TW201020300A - Coating composition, method of antifouling treatment and antifouling substrate - Google Patents

Abstract

Provided are a coating composition with which an antifouling film having excellent antifouling properties, being transparent, and having durability sufficient for practical use can be formed at low cost; a method of antifouling treatment; and an antifouling substrate. The coating composition comprises a solvent, and dissolved therein, a compound represented by Formula 1 containing a perfluoroalkylene ether group in the molecular main chain and containing a hydrolyzable group containing a silicon atom in a side chain. The solvent is a mixed solvent of fluorinated solvents containing at least one of fluorinated hydrocarbon and fluorinated ether. The fluorinated solvents have a boiling point at 1 atm of 40 DEG C or higher and 70 DEG C or lower, and a difference between the highest and lowest boiling points of the mixed fluorinated solvents is within 25 DEG C.

Description

201020300 六、發明說明： 【發明所屬之技術領域】 本發明係關於塗佈用組成物、防污處理方法及防污性 基材，尤其是關於可賦予防污性之塗佈用組成物、防污處 理方法及以該方法進行防污處理之行動電話。 【先前技術】 ❹ 行動電話之顯示面、液晶面板或觸控面板之顯示面、 眼鏡鏡片等由於人之使用，而附著有皮脂、指紋、汗水、 化妝品等。因此，作爲用以使髒污不容易附著且髒污擦拭 容易之表面處理，有施行防污處理之情況。 * 防污處理爲在基材表面上以薄膜狀塗佈具有防污性之 - 物質者。薄膜之原料大多利用氟烷基樹脂或聚矽氧系樹脂 ’其中包含全氟聚醚基之化合物由於其表面能小，又由於 包含醚鍵故分子構造柔軟，因此已知可發揮優異之防污性 Φ 。以薄膜狀塗佈該等時，爲了確保基材與薄膜之密著性， 通常係以在同一化合物中導入可水解之基而成者作爲原料 〇 例如專利第3449070號提出藉由真空蒸鑛法以薄膜狀 塗佈全氟聚醚改質矽烷之方法。然而，真空蒸鍍法需要昂 貴的生產設備’且由於生產性低，而有生產成本高之問題 。又’可以真空蒸鍍法薄膜化之原料由於其分子量限制在 約5000以下者’因此有無法利用高功能之長鏈型原料之 問題。 201020300 因此，可以低成本生產之浸漬法、噴佈法等濕式塗佈 法受到矚目。 然而，過去之濕式塗佈法係將目的化合物溶於可溶之 溶劑中而溶液化，並塗佈於基材表面上，但由於目的化合 物包含水解基，因此溶液暴露於大氣中時，大氣中之水份 與化合物反應，使溶液凝膠化，而有目的化合物粒子化之 問題。 又，浸漬法由於溶液長時間暴露於大氣中，使溶液顯 © 著變質，而發生原料之利用效率、被膜品質之問題，結果 有生產成本提高之問題。又於浸漬法，由於依原理所形成 之被膜非以一層分子堆積，因此形成實用上具有足夠耐久 性之被膜有其困難。 ^ 噴佈法由於縮短溶液暴露於大氣中之時間，因此可避 - 免溶液變質。又由於生產性亦高，容易大面積化，因而可 稱爲朝向大量生產之工法。 然而，自噴佈噴嘴噴射出液滴附著於基材表面上，潤 Θ 濕擴散，使溶劑乾燥而使目的化合物於表面薄膜化之過程 中，有原料高分子粒子化使被膜白濁之問題。 專利文獻1 :特許第3449070號 【發明內容】 [發明欲解決之課題] 本發明係爲了解決上述問題而完成者，因此本發明之 目的爲提供一種可以低成本形成防污性優異，透明、實用 -6 - 201020300 上具有足夠之耐久性之防污被膜之塗佈用組成物，防污處 理方法及防污性基材。 [用以解決課題之手段] 本發明之塗佈用組成物之特徵爲將分子主鏈內含有全 氟伸烷基醚基、側鏈上含有包含矽原子之水解性基之化合 物溶解於溶劑中而成之組成物。該組成物中’上述溶劑之 Φ 特徵爲包含氟化烴及氟化醚之至少一種之氟系溶劑相互之 混合溶劑，上述氟系溶劑在1大氣壓下之沸點爲4〇°C以上 7(TC以下，混合之上述氟系溶劑之沸點之最大値與最小値 之差爲25°c以內 • 尤其上述化合物之特徵爲以下述式（1)表示之化合物： [化3]201020300 VI. [Technical Field] The present invention relates to a coating composition, an antifouling treatment method, and an antifouling substrate, and more particularly to a coating composition capable of imparting antifouling properties and prevention Pollution treatment method and mobile phone using the method for antifouling treatment. [Prior Art] 显示 The display surface of the mobile phone, the display surface of the LCD panel or the touch panel, the spectacle lens, etc. are attached to sebum, fingerprints, sweat, cosmetics, etc. due to human use. Therefore, there is a case where the antifouling treatment is performed as a surface treatment for making the stain less likely to adhere and the soiling is easy. * Antifouling treatment is a substance that is antifouling-coated on the surface of a substrate in the form of a film. Most of the raw materials of the film use a fluoroalkyl resin or a polyoxyl resin. The compound containing a perfluoropolyether group has a small surface energy and a soft molecular structure because it contains an ether bond, so that it is known to exhibit excellent antifouling properties. Sex Φ. When coating the film in the form of a film, in order to ensure the adhesion between the substrate and the film, it is generally used as a raw material by introducing a hydrolyzable group into the same compound. For example, Patent No. 3449070 is proposed by vacuum distillation. A method of coating a perfluoropolyether to modify decane in a film form. However, the vacuum evaporation method requires expensive production equipment' and has a problem of high production cost due to low productivity. Further, since the raw material which can be thinned by vacuum vapor deposition is limited to a molecular weight of about 5,000 or less, there is a problem that a long-chain raw material having high function cannot be utilized. 201020300 Therefore, wet coating methods such as dipping method and spray method which can be produced at low cost have attracted attention. However, in the past, the wet coating method dissolves the target compound in a soluble solvent and coats it on the surface of the substrate, but since the target compound contains a hydrolyzable group, the solution is exposed to the atmosphere, the atmosphere The water reacts with the compound to gel the solution, and the target compound is particleized. Further, in the immersion method, since the solution is exposed to the atmosphere for a long period of time, the solution is deteriorated, and the utilization efficiency of the raw material and the quality of the film are caused, and as a result, the production cost is increased. Further, in the dipping method, since the film formed by the principle is not deposited by a single layer of molecules, it is difficult to form a film which is practically durable enough. ^ The spray method avoids the deterioration of the solution by shortening the exposure time of the solution to the atmosphere. Moreover, since it is also highly productive and easy to be large-area, it can be called a method of mass production. However, the droplets are ejected from the nozzle to adhere to the surface of the substrate, and the wet diffusion is carried out to dry the solvent, so that the target compound is crystallized during the film formation, and the film is turbid. [Patent Document 1] Patent No. 3449070 [Disclosure] [Problems to be Solved by the Invention] The present invention has been made to solve the above problems, and an object of the present invention is to provide an excellent antifouling property at a low cost, which is transparent and practical. -6 - 201020300 A coating composition having an antifouling film having sufficient durability, an antifouling treatment method, and an antifouling substrate. [Means for Solving the Problem] The coating composition of the present invention is characterized in that a compound having a perfluoroalkyl ether group in a molecular main chain and a hydrolyzable group containing a ruthenium atom in a side chain is dissolved in a solvent. The composition of the composition. In the composition, the Φ characteristic of the solvent is a mixed solvent of a fluorine-based solvent containing at least one of a fluorinated hydrocarbon and a fluorinated ether, and the boiling point of the fluorine-based solvent at 4 atm is 4 〇 ° C or more and 7 (TC). In the following, the difference between the maximum enthalpy and the minimum enthalpy of the boiling point of the fluorine-based solvent to be mixed is within 25 ° C. In particular, the compound is characterized by a compound represented by the following formula (1): [Chemical 3]

Rf^OCF2CF2 CF2-^-〇-(CF2Rf^OCF2CF2 CF2-^-〇-(CF2

•Η (1) 式中，Rf表示碳數1~16之直鏈狀或分支狀全氟烷基 ，Y表示氫原子或碳數1〜3之烷基，R1表示選自鹵素原子 、-OR3 基、-OCOR3 基、-OC(R3) = C(R4)2 基、-ON = C(R3)2 基及-ON = C(R5)2基之至少一基，R3表示脂肪族烴基或芳 香族烴基，R4表示氫原子或碳數1〜3之烷基，R5表示碳 數3〜6之二價脂肪族烴基，q表示1〜50之整數，m表示 〇~2之整數，r表示1〜10之整數。 201020300 另外，特徵爲溶解以式（1)表示之化合物之氟系溶劑爲 1，1，1，3,3-五氟丁院、全氟己院、1,1,1,2,2,3,3,4,5,5,5-十 一氟-4-(三氟甲基）戊烷或甲基九氟丁基醚。Η (1) wherein Rf represents a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R1 represents a halogen atom selected from -OR3. a group of -OCOR3 groups, -OC(R3) = C(R4)2 groups, -ON = C(R3)2 groups and -ON = at least one group of C(R5)2 groups, and R3 represents an aliphatic hydrocarbon group or aroma a hydrocarbon group, R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R5 represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms, q represents an integer of 1 to 50, m represents an integer of 〇~2, and r represents 1 An integer of ~10. 201020300 In addition, the fluorine-based solvent characterized by dissolving the compound represented by the formula (1) is 1,1,1,3,3-pentafluorobutyl, perfluorohexan, 1,1,1,2,2,3 , 3,4,5,5,5-undefluoro-4-(trifluoromethyl)pentane or methyl nonafluorobutyl ether.

