201035259 六、發明說明： 【發明所屬之技術領域】 種耐候自潔 本發明係有關於塗層’且特別是有關於 塗層。 【先前技術】 Ο ❹ 自潔（self-cleaning)塗層由於具有超低表面▲匕 污垢之附著，使表面常保清潔，因此能應用作避免 或撥水塗料。然而由於超低表面能的關係，卜防污 材之間的接著性極差，使用壽命無法延長，層與基 戶外之塗層疏水性會隨著使用時間之增加而逐漸降H 亞洲南>5染、高溫高熱的氣候下，建築-在 就有污染產生。 ^@1個月 德國專利腦7725U為表面自潔之創始料 出微結構與疏水材料結合的自潔材料，但是 ^ & 著性不佳且機械強度不足。 、”，在於，、附 歐洲專利ΕΡ 164〇419揭蒙—錄6、知太店 將黏胸與樹脂相混，之後進= 著性佳，但是自織果㈣^^錢㈣製得，其接 =專利TW4傷4利式形絲汚薄膜，可 于J低表面能結構，但其無法製作成塗層。 揭露1自組㈣自潔塗層’藉 :=式改質奈米粒子，再加上有機樹脂形成自潔塗 果較=而其添加有機樹脂之接觸角不超過145纟，自潔效 3 201035259 曰本專利JP 2005343924利用親水性方式製作自潔塗 層，雖然親水性塗層較無接著性問題，但是其防汚性效果 較一般疏水性塗層差。 為了解決塗層與基材之間的接著性的問題，以及增加 塗層之耐候性，業界亟需提出一種接著性佳之耐候自潔的 塗層。 【發明内容】 0 本發明提供一種耐候自潔塗層，包括：一基材；一高 而寸候底漆塗層’位於該基材之上，其中該局耐候底漆塗層 至少包括高耐候樹脂或無機成份添加劑；以及一高接觸角 塗層，位於該高耐候底漆塗層之上，其中該高接觸角塗層 之水接觸角大於約130度。 本發明另提供一種耐候自潔塗層之形成方法，包括以 下步驟：提供一基材；塗佈一南财候底漆塗層於該基材之 上，其中該高耐候底漆塗層至少包括高耐候樹脂或無機成 © 份添加劑；乾燥或固化該高耐候底漆塗層；塗佈一高接觸 角塗層於該高耐候底漆塗層之上；以及乾燥或固化該高接 觸角塗層，其中該高接觸角塗層之水接觸角大於約130度。 為讓本發明之上述和其他目的、特徵、和優點能更明 顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳 細說明如下： 【實施方式】 201035259 本發明提供一種耐候自.、替淨θ 矢目，絜塗層1〇〇，請參見第 包括：-基材10,其可包括水、、尸 b見弟1圖其 i祜水泥、石材、木材、玻璃、 膠、金屬、陶U高分不柯玻瑪塑 …、向基材10之選擇並不以此為 限，亦可使用其他材質；^ ^ 1Λ L . ^ 一 回耐候底漆塗層20，位於基材 10之上，以及一尚接觸角塗声 一 20之上。 θ 30，位於尚耐候底漆塗層 上述之高而t候底漆塗層2n + r~ —丄 /+ , ^ 土增20之厚度為約1〜500 μπι，較201035259 VI. Description of the invention: [Technical field to which the invention pertains] Weather-resistant self-cleaning The present invention relates to coatings' and in particular to coatings. [Prior Art] Ο self Self-cleaning coatings can be used as a avoidance or water-repellent coating due to the adhesion of ultra-low surface ▲ 污 dirt to keep the surface clean. However, due to the ultra-low surface energy relationship, the adhesion between the anti-fouling materials is extremely poor, the service life cannot be extended, and the hydrophobicity of the coating between the layer and the base outdoors gradually decreases with the increase of the use time. 5 In the climate of dyeing, high temperature and high heat, the building - there is pollution. ^@1 month The German patent brain 7725U is a self-cleaning material that combines microstructure and hydrophobic materials for the self-cleaning of surface self-cleaning, but ^ & poor performance and insufficient mechanical strength. ",,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Connect = patent TW4 injury 4 Lee-shaped silk film, can be used in J low surface energy structure, but it can not be made into a coating. Exposure 1 self-group (four) self-cleaning coating 'borrow: = modified nano particles, and then Adding organic resin to form self-cleaning coating fruit = and its contact angle of adding organic resin is not more than 145 纟, self-cleaning effect 3 201035259 曰 Patent JP 2005343924 uses hydrophilic method to make self-cleaning coating, although hydrophilic coating There is no adhesion problem, but its antifouling effect is worse than that of general hydrophobic coating. In order to solve the problem of adhesion between coating and substrate, and increase the weather resistance of coating, the industry needs to propose a good adhesion. Weather-resistant self-cleaning coating. [Invention] The present invention provides a weather-resistant self-cleaning coating comprising: a substrate; a high-priming primer coating is disposed on the substrate, wherein the weathering resistance is The lacquer coating includes at least a high weathering resin or an inorganic component additive; And a high contact angle coating on the high weathering primer coating, wherein the high contact angle coating has a water contact angle greater than about 130 degrees. The present invention further provides a method for forming a weather resistant