.5 to 5 parts by weight with respect to 100 parts by weight of silsesquioxane.
これは、ラジカル重合開始剤が０．５重量部未満であると、硬化が不十分でコーティング材の硬度が低く耐摩耗性等の強靱性が得られず、５重量部を超えると、硬化後のシリカコーティング膜中にボイドを生じやすくなるためである。 This is because if the radical polymerization initiator is less than 0.5 parts by weight, the curing is insufficient and the hardness of the coating material is low, and toughness such as wear resistance cannot be obtained. This is because voids are easily generated in the silica coating film.
上述したコーティング材を上記基材に塗布し、これを硬化して基材の表面にシリカコーティング膜を形成すると、本実施形態に係る高撥水・高しゅう動性製品が得られる。 When the coating material described above is applied to the substrate and cured to form a silica coating film on the surface of the substrate, the highly water-repellent and highly slidable product according to this embodiment is obtained.
次に、本実施形態の作用を説明する。 Next, the operation of this embodiment will be described.
本実施形態に係るコーティング材は、反応性官能基を有するシルセスキオキサンと改質ふっ素樹脂とからなり、シルセスキオキサン１００重量部に対し、改質ふっ素樹脂を１０〜１００重量部含有している。 The coating material according to this embodiment comprises a silsesquioxane having a reactive functional group and a modified fluororesin, and contains 10 to 100 parts by weight of the modified fluororesin with respect to 100 parts by weight of the silsesquioxane. ing.
シルセスキオキサンは、シリカコーティング膜表面に耐水性、耐摩耗性を付与し、改質ふっ素樹脂は、シリカコーティング膜の表面に局在することにより、撥水性、撥油性を付与する。 Silsesquioxane imparts water resistance and abrasion resistance to the surface of the silica coating film, and the modified fluororesin provides water repellency and oil repellency by being localized on the surface of the silica coating film.
つまり、本実施形態のコーティング材で基材表面にシリカコーティング膜を形成することで、その基材に撥水性、耐摩耗性を共に付与できる。 That is, by forming a silica coating film on the substrate surface with the coating material of this embodiment, both the water repellency and wear resistance can be imparted to the substrate.
また、本実施形態に係るコーティング材により形成されたシリカコーティング膜は、耐熱性を有しており、例えば、プラスチック等の可燃性の有機基材にコートすることにより、これを耐熱性とするだけでなく、それらの強度も格段に向上させることができる。 Further, the silica coating film formed by the coating material according to the present embodiment has heat resistance. For example, by coating a flammable organic base material such as plastic, the silica coating film only has heat resistance. In addition, their strength can be significantly improved.
すなわち、本実施形態に係るコーティング材は、基材に撥水・高しゅう動性を共に付与するだけではなく、特に、有機素材からなる有機基材の強度を向上させ、高耐久性化と長寿命化を実現できる。 That is, the coating material according to the present embodiment not only imparts both water repellency and high slidability to the base material, but also improves the strength of the organic base material made of an organic material, and makes it highly durable and long. Life expectancy can be realized.
さらに、本実施形態に係るコーティング材は、熱硬化で用いる場合、シルセスキオキサン１００重量部に対し過酸化物重合開始剤またはカチオン重合開始剤を０．５〜５重量部の範囲内で含有している。 Furthermore, the coating material according to this embodiment contains a peroxide polymerization initiator or a cationic polymerization initiator in a range of 0.5 to 5 parts by weight with respect to 100 parts by weight of silsesquioxane when used in thermosetting. is doing.
これにより、コーティング材の硬化が不十分であったり、硬化後のシリカコーティング膜中にボイドを生じることがなくなり、十分な強度を有するシリカコーティング膜を形成できる。 Thus, the coating material is not sufficiently cured, and voids are not generated in the cured silica coating film, and a silica coating film having sufficient strength can be formed.
また、本実施形態に係るコーティング材は、光硬化で用いる場合、前記シルセスキオキサン１００重量部に対しラジカル重合開始剤を０．５〜５重量部の範囲内で含有している。 Moreover, the coating material which concerns on this embodiment contains the radical polymerization initiator in the range of 0.5-5 weight part with respect to 100 weight part of said silsesquioxane, when using by photocuring.
これにより、熱硬化の場合と同様に、十分な強度を有するシリカコーティング膜を形成できる。 Thereby, the silica coating film which has sufficient intensity | strength can be formed similarly to the case of thermosetting.