本發明之防污處理方法之特徵爲藉由在無機基材之表 面、或在無機或有機基材上形成之無機表面膜之表面上施 加塗佈，藉此進行防污處理之防污處理方法，於上述無機 基材表面或無機表面膜表面之塗層係以噴佈法塗佈上述本 發明之塗佈用組成物而成之塗層。 H 尤其，上述無機表面膜爲以噴佈法塗佈聚矽氮烷溶液 所形成之無機表面膜。 本發明之防污性基材爲在基材表面或於基材上形成之 無機表面膜之表面上具有防污層之防污性基材，其特徵爲 ^ 上述防污層爲藉由本發明之防污處理方法形成之防污層。 尤其，其特徵爲上述防污性基材係具有圖像顯示部且 於該圖像顯示部之表面上形成有上述耐防污層之行動電話 [發明效果] 本發明之塗佈用組成物由於以式（1)表示之化合物使用 具有特定構造及沸點之複數種混合溶劑作爲溶劑，因此可 以低成本形成防污性優異、透明，且在實用上具有足夠耐 久性之被膜。 【實施方式】 -8 - 201020300 可使用於本發明中之於分子主鏈內包含全氟伸烷基醚 基，側鏈中包含含矽原子之水解性基之化合物爲作爲塗佈 用組成物之溶質之化合物。 上述全氟伸烷基醚基係以下述式ο-1)表示，上述含矽 原子之水解性基係以下述式（1-2)表示： [化4] —^OCnFin+i^— (1—1) 4CT 七 Si-(Bf)3 (1-2) 式（1-1)中，η表示 1〜5之整數，式（1-2)中，m表示 〇〜2之整數，R1表示可水解基。 全氟伸烷基醚基內之醚鍵之出現頻率並無特別限制， 可使用以-(〇CF2)-、-(〇C2F4)-、-(OC3F6)-、-(〇C4F8)-等作 爲重複單位以單獨或複數種組合形成之全氟伸烷基醚基。 又，全氟伸烷基醚基一邊端部較好爲η爲1以上之CnF2n+1-基。 側鏈上具有之包含矽原子之水解性基較好爲塗佈中形 成塗膜時藉由水之作用分解之基即可，且以上述式（1-2)表 示。 R1舉例爲例如鹵素原子、-〇R3基、-OCOR3基 、-oc(r3) = c(r4)2 基、-〇N = C(R3)2 基、-on=c(r5)2 基 等。其中，R3表示脂肪族烴基或芳香族烴基，R4表示氫 原子或碳數1〜3之烷基，R5表示碳數3 ~6之二價脂肪族烴 201020300 基。 本發明中，較佳之R1爲於使用以式（1)表示之化合物 作爲溶質時，可更抑制被膜白濁發生之氯原子、-OCH3基 、-OC2H5 基。 可使用於上述本發明之化合物之較佳實例舉例爲以式 (1)表示之化合物。The antifouling treatment method of the present invention is characterized in that the antifouling treatment method is performed by applying a coating on the surface of an inorganic substrate or an inorganic surface film formed on an inorganic or organic substrate, thereby performing an antifouling treatment. The coating layer on the surface of the inorganic substrate or the surface of the inorganic surface film is coated with the coating composition of the present invention by a spray coating method. H In particular, the above inorganic surface film is an inorganic surface film formed by coating a polyazirane solution by a spray method. The antifouling substrate of the present invention is an antifouling substrate having an antifouling layer on the surface of the substrate or the surface of the inorganic surface film formed on the substrate, wherein the antifouling layer is the present invention. The antifouling layer formed by the antifouling treatment method. In particular, the antifouling substrate is a mobile phone having an image display portion and having the antifouling layer formed on the surface of the image display portion. [Effect of the invention] The coating composition of the present invention is Since the compound represented by the formula (1) uses a plurality of mixed solvents having a specific structure and a boiling point as a solvent, it is possible to form a film which is excellent in antifouling property, is transparent, and has practically sufficient durability at a low cost. [Embodiment] -8 - 201020300 The compound containing a perfluoroalkyl ether group in the main chain of the present invention and containing a hydrolyzable group containing a ruthenium atom in the side chain can be used as a coating composition. Solute compound. The perfluoroalkylene ether group is represented by the following formula ο-1), and the hydrolyzable group containing a ruthenium atom is represented by the following formula (1-2): [Chemical 4] —^OCnFin+i^— (1 —1) 4CT 七Si-(Bf)3 (1-2) In the formula (1-1), η represents an integer of 1 to 5, and in the formula (1-2), m represents an integer of 〇~2, and R1 represents Hydrolyzable group. The frequency of occurrence of the ether bond in the perfluoroalkylene ether group is not particularly limited, and -(〇CF2)-, -(〇C2F4)-, -(OC3F6)-, -(〇C4F8)-, etc. may be used as The repeat unit is a perfluoroalkylene ether group formed by a combination of a single or a plurality of combinations. Further, the one end of the perfluoroalkylene ether group is preferably a CnF2n+1- group having η of 1 or more. The hydrolyzable group containing a ruthenium atom in the side chain is preferably a group which is decomposed by the action of water when forming a coating film in coating, and is represented by the above formula (1-2). R1 is exemplified by, for example, a halogen atom, a -R3 group, an -OCOR3 group, -oc(r3) = c(r4)2 group, -〇N = C(R3)2 group, -on=c(r5)2 group, and the like. . Here, R3 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R5 represents a divalent aliphatic hydrocarbon having a carbon number of 3 to 6 201020300. In the present invention, it is preferred that when a compound represented by the formula (1) is used as a solute, the chlorine atom, the -OCH3 group, and the -OC2H5 group in which the film is clouded can be further suppressed. A preferred example of the compound used in the above invention can be exemplified by the compound represented by the formula (1).