self-cleaning coating, including The following steps: providing a substrate; coating a south weathering primer coating on the substrate, wherein the high weathering primer coating comprises at least a high weathering resin or an inorganic additive; drying or curing the high a weathering primer coating; coating a high contact angle coating on the high weathering primer coating; and drying or curing the high contact angle coating, wherein the high contact angle coating has a water contact angle greater than about 130 The above and other objects, features, and advantages of the present invention will become more apparent and understood. Provide a weather-resistant, tidy θ-yellow, 絜 coating 1 〇〇, see the inclusion: - substrate 10, which can include water, corpse b see brother 1 figure its i 祜 cement, stone, wood, Glass, glue, metal, ceramic U high scores ..., the choice of the substrate 10 is not limited thereto, and other materials can be used; ^ ^ 1Λ L . ^ A weather resistant primer coating 20, located on the substrate 10, and a contact angle coating Above 20. θ 30, located in the above-mentioned high-grade primer coating 2n + r~ —丄/+ , ^ soil thickness 20 thickness is about 1~500 μπι,
佳為約5〜50 μιη ’其包括宾科枝从 __ ° $候樹脂或無機添加劑，其中 南耐候樹脂佔高财候底漆f > 食罜層20之比例為約5-70重量％， 較佳為約10-40重量〇/0，里白虹廊上 ”已括屢克力樹脂（acrylic resin)、 石夕利康樹脂（smcone resin)、月旨肪族環氧樹脂（御⑽ epoxy resin)、脂肪族聚胺_樹脂⑽沖此p〇i声拙咖 _)、上述之衍生物、或上述之纽合。而無機添加劑至少 佔南耐候底漆塗層2G之比例3()%重量以上，為約3㈣Good for about 5~50 μιη 'It includes a branch of Benzene from __ ° $ resin or inorganic additives, of which South weather resistant resin accounts for high-currency primer f > chyme layer 20 ratio is about 5-70% by weight Preferably, it is about 10-40 weights 〇/0, and the white rainbow porch has been included in the acrylic resin, smcone resin, and the moon-based aliphatic epoxy resin (10) epoxy resin. ), aliphatic polyamine _ resin (10) rushed to this p〇i 拙 拙 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Above, about 3 (four)
重量％，較佳為約60-90重量％，其包括二氧化石夕（si〇2)、 二氧化鈦(Ti〇2)、錢舞（CaC()3)、氧化鋅（Ζη〇)、氧化铭 (AlxOy)、黏土（clay)、二氧化鍅(Zr〇)、氧化鐵(F^〇y)或上 述之組合。此外，高耐候底漆塗層2〇之高耐候樹脂或無機 添加劑具有下列至少一種能與該高接觸角塗層3〇產生化 學鍵結之官能基：OH、COOH、NH2、CONH2、NCO、SH、 乙炸基、壤氣基、或上述之組合。 此處需注意的是，由於高耐候底漆塗層20之成份中包 括高強度鍵結，例如Si-Ο鍵結，此鍵能為約452 KJ/mol， 其相較於一般有機成份，例如C-N(73 KJ/mol)、C-0(358 .201035259 KJ/mol)之鍵能高，因此，能提高底漆塗層之耐候性。 上述之南接觸角塗層30包括一疏水劑，一微米或奈米 粒子與一微結構形成助劑，其厚度為約0.2〜5〇〇 μιη，較佳 為約5〜50 μιη。其中疏水劑包括矽系疏水劑、氟系疏水劑 或長鏈碳氫化合物；而微米或奈米粒子具有SiR、TiR、ZnR 或 AIR 官能基，其中 r 為 〇H、COOH、NH2、CONH2、 NCO、SH、乙烯基或環氧基，例如商用之矽土微粒，且微 米或奈米粒子之粒徑為1 nm-100 μιη;而微結構形成助劑 Ο 包括官能化烧氧基石夕烧(functional alkoxysilane)、胺基三烧 氧基矽烷(amino trialkyoxysilane)或鹼性化合物。高接觸角 塗層30之製作方法如下，首先提供一微米或奈米粒子，接 著以疏水劑與微結構形成助劑處理上述微粒，或以黏著劑 或交聯劑處理微粒結構，關於高接觸角塗層30之詳細組成 與製法請參考台灣專利公開號200621919與200621920。 由上述方法製得之高接觸角塗層30，其具有高疏水、 疏油特性’其水接觸角大於約13〇度，較佳大於約150度， ® 而其一蛾甲烧接觸角大於約130度，較佳大於約150度。 本發明之技術特徵在於，藉由底漆塗層20具有下列至 少一種此與該局接觸角塗層30產生化學键結之官能基： OH、COOH、NH2、CONH2、NCO、SH、乙烯基、環氧基、 或上述之組合’讓上述官能基與高接觸角塗層3〇之官能 基，例如 OH、COOH、NH2、CONH2、NCO、SH、乙烯基、 環氧基、或上述之组合，兩者之間產生化學鍵結，因而提 高高接.觸角塗層30與基材1〇之附著性，進而延長高接觸 角塗層30之使用壽命。 6 201035259 此處須注意的是，習知技術中，由於高接觸角塗層3〇 為低表面能材料，其與基材1 〇之間的接著性不佳，因此， 本發明藉由高耐候底漆塗層20 ’用以增加基材10與高接 觸角塗層30之間的接著性。 本發明之耐候自潔塗層經過耐刷洗測試，經過astm D2486之1000次以上之刷洗次數，其水接觸角仍大於13〇 度。另外’本發明之耐候自潔塗層經過ASTM G154紫外線 耐候測試，在照光600小時以上，其水接觸角仍大於13〇 ^ 度’且滑落角（sliding angle)仍小於5度。由此可知，本發 明之耐候自潔塗層不但具有高度耐刷洗特性，且具有優異 的耐候特性，因此特別適合應用於建築塗料，其他可能的 應用包括交通工具、無線通訊、衛浴、究磚、紡織、光學 工業或表面處理等行業。 本發明之弟一貫施例’请參見第2圖，其為.一種隔熱 耐候自潔塗層200 ’其中標號與第1圖相同者代表相同結 ❹ 構’在此不再贅述’其主要差別在於基材10與底漆塗層 20之間尚包括一隔熱塗層15，此隔熱塗層15可為市售之 隔熱塗料’藉由此隔熱塗層15之幫助，可使此耐候自潔塗 層200具有不錯之隔熱效果，其熱傳導小於約〇.2 w/m。 本發明另外提供一種耐候自潔塗層之形成方法，請參 見第1圖’包括以下步驟：提供一基材1〇，其中基材10 之選擇同前所述。