201221499 六、發明說明： 【發明所屬之技術領域】 本發明涉及聚環氧丙烷或環氧乙烷-環氧丙烷共聚物作為用於 複合保溫系統的黏結和抹面砂漿中的助黏添加劑的用途。 【先前技術】 為了製備複合保溫系統（CTIS)，將保溫板（通常為由聚苯乙烯 所組成的硬質發泡板）藉由黏結砂漿固定至磚石建築，接著將抹 面砂漿以及通常被併入該層中的紡織纖維織物或纖維施用至保溫 板，並且最後用修整灰泥或抹灰將所述複合系統覆蓋。此類黏結 砂漿和抹面砂漿的重要性質為新砂漿具有良好的加工性並且在固 化的砂漿組合物中具有高撓曲性和抗衝擊性、良好的水蒸氣滲透 性、防水性、與礦物基材的良好的黏附性，以及與保溫材料，特 別是聚苯乙烯板的良好的黏附性。 為了獲得最佳的性質，黏結砂漿和抹面砂漿的基礎配方因此用 基於烯鍵式不飽和單體的熱塑性聚合物進行改性。通常使用基於 上述熱塑性聚合物的水可再分散聚合物粉末改性包含礦物黏合劑 (mineral binder )的乾砂漿。此聚合物改性作用可得符合上述要 求的砂漿組合物。 但是，在特定的氣候條件下，如高大氣濕度和高溫環境，上述 砂漿組合物對聚苯乙烯基材的黏附並不令人滿意。 在US 2007/0256600 A1中，使用填酸單醋、二S旨和三醋於此目 的的助黏劑。但是，這些添加劑昂貴的價格是一個缺點。 201221499 藉由加入芳族聚醚改良對聚苯乙烯基材的黏附記载於EP 0698586 A1中。其中的缺點為出現關於使用此類化合物的生態問 題。 因此本發明的目的為改良黏結砂漿和抹面砂漿對聚笨乙烯表面 的黏附並且克服上述缺點。 該目的是藉由使用聚環氧丙烷或環氧乙烷-環氧丙烷共聚物來 實現的》 【發明内容】 從EP 0573036 B1已知聚環氧丙烷（聚丙二醇）為降低收縮添 加劑（shrinkage-reducing additive )。DE-A 1935507 提及聚丙二醇 作為用於砂漿組合物或混凝土組合物的消泡劑。在WO 01/04212 A1中，使用苯酚-甲醛縮合物和聚氧伸烷基化合物 (polyoxyalkylene compounds)的組合用於改良水可再分散聚合物 粉末的再分散性。 本發明提供聚環氧丙烷或環氧乙烷-環氧丙烷共聚物作為用於 複合保溫系統的黏結和抹面砂毁中的助黏添加劑的用途。 【實施方式】 化學式H-[0CH2CH2CH2]n-0H之合適的聚環氧丙院（聚丙二醇） 通常為π=5至70者’其約對應於400至4000克/莫耳的重量平均 分子量。較佳為重量平均分子量為1〇〇〇至4〇〇〇克/莫耳的聚環氧 丙烧，尤佳為2000至4000克/莫耳的聚環氧丙院。包含環氧乙烧 和環氧丙烷單體單元（ΕΟ-ΡΟ共聚物）且重量平均分子量為4〇〇 201221499 至4000克/莫耳-的共聚物也是適合的。較最佳為具有大於50莫耳 % PO單元的EO-PO共聚物。 一般而言，在每種情況下，以聚合物粉末c)的量計，使用0.05 至5重量％，較佳0.2至2重量％的聚環氧丙烷或環氧乙烷-環氧丙 烷共聚物用於改良黏附。 用於複合保溫系統的黏結和抹面砂漿通常以乾砂漿組合物的形 式提供並且在建築地點與水混合。所述乾砂漿組合物包含a)—或 多種礦物黏合劑，b)—或多種填充劑；c)一或多種基於烯鍵式不飽 和單體並且玻璃轉變溫度Tg為-25°C至+25°C的水可再分散聚合 物粉末；以及視需要d)另外的添加劑。 適合的礦物黏合劑a)係如水泥，特別係波特蘭水泥、高鋁水泥、 凝灰岩水泥、礦渣水泥、鎂氧水泥、磷酸鹽水泥或高爐礦渣水泥 以及混合水泥、填充水泥、飛灰、微矽粉、石灰和石膏。較佳使 用波特蘭水泥、高鋁水泥和礦渣水泥以及混合水泥、填充水泥、 石灰和石膏。一般而言，在每種情況下，以乾砂漿組合物的總重 量計，所述乾砂漿組合物包含5至50重量％，較佳為10至30重 量％的礦物黏合劑。 適合的填充劑b)之例子為矽砂、石英粉、碳酸鈣、白雲石、矽 酸鋁、黏土、白堊、白色熟石灰、滑石或雲母，以及輕質填充劑 例如浮石、氣泡玻璃、充氣混凝土、珍珠岩、蛭石、碳奈米管 (CNT)。還可使用所述填充劑之任意混合物。較佳為矽砂、石英 粉、碳酸鈣、白堊或白色熟石灰。一般而言，在每種情況中，以 乾砂漿組合物的總重計，所述乾砂漿組合物包含30至90重量％， 201221499 較佳為40至80重量％的填充劑。 用於乾砂漿組合物的另外的常用添加劑d)為增稠劑，例如多糖 (如纖維素醚和改性的纖維素醚）、澱粉醚、瓜爾膠、三仙膠、層 狀石夕酸鹽、聚幾酸（如聚丙稀酸及其偏醋（partial esters)以及可 視需要地被縮醛化或被疏水改性的聚乙烯醇）、酪蛋白以及締合型 增稠劑。常用添加劑還包括緩凝劑例如羥基羧酸或二羧酸或其 鹽、糖、草酸、琥珀酸、酒石酸、葡萄糖酸' 檸檬酸、蔗糖、葡 萄糖、果糖、山梨醇、新戊四醇。常用添加劑為促凝劑，例如無 機酸或有機酸的鹼金屬鹽或鹼土金屬鹽。可能被提及的另外的添 加劑為：疏水劑、防腐劑、成膜劑、分散劑、泡沫穩定劑、消泡 劑和阻燃劑（例如氫氧化紹）。 根據添加劑的類型，以常用量使用添加劑d)。一般而言，在每 種情況下，以乾砂漿組合物的總重量計，所述量為0.1至10重量 %。 水可再分散聚合物粉末c)是藉由在保護性膠體的存在下乾燥基 礎聚合物的對應含水分散體而獲得的粉末混合物。由於此製備方 法，分散體之細微分散樹脂被封包在足量的水溶性保護性膠體 中。乾燥時，保護性膠體的作用就像防止顆粒黏在一起的殼。當 再分散於水中時，保護性膠體再次溶於水中並且獲得原始聚合物 顆粒的含水分散體（Schulze J.，TIZ, No. 9, 1985)。 烯鍵式不飽和單體的適合的聚合物是基於一或多種選自以下群 組中的單體的聚合物：乙烯基酯、（甲基）丙烯酸酯、乙烯基芳族化 合物、烯烴、1,3-二烯和乙烯基鹵化物以及視需要可與其共聚合的 201221499 另外的單體。 適合的乙稀基酯為具有1至15個碳原子的叛酸的乙稀基酯。較 佳為乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2_乙基己酸乙稀酯、 月桂酸乙烯酯、乙酸1-曱基乙烯酯' 三甲基乙酸乙烯酯以及具有 9至11個碳原子的α支鏈單缓酸的乙稀基酯，例如Ve〇Va9R或 VeoVal 0R ( Resolution的商品名）。尤佳為乙酸乙烯酯。 來自丙烯酸酯或曱基丙烯酸酯中適合的單體是具有丨至15個碳 原子的無支鏈醇或支鏈醇的酯。較佳的曱基丙烯酸酯或丙烯酸酯 是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、 丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、曱基丙烯酸正丁 酯、丙烯酸三級丁酯、曱基丙烯酸三級丁酯、丙烯酸2_乙基己酯。 尤佳為丙浠酸甲酯、甲基丙烯酸甲酯、丙稀酸正丁酯、丙稀酸三 級丁 S旨以及丙稀酸2 -乙基己g旨。 較佳的乙烯基芳族化合物是苯乙烯、曱基苯乙烯和乙烯基甲 笨。較佳的乙烯基_化物是氣乙烯。較佳的烯烴是乙烯、丙烯， 而較佳的一烯是1,3-丁二稀和異戊二稀。 以單體混合物的總重量計，還可視需要地共聚合〇」至5重量％ 的輔助單體。較佳為使用〇.5至2 5重量％的輔助單體。辅助單體 的例子是烯鍵式不飽和單羧酸和二羧酸，較佳為丙烯酸' 曱基丙 烯酸、反丁烯二酸（fumaricacid)和馬來酸（maleicadd);烯鍵 式不飽#曱醯胺（carb〇xamjde)和碳腈（carb〇nic nitriie)，較佳 為丙烯醯胺和丙烯腈；反丁烯二酸和馬來酸的單酯和二酯，例如 一乙自曰和一異丙酯以及馬來酸酐；烯鍵式不飽和磺酸或其鹽，較 201221499 佳為乙烯基磺酸、2-丙烯醯胺基-2-甲基丙磺酸。另外的例子為預 交聯共聚單體，例如多烯鍵式不飽和共聚單體（例如鄰苯二甲酸 二烯丙酯、己二酸二乙烯酯、馬來酸二烯丙酯、甲基丙烯酸烯丙 酯或三聚氰酸三烯丙酯），或是後交聯共聚單體（例如丙烯醯胺基 乙醇酸（AGA)、甲基丙烯醯胺基乙醇酸曱酯（MMAG)、N-羥甲 基丙烯醯胺（NMA)、N-羥曱基甲基丙烯醯胺、N-羥曱基胺曱酸 烯丙酯、烷基醚例如異丁氧基醚或N-羥甲基丙烯醯胺、N-羥曱基 曱基丙烯醯胺和N-羥甲基胺曱酸烯丙酯的酯）。諸如曱基丙烯酸 環氧丙酯和丙烯酸環氧丙酯的環氧官能基的共聚單體也是適合 的。另外的例子為矽官能基共聚單體，例如丙烯醯氧基丙基三（烷 氧基）矽烷和甲基丙烯醢氧基丙基三（烷氧基）矽烷、乙烯基三烷氧 基矽烷和乙烯基曱基二烷氧基矽烷，其中例如乙氧基和乙氧基丙 二醇醚基團可以烷氧基的形式存在。可提及的還有具有羥基或CO 基團的單體，例如曱基丙烯酸羥基烷基酯和丙烯酸羥基烷基酯（如 丙烯酸羥基乙基酯、丙烯酸羥基丙基酯或丙烯酸羥基丁基酯、或 甲基丙烯酸羥基乙基酯、曱基丙烯酸羥基丙基酯或甲基丙烯酸羥 基丁基酯以及諸如二丙酮丙烯醯胺和丙烯酸乙醯乙醯氧基乙酯或 甲基丙烯酸乙醯乙醯氧基乙酯的化合物）。 選擇單體和共聚單體的重量比從而得到-25°C至+25°C，較佳為 -10°C至+ l〇°C，尤佳為-l〇°C至〇°C的玻璃轉變溫度Tg。可藉由差 示掃描量熱法（DSC)以已知的方式測定聚合物的玻璃轉變溫度 Tg (測定曲線的反曲點）。也可根據Fox方程式預先近似地計算出 Tg。根據 Fox T. G.，Bull· Am. Physics Soc. 1，3，第 123 頁（1956): 1/Tg = xl/Tgl + x2/Tg2 + …+ xn/Tgn，其中 xn 是單 Hn 的質量分 201221499 率（重量％/ 100>，Tgn是單體η均聚物之玻璃轉變溫度（以絕對 溫度表示）。均聚物的Tg值在Polymer Handbook第2版，J. Wiley & Sons, New York (1975)中可查得。 