本実施形態に係る高撥水・高しゅう動性製品は、本実施形態に係るコーティング材を基板に塗布し、これを硬化するという簡便な方法により製造できる。 The highly water-repellent and highly slidable product according to this embodiment can be manufactured by a simple method in which the coating material according to this embodiment is applied to a substrate and cured.
また、本実施形態に係る高撥水・高しゅう動性製品は、形成されたシリカコーティング膜表面が緻密なシリカ構造を有するため、耐水性に優れており、汚れを簡易に拭き取ったり洗い流したりできる利点を有する。 In addition, since the surface of the formed silica coating film has a dense silica structure, the highly water-repellent and highly slidable product according to the present embodiment has excellent water resistance, and can easily wipe off or wash away dirt. Have advantages.
基材として、アルミ板を使用して高撥水・高しゅう動性製品を作製した。 A highly water-repellent and highly slidable product was produced using an aluminum plate as the substrate.
（１）製品の作製
トリエトキシシランとビニルトリメトキシシランとを加水分解し共重合させることにより、ビニル基を有するシルセスキオキサン１を合成した。また、トリエトキシシランと３アクリロキシプロピルトリメトキシシランとを加水分解し共重合させることによりアクリロイル基を有するシルセスキオキサン２を合成した。これらのシルセスキオキサンに改質ふっ素樹脂と、ラジカル重合開始剤としてアセトフェノン（または過酸化物重合開始剤としてベンゾイルパーオキサイド）とを添加し分散させ、コーティング材とした。厚さ２ｍｍのアルミ表面に、エタノールをスプレーした後、赤外線ランプで乾燥し、これを３回繰り返し表面の洗浄を行った。その後、前述のコーティング材をスピンコートにより塗布し、紫外線（波長１００〜４００ｎｍ）または熱によって硬化させ、厚さ３０μｍのコーティング膜を得た。
(1) Production of product Silsesquioxane 1 having a vinyl group was synthesized by hydrolyzing and copolymerizing triethoxysilane and vinyltrimethoxysilane. Further, silsesquioxane 2 having an acryloyl group was synthesized by hydrolyzing and copolymerizing triethoxysilane and 3-acryloxypropyltrimethoxysilane. A modified fluororesin and acetophenone as a radical polymerization initiator (or benzoyl peroxide as a peroxide polymerization initiator) were added and dispersed in these silsesquioxanes to form a coating material. After spraying ethanol on the aluminum surface having a thickness of 2 mm, it was dried with an infrared lamp, and this was repeated three times to clean the surface. Thereafter, the above-described coating material was applied by spin coating and cured by ultraviolet rays (wavelength 100 to 400 nm) or heat to obtain a coating film having a thickness of 30 μm.
改質ふっ素樹脂の原料ふっ素樹脂には、ＰＴＦＥ（Ｐ−１９２ 旭硝子製）を使用した。このＰＴＦＥを、酸素濃度が０．１３３ｋＰａ（１ｔｏｒｒ）、窒素濃度が１０１．１９２ｋＰａ（７５９ｔｏｒｒ）の大気圧下（１０１．３２５ｋＰａ（７６０ｔｏｒｒ））、３４０℃の温度のもとで電子線（加速電圧２ＭｅＶ）を１００ｋＧｙ照射し、改質を行った。これをジェットミルにより平均粒径２０μｍに微粉砕した。 PTFE (manufactured by Asahi Glass Co., Ltd.) was used as the raw material fluorine resin for the modified fluororesin. The PTFE was subjected to an electron beam (acceleration voltage of 2 MeV) under an atmospheric pressure (101.325 kPa (760 torr)) at an oxygen concentration of 0.133 kPa (1 torr) and a nitrogen concentration of 101.192 kPa (759 torr) at a temperature of 340 ° C. ) Was irradiated with 100 kGy for modification. This was finely pulverized to a mean particle size of 20 μm by a jet mill.
以上のようにして、表１に示す実施例１〜５および比較例１〜４の製品を作製した。 As described above, the products of Examples 1 to 5 and Comparative Examples 1 to 4 shown in Table 1 were produced.
（２）試験方法及び結果
実施例１〜５および比較例１〜４の製品について、耐熱性、撥水性を評価し、さらに耐久性・長寿命化の指標としてしゅう動特性を評価した。
(2) Test method and results For the products of Examples 1 to 5 and Comparative Examples 1 to 4, the heat resistance and water repellency were evaluated, and the sliding characteristics were evaluated as indicators of durability and long life.