塗佈一高耐候底漆塗層20於基材1〇之 上’其厚度為約1〜500 μιη ’較佳為約5〜50 μιη，其包括高 耐候樹脂’例如壓克力樹脂（acrylic resin)、梦利康樹脂 (silicone resin)、脂肪族ί哀氧樹脂（aHphatic epoxy resin)、脂 •201035259% by weight, preferably about 60-90% by weight, including magnet dioxide (si〇2), titanium dioxide (Ti〇2), Qianwu (CaC()3), zinc oxide (Ζη〇), oxidation (AlxOy), clay, cerium oxide (Zr 〇), iron oxide (F^〇y) or a combination thereof. In addition, the high weathering resistant coating of the high weathering resistant resin or inorganic additive has at least one of the following functional groups capable of chemically bonding with the high contact angle coating: OH, COOH, NH2, CONH2, NCO, SH, B. Fried base, ground gas base, or a combination of the above. It should be noted here that since the composition of the high weathering primer coating 20 includes high strength bonding, such as Si-Ο bonding, the bond energy is about 452 KJ/mol, which is compared to general organic components, for example. The bond energy of CN (73 KJ/mol) and C-0 (358 .201035259 KJ/mol) is high, and therefore, the weather resistance of the primer coating can be improved. The south contact angle coating 30 described above comprises a hydrophobic agent, a micron or nanoparticle and a microstructure forming aid having a thickness of about 0.2 to 5 μm, preferably about 5 to 50 μm. The hydrophobic agent includes a lanthanide hydrophobic agent, a fluorine-based hydrophobic agent or a long-chain hydrocarbon; and the micro- or nano-particle has a SiR, TiR, ZnR or AIR functional group, wherein r is 〇H, COOH, NH2, CONH2, NCO , SH, vinyl or epoxy, such as commercial alumina particles, and micron or nano particles having a particle size of 1 nm to 100 μm; and microstructure forming aids including functionalized activating oxygen Alkoxysilane), amino trialkyoxysilane or a basic compound. The high contact angle coating 30 is produced by first providing one micron or nanoparticle, followed by treating the microparticles with a hydrophobic agent and a microstructure forming aid, or treating the particulate structure with an adhesive or a crosslinking agent, with respect to a high contact angle. For detailed composition and preparation of the coating 30, please refer to Taiwan Patent Publication Nos. 200621919 and 200621920. The high contact angle coating 30 produced by the above method has a high hydrophobicity and oleophobic property, and its water contact angle is greater than about 13 degrees, preferably greater than about 150 degrees, and the contact angle of a moth beating is greater than about 130 degrees, preferably greater than about 150 degrees. The present invention is characterized in that the primer coating 20 has at least one of the following functional groups which are chemically bonded to the local contact angle coating 30: OH, COOH, NH2, CONH2, NCO, SH, vinyl, An epoxy group, or a combination thereof, is a combination of a functional group of the above functional group and a high contact angle coating layer, such as OH, COOH, NH2, CONH2, NCO, SH, a vinyl group, an epoxy group, or a combination thereof. A chemical bond is formed between the two, thereby improving the adhesion of the high contact. The tentacles 30 to the substrate 1 and thereby prolonging the service life of the high contact angle coating 30. 