Rf所表示之碳數1〜16之直鏈狀或分支狀全氟烷基舉 例爲三氟甲基、全氟乙基、全氟丙基、全氟丁基、全氟戊 @ 基等。 Y所表示之碳數1~3之烷基舉例爲甲基、乙基、丙基 〇 q表示1〜50，較好18~3 0，更好22~2 6之整數，m表 · 示0~2，較好0之整數，r表示1〜10，較好1〜5之整數。 .The linear or branched perfluoroalkyl group having 1 to 16 carbon atoms represented by Rf is exemplified by a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group or the like. The alkyl group having 1 to 3 carbon atoms represented by Y is exemplified by methyl, ethyl and propyl 〇q, and represents an integer of 1 to 50, preferably 18 to 30, more preferably 22 to 2 6 , and m is shown as 0. ~2, preferably an integer of 0, and r represents an integer of 1 to 10, preferably 1 to 5. .

以式（1)表示之氟化合物可藉由使市售之全氟聚醚經矽 烷處理獲得。該方法揭示於例如特開平1-294709號公報 中。 G 構成可於本發明使用之混合溶劑之成分之含有氟化烴 及氟化醚之至少一種之氟系溶劑之沸點在一大氣壓下爲 40t以上70°C以下。又，混合溶劑中之氟系溶劑之沸點之 最大値與最小値之差在2 5 °C以內，較好在2 0 °C以內。 較佳之混合溶劑之構成爲於一大氣壓下之沸點爲40°C 以上70°C以下之氟系溶劑1，與相對於該溶劑1之沸點具 有20°C以內之沸點差之氟系溶劑2之混合溶劑。 滿足上述沸點條件之二種以上之溶劑而成之塗佈劑經 -10- 201020300 噴佈塗覆混合時，可知可獲得膜厚不均受到抑制且透明之 被膜。 非以混合溶劑，而爲使用一種類溶劑之塗佈劑以噴佈 法塗覆時’被膜容易白濁，且獲得透明薄膜之條件範圍（ 例如’塗佈時氛圍之濕度與溫度等）顯著狹窄，結果成爲 高成本製程。又，組合有沸點差超過2 5 t之溶劑將損及被 膜之膜厚均勻性’發生可以目視辨識出的不均勻。使用沸 φ 點高於70°C之溶劑時至乾燥爲止之時間變長，相反地使用 沸點未達40°C之低溶劑時，自噴槍噴射之塗佈組成物之液 滴在到達基材之前即粉末化，而無法獲得透明薄膜。其機 制尙不明確’但以上述之溶劑組成可抑制膜厚之不均而獲 " 得透明被膜。 . 本發明中使用之溶劑，若考慮到對環境破壞之影響、 生產時之安全性、取得性等，較好爲選自1,1，1，3,3-五氟丁 烷（沸點 40°C)、全氟己烷（沸點 56。〇、1，1，1，2,2,3,3,4,5,5,5-O 十—氟_4_(三氟甲基）戊烷（沸點56。〇 '甲基九氟丁基醚（ 沸點6 1 °C )中之兩種以上之溶劑並經混合而成者。尤其是 選擇混合沸點差爲20 °C以內之兩種以上溶劑而成者較佳。 又，混合溶劑之混合比例相對於混合溶劑全體，較好 混合至少一種之成分爲1重量％以上，更好2重量％以上 者。 再者’上述溶劑中可混合可調整潤濕性等諸特性之助 劑。 本發明之塗佈用組成物可使用將基材浸漬於塗佈用組 -11 - 201020300 成物中之浸漬法，於基材上以噴霧狀塗佈該塗佈用組成物 之噴佈法，邊使基材旋轉邊滴下塗佈用組成物之旋轉塗佈 法等濕式製程，使用塗佈用組成物之溶劑之真空蒸鍍法等 之乾式製程等之習知方法塗佈於表面上形成防污層。 該等中，可知以噴佈法形成之防污層比其他方法形成 者之耐磨耗性更優異。又，就材·料之利用效率、生產性之 觀點而言，噴佈法亦比其他方法有利。因此，最佳之塗佈 方法爲噴佈法。 @ 形成上述防污層之基材可舉例爲無機基材或有機基材 〇 無機基材舉例爲玻璃、金屬、陶瓷等。該等中，較好 爲透明或半透明之玻璃、陶瓷等。 ' 有機基材舉例爲塑膠、橡膠、彈性體等。該等中，較 《 好爲透明或半透明之塑膠，最好爲丙烯酸系樹脂、聚碳酸 酯樹脂等。The fluorine compound represented by the formula (1) can be obtained by subjecting a commercially available perfluoropolyether to treatment with decane. This method is disclosed in, for example, Japanese Laid-Open Patent Publication No. Hei No. Hei. G The fluorine-based solvent containing at least one of a fluorinated hydrocarbon and a fluorinated ether which is a component of the mixed solvent used in the present invention has a boiling point of 40 t or more and 70 ° C or less at atmospheric pressure. Further, the difference between the maximum enthalpy and the minimum enthalpy of the boiling point of the fluorine-based solvent in the mixed solvent is within 25 ° C, preferably within 20 ° C. The preferred mixed solvent is a fluorine-based solvent 1 having a boiling point of 40 ° C or more and 70 ° C or less at a pressure of atmospheric pressure, and a fluorine-based solvent 2 having a boiling point difference of 20 ° C or less with respect to the boiling point of the solvent 1 Mixed solvent. When a coating agent obtained by dissolving two or more kinds of solvents of the above-mentioned boiling point conditions was spray-coated with -10-201020300, it was found that a film having a suppressed film thickness unevenness and a transparent film was obtained. When the coating is applied by a spray method using a solvent-like coating agent, the film is easily clouded, and the range of conditions for obtaining a transparent film (for example, 'the humidity and temperature of the atmosphere at the time of coating, etc.) is remarkably narrow. The result becomes a high-cost process. Further, the combination of a solvent having a boiling point difference of more than 25 t will impair the uniformity of the film thickness uniformity of the film. When the solvent having a boiling point higher than 70 ° C is used, the time until drying becomes longer, and when a low solvent having a boiling point of less than 40 ° C is used, the droplet of the coating composition sprayed from the spray gun before reaching the substrate That is, powdering, and a transparent film cannot be obtained. The mechanism is not clear, but the composition of the above solvent can suppress the unevenness of the film thickness and obtain a transparent film. The solvent used in the present invention is preferably selected from 1,1,1,3,3-pentafluorobutane (boiling point 40°) in consideration of effects on environmental damage, safety during production, and availability. C), perfluorohexane (boiling point 56. 〇, 1,1,1,2,2,3,3,4,5,5,5-O dec-fluoro_4_(trifluoromethyl)pentane ( a solvent having a boiling point of 56. 〇 'methyl nonafluorobutyl ether (boiling point 6 1 ° C) and a mixture of two or more solvents, especially two or more solvents having a difference in boiling point of 20 ° C or less Further, the mixing ratio of the mixed solvent is preferably 1% by weight or more, more preferably 2% by weight or more, based on the total amount of the mixed solvent. Further, the solvent can be mixed and adjusted in the above solvent. The coating composition of the present invention can be applied by spraying a substrate onto a substrate by a dipping method in which a substrate is immersed in a coating group -11 - 201020300. A wet process such as a spin coating method in which a coating composition is dropped while a substrate is rotated, and a solvent such as a coating composition is used for vacuum evaporation using a solvent for a coating composition. A conventional method such as a dry process is applied to the surface to form an antifouling layer. In the above, it is understood that the antifouling layer formed by the spray method is more excellent in abrasion resistance than those formed by other methods. From the viewpoint of utilization efficiency and productivity of the material, the spray method is also advantageous than other methods. Therefore, the optimum coating method is the spray method. @ The substrate forming the above antifouling layer can be exemplified by an inorganic substrate. Or an organic substrate 〇 an inorganic substrate is exemplified by glass, metal, ceramics, etc. Among these, a transparent or translucent glass, ceramic, etc. are preferable. 'The organic substrate is exemplified by plastic, rubber, elastomer, etc. Medium, "good for transparent or translucent plastic, preferably acrylic resin, polycarbonate resin, etc.

