1261615 ' 九、發明說明： ^【發明所屬之技術領域】 本發明係關於一種疏水結構及其製法，尤指-種形成 於基材表面之疏水結構及其製法。 【先前技術】 近年來，由於人們對於日常生活用品薄型化與微小化 促，多數產業邁入奈米科技的時代。除了生活週 ,^豕毛用°°外’自清潔(seif_cieaning)產品的功能及應用 也由於對-般民生產品降低維護成本及提高產品品質上 々而大幅地提升其市場需求’並使自清潔塗層材料 的爾市場上備受嗎目。自清潔塗層材料的用途，例如 幕玻璃、廚房衛浴等之塗層可降低維護成本； 應用在场能電池、衛星天線表面、汽車前擔玻 、、主 漂疏水塗層可提高產品品質 ^ 外殼上可降低因阻力造成的心與飛行器 ._塗層材料之研=的=;=產生的廢氣污染。 :=蓮花效應(L~)，再加上低表面:二 表面特性，可使塗層材料之水滴接觸角大於1〇〇 降低水滴及油滴之沾附。 口而 現有技術在自清潔塗層材料之結構設計上， 結構以達到疏水自清潔功能。其多層結構分別具備 =性、粗縫表面結構、超低表面能等不同特性，但目前 此超疏水結構多面㉟#、 久性不足之問題。， -不足、透明性差及耐 1830]p〇] 5 1261615 … 例如»vm,865 號 1 5,674,625 號及帛 M23,863 Ί關專利揭示利用溶I凝膠⑽训的方式製作無機物 、二液’經塗佈形成_結構表面。上述方法中除了溶膠-，勝需製作兩種以上溶液的繁瑣製程外，其餘製程，如凝 .膠的形成與乾燥的過程，需費力地將條件控制好以防止相 分離(phase S啊ation)的發生，且其製品的疏水角不足。 冷||塗液系統本質上為鬆散結構，於 劑去除過程中，若栌制不木^ 3 φ , ^ 右才工制不^，溥艇極易因表面張力不平衡 而破裂’或是析出金屬氧化物發生聚集現象⑽以， 而無法獲得奈米級結構薄膜。 羽士 ^ ΜΑ322號及第6,623,863號美國專利揭示使用溶 膠·'凝膠法及將矽氧烷化合物與氟矽化合物混合後塗佈形 成，水表面，但是此製法有接著性不佳的問題。而美國專 J第5、,296,282號係利用添加絲狀物（出犯加加）以增加粗链 度，然而此製法會造成粗糙結構的不連續，進而造成疏 魯性不足。 爪 • ^第5,693,236號美國專利揭示將針狀結構材料的外層 ：堡佈一層疏水物質並與黏著劑混合，再將其塗佈於基材上 ，以達到超疏水效果。但是其製造成本較高，因針狀結構 材料較為昂貴，而且針狀結構的粒徑較大，易造成不透明 或低透明度之表面。 第6,306,506號美國專利揭示利用氬（Ar)電漿之方式 製作粗糙表面。該製程較為複雜不易控制，且其所需費用 18301P0] 1261615 、”不上所边’現有疏水性奈米粗糙表 、！於:由於多層結構中各層之界面多為不同性術瓶頸 高分子、無機氧化物、低表面能分子），^材制t斤接 1、粗糖表面結構、超低表面能等不同特性之^具矣備 ，斗寸別是含有低表面能特 粗I表面 ·;另外，目前使用於自: 通吊黏著性也相對欠佳 ..燒偶合劑或高分子在^ 之氣系樹脂或疏水性石夕氧 釗次阿刀子在無粗糙結構之搭配下， 水性能約僅能水滴 早—材料之疏 _^法相水滴接觸角 米級結構粗趟表面，在未=用，凝膠法所製作之微 夠硬度，因此長期使溫燒結之過程無法具備足 可見光波長約為： 技術所製成之粗Μ表面容 級粉體或溶膠-凝膠 結果，因而如何在不影無法穿透或散射之 之連續相粗韃表面結構二 提下，製作奈米等級 料除具有低表面能特性外 Α挑我;低表面能材 麵等缺點，使得現今技術無法：::::=及『 好的接著特性或長期的產品耐用性“的透先度、良 料之存:上述問題，為了因應自清潔塗層材 前述習知技術之各 【發明内容】 、‘'、、别亟欲解決的課題。 本毛明之-目的係提供—種基材表面之疏水結構及 18301P01 7 1261615 其製：，以提供梳水結構之高硬度特性。 發明之次一目的係提供一 及其製法，以提供梳水結之、古：基材表面之疏水結構 構之咼透明特性。 么月之另一目的係提伊— 及其製法，以提供梳水結之、，基材表面之疏水結構 。偁之耐磨耗特性。 本舍明之再一目的係接 一 及其製法，以接 士、〃—種基材表面之疏水結構 =叫供疏水結構之優異疏水性。 為達上述其其他目的， 水結構，係包括：一奈米，从供一種基材表面之疏 Φ ^ Λ- ” \ ^，形成於該基材表面，传 由〜之奈未無機物與有機物 係 水塗層，形成於該奈米粗糙層表面。-而成，以及—疏 W述該奈米無機物係為金 氧化物係選自例如二氧化矽之功〃'勿季“土地，该金屬 鈦乳化物：及例如二氧化鍅之鍅氧化物之其中一：之 忒奈米無機物之顆粒間係為連續 物例如矽氧鍵之化學鍵鍵处。、π 稭由有機 之界面，你一山士 6亥示米粗糙層與該基材表面 粗糙層與該疏水法爲夕w /建之化子鍵鍵結。該奈米 化學鍵鍵結1 土 θ "面’係藉由有機物例如發氧鍵之 。該奈米粗糙層之平均粗糙度係介 。而该奈米粗縫層之厚产介 介於〗5 1ΠΛ 又；丨於丨丨加至〗50nm之間，較佳係 ’丨方；1 nm至1 〇〇nrn之間。兮太伞> 。亥不未热機物之粒徑係介於1〇nm 1〇〇nm之間，較佳係介於1〇_至50腿之間。 該疏水塗層係由低表面能材料所構成。較佳係選自含 18301P01 8 1261615 、 氟及矽之其中一種高分子，例如含烷基之氯矽烷化合物 、 （alkyl group- containing chi or 〇 silanes)、含氟：)：完基之三氣石夕 院化合物（fluoroalkyl group-containing trichlorosilanes)、含 氟烧基之三院氧石夕烧化合物（fluoroalkyl group-containing trialkoxysilanes)、含氟烧基之三醯氧石夕烧化合物 (fluoroalkyl group-containing triacyloxysilanes)、含氟烧基 之三異氰酸S旨石夕:)：完化合物（fluoroalkyl group- containing triisocyanatesilanes)、含烧基之烧氧石夕烧化合物（alkyl • group- containing alkoxy silanes)、含烧基之醯氧石夕炫化合 物（alkyl group-containing acyloxysilanes)及含：)：完基之異氰 酉曼酉旨石夕烧 4匕合物（alkyl group- containing isocyanatesilanes) 之其中一者。 本發明復提供一種基材表面之疏水結構製法，係包括 :提供基材、有機-無機按混材料及低表面能材料，塗佈有 機-無機摻混材料於該基材表面，並經高溫燒結而於該基材 φ表面形成一奈米粗糙層；以及塗佈低表面能材料，以於該 -: 奈米粗链層表面形成疏水塗層。 ·； 前述該有機-無機摻混材料係混合奈米無機物與有機 聚合物。較佳地該奈米無機物係可為金屬氧化物與無機化 合物之其中一者。金屬氧化物係可選自例如二氧化石夕之石夕 氧化物、例如二氧化鈦之鈦氧化物、及例如二氧化錯之錄 氧化物之其中一者。無機化合物係為選自三曱基乙氧基石夕 烷（TMOS)、四乙氧基矽烷（TEOS)及三乙氧基鈦（TEOTi)之 其中一者。該奈米無機物之粒徑係介於1 Onm至1 OOnm之 9 18301P01 1261615 間，較佳係係介於1 Onm至50nm之間。 該有機聚合物係為具有烯基之高分子化合物，且其分 子量範圍為500至100000者，較佳係為5000至75000者 ，最佳係為10000至55000。該高分子化合物係為選自聚 乙稀基吼略:)：完酮及聚乙烯醇之其中一者。而該有機-無機摻 混材料含有1至50重量％之有機聚合物。該有機-無機摻 混材料塗佈於基材表面之濕膜厚度介於1 〇〇 nm至1 OOOnm 之間，較佳係介於100 nm至500nm之間。 該奈米無機物係經由酸驗度控制其氧化物粒徑，經產 生溶膠凝膠反應而與有機聚合物形成微相分離結構。該酸 鹼度控制係可介於pH 3至13之間，較佳係介於PH 7至 13之間。 該高溫燒結之溫度係介於300°C至800°C之間。較佳地 ，係於300°C至600°C之間的溫度烘烤達成。 該低表面能材料係為選自含氟及矽之其中一種高分子 。較佳地，該高分子係為選自含烧基之氯石夕烧化合物（alkyl group- containing chlorosilanes)、含氟烧基之三氯石夕：!