200401789 玖、發明說明： [發明所屬之技術領域] 本么明關於當作環氧樹脂用硬化劑的含經基之聚鱗胺 基甲酸_胺，關於一種含有這些產物當作調配成分的可固 化組成物’其產生低交聯度的彈性、耐化學性熱固性塑料 ’尤其是經由使用長鏈聚醚胺基甲酸酯胺當作環氧樹脂用 硬化劑。本發明亦關於使用這些可固化組成物於生產模製 品和塗料。 [先前技術] J辰氧樹脂已經廣泛使用於生產防蝕塗料、耐磨塗料、 鑄造用複合物及黏合劑，其具有出色的機械強度和良好的 耐化學性。由於它們的交聯密度，故經胺固化的環氧樹脂 ’尤其那些基於二苯基丙烷和環氧氣丙烷者係硬且脆的， 具有玻璃轉移範圍在20°C以上。 實務上，經胺固化的環氧樹脂之高硬度和高強度係非 經常必要的，而常常希望彈性化及減少脆性。為了這些要 求’至今已經採用各式各樣的方法，但是未必令人滿意。 原則上’可藉由降低交聯密度而内部地及藉由添加塑 化劑而外部地增加彈性化度。 外部彈性化劑係不反應性且不併入熱固性塑料網絡内 匕們猎由填充空隙而將網絡膨服。外部塑化劑包括焦油 、肽酸酯、高沸點醇類、二醇、酮樹脂、乙烯基聚合物及 類似產物，它們不與環氧樹脂和胺硬化劑反應。此種改質 係僅適合於某些用途。其對彈性的貢獻係極小的，因為其 200401789 對於玻璃軟化範圍沒有實質影響，反而大大毁壞熱固性塑 料的結構。可藉由減少硬化劑的官能度而達成環氧樹脂的 内部彈性化’例如敘述於DE-A 22 00 717中。 傳統上有一段長時間，且至可觀的程度，已經有以單 體和二聚㈣酸為基礎的長鏈低官能度胺基醯胺。然而， 以這些胺基醯胺為基礎的熱固性塑料之撓性對許多用途而 言係太低了。 由DE-A 1〇 90 803亦知道藉由含有聚胺基甲酸酯來改 良該些系統。 DE-C 24 18 041揭示一種生產彈性化模製品及片狀結 構之方法其中所用的硬化劑包括DE-C 24 62 791中所述 的聚醚胺，其含有胺基甲酸酯基。 攻些硬化劑產生具有良好彈性的熱固性塑料，但是實 務上發現可固化組成物的相當高黏度將是一種阻礙。再者 ’該些複合物具有差的表面品質。然，良好的表面係所 希望的，尤其當該產品係用當作單層塗料時。 因此本發明一目的為提供一種新的、比較低密度的調 配成分，其用於可固化組成物，&意圖係以它們的特性為 基礎，該調配成分特別地應能產生具有良好表面性質的彈 性化模製品。 [發明内容] 現已令人驚異地發現可用特定的新聚鱗胺基甲酸g旨胺 來達成此目的。本發明因此亦提供―種當作環氧樹月旨用硬 化劑的含㈣之《胺基甲㈣胺，其係由以下步驟所獲 200401789 Α'θ . 付· (a)使聚伸烷基聚醚多元醇與環氧氯丙烷以5:1至ι:1 的莫耳比（較佳1 ·· 1)來進行反應，以產生一種通式⑴的含經 基之聚伸烧二醇單縮水甘油_，可能的話尚含有自由聚伸 烷二醇 R H2C—C—C—O—C—C-~〇—Η Ο Η2 Η, ⑴， 其中R=-H或-CH3，且η=1至100，較佳3至50， (b) 經由式（I)的聚伸烷二醇單縮水甘油醚之羥基，更進 一步地連接至二異氰酸酯或聚異氰酸酯，以產生聚胺基曱 酸酯環氧化物，及 (c) 接著由聚胺基甲酸酯環氧化物和一在每分子中含有 至少兩個反應性胺氫的胺來形成加成物，聚胺基甲酸酯環 氧化物與胺的莫耳比係介於1:1 0和1 ·· 〇 · 5之間，較佳為 作為胺，原則上可能使用那些含有至少兩個反應性胺 氫原子者，例如為雜環胺如呢啡、N-胺基乙基派啡；環脂 族胺如異佛爾酮二胺、1，2-(1，3;1，4)_二胺基環己烷、胺基 丙基環己胺、三環十二烷二胺（TCD);芳脂族胺如伸二曱 苯二胺；脂族，視需要經取代的胺，如伸乙二胺、伸丙二 胺、六亞甲基二胺、2,2,4(2,4,4)·三甲基六亞甲基二胺、2-甲基五亞曱基二胺；醚胺如1，7-二胺基-4-噁庚烷、1，1〇_二 胺基_4,7-二噁癸烷、ι，ΐ4·二胺基-4,7，l〇-三噁十四烷、 1，20-二胺基-4，17_二噁廿烷，尤其ι，12-二胺基_4，、二噁十 200401789 烷。亦可以使用以丙氧基化 的醚二胺（Texaco的，，Jeffamines⑧，^ 一酉予及多兀醇為基礎 伸烷基多胺，二伸乙三胺、二伯。再者，亦可以使用多 —狎乙四胺、- μ 伸丙四胺，及高分子量胺類或加 人：伸丙三胺、三 產物。較佳為使用多伸乙多冑，如伸乙“由胺氫的縮合 、Ν-胺基乙㈣啩及環脂族 ：：、二伸乙三胺 基環己胺。 異佛爾酮二胺或胺丙 依本發明之用於連接聚伸燒二 酸酯係商業上慣用的脂族、芳 、、目7甘油醚的異氰 酸酯或多官能二異氰酸酯以及它三 方鉍一八虱 包括以下者：伸甲苯美-里* " 可提及的例子 π Τ丰暴一異鼠酸酯、丄 、異佛爾酮二異氰酸酯、亞甲基显二：二異氰酸酯 基二異氰酸酯。所用的-里氰t /、虱酉文苯酉曰）、四亞曱 酸酯、六亞甲基二異氰酸酽月里A添 丰悬一異貳 與Μ 4 — 鼠文酉曰及異佛爾酮二異氰酸酯。所列 舉的並不完全，但是不必說，盔 σ 為了連接聚伸燒二醇單缩 甘油鱗’原則上可以使用所有 ~早&水 酯。經由聚伸烷二醇和異氰 虱酉文 町π八齓馱0日的選擇，可以調整性 例如彈性。例如’選擇較短的聚伸貌二醇，則致 少的彈性’或選擇較長的的聚伸炫二醇，則通常導致較多 的撓性。 依此方式所獲得的含經基之預聚合聚鍵腰基甲酸醋係 為比車乂低黏度的液體。本發明的加成物可被使用當作可固 化組成物用的調配成分，較佳為當作生產彈性模製品、塗 料、泡沫H料環氧樹脂之固化劑。作為@化劑時，可單 10 200401789 獨使用聚醚胺基甲酸醋胺或與其它此領域中所慣用的胺硬 化劑混合。 本發明因此又提供一種可固化組成物，其包括⑴一種 在分子中具有平均超過一個環氧化物基的環氧樹脂，及（11) 本發明的含羥基之聚醚胺基甲酸酯胺。（1)對（π)的混合比 一方面係取決於聚醚胺基曱酸酯胺的胺當量，而另一方面 係取決於環氧化合物的環氧化物當量，且量可在i〇phr(每 一百份樹脂I的份）和lOOOphr間。然而為了調整某些性質 ，聚醚胺基曱酸酯胺（II)的用量亦可偏離該理論混合比，且 亦為相對於環氧樹脂而言的次化學計算量或超化學計算量 〇 不僅本發明的含羥基之聚醚胺基甲酸酯胺本身，而且 該可固化組絲，料人驚異地具有比已知胺基醯胺和由 其所製備的可固化組成物遠較低的黏度。再者，本發明之 可固化組成物固化後所獲得的表面之特色為低的結構化程 度及水合物形成以及低程度的油脂膜發展。 該可固化組成物可更包括環氧樹脂科技中所慣用的添 U以及其匕固化劑’尤其胺系固化劑。慣用的胺硬化劑 =脂族胺’例如多伸乙多胺及多伸丙多胺，例如二伸乙三 =一伸丙三胺、2,4,4(2,2,4>三甲基六亞甲基二胺；環脂 族胺5如1-胺基-3-胺基甲基_3,5,5_三甲基環己烷，亦稱為 異佛爾綱二胺，及3,3、二甲基·4,4，_二胺基二環己基甲烷 ;雜環胺，如呢畊；長鏈聚醚胺，如1，丨2-二胺基_4,8·二噁 十一烷，芳族胺，如伸苯二胺、二胺基二苯基甲烷、由中 200401789 性或合成脂肪酸和多胺所形成的聚醯胺基胺；胺加成物； 及s分-酸-胺縮合物。 本發明的含羥基之聚醚胺基曱酸酯胺可依已知的方式 與其它調配用成分如黏度調整劑、加速劑如三級胺、亞磷 酸三苯酯、烷基酚調配，或與快速硬化劑如木尼鹼調配。 以本發明的硬化劑或硬化劑混合物，可熱和冷地固化 所用的環氧樹脂（1)。它們在每分子中含有平均超過一個環 氧化物基且可為單經醇或多經醇如丙三醇、氣化二苯基丙 烷的縮水甘油醚，或為多羥酚，如間苯二酚、二酚基丙烧 · 或盼·ι缩合產物的縮水甘油喊。亦可以使用多元叛酸如六 虱本一曱酸或二聚脂肪酸的縮水甘油醚。 