透明或半透明之基材多數爲用於行動電話、各種顯示 G 器等顯示部之情況，而爲特別需要形成防污層之基材之故 〇 基材之形狀較好爲薄膜或薄片狀，但並無特別限制， 若爲塗佈面爲平面或平滑之曲面則均可作爲形成防污層之 基材。又，亦可於基材上預先施加硬塗層、抗反射塗層、 防眩塗層等其他表面處理。 無機基材或有機基材之表面上較好設置無機表面膜。 尤其是在有機基材之表面上設置無機表面膜較佳。藉由設 -12- 201020300 置無機表面膜，可提高防污層之密著力。 至於無機表面膜可依據製品要求之規格 、半導體膜、氧化膜、氮化膜、氧氮化膜等 之厚度較好形成爲確保防污塗層之密著性所 之厚度，爲0·01~1μιη之範圍，更好爲0.05, 。但’基於防污性以外之製品要求規格有必 外之無機膜時，當然亦可成爲適當之膜厚。 φ 對基材表面形成無機表面膜可以噴佈法 鍍法、CVD法等習知之形成方法成膜。 形成以式（1)表示之化合物之防污層時， 氮烷溶液，以噴佈法塗佈並經乾燥而成之無 •.得實用上足夠之耐磨耗性。又，就生產成本 . 點而言，由於以噴佈法塗佈聚矽氮烷溶液形 之方法亦與其他方法同樣的優異，因此無機 該方法形成。 φ 聚矽氮烷溶液係由ΑΖ電子材料公司銷 劑之種類等配合基材之種類、膜厚、噴佈條 行稀釋 '濃縮者即可。再者，噴佈塗佈聚矽 載體氣體較好爲極力不含水分之氣體，且就 ' 言以氮氣最適當。另外，若依據需要而將乾 ' 烷系無機膜放置於高濕度氛圍中，或者藉由 ，亦可促進朝氧化矽之轉化。 本發明之防污性基材爲行動電話之顯示 或觸控面板之顯示面、眼鏡鏡片等之容易附 而選擇金屬膜 。無機表面膜 需之最小限度 -0.2 μιη之範圍 要在該範圍以 、溶膠法、濺 可知使用聚矽 機表面膜可獲 、生產性之觀 成無機表面膜 表面膜較好以 售，濃度、溶 件等，適宜進 氮烷時使用之 成本之觀點而 燥後之聚矽氮 施加光或熱能 面、液晶面板 著皮脂、指紋 -13- 201020300 、汗水、化妝品等之基材表面上進行上述之防污處理者。 以下，針對使用本發明之塗佈用組成物形成防污層之 行動電話之例，使用圖面加以說明。 圖1及圖2爲顯示行動電話之一例之圖。 圖1顯示行動電話全體，係由於通話等使用之各種操 作鍵1，電話相關之各種資訊（電話號碼、電波狀態、電池 殘餘量等）或畫面顯示部之畫面顯示裝置2、麥克風3、喇 叭4所構成。畫面顯示裝置2具體而言舉例有液晶顯示器 @ (LCD)或有機電致發光顯示器（有機EL顯示器）等。 圖2顯示圖1之剖面AA’。畫面顯示裝置2設置於行 動電話之框體5之內部，畫面顯示裝置2之上設置透過窗 構件6。透過窗構件6 —般爲光透過率良好之樹脂性，其 — 材質可爲丙烯酸、聚碳酸酯等。 · 本發明爲將無機表面膜6a與由式（1)表示之化合物形 成之防污層6b依序設置於透過窗構件6上者。 透明無機表面膜6a係藉由濺鍍法形成於透過窗構件6 〇 上。無機表面膜6a之材料可利用聚矽氮烷系無機膜。 又’表面之防污層6b可使用以式（〗）表示之化合物作 爲溶質之塗佈用組成物，以噴佈法經塗佈·乾燥而形成。 實施例 以下列方法評價防污處理後之基材。說明評價項目與 評價方法。 -14 * 201020300 (評價1)外觀 在暗室內於螢光燈500流明以上之照度下目視觀察評 價樣品，判定被膜有無白濁、不均勻。 (評價2)皮脂附著性 將評價樣品抵壓在面頰上，以目視觀察皮脂之附著狀 態。評價基準係以未經處理之青板玻璃之附著狀態設爲不 φ 良，相較於此的皮脂附著狀態明顯較少者設爲良好。 (評價3)皮脂除去性 以纖維素製不織布（旭化成公司製造之BENCOTE)輕輕 的來回擦拭下述（評價4)之評價樣品1 0次，以目視觀察皮 . 脂殘留。評價基準以幾乎不殘留皮脂者設爲良好，明顯殘 留者設爲不良。 φ (評價4)耐磨耗性 以9_8N/cm2之荷重將影印用紙（ASKUL製造之SUPER-WHITE)抵壓向樣品，來回滑動，測定滑動部之對水之接 觸角，測定接觸角低於90°爲止之滑動次數。試驗進行三 ' 次以上，評價其平均値。另外，若以該試驗方法進行五萬 次左右之耐磨耗性，則認爲實用上具有足夠之耐磨耗性。 又，以下之實施例、比較例中所述之膜厚係藉由膜厚 計（偏光解析計）（溝尻光學公司製造之DHA-FR)測定與評價 樣品同時形成之Si(10 0)基板上之被膜。又接觸角爲藉由 -15- 201020300 接觸角計（協和界面科學公司製造之DM1 00)測定評價樣品 表面對水之接觸角而測定。 實施例1 準備將1重量份之以下述式（2)表示之化合物溶解於4 重量份之全氟己烷（沸點56。〇及195重量份之1，1，1，3,3-五氟丁烷（沸點40。〇之混合溶劑中而成之組成物作爲塗佈 用組成物。以噴佈法將該塗佈組成物塗佈於玻璃基板（AS-ONE公司製造之載玻璃S1225)上，且在5(TC下乾燥30分 鐘。形成之防污層之膜厚爲8.4nm，接觸角爲116。。被膜 之外觀並無不均而爲透明，皮脂附著性、皮脂除去性亦均 良好。又耐磨耗性爲95,763次。結果列於表1。 [化5] C3F7"(〇CF2CF2 CF七 •Η (2) rl-10The transparent or translucent substrate is mostly used for a display unit such as a mobile phone or a display G, and is particularly required to form a substrate of an antifouling layer. The shape of the substrate is preferably a film or a sheet. However, it is not particularly limited, and if it is a flat surface or a smooth curved surface, it can be used as a substrate for forming an antifouling layer. Further, other surface treatment such as a hard coat layer, an anti-reflective coating layer, or an anti-glare coating layer may be applied to the substrate in advance. An inorganic surface film is preferably provided on the surface of the inorganic substrate or the organic substrate. In particular, it is preferred to provide an inorganic surface film on the surface of the organic substrate. By setting the inorganic surface film on -12-201020300, the adhesion of the anti-fouling layer can be improved. As for the inorganic surface film, the thickness of the semiconductor film, the oxide film, the nitride film, the oxynitride film, etc., which is required to meet the requirements of the product, is preferably formed to ensure the adhesion of the antifouling coating layer, which is 0·01~ The range of 1 μιη, more preferably 0.05. However, when an inorganic film other than the anti-fouling property is required, the film thickness may be appropriately set. φ The inorganic surface film is formed on the surface of the substrate by a conventional forming method such as a spray coating method or a CVD method. When the antifouling layer of the compound represented by the formula (1) is formed, the azane solution is applied by a spray coating method and dried to obtain a practically sufficient abrasion resistance. Further, in terms of production cost, since the method of coating the polyazirane solution by the spray method is also excellent as in other methods, the inorganic method is formed. The φ polyazane solution is prepared by blending the type of the substrate with the type of the substrate, the film thickness, and the spray strip. Further, the spray coating of the polyfluorene carrier gas is preferably a gas which does not contain moisture as much as possible, and it is most appropriate to use nitrogen gas. Further, if the dry 'alkyl-based inorganic film is placed in a high-humidity atmosphere as needed, or by conversion, the conversion to cerium oxide can be promoted. The antifouling substrate of the present invention is a metal film selected from the display of a mobile phone or the display surface of a touch panel, an eyeglass lens or the like. Insulin surface film minimum required -0.2 μιη range to be in this range, sol method, splashing knows the use of polythene machine surface film can be obtained, the production of the view into the inorganic surface film surface film is better for sale, concentration, dissolution The above-mentioned defense is carried out on the surface of the substrate such as the surface of the substrate after the drying of the polypyrene nitrogen applied light or thermal energy surface, the liquid crystal panel with sebum, the fingerprint-13-201020300, the sweat, the cosmetics, etc. Stainer. Hereinafter, an example of a mobile phone in which an antifouling layer is formed using the coating composition of the present invention will be described with reference to the drawings. 