：完化 合物（fluoroalkyl group-containing trichlor〇silanes)、含氟烧 基之三烧氧石夕烧化合物（fluoroalkyl group-containing trialkoxysilanes)、含敦;)：完基之三驢氧石夕烧化合物 (fluoroalkyl group-containing triacyloxysilanes) ^ 含氟烧基 之三異氰酸酯石夕烧化合物（fluoroalkyl group- containing triisocyanatesilanes)、含烧基之烧氧石夕烧化合物（alkyl group- containing alkoxysilanes)、含院基之醯氧石夕烧化合 10 18301P01 1261615 ° (alkyl gl〇UP' C〇ntaining isocyanatesilanes) 中-m為選自破璃基材、料基材及金屬基材之其 種。而於㈣燒結之前，復可包括 溫熟化步驟。 』吋之至 根據本發明之方法所製成之疏水結構，其無機化合物 :面為化學鍵鍵結，且該化學鍵切氧鍵者。而該奈米無 機物間為連續相結構，因此，本笋 ’、 疏水性、耐磨耗、高透日月、# 4、、、口構具有優異 且其製法可將製程簡單化、成本經濟化及加工有it優 點，進而提升產業的整體競爭力。另一方之 =構係利用奈米複合材料的複合特性所製成，是以提= 了…、機材料的剛性卻也能同時提高有機材料的韌性。 【實施方式】 以下兹藉由具體實施例，進—步詳述本發明之特點及 功效。惟該等實施細節僅係用以說明本發明之特點，而非 用以限制本發明之範疇： j施例-~ 奈米粗糙層之製造方法與其塗佈方法： 於室溫中，依莫耳數比Mm?在雙頸圓底瓶中 依序置入125克之乙醇、〗5克之四乙氧矽烷 (tetraethoxysU·)及4.15克（36_%)之氫氧化敍，並將盆 授拌均勻3〇分鐘使成透明溶液。接著，在啊的條件下 18301P0] 11 1261615 ’進打，流反應8小時。當該反應完成後，將之置於室溫 下’ & _攪拌2G小時，以製得無機粉體分散液。 另外，將ίο克之聚乙烯基D比略朗（⑽yvinyi 咖_刪；分子量55〇〇〇)與19〇克之乙醇於室溫下㈣ 0分鐘使其完全溶解，以製得有機溶液。 接者，依7 :3的體積比將無機溶液與有機溶液於室溫 下均勾攪拌60分鐘，使生成塗佈所需之有機-無機 液。 利用旋轉塗佈機以轉速u〇〇rpm，方走轉時間15咖 ’每次吸取1.5毫升之有機無機混合溶液的條件下，於破 璃試片上進行旋轉塗佈！次。接著，將該試片置於室溫下 20小時以進行室溫熟化。 接著，將熟化後之玻璃試片置於高溫烘箱内，並從25 c至加熱1G(rc ’在1G(rc下維持1小時；接著再從10(rc 加熱至6崎，再將其自然冷卻至室溫以形成具奈米粗链 層之玻璃片。上述之加熱步驟是以每分鐘上 溫方式所達成。 .C之升 疏水塗層之製造方法與低表面能材料塗佈方法： 於室溫下，在雙頸圓底瓶中依序置入23·7克之異丙醇 (isopropyl alcohol)、1克之正十七氟十烷基三曱氧基矽烧予 (heptadecafluorodecyltrimeth〇xysiiane)& 〇 3 克之純 κ 75毫克之硝酸（0.1 N)，並將其攪拌均勻2小時，進^水解 反應。 反應完成後加人5克之4A分子筛，進行脫水、縮合 ]8301P〇i 12 1261615 :=並將其置於―室溫下18小時。反應完成後以濾、紙 心 φ，形成氟烷矽化合物溶液（FAS溶液）。 利用旋轉塗佈機以轉速11〇〇 ，每次吸取μ - 1 、iUUlPm ，旋轉時間15sec 璃片上，〜·、、$升之FAS溶液以滴於具奈米粗链層之玻 5分鐘的條件T，於玻璃試片上進 仃旋轉塗佈3次。 、力工疋 將塗佈元成之玻璃片置於供箱中以14〇t：供烤！小時 。取出之試片，即為一且有 、/、有Ί、口構之基材。所形成包含 二二、:“-疏水塗層之疏水結構掃描式電子顯微鏡圖 τ於第10，其原子力顯微圖（AFM)示於第2圖。而 弟1圖及第2圖可知’根據本發明之方法 =形㈣等級之疏水結構，且該疏水結構之奈綱 層為連續相。 實施例二 重稷貫施例一之步驟，將聚乙烯基吡咯烷酮 # (f〇IyvinyIpyrrolidone)置換為分子量1〇〇〇〇，其餘步驟同 實施例一。其SEM結果示於第3圖。 實施例三 於室溫下，在雙頸圓底瓶中依序置入50克之乙醇、」 克之四乙氧矽烷（tetraethoxySilane)及 3·〇27 克（36 wt%)之 濃鹽酸，並將其以磁石攪拌均勻19小時，製得無機溶液 另外’將10克之聚乙烯基吡咯烷酮（p〇Iyvinyl pyrrolidone;分子量55000)與19〇克之乙醇於室溫下攪拌 18301P0] 13 ^261615 30分鐘使其完全溶解，以製得有機溶液。 接著，依7 :3的體積比將無機溶液與有機溶液於室溫 :均勻攪拌60分鐘，使生成塗佈所需之有機_無機混合溶 利用旋轉塗佈機以轉速1100rpm ，旋轉時間Msec :每次吸取丨.5毫升之有機·無機混合溶液的條件下，於玻 璃試片上進行旋轉塗佈1次。接著，將該試片置於室溫下 2〇小時以進行室溫熟化。 、μ 接著，將熟化後之玻璃試片置於高溫烘箱内，並彳“ Μ =加熱UKTcuocrc下維持丄小時；接著再從 加Λ、、至000C：,再將其自然冷卻至室溫以形成且太 層之玻璃片。上述之加熱步驟是以每分鐘上升;:=二 溫方式所達成。 低表面能材料之製造方法與其塗佈方法： 於室溫下，在雙頸圓底瓶中依序置入23 7克之異丙醇 # (isopropyulc0h0l)、！克之正十七氟十烷基三甲氧基矽烷 (heptadecafiuorodecyitrimeth〇xysilane)& 〇 3 克之純水及 75毫克之硝酸（0.1 N)’並將其攪拌均勻2小時，進^水解 反應。 反應完成後加入5克之4A分子筛，進行脫水、縮和 聚合反應，並將其置於室溫下18小時。反應完成後以濾紙 過濾分子篩，形成氟烷矽化合物溶液（FAS溶液）。 —利用旋轉塗佈機以轉速1100卬111 ，旋轉時間 ’每次吸取1.5毫升之FAS溶液以滴於具奈米粗键層之玻 18301P01 14 x厶〇1615 續片上，每次塗佈間隔 λ 行旋轉塗佈3次。 刀釦的條件下，於玻璃試片上進 將塗佈完成之破鴣 。取出之試片，即為 置於艇箱…4(TC供烤！小時 示於第4圖。 ，、有疏水結構之基材。其SEM結果 疏水結構之特性分析 將實施例1、2、3 # 4 y、… 度及鉛筆硬度之測n "以下述方法作接觸角、透明 4“ 度之/貝“式，測試結果如表一。 保持水平(試片需為平坦，無扭曲， 近表面），水、m2 )從微量針筒滴出（盡量靠 ^ / 時，針的尖端仍於水滴内部(水滴 正央）’ t哭移離針筒（針筒不可收縮、劇烈移動， 而造成水滴體積/位置變化）。量測水滴之左右兩側之接觸 角:各兩次’共四個數據。於同一基材表面上’另找四個 不同之位置，重複上述步驟，進行量測，總共2〇個數據， 求其平均值。 透明度測試-A S TM D ] 7 4 7 - 9 7 使用6式片尺寸為50nim* 100mm，試片先以有積分球之 色差計’測得可見光透光率（％)。於溫度45± 下之，將 試片置於裝置内，使試片（A)與Blank(B)距離光源230mm ，以CNS 10986之UV照射裝置，照射looo小時。再量 測邛見光透光率（％)。計算測試前後之可見光透光率（❻/。）之 差值（絕對值）。 15 18301P01 1261615 3363-92^ 於環境溫度23土 2°C，相對濕度50土 5〇/〇下，將試片放 :超：16小時。將錯筆以削錯筆機削成尖頭，平滑：圓形 =紙，於垂直方向磨鉛筆頭，使呈平坦無破損、 貝/、熙砰裂之筆頭（5〜6mm)。從最硬之鉛 力：下的二:)’再往後— r至〗一。測試至㈣無法晝穿塗層 :’可以放大鏡辅助；鉛筆頭於過程 晝出痕跡之最微筆，二 此f層之硬度。至少重複測試—次至結果相同。