1275620 九、發明說明： 【發明所屬之技術領域】 本發明係相關於可形成具高耐候性的塗膜之塗表用塗 料組成物。本發明的塗表用塗料組成物對無機建材用途特別 有助益。 【先前技術】 一般，使用陶瓷工業基材等無機質材作爲大樓和住宅等 的戶外裝潢材料和屋頂瓦，或室內裝潢材料等建材，爲要使 其具有耐候性和耐水性、耐凍害性等，通常在其表面塗抹丙 烯酸樹脂類、矽樹脂類、氟樹脂類等塗表用塗料。 先前，因上述塗料係有機溶劑類，爲要減少環境污染遂 以水性塗料取代之，無機建材用的塗表用塗料組成物係以丙 烯酸乳膠和丙烯酸矽乳膠爲漆料成分的塗料爲主流。特別胃 從耐候性的觀點考量以丙烯酸矽乳膠類較理想，例如掺合@ 烷偶合劑，以含有烷氧矽烷基之單體爲共聚成分，或乳膠^ 行聚合時或聚合後熱掺合烷氧基矽烷化合物之有機·無機胃 合粒子乳膠等方法（參考例如申請專利文獻1、申請專利& 獻2、申請專利文獻3、申請專利文件4)。 【申請專利文獻1】 特開昭58- 1 805 63號公報 【申請專利文獻2】 特開平8-3409號公報 【申請專利文獻3】 特開平1 0- 1 83046號公報 1275620 【申請專利文獻4】 特開2002-12816號公報 【發明內容】 【解決發明的課題】 近年，確保住宅品質的意向高漲，住宅用塗膜亦講求長 期不需維修化，維持成膜性等塗膜性能，且如何提升耐候性 亦成爲重要的問題。 本發明的目的係提供一種可形成具高耐候性且成膜性 、耐水性、耐凍害性優越的塗膜，且對陶瓷工業基材等無機 建材用途有助益之塗表用塗料組成物。 【解決課題的方法】 本發明係相關於 1 · 一種塗表用塗料組成物，其特徵係含有（A)共聚物乳 膠及（B)下述一般式[Technical Field] The present invention relates to a coating composition for a coating sheet which can form a coating film having high weather resistance. The coating composition for a surface coating of the present invention is particularly useful for the use of inorganic building materials. [Prior Art] In general, inorganic materials such as ceramic industrial substrates are used as building materials such as buildings and houses, roofing tiles, and building materials such as interior materials, in order to make them weather resistant, water resistant, and freeze-resistant. Usually, a surface coating material such as an acrylic resin, an anthracene resin or a fluororesin is applied to the surface. Previously, because the above-mentioned coatings are organic solvents, in order to reduce environmental pollution, water-based paints have been substituted, and coating compositions for inorganic building materials are mainly made of acrylic latex and acrylic acid latex as paint components. In particular, from the viewpoint of weather resistance, it is preferable to use an acrylic acrylate emulsion, for example, a blending of an alkane coupling agent, a copolymer containing an alkoxyalkyl group as a copolymerization component, or a thermal blending of an alkane during polymerization or polymerization. A method of an organic-inorganic gastric-integrated particle emulsion of a oxydecane compound (refer to, for example, Patent Application No. 1, Patent Application & Application No. 2, Patent Application No. 3, and Patent Application No. 4). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 】 】 】 】 】 】 】 】 】 】 】 】 】 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 Improving weather resistance has also become an important issue. An object of the present invention is to provide a coating material composition which can form a coating film which is excellent in weather resistance, is excellent in film formability, water resistance and freeze resistance, and which is useful for inorganic building materials such as ceramic industrial substrates. [Means for Solving the Problem] The present invention relates to a coating composition for a surface coating comprising (A) copolymer latex and (B) the following general formula
(式中’R1及R2爲相同或相異的甲基或烷氧基，R3爲碳 數1〜4的烷基或環氧丙基，R4爲—r5(〇 R6)n(〇 R7)m〇z(R5 爲碳數1〜4的伸烷基，R6及R7爲碳數2〜4的伸烷基，Z爲 氫原子、烷基或乙酸基’ m爲〇〜；[，〇〇〇，η爲0〜1，000，且 m + n$2。）表示的羥伸烷基，ρ爲1〜i，〇〇〇，q爲1〜1，〇〇〇。） 表示的重量平均分子量500〜3〇,〇〇〇的聚有機矽氧烷之塗表 1275620 用塗料組成物，相對於（A)成分1 〇〇重量份（固形分），此（B) 成分的使用量爲〇·1〜50重量份（固形分）， 2 ·如第1項之塗表用塗料組成物，其中共聚物乳膠（Α) 係於水及乳化劑的共存下，使用聚合性不飽和單體混合物以 多階段的方式乳化聚合製成的乳膠，此乳膠粒子的中心部份 的共聚物之玻璃轉移溫度（TgA)爲-40〜35°C，此乳膠粒子的 最外殼部份的共聚物之玻璃轉移溫度（TgB)爲25〜100°C，此 TgB比TgA至少高20°C以上之共聚物乳膠， 3 ·如第1或2項之塗表用塗料組成物，其中共聚物乳膠 (A)係一種含有由0〜20重量％含烷氧矽烷基的聚合性不飽和 單體、0〜70重量％含環烷基的聚合性不飽和單體及0〜100重 量％的其他聚合性不飽和單體組成的單體混合物經乳化聚合 而得的丙烯酸共聚物⑴的存在下，加入由0〜20重量％含烷 氧矽烷基的聚合性不飽和單體、〇〜70重量％含環烷基的聚合 性不飽和單體及10〜100重量％的其他聚合性不飽和單體組 成的單體混合物經乳化聚合而製得的丙烯酸共聚物（ii)之芯 部/殼部乳膠， 4. 如第1項之塗表用塗料組成物，其中聚有機矽氧烷（B) 中，R3係至少一種選自於乙基、丙基及環氧丙基之族群， 5. —種塗裝無機質材之製法，其特徵係於保養無機質材 之前或之後塗裝保護層，其次塗裝第1〜4項中任一項之塗表 用塗料組成物。 【發明的效果】 本發明中，因（B)成分聚有機矽氧烷定向於塗膜表層， 1275620 可形成具有高耐候性且成膜性、耐水性、耐凍害性等優越之 塗膜。 本發明中，（B)成分因烷氧矽烷基直接鍵結在矽氧烷鏈 上’和丨兀氧砍丨兀基Pra者丨兀基間接鍵結在5夕氧院鍵的情形相較 ，因不具分枝的化學結構故不易影響由立體障礙而來對塗膜 表層的定向。且，聚矽氧烷的低極性以及和（A)成分的極性 差之故，可促進在塗膜表面的定向。又與適度的親水性基鍵 結，可同時具有無塗膜缺點之平滑塗膜。 又，（A)成分若含有烷氧矽烷基時，因與部分（B)成分反 應，經過一段時間（B)成分亦不會從塗膜滲出，可維持長時 間的耐候性。 因此本發明的塗表用塗料組成物對使用爲大樓、住宅等 的外部裝潢材料和屋頂瓦，或內部裝潢材料等建築材料隻陶 瓷工業類建材等無機建材之用途有助益。 【實施方式】 本發明中可使用以往公知的乳膠作爲共聚物乳膠（A)， 無特別的限制，例如丙烯酸類、矽類、聚胺甲酸類、氟類等 乳膠，特別是從耐候性、抗阻塞性等的觀點，於水及乳化劑 的共存下，使用聚合性不飽和單體混合物以多階段的方式乳 化聚合製成的乳膠，此乳膠粒子的中心部份的共聚物之玻璃 轉移溫度（TgA)爲-40〜35t，較理想爲-30〜20°C，此乳膠粒 子的最外殼部份的共聚物之玻璃轉移溫度（TgB)爲2 5〜100°C ，較理想爲40〜90°C，此TgB比TgA至少高20°C以上，較 理想爲高25 °C以上之多層結構粒子狀的乳膠較理想。 1275620 此TgA若低於-4(TC，形成塗膜易發生阻塞，若高於 3 5 °C ’其成膜性和低溫物性（凍結溶解試驗）等低落較不理想 。又，TgB若低於25 °C，形成塗膜易發生阻塞，若高於 1 00 °C，其成膜性和低溫物性（凍結溶解試驗）等低落較不理 想。且此TgB若不比TgA至少高20°C以上，則無法同時具 有形成塗膜的阻塞性和成膜性、低溫物性（凍結溶解試驗）等 較不理想。 又，本說明書中，可依據下式算出共聚物的玻璃轉移溫 度（°c )。 