較佳為乙酸乙烯酯與1至50重量％乙烯的共聚物； 乙酸乙烯酯與1至50重量％乙烯和1至50重量％之一或多種選自 以下群組中的其他共聚單體的共聚物：羧酸基團中具有1至12個 碳原子的乙烯基酯，例如丙酸乙烯酯、月桂酸乙烯酯，具有9至 13個碳原子的α支鏈羧酸的乙烯基酯，例如VeoVa9、VeoValO、 VeoVall ； 乙酸乙烯酯、1至50重量％乙烯和較佳1至60重量％的具有1至 15個碳原子的無支鏈醇或支鏈醇的（甲基）丙烯酸酯（特別是丙烯 酸正丁酯或丙烯酸-2-乙基己酯）的共聚物；以及 包含30至75重量％乙酸乙烯酯、1至30重量％月桂酸乙烯酯或 具有9至11個碳原子的α支鏈羧酸的乙烯基酯、以及1至30重 量％的具有1至15個碳原子的無支鏈醇或支鏈醇的（曱基）丙烯酸 酯（特別是丙烯酸正丁酯或丙烯酸2-乙基己酯）的共聚物，其另 外包含1至40重量°/〇乙烯； 包含乙酸乙烯酯、1至50重量％乙烯和1至60重量％氣乙烯的共 聚物； 其中聚合物可另外包含指定量的上述輔助單體，並且在每種情況 中以重量％表示的數值合計為100重量％。 較佳者還有（甲基）丙稀酸S旨聚合物，例如丙稀酸正丁醋或丙烯酸 2-乙基己酯的共聚物或曱基丙烯酸曱酯與丙烯酸正丁酯和/或丙烯 201221499 酸2-乙基己酯的共聚物； ' 具有一或多個選自以下群組中的單體的苯乙烯-丙烯酸酯共聚 物：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙 烯酸2-乙基己酯； 具有一或多個選自以下群組中的單體的乙酸乙烯酯-丙烯酸酯共 聚物：丙烯酸曱酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、 丙稀酸2-乙基己酯和視需要的乙浠； 苯乙烯-1，3-丁二烯共聚物； 其中聚合物可另外包含指定量的上述輔助單體，並且在每種情況 中以重量％表示的數值合計為1 00重量％。 極佳的水可再分散聚合物粉末c)含有：包含乙酸乙烯酯和5至 50重量％乙烯的共聚物，或 包含乙酸乙稀酯、1至50重量％乙稀和1至5〇重量％具有9至11 個碳原子的α支鏈單羧酸的乙烯基酯的共聚物，或 包含30至75重量％乙酸乙烯酯、1至3〇重量％月桂酸乙烯酯或 具有9至11個碳原子的α支鏈羧酸的乙烯基酯以及1至3〇重量 %具有1至15個碳原子的無支鏈醇或支鏈醇的（甲基）丙烯酸酯的 共聚物，其另外包含1至40重量％乙烯，或 包含乙酸乙烯酯、5至50重量％乙烯和1至6〇重量％氣乙烯的共 聚物， 其中所述聚合物可另包含指定量的上述輔助單體，並且在每種情 況中以重量％表示的數值合計為1〇〇重量0/〇。 在保護性膠體的存在下藉由乳液聚合法或者藉由懸浮聚合法製 201221499 備聚合物，較佳為藉由乳液聚合法製備，其中聚合溫度通常為20 °C 至l〇〇°C，較佳為60°C至90°C，並且其中氣體共聚單體例如乙烯 的共聚合還可以在超大氣壓力下（通常在5巴至100巴範圍）進 行。藉由常用於乳液聚合或懸浮聚合的水溶性引發劑或單體可溶 性引發劑或氧化還原引發劑組合引發聚合。非水溶性引發劑的例 子是過硫酸鈉、過氧化氫、偶氮雙異丁腈。單體可溶性引發劑的 實施例是二（十六烷基）過氧化二碳酸酯、二（環己基）過氧化二碳酸 酯、過氧化二苯甲醯。以單體的總重量計，所述引發劑通常以0.01 至0.5重量％的量使用。所使用的氧化還原引發劑是所提及的引發 劑和還原劑的組合。適合的還原劑是例如亞硫酸鈉、羥基甲基亞 確酸鈉和抗壞血酸。以單體的總重量計，還原劑的量較佳為0.01 至0.5重量％。 為了控制分子量，可在聚合期間使用調節物質。如果使用調節 劑，以待聚合的單體計，一般係以0.01至5.0重量％的量使用， 並且分別引入或者與反應組分預混合。此類物質的例子為正十二 烷基硫醇、三級十二烷基硫醇、巯基丙酸、毓基丙酸曱酯、異丙 醇和乙醛。較佳為不使用調節物質。 為了穩定聚合混合物，使用保護性膠體，視需要地與乳化劑組 合使用。適合的保護性膠體是部分水解或完全水解的聚乙烯醇； 聚乙烯°比洛咬酮（polyvinylpyrrolidone);聚乙浠縮醒·;水溶形式 的多醣，例如澱粉（直鏈澱粉和支鏈澱粉）或糊精或環糊精、纖 維素及其羧甲基、曱基、羥乙基、羥丙基衍生物；蛋白質例如酪 蛋白或路蛋白鹽、大豆蛋白、明膠；木素項酸鹽（lignosulphonate ); 201221499 合成聚合物例如聚（曱基）丙_'(甲基）丙稀酸無基官能基共聚 單體單元的共聚物、聚（甲基）丙職胺、聚乙職賴及其水溶性 共聚物；三聚氰胺-甲酸績酸醋、萘-曱駿魏醋、苯乙稀-馬來酸 和乙稀基醚·馬來酸共聚物；陽離子賴性膠體（例如具有包含四 級敍基_單體單元的聚合物）。較佳為部分水解的或完全水解的 聚乙稀醇。尤佳為水解度為8G至95莫耳％並且在4%濃度水溶液 中的 Happier 黏度為 i 至 30 mPas ( H0ppier 法，2〇t 下，DIN 53〇15) 的部分水解的聚乙烯醇。 聚合完成後’可藉由已知方法進行後聚合反應（例如由氧化還 原催化劑引發的後聚合反應）以除去殘留單體。也可藉由蒸館除 去揮發誠料體’較料在減祕件下崎，並魏需要地使 用惰性挾帶氣體例如空氣、氮氣或蒸汽經過混合物中或混合物 上。能夠以此方法獲得的含水分散體具有3〇至75重量％，較佳 50至60重量％的固體含量。 為了製造水可再分散聚合物粉末，視需要在加入作為乾燥助劑 的另外的保護性膠體之後，如藉由流化床乾燥、冷;東乾燥或喷霧 乾燥的方法將分散體乾燥《較佳地，分散體係以喷霧乾燥❶喷霧 乾燥在常用的喷霧乾燥設備中進行，能夠藉由單流體雙流體或 多流體喷嘴或藉由轉盤進行霧化。出口溫度通常選自45。匚至 120 C的範圍，較佳為60 C至90°C，取決於設備、樹脂的Tg和所 欲的乾燥程度。經由固體含量設定待霧化進料的黏度，從而獲得< 500 mPas ( 20 rpm和23。(：下的Brookfield黏度）的數值，較佳為 < 250 mPas的數值《待霧化的分散體的固體含量為>35%，較佳為 12 > 40%。 - 201221499 一般而言，以分散體的聚合物組分計，使用總量為0.5至30重 量％的乾燥助劑，即在乾燥作業之前保護性膠體的總量應為至少1 至30重量％，以聚合物組分計，較佳為使用5至20重量％，以聚 合物組分計。 適合的乾燥助劑為本領域技術人員公知，且為如上述保護性膠 體。較佳為水解度為80至95莫耳％並且在4%濃度水溶液中 Happier 黏度為 1 至 30mPas (20°C 下 Hiippler 法，DIN 53015 )的 部分水解的聚乙烯醇。 在霧化時，以基礎聚合物計，含量最多至1.5重量％的消泡劑常 常被發現是有利的。為了藉由改良結塊穩定性而增加保存時間， 特別是在具有低玻璃轉變溫度的粉末的情況下，可以在所得之粉 末中加入抗結塊劑（防結塊劑），以聚合物組分的總重量計，較佳 為1至30重量％的量。結塊劑的例子是碳酸鈣或碳酸鎂、滑石、 石膏、矽石、高嶺土（如偏高嶺土）、粒徑尺寸較佳在10奈米至 10微米範圍的矽酸鹽。較佳為將聚環氧丙烷或環氧乙烷-環氧丙烷 共聚物組分與水可再分散聚合物粉末組分一起加入用於黏結或抹 面砂漿的乾砂漿配方中。為實現這一目的，在藉由聚合製備聚合 物分散體之前或在所述製備過程中加入聚環氧丙烷或環氧乙烷-環氧丙烷共聚物組分。還可在喷霧乾燥聚合物分散體之前加入聚 環氧丙烷或環氧乙烷-環氧丙烷共聚物組分。 一般而言，藉由在傳統粉末混合設備中將組分a)至d)以及根據 本發明視需要的助黏添加-劑（如果其未與聚合物粉末組分添加） 13 201221499 混合並均質化以製造乾砂漿組合物，從而提梃乾砂漿。在製備前 加入用於加工以得到可立即使用的砂漿所必需的量的水。還可將 單獨的組分a)至d)以及根據本發明視需要的助黏添加劑（如果其 不與聚合物粉末組分加入）分別地與水混合以得到可立即使用的 砂漿。 如果助黏添加劑在正常條件下為液體，則可將其應用於如矽石 的固體支撐材料，並且以該形式將其加入聚合物粉末或乾砂漿組 合物中。 在根據本發明的用途中，較佳將用於複合保溫系統的黏結和抹 面砂漿用於聚乙烯板和岩棉模製品的黏結和加固。 以下實施例用於舉例說明本發明： 在（比較）實施例1至4中，使用以下可再分散聚合物粉末： 分散體粉末1 : 基於Tg為-7°C的乙酸乙烯酯-乙烯共聚物和聚乙烯醇保護性膠 體以及以分散體粉末計1.0重量％的重量平均分子量為約430的聚 丙二醇（BASF的PluriolRP400)的分散體粉末。 分散體粉末2 : 基於Tg為-7°C的乙酸乙烯酯-乙烯共聚物和聚乙烯醇保護性膠 體以及以分散體粉末計1.0重量％的重量平均分子量為約2000的 聚丙二醇（BASF的PluriolRP2000)的分散體粉末。 分散體粉末3 : 201221499 基於Tg為-7。(：的乙酸乙烯酯-體的分散體粉末。 分散體粉末4 : 乙烯共聚物和聚乙烯醇保護性膠 基於Tg為·η：的乙酸乙_•乙稀共聚物和聚乙烯醇保護性膠 體以及以分散體粉末計L0重量％的芳族聚醚的分散體粉末。夕 為了製備.（比較）實施例1至4的可立即使用的砂裝，在每種 情況中將表1所示的組分以其中所示的量與表丨中所示量的水混 合’以得到可立即使用的砂毁。 為了測試砂漿，在每種情況中以4毫米的層厚度將它們作為抹 面砂漿施用至EPS (膨脹聚苯乙烯）板。 在抹面層固化並且將測試樣品保存後’根據DIN 18555·6中的 檢測方法測疋EPS板上的黏結扯離強度（adhesive pull strength ) 和拔出（pull-out)。將樣品在兩種不同的條件下保存： 在23°C和50%相對濕度（SC)下在標準條件下保存14天，或 者在標準條件下保存12天隨後於23°C下在水中保存2天。 測試結果總結於表1中。 結果顯示當使用根據本發明改性的砂漿時與保溫板的黏附有顯 著改良（實施例1和2)，參見實施例1和2與比較實施例3和4 的黏結扯離強度和EPS拔出的比較。具體而言，在水中保存後黏 附僅有不顯著的減弱（實施例1，實施例2)，而在比較實施例的 情況中，黏附結合的品質（其在各情況中皆已偏低）於水中保存 後被進一步顯著破壞（參見EPS拔出）。