p為1261615 ' IX. Description of the invention: ^ [Technical field to which the invention pertains] The present invention relates to a hydrophobic structure and a process for the preparation thereof, and more particularly to a hydrophobic structure formed on a surface of a substrate and a process for the preparation thereof. [Prior Art] In recent years, most industries have entered the era of nanotechnology because of the thinning and miniaturization of daily necessities. In addition to the life week, the function and application of the 'self-cleaning (seif_cieaning) product is also greatly improved by the maintenance of the maintenance cost and the improvement of the product quality of the ordinary people's products. The layer of materials is well received in the market. The use of self-cleaning coating materials, such as curtain glass, kitchen and bathroom coatings, can reduce maintenance costs; application in field energy batteries, satellite antenna surfaces, automotive front glass, and main bleaching hydrophobic coatings can improve product quality. It can reduce the heart and the aircraft caused by the resistance. The research of the coating material === the generated exhaust gas pollution. :=Lotus effect (L~), plus low surface: two surface characteristics, the contact angle of the coating material can be greater than 1〇〇 to reduce the adhesion of water droplets and oil droplets. The prior art is designed in the structure of the self-cleaning coating material to achieve a hydrophobic self-cleaning function. The multi-layer structure has different characteristics such as = sex, rough surface structure and ultra-low surface energy, but at present, the superhydrophobic structure has multiple faces of 35# and is insufficient in durability. , - Insufficient, poor transparency and resistance to 1830] p〇] 5 1261615 ... For example, »vm, 865 No. 1, 5, 674, 625 and 帛 M23, 863 Shaoguan patent reveals the use of dissolved I gel (10) training to make inorganic, two liquid ' Coating forms a structural surface. In addition to the sol- ing process of the above method, in addition to the cumbersome process of making two or more solutions, the other processes, such as the formation and drying process of the gel, require laborious control of the conditions to prevent phase separation (phase S ation). Occurs, and the hydrophobic angle of the product is insufficient. The cold||coating system is essentially a loose structure. In the process of removing the agent, if it is not wood ^ 3 φ , ^ right is not working, the boat is easily broken due to surface tension imbalance ' or precipitation The metal oxide is aggregated (10) so that a nano-sized structural film cannot be obtained. U.S. Patent Nos. 322 and 6,623,863 disclose the use of a sol-gel method and a mixture of a siloxane compound and a fluoroquinone compound to form a water surface, but this method has a problem of poor adhesion. In the United States, J, No. 5, No. 296, 282 uses the addition of filaments (invasion plus addition) to increase the coarse chain. However, this method causes discontinuity of the rough structure, which in turn causes insufficient stagnation. The US Patent No. 5,693,236 discloses the outer layer of a needle-like structural material: a layer of hydrophobic material is mixed with an adhesive and applied to a substrate to achieve a superhydrophobic effect. However, the manufacturing cost is high, because the needle-like structure material is relatively expensive, and the needle-like structure has a large particle size, which is liable to cause an opaque or low-transparent