1 / Tg(°K) = (Wl / T1)+ (W2/T2) + *··(wherein R1 and R2 are the same or different methyl or alkoxy groups, R3 is an alkyl group having 1 to 4 carbon atoms or a glycidyl group, and R4 is -r5(〇R6)n(〇R7)m 〇z (R5 is an alkylene group having 1 to 4 carbon atoms, R6 and R7 are an alkylene group having 2 to 4 carbon atoms, and Z is a hydrogen atom, an alkyl group or an acetic acid group 'm is 〇~; [, 〇〇〇 , η is 0 to 1,000, and m + n$2.) represents a hydroxyalkylene group, ρ is 1 to i, 〇〇〇, q is 1 to 1, 〇〇〇.) represents a weight average molecular weight of 500. ~3〇, 聚 聚 polyorganoxane coating table 1275620 coating composition, relative to (A) component 1 〇〇 by weight (solids), the use of this (B) component is 〇·1 ～50 parts by weight (solids), 2. The coating composition for coating according to item 1, wherein the copolymer latex (Α) is in the coexistence of water and an emulsifier, and a mixture of polymerizable unsaturated monomers is used. a latex produced by emulsion polymerization in a stage manner, wherein the copolymer of the central portion of the latex particles has a glass transition temperature (TgA) of -40 to 35 ° C, and the glass transition temperature of the copolymer of the outermost portion of the latex particles (TgB) is 25~100 °C, this a copolymer latex having a TgB of at least 20 ° C higher than TgA, and a coating composition according to item 1 or 2, wherein the copolymer latex (A) is one containing 0 to 20% by weight of an alkoxylated alkane. Emulsified polymerization of a monomeric mixture of a polymerizable unsaturated monomer, 0 to 70% by weight of a cycloalkyl-containing polymerizable unsaturated monomer, and 0 to 100% by weight of another polymerizable unsaturated monomer In the presence of the acrylic copolymer (1), 0 to 20% by weight of an alkoxyalkyl group-containing polymerizable unsaturated monomer, 〇 70% by weight of a cycloalkyl group-containing polymerizable unsaturated monomer, and 10 to 100% by weight are added. a core/shell emulsion of an acrylic copolymer (ii) obtained by emulsion polymerization of a monomer mixture of other polymerizable unsaturated monomers, 4. A coating composition for coating according to item 1, wherein the composition is In the organooxane (B), R3 is at least one selected from the group consisting of ethyl, propyl and epoxypropyl groups, and a method for preparing an inorganic material, which is characterized before or after the maintenance of the inorganic material. Coating the protective layer, and then coating the coating composition of any one of items 1 to 4 . [Effect of the Invention] In the present invention, since the polyorganosiloxane of the component (B) is oriented on the surface layer of the coating film, 1275620 can form a coating film having high weather resistance, film forming property, water resistance, and freeze resistance. In the present invention, the component (B) is directly bonded to the oxime chain by the alkoxyalkyl group, and the indirect bonding of the sulfonium group to the sulfonium group is indirectly bonded to the oxime bond. Because of the non-branched chemical structure, it is not easy to affect the orientation of the coating film surface caused by steric obstacles. Further, the low polarity of the polyoxyalkylene and the difference in polarity of the component (A) promote the orientation on the surface of the coating film. Further, it is bonded to a moderately hydrophilic group, and can simultaneously have a smooth coating film having no coating film defects. Further, when the component (A) contains an alkoxyalkyl group, it reacts with the component (B), and the component (B) does not bleed out from the coating film over a period of time, and the weather resistance for a long period of time can be maintained. Therefore, the coating composition for a surface coating of the present invention is useful for the use of an exterior building material such as a building or a house, a roofing tile, or a building material such as an interior material, such as ceramic industrial building materials. [Embodiment] In the present invention, a conventionally known latex can be used as the copolymer latex (A), and is not particularly limited, and examples thereof include latexes such as acrylics, anthraquinones, polyamines, and fluorines, particularly from weather resistance and resistance. From the viewpoint of obstruction, etc., in the coexistence of water and an emulsifier, a latex obtained by emulsion polymerization of a polymerizable unsaturated monomer mixture in a multistage manner, a glass transition temperature of a copolymer of a central portion of the latex particles ( The TgA) is -40 to 35 t, preferably -30 to 20 ° C, and the copolymer of the outermost portion of the latex particles has a glass transition temperature (TgB) of 25 to 100 ° C, preferably 40 to 90 ° C. At °C, this TgB is at least 20 ° C higher than TgA, and more preferably a multilayered particulate latex having a height of 25 ° C or higher. 1275620 If the TgA is lower than -4 (TC, it is easy to block the coating film, if it is higher than 35 °C, its film forming property and low temperature physical property (freeze dissolution test) are less than ideal. Moreover, if TgB is lower than TgB At 25 °C, the formation of the coating film is prone to blockage. If it is higher than 100 °C, the film formation and low temperature physical properties (freeze dissolution test) are less than ideal, and if the TgB is not higher than TgA by at least 20 °C, Further, it is not preferable to have both an obstructive property and a film forming property to form a coating film, a low-temperature physical property (freeze dissolution test), etc. In the present specification, the glass transition temperature (°c) of the copolymer can be calculated according to the following formula. / Tg(°K) = (Wl / T1)+ (W2/T2) + *··