201221499 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to the use of a polypropylene oxide or an ethylene oxide-propylene oxide copolymer as an adhesion promoting additive in a bonding and plastering mortar for a composite thermal insulation system. [Prior Art] In order to prepare a composite thermal insulation system (CTIS), a thermal insulation board (usually a rigid foamed board composed of polystyrene) is fixed to a masonry building by a bonding mortar, and then the plastering mortar is usually incorporated. The woven fabric or fibers in the layer are applied to the insulation board and the composite system is finally covered with a finishing plaster or plaster. An important property of such bonded mortars and plasters is that the new mortar has good processability and has high flexibility and impact resistance in the cured mortar composition, good water vapor permeability, water repellency, and mineral substrates. Good adhesion, as well as good adhesion to insulation materials, especially polystyrene sheets. In order to obtain optimum properties, the base formulation of the bonding mortar and the plastering mortar is thus modified with a thermoplastic polymer based on an ethylenically unsaturated monomer. The dry mortar containing a mineral binder is usually modified using a water redispersible polymer powder based on the above thermoplastic polymer. This polymer modification provides a mortar composition that meets the above requirements. However, under certain climatic conditions, such as high atmospheric humidity and high temperature environments, the adhesion of the above mortar composition to polystyrene substrates is not satisfactory. In US 2007/0256600 A1, an adhesion promoter for the use of acid mono-, vine, and triacetate is used. However, the expensive price of these additives is a disadvantage. 201221499 Adhesion to polystyrene substrates by the addition of aromatic polyethers is described in EP 0698586 A1. The disadvantage is the emergence of ecological problems with the use of such compounds. It is therefore an object of the present invention to improve the adhesion of the bonding mortar and the plaster to the surface of the polystyrene and to overcome the above disadvantages. This object is achieved by the use of a polypropylene oxide or an ethylene oxide-propylene oxide copolymer. [Inventive content] Polypropylene oxide (polypropylene glycol) is known from EP 0 573 036 B1 as a shrinking additive (shrinkage- Reducing additive ). DE-A 1 935 507 mentions polypropylene glycol as an antifoaming agent for mortar compositions or concrete compositions. In WO 01/04212 A1, a combination of a phenol-formaldehyde condensate and a polyoxyalkylene compound is used to improve the redispersibility of the water redispersible polymer powder. The present invention provides the use of a polypropylene oxide or ethylene oxide-propylene oxide copolymer as a co-adhesive additive for bonding and plastering of composite insulation systems. [Embodiment] A suitable poly(propylene oxide) (polypropylene glycol) of the formula H-[0CH2CH2CH2]n-0H is usually π = 5 to 70, which corresponds to a weight average molecular weight of 400 to 4000 g/mol. It is preferably a polyepoxypropylene having a weight average molecular weight of from 1 to 4 g/m, particularly preferably from 2,000 to 4,000 g/mole. Copolymers comprising ethylene oxide and propylene oxide monomer units (ruthenium-iridium copolymer) and having a weight average molecular weight of 4〇〇201221499 to 4000 g/mole are also suitable. More preferably, it is an EO-PO copolymer having more than 50 mole % PO units. In general, in each case, from 0.05 to 5% by weight, preferably from 0.2 to 2% by weight, of the polypropylene oxide or ethylene oxide-propylene oxide copolymer, based on the amount of polymer powder c) Used to improve adhesion. Adhesive and plastering mortars for use in composite insulation systems are typically provided in the form of a dry mortar composition and mixed with water at the building site. The dry mortar composition comprises a) - or a plurality of mineral binders, b) - or a plurality of fillers; c) one or more based on ethylenically unsaturated monomers and having a glass transition temperature Tg of -25 ° C to +25 °C water redispersible polymer powder; and optionally d) additional additives. Suitable mineral binders a) are cement, especially Portland cement, high alumina cement, tuff cement, slag cement, magnesia cement, phosphate