surface. U.S. Patent No. 6,306,506 discloses the use of argon (Ar) plasma to produce a rough surface. The process is more complicated and difficult to control, and its cost is 18301P0] 1261615, "not on the side" existing hydrophobic nano-roughness table, !: Since the interface of each layer in the multi-layer structure is different, the bottleneck polymer, inorganic Oxide, low surface energy molecule), ^ material made of t kg, 1, rough sugar surface structure, ultra-low surface energy and other characteristics of the preparation, the bucket size is low surface energy extra coarse I surface · In addition, Currently used in: Self-adhesive adhesion is also relatively poor.. Burning coupler or polymer in the gas resin or hydrophobic Shixia oxime sub-knife in the absence of rough structure, the water performance can only be Water droplets early—material sparseness _^ method phase water droplet contact angle meter structure rough surface, in the non-use, gel method is made of micro-hardness, so long-term temperature sintering process can not have enough visible wavelength: Technology The resulting rough surface-capacity powder or sol-gel results, so how to make a nano-scale material with low surface energy without mentioning the continuous phase rough surface structure that cannot penetrate or scatter Picking me out of the characteristics; Shortcomings such as surface energy materials make today's technology impossible:::::= and "good adhesion characteristics or long-term product durability": the above problems, in order to respond to self-cleaning coatings Each of the above-mentioned prior art [inventions], '', and other problems to be solved. The purpose of the present invention is to provide a hydrophobic structure on the surface of a substrate and 18301P01 7 1261615 to provide high hardness characteristics of the comb structure. A second object of the invention is to provide a method and method for providing a water-repellent, ancient: hydrophobic structure of a hydrophobic structure on a substrate surface. Another purpose of the month is Tye – and its method of production, to provide a water-repellent, hydrophobic structure on the surface of the substrate. The wear resistance characteristics of 偁. A further object of the present invention is to tie it to a method of making a hydrophobic structure on the surface of a substrate, such as a hydrophobic structure. In order to achieve the other purposes described above, the water structure comprises: a nanometer, formed on the surface of the substrate from a surface of a substrate, Φ ^ Λ-" \ ^, which is passed from the water to the organic matter and the organic water. a coating formed on the surface of the nano-rough layer. The nano inorganic system is a gold oxide selected from the group consisting of, for example, cerium oxide. And: one of the cerium oxides such as cerium oxide: the granules of the cerium nano-mineral are at the chemical bond of a continuous substance such as a hydrazine bond. , π straw from the organic interface, you a mountain 6 6 示 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米 米The nano chemical bond 1 soil θ "face' is made by an organic substance such as an oxygen bond. The average roughness of the nano-rough layer is introduced. The thickness of the nano-rough layer is between 〖5 1 ΠΛ and 丨 丨丨 to 〗 50 nm, preferably between 1 丨; 1 nm to 1 〇〇 nrn.