特佳為使用以環氧氯丙烷和二酚基丙烷為基礎的液態 環氧樹脂，其之環氧化物值為04_06環氧化物基/100克 樹脂。 4若須要，亦可以使用當作反應性稀釋劑的單官能脂族 和芳族縮水甘油趟’如丁基縮水甘油祕、苯基縮水甘油醚 丄或縮水甘油酯，如丙烯酸縮水甘油酯，或環氧化物，如 _ 笨乙婦氧化物，或多官能二縮水甘油或三縮水甘油醚，尤 其是具有低分子量者。 使具有低父聯度的長鏈聚醚胺基甲酸酯胺與具有高交 ^性胺調配物組合；係能在寬廣範圍内調整反應性樹脂組 成物的性貝’如黏度、反應性等等，以及調整熱固性塑料 的丨生貝，如彈性、交聯密度、機械強度及耐化學性。 就用於^料、黏合劑黏接或鑄造用的反應性樹脂組成 12 200401789 物之調配物而言，慣用的填料（基於礦物及基於有機者）、 顏料、塑化劑、加速劑、溶劑及其它佐劑係適合的。就泡 沫體的製造而$，可以使用此領域中所慣用的發泡劑，尤 其會放出氫的矽烷化合物。 當需要有效的基材黏附性、良好的耐化學性、橋接基 材中的裂縫及為了減少内部應力，包括在比較低溫需要這 些品質的應用時，可特別有利地採用本發明的組成物。 因此一個重要的用途領域之例子為混凝土之裂縫橋接 用塗料，例如用於工業地板、不可滲透性安全盆或加熱用 _ 油槽。由於它們對於鐵和混凝土對出色的黏附性以及可調 整的彈性，故本發明的組成物附帶地適合當作接合、黏著 及不透液、裂縫-橋接用隔膜。低收縮和低應力的固化亦容 許生產大型模製品或成形零件。 本發明更提供一種製成形零件、塗料和泡沫體的方法 ，其特徵在於使用本發明的可固化組成物來生產該成形零 件。 ’ 本發明更提供一種固化產品，其可由固化本發明的組籲 成物而獲得。 [實施方式] 實施例1 :反應物的寧靖 (A)聚伸烧二醇單縮水分汕μ (Α1)由2000克聚丙二醇（莫耳重量2〇〇〇，oh值： 5 6)(1莫耳）與92·5克環氧氣丙烷（1莫耳），依已知的方法 ，即於三氟化硼醚化物的存在下作加成反應，及於氫氧化 13 200401789 鈉水溶液的存在下開環， 水甘油m有…克聚丙二醇單縮 ，…、有以下特徵：環氧化物值·· 〇 物基/1〇〇克樹脂…量⑽…黏度： 4〇〇mPm Rot()visk。⑧（燒杯裝置）依照礙商規 ;羥基數：26。 (A2)類似於實施例（A1)，由聚乙二醇（莫耳重量 1065)(1莫耳）與92.5克環氧氣丙烧（1莫耳）來製備聚乙二 醇單縮水甘油鍵，其環氧化物值：請環氧化物基/ι〇〇克 樹脂；氣含量（ASTM): G.1%;黏度/2代：豬油狀固體； 羥基數：49。 (A3)類似於實施例（A1)，由丙三醇/環氧丙烷加成物（ 莫耳重量約150〇)(1莫耳）與185克環氧氣丙烷（2莫耳）來 製備二官能縮水甘油醚，其環氧化物值· 〇· 1 〇環氧化物基 /100克樹脂；氣含量（ASTM) : 0.1% ;黏度/25 t : 170mPa*s ;經基數：34。 (b)聚_胺基甲酸酯環氣化物之_借 (Β1)在氮氣下於反應槽内加入2157克聚伸烷二醇單縮 水甘油醚（=1經基當量）（Α1)和0.2克月桂酸二丁錫。在約 60°C，連續添加111克異佛爾酮二異氰酸酯（1異氰酸醋當 K )’其歷經約15分。隨後攪摔混合物3 〇分鐘直到反廡完 成為止。 產物之環氧化物值為0.041莫耳環氧化物/1〇〇克。 (C)聚醚胺基甲酸酯胺之製備 (C1)在氮氣下於反應槽内加入23 80克（1環氧化物當量 14 200401789 )(B 1)下所製備的聚醚胺基甲酸酯環氧化物，及在室溫將 129克（1莫耳）N-胺基乙基派啡（NAEP)計量加入，其歷經 一小時。在NAEP的添加後，將混合物加熱到内溫為100 °C，其歷經30分鐘。隨後在100°C攪拌30分鐘直到反應 完成為止。所得到的含羥基之聚醚胺基甲酸酯胺具有以下 特徵：胺值：（mm KOH/g物質）：45 ;加登納色值：1-2 ; 黏度 3.0Pa*s。 類似於上述實施例，製備表1中所列的加成物。 表1 實施例 PAGMGE1) PAGMGE [莫耳] 異氰酸酯2) 異氰酸酯 [莫耳] 胺3) 胺[莫耳] V4) 2 A1 2 IPDI 1 NAEP 2 3.0 3 A2 2 IPDI 1 NAEP 2 4.9 4 A3 2 TDI 1 NAEP 4 9.7 5 A1 2 TDI 1 ED 350 2 12.0 6 A1 2 MDI 1 XDA 2 2.7 7 A2 2 MDI 1 DETA 2 2.4 8 A2 2 HMDI 1 D230 2 1.9 9 A3 2 HMDI 1 TMD 4 8.8 10 A3 2 TDI 1 DETA 3 16.9 11 A1 2 TDI 1 D230 1.5 3.8 12 A3 2 IPDI 1 XDA 3 19.8 註： 1 PAGMG 聚伸烷二醇單縮水甘油醚 2 IPDI 異佛爾酮二異氰酸酉旨 TDI 伸甲苯基二異氰酸酯 TMDI 四亞甲基二異氰酸酯 MDI 亞曱基二（異氰酸苯酯） HMDI 六亞甲基二異氰酸酯 200401789 3 NAEP 胺基乙基哌畊 ED 350 來自單體脂肪酸的胺基醯, XDA 伸二甲苯二胺 DETA 二伸乙三胺 D 230 聚氧化伸丙二胺（Texaco) TMD 三甲基六亞甲基二胺 4 V 在25C黏度，單位pa*s 應用例 不透液、裂縫橋接用隔膜之實施例 使51.75公斤實施例丨之聚醚胺基甲酸酯胺、914公 斤二曱基六亞甲基二胺（異構物混合物）、9·丨4公斤椰子脂 肪胺、26.73公斤壬基酚及3·25公斤2,4,4•三（二甲基胺基 甲基）酚互相混合，隨後使此混合物與82公斤由86%二酚 基丙烷樹脂（雙酚A，環氧化物值為〇·52環氧化物基/1〇〇 克樹脂）和14%長鏈單官能反應性稀釋劑（以Ερ值〇·33的 C^/Cm脂肪醇為基礎）所構成的混合物進行強烈攪拌。將 混合物展佈在混凝土區域上，以塗覆約3毫米的塗層厚度 。約25公斤的工業標準容器之加工時間在室溫係約3〇分 鐘。 於室溫約24小時後，隔膜係可供使用的，而在室溫7 八使’測里以下物理值·抗拉強度：7.2N/mm2(DIN 54455) ;耐撕裂蔓延性：16.0N/mm2(DIN 54455);伸長率： 980/〇(DIN 53507) 〇 於8 0 C額外地熱老化7天後，在冷卻至室溫後測量以 200401789 下值（23°C /24小時）： 抗拉強度：6.8N/mm2 ;耐撕裂蔓延性：i5 5N/mm2 ; 伸長率：115%。在-10 °C測量以下值：抗拉強度： 28.0N/mm2 ;耐撕裂蔓延性：28·7Ν/ηπη2 ;伸長率：32%。 [跑例14 :不透液、裂縫橋接用隔膜之實施例 使67.30公斤實施例3之聚醚胺基甲酸酯胺、5.69公 斤三甲基六亞甲基二胺（異構物混合物）、5·69公斤椰子脂 肪胺、16.63公斤壬基酚及4_7〇公斤2,4，弘三（二甲基胺基 甲基）酚互相混合，隨後使此混合物與82公斤由86%二酚 基丙烷樹脂（雙酚Α，環氧化物值為〇·52環氧化物基/ι〇〇 克樹脂）和14%長鏈單官能反應性稀釋劑（以Ερ值〇·33的 Cu/Cw脂肪醇為基礎）所構成的混合 將混合物展佈在混凝土區域上，以塗覆約、=米的塗 層厚度。約25公斤的工業標準容器之加工時間在室溫係 約40分鐘。 於室溫約24小時後，隔膜係可供使用#，而在室溫7 天後’測量以下物理值：抗拉強度：12 4N/mm2(DiN 54455);耐撕裂蔓延性：9.2N/mm2(DiN 54455广伸長 59%(DIN 53507) 〇 於8(TC額外地熱老化7天後，在冷卻至室溫後測量以 下值（23t/24小時）： H.4N/mm2 ； 抗拉強度：7.9N/mm2;耐撕裂蔓延性 :抗拉強度·· 伸長率：42%。