6 201035259 It should be noted here that in the prior art, since the high contact angle coating 3 〇 is a low surface energy material, the adhesion between the substrate and the substrate 1 不 is poor, and therefore, the present invention is highly weather resistant. The primer coating 20' serves to increase the adhesion between the substrate 10 and the high contact angle coating 30. The weather-resistant self-cleaning coating of the present invention has been subjected to a brush-resistant test, and the water contact angle of the astm D2486 is more than 13 degrees. Further, the weather-resistant self-cleaning coating of the present invention was subjected to the ASTM G154 ultraviolet weathering test, and the water contact angle was still greater than 13 〇 ^ degrees and the sliding angle was still less than 5 degrees after illumination for more than 600 hours. It can be seen that the weather-resistant self-cleaning coating of the invention not only has high scrubbing resistance, but also has excellent weather resistance, so it is particularly suitable for use in architectural coatings, and other possible applications include transportation, wireless communication, sanitary ware, brick, Textile, optical industry or surface treatment industries. The invention of the present invention consistently applies 'see FIG. 2, which is an insulated and weather-resistant self-cleaning coating 200', wherein the same reference numerals as in the first drawing represent the same structure, and the main difference is not described here. Between the substrate 10 and the primer coating 20, a thermal barrier coating 15 is also included. The thermal barrier coating 15 can be a commercially available thermal barrier coating. The weather-resistant self-cleaning coating 200 has a good thermal insulation effect with a heat transfer of less than about 〇2 w/m. The present invention further provides a method of forming a weather-resistant self-cleaning coating, see Fig. 1 'comprising the steps of providing a substrate 1 in which the substrate 10 is selected as described above. Coating a high weathering primer coating 20 on the substrate 1' with a thickness of about 1 to 500 μm, preferably about 5 to 50 μm, including a high weather resistant resin such as acrylic resin ), silicone resin, aHphatic epoxy resin, fat•201035259
肪族聚胺酯樹脂（aliphatic polyurethane resin)、上述之衍生 物、或上述之组合。此外，高耐候底漆塗層20尚可添加無 機添加劑’例如二氧化矽（Si02)、二氧化鈦(Ti〇2)、碳酸鈣 (CaC03)、氧化鋅（ZnO)、氧化銘（AlxOy)、黏土（clay)、二氧 化锆(ZrO)、氧化鐵(Fex〇y)或上述之組合。藉由高耐候底漆 塗層.20之成份，例如Si-Ο鍵結（鍵能為約452 KJ/mol)，其 相較於一般有機成份，例如C-N(73 KJ/mol)、C-0(358 KJ/mol)之鍵能咼’因此’能提高底漆塗層2〇之耐候性。 此外，高耐候底漆塗層20之高耐候樹脂或無機添加劑之官 能基包括 OH、C00H、NH2、CONH2、NCO、SH、乙烯基、 環氧基、或上述之組合。 而高耐候底漆塗層20所選擇之溶劑包括醇類、水、酯 類、醚類、苯衍生物，然而溶劑之選擇並不以此為限，' 要能將底漆成份均勻分散、溶解之溶劑皆可使用。之後爹 燥或固化高耐候底漆塗層2〇，經過乾燥或固化步驟之後^ 高耐候底漆塗層20之固含量為約1〇〜95〇/〇。 接著塗佈―高接觸角塗層30於底漆塗層2〇之 中高接觸角塗層30之厚度為約〇2〜5〇〇μπι，較佳為約其 μιη’其中*接觸角塗層3〇之材料與其製備方式、5〇 在此不再贅述。以及乾燥或固化高接觸肖塗層30，4 ’ 燥或固化步驟之後，高接觸角塗層3()之 :過乾 %。 里為約1〜6〇 本發明之技術特徵在於，藉由底漆塗層2〇 高接觸角塗層3Q之間產生化學鍵結，因而 ^基與 高接觸角塗層30之間的妓裟以e ^ 土材10與 之間的接者性，進而延長高接觸角塗層 8 .201035259 30之使用壽命。 此外，可於塗佈高耐候底漆塗層2〇於基材1〇之前， 另塗佈一隔熱塗層15於基材1〇之上，此隔熱塗層可為市 售之隔熱材料，其可提高耐候自潔塗層之隔熱效果。 上述提及之塗佈方式為溶液塗佈方法’其包括旋轉塗 佈（spin coating)、棒狀塗佈（bar coating)、浸潰塗佈（dip coating)、滾同塗佈（roll coating)、喷霧塗佈（spray coating)、 凹版式塗佈(gravure coating)、喷墨印刷（ink jet printing)、 ❹狹縫塗佈（sl〇t coating)或刮刀塗佈（blade coating)。上述提及 之所有乾燥或固化之步驟係於室溫下至2 〇 〇 °C的溫度下進 行，然而，熟知此技藝之人士應得知，乾燥或固化的溫度 會隨著塗層的種類、化學品固化的條件與塗層之厚度而改 變。 綜上所述’本發明之耐候自潔塗層可以提供之優點在 於藉由高耐候底漆塗層與高接觸角塗層產生化學鍵結，增 ❹加基材與高接觸角塗層之間的接著性，進而延長高接觸角 塗層之使用壽命，使得耐候自潔塗層具有高度耐刷洗特性 與耐候特性。此外’於基材與高耐候底漆塗層之間增加隔 熱塗層，能提供額外之隔熱效果。 【實施例】 實施例1 混合15 g二氧化鈦(Ti〇2)、65 g含有官能基之Si〇2 粒子、10 g壓克力樹脂與10 g矽利康樹脂（無機成份共佔 80 /〇)’在室溫下攪拌一小時’以喷塗方式均勻噴塗於水泥 9 201035259 板或聚氯乙烯(poly vinyl chloride, PVC)板表面，室溫下乾 燥24小時，以製得一底漆塗層。 混合 4 g 四乙氧基矽烷(tetraethoxySiiane, TE0S)、1.5 g 2·胺基-2-曱基胺(AMP)、20 g乙醇與ΐ·ι g水，再加入2 g 氨水（ammonia water)與0.6g的聚二甲基石夕氧烷（poly dimethylsiloxane, PDMS)後，於室溫下反應24小時，再加 入1.2g之3,4-環氧基環己基甲基-3,4-環氧基環己烷碳酸酯 (3,4-epoxycy clohexylmethyl Ο 3,4-epoxycyclohexanecarboxylate)，室溫下反應；[小時。