兮太伞>. The particle size of the non-thermal machine is between 1 〇 nm and 1 〇〇 nm, preferably between 1 〇 and 50 legs. The hydrophobic coating is composed of a low surface energy material. Preferably, it is selected from the group consisting of 18301P01 8 1261615, fluorine and antimony, such as alkyl group-containing chi or silanes, fluorine:): complete trisulfide Fluoroalkyl group-containing trichlorosilanes, fluoroalkyl group-containing trialkoxysilanes, fluoroalkyl group-containing triacyloxysilanes Fluorinated triisoisocyanate S is a fluoroalkyl group-containing triisocyanate silanes, alkyl-group-containing alkoxy silanes, and a burn-containing group. The alkyl group-containing acyloxysilanes and one of: alkyl group-containing isocyanate silanes. The invention provides a method for preparing a hydrophobic structure on a surface of a substrate, comprising: providing a substrate, an organic-inorganic mixed material and a low surface energy material, coating an organic-inorganic blending material on the surface of the substrate, and sintering at a high temperature Forming a nano-rough layer on the surface of the substrate φ; and coating a low surface energy material to form a hydrophobic coating on the surface of the -: nano-bundle layer. The foregoing organic-inorganic blending material is a mixture of a nano inorganic substance and an organic polymer. Preferably, the nano inorganic system is one of a metal oxide and an inorganic compound. The metal oxide may be selected, for example, from one of the cerium oxides of the cerium oxide, the titanium oxide such as titanium dioxide, and the oxide of the oxidizing error. The inorganic compound is one selected from the group consisting of trimethyl ethoxy oxalate (TMOS), tetraethoxy decane (TEOS), and triethoxy titanium (TEOTi). The particle size of the nano-inorganic material is between 9 18301 P01 1261615 of 1 Onm to 1000 nm, and preferably the system is between 1 Onm and 50 nm. The organic polymer is a polymer compound having an alkenyl group, and its molecular weight ranges from 500 to 100,000, preferably from 5,000 to 75,000, and most preferably from 10,000 to 55,000. The polymer compound is one selected from the group consisting of polyethylene: ketone and polyvinyl alcohol. The organic-inorganic blend material contains from 1 to 50% by weight of the organic polymer. The organic-inorganic blend material is applied to the surface of the substrate at a wet film thickness of between 1 〇〇 nm and 10,000 nm, preferably between 100 nm and 500 nm. The nano inorganic substance controls the particle diameter of the oxide by acidity measurement, and forms a microphase-separated structure with the organic polymer by a sol-gel reaction. The acidity control system can be between pH 3 and 13, preferably between pH 7 and 13. The high temperature sintering temperature is between 300 ° C and 800 ° C. Preferably, the baking is achieved at a temperature between 300 ° C and 600 ° C. The low surface energy material is one selected from the group consisting of fluorine and rhodium. Preferably, the polymer is selected from the group consisting of alkyl group-containing chlorosilanes and fluoroalkyl group-containing trichlor〇silanes. ), fluoroalkyl group-containing trialkoxysilanes, containing fluoroalkyl group-containing triacyloxysilanes ^ fluoroalkyl group Fluoroalkyl group-containing triisocyanate silanes, alkyl group-containing alkoxysilanes, and agglomerated oxime oxides 10 18301P01 1261615 ° (alkyl gl〇 UP' C〇ntaining isocyanatesilanes) Medium-m is selected from the group consisting of a glass substrate, a material