Tg(°C ) = Tg(eK)-273 各式中W1、W2···係使用於共聚作用中的各單體之重量 %，ΤΙ、T2…係各單體的同質聚合物之Tg(eK)。又，ΤΙ、T2... 係根據聚合物手冊（Secend Edition，J.Brandup. E.H.Immergut編）之値。又，單體的同質聚合物的Tg不確 定時的玻璃轉移溫度（°C )可視爲靜態玻璃轉移溫度（°C )，例 如使用差示掃描熱量計「DSC-50Q型」（島津製作所製、商 品名），將試驗品置於測定杯中，抽成真空待溶劑完全去除 後，以3°C /分的升溫速度測定-100〜100 °C的範圍內的熱量 變化，以低溫側最初的基線的變化點作爲靜態玻璃轉移溫度 〇 一般，使用於上述乳化聚合的聚合性不飽和單體混合物 ’係根據期望的性能適當地選自含烷氧矽烷基的聚合性不飽 和單體、含環烷基的聚合性不飽和單體及其他的聚合性不飽 1275620 和單體等。 含烷氧矽烷基的聚合性不飽和單體，例如可使用1種或 2種以上的乙烯三甲氧基矽烷、乙烯三乙氧基矽烷、乙烯三 丙氧基矽烷、乙烯三丁氧基矽烷、（甲基）丙烯醯基羥甲基三 甲氧基矽烷、（甲基）丙烯醯基羥乙基三甲氧基矽烷、（甲基) 丙烯醯基羥丙基三甲氧基矽烷、（甲基）丙烯醯基羥丙基三乙 氧基矽烷、（甲基）丙烯醯基羥乙基三乙氧基矽烷、（甲基）丙 烯醯基羥丙基三丁氧基矽烷等。 又，本說明書中的「（甲基）丙烯醯基」表示爲「丙烯醯 基或甲基丙烯醯基」。 含環烷基的聚合性不飽和單體，例如可使用1種或2種 以上的環戊基（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、甲 基環己基（甲基）丙烯酸酯、第三丁基環己基（甲基）丙烯酸酯 、羥甲基環己基（甲基）丙烯酸酯、環辛基（甲基）丙烯酸酯、 環葵基（甲基）丙烯酸酯、環十二基（甲基）丙烯酸酯等。 其他的聚合性不飽和單體，例如可使用1種或2種以上 的甲基（甲基）丙烯酸酯、乙基（甲基）丙烯酸酯、正丙基（甲基 )丙烯酸酯、異丙基（甲基）丙烯酸酯、正丁基（甲基）丙烯酸酯 、異丁基（甲基）丙烯酸酯、第三丁基（甲基）丙烯酸酯、2-乙 基己基丙烯酸酯、正辛基（甲基）丙烯酸酯、月桂基（甲基）丙 烯酸酯、異冰片基（甲基）丙烯酸酯、硬脂醯基（甲基）丙烯酸 酯等丙烯酸或甲基丙烯酸的烷基酯；2-羥乙基（甲基）丙烯酸 酯、羥丙基（甲基）丙烯酸酯、2,3-二羥丁基（甲基）丙烯酸酯、 4-羥丁基（甲基）丙烯酸酯、聚乙二醇單元（甲基）丙烯酸酯等 -10· 1275620 多元醇和丙烯酸或甲基丙烯酸的單元酯化物、此多元醇和丙 烯酸或甲基丙烯酸的單元酯化物中，使ε -己內酯開環聚合的 化合物等含羥基的聚合性不飽和單體；丙烯酸、甲基丙烯酸 、馬來酸、馬來酸酐等含羧基的聚合性不飽和單體；Ν，Ν-二甲基胺基乙基（甲基）丙烯酸酯、Ν，Ν-二乙基胺基乙基（甲基 )丙烯酸酯、Ν,Ν-二甲基胺基丙基（甲基）丙烯酸酯等胺基烷基 (甲基）丙烯酸酯；丙烯醯胺、甲基丙烯醯胺、Ν，Ν-二甲基胺 基乙基（甲基）丙烯醯胺、Ν,Ν-二乙基胺基乙基（甲基）丙烯醯 胺、Ν,Ν-二甲基胺基丙基（甲基）丙烯醯胺、Ν-羥甲基丙烯醯 胺、Ν-羥甲基丙烯醯胺甲醚、Ν-羥甲基丙烯醯胺丁醚等（甲 基）丙烯醯胺或其衍生物；丙烯腈、甲基丙烯腈、醋酸乙烯 、苯乙烯、乙烯甲苯、α甲基苯乙烯；2-(2’-羥-5’-甲基丙烯 醯羥乙基苯基）-2Η-苯并三唑、4-(甲基）丙烯醯-ί，2,2,6,6-五 甲基哌啶等。 上述多階段的乳化聚合，係將選自上述聚合性不飽和單 體的適當混合物進行公知的乳化聚合以此爲第一階段，製得 的共聚物（相當於芯部分）的共存下，依序進行第二階段之後 的乳化聚合。 本發明中，上述多層結構粒子狀的共聚物乳膠（Α)，係 一種含由0〜20重量％含烷氧矽烷基的聚合性不飽和單體，較 理想爲0.1〜15重量％、0〜70重量％含環烷基的聚合性不飽和 單體，較理想爲0〜50重量％、10〜100重量％含其他的聚合性 不飽和單體，較理想爲35〜99.9重量％組成的單體混合物經 乳化聚合而得的丙烯酸共聚物⑴的共存下，加入由〇〜20重 1275620 量％含烷氧矽烷基的聚合性不飽和單體，較理想爲0.1〜1 5重 量％、0〜70重量％含環烷基的聚合性不飽和單體，較理想爲 0〜50重量％、10〜100重量％含其他的聚合性不飽和單體，較 理想爲3 5〜9 9 · 9重量％組成的單體混合物經乳化聚合而得的 丙烯酸共聚物（ii)之芯部/殼部乳膠，從製得的塗膜的耐候 性、耐水性、耐凍害性等觀點考量特別理想。 上述的芯部/殻部乳膠中，含烷氧矽烷基的聚合性不飽 和單體在芯部及殼部皆被聚合，從製得的塗膜的耐候性、耐 溫水性之觀點考量較理想，又，從反應性和塗料的儲存性的 平衡之觀點考量，此含烷氧矽烷基的聚合性不飽和單體的烷 氧基爲乙氧基特別理想。此烷氧基若爲甲氧基，因縮合反應 迅速故塗料的儲存性差，另一方面，若爲丙氧基以上碳數較 多時，因縮合反應緩慢故提升耐候性的效果不明顯較不理想 。從耐候性的觀點考量，上述的芯部/殼部乳膠中，含環烷 基的聚合性不飽和單體，在殼部較多而被共聚合的情形較佳 〇 上述的芯部/殻部乳膠中，芯部和殻部的重量比爲1 〇 /90~90/10，較理想爲20/80〜80/20的範圍內。若脫離 此範圍，芯部較少會導致塗膜的成膜性低落，若芯部較多.則 塗膜的抗阻塞性低落皆不理想。 上述的共聚物乳膠（A)進行乳化聚合時使用的乳化劑， 可依據期望的特性採用例如二烷基磺基琥珀酸鈉、十二基苯 磺酸鈉、月桂基硫酸鈉、聚環氧乙烷烷基苯基醚硫酸鈉及烷 基二苯基醚二磺酸鈉等陰離子性乳化劑；聚環氧乙烷高級醇 -12- 1275620 醚及聚環氧乙烷烷基苯基醚等非離子性乳化劑，又，含自由 基聚合性雙鍵的陰離子性或陽離子性之反應性乳化劑等。 上述的共聚物乳膠（A)進行乳化聚合時，特別以陰離子 性反應乳化劑較理想，此類反應性乳化劑，例如含（甲基）烯 丙基、丙烯基、丁烯基等自由基聚合性不飽和基和聚環氧烷 基的磺酸鈉鹽和磺酸鈉胺鹽等，市販品例如「福貼姆」（商 品名，花王（股）製）、「愛魯米爾」（商品名，三洋化成（股）製） 、「兒可龍」（商品名，第一工業製藥（股）製）等。 進行上述的乳化聚合時，一般，在水及上述乳化劑的共 存下使用聚合引發劑進行乳化聚合較理想，亦可依需求使用 硫醇類等鏈轉移劑。可使用的聚合引發劑例如過氧硫酸鉀、 過氧硫酸鈉、過氧硫酸銨、偶氮雙氰戊酸、2,2’-偶氮雙〔2-甲基(2-羥乙基）二乙基甲酮醯胺〕等有機偶氮類化合物類 、過氧化苯醯、二第三丁基羥過氧化物等有機過氧化物類等 〇 依據上述製得的共聚物乳膠（A)，其平均粒子徑爲 0·02 〜0·5μιη、〇·1 〜〇·3μιη 的範圍內。 本發明的聚有機矽氧烷（Β)，係上述一般式表示的聚有 機矽氧烷，塗膜形成後局部存在於表層之含聚係氧烷化合物 。通常，在塗料化時掺合使用此聚有機矽氧烷。 上述一般式中，R1及R2爲相同或相異的甲基或甲氧基 、乙氧基等烷氧基，特別以甲基較理想。 上述一般式中，R3爲碳數1〜4的烷基或環氧丙基。烷基 例如甲基、乙基、丙基、丁基等。其中，從塗料的儲藏安定 -13- 1275620 性的觀點考量，以至少一種選自乙基、丙基、環氧丙基等較 理想。 上述一般式中，R4爲一R5(0 R6)n(〇 R7)m〇Z(R5爲碳數 1〜4的伸烷基，R6及R7爲碳數2〜4的伸烷基，Z爲氫原子 、烷基或乙酸基，❿爲〇〜1，000，η爲0〜1，000，且m + n22 。）表示的經伸院基。又，m + n爲2〜2,000，以2〜500較適當 〇 又，p爲1~1，000較理想爲1〜300，q爲1〜1，〇〇〇較理想 爲1〜300。P若超過1,000則塗料的儲存安定性低落，若小 於1則製得的塗膜易裂開較不理想。又，q若超過1，〇 〇 〇則 塗料的儲存安定性低落，老小於1則製得的塗膜易裂開較不 理想。 上述的聚有機矽氧烷（B)的重量平均分子量爲 500〜30,000，較理想爲1，000〜10,000的範圍內。此聚合平均 分子量若小於5 00則塗料的儲存安定性低落，另一方面，若 超過30,000則不易在塗膜表層上定域化，提升製得塗膜的 耐候性之效果不明顯較不理想。其重量平均分子量，係將膠 體色譜分析法測得的分子量以聚苯乙烯的分子量爲基準經 換算所得之値。 本發明中，相對於共聚物乳膠（A) 100重量份（固形分） ’上述（B)成分的用量爲〇·ΐ〜50重量分，較理想爲0·5〜30重 量分（固形分）。若其用量小於0.1重量分，則增強耐候性的 效果不彰，若超過50重量分，則易發生成膜性不佳，且塗 料的儲存安定性低落較不理想。 -14- 1275620 上述（B)成分添加於水性塗料之方法，係直接添加並強 制攪拌混合，或使用乳化劑使水分散化等方法，惟，從增強 耐候性的觀點考量以前者的方法較理想。 本發明的塗表用塗料組成物中，亦可依需求適當地合上 述（A)成分之外的水溶性或水分散性樹脂、著色顏料和體質 顏料等顏料類、分散劑、有機溶劑、pH調節劑、消泡劑、 增稠劑、黏性調節劑、成膜輔助劑、紫外線吸收劑、光安定 劑、抗凍結劑、表面調節劑、增塑劑、防腐劑、抗氧化劑等Tg(°C) = Tg(eK)-273 In each formula, W1, W2··· are the weight % of each monomer used in the copolymerization, and the Tg of the homopolymer of each monomer of ΤΙ, T2... eK). Further, ΤΙ, T2... are based on the Polymer Handbook (Secend Edition, edited by J. Brandup. E.H. Immergut). In addition, the glass transition temperature (°C) when the Tg of the homopolymer of the monomer is not determined can be regarded as the static glass transition temperature (°C), and for example, a differential scanning calorimeter “DSC-50Q type” (manufactured by Shimadzu Corporation) Product name), the test article is placed in the measuring cup, and the vacuum is evacuated. After the solvent is completely removed, the heat change in the range of -100 to 100 °C is measured at a temperature rising rate of 3 ° C /min. The change point of the baseline is as a static glass transition temperature 〇, and the polymerizable unsaturated monomer mixture used in the above emulsion polymerization is appropriately selected from alkoxyalkyl group-containing polymerizable unsaturated monomer, ring-containing according to desired properties. Alkyl polymerizable unsaturated monomers and other polymerizable unsaturated 1275620 and monomers. As the alkoxyalkyl group-containing polymerizable unsaturated monomer, for example, one type or two or more types of ethylene trimethoxy decane, ethylene