以 喷塗方式均勻噴塗於底漆塗層之上，室温下乾燥24小時， 以製得一财候自潔塗層。 實施例2 同實施例1，但底漆塗層更換成具有COOH之壓克力 樹脂60g與Ti02 40g與水混合均勻（無機成分佔40%)。 〇 實施例3 同實施例1 ’但不添加3,4-環氧基環己基曱基_3,4-環氧 基樣己娱《碳酸酯（3,4-Epoxycyclohexyl 瓜 ethyl 3,4-epoxycyclohexanecarboxylate) ° 比較例1 同實施例1，但不添加底漆塗層。 比較例2 10 201035259 同實施例1，但底漆塗層更換成為氟素系統之德亞樹脂 的 NEW GAMET 2300。 比較例3 同貫施例1但將3,4-環氧基環己基曱基从環氧基環 己烧石反酉文 3 曰(3,4-ep〇xycyclohexylmethyl 3，4-eP〇Xycydohexanecarboxylate)改為雙酚 a 二環氧甘油醚 (bisphenol A diglycidyl ether) ° ο 比較例4 同實施例1，但更改咼接觸角塗層。高接觸角塗層之製 備方式如下：混合4 g商用矽土微粒（163〇s長春石化；固 含量30 %，粒徑16 nm)、1,5 g 2-胺基-2-曱基-1-丙醇 (AMP-95)、21 g乙醇與1.1 g水’在室溫下反應30分鐘， 之後加入0.75 g聚一甲基石夕氧院(poly dimethylsiloxane, PDMS)與0.75 g 3-氨基丙基三乙氧基曱矽烷 ❹ （3-aminopropyl)triethoxysilane，APS)，控制 pH 值在 10-13 間，在室溫下反應4天’即可製得高接觸角塗層。之後以 喷塗方式均勻喷塗於底漆塗層之上，在室溫下乾燥24小 時，以製得一耐候自潔塗層。 比較例5 市售耐候塗料德亞樹脂之NEW GAMET 2300，以喷塗 方式均勻喷塗於水泥板或聚氯乙烯（poly vinyl chloride, PVC)板表面，室溫下乾燥24小時，以製得一财候塗層。 201035259 將實施例1〜3與比較例1〜5之塗層，以下述方式進行 評估’所得結果列於表1、表2 : 接觸角：以接觸角量侧儀（AST Product，Inc.型號 OPTIMA XE)量測其接觸角，水滴體積2.5μ1。 耐刷洗測試：測試方式ASTM D2486，設備廠商Sheen Instrument LTD，型號 Wet abrasion scrub tester 903。 紫外線耐候測試：測試方式ASTM G154，設備廠商 〇 Altas，型號 UV 2000。 表1 水接觸角 刷洗次數 0次 100次 1000 次 2000 次 4000 次 實施例1 >155。 149。 145° 142° 130° 實施例2 >155。 148。 138。 138。 133。 實施例3 >155。 145° 138。 130。 130。 比較例1 >155。 120。 <100。 < 100° <100。 比較例2 >155。 126° < 100° <100。 < 100° 比較例3 >155。 146° 140。 143。 145。 比較例4 138° 119。 < 100° <100。 < 100° 比較例5 84.54° 83.5° 78.2° 75.6° 73.Γ 12 201035259 表2An aliphatic polyurethane resin, a derivative thereof, or a combination thereof. In addition, the high weathering primer coating 20 can be added with inorganic additives such as cerium oxide (SiO 2 ), titanium dioxide (Ti 〇 2 ), calcium carbonate (CaC03), zinc oxide (ZnO), oxidized (AlxOy), clay ( Clay), zirconium dioxide (ZrO), iron oxide (Fex〇y) or a combination thereof. By the composition of the high weathering primer coating .20, for example Si-Ο bond (bond energy is about 452 KJ/mol), compared to general organic components, such as CN (73 KJ/mol), C-0 The bond of (358 KJ/mol) can improve the weatherability of the primer coating. Further, the functional base of the high weathering resistant resin or inorganic additive of the high weathering primer coating 20 includes OH, C00H, NH2, CONH2, NCO, SH, vinyl, epoxy, or a combination thereof. The solvent selected for the high weathering primer coating 20 includes alcohols, water, esters, ethers, and benzene derivatives. However, the choice of solvent is not limited to this, 'to be able to uniformly disperse and dissolve the primer components. The solvent can be used. Thereafter, the high weathering primer coating is dried or cured. After the drying or curing step, the solid content of the high weathering primer coating 20 is about 1 〇 to 95 Å/〇. Then coating the "high contact angle coating 30" in the primer coating layer 2, the thickness of the high contact angle coating layer 30 is about 〜2~5〇〇μπι, preferably about μηη' where *contact angle coating 3 The materials of the crucible and the preparation method thereof are not repeated here. And after drying or curing the high contact Shaw coating 30, 4 ' drying or curing step, the high contact angle coating 3 (): over dry %. The invention is characterized in that it is about 1 to 6 〇. The technical feature of the present invention is that a chemical bond is formed between the primer layer 2 〇 high contact angle coating 3Q, and thus the 之间 between the base and the high contact angle coating 30 is e ^ The connection between the soil material 10 and the service life of the high contact angle coating 8.201035259 30. In addition, before applying the high weathering primer coating 2 to the substrate, a