200401789 发明, Description of the invention: [Technical field to which the invention belongs] The present invention relates to a polyphenylalanine amine containing a warp group as a hardener for epoxy resins, and a curable composition containing these products as a formulation ingredient The composition 'is an elastic, chemically resistant thermosetting plastic which produces a low degree of cross-linking', especially by using a long-chain polyetherurethaneamine as a hardener for epoxy resins. The invention also relates to the use of these curable compositions in the production of molded articles and coatings. [Previous technology] J Chen oxygen resin has been widely used in the production of anti-corrosion coatings, wear-resistant coatings, casting compounds and adhesives, which have excellent mechanical strength and good chemical resistance. Due to their cross-linking density, amine-cured epoxy resins', especially those based on diphenylpropane and epoxypropane, are hard and brittle and have a glass transition range above 20 ° C. In practice, the high hardness and strength of amine-cured epoxy resins are not often necessary, and elasticity and reduced brittleness are often desired. Various methods have been adopted for these requirements', but they are not necessarily satisfactory. In principle, 'the degree of elasticity can be increased internally and externally by adding a plasticizer by reducing the crosslinking density. The external elasticizers are non-reactive and are not incorporated into the thermoset plastic network. The daggers fill the network by filling the voids. External plasticizers include tars, peptidates, high boiling alcohols, glycols, ketone resins, vinyl polymers, and similar products that do not react with epoxy resins and amine hardeners. This modification is only suitable for certain applications. Its contribution to elasticity is minimal because its 200401789 has no substantial effect on the softening range of the glass, but rather greatly destroys the structure of the thermoset plastic. The internal elasticity of the epoxy resin can be achieved by reducing the functionality of the hardener, for example, as described in DE-A 22 00 717. Traditionally for a long time, and to a considerable extent, there have been long-chain, low-functionality aminoamidoamines based on monomers and dimer acid. However, the flexibility of thermosetting plastics based on these aminoamines is too low for many applications. It is also known from DE-A 1090 803 to improve these systems by containing polyurethanes. DE-C 24 18 041 discloses a method for producing elastic molded articles and sheet structures in which the hardener used includes a polyetheramine as described in DE-C 24 62 791, which contains a urethane group. Attacking these hardeners produces thermoset plastics with good elasticity, but in practice it has been found that the relatively high viscosity of the curable composition will be an obstacle. Furthermore, the compounds have poor surface quality. However, a good surface system is desirable, especially when the product is used as a single layer coating. It is therefore an object