1 and 2 are diagrams showing an example of a mobile phone. Fig. 1 shows the entire mobile phone, which is various operation keys 1 used for a call or the like, various information related to the telephone (telephone number, radio wave state, battery residual amount, etc.) or screen display device 2 of the screen display portion, microphone 3, speaker 4 Composition. The screen display device 2 is specifically exemplified by a liquid crystal display @ (LCD) or an organic electroluminescence display (organic EL display). Figure 2 shows a section AA' of Figure 1. The screen display device 2 is disposed inside the casing 5 of the mobile phone, and the transmission window member 6 is disposed on the screen display device 2. The window member 6 is generally a resin having a good light transmittance, and the material may be acrylic or polycarbonate. In the present invention, the inorganic surface film 6a and the antifouling layer 6b formed of the compound represented by the formula (1) are sequentially disposed on the transmission window member 6. The transparent inorganic surface film 6a is formed on the transmission window member 6 by sputtering. As the material of the inorganic surface film 6a, a polyazane-based inorganic film can be used. Further, the surface antifouling layer 6b can be formed by applying and drying a compound represented by the formula (J) as a coating composition for a solute by a spray coating method. Examples The substrate after the antifouling treatment was evaluated by the following method. Explain the evaluation project and evaluation method. -14 * 201020300 (Evaluation 1) Appearance The evaluation sample was visually observed under a illuminance of 500 lumens or more in a dark room to determine whether the film was cloudy or uneven. (Evaluation 2) Sebum adhesion The evaluation sample was pressed against the cheek to visually observe the adhesion state of sebum. The evaluation criteria were such that the state of adhesion of the untreated green sheet glass was not good, and it was good that the sebum adhesion state was significantly smaller than this. (Evaluation 3) Sebum-removing property The evaluation sample of the following (Evaluation 4) was gently rubbed back and forth 10 times with a non-woven fabric made of cellulose (BencoTE, manufactured by Asahi Kasei Corporation), and the residue was visually observed. The evaluation criteria were set to be good for those who had almost no sebum remaining, and those with obvious residuals were bad. Φ (Evaluation 4) Abrasion resistance The photocopying paper (SUPER-WHITE manufactured by ASKUL) was pressed against the sample at a load of 9_8 N/cm2, and slid back and forth to measure the contact angle of the sliding portion with respect to water, and the contact angle was determined to be less than 90. The number of slides until °. The test was carried out three or more times and the average enthalpy was evaluated. Further, if the abrasion resistance of about 50,000 times is carried out by the test method, it is considered to have practical wear resistance. In addition, the film thickness described in the following examples and comparative examples was measured on a Si (10 0) substrate formed simultaneously with the evaluation sample by a film thickness meter (polarization analyzer) (DHA-FR manufactured by Gully Optical Co., Ltd.). The film. Further, the contact angle was measured by measuring the contact angle of the surface of the sample with water by a contact angle meter (DM1 00 manufactured by Kyowa Interface Science Co., Ltd.) of -15-201020300. Example 1 1 part by weight of a compound represented by the following formula (2) was dissolved in 4 parts by weight of perfluorohexane (boiling point 56. 〇 and 195 parts by weight of 1,1,1,3,3-pentafluoro A composition obtained by mixing butane (a boiling point of 40 Å in a mixed solvent) is applied as a coating composition. The coating composition is applied onto a glass substrate (glass-coated glass S1225 manufactured by AS-ONE Co., Ltd.) by a spray method. And dried at 5 (TC for 30 minutes. The film thickness of the formed antifouling layer was 8.4 nm, and the contact angle was 116. The appearance of the film was not uneven and was transparent, and sebum adhesion and sebum removal were also good. The wear resistance was 95,763 times. The results are shown in Table 1. [Chemical 5] C3F7"(〇CF2CF2 CF七•Η (2) rl-10

Si-(〇CM3X 式（2)中，側鏈上具有三甲氧基矽烷之重複單位之重複 數1-10係表示重複數1〜10之混合物。 實施例2 準備將1重量份之以上述式（2)表示之化合物溶解於4重 量份之全氟己烷（沸點56°C)及195重量份之l，l,l,2,2,3,3,4,5,5,5-十一氟_(三氟甲基）戊烷（沸點56°C)之混合溶劑中而成之組 201020300 成物作爲塗佈用組成物。以噴佈法將該塗佈組成物塗佈於 玻璃基板（AS-ΟΝΕ公司製造之載玻璃S 1 225)上，在50°C 下乾燥30分鐘。形成之防污層之膜厚爲9.2nm，接觸角爲 115°。被膜之外觀並無不均而爲透明，皮脂附著性、皮脂 除去性亦均良好。又耐磨耗性爲8 8,140次。結果列於表1 中〇 φ 實施例3 準備將1重量份之以上述式（2)表示之化合物溶解於4 重量份之全氟己烷（沸點56t)及195重量份之甲基九氟丁 基醚（沸點611)之混合溶劑中而成之組成物作爲塗佈用組In the formula (2), the repeating number of the repeating unit having a trimethoxydecane in the side chain of 1-10 is a mixture of the repeating numbers of 1 to 10. Example 2 Preparing 1 part by weight of the above formula (2) The compound is dissolved in 4 parts by weight of perfluorohexane (boiling point 56 ° C) and 195 parts by weight of 1,1,1,2,2,3,3,4,5,5,5- A group of 201020300, which is a mixture of monofluoro-(trifluoromethyl)pentane (boiling point of 56 ° C), is used as a coating composition. The coating composition is applied to a glass substrate by a spray method. (glass-coated glass S 1 225 manufactured by AS-A) was dried at 50 ° C for 30 minutes. The film thickness of the formed anti-fouling layer was 9.2 nm, and the contact angle was 115 °. The appearance of the film was not uneven. It was transparent, sebum adhesion and sebum removal were also good, and the abrasion resistance was 8,8,140 times. The results are shown in Table 1 〇φ Example 3 Preparation of 1 part by weight of the compound represented by the above formula (2) A composition obtained by dissolving in a mixed solvent of 4 parts by weight of perfluorohexane (boiling point 56t) and 195 parts by weight of methyl nonafluorobutyl ether (boiling point 611) as a coating group