耐熱性は、上記コーティング材１０ｍｇを常温で真空中（圧力１．３Ｐａ（１０−２ｔｏｒｒ））、２４時間乾燥後、熱天秤（窒素５０ｍＬ／分、昇温速度１０℃／分）を用い、３０℃から２００℃まで上げ３０℃と２００℃での重量を測定し、両者の差から変化率を算出した。 For heat resistance, 10 mg of the coating material was vacuumed at room temperature (pressure 1.3 Pa (10 −2 torr)), dried for 24 hours, and then using a thermobalance (nitrogen 50 mL / min, temperature rising rate 10 ° C./min) The temperature at 30 ° C. and 200 ° C. was measured from 30 ° C. to 200 ° C., and the rate of change was calculated from the difference between the two.
撥水性については、接触角計（ＣＡ−Ｄ型 協和界面化学株式会社製）を用い、液滴径１．９ｍｍに調整し水の接触角により評価した。 The water repellency was evaluated by using a contact angle meter (CA-D type manufactured by Kyowa Interface Chemical Co., Ltd.) to adjust the droplet diameter to 1.9 mm and using the contact angle of water.
しゅう動特性については、次の方法により行った。試験にはリングオンデスク摩耗試験装置を使用し、ＪＩＳＫ７２１８に準じ、ＳＵＳ３０４製の円筒リング（外径２５．６ｍｍ、内径２０．６ｍｍ、平均粗さ０．６μｍ）と前記試験片をしゅう動させた。圧力０．１ＭＰａ、速度５０ｍ／分の条件で行い、雰囲気は空気中、２０℃とし、２０分後の比摩耗量および摩擦係数を測定した。 The sliding characteristics were measured by the following method. For the test, a ring-on-desk wear test apparatus was used, and in accordance with JISK7218, the SUS304 cylindrical ring (outer diameter 25.6 mm, inner diameter 20.6 mm, average roughness 0.6 μm) and the test piece were slid. . The pressure was 0.1 MPa, the speed was 50 m / min, the atmosphere was 20 ° C. in air, and the specific wear amount and the friction coefficient after 20 minutes were measured.
比摩耗量ＶＳＡは、２０分後の重量減少（摩耗量Ｖ）を測定し、下記の式（１）から求めた。 The specific wear amount V SA was obtained from the following formula (1) by measuring the weight loss (wear amount V) after 20 minutes.
ＶＳＡ＝Ｖ／（Ｐ・Ｌ） （１）
Ｖ：摩耗量、Ｐ：試験荷重、Ｌ：平均滑り距離
試験結果を表１にまとめて示す。
V SA = V / (P · L) (1)
V: Wear amount, P: Test load, L: Average slip distance The test results are summarized in Table 1.
表１に示すとおり、本発明に基づく実施例１〜５は接触角が高く撥水性に優れ、しかも耐摩耗性が良好であり更に摩擦係数も低く、低摩擦性に優れる特徴を有していることがわかる。 As shown in Table 1, Examples 1 to 5 based on the present invention have the characteristics that the contact angle is high, the water repellency is excellent, the wear resistance is good, the friction coefficient is low, and the low friction property is excellent. I understand that.
これに対し、改質ふっ素樹脂を混合していない比較例１は接触角が低く撥水性に劣り、耐摩耗性も低い。また改質されていないふっ素樹脂を用いた比較例２は分散性が悪く、比較例１と同様、接触角が低く撥水性に劣り、耐摩耗性も低い。改質ふっ素樹脂の混和量が限定値未満（１０重量部未満）の比較例３は、接触角が低く撥水性に劣り、耐摩耗性が低く、一方改質ふっ素樹脂の混和量が限定値（１００重量部）を超えた比較例４では、耐摩耗性が低下している。 On the other hand, Comparative Example 1 in which the modified fluororesin was not mixed has a low contact angle, inferior water repellency, and low wear resistance. Further, Comparative Example 2 using an unmodified fluorine resin has poor dispersibility, and, like Comparative Example 1, has a low contact angle, poor water repellency, and low wear resistance. In Comparative Example 3 in which the amount of the modified fluororesin is less than the limit value (less than 10 parts by weight), the contact angle is low, the water repellency is poor, and the wear resistance is low. In Comparative Example 4 exceeding 100 parts by weight, the wear resistance is lowered.
以上説明してきた実施例と比較例との対比からも明らかなように、本発明によれば、高撥水・高しゅう動性に優れた耐摩耗性を付与でき、有機ポリマの応用範囲を広げる上で大きく貢献するものである。 As is clear from the comparison between the examples described above and the comparative examples, according to the present invention, wear resistance excellent in high water repellency and high slidability can be imparted, and the application range of organic polymers is expanded. This is a significant contribution.
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