of the present invention to provide a new, relatively low-density formulating ingredient for use in curable compositions, which is intended to be based on their characteristics. The formulating ingredient should in particular be capable of producing Elastic molding. [Summary of the Invention] It has now surprisingly been found that this purpose can be achieved with a specific novel polyphosphonium amine g. Therefore, the present invention also provides a kind of amidoamine containing amidine as a curing agent for epoxy resin, which is obtained by the following steps: 200401789 Α′θ. Fu · (a) Make polyalkylene The polyether polyol is reacted with epichlorohydrin at a molar ratio of 5: 1 to ι: 1 (preferably 1 ·· 1) to produce a radically-containing polyextruded diol monomer of the general formula ⑴ Glycidyl _, if possible also contains free polyalkylene glycol R H2C—C—C—O—C—C- ~ 〇—Ο 〇 2Η, ⑴, where R = -H or -CH3, and η = 1 To 100, preferably 3 to 50, (b) further connected to a diisocyanate or polyisocyanate via the hydroxyl group of a polyalkylene glycol monoglycidyl ether of formula (I) to generate a polyamino ring Oxide, and (c) an adduct is then formed from a polyurethane epoxide and an amine containing at least two reactive amine hydrogens per molecule, the polyurethane epoxide and Mole ratio of amine is between 1: 10 and 1 ···· 0.5, preferably as amine. In principle, those containing at least two reactive amine hydrogen atoms may be used, such as heterocyclic amines such as Morphine, N-aminoethylpyridine; cycloaliphatic amines such as isophorone diamine, 1,2- (1,3; 1,4) _diaminocyclohexane, aminopropylcyclohexylamine, Tricyclododecanediamine (TCD); araliphatic amines such as dianediophenylenediamine; aliphatic, optionally substituted amines such as ethylenediamine, propylenediamine, hexamethylenediamine, 2,2,4 (2,4,4) · trimethylhexamethylenediamine, 2-methylpentamethylene diamine; ether amines such as 1,7-diamino-4-oxheptane , 1,10-diamino-4,7-dioxane, 1,4,4-diamino-4,7,10-trioxatetradecane, 1,20-diamine-4, 17-dioxanane, especially ι, 12-diamino-4, dioxa 200401789 alkane. It is also possible to use propoxylated ether diamines (Texaco, Jeffamines ⑧, 酉 酉 酉 and polyols based on alkylene polyamines, ethylene glycol triamine, dibo. Also, you can use Poly-tetramethylenetetramine,-μ-methylenetetramine, and high molecular weight amines or additions: polymethylenetriamine, tertiary products. It is preferred to use polymethylenetetramethylene, such as "ethylene condensation by amine hydrogen" , N-aminoacetamidine and cycloaliphatic ::, diethylene glycol trihexyl cyclohexylamine. Isophorone diamine or aminopropyl according to the present invention is used for the connection of polyethylene terephthalate. Commonly used aliphatic, aromatic, and polyisocyanates of triglycerides and polyfunctional diisocyanates and their trismuth bismuths include the following: Tosylate-Li * " Examples that can be mentioned π Acid esters, pyrene, isophorone diisocyanate, methylene hexamethylene: diisocyanate diisocyanate. Used-cyanide t /, glutenyl benzoate, tetramethylene ester, hexamethylene In the month of diisocyanate, A Tianfeng hangs an isocyanate with M 4 —Mormonium and isophorone diisocyanate. The listed ones are not All, but needless to say, the helmet σ can be used in principle to connect polyendocylide monoglycerol scales' all ~ early & water esters. Via polyendanediol and isocyanate 酉 文 町 π 八日 0th The choice can be adjusted, such as elasticity. For example, 'choose a shorter poly-elongated diol, there is less elasticity' or choose a longer poly-elongated diol, which usually results in more flexibility. The base-containing prepolymerized polybonded waist-based formic acid vinegar is a liquid having a lower viscosity than that of carcass. The adduct of the present invention can be used as a formulation component for a curable composition, and is preferably Used as a curing agent for the production of elastic molded products, coatings, and foamed epoxy resins. When used as a chemical, it can be used alone 10 200401789 alone or mixed with other amine hardeners commonly used in this field The present invention therefore provides a curable composition comprising: (i) an epoxy resin having an average of more than one epoxide group in the molecule; and (11) a hydroxyl-containing polyetherurethane amine of the present invention (1) Mixing ratio to (π) It depends on the amine equivalent of the polyetheraminophosphonate amine, and on the other hand it depends on the epoxide equivalent of the epoxy compound, and the amount can be between 100 phr (parts per hundred resin I) and 1,000 phr However, in order to adjust some properties, the amount of polyetheraminophosphonate amine (II) can also deviate from the theoretical mixing ratio, and it is also a substoichiometric or superstoichiometric amount relative to the epoxy resin. 〇Not only the hydroxyl-containing polyetherurethaneamine of the present invention itself, but also the curable group yarn surprisingly has a far lower level than the known amidoamines and curable compositions prepared therefrom. In addition, the surface obtained after curing of the curable composition of the present invention is characterized by a low degree of structuring and hydrate formation, and a low degree of development of a grease film. The curable composition may further include additives commonly used in epoxy resin technology and its curing agent ', especially an amine curing agent. Commonly used amine hardeners = aliphatic amines such as polyethylene glycol and polypropylene glycol, such as ethylene glycol = ethylene glycol triamine, 2,4,4 (2,2,4 > trimethylhexamine Methylene diamine; cycloaliphatic amine 5 such as 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, also known as isophorda diamine, and 3, 3. Dimethyl · 4,4, _diaminodicyclohexylmethane; Heterocyclic amines, such as woolen; Long chain polyetheramines, such as 1, 2-diamino_4,8 · dioxa Monoalkanes, aromatic amines, such as phenylenediamine, diaminodiphenylmethane, polyamidoamines formed from 200,401,789 or synthetic fatty acids and polyamines; amine adducts; and s-acids -Amine condensates. The hydroxyl-containing polyetheraminophosphonate amines of the present invention can be combined with other formulation ingredients such as viscosity modifiers, accelerators such as tertiary amines, triphenyl