— 成物。以噴佈法將該塗佈組成物塗佈於玻璃基板（AS-ONE - 公司製造之載玻璃S 1 225)上，在50°C下乾燥30分鐘。形 成之防污層之膜厚爲8.8nm，接觸角爲116°。被膜之外観 並無不均而爲透明，皮脂附著性、皮脂除去性亦均良好。 φ 又耐磨耗性爲92,598次。結果列於表1中。 實施例4 以噴佈法將聚矽氮烷溶液（AZ電子材料公司製造之 AQUAMICA NL120A-05)塗佈於附硬塗層之丙烯酸基板（三 菱Rayon公司製造之ACRYLITE MR-200)上，在大氣氛圍 中放置一晝夜形成聚矽氮烷薄膜（膜厚93 inn)。隨後，在與 實施例2相同之條件下以噴佈法塗佈實施例2使用之塗佈 組成物。防污層之膜厚爲8.5ηιη，接觸角爲1 17°。 •17- 201020300 被膜之外觀並無不均而爲透明，皮脂附著性、皮脂除 去性亦均良好。又耐磨耗性爲6 6，0 3 1次。 比較例1 準備將1重量份之以上述式（2)表示之化合物溶解於 199重量份之全氟己烷（沸點56°C)中而成之組成物作爲塗 佈組成物。在與實施例1相同之條件下以噴佈法將該塗佈 組成物塗佈於玻璃基板（AS-ONE公司製造之載玻璃si 22 5) 上。被膜之外觀明顯白濁。由於被膜外觀不良，故終止皮 脂附著性、皮脂去除性及耐磨耗性評價。 比較例2 準備將1重量份之以上述式（2)表示之化合物溶解於4 . 重量份之全氟己烷（沸點56t)及195重量份之旭硝子公司 製造之Novec HFE7200(沸點76°C)之混合溶劑中而成之組 成物作爲塗佈組成物。在與實施例1相同之條件下以噴佈 ◎ 法將該塗佈組成物塗佈於玻璃基板（AS-ΟΝΕ公司製造之載 玻璃S1225)上。被膜之外觀雖爲透明，但發生以目視可辨 識之圓形模樣（不均勻）。由於被膜之外觀不良，故終止皮 脂附著性、皮脂除及耐磨耗性之評價。 比較例3 準備將1重量份之以上述式（2)表示之化合物溶解於4 重量份之全氟己烷（沸點56 °C)及195重量份之住友3M公 -18- 201020300 司製造之FLUORINERT F C - 4 0 (沸點1 5 5 °C )之混合溶劑中 而成者作爲塗佈組成物。在與實施例1相同之條件下以噴 佈法將該塗佈組成物塗佈於玻璃基板（AS-ΟΝΕ公司製造之 載玻璃S 1 225)上。被膜之外觀雖爲透明，但發生以目視可 辨識之不定形（變形蟲狀）之不均。由於被膜之外觀不良， 故終止皮脂附著性、皮脂除及耐磨耗性之評價。 φ 比較例4 以噴佈法將實施例2中使用之塗佈組成物直接塗佈於 實施例4中使用之附硬質塗層之丙烯酸基板上。防污層之 膜厚爲9.9nm，接觸角爲116°。被膜之外觀並無不均而爲 ' 透明，皮脂附著性、皮脂除去性亦均良好。但，耐磨耗性 . 低至7,379次。 比較例5 φ 以真空蒸鍍法將實施例2中使用之塗佈組成物之溶質 成膜於實施例2中使用之玻璃基板上。真空蒸鍍之背景壓 力爲1 0_3 P a左右，且將置於玻璃製坩堝中之塗佈組成物之 溶質在30分鐘內自室溫升溫至500°C。形成之被膜之膜厚 ' 爲7.2nm，接觸角爲1 17°。被膜之外觀並無不均而爲透明 _ ，皮脂附著性、皮脂除去性亦均良好。但，耐磨耗性爲 42,217次，較實施例2低。 比較例6 -19- 201020300 以浸漬法將實施例2中使用之塗佈組成物成膜於實施 例2中使用之玻璃基板上。浸漬法係在室溫下浸漬24小 時，且以10mm/秒之速度拉提。形成之被膜膜厚爲5nm以 下，無法被測定。另外，接觸角爲117°。被膜之外觀並無 不均而爲透明，皮脂附著性、皮脂除去性亦均良好。但， 耐磨耗性低至4,7 0 1次。 以濺鍍法於實施例4中使用之附硬塗層之丙烯酸基板 上形成Si02薄膜（膜厚lOlnm)。濺鍍係以離子束進行，使 背景壓力成爲10_3Pa左右，且對熔融石英標靶照射700eV 之Ar離子束。隨後，以噴佈法塗佈實施例2中使用之塗 - 佈劑。防污層之膜厚爲8.9nm，接觸角爲1 15。。被膜之外 . 觀並無不均而爲透明，皮脂附著性、皮脂除去性亦均良好 。但’耐磨耗性爲20,558次，比實施例4低。 各實施例與各比較例之結果槪述於表1。又，表1中 φ ’溶劑A表示全氟己烷（沸點56。〇，溶劑b表示丨，；!五 氟丁烷（沸點40。〇,溶劑C爲 氟-(二氟甲基）戊烷（沸點56°c)，溶劑D爲甲基九氟丁基醚 (沸點61°C)，溶劑E爲旭硝子公司製造之N〇vecHFE7200( ' 沸點76C)’溶劑F爲住友3M公司製造之FLUORINERT 1^-4 0(沸點155°(：)。 -20- 201020300 [表i] 塗佈組成物 基材 無機表 面膜 塗佈 方法 評價結果 溶質 溶劑 1 溶劑 2 外觀 皮脂 附著性 皮脂 除去性 耐磨耗 性(次） 實施例1 式(2) A B 玻璃 4nr Μ 噴佈法 良好 良好 良好 95,763 實施例2 式(2) A C 玻璃 Μ 噴佈法 良好 良好 良好 88,140 實施例3 式(2) A D 玻璃 m 噴佈法 良好 良好 良好 92,598 實施例4 式(2) A C 丙烯酸 聚矽 氮院 噴佈法 良好 良好 良好 66,031 比較例1 式(2) A fte y»\\ 玻璃 姐 <n、N 噴佈法 白濁 _ _ 比較例2 式(2) A E 玻璃 4E 噴佈法 圓形 不均 - - - 比較例3 式(2) A F 玻璃 Μ y\\\ 噴佈法 不定形 不均 - - - 比較例4 式(2) A C 丙烯酸 Μ 噴佈法 良好 良好 良好 7,379 比較例5 式(2) A C 玻璃 Μ 真空蒸 鍍法 良好 良好 良好 42,217 比較例ό 式(2) A c 玻璃 4nr 無 浸漬法 良好 良好 良好 4,701 比較例7 式⑵ A c 丙烯酸 濺鍍 Si02 噴佈法 良好 良好 良好 20,558 [產業上利用之可能性] φ 藉由本發明之塗佈組成物及表面處理方法，可以低成 本形成防污性優異、爲透明、且實用上具有足夠耐久之防 污被膜，故可利用於行動電話、顯示裝置等中。 ' 【圖式簡單說明】 ' 圖1爲顯示本發明之行動電話之實施形態之一例之外 觀圖。 圖2爲顯示圖1之剖面AA'之槪略圖。 -21 - 201020300 【主要元件符號說明】 1 :操作鍵 2 :畫面顯示裝置 3 :麥克風（發話口） 4 :喇叭（收話口） 5 :框體 6 :透過窗構件 6a :無機表面膜 @ 6b :防污層 -22-— adult. This coating composition was applied onto a glass substrate (glass-coated glass S 1 225 manufactured by AS-ONE - Co., Ltd.) by a spray method, and dried at 50 ° C for 30 minutes. The film thickness of the formed antifouling layer was 8.8 nm, and the contact angle was 116°. The outer layer of the film was not uneven and was transparent, and the sebum adhesion property and sebum removal property were also good. φ has an abrasion resistance of 92,598 times. The results are shown in Table 1. Example 4 A polyazide solution (AQUAMICA NL120A-05 manufactured by AZ Electronic Materials Co., Ltd.) was applied onto a hard-coated acrylic substrate (ACRYLITE MR-200 manufactured by Mitsubishi Rayon Co., Ltd.) by a spray method at atmospheric atmosphere. A film of polydecazane (film thickness 93 inn) was formed in the atmosphere for a day and night. Subsequently, the coating composition used in Example 2 was applied by a spray method under the same conditions as in Example 2. The anti-fouling layer has a film thickness of 8.5 ηηη and a contact angle of 1 17°. • 17- 201020300 The appearance of the film is not uniform and transparent, and the sebum adhesion and sebum removal properties are also good. The wear resistance is 6 6,0 3 1 times. Comparative Example 1 A composition obtained by dissolving 1 part by weight of the compound represented by the above formula (2) in 199 parts by weight of perfluorohexane (boiling point: 56 ° C) was prepared as a coating composition. This coating composition was applied onto a glass substrate (glass-coated si 22 5 manufactured by AS-ONE Co., Ltd.) by a spray method under the same conditions as in Example 1. The appearance of the film was obviously cloudy. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removal property, and abrasion resistance was terminated. Comparative Example 2 1 part by weight of the compound represented by the above formula (2) was dissolved in 4 parts by weight of perfluorohexane (boiling point 56 t) and 195 parts by weight of Novec HFE 7200 (boiling point 76 ° C) manufactured by Asahi Glass Co., Ltd. The composition obtained in the mixed solvent is used as a coating composition. This coating composition was applied onto a glass substrate (glass-coated glass S1225 manufactured by AS-A) under the same conditions as in Example 1 by a spray coating method. Although the appearance of the film is transparent, a circular pattern (non-uniform) which is visually identifiable occurs. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removal, and abrasion resistance was terminated. Comparative Example 3 1 part by weight of a compound represented by the above formula (2) was dissolved in 4 parts by weight of perfluorohexane (boiling point: 56 ° C) and 195 parts by weight of FLUORINERT manufactured by Sumitomo 3M -18-201020300 A mixed solvent of FC - 4 0 (boiling point 15 5 ° C) was used as a coating composition. This coating composition was applied onto a glass substrate (glass-loaded glass S 1 225 manufactured by AS-A) under the same conditions as in Example 1 by a spray method. Although the appearance of the film is transparent, unevenness of the amorphous shape (anamorphic shape) which is visually recognizable occurs. Since the appearance of the film was poor, the evaluation of sebum adhesion, sebum removal, and abrasion resistance was terminated. φ Comparative Example 4 The coating composition used in Example 2 was directly applied onto the hard coated acrylic substrate used in Example 4 by a spray method. The anti-fouling layer had a film thickness of 9.9 nm and a contact angle of 116°. The appearance of the film was not uniform and was 'transparent, and the sebum adhesion property and sebum removal property were also good. However, the wear resistance is as low as 7,379 times. Comparative Example 5 φ The solute of the coating composition used in Example 2 was formed into a film on the glass substrate used in Example 2 by a vacuum deposition method. The background pressure of the vacuum evaporation was about 10_3 P a, and the solute of the coating composition placed in the glass crucible was heated from room temperature to 500 ° C in 30 minutes. The film thickness of the formed film was 7.2 nm, and the contact angle was 1 17°. The appearance of the film was not uniform and was transparent _, and sebum adhesion and sebum removal were also good. However, the abrasion resistance was 42,217 times, which was lower than that of Example 2. Comparative Example 6 -19-201020300 The coating composition used in Example 2 was formed into a film on the glass substrate used in Example 2 by a dipping method. The impregnation method was immersed at room temperature for 24 hours and pulled at a rate of 10 mm/sec. The formed film thickness was 5 nm or less and could not be measured. In addition, the contact angle was 117°. The appearance of the film was not uniform and was transparent, and the sebum adhesion property and sebum removal property were also good. However, the wear resistance is as low as 4,700 times. A SiO 2 film (film thickness: 10 nm) was formed by sputtering on the hard-coated acrylic substrate used in Example 4. The sputtering was performed with an ion beam, the background pressure was about 10_3 Pa, and the fused silica target was irradiated with an Ar ion beam of 700 eV. Subsequently, the coating-coating agent used in Example 2 was applied by a spray coating method. The film thickness of the antifouling layer was 8.9 nm, and the contact angle was 1 15 . . Outside the film. The view is not uneven and transparent, and sebum adhesion and sebum removal are also good. However, the abrasion resistance was 20,558 times, which was lower than that of Example 4. The results of the respective examples and comparative examples are summarized in Table 1. Further, in Table 1, φ 'solvent A represents perfluorohexane (boiling point 56. 〇, solvent b represents 丨, ;! pentafluorobutane (boiling point 40. 〇, solvent C is fluoro-(difluoromethyl)pentane) (Boiling point 56 ° C), solvent D is methyl nonafluorobutyl ether (boiling point 61 ° C), solvent E is N〇vecHFE7200 ( 'boiling point 76C)' solvent F manufactured by Asahi Glass Co., Ltd. FLUORINERT 1 manufactured by Sumitomo 3M ^-4 0 (boiling point 155° (:). -20- 201020300 [Table i] Coating composition substrate inorganic surface film coating method evaluation result solute solvent 1 solvent 2 appearance sebum adhesion sebum removal wear resistance (次) Example 1 Formula (2) AB Glass 4nr 喷 Spraying method is good and good 95,763 Example 2 Formula (2) AC glass Μ Spraying method is good and good 88, 140 Example 3 Formula (2) AD glass m Spraying cloth Good and good method 92,598 Example 4 Formula (2) AC Acrylic polyfluoride nitrogen spray method Good and good 66,031 Comparative example 1 Formula (2) A fte y»\\ Glass sister <n, N Spraying white turbidity _ _ Comparative Example 2 Formula (2) AE Glass 4E Spraying method Circular unevenness - - - Comparative Example 3 Formula (2) AF Glass Μ y\\\ Disproportionate unevenness in the spray method - - - Comparative Example 4 Formula (2) AC Acrylic acid 喷 Spraying method is good and good 7,379 Comparative Example 5 Formula (2) AC glass crucible Vacuum evaporation method is good and good 42,217 Comparative Example 式 Formula (2) A c Glass 4nr No immersion method Good good Good 4,701 Comparative Example 7 Formula (2) A c Acrylic acid sputtered SiO 2 Spraying method is good and good 20,558 [Probability of industrial use] φ By the coating of the present invention The cloth composition and the surface treatment method can form an antifouling film which is excellent in antifouling property and transparent, and which is practically durable enough at low cost, and can be used in a mobile phone, a display device, etc. ' [Simple description of the drawing] Fig. 1 is an external view showing an embodiment of a mobile phone according to the present invention. Fig. 2 is a schematic view showing a section AA' of Fig. 1. -21 - 201020300 [Description of main component symbols] 1: Operation key 2: Screen Display device 3: microphone (speaking port) 4: speaker (receiving port) 5: frame 6: transmission window member 6a: inorganic surface film @ 6b: antifouling layer-22-