triethoxy decane, ethylene tripropoxy decane, and ethylene tributoxy decane can be used. (Meth)acryloylhydroxymethyltrimethoxydecane, (meth)acryloylhydroxyethyltrimethoxydecane, (meth)acryloylhydroxypropyltrimethoxydecane, (meth)propene Mercaptohydroxypropyltriethoxydecane, (meth)acryloylhydroxyethyltriethoxydecane, (meth)acryloylhydroxypropyltributoxydecane, and the like. Further, the "(meth)acrylonitrile group" in the present specification means "acryloalkyl group or methacryl group". As the cycloalkyl group-containing polymerizable unsaturated monomer, for example, one type or two or more types of cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and methylcyclohexyl (meth) acrylate can be used. Ester, tert-butylcyclohexyl (meth) acrylate, hydroxymethylcyclohexyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclopropyl (meth) acrylate, ring twelve Base (meth) acrylate and the like. As the other polymerizable unsaturated monomer, for example, one type or two or more types of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl group can be used. (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl ( An alkyl ester of acrylic acid or methacrylic acid such as methyl acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate or stearyl methacrylate; 2-hydroxyethyl Base (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol unit (Meth) acrylate, etc. - 10,756,620, a unit ester of a polyhydric alcohol and acrylic acid or methacrylic acid, a compound of this polyhydric alcohol, and a unitary ester of acrylic acid or methacrylic acid, a compound which ring-opens ε-caprolactone, etc. Hydroxy polymerizable unsaturated monomer; acrylic acid, methacrylic acid a carboxyl group-containing polymerizable unsaturated monomer such as maleic acid or maleic anhydride; hydrazine, hydrazine-dimethylaminoethyl (meth) acrylate, hydrazine, hydrazine-diethylaminoethyl (A) Aminoalkyl (meth) acrylate such as acrylate, hydrazine, hydrazine-dimethylaminopropyl (meth) acrylate; acrylamide, methacrylamide, hydrazine, hydrazine-dimethyl Aminoethyl (meth) acrylamide, hydrazine, hydrazine-diethylaminoethyl (meth) acrylamide, hydrazine, hydrazine-dimethylaminopropyl (meth) acrylamide , (meth) acrylamide or its derivatives such as hydrazine-hydroxymethyl acrylamide, hydrazine-hydroxymethyl propylene decyl methyl ether, hydrazine-hydroxymethyl propylene decyl butyl ether; acrylonitrile, methacryl Nitrile, vinyl acetate, styrene, vinyl toluene, alpha methyl styrene; 2-(2'-hydroxy-5'-methacryl oxime hydroxyethylphenyl)-2 fluorene-benzotriazole, 4-(A) Base) acrylonitrile-ί, 2,2,6,6-pentamethylpiperidine, and the like. The multistage emulsion polymerization is carried out by subjecting a suitable mixture selected from the above polymerizable unsaturated monomers to a known emulsion polymerization as a first stage, and the obtained copolymer (corresponding to a core portion) is coexistent, in order The emulsion polymerization after the second stage is carried out. In the present invention, the above-mentioned multilayered particulate copolymer latex is a polymerizable unsaturated monomer containing 0 to 20% by weight of an alkoxyalkyl group-containing alkyl group, more preferably 0.1 to 15% by weight, 0%. 70% by weight of the cycloalkyl-containing polymerizable unsaturated monomer, preferably 0 to 50% by weight, 10 to 100% by weight, based on the other polymerizable unsaturated monomer, more preferably 35 to 99.9% by weight. In the coexistence of the acrylic copolymer (1) obtained by emulsion polymerization of the bulk mixture, a polymerizable unsaturated monomer having an alkoxyalkyl group content of from 〇20 to 1275620% by weight is added, preferably 0.1 to 15% by weight, 0~. 70% by weight of a cycloalkyl-containing polymerizable unsaturated monomer, more preferably 0 to 50% by weight, and 10 to 100% by weight of other polymerizable unsaturated monomer, more preferably 3 5 to 9 9 · 9 by weight The core/shell latex of the acrylic copolymer (ii) obtained by emulsion polymerization of the monomer mixture of the % composition is particularly preferable from the viewpoints of weather resistance, water resistance, and freeze resistance of the obtained coating film. In the core/shell emulsion described above, the alkoxyalkyl group-containing polymerizable unsaturated monomer is polymerized in both the core portion and the shell portion, and is preferably considered from the viewpoints of weather resistance and temperature resistance of the obtained coating film. Further, from the viewpoint of the balance between the reactivity and the storage property of the coating material, the alkoxy group of the alkoxyalkyl group-containing polymerizable unsaturated monomer is particularly preferably an ethoxy group. When the alkoxy group is a methoxy group, the storage property of the coating is poor due to a rapid condensation reaction. On the other hand, when the number of carbon atoms is more than a propoxy group, the effect of improving the weather resistance is not significant because the condensation reaction is slow. ideal. From the viewpoint of weather resistance, in the core/shell emulsion described above, the cycloalkyl group-containing polymerizable unsaturated