phosphite, alkyl groups, etc. in a known manner. Formulated with phenol, or with a fast hardener such as Muni base. The hardener or hardener mixture of the present invention can be used to heat and cold cure epoxy resins (1). They contain more than one ring per molecule on average Oxide-based and may be a monohydric alcohol or a polyhydric alcohol such as propane Glycidyl ether of alcohol, vaporized diphenylpropane, or glycidol which is a polyhydric phenol, such as resorcinol, diphenol-based propylene, or pancondensate. Polyvalent acid such as six Glycidyl ether of dibenzylic acid or dimer fatty acid. It is particularly preferred to use liquid epoxy resin based on epichlorohydrin and diphenol propane, whose epoxide value is 04_06 epoxide group / 100 Grams of resin. 4 Monofunctional aliphatic and aromatic glycidols can also be used as reactive diluents if needed, such as butyl glycidol, phenyl glycidyl ether, or glycidyl esters, such as glycidyl acrylate. Esters, or epoxides, such as acetophenone oxide, or polyfunctional diglycidyl or triglycidyl ethers, especially those with a low molecular weight. Make long-chain polyether urethanes with a low degree of parenting. The combination of amines and amine formulations with high crosslinkability; the ability to adjust the properties of the reactive resin composition such as viscosity and reactivity over a wide range; and the adjustment of thermosetting plastics such as elasticity and crosslink density , Mechanical strength and chemical resistance For the formulation of reactive resin composition 12 200401789 for materials, adhesives or casting, conventional fillers (based on minerals and organics), pigments, plasticizers, accelerators , Solvents and other adjuvants are suitable. For the manufacture of foams, foaming agents commonly used in this field can be used, especially silane compounds that emit hydrogen. When effective substrate adhesion and good resistance are required The composition of the present invention can be particularly advantageously used chemically, to bridge cracks in the substrate, and to reduce internal stresses, including applications that require these qualities at relatively low temperatures. Therefore, an example of an important field of use is crack bridging in concrete Coatings, such as for industrial floors, impervious safety basins or heating oil tanks. Due to their excellent adhesion to iron and concrete and adjustable elasticity, the composition of the present invention is incidentally suitable as a diaphragm for bonding, adhesion, and liquid-tight, crack-bridging. Low shrinkage and low-stress curing also allow the production of large molded articles or shaped parts. The present invention further provides a method for forming shaped parts, coatings, and foams, which is characterized by using the curable composition of the present invention to produce the shaped parts. The present invention further provides a cured product obtained by curing the composition of the present invention. [Embodiment] Example 1: The reactant Ningjing (A) poly-elongated diol mono-condensation amount (μ1) consists of 2000 g polypropylene glycol (mole weight 2000, oh value: 5 6) (1 Moore) and 