Claims (1)

201020300 七、申請專利範圍： 1. 一種塗佈用組成物，其係將於分子主鏈內含有全氟 伸烷基醚基，側鏈上含有包含矽原子之水解性基之化合物 溶解於溶劑中而成之塗佈用組成物，其特徵爲 前述溶劑爲包含氟化烴及氟化醚之至少一種之氟系溶 劑相互之混合溶劑，前述氟系溶劑在1大氣壓下之沸點爲 4 0 °C以上7 0 °C以下，前述混合溶劑中之前述氟系溶劑之沸 φ 點之最大値與最小値之差爲25。(：以內。 2_如申請專利範圍第1項之塗佈用組成物，其中前述 全氟伸院基醚基以下式（1-1)表示，前述包含砂原子之水解 性基以下式（1 - 2 )表示： [化1] —(〇 C〇 Fin+1 (i—i) 卜(R)3 0-2) ❹ (式中，η爲1~5之整數，m爲〇〜2之整數，R1表示可水 解之基）。 3 .如申請專利範圍第2項之塗佈用組成物，其中前述 化合物爲以下式（1)表不之化合物： [化2] Rf-(〇CF2CF2 CF,-^-〇-(CF2 心ί—201020300 VII. Patent application scope: 1. A coating composition containing a perfluoroalkyl ether group in a molecular main chain, and a compound containing a hydrolyzable group containing a ruthenium atom in a side chain is dissolved in a solvent. The coating composition is characterized in that the solvent is a mixed solvent of a fluorine-based solvent containing at least one of a fluorinated hydrocarbon and a fluorinated ether, and the fluorine-based solvent has a boiling point of 40 ° C at 1 atm. Above 70 ° C, the difference between the maximum enthalpy and the minimum enthalpy of the boiling point φ of the fluorine-based solvent in the mixed solvent is 25. (2) The coating composition according to the first aspect of the invention, wherein the perfluoro-extension-based ether group is represented by the following formula (1-1): the hydrolyzable group containing the sand atom is represented by the following formula (1) - 2 ) means: [Chemical 1] - (〇C〇Fin+1 (i-i) Bu (R)3 0-2) ❹ (where η is an integer from 1 to 5, m is 〇~2 The formula of the coating of the second aspect of the invention, wherein the compound is a compound represented by the following formula (1): [Chemical 2] Rf-(〇CF2CF2 CF ,-^-〇-(CF2 heart ί— ⑴ -23- 201020300 (式中，Rf表示碳數1~16之直鏈狀或分支狀全氟烷基’ Y表 示氫原子或碳數1~3之烷基，R1表示選自鹵素原子' -OR3 基、-OCOR3 基 ' -oc(r3)=c(r4)2 基、-on=c(r3)2 基及-on=c(r5)2 基之至少一基，R3表示脂肪族烴基或芳香族烴基，R4表示 氫原子或碳數1〜3之烷基，R5表示碳數3~6之二價脂肪族 烴基，q表示1〜50之整數，m表示0〜2之整數，r表示 1~1〇之整數）。 ❹ 4. 如申請專利範圍第3項之塗佈用組成物，其中前述 R1爲選自氯原子、-OCH3基及-OC2H5基之至少一基。 5. 如申請專利範圍第1項之塗佈用組成物，其中前述氟 系溶劑爲1,1,1,3,3-五氟丁烷、全氟己烷、1,1，1，2,2,3,3,4,5,5,5- · 十一氟-4-(三氟甲基）戊烷或甲基九氟丁基醚》 . 6. 如申請專利範圍第1項之塗佈用組成物，其中前 述混合溶劑爲選自1，1，1,3,3 -五氟丁烷、全氟己烷、 1，1，1，2,2,3,3,4,5,5,5-十一氟-4-(三氟甲基）戊烷及甲基九氟丁 @ 基醚之兩種氟系溶劑之混合溶劑。 7. —種防污處理方法，其爲藉由在無機基材之表面、 或無機或有機基材上形成之無機表面膜之表面上施加塗層 藉此進行防污處理之防污處理方法，其特徵爲 — 於前述無機基材之表面或無機表面膜之表面之塗層係 以噴佈法塗佈申請專利範圍第1項之塗佈用組成物而成之 塗層。 8. 如申請專利範圍第7項之防污處理方法，其中前述 -24- 201020300 無機表面膜爲以噴佈法塗佈聚矽氮烷溶液所形成之無機表 面膜。 9.一種防污性基材，其爲在基材表面或於基材上形成 之無機表面膜之表面上具有防污層之防污性基材，其特徵 爲 前述防污層爲藉由申請專利範圍第7項之防污處理$ 法形成之防污層。 1 〇· —種防污性基材，其特徵爲前述防污性基材係具 有圖像顯市部且於該圖像顯不部之表面上形成有申請專手丨j 範圍第9項之耐防‘污層之行動電話。 ❹ -25-(1) -23- 201020300 (wherein Rf represents a linear or branched perfluoroalkyl group having a carbon number of 1 to 16 'Y represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R1 represents a halogen atom selected from - OR3 group, -OCOR3 group '-oc(r3)=c(r4)2 group, -on=c(r3)2 group and at least one group of -on=c(r5)2 group, R3 represents an aliphatic hydrocarbon group or An aromatic hydrocarbon group, R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R5 represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms, q represents an integer of 1 to 50, m represents an integer of 0 to 2, and r represents An integer from 1 to 1). 4. The coating composition according to claim 3, wherein the above R1 is at least one selected from the group consisting of a chlorine atom, an -OCH3 group, and an -OC2H5 group. 5. The coating composition according to claim 1, wherein the fluorine-based solvent is 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2, 2,3,3,4,5,5,5- · undecafluoro-4-(trifluoromethyl)pentane or methyl nonafluorobutyl ether. 6. Apply as coated in item 1 of the patent application a composition for cloth, wherein the mixed solvent is selected from the group consisting of 1,1,1,3,3-pentafluorobutane, perfluorohexane, 1,1,1,2,2,3,3,4,5, A mixed solvent of two fluorine-based solvents of 5,5-undefluoro-4-(trifluoromethyl)pentane and methyl nonafluorobutane@yl ether. 7. An antifouling treatment method which is an antifouling treatment method which performs an antifouling treatment by applying a coating on a surface of an inorganic substrate or an inorganic surface film formed on an inorganic or organic substrate, It is characterized in that the coating layer on the surface of the inorganic substrate or the surface of the inorganic surface film is coated by coating with a coating composition of the first application of the patent application. 8. The antifouling treatment method according to item 7 of the patent application, wherein the -24-201020300 inorganic surface film is an inorganic surface film formed by spraying a polyxazane solution by a spray method. An antifouling substrate which is an antifouling substrate having an antifouling layer on a surface of a substrate or an inorganic surface film formed on the substrate, wherein the antifouling layer is applied by Anti-fouling treatment formed by the anti-fouling treatment of Article 7 of the patent scope. 1 〇 — 防 防 防 防 防 防 防 防 防 防 防 防 防 前述 前述 前述 防 前述 前述 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防 防Anti-staining mobile phone. ❹ -25-