thermal barrier coating 15 may be applied on the substrate 1 , which may be a commercially available thermal insulation coating. A material that enhances the thermal insulation of the weather-resistant self-cleaning coating. The coating method mentioned above is a solution coating method which includes spin coating, bar coating, dip coating, roll coating, Spray coating, gravure coating, ink jet printing, slit coating or blade coating. All of the drying or curing steps mentioned above are carried out at room temperature to 2 ° C. However, those skilled in the art will recognize that the drying or curing temperature will vary with the type of coating, The conditions under which the chemical cures vary with the thickness of the coating. In summary, the weather-resistant self-cleaning coating of the present invention can provide the advantage of chemical bonding between a high weathering primer coating and a high contact angle coating, between the substrate and the high contact angle coating. Subsequent, thereby extending the service life of the high contact angle coating, so that the weather-resistant self-cleaning coating has high scrub resistance and weather resistance. In addition, the addition of a thermal barrier between the substrate and the high weather-resistant primer coating provides additional insulation. EXAMPLES Example 1 15 g of titanium dioxide (Ti〇2), 65 g of functional group-containing Si〇2 particles, 10 g of acrylic resin and 10 g of lycopene resin (inorganic component of 80 /〇) were mixed. Stir at room temperature for one hour. Spray evenly on the surface of cement 9 201035259 plate or polyvinyl chloride (PVC) plate and dry at room temperature for 24 hours to obtain a primer coating. Mix 4 g of tetraethoxySianee (TE0S), 1.5 g of 2,amino-2-mercaptoamine (AMP), 20 g of ethanol and ΐ·ι g water, then add 2 g of ammonia water and After 0.6 g of polydimethyl dimethyl siloxane (PDMS), react at room temperature for 24 hours, and then add 1.2 g of 3,4-epoxycyclohexylmethyl-3,4-epoxy. 3,4-epoxycy clohexylmethyl Ο 3,4-epoxycyclohexanecarboxylate, reaction at room temperature; [hour. It was sprayed evenly on the primer coating and dried at room temperature for 24 hours to obtain a self-cleaning coating. Example 2 Same as Example 1, except that the primer coating was changed to an acrylic resin having COOH. 60 g of the resin and 40 g of TiO 2 were uniformly mixed with water (inorganic component accounted for 40%). Example 3 Same as Example 1 'but without adding 3,4-epoxycyclohexyldecyl_3,4-epoxy-like octopus carbonate (3,4-Epoxycyclohexyl melon ethyl 3,4-epoxycyclohexanecarboxylate ° Comparative Example 1 Same as Example 1, but without the addition of a primer coating. Comparative Example 2 10 201035259 Same as Example 1, but the primer coating was replaced with NEW GAMET 2300 which became the De-resin of the fluorine system. Comparative Example 3 Coherent Example 1 but 3,4-epoxycyclohexylfluorenyl from 3,4-ep〇xycyclohexylmethyl 3,4-eP〇Xycydohexanecarboxylate Change to bisphenol A diglycidyl ether ° ο Comparative Example 4 Same as Example 1, except that the 咼 contact angle coating was modified. The high contact angle coating was prepared as follows: 4 g of commercial alumina particles (163 〇s of Changchun Petrochemical; solid content 30%, particle size 16 nm), 1,5 g 2-amino-2-mercapto-1 -propanol (AMP-95), 21 g of ethanol and 1.1 g of water' were reacted at room temperature for 30 minutes, after which 0.75 g of polydimethyl dimethyl siloxane (PDMS) and 0.75 g of 3-amino propylene were added. 