cement or blast furnace slag cement and mixed cement, filled cement, fly ash, micro Powdered, lime and gypsum. It is preferred to use Portland cement, high alumina cement and slag cement as well as mixed cement, filled cement, lime and gypsum. In general, the dry mortar composition comprises, in each case, from 5 to 50% by weight, preferably from 10 to 30% by weight, of the mineral binder, based on the total weight of the dry mortar composition. Examples of suitable fillers b) are cerium sand, quartz powder, calcium carbonate, dolomite, aluminum silicate, clay, chalk, white slaked lime, talc or mica, and lightweight fillers such as pumice, bubble glass, aerated concrete, Perlite, vermiculite, carbon nanotubes (CNT). Any mixture of the fillers can also be used. It is preferably cerium, quartz powder, calcium carbonate, chalk or white slaked lime. In general, in each case, the dry mortar composition comprises from 30 to 90% by weight, 201221499, preferably from 40 to 80% by weight, based on the total weight of the dry mortar composition. Further common additives for dry mortar compositions, d) are thickeners, such as polysaccharides (such as cellulose ethers and modified cellulose ethers), starch ethers, guar gums, trisin, layered oxalic acid Salts, polyacids (such as polyacrylic acid and its partial esters and polyvinyl alcohol which may optionally be acetalized or hydrophobically modified), casein and associative thickeners. Commonly used additives also include retarders such as hydroxycarboxylic acids or dicarboxylic acids or their salts, sugars, oxalic acid, succinic acid, tartaric acid, gluconic acid 'citric acid, sucrose, glucose, fructose, sorbitol, and neopentyl alcohol. A commonly used additive is a coagulant such as an alkali metal salt or an alkaline earth metal salt of an inorganic acid or an organic acid. Additional additives that may be mentioned are: hydrophobic agents, preservatives, film formers, dispersants, foam stabilizers, defoamers, and flame retardants (e.g., hydrazine hydroxide). The additive d) is used in a usual amount depending on the type of the additive. Generally, in each case, the amount is from 0.1 to 10% by weight based on the total weight of the dry mortar composition. The water redispersible polymer powder c) is a powder mixture obtained by drying a corresponding aqueous dispersion of the base polymer in the presence of a protective colloid. Due to this preparation method, the finely divided resin of the dispersion is encapsulated in a sufficient amount of the water-soluble protective colloid. When dry, the protective colloid acts like a shell that prevents the particles from sticking together. When redispersed in water, the protective colloid is redissolved in water and an aqueous dispersion of the original polymer particles is obtained (Schulze J., TIZ, No. 9, 1985). Suitable polymers of ethylenically unsaturated monomers are polymers based on one or more monomers selected from the group consisting of vinyl esters, (meth) acrylates, vinyl aromatic compounds, olefins, 1 , 3-diene and vinyl halides and, if desired, additional monomers of 201221499 copolymerizable therewith. Suitable vinyl esters are the acidified vinyl esters having from 1 to 15 carbon atoms. Preferred is vinyl acetate, vinyl propionate, vinyl butyrate, ethyl 2-ethylhexanoate, vinyl laurate, 1-mercapto vinyl acetate trimethyl vinyl acetate and having 9 to A 4-branched mono-sulphuric acid ethylene ester of 11 carbon atoms, such as VeVa9R or VeoVal 0R (trade name of Resolution). It is especially preferred to be vinyl acetate. Suitable monomers from acrylate or mercapto acrylate are esters of unbranched or branched alcohols having from 丨 to 15 carbon atoms. Preferred mercapto acrylates or acrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, methacrylic acid. Butyl ester, butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate. More preferably, it is methyl propyl acrylate, methyl methacrylate, n-butyl acrylate, acrylic acid, and 2-ethylhexyl acrylate. Preferred vinyl aromatic compounds are styrene, mercaptostyrene and vinyl. A preferred vinyl group is ethylene. Preferred olefins are ethylene and propylene, and preferred monoolefins are 1,3-butadiene and isoprene. It is also possible to copolymerize 〇 to 