monomer is preferably copolymerized in the shell portion, preferably in the above-mentioned core/shell portion. In the latex, the weight ratio of the core portion to the shell portion is 1 〇/90 to 90/10, preferably 20/80 to 80/20. If it is out of this range, the core portion will be less likely to cause film formation of the coating film to be lowered, and if the core portion is large, the anti-blocking property of the coating film is not preferable. The above-mentioned copolymer latex (A) is used as an emulsifier for emulsion polymerization, and may be, for example, sodium dialkyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate or polyepoxy resin depending on desired characteristics. Anionic emulsifiers such as sodium alkyl phenyl ether ether and sodium alkyl diphenyl ether disulfonate; non-ethylene oxide higher alcohol-12-1275620 ether and polyethylene oxide alkyl phenyl ether An ionic emulsifier, or an anionic or cationic reactive emulsifier containing a radically polymerizable double bond. When the above copolymer latex (A) is subjected to emulsion polymerization, it is particularly preferable to use an anionic reactive emulsifier such as a radical polymerization of a (meth)allyl group, a propenyl group or a butenyl group. Sodium sulfonate and sodium sulfonate amine salt of a polyunsaturated group and a polyalkylene oxide group, such as "Fujimu" (trade name, Kao (share) system), "Ermumir" (trade name) , Sanyo Chemical (share) system, "Children's Dragon" (trade name, first industrial pharmaceutical (share) system). In the above emulsion polymerization, it is preferred to carry out emulsion polymerization using a polymerization initiator in the presence of water and the above emulsifier, and a chain transfer agent such as a mercaptan may be used as needed. A polymerization initiator which can be used, for example, potassium peroxysulfate, sodium peroxodisulfate, ammonium peroxosulfate, azobiscyanovaleric acid, 2,2'-azobis[2-methyl(2-hydroxyethyl)di An organic azo compound such as ethyl ketone oxime, an organic peroxide such as benzoquinone or ditributyl hydroxy peroxide, or the like, which is obtained according to the above-mentioned copolymer latex (A). The average particle diameter is in the range of 0·02 〜0·5 μιη, 〇·1 〇 3·3 μιη. The polyorganosiloxane (Β) of the present invention is a polyoxyalkylene compound which is present in the surface layer after the coating film is formed, and is a polyoxyalkylene compound which is present in the surface layer after the formation of the coating film. Usually, the polyorganosiloxane is blended at the time of coating. In the above general formula, R1 and R2 are the same or different methyl or methoxy groups such as methoxy or ethoxy groups, and particularly preferably a methyl group. In the above general formula, R3 is an alkyl group having 1 to 4 carbon atoms or a glycidyl group. Alkyl groups such as methyl, ethyl, propyl, butyl and the like. Among them, at least one selected from the group consisting of ethyl, propyl, epoxypropyl and the like is preferable from the viewpoint of the storage stability of the coating material -13 - 1275620. In the above general formula, R4 is a R5(0 R6)n(〇R7)m〇Z (R5 is an alkylene group having 1 to 4 carbon atoms, R6 and R7 are an alkylene group having 2 to 4 carbon atoms, and Z is A hydrogen atom, an alkyl group or an acetate group, ❿ is 1,000~1,000, η is 0 to 1,000, and m + n22 . Further, m + n is 2 to 2,000, and 2 to 500 is more appropriate. Further, p is preferably 1 to 1,000, preferably 1 to 300, q is 1 to 1, and more preferably 1 to 300. If the P exceeds 1,000, the storage stability of the coating is low, and if it is less than 1, the coating film produced is less likely to be cracked. Further, if q exceeds 1, the storage stability of the coating is low, and if the coating is less than 1, the coating film is less likely to be cracked. The above polyorganosiloxane (B) has a weight average molecular weight of from 500 to 30,000, more preferably from 1,000 to 10,000. If the average molecular weight of the polymerization is less than 500, the storage stability of the coating is low. On the other hand, if it exceeds 30,000, it is difficult to localize the surface layer of the coating film, and the effect of improving the weather resistance of the coating film is not so remarkable. The weight average molecular weight is obtained by converting the molecular weight measured by colloidal chromatography based on the molecular weight of polystyrene. In the present invention, the amount of the above component (B) is from 〇·ΐ to 50 parts by weight, preferably from 0.5 to 30 parts by weight (solid content), relative to 100 parts by weight of the copolymer latex (A) (solid content). . If the amount is less than 0.1 part by weight, the effect of enhancing the weather resistance is not good, and if it exceeds 50 parts by weight, the film formability is liable to occur, and the storage stability of the coating is lowered. -14- 1275620 The method of adding the above-mentioned component (B) to a water-based paint is a method of directly adding and forcibly stirring and mixing, or dispersing water by using an emulsifier, but the method of the former is considered to be advantageous from the viewpoint of enhancing weather resistance. . In the coating composition for a surface coating of the present invention, a pigment such as a water-soluble or water-dispersible resin, a coloring pigment, and an extender pigment other than the above component (A), a dispersing agent, an organic solvent, and a pH may be appropriately blended as needed. Conditioning agent, antifoaming agent, thickening agent, viscosity adjusting agent, film forming auxiliary agent, ultraviolet absorber, light stabilizer, antifreeze agent, surface conditioner, plasticizer, preservative, antioxidant, etc.