3-aminopropyltriethoxysilane (APS), which controls the pH between 10 and 13 and reacts at room temperature for 4 days, can produce a high contact angle coating. Then, it was sprayed evenly on the primer coating and dried at room temperature for 24 hours to obtain a weather-resistant self-cleaning coating. Comparative Example 5 NEW GAMET 2300, a commercially available weathering resistant coating, was sprayed onto the surface of a cement board or a polyvinyl chloride (PVC) board and dried at room temperature for 24 hours to obtain a Financial coating. 201035259 The coatings of Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated in the following manners. The results obtained are shown in Table 1, Table 2: Contact angle: side angle meter (AST Product, Inc. model OPTIMA) XE) The contact angle was measured and the volume of water droplets was 2.5 μl. Washing resistance test: test method ASTM D2486, equipment manufacturer Sheen Instrument LTD, model Wet abrasion scrub tester 903. UV weathering test: Test method ASTM G154, equipment manufacturer 〇 Altas, model UV 2000. Table 1 Water contact angle Number of brushing 0 times 100 times 1000 times 2000 times 4000 times Example 1 > 155. 149. 145° 142° 130° Example 2 > 155. 148. 138. 138. 133. Example 3 > 155. 145° 138. 130. 130. Comparative Example 1 > 155. 120. <100. < 100 ° < 100. Comparative Example 2 > 155. 126° < 100° < 100. < 100° Comparative Example 3 > 155. 146° 140. 143. 145. Comparative Example 4 138 ° 119. < 100 ° < 100. < 100° Comparative Example 5 84.54° 83.5° 78.2° 75.6° 73.Γ 12 201035259 Table 2
水接觸角 紫外線測試 100 hr 200 hr 600 hr 實施例1 〇 〇 〇 實施例2 〇 〇 X 實施例3 〇 〇 〇 比較例1 X X X 比較例2 X X X 比較例3 X X X 比較例4 〇 X X 〇：合格，滑落角< 5° ，且接觸角> 130° X :不合格，滑落角> 5° ，且接觸角< 130° 表1為實施例1〜3與比較例1〜5經過刷洗測試之實驗 結果，結果顯示，只有實施例1〜3與比較例3可承受ASTM D2486 1000次以上之刷洗。 > 比較例1由於沒有底漆，基材與高接觸角塗層間接著 性差，财刷洗性差。比較例2底漆為說素樹脂無法於面漆 產生化學鍵結，所以耐刷洗性差。比較例3添加非耐候之 雙驗 A 二環氧甘油醚(Bisphenol A diglycidyl ether)，雖然 可以通過耐刷洗測試，但在表2之QUV測試中無法通過 100hr以上之測試。比較例4是由市售silica由於SiOH含 量少，再加上接觸角低，所以接著性與自潔性較差。比較 * 例5為一般耐候塗料，雖然可以通過2000小時以上之耐候 13 201035259 效果，但是沒有自潔能力，接觸角僅有85度。 Ο 表2為實施例1〜3與比較例1〜4之照射時間對水 接觸角之關係圖，當水接觸角約大，表不疏水效果越佳。 其中實施例1〜3經過QUV照射200小時以上之測試，尤其 實施例1、3由於採用無機成份較向之添加劑與耐候樹月旨、， 所以耐候性最高。實施例2僅無機成份較低之添加創與耐 候樹脂，所以QUV僅可以通過200hr，其水接觸角仍大於 13〇度；而比較例1〜3無法經過QUV P、?、射1〇〇小時，其水 接觸角已經降低至130度以下；而比較例4由於接著性與 自潔性差，所以無法通過QUV照射200小時測試。 ’、 由表1〜2實驗結果得知’本發明實施例1〜3之耐候自 潔塗層不但具有高度耐刷洗特性，且具有優異的耐候特性。 實施例4 同貝把例1，差別在於底漆畫層之前，塗佈商用隔熱漆 水°己水性财熱漆），刷塗塗饰約500 μιη，室溫下乾燥24小 時，之後再依序塗佈實施例！所述的各層。 & 3列出一般鬲分子、實施例1與實施例4之熱傳導 此力’只驗結果减不’相較於一般高分子與實施例i (不含 ^熱塗層），實施例4 (具有隔熱塗層）之隔熱效果最佳，其 熱傳導小於G.2 W/m ’且其全太陽熱反射率（TSR)大於80 %。 201035259 表3 一般高分子 實施例1 實施例4 (不含隔 (具有隔熱 熱塗層） 塗層） 熱傳導(W/m) 0.3 〜0.8 0.96 0.13 〜0.2 TSR - 〜75 % > 80 % (total solar reflection) 水接觸角 <100。 >150。 > 150° 雖然本發明已以數個較佳實施例揭露如上，然其並非 用以限定本發明，任何所屬技術領域中具有通常知識者， 在不脫離本發明之精神和範圍内，當可作任意之更動與潤 飾，因此本發明之保護範圍當視後附之申請專利範圍所界 定者為準。Water contact angle UV test 100 hr 200 hr 600 hr Example 1 〇〇〇 Example 2 〇〇X Example 3 〇〇〇Comparative Example 1 XXX Comparative Example 2 XXX Comparative Example 3 XXX Comparative Example 4 〇XX 〇: Qualified, Slip angle < 5°, and contact angle > 130° X : unacceptable, slip angle > 5°, and contact angle < 130° Table 1 is a brush test of Examples 1 to 3 and Comparative Examples 1 to 5 As a result of the experiment, it was revealed that only Examples 1 to 3 and Comparative Example 3 can withstand ASTM D2486 1000 or more brushing. > In Comparative Example 1, since there was no primer, the adhesion between the substrate and the high contact angle coating was poor, and the cleaning performance was poor. In the comparative example 2, the primer resin was incapable of producing a chemical bond in the top coat, so that the brushing resistance was poor. Comparative