substrate and a metal substrate. And before (4) sintering, the complex may include a temperature curing step. The hydrophobic structure produced by the method of the present invention has an inorganic compound: the surface is a chemical bond, and the chemical bond is an oxygen bond. The nano inorganic material has a continuous phase structure, so the bamboo shoots, hydrophobicity, wear resistance, high permeability, and the mouth structure are excellent, and the preparation method can simplify the process and cost. And processing has its advantages, which in turn enhances the overall competitiveness of the industry. The other side = the structure is made of the composite properties of the nanocomposite, so that the rigidity of the machine material can also improve the toughness of the organic material. [Embodiment] Hereinafter, the features and effects of the present invention will be further described in detail by way of specific examples. However, the details of the implementation are merely illustrative of the invention and are not intended to limit the scope of the invention: j Example -~ Nano-rough layer manufacturing method and coating method: at room temperature, Imol The ratio Mm? is placed in a double neck round bottom bottle with 125 grams of ethanol, 5 grams of tetraethoxys (U) and 4.15 grams (36%) of hydrogen hydroxide, and the pots are evenly mixed 3 times. Make a clear solution in minutes. Then, under the condition of 18301P0] 11 1261615 ’, the reaction was carried out for 8 hours. When the reaction was completed, it was stirred at room temperature for 2 G hours to prepare an inorganic powder dispersion. Further, an organic solution was prepared by dissolving the polyethylene D of ίο克 in a ratio of slightly latitude ((10) yvinyi coffee; molecular weight 55 〇〇〇) to 19 gram of ethanol at room temperature (iv) for 0 minutes. Then, the inorganic solution and the organic solution were stirred at room temperature for 60 minutes at a volume ratio of 7:3 to form an organic-inorganic liquid required for coating. Rotary coating on the glass test piece by using a spin coater at a speed of 〇〇 rpm and a running time of 15 kPa each time to take 1.5 ml of the organic-inorganic mixed solution! Times. Next, the test piece was allowed to stand at room temperature for 20 hours to be aged at room temperature. Next, place the cured glass test piece in a high temperature oven and heat it from 25 c to 1 G (rc ' at 1 G (1 hour at rc; then heat it from 10 (rc to 6 s, then cool it naturally) To room temperature to form a glass sheet with a nano-layer of thick nano-chain. The above heating step is achieved by an upper temperature per minute method. The manufacturing method of the C-liter hydrophobic coating and the coating method of the low surface energy material: Under warming, put 23.7 grams of isopropyl alcohol and 1 gram of n-heptadecafluorodecyltrimeth〇xysiiane & 〇 in a double-necked round bottom bottle. 3 g of pure κ 75 mg of nitric acid (0.1 N), and stir it evenly for 2 hours to carry out the hydrolysis reaction. After the reaction is completed, add 5 g of 4A molecular sieve for dehydration and condensation] 8301 P〇i 12 1261615 := It was placed at room temperature for 18 hours. After completion of the reaction, the solution of the fluorocarbon alkane compound (FAS solution) was formed by filtration and paper core φ. Using a spin coater at a speed of 11 Torr, each time sucking μ - 1 , iUUlPm , rotating time 15sec on the glass, ~·,, $ liter of