92.5 grams of epoxy propane (1 Moore), according to known methods, in the presence of a boron trifluoride etherate addition reaction, and in the presence of 13 200401789 sodium hydroxide aqueous solution Ring-opening, water glycerol m has ... grams of polypropylene glycol monocondensation, ..., has the following characteristics: epoxide value ... ○ base / 100 grams of resin ... amount ⑽ ... viscosity: 400 mPm Rot () visk. ⑧ (beaker device) in accordance with commercial regulations; hydroxyl number: 26. (A2) Similar to Example (A1), a polyethylene glycol monoglycidyl bond was prepared from polyethylene glycol (mole weight 1065) (1 mole) and 92.5 g of epoxy propane (1 mole), Its epoxide value: please epoxide-based / ιιοg resin; gas content (ASTM): G.1%; viscosity / 2 generation: lard-like solid; hydroxyl number: 49. (A3) Similar to Example (A1), a difunctional was prepared from a glycerol / propylene oxide adduct (mole weight of about 150) (1 mole) and 185 g of epoxy propane (2 moles) Glycidyl ether, its epoxide value · 〇 · 10 epoxide group / 100 grams of resin; gas content (ASTM): 0.1%; viscosity / 25 t: 170mPa * s; warp base: 34. (b) Poly (urethane ring gas) _ (B1) Under nitrogen, add 2157 grams of polybutanediol monoglycidyl ether (= 1 basis equivalent) (Α1) and 0.2 Grams of dibutyltin laurate. At about 60 ° C, 111 g of isophorone diisocyanate (1 isocyanate when K) 'was continuously added, which lasted about 15 minutes. Then stir the mixture for 30 minutes until the reaction is complete. The epoxide value of the product was 0.041 Mo earring oxide / 100 g. (C) Preparation of polyether carbamate amine (C1) 23 80 g (1 epoxide equivalent 14 200401789) of polyether carbamate prepared under nitrogen in a reaction tank under nitrogen Ester epoxide, and 129 grams (1 mole) of N-aminoethylpyrophine (NAEP) was metered in at room temperature over an hour. After the addition of NAEP, the mixture was heated to an internal temperature of 100 ° C for 30 minutes. It was then stirred at 100 ° C for 30 minutes until the reaction was completed. The obtained hydroxyl-containing polyetherurethaneamine has the following characteristics: amine value: (mm KOH / g substance): 45; Gardner color value: 1-2; viscosity 3.0 Pa * s. Similar to the above examples, the adducts listed in Table 1 were prepared. Table 1 Examples PAGMGE1) PAGMGE [Mole] isocyanate 2) Isocyanate [Mole] Amine 3) Amine [Mole] V4) 2 A1 2 IPDI 1 NAEP 2 3.0 3 A2 2 IPDI 1 NAEP 2 4.9 4 A3 2 TDI 1 NAEP 4 9.7 5 A1 2 TDI 1 ED 350 2 12.0 6 A1 2 MDI 1 XDA 2 2.7 7 A2 2 MDI 1 DETA 2 2.4 8 A2 2 HMDI 1 D230 2 1.9 9 A3 2 HMDI 1 TMD 4 8.8 10 A3 2 TDI 1 DETA 3 16.9 11 A1 2 TDI 1 D230 1.5 3.8 12 A3 2 IPDI 1 XDA 3 19.8 Note: 1 PAGMG Polyalkylene glycol monoglycidyl ether 2 IPDI Isophorone diisocyanate purpose TDI Dimethylbenzene diisocyanate TMDI Tetramethylene diisocyanate MDI Methylidene bis (phenyl isocyanate) HMDI Hexamethylene diisocyanate 200401789 3 NAEP Amino ethyl piperidine ED 350 Amine fluorene from monomer fatty acids, XDA xylene diamine DETA Ethylene Triamine D 230 Polyoxypropylene Diamine (Texaco) TMD Trimethylhexamethylene diamine 4 V viscosity at 25C, unit pa * s Application Example Liquid-impermeable, crack