上述的紫外線吸收劑，例如2-(2-羥基-3,5-二-叔-戊基 苯基）-2H-苯并三唑、異辛基-3-(3-(2H-苯并三唑-2-基）-5-第 三丁基-4-羥苯基丙酸酯、2-〔 2-羥基-3，5-二- (1,1-二甲基苯 炔）苯基〕-2H-苯并三唑、2_〔 2-羥基-3-二甲基苄基-5-二 -(1，1，3,3-四甲基丁基）苯基〕-211-苯并三唑、甲基-3-〔3-第 三丁基- 5-(2H-苯并三唑-2-基）-4-羥苯基〕丙酸酯/聚乙二醇 300的縮合物等苯并三唑類衍生物；2-〔 -4-〔（2-羥基-十二 基羥基丙基）羥基〕-2-羥基丙基-4,6-雙（2,4-二甲基苯墓 )-1，3,5-三嗪等三嗪類衍生物；乙烷二醯胺-N_(2-乙氧苯基 )-N’-(2_乙基苯基）-(氧代醯胺）、乙烷二醯胺-N-(2-乙氧苯 基）-N’-(4-異十二基苯基）-(氧代醯胺）等草酸醯替苯胺類 衍生物。這些添加劑事先和上述的（B)成分混合，進行塗料 化時掺合這些混合物，藉此，可在塗膜表層與（B)成分共同 、 定域化，具有加倍的效果。 本發明中，保養無機質材之前或之後塗裝保護層，其次 •15- 1275620 塗裝上述製得的塗表用塗料組成物，可製造塗裝無機質材。 上述的無機質材例如混凝土、泥漿、輕量氣泡混凝土 (ALC)、氣泡混凝土、磚、瓦、板岩、矽酸鈣板、陶瓷器、 瓷磚、玻璃、石材、木片水泥板、水泥押出成形板等，特別 以木纖維增強水泥板類、纖維增強水泥板類、纖維增強水泥 矽酸釣板類等陶瓷工業基材較理想。 通常，上述無機質材係於形成板狀後進行一次保養、塗 抹管道（in-line)保護層、乾燥、高壓釜保養、切削加工、預 熱後塗裝二次保護層，其次進行乾燥而製得保護層板。 上述保養無機質材之前或之後塗裝的保護層，無特別的 限制可使用過去公知的保護層，例如丙烯酸胺甲酸類、丙烯 酸類、環氧類、矽類等有機溶劑型或水性保護層等。塗裝此 保護層的方法可採用過去公知的塗裝方法。 本發明的塗表用塗料組成物之塗裝方法無特別的限制 ，可採用過去公知的塗裝方法，例如滾軸、刷毛、浸漬、輥 塗機、空氣塗裝、無空氣塗裝、幕式流動塗料器、增粘塗料 器等。此塗裝膜的厚度係乾燥膜的厚度爲5〜ΙΟΟμιη，又以 10〜80μπι的範圍較理想。可在室溫下進行乾燥，或在50〜 2〇(TC的溫度下加熱10秒〜30分鐘。 【實例】 以下，舉出實例更詳細地說明本發明。又，「份」及「 % J分別表示爲「重量份」及「重量％」。 共聚物乳膠（A)之製造 製造例1 -16- 1275620 在具有溫度計、恆溫器、攪拌器、回流式冷卻器、及滴 漏裝置的容量2公升之反應器中，放入50份去離子水、0.05 份十二基苯磺酸蘇打，並加熱至82 °C。於其他容器中添加 3 8份去離子水、3份十二基苯磺酸蘇打、〇. 1 5份作爲聚合引 發劑的過氧硫酸銨，充分攪拌後，於其中加入下列的單體混 合物並充分攪拌，可得單體乳化物（1)。 環己基甲基丙烯酸酯 20份 甲基甲基丙烯酸酯 10份 正丁基丙烯酸酯 29.6 份 正丁基甲基丙烯酸酯 9份 乙烯三乙氧基矽烷 〇·7份 甲基丙烯酸 0.7份 以3小時的時間將此乳化物（1)滴入反應容器中。其次 ’在其他容器中添加1 6份去離子水、1 . 5份十二基苯磺酸蘇 打、0.05份過氧硫酸銨，充分攪拌後，於其中加入下列的單 體混合物並充分攪拌，可得單體乳化物（2)。 環己基甲基丙烯酸酯 15份 甲基甲基丙烯酸酯· 10份 正丁基丙烯酸酯 2份 正丁基甲基丙烯酸酯 2.4份 乙烯三乙氧基矽烷 0.3份 甲基丙烯酸 〇 · 3份 上述單體乳化物（1)完全滴入容器後，再以1小時的時 間將上述單體乳化物（2)滴入其中，之後，於82 °C經過2小 •17- 1275620 時的釀成後冷卻至4 0 °C，製得乳白色的共聚物乳膠（a -1)。 此乳白色的共聚物乳膠（A-1)的固形分爲47.7%，芯部/殼部 乳膠粒子的平均粒子徑爲1 30nm。 製造例2〜5 在製造例1中，除了使用單體乳化物（1 )及單體乳化物（2) 的各單體組成如下表1所示之外，和製造例1相同之製法， 可得共聚物乳膠（A - 2 )〜（A - 5 )。又，製造例5中，使用同量的 「艾科艾濃H S - 1 0 2 5」（第一工業製藥公司製，反應性乳化劑） 取代製造例1中的乳化劑十二基苯磺酸蘇打。 【表1】 _ 實例 1 2 3 4 5 共聚物乳膠名 A-1 A-2 Ad A-4 A-5 乳化物（1)單 環己基甲基丙烯酸酯 20.0 20.0 20.0 體組成 甲基甲基丙烯酸酯 10.0 26.3 10.0 26.3 10.0 正丁基丙烯酸酯 29.6 33.3 33.3 34.0 29.6 正丁基甲基丙烯酸酯 9.0 9.0 9.0 9.0 9.0 乙烯三乙氧基矽烷 0.7 0.7 0.7 甲基丙烯酸 0.7 0.7 0.7 0.7 0.7 乳化物(2)單 環己基甲基丙烯酸酯 15.0 15.0 15.0 體組成 甲基甲基丙烯酸酯 10.0 21.2 10.0 21.5 10.0 正丁基丙烯酸酯 2.0 3.5 5.0 3.5 2.0 正丁基甲基丙烯酸酯 2.4 4.7 2.7 4.7 2.4 乙烯三乙氧基矽烷 0.3 0.3 0.3 甲基丙烯酸 0.3 0.3 0.3 0.3 0.3 Tg(°〇 芯部 1.1 0 0.5 -0.6 1.1 殼部 61.2 60.9 61.6 62.2 61.2 -18· 1275620 顏料糊的製作 將2份「BYK-1 90」（比格化學公司製，商品名，分散樹脂 )、5 0份去離子水、及1 00份鈦白混合，並以搖動輸漆器進 行分散處理後，製成固形分爲67%的顏料糊。 水件塗料的製作 實例1〜7及比較例1〜4 依據表2所示，掺合上述製造例1〜5製得的共聚物乳膠 、聚矽氧烷化合物、顏料糊等，攪拌混合後添加0.1份氨調 整pH約爲8〜9，製得固形分爲54%的各種水性塗料。又， 實例6的塗料係將聚矽氧烷化合物和紫外線吸收劑預先混合 後，再與其他成分攪拌混合而製得。又，表2所示爲周形分 ，表2中的聚矽氧烷化合物（1)〜（3)如下所示。製得的各種 水性塗料需進行下述的性能試驗。結果如表3所示。 (1) :上述的一般式中，R1及R2爲甲基，R3爲乙基，R4 爲一CH2 CH2 CH2 (0 CH2 CH2)30 CH3，p 爲 32，q 爲 5，重 量平均分子量約爲5,000之聚有機矽氧烷。 (2) ··上述的一般式中，R1及R2爲甲基，r3爲乙基，p 爲37, q爲0,重量平均分子量約爲1 0,000之聚有機矽氧烷 〇 (3) :上述的一般式中，R1及R2爲甲基，R4爲一ch2 ch2 CH2 (〇 CH2 CH2)30 CH3，p爲〇，q爲37，重量平均分子量 約爲4，0 0 〇之聚有機矽氧烷。 (註1)紫外線吸收劑：「TINUVIN3 84」係汽巴嘉基特殊 化學品公司製，異辛基-3-(3-(2H -苯并三卩坐-2 -基）-5 -第三丁 -19- 1275620 基羥苯基丙酸酉旨 【表2】 實例 比較例 1 2 3 4 5 6 7 1 2 3 4 共聚物乳膠 A-1 1〇〇 100 100 100 100 100 100 A-2 100 A-3 100 A-4 100 A-5 100 Texanol 10 10 10 10 10 10 10 10 10 10 10 顏料糊 74 74 74 74 74 74 0 74 74 74 74 聚有機矽氧烷（1) 3 3 3 3 3 3 3 70 聚有機矽氧烷P) 3 聚有機矽氧烷(3) 3 紫外線吸收劑(註1) 2 生能試驗^^ (* 1)耐候性：在已塗裝保護層的板岩板上塗裝實例及比 較例的各種水性塗料，使其乾燥膜厚度爲3 〇 μιη，於} 2 〇艽進 行2 0分鐘乾燥製成各試驗塗板。測定此時的試驗塗板的6〇。 - 60。鏡面反射率作爲初期光澤値（以此作爲光澤維持率的 試驗開始時間，亦即零時間）。 接著’使用日光型老化試驗器（斯佳試驗機（股）製），進 行增進耐候性試驗（降雨循環；1 2分/小時，黑控制板溫度 6 0〜66°C )。測定試驗時間5 00 0小時後的60° - 60°鏡面反射 -20- 1275620 率作爲最終的光澤値，將此値除以初期光澤値，算出此値作 爲光澤保持率。 ◎:光澤保持率大於80%，無外觀變化 〇：光澤保持率大於79〜70%，無外觀變化 △:光澤保持率爲69〜50%，稍微變色 X :光澤保持率小於50%，明顯變色 (* 2)抗阻塞性：和上述（*1)相同做法，分別製作2枚各 種試驗塗板。使2枚的塗裝面相互接觸，在40 °C的條件下使 用阻塞性測試器，施加1 kg/ cm2的重量經時1 20分鐘，以 目視的方法評估塗膜的外觀變化。 〇：無變化 △:殘留稍有阻力的痕跡 X :塗膜發生黏著無法分開 (*3)成膜性：使用薄層塗布器ι〇〇μιη，在玻璃板 (7 0 X 1 5 0 X 4 m m)上塗裝實例及比較例的各種水性塗料，在5 °c 的恆溫室中乾燥24小時，製作用於成膜性評估的各試驗塗 板。將試驗塗板的塗膜置於1 0倍的放大透鏡下觀察其表面 ，評估裂痕的狀態。 〇：無裂痕 △:部分出現細微的裂痕 X :全部出現裂痕 (* 4 )耐凍害性：和上述（* 1 )相同的做法，將製得的各試 驗塗板置於空氣中，以在-2 0 °C凍結2小時和在2 0 t的水中 融解1小時爲一個循環，使各試驗塗板經過3 00個循環試驗 -21- 1275620 後，評估塗膜的狀態。 