FAS solution to drip The condition T of the thick chain layer of the rice for 5 minutes was spin-coated on the glass test piece for 3 times. The work piece was placed in the box for 14 〇t: for baking! The test piece taken out is a substrate having and/or having a crucible and a mouth structure. The formed dichroic consisting of: "--hydrophobic coating hydrophobic structure scanning electron micrograph τ at the 10th, its atomic force The micrograph (AFM) is shown in Fig. 2. The first and second figures show that the method according to the present invention has a hydrophobic structure of the grade (four) grade, and the nematic layer of the hydrophobic structure is a continuous phase. The procedure of Example 1 was repeated, and polyvinylpyrrolidone # (f〇Iyviny Ipyrrolidone) was replaced by a molecular weight of 1 Torr, and the remaining steps were the same as in Example 1. The SEM results are shown in Fig. 3. Example 3 Under temperature, 50 g of ethanol, "tetraethoxySilane" and 3 · 〇 27 g (36 wt%) of concentrated hydrochloric acid were placed in a double-necked round bottom bottle and stirred evenly with a magnet. In an hour, an inorganic solution is obtained by additionally '10 g of polyvinylpyrrolidone (p〇Iyvinyl pyrrolidon) e; molecular weight 55000) and 19 gram of ethanol were stirred at room temperature at 18301 P0] 13 ^ 261 615 for 30 minutes to completely dissolve to prepare an organic solution. Next, the inorganic solution and the organic solution were placed in the chamber at a volume ratio of 7:3. Temperature: evenly stir for 60 minutes, so that the organic-inorganic mixed solution required for coating formation can be rotated at a speed of 1100 rpm and a rotation time of Msec at a rotation speed of 1 rpm: each time a 毫升5 ml of an organic/inorganic mixed solution is taken, Spin coating was applied once on the glass test piece. Next, the test piece was allowed to stand at room temperature for 2 hours to be aged at room temperature. Then, the matured glass test piece is placed in a high-temperature oven and maintained at UK 加热 = heated UKTcuocrc for 丄 hours; then from Λ, to 000C:, and then naturally cooled to room temperature to form And the glass layer of the too layer. The above heating step is achieved by rising every minute;:=two temperature method. The manufacturing method of low surface energy material and the coating method thereof: at room temperature, in the double neck round bottom bottle Into 23 7 grams of isopropanol # (isopropyulc0h0l), gram of n-hexadecafluorodecyltrimethoxydecane (heptadecafiuorodecyitrimeth〇xysilane) & 〇 3 grams of pure water and 75 mg of nitric acid (0.1 N) 'and The mixture was stirred for 2 hours, and the hydrolysis reaction was carried out. After the reaction was completed, 5 g of 4A molecular sieve was added to carry out dehydration and condensation polymerization, and it was allowed to stand at room temperature for 18 hours. After the reaction was completed, the molecular sieve was filtered with a filter paper to form fluorine. Alkane oxime compound solution (FAS solution) - Using a spin coater at a speed of 1100 卬 111, rotating time 'Each 1.5 mL of FAS solution per drop to the glass with a nano bond layer 18301P01 14 x 厶〇 1615 continued Chip Rotate and apply 3 times per coating interval λ. Under the condition of knife and buckle, the coating will be finished on the glass test piece. The sample taken out is placed in the boat... 4 (TC for baking! The hour is shown in Fig. 4. The substrate