bridging diaphragm example 51.75 kg of the polyether urethane amine of Example 丨, 914 kg of difluorenylhexamethylene diamine (Isomer mixture), 9 · 4 kg of coconut fatty amine, 26.73 kg of nonylphenol and 3.25 kg of 2,4,4 · tris (dimethylaminomethyl) phenol are mixed with each other, and then the mixture is made With 82 kg of 86% diphenol-based propane resin (bisphenol A, epoxide value of 0.52 epoxide-based / 100 g resin) and 14% long-chain monofunctional reactive diluent (with Ερ value C./Cm fatty alcohol (based on 0.33) was vigorously stirred. The mixture is spread over the concrete area to apply a coating thickness of about 3 mm. The processing time of an industrial standard container of about 25 kg is about 30 minutes at room temperature. After about 24 hours at room temperature, the diaphragm is ready for use, and at room temperature, the following physical values and tensile strength are measured: 7.2N / mm2 (DIN 54455); tear propagation resistance: 16.0N / mm2 (DIN 54455); Elongation: 980 / 〇 (DIN 53507) 〇 After additional heat aging at 80 C for 7 days, after cooling to room temperature, the value measured at 200401789 (23 ° C / 24 hours): Tensile strength: 6.8N / mm2; Tear resistance: i5 5N / mm2; Elongation: 115%. The following values were measured at -10 ° C: tensile strength: 28.0 N / mm2; tear propagation resistance: 28 · 7N / ηπη2; elongation: 32%. [Run Example 14: An example of a liquid-impermeable, crack-bridging diaphragm uses 67.30 kg of the polyether carbamate amine of Example 3, 5.69 kg of trimethylhexamethylene diamine (isomer mixture), 5.69 kg of coconut fatty amine, 16.63 kg of nonylphenol and 4 to 70 kg of 2,4, bis (dimethylaminomethyl) phenol were mixed with each other, and then this mixture was mixed with 82 kg of 86% diphenol propane Resin (bisphenol A, epoxide value of 0.52 epoxide group per mil of resin) and 14% long-chain monofunctional reactive diluent (using Cu / Cw fatty alcohol with an ρ value of 0.33 as The basic composition) spreads the mixture over the concrete area to apply a coating thickness of approx. The processing time of an industrial standard container of about 25 kg is about 40 minutes at room temperature. After about 24 hours at room temperature, the diaphragm system is ready for use #, and after 7 days at room temperature, the following physical values are measured: tensile strength: 12 4N / mm2 (DiN 54455); tear propagation resistance: 9.2N / mm2 (DiN 54455 wide elongation 59% (DIN 53507)) 〇 After 8 (TC additional 7 days of thermal aging, after cooling to room temperature, the following values were measured (23t / 24 hours): H.4N / mm2; tensile strength: 7.9N / mm2; Tear propagation resistance: Tensile strength · Elongation: 42%.
伸長率·· 52%。在-1(rc測量以下值 18.9N/mm2 ;耐撕裂蔓延性·· 15.4N/mm2 ; 17 200401789 由上述黏結劑調配物開始，亦可以生產經填充的彈性 地板塗料、鑄造用複合物及彈性化黏合劑以及彈性環氧樹 脂/硬化劑泡沫體。Elongation · 52%. The following values are measured at -1 (rc: 18.9N / mm2; resistance to tear propagation ... 15.4N / mm2; 17 200401789 Starting from the above-mentioned adhesive formulations, it is also possible to produce filled elastic floor coatings, casting compounds and Elastic adhesive and elastic epoxy / hardener foam.
1818