〇：無裂痕 △:部分出現細微的裂痕 X :全部出現裂痕 【表3】The above ultraviolet absorber, for example, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)-2H-benzotriazole, isooctyl-3-(3-(2H-benzotrim) Zin-2-yl)-5-tert-butyl-4-hydroxyphenylpropionate, 2-[2-hydroxy-3,5-di-(1,1-dimethylphenyl)phenyl] -2H-benzotriazole, 2-[2-hydroxy-3-dimethylbenzyl-5-di-(1,1,3,3-tetramethylbutyl)phenyl]-211-benzotriene Benzene such as condensate of azole, methyl-3-[3-t-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate/polyethylene glycol 300 And triazole derivatives; 2-[-4-[(2-hydroxy-dodecylhydroxypropyl)hydroxy]-2-hydroxypropyl-4,6-bis (2,4-dimethylbenzene tomb) a triazine derivative such as-1,3,5-triazine; ethanediamine-N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)-(oxoguanamine) , oxadiamine-N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl)-(oxodecylamine) and other oxalic acid anilide derivatives. These additives It is mixed with the above-mentioned component (B) in advance, and these mixtures are blended at the time of coating, whereby the surface layer of the coating film and the component (B) can be localized and localized. In the present invention, the protective layer is applied before or after the maintenance of the inorganic material, and then the coating composition for coating is prepared by coating the above-mentioned coating composition for coating. The above inorganic material such as concrete is prepared. , mud, lightweight concrete (ALC), bubble concrete, brick, tile, slate, calcium silicate board, ceramics, ceramic tile, glass, stone, wood chip cement board, cement extrusion forming board, etc., especially enhanced with wood fiber Ceramic industrial substrates such as cement board, fiber reinforced cement board, fiber reinforced cement citric acid fishing board, etc. are ideal. Generally, the above inorganic material is subjected to maintenance and in-line protective layer after forming a plate. , drying, autoclave maintenance, cutting, preheating, coating the secondary protective layer, and then drying to obtain a protective laminate. The protective layer applied before or after the maintenance of the inorganic material is not particularly limited. A well-known protective layer, such as an organic solvent type such as acrylamide, acrylic, epoxy, or anthracene, or an aqueous protective layer. The coating method of the coating composition for coatings of the present invention is not particularly limited, and a conventionally known coating method such as a roller, a bristles, a dipping, a roll coater can be employed. , air coating, airless coating, curtain flow coating device, thickening coating device, etc. The thickness of the coating film is 5~ΙΟΟμιη, and the range of 10~80μπι is ideal. Drying is carried out at room temperature or at 50 ° 2 Torr (temperature of TC for 10 seconds to 30 minutes.) [Examples] Hereinafter, the present invention will be described in more detail by way of examples. Also, "parts" and "% J are expressed as "parts by weight" and "% by weight", respectively. Production of Copolymer Latex (A) Production Example 1 -16 - 1275620 In a reactor having a thermometer, a thermostat, a stirrer, a reflux cooler, and a drip device having a capacity of 2 liters, 50 parts of deionized water, 0.05 part of dodecylbenzenesulfonic acid soda and heated to 82 °C. Adding 38 parts of deionized water, 3 parts of sodium dodecylbenzenesulfonate soda, hydrazine to other containers, and adding 5 parts of ammonium peroxodisulfate as a polymerization initiator, after thoroughly stirring, the following monomer mixture is added thereto. Stir well to obtain a monomer emulsion (1). Cyclohexyl methacrylate 20 parts methyl methacrylate 10 parts n-butyl acrylate 29.6 parts n-butyl methacrylate 9 parts ethylene triethoxy decane 〇 7 parts methacrylic acid 0.7 parts in 3 hours This emulsion (1) was dropped into the reaction vessel. Next, add 16 parts of deionized water, 1.5 parts of dodecylbenzenesulfonic acid soda, 0.05 parts of ammonium peroxodisulfate in other containers, stir well, add the following monomer mixture and stir well. A monomer emulsion (2) is obtained. Cyclohexyl methacrylate 15 parts methyl methacrylate · 10 parts n-butyl acrylate 2 parts n-butyl methacrylate 2.4 parts ethylene triethoxy decane 0.3 parts ruthenium methacrylate · 3 parts of the above monomers emulsified After the substance (1) is completely dropped into the container, the monomer emulsion (2) is dropped into the container for 1 hour, and then cooled at 4 ° 17 to 1775620 at 82 ° C and then cooled to 4 A milky white copolymer latex (a-1) was obtained at 0 °C. The milky white copolymer latex (A-1) had a solid content of 47.7%, and the core/shell latex particles had an average particle diameter of 1 30 nm. Production Examples 2 to 5 In Production Example 1, except that each monomer composition using the monomer emulsion (1) and the monomer emulsion (2) is as shown in Table 1 below, the same production method as in Production Example 1 may be employed. A copolymer latex (A-2)~(A-5) was obtained. Further, in Production Example 5, the same amount of "Ekko Essex HS - 1 0 2 5" (manufactured by Daiichi Kogyo Co., Ltd., a reactive emulsifier) was used instead of the emulsifier dodecylbenzenesulfonic acid in Production Example 1. soda. [Table 1] _ Example 1 2 3 4 5 Copolymer latex name A-1 A-2 Ad A-4 A-5 Emulsion (1) Monocyclohexyl methacrylate 20.0 20.0 20.0 Body composition methyl methacrylic acid Ester 10.0 26.3 10.0 26.3 10.0 n-Butyl acrylate 29.6 33.3 33.3 34.0 29.6 n-Butyl methacrylate 9.0 9.0 9.0 9.0 9.0 Ethylene triethoxy decane 0.7 0.7 0.7 Methacrylic acid 0.7 0.7 0.7 0.7 0.7 Emulsion (2) Single ring Hexyl methacrylate 15.0 15.0 15.0 Body composition Methyl methacrylate 10.0 21.2 10.0 21.5 10.0 n-Butyl acrylate 2.0 3.5 5.0 3.5 2.0 n-Butyl methacrylate 2.4 4.7 2.7 4.7 2.4 Ethylene