Example 3 added a non-weatherable Bisphenol A diglycidyl ether. Although it was able to pass the scrub resistance test, it was not able to pass the test of 100 hr or more in the QUV test of Table 2. In Comparative Example 4, since commercially available silica has a small content of SiOH and a low contact angle, the adhesion and self-cleaning property are inferior. Comparison * Example 5 is a general weathering coating. Although it can pass the weather resistance of more than 2000 hours 13 201035259, it has no self-cleaning ability and the contact angle is only 85 degrees. Ο Table 2 is a graph showing the relationship between the irradiation time and the water contact angle of Examples 1 to 3 and Comparative Examples 1 to 4. When the water contact angle is about large, the surface non-hydrophobic effect is better. Among them, Examples 1 to 3 were tested by QUV irradiation for 200 hours or more, and in particular, Examples 1 and 3 have the highest weather resistance due to the use of an inorganic component and a weathering tree. In Example 2, only the inorganic component was added to the weathering resin, so the QUV could pass only 200 hr, and the water contact angle was still greater than 13 ;. However, Comparative Examples 1 to 3 could not pass the QUV P, ?, and shot for 1 hour. The water contact angle has been lowered to 130 degrees or less; and Comparative Example 4 cannot be tested by the QUV for 200 hours due to poor adhesion and self-cleaning property. From the experimental results of Tables 1 to 2, it was found that the weather-resistant self-cleaning coatings of Examples 1 to 3 of the present invention not only have high scrub resistance characteristics, but also have excellent weather resistance. Example 4 Same as the shell example 1, the difference is that before the primer layer is painted, the commercial heat-insulating paint water is coated with water-based paint, and the paint is applied for about 500 μm, and dried at room temperature for 24 hours, and then Order coating example! The layers described. & 3 lists the general enthalpy molecules, the heat conduction of Example 1 and Example 4, the force of the test is 'only the result is minus' compared to the general polymer and the example i (excluding the thermal coating), Example 4 ( It has the best thermal insulation effect, its thermal conduction is less than G.2 W/m ' and its total solar thermal reflectivity (TSR) is more than 80%. 201035259 Table 3 General Polymer Example 1 Example 4 (without barrier (with thermal barrier coating) Coating) Heat conduction (W/m) 0.3 ～0.8 0.96 0.13 〜0.2 TSR - 〜75 % > 80 % ( Total solar reflection) Water contact angle <100. >150. < 150° While the present invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the invention, and the scope of the invention may be The scope of protection of the present invention is defined by the scope of the appended claims.
^5 .201035259 【圖式簡單說明】 第1圖為一剖面圖，用以說明本發明實施例的耐候自 潔塗層。 ' 第2圖為一剖面圖 候自潔塗層。 用以說明本發明實施例之隔熱耐 【主要元件符號說明】 10〜基材 ❹ 15〜隔熱塗層 20〜高耐候底漆塗層 30〜向接觸角塗層 100〜耐候自潔塗層 200〜隔熱耐候自潔塗層 ❹^5 .201035259 [Simple Description of the Drawings] Fig. 1 is a cross-sectional view for explaining the weather-resistant self-cleaning coating of the embodiment of the present invention. ' Figure 2 is a cross-sectional view of the self-cleaning coating. For explaining the heat insulation resistance of the embodiment of the present invention [main component symbol description] 10~substrate❹ 15~heat insulation coating 20~high weathering primer coating 30~contact angle coating 100~weathering self-cleaning coating 200~Insulation and weatherproof self-cleaning coating❹