with a hydrophobic structure. The SEM results of the hydrophobic structure are analyzed by the following methods: 1, 2, 3 # 4 y, ... degree and pencil hardness test n " Contact angle, transparent 4" degree / shell", the test results are shown in Table 1. Maintain the level (the test piece needs to be flat, no distortion, near the surface), water, m2) drip from the micro-cylinder (as far as possible ^ / At the same time, the tip of the needle is still inside the water droplet (the center of the water droplet). The crying moves away from the syringe (the syringe is not shrinkable and moves violently, causing the volume/position change of the water droplet). The contact angle of the left and right sides of the water droplet is measured: Each time 'four total data. On the same substrate surface' find another four different positions, repeat the above steps, measure, a total of 2 data, and find the average. Transparency test - AS TM D ] 7 4 7 - 9 7 The size of the 6-piece piece is 50nim* 100mm, and the test piece first has the color difference of the integrating sphere. Measure the visible light transmittance (%). Under the temperature of 45±, place the test piece in the device, and make the test piece (A) and Blank (B) 230mm away from the light source, and use the UV irradiation device of CNS 10986. After illuminating the looo hour, measure the light transmittance (%) and calculate the difference (absolute value) of the visible light transmittance (❻/.) before and after the test. 15 18301P01 1261615 3363-92^ At ambient temperature 23 soil 2 ° C, relative humidity 50 soil 5 〇 / 〇, the test piece placed: super: 16 hours. The wrong pen is cut into a pointed tip with a shaving pen, smooth: round = paper, the pencil head is ground in the vertical direction, so that the pen is flat and without damage, and the pen is broken (5~6mm). From the hardest lead: the next two:) 'and then back' r to the first one. Test to (4) can not pierce the coating: 'Can be assisted by a magnifying glass; the pencil tip is the most microscopic pen in the process, and the hardness of the f layer. Repeat the test at least - the same time to the same result. p is
T 面 /、透明度及硬度也較其他習知的產品更為優I。、）’ 上述貫施例僅例示性說明本及 非用於限制本發明。任何熟h s /理及其功效，而 背本發明之精神及範疇下， 之人士均可在不違 變 範 。因此，本發明之權力保護範、广例進行修傅與改 圍所列。 h圍，應如後述之申請專利 I83〇lp〇] 16 1261615 【圖式簡單說明】 第1圖為實施例1所製得之疏水結構之電子 (SEM) 〇 顯微鏡圖 第2圖為實施例1所製得之疏水結構之原子力 圖（AFM)。 顯微鏡 第3圖為實施例2所製得之疏水結構之掃描 微鏡圖（SEM)。 田式t子顯 第4圖為實施例3所製得之疏水結構之掃插式 微鏡圖（SEM) 電子顯 l83〇lp〇l 17T surface / transparency and hardness are also superior to other known products. The above-described embodiments are merely illustrative of the present invention and are not intended to limit the present invention. Any person who is familiar with the singularity and its efficacy, and who is in the spirit and scope of the invention, may not violate the norm. Therefore, the power protection and the general examples of the present invention are set forth in the revision and revision. H, should be as described later, the patent application I83〇lp〇] 16 1261615 [Simple description of the drawings] Figure 1 is the electron (SEM) of the hydrophobic structure prepared in Example 1 〇 microscope image Figure 2 is the first embodiment Atomic force diagram (AFM) of the resulting hydrophobic structure. Microscope Fig. 3 is a scanning micromirror (SEM) of the hydrophobic structure prepared in Example 2. Fig. 4 shows the sweeping type of the hydrophobic structure prepared in Example 3 (SEM) electronic display l83〇lp〇l 17