triethoxy decane 0.3 0.3 0.3 Methacrylic acid 0.3 0.3 0.3 0.3 0.3 Tg (°〇 core part 1.1 0 0.5 -0.6 1.1 Shell part 61.2 60.9 61.6 62.2 61.2 -18· 1275620 Preparation of pigment paste 2 parts of “BYK-1 90” (made by Bige Chemical Co., Ltd.) , product name, dispersion resin), 50 parts of deionized water, and 100 parts of titanium dioxide mixed, and dispersed by a shake varnisher to prepare a pigment paste with a solid content of 67%. Examples 1 to 7 and Comparative Examples 1 to 4 According to Table 2, the copolymer latex, the polyoxyalkylene compound, the pigment paste, and the like obtained in the above Production Examples 1 to 5 were blended, stirred and mixed, and then 0.1 part of ammonia was added to adjust the pH. Approximately 8 to 9 were prepared to obtain various aqueous coatings having a solid content of 54%. Further, the coating of Example 6 was prepared by premixing a polyoxyalkylene compound and an ultraviolet absorber, and then mixing and mixing with other components. Table 2 shows the weekly components, and the polyoxyalkylene compounds (1) to (3) in Table 2 are shown below. The various aqueous coatings prepared are subjected to the following performance tests. The results are shown in Table 3. (1): In the above general formula, R1 and R2 are methyl, R3 is ethyl, R4 is a CH2 CH2 CH2 (0 CH2 CH2)30 CH3, p is 32, q is 5, and the weight average molecular weight is about a polyorganosiloxane of 5,000. (2) In the above general formula, R1 and R2 are methyl, r3 is ethyl, p is 37, q is 0, and polyorganoindene having a weight average molecular weight of about 10,000 Oxane oxime (3): In the above general formula, R1 and R2 are methyl groups, R4 is a ch2 ch2 CH2 (〇CH2 CH2)30 CH3, p is 〇, q is 37, weight average molecular weight A polyorganooxynonane of about 4,0 0 。. (Note 1) UV absorber: "TINUVIN3 84" is made by Ciba Specialty Chemicals, Inc., isooctyl-3-(3-(2H-benzotriazin-2-yl)-5 - third Ding-19- 1275620 hydroxyphenylpropionic acid 【 [Table 2] Example Comparative Example 1 2 3 4 5 6 7 1 2 3 4 Copolymer Latex A-1 1〇〇100 100 100 100 100 100 A-2 100 A-3 100 A-4 100 A-5 100 Texanol 10 10 10 10 10 10 10 10 10 10 10 Pigment paste 74 74 74 74 74 74 0 74 74 74 74 Polyorganooxane (1) 3 3 3 3 3 3 3 70 polyorganooxane P) 3 polyorganosiloxane (3) 3 UV absorber (Note 1) 2 Biomass test ^^ (* 1) Weather resistance: slate board coated with protective layer Each of the water-based paints of the coating examples and the comparative examples was applied to have a dry film thickness of 3 〇μιη, and dried at 20 ° for 20 minutes to prepare test panels. 6 〇 of the test plate at this time was measured. - 60. The specular reflectance is used as the initial gloss 値 (as the test start time of the gloss maintenance rate, that is, zero time). Then, using a daylight type aging tester (manufactured by Sijia Tester Co., Ltd.), an improved weather resistance test (rain cycle; 12 minutes/hour, black control panel temperature of 60 to 66 ° C) was carried out. 60 ° - 60 ° specular reflection after the test time of 500 hours was measured. -20 - 1275620 rate was used as the final gloss 値, and this enthalpy was divided by the initial gloss 値, and the enthalpy was calculated as the gloss retention. ◎: gloss retention rate is greater than 80%, no appearance change 〇: gloss retention rate is greater than 79~70%, no appearance change △: gloss retention is 69~50%, slightly discolored X: gloss retention is less than 50%, obvious discoloration (*2) Anti-blocking property: Two test panels were prepared in the same manner as in the above (*1). The two coating surfaces were brought into contact with each other, and an obstructive tester was applied at 40 ° C, and a weight of 1 kg/cm 2 was applied for 1 to 20 minutes to visually evaluate the appearance change of the coating film. 〇: No change △: Traces of slight resistance to residue X: Adhesion of the coating film cannot be separated (*3) Film-forming property: Using a thin coater ι〇〇μηη, on a glass plate (7 0 X 1 5 0 X 4 Mm) Each of the water-based paints of the upper coating examples and the comparative examples was dried in a constant temperature chamber at 5 ° C for 24 hours to prepare test test sheets for evaluation of film formation. The coating film of the test plate was placed under a magnifying lens of 10 times to observe the surface, and the state of the crack was evaluated. 〇: no cracks △: some cracks appear in part X: all cracks appear (* 4) Frost resistance: The same test method as above (* 1 ), the test panels prepared in the air are placed in the air at -2 The state of the coating film was evaluated by freezing at 0 °C for 2 hours and melting for 1 hour in 20 t of water for one cycle, and after each test plate was subjected to 300 cycles of the test -21 - 1275620. 〇: no cracks △: slight cracks appear in part X: all cracks appear [Table 3]
實例 比較例 1 2 3 4 5 6 7 1 2 3 4 耐候性 ◎ 〇 〇 〇 〇 ◎ 〇 X 〇 X ◎ 抗阻塞性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 成膜性 〇 〇 〇 〇 〇 〇 〇 〇 X 〇 X 耐凍害性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X -22-EXAMPLES Comparative Example 1 2 3 4 5 6 7 1 2 3 4 Weather resistance ◎ 〇〇〇〇 ◎ 〇 X 〇 X ◎ Anti-blocking 〇〇〇〇〇〇〇〇〇〇〇 Film-forming property 〇〇〇〇〇〇 〇〇X 〇X Frost resistance 〇〇〇〇〇〇〇〇〇〇X -22-