5% by weight of the auxiliary monomer, based on the total weight of the monomer mixture. It is preferred to use from 5 to 25 % by weight of auxiliary monomers. Examples of auxiliary monomers are ethylenically unsaturated monocarboxylic acids and dicarboxylic acids, preferably acrylic acid methacrylic acid, fumaric acid and maleic acid; ethylenic unsaturated Carbene xamjde and carbonitrile nitriie, preferably acrylamide and acrylonitrile; monoesters and diesters of fumaric acid and maleic acid, such as monoethyl hydrazine and Monoisopropylate and maleic anhydride; ethylenically unsaturated sulfonic acid or a salt thereof, preferably vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, compared to 201221499. Further examples are pre-crosslinking comonomers, such as multiethylenically unsaturated comonomers (eg diallyl phthalate, divinyl adipate, diallyl maleate, methacrylic acid) Allyl ester or triallyl cyanurate), or post-crosslinking comonomer (eg acrylamide glycolic acid (AGA), methacrylamide decyl glycolate (MMAG), N- Hydroxymethyl acrylamide (NMA), N-hydroxydecyl methacrylamide, allyl hydroxyguanidino phthalate, alkyl ethers such as isobutoxy ether or N-methylol propylene oxime An ester of an amine, N-hydroxydecylmercaptodecylamine and allyl N-methylolamine decanoate). Ethylene functional comonomers such as methacrylic acid propylene acrylate and propylene acrylate acrylate are also suitable. Further examples are hydrazine functional comonomers such as propylene methoxy propyl tris (alkoxy) decane and methacryloxypropyl tris (alkoxy) decane, vinyl trialkoxy decane and Vinyl decyl dialkoxy decane wherein, for example, an ethoxy group and an ethoxy propylene glycol ether group may be present in the form of an alkoxy group. Mention may also be made of monomers having a hydroxyl or CO group, such as hydroxyalkyl methacrylate and hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate, Or hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate; and acrylamide such as diacetone and acetoxyethyl acrylate or acetamidine methacrylate a compound of a base ethyl ester). Selecting the weight ratio of monomer to comonomer to obtain -25 ° C to +25 ° C, preferably -10 ° C to + l ° ° C, particularly preferably - l ° ° ° C to ° ° C glass Transition temperature Tg. The glass transition temperature Tg of the polymer (the inflection point of the measurement curve) can be determined in a known manner by differential scanning calorimetry (DSC). Tg can also be calculated approximately in advance according to the Fox equation. According to Fox TG, Bull· Am. Physics Soc. 1, 3, p. 123 (1956): 1/Tg = xl/Tgl + x2/Tg2 + ... + xn/Tgn, where xn is the mass of a single Hn 201221499 rate (wt%/100>, Tgn is the glass transition temperature of the monomer η homopolymer (expressed in absolute temperature). The Tg value of the homopolymer is in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) A copolymer of vinyl acetate and 1 to 50% by weight of ethylene; a vinyl acetate with 1 to 50% by weight of ethylene and 1 to 50% by weight of one or more selected from the group below. Copolymers of other comonomers: vinyl esters having from 1 to 12 carbon atoms in the carboxylic acid group, such as vinyl propionate, vinyl laurate, alpha-branched carboxylic acids having from 9 to 13 carbon atoms a vinyl ester such as VeoVa9, VeoValO, VeoVall; vinyl acetate, 1 to 50% by weight of ethylene and preferably 1 to 60% by weight of an unbranched alcohol or a branched alcohol having 1 to 15 carbon atoms (methyl) a copolymer of an acrylate (particularly n-butyl acrylate or 2-ethylhexyl acrylate); and comprising 30 to 75% by weight Vinyl acetate, 1 to 30% by weight of vinyl laurate or a vinyl ester of an α-branched carboxylic acid having 9 to 11 carbon atoms, and 1 to 30% by weight of unbranched chain having 1 to 15 carbon atoms a copolymer of a (mercapto) acrylate of an alcohol or a branched alcohol (particularly n-butyl acrylate or 2-ethylhexyl acrylate) additionally comprising from 1 to 40 parts by weight per oxime of ethylene; comprising vinyl acetate, 1 a copolymer of up to 50% by weight of ethylene and 1 to 60% by weight of ethylene; wherein the polymer may additionally comprise a specified amount of the abovementioned auxiliary monomers, and the value expressed in % by weight in each case is 100% by weight in total. Also preferred are (meth)acrylic acid S polymers, such as copolymers of n-butyl acrylate or 2-ethylhexyl acrylate or decyl methacrylate with n-butyl acrylate and/or propylene 201221499 a copolymer of 2-ethylhexyl acid; 'styrene-acrylate copolymer having one or more monomers selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate Ester, 2-ethylhexyl acrylate; having one or more selected from Vinyl acetate-acrylate copolymers of monomers in the group: decyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally acetamidine; benzene An ethylene-1,3-butadiene copolymer; wherein the polymer may additionally contain a specified amount of the above auxiliary monomers, and the value expressed in % by weight in each case is 100% by weight in total. The redispersible polymer powder c) comprises: a copolymer comprising vinyl acetate and 5 to 50% by weight of ethylene, or comprising ethylene carbonate, 1 to 50% by weight of ethylene and 1 to 5 % by weight of 9 to 11 a copolymer of a vinyl ester of a carbon-chain alpha-branched monocarboxylic acid, or comprising 30 to 75% by weight of vinyl acetate, 1 to 3 % by weight of vinyl laurate or an α-branched chain having 9 to 11 carbon atoms a vinyl ester of a carboxylic acid and 1 to 3% by weight of a copolymer of a (branched) alcohol or a branched alcohol (meth) acrylate having 1 to 15 carbon atoms, which additionally comprises 1 to 40% by weight of ethylene, Or a total of vinyl acetate, 5 to 50% by weight of ethylene and 1 to 6 % by weight of ethylene The polymer, wherein the polymer may further comprise a specified amount of the above auxiliary monomer, and the value expressed in % by weight in each case is 1 〇〇 by weight / 〇. The 201221499 preparation polymer is prepared by emulsion polymerization or by suspension polymerization in the presence of a protective colloid, preferably by emulsion polymerization, wherein the polymerization temperature is usually from 20 ° C to 10 ° C, preferably. It is from 60 ° C to 90 ° C and that the copolymerization of gaseous comonomers such as ethylene can also be carried out at superatmospheric pressure (typically in the range from 5 bar to 100 bar). The polymerization is initiated by a water-soluble initiator or a monomeric soluble initiator or a redox initiator combination which is commonly used in emulsion polymerization or suspension polymerization. Examples of the water-insoluble initiator are sodium persulfate, hydrogen peroxide, and azobisisobutyronitrile. Examples of the monomeric soluble initiator are di(hexadecyl)peroxydicarbonate, di(cyclohexyl)peroxydicarbonate, and dibenzoyl peroxide. The initiator is usually used in an amount of from 0.01 to 0.5% by weight based on the total weight of the monomers. The redox initiator used is the combination of the initiator and the reducing agent mentioned. Suitable reducing agents are, for example, sodium sulfite, sodium hydroxymethyl sulphate and ascorbic acid. The amount of the reducing agent is preferably from 0.01 to 0.5% by weight based on the total weight of the monomers. In order to control the molecular weight, a conditioning substance can be used during the polymerization. If a regulator is used, it is generally used in an amount of from 0.01 to 5.0% by weight, based on the monomers to be polymerized, and is introduced separately or premixed with the reaction components. Examples of such materials are n-dodecyl mercaptan, tertiary lauryl mercaptan, mercaptopropionic acid, decyl propionate, isopropanol and acetaldehyde. It is preferred not to use a conditioning substance. In order to stabilize the polymerization mixture, a protective colloid is used, optionally in combination with an emulsifier. Suitable protective colloids are partially hydrolyzed or fully hydrolyzed polyvinyl alcohol; polyvinylpyrrolidone; polyacetylated awkward; water soluble forms of polysaccharides such as starch (amylose and amylopectin) Or dextrin or cyclodextrin, cellulose and its carboxymethyl, thiol, hydroxyethyl, hydroxypropyl derivatives; proteins such as casein or road protein salts, soy protein, gelatin; lignin oil (lignosulphonate) 201221499 Synthetic polymer such as poly(fluorenyl)propanyl-(meth)acrylic acid copolymer-free comonomer unit copolymer, poly(methyl)propionamine, poly-binder and its water-soluble Copolymer; melamine-formic acid vinegar, naphthalene-anthraquinone vinegar, styrene-maleic acid and ethylene ether·maleic acid copolymer; cationic lyotropic colloid (for example, having a four-stage Polymer of monomer unit). Preferably, the partially hydrolyzed or fully hydrolyzed polyethylene glycol. More preferably, the partially hydrolyzed polyvinyl alcohol having a degree of hydrolysis of from 8 G to 95 mol% and a Happier viscosity in a 4% aqueous solution of from i to 30 mPas (H0ppier method, 2 〇t, DIN 53〇15). After the completion of the polymerization, post-polymerization (e.g., post-polymerization initiated by an oxidation reduction catalyst) can be carried out by a known method to remove residual monomers. It is also possible to remove the volatilized body by the steaming house, which is used to reduce the secret parts, and to use an inert gas such as air, nitrogen or steam through the mixture or mixture. The aqueous dispersion obtainable by this method has a solid content of from 3 to 75% by weight, preferably from 50 to 60% by weight. In order to produce a water redispersible polymer powder, the dispersion is dried, as desired, by addition of an additional protective colloid as a drying aid, such as by fluidized bed drying, cold, east drying or spray drying. Preferably, the dispersion is spray dried by spray drying in a conventional spray drying apparatus and can be atomized by a single fluid two-fluid or multi-fluid nozzle or by a turntable. The outlet temperature is typically selected from 45. The range of 匚 to 120 C, preferably 60 C to 90 ° C, depends on the equipment, the Tg of the resin, and the desired degree of drying. The viscosity of the feed to be atomized is set via the solid content to obtain a value of < 500 mPas (20 rpm and 23 (: Brookfield viscosity), preferably < 250 mPas, "dispersion to be atomized" The solid content is > 35%, preferably 12 > 40%. - 201221499 In general, a total of 0.5 to 30% by weight of a drying aid is used, based on the polymer component of the dispersion, The total amount of protective colloid before drying should be at least 1 to 30% by weight, based on the polymer component, preferably 5 to 20% by weight, based on the polymer component. Suitable drying aids are in the field. It is well known to the skilled person and is a protective colloid as described above. Preferably, the degree of hydrolysis is from 80 to 95 mol% and the Happier viscosity in a 4% aqueous solution is from 1 to 30 mPas (Hiippler method at 20 ° C, DIN 53015). Hydrolyzed polyvinyl alcohol. Defoaming agents up to 1.5% by weight, based on the base polymer, are often found to be advantageous when atomized. In order to increase the shelf life by improving the stability of the agglomerates, especially in A powder with a low glass transition temperature An anti-caking agent (anti-caking agent) may be added to the obtained powder in an amount of preferably from 1 to 30% by weight based on the total weight of the polymer component. An example of an agglomerating agent is calcium carbonate or Magnesium carbonate, talc, gypsum, vermiculite, kaolin (such as metakaolin), niobate having a particle size of preferably from 10 nm to 10 μm, preferably polypropylene oxide or ethylene oxide-ring The oxypropane copolymer component is added to the dry mortar formulation for bonding or plastering mortar together with the water redispersible polymer powder component. To accomplish this, prior to or during the preparation of the polymer dispersion by polymerization The polypropylene oxide or ethylene oxide-propylene oxide copolymer component is added during the preparation. The polypropylene oxide or ethylene oxide-propylene oxide copolymer group may also be added before the spray drying of the polymer dispersion. In general, by mixing components a) to d) and if necessary in accordance with the present invention in a conventional powder mixing apparatus, if it is not added to the polymer powder component, 13 201221499 Homogenization to make a dry mortar composition, thereby Dry the mortar. The amount of water necessary to process to obtain a ready-to-use mortar is added prior to preparation. The individual components a) to d) and the co-adhesive additives as required according to the invention (if they are not added to the polymer powder component) can also be separately mixed with water to give a ready-to-use mortar. If the co-adhesive additive is a liquid under normal conditions, it can be applied to a solid support material such as vermiculite and added to the polymer powder or dry mortar composition in this form. In the use according to the invention, the bonding and smearing mortar for the composite insulation system is preferably used for the bonding and reinforcement of polyethylene sheets and rock wool moldings. The following examples are intended to illustrate the invention: In (Comparative) Examples 1 to 4, the following redispersible polymer powders were used: Dispersion powder 1 : Vinyl acetate-ethylene copolymer based on Tg -7 ° C And a polyvinyl alcohol protective colloid and 1.0% by weight of a dispersion powder of polypropylene glycol (Pluriol RP400 of BASF) having a weight average molecular weight of about 430, based on the dispersion powder. Dispersion powder 2: based on a vinyl acetate-ethylene copolymer having a Tg of -7 ° C and a polyvinyl alcohol protective colloid and 1.0% by weight of polypropylene glycol having a weight average molecular weight of about 2000 based on the dispersion powder (Pluriol RP2000 of BASF) Dispersion powder. Dispersion Powder 3 : 201221499 Based on a Tg of -7. (: vinyl acetate-body dispersion powder. Dispersion powder 4: ethylene copolymer and polyvinyl alcohol protective adhesive based on Tg: η: acetic acid ethyl acetate copolymer and polyvinyl alcohol protective colloid And a dispersion powder of an aromatic polyether in an amount of L0% by weight based on the dispersion powder. In order to prepare. (Comparative) the ready-to-use sands of Examples 1 to 4, in each case the one shown in Table 1 The components are mixed with the amount of water shown in the table in the amounts indicated therein to give ready-to-use sand. For the purpose of testing the mortars, in each case they are applied as a plastering mortar to a layer thickness of 4 mm to EPS (expanded polystyrene) board. After curing the surface layer and preserving the test sample, 'adhesive pull strength and pull-out (pull-) are measured according to the test method in DIN 18555·6. Out). Store the sample under two different conditions: 14 days at 23 ° C and 50% relative humidity (SC) under standard conditions, or 12 days under standard conditions and then at 23 ° C Stored in water for 2 days. The test results are summarized in Table 1. The results show that there is a significant improvement in adhesion to the thermal insulation board when using the mortar modified according to the present invention (Examples 1 and 2), see the adhesion tear strength and EPS pull-out of Examples 1 and 2 and Comparative Examples 3 and 4. In particular, there was only an insignificant decrease in adhesion after storage in water (Example 1, Example 2), while in the case of the comparative example, the quality of adhesion (which was biased in each case) Low) is further significantly damaged after storage in water (see EPS pull-out).
15 201221499 表1 : 實施例 1 實施例 2 比較實施 例3 比較實施 例4 配方（以重量份數表示的組分） 白水泥42,5 283.5 283.5 283.5 283.5 石夕砂AKW 9a 510 510 510 510 碳酸鈣MHS 190 190 190 190 纖維素醚MH 10001 P4 1.5 1.5 1.5 1.5 分散體粉末1 15 分散體粉末2 15 分散體粉末3 15 分散體粉末4 15 每1000克中的水（毫升） 220 220 220 220 測試結果 黏結扯離強度（牛頓/平方毫 米）（14 天 SC) 0.12 0.12 0.07 0.09 黏結扯離強度（牛頓/平方毫 米） (12 天 SC+2 天 H20) 0.10 0.10 0.04 0.05 EPS 拔出 ％ ( 14 天 SC) 100 95 10 45 EPS拔出％ (12 天 SC+2 天 H20) 90 90 5 25 【圖式簡單說明】 (無） 【主要元件符號說明】 (無） 1615 201221499 Table 1: Example 1 Example 2 Comparative Example 3 Comparative Example 4 Formulation (components in parts by weight) White cement 42, 5 283.5 283.5 283.5 283.5 Shi Xisha AKW 9a 510 510 510 510 Calcium carbonate MHS 190 190 190 190 Cellulose ether MH 10001 P4 1.5 1.5 1.5 1.5 Dispersion powder 1 15 Dispersion powder 2 15 Dispersion powder 3 15 Dispersion powder 4 15 Water per 1000 g (ml) 220 220 220 220 Test results Bonding strength (Newton/mm2) (14 days SC) 0.12 0.12 0.07 0.09 Bonding strength (Newtons/mm2) (12 days SC+2 days H20) 0.10 0.10 0.04 0.05 EPS Pull out % ( 14 days SC 100 95 10 45 EPS pull-out % (12 days SC+2 days H20) 90